CN103288648A - N-octane amine oxalate and preparation method and application thereof - Google Patents

N-octane amine oxalate and preparation method and application thereof Download PDF

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CN103288648A
CN103288648A CN2013101324056A CN201310132405A CN103288648A CN 103288648 A CN103288648 A CN 103288648A CN 2013101324056 A CN2013101324056 A CN 2013101324056A CN 201310132405 A CN201310132405 A CN 201310132405A CN 103288648 A CN103288648 A CN 103288648A
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positive
oxalate
alkanamine
ethyl alcohol
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邸友莹
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Liaocheng University
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Abstract

The invention provides n-octane amine oxalate and a preparation method thereof. The preparation method comprises the following steps: dissolving oxalic acid in absolute ethyl alcohol at first; then adding n-octane amine drop by drop, wherein a white precipitate is produced immediately; carrying out heating reflux and allowing the precipitate to be dissolved during heating; cooling to room temperature and carrying out pumping filtration and washing with absolute ethyl alcohol; dissolving an obtained white solid product in a great amount of absolute ethyl alcohol and allowing the solvent to be naturally volatilized at room temperature so as to obtain a colorless transparent block crystal; and carrying out re-crystallization with absolute ethyl alcohol so as to obtain an n-octane amine oxalate crystal. The preparation method provided by the invention is simple and environment-friendly and provides a novel approach for development of phase change materials.

Description

Positive eight alkanamine oxalate and its preparation method and application
Technical field
The invention belongs to the synthetic field of Chemicals, specifically relate to the preparation method of positive eight alkanamine oxalate and its crystalline structure and to the research of its solid-solid phase-change energy-storage property matter aspect.
Background technology
Energy problem has become the important factor of a restriction countries in the world economy and social development speed, and phase-changing energy storage material is exactly energy-conservation and solves a kind of exotic materials of energy storages and utilization.According to the latent heat of phase change material, control energy absorption and release can improve rate of energy.At present, phase-changing energy storage material has obtained studying more widely, and obtains using more widely in fields such as sun power utilization, phase change energy-storage type air-conditioning, insulation clothes, energy storage cookers.In recent years because the positive alkanamine of long-chain and metal chloride reaction can generate a kind of title complex with perovskite structure, this class title complex is showing very big solid-to-solid transition heat in certain warm area, can be used as a kind of potential energy storage material and paid close attention to widely.Because the inorganic acid salt of the positive alkanamine of long-chain and the structure of organic acid salt are similar to long-chain metal acid alkane ammonium complex structure, and there is not heavy metal in the inorganic acid salt of the positive alkanamine of long-chain and the organic acid salt, therefore this class material is a kind of potential novel nontoxic, the phase-changing energy storage material of environment-friendly type.Many traditional characterization methods such as infrared spectra, nuclear magnetic resonance spectrum, mass spectrum etc. be in the successful utilization of this compounds, for its research provides important guarantee, and the development and application of x-ray diffraction technique more it provides intuitively and accurately structural information.The thermal capacitance of material is one of its most basic thermodynamic property, and the thermodynamic property of material phase transition process is that material is as the important evidence of phase change material.Adiabatic calorimeter is to obtain the material thermal capacitance and calculate the most reliable research means of various thermodynamic(al)functions.Utilize the thermal capacitance of accurate Automatic Adiabatic calorimeter measurement title complex and obtain its Shu Ping thermal capacitance value and the basic thermodynamic datas such as enthalpy, entropy and Gibbs free energy during with respect to 298.15 K.For the phase transformation peak that occurs on the thermal capacitance curve, in conjunction with the TG/DSC technology it is analyzed and studies, can infer its solid-solid phase-change mechanism.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of positive eight alkanamine oxalate and preparation method thereof.
Positive eight alkanamine oxalate, structural formula is as follows:
Figure DEST_PATH_782467DEST_PATH_IMAGE002
The present invention also provides the preparation method of positive eight alkanamine oxalate, at first oxalic acid is dissolved in an amount of dehydrated alcohol; Dropwise drip positive eight alkanamines then, the adularescent precipitation produces at once; Reflux, resolution of precipitate in the heat-processed; Cool to room temperature, suction filtration is also used absolute ethanol washing; The white solid product that obtains is dissolved in a large amount of dehydrated alcohols, and room temperature nature solvent flashing obtains the water white transparency bulk crystals; Use the dehydrated alcohol recrystallization, get just eight alkanamine oxalate.
Foregoing preparation method, preferably scheme is, positive eight alkanamines and oxalic acid mol ratio=2: 1.
Foregoing preparation method, preferred scheme is that reflux 4-10 h(is preferred, reflux 6 h).
Foregoing preparation method, preferred scheme are that suction filtration is also used absolute ethanol washing three times.
The present invention also provides the application of positive eight alkanamine oxalate as phase-changing energy storage material.
Preparation method provided by the invention is simple, and environmental friendliness is for the exploitation phase-changing energy storage material provides new way.
Description of drawings
Fig. 1 is (C 8H 17NH 3) 2C 2O 4(s) molecular structure.
Fig. 2 is the transoid conformation of the organic carbochain of positive eight alkanamine oxalate.
Fig. 3 is (C 8H 17NH 3) 2C 2O 4(s) thermal capacitance curve.
Fig. 4 is (C 8H 17NH 3) 2C 2O 4(s) TG/DSC curve.
Embodiment
Describe technical scheme of the present invention in detail below in conjunction with embodiment and accompanying drawing, but protection domain is not by this restriction.
Embodiment: the result of study of the preparation method of positive eight alkanamine oxalate and its crystalline structure, low temperature thermal capacitance and DSC.
Positive eight alkanamine oxalate structural formulas:
Figure 699607DEST_PATH_IMAGE004
The preparation method of positive eight alkanamine oxalate, step is: (C 8H 17NH 3) 2C 2O 4(s) preparation: at first oxalic acid is dissolved in (preferred, per 0.3 ~ 0.6 mmol oxalic acid is dissolved in the 100 mL dehydrated alcohols) in an amount of dehydrated alcohol, then according to mol ratio n(CH 3(CH 2) 7NH 2): n(H 2C 2O 42H 2O)=2: 1, dropwise dripping positive eight alkanamines of respective amount, the adularescent precipitation produces at once.Reflux 6 h, heating (preferred, to 50-70 ℃) resolution of precipitate.Cool to room temperature, suction filtration is also used absolute ethanol washing three times.The white solid product that obtains is dissolved in a large amount of dehydrated alcohols, at room temperature nature solvent flashing, obtains the water white transparency bulk crystals.Use the dehydrated alcohol recrystallization.
One, the single crystal structure analysis of positive eight alkanamine oxalate
The molecular structure of positive eight alkanamine oxalate as shown in Figure 1, what organic carbochain all presented is orderly transoid conformation.Not only there is the electrostatic interaction of zwitterion in the molecule, also has N-H ... the O hydrogen bond action.In Fig. 2 from aLook on the direction, can find that negatively charged ion oxalate layer is passed through the hydrogen bond action double team by positively charged ion organic chain layer and, this structure is just as one " sandwich ".Positive eight alkanamine oxalate also can form similar and structure phospholipid bilayer in structure cell is piled up, and have model ylid bloom action power between the organic chain.Hydrogen bond action makes (C 8H 17NH 3) 2C 2O 4(s) exist A-bThe plane has formed a two-dimension netted supramolecular structure as shown in Figure 2.The refine result of positive eight alkanamine oxalate, main bond distance's bond angle, the bond distance of hydrogen bond and bond angle are listed in respectively among the table 1-3.
The crystallographic data of the positive eight alkanamine oxalate of table 1 and refine result
Figure 541662DEST_PATH_IMAGE006
The main bond distance [] of the positive eight alkanamine oxalate of table 2 and bond angle [°]
Figure 936871DEST_PATH_IMAGE008
The hydrogen bond bond distance [] of the positive alkanamine oxalate of table 3 and bond angle [°]
Figure 751243DEST_PATH_IMAGE010
Two, the thermodynamic study of positive eight alkanamine oxalate
(1) (C 8H 17NH 3) 2C 2O 4(s) phase research: (C 8H 17NH 3) 2C 2O 4(s) experiment thermal capacitance the results are shown in table 4 and is plotted among Fig. 3.Thermal capacitance curve at warm area 78 ~ 333 K materials is level and smooth increasing progressively continuously, this explanation (C 8H 17NH 3) 2C 2O 4(s) be stable in this warm area structure, do not decompose, associate thermal anomaly phenomenons such as phase transformation.But can find that in the later temperature range of 333 K three tangible endotherm(ic)peaks appear in warm area 334 ~ 374 K scopes.At transition temperature area, through three replicate measurement thermal capacitances, the result who obtains is shown in the illustration among Fig. 3.Not weightless at warm area 334 ~ 374 K places by the TG/DTG specimen, before the fusing point warm area, there is not weightlessness yet.Therefore these three endotherm(ic)peaks are because the solid-to-solid transition of material causes.First endotherm(ic)peak may be because the destruction of intermolecular model ylid bloom action power causes, the fracture of second endotherm(ic)peak possibility hydrogen bond causes.The 3rd endotherm(ic)peak is because the part " fusing " of organic chain causes.
Table 4 (C 8H 17NH 3) 2C 2O 4(s) experiment thermal capacitance value
T (K) C p , m (J×K -1×mol -1) T (K) C p , m (J×K -1×mol -1) T (K) C p , m (J×K -1×mol -1)
78.3175 76.9533 185.806 349.597 315.920 614.210
80.6744 82.3568 188.449 356.952 318.038 619.609
83.0313 88.2106 192.010 365.086 320.120 625.530
85.3168 94.9649 194.880 371.253 322.180 631.360
87.5309 100.819 199.617 379.153 324.282 636.461
89.6735 107.123 202.488 385.512 326.292 641.851
91.8162 112.301 206.005 393.220 328.373 647.165
93.8874 117.705 208.947 398.038 330.420 653.900
95.9586 124.234 212.464 405.939 332.470 659.290
97.9584 130.088 217.129 413.647 334.498 672.701
99.9582 136.167 219.928 419.323 336.200 1519.88
101.887 142.020 222.440 424.228 338.301 769.051
103.815 146.523 225.024 428.759 340.860 695.900
105.743 152.602 227.536 433.711 342.943 718.832
107.600 157.781 229.945 438.312 344.990 746.600
109.457 163.859 232.632 442.867 346.490 2505.51
111.314 167.237 234.928 447.726 346.950 12404.7
113.100 173.541 237.943 453.518 347.070 18299.7
114.885 179.394 241.388 459.591 347.190 16965.5
116.742 183.222 244.833 467.112 347.400 10930.0
118.456 188.851 247.560 472.204 348.740 2245.45
121.456 197.406 250.287 478.464 351.603 1544.53
124.527 205.962 253.086 484.023 353.923 1167.88
127.098 210.690 255.871 488.744 356.459 774.891
129.598 218.570 258.727 495.274 358.684 791.241
132.241 225.099 261.584 500.902 360.720 797.410
134.812 230.052 264.426 506.651 362.799 812.847
137.383 237.707 267.225 511.585 364.880 826.277
139.954 244.687 270.083 517.788 366.880 859.330
142.525 249.640 272.940 524.317 368.600 1252.85
145.096 256.845 275.726 531.072 369.750 2082.28
147.596 262.009 278.725 535.575 370.960 1270.84
150.239 269.099 281.654 541.879 372.880 909.570
152.738 274.588 284.522 548.099 374.840 859.220
155.238 280.253 287.536 553.869 376.630 862.990
157.809 284.981 289.904 558.196 378.370 867.870
160.238 290.497 292.273 563.585 380.110 868.620
162.809 296.538 295.144 569.886 381.780 873.170
165.237 302.317 298.009 575.200 383.373 880.000
167.880 308.096 300.167 580.438 385.239 885.255
170.451 314.137 303.397 586.663 386.603 888.058
172.951 319.435 306.555 593.191 388.158 894.015
175.665 326.640 309.569 599.492 389.904 899.620
178.307 331.368 311.292 603.895 391.483 906.978
182.093 340.667 313.014 608.526
Long-chain nalka amine is inorganic can solid-to-solid transition to occur at the measurement warm area with organic acid salt, these solid-solid phase phase enthalpy of transition and entropy can utilize following formula to calculate (Tan Zhicheng, Zhou Lixing, Chen Shuxia, Deng. foundation and the demarcation [J] of the accurate Automatic Adiabatic calorimeter assembly of 80 – 400K. Chinese science B collects, 1983,13 (6): 497 – 505) (Tan Zhicheng, Liu Beiping, Yan Junbiao, Deng. the foundation [J] of the full-automatic adiabatic Calorimetry system of a kind of novel 80 ~ 400 K high precision. computer and applied chemistry, 2003,20 (3): 265 – 268):
Figure 2013101324056100002DEST_PATH_IMAGE011
Formula (1)
Figure 636022DEST_PATH_IMAGE012
Formula (2)
In the formula, T iBe certain the lower slightly temperature spot of temperature than the beginning phase transformation, T TrsBe phase transition temperature, T fBe than certain the slightly high temperature spot of temperature that finishes phase transformation, C P(i) Be that temperature is T iThe time material molecular heat capacity; C P(f) Be that temperature is T fThe time material molecular heat capacity; QFor with sample and sample pool from T i~ T fThe total heat of introducing, nBe the amount of substance of sample, H 0Be that the sky sample pool is at warm area T i~ T fThermal capacitance.D Trs S mIt is the solid-to-solid transition entropy of sample.
Utilize formula (1) and (2) to obtain enthalpy of phase change and the phase transformation entropy of positive eight alkanamine oxalate.The results are shown in Table 5 for phase transformation peak temperature, enthalpy of phase change and phase transformation entropy that three repeated experiments of positive eight alkanamine oxalate obtain.
The positive eight alkanamine oxalate of table 5 repeat thermal capacitance in transition temperature area three series and measure the phase transformation result who obtains
Figure 2013101324056100002DEST_PATH_IMAGE013
The suitable phase transition temperature of three kinds of material phase transition process as can be seen from Table 5, enthalpy of phase change is big, reversibility and the circulation ratio of phase transformation are very good, this just illustrates that they have very big value and the potentiality of using as phase-changing energy storage material, are expected to have important application prospects in fields such as storage of solar energy and industrial afterheat recovery.

Claims (6)

1. positive eight alkanamine oxalate is characterized in that structural formula is as follows:
Figure 889655DEST_PATH_IMAGE001
。
2. the preparation method of positive eight alkanamine oxalate as claimed in claim 1 is characterized in that, at first oxalic acid is dissolved in the dehydrated alcohol; Drip positive eight alkanamines then, the adularescent precipitation produces at once; Reflux, the thermal precipitation dissolving; Cool to room temperature, suction filtration is also used absolute ethanol washing; The white solid product that obtains is dissolved in a large amount of dehydrated alcohols, and room temperature nature solvent flashing obtains the water white transparency bulk crystals; Use the dehydrated alcohol recrystallization, get just eight alkanamine oxalate crystal.
3. preparation method as claimed in claim 2 is characterized in that, positive eight alkanamines and oxalic acid mol ratio=and 2: 1.
4. preparation method as claimed in claim 2 is characterized in that, reflux 4-10 h(is preferred, reflux 6 h).
5. preparation method as claimed in claim 2 is characterized in that, suction filtration is also used absolute ethanol washing three times.
6. positive eight alkanamine oxalate as claimed in claim 1 are as the application of phase-changing energy storage material.
CN2013101324056A 2013-04-17 2013-04-17 N-octane amine oxalate and preparation method and application thereof Pending CN103288648A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103553926A (en) * 2013-10-30 2014-02-05 聊城大学 (C8H17NH3)2[ZnBr4](s) and preparation method and application thereof

Citations (2)

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Publication number Priority date Publication date Assignee Title
US3976669A (en) * 1972-10-02 1976-08-24 Sun Ventures, Inc. Tertiary diamides
CN1165136A (en) * 1996-05-14 1997-11-19 谷传香 Method for preparing methyl sulfonic acid

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3976669A (en) * 1972-10-02 1976-08-24 Sun Ventures, Inc. Tertiary diamides
CN1165136A (en) * 1996-05-14 1997-11-19 谷传香 Method for preparing methyl sulfonic acid

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
LI-JUN ZHANG，等: "Crystal structure and thermochemical properties of n-octanammonium oxalate (C8H17NH3)2C2O4(s)", 《J. CHEM. THERMODYNAMICS》 *
赵杰，等: "有机相变储能材料研究进展", 《中国科技论文在线》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103553926A (en) * 2013-10-30 2014-02-05 聊城大学 (C8H17NH3)2[ZnBr4](s) and preparation method and application thereof

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Application publication date: 20130911