Alkyl Phosphite Inhibitors for Frontal Ring-Opening Metathesis Polymerization Greatly Increase Pot Life

Ian D. Robertson; Leon M. Dean; Gabriel E. Rudebusch; Nancy R. Sottos; Scott R. White; Jeffrey S. Moore

doi:10.1021/acsmacrolett.7b00270

Alkyl Phosphite Inhibitors for Frontal Ring-Opening Metathesis Polymerization Greatly Increase Pot Life

Ian D. Robertson, Leon M. Dean, Gabriel E. Rudebusch, Nancy R. Sottos, Scott R. White, Jeffrey S. Moore

Research output: Contribution to journal › Article › peer-review

Abstract

Frontal ring-opening metathesis polymerization (FROMP) has potential for use in rapid fabrication of structural polymers. However, the high activity of the ruthenium catalyst used for FROMP has limited the working time to <1 h. We report the use of alkyl phosphites as inhibitors for Grubbs' type catalysts to substantially extend working time. Subtle changes in alkyl phosphite structure are shown to impact both pot life and frontal velocity. Specifically, by varying phosphite structure and concentration, we are able to control pot life between 0.25 and 30 h while still allowing FROMP to proceed at velocities between 1 and 8 cm/min to yield fully cured thermoset polymers. These results are of interest for conventional ROMP synthesis and may open the way to new FROMP-based manufacturing possibilities.

Original language	English (US)
Pages (from-to)	609-612
Number of pages	4
Journal	ACS Macro Letters
Volume	6
Issue number	6
DOIs	https://doi.org/10.1021/acsmacrolett.7b00270
State	Published - Jun 20 2017

ASJC Scopus subject areas

Organic Chemistry
Polymers and Plastics
Inorganic Chemistry
Materials Chemistry

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10.1021/acsmacrolett.7b00270

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title = "Alkyl Phosphite Inhibitors for Frontal Ring-Opening Metathesis Polymerization Greatly Increase Pot Life",

abstract = "Frontal ring-opening metathesis polymerization (FROMP) has potential for use in rapid fabrication of structural polymers. However, the high activity of the ruthenium catalyst used for FROMP has limited the working time to <1 h. We report the use of alkyl phosphites as inhibitors for Grubbs' type catalysts to substantially extend working time. Subtle changes in alkyl phosphite structure are shown to impact both pot life and frontal velocity. Specifically, by varying phosphite structure and concentration, we are able to control pot life between 0.25 and 30 h while still allowing FROMP to proceed at velocities between 1 and 8 cm/min to yield fully cured thermoset polymers. These results are of interest for conventional ROMP synthesis and may open the way to new FROMP-based manufacturing possibilities.",

author = "Robertson, {Ian D.} and Dean, {Leon M.} and Rudebusch, {Gabriel E.} and Sottos, {Nancy R.} and White, {Scott R.} and Moore, {Jeffrey S.}",

note = "Funding Information: I.R. also thanks the U.S. Department of Defense for a National Defense Science and Engineering Graduate Fellowship. L.D. thanks the National Science Foundation for a Graduate Research Fellowship. This research was supported by the Air Force Office of Scientific Research through Award FA9550-16-1-0017. Publisher Copyright: {\textcopyright} 2017 American Chemical Society.",

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doi = "10.1021/acsmacrolett.7b00270",

language = "English (US)",

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AU - Robertson, Ian D.

AU - Dean, Leon M.

AU - Rudebusch, Gabriel E.

AU - Sottos, Nancy R.

AU - White, Scott R.

AU - Moore, Jeffrey S.

N1 - Funding Information: I.R. also thanks the U.S. Department of Defense for a National Defense Science and Engineering Graduate Fellowship. L.D. thanks the National Science Foundation for a Graduate Research Fellowship. This research was supported by the Air Force Office of Scientific Research through Award FA9550-16-1-0017. Publisher Copyright: © 2017 American Chemical Society.

PY - 2017/6/20

Y1 - 2017/6/20

N2 - Frontal ring-opening metathesis polymerization (FROMP) has potential for use in rapid fabrication of structural polymers. However, the high activity of the ruthenium catalyst used for FROMP has limited the working time to <1 h. We report the use of alkyl phosphites as inhibitors for Grubbs' type catalysts to substantially extend working time. Subtle changes in alkyl phosphite structure are shown to impact both pot life and frontal velocity. Specifically, by varying phosphite structure and concentration, we are able to control pot life between 0.25 and 30 h while still allowing FROMP to proceed at velocities between 1 and 8 cm/min to yield fully cured thermoset polymers. These results are of interest for conventional ROMP synthesis and may open the way to new FROMP-based manufacturing possibilities.

AB - Frontal ring-opening metathesis polymerization (FROMP) has potential for use in rapid fabrication of structural polymers. However, the high activity of the ruthenium catalyst used for FROMP has limited the working time to <1 h. We report the use of alkyl phosphites as inhibitors for Grubbs' type catalysts to substantially extend working time. Subtle changes in alkyl phosphite structure are shown to impact both pot life and frontal velocity. Specifically, by varying phosphite structure and concentration, we are able to control pot life between 0.25 and 30 h while still allowing FROMP to proceed at velocities between 1 and 8 cm/min to yield fully cured thermoset polymers. These results are of interest for conventional ROMP synthesis and may open the way to new FROMP-based manufacturing possibilities.

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Alkyl Phosphite Inhibitors for Frontal Ring-Opening Metathesis Polymerization Greatly Increase Pot Life

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