Kinetic Behavior of Atom Transfer Radical Polymerization of Dimethacrylates
Bibliographic record
Abstract
Abstract Summary: The reaction behavior and kinetics of the atom transfer radical polymerization (ATRP) of poly(ethylene glycol) dimethacrylates (PEGDMA) were studied with respect to polymerization rate, vinyl conversion and the development of a crosslinked network. The polymerization rates were much slower than the corresponding conventional free radical polymerizations with the ATRP systems exhibiting milder autoacceleration. The linear relationship of the semi‐logarithmic kinetic plot of ln([M]0/[M]) vs. time did not provide good evidence for any living nature of the system because of the combined effects of diffusion controlled radical deactivation and diffusion controlled monomer propagation. The influence of the spacer length (CH2CH2O)x between the vinyl moieties of the dimethacrylates on the polymerization kinetics was examined. The polymerization rate and final vinyl conversion increased as value of x decreased from 14 to 9 to 4. These increases in rate and conversion were caused by a more rigid network structure with shorter spacer lengths, and thus more restricted diffusion of the catalyst/ligand complexes that impeded the radical deactivation. The effect of temperature on the polymerization rate and final vinyl conversion were also investigated. Apparent rate constants versus vinyl conversions for the ATRP of PEGDMA with the different spacer lengths at 100 °C. magnified image Apparent rate constants versus vinyl conversions for the ATRP of PEGDMA with the different spacer lengths at 100 °C.
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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 | 0.001 |
| 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 | 0.001 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.001 |
| Insufficient payload (model declined to judge) | 0.002 | 0.001 |
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".