Backbone-Photodegradable Polymers by Incorporating Acylsilane Monomers via Ring-Opening Metathesis Polymerization

Huang, Banruo; Wei, Mufeng; Vargo, Emma; Qian, Yiwen; Xu, Ting; Toste, F. Dean

doi:10.1021/jacs.1c06836

Backbone-Photodegradable Polymers by Incorporating Acylsilane Monomers via Ring-Opening Metathesis Polymerization

Journal Article · Fri Oct 22 00:00:00 EDT 2021 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.1c06836· OSTI ID:1963429

Huang, Banruo ^[1]; Wei, Mufeng ^[2]; Vargo, Emma ^[2]; Qian, Yiwen ^[2]; ^[3]; ^[1]

Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); University of California, Berkeley, CA (United States)
University of California, Berkeley, CA (United States)
University of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Materials Sciences Division

Materials capable of degradation upon exposure to light hold promise in a diverse range of applications including biomedical devices and smart coatings. Despite the rapid access to macromolecules with diverse compositions and architectures enabled by ring-opening metathesis polymerization (ROMP), a general strategy to introduce facile photodegradability into these polymers is lacking. Here, we report copolymers synthesized via ROMP that can be degraded by cleaving the backbone in both solution and solid states under irradiation with a 52 W, 390 nm Kessil LED to generate heterotelechelic low-molecular-weight fragments. To the best of our knowledge, this work represents the first instance of the incorporation of acylsilanes into a polymer backbone. Mechanistic investigation of the degradation process supports the intermediacy of an α-siloxy carbene, formed via a 1,2-photo Brook rearrangement, which undergoes insertion into water followed by cleavage of the resulting hemiacetal.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: National Institutes of Health (NIH); USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1963429

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 43 Vol. 143; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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