Functional Nitroxyls for Use in Delayed-Onset Polyolefin Cross-Linking
Bibliographic record
Abstract
A new approach to controlling the dynamics and yields of polyolefin radical cross-linking is described, wherein 4-acryloyloxy-2,2,6,6-tetramethylpiperidine- N -oxyl (AOTEMPO) is used to quench macroradicals in the early stages of the process and to subsequently generate a covalent network through the oligomerization of polymer-bound acrylate functionality. Selectivity of alkyl radical trapping by AOTEMPO to give alkoxyamine intermediates in preference to acrylate addition products is discovered using model compound studies and through rheological measurements of linear low density polyethylene cross-linking. The latter demonstrate the ability of AOTEMPO to delay the onset of cross-linking while not compromising the cross-link density of the resulting thermoset. The influences of reagent loadings, peroxide decomposition rates, and the structure of polymerizable functionality are quantified and discussed.
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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 | 0.000 | 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".