The Mechanism of Copolymer Retention in Interactive Polymer Chromatography. I. Critical Point of Adsorption for Statistical Copolymers

Brun, Yefim

doi:10.1081/jlc-100102075

Cited by 66 publications

(46 citation statements)

References 79 publications

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“…They assumed that only one monomer type was adsorptive. The simulation results were found in good agreement with a theoretical equation proposed by Brun [120]. Subsequently, the selective adsorption of a heteropolymer on heterogeneous surfaces was examined [121,122].…”

Section: Predicting Chromatographic Separation For Polyolefins Based supporting

confidence: 73%

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A review on the development of liquid chromatography systems for polyolefins

Macko¹,

Brüll²,

Zhu

et al. 2010

J of Separation Science

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Polyolefins are the most widely produced synthetic polymer commodity and are found in countless applications ranging from bottles, packaging films to bullet-proof jackets, etc. Such widely different applications rely on high variability in the physical properties of polyolefins, which is a result of variations in microstructure, chemical composition and molar mass. Though polyolefins contain only carbon (C) and hydrogen (H) atoms, the microstructures of polyolefins are extremely variable, differing in the nature of the monomers (e.g. ethylene versus propylene), the degree of branching, chemical composition in the case of copolymers and finally their molar masses. Production, research and development of polyolefins require the analysis of polyolefin samples in terms of all these parameters. Development of efficient and robust analytical techniques based on the interactive LC is reviewed. The needed computational/theoretical studies to understand the retention mechanism in the newly developed chromatography systems are discussed.

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Section: Predicting Chromatographic Separation For Polyolefins Based supporting

confidence: 73%

“…The symbols represent the CAP determined by the simulation, whereas the lines are the plots according to Brun's theoretical equation [120]. From [123] with permission.…”

Section: Discussionmentioning

confidence: 99%

A review on the development of liquid chromatography systems for polyolefins

Macko¹,

Brüll²,

Zhu

et al. 2010

J of Separation Science

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“…We showed previously [16] that the chromatographic behavior of any ergodic statistical copolymer is similar to that of a homopolymer with some effective segment interaction energy e eff , even when segment interaction energies, e i , of the individual monomer units A i are different from each other. This effective energy e eff is a function of the individual values e i .…”

Section: Cpa For Statistical Copolymersmentioning

confidence: 96%

“…But the separation by chemical composition is not the only possible application of this technique. We showed theoretically [16] that CPA for statistical copolymers depends not only on chemical composition but also on microstructure (blockiness) of the polymer chains. It has been predicted that blockiness always increases retention, so that among two polymer chains with the same chemical composition the one with more blocky sequence distribution will elute later than its more random counterpart [16].…”

Section: Introductionmentioning

confidence: 98%

“…We showed theoretically [16] that CPA for statistical copolymers depends not only on chemical composition but also on microstructure (blockiness) of the polymer chains. It has been predicted that blockiness always increases retention, so that among two polymer chains with the same chemical composition the one with more blocky sequence distribution will elute later than its more random counterpart [16]. In the current publication, we further discuss the application of gradient elution for separation of copolymers by microstructure, and for the first time provide experimental confirmation of the theory of such separation.…”

Section: Introductionmentioning

confidence: 98%

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Characterization of synthetic copolymers by interaction polymer chromatography: Separation by microstructure

Brun

Foster

2010

J of Separation Science

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Gradient elution of synthetic polymers has been studied both theoretically and experimentally using normal and reversed-phase HPLC systems. An accurate equation describing the gradient elution of polymer-homologous series in the context of continuous random-flight model of a flexible polymer chain interacting with attractive surface of the porous material has been derived and experimentally verified against a series of narrow polystyrene standards. Both the theory and the experiment predict the existence of molar mass-independent gradient elution at critical point of adsorption (CPA). The extension of the theory to synthetic copolymers predicts the existence of the CPA for statistical copolymers and describes its dependence on chemical composition and microstructure (blockiness) of the polymer chains. One of the important theoretical conclusions is that blockiness always increases the retention, so that blockier polymer chains elute later than their more random counterparts with the same chemical composition. This prediction has been confirmed experimentally using block and statistical styrene-methylmethacrylate copolymers. Block copolymers do not have CPA and always elute between critical points of the corresponding homopolymers. The retention depends on the polymer molar mass and increases with the length of the blocks from a stronger absorbing monomer. These findings provide theoretical and experimental bases for separation of statistical and block copolymers by chemical composition and microstructure of polymer chains.

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Chromatography, HPLC

Brun¹

2001

Encyclopedia of Polymer Science and Technology

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A comprehensive review of high performance liquid chromatography (hplc) of biological and synthetic polymers is presented. Instrumentation, individual modes of separation, theoretical background (both thermodynamic and dynamic factors), and applications are discussed. High performance liquid chromatography is widely used for isolation and purification of biopolymers and analysis of additives in complex polymer formulations. The potential of hplc for bioseparations is analyzed in the light of recent development in reversed‐phase, hydrophobic‐interaction, and ion‐exchange chromatographies. Miniaturization of separation and other problems related to coupling column chromatography to mass spectrometer detection, as well as multidimensional separations, are considered in some detail. High performance liquid chromatography is a powerful tool for characterization of synthetic and natural polymers by separating individual fractions by molecular weight, chemical composition, functional groups, etc. Normal‐ or reversed‐phase gradient separation of synthetic copolymers and polymer blends provides information about polymer's chemical composition distribution, and is considered as a technique complimentary to size‐exclusion chromatography. Two‐dimensional copolymer characterization is achieved by coupling two different modes of chromatographic separation consequently, which can result in determination of both molecular weight and chemical composition distributions of synthetic copolymers.

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The Mechanism of Copolymer Retention in Interactive Polymer Chromatography. I. Critical Point of Adsorption for Statistical Copolymers

Cited by 66 publications

References 79 publications

A review on the development of liquid chromatography systems for polyolefins

A review on the development of liquid chromatography systems for polyolefins

Characterization of synthetic copolymers by interaction polymer chromatography: Separation by microstructure

Chromatography, HPLC

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