High-speed organocatalytic polymerization of a renewable methylene butyrolactone by a phosphazene superbase

Handle URI:
http://hdl.handle.net/10754/563184
Title:
High-speed organocatalytic polymerization of a renewable methylene butyrolactone by a phosphazene superbase
Authors:
Schmitt, Meghan L.; Falivene, Laura; Caporaso, Lucia; Cavallo, Luigi ( 0000-0002-1398-338X ) ; Chen, Eugene You Xian
Abstract:
The organic phosphazene superbase, 1-tert-butyl-4,4,4-tris(dimethylamino)- 2,2-bis[tris(dimethylamino)phosphoranylid-enamino]-2λ5, 4λ5-catenadi(phosphazene) (t-Bu-P4), is found to directly initiate high-speed polymerization of the biomass-derived renewable γ-methyl-α-methylene-γ-butyrolactone (MMBL), in contrast to other polymerization systems using t-Bu-P4 which typically require addition of an organic acid or a nucleophile as a co-initiating component. This MMBL polymerization by t-Bu-P4 alone is extremely rapid; even with a low t-Bu-P4 loading of 0.1 mol% or 0.02 mol%, quantitative monomer conversion is achieved in 20 s or 1 min, respectively, affording medium to high molecular weight PMMBL bioplastics in a catalytic fashion. The combined experimental and theoretical/computational studies have yielded mechanisms of chain initiation through abstraction of a proton from a monomer by t-Bu-P 4, essentially barrier-less chain propagation through rapid conjugate addition of the enolate anion stabilized by the nano-size cation [t-Bu-P 4H]+ to the monomer, and chain termination through chain transfer to the monomer which generates a saturated termination chain end and the [t-Bu-P4H]+-stabilized anionic active species that starts a new chain. This journal is © the Partner Organisations 2014.
KAUST Department:
KAUST Catalysis Center (KCC); Physical Sciences and Engineering (PSE) Division; Chemical Science Program
Publisher:
Royal Society of Chemistry (RSC)
Journal:
Polymer Chemistry
Issue Date:
2014
DOI:
10.1039/c3py01579c
Type:
Article
ISSN:
17599954
Sponsors:
This work was supported by the US National Science Foundation (NSF-1300267) for the study carried out at Colorado State University. We thank Dr Yuetao Zhang for some initial experiments. LC thanks the HPC team of Enea (http://www.enea.it) for using the ENEA-GRID and the HPC facilities CRESCO (http://www.cresco.enea.it) in Portici, Italy.
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorSchmitt, Meghan L.en
dc.contributor.authorFalivene, Lauraen
dc.contributor.authorCaporaso, Luciaen
dc.contributor.authorCavallo, Luigien
dc.contributor.authorChen, Eugene You Xianen
dc.date.accessioned2015-08-03T11:37:41Zen
dc.date.available2015-08-03T11:37:41Zen
dc.date.issued2014en
dc.identifier.issn17599954en
dc.identifier.doi10.1039/c3py01579cen
dc.identifier.urihttp://hdl.handle.net/10754/563184en
dc.description.abstractThe organic phosphazene superbase, 1-tert-butyl-4,4,4-tris(dimethylamino)- 2,2-bis[tris(dimethylamino)phosphoranylid-enamino]-2λ5, 4λ5-catenadi(phosphazene) (t-Bu-P4), is found to directly initiate high-speed polymerization of the biomass-derived renewable γ-methyl-α-methylene-γ-butyrolactone (MMBL), in contrast to other polymerization systems using t-Bu-P4 which typically require addition of an organic acid or a nucleophile as a co-initiating component. This MMBL polymerization by t-Bu-P4 alone is extremely rapid; even with a low t-Bu-P4 loading of 0.1 mol% or 0.02 mol%, quantitative monomer conversion is achieved in 20 s or 1 min, respectively, affording medium to high molecular weight PMMBL bioplastics in a catalytic fashion. The combined experimental and theoretical/computational studies have yielded mechanisms of chain initiation through abstraction of a proton from a monomer by t-Bu-P 4, essentially barrier-less chain propagation through rapid conjugate addition of the enolate anion stabilized by the nano-size cation [t-Bu-P 4H]+ to the monomer, and chain termination through chain transfer to the monomer which generates a saturated termination chain end and the [t-Bu-P4H]+-stabilized anionic active species that starts a new chain. This journal is © the Partner Organisations 2014.en
dc.description.sponsorshipThis work was supported by the US National Science Foundation (NSF-1300267) for the study carried out at Colorado State University. We thank Dr Yuetao Zhang for some initial experiments. LC thanks the HPC team of Enea (http://www.enea.it) for using the ENEA-GRID and the HPC facilities CRESCO (http://www.cresco.enea.it) in Portici, Italy.en
dc.publisherRoyal Society of Chemistry (RSC)en
dc.titleHigh-speed organocatalytic polymerization of a renewable methylene butyrolactone by a phosphazene superbaseen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentChemical Science Programen
dc.identifier.journalPolymer Chemistryen
dc.contributor.institutionDepartment of Chemistry, Colorado State University, Fort Collins CO 80523-1872, United Statesen
dc.contributor.institutionDipartimento di Chimica e Biologia, Università di Salerno, Via Ponte don Melillo, I-84084 Fisciano, Italyen
kaust.authorCavallo, Luigien
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