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

In recent years, the sustainability is becoming increasingly important for the chemical industry; thus, the use of renewable resources has gained interest in polymer applications. Vegetable oils are extracted primarily from the seeds of oilseed plants. Their competitive cost, worldwide availability, and built-in functionality (ester functions and insaturations) make them attractive. The development of oleochemicals has been carried out from two distinct ways. The first one corresponds to the double-bond modification 1 of crude oils or fatty acid derivatives. The second one is the carboxylic acid group modification of vegetable oils. 2 The chemical functionalizations of unsaturated oils to produce polyols have been widely developed to prepare new polyurethane structures, which depend on triglyceride and isocyanate reagents used. 3À5 These polyols are mainly obtained from intermediate epoxy oil either in one or two steps. The onestep reaction consists of the in-situ epoxidation followed by hydroxylation using acetic and sulfuric acids and hydrogen peroxide. 6 The two-step reaction deals with the triglyceride epoxidation followed by the ring-opening of oxirane, based on the use of difunctional molecules such as alcohols 7 or amines, 8 obtaining polyols from vegetable oils. Moreover, vegetable oil double bonds were converted into primary alcohols through hydroformylation followed by hydrogenation. 9 Eventually, ozonolysis was used to obtain polyols with terminal primary hydroxyl groups and different functionalities from natural vegetable oil and synthetic triglycerides. 10 Those functionalization processes usually require at least two-step reaction and sometimes expensive catalysts.Radical additions, such as thiolÀene coupling (TEC), are very attractive. A lot of unsaturated polymers were thus functionalized 11À14 from thiolÀene addition. So far, TEC reactions have mainly been used both to polymerize and to cross-link fatty acids 15À17 and triglycerides 18 by using polyfunctional thiols. 19 In addition, from TEC reaction, an effective optimization of vegetable oils lubricating property was performed either in one step or after grafting of mercaptosilanes on metallic surfaces. 20 Recently, Meier et al. synthesized polyols by TEC from methyl 10-undecenoate and thiol alcohol without initiator. These polyols were used as polyester precursors. 21 TEC reaction belongs to a set of reactions named "click" reactions 22À24 characterized by high yields, simple reaction ABSTRACT: A model study of the radical addition of 2-mercaptoethanol onto oleic acid was performed under mild conditions (generation of radicals under UV light at room temperature without any photoinitiator). To evaluate the efficiency and the robustness of thiolÀene reaction, experimental parameters were varied, such as the irradiation intensity (ranging from 0.5 to 15.0 W/cm 2 ), the thiol/double bond ratio (ranging from 1.2/1 to 5.0/1), the solvent/double bond ratio (ranging from 0/1 to 500/1), and the number of double bonds per chain. It was especially shown...