The Effect of Intramolecular Transfer to Polymer on Stationary Free Radical Polymerization of Alkyl Acrylates
Bibliographic record
Abstract
New expressions that account for the formation of acrylate midchain radicals by intramolecular transfer and their subsequent propagation, termination, and transfer events have been derived for polymerization rate, average chain-length, and chain-length distribution under stationary conditions. The nonidealities observed in previous kinetic studies are captured in a single lumped rate coefficient, θ, that controls the apparent order of rate on monomer concentration. Applied to rate data from the literature, the treatment yields consistent estimates for θ and k p / k t 0.5 for butyl acrylate polymerization at 50 °C. Combining these ratios with chain-end propagation values determined by pulsed-laser polymerization, intramolecular transfer rate coefficients estimated from 13 C NMR data, and/or radical concentrations measured by ESR provides a new means to estimate the individual rate coefficients for acrylate polymerization systems. It is also shown that estimates for butyl acrylate transfer to monomer rate coefficients obtained from chain-length distributions are valid even in the presence of acrylate backbiting events.
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How this classification was reachedexpand
Full frame machine prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. The Gemma side is a direct model label for every work in the frame, read from the title-only record. The Codex side is a classifier learned from the 10,348 direct Codex labels and calibrated to design-weighted sample rates; fields without enough sample support carry no Codex call. Candidate is the union of the two sides; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels.
Distilled classifier scores by category (both heads)
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.001 | 0.002 |
| Meta-epidemiology (narrow) | 0.001 | 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 | 0.001 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.001 |
| Insufficient payload (model declined to judge) | 0.001 | 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 source (direct Gemma or distilled Codex), 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".