Randomly-branched polymers by size exclusion chromatography with triple detection : computer simulation study for estimating errors in the distribution of molar mass and branching degree

This article theoretically evaluates the biases introduced into the distributions of molar masses (MMD) and the number of long chain branches per molecule (LCBD), when randomly-branched polymers are analyzed by size exclusion chromatography (SEC) with molar mass-sensitive detectors. The MMD of a po...

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Autores principales: Vega, Jorge Rubén, Clementi, Luis Alberto, Meira, Gregorio
Formato: Artículo acceptedVersion
Lenguaje:Inglés
Publicado: 2018
Materias:
Randomly-Branched Polymers
Distribution of 5 Molar Mass
Branching Degreea
Acceso en línea:http://hdl.handle.net/20.500.12272/3108
Aporte de:
RIA - Repositorio Institucional Abierto (UTN) de Universidad Tecnológica Nacional
id I68-R174-20.500.12272-3108
record_format dspace
spelling I68-R174-20.500.12272-31082023-06-28T22:53:53Z Randomly-branched polymers by size exclusion chromatography with triple detection : computer simulation study for estimating errors in the distribution of molar mass and branching degree Vega, Jorge Rubén Clementi, Luis Alberto Meira, Gregorio Randomly-Branched Polymers Distribution of 5 Molar Mass Branching Degreea This article theoretically evaluates the biases introduced into the distributions of molar masses (MMD) and the number of long chain branches per molecule (LCBD), when randomly-branched polymers are analyzed by size exclusion chromatography (SEC) with molar mass-sensitive detectors. The MMD of a polymer with tetrafunctional branch units has been calculated with the Stockmayer equation (1943); and an ideal SEC analysis has been simulated that assumes u-solvent, perfect measurements, and perfect fractionation by hydrodynamic volume except for a minor mixing in the detector cells. In ideal SEC, a negligible bias is introduced into the MMD, with the local dispersity exhibiting a maximum of 1.0035 at the high molar masses. This result is consistent with previous theoretical investigations, but differs qualitatively from experimental observationsofpolymerscontainingshort-andlong-chain branches. When including band broadening in the columns while still assuming perfect measurements, the MMDremainsessentiallyunbiased.Incontrast,poorMMD estimates are obtained when the chromatograms are contaminated with additive noise. Only qualitative estimates of the LCBD are possible, due to theoretical limitations combined with propagation of errors in a highly nonlinear calculation procedure. Fil: Vega, Jorge Rubén. Universidad Tecnológica Nacional. Facultad Regional Santa Fe Fil: Clementi, Luis Alberto. Universidad Tecnológica Nacional. Facultad Regional Santa Fe. CONICET. Argentina Fil: Meira, Gregorio. CONICET. Argentina Peer Reviewed 2018-09-11T20:06:33Z 2018-09-11T20:06:33Z 2013 info:eu-repo/semantics/article info:eu-repo/semantics/acceptedVersion info:ar-repo/semantics/artículo Randomly-Branched Polymers by Size Exclusion Chromatography with Triple Detection: Computer Simulation Study for Estimating Errors in the Distribution of Molar Mass and Branching Degree / Macromol. Theor and Simul http://hdl.handle.net/20.500.12272/3108 eng Tecnicas numéricas de estimación y optimización: aplicaciones en problemas de nanotecnología y de energía eléctrica - Código: 25/0147 info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by-nc-sa/4.0/ Condiciones de Uso desde su aprobación Atribución-NoComercial-CompartirIgual 4.0 Internacional application/pdf
institution Universidad Tecnológica Nacional
institution_str I-68
repository_str R-174
collection RIA - Repositorio Institucional Abierto (UTN)
language Inglés
topic Randomly-Branched Polymers
Distribution of 5 Molar Mass
Branching Degreea
spellingShingle Randomly-Branched Polymers
Distribution of 5 Molar Mass
Branching Degreea
Vega, Jorge Rubén
Clementi, Luis Alberto
Meira, Gregorio
Randomly-branched polymers by size exclusion chromatography with triple detection : computer simulation study for estimating errors in the distribution of molar mass and branching degree
topic_facet Randomly-Branched Polymers
Distribution of 5 Molar Mass
Branching Degreea
description This article theoretically evaluates the biases introduced into the distributions of molar masses (MMD) and the number of long chain branches per molecule (LCBD), when randomly-branched polymers are analyzed by size exclusion chromatography (SEC) with molar mass-sensitive detectors. The MMD of a polymer with tetrafunctional branch units has been calculated with the Stockmayer equation (1943); and an ideal SEC analysis has been simulated that assumes u-solvent, perfect measurements, and perfect fractionation by hydrodynamic volume except for a minor mixing in the detector cells. In ideal SEC, a negligible bias is introduced into the MMD, with the local dispersity exhibiting a maximum of 1.0035 at the high molar masses. This result is consistent with previous theoretical investigations, but differs qualitatively from experimental observationsofpolymerscontainingshort-andlong-chain branches. When including band broadening in the columns while still assuming perfect measurements, the MMDremainsessentiallyunbiased.Incontrast,poorMMD estimates are obtained when the chromatograms are contaminated with additive noise. Only qualitative estimates of the LCBD are possible, due to theoretical limitations combined with propagation of errors in a highly nonlinear calculation procedure.
format Artículo
acceptedVersion
Artículo
author Vega, Jorge Rubén
Clementi, Luis Alberto
Meira, Gregorio
author_facet Vega, Jorge Rubén
Clementi, Luis Alberto
Meira, Gregorio
author_sort Vega, Jorge Rubén
title Randomly-branched polymers by size exclusion chromatography with triple detection : computer simulation study for estimating errors in the distribution of molar mass and branching degree
title_short Randomly-branched polymers by size exclusion chromatography with triple detection : computer simulation study for estimating errors in the distribution of molar mass and branching degree
title_full Randomly-branched polymers by size exclusion chromatography with triple detection : computer simulation study for estimating errors in the distribution of molar mass and branching degree
title_fullStr Randomly-branched polymers by size exclusion chromatography with triple detection : computer simulation study for estimating errors in the distribution of molar mass and branching degree
title_full_unstemmed Randomly-branched polymers by size exclusion chromatography with triple detection : computer simulation study for estimating errors in the distribution of molar mass and branching degree
title_sort randomly-branched polymers by size exclusion chromatography with triple detection : computer simulation study for estimating errors in the distribution of molar mass and branching degree
publishDate 2018
url http://hdl.handle.net/20.500.12272/3108
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