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, Robert H. Grubbs

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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-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium (6) and (1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(o-isopropoxyphenylmethylene)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.

Original languageEnglish
Pages (from-to)8190-8195
Number of pages6
JournalMacromolecules
Volume47
Issue number23
DOIs
Publication statusPublished - 9 Dec 2014

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Cyclopentanes
Ruthenium
Ring opening polymerization
Hydroxyl Radical
Polymers
Alcohols
Copolymers
Strain energy
Enthalpy
Chemical activation
Homopolymerization
Copolymerization
Hydrogenation
Propylene
Entropy
Polymerization
Thermodynamics
Catalysts

ASJC Scopus subject areas

  • Organic Chemistry
  • Materials Chemistry
  • Polymers and Plastics
  • Inorganic Chemistry

Cite this

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title = "One-pot synthesis of poly(vinyl alcohol) (PVA) copolymers via ruthenium catalyzed equilibrium ring-opening metathesis polymerization of hydroxyl functionalized cyclopentene",
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-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium (6) and (1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(o-isopropoxyphenylmethylene)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.",
author = "Robert Tuba and Mohammed Al-Hashimi and Bazzi, {Hassan S.} and Grubbs, {Robert H.}",
year = "2014",
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T1 - One-pot synthesis of poly(vinyl alcohol) (PVA) copolymers via ruthenium catalyzed equilibrium ring-opening metathesis polymerization of hydroxyl functionalized cyclopentene

AU - Tuba, Robert

AU - Al-Hashimi, Mohammed

AU - Bazzi, Hassan S.

AU - Grubbs, Robert H.

PY - 2014/12/9

Y1 - 2014/12/9

N2 - 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-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium (6) and (1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(o-isopropoxyphenylmethylene)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.

AB - 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-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium (6) and (1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(o-isopropoxyphenylmethylene)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.

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