One-Step Poly(styrene-<i>alt</i>-maleic anhydride)-<i>block</i>-poly(styrene) Copolymers with Highly Alternating Styrene/Maleic Anhydride Sequences Are Possible by Nitroxide-Mediated Polymerization
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Bibliographic record
Abstract
Styrene/maleic anhydride (S/MA) copolymerizations at initial molar MA feed concentrations f MA,0 = 0.10−0.55 were done at 80−110 °C in 50 wt % 1,4-dioxane using 5 mol % { tert -butyl-[1-(diethoxyphosphoryl)-2,2-dimethylpropyl]amino}oxidanyl (SG1) relative to -2-({ tert -butyl-[1-(diethoxyphosphoryl)-2,2-(dimethylpropyl)amino}oxy)-2-methylpropionic acid (BlocBuilder). As f MA,0 increased, the apparent rate constants increased dramatically. Copolymerizations performed with nearly equimolar feeds f MA,0 = 0.45−0.55 at 110 °C had apparent rate constants ∼20 times that of styrene at the same temperature. S/MA copolymerizations performed at 110 °C with practically equimolar feeds resulted in nearly alternating S/MA/S structures while those performed with f MA,0 = 0.1−0.4 possessed little to no S/MA/S alternating structures as indicated by 13 C NMR spectroscopy. However, NMP of S/MA done at 90 °C with a styrene-rich feed composition ( f MA,0 = 0.2) resulted in a poly(S- alt -MA)- block -poly(S) diblock in a single step. 13 C NMR revealed two significant populations of triads corresponding to S/MA/S alternating sequences and to S/S/S homopoly(styrene) sequences. BlocBuilder enabled the polymerization of these one-step block copolymers with a strictly alternating S/MA first block by NMP, thus permitting NMP to join reversible addition−fragmentation transfer polymerization as another controlled radical polymerization method to attain alternating S/MA microstructures.
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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) | 0.001 | 0.001 |
| Meta-epidemiology (broad) | 0.001 | 0.000 |
| Bibliometrics | 0.000 | 0.001 |
| Science and technology studies | 0.001 | 0.000 |
| Scholarly communication | 0.000 | 0.001 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.000 | 0.001 |
| Insufficient payload (model declined to judge) | 0.000 | 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