CN105837580B - A kind of one-dimensional chain low temperature phase change compound, preparation method and applications - Google Patents
A kind of one-dimensional chain low temperature phase change compound, preparation method and applications Download PDFInfo
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- CN105837580B CN105837580B CN201610268867.4A CN201610268867A CN105837580B CN 105837580 B CN105837580 B CN 105837580B CN 201610268867 A CN201610268867 A CN 201610268867A CN 105837580 B CN105837580 B CN 105837580B
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- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
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Abstract
The invention belongs to phase-change material field, discloses a kind of one-dimensional chain low temperature phase change compound, preparation method and applications.The chemical formula of the phase transition compound is C9H20B3F12N2Na, at a temperature of 150K, crystal belongs to hexagonal crystal system, space group P63；At a temperature of 123K, crystal is monoclinic system, space group P21/c；Na will be contained+Soluble compound and triethylene diamine derivative mixing using the self assembly of solution nature solvent flashing be made product；The compound with low temperature one-dimensional catenary structure phase transition property of the present invention, used material preparation process is simple, easy to operate, sufficient raw, production cost is low, yield is high and reproducible；In general solvent is not readily dissolved in, heat decomposition temperature point is of a relatively high, and crystal grain is uniform.Such phase-change material all has the application of very big potentiality in fields such as textile garment, chamber planting, building trades.
Description
Technical field
The invention belongs to phase-change material field, and in particular to a kind of one-dimensional chain at low temperature with low temperature phase change property
Structure compound containing sodium salt, preparation method and applications.
Background technology
Phase-change material, abbreviation PCM, it is the phase transformation storage material for caning absorb or releasing energy during phase-state change, it
Unnecessary energy storage can be got up, be discharged again when needing energy.Phase transition process refers to material in certain bar
Isothermal or approximate isothermal are maintained under part, and with substantial amounts of energy absorption or the phase-state change process of release.This characteristic
Constituting phase-change material has very wide variety of theoretical foundation.
From the point of view of current domestic and international present Research, research for high performance one-dimensional catenary structure phase-change material and open
Hair application is still in developing stage, such as Y.Zhang, W.Q.Liao, D.W.Fu, H.Y.Ye, Z.N.Chen, R.G.Xiong,
J.Am.Chem.Soc.2015,137,4928；Y.Zhang,W.Q.Liao,D.W.Fu,H.Y.Ye,C.M.Liu,Z.N.Chen,
R.G.Xiong,Adv.Mater.2015,27,3942；H.Y.Ye,Q.H.Zhou,X.H.Niu,W.Q.Liao,D.W.Fu,
Studied in Y.Zhang, Y.M.You, J.L.Wang, Z.N.Chen, R.G.Xiong.In recent years, there is cholesteric-nematic transition
Metal organic borate cause the great research interest of people, this kind of hybrid inorganic-organic materials by well-designed and
Regulation and control, can make full use of inorganic material and the respective advantage of organic material, reach the effect maximized favourable factors and minimized unfavourable ones, be that such material is in
Reveal the property of novelty.
The coordination that 1,4- diazabicylos [2,2,2] octane (Dabco) is directly formed with some metal salts or inorganic acid
Compound is undergone phase transition at low temperature, and then shows good dielectric and ferroelectric property, therefore to DABCO series complexs
Phase transformation, ferroelectricity Quality Research gradually increase.Huang Dengdeng " DABCO series derivates synthesis, characterize and its phase transition property grind
Study carefully " in by modifying Dabco, be then coordinated with metal salt or inorganic acid, and then the phase-change material of acquisition is entered
Research is gone.The main work for having carried out four aspects：(1) with (Dabco-CH2Cl)+·Cl-For construction unit, respectively with mistake
Cross metal ion (Cd2+、Mn2+、Cu2+) reaction, three kinds of metals-organic with reversible transition property are obtained by solwution method and matched somebody with somebody
Position compound.(2) with (Dabco-CH2Cl)+·Cl-For construction unit, respectively with perchlorate and tetrafluoroborate ion
Reaction, two kinds of molecular ion reversible transition compounds are obtained by solwution method.(3) with CH3-Dabco-CH3)2+·2Br-To construct
Unit, react to obtain an organic molecular species ion phase transition compound with perchlorate.(4) with [(CH3)2CH-Dabco-CH
(CH3)2]2+·2Br-For construction unit, respectively with transition metal ions Mn2+、Co2+、Zn2+Reaction, three kinds are obtained by solwution method
Metal-organic coordination compounds with reversible transition property.
Tetrafluoroborate ion is the positive tetrahedron structure of high degree of symmetry, easily unordered in high-temperature-phase, with the drop of temperature
Low, acid ion easily induces dielectric and ferroelectric generation by disorder to order.
At present, research breadth and depth of the people to Dabco derivatives is still shallow, different Dabco derivatives from it is different
Phase transition property caused by ligands requires further study developing.
The content of the invention
Goal of the invention：In order to overcome the deficiencies in the prior art, the invention provides one kind to have low temperature one-dimensional chain
The compound and preparation method and applications of shape structural phase changed properties, intend by well-designed regulation and control sodium tetrafluoroborate metal ion
Salt can be as the compound that phase-change material uses to prepare with organic material so that and preparation technology is simple, easy to operate, and further
Expand the breadth and depth of phase-change material application.
Technical scheme：To achieve the above object, the present invention uses following technical scheme：
A kind of one-dimensional chain low temperature phase change compound, the chemical formula of the phase transition compound is C9H20B3F12N2Na。
Further, the construction unit of the phase transition compound is：At a temperature of 150K, crystal belongs to hexagonal crystal system, empty
Between group be P63；At a temperature of 123K, crystal is monoclinic system, space group P21/c。
Present invention further proposes the preparation method of above-mentioned one-dimensional chain low temperature phase change compound, comprise the following steps：
At normal temperatures, Na will be contained+Soluble compound and triethylene diamine derivative be respectively put into beaker, be slowly added to distilled water
Stirring and dissolving, then two beaker solution are mutually merged again, tetrafluoro boric acid is slowly added dropwise in fume hood, after stirring,
A period of time is stood at room temperature, that is, obtains the phase transition compound C9H20B3F12N2Na。
Further, it is described to contain Na+Soluble compound be containing Na+Soluble borate, wherein it is preferred that tetrafluoro boric acid
Sodium.With Na+Centered on pass through B-F-Na-F-B keys formed one-dimensional catenary structure.
Further, it is pungent to be selected from bromination 1- isopropyls-Isosorbide-5-Nitrae-diazabicylo [2.2.2] for the triethylene diamine derivative
Alkane.
Further, it is described to contain Na+The mol ratio of soluble compound and triethylene diamine derivative be 1：1–3.
Further, it is described to contain Na+Soluble compound and tetrafluoro boric acid mol ratio be 1：2.
Preferably, the invention provides a kind of specific steps of the preparation method of above-mentioned phase transition compound：At normal temperatures, divide
10mmol sodium tetrafluoroborates and 10mmol brominations 1- isopropyls-Isosorbide-5-Nitrae-diazabicylo [2.2.2] octane are not put into beaker,
Distilled water stirring and dissolving is slowly added to, the volume of distilled water is respectively 10-15mL, then again mutually merges two beaker solution,
The slow 20mmol tetrafluoro boric acids in fume hood, after stirring, a period of time is stood at room temperature, that is, obtain described with low
The compound C of warm phase transition property9H20B3F12N2Na。
The invention also provides described one-dimensional chain low temperature phase change compound in textile garment, chamber planting, building row
Application in industry field.
Beneficial effect：Compared with prior art, the present invention has advantages below：
(1) low temperature phase change compound of the invention, is soluble in the big solvent of polarity, such as：Ethylene glycol, dimethyl sulfoxide etc.；No
The small solvent of polarity is dissolved in, such as：Hexamethylene etc., heat decomposition temperature point is of a relatively high, and crystal grain is uniform；
(2) preparation method provided by the invention be at ambient temperature, by solution nature solvent flashing self assembly,
Material structure stability is higher, and the structural controllability of this compound compared with it is strong, yield is high and reproducible, preparation method letter
Single, easy to operate, used sufficient raw, production cost are low；
(3) low temperature phase change compound proposed by the present invention, all has in fields such as textile garment, chamber planting, building trades
There is the application of very big potentiality.
Brief description of the drawings
Fig. 1 is phase transition compound C of the present invention9H20B3F12N2Na synthetic route chart；
Fig. 2 is phase transition compound C in embodiment 19H20B3F12N2Na structure cells (Fig. 2 a 150K, Fig. 2 b at different temperatures
Variation diagram 123K)；
Fig. 3 is phase transition compound C in embodiment 19H20B3F12N2The one-dimensional catenary structure that Na is formed；
Fig. 4 is phase transition compound C in embodiment 19H20B3F12N2Na infrared spectrum；
Fig. 5 is phase transition compound C in embodiment 19H20B3F12N2Na powder PXRD diffraction patterns；
Fig. 6 is phase transition compound C in embodiment 19H20B3F12N2Na thermogravimetric TGA analysis charts；
Fig. 7 is phase transition compound C in embodiment 19H20B3F12N2Na means of differential scanning calorimetry dsc analysis figure；
Fig. 8 is phase transition compound C in embodiment 19H20B3F12N2Na dielectric scanning figure at different frequencies.
Embodiment
The present invention is further explained with reference to the accompanying drawings and examples.
Fig. 1 is the compounds of this invention C9H20B3F12N2Na synthetic route chart.Embodiment 1-4 is prepared according to this synthetic route
Low temperature phase change compound.
Embodiment 1
During room temperature, 10mmol sodium tetrafluoroborates and 10mmol triethylene diamines derivative are filled in 10mL distilled water respectively
Divide and be stirred, after then two solution are sufficiently mixed, 20mmol tetrafluoro boric acid is slowly added dropwise, by standing, solvent is slow
Volatilization crystallizes to obtain a kind of compound with low temperature phase change property certainly.
Embodiment 2
During room temperature, 10mmol sodium tetrafluoroborates and 30mmol triethylene diamines derivative are filled in 10mL distilled water respectively
Divide and be stirred, after then two solution are sufficiently mixed, 20mmol tetrafluoro boric acid is slowly added dropwise, by standing, solvent is slow
Volatilization crystallizes to obtain a kind of compound with low temperature phase change property certainly.
Embodiment 3
During room temperature, 10mmol sodium tetrafluoroborates and 20mmol triethylene diamines derivative are filled in 10mL distilled water respectively
Divide and be stirred, after then two solution are sufficiently mixed, 20mmol tetrafluoro boric acid is slowly added dropwise, by standing, solvent is slow
Volatilization crystallizes to obtain a kind of compound with low temperature phase change property certainly.
Embodiment 4
During room temperature, 10mmol sodium tetrafluoroborates and 10mmol triethylene diamines derivative are filled in 15mL distilled water respectively
Divide and be stirred, after then two solution are sufficiently mixed, 20mmol tetrafluoro boric acid is slowly added dropwise, by standing, solvent is slow
Volatilization crystallizes to obtain a kind of compound with low temperature phase change property certainly.
Phase transition compound crystal prepared by embodiment 1 is analyzed, chooses the monocrystalline of suitable size under the microscope,
With through graphite monochromatised Mo K alpha rays during room temperatureDetermined on Bruker Apex IICCD diffractometers
The X-ray diffraction structure of monocrystalline, the crystallographic parameter of the phase transition compound the results are shown in Table 1.Semiempirical is carried out with SADABS methods
Absorption correction, cell parameter determine that data convert and structure elucidation use SAINT and SHELXL programs respectively with least square method
Bag is completed, and all non-hydrogen atoms carry out anisotropy refine with complete matrix least square method, and the unit cell of compound changes such as Fig. 2 institutes
Show.Under the conditions of 150K (Fig. 2 a), Na ions are in the octoploids structure of distortion, and are mutually interconnected by Na-F keys and B atoms
Connect；When temperature drops to 123K (Fig. 2 b), triethylene diamine derivative ring is distorted.
The crystallographic data of the compound of table 1
Fig. 3 is compound C9H20B3F12N2Na one-dimensional catenary structure.Na atoms are in the octahedral structure of distortion, and
It is connected with each other by Na-F keys and three B atoms, forms one-dimensional catenary structure.
To the infrared spectrum characterization of the compound in embodiment 1, as shown in Figure 4.In 3421cm-1Place, have one it is strong
Absworption peak, it is the stretching vibration absworption peak of C-H singly-bounds on triethylene diamine derivative；In 1476cm-1There is a strong absorption
Peak, it is the flexural vibrations absworption peak of C -- C single bond.
Fig. 5 is the PXRD analysis and characterizations to the compound in embodiment 1, and simulation is can be seen that from powder PXRD diffraction patterns
Diffraction maximum measures the fine of diffraction maximum contrast with actual experiment, illustrates that compound has very high phase purity.
Fig. 6 is that the thermogravimetric analysis to the compound in embodiment 1 characterizes, as can be seen that compound has from thermogravimetric analysis
Very high stability.But with the rise of temperature, at 150 DEG C or so, the one-dimensional catenary structure in compound starts to decompose；
After 200 DEG C, the triethylene diamine derivant structure in compound starts to cave in.
Phase transition performance research, specific steps are carried out to the compound in embodiment 1 using differential scanning calorimetric analysis (DSC)
It is as follows：This compound 8.17mg is weighed, then on Perkin-Elmer Diamond DSC testers, is in heating and cooling
Tested under 5K/min speed, the DSC scanning figures of this compound are as shown in Figure 7.Found from Fig. 7, heating up and dropping
During temperature, the compound is undergone phase transition, and when cooling is in 176.4K, there is obvious exothermic peak, when heating is 186.9K,
There is obvious endothermic peak, illustrate the generation of this compound is mutually changed into single order phase transformation.
Phase transition performance research is carried out to the compound in embodiment 1 using dielectric scanning, comprised the following steps that：Choose this
The appropriate sample of compound, the original shape testing sample that thickness is 0.6mm is processed as on tablet press machine, in the both sides up and down of tabletting,
Conductive silver glue is coated, is then tested on Tonghui TH2828A measurement instrument.We are to obtained this compound
Research is found：Under different frequency scanning, dielectric difference peak is not occurred near transformation temperature, it may be possible to due to macromolecular
Rotate, cause the disappearance of dielectric difference.The dielectric scanning result of the compound is as shown in Figure 8.
Above description is some optimal modes and other embodiment for implementing the present invention, simply to the skill of the present invention
Explanation example effect is played in art design, and it is not intended to limit the scope of the present invention, and those skilled in the art are not departing from
In the spirit and scope of technical solution of the present invention, modify and equivalent substitution, all should fall within the scope and spirit of the invention.
Claims (8)
- A kind of 1. one-dimensional chain low temperature phase change compound, it is characterised in that：The chemical formula of the phase transition compound is C9H20B3F12N2Na, the structure of the compound are
- 2. one-dimensional chain low temperature phase change compound according to claim 1, it is characterised in that：The knot of the phase transition compound Structure unit is：At a temperature of 150K, crystal belongs to hexagonal crystal system, space group P63；At a temperature of 123K, crystal is monoclinic crystal System, space group P21/c。
- A kind of 3. preparation method of one-dimensional chain low temperature phase change compound according to claim 1, it is characterised in that：It is described Preparation method comprises the following steps：At normal temperatures, Na will be contained+Soluble compound be respectively put into triethylene diamine derivative In beaker, distilled water stirring and dissolving is slowly added to, then two beaker solution are mutually merged again, four are slowly added dropwise in fume hood Fluoboric acid, after stirring, a period of time is stood at room temperature, that is, obtains the phase transition compound C9H20B3F12N2Na；It is described Triethylene diamine derivative is selected from bromination 1- isopropyls-Isosorbide-5-Nitrae-diazabicylo [2.2.2] octane.
- 4. the preparation method of one-dimensional chain low temperature phase change compound according to claim 3, it is characterised in that：It is described to contain Na+ Soluble compound be containing Na+Soluble borate.
- 5. the preparation method of one-dimensional chain low temperature phase change compound according to claim 4, it is characterised in that：It is described to contain Na+ Soluble borate be sodium tetrafluoroborate.
- 6. the preparation method of one-dimensional chain low temperature phase change compound according to claim 3, it is characterised in that：It is described to contain Na+ The mol ratio of soluble compound and triethylene diamine derivative be 1：1–3.
- 7. the preparation method of one-dimensional chain low temperature phase change compound according to claim 3, it is characterised in that：It is described to contain Na+ Soluble compound and tetrafluoro boric acid mol ratio be 1：2.
- 8. the preparation method of the one-dimensional chain low temperature phase change compound according to claim any one of 3-7, it is characterised in that： The amount of the sodium tetrafluoroborate and the material of bromination 1- isopropyls-Isosorbide-5-Nitrae-diazabicylo [2.2.2] octane is respectively 10mmol, The volume of distilled water is respectively 10-15mL, and the amount of the material of the tetrafluoro boric acid of dropwise addition is 20mmol.
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| CN108794465A (en) * | 2018-07-24 | 2018-11-13 | 江苏科技大学 | Manganese chloride fluorescent chemicals and its preparation based on 1- isopropyl -1- azabicyclics [2.2.2] octane and application |
| CN109369691B (en) * | 2018-11-15 | 2021-02-26 | 江苏科技大学 | High-temperature phase change compound and preparation method and application thereof |
| CN109761972A (en) * | 2019-01-29 | 2019-05-17 | 德鹿新材料技术(上海)有限公司 | A kind of green fluorescent material, insulation composite coating and preparation method thereof |
| CN110724275B (en) * | 2019-10-21 | 2022-02-15 | 新疆农业大学 | Molybdenum-based supermolecular phase-change crystal material and preparation method thereof |
| CN115181028B (en) * | 2021-04-06 | 2024-05-07 | 中国科学院物理研究所 | Solid-state pressure heating material and preparation method and application thereof |
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