Abstract
Controlling the monomer sequence of synthetic polymers is a grand challenge in polymer science. Conventional sequence control has been achieved in dispersed polymers by exploiting the kinetic tendencies of monomers and their order of addition. While the sequence of blocks in multiblock copolymers can be readily tuned using sequential addition of monomers (SAM), control over the sequence distribution is eroded as the targeted block size approaches a single monomer unit (i.e., Xn ∼ 1) due to the stochastic nature of chain-growth reactions. Thus, unique monomers are needed to ensure precise single additions. Herein, we investigate common classes of cyclic olefin monomers for ring-opening metathesis polymerization (ROMP) to identify monomers for single unit addition during sequential monomer addition synthesis. Through careful analysis of polymerization kinetics, we find that easily synthesized oxanorbornene imide monomers are suitable for single-addition reactions. With the identified monomers, we demonstrate the synthesis of multiblock copolymers containing up to three precise functionalization sites and singly cross-linked four-armed star copolymers. We envision that expanded kinetic analyses of monomer reactivities in ROMP reactions will enable novel polymer synthesis capabilities such as the autonomous synthesis of sequence-defined polymers or one-shot multiblock copolymer syntheses.
| Original language | English |
|---|---|
| Pages (from-to) | 7931-7938 |
| Number of pages | 8 |
| Journal | Macromolecules |
| Volume | 56 |
| Issue number | 19 |
| DOIs | |
| State | Published - Oct 10 2023 |
Funding
This research was sponsored by the Laboratory Directed Research and Development Program of Oak Ridge National Laboratory managed by UT-Battelle LLC for the U.S. DOE. MALD-TOF MS was conducted as part of a user project at the Center for Nanophase Materials Sciences (CNMS), which is a US Department of Energy, Office of Science User Facility at Oak Ridge National Laboratory. H.Z. is currently supported by the Center for Structural Molecular Biology, sponsored by the Office of Biological and Environmental Research. The authors thank Tomonori Saito for their review of the manuscript. This manuscript has been authored by UT-Battelle LLC under contract DE-AC05-00OR22725 with the U.S. Department of Energy (DOE). The U.S. government retains, and the publisher, by accepting the article for publication, acknowledges that the U.S. government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for U.S. government purposes. DOE will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan ( http://energy.gov/downloads/doe-public-access-plan ). The authors thank Tomonori Saito for their review of the manuscript. This manuscript has been authored by UT-Battelle LLC under contract DE-AC05-00OR22725 with the U.S. Department of Energy (DOE). The U.S. government retains, and the publisher, by accepting the article for publication, acknowledges that the U.S. government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for U.S. government purposes. DOE will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan (http://energy.gov/downloads/doe-public-access-plan).
| Funders | Funder number |
|---|---|
| Center for Structural Molecular Biology | |
| DOE Public Access Plan | |
| U.S. Government | |
| U.S. Department of Energy | |
| Biological and Environmental Research | |
| Oak Ridge National Laboratory | |
| UT-Battelle | DE-AC05-00OR22725 |