CN106622052B - A kind of preparation method of nanocapsules - Google Patents
A kind of preparation method of nanocapsules Download PDFInfo
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- CN106622052B CN106622052B CN201611038250.XA CN201611038250A CN106622052B CN 106622052 B CN106622052 B CN 106622052B CN 201611038250 A CN201611038250 A CN 201611038250A CN 106622052 B CN106622052 B CN 106622052B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J13/043—Drying and spraying
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- C—CHEMISTRY; METALLURGY
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- 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 kind of preparation methods of nanocapsules, it is characterised in that uses amphiphatic nanometer disk in emulsifying process early period and makees interface stability particle, and is aided with the stabilization of anionic surfactant.Specifically: heating phase-change material, which is allowed to melt completely, forms oily phase；Surfactant is proportionally added into aqueous solution and forms water phase；Amphiphilic nano disk is proportionally added into formation ethyl alcohol phase in ethanol solution.The above three-phase is mixed in proportion, slight concussion can form the nanoemulsions of phase-change material.Nanoemulsions system is placed under the synthetic technological condition of cyst wall, the synthesis of nanocapsules can be completed.The preparation method that the present invention refers to is not required to that any mechanical external force is taken to can be completed, and simple process is easy to operate；The nanocapsules regular appearance of preparation, surface be smooth, uniform particle sizes, and the partial size of Nano capsule can be effectively controlled by changing nanometer disk and proportion of surfactant.
Description
Technical field
The invention belongs to technical field of function materials, it is related to a kind of cooperateing with using amphiphilic nano disk and surfactant
The method that effect prepares nanocapsules.
Background technique
In recent years, with microelectric technique, fuel cell, transport service, industrial manufacturing industry, aerospace, building, weaving,
The rapid development of the industry such as military, using energy source and communication, new project is proposed to field of heat transfer.These fields are directed to
To the problem of phase-change material accumulation of heat, but due to phase-change material there is some critical defects in use (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.Currently, most common microencapsulated phase change material partial size is in micron-scale, microcapsules technology refers to solid
The core material of grain, liquid, gas or ghost as capsule, forms the mistake of one layer of continuous and very thin packing with filmogen outside it
Journey.Its technology of preparing originates from the 1950s, being grown rapidly in the mid-1970s, occurs 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 it is used as hot-fluid
The latent heat type microcapsules that body is strengthened, can greatly strengthening fluid heat transfer property, but still have its shortcoming: easily causing mill
The bad results such as damage, blocking.If the partial size of capsule is down to nano-scale, i.e. nano capsule phase change material, these problems will have
Improved.Since late 1970s Narty etc. proposes Nano capsule concept first, people grind nanoencapsulated drug
Study carefully it is more, and to nano capsule phase change material study it is relatively fewer, start to walk it is also later.
Zhang etc. is reported using n-octadecane as capsule-core, and melamine formaldehyde resin is cyst material, in-situ polymerization system
The nano capsule phase change material for being 770nm for average grain diameter.Luo etc. has been synthesized using fine emulsion polymerization using paraffin as capsule
Core, polystyrene are cyst wall, and average grain diameter is the capsule of 100nm.Park etc. has been synthesized by fine emulsion polymerization is with paraffin
Core, the stable spherical Nano capsule that polystyrene is shell, show there is good thermal stability by DSC freeze-thaw cycle experiment
And release performance, the heat of transformation reach as high as 145kJkg-1.In addition, Momoda etc. is reported with arachidic acid, trimethylolethane
Equal phase-change materials are capsule-core, and Organosilicon Polymers are the Nano capsule of cyst wall, which can be applied in fuel cell
Liquid.Nanoencapsulation phase-change material technology not only overcomes the limitation of microencapsulated phase change material application, but also is improving phase transformation
Materials'use efficiency has broad application prospects in terms of widening application field.
Current existing Nano capsule preparation method is generally existing complicated for operation, at high cost, the phase transformation glue finally prepared
Capsule granular size is different, is not suitable for industrial mass production.Invention describes a kind of novel Nano capsule preparation methods, no
Any mechanical external force need to be taken to can be completed, simple process is easy to operate；The nanocapsules regular appearance of preparation,
Surface is smooth, uniform particle sizes, and the partial size of Nano capsule can be effectively controlled by changing nanometer disk and proportion of surfactant.
Summary of the invention
The present invention uses amphiphilic nano dish in emulsifying process against the above deficiency, in the early period of nanocapsules
Piece and surfactant form nanoemulsions using the synergistic effect coating phase-change materials of the two.The method makes phase-change material
Emulsifying step be simplified, do not need to can be completed using any mechanical external force.Meanwhile even if the strong of external force is not cut
It cuts, 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 disk: the disk material alpha zirconium phosphate that synthesis particle size is 300nm or so is pressed
Certain molar ratio takes modified material octadecylisocyanate and disk material alpha zirconium phosphate respectively.Made with organic solvent toluene
For solvent, reacted 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 disk.It is molten with water
Agent is added tetrabutylammonium hydroxide amine according to molar ratio 1:1 and carries out intercalation stripping, obtains the amphiphilic disk particle basic zirconium phosphate of single layer
(α-ZrP-ODI) aqueous solution.
(2) preparation of aqueous dispersant and amphiphilic disk ethanol solution:: surfactant is weighed with assay balance
It is dissolved in deionized water, is made into the aqueous dispersant that concentration is 0.1%~10%, takes amphiphilic disk a-Zrp-ODI water-soluble
Liquid is scattered in dehydrated alcohol, and being made into concentration is 0.1%~10% amphiphilic disk ethanol solution.
(3) preparation of phase-change material nanoemulsions: weighing phase-change material with assay balance, to be scattered in previous step prepared
Aqueous dispersant is made into oil water mixture, then adds previous step prepared amphiphilic disk ethanol solution hand half a minute
Form colostric fluid.
(4) a certain amount of inducing agent azodiisobutyronitrile and styrene list the preparation of nanocapsules: are weighed
Body is added in colostric fluid prepared by previous step, and it is small to be placed in 70 DEG C of constant temperature 5 in electric drying oven with forced convection with hand rolling half a minute
When, obtain wax phase change Nano capsule lotion.
(5) post-processing of nanocapsules: by ethyl alcohol centrifuge washing 2 times of the lotion heat after reaction, go from
Sub- water centrifuge washing is primary, and sample is finally put into freeze drying box is drying over night to obtain wax phase change Nano capsule.
Surfactant in step (2) is the surfactant of anionic, preferably neopelex；
The phase-change material of step (3) is alkane compound n-tetradecane, hexadecane, n-octadecane, NSC 77136, just
The paraffin phase change materials such as eicosane.
Centrifugal rotational speed with ethyl alcohol centrifuge washing is 3000r/min, is persistently centrifuged 3 minutes, with deionized water centrifuge washing
Centrifugal rotational speed be 8000r/min, continue 5 minutes.The temperature of ethyl alcohol and deionized water is controlled at 40~50 degrees Celsius.
Nanocapsules preparation method proposed by the present invention is existed by amphiphilic nano disk and surfactant
Absorption is stablized at oil/water interface, is avoided the mutual collision and fusion of phase-change material cream pearl, is reduced nanocapsules
Grain diameter, the Nano capsule particle size prepared is uniform.This method is simplified the emulsion process of phase-change material, section
About the energy, it can be achieved that nanocapsules mass production.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of one nanocapsules of the embodiment of the present invention
Fig. 2 is the scanning electron microscope (SEM) photograph of two nanocapsules of the embodiment of the present invention
Specific embodiment
It will be helpful to understand the present invention by following embodiment, but be not intended to limit the contents of the present invention.
Embodiment one
(1) preparation of amphiphilic nano disk: the disk like particle that synthesis particle size is 300nm or so.Basic zirconium phosphate disk like
Colloid is to be mixed by ZrCl2O8H2O and phosphoric acid according to the ratio of 1:10, and be added in pyroreaction kettle and be heated to 200 DEG C
For 24 hours, then drying obtains white powder in thermostatic drying chamber for centrifuge washing 3~4 times for heat preservation.It uses again and passes through X-ray diffraction (X-
Ray diffraction, abbreviation XRD) test, determine whether above-mentioned synthesized white powder is alpha zirconium phosphate；Utilize scanning
The microscopic appearance of electron microscope (Scanning Electron Microscopy, abbreviation SEM) observation powder.Amphiphilic modification
Then mixed by basic zirconium phosphate and octadecylisocyanate according to the ratio of molar ratio 10:1, using toluene as solvent, nitrogen atmosphere, In
90 DEG C of sealings are stirred to react 24 hours, and last centrifuge washing obtains modified zirconium phosphate, takes water as a solvent, and adds according to molar ratio 1:1
Enter tetrabutylammonium hydroxide amine and carry out intercalation stripping, obtains the amphiphilic disk particle basic zirconium phosphate (α-ZrP-ODI) of single layer.
(2) surface of 0.02g the preparation of aqueous dispersant and amphiphilic disk ethanol solution: 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%,
For the amphiphilic disk a-Zrp-ODI aqueous dispersion of 0.5ml in 10ml dehydrated alcohol, being made into concentration is 0.15% amphiphilic disk
Ethanol solution.
(3) preparation of phase-change material nanoemulsions: previous step is scattered in the nonadecane that assay balance weighs 0.2g and is matched
The 10ml aqueous dispersant of system, being made into its mass ratio of oil water mixture is 1:50, then adds the prepared parents of previous step
Property disk 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 colostric fluid prepared by previous step, it is dry to be placed in electric heating air blast with hand rolling half a minute
70 in dry case.C constant temperature 5 hours, obtain wax phase change Nano capsule lotion.
(5) it the post-processing of nanocapsules: is centrifuged with 50 DEG C of twice of hot ethanol centrifuge washings and deionized water
A phase transformation capsule lotion is washed, obtains phase transformation Nano capsule powder by freeze-drying.
Embodiment two
(1) surface of 0.04g the preparation of aqueous dispersant and amphiphilic disk ethanol solution: 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 dehydrated alcohol, be made into concentration is amphiphilic disk a-Zrp-ODI aqueous dispersion in 0.5ml embodiment one
0.15% amphiphilic disk ethanol solution.
(2) preparation of phase-change material nanoemulsions: previous step is scattered in the nonadecane that assay balance weighs 0.2g and is matched
The 10ml aqueous dispersant of system, being made into its mass ratio of oil water mixture is 1:50, then adds the prepared parents of previous step
Property disk 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 colostric fluid prepared by previous step, it is dry to be placed in electric heating air blast with hand rolling half a minute
70 in dry case.C constant temperature 5 hours, obtain wax phase change Nano capsule lotion.
(4) become the post-processing of material nano capsule: being washed with 50 DEG C of twice of hot ethanol centrifuge washings and deionized water centrifugation
A phase transformation capsule lotion is washed, obtains phase transformation Nano capsule powder by freeze-drying.
By embodiment as can be seen that the nanocapsules regular appearance of preparation, surface is smooth, uniform particle sizes,
And the partial size of Nano capsule can be effectively controlled by changing nanometer disk and proportion of surfactant.
Claims (5)
1. a kind of preparation method of nanocapsules, preparation method includes the preparation of amphiphilic nano disk, dispersing agent
Aqueous solution and the preparation of amphiphilic disk ethanol solution, the preparation of phase-change material nanoemulsions, nanocapsules system
Standby, nanocapsules post-processings；It is characterized in that, the preparation of the phase-change material nanoemulsions is to use assay balance
It weighs phase-change material and is scattered in the prepared aqueous dispersant of previous step, be made into oil water mixture, then add previous step and matched
The amphiphilic disk ethanol solution of system hand half a minute forms colostric fluid；The preparation of the nanocapsules: one is weighed
Quantitative inducing agent azodiisobutyronitrile and styrene monomer are added in colostric fluid prepared by previous step, shake half with hand
Minute is placed in 70 DEG C constant temperature 5 hours in electric drying oven with forced convection, obtains wax phase change Nano capsule lotion；
The preparation of the amphiphilic nano disk includes: to synthesize the disk material alpha zirconium phosphate that particle size is 300nm or so,
Modified material octadecylisocyanate and disk material alpha zirconium phosphate are taken respectively by certain molar ratio；With organic solvent toluene
As solvent, reacted 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 disk；With water
For solvent, tetrabutylammonium hydroxide amine is added according to molar ratio 1:1 and carries out intercalation stripping, obtains the amphiphilic disk α-of single layer
ZrP-ODI aqueous solution；
The aqueous dispersant is using the surfactant of anionic as dispersing agent.
2. the preparation method of nanocapsules described in claim 1, which is characterized in that aqueous dispersant with
The preparation of amphiphilic disk ethanol solution: weighing surfactant with assay balance and be dissolved in deionized water, is made into concentration and is
0.1% ~ 10% aqueous dispersant takes amphiphilic disk a-Zrp-ODI aqueous dispersion in dehydrated alcohol, is made into concentration
For 0.1% ~ 10% amphiphilic disk ethanol solution.
3. the preparation method of nanocapsules described in claim 1, which is characterized in that phase-change material nanometre glue
The post-processing of capsule: by ethyl alcohol centrifuge washing 2 times of the lotion heat after reaction, deionized water centrifuge washing is primary, finally will
Sample is put into that freeze drying box is drying over night to obtain wax phase change Nano capsule.
4. the preparation method of nanocapsules described in claim 3, which is characterized in that ethyl alcohol centrifuge washing
Centrifugal rotational speed is 3000r/min, is persistently centrifuged 3 minutes, and the centrifugal rotational speed with deionized water centrifuge washing is 8000r/min,
Continue 5 minutes；The temperature of ethyl alcohol and deionized water is controlled at 40 ~ 50 degrees Celsius.
5. the preparation method of nanocapsules described in claim 1, which is characterized in that the phase-change material is
Refer to the paraffin phase change materials such as alkane compound n-tetradecane, hexadecane, n-octadecane, NSC 77136, n-eicosane.
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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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