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One-Pot Synthesis of Poly(vinyl alcohol) (PVA) Copolymers via Ruthenium Catalyzed Equilibrium Ring-Opening Metathesis Polymerization of Hydroxyl Functionalized Cyclopentene

Tuba, Robert and Al-Hashimi, Mohammed and Bazzi, Hassan S. and Grubbs, Robert H. (2014) One-Pot Synthesis of Poly(vinyl alcohol) (PVA) Copolymers via Ruthenium Catalyzed Equilibrium Ring-Opening Metathesis Polymerization of Hydroxyl Functionalized Cyclopentene. Macromolecules, 47 (23). pp. 8190-8195. ISSN 0024-9297. https://resolver.caltech.edu/CaltechAUTHORS:20150116-090031533

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Abstract

Well-defined poly(vinyl alcohol-alt-propenylene) (4) was synthesized in one-pot reaction via equilibrium ring-opening metathesis polymerization (ROMP) or acyclic diene metathesis (ADMET) of nonprotected 3-cyclopentene-1-ol (2) and 1,6-heptadiene-4-ol using (1,3-bis(2,4,6-trimethylphenyl)-2-midazolidinylidene)dichloro(phenylmet hylene)(tricyclohexylphosphine)ruthenium (6) and (1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(o-isoprop oxyphenylmethylene)ruthenium (7) metathesis catalysts. The activation enthalpy and entropy of the equilibrium ROMP were determined as ΔH = -6.2 kcal mol^(-1) and ΔS = -18.9 cal mol^(-1) K^(-1). The observed thermodynamic parameters were supported by computational studies. The calculated ring strain energy for 2 (-6.8 kcal mol^(-1) is comparable with the observed activation enthalpy for its equilibrium ROMP reaction catalyzed by 6 or 7. The cis:trans olefinic bond ratio analysis indicated a 20:80 cis:trans selectivity. The hydrogenation of 4 resulted in poly(vinyl alcohol-alt-propylene) (11) in high yield. Because of the similar ring strain energies of cyclopentene (1) and 2, the equilibrium copolymerization results in a polymer having randomly distributed dyads. In general, it means that the polymer formed contains approximately 50% alternating polymer, 25% 3, and 25% 4 homopolymer dyads as expected for a random polymerization.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ma501976vDOIArticle
http://pubs.acs.org/doi/abs/10.1021/ma501976vPublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/ma501976vRelated ItemSupporting Information
ORCID:
AuthorORCID
Al-Hashimi, Mohammed0000-0001-6015-2178
Bazzi, Hassan S.0000-0002-5702-0091
Grubbs, Robert H.0000-0002-0057-7817
Additional Information:© 2014 American Chemical Society. Received: September 24, 2014. Revised: November 7, 2014. Published: November 25, 2014. The authors thank Texas A&M University at Qatar and Qatar Petrochemical Company (QAPCO) for financial support.
Funders:
Funding AgencyGrant Number
Qatar Texas A&M UniversityUNSPECIFIED
Qatar Petrochemical company (QAPCO)UNSPECIFIED
Issue or Number:23
Record Number:CaltechAUTHORS:20150116-090031533
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20150116-090031533
Official Citation:One-Pot Synthesis of Poly(vinyl alcohol) (PVA) Copolymers via Ruthenium Catalyzed Equilibrium Ring-Opening Metathesis Polymerization of Hydroxyl Functionalized Cyclopentene Robert Tuba, Mohammed Al-Hashimi, Hassan S. Bazzi, and Robert H. Grubbs Macromolecules 2014 47 (23), 8190-8195
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:53809
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:16 Jan 2015 18:31
Last Modified:03 Oct 2019 07:52

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