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Synthesis of ABA Triblock Copolymers of Norbornenes and 7-Oxanorbornenes via Living Ring-Opening Metathesis Polymerization Using Well-Defined, Bimetallic Ruthenium Catalysts

Weck, Marcus and Schwab, Peter and Grubbs, Robert H. (1996) Synthesis of ABA Triblock Copolymers of Norbornenes and 7-Oxanorbornenes via Living Ring-Opening Metathesis Polymerization Using Well-Defined, Bimetallic Ruthenium Catalysts. Macromolecules, 29 (5). pp. 1789-1793. ISSN 0024-9297. doi:10.1021/ma9513426. https://resolver.caltech.edu/CaltechAUTHORS:20180719-143039221

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Abstract

Norbornene and 7-oxanorbornene derivatives were polymerized by ring-opening metathesis polymerization (ROMP) in a living manner by employing three new well-defined, bimetallic ruthenium catalysts (PR3)2Cl2Ru(CH-p-C6H4C(H))RuCl2(PR3)2 [R = Ph, 1; R = Cy (cyclohexyl), 2; R = Cyp (cyclopentyl), 3] as initiators to obtain ABA triblock copolymers with low polydispersities. 1−3 were synthesized via alkylidene transfer from 1,4-bis(α-diazomethyl)benzene to RuCl2(PPh3)3 and subsequent phosphine exchange. Reactions of 7-oxanorbornenes 5 and 6 or a silicon-containing norbornene 7 with 3 resulted in polymers with low polydispersities ranging from 1.10 to 1.22, while polymerizations initiated by 2 displayed higher polydispersities ranging from 1.20 to 1.35. Polymerizations of 5−7 catalyzed by 2 and 3 fulfill the requirements for a living polymerization. However, catalyst 1 is not reactive enough to polymerize functionalized norbornenes or 7-oxanorbornenes. The living polymerizations were successfully used to prepare three ABA triblock copolymers of monomers 5−7. In all cases, these ABA triblock copolymers have higher molecular weights than the homopolymers, and all polydispersities remained low.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://dx.doi.org/10.1021/ma9513426DOIArticle
ORCID:
AuthorORCID
Grubbs, Robert H.0000-0002-0057-7817
Additional Information:© 1996 American Chemical Society. Received September 8, 1995; Revised Manuscript Received December 8, 1995. This work was supported by the National Science Foundation. P.S. thanks the Alexander von Humboldt Foundation for a Feodor Lynen postdoctoral fellowship. We are especially grateful to David Lynn for helpful comments.
Funders:
Funding AgencyGrant Number
NSFUNSPECIFIED
Alexander von Humboldt FoundationUNSPECIFIED
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Other Numbering System NameOther Numbering System ID
Arnold and Mabel Beckman Laboratories of Chemical Synthesis9135
Issue or Number:5
DOI:10.1021/ma9513426
Record Number:CaltechAUTHORS:20180719-143039221
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20180719-143039221
Official Citation:Synthesis of ABA Triblock Copolymers of Norbornenes and 7-Oxanorbornenes via Living Ring-Opening Metathesis Polymerization Using Well-Defined, Bimetallic Ruthenium Catalysts Marcus Weck, Peter Schwab, and Robert H. Grubbs Macromolecules 1996 29 (5), 1789-1793 DOI: 10.1021/ma9513426
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:88015
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:19 Jul 2018 21:45
Last Modified:16 Nov 2021 00:22

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