Mechanisms for anionic butadiene polymerization with alkyl lithium species
Bibliographic record
Abstract
Anionic butadiene polymerization by means of [Li-polybutadienyl] x species (x = 1–6, 8) without polar agents was investigated by means of density functional theory (DFT) under conditions relevant to industrial application, namely in a low-dielectric hydrocarbon solvent and at room temperature. The calculations indicate that the dimeric and tetrameric catalyst species together account for the bulk of Li-polybutadienyl species in the polymerization mixture under typical conditions. It is likely that each type of oligomer produces its own “fingerprint” signature polymer microstructure, as there is a systematic variation in the amounts of 1,2- and 1,4-insertions as well as in the preference of cis- and trans-butadiene. According to the calculations, higher aggregated Li species tend to produce more 1,2-insertions and prefer trans- over cis-butadiene insertion, while the dimer prefers trans-butadiene and 1,4-insertions. The dimer closely reproduces the experimentally observed polybutadiene microstructure (5%–10% 1,2-insertion, approximately equal ratios of cis and trans units with a slight predominance of trans). The monomeric catalyst species shows a clear preference for insertion of cis-butadiene over trans-butadiene. Thus, the monomer species is predicted to be present in the polymerization mixture in very small concentrations under normal conditions and the overall polymerization is predicted to be mainly carried out by the dimeric catalyst species.
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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) | 0.002 | 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".