CN1312249C - Nano cellulose solid-solid phase transition material and its preparing method - Google Patents
Nano cellulose solid-solid phase transition material and its preparing method Download PDFInfo
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Abstract
The present invention relates to a nano cellulose microcrystalline solid-solid phase change material and a preparation method thereof. The present invention is characterized in that 19.8 to 82.0% of polyethylene glycol comprising active groups at one end or two ends, 0 to 55.1% of cross-linking agent and 4.0 to 69.5% of reactant with nano cellulose microcrystalline or derivatives thereof are added in a heterogeneous system, the polyethylene glycol comprising active groups at one end or two ends is used as an energy storage functional group and is grafted to a framework material of the nanometer cellulose microcrystalline or the derivatives thereof via ultraviolet radiation. The nano cellulose microcrystalline solid-solid phase change material of the present invention has the maximum phase change enthalpy of more than 110 J/g, phase change temperature is from 0 to 60 DEG C, the material can keep a good solid state before and after the phase change and can not generate phase separation, etc. The present invention has the advantages of no toxicity, no harm, low cost and simple preparation process and can be widely used on the occasions of fabrics, solar energy utilization, phase change energy storage air conditioners, glass houses, temperature control devices, etc.
Description
Technical field
The present invention relates to a kind of phase change material, relate to a kind of nano-cellulose solid-solid phase change material specifically, also relate to the preparation method of this phase change material.
Background technology
Phase change material is the energy storage material of present widespread use, and along with the arrival of energy dilemma, it is used in real life will be more extensive.According to the difference of phase transformation mode, phase change material can be divided into solid-liquid phase change material and solid-solid phase transition material.The most frequently used phase change material is the solid-liquid phase change material both at home and abroad at present, but because it has liquid phase to generate in phase transition process, must encapsulate and could use with container, otherwise has the danger of liquid phase leakage and corrosion and contaminate environment.And shortcomings such as that solid-liquid phase change material liquid material generally also existed was cold, be separated, energy-storage property decline and packaging container price height.
Common solid-solid phase transition material has polyalcohols and high score subclass, wherein the polyalcohols energy storage material is being heated more than the solid-solid phase-change temperature, when becoming plastic crystals by the crystalline state solid, because of plastic crystal has very big vapour pressure, volatile loss, so that still need use container sealing when it uses, also be difficult to widespread use.Macromolecular grafted class solid-solid phase transition material is the energy storage material that application prospect is arranged most by contrast, its stable performance, but general straight forming, and needn't be contained in the container.But the enthalpy of phase change of this class phase change material that makes at present is less, and stability neither be fine.The preparation method of present macromolecular grafted class solid-solid phase-change energy-storage material mainly is to use linking agent by chemical heat polymeric method the energy storage group to be grafted on the framework material, in Chinese patent ZL99117105.5 and ZL99117071.7, be in homogeneous system, use linking agent phase change material and certain carrier matrix to be combined by thermopolymerization.It seems on the macroscopic view, taken place crosslinked between energy storage group and the framework material, but from microcosmic, homopolymerization has taken place in this phase change material to a great extent, promptly there are the framework material and the framework material of very big part crosslinked, energy storage group and energy storage group are crosslinked, phenomenons such as this just makes and may be separated in the phase transformation use, liquid phase leakage, thereby the preparation technology of this phase change material also becomes complicated more.In United States Patent (USP) [US 863 274 (1992)] and [US371 779 (1989)], then be to adopt chemical method to prepare phase change material, not only the enthalpy of phase change of phase change material is little, and the stability of material is also bad.
Summary of the invention
The objective of the invention is to develop a kind of non-homopolymerization and the stable solid-solid phase transition material that high enthalpy of phase change is arranged.Another purpose is to develop the preparation method of this phase change material.
The present invention utilizes polyoxyethylene glycol and the nano-cellulose or derivatives thereof that UV-irradiation contains active group with one or both ends to carry out radical polymerization, polyoxyethylene glycol is grafted on the nano-cellulose high-molecular bone frame material as the energy-storage function group, can both keep good solid state before and after the solid-solid phase transition material material phase transformation that obtains, stable performance, enthalpy of phase change is big, the generation of no homopolymer, thus realized purpose of the present invention.
A kind of nano cellulose solid-solid phase transition material of the present invention, its structure is that the polyoxyethylene glycol that active group is contained in one or both ends is fixed on the high-molecular bone frame material, it is characterized in that this high-molecular bone frame material is the nano-cellulose or derivatives thereof, and be in nonhomogeneous system, obtained by the following reactant reaction of forming: reaction-ure mixture is a massfraction 100%, wherein to contain the polyoxyethylene glycol of active group be 19.8%～82.0% in one or both ends, linking agent be 0%～55.1% and the nano-cellulose or derivatives thereof be 4.0%～69.5%.
The active group of described polyoxyethylene glycol can be hydroxyl or carboxyl, the relative molecular mass of described polyoxyethylene glycol preferably 400～10000.
Described nano-cellulose derivative can be the nano-cellulose through chemically modified, for example with nano-cellulose hydroxyl carboxymethylation, hydroxyethylation, acylations etc.
Described linking agent can be an acrylic acid or the like, the acrylate chloride class, acrylic amide, epoxies, the dibasic acid anhydride class, diisocyanate compound, wherein the diisocyanates linking agent can be a tolylene diisocyanate, 4, the 4-diphenylmethanediisocyanate, hexamethylene diisocyanate), 1, the 5-naphthalene diisocyanate, 2,6-two isocyanato methyl caproates, the mphenylenedimethylim-vulcabond, PPDI, m-benzene diisocyanate etc., the epoxies linking agent can be an oxyethane, epoxy chloropropane, the mixture of one or more in the propylene oxide, dibasic acid anhydride class linking agent can be maleic anhydride or diacetyl oxide etc.
The preparation method of a kind of nano cellulose solid-solid phase transition material of the present invention, it is characterized in that being reacted by the following reactant of forming: reaction-ure mixture is a massfraction 100%, wherein the polyoxyethylene glycol 19.8%～82.0% of active group is contained in one or both ends, linking agent 0%～55.1% and nano-cellulose or derivatives thereof 4.0%～69.5%, its reaction may further comprise the steps:
(1) with solvent polyoxyethylene glycol, the linking agent wiring solution-forming of active group, nano-cellulose or derivatives thereof solvent dispersion are contained in one or both ends respectively;
(2) with above-mentioned join one or both ends contain the polyglycol solution of active group and nano-cellulose or derivatives thereof dispersion liquid separately or together or successively with linking agent or step (1) join cross-linking agent solution mixes, react;
(3) step (1) is joined one or both ends contain the polyglycol solution of active group and reaction solution that nano-cellulose derivative dispersion liquid mixes or step (2) is obtained mixes, in the presence of photosensitizers, in the ultraviolet producer, react, with gained reaction product drying.
The active group of the polyoxyethylene glycol described in the described preparation method can be hydroxyl or carboxyl, as carboxymethyl, propyloic etc., and the relative molecular mass of described polyoxyethylene glycol preferably 400～10000; It is spherical or bar-shaped that described nano-cellulose is, described nano-cellulose derivative can be the nano-cellulose through chemically modified, for example, can not use linking agent when making framework material among the preparation method with the nano-cellulose of hydroxyl carboxymethylation, acylations with nano-cellulose hydroxyl carboxymethylation, hydroxyethylation, acylations etc.; Described linking agent can be acrylic acid or the like, acrylate chloride class, acrylic amide, dibasic acid anhydride class, diisocyanate compound etc., wherein the diisocyanates linking agent can be a tolylene diisocyanate, 4,4-diphenylmethanediisocyanate, hexamethylene diisocyanate), 1,5-naphthalene diisocyanate, 2,6-two isocyanato methyl caproates, mphenylenedimethylim-vulcabond, PPDI, m-benzene diisocyanate etc., dibasic acid anhydride class linking agent can be maleic anhydride or diacetyl oxide etc.
The solvent that is used to dissolve described polyoxyethylene glycol, linking agent in the described step (1) can be methylene dichloride, benzene, toluene or acetone etc.; Can also add basic metal as properties-correcting agent; The solvent that is used for the plain or derivatives thereof framework material of dispersion of nanofibers can be dimethyl formamide, N,N-DIMETHYLACETAMIDE or dimethyl sulfoxide (DMSO) etc.
Preferably adopt the method that drips in the described step (2), described polyglycol solution and nano-cellulose or derivatives thereof dispersant liquid drop can be joined in linking agent or its solution, also linking agent or its drips of solution can be added in above-mentioned two liquid, reaction can catalyzer and or stopper in the presence of carry out, catalyzer and stopper can with the described polyglycol solution of adding before linking agent mixes with or nano-cellulose or derivatives thereof dispersion liquid in, described catalyzer can be a pyridine, triethylamine or tosic acid etc., described stopper can be Resorcinol, benzoquinones etc.
Photosensitizers described in the described step (3) can be fragrant ketone such as benzophenone, thioxanthone etc.; Described ultraviolet producer can adopt commercially available each model, and generator power influences the reaction times, and the reaction times that power greatly then needs is short, the little long reaction time that then needs of power.
The enthalpy of phase change maximum of nano cellulose solid-solid phase transition material of the present invention can reach more than the 110J/g, and transformation temperature is at 0～60 ℃, and can both keep good solid state before and after phase transformation, and phenomenon such as can not be separated.
The present invention compares with Chinese patent ZL99117105.5 and ZL99117071.7 and has the following advantages:
1. the present invention adopts ultraviolet Technology to prepare phase change material, has simplified the preparation process of phase change material, and has avoided the homopolymerization phenomenon of thermopolymerization, and the phase change material that obtains can not be separated, and is a kind of solid-solid phase transition material truly;
2. the present invention selects for use nano-cellulose as framework material, be spherical or bar-shaped nano-cellulose owing to use, thereby it is little to have size, specific surface area is big, the chemical reactivity advantages of higher, make the percentage of grafting of energy-storage function base on framework material improve greatly, thereby phase change material has had higher enthalpy of phase change;
3. applied in the above-mentioned patent is Microcrystalline Cellulose, particle is bigger, ventilation property was poor when made phase change material was used for fabric, and the present invention uses nano-cellulose as framework material, its particle is less, when being used as fabric fibre, ventilation property, static resistance, water-absorbent etc. is preferably arranged, and do not need propping material, can use separately.
Because above-mentioned advantage, phase change material of the present invention can be widely used in multiple occasions such as fabric, sun power utilization, phase change energy-storage type air-conditioning, glasshouse, temperature control equipment, because it is nontoxic, cost is low, preparation technology is simple, is with a wide range of applications.
Embodiment
Following embodiment further specifies of the present invention, but the invention is not restricted to following embodiment.
Embodiment 1:
Taking by weighing average molecular mass and be 6000 polyoxyethylene glycol 20 grams is dissolved in 30 milliliters the methylene dichloride and obtains solution, measuring 10 milliliters of acrylate chlorides (about 11.138g) is dissolved in 15 milliliters the methylene dichloride and obtains solution, and be divided into two parts, take by weighing nano-cellulose 2 gram make its be dispersed in the dimethyl formamide suspension; In polyglycol solution, add several pyridine catalysts (about 0.9g), under 0 ℃, respectively polyglycol solution and nano-cellulose suspension are added drop-wise in the acrylate chloride solution in batches, and slowly stir, react after 6 hours, above-mentioned two reaction solutions are poured on to be mixed together stir, add the 1.6g benzophenone, then mixed solution is put into ultraviolet producer (GE:LU400/T/40; 400W), use UV-irradiation 1h, at last with the product drying, obtain nano cellulose solid-solid phase transition material of the present invention, recording its enthalpy of phase change is 112J/g.
Embodiment 2:
Take by weighing average molecular mass and be 6000 poly glycol monomethyl ether 20 grams be dissolved in 60 milliliters of acetone solution, take by weighing nano-cellulose 2 grams make its be dispersed in the N,N-DIMETHYLACETAMIDE suspension; In poly glycol monomethyl ether solution and nano-cellulose suspension, add catalyzer tosic acid and stopper benzoquinones respectively, in poly glycol monomethyl ether solution and nano-cellulose suspension, dripping about 2.3 milliliters (about 2.415g) of excessive propene acid under 80～100 ℃ respectively, react after 10 hours, poly glycol monomethyl ether and vinylformic acid reaction solution joined in nano-cellulose and the vinylformic acid reaction solution stir, add 1.2g photosensitizers benzophenone, then mixed solution is put into ultraviolet producer (GE:LU400/T/40; 400W), use UV-irradiation 1h, at last with the product drying, promptly obtain nano cellulose solid-solid phase transition material of the present invention, and this phase change material is carried out the DSC test, its enthalpy of phase change is 56J/g.
Embodiment 3:
Take by weighing average molecular mass and be 4000 polyoxyethylene glycol 20 grams be dissolved in 50 milliliters of toluene solution, take by weighing nano-cellulose 2 grams make its be dispersed in the dimethyl formamide suspension; In polyglycol solution, added 0.1 gram sodium stirring reaction 12 hours, and after filtering, under 0 ℃, in solution, dripped acrylate chloride 5 milliliters (about 5.569g) again and continue reaction 10 hours; Directly in nano-cellulose suspension, dripping 5 milliliters of reactions of acrylate chloride 6 hours under 0 ℃; Polyoxyethylene glycol and acrylate chloride reaction solution poured in nano-cellulose and the acrylate chloride reaction solution stir, add 1.6g photosensitizers benzophenone, then mixed solution is put into ultraviolet producer (GE:LU400/T/40; 400W), use UV-irradiation 1h, the product drying promptly gets nano cellulose solid-solid phase transition material of the present invention, and this phase change material is carried out the DSC test, and its enthalpy of phase change is 72J/g.
Embodiment 4:
Take by weighing average molecular mass and be 1000 polyoxyethylene glycol 20 grams be dissolved in 30 milliliters the methylene dichloride solution, take by weighing nano-cellulose 2 grams make its be dispersed in the dimethyl formamide suspension; In polyglycol solution and nano-cellulose suspension, add respectively under 40～60 ℃ the reaction of Mono Chloro Acetic Acid 2.5 gram after 4 hours carboxymethylated polyglycol solution of hydroxyl and the carboxymethylated nano-cellulose suspension of hydroxyl, 15 milliliters of (about 25.5g) reactions of thionyl chloride made carboxymethyl nano-cellulose acylations get acylations nano-cellulose suspension after 4 hours in hydroxyl carboxymethylation nano-cellulose suspension, carboxymethylated polyglycol solution of hydroxyl and acylations nano-cellulose suspension are mixed stirring, add the 1.6g photosensitizers, then mixed solution is put into ultraviolet producer (GE:LU400/T/40; 400W), use UV-irradiation 1h, the product drying promptly gets nano cellulose solid-solid phase transition material of the present invention, and this phase change material is carried out the DSC test, and its enthalpy of phase change is 40J/g.
Embodiment 5:
Take by weighing average molecular mass and be 10000 polyoxyethylene glycol 20 grams be dissolved in 30 milliliters the methylene dichloride solution, measure acrylate chloride 10 milliliters (11.138g) be dissolved in 15 milliliters of methylene dichloride solution, and be divided into two parts, take by weighing carboxymethyl nano-cellulose 2 gram make its be dispersed in the dimethyl formamide suspension; In polyglycol solution, add catalyst of triethylamine, under 0 ℃, respectively polyglycol solution and carboxymethyl nano-cellulose suspension are added drop-wise in the acrylate chloride solution in batches, and slowly stir, react after 6 hours, two reaction solutions are poured on to be mixed together stir, add 1.5g photosensitizers benzophenone, then mixed solution is put into ultraviolet producer (GE:LU400/T/40; 400W), use UV-irradiation 1h, at last product is drying to obtain nano cellulose solid-solid phase transition material of the present invention, and this phase change material is carried out the DSC test, its enthalpy of phase change is 12J/g.
Embodiment 6:
Take by weighing average molecular mass and be 2000 polyoxyethylene glycol 6g be dissolved in 15 milliliters of methylene dichloride solution, measure tolylene diisocyanate 3.2g be dissolved in 30 milliliters of acetone solution, take by weighing nano-cellulose 21g make its be dispersed in the dimethyl formamide suspension; After preparing solution, add 1 catalyzer di lauric dibutyl ester at polyglycol solution, then this solution slowly is added drop-wise in the above-mentioned tolylene diisocyanate solution and stirs, with this liquid and nano-cellulose suspension mixing and stirring, and put it into ultraviolet producer (GE:LU400/T/40 after dropwising; Irradiation 25min 400W) after reaction finishes, is drying to obtain nano cellulose solid-solid phase transition material of the present invention with the product processing, and this phase change material is carried out the DSC test, and its enthalpy of phase change is 25J/g.
Embodiment 7:
Take by weighing average molecular mass and be 1000 polyoxyethylene glycol 10g be dissolved in 10 milliliters of toluene solutions solution, take by weighing carboxymethyl nano-cellulose 4g be scattered in the N,N-DIMETHYLACETAMIDE suspension; Above-mentioned two liquid are mixed, add 0.4g catalyzer tosic acid, this mixed solution is put into ultraviolet producer (GE:LU400/T/40; 250W) behind the irradiation 2.5h, with the product drying, promptly get nano cellulose solid-solid phase transition material of the present invention, surveying its enthalpy of phase change is about 6J/g.
Embodiment 8:
Take by weighing average molecular mass and be 2000 polyoxyethylene glycol 20g be dissolved in 15 milliliters of methylene dichloride solution, under the N2 gas shiled, 0 ℃ drips 5 milliliters of acrylate chlorides (about 5.569g) down, dropwises and reacts 6h; Take by weighing nano-cellulose 5g make its be scattered in the N,N-DIMETHYLACETAMIDE suspension B, under 0 ℃ after it adds 8 milliliters of (about 7g) reactions of oxyethane (hydroxyethylation) 1.5h, then drip 8 milliliters of acrylate chlorides (about 8.9g), dropwise and react 6h; After above-mentioned two reaction solutions are mixed, put into ultraviolet producer (400W) irradiation 1h, after reaction finishes, product handled being drying to obtain described phase change material.Surveying its enthalpy of phase change is 15J/g.
Claims (8)
1. nano cellulose solid-solid phase transition material; its structure is that the polyoxyethylene glycol that active group is contained in one or both ends is fixed on the high-molecular bone frame material; it is characterized in that this high-molecular bone frame material is the nano-cellulose or derivatives thereof; and be in nonhomogeneous system; obtained by the following reactant reaction of forming: reaction-ure mixture is a massfraction 100%; wherein the polyoxyethylene glycol 19.8%～82.0% of active group is contained in one or both ends; linking agent 0%～55.1% and nano-cellulose or derivatives thereof 4.0%～69.5%; the relative molecular mass of described polyoxyethylene glycol is 400～10000; the active group of described polyoxyethylene glycol is hydroxyl or carboxyl, and described nano-cellulose derivative is the hydroxyl carboxymethylation; the nano-cellulose of hydroxyethylation or acylations.
2. a kind of nano cellulose solid-solid phase transition material according to claim 1 is characterized in that described linking agent is acrylic acid or the like, acrylate chloride class, acrylic amide, dibasic acid anhydride class or diisocyanate compound.
3. a kind of nano cellulose solid-solid phase transition material according to claim 2, it is characterized in that described diisocyanates linking agent is a tolylene diisocyanate, 4,4-diphenylmethanediisocyanate, hexamethylene diisocyanate, 1,5-naphthalene diisocyanate, 2,6-two isocyanato methyl caproates, mphenylenedimethylim-vulcabond, PPDI or ask phenylene diisocyanate, described dibasic acid anhydride class linking agent is maleic anhydride or diacetyl oxide.
4. the preparation method of a nano cellulose solid-solid phase transition material, it is characterized in that being reacted by the following reactant of forming: reaction-ure mixture is a massfraction 100%, wherein the polyoxyethylene glycol 19.8%～82.0% of active group is contained in one or both ends, linking agent 0%～55.1% and nano-cellulose or derivatives thereof 4.0%～69.5%, its reaction may further comprise the steps:
(1) with solvent polyoxyethylene glycol, the linking agent wiring solution-forming of active group, nano-cellulose or derivatives thereof solvent dispersion are contained in one or both ends respectively;
(2) with above-mentioned join one or both ends contain the polyglycol solution of active group and nano-cellulose or derivatives thereof dispersion liquid separately or together or successively with linking agent or step (1) join cross-linking agent solution mixes, react;
(3) step (1) is joined one or both ends contain the polyglycol solution of active group and reaction solution that nano-cellulose derivative dispersion liquid mixes or step (2) is obtained mixes, in the presence of photosensitizers, in the ultraviolet producer, react, with gained reaction product drying;
The relative molecular mass of the polyoxyethylene glycol described in the preparation method is 400～10000, and the active group of described polyoxyethylene glycol is hydroxyl or carboxyl, and described nano-cellulose derivative is the nano-cellulose of hydroxyl carboxymethylation, hydroxyethylation or acylations.
5. the preparation method of a kind of nano cellulose solid-solid phase transition material according to claim 4 is characterized in that described linking agent is acrylic acid or the like, acrylate chloride class, acrylic amide, dibasic acid anhydride class, diisocyanates.
6. the preparation method of a kind of nano cellulose solid-solid phase transition material according to claim 5, it is characterized in that described diisocyanates linking agent is a tolylene diisocyanate, 4,4-diphenylmethanediisocyanate, hexamethylene diisocyanate, 1,5-naphthalene diisocyanate, 2,6-two isocyanato methyl caproates, mphenylenedimethylim-vulcabond, PPDI or m-benzene diisocyanate, described dibasic acid anhydride class linking agent is maleic anhydride or diacetyl oxide.
7. according to the preparation method of claim 4 or 5 or 6 described-kind of nano cellulose solid-solid phase transition materials, the solvent that it is characterized in that being used in the step (1) dissolving described polyoxyethylene glycol is methylene dichloride, benzene, toluene or acetone, dissolving back or adding basic metal are as properties-correcting agent, the solvent that is used to dissolve linking agent is methylene dichloride, benzene, toluene or acetone, and the solvent that is used for the plain or derivatives thereof of dispersion of nanofibers is dimethyl formamide, N,N-DIMETHYLACETAMIDE or dimethyl sulfoxide (DMSO); And solution mixes the method that drips that adopts in the described step (2), described polyglycol solution and nano-cellulose or derivatives thereof dispersant liquid drop are added in linking agent or its solution, or linking agent or its solution be added drop-wise to respectively in above-mentioned two liquid, reaction can catalyzer and or stopper in the presence of carry out, catalyzer and stopper can with the described polyglycol solution of adding before linking agent mixes with or nano-cellulose or derivatives thereof dispersion liquid in; And the photosensitizers described in the step (3) is an aromatic ketone compounds.
8. the preparation method of a kind of nano cellulose solid-solid phase transition material according to claim 7, it is characterized in that described catalyzer is pyridine, triethylamine or tosic acid, described stopper is Resorcinol or benzoquinones, and described photosensitizers is benzophenone or thioxanthone.
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| CN116285620A (en) * | 2022-12-30 | 2023-06-23 | 宁波天益医疗器械股份有限公司 | Hydrophilic anticoagulation coating of pump tube for extracorporeal circulation pipeline and preparation method thereof |
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| CN1165174A (en) * | 1996-12-30 | 1997-11-19 | 中国科学院广州化学研究所 | Solid-solid phase shift energy-storage temp. control fucntion material and its preparation |
| US6004662A (en) * | 1992-07-14 | 1999-12-21 | Buckley; Theresa M. | Flexible composite material with phase change thermal storage |
| CN1247216A (en) * | 1999-09-08 | 2000-03-15 | 中国科学院广州化学研究所 | Reticular solid-solid phase change material and its preparing process |
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| US4572864A (en) * | 1985-01-04 | 1986-02-25 | The United States Of America As Represented By The United States Department Of Energy | Composite materials for thermal energy storage |
| US6004662A (en) * | 1992-07-14 | 1999-12-21 | Buckley; Theresa M. | Flexible composite material with phase change thermal storage |
| CN1165174A (en) * | 1996-12-30 | 1997-11-19 | 中国科学院广州化学研究所 | Solid-solid phase shift energy-storage temp. control fucntion material and its preparation |
| CN1247216A (en) * | 1999-09-08 | 2000-03-15 | 中国科学院广州化学研究所 | Reticular solid-solid phase change material and its preparing process |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101967697A (en) * | 2010-10-20 | 2011-02-09 | 东华大学 | Method for preparing biodegradable solid-solid phase transition nano fibers or fiber membranes |
| CN101967697B (en) * | 2010-10-20 | 2012-05-09 | 东华大学 | Method for preparing biodegradable solid-solid phase transition nano fibers or fiber membranes |
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| CN1710012A (en) | 2005-12-21 |
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