CN105837581B - A kind of low temperature phase change compound, preparation method and applications containing hexafluoro-phosphate radical - Google Patents
A kind of low temperature phase change compound, preparation method and applications containing hexafluoro-phosphate radical Download PDFInfo
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- CN105837581B CN105837581B CN201610271074.8A CN201610271074A CN105837581B CN 105837581 B CN105837581 B CN 105837581B CN 201610271074 A CN201610271074 A CN 201610271074A CN 105837581 B CN105837581 B CN 105837581B
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Abstract
The invention belongs to phase-change material field, discloses a kind of low temperature phase change compound, preparation method and applications containing hexafluoro-phosphate radical.The chemical formula of the compound is：C9H20P2F12N2, at a temperature of 296K, crystal category rhombic system, space group Pbca；At a temperature of 123K, crystal is monoclinic system, space group P21/c.During room temperature, triethylene diamine derivative and hexafluorophosphoric acid are reacted, crystallizing self assembly by the slow evaporating solution of room temperature is made the phase transition compound.The compound with low temperature phase change 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.The phase transition compound 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 low temperature phase change compound containing hexafluoro-phosphate radical, prepare
Method and its application.
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, simple molecular ion type phase-change material causes increasing note
Anticipate power, such as Liu, M.L.Acta Crystal Sec E.2012, E68, m652；Chen,L.Z.；Huang,D.D.；Pan,
Q.J.；Ge,J.Z.RSC Adv.2015,5,13488；W.Zhang,H.Y.Ye,H.L.Cai,J.Z.Ge,R.G.Xiong
S.D.Huang,J.Am.Chem.Soc.,2010,132,7300；Y.Zhang,W.Zhang,S.H.Li,Q.Ye,H.L.Cai,
Studied in F.Deng, R.G.Xiong, S.D.Huang, J.Am.Chem.Soc., 2012,134,11044.Due to temperature
The change of degree, the conversion of the order-disorder of acid ion, the generation of phase transformation can be caused.This kind of hybrid inorganic-organic materials pass through
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
Such material shows 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.By being modified Isosorbide-5-Nitrae-diazabicylo [2,2,2] octane, the three of gained
Ethylene diamine derivative forms the phase transition compound with dielectric property with metal salt or inorganic acid, wherein conventional inorganic acid is
Perchloric acid and tetrafluoro boric acid.At present, still shallow, the different Dabco derivatives of research breadth and depth of the people to Dabco derivatives
From different ligands caused by dielectric property or phase transition property require further study developing.
The content of the invention
Goal of the invention：In order to overcome the deficiencies in the prior art, the present invention provides a kind of tool containing hexafluoro-phosphate radical
There are molecular ion based compound, the preparation method and applications of low temperature phase change property, pass through well-designed regulation and control triethylene diamine
Derivative can be as the compound that phase-change material uses to prepare with acid material, and further expands phase-change material application
Breadth and depth.
Technical scheme：To achieve the above object, the present invention uses following technical scheme：
A kind of low temperature phase change compound containing hexafluoro-phosphate radical, the chemical formula of the compound is C9H20P2F12N2。
Further, the construction unit of the compound is：At a temperature of 296K, crystal category rhombic system, space group is
Pbca；At a temperature of 123K, crystal is monoclinic system, space group P21/c。
Present invention further proposes the preparation method of the above-mentioned low temperature phase change compound containing hexafluoro-phosphate radical, including it is as follows
Step：At normal temperatures, triethylene diamine derivative is put into beaker, is slowly added to distilled water stirring and dissolving, be subsequently placed in logical
In wind kitchen, hexafluorophosphoric acid is slowly added dropwise, while adding the stirring of distillation waterside, then filters, takes subnatant, when standing one section at room temperature
Between, self assembly is crystallized by the slow evaporating solution of room temperature and obtains the low temperature phase change compound C9H20P2F12N2。
Preferably, the triethylene diamine derivative is that bromination 1- isopropyls-Isosorbide-5-Nitrae-diazabicylo [2.2.2] is pungent
Alkane.
Preferably, the mol ratio of bromination 1- isopropyls-Isosorbide-5-Nitrae-diazabicylo [2.2.2] octane and hexafluorophosphoric acid
For 1：2–4.
Preferably, the material of bromination 1- isopropyls-Isosorbide-5-Nitrae-diazabicylo [2.2.2] octane and hexafluorophosphoric acid
Amount be respectively 10mmol and 20mmol, for dissolving the distillation of bromination 1- isopropyls-Isosorbide-5-Nitrae-diazabicylo [2.2.2] octane
The volume of water is 10mL.
Present invention also offers the above-mentioned low temperature phase change compound containing hexafluoro-phosphate radical in textile garment, chamber planting, build
Build the application in industry field.
Beneficial effect：Compared with prior art, the present invention has advantages below：
(1) hexafluorophosphoric acid chosen, has very high symmetry, at different temperature, hexafluoro-phosphate radical easily occurs
The transformation of order-disorder, easily cause the generation of phase transformation；
(2) bromination 1- isopropyls-Isosorbide-5-Nitrae-diazabicylo [2.2.2] octane selected is a kind of aminated compounds, easily
Acid-base neutralization reaction occurs with the hexafluorophosphoric acid of acidity, improves the possibility of phase-change product synthesis.
(3) 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；
(4) 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 the compounds of this invention C9H20P2F12N2Synthetic route chart；
Fig. 2 is chemicals C in embodiment 19H20P2F12N2Structure cell is at different temperatures (Fig. 2 a 296K, Fig. 2 b 123K)
Variation diagram；
Fig. 3 is compound C in embodiment 19H20P2F12N2The one-dimensional chain hydrogen bond structure figure of formation；
Fig. 4 is compound C in embodiment 19H20P2F12N2Infrared spectrum；
Fig. 5 is compound C in embodiment 19H20P2F12N2Powder PXRD diffraction patterns；
Fig. 6 is compound C in embodiment 19H20P2F12N2Thermogravimetric TGA analysis charts；
Fig. 7 is compound C in embodiment 19H20P2F12N2Means of differential scanning calorimetry dsc analysis figure；
Fig. 8 is compound C in embodiment 19H20P2F12N2The dielectric scanning figure under 100kHZ and 1MHZ frequencies.
Embodiment
The present invention is further explained with reference to the accompanying drawings and examples.Fig. 1 is the compounds of this invention
C9H20P2F12N2Synthetic route chart.Embodiment 1-4 prepares low temperature phase change compound according to this synthetic route.
Embodiment 1
At normal temperatures, 10mmol triethylene diamine derivatives are put into beaker, it is molten is slowly added to the stirring of 10ml distilled water
Solution, is subsequently placed in ventilating kitchen, 20mmol hexafluorophosphoric acids is slowly added dropwise, while adding 5ml distillations waterside stirring, rear filtering, takes under it
Layer clear liquid, stands a period of time at room temperature, and crystallizing self assembly by the slow evaporating solution of room temperature obtains described having low-temperature phase
The compound of change nature.
Embodiment 2
At normal temperatures, 10mmol triethylene diamine derivatives are put into beaker, it is molten is slowly added to the stirring of 10ml distilled water
Solution, is subsequently placed in ventilating kitchen, 30mmol hexafluorophosphoric acids is slowly added dropwise, while adding 5ml distillations waterside stirring, rear filtering, takes under it
Layer clear liquid, stands a period of time at room temperature, and crystallizing self assembly by the slow evaporating solution of room temperature obtains described having low-temperature phase
The compound of change nature.
Embodiment 3
At normal temperatures, 10mmol triethylene diamine derivatives are put into beaker, it is molten is slowly added to the stirring of 10ml distilled water
Solution, is subsequently placed in ventilating kitchen, 40mmol hexafluorophosphoric acids is slowly added dropwise, while adding 10ml distillations waterside stirring, rear filtering, takes under it
Layer clear liquid, stands a period of time at room temperature, and crystallizing self assembly by the slow evaporating solution of room temperature obtains described having low-temperature phase
The compound of change nature.
Embodiment 4
At normal temperatures, 10mmol triethylene diamine derivatives are put into beaker, it is molten is slowly added to the stirring of 10ml distilled water
Solution, is subsequently placed in ventilating kitchen, 20mmol hexafluorophosphoric acids is slowly added dropwise, while adding 10ml distillations waterside stirring, rear filtering, takes under it
Layer clear liquid, stands a period of time at room temperature, and crystallizing self assembly by the slow evaporating solution of room temperature obtains described having low-temperature phase
The compound of change nature.
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 II CCD 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 296K (Fig. 2 a), there is an independent [C in structure cell9H20N2]2+Cation, two hexafluoro-phosphate radical the moon from
Son, wherein there is a hexafluoro-phosphate radical to be in disordered state, each F atom occupies two positions；When temperature drops to 123K
(Fig. 2 b), contain two independent [C in structure cell9H20N2]2+Cation, four hexafluoro-phosphate radical anion, wherein there is one six
Fluorophosphoric acid root is in disordered state, and triethylene diamine derivative ring is distorted.
The crystallographic data of the compound of table 1
Fig. 3 is compound C9H20P2F12N2One-dimensional chain hydrogen bond structure figure.From the structure it can be seen from the figure that [C9H20N2
]2+Cation is connected with each other with hexafluoro-phosphate radical by N-HF and C-HF hydrogen bonds, forms one-dimensional chain hydrogen bond knot
Structure.
To the infrared spectrum characterization of the compound in embodiment 1, as shown in Figure 4.In 3457cm-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 1428cm-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 chemical combination from thermogravimetric analysis (TGA)
Thing has very high stability.But with the rise of temperature, at 250 DEG C or so, the triethylene diamine derivative in compound
Structure starts to cave in, and is caved in completely to 400 DEG C of tiled configurations.
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 2.67mg 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.Find from Fig. 7, exist in cooling
During 130.9K, there is obvious exothermic peak, when heating is 135.4K, there is obvious endothermic peak, illustrate that this compound occurs
Be 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 0.5mm 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 100kHZ and 1MHZ frequency scanning, under heating and cooling mode, occur significantly may be used in 140K or so
Inverse dielectric difference peak, the dielectric scanning result of the compound are 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 (5)
- A kind of 1. low temperature phase change compound containing hexafluoro-phosphate radical, it is characterised in that：The chemical formula of the compound is C9H20P2F12N2, the structural formula of the compound is
- 2. the low temperature phase change compound according to claim 1 containing hexafluoro-phosphate radical, it is characterised in that：The compound Construction unit is：At a temperature of 296K, crystal category rhombic system, space group Pbca；At a temperature of 123K, crystal is monoclinic crystal System, space group P21/c。
- 3. a kind of preparation method of the low temperature phase change compound according to claim 1 containing hexafluoro-phosphate radical, its feature exist In：The preparation method comprises the following steps：At normal temperatures, triethylene diamine derivative is put into beaker, is slowly added to steam Distilled water stirring and dissolving, is subsequently placed in ventilating kitchen, and hexafluorophosphoric acid is slowly added dropwise, and distilled water stirring and dissolving is slowly added dropwise, then mistake Filter, takes subnatant, stands a period of time at room temperature, and crystallizing self assembly by the slow evaporating solution of room temperature obtains the low temperature Phase transition compound C9H20P2F12N2；The triethylene diamine derivative is bromination 1- isopropyl -1,4- diazabicylos [2.2.2] Octane.
- 4. the preparation method of the low temperature phase change compound according to claim 3 containing hexafluoro-phosphate radical, it is characterised in that：Institute The mol ratio for stating bromination 1- isopropyl -1,4- diazabicylos [2.2.2] octanes and hexafluorophosphoric acid is 1：2–4.
- 5. the preparation method of the low temperature phase change compound according to claim 4 containing hexafluoro-phosphate radical, it is characterised in that：Institute The amount for stating the material of bromination 1- isopropyls-Isosorbide-5-Nitrae-diazabicylo [2.2.2] octane and hexafluorophosphoric acid is respectively 10mmol and 20- 40mmol, it is 10mL for dissolving the volume of distilled water of bromination 1- isopropyls-Isosorbide-5-Nitrae-diazabicylo [2.2.2] octane.
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| CN113429362A (en) * | 2021-06-01 | 2021-09-24 | 南昌大学 | Cyclic amine perchloric acid reversible phase-change material and preparation method thereof |
| CN113604204B (en) * | 2021-07-27 | 2022-05-31 | 中国科学院金属研究所 | Application of inorganic plastic crystal material in solid refrigeration |
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| Hydrothermal Syntheses, Crystal Structures,TGA and Electrochemistry Properties of Two Metal-organic Coordination Compounds Based on 4-((1H-1,2,4-triazol-1-yl)methyl)-[1,1-biphenyl]-2-carbonitril;HUANG Deng-Deng,et al.,;《Chinese J. Struct. Chem.》;20151231;第34卷(第1期);第123-132页 * |
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