Reversible Redox Crosslinking of Thiopropylsilicones
Why this work is in the frame
A frame that forgets how it found something cannot be audited. These are the routes that admitted this work.
Bibliographic record
Abstract
Abstract Most silicone elastomers are thermosets. As a response to the new paradigm of polymer recyclability, the development of silicone elastomers that can be reversibly and repeatedly cured and uncrosslinked using redox conditions is reported. Thiopropyl‐modified silicones are oxidized to elastomers with disulfide crosslinks using the organosoluble oxidant PhI(OAc) 2 . As with any elastomer, mechanical properties can be tuned by varying crosslink density. Thermal stabilities in air show that the products are comparable to traditional silicone thermosets, with degradation only starting over 300 °C. Uncrosslinking back to the same thiopropyl‐modified silicones involves reductive S–S bridge cleavage using a Piers–Rubinsztajn reaction with hydrosilanes catalyzed by B(C 6 F 5 ) 3 ; HSiMe 2 OSiMe 3 is identified as a convenient reducing agent. The initially formed silicone‐(CH 2 ) 3 S‐SiMe 2 OSiMe 3 products need deprotection with water in isopropanol/water to completely regenerate the thiopropylsilicones. This oxidation/reduction crosslinking/uncrosslinking cycle is practiced thrice, with a yield of 89% per cycle, with essentially no change in the Young's moduli of the elastomers, or 1 H NMR spectra of the uncrosslinked fluids after reduction. Further oxidation of disulfide groups on the elastomer surface permanently and significantly improved water wettability.
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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 | 0.000 |
| Open science | 0.001 | 0.001 |
| 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