An investigation of solvolytic reactions and exploration of 2-(dimethylamino)ethyl methacrylate/methyl acrylate free radical copolymerization kinetics
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Bibliographic record
Abstract
In-situ NMR is used to determine individual monomer conversion profiles and thus comonomer composition drifts vs. overall monomer conversion for the radical copolymerization of 2-(dimethylamino)ethyl methacrylate (DMAEMA) with methyl acrylate (MA) in dimethyl sulfoxide, toluene, ethanol (EtOH), and an ethanol/water mixture containing 75 wt% EtOH. A faster incorporation of DMAEMA was observed in the copolymer compared to MA in all systems, with the data used to estimate reactivity ratios. In addition, the copolymer composition-averaged propagation rate coefficients ( ) were obtained using the pulsed laser polymerization – size exclusion chromatography (PLP-SEC) technique for the system in bulk and in EtOH. While the terminal model provided a good representation of copolymer composition, the penultimate model was needed to represent DMAEMA-MA behavior. When DMAEMA and MA were present in water-rich EtOH/water mixtures, the solvolysis of DMAEMA formed methacrylic acid (MAA) and ethyl methacrylate (EMA), potentially leading to formation of a tetrapolymer. While the kinetics of this more complex system was not studied, it was demonstrated that the influence of monomer solvolysis can be important for DMAEMA copolymerization in aqueous solvent mixtures.
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Full frame distilled prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. Learned from the 10,348 direct Codex labels and 10,348 direct Gemma labels. Candidate is the union of thresholded teacher heads; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels or direct frontier model labels.
Codex and Gemma teacher scores by category
| 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 | 0.001 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.000 | 0.000 |
Machine scores (provisional)
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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 it