Development of chromatographic method for the determination of degree of polymerisation of polyglycerols and polyglycerol fatty acid esters

Meulenaer, Bruno De; Vanhoutte, Bert; Huyghebaert, André

doi:10.1007/bf02490694

Cited by 28 publications

(24 citation statements)

References 21 publications

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“…On the other hand, the use of orthogonal protective groups and of selective reactions yielded a large range of amphiphilic molecules bearing different kind of fatty chain (length, unsaturations, position on the polar head, ester or ether bond). Jusqu'à présent, la multiplicité des structures produites ainsi que l'absence d'étalon de référence a véritablement freiné les méthodes d'analyses chromatographiques [4][5][6][7]. Les études des propriétés physicochimiques ont également été uniquement réalisées sur ces mélanges de dérivés d'oligoglycérols [8,9].…”

Section: Discussionunclassified

“…Ces composés peuvent résulter de réactions de condensation intramoléculaire à partir d'oligomères linéaires ou ramifiés [5]. Ils sont généralement décrits comme des sous-produits minoritaires des réactions de polymérisation, dont la présence n'est pas souhaitée et que les producteurs cherchent plutôt à minimiser.…”

Section: Préparation D'oligoglycérols Cycliquesunclassified

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Synthèse de polyglycérols linéaires et cycliques. Tensioactifs polyglycérylés : synthèse et caractérisations

Debaig¹,

Benvegnu²,

Plusquellec³

2002

OCL

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Résumé : Le glycérol est l'un des principaux sous-produits de l'oléochimie. Un des axes de recherche pour valoriser ce co-produit demeure la production de polyglycérols et d'esters de polyglycérols, tensioactifs non ioniques. Cependant, ceux-ci sont généralement préparés industriellement dans des conditions drastiques (milieu caustique et températures élevées), générant des mélanges complexes d'oligomères de composition moléculaire mal définie. C'est dans ce contexte qu'un programme européen a été initié dans le but de préparer des échantillons standard et d'établir des corrélations structure/activité (analyse, performances, environnement) par une étude plus fondamentale sur les oligomères du glycérol et leurs esters. Notre travail a consisté à mettre au point des voies d'accès à des oligoglycérols linéaires et cycliques, de degré 2 à 5, ainsi que des monoesters et monoéthers d'acides gras, de structure parfaitement définie, en privilégiant des synthèses courtes et efficaces pour obtenir des échantillons de plusieurs grammes. Les stratégies pour les structures linéaires reposent dans un premier temps sur des synthèses convergentes impliquant l'ouverture régiospécifique d'époxydes. La préparation de dimères cycliques du glycérol repose sur des réactions d'iodocyclisation, alors que les oligomères cycliques de degré 3 à 5 ont été préparés via la condensation de deux fragments linéaires. Dans un deuxième temps, le choix de groupes protecteurs orthogonaux et de réactions sélectives a permis de synthétiser une gamme de molécules amphiphiles de structure définie, en faisant varier aussi bien la tête polaire (nombre d'unités glycérol impliquées) que la chaîne hydrophobe (longueur, insaturation, position sur la tête polaire, liaison chimique ester ou éther). Summary :Glycerol is one of the main by-products of oleochemistry. In order to develop the possible uses of this by-product, research can focus on the production of polyglycerols and their non-ionic surfactants. However, they are usually prepared under drastic conditions (caustic media and high temperatures) leading to complex mixtures of undefined oligomers. In this context, a European Program started to prepare authentic standards of oligomers of glycerol as well as corresponding surfactants and to establish relations between structures and activity. This work describes a new means of access to authentic standards of linear and cyclic oligoglycerols and their mono-esters or mono-ethers with well-defined structures and determined degrees of polymerisation from 2 to 5, through short and efficient syntheses allowing further scaling up. On the one hand, linear oligomers were obtained by means of a convergent approach based on regioselective opening of epoxides. Iodocyclisation reactions involving unsaturated alcohols permitted to build cyclic diglycerols, whereas larger cycles were prepared thanks to the condensation of two linear fragments. On the other hand, the use of orthogonal protective groups and of selective reactions yielded a large range of amphiphilic molec...

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Section: Discussionunclassified

Section: Préparation D'oligoglycérols Cycliquesunclassified

Synthèse de polyglycérols linéaires et cycliques. Tensioactifs polyglycérylés : synthèse et caractérisations

Debaig¹,

Benvegnu²,

Plusquellec³

2002

OCL

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“…The hydrophilic properties of the emulsifi er, which can be expressed as the HLB value, are a function of the molecular weight of the esterifi ed fatty acid, the degree of esterifi cation of hydroxyl groups and the number of glycerol units forming the polyglycerol backbone. For a given hydrocarbon chain length of fatty acid and the degree of esterifi cation, the hydrophilic properties of the emulsifi er increase with the molecular weight of polyglycerol 8 . Mixed surfactant systems are used in many applications.…”

Section: Introductionmentioning

confidence: 99%

Emulsifiers from renewable materials: an eco-friendly synthesis and properties

Szeląg¹,

Sadecka²,

Pawłowicz³

et al. 2013

Polish Journal of Chemical Technology

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The focus of this study was the preparation of novel bio based polyglycerol emulsifi ers characterized by a one pot synthesis, thus by modifi ed properties with respect to interfacial activity and effectiveness as emulsion stabilizers. The fi nal products of the esterifi cation process, carried out in the presence of carboxylates were used directly as emulsifi ers (without purifi cation or fractionation). Polyglycerol emulsifi ers obtained in proposed conditions can be tailored to stabilize the defi ned emulsion system. The modifi cation of the surface activity of emulsifi ers may be obtained by programming the fatty acid acyl group in the polyglycerol ester as well as the hydrocarbon chain length in sodium soap and concentration of this compound in the reaction mixture.

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“…Thus, liquid chromatography (LC) is the only chromatographic technique that can be used for separation of PGE samples containing highly polymerized polyglycerols. Several research groups have used LC for analysis of selectively synthesized oligoglycerols [22,25] and PGE [8, 26 -29], but, to the authors' knowledge, separation of a highly complex PGE sample has never been published before.…”

Section: Introductionmentioning

confidence: 99%

“…The complexity is dependent on several factors: (i) the degree of glycerol polymerization (the trimers or tetramers are normally the most abundant), (ii) the linear, branched, or cyclic structure of the polyglycerol moiety, (iii) the purity of the fatty acids, and (iv) the position and the number of fatty acids bonded to each polyglycerol molecule. Especially, the polyglycerol moiety has a pronounced effect on the PGE complexity, since the number of possible linear, branched, and cyclic isomers increases exponentially with the degree of glycerol polymerization [22]. Separation of complex PGE mixtures is therefore a very challenging task, independent of what type of chromatographic technique is used.…”

Section: Introductionmentioning

confidence: 99%

Characterization of complex mixtures of polyglycerol fatty acid esters using temperature and solvent gradients in packed capillary LC

Andersen¹,

Holm²,

Skuland³

et al. 2003

J of Separation Science

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Characterization of complex mixtures of polyglycerol fatty acid esters using temperature and solvent gradients in packed capillary LC A highly complex sample of polyglycerol fatty acid esters has been characterized using both temperature gradient and solvent gradient reversed-phase packed capillary LC coupled to ELSD and ESI-TOF-MS. The techniques showed fairly similar performance in terms of selectivity and efficiency, providing a nice separation of not only the polyglycerol mono-, di-, tri-and tetra-fatty acid esters, but also the non-reacted polyglycerols. The different groups were identified by coupling the packed capillary LC system to a TOF-MS using an electrospray interface, although the identification of the latest eluting groups in the temperature gradient separation was hampered due to significant column bleeding at elevated column temperatures. By calculating the peak areas in the ELSD chromatograms, the PGE sample was estimated to contain 20.2 l 0.4 and 22.6 l 0.5% non-reacted polyglycerols, 44.4 l 1.9 and 34.1 l 1.4% mono-fatty acid esters, 26.2 l 1.5 and 27.9 l 1.7% di-fatty acid esters, 7.7 l 0.7 and 12.6 l 1.0% tri-fatty acid esters, and 1.4 l 0.2 and 2.8 l 0.3% tetra-fatty acid esters in temperature and solvent gradient mode (n = 3), respectively. The intra-day precision of the retention times was 0.5 -1.4% (n = 3) in the temperature gradient mode, while it was 0.3 -1.7% (n = 3) in the solvent gradient mode.

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Development of chromatographic method for the determination of degree of polymerisation of polyglycerols and polyglycerol fatty acid esters

Cited by 28 publications

References 21 publications

Synthèse de polyglycérols linéaires et cycliques. Tensioactifs polyglycérylés : synthèse et caractérisations

Synthèse de polyglycérols linéaires et cycliques. Tensioactifs polyglycérylés : synthèse et caractérisations

Emulsifiers from renewable materials: an eco-friendly synthesis and properties

Characterization of complex mixtures of polyglycerol fatty acid esters using temperature and solvent gradients in packed capillary LC

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