CN117304881A - Phase-change microcapsule material and preparation method and application thereof - Google Patents
Phase-change microcapsule material and preparation method and application thereof Download PDFInfo
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- CN117304881A CN117304881A CN202311251503.1A CN202311251503A CN117304881A CN 117304881 A CN117304881 A CN 117304881A CN 202311251503 A CN202311251503 A CN 202311251503A CN 117304881 A CN117304881 A CN 117304881A
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- 239000000463 material Substances 0.000 title claims abstract description 94
- 239000003094 microcapsule Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 28
- 239000011162 core material Substances 0.000 claims abstract description 27
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 24
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229920000147 Styrene maleic anhydride Polymers 0.000 claims abstract description 22
- 229920005603 alternating copolymer Polymers 0.000 claims abstract description 22
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 230000001105 regulatory effect Effects 0.000 claims abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229920002635 polyurethane Polymers 0.000 claims abstract description 4
- 239000004814 polyurethane Substances 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 4
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 3
- 229920001807 Urea-formaldehyde Polymers 0.000 claims abstract description 3
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 claims abstract description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims description 36
- 230000008859 change Effects 0.000 claims description 34
- 239000000839 emulsion Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 17
- 239000004753 textile Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 4
- 238000005538 encapsulation Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000006068 polycondensation reaction Methods 0.000 claims description 2
- 239000004744 fabric Substances 0.000 abstract description 15
- 238000005338 heat storage Methods 0.000 abstract description 13
- 239000012782 phase change material Substances 0.000 abstract description 13
- 238000003756 stirring Methods 0.000 description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000003995 emulsifying agent Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 238000012695 Interfacial polymerization Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000011010 flushing procedure Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol group Chemical group C(CCCCCCCCCCCCCCC)O BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
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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
-
- 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
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/53—Polyethers
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Dispersion Chemistry (AREA)
- Textile Engineering (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention provides a phase-change microcapsule material, a preparation method and application thereof, wherein the phase-change microcapsule material comprises a wall material and a core material; the wall material comprises at least one of silicon dioxide, titanium dioxide, melamine or urea-formaldehyde resin; the preparation raw materials of the core material comprise polyethylene glycol, a second compound and styrene-maleic anhydride alternating copolymer; the second compound comprises polyurethane and/or cyclohexane. In the invention, the phase-change microcapsule material has good heat storage capacity, higher thermal stability and shape stability, and good phase-change circularity and durability; the phase-change microcapsule material is used for fabric, and the special heat storage and release properties of the phase-change material can be utilized to endow the fabric with a temperature regulating function.
Description
Technical Field
The invention belongs to the technical field of textile materials, and particularly relates to a phase-change microcapsule material, a preparation method and application thereof.
Background
The phase change material can absorb or release energy from the outside through the state transition of the phase change material in a certain temperature range, and the environmental temperature in a certain range can be regulated. The phase change material is widely paid attention to by researchers due to the characteristic of the phase change material, but the phase change material has the problems of phase separation, corrosiveness, easy loss and the like in the use process, so the application is greatly limited. Based on the method, the preparation of the phase change material microcapsule is rapidly developed, and the phase change material microcapsule is coated by a wall material and isolated from the external environment, so that the core material is well protected; therefore, the phase-change microcapsules are widely applied and are applied to the textile field.
At present, the materials and the preparation methods of the phase change material microcapsule are various, and the chemical method preparation process is also mature, including an in-situ polymerization method, an interfacial polymerization method and the like; the in-situ polymerization method has low cost, and the prepared microcapsule has better compactness and stability, but inevitably has free formaldehyde, thereby causing environmental protection problem. The interfacial polymerization method avoids the problem of free formaldehyde, but the reaction rate is difficult to control in the reaction process, so that the compactness and stability of the wall material are poor, and the core material is easy to lose in the actual use process, so that the application range of the microcapsule phase change material is limited.
Therefore, the development of the phase-change microcapsule with good stability, good heat storage capacity, good phase-change cyclicity and good durability and the preparation method thereof is a problem to be solved in the field.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a phase-change microcapsule material, and a preparation method and application thereof. The phase-change microcapsule material has good heat storage capacity, higher thermal stability and shape stability, and good phase-change circularity and durability; the phase change microcapsule material is used for the fabric, and the peculiar heat storage and release properties of the phase change material are utilized to form microclimate in a certain area around the finished fabric, so that the fabric has a certain temperature regulating function, and the heat storage and temperature regulating textile is formed, thereby improving the thermal comfort of the fabric and increasing the added value of the textile.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a phase change microcapsule material comprising a wall material and a core material; the wall material comprises at least one of silicon dioxide, titanium dioxide, melamine or urea-formaldehyde resin; the preparation raw materials of the core material comprise polyethylene glycol, a second compound and styrene-maleic anhydride alternating copolymer; the second compound comprises polyurethane and/or cyclohexane.
In the invention, styrene-maleic anhydride alternating copolymer is used as an emulsifier, and the surface tension is reduced by adsorbing on the surface of particles, so that the dispersion of the particles is promoted, and the obtained microcapsule has narrow and uniform particle size distribution; and the phase change microcapsule material has good heat storage and release capacity, good stability, better phase change cycle performance and durability and long service life by selecting specific core materials and wall materials for compounding, and can be used for fabrics, so that the fabrics have a temperature adjusting function and are comfortable to use.
Preferably, the core material is prepared from polyethylene glycol 97.5-98.2% (e.g., 97.5%, 97.6%, 97.7%, 97.8%, 97.9%, 98%, 98.1%, 98.2%, etc.), a second compound 1-1.5% (e.g., 1%, 1.05%, 1.1%, 1.15%, 1.2%, 1.25%, 1.3%, 1.35%, 1.4%, 1.45%, 1.5%, etc.), and a styrene-maleic anhydride alternating copolymer 0.8-1% (e.g., 0.8%, 0.81%, 0.82%, 0.83%, 0.84%, 0.85%, 0.86%, 0.87%, 0.88%, 0.89%, 0.9%, 0.91%, 0.92%, 0.93%, 0.94%, 0.95%, 0.96%, 0.97%, 0.98%, 0.99%, 1%, etc.).
The polyethylene glycol preferably has a number average molecular weight of 1000 to 3000, and may be 1000, 1200, 1400, 1600, 1800, 2000, 2200, 2400, 2600, 2800, 3000, or the like, for example.
Preferably, the mass ratio of the core material to the wall material is 1 (0.2-0.8), wherein the specific value in (0.2-0.8) can be, for example, 0.2, 0.22, 0.24, 0.26, 0.28, 0.3, 0.32, 0.34, 0.36, 0.38, 0.4, 0.42, 0.44, 0.46, 0.48, 0.5, 0.52, 0.54, 0.56, 0.58, 0.6, 0.62, 0.64, 0.66, 0.68, 0.7, 0.72, 0.74, 0.76, 0.78, 0.8, etc.
Preferably, the particle size of the phase change microcapsule material is 400 to 900nm, for example, 400nm, 450nm, 500nm, 550nm, 600nm, 650nm, 700nm, 750nm, 800nm, 850nm, 900nm, etc.
In the invention, the particle size of the phase-change microcapsule material is smaller than 400nm, and the enthalpy value is reduced; above 900nm, the coating stability becomes poor.
Preferably, the encapsulation efficiency of the phase change microcapsule material is more than or equal to 87%, for example, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, etc.
Preferably, the phase change microcapsule material has a phase change enthalpy of 140-160J/g, for example, 140J/g, 145J/g, 150J/g, 155J/g, 160J/g, etc.
In a second aspect, the present invention provides a method for preparing the phase-change microcapsule material according to the first aspect, the method comprising the steps of:
mixing the wall material and the core material, and performing emulsion polycondensation to obtain the phase-change microcapsule material.
Preferably, the preparation method comprises the following steps:
(1) Mixing polyethylene glycol, a second compound and styrene-maleic anhydride alternating copolymer to obtain emulsion A;
(2) Mixing the emulsion A obtained in the step (1) with a precursor of a wall material, and standing to obtain the phase-change microcapsule material.
Preferably, the temperature of the mixing in the step (1) is 60 to 70 ℃, for example, 60 ℃, 62 ℃, 64 ℃, 66 ℃, 68 ℃, 70 ℃ and the like; the mixing time is 1 to 2 hours, and may be, for example, 1 hour, 1.2 hours, 1.4 hours, 1.6 hours, 1.8 hours, 2 hours, or the like.
Preferably, the rotational speed of the mixing in step (1) is 800 to 1000rpm, and may be, for example, 800rpm, 820rpm, 850rpm, 880rpm, 900rpm, 920rpm, 950rpm, 980rpm, 1000rpm, etc.
Preferably, the temperature of the mixing in the step (2) is 60 to 70 ℃, for example, 60 ℃, 62 ℃, 64 ℃, 66 ℃, 68 ℃, 70 ℃ and the like; the mixing time is 30-45 min, for example, 30min, 32min, 34min, 36min, 38min, 40min, 42min, 44min, 45min, etc.
Preferably, the rotational speed of the mixing in step (2) is 200 to 500rpm, and may be, for example, 200rpm, 220rpm, 250rpm, 280rpm, 300rpm, 320rpm, 340rpm, 360rpm, 380rpm, 400rpm, 420rpm, 440rpm, 460rpm, 480rpm, 500rpm, etc.
Preferably, the step (2) further comprises the step of adding acid to continue mixing after the mixing.
In the present invention, the acid includes hydrochloric acid.
Preferably, the rotation speed of the continuous mixing of the added acid is 400-600 rpm, for example, 400rpm, 420rpm, 440rpm, 460rpm, 480rpm, 500rpm, 520rpm, 540rpm, 560rpm, 580rpm, 600rpm and the like can be used; the time is 3 to 4 hours, and may be, for example, 3 hours, 3.2 hours, 3.4 hours, 3.6 hours, 3.8 hours, 4 hours, etc.
Preferably, the temperature of the standing in the step (2) is 60 to 70 ℃, for example, 60 ℃, 62 ℃, 64 ℃, 66 ℃, 68 ℃, 70 ℃ and the like; the standing time is 5 to 6 hours, and may be, for example, 5 hours, 5.2 hours, 5.4 hours, 5.6 hours, 5.8 hours, 6 hours, or the like.
Preferably, the step of washing and/or drying is included after the standing.
In the invention, the product is completely precipitated by standing, filtered, washed for 3-4 times and dried for 12-16 hours at 60-70 ℃.
As a preferable technical scheme of the invention, the preparation method comprises the following steps:
(1) Mixing polyethylene glycol, a second compound and 0.8-1% of styrene-maleic anhydride alternating copolymer for 1-2 h at the temperature of 60-70 ℃ and the rotating speed of 800-1000 rpm to obtain emulsion A;
(2) Mixing the emulsion A obtained in the step (1) with a precursor of a wall material at the temperature of 60-70 ℃ and the rotating speed of 200-500 rpm for 30-45 min, adding acid into the mixture, continuously mixing the mixture for 3-4 h at the rotating speed of 400-600 rpm, and then standing the mixture for 5-6 h at the temperature of 60-70 ℃ to obtain the phase-change microcapsule material.
According to the preparation method provided by the invention, the emulsion polymerization method is adopted, so that the obtained wall material of the phase-change microcapsule has good compactness and stability, the coating rate is high, the problem of free formaldehyde is avoided, the process is simple, the environment is protected, and the cost is low.
In the invention, styrene-maleic anhydride alternating copolymer is used as an emulsifier, and the surface tension is reduced by adsorbing on the surface of particles, so that the dispersion of the particles is promoted, and the microcapsules with narrow and uniform particle size distribution are obtained; when the usage amount of the emulsifier is too large, the oil phase cannot be wrapped by the oil-water interface, so that the wall material is thinned, and the wrapping rate is reduced.
According to the invention, the stirring speed in the preparation process is controlled, so that the phase-change microcapsule material with good morphology and uniform particle size distribution can be obtained; when the stirring speed is too high, the internal fluid changes from a advection state to a turbulent state, and the particle size distribution is severely changed.
In a third aspect, the present invention provides a textile material comprising a phase change microcapsule material according to the first aspect.
Preferably, the textile material has a temperature regulating function.
The numerical ranges recited herein include not only the recited point values, but also any point values between the recited numerical ranges that are not recited, and are limited to, and for the sake of brevity, the invention is not intended to be exhaustive of the specific point values that the recited range includes.
Compared with the prior art, the invention has the beneficial effects that:
the phase change microcapsule material provided by the invention is of a core-shell structure, has regular spherical morphology and uniform particle size distribution, has encapsulation efficiency of more than 87%, and has phase change enthalpy of about 140-160J/g; the heat storage capacity is good, the thermal stability and the shape stability are high, and the phase change circularity and the durability are good; after 100 times of heating-cooling cycles, the heat storage capacity is still good; the phase change microcapsule material is used for the fabric, and the peculiar heat storage and release properties of the phase change material are utilized to form microclimate in a certain area around the finished fabric, so that the fabric has a certain temperature regulating function, and a heat storage and temperature regulating textile is formed, thereby improving the thermal comfort of the fabric and increasing the added value of the textile; and the cost is low and the environment is protected.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a phase-change microcapsule material, which comprises a wall material and a core material; the mass ratio of the wall material to the core material is 0.5:1; the preparation method of the phase-change microcapsule material comprises the following steps:
adding 97.9% polyethylene glycol (PEG 2000), 1.2% cyclohexane and 0.9% styrene-maleic anhydride alternating copolymer into a three-neck flask in an oil bath at 70 ℃ for fully mixing, and vigorously stirring for 1h at a stirring speed of 900rpm to obtain a uniform emulsion system; then adding a formula amount of ethyl silicate as a silicon source, and continuously stirring for 35min at 400rpm to maintain a stable emulsion system; finally, adding 5% hydrochloric acid aqueous solution into the emulsion, continuously stirring for 4 hours at the stirring speed of 500rpm, stopping stirring after the reaction is finished, standing for 6 hours at the temperature of 60 ℃ to enable the mixture to precipitate completely, filtering the mixed solution, and drying for 16 hours at the temperature of 60 ℃ after 3 times of flushing to obtain the phase change microcapsule material with the particle size of 500 nm.
Example 2
The embodiment provides a phase-change microcapsule material, which comprises a wall material (silicon dioxide) and a core material; the mass ratio of the wall material to the core material is 0.3:1; the preparation method of the phase-change microcapsule material comprises the following steps:
adding 98% polyethylene glycol (PEG 2000), 1.15% cyclohexane and 0.85% styrene-maleic anhydride alternating copolymer into a three-neck flask in an oil bath at 65 ℃ for fully mixing, and vigorously stirring for 2 hours at a stirring speed of 820rpm to obtain a uniform emulsion system; then adding a formula amount of ethyl silicate as a silicon source, and continuously stirring for 45min at a stirring speed of 300rpm to maintain a stable emulsion system; finally, adding 5% hydrochloric acid aqueous solution into the emulsion, continuously stirring for 3 hours at the stirring speed of 600rpm, stopping stirring after the reaction is finished, standing for 5 hours at the temperature of 65 ℃ to enable the mixture to precipitate completely, filtering the mixed solution, and drying for 16 hours at the temperature of 60 ℃ after 3 times of flushing to obtain the phase change microcapsule material with the particle size of 600 nm.
Example 3
The embodiment provides a phase-change microcapsule material, which comprises a wall material and a core material; the mass ratio of the wall material to the core material is 0.7:1; the preparation method of the phase-change microcapsule material comprises the following steps:
adding 97.7% polyethylene glycol (PEG 2000), 1.5% polyurethane and 0.8% styrene-maleic anhydride alternating copolymer into a three-neck flask in an oil bath at 70 ℃ for fully mixing, and vigorously stirring for 2 hours at 980rpm to obtain a uniform emulsion system; then adding a formula amount of ethyl silicate as a silicon source, and continuously stirring for 30min at 480rpm to maintain a stable emulsion system; finally, adding 5% hydrochloric acid aqueous solution into the emulsion, continuously stirring for 3 hours at the stirring speed of 400rpm, stopping stirring after the reaction is finished, standing for 5 hours at 65 ℃ to enable the mixture to precipitate completely, filtering the mixed solution, and drying for 16 hours at 60 ℃ after 3 times of flushing to obtain the phase change microcapsule material with the particle size of 650 nm.
Example 4
The present embodiment provides a phase-change microcapsule material, which is different from embodiment 1 only in that the mass ratio of the wall material to the core material is 0.1:1, and other components, amounts and preparation methods are the same as embodiment 1.
Example 5
The present embodiment provides a phase-change microcapsule material, which is different from embodiment 1 only in that the mass ratio of the wall material to the core material is 1:1, and other components, amounts and preparation methods are the same as embodiment 1.
Example 6
The present example provides a phase-change microcapsule material, which is different from example 1 only in that the content of the styrene-maleic anhydride alternating copolymer is 1.5%, the amount of polyethylene glycol and cyclohexane is adjusted so that the total amount is 100% (the ratio of polyethylene glycol to cyclohexane is unchanged), and other components, amounts and preparation methods are the same as example 1.
Example 7
The present example provides a phase-change microcapsule material, which is different from example 1 only in that the content of the styrene-maleic anhydride alternating copolymer is 0.5%, the amount of polyethylene glycol and cyclohexane is adjusted so that the total amount is 100% (the ratio of polyethylene glycol to cyclohexane is unchanged), and other components, amounts and preparation methods are the same as example 1.
Example 8
The present example provides a phase-change microcapsule material, which is different from example 1 only in that the cyclohexane content is 2%, the amount of the polyethylene glycol and styrene-maleic anhydride alternating copolymer is adjusted so that the total amount is 100% (the ratio of the polyethylene glycol and styrene-maleic anhydride alternating copolymer is unchanged), and other components, amounts and preparation methods are the same as example 1.
Example 9
This example provides a phase change microcapsule material differing from example 1 only in that in the preparation method, the rotational speed of mixing polyethylene glycol (PEG 2000), cyclohexane and styrene-maleic anhydride alternating copolymer is 1200rpm; adding the ethyl silicate with the formula amount as a silicon source, and stirring at a speed of 100rpm; the stirring speed of the aqueous solution of hydrochloric acid was 700rpm, and the other components, amounts and preparation methods were the same as in example 1.
Example 10
The present embodiment provides a phase-change microcapsule material, which differs from embodiment 1 only in that the phase-change microcapsule material is prepared by adopting an interfacial polymerization method, and specifically includes: mixing ethyl silicate, polyethylene glycol and cyclohexane to obtain a solution A; then mixing the styrene-maleic anhydride alternating copolymer with water to obtain a solution B; adding the solution B into the solution A, shearing and emulsifying for 10min at 10000rpm by using a high-speed shearing emulsifying machine, transferring the obtained emulsion into a three-mouth bottle, reacting at 70 ℃ for 12 hours, forming a polymer film on the surface of a core material by using monomers during polymerization reaction, gradually forming a capsule shell, separating, washing and drying to obtain the phase-change microcapsule material, wherein the raw material consumption is the same as that of the embodiment 1.
Comparative example 1
This comparative example provides a phase change microcapsule material which differs from example 1 only in that the polyethylene glycol is replaced with cetyl alcohol, and other components, amounts and preparation methods are the same as example 1.
Comparative example 2
This comparative example provides a phase change microcapsule material which differs from example 1 only in that the styrene-maleic anhydride alternating copolymer is replaced with an isobutylene-maleic anhydride copolymer, and other components, amounts and preparation methods are the same as example 1.
Performance testing
(1) Particle size: nano particle size potentiometric analyzer Nano-ZS90Malvern (united states);
(2) Coating ratio = microcapsule phase change enthalpy/microcapsule core phase change enthalpy 100%;
(3) Enthalpy of phase change: differential Scanning Calorimetry (DSC) Q2000 american TA company;
(4) Durability: GBT 8629-2017 textile trials were tested with home wash and dry procedure 4N method water wash.
The specific test results are shown in table 1.
TABLE 1
As can be seen from Table 1, the phase change microcapsule material provided by the invention uses polyethylene glycol as a core material, and the contents of the core material and the wall material are controlled to be in a specific proportion, and meanwhile, styrene-maleic anhydride alternating copolymer is used as an emulsifier, so that the phase change microcapsule material obtained by emulsion polymerization has the advantages of regular morphology, uniform particle size, good heat storage capacity, higher thermal stability and shape stability, and good phase change circularity and durability; the phase-change microcapsule material is used for fabric, and the peculiar heat storage and release properties of the phase-change material can be utilized to form microclimate in a certain area around the finished fabric, so that the temperature regulating function of the fabric can be endowed.
While the foregoing is directed to embodiments of the present invention, other and further details of the invention may be had by the present invention, it should be understood that the foregoing description is merely illustrative of the present invention and that no limitations are intended to the scope of the invention, except insofar as modifications, equivalents, improvements or modifications are within the spirit and principles of the invention.
Claims (10)
1. A phase change microcapsule material, characterized in that the phase change microcapsule material comprises a wall material and a core material;
the wall material comprises at least one of silicon dioxide, titanium dioxide, melamine or urea-formaldehyde resin;
the preparation raw materials of the core material comprise polyethylene glycol, a second compound and styrene-maleic anhydride alternating copolymer;
the second compound comprises polyurethane and/or cyclohexane.
2. The phase-change microcapsule material according to claim 1, wherein the core material is prepared from 97.5 to 98.2% by mass of polyethylene glycol, 1 to 1.5% by mass of a second compound and 0.8 to 1% by mass of a styrene-maleic anhydride alternating copolymer;
preferably, the polyethylene glycol has a number average molecular weight of 1000 to 3000.
3. The phase-change microcapsule material according to claim 1 or 2, wherein the mass ratio of the core material to the wall material is 1 (0.2 to 0.8).
4. A phase change microcapsule material according to any of claims 1-3, characterized in that the particle size of the phase change microcapsule material is 400-900 nm;
preferably, the encapsulation rate of the phase change microcapsule material is more than or equal to 87%;
preferably, the phase change microcapsule material has a phase change enthalpy of 140-160J/g.
5. A method of preparing a phase change microcapsule material according to any of claims 1-4, comprising the steps of:
mixing the wall material and the core material, and performing emulsion polycondensation to obtain the phase-change microcapsule material.
6. The preparation method according to claim 5, characterized in that the preparation method comprises:
(1) Mixing polyethylene glycol, a second compound and styrene-maleic anhydride alternating copolymer to obtain emulsion A;
(2) Mixing the emulsion A obtained in the step (1) with a precursor of a wall material, and standing to obtain the phase-change microcapsule material.
7. The method according to claim 6, wherein the temperature of the mixing in the step (1) is 60 to 70 ℃ and the mixing time is 1 to 2 hours;
preferably, the rotational speed of the mixing in step (1) is 800-1000 rpm.
8. The method according to claim 6 or 7, wherein the temperature of the mixing in the step (2) is 60 to 70 ℃ and the mixing time is 30 to 45 minutes;
preferably, the rotational speed of the mixing in step (2) is 200-500 rpm;
preferably, the step (2) further comprises the step of adding acid to continue mixing after the mixing;
preferably, the rotation speed of the continuous mixing of the added acid is 400-600 rpm, and the time is 3-4 hours;
preferably, the temperature of the standing in the step (2) is 60-70 ℃, and the standing time is 5-6 h;
preferably, the step of washing and/or drying is included after the standing.
9. The preparation method according to any one of claims 5 to 8, characterized in that the preparation method comprises the steps of:
(1) Mixing polyethylene glycol, a second compound and 0.8-1% of styrene-maleic anhydride alternating copolymer for 1-2 h at the temperature of 60-70 ℃ and the rotating speed of 800-1000 rpm to obtain emulsion A;
(2) Mixing the emulsion A obtained in the step (1) with a precursor of a wall material at the temperature of 60-70 ℃ and the rotating speed of 200-500 rpm for 30-45 min, adding acid into the mixture, continuously mixing the mixture for 3-4 h at the rotating speed of 400-600 rpm, and then standing the mixture for 5-6 h at the temperature of 60-70 ℃ to obtain the phase-change microcapsule material.
10. A textile material, characterized in that it comprises a phase change microcapsule material according to any one of claims 1-4;
preferably, the textile material has a temperature regulating function.
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