Effect of dilution on branching and gelation in living copolymerization of monomer and divinyl cross-linker: Modeling using dynamic lattice liquid model (DLL) and Flory–Stockmayer (FS) model

Polanowski, Piotr; Jeszka, J.K.; Li, Wenwen; Matyjaszewski, Krzysztof

doi:10.1016/j.polymer.2011.08.055

Cited by 52 publications

(55 citation statements)

References 24 publications

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“…This is also of importance for hyperbranched polymers [23], due to the high density of neighboring reactive groups. It is acknowledged dilution increases the likelihood of intramolecular loop formation due to the reduced probability inter-molecular reaction between diluted molecules [55,57,63]. Following Dušková-Smrčková et al [57], we have observed that, in the formulations with a lower LP800 content, the ratio ‫ݔ‬ ‫ݔ‬ ,ௗ ⁄ scales well with the stoichiometric ratio, ‫ݎ‬ , that is approximately equivalent to the inverse of the amine concentration in the formulation.…”

Section: Comparison Of Theory With Experimentssupporting

confidence: 65%

Structural analysis of the curing of epoxy thermosets crosslinked with hyperbranched poly(ethyleneimine)s

Fernández‐Francos

Ramis

2015

European Polymer Journal

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The network build-up process during curing of an epoxy resin using a hyperbranched poly(ethyleneimine) as crosslinking agent has been studied from a theoretical and experimental point of view. A systematic analysis taking into account the stoichiometry of the curing process has been performed. Conversion at gelation has been studied by thermomechanical analysis (TMA) and differential scanning calorimetry (DSC). Crosslinking density has been studied by dynamomechanical analysis (DMA). Gel fraction after extraction in organic solvents has also been determined. The experimental results have been compared with a theoretical network build-up model based on the random recombination of structural fragments, showing good agreement between theory and experimental results, but deviations from the ideal epoxy-amine polycondensation appear as a consequence of the dilution of the hyperbranched crosslinker in off-stoichiometric formulations.  Expressions for relevant pre-gel and post-gel statistical averages are derived.  Experimental validation of predicted crosslinking and gelation is performed.  Nonidealities due to the densely branched structure of the crosslinker are described. ABSTRACTThe network build-up process during curing of an epoxy resin using a hyperbranched poly(ethyleneimine)as crosslinking agent has been studied from a theoretical and experimental point of view. A systematic analysis taking into account the stoichiometry of the curing process has been performed. Conversion at gelation has been studied by thermomechanical analysis (TMA) and differential scanning calorimetry (DSC). Crosslinking density has been studied by dynamomechanical analysis (DMA). Gel fraction after extraction in organic solvents has also been determined. The experimental results have been compared with a theoretical network build-up model based on the random recombination of structural fragments,showing good agreement between theory and experimental results, but deviations from the ideal epoxyamine polycondensation appear as a consequence of the dilution of the hyperbranched crosslinker in offstoichiometric formulations.

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Section: Comparison Of Theory With Experimentssupporting

confidence: 65%

Structural analysis of the curing of epoxy thermosets crosslinked with hyperbranched poly(ethyleneimine)s

Fernández‐Francos

Ramis

2015

European Polymer Journal

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“…[33] Similar conclusions were also found in the RAFT copolymerization of MVMs and monovinyl monomers. [36,37] Other studies have shown that the existence of partial intramolecular cyclization led to a discrepancy from F-S theory if the polymerization was conducted under dilute conditions. [12,30,35] By copolymerizing methyl acrylate (MA) and ethylene glycol diacrylate (EGDA), [35] they found that gelation occurred when the concentration of the reacted pendant vinyl groups was larger than that of primary chains and that the resulting gel had a more homogeneous structure.…”

Section: Copolymerization As Cross-linkersmentioning

confidence: 99%

“…Their subsequent simulation studies showed that intramolecular cyclization occurred in this ATRP copolymerization system. [36,37] Other studies have shown that the existence of partial intramolecular cyclization led to a discrepancy from F-S theory if the polymerization was conducted under dilute conditions. [34,38]…”

Section: Copolymerization As Cross-linkersmentioning

confidence: 99%

Controlled Polymerization of Multivinyl Monomers: Formation of Cyclized/Knotted Single‐Chain Polymer Architectures

et al. 2016

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Seventy years ago, Flory and Stockmayer predicted that the polymerization of multivinyl monomers (MVMs) would inevitably lead to insoluble cross-linked gel networks. Since then, the use of MVMs has largely been limited to as cross-linking agents. More recently, however, polymerization strategies such as reversible deactivation radical polymerization (RDRP) have paved the way for the exploration of new possibilities in terms of both polymer architectures and functional capabilities. This Minireview provides historical context to the problem of polymerizing MVMs, before highlighting how RDRP has led to the formation of new cyclized/knotted polymer structures. Although the potential of such cyclized/knot polymer architectures is far from being fulfilled, some emerging applications are discussed.

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“…[23] The synthesis of polymer networks by these RDRP techniques, in principle also allows the production of less heterogeneous structures (in terms of crosslink density distribution), as reviewed in the literature. [20,[23][24][25][26][27][28] The modeling of the kinetics of copolymerization of vinyl/divinyl monomers in the presence of Iniferter, [29] ATRP, [30][31][32][33][34][35][36][37][38][39] NMRP, [28,36,38,[40][41][42][43] and RAFT [44][45][46][47][48][49][50] controllers has started to be addressed in the literature. Galerkin finite element (GFE), [51] Monte Carlo (MC), [51] and other kinetic methods, including the method of moments, with either monofunctional [40] or multifunctional techniques [28,49,50] have been used.…”

Section: Introductionmentioning

confidence: 99%

Modeling the Kinetics of Monolith Formation by RAFT Copolymerization of Styrene and Divinylbenzene

López‐Domínguez

Hernández‐Ortiz

Barlow

et al. 2014

Macromol. React. Eng.

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The synthesis of monoliths by reversible addition‐fragmentation chain transfer (RAFT) copolymerization of styrene and divinylbenzene (DVB) at high‐crosslinker content is studied using the recently reported multifunctional polymer molecule approach. The agreement between model predictions, incorporating diffusion‐control, and experimental data from CSIRO is good for all cases analyzed. This includes examples with high‐crosslinker concentrations, which cause deviation from some of the simplifying assumptions imposed in the model.

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Effect of dilution on branching and gelation in living copolymerization of monomer and divinyl cross-linker: Modeling using dynamic lattice liquid model (DLL) and Flory–Stockmayer (FS) model

Cited by 52 publications

References 24 publications

Structural analysis of the curing of epoxy thermosets crosslinked with hyperbranched poly(ethyleneimine)s

Structural analysis of the curing of epoxy thermosets crosslinked with hyperbranched poly(ethyleneimine)s

Controlled Polymerization of Multivinyl Monomers: Formation of Cyclized/Knotted Single‐Chain Polymer Architectures

Modeling the Kinetics of Monolith Formation by RAFT Copolymerization of Styrene and Divinylbenzene

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