Modeling of Nitroxide‐Mediated Semibatch Radical Polymerization
Bibliographic record
Abstract
Abstract A mechanistic model is developed for high‐temperature (138 °C) styrene semibatch thermally and conventionally initiated FRP, as well as NMP with a two‐component initiating system (tert‐butyl peroxyacetate, 4‐hydroxy‐TEMPO). The model, using kinetic coefficients from literature, provides a good representation of the FRP experimental results. Implementation of a gel effect correlation to represent the change in the diffusion‐controlled termination rate coefficient with conversion improves the fit to the thermally initiated system, but is not required to represent the production of low molecular weight material ($\overline M _{\rm n} < 10\,000$ Dalton) by conventionally initiated FRP or NMP. The low initiator efficiency found in NMP is well explained by a reaction network involving combination of free nitroxide with methyl radicals formed from initiator decomposition. magnified image
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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 | 0.000 | 0.000 |
| 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 | 0.000 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.001 | 0.000 |
| Insufficient payload (model declined to judge) | 0.003 | 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".