CN101942290A - Method for preparing polyethylene glycol/silicon dioxide composite shape-stabilized phase change energy storage material and product thereof - Google Patents
Method for preparing polyethylene glycol/silicon dioxide composite shape-stabilized phase change energy storage material and product thereof Download PDFInfo
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Abstract
The invention discloses a method for preparing a polyethylene glycol/silicon dioxide composite shape-stabilized phase change energy storage material and a product thereof. The method comprises the following steps of: dissolving polyethylene glycol serving as a work substance into water in an amount of between 0.2 and 1.0g/ml to obtain water solution of the polyethylene glycol; dripping a side product SiCl4 of polycrystalline silicon into the obtained water solution of the polyethylene glycol for a hydrolysis and sol-gel reaction to form gel with a three-dimensional network structure; drying the gel to prepare powder, removing water and hydrogen chloride from the powder; and dripping a modifier for modifying the surface of the powder hydrophobically in an amount which accounts for 0.1 to 1.5 weight percent of the powder at the temperature of 80 DEG C under the protection of nitrogen for surface modification to obtain the polyethylene glycol/silicon dioxide composite shape-stabilized phase change energy storage material. The method can change wastes into valuables and reduce the manufacturing cost of the product by using the side product SiCl4 of the polycrystalline as a silicon source, and is favorable for the industrial production and wide popularization and application of the SiO2 shape-stabilized phase change energy storage material.
Description
Affiliated technical field
The present invention relates to the heat energy energy storage material, especially polyoxyethylene glycol/silicon-dioxide composite shape-setting phase-changing energy storage material is made the field.
Background technology
Siemens produces in the polysilicon process with improvement, can produce a large amount of by product-silicon tetrachlorides, and 1 kilogram of polysilicon of every production will produce 10-15 kilogram silicon tetrachloride.And silicon tetrachloride is the liquid that a kind of poisonous and harmful has severe corrosive, and is if do not recycle, very big to environment and human body safety hazard.According to statistics, China built and the polysilicon producer that builds have 40 surplus family, the comprehensive utilization of silicon tetrachloride has become the technical bottleneck of restriction China polysilicon Sustainable development.At present, the comprehensive utilization of silicon tetrachloride mainly contains both direction: the one, the silicon tetrachloride of reduction in the tail gas is translated into the raw material-trichlorosilane of polysilicon by high temperature or low temperature hydrogenation, return production of polysilicon system direct production polysilicon again, but can only utilize a part.The 2nd, produce other Chemicals with silicon tetrachloride, as white carbon black, tetraethyl silicate and organosilicon product etc., but because the cost and the question of market also can't digest a large amount of silicon tetrachloride that production of polysilicon produces.Therefore, it is imperative to seek the silicon tetrachloride comprehensive utilization technique that a kind of cost is low, energy consumption is low and market outlook are wide.Phase change energy storage technology has become the focus that scientific circles and industrial community are paid close attention to as a kind of new energy-saving and emission-reduction mode.The characteristics that phase-changing energy storage material utilizes material to absorb energy and release energy in phase transition process realize the storage and the utilization of energy, alleviate the imbalance between supply and demand of energy on room and time, reach the purpose that improves energy use efficiency.Therefore in the society that the energy and environmental problem are serious day by day now, phase-changing energy storage material has important value in fields such as building energy conservation, sun power utilization, waste heat recovery and electric power peak load shiftings, receives much attention in various fields such as the energy, material, aerospace, weaving, electric power and building.
According to the difference of phase transition process physical form, Gu the phase-change accumulation energy material can be divided into solid-liquid, solid-gas, liquid-gas, solid-four kinds.Volume change is big before and after the phase transformation Gu-gas and liquid-gas phase becomes ergastic substances, during use a lot of complex appts to be arranged, therefore less use in practical engineering application, and the common energy storage density of solid-solid phase-change ergastic substances is too little, system applicatory is few, also less in actual applications use.Solid-liquid phase change energy storage material energy storage density is big, phase transformation front and back volume change is little, and approximately constant temperature, have broad application prospects in practical engineering application, yet flowability after its phase transformation and corrodibility is the outstanding problem in its use.Technological method mobile and corrosion problems mainly contains encapsulated and settingization after solving at present the phase transformation of solid-liquid phase change energy storage material, soon phase-changing energy storage material be embedded into have three-dimensional net structure, in the compound of laminate structure or vesicular structure.SiO
2As a kind of inexpensive and porous mass that specific surface area is big, be widely used in the setting modification of solid-liquid phase change ergastic substances, SiO
2The preparation method of setting phase change energy storage material mainly contains two kinds, and the one, the vacuum plunging, i.e. employing vacuumizing decompression makes porous material take off absorption, and the effect that the phase-change accumulation energy material after the phase transformation is pressed at air is pushed down in the pore space structure of how empty material; The 2nd, sol-gel method is about to the phase-change accumulation energy substance dissolves or is dispersed in the water, and the method by sol-gel method is to the modification that formalizes of phase-change accumulation energy material.The vacuum plunging mainly seals the phase-change accumulation energy material by " capillary " physisorption of vesicular structure, and network confinement even the bonding action of sol-gel by vesicular structure " capillary " physical adsorption, polymer network structure seals the phase-change accumulation energy material.Therefore, compare with the vacuum plunging, sol-gel method prepares SiO
2The leakage efficiency of setting phase change energy storage material is higher, and sealing property is better.
Disclosed at present sol-gel method prepares SiO
2The silicon source of setting phase change energy storage material mainly is water glass and silicoorganic compound, and preparation process often needs to add promotor, owing to be thermo-negative reaction, also need additional heating source, not only raw materials cost is higher, and the production cycle is longer, production technique is complicated, and production cost is also higher, is unfavorable for SiO
2The suitability for industrialized production of setting phase change energy storage material has limited SiO greatly
2The engineering of setting phase change energy storage material is used.
Summary of the invention
Above shortcoming in view of prior art, the objective of the invention is to overcome the deficiencies in the prior art, studying a kind of is the polyoxyethylene glycol/silicon-dioxide composite shape-setting phase-changing energy storage material and preparation method thereof in silicon source with the silicon tetrachloride as by-product of polysilicon, and to grope silicon tetrachloride be the rational process program in silicon source, making it both can turn waste into wealth, can reduce production cost of products again, help SiO
2The suitability for industrialized production of setting phase change energy storage material and applying widely.
The objective of the invention is to realize by following means.
The preparation method of polyoxyethylene glycol/silicon-dioxide composite shape-setting phase-changing energy storage material comprises the steps:
(1) the peek average molecular weight is that two kinds of polyoxyethylene glycol in the polyoxyethylene glycol of 600-20000 or the polyoxyethylene glycol that number-average molecular weight is 600-20000 mix by 0.5-1/1 and obtain the operation material polyoxyethylene glycol, the operation material polyoxyethylene glycol is dissolved in the water by 0.2-1.0g/ml, obtains the polyoxyethylene glycol aqueous solution;
(2) with polysilicon by product SiCl
4Be added drop-wise in the polyoxyethylene glycol aqueous solution of step (1) gained, the gel that hydrolysis and sol gel reaction form three-dimensional net structure takes place;
(3) gel drying that step (2) is obtained is smashed to pieces, makes powder;
(4) powder that step (3) is obtained dewaters and hydrogenchloride; under nitrogen protection; under 80 ℃ of temperature; drip the properties-correcting agent that makes its surface hydrophobicity modification by the 0.1-1.5% weight that accounts for described powder; behind the surface modification 3h; lower the temperature, stop stirring, backflow and logical nitrogen, obtain polyoxyethylene glycol/silicon-dioxide composite shape-setting phase-changing energy storage material.
The present invention also aims to, obtain a kind of polyoxyethylene glycol/silicon-dioxide composite shape-setting phase-changing energy storage material, make that polyoxyethylene glycol is embedded in the mesh structural porous structure of silicon-dioxide more securely in the gained material.
Described energy storage material is made of carrier matrix and operation material, and carrier matrix is a silica dioxide gel, accounts for the 15-60% of composite shape-setting phase-changing energy storage material total mass; Operation material is polyoxyethylene glycol or polyoxyethylene glycol mixture, accounts for the 40-85% of composite shape-setting phase-changing energy storage material total mass.
Adopt method of the present invention, with production of polysilicon by product SiCl
4Be the silicon source, both can turn waste into wealth, can reduce production cost of products again, help SiO
2The suitability for industrialized production of setting phase change energy storage material and applying widely.
Product of the present invention has the reticulated structure silicon-dioxide of high-specific surface area, multi-cellular structure.The silicon hydroxyl (Si-OH) of the capillary adsorption by microvoid structure, network confinement, bonding action and the silica sphere of network structure and polyoxyethylene glycol terminal hydroxy group (CH
2-hydrogen bond action between OH) is embedded into polyoxyethylene glycol in the mesh structural porous structure of silicon-dioxide firmly.When the generation solid-liquid changed mutually, the polyoxyethylene glycol liquid that can not leaked out from silicon dioxide skeleton.Powder after the modification can adopt tabletting machine to make variform polyoxyethylene glycol/silicon-dioxide composite shape-setting phase-changing energy storage material block.
Description of drawings
Fig. 1 is the DSC curve (embodiment 1) of polyoxyethylene glycol and polyoxyethylene glycol/silicon-dioxide composite shape-setting phase-changing energy storage material;
Fig. 2 is the TG curve (embodiment 1) of polyoxyethylene glycol/silicon-dioxide composite shape-setting phase-changing energy storage material;
Fig. 3 is the scanning electron microscope of polyoxyethylene glycol/silicon-dioxide composite shape-setting phase-changing energy storage material
Figure (embodiment 1).
Fig. 4 is the proportioning and the materials table of various embodiments of the present invention.
Embodiment
Operation material of the present invention is that number-average molecular weight is the polyoxyethylene glycol of 600-20000 or number-average molecular weight two kinds of mixtures that polyoxyethylene glycol obtains by 0.5-1/1 in the different number-average molecular weights of 600-20000 scope, preferred number average molecular weight is 600,800,1000,1500,2000,3000,4000 and 6000 polyoxyethylene glycol, i.e. PEG-600, PEG-800, PEG-1000, PEG-1500, PEG-2000, PEG-3000, PEG-4000 and PEG-6000.
Principle of work of the present invention is as follows: by production of polysilicon by product SiCl
4Hydrolysis produce HCl and silicic acid, polymerization generation sol gel reaction very easily takes place in silicic acid under HCl catalysis, obtain the reticulated structure silicon-dioxide of high-specific surface area, multi-cellular structure.The silicon hydroxyl (Si-OH) of the capillary adsorption by microvoid structure, network confinement, bonding action and the silica sphere of network structure and polyoxyethylene glycol terminal hydroxy group (CH
2-hydrogen bond action between OH) is embedded into polyoxyethylene glycol in the mesh structural porous structure of silicon-dioxide firmly.When the generation solid-liquid changed mutually, the polyoxyethylene glycol liquid that can not leaked out from silicon dioxide skeleton.The silicon hydroxyl is arranged owing to polyoxyethylene glycol/silicon dioxide powder surface is remaining, and responsive to airborne moisture content, moisture easily is adsorbed on powder surface, therefore, needs to add silane coupling agent or Resins, epoxy and solidifying agent thereof it is carried out surface modification.
Embodiment 1
Step: under (1) room temperature, 12.0gPEG-6000 is dissolved in the 15.0ml water obtains polyglycol solution, under magnetic stirrer, slowly drip production of polysilicon by product SiCl
45.73ml, make whole gelations.Gel taken out places watch-glass, and watch-glass is put into air dry oven, under 80 ℃, be dried to constant weight, obtain xerogel, xerogel is taken out, in mortar, smash to pieces, change over to again in the watch-glass, with powerful mechanical crusher pulverize powder.(2) powder is changed under 40 ℃, vacuumize dry 2.5 hours in the vacuum drying oven; further remove water outlet and hydrogenchloride; then this powder is packed in the 250ml four-hole bottle that agitator, nitrogen tube, return line, dropping funnel are housed; under nitrogen protection; in powder gross weight 0.5% ratio, drip silane resin acceptor kh-550, behind the surface modification 3h under 80 ℃ of temperature; lower the temperature, stop stirring, backflow and logical nitrogen, obtain polyoxyethylene glycol/silicon-dioxide composite shape-setting phase-changing energy storage material.(3) take by weighing polyoxyethylene glycol/silicon-dioxide composite shape-setting phase-changing energy storage material powder that 5.0g makes, be tiled in the clean watch-glass, form the skim sample powder, in 100 ℃, placed 1 hour, take out the back and in watch-glass, do not observed the polyoxyethylene glycol adhesion, illustrating does not have polyoxyethylene glycol generation seepage flow, and silicon-dioxide has played good setting effect to polyoxyethylene glycol.Fig. 1 is the DSC curve of polyoxyethylene glycol and polyoxyethylene glycol/silicon-dioxide composite shape-setting phase-changing energy storage material.The phase transformation enthalpy of polyoxyethylene glycol/silicon-dioxide composite shape-setting phase-changing energy storage material is 133.4J/g, and the phase transformation enthalpy of the pure polyoxyethylene glycol of operation material is 158.0J/g, and carrier matrix silicon-dioxide does not undergo phase transition in test specification.Fig. 2 is the TG curve of polyoxyethylene glycol/silicon-dioxide composite shape-setting phase-changing energy storage material, and the temperature of silicon-dioxide and polyoxyethylene glycol/silicon-dioxide composite shape-setting phase-changing energy storage material weightlessness 5% is 148 ℃, and maximum heat weight loss rate temperature is 178 ℃.Fig. 3 is the sem photograph of polyoxyethylene glycol/silicon-dioxide composite shape-setting phase-changing energy storage material, and the vesicular structure of carrier matrix silicon-dioxide disappears, and silicon-dioxide has played good coating effect to polyoxyethylene glycol.In this example, polyoxyethylene glycol accounts for 80% of composite shape-setting phase-changing energy storage material total mass.
Step: under (1) room temperature, 17.0gPEG-20000 is dissolved in the 17.0ml water obtains polyglycol solution, under magnetic stirrer, slowly drip production of polysilicon by product SiCl
45.74ml, make whole gelations.Gel taken out places watch-glass, and watch-glass is put into air dry oven, under 80 ℃, be dried to constant weight, obtain xerogel, xerogel is taken out, in mortar, smash to pieces, change over to again in the watch-glass, with powerful mechanical crusher pulverize powder.(2) powder is changed under 40 ℃, vacuumize dry 2.0 hours in the vacuum drying oven; further remove and anhydrate and hydrogenchloride; then this powder is packed in the 250ml four-hole bottle that agitator, nitrogen tube, return line, dropping funnel are housed; under nitrogen protection; in powder gross weight 0.1% ratio, drip silane coupling agent KH-560, behind the surface modification 3h under 80 ℃ of temperature; lower the temperature, stop stirring, backflow and logical nitrogen, obtain polyoxyethylene glycol/silicon-dioxide composite shape-setting phase-changing energy storage material.(3) take by weighing polyoxyethylene glycol/silicon-dioxide composite shape-setting phase-changing energy storage material powder that 5.0g makes, be tiled in the clean watch-glass, form the skim sample powder, in 100 ℃, placed 1 hour, take out the back and in watch-glass, do not observed the polyoxyethylene glycol adhesion, illustrating does not have polyoxyethylene glycol generation seepage flow, and silicon-dioxide has played good setting effect to polyoxyethylene glycol.In this example, polyoxyethylene glycol accounts for 85% of composite shape-setting phase-changing energy storage material total mass.
Embodiment 3
Step: under (1) room temperature, 14.0gPEG-10000 is dissolved in the 20.0ml water obtains polyglycol solution, under magnetic stirrer, slowly drip production of polysilicon by product SiCl
411.5ml, make whole gelations.Gel taken out places watch-glass, and watch-glass is put into air dry oven, under 80 ℃, be dried to constant weight, obtain xerogel, xerogel is taken out, in mortar, smash to pieces, change over to again in the watch-glass, with powerful mechanical crusher pulverize powder.(2) powder is changed under 40 ℃, vacuumize dry 3.0 hours in the vacuum drying oven; further remove and anhydrate and hydrogenchloride; then this powder is packed in the 250ml four-hole bottle that agitator, nitrogen tube, return line, dropping funnel are housed; under nitrogen protection; in powder gross weight 0.3% ratio, drip silane coupling agent KH-570, behind the surface modification 3h under 80 ℃ of temperature; lower the temperature, stop stirring, backflow and logical nitrogen, obtain polyoxyethylene glycol/silicon-dioxide composite shape-setting phase-changing energy storage material.(3) take by weighing polyoxyethylene glycol/silicon-dioxide composite shape-setting phase-changing energy storage material powder that 5.0g makes, be tiled in the clean watch-glass, form the skim sample powder, in 100 ℃, place 10min, take out the back and in watch-glass, do not observed the polyoxyethylene glycol adhesion, illustrating does not have polyoxyethylene glycol generation seepage flow, and silicon-dioxide has played good setting effect to polyoxyethylene glycol.In this example, polyoxyethylene glycol accounts for 70% of composite shape-setting phase-changing energy storage material total mass.
Embodiment 4
Step: under (1) room temperature, 12.0gPEG-2000 is dissolved in the 24.0ml water obtains polyglycol solution, under magnetic stirrer, slowly drip production of polysilicon by product SiCl
415.32ml, make whole gelations.Gel taken out places watch-glass, and watch-glass is put into air dry oven, under 80 ℃, be dried to constant weight, obtain xerogel, xerogel is taken out, in mortar, smash to pieces, change over to again in the watch-glass, with powerful mechanical crusher pulverize powder.(2) powder is changed under 40 ℃, vacuumize dry 3.0 hours in the vacuum drying oven; further remove and anhydrate and hydrogenchloride; then this powder is packed in the 250ml four-hole bottle that agitator, nitrogen tube, return line, dropping funnel are housed; under nitrogen protection; in powder gross weight 1.0% ratio, drip silane resin acceptor kh-550, behind the surface modification 3h under 80 ℃ of temperature; lower the temperature, stop stirring, backflow and logical nitrogen, obtain polyoxyethylene glycol/silicon-dioxide composite shape-setting phase-changing energy storage material.(3) take by weighing polyoxyethylene glycol/silicon-dioxide composite shape-setting phase-changing energy storage material powder that 5.0g makes, be tiled in the clean watch-glass, form the skim sample powder, in 100 ℃, placed 1 hour, take out the back and in watch-glass, do not observed the polyoxyethylene glycol adhesion, illustrating does not have polyoxyethylene glycol generation seepage flow, and silicon-dioxide has played good setting effect to polyoxyethylene glycol.In this example, polyoxyethylene glycol accounts for 60% of composite shape-setting phase-changing energy storage material total mass.
Embodiment 5
Step: under (1) room temperature, 10.0gPEG-1000 is dissolved in the 33.3ml water obtains polyglycol solution, under magnetic stirrer, slowly drip production of polysilicon by product SiCl
419.1ml, make whole gelations.Gel taken out places watch-glass, and watch-glass is put into air dry oven, under 80 ℃, be dried to constant weight, obtain xerogel, xerogel is taken out, in mortar, smash to pieces, change over to again in the watch-glass, with powerful mechanical crusher pulverize powder.(2) powder is changed under 40 ℃, vacuumize dry 3.5 hours in the vacuum drying oven; further remove and anhydrate and hydrogenchloride; then this powder is packed in the 250ml four-hole bottle that agitator, nitrogen tube, return line, dropping funnel are housed; under nitrogen protection; in powder gross weight 1.2% ratio, drip silane coupling agent KH-560, behind the surface modification 3h under 80 ℃ of temperature; lower the temperature, stop stirring, backflow and logical nitrogen, obtain polyoxyethylene glycol/silicon-dioxide composite shape-setting phase-changing energy storage material.(3) take by weighing polyoxyethylene glycol/silicon-dioxide composite shape-setting phase-changing energy storage material powder that 5.0g makes, be tiled in the clean watch-glass, form the skim sample powder, in 100 ℃, placed 1 hour, take out the back and in watch-glass, do not observed the polyoxyethylene glycol adhesion, illustrating does not have polyoxyethylene glycol generation seepage flow, and silicon-dioxide has played good setting effect to polyoxyethylene glycol.In this example, polyoxyethylene glycol accounts for 50% of composite shape-setting phase-changing energy storage material total mass.
Embodiment 6
Step: under (1) room temperature, 8.0gPEG-600 is dissolved in the 40.0ml water obtains polyglycol solution, under magnetic stirrer, slowly drip production of polysilicon by product SiCl
423.0ml, make whole gelations.Gel taken out places watch-glass, and watch-glass is put into air dry oven, under 80 ℃, be dried to constant weight, obtain xerogel, xerogel is taken out, in mortar, smash to pieces, change over to again in the watch-glass, with powerful mechanical crusher pulverize powder.(2) powder is changed under 40 ℃, vacuumize dry 4.0 hours in the vacuum drying oven; further remove and anhydrate and hydrogenchloride; then this powder is packed in the 250ml four-hole bottle that agitator, nitrogen tube, return line, dropping funnel are housed; under nitrogen protection, under 80 ℃ of temperature, in powder gross weight 1.5% ratio; drip silane coupling agent KH-560; behind the surface modification 3h, lower the temperature, stop stirring, backflow and logical nitrogen, obtain polyoxyethylene glycol/silicon-dioxide composite shape-setting phase-changing energy storage material.(3) take by weighing polyoxyethylene glycol/silicon-dioxide composite shape-setting phase-changing energy storage material powder that 5.0g makes, be tiled in the clean watch-glass, form the skim sample powder, in 100 ℃, placed 1 hour, take out the back and in watch-glass, do not observed the polyoxyethylene glycol adhesion, illustrating does not have polyoxyethylene glycol generation seepage flow, and silicon-dioxide has played good setting effect to polyoxyethylene glycol.In this example, polyoxyethylene glycol accounts for 40% of composite shape-setting phase-changing energy storage material total mass.
Embodiment 7
Step: under (1) room temperature, 10.0gPEG-800 is dissolved in the 33.3ml water obtains polyglycol solution, under magnetic stirrer, slowly drip production of polysilicon by product SiCl
419.1ml, make whole gelations.Gel taken out places watch-glass, and watch-glass is put into air dry oven, under 80 ℃, be dried to constant weight, obtain xerogel, xerogel is taken out, in mortar, smash to pieces, change over to again in the watch-glass, with powerful mechanical crusher pulverize powder.(2) powder is changed under 40 ℃, vacuumize dry 2.5 hours in the vacuum drying oven; further remove and anhydrate and hydrogenchloride; then this powder is packed in the 250ml four-hole bottle that agitator, nitrogen tube, return line, dropping funnel are housed; under nitrogen protection; under 80 ℃ of temperature in powder gross weight 1.0% ratio; drip epoxy resin E-44 and low molecular polyamides solidifying agent thereof; behind the surface modification 3h; lower the temperature, stop stirring, backflow and logical nitrogen, obtain polyoxyethylene glycol/silicon-dioxide composite shape-setting phase-changing energy storage material.(3) take by weighing polyoxyethylene glycol/silicon-dioxide composite shape-setting phase-changing energy storage material powder that 5.0g makes, be tiled in the clean watch-glass, form the skim sample powder, in 100 ℃, placed 1 hour, take out the back and in watch-glass, do not observed the polyoxyethylene glycol adhesion, illustrating does not have polyoxyethylene glycol generation seepage flow, and silicon-dioxide has played good setting effect to polyoxyethylene glycol.In this example, polyoxyethylene glycol accounts for 50% of composite shape-setting phase-changing energy storage material total mass.
Embodiment 8
Step: under (1) room temperature, 12.0gPEG (PEG-20000/PEG-6000=1/2) is dissolved in the 24.0ml water obtains polyglycol solution, under magnetic stirrer, slowly drip production of polysilicon by product SiCl
45.73ml, make whole gelations.Gel taken out places watch-glass, and watch-glass is put into air dry oven, under 80 ℃, be dried to constant weight, obtain xerogel, xerogel is taken out, in mortar, smash to pieces, change over to again in the watch-glass, with powerful mechanical crusher pulverize powder.(2) powder is changed under 40 ℃, vacuumize dry 2.5 hours in the vacuum drying oven; further remove and anhydrate and hydrogenchloride; then this powder is packed in the 250ml four-hole bottle that agitator, nitrogen tube, return line, dropping funnel are housed; under nitrogen protection; in powder gross weight 0.5% ratio, drip silane coupling agent KH-560, behind the surface modification 3h under 80 ℃ of temperature; lower the temperature, stop stirring, backflow and logical nitrogen, obtain polyoxyethylene glycol/silicon-dioxide composite shape-setting phase-changing energy storage material.(3) take by weighing polyoxyethylene glycol/silicon-dioxide composite shape-setting phase-changing energy storage material powder that 5.0g makes, be tiled in the clean watch-glass, form the skim sample powder, in 100 ℃, placed 1 hour, take out the back and in watch-glass, do not observed the polyoxyethylene glycol adhesion, illustrating does not have polyoxyethylene glycol generation seepage flow, and silicon-dioxide has played good setting effect to polyoxyethylene glycol.In this example, the polyoxyethylene glycol mixture accounts for 80% of composite shape-setting phase-changing energy storage material total mass.The amount ratio of the polyoxyethylene glycol of different number-average molecular weights is 0.5/1.
Embodiment 9
Step: under (1) room temperature, 12.0gPEG (PEG-6000/PEG-600=1/1) is dissolved in the 24.0ml water obtains polyglycol solution, under magnetic stirrer, slowly drip production of polysilicon by product SiCl
45.73ml, make whole gelations.Gel taken out places watch-glass, and watch-glass is put into air dry oven, under 80 ℃, be dried to constant weight, obtain xerogel, xerogel is taken out, in mortar, smash to pieces, change over to again in the watch-glass, with powerful mechanical crusher pulverize powder.(2) powder is changed under 40 ℃, vacuumize dry 2.5 hours in the vacuum drying oven; further remove and anhydrate and hydrogenchloride; then this powder is packed in the 250ml four-hole bottle that agitator, nitrogen tube, return line, dropping funnel are housed; under nitrogen protection; in powder gross weight 0.5% ratio, drip silane coupling agent KH-570, behind the surface modification 3h under 80 ℃ of temperature; lower the temperature, stop stirring, backflow and logical nitrogen, obtain polyoxyethylene glycol/silicon-dioxide composite shape-setting phase-changing energy storage material.(3) take by weighing polyoxyethylene glycol/silicon-dioxide composite shape-setting phase-changing energy storage material powder that 5.0g makes, be tiled in the clean watch-glass, form the skim sample powder, in 100 ℃, placed 1 hour, take out the back and in watch-glass, do not observed the polyoxyethylene glycol adhesion, illustrating does not have polyoxyethylene glycol generation seepage flow, and silicon-dioxide has played good setting effect to polyoxyethylene glycol.In this example, the polyoxyethylene glycol mixture accounts for 80% of composite shape-setting phase-changing energy storage material total mass.The amount ratio of the polyoxyethylene glycol of different number-average molecular weights is 1/1.
Embodiment 10
Step: under (1) room temperature, 12.0gPEG (PEG-10000/PEG-4000=4/5) is dissolved in the 24.0ml water obtains polyglycol solution, under magnetic stirrer, slowly drip production of polysilicon by product SiCl
45.73ml, make whole gelations.Gel taken out places watch-glass, and watch-glass is put into air dry oven, under 80 ℃, be dried to constant weight, obtain xerogel, xerogel is taken out, in mortar, smash to pieces, change over to again in the watch-glass, with powerful mechanical crusher pulverize powder.(2) powder is changed under 40 ℃, vacuumize dry 2.5 hours in the vacuum drying oven; further remove and anhydrate and hydrogenchloride; then this powder is packed in the 250ml four-hole bottle that agitator, nitrogen tube, return line, dropping funnel are housed; under nitrogen protection; under 80 ℃ of temperature in powder gross weight 0.5% ratio; drip epoxy resin E-44 and polyamide-based epoxy curing agent thereof; behind the surface modification 3h; lower the temperature, stop stirring, backflow and logical nitrogen, obtain polyoxyethylene glycol/silicon-dioxide composite shape-setting phase-changing energy storage material.(3) take by weighing polyoxyethylene glycol/silicon-dioxide composite shape-setting phase-changing energy storage material powder that 5.0g makes, be tiled in the clean watch-glass, form the skim sample powder, in 100 ℃, placed 1 hour, take out the back and in watch-glass, do not observed the polyoxyethylene glycol adhesion, illustrating does not have polyoxyethylene glycol generation seepage flow, and silicon-dioxide has played good setting effect to polyoxyethylene glycol.In this example, the polyoxyethylene glycol mixture accounts for 80% of composite shape-setting phase-changing energy storage material total mass.The amount ratio of the polyoxyethylene glycol of different number-average molecular weights is 0.8/1.
Embodiment 11
Step: under (1) room temperature, 12.0gPEG (PEG-10000/PEG-2000=3/5) is dissolved in the 24.0ml water obtains polyglycol solution, under magnetic stirrer, slowly drip production of polysilicon by product SiCl
45.73ml, make whole gelations.Gel taken out places watch-glass, and watch-glass is put into air dry oven, under 80 ℃, be dried to constant weight, obtain xerogel, xerogel is taken out, in mortar, smash to pieces, change over to again in the watch-glass, with powerful mechanical crusher pulverize powder.(2) powder is changed under 40 ℃, vacuumize dry 2.5 hours in the vacuum drying oven; further remove and anhydrate and hydrogenchloride; then this powder is packed in the 250ml four-hole bottle that agitator, nitrogen tube, return line, dropping funnel are housed; under nitrogen protection; under 80 ℃ of temperature in powder gross weight 0.5% ratio; drip epoxy resin E-44 and low molecular polyamides solidifying agent thereof; behind the surface modification 3h; lower the temperature, stop stirring, backflow and logical nitrogen, obtain polyoxyethylene glycol/silicon-dioxide composite shape-setting phase-changing energy storage material.(3) take by weighing polyoxyethylene glycol/silicon-dioxide composite shape-setting phase-changing energy storage material powder that 5.0g makes, be tiled in the clean watch-glass, form the skim sample powder, in 100 ℃, placed 1 hour, take out the back and in watch-glass, do not observed the polyoxyethylene glycol adhesion, illustrating does not have polyoxyethylene glycol generation seepage flow, and silicon-dioxide has played good setting effect to polyoxyethylene glycol.In this example, the polyoxyethylene glycol mixture accounts for 80% of composite shape-setting phase-changing energy storage material total mass.The amount ratio of the polyoxyethylene glycol of different number-average molecular weights is 0.8/1.
Material used in last embodiment is technical grade.Wherein: the Resins, epoxy trade mark: E-44, producer: jiangsu wuxi resin processing plant.Solidifying agent: 650# polyamide curing agent, producer: Jiangxi, Jiangxi Province westernization worker company limited.Polyoxyethylene glycol: PEG-600, PEG-800, PEG-1000, PEG-1500, PEG-2000, PEG-3000, PEG-4000 and PEG-6000 producer: the Long Huagongshijichang of Chengdu section.
Compared with prior art, characteristics of the present invention are significantly, can be summarized as follows
(1) adopts polysilicon by product SiCl
4Be the silicon source, because the high reaction activity of Si-Cl at room temperature just can react rapidly with water, and emit a large amount of heats, production process need not heating, and energy consumption is low.
(2) adopt polysilicon by product SiCl
4Be the silicon source, the high reaction activity owing to Si-Cl at room temperature just can react rapidly with water, and is with short production cycle.
(3) adopt polysilicon by product SiCl
4Be the silicon source, because Si-Cl and water react rapidly when generating silicic acid, also produce HCl, HCl can be used as the promotor of sol-gelization, therefore need not additionally to add promotor.
(4) adopt polysilicon by product SiCl
4Be the silicon source, it is low to compare other silicon source raw materials cost, and provides the silicon tetrachloride that a kind of cost is low, energy consumption is low and market outlook are wide comprehensive utilization technique for production of polysilicon enterprise.
Adopting Resins, epoxy and solidifying agent thereof is surface hydrophobicity properties-correcting agent, on the one hand, the epoxide group of Resins, epoxy both can with the silicon hydroxyl generation chemical reaction on surface, unreacted silicon hydroxyl and Resins, epoxy can form hydrogen bond, have the intensive interaction; Three-dimensional net structure hydrophobic structure behind the epoxy resin cure on the other hand improves the surface hydrophobicity of the product of polyoxyethylene glycol/silicon-dioxide composite shape-setting phase-changing energy storage material greatly.Consider the convenience of production process, surface hydrophobicity properties-correcting agent preferred epoxy E-44 and liquid polyamide-based epoxy curing agent.
Claims (9)
1. the preparation method of polyoxyethylene glycol/silicon-dioxide composite shape-setting phase-changing energy storage material is characterized in that comprising the steps:
(1) the peek average molecular weight is that two kinds of polyoxyethylene glycol in the polyoxyethylene glycol of 600-20000 or the polyoxyethylene glycol that number-average molecular weight is 600-20000 mix by 0.5-1/1 and obtain the operation material polyoxyethylene glycol, the operation material polyoxyethylene glycol is dissolved in the water by 0.2-1.0g/ml, obtains the polyoxyethylene glycol aqueous solution;
(2) with polysilicon by product SiCl
4Be added drop-wise in the polyoxyethylene glycol aqueous solution of step (1) gained, the gel that hydrolysis and sol gel reaction form three-dimensional net structure takes place;
(3) gel drying that step (2) is obtained is smashed to pieces, makes powder;
(4) powder that step (3) is obtained dewaters and hydrogenchloride; under nitrogen protection; under 80 ℃ of temperature; drip the properties-correcting agent that makes its surface hydrophobicity modification by the 0.1-1.5% weight that accounts for described powder; behind the surface modification 3h; lower the temperature, stop stirring, backflow and logical nitrogen, obtain polyoxyethylene glycol/silicon-dioxide composite shape-setting phase-changing energy storage material.
2. the preparation method of the polyoxyethylene glycol/silicon-dioxide composite shape-setting phase-changing energy storage material according to claim 1, it is characterized in that described operation material polyoxyethylene glycol can be following two kinds of forms: number-average molecular weight is at the single polyoxyethylene glycol of 600-20000, number-average molecular weight two kinds of mixtures that polyoxyethylene glycol obtains by 0.5-1/1 in the different number-average molecular weights of 600-20000 scope.
3. the preparation method of the polyoxyethylene glycol/silicon-dioxide composite shape-setting phase-changing energy storage material according to claim 1, it is characterized in that, drying described in the step (3) is to place 80 ℃ of air dry oven forced air dryings to constant weight gel, is cooled to after room temperature takes out, and smashs to pieces and obtains powder.
4. the preparation method of the polyoxyethylene glycol according to claim 1/silicon-dioxide composite shape-setting phase-changing energy storage material is characterized in that, dewatering and hydrogenchloride described in the step (4) is that powder was vacuumized under 40 ℃ dry 2-4 hour.
5. the preparation method of the polyoxyethylene glycol according to claim 1/silicon-dioxide composite shape-setting phase-changing energy storage material is characterized in that, described to make the properties-correcting agent of its surface hydrophobicity modification be one of following material: silane coupling agent, Resins, epoxy and solidifying agent thereof.
6. the preparation method of the polyoxyethylene glycol/silicon-dioxide composite shape-setting phase-changing energy storage material according to claim 5, it is characterized in that, described Resins, epoxy and solidifying agent thereof are epoxy resin E-44, E-42, E-51, and solidifying agent is liquid amine and acid anhydride based epoxy resin curing agent.
7. the preparation method of the polyoxyethylene glycol according to claim 6/silicon-dioxide composite shape-setting phase-changing energy storage material is characterized in that, described Resins, epoxy and solidifying agent preferred epoxy E-44 thereof and liquid polyamide-based epoxy curing agent.
8. the preparation method of the polyoxyethylene glycol/silicon-dioxide composite shape-setting phase-changing energy storage material according to claim 5, it is characterized in that described silane coupling agent comprises: aminopropyl triethoxysilane KH-550, glycidyl ether oxygen propyl trimethyl silane KH-560, methacryloxypropyl trimethoxy silane KH-570.
9. the polyoxyethylene glycol that makes by claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 methods/silicon-dioxide composite shape-setting phase-changing energy storage material, constitute by carrier matrix and operation material, it is characterized in that: carrier matrix is a silica dioxide gel, accounts for the 15-60% of composite shape-setting phase-changing energy storage material total mass; Operation material is polyoxyethylene glycol or polyoxyethylene glycol mixture, accounts for the 40-85% of composite shape-setting phase-changing energy storage material total mass.
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