Advanced search
2 files | 1.05 MB

Straightforward synthesis of functionalized cyclic polymers in high yield via RAFT and thiolactone-disulfide chemistry

(2013) POLYMER CHEMISTRY. 4(1). p.184-193
Author
Organization
Abstract
An efficient synthetic pathway toward cyclic polymers based on the combination of thiolactone and disulfide chemistry has been developed. First, heterotelechelic linear polystyrene (PS) containing an alpha-thiolactone (TLa) and an omega-dithiobenzoate group was synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization, employing a newly designed TLa-bearing chain transfer agent (CTA). The subsequent reaction of this heterotelechelic polymer with an amine, which acts as a nucleophile for both the TLa and dithiobenzoate units, generated the alpha,omega-thiol-telechelic PS under ambient conditions without the need for any catalyst or other additives. The arrangement of thiols under a high dilution afforded single cyclic PS (c-PS) through an oxidative disulfide linkage. The cyclic PS (c-PS) disulfide ring formation was evidenced by SEC, MALDI-TOF MS and H-1-NMR characterization. Moreover, we demonstrated a controlled ring opening via either disulfide reduction or thiol-disulfide exchange to enable easy and clean topology transformation. Furthermore, to illustrate the broad utility of this synthetic methodology, different amines including functional ones were employed, allowing for the one-step preparation of functionalized cyclic polymers with high yields.
Keywords
TOPOLOGIES, RING-CLOSURE, POLYSTYRENES, EFFICIENT ROUTE, MASS-SPECTROMETRY, COVALENT FIXATION, RADICAL POLYMERIZATION, BLOCK-COPOLYMERS, KeyWords Plus: FRAGMENTATION-CHAIN-TRANSFER, CLICK CHEMISTRY

Downloads

  • (...).pdf
    • full text
    • |
    • UGent only
    • |
    • PDF
    • |
    • 486.41 KB
  • Revised MS Milan Stamenovic Straightforward synthesis 2013 .pdf
    • full text
    • |
    • open access
    • |
    • PDF
    • |
    • 565.29 KB

Citation

Please use this url to cite or link to this publication:

Chicago
Stamenović, Milan M., Pieter Espeel, Eisuke Baba, Takuya Yamamoto, Yasuyuki Tezuka, and Filip Du Prez. 2013. “Straightforward Synthesis of Functionalized Cyclic Polymers in High Yield via RAFT and Thiolactone-disulfide Chemistry.” Polymer Chemistry 4 (1): 184–193.
APA
Stamenović, M. M., Espeel, P., Baba, E., Yamamoto, T., Tezuka, Y., & Du Prez, F. (2013). Straightforward synthesis of functionalized cyclic polymers in high yield via RAFT and thiolactone-disulfide chemistry. POLYMER CHEMISTRY, 4(1), 184–193.
Vancouver
1.
Stamenović MM, Espeel P, Baba E, Yamamoto T, Tezuka Y, Du Prez F. Straightforward synthesis of functionalized cyclic polymers in high yield via RAFT and thiolactone-disulfide chemistry. POLYMER CHEMISTRY. 2013;4(1):184–93.
MLA
Stamenović, Milan M., Pieter Espeel, Eisuke Baba, et al. “Straightforward Synthesis of Functionalized Cyclic Polymers in High Yield via RAFT and Thiolactone-disulfide Chemistry.” POLYMER CHEMISTRY 4.1 (2013): 184–193. Print.
@article{3093118,
  abstract     = {An efficient synthetic pathway toward cyclic polymers based on the combination of thiolactone and disulfide chemistry has been developed. First, heterotelechelic linear polystyrene (PS) containing an alpha-thiolactone (TLa) and an omega-dithiobenzoate group was synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization, employing a newly designed TLa-bearing chain transfer agent (CTA). The subsequent reaction of this heterotelechelic polymer with an amine, which acts as a nucleophile for both the TLa and dithiobenzoate units, generated the alpha,omega-thiol-telechelic PS under ambient conditions without the need for any catalyst or other additives. The arrangement of thiols under a high dilution afforded single cyclic PS (c-PS) through an oxidative disulfide linkage. The cyclic PS (c-PS) disulfide ring formation was evidenced by SEC, MALDI-TOF MS and H-1-NMR characterization. Moreover, we demonstrated a controlled ring opening via either disulfide reduction or thiol-disulfide exchange to enable easy and clean topology transformation. Furthermore, to illustrate the broad utility of this synthetic methodology, different amines including functional ones were employed, allowing for the one-step preparation of functionalized cyclic polymers with high yields.},
  author       = {Stamenovi\'{c}, Milan M. and Espeel, Pieter and Baba, Eisuke and Yamamoto, Takuya and Tezuka, Yasuyuki and Du Prez, Filip},
  issn         = {1759-9954},
  journal      = {POLYMER CHEMISTRY},
  keyword      = {TOPOLOGIES,RING-CLOSURE,POLYSTYRENES,EFFICIENT ROUTE,MASS-SPECTROMETRY,COVALENT FIXATION,RADICAL POLYMERIZATION,BLOCK-COPOLYMERS,KeyWords Plus: FRAGMENTATION-CHAIN-TRANSFER,CLICK CHEMISTRY},
  language     = {eng},
  number       = {1},
  pages        = {184--193},
  title        = {Straightforward synthesis of functionalized cyclic polymers in high yield via RAFT and thiolactone-disulfide chemistry},
  url          = {http://dx.doi.org/10.1039/c2py20751f},
  volume       = {4},
  year         = {2013},
}

Altmetric
View in Altmetric
Web of Science
Times cited: