CN100447316C - Phase-change energy-storage ultra-fine composite fiber and preparation method and application thereof - Google Patents
Phase-change energy-storage ultra-fine composite fiber and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a phase-variable energy storage ultra-fine composite fiber, relative production and application, wherein said fiber can be formed by polymer carrier and phase-variable material in different quality ratio; said phase-variable material is distributed inside the fiber or on the surface of fiber; the phase-variable material on the surface of fiber is crosslinked to the polymer carrier via crosslinker, to be fixed on the surface, to obtain the phase-variable energy-storage ultra-fine composite fiber. The invention can keep the shape of fiber before and after phase change, without phase separation. And it has low cost, simple production and reliable process, to be used in biological and medical material, etc.
Description
Technical field
The present invention relates to a kind of phase-change energy-storage ultra-fine composite fiber, be meant that specifically a kind of is the fixed phase change energy-storage ultra-fine composite fiber and its production and application of carrier with the polymer.
Background technology
Phase-change material has the advantages that thermal storage density is big, hold the approximate isothermal of exothermic process, can reach the purpose that energy stored and discharged and regulated energy supply and demand mismatch, is one of energy storage material of present extensive use.Phase-change material generally is divided into solid-solid phase-change, solid-liquid phase change, solid-gas phase change and liquid-gas phase according to phase transition process and becomes.Because both produce a large amount of gases the back in phase transition process, the phase-change material Volume Changes is big, although bigger enthalpy of phase change is arranged, in actual applications seldom.Therefore, Gu have only solid-and the solid-liquid phase change material be only Focal Point of Common Attention.
The solid-liquid phase change material uses at present both at home and abroad more, but this type of material needs to have increased heat transfer resistance on the one hand with the special installation encapsulation in application, has increased the volume and the cost of system on the other hand.In order to solve the shortcoming of solid-liquid phase change material, setting solid-liquid composite high-molecular phase-change material has appearred, and promptly use the higher macromolecular material of a kind of fusing point as carrier matrix, evenly mix with phase change material, form the high molecular phase change composite.When undergoing phase transition, because the supporting role of carrier matrix, though phase change material is transformed from the solidified state into liquid state, whole composite still can keep the shape and the material property of its solid to a certain extent.For example number of patent application is that " 03129652.1 ", denomination of invention are the patent of invention of " a kind of phase transformation composite spinning stoste and preparation and application ", adopt the high-voltage electrostatic field spining technology that macromolecule carrier and phase change material are dissolved in and carry out spinning in the homogeneous solvent, obtained setting solid-liquid phase change energy-storage fibre.But, because this fibrous material is the simple physical blend of macromolecule and phase change material, and the physical force that is relied between the two relatively a little less than, material after repeatedly using, easily undergo phase transition material and carrier desorption, leak and ooze out and macroscopical two phenomenons such as be separated.
The solid-solid phase transition material coefficient of expansion is less, does not have the cold-peace phenomenon of phase separation, and toxicity corrosivity is little, no leakage problem; Form simultaneously and stablize, the phase transformation good reversibility, long service life, device is simple.Wherein polyalcohols is a class solid-solid phase transition material the most general in the practical application.Yet,, become plastic crystals by crystalline state because polyalcohol is heated to the solid-solid phase-change temperature when above, plastic crystal has very big vapour pressure, is easy to distillation, thereby still needs container encloses when causing it to use, and be airtight pressure vessel, this can not embody the superiority of solid-solid phase transition material.Number of patent application is that " 200510035527.9 ", denomination of invention are the patent of invention of " a kind of nano cellulose solid-solid phase transition material and preparation method thereof ", by heterogeneous system grafting polyethylene glycol on microcrystalline cellulose, made solid-solid phase-change energy-storage material, solved the problem of polyalcohol distillation, but the shortcoming of this material is to cause that the material monolithic enthalpy of phase change is low, heat conductivility is relatively poor because the phase change material percent grafting is low.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art, Gu primary and foremost purpose of the present invention is to provide a kind of enthalpy of phase change height, Heat stability is good, the difficult phase-change energy-storage ultra-fine composite fiber of consolidating-combining with the setting solid-liquid that is separated.
Another object of the present invention is to provide a kind of preparation method of above-mentioned superfine composite fiber.
A further object of the present invention is to provide a kind of application of above-mentioned superfine composite fiber.
Purpose of the present invention is achieved through the following technical solutions: a kind of phase-change energy-storage ultra-fine composite fiber, form by the polymer support and the phase change material of different quality ratio; Described phase change material is distributed in the inside and the surface of superfine composite fiber, and the phase change material that is distributed in the surface is appropriately crosslinked by crosslinking agent and polymer support; The average diameter of described superfine composite fiber is between 50nm～10 μ m; Described polymer support and phase change material by the quality proportioning are: 100 parts of polymer supports, 10～250 parts of phase change materials.
Described phase-change energy-storage ultra-fine composite fiber enthalpy of phase change scope is 5～250J/g, and the phase transition temperature scope is 30～185 ℃.
Described polymer support is natural macromolecular material or artificial synthesized polymer material; Described phase change material is polyalcohols or long-chain fat acids; Described crosslinking agent is binary acids crosslinking agent, dibasic acid anhydride class crosslinking agent or diisocyanates crosslinking agent etc.
Described natural macromolecular material comprises cellulose and derivative, chitin and derivative thereof, starch and derivative thereof.Described cellulose and derivative thereof are cellulose, methylcellulose, ethyl cellulose, cyanethyl cellulose, ethyl cyanide ethyl cellulose, cellulose acetate, Carboxymethyl Cellulose, hydroxyethylcellulose, hydroxypropyl cellulose, carboxymethyl cellulose, and their derivative; Described artificial synthesized polymer material is polyvinyl alcohol, polyvinylpyrrolidone, polystyrene, polymethyl methacrylate, polyvinyl chloride, polyacrylonitrile, polyethylene terephthalate, Merlon, polyurethane or polyethylene glycol oxide etc.
Described polyalcohols is that pentaerythrite, neopentyl glycol, penta glycerol or weight average molecular weight are 1000～35000 polyethylene glycol etc.; Described long-chain fat acids is stearic acid and derivative thereof.
Described binary acids crosslinking agent is ethanedioic acid, succinic acid, glutaric acid or adipic acid etc.; Described dibasic acid anhydride class crosslinking agent is acetic anhydride, maleic anhydride or phthalic anhydride etc., described diisocyanates crosslinking agent is a toluene-2,4-diisocyanate, 1,6-hexylidene diisocyanate, methylenediphenyl diisocyanates, hexamethylene diisocyanate, PPDI or m-benzene diisocyanate etc.
A kind of preparation method of phase-change energy-storage ultra-fine composite fiber comprises the steps:
(1) earlier polymer support and phase change material are dissolved in the solvent by the certain mass ratio, stirring forms blend spinning solution; Described polymer support and phase transition compound by the quality proportioning are: 100 parts of polymer supports, 10～250 parts of phase change materials.
(2) blend spinning solution is carried out spinning by the high-voltage electrostatic spinning method, obtain the superfine fibre of average diameter between 50nm～10 μ m; Described spinning actual conditions is: spinning voltage is 5～70kV, and the distance between spinning head and the collecting board is 5～50cm, and spinning solution sample introduction flow velocity is 0.1～20mL/h, and ambient temperature is 15～35 ℃, and relative air humidity is 40～90%.
(3) immersion of gained superfine fibre is contained in the solution that mass fraction is 1.0～100% crosslinking agents, by adding catalyst or using ultra violet lamp, carry out surface-crosslinked modification 10min～5h, with the superfine fibre drying after the modification, obtain phase-change energy-storage ultra-fine composite fiber then.
Polymer support described in the step (1) is natural macromolecular material or artificial synthesized polymer material; Described phase change material is polyalcohols or long-chain fat acids; Described solvent is water, oxolane, acetone, N, a kind of mixture of or any two kinds of solvents in dinethylformamide, N,N-dimethylacetamide, ethanol, carrene, chloroform, isopropyl alcohol, the hexafluoroisopropanol.
Crosslinking agent described in the step (3) is binary acids crosslinking agent, dibasic acid anhydride class crosslinking agent or diisocyanates crosslinking agent etc.; Described catalyst is that mass fraction is 0.1～1% dibutyl tin dilaurate, 0.1～1% dibutyl diethylene glycol tin, 0.1～1% dibutyl dipropylene glycol tin or dibutyl diallyl tin of 0.1～1% etc.
Above-mentioned phase-change energy-storage ultra-fine composite fiber can be widely used in biological and various fields such as medical material, warming material, high functional material, temperature control protective articles.
The present invention is mixed with blend spinning solution by a certain percentage with polymer support and phase change material, makes the superfine fibre of average diameter in 50nm～10 mu m ranges by the high-voltage electrostatic field spin processes; Carry out appropriately crosslinked to phase change material and the polymer support that is distributed in the superfine fibre surface then, be fixed on the superfine fibre surface, Gu make enthalpy of phase change height, Heat stability is good, the difficult phase-change energy-storage ultra-fine composite fiber of consolidating-combining that is separated with the setting solid-liquid.
The present invention compared with prior art, its advantage and beneficial effect are:
1, phase-change energy-storage ultra-fine composite fiber of the present invention had both had higher enthalpy of phase change; Go up the effect of the chemical bond of crosslinking agent again by the surface, make material in use phase change material be difficult for desorption from carrier, therefore combine the advantage of solid-liquid and solid-solid phase transition material.
2, phase-change energy-storage ultra-fine composite fiber of the present invention, because the average diameter of fiber is at nanometer (50nm～10 μ m) in the micron order scope, so material has huge specific area, good permeability and excellent adjustment performance.
3, the natural polymer carrier selected for use of the present invention cellulose family carrier wide material sources especially are cheap and easy to get, nontoxic; And preparation method's (high-voltage electrostatic spinning method) technology is simple, with low cost, and production process is reliable.
The specific embodiment
The present invention is further described in detail below in conjunction with embodiment, but embodiments of the present invention are not limited thereto.
Embodiment 1
Respectively with acetone and N; the N-dimethylacetylamide mixes with mass ratio at 2: 1; add cellulose acetate (CA; number-average molecular weight 29000, degree of substitution with acetyl group 2.5) being mixed with mass fraction is 15% solution, adds polyethylene glycol-4000 (PEG-4000 then; mass ratio CA: PEG-4000=1: 1); after mechanical agitation evenly forms blend spinning solution,, obtain superfine fibre with carrying out spinning by the high-voltage electrostatic spinning method in its fluid reservoir that has spinning head of packing into.Ambient temperature is 25 ℃ during spinning, and relative humidity is 65%, and the electric field spinning voltage is 12kV, and the distance between spinning head and the collecting board is 15cm, spinning solution sample introduction flow velocity 0.5mL/h.
Then the gained superfine fibre is immersed contain mass fraction be 25.0% 1, in the diethyl ether solution of 6-hexylidene diisocyanate, the adding mass fraction is 0.1% dibutyl tin dilaurate, (25 ℃ of room temperatures, react 4h down down together), take out the back and use deionized water washing 3 times, dry 8h in room temperature, vacuum drying oven.
Measuring its average diameter by stereoscan photograph is 570nm; By the DSC test, enthalpy of phase change is 95.03J/g, and phase transition temperature is 43.7 ℃.
Embodiment 2
Respectively with acetone and N; the N-dimethylacetylamide mixes with mass ratio at 5: 1; add cellulose acetate (CA; number-average molecular weight 29000, degree of substitution with acetyl group 2.5) being mixed with mass fraction is 20% solution, adds polyethylene glycol-10000 (PEG-10000 then; mass ratio CA: PEG-10000=9: 1); after mechanical agitation evenly forms blend spinning solution,, obtain superfine fibre with carrying out spinning by the high-voltage electrostatic spinning method in its fluid reservoir that has spinning head of packing into.Ambient temperature is 20 ℃ during spinning, and relative humidity is 85%, and the electric field spinning voltage is 8kV, and the distance between spinning head and the collecting board is 10cm, spinning solution sample introduction flow velocity 3.0mL/h.
Then the gained superfine fibre is immersed and contain in the toluene solution that mass fraction is 40.0% adipic acid, the adding mass fraction is 0.6% dibutyl tin dilaurate, react 2.5h under the room temperature, take out the back and use deionized water washing 3 times, dry 8h in room temperature, vacuum drying oven.
Measuring its average diameter by stereoscan photograph is 1520nm; By the DSC test, enthalpy of phase change is 5.44J/g, and phase transition temperature is 53.4 ℃.
Embodiment 3
Respectively with acetone and N; the N-dimethylacetylamide mixes with mass ratio at 3: 1; add cellulose acetate (CA; number-average molecular weight 29000, degree of substitution with acetyl group 2.5) being mixed with mass fraction is 12% solution, adds polyethylene glycol-20000 (PEG-20000 then; mass ratio CA: PEG-20000=3: 2); after mechanical agitation evenly forms blend spinning solution,, obtain superfine fibre with carrying out spinning by the high-voltage electrostatic spinning method in its fluid reservoir that has spinning head of packing into.Ambient temperature is 35 ℃ during spinning, and relative humidity is 55%, and the electric field spinning voltage is 35kV, and the distance between spinning head and the collecting board is 25cm, spinning solution sample introduction flow velocity 6.5mL/h.
Then the gained superfine fibre is immersed that to contain mass fraction be in 100% the solution of acetic anhydride, to use 250W ultra violet lamp 1.5h, take out the back and use deionized water washing 3 times, dry 8h in room temperature, vacuum drying oven.
Measuring its average diameter by stereoscan photograph is 920nm; By the DSC test, enthalpy of phase change is 99.92J/g, and phase transition temperature is 60.2 ℃.
Embodiment 4
Respectively absolute ethyl alcohol and carrene are mixed with mass ratio at 2: 1, add hydroxypropyl cellulose (HPC, number-average molecular weight 100000, hydroxypropyl substitution value 1.8) is mixed with mass fraction in and is 10% solution, add then polyethylene glycol-6000 (PEG-6000, mass ratio CA: PEG-6000=2: 3), after mechanical agitation evenly forms blend spinning solution, with carrying out spinning by the high-voltage electrostatic spinning method in its fluid reservoir that has spinning head of packing into, obtain superfine fibre.Ambient temperature is 25 ℃ during spinning, and relative humidity is 75%, and the electric field spinning voltage is 25kV, and the distance between spinning head and the collecting board is 20cm, spinning solution sample introduction flow velocity 1.0mL/h.
Then the gained superfine fibre is immersed and contain in the toluene solution that mass fraction is 50.0% toluene-2,4-diisocyanate, the adding mass fraction is 0.3% dibutyl diethylene glycol tin, react 2h under the room temperature, take out the back and use deionized water washing 3 times, dry 8h in room temperature, vacuum drying oven.
Measuring its average diameter by stereoscan photograph is 1820nm; By the DSC test, enthalpy of phase change is 118.76J/g, and phase transition temperature is 68.5 ℃.
Embodiment 5
Respectively with oxolane and N, the N-dimethylacetylamide mixes with mass ratio at 1: 1, add cyanethyl cellulose (CEC, number-average molecular weight 96000, ethyl substitution value 2.0) is mixed with mass fraction in and is 13% solution, add polyethylene glycol-2000 (PEG-2000 then, mass ratio CEC: PEG-2000=2: 5), after mechanical agitation evenly forms blend spinning solution,, obtain superfine fibre with carrying out spinning by the high-voltage electrostatic spinning method in its fluid reservoir that has spinning head of packing into.Ambient temperature is 20 ℃ during spinning, and relative humidity is 40%, and the electric field spinning voltage is 40kV, and the distance between spinning head and the collecting board is 30cm, spinning solution sample introduction flow velocity 20mL/h.
Then the gained superfine fibre being immersed mass fraction is 100%1, in the solution of 6-hexylidene diisocyanate, the adding mass fraction is 0.5% dibutyl tin dilaurate, reacts 10min under the room temperature, take out the back and use deionized water washing 3 times, dry 8h in room temperature, vacuum drying oven.
Measuring its average diameter by stereoscan photograph is 2850nm; By the DSC test, enthalpy of phase change is 152.35J/g, and phase transition temperature is 41.7 ℃.
Embodiment 6
Respectively with oxolane and N, the N-dimethylacetylamide mixes with mass ratio at 2: 1, join ethyl cellulose (EC, number-average molecular weight 64000, ethyl substitution value 2.8) is mixed with mass fraction in and is 16% solution, add pentaerythrite (PE then, mass ratio EC: PE=1: 1), after mechanical agitation evenly forms blend spinning solution, will carry out spinning by the high-voltage electrostatic spinning method in its fluid reservoir that has spinning head of packing into, obtain fiber, ambient temperature is 25 ℃ during spinning, and relative humidity is 65%, and the electric field spinning voltage is 16kV, distance between spinning head and the collecting board is 20cm, spinning solution sample introduction flow velocity 2.0mL/h.
Then the gained superfine fibre is immersed mass fraction and is 15.0% 1, in the diethyl ether solution of 6-industry hexyl diisocyanate, the adding mass fraction is 0.1% dibutyl tin dilaurate, reacts 5h under the room temperature, take out the back and use deionized water washing 3 times, dry 8h in room temperature, vacuum drying oven.
Measuring its average diameter by stereoscan photograph is 620nm; By the DSC test, enthalpy of phase change is 195.78J/g, and phase transition temperature is 162.5 ℃.
Embodiment 7
Chitin (number-average molecular weight 89000) is dissolved in to be mixed with mass fraction in the hexafluoroisopropanol be 5% solution, (quality is than chitin: neopentyl glycol=3: 2) to add neopentyl glycol then, after mechanical agitation evenly forms blend spinning solution, blend spinning solution packed into carry out spinning by the high-voltage electrostatic spinning method in the fluid reservoir that has spinning head, obtain superfine fibre.Ambient temperature is 15 ℃ during spinning, and relative humidity is 90%, and the electric field spinning voltage is 65kV, and the distance between spinning head and the collecting board is 40cm, spinning solution sample introduction flow velocity 0.1mL/h.
Then the gained superfine fibre is immersed mass fraction and be in the hexane solution of 10.0% PPDI, use 250W ultra violet lamp 3h, take out the back and use deionized water washing 3 times, dry 8h in room temperature, vacuum drying oven.
Measuring its average diameter by stereoscan photograph is 5336nm; By the DSC test, enthalpy of phase change is 65.51J/g, and phase transition temperature is 35.3 ℃.
Embodiment 8
Respectively absolute ethyl alcohol and acetone are mixed with mass ratio at 1: 1, add PVP (PVP, number-average molecular weight 53000) being mixed with mass fraction is 18% solution, add pentaerythrite (PE then, mass ratio PVP: PE=3: 2), after mechanical agitation evenly forms blend spinning solution,, obtain superfine fibre with carrying out spinning by the high-voltage electrostatic spinning method in its fluid reservoir that has spinning head of packing into.Ambient temperature is 25 ℃ during spinning, and relative humidity is 70%, and the electric field spinning voltage is 40kV, and the distance between spinning head and the collecting board is 5cm, spinning solution sample introduction flow velocity 10.0mL/h.
Then the gained superfine fibre is immersed contain 1.0% 1, in the hexane solution of 6-hexylidene diisocyanate, use 250W ultra violet lamp 4.5h, take out the back and use deionized water washing 3 times, dry 8h in room temperature, vacuum drying oven.
Measuring its average diameter by stereoscan photograph is 6850nm; By the DSC test, enthalpy of phase change is 188.56J/g, and phase transition temperature is 180.23 ℃.
Embodiment 9
With polyacrylonitrile (PAN, number-average molecular weight 45000) is dissolved in N, be mixed with mass fraction in the dinethylformamide and be 12% solution, add polyethylene glycol-6000 (PEG-6000 then, PAN: PEG-6000=10: 1), after mechanical agitation evenly forms blend spinning solution,, obtain superfine fibre with carrying out spinning by the high-voltage electrostatic spinning method in its fluid reservoir that has spinning head of packing into.Ambient temperature is 20 ℃ during spinning, and relative humidity is 60%, and the electric field spinning voltage is 20kV, and the distance between spinning head and the collecting board is 10cm, spinning solution sample introduction flow velocity 15.0mL/h.
Then the gained superfine fibre is immersed and contain in the toluene solution that mass fraction is 30.0% PPDI, the adding mass fraction is 1.0% dibutyl tin dilaurate, react 4h under the room temperature, take out the back and use deionized water washing 3 times, dry 8h in room temperature, vacuum drying oven.
Measuring its average diameter by stereoscan photograph is 830nm; By the DSC test, enthalpy of phase change is 5.65J/g, and phase transition temperature is 55.0 ℃.
Embodiment 10
Respectively with N, dinethylformamide and toluene mix with mass ratio at 1: 9, add polymethyl methacrylate (PMMA, number-average molecular weight 63000) being mixed with mass fraction is 10% solution, add pentaerythrite (mass ratio PMMA: PA=3: 7) then, after mechanical agitation evenly forms blend spinning solution,, obtain superfine fibre with carrying out spinning by the high-voltage electrostatic spinning method in its fluid reservoir that has spinning head of packing into.Ambient temperature is 25 ℃ during spinning, and relative humidity is 45%, and the electric field spinning voltage is 70kV, and the distance between spinning head and the collecting board is 50cm, spinning solution sample introduction flow velocity 6.0mL/h.
Then the gained superfine fibre is immersed in the diethyl ether solution contain 85.0% hexamethylene diisocyanate, add mass fraction again and be 0.8% dibutyl tin dilaurate, react 3h under the room temperature, take out the back and use deionized water washing 3 times, dry 8h in room temperature, vacuum drying oven.
Measuring its average diameter by stereoscan photograph is 8340nm; By the DSC test, enthalpy of phase change is 250.30J/g, and phase transition temperature is 178.6 ℃.
Embodiment 11
With polyethylene glycol oxide (PEO, number-average molecular weight 58000) is dissolved in that to be mixed with mass fraction in the chloroform be 6% solution, add polyethylene glycol-1000 (PEG-1000 then, PEO: PEG-1000=1: 1), after mechanical agitation evenly forms blend spinning solution, with carrying out spinning by the high-voltage electrostatic spinning method in its fluid reservoir that has spinning head of packing into, obtain superfine fibre.Ambient temperature is 25 ℃ during spinning, and relative humidity is 60%, and the electric field spinning voltage is 5kV, and the distance between spinning head and the collecting board is 15cm, spinning solution sample introduction flow velocity 1.5mL/h.
Then the gained superfine fibre is contained and immerse that to contain mass fraction be in 100% the phthalic acid anhydride solution, to use 250W ultra violet lamp 2h, take out the back and use deionized water washing 3 times, dry 8h in room temperature, vacuum drying oven.
Measuring its average diameter by stereoscan photograph is 1120nm; By the DSC test, enthalpy of phase change is 65.22J/g, and phase transition temperature is 34.1 ℃.
Embodiment 12
With polyvinyl alcohol (PVA, number-average molecular weight 72000) is dissolved in that to be mixed with mass fraction in the deionized water be 7% solution, add polyethylene glycol-10000 (PEG-10000 then, PVA: PEG-10000=7: 3), after mechanical agitation evenly forms blend spinning solution, with carrying out spinning by the high-voltage electrostatic spinning method in its fluid reservoir that has spinning head of packing into, obtain superfine fibre.Ambient temperature is 22 ℃ during spinning, and relative humidity is 60%, and the electric field spinning voltage is 25kV, and the distance between spinning head and the collecting board is 15cm, spinning solution sample introduction flow velocity 2.5mL/h.
Then the gained superfine fibre is contained to immerse and contain in the toluene solution that mass fraction is 5.0% adipic acid, the adding mass fraction is 0.7% dibutyl dipropylene glycol tin, react 5h under the room temperature, take out the back and use ether washing 3 times, dry 8h in room temperature, vacuum drying oven.
Measuring its average diameter by stereoscan photograph is 820nm; By the DSC test, enthalpy of phase change is 35.58J/g, and phase transition temperature is 58.6 ℃.
As mentioned above, can realize the present invention preferably.
Claims (7)
1, a kind of preparation method of phase-change energy-storage ultra-fine composite fiber is characterized in that comprising the steps:
(1) earlier polymer support and phase change material are dissolved in the solvent by the certain mass ratio, stirring forms blend spinning solution; Described polymer support and phase change material by the quality proportioning are: 100 parts of polymer supports, 10～250 parts of phase change materials;
(2) blend spinning solution is carried out spinning by the high-voltage electrostatic spinning method, obtain the superfine fibre of average diameter between 50nm～10 μ m; Described spinning actual conditions is: spinning voltage is 5～70kV, and the distance between spinning head and the collecting board is 5～50cm, and spinning solution sample introduction flow velocity is 0.1～20mL/h, and ambient temperature is 15～35 ℃, and relative air humidity is 40～90%;
(3) immersion of gained superfine fibre is contained in the solution that mass fraction is 1.0～100% crosslinking agents, by adding catalyst or ultra violet lamp, carry out surface-crosslinked modification 10min～5h, with the superfine fibre drying after the modification, obtain phase-change energy-storage ultra-fine composite fiber then;
Described catalyst is that mass fraction is 0.1～1% dibutyl tin dilaurate, 0.1～1% dibutyl diethylene glycol tin, 0.1～1% dibutyl dipropylene glycol tin or 0.1～1% dibutyl diallyl tin.
2, the preparation method of a kind of phase-change energy-storage ultra-fine composite fiber according to claim 1 is characterized in that: the described phase-change energy-storage ultra-fine composite fiber enthalpy of phase change scope for preparing is 5～250J/g, and the phase transition temperature scope is 30～185 ℃.
3, the preparation method of a kind of phase-change energy-storage ultra-fine composite fiber according to claim 1 is characterized in that: the polymer support described in the step (1) is natural macromolecular material or artificial synthesized polymer material; Described phase change material is polyalcohols or long-chain fat acids; Described solvent is water, oxolane, acetone, N, a kind of mixture of or any two kinds of solvents in dinethylformamide, N,N-dimethylacetamide, ethanol, carrene, chloroform, isopropyl alcohol, the hexafluoroisopropanol;
Crosslinking agent described in the step (3) is binary acids crosslinking agent, dibasic acid anhydride class crosslinking agent or diisocyanates crosslinking agent.
4, the preparation method of a kind of phase-change energy-storage ultra-fine composite fiber according to claim 3 is characterized in that: described natural macromolecular material comprises cellulose and derivative, chitin and derivative thereof or starch and derivative thereof; Described artificial synthesized polymer material is polyvinyl alcohol, polyvinylpyrrolidone, polystyrene, polymethyl methacrylate, polyvinyl chloride, polyacrylonitrile, polyethylene terephthalate, Merlon, polyurethane or polyethylene glycol oxide.
5, the preparation method of a kind of phase-change energy-storage ultra-fine composite fiber according to claim 4 is characterized in that: described cellulose and derivative thereof are cellulose, methylcellulose, ethyl cellulose, cyanethyl cellulose, cellulose acetate, Carboxymethyl Cellulose, hydroxyethylcellulose, hydroxypropyl cellulose or carboxymethyl cellulose.
6, the preparation method of a kind of phase-change energy-storage ultra-fine composite fiber according to claim 3 is characterized in that: described polyalcohols is that pentaerythrite, neopentyl glycol, penta glycerol or weight average molecular weight are 1000～35000 polyethylene glycol; Described long-chain fat acids is stearic acid and derivative thereof.
7, the preparation method of a kind of phase-change energy-storage ultra-fine composite fiber according to claim 3 is characterized in that: described binary acids crosslinking agent is ethanedioic acid, succinic acid, glutaric acid or adipic acid; Described dibasic acid anhydride class crosslinking agent is acetic anhydride, maleic anhydride or phthalic anhydride; Described diisocyanates crosslinking agent is a toluene-2,4-diisocyanate, 1,6-hexylidene diisocyanate, methylenediphenyl diisocyanates, hexamethylene diisocyanate, PPDI or m-benzene diisocyanate.
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