Isomerization of Linear to Hyperbranched Polymers: Two Isomeric Lactones Converge via Metastable Isostructural Polyesters to a Highly Branched Analogue

Grant W. Fahnhorst; Daniel E. Stasiw; William B. Tolman; Thomas R. Hoye

doi:10.1021/acsmacrolett.8b00621

Isomerization of Linear to Hyperbranched Polymers: Two Isomeric Lactones Converge via Metastable Isostructural Polyesters to a Highly Branched Analogue

Grant W. Fahnhorst, Daniel E. Stasiw, William B. Tolman, Thomas R. Hoye

Chemistry (Twin Cities)

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

4 Scopus citations

Abstract

We report here the Zn(II)-catalyzed convergence of two metastable and isostructural polyesters to an isomeric polymer having a hyperbranched architecture. Ring-opening transesterification polymerization (ROTEP) of 4-carbomethoxyvalerolactone (CMVL) under Brønsted catalysis is known to give the linear polyester PCMVL. We show here that this can be isomerized to the equilibrated (and highly branched) polyester EQ-PCMVL. Analysis of the fragments obtained from eliminative degradation of EQ-PCMVL were critical in the formulation of its structure. The isomerization of PCMVL to EQ-PCMVL is a direct consequence of the presence of the second ester functional group in the CMVL ester-lactone, a rarely studied class of monomer. Zn(II)-catalysis of the ROTEP of the isomeric β-lactone, 2-(2-carbomethoxyethyl)propiolactone (isoCMVL), as well as isomerization of the isostructural linear homopolymer derived from that isomeric monomer, led to the same EQ-PCMVL. These results suggest a new strategy for the introduction of branching into various polyesters.

Original language	English (US)
Pages (from-to)	1144-1148
Number of pages	5
Journal	ACS Macro Letters
Volume	7
Issue number	10
DOIs	https://doi.org/10.1021/acsmacrolett.8b00621
State	Published - Oct 16 2018

Bibliographical note

Funding Information:
Financial support for this work was provided by the Center for Sustainable Polymers at the University of Minnesota, an NSF-supported Center for Chemical Innovation (CHE-1413862). Some of the NMR data were obtained with an instrument whose purchase was enabled by the NIH Shared Instrumentation Grant Program (S10OD011952).

Publisher Copyright:
Copyright © 2018 American Chemical Society.

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abstract = "We report here the Zn(II)-catalyzed convergence of two metastable and isostructural polyesters to an isomeric polymer having a hyperbranched architecture. Ring-opening transesterification polymerization (ROTEP) of 4-carbomethoxyvalerolactone (CMVL) under Br{\o}nsted catalysis is known to give the linear polyester PCMVL. We show here that this can be isomerized to the equilibrated (and highly branched) polyester EQ-PCMVL. Analysis of the fragments obtained from eliminative degradation of EQ-PCMVL were critical in the formulation of its structure. The isomerization of PCMVL to EQ-PCMVL is a direct consequence of the presence of the second ester functional group in the CMVL ester-lactone, a rarely studied class of monomer. Zn(II)-catalysis of the ROTEP of the isomeric β-lactone, 2-(2-carbomethoxyethyl)propiolactone (isoCMVL), as well as isomerization of the isostructural linear homopolymer derived from that isomeric monomer, led to the same EQ-PCMVL. These results suggest a new strategy for the introduction of branching into various polyesters.",

author = "Fahnhorst, {Grant W.} and Stasiw, {Daniel E.} and Tolman, {William B.} and Hoye, {Thomas R.}",

note = "Funding Information: Financial support for this work was provided by the Center for Sustainable Polymers at the University of Minnesota, an NSF-supported Center for Chemical Innovation (CHE-1413862). Some of the NMR data were obtained with an instrument whose purchase was enabled by the NIH Shared Instrumentation Grant Program (S10OD011952). Publisher Copyright: Copyright {\textcopyright} 2018 American Chemical Society.",

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doi = "10.1021/acsmacrolett.8b00621",

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AU - Stasiw, Daniel E.

AU - Tolman, William B.

AU - Hoye, Thomas R.

N1 - Funding Information: Financial support for this work was provided by the Center for Sustainable Polymers at the University of Minnesota, an NSF-supported Center for Chemical Innovation (CHE-1413862). Some of the NMR data were obtained with an instrument whose purchase was enabled by the NIH Shared Instrumentation Grant Program (S10OD011952). Publisher Copyright: Copyright © 2018 American Chemical Society.

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N2 - We report here the Zn(II)-catalyzed convergence of two metastable and isostructural polyesters to an isomeric polymer having a hyperbranched architecture. Ring-opening transesterification polymerization (ROTEP) of 4-carbomethoxyvalerolactone (CMVL) under Brønsted catalysis is known to give the linear polyester PCMVL. We show here that this can be isomerized to the equilibrated (and highly branched) polyester EQ-PCMVL. Analysis of the fragments obtained from eliminative degradation of EQ-PCMVL were critical in the formulation of its structure. The isomerization of PCMVL to EQ-PCMVL is a direct consequence of the presence of the second ester functional group in the CMVL ester-lactone, a rarely studied class of monomer. Zn(II)-catalysis of the ROTEP of the isomeric β-lactone, 2-(2-carbomethoxyethyl)propiolactone (isoCMVL), as well as isomerization of the isostructural linear homopolymer derived from that isomeric monomer, led to the same EQ-PCMVL. These results suggest a new strategy for the introduction of branching into various polyesters.

AB - We report here the Zn(II)-catalyzed convergence of two metastable and isostructural polyesters to an isomeric polymer having a hyperbranched architecture. Ring-opening transesterification polymerization (ROTEP) of 4-carbomethoxyvalerolactone (CMVL) under Brønsted catalysis is known to give the linear polyester PCMVL. We show here that this can be isomerized to the equilibrated (and highly branched) polyester EQ-PCMVL. Analysis of the fragments obtained from eliminative degradation of EQ-PCMVL were critical in the formulation of its structure. The isomerization of PCMVL to EQ-PCMVL is a direct consequence of the presence of the second ester functional group in the CMVL ester-lactone, a rarely studied class of monomer. Zn(II)-catalysis of the ROTEP of the isomeric β-lactone, 2-(2-carbomethoxyethyl)propiolactone (isoCMVL), as well as isomerization of the isostructural linear homopolymer derived from that isomeric monomer, led to the same EQ-PCMVL. These results suggest a new strategy for the introduction of branching into various polyesters.

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Isomerization of Linear to Hyperbranched Polymers: Two Isomeric Lactones Converge via Metastable Isostructural Polyesters to a Highly Branched Analogue

Abstract

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