CN114479769A - Preparation method of silicon dioxide-coated paraffin phase-change nano microcapsule - Google Patents
Preparation method of silicon dioxide-coated paraffin phase-change nano microcapsule Download PDFInfo
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 239000012188 paraffin wax Substances 0.000 title claims abstract description 88
- 239000003094 microcapsule Substances 0.000 title claims abstract description 68
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 48
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000002844 melting Methods 0.000 claims abstract description 31
- 230000008018 melting Effects 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000839 emulsion Substances 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 16
- YDRZJWKZPYIXQX-UHFFFAOYSA-N N1=CC=CC=C1.C(CCCCCCCCCCCCCCC)(=O)O Chemical compound N1=CC=CC=C1.C(CCCCCCCCCCCCCCC)(=O)O YDRZJWKZPYIXQX-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- 239000003960 organic solvent Substances 0.000 claims abstract description 15
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 12
- 238000004134 energy conservation Methods 0.000 claims abstract description 11
- 238000001704 evaporation Methods 0.000 claims abstract description 11
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002440 industrial waste Substances 0.000 claims abstract description 6
- 238000011084 recovery Methods 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims abstract description 5
- 229950004354 phosphorylcholine Drugs 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 3
- 230000008859 change Effects 0.000 claims description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 14
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 235000021314 Palmitic acid Nutrition 0.000 claims description 8
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 7
- 239000002088 nanocapsule Substances 0.000 claims description 7
- -1 palmitic acid succinimide ester Chemical class 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 5
- WKJRYVOTVRPAFN-UHFFFAOYSA-N 2-pyridin-1-ium-4-ylacetic acid;chloride Chemical compound Cl.OC(=O)CC1=CC=NC=C1 WKJRYVOTVRPAFN-UHFFFAOYSA-N 0.000 claims description 3
- JMTMSDXUXJISAY-UHFFFAOYSA-N 2H-benzotriazol-4-ol Chemical compound OC1=CC=CC2=C1N=NN2 JMTMSDXUXJISAY-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- NPZTUJOABDZTLV-UHFFFAOYSA-N hydroxybenzotriazole Substances O=C1C=CC=C2NNN=C12 NPZTUJOABDZTLV-UHFFFAOYSA-N 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- 239000012782 phase change material Substances 0.000 abstract description 19
- 238000004146 energy storage Methods 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 5
- 239000004753 textile Substances 0.000 abstract description 3
- 239000002775 capsule Substances 0.000 abstract description 2
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 2
- 239000011147 inorganic material Substances 0.000 abstract description 2
- 230000009970 fire resistant effect Effects 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 23
- 238000002425 crystallisation Methods 0.000 description 11
- 230000008025 crystallization Effects 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 11
- 238000011161 development Methods 0.000 description 8
- 238000005338 heat storage Methods 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 239000010408 film Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 238000007726 management method Methods 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000007832 Na2SO4 Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- OTNHQVHEZCBZQU-UHFFFAOYSA-N (2,5-dioxopyrrolidin-1-yl) hexadecanoate Chemical compound CCCCCCCCCCCCCCCC(=O)ON1C(=O)CCC1=O OTNHQVHEZCBZQU-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- XHFLOLLMZOTPSM-UHFFFAOYSA-M sodium;hydrogen carbonate;hydrate Chemical class [OH-].[Na+].OC(O)=O XHFLOLLMZOTPSM-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- 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 a preparation method of a phase-change nano microcapsule coated with silicon dioxide and paraffin, which is characterized in that 1, 2-distearoyl-sn-propanetriyl-3-phosphorylcholine and pyridine palmitate are dissolved in an organic solvent; evaporating under reduced pressure, adding water into the film, performing ultrasonic treatment to obtain emulsion, adding paraffin into the emulsion, and continuing ultrasonic treatment; adding water and tetraethyl orthosilicate into the paraffin emulsion, and stirring; and centrifuging the mixed solution, and washing with water to obtain the silicon dioxide-coated paraffin phase-change nano microcapsule. The outer layer of the nano microcapsule adopts inorganic material silicon dioxide which is low in cost, good in film forming property, non-degradable, wear-resistant and fire-resistant as a capsule material, the phase change material is paraffin with different melting points, and the nano microcapsule has the characteristics of small particle size, no leakage, no loss, low cost, long service life, high energy storage efficiency and the like, can furthest exert the energy storage efficiency of the phase change material, and is expected to be widely applied to the fields of battery thermal management, building energy conservation, industrial waste heat recovery, solar heat utilization, constant-temperature textiles and the like.
Description
[ technical field ] A method for producing a semiconductor device
The invention belongs to the field of phase change material preparation, and particularly relates to a preparation method of a silicon dioxide-coated paraffin phase change nano microcapsule.
[ background of the invention ]
With the increasing global energy crisis, energy conservation and effective utilization of energy are important strategic targets for sustainable development in China. China is a country with poor energy and needs more energy support with the rapid development of economy. The practical problem is that energy is increasingly in short supply, and energy conservation is urgent. The basis of human survival and development is energy, China is one of the major energy consuming countries, and excessive consumption of non-renewable energy has caused more and more serious environmental problems, so that measures of changing energy utilization modes, realizing energy conservation and emission reduction, developing and utilizing renewable energy and the like become important ways of reducing environmental pollution, relieving energy supply and demand contradictions, changing economic growth modes and adjusting energy structures. Meanwhile, improving the utilization rate of the existing energy is another important way to relieve the energy crisis. Among a plurality of energy utilization modes, the heat storage technology is one of effective means for protecting the environment and improving the energy utilization rate, and the efficient and low-cost heat energy storage technology and method are developed, so that the contradiction between energy supply and demand can be solved, the heat energy utilization rate is improved, and the effects of energy conservation and emission reduction can be achieved. In addition, the medium and long-term scientific and technological development planning outline of China has already listed energy as the key field, and the large-scale development and utilization of renewable energy (such as solar energy and the like) is the subject of priority development. Therefore, from the needs of national economy and social development, researches on heat energy utilization and storage technologies should be vigorously carried out in order to achieve the aims of energy conservation and emission reduction and low-carbon economy in China and promote heat energy to achieve comprehensive utilization of multiple energy levels in a wider range and at a higher level. The heat energy storage is one of key technologies for improving the heat energy utilization efficiency, and plays an important role in relieving the energy crisis.
An efficient thermal energy storage system must have a long service life, a high heat exchange efficiency and a large specific heat capacity. Among various heat storage technologies, a latent heat storage technology based on Phase Change Materials (PCMs) is an important one, and in order to meet the requirements of practical heat storage applications, the Phase Change energy storage technology is considered as one of the most effective ways for heat storage, and has great prospects in the fields of battery heat management, building energy conservation, industrial waste heat recovery, solar heat utilization and the like. For example, PCMs can be used as passive heat dissipation systems in the field of electronic cooling, such as electronic chips and power batteries of electric vehicles. PCMs can be used in aerospace fields such as artificial satellites and spacecraft to solve the problem of thermostatic control of instruments or materials. PCMs can be used as heat sources in the fields of solar absorption/adsorption refrigeration, solar air conditioning systems and passive solar heat utilization. PCMs can be used as temperature buffer media to realize human body comfort in the textile fields of textile fibers, constant temperature clothes and the like. High performance phase change materials are, of course, the key to developing efficient latent heat storage systems.
The storage (heat storage and cold storage) of energy by utilizing the phase change latent energy heat of the phase change material is a novel environment-friendly energy-saving technology, but most phase change materials have the problems of volume change, canker, easy leakage and the like in the heating and cooling processes, so that the application of the phase change materials is limited, and the microcapsule technology is the most widely applied solution technology. The phase-change microcapsule has a remarkable prospect in the fields of battery thermal management, building energy conservation, industrial waste heat recovery, solar heat utilization and the like, however, the phase-change microcapsule is still in the development and research stage, large-scale industrial production and application are not obtained, and a plurality of problems need to be further researched and solved, and the method mainly comprises the following steps: (1) the traditional phase change microcapsule has large particle size (10-1000 mu m), small specific surface area and low energy storage efficiency, and the self energy storage performance of the phase change material needs to be improved; (2) the stability is poor, the leakage is easy, and the stability, the durability and the compatibility of the phase change microcapsule are urgently needed to be improved; (3) the cost is high, the process is complex, the synthesis process needs to be simplified, and the cost of the phase-change microcapsule is reduced.
[ summary of the invention ]
Aiming at the defects, the invention provides a preparation method of dozens of nanometer phase change microcapsules by selecting silicon dioxide with wide sources and good biocompatibility as a capsule material of the nanometer microcapsules and paraffin as a phase change material.
The purpose of the invention is realized by the following modes:
the invention provides a preparation method of a silicon dioxide-coated paraffin nano microcapsule, which comprises the following steps:
1) completely dissolving 1, 2-distearoyl-sn-propanetriyl-3-phosphorylcholine and pyridine palmitate in an organic solvent at 65 ℃ to obtain a mixed solution;
2) evaporating the mixed solution obtained in the step 1) under reduced pressure to obtain a layer of film, adding water into the film, carrying out ultrasonic treatment at 65 ℃ to obtain emulsion, adding paraffin into the emulsion, and continuing ultrasonic treatment;
3) adding water and tetraethyl orthosilicate into the paraffin emulsion subjected to ultrasonic treatment in the step 2), and stirring at room temperature for 20-30 hours;
4) centrifuging the mixed solution obtained after stirring in the step 3), and washing with water to obtain the silicon dioxide-coated paraffin phase-change nano microcapsule.
Further, the organic solvent in the step 1) is chloroform, and the w/w/v ratio of the 1, 2-distearoyl-sn-propanetriyl-3-phosphorylcholine, the palmitic acid pyridine and the organic solvent is 16:1: 9.
Further, the pyridine palmitate in the step 1) is obtained by the following steps:
a. dissolving palmitic acid and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride in dry DMF (dimethyl formamide) in an ice bath, adding N-hydroxysuccinimide, stirring for 6 hours under the protection of argon, evaporating under reduced pressure to obtain a colorless solid, and purifying by using a silica gel column to obtain palmitic acid succinimide ester;
b. dropwise adding the palmitic acid succinimide ester to 1, 2-ethylenediamine, stirring for 2 hours, and then carrying out reduced pressure evaporation to obtain palmitic acid amino;
c. 4-pyridine acetic acid hydrochloride is dissolved in DMF, then 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, hydroxybenzotriazole and triethylamine are added, palmitic acid amino is added to the mixed solution, and after stirring for 15 hours at 50 ℃, recrystallization is carried out to obtain pyridine palmitate.
Further, the paraffin wax in the step 2) is paraffin wax with different melting point ranges.
Further, the ultrasonic treatment in the step 2) is ultrasonic treatment for 10-20min under the condition of 200 and 400W of power.
Further, the reduced-pressure evaporation described in step 2) is performed under 0.1 atmosphere in a rotary evaporator.
Further, the volume ratio of the water to the tetraethyl orthosilicate in the step 3) is 60: 1.
Preferably, the different melting points of the paraffin wax are in the ranges of 29 ℃, 37 ℃, 45 ℃ and 52 ℃, respectively.
The invention also provides a silicon dioxide-coated paraffin phase change nano microcapsule, wherein the average grain diameter of the nano microcapsule is less than 100 nm.
The invention also provides application of the silicon dioxide-coated paraffin phase-change nano microcapsule in battery heat management, building energy conservation, industrial waste heat recovery and solar heat utilization.
The invention has the characteristics and beneficial effects that:
1. compared with the traditional micron-sized microcapsule, the nanometer phase change microcapsule prepared by the method of the invention by utilizing the nanometer material technology has large specific surface area and high stability, and can remarkably improve the energy storage efficiency;
2. in order to improve compatibility and prolong service life, the method constructs that the outer layer adopts inorganic material silicon dioxide with low cost, good film forming property, no degradation, wear resistance and fire resistance;
3. the nano phase change microcapsule has the characteristics of high energy storage efficiency, no leakage, no loss, low cost, long service life and the like, can furthest exert the energy storage efficiency of the phase change material, reduce the cost, realize large-scale industrialization, and is expected to be widely applied in the fields of battery thermal management, building energy conservation, industrial waste heat recovery, solar heat utilization and the like.
4. The phase-change nano microcapsule of the silicon dioxide-coated paraffin prepared by the invention has the advantages that the average grain diameter is less than 100nm, the highest content of the paraffin can reach about 70%, the encapsulation rate reaches more than 85%, the phase-change nano microcapsule has higher phase-change latent heat and higher stability, and the phase-change enthalpy is reduced by less than 1% after 100 times of circulation.
5. The method has the advantages of simple process, low production cost and equipment investment cost, no pollutant generation, stable and reliable product quality and very wide application prospect.
[ description of the drawings ]
FIG. 1 is a TEM image of silica-coated paraffin phase-change nanocapsule of the present invention.
FIG. 2 is a diagram of a silicon dioxide coated paraffin phase change nano microcapsule of the present invention.
FIG. 3 is a graph showing the differential thermal crystallization of phase-change nano-microcapsules prepared from paraffin (29 ℃) and silica-coated paraffin (29 ℃). (a) Paraffin wax; (b) paraffin @ SiO2。
FIG. 4 is a graph of the differential thermal melting curve of the phase-change nano-microcapsule prepared by using paraffin wax (29 ℃) and silica-coated paraffin wax (29 ℃). (a) Paraffin wax; (b) paraffin @ SiO2。
FIG. 5 is a TGA diagram of phase change nanocapsules prepared from paraffin wax (29 deg.C) and silica-coated paraffin wax (29 deg.C) used in the present invention.
[ detailed description ] embodiments
The principles and features of this invention are described in conjunction with the following examples, which are set forth merely to illustrate the invention and are not intended to limit the scope of the invention.
Example 1: preparation of pyridine palmitate
Palmitic acid (15 g, 60mmol) and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC-HCl, 17 g, 90mmol) were dissolved in dry dimethylformamide (DMF, 600mL) on ice bath, then N-hydroxysuccinimide (10g, 90mmol) was added, the mixed solution was stirred at room temperature under argon protection for 6 hours, the solvent was evaporated under reduced pressure using a rotary evaporator to give a product which was dissolved with ethyl acetate, washed three times with water and brine to give organic phases which were combined and combined with Na2SO4Drying, evaporating under reduced pressure to obtain colorless solid, purifying the obtained solid with silica gel column, and finally purifying with dichloromethane as eluent to obtain palmitic acid succinimide ester; palmitate succinimidyl ester (7.1g) was added dropwise to 1, 2-ethylenediamine (27mL, 0.4mol) in dichloromethane (300mL) at room temperature under argon, stirred for 2 hours, diluted with chloroform, washed three times with water and brine, the organic phases combined, and Na2SO4After drying for 4 hours, evaporating under reduced pressure to obtain palmitic acid amino groups; 4-Pyridineacetic acid hydrochloride (4.3g, 5.0mmol) was dissolved in dry DMF (300mL) under argon protection at room temperature, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (12g, 60mmol), hydroxybenzotriazole (9.2g, 60mmol) and dry triethylamine (13mL, 93mmol) were added to the DMF solution, followed by the addition of palmitylamino (3.0g, 10mmol) to the mixture, stirring at 50 ℃ for 15 h, addition of saturated NaHCO3Precipitating to obtain yellow pigmentA colored solid, with saturated NaHCO3And deionized water for 3 times, followed by recrystallization from methanol to give pyridine palmitate as a white solid.
The following pyridines palmitate used in examples 2-5 were all prepared by the method of example 1.
Example 2: preparation of silicon dioxide coated paraffin phase change nano microcapsule with melting point of 29 DEG C
The method comprises the following specific steps:
1, 2-distearoyl-sn-propanetriyl-3-phosphocholine (500mg, 0.63mmol) and pyridine palmitate (33mg, 79. mu. mol) were completely dissolved in 300mL of chloroform at 65 ℃. The organic solvent was evaporated under reduced pressure in a rotary evaporator to obtain a thin film, and then kept under vacuum for 12 hours to remove the remaining organic solvent. 300mL of water was added to the resulting film, and the mixture was sonicated at 65 ℃ for 10 minutes to give an emulsion. Next, 6.0g of paraffin wax having a melting point of 29 ℃ was added to the emulsion, stirred for 10 minutes, and sonicated for 10 minutes. 600mL of water and 10mL of tetraethyl orthosilicate are then added to the emulsion, followed by stirring at room temperature for 24 hours. The obtained mixed solution is centrifuged (14000g for 10 minutes), and washed with water (20mL) for 3 times to obtain the paraffin phase-change nano microcapsule with the melting point of 29 ℃ wrapped by silicon dioxide.
The average grain diameter of the paraffin phase-change nano-microcapsule is about 45nm, and the paraffin content is 68%.
Example 3: preparation of silica-coated paraffin phase-change nano microcapsule with melting point of 37 DEG C
The method comprises the following specific steps:
1, 2-distearoyl-sn-propanetriyl-3-phosphocholine (500mg, 0.63mmol) and pyridine palmitate (33mg, 79. mu. mol) were completely dissolved in 300mL of chloroform at 65 ℃. The organic solvent was evaporated under reduced pressure in a rotary evaporator to obtain a thin film, and then kept under vacuum for 12 hours to remove the remaining organic solvent. 300mL of water was added to the resulting film, and the mixture was sonicated at 65 ℃ for 10 minutes to give an emulsion. Next, 6.0g of paraffin wax having a melting point of 37 ℃ was added to the emulsion, stirred for 10 minutes, and sonicated for 10 minutes. 600mL of water and 10mL of tetraethyl orthosilicate are then added to the emulsion, followed by stirring at room temperature for 24 hours. The obtained mixed solution is centrifuged (14000g for 10 minutes), and washed with water (20mL) for 3 times to obtain the paraffin phase-change nano microcapsule with the melting point of 29 ℃ wrapped by silicon dioxide.
The average grain diameter of the paraffin phase-change nano-microcapsule is about 48nm, and the paraffin content is 68%.
Example 4: preparation of silicon dioxide coated paraffin phase change nano microcapsule with melting point of 45 DEG C
The method comprises the following specific steps:
1, 2-distearoyl-sn-propanetriyl-3-phosphocholine (500mg, 0.63mmol) and pyridine palmitate (33mg, 79. mu. mol) were completely dissolved in 300mL of chloroform at 65 ℃. The organic solvent was evaporated under reduced pressure in a rotary evaporator to obtain a thin film, and then kept under vacuum for 12 hours to remove the remaining organic solvent. 300mL of water was added to the resulting film, and the mixture was sonicated at 65 ℃ for 10 minutes to give an emulsion. Next, 6.0g of paraffin wax having a melting point of 45 ℃ was added to the emulsion, stirred for 10 minutes, and sonicated for 10 minutes. 600mL of water and 10mL of tetraethyl orthosilicate are then added to the emulsion, followed by stirring at room temperature for 24 hours. The obtained mixed solution is centrifuged (14000g for 10 minutes), and washed with water (20mL) for 3 times to obtain the paraffin phase-change nano microcapsule with the melting point of 29 ℃ wrapped by silicon dioxide.
The average grain diameter of the paraffin phase-change nano-microcapsule is about 43nm, and the paraffin content is 66%.
Example 5: preparation of silicon dioxide coated paraffin phase-change nano microcapsule with melting point of 52 DEG C
The method comprises the following specific steps:
1, 2-distearoyl-sn-propanetriyl-3-phosphocholine (500mg, 0.63mmol) and pyridine palmitate (33mg, 79. mu. mol) were completely dissolved in 300mL of chloroform at 65 ℃. The organic solvent was evaporated under reduced pressure in a rotary evaporator to obtain a thin film, and then kept under vacuum for 12 hours to remove the remaining organic solvent. 300mL of water was added to the resulting film, and the mixture was sonicated at 65 ℃ for 10 minutes to give an emulsion. Next, 6.0g of paraffin wax having a melting point of 52 ℃ was added to the emulsion, stirred for 10 minutes, and sonicated for 10 minutes. 600mL of water and 10mL of tetraethyl orthosilicate are then added to the emulsion, followed by stirring at room temperature for 24 hours. The obtained mixed solution is centrifuged (14000g for 10 minutes), and washed with water (20mL) for 3 times to obtain the paraffin phase-change nano microcapsule with the melting point of 29 ℃ wrapped by silicon dioxide.
The average grain diameter of the paraffin phase-change nano-microcapsule is about 52nm, and the paraffin content is 67%.
The performance test of the silica-coated paraffin phase-change nanocapsule of the present invention will be described below.
Experimental example 1: projection electron microscope (TEM) analysis
The morphology, microstructure and particle size of the synthesized phase change nano microcapsule sample are observed by a field emission transmission electron microscope (Hitachi HF5000) of Hitachi corporation, and the accelerating voltage is 70 kV.
Fig. 1 shows a transmission electron microscope image of the prepared silica-coated paraffin nano-microcapsule. As is apparent from fig. 1, the prepared phase-change nano-microcapsule shows a good spherical morphology with an average particle diameter of about 45nm, a compact and smooth surface, and no defects. It can also be seen from fig. 1 that the prepared silica-coated paraffin phase-change nano-microcapsule is really a clear core-shell structure, paraffin is used as the inner core of the microcapsule, and silica is used as the outer shell layer. Figure 2 shows that the dried silica-coated paraffin nanocapsule is colorless micronic solid.
Experimental example 2: differential thermal (DSC) analysis
A differential scanning calorimeter is adopted to test the phase change temperature and the phase change enthalpy of paraffin and phase change nano microcapsule samples in two processes of melting and crystallizing, the temperature test range is that the temperature rise rate is 5 ℃/min, and the sample weight is about 0 ℃ to 80 ℃. All samples were dried and their thermal history was removed prior to testing. The durability of the samples was examined by subjecting the samples to a thermal cycling test in the range of 0 ℃ to 80 ℃ under the same test conditions, with a cycle time of 100.
Fig. 3 and 4 show DSC phase transition curves of paraffin wax with a melting point of 29 c, from which it can be seen that the melting peak and crystallization peak of 29 c paraffin wax pure and silica-coated nanocapsules both exhibit a unimodal form, with corresponding melting and crystallization temperatures of 29.4 c and 33.8 c, respectively. In the aspect of stability, after the silica is wrapped and after 100 times of hot-cold cycles, the melting enthalpy and the crystallization enthalpy are very stable and almost not changed, while the melting enthalpy of a pure paraffin sample is very unstable and is reduced by more than 30%.
Melting temperature (T) obtained by analyzing the main absorption peaks by using TA Universal Analysis 2000 thermal Analysis softwarem) Crystallization temperature (T)c) Melting enthalpy value (Δ H)m) And enthalpy of crystallization (. DELTA.H)c) The data are shown in table 1. As can be seen from the data in Table 1, the melting temperature and the melting enthalpy of the paraffin are 31.4 ℃ and 176.2kJ/kg, respectively, and the crystallization temperature and the crystallization enthalpy are 28.7 ℃ and 179.3kJ/kg, respectively; the melting temperature and the melting enthalpy of the nano-microcapsule after being coated by the silicon dioxide are respectively 32.1 ℃ and 121.1kJ/kg, and the crystallization temperature and the crystallization enthalpy are respectively 29.5 ℃ and 119.5 kJ/kg.
Table 1: phase change parameter of paraffin and silicon dioxide coated nano microcapsule
Experimental example 3: thermogravimetric (TGA) analysis
Weighing about 5mg of paraffin and paraffin phase change nano microcapsule sample, and performing thermogravimetric analysis by using a D8 type thermogravimetric analyzer produced by American TA company, wherein the test temperature range is 50-450 ℃, the temperature rise rate is 10 ℃/min, and N is2The flow rate was 50mL/min and the results were analyzed using Origin mapping software.
As can be seen in fig. 5, the heat loss curve for paraffin wax reaches a maximum degradation rate at 165 c and the mass has almost decreased to 0 at 205 c, indicating that the paraffin wax has completely decomposed and volatilized. And in Paraffin @ SiO2In the heat loss curve of (2), the nano microcapsule reaches the maximum decomposition rate at 163 ℃, and compared with pure paraffin, the maximum degradation rate is about 80%, which shows that SiO2The phase-change nano microcapsule is used as a wall material to improve the thermal stability of the microcapsule, and the prepared phase-change nano microcapsule has good coating property on phase-change materials.
Experimental example 4: coating rate and coating efficiency of nano-microcapsules
Since silica is not a phase change material, it does not have the ability to store and release thermal energy. The heat storage and release capabilities of the microcapsules are all derived from the internal phase change material. Therefore, the thermal storage capacity of the microcapsules depends on the amount of paraffin coated in the microcapsules. The phase change property of the phase change microcapsule is generally characterized by two parameters of coating rate (R) and coating efficiency (E), and is shown in Table 2.
R＝ΔHm/ΔHm-paraffin×100％
E＝(ΔHm+ΔHc)/(ΔHm-paraffin+ΔHc-paraffin)×100％
Wherein, Δ Hm-paraffinAnd Δ Hc-paraffinRespectively represent the melting enthalpy and the crystallization enthalpy of the paraffin.
Table 2: coating rate (R) and coating efficiency (E) in phase change nano-microcapsules
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Claims (10)
1. A preparation method of a silicon dioxide coated paraffin phase change nano microcapsule is characterized by comprising the following steps:
1) completely dissolving 1, 2-distearoyl-sn-propanetriyl-3-phosphorylcholine and pyridine palmitate in an organic solvent at 65 ℃ to obtain a mixed solution;
2) evaporating the mixed solution obtained in the step 1) under reduced pressure to obtain a layer of film, adding water into the film, carrying out ultrasonic treatment at 65 ℃ to obtain emulsion, adding paraffin into the emulsion, and continuing ultrasonic treatment;
3) adding water and tetraethyl orthosilicate into the paraffin emulsion subjected to ultrasonic treatment in the step 2), and stirring at room temperature for 20-30 hours;
4) centrifuging the mixed solution obtained after stirring in the step 3), and washing with water to obtain the silicon dioxide-coated paraffin phase-change nano microcapsule.
2. The method for preparing the silica-coated paraffin phase-change nano-microcapsule according to claim 1, wherein the organic solvent in step 1) is chloroform, and the w/w/v ratio of the 1, 2-distearoyl-sn-propanetriyl-3-phosphorylcholine, the pyridine palmitate and the organic solvent is 16:1: 9.
3. The preparation method of the silica-coated paraffin phase-change nano-microcapsule according to claim 1, wherein the pyridine palmitate in the step 1) is obtained through the following steps:
a. dissolving palmitic acid and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride in dry DMF (dimethyl formamide) in an ice bath, adding N-hydroxysuccinimide, stirring for 6 hours under the protection of argon, and then evaporating under reduced pressure to obtain a colorless solid, wherein the solid is purified by using a silica gel column to obtain palmitic acid succinimide ester;
b. dropwise adding the palmitic acid succinimide ester into 1, 2-ethylenediamine, stirring for 2 hours, and evaporating under reduced pressure to obtain palmitic acid amino;
c. dissolving 4-pyridine acetic acid hydrochloride in DMF to obtain a mixed solution, adding 1- (3-dimethylaminopropyl) -3-ethyl carbodiimide hydrochloride, hydroxybenzotriazole and triethylamine, adding palmitic acid amino into the mixed solution, stirring at 50 ℃ for 15 hours, and then recrystallizing to obtain pyridine palmitate.
4. The method for preparing phase-change nano microcapsules coated with silicon dioxide according to claim 1, wherein the paraffin wax in step 2) is paraffin wax with different melting point ranges.
5. The preparation method of the silica-coated paraffin phase-change nanocapsule as claimed in claim 1, wherein the ultrasonic treatment in step 2) is ultrasonic treatment at power of 200-400W for 10-20 min.
6. The method for preparing phase-change nano-microcapsule coated with silica and paraffin according to claim 1, wherein the reduced pressure evaporation in step 2) is performed in a rotary evaporator under a pressure of less than 0.1 atm.
7. The method for preparing the phase-change nano microcapsule coated with silicon dioxide and paraffin according to claim 1, wherein the volume ratio of the water to the tetraethyl orthosilicate in the step 3) is 60: 1.
8. The method for preparing the phase-change nano microcapsule of paraffin wrapped by silicon dioxide according to claim 4, wherein the different melting point ranges of the paraffin are 29 ℃, 37 ℃, 45 ℃ and 52 ℃.
9. A silica-coated paraffin phase-change nano-microcapsule obtained by the preparation method according to any one of claims 1 to 8, having an average particle size of less than 100 nm.
10. Use of the silica-coated paraffin phase-change nanocapsule of claim 9 in battery thermal management, building energy conservation, industrial waste heat recovery and solar thermal utilization.
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