CN108276854A - Phase-change microcapsule and its preparation method and application - Google Patents
Phase-change microcapsule and its preparation method and application Download PDFInfo
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
- C09D143/04—Homopolymers or copolymers of monomers containing silicon
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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
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
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- 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
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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- 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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention discloses a kind of phase-change microcapsule and preparation method thereof, the phase-change microcapsule, including shell and the capsule-core that is wrapped in the shell, the cyst wall of shell contain the polymer material of the repeated monomer unit formed by following monomer：The weight ratio of shell and capsule-core is：Shell: capsule-core=1: 1~9；(A) acrylic acid C1~C24The C of Arrcostab or methacrylic acid1~C2440~80wt% of one or more of Arrcostab；(B) 20~60wt% of long-chained monomer, long-chained monomer general formula are：CH2=CR1COO(CH2CH2O)m‑(CH3CHCH2O)nR2, capsule-core is organic phase change material.The product of the present invention is in practical applications, there is good dispersion stabilization especially in the application of aqueous matrix or inorganic material, further increase its energy storage, simultaneously long-chain hydrophilic radical can enhance the interface interaction power between phase-change microcapsule and matrix, avoid material in the application intensity decline the problems such as.
Description
Technical field
The invention belongs to phase-change microcapsule preparation method technical fields.
Background technology
Phase-change material refers to varying with temperature and changing state of matter and can provide the substance of latent heat, i.e., is inhaled from external environment
It receives heat or outwardly environment releases heat, to achieve the purpose that energy utilization and control environment temperature.Although phase-change material
With higher latent heat of phase change, have a wide range of applications in temperature control and heat storage field, but phase-change material
The problem of easily reacting there is also volume change and with ambient enviroment significantly limits its application range.
Microcapsules technology is using film forming cyst wall by volatile, easy leakage or liquid or solid material with reactivity
It is encapsulated in shell and forms molecule.Phase-change microcapsule is exactly will be in phase-change material package to capsule using microcapsules technology
Portion, the phase-change material of microencapsulation have the heat transfer area of bigger, and the volume change of material, carries when can control phase transition well
The stability of high phase-change material.Phase-change microcapsule can be applied to various fields, as building energy conservation, textile garment, food industry,
Functional thermal fluid and military field etc..But in practical applications, especially in aqueous matrix or inorganic material matrix
In, phase-change microcapsule exists more disperses uneven, the weaker problem with the interface binding power of base material, to influence material most
Whole performance.It there is now partial monopoly and disclose the method for improving phase-change material dispersibility.
Patent CN 1570014 discloses a kind of preparation method of the phase-changing energy-storing microcapsules of composite shell, microcapsule shell
For the melamine resin or melamine condensation copolymerization resin being modified through PEG200, the modified resin is in spite of hydrophilic functional group, but chain
Length is shorter, and aqueous areas thickness is insufficient, can not assign phase-change microcapsule sufficient hydrophilicity.
Patent CN 106674513 discloses a kind of phosphorous preparation side with the modified polyether polylol of phase-change accumulation energy segment
Method, the modified polyether polylol, by fully reacting for its P-Cl key and OH, phase transformation are stored up using phosphorus oxychloride as coupling agent
Energy substance polyethylene glycol is keyed in polyether polyol, and reactive hydroxyl end group can be reacted with isocyanates, is improved phase-change material and is existed
Dispersibility in polyurethane system.The terminal hydroxy group of the modified formation of the patent is the dispersion problem being directed in polyurethane system,
It is not strong for the applicability of other systems, especially inorganic system.
In organic-silicon-modified phase-change microcapsule disclosed in patent CN 104592803, polymerized monomer and core material need to pass through pre- breast
Change, emulsion polymerization and post-processing improve emulsion particle and exist to reduce the cohesion of the collision between phase-change microcapsule emulsion particle
Dispersibility in coating.A kind of graphene oxide dispersing type composite phase change energy-storing microcapsules described in patent CN 105860936,
After preparing graphene oxide, binary phase-change material and modification infusorial earth, iterates through graphene and be wrapped to form to carry
Body diatomite is core, and phase-change material is traction body, and graphene oxide is outer protective film, is made to which microcapsules be repeated
Form the system of a cycle, enhancing dispersibility.Stepped temperature adjustment phase-change microcapsule disclosed in patent CN 103933913 uses
Pre-emulsion polymerization prepares lauryl alcohol, solid paraffin is the microcapsules performed polymer of core material, then prepares propylene by free radical polymerization
It is micro- further to be polymerize with acrylic acid pre-emulsion the stepped phase-change accumulation energy of formation by sour pre-emulsion in the reactor for microcapsules performed polymer
Capsule lotion improves the problem of microcapsules are as filler bad dispersibility.The above patent need to undergo repeatedly processing or iterative cycles or
The process repeatedly polymerizeing has that preparation process is complex.
Invention content
The purpose of the present invention is disclosing a kind of phase-change microcapsule and its preparation method and application, to overcome the prior art to exist
Defect.
The phase-change microcapsule, including shell and the capsule-core being wrapped in the shell, the cyst wall of the shell
Polymer material containing the repeated monomer unit formed by following monomer：
The weight ratio of shell and capsule-core is：Shell: capsule-core=1: 1~9；
(A) acrylic acid C1~C24The C of Arrcostab or methacrylic acid1~C24One or more of Arrcostab 40~
80wt%, preferably 50~70wt%；
The acrylic acid C1~C24Arrcostab is selected from methyl acrylate, ethyl acrylate, n-propyl, acrylic acid
N-butyl, isobornyl acrylate, cyclohexyl acrylate, n-octyl, isopropyl acrylate, isobutyl acrylate, third
The secondary butyl ester of olefin(e) acid, tert-butyl acrylate, lauryl ester, acrylic acid 2- diethyl acetamidomalonates, octadecyl ester；
The C of the methacrylic acid1~C24Arrcostab is selected from methyl methacrylate, ethyl methacrylate, methyl
N-propyl, n-BMA, isobornyl methacrylate, cyclohexyl methacrylate, methacrylic acid
The secondary butyl ester of n-octyl, isopropyl methacrylate, Isobutyl methacrylate, methacrylic acid, Tert-butyl Methacrylate, first
Base lauryl ester, methacrylic acid 2- diethyl acetamidomalonates, methacrylic acid octadecane ester；
(B) 20~60wt% of long-chained monomer, preferably 30~50wt%；
The long-chained monomer general formula is：CH2=CR1COO(CH2CH2O)m-(CH3CHCH2O)nR2；
Wherein：
R1Represent H or CH3；
R2Represent alkyl, hydroxyl, alkoxy；
M=0~50, n=0~50, m and n are not simultaneously 0.
Preferred long-chained monomer is selected from such as polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, gathers
Ethylene glycol monomethyl ether methacrylate, polyethylene glycol dimethacrylate, methoxypolyethylene glycol methacrylate, poly- the third two
Alcohol dimethylacrylate, poly- (ethylene glycol and 1,2-propylene glycol) methacrylate.
The capsule-core is organic phase change material；
Preferably, the organic phase change material is selected from one or more of following compounds：
Saturated or unsaturated C10~C40Aliphatic hydrocarbon, as n-tetradecane, n-pentadecane, hexadecane, n-heptadecane,
N-octadecane, NSC 77136, n-eicosane, Heneicosane, n-docosane, n-tricosane, n-tetracosane, positive 20
Five alkane, n-hexacosane, heptacosane, positive octacosane, hexamethylene, hexahydrotoluene, cyclooctane, cyclodecane；
Arene compound, such as benzene, naphthalene, biphenyl, ortho-terphenyl, meta-terphenyl, toluene, dimethylbenzene, ethylo benzene, isopropyl
Benzene, C1~C40Alky-substituted aromatic hydrocarbon；
Saturated or unsaturated C6~C30Aliphatic acid, such as lauric acid, stearic acid, oleic acid, behenic acid, capric acid, Shan Yu
Acid, myristic acid, palmitic acid；
Alcohol, such as ethyl alcohol, propylene glycol, butanediol, pentanediol, hexylene glycol, polyethylene glycol, Glycerin, hexanol, pungent
Alcohol, cyclohexanol, n-dodecanol, tetradecanol, positive hexadecanol, benzoyl alcohol, laruyl alcohol, octadecanol, oleyl alcohol, nutmeg
Alcohol, cetanol, coconut fatty alcohols, oxo alcohol；
C6~C30Fatty amine, such as decyl amine, lauryl amine, tetradecy lamine, cetylamine；
C1~C10Fatty acid alkyl esters, such as palmitate, methyl stearate, methyl hexadecanoate, palmitic acid octadecane
Base ester, methyl cinnamate；
Natural and synthetic wax, as montanic acid wax, Montan-ester waxes, Carnauba wax, polyethylene wax, oxidized wax, polyvinylether wax,
Ethane-acetic acid ethyenyl ester wax, hard wax；
Halogenated hydrocarbons, such as dichloromethane, chloroform, tetrachloromethane, trichloro ethylene, tetrachloro-ethylene, ethlyene dichloride, fluorine chlorine
Hydrocarbon, bromobenzene, chlorinated paraffin, bromo pentadecane, bromo-octadecane, bromo nonadecane, bromo eicosane, bromo docosane；
And petroleum ether, paraffin, diethyl ether, butyl oxide, anisole, 1,4- dioxane, tetrahydrofuran, dimethyl contracting
Aldehyde, glycol ether, diethylene glycol ether, polyglycol ether, acetonitrile, carbon disulfide, sulfolane, nitromethane, nitrobenzene, nutmeg
Sour myristin, isopropyl myristate, oleic acid cetyl ester, terpenes, terpenoid, stearic amide, ethylidene isolenic acid
Amide, hydroxyl dimethoxym ethane base behenamide, N- phenyl-N '-tristearin uride, pyridine.
The average particle size particle size of the phase-change microcapsule is 0.5~100 μm, and wherein particle size can be with well known side
Method, such as adjusted by shearing force, rotating speed and concentration mode.
The preparation method of the phase-change microcapsule, includes the following steps：By water phase at 40 DEG C, oil phase, stirring is added
Polymerisation collects the phase-change microcapsule then from reaction product；
The collection method is conventional, including is filtered, washing and vacuum drying；
10~40 hours dry in 25~80 DEG C of vacuum drying ovens, preferably vacuum drying temperature is 30~60 DEG C, the time 20
~30 hours；
Polymerisation usually carries out at 30~100 DEG C, and preferable polymerization temperature is 40~90 DEG C.
Polymerization reaction time is usually 1~20 hour, and the preferred polymeric time is 2~15 hours.
The water phase includes following weight percentage components：
Preferably, the water phase includes following weight percentage components：
The oil phase includes following weight percentage components：
In monomer, acrylic acid C1~C24The C of Arrcostab or methacrylic acid1~C24One or more of Arrcostab 40~80
Wt%, preferably 50~70wt%, 20~60wt% of long-chained monomer, preferably 30~50wt%；
Preferably, the oil phase includes following weight percentage components：
In monomer, acrylic acid C1~C24The C of Arrcostab or methacrylic acid1~C24One or more of Arrcostab 50~70
Wt%, 30~50wt% of long-chained monomer；
Water phase and the weight ratio of oil phase are：Water phase: oil phase=2~20: 1；
The radical initiator is oil soluble peroxides or azo-compound, and preferred radical initiator is selected from
New peroxide tert-butyl caprate, peroxidating neopentanoic acid tert-pentyl ester, dilauroyl peroxide, peroxidating 2 ethyl hexanoic acid uncle penta
Bis- (2,4- dimethyl) isobutyl cyanides of ester, 2,2 '-azos, 2,2 '-azos two (2- methylbutyronitriles), biphenyl acyl peroxide, mistake
Aoxidize (2 ethyl hexanoic acid) tert-butyl ester, di-t-butyl peroxide, 2,5- dimethyl -2,5- bis(t-butylperoxy)s hexane, mistake
Hydrogen oxide isopropylbenzene, peroxidating bis- (3,5,5- trimethyl acetyls), 4,4 '-azodiisobutyronitriles, azobisisoheptonitrile, peroxidating
The neopentanoic acid tert-butyl ester, dibenzoyl peroxide, bis- (chloro benzoyl peroxides), crosses two carbonic acid at azo-bis-iso-dimethyl
Bis- (2- the ethyihexanoylperoxies) -2,5- dimethylhexanes of dicyclohexyl maleate, tert-butyl peroctoate, 2,5-, t-amyl peroxy -2- ethyls
Bis- (2- the ethyihexanoylperoxies) -2,5- dimethylhexanes of hexane, 2,2 '-azos, bis- pungent valeryl -2,5- dimethyl of 2,5- oneself
One or more of bis- (the new capryl peroxides of 2-) -2,5- dimethylhexanes of alkane, 2,5-；
The crosslinking agent is selected from divinylbenzene, ethylene glycol two (methyl) acrylate, diethylene glycol dimethyl allene
Acid esters, triethylene glycol dimethacrylate, 1,3- dimethacrylates, 1,4- butanediol dimethacrylates
Ester, ethylene glycol dimethacrylate, 1,6-HD dimethylacrylate, glycerol dimethacrylate, 1,3- fourths two
Alcohol dimethylacrylate, neopentylglycol dimethacrylate, 1,10- decanediols dimethylacrylate, trimethacrylate
Sour pentaerythritol ester, pentaerythritol tetramethacrylate, dipentaerythritol hexamethacrylate, methacrylic acid allyl
Ester, trimethylol-propane trimethacrylate, polyethylene glycol (200) dimethylacrylate, polyethylene glycol (400) dimethyl
Acrylate, polyethylene glycol (600) dimethylacrylate, triallyl isocyanate, Triallyl isocyanurate, diethyl
Alkene ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethyleneglycol divinylether, tetraethylene glycol divinyl
Base ether, trimethacrylate acid pentaerythritol ester, dipentaerythritol hexamethacrylate or trimethylol propane trimethyl propylene
One or more of acid esters；
The dispersion stabilizer is selected from colloidal silicon dioxide, colloidal clays, calcium carbonate, calcium phosphate, calcium sulfate, calcium oxalate
Or one or more of barium carbonate；
The stably dispersing auxiliary agent is selected from stably dispersing auxiliary agent methylcellulose, the methylhydroxypropyl of polymer electrolyte
Element, polyvinyl alcohol, gelatin, polyvinylpyrrolidone, polyethylene oxide, chlorination dialkyl dimethyl ammonium, chlorination alkyl trimethyl
Ammonium, sodium alkyl sulfate, sodium alkyl sulfonate, alkyl dimethyl aminoacetic acid glycine betaine or alkyl dihydroxyethyl aminoacetic acid beet
One or more of alkali；
The electrolyte is selected from sodium chloride, potassium chloride, lithium chloride, magnesium chloride, calcium chloride, carbon acid sodium, lithium sulfate, sulphur
One or more of sour sodium, potassium sulfate, magnesium sulfate, ammonium sulfate, sodium carbonate or benzoic acid；
During oil phase and Aqueous dispersions, the paddling process such as mixer for well-distribution, electric mixer, ultrasonic wave can be passed through
Dispersion method is carried out using dispersing methods such as the static dispersion method such as static mixer, microchannel methods.High speed machine shearing rotating speed be
500~10000 turns, the time is 10~100 minutes, and preferably rotating speed is 800~8000 turns, and the time is 20~60 minutes.
In addition, in order to reduce the content of residual monomer, after microcapsules are formed, radical initiator can be rejoined,
Start post-polymerization.
Post-polymerization temperature is usually 60~90 DEG C, and the reaction time is usually 0.5~5h.
The phase-change microcapsule of the present invention can the directly application in the form of aqueous dispersion of microcapsules or powder.
As needed, the microcapsules formed after present invention polymerization can also be separated by spray drying process, stream of hot air
Inlet temperature is usually 100~180 DEG C, and outlet temperature is usually 50~80 DEG C.Aqueous polymer dispersions are sprayed in stream of hot air
Pass through in mist, fine powder is detached usually using cyclone separator or filter separator from the air-flow.The waterborne polymeric of spraying
Dispersion conveying preferably parallel with stream of hot air.
As needed, spray adjuvants can be added in spray drying to promote progress or the low dust-laden of realization of drying process
Amount, improves the particle characteristics such as redispersibility at free mobility.
The spray adjuvants can be selected from polyvinyl alcohol water-soluble polymer, the polyvinyl acetate of partial hydrolysis, fibre
Dimension plain derivative such as hydroxyethyl cellulose, carboxymethyl cellulose, methylcellulose, methyl hydroxyethylcellulose, methylhydroxypropyl
One or more of cellulose, starch, polyvinylpyrrolidone, nvp copolymer, gelatin.
The phase-change microcapsule of the present invention is widely used, one of them wide application field is aqueous insulation insulating moulding coating.
Phase-change microcapsule is added in water paint to be absorbed when can utilize phase-change material phase transformation in microcapsules and discharge a large amount of latent heat, to
Reach insulation, temperature control and energy-efficient effect.Phase-change microcapsule traditional at present is applied to water paint, since it is in resin
Dispersion effect in material is bad, affects the stability and heat insulating effect of coating to a certain extent, while phase transformation is micro-
The introducing of capsule can also reduce the adhesion strength of coating, and then influence its performance.The phase-change microcapsule of the present invention can improve
The problem present on.
The beneficial effects of the invention are as follows：
Long-chained monomer used in the present invention polymerize to form resin shell with other ethylenically unsaturated monomers, wherein long-chain substance
Strand among and/or the longer a large amount of hydrophilic radicals of end chain length greatly improve the hydrophily of phase-change microcapsule
It can so that product of the invention in practical applications, has good especially in the application of aqueous matrix or inorganic material
Dispersion stabilization further increases its energy storage, while long-chain hydrophilic radical can enhance between phase-change microcapsule and matrix
Interface interaction power, avoid material in the application intensity decline the problems such as.
Specific implementation mode
The analysis of phase-change microcapsule uses following method：
(1) average grain diameter and particle diameter distribution
(American-European gram instrument is limited by LS-609 types laser particle size analyzer for the average grain diameter and particle diameter distribution of phase-change microcapsule
Company) it measures.The phase-change microcapsule of drying is fully ground into powder and is scattered in distilled water, after ultrasonic wave dispersion, is utilized
Light scattering principle measures the particles size and distribution of phase-change microcapsule.Wherein D50For average grain diameter, particle diameter distribution SPAN=D50/
(D90-D10)。
The analysis of thermal insulation coatings uses following method：
(1) heat-proof quality
Coating is coated on the calcium silicate board with microporous of 100mm × 100mm × 5mm, after natural drying with 500W iodine-tungsten lamps light source,
The temperature difference testing device of temp probe and temperature recording instrument is tested, and using calcium silicate board with microporous as blank control sample, tests coating
The heat-insulated temperature difference.
(2) adhesion strength
Ground is carbon steel sheet, and paint film average thickness is 150 μm, is tested with elcometer106 spring drawing adhesive force
Instrument surveys its adhesive force to get to paint adhesion intensity using hubbing.
Embodiment 1：
Water phase：
Oil phase：
Preparation method：
By water phase at 40 DEG C, oil phase is added and is stirred to react 40 minutes, and at such a temperature under the rotating speed of 800rpm
Stirring 2 hours is continued to, is then filtered, solids is collected, is washed, it is 20 hours dry in 50 DEG C of vacuum drying oven, you can to obtain
Obtain the phase-change microcapsule.
Embodiment 2：
Water phase：
Oil phase：
Preparation method：
By water phase at 40 DEG C, oil phase is added and is stirred to react 40 minutes, is maintained at 60 DEG C under the rotating speed of 3500rpm
Stirring 9 hours, then filters, and collects solids, washes, 24 hours dry in 50 DEG C of vacuum drying oven, you can described in obtaining
Phase-change microcapsule.
Embodiment 3：
Water phase：
Oil phase：
Preparation method：
By water phase at 40 DEG C, oil phase is added and is stirred to react 40 minutes, is maintained at 90 DEG C under the rotating speed of 8000rpm
Stirring 15 hours, then filters, and collects solids, washes, 20 hours dry in 50 DEG C of vacuum drying oven, you can described in obtaining
Phase-change microcapsule.
The phase-change microcapsule of each embodiment forms and performance is shown in Table 1.
Embodiment 4
Under the rotating speed of 500r/min, 400g water, 8g hydroxyethyl celluloses, 3g auxiliary agents 2- are sequentially added into reactor
Amino-2-methyl -1- propyl alcohol, 5g polyoxyethylene aliphatic alcohol ethers, 40g ethylene glycol, stirring 15min makes each component fill after the completion of addition
Divide and is uniformly mixed；Mixing speed is increased to 1200r/min, the micro- glue of phase transformation that 35g is prepared according to 2 the method for embodiment is added
Capsule continues to stir 20min；Mixing speed is reduced to 1000r/min, 410g silicone acrylic emulsions are added, 20min is stirred after addition
It is set to be sufficiently mixed uniformly, to which the insulating mold coating containing phase-change microcapsule be prepared.
Comparative example 1
Water phase：
Oil phase：
By water phase at 40 DEG C, oil phase is added and is stirred to react 40 minutes, is maintained at 60 DEG C under the rotating speed of 3500rpm
Stirring 9 hours, then filters, and collects solids, washes, 24 hours dry in 50 DEG C of vacuum drying oven, you can described in obtaining
Phase-change microcapsule.
Comparative example 2
Under the rotating speed of 500r/min, 400g water, 8g hydroxyethyl celluloses, 3g auxiliary agents 2- are sequentially added into reactor
Amino-2-methyl -1- propyl alcohol, 5g polyoxyethylene aliphatic alcohol ethers, 40g ethylene glycol, stirring 15min makes each component fill after the completion of addition
Divide and is uniformly mixed；Mixing speed is increased to 1200r/min, the micro- glue of phase transformation that 35g is prepared according to 1 the method for comparative example is added
Capsule continues to stir 20min；Mixing speed is reduced to 1000r/min, 410g silicone acrylic emulsions are added, 20min is stirred after addition
It is set to be sufficiently mixed uniformly, to which the insulating mold coating containing phase-change microcapsule be prepared.
1 phase-change microcapsule of table forms and performance
It can be found that the particle diameter distribution of each phase-change microcapsule is equal by the particles size and distribution result of phase-change microcapsule in table 1
It is even.
Thermal insulation coatings performance of the table 2 containing phase-change microcapsule
| Coating property | Embodiment 4 | Comparative example 2 |
| Basic performance | It is uniformly dispersed, is not layered | Dispersion is more uneven, there is layering |
| The heat-insulated temperature difference (DEG C) | 16 | 10 |
| Adhesion strength (MPa) | 6.3 | 5.1 |
By being found in thermal insulation coatings the performance test results of the table 2 containing phase-change microcapsule, the phase transformation containing long-chained monomer is used
Coating dispersion made from microcapsules is more uniformly distributed, and does not occur lamination during storage, storage stability is good, this is because long-chain
Monomer imparts phase-change microcapsule more preferably hydrophilicity, and then it is made to have better dispersion stabilization in water paint,
Energy storage is also further improved；And long-chain hydrophilic radical can enhance the interface between phase-change microcapsule and aqueous matrix
Active force, therefore the thermal insulation coatings adhesion strength prepared by the embodiment 4 containing long-chained monomer phase-change microcapsule is apparently higher than pair
Ratio 2 uses the coating obtained by common phase-change microcapsule.
Claims (11)
1. phase-change microcapsule, which is characterized in that including shell and the capsule-core being wrapped in the shell, the capsule of the shell
Wall contains the polymer material of the repeated monomer unit formed by following monomer：
The weight ratio of shell and capsule-core is：Shell: capsule-core=1: 1~9；
(A) acrylic acid C1~C24The C of Arrcostab or methacrylic acid1~C2440~80wt% of one or more of Arrcostab；
(B) 20~60wt% of long-chained monomer；
The long-chained monomer general formula is：CH2=CR1COO(CH2CH2O)m-(CH3CHCH2O)nR2；
Wherein：
R1Represent H or CH3；
R2Represent alkyl, hydroxyl, alkoxy；
It is 0 when m=0~50, n=0~50, m and n difference；
The capsule-core is organic phase change material.
2. phase-change microcapsule according to claim 1, which is characterized in that the acrylic acid C1~C24Arrcostab is selected from third
E pioic acid methyl ester, ethyl acrylate, n-propyl, n-butyl acrylate, isobornyl acrylate, cyclohexyl acrylate, third
Olefin(e) acid n-octyl, isopropyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, lauryl
Ester, acrylic acid 2- diethyl acetamidomalonates, octadecyl ester；
The C of the methacrylic acid1~C24Arrcostab is selected from methyl methacrylate, ethyl methacrylate, metering system
Sour n-propyl, n-BMA, isobornyl methacrylate, cyclohexyl methacrylate, methacrylic acid are just pungent
The secondary butyl ester of ester, isopropyl methacrylate, Isobutyl methacrylate, methacrylic acid, Tert-butyl Methacrylate, methyl-prop
Olefin(e) acid dodecane ester, methacrylic acid 2- diethyl acetamidomalonates, methacrylic acid octadecane ester.
3. phase-change microcapsule according to claim 1, which is characterized in that the long-chained monomer is selected from such as polyethyleneglycol
Methacrylate, polypropylene glycol monomethacrylate, methoxypolyethylene glycol methacrylate, polyethylene glycol dimethyl propylene
Olefin(e) acid ester, methoxypolyethylene glycol methacrylate, polypropylene glycol dimethacrylate, poly- (ethylene glycol and 1,2-propylene glycol) methyl
Acrylate.
4. phase-change microcapsule according to claim 2, which is characterized in that the long-chained monomer is selected from such as polyethyleneglycol
Methacrylate, polypropylene glycol monomethacrylate, methoxypolyethylene glycol methacrylate, polyethylene glycol dimethyl propylene
Olefin(e) acid ester, methoxypolyethylene glycol methacrylate, polypropylene glycol dimethacrylate, poly- (ethylene glycol and 1,2-propylene glycol) methyl
Acrylate.
5. phase-change microcapsule according to claim 1, which is characterized in that the organic phase change material is selected from following chemical combination
One or more of object：
Saturated or unsaturated C10~C40Aliphatic hydrocarbon, arene compound, saturated or unsaturated C6~C30Aliphatic acid, alcohol,
C6~C30Fatty amine, C1~C10Fatty acid alkyl esters, natural and synthetic wax, halogenated hydrocarbons, petroleum ether, paraffin, diethyl ether, two fourths
Ether, anisole, 1,4- dioxane, tetrahydrofuran, dimethylacetal, glycol ether, diethylene glycol ether, polyglycol ether, second
Nitrile, carbon disulfide, sulfolane, nitromethane, nitrobenzene, myristyl myristate, isopropyl myristate, oleic acid hexadecane
Base ester, terpenes, terpenoid, stearic amide, ethylidene isolenic acid amide, hydroxyl dimethoxym ethane base behenamide, N- phenyl-N '-
One or more of stearic uride or pyridine.
6. phase-change microcapsule according to claim 5, which is characterized in that the organic phase change material is selected from positive 14
Alkane, n-pentadecane, hexadecane, n-heptadecane, n-octadecane, NSC 77136, n-eicosane, Heneicosane, positive 22
Alkane, n-tricosane, n-tetracosane, pentacosane, n-hexacosane, heptacosane, positive octacosane, hexamethylene,
Hexahydrotoluene, cyclooctane, cyclodecane, benzene, naphthalene, biphenyl, ortho-terphenyl, meta-terphenyl, toluene, dimethylbenzene, ethylo benzene, isopropyl
Benzene, C1~C40Alky-substituted aromatic hydrocarbon, lauric acid, stearic acid, oleic acid, behenic acid, capric acid, behenic acids, myristic acid, palm fibre
Palmitic acid acid, ethyl alcohol, propylene glycol, butanediol, pentanediol, hexylene glycol, polyethylene glycol, 1,2,3- glycerine, hexanol, octanol, cyclohexanol,
N-dodecanol, tetradecanol, positive hexadecanol, benzoyl alcohol, laruyl alcohol, octadecanol, oleyl alcohol, myristyl alcohol, cetanol, coconut palm
Seed oil fatty alcohol, oxo alcohol, decyl amine, lauryl amine, tetradecy lamine, cetylamine, palmitate, methyl stearate, palmitic acid
Methyl esters, palmitic acid stearyl, methyl cinnamate, montanic acid wax, Montan-ester waxes, Carnauba wax, polyethylene wax, oxidized wax,
Polyvinylether wax, ethane-acetic acid ethyenyl ester wax, hard wax, dichloromethane, chloroform, tetrachloromethane, trichloro ethylene, four chloroethenes
Alkene, ethlyene dichloride, fluorochlorohydrocarbon, bromobenzene, chlorinated paraffin, bromo pentadecane, bromo-octadecane, bromo nonadecane, bromo eicosane,
Bromo docosane.
7. phase-change microcapsule according to claim 5, which is characterized in that the average particle size particle size of the phase-change microcapsule
It is 0.5~100 μm.
8. according to the preparation method of claim 1~7 any one of them phase-change microcapsule, which is characterized in that including following step
Suddenly：The oil phase that water phase is added stirs polymerisation, then from reaction product, collects the phase-change microcapsule, polymerization is anti-
30~100 DEG C are should be, polymerization reaction time is 1~20 hour.
9. the preparation method of phase-change microcapsule according to claim 8, which is characterized in that the water phase includes following weight
Measure the component of percentage：
The oil phase includes following weight percentage components：
In monomer, acrylic acid C1~C24The C of Arrcostab or methacrylic acid1~C24One or more of Arrcostab 40~
80wt%, long-chained monomer 20~60%；
Water phase and the weight ratio of oil phase are：Water phase: oil phase=2~20: 1.
10. the preparation method of phase-change microcapsule according to claim 9, which is characterized in that the radical initiator
For oil soluble peroxides or azo-compound；
The crosslinking agent be selected from divinylbenzene, ethylene glycol two (methyl) acrylate, dimethacrylate,
Triethylene glycol dimethacrylate, 1,3- dimethacrylates, 1,4- butanediol dimethylacrylates, diformazan
Base acrylic acid glycol ester, 1,6-HD dimethylacrylate, glycerol dimethacrylate, 1,3 butylene glycol dimethyl
Acrylate, neopentylglycol dimethacrylate, 1,10- decanediols dimethylacrylate, trimethacrylate acid Ji Wusi
Alcohol ester, pentaerythritol tetramethacrylate, dipentaerythritol hexamethacrylate, allyl methacrylate, three hydroxyl first
Base propane trimethyl acrylic ester, polyethylene glycol (200) dimethylacrylate, polyethylene glycol (400) dimethylacrylate,
Polyethylene glycol (600) dimethylacrylate, triallyl isocyanate, Triallyl isocyanurate, divinyl ether, second
Divinyl ether, diethylene glycol divinyl ether, triethyleneglycol divinylether, tetraethylene glycol divinyl ether, front three
One in base acrylate, pentaerythritol, dipentaerythritol hexamethacrylate or trimethylol-propane trimethacrylate
Kind or more；
The dispersion stabilizer is selected from the mixture of one or more of following compounds (containing two kinds)：Colloid dioxy
One or more of SiClx, colloidal clays, calcium carbonate, calcium phosphate, calcium sulfate, calcium oxalate or barium carbonate；
The stably dispersing auxiliary agent be selected from the stably dispersing auxiliary agent methylcellulose of polymer electrolyte, methylhydroxypropylcellulose,
Polyvinyl alcohol, gelatin, polyvinylpyrrolidone, polyethylene oxide, chlorination dialkyl dimethyl ammonium, alkyl trimethylammonium chloride,
Sodium alkyl sulfate, sodium alkyl sulfonate, alkyl dimethyl aminoacetic acid glycine betaine or alkyl dihydroxyethyl aminoacetic acid glycine betaine
One or more of；
The electrolyte is selected from sodium chloride, potassium chloride, lithium chloride, magnesium chloride, calcium chloride, carbon acid sodium, lithium sulfate, sulfuric acid
One or more of sodium, potassium sulfate, magnesium sulfate, ammonium sulfate, sodium carbonate or benzoic acid.
11. according to the application of claim 1~7 any one of them phase-change microcapsule, which is characterized in that be used to prepare aqueous guarantor
Warm insulating moulding coating.
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