Amines are key intermediates in the chemical industry due to their nucleophilic characteristic which confers a high reactivity to them. Thus, they are key monomers for the synthesis of polyamides, polyureas, polyepoxydes, which are all of growing interest in automotive, aerospace, building, or health applications. Despite a growing interest for biobased monomers and polymers, and particularly polyamides, it should be noticed that very few natural amines are available. Actually, there is only chitosan and poly(lysine). In this review we present both fundamental and applied research on the synthesis of biobased primary and secondary amines with current available biobased resources. Their use is described as a building block for material chemistry. Hence, we first recall some background on the synthesis of amines, including the reactivity of amines. Second we focus on the synthesis of biobased amines from all sorts of biomass, from carbohydrate, terpenes, or oleochemical sources. Third, because they need optimization and technological developments, we discuss some examples of their use for the creation of biobased polymers. We conclude with the future of the synthesis of biobased amines and their use in different applications.

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International audienceOver the last few years, more and more papers have been devoted to phosphorus-containing polymers, mainly due to their fire resistance, excellent chelating and metal-adhesion properties. Nevertheless, sustainability, reduction of environmental impacts and green chemistry are increasingly guiding the development of the next generation of materials. The use of bio-based polymer matrices might allow the reduction of environmental impacts by using renewable carbon and by achieving more easily biodegradable or reusable materials. The aim of this review is to present both fundamental and applied research on the phosphorylation of renewable resources, through reactions on naturally occurring functions, and their use in biobased polymer chemistry and applications. In the first section, different strategies for the introduction of phosphorus-containing functions on organic backbones are described. In the following sections, the main families of chemicals based on renewable resources are covered: namely polysaccharides (cellulose, chitosan, starch, dextran etc.), biophenols (lignins, biobased phenolic compounds, cardanol etc.), triglycerides (oils, glycerol) and hydroxy acid compounds

In this work, phloroglucinol was used as a renewable resource to prepare an epoxy monomer and phosphorus containing reactive flame retardant (FR). These building blocks were reacted with diamines to obtain partly or fully bio-based flame retardant epoxy resins. It was highlighted that the glass transition temperature of the materials was tightly related to the functionality of the reactive monomers and the resulting crosslink density. Thermal stability and char yield of the thermosets seems to be mainly governed by the aromaticity of the monomers, the linking rate of the aromatic ring and the phosphorus content. Phosphorus FR are more efficient in intrinsically poorly charring matrices. It was evidenced that the flammability of bio-based epoxies can be monitored by two strategies: (i) choosing bio-based monomers with high charring ability and low combustion energy, (ii) incorporating bio-based phosphorus-containing reactive FR in the polymer network.

The increasing price of barrels of oil, the global warming and other environmental problems favour the use of renewable resources to replace the petroleum based polymers used in various applications. Recently, fatty acids (FA) and their derivatives have appeared as one of the most promising candidates to afford novel and innovative biobased (co)polymers because of their ready availability, their low toxicity and their high versatility. However, the current literature mostly focused on FA-based polymers prepared by condensation polymerization or oxypolymerization while only few works have been devoted to radical polymerization due to the low reactivity of FA through radical process. Thus, the aim of this article is to give an overview of (i) the most common synthetic pathways reported in literature to provide suitable monomers from FA and their derivatives for radical polymerization, (ii) the available radical processes to afford FA-based (co)polymers and (iii) the different applications in which FAbased (co)polymers have been used since the last few years.

A new efficient type I photoinitiator derived from vanillin was synthesized to initiate, according to a green photoinduced process, the free-radical polymerization (FRP) of acrylate monomers in a reduced time and under air. Interestingly, this unprecedented photoinitiator lead to high acrylate conversions even under air, with a higher efficiency than some reference photoinitiating systems commonly used in FRP.

Syntheses of novel biobased PolyHydroxyUrethane (PHU) have been performed from Jojoba and castor oil. Cyclic carbonate monomers with various functionality were synthesized from both jojoba and castor oils. Pendant cyclic carbonate groups were obtained by a two-step reaction: thiol-ene coupling with thioglycolic acid followed by esterification with glycerin carbonate. These novel cyclic carbonate monomers exhibited higher reactivity than previous intra-chain plant oil-based cyclic carbonates. Di-functional jojoba oil-based cyclic carbonate was synthesized for the first time. PHUs were obtained by aminolysis of plant oil-based cyclic carbonates with various aliphatic and aromatic diamines. Structured linear and cross-linked PHUs were obtained with Tg ranging from-45 to 20°C. The different PHU materials were characterized by SEC, FTIR, DSC, ATG and DMA measurements. These results showed the potentiality of this environmentally friendly approach to prepare plant oils-based PHU materials with interesting performances.

The increasing concern about the environmental impact of physical blowing agents (PBAs) favours the use of chemical blowing agents (CBAs) to replace controversial PBAs. Blowing agents are key compounds in order to obtain polymer foams. Indeed, blowing agents are crucial additives that release gas needed to blow polymer foams. CBA compounds have been widely studied in recent decades, and today if new CBA are studied, one of the challenges remains to adapt the use of CBA to new polymers or new formulations. Only a handful of books present different CBAs commercially available but in these documents, the presentation of CBAs is not enough complete to understand potential or limits. Thus, our work is focused on the most common, both inorganic and organic chemical blowing agents and highlights the specifications of these CBAs, with their advantages and drawbacks, and finally presents promising perspectives.