Mechanically Mediated Atom Transfer Radical Polymerization: Exploring Its Potential at High Conversions
Bibliographic record
Abstract
A well-controlled atom transfer radicfal polymerization of methyl acrylate (MA) was realized by mechanical mediation (mechanoATRP) in dimethyl sulfoxide (DMSO, 50% v/v). High conversions of typically over 90% were achieved. The resulting polymers had well-controlled molecular weights and very low dispersities ( Đ = 1.03–1.09). No polymerization of MA was observed under various conditions from bulk up to 33.3% DMSO (v/v) solution. It was found that adding an equivalent volume of DMSO with respect to MA activated the polymerization. This finding suggested that DMSO played a crucial role in the mechanoATRP of MA. DMSO not only improved the solubility of CuBr 2 complex but also facilitated an electron transfer process in the mechanical reduction of CuBr 2 . For a proof of the concept, a DMSO analogue acrylate, 2-(methylsulfinyl)ethyl acrylate (MSEA), was also polymerized. In addition, the high chain-end functionality of the polymers collected at ∼95% conversion was confirmed by 1 H NMR, MALDI-ToF-MS, and in-situ chain extension experiments. The extended chain polymers were characterized and found to have predicted molecular weights and low dispersities ( Đ = 1.06). Chain extension in the presence of residual oxygen still yielded a well-controlled molecular weight but a slightly higher dispersity of 1.11. This work provided an in-depth insight into the mechanoATRP and demonstrated its good potential in producing well-defined polymers at high conversions.
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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 | 0.001 |
| 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".