Fusing light-induced step-growth processes with RAFT chemistry for segmented copolymer synthesis : a synergetic experimental and kinetic modeling study
- Author
- Thomas Gegenhuber, Lies De Keer, Anja Goldmann, Paul Van Steenberge (UGent) , Jan Mueller, Marie-Françoise Reyniers (UGent) , Jan Menzel, Dagmar D'hooge (UGent) and Christopher Barner-Kowollik
- Organization
- Abstract
- We pioneer the synthesis of well-defined high molar mass segmented copolymers, employing a unique combination of step-growth and reversible addition−fragmentation chain transfer (RAFT) polymerization. The step-growth precursor polymer is obtained via the ambient temperature UV-light-induced Diels−Alder reaction of 6′-(propane-1,3- diylbis(oxy))bis(2-methylbenzaldehyde) (AA monomer) and di(isopropionic ethyl ester fumarate) trithiocarbonate (BB monomer). Unconventional off-stoichiometric conditions (r = [AA]0:[BB]0 = 1.5−1.75) are employed to ensure a sufficiently high incorporation of BB in the step-growth product (1200 ≤ Mn/g mol−1 ≤ 3950). The optimum r value is based on a detailed product distribution analysis, comparing experimental and bivariate kinetic Monte Carlo generated data, using a scheme of over 200 reactions. The analysis highlights the unexpected occurrence of AA homopolymerization and the ligation of the resulting AA segments at higher reaction times. The precursor step-growth polymer is successfully transformed into a segmented copolymer via insertion of styrene by RAFT polymerization at 60 °C (11 200 ≤ Mn/g mol−1 ≤ 53 400), as confirmed both experimentally and through simulations.
- Keywords
- FRAGMENTATION-CHAIN TRANSFER, TRANSFER RADICAL POLYMERIZATION, DIELS-ALDER CHEMISTRY, END-GROUP REMOVAL, POLYMERS ADVANCES, TRANSFER AGENTS, STAR POLYMERS, DESIGN, LIGATION, CONJUGATION
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Citation
Please use this url to cite or link to this publication: http://hdl.handle.net/1854/LU-8536801
- MLA
- Gegenhuber, Thomas, et al. “Fusing Light-Induced Step-Growth Processes with RAFT Chemistry for Segmented Copolymer Synthesis : A Synergetic Experimental and Kinetic Modeling Study.” MACROMOLECULES, vol. 50, 2017, pp. 6451–67, doi:10.1021/acs.macromol.7b01394.
- APA
- Gegenhuber, T., De Keer, L., Goldmann, A., Van Steenberge, P., Mueller, J., Reyniers, M.-F., … Barner-Kowollik, C. (2017). Fusing light-induced step-growth processes with RAFT chemistry for segmented copolymer synthesis : a synergetic experimental and kinetic modeling study. MACROMOLECULES, 50, 6451–6467. https://doi.org/10.1021/acs.macromol.7b01394
- Chicago author-date
- Gegenhuber, Thomas, Lies De Keer, Anja Goldmann, Paul Van Steenberge, Jan Mueller, Marie-Françoise Reyniers, Jan Menzel, Dagmar D’hooge, and Christopher Barner-Kowollik. 2017. “Fusing Light-Induced Step-Growth Processes with RAFT Chemistry for Segmented Copolymer Synthesis : A Synergetic Experimental and Kinetic Modeling Study.” MACROMOLECULES 50: 6451–67. https://doi.org/10.1021/acs.macromol.7b01394.
- Chicago author-date (all authors)
- Gegenhuber, Thomas, Lies De Keer, Anja Goldmann, Paul Van Steenberge, Jan Mueller, Marie-Françoise Reyniers, Jan Menzel, Dagmar D’hooge, and Christopher Barner-Kowollik. 2017. “Fusing Light-Induced Step-Growth Processes with RAFT Chemistry for Segmented Copolymer Synthesis : A Synergetic Experimental and Kinetic Modeling Study.” MACROMOLECULES 50: 6451–6467. doi:10.1021/acs.macromol.7b01394.
- Vancouver
- 1.Gegenhuber T, De Keer L, Goldmann A, Van Steenberge P, Mueller J, Reyniers M-F, et al. Fusing light-induced step-growth processes with RAFT chemistry for segmented copolymer synthesis : a synergetic experimental and kinetic modeling study. MACROMOLECULES. 2017;50:6451–67.
- IEEE
- [1]T. Gegenhuber et al., “Fusing light-induced step-growth processes with RAFT chemistry for segmented copolymer synthesis : a synergetic experimental and kinetic modeling study,” MACROMOLECULES, vol. 50, pp. 6451–6467, 2017.
@article{8536801,
abstract = {{We pioneer the synthesis of well-defined high molar mass segmented copolymers, employing a unique combination of step-growth and reversible addition−fragmentation chain transfer (RAFT) polymerization. The step-growth precursor polymer is obtained via the ambient temperature UV-light-induced Diels−Alder reaction of 6′-(propane-1,3-
diylbis(oxy))bis(2-methylbenzaldehyde) (AA monomer) and di(isopropionic ethyl ester fumarate) trithiocarbonate (BB
monomer). Unconventional off-stoichiometric conditions (r = [AA]0:[BB]0 = 1.5−1.75) are employed to ensure a sufficiently high incorporation of BB in the step-growth product (1200 ≤ Mn/g mol−1 ≤ 3950). The optimum r value is based on a detailed product distribution analysis, comparing experimental and bivariate kinetic Monte Carlo generated data, using a scheme of over 200 reactions. The analysis highlights the unexpected occurrence of AA homopolymerization and the ligation of the resulting AA segments at higher reaction times. The precursor step-growth polymer is successfully transformed into a segmented copolymer via insertion of styrene by RAFT polymerization at 60 °C (11 200 ≤ Mn/g mol−1 ≤ 53 400), as confirmed both experimentally and through simulations.}},
author = {{Gegenhuber, Thomas and De Keer, Lies and Goldmann, Anja and Van Steenberge, Paul and Mueller, Jan and Reyniers, Marie-Françoise and Menzel, Jan and D'hooge, Dagmar and Barner-Kowollik, Christopher}},
issn = {{0024-9297}},
journal = {{MACROMOLECULES}},
keywords = {{FRAGMENTATION-CHAIN TRANSFER,TRANSFER RADICAL POLYMERIZATION,DIELS-ALDER CHEMISTRY,END-GROUP REMOVAL,POLYMERS ADVANCES,TRANSFER AGENTS,STAR POLYMERS,DESIGN,LIGATION,CONJUGATION}},
language = {{eng}},
pages = {{6451--6467}},
title = {{Fusing light-induced step-growth processes with RAFT chemistry for segmented copolymer synthesis : a synergetic experimental and kinetic modeling study}},
url = {{http://doi.org/10.1021/acs.macromol.7b01394}},
volume = {{50}},
year = {{2017}},
}
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