CN110105925A - Cetylamine/silicon dioxide composite shape-stabilized phase phase-change material preparation method - Google Patents
Cetylamine/silicon dioxide composite shape-stabilized phase phase-change material preparation method Download PDFInfo
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- CN110105925A CN110105925A CN201910424257.2A CN201910424257A CN110105925A CN 110105925 A CN110105925 A CN 110105925A CN 201910424257 A CN201910424257 A CN 201910424257A CN 110105925 A CN110105925 A CN 110105925A
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- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
- C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
Abstract
The invention discloses cetylamine/silicon dioxide composite shape-stabilized phase phase-change material preparation methods, comprising: at 15~50 DEG C cetylamine is dissolved in isopropanol, then deionized water is added thereto, obtain mixed solution；Then the mixing of the ethanol solution and hydrochloric acid of 3- aminopropyl -3- Ethoxysilane is added to immediately in the mixed solution, finally ethyl orthosilicate is added thereto and is reacted, obtain final product after dry.The method of the present invention simple process, it is easy to accomplish；The problem of using cetylamine produced by the present invention/silicon dioxide composite shape-stabilized phase phase-change material, enthalpy of phase change is high, has good packaging effect, and Product transport is simple, can effectively solve the liquid phase leakage that material occurs in use.
Description
Technical field
The invention belongs to phase-change accumulation energy fields, and in particular to the preparation of cetylamine/silicon dioxide composite shape-stabilized phase phase-change material
Method.
Background technique
Phase-change material refers to that own temperature remains unchanged when phase transformation occurs, and is but absorbed, is stored in the form of latent heat
And the material of release heat.Phase-change material is as a kind of advanced energy storage material, because of its energy storage density with higher, stabilization
Chemical structure and excellent temperature modulating properties and the extensive concern by every field, for example, solar energy storage, intelligence are protected
Thermal protection, waste heat recycling of the textile, electronic device of temperature etc..Wherein, solid-liquid phase change material with its higher storage density,
The features such as phase transformation volume change is small, degree of supercooling is small becomes the most viable and most practical valence that current researcher is unanimously thought
The phase-change material of value.But in practical applications, there is liquid phase substance leakage in most solid-liquid phase change materials.
One of the approach of mobility and corrosion problems (that is, leakage problem) after solution solid-liquid phase change material phase transformation at present
Exactly develop shaping phase-change material.Shaping phase-change material is will using capsule, porous material or high molecular material etc. as support
Phase-change material is included in short space one by one, and certain shape is maintained when guaranteeing phase transformation.That is, selecting a kind of fusing point higher
Material be matrix, by phase-change material dispersion wherein, constitute composite shape-setting phase-change material.This material when undergoing phase transition, by
In the supporting role of basis material, although phase-change material is liquid by Solid State Transformation, entire composite phase-change material is still maintained
In former solid state.This kind of material is not required to encapsulation utensil, reduces packaging cost and encapsulation difficulty, avoids the danger of material leakage
Danger, increases the safety used, reduces the heat transfer resistance of container.
SiO2As a kind of inexpensive and large specific surface area porous mass, because its is cheap, nontoxic, can enhance other materials
Anti-aging, the chemical property of material, and the setting for being widely used in solid-liquid phase change ergastic substances is modified.SiO2Fixed phase change energy storage
The preparation method of material, there are mainly two types of, first is that vacuum plunging, i.e., use, which vacuumizes decompression, makes porous material De contamination, phase
Phase-change accumulation energy substance after change is pressed into the hole configurations of more empty materials under the action of air pressure；Second is that sol-gel method, i.e.,
Phase-change accumulation energy substance is dissolved or dispersed in water, setting modification is carried out to phase-change accumulation energy substance by the method for sol-gel.
But the silicon dioxide composite shape-stabilized phase phase-change material of existing report, wherein the amount of phase change material is very low, limits enthalpy of phase change
It is promoted, then limits its application in actual production.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of cetylamine/silicon dioxide composite shape-stabilized phase phase-change material systems
Preparation Method realizes the raising of the phase change material content in composite shape-setting phase-change material by simple process, to mention significantly
High enthalpy of phase change, energy-storage property is good, moreover, composite shape-setting phase-change material obtained is not revealed more than phase transition temperature, produces
Product transport is simple, the liquid phase leakage that material occurs in use is solved the problems, such as, in addition, composite shape-setting obtained
Phase-change material thermal stability is good, using reliable.
In order to achieve the above objectives, the present invention adopts the following technical scheme:
Cetylamine/silicon dioxide composite shape-stabilized phase phase-change material preparation method, comprising the following steps:
(1) cetylamine is added in isopropanol, 15~50 DEG C of revolving speed uniform stirrings 20 with 400~600r/min~
30 minutes, form the first mixed solution；
(2) deionized water is added in the first mixed solution, is continued in 15~50 DEG C of revolving speeds with 400~600r/min
Uniform stirring 15~30 minutes, obtain the second mixed solution；
(3) by after the ethanol solution of 3- aminopropyl -3- Ethoxysilane and mixed in hydrochloric acid, it is molten that it is poured into the second mixing immediately
In liquid, 15~50 DEG C with the revolving speed of 400~600r/min under uniform stirring 6 minutes, obtain third mixed solution；
(4) ethyl orthosilicate is added in third mixed solution, it is uniform with the revolving speed of 400~600r/min at 15~50 DEG C
Stirring 6~12 hours；
(5) 48~96 hours dry at 40~80 DEG C, obtain cetylamine/silicon dioxide composite shape-stabilized phase phase-change material；
Wherein, 7~9g of cetylamine, deionized water 10mL, isopropanol 60mL；The ethyl alcohol of 3- aminopropyl -3- Ethoxysilane
The volume ratio of 1~2mL of solution, hydrochloric acid 0.667mL, 3- aminopropyl -3- Ethoxysilane and ethyl alcohol is 1:19, hydrochloric acid it is mole dense
Degree is 0.2mol/L；Ethyl orthosilicate 0.25mL.
In a specific embodiment of the invention, the ethanol solution of 3- aminopropyl -3- Ethoxysilane is ready-to-use.
In a specific embodiment of the invention, the temperature in step (1)~(4) is 50 DEG C.
In a specific embodiment of the invention, cetylamine 7g, deionized water 10mL, isopropanol 60mL；3- aminopropyl -3-
The volume ratio of the ethanol solution 1mL of Ethoxysilane, hydrochloric acid 0.667mL, 3- aminopropyl -3- Ethoxysilane and ethyl alcohol is 1:
19, the molar concentration of hydrochloric acid is 0.2mol/L；Ethyl orthosilicate 0.25mL.
In a specific embodiment of the invention, cetylamine 9g, deionized water 10mL, isopropanol 60mL；3- aminopropyl -3-
The volume ratio of the ethanol solution 1mL of Ethoxysilane, hydrochloric acid 0.667mL, 3- aminopropyl -3- Ethoxysilane and ethyl alcohol is 1:
19, the molar concentration of hydrochloric acid is 0.2mol/L；Ethyl orthosilicate 0.25mL.
The present invention also provides cetylamine prepared by the above method/silicon dioxide composite shape-stabilized phase phase-change materials.
In a specific embodiment of the invention, the cetylamine/silicon dioxide composite shape-stabilized phase phase-change material enthalpy of phase change
Higher than 205J/g.
In the present invention, using cetylamine as phase change material, using sol-gal process, it is compound to obtain cetylamine/silica
Shaping phase-change material.Wherein, 3- aminopropyl -3- Ethoxysilane and contact with moisture, in 3- aminopropyl -3- Ethoxysilane -
NH2Hydrolysis occurs and generates silicone hydroxyl (Si-OH), dehydrating condensation forms oligomer between Si-OH；It adds it to containing ten
The amino (- NH on Si-OH and cetylamine surface after in second mixed solution of hexamine, in oligomer2) hydrogen bond is formed, and
And due to the presence of HCl so that amino Partial protons in 3- aminopropyl -3- Ethoxysilane and it is positively charged；Meanwhile by
It is located near pH=2 in the isoelectric point of silica, it is negatively charged between the silicate oligomer that TEOS is hydrolyzed to form, when positive silicic acid second
Ester (TEOS) is added in third mixed solution, positive and negative charge interaction, 3- aminopropyl -3- Ethoxysilane and positive silicic acid second
Ester cohydrolysis, polycondensation, self assembly simultaneously form nanoparticle, meanwhile, the 3- aminopropyl -3- Ethoxysilane of protonation makes nanometer
A certain amount of positive charge of particle band and be stabilized, effectively prevent the reunion of nanoparticle.Since nanoparticle has big
Specific surface area and strong interfacial effect can coat more cetylamines therebetween, and will not be from the three-dimensional manometer of nanoparticle
It is leaked in network, solid-state is still presented in the above composite material of melting temperature, shows as solid-solid phase-change process；Phase transformation
Cheng Zhong, nanoparticle can be used as the core of crystal growth, and the thermal conductivity of nano-fluid has raising by a relatively large margin than base fluid, performance
It is different from the thermal conduction characteristic of conventional solid liquid mixture out.Gained final product cetylamine/silicon dioxide composite shape-stabilized phase phase-change material
Enthalpy of phase change be higher than 205J/g, energy-storage property is good；Phase transition temperature is 30~50 DEG C, is not revealed more than phase transition temperature, is sealed
Dress works well；After 50 heating-cooling circulations, DSC curve is almost unchanged, and thermal stability is good, has excellent energy storage can
By property.
Compared with prior art, the invention has the following beneficial technical effects:
1, in cetylamine prepared by the present invention/silicon dioxide composite shape-stabilized phase phase-change material, cetylamine content is high, product phase transformation
Enthalpy is high, does not reveal more than phase transition temperature, thermal stability is good.
2, preparation method simple process of the present invention, it is easy to accomplish, it is at low cost, it is suitble to industrialized production.
Detailed description of the invention
Fig. 1 a is cetylamine/silicon dioxide composite shape-stabilized phase phase-change material infrared light that the embodiment of the present invention 1 is prepared
Spectrogram.
Fig. 1 b is the raw materials used infrared spectrum comparison diagram with products therefrom of the embodiment of the present invention 1.
Fig. 2 a and Fig. 2 b are that cetylamine/silicon dioxide composite shape-stabilized phase phase-change material that the embodiment of the present invention 1 is prepared exists
Stereoscan photograph under different amplification.
Fig. 3 is cetylamine/silicon dioxide composite shape-stabilized phase phase-change material DSC curve that the embodiment of the present invention 1 is prepared
Figure.
Fig. 4 is the DSC curve figure for the final product that comparative example 1 is prepared.
Fig. 5 is the DSC curve figure for the final product that comparative example 2 is prepared.
Fig. 6 is the DSC curve figure for the final product that comparative example 3 is prepared.
Fig. 7 is cetylamine/silicon dioxide composite shape-stabilized phase phase-change material DSC curve that the embodiment of the present invention 2 is prepared
Figure.
Fig. 8 is cetylamine/silicon dioxide composite shape-stabilized phase phase-change material DSC curve that the embodiment of the present invention 3 is prepared
Figure.
Specific embodiment
In order to better illustrate the present invention, it is easy to understand technical solution of the present invention, with reference to the accompanying drawing and is embodied
Example, invention is further described in detail.It should be understood that following embodiments is merely to illustrate the present invention, do not represent or
The scope of the present invention is limited, protection scope of the present invention is subject to claims.
Reagents or instruments used without specified manufacturer in following embodiment is the routine that can be commercially available
Product.
Embodiment 1
It measures 60 milliliters of isopropanols (IPA) to be placed in 100 milliliters of round-bottomed flask, then weighs 7 grams of (29.0mmol) 16
Amine (HDA) is added thereto, and is 50 DEG C in temperature, under conditions of revolving speed is 500r/min, uniform stirring 30 minutes, and so that cetylamine
It is evenly dispersed and be quickly substantially soluble in isopropanol, and the volatilization of isopropanol is reduced as far as possible, to be formed uniform colorless and transparent
The first mixed solution.
Measure 10 ml deionized water (H2O it) is added in the first mixed solution, is then 50 DEG C in temperature, revolving speed is
Continue uniform stirring 15 minutes under conditions of 500r/min, obtains the second mixed solution.
By the ethanol solution of the 3- aminopropyl -3- Ethoxysilane of 1mL (3- aminopropyl -3- Ethoxysilane and ethyl alcohol
Volume ratio 1:19, ready-to-use, ethyl alcohol is that 99.5% analysis is pure) and 0.667mL molar concentration be the mixed in hydrochloric acid of 0.2mol/L
It in 50mL beaker, then is quickly adding into the second mixed solution immediately, is 50 DEG C in temperature, revolving speed is 500r/min's
Under the conditions of, continue uniform stirring 6 minutes, obtains third mixed solution.
It measures 0.25 milliliter of (1.1mmol) ethyl orthosilicate (TEOS) to be added in third mixed solution, is 50 in temperature
DEG C, under conditions of revolving speed is 500r/min, continue uniform stirring 12 hours, so that TEOS is fully hydrolyzed and is not in reunite now
As；Then, 48 hours dry in the drying box that temperature is 50 DEG C, obtain final product.
Composition, structure and the morphology characterization of product:
Fig. 1 a is the infrared spectrogram of final product that above-described embodiment 1 is prepared, in Fig. 1 a, 1081 and 720cm-1Place
It is the bending vibration absorption peak of Si-O key, 968cm-1Place is the bending vibration absorption peak of Si-OH, 3332cm-1Place is N-H group
Stretching vibration absworption peak, 2918 and 2851cm-1Place is the asymmetric stretching vibration peak and symmetrical stretching vibration peak of methyl respectively,
2920 and 2846cm-1It is the asymmetric stretching vibration peak and symmetrical stretching vibration peak of methylene respectively.
Fig. 1 b is the raw materials used infrared spectrum comparison diagram with products therefrom of above-described embodiment 1.In Fig. 1 b, curve (a) is
The final product that embodiment 1 obtains is through being sintered obtained SiO2Ghost, curve (b) are raw material cetylamine, (c) are obtained for embodiment 1
The final product arrived, comparison find do not have new absorption peak to generate in the infrared spectrogram of final product, illustrate in composite material
Not new group generates, and cetylamine and silica are only the compound relationship of physics during the preparation process, not generation
Reaction is learned, because without generating new substance.
That is, can determine that the final product that above-described embodiment 1 is prepared is cetylamine/dioxy in conjunction with Fig. 1 a and Fig. 1 b
SiClx composite material.
SEM test is carried out to final product, stereoscan photograph is as shown in Figure 2 a and 2 b, can from Fig. 2 a and Fig. 2 b
Substantially spherical in shape to material, surface is in opposite continuous phase substantially, can't see apparent pore structure, has illustrated cetylamine (HDA)
Basic insertion SiO2In three-dimensional net structure；And composite material granular size does not generate agglomeration in nanometer range, uniformly
Property is good, illustrates that cetylamine is distributed to well in silica spatial network, silica plays the role of matrix.This dispersion
Form provides good mechanical strength for entire compound.Therefore, it can guarantee that composite material keeps solid in phase transition process
The problem of shape, the cetylamine leakage that will not have melted.
The performance evaluation of product:
Dsc analysis is carried out to final product according to the following steps:
Under high pure nitrogen atmosphere, 5~10mg of sample size, heating rate 10 DEG C/min, throughput 50mL/min, scanning temperature
Range is spent from -10 DEG C~110 DEG C.Using the DSC8000 heat differential scanning calorimeter instrument (DSC) of PerkinElmer company, the U.S., survey
Phase transition temperature and enthalpy of phase change in test agent heating-temperature-fall period.First with 10 DEG C/min from -10 DEG C~110 DEG C, constant temperature is kept
3min eliminates thermal history；Then -10 DEG C (temperature-fall periods) are cooled to from 110 DEG C with 10 DEG C/min；Again with 10 DEG C/min from -10
It DEG C is warming up to 110 DEG C (temperature-rise periods), the phase transition temperature and enthalpy of phase change of analysis test temperature-fall period and temperature-rise period.
The DSC curve for the final product that above-described embodiment 1 is prepared is as shown in figure 3, carrier matrix silica is being surveyed
It is not undergone phase transition in examination range, the phase transformation enthalpy that product can be calculated from the DSC curve of Fig. 3 is 214.9J/g, be can be used as
Energy storage material uses.
Further, after carrying out 50 heating-cooling circulations to final product, then DSC test is carried out, as the result is shown: final
The first time of product melts and the DSC curve of the 50th melting and crystallization process of the DSC curve of crystallization process and final product
It is almost consistent.The phase transformation enthalpy that product after the 50th heating-cooling recycles is calculated is 212.9J/g, illustrates that final product has
There is excellent cycle performance, thermal stability is good, has excellent energy storage reliability.50 heating-cooling circulation front and back cetylamines/
Silicon dioxide composite shape-stabilized phase phase-change material performance data is as shown in table 1 below.
1:50 heating-cooling circulation front and back cetylamine/silicon dioxide composite shape-stabilized phase phase-change material performance data of table
| Crystallization temperature T (DEG C) | Crystallization enthalpy Δ H (J/g) | Melting temperature T (DEG C) | Melting enthalpy Δ H (J/g) | |
| 1st time | 36.13 | 210.8 | 46.51 | 214.9 |
| 50th time | 36.23 | 209.6 | 46.46 | 212.9 |
Performance evaluation is packaged to final product according to the following steps:
Final product made from 5g is weighed, is laid in clean surface plate, a thin layer sample powder is formed, at 100 DEG C
Middle placement 1h, cetylamine adherency has not been observed on surface in surface plate after taking-up, illustrates do not have cetylamine to permeate, dioxy
SiClx plays the role of good setting to cetylamine, and composite phase-change material has shape retentivity, reaches setting purpose, i.e.,
Obtain cetylamine/silicon dioxide composite shape-stabilized phase phase-change material.
To sum up, according to the above test result, it can be found that:
The preparation gained final product of embodiment 1 is cetylamine/silicon dioxide composite shape-stabilized phase phase-change material, and phase transformation enthalpy is
214.9J/g, since silica plays the role of good setting to cetylamine, final product has excellent encapsulation performance,
Also, after final product undergoes 50 heating-cooling circulations, DSC curve is almost unchanged, illustrates that its thermal stability is good, has
Excellent energy storage reliability.
Comparative example 1
It measures 60 milliliters of isopropanols (IPA) to be placed in 100 milliliters of round-bottomed flask, then weighs 7 grams of (29.0mmol) 16
Amine (HDA) is added thereto, and is 50 DEG C in temperature, under conditions of revolving speed is 500r/min, uniform stirring 30 minutes, is formed uniform nothing
The first transparent mixed solution of color.
Measure 10 ml deionized water (H2O it) is added in the first mixed solution, is then 50 DEG C in temperature, revolving speed is
Continue uniform stirring 15 minutes under conditions of 500r/min, obtains the second mixed solution.
It measures 0.25 milliliter of (1.1mmol) ethyl orthosilicate (TEOS) to be added in the second mixed solution, is 50 in temperature
DEG C, under conditions of revolving speed is 500r/min, continue uniform stirring 12 hours, it is then, dry in the drying box that temperature is 50 DEG C
48 hours, obtain product.
Dsc analysis, DSC curve such as Fig. 4 institute are carried out to above-mentioned final product according to the step identical with embodiment 1
Show, DSC test shows: the phase transformation enthalpy that product is prepared in comparative example 1 is 118.6J/g.
It can be seen that: it is different from embodiment 1, isopropanol is only used only in comparative example 1 without introducing 3- aminopropyl -3- second
The alcohol hydrochloric acid solution of oxysilane, therefore, the enthalpy of phase change of 1 products therefrom of comparative example are substantially less than the embodiment 1 of similarity condition
Gained final product.
Comparative example 2
It measures 60 milliliters of isopropanols (IPA) to be placed in 100 milliliters of round-bottomed flask, then weighs 7 grams of (29.0mmol) 16
Amine (HDA) is added thereto, and is 50 DEG C in temperature, under conditions of revolving speed is 500r/min, uniform stirring 30 minutes, is formed uniform nothing
The first transparent mixed solution of color.
Measure 10 ml deionized water (H2O it) is added in the first mixed solution, is then 50 DEG C in temperature, revolving speed is
Continue uniform stirring 15 minutes under conditions of 500r/min, obtains the second mixed solution.
By the ethanol solution of the 3- aminopropyl -3- Ethoxysilane of 7mL (3- aminopropyl -3- Ethoxysilane and ethyl alcohol
Volume ratio 1:19) and 0.667mL molar concentration be 0.2mol/L mixed in hydrochloric acid in 50mL beaker, then immediately by its rapidly plus
Enter into the second mixed solution, is 50 DEG C in temperature, under conditions of revolving speed is 500r/min, continues uniform stirring 6 minutes, obtain
Third mixed solution.
It measures 0.25 milliliter of (1.1mmol) ethyl orthosilicate (TEOS) to be added in third mixed solution, is 50 in temperature
DEG C, under conditions of revolving speed is 500r/min, continue uniform stirring 12 hours, it is then, dry in the drying box that temperature is 50 DEG C
48 hours, obtain product.
According to the step identical with embodiment 1 to above-mentioned product carry out dsc analysis, DSC curve as shown in figure 5,
DSC test shows: the phase transformation enthalpy that product is prepared in comparative example 2 is 163.6J/g.
Product made from 5g comparative example 2 is weighed, is laid in clean surface plate, a thin layer sample powder is formed, 100
1h is placed in DEG C, has been observed a small amount of cetylamine adherency after taking-up in surface plate, has been illustrated that cetylamine is permeated.
It can be seen that, in comparative example 2 dosage of the ethanol solution of 3- aminopropyl -3- Ethoxysilane different from embodiment 1
Greatly, the enthalpy of phase change of products therefrom is significantly lower than 1 gained final product of embodiment, moreover, the encapsulation of 2 products therefrom of comparative example is imitated
Fruit is also obviously not so good as 1 gained final product of embodiment.
Comparative example 3
It measures 60 milliliters of isopropanols (IPA) to be placed in 100 milliliters of round-bottomed flask, then weighs 7 grams of (29.0mmol) 16
Amine (HDA) is added thereto, and is 70 DEG C in temperature, under conditions of revolving speed is 500r/min, uniform stirring 30 minutes, is formed uniform nothing
The first transparent mixed solution of color.
Measure 10 ml deionized water (H2O it) is added in the first mixed solution, is then 70 DEG C in temperature, revolving speed is
Continue uniform stirring 15 minutes under conditions of 500r/min, obtains the second mixed solution.
By the ethanol solution of the 3- aminopropyl -3- Ethoxysilane of 1mL (3- aminopropyl -3- Ethoxysilane and ethyl alcohol
Volume ratio 1:19) and 0.667mL molar concentration be 0.2mol/L mixed in hydrochloric acid in 50mL beaker, then immediately by its rapidly plus
Enter into the second mixed solution, is 70 DEG C in temperature, under conditions of revolving speed is 500r/min, continues uniform stirring 6 minutes, obtain
Third mixed solution.
It measures 0.25 milliliter of (1.1mmol) ethyl orthosilicate (TEOS) to be added in third mixed solution, is 70 in temperature
DEG C, under conditions of revolving speed is 500r/min, continue uniform stirring 12 hours, it is then, dry in the drying box that temperature is 50 DEG C
48 hours, obtain product.
Dsc analysis is carried out to above-mentioned product according to the step identical with embodiment 1 and encapsulation performance is tested,
DSC curve is as shown in Figure 6.Test shows: the phase transformation enthalpy that product is prepared in comparative example 3 is 170.1J/g, and cetylamine is sent out
Infiltration is given birth to.
It can be seen that it is different to carry out reaction from 50 DEG C in embodiment 1, reaction temperature is 70 DEG C in comparative example 3, comparative example 3
The enthalpy of phase change of products therefrom is significantly lower than 1 gained final product of embodiment, moreover, the packaging effect of 3 gained comparative example 3 of comparative example
Also obviously it is not so good as 1 gained final product of embodiment.
Embodiment 2
It measures 60 milliliters of isopropanols (IPA) to be placed in 100 milliliters of round-bottomed flask, then weighs 7 grams of (29.0mmol) 16
Amine (HDA) is added thereto, and is 20 DEG C in temperature, under conditions of revolving speed is 500r/min, uniform stirring 30 minutes, and so that cetylamine
It is evenly dispersed and be quickly substantially soluble in isopropanol, and the volatilization of isopropanol is reduced as far as possible, to be formed uniform colorless and transparent
The first mixed solution.
Measure 10 ml deionized water (H2O it) is added in the first mixed solution, is then 20 DEG C in temperature, revolving speed is
Continue uniform stirring 15 minutes under conditions of 500r/min, obtains the second mixed solution.
By the ethanol solution of the 3- aminopropyl -3- Ethoxysilane of 1mL (3- aminopropyl -3- Ethoxysilane and ethyl alcohol
Volume ratio 1:19, ready-to-use, ethyl alcohol is that 99.5% analysis is pure) and 0.667mL molar concentration be the mixed in hydrochloric acid of 0.2mol/L
It in 50mL beaker, then is quickly adding into the second mixed solution immediately, is 20 DEG C in temperature, revolving speed is 500r/min's
Under the conditions of, continue uniform stirring 6 minutes, obtains third mixed solution.
It measures 0.25 milliliter of (1.1mmol) ethyl orthosilicate (TEOS) to be added in third mixed solution, is 20 in temperature
DEG C, under conditions of revolving speed is 500r/min, continue uniform stirring 12 hours, so that TEOS is fully hydrolyzed and is not in reunite now
As；Then, 48 hours dry in the drying box that temperature is 50 DEG C, obtain final product.
Above-mentioned final product is tested according to the step identical with embodiment 1, test result shows: being implemented
The final product that example 2 is prepared is also cetylamine/silicon dioxide composite shape-stabilized phase phase-change material, enthalpy of phase change 208.3J/g, and
And there is no cetylamine to permeate.The DSC curve of final product made from embodiment 2 is as shown in Figure 7.
Embodiment 3
It measures 60 milliliters of isopropanols (IPA) to be placed in 100 milliliters of round-bottomed flask, then weighs 9 grams of (37.0mmol) 16
Amine (HDA) is added thereto, and is 50 DEG C in temperature, under conditions of revolving speed is 500r/min, uniform stirring 30 minutes, and so that cetylamine
It is evenly dispersed and be quickly substantially soluble in isopropanol, and the volatilization of isopropanol is reduced as far as possible, to be formed uniform colorless and transparent
The first mixed solution.
Measure 10 ml deionized water (H2O it) is added in the first mixed solution, is then 50 DEG C in temperature, revolving speed is
Continue uniform stirring 15 minutes under conditions of 500r/min, obtains the second mixed solution.
By the ethanol solution of the 3- aminopropyl -3- Ethoxysilane of 1mL (3- aminopropyl -3- Ethoxysilane and ethyl alcohol
Volume ratio 1:19, ready-to-use, ethyl alcohol is that 99.5% analysis is pure) and 0.667mL molar concentration be the mixed in hydrochloric acid of 0.2mol/L
It in 50mL beaker, then is quickly adding into the second mixed solution immediately, is 50 DEG C in temperature, revolving speed is 500r/min's
Under the conditions of, continue uniform stirring 6 minutes, obtains third mixed solution.
It measures 0.25 milliliter of (1.1mmol) ethyl orthosilicate (TEOS) to be added in third mixed liquor, is 50 DEG C in temperature,
Under conditions of revolving speed is 500r/min, continue uniform stirring 12 hours, so that TEOS is fully hydrolyzed and is not in agglomeration；
Then, 48 hours dry in the drying box that temperature is 50 DEG C, obtain final product.
Above-mentioned final product is tested according to the step identical with embodiment 1, test result shows: being implemented
The final product that example 3 is prepared is also cetylamine/silicon dioxide composite shape-stabilized phase phase-change material, enthalpy of phase change 216.6J/g, and
And there is no cetylamine to permeate.The DSC curve of final product made from embodiment 3 is as shown in Figure 8.
The performance data of above-described embodiment 1~3 and the composite material of comparative example 1~3 is summarized and compared, it is as follows
Shown in table 2.From table 2 it can be seen that cetylamine/silicon dioxide composite shape-stabilized phase phase transformation the material prepared using method provided by the invention
Expect (Examples 1 to 3), enthalpy of phase change is apparently higher than comparative example 1~3.Moreover, utilizing the 16 of method provided by the invention preparation
Amine/silicon dioxide composite shape-stabilized phase phase-change material (Examples 1 to 3) all shows solid during phase transition and turns to solid
Become, no liquid occurs, and encapsulation performance is substantially better than comparative example 1~3.
Table 2: cetylamine/silica shaping phase-change material performance data
| Melting peak temperature (DEG C) | Melting enthalpy (J/g) | Peak crystallization temperature (DEG C) | It crystallizes heat content (J/g) | |
| Embodiment 1 | 46.5 | 214.9 | 36.1 | 210.8 |
| Comparative example 1 | 46.1 | 118.6 | 32.1 | 117.1 |
| Comparative example 2 | 45.6 | 163.6 | 36.7 | 168.5 |
| Comparative example 3 | 45.3 | 170.1 | 36.6 | 167.5 |
| Embodiment 2 | 46.3 | 208.3 | 36.5 | 201.4 |
| Embodiment 3 | 46.5 | 216.6 | 36.6 | 211.9 |
It should be noted that embodiment described above for explaining only the invention, is not constituted to of the invention any
Limitation, by referring to exemplary embodiments, invention has been described, it should be appreciated that word used in it is descriptive
With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it relates to
And specific method, material and embodiment, it is not intended that the present invention is limited to particular case disclosed in it, on the contrary, this hair
It is bright to can be extended to other all methods and applications with the same function.
Claims (6)
1. cetylamine/silicon dioxide composite shape-stabilized phase phase-change material preparation method, comprising the following steps:
(1) cetylamine is added in isopropanol, in 15~50 DEG C of 20~30 points of revolving speed uniform stirring with 400~600r/min
Clock forms the first mixed solution；
(2) deionized water is added in the first mixed solution, is continued in 15~50 DEG C of revolving speeds with 400~600r/min uniform
Stirring 15~30 minutes, obtains the second mixed solution；
(3) by after the ethanol solution of 3- aminopropyl -3- Ethoxysilane and mixed in hydrochloric acid, it is poured into the second mixed solution immediately
In, 15~50 DEG C with the revolving speed of 400~600r/min under uniform stirring 6 minutes, obtain third mixed solution；
(4) ethyl orthosilicate is added in third mixed solution, in 15~50 DEG C of revolving speed uniform stirrings with 400~600r/min
6~12 hours；
(5) 48~96 hours dry at 40~80 DEG C, obtain cetylamine/silicon dioxide composite shape-stabilized phase phase-change material；
Wherein, 7~9g of cetylamine, deionized water 10mL, isopropanol 60mL；The ethanol solution 1 of 3- aminopropyl -3- Ethoxysilane
The volume ratio of~2mL, hydrochloric acid 0.667mL, 3- aminopropyl -3- Ethoxysilane and ethyl alcohol is 1:19, and the molar concentration of hydrochloric acid is
0.2mol/L；Ethyl orthosilicate 0.25mL.
2. preparation method as described in claim 1, which is characterized in that the temperature in step (1)~(4) is 50 DEG C.
3. preparation method as described in claim 1, which is characterized in that cetylamine 7g, deionized water 10mL, isopropanol 60mL；
The ethanol solution 1mL of 3- aminopropyl -3- Ethoxysilane, hydrochloric acid 0.667mL, 3- aminopropyl -3- Ethoxysilane and ethyl alcohol
Volume ratio is 1:19, and the molar concentration of hydrochloric acid is 0.2mol/L；Ethyl orthosilicate 0.25mL.
4. preparation method as described in claim 1, which is characterized in that cetylamine 9g, deionized water 10mL, isopropanol 60mL；
The ethanol solution 1mL of 3- aminopropyl -3- Ethoxysilane, hydrochloric acid 0.667mL, 3- aminopropyl -3- Ethoxysilane and ethyl alcohol
Volume ratio is 1:19, and the molar concentration of hydrochloric acid is 0.2mol/L；Ethyl orthosilicate 0.25mL.
5. the cetylamine as made from preparation method as described in any one of claims 1 to 4/silicon dioxide composite shape-stabilized phase phase transformation
Material.
6. cetylamine as claimed in claim 5/silicon dioxide composite shape-stabilized phase phase-change material, which is characterized in that its enthalpy of phase change is high
In 205J/g.
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