CN112007593A - Titanium dioxide phase change microcapsule material taking titanyl sulfate as titanium source and preparation method thereof - Google Patents
Titanium dioxide phase change microcapsule material taking titanyl sulfate as titanium source and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a titanium dioxide phase change microcapsule material taking titanyl sulfate as a titanium source and a preparation method thereof. The phase-change microcapsule material is prepared by taking titanyl sulfate as a titanium source, preparing and taking alkyl triethoxysilane modified titanium dioxide as a wall material and taking paraffin as a core material and adopting a direct precipitation method. According to the invention, the polymerization rate of the titanium dioxide precursor and the compatibility of the wall material and the core material are regulated and controlled by introducing the organic group through the grafting of the alkyl triethoxysilane, so that the phenomena of uneven thickness of the wall material and self-polymerization of the wall material are reduced, the utilization rate of the wall material is further improved, and the coating rate of the phase-change microcapsule material is obviously improved by 6.72-48.06%; the reaction preparation method has simple and controllable process, and the raw material titanyl sulfate is cheap and easy to obtain, non-toxic and pollution-free, and is easier to realize industrialization; the phase change microcapsule material can be widely applied to the fields of construction, textile, aerospace, medicine and the like.
Description
Technical Field
The invention relates to a phase change microcapsule material and a preparation method thereof, in particular to a titanium dioxide phase change microcapsule material taking titanyl sulfate as a titanium source and a preparation method thereof.
Background
The phase-change material is a special material which is subjected to phase change in a certain temperature range to release high-density energy and keep the temperature basically unchanged, and becomes a hot spot of domestic and foreign research because the phase-change material has the characteristic of absorbing and releasing a large amount of energy through self phase change. The paraffin is a common phase-change material, has the advantages of low phase-change temperature, large phase-change enthalpy and the like, and is non-toxic, corrosion-resistant and low in price. After paraffin is microencapsulated, the paraffin microcapsule has the advantages of stable property and leakage prevention, increases the heat conduction area, improves the heat conductivity, and has wide application prospect in the fields of buildings, textiles, aerospace, medicine and the like.
Titanium dioxide is a common inorganic wall material, and in past researches, organic substances such as butyl titanate are mostly used as a titanium source of microcapsules. Patent CN108300412A Madaichun et al uses tetrabutyl titanate as an organic titanium source as a titanium dioxide precursor, and prepares a titanium dioxide-coated phase-change microcapsule in a non-aqueous emulsion system by an in-situ polymerization method. Although titanium dioxide phase change microcapsule products prepared by organic titanium sources reported in documents have high thermal conductivity and thermal stability, organic raw materials such as tetrabutyl titanate are relatively expensive and high in toxicity, hydrolysis is insufficient in the preparation process, and the titanium dioxide phase change microcapsule products are limited to be used as titanium dioxide raw materials for industrial production of microcapsule phase change materials.
In recent years, there are many articles reported in the literature for preparing phase-change microcapsules by using titanium dioxide as a wall material. For example, Zhonglong et al [ Zhonglong, Wangbangming, Tianyuyi, Liuyin, Huaquan county, Liuli, Luleiming, Tangjianwei, preparation and characterization of a titanium dioxide-coated paraffin phase-change microcapsule [ J ]. modernization, 2019,39(03):82-86 ] A phase-change microcapsule using titanium dioxide as a wall material and paraffin as a core material was prepared by adding a titanium dioxide precursor into a paraffin emulsion by a sol-gel method and adjusting the pH value by using hydrochloric acid. The microcapsule obtained by experiments has good coating effect, centralized particle size distribution and good thermal stability. But the titanium source used by the method is butyl titanate, so that the method is not only expensive, but also has a toxic effect, and the wall material still has the phenomena of uneven thickness and self-aggregation. Zhao et al [ Liang Zhao, Hao Wang, Jie Luo, Yuan Liu, Guolin Song, Guoyi tang, fabric and properties of microencapsulated n-octade with TiO 2 shells as thermal Energy storage materials [ J ] Solar Energy,2016,127 ] prepared microcapsules with octadecane as core material and titanium dioxide as wall material using sol-gel method. Tetrabutyl titanate is used as a titanium source, n-octadecane and absolute ethyl alcohol are prepared into mixed emulsion, and the microcapsule obtained through experiments has a smoother and smoother surface and better thermal stability. But the titanium source tetrabutyl titanate is expensive and the prepared microcapsule is also seriously bonded, and the problems seriously limit the application of the titanium source tetrabutyl titanate in the practical production.
Disclosure of Invention
The invention aims to solve the technical problem of providing a titanium dioxide phase change microcapsule material taking titanyl sulfate as a titanium source and a preparation method thereof.
In order to solve the technical problems, the invention adopts the technical scheme that: a preparation method of a titanium dioxide phase change microcapsule material taking titanyl sulfate as a titanium source is prepared by taking paraffin as a core material of a phase change material and titanium dioxide as a wall material through a direct precipitation method and comprises the following steps:
(1) preparation of titanium dioxide precursor solution
Preparing a titanyl sulfate aqueous solution, adding alkyl triethoxysilane and absolute ethanol, and uniformly stirring for later use, wherein the titanyl sulfate comprises the following components in percentage by mass: water: alkyl triethoxy silane: absolute ethyl alcohol (2-3.33): 80: (6.66-8): 10;
(2) preparation of phase-change paraffin emulsion
Preparing paraffin, an emulsifier and an ammonia water solution with the mass fraction of 10% according to the mass ratio of 10:0.6:20, heating, and emulsifying under mechanical stirring to form phase-change emulsion after the paraffin of the core material is completely melted;
(3) preparation of modified phase-change microcapsule material
Dropwise adding the titanium dioxide precursor solution prepared in the step (1) into the phase-change paraffin emulsion prepared in the step (2) within 20min under mechanical stirring, adjusting the pH to 2-3 after dropwise adding, cooling to room temperature after heating reaction for 4h, standing, dehydrating by using a centrifugal machine, washing and filtering by using pure water and absolute ethyl alcohol in sequence, and drying in vacuum to obtain the phase-change microcapsule material of titanium dioxide coated paraffin modified by alkyl triethoxysilane.
The mass ratio of the paraffin consumption to the titanyl sulfate in the step (1) is (1: 2-2: 1).
In the step (1), the modifier alkyltriethoxy silane is any one of methyltriethoxysilane MTES, propyltriethoxy silane PTES, octyltriethoxy silane OTES and isobutyltriethoxy silane, and the mass ratio of the dosage of the alkyltriethoxy silane to the dosage of the titanyl sulfate is (1: 2-1: 4).
The emulsifier in the step (2) is any one of a mixture of Sodium Dodecyl Sulfate (SDS) and polyoxyethylene octyl phenol ether-10 or poloxamer, wherein the mass ratio of the SDS to the polyoxyethylene octyl phenol ether-10 is 2: 1.
The titanium dioxide phase change microcapsule material prepared by the preparation method takes titanyl sulfate as a titanium source.
The invention has the beneficial effects that:
(1) the titanyl sulfate is selected as a precursor of titanium dioxide, is cheap and easy to obtain, and is non-toxic and pollution-free.
(2) The phase-change microcapsule material is prepared by a direct precipitation method for the first time, and the reaction operation is simple and controllable.
(3) The coating rate of the microcapsule material is obviously improved by modifying titanium dioxide, and the coating rate of the modified phase-change microcapsule material is 43.36-83.70%, which is improved by 6.72-48.06% compared with the coating rate of the unmodified microcapsule material.
Drawings
FIG. 1 is a differential thermogram of the titanium dioxide coated phase change microcapsule materials described in examples 1, 2, 3 and 4 of the present invention.
FIG. 2 is a differential thermogram of the titanium dioxide coated phase change microcapsule materials described in examples 1, 3, 5, 6 and 7 of the present invention.
FIG. 3 is a differential thermogram of the titanium dioxide coated phase change microcapsule materials according to examples 1, 3, 8 and 9 of the present invention.
Fig. 4 is a differential thermal analysis diagram of the titanium dioxide-coated phase change microcapsule materials described in examples 1, 3, 10, and 11 of the present invention.
Fig. 5 is a differential thermal analysis diagram of the titanium dioxide coated phase change microcapsule materials according to examples 1, 3 and 12 of the present invention.
Fig. 6 is an image of the unmodified titanium dioxide-coated paraffin phase-change microcapsule material according to embodiment 1 of the present invention under a scanning electron microscope 18000 times.
Fig. 7 is an image of the modified titanium dioxide-coated paraffin phase-change microcapsule material according to embodiment 3 of the present invention under a scanning electron microscope of 2000 times.
Fig. 8 is an image of the modified titanium dioxide-coated paraffin phase-change microcapsule material according to embodiment 3 of the present invention under a scanning electron microscope 14000 times.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely with reference to the accompanying drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments obtained by a person skilled in the art without making any inventive step are within the scope of the present invention.
The invention relates to a preparation method of a titanium dioxide phase change microcapsule material taking titanyl sulfate as a titanium source, which is prepared by taking paraffin as a core material of the phase change material and titanium dioxide as a wall material through a direct precipitation method and comprises the following steps:
(1) preparation of titanium dioxide precursor solution
Preparing a titanyl sulfate aqueous solution, adding alkyl triethoxysilane and absolute ethanol, and uniformly stirring for later use, wherein the titanyl sulfate comprises the following components in percentage by mass: water: alkyl triethoxy silane: absolute ethyl alcohol (2-3.33): 80: (6.66-8): 10;
(2) preparation of phase-change paraffin emulsion
Preparing paraffin, an emulsifier and an ammonia water solution with the mass fraction of 10% according to the mass ratio of 10:0.6:20, heating, and emulsifying under mechanical stirring to form phase-change emulsion after the paraffin of the core material is completely melted;
(3) preparation of modified phase-change microcapsule material
Dropwise adding the titanium dioxide precursor solution prepared in the step (1) into the phase-change paraffin emulsion prepared in the step (2) within 20min under mechanical stirring, adjusting the pH to 2-3 after dropwise adding, cooling to room temperature after heating reaction for 4h, standing, dehydrating by using a centrifugal machine, washing and filtering by using pure water and absolute ethyl alcohol in sequence, and drying in vacuum to obtain the phase-change microcapsule material of titanium dioxide coated paraffin modified by alkyl triethoxysilane.
The mass ratio of the paraffin consumption to the titanyl sulfate in the step (1) is (1: 2-2: 1).
In the step (1), the modifier alkyltriethoxy silane is any one of methyltriethoxysilane MTES, propyltriethoxy silane PTES, octyltriethoxy silane OTES and isobutyltriethoxy silane, and the mass ratio of the dosage of the alkyltriethoxy silane to the dosage of the titanyl sulfate is (1: 2-1: 4).
The emulsifier in the step (2) is any one of a mixture of Sodium Dodecyl Sulfate (SDS) and polyoxyethylene octyl phenol ether-10 or poloxamer, wherein the mass ratio of the SDS to the polyoxyethylene octyl phenol ether-10 is 2: 1.
The titanium dioxide phase change microcapsule material prepared by the preparation method takes titanyl sulfate as a titanium source.
The invention overcomes the defect that in the prior art, the phase-change microcapsule material is prepared by using expensive butyl titanate as a raw material, titanyl sulfate as a titanium source, alkyl triethoxysilane as a modifier and phase-change material paraffin as a core material by a direct precipitation method. The alkyl triethoxysilane modified titanium dioxide precursor is grafted to introduce organic groups, so that the phenomena of uneven wall material thickness and self-aggregation are reduced, and the utilization rate of the wall material and the coating rate of the microcapsule material are improved.
Example 1
The preparation method of the unmodified titanium dioxide coated paraffin phase change microcapsule material comprises the following steps:
phase change material paraffin is used as a core material, titanyl sulfate is used as a titanium source, and the mass ratio of the core material paraffin to the wall material is 1: 1.
(1) taking titanyl sulfate and pure water to prepare a solution, wherein the ratio of the titanyl sulfate to the pure water is as follows: water 10: 90, respectively;
(2) adding 10g of paraffin, 0.4g of Sodium Dodecyl Sulfate (SDS), 0.2g of polyoxyethylene octyl phenol ether-10 (op-10) and 40g of 10% ammonia water solution into a three-necked bottle, heating in a water bath, and forming phase-change emulsion under mechanical stirring after the paraffin of a core material is completely melted;
(3) dropwise adding the titanium dioxide precursor solution prepared in the step (1) into the phase-change paraffin emulsion prepared in the step (2) within 20min by using a dropping funnel, after dropwise adding, dropwise adding a certain amount of 10% ammonia water solution to adjust the pH to 2.5, heating to react for 4h, cooling to room temperature, standing, dehydrating the sample by using a centrifugal machine, washing and filtering by using pure water and absolute ethyl alcohol in sequence, and drying in vacuum to obtain the unmodified titanium dioxide phase-change microcapsule material. In order to test the coating rate of the unmodified phase change microcapsule material, DSC differential thermal analysis is carried out on the unmodified phase change microcapsule material, and the coating rate is calculated according to the phase change enthalpy value of the unmodified phase change microcapsule material. The result shows that the coating rate of the unmodified titanium dioxide phase change microcapsule material is 35.64 percent.
Example 2
Phase change material paraffin is used as a core material, titanyl sulfate is used as a titanium source, methyltriethoxysilane is used as a modifier, and the mass ratio of the dosage of the modifier to the dosage of the titanyl sulfate is 1: 3, the mass ratio of the core material paraffin to the wall material is 1: 1.
(1) adding titanyl sulfate into water to prepare a solution, adding methyl triethoxysilane and absolute ethanol, and uniformly stirring for later use, wherein the mass ratio of each component is titanyl sulfate: water: methyltriethoxysilane: absolute ethanol ═ 7.5: 80: 2.5: 10;
(2) adding 10g of paraffin, 0.4g of Sodium Dodecyl Sulfate (SDS), 0.2g of polyoxyethylene octyl phenol ether-10 (op-10) and 40g of 10% ammonia water solution into a three-necked bottle, heating in a water bath, and forming phase-change emulsion under mechanical stirring after the paraffin of a core material is completely melted;
(3) dropwise adding the titanium dioxide precursor solution prepared in the step (1) into the phase-change paraffin emulsion prepared in the step (2) within 20min by using a dropping funnel, after dropwise adding, dropwise adding a certain amount of 10% ammonia water solution to adjust the pH to 2, heating to react for 4h, cooling to room temperature, standing, dehydrating a sample by using a centrifugal machine, washing and filtering by using pure water and absolute ethyl alcohol in sequence, and drying in vacuum to obtain the methyltriethoxysilane modified titanium dioxide phase-change microcapsule material. In order to test the change of the coating rate of the modified phase-change microcapsule material, DSC differential thermal analysis is carried out on the modified phase-change microcapsule material, and the coating rate is calculated according to the phase-change enthalpy value of the modified phase-change microcapsule material. The result shows that under the reaction condition of PH 2, the coating rate of the titanium dioxide phase change microcapsule material modified by the methyltriethoxysilane is 79.78%.
Example 3
Phase change material paraffin is used as a core material, titanyl sulfate is used as a titanium source, methyltriethoxysilane is used as a modifier, and the mass ratio of the dosage of the modifier to the dosage of the titanyl sulfate is 1: 3, the mass ratio of the core material paraffin to the wall material is 1: 1.
(1) adding titanyl sulfate into water to prepare a solution, adding methyl triethoxysilane and absolute ethanol, and uniformly stirring for later use, wherein the mass ratio of each component is titanyl sulfate: water: methyltriethoxysilane: absolute ethanol ═ 7.5: 80: 2.5: 10;
(2) adding 10g of paraffin, 0.4g of Sodium Dodecyl Sulfate (SDS), 0.2g of polyoxyethylene octyl phenol ether-10 (op-10) and 40g of 10% ammonia water solution into a three-necked bottle, heating in a water bath, and forming phase-change emulsion under mechanical stirring after the paraffin of a core material is completely melted;
(3) dropwise adding the titanium dioxide precursor solution prepared in the step (1) into the phase-change paraffin emulsion prepared in the step (2) within 20min by using a dropping funnel, after the dropwise addition is finished, dropwise adding a certain amount of 10% ammonia water solution to adjust the pH to 2.5, heating to react for 4h, cooling to room temperature, standing, dehydrating the sample by using a centrifugal machine, washing and filtering by using pure water and absolute ethyl alcohol in sequence, and drying in vacuum to obtain the methyl triethoxysilane modified titanium dioxide phase-change microcapsule material. In order to test the change of the coating rate of the modified phase-change microcapsule material, DSC differential thermal analysis is carried out on the modified phase-change microcapsule material, and the coating rate is calculated according to the phase-change enthalpy value of the modified phase-change microcapsule material. The result shows that the coating rate of the titanium dioxide phase change microcapsule material modified by the methyltriethoxysilane is 83.70% under the reaction condition of pH 2.5.
Example 4
Phase change material paraffin is used as a core material, titanyl sulfate is used as a titanium source, methyltriethoxysilane is used as a modifier, and the mass ratio of the dosage of the modifier to the dosage of the titanyl sulfate is 1: 3, the mass ratio of the core material paraffin to the wall material is 1: 1.
(1) adding titanyl sulfate into water to prepare a solution, adding methyl triethoxysilane and absolute ethanol, and uniformly stirring for later use, wherein the mass ratio of each component is titanyl sulfate: water: methyltriethoxysilane: absolute ethanol ═ 7.5: 80: 2.5: 10;
(2) adding 10g of paraffin, 0.4g of Sodium Dodecyl Sulfate (SDS), 0.2g of polyoxyethylene octyl phenol ether-10 (op-10) and 40g of 10% ammonia water solution into a three-necked bottle, heating in a water bath, and forming phase-change emulsion under mechanical stirring after the paraffin of a core material is completely melted;
(3) dropwise adding the titanium dioxide precursor solution prepared in the step (1) into the phase-change paraffin emulsion prepared in the step (2) within 20min by using a dropping funnel, after dropwise adding, dropwise adding a certain amount of 10% ammonia water solution to adjust the pH to 3, heating to react for 4h, cooling to room temperature, standing, dehydrating a sample by using a centrifugal machine, washing and filtering by using pure water and absolute ethyl alcohol in sequence, and drying in vacuum to obtain the methyltriethoxysilane modified titanium dioxide phase-change microcapsule material. In order to test the change of the coating rate of the modified phase-change microcapsule material, DSC differential thermal analysis is carried out on the modified phase-change microcapsule material, and the coating rate is calculated according to the phase-change enthalpy value of the modified phase-change microcapsule material. The result shows that under the reaction condition of PH 3, the coating rate of the titanium dioxide phase change microcapsule material modified by the methyltriethoxysilane is 63.30%.
Example 5
Phase change material paraffin is used as a core material, titanyl sulfate is used as a titanium source, propyl triethoxysilane is used as a modifier, and the mass ratio of the modifier to the titanyl sulfate is 1: 3, the mass ratio of the core material paraffin to the wall material is 1: 1.
(1) adding titanyl sulfate into water to prepare a solution, adding propyl triethoxysilane and absolute ethanol, and uniformly stirring for later use, wherein the mass ratio of each component is titanyl sulfate: water: propyltriethoxysilane: absolute ethanol ═ 7.5: 80: 2.5: 10;
(2) adding 10g of paraffin, 0.4g of Sodium Dodecyl Sulfate (SDS), 0.2g of polyoxyethylene octyl phenol ether-10 (op-10) and 40g of 10% ammonia water solution into a three-necked bottle, heating in a water bath, and forming phase-change emulsion under mechanical stirring after the paraffin of a core material is completely melted;
(3) dropwise adding the titanium dioxide precursor solution prepared in the step (1) into the phase-change paraffin emulsion prepared in the step (2) within 20min by using a dropping funnel, after dropwise adding, dropwise adding a certain amount of 10% ammonia water solution to adjust the pH to 2.5, heating to react for 4h, cooling to room temperature, standing, dehydrating a sample by using a centrifugal machine, washing and filtering by using pure water and absolute ethyl alcohol in sequence, and drying in vacuum to obtain the propyltriethoxysilane modified titanium dioxide phase-change microcapsule material. In order to test the change of the coating rate of the modified phase-change microcapsule material, DSC differential thermal analysis is carried out on the modified phase-change microcapsule material, and the coating rate is calculated according to the phase-change enthalpy value of the modified phase-change microcapsule material. The result shows that the coating rate of the titanium dioxide phase change microcapsule material modified by the propyltriethoxysilane is 57.16%.
Example 6
The phase change material paraffin is used as a core material, titanyl sulfate is used as a titanium source, octyl triethoxysilane is used as a modifier, and the mass ratio of the modifier to the titanyl sulfate is 1: 3, the mass ratio of the core material paraffin to the wall material is 1: 1.
(1) adding titanyl sulfate into water to prepare a solution, adding octyl triethoxysilane and absolute ethanol, and uniformly stirring for later use, wherein the mass ratio of each component is titanyl sulfate: water: octyl triethoxysilane: absolute ethanol ═ 7.5: 80: 2.5: 10;
(2) adding 10g of paraffin, 0.4g of Sodium Dodecyl Sulfate (SDS), 0.2g of polyoxyethylene octyl phenol ether-10 (op-10) and 40g of 10% ammonia water solution into a three-necked bottle, heating in a water bath, and forming phase-change emulsion under mechanical stirring after the paraffin of a core material is completely melted;
(3) dropwise adding the titanium dioxide precursor solution prepared in the step (1) into the phase-change paraffin emulsion prepared in the step (2) within 20min by using a dropping funnel, after the dropwise addition is finished, dropwise adding a certain amount of 10% ammonia water solution to adjust the pH to 2.5, heating to react for 4h, cooling to room temperature, standing, dehydrating the sample by using a centrifugal machine, washing and filtering by using pure water and absolute ethyl alcohol in sequence, and drying in vacuum to obtain the octyltriethoxysilane modified titanium dioxide phase-change microcapsule material. In order to test the change of the coating rate of the modified phase-change microcapsule material, DSC differential thermal analysis is carried out on the modified phase-change microcapsule material, and the coating rate is calculated according to the phase-change enthalpy value of the modified phase-change microcapsule material. The result shows that the coating rate of the titanium dioxide phase change microcapsule material modified by the octyl triethoxysilane is 48.34%.
Example 7
Phase change material paraffin is used as a core material, titanyl sulfate is used as a titanium source, isobutyl triethoxy silane is used as a modifier, and the mass ratio of the dosage of the modifier to the dosage of titanyl sulfate is 1: 3, the mass ratio of the core material paraffin to the wall material is 1: 1.
(1) adding titanyl sulfate into water to prepare a solution, adding isobutyl triethoxysilane and absolute ethanol, and uniformly stirring for later use, wherein the mass ratio of each component is titanyl sulfate: water: isobutyl triethoxysilane: absolute ethanol ═ 7.5: 80: 2.5: 10;
(2) adding 10g of paraffin, 0.4g of Sodium Dodecyl Sulfate (SDS), 0.2g of polyoxyethylene octyl phenol ether-10 (op-10) and 40g of 10% ammonia water solution into a three-necked bottle, heating in a water bath, and forming phase-change emulsion under mechanical stirring after the paraffin of a core material is completely melted;
(3) dropwise adding the titanium dioxide precursor solution prepared in the step (1) into the phase-change paraffin emulsion prepared in the step (2) within 20min by using a dropping funnel, after the dropwise addition is finished, dropwise adding a certain amount of 10% ammonia water solution to adjust the pH to 2.5, heating to react for 4h, cooling to room temperature, standing, dehydrating the sample by using a centrifugal machine, washing and filtering by using pure water and absolute ethyl alcohol in sequence, and drying in vacuum to obtain the isobutyl triethoxy silane modified titanium dioxide phase-change microcapsule material. In order to test the change of the coating rate of the modified phase-change microcapsule material, DSC differential thermal analysis is carried out on the modified phase-change microcapsule material, and the coating rate is calculated according to the phase-change enthalpy value of the modified phase-change microcapsule material. The result shows that the coating rate of the titanium dioxide phase change microcapsule material modified by the isobutyl triethoxy silane is 43.36%.
Example 8
Phase change material paraffin is used as a core material, titanyl sulfate is used as a titanium source, methyltriethoxysilane is used as a modifier, and the mass ratio of the dosage of the modifier to the dosage of the titanyl sulfate is 1:4, the mass ratio of the core material paraffin to the wall material is 1: 1.
(1) adding titanyl sulfate into water to prepare a solution, adding methyl triethoxysilane and absolute ethanol, and uniformly stirring for later use, wherein the mass ratio of each component is titanyl sulfate: water: methyltriethoxysilane: absolute ethanol ═ 8: 80: 2: 10;
(2) adding 10g of paraffin, 0.4g of Sodium Dodecyl Sulfate (SDS), 0.2g of polyoxyethylene octyl phenol ether-10 (op-10) and 40g of 10% ammonia water solution into a three-necked bottle, heating in a water bath, and forming phase-change emulsion under mechanical stirring after the paraffin of a core material is completely melted;
(3) dropwise adding the titanium dioxide precursor solution prepared in the step (1) into the phase-change paraffin emulsion prepared in the step (2) within 20min by using a dropping funnel, after dropwise adding, dropwise adding a certain amount of 10% ammonia water solution to adjust the pH to 2.5, heating to react for 4h, cooling to room temperature, standing, dehydrating the sample by using a centrifugal machine, washing and filtering by using pure water and absolute ethyl alcohol in sequence, and drying in vacuum to obtain the methyl triethoxysilane modified titanium dioxide phase-change microcapsule material. In order to test the change of the coating rate of the modified phase-change microcapsule material, DSC differential thermal analysis is carried out on the modified phase-change microcapsule material, and the coating rate is calculated according to the phase-change enthalpy value of the modified phase-change microcapsule material. The result shows that the mass ratio of the modifier to the titanyl sulfate is 1: and when 4, the coating rate of the titanium dioxide phase change microcapsule material modified by the methyl triethoxysilane is 19.24%.
Example 9
Phase change material paraffin is used as a core material, titanyl sulfate is used as a titanium source, methyltriethoxysilane is used as a modifier, and the mass ratio of the dosage of the modifier to the dosage of the titanyl sulfate is 1:2, the mass ratio of the core material paraffin to the wall material is 1: 1.
(1) adding titanyl sulfate into water to prepare a solution, adding methyl triethoxysilane and absolute ethanol, and uniformly stirring for later use, wherein the mass ratio of each component is titanyl sulfate: water: methyltriethoxysilane: absolute ethanol ═ 6.66: 80: 3.33: 10;
(2) adding 10g of paraffin, 0.4g of Sodium Dodecyl Sulfate (SDS), 0.2g of polyoxyethylene octyl phenol ether-10 (op-10) and 40g of 10% ammonia water solution into a three-necked bottle, heating in a water bath, and mechanically stirring to form a phase-change material emulsion after the paraffin of a core material is completely melted;
(3) dropwise adding the titanium dioxide precursor solution prepared in the step (1) into the phase-change paraffin emulsion prepared in the step (2) within 20min by using a dropping funnel, after dropwise adding, dropwise adding a certain amount of 10% ammonia water solution to adjust the pH to 2.5, heating to react for 4h, cooling to room temperature, standing, dehydrating the sample by using a centrifugal machine, washing and filtering by using pure water and absolute ethyl alcohol in sequence, and drying in vacuum to obtain the methyl triethoxysilane modified titanium dioxide phase-change microcapsule material. In order to test the change of the modified coating rate, the phase change microcapsule material is subjected to DSC differential thermal analysis, and the coating rate is calculated according to the phase change enthalpy value of the phase change microcapsule material. The result shows that the mass ratio of the modifier to the titanyl sulfate is 1: and 2, the coating rate of the titanium dioxide phase change microcapsule material modified by the methyl triethoxysilane is 52.80 percent.
Example 10
Phase change material paraffin is used as a core material, titanyl sulfate is used as a titanium source, methyltriethoxysilane is used as a modifier, and the mass ratio of the dosage of the modifier to the dosage of the titanyl sulfate is 1: 3, the mass ratio of the core material paraffin to the wall material is 1: 2.
(1) adding titanyl sulfate into water to prepare a solution, adding methyl triethoxysilane and absolute ethanol, and uniformly stirring for later use, wherein the mass ratio of each component is titanyl sulfate: water: methyltriethoxysilane: absolute ethanol ═ 7.5: 80: 2.5: 10;
(2) adding 5g of paraffin, 0.2g of Sodium Dodecyl Sulfate (SDS), 0.1g of polyoxyethylene octyl phenol ether-10 (op-10) and 40g of 10% ammonia water solution into a three-necked bottle, heating in a water bath, and mechanically stirring to form a phase-change material emulsion after the paraffin of a core material is completely melted;
(3) dropwise adding the titanium dioxide precursor solution prepared in the step (1) into the phase-change paraffin emulsion prepared in the step (2) within 20min by using a dropping funnel, after dropwise adding, dropwise adding a certain amount of 10% ammonia water solution to adjust the pH to 2.5, heating to react for 4h, cooling to room temperature, standing, dehydrating the sample by using a centrifugal machine, washing and filtering by using pure water and absolute ethyl alcohol in sequence, and drying in vacuum to obtain the methyl triethoxysilane modified titanium dioxide phase-change microcapsule material. In order to test the change of the modified coating rate, the phase change microcapsule material is subjected to DSC differential thermal analysis, and the coating rate is calculated according to the phase change enthalpy value of the phase change microcapsule material. The results show that, at a core-to-wall ratio of 1: and 2, the coating rate of the titanium dioxide phase change microcapsule material modified by the methyl triethoxysilane is 27.90%.
Example 11
Phase change material paraffin is used as a core material, titanyl sulfate is used as a titanium source, methyltriethoxysilane is used as a modifier, and the mass ratio of the dosage of the modifier to the dosage of the titanyl sulfate is 1: 3, the mass ratio of the core material paraffin to the wall material is 2: 1.
(1) adding titanyl sulfate into water to prepare a solution, adding methyl triethoxysilane and absolute ethanol, and uniformly stirring for later use, wherein the mass ratio of each component is titanyl sulfate: water: methyltriethoxysilane: absolute ethanol ═ 3.75: 40: 1.25: 5;
(2) adding 10g of paraffin, 0.4g of Sodium Dodecyl Sulfate (SDS), 0.2g of polyoxyethylene octyl phenol ether-10 (op-10), 20g of 10% ammonia water solution and 20g of pure water into a three-necked bottle, heating in a water bath, and mechanically stirring to form a phase-change emulsion after the paraffin of the core material is completely melted;
(3) dropwise adding the titanium dioxide precursor solution prepared in the step (1) into the phase-change paraffin emulsion prepared in the step (2) within 20min by using a dropping funnel, after dropwise adding, dropwise adding a certain amount of 10% ammonia water solution to adjust the pH to 2.5, heating to react for 4h, cooling to room temperature, standing, dehydrating the sample by using a centrifugal machine, washing and filtering by using pure water and absolute ethyl alcohol in sequence, and drying in vacuum to obtain the methyl triethoxysilane modified titanium dioxide phase-change microcapsule material. In order to test the change of the coating rate of the modified phase-change microcapsule material, DSC differential thermal analysis is carried out on the modified phase-change microcapsule material, and the coating rate is calculated according to the phase-change enthalpy value of the modified phase-change microcapsule material. The results show that, at a core-to-wall ratio of 2: when the coating rate is 1, the coating rate of the titanium dioxide phase change microcapsule material modified by the methyltriethoxysilane is 68.42 percent.
Example 12
Phase change material paraffin is used as a core material, titanyl sulfate is used as a titanium source, methyltriethoxysilane is used as a modifier, and the mass ratio of the dosage of the modifier to the dosage of the titanyl sulfate is 1: 3, the mass ratio of the core material paraffin to the wall material is 1: 1.
(1) adding titanyl sulfate into water to prepare a solution, adding methyl triethoxysilane and absolute ethanol, and uniformly stirring for later use, wherein the mass ratio of each component is titanyl sulfate: water: methyltriethoxysilane: absolute ethanol ═ 7.5: 80: 2.5: 10;
(2) adding 10g of paraffin, 0.6g of poloxamer and 40g of 10% ammonia water solution into a three-necked bottle, heating in a water bath, and mechanically stirring to form phase-change emulsion after the paraffin of the core material is completely melted;
(3) dropwise adding the titanium dioxide precursor solution prepared in the step (1) into the phase-change paraffin emulsion prepared in the step (2) within 20min by using a dropping funnel, after dropwise adding, dropwise adding a certain amount of 10% ammonia water solution to adjust the pH to 2.5, heating to react for 4h, cooling to room temperature, standing, dehydrating the sample by using a centrifugal machine, washing and filtering by using pure water and absolute ethyl alcohol in sequence, and drying in vacuum to obtain the methyl triethoxysilane modified titanium dioxide phase-change microcapsule material. In order to test the change of the coating rate of the modified phase-change microcapsule material, DSC differential thermal analysis is carried out on the modified phase-change microcapsule material, and the coating rate is calculated according to the phase-change enthalpy value of the modified phase-change microcapsule material. The result shows that when the emulsifier is poloxamer, the coating rate of the titanium dioxide phase change microcapsule material modified by the methyltriethoxysilane is 71.03%.
The results of the above example are shown in FIGS. 1-8.
In summary, the disclosure of the present invention is not limited to the above-mentioned embodiments, and persons skilled in the art can easily set forth other embodiments within the technical teaching of the present invention, but such embodiments are included in the scope of the present invention.
Claims (5)
1. A preparation method of a titanium dioxide phase change microcapsule material taking titanyl sulfate as a titanium source is characterized in that paraffin is taken as a core material of the phase change material, titanium dioxide is taken as a wall material, and the titanium dioxide phase change microcapsule material is prepared by a direct precipitation method and comprises the following steps:
(1) preparation of titanium dioxide precursor solution
Preparing a titanyl sulfate aqueous solution, adding alkyl triethoxysilane and absolute ethanol, and uniformly stirring for later use, wherein the titanyl sulfate comprises the following components in percentage by mass: water: alkyl triethoxy silane: absolute ethyl alcohol (2-3.33): 80: (6.66-8): 10;
(2) preparation of phase-change paraffin emulsion
Preparing paraffin, an emulsifier and an ammonia water solution with the mass fraction of 10% according to the mass ratio of 10:0.6:20, heating, and emulsifying under mechanical stirring to form phase-change emulsion after the paraffin of the core material is completely melted;
(3) preparation of modified phase-change microcapsule material
Dropwise adding the titanium dioxide precursor solution prepared in the step (1) into the phase-change paraffin emulsion prepared in the step (2) within 20min under mechanical stirring, adjusting the pH to 2-3 after dropwise adding, cooling to room temperature after heating reaction for 4h, standing, dehydrating by using a centrifugal machine, washing and filtering by using pure water and absolute ethyl alcohol in sequence, and drying in vacuum to obtain the phase-change microcapsule material of titanium dioxide coated paraffin modified by alkyl triethoxysilane.
2. The method for preparing the titanium dioxide phase change microcapsule material by taking the titanyl sulfate as the titanium source according to claim 1, wherein the mass ratio of the dosage of the paraffin to the titanyl sulfate in the step (1) is (1: 2-2: 1).
3. The method for preparing a titanium dioxide phase change microcapsule material using titanyl sulfate as a titanium source according to claim 1, wherein in the step (1), the alkyl triethoxy silane as a modifier is any one of methyl triethoxy silane MTES, propyl triethoxy silane PTES, octyl triethoxy silane OTES and isobutyl triethoxy silane, and the mass ratio of the amount of the alkyl triethoxy silane to the amount of titanyl sulfate is (1: 2-1: 4).
4. The method for preparing titanium dioxide phase change microcapsule material using titanyl sulfate as titanium source according to claim 1, wherein the emulsifier in step (2) is any one of a mixture of Sodium Dodecyl Sulfate (SDS) and polyoxyethylene octylphenol ether-10 or poloxamer, wherein the amount by mass ratio of the SDS to the polyoxyethylene octylphenol ether-10 is 2: 1.
5. The titanium dioxide phase change microcapsule material using titanyl sulfate as a titanium source prepared by the preparation method according to any one of claims 1 to 4.
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