Preparation, Thermal Behavior, and Conformational Stability of HMX/Cyclopentanone Cocrystallization
"> Figure 1
<p>Optical microscope images of (<b>a</b>) raw HMX and (<b>b</b>) HMX/cyclopentanone cocrystallization and (<b>c</b>,<b>d</b>) polarized microscope images of HMX/cyclopentanone cocrystallization.</p> "> Figure 2
<p>XRD patterns of pure β-HMX, α-HMX, raw-HMX, and HMX/cyclopentanone cocrystallization.</p> "> Figure 3
<p>FT−IR spectra of the raw materials and the cocrystallization.</p> "> Figure 4
<p>TG−DTG curves of HMX/cyclopentanone cocrystallization.</p> "> Figure 5
<p>DSC curves of pure β-HMX, α-HMX, and HMX/cyclopentanone cocrystallization.</p> "> Figure 6
<p>High-pressure DSC curves of pure β-HMX and HMX/cyclopentanone cocrystallization.</p> "> Figure 7
<p>The curve of heat−flow of HMX in cyclopentanone.</p> "> Figure 8
<p>The relationship of reaction rate constant (<span class="html-italic">k</span>) versus temperature (<span class="html-italic">T</span>) for the dissolution of HMX in cyclopentanone (the red line is the best−fit line).</p> "> Figure 9
<p>Screenshots of MD simulations of HMX in cyclopentanone at 313.15 K: (<b>a</b>) 0 ps; (<b>b</b>) 345 ps; (<b>c</b>) 666 ps; and (<b>d</b>) 670 ps. (HMX molecules are represented by a ball-and-stick, and cyclopentanone molecules are represented by a line.).</p> "> Figure 10
<p>α-HMX and cyclopentanone dimer structures optimized at the ωB97XD/6-311G(d,p) level ((<b>a</b>) α-HMX/α-HMX; (<b>b</b>) cyclopentanone/cyclopentanone; (<b>c</b>) α-HMX/cyclopentanone).</p> "> Figure 11
<p>(<b>a</b>) Final structures after equilibrated for by after molecular dynamics simulation; (<b>b</b>) Interaction of HMX with cyclopentanone (The dashed line indicates the distance between the O atom of the cyclopentanone carbonyl and the four methylene H atom of HMX in Å).</p> ">
Abstract
:1. Introduction
2. Materials and Methods
2.1. Materials
2.2. Preparation of HMX/Cyclopentanone Cocrystalation
2.3. Characterization of HMX/Cyclopentanone Cocrystalation
2.4. Calorimeter Experiment of HMX in Cyclopentanone
2.5. Computation
3. Results and Discussion
3.1. Crystal Morphology of HMX/Cyclopentanone Cocrystallization
3.2. Chemical Characterization of HMX/Cyclopentanone Cocrystallization
3.3. Thermochemical Behavior of HMX in Cyclopentanone
3.4. Kinetics of the Dissolution Process
3.5. Conformation Stability of HMX Molecule in Cyclopentanone
4. Conclusions
Author Contributions
Funding
Data Availability Statement
Acknowledgments
Conflicts of Interest
Appendix A
T (K) | m (mg) | t (s) | −(dH/dt)i (mJ/s) | () i | (kJ/mol) |
---|---|---|---|---|---|
303.15 | 2.58 | 200 | −0.0289 | 0.1277 | 10.5044 |
400 | −0.0315 | 0.2932 | |||
600 | −0.0300 | 0.4515 | |||
800 | −0.0269 | 0.5931 | |||
1000 | −0.0235 | 0.7119 | |||
1200 | −0.0200 | 0.8051 | |||
1400 | −0.0174 | 0.8768 | |||
308.15 | 2.82 | 200 | −0.0561 | 0.2833 | 10.9809 |
400 | −0.0405 | 0.5069 | |||
600 | −0.0293 | 0.6591 | |||
800 | −0.0210 | 0.7629 | |||
1000 | −0.0168 | 0.8364 | |||
1200 | −0.0129 | 0.8899 | |||
1400 | −0.0103 | 0.9293 | |||
313.15 | 2.88 | 200 | 0.1960 | 0.2295 | 18.8202 |
400 | 0.1291 | 0.4536 | |||
600 | 0.0832 | 0.6144 | |||
800 | 0.0551 | 0.7329 | |||
1000 | 0.0328 | 0.8213 | |||
1200 | 0.0187 | 0.8868 | |||
1400 | 0.0068 | 0.9352 | |||
318.15 | 2.77 | 200 | 0.2192 | 0.2527 | 15.8023 |
400 | 0.1753 | 0.4945 | |||
600 | 0.1350 | 0.6775 | |||
800 | 0.1016 | 0.8112 | |||
1000 | 0.0727 | 0.9030 | |||
1200 | 0.0503 | 0.9595 | |||
1400 | 0.0324 | 0.9884 | |||
323.15 | 2.56 | 200 | 0.1416 | 0.2280 | 11.9946 |
400 | 0.1041 | 0.4934 | |||
600 | 0.0687 | 0.6831 | |||
800 | 0.0433 | 0.8098 | |||
1000 | 0.0278 | 0.8922 | |||
1200 | 0.0183 | 0.9456 | |||
1400 | 0.0097 | 0.9793 |
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T (K) | a (mol) | b (mol/L) | Q (J) | dissH (kJ/mol) |
---|---|---|---|---|
303.15 | 8.71 | 0.87 | 0.0915 | 10.50 |
308.15 | 9.52 | 0.95 | 0.1046 | 10.98 |
313.15 | 9.72 | 0.97 | 0.1868 | 19.21 |
318.15 | 9.35 | 0.94 | 0.1496 | 16.00 |
323.15 | 8.67 | 0.86 | 0.1047 | 12.11 |
T (K) | n | lnk | r |
---|---|---|---|
303.15 | 0.3549 | −5.6641 | 0.9940 |
308.15 | 0.7911 | −5.0505 | 0.9940 |
313.15 | 1.3185 | −4.1569 | 0.9935 |
318.15 | 0.4623 | −4.2205 | 0.9901 |
323.15 | 0.7517 | −4.2940 | 0.9947 |
Etot (a.u.) | s 1 (kcal/mol) | EBSSE 2 (kcal/mol) | ’s 3 (kcal/mol) | |
---|---|---|---|---|
α-HMX/cyclopentanone | −1467.05 | −14.04 | 2.29 | −11.75 |
α-HMX dimer | −2392.99 | −16.45 | 3.15 | −13.30 |
Cyclopentanone dimer | −541.12 | −9.73 | 2.24 | −7.49 |
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Tao, Y.; Jin, S.; Wang, T.; She, C.; Chen, K.; Wang, J.; Li, L. Preparation, Thermal Behavior, and Conformational Stability of HMX/Cyclopentanone Cocrystallization. Crystals 2024, 14, 711. https://doi.org/10.3390/cryst14080711
Tao Y, Jin S, Wang T, She C, Chen K, Wang J, Li L. Preparation, Thermal Behavior, and Conformational Stability of HMX/Cyclopentanone Cocrystallization. Crystals. 2024; 14(8):711. https://doi.org/10.3390/cryst14080711
Chicago/Turabian StyleTao, Yuting, Shaohua Jin, Tongbin Wang, Chongchong She, Kun Chen, Junfeng Wang, and Lijie Li. 2024. "Preparation, Thermal Behavior, and Conformational Stability of HMX/Cyclopentanone Cocrystallization" Crystals 14, no. 8: 711. https://doi.org/10.3390/cryst14080711