Casein-based conjugates and graft copolymers. Synthesis, properties, and applications.

Biobased natural polymers, including polymers of natural origin such as casein, are growing rapidly in the light of the environmental pollution caused by many mass-produced commercial synthetic polymers. Although casein has interesting intrinsic properties, especially for the food industry, numerous chemical reactions have been carried out to broaden the range of its properties, most of them preserving casein's nontoxicity and biodegradability. New conjugates and graft copolymers have been developed especially by Maillard reaction of the amine functions of the casein backbone with the aldehyde functions of sugars, polysaccharides, or other molecules. Carried out with dialdehydes, these reactions lead to the cross-linking of casein giving three-dimensional polymers. Acylation and polymerization of various monomers initiated by amine functions are also described. Other reactions, far less numerous, involve alcohol and carboxylic acid functions in casein. This review provides an overview of casein-based conjugates and graft copolymers, their properties, and potential applications.

Chemical modification of edible sodium caseinate: A new grafting method of oleic acid. Characterization and thermal properties of the conjugate.

Sodium caseinate is a well-known amphiphilic protein derived from natural products currently used for the preparation of edible films. To improve some properties, especially to decrease the hydrophilicity and water solubility of the caseinate, the covalent grafting of a hydrophobic edible fatty acid, namely oleic acid, onto caseinate, appears to be a solution. We describe a new synthesis method for the chemical modification of sodium caseinate involving the synthesis of an acid chloride derivative from oleic acid and a phase transfer catalysis reaction in a biphasic medium. Under these conditions, free amine and alcohol groups of the caseinate are likely to be grafted with a fairly high (>50 %) substitution degree. The caseinate derivative is finely characterized, in particular by DOSY NMR, to assess the formation of a casein/oleic acid grafted compound as well as the absence of residual oleic acid.

A Comparative Study on Crystallisation for Virgin and Recycled Polyethylene Terephthalate (PET): Multiscale Effects on Physico-Mechanical Properties.

Poly(Ethylene Terephthalate) (PET) is one of the most used polymers for packaging applications. Modifications induced by service conditions and the means to make this matter circular have to be understood to really close the loop (from bottle to bottle for example). Physico-chemical properties, crystalline organisation, and mechanical behaviour of virgin PET (vPET) are compared with those of recycled PET (rPET). Using different combined experimental methods (Calorimetry, Small Angle X-ray Scattering [SAXS], Atomic Force Microscopy [AFM], Dynamic Mechanical Analysis [DMA], and uniaxial tensile test), it has been proven that even if there is no change in the crystallinity of PET, the crystallisation process shows some differences (size and number of spherulites). The potential impact of these differences on local mechanical characterisation is explored and tends to demonstrate the development of a homogeneous microstructure, leading to well-controlled and relevant local mechanical property characterisation. The main contribution of the present study is a better understanding of crystallisation of PET and recycled PET during forming processes such as thermoforming or Injection Stretch Blow Moulding (ISBM), during which elongation at the point of breaking can depend on the microstructure conditioned by the crystallisation process.