CN113429362A - Cyclic amine perchloric acid reversible phase-change material and preparation method thereof - Google Patents
Cyclic amine perchloric acid reversible phase-change material and preparation method thereof Download PDFInfo
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- CN113429362A CN113429362A CN202110610967.1A CN202110610967A CN113429362A CN 113429362 A CN113429362 A CN 113429362A CN 202110610967 A CN202110610967 A CN 202110610967A CN 113429362 A CN113429362 A CN 113429362A
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- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 150000001412 amines Chemical class 0.000 title claims abstract description 20
- 239000012782 phase change material Substances 0.000 title claims abstract description 19
- 230000002441 reversible effect Effects 0.000 title claims abstract description 19
- 125000004122 cyclic group Chemical group 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title description 8
- QBPPRVHXOZRESW-UHFFFAOYSA-N 1,4,7,10-tetraazacyclododecane Chemical compound C1CNCCNCCNCCN1 QBPPRVHXOZRESW-UHFFFAOYSA-N 0.000 claims abstract description 63
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 12
- 229910001914 chlorine tetroxide Inorganic materials 0.000 claims abstract description 9
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000013078 crystal Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims 1
- 238000004891 communication Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 4
- 230000007123 defense Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 7
- 230000007704 transition Effects 0.000 description 7
- 238000000634 powder X-ray diffraction Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- -1 cyclic amine Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
- C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
- H10N70/20—Multistable switching devices, e.g. memristors
- H10N70/231—Multistable switching devices, e.g. memristors based on solid-state phase change, e.g. between amorphous and crystalline phases, Ovshinsky effect
- H10N70/235—Multistable switching devices, e.g. memristors based on solid-state phase change, e.g. between amorphous and crystalline phases, Ovshinsky effect between different crystalline phases, e.g. cubic and hexagonal
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
- H10N70/801—Constructional details of multistable switching devices
- H10N70/881—Switching materials
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
The invention discloses a cyclic amine perchloric acid reversible phase-change material, which is obtained by reacting 1, 4, 7, 10-tetraazacyclododecane (cyclen) and perchloric acid in methanol solution according to the molar ratio of 1: 1, 1: 2 and 1: 3 respectively, and the molecular structural formula of the material is [ cyclen (ClO)4)](1),[cyclen(ClO4)2](2) And [ cyclen (ClO)4)3](3). The invention synthesizes the reversible phase-change material by using cheap and easily obtained 1, 4, 7, 10-tetraazacyclododecane and perchloric acid as raw materials. The invention can be applied to the fields of high and new technology industries such as wearable devices, biomedical devices, flexible robots, communication, sensing and the like, national defense equipment and the like.
Description
Technical Field
The invention relates to a preparation method of 3 cyclic amine perchloric acid materials which are flexible, easy to process, simple to synthesize, high in yield, good in purity, energy-saving and environment-friendly, and the molecular formula of the materials is [ cyclen (ClO)4)](1),[cyclen(ClO4)2](2) And [ cyclen (ClO)4)3](3)。
Background
The phase transition refers to a phenomenon that macroscopic properties or structures of crystals are promoted to be changed under the condition that chemical compositions are not changed and under the condition that other physical or chemical conditions such as temperature and time are changed. Along with the occurrence of structural phase change, the ordered degree and symmetry of the crystal are changed, the disordered structure of the high-temperature phase generally has high symmetry, and the ordered structure of the low-temperature phase reduces the symmetry. The crystal can generate different phase states due to different temperatures, and the structural properties of the crystal are different in different phase states. In recent years, the application of phase change materials in information storage, signal processing, acousto-optic devices, switchable dielectric devices and the like has attracted close attention of researchers in material technology and energy utilization at home and abroad. The phase change material is widely applied to the fields of aerospace, military, communication, electric power and the like. The phase change material with excellent performance is searched by a chemical method, so that the method has wide application prospect. Phase change materials have great potential for use in heat and information storage because they can be switched between different phases (and properties) under an external stimulus. Phase change materials have great potential for use in heat and information storage because they can be switched between different phases (and properties) under an external stimulus.
Disclosure of Invention
Aiming at the defects and problems in the prior art, the invention aims to provide a cyclic amine perchloric acid reversible phase change material and a preparation method thereof, and relates to 3 cyclic amine perchloric acid materials which are flexible, easy to process, simple to synthesize, high in yield, good in purity, energy-saving and environment-friendly.
The invention is realized by the following technical scheme:
the invention provides a cyclic amine perchloric acid reversible phase-change material, which is synthesized by taking 1, 4, 7, 10-tetraazacyclododecane (cyclen) and perchloric acid as raw materials, and the molecular general formula of the structure of the material is [ cyclen (ClO)4)n]N is an integer of 1 to 3; the phase change process of the material is reversible.
The invention also provides a preparation method of the cyclic amine perchloric acid reversible phase change material, which comprises the steps of taking 1, 4, 7, 10-tetraazacyclododecane as organic amine, respectively mixing the organic amine with perchloric acid in a molar ratio of 1: 1, 1: 2 and 1: 3 in a methanol solution, heating the mixture until the mixture is heated to the temperature of 1: 1, 1: 2 and 1: 3333K is stirred again for reaction until the solution is clear and transparent; after the reaction is finished, crystals are separated out by adopting a slow programmed cooling method, and are filtered, separated and dried to obtain three cyclic amine perchloric acid reversible phase-change materials which are respectively [ cyclen (ClO)4)],[cyclen(ClO4)2]And [ cyclen (ClO)4)3]。
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention prepares [ cyclo (ClO) by utilizing the advantages of strong coordination capability of 1, 4, 7, 10-tetraazacyclododecane, selective action of a cavity structure on organic anions, easy generation of disordered structures of cyclic amine and tetrahedral inorganic anions at high temperature, low price and easy obtainment4)](1),[cyclen(ClO4)2](2) And [ cyclen (ClO)4)3](3) Three cyclic amine perchloric acid reversible phase change materials.
(2) The reaction solution is crystallized by adopting a slow programmed cooling method, the filtrate after the cyclic amine perchloric acid crystal is obtained by separation can be continuously volatilized at normal temperature to separate out the crystal, and the purposes of reducing cost, saving energy and protecting environment are achieved.
(3) The invention utilizes 1, 4, 7, 10-tetraazacyclododecane and perchloric acid for reaction, and has the characteristics of simple operation, high yield, high purity and the like.
(4) The material can be applied to the fields of high and new technology industries such as wearable devices, biomedical devices, flexible robots, communication, sensing and the like, national defense equipment and the like.
Drawings
FIG. 1 shows [ cyclen (ClO) prepared in example 1 of the present invention4)1]Crystal structure at different temperatures (253K on the left, 298K on the right);
FIG. 2 shows [ cyclen (ClO) prepared in example 1 of the present invention4)]Powder X-ray diffraction pattern of (a);
FIG. 3 shows [ cyclen (ClO) prepared in example 1 of the present invention4)]Heating-cooling schematic by DSC;
FIG. 4 is [ cyclen (ClO) prepared in example 2 of the present invention4)2]Crystal structure at different temperatures (298K left, 323K right);
FIG. 5 shows [ cyclen (ClO) prepared in example 2 of the present invention4)2]Powder X-ray diffraction pattern of (a);
FIG. 6 is [ cyclen (ClO) prepared in example 2 of the present invention4)2]Heating-cooling schematic by DSC;
FIG. 7 shows [ cyclen (ClO) prepared in example 3 of the present invention4)3]Crystal structures at different temperatures (298K on the left, 373K on the right);
FIG. 8 is [ cyclen (ClO) prepared in example 3 of the present invention4)3]Powder X-ray diffraction pattern of (a);
FIG. 9 is [ cyclen (ClO) prepared in example 3 of the present invention4)3]Schematic heating-cooling by DSC.
Detailed Description
The invention will be further described with reference to the accompanying drawings.
EXAMPLE 1 preparation of [ cyclen (ClO)4)](1)
Cyclen (0.1725g, 1mmol) was added to the beaker, 5mL of methanol solution was added dropwise thereto, heated with stirring until dissolved, and 70% w/w perchloric acid solution (0.1430g, 1mmol) was added dropwise. Heating to 333K and stirring at constant temperature until the mixed solution is clear and transparent. Precipitating colorless blocky crystal by slow programmed solution cooling method, filtering, separating, and vacuum drying the filtered crystal to obtain [ cyclen (ClO)4)]. The filtered filtrate is volatilized again at normal temperature, and crystals can be separated out.
As shown in FIG. 1, [ cyclen (ClO)4)1](1) Crystal structure at different temperatures (253K on the left, 298K on the right).
As shown in FIG. 2, [ cyclen (ClO)4)](1) The powder X-ray diffraction of (a) shows a single pure sample.
As shown in fig. 3, DSC test showed that compound 1 had a reversible phase transition with a phase transition point of 259K.
EXAMPLE 2 preparation of [ cyclen (ClO4)2](2)
Cyclen (0.1725g, 1mmol) was dissolved in a 5mL beaker of methanol solution. Heating the mixture to dissolve under constant magnetic stirring, and adding70% w/w perchloric acid solution (0.2860g, 2mmol), the mixture was heated to 333K and stirred until the precipitate dissolved. And obtaining the colorless needle-shaped single crystal by adopting a solution slow programmed cooling method. Filtering, separating, and vacuum drying the filtered crystal to obtain [ cyclen (ClO)4)2]。
As shown in FIG. 4, [ cyclen (ClO)4)2]Crystal structure at different temperatures (298K left, 323K right).
As shown in FIG. 5, [ cyclen (ClO)4)2]The powder X-ray diffraction of (a) shows a single pure sample.
As shown in fig. 6, DSC test showed that compound 2 had a reversible phase transition with a phase transition point of 309K.
EXAMPLE 3 preparation of [ cyclen (ClO)4)3](3)
Cyclen (0.1725g, 1mmol) was dissolved in a 5mL beaker of methanol solution. The mixture was heated to dissolution under constant magnetic stirring, and a 70% w/w perchloric acid solution (0.4290g, 3mmol) was added to the beaker and the mixture was found to be incompletely dissolved, and 3ml deionized water solution was added dropwise thereto and heated to 333K with constant stirring until the mixed solution was clear and transparent. Precipitating colorless blocky monocrystal by adopting a solution slow programmed cooling method, filtering and separating, and performing vacuum drying on the filtered crystal to obtain [ cyclen (ClO)4)3]。
As shown in FIG. 7, [ cyclen (ClO)4)3]Crystal structure at different temperatures (298K on the left, 373K on the right).
As shown in FIG. 8, [ cyclen (ClO)4)3]The powder X-ray diffraction of (a) shows a single pure sample.
As shown in fig. 9, DSC test showed that compound 3 had reversible phase transition with a phase transition point of 351K.
From examples 1-3, the present invention discloses three cyclic amine perchloric acid reversible phase change materials: [ cyclen (ClO4) ] (1), [ cyclen (ClO4)2] (2) and [ cyclen (ClO4)3] (3), obtained by reacting 1, 4, 7, 10-tetraazacyclododecane (cyclen) and perchloric acid in a methanol solution in a molar ratio of 1: 1, 1: 2, 1: 3, respectively. The invention synthesizes the reversible phase-change material by using cheap and easily obtained 1, 4, 7, 10-tetraazacyclododecane and perchloric acid as raw materials. The invention can be applied to the fields of high and new technology industries such as wearable devices, biomedical devices, flexible robots, communication, sensing and the like, national defense equipment and the like.
The foregoing merely represents preferred embodiments of the invention, which are described in some detail and detail, and therefore should not be construed as limiting the scope of the invention. It should be noted that, for those skilled in the art, various changes, modifications and substitutions can be made without departing from the spirit of the present invention, and these are all within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (4)
1. The cyclic amine perchloric acid reversible phase-change material is characterized in that: the material is synthesized by taking 1, 4, 7, 10-tetraazacyclododecane (cyclen) and perchloric acid as raw materials, and the molecular general formula of the structure of the material is [ cyclen (ClO)4)n]N is an integer of 1 to 3; the phase change process of the material is reversible.
2. The method for preparing a cyclic amine perchloric acid reversible phase change material according to claim 1, characterized in that: the method comprises the steps of taking 1, 4, 7, 10-tetraazacyclododecane as organic amine, heating the organic amine and perchloric acid in a methanol solution to 333K, stirring and reacting until the solution is clear and transparent, precipitating crystals by adopting a slow programmed cooling method after the reaction is finished, filtering, separating and drying to obtain the cyclic amine perchloric acid reversible phase-change material.
3. The method of claim 2, wherein: after the reaction is finished, the filtered filtrate is volatilized at normal temperature again to separate out the high-purity cyclic amine perchloric acid material.
4. The method of claim 2, wherein: 1, 4, 7, 10-tetraazacyclododecane and perchloric acid are reacted in a molar ratio of 1: 1, 1: 2, 1: 3 to form [ cyclen (ClO)4)],[cyclen(ClO4)2]And [ cyclen (ClO)4)3]。
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105837581A (en) * | 2016-04-27 | 2016-08-10 | 江苏科技大学 | Hexafluorophosphate containing low-temperature phase change compound and preparation method and application thereof |
CN108264491A (en) * | 2016-12-30 | 2018-07-10 | 山东威智医药工业有限公司 | The preparation method of Cyclen -1,4,7,10- tetraacethyls |
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Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN105837581A (en) * | 2016-04-27 | 2016-08-10 | 江苏科技大学 | Hexafluorophosphate containing low-temperature phase change compound and preparation method and application thereof |
CN108264491A (en) * | 2016-12-30 | 2018-07-10 | 山东威智医药工业有限公司 | The preparation method of Cyclen -1,4,7,10- tetraacethyls |
Non-Patent Citations (2)
Title |
---|
XU FENG等: "A Hydrogen Bond Stabilized 3D Network Built from Pyrazine-2,3,5,6-tetracarboxylic Acid and 8-Hydroxyquinoline", 《结构化学》 * |
张秀秀: "新型环胺+四面体酸有机无机杂化分子的合成及性质研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
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