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We report the mild functionalization of polystyrene with primary amines and other nitrogen groups through sp3 C–H imination. This process significantly increases hydrophilicity without deterioration of molecular weight or thermal properties, and provides a handle for further covalent modification. This work will enable the upcycling and diversification of commodity polyolefins.
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This content will become publicly available on May 21, 2026
Blocky Selective Postpolymerization C–H Functionalization of Polyolefins
Abstract C–H functionalization of commodity polyolefins affords functional materials derived from a high‐volume, low‐cost resource. However, current postpolymerization modification strategies result in randomly distributed functionalization along the length of the polymer backbone, which has a negative impact on the crystallinity of the resultant polymers, and thus the thermomechanical properties. Here, we demonstrate an amidyl radical mediated C–H functionalization of polyolefins to access blocky microstructures, which exhibit a higher crystalline fraction, larger crystallite size, and improved mechanical properties compared to their randomly functionalized analogues. Taking inspiration from the site‐selective C–H functionalization of small molecules, we leverage the steric protection provided by crystallites and target polymer functionalization to amorphous domains in a semicrystalline polyolefin gel. The beneficial outcomes of blocky functionalization are independent of the identity of the pendant functional group that is installed through functionalization. The decoupling of functional group incorporation and crystallinity highlights the promise in accessing nonrandom microstructures through selective functionalization to circumvent traditional tradeoffs in postpolymerization modification, with potential impact in advanced materials and upcycling plastic waste.
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- Award ID(s):
- 2304548
- PAR ID:
- 10649745
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Angewandte Chemie International Edition
- Volume:
- 64
- Issue:
- 30
- ISSN:
- 1433-7851
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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