Cobaltoporphyrin-Catalyzed CO 2 /Epoxide Copolymerization: Selectivity Control by Molecular Design

Handle URI:
http://hdl.handle.net/10754/597791
Title:
Cobaltoporphyrin-Catalyzed CO 2 /Epoxide Copolymerization: Selectivity Control by Molecular Design
Authors:
Anderson, Carly E.; Vagin, Sergei I.; Xia, Wei; Jin, Hanpeng; Rieger, Bernhard
Abstract:
A series of cobalt(III) chloride porphyrin complexes of the general formula 5,10,15,20-tetra(p-alkoxy)phenylporphyrin cobalt chloride (4b-e) and the related 5,10,15,20-tetra(p-nitro)phenylporphyrin cobalt chloride (4f) are presented and their reactivity toward propylene oxide (PO)/CO 2 coupling/copolymerization is explored. While the nitro-substituted complex (4f), in conjunction with an onium salt, shows moderate activity toward cyclization, the 4b-e/onium systems show superior copolymerization activity in comparison to tetraphenylporphyrin Co(III) chloride (4a) with high selectivity and conversion to poly(propylene carbonate) (PPC). A comprehensive copolymerization behavior study of the alkoxy-substituted porphyrin complexes 4b-e in terms of reaction temperature and CO 2 pressure is presented. Complexes bearing longer alkoxy-substituents demonstrate the highest polymerization activity and molecular weights, however all substituted catalyst systems display a reduced tolerance to increased temperature with respect to PPC formation. Studies of the resulting polymer microstructures show excellent head-to-tail epoxide incorporation and near perfectly alternating poly(carbonate) character at lower polymerization temperatures. © 2012 American Chemical Society.
Citation:
Anderson CE, Vagin SI, Xia W, Jin H, Rieger B (2012) Cobaltoporphyrin-Catalyzed CO 2 /Epoxide Copolymerization: Selectivity Control by Molecular Design . Macromolecules 45: 6840–6849. Available: http://dx.doi.org/10.1021/ma301205g.
Publisher:
American Chemical Society (ACS)
Journal:
Macromolecules
KAUST Grant Number:
UK-C0020; KSA-C0069
Issue Date:
11-Sep-2012
DOI:
10.1021/ma301205g
Type:
Article
ISSN:
0024-9297; 1520-5835
Sponsors:
We gratefully acknowledge the King Abdullah University of Science and Technology (KAUST), Award No. UK-C0020, KSA-C0069, for financial support. Ms. A. Jonovic is thanked for technical support with TGA and GPC measurements. Mr. V. Bretzler is acknowledged for helpful comments with the preparation of this manuscript.
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Publications Acknowledging KAUST Support

Full metadata record

DC FieldValue Language
dc.contributor.authorAnderson, Carly E.en
dc.contributor.authorVagin, Sergei I.en
dc.contributor.authorXia, Weien
dc.contributor.authorJin, Hanpengen
dc.contributor.authorRieger, Bernharden
dc.date.accessioned2016-02-25T12:56:47Zen
dc.date.available2016-02-25T12:56:47Zen
dc.date.issued2012-09-11en
dc.identifier.citationAnderson CE, Vagin SI, Xia W, Jin H, Rieger B (2012) Cobaltoporphyrin-Catalyzed CO 2 /Epoxide Copolymerization: Selectivity Control by Molecular Design . Macromolecules 45: 6840–6849. Available: http://dx.doi.org/10.1021/ma301205g.en
dc.identifier.issn0024-9297en
dc.identifier.issn1520-5835en
dc.identifier.doi10.1021/ma301205gen
dc.identifier.urihttp://hdl.handle.net/10754/597791en
dc.description.abstractA series of cobalt(III) chloride porphyrin complexes of the general formula 5,10,15,20-tetra(p-alkoxy)phenylporphyrin cobalt chloride (4b-e) and the related 5,10,15,20-tetra(p-nitro)phenylporphyrin cobalt chloride (4f) are presented and their reactivity toward propylene oxide (PO)/CO 2 coupling/copolymerization is explored. While the nitro-substituted complex (4f), in conjunction with an onium salt, shows moderate activity toward cyclization, the 4b-e/onium systems show superior copolymerization activity in comparison to tetraphenylporphyrin Co(III) chloride (4a) with high selectivity and conversion to poly(propylene carbonate) (PPC). A comprehensive copolymerization behavior study of the alkoxy-substituted porphyrin complexes 4b-e in terms of reaction temperature and CO 2 pressure is presented. Complexes bearing longer alkoxy-substituents demonstrate the highest polymerization activity and molecular weights, however all substituted catalyst systems display a reduced tolerance to increased temperature with respect to PPC formation. Studies of the resulting polymer microstructures show excellent head-to-tail epoxide incorporation and near perfectly alternating poly(carbonate) character at lower polymerization temperatures. © 2012 American Chemical Society.en
dc.description.sponsorshipWe gratefully acknowledge the King Abdullah University of Science and Technology (KAUST), Award No. UK-C0020, KSA-C0069, for financial support. Ms. A. Jonovic is thanked for technical support with TGA and GPC measurements. Mr. V. Bretzler is acknowledged for helpful comments with the preparation of this manuscript.en
dc.publisherAmerican Chemical Society (ACS)en
dc.titleCobaltoporphyrin-Catalyzed CO 2 /Epoxide Copolymerization: Selectivity Control by Molecular Designen
dc.typeArticleen
dc.identifier.journalMacromoleculesen
dc.contributor.institutionTechnische Universitat Munchen, Munich, Germanyen
kaust.grant.numberUK-C0020en
kaust.grant.numberKSA-C0069en
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