Vinyl pivalate Propagation Kinetics in Radical Polymerization
Bibliographic record
Abstract
Radical propagation kinetics of the bulk homopolymerizations of vinyl pivalate (VPi) and vinyl benzoate (VBz) have been studied using pulsed‐laser polymerization (PLP) combined with size exclusion chromatography (SEC). As part of the study, the Mark–Houwink parameters of poly(VPi) and poly(VBz) in tetrahydrofuran are determined using a triple detector SEC. The observed significant increase (by ≈ 20%) of the bulk VPi propagation rate coefficient ( k p ) as pulse repetition rate is increased from 200 to 500 Hz is similar to that reported for vinyl acetate (VAc). Data collected in the temperature range of 25–85 °C for VPi is well fit by the Arrhenius relation ln( k p /L mol −1 s −1 ) = 15.73−2093( T /K). The activation energy is similar to that found for vinyl acetate (VAc), with k p values higher by ≈ 50%. PLP studies in ethyl acetate and in heptane find no substantial solvent effect on VPi or VAc k p values. Attempts to measure the propagation kinetics of VBz by PLP are not successful, suggesting that significant radical stabilization occurs for the system. Small‐scale batch polymerization experiments demonstrate relative polymerization rates of these vinyl ester monomers that are consistent with the PLP results. image
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How this classification was reachedexpand
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 itClassification
machine, unvalidatedMachine predicted; a candidate call from one teacher head, not a consensus.
How this classification was reached, model by model and score by score, is at the end of the page under "How this classification was reached".