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Chain Transfer in the Ring-Opening Metathesis Polymerization of Cyclooctadiene Using Discrete Metal Alkylidenes

Hillmyer, Marc A. and Grubbs, Robert H. (1995) Chain Transfer in the Ring-Opening Metathesis Polymerization of Cyclooctadiene Using Discrete Metal Alkylidenes. Macromolecules, 28 (25). pp. 8662-8667. ISSN 0024-9297. doi:10.1021/ma00129a027. https://resolver.caltech.edu/CaltechAUTHORS:20180313-145155358

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Abstract

The ring-opening metathesis polymerization of cyclooctadiene (COD) in the presence of a difunctional chain transfer agent (CTA) was investigated. The effect of the CTA structure and choice of metathesis catalyst on the overall efficiency of the polymerization reaction is discussed. A separation of the oxygen functionality from the olefin in the CTA by two methylene units significantly enhances the stability of the discrete, tungsten-based metathesis catalyst used for these polymerizations. Furthermore, a more robust well-defined metathesis catalyst based on molybdenum was more effective than the tungsten-based catalyst. The preparation oflow-molecular-weight hydroxytelechelic polybutadienes with one type of regiochemistry, number-average functionalities that approach 2.0, and in high yield was accomplished.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/ma00129a027DOIArticle
https://pubs.acs.org/doi/abs/10.1021/ma00129a027PublisherArticle
ORCID:
AuthorORCID
Hillmyer, Marc A.0000-0001-8255-3853
Grubbs, Robert H.0000-0002-0057-7817
Additional Information:© 1995 American Chemical Society. Received May 23, 1995; Revised Manuscript Received September 12, 1995. Funding for this research was provided by the National Science Foundation, Thiokol Corp., and Miles Inc. M.A.H. is the recipient of a graduate fellowship from IBM, for which he is grateful. We would like to thank Professor J. M. DeSimone, Professor R. W. Linton, and Anna Belu at the University of North Carolina for performing the TOF-SIMS analysis. Neftali Morales, a participant in the Minority Undergraduate Research Fellowship (MURF) program at Caltech, provided technical assistance in the preparation of the chain transfer agents described within.
Funders:
Funding AgencyGrant Number
NSFUNSPECIFIED
Thiokol Chemical CorporationUNSPECIFIED
Miles Inc.UNSPECIFIED
IBMUNSPECIFIED
Caltech Minority Undergraduate Research Fellowship (MURF)UNSPECIFIED
Other Numbering System:
Other Numbering System NameOther Numbering System ID
Caltech Arnold and Mabel Laboratories of Chemical Synthesis9606
Issue or Number:25
DOI:10.1021/ma00129a027
Record Number:CaltechAUTHORS:20180313-145155358
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20180313-145155358
Official Citation:Chain Transfer in the Ring-Opening Metathesis Polymerization of Cyclooctadiene Using Discrete Metal Alkylidenes. Marc A. Hillmyer and Robert H. Grubbs. Macromolecules 1995 28 (25), 8662-8667. DOI: 10.1021/ma00129a027
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:85286
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:13 Mar 2018 21:59
Last Modified:15 Nov 2021 20:27

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