Mechanism of Propylene Oxide Polymerization Promoted by N-Heterocyclic Olefins
KAUST DepartmentChemical Science Program
KAUST Catalysis Center (KCC)
Physical Science and Engineering (PSE) Division
Online Publication Date2017-01-25
Print Publication Date2017-02-09
Permanent link to this recordhttp://hdl.handle.net/10754/623866
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AbstractWe report a mechanistic DFT investigation of the organopolymerization of propylene oxide (PO) promoted by N-heterocyclic olefins (NHOs) in combination with benzylic alcohol (BnOH). Calculations support the experimentally based hypothesis of two competing pathways, namely, the anionic and zwitterionic pathways. The former is based on an acid–base cooperativity between BnOH and the NHO, promoting ring opening of PO by BnO–. The latter occurs through the formation of a zwitterionic adduct by nucleophilic attack of the exocyclic carbon atom of the NHO on the PO, with the concerted ring opening of PO. The two initiating species cannot interconvert, and chain elongation can proceed from both initiation adducts. Potential energy surfaces were computed for a set of NHOs to clarify the effects of the steric and electronic properties of the NHO on the system reactivity. The results achieved represent useful insight toward the synthesis of PPO with better properties with respect to the polymer obtained with the experimental tested systems because the computationally proposed NHO system is the only one that favors the mechanism leading to higher molecular weight.
CitationAl Ghamdi M, Cavallo L, Falivene L (2017) Mechanism of Propylene Oxide Polymerization Promoted by N-Heterocyclic Olefins. The Journal of Physical Chemistry C 121: 2730–2737. Available: http://dx.doi.org/10.1021/acs.jpcc.6b10977.
SponsorsThis work was supported by funding from King Abdullah University of Science and Technology (KAUST).
PublisherAmerican Chemical Society (ACS)