Efficient Cross-Linking Through C-H Bond Insertion of Unfunctionalized Commodity Materials Using Diazirine-Containing Polymers

Overview

Journal ACS Macro Lett

Publisher American Chemical Society

Specialty Chemistry

Date 2024 Nov 8

PMID 39513545

Authors

Mizhi Xu

Banruo Huang

Haley K Beech

Patrick T Getty

Juan Manuel Uruena

Craig J Hawker

Affiliations

Soon will be listed here.

Abstract

The synthesis and application of multifunctional diazirine-containing polymers for on-demand cross-linking of unfunctionalized commodity polymers through C-H bond insertion is demonstrated. While small-molecule diazirine cross-linkers have seen important applications such as plastic compatibilization and photopatterning, the high degree of functionalization of polymer-based diazirine cross-linkers offers promise for enhanced compatibility based on polymer blending and increased efficiency due to controllable multivalency. As a demonstrative example, unfunctionalized linear poly(-butyl acrylate) (PBA) can be cross-linked using various polymeric cross-linkers with diazirine contents as low as 0.8 wt % in 1 min under photochemical conditions. With gel fractions up to 95%, tunable rheological behavior is observed with increasing cross-linker loadings, consistent with a transition from entangled branched polymers to a cross-linked network. Moreover, the synthetic stability of the diazirine units can be exploited to prepare diazirine-containing polymers based on a variety of different backbones, from vinyl copolymers to poly(dimethylsiloxane) (PDMS), which allows successful photopatterning using a commercial 3D printer.

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