Polymer chain extension in semibatch emulsion polymerization with RAFT‐based transfer agent: The influence of reaction conditions on polymerization rate and product properties

Altarawneh, Ibrahem; Gomes, Vincent G.; Srour, M.H.

doi:10.1002/app.30752

Cited by 10 publications

(9 citation statements)

References 43 publications

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“…A* [103,493] (St) [510,511] (BA) [112] (BA) [511] (MA) [511] NIPAm [112] VAc [512] VPv [513] NVC [514] NVP [103,493,515] NVP [513] NVPip [516] NVC [514,515] VAc/VPv [513] (BA-b-St) [511] (MA-b-St) [511] BA-b-NIPAm [112] NVC-b-Ac [514] NVP-b-NVC [515] NVPip-b-VAc [516] NVC-b-NVP [515] NVC-b-VAc [514] (NIPAm/NVPI) [517] (Continued ) [512] (VAc) [512] (230) [512] (230-b-VAc) [512] 231…”

Section: O S S Cnmentioning

confidence: 99%

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Living Radical Polymerization by the RAFT Process – A Third Update

2012

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This paper provides a third update to the review of reversible deactivation radical polymerization (RDRP) achieved with thiocarbonylthio compounds (ZC(¼S)SR) by a mechanism of reversible addition-fragmentation chain transfer ( Chem. 2009Chem. , 62, 1402. This review cites over 700 publications that appeared during the period mid 2009 to early 2012 covering various aspects of RAFT polymerization which include reagent synthesis and properties, kinetics and mechanism of polymerization, novel polymer syntheses, and a diverse range of applications. This period has witnessed further significant developments, particularly in the areas of novel RAFT agents, techniques for end-group transformation, the production of micro/nanoparticles and modified surfaces, and biopolymer conjugates both for therapeutic and diagnostic applications.

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Section: O S S Cnmentioning

confidence: 99%

“…In this context several groups have studied the kinetics of the RAFT emulsion polymerization of St [495,510] with xanthate RAFT agents. A detailed study of RAFT microemulsion of BA with xanthate RAFT agents has also been performed.…”

Section: Raft Polymerization In Heterogeneous Mediamentioning

confidence: 99%

Living Radical Polymerization by the RAFT Process – A Third Update

2012

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“…Despite that the investigation of RAFT in (mini)emulsion polymerization can be advantageous to investigate the plausibility of the chosen retardation model, a detailed kinetic study over a wide range of theoretically relevant RAFT addition, fragmentation, and cross-termination rate coefficients as a function of the average particle size is still lacking. Most kinetic modeling studies on RAFT (mini)emulsion polymerization are simplified [ 23 , 32 , 100 , 101 , 102 , 103 , 104 , 105 , 106 , 107 , 108 , 109 , 110 , 111 , 112 ] with the common assumption [ 23 , 103 , 104 , 110 , 112 ] of a zero-one system, hence, either droplets/particles contain one or no radical at all. For example, Altarawneh et al [ 103 , 104 ] used a zero-one model to describe the RAFT emulsion polymerization of styrene mediated by O -ethylxanthyl ethyl propionate.…”

Section: Introductionmentioning

confidence: 99%

Modeling of Miniemulsion Polymerization of Styrene with Macro-RAFT Agents to Theoretically Compare Slow Fragmentation, Ideal Exchange and Cross-Termination Cases

et al. 2019

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A 5-dimensional Smith-Ewart based model is developed to understand differences for reversible addition-fragmentation chain transfer (RAFT) miniemulsion polymerization with theoretical agents mimicking cases of slow fragmentation, cross-termination, and ideal exchange while accounting for chain length and monomer conversion dependencies due to diffusional limitations. The focus is on styrene as a monomer, a water soluble initiator, and a macro-RAFT agent to avoid exit/entry of the RAFT leaving group radical. It is shown that with a too low RAFT fragmentation rate coefficient it is generally not afforded to consider zero-one kinetics (for the related intermediate radical type) and that with significant RAFT cross-termination the dead polymer product is dominantly originating from the RAFT intermediate radical. To allow the identification of the nature of the RAFT retardation it is recommended to experimentally investigate in the future the impact of the average particle size (dp) on both the monomer conversion profile and the average polymer properties for a sufficiently broad dp range, ideally including the bulk limit. With decreasing particle size both a slow RAFT fragmentation and a fast RAFT cross-termination result in a stronger segregation and thus rate acceleration. The particle size dependency is different, allowing further differentiation based on the variation of the dispersity and end-group functionality. Significant RAFT cross-termination is specifically associated with a strong dispersity increase at higher average particle sizes. Only with an ideal exchange it is afforded in the modeling to avoid the explicit calculation of the RAFT intermediate concentration evolution.

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“…While in the case of nonionic surfactants, the continuous addition of surfactants will increase the steric effect, making it harder for the monomer molecules to approach each other which will eventually lead to the formation of small size particles. The increase in the number of micelles affords a high number of active centers in the polymerization initiation step, resulting in faster monomer conversion rates and smaller size particles [25,26].…”

Section: The Effect Of Surfactant Concentrationmentioning

confidence: 99%