Mechanistic Investigations of a Series of Porphyrin Metal (III) Catalysts with Al, Cr or Co Centers for the Synthesis of Polyethers, Polycarbonates and Polyesters

Mechanistic Investigations of a Series of Porphyrin Metal (III) Catalysts with Al, Cr or Co Centers for the Synthesis of Polyethers, Polycarbonates and Polyesters

Bibliographic Details
Main Author: Chatterjee, Chandrani
Language:English
Published: The Ohio State University / OhioLINK 2012
Subjects:
Chemistry
epoxide
CO2
copolymerization
porphyrin metal catalyst systems
cocatalysts
react IR study
polymer quality
Online Access:http://rave.ohiolink.edu/etdc/view?acc_num=osu1345501920
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spelling ndltd-OhioLink-oai-etd.ohiolink.edu-osu13455019202021-08-03T06:06:17Z Mechanistic Investigations of a Series of Porphyrin Metal (III) Catalysts with Al, Cr or Co Centers for the Synthesis of Polyethers, Polycarbonates and Polyesters Chatterjee, Chandrani Chemistry epoxide CO2 copolymerization porphyrin metal catalyst systems cocatalysts react IR study polymer quality In the modern era the production of chemicals from sustainable natural resources as an alternative to petrochemicals is an absolute necessity. Among the major commodity polymers, potential candidates for synthesis from renewable natural resources are polyesters and polycarbonates. A series of porphyrin metal (III) compounds of general formula LMX (L = tetraphenylporphyrin (TPP), octaethylporphyrin (OEP), tetrakispentafluorophenylporphyrin (TFPP), M = aluminum, chromium, cobalt, X = Cl, OEt (for Al); Cl, OAc, OH (for Cr); Cl, OAc (for Co)) has been synthesized and used as catalysts to produce polypropylene carbonate and propylene carbonate. These catalysts are further investigated for the copolymerization of propylene oxide with succinic anhydride (SA) or phthalic anhydride (PA) to produce polypropylene succinate and polypropylene phthalate. The metal catalyzed copolymerization process provides an alternative “greener” synthetic route to the preparation of these polymers using renewable feedstocks e.g. CO2 and succinic acid.The electronic nature of the porphyrin ligand, the choice of metal center and the addition of Lewis basic cocatalysts e.g. DMAP or PPN+Cl- showed dramatic influence on the catalytic TOF, product selectivity and polymer quality. Detailed kinetic and mechanistic investigations were carried out to elucidate the nature of various reactive intermediates i.e. M-alkoxide, M-carbonate and M-carboxylates, involved in the polymerization processes. These comparative analyses show how the electronic environment around the metal center and the binding of added Lewis base cocatalysts influence the reactivity of the various metal-oxygenate intermediates, and thereby control the individual reaction steps and equilibria involved in the polymerization processes. 2012-08-31 English text The Ohio State University / OhioLINK http://rave.ohiolink.edu/etdc/view?acc_num=osu1345501920 http://rave.ohiolink.edu/etdc/view?acc_num=osu1345501920 unrestricted This thesis or dissertation is protected by copyright: all rights reserved. It may not be copied or redistributed beyond the terms of applicable copyright laws.
collection NDLTD
language English
sources NDLTD
topic Chemistry
epoxide
CO2
copolymerization
porphyrin metal catalyst systems
cocatalysts
react IR study
polymer quality
spellingShingle Chemistry
epoxide
CO2
copolymerization
porphyrin metal catalyst systems
cocatalysts
react IR study
polymer quality
Chatterjee, Chandrani
Mechanistic Investigations of a Series of Porphyrin Metal (III) Catalysts with Al, Cr or Co Centers for the Synthesis of Polyethers, Polycarbonates and Polyesters
author Chatterjee, Chandrani
author_facet Chatterjee, Chandrani
author_sort Chatterjee, Chandrani
title Mechanistic Investigations of a Series of Porphyrin Metal (III) Catalysts with Al, Cr or Co Centers for the Synthesis of Polyethers, Polycarbonates and Polyesters
title_short Mechanistic Investigations of a Series of Porphyrin Metal (III) Catalysts with Al, Cr or Co Centers for the Synthesis of Polyethers, Polycarbonates and Polyesters
title_full Mechanistic Investigations of a Series of Porphyrin Metal (III) Catalysts with Al, Cr or Co Centers for the Synthesis of Polyethers, Polycarbonates and Polyesters
title_fullStr Mechanistic Investigations of a Series of Porphyrin Metal (III) Catalysts with Al, Cr or Co Centers for the Synthesis of Polyethers, Polycarbonates and Polyesters
title_full_unstemmed Mechanistic Investigations of a Series of Porphyrin Metal (III) Catalysts with Al, Cr or Co Centers for the Synthesis of Polyethers, Polycarbonates and Polyesters
title_sort mechanistic investigations of a series of porphyrin metal (iii) catalysts with al, cr or co centers for the synthesis of polyethers, polycarbonates and polyesters
publisher The Ohio State University / OhioLINK
publishDate 2012
url http://rave.ohiolink.edu/etdc/view?acc_num=osu1345501920
work_keys_str_mv AT chatterjeechandrani mechanisticinvestigationsofaseriesofporphyrinmetaliiicatalystswithalcrorcocentersforthesynthesisofpolyetherspolycarbonatesandpolyesters
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