Counterion Effects on Propylene Polymerization Using Two-State <i>a</i><i>nsa</i>-Metallocene Complexes
Bibliographic record
Abstract
Propylene polymerization using unsymmetrical, ansa-metallocene complexes Me(2)Y(Ind)CpMMe(2) (Y = Si, C, M = Zr, Y = C, M = Hf) and the co-initiators methyl aluminoxane (PMAO), B(C(6)F(5))(3), and [Ph(3)C][B(C(6)F(5))(4)] was studied at a variety of propylene concentrations. Modeling of the polymer microstructure reveals that the catalysts derived from Me(2)Si(Ind)CpZrMe(2) and each of these co-initiators function under conditions where chain inversion is much faster than propagation (Curtin-Hammett conditions). Surprisingly, the microstructure of the PP formed was essentially unaffected by the nature of the counterion, suggesting similar values for the fundamental parameters inherent to two-state catalysts. The tacticity of PP was sensitive to changes in [C(3)H(6)] in the case of catalysts derived from Me(2)C(Ind)CpHfMe(2) and PMAO, or [Ph(3)C][B(C(6)F(5))(4)], but the average tacticity of the polymer produced at a given [C(3)H(6)] decreased in the order [Ph(3)C][B(C(6)F(5))(4)] > PMAO. With B(C(6)F(5))(3), the polymer formed was more stereoregular, and its microstructure was invariant to changes in monomer concentration. The PP pentad distributions in this case could be modeled by assuming that all three catalyst/cocatalyst combinations function with different values for the relative rates of insertion to inversion (Delta) but otherwise feature essentially invariant, intrinsic stereoselectivity for monomer insertion (alpha, beta), while the relative reactivity/stability (g/K) of the isomeric ion-pairs present seems to be only modestly affected, if at all. Similar conclusions can also be made about the published propylene polymerization behavior of the C(s)-symmetric Me(2)C(Flu)CpZrMe(2) complex with different counterions. For every counterion investigated, the principle difference appears to be the operating regime (Delta) rather than intrinsic differences in insertion stereoselectivity (alpha). Surprisingly, the ordering of the various counterions with respect to Delta does not agree with commonly accepted ideas about their coordinating ability. In particular, catalysts when activated with B(C(6)F(5))(3) appear to function at low values of Delta as compared to those featuring B(C(6)F(5))(4) (less coordinating) and FAl[(o-C(6)F(5))C(6)F(4)](3) (more coordinating) or PMAO (more coordinating) counterions where the ordering in Delta is MeB(C(6)F(5))(3) < B(C(6)F(5))(4) < FAl[(o-C(6)F(5))C(6)F(4)](3) approximately PMAO. Possible reasons for this behavior are discussed.
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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) | 0.001 | 0.001 |
| 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".