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

Enright, Thomas E.; Cunningham, Michael F.

doi:10.1002/mren.201100007

Cited by 6 publications

(1 citation statement)

References 31 publications

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“…In previous studies, the polymerization of styrene and butyl acrylate in (mini)emulsions using tubular flow reactors has been investigated. ,− However, the major problems when using tubular reactors for emulsion polymerization are coalescence and fouling or clogging of the reactor . Furthermore, the problems of coalescence, time- and energy-consuming preparation of the emulsion, and using toxic solvents for the continuous phase are circumvented in precipitation polymerization.…”

Section: Introductionmentioning

confidence: 99%

From Batch to Continuous Precipitation Polymerization of Thermoresponsive Microgels

Wolff

Kather

Breisig

et al. 2018

ACS Appl. Mater. Interfaces

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Microgels are commonly synthesized in batch experiments, yielding quantities sufficient to perform characterization experiments for physical property studies. With increasing attention on the application potential of microgels, little attention is yet paid to the questions (a) whether they can be produced continuously on a larger scale, (b) whether synthesis routes can be easily transferred from batch to continuous synthesis, and (c) whether their properties can be precisely controlled as a function of synthesis parameters under continuous flow reaction conditions. We present a new continuous synthesis process of two typical but different microgel systems. Their size, size distribution, and temperature-responsive behavior are compared in depth to those of microgels synthesized using batch processes, and the influence of premixing and surfactant is also investigated. For the surfactant-free poly( N-vinylcaprolactam) and poly( N-isopropylacrylamide) systems, microgels are systematically smaller, while the actual size is depending on the premixing of the reaction solutions. However, by the use of a surfactant, the size difference between batch and continuous preparation diminishes, resulting in equal-sized microgels. Temperature-induced swelling-deswelling of microgels synthesized under continuous flow conditions was similar to that of their analogues synthesized using the batch polymerization process. Additionally, investigation of the internal microgel structure using static light scattering showed no significant changes between microgels prepared under batch and continuous conditions. The work encourages synthesis concepts of sequential chemical conditions in continuous flow reactors to prepare precisely tuned new microgel systems.

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Section: Introductionmentioning

confidence: 99%

From Batch to Continuous Precipitation Polymerization of Thermoresponsive Microgels

Wolff

Kather

Breisig

et al. 2018

ACS Appl. Mater. Interfaces

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Nitroxide‐Mediated Polymerization

Vivaldo‐Lima

Jaramillo‐Soto

Penlidis

2016

Encyclopedia of Polymer Science and Technology

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Nitroxide‐mediated polymerization (NMP) has been studied abundantly in the past three decades. There are several very good and recent reviews on the topic available in the literature. Although in this article we provide an overview on the research efforts focused on the polymer chemistry of NMP, our emphasis is placed on research aspects of NMP from a polymer reaction engineering perspective. Namely, we emphasize the use of engineering tools (such as mathematical modeling) on the design, analysis, and control of NMP processes (process engineering) and the well‐defined microstructures obtained by NMP (product engineering). These aspects are not sufficiently discussed or even included in previous reviews on NMP. Despite of all the intensive research programs carried out in academia and industrial research centers over 30 years, there are still several issues that limit the commercial exploitation of NMP. These issues, which include slow polymerization rates, reduced amount of monomers amenable for polymerization by NMP, low molecular weights, and insufficient commercial availability of NMP controllers, are also discussed.

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History of nitroxide mediated polymerization in Canada

Marić

2021

Can J Chem Eng

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Nitroxide mediated polymerization (NMP), sometimes known as stable free radical polymerization (SFRP), is considered one of the main types of reversible deactivation radical polymerization (RDRP) that have emerged as a major advance in polymer synthesis in the past 30 years. This review examines NMP's development from a uniquely Canadian perspective. Inspired by reports of a reversible equilibrium between the TEMPO persistent radical and a growing polymeric radical chain, researchers at the Xerox Research Centre of Canada (XRCC) reported radical polymerizations of styrene with hallmarks typically associated with living polymerizations: linear degree of polymerization of with conversion, narrow molecular weight distributions, and ability to re‐initiate the chain end with additional monomer. This effort expanded to polymerizations in dispersed aqueous media (eg, miniemulsion) and to polymerizations directed for various architectures (block, graft, star), but NMP was ultimately generally limited to styrenic monomers. Consequently, NMP trailed other RDRP methods, such as atom transfer radical polymerization (ATRP) and reversible addition fragmentation transfer polymerization (RAFT), due to its limited monomer choice. With the advent of second‐generation alkoxyamine initiators, however, the range of monomers polymerizable in a controlled manner greatly expanded to include acrylates, acrylamides, and eventually methacrylates (under certain conditions), providing renewed impetus towards using NMP. Consequently, Canadian researchers applied these new alkoxyamines for more versatile polymers, resulting in products such as stimuli‐responsive polymers, CO2‐switchable latexes, bio‐hybrid composites, organic photovoltaic materials, and photolithographic materials. The chronological progression of the developments in NMP from various Canadian laboratories highlights these achievements in new polymeric materials.

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

Cited by 6 publications

References 31 publications

From Batch to Continuous Precipitation Polymerization of Thermoresponsive Microgels

From Batch to Continuous Precipitation Polymerization of Thermoresponsive Microgels

Nitroxide‐Mediated Polymerization

History of nitroxide mediated polymerization in Canada

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