Continuous Monitoring of the Effect of Changing Solvent Conditions on Polyelectrolyte Conformations and Interactions

Bayly, Erica; Brousseau, Jean-Luc; Reed, Wayne F.

doi:10.1080/10236660214596

Cited by 10 publications

(5 citation statements)

References 35 publications

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“…Automatic continuous mixing (ACM) , was used to compute the second virial coefficient, A 2 , and to cross-check ACOMP values for M w and [η] w of the endproducts. The experiments were carried out with a Shimadzu gradient mixer and the same detector train as above.…”

Section: Methodsmentioning

confidence: 99%

Monitoring the Synthesis and Properties of Copolymeric Polycations

et al. 2008

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The kinetics; evolution of molar mass; solution conductivity, sigma; intrinsic viscosity; and average composition drift; and distribution were determined by monitoring the synthesis of copolymeric polycations of acrylamide (Am) and [2-(acryloyloxy)ethyl]-trimethylammonium chloride (Q9). The quantitative relationship between diminishing sigma and charged co-monomers incorporation was monitored for the first time and provided novel data on counterion condensation, which occurs gradually over a broad composition regime. This new capability allows predictions concerning the relationship between copolymer composition and linear charge density, xi, to be tested and models of trivariate mass, composition, and xi distributions to be built. This approach, hence, brings together the previously disparate fields of synthetic chemistry of copolymers and physical chemical properties of polyelectrolytes. Monitoring was achieved with a new implementation of the ACOMP (automatic continuous online monitoring of polymerization reactions) platform. Reactivity ratios determined by ACOMP were rQ9 = 0.47 and rAm = 1.10. Opposite trends in composition drift and final molar mass were found; low starting percentage of Q9 led to low composition drift and high molar mass, whereas the opposite was found at high starting percentage of Q9. Complementary end-product analysis by multidetector gel permeation chromatography supported the ACOMP results. End-product polyelectrolyte properties were characterized by automatic continuous mixing, revealing that combined electrostatic persistence length and excluded volume effects led to the expected large changes in polyelectrolyte conformation and interactions. These results set the groundwork for semibatch control of molar mass, composition, and xi, and eventually for monitoring and control for inverse emulsion-based reactions of this type.

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Section: Methodsmentioning

confidence: 99%

Monitoring the Synthesis and Properties of Copolymeric Polycations

et al. 2008

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“…ACM has recently been used for determining properties of uncharged polymers, effects of ionic strength on polyelectrolyte scattering and viscosity, , and complex association and polyelectrolyte behavior of charged surfactants and neutral polymers …”

Section: Methodsmentioning

confidence: 99%

Effect of Valence and Chemical Species of Added Electrolyte on Polyelectrolyte Conformations and Interactions

Sorci

Reed

2003

Macromolecules

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The effect of added electrolyte (AE) valence and species on polyelectrolytes was studied using automatic, continuous mixing (ACM), allowing measurements over composition gradients. The second virial coefficient A 2 was decomposed into contributions from an electrostatically sensitive meansquare gyration radius 〈S 2 〉 and an external electrostatic field. 〈S 2 〉 matched predictions of combined electrostatic persistence length and excluded-volume theories, without adjustable parameters. A2 was modeled via an equivalent, soft-core, expansible, charged sphere. Whereas the scaling behavior of 〈S 2 〉, intrinsic viscosity [η], and A2 was the same for all AE, the prefactors strongly depended on AE symmetry and valence. At given ionic strength 〈S 2 〉, [η], A2, effective linear charge density, and expansible sphere surface potential are less for divalent than monovalent AE. Different ion species for a given valence class showed second-order effects following a Hoffmeister series. ACM should also prove valuable for investigating AE-induced phase transitions in polyelectrolytes like DNA and proteins.

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“…Gradient pumps are used to create selected paths in the composition space of the solution, and light scattering and viscosity data are gathered over the path, and the RI and/or UV detectors are used to compute the solute concentrations at each point of the path. Examples include determination of effects of added electrolyte on polyelectrolyte dimensions, interactions and hydrodynamics,32, 33 ion‐specific effects and interactions of surfactants, polymers, aromatic molecules and electrolytes 34. Figure 6 gives an example of ACM data showing the effect of increasing electrolyte (NaCl) concentration on the LS and viscosity of a highly charged, linear polyelectrolyte, sodium hyaluronate (HA).…”

Section: Related Complementary Methodsmentioning

confidence: 99%

Automatic continuous online monitoring of polymerization reactions (ACOMP)

Alb

Drenski

Reed

2007

Polymer International

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A brief overview of the principles and associated instrumentation used to monitor polymerization reactions by automatic continuous online monitoring of polymerization reactions (ACOMP) is presented. ACOMP can be used as an analytical method in R&D, as a tool for reaction optimization at the bench and pilot plant level and, eventually, for feedback control of full‐scale reactors. ACOMP measures in a model‐independent fashion the evolution of average molar mass and intrinsic viscosity, monomer conversion kinetics and, in the case of copolymers, also the average composition drift and distribution. A summary of areas of ACOMP application is given, which include free radical and controlled radical homo‐ and copolymerization, polyelectrolyte synthesis, heterogeneous phase reactions, including emulsion polymerization, adaptation to batch and continuous reactors, and modifications of polymers. Finally, a brief sketch of two novel complementary methods is given: automatic continuous mixing (ACM) and simultaneous multiple sample light scattering (SMSLS). Copyright © 2007 Society of Chemical Industry

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Continuous Monitoring of the Effect of Changing Solvent Conditions on Polyelectrolyte Conformations and Interactions

Cited by 10 publications

References 35 publications

Monitoring the Synthesis and Properties of Copolymeric Polycations

Monitoring the Synthesis and Properties of Copolymeric Polycations

Effect of Valence and Chemical Species of Added Electrolyte on Polyelectrolyte Conformations and Interactions

Automatic continuous online monitoring of polymerization reactions (ACOMP)

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