CN103804558A - Nano phase change material emulsion wide in temperature change range and preparation method thereof - Google Patents
Nano phase change material emulsion wide in temperature change range and preparation method thereof Download PDFInfo
- Publication number
- CN103804558A CN103804558A CN201210461555.7A CN201210461555A CN103804558A CN 103804558 A CN103804558 A CN 103804558A CN 201210461555 A CN201210461555 A CN 201210461555A CN 103804558 A CN103804558 A CN 103804558A
- Authority
- CN
- China
- Prior art keywords
- change material
- phase change
- water
- emulsion
- initiator
- 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.)
- Pending
Links
Images
Landscapes
- Manufacturing Of Micro-Capsules (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention provides nano phase change material emulsion wide in temperature change range and a preparation method thereof. The preparation method comprises the following steps: (1) adding a mixing solution containing a monomer, a chain transfer agent and a cross-linking agent to a molten phase change material to form an oil phase; (2) dissolving an emulsifying agent AOS and sodium hydrogen carbonate in water to obtain an aqueous phase; (3) dropping the oil phase to the aqueous phase, and shearing and emulsifying to obtain fine emulsion; (4) adding an initiator to initiate polymerization at 68-70 DEG C to obtain the nano phase change material emulsion wide in temperature change range. The nano capsule phase change material prepared from the polymerizable emulsifying agent has the advantages of good shear resistance, excellent freeze-thaw stability, good electrolyte resistance and good water resistance, wide temperature change range and the like, so that the phase change material is applicable to severe conditions as well, thus widening application scope.
Description
Technical field
The present invention relates to a kind of preparation method of nano capsule phase change material emulsion, particularly adopt a kind of polymerisable emulsifier alpha-olefin sodium sulfonate (AOS) of business level scale to prepare nano capsule phase change material, be suitable for the application scenario of 20-60 ℃ of scope decalescence and heat release.
Background technology
For avoiding phase change material in use to occur to leak and deformation, people generally use after being combined into microcapsule coated phase change material.Current phase change material organic/inorganic substance matter and the organic substance of micro encapsulation, wherein disclosed organic substance phase change material has paraffin (CN201110380869), higher alkane, dodecanol, lipid acid, polyoxyethylene glycol and phase transformation polymkeric substance etc.
Compared with microcapsule, nano capsule phase change material due to have less size, larger heat transfer area and faster storage/rate of heat release become the focus of research and development.In recent years, people have successfully prepared the coated phase change material of multiple Nano capsule by mini-emulsion polymerization technology, for example open source literature (Fang Y T, et al.Preparation and characterization of novel nanoencapsulated phase change materials[J] .Energy Conversion and Management, 2008,49:3704 – 3707) adopt mini-emulsion polymerization technology to prepare octadecane/polystyrene phase material.
Prepare in nano capsule phase change material process at fine emulsion polymerization, distinct issues are compared with microcapsule, and emulsifier is larger, and the size of the stable and particle of the character of emulsifying agent to emulsion produces material impact.Common emulsifying agent is adsorbed on polymer beads sub-surface by physical action, and its emulsion is easy loss of stability under the condition such as high, freezing or high-shear in ionic strength.This just means that envrionment conditions acute variation will cause coming off of emulsifying agent on phase change material particle, and causes emulsion loss of stability.Different from common emulsifying agent, polymerisable emulsifier due to can with monomer copolymerization, after polymerization, emulsifying agent becomes the integral part of capsule wall material, make this emulsion can be high in ionic strength, freezing or the mal-condition such as high-shear under still there is the unsettled ability of opposing.Document (Chen ZH, et al.Preparation, characterization and thermal properties of nanocapsules containing phase change material n-dodecanol by miniemulsion polymerizationwith polymerizable emulsifie[J] .Applied Energy 91 (2012) 7-12) report and prepared octadecane/PMMA nano capsule phase change material with polymerisable emulsifier DNS-86.But, because the cost of this polymerisable emulsifier is high, be not also the emulsifying agent of business level scale, and the temperature of octadecane become be limited in scope, this has just limited the further application of this phase change material miniemulsion.
Summary of the invention
The object of this invention is to provide nano phase change material emulsion of a kind of wide temperature change scope and preparation method thereof, to overcome the defect of phase change material miniemulsion prepared by common emulsifying agent, can reduce costs, widen its range of application simultaneously.
The preparation method of the nano capsule phase change material emulsion of wide temperature change scope of the present invention, comprises the steps:
(1) mixing solutions that contains monomer, chain-transfer agent, linking agent is joined in the phase change material of molten state and form oil phase;
The mass percent of the mixing solutions of described monomer, chain-transfer agent, linking agent is:
Monomer 92.0 ~ 96.2%,
Chain-transfer agent 0 ~ 3.5%,
Linking agent 3.8 ~ 4.6%;
Component percentages sum equals 100%.
Preferably, the mass percent of the mixing solutions of described monomer, chain-transfer agent, linking agent is:
Monomer 92.5 ~ 96.0%,
Chain-transfer agent 0 ~ 3.3%,
Linking agent 3.8 ~ 4.6%;
Component percentages sum equals 100%.
Described monomer is selected from a kind of in methyl methacrylate, vinylbenzene, t-butyl styrene or Vinyl toluene or two kinds;
Said chain-transfer agent is selected from positive hexylmercaptan or lauryl mercaptan;
Described linking agent is selected from the compound that at least contains two unconjugated olefines unsaturated double-bonds, or at least contains an olefines unsaturated double-bond and another multi-functional material for carboxyl or hydroxyl; Preferably Vinylstyrene, allyl methyl vinylformic acid, Ethylene glycol dimethacrylate or ethylene glycol diacrylate;
It is the normal paraffin that 20～40 paraffin or carbonatoms are 16～27 that said phase change material is selected from carbonatoms, and phase change material consumption is 19%～33wt% of oil phase total amount;
(2) by emulsifying agent AOS and the water-soluble formation water of sodium bicarbonate;
The chemical name of described AOS is alpha-olefin sodium sulfonate (molecular formula R (CH
2)
ncH=CH-SO
3na, n=14-18), its mass concentration in water is 0.1～0.5wt%;
The mass concentration of sodium bicarbonate in water is 0.025 ~ 0.05wt%;
(3) under stirring, oil phase is added drop-wise in water, obtains thick emulsion, then emulsification pretreatment, and the shear line speed of shearing is 11.5-18.4m/s, shear time is 15-30min, obtains miniemulsion;
The mass ratio of water/oil phase is 5.6 ~ 7.6;
(4) at 68～70 ℃ of temperature, pass into nitrogen 30min, the oxygen in reactor is removed in displacement, adds initiator initiated polymerization, keeps after temperature 4-6h, and polyreaction finishes, and obtains the nano phase change material emulsion of described wide temperature change scope;
Said initiator is radical type initiator, is selected from over cure acids initiator or azo-initiator; Preferably Potassium Persulphate, ammonium persulphate, Diisopropyl azodicarboxylate;
Water soluble starter adds in batches, before adding, is dissolved in advance in water;
Oil-soluble initiator directly adds in the oil phase containing monomer;
The effect of invention
The polymerisable emulsifier AOS that the present invention adopts is a kind of polymerisable emulsifier of business level scale.AOS reliable in quality, technical maturity, there is good soil removability, even if also demonstrate the feature that soil removability does not reduce in hard water.
It is good that nano capsule phase change material emulsion prepared by the polymerisable emulsifier that the present invention adopts has anti-shear performance, freeze-thaw stability is good, electrolyte-resistant, water-tolerant, the advantages such as range of temperature is wide, phase change material can be used under more severe condition, widen its use range, for example, under rainwash, also difficult drop-off and overcome conventional emulsifier and cause polyalcohol emulsion particle film forming defect because of migration of emulsifying agent, can well be applied to exterior coating and cement, in brick and tile, especially in desert and the larger area of the temperature difference effective especially, can also serve as the fabric coating material of sportwear.
Accompanying drawing explanation
The infared spectrum of the raw materials used AOS of Fig. 1 embodiment, X-coordinate is wave number, unit is cm
-1, ordinate zou is transmitance, unit is %;
Fig. 2 is embodiment 1 gained nano capsule phase change material infrared spectrum, and X-coordinate is wave number, and unit is cm
-1, ordinate zou is transmitance, unit is %;
Fig. 3 is the transmission electron microscope photo of embodiment 1 gained nano capsule phase change material, scale 200nm;
Fig. 4 is the DSC figure of embodiment phase change material paraffin used, and first curve is intensification situation, and second curve is cooling situation;
Fig. 5 is the DSC figure of embodiment 3 gained nano capsule phase change materials, and first curve is intensification situation, and second curve is cooling situation.
Embodiment
The measuring method of average particle size particle size: latex particle is diluted to after suitable concentration with deionized water, with the test of MS-2000 type laser particle analyzer, using D50 as its median size.
Transformation temperature scope measuring method: adopt the dried product of Dianond DS type differential scanning calorimeter test breakdown of emulsion, sweep limit is-10 ℃～120 ℃, heats up and rate of temperature fall is 10 ℃/min, N
2protection, Al
2o
3reference.
Nano capsule phase change material emulsion mechanical stability is evaluated: 50ml emulsion is placed in to 100ml beaker, then at room temperature disperses 10min with miniature high-speed mark machine with the rotating speed of 4000rpm, if there is not gel, judge the good stability of emulsion; Occur a small amount of gel, it is qualified to be judged to be; All gel is defective.
Nano capsule phase change material emulsion stability in storage is evaluated: the product 15ml after polymerization is put into the 20ml bottle of bottle cap and placed 3 months under room temperature, observation has or not precipitation or demixing phenomenon, if without precipitation or demixing phenomenon, judge that emulsion has excellent storage stability; Without precipitating but having layering, it is qualified to be judged to be; Have precipitation and layering be judged to be defective.
Nano capsule phase change material emulsion freeze-stable is evaluated: the emulsion 10ml after polymerization is placed after 24 hours in-4 ℃ of refrigerators, at room temperature place again and within 24 hours, allow the frozen glue observation of naturally thawing, if without oil spill, coalescent, demixing phenomenon, judge that emulsion has good freeze-stable; Without oil spill, coalescent, but there is layering, judge that emulsion freeze-stable is qualified; Appearance oil spill or agglomeration phenomena, judge that emulsion freeze-stable is defective.
Embodiment 1
(1) mixing solutions of 10g vinylbenzene, 1.5g methyl methacrylate and 0.5g Vinylstyrene is added to containing in 60 ℃ of fused solutions of 0.4g n-Hexadecane and 5.0g paraffin (phase transition performance of paraffin used is shown in accompanying drawing 4), continues to stir 10min and form oil phase A;
By 0.4g polymerisable emulsifier AOS(Shanghai Bo great chemical company product, molecular formula R (CH
2)
ncH=CH-SO
3na, n=14-18, its infared spectrum is shown in accompanying drawing 2), 0.025g sodium bicarbonate joins in 100g deionized water, mixes formation aqueous phase B;
(3) under magnetic agitation, oil phase A is added drop-wise in aqueous phase B, drip rear continuation stirring 30min and form thick emulsion.
(2) thick emulsion is sheared to (shears used is the WG500CY type laboratory high-shear emulsion machine that Shanghai Weiyu Electromechanical Equipment Manufacture Co. Ltd. produces) with high-shear machine, velocity of shear is 13000rpm, after shear time 20min, obtains miniemulsion.
(3) miniemulsion is poured into and be furnished with agitator, in the four-hole boiling flask of reflux condensing tube, nitrogen tube, flask be placed in to the water-bath of 68 ℃, pass into the deoxygenation of 30min nitrogen.0.15g Potassium Persulphate is dissolved in 15ml deionized water, adds 50% at the polyreaction initial stage respectively, after reaction 3h, add remaining 50%.After 6h, polyreaction finishes, and product is poured out after cooling.
The infared spectrum of product is shown in accompanying drawing 1, from relatively can finding out of accompanying drawing 1 and accompanying drawing 2: 2957-2849cm
-1multi-absorption peak is aliphatics C-H stretching vibration, 1464,1473cm
-1for C-H flexural vibration, 721cm
-1for CH
2absorption peak, illustrate that AOS has participated in polyreaction.
The average particle size particle size that is measured nano capsule phase change material by transmission electron microscope photo is 230nm, and its pattern is shown in accompanying drawing 3.The transformation temperature scope of product and stability are in table 1.
Embodiment 2
According to the method for embodiment 1, difference is to replace n-Hexadecane and paraffin with 5g n-Hexadecane as phase change material, and shear time is 15min.
The performance of products therefrom is in table 2.
Embodiment 3
According to the identical method of embodiment 1, difference is that the consumption of methyl methacrylate is 0.5g, and the consumption of n-Hexadecane and the consumption of paraffin are respectively 0g and 3g, and polymerization reaction time is 5h.
The DSC of products therefrom is shown in accompanying drawing 5, and other performance is in table 1.
Embodiment 4
(1) mixing solutions of 10g vinylbenzene, 1.5g methyl methacrylate, 0.5g allyl methyl vinylformic acid and the positive hexylmercaptan of 0.4g is joined in 60 ℃ of fused solutions of 3.0g paraffin (paraffin identical with embodiment 1), continue to stir 10min and form oil phase; By the 0.2g polymerisable emulsifier AOS(product identical with embodiment 1), 0.025g sodium bicarbonate joins in 100g deionized water, mixes formation water; Under magnetic agitation, oil phase is added drop-wise in water, drip rear continuation stirring 30min and form thick emulsion.
(2) thick emulsion is sheared to (shears used is the WG500CY type laboratory high-shear emulsion machine that Shanghai Weiyu Electromechanical Equipment Manufacture Co. Ltd. produces) with high-shear machine, velocity of shear is 13000rpm, after shear time 20min, obtains miniemulsion.
(3) miniemulsion is poured into and be furnished with agitator, in the four-hole boiling flask of reflux condensing tube, nitrogen tube, flask be placed in to the water-bath of 70 ℃, pass into the deoxygenation of 30min nitrogen.0.15g Potassium Persulphate is dissolved in 15ml deionized water, adds 50% at the polyreaction initial stage respectively, after reaction 3h, add remaining 50%.After 6h, polyreaction finishes, and product is poured out after cooling.
The performance of product is in table 1.
Embodiment 5
According to the identical method of embodiment 4, difference is to replace allyl methyl vinylformic acid with Vinylstyrene, and adds 0.2g Diisopropyl azodicarboxylate, and with 5g n-Hexadecane replacement 3g paraffin, in water, the consumption of AOS and sodium bicarbonate is respectively 0.4g and 0.05g.
The performance of product is in table 1.
Embodiment 6
(1) mixing solutions of 10g methyl methacrylate, 0.5g Vinylstyrene and the positive hexylmercaptan of 0.4g is joined in 60 ℃ of fused solutions of 3.0g paraffin (paraffin identical with embodiment 1), continue to stir 10min and form oil phase; By the 0.3g polymerisable emulsifier AOS(product identical with embodiment 1) and 0.025g sodium bicarbonate join in 100g deionized water, mix formation water; Under magnetic agitation, oil phase is added drop-wise in water, drip rear continuation stirring 30min and form thick emulsion.
(2) thick emulsion is sheared to (shears used is the WG500CY type laboratory high-shear emulsion machine that Shanghai Weiyu Electromechanical Equipment Manufacture Co. Ltd. produces) with high-shear machine, velocity of shear is 13000rpm, after shear time 20min, obtains miniemulsion.
(3) miniemulsion is poured into and be furnished with agitator, in the four-hole boiling flask of reflux condensing tube, nitrogen tube, flask be placed in to the water-bath of 70 ℃, pass into the deoxygenation of 30min nitrogen.0.2g Potassium Persulphate is dissolved in 15ml deionized water, adds 50% at the polyreaction initial stage respectively, after reaction 3h, add remaining 50%.After 6h, polyreaction finishes, and product is poured out after cooling.
The performance of product is in table 1.
The performance of table 1 embodiment 1～6 nano capsule phase change material
Claims (7)
1. the preparation method of the nano phase change material emulsion of wide temperature change scope, is characterized in that, comprises the steps:
(1) mixing solutions that contains monomer, chain-transfer agent, linking agent is joined in the phase change material of molten state and form oil phase;
Described monomer is selected from a kind of in methyl methacrylate, vinylbenzene, t-butyl styrene or Vinyl toluene or two kinds;
It is the normal paraffin that 20～40 paraffin or carbonatoms are 16～27 that said phase change material is selected from carbonatoms, and phase change material consumption is 19%～33wt% of oil phase total amount;
(2) by emulsifying agent AOS and the water-soluble formation water of sodium bicarbonate;
(3) under stirring, oil phase is added drop-wise in water, obtains thick emulsion, and then emulsification pretreatment, obtains miniemulsion;
(4) at 68～70 ℃ of temperature, pass into nitrogen 30min, the oxygen in reactor is removed in displacement, adds initiator initiated polymerization, keeps, after temperature 4-6h, obtaining the nano phase change material emulsion of described wide temperature change scope.
2. method according to claim 1, is characterized in that, the mass percent of the mixing solutions of described monomer, chain-transfer agent, linking agent is: monomer 92.0 ~ 96.2%, chain-transfer agent 0 ~ 3.5%, linking agent 3.8 ~ 4.6%; Component percentages sum equals 100%.
3. method according to claim 2, is characterized in that, said chain-transfer agent is selected from positive hexylmercaptan or lauryl mercaptan;
Described linking agent is selected from the compound that at least contains two unconjugated olefines unsaturated double-bonds, or at least contains an olefines unsaturated double-bond and another multi-functional material for carboxyl or hydroxyl.
4. method according to claim 1, is characterized in that, in step (2), by emulsifying agent AOS and the water-soluble formation water of sodium bicarbonate, its mass concentration in water is 0.1～0.5wt%; The mass concentration of sodium bicarbonate in water is 0.025 ~ 0.05wt%.
5. method according to claim 1, is characterized in that, the mass ratio of water/oil phase is 5.6 ~ 7.6.
6. method according to claim 1, is characterized in that, said initiator is radical type initiator, is selected from over cure acids initiator or azo-initiator; Water soluble starter adds in batches, before adding, is dissolved in advance in water; Oil-soluble initiator directly adds in the oil phase containing monomer.
7. the nano phase change material emulsion of the wide temperature change scope of preparing according to method described in claim 1～6 any one.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210461555.7A CN103804558A (en) | 2012-11-15 | 2012-11-15 | Nano phase change material emulsion wide in temperature change range and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210461555.7A CN103804558A (en) | 2012-11-15 | 2012-11-15 | Nano phase change material emulsion wide in temperature change range and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103804558A true CN103804558A (en) | 2014-05-21 |
Family
ID=50701986
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210461555.7A Pending CN103804558A (en) | 2012-11-15 | 2012-11-15 | Nano phase change material emulsion wide in temperature change range and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103804558A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109135680A (en) * | 2017-06-28 | 2019-01-04 | 无锡新祥恒包装科技有限公司 | One kind keeping the temperature 12 ~ 18 DEG C of phase change cold accumulating agents for insulin |
| CN109777366A (en) * | 2019-01-30 | 2019-05-21 | 杭州鲁尔新材料科技有限公司 | A kind of preparation method of the pumpable formula phase transformation lotion of low temperature |
| CN109913177A (en) * | 2019-03-04 | 2019-06-21 | 河北工业大学 | Double phase-change accumulation energy automatically cleaning materials for walls and its application |
| CN111763499A (en) * | 2020-06-09 | 2020-10-13 | 上海电力大学 | Micro-nano emulsion phase change material, phase change heat exchange tube and preparation method of phase change material |
| CN113462364A (en) * | 2021-07-01 | 2021-10-01 | 东莞理工学院 | Two-dimensional material MXene stable water-based phase-change emulsion and preparation method thereof |
| CN115029108A (en) * | 2022-06-09 | 2022-09-09 | 北京科技大学 | Heat-conducting enhanced organic phase change microcapsule, preparation method and application |
| CN115287044A (en) * | 2021-05-04 | 2022-11-04 | 纳米及先进材料研发院有限公司 | Rupture-resistant and easy-to-disperse nano-capsule phase change material and synthesis method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1695788A (en) * | 2005-03-29 | 2005-11-16 | 东华大学 | Synthesizing microcapsules of storing energy through phase change by using method of emulsion polymerization |
| CN101255258A (en) * | 2007-03-01 | 2008-09-03 | 香港理工大学 | Functional latex as well as preparation method and uses thereof |
| CN101537333A (en) * | 2009-04-02 | 2009-09-23 | 浙江大学 | Redispersible submicron polymer hollow capsule and preparation method thereof |
| CN101544712A (en) * | 2009-04-02 | 2009-09-30 | 浙江大学 | Method for preparing phase-transition capsule dispersion liquid through mini-emulsion polymerization |
| CN101870861A (en) * | 2010-05-25 | 2010-10-27 | 北京交通大学 | Infrared magnetic phase change material and preparation method thereof |
| CN102492397A (en) * | 2011-11-25 | 2012-06-13 | 河南科技大学 | Preparation method of microencapsulated phase change material with high phase change latent heat value |
| CN102653671A (en) * | 2011-03-02 | 2012-09-05 | 中国科学院化学研究所 | Phase change microcapsule with complex structure and preparation method thereof |
| CN102733192A (en) * | 2012-04-09 | 2012-10-17 | 福建众和股份有限公司 | Finishing technology of nano-grade phase-change microcapsule heat-accumulation temperature-adjustment intelligent textile fabric printed cloth |
-
2012
- 2012-11-15 CN CN201210461555.7A patent/CN103804558A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1695788A (en) * | 2005-03-29 | 2005-11-16 | 东华大学 | Synthesizing microcapsules of storing energy through phase change by using method of emulsion polymerization |
| CN101255258A (en) * | 2007-03-01 | 2008-09-03 | 香港理工大学 | Functional latex as well as preparation method and uses thereof |
| CN101537333A (en) * | 2009-04-02 | 2009-09-23 | 浙江大学 | Redispersible submicron polymer hollow capsule and preparation method thereof |
| CN101544712A (en) * | 2009-04-02 | 2009-09-30 | 浙江大学 | Method for preparing phase-transition capsule dispersion liquid through mini-emulsion polymerization |
| CN101870861A (en) * | 2010-05-25 | 2010-10-27 | 北京交通大学 | Infrared magnetic phase change material and preparation method thereof |
| CN102653671A (en) * | 2011-03-02 | 2012-09-05 | 中国科学院化学研究所 | Phase change microcapsule with complex structure and preparation method thereof |
| CN102492397A (en) * | 2011-11-25 | 2012-06-13 | 河南科技大学 | Preparation method of microencapsulated phase change material with high phase change latent heat value |
| CN102733192A (en) * | 2012-04-09 | 2012-10-17 | 福建众和股份有限公司 | Finishing technology of nano-grade phase-change microcapsule heat-accumulation temperature-adjustment intelligent textile fabric printed cloth |
Non-Patent Citations (2)
| Title |
|---|
| 刘涛 等: "细乳液聚合法可聚合乳化剂制备高稳定性纳米色料的研究", 《材料导报》 * |
| 周春华 等: "可聚合乳化剂合成苯乙烯-丙烯酸丁酯-α-烯烃磺酸钠共聚物乳液", 《化学学报》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109135680A (en) * | 2017-06-28 | 2019-01-04 | 无锡新祥恒包装科技有限公司 | One kind keeping the temperature 12 ~ 18 DEG C of phase change cold accumulating agents for insulin |
| CN109777366A (en) * | 2019-01-30 | 2019-05-21 | 杭州鲁尔新材料科技有限公司 | A kind of preparation method of the pumpable formula phase transformation lotion of low temperature |
| CN109777366B (en) * | 2019-01-30 | 2021-05-04 | 杭州鲁尔新材料科技有限公司 | Preparation method of low-temperature pumpable phase-change emulsion |
| CN109913177A (en) * | 2019-03-04 | 2019-06-21 | 河北工业大学 | Double phase-change accumulation energy automatically cleaning materials for walls and its application |
| CN111763499A (en) * | 2020-06-09 | 2020-10-13 | 上海电力大学 | Micro-nano emulsion phase change material, phase change heat exchange tube and preparation method of phase change material |
| CN115287044A (en) * | 2021-05-04 | 2022-11-04 | 纳米及先进材料研发院有限公司 | Rupture-resistant and easy-to-disperse nano-capsule phase change material and synthesis method thereof |
| CN113462364A (en) * | 2021-07-01 | 2021-10-01 | 东莞理工学院 | Two-dimensional material MXene stable water-based phase-change emulsion and preparation method thereof |
| CN113462364B (en) * | 2021-07-01 | 2023-03-03 | 东莞理工学院 | Two-dimensional material MXene stable water-based phase-change emulsion and preparation method thereof |
| CN115029108A (en) * | 2022-06-09 | 2022-09-09 | 北京科技大学 | Heat-conducting enhanced organic phase change microcapsule, preparation method and application |
| CN115029108B (en) * | 2022-06-09 | 2023-09-15 | 北京科技大学 | Heat conduction enhanced organic phase change microcapsule, preparation method and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103804558A (en) | Nano phase change material emulsion wide in temperature change range and preparation method thereof | |
| CN102030483B (en) | Preparation method of porous antireflection film formed by nanopolymer hollow particles | |
| CN104530302B (en) | A kind of Ludox/polyacrylate dispersion of high silicon content and preparation method thereof | |
| CN104844751B (en) | A kind of micron-level crosslinked polymer hollow microsphere and preparation method thereof | |
| CN1869090B (en) | High oil absorption resin based on rubber and its preparation method | |
| CN101544712A (en) | Method for preparing phase-transition capsule dispersion liquid through mini-emulsion polymerization | |
| CN104231168A (en) | Polymer microsphere temporary plugging agent with ultralow interfacial tension and preparation method thereof | |
| CN104650816A (en) | Low-temperature phase-change energy storage microcapsule and preparation method thereof | |
| CN102433108A (en) | Temperature-resistance salt-resistance filtrate reducer for drilling fluid and preparation method thereof | |
| CN106281147A (en) | A kind of water base binders for electrodes and preparation method | |
| CN102731738B (en) | Polyhedral oligomeric silsesquioxane (POSS) based patterned nano microsphere and preparation method thereof | |
| CN104650828A (en) | Wettability reversal agent, preparation method of wettability reversal agent, reservoir protection agent composition, drilling fluid for low-permeability and ultra-low permeability reservoir and application of drilling fluid | |
| CN103450856A (en) | Microcapsule composite phase change material based on inorganic hydrous salt as well as preparation method and application thereof | |
| NO333327B1 (en) | Cementing mix and its use for cementing oil wells and the like | |
| CN106478904A (en) | A kind of preparation method of the segmented copolymer material with temperature and pH-sensitivity | |
| CN103172774B (en) | The preparation method of the narrow dispersion polyethylene alcohol of high-polymerization degree and application thereof | |
| CN101974138B (en) | Method for preparing amphiphilic gradient copolymer | |
| CN103193991A (en) | Preparation method of bonding polyaniline on surfaces of styrene-acrylate copolymer emulsion particles | |
| CN104926987B (en) | Hydrophobic associating crosslinked microspheres and preparation method thereof | |
| CN103146115A (en) | Polyhedral oligomeric silasesquioxane (POSS)-based load metal nanoparticle and preparation method thereof | |
| CN107417856B (en) | Stable thermoreversible color-changing core-shell polymer emulsion with hysteresis effect and preparation method thereof | |
| CN104117330A (en) | Preparation method for twice coating of low-temperature phase change microcapsule | |
| CN108623734A (en) | A kind of preparation method of polymeric hollow microsphere | |
| CN108219186A (en) | The fluorine-containing porous material of micro-aperture is prepared based on polylactic acid induction thickening effect | |
| CN109126649B (en) | Method for preparing microcapsule by using block copolymer as microcapsule wall material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140521 |