Ethylene Glycol Dicyclopentenyl (Meth)Acrylate Homo and Block Copolymers via Nitroxide Mediated Polymerization
Bibliographic record
Abstract
Nitroxide-mediated polymerization (NMP), (homo and block copolymerization with styrene (S) and butyl methacrylate/S) of ethylene glycol dicyclopentenyl ether (meth)acrylates (EGDEA and EGDEMA) was studied using BlocBuilder alkoxyamines. EGDEA homopolymerization was not well-controlled, independent of temperature (90–120 °C), or additional free nitroxide (0–10 mol%) used. Number average molecular weights (Mn) achieved for poly(EGDEA) were 4.0–9.5 kg mol−1 and were accompanied by high dispersity (Ð = Mw/Mn = 1.62–2.09). Re-initiation and chain extension of the poly(EGDEA) chains with styrene (S) indicated some block copolymer formation, but a high fraction of chains were terminated irreversibly. EGDEA-stat-S statistical copolymerizations with a low mol fraction S in initial feed, fS,0 = 0.05, were slightly better controlled compared to poly(EGDEA) homopolymerizations (Ð was reduced to 1.44 compared to 1.62 at similar conditions). EGDEMA, in contrast, was successfully polymerized using a small fraction of S (fS,0 ~ 10 mol%) to high conversion (72%) to form well-defined EGDEMA-rich random copolymer (molar composition = FEGDEMA = 0.87) of Mn = 14.3 kg mol−1 and Ð = 1.38. EGDEMA-rich compositions were also polymerized with the unimolecular succinimidyl ester form of BlocBuilder initiator, NHS-BlocBuilder with similar results, although Ðs were higher ~1.6. Chain extensions resulted in monomodal shifts to higher molecular weights, indicating good chain end fidelity.
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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".