CN101544712A - Method for preparing phase-transition capsule dispersion liquid through mini-emulsion polymerization - Google Patents
Method for preparing phase-transition capsule dispersion liquid through mini-emulsion polymerization Download PDFInfo
- Publication number
- CN101544712A CN101544712A CN200910097287A CN200910097287A CN101544712A CN 101544712 A CN101544712 A CN 101544712A CN 200910097287 A CN200910097287 A CN 200910097287A CN 200910097287 A CN200910097287 A CN 200910097287A CN 101544712 A CN101544712 A CN 101544712A
- Authority
- CN
- China
- Prior art keywords
- phase
- mini
- emulsion polymerization
- dispersion liquid
- transition
- 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
- Polymerisation Methods In General (AREA)
Abstract
The invention discloses a method for preparing a phase-transition capsule dispersion liquid through mini-emulsion polymerization, which uses a random copolymer containing dithio-ester radical at the chain end as a chain transfer agent and an emulsifier to perform active radical mini-emulsion polymerization and obtain a phase-transition material microcapsule of which the particle size is between 50 and 500 nanometers through in-situ polymerization. The capsule wall material of the microcapsule is a polymer polymerized from one or more vinyl monomers or more vinyl monomers, the capsule core substance is long-chain alkane or paraffin wax of C8 to C30, and the phase-transition temperature is between 10 and 80 DEG C. The random copolymer chain transfer agent can be synthesized through simple one-step reversible addition fragmentation chain transfer active radical copolymerization, which is convenient to adjust the ratio of a core material to a shell polymer and can improve the emulsion stability. The method for preparing a nano-capsule through soapless mini-emulsion polymerization overcomes the defects of other emulsifiers, which not only has a simple process and is easy to achieve industrial production, but also has good environmental protection significance.
Description
Technical field
The present invention relates to a kind of mini-emulsion polymerization preparation method of phase-transition capsule dispersion liquid.
Background technology
Phase change material is a kind of material that the transformation of solid, liquid, gas phase can take place, and it has huge latent heat of phase change, can absorb, store or discharge a large amount of heats under substantially invariable temperature (being phase transition temperature).Phase change material mainly is divided into solid-solid phase change, solid-liquid phase change, liquid-gas phase change, solid-the gas phase change energy-storage material according to phase deformation type, phase transition process; Can be divided into high, medium and low temperature phase change material according to the transformation temperature scope; Can be divided into inorganic, organic (polymer) phase change material again according to its composition.In recent years, the applied research of phase change material has expanded to aspects such as intelligent automatic air-conditioning and construction thing, wrapping material, pipe container, electrical and electronic component, insulation clothes, energy storage cooker.Organic paraffin class alkane has different fusing points and ctystallizing point, changes in the phase change material the not blending ratio of alkane of the same race, can obtain different transformation temperature scopes.And this phase-change wax nontoxicity, do not corrode, non-hygroscopic, it is stable that its thermal characteristics keeps in life-time service, and latent heat of phase change reaches 100～300J/g, and raw materials cost is very low, is a kind of phase change material that is most widely used now.Because solid-liquid phase transition material liquid state occurs in the phase transition process, in case phase change material leaks, phase change material just can't recycle so, and the while may cause problem of environmental pollution.Therefore, generally be to take the method for micro encapsulation that phase change material is wrapped up with the organic or inorganic thing.The method of existing micro encapsulation generally can obtain micron to millimetre-sized capsule, because particle is too big, it is stable that its dispersion system is difficult to keep, and therefore needs the composite again in use latex that is dispersed into, not only technology is loaded down with trivial details, energy consumption is very big, and cyst wall prescription modulability is very poor.
The art of this patent will propose a kind of based on reversible addition-chain rupture chain transfer activity polymerization (ReversibleAddition-Fragmentation train Transfer Polymerization), be called for short the RAFT technology, used chain-transfer agent claims RAFT reagent) the mini-emulsion polymerization method of mechanism prepares the stabilized nanoscale capsule emulsion of size in 50～500 nanometers.RAFT (Reversible Addition-Fragmentationtrain Transfer Polymerization) RAFT technology, it is a kind of active free radical polymerization, can effectively control the polymkeric substance of synthetic special construction of all kinds, as block polymer, Gradient distribution polymkeric substance.The present invention utilizes hydrophilic monomer and hydrophobic monomer, has synthesized to contain different parents' random copolymers chain transfers (RAFT) reagent of forming, and the end of the chain of this macromole RAFT reagent contains two monothioester groups.These parents' random copolymers macromole RAFT reagent has surfactivity preferably, forms multipoint adsorption easily in small droplet/water termination, improves the stability of emulsion.After profit disperses through high-shear, do not need to add other emulsifying agents, just can obtain stable size is 50～500nm miniemulsion drop.And these amphiphilic random copolymers macromole RAFT reagent will self-assembly between miniemulsion drop water-oil interface, behind initiated polymerization, macromole RAFT reagent itself is exactly a kind of chain-transfer agent efficiently, and free radical will constantly shift chainpropagation by the RAFT reaction between water-oil interface.Therefore in polymerization process, free radical constrains in the outside surface of oil droplet, and initiated polymerization forms polymer chain, shows the living polymerization feature in the polymerization process, and the polymer chain ecto-entad is grown, and forms the capsule of polymkeric substance shell at last.In preparation miniemulsion process, can prepare the Nano capsule of different nucleocapsid ratios easily by adjusting core material and monomeric consumption.Can design the capsule of various different shell thicknesses by this method easily, the Nano capsule of shell layer has Application Prospect in light heat-insulating material.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of mini-emulsion polymerization preparation method of phase-transition capsule dispersion liquid is provided.
The mini-emulsion polymerization preparation method of phase-transition capsule dispersion liquid comprises the steps:
1) with phase change materials, one or more vinyl monomers of 10～100 weight parts or the multi-vinyl monomer of 5～50 weight parts, the oil-soluble initiator of 0.01～10 weight part mixes, and forms oil solution;
2) end of the chain with 0.1～5 weight part contains this chain transfer agents of parents' random copolymers of two monothioester groups and the alkaline matter of 0.1～10 weight part, is dissolved in 50～400 weight parts waters, forms the aqueous solution;
3) aqueous solution and oil solution is mixed, through magnetic agitation 10～40 minutes, pulverize down through high shear field again and form miniemulsion;
4) miniemulsion is moved into reactor, be warming up to 50～95 ℃, polyreaction 2～10 hours slowly cools to the emulsion that discharging after the room temperature obtains Nano capsule.
The molecular structural formula that the described end of the chain contains this chain transfer of parents' random copolymers (RAFT) reagent of two monothioester groups is:
Wherein, the Z group is phenyl, phenmethyl, methyl, ethyl, propyl group, sec.-propyl, butyl and isomer thereof, amyl group and isomer thereof, oxyethyl group, methoxyl group mercaptan, second sulfydryl, 2-methyl-prop sulfydryl, dodecane sulfydryl; The R group is the oligopolymer of a kind of hydrophilic monomer and hydrophobic monomer copolymerization, and wherein containing hydrophilic units is 60～80%, and hydrophobic unit is 20～40%.
The molecular weight that the end of the chain contains this fracture addition of the parents' random copolymers chain transfer agents of two monothioester groups is 1500～10000.Hydrophilic monomer is vinylformic acid, methacrylic acid, acrylamide, Sodium styrene sulfonate or hydroxyethyl methacrylate ethanol; Hydrophobic monomer is methacrylic acid, methyl acrylate, ethyl propenoate, n-butyl acrylate, the special butyl ester of vinylformic acid, methyl methacrylate, butyl methacrylate, Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate, vinylformic acid lauryl alcohol ester, vinylbenzene, Vinyl toluene, t-butyl styrene, vinyl pyrrolidone or N hydroxymethyl acrylamide.Phase change materials is long chain alkane or the paraffin of C8～C30.
Vinyl monomer is methacrylic acid, methyl acrylate, ethyl propenoate, n-butyl acrylate, the special butyl ester of vinylformic acid, methyl methacrylate, butyl methacrylate, Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate, vinylformic acid lauryl alcohol ester, vinylbenzene, Vinyl toluene, t-butyl styrene, vinyl pyrrolidone or N hydroxymethyl acrylamide; Described multi-vinyl monomer is Vinylstyrene, Ethylene glycol dimethacrylate, allyl methyl vinylformic acid, ethylene glycol diacrylate, diacrylate butanediol ester, tetramethylene dimethacrylate, dimethacrylate DOPCP, hexanodioic acid dimethacrylate, dimethacrylate triglycol, dimethacrylate Tetraglycol 99, TriMethylolPropane(TMP) or a tetramethylolmethane tetramethyl-vinylformic acid.
Oil-soluble initiator is water-soluble azo-initiator or the peroxide initiator that is not more than 0.5 gram/every kg water; Alkaline matter is sodium hydroxide, yellow soda ash, sodium bicarbonate, ammoniacal liquor or aniline.The instrument of high shear forces is cell pulverization ultrasonic apparatus, homogenizer or high pressure miniflow dispersing apparatus.
The present invention adopts the dispersion agent of parents' random copolymers RAFT reagent as miniemulsion, its preparation technology is simple, it is connected by chemical bond with the polymkeric substance shell after the polymerization, become the part of polymkeric substance shell, saved and used other emulsifying agents, subsequent applications has been saved aftertreatment tretolite operation, and environmental protection, energy-conservation.Simultaneously, parents' random copolymers RAFT reagent dissolves in the alkaline aqueous solution, therefore can regulate phase change materials and monomer usage ratio easily, the synthetic phase change materials capsule that obtains different polymkeric substance shells.
Description of drawings
Fig. 1 is the transmission electron microscope photo of the last phase-transition capsule dispersion emulsion of embodiment 1;
Fig. 2 is the transmission electron microscope photo of the last phase-transition capsule dispersion emulsion of embodiment 2;
Fig. 3 is the transmission electron microscope photo of the last phase-transition capsule dispersion emulsion of embodiment 3;
Fig. 4 is the transmission electron microscope photo of the last phase-transition capsule dispersion emulsion of embodiment 4;
Fig. 5 is the transmission electron microscope photo of the last phase-transition capsule dispersion emulsion of embodiment 5;
Fig. 6 is the transmission electron microscope photo of the last phase-transition capsule dispersion emulsion of embodiment 6.
Embodiment
The molecular structural formula that the end of the chain contains this fracture addition of the parents' random copolymers chain transfer agents (RAFT) of two monothioester groups is:
Wherein the Z group is phenyl, phenmethyl, methyl, ethyl, propyl group, sec.-propyl, butyl and isomer thereof, amyl group and isomer thereof, oxyethyl group, methoxyl group mercaptan, second sulfydryl, 2-methyl-prop sulfydryl, dodecane sulfydryl; The R group is the oligopolymer of the copolymerization of a kind of hydrophilic monomer and hydrophobic monomer.Variation combination according to Z group and R group can obtain multiple structure.
Used oligopolymer RAFT chemical structure skeleton symbol mainly contains following 4 kinds in the invention process:
Random oligopolymer RAFT (1), by vinylformic acid and vinylbenzene at 2-[(dodecane sulfane base) the sulfo-acyl group]-carry out solution random copolymerization under the sulfane base propionic acid chain-transfer agent to obtain.Wherein vinylformic acid contains 15 unit, and vinylbenzene contains 10 unit.
Random oligopolymer RAFT (2), by methacrylic acid and vinylbenzene at 4-cyano group-4-[(dodecane sulfane base) the sulfo-acyl group]-carry out solution random copolymerization under the sulfane base valeric acid chain-transfer agent to obtain.Wherein methacrylic acid contains 20, and vinylbenzene contains 10.
Random oligopolymer RAFT (3) carries out solution random copolymerization by vinylformic acid and vinylbenzene and obtains under the two thioesters chain-transfer agents of styroyl-1-phenylethyl alcohol.Wherein vinylformic acid contains 10, and vinylbenzene contains 5.
Random oligopolymer RAFT (4) carries out solution random copolymerization by vinylformic acid and methacrylic acid lauryl alcohol ester and obtains under the two thioesters chain-transfer agents of phenyl-1-phenylethyl alcohol.Wherein vinylformic acid contains 12, and vinylbenzene contains 5.
Embodiment 1:
1) with 5 gram solid paraffins, 15 gram methyl methacrylates, 0.08 gram Diisopropyl azodicarboxylate mixes, and forms oil solution;
2) with 0.8 gram parents' random macromolecular chain transfer agent RAFT reagent (1) and 0.2 gram potassium hydroxide, be dissolved in the 100 gram water, form the aqueous solution;
3) aqueous solution and oil solution are mixed pre-emulsification 10 minutes, form miniemulsion down through the ultrasonic device effect of cell pulverization again;
4) miniemulsion is moved into reactor, be warming up to 50 ℃, polyreaction 10 hours slowly cools to the emulsion that discharging after the room temperature obtains Nano capsule.
Embodiment 2:
1) with 4 gram n-hexadecanes, 16 gram vinylbenzene, 0.1 gram Diisopropyl azodicarboxylate mixes the formation oil solution;
2) with 0.6 gram parents' random macromolecular chain transfer agent RAFT reagent (2) and 0.1 gram sodium hydroxide, be dissolved in the 70 gram water, form the aqueous solution;
3) aqueous solution and oil solution are mixed pre-emulsification 30 minutes, form miniemulsion down through the ultrasonic device effect of cell pulverization again;
4) miniemulsion is moved into reactor, be warming up to 80 ℃, polyreaction 6 hours slowly cools to the emulsion that discharging after the room temperature obtains Nano capsule.
Embodiment 3:
1) with 10 gram nonadecanes, 10 gram butyl acrylates, 0.3 gram dimethacrylate DOPCP, 0.1 gram diphenyl peroxide formic acid mixes, and forms oil solution;
2) with 0.3 gram parents' random macromolecular chain transfer agent RAFT reagent (3) and 0.2 gram sodium hydroxide, be dissolved in the 50 gram water, form the aqueous solution;
3) aqueous solution and oil solution are mixed pre-emulsification 30 minutes, circulating down through homogenizer forms miniemulsion 2 times again;
4) miniemulsion is moved into reactor, be warming up to 95 ℃, polyreaction 2 hours slowly cools to the emulsion that discharging after the room temperature obtains Nano capsule.
Embodiment 4:
1) with 2 gram n-hexadecanes, 6 gram nonanes, 12 gram methyl acrylates and 0.3 gram dimethacrylate triglycol, 0.1 gram Diisopropyl azodicarboxylate mixes, and forms oil solution;
2) with 0.1 gram parents' random macromolecular chain transfer agent RAFT reagent (2) and 0.1 gram sodium hydroxide, be dissolved in the 100 gram water, form the aqueous solution;
3) aqueous solution and oil solution are mixed pre-emulsification 30 minutes, form miniemulsion 3 times through the circulation of high pressure miniflow decollator again;
4) miniemulsion is moved into reactor, be warming up to 70 ℃, polyreaction 4 hours slowly cools to the emulsion that discharging after the room temperature obtains Nano capsule.
Embodiment 5:
1) with 5 gram Octadecanes, 10 gram vinylbenzene, 0.01 gram Diisopropyl azodicarboxylate mixes, and forms oil solution;
2) with the ammoniacal liquor of 0.1 gram parents' random macromolecular chain transfer agent RAFT reagent (4) and 1 gram 10%, be dissolved in the 50 gram water, form the aqueous solution;
3) aqueous solution and oil solution are mixed pre-emulsification 30 minutes, form miniemulsion 3 times through the circulation of high pressure miniflow decollator again;
4) miniemulsion is moved into reactor, be warming up to 80 ℃, polyreaction 4 hours slowly cools to the emulsion that discharging after the room temperature obtains Nano capsule.
Embodiment 6:
1) with the positive triacontane of 100 grams, 50 gram methyl methacrylates, 50 gram Ethylene glycol dimethacrylate, 10 gram diphenyl peroxide formic acid mix, and form oil solution;
2) with 5 gram part parents' random macromolecular chain transfer agent RAFT reagent (3) and 10 gram potassium hydroxide, be dissolved in the 400 gram water, form the aqueous solution;
3) aqueous solution and oil solution are mixed pre-emulsification 40 minutes, form miniemulsion down through the ultrasonic device effect of cell pulverization again;
4) miniemulsion is moved into reactor, be warming up to 65 ℃, polyreaction 10 hours slowly cools to the emulsion that discharging after the room temperature obtains Nano capsule.
The capsular every performance of the hollow that embodiment in this invention of table 1 prepares little (receiving) rice.
| Embodiment | Median size (nm) | Morphological structure | Stability | The nucleocapsid ratio |
| 1 | 80.3 | Nucleocapsid | Good | 1：3 |
| 2 | 150.4 | Nucleocapsid | Good | 1：4 |
| 3 | 157.1 | Nucleocapsid | Good | 1：1 |
| 4 | 500 | Nucleocapsid | Good | 1：3 |
| 5 | 108.5 | Nucleocapsid | Good | 1：2 |
| 6 | 110.7 | Nucleocapsid | Good | 2：1 |
Claims (9)
1. the mini-emulsion polymerization preparation method of a phase-transition capsule dispersion liquid is characterized in that, comprises the steps:
1) with phase change materials, one or more vinyl monomers of 10～100 weight parts or the multi-vinyl monomer of 5～50 weight parts, the oil-soluble initiator of 0.01～10 weight part mixes, and forms oil solution;
2) end of the chain with 0.1～5 weight part contains this chain transfer agents of parents' random copolymers of two monothioester groups and the alkaline matter of 0.1～10 weight part, is dissolved in 50～400 weight parts waters, forms the aqueous solution;
3) aqueous solution and oil solution is mixed, through magnetic agitation 10～40 minutes, pulverize down through high shear field again and form miniemulsion;
4) miniemulsion is moved into reactor, be warming up to 50～95 ℃, polyreaction 2～10 hours slowly cools to the emulsion that discharging after the room temperature obtains Nano capsule.
2. the mini-emulsion polymerization preparation method of a kind of phase-transition capsule dispersion liquid according to claim 1 is characterized in that, the molecular structural formula that the described end of the chain contains this chain transfer agents of parents' random copolymers of two monothioester groups is:
Wherein, the Z group is phenyl, phenmethyl, methyl, ethyl, propyl group, sec.-propyl, butyl and isomer thereof, amyl group and isomer thereof, oxyethyl group, methoxyl group mercaptan, second sulfydryl, 2-methyl-prop sulfydryl, dodecane sulfydryl; The R group is the oligopolymer of a kind of hydrophilic monomer and hydrophobic monomer copolymerization, and wherein containing hydrophilic units is 60～80%, and hydrophobic unit is 20～40%.
3. the mini-emulsion polymerization preparation method of a kind of phase-transition capsule dispersion liquid according to claim 1 and 2 is characterized in that, the molecular weight that the described end of the chain contains this chain transfer agents of parents' random copolymers of two monothioester groups is 1500～10000.
4. the mini-emulsion polymerization preparation method of a kind of phase-transition capsule dispersion liquid according to claim 2 is characterized in that, described hydrophilic monomer is vinylformic acid, methacrylic acid, acrylamide, Sodium styrene sulfonate or hydroxyethyl methacrylate ethanol; Hydrophobic monomer is methacrylic acid, methyl acrylate, ethyl propenoate, n-butyl acrylate, the special butyl ester of vinylformic acid, methyl methacrylate, butyl methacrylate, Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate, vinylformic acid lauryl alcohol ester, vinylbenzene, Vinyl toluene, t-butyl styrene, vinyl pyrrolidone or N hydroxymethyl acrylamide.
5. the mini-emulsion polymerization preparation method of a kind of phase-transition capsule dispersion liquid according to claim 1 is characterized in that, described phase change materials is long chain alkane or the paraffin of C8～C30.
6. the mini-emulsion polymerization preparation method of a kind of phase-transition capsule dispersion liquid according to claim 1, it is characterized in that described vinyl monomer is methacrylic acid, methyl acrylate, ethyl propenoate, n-butyl acrylate, the special butyl ester of vinylformic acid, methyl methacrylate, butyl methacrylate, Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate, vinylformic acid lauryl alcohol ester, vinylbenzene, Vinyl toluene, t-butyl styrene, vinyl pyrrolidone or N hydroxymethyl acrylamide; Described multi-vinyl monomer is Vinylstyrene, Ethylene glycol dimethacrylate, allyl methyl vinylformic acid, ethylene glycol diacrylate, diacrylate butanediol ester, tetramethylene dimethacrylate, dimethacrylate DOPCP, hexanodioic acid dimethacrylate, dimethacrylate triglycol, dimethacrylate Tetraglycol 99, TriMethylolPropane(TMP) or a tetramethylolmethane tetramethyl-vinylformic acid.
7. the mini-emulsion polymerization preparation method of a kind of phase-transition capsule dispersion liquid according to claim 1 is characterized in that, described oil-soluble initiator is water-soluble azo-initiator or the peroxide initiator that is not more than 0.5 gram/every kg water;
8. the mini-emulsion polymerization preparation method of a kind of phase-transition capsule dispersion liquid according to claim 1 is characterized in that, described alkaline matter is sodium hydroxide, yellow soda ash, sodium bicarbonate, ammoniacal liquor or aniline.
9. the mini-emulsion polymerization preparation method of a kind of phase-transition capsule dispersion liquid according to claim 1 is characterized in that, the instrument of described high shear forces is cell pulverization ultrasonic apparatus, homogenizer or high pressure miniflow dispersing apparatus.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910097287A CN101544712A (en) | 2009-04-02 | 2009-04-02 | Method for preparing phase-transition capsule dispersion liquid through mini-emulsion polymerization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910097287A CN101544712A (en) | 2009-04-02 | 2009-04-02 | Method for preparing phase-transition capsule dispersion liquid through mini-emulsion polymerization |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101544712A true CN101544712A (en) | 2009-09-30 |
Family
ID=41192105
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910097287A Pending CN101544712A (en) | 2009-04-02 | 2009-04-02 | Method for preparing phase-transition capsule dispersion liquid through mini-emulsion polymerization |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101544712A (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504326A (en) * | 2011-09-28 | 2012-06-20 | 浙江大学 | Method for preparing super thermal isolation polymer materials from polymer nanometer hollow capsules |
| CN102516435A (en) * | 2011-11-21 | 2012-06-27 | 浙江大学 | Method for preparing porous material by reversible addition fragmentation chain transfer polymerization of high internal phase emulsion |
| CN103804558A (en) * | 2012-11-15 | 2014-05-21 | 上海华明高技术（集团）有限公司 | Nano phase change material emulsion wide in temperature change range and preparation method thereof |
| CN103890087A (en) * | 2011-10-21 | 2014-06-25 | 普立万公司 | Thermoplastic elastomer compounds exhibiting high latent heat of fusion in solid state |
| CN105026437A (en) * | 2013-02-15 | 2015-11-04 | 阿科玛法国公司 | Use of methyl mercapto-esters as chain transfer agents |
| CN106366263A (en) * | 2016-08-31 | 2017-02-01 | 中山安康德美生物科技有限公司 | Linear block copolymer, dendritic nano-silver composite and preparation methods of linear block copolymer and dendritic nano-silver composite |
| CN107337745A (en) * | 2017-08-04 | 2017-11-10 | 西北工业大学 | A kind of preparation method of water-in-oil type polymer microcapsule |
| CN109503751A (en) * | 2018-11-07 | 2019-03-22 | 南通泰诺新材料科技有限公司 | A kind of aqueous ink used for plastic lotion and preparation method thereof towards table print |
| 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 |
| CN110820068A (en) * | 2019-10-17 | 2020-02-21 | 浙江大学 | Preparation method of phase change fiber |
| CN111087513A (en) * | 2019-12-17 | 2020-05-01 | 浙江工业大学 | Preparation method of amphiphilic surfactant and controllable preparation method of zwitter-ion nano hollow capsule |
| CN115322511A (en) * | 2022-09-14 | 2022-11-11 | 英创新材料(绍兴)有限公司 | Phase-change heat storage material elastic film and preparation method thereof |
-
2009
- 2009-04-02 CN CN200910097287A patent/CN101544712A/en active Pending
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504326A (en) * | 2011-09-28 | 2012-06-20 | 浙江大学 | Method for preparing super thermal isolation polymer materials from polymer nanometer hollow capsules |
| CN102504326B (en) * | 2011-09-28 | 2013-08-07 | 浙江大学 | Method for preparing super thermal isolation polymer materials from polymer nanometer hollow capsules |
| CN103890087A (en) * | 2011-10-21 | 2014-06-25 | 普立万公司 | Thermoplastic elastomer compounds exhibiting high latent heat of fusion in solid state |
| CN102516435A (en) * | 2011-11-21 | 2012-06-27 | 浙江大学 | Method for preparing porous material by reversible addition fragmentation chain transfer polymerization of high internal phase emulsion |
| CN103804558A (en) * | 2012-11-15 | 2014-05-21 | 上海华明高技术（集团）有限公司 | Nano phase change material emulsion wide in temperature change range and preparation method thereof |
| CN105026437A (en) * | 2013-02-15 | 2015-11-04 | 阿科玛法国公司 | Use of methyl mercapto-esters as chain transfer agents |
| CN106366263B (en) * | 2016-08-31 | 2018-11-13 | 中山安康德美生物科技有限公司 | Linear block copolymers, dendritic nano-silver composite material and preparation method |
| CN106366263A (en) * | 2016-08-31 | 2017-02-01 | 中山安康德美生物科技有限公司 | Linear block copolymer, dendritic nano-silver composite and preparation methods of linear block copolymer and dendritic nano-silver composite |
| CN107337745A (en) * | 2017-08-04 | 2017-11-10 | 西北工业大学 | A kind of preparation method of water-in-oil type polymer microcapsule |
| CN109503751A (en) * | 2018-11-07 | 2019-03-22 | 南通泰诺新材料科技有限公司 | A kind of aqueous ink used for plastic lotion and preparation method thereof towards table print |
| 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 |
| CN110820068A (en) * | 2019-10-17 | 2020-02-21 | 浙江大学 | Preparation method of phase change fiber |
| CN111087513A (en) * | 2019-12-17 | 2020-05-01 | 浙江工业大学 | Preparation method of amphiphilic surfactant and controllable preparation method of zwitter-ion nano hollow capsule |
| CN111087513B (en) * | 2019-12-17 | 2022-05-17 | 浙江工业大学 | Preparation method of amphiphilic surfactant and controllable preparation method of zwitterion nano hollow capsule |
| CN115322511A (en) * | 2022-09-14 | 2022-11-11 | 英创新材料(绍兴)有限公司 | Phase-change heat storage material elastic film and preparation method thereof |
| CN115322511B (en) * | 2022-09-14 | 2024-04-02 | 英创新材料(绍兴)有限公司 | Elastic film of phase-change heat storage material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101544712A (en) | Method for preparing phase-transition capsule dispersion liquid through mini-emulsion polymerization | |
| Chen et al. | Preparation, characterization and thermal properties of nanocapsules containing phase change material n-dodecanol by miniemulsion polymerization with polymerizable emulsifier | |
| CN101670256B (en) | Preparation method of phase change material microcapsule | |
| Chaiyasat et al. | Preparation of poly (divinylbenzene) microencapsulated octadecane by microsuspension polymerization: oil droplets generated by phase inversion emulsification | |
| CN104844751B (en) | A kind of micron-level crosslinked polymer hollow microsphere and preparation method thereof | |
| CN102516435B (en) | Method for preparing porous material by reversible addition fragmentation chain transfer polymerization of high internal phase emulsion | |
| CN111774017B (en) | Phase change microcapsule based on polymer shell and manufacturing method thereof | |
| CN110820068B (en) | Preparation method of phase change fiber | |
| CN105056854A (en) | Preparation method for nanometer TiO2 modified composite phase change microcapsule | |
| CN100336834C (en) | Process for preparing micro capsule of imitating active fine emulsion polymerizing by oil-soluble initiating agent | |
| CN104629690A (en) | Organic-inorganic substance compounded phase change energy storage microcapsule and preparation method thereof | |
| CN102675951A (en) | Water-repellent modified association thickening agent and preparation method thereof | |
| CN106478904A (en) | A kind of preparation method of the segmented copolymer material with temperature and pH-sensitivity | |
| JP5400808B2 (en) | Emulsifier-free polymerization method of acrylic ester emulsion | |
| CN100348625C (en) | Process for preparing microcapsule by initiating active fine emulsion polymerization of water-soluble initiating agent | |
| CN101480596A (en) | Method for preparing phase-change energy-storage nano capsule powder and use thereof | |
| CN103450856A (en) | Microcapsule composite phase change material based on inorganic hydrous salt as well as preparation method and application thereof | |
| CN103304718B (en) | A kind of preparation method of Large stone high-crosslinking-degree polyacrylic ester tiny balloon | |
| CN102267719A (en) | Simple method for preparing titanium dioxide multi-shell hollow spheres and sphere-in-sphere structure | |
| CN104117330B (en) | The preparation method that a kind of low-temperature phase-change micro-capsule secondary is coated | |
| CN109794209A (en) | A kind of preparation method coating phase-change material polyurea microcapsule | |
| CN103804558A (en) | Nano phase change material emulsion wide in temperature change range and preparation method thereof | |
| CN106147718A (en) | A kind of microcapsules of storing energy through phase change and preparation method thereof | |
| CN104437284A (en) | Preparation method of phase change microcapsule | |
| CN108003840A (en) | A kind of preparation method of phase change material emulsion |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C53 | Correction of patent for invention or patent application | ||
| CB03 | Change of inventor or designer information |
Inventor after: Lu Fujun Inventor after: Luo Yingwu Inventor before: Lu Fu Inventor before: Luo Yingwu |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: INVENTOR; FROM: LU FU LUO YINGWU TO: LU FUJUN LUO YINGWU |
|
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20090930 |