CN1263821C - High molecular solid/solid phase changing material with net type and comb type mixed structure and its preparing method - Google Patents
High molecular solid/solid phase changing material with net type and comb type mixed structure and its preparing method Download PDFInfo
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- CN1263821C CN1263821C CN 200410051663 CN200410051663A CN1263821C CN 1263821 C CN1263821 C CN 1263821C CN 200410051663 CN200410051663 CN 200410051663 CN 200410051663 A CN200410051663 A CN 200410051663A CN 1263821 C CN1263821 C CN 1263821C
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Abstract
The present invention relates to a high molecular solid-solid phase change material with a mesh and comb mixing structure. The present invention is characterized in that a molecule of polyethylene glycol with two activity terminal groups and a molecule of polyethylene glycol with one activity terminal group are fixed on a molecule of a high molecular framework material so as to form the three-dimensional mesh and comb mixing structure. The material of the present invention has a large phase change enthalpy which can reach 120 J/g. The phase change temperature of the material is moderate and can be changed and adjusted between 0 DEG C and 65 DEG C. The material can maintain a good solid state before and after phase change, and the unstable phenomena of supercooling, chromatography, etc. can not occur. The present invention has the advantages of high mechanical strength, high solvent resistance, good processability, no toxicity, no harm, no leakage, no corrosion, no pollution, long service life, simple preparation method, low cost, abundant raw material source, good framework material stability, etc. The material can be widely used in the civil and military fields of solar energy utilization, waste heat recovery, intelligent automatic air conditioner buildings, glass houses, phase change energy storage air conditioners, electric appliance temperature maintenance, temperature control garments, etc.
Description
Technical field
The present invention relates to a kind of macromolecular solid solid phase change material and preparation method thereof with netted and pectination mixed structure.
Background technology
Energy storage material has a very wide range of applications in practice, and the most frequently used both at home and abroad is solid-liquid phase change material, must be during use with container sealing, otherwise can be because of leakage etching apparatus and contaminate environment; And the material with solid-solid phase change characteristic just can overcome this shortcoming.Common solid-solid phase change 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 when using to seal, also be difficult to obtain practical application with container; High score subclass phase change material comprises polymer blended class and macromolecular grafted class.Low melting point operation material in the polymer blended class phase change material is after fusion, make operation material leakage, contaminate environment by occurring being separated between diffusive migration effect and carrier matrix, and performances such as the hardness of whole material, intensity, snappiness all are subjected to very big influence after the blend, shorten work-ing life, easily wear out so that cause; Because ubiquity desorption and noted phase separation phenomena in the co-mixing system, do not have the solid-solid phase change characteristic, so its practicality is not strong.And macromolecular grafted class solid-solid phase change 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 generally less, and stability neither be good especially.
According to aforementioned, the preparation method of phase-changing energy storage material mainly contains two classes at present: a class adopts physical method to make, and another kind of is to adopt the chemical process preparation.Adopt physical method to prepare phase change material, as Japanese Patent JP 06 235 592 (1994) and JP 01 294 787 (1989), be to utilize adsorption (being Intermolecular Forces) or encapsulation technology that various phase change materials and certain carrier matrix are combined, make phase change material on macroscopic view, lose flowability, but the essence that still has solid-liquid phase change on microcosmic, this class material is referred to as the solid-liquid phase change material of dimensionally stable on document.Phase transformation storage (heat) the energy material that this class is made with the blend form, the low melting point operation material is after fusion, make operation material leakage, contaminate environment by occurring being separated between diffusive migration effect and carrier matrix, and performances such as the hardness of whole material, intensity, snappiness all can be subjected to very big influence after the blend, to such an extent as to shorten work-ing life, easily aging, so its practicality is not strong.Adopt the phase change material of chemical process preparation, as U.S. Pat 863 274 (1992) and US 371 779 (1989), what they adopted is heterogeneous reaction system, only can grafting on cellulosic surface, therefore the material phase transformation enthalpy of preparation is less, is 15～30 Jiao/grams to the maximum.In addition, the stability of this class material neither be fine, and anti-bleaching of the fiber of making and washing fastness are relatively poor, through repeatedly using or washing, the decline that scission of link causes energy-storage property takes place easily, and these have also all limited its development.
In addition, in Chinese patent " reticular solid-solid phase change material and preparation thereof " [ZL99117071.7] and " thermoplasticity solid-solid phase change material and preparation thereof " [ZL99117105.5], also adopt chemical process to prepare solid-solid phase change material, compare with foregoing phase change material, have bigger enthalpy of phase change, and transformation temperature can be regulated.Wherein, reticular solid-solid phase change material has excellent rerum naturas such as good mechanical property, ageing-resistant, anti-solvent, and shortcoming is that processing characteristics is poor slightly when making large-sized object; And the solid-solid phase change material of pectination is quite excellent aspect processing characteristics, but use temperature can not be too high, otherwise physical strength can descend to some extent.
Summary of the invention
The object of the present invention is to provide a kind of novel have netted and the macromolecular solid solid phase change material pectination mixed structure, make it not only have bigger enthalpy of phase change, transformation temperature can be regulated, have concurrently netted simultaneously and pectinate solid-solid phase change material advantage separately, good processability not only, use temperature also can increase substantially, and solves above-mentioned variety of issue; Another object of the present invention provides this preparation methods.
The object of the invention realizes by following technical scheme.
Providing a kind of has netted and the macromolecular solid solid phase change material pectination mixed structure, its structure is that the organic materials of the high enthalpy of phase change of low melting point is fixed on high-melting-point or the infusibility skeleton with chemical bond, it is characterized in that the polyoxyethylene glycol that will have two active end groups is fixed on the high-molecular bone frame material with the polyoxyethylene glycol with an active end group, form three-dimensional netted and mixed structure pectination, all keep solid state before and after its phase transformation, its enthalpy of phase change is 120J/g to the maximum, and transformation temperature is adjustable between 0～65 ℃; The described polyoxyethylene glycol relative molecular mass with having an active end group with two active end groups all is 200～3 000 000.
Described polyoxyethylene glycol relative molecular mass the best with having an active end group with two active end groups is 1 000～50 000; Described active end group is the end group with reactive behavior, can be hydroxyl, carboxyl, aldehyde radical, amino, halogeno-group, phenyl, sulfonic group and its esters, vinyl.
Described high-molecular bone frame material can be one or more the material in polyolefins, polyphenyl olefines, polyvinyl alcohol, nylon-type, polyamide-based, polyurethanes, polyacrylate(s), epoxies, silicone based macromolecular material etc.
Described linking agent can be: tolylene diisocyanate (TDI), 4,4 '-diphenylmethanediisocyanate (MDI), hexamethylene diisocyanate (HDI), 1,5-naphthalene diisocyanate (NDI), poly methylene poly phenyl poly isocyanate (PAPI), 2,6-two isocyanato methyl caproates (LDI), mphenylenedimethylim-vulcabond (XDI), PPDI, m-benzene diisocyanate etc.
The present invention also provides a kind of preparation method with macromolecular solid solid phase change material of netted and pectination mixed structure, comprises the steps: to make solution with dissolution with solvents with having after polyoxyethylene glycol two active end groups and that have an active end group mixes; The high-molecular bone frame material is also made solution with dissolution with solvents; Two solution mix, at linking agent or active basic metal for example potassium, sodium or highly basic for example in the presence of potassium hydroxide, the sodium hydroxide, in homogeneous reaction system or heterogeneous reaction system, fully reaction, products therefrom promptly obtains phase change material of the present invention after washing drying, described high-molecular bone frame material, two kinds of polyoxyethylene glycol and linking agent or active basic metal or highly basic three's proportioning is a mass ratio 0.3～69: 30～99.4: 0.05～20, and total amount is 100 mass parts; The relative molecular mass of described two kinds of polyoxyethylene glycol all is 200～3 000 000, and the best is 1 000～50 000, and the polyoxyethylene glycol that has an active end group during it is formed is a massfraction 5%～95%,, the best is 20%～80%.
Described linking agent, active basic metal and alkaline effect all are to make described two kinds of polyoxyethylene glycol to be fixed on the high-molecular bone frame material, preferred active basic metal and highly basic.When using linking agent, linking agent is fixed on bridge on the high-molecular bone frame material as polyoxyethylene glycol, becomes the part that phase change material structure of the present invention is formed after the reaction; When the halo derivatives of described macromolecular scaffold material selection polyolefins or polyphenyl olefines, can select for use active basic metal and highly basic that two kinds of polyoxyethylene glycol are fixed on the high-molecular bone frame material, they will be washed and remove after the reaction, not participate in phase change material structure of the present invention and form; The halo derivatives of described polyolefins or polyphenyl olefines preferred its chlorinated derivative, for example chlorinatedpolyethylene, Chlorinated Polypropylene III, chloromethyl polystyrene etc.When adopting active basic metal, preferably earlier active basic metal is added in the solution of above-mentioned two kinds of polyoxyethylene glycol, fully add again in the macromolecular scaffold material solution after the reaction, mix fully reaction of back.
Used two kinds of polyoxyethylene glycol, high-molecular bone frame material and linking agent as previously mentioned among the preparation method of the present invention.
React selected solvent system and can be non-aqueous system such as toluene, dimethylbenzene and other aromatic hydrocarbons, ester class, ketone system; Also can be aqueous systems.
Solid-solid phase change material provided by the present invention has been compared following advantage with existing phase change material:
(1) enthalpy of phase change is bigger, can reach 120J/g;
(2) transformation temperature is suitable, can change and regulate at 0～65 ℃;
(3) before and after transformation temperature, can both keep good solid state, not have wild effects such as cold-peace chromatography;
(4) have physical strength, solvent resistance and processibility preferably;
(5) have nontoxic, do not have to leak, advantages such as no burn into is pollution-free, long service life;
(6) preparation method is simple, cost is lower;
The starting material source of (7) using is abundant, the framework material good stability.
Phase change material of the present invention can be widely used in civil and military fields such as sun power utilization, waste heat recovery, intelligent automatic air-conditioning and construction thing, glasshouse, phase-changing energy-storing type air-conditioning, electrical equipment constant temperature, temperature-controlled garment.Because it is nontoxic, cost is low, but large-scale industrialization production, thereby can bring huge economic benefit and social benefit, be with a wide range of applications.
Embodiment
Following experiment and operational instances are further to explanation of the present invention, should not be used as limitation of the present invention.
Embodiment 1:
Taking by weighing average molecular mass and be 6000 polyoxyethylene glycol 22.8 grams is that 6000 poly glycol monomethyl ether 1.2 grams are dissolved in the 60mL toluene with average molecular mass, heats under nitrogen protection, and temperature is controlled at 100～120 ℃, solution A.Adding sodium Metal 99.5 0.18 restrains in solution A, reacts to get solution C after 20 hours.Take by weighing 0.43 gram Chlorinated Polypropylene III and add 30mL toluene, heat under nitrogen protection, optimum temps is 80～100 ℃, gets solution B.Evenly drip solution C in solution B, fully reacted 10 hours, with toluene volatilization wherein, washing back and finish-drying promptly obtain solid-solid phase change material of the present invention.After tested, the enthalpy of phase change of this phase change material is 114.2J/g, and transformation temperature is 56.76 ℃.In reactant by massfraction: two kinds of polyoxyethylene glycol are 97.52%, and sodium is 0.73%, and Chlorinated Polypropylene III is 1.75%.
Embodiment 2:
Take by weighing average molecular mass and be 10000 polyoxyethylene glycol 10 grams and average molecular mass and be 5000 poly glycol monomethyl ether 10 grams and be dissolved in together in the 40mL dimethylbenzene, heat under nitrogen protection, temperature is controlled at 150～170 ℃, must solution A.Adding 0.10 restrains sodium Metal 99.5 in solution A, reacts to get solution C after 24 hours.Add 30mL dimethylbenzene in 0.54 gram Chlorinated Polypropylene III, heat under nitrogen protection, controlled temperature gets solution B between 80～100 ℃.Solution C evenly is added dropwise in the solution B, fully react 12 hours after, with the volatilization of wherein dimethylbenzene, washing back finish-drying promptly obtains solid-solid phase change material of the present invention.The enthalpy of phase change of this material is 89.05J/g, and transformation temperature is 52.86 ℃.In reactant by massfraction: two kinds of polyoxyethylene glycol amounts are 96.9%, and sodium is 0.48%, and Chlorinated Polypropylene III is 2.62%.
Embodiment 3:
Take by weighing average molecular mass and be 4000 polyoxyethylene glycol 20 grams and average molecular mass and be 4000 poly glycol monomethyl ether 10 grams and be dissolved in the 40mL toluene, heat under nitrogen protection, temperature is controlled at 60～80 ℃, must solution A.Adding 0.49 restrains potassium metal in solution A, reacts to get solution C after 20 hours.Between 80～100 ℃ and under nitrogen protection, get solution B in the 50mL toluene with being dissolved in the 1.48 gram chloromethyl polystyrene.In solution B, evenly drip solution C.Fully reaction is after 10 hours, and with toluene volatilization wherein, washing back and finish-drying promptly obtain solid-solid phase change material of the present invention.In reactant by massfraction: two kinds of polyoxyethylene glycol are 93.84%, and potassium is 1.53%, and the chloromethyl polystyrene is 4.63%.
Embodiment 4:
In three-necked flask, add average molecular mass and be 6000 polyoxyethylene glycol 12 grams, average molecular mass and be the sodium hydroxide solution and the 0.5 gram catalyst B u of 10000 poly glycol monomethyl ether 20 grams, chlorinatedpolyethylene 0.33 gram and 20 grams 33%
4NBr.Temperature of reaction is controlled at 50～70 ℃, stirs 30 hours.After overcooling, suction filtration, washing, drying, the solid-solid phase change material that promptly obtains not only tridimensional network but also have pectination.In reactant by massfraction: two kinds of polyoxyethylene glycol are 82.20%, and sodium hydroxide is 16.95%, and chlorinatedpolyethylene is 0.85%.
Embodiment 5:
At 80 gram solid contents is in 50% the polypropylene provided with hydroxyl group acid resin solution, adding average molecular mass and be 6000 polyoxyethylene glycol 10 grams and average molecular mass is that 6000 poly glycol monomethyl ethers 10 restrain, after polyoxyethylene glycol and poly glycol monomethyl ether dissolve fully, add 1.1 gram tolylene diisocyanates (TDI-80), add catalyzer dibutyl tin dilaurate 0.001 gram again, after stirring, then mixture is placed baking oven, controlled temperature is between 80～90 ℃; About half an hour the reaction finish, make it drying after, it promptly gets phase change material of the present invention to temperature control in 110 ℃ of finish-dryings again.In reactant by massfraction: two kinds of polyoxyethylene glycol are 32.73%, and tolylene diisocyanate is 1.8%, and the polypropylene provided with hydroxyl group acid resin is 65.47%.
Claims (10)
1. one kind has netted and the macromolecular solid solid phase change material pectination mixed structure, its structure is that the organic materials of the high enthalpy of phase change of low melting point is fixed on high-melting-point or the infusibility skeleton with chemical bond, it is characterized in that the polyoxyethylene glycol that will have two active end groups is fixed on the high-molecular bone frame material with the polyoxyethylene glycol with an active end group, form three-dimensional netted and mixed structure pectination, all keep solid state before and after its phase transformation, its enthalpy of phase change is 120J/g to the maximum, and transformation temperature is adjustable between 0～65 ℃; And prepare by following method:
To have and make solution with dissolution with solvents after polyoxyethylene glycol two active end groups and that have an active end group mixes; The high-molecular bone frame material is also made solution with dissolution with solvents; Two solution mix, in the presence of linking agent or active basic metal or highly basic, and in homogeneous reaction system or heterogeneous reaction system, fully reaction; Described high-molecular bone frame material, two kinds of polyoxyethylene glycol and linking agent or active basic metal or highly basic three's proportioning is a mass ratio 0.3～69: 30～99.4: 0.05～20, and total amount is 100 mass parts; The described relative molecular mass with having the polyoxyethylene glycol of an active end group with two active end groups all is 200～3000000; The polyoxyethylene glycol that has an active end group during described two kinds of polyoxyethylene glycol are formed is a massfraction 5%～95%.
2. a kind of have netted and the macromolecular solid solid phase change material pectination mixed structure according to claim 1 is characterized in that described to have polyoxyethylene glycol relative molecular mass two active end groups and that have an active end group be 1000～50000; Described active end group is hydroxyl, carboxyl, aldehyde radical, amino, halogeno-group, phenyl, sulfonic group or its esters or vinyl.
3. a kind of have netted and the macromolecular solid solid phase change material pectination mixed structure according to claim 1 is characterized in that described high-molecular bone frame material is one or more the material in polyolefins, polyphenyl olefines, polyvinyl alcohol, nylon-type, polyamide-based, polyurethanes, polyacrylate(s), epoxies, the silicone based macromolecular material; Described linking agent is: tolylene diisocyanate, 4,4 '-diphenylmethanediisocyanate, hexamethylene diisocyanate, 1,5-naphthalene diisocyanate, poly methylene poly phenyl poly isocyanate, 2,6-two isocyanato methyl caproates, mphenylenedimethylim-vulcabond, PPDI or m-benzene diisocyanate.
4. the preparation method with macromolecular solid solid phase change material of netted and pectination mixed structure comprises the steps: to make solution with dissolution with solvents with having after polyoxyethylene glycol two active end groups and that have an active end group mixes; The high-molecular bone frame material is also made solution with dissolution with solvents; Two solution mix, in the presence of linking agent or active basic metal or highly basic, and in homogeneous reaction system or heterogeneous reaction system, fully reaction, products therefrom promptly obtains the described phase change material of claim 1 after washing drying; Described high-molecular bone frame material, two kinds of polyoxyethylene glycol and linking agent or active basic metal or highly basic three's proportioning is a mass ratio 0.3～69: 30～99.4: 0.05～20, and total amount is 100 mass parts; The described relative molecular mass with having the polyoxyethylene glycol of an active end group with two active end groups all is 200～3000000; The polyoxyethylene glycol that has an active end group during described two kinds of polyoxyethylene glycol are formed is a massfraction 5%～95%.
5. a kind of preparation method with macromolecular solid solid phase change material of netted and pectination mixed structure according to claim 4 is characterized in that described active end group is hydroxyl, carboxyl, aldehyde radical, amino, halogeno-group, phenyl, sulfonic group or its esters or vinyl.
6. a kind of preparation method with macromolecular solid solid phase change material of netted and pectination mixed structure according to claim 4 is characterized in that the described polyoxyethylene glycol relative molecular mass with having an active end group with two active end groups is 1000～50000; The polyoxyethylene glycol that has an active end group during described two kinds of polyoxyethylene glycol are formed is a massfraction 20%～80%.
7. a kind of preparation method with macromolecular solid solid phase change material of netted and pectination mixed structure according to claim 4 is characterized in that described high-molecular bone frame material is one or more the material in polyolefins, polyphenyl olefines, polyvinyl alcohol, nylon-type, polyamide-based, polyurethanes, polyacrylate(s), epoxies, the silicone based macromolecular material; Described linking agent is: tolylene diisocyanate, 4,4 '-diphenylmethanediisocyanate, hexamethylene diisocyanate, 1,5-naphthalene diisocyanate, poly methylene poly phenyl poly isocyanate, 2,6-two isocyanato methyl caproates, mphenylenedimethylim-vulcabond, PPDI or m-benzene diisocyanate.
8. a kind of preparation method with macromolecular solid solid phase change material of netted and pectination mixed structure according to claim 4 is characterized in that solvent is non-aqueous system or aqueous systems.
9. according to claim 4 or 5 or 6 or 8 described a kind of preparation methods, it is characterized in that described high-molecular bone frame material is the chlorinated derivative of polyolefins or polyphenyl olefines with macromolecular solid solid phase change material of netted and pectination mixed structure; Described active basic metal is potassium or sodium, and described highly basic is potassium hydroxide or sodium hydroxide.
10. according to claim 4 or 5 or 6 or 8 described a kind of preparation methods with macromolecular solid solid phase change material of netted and pectination mixed structure, it is characterized in that described high-molecular bone frame material is the chlorinated derivative of polyolefins or polyphenyl olefines, adopt potassium metal or sodium, earlier potassium metal or sodium are added in the solution of described two kinds of polyoxyethylene glycol, fully add again in the macromolecular scaffold material solution after the reaction, mix fully reaction of back.
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| CN 200410051663 CN1263821C (en) | 2004-09-29 | 2004-09-29 | High molecular solid/solid phase changing material with net type and comb type mixed structure and its preparing method |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102060972B (en) * | 2010-11-26 | 2013-07-24 | 天津工业大学 | Method for preparing comb-shaped polymer solid-solid phase change material |
| US9293617B2 (en) | 2012-12-10 | 2016-03-22 | Honeywell International Inc. | Copolymer of phase change material for thermal management of PV modules |
| CN104327801B (en) * | 2014-10-11 | 2017-07-21 | 徐州工业职业技术学院 | A kind of technique easily-controllable high score subclass solid-solid phase change material and chemical preparation process |
| CN104788684B (en) * | 2015-05-13 | 2017-08-29 | 河北科技大学 | A kind of preparation method of difunctional brush solid-solid phase change energy storage material |
| CN105752486B (en) * | 2016-02-24 | 2018-07-31 | 松冷（武汉）科技有限公司 | A kind of phase-change heat-preserving board and preparation method thereof, phase-transition heat-preserving case |
| CN107602795A (en) * | 2017-09-18 | 2018-01-19 | 武汉纺织大学 | The method that graft copolymerization prepares solid-solid phase change material |
| CN109504351B (en) * | 2018-12-20 | 2021-03-26 | 大连理工大学 | Polyether-based composite phase change energy storage material and preparation method thereof |
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