Polymeric materials, in particular PVC, can find various industrial utilizations thanks to the use of plasticizers added during their processing. The most famous applications include wires and cables, coatings, flooring, paintings, packaging… After some generalities concerning plasticization theories and the description of plasticized petro‐ and bio‐based polymers, this review details the well‐known different petro‐based plasticizers and more particularly phthalates which represent the most important category of PVC plasticizers. Owing to migration problems, impact on the human health and the environment, alternative candidates have been developed by researchers. Renewable resources and their wastes offer a large platform for the design of bio‐based plasticizers using polysaccharidic or lipidic structures. In an in‐depth analysis, the bio‐based plasticizer structures, their groups and substituents (ester groups, alkyl chains, aromatic rings…) are gathered and examined in order to be able to predict their plasticizing efficiency and design new molecular and macromolecular plasticizers from natural resources. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 11–33

Bio‐based plasticizers bearing moieties exhibiting flame retardancy properties [dimethyl (methyl oleate)phosphonate (PMO), diethyl (methyl oleate)phosphonate (PMO2), dimethyl (methyl linoleate)phosphonate (PML), dimethyl (dimethyl oleate)phosphonate (PDE)] are synthesized from methyl oleate, methyl linoleate, and oleic diacid through free‐radical addition of dialkyl phosphonates. Soft PVC is prepared from PMO, PMO2, PML, and PDE primary plasticizers and compared to materials containing usual diisononyl phthalate DINP. Rheological behavior, thermal stability, mechanical properties, and flame resistance performances of these PVC films are carefully investigated. The presence of the phosphonate group into the plasticizer structure explains the best thermal stability of the PVC films based on phosphonated plasticizer than that of based on DINP. Regarding all these results, PMO and PDE can be considered as efficient flame retardant primary plasticizers for PVC and can substitute phthalates in soft PVC based materials. Practical Applications: These biobased additives are elaborated as plasticizers for PVC improving flame retardancy. Lipids were investigated as additives for polymeric materials. Looking at replacing phthalates in soft PVC formulations, phosphonated lipids demonstrate both a flame‐retardant efficiency and plasticizing properties (mechanical properties, gelation temperature) for this polymer.