A PLP‐SEC Investigation of Di(Ethylene Glycol) Methyl Ether Methacrylate Radical Polymerization Propagation Kinetics in Solution
Bibliographic record
Abstract
ABSTRACT The pulsed laser polymerization size exclusion chromatography (PLP‐SEC) technique is used to explore the impact of solvent polarity and composition—from bulk to ethanol (EtOH) /water mixtures to aqueous solutions and dimethyl sulfoxide (DMSO)—on the homopropagation kinetics of di(ethylene glycol) methyl ether methacrylate (DEGMEMA) between 30 and 90°C. The variation in the propagation rate coefficient ( k p ) is attributed to entropic factors, as the activation energy remains approximately constant across all solvent mixtures at a value characteristic of other methacrylates (∼ 21 kJ·mol −1 ). The exception to this generalization is for EtOH, where activation energy is lowered by 3–4 kJ·mol −1 , and the k p for a solution containing 50 wt.% DEGMEMA is lower than the bulk values. DEGMEMA k p values increase as monomer content is decreased from 50 to 10 wt.% in DMSO, EtOH, and EtOH/H 2 O solvents. Most notably, the k p of 5 wt.% DEGMEMA in water (close to its solubility limit) is higher by a factor of 12 compared to the bulk system. These new results for a member of the PEGylated monomer family also provide insight into the increase in chain‐growth rates expected for non‐functional methacrylates between bulk (i.e., particle) and aqueous phases in emulsion polymerization systems.
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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 | 0.001 |
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".