CN101851336A - Method for preparing shape-stabilized phase change material by using acrylic fiber waste silks - Google Patents
Method for preparing shape-stabilized phase change material by using acrylic fiber waste silks Download PDFInfo
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- 239000002699 waste material Substances 0.000 title claims abstract description 56
- 239000012782 phase change material Substances 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 22
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 30
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 9
- LGRFSURHDFAFJT-UHFFFAOYSA-N phthalic anhydride Chemical group C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 9
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 8
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 17
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- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
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Abstract
The invention relates to a method for preparing a shape-stabilized phase change material by using acrylic fiber waste silks. The method comprises the following steps of: hydrolyzing the acrylic fiber waste silks into alkali liquid, obtaining an acrylic fiber hydrolysis product through ethanol precipitation, and then swelling and dissolving the acrylic fiber hydrolysis product; and mixing and reacting the acrylic fiber hydrolysis product and a mixture of polyethylene glycol, chain extender, catalyst and solvent to obtain a graft copolymer of the acrylic fiber hydrolysis product and the polyethylene glycol, wherein the graft copolymer has the solid-solid phase change characteristic. The shape-stabilized phase change material prepared by the method has the advantages of high heat enthalpy value, excellent thermal stability, simple preparation method, low cost, reclamation and recycle of the solvent and the like; and the method is a technique capable of realizing resource reutilization, energy conservation and environmental protection, and has broad market application space.
Description
Technical field
The present invention relates to the phase-changing energy storage material technical field, be specifically related to a kind of method of utilizing acrylic fibres waste silk to prepare shaping phase-change material.
Background technology
Current, the countries in the world Economic development is faced with two hang-ups, the one, energy dilemma, the 2nd, environmental pollution jointly.China is acrylic fibers (formal name used at school polyacrylonitrile fibre) production and consumption big countries, domestic market acrylic fibers total amount consumed is about 1,300,000 tons at present, the annual waste and old acrylic fibers total amount that produces is about 100,000 tons, if it is not recycled, can cause environmental pollution on the one hand, can cause the waste of resource on the other hand, therefore strengthen the recycling of waste and old acrylic fibers, turn waste into wealth, not only can realize the regeneration of resource, and reduce environmental pollution, realize Sustainable development, be that cost is low, high efficiency, the competent emerging project of resource, have vast potential for future development.
Different with other thermoplastic polymer, acrylic fibers can not regenerate, can not reclaim monomer with the method for thermo-cracking because of structural reason by heat fusing granulation again, but exist active cyano group (CN), can utilize cyano group to transform, acrylic fibers are reclaimed and utilize in its molecular structure.Existing report obtains polyacrylic acid or sodium polyacrylate with waste and old acrylic fibers hydrolysis, is used to prepare High hydrophilous resin, ion-exchange fiber, drilling well additive etc., but the rarely seen report of using it for the preparation phase change material.
Phase change material can excite the startup neither endothermic nor exothermic under different temperature, when temperature was higher than a certain threshold value, material phase transformation and absorbing heat no longer raise temperature; When temperature is lower than a certain threshold value, material phase transformation and heat release no longer reduces temperature, this supply and demand problem that can effectively alleviate the energy to the storage and the release action of energy in the reversible transformation process, to the recycling of industrial waste heat and waste heat, it is significant to improve rate of energy.
Polyoxyethylene glycol (PEG) enthalpy of phase change height, thermal hysteresis effect be low, do not have be separated, the temperature range of choice is wide, is a kind of polymeric phase change material of excellent performance.The solid-liquid phase change material of the PEG base that document is reported as PEG and inorganic particulate, polypropylene material blend such as (PP), can obtain phase change material, but have problems such as phase change material seepage.The phase change material of the present invention preparation be with the end of the chain of crystallization PEG by chemical reaction be grafted on that fusing point is higher, intensity is big, on the hydrolysate of constitutionally stable skeleton polymer acrylic fibers (being called for short HPAN), therefore when being heated, phase transformation from the crystalline state to the amorphous state takes place in low-melting crystallinity PEG side chain, and the dystectic HPAN main chain that does not melt as yet supports the structure of whole material as framework material, and limited the macro-flow of low melting point PEG, made material still keep solid state on the whole.This phase change material phase transition process form stable, hot energy storage and weather resistance are good, are the phase change materials that has the market development prospect, can obtain in fields such as textile garment, energy-saving building materials and some special dimension such as military project, aerospace to use.
Summary of the invention
Technical problem to be solved by this invention is: a kind of technology and method that utilizes acrylic fibres waste silk to prepare shaping phase-change material is provided, and purpose has two aspects: one provides a kind of acrylic fibres waste silk comprehensive utilization technique; Two provide a kind of energy storage material.Phase change material of the present invention also has higher enthalpy, heat-insulating property preferably except that the characteristics that possess common shaping phase-change material.Therefore it can be used as a kind of new phase change material and is applied in accumulation of heat and energy-saving field widely.
The concrete steps that the present invention realizes are as follows:
The first step, under 130 ℃~150 ℃, with acrylic fibres waste silk hydrolysis 2~3h in 5%~15% alkali lye,, regulate pH to 6~7 with hydrochloric acid by ethanol sedimentation, obtain acrylic fiber hydrolysis product (HPAN).
Second the step, in the A reactor, acrylic fiber hydrolysis product is carried out swelling, dissolving; Add polyoxyethylene glycol, chainextender, catalyzer and solvent in the B reactor, 80~90 ℃ stir 30~60 minutes after, with dissolve in the A reactor, the swollen acrylic fiber hydrolysis product pours the B reactor into; React after 5~15 minutes, occur white flocks in the reactor, this white flocks is the precipitation forms of graft copolymer (HPAN-g-PEG), and it has the fixed phase change feature.
The structure of the shaping phase-change material that is obtained is seen accompanying drawing 1.
Wherein, the number-average molecular weight of polyoxyethylene glycol is 2000~10000.
Chainextender is phthalandione four butyl esters (TBT), and the consumption of phthalandione four butyl esters and the mass ratio of phase change material are 1: 4.17~1: 12.5.
Catalyzer is a dibutyl tin laurate, and catalyst consumption is 1.75%~1.875 (TBT) % of chainextender quality.
In the present invention, in the first step, consider cost and environmental protection, the alkaline hydrolysis temperature of acrylic fibres waste silk is 130~150 ℃, and alkali concn is 5%~10%.
The polyoxyethylene glycol number-average molecular weight is 2000~6000 described in second step, is preferably 4000~6000, to guarantee prepared phase change material higher phase transformation enthalpy and suitable transformation temperature is arranged.
Compare with other disclosed setting phase change energy storage material and preparation method, the present invention has following advantage:
1, the propping material of shaping phase-change material of the present invention is selected the acrylic fibres waste silk hydrolysate, has solved acrylic fibres waste silk and has recycled a difficult problem, has realized resource reutilization, has reduced environmental pollution.
2, the enthalpy of phase change of the prepared shaping phase-change material of the present invention is higher, surpasses 100J/g.
3, the prepared shaping phase-change material of the present invention has good morphological stability and thermostability, even still can keep solid-form Gu temperature reaches 120 ℃.Its reason is the terminal hydroxy group and the acrylic fibres waste silk hydrolysate generation graft copolymerization of polyoxyethylene glycol, polyoxyethylene glycol is fixed on the acrylic fibres waste silk hydrolysate with the form of chemical bond, when phase transformation from the crystalline state to the amorphous state takes place in low-melting crystallinity PEG side chain, the dystectic HPAN main chain that does not melt supports the structure of whole material as framework material as yet, and limited the macro-flow of low melting point PEG, made material still keep solid state on the whole.And make temperature surpass the melt temperature of polyoxyethylene glycol, can not separate, seepage yet.
4, preparation technology of the present invention is simple, the raw material acrylic fibres waste silk price that adopts low, solvent can recycle and reuse, therefore the phase change material that obtains has lower production cost.
Description of drawings
Fig. 1, phase change material characterization of molecules.
The shaping phase-change material polarizing microscope picture that Fig. 2, the inventive method prepare.
The shaping phase-change material DSC graphic representation that Fig. 3, the inventive method prepare.
The shaping phase-change material insulation curve that Fig. 4, the inventive method prepare.
Embodiment
Embodiment 1
The preparation of the first step, acrylic fibres waste silk hydrolysate: PAN waste silk 5g, sodium hydroxide 5g, deionized water 95ml are added in the there-necked flask of 250ml, 130 ℃ of following stirring and refluxing, treat that waste silk dissolves fully, be cooled to room temperature, after adding the ethanol precipitating of 20ml95%, and regulate precipitating thing pH value with 0.1mol/L hydrochloric acid and be slightly less than 7, behind the stirring 30min, be washed till neutrality with ethanol again, 95 ℃ of vacuum-dryings are standby.
The preparation of second step, phase change material: take by weighing 2g acrylic fibres waste silk hydrolysate in the Erlenmeyer flask A of 150mL, add solvent N, dinethylformamide (DMF) 20ml dissolving swelling 2h; Take by weighing polyoxyethylene glycol (6000) 5g, chainextender phthalandione four butyl esters (TBT) 0.8g, catalyzer dibutyl tin laurate 0.015g in the Erlenmeyer flask B of another 150mL, add DMF20ml, stirred 60 minutes in 90 ℃ of lower magnetic forces, pour the solution of acrylic fibres waste silk hydrolysate into Erlenmeyer flask B then, react after 10 minutes, remove solvent with distillation under vacuum, obtain shaping phase-change material.
Above-mentioned shaping phase-change material is carried out polarized light microscope observing, surpassing more than the PEG melt temperature, PEG can not ooze out (see figure 2), and when temperature surpassed 120 ℃, phase change material still kept solid form.This is that PEG is a phase-changing energy storage material because in this phase change material, and the acrylic fibres waste silk hydrolysate is a framework material.Because PEG is connected on the acrylic fibres waste silk hydrolysate macromolecular main chain by chemical bond-linking, although PEG presents solid-liquid phase change in the transformation temperature scope, but be not enough to break away from the macromolecular constraint of acrylic fibres waste silk hydrolysate and can only be completely fixed on the hydrolysate macromolecular skeleton, thereby lost macro-flow.
By differential scanning research (seeing PCM-1 among Fig. 3), prepared phase change material melting peak occurs at 68 ℃, peak crystallization occurs at 35 ℃, and the peak area of peak crystallization is less than melting peak.This is that the PEG macromole is subjected to the constraint of chemical bond because PEG is grafted on the macromolecular side chain of acrylic fibres waste silk hydrolysate, and free active ability is restricted, and can not form perfect crystallization.Calculate as can be known by enthalpy, the enthalpy of prepared phase change material is 106J/g.
Prepared phase change material is carried out the heat retaining property test, by the analysis of cooling curve (see figure 4) as can be known, the prepared phase change material of the present invention begins to occur temperature platform at 43 ℃, and it is on the rise, and temperature platform is kept 8min, illustrates that the prepared phase change material of invention has heat-insulating property preferably.
Embodiment 2
The preparation of the first step, acrylic fibres waste silk hydrolysate: PAN waste silk 5g, sodium hydroxide 10g, deionized water 90ml are added in the there-necked flask of 250ml, 150 ℃ of following stirring and refluxing, treat that waste silk dissolves fully, be cooled to room temperature, after adding the ethanol precipitating of 20ml95%, and regulate precipitating thing pH value with 0.1mol/L hydrochloric acid and be slightly less than 7, behind the stirring 30min, be washed till neutrality with ethanol again, 95 ℃ of vacuum-dryings are standby.
The preparation of second step, phase change material: take by weighing 2g acrylic fibres waste silk hydrolysate in the Erlenmeyer flask A of 150mL, add N, dinethylformamide (DMF) 20ml dissolving swelling 2h; Take by weighing polyoxyethylene glycol (2000) 5g, chainextender phthalandione four butyl esters (TBT) 0.4g, catalyzer dibutyl tin laurate 0.007g in the Erlenmeyer flask B of another 150mL, add DMF20ml, stir 1h in 80 ℃ of lower magnetic forces, pour the solution of acrylic fibres waste silk hydrolysate into Erlenmeyer flask B then, behind the reaction 10min, remove solvent with distillation under vacuum, obtain shaping phase-change material.
Embodiment 3
The preparation of the first step, acrylic fibres waste silk hydrolysate: PAN waste silk 5g, sodium hydroxide 10g, deionized water 90ml are added in the there-necked flask of 250ml, 140 ℃ of following stirring and refluxing, treat that waste silk dissolves fully, be cooled to room temperature, after adding the ethanol precipitating of 20ml95%, and regulate precipitating thing pH value with 0.1mol/L hydrochloric acid and be slightly less than 7, behind the stirring 30min, be washed till neutrality with ethanol again, 95 ℃ of vacuum-dryings are standby.
The preparation of phase change material: take by weighing 4g acrylic fibres waste silk hydrolysate in the Erlenmeyer flask A of 150mL, add N, dinethylformamide (DMF) 20ml dissolving swelling 2h; Take by weighing polyoxyethylene glycol (4000) 5g, chainextender phthalandione four butyl esters (TBT) 0.8g, catalyzer dibutyl tin laurate 0.015g in the Erlenmeyer flask B of another 150mL, add DMF20ml, stir 1h in 80 ℃ of lower magnetic forces, pour the solution of acrylic fibres waste silk hydrolysate into Erlenmeyer flask B then, behind the reaction 10min, remove solvent with distillation under vacuum, obtain shaping phase-change material.
Embodiment 4
The preparation of the first step, acrylic fibres waste silk hydrolysate: PAN waste silk 5g, sodium hydroxide 10g, deionized water 90ml are added in the there-necked flask of 250ml, 140 ℃ of following stirring and refluxing, treat that waste silk dissolves fully, be cooled to room temperature, after adding the ethanol precipitating of 20ml95%, and regulate precipitating thing pH value with 0.1mol/L hydrochloric acid and be slightly less than 7, behind the stirring 30min, be washed till neutrality with ethanol again, 95 ℃ of vacuum-dryings are standby.
The preparation of second step, phase change material: take by weighing 4g acrylic fibres waste silk hydrolysate in the Erlenmeyer flask A of 150mL, add N, dinethylformamide (DMF) 20ml dissolving swelling 2h; Take by weighing polyoxyethylene glycol (6000) 5g, chainextender phthalandione four butyl esters (TBT) 0.4g, catalyzer dibutyl tin laurate 0.007g in the Erlenmeyer flask B of another 150mL, add DMF20ml, stir 1h in 90 ℃ of lower magnetic forces, pour the solution of acrylic fibres waste silk hydrolysate into Erlenmeyer flask B then, behind the reaction 10min, remove solvent with distillation under vacuum, obtain shaping phase-change material.
Embodiment 5
The preparation of acrylic fibres waste silk hydrolysate: PAN waste silk 5g, sodium hydroxide 10g, deionized water 90ml are added in the there-necked flask of 250ml, 140 ℃ of following stirring and refluxing, treat that waste silk dissolves fully, be cooled to room temperature, after adding the ethanol precipitating of 20ml 95%, and regulate precipitating thing pH value with 0.1mol/L hydrochloric acid and be slightly less than 7, behind the stirring 30min, be washed till neutrality with ethanol again, 95 ℃ of vacuum-dryings are standby.
The preparation of phase change material: take by weighing 3g acrylic fibres waste silk hydrolysate in the Erlenmeyer flask A of 150mL, add N, dinethylformamide (DMF) 20ml dissolving swelling 2h; Take by weighing polyoxyethylene glycol (6000) 5g, chainextender phthalandione four butyl esters (TBT) 1.2g, catalyzer dibutyl tin laurate 0.022g in the Erlenmeyer flask B of another 150mL, add DMF20ml, stir 1h with 80 ℃ of lower magnetic forces, pour the solution of acrylic fibres waste silk hydrolysate into Erlenmeyer flask B then, behind the reaction 10min, remove solvent with distillation under vacuum, obtain shaping phase-change material.
Claims (6)
1. method of utilizing acrylic fibres waste silk to prepare shaping phase-change material is characterized in that utilizing the reaction of the hydrolysate grafting polyoxyethylene glycol of acrylic fibres waste silk to obtain shaping phase-change material, and concrete preparation process is as follows:
The first step, under 130 ℃~150 ℃, with acrylic fibres waste silk hydrolysis 2~3h in 5%~15% alkali lye,, regulate pH to 6~7 with hydrochloric acid by ethanol sedimentation, obtain acrylic fiber hydrolysis product;
Second the step, in the A reactor, acrylic fiber hydrolysis product is carried out swelling, dissolving; Add polyoxyethylene glycol, chainextender, catalyzer and solvent in the B reactor, 80~90 ℃ stir 30~60 minutes after, with dissolve in the A reactor, the swollen acrylic fiber hydrolysis product pours the B reactor into; React after 5~15 minutes, occur white flocks in the reactor;
Wherein, chainextender is phthalandione four butyl esters, and catalyzer is a dibutyl tin laurate.
2. a kind of method of utilizing acrylic fibres waste silk to prepare shaping phase-change material according to claim 1, the temperature that it is characterized in that the hydrolysis in alkali lye described in the first step are 130 ℃~150 ℃.
3. a kind of method of utilizing acrylic fibres waste silk to prepare shaping phase-change material according to claim 1 is characterized in that the number-average molecular weight of described polyoxyethylene glycol is 2000~10000, is preferably 4000~6000 in second step.
4. a kind of method of utilizing acrylic fibres waste silk to prepare shaping phase-change material according to claim 1 is characterized in that described chainextender is phthalandione four butyl esters in second step, and the mass ratio of its consumption and phase change material is 1: 4.17~1: 12.5.
5. a kind of method of utilizing acrylic fibres waste silk to prepare shaping phase-change material according to claim 1 is characterized in that described catalyzer is a dibutyl tin laurate in second step, and its consumption is 1.75%~1.875% of a chainextender quality.
6. a kind of method of utilizing acrylic fibres waste silk to prepare shaping phase-change material according to claim 1 is characterized in that the graft reaction temperature is 80~90 ℃ in second step.
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Cited By (3)
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CN102002771A (en) * | 2010-10-21 | 2011-04-06 | 大连工业大学 | Phase-change microcapsule heat storage and temperature adjustment polyacrylonitrile fiber and wet spinning preparation method thereof |
CN102220660A (en) * | 2011-05-20 | 2011-10-19 | 大连工业大学 | Method for preparing high phase transition enthalpy phase transition temperature-adjusting fiber from hydrolysis products of waste acrylic yarn |
CN109690267A (en) * | 2016-07-11 | 2019-04-26 | 因特瑞有限公司 | Time-temperature indicating label |
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Publication number | Priority date | Publication date | Assignee | Title |
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CN102002771A (en) * | 2010-10-21 | 2011-04-06 | 大连工业大学 | Phase-change microcapsule heat storage and temperature adjustment polyacrylonitrile fiber and wet spinning preparation method thereof |
CN102220660A (en) * | 2011-05-20 | 2011-10-19 | 大连工业大学 | Method for preparing high phase transition enthalpy phase transition temperature-adjusting fiber from hydrolysis products of waste acrylic yarn |
CN102220660B (en) * | 2011-05-20 | 2013-04-17 | 大连工业大学 | Method for preparing high phase transition enthalpy phase transition temperature-adjusting fiber from hydrolysis products of waste acrylic yarn |
CN109690267A (en) * | 2016-07-11 | 2019-04-26 | 因特瑞有限公司 | Time-temperature indicating label |
CN109690267B (en) * | 2016-07-11 | 2022-02-01 | 因特瑞有限公司 | Time temperature indicating label |
US11398167B2 (en) | 2016-07-11 | 2022-07-26 | Intray Ltd. | Time temperature indicator label |
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