CN105602530B - A kind of preparation method of organogel composite phase-change material - Google Patents
A kind of preparation method of organogel composite phase-change material Download PDFInfo
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Abstract
The invention belongs to composite phase-change material fields, and in particular to a kind of preparation method of organogel composite phase-change material.Preparation method prepares a kind of covalent organogel carrier first, and different ligands is selected according to the size of core material and type, preferably to match the phase transformation core material to be loaded；Using solution dipping method, organogel carrier material is dispersed by configured phase transformation core material solution, phase transformation core material is adsorbed using the active force in gel duct, removes solvent at relatively high temperatures, obtain covalent organogel composite phase-change material.The present invention has the advantages that 1) develop a kind of novel organogel composite phase-change material；2) for the composite phase-change material prepared by not only it is possible to prevente effectively from the problem of phase transformation core material is revealed, and core material selection is extensive, energy storage density is high；It is suitble to the energy storage of different temperatures section and temperature control, has a wide range of application；3) with composite phase-change material excellent heat transfer properties prepared by the present invention, good cycling stability, simple process, suitable large-scale production.
Description
Technical field:
The invention belongs to composite phase-change material fields, and in particular to a kind of preparation side of organogel composite phase-change material
Method.
Background technique:
Traditional fossil energy is replaced to be energy sustainable development with renewable energy such as solar energy, wind energy, geothermal energy, ocean energies
The only way of exhibition.Currently, these new energy effective rates of utilization are low, supply and demand is limited there are temporal difference
Its practical application.Therefore, it develops new energy storage technology and realizes that the efficient and rational utilization of new energy becomes especially urgent.Phase-change material
(PhaseChangeMaterials, PCMs) can absorb/discharge in phase transition process as the core and key of energy storage skill big
Calorimetric energy, it can be achieved that thermal energy storage and energy room and time transfer.However, pure phase-change material (mainly solid-
Liquid phase-change material) there is the problems such as leakage and low thermal conductivity such as liquid phase, greatly limit its application.By developing composite phase-change
It is the effective way to solve the above problems in shell or porous carrier that phase-change material is packaged in by material.Patent CN104194732A
Disclose the preparation method of a kind of diatomite and paraffin composite phase change material.It is multiple that CN103436240A discloses a kind of foam metal
Close phase-change material and preparation method thereof.To a certain extent, these preparation methods solve phase-change material in phase transition process
Leakage problem.But the disadvantages of that there is specific surface areas is small for carrier material used, and pore volume is small, and pore-size distribution is relatively narrow, cause
Composite phase-change material load capacity is low, potential heat value is low, limits its practical application.Therefore, it develops a kind of with high-ratio surface
Long-pending, high porosity porous material is of great significance for phase-changing energy storage material application.
Organogel is a kind of three-dimensional crosslinked network polymer, by cross-linked network and the solvent being dispersed in network gap point
Son is constituted.Its physicochemical properties is unique, is that a kind of viscoplasticity is extraordinary " soft substance ", has both the property of solid and liquid:
Wherein cross-linked network plays a supportive role, and gel is enable to keep certain form as solid；Full of entire gel network
Solvent molecule has motility and mobility as liquid, and internetwork small-molecule substance can be with free diffusing, Ke Yijin
Inside row gel or the energy between outside, substance and information exchange.In addition, gel and covalent organic framework
(CovalentOrganicFramework, COF) is similar, and the porosity of specific surface area and superelevation with super large utilizes this
Characteristic can use it to absorption phase transformation core material, the gel composite phase-change material of preparation high load amount, high circulation usability.
Summary of the invention:
It is an object of the invention to develop a kind of organic gel materials, and as carrier adsorption phase transformation core material, system
Standby organogel composite phase-change material.It, can Effective Regulation gel and phase by the selection to ligand according to different phase-change materials
The active force for becoming core material optimizes the energy storage effect of composite phase-change material, solves leakage of phase-change material during phase transition and asks
Topic.Gained organogel composite phase-change material has energy storage density big, and cyclicity is good, cheap and have a wide range of application excellent
Gesture.
The technical scheme is that 1) prepare organic wet gel, solvent point by the condensation reaction of amino and aldehyde first
Son is in the network structure of organic wet gel, in occupation of the hole of wet gel；2) it after dissolving phase-change material with solvent, is added to
It in above-mentioned wet gel and is uniformly mixed, said mixture is heated, with the volatilization of solvent molecule, phase-change material is slowly impregnated into
In gel network structure, to obtain organogel composite phase-change material.
Specific preparation step are as follows:
(1) preparation of gel:
Aldehyde and two amine ligands are added in solvent and are configured to homogeneous phase solution, is added a certain amount of 1~5M's into solution
Acetum, sealing is put into 40~150 DEG C of baking oven after being uniformly dispersed, and keeps the temperature 24-72h, and cooled and filtered is simultaneously washed repeatedly
It washs, obtains organic wet gel.Wherein, aldehyde: two amine ligands: sour molar ratio are as follows: 1~50:1~50:0~10.
(2) the covalently preparation of organogel composite phase-change material:
It weighs a certain amount of soluble phase-change material and is dissolved in formation phase transformation core material in coordinative solvent, phase transformation core material is added
It is uniformly mixed into the container for filling above-mentioned wet gel, said mixture is heated, removal solvent impregnates phase-change material slowly
Into gel network structure to get arrive organogel composite phase-change material.The matter of soluble phase-change material and organogel matrix
Amount is than being 1~100:1~100.
Aldehyde ligand described in step (1) includes: four arm aldehyde, terephthalaldehyde, butanedial, one kind of hexandial etc. or several
Kind.
Two amine ligands described in step (1) include: p-phenylenediamine, 2,5- dimethyl-p-phenylenediamines, the fluoro- 5- methyl-1 of 2-,
4- phenylenediamine, 2- nitro is to phenylenediamine, the chloro- 5- methyl-1 of 2-, 4- phenylenediamine, 2,3,5,6- tetramethyls-Isosorbide-5-Nitrae-phenylenediamine, and 3,
4'- diaminodiphenyl-methane, 4,4 '-diaminodiphenyl-methanes, 4,4'- diaminobenzophenones, 4,4'- diamino -3,
3'- dimethyl diphenyl methane, 2,2- bis- (4- aminophenyl) propane, 4,4'- di-2-ethylhexylphosphine oxides (2,6- dimethylaniline), 4- (4-
Amino -2,5- dimethyl benzyl) -2,5- dimethylaniline, 1,1- bis- (4- aminophenyl) hexamethylenes, 4,4'- di-2-ethylhexylphosphine oxide (2-
Ethyl -6- methylaniline), 4,4'- di-2-ethylhexylphosphine oxides (2,6- diethylaniline), bis- (the 4- aminophenyl)-Isosorbide-5-Nitrae-diisopropyls of α, α ' -
Base benzene, the one or more of Isosorbide-5-Nitrae-phenylene two [[4- (4- amino-benzene oxygen) phenyl] ketone] etc..
Step (1) and step (2) described solvent include: dehydrated alcohol, anhydrous methanol, water, methylene chloride, chloroform,
Tetrahydrofuran, acetonitrile, toluene, Isosorbide-5-Nitrae dioxane, n,N-Dimethylformamide, N, N- diethylformamide etc. are one such
Or it is several.
Soluble phase-change material described in step (2) includes:
Polyalcohols specifically include polyethylene glycol (average molecular weight 1000-20000), pentaerythrite, neopentyl glycol
Deng；
Fatty acid specifically includes stearic acid, myristic acid, palmitinic acid, capric acid, lauric acid, pentadecanoic acid, decanedioic acid
Deng；
Paraffin class specifically includes paraffin -58 etc.；Polyoxyethylene ether specifically includes c16e2；brij-52；brij-56；
brij-58；brij-58(r)；brij(r)-52；brij(r)-56；brij(r)-58；
Linear paraffin specifically includes decane, n-tetradecane, hexadecane, n-octadecane；
The crystallization water and salt, specifically include washing soda, sal glauberi, ten hydrogen phosphate dihydrate sodium, calcium chloride hexahydrate,
Sodium acetate trihydrate, five water sodium thiosulfate.
The present invention has the advantages that 1) develop a kind of novel organogel composite phase-change material；2) compound phase prepared by
Become material not only it is possible to prevente effectively from the problem of phase transformation core material is revealed, and core material selection is extensive, energy storage density is high；It is suitble to difference
Temperature range energy storage and temperature control, have a wide range of application；3) steady with composite phase-change material excellent heat transfer properties prepared by the present invention, circulation
Qualitative good, simple process is suitble to large-scale production.
Detailed description of the invention
Fig. 1 is that case study on implementation 1 of the present invention obtains Cog-4CH3Xerogel, PEG6000 and PEG6000 load capacity are 85%
PEG6000@Cog-4CH3The FT-IR of composite phase-change material schemes.
Fig. 2 is that case study on implementation 1 of the present invention obtains Cog-4CH3When xerogel, PEG6000 and PEG6000 load capacity are 85%
PEG6000@Cog-4CH3The XRD diagram of composite phase-change material.
Fig. 3 is that case study on implementation 1 of the present invention obtains Cog-4CH3When xerogel, PEG6000 and PEG6000 load capacity are 85%
PEG6000@Cog-4CH3The TGA of composite phase-change material schemes.
Fig. 4 is that case study on implementation 1 of the present invention obtains PEG6000@Cog- when PEG6000 and PEG6000 load capacity is 85%
4CH3The DSC of composite phase-change material schemes.
Fig. 5 is that case study on implementation 2 of the present invention obtains Cog-CH3When xerogel, PEG4000 and PEG4000 load capacity are 85%
PEG6000@Cog-CH3The FT-IR of composite phase-change material schemes.
Fig. 6 is that invention case study on implementation 2 obtains Cog-CH3When xerogel, PEG4000 and PEG4000 load capacity are 85%
PEG6000@Cog-CH3The XRD diagram of composite phase-change material.
Fig. 7 is that case study on implementation 2 of the present invention obtains PEG6000@Cog- when PEG4000 and PEG4000 load capacity is 85%
CH3The DSC of composite phase-change material schemes.
Specific embodiment
Case study on implementation 1
(1) by tetra- arm aldehyde of 0.11g, 0.0657g2,3,5,6- tetramethyls-Isosorbide-5-Nitrae-phenylenediamine is added to Isosorbide-5-Nitrae-dioxy of 5mL
In six rings then ultrasonic disperse is added 0.4mL3M acetum, is put into 100 DEG C of baking oven after shaking up to transparent, stands for 24 hours,
Product is washed repeatedly with dehydrated alcohol, obtains Cog-4CH3Gel.
(2) by a certain amount of phase transformation core material PEG6000, (PEG6000 accounts for PEG6000 and Cog-4CH3The hundred of gel gross mass
Divide than being respectively 50%, 60%, 70%, 80%, 85%) it is dissolved in 10mL ethyl alcohol, gel rubber material is added after evenly dispersed
In container, 8h is stood at 60 DEG C, and covalent organogel base composite phase-change material is obtained after finally removing solvent.
Case study on implementation 2
(1) by tetra- arm aldehyde of 0.11g, 0.0545g2,5 ,-dimethyl-p-phenylenediamine is added in Isosorbide-5-Nitrae-dioxane of 5mL
Then ultrasonic disperse is added 0.4mL3M acetum, is put into 100 DEG C of baking oven after shaking up to transparent, stand for 24 hours, by product
It is washed repeatedly with dehydrated alcohol, obtains Cog-CH3Gel.
(2) by a certain amount of phase transformation core material PEG4000, (PEG4000 accounts for the hundred of PEG4000 and Cog-CH3 gel gross mass
Divide than being respectively 50%, 60%, 70%, 80%, 85%) it is dissolved in 10mL ethyl alcohol, gel rubber material is added after evenly dispersed
In container, 8h is stood at 60 DEG C, and covalent organogel base composite phase-change material is obtained after finally removing solvent.
Claims (5)
1. a kind of preparation method of organogel composite phase-change material, it is characterised in that: specific preparation step are as follows:
(1) preparation of gel:
Aldehyde and two amine ligands are added in solvent and are configured to homogeneous phase solution, the acetic acid that a certain amount of 1 ~ 5M is added into solution is molten
Liquid, sealing is put into 40 ~ 150 DEG C of baking oven after being uniformly dispersed, and keeps the temperature 24-72 h, and cooled and filtered is simultaneously washed repeatedly, obtained
To organic wet gel；Wherein, aldehyde: two amine ligands: the molar ratio of acetic acid are as follows: [1,50]: [1,50]: (0,10]；
(2) the covalently preparation of organogel composite phase-change material:
It weighs a certain amount of soluble phase-change material and is dissolved in formation phase transformation core material in coordinative solvent, phase transformation core material is added to Sheng
Have in the container of step (1) organic wet gel and be uniformly mixed, mixture is heated, removal solvent soaks phase-change material slowly
Stain arrives organogel composite phase-change material into gel network structure；Soluble phase-change material and organogel matrix
Mass ratio is 1 ~ 100:1 ~ 100；
Aldehyde ligand described in step (1) includes: one or more of four arm aldehyde, terephthalaldehyde, butanedial, hexandial.
2. a kind of preparation method of organogel composite phase-change material as described in claim 1, it is characterised in that: step (1) institute
Two amine ligands stated include: p-phenylenediamine, 2,5- dimethyl-p-phenylenediamine, the fluoro- 5- methyl-1 of 2-, 4- phenylenediamine, 2- nitro pair
The chloro- 5- methyl-1 of phenylenediamine, 2-, 4- phenylenediamine, 2,3,5,6- tetramethyl -1,4- phenylenediamine, 3,4'- diamino-diphenyl first
Alkane, 4,4 '-diaminodiphenyl-methanes, 4,4'- diaminobenzophenone, 4,4'- diamino -3,3'- dimethyl diphenyl methane,
Bis- (4- aminophenyl) propane of 2,2-, 4,4' methylene bis (2,6- dimethylaniline), 4-(4- amino -2,5- dimethylbenzyl
Base) -2,5- dimethylaniline, bis- (4- aminophenyl) hexamethylenes of 1,1-, 4,4' methylene bis (2- ethyl -6- methylaniline),
4,4' methylene bis (2,6- diethylaniline), α, bis- (4- the aminophenyl) -1,4- diisopropyl benzenes of α ' -, 1,4- phenylene two
One or more of [[4-(4- amino-benzene oxygen) phenyl] ketone].
3. a kind of preparation method of organogel composite phase-change material as described in claim 1, it is characterised in that: step (1) and
Step (2) described solvent are as follows: dehydrated alcohol, anhydrous methanol, water, methylene chloride, chloroform, tetrahydrofuran, acetonitrile, toluene,
1,4- dioxane, N,N-dimethylformamide, N, N- diethylformamide are one such or several.
4. a kind of preparation method of organogel composite phase-change material as described in claim 1, it is characterised in that: step (2) institute
The soluble phase-change material stated includes:
Polyalcohols；
Fatty acid；
Paraffin class；
Polyoxyethylene ether；
Linear paraffin；
The crystallization water and salt.
5. a kind of preparation method of organogel composite phase-change material as claimed in claim 4, it is characterised in that:
The polyalcohols are polyethylene glycol, pentaerythrite, neopentyl glycol, and the polyethylene glycol average molecular weight is 1000-
20000；
The fatty acid is stearic acid, myristic acid, palmitinic acid, capric acid, lauric acid, pentadecanoic acid, decanedioic acid；
The paraffin class is paraffin -58；
The polyoxyethylene ether is c16e2, brij-52, brij-56, brij-58, brij-58 (r), brij (r) -52, brij
(r)-56,brij(r)-58；
The linear paraffin includes decane, n-tetradecane, hexadecane, n-octadecane；
The crystallization water and salt include washing soda, sal glauberi, ten hydrogen phosphate dihydrate sodium, calcium chloride hexahydrate, three water
Sodium acetate, five water sodium thiosulfate.
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| CN103936953A (en) * | 2014-04-22 | 2014-07-23 | 中国石油大学(北京) | Synthetic method of phase change material polytetramethylene glycol amine aldehyde condensation crosslinking copolymer |
| US11130895B2 (en) * | 2016-09-20 | 2021-09-28 | Aspen Aerogels, Inc. | Aerogel composites having thermal storage capacity |
| CN106514800B (en) * | 2016-11-15 | 2019-07-12 | 郑州一安水性高分子材料有限公司 | Flame retardant type log cabin Special composite board material without formaldehyde and preparation method thereof |
| CN106675525A (en) * | 2016-11-25 | 2017-05-17 | 贺迈新能源科技（上海）有限公司 | Phase change cold storage material with double phase change points and preparation method thereof |
| CN107822198B (en) * | 2017-09-18 | 2019-11-08 | 四川三联卷烟材料有限公司 | A kind of non-burning cigarette aerosol coolant and preparation method thereof of heating |
| CN110124105B (en) * | 2019-04-15 | 2021-10-29 | 杭州电子科技大学 | Preparation method of biological 3D printing ink capable of regulating and controlling gel-sol phase transition temperature |
| CN111808577A (en) * | 2020-05-27 | 2020-10-23 | 纯钧新材料(深圳)有限公司 | High-stability composite phase-change gel for cold chain transportation of 2-8 ℃ medicines |
| CN112536004B (en) * | 2020-12-03 | 2022-10-14 | 航天特种材料及工艺技术研究所 | High-temperature-resistant elastic graphene aerogel material and preparation method thereof |
| CN113265229B (en) * | 2021-06-04 | 2022-10-14 | 南方科技大学 | Phase-change gel material and preparation method and application thereof |
| CN114305852A (en) * | 2022-03-10 | 2022-04-12 | 北京科技大学 | Phase change material cold compress paste |
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| CN104772088A (en) * | 2015-04-02 | 2015-07-15 | 北京科技大学 | Template-free preparation method of hollow micro-spherical polymers with covalent organic frameworks (COFs) |
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