The temperature dependence of the Hildebrand solubility parameters of selected hydrocarbon polymers and hydrocarbon solvents: a molecular dynamics investigation
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Bibliographic record
Abstract
Abstract Context To determine the miscibility of liquids at high temperatures using the concept of Hildebrand solubility parameter $$\delta$$ <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> <mml:mi>δ</mml:mi> </mml:math> , the current practice is to examine the difference in $$\delta$$ <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> <mml:mi>δ</mml:mi> </mml:math> between two liquids at room temperature, assuming that $$\delta$$ <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> <mml:mi>δ</mml:mi> </mml:math> is not sensitive to temperature . However, such an assumption may not be valid for certain polymer blends and solutions. Therefore, a knowledge of the δ values of the liquids of interest at high temperatures is desirable. The determination of δ at high temperatures, especially for high-molecular-weight polymers, is impossible, as polymers have vapor pressures of zero. To this end, molecular dynamics (MD) simulations provide a practical means for determining δ over a wide range of temperatures. In this work, we study the temperature dependence of $$\delta$$ <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> <mml:mi>δ</mml:mi> </mml:math> of five hydrocarbon polymers: polyethylene (PE), isotactic and atactic polypropylene ( i -PP and a -PP), polyisobutylene (PIB), and polyisoprene (PI) in five hydrocarbon solvents: n -pentane, n -hexane, n -dodecane, isobutene, and cyclohexane. The polymers are modeled as monodisperse chains with 100 repeat units. The average δ values of PE, i -PP, a -PP, PIB, and PI at 300 K are determined as 18.6, 14.9, 14.6, 14.3, and 16.4 MPa 1/2 , respectively, in a good agreement with experimental data. The δ values of these polymers at various temperatures are also determined. The temperature dependence of δ is fitted to two linear equations, one above and the other below the polymer’s glass transition temperature T g . The δ values are more sensitive to temperature at T ≥ T g . The T g values of the polymers, determined based upon their specific volumes and δ values agree with the experiment qualitatively. The determination of the temperature dependence of δ has a great potential for industrial applications, such as determining miscibility, developing polymeric organogelators as flocculants and oil spill treating agents, and identifying potential solvents and ideal processing temperatures. Methods The MD simulations are performed using the GROMACS 2022.3 package with optimized potential for liquid simulations-all atom (OPLS-AA) force field parameters. All polymers are built as extended chains using CHARMM-GUI Polymer Builder. Graphical Abstract
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Full frame distilled prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. Learned from the 10,348 direct Codex labels and 10,348 direct Gemma labels. Candidate is the union of thresholded teacher heads; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels or direct frontier model labels.
Codex and Gemma teacher scores by category
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.000 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.000 | 0.000 |
Machine scores (provisional)
The two teacher heads of the student model, read on this work. A score orders the frame for review; it never asserts a category, and the validation status ships verbatim with every row.
Baseline scores from an immature model (maturity gate not passed, 7 training rounds). Scores rank; they never assert a category.
score_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from it