CN103769021B - A kind of preparation method of Organic-inorganic composite cyst wall accumulation energy microcapsule - Google Patents
A kind of preparation method of Organic-inorganic composite cyst wall accumulation energy microcapsule Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of Organic-inorganic composite cyst wall accumulation energy microcapsule.The method, by organic phase change material and surfactant mixing, adds thermal agitation and obtains uniform oil phase material; Get silica containing Ludox and ethyl orthosilicate that mass ratio is 1:1 ~ 10:1 again, add in deionized water and make aqueous phase material; Then oil phase material is joined in aqueous phase material, dispersed one-tenth emulsion; Add polyisocyanates and crosslinking agent subsequently, at the former temperature of maintenance and speed of agitator, obtain the microcapsules with Organic-inorganic composite cyst wall; Namely product is obtained after finally vacuum filtration, washing, drying being carried out to the liquid obtained.The microcapsules of storing energy through phase change of the method gained can be used for multiple field such as building energy conservation and pipeline storage tank thermal insulation, and this effect microcapsule wall has the advantage of organic material and inorganic material concurrently, and life cycle is longer.
Description
Technical field
The present invention relates to the preparation method of microcapsules of storing energy through phase change, is more particularly about a kind of preparation method with Organic-inorganic composite cyst wall accumulation energy microcapsule.
Background technology
Microcapsules of storing energy through phase change, owing to can absorbing in transition temperature range, storing, distributing a large amount of latent heat, reaches and controls ambient temperature and energy-conservation object, thus receive more concern; In fields such as refrigeration air-conditioner, building energy conservation, pipeline insulation, waste heat recoveries, there is prospect widely.Microcapsules of storing energy through phase change is divided into two parts usually, i.e. cyst wall and nucleation material, within wherein nucleation material is coated on cyst material.The material that can be used in preparing effect microcapsule wall is a lot, is mainly divided into organic and mineral-type two kinds.Organic comprises various polymer, as melamine-formaldehyde resin, Lauxite, polyurethane and gelatin-formaldehyde resin etc.; Mineral-type is the silica cyst wall that generates after hydrolysis of ethyl orthosilicate or Ludox mainly; And mostly there is certain weak point in these existing cyst materials, as short in poor heat stability, life cycle, exist toxic and side effect, with matrix material poor compatibility etc.
CN1161364A discloses the preparation method of a kind of melamine resin as the microcapsules of storing energy through phase change of cyst wall, and because melamine resin is more crisp, make the microcapsules mechanical performance that obtains poor, life cycle is shorter.Also because the heat endurance of melamine resin is lower, microcapsules are caused to there is certain hidden danger on fire.
The people such as Cho (Collid.Polym.Sci., 2002,280,260 ~ 266) research shows, in emulsion system, adopt that interfacial polymerization take n-octadecane as core, polyureas synthesized smooth surface and particle diameter is about 1 μm of microcapsules for shell material, its phase transition temperature is 28 ~ 30 DEG C, suitable with n-octadecane, enthalpy of phase change is slightly less than paraffin compound.Owing to using polyureas to do cyst wall, pliability and the mechanical performance of this microcapsule capsule wall material increase; But polyureas is as raw material, in production and use procedure, still can discharges pernicious gas, healthy and production equipment are damaged; The cyst wall that the method is used is simultaneously organic material, having combustion-supporting potential threat, therefore there is certain hidden danger when being applied to civilian building materials.
The people such as Fang (Chem.Eng.J.2010,163,154 ~ 159) research shows, adopt sol-gel process can prepare the microcapsule phase-change energy storage material with inorganic cyst wall, because microcapsules volume is light and handy, and cyst wall is inorganic material, decrease combustion-supporting risk, thus may be used for the manufacture process of multiple energy storage building materials.But, the raw material that the coated with silica phase-change material of people's inventions such as Fang uses is ethyl orthosilicate, and its price is higher, and the pliability of silica is poor in addition, easy fragmentation, the existence of these shortcomings have impact on the practical application of high-performance composite phase-change energy storage material.
CN101333432A discloses a kind of preparation method of paraffin composite phase change energy storage material of shaped by silica sol.The method for raw material, allows the mixture of paraffin and silicic acid separate out from system with Ludox, paraffin, obtains the paraffin class setting composite phase-change energy storage material of shaped by silica sol.Although the inexpensive Ludox of the method instead of more expensive ethyl orthosilicate as cyst material, but still there is some problems, mainly Ludox hydrolysis generates the process entails harshness of silica, cause silica wall thickness and microcapsule size uneven, affect the quality of microcapsules; And silica belongs to inorganic substances, by these microcapsules and organic matrix blending, compound tense, its compatibility is poor.
Summary of the invention
In view of weak point of the prior art, the invention provides a kind of preparation method of Organic-inorganic composite cyst wall accumulation energy microcapsule.The microcapsules of storing energy through phase change of the method gained can be used for multiple field such as building energy conservation and pipeline storage tank thermal insulation, and this effect microcapsule wall has the advantage of organic material and inorganic material concurrently, and life cycle is longer.
The preparation method of Organic-inorganic composite cyst wall accumulation energy microcapsule of the present invention, comprises the following steps:
(1) by the surfactant of the organic phase change material of 5 ~ 30 parts and 0.5 ~ 10 part, heat at 30 ~ 80 DEG C, stir under 500 ~ 1500 revs/min, obtain the oil phase material mixed;
(2) getting silica quality percentage composition is the Ludox of 25% ~ 65% and the ethyl orthosilicate of 10 ~ 40 parts, wherein the mass ratio of Ludox and ethyl orthosilicate is 1:1 ~ 10:1, add in the deionized water of 30 ~ 80 parts, stir under 500 ~ 1000 revs/min under room temperature, mix and make aqueous phase material;
(3) joined by the oil phase material of step (1) in the aqueous phase material of step (2), heat at 30 ~ 80 DEG C, stir under 500 ~ 1500 revs/min, mixing time 20 ~ 100 minutes, makes oil phase material dispersed one-tenth emulsion in aqueous phase; Add rapidly the polyisocyanates of 30 ~ 70 parts subsequently, add the crosslinking agent of 1 ~ 10 part simultaneously, at the former temperature of maintenance and speed of agitator, stablize 3 ~ 10 minutes, obtain the microcapsules with Organic-inorganic composite cyst wall;
(4) namely product is obtained after the liquid obtained step (3) carries out vacuum filtration, washing, drying.
In the present invention, the organic phase change material used in step (1), is generally paraffin, C
14~ C
22n-alkane, C
9~ C
18higher fatty acids and ester class in one or more, preferentially select 18
#paraffin, 20
#paraffin, 25
#paraffin, 30
#paraffin, 45
#paraffin, 58
#one or more in paraffin or BS etc.The phase transition temperature of organic phase change material is 18 ~ 60 DEG C.
In the present invention, the surfactant used in step (1) is polyethylene glycol, one or more in sucrose ester, polysorbate, octadecyl benzenesulfonic acid, lauryl sodium sulfate, sodium tetradecyl sulfate, sodium hexadecyl sulfate etc., is preferably one or both in lauryl sodium sulfate and sodium tetradecyl sulfate.
In the present invention, the polyisocyanates used in step (3) is toluene di-isocyanate(TDI), one or more in MDI, polymethylene multi-phenenyl isocyanate, IPDI, is preferably polymethylene multi-phenenyl isocyanate.
In the present invention, the crosslinking agent used in step (3) is ethylenediamine, water-soluble epoxy resin, containing one or more in the poly-carbodiimide (PCDI) of-NCN, be preferably poly-carbodiimide.
In the present invention, in step (4), the suction of vacuum filtration is 3 ~ 9kPa, and be preferably 5 ~ 7kPa, the time is 30 minutes.Baking temperature is 50 ~ 100 DEG C, and be preferably 60 ~ 80 DEG C, the time is 10 ~ 30 hours, is preferably 12 ~ 20 hours.
Organic-inorganic composite cyst wall accumulation energy microcapsule prepared by the inventive method, can there is polycondensation reaction with the-NCO in polyisocyanates in the Si-OH group in aqueous phase material, inorganic cyst material and organic cyst material are combined; After adding crosslinking agent, at the former temperature of maintenance and speed of agitator, between inorganic phase and organic phase, form chemical bond, obtain the microcapsules of the composite sac wall material polyurethane-polysiloxane with organic-inorganic copolymer characteristic.
Organic-inorganic composite cyst wall accumulation energy microcapsule prepared by the inventive method is made up of cyst wall and the organic phase change material be coated in cyst wall, in microcapsules, the mass percentage of organic phase change material is 50% ~ 90%, in cyst material, the mass percentage of silica is 10% ~ 40%, the mass percentage of polyurethane is 40% ~ 90%, spherical in shape, average grain diameter 1 ~ 10 μm.
Microcapsules prepared by the present invention can be widely used in the fields such as energy saving building, energy-saving and temperature-regulating coating, thermal control material, high-performance apparel.
Compared with prior art, tool of the present invention has the following advantages:
(1) microcapsules of storing energy through phase change of the present invention, its cyst wall is made up of inorganic material and organic material compound, possesses the advantage that the Heat stability is good of inorganic material, mechanical strength and oxidation resistance are high simultaneously, and organic material elasticity and the good feature of pliability.In addition, because cyst wall is composite organic-inorganic material, so the range of application of these microcapsules is wider, the dual needs of organic matrix and inorganic matrix can namely be met.
(2) in cyst wall formation, select Ludox and ethyl orthosilicate simultaneously as inorganic part, both can reduce the simple high cost using ethyl orthosilicate to cause, also can solve Ludox hydrolysis and generate the uneven deficiency of silica dispersion; Select the polyisocyanates containing-NCO and Si-OH group generation polycondensation reaction, make organic moiety and inorganic part by chemical reaction natural combination to together with, again through crosslinking agent effect, by bond synthesis such as intermolecular force, hydrogen bond, ionic bond or covalent bonds, make between inorganic part and organic moiety, to produce stronger interface cohesion, can overcome the shortcoming of inorganic part and organic moiety secondary separation, namely obtained compound cyst wall microcapsules life cycle is more permanent.
(3) microcapsules prepared of the present invention, not containing toxic side effect component in cyst material, and due to the use of inorganic material, make its good thermal stability, fire retardant performance is high, namely has environmental protection, durable, fire-retardant in one concurrently.
(4) the present invention is on the basis of conventional emulsion polymerizations method, adds in-situ polymerization technology, makes cyst wall firmer in forming process, and the pattern of microcapsules is more even, is convenient to future and matrix material blending.
(5) preparation technology of the present invention is simple, controllability strong, utilizes existing industrial processing technology, and almost cost free increases, and substantially increases production efficiency, is suitable for industrial-scale production and promotes.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in detail.In the present invention, described number is mass parts.
Embodiment 1
Get paraffin and 2 parts of sodium tetradecyl sulfates that 10 parts of phase transition temperatures are 30 DEG C, heat in 50 DEG C of water-baths, 800 revs/min stir and make oil phase material.
Get Ludox and ethyl orthosilicate 15 parts that silica quality percentage composition is 30%, the two mass ratio is 3:1, adds in 50 parts of deionized waters under room temperature, and 700 revs/min are stirred 20 minutes, make aqueous phase material.
Dropwise joined in the aqueous phase of stirring by oil phase material under 50 DEG C of heating water baths, rotating speed is 1000 revs/min, and mixing time obtains stable emulsion in 30 minutes.Add 40 parts of polymethylene multi-phenenyl isocyanates fast, and add 3 parts of poly-carbodiimides, Keep agitation 5 minutes, obtain the microcapsule solution that polyurethane-polysiloxane is cyst wall.Namely microcapsules of storing energy through phase change A is obtained again after vacuum filtration (suction is 5kPa, 30 minutes time), washing, dry (temperature is 60 DEG C, 12 hours time).
Embodiment 2
In embodiment 1, the paraffin number of 30 DEG C is increased to 20 parts, other material and operating condition constant, obtained microcapsules of storing energy through phase change B.
Embodiment 3
In embodiment 1, keep other material and operating condition constant, sodium tetradecyl sulfate is increased to 6 parts, obtained microcapsules of storing energy through phase change C.
Embodiment 4
In embodiment 1, be that Ludox and the ethyl orthosilicate number of 30% brings up to 35 parts by silica quality percentage composition, other condition and material constant, obtained microcapsules of storing energy through phase change D.
Embodiment 5
In embodiment 1, keep other material and operating condition constant, the Ludox getting silica quality percentage composition 45% reacts, obtained microcapsules of storing energy through phase change E.
Embodiment 6
In embodiment 1, keep other material and operating condition constant, the ratio of Ludox and ethyl orthosilicate is changed into 5:1, obtained microcapsules of storing energy through phase change F.
Embodiment 7
In embodiment 1, keep other material and operating condition constant, add 60 parts of polymethylene multi-phenenyl isocyanates, obtained microcapsules of storing energy through phase change G.
Embodiment 8
In embodiment 1, keep other material and operating condition constant, add 7 parts of poly-carbodiimides, obtained microcapsules of storing energy through phase change H.
Embodiment 9
In embodiment 1, keep other material and operating condition constant, change suction into 7kPa, baking temperature changes 80 DEG C into, and the time changes 20 hours into, obtains accumulation energy microcapsule I.
Comparative example 1
According to Collid.Polym.Sci., 2002,280, the description in 260 ~ 266, in polyureas, drip triethanolamine adjust ph is that 8.5,70 DEG C of constant temperature stir 1h with 400r/min, adds the prepolymer solution that appropriate deionized water forms transparent and stable, for subsequent use.At 60 DEG C, the sodium chloride of the solid paraffin of melting with deionized water, aqueous phase quality 10% is mixed, add the emulsifying agent of core quality 4%, pour in there-necked flask, 3000r/min emulsification 30min; 1200r/min emulsification 30min under atoleine normal temperature.Reduce rotating speed, with 10% citric acid solution to core material emulsion acid adjustment, pH value is reduced to 6; Drip prepolymer solution in emulsion, 70 DEG C of isothermal reactions, drip the citric acid solution of 10%, regulate solution ph to be 4.5, add a small amount of aqueous ammonium chloride solution and be cured, raised temperature to 80 DEG C, insulation reaction 2h.Product benzinum and deionized water respectively wash 2 times, suction filtration, and in vacuum drying oven, 60 DEG C of oven dry, obtain Powdered microcapsules J.
Comparative example 2
According to the description in CN101333432A, by the Ludox 100mL of 20% concentration, join in 500mL beaker, add 100mL deionized water, stir, obtain SiO
2content is the silicon hydrosol of 10%.Put into 10g paraffin wax, 2mL surfactant and 0.1g alum again, heat 2h at 80 DEG C, rapid stirring, form emulsion.Continue to add urea as precipitating reagent, stir 2h, adularescent Precipitation.Spend deionized water 3 times, vacuum drying 24h at 80 DEG C, obtained a kind of microcapsules of storing energy through phase change K.
Comparative example 3
In embodiment 1, keep other material and operating condition constant, only ethyl orthosilicate is added in the process making aqueous phase material, oil phase material is being added in aqueous phase material process, do not add organic cyst material polymethylene multi-phenenyl isocyanate, the i.e. independent cyst material using teos hydrolysis generation silica as microcapsules, obtained microcapsules of storing energy through phase change L.
Comparative example 4
In embodiment 1, keep other material and operating condition constant, only ethyl orthosilicate is added in the process making aqueous phase material, the inorganic cyst material of silica as microcapsules is generated using teos hydrolysis, oil phase material is being added in aqueous phase material process, add organic cyst material polymethylene multi-phenenyl isocyanate, obtained microcapsules of storing energy through phase change M.
First heat stability test is carried out to the microcapsules of storing energy through phase change of preparation, i.e. fire resistance test; Fire resistance is same under measuring and adopting oxygen index method/GB/T2406-93().So-called oxygen index method refers to, in nature air, the volumetric concentration of oxygen is 21%(and oxygen index (OI) 21), theoretically, the oxygen index (OI) of any material is only greater than 21, and it just has self-extinguishment namely to reach the target stoping burning in atmosphere.Find through test, the oxygen index (OI) of A ~ M sample is respectively 25,24,25,26,26,26,23,25,25,19,28,28 and 24, and the flame retardant effect namely with the microcapsules of inorganic cyst wall structure is better.
Secondly, carry out physicochemical property detection to microcapsules of storing energy through phase change, result is as shown in table 1.
Table 1A ~ M sample physicochemical property test result
| Microcapsules | Compressive strength/KPa | Potential heat value/kJkg -1 | Compatible | Life cycle |
| A | 350 | 85.5 | Organic and inorganic carrier | 1000 continuous circulations are without leakage |
| B | 348 | 101.6 | Organic and inorganic carrier | 1000 continuous circulations are without leakage |
| C | 320 | 74.1 | Organic and inorganic carrier | 1000 continuous circulations are without leakage |
| D | 300 | 75.5 | Organic and inorganic carrier | 1000 continuous circulations are without leakage |
| E | 287 | 73.3 | Organic and inorganic carrier | 1000 continuous circulations are without leakage |
| F | 323 | 78.6 | Organic and inorganic carrier | 1000 continuous circulations are without leakage |
| G | 370 | 78.9 | Organic and inorganic carrier | 1000 continuous circulations are without leakage |
| H | 375 | 83.2 | Organic and inorganic carrier | 1000 continuous circulations are without leakage |
| I | 345 | 83.1 | Organic and inorganic carrier | 1000 continuous circulations are without leakage |
| J | 225 | 69.3 | Organic carrier | 1000 continuous circulations are without leakage |
| K | 245 | 51.2 | Inorganic carrier | 500 times continuous circulation has leakage |
| L | 253 | 57.7 | Inorganic carrier | 500 times continuous circulation has leakage |
| M | 340 | 80.6 | Organic and inorganic carrier | 1000 continuous circulations are without leakage |
As seen from Table 1, use microcapsules prepared by composite organic-inorganic material, its mechanical performance is better than microcapsules prepared by single cyst material.Compressive strength test result shows, has the accumulation energy microcapsule of polyurethane-polysiloxane compound cyst wall, and most intensity is greater than 300KPa, has namely fully demonstrated that inorganic material hardness is high, the advantage of organic material good toughness.Be used alone microcapsules (as shown in K) prepared by Ludox, because dispersiveness is even not, cause the clad ratio of paraffin wax emulsions lower, namely gained microcapsules potential heat value declines; And silica cyst wall is more crisp, long-time continuous uses and there will be Fragmentation Phenomena, causes phase-change material to run off, and thermal storage performance declines.
In addition, in the preferable range of organic phase change material, improve organic phase change material number, the content of capsule capsula interna core material can be increased, namely improve the potential heat value of obtained microcapsules.Surfactant is too much unsuitable, otherwise in paraffin wax emulsions, bubble is too much, affects covered effect, causes microcapsules potential heat value to decline (as shown at c).Inorganic component in cyst wall and organic component, only under the proportioning of the best, just can obtain the highest compression strength values, if silica composition is too much, compound cyst wall will become more crisp, and namely compressive strength declines (as shown in E).Crosslinking agent suitably increases number in preferable range, can improve inorganic component and organic component in conjunction with effect, thus improve compressive strength.In addition, the microcapsules of compound cyst wall can be applicable to the needs of inorganic carrier and organic carrier simultaneously, namely have applicability widely.
Claims (11)
1. a preparation method for Organic-inorganic composite cyst wall accumulation energy microcapsule, comprises the following steps:
(1) by the surfactant of the organic phase change material of 5 ~ 30 parts and 0.5 ~ 10 part, heat at 30 ~ 80 DEG C, stir under 500 ~ 1500 revs/min, obtain the oil phase material mixed;
(2) getting silica quality percentage composition is the Ludox of 25% ~ 65% and the ethyl orthosilicate of 10 ~ 40 parts, wherein the mass ratio of Ludox and ethyl orthosilicate is 1:1 ~ 10:1, add in the deionized water of 30 ~ 80 parts, stir under 500 ~ 1000 revs/min under room temperature, mix and make aqueous phase material;
(3) joined by the oil phase material of step (1) in the aqueous phase material of step (2), heat at 30 ~ 80 DEG C, stir under 500 ~ 1500 revs/min, mixing time 20 ~ 100 minutes, makes oil phase material dispersed one-tenth emulsion in aqueous phase; Add rapidly the polyisocyanates of 30 ~ 70 parts subsequently, add the crosslinking agent of 1 ~ 10 part simultaneously, at the former temperature of maintenance and speed of agitator, stablize 3 ~ 10 minutes, obtain the microcapsules with Organic-inorganic composite cyst wall;
(4) namely product is obtained after the liquid obtained step (3) carries out vacuum filtration, washing, drying.
2. in accordance with the method for claim 1, it is characterized in that: in step (1), the consumption of organic phase change material is 10 ~ 20 parts, and the consumption of surfactant is 2 ~ 6 parts.
3. in accordance with the method for claim 1, it is characterized in that: the organic phase change material that step (1) uses is paraffin, C
14~ C
22n-alkane, C
9~ C
18higher fatty acids and ester class in one or more.
4. in accordance with the method for claim 1, it is characterized in that: the organic phase change material that step (1) uses is 18
#paraffin, 20
#paraffin, 25
#paraffin, 30
#paraffin, 45
#paraffin, 58
#one or more in paraffin or BS.
5. according to the method described in claim 1,2,3 or 4, it is characterized in that: the phase transition temperature of the organic phase change material that step (1) uses is 18 ~ 60 DEG C.
6. according to the method described in claim 1 or 2, it is characterized in that: the surfactant that step (1) uses is polyethylene glycol, one or more in sucrose ester, polysorbate, octadecyl benzenesulfonic acid, lauryl sodium sulfate, sodium tetradecyl sulfate, sodium hexadecyl sulfate.
7. in accordance with the method for claim 1, it is characterized in that: in step (2), the silica quality percentage composition of Ludox is 30% ~ 45%, and the consumption of ethyl orthosilicate is 15 ~ 35 parts, and the mass ratio of Ludox and ethyl orthosilicate is 3:1 ~ 5:1.
8. in accordance with the method for claim 1, it is characterized in that: in step (3), the consumption of polyisocyanates is 40 ~ 60 parts, and the consumption of crosslinking agent is 3 ~ 7 parts.
9. according to the method described in claim 1 or 8, it is characterized in that: the polyisocyanates used in step (3) is toluene di-isocyanate(TDI), one or more in MDI, polymethylene multi-phenenyl isocyanate, IPDI.
10. in accordance with the method for claim 1, it is characterized in that: the crosslinking agent used in step (3) is ethylenediamine, water-soluble epoxy resin, containing one or more in the poly-carbodiimide (PCDI) of-NCN.
11. in accordance with the method for claim 1, it is characterized in that: in step (4), the suction of vacuum filtration is 3 ~ 9kPa, and the time is 30 minutes; Baking temperature is 50 ~ 100 DEG C, and the time is 10 ~ 30 hours.
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| CN101503618A (en) * | 2009-03-09 | 2009-08-12 | 中国科学技术大学 | Silicon dioxide gel micro-encapsulated phase change energy storage material and preparation thereof |
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