Controlled Radical Grafting: Nitroxyl-Mediated Maleation of Model Hydrocarbons
Bibliographic record
Abstract
An exploration of nitroxyl-mediated polymerization principles for the synthesis of maleated polyethylene (PE) and polybutadiene (PBD) is presented. Thermolysis and disproportionation rates for eight alkoxyamines of relevance to PE and PBD modification are reported, including heptan-3-yl- and hept-5-en-3-yl-based alkoxyamines of 2,2,6,6-tetramethylpiperidinyloxyl, 2,2,5-trimethyl-4-phenyl-3-azahexane-3-oxyl, and 1,1,3,3-tetramethylisoindolin-2-yloxyl. The mediation of heptan-3-yl radical activity was complicated by extensive disproportionation of the alkoxyamines to olefin and the corresponding hydroxylamine. The hept-5-en-3-yl-based alkoxyamines underwent C−O bond homolysis without incurring significant disproportionation, and the addition of maleic anhydride (MAn) to the liberated allylic radical proceeded at a rate comparable to that of nitroxyl trapping. However, rapid disproportionation of the succinyl-based alkoxyamines arrested grafting after a single MAn addition. The consequences for controlled radical grafting of maleic anhydride to polymers are 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) | 0.000 | 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) | 0.001 | 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".