CN111774017B - Phase change microcapsule based on polymer shell and manufacturing method thereof - Google Patents
Phase change microcapsule based on polymer shell and manufacturing method thereof Download PDFInfo
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- CN111774017B CN111774017B CN202010661859.2A CN202010661859A CN111774017B CN 111774017 B CN111774017 B CN 111774017B CN 202010661859 A CN202010661859 A CN 202010661859A CN 111774017 B CN111774017 B CN 111774017B
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- phase
- phase change
- janus particles
- change
- change microcapsule
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- 239000012782 phase change material Substances 0.000 claims abstract description 71
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- 238000000034 method Methods 0.000 claims abstract description 36
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- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 claims description 3
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- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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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)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dispersion Chemistry (AREA)
- Physics & Mathematics (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention provides a phase change microcapsule based on a polymer shell and a manufacturing method thereof. The phase change microcapsule based on a polymer shell layer of the present invention comprises: the phase change composite wall material comprises a phase change core material and a composite wall material coating the phase change core material, wherein the composite wall material is formed by a wall material composition containing Janus particles and a shell layer polymer. The phase change microcapsule based on the polymer shell layer has controllable phase change temperature, high heat storage density and high enthalpy retention rate. The manufacturing method of the phase change microcapsule based on the polymer shell layer can freely regulate and control the phase change temperature of the phase change material, efficiently control the proportion of the phase change material and Janus particles, and has the advantages of simple process, short production period and industrial mass production prospect.
Description
Technical Field
The invention relates to a phase change microcapsule based on a polymer shell and a manufacturing method thereof, in particular to a high enthalpy phase change microcapsule with controllable phase change temperature, high heat storage density and high enthalpy retention rate and a manufacturing method thereof.
Background
Increasing energy consumption requires that people be able to produce, store and utilize energy more efficiently. Waste of heat energy, which is one of the earliest energy sources used by human beings, is a considerable phenomenon, and it is an unbearable technical challenge to save heat energy and improve the use efficiency of heat energy. The storage (cold accumulation and heat accumulation) of energy by utilizing the phase change latent heat of the phase change material is a novel environment-friendly energy-saving technology, has the advantages of small temperature change and high heat accumulation density, and has wide application prospects in the fields of solar energy utilization, recovery of industrial waste heat and waste heat, energy conservation of air conditioners, building heating and the like. Since the phase change material manages thermal energy by utilizing the heat absorption and release phenomenon during the solid-liquid transition, leakage in a liquid state, deformation during the solid-liquid transition, and the like are important defects in the actual use of the phase change material.
Microencapsulation of phase change materials is an important technical solution to address the above-mentioned leakage and deformation. The technology generally firstly utilizes an emulsification technology to obtain uniformly dispersed phase-change material droplets (particles); then coating a shell layer with stable performance on the surface of the phase-change material particles by a chemical or physical means; when the phase change microcapsule is finally obtained in the phase change process, the phase change core is subjected to solid-liquid conversion, and the shell layer is kept in a solid state, so that the leakage and deformation of the phase change material are solved. Therefore, the key point of the microcapsule technology lies in the emulsification of the phase-change material and the preparation of a stable shell layer.
The emulsification process of the phase-change microcapsule can be selected from conventional emulsifiers, such as sodium salt hydrolysate of ethylene methyl ether-maleic anhydride copolymer, sodium salt hydrolysate of isobutylene-maleic anhydride copolymer, sodium salt hydrolysate of styrene-maleic anhydride copolymer, sodium salt hydrolysate of ethylene-maleic anhydride copolymer, copolymer obtained by copolymerizing acrylic acid or methacrylic acid with styrene, ethylene, vinyl alcohol, vinyl acetate, methacrylamide, isobutylene, acrylate, methacrylate or acrylonitrile, polyvinylbenzene sulfonic acid, sodium polyvinylbenzene sulfonate, emulsifier OP-5, emulsifier OP-10, Tween20 (Tween20), Tween60 (Tween60), Tween80 (Tween80), polyethylene glycol octylphenyl ether X-100(TritonX-100), sodium dodecyl sulfate, and the like, Sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate, hexadecyl trimethyl ammonium bromide, dioctyl sodium sulfosuccinate, etc. In recent years, Pickering emulsions have also been widely used for the preparation of phase change microcapsules, and various nanoparticles can be used as stabilizers for Pickering emulsions, such as titanium dioxide, aluminum oxide, zinc oxide, zirconium oxide, iron oxide, silicon dioxide, graphene oxide, kaolinite minerals, attapulgite, multiwall carbon nanotubes, and the like.
According to different preparation methods, phase change microcapsules with different shell materials (wall materials) can be obtained, and currently, most shell materials are single organic matters or inorganic matters. Examples of the organic wall material include: a polyurethane wall material mentioned in patent document 1, a polyurea wall material mentioned in patent document 2, a melamine-modified urea resin-based wall material mentioned in patent document 3, and the like. Examples of the inorganic wall material include: a silica-based wall material mentioned in patent document 4, a phase change microcapsule obtained by condensing graphene oxide on the surface of a phase change material mentioned in patent document 5, and the like.
However, the phase-change microcapsules disclosed at present still have certain defects, and the inventors of the present invention have found through extensive research that the main problems are derived from the intrinsic disadvantages and shortcomings of different phase-change microcapsule preparation technologies.
Although the emulsification process of the phase-change microcapsules is flexible and controllable, the defects of different emulsification means cannot be ignored. For example, conventional low molecular weight emulsifiers can only form stable emulsions at large use levels, and the use of large amounts of emulsifiers increases costs and environmental stress; the macromolecular emulsifier has higher cost and poorer stability; the nanoparticles used in the Pickering emulsion need to be surface modified, so that the process is increased, and the stability of the product is difficult to ensure.
On the other hand, a single organic wall material or inorganic wall material is another non-negligible defect of the phase change microcapsules at present. Although organic wall materials such as polyurethane, melamine-modified urea-formaldehyde resin, melamine-formaldehyde resin, etc. have a good encapsulation effect, the thermal conductivity is low, and a large amount of volatile organic compounds (e.g., formaldehyde) remain in the coated phase change material, which greatly limits the application of the phase change material. Furthermore, most organic wall materials are combustible, and have a plurality of potential safety hazards. In addition, most inorganic wall materials have the advantages of certain flame retardance, relatively constant phase transition temperature, relatively high energy storage density and the like, but have poor packaging effect and relatively brittle wall materials, so that the application of the inorganic wall materials is limited.
Documents of the prior art
Patent document
Patent document 1: CN 110255959A
Patent document 2: CN 110215885A
Patent document 3: CN 107722943A
Patent document 4: CN 107513375A
Patent document 5: CN 103752234A
Disclosure of Invention
Problems to be solved by the invention
One of the objectives of the present invention is to provide a high enthalpy phase change microcapsule with controllable phase change temperature, high heat storage density and high enthalpy retention rate.
In addition, another purpose of the present invention is to provide a method for manufacturing a high enthalpy phase change microcapsule, which can freely adjust and control the phase change temperature of the phase change material, can efficiently control the ratio of the phase change material to the Janus particles, and has the advantages of simple process, short production period and industrial mass production prospect.
Means for solving the problems
The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that, from the designability of Janus granules: the present invention has been accomplished by solving the above problems by obtaining a polymer shell by inducing phase separation through polymerization in a pincering emulsion having stable Janus particles, thereby obtaining a phase change microcapsule having an adjustable phase change temperature and a high enthalpy retention rate.
The present invention has been completed based on the above findings. Namely, the present invention is as follows.
[1] A polymer shell based phase change microcapsule comprising: a phase-change core material and a composite wall material coating the phase-change core material,
wherein the composite wall material is formed from a wall material composition comprising a Janus particle and a shell polymer.
[2] The phase change microcapsule according to [1], wherein the Janus particle comprises an inorganic-polymer type Janus particle, a polymer-polymer type Janus particle, or an inorganic-inorganic type Janus particle.
[3] The phase-change microcapsule according to [1] or [2], wherein the phase-change core material is formed of a phase-change composition containing a phase-change material including at least one selected from the group consisting of hydrocarbon compounds, fatty acid compounds, alcohol compounds, and ester compounds.
[4] The phase-change microcapsule according to [3], wherein the hydrocarbon compound comprises at least one selected from the group consisting of an aliphatic hydrocarbon-based compound having 8 to 100 carbon atoms, an aromatic hydrocarbon-based compound having 6 to 120 carbon atoms, an alicyclic hydrocarbon-based compound having 6 to 100 carbon atoms, and paraffin,
the fatty acid-series compound includes at least one selected from the group consisting of capric acid, lauric acid, myristic acid, pentadecanoic acid, stearic acid, and arachidic acid,
the alcohol compound includes at least one selected from the group consisting of erythritol, dodecanol, tetradecanol, hexadecanol, and erythritol,
the ester compound includes at least one selected from the group consisting of cellulose laurate and cetyl stearate.
[5] The phase-change microcapsule according to any one of [1] to [4], wherein the shell polymer is obtained by a polymerization reaction-induced phase separation method,
preferably, the polymerization monomer forming the shell layer polymer includes at least one selected from the group consisting of a styrenic monomer, a (meth) acrylate monomer, and a diene monomer.
[6] The phase-change microcapsule according to any one of [1] to [5], wherein the phase-change microcapsule has a latent heat of phase change of 20 to 250J/g,
preferably, the enthalpy retention rate of the phase-change microcapsule is 20-99%,
preferably, the average particle diameter of the phase-change microcapsule is 0.1-500 μm,
preferably, the phase change temperature of the phase change microcapsule is-50 to 150 ℃.
[7] A method for manufacturing a polymer shell-based phase change microcapsule according to any one of [1] to [6], comprising:
(a) preparing a dispersed phase: dissolving a polymerization monomer and an initiator in a molten phase-change material, and taking the dispersion system as a disperse phase;
(b) preparing a continuous phase: dispersing the Janus particles in a polar solvent, wherein the dispersion system is used as a continuous phase;
(c) dispersing the dispersed phase obtained in the step (a) in the continuous phase obtained in the step (b) to form a Pickering emulsion; and
(d) and (c) initiating polymerization reaction of the Pickering emulsion obtained in the step (c) under the conditions of heating, normal temperature or illumination to obtain the phase-change microcapsule.
[8] The production method according to [7], wherein in the step (a), the mass ratio of the polymerized monomer to the phase change material is 1:0.1 to 1:100, preferably 1:1 to 1:10,
preferably, the polymerized monomer includes at least one selected from the group consisting of styrenic monomers, (meth) acrylate monomers, and diene monomers,
preferably, the phase change material includes at least one selected from the group consisting of hydrocarbon compounds, fatty acid compounds, alcohol compounds, and ester compounds.
[9] The production method according to [7], wherein in the step (b), the concentration of the Janus particles is 0.05 to 5%, preferably 0.1 to 2%;
preferably, the polar solvent includes at least one selected from the group consisting of water, methanol, ethylene glycol, propylene glycol, glycerol, tetrahydrofuran, formamide, N' -dimethylformamide, and dimethyl sulfoxide,
preferably, the Janus particles comprise inorgano-polymeric Janus particles, polymer-polymeric Janus particles, or inorgano-inorgano Janus particles.
[10] The production method according to [7], wherein in the step (c), the volume ratio of the dispersed phase to the continuous phase is 1:1 to 1:100, preferably 1:1 to 1:50,
preferably, in the step (c), the Pickering emulsion is emulsified by high-speed shearing or ultrasonic wave,
preferably, the shearing speed of the high-speed shearing emulsification is 1000-25000 rpm, the shearing time is 0.5-30 min,
preferably, the ultrasonic frequency during ultrasonic emulsification is 1000-40000 Hz, and the ultrasonic emulsification time is 5-60 min.
[11] The production method according to [7], wherein in the step (d), the polymerization reaction includes radical polymerization, redox polymerization, or photo-initiated polymerization,
preferably, the reaction temperature of the free radical polymerization is 50-90 ℃, preferably 60-80 ℃, the reaction time is 0.5-72 hours, preferably 8-48 hours,
preferably, the reaction temperature of the redox polymerization is-80-60 ℃, preferably 0-40 ℃, the reaction time is 0.5-72 hours, preferably 8-48 hours,
preferably, the photo-initiated polymerization is irradiated by 10-760 nm, preferably 200-760 nm, ultraviolet-visible light at room temperature, and the reaction time is 2-120 min, preferably 5-60 min.
[12] The method for manufacturing a phase-change microcapsule according to [7], wherein the method further comprises:
(e) and (d) a post-treatment step of separating, washing and drying the phase-change microcapsules obtained in the step (d).
ADVANTAGEOUS EFFECTS OF INVENTION
According to the invention, Janus particles are assembled at a two-phase interface, and the phase change microcapsule based on the polymer shell is obtained by inducing phase separation through a polymerization reaction, so that the phase change core material is coated and shaped, and the high enthalpy phase change microcapsule with stable structure, stable performance and controllable cost can be obtained. In addition, the Janus particles are used as a part of the wall material of the phase change microcapsule, and the obtained wall material can have the advantages of both organic wall materials and inorganic wall materials.
The phase change microcapsule based on the polymer shell layer has the characteristics of controllable phase change temperature, high heat storage density and high enthalpy retention rate.
In addition, the manufacturing method of the high enthalpy phase change microcapsule can freely regulate and control the phase change temperature of the phase change material, and can efficiently control the proportion of the phase change material and Janus particles, thereby well realizing that the phase change microcapsule is controllable in structure and composition. In addition, the manufacturing method of the high enthalpy phase change microcapsule has the advantages of simple process, short production period, high raw material conversion rate, convenient operation and industrial mass production prospect. Moreover, the raw materials are pollution-free, and the environment-friendly requirement is met.
Drawings
Fig. 1 is a partial flow diagram of a method of manufacturing high enthalpy phase change microcapsules according to an exemplary embodiment of the present invention.
FIG. 2 shows SiO in example 1 of the present invention2-scanning electron micrographs of PS Janus particles.
Fig. 3 is a scanning electron microscope image of high enthalpy phase change microcapsules according to example 1 of the present invention at different magnifications.
Fig. 4 is a scanning electron microscope image of the shell layer of the high enthalpy phase change microcapsule according to example 1 of the present invention.
FIG. 5 shows SiO in example 2 of the present invention2-scanning electron micrographs of PS Janus particles.
Fig. 6 is a scanning electron microscope image of high enthalpy phase change microcapsules according to example 2 of the present invention at different magnifications.
Fig. 7 is a scanning electron microscope image of the shell layer of the high enthalpy phase change microcapsule according to embodiment 2 of the present invention.
Detailed Description
The present invention will be described in detail below. The technical features described below are explained based on typical embodiments and specific examples of the present invention, but the present invention is not limited to these embodiments and specific examples. It should be noted that:
in the present specification, the "(meth) acrylate" used includes the meanings of "methacrylate" and "acrylate"; the "(meth) acrylic acid" used includes the meaning of "methacrylic acid" as well as "acrylic acid".
In the present specification, the numerical range represented by "numerical value a to numerical value B" means a range including the end point numerical value A, B.
In the present specification, the numerical ranges indicated by "above" or "below" mean the numerical ranges including the numbers.
In the present specification, the meaning of "may" includes both the meaning of performing a certain process and the meaning of not performing a certain process.
As used herein, the term "optional" or "optional" is used to indicate that certain substances, components, performance steps, application conditions, and the like are used or not used.
In the present specification, the unit names used are all international standard unit names, and the "%" used means weight or mass% content, if not specifically stated.
In the present specification, the term "particle diameter" as used herein means an "average particle diameter" unless otherwise specified, and can be measured by a commercial particle sizer.
Reference throughout this specification to "some particular/preferred embodiments," "other particular/preferred embodiments," "embodiments," or the like, means that a particular element (e.g., feature, structure, property, and/or characteristic) described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various embodiments.
< phase-change microcapsules based on Polymer Shell >
The phase change microcapsule based on a polymer shell layer of the present invention comprises: a phase-change core material and a composite wall material coating the phase-change core material,
wherein the composite wall material is formed from a wall material composition comprising a Janus particle and a shell polymer.
In the invention, the phase change core material is encapsulated in the composite wall material, and the composite wall material is formed by the wall material composition containing Janus particles and shell polymers, so that the phase change microcapsule with stable structure and performance can be obtained.
The Janus particles used in the invention have extremely strong designability and can meet various industrial design requirements. In addition, Janus particles have extremely strong emulsifying property, and the physical and chemical properties of the Janus particles different from those of the Janus particles at two ends can reduce the water-oil interface energy like an emulsifier. Also, Janus particles can have a Pickering effect at the water-oil interface as traditional nanoparticles. Thus, Janus particles combine the advantages of traditional emulsifiers with nanoparticles to obtain emulsions with excellent stability in very small amounts.
In addition, the invention utilizes Janus particles to assemble at a two-phase interface, obtains the phase change microcapsule based on the polymer shell layer by a polymerization reaction induced phase separation method, and has the advantages of both organic wall materials and inorganic wall materials. According to the invention, the wall material composition containing Janus particles and the shell polymer is used for forming the wall material, so that the high enthalpy phase change microcapsule with stable structure, stable performance and controllable cost can be obtained.
In some preferred embodiments, the average particle size of the phase change microcapsule based on a polymer shell layer of the present invention is 0.1 to 500. mu.m, preferably 10 to 250. mu.m, and more preferably 20 to 150. mu.m. By controlling the average particle size of the phase change microcapsule based on the polymer shell layer within the range, good interface compatibility can be obtained, the enthalpy retention rate is high, the heat conductivity can be further improved, and the application fields and occasions of the phase change microcapsule are expanded.
In some preferred embodiments, the phase transition temperature of the polymer shell-based phase transition microcapsule of the present invention is-50 to 200 ℃, preferably-50 to 150 ℃, and more preferably-20 to 120 ℃. By enabling the phase change temperature of the phase change microcapsule based on the polymer shell layer to fall within the range, the application of energy allocation, temperature control, energy absorption, memory storage and the like in actual production and life can be facilitated.
In some preferred embodiments, the enthalpy retention rate of the phase change microcapsule based on a polymer shell layer of the present invention is 20 to 99%, preferably 75 to 95%, and more preferably 80 to 93%. Compared with the phase change microcapsule prepared by the traditional method, the phase change microcapsule based on the polymer shell layer has high enthalpy retention rate, so that the phase change microcapsule can absorb and release more heat during working, and the phase change microcapsule with the high enthalpy value has wide application in the fields of aerospace, buildings, automobiles, environmental protection, textile and clothing and the like.
The enthalpy retention rate of the phase-change microcapsule based on the polymer shell layer is similar to the content of the phase-change material in value and can be calculated by melting enthalpy or crystallization enthalpy, and the calculation method comprises the following steps:
enthalpy retention rate ═ Δ Hm/ΔHm0×100％；
Enthalpy retention rate ═ Δ Hc/ΔHc0×100％；
Wherein, Δ Hm0Is the melting enthalpy, Δ H, of the phase change materialmThe melting enthalpy, Delta H, of the obtained high enthalpy phase change microcapsulesc0Is the enthalpy of crystallization, Δ H, of the phase change materialcThe crystallization enthalpy of the obtained high enthalpy value phase change microcapsule is obtained.
In some preferred embodiments, the latent heat of phase change of the phase change microcapsule based on a polymer shell layer of the present invention is 20 to 250J/g, preferably 100 to 250J/g, and more preferably 120 to 250J/g. By making the latent heat of phase change of the phase change microcapsules based on the polymer shell layer fall within the above range, higher latent heat storage can be obtained.
Hereinafter, each structure of the phase change microcapsule having a polymer shell layer according to the present invention will be described in detail.
(composite wall material)
The composite wall material of the present invention is formed from a wall material composition comprising a Janus particle and a shell polymer.
In the invention, the wall material is prepared by adopting a polymerization reaction induced phase separation method. The dispersed phase-change material is dissolved with a polymerization monomer, the polymerization monomer is initiated by an initiator to generate a polymerization reaction to form macromolecules, and the macromolecules are separated due to the reduction of the solubility of the macromolecules in the phase-change material and deposited on an interface of the emulsion to form a shell layer. Meanwhile, Janus particles serving as an emulsion stabilizer are coated on the shell layer, so that the composite wall material is formed.
In some preferred embodiments of the present invention, the composite wall material of the present invention is preferably composed of Janus particles and a shell polymer.
[ Janus particle ]
In the present invention, the term "Janus particles" refers to Janus particles in the broad sense of the art, i.e. not only particles that are not structurally morphologically symmetric (anisotropic), but also particles that are compositionally asymmetric, or both.
In some preferred embodiments of the invention, the Janus particles comprise, for example, silica-polystyrene (SiO)2-PS) Janus particles, silica-polyacrylamide (SiO)2-PAM) inorganic-polymeric Janus particles such as Janus particles; polymer-polymer type Janus particles such as polystyrene-polyacrylate (PS-polyacrylate) Janus particles; or as silica-ferroferric oxide (SiO)2-Fe3O4) Janus particle, silica-Silver (SiO)2-Ag) Janus particles and the like. Of these, inorganic-polymeric Janus particles or inorganic-inorganic Janus particles are preferable. In some preferred embodiments, the inorganic-inorganic Janus particles are preferably inorganic-metallic Janus particles or metallic-metallic Janus particles.
In some preferred embodiments, the Janus particles of the present invention have a hydrophilic portion and a hydrophobic portion.
In some preferred embodiments, the hydrophilic portion of the Janus particles of the present invention can have hydroxyl groups (e.g., alcoholic hydroxyl groups, silicon hydroxyl groups, phenolic hydroxyl groups, etc.), ether groups, amide groups, carboxyl groups, anhydrides or salts thereof, and the like.
In some embodiments, the hydrophilic portion of the Janus particles of the present invention can be comprised of an organic or inorganic material. Examples of the organic substance-forming monomer constituting the hydrophilic portion include, but are not limited to, acrylic monomers, pyrrolidone monomers, acrylamide monomers, (poly) ethylene glycol monomers, (poly) propylene glycol monomers, and the like. These monomers may be used alone or in combination of two or more. Examples of the inorganic substance constituting the hydrophilic portion include, but are not limited to, silicon monoxide, silicon dioxide, titanium dioxide, aluminum oxide, and the like. These inorganic substances may be used alone or in combination of two or more. In some preferred embodiments, the hydrophilic portion of the Janus particles of the present invention preferably comprises an inorganic substance, more preferably comprises silica.
In some embodiments, the hydrophobic portion of the Janus particles of the present invention comprises an organic substance. Examples of the organic substance-forming monomer constituting the hydrophobic portion include, without limitation, styrene-based monomers (e.g., styrene, p-methylstyrene, α -methylstyrene, etc.), (meth) acrylate-based monomers (e.g., methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, etc.), silane-based monomers, siloxane-based monomers, olefin-based monomers, acetal-based monomers, and the like. These monomers may be used alone or in combination of two or more. In some preferred embodiments, the hydrophobic portion of the Janus particles of the present invention preferably comprises a polystyrene-based resin or a poly (meth) acrylate-based resin.
In some preferred embodiments, the combination of hydrophilic and hydrophobic moieties (hydrophilic/hydrophobic) of the Janus particles of the present invention may be exemplified by: silica/polystyrene, silica/poly (meth) acrylate-based monomer, silica/polystyrene-divinylbenzene, silica/poly (meth) acrylate-based monomer-divinylbenzene, silica/polystyrene- (meth) acrylate-based monomer-divinylbenzene, titania/polystyrene-divinylbenzene, titania/poly (meth) acrylate-based monomer-divinylbenzene, and the like.
Specific examples of the Janus particles include: silica-polystyrene Janus particles (SiO)2-PS), silica-polyacrylamide Janus particles (SiO)2-PAM)Polystyrene-polyacrylonitrile Janus particles (PS-PAN), polystyrene-polyacrylate Janus particles (PS-polyacrylate), silica-silver Janus particles (SiO-particles)2-Ag), silica-ferroferric oxide Janus particles (SiO)2-Fe3O4) And the like.
The shape of the Janus particles of the present invention is not particularly limited, and examples thereof include various shapes such as a sphere, a snowman, a dumbbell, a rod, a butterfly, a mushroom, a bullet, a semi-raspberry, a cone, a sheet, a cylinder, and a hamburger. From the viewpoint of achieving the technical effects of the present invention more favorably, the Janus particles of the present invention are preferably those having asymmetric structural morphology, and examples thereof include: has snowman-shaped, dumbbell-shaped, semi-raspberry-shaped, mushroom-shaped and other shapes.
In some preferred embodiments, the Janus particles of the present invention are preferably those having a snowman shape. In the present invention, the term "snowman-like" refers to a three-dimensional structure (as shown in fig. 2) in which two spheres (or approximate spheres) of different sizes are stacked in a partially overlapping manner.
In some embodiments, the Janus particles of the present invention preferably have a size of 20 to 2000nm, more preferably 100 to 1000 nm. In the case where the Janus particles of the present invention are snowman-shaped Janus particles, the ratio of the diameters of the two spheres constituting the "snowman-shape" is preferably 1:9 to 9:1, and more preferably 1:4 to 4: 1.
The preparation method of the Janus particles is not particularly limited, and the Janus particles can be prepared by a method generally used in the art. For example, it can be prepared by a surface selective modification method, an emulsion polymerization method, a seeded emulsion polymerization method, a phase separation method, microfabrication and self-assembly, a dispersion polymerization method, and the like.
In some preferred embodiments, the preparation method of the Janus particles of the present invention can refer to the preparation method of the Janus particles disclosed in chinese patent application CN105440218A, for example. Specifically, the preparation method of the Janus particles comprises the following steps: dispersing polymer particles in water to obtain a seed solution; emulsifying a silane coupling agent, an emulsifying agent, an initiator and the like, adding the emulsified silane coupling agent, the emulsifying agent, the initiator and the like into the seed solution, and carrying out polymerization reaction under mechanical stirring to obtain a suspension of Janus particles; and (3) carrying out spray drying or freeze drying on the obtained suspension of the Janus particles to obtain the Janus particles.
[ Shell Polymer ]
In the present invention, the shell polymer is obtained by phase-inversion induced phase separation of the polymerized monomers during polymerization.
Examples of the polymerizable monomer include: styrene monomers, (meth) acrylate monomers, and diene monomers. These may be used alone or in combination of 2 or more. Among these, styrene-based monomers or (meth) acrylate-based monomers are preferable.
Specific examples of the polymerizable monomer are not particularly limited, and include, for example: styrene, divinylbenzene, methyl acrylate, butyl acrylate, methyl methacrylate, glycidyl methacrylate, 1, 6-hexanediol diacrylate, polyethylene glycol dimethacrylate, butadiene, isoprene, and the like. In some preferred embodiments, the polymerized monomer is preferably styrene, divinylbenzene, methyl acrylate, butyl acrylate, methyl methacrylate, glycidyl methacrylate, 1, 6-hexanediol diacrylate or polyethylene glycol dimethacrylate to obtain a cross-linked shell polymer, which ensures the mechanical strength and toughness of the phase-change microcapsule.
The content of the shell polymer is not particularly limited, and the amount of the shell polymer to be blended is preferably 10 to 1000 parts by mass per 100 parts by mass of the Janus particles. When the content ratio of the shell polymer is within the above range, a phase change microcapsule having excellent mechanical strength and toughness can be obtained.
(phase change core material)
In the present invention, the phase change core material is formed of a phase change composition including a phase change material.
The term "phase change material" as used herein refers to a material that has the ability to absorb or release heat to regulate heat transfer in or within a temperature stability range. The temperature stability range may include a particular transition temperature or a range of transition temperatures. In some cases, a phase change material may be able to inhibit heat transfer for a period of time as the phase change material absorbs or releases heat, typically as the phase change material undergoes a transition between two states. This action is typically temporary and does not occur until the latent heat of the phase change material is absorbed or released during the heating or cooling process. Heat can be stored or removed from the phase change material, and the phase change material typically can be effectively replenished by a source that emits or absorbs heat. For some embodiments, the phase change material may be a mixture of two or more materials. By selecting two or more different materials and forming a mixture, the temperature stability range can be adjusted for any desired application. The resulting mixture, when incorporated into the phase change microcapsules described herein, may exhibit two or more different transition temperatures or a single modified transition temperature.
In the present invention, the phase change material includes hydrocarbon compounds, fatty acid compounds, alcohol compounds, ester compounds, and the like. These may be used alone or in combination of 2 or more. Among these, the phase change material is preferably a hydrocarbon compound, so that the heat conductive property can be effectively improved. Further, when a hydrocarbon compound is used, it is easily available, and a phase change microcapsule having stable characteristics can be obtained using an inexpensive material.
Examples of the hydrocarbon compounds include: an aliphatic hydrocarbon group compound having 8 to 100 carbon atoms (preferably an aliphatic hydrocarbon group compound having 10 to 80 carbon atoms, more preferably an aliphatic hydrocarbon group compound having 15 to 50 carbon atoms, further preferably an aliphatic hydrocarbon group compound having 18 to 30 carbon atoms), an aromatic hydrocarbon group compound having 6 to 120 carbon atoms (preferably an aromatic hydrocarbon group compound having 8 to 100 carbon atoms, more preferably an aromatic hydrocarbon group compound having 10 to 50 carbon atoms, further preferably an aromatic hydrocarbon group compound having 12 to 30 carbon atoms), an alicyclic hydrocarbon group compound having 6 to 100 carbon atoms (preferably an alicyclic hydrocarbon group compound having 6 to 80 carbon atoms, more preferably an alicyclic hydrocarbon group compound having 6 to 50 carbon atoms, further preferably an alicyclic hydrocarbon group compound having 6 to 30 carbon atoms), a method for producing the same, and a method for producing the same, Paraffin (melting point 5-80 ℃ C.), and the like.
The aliphatic hydrocarbon-based compound having 8 to 100 carbon atoms may be a linear or branched aliphatic hydrocarbon-based compound, and examples thereof include, but are not limited to, n-octadecane, n-nonadecane, n-eicosane, n-heneicosane, n-docosane, n-tetracosane, n-pentacosane, n-hexacosane, n-heptacosane, n-octacosane, and the like.
Examples of the aromatic hydrocarbon-based compound having 6 to 120 carbon atoms include, but are not limited to, benzene, naphthalene, biphenyl, ortho-terphenyl, n-terphenyl, and the like. In some embodiments, the aromatic hydrocarbyl compound having 6 to 120 carbon atoms may be a substituted aromatic hydrocarbyl compound having 6 to 100 carbon atoms, preferably C1-C40An alkyl-substituted aromatic hydrocarbon-based compound having 6 to 100 carbon atoms. C1-C40Examples of alkyl-substituted aromatic hydrocarbyl compounds include, but are not limited to, dodecylbenzene, tetradecylbenzene, hexadecylbenzene, hexylnaphthalene, decylnaphthalene, and the like.
Examples of the alicyclic hydrocarbon compound having 6 to 100 carbon atoms include, but are not limited to, cyclohexane, cyclooctane, cyclodecane and the like.
The fatty acid-series compound is preferably a saturated or unsaturated C6-C30Fatty acids, examples of which include, but are not limited to, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, and the like. These may be used alone or in combination of 2 or more.
As the alcohol compound, C is preferred3-C20Fatty alcohols, examples of which include, but are not limited to, glycerol, erythritol, dodecanol, tetradecanol, hexadecanol, erythritol, stearyl alcohol, oleyl alcohol, mixtures such as coconut fatty alcohol, and so-called oxo alcohols obtained by hydroformylating α -olefins and further reacting, and the like. These may be used alone or in combination of 2 or more.
As the ester compound, C of a fatty acid is preferred1-C30Alkyl esters, examples of which include, but are not limited to, cetyl stearate, cellulose laurate, propyl palmitate, methyl stearate, methyl palmitate, and the like. These may be used alone or in combination of 2 or more.
The choice of phase change material may depend on the latent heat and transition temperature of the phase change material. The latent heat of a phase change material is typically associated with its ability to reduce or eliminate heat transfer. In some cases, the latent heat of the phase change material can be at least about 40J/g, such as at least about 50J/g, at least about 60J/g, at least about 70J/g, preferably at least about 80J/g, particularly preferably at least about 90J/g, and most preferably at least about 100J/g. Thus, for example, the latent heat of the phase change material may be in the range of 40 to 400J/g, preferably 60 to 400J/g, particularly preferably 80 to 400J/g, and most preferably 100 to 400J/g. The transition temperature of a phase change material is typically related to a desired temperature or a desired temperature range that can be maintained by the phase change material. In some cases, the transition temperature of the phase change material may be in the range of-10 to 110 deg.C, such as 0 to 100 deg.C, 0 to 50 deg.C, 10 to 50 deg.C, preferably 15 to 45 deg.C, particularly preferably 22 to 40 deg.C, and most preferably 22 to 28 deg.C.
< method for producing phase-change microcapsules based on Polymer Shell >
The manufacturing method of the phase change microcapsule based on the polymer shell layer comprises the following steps:
(a) preparing a dispersed phase: dissolving a polymerization monomer and an initiator in a molten phase-change material, and taking the dispersion system as a disperse phase;
(b) preparing a continuous phase: dispersing the Janus particles in a polar solvent, wherein the dispersion system is used as a continuous phase;
(c) dispersing the dispersed phase obtained in the step (a) in the continuous phase obtained in the step (b) to form a Pickering emulsion; and
(d) and (c) initiating polymerization reaction of the Pickering emulsion obtained in the step (c) under illumination, normal temperature or heating condition to obtain the polymer shell-based phase change microcapsule of the invention.
In addition, in the case where the effect of the present invention is not impaired, means such as optional pretreatment and post-treatment may be used in combination with the above-described steps according to actual production conditions or needs.
In a preferred embodiment of the present invention, the method for manufacturing a phase change microcapsule based on a polymer shell layer of the present invention may further comprise: (e) and (d) a post-treatment step of separating, washing and drying the phase-change microcapsules obtained in the step (d).
Fig. 1 is a partial flow chart of a method for manufacturing a polymer shell-based phase-change microcapsule according to an exemplary embodiment of the present invention. As shown in fig. 1, after the dispersed phase is prepared, in the prepared continuous phase described in step (b), Janus particles are dispersed in a polar solvent, and the dispersion is used as a continuous phase. And then, dispersing the dispersed phase into the continuous phase to form Pickering emulsion, and initiating polymerization reaction under the conditions of illumination, normal temperature or heating to obtain the phase change microcapsule based on the polymer shell.
The above-described respective steps will be described in detail below.
Process (a)
In step (a) of the present invention, a dispersed phase is prepared: the polymeric monomer and initiator are dissolved in the molten phase change material, and the dispersion is used as the dispersed phase.
Examples of the polymerizable monomer include: styrene monomers, (meth) acrylate monomers, diene monomers, and the like. These may be used alone or in combination of 2 or more. Among these, styrene-based monomers or (meth) acrylate-based monomers are preferable.
Examples of the polymerizable monomer are not particularly limited, and include, for example: styrene, divinylbenzene, methyl acrylate, butyl acrylate, methyl methacrylate, ethylene glycol dimethacrylate, glycidyl methacrylate, 1, 6-hexanediol diacrylate, polyethylene glycol dimethacrylate, butadiene, isoprene, and the like. In some preferred embodiments, the polymerized monomer is preferably styrene, divinylbenzene, methyl acrylate, butyl acrylate, methyl methacrylate, glycidyl methacrylate, 1, 6-hexanediol diacrylate, ethylene glycol dimethacrylate, or polyethylene glycol dimethacrylate, to ensure the mechanical strength and toughness of the phase-change microcapsule.
Examples of the initiator system include: free radical initiation systems, redox initiation systems, photoinitiation systems, and the like.
The initiator is not particularly limited, and examples thereof include: azobisisobutyronitrile, dibenzoyl peroxide, cumene hydroperoxide, dibenzoyl peroxide/dimethylaniline, cumene hydroperoxide/4-methoxy-N, N-dimethylaniline, 2-hydroxy-methylphenylpropane-1-one (Darocur 1173), isopropylthioxanthone and the like. In some preferred embodiments, the initiator is preferably azobisisobutyronitrile, dibenzoyl peroxide/dimethylaniline, Darocur 1173 to ensure the polymerization reaction, and finally, the phase-change microcapsule shell with mechanical strength and toughness is effectively obtained.
Examples of the phase change material include: hydrocarbon compounds, fatty acid compounds, alcohol compounds, ester compounds, and the like. These may be used alone or in combination of 2 or more. Among these, the phase change material is preferably a hydrocarbon compound from the viewpoint of further enhancing the enthalpy of phase change.
Examples of the hydrocarbon compound, the fatty acid compound, the alcohol compound, and the ester compound include the same hydrocarbon compound, the fatty acid compound, the alcohol compound, and the ester compound used for the phase change material of the phase change microcapsule, and the same modes can be used.
In the step (a) of the present invention, the content of the polymerized monomer is preferably 1 to 50 parts by mass, more preferably 10 to 40 parts by mass, based on 100 parts by mass of the phase change material.
When the amount of the polymerization monomer is 1 part by mass or more, a phase-change microcapsule having excellent mechanical strength and toughness can be obtained. In addition, if the amount of the polymerization monomer is 50 parts by mass or less, the enthalpy retention rate of the high enthalpy phase change microcapsule of the present invention is increased.
In some preferred embodiments, the mass ratio of the polymerized monomer to the phase change material is preferably 1:0.1 to 1:100, and preferably 1:1 to 1: 10. By setting the mass ratio of the monomer to the phase change material within the above range, the high enthalpy phase change microcapsule of the present invention can have stronger mechanical properties and enthalpy retention rate.
In the present invention, the mass ratio of the initiator to the polymerizable monomer is preferably 0.1:100 to 10:100, and preferably 0.5:100 to 5: 100. By setting the mass ratio of the initiator to the polymerizable monomer within the above range, a shell polymer having good mechanical properties can be obtained in a relatively short time.
In the present invention, the preparation of the dispersed phase can be carried out by a conventional method. For example, the dispersed phase can be easily prepared by mixing the above components and sufficiently stirring and mixing them. The manner of charging the polymerization monomer and the initiator is not particularly limited, and the polymerization monomer and the initiator may be charged at once or in portions.
The preparation time and the preparation temperature are not particularly limited. In some preferred embodiments of the present invention, from the viewpoint of obtaining an excellent dispersed phase by thorough mixing, it is preferable that the polymerization monomer and the initiator are dissolved in the melted phase change material at a temperature higher than the melting temperature of the phase change material, and the preparation time is 1 to 30 min.
Step (b)
In step (b) of the present invention, a continuous phase is prepared: janus particles are dispersed in a polar solvent, and the dispersion is taken as a continuous phase.
The Janus particles are the same as those used for the wall material of the phase change microcapsule, and the same modes can be used.
In the invention, the concentration of Janus particles, the difference of the sizes of two ends, the difference of hydrophilicity and hydrophobicity of the two ends and the like all influence the prepared Pickering emulsion. In the step (b) of the present invention, the concentration of the Janus particles is preferably 0.05 to 5%, more preferably 0.1 to 2%, and still more preferably 0.2 to 2%. The Janus particle has a preferred ratio of the sizes of the two ends of 0.2: 1-2: 1, and more preferably 0.5: 1-1.5: 1. In some preferred embodiments, the Janus particles are preferably inorganic-polymeric Janus particles or inorganic-inorganic Janus particles.
In the present invention, the Janus particle surface charge state can be adjusted by adding soluble salts (e.g., sodium chloride, potassium chloride, barium chloride, calcium chloride, sodium carbonate, sodium bicarbonate, sodium sulfate, potassium sulfate, sodium nitrate, potassium nitrate, or calcium nitrate).
Examples of the polar solvent include: water, methanol, ethylene glycol, propylene glycol, glycerol, tetrahydrofuran, formamide, N' -dimethylformamide, dimethyl sulfoxide, and the like. These may be used alone or in combination of 2 or more. Among these, the polar solvent is preferably at least one selected from the group consisting of water, glycerol, N' -dimethylformamide, and dimethyl sulfoxide.
In the present invention, the preparation of the continuous phase can be carried out by a conventional method. For example, the continuous phase is formulated by compounding the above-mentioned respective ingredients and uniformly dispersing by ultrasound.
The preparation time and the preparation temperature are not particularly limited. In some preferred embodiments of the present invention, from the viewpoint of obtaining an excellent continuous phase by uniform dispersion, it is preferable that the Janus particles are dispersed in the polar solvent at room temperature (for example, 20 to 25 ℃) for a preparation time of 1 to 30 min.
Step (c)
In the step (c) of the present invention, the dispersed phase obtained in the step (a) is dispersed in the continuous phase obtained in the step (b) to form a Pickering emulsion.
More specifically, in the step (c) of the present invention, the dispersed phase obtained in the step (a) is dispersed in the continuous phase obtained in the step (b), and the Janus particles are assembled at the interface of the two phases with the aid of a shear to perform an emulsification stabilizing function, thereby forming a Pickering emulsion.
In the step (c) of the present invention, the volume ratio of the dispersed phase to the continuous phase is preferably 1:1 to 1:100, more preferably 1:1 to 1: 50. By making the volume ratio of the dispersed phase to the continuous phase fall within the above range, a more stable emulsion can be obtained, the dispersed phase size can be better controlled, and thus the production efficiency can be improved.
In the step (c) of the present invention, the emulsification is preferably high-speed shear emulsification or ultrasonic emulsification. Under the condition of using high-speed shearing emulsification, the shearing speed of the high-speed shearing emulsification is within the range of 1000-25000 rpm, and the shearing time is within the range of 0.5-30 min. When ultrasonic emulsification is used, the ultrasonic frequency during ultrasonic emulsification is 1000 to 40000Hz, and the ultrasonic emulsification time is 5 to 60min, preferably 10 to 60 min.
Step (d)
In the step (d) of the present invention, the Pickering emulsion obtained in the step (c) is subjected to polymerization reaction under light irradiation, at normal temperature (23 to 25 ℃) or under heating to obtain the phase change microcapsule based on the polymer shell.
According to the invention, in step (d), the polymerization conditions are generally determined by the initiator system chosen. In some preferred embodiments, the polymerization reaction comprises free radical polymerization, redox polymerization, or photo-initiated polymerization.
Under the condition of a free radical initiation system, the reaction temperature is 50-90 ℃, and preferably 60-80 ℃; the reaction time is 0.5-72 h, preferably 8-48 h. Under the condition of a redox initiation system, the reaction temperature is-80-60 ℃, preferably 0-40 ℃, and the reaction time is 0.5-72 hours, preferably 8-48 hours. In the case of a photoinitiation system, the ultraviolet-visible light irradiation is performed at room temperature (23-25 ℃) with the wavelength of 10-760 nm, preferably 200-760 nm, and the reaction time is 2-120 min, preferably 5-60 min, and more preferably 5-30 min.
Step (e)
In the step (e) of the present invention, the phase-change microcapsules obtained in the step (d) are separated, washed and dried.
The separation method is not particularly limited, and means such as centrifugation and suction filtration may be used alone or in combination depending on the actual system.
In some embodiments, in step (e) of the present invention, the phase-change microcapsule mixed system mixed with Janus particles is centrifuged or filtered to obtain a solid phase product, which is then washed and dried to obtain the high enthalpy phase-change microcapsules of the present invention.
In some embodiments of the present invention, the centrifugal treatment may be performed by using a centrifuge to separate the above-mentioned mixed system, so as to obtain the high enthalpy phase change microcapsule of the present invention. The centrifugation conditions are not particularly limited, and for example, the centrifugation speed is 3000 to 15000rpm, and the centrifugation time is 2 to 30 minutes. The suction filtration treatment can separate the mixed system by using a suction filtration device to obtain the high enthalpy phase change microcapsule. The conditions for the suction filtration are not particularly limited, and the pore diameter of the filter paper for suction filtration may be 50 to 500. mu.m, for example.
The drying method is not particularly limited, and a conventional drying method such as freeze drying or spray drying may be used.
Examples
The present invention will be described in further detail below with reference to examples, but the present invention is not limited to these examples.
[ weight percentage of phase change material in phase change microcapsules ]
And obtaining the mass percentage of the phase-change material in the phase-change microcapsule by adopting Thermal Gravimetric Analysis (TGA). Specifically, dried phase change microcapsules were placed in an alumina crucible and the thermogravimetric profile of the sample was tested using TGA (TA Q500) under air atmosphere. The test temperature range is 25-800 ℃, and the heating rate is 10 ℃/min. Finally, the mass percentage of the phase-change material in the phase-change microcapsules can be obtained by comparing the thermal weight loss value of the phase-change material with the mass of the original phase-change microcapsules:
the mass percentage of the phase-change material in the phase-change microcapsule is mPCM/m0×100％；
Wherein m isPCMIs the thermal weight loss value, m, of the phase change material0Is the quality of the original phase-change microcapsule.
[ enthalpy retention ratio (heat storage retention ratio) ]
And (3) analyzing and testing the enthalpy retention rate of the phase-change microcapsules by Differential Scanning Calorimetry (DSC). Specifically, the dried phase change microcapsules are placed in an aluminum crucible, and DSC (TA Q2000) is adopted to test the melting phase change enthalpy, the crystallization phase change enthalpy, the melting phase change temperature and the crystallization phase change temperature of the sample. The test temperature range is 10-80 ℃, and the temperature rise and fall speed is 10 ℃/min. Finally, the enthalpy value retention rate of the Janus phase change microcapsules can be obtained by comparing the phase change point enthalpy value of the Janus phase change microcapsules with the phase change point enthalpy value of the original phase change material:
enthalpy retention rate ═ Δ Hm/ΔHm0×100％；
Enthalpy retention rate ═ Δ Hc/ΔHc0×100％；
Wherein, Δ Hm0Is the melting enthalpy, Δ H, of the phase change materialmThe melting enthalpy, Delta H, of the obtained high enthalpy phase change microcapsulesc0Is the enthalpy of crystallization, Δ H, of the phase change materialcThe crystallization enthalpy of the obtained high enthalpy value phase change microcapsule is obtained.
Example 1
2SiO-Preparation of PS Janus particles
0.15g of Azobisisobutyronitrile (AIBN) was dissolved in 15.00g of Divinylbenzene (DVB) and 0.15g of Sodium Dodecyl Sulfate (SDS) was dissolved in 800.00g of water. Mixing the two solutions, and performing ultrasonic emulsification for 3min to obtain DVB monomer emulsion. Then 25.00g of freeze-dried HP-433 Polystyrene (PS) hollow spheres were dispersed in the monomer emulsion. Stirring for 8h at room temperature to promote DVB to swell PS hollow spheres. And then heating to 70 ℃, and reacting for 12h to obtain the cross-linked PS hollow sphere dispersion liquid. Finally, the seed ball dry powder is obtained by washing with ethanol and water and freeze drying. 10.00g of the dry powder of the seed balls was dispersed in 200.00g of water and the system was warmed to 70 ℃. 6.00g of 3- (methacryloyloxy) propyltrimethoxysilane (MPS), 6.00g of a 1 wt% aqueous potassium persulfate (KPS) solution and 0.20g of SDS were added to 100.00g of water, and ultrasonic emulsification was performed to obtain an MPS monomer emulsion. Gradually dropping the MPS monomer emulsion into the dispersion liquid of the seed ball within 30min, and keeping stirring and reacting for 24 h. Then, 10.00mL of 28 wt% aqueous ammonia was added to the above mixed solution and the reaction was continued for 1 hour to ensure completion of the reaction. The product is subjected to ethanol and deionized waterWashing and freeze-drying to obtain SiO2-PS Janus particles.
SiO obtained by the above production2The SEM of the-PS Janus particles is shown in FIG. 2.
Preparation of phase-change microcapsule based on polymer shell
1.2mL of divinylbenzene, 2.4mL of styrene, and 0.04g of photoinitiator Darocur 1173 (2-hydroxy-methylphenylpropane-1-one) were added to 10.0g of molten paraffin wax (Tm48-50 ℃) and then mixed thoroughly to form a dispersed phase. 1.0g of SiO prepared as described above was added2Dispersing PS Janus particles into 100.0g of water, adding 1.0g of common salt after uniform ultrasonic dispersion to adjust the surface charge state of the Janus particles, and taking the dispersion as a continuous phase. Adding the dispersed phase into the continuous phase, shearing and emulsifying for 10min at 10000rpm by using a high-speed shearing emulsifying machine, transferring the obtained Pickering emulsion into a three-mouth bottle, and reacting for 15min under the irradiation of ultraviolet light. And obtaining the high enthalpy phase change microcapsule dry powder by centrifugal separation, washing and further freeze drying.
The scanning electron microscope photographs of the phase change microcapsule based on the polymer shell prepared by this example under different magnifications are shown in fig. 3. As can be seen from fig. 3, the phase change microcapsule based on a polymer shell prepared in this example has a uniform particle size and good coating properties. Further, as can be seen from the enlarged view shown in fig. 3 (b), the phase change core material is well encapsulated within the composite wall material. From fig. 4, the composite wall material formed by the shell polymer and the Janus particle is confirmed.
In the phase change microcapsule based on the polymer shell layer prepared in this embodiment, the particle size of the phase change microcapsule based on the polymer shell layer is 36.3 ± 9.7 μm; the phase-change material accounts for 91.2 percent of the mass of the phase-change microcapsule; the enthalpy retention rate of the phase-change microcapsule based on the polymer shell layer is 90.6 percent; the phase change temperature of the phase change microcapsule based on the polymer shell layer is 36.5 ℃ and 55.2 ℃; the latent heat of phase change of the phase change microcapsule based on the polymer shell layer is 162.6J/g.
The results show that the phase change microcapsule based on the polymer shell layer has extremely high enthalpy retention rate, and the phase change temperature can be regulated within-50-150 ℃.
Example 2
2SiO-Preparation of PS Janus particles
SiO2The preparation of-PS Janus particles was similar to example 1 except that the amount of 3- (methacryloyloxy) propyltrimethoxysilane (MPS) used was varied to obtain a larger silica end. The method comprises the following specific steps: 0.15g of Azobisisobutyronitrile (AIBN) was dissolved in 15.00g of Divinylbenzene (DVB) and 0.15g of Sodium Dodecyl Sulfate (SDS) was dissolved in 800.00g of water. Mixing the two solutions, and performing ultrasonic emulsification for 3min to obtain DVB monomer emulsion. Then 25.00g of freeze-dried HP-433 Polystyrene (PS) hollow spheres were dispersed in the monomer emulsion. Stirring for 8h at room temperature to promote DVB to swell PS hollow spheres. And then heating to 70 ℃, and reacting for 12h to obtain the cross-linked PS hollow sphere dispersion liquid. Finally, the seed ball dry powder is obtained by washing with ethanol and water and freeze drying. 10.00g of the dry powder of the seed balls was dispersed in 200.00g of water and the system was warmed to 70 ℃. 9.00g of 3- (methacryloyloxy) propyltrimethoxysilane (MPS), 9.00g of a 1 wt% aqueous potassium persulfate (KPS) solution and 0.20g of SDS were added to 100.00g of water, and ultrasonic emulsification was performed to obtain an MPS monomer emulsion. Gradually dropping the MPS monomer emulsion into the dispersion liquid of the seed ball within 30min, and keeping stirring and reacting for 24 h. Then, 10.00mL of 28 wt% aqueous ammonia was added to the above mixed solution and the reaction was continued for 1 hour to ensure completion of the reaction. Washing the product with ethanol and deionized water, and freeze-drying to obtain SiO2-PS Janus particles.
SiO obtained by the above production2The SEM of the-PS Janus particles is shown in FIG. 5.
Preparation of phase-change microcapsule based on polymer shell
1.2mL of ethylene glycol dimethacrylate, 2.4mL of n-butyl acrylate, and 0.04g of the initiator Azobisisobutyronitrile (AIBN) were added to 10.0g of paraffin wax (TmAnd (48-50 ℃) and then dispersed fully to form a dispersed phase. 0.1g of SiO prepared as described above was added2-PS Janus particles dispersed in 100.0g of water, ultrasonically dispersedAfter homogenizing, 1.0g of common salt was added to adjust the surface charge state of Janus particles, and the dispersion was used as a continuous phase. Adding the dispersed phase into the continuous phase, shearing and emulsifying for 10min at 10000rpm by using a high-speed shearing emulsifying machine, transferring the obtained Pickering emulsion into a three-mouth bottle, and reacting for 12h at 70 ℃ under mechanical stirring. And obtaining the phase-change microcapsule dry powder based on the polymer shell layer by centrifugal separation, washing and further freeze drying.
The scanning electron microscope photographs of the phase change microcapsule based on the polymer shell prepared by this example under different magnifications are shown in fig. 6. As can be seen from fig. 6, the phase change microcapsules based on polymer shells prepared in this example have uniform particle size and good coating properties. Further, as can be seen from the enlarged view shown in fig. 6 (b), the phase change core material is well encapsulated within the wall material. From fig. 7, the composite wall material formed by the shell polymer and the Janus particle is confirmed.
In the phase change microcapsule based on the polymer shell layer prepared in this embodiment, the particle size of the phase change microcapsule based on the polymer shell layer is 28.4 ± 3.1 μm; the phase-change material accounts for 90.2 percent of the mass of the phase-change microcapsule; the enthalpy retention rate of the phase change microcapsule based on the polymer shell layer is 89.6 percent; the phase change temperature of the phase change microcapsule based on the polymer shell layer is 36.0 ℃ and 54.8 ℃; the latent heat of phase change of the phase change microcapsule based on the polymer shell layer is 160.8J/g.
The results show that the high enthalpy phase change microcapsule has high enthalpy retention rate, and the phase change temperature can be regulated within-50-150 ℃.
Having described embodiments of the present disclosure, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the disclosed embodiments. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments. The terminology used herein is chosen in order to best explain the principles of the embodiments, the practical application, or improvements made to the technology in the marketplace, or to enable others of ordinary skill in the art to understand the embodiments disclosed herein.
Industrial applicability
The phase change microcapsule based on the polymer shell layer has the characteristics of controllable phase change temperature, high heat storage density, excellent heat conduction performance and high enthalpy retention rate, and can be widely applied to the fields of textile, building energy conservation, electronic component heat management, waste heat recovery and the like and the military fields of space heat protection materials, weapon equipment warehouse wall temperature control, wearable equipment and the like. In addition, the manufacturing method of the phase change microcapsule based on the polymer shell layer has the advantages of simple process, short production period, high raw material conversion rate, convenient operation and industrial mass production prospect.
Claims (27)
1. A phase change microcapsule based on a polymer shell, comprising: a phase-change core material and a composite wall material coating the phase-change core material,
wherein the composite wall material is composed of Janus particles and shell polymers,
the average grain diameter of the phase-change microcapsule is 20-150 mu m,
the Janus particles are silica-polystyrene Janus particles,
the polymerization monomers forming the shell layer polymer comprise styrene monomers or (meth) acrylate monomers,
the styrene monomers are styrene and divinylbenzene.
2. The phase-change microcapsule according to claim 1, wherein the phase-change core material is formed of a phase-change composition comprising a phase-change material including at least one selected from the group consisting of hydrocarbon compounds, fatty acid compounds, alcohol compounds, and ester compounds.
3. The phase-change microcapsule according to claim 2, wherein said hydrocarbon compound comprises at least one selected from the group consisting of an aliphatic hydrocarbon-based compound having 8 to 100 carbon atoms, an aromatic hydrocarbon-based compound having 6 to 120 carbon atoms, an alicyclic hydrocarbon-based compound having 6 to 100 carbon atoms, and paraffin wax,
the fatty acid-series compound includes at least one selected from the group consisting of capric acid, lauric acid, myristic acid, pentadecanoic acid, stearic acid, and arachidic acid,
the alcohol compound includes at least one selected from the group consisting of erythritol, dodecanol, tetradecanol, hexadecanol, and erythritol,
the ester compound includes at least one selected from the group consisting of cellulose laurate and cetyl stearate.
4. Phase change microcapsules according to claim 1 or 2 characterized in that the shell polymer is obtained by polymerization induced phase separation.
5. The phase-change microcapsule according to claim 1 or 2, wherein the phase-change microcapsule has a latent heat of phase change of 20 to 250J/g.
6. The phase-change microcapsule according to claim 1 or 2, wherein the enthalpy retention rate of the phase-change microcapsule is 20 to 99%.
7. The phase-change microcapsule according to claim 1 or 2, wherein the phase-change temperature of the phase-change microcapsule is-50 to 150 ℃.
8. A method for manufacturing a polymer shell based phase change microcapsule according to any one of claims 1 to 7, comprising:
(a) preparing a dispersed phase: dissolving a polymerization monomer and an initiator in a molten phase-change material, and taking the dispersion system as a disperse phase;
(b) preparing a continuous phase: dispersing the Janus particles in a polar solvent, wherein the dispersion system is used as a continuous phase;
(c) dispersing the dispersed phase obtained in the step (a) in the continuous phase obtained in the step (b) to form a Pickering emulsion; and
(d) initiating polymerization reaction of the Pickering emulsion obtained in the step (c) under the conditions of heating, normal temperature or illumination to obtain the phase-change microcapsule,
the polymerized monomer comprises styrene monomers or (methyl) acrylate monomers,
the styrene monomer is styrene and divinyl benzene,
the Janus particles are silica-polystyrene Janus particles.
9. The method according to claim 8, wherein in the step (a), the mass ratio of the polymerized monomer to the phase change material is 1:0.1 to 1: 100.
10. The method according to claim 8, wherein in the step (a), the mass ratio of the polymerized monomer to the phase change material is 1:1 to 1: 10.
11. The manufacturing method according to claim 8, wherein the phase change material includes at least one selected from the group consisting of hydrocarbon compounds, fatty acid compounds, alcohol compounds, and ester compounds.
12. The production method according to claim 8, wherein in the step (b), the concentration of the Janus particles is 0.05 to 5%.
13. The production method according to claim 8, wherein in the step (b), the concentration of the Janus particles is 0.1 to 2%.
14. The production method according to claim 8, wherein the polar solvent includes at least one selected from the group consisting of water, methanol, ethylene glycol, propylene glycol, glycerol, tetrahydrofuran, formamide, N' -dimethylformamide, and dimethyl sulfoxide.
15. The production method according to claim 8, wherein in the step (c), the volume ratio of the dispersed phase to the continuous phase is 1:1 to 1: 100.
16. The production method according to claim 8, wherein in the step (c), the volume ratio of the dispersed phase to the continuous phase is 1:1 to 1: 50.
17. The production method according to claim 8, wherein in the step (c), the Pickering emulsion is emulsified by high-speed shearing or ultrasonic emulsification.
18. The method according to claim 17, wherein the high-speed shearing emulsification has a shearing speed of 1000 to 25000rpm and a shearing time of 0.5 to 30 min.
19. The method according to claim 17, wherein the ultrasonic frequency at the time of ultrasonic emulsification is 1000 to 40000Hz, and the time of ultrasonic emulsification is 5 to 60 min.
20. The method according to claim 8, wherein in the step (d), the polymerization reaction includes radical polymerization, redox polymerization, or photo-initiated polymerization.
21. The method according to claim 20, wherein the reaction temperature of the radical polymerization is 50 to 90 ℃ and the reaction time is 0.5 to 72 hours.
22. The method according to claim 20, wherein the reaction temperature of the radical polymerization is 60 to 80 ℃ and the reaction time is 8 to 48 hours.
23. The production method according to claim 20, wherein the redox polymerization is carried out at a reaction temperature of-80 to 60 ℃ for a reaction time of 0.5 to 72 hours.
24. The production method according to claim 20, wherein the redox polymerization is carried out at a reaction temperature of 0 to 40 ℃ for a reaction time of 8 to 48 hours.
25. The method of claim 20, wherein the photo-initiated polymerization is performed at room temperature with 10-760 nm UV-visible light irradiation for 2-120 min.
26. The method of claim 20, wherein the photo-initiated polymerization is performed at room temperature by irradiation with 200-760 nm UV-visible light for 5-60 min.
27. The manufacturing method according to claim 8, characterized by further comprising: (e) and (d) a post-treatment step of separating, washing and drying the phase-change microcapsules obtained in the step (d).
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| CN113105838A (en) * | 2021-05-12 | 2021-07-13 | 苏州环明电子科技有限公司 | Programmable stepped heat dissipation and temperature control film for electronic equipment |
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