Nitroxide‐Mediated Polymerization of Styrene in a Continuous Tubular Reactor

Enright, Thomas E.; Cunningham, Michael F.; Keoshkerian, Barkev

doi:10.1002/marc.200400531

Cited by 67 publications

(53 citation statements)

References 21 publications

(16 reference statements)

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“…They also studied the influence of the rateaccelerating additive camphorsulfonic acid (CSA) in heterogeneous styrene miniemulsion polymerizations with TEMPO/BPO and HTEMPO/BPO systems, respectively [6]. Enright [7] first used a continuous tubular reactor apparatus and studied styrene miniemulsion polymerizations at 135uC using oligomers of polystyrene as a cosurfactant. The results indicated obvious living characteristics of polymerization and the polydispersity index (PDI) of the product was less than 1.4.…”

Section: Introductionmentioning

confidence: 99%

Controlled/living photopolymerization of methyl methacrylate in miniemulsion mediated by HTEMPO

2008

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Controlled/living photopolymerization of methyl methacrylate (MMA) in miniemulsion mediated by 4-hydroxy-2,2,6,6-tetramethyl-piperidinyloxy (HTEMPO) was carried out at ambient temperatures. MMA miniemulsion was prepared by using an anionic surfactant with cetylalcohol as a co-stabilizer. The photopolymerization led to stable lattices and they were obtained with no coagulation during synthesis and no destabilization over time. It was found that the obtained MMA homopolymers exhibited relatively narrow molecular weight distribution (PDI 5 1.27 2 1.36) which was characterized by GPC. The plots of number-average molecular weight in (M n ) vs. conversion and ln([M 0 ]/[M]) vs. time both were linear indicating that the reaction was a controlled/living free radical polymerization.

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Section: Introductionmentioning

confidence: 99%

Controlled/living photopolymerization of methyl methacrylate in miniemulsion mediated by HTEMPO

2008

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“…We have done a series of studies to demonstrate the feasibility of aqueous miniemulsion‐based NMP reactions in a continuous tubular reactor 13, 14. As the studies have progressed, there has been interest in characterizing the residence time distribution (RTD).…”

Section: Introductionmentioning

confidence: 99%

“…Initial NMP miniemulsion studies have shown that there is minimal difference in molecular weight distribution between materials prepared in a batch reactor versus continuous tubular reactor,14 suggesting a narrow RTD. However, it was also shown that conversion was slightly lower in the continuous tubular reactor compared to batch, and this was attributed to axial mixing effects.…”

Section: Introductionmentioning

confidence: 99%

Residence Time Distribution Study of a Living/Controlled Radical Miniemulsion Polymerization System in a Continuous Tubular Reactor

Enright¹,

Cunningham²

2011

Macro Reaction Engineering

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Residence time distribution (RTD) studies were done to determine the flow characteristics in a continuous tubular reactor. Pulse tracer experiments were done at different flow rates and temperatures, and a comparison was made between a homogeneous aqueous salt mixture versus a heterogeneous miniemulsion mixture. The heterogeneous system was studied under two different conditions, one with a monomer‐in‐water droplet dispersion and one with fully formed polymer particles dispersed in water. There were differences observed between all of the systems tested and none of them matched an ideal plug flow condition. The reactor contains stagnant zones of varying volume and tracer spreading was observed in all cases. The dispersion model was found to model the system quite well in most cases.

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“…Related to the specific topic of CLRP processes carried out in tubular reactors, Enright et al24 showed the feasibility of NMRP of styrene in such reactors. Zhang and Ray13 developed a mathematical model for NMRP in a tubular reactor with axial dispersion, and compared their model predictions against experimental data for batch polymerization.…”

Section: Introductionmentioning

confidence: 99%

Grade Transition Dynamic Optimization of the Living Nitroxide‐Mediated Radical Polymerization of Styrene in a Tubular Reactor

Zitlalpopoca-Soriano

Vivaldo‐Lima

Flores‐Tlacuahuac

2010

Macro Reaction Engineering

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In this work, the dynamic optimization of tubular reactors where nitroxide‐mediated radical polymerization (NMRP) of styrene takes place is performed. The effect of potential manipulated variables is addressed. The system is governed by partial differential equations (PDEs). The PDEs are discretized spatially giving rise to a differential‐algebraic equation (DAE) system. The DAE optimization problem is then solved using a simultaneous approach wherein the differential and the algebraic variables are fully discretized leading to a large‐scale nonlinear programming (NLP) problem. The resulting optimization problem is solved using an interior point algorithm capable of handling large‐scale NLPs.

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Nitroxide‐Mediated Polymerization of Styrene in a Continuous Tubular Reactor

Cited by 67 publications

References 21 publications

Controlled/living photopolymerization of methyl methacrylate in miniemulsion mediated by HTEMPO

Controlled/living photopolymerization of methyl methacrylate in miniemulsion mediated by HTEMPO

Residence Time Distribution Study of a Living/Controlled Radical Miniemulsion Polymerization System in a Continuous Tubular Reactor

Grade Transition Dynamic Optimization of the Living Nitroxide‐Mediated Radical Polymerization of Styrene in a Tubular Reactor

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