Versatile Initiators for Macromonomer Syntheses of Acrylates, Methacrylates, and Styrene by Atom Transfer Radical Polymerization
Bibliographic record
Abstract
Novel vinyl-containing initiators 2-vinyloxyethyl 2-bromoisobutyrate (VBIB) and 3-vinyloxylpropyl trichloroacetamide (VTCA) were synthesized for the preparation of vinyl-terminated macromonomers of different monomers by atom transfer radical polymerization (ATRP). Catalyzed by CuBr/hexamethyltriethylenetetramine (CuBr/HMTETA), the ATRP processes initiated by VBIB (for MMA, DMAEMA, and styrene) and VTCA (for MMA and DMAEMA) followed a first-order kinetics with respect to the monomer concentration. The molecular weights of the resulting polymers were very close to their calculated values and increased with the conversion. The GPC traces showed that the vinyl moiety in the initiators did not participate the polymerization at conversions below 80% during the ATRP processes of DMAEMA in bulk and those of MMA and styrene in γ-butyrolactone (γBL). VBIB also initiated methyl acrylate (MA) and butyl acrylate (BA) with first-order kinetics in the early stage of the polymerization; however, the process deviated from the first-order kinetics at high conversions due to reactions of the vinyl moieties. By terminating the ATRP of MA and BA at the early stage, the corresponding macromonomers were also obtained. 1 H NMR confirmed that all polymer chains contained vinyl terminal groups derived from initiators.
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How this classification was reachedexpand
Full frame machine prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. The Gemma side is a direct model label for every work in the frame, read from the title-only record. The Codex side is a classifier learned from the 10,348 direct Codex labels and calibrated to design-weighted sample rates; fields without enough sample support carry no Codex call. Candidate is the union of the two sides; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels.
Distilled classifier scores by category (both heads)
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.000 | 0.000 |
| Meta-epidemiology (narrow) | 0.001 | 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 | 0.001 |
| Insufficient payload (model declined to judge) | 0.001 | 0.001 |
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 source (direct Gemma or distilled Codex), 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".