The Quest for Converting Biorenewable Bifunctional α-Methylene-γ-butyrolactone into Degradable and Recyclable Polyester: Controlling Vinyl-Addition/Ring-Opening/Cross-Linking Pathways
Type
ArticleKAUST Department
Chemical Science ProgramKAUST Catalysis Center (KCC)
Physical Science and Engineering (PSE) Division
Date
2016-10-19Online Publication Date
2016-10-19Print Publication Date
2016-11-02Permanent link to this record
http://hdl.handle.net/10754/622483
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α-Methylene-γ-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 γ-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 Mn 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 thermochemically. Computational studies provided the theoretical basis for, and a mechanistic understanding of, the three different polymerization processes and the origin of the chemoselectivity.Citation
Tang X, Hong M, Falivene L, Caporaso L, Cavallo L, et al. (2016) The Quest for Converting Biorenewable Bifunctional α-Methylene-γ-butyrolactone into Degradable and Recyclable Polyester: Controlling Vinyl-Addition/Ring-Opening/Cross-Linking Pathways. Journal of the American Chemical Society 138: 14326–14337. Available: http://dx.doi.org/10.1021/jacs.6b07974.Sponsors
This work was supported by the US National Science Foundation (NSF-1300267) for the study carried out at Colorado State University and by the funding from King Abdullah University of Science and Technology (KAUST) for the study performed at KAUST.Publisher
American Chemical Society (ACS)Additional Links
http://dx.doi.org/10.1021/jacs.6b07974ae974a485f413a2113503eed53cd6c53
10.1021/jacs.6b07974