CN106622052A - A method of preparing a phase-change material nanometer capsule - Google Patents
A method of preparing a phase-change material nanometer capsule Download PDFInfo
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- CN106622052A CN106622052A CN201611038250.XA CN201611038250A CN106622052A CN 106622052 A CN106622052 A CN 106622052A CN 201611038250 A CN201611038250 A CN 201611038250A CN 106622052 A CN106622052 A CN 106622052A
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- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/04—Making microcapsules or microballoons by physical processes, e.g. drying, spraying
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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
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Abstract
A method of preparing a phase-change material nanometer capsule is disclosed. The method is characterized in that amphiphilic nanometer disks are adopted as interface stabilizing particles in an earlier-stage emulsification process, and a stabilizing function of an anionic surfactant is adopted as assistance. The method includes heating a phase-change material to fully melt the phase-change material to form an oil phase; adding the surfactant into an aqueous solution according to a ratio to form a water phase; adding the amphiphilic nanometer disks into an ethanol solution according to a ratio to form an ethanol phase; mixing the oil phase, the water phase and the ethanol phase according to a ratio; slightly vibrating the mixture to form a nanometer emulsion of the phase-change material; and allowing the nanometer emulsion system to be under synthesis process conditions of capsule walls, and then synthesis of a phase-change material nanometer capsule can be finished. The method does not need external mechanical force, and is simple in process and convenient to operate. The prepared phase-change material nanometer capsule has structured morphology, smooth surfaces and a uniform particle diameter. The particle diameter of the nanometer capsule can be effectively controlled through changing the ratio of the nanometer disks to the surfactant.
Description
Technical field
The invention belongs to technical field of function materials, is related to one kind and is cooperateed with using amphiphilic nano video disc and surfactant
The method that effect prepares nanocapsules.
Background technology
In recent years, with microelectric technique, fuel cell, transport service, industrial manufacturing industry, Aero-Space, building, weaving,
Developing rapidly for the industry such as military, using energy source and communication, to field of heat transfer new problem is proposed.These fields are directed to
To the problem of phase-change material accumulation of heat, but because phase-change material has in use some critical defects (such as：Corrosivity, shakiness
Qualitative, supercooling, heat transfer property difference etc.), limit its large-scale application industrially.It is effective by phase-change material capsule
One of method of modifying.At present, in micron-scale, microcapsules technology refers to solid the most frequently used microencapsulated phase change material particle diameter
Grain, liquid, gas or ghost form the mistake of one layer of continuous and very thin packing with filmogen as the core of capsule outside it
Journey.Its technology of preparing originates from the 1950's, and in the mid-1970s fast development is obtained, and occurs in that during this period many micro-
Encapsulated products and technique, and it is widely used in the multiple fields such as medicine, food, coating, ink, additive.Such as hot-fluid
The latent heat type microcapsules of body reinforcing, can greatly strengthening fluid heat transfer property, but still have its weak point：Easily cause mill
The bad results such as damage, blocking.If the particle diameter of capsule is down to into nano-scale, i.e. nano capsule phase change material, these problems will have
Improved.Since proposing Nano capsule concept first from late 1970s Narty etc., people grind to nanoencapsulated drug
Study carefully more, and relatively fewer is studied to nano capsule phase change material, its starting is also later.
Zhang etc. is reported with n-octadecane as capsule-core, and melamine formaldehyde resin is cyst material, in-situ polymerization system
For the nano capsule phase change material that average grain diameter is 770nm.Luo etc. has synthesized with paraffin as capsule using fine emulsion polymerization
Core, polystyrene are cyst wall, and average grain diameter is the capsule of 100nm.Park etc. has been synthesized by fine emulsion polymerization
Core, polystyrene are the stable spherical Nano capsule of shell, are shown by DSC freeze-thaw cycle experiments, with good heat endurance
And release performance, the heat of transformation reaches as high as 145kJkg-1.Additionally, Momoda etc. is reported with arachidic acid, trimethylolethane
It is capsule-core Deng phase-change material, Organosilicon Polymers are the Nano capsule of cyst wall, the functional thermal fluid can be applicable in fuel cell
Liquid.Nanoencapsulation phase-change material technology not only overcomes the limitation of microencapsulated phase change material application, and is improving phase transformation
Materials'use efficiency, widens application aspect and has broad application prospects.
Current existing Nano capsule preparation method generally existing complex operation, high cost, its final phase transformation glue for preparing
Capsule granular size differs, and is not suitable for industrial mass production.Invention describes a kind of new Nano capsule preparation method, no
Complete by any mechanical external force need to be taken, process is simple is easy to operate；The nanocapsules regular appearance of preparation,
Surface is smooth, uniform particle sizes, and by change nanometer video disc and proportion of surfactant can effective control Nano capsule particle diameter.
The content of the invention
The present invention is not enough for more than, and amphiphilic nano dish is adopted in the early stage emulsifying process of nanocapsules
Piece and surfactant, using the synergy coating phase-change materials of the two nanoemulsions are formed.The method causes phase-change material
Emulsifying step be simplified, it is not necessary to can complete using any mechanical external force.Meanwhile, even if cutting strongly without external force
Cut, the particle diameter distribution of nanocapsules is still uniform, and capsule grain diameter size can regulate and control.
Technical scheme is as follows:
(1) preparation of amphiphilic nano video disc：Synthesis particle size is the video disc material alpha zirconium phosphate of 300nm or so, is pressed
Certain mol ratio takes respectively material modified octadecylisocyanate and video disc material alpha zirconium phosphate.With organic solvent toluene work
For solvent, react 24 hours at a high temperature of 90 DEG C of nitrogen environment.It is then centrifuged for washing and is dried to obtain modified video disc.With water as molten
Agent, according to mol ratio 1:1 addition tetrabutylammonium hydroxide amine carries out intercalation stripping, obtains the amphiphilic video disc particle basic zirconium phosphate of individual layer
(α-ZrP-ODI) aqueous solution.
(2) preparation of aqueous dispersant and amphiphilic video disc ethanol solution：：Surfactant is weighed with assay balance
In being dissolved in deionized water, the aqueous dispersant that concentration is 0.1%～10% is made into, takes amphiphilic video disc a-Zrp-ODI water-soluble
Liquid is scattered in absolute ethyl alcohol, is made into concentration for 0.1%～10% amphiphilic video disc ethanol solution.
(3) preparation of phase-change material nanoemulsions：Phase-change material is weighed with assay balance be scattered in what previous step was prepared
Aqueous dispersant, is made into oil water mixture, then adds amphiphilic video disc ethanol solution hand half a minute that previous step is prepared
Form colostric fluid.
(4) preparation of nanocapsules：Weigh a certain amount of inducing agent azodiisobutyronitrile and styrene list
Body, is added in the colostric fluid prepared by previous step, is placed in 70 DEG C of constant temperature 5 in electric drying oven with forced convection with hand rolling half a minute little
When, obtain wax phase change Nano capsule emulsion.
(5) post processing of nanocapsules：By the ethanol centrifuge washing 2 times of reacted emulsion heat, go from
Sub- water centrifuge washing once, finally by sample is put into that freeze drying box is drying over night to obtain wax phase change Nano capsule.
Surfactant in step (two) for anionic surfactant, preferred neopelex；
The phase-change material of step (three) is alkane compound n-tetradecane, hexadecane, n-octadecane, NSC 77136, just
The paraffin phase change materials such as eicosane.
Centrifugal rotational speed with ethanol centrifuge washing is 3000r/min, is persistently centrifuged 3 minutes, deionized water centrifuge washing
Centrifugal rotational speed be 8000r/min, continue 5 minutes.The temperature control of ethanol and deionized water is at 40～50 degrees Celsius.
Nanocapsules preparation method proposed by the present invention is existed by amphiphilic nano video disc and surfactant
The stable absorption at oil/water interface, it is to avoid the mutual collision and fusion of phase-change material breast pearl, reduces nanocapsules
Grain diameter, the Nano capsule particle size prepared is homogeneous.The method is simplified the emulsion process of phase-change material, section
About the energy, is capable of achieving the production in enormous quantities of nanocapsules.
Description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of the nanocapsules of the embodiment of the present invention one
Fig. 2 is the scanning electron microscope (SEM) photograph of the nanocapsules of the embodiment of the present invention two
Specific embodiment
Will be helpful to understand the present invention by following examples, but be not intended to limit present disclosure.
Embodiment one
(1) preparation of amphiphilic nano video disc：Synthesis particle size is the disk like particle of 300nm or so.Basic zirconium phosphate disk like
Colloid is according to 1 by ZrCl2O8H2O and phosphoric acid:10 ratio mixing, and be added in pyroreaction kettle and be heated to 200 DEG C
Insulation 24h, 3～4 times then drying obtains white powder to centrifuge washing in thermostatic drying chamber.Again with by X-ray diffraction (X-
Ray diffraction, abbreviation XRD) test, determine whether above-mentioned synthesized white powder is alpha zirconium phosphate；Using scanning
Electron microscope (Scanning Electron Microscopy, abbreviation SEM) observes the microscopic appearance of powder.It is amphiphilic modified
Then by basic zirconium phosphate and octadecylisocyanate according to mol ratio 10:1 ratio mixing, with toluene as solvent, nitrogen atmosphere,
90 DEG C seal stirring reaction 24 hours, and last centrifuge washing obtains modified zirconium phosphate, with water as solvent, according to mol ratio 1:1 adds
Entering tetrabutylammonium hydroxide amine carries out intercalation stripping, obtains the amphiphilic video disc particle basic zirconium phosphate (α-ZrP-ODI) of individual layer.
(2) preparation of aqueous dispersant and amphiphilic video disc ethanol solution：The surface of 0.02g is weighed with assay balance
Activating agent neopelex is dissolved in the deionized water of 10ml, is made into the aqueous dispersant that concentration is 0.2%,
The amphiphilic video disc a-Zrp-ODI aqueous dispersions of 0.5ml are made into concentration for 0.15% amphiphilic video disc in 10ml absolute ethyl alcohols
Ethanol solution.
(3) preparation of phase-change material nanoemulsions：The nonadecane for weighing 0.2g with assay balance is scattered in previous step and is matched somebody with somebody
The 10ml aqueous dispersants of system, are made into its mass ratio of oil water mixture for 1:50, then add the parents that previous step is prepared
Property video disc ethanol solution hand half a minute form colostric fluid.
(4) preparation of nanocapsules：The azodiisobutyronitrile (AIBN) for weighing 0.002g with assay balance is molten
In the styrene monomer of 1ml, it is added in the colostric fluid prepared by previous step, is placed in electric heating air blast with hand rolling half a minute and does
70 in dry case.C constant temperature 5 hours, obtains wax phase change Nano capsule emulsion.
(5) post processing of nanocapsules：It is centrifuged with 50 DEG C of twice of hot ethanol centrifuge washings and deionized water
A time phase transformation capsule emulsion of washing, through freeze-drying phase transformation Nano capsule powder is obtained.
Embodiment two
(1) preparation of aqueous dispersant and amphiphilic video disc ethanol solution：The surface of 0.04g is weighed with assay balance
Activating agent neopelex is dissolved in the deionized water of 10ml, is made into the aqueous dispersant that concentration is 0.2%,
In 10ml absolute ethyl alcohols, be made into concentration is amphiphilic video disc a-Zrp-ODI aqueous dispersions in 0.5ml embodiments one
0.15% amphiphilic video disc ethanol solution.
(2) preparation of phase-change material nanoemulsions：The nonadecane for weighing 0.2g with assay balance is scattered in previous step and is matched somebody with somebody
The 10ml aqueous dispersants of system, are made into its mass ratio of oil water mixture for 1:50, then add the parents that previous step is prepared
Property video disc ethanol solution hand half a minute form colostric fluid.
(3) preparation of nanocapsules：The azodiisobutyronitrile (AIBN) for weighing 0.002g with assay balance is molten
In the styrene monomer of 1ml, it is added in the colostric fluid prepared by previous step, is placed in electric heating air blast with hand rolling half a minute and does
70 in dry case.C constant temperature 5 hours, obtains wax phase change Nano capsule emulsion.
(4) post processing of material nano capsule is become：Washed with 50 DEG C of twice of hot ethanol centrifuge washings and deionized water centrifugation
A phase transformation capsule emulsion is washed, through freeze-drying phase transformation Nano capsule powder is obtained.
By embodiment as can be seen that the nanocapsules regular appearance for preparing, surface is smooth, uniform particle sizes,
And by change nanometer video disc and proportion of surfactant can effective control Nano capsule particle diameter.
Claims (6)
1. a kind of preparation method of nanocapsules, preparation method includes preparation, the dispersant of amphiphilic nano video disc
The preparation of the aqueous solution and amphiphilic video disc ethanol solution, the preparation of phase-change material nanoemulsions, the system of nanocapsules
Standby, nanocapsules post processings；Characterized in that, the preparation of the phase-change material nanoemulsions is to use assay balance
Weigh phase-change material and be scattered in the aqueous dispersant that previous step is prepared, be made into oil water mixture, then add previous step and matched somebody with somebody
Amphiphilic video disc ethanol solution hand half a minute of system forms colostric fluid；The preparation of the nanocapsules：Weigh one
Quantitative inducing agent azodiisobutyronitrile and styrene monomer, are added in the colostric fluid prepared by previous step, and with hand half is shaken
Minute is placed in electric drying oven with forced convection 70 DEG C of constant temperature 5 hours, obtains wax phase change Nano capsule emulsion.
2. the preparation method of the nanocapsules described in claim 1, it is characterised in that the system of amphiphilic nano video disc
It is standby to include：Synthesis particle size is the video disc material alpha zirconium phosphate of 300nm or so, is taken respectively by certain mol ratio material modified
Octadecylisocyanate and video disc material alpha zirconium phosphate.Using organic solvent toluene as solvent, the high temperature that 90 DEG C of nitrogen environment
Lower reaction 24 hours；It is then centrifuged for washing and is dried to obtain modified video disc；With water as solvent, according to mol ratio 1:1 adds the tetrabutyl
Oxyammonia carries out intercalation stripping, obtains amphiphilic video disc particle basic zirconium phosphate (α-ZrP-ODI) aqueous solution of individual layer.
3. the preparation method of the nanocapsules described in claim 1, it is characterised in that aqueous dispersant and parents
The preparation of property video disc ethanol solution：Weigh surfactant with assay balance to be dissolved in deionized water, be made into concentration for 0.1%～
10% aqueous dispersant, takes amphiphilic video disc a-Zrp-ODI aqueous dispersions in absolute ethyl alcohol, and being made into concentration is
0.1%～10% amphiphilic video disc ethanol solution.
4. the preparation method of the nanocapsules described in claim 1, it is characterised in that nanocapsules
Post processing：By the ethanol centrifuge washing 2 times of reacted emulsion heat, deionized water centrifuge washing once, is finally put in sample
Enter that freeze drying box is drying over night to obtain wax phase change Nano capsule.
5. the preparation method of the nanocapsules described in claim 4, it is characterised in that the centrifugation of ethanol centrifuge washing
Rotating speed is 3000r/min, is persistently centrifuged 3 minutes, and the centrifugal rotational speed of deionized water centrifuge washing is 8000r/min, continues 5 points
Clock；The temperature control of ethanol and deionized water is at 40～50 degrees Celsius.
6. the preparation method of the nanocapsules described in claim 1, it is characterised in that the phase-change material refers to alkane
The paraffin phase change materials such as hydrocarbon compound n-tetradecane, hexadecane, n-octadecane, NSC 77136, n-eicosane, surfactant
For the surfactant of anionic.
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| CN108300422A (en) * | 2018-02-05 | 2018-07-20 | 陕西科技大学 | Temperature-adjusting type silica wall material phase transformation Nano capsule and preparation method thereof |
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| CN104449590A (en) * | 2014-12-05 | 2015-03-25 | 中国工程物理研究院化工材料研究所 | Phase-change energy-storage material nanocapsule and preparation method thereof |
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| CN104449590A (en) * | 2014-12-05 | 2015-03-25 | 中国工程物理研究院化工材料研究所 | Phase-change energy-storage material nanocapsule and preparation method thereof |
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| XUEZHEN WANG,ETAL.,: "Nano-encapsulated PCM via Pickering Emulsification", 《SCIENTIFIC REPORTS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108300422A (en) * | 2018-02-05 | 2018-07-20 | 陕西科技大学 | Temperature-adjusting type silica wall material phase transformation Nano capsule and preparation method thereof |
| CN108300422B (en) * | 2018-02-05 | 2021-03-02 | 陕西科技大学 | Temperature-regulating type silicon dioxide wall material phase change nanocapsule and preparation method thereof |
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