4-dimensional modeling strategy for an improved understanding of miniemulsion NMP of acrylates initiated by SG1-macroinitiator
- Author
- Paul Van Steenberge (UGent) , Dagmar D'hooge (UGent) , Marie-Françoise Reyniers (UGent) , Guy Marin (UGent) and M.F. Cunningham
- Organization
- Abstract
- For the first time, a kinetic model considering four-dimensional SmithEwart equations is presented to simultaneously calculate the time evolution of the conversion, number-average chain length, dispersity, end-group functionality (EGF), and short chain branching (SCB) content for the miniemulsion NMP of n-butyl acrylate (nBuA), initiated by poly(nBuA)-(N-tert-butyl-N-(1-diethylphosphono-2,2-dimethylpropyl) at 393 K ([nBuA](0):[poly(nBuA)-SG1](0) = 300). On the basis of literature kinetic and diffusion parameters, model analysis reveals that backbiting cannot be neglected for an accurate description of the NMP characteristics, despite the low number of SCBs formed per chain (ca. 2) and that the small loss of EGF at low conversions is mainly caused by chain transfer to monomer. SG1 partitioning (partitioning coefficient G = 50) between the organic and aqueous phase increases the dispersity and polymerization rate at low particle diameters (dp < ca. 50 nm) with a limited effect on the EGF profile. However, the extent of these increases is very sensitive to the G value, highlighting the relevance of its accurate experimental determination in future studies.
- Keywords
- MEDIATED RADICAL POLYMERIZATION, N-BUTYL ACRYLATE, DIFFUSION-CONTROLLED REACTIONS, DISPERSED SYSTEMS, CHAIN TRANSFER, MULTIBLOCK COPOLYMERS, METHYL-METHACRYLATE, RAFT POLYMERIZATION, HIGH CONVERSION, NITROXIDE
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Citation
Please use this url to cite or link to this publication: http://hdl.handle.net/1854/LU-5874228
- MLA
- Van Steenberge, Paul, et al. “4-Dimensional Modeling Strategy for an Improved Understanding of Miniemulsion NMP of Acrylates Initiated by SG1-Macroinitiator.” MACROMOLECULES, vol. 47, no. 22, 2014, pp. 7732–41, doi:10.1021/ma501746r.
- APA
- Van Steenberge, P., D’hooge, D., Reyniers, M.-F., Marin, G., & Cunningham, M. F. (2014). 4-dimensional modeling strategy for an improved understanding of miniemulsion NMP of acrylates initiated by SG1-macroinitiator. MACROMOLECULES, 47(22), 7732–7741. https://doi.org/10.1021/ma501746r
- Chicago author-date
- Van Steenberge, Paul, Dagmar D’hooge, Marie-Françoise Reyniers, Guy Marin, and M.F. Cunningham. 2014. “4-Dimensional Modeling Strategy for an Improved Understanding of Miniemulsion NMP of Acrylates Initiated by SG1-Macroinitiator.” MACROMOLECULES 47 (22): 7732–41. https://doi.org/10.1021/ma501746r.
- Chicago author-date (all authors)
- Van Steenberge, Paul, Dagmar D’hooge, Marie-Françoise Reyniers, Guy Marin, and M.F. Cunningham. 2014. “4-Dimensional Modeling Strategy for an Improved Understanding of Miniemulsion NMP of Acrylates Initiated by SG1-Macroinitiator.” MACROMOLECULES 47 (22): 7732–7741. doi:10.1021/ma501746r.
- Vancouver
- 1.Van Steenberge P, D’hooge D, Reyniers M-F, Marin G, Cunningham MF. 4-dimensional modeling strategy for an improved understanding of miniemulsion NMP of acrylates initiated by SG1-macroinitiator. MACROMOLECULES. 2014;47(22):7732–41.
- IEEE
- [1]P. Van Steenberge, D. D’hooge, M.-F. Reyniers, G. Marin, and M. F. Cunningham, “4-dimensional modeling strategy for an improved understanding of miniemulsion NMP of acrylates initiated by SG1-macroinitiator,” MACROMOLECULES, vol. 47, no. 22, pp. 7732–7741, 2014.
@article{5874228, abstract = {{For the first time, a kinetic model considering four-dimensional SmithEwart equations is presented to simultaneously calculate the time evolution of the conversion, number-average chain length, dispersity, end-group functionality (EGF), and short chain branching (SCB) content for the miniemulsion NMP of n-butyl acrylate (nBuA), initiated by poly(nBuA)-(N-tert-butyl-N-(1-diethylphosphono-2,2-dimethylpropyl) at 393 K ([nBuA](0):[poly(nBuA)-SG1](0) = 300). On the basis of literature kinetic and diffusion parameters, model analysis reveals that backbiting cannot be neglected for an accurate description of the NMP characteristics, despite the low number of SCBs formed per chain (ca. 2) and that the small loss of EGF at low conversions is mainly caused by chain transfer to monomer. SG1 partitioning (partitioning coefficient G = 50) between the organic and aqueous phase increases the dispersity and polymerization rate at low particle diameters (dp < ca. 50 nm) with a limited effect on the EGF profile. However, the extent of these increases is very sensitive to the G value, highlighting the relevance of its accurate experimental determination in future studies.}}, author = {{Van Steenberge, Paul and D'hooge, Dagmar and Reyniers, Marie-Françoise and Marin, Guy and Cunningham, M.F.}}, issn = {{0024-9297}}, journal = {{MACROMOLECULES}}, keywords = {{MEDIATED RADICAL POLYMERIZATION,N-BUTYL ACRYLATE,DIFFUSION-CONTROLLED REACTIONS,DISPERSED SYSTEMS,CHAIN TRANSFER,MULTIBLOCK COPOLYMERS,METHYL-METHACRYLATE,RAFT POLYMERIZATION,HIGH CONVERSION,NITROXIDE}}, language = {{eng}}, number = {{22}}, pages = {{7732--7741}}, title = {{4-dimensional modeling strategy for an improved understanding of miniemulsion NMP of acrylates initiated by SG1-macroinitiator}}, url = {{http://doi.org/10.1021/ma501746r}}, volume = {{47}}, year = {{2014}}, }
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