Effect of Reversible Addition−Fragmentation Transfer (RAFT) Reactions on (Mini)emulsion Polymerization Kinetics and Estimate of RAFT Equilibrium Constant
Bibliographic record
Abstract
The Smith−Ewart equation has been modified to describe the kinetics of reversible addition−fragmentation transfer (RAFT) (mini)emulsion polymerization. Two types of radicals (propagating and intermediate) are taken into account. The influence of RAFT reactions on the (mini)emulsion polymerization kinetics is investigated using the modified Smith−Ewart theory. In a simplified zero−one case, the average number of propagating radicals per particle can be described by n̄ RAFT -1 = n̄ blank -1 + 2 K [RAFT] 0, where K is the RAFT equilibrium coefficient. It is found that the rate retardation is an intrinsic kinetic property of RAFT (mini)emulsion polymerization. The miniemulsion polymerization of styrene is also carried out with styrene oligomers of 1-phenylethylphenyl dithioacetate (PS−PEPDTA) and 2-cyranoprop-2-yl dithiobenzoate (PS−CPDB) as the RAFT agents. The experimental n̄ data are well described by the theory. The K values are estimated to be 314 L/mol for PS−CPDB and 22 L/mol for PS−PEPDTA. The fragmentation rate coefficients appear to be on the order of magnitude of 10 4 −10 5 s -1 .
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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 | 0.001 | 0.003 |
| Meta-epidemiology (narrow) | 0.001 | 0.000 |
| Meta-epidemiology (broad) | 0.001 | 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) | 0.001 | 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".