CN102190793B - Dendritic organic nano composite phase change thermal storage material and preparation method thereof - Google Patents
Dendritic organic nano composite phase change thermal storage material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a dendritic organic nano composite phase change thermal storage material and a preparation method thereof. The preparation method comprises the following steps of: (1) adding mixed solution of ethylenediamine and methanol into methyl acrylate and a phase change material, reacting, standing, collecting lower-layer liquid, crystallizing, and collecting crystals; (2) adding a product in the step (1) into ethylenediamine and the phase change material, reacting, standing, collecting lower-layer liquid, crystallizing, and collecting crystals; (3) adding a product in the step (2) into the methyl acrylate and the phase change material, reacting, standing, collecting lower-layer liquid, crystallizing, and collecting crystals; and (4) adding a product in the step (3) into the ethylenediamine and the phase change material, reacting, standing, collecting lower-layer liquid, crystallizing, and collecting crystals to obtain the dendritic organic nano composite phase change thermal storage material. The dendritic organic nano composite phase change thermal storage material has high energy storage density, constant temperature control, and obvious energy-saving effect, is well compatible with a polymer matrix, and has important significance for multiple fields such as aerospace and the like.
Description
Technical field
The present invention relates to a kind of organic nano composite phase-change heat-storage material and preparation method thereof.
Background technology
Along with more highlighting the energy and environmental problem day, energy-saving and emission-reduction enjoy international community to pay close attention to, and the energy effectively utilizes and the energy storage is the important means that realizes energy-saving and emission-reduction.
Phase change energy storage technology is to utilize the latent heat of phase change of material to realize absorption, storage and the release of energy, effectively utilizes to become with energy-saving field at the energy and studies one of focus.The various countries researchist has carried out deep research to the theoretical and application of solid-liquid phase change energy storage since the sixties in 20th century.Phase-changing energy storage material is meant in its thing phase change process, can carry out energy exchange (absorb heat or emit heat to external environment from external environment) with external environment, thereby reaches the material that control environment temperature and energy utilize purpose.
Utilizing the latent heat of phase change of phase change material to realize the storage and the utilization of energy, improve efficiency and exploitation renewable energy source, is forward position research direction that ten minutes enlivens in energy science and the material science in recent years.
The crucial difficult point of phase change energy storage technology has: the one, and phase change material exists the mobile leakage problem of liquid phase, the corrosion problems that particularly also exists for inorganic hydrated salt class phase change material after solid-liquid phase change takes place; The 2nd, the standing storage problem of organic molecule phase change material; The 3rd, the heat exchange efficiency problem of phase transition process.According to the result of study of the Ismail of MIT, square being directly proportional of the time that the phase transition process of object is accomplished and its equivalent redius, the phase change material volume is more little, and the heat exchange efficiency of its phase transition process is just high more, and the time of completion is just short more.That is the volume that, reduces phase change material is the effective ways that improve the phase transition process heat exchange efficiency.
At present; The nano phase change energy storage capsule powder that (CN200810202404, a kind of preparation method of phase-change energy-storage nano capsule powder and application thereof) such as the Zhang Dong of Tongji University reported is though energy storage efficiency is high; But poor with the consistency of polymeric matrix, need further to improve.
Dendritic polymer is a nova that was born in recent years and obtained developing rapidly, in material science, rise rapidly.Because its highly branched structure makes this compounds have special nature and function with unique monodispersity.Compare with linear macromolecule, the synthetic employing multistep multiple method of dendritic polymer, in the process that progressively increases, the relative molecular mass in each step is accurately controllable, and can select different branch subalgebras according to different purposes; Dendritic polymer has the geometrical symmetry of height, makes it become the ideal model of function sub-micron ball; Dendritic polymer has inner porous three-dimensional structure, and the end group that surface enrichment is a large amount of makes macromole have preferable reactive behavior; Dendritic polymer inside has a large amount of cavitys, helps the carrying out of Journal of Molecular Catalysis reaction; Owing to have accurate molecular structure, dendritic polymer is difficult to crystallization, also do not have chain and twine, thereby solvability, compatibility improves greatly; In addition, because highly branched topological form makes the dendriform molecule in three-dimensional space, have proximate globosity, its size between a few nanometer to tens nanometers, is typical nano material generally.Therefore, the dendritic polymer particular structure makes it be expected to become the breach that solves above-mentioned bottleneck problem.
Summary of the invention
The purpose of this invention is to provide a kind of dendriform organic nano composite phase-change heat-storage material and preparation method thereof, to overcome the defective of current material.
The preparation method of dendriform organic nano composite phase-change heat-storage material of the present invention comprises the steps:
(1), adds the mixing solutions of quadrol and methyl alcohol, 60～80 ℃ of reaction 24～36h with methyl acrylate and phase change material; Leave standstill, collect lower floor's liquid, methyl alcohol is wherein removed in distillation; Product after the distillation is dissolved in the acetone; At 0～10 ℃ of following crystallization 10～20h, collect crystallisate, obtain 0.5 generation dendriform organic nano composite phase-change heat-storage material;
Said phase change material is Na
2SO
410H
2O, CaCl
26H
2O, Na
2CO
310H
2O, NSC 6366, tetramethylolmethane, paraffin or Triple Pressed Stearic Acid etc.;
Quadrol: methyl alcohol=1: 2～4, preferred 1: 3, mol ratio;
Quadrol: methyl acrylate=1: 6～8, preferred 1: 7, mol ratio;
Quadrol: phase change material=1: 0.2～0.4, preferred 1: 0.3, mol ratio;
(2), add the product of step (1), 80～100 ℃ of reaction 36～48h with quadrol and phase change material; Leave standstill, collect lower floor's liquid, methyl alcohol and quadrol wherein removed in distillation; Product after the distillation is dissolved in the acetone; At 0～10 ℃ of following crystallization 20～30h, collect crystallisate, obtain 1 generation dendriform organic nano composite phase-change heat-storage material;
Said phase change material is Na
2SO
410H
2O, CaCl
26H
2O, Na
2CO
310H
2O, NSC 6366 and tetramethylolmethane, paraffin or Triple Pressed Stearic Acid etc.;
The product of step (1): quadrol=1: 7～9, preferred 1: 8, mol ratio.
The product of step (1): phase change material=1: 0.3～0.5, preferred 1: 0.4, mol ratio.
(3), add the product of step (2), 100～120 ℃ of reaction 48～60h with methyl acrylate and phase change material; Leave standstill, collect lower floor's liquid, methyl alcohol is wherein removed in distillation; Product after the distillation is dissolved in the acetone; At 0～10 ℃ of following crystallization 30～40h, collect crystallisate, obtain 1.5 generation dendriform organic nano composite phase-change heat-storage material;
Said phase change material is Na
2SO
410H
2O, CaCl
26H
2O, Na
2CO
310H
2O, NSC 6366, tetramethylolmethane, paraffin or Triple Pressed Stearic Acid etc.;
The product of step (2): methyl acrylate=1: 8～10, preferred 1: 9, mol ratio;
The product of step (2): phase change material=1: 0.4～0.6, preferred 1: 0.5, mol ratio;
(4), add the product of step (3), 120～140 ℃ of reaction 60～72h with quadrol and phase change material; Leave standstill, collect lower floor's liquid, methyl alcohol and quadrol wherein removed in distillation; Product after the distillation is dissolved in the acetone; At 0～10 ℃ of following crystallization 40～50h, collect crystallisate, obtain dendriform organic nano composite phase-change heat-storage material;
Said phase change material is Na
2SO
410H
2O, CaCl
26H
2O, Na
2CO
310H
2O, NSC 6366, tetramethylolmethane, paraffin or Triple Pressed Stearic Acid etc.;
The product of step (3): quadrol=1: 8～10, preferred 1: 9, mol ratio.
The product of step (3): phase change material=1: 0.5～0.7, preferred 1: 0.6, mol ratio.
The dendriform organic nano composite phase-change heat-storage material of method preparation of the present invention; With the inner lar nanometric cavities of dendritic macromole as carrier packing phase change material; Its advantage is; Good with the polymeric matrix consistency; Energy storage density height, advantages of small volume, temperature control is constant, energy-saving effect is remarkable, heat exchange efficiency is high, be easy to advantage such as control, has important use value and wide prospect in various fields such as aerospace, sun power utilization, heating and air-conditioning, power supply system optimization, engineering in medicine, military engineering, accumulation of heat buildings.
Embodiment
Adopt the latent heat of phase change of the final dendriform organic nano composite phase-change heat-storage material of dsc test; Adopt transmission electron microscope method to observe the size of particles of final dendriform organic nanocomposite.
Embodiment 1
1mol quadrol and 2mol methyl alcohol are joined in the there-necked flask that has magnetic agitation, reflux condensing tube and TM, under 30 ℃ of agitation conditions, stir 40min, quadrol is dissolved fully.
Add 6mol methyl acrylate and 0.2mol Na
2SO
410H
2O behind 80 ℃ of reaction 24h, changes reaction mixture in the separating funnel over to, leaves standstill 1h, tells lower floor's liquid, washes a layer liquid with methyl alcohol.Under 80 ℃ of pressure with 150Pa, carry out underpressure distillation and remove remaining methyl alcohol.
With the distillation after product be dissolved in the 100mL acetone, place 0 ℃ refrigerator crystallization 20h, negative pressure filtration, drying, white crystal, promptly 0.5 generation dendriform organic nano composite phase-change heat-storage material.
1mol 0.5 generation phase-change heat-storage material is joined in the there-necked flask that has magnetic agitation, reflux condensing tube and TM, add 7mol quadrol and 0.3mol Na
2SO
410H
2O behind 100 ℃ of reaction 36h, changes reaction mixture in the separating funnel over to, leaves standstill 2h, tells lower floor's liquid, with methanol wash lower floor liquid.Under 70 ℃ of pressure with 250Pa, carry out underpressure distillation and remove excessive methanol and raw material quadrol.
With the distillation after product be dissolved in the 150mL acetone, place 0 ℃ refrigerator crystallization 30h, negative pressure filtration, drying, white crystal, promptly 1 generation dendriform organic nano composite phase-change heat-storage material.
1mol 1 generation phase-change heat-storage material is joined in the there-necked flask that has magnetic agitation, reflux condensing tube and TM.Add 8mol methyl acrylate and 0.4mol Na
2SO
410H
2O behind 120 ℃ of reaction 48h, changes reaction mixture in the separating funnel over to, leaves standstill 3h, tells lower floor's liquid, washes a layer liquid with methyl alcohol.Under 60 ℃ of pressure with 300Pa, carry out underpressure distillation and remove excessive methanol and the sour methyl esters of raw material propylene.
With the distillation after product be dissolved in the 200mL acetone, place 0 ℃ refrigerator crystallization 40h, negative pressure filtration, drying, white crystal, promptly 1.5 generation dendriform organic nano composite phase-change heat-storage material.
1mol 1.5 generation phase-change heat-storage material is joined in the there-necked flask that has magnetic agitation, reflux condensing tube and TM.Adopt and add 8mol quadrol and 0.5mol Na
2SO
410H
2O behind 140 ℃ of reaction 60h, changes reaction mixture in the separating funnel over to, leaves standstill 4h, tells lower floor's liquid, washes a layer liquid with methyl alcohol.Under 50 ℃ of pressure with 350Pa, carry out underpressure distillation and remove excessive methanol and raw material quadrol.
Product after the distillation is dissolved in the 250mL acetone, places 0 ℃ refrigerator crystallization 50h, negative pressure filtration, drying get white crystal, promptly final dendriform organic nano composite phase-change heat-storage material.
The size of particles of latent heat of phase change and organic nanocomposite is seen table 1.
Embodiment 2
1mol quadrol and 3mol methyl alcohol are joined in the there-necked flask that has magnetic agitation, reflux condensing tube and TM, under 40 ℃ of agitation conditions, stir 30min, 7 diamines are dissolved fully.
Add 7mol methyl acrylate and 0.3mol tetramethylolmethane, behind 70 ℃ of reaction 30h, reaction mixture is changed in the separating funnel, leave standstill 2h, tell lower floor's liquid, wash a layer liquid with methyl alcohol.Under 85 ℃ of pressure with 120Pa, carry out underpressure distillation and remove remaining methyl alcohol.
With the distillation after product be dissolved in the 120mL acetone, place 5 ℃ refrigerator crystallization 15h, negative pressure filtration, drying, white crystal, promptly 0.5 generation dendriform organic nano composite phase-change heat-storage material.
1mol 0.5 generation phase-change heat-storage material is joined in the there-necked flask that has magnetic agitation, reflux condensing tube and TM.Adopt adding 8mol quadrol and 0.4mol tetramethylolmethane, behind 90 ℃ of reaction 42h, reaction mixture is changed in the separating funnel, leave standstill 3h, tell lower floor's liquid, with methanol wash lower floor liquid.Under 75 ℃ of pressure with 220Pa, carry out underpressure distillation and remove excessive methanol and raw material quadrol.
With the distillation after product be dissolved in the 180mL acetone, place 5 ℃ refrigerator crystallization 25h, negative pressure filtration, drying, white crystal, promptly 1 generation dendriform organic nano composite phase-change heat-storage material.
1mol 1 generation phase-change heat-storage material is joined in the there-necked flask that has magnetic agitation, reflux condensing tube and TM.Add 9mol methyl acrylate and 0.5mol tetramethylolmethane, behind 110 ℃ of reaction 54h, reaction mixture is changed in the separating funnel, leave standstill 4h, tell lower floor's liquid, wash a layer liquid with methyl alcohol.Under 65 ℃ of pressure with 220Pa, carry out underpressure distillation and remove excessive methanol and the sour methyl esters of raw material propylene.
With the distillation after product be dissolved in the 220mL acetone, place 5 ℃ refrigerator crystallization 35h, negative pressure filtration, drying, white crystal, promptly 1.5 generation dendriform organic nano composite phase-change heat-storage material.
1mol 1.5 generation phase-change heat-storage material is joined in the there-necked flask that has magnetic agitation, reflux condensing tube and TM.Add 9mol quadrol and 0.6mol tetramethylolmethane, behind 130 ℃ of reaction 66h, reaction mixture is changed in the separating funnel, leave standstill 5h, tell lower floor's liquid, wash a layer liquid with methyl alcohol.Under 55 ℃ of pressure with 320Pa, carry out underpressure distillation and remove excessive methanol and raw material quadrol.
Product after the distillation is dissolved in the 280mL acetone, places 5 ℃ refrigerator crystallization 45h, negative pressure filtration, drying get white crystal, i.e. dendriform organic nano composite phase-change heat-storage material.
The size of particles of latent heat of phase change and organic nanocomposite is seen table 1.
Embodiment 3
Just 1mol quadrol and 4mol methyl alcohol join in the there-necked flask that has magnetic agitation, reflux condensing tube and TM, under 50 ℃ of agitation conditions, stir 20min, and quadrol is dissolved fully.
Add 8mol methyl acrylate and 0.4mol paraffin, behind 60 ℃ of reaction 36h, reaction mixture is changed in the separating funnel, leave standstill 3h, tell lower floor's liquid, wash a layer liquid with methyl alcohol.Under 90 ℃ of pressure with 100Pa, carry out underpressure distillation and remove remaining methyl alcohol.
With the distillation after product be dissolved in the 150mL acetone, place 10 ℃ refrigerator crystallization 10h, negative pressure filtration, drying, white crystal, promptly 0.5 generation dendriform organic nano composite phase-change heat-storage material.
1mol 0.5 generation phase-change heat-storage material is joined in the there-necked flask that has magnetic agitation, reflux condensing tube and TM.Add 9mol quadrol and 0.5mol paraffin, behind 80 ℃ of reaction 48h, reaction mixture is changed in the separating funnel, leave standstill 4h, tell lower floor's liquid, with methanol wash lower floor liquid.Under 80 ℃ of pressure with 200Pa, carry out underpressure distillation and remove excessive methanol and raw material quadrol.
With the distillation after product be dissolved in the 200mL acetone, place 10 ℃ refrigerator crystallization 20h, negative pressure filtration, drying, white crystal, promptly 1 generation dendriform organic nano composite phase-change heat-storage material.
1mol 1 generation phase-change heat-storage material is joined in the there-necked flask that has magnetic agitation, reflux condensing tube and TM.Add 10mol methyl acrylate and 0.6mol paraffin, behind 100 ℃ of reaction 60h, reaction mixture is changed in the separating funnel, leave standstill 5h, tell lower floor's liquid, wash a layer liquid with methyl alcohol.Under 60 ℃ of pressure with 250Pa, carry out underpressure distillation and remove excessive methanol and the sour methyl esters of raw material propylene.
With the distillation after product be dissolved in the 250mL acetone, place 10 ℃ refrigerator crystallization 30h, negative pressure filtration, drying, white crystal, promptly 1.5 generation dendriform organic nano composite phase-change heat-storage material.
1mol 1.5 generation phase-change heat-storage material is joined in the there-necked flask that has magnetic agitation, reflux condensing tube and TM.Add 10mol quadrol and 0.7mol paraffin, behind 120 ℃ of reaction 72h, reaction mixture is changed in the separating funnel, leave standstill 6h, tell lower floor's liquid, wash a layer liquid with methyl alcohol.Under 60 ℃ of pressure with 300Pa, carry out underpressure distillation and remove excessive methanol and raw material quadrol.
Product after the distillation is dissolved in the 300mL acetone, places 10 ℃ refrigerator crystallization 40h, negative pressure filtration, drying get white crystal, i.e. dendriform organic nano composite phase-change heat-storage material.
The size of particles of latent heat of phase change and organic nanocomposite is seen table 1.
Table 1 latent heat of phase change and size of particles
| Embodiment | Latent heat of phase change (J/g) | Median size (nm) |
| 1 | 200 | 30 |
| 2 | 220 | 40 |
| 3 | 240 | 50 |
Claims (7)
1. the preparation method of dendriform organic nano composite phase-change heat-storage material is characterized in that, comprises the steps:
(1) with methyl acrylate and phase change material, add the mixing solutions of quadrol and methyl alcohol, reaction is left standstill, and collects lower floor's liquid, removes the product crystallization in acetone behind the methyl alcohol wherein, the collection crystallisate;
(2) with quadrol and phase change material, add the product of step (1), reaction is left standstill, and collects lower floor's liquid, removes wherein methyl alcohol and the crystallization in acetone of the product behind the quadrol, collects crystallisate;
(3) with methyl acrylate and phase change material, add the product of step (2), reaction is left standstill, and collects lower floor's liquid, and crystallisate is collected in product crystallization in acetone of removing methyl alcohol wherein;
(4) with quadrol and phase change material, add the product of step (3), reaction is left standstill, and collects lower floor's liquid, removes wherein methyl alcohol and the crystallization in acetone of the product behind the quadrol, collects crystallisate, obtains dendriform organic nano composite phase-change heat-storage material;
In the step (1):
Quadrol: methyl alcohol=1: 2～4, mol ratio;
Quadrol: methyl acrylate=1: 6～8, mol ratio;
Quadrol: phase change material=1: 0.2～0.4, mol ratio;
In the step (2):
The product of step (1): quadrol=1: 7～9, mol ratio;
The product of step (1): phase change material=1: 0.3～0.5, mol ratio;
In the step (3):
The product of step (2): methyl acrylate=1: 8～10, mol ratio;
The product of step (2): phase change material=1: 0.4～0.6, mol ratio;
In the step (4):
The product of step (3): quadrol=1: 8～10, mol ratio;
The product of step (3): phase change material=1: 0.5～0.7, mol ratio.
2. method according to claim 1 is characterized in that, in the step (1), 60～80 ℃ of reaction 24～36h are at 0～10 ℃ of following crystallization 10～20h;
In the step (2), 80～100 ℃ of reaction 36～48h are at 0～10 ℃ of following crystallization 20～30h;
In the step (3), 100～120 ℃ of reaction 48～60h are at 0～10 ℃ of following crystallization 30～40h;
In the step (4), 120～140 ℃ of reaction 60～72h are at 0～10 ℃ of following crystallization 40～50h.
3. method according to claim 1 and 2 is characterized in that, said phase change material is Na
2SO
410H
2O, CaCl
26H
2O, Na
2CO
310H
2O, NSC 6366, tetramethylolmethane, paraffin or Triple Pressed Stearic Acid.
4. method according to claim 1 is characterized in that, in the step (1):
Quadrol: methyl alcohol=1: 3, mol ratio;
Quadrol: methyl acrylate=1: 7, mol ratio;
Quadrol: phase change material=1: 0.3, mol ratio.
5. method according to claim 1 is characterized in that, in the step (2):
The product of step (1): quadrol=1: 8, mol ratio;
The product of step (1): phase change material=1: 0.4, mol ratio.
6. method according to claim 1 is characterized in that, in the step (3):
The product of step (2): methyl acrylate=1: 9, mol ratio;
The product of step (2): phase change material=1: 0.5, mol ratio.
7. the dendriform organic nano composite phase-change heat-storage material for preparing according to each described method of claim 1～6.
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| CN1631936A (en) * | 2003-12-24 | 2005-06-29 | 上海市血液中心 | Polyamide-amine type branch-shape polymer nano materials, synthesis method and use thereof |
| CN101530772A (en) * | 2009-03-13 | 2009-09-16 | 清华大学深圳研究生院 | Preparing method for phase transited stored energy microcapsule covered with an organic polymer material |
| CN101704948A (en) * | 2009-12-02 | 2010-05-12 | 大庆石油学院 | Method for synthesizing dendritic phenolic antioxidant |
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| CN1631936A (en) * | 2003-12-24 | 2005-06-29 | 上海市血液中心 | Polyamide-amine type branch-shape polymer nano materials, synthesis method and use thereof |
| CN101530772A (en) * | 2009-03-13 | 2009-09-16 | 清华大学深圳研究生院 | Preparing method for phase transited stored energy microcapsule covered with an organic polymer material |
| CN101704948A (en) * | 2009-12-02 | 2010-05-12 | 大庆石油学院 | Method for synthesizing dendritic phenolic antioxidant |
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