阅读说明：本技术 环胺高氯酸可逆相变材料及其制备方法 (Cyclic amine perchloric acid reversible phase-change material and preparation method thereof ) 是由 魏振宏 蔡琥 饶文俊 何文慧 于 2021-06-01 设计创作，主要内容包括：本发明公开了环胺高氯酸可逆相变材料,该材料由1,4,7,10-四氮杂环十二烷(cyclen)和高氯酸在甲醇溶液中分别以摩尔比1∶1,1∶2,1∶3的比例反应获的,其分子结构式分布为[cyclen(ClO-4)](1),[cyclen(ClO-4)-2](2)和[cyclen(ClO-4)-3](3)。本发明利用便宜易得的1,4,7,10-四氮杂环十二烷与高氯酸为原料,合成了具有可逆相变材料。本发明可应用于可穿戴器件、生物医药装置、柔性机器人、通信、传感等高新技术产业和国防装备等领域。(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(ClO 4 ) 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.)

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]。

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.