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

This Review is focused on the growing interest brought to phosphorus-containing organic materials for applications in the biomedical field, mainly because of their properties such as biocompatibility, hemocompatibility, and protein adsorption resistance. It mainly describes relevant works achieved on these materials for various applications: dentistry, regenerative medicine, and drug delivery. Special attention was given to 2-methacryloyloxyethyl phosphorylcholine (MPC) monomer as the latter appeared of great importance because of its biomimetic structure due to the presence of the phospholipid group on its structure. As a result, much research effort is currently concentrated on the development of phosphorylcholine-containing (co)polymers that represent a promising class of materials.

Polyoxazolines (POx) are increasingly studied as polymeric building blocks due to the possibility of affording tunable properties. Additionally, as it was proved that biocompatibility and stealth behavior of POx are similar to that of poly(ethylene glycol) (PEG), it became challenging to develop polyoxazoline-based (co)polymers. Even if POx have a lot of advantages, they also show an important drawback as it is to date impossible to prepare high molecular weight polyoxazolines, with low polydispersity indexes. So, it appears important to judiciously functionalize them. This review covers the multiple ways of functionalization of polyoxazolines.The use of functional initiators, functional terminating agents, and 2-R-2-oxazolines with R functional side group is detailed. In conclusion, some perspectives on POxfunctionalizations are also reported, with functions permitting selective "click" reactions.

A novel vegetable oil-based polyamine issued from grapeseed oil (GSO) was prepared using cysteamine chloride (CAHC) by thiol-ene coupling (TEC). The structure of the polyamine oil (AGSO) was carefully examined using a large range of chemical analyses (FTIR, 1 H NMR and 13 C NMR, LC-MS…). The effects of the amination of GSO on the vegetable oil properties were also studied using viscosimetry. Then, AGSO was employed as a novel curing agent for bio-based epoxy resin. The thermal crosslinking reaction between AGSO and epoxi-dized linseed oil (ELO) was studied by DSC and rheology. This study also dealt with the definition of the thermomechanical properties of the final material obtained by the mixing and curing of AGSO with ELO in stoichiometric proportions.

The polymerization of methyl methacrylate (MMA) initiated by 2,2‘-azobis(isobutyronitrile) (AIBN) as radical initiator in the presence of iodine (I2) was studied at different temperatures (T = 70 °C and 80 °C). This process, called reverse iodine transfer polymerization (RITP), is based on the direct reaction of radicals with molecular iodine. RITP efficiently controls the molecular weight (determined by size exclusion chromatography, SEC) and the structure of the polymer chains (confirmed by 1H and 13C NMR spectroscopy). For instance, PMMA samples of M n,SEC = 2300 g mol-1 and polydispersity index PDI = M w/M n = 1.5 (M n,theoretical = 2300 g mol-1), M n,SEC = 4600 g mol-1 and PDI = 1.6 (M n,theoretical = 4700 g mol-1), M n,SEC = 9600 g mol-1 and PDI = 1.6 (M n,theoretical = 10 000 g mol-1), and M n,SEC = 19 200 g mol-1 and PDI = 1.5 (M n,theoretical = 18400 g mol-1) were successfully prepared by RITP. The polymerization was followed by on-line 1H NMR spectroscopy, and the conversion of iodine was followed by titration with a thiol (thioglycolic acid). It was shown by SEC, titration of iodine, gas chromatography, and NMR analyses that RITP was split into two different periods:  a first “inhibition” period during which iodine is consumed to form very short ω-iodotelomers, and a second period where the polymerization follows the kinetics of a conventional free radical polymerization governed by degenerative chain transfer. The degenerative chain transfer constant was estimated to be C ex ≈ 2.6 at T = 80 °C. Last, the iodine-end-capped structure of the polymers was demonstrated by different analytical techniques, and the iodine functionality of the PMMA chains was up to 95%.

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