CN101701146B - Phase-change material microcapsule and preparation method thereof - Google Patents
Phase-change material microcapsule and preparation method thereof Download PDFInfo
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- CN101701146B CN101701146B CN2009100709036A CN200910070903A CN101701146B CN 101701146 B CN101701146 B CN 101701146B CN 2009100709036 A CN2009100709036 A CN 2009100709036A CN 200910070903 A CN200910070903 A CN 200910070903A CN 101701146 B CN101701146 B CN 101701146B
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Abstract
The invention relates to a phase-change material microcapsule and a preparation method thereof. The microcapsule is prepared by a mixed liquor of an oil-phase component and an aqueous phase component; the oil-phase component accounts for 9-30% of the mixed liquor according to the mass percentage (the same below); the oil-phase component comprises 28-49% of free radical polymerization monomer, 1-9% of crosslinker, 44-70% of organic phase-change material and 1-2% of initiating agent; the aqueous phase component comprises 80-90% of deionized water and 1-20% of emulsifier; the surface of the microcapsule has one or more than hollows, the average grain diameters of which are less than or equal to 90mum and the total volume of which accounts for 20-40% of the microcapsule according to the volume percent; the thermal decomposition temperature of the microcapsule is larger than or equal to 230 DEG C. The preparation method adopts the mass percent composition of the microcapsule and the following technique: firstly, the well-mixed oil phase component is added into the well-mixed aqueous phase solution in the temperature I and the stirring speed I, and stirred into a mixed emulsion in the stirring speed II; and then the temperature of the mixed emulsion is raised to II; and finally the mixed emulsion is filtered, separated, mixed, washed with deionized water for 2 to 5 times after being fully stirred, thus obtaining the microcapsule wet cake; or the microcapsule wet cake is dried till reaching constant weight, thus obtaining the microcapsule dry powder.
Description
Technical field
The present invention relates to the phase-change material micro-capsule technology, specifically is a kind ofly to have thermal energy storage and utilize phase-change material micro-capsule of function and preparation method thereof.
Background technology
Phase change material is to be studied discovery the sixties in 20th century, is developed a kind of energy-conserving and environment-protective material of application after the seventies in 20th century, also is a kind of energy storage material of cleaning.Phase change material can absorb or emit a large amount of latent heats of phase change in phase transition process, be widely used in fields such as Heating,Ventilating and Air Conditioning (HVAC), energy saving building, sun power utilization, clothes, and is significant aspect " energy-conservation, reduction of discharging ".Phase-change material micro-capsule is a kind of phase change material particulate that adopts macromolecular material, metallic substance or non-metallic material etc. to coat.Can realize the permanent solid state of phase change material by micro encapsulation,, also seepage can not take place, thereby widen the Application Areas of phase-change material micro-capsule even the phase change material in the microcapsule is in liquid state.But the heat decomposition temperature of general phase-change material micro-capsule (in constant heatingrate's process, the temperature on microcapsule quality-temperature curve during microcapsule mass loss 5%) only is (Zhang Xingxiang etc., colloid and polymer science (Colloid﹠amp about 150 ℃; Polymer Science), 2004,88 (2): 330～336), the coating that promptly is used in fabric is handled, and (J. gold, Zhao G., textile research magazine (Textile Research Journal), 2002,72:1093～1098) sometimes also are difficult to meet the demands.This phase-change material micro-capsule can only be used as general hot-fluid or energy saving building material.
The major cause that the phase-change material micro-capsule heat decomposition temperature is lower is: the thermal expansivity of capsule-core (phase change material) and cyst wall is different, and the thermal expansivity of capsule-core is usually greater than cyst wall, capsule-core expansible speed is greater than cyst wall when being heated, cyst wall breaks under the internal pressure effect, and the capsule-core on effusion cyst wall surface decomposes, oxidation, distillation etc.Because when adopting phase-change material micro-capsule to have the fiber of heat absorption memory function for the preparation of substance melt-spinning, the heat decomposition temperature that requires phase change material at least will be about 230 ℃ (Zhang Xingxiang etc., Materials science magazine (Joumal of Materials Science), 2005,40:3729～3734), when being used as high-temperature infrared camouflage coating material, heat decomposition temperature is higher, and general microcapsule technology of preparing is difficult to prepare the phase-change material micro-capsule of high-temperature resistant.Applicant's patent formerly (CN1459330A) discloses one and added the easy volatile material in capsule-core, utilize the cyst wall commute volatile matter perviousness characteristics high than phase change material, microcapsule after thermal treatment is shaped, reserve the expansion space inner formation of microcapsule after removing the easy volatile material, thereby enough expansion spaces when being heated, phase-change material micro-capsule are arranged, be unlikely to cause breaking rapidly of cyst wall, improved heat decomposition temperature significantly, the heat resisting temperature of phase-change material micro-capsule reaches 269 ℃.But this technology has reduced the effective content of phase change material in the microcapsule, and is unfavorable for the phase-change material micro-capsule of preparation high enthalpy value.Chinese invention patent (CN1570014A) discloses a kind of preparation composite shell phase-change material micro-capsule technology.This technology by the melamine resin outer wall of internal layer once more coating modification melamine resin cyst wall prepare the good microcapsule of cyst wall physical and mechanical property, obviously, this technology has increased processing step, makes preparation process complicated more.
Summary of the invention
At the deficiencies in the prior art, the technical problem that quasi-solution of the present invention is determined is that a kind of phase-change material micro-capsule and preparation method thereof is provided.This phase-change material micro-capsule has heat decomposition temperature height, characteristics such as excellent property; This preparation method's technology is simple, easy to operate, applied widely, is convenient to industrial implementation.
The technical scheme that the present invention solves described microcapsulary problem is, designs a kind of phase-change material micro-capsule, it is characterized in that these microcapsule are made by the mixed solution of oil phase component and water component, and wherein to account for the mass percent of mixed solution be 9～30% to oil phase component; The mass percent of described oil phase component consists of:
Free yl polymerizating monomer 28～49%;
Linking agent 1～9%;
Organic phase change material 44～70%;
The mass percent of described water component consists of:
Deionized water 80～99%;
The mass percent sum of each component of aqueous phase is 100%.
The surface of described phase-change material micro-capsule has the depression that differs in size more than or, median size≤90 μ m, and it is 20～40% that the cumulative volume of described depression accounts for the microcapsule volume percent; The heat decomposition temperature of microcapsule 〉=230 ℃;
Described free yl polymerizating monomer is meant vinylformic acid C
1～C
6Alkyl ester, methacrylic acid C
1～C
6In alkyl ester, vinylbenzene and the vinyl toluene 1～3 kind; Described vinylformic acid C
1～C
6Alkyl ester is meant methyl acrylate, ethyl propenoate, vinylformic acid n-propyl, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, the just own ester of vinylformic acid, the own ester of vinylformic acid 2-or the own ester of vinylformic acid 3-; Described methacrylic acid C
1～C
6Alkyl ester is meant the just own ester of methyl methacrylate, Jia Jibingxisuanyizhi, n propyl methacrylate, isopropyl methacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, methacrylic acid, the own ester of methacrylic acid 2-or the own ester of methacrylic acid 3-;
Described linking agent is meant the oil soluble free yl polymerizating monomer with 2～4 functional groups, comprises in Ethylene glycol dimethacrylate, dimethyl allene acid propylene glycol ester, tetramethylene dimethacrylate, dimethacrylate hexylene glycol ester, ethylene glycol diacrylate, diacrylate propylene glycol ester, hexanediol diacrylate, trimethylammonium vinylformic acid glycerine ester, three vinylformic acid glycerine esters, pentaerythritol tetramethacrylate and pentaerythritol tetracrylate and the divinylbenzene any one;
Described organic phase change material is meant with general formula C
nH
2n+2The normal paraffin compounds of (n=12～32) expression is with general formula C
nH
2n+1The halo normal paraffin compounds of X (n=12～32) expression and with general formula C
mH
2m+1COOCH
2C
pH
2p+1(n=12～32, m=10～20, p=4～10) expression fatty acid ester in any 1～3 kind;
Described initiator is meant radical polymerization initiator, comprises a kind of in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) and the benzoyl peroxide;
Described emulsifying agent is meant a kind of in anionic emulsifier, cationic emulsifier and the nonionic emulsifying agent; Described anionic emulsifier is meant alkylbenzene sulfonate, sulfonated alkyl naphathalene, alkylsulfonate, dialkyl succinylsuccinate sulfonated ester, alkyl biphenyl base ether sulfonate, N-methyl fatty acyl amido taurate or N-alkyl acylsarcosine salt; Described cationic emulsifier is meant ammonium salt type emulsifying agent or quaternary emulsifying agent; Described nonionic emulsifying agent is meant a kind of in alkylphenol polyoxyethylene, benzylphenol Soxylat A 25-7, styroyl phenol polyethenoxy ether, aliphatic amine polyoxyethylene ether, fatty alcohol-polyoxyethylene ether and styroyl phenol polyethenoxy ether and the styroyl phenol polyoxypropylene ethers emulsifying agent.
The technical scheme that the present invention solves described preparation method's technical problem is, design a kind of phase-change material micro-capsule preparation method, this preparation method adopts phase-change material micro-capsule mass percent of the present invention to form and following technology: at first, under temperature I and stirring velocity I, the mixture of free yl polymerizating monomer, linking agent, organic phase change material and the initiator of described mass percent is stirred, make oil phase component; Under temperature I and stirring velocity I, the emulsifying agent of described mass percent is joined in the deionized water, make even water component solution; Then, made oil phase component is joined in the aqueous phase solution, keep temperature I constant, and stir into homogeneous latex emulsion with stirring velocity II; Temperature with mixed emulsion rises to temperature II again, after churning time I stirs, reacts and finishes in 2～5 hours; Stop to stir, cooling water circulation is to room temperature, the filtering separation mixed emulsion, behind the deionized water rinsing product of 3～5 times of phase-change material micro-capsule quality 2～5 times, promptly obtain the wet cake of phase-change material micro-capsule, perhaps in vacuum drying oven, be dried to constant weight, promptly obtain phase-change material micro-capsule dry powder; Described temperature I is 40～60 ℃; Temperature II is 61～90 ℃; Stirring velocity I is 100～999r/min; Stirring velocity II is 1000～10000r/min; Churning time I is 1～8 hour.
Compared with prior art, phase-change material micro-capsule of the present invention is owing to adopt the novel polymeric technology, make polymerization single polymerization monomer be diffused into the interface polymerization takes place by oil phase, in oil phase, form and reserve the expansion space, and in polymerization single polymerization monomer, contain two functional groups or polyfunctional monomer certainly, after reaction finishes, can form cyst wall, thereby have resistant to elevated temperatures characteristics with crosslinking structure; The preparation method of phase-change material micro-capsule of the present invention is owing to adopt good emulsifying and help emulsifying technology, thus the phase-change material micro-capsule of preparing to have a particle diameter little, and technology is simple, and is easy to operate, applied widely, is convenient to industrial implementation.
Description of drawings
Fig. 1 in the phase-change material micro-capsule preparation process of the present invention during copolymerization microcapsule be recessed to form the synoptic diagram of process; Wherein, 1-drop; 2-reacts beginning; The 3-compound is transferred to the interface; The 4-cyst wall forms, and enlarged in thickness; The 5-reaction is carried out; 6-is recessed to form; The 7-cooling; The 8-hollow volume strengthens.
Fig. 2 is the electron scanning micrograph figure of a kind of embodiment of phase-change material micro-capsule of the present invention.
Fig. 3 is the electron scanning micrograph figure of the another kind of embodiment of phase-change material micro-capsule of the present invention.
Embodiment
Further narrate the present invention below in conjunction with embodiment and accompanying drawing thereof:
The phase-change material micro-capsule (abbreviation microcapsule) of the present invention design is characterized in that these microcapsule are made by the mixed solution of oil phase component and water component, and wherein to account for the mass percent of mixed solution be 9～30% to oil phase component; The oil phase component mass percent is lower than 9%, and production efficiency is low; And the oil phase component mass percent is greater than 30%, the emulsification difficulty, and the difficulty of preparation phase-change material micro-capsule significantly increases.
The mass percent of described oil phase component consists of:
Free yl polymerizating monomer 28～49%;
Linking agent 1～9%;
Organic phase change material 44～70%;
The quality percentage composition of described water component is:
Deionized water 80～99%;
The surface of described phase-change material micro-capsule has the depression that differs in size more than or, median size≤90 μ m, the mass percent that capsule-core accounts for microcapsule is 44～70%, the per-cent that the cumulative volume of one or more depressions on the cyst wall accounts for the microcapsule volume is 20～40%, the heat decomposition temperature of microcapsule 〉=230 ℃.
The described free yl polymerizating monomer of microcapsule of the present invention is meant vinylformic acid C
1～C
6Alkyl ester, methacrylic acid C
1～C
6In alkyl ester, vinylbenzene and the vinyl toluene 1～3 kind; Described vinylformic acid C
1～C
6Alkyl ester is meant methyl acrylate, ethyl propenoate, vinylformic acid n-propyl, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, the just own ester of vinylformic acid, the own ester of vinylformic acid 2-or the own ester of vinylformic acid 3-; Described methacrylic acid C
1～C
6Alkyl ester is meant the just own ester of methyl methacrylate, Jia Jibingxisuanyizhi, n propyl methacrylate, isopropyl methacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, methacrylic acid, the own ester of methacrylic acid 2-or the own ester of methacrylic acid 3-etc.
The described linking agent of microcapsule of the present invention is meant the oil soluble free yl polymerizating monomer with 2～4 functional groups, comprises a kind of in Ethylene glycol dimethacrylate, dimethyl allene acid propylene glycol ester, tetramethylene dimethacrylate, dimethacrylate hexylene glycol ester, ethylene glycol diacrylate, diacrylate propylene glycol ester, hexanediol diacrylate, trimethylammonium vinylformic acid glycerine ester, three vinylformic acid glycerine esters, pentaerythritol tetramethacrylate and pentaerythritol tetracrylate and the divinylbenzene etc.Linking agent of the present invention is significant.Though when not using linking agent, also can prepare phase-change material micro-capsule, when its cyst wall uses under hot environment, fusion can take place in cyst wall, or is converted into viscous state by vitreous state, and the cyst wall physical mechanical strength reduces rapidly, cause capsule-core to overflow, be difficult to satisfy service requirements.Therefore, change the kind and the mass percent of polymerization single polymerization monomer and linking agent in any case, the mass percent of linking agent is non-vanishing all the time in the constituent of microcapsule of the present invention, and to guarantee to form cross-linked network, cyst wall fusion takes place or be transformed into viscous state at the Shi Buhui that is heated.
The mass percent ideal range that capsule-core in the microcapsule of the present invention (organic phase change material) accounts for microcapsule is 44～70%.Reduce the accounting content of capsule-core, increase wall thickness, can improve the resistance toheat of microcapsule, but can reduce the energy storage effect of microcapsule; And the accounting content of increasing capsule-core then causes the cyst wall attenuation easily, and the phase-change material micro-capsule resistance toheat is descended.
The described organic phase change material of microcapsule of the present invention is meant with general formula C
nH
2n+2The normal paraffin compounds of (n=12～32) expression is with general formula C
nH
2n+1The halo normal paraffin compounds of X (n=12～32) expression and with general formula C
mH
2m+1COOCH
2C
pH
2p+1(n=12～32, m=10～20, p=4～10) expression fatty acid ester in any 1～3 kind.Why selecting (n=12～32, m=10～20, p=4～10) respectively, mainly is to consider that the neither endothermic nor exothermic temperature of selected normal paraffin, halo normal paraffin and fatty acid ester is in-40～60 ℃ scope.Studies show that the phase change material of this temperature range is the most extensive in range of application energy-conservation and that improve aspect the hydrophobicity.And when selecting for use two kinds and above phase change material mixture as phase change material, should also be noted that the exothermic temperature that can not make a kind of phase change material is overlapping with the endothermic temperature of another kind of or multiple phase change material, in order to avoid make the heat accumulation defunctionalization, or heat absorption, exothermic temperature change.
The described initiator of microcapsule of the present invention is meant radical polymerization initiator, is meant Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) or benzoyl peroxide especially, but other the known technology about radical polymerization initiator also is applicable to the present invention.
The described emulsifying agent of microcapsule of the present invention is meant anionic emulsifier, cationic emulsifier or nonionic emulsifying agent, and described anionic emulsifier comprises a kind of in alkylbenzene sulfonate, sulfonated alkyl naphathalene, alkylsulfonate, dialkyl succinylsuccinate sulfonated ester, alkyl biphenyl base ether sulfonate, N-methyl fatty acyl amido taurate and the N-alkyl acylsarcosine salt; Described cationic emulsifier is meant ammonium salt type emulsifying agent or quaternary emulsifying agent; Described nonionic emulsifying agent is meant a kind of in alkylphenol polyoxyethylene, benzylphenol Soxylat A 25-7, styroyl phenol polyethenoxy ether, aliphatic amine polyoxyethylene ether, fatty alcohol-polyoxyethylene ether and styroyl phenol polyethenoxy ether and the styroyl phenol polyoxypropylene ethers emulsifying agent.
Can add mass percent in the microcapsule water component of the present invention as required and be 0.1～1% assistant for emulsifying agent.Described assistant for emulsifying agent is meant some material that is formed with promoter action to emulsion, comprises a kind of in 1-lauryl alcohol, 1-tetradecyl alcohol, 1-hexadecanol and the 1-stearyl alcohol etc.If the used emulsifying agent of aqueous phase can make mixture form the good emulsion of emulsification, then needn't add assistant for emulsifying agent.
In like manner, can add mass percent in the microcapsule water component of the present invention as required is 0.1～1% stablizer.Described stablizer is meant the stable material that promoter action is arranged to emulsion, comprises a kind of in polyvinyl alcohol, polyvinylpyrrolidone, polyoxyethylene glycol, polyoxyethylene and the polyoxypropylene etc.Stablize good emulsion, then needn't add stablizer if the used emulsifying agent of aqueous phase can make mixture form.
Described assistant for emulsifying agent and stablizer can add separately, also can add simultaneously.Add assistant for emulsifying agent or/and behind the stablizer, the deionized water of aqueous phase consists of 100% or/and the mass percent of emulsifying agent is formed increase or the minimizing that should do corresponding proportion with the mass percent that guarantees each component.The water mass percent composition that for example adds assistant for emulsifying agent and stablizer simultaneously can be adjusted to:
Deionized water 80～98%;
Assistant for emulsifying agent 0.1～1%;
Stablizer 0.1～1%.
The present invention has designed described phase-change material micro-capsule preparation method (hereinafter to be referred as the preparation method) simultaneously, this preparation method adopts phase-change material micro-capsule mass percent of the present invention to form and following technology: at first, under temperature I and stirring velocity I, the mixture of free yl polymerizating monomer, linking agent, organic phase change material and the initiator of described mass percent is stirred, make oil phase component; Under temperature I and stirring velocity I, the emulsifying agent of described mass percent is joined in the deionized water, make even water component solution; Then, made oil phase component is joined in the aqueous phase solution, keep temperature I constant, and stir into homogeneous latex emulsion with stirring velocity II; Temperature with mixed emulsion rises to temperature II again, after churning time I stirs, reacts and finishes in 2～5 hours; Stop to stir, cooling water circulation is to room temperature, the filtering separation mixed emulsion, behind the deionized water rinsing product of 3～5 times of phase-change material micro-capsule quality 2～5 times, promptly obtain the wet cake of phase-change material micro-capsule, perhaps in vacuum drying oven, be dried to constant weight, promptly obtain phase-change material micro-capsule dry powder.
When containing described assistant for emulsifying agent or stablizer in the water component of the present invention, when perhaps containing described assistant for emulsifying agent and stablizer simultaneously, preparation method of the present invention is when preparation water component solution, to join described assistant for emulsifying agent and/or stablizer and emulsifying agent in the lump in the deionized water, simple.Certainly, the present invention does not get rid of other adding methods.
Described free yl polymerizating monomer of preparation method of the present invention and linking agent use after stopper is removed in underpressure distillation, and underpressure distillation removes the stopper technology and technology does not exceed the known technology scope.
The scope of the described temperature I of preparation method of the present invention is 40～60 ℃.The principle of its selection is, guarantees that organic phase change material is in liquid state, so that carry out emulsification smoothly, is lower than the kick off temperature of initiator simultaneously again, in order to avoid be polymerization reaction take place before forming stable emulsion.
The scope of described temperature II is 61～90 ℃.The principle of its selection is, guarantees to make the normal initiated polymerization of initiator, be unlikely to again to make polymerization rate too fast simultaneously, and it is too fast to evaporate the water, and influences the stability of preparation process.
Described stirring velocity I is meant and can guarantees to make oil phase and the mixed uniformly speed of water.Choosing of stirring velocity I do not exceed the technique known scope.Specifically choosing of stirring velocity I is relevant with the form that stirs (anchor formula, oar formula, centrifugal shearing) and the length and the shape of blade.Stirring velocity I is generally 100～999r/min.
Described stirring velocity II is meant and can guarantees to make oil phase to form the speed of the emulsion droplet of appropriate diameter at the aqueous phase homodisperse.Stirring velocity II is a high-speed stirring, and specifically choosing of stirring velocity is relevant with the form that stirs (anchor formula, oar formula, centrifugal shearing) and the length and the shape of blade.Usually stirring velocity II is obviously greater than stirring velocity I.Stirring velocity II is generally 1000～10000r/min.
Described churning time I is meant and can makes Raolical polymerizable finish the required time.Choosing of churning time I do not exceed the technique known scope.Choosing of churning time I and polymerization single polymerization monomer, linking agent, initiator, temperature II is relevant, generally between 1～8 hour, is preferably between 3～6 hours, can choose according to the situation of the phase-change material micro-capsule of preparation.
The surface of preparation method's gained phase-change material micro-capsule of the present invention has the depression (referring to Fig. 2,3) that differs in size more than or, median size≤90 μ m, and heat decomposition temperature 〉=230 ℃, the mass percent that capsule-core accounts for microcapsule is 44～70%.
Formation mechanism (referring to Fig. 1) summary of surface of microcapsule depression of the present invention is: 1 stirring and emulsifying formation drop-2 reaction beginning-3 polymkeric substance are transferred to interface-4 cyst wall and are formed, and enlarged in thickness-5 reaction is carried out-6 and is recessed to form the increasing of-7 coolings-8 hollow volume, obtains the product microcapsule.
The high reason of microcapsule heat decomposition temperature of the present invention is: but the polymerization single polymerization monomer of polymerization reaction take place, linking agent and organic phase change material and initiator etc. are in oil phase together, under temperature II, the reaction of polymerization single polymerization monomer and linking agent forms co-polymer membrane and is deposited on oil phase and water at the interface, polymerization single polymerization monomer in the oil phase and linking agent constantly are diffused at the interface and copolymerization takes place in continuation, be deposited on the inwall of co-polymer membrane, make the thickness of film increasing, form the cyst wall of microcapsule; Because the density of polymerization single polymerization monomer and linking agent is less than the density of multipolymer, polymerization single polymerization monomer and the linking agent of participating in copolymerization are many more, it is obvious more that this density difference shows, thereby cause cyst wall in copolymerization process, constantly to shrink, form one or more depressions that differ in size on cyst wall, polymerization single polymerization monomer in oil phase and linking agent almost total overall reaction finish; Changed into by liquid state in the solid-state process at capsule-core, because the density of crystal form is greater than molten state, volumetric shrinkage can further take place in microcapsule, causes the depression size to strengthen and/or increases.
Different according to used polymerization single polymerization monomer and linking agent kind and mass percent example, it is 20～40% that the cumulative volume of one or more depressions on the cyst wall accounts for the microcapsule volume percent.After on the cyst wall one or more are recessed in phase-change material micro-capsule and are heated, capsule-core (organic phase change material) is when expanding, fade away, 20～40% reservation expansion space is provided for capsule-core, thereby can prevent effectively that cyst wall from breaking, avoid causing capsule-core from microcapsule, to flow out and/or overflow and decompose, thereby the heat decomposition temperature of phase-change material micro-capsule can be improved more than 80 ℃, thereby make phase-change material micro-capsule can satisfy the service requirements of hot environment.
Wet cake of phase-change material micro-capsule of the present invention or dry powder can be used for hot-fluid, heat resisting coating, energy-saving building material and fibre modifier etc.
The surface topography of phase-change material micro-capsule of the present invention and the sign of performance are all used following equipment except that indicating especially:
Adopt the shape and the diameter of Olympus BX-51 observation by light microscope emulsion droplet.
Adopt the surface topography of the phase-change material micro-capsule behind observation drying, the metal spraying on the Czech Quanta200 type scanning electronic microscope.
Adopt China's pick size-grade distribution of making the LA-300 of institute type laser particle size distribution instrument test phase-change material micro-capsule suspension liquid.
Adopt NETZSCH DSC 200F3 differential scanning calorimeter (DSC), under nitrogen protection, test the DSC scanning curve of 10 ℃/min temperature-rise period and-10 ℃/min temperature-fall period, obtain the suction exothermic temperature and the heat content of phase-change material micro-capsule.
Adopt NETZSCH, STA409PC/PG TG-DTA thermogravimetric analyzer (TG) is measured the heat decomposition temperature (temperature of weightless 5wt%) of exsiccant phase-change material micro-capsule in nitrogen with 10 ℃/min temperature-rise period.
The present invention does not address part and is applicable to prior art.
Provide specific embodiments of the invention below: but specific embodiment only is in order to be described in further detail this explanation, not limit claim of the present invention.
Microcapsule mass percent composition is designed to:
Oil phase 190g, wherein free yl polymerizating monomer comprises methyl acrylate (MA) 28g, n-BMA 10g, vinylbenzene (St) 15g, linking agent trimethylammonium vinylformic acid glycerine ester 18g, phase change material 1-bromo-octadecane (Broct) 117g and initiator 2,2'-Azobis(2,4-dimethylvaleronitrile) 2g.
Water 1000g, deionized water (abbreviation water) 970g wherein, emulsifier sodium lauryl sulfate 10g, assistant for emulsifying agent 1-tetradecyl alcohol and 10g and stablizer polyoxyethylene glycol (number-average molecular weight 600) 10g.
The mass percent that oil phase accounts for mixing liquid is 16%.
The preparation method of microcapsule is: at first, under the stirring velocity I of 40 ℃ temperature I and 600rpm, the mixture of free yl polymerizating monomer, linking agent, organic phase change material and the initiator of described mass percent is stirred, make oil phase; Under the stirring velocity I of 40 ℃ temperature I and 600rpm, described mass percent emulsifying agent, assistant for emulsifying agent and stablizer are joined in the deionized water, make even water component solution; Then, made oil phase component is joined in the aqueous phase solution, keep temperature I constant, and stir the formation homogeneous latex emulsion with 8000rpm stirring velocity II; Again the temperature of mixed emulsion is risen to 80 ℃ temperature II, after the churning time I of 15min stirs, react and finished in 3 hours; Stop to stir, cooling water circulation is to room temperature, and the filtering separation mixed emulsion behind the deionized water rinsing product of quality 2500g 3 times, is dried to constant weight in 50 ℃ of vacuum drying ovens, promptly obtain phase-change material micro-capsule dry powder.
After testing, the median size of gained phase-change material micro-capsule is 4.1 μ m, endothermic temperature (T
m) 28.1 ℃, melting enthalpy (Δ H
m) 128J/g, exothermic temperature (T
c) 21.1 ℃, crystallization heat content (Δ H
c) 129J/g, the mass percent of Broct is 61% in the microcapsule, the per-cent that the hollow volume that calculates according to the density difference of free radical polymerizable monomer and multipolymer accounts for the microcapsule volume is 25%, the per-cent that the hollow volume that calculates according to the density difference of Broct before and after the crystallization accounts for the microcapsule volume is 15%, the per-cent that the depression cumulative volume of surface of microcapsule accounts for the microcapsule volume is 40%, heat decomposition temperature (T
d) 255 ℃.
The mass percent of microcapsule consists of:
Oil phase 600g, wherein free yl polymerizating monomer comprises vinyl toluene (MSt) 265g, linking agent divinylbenzene (DVB) 28g, phase change material 1-bromo eicosane (Brei) 300g and free crowd initiator Diisopropyl azodicarboxylate (AIBN) 7g.
Water 2400g, water 2352g wherein, emulsifying agent oleic acid sorbitol ester (this class 80) 24g, stablizer polyvinyl alcohol (polymerization degree 1750, degree of hydrolysis 98%) 24g.
The mass percent that oil phase accounts for mixed solution is 20%.
The preparation method of microcapsule is: at first, under the stirring velocity I of 60 ℃ temperature I and 800rpm, the mixture of free yl polymerizating monomer, linking agent, organic phase change material and the initiator of described mass percent is stirred, make oil phase; Under the stirring velocity I of 60 ℃ temperature I and 800rpm, described mass percent emulsifying agent, assistant for emulsifying agent and stablizer are joined in the deionized water, make even water component solution; Then, made oil phase component is joined in the aqueous phase solution, keep temperature I constant, and stir the formation homogeneous latex emulsion with 5400rpm stirring velocity II; Again the temperature of mixed emulsion is risen to 80 ℃ temperature II, finished in 5 hours through 5400rpm stirring velocity II stirring reaction; Stop to stir, cooling water circulation is to room temperature, and the filtering separation mixed emulsion behind the deionized water rinsing product of quality 1800g 3 times, obtains the wet cake of phase-change material micro-capsule.
The wet cake of present embodiment gained microcapsule detects after 50 ℃ of vacuum drying ovens are dried to constant weight, and use scanning electronic microscope observation: the median size of 1-bromo eicosane microcapsule is 18.2 μ m (referring to Fig. 2), endothermic temperature (T
m) 34.0 ℃, melting enthalpy (Δ H
m) 129J/g, exothermic temperature (T
c) 25.1 ℃, crystallization heat content (Δ H
c) 127J/g, the mass percent of Brei is 57% in the microcapsule, the per-cent that the hollow volume that calculates according to the density difference of free radical polymerizable monomer and multipolymer accounts for the microcapsule volume is 24%, according to the density difference of 1-bromo eicosane before and after the crystallization calculate because the hollow volume that crystallization causes accounts for the per-cent of microcapsule volume is 15%, the per-cent that the depression cumulative volume of surface of microcapsule accounts for the microcapsule volume is 39% (also can adopt among the remaining embodiment identical method of calculation obtain caving in cumulative volume account for the per-cent of microcapsule volume), heat decomposition temperature (T
d) 261 ℃.
Adopt the processing condition identical with embodiment 2, only change the mass percent of 1-bromo eicosane and polymerization single polymerization monomer and linking agent, obtain the different phase-change material micro-capsule of 1-bromo eicosane content, its performance is as shown in table 1.The mass percent composition of embodiment 3-5 microcapsule is respectively:
The mass percent that embodiment 3～5 oil phases account for mixed solution is respectively 18%, 22% and 24%.
The performance table of the phase-change material micro-capsule of the different polymerization single polymerization monomer-linking agents of table 1/1-bromo eicosane mass ratio
Data increase with polymerization single polymerization monomer-linking agent/phase change material mass ratio as can be seen from table 1, and the heat-resistant stability of 1-bromo eicosane microcapsule improves.
The mass percent of microcapsule consists of:
Oil phase 600g, wherein free yl polymerizating monomer comprises that methyl methacrylate (MMA) 15g, Jia Jibingxisuanyizhi (EMA) 20g and butyl acrylate are polymerization single polymerization monomer 17g, the linking agent Ethylene glycol dimethacrylate is linking agent 6g, phase change material n-butyl stearate 120g and free crowd initiator 2,2'-Azobis(2,4-dimethylvaleronitrile) 2g.
Water 1100g, water 900g wherein, emulsifying agent phenylethylene-maleic anhydride sodium salt (SMA, solid content 19%, Shanghai Leather Chemical Plant) 200g.
The mass percent that oil phase accounts for mixing liquid is 14%.
The preparation method of microcapsule is: at first, under the stirring velocity I of 55 ℃ temperature I and 600rpm, the mixture of free yl polymerizating monomer, linking agent, organic phase change material and the initiator of described mass percent is stirred, make oil phase; Under the stirring velocity I of 55 ℃ temperature I and 600rpm, described mass percent emulsifying agent is joined in the deionized water, make even water component solution; Then, made oil phase component is joined in the aqueous phase solution, mix liquid 15min with the speed of 1600rpm, the emulsion that obtains is warming up to 75 ℃, reacts 4.5 hours.Stop heating and stirring, cooling water circulation filters to room temperature, leaches thing 3 times with the 2000g deionized water wash, and 50 ℃ of vacuum drying ovens are dried to constant weight.
Present embodiment gained microcapsule are through scanning electronic microscope observation, the depression that varying in size appears in the surface of n-butyl stearate microcapsule (referring to Fig. 3), and the median size that laser particle analyzer is measured is 89 μ m, endothermic temperature (T
m) 23.0 ℃, melting enthalpy (Δ H
m) 92J/g, exothermic temperature (T
c) 13.1 ℃, crystallization heat content (Δ H
c) 93J/g, the mass percent of n-butyl stearate is 66% in the microcapsule, heat decomposition temperature (T
d) 243 ℃.
The mass percent composition of embodiment 7～12 microcapsule is respectively:
Embodiment 9, and oil phase 148g consists of MEA25%, MAA10%, BDHA3%, NSC 62789 61%, initiator 1%;
Embodiment 10, and oil phase 114g consists of MEA32%, MAA13%, BDHA4%, NSC 62789 49%, initiator 2%;
Embodiment 11, and oil phase 114g consists of MEA31%, MAA13%, BDHA5%, NSC 62789 49%, initiator 2%;
Embodiment 12, and oil phase 114g consists of MEA26%, MAA13%, BDHA9%, NSC 62789 49%, initiator 2%.
Water 1100g, water 91%, SMA9%.
The mass percent that oil phase accounts for mixed solution is respectively 15%, 14%, 12%, 9%, 9% and 9%.
(SMA, solid content 19%, Shanghai Leather Chemical Plant) joins in the 1000g deionized water with 100g phenylethylene-maleic anhydride sodium salt, and under 60 ℃, 600rpm stirs, and obtains water.With ethyl propenoate (EA) and methyl methacrylate (MMA) is polymerization single polymerization monomer, is linking agent with the own diester of diacrylate (BDHA), and benzoyl peroxide (BPO) is an initiator, presses the proportional arrangement oil phase in the table 2.Oil phase is joined aqueous phase, mix liquid 15min with the speed of 1200rpm, the emulsion that obtains is warming up to 75 ℃, reacts 4.5 hours.Stop heating and stirring, cooling water circulation filters to room temperature, leaches thing 3 times with the 2000g deionized water wash, and 50 ℃ of vacuum drying ovens are dried to constant weight promptly.
The performance of the NSC 62789 microcapsule that embodiment 7～12 obtains is as shown in table 2.
Different polymerization single polymerization monomer-the linking agents of table 2/NSC 62789 quality is than the performance table of microcapsule
" ratio " in the table 2 is the mass ratio of polymerization single polymerization monomer-linking agent/NSC 62789; " mass percent " is the mass percent (wt%) of NSC 62789.
Embodiment 13
With the Jia Jibingxisuanyizhi among the vinylbenzene replacement embodiment 6, other component ratios and processing parameter are constant, make the n-butyl stearate microcapsule.
The median size of present embodiment microcapsule is 84 μ m, endothermic temperature (T
m) 23.1 ℃, melting enthalpy (Δ H
m) 91J/g, exothermic temperature (T
c) 13.0 ℃, crystallization heat content (Δ H
c) 92J/g, the mass percent of n-butyl stearate is 65% in the microcapsule, heat decomposition temperature (T
d) 245 ℃.
Embodiment 14
With the own diester of dimethacrylate among the divinylbenzene replacement embodiment 6, other component ratios and processing parameter are constant, make the n-butyl stearate microcapsule.
The median size of present embodiment microcapsule is 82 μ m, endothermic temperature (T
m) be 23.3 ℃, melting enthalpy (Δ H
m) 93J/g, exothermic temperature (T
c) 13.2 ℃, crystallization heat content (Δ H
c) 94J/g, the mass percent of n-butyl stearate is 66% in the microcapsule, heat decomposition temperature (T
d) be 243 ℃.
Embodiment 15
With the n-butyl stearate among the 1-bromohexadecane replacement embodiment 6, other component ratios and processing parameter are constant, make 1-bromohexadecane microcapsule.
The median size of present embodiment microcapsule is 76 μ m, endothermic temperature (T
m) 14.3 ℃, melting enthalpy (Δ H
m) 90J/g, exothermic temperature (T
c) 6.4 ℃, crystallization heat content (Δ H
c) 92J/g, the mass percent of 1-bromohexadecane is 65% in the microcapsule, heat decomposition temperature (T
d) 252 ℃.
Embodiment 16
With the n-butyl stearate among the positive butyl ester replacement of the 1-dodecylic acid embodiment 6, other component ratios and processing parameter are constant, make the positive butyl ester microcapsule of 1-dodecylic acid.
The median size of present embodiment microcapsule is 83 μ m, heat decomposition temperature (T
d) 249 ℃.
Embodiment 17
The mass percent of microcapsule consists of:
Oil phase 150g, free yl polymerizating monomer methyl methacrylate (MMA) 19g wherein, the own ester 10g of vinylformic acid 3-, vinylbenzene (St) 5g, linking agent pentaerythritol tetramethacrylate 8g, initiator benzoyl peroxide 3g.
Water 350g, comprising water 300g, emulsifier polyoxyethylene sorbitan monopalmitate (polysorbate40) 38g, assistant for emulsifying agent 1-tetradecyl alcohol 12g.
Oil phase accounts for the mass percent 30% of mixed solution.
The preparation method of microcapsule is: at first, under the stirring velocity I of 50 ℃ temperature I and 700rpm, the mixture of free yl polymerizating monomer, linking agent, organic phase change material and the initiator of described mass percent is stirred, make oil phase; Under the stirring velocity I of 50 ℃ temperature I and 700rpm, described mass percent emulsifying agent is joined in the deionized water, make even water component solution; Oil phase is joined aqueous phase, mix liquid 12min with the speed of 9000rpm, the emulsion that obtains is warming up to 90 ℃, reacts 4.5 hours.Stop heating and stirring, cooling water circulation filters to room temperature, leaches thing 3 times with the 2000g deionized water wash, and 50 ℃ of vacuum drying ovens are dried to constant weight promptly.
After testing, the median size of present embodiment microcapsule is 6.6 μ m, endothermic temperature (T
m) 65.1 ℃, melting enthalpy (Δ H
m) 160J/g, exothermic temperature (T
c) 54.1 ℃, crystallization heat content (Δ H
c) 161J/g, the mass percent of positive triacontane is 70% in the microcapsule, heat decomposition temperature (T
d) 233 ℃.
Embodiment 18
The speed with 1600rpm among the embodiment 6 is mixed liquid 15min, and the speed that changes into 8500rpm mixes liquid 15min, and other components and processing parameter are constant, and the median size of the n-butyl stearate microcapsule that obtain is 5.4 μ m, heat decomposition temperature (T
d) 241 ℃.This explanation improves the median size that stirring velocity II can significantly reduce microcapsule, for control particle diameter technology provides foundation.
Claims (4)
1. phase-change material micro-capsule is characterized in that these microcapsule are made through preparation method described later by the mixed solution of oil phase component and water component, and wherein to account for the mass percent of mixed solution be 9～30% to oil phase component; The mass percent of described oil phase component consists of:
Free yl polymerizating monomer 28～49%;
Linking agent 1～9%;
Organic phase change material 44～70%;
Initiator 1～2%, the mass percent sum of each component is 100% in the oil phase;
The mass percent of described water component consists of:
Deionized water 80～99%;
Emulsifying agent 1～20%; The mass percent sum of each component of aqueous phase is 100%;
The surface of described phase-change material micro-capsule has the depression that differs in size more than or, median size≤90 μ m, and the mass percent that capsule-core accounts for microcapsule is 44～70%, it is 20～40% that the cumulative volume of described depression accounts for the microcapsule volume percent; The heat decomposition temperature of microcapsule 〉=230 ℃;
Described free yl polymerizating monomer is meant vinylformic acid C
1～C
6Alkyl ester, methacrylic acid C
1～C
6In alkyl ester, vinylbenzene and the vinyl toluene 1～3 kind; Described vinylformic acid C
1～C
6Alkyl ester is meant methyl acrylate, ethyl propenoate, vinylformic acid n-propyl, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, the just own ester of vinylformic acid, the own ester of vinylformic acid 2-or the own ester of vinylformic acid 3-; Described methacrylic acid C
1～C
6Alkyl ester is meant the just own ester of methyl methacrylate, Jia Jibingxisuanyizhi, n propyl methacrylate, isopropyl methacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, methacrylic acid, the own ester of methacrylic acid 2-or the own ester of methacrylic acid 3-;
Described linking agent is meant the oil soluble free yl polymerizating monomer with 2～4 functional groups, comprises in Ethylene glycol dimethacrylate, dimethyl allene acid propylene glycol ester, tetramethylene dimethacrylate, dimethacrylate hexylene glycol ester, ethylene glycol diacrylate, diacrylate propylene glycol ester, hexanediol diacrylate, trimethylammonium vinylformic acid glycerine ester, three vinylformic acid glycerine esters, pentaerythritol tetramethacrylate and pentaerythritol tetracrylate and the divinylbenzene any one;
Described organic phase change material is meant with general formula C
nH
2n+2, the normal paraffin compounds of n=12～32 expressions is with general formula C
nH
2n+1X, the halo normal paraffin compounds of n=12～32 expression and with general formula C
mH
2m+1COOCH
2C
pH
2p+1, n=12～32, m=10～20, in the fatty acid ester of p=4～10 expression any 1～3 kind;
Described initiator is meant radical polymerization initiator, comprises a kind of in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) and the benzoyl peroxide;
Described emulsifying agent is meant a kind of in anionic emulsifier, cationic emulsifier and the nonionic emulsifying agent; Described anionic emulsifier is meant alkylbenzene sulfonate, sulfonated alkyl naphathalene, alkylsulfonate, dialkyl succinylsuccinate sulfonated ester, alkyl biphenyl base ether sulfonate, N-methyl fatty acyl amido taurate or N-alkyl acylsarcosine salt; Described cationic emulsifier is meant ammonium salt type emulsifying agent or quaternary emulsifying agent; Described nonionic emulsifying agent is meant a kind of in alkylphenol polyoxyethylene, benzylphenol Soxylat A 25-7, styroyl phenol polyethenoxy ether, aliphatic amine polyoxyethylene ether, fatty alcohol-polyoxyethylene ether and styroyl phenol polyethenoxy ether and the styroyl phenol polyoxypropylene ethers emulsifying agent;
Described preparation method adopts following technology: at first, under temperature I and stirring velocity I, the mixture of free yl polymerizating monomer, linking agent, organic phase change material and the initiator of described mass percent is stirred, make oil phase component; Under temperature I and stirring velocity I, the emulsifying agent of described mass percent is joined in the deionized water, make even water component solution; Then, made oil phase component is joined in the aqueous phase solution, keep temperature I constant, and stir into homogeneous latex emulsion with stirring velocity II; Temperature with mixed emulsion rises to temperature II again, after churning time I stirs, reacts and finishes in 2～5 hours; Stop to stir, cooling water circulation is to room temperature, the filtering separation mixed emulsion, behind the deionized water rinsing product of 3～5 times of phase-change material micro-capsule quality 2～5 times, promptly obtain the wet cake of phase-change material micro-capsule, perhaps in vacuum drying oven, be dried to constant weight, promptly obtain phase-change material micro-capsule dry powder; Described temperature I is 40～60 ℃; Temperature II is 61～90 ℃; Stirring velocity I is 100～999r/min; Stirring velocity II is 1000～10000r/min; Churning time I is 1～8 hour.
2. phase-change material micro-capsule according to claim 1, it is characterized in that also comprising in the quality percentage composition of water component of these microcapsule 0.1～1% assistant for emulsifying agent or/and 0.1～1% stablizer, the mass percent sum of each component of aqueous phase is 100%; Described assistant for emulsifying agent is meant 1-lauryl alcohol, 1-tetradecyl alcohol, 1-hexadecanol or 1-stearyl alcohol; Described stablizer is meant a kind of in polyvinyl alcohol, polyvinylpyrrolidone, polyoxyethylene glycol, polyoxyethylene and the polyoxypropylene.
3. phase-change material micro-capsule according to claim 1, when it is characterized in that containing described assistant for emulsifying agent or stablizer in the described water component, when perhaps containing described assistant for emulsifying agent and stablizer simultaneously, when preparation water component solution, join described assistant for emulsifying agent and/or stablizer and emulsifying agent in the deionized water in the lump.
4. phase-change material micro-capsule according to claim 1 is characterized in that described churning time I is 3～6 hours.
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