CN108485608A - Method for reducing supercooling degree of normal alkane energy storage material microcapsule - Google Patents
Method for reducing supercooling degree of normal alkane energy storage material microcapsule Download PDFInfo
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- 239000003094 microcapsule Substances 0.000 title claims abstract description 114
- 238000004146 energy storage Methods 0.000 title claims abstract description 93
- 239000011232 storage material Substances 0.000 title claims abstract description 92
- 238000004781 supercooling Methods 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 42
- 150000001335 aliphatic alkanes Chemical class 0.000 title abstract description 17
- 239000002667 nucleating agent Substances 0.000 claims abstract description 61
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 59
- 150000001875 compounds Chemical class 0.000 claims abstract description 38
- 239000004640 Melamine resin Substances 0.000 claims abstract description 36
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 18
- 239000013078 crystal Substances 0.000 claims abstract description 18
- 229920001046 Nanocellulose Polymers 0.000 claims abstract description 14
- 238000010899 nucleation Methods 0.000 claims abstract description 11
- 230000006911 nucleation Effects 0.000 claims abstract description 11
- 230000000694 effects Effects 0.000 claims abstract description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 43
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 238000002156 mixing Methods 0.000 claims description 30
- 229920000642 polymer Polymers 0.000 claims description 29
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 23
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 238000007792 addition Methods 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 15
- 239000012153 distilled water Substances 0.000 claims description 14
- 239000000839 emulsion Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 12
- 150000001721 carbon Chemical group 0.000 claims description 11
- 206010011732 Cyst Diseases 0.000 claims description 9
- 208000031513 cyst Diseases 0.000 claims description 9
- 230000033228 biological regulation Effects 0.000 claims description 7
- 238000005352 clarification Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 239000006210 lotion Substances 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 abstract description 13
- 230000008025 crystallization Effects 0.000 abstract description 13
- 239000003795 chemical substances by application Substances 0.000 abstract description 7
- 239000002775 capsule Substances 0.000 abstract description 6
- 125000004432 carbon atom Chemical group C* 0.000 abstract 1
- 239000002131 composite material Substances 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- 239000011162 core material Substances 0.000 description 36
- CBFCDTFDPHXCNY-UHFFFAOYSA-N icosane Chemical compound CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 description 22
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 18
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 14
- HOWGUJZVBDQJKV-UHFFFAOYSA-N docosane Chemical compound CCCCCCCCCCCCCCCCCCCCCC HOWGUJZVBDQJKV-UHFFFAOYSA-N 0.000 description 12
- VAMFXQBUQXONLZ-UHFFFAOYSA-N n-alpha-eicosene Natural products CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 description 11
- 238000004132 cross linking Methods 0.000 description 8
- NDJKXXJCMXVBJW-UHFFFAOYSA-N heptadecane Chemical compound CCCCCCCCCCCCCCCCC NDJKXXJCMXVBJW-UHFFFAOYSA-N 0.000 description 8
- FIGVVZUWCLSUEI-UHFFFAOYSA-N tricosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCC FIGVVZUWCLSUEI-UHFFFAOYSA-N 0.000 description 8
- 239000012782 phase change material Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 5
- 229920002678 cellulose Polymers 0.000 description 5
- 239000001913 cellulose Substances 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 5
- 229940038384 octadecane Drugs 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- -1 carbon atom fatty alcohol Chemical class 0.000 description 3
- LQERIDTXQFOHKA-UHFFFAOYSA-N nonadecane Chemical compound CCCCCCCCCCCCCCCCCCC LQERIDTXQFOHKA-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229920000128 polypyrrole Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
- C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention provides a method for reducing supercooling degree of n-alkane energy storage material microcapsules, which is characterized by comprising the following steps of: the method comprises the steps of preparing a composite capsule core mixed system, preparing a melamine resin prepolymer, preparing an O/W system and preparing an energy storage and temperature adjustment microcapsule. The invention selects two nucleating agents for compounding, namely selects the same compound with the carbon atom number higher than (n + 1) - (n + 2) of the phase change agent as the nucleating agent of homogeneous nucleation, and combines the heterogeneous nucleation of the nanocellulose crystal at the same time, thereby greatly reducing the supercooling degree of the normal alkane energy storage material microcapsule through the mutual combination of the two nucleating effects. Compared with the prior art, the supercooling degree of the normal alkane energy storage material microcapsule prepared by the invention is reduced by 3.6-5.0 ℃, and basically the theoretical crystallization temperature difference of the normal alkane energy storage material microcapsule with the normal alkane energy storage material microcapsule is kept to be not much.
Description
Technical field
The present invention relates to energy-saving and temperature-regulating microcapsules technology field, more particularly to a kind of reduction N-alkanes hydro carbons energy storage material is micro-
The technical method of capsule degree of supercooling.
Background technology
Degree of supercooling refers to the difference of theoretical crystallization temperature and the crystallization scene temperature actually given, is a temperature difference.Reason
All it is known by crystallization temperature, practical crystallization temperature needs to measure, to provide temperature difference.
The supercooling crystalline polamer of energy storage material microcapsules is a kind of physical phenomenon of generally existing, mainly due to glue
The reduction of capsule grain size, the heterogeneous nucleation agent in each capsule is fewer and fewer, causes heterogeneous nucleation crystallization difficult, and mainly with homogeneous
Based on nucleation and crystallization, crosses the heat that cold crystallization so that fiber stores and discharged within the scope of lower temperature or wider temperature, from
And lower or lose temp regulating function.
It is mainly that outer Added Nucleating Agents promote its heterogeneous nucleation to crystallize to inhibit the method for the supercooling of phase-change material, common to be nucleated
Agent has high carbon atom fatty alcohol, inorganic matter, nano-particle etc..However, the addition of nucleating agent can reduce phase-change material in microcapsules
Content, and further decline with the increase of addition；High carbon atom fatty alcohol（Hydroxyl has hydrophily）And sodium chloride（Have
Breaking）Microencapsulated phase change material can be made to be easy to happen reunion when Deng as nucleating agent；The nothing being generally added in the prior art
Machine nano-particle is poor because considering its intersolubility between core material, is not a kind of ideal nucleating agent.
Chinese patent CN201510359606.9 discloses a kind of low degree of supercooling phase-change material micro-capsule and preparation method thereof.
The technology is by N, and at least one of N- acrylamides and n-isopropyl acrylamide are added as supercooling inhibitor
Into capsule-core component, polymer is generated in follow-up polymerization process, plays the role of heterogeneous nucleation, it is micro- to reduce phase-change material
The degree of supercooling of capsule.But due to N, N- acrylamides and n-isopropyl acrylamide are as water-soluble and assistant for emulsifying agent object
Matter, and part can react with cyst wall, be eventually used for limited as the part of heterogeneous nucleation agent, limit the hair of effect
It waves.
Chinese patent CN 102876297A disclose a kind of low degree of supercooling phase-change material micro-capsule and preparation method thereof.It should
Method is the two-stage polymerization method using polypyrrole as heterogeneous nucleation agent（One-step polymerization forms cyst wall, and two steps polymerize to form polypyrrole）It closes
At low degree of supercooling phase-change material micro-capsule, preparation process is complex, the problem of there is also color changes of same microcapsules.
Chinese patent CN201410854746.9 discloses a kind of low degree of supercooling intensity controlled bilayer wall material phase-change microcapsule.
The internal layer wall material of low crosslinking degree is selected to improve the surfusion of phase-change microcapsule in the patented technology, but this method utilizes low cross-linking
The internal layer wall material improvement surfusion of degree is simultaneously infeasible, does not provide the nucleus of crystallization, seriously affects its microcapsules crystallization effect.
Chinese patent CN201110235098.5 discloses a kind of alkane microcapsules and its preparation side for inhibiting that phase transformation is subcooled
Method and application.In the patented technology using carbon atom number be 22 to 40 normal alkane as nucleating agent, although the technology use
Nucleating agent is same class compound with phase transition agent, and the carbon atom number of alkane nucleating agent is more than the carbon atom number of alkane phase transition agent,
But since carbon atom number difference is excessive, the difference such as solidification point of the two are excessive so that the performance of microcapsules plays not ideal enough.
Invention content
In view of the problems existing in the prior art, the purpose of the present invention is to provide a kind of reduction N-alkanes hydro carbons energy storage materials
The method of microcapsules degree of supercooling, using N-alkanes hydro carbons energy storage material microcapsules made from this method supercooling crystalline polamer substantially
Improve, the degree of supercooling for the N-alkanes hydro carbons energy storage material microcapsules that the present invention is prepared compared with prior art, reduce by 3.6 ~
5.0 DEG C, and the preparation method is simple for process, it is easy to operate, it is convenient for industrialized implementation.
To achieve the above object, the present invention adopts the following technical scheme that：
A method of N-alkanes hydro carbons energy storage material microcapsules degree of supercooling is reduced, is with N-alkanes hydro carbons energy storage material（Carbon is former
Subnumber is n, 16≤n≤22）It is compound capsule-core with nucleating agent.
Nucleating agent used includes two kinds of substances, and a kind of for carbon atom number, 1 ~ 2 just more than the phase transition agent used in capsule-core
Structure paraffinic materials, i.e., nucleating agent used is that carbon atom number is（n+1）~（n+2）N-alkane material；Another nucleating agent is straight
Diameter is 10 ~ 30nm, and length is the nano cellulose crystal of 50 ~ 100nm.
Since the high n-alkane material of carbon atom number is compared with n-alkane class phase transformation energy storage material, there is higher knot
Brilliant temperature, but since carbon atom number is not much different, therefore the crystallization temperature of the two does not have bigger difference, carbon is former in crystallization process
The high n-alkane material preferential crystallization of subnumber serves as the nucleus of core materials, is not equivalent to very much homogeneously in view of the two structural difference
Nucleation is be combined with each other, significantly in combination with the heterogeneous nucleating effect of nano cellulose crystal by both nucleations
Reduce the degree of supercooling of N-alkanes hydro carbons energy storage material microcapsules.
The N-alkanes hydro carbons energy storage material microcapsules prepared using this method are by weight percentage by compound capsule-core and capsule
Wall forms, and the compound capsule-core is according to the raw material of weight percent by N-alkanes hydro carbons energy storage material 95.2~98.6%, nucleation
Agent n-alkane material 1.0~3.0% and nucleating agent nano cellulose crystal 0.4~1.8% form.
A method of N-alkanes hydro carbons energy storage material microcapsules degree of supercooling is reduced, including prepares compound capsule-core mixture
It is, prepares melamine resin performed polymer, prepare O/W systems, prepare energy-saving and temperature-regulating microcapsules, concrete scheme is：
1, by compound capsule-core（N-alkanes hydro carbons energy storage material（Carbon atom number is n, 16≤n≤22）, nucleating agent n-alkane material
（（n+1）~（n+2））, nucleating agent nano cellulose crystal, three is in mass ratio（95.2~98.6）∶（1.0~3.0）：
（0.4~1.8））, compound capsule-core is added in mixing kettle, is stirred at 35 ~ 50 DEG C of temperature and the mixing speed of 400 ~ 1000rpm
30 ~ 60min is mixed, is uniformly mixed, prepares compound capsule-core mixed system.
2, with thermometer, agitating paddle, condenser reaction kettle in melamine, glutaraldehyde and appropriate distilled water is added,
In, melamine, glutaraldehyde ratio be（3~6）:1, the mass ratio of the gross mass and distilled water of melamine and glutaraldehyde is 1:（1~
4）, and be added after sodium hydroxide adjusts pH to 8.0~9.5 and be warming up to 80~90 DEG C and reacted, it is added after solution becomes clarification
PVA, PVA addition are the 2.0%~8.0% of melamine content, and temperature is down to 65~72 DEG C, then 50 ~ 60 min of isothermal reaction is used
PH is to neutrality for sodium hydroxide regulation system, and be cooled to 45~50 DEG C it is spare, prepare melamine resin performed polymer.
3, in melamine resin performed polymer made from the compound capsule-core mixed system for preparing step 1 and step 2 it is effective at
Part is 50 in mass ratio:50~60:After 40 ratio mixing, in temperature 45 C~50 DEG C with 2500~8000rpm of mixing speed
60~180min of stirring obtains lotion, and N-alkanes hydro carbons energy storage material microcapsule emulsion system is made, and forms O/W systems.
4, N-alkanes hydro carbons energy storage material microcapsule emulsion system is transferred in reaction kettle, is sufficiently stirred, temperature is steady
It is fixed to 80~85 DEG C, adjust pH to 5.5~6.5 and react 30~40min so that flexible melamine resin performed polymer crosslinking, prepare with
N-alkanes hydro carbons energy storage material is capsule-core, and melamine resin is the energy-saving and temperature-regulating microcapsules of cyst wall, after polymerize adjusting pH to neutrality,
Natural cooling stops stirring to get to N-alkanes hydro carbons energy storage material microcapsules, and the degree of supercooling of the microcapsules substantially reduces, grain size
D90≤2.128μm。
Beneficial effects of the present invention：
（1）The present invention selects higher than the carbon atom number of phase transition agent（n+1）~（n+2）Same class compound be homogeneous nucleation at
Core agent is be combined with each other by both nucleations, is substantially reduced in combination with the heterogeneous nucleating effect of nano cellulose crystal
The degree of supercoolings of N-alkanes hydro carbons energy storage material microcapsules.The N-alkanes hydro carbons energy storage material microcapsules that the present invention is prepared
Degree of supercooling compared with prior art, reduces by 3.6 ~ 5.0 DEG C, is kept substantially and is tied with the theory of original N-alkanes hydro carbons energy storage material
Brilliant temperature difference is few.
（2）The N-alkanes hydro carbons energy storage material microcapsules that the present invention is prepared, degree of supercooling are 0.7-2.1 DEG C；Than independent
Add nucleating agent n-alkane material（（n+1）~（n+2））The N-alkanes hydro carbons energy storage material microcapsules of preparation are compared, degree of supercooling
Reduce 3.3-5 DEG C；Compared with the N-alkanes hydro carbons energy storage material microcapsules for not adding nucleating agent, degree of supercooling reduces 6.9-12.7
℃。
The following describes the present invention in detail with reference to examples.
Specific implementation mode
Hereinafter, preferred embodiments of the present invention will be described, it should be understood that preferred embodiment described herein is only used
In the description and interpretation present invention, it is not intended to limit the present invention.
Embodiment 1：A method of reducing N-alkanes hydro carbons energy storage material microcapsules degree of supercooling
Include the following steps：
Step 1 prepares compound capsule-core mixed system
By compound capsule-core（Hexadecane, nucleating agent n-heptadecane, nucleating agent nano cellulose crystal, three are in mass ratio
95.2:3.0:1.8）It is added in mixing kettle, 30min is stirred at 35 DEG C of temperature and the mixing speed of 1000rpm, mixing is equal
It is even, prepare compound capsule-core mixed system.
Step 2 prepares melamine resin performed polymer
With thermometer, agitating paddle, condenser reaction kettle in melamine, glutaraldehyde and appropriate distilled water is added, wherein it is close
Amine, glutaraldehyde ratio be 3:1, the mass ratio of the gross mass and distilled water of melamine and glutaraldehyde is 1:1, and sodium hydroxide is added
It is warming up to 80 DEG C after adjusting pH to 8.0 to be reacted, PVA is added after solution becomes clarification, PVA additions are melamine content
2.0%, temperature is down to 65 DEG C, isothermal reaction 60min, then use sodium hydroxide regulation system pH to neutrality, and be cooled to 45 DEG C it is standby
With preparing melamine resin performed polymer.
Step 3 prepares O/W systems
Compound capsule-core mixed system prepared by step 1 is with the effective ingredient in melamine resin performed polymer made from step 2 by matter
Amount is than being 50:After 50 ratio mixing, lotion is obtained with mixing speed 2500rpm stirrings 180min in temperature 45 C, is made just
Hexadecane energy storage material microcapsule emulsion system forms O/W systems.
Step 4 prepares energy-saving and temperature-regulating microcapsules
Hexadecane energy storage material microcapsule emulsion system is transferred in reaction kettle, is sufficiently stirred, temperature is stablized to 80 DEG C,
It adjusts pH to 5.5 and reacts 40min so that flexible melamine resin performed polymer crosslinking, prepare preparation is with hexadecane energy storage material
Capsule-core, melamine resin are the energy-saving and temperature-regulating microcapsules of cyst wall, pH are adjusted after having polymerize to neutrality, natural cooling stops stirring, should
The degree of supercooling of microcapsules substantially reduces, and the grain size D90 of microcapsules is 2.128 μm.
After testing, the FCTA temprature of hexadecane energy storage material is 16.7 DEG C, not the hexadecane storage of Added Nucleating Agents
The FCTA temprature of energy material microcapsule is 9.6 DEG C, and degree of supercooling is 7.7 DEG C, individually adds positive the ten of nucleating agent n-heptadecane
The FCTA temprature of six alkane energy storage material microcapsules is 11.6 DEG C, and degree of supercooling is 4.1 DEG C, is prepared using 1 method of embodiment
The FCTA temprature of energy storage material microcapsules is 15.9 DEG C, and degree of supercooling is 0.8 DEG C.
Therefore, the microcapsules prepared using 1 method of embodiment（Add nucleating agent n-heptadecane and nucleating agent nano-cellulose
Crystal）Compared with the individually degree of supercooling of the hexadecane energy storage material microcapsules of addition nucleating agent n-heptadecane, 3.3 DEG C are reduced.
Embodiment 2：A method of reducing N-alkanes hydro carbons energy storage material microcapsules degree of supercooling
Include the following steps：
Step 1 prepares compound capsule-core mixed system
By compound capsule-core（N-octadecane, nucleating agent NSC 77136, nucleating agent nano cellulose crystal, three are in mass ratio
96.5:2.3:1.2）It is added in mixing kettle, stirs 36min at 38 DEG C of temperature and the mixing speed of 816rpm, be uniformly mixed,
Prepare compound capsule-core mixed system.
Step 2 prepares melamine resin performed polymer
With thermometer, agitating paddle, condenser reaction kettle in melamine, glutaraldehyde and appropriate distilled water is added, wherein it is close
Amine, glutaraldehyde ratio be 4:1, the mass ratio of the gross mass and distilled water of melamine and glutaraldehyde is 1:2, and sodium hydroxide is added
It is warming up to 82 DEG C after adjusting pH to 8.3 to be reacted, PVA is added after solution becomes clarification, PVA additions are melamine content
3.6%, temperature is down to 68 DEG C, isothermal reaction 58min, then uses sodium hydroxide regulation system pH to neutrality, and be cooled to 47 DEG C
It is spare, prepare melamine resin performed polymer.
Step 3 prepares O/W systems
Compound capsule-core mixed system prepared by step 1 is with the effective ingredient in melamine resin performed polymer made from step 2 by matter
Amount is than being 55:After 45 ratio mixing, lotion is obtained with mixing speed 3800rpm stirrings 126min 46 DEG C in temperature, is made just
Structure alkanes energy storage material microcapsule emulsion system forms O/W systems.
Step 4 prepares energy-saving and temperature-regulating microcapsules
N-octadecane energy storage material microcapsule emulsion system is transferred in reaction kettle, is sufficiently stirred, temperature is stablized to 81 DEG C,
It adjusts pH to 5.8 and reacts 38min so that flexible melamine resin performed polymer crosslinking, prepare preparation is with n-octadecane energy storage material
Capsule-core, melamine resin are the energy-saving and temperature-regulating microcapsules of cyst wall, pH are adjusted after having polymerize to neutrality, natural cooling stops stirring, should
The degree of supercooling of microcapsules substantially reduces, and the grain size D90 of microcapsules is 2.116 μm.
After testing, the FCTA temprature of n-octadecane energy storage material is 25.5 DEG C, not the n-octadecane storage of Added Nucleating Agents
The FCTA temprature of energy material microcapsule is 16.8 DEG C, and degree of supercooling is 8.7 DEG C；Individually positive the ten of addition nucleating agent NSC 77136
The FCTA temprature of eight alkane energy storage material microcapsules is 20.8 DEG C, and degree of supercooling is 4.7 DEG C；It is prepared using 2 method of embodiment
The FCTA temprature of energy storage material microcapsules is 24.5 DEG C, and degree of supercooling is 1.0 DEG C；
Therefore, the microcapsules prepared using 2 method of embodiment（It adds nucleating agent NSC 77136 and nucleating agent nano-cellulose is brilliant
Body）Compared with the individually degree of supercooling of the n-octadecane energy storage material microcapsules of addition nucleating agent NSC 77136,3.7 DEG C are reduced.
Embodiment 3：A method of reducing N-alkanes hydro carbons energy storage material microcapsules degree of supercooling
Include the following steps：
Step 1 prepares compound capsule-core-mixed system
By compound capsule-core（N-eicosane, nucleating agent n-docosane, nucleating agent nano cellulose crystal, three are in mass ratio
97.1：1.8：1.1）It is added in mixing kettle, stirs 44min at 43 DEG C of temperature and the mixing speed of 690rpm, be uniformly mixed,
Prepare compound capsule-core-mixed system.
Step 2 prepares melamine resin performed polymer
With thermometer, agitating paddle, condenser reaction kettle in melamine, glutaraldehyde and appropriate distilled water is added, wherein it is close
Amine, glutaraldehyde ratio be 5:1, the mass ratio of the gross mass and distilled water of melamine and glutaraldehyde is 1:3, and sodium hydroxide is added
It is warming up to 85 DEG C after adjusting pH to 8.6 to be reacted, PVA is added after solution becomes clarification, PVA additions are melamine content
5.2%, temperature is down to 70 DEG C, isothermal reaction 55min, then use sodium hydroxide regulation system pH to neutrality, and be cooled to 48 DEG C it is standby
With preparing melamine resin performed polymer.
Step 3 prepares O/W systems
Compound capsule-core mixed system prepared by step 1 is with the effective ingredient in melamine resin performed polymer made from step 2 by matter
Amount is than being 58:After 42 ratio mixing, lotion is obtained with mixing speed 5600rpm stirrings 102min 48 DEG C in temperature, is made just
Structure alkanes energy storage material microcapsule emulsion system forms O/W systems.
Step 4 prepares energy-saving and temperature-regulating microcapsules
N-eicosane energy storage material microcapsule emulsion system is transferred in reaction kettle, is sufficiently stirred, temperature is stablized to 82 DEG C,
It adjusts pH to 6.2 and reacts 35min so that flexible melamine resin performed polymer crosslinking, prepare preparation is with n-eicosane energy storage material
Capsule-core, melamine resin are the energy-saving and temperature-regulating microcapsules of cyst wall, pH are adjusted after having polymerize to neutrality, natural cooling stops stirring, should
The degree of supercooling of microcapsules substantially reduces, and the grain size D90 of microcapsules is 2.036 μm.
After testing, the FCTA temprature of n-eicosane energy storage material microcapsules is 30.6 DEG C, not positive the two of Added Nucleating Agents
The FCTA temprature of ten alkane energy storage material microcapsules is 20.5 DEG C, and degree of supercooling is 10.1 DEG C；Individually addition nucleating agent positive 20
The FCTA temprature of the n-eicosane energy storage material microcapsules of dioxane is 24.3 DEG C, and degree of supercooling is 6.3 DEG C, using embodiment 3
The FCTA temprature of n-eicosane energy storage material microcapsules prepared by method is 28.3 DEG C, and degree of supercooling is 1.3 DEG C；
Therefore, the energy storage material microcapsules prepared using 3 method of embodiment（Add nucleating agent n-docosane and nucleating agent nanometer
Cellulose crystals）Compared with the individually n-eicosane energy storage material microcapsules of addition nucleating agent n-docosane, degree of supercooling reduces
5.0℃。
Embodiment 4：A method of reducing N-alkanes hydro carbons energy storage material microcapsules degree of supercooling
Include the following steps：
Step 1 prepares compound capsule-core mixed system
By compound capsule-core（N-docosane, nucleating agent n-tricosane, nucleating agent nano cellulose crystal, three is in mass ratio
It is 97.9:1.5:0.6）It is added in mixing kettle, 53min is stirred at 48 DEG C of temperature and the mixing speed of 555rpm, mixing is equal
It is even, prepare compound capsule-core mixed system.
Step 2 prepares melamine resin performed polymer
With thermometer, agitating paddle, condenser reaction kettle in melamine, glutaraldehyde and appropriate distilled water is added, wherein it is close
Amine, glutaraldehyde ratio be 6:1, the mass ratio of the gross mass and distilled water of melamine and glutaraldehyde is 1:3, and sodium hydroxide is added
It is warming up to 88 DEG C after adjusting pH to 9.0 to be reacted, PVA is added after solution becomes clarification, PVA additions are melamine content
6.8%, temperature is down to 71 DEG C, isothermal reaction 53min, then use sodium hydroxide regulation system pH to neutrality, and be cooled to 49 DEG C it is standby
With preparing melamine resin performed polymer.
Step 3 prepares O/W systems
Compound capsule-core mixed system prepared by step 1 is with the effective ingredient in melamine resin performed polymer made from step 2 by matter
Amount is than being 60:After 40 ratio mixing, lotion is obtained with mixing speed 7160rpm stirrings 85min 49 DEG C in temperature, positive structure is made
Alkanes energy storage material microcapsule emulsion system forms O/W systems.
Step 4 prepares energy-saving and temperature-regulating microcapsules
N-docosane energy storage material microcapsule emulsion system is transferred in reaction kettle, is sufficiently stirred, temperature is stablized to 83
DEG C, it adjusts pH to 6.4 and reacts 33min so that flexible melamine resin performed polymer crosslinking is prepared with n-docosane energy storage material
Material is capsule-core, and melamine resin is the energy-saving and temperature-regulating microcapsules of cyst wall, pH is adjusted after having polymerize to neutrality, natural cooling stopping is stirred
It mixes, the degree of supercooling of the microcapsules substantially reduces, and the grain size D90 of microcapsules is 1.996 μm.
After testing, the FCTA temprature of n-docosane energy storage material is 44.4 DEG C, not the n-eicosane of Added Nucleating Agents
The FCTA temprature of energy storage material microcapsules is 29.6 DEG C, and degree of supercooling is 14.8 DEG C；Individually addition nucleating agent n-tricosane
N-docosane energy storage material microcapsules FCTA temprature be 38.7 DEG C, degree of supercooling be 6.7 DEG C；
Use the FCTA temprature of n-eicosane energy storage material microcapsules prepared by 4 method of embodiment for 42.3 DEG C, degree of supercooling
It is 2.1 DEG C；
Therefore, the energy storage material microcapsules prepared using 4 method of embodiment（Add nucleating agent n-tricosane and nucleating agent nanometer
Cellulose crystals）It is reduced with the degree of supercooling of the n-docosane energy storage material microcapsules of independent addition nucleating agent n-tricosane
4.6℃。
Embodiment 5：A method of reducing N-alkanes hydro carbons energy storage material microcapsules degree of supercooling
Include the following steps：
Step 1 prepares compound capsule-core mixed system
By compound capsule-core（N-octadecane, nucleating agent n-eicosane, nucleating agent nano cellulose crystal, three are in mass ratio
98.6:1.0:0.4）It is added in mixing kettle, 60min is stirred under the mixing speed of temperature 50 C and 400rpm, be uniformly mixed,
Prepare compound capsule-core mixed system.
Step 2 prepares melamine resin performed polymer
With thermometer, agitating paddle, condenser reaction kettle in melamine, glutaraldehyde and appropriate distilled water is added, wherein it is close
Amine, glutaraldehyde ratio be 6:1, the mass ratio of the gross mass and distilled water of melamine and glutaraldehyde is 1:4, and sodium hydroxide is added
It is warming up to 90 DEG C after adjusting pH to 9.5 to be reacted, PVA is added after solution becomes clarification, PVA additions are melamine content
8.0%, temperature is down to 72 DEG C, isothermal reaction 50min, then use sodium hydroxide regulation system pH to neutrality, and be cooled to 50 DEG C it is standby
With preparing melamine resin performed polymer.
Step 3 prepares O/W systems
Compound capsule-core mixed system prepared by step 1 is with the effective ingredient in melamine resin performed polymer made from step 2 by matter
Amount is than being 60:After 40 ratio mixing, lotion is obtained with mixing speed 8000rpm stirrings 60min in temperature 50 C, positive structure is made
Alkanes energy storage material microcapsule emulsion system forms O/W systems.
Step 4 prepares energy-saving and temperature-regulating microcapsules
N-octadecane energy storage material microcapsule emulsion system is transferred in reaction kettle, is sufficiently stirred, temperature is stablized to 85 DEG C,
It adjusts pH to 6.5 and reacts 30min so that flexible melamine resin performed polymer crosslinking, prepare preparation is with n-octadecane energy storage material
Capsule-core, melamine resin are the energy-saving and temperature-regulating microcapsules of cyst wall, pH are adjusted after having polymerize to neutrality, natural cooling stops stirring, should
The degree of supercooling of microcapsules substantially reduces, and the grain size D90 of microcapsules is 2.085 μm.
After testing, the FCTA temprature of n-octadecane energy storage material is 25.5 DEG C, not the n-octadecane storage of Added Nucleating Agents
The FCTA temprature of energy material microcapsule is 16.8 DEG C, and degree of supercooling is 8.7 DEG C；Individually positive the ten of addition nucleating agent n-eicosane
The FCTA temprature of eight alkane energy storage material microcapsules is 21.2 DEG C, and degree of supercooling is 4.3 DEG C；It is prepared using 5 method of embodiment
The FCTA temprature of n-octadecane energy storage material microcapsules is 24.8 DEG C, and degree of supercooling is 0.7 DEG C；
Therefore, the energy storage material microcapsules prepared using 5 method of embodiment（Add nucleating agent n-eicosane and nucleating agent Nanowire
Tie up cellulose crystal）, compared with the individually degree of supercooling of the n-octadecane energy storage material microcapsules of addition nucleating agent n-eicosane, reduce
3.6℃。
Unless specifically indicated, the ratio that the present invention uses is mass ratio；The percentage of use is quality percentage
Than.
Finally it should be noted that：The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention,
Although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, still may be used
With technical scheme described in the above embodiments is modified, all within the spirits and principles of the present invention, made by appoint
What modification, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of method reducing N-alkanes hydro carbons energy storage material microcapsules degree of supercooling, it is characterised in that：The method, including system
Standby compound capsule-core mixed system prepares melamine resin performed polymer, prepares O/W systems, prepares energy-saving and temperature-regulating microcapsules.
2. a kind of method reducing N-alkanes hydro carbons energy storage material microcapsules degree of supercooling according to claim 1, feature
It is：The compound capsule-core, including N-alkanes hydro carbons energy storage material and nucleating agent；The N-alkanes hydro carbons energy storage material, carbon are former
Subnumber is 16-22.
3. a kind of method reducing N-alkanes hydro carbons energy storage material microcapsules degree of supercooling according to claim 2, feature
It is：The nucleating agent is composed of n-alkane material and nano cellulose crystal；The carbon of the n-alkane material is former
Subnumber 1-2 more than the carbon atom number of N-alkanes hydro carbons energy storage material is a, plays the role of homogeneous nucleation.
4. a kind of method reducing N-alkanes hydro carbons energy storage material microcapsules degree of supercooling according to claim 3, feature
It is：The nano cellulose crystal, a diameter of 10 ~ 30nm, length are 50 ~ 100nm, play heterogeneous nucleating effect.
5. a kind of method reducing N-alkanes hydro carbons energy storage material microcapsules degree of supercooling according to claim 1, feature
It is：The compound capsule-core is made of following raw material by weight percentage：N-alkanes hydro carbons energy storage material 95.2~
98.6%, nucleating agent n-alkane material 1.0~3.0%, nucleating agent nano cellulose crystal 0.4~1.8%.
6. a kind of method reducing N-alkanes hydro carbons energy storage material microcapsules degree of supercooling according to claim 1, feature
It is：It is described to prepare compound capsule-core mixed system, compound capsule-core is added in mixing kettle, 35 ~ 50 DEG C of temperature and 400 ~
30 ~ 60min is stirred under the mixing speed of 1000rpm, is uniformly mixed, is prepared compound capsule-core mixed system.
7. a kind of method reducing N-alkanes hydro carbons energy storage material microcapsules degree of supercooling according to claim 1, feature
It is：It is described to prepare melamine resin performed polymer, melamine, glutaraldehyde and distilled water is added, wherein melamine, glutaraldehyde ratio be
3:1~6:1, the mass ratio of the gross mass and distilled water of melamine and glutaraldehyde is 1:1~1:4, and sodium hydroxide is added and adjusts pH
It is warming up to 80~90 DEG C after to 8.0~9.5 to be reacted, PVA is added after solution becomes clarification, PVA additions are melamine content
2.0%~8.0%, temperature is down to 65~72 DEG C, 50 ~ 60 min of isothermal reaction, then use sodium hydroxide regulation system pH into
Property, and be cooled to 45~50 DEG C it is spare, prepare melamine resin performed polymer.
8. a kind of method reducing N-alkanes hydro carbons energy storage material microcapsules degree of supercooling according to claim 1, feature
It is：The compound capsule-core mixed system of preparation is by the preparation O/W systems in mass ratio with melamine resin performed polymer obtained
50:50~60:After 40 ratio mixing, temperature 45 C~50 DEG C with mixing speed 2500~8000rpm stirring 60~
180min obtains lotion, and N-alkanes hydro carbons energy storage material microcapsule emulsion system is made, and forms O/W systems.
9. a kind of method reducing N-alkanes hydro carbons energy storage material microcapsules degree of supercooling according to claim 1, feature
It is：It is described to prepare energy-saving and temperature-regulating microcapsules, N-alkanes hydro carbons energy storage material microcapsule emulsion O/W systems are transferred to reaction kettle
In, it is sufficiently stirred, temperature is stablized to 80~85 DEG C, adjust pH to 5.5~6.5 and react 30~40min, prepare with n-alkane
Class energy storage material is capsule-core, and melamine resin is the energy-saving and temperature-regulating microcapsules of cyst wall, and pH is adjusted after having polymerize to neutrality, natural cooling
Stop stirring to get to N-alkanes hydro carbons energy storage material microcapsules.
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