Thermoplastic starch/polyvinyl alcohol blends modification by citric acid-glycerol polyesters. 2023

Jennifer M Castro, and Mercedes G Montalbán, and Noelia Martínez-Pérez, and Daniel Domene-López, and Juana M Pérez, and Francisco M Arrabal-Campos, and Ignacio Fernández, and Ignacio Martín-Gullón, and Juan C García-Quesada
Chemical Engineering Department, University of Alicante, Apartado 99, 03080 Alicante, Spain; Institute of Chemical Process Engineering, University of Alicante, Apartado 99, 03080 Alicante, Spain.

Thermoplastic starch/polyvinyl alcohol (TPS/PVA) films have limitations for being used in long-term applications due to starch retrogradation. This leads to plasticizer migration, especially when low molecular weight plasticizers such as glycerol, are used. In this work, we employed mixtures of oligomers based on glycerol citrates with higher molecular weight than glycerol as plasticizers for potato-based TPS/PVA blends obtained by melt-mixing. This constitutes an alternative to reduce plasticizer migration while keeping high swelling degree, and to provide high mechanical performance. The novelty lies in the usage of these oligomers by melt-mixing technique, aspect not deeply explored previously and that represents the first step towards industrial scalability. Prior to the blending process, oligomers mixtures were prepared with different molar ratios of citric acid (0-40 mol%) and added them. This minimizes the undesirable hydrolysis effect of free carboxylic groups on starch chains. The results demonstrated that the migration of plasticizers in TPS/PVA blends decreased by up to 70 % when the citric acid content increased. This reduction was attributed to the higher molecular weight (the majority in the range 764-2060 Da) and the 3D structure of the oligomers compared to using raw glycerol. Furthermore, the films exhibited a 150 % increase in Young's modulus and tensile strength without a reduction in elongation at break, while maintaining a high gel content, due to a moderate crosslinking.

UI MeSH Term Description Entries
D010968 Plasticizers Materials incorporated mechanically in plastics (usually PVC) to increase flexibility, workability or distensibility; due to the non-chemical inclusion, plasticizers leach out from the plastic and are found in body fluids and the general environment. Plasticizer
D011091 Polyesters Polymers of organic acids and alcohols, with ester linkages--usually polyethylene terephthalate; can be cured into hard plastic, films or tapes, or fibers which can be woven into fabrics, meshes or velours. Polyester
D011142 Polyvinyl Alcohol A polymer prepared from polyvinyl acetates by replacement of the acetate groups with hydroxyl groups. It is used as a pharmaceutic aid and ophthalmic lubricant as well as in the manufacture of surface coatings artificial sponges, cosmetics, and other products. Liquifilm Tears,Polyviol,Alcohol, Polyvinyl,Tears, Liquifilm
D005990 Glycerol A trihydroxy sugar alcohol that is an intermediate in carbohydrate and lipid metabolism. It is used as a solvent, emollient, pharmaceutical agent, or sweetening agent. 1,2,3-Propanetriol,Glycerin,1,2,3-Trihydroxypropane,Glycerine
D013213 Starch Any of a group of polysaccharides of the general formula (C6-H10-O5)n, composed of a long-chain polymer of glucose in the form of amylose and amylopectin. It is the chief storage form of energy reserve (carbohydrates) in plants. Amylomaize Starch,Amylum,Cornstarch,Keoflo,Starch, Amylomaize
D019343 Citric Acid A key intermediate in metabolism. It is an acid compound found in citrus fruits. The salts of citric acid (citrates) can be used as anticoagulants due to their calcium chelating ability. Citrate,Anhydrous Citric Acid,Citric Acid Monohydrate,Citric Acid, Anhydrous,Uralyt U

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