A Monte Carlo study on LCCC characterization of graft copolymers at the critical condition of side chains

Zhu, Yutian; Ziebarth, Jesse D.; Fu, Chao; Wang, Yongmei

doi:10.1016/j.polymer.2015.04.067

Cited by 15 publications

(11 citation statements)

References 31 publications

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“…Therefore, individual blocks of a block copolymer have been characterized by LCCC under the critical conditions of each block often . Rigorous experimental examination of the theoretical prediction revealed that the block under critical condition is not completely invisible, but LCCC allows reasonable estimation of the individual block length. ,, Here we set the elution condition as SEC for the visible blocks and tried to estimate the size of the visible block using the calibration curve made with the corresponding homopolymer standards. Figures and show the LCCC chromatograms under the critical adsorption conditions of homo-PI and homo-PS to estimate the MW of PS backbone and PI branches using the calibration curve of standard homo-PS and homo-PI, respectively.…”

Section: Resultsmentioning

confidence: 99%

“…The chromatographic critical condition for a homopolymer is defined as the condition where the size exclusion effect is precisely compensated by the interaction effect. − At this condition, the retention of a homopolymer becomes independent of MW. The LCCC analysis of block copolymers is based on the assumption that a block at the critical condition of the same homopolymer is chromatographically “invisible”, and the retention of a block copolymer is governed solely by the other blocks in the block copolymer. ,, Although both experimental and simulation studies showed that the block under the critical condition is not fully invisible, LCCC analysis can provide a good MW estimate of individual blocks. − …”

Section: Introductionmentioning

confidence: 99%

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Synthesis and Characterization of an Exact Polystyrene-graft-polyisoprene: A Failure of Size Exclusion Chromatography Analysis

Lee

Chang

et al. 2017

Macromolecules

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An exact polystyrene-graf t-polyisoprene (PS-g-PI) synthesized by iterative anionic polymerization and graft reaction using diphenylethylene functional groups was characterized by liquid chromatography. As-prepared graft copolymer contains various byproducts other than the target PS-g-PI. After the fractionation by size exclusion chromatography (SEC), the PS-g-PI appears quite homogeneous by SEC analysis, but the temperature gradient interaction chromatography (TGIC) separation with respect to the PI branch number showed a significantly wide distribution in the number of PI grafts. The resolved TGIC peaks were fractionated, and the molecular weight of each block (backbone or branches) was estimated by liquid chromatography at critical condition (LCCC) analysis at the critical adsorption condition of the opposite block. The composition determined by LCCC analysis and 1 H NMR analysis yielded a reasonably self-consistent result. Through this study, we demonstrated that SEC analysis of this type of branched copolymers can lead to erroneous result and needs to be done with proper caution.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Synthesis and Characterization of an Exact Polystyrene-graft-polyisoprene: A Failure of Size Exclusion Chromatography Analysis

Lee

Chang

et al. 2017

Macromolecules

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“…For graft copolymers, when the side chain is set in the LCCC condition, the side chain impacts the elution of graft copolymer similarly, but to an even greater extent because of a higher number of grafts attached to the backbone. 65 Introducing the excluded volume effect in the SAW chain makes the overall …”

Section: Partitioning Of Block Copolymers or Grafted Copolymersmentioning

confidence: 99%

Interactions of complex polymers with nanoporous substrate

Ziebarth

Wang

2016

Soft Matter

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With the advance of polymer synthesis, polymers that possess unique architectures such as stars or cyclic chains, and unique chemical composition distributions such as block copolymers or statistical copolymers have become frequently encountered. Characterization of these complex polymer systems drives the development of interactive chromatography where the adsorption of polymers on the porous substrate in chromatography columns is finely tuned. Liquid Chromatography at the Critical Condition (LCCC) in particular makes use of the existence of the Critical Adsorption Point (CAP) of polymers on solid surfaces and has been successfully applied to characterization of complex polymer systems. Interpretation and understanding of chromatography behaviour of complex polymers in interactive chromatography motivates theoretical/computational studies on the CAP of polymers and partitioning of these complex polymers near the CAP. This review article covers the theoretical questions encountered in chromatographic studies of complex polymers.

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“…The computer simulation is an intelligent, powerful, and extraordinarily suitable approach for the investigation of the above-listed interrelated processes. Although the bulk-pore (also called the twin-box) model has been well developed and extensively employed in simulations of the partitioning of various polymers [ 24 , 25 , 26 , 27 , 28 , 29 , 30 , 31 , 32 , 33 , 34 , 35 , 36 , 37 , 38 ], to the best of our knowledge, the computer-aided interpretation of LC data on the partitioning of associating polymers has not yet been published. In this work, we study the bulk association of block copolymers in a selective solvent, and their partitioning and adsorption on porous media.…”

Section: Introductionmentioning

confidence: 99%

Modeling the Phase Equilibria of Associating Polymers in Porous Media with Respect to Chromatographic Applications

et al. 2022

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Associating copolymers self-assemble during their passage through a liquid chromatography (LC) column, and the elution differs from that of common non-associating polymers. This computational study aims at elucidating the mechanism of their unique and intricate chromatographic behavior. We focused on amphiphilic diblock copolymers in selective solvents, performed the Monte Carlo (MC) simulations of their partitioning between a bulk solvent (mobile phase) and a cylindrical pore (stationary phase), and investigated the concentration dependences of the partition coefficient and of other functions describing the phase behavior. The observed abruptly changing concentration dependences of the effective partition coefficient demonstrate the significant impact of the association of copolymers with their partitioning between the two phases. The performed simulations reveal the intricate interplay of the entropy-driven and the enthalpy-driven processes, elucidate at the molecular level how the self-assembly affects the chromatographic behavior, and provide useful hints for the analysis of experimental elution curves of associating polymers.

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A Monte Carlo study on LCCC characterization of graft copolymers at the critical condition of side chains

Cited by 15 publications

References 31 publications

Synthesis and Characterization of an Exact Polystyrene-graft-polyisoprene: A Failure of Size Exclusion Chromatography Analysis

Synthesis and Characterization of an Exact Polystyrene-graft-polyisoprene: A Failure of Size Exclusion Chromatography Analysis

Interactions of complex polymers with nanoporous substrate

Modeling the Phase Equilibria of Associating Polymers in Porous Media with Respect to Chromatographic Applications

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