CN102391839B - Supercooling phase change-inhibiting alkane microcapsule and preparation and application thereof - Google Patents
Supercooling phase change-inhibiting alkane microcapsule and preparation and application thereof Download PDFInfo
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- CN102391839B CN102391839B CN 201110235098 CN201110235098A CN102391839B CN 102391839 B CN102391839 B CN 102391839B CN 201110235098 CN201110235098 CN 201110235098 CN 201110235098 A CN201110235098 A CN 201110235098A CN 102391839 B CN102391839 B CN 102391839B
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- 239000003094 microcapsule Substances 0.000 title claims abstract description 78
- 150000001335 aliphatic alkanes Chemical class 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000004781 supercooling Methods 0.000 title abstract description 5
- 230000002401 inhibitory effect Effects 0.000 title abstract 2
- 239000000839 emulsion Substances 0.000 claims abstract description 33
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 13
- 239000004640 Melamine resin Substances 0.000 claims abstract description 9
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 230000005764 inhibitory process Effects 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 51
- 238000003756 stirring Methods 0.000 claims description 43
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 229920000147 Styrene maleic anhydride Polymers 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 19
- 229940094933 n-dodecane Drugs 0.000 claims description 19
- 230000007704 transition Effects 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 18
- 230000009466 transformation Effects 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 10
- ZYURHZPYMFLWSH-UHFFFAOYSA-N octacosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC ZYURHZPYMFLWSH-UHFFFAOYSA-N 0.000 claims description 10
- KUPLEGDPSCCPJI-UHFFFAOYSA-N tetracontane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC KUPLEGDPSCCPJI-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 230000001105 regulatory effect Effects 0.000 claims description 9
- HOWGUJZVBDQJKV-UHFFFAOYSA-N docosane Chemical compound CCCCCCCCCCCCCCCCCCCCCC HOWGUJZVBDQJKV-UHFFFAOYSA-N 0.000 claims description 8
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000008098 formaldehyde solution Substances 0.000 claims description 7
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 4
- 238000009413 insulation Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 abstract 4
- 239000002667 nucleating agent Substances 0.000 abstract 4
- 239000011162 core material Substances 0.000 abstract 3
- 239000011257 shell material Substances 0.000 abstract 3
- 230000002776 aggregation Effects 0.000 abstract 1
- 238000004220 aggregation Methods 0.000 abstract 1
- 238000011065 in-situ storage Methods 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- YDLYQMBWCWFRAI-UHFFFAOYSA-N hexatriacontane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC YDLYQMBWCWFRAI-UHFFFAOYSA-N 0.000 description 8
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 8
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 244000248349 Citrus limon Species 0.000 description 5
- 235000005979 Citrus limon Nutrition 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 238000005352 clarification Methods 0.000 description 5
- 239000012782 phase change material Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- YCOZIPAWZNQLMR-UHFFFAOYSA-N heptane - octane Natural products CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 4
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 4
- 239000012188 paraffin wax Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical class CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- GWVDBZWVFGFBCN-UHFFFAOYSA-N tetratriacontane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC GWVDBZWVFGFBCN-UHFFFAOYSA-N 0.000 description 2
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
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Abstract
The invention discloses a supercooling phase change-inhibiting alkane microcapsule and preparation and application thereof. The size of the alkane microcapsule is within a range from 0.1Mu m to 100Mu m, the alkane microcapsule consists of shell materials and core materials, the shell materials are melamine resin, the core materials are n-alkane phase change agent and n-alkane nucleating agent, the carbon atom number of the n-alkane phase change agent is twelve to twenty eight, and the carbon atom number of the n-alkane nucleating agent is twenty two to forty. The preparation method for the alkane microcapsule, which is disclosed by the invention, is an in-situ polymerization method, and the preparation process includes core material emulsion preparation, shell material prepolymer preparation and alkane microcapsule preparation. For the same type of alkane microcapsule, the carbon atom number of the nucleating agent is greater than the carbon atom number of the phase change agent, and the nucleating agent and the phase change agent can be formed into gel. The invention has the advantages that: the alkane microcapsule has the characteristics of supercooling phase change inhibition, smooth surface and aggregation resistance, the preparation process for the alkane microcapsule is simple, and the application range is wide.
Description
Technical field
The present invention relates to a kind of alkane microcapsule and preparation and application thereof that suppressed cold phase transformation, belong to the phase change material technology.
Background technology
Organic alkane is the phase change material that a class is used under the certain temperature environment.Organic alkane is wrapped in the microcapsule, namely obtain the alkane microcapsule.Phase-change microcapsule has obtained in fields such as aerospace, weavings using widely.But there is surfusion in the alkane microcapsule, and its condensate depression (difference between melt temperature and the Tc) diminishes with the particle diameter of microcapsule and increases (Y.Yamagishi, T.Sugeno, T.Ishige. " Anevaluation of microencapsulated PCM for use in cold energy transportation medium ", IEEE 1996,3:2077-2083), make its can not undergo phase transition, absorb in specific temperature/discharge heat of phase transformation, hindered its practical application.
US Patent No. 2004/0076826 is pointed out, be that carbonatoms is 13 to 28 n-tridecane to the phase-change microcapsule of the positive organic alkane of octacosane concerning core, the monobasic nalka alcohols or the positive alkyl amino derivative of monobasic that add relative content in the core and be organic alkane of 0.1% to 15% are made nucleator, the surfusion that can suppress microcapsule, but studies show that, add a spot of alcohol derivatives in organic alkane microcapsule core and make nucleator, though can suppress the surfusion of organic alkane microcapsule, but can make that microcapsule are easy to reunite after adding these materials, it is very coarse that the surface becomes, this may be (the Y.F.Fan that hydroxyl on the alcohol and microcapsule wall material react and cause, X.X.Zhang, X.C.Wang, J.Li, Q.B.Zhu. " Super-cooling prevention of microencapsulated phase change material ", Thermochimica Acta, 2004,413 (1-2): 1-6; Xing-Xiang Zhang, Yao-feng Fan, Xiao-ming Tao, Kit-lun Yick. " Crystallization and prevention of supercooling of microencapsulated n-alkanes ", Journal of Colloid and Interface Science, 2005,281 (2): 299-306).In addition, amino on the amino derivative also surface of the phase-change microcapsule of feasible preparation becomes very coarse, microcapsule are reunited together, be difficult to scatter, be unfavorable for the further industrialized application of microcapsule, it therefore one is that the very coarse microcapsule in surface of reuniting together are difficult to be uniformly dispersed in the big external phase of viscosity as disperse phase; It two is that the rough surface of microcapsule will be difficult to fully contact with external phase therefore.The situation that sodium-chlor is made nucleator also studied in above-mentioned article, and the surface of the microcapsule of this method preparation also is coarse and easy reunion; Make nucleator for paraffin, can not make the surface of microcapsule become coarse though in above-mentioned research, proved paraffin, microcapsule are become be easy to reunite, but because paraffin itself is mixture, the transformation temperature scope is bigger, therefore suppress also to make the transformation temperature scope of microcapsule increase when organic alkane is cold excessively, so reduced the relatively hot absorption/burst size in the fixed temperature interval of microcapsule, because each components contents of paraffin is unfixing, therefore can not quantitatively adjust the cold situation of mistake of microcapsule simultaneously.
The method of the organic alkane microcapsule of existing inhibition surfusion is not seen and is utilized the gel factor to make the phase change material nucleator, in order to the surfusion of quantitative control phase-change microcapsule, and can avoid destroying research report or the patent of invention of microcapsule pattern.
Summary of the invention
The object of the present invention is to provide a kind of alkane microcapsule and preparation and application thereof that suppressed cold phase transformation, these alkane microcapsule have and suppressed cold phase transformation, smooth surface and difficult reunion characteristics, and its preparation process is simple, and is of many uses.
For achieving the above object, the present invention is realized by following technical proposals, a kind of alkane microcapsule that suppressed cold phase transformation, it is characterized in that, these microcapsule are spherical in shape, particle diameter is 0.1 μ m～100 μ m, it is (0.05-0.5) by mass ratio: (0.95-0.5) wall material and core are formed, wherein, the wall material is melamine resin, and core is (0.999～0.95) by alkane phase transition agent and alkane nucleator by mass ratio: (0.001～0.05) and form greater than the carbonatoms of alkane phase transition agent by the carbonatoms of alkane nucleator.
Above-mentioned alkane phase transition agent is selected from a kind of or a kind of mixture among the extremely positive octacosane of n-dodecane.
What above-mentioned alkane nucleator was n-docosane to the positive tetracontane is a kind of.
Above-mentioned inhibition the preparation method of alkane microcapsule of cold phase transformation, it is characterized in that comprising following process:
1) core emulsion preparation
(1) under the stirring velocity of 50～80 ℃ of temperature and 400～1400rpm, styrene-maleic anhydride copolymer (SMA) is added in the deionized water, and be 6.5～9.5 with the pH value of NaOH solution regulator solution, obtain mass concentration and be 2～6% styrene-maleic anhydride copolymer solution;
(2) stir down, with extremely positive the octacosane a kind of or a kind of mixture wherein of alkane phase transition agent n-dodecane, with a kind of to the positive tetracontane of alkane nucleator n-docosane, be (0.999～0.95) by both by mass ratio: (0.001～0.05) and evenly mix by the carbonatoms of the alkane nucleator carbonatoms greater than the alkane phase transition agent makes the mixture of phase transition agent and nucleator;
(3) the styrene-maleic anhydride copolymer solution of the mixture of the phase transition agent that step (2) is prepared and nucleator and step (1) system, press mass ratio 1: after mix (2～10), stir 10～40min with stirring velocity 2000～20000rpm for 50 ℃～80 ℃ in temperature and obtain emulsion, and be 3.5～5.5 with the pH that citric acid is regulated this emulsion, make alkane phase-change microcapsule core emulsion;
2) wall material performed polymer preparation
Be 34～41% formaldehyde solution and deionized water by mass ratio 1 with trimeric cyanamide and massfraction: (1～3): (1～10) preparation mixed solution, the pH value of regulating mixed solution with NaOH solution is 6.5～9.5, obtains melamine resin (PMF) prepolymer solution wall material 50 ℃～80 ℃ of temperature and under stirring;
3) alkane microcapsule preparation
It is 30～60 ℃ in temperature, stirring velocity is under the condition of 1000～1400rpm, set by step 2) mass ratio of the alkane microcapsule core emulsion of the melamine resin prepolymer solution of system and step 1) system is 1: (2～10), the melamine resin prepolymer drips of solution is added in the alkane microcapsule core emulsion, drip 20～30min, keeping temperature to be 30～60 ℃ after dripping is 1000～1400rpm with stirring velocity, reaction 0.5～2h, be warming up to 70～90 ℃ with 1～6 ℃/min of temperature rise rate again, continue reaction 1～6h, stop heating and stirring then, with deionized water wash, the alkane microcapsule of the cold phase transformation that was inhibited after the drying.
The inhibition of above-mentioned or method for preparing the application of alkane microcapsule of cold phase transformation, for the preparation of thermal insulation coatings or matrix material.
The invention has the advantages that selected nucleator and phase transition agent are same compounds, nucleator and phase transition agent can dissolve each other, and can form gel with phase transition agent, so microcapsule are in forming process, pattern can not be subjected to the influence of nucleator, its smooth surface is difficult for reuniting good dispersity.This type of nucleator can suppress the surfusion of organic alkane microcapsule well.Can prepare the various alkane microcapsule of different transformation temperatures according to application requiring.The microcapsule that the present invention relates to are mixed in other macromolecular material such as Resins, epoxy, urethane, the silicone resin, make thermal insulation coatings or matrix material, make it be applied to improve fields such as thermo-efficiency, control temperature, energy storage.
Description of drawings
The inhibition of Fig. 1: embodiment 1 preparation the SEM photo of alkane microcapsule of cold phase transformation.
Fig. 2: differential scanning calorimetric (DSC) graphic representation of organic alkane phase change material.
Among the figure: a1: the temperature lowering curve of n-dodecane; B1: the temperature lowering curve of n-dodecane microcapsule; The temperature lowering curve of the n-dodecane microcapsule that contain the 3wt% n-hexatriacontane of c1: embodiment 1 preparation; A2: the heating curve of n-dodecane; B2: the heating curve of n-dodecane microcapsule; The heating curve of the n-dodecane microcapsule that contain 3% n-hexatriacontane of c2: embodiment 1 preparation.
The Tc of n-dodecane is-14.2 ℃ as seen from Figure 2, and the crystallization start temperature of n-dodecane microcapsule is-23.4 ℃, and the crystallization start temperature of the n-dodecane microcapsule that contain the gel factor that the present invention is prepared is-15.6 ℃.This shows that nucleator used in the present invention can suppress the cold phase transition phenomena of mistake of alkane microcapsule well.
Embodiment
Embodiment 1
5g SMA is dissolved in the 95mL deionized water, and regulating pH value with the NaOH solution of 1M is 8, and temperature is set at 60 ℃, is stirred to the stirring velocity of 600rpm that pressed powder dissolves fully, solution is clarified, and obtains SMA solution.Be that 37% formaldehyde solution, 20mL deionized water mix with 5g trimeric cyanamide, 8.6mL massfraction, the control temperature is 60 ℃, regulate between pH value to 8～9 with the NaOH solution of 1M, be stirred to the solution clarification with the stirring velocity of 600rpm, obtain the PMF prepolymer solution.15g n-dodecane and 0.45g n-hexatriacontane are mixed, add above-mentioned SMA solution, stir 10min 60 ℃ of stirring velocitys with 3000rpm and obtain emulsion, the stirring velocity with 1200rpm continues to stir again, lemon acid for adjusting pH with 1M is 4.6, and emulsion is cooled to 45 ℃.The PMF resin prepolymer slowly is added dropwise to emulsion, dropwises in half an hour.Speed with 2 ℃/min rises to 80 ℃ with emulsion temperature, reaction 4h.Stop heating and stirring, with deionized water wash, obtain the alkane microcapsule after the drying.
The alkane microcapsule of preparation are spheroidal, and median size is 9.6 ± 3.1 μ m, and smooth surface is not reunited.With respect to the n-dodecane microcapsule that do not add the gel factor, its condensate depression of n-dodecane microcapsule that contains the 3wt% n-hexatriacontane reduces, and its crystallization start temperature is consistent with the Tc of n-dodecane.
Embodiment 2
6g SMA is dissolved in the 95mL deionized water, and regulating pH value with 1M NaOH solution is 8, and temperature is set at 60 ℃, is stirred to the stirring velocity of 600rpm that pressed powder dissolves fully, solution is clarified, and obtains SMA solution.Be that 37% formaldehyde solution, 25mL deionized water mix with 4g trimeric cyanamide, 8mL massfraction, the control temperature is 60 ℃, regulate between pH value to 8～9 with the NaOH solution of 1M, be stirred to the solution clarification with the stirring velocity of 600rpm, obtain the PMF prepolymer solution.10g n-dodecane and 5g n-tetradecane and the positive tetratriacontane of 0.45g are mixed, add above-mentioned SMA solution, stir 15min at 55 ℃ of rotating speeds with 2700rpm and obtain emulsion, continue to stir with the rotating speed about 1300rpm again, lemon acid for adjusting pH with 1M is 4.4, and emulsion is cooled to 40 ℃.The PMF resin prepolymer slowly is added dropwise to emulsion, dropwises in half an hour.Speed with 4 ℃/min rises to 85 ℃ with emulsion temperature, reaction 3h.Stop heating and stirring, with deionized water wash, obtain the alkane microcapsule after the drying.
Embodiment 3
7g SMA is dissolved in the 100mL deionized water, and regulating pH value with 1M NaOH solution is 8, and temperature is set at 60 ℃, is stirred to the stirring velocity of 400rpm that pressed powder dissolves fully, solution is clarified, and obtains SMA solution.Be that 40% formaldehyde solution, 18mL deionized water mix with 6g trimeric cyanamide, 9mL massfraction, the control temperature is 60 ℃, regulate between pH value to 8～9 with the NaOH solution of 1M, be stirred to the solution clarification with the stirring velocity of 500rpm, obtain the PMF prepolymer solution.5g n-dodecane and 10g n-tetradecane and positive three octadecanes of 0.15g are mixed, add above-mentioned SMA solution, stir 12min at 65 ℃ of rotating speeds with 2400rpm and obtain emulsion, continue to stir with the rotating speed about 800rpm again, lemon acid for adjusting pH with 1M is 4.5, and emulsion is cooled to 45 ℃.The PMF resin prepolymer slowly is added dropwise to emulsion, dropwises in half an hour.Speed with 1 ℃/min rises to 77 ℃ with emulsion temperature, reaction 3h.Stop heating and stirring, with deionized water wash, obtain the alkane microcapsule after the drying.
Embodiment 4
8g SMA is dissolved in the 105mL deionized water, and regulating pH value with 1M NaOH solution is 8, and temperature is set at 60 ℃, is stirred to the stirring velocity of 400rpm that pressed powder dissolves fully, solution is clarified, and obtains SMA solution.Be that 40% formaldehyde solution, 28mL deionized water mix with 8g trimeric cyanamide, 12mL massfraction, the control temperature is 60 ℃, regulate between pH value to 8～9 with the NaOH solution of 1M, be stirred to the solution clarification with the stirring velocity of 800rpm, obtain the PMF prepolymer solution.5g n-tetradecane and 10g n-hexadecane and the positive tetracontane of 0.3g are mixed, add above-mentioned SMA solution, stir 10min at 60 ℃ of rotating speeds with 2500rpm and obtain emulsion, the rotating speed with 1200rpm continues to stir again, lemon acid for adjusting pH with 1M is 5, and emulsion is cooled to 55 ℃.The PMF resin prepolymer slowly is added dropwise to emulsion, dropwises in half an hour.Speed with 1 ℃/min rises to 80 ℃ with emulsion temperature, reaction 4h.Stop heating and stirring, with deionized water wash, obtain the alkane microcapsule after the drying.
Embodiment 5
5g SMA is dissolved in the 95mL deionized water, and regulating pH value with 1M NaOH solution is 8, and temperature is set at 60 ℃, is stirred to the stirring velocity of 400rpm that pressed powder dissolves fully, solution is clarified, and obtains SMA solution.Be that 40% formaldehyde solution, 23mL deionized water mix with 6g trimeric cyanamide, 10mL massfraction, the control temperature is 60 ℃, regulate between pH value to 8～9 with the NaOH solution of 1M, be stirred to the solution clarification with the stirring velocity of 800rpm, obtain the PMF prepolymer solution.2g n-tetradecane and 13g n-hexadecane and positive three octadecanes of 0.15g are mixed, add above-mentioned SMA solution, stir 10min at 60 ℃ of rotating speeds with 2600rpm and obtain emulsion, continue to stir with the rotating speed about 1500rpm again, lemon acid for adjusting pH with 1M is 4.8, and emulsion is cooled to 50 ℃.The PMF resin prepolymer slowly is added dropwise to emulsion, dropwises in half an hour.Speed with 4 ℃/min rises to 85 ℃ with emulsion temperature, reaction 5h.Stop heating and stirring, with deionized water wash, obtain the alkane microcapsule after the drying.
Prepared alkane microcapsule are mixed in other macromolecular material such as Resins, epoxy, urethane, the silicone resin, make to have microcapsule thermal insulation coatings or the matrix material that suppressed cold function.
Claims (3)
1. alkane microcapsule that suppressed cold phase transformation, it is characterized in that, these alkane microcapsule are spherical in shape, particle diameter is 0.1 μ m～100 μ m, it is (0.05-0.5) by mass ratio: (0.95-0.5) wall material and core are formed, wherein, the wall material is melamine resin, core is (0.999～0.95) by alkane phase transition agent and alkane nucleator in mass ratio: (0.001～0.05) ratio, and the carbonatoms of pressing the alkane nucleator is formed greater than the carbonatoms of alkane phase transition agent, and described alkane phase transition agent is selected from one or more mixtures among the extremely positive octacosane of n-dodecane; What described alkane nucleator was n-docosane to the positive tetracontane is a kind of.
2. one kind prepares the described method that suppressed the alkane microcapsule of cold phase transformation of claim 1, it is characterized in that comprising following process:
1) core emulsion preparation
(1) 50～80 ℃ of temperature and under stirring, styrene-maleic anhydride copolymer is added in the deionized water, and be 6.5～9.5 with the pH value of NaOH solution regulator solution, obtain mass concentration and be 2～6% styrene-maleic anhydride copolymer solution;
(2) stir down, with extremely positive octacosane one or more mixtures wherein of alkane phase transition agent n-dodecane, with a kind of to the positive tetracontane of alkane nucleator n-docosane, in both in mass ratio (0.999～0.95): (0.001～0.05) ratio and evenly mix by the carbonatoms of the alkane nucleator carbonatoms greater than the alkane phase transition agent makes the mixture of phase transition agent and nucleator;
(3) the styrene-maleic anhydride copolymer solution of the mixture of the phase transition agent that step (2) is made and nucleator and step (1) system, press mass ratio 1: after mix (2～10), stir 10～40min with stirring velocity 2000～20000rpm for 50 ℃～80 ℃ in temperature and obtain emulsion, and be 3.5～5.5 with the pH that citric acid is regulated this emulsion, make alkane phase-change microcapsule core emulsion;
2) wall material performed polymer preparation
Be 34～41% formaldehyde solution and deionized water by mass ratio 1 with trimeric cyanamide and massfraction: (1～3): (1～10) preparation mixed solution, the pH value of regulating mixed solution with NaOH solution is 6.5～9.5, obtains melamine resin prepolymer solution wall material 50 ℃～80 ℃ of temperature and under stirring;
3) alkane microcapsule preparation
It is 30～60 ℃ in temperature, stirring velocity is under the condition of 1000～1400rpm, set by step 2) mass ratio of the alkane microcapsule core emulsion of the melamine resin prepolymer solution of system and step 1) system is 1: (2～10), the melamine resin prepolymer drips of solution is added in the alkane microcapsule core emulsion, drip 20～30min, keeping temperature to be 30～60 ℃ after dripping is 1000～1400rpm with stirring velocity, reaction 0.5～2h, be warming up to 70～90 ℃ with 1～6 ℃/min of temperature rise rate again, continue reaction 1h～6h, stop heating and stirring then, with deionized water wash, the alkane microcapsule of the cold phase transformation that was inhibited after the drying.
One kind by claim 1 described or by the prepared inhibition of claim 2 method the application of alkane microcapsule of cold phase transformation, for the preparation of thermal insulation coatings.
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| CN102719227A (en) * | 2012-05-08 | 2012-10-10 | 广西桂邦生物能源有限公司 | Preparation method for high stable phase transition emulsion |
| CN102786817A (en) * | 2012-07-26 | 2012-11-21 | 天津大学 | Silica-supported organic alkane phase change material, and preparation method and application thereof |
| CN105368245A (en) * | 2015-12-26 | 2016-03-02 | 孝感巨核新材料科技有限公司 | Phase-change interior wall coating with energy storage and temperature adjustment functions and preparation method of coating |
| 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 |
| CN110951465A (en) * | 2019-12-13 | 2020-04-03 | 天津优米优科技有限公司 | Novel phase change capsule and preparation method thereof |
| CN113648943B (en) * | 2021-08-31 | 2023-07-25 | 广东工业大学 | Method for reducing supercooling degree of alkane phase-change microcapsule by using different shell materials, microcapsule prepared by method and application of microcapsule |
| CN117447971A (en) * | 2023-12-25 | 2024-01-26 | 东北农业大学 | Preparation method of n-tetradecane phase-change microcapsule powder and anti-icing coating |
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