CN103769021A - Preparation method of organic-inorganic composite capsule wall energy-storage microcapsule - Google Patents
Preparation method of organic-inorganic composite capsule wall energy-storage microcapsule Download PDFInfo
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Abstract
The invention discloses a preparation method of an organic-inorganic composite capsule wall energy-storage microcapsule. The method is as below: mixing an organic phase change material and a surface active agent, heating with stirring to obtain an even oil phase material; adding silica-containing silica sol and ethyl orthosilicate in a mass ratio of 1:1-10:1 into deionized water to prepare a water phase material; then adding an oil phase material into the water phase material, and uniformly dispersing into an emulsion; then adding polyisocyanate and a crosslinking agent, maintaining the original temperature and stirring speed, so as to obtain the microcapsule with the organic-inorganic composite capsule wall; and finally, conducting vacuum filtration, washing and drying on the obtained liquid substance to obtain the product. The phase change energy-storage microcapsule obtained by the method can be used in several fields such as building energy saving and insulation of pipeline storage tank, and the capsule wall of the microcapsule has the advantages of organic material and inorganic material and longer cycle of usage.
Description
Technical field
The present invention relates to the preparation method of microcapsules of storing energy through phase change, more specifically say the preparation method who there is the compound cyst wall accumulation energy microcapsule of organic and inorganic about a kind of.
Background technology
Microcapsules of storing energy through phase change, owing to can absorbing within the scope of phase transition temperature, storing, distribute a large amount of latent heat, reaches and controls ambient temperature and energy-conservation object, thereby received more concern; There is prospect widely in fields such as refrigeration air-conditioner, building energy conservation, pipeline insulation, waste heat recoveries.Microcapsules of storing energy through phase change is divided into two parts conventionally, i.e. cyst wall and nucleation material, and wherein nucleation material is coated in cyst material.Can be used in that to prepare the material of microcapsules cyst wall a lot, be mainly divided into two kinds of organic and mineral-type.Organic comprises various polymer, as melamine-formaldehyde resin, Lauxite, polyurethane and gelatin-formaldehyde resin etc.; Mineral-type is mainly the silica cyst wall that ethyl orthosilicate or Ludox generate after hydrolysis; And these existing cyst materials mostly exist certain weak point, as short in poor heat stability, life cycle, have a toxic and side effect, poor etc. with matrix material compatibility.
CN1161364A disclose a kind of with melamine resin as the preparation method of the microcapsules of storing energy through phase change of cyst wall, because melamine resin is more crisp, make the microcapsules mechanical performance that makes poor, life cycle is shorter.Also, because the heat endurance of melamine resin is lower, cause microcapsules to have certain hidden danger on fire.
The people such as Cho (Collid. Polym. Sci., 2002,280,260～266) research shows, in emulsion system, adopt interfacial polymerization take n-octadecane as core, polyureas synthesized smooth surface and particle diameter is about 1 μ m microcapsules as shell material, its phase transition temperature is 28～30 ℃, 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, as raw material, still can discharge pernicious gas in production and use procedure, and healthy and production equipment are damaged; The method cyst wall used is organic material simultaneously, has combustion-supporting potential threat, therefore in the time being applied to civilian building materials, has certain hidden danger.
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, reduce combustion-supporting risk, thereby can be 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, easily broken, the existence of these shortcomings has affected 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, take Ludox, paraffin as raw material, allows the mixture of paraffin and silicic acid separate out from system, obtains the paraffin class setting composite phase-change energy storage material of shaped by silica sol.Although the method has substituted more expensive ethyl orthosilicate as cyst material with inexpensive Ludox, but still there is some problems, it is mainly the range request harshness excessively that Ludox hydrolysis generates silica, cause silica wall thickness and microcapsule size inhomogeneous, 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 the preparation method of the compound cyst wall accumulation energy microcapsule of a kind of organic and inorganic.The microcapsules of storing energy through phase change of the method gained can be used for multiple fields such as building energy conservation and the insulation of pipeline storage tank, and this microcapsules cyst wall has the advantage of organic material and inorganic material concurrently, and life cycle is longer.
The preparation method of the compound cyst wall accumulation energy microcapsule of organic and inorganic 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, heating at 30～80 ℃, stirs the oil phase material that obtains mixing under 500～1500 revs/min;
(2) get Ludox that silica quality percentage composition is 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, under room temperature, under 500～1000 revs/min, stir, mix and make water material;
(3) oil phase material of step (1) is joined in the water material of step (2), heating at 30～80 ℃ is stirred under 500～1500 revs/min, and mixing time 20～100 minutes, makes oil phase material dispersed one-tenth emulsion in water; Add rapidly subsequently the polyisocyanates of 30～70 parts, add the crosslinking agent of 1～10 part simultaneously, under the former temperature of maintenance and speed of agitator, stablize 3～10 minutes, obtain having the microcapsules of the compound cyst wall of organic and inorganic;
(4) liquid step (3) being obtained carries out vacuum filtration, washing, obtains product after dry.
In the present invention, the organic phase change material using 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 ℃.
In the present invention, the surfactant using in step (1) is one or more in polyethylene glycol, sucrose ester, polysorbate, octadecyl benzene sulfonic 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 using in step (3) is one or more in toluene di-isocyanate(TDI), MDI, polymethylene multi-phenenyl isocyanate, IPDI, is preferably polymethylene multi-phenenyl isocyanate.
In the present invention, the crosslinking agent using in step (3), for ethylenediamine, water-soluble epoxy resin, containing one or more in the poly-carbodiimide (PCDI) of-NCN, is preferably poly-carbodiimide.
In the present invention, in step (4), the suction of vacuum filtration is 3～9kPa, is preferably 5～7kPa, and the time is 30 minutes.Baking temperature is 50～100 ℃, is preferably 60～80 ℃, and the time is 10～30 hours, is preferably 12～20 hours.
The compound cyst wall accumulation energy microcapsule of organic and inorganic prepared by the inventive method, the Si-OH group in water material can with polyisocyanates in-there is polycondensation reaction, inorganic cyst material and organic cyst material combined in NCO; Add after crosslinking agent, keeping, under former temperature and speed of agitator, forming chemical bond between inorganic phase and organic phase, obtain the microcapsules of the composite sac wall material polyurethane-polysiloxane with organic and inorganic copolymer characteristic.
The compound cyst wall accumulation energy microcapsule of organic and inorganic prepared by the inventive method is made up of cyst wall and the organic phase change material being coated in cyst wall, in microcapsules, the quality percentage composition of organic phase change material is 50%～90%, in cyst material, the quality percentage composition of silica is 10%～40%, the quality percentage composition of polyurethane is 40%～90%, spherical in shape, average grain diameter 1～10 μ m.
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 by inorganic material and organic material is compound forms, and possesses Heat stability is good, mechanical strength and the high advantage of anti-oxidant intensity of inorganic material 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, can meet the dual needs of organic matrix and inorganic matrix.
(2) aspect cyst wall formation, select Ludox and ethyl orthosilicate simultaneously as inorganic part, both can reduce expensive that simple use ethyl orthosilicate causes, also can solve Ludox hydrolysis generation silica and disperse uneven deficiency; The polyisocyanates of contain-NCO of selection and Si-OH group generation polycondensation reaction, make organic moiety and inorganic part by chemical reaction natural combination to together with, pass through again crosslinking agent effect, synthetic by bonds such as intermolecular force, hydrogen bond, ionic bond or covalent bonds, make the stronger interface combination of generation between inorganic part and organic moiety, can overcome the shortcoming of inorganic part and organic moiety secondary separation, the compound cyst wall microcapsules life cycle making is more permanent.
(3) microcapsules that prepared by the present invention, containing toxic side effect component, and due to the use of inorganic material, make its good thermal stability in cyst material, and fire retardant performance is high, has environmental protection, durable, fire-retardant in one concurrently.
(4) the present invention, on the basis of conventional emulsion polymerization, 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 is strong, utilizes existing industrial processes technology, and almost cost free increases, and has greatly improved production efficiency, is suitable for industrial-scale production and promotes.
The specific embodiment
Below in conjunction with embodiment, the present invention is described in detail.In the present invention, described umber is mass parts.
Embodiment 1
Get 10 parts of phase transition temperatures and be paraffin and 2 parts of sodium tetradecyl sulfates of 30 ℃, in 50 ℃ of water-baths, heat, 800 revs/min stir and make oil phase material.
Get 15 parts of Ludox that silica quality percentage composition is 30% and ethyl orthosilicates, 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 water material.
Under 50 ℃ of heating water baths, oil phase material is dropwise joined in the water of stirring, rotating speed is 1000 revs/min, and mixing time obtains stable emulsion for 30 minutes.Add fast 40 parts of polymethylene multi-phenenyl isocyanates, and add 3 parts of poly-carbodiimides, continue to stir 5 minutes, obtain the microcapsule solution that polyurethane-polysiloxane is cyst wall.After vacuum filtration (suction is 5kPa, 30 minutes time), washing, dry (temperature is 60 ℃, 12 hours time), obtain microcapsules of storing energy through phase change A again.
Embodiment 2
In embodiment 1, the paraffin umber of 30 ℃ is increased to 20 parts, other material and operating condition are constant, make 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, make microcapsules of storing energy through phase change C.
Embodiment 4
In embodiment 1, the Ludox that is 30% by silica quality percentage composition and ethyl orthosilicate umber are brought up to 35 parts, and other condition and material are constant, make microcapsules of storing energy through phase change D.
Embodiment 5
In embodiment 1, keep other material and operating condition constant, the Ludox of getting silica quality percentage composition 45% reacts, and makes 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, make 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, make 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, make 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 ℃ into, and the time changes 20 hours into, obtains accumulation energy microcapsule I.
Comparative example 1
According to Collid. Polym. Sci., the description in 2002,280,260～266, to dripping triethanolamine in polyureas, to regulate pH value be that 8.5,70 ℃ of constant temperature stir 1h with 400 r/min, adds the prepolymer solution of appropriate deionized water formation transparent and stable, for subsequent use.At 60 ℃, the solid paraffin of melting is mixed with the sodium chloride of deionized water, water quality 10%, 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, to the acid adjustment of core emulsion, pH value is reduced to 6 with 10% citric acid solution; Drip prepolymer solution in emulsion, 70 ℃ of isothermal reactions, drip 10% citric acid solution, and regulator solution pH value is 4.5, adds a small amount of aqueous ammonium chloride solution to be cured, rising temperature to 80 ℃, insulation reaction 2h.Product respectively washs 2 times by benzinum and deionized water, suction filtration, and 60 ℃ of oven dry in vacuum drying oven, 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 10% the silicon hydrosol.Put into 10g paraffin wax, 2mL surfactant and 0.1g alum again, heat 2h at 80 ℃, rapid stirring, forms emulsion.Continue to add urea as precipitating reagent, stir 2h, adularescent Precipitation.With deionized water washing 3 times, vacuum drying 24h at 80 ℃, makes a kind of microcapsules of storing energy through phase change K.
Comparative example 3
In embodiment 1, keep other material and operating condition constant, in the process of making water material, only add ethyl orthosilicate, oil phase material being added in water material process, do not add organic cyst material polymethylene multi-phenenyl isocyanate, generate the cyst material of silica as microcapsules using teos hydrolysis separately, make microcapsules of storing energy through phase change L.
Comparative example 4
In embodiment 1, keep other material and operating condition constant, in the process of making water material, only add ethyl orthosilicate, generate the inorganic cyst material of silica as microcapsules using teos hydrolysis, oil phase material being added in water material process, add organic cyst material polymethylene multi-phenenyl isocyanate, make microcapsules of storing energy through phase change M.
First the microcapsules of storing energy through phase change of preparation is carried out to heat stability test, i.e. fire resistance test; Fire resistance is measured under employing oxygen index method/GB/T2406-93(same).So-called oxygen index method refers to, in nature air, the volumetric concentration of oxygen is that 21%(is oxygen index (OI) 21), theoretically, the oxygen index (OI) of any material is only greater than 21, and it just has self-extinguishment to reach the target that stops burning in air.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 of microcapsules with inorganic cyst wall structure is better.
Secondly, microcapsules of storing energy through phase change is carried out to physicochemical property detection, result is as shown in table 1.
Table 1 A～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, the microcapsules that use composite organic-inorganic material to prepare, its mechanical performance is better than microcapsules prepared by single cyst material.Compressive strength test result shows to have the accumulation energy microcapsule of the compound cyst wall of polyurethane-polysiloxane, and most intensity is greater than 300KPa, has fully demonstrated that inorganic material hardness is high, the advantage of organic material good toughness.The microcapsules (as shown in K) that separately use Ludox to prepare, because dispersiveness is even not, cause the clad ratio of paraffin wax emulsions lowlyer, and gained microcapsules potential heat value declines; And silica cyst wall is more crisp, long-time continuous is used 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 umber, can increase the content of capsule capsula interna core material, improve the potential heat value that makes microcapsules.Surfactant is too much unsuitable, otherwise in paraffin wax emulsions, bubble is too much, affects covered effect, causes microcapsules potential heat value decline (as shown in C).Inorganic component in cyst wall and organic component only, under best proportioning, just can obtain the highest compression strength values, if silica composition is too much, it is more crisp that compound cyst wall will become, i.e. compressive strength decline (as shown in E).Crosslinking agent suitably increases umber in preferable range, can improve the combination effect of inorganic component and organic component, thereby improves compressive strength.In addition, the microcapsules of compound cyst wall can be applicable to the needs of inorganic carrier and organic carrier simultaneously, have applicability widely.
Claims (11)
1. a preparation method for the compound cyst wall accumulation energy microcapsule of organic and inorganic, comprises the following steps:
(1), by the surfactant of the organic phase change material of 5～30 parts and 0.5～10 part, heating at 30～80 ℃, stirs the oil phase material that obtains mixing under 500～1500 revs/min;
(2) get Ludox that silica quality percentage composition is 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, under room temperature, under 500～1000 revs/min, stir, mix and make water material;
(3) oil phase material of step (1) is joined in the water material of step (2), heating at 30～80 ℃ is stirred under 500～1500 revs/min, and mixing time 20～100 minutes, makes oil phase material dispersed one-tenth emulsion in water; Add rapidly subsequently the polyisocyanates of 30～70 parts, add the crosslinking agent of 1～10 part simultaneously, under the former temperature of maintenance and speed of agitator, stablize 3～10 minutes, obtain having the microcapsules of the compound cyst wall of organic and inorganic;
(4) liquid step (3) being obtained carries out vacuum filtration, washing, obtains product after dry.
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. it is characterized in that in accordance with the method for claim 1: the organic phase change material that step (1) is used is paraffin, C
14～C
22n-alkane, C
9～C
18higher fatty acids and ester class in one or more.
4. it is characterized in that in accordance with the method for claim 1: the organic phase change material that step (1) is used is 18
#paraffin, 20
#paraffin, 25
#paraffin, 30
#paraffin, 45
#paraffin, 58
#one or more in paraffin or BS etc.
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) is used is 18～60 ℃.
6. according to the method described in claim 1 or 2, it is characterized in that: the surfactant that step (1) is used is one or more in polyethylene glycol, sucrose ester, polysorbate, octadecyl benzene sulfonic acid, lauryl sodium sulfate, sodium tetradecyl sulfate, sodium hexadecyl sulfate etc.
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 using in step (3) is one or more in toluene di-isocyanate(TDI), MDI, polymethylene multi-phenenyl isocyanate, IPDI.
10. it is characterized in that in accordance with the method for claim 1: the crosslinking agent using in step (3) is for 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 ℃, and the time is 10～30 hours.
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