Impact of Quenching Agents on Internal Associations and Structure of Amine-Functionalized Polyolefins
Bibliographic record
Abstract
We investigated the impact of intermolecular interactions on rheomechanical and self-healing properties of poly(cyclooctene) functionalized with an N -methyl aniline derivative, a form of aminated polyethylene (APE). The amine groups in APEs form reversible associations that aggregate due to the polarity difference with the nonpolar backbone. The structure of the aggregates impacts the long-term self-healing and rheological properties. Potassium tri(1-pyrazolyl) borohydride (KTp) was introduced as a bulky quenching agent during synthesis to efficiently hinder the aggregation of APE’s amine groups. KTp’s shielding effect was compared to that of ethyl vinyl ether (EVE), a standard quenching agent for ring-opening metathesis polymerization (ROMP) using rheology, dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC), and nuclear magnetic resonance (NMR). When quenched with either EVE or KTp, APEs retained natural viscoelastic behavior. However, when exposed to high temperature, stronger aggregates formed in the EVE-quenched APE compared to the KTp-quenched APE, causing delayed relaxation dynamics and an increase in T g . KTp enhanced the self-healing recovery of APE after prolonged heat exposure, as a sufficient concentration of active groups remained available at the interface to reassociate after damage. 1 H NMR spectroscopic analysis confirmed these findings, supporting the rheological and self-healing observations. This work shows that macroscopic properties can be controlled by tuning the intermolecular associating states.
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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) | 0.000 | 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) | 0.001 | 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 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".