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Copolymerization of carbon dioxide and butadiene via a lactone intermediate


Although carbon dioxide has attracted broad interest as a renewable carbon feedstock, its use as a monomer in copolymerization with olefins has long been an elusive endeavour. A major obstacle for this process is that the propagation step involving carbon dioxide is endothermic; typically, attempted reactions between carbon dioxide and an olefin preferentially yield olefin homopolymerization. Here we report a strategy to circumvent the thermodynamic and kinetic barriers for copolymerizations of carbon dioxide and olefins by using a metastable lactone intermediate, 3-ethylidene-6-vinyltetrahydro-2H-pyran-2-one, which is formed by the palladium-catalysed condensation of carbon dioxide and 1,3-butadiene. Subsequent free-radical polymerization of the lactone intermediate afforded polymers of high molecular weight with a carbon dioxide content of 33 mol% (29 wt%). Furthermore, the protocol was applied successfully to a one-pot copolymerization of carbon dioxide and 1,3-butadiene, and one-pot terpolymerizations of carbon dioxide, butadiene and another 1,3-diene. This copolymerization technique provides access to a new class of polymeric materials made from carbon dioxide.

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Figure 1: Tentative energy diagram of carbon dioxide/ethylene copolymerization and carbon dioxide/butadiene copolymerization.
Figure 2: The concept of this study: copolymerization of carbon dioxide and 1,3-butadiene via a lactone intermediate, 3-ethylidene-6-vinyltetrahydro-2H-pyran-2-one (1).
Figure 3: 13C NMR spectra and the assignments for poly-1.
Figure 4: Proposed reaction pathways to form repeating units of α, β and γ.


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This work was supported by the Funding Program for Next Generation World-Leading Researchers, Green Innovation and the Global COE Program ‘Chemistry Innovation through Cooperation of Science and Engineering’ from the Ministry of Education, Culture, Sports, Science and Technology (MEXT)/Japan Society for the Promotion of Science, Japan, and a Grant-in-Aid for Innovative Areas ‘Molecular Activation Directed toward Straightforward Synthesis’ from MEXT, Japan. The theoretical calculations were performed using computational resources provided by the Research Center for Computational Science, National Institutes of Natural Sciences, Okazaki, Japan. We are grateful to H. Sugimoto, H. Goto and S. Honda (Tokyo University of Science) for right-angle laser-light scattering (RALLS) analyses for the molecular weights of polymers, and to B. P. Carrow (Princeton University) for careful proofreading.

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All authors designed the studies, discussed the results and wrote the paper. R.N. performed all the experimental and computational work.

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Correspondence to Kyoko Nozaki.

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Nakano, R., Ito, S. & Nozaki, K. Copolymerization of carbon dioxide and butadiene via a lactone intermediate. Nature Chem 6, 325–331 (2014).

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