A Semi‐Batch Process for Nitroxide Mediated Radical Polymerization
Bibliographic record
Abstract
Abstract Summary: A semi‐batch process using nitroxide mediated polymerization, was explored for the design of low molecular weight solvent‐borne coatings, typical of those used in the automotive industry. While living radical polymerization (LRP) offers many advantages in the control of polymer chain microstructure that may confer important physical and chemical property benefits to coatings, adapting LRP to a semi‐batch process poses significant challenges in the design and operation of the process. Using styrene monomer, various two‐component initiating systems (free radical initiator, 4‐hydroxy‐TEMPO) were studied to understand the effects of different initiators on the course of polymerization. In addition, an alkoxyamine was synthesized and used as the initiating source. The initiators Luperox 7M75 and Luperox 231 give higher polymerization rates and reasonable control over polymerization, while benzoyl peroxide (BPO), Vazo 67, and the alkoxyamine are less effective. The number of polymer chains in the final product is always less than the theoretical value, reflecting poor initiation efficiency, probably resulting from undesirable termination reactions that become important due to the nature of the semi‐batch process. Adding camphorsulfonic acid (CSA) or charging initiator concurrently with monomer during semi‐batch feed, can increase the polymerization rate while maintaining the living character of the polymerization. The copolymerization of styrene and butyl acrylate is also shown to exhibit living character. Schematic representation of the exchange reaction to produce N ‐TEMPO capped polymer chains. magnified image Schematic representation of the exchange reaction to produce N ‐TEMPO capped polymer chains.
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How this classification was reachedexpand
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 | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| 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 itClassification
machine, unvalidatedMachine predicted; a candidate call from one teacher head, 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".