Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 138, Issue 43, Pages 14326-14337Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.6b07974
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Funding
- US National Science Foundation [NSF-1300267]
- King Abdullah University of Science and Technology (KAUST)
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1300267] Funding Source: National Science Foundation
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alpha-Methylene-gamma-butyrolactone (MBL), a naturally occurring and biomass-sourced bifunctional monomer, contains both a highly reactive exocyclic C=C bond and a highly stable five-membered gamma-butyrolactone ring. Thus, all previous work led to exclusive vinyl-addition polymerization (VAP) product P(MBL)(VAP). Now, this work reverses this conventional chemoselectivity to enable the first ring-opening polymerization (ROP) of MBL, thereby producing exclusively unsaturated polyester, P(MBL)(ROP) with M-n up to 21.0 kg/mol. This elusive goal was achieved through uncovering the thermodynamic, catalytic, and processing conditions. A third reaction pathway has also been discovered, which is a crossover propagation between VAP and ROP processes; thus affording cross-linked polymer P(MBL)(CLP). The formation of the three types of polymers, P(MBL)(VAP); P(MBL)(CLP), and P(MBL)(ROP), can be readily controlled by adjusting the catalyst (La)/initiator (ROH) ratio, which is determined by the unique chemoselectivity of the La-X (X = OR, NR2, R) group. The resulting P(MBL)(ROP) is degradable and can be readily postfunctionalized into cross-linked or thiolated materials but, more remarkably, can also be fully recycled back to its monomer thermochernically. Computational studies provided the theoretical basis for, and a mechanistic understanding of; the three different polymerization processes and the origin of the chemoselectivity.
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