Poly(<i>tert</i>-butyl methacrylate/styrene) Macroinitiators as Precursors for Organo- and Water-Soluble Functional Copolymers Using Nitroxide-Mediated Controlled Radical Polymerization
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Bibliographic record
Abstract
Styrene/ tert -butyl methacrylate (S/TBMA) mixtures, with initial TBMA molar feed compositions f TBMA,0 = 0.1−0.92, were copolymerized by nitroxide-mediated polymerization (NMP) in bulk at 90 °C using 10 mol % { tert -butyl[1-(diethoxyphosphoryl)-2,2-dimethylpropyl]amino} nitroxide (SG1) relative to 2-({ tert -butyl[1-(diethoxyphosphoryl)-2,2-dimethylpropyl]amino}oxy)-2-methylpropionic acid unimolecular initiator (BlocBuilder) to form SG1-terminated macroinitiators. k p K values ( k p = propagation rate constant, K = equilibrium constant) for S/TBMA increased significantly as f TBMA,0 increased, with k p K = (7.4 ± 0.03) × 10 −7 to (5.4 ± 0.9) × 10 −5 s −1 . Copolymer reactivity ratios were r TBMA = 0.13−0.27 and r S = 0.43−0.59 using Fineman−Ross, Kelen−Tüdos, and nonlinear least-squares fitting to the Mayo−Lewis terminal model. All S/TBMA copolymers (number-average molecular weight M̅ n = 4.5−15.6 kg mol −1 ) exhibited low polydispersities ( M̅ w / M̅ n ≤ 1.30), and M̅ n exhibited linear behavior with conversion up to 25−40% and monomodal molecular weight distributions. TBMA-rich copolymer ( M̅ n = 14.2 kg mol −1 and M̅ w / M̅ n = 1.30) was shown to have a high degree of “livingness” based upon 31 P NMR measurements for the SG1 end group (≈75%), and successful reinitiations of fresh batches of styrene, tert -butylstyrene, N -isopropylacrylamide, and a ternary mixture of glycidyl methacrylate/methyl methacrylate/styrene (all products were monomodal with M̅ n = 17.8−81.0 kg mol −1 and M̅ w / M̅ n = 1.33−1.59).
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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) | 0.001 | 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 | 0.000 |
| 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 it