The Quest for Converting Biorenewable Bifunctional α-Methylene-γ-butyrolactone into Degradable and Recyclable Polyester: Controlling Vinyl-Addition/Ring-Opening/Cross-Linking Pathways

Handle URI:
http://hdl.handle.net/10754/622483
Title:
The Quest for Converting Biorenewable Bifunctional α-Methylene-γ-butyrolactone into Degradable and Recyclable Polyester: Controlling Vinyl-Addition/Ring-Opening/Cross-Linking Pathways
Authors:
Tang, Xiaoyan; Hong, Miao; Falivene, Laura ( 0000-0003-1509-6191 ) ; Caporaso, Lucia; Cavallo, Luigi ( 0000-0002-1398-338X ) ; Chen, Eugene Y X
Abstract:
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.
KAUST Department:
KAUST Catalysis Center (KCC); Physical Sciences and Engineering (PSE) Division
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.
Publisher:
American Chemical Society (ACS)
Journal:
Journal of the American Chemical Society
Issue Date:
4-Oct-2016
DOI:
10.1021/jacs.6b07974
Type:
Article
ISSN:
0002-7863; 1520-5126
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.
Additional Links:
http://dx.doi.org/10.1021/jacs.6b07974
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorTang, Xiaoyanen
dc.contributor.authorHong, Miaoen
dc.contributor.authorFalivene, Lauraen
dc.contributor.authorCaporaso, Luciaen
dc.contributor.authorCavallo, Luigien
dc.contributor.authorChen, Eugene Y Xen
dc.date.accessioned2017-01-02T09:28:33Z-
dc.date.available2017-01-02T09:28:33Z-
dc.date.issued2016-10-04en
dc.identifier.citationTang 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.en
dc.identifier.issn0002-7863en
dc.identifier.issn1520-5126en
dc.identifier.doi10.1021/jacs.6b07974en
dc.identifier.urihttp://hdl.handle.net/10754/622483-
dc.description.abstractα-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.en
dc.description.sponsorshipThis 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.en
dc.publisherAmerican Chemical Society (ACS)en
dc.relation.urlhttp://dx.doi.org/10.1021/jacs.6b07974en
dc.titleThe Quest for Converting Biorenewable Bifunctional α-Methylene-γ-butyrolactone into Degradable and Recyclable Polyester: Controlling Vinyl-Addition/Ring-Opening/Cross-Linking Pathwaysen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.identifier.journalJournal of the American Chemical Societyen
dc.contributor.institutionDepartment of Chemistry, Colorado State University, Fort Collins, Colorado 80523-1872, United Statesen
dc.contributor.institutionDipartimento di Chimica e Biologia, Università di Salerno, Via Papa Paolo Giovanni II, I-84084, Fisciano, Italyen
kaust.authorFalivene, Lauraen
kaust.authorCavallo, Luigien
All Items in KAUST are protected by copyright, with all rights reserved, unless otherwise indicated.