Norbornene-containing dithiocarbamates for use in reversible addition-fragmentation chain transfer (RAFT) polymerization and ring-opening metathesis polymerization (ROMP)

Jeffrey C. Foster; Scott C. Radzinski; Sally E. Lewis; Matthew B. Slutzker; John B. Matson

doi:10.1016/j.polymer.2015.10.028

Norbornene-containing dithiocarbamates for use in reversible addition-fragmentation chain transfer (RAFT) polymerization and ring-opening metathesis polymerization (ROMP)

Jeffrey C. Foster, Scott C. Radzinski, Sally E. Lewis, Matthew B. Slutzker, John B. Matson

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

19 Scopus citations

Abstract

Two new dithiocarbamate chain transfer agents (CTAs) with norbornene-containing Z-groups were prepared for use in reversible addition-fragmentation chain transfer (RAFT) polymerization. CTA 1b, which contains an electron deficient norbornene imide Z-group, was found to effectively mediate RAFT polymerization of 2° more activated monomers (MAMs) but did not facilitate RAFT of 3° MAMs or less activated monomers (LAMs). In contrast, CTA 2, derived from a norbornene amine, was well suited for the polymerization of LAMs, but did not control RAFT of MAMs. Poly(vinyl acetate) (PVAc), prepared by RAFT polymerization mediated by CTA 2, possessed the expected CTA-derived α- and ω-end groups. Ring-opening metathesis polymerization (ROMP) of 2 was carried out, and full conversion to polymer was achieved within 20 min. Based on this result, ROMP grafting-through of a PVAc macromonomer derived from CTA 2 was carried out, resulting in the formation of a well-defined PVAc bottlebrush polymer with a narrow molecular weight distribution.

Original language	English
Pages (from-to)	205-211
Number of pages	7
Journal	Polymer
Volume	79
DOIs	https://doi.org/10.1016/j.polymer.2015.10.028
State	Published - Nov 19 2015
Externally published	Yes

Funding

This work was supported by the Army Research Office ( W911NF-14-1-0322 ) and the American Chemical Society Petroleum Research Fund ( 54884-DNI7 ). We thank Materia for catalyst as well as Hannah Tecson and Kyle Moran for experimental assistance. We also thank Prof. Amanda J. Morris (Virginia Tech) for use of instruments.

Funders	Funder number
Army Research Office	W911NF-14-1-0322
American Chemical Society Petroleum Research Fund	54884-DNI7

Keywords

RAFT polymerization
graft polymer
poly(vinyl acetate)

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10.1016/j.polymer.2015.10.028

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@article{dba69b1276064583857ad4e789daeb83,

title = "Norbornene-containing dithiocarbamates for use in reversible addition-fragmentation chain transfer (RAFT) polymerization and ring-opening metathesis polymerization (ROMP)",

abstract = "Two new dithiocarbamate chain transfer agents (CTAs) with norbornene-containing Z-groups were prepared for use in reversible addition-fragmentation chain transfer (RAFT) polymerization. CTA 1b, which contains an electron deficient norbornene imide Z-group, was found to effectively mediate RAFT polymerization of 2° more activated monomers (MAMs) but did not facilitate RAFT of 3° MAMs or less activated monomers (LAMs). In contrast, CTA 2, derived from a norbornene amine, was well suited for the polymerization of LAMs, but did not control RAFT of MAMs. Poly(vinyl acetate) (PVAc), prepared by RAFT polymerization mediated by CTA 2, possessed the expected CTA-derived α- and ω-end groups. Ring-opening metathesis polymerization (ROMP) of 2 was carried out, and full conversion to polymer was achieved within 20 min. Based on this result, ROMP grafting-through of a PVAc macromonomer derived from CTA 2 was carried out, resulting in the formation of a well-defined PVAc bottlebrush polymer with a narrow molecular weight distribution.",

keywords = "RAFT polymerization, graft polymer, poly(vinyl acetate)",

author = "Foster, {Jeffrey C.} and Radzinski, {Scott C.} and Lewis, {Sally E.} and Slutzker, {Matthew B.} and Matson, {John B.}",

year = "2015",

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doi = "10.1016/j.polymer.2015.10.028",

language = "English",

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T1 - Norbornene-containing dithiocarbamates for use in reversible addition-fragmentation chain transfer (RAFT) polymerization and ring-opening metathesis polymerization (ROMP)

AU - Foster, Jeffrey C.

AU - Radzinski, Scott C.

AU - Lewis, Sally E.

AU - Slutzker, Matthew B.

AU - Matson, John B.

PY - 2015/11/19

Y1 - 2015/11/19

N2 - Two new dithiocarbamate chain transfer agents (CTAs) with norbornene-containing Z-groups were prepared for use in reversible addition-fragmentation chain transfer (RAFT) polymerization. CTA 1b, which contains an electron deficient norbornene imide Z-group, was found to effectively mediate RAFT polymerization of 2° more activated monomers (MAMs) but did not facilitate RAFT of 3° MAMs or less activated monomers (LAMs). In contrast, CTA 2, derived from a norbornene amine, was well suited for the polymerization of LAMs, but did not control RAFT of MAMs. Poly(vinyl acetate) (PVAc), prepared by RAFT polymerization mediated by CTA 2, possessed the expected CTA-derived α- and ω-end groups. Ring-opening metathesis polymerization (ROMP) of 2 was carried out, and full conversion to polymer was achieved within 20 min. Based on this result, ROMP grafting-through of a PVAc macromonomer derived from CTA 2 was carried out, resulting in the formation of a well-defined PVAc bottlebrush polymer with a narrow molecular weight distribution.

AB - Two new dithiocarbamate chain transfer agents (CTAs) with norbornene-containing Z-groups were prepared for use in reversible addition-fragmentation chain transfer (RAFT) polymerization. CTA 1b, which contains an electron deficient norbornene imide Z-group, was found to effectively mediate RAFT polymerization of 2° more activated monomers (MAMs) but did not facilitate RAFT of 3° MAMs or less activated monomers (LAMs). In contrast, CTA 2, derived from a norbornene amine, was well suited for the polymerization of LAMs, but did not control RAFT of MAMs. Poly(vinyl acetate) (PVAc), prepared by RAFT polymerization mediated by CTA 2, possessed the expected CTA-derived α- and ω-end groups. Ring-opening metathesis polymerization (ROMP) of 2 was carried out, and full conversion to polymer was achieved within 20 min. Based on this result, ROMP grafting-through of a PVAc macromonomer derived from CTA 2 was carried out, resulting in the formation of a well-defined PVAc bottlebrush polymer with a narrow molecular weight distribution.

KW - RAFT polymerization

KW - graft polymer

KW - poly(vinyl acetate)

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Norbornene-containing dithiocarbamates for use in reversible addition-fragmentation chain transfer (RAFT) polymerization and ring-opening metathesis polymerization (ROMP)

Abstract

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Keywords

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