Aqueous Ring-Opening Metathesis Polymerization of Carboximide-Functionalized 7-Oxanorbornenes

Marc A. Hillmyer; Robert H. Grubbs; Christine Lepetit; Dominic V. McGrath; Bruce M. Novak

doi:10.1021/ma00039a004

Aqueous Ring-Opening Metathesis Polymerization of Carboximide-Functionalized 7-Oxanorbornenes

Marc A. Hillmyer, Robert H. Grubbs, Christine Lepetit, Dominic V. McGrath, Bruce M. Novak

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103 Scopus citations

Abstract

The ring-opening metathesis polymerization (ROMP) of exo-N-methyl-7-oxabicyclo[2.2.1]- hept-5-ene-2,3-dicarboximide (1) was accomplished in aqueous solution under mild conditions using the simple ruthenium(II) coordination complex Ru^II(H₂O)₆(tos)₂ (tos = p-toluenesulfonate) (2). The polymerization yield was nearly quantitative. The resultant high molecular weight polymer (poly-1) exhibited a glass transition temperature (T_g) of 225 °C and was thermally stable up to 402 °C. The thermal and radiative stabilities of poly-1 were further investigated. Poly-1 was hydrogenated to yield its saturated analogue, which had a lower T_g (170 °C) but a higher temperature of decomposition (430 °C). Complex 2 was deactivated by coordination of free maleimides formed during the polymerization of carboximide-functionalized monomers capable of undergoing retro Diels-Alder chemistry. The scope of this polymerization was therefore limited to carboximide-functionalized monomers that are stable toward retro Diels-Alder reactions at the polymerization temperature. Both ruthenium (II)-1 and ruthenium(II)-N-methylmaleimide olefin complexes were identified.

Original language	English (US)
Pages (from-to)	3345-3350
Number of pages	6
Journal	Macromolecules
Volume	25
Issue number	13
DOIs	https://doi.org/10.1021/ma00039a004
State	Published - Jun 1 1992
Externally published	Yes

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title = "Aqueous Ring-Opening Metathesis Polymerization of Carboximide-Functionalized 7-Oxanorbornenes",

abstract = "The ring-opening metathesis polymerization (ROMP) of exo-N-methyl-7-oxabicyclo[2.2.1]- hept-5-ene-2,3-dicarboximide (1) was accomplished in aqueous solution under mild conditions using the simple ruthenium(II) coordination complex RuII(H2O)6(tos)2 (tos = p-toluenesulfonate) (2). The polymerization yield was nearly quantitative. The resultant high molecular weight polymer (poly-1) exhibited a glass transition temperature (Tg) of 225 °C and was thermally stable up to 402 °C. The thermal and radiative stabilities of poly-1 were further investigated. Poly-1 was hydrogenated to yield its saturated analogue, which had a lower Tg (170 °C) but a higher temperature of decomposition (430 °C). Complex 2 was deactivated by coordination of free maleimides formed during the polymerization of carboximide-functionalized monomers capable of undergoing retro Diels-Alder chemistry. The scope of this polymerization was therefore limited to carboximide-functionalized monomers that are stable toward retro Diels-Alder reactions at the polymerization temperature. Both ruthenium (II)-1 and ruthenium(II)-N-methylmaleimide olefin complexes were identified.",

author = "Hillmyer, {Marc A.} and Grubbs, {Robert H.} and Christine Lepetit and McGrath, {Dominic V.} and Novak, {Bruce M.}",

year = "1992",

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doi = "10.1021/ma00039a004",

language = "English (US)",

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T1 - Aqueous Ring-Opening Metathesis Polymerization of Carboximide-Functionalized 7-Oxanorbornenes

AU - Hillmyer, Marc A.

AU - Grubbs, Robert H.

AU - Lepetit, Christine

AU - McGrath, Dominic V.

AU - Novak, Bruce M.

PY - 1992/6/1

Y1 - 1992/6/1

N2 - The ring-opening metathesis polymerization (ROMP) of exo-N-methyl-7-oxabicyclo[2.2.1]- hept-5-ene-2,3-dicarboximide (1) was accomplished in aqueous solution under mild conditions using the simple ruthenium(II) coordination complex RuII(H2O)6(tos)2 (tos = p-toluenesulfonate) (2). The polymerization yield was nearly quantitative. The resultant high molecular weight polymer (poly-1) exhibited a glass transition temperature (Tg) of 225 °C and was thermally stable up to 402 °C. The thermal and radiative stabilities of poly-1 were further investigated. Poly-1 was hydrogenated to yield its saturated analogue, which had a lower Tg (170 °C) but a higher temperature of decomposition (430 °C). Complex 2 was deactivated by coordination of free maleimides formed during the polymerization of carboximide-functionalized monomers capable of undergoing retro Diels-Alder chemistry. The scope of this polymerization was therefore limited to carboximide-functionalized monomers that are stable toward retro Diels-Alder reactions at the polymerization temperature. Both ruthenium (II)-1 and ruthenium(II)-N-methylmaleimide olefin complexes were identified.

AB - The ring-opening metathesis polymerization (ROMP) of exo-N-methyl-7-oxabicyclo[2.2.1]- hept-5-ene-2,3-dicarboximide (1) was accomplished in aqueous solution under mild conditions using the simple ruthenium(II) coordination complex RuII(H2O)6(tos)2 (tos = p-toluenesulfonate) (2). The polymerization yield was nearly quantitative. The resultant high molecular weight polymer (poly-1) exhibited a glass transition temperature (Tg) of 225 °C and was thermally stable up to 402 °C. The thermal and radiative stabilities of poly-1 were further investigated. Poly-1 was hydrogenated to yield its saturated analogue, which had a lower Tg (170 °C) but a higher temperature of decomposition (430 °C). Complex 2 was deactivated by coordination of free maleimides formed during the polymerization of carboximide-functionalized monomers capable of undergoing retro Diels-Alder chemistry. The scope of this polymerization was therefore limited to carboximide-functionalized monomers that are stable toward retro Diels-Alder reactions at the polymerization temperature. Both ruthenium (II)-1 and ruthenium(II)-N-methylmaleimide olefin complexes were identified.

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Aqueous Ring-Opening Metathesis Polymerization of Carboximide-Functionalized 7-Oxanorbornenes

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