Hydrolytically-degradable homo- and copolymers of a strained exocyclic hemiacetal ester

Angelika E. Neitzel, Leonel Barreda, Jacob T. Trotta, Grant W. Fahnhorst, Thomas J. Haversang, Thomas R. Hoye, Brett P. Fors, Marc A. Hillmyer

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22 Scopus citations


We report the cationic ring-opening homo- and copolymerization of the 7-membered exocyclic hemiacetal ester 7-methoxyoxepan-2-one (MOPO) to afford poly(7-methoxyoxepan-2-one) [poly(MOPO)] and its copolymers with isobutyl vinyl ether (IBVE) that achieve essentially quantitative conversions of MOPO. The amorphous homopolymer is characterized by a low glass transition temperature of Tg = -37 °C and is readily degraded under both acidic and basic conditions at the labile acylacetal linkages. With triflic acid as the cationic initiator the homopolymerization proceeds by an uncontrolled active chain end mechanism to reproducibly yield poly(MOPO) of Mn ∼ 20 kg mol-1. The monomer was also polymerized by a photoinitiated process using a dithiocarbamate or trithiocarbonate chain transfer agent and the photocatalyst 2,4,6-tris(p-4-methoxyphenyl)pyrylium tetrafluoroborate. Lower molar mass polymers were recovered at high initial concentrations of dithiocarbamate as compared to no chain transfer agent, indicating some ability to control polymer molar mass. Photoinitiated copolymerization of MOPO and IBVE afforded a tapered copolymer with MOPO-MOPO, IBVE-MOPO, and IBVE-IBVE linkages that degraded into low molar mass poly(IBVE) fragments in hydrochloric acid through hydrolysis of the acylacetal linkages resulting from ring-opened MOPO units in the backbone.

Original languageEnglish (US)
Pages (from-to)4573-4583
Number of pages11
JournalPolymer Chemistry
Issue number33
StatePublished - Sep 7 2019

Bibliographical note

Funding Information:
This work was supported by the Center for Sustainable Polymers at the University of Minnesota, a National Science Foundation supported Center for Chemical Innovation (CHE-1413862). This work made use of the Cornell Center for Materials Research Shared Facilities that are supported through the NSF MRSEC program (DMR-1120296). B. P. F. thanks 3M for a Non-Tenured Faculty Award. This work made use of the NMR Facility at Cornell University that is supported, in part, by the NSF under the award number CHE-1531632.

Publisher Copyright:
© The Royal Society of Chemistry 2019.


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