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Computational Insights on the Challenges for Polymerizing Polar Monomers

Philipp, Dean M. and Muller, Richard P. and Goddard, William A., III and Storer, Joey and McAdon, Mark and Mullins, Mike (2002) Computational Insights on the Challenges for Polymerizing Polar Monomers. Journal of the American Chemical Society, 124 (34). pp. 10198-10210. ISSN 0002-7863. doi:10.1021/ja0157705. https://resolver.caltech.edu/CaltechAUTHORS:20170509-161314947

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Abstract

Taking Pd di-imine catalysts as an example, we use first principles density functional theory (B3LYP/6-31G*) to investigate the chain propagation steps for polymerization of polar monomers. We start with the complex formed from insertion of ethylene into the polymer chain and consider insertion into the Pd−C bond for each of four polar monomers:  methyl acrylate, vinyl acetate, vinyl chloride, and acrylonitrile. We find 2,1-insertion is favored in each case (by 3 to 5 kcal/mol), resulting in a product with a strong interaction of the polar group for the growing polymer chain with the metal. Next, we insert another unit of the same polar monomer or an ethylene unit (except for acrylonitrile). We optimize the structures for all important intermediates and transition states using a continuum dielectric to account for solvation effects. These studies pinpoint the critical difficulties in designing catalysts to polymerize polar monomers.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ja0157705DOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja0157705PublisherArticle
ORCID:
AuthorORCID
Goddard, William A., III0000-0003-0097-5716
Additional Information:© 2002 American Chemical Society. Received March 6, 2001. Revised Manuscript Received February 23, 2002. Publication Date (Web): July 31, 2002. This work was supported by the Dow Chemical Company. The facilities of the MSC were partly funded by NSF CHE and ARO/DURIP and are also supported by grants from DOE-ASCI, ARO/MURI, Chevron, NIH, ONR, 3M, Seiko-Epson, Avery-Dennison, Kellogg's, General Motors, Beckman Institute, Asahi Chemical, and Nippon Steel.
Funders:
Funding AgencyGrant Number
Dow Chemical CompanyUNSPECIFIED
NSFUNSPECIFIED
Army Research Office (ARO)UNSPECIFIED
Department of Energy (DOE)UNSPECIFIED
ChevronUNSPECIFIED
NIHUNSPECIFIED
Office of Naval Research (ONR)UNSPECIFIED
3MUNSPECIFIED
Seiko-EpsonUNSPECIFIED
Avery-DennisonUNSPECIFIED
Kellogg'sUNSPECIFIED
General MotorsUNSPECIFIED
Caltech Beckman InstituteUNSPECIFIED
Asahi ChemicalUNSPECIFIED
Nippon SteelUNSPECIFIED
Issue or Number:34
DOI:10.1021/ja0157705
Record Number:CaltechAUTHORS:20170509-161314947
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20170509-161314947
Official Citation:Computational Insights on the Challenges for Polymerizing Polar Monomers Dean M. Philipp, Richard P. Muller, William A. Goddard, III, Joey Storer, Mark McAdon, and Mike Mullins Journal of the American Chemical Society 2002 124 (34), 10198-10210 DOI: 10.1021/ja0157705
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:77318
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:16 May 2017 21:57
Last Modified:15 Nov 2021 17:29

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