Diffusion (DOSY) 1H NMR as an Alternative Method for Molecular Weight Determination of Poly(ethylene furanoate) (PEF) Polyesters

Rosenboom, Jan‐Georg; Roo, Jonathan De; Storti, Giuseppe; Morbidelli, Massimo

doi:10.1002/macp.201600436

Cited by 29 publications

(38 citation statements)

References 31 publications

(84 reference statements)

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“…We have previously shown that diffusion ordered spectroscopy (DOSY‐NMR) has potential for use in monitoring lignin MW . This technique initially measures the diffusivity of molecules in solution and this parameter can then be related to the MW of both small molecules, and polymers including lignin ,. In our previous report, diffusion coefficients of lignin fractions of variable MW were linearly correlated with MW data generated via GPC using the Mark‐Houwink‐Sakurada (MHS) relationship .…”

Section: Introductionmentioning

confidence: 99%

Using Fractionation and Diffusion Ordered Spectroscopy to Study Lignin Molecular Weight.

et al. 2019

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Recent reports demonstrate that applications of the biopolymer lignin can be helped by the use of a fraction of the lignin which has an optimal molecular weight range. Unfortunately, the current methods used to determine lignin's molecular weight are inconsistent or not widely accessible. Here, an approach that relies on 2D DOSY NMR analysis is described that provides a measure of lignin's molecular weight. Consistent results were obtained using this well‐established NMR technique across a range of lignins.

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Section: Introductionmentioning

confidence: 99%

Using Fractionation and Diffusion Ordered Spectroscopy to Study Lignin Molecular Weight.

et al. 2019

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“…

Jerschow and Müller [8] and with pulsed field gradient diffusion experiments already by Callaghan and Pinder. [9] Recent papers demonstrated the power of diffusion experiments for the determination of molar masses of poly(ethylene furanoate) polyesters, [10] polystyrene (PS), [11] poly(methyl methacrylate) (PMMA), [11,12] as well as polyethylene glycol. [12,13] Other DOSY applications presented by Li et al described the determination of molar masses of polymers in diverse living/controlled polymerizations.

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confidence: 99%

Quantitative Studies of Block Copolymers and Their Containing Homopolymer Components by Diffusion Ordered Spectroscopy

Hiller

2019

Macro Chemistry & Physics

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Several polystyrene‐b‐poly(methyl methacrylate) (PS‐b‐PMMA) and polyisoprene‐b‐PMMA (PI‐b‐PMMA) block copolymers are studied with high‐resolution diffusion ordered spectroscopy (DOSY) in order to quantify the amounts and molar masses of the copolymers and the containing homopolymers. These studies are particularly challenging because these homopolymers and one block of the copolymers consist of the same monomer type with different molar masses and compositions and cause a total overlap of these polymer components in the NMR spectra. However, DOSY can be proven as a powerful tool for separation and quantification of these moieties. Whereas exponential fittings only deliver averaged diffusion data, biexponential fittings of the individual magnetization curves can separate the overlapping polymer parts. This DOSY approach can be successfully tested for different blends of PS as well as PS and PS‐b‐PMMA of different molar masses and weighed compositions. The DOSY separation is also compared to size exclusion chromatography (SEC). In the case of the PS‐b‐PMMA and PI‐b‐PMMA block copolymers, DOSY identifies the contaminations with homopolymers, quantifies their individual amounts as well as determines the molar masses of both the copolymers and homopolymers. Two mathematical evaluations are used for quantifying these homopolymers with DOSY. These results are compared with the online coupling of SEC and NMR.

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“…With this respect, a promising method to access on-line the propagation and termination rate is represented by in-situ diffusion-ordered spectroscopy (DOSY) NMR [28], which might allow for measuring at the same time the residual monomer concentration and molecular weight. Furthermore, relevant information about the solution behavior of polar and ionizable molecules such as the MAA monomer and polymer as well as their interactions with the reaction environment (i.e., water and electrolytes) could be obtained by the application of computational chemistry, namely molecular dynamics simulations.…”

Section: Discussionmentioning

confidence: 99%

Aqueous Free-Radical Polymerization of Non-Ionized and Fully Ionized Methacrylic Acid

2017

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Water-soluble, carboxylic acid monomers are known to exhibit peculiar kinetics when polymerized in aqueous solution. Namely, their free-radical polymerization rate is affected by several parameters such as monomer concentration, ionic strength, and pH. Focusing on methacrylic acid (MAA), even though this monomer has been largely addressed, a systematic investigation of the effects of the above-mentioned parameters on its polymerization rate is missing, in particular in the fully ionized case. In this work, the kinetics of non-ionized and fully ionized MAA are characterized by in-situ nuclear magnetic resonance (NMR). Such accurate monitoring of the reaction rate enables the identification of relevant but substantially different effects of the monomer and electrolyte concentration on polymerization rate in the two ionization cases. For non-ionized MAA, the development of a kinetic model based on literature rate coefficients allows us to nicely simulate the experimental data of conversion versus time at a high monomer concentration. For fully ionized MAA, a novel propagation rate law accounting for the electrostatic interactions is proposed: the corresponding model is capable of predicting reasonably well the electrolyte concentration effect on polymerization rate. Nevertheless, further kinetic information in a wider range of monomer concentrations would be welcome to increase the reliability of the model predictions.

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Diffusion (DOSY) 1H NMR as an Alternative Method for Molecular Weight Determination of Poly(ethylene furanoate) (PEF) Polyesters

Cited by 29 publications

References 31 publications

Using Fractionation and Diffusion Ordered Spectroscopy to Study Lignin Molecular Weight.

Using Fractionation and Diffusion Ordered Spectroscopy to Study Lignin Molecular Weight.

Quantitative Studies of Block Copolymers and Their Containing Homopolymer Components by Diffusion Ordered Spectroscopy

Aqueous Free-Radical Polymerization of Non-Ionized and Fully Ionized Methacrylic Acid

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