Impact of Macromonomer Molar Mass and Feed Composition on Branch Distributions in Model Graft Copolymerizations

Aristotelis Zografos; Nathaniel A. Lynd; Frank S. Bates; Marc A. Hillmyer

doi:10.1021/acsmacrolett.1c00640

Impact of Macromonomer Molar Mass and Feed Composition on Branch Distributions in Model Graft Copolymerizations

Aristotelis Zografos, Nathaniel A. Lynd, Frank S. Bates, Marc A. Hillmyer

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

16 Scopus citations

Abstract

Graft polymers are useful in a versatile range of material applications. Understanding how changes to the grafted architecture, such as the grafting density (z), the side-chain degree of polymerization (N_sc), and the backbone degree of polymerization (N_bb), affect polymer properties is critical for accurately tuning material performance. For graft-through copolymerizations, changes to N_sc and z are controlled by the macromonomer degree of polymerization (N_MM) and the initial fraction of the macromonomer in the feed (f_MM⁰), respectively. We show that changes to these parameters can influence the copolymerization reactivity ratios and, in turn, impact the side-chain distribution along a graft polymer backbone. Poly((±)-lactide) macromonomers with N_MM values as low as ca. 1 and as high as 72 were copolymerized with a small-molecule dimethyl ester norbornene comonomer over a range of f_MM⁰ values (0.1 ≤ f_MM⁰ ≤ 0.8) using ring-opening metathesis polymerization (ROMP). Monomer conversion was determined using ¹H nuclear magnetic resonance spectroscopy, and the data were fit with terminal and nonterminal copolymerization models. The results from this work provide essential information for manipulating N_sc and z while maintaining synthetic control over the side-chain distribution for graft-through copolymerizations.

Original language	English (US)
Pages (from-to)	1622-1628
Number of pages	7
Journal	ACS Macro Letters
Volume	10
Issue number	12
DOIs	https://doi.org/10.1021/acsmacrolett.1c00640
State	Published - Dec 21 2021

Bibliographical note

Funding Information:
Support for this work was provided by the National Science Foundation (NSF) Center for Sustainable Polymers (CHE-1901635) at the University of Minnesota,as well as the NSF Graduate Research Fellowship Program (DGE-1839286). H NMR experiments were conducted at the University of Minnesota Nuclear Magnetic Resonance Laboratory using an instrument that is supported by the Director, National Institutes of Health (S10OD011952). The content of this work is solely the responsibility of the authors and does not necessarily represent the official views of the National Institutes of Health. We thank Dr. Alice B. Chang, Dr. Michael G. Hyatt, Dr. Michael B. Sims, Dr. Christopher DeRosa, and Dr. Lucie Fournier for helpful discussions and insight regarding polymer and monomer synthesis. We also acknowledge Dr. Alice B. Chang and Dr. Christopher DeRosa for providing the exo, exo-norbornene alcohol initiator used to synthesize the macromonomers. Lastly, we thank Dr. Letitia Yao, Dr. Michael B. Sims, and Claire Dingwell for their helpful insights regarding NMR characterization. 1

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© 2021 American Chemical Society.

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title = "Impact of Macromonomer Molar Mass and Feed Composition on Branch Distributions in Model Graft Copolymerizations",

abstract = "Graft polymers are useful in a versatile range of material applications. Understanding how changes to the grafted architecture, such as the grafting density (z), the side-chain degree of polymerization (Nsc), and the backbone degree of polymerization (Nbb), affect polymer properties is critical for accurately tuning material performance. For graft-through copolymerizations, changes to Nsc and z are controlled by the macromonomer degree of polymerization (NMM) and the initial fraction of the macromonomer in the feed (fMM0), respectively. We show that changes to these parameters can influence the copolymerization reactivity ratios and, in turn, impact the side-chain distribution along a graft polymer backbone. Poly((±)-lactide) macromonomers with NMM values as low as ca. 1 and as high as 72 were copolymerized with a small-molecule dimethyl ester norbornene comonomer over a range of fMM0 values (0.1 ≤ fMM0 ≤ 0.8) using ring-opening metathesis polymerization (ROMP). Monomer conversion was determined using 1H nuclear magnetic resonance spectroscopy, and the data were fit with terminal and nonterminal copolymerization models. The results from this work provide essential information for manipulating Nsc and z while maintaining synthetic control over the side-chain distribution for graft-through copolymerizations.",

author = "Aristotelis Zografos and Lynd, \{Nathaniel A.\} and Bates, \{Frank S.\} and Hillmyer, \{Marc A.\}",

note = "Funding Information: Support for this work was provided by the National Science Foundation (NSF) Center for Sustainable Polymers (CHE-1901635) at the University of Minnesota,as well as the NSF Graduate Research Fellowship Program (DGE-1839286). H NMR experiments were conducted at the University of Minnesota Nuclear Magnetic Resonance Laboratory using an instrument that is supported by the Director, National Institutes of Health (S10OD011952). The content of this work is solely the responsibility of the authors and does not necessarily represent the official views of the National Institutes of Health. We thank Dr. Alice B. Chang, Dr. Michael G. Hyatt, Dr. Michael B. Sims, Dr. Christopher DeRosa, and Dr. Lucie Fournier for helpful discussions and insight regarding polymer and monomer synthesis. We also acknowledge Dr. Alice B. Chang and Dr. Christopher DeRosa for providing the exo, exo-norbornene alcohol initiator used to synthesize the macromonomers. Lastly, we thank Dr. Letitia Yao, Dr. Michael B. Sims, and Claire Dingwell for their helpful insights regarding NMR characterization. 1 Publisher Copyright: {\textcopyright} 2021 American Chemical Society.",

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doi = "10.1021/acsmacrolett.1c00640",

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T1 - Impact of Macromonomer Molar Mass and Feed Composition on Branch Distributions in Model Graft Copolymerizations

AU - Zografos, Aristotelis

AU - Lynd, Nathaniel A.

AU - Bates, Frank S.

AU - Hillmyer, Marc A.

N1 - Funding Information: Support for this work was provided by the National Science Foundation (NSF) Center for Sustainable Polymers (CHE-1901635) at the University of Minnesota,as well as the NSF Graduate Research Fellowship Program (DGE-1839286). H NMR experiments were conducted at the University of Minnesota Nuclear Magnetic Resonance Laboratory using an instrument that is supported by the Director, National Institutes of Health (S10OD011952). The content of this work is solely the responsibility of the authors and does not necessarily represent the official views of the National Institutes of Health. We thank Dr. Alice B. Chang, Dr. Michael G. Hyatt, Dr. Michael B. Sims, Dr. Christopher DeRosa, and Dr. Lucie Fournier for helpful discussions and insight regarding polymer and monomer synthesis. We also acknowledge Dr. Alice B. Chang and Dr. Christopher DeRosa for providing the exo, exo-norbornene alcohol initiator used to synthesize the macromonomers. Lastly, we thank Dr. Letitia Yao, Dr. Michael B. Sims, and Claire Dingwell for their helpful insights regarding NMR characterization. 1 Publisher Copyright: © 2021 American Chemical Society.

PY - 2021/12/21

Y1 - 2021/12/21

N2 - Graft polymers are useful in a versatile range of material applications. Understanding how changes to the grafted architecture, such as the grafting density (z), the side-chain degree of polymerization (Nsc), and the backbone degree of polymerization (Nbb), affect polymer properties is critical for accurately tuning material performance. For graft-through copolymerizations, changes to Nsc and z are controlled by the macromonomer degree of polymerization (NMM) and the initial fraction of the macromonomer in the feed (fMM0), respectively. We show that changes to these parameters can influence the copolymerization reactivity ratios and, in turn, impact the side-chain distribution along a graft polymer backbone. Poly((±)-lactide) macromonomers with NMM values as low as ca. 1 and as high as 72 were copolymerized with a small-molecule dimethyl ester norbornene comonomer over a range of fMM0 values (0.1 ≤ fMM0 ≤ 0.8) using ring-opening metathesis polymerization (ROMP). Monomer conversion was determined using 1H nuclear magnetic resonance spectroscopy, and the data were fit with terminal and nonterminal copolymerization models. The results from this work provide essential information for manipulating Nsc and z while maintaining synthetic control over the side-chain distribution for graft-through copolymerizations.

AB - Graft polymers are useful in a versatile range of material applications. Understanding how changes to the grafted architecture, such as the grafting density (z), the side-chain degree of polymerization (Nsc), and the backbone degree of polymerization (Nbb), affect polymer properties is critical for accurately tuning material performance. For graft-through copolymerizations, changes to Nsc and z are controlled by the macromonomer degree of polymerization (NMM) and the initial fraction of the macromonomer in the feed (fMM0), respectively. We show that changes to these parameters can influence the copolymerization reactivity ratios and, in turn, impact the side-chain distribution along a graft polymer backbone. Poly((±)-lactide) macromonomers with NMM values as low as ca. 1 and as high as 72 were copolymerized with a small-molecule dimethyl ester norbornene comonomer over a range of fMM0 values (0.1 ≤ fMM0 ≤ 0.8) using ring-opening metathesis polymerization (ROMP). Monomer conversion was determined using 1H nuclear magnetic resonance spectroscopy, and the data were fit with terminal and nonterminal copolymerization models. The results from this work provide essential information for manipulating Nsc and z while maintaining synthetic control over the side-chain distribution for graft-through copolymerizations.

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Impact of Macromonomer Molar Mass and Feed Composition on Branch Distributions in Model Graft Copolymerizations

Abstract

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