CN104893671B - A kind of carbamates gelator composite shape-setting phase-change material and preparation method thereof - Google Patents
A kind of carbamates gelator composite shape-setting phase-change material and preparation method thereof Download PDFInfo
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Abstract
The present invention discloses a kind of carbamates gelator composite shape-setting phase-change material and preparation method thereof.The shaping phase-change material of the present invention is made of following methods：(1) phase-change material 85~99.5%, carbamates gelator 0.5~15% are weighed by mass percentage；(2) described carbamates gelator is added to in described phase-change material heating stirring transparent mixture is made to being completely dissolved；(3) described transparent mixture is placed in mould, natural cooling obtains composite shape-setting phase-change material.The present invention is used as heat-storing material using solid-liquid phase change material, using backing material of the spacial framework that organic micromolecule gel factor is self-assembly of as phase-change material, the shaping phase-change material that enthalpy of phase change is high, preparation cost is low, preparation technology is simple, application performance is good can be obtained.
Description
Technical field
The present invention relates to a kind of shaping phase-change material and preparation method thereof, and in particular to a kind of carbamate gellike because
Sub- composite shape-setting phase-change material and preparation method thereof.
Background technology
Phase-change material (PCMs) is to carry out energy storage with a large amount of heat absorptions and exothermic effect in phase transition process using material
Deposit the general designation with the material of temperature adjusting.Phase-change material building energy conservation, road traffic, Modern Greenhouse of Agriculture, Solar use,
The refrigeration and transport of food, health care, electronic equipment dissipating heat, sportsman's cooling and warming dress ornament, special temperature-controlled garment, space flight
The numerous areas such as scientific and technological, military infrared camouflage, electric power peak load shifting, industrial exhaust heat storage utilization, energy recovery have wide
Application prospect.
By the typoiogical classification of phase transition process, phase-change material can be divided into solid-liquid phase change, solid-solid phase-change, solid-gas phase transformation, liquid-
Gas phase becomes four kinds of phase-change materials.Development at present is very fast, study and what application was more is solid-liquid phase change material and solid-solid phase-change material
Material.The major advantage of solid-liquid phase change material is cheap and easy to get, and phase transformation enthalpy is higher.But it has liquid phase generation in phase transformation, has
Certain mobility, it is therefore necessary to there is container splendid attire and container must seal, corroded with prevent leakage or pollute environment, and
Container must be for phase-change material it is inert, this shortcoming greatly fettered solid-liquid phase change material in practice should
With.Solid-solid phase transition material has many good qualities compared with solid-liquid phase change material：When contained without container, it is easy to use；Second,
Stable performance, service life length；Third, the coefficient of expansion is smaller, Volume Changes are small.But solid-solid phase transition material species is less, phase transformation
Enthalpy is smaller, and heat conductivility is poor, has also fettered its application in practice.Comprehensive solid-liquid phase change material and solid-solid phase transition material
Advantage and disadvantage, there is the solid-liquid phase change material of a major class dimensionally stable, it is mainly made up of two parts：When operation material, one
As be organic solid-liquid phase change material, realize the storage of energy and release using its solid-liquid phase change.It is another be carrier matrix (or
Claim backing material), its main function is after operation material is undergone phase transition, to play skeletal support in system, suppresses
The flowing and deformation of material, make shaping phase-change material macroscopically keep shape to fix.At present, the method for preparing shaping phase-change material
Mainly there are microcapsule method, inorganic material absorption method and high polymer material fixation.
Microcapsule method is that solid-liquid phase change material is overmolding into one kind side with nucleocapsid structure particulate by filmogen
Method, obtained particulate are referred to as microcapsules, are made up of cyst wall and capsule-core two parts, and in phase transition process, solid-liquid phase occurs for capsule-core
Become, and cyst wall remains solid-state.Therefore, such phase-change material is macroscopically showing as solid particle, no liquid leakage.Microcapsules
Phase-change material is typically used as capsule-core, polymer or inorganic using solid-liquid phase change materials such as paraffin, aliphatic acid, polyethylene glycol (PEG)
Material is cyst wall.The red grades (CN102417812A) of Lanzhou University of Science ＆ Technology Guo Jun coat positive 14 with carbamide prepolymer
Alcohol prepares phase-change microcapsule, and wherein tetradecanol mass fraction is 60~70%, and carbamide prepolymer mass fraction is
30~40%.Donghua University in big eastern (CN1695788A) using vinyl and bi-vinyl class monomer as outer cover polymer source,
Using oil-soluble phase-change material as core, microcapsules of storing energy through phase change, wherein phase-change material quality percentage are prepared using emulsion polymerization
Number is 10~30%.
Inorganic material absorption method is that solid-liquid phase change material is sucked to the stratiform knot of Inorganic material carrier under high temperature or vacuum
In structure or bigger serface micropore.When solid-liquid phase change occurs for phase-change material, liquid is fixed on micropore or interlayer, and liquid is not
It can flow out so that this shaping phase-change material is macroscopically showing as solid state.The Inorganic material carrier of selection mainly has swollen
Swollen graphite, vermiculite, galapectite, expanded perlite, diatomite, montmorillonite, activated carbon etc..Southeast China University Li Min
(CN103059817A) organic phase changing matter and curing agent are mixed in the molten state and generates prepolymer, prepolymer is poured into a mould
Into in the large pore material such as porous graphite hole, composite shape-setting phase-change material is obtained higher than solidification under conditions of raw material phase transition temperature,
The content of organic phase changing matter is 50~85% during it is formulated, and the content of carrier matrix mutually should be 50~15%.The Chinese Academy of Sciences
For Dalian Chemical Physics Research Institute Sun Li virtuous (CN102977858A) using aliphatic acid mixed acid system as phase-change material, expanded graphite is load
Body, when expanded graphite accounts for composite phase-change material 10%, the phase transition temperature of the composite phase-change heat-storage material is 19.6 DEG C, and phase transformation is dived
Heat is 145.5kJ/kg, thermal conductivity factor 0.723Wm-1·K-1, the phase of composite after further being shaped with composite paint
Temperature is 18.6 DEG C, latent heat of phase change 92.4kJ/kg.
High polymer material fixation can be divided into physical blending process and chemical reaction method again.Physical blending process is by polymer
Backing material and phase change material are melted or solution blending, and phase-change material is evenly distributed on to the network structure of polymer formation
In, when solid-liquid phase change occurs, due to the supporting role of polymer network, the shaping phase-change material that shaping is blended does not flow macroscopically
It is dynamic, no liquid leakage.The polymer of selection mainly has cellulose, chitosan, polymethyl methacrylate (PMMA), high density to gather
Ethene, low density polyethylene (LDPE), LLDPE, polyureas, polypropylene, polyvinyl alcohol and polyaniline etc..The Chinese Academy of Sciences
Guangzhou chemistry institute Guo Yuan waits by force (CN1165174；CN1165174) by the polyethylene glycol of different molecular weight and cellulose, fibre
Tie up solution blending after plain derivative, chitosan etc. are dissolved with solvent and prepare compound polyethylene glycol solid phase change material.Work as blending
When the backing material such as cellulose, cellulose derivative, chitosan mass ratio is higher than 15% in thing, blend shows solid-state phase changes
Behavior.The degree of polymerization containing hydroxyl, amino, carboxyl, carbonyl, acyl group is also by they by solution blending or melt-blending process
100~3000 polarity macromolecule and molecular weight is 140~200000 crystallinity or thermal plastic high polymer and the compound system of organic acid
Standby solid-solid phase change material.The grand grade (CN1506434) of Chinese University of Science and Technology's leaf is with two-roll mill by paraffin and polyethylene blend system
Standby shaping phase-change material, Quality of Paraffin Waxes content are 75%.(solar energy journal, 2001,22 (4) such as South China Science ＆ Engineering University Xiao Min:
427) 56~58 DEG C of paraffin of fusing point and thermoplastic elastomer (TPE) are formed into composite phase-change material, the mass fraction of paraffin for 20~
80%.Chemical reaction method is that phase-change material is fixed on into polymer or inorganic material using the methods of in-situ polymerization, sol-gel
In three-dimensional network, reach setting purpose.Pass through situ aggregation method, Wuhan University of Technology Zhang Lei (Energy, 2012,39 (1):
294) it is PEG and PMMA is compound, virtuous (the Journal of Thermal of Dalian Chemiclophysics Inst., Chinese Academy of Sciences Sun Li
Analysis and Calorimetry,2008,91(2):455) tetradecyl alchohol and polyaniline is compound, Institutes Of Technology Of Changsha was once huge
Billows (CN103146351A) are compound with polyaniline by long chain fatty acids, and polymer network shaping phase-change material has been made.By molten
Glue-gel method, Nanjing University Fang Guiyin (CN102260483A) select laurate and hexadecane, South China Science ＆ Engineering University side's Yutang
(CN1793277；) and Lee Singapore of Peking University (European Polymer Journal, 2012,48 (4) CN1322091:
803) PEG is chosen, and Hunan University Zhou Xiangfa (Chemical Engineering Research and Design, 2010,88
(8):1013) SiO is distributed it to as phase-change material using paraffin2Three-dimensional net structure in be prepared for a series of setting
Phase-change material.
In prepared by the shaping phase-change material reported, the weight/mass percentage composition as the carrier matrix of backing material is higher,
The weight/mass percentage composition of phase transformation operation material is relatively low, necessarily causes the reduction of enthalpy of phase change；And grafting, the blending or micro- generally used
The relative raising of phase-change material cost that is encapsulated to wait complicated preparation technology, will also making preparation.
In recent years, it has been found that some small molecular organic compounds (even below 1wt%) can make at very low concentrations
Most of organic solvent gelations, whole system is formed the material of similar memory fluid or solid, referred to as molecular gel or
Organogel.This kind of small molecular organic compounds are referred to as Gelator (being temporarily translated into gelator).Prepare the letter of organogel method
Just：Gelator is dissolved by heating in organic solvent, is cooled to room temperature, gelator spontaneously gathers in cooling procedure
Collect, be assembled into ordered structure, form three-dimensional network system, so as to reach the constraint effect to solvent, and the process is thermal reversion
Process.The research for gelator is concentrated mainly on the gelation of ordinary organic solvents at present, and gelator is applied to
Report in phase-change material is less.University Of Tianjin Song Jian (Solar Energy Materials and Solar Cells,
2011,95(4):1213；Thermochimica Acta,2013,554:54；Functional material, 2013,44 (13):1943；RSC
Advances,2015,5(28):21733) glycosyl acetal analog derivative is dissolved in paraffin, tetradecyl alchohol, octadecyl alcolol, positive 18
In the phase-change materials such as alkane, ethyl palmitate, phase transformation physical gel is made after cooling.Such phase change gel is with a small amount of glycosyl acetals
The supramolecular network structure that gelator is assembled into by hydrogen bond is backing material, reaches more than phase transition temperature in phase-change material
When, gel network does not disassociate, and so as to keep stable gel state, material leakage is not undergone phase transition, so as to obtain one kind
The shaping phase-change material of high phase transformation enthalpy.But the design of the serial gelator considers compatible with the phase-change material such as paraffin
Sex chromosome mosaicism, the network structure and the interphase interaction of phase-change material that gelator is formed are smaller, easily cause phase transformation component under high temperature
Leakage and phase separation.Chinese patent (CN103773321A) provides a kind of amide-type gelator composite shape-setting phase transformation material
Material, there is in selected gelator structure the long alkane chain structure compatible with the phase-change material such as paraffin, hydrogen bond can be passed through
Network structure is self-assembly of etc. non-covalent bond effect, reaches setting supporting role；Meanwhile have in gelator structure and stone
The compatible long alkane chain structure of the phase-change materials such as wax, gelator can be increased and interacted with phase-change material, reduce slip,
But the synthesis technique of the serial gelator is still more complicated.
The content of the invention
It is an object of the invention to overcome deficiency of the prior art, a kind of enthalpy of phase change height is developed, preparation cost is low, system
Standby technique is simple, application performance it is good there is gelator supramolecular network structure as the shaping phase-change material supported.
The present invention central scope be：The carbamates prepared from diisocyanate with unary alcohol compound is had
Machine gelator is the backing material of shaping phase-change material, and solid-liquid phase change material is operation material, passes through simple melt blending
Method prepares shaping phase-change material.By the organogel factor under the non-covalent bond effects such as hydrogen bond self assembled three-dimensional oversubscription subnet
Network structure, reach the supporting role that shaped to solid-liquid phase change material, phase-change material is macroscopically presented more than phase transition temperature and do not flow
Dynamic solid property.
The present invention realizes in the following way：
A kind of carbamates gelator composite shape-setting phase-change material, including by mass percentage such as the following group
Point：Phase-change material 85~99.5%, carbamates gelator 0.5~15%.
Described phase-change material preferred content be 90~99%, carbamates gelator preferred content be 1~
10%.
Described phase-change material is selected from：Alkane paraffin, ceresine or beeswax that carbon number is 18~600, carbon number 8
The higher aliphatic, polyethylene glycol, polyethylene or poly- third that~30 higher fatty acids or fatty acid ester, carbon number are 8~30
Mixture more than one or both of alkene.
Described phase-change material be preferably atoleine, solid paraffin, n-octadecane, octadecyl alcolol, hexadecanol, tetradecyl alchohol,
Lauryl alcohol, Decanol, stearic acid, butyl stearate, stearine, palmitic acid, myristic acid, laurate, capric acid, poly- second
Mixture more than one or both of glycol, polyethylene or polypropylene.
Described carbamates gelator is carbamates organic micromolecule gel factor, its chemical constitution
Formula is：
M is selected from one kind of following structures in formula：
R is selected from one kind of following structures：
Wherein, m=6~18, n=2~10.
The preparation method of above-mentioned carbamates gelator composite shape-setting phase-change material, comprises the following steps：
(1) weigh respectively by mass percentage phase-change material 85~99.5%, carbamates gelator 0.5~
15%；
(2) the above-mentioned carbamates gelator weighed is added in the above-mentioned phase-change material weighed, heating is stirred
Mix to being completely dissolved and transparent mixture is made；
(3) above-mentioned transparent mixture natural cooling is obtained into composite shape-setting phase-change material.
Compared with prior art, the beneficial effects of the present invention are：
(1) present invention is using solid-liquid phase change material as operation material, with carbamates gelator in phase-change material
Formation gel reaches the constraint supporting role to phase-change material, and addition gelator ratio is small, and enthalpy of phase change loss is small, is obtained
Shaping phase-change material enthalpy of phase change is high.
(2) composite Repeat-heating of the invention can still form shaping phase-change material after cooling down again, have well
Reprocess property.
(3) the carbamates gelator selected by the present invention, preparation method is simple, passes through diisocyanate and one
First alcohol simple reaction can obtain the gelator of high yield, and preparation cost is cheap, sufficient raw.The amino of the present invention simultaneously
Formate ester gelator composite shape-setting phase-change material preparation technology is simple, and preparation condition is easily controllable, and preparation cost is relatively low, tool
There are good application performance and wide application prospect.
Embodiment
Gelator composite phase-change energy storage material enthalpy of phase change method of testing：Using PE companies DSC-Q10 means of differential scanning calorimetry
Instrument (DSC) Range of measuring temp is 0 DEG C~100 DEG C, nitrogen atmosphere protection, heating rate：10 DEG C/min, rate of temperature fall：10℃/
min。
Gel disassociates temperature (TD) and gel-sol temperature (TGS) test use test tube gradient method：Phase change gel will be housed
The test tube bottom of material is inserted in transparent oil bath down, then oil bath is heated up with 2 DEG C/min speed.When being warming up to certain temperature
When, test tube is tilted, if gel can flow just, it is determined that the temperature is that gel agglomerates structure disassociates temperature (TD).When
There is TDFollow-up temperature of continuing rising, and temperature when gel to be all dissolved as to liquid is defined as gel-sol phase transition temperature (TGS)。
It will be helpful to understand the present invention by following instance, but be not intended to limit present disclosure.
Embodiment 1
The carbamates gelator that the present embodiment is selected is (the carbamic acid octadecyl of diphenyl-methane -4,4 '-two
Ester) (MDCM-18), its structural formula is：
The solid paraffin 4.0g that fusing point is 56~58 DEG C, enthalpy of phase change is 189.3J/g is taken, in 25mm × 40mm sample bottles
Melt, add gelator MDCM-18, it is 3% to be allowed to mass percent, and heating stirring to being completely dissolved, clarify by thing to be mixed
Afterwards, gelator composite shape-setting phase-change material is made in natural cooling.
It is 180.3J/g that shaping phase-change material obtained by the present embodiment tests enthalpy of phase change through differential scanning calorimeter (DSC),
Phase transition temperature is 58.6 DEG C.The gel that test tube gradient method measures phase change gel disassociates temperature as 98 DEG C, and gel-sol temperature is
102℃。
Embodiment 2
Carbamates gelator selected by the present embodiment is the same as embodiment 1.
The solid paraffin 4.0g that fusing point is 56~58 DEG C, enthalpy of phase change is 189.3J/g is taken, in 25mm × 40mm sample bottles
Melt, add gelator MDCM-18, it is 1% to be allowed to mass percent, and heating stirring to being completely dissolved, clarify by thing to be mixed
Afterwards, gelator composite shape-setting phase-change material is made in natural cooling.
It is 178.4J/g that shaping phase-change material obtained by the present embodiment tests enthalpy of phase change through differential scanning calorimeter (DSC),
Phase transition temperature is 58.7 DEG C.The gel that test tube gradient method measures phase change gel disassociates temperature as 89 DEG C, and gel-sol temperature is 92
℃。
Embodiment 3
Carbamates gelator selected by the present embodiment is the same as embodiment 1.
The solid paraffin 4.0g that fusing point is 56~58 DEG C, enthalpy of phase change is 189.3J/g is taken, in 25mm × 40mm sample bottles
Melt, add gelator MDCM-18, it is 6% to be allowed to mass percent, and heating stirring to being completely dissolved, clarify by thing to be mixed
Afterwards, gelator composite shape-setting phase-change material is made in natural cooling.
Shaping phase-change material obtained by the present embodiment tests enthalpy of phase change 181.1J/g through differential scanning calorimeter (DSC) and is,
Phase transition temperature is 58.7 DEG C.The gel that test tube gradient method measures phase change gel disassociates temperature as 103 DEG C, and gel-sol temperature is
106℃。
Embodiment 4
Carbamates gelator selected by the present embodiment is the same as embodiment 1.
PEG-4000 (PEG-6000) 4.0g that fusing point is 65~67 DEG C, enthalpy of phase change is 169.7J/g is taken, in 25mm
Melt in × 40mm sample bottles, add gelator MDCM-18, be allowed to mass percent as 3%, heating stirring is to completely molten
Solution, after thing clarification to be mixed, gelator composite shape-setting phase-change material is made in natural cooling.
It is 166.2J/g that shaping phase-change material obtained by the present embodiment tests enthalpy of phase change through differential scanning calorimeter (DSC),
Phase transition temperature is 66.1 DEG C.The gel that test tube gradient method measures phase change gel disassociates temperature as 99 DEG C, and gel-sol temperature is
101℃。
Embodiment 5
The carbamates gelator that the present embodiment is selected is (the carbamic acid cetyl of diphenyl-methane -4,4 '-two
Ester) (MDCM-16), its structural formula is：
The solid paraffin 4.0g that fusing point is 56~58 DEG C, enthalpy of phase change is 189.3J/g is taken, in 25mm × 40mm sample bottles
Melt, add gelator MDCM-16, it is 3% to be allowed to mass percent, and heating stirring to being completely dissolved, clarify by thing to be mixed
Afterwards, gelator composite shape-setting phase-change material is made in natural cooling.
It is 179.4J/g that shaping phase-change material obtained by the present embodiment tests enthalpy of phase change through differential scanning calorimeter (DSC),
Phase transition temperature is 58.3 DEG C.The gel that test tube gradient method measures phase change gel disassociates temperature as 97 DEG C, and gel-sol temperature is
102℃。
Embodiment 6
The carbamates gelator that the present embodiment is selected is hexa-methylene two (octadecyl carbamate)
(HDCM-18), its structural formula is：
The solid paraffin 4.0g that fusing point is 56~58 DEG C, enthalpy of phase change is 189.3J/g is taken, in 25mm × 40mm sample bottles
Melt, add gelator HDCM-18, it is 3% to be allowed to mass percent, and heating stirring to being completely dissolved, clarify by thing to be mixed
Afterwards, gelator composite shape-setting phase-change material is made in natural cooling.
It is 178.0J/g that shaping phase-change material obtained by the present embodiment tests enthalpy of phase change through differential scanning calorimeter (DSC),
Phase transition temperature is 58.5 DEG C.The gel that test tube gradient method measures phase change gel disassociates temperature as 87 DEG C, and gel-sol temperature is 89
℃。
Embodiment 7
Carbamates gelator selected by the present embodiment is the same as embodiment 6.
The solid paraffin 4.0g that fusing point is 56~58 DEG C, enthalpy of phase change is 189.3J/g is taken, in 25mm × 40mm sample bottles
Melt, add gelator HDCM-18, it is 2% to be allowed to mass percent, and heating stirring to being completely dissolved, clarify by thing to be mixed
Afterwards, gelator composite shape-setting phase-change material is made in natural cooling.
It is 178.1J/g that shaping phase-change material obtained by the present embodiment tests enthalpy of phase change through differential scanning calorimeter (DSC),
Phase transition temperature is 58.4 DEG C.The gel that test tube gradient method measures phase change gel disassociates temperature as 81 DEG C, and gel-sol temperature is 84
℃。
Embodiment 8
Carbamates gelator selected by the present embodiment is the same as embodiment 6.
The solid paraffin 4.0g that fusing point is 56~58 DEG C, enthalpy of phase change is 189.3J/g is taken, in 25mm × 40mm sample bottles
Melt, add gelator HDCM-18, it is 6% to be allowed to mass percent, and heating stirring to being completely dissolved, clarify by thing to be mixed
Afterwards, gelator composite shape-setting phase-change material is made in natural cooling.
It is 178.9J/g that shaping phase-change material obtained by the present embodiment tests enthalpy of phase change through differential scanning calorimeter (DSC),
Phase transition temperature is 58.5 DEG C.The gel that test tube gradient method measures phase change gel disassociates temperature as 98 DEG C, and gel-sol temperature is
100℃。
Embodiment 9
Carbamates gelator selected by the present embodiment is the same as embodiment 6.
The PEG-60004.0g that fusing point is 65~67 DEG C, enthalpy of phase change is 169.7J/g is taken, in 25mm × 40mm sample bottles
Melt, add gelator HDCM-18, it is 3% to be allowed to mass percent, and heating stirring to being completely dissolved, clarify by thing to be mixed
Afterwards, gelator composite shape-setting phase-change material is made in natural cooling.
It is 165.9J/g that shaping phase-change material obtained by the present embodiment tests enthalpy of phase change through differential scanning calorimeter (DSC),
Phase transition temperature is 66.0 DEG C.The gel that test tube gradient method measures phase change gel disassociates temperature as 86 DEG C, and gel-sol temperature is 88
℃。
Embodiment 10
The carbamates gelator that the present embodiment is selected is hexa-methylene two (carbamic acid cetyl ester)
(HDCM-16), its structural formula is：
The solid paraffin 4.0g that fusing point is 56~58 DEG C, enthalpy of phase change is 189.3J/g is taken, in 25mm × 40mm sample bottles
Melt, add gelator HDCM-16, it is 3% to be allowed to mass percent, and heating stirring to being completely dissolved, clarify by thing to be mixed
Afterwards, gelator composite shape-setting phase-change material is made in natural cooling.
It is 178.2J/g that shaping phase-change material obtained by the present embodiment tests enthalpy of phase change through differential scanning calorimeter (DSC),
Phase transition temperature is 58.9 DEG C.The gel that test tube gradient method measures phase change gel disassociates temperature as 88 DEG C, and gel-sol temperature is 90
℃。
Embodiment 11
The carbamates gelator that the present embodiment is selected is Toluene-2,4-diisocyanate, 4- bis- (carbamic acid hexyl ester) (TDCM-
6), its structural formula is：
The solid paraffin 4.0g that fusing point is 56~58 DEG C, enthalpy of phase change is 189.3J/g is taken, in 25mm × 40mm sample bottles
Melt, add gelator TDCM-6, it is 6% to be allowed to mass percent, and heating stirring to being completely dissolved, clarify by thing to be mixed
Afterwards, gelator composite shape-setting phase-change material is made in natural cooling.
It is 178.8J/g that shaping phase-change material obtained by the present embodiment tests enthalpy of phase change through differential scanning calorimeter (DSC),
Phase transition temperature is 58.4 DEG C.The gel that test tube gradient method measures phase change gel disassociates temperature as 102 DEG C, and gel-sol temperature is
104℃。
Embodiment 12
Carbamates gelator selected by the present embodiment is the same as embodiment 11.
The solid paraffin 4.0g that fusing point is 56~58 DEG C, enthalpy of phase change is 189.3J/g is taken, in 25mm × 40mm sample bottles
Melt, add gelator TDCM-6, it is 8% to be allowed to mass percent, and heating stirring to being completely dissolved, clarify by thing to be mixed
Afterwards, gelator composite shape-setting phase-change material is made in natural cooling
It is 178.3J/g that shaping phase-change material obtained by the present embodiment tests enthalpy of phase change through differential scanning calorimeter (DSC),
Phase transition temperature is 58.4 DEG C.The gel that test tube gradient method measures phase change gel disassociates temperature as 117 DEG C, and gel-sol temperature is
120℃。
Embodiment 13
Carbamates gelator selected by the present embodiment is the same as embodiment 11.
The PEG-60004.0g that fusing point is 65~67 DEG C, enthalpy of phase change is 169.7J/g is taken, in 25mm × 40mm sample bottles
Melt, add gelator TDCM-6, it is 6% to be allowed to mass percent, and heating stirring to being completely dissolved, clarify by thing to be mixed
Afterwards, gelator composite shape-setting phase-change material is made in natural cooling.
Shaping phase-change material obtained by the present embodiment tests enthalpy of phase change 167.5J/g through differential scanning calorimeter (DSC) and is,
Phase transition temperature is 66.2 DEG C.The gel that test tube gradient method measures phase change gel disassociates temperature as 101 DEG C, and gel-sol temperature is
103℃。
Embodiment 14
The carbamates gelator that the present embodiment is selected is Toluene-2,4-diisocyanate, 4- bis- (carbamic acid octyl group ester) (TDCM-
8), its structural formula is：
The solid paraffin 4.0g that fusing point is 56~58 DEG C, enthalpy of phase change is 189.3J/g is taken, in 25mm × 40mm sample bottles
Melt, add gelator TDCM-8, it is 6% to be allowed to mass percent, and heating stirring to being completely dissolved, clarify by thing to be mixed
Afterwards, gelator composite shape-setting phase-change material is made in natural cooling
It is 178.9J/g that shaping phase-change material obtained by the present embodiment tests enthalpy of phase change through differential scanning calorimeter (DSC),
Phase transition temperature is 58.8 DEG C.The gel that test tube gradient method measures phase change gel disassociates temperature as 87 DEG C, and gel-sol temperature is 89
℃。
Claims (4)
1. a kind of carbamates gelator composite shape-setting phase-change material, it is characterised in that comprising by mass percentage
Following component：Phase-change material 85 ~ 99.5%, carbamates gelator 0.5 ~ 15%；
Described carbamates gelator is carbamates organic micromolecule gel factor, its chemical structural formula
For：
The one kind of M in following structures in formula：
The one kind of R in following structures：
。
2. carbamates gelator composite shape-setting phase-change material according to claim 1, it is characterised in that：It is described
The content of phase-change material be 90 ~ 99%, the content of carbamates gelator is 1 ~ 10%.
3. carbamates gelator composite shape-setting phase-change material according to claim 1 or 2, it is characterised in that：
Described phase-change material is atoleine, solid paraffin, n-octadecane, octadecyl alcolol, hexadecanol, tetradecyl alchohol, lauryl alcohol, the positive last of the ten Heavenly stems
Alcohol, stearic acid, butyl stearate, stearine, palmitic acid, myristic acid, laurate, capric acid, polyethylene glycol, polyethylene
Or mixture more than one or both of polypropylene.
4. the preparation method of the carbamates gelator composite shape-setting phase-change material described in any one of claims 1 to 3,
It is characterized in that comprise the following steps：
（1）Phase-change material 85 ~ 99.5%, carbamates gelator 0.5 ~ 15% are weighed by mass percentage；Or phase transformation material
Material 90 ~ 99%%, carbamates gelator 1 ~ 10%；
（2）By step（1）Obtained carbamates gelator is added in phase-change material, heating stirring to completely it is molten
Solution, transparent mixture is made；
（3）By step（2）Obtained transparent mixture natural cooling, obtains composite shape-setting phase-change material.
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| CN106831412A (en) * | 2017-01-16 | 2017-06-13 | 南京工业大学 | The preparation method of butanediol fatty acid ester and its application as gelator |
| ES2677444B1 (en) * | 2017-02-01 | 2019-05-09 | Gamesa Innovation & Technology S L | Use of phase change materials to slow the formation of ice or produce de-icing in wind turbines |
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| CN111647389A (en) * | 2020-06-17 | 2020-09-11 | 塔里木大学 | Preparation method and product of phase change coolant |
| CN113136200A (en) * | 2021-04-27 | 2021-07-20 | 湘潭大学 | Circular polarization luminous liquid crystal physical gel material and preparation method thereof |
| CN116162044B (en) * | 2023-03-06 | 2024-03-01 | 湖北航天化学技术研究所 | Organogel factor and organogel material, and preparation method and application thereof |
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