CN104927779B - A kind of super-hydrophobic microcapsules of phase-change material and preparation method thereof - Google Patents
A kind of super-hydrophobic microcapsules of phase-change material and preparation method thereof Download PDFInfo
- Publication number
- CN104927779B CN104927779B CN201510379883.6A CN201510379883A CN104927779B CN 104927779 B CN104927779 B CN 104927779B CN 201510379883 A CN201510379883 A CN 201510379883A CN 104927779 B CN104927779 B CN 104927779B
- Authority
- CN
- China
- Prior art keywords
- microcapsules
- phase
- change material
- super
- hydrophobic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Manufacturing Of Micro-Capsules (AREA)
Abstract
A kind of super-hydrophobic microcapsules of phase-change material and preparation method thereof, belong to functional material preparing technical field.Softgel shell including capsule-core and the micro-nano multilevel hierarchy of outer surface band, is calculated by mass percentage, and the content of capsule-core is 60~90wt%, and the content of the softgel shell of the micro-nano multilevel hierarchy of outer surface band is 10~40wt%；The microcapsules average diameter is 10~1000 μm, and softgel shell average thickness is 100~500nm, and softgel shell outer surface average particle diameter is 150~650nm.The super-hydrophobic microcapsules of phase-change material that the present invention obtains have many advantages, such as that structure-controllable, core content are high, super-hydrophobicity is strong, thermal stability is good；And the preparation process of microcapsules is simple, environmentally friendly, easy to operate, applied widely, raw material is cheap and easy to get, it is easy to accomplish industrialization large-scale production and application.
Description
Technical field
The present invention relates to a kind of phase-change material coating technologies, and in particular to a kind of super-hydrophobic microcapsules of phase-change material and its system
Preparation Method belongs to functional material preparing technical field.
Background technology
Phase-change material (Phase Change Material) is that one kind mutually can be absorbed or discharged greatly by changing itself object
Amount latent heat of phase change has good energy storage and temperature control ability to keep substance temperature-resistant or that variation is little.As a kind of new
Type energy-saving material, phase-change material have been widely used in the fields such as space flight boat clothes, building coating, spinning coating, refrigeration control.Phase
Organic and inorganic two major class can be divided by becoming material, and organic phase change material includes alkanes, alcohol acids and high score subclass.Wherein,
Organic alkane phase-change material has many advantages, such as that non-toxic and tasteless, transformation temperature is controllable, environmental suitability is strong and phase transition process continuous-stable,
It is with a wide range of applications.
Since phase-change material is easily leaked in solid-liquid transformation, etched the matrix is unfavorable for recycling.Document (Solar
Energy Materials＆Solar Cells, 2010,94,1235-1240.) propose it is a kind of by phase-change material by macromolecule
Material wraps up the mode that microcapsules are made, and can effectively solve the leakage problem of phase-change material.Microcapsules technology refers to use high score
Sub- film forming matter package solid, liquid or gas material, the technology of substance of the generation with nucleocapsid, the thirties in last century quilt
It is proposed starts, and is initially applied to procrypsis pressure-sensitive carbon paper, has been widely used in cosmetics, pesticide, food, medicine and other fields.
Microcapsules technology and phase-change material are combined, the problems such as leakage when can effectively solve phase-change material liquid condition, corrosion, increased
Strong safety and stability is the applications expanding scope of phase-change material.Chinese patent (CN1161364A) discloses one kind
By the use of melamine resin as the phase-changing energy storage material microcapsules of shell, but since melamine resin is more crisp, phase-change accumulation energy material obtained
Material microcapsules mechanicalness is poor, poor durability.Chinese patent (CN200910105980.0) proposes a kind of high-molecular organic material
The microcapsules of storing energy through phase change preparation method of cladding prepares shape using high-molecular organic material as wall material by emulsion polymerization way
Rule, good dispersion, even particle size distribution, cyst wall good airproof performance and the good phase-transition energy-storage microcapsules material of chemical stability；It but should
The auxiliary agent used in method is wide in variety, and dosage is big, thus residual impurity is more in product, complex process.
Thermal stability is the key property of microcapsules, if core is different with shell coefficient of thermal expansion, microcapsules meeting at high temperature
Burst failure.In fields such as spinning coating, fiber manufacture, high temperature-proof coating materials in application, have to microcapsules thermal stability compared with
High request, therefore the thermal stability for improving microcapsules is of great significance.Improve one of important channel of microcapsules thermal stability
To improve the heat resistance of wall material.Yoshioka etc. using organopolysiloxane as wall material (US Patent 4,024,306,1977),
The higher microcapsules of heat resistance are made by the method for improving the cyst wall degree of cross linking；The heat that this method preferably improves microcapsules is steady
It is qualitative, but complex process, it is difficult to large-scale application.Li Yuanjie etc. proposes a kind of logical in patent (CN200810157553.2)
It crosses and chemical modification is carried out to melamine resin, introduce benzene ring structure in the molecule and prepare the micro- glue of high temperature resistant type phase-change material
The method of capsule；Microcapsules made from this method have higher thermal stability, but complex process, also exist in preparation process free
The shortcomings of content of formaldehyde is high limits the extensive use of the phase-change material.
Super-hydrophobic phenomenon is found in the distinctive automatic cleaning action of lotus leaf at first, has been widely studied at present and applied to numerous
Field.Military favorable to the people grade (Adv.Funct.Mater., 2015,25,1035-1041.) is with titanium dioxide and silica dioxide nano particle
Son is prepared for the microcapsules of ultraviolet light response, the microcapsules quilt for method of the Pickering reagents through Pickering emulsion polymerizations
It is added in water paint and is coated in various substrates, obtains super-hydrophobic coat.But the microcapsules sheet that this method obtains
Body does not have super-hydrophobicity, and the process for separating precipitation polymer is numerous and diverse, need to add in demulsifier or flocculating agent, and auxiliary agent is wide in variety,
Dedoping step is complicated.If super-hydrophobic technology can be applied in phase-change material micro-capsule, it is self-cleaning anti-that its can be just assigned simultaneously
Dirty and selfreparing anti-corrosion function, will have important practical significance in fields such as building coating, spinning coatings.
The content of the invention
The present invention for background technology there are the defects of, it is proposed that a kind of super-hydrophobic microcapsules of phase-change material and its preparation side
Method.The super-hydrophobic microcapsules of the phase-change material have many advantages, such as that structure-controllable, core content are high, super-hydrophobicity is strong, thermal stability is good；
And the preparation process of microcapsules is simple, environmentally friendly, easy to operate, applied widely, raw material is cheap and easy to get, it is easy to accomplish work
Industryization mass produces and application.
Technical scheme is as follows：
A kind of super-hydrophobic microcapsules of phase-change material, the softgel shell including capsule-core and the micro-nano multilevel hierarchy of outer surface band, by matter
Measure percentage calculation, the content of capsule-core is 60~90wt%, the content of the softgel shell of the micro-nano multilevel hierarchy of outer surface band for 10~
40wt%；The microcapsules average diameter be 10~1000 μm, softgel shell average thickness be 100~500nm, softgel shell outer surface particle
Average diameter is 150~650nm.
Further, the static contact angle of the surface of the super-hydrophobic microcapsules of the phase-change material and water is 150~170 °.
Further, the ingredient of the capsule-core and mass percentage are：80~95wt% of organic phase change material, reactivity
5~20wt% of hydrophobic compound.
Further, the organic phase change material is with general formula CnH2n+2The N-alkanes hydrocarbon that (n=12~32) represent
Object, with general formula CnH2n+1X (n=12~32) represent halogenated N-alkanes hydrocarbon compound and with general formula CmH2m+1COOCH2CpH2p+1
It is at least one kind of in the aliphatic ester that (m=10~20, p=4~10) represent.
Further, the reactive hydrophobic compound is with general formula OCN (CH2)kThe two of NCO (k=4~12) expressions are different
Cyanate linear paraffin class compound, 1H, 1H, 2H, 2H- perfluoro capryls triethoxysilane, 1H, 1H, 2H, 2H- perfluoro decyls
It is at least one kind of in triethoxysilane, cyanoacrylate and its derivative.The cyanoacrylate and its derivative are cyanogen
Base methyl acrylate, cyanacrylate, Tisuacryl, octyl 2-cyanoacrylate etc..
Further, the softgel shell is Lauxite, is obtained by the reaction by formaldehyde and urea polycondensation, wherein, formaldehyde and urine
The mass ratio of element is 1:0.37~1:2.22.
The present invention also provides a kind of preparation methods of the super-hydrophobic microcapsules of phase-change material, comprise the following steps：
The preparation of step 1, shell material prepolymer：By the formalin in mass ratio 1 that urea and mass percentage concentration are 37%:
1~1:6 mixing adjust pH to 7~12 with alkali, are stirred to react 0.5~2h at 60~80 DEG C, obtain colorless and transparent liquid,
The as aqueous solution of shell material urea-formaldehyde prepolymer；
The preparation of step 2, core：Organic phase change material and reactive hydrophobic compound are stirred at 30~70 DEG C
It is even, obtain core；Wherein, the mass percentage of organic phase change material be 80~95wt%, reactive hydrophobic compound quality
Percentage composition is 5~20wt%；
The preparation of step 3, microcapsules：By urea-formaldehyde prepolymer aqueous solution that step 1 obtains and contain mass percent
The aqueous solution that concentration is 0.5~3% surfactant and mass percent concentration is 0.1~1% polyphenol example 1 in mass ratio:5
~1:15 are mixed with water phase, and the step 2 of 0.05~0.2 times of water phase quality is equivalent to addition after acid adjusting water phase pH to 1~3
The liquid core being prepared, and 5~20min is stirred at 20~60 DEG C with the speed of 300~1500rpm, reduce stirring speed
Degree reacts 10~25min to 200~1000rmp, further reduces mixing speed to 100~300rpm the reaction was continued 30min, so
After be warming up to 50~70 DEG C reaction 0.5~5h, products therefrom successively through deionized water, mass percent concentration be 5% ethyl alcohol
After aqueous solution washs 3~5 times, 36~60h is dried in filtering at room temperature；It is super-hydrophobic micro- to obtain phase-change material of the present invention
Capsule.
Further, alkali described in step 1 is any one in sodium hydroxide, potassium hydroxide, triethanolamine, sodium carbonate etc.
Kind；Surfactant described in step 3 is ethylene maleic acid anhydride copolymer, styrene-maleic anhydride copolymer, dodecyl
Benzene sulfonic acid sodium salt, lauryl sodium sulfate, sorbitan fatty acid ester, alkylphenol polyoxyethylene ether compound, gelatin, Arab
At least one of glue etc.；Polyphenol described in step 3 for resorcinol, catechol, dopamine, hydroquinone, 1,2,3,-thrihydroxy-benzene,
At least one of phloroglucin, epigallocatechin, Epigallo-catechin gallate (EGCG), tannic acid etc.；In step 3
The acid is any one in citric acid, acetic acid, formic acid, hydrochloric acid, nitric acid, sulfuric acid etc..
Further, organic phase change material described in step 2 is with general formula CnH2n+2The n-alkane that (n=12~32) represent
Class compound, with general formula CnH2n+1X (n=12~32) represent halogenated N-alkanes hydrocarbon compound and with general formula CmH2m+ 1COOCH2CpH2p+1It is at least one kind of in the aliphatic ester that (m=10~20, p=4~10) represent；Reactivity is hydrophobic described in step 2
Compound is with general formula OCN (CH2)kThe diisocyanate linear paraffin class compound of NCO (k=4~12) expressions, 1H, 1H, 2H,
2H- perfluoro capryls triethoxysilane, 1H, 1H, 2H, 2H- perfluoro decyls triethoxysilane, cyanoacrylate and its derivative
It is at least one kind of in object.The cyanoacrylate and its derivative are Methyl 2-cyanoacrylate, cyanacrylate, cyano
Butyl acrylate, octyl 2-cyanoacrylate etc..
Beneficial effects of the present invention are：
1st, the super-hydrophobic microcapsules of phase-change material provided by the invention, size and microstructure are adjustable, and core content is high.
2nd, the super-hydrophobic microcapsules of phase-change material provided by the invention, high temperature resistance is notable, the phase transformation material after cladding
Material has excellent thermal stability.
3rd, the super-hydrophobic microcapsules of phase-change material provided by the invention have prominent super-hydrophobicity, and its super-hydrophobicity
Storage stability and excellent heat stability.
4th, the super-hydrophobic microcapsules of phase-change material provided by the invention, cladding phase-change material have excellent thermmal storage and
Releasability, and degree of supercooling is relatively low.
5th, the super-hydrophobic microcapsules of phase-change material provided by the invention, its preparation method is simple, it is easily-controllable, efficient, be easy to advise greatly
Mould produces, raw materials used cheap and easy to get, environmentally friendly, is with a wide range of applications in fields such as energy-saving and environmental protection.
Description of the drawings
Fig. 1 is scanning electron microscopy of the obtained super-hydrophobic microcapsules of phase-change material of embodiment 1 under different amplification
Mirror (SEM) figure；Wherein, a is the SEM figures of 500 times of lower super-hydrophobic microcapsules of phase-change material of amplification, and b is 10000 times of lower phase transformations of amplification
The SEM figures of the super-hydrophobic surface of microcapsule of material, Fig. 1 c and Fig. 1 d are respectively the phase transformation material for amplifying and being ruptured under 1000 times and 10000 times
Expect the SEM figures of super-hydrophobic microcapsules；
Fig. 2 be embodiment 1 obtain the super-hydrophobic microcapsules of phase-change material, microcapsule shell, pure octadecane phase-change material is in nitrogen
Atmosphere enclose in thermogravimetric curve, heating rate be 10 DEG C/min；
Fig. 3 be the obtained super-hydrophobic microcapsules of phase-change material of embodiment 1 after different condition is handled its surface to the quiet of water
State contact angle schematic diagram；Fig. 3 a are static contact angle schematic diagram of the initial super-hydrophobic surface of microcapsule of phase-change material to water, are schemed
3b is that the super-hydrophobic surface of microcapsule of phase-change material shows the static contact angle of water after being preserved 80 days in glass container at room temperature
Be intended to, Fig. 3 c for the initial super-hydrophobic microcapsules of phase-change material under nitrogen atmosphere 250 DEG C of heating 30min postcoolings to after room temperature,
Its surface is to the static contact angle schematic diagram of water；
Fig. 4 be embodiment 1 obtain the super-hydrophobic microcapsules of phase-change material, microcapsule shell, pure octadecane phase-change material is through difference
Suction exotherm after the elimination thermal history that scanning calorimeter instrument (DSC) measures, temperature rate is 10 DEG C/min.
Specific embodiment
Embodiment 1
A kind of preparation method of the super-hydrophobic microcapsules of phase-change material, comprises the following steps：
The preparation of step 1, shell material prepolymer：2.5g urea and 6.33g mass percent concentrations is water-soluble for 37% formaldehyde
Liquid mixes, and adjusts its pH to 8 with 1mol/L sodium hydrate aqueous solutions, 1h is stirred to react at 70 DEG C, obtain colorless and transparent liquid
Body is the aqueous solution of shell material urea-formaldehyde prepolymer；Urea and the quality that mass percent concentration is 37% formalin
Than for 1：2.532；
The preparation of step 2, core：By 9g octadecanes and 1g hexamethylene diisocyanates, heating stirring mixes at 50 DEG C
30min obtains core to homogeneous transparent；The mass ratio of octadecane and hexamethylene diisocyanate is 9：1；
The preparation of step 3, microcapsules：Whole urea-formaldehyde prepolymer aqueous solutions that step 1 is obtained contain matter with 75mL
Amount percent concentration is 0.55% ethylene maleic acid anhydride copolymer and mass percent concentration is the water-soluble of 0.35% resorcinol
Liquid is mixed with water phase, after adjusting water phase pH to 1.5 with aqueous citric acid solution, whole liquid cores that a dropping step 2 is prepared
Material, and 15min is stirred at 40 DEG C with the speed of 800rpm, it reduces mixing speed and reacts 15min to 400rmp, further reduce
Mixing speed then raises temperature to 55 DEG C of reaction 1h, is cooled to room temperature, products therefrom passes through successively to 200rpm the reaction was continued 30min
After deionized water, the ethanol water that mass percent concentration is 5% wash 3~5 times, 48h is dried in filtering at room temperature；
To the super-hydrophobic microcapsules of phase-change material of the present invention.
The appearance for the super-hydrophobic microcapsules of phase-change material that the present embodiment obtains is the particle of white fluffy.Fig. 1 is embodiment 1
Scanning electron microscope (SEM) figure of the obtained super-hydrophobic microcapsules of phase-change material under different amplification；As shown in Figure 1,
The microcapsules are spherical in shape, and a diameter of 144.3 ± 24.2 μm, surface forms micro-nano by the particle of 317.0 ± 58.9nm of diameter
Multilevel hierarchy, and with significant nucleocapsid structure, the octadecane of visible solid state in core, shell thickness for 266.8 ±
60.7nm。
The super-hydrophobic microcapsules of phase-change material that the present embodiment obtains measure its thermal stability through thermogravimetric analysis, as shown in Figure 2.
Wherein, pure octadecane phase-change material is purchase gained, and microcapsule shell obtains for the microcapsules separating treatment that the present embodiment obtains.
Temperature during its thermal weight loss 5% of microcapsules that the present embodiment obtains is 163 DEG C, the temperature during thermal weight loss 5% of purer octadecane
(135 DEG C) are 28 DEG C high.Further, the temperature corresponding to its maximum heat weight loss rate of the microcapsules of the present embodiment is respectively 244
DEG C and 349 DEG C, (204 DEG C) of temperature corresponding to the maximum heat weight loss rate of purer octadecane is 40 DEG C and 105 DEG C high respectively.This
Outside, the phase-change material mass percentage that the microcapsules of the present embodiment are measured through thermogravimetric analysis is 83.8%.The above results show
The phase-change material of microcapsule coated has excellent stability and high content.
Water droplet is in subsphaeroidal in surface of microcapsule manufactured in the present embodiment, and the present embodiment is measured by contact angle tester
Microcapsules are in air 165.1 ± 0.8 ° (as shown in Figure 3a) to the static contact angle of 5 μ L water, and it is excellent to show that microcapsules have
Super-hydrophobicity.Further, its surface is to 5 μ L after the microcapsules of the present embodiment preserve 80 days in glass container at room temperature
The static contact angle of water is 165 ± 0.7 ° (as shown in Figure 3b), shows that microcapsules have sufficiently stable super-hydrophobicity.This implementation
250 DEG C of heating 30min postcoolings are to after room temperature in a nitrogen atmosphere for the microcapsules of example, and surface is to the static contact angle of 5 μ L water
For 167.4 ± 0.3 ° (as shown in Figure 3c), show that the super-hydrophobic of microcapsules has excellent thermal stability.
The super-hydrophobic microcapsules of phase-change material that the present embodiment obtains measure its song of suction heat release after eliminating thermal history through DSC
Line, as shown in Figure 4.Wherein, pure octadecane phase-change material is purchase gained, and microcapsule shell divides for the microcapsules that the present embodiment obtains
It is obtained from processing.As shown in Figure 4, its endothermic temperature of the microcapsules of the present embodiment (Tm) 32.1 DEG C, melting enthalpy (Δ Hm)
173.6J/g, exothermic temperature (Tc) 20.2 DEG C, crystallization heat content (Δ Hc) 172.4J/g, close to the T of pure octadecanem(30.5℃)、Δ
Hm(217.4J/g)、Tc(23.2℃)、ΔHc(217.1)J/g.In addition, its degree of supercooling of the microcapsules of the present embodiment (Δ Ts) be
2.4 DEG C, the Δ T with pure octadecanes(2.4 DEG C) are consistent.The above results show to have by the phase-change material of microcapsule coated excellent
Different thermmal storage and releasability, and degree of supercooling is relatively low.
Embodiment 2
A kind of preparation method of the super-hydrophobic microcapsules of phase-change material, comprises the following steps：
The preparation of step 1, shell material prepolymer：2.5g urea and 6.33g mass percent concentrations is water-soluble for 37% formaldehyde
Liquid mixes, and adjusts its pH to 8 with 1mol/L sodium hydrate aqueous solutions, 1h is stirred to react at 70 DEG C, obtain colorless and transparent liquid
Body is the aqueous solution of shell material urea-formaldehyde prepolymer；Urea and the quality that mass percent concentration is 37% formalin
Than for 1：2.532；
The preparation of step 2, core：By 9g octadecanes and 1g hexamethylene diisocyanates, heating stirring mixes at 50 DEG C
30min obtains core to homogeneous transparent；The mass ratio of octadecane and hexamethylene diisocyanate is 9：1；
The preparation of step 3, microcapsules：Whole urea-formaldehyde prepolymer aqueous solutions that step 1 is obtained contain matter with 75mL
Amount percent concentration is 0.55% ethylene maleic acid anhydride copolymer and mass percent concentration is the water-soluble of 0.35% resorcinol
Liquid is mixed with water phase, after adjusting water phase pH to 1.5 with aqueous citric acid solution, whole liquid cores that a dropping step 2 is prepared
Material, and 15min is stirred at 40 DEG C with the speed of 900rpm, it reduces mixing speed and reacts 15min to 450rmp, further reduce
Mixing speed then raises temperature to 55 DEG C of reaction 1h, is cooled to room temperature, products therefrom passes through successively to 200rpm the reaction was continued 30min
After deionized water, the ethanol water that mass percent concentration is 5% wash 3~5 times, 48h is dried in filtering at room temperature；
To the super-hydrophobic microcapsules of phase-change material of the present invention.
Its appearance of the present embodiment obtains super-hydrophobic microcapsules of phase-change material is the particle of white fluffy.SEM the result shows that
The microcapsules are spherical in shape, and a diameter of 79.8 ± 16.6 μm, surface forms micro-nano by the particle of 218.0 ± 65.9nm of diameter
Multilevel hierarchy, and with significant nucleocapsid structure, the octadecane of visible solid state in core, shell thickness for 143.9 ±
30.0nm。
The super-hydrophobic microcapsules of phase-change material that the present embodiment obtains measure its thermal stability through thermogravimetric analysis：The present embodiment obtains
Temperature during its thermal weight loss 5% of microcapsules arrived is 163 DEG C, and the temperature (135 DEG C) during the thermal weight loss 5% of purer octadecane is high by 28
℃.Further, the temperature corresponding to its maximum heat weight loss rate of the microcapsules that the present embodiment obtains is respectively 243 DEG C and 345
DEG C, (204 DEG C) of temperature corresponding to the maximum heat weight loss rate of purer octadecane is 39 DEG C and 101 DEG C high respectively.In addition, through thermogravimetric
The phase-change material mass percentage that analysis measures the microcapsules of the present embodiment is 80.4%.The above results show microcapsule coated
Phase-change material have excellent stability and high content.
Water droplet is in subsphaeroidal in the surface of microcapsule of the present embodiment, and micro- glue of the present embodiment is measured by contact angle tester
Capsule is in air 163.5 ± 0.7 ° to the static contact angle of 5 μ L water, shows that microcapsules have excellent super-hydrophobicity.Into one
With walking, its surface is to the static contact angle of 5 μ L water after the microcapsules of the present embodiment preserve 80 days in glass container at room temperature
For 163.1 ± 0.7 °, show that microcapsules have sufficiently stable super-hydrophobicity.In addition, the microcapsules of the present embodiment are in blanket of nitrogen
For lower 250 DEG C of heating 30min postcoolings to after room temperature, surface is 166.1 ± 0.7 ° to the static contact angle of 5 μ L water, is shown micro-
The super-hydrophobic of capsule has excellent thermal stability.
The super-hydrophobic microcapsules of phase-change material that the present embodiment obtains measure its song of suction heat release after eliminating thermal history through DSC
Line.Its T of the microcapsules of the present embodimentmFor 31.3 DEG C, Δ HmFor 184.5J/g, TcFor 21 DEG C, Δ HcFor 184.2J/g, close to pure
The T of octadecanem(30.5℃)、ΔHm(217.4J/g)、Tc(23.2℃)、ΔHc(217.1)J/g.In addition, the present embodiment is micro-
The Δ T of capsulesFor 2.3 DEG C, the Δ T with pure octadecanes(2.4 DEG C) are basically identical.The above results show through microcapsule coated
Phase-change material has excellent thermmal storage and releasability, and degree of supercooling is relatively low.
Embodiment 3
A kind of preparation method of the super-hydrophobic microcapsules of phase-change material, comprises the following steps：
The preparation of step 1, shell material prepolymer：2.5g urea and 6.33g mass percent concentrations is water-soluble for 37% formaldehyde
Liquid mixes, and adjusts its pH to 8 with 1mol/L sodium hydrate aqueous solutions, 1h is stirred to react at 70 DEG C, obtain colorless and transparent liquid
Body is the aqueous solution of shell material urea-formaldehyde prepolymer；Urea and the quality that mass percent concentration is 37% formalin
Than for 1：2.532；
The preparation of step 2, core：By 9g octadecanes and 1g hexamethylene diisocyanates, heating stirring mixes at 50 DEG C
30min obtains core to homogeneous transparent；The mass ratio of octadecane and hexamethylene diisocyanate is 9：1；
The preparation of step 3, microcapsules：Whole urea-formaldehyde prepolymer aqueous solutions that step 1 is obtained have quality with 75mL
The aqueous solution that percent concentration is 0.55% ethylene maleic acid anhydride copolymer and mass percent concentration is 0.35% resorcinol
Water phase is mixed with, after adjusting water phase pH to 1.5 with aqueous citric acid solution, whole liquid cores that a dropping step 2 is prepared,
And 15min is stirred at 40 DEG C with the speed of 700rpm, it reduces mixing speed and reacts 15min to 350rmp, further reduce and stir
Speed is mixed to 200rpm the reaction was continued 30min, 55 DEG C of reaction 1h is then raised temperature to, is cooled to room temperature, products therefrom is successively through going
After ionized water, the ethanol water that mass percent concentration is 5% wash 3~5 times, 48h is dried in filtering at room temperature；It obtains
The super-hydrophobic microcapsules of phase-change material of the present invention.
Its appearance of the present embodiment obtains super-hydrophobic microcapsules of phase-change material is the particle of white fluffy.The result table of SEM
The bright microcapsules are spherical in shape, a diameter of 204.9 ± 28.8 μm, surface by the particle of 477.1 ± 106.3nm of diameter form it is micro--
The multilevel hierarchy of nanometer, and with significant nucleocapsid structure, the octadecane of visible solid state in core, shell thickness for 402.1 ±
65.4nm。
The super-hydrophobic microcapsules of phase-change material that the present embodiment obtains measure its thermal stability through thermogravimetric analysis.The present embodiment
Temperature during its thermal weight loss 5% of microcapsules is 163 DEG C, and the temperature (135 DEG C) during the thermal weight loss 5% of purer octadecane is 28 DEG C high.
Further, the temperature corresponding to its maximum heat weight loss rate of the microcapsules of the present embodiment is respectively 241 DEG C and 344 DEG C, purer
(204 DEG C) of temperature corresponding to the maximum heat weight loss rate of octadecane is 37 DEG C and 100 DEG C high respectively.In addition, it is surveyed through thermogravimetric analysis
The phase-change material mass percentage for determining the microcapsules of the present embodiment is 88.7%.The above results show the phase transformation of microcapsule coated
Material has excellent stability and high content.
Water droplet is in subsphaeroidal in the surface of microcapsule of the present embodiment, and micro- glue of the present embodiment is measured by contact angle tester
Capsule is in air 166.2 ± 0.3 ° to the static contact angle of 5 μ L water, shows that microcapsules have excellent super-hydrophobicity.Into one
Step, its surface is to the static contact angle of 5 μ L water after the microcapsules of the present embodiment preserve 80 days in glass container at room temperature
For 166.1 ± 0.3 °, show that microcapsules have sufficiently stable super-hydrophobicity.In addition, the microcapsules of the present embodiment are in blanket of nitrogen
Lower 250 DEG C of heating 30min postcoolings are 167.7 ± 0.5 ° to the static contact angle of 5 μ L water to its surface of room temperature, show microcapsules
It is super-hydrophobic have excellent thermal stability.
The super-hydrophobic microcapsules of phase-change material that the present embodiment obtains measure its song of suction heat release after eliminating thermal history through DSC
Line.Its T of the microcapsules of the present embodimentmFor 30.8 DEG C, Δ HmFor 175.2J/g, TcFor 20.3 DEG C, Δ HcFor 175J/g, close to pure
The T of octadecanem(30.5℃)、ΔHm(217.4J/g)、Tc(23.2℃)、ΔHc(217.1)J/g.In addition, the present embodiment is micro-
The Δ T of capsulesFor 2.5 DEG C, the Δ T with pure octadecanes(2.4 DEG C) are basically identical.The above results show through microcapsule coated
Phase-change material has excellent thermmal storage and releasability, and degree of supercooling is relatively low.
Embodiment 4
A kind of preparation method of the super-hydrophobic microcapsules of phase-change material, comprises the following steps：
The preparation of step 1, shell material prepolymer：2.5g urea and 6.33g mass percent concentrations is water-soluble for 37% formaldehyde
Liquid mixes, and adjusts its pH to 8 with 1mol/L sodium hydrate aqueous solutions, 1h is stirred to react at 70 DEG C, obtain colorless and transparent liquid
Body is the aqueous solution of shell material urea-formaldehyde prepolymer；Urea and the quality that mass percent concentration is 37% formalin
Than for 1：2.532；
The preparation of step 2, core：By 9g octadecanes and 1g hexamethylene diisocyanates, heating stirring mixes at 50 DEG C
30min obtains core to homogeneous transparent；The mass ratio of octadecane and hexamethylene diisocyanate is 9：1；
The preparation of step 3, microcapsules：Whole urea-formaldehyde prepolymer aqueous solutions that step 1 is obtained contain matter with 75mL
Amount percent concentration is 0.55% ethylene maleic acid anhydride copolymer and mass percent concentration is the water-soluble of 0.35% resorcinol
Liquid is mixed with water phase, after adjusting water phase pH to 1.5 with aqueous citric acid solution, whole liquid cores that a dropping step 2 is prepared
Material, and 15min is stirred at 40 DEG C with the speed of 1000rpm, it reduces mixing speed and reacts 15min to 500rmp, further drop
Low mixing speed then raises temperature to 55 DEG C of reaction 1h, is cooled to room temperature, products therefrom is successively to 200rpm the reaction was continued 30min
After deionized water, the ethanol water that mass percent concentration is 5% wash 3~5 times, 48h is dried in filtering at room temperature；
Obtain the super-hydrophobic microcapsules of phase-change material of the present invention.
Its appearance of the present embodiment obtains super-hydrophobic microcapsules of phase-change material is the particle of white fluffy.The result table of SEM
The bright microcapsules are spherical in shape, a diameter of 48.5 ± 10.3 μm, surface by the particle of 183.8 ± 44.6nm of diameter form it is micro--receive
The multilevel hierarchy of rice, and with significant nucleocapsid structure, the octadecane of visible solid state in core, shell thickness for 126.2 ±
15.7nm。
The super-hydrophobic microcapsules of phase-change material that the present embodiment obtains measure its thermal stability through thermogravimetric analysis.It is the result shows that micro-
The phase-change material of capsule cladding has excellent stability and high content.
Water droplet is in subsphaeroidal in the surface of microcapsule of the present embodiment, and micro- glue of the present embodiment is measured by contact angle tester
Capsule is in air 159.3 ± 0.5 ° to the static contact angle of 5 μ L water, shows that microcapsules have excellent super-hydrophobicity.Into one
Step, its surface is to the static contact angle of 5 μ L water after the microcapsules of the present embodiment preserve 80 days in glass container at room temperature
For 158.8 ± 0.6 °, show that microcapsules have sufficiently stable super-hydrophobicity.In addition, the microcapsules of the present embodiment are in blanket of nitrogen
Lower 250 DEG C of heating 30min postcoolings are 163.7 ± 0.4 ° to the static contact angle of 5 μ L water to its surface of room temperature, show microcapsules
It is super-hydrophobic have excellent thermal stability.
The super-hydrophobic microcapsules of phase-change material that the present embodiment obtains measure its song of suction heat release after eliminating thermal history through DSC
Line.The result shows that there is excellent thermmal storage and releasability by the phase-change material of microcapsule coated, and degree of supercooling is relatively low.
Claims (5)
1. a kind of super-hydrophobic microcapsules of phase-change material, the softgel shell including capsule-core and the micro-nano multilevel hierarchy of outer surface band, by quality
Percentage calculation, the content of capsule-core are 60~90wt%, the content of the softgel shell of the micro-nano multilevel hierarchy of outer surface band for 10~
40wt%；The microcapsules average diameter be 10~1000 μm, softgel shell average thickness be 100~500nm, softgel shell outer surface particle
Average diameter is 150~650nm；
The ingredient and mass percentage of the capsule-core be：80~95wt% of organic phase change material, reactive hydrophobic compound 5~
20wt%；The organic phase change material is with general formula CnH2n+2The N-alkanes hydrocarbon compound of expression, with general formula CnH2n+1X is represented
Halogenated N-alkanes hydrocarbon compound and with general formula CmH2m+1COOCH2CpH2p+1It is at least one kind of in the aliphatic ester of expression, wherein,
M=10~20, n=12~32, p=4~10；The reactive hydrophobic compound is with general formula OCN (CH2)kThe two of NCO expressions
Isocyanates linear paraffin class compound, 1H, 1H, 2H, 2H- perfluoro capryls triethoxysilane, 1H, 1H, 2H, the 2H- perfluor last of the ten Heavenly stems
It is at least one kind of in ethyl triethoxy silicane alkane, cyanoacrylate and its derivative, wherein, k=4~12；
The softgel shell is Lauxite, is obtained by the reaction by formaldehyde and urea polycondensation, wherein, the mass ratio of formaldehyde and urea is 1:
0.37~1:2.22；
The surface of the super-hydrophobic microcapsules of phase-change material and the static contact angle of water are 150~170 °.
2. the preparation method of the super-hydrophobic microcapsules of phase-change material as described in claim 1, comprises the following steps：
The preparation of step 1, shell material prepolymer：By the formalin in mass ratio 1 that urea and mass percentage concentration are 37%:1~
1:6 mixing adjust pH to 7~12 with alkali, are stirred to react 0.5~2h at 60~80 DEG C, obtain colorless and transparent liquid, are
The aqueous solution of shell material urea-formaldehyde prepolymer；
The preparation of step 2, core：Organic phase change material and reactive hydrophobic compound at 30~70 DEG C are stirred evenly, obtained
To core；Wherein, the mass percentage of organic phase change material is 80~95wt%, and reactive hydrophobic compound quality percentage contains
It measures as 5~20wt%；
The preparation of step 3, microcapsules：By urea-formaldehyde prepolymer aqueous solution that step 1 obtains and contain mass percent concentration
For the aqueous solution example 1 in mass ratio that 0.5~3% surfactant and mass percent concentration are 0.1~1% polyphenol:5~1:
15 are mixed with water phase, prepared by the step 2 that 0.05~0.2 times of water phase quality is equivalent to addition after acid adjusting water phase pH to 1~3
Obtained liquid core, and 5~20min is stirred at 20~60 DEG C with the speed of 300~1500rpm, reduce mixing speed extremely
200~1000rmp reacts 10~25min, further reduces mixing speed to 100~300rpm the reaction was continued 30min, Ran Housheng
Temperature to 50~70 DEG C reaction 0.5~5h, products therefrom successively through deionized water, mass percent concentration be 5% ethyl alcohol it is water-soluble
After liquid washs 3~5 times, 36~60h is dried in filtering at room temperature；Obtain the super-hydrophobic microcapsules of the phase-change material.
3. the preparation method of the super-hydrophobic microcapsules of phase-change material according to claim 2, which is characterized in that described in step 1
Alkali is any one in sodium hydroxide, potassium hydroxide, triethanolamine, sodium carbonate.
4. the preparation method of the super-hydrophobic microcapsules of phase-change material according to claim 2, which is characterized in that institute in step 3
Surfactant is stated as ethylene maleic acid anhydride copolymer, styrene-maleic anhydride copolymer, neopelex, 12
At least one in sodium alkyl sulfate, sorbitan fatty acid ester, alkylphenol polyoxyethylene ether compound, gelatin, Arabic gum
Kind.
5. the preparation method of the super-hydrophobic microcapsules of phase-change material according to claim 2, which is characterized in that institute in step 3
Polyphenol is stated as resorcinol, catechol, dopamine, hydroquinone, 1,2,3,-thrihydroxy-benzene, phloroglucin, epigallocatechin, table
At least one of nutgall catechin gallic acid ester, tannic acid；Acid described in step 3 is citric acid, acetic acid, formic acid, salt
Any one in acid, nitric acid, sulfuric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510379883.6A CN104927779B (en) | 2015-07-01 | 2015-07-01 | A kind of super-hydrophobic microcapsules of phase-change material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510379883.6A CN104927779B (en) | 2015-07-01 | 2015-07-01 | A kind of super-hydrophobic microcapsules of phase-change material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104927779A CN104927779A (en) | 2015-09-23 |
| CN104927779B true CN104927779B (en) | 2018-05-18 |
Family
ID=54115214
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510379883.6A Expired - Fee Related CN104927779B (en) | 2015-07-01 | 2015-07-01 | A kind of super-hydrophobic microcapsules of phase-change material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104927779B (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105233768B (en) * | 2015-09-29 | 2017-07-21 | 浙江理工大学 | A kind of method and product for preparing poly-dopamine silicon substrate complex microsphere |
| CN105838334A (en) * | 2016-04-27 | 2016-08-10 | 江苏箭鹿毛纺股份有限公司 | Preparing method for heat storing and temperature adjusting phase change microcapsules |
| CN106380112B (en) * | 2016-08-30 | 2019-01-04 | 长安大学 | Hydrophobic microcapsules are in the application for improving agent on crack resistance of concrete permeability |
| CN107815877A (en) * | 2017-10-16 | 2018-03-20 | 安踏（中国）有限公司 | A kind of method for sorting of floride-free water-proof finish liquid and floride-free waterproof fabric |
| CN108485608B (en) * | 2018-02-26 | 2020-08-28 | 恒天海龙（潍坊）新材料有限责任公司 | Method for reducing supercooling degree of normal alkane energy storage material microcapsule |
| CN110559957B (en) * | 2019-07-24 | 2020-10-27 | 广州市香港科大霍英东研究院 | Phase change microcapsule with high blending fluidity and high phase change latent heat and preparation method thereof |
| CN110627402B (en) * | 2019-09-29 | 2021-11-19 | 北京工业大学 | Cement-based composite phase-change heat-storage temperature-regulating material based on mixed ester phase-change microcapsules |
| CN111117320A (en) * | 2019-12-12 | 2020-05-08 | 山东科技大学 | Fe2+/Fe3+Self-repairing agent for induced self-repairing nanotube and preparation method and application thereof |
| CN111534190B (en) * | 2020-03-12 | 2022-01-25 | 复旦大学 | Double-response self-repairing super-hydrophobic coating material and preparation method thereof |
| CN111607300A (en) * | 2020-06-21 | 2020-09-01 | 武汉露能科技有限公司 | Durable anti-icing low-surface-energy material for wind power blade and preparation method thereof |
| CN113831758A (en) * | 2021-09-09 | 2021-12-24 | 广东职业技术学院 | Thermochromic microcapsule dye and preparation method and application thereof |
| CN113617306A (en) * | 2021-09-13 | 2021-11-09 | 武汉中科先进技术研究院有限公司 | Preparation method of high-thermal-conductivity super-hydrophobic phase change microcapsule |
| CN114199058B (en) * | 2021-11-29 | 2024-02-20 | 南方科技大学 | Thermochemical energy storage microcapsule and preparation method thereof |
| CN116814224B (en) * | 2023-06-29 | 2024-03-08 | 合肥芯能相变新材料科技有限公司 | Low-supercooling-degree phase-change microcapsule and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101310852A (en) * | 2008-04-23 | 2008-11-26 | 东华大学 | Preparation method of temperature sensitive type microcapsule coated by hydrophobic core material |
| CN101376800A (en) * | 2008-10-07 | 2009-03-04 | 山东省科学院新材料研究所 | High temperature resistant type phase-change material micro-capsule and preparation thereof |
| CN103146197A (en) * | 2013-03-11 | 2013-06-12 | 深圳大学 | Method for preparing lyophobic heat conduction material with micro-nano core-shell structure |
| WO2013103595A1 (en) * | 2012-01-03 | 2013-07-11 | Phase Change Energy Solutions, Inc. | Compositions comprising latent heat storage materials and methods of making the same |
-
2015
- 2015-07-01 CN CN201510379883.6A patent/CN104927779B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101310852A (en) * | 2008-04-23 | 2008-11-26 | 东华大学 | Preparation method of temperature sensitive type microcapsule coated by hydrophobic core material |
| CN101376800A (en) * | 2008-10-07 | 2009-03-04 | 山东省科学院新材料研究所 | High temperature resistant type phase-change material micro-capsule and preparation thereof |
| WO2013103595A1 (en) * | 2012-01-03 | 2013-07-11 | Phase Change Energy Solutions, Inc. | Compositions comprising latent heat storage materials and methods of making the same |
| CN103146197A (en) * | 2013-03-11 | 2013-06-12 | 深圳大学 | Method for preparing lyophobic heat conduction material with micro-nano core-shell structure |
Non-Patent Citations (1)
| Title |
|---|
| A Versatile Approach towards Multifunctional Robust Microcapsules with Tunable, Restorable, and Solvent-Proof Superhydrophobicity for Self-Healing and Self-Cleaning Coatings;Gang Wu等;《ADVANCED FUNCTIONAL MATERIALS》;20141109;第24卷(第43期);第6752页左栏倒数第16-10行、右栏第7-27行，第6754页右栏倒数第7-1行，第6755页左栏第1-2行，第6759页右栏倒数第32-3行，图1，图2，表1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104927779A (en) | 2015-09-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104927779B (en) | A kind of super-hydrophobic microcapsules of phase-change material and preparation method thereof | |
| Yuan et al. | Preparation and characterization of poly (urea-formaldehyde) microcapsules filled with epoxy resins | |
| He et al. | Facile flexible reversible thermochromic membranes based on micro/nanoencapsulated phase change materials for wearable temperature sensor | |
| Yuan et al. | Preparation and properties of poly (urea–formaldehyde) microcapsules filled with epoxy resins | |
| CN108425248B (en) | Preparation method of nano temperature-controlled slow-release aromatic microcapsule | |
| Yuan et al. | Thermal stability of microencapsulated epoxy resins with poly (urea–formaldehyde) | |
| CN105399889A (en) | Hybridization wall material nano-capsules made of phase change energy storage material and preparation method of hybridization wall material nano-capsules | |
| CN107159070A (en) | Self-repairing microcapsule and preparation method thereof, coating, coating and epoxy resin composite material | |
| WO2023039972A1 (en) | Dual-layer urea-formaldehyde shell phase change microcapsule, and preparation method therefor and application thereof | |
| CN102876297B (en) | A kind of low condensate depression phase-change material micro-capsule and preparation method thereof | |
| CN102728288A (en) | Method for enhancing capsule wall toughness of self-repairing microcapsules, and self-repairing microcapsules prepared by the same | |
| CN112473581B (en) | Preparation method of organic-inorganic double-layer composite wall material magnetic phase change microcapsule | |
| CN104892851B (en) | A kind of preparation method of polymer hollow particles | |
| CN111059949B (en) | Novel reinforced composite phase-change fluid and preparation method and application thereof | |
| CN106732217B (en) | A kind of preparation method of polymer microballoon | |
| CN114452907B (en) | Microcapsule for temperature control and self-repairing of well cementation cement sheath and preparation method thereof | |
| Geng et al. | Influences of PVA modification on performance of microencapsulated reversible thermochromic phase change materials for energy storage application | |
| An et al. | Synthesis and characterization of robust SiO2-phase change materials (PCM) microcapsules | |
| CN104437284A (en) | Preparation method of phase change microcapsule | |
| CN102850915A (en) | Water light cured top coating and preparation method thereof | |
| CN105944633B (en) | A kind of preparation method of mould-proof-type casein base SiO 2 hybrid microcapsules | |
| CN112280353B (en) | Antibacterial and ultraviolet-resistant thermochromic wax color paint and preparation method thereof | |
| CN106085231A (en) | A kind of thermoprint aqueous mould release and preparation method thereof | |
| WO2018040251A1 (en) | Photoinitiated repairing microcapsule preparation method | |
| CN107715811B (en) | Self-repairing microcapsule for aqueous coating on surface of wood material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180518 Termination date: 20210701 |