Epoxidation is an effective method for enhancing the plasticizing properties of biobased oils for the plasticization of poly(vinyl chloride) (PVC), among other applications. Epoxy groups not only increase the affinity with PVC but also enhance its thermal and mechanical properties. Cashew nut shell liquid (CNSL), an inedible oil derived from agricultural waste, comprises cardanol, cardol, and anacardic acid. These compounds, phenols with long alkyl chains, contain unsaturation that can be epoxidized. This project aims to evaluate the feasibility of utilizing technical CNSL (80% cardanol and 20% cardol) as a PVC plasticizer. Various plasticizers were synthesized from pure cardanol or technical CNSL through esterification and epoxidation to enhance compatibility with PVC and plasticizing properties. Notably, as far as we know, mixtures of cardanol and cardol derivatives have been epoxidized for the first time. The chemical structures of these plasticizers were fully characterized using 1H nuclear magnetic resonance (NMR) spectroscopy. Furthermore, the mechanical properties, thermal stability, and chemical resistance of PVC films plasticized with these additives were investigated.Practical Applications: Cardanol, once esterified and epoxidized, has demonstrated good plasticizing capabilities for certain polymers including PVC. This naturally occurring product is obtained after distillation of a crude oil from the shell of cashew nuts, the cashew nutshell liquid (CNSL). Other components present in this oil, such as cardol, have also demonstrated significant pertinence in the plasticization of PVC. Using the crude oil or a mixture of components as precursors for plasticizers for PVC would reduce the cost of the plasticizing agent and avoid possible loss or waste linked to the separation of the raw compounds, currently carried out.

For the first time, a mixture of cardanol and cardol esters has been studied as plasticizers for PVC. From our previous work, it has been established that the favorable plasticizing properties of cardol for PVC materials exist. Hence, the utilization of cashew nutshell liquid (CNSL), a naturally occurring mixture of cardanol and cardol, as a PVC plasticizer presents an intriguing prospect. While major studies focused on cardanol-based PVC plasticizers, their extraction process entails time-consuming, energy-intensive, and costly steps, thereby limiting market competitiveness. The aim of this study is not to focus on pure cardol or pure cardanol, as previously conducted, but instead to focus on the naturally derived mixtures obtained through CNSL extraction. Various ester plasticizers with different alkyl length chains were synthesized from various CNSL mixtures, containing different ratios of cardanol and cardol. The chemical structure of these plasticizers was fully characterized by using 1H NMR spectroscopy, while the rheological properties of plastisol, mechanical properties, and thermal stability of plasticized PVC films were investigated. Through this exploration, insights into the potential of CNSL-derived esters as efficient PVC plasticizers are elucidated, offering promising alternatives with reduced processing complexities and enhanced market viability.

Polyols are versatile molecules present in many polymer materials that are used and often essential in daily life. However, most bio-based polyols are derived from sugar or vegetable oil, and thus, their production directly competes with the food industry. In this case, CNSL is a promising non-edible renewable resource, which is directly extracted from the shell of cashew nuts. The interesting chemical structure of CNSL and its derivatives (cardanol and cardol) has led to the synthesis of original polyols with hydrophobic and internal plasticizing properties. Useful for the development of additives such as surfactants and soft polymers, CNSL polyols are progressively occupying a unique position in the polymer industry. This review focuses on the use of CNSL as a building block for various polyols. Many different chemical pathways leading to CNSL-based polyols are reviewed and evaluated. Furthermore, we focus on the use of these CNSL-based polyols as surfactants and polymer precursors and the contribution of their specific chemical structure (aromatic ring and long unsaturated alkyl chain) to the properties of the resulting polyesters or polyurethanes.

Two series of sugar esters with alkyl chain lengths varying from 5 to 12 carbon atoms, and with a head group consisting of glucose or galactose moieties, were synthesized. Equilibrium surface tension isotherms were measured, yielding critical micellar concentration (CMC) surface tensions at CMC (γcmc) and minimum areas at the air–water interface (Amin). In addition, Krafft temperatures (Tks) were measured to characterize the ability of molecules to dissolve in water, which is essential in numerous applications. As a comparison to widely used commercial sugar-based surfactants, those measurements were also carried out for four octyl d-glycosides. Impacts of the linkages between polar and lipophilic moieties, alkyl chain lengths, and the nature of the sugar head group on the measured properties were highlighted. Higher Tk and, thus, lower dissolution ability, were found for methyl 6-O-acyl-d-glucopyranosides. CMC and γcmc decreased with the alkyl chain lengths in both cases, but Amin did not appear to be influenced. Both γcmc and Amin appeared independent of the ester group orientation. Notably, alkyl (methyl α-d-glucopyranosid)uronates were found to result in noticeably lower CMC, possibly due to a closer distance between the carbonyl function and the head group.

Since their appearance and commercialization, phenolic resins have been widely used and adopted in many sectors of activity. Produced from phenol and formaldehyde, these thermosetting materials are now being singled out because of the dangerousness of their precursors as well as the fossil raw material from which they are produced. To address and deal with the current general issue on the reduction of the impact of human activity on the environment, this review details and evaluates current studies on alternative molecules that can be used instead of phenol and formaldehyde in the synthesis of phenolic resins. After a contextualizing introduction and a quick review of what phenolic resins are and how these materials are obtained, two main parts are devoted to the platform molecules likely to replace phenol, first, and formaldehyde, second. Finally, the author gives his opinion on the future potential of research concerning the substitution of these molecules and the future of phenolic resins.

Poly(vinyl chloride) (PVC) is a widely employed plastic across diverse industries and is often associated with plasticizers, additives that decrease the inherent rigidity and brittleness of the material. Conventional phthalate-based plasticizers raise substantial toxicity concerns, encouraging the exploration of bio-based alternatives. One such alternative is the inedible oil, cashew nutshell liquid (CNSL), mainly composed of cardanol and cardol. Recent efforts have focused on developing a cardanol-based PVC plasticizers but the isolation of cardanol involves time-consuming, energy-intensive, and costly steps, limiting its market competitiveness. This study aims to assess for the first time, the efficiency of cardol esters, synthesized using acetic acid and different fatty acids (octanoic acid and myristic acid), in order to evaluate the influence of the alkyl chain on plasticizer properties. The chemical structures of these plasticizers were fully characterized by 1H NMR spectroscopy, and the mechanical properties and thermal behavior of PVC films plasticized with these additives were investigated. Finally, the endocrine activity was evaluated for cardol and cardanol acetates. Application of cardol esters as plasticizers for flexible PVC products. Synthesis of additives until mechanical, thermal and reproductive toxicity of platicized PVC samples were investigated. image

With growing environmental concerns and the depletion of petrochemical resources, biomass-derived chemicals have garnered significant attention. Biomass-derived plasticizers have been widely studied as alternatives to toxic petroleum-based plasticizers. However, the bioressources used for their synthesis, an inedible oil derived from agricultural waste, containing cardanol, cardol and anacardic acid, is attracting new interest. Recent research has focused on cardanol-based plasticizers for various polymers such as PVC, PLA, AC and rubber. Cardanol-based biobased plasticizers offer advantages such as renewability, solvent-resistant extraction and efficient plasticizing performance, making them potentially suitable for partial or total replacement of petroleum-based plasticizers. In this study, we discuss the different types of cardanol-based plasticizers according to their chemical structure, functional groups and applications in polymers. The aim of this study is to increase the interest of researchers in biobased plasticizers based on CNSL derivatives.

Aims Our understanding of the rhizosphere is limited by the lack of techniques for in situ live microscopy. Current techniques are either destructive or unsuitable for observing chemical changes within the pore space. To address this limitation, we have developed artificial substrates, termed smart soils, that enable the acquisition and 3D reconstruction of chemical sensors attached to soil particles. Methods The transparency of smart soils was achieved using polymer particles with refractive index matching that of water. The surface of the particles was modified both to retain water and act as a local sensor to report on pore space pH via fluorescence emissions. Multispectral signals were acquired from the particles using a light sheet microscope, and machine learning algorithms predicted the changes and spatial distribution in pH at the surface of the smart soil particles. Results The technique was able to predict pH live and in situ within ± 0.5 units of the true pH value. pH distribution could be reconstructed across a volume of several cubic centimetres around plant roots at 10 μm resolution. Using smart soils of different composition, we revealed how root exudation and pore structure create variability in chemical properties. Conclusion Smart soils captured the pH gradients forming around a growing plant root. Future developments of the technology could include the fine tuning of soil physicochemical properties, the addition of chemical sensors and improved data processing. Hence, this technology could play a critical role in advancing our understanding of complex rhizosphere processes.

Oxidative cleavage of cardanol to a single-component AB monomer allows the preparation of bio-based formaldehyde-free phenolic resins.

CNSL is a crude oil extracted from cashew nutshells. Among the renewable resource materials available, CNSL is considered as an important starting material due to its abundant availability and low cost. Depending on the extraction method, it is possible to obtain an oil with different grades of quality. Once purified, bio-based phenolic compounds of great interest are isolated: cardanol, cardol, and anacardic acid. Many and diverse reactive sites are present on these molecules such as aromatic ring, phenolic hydroxyl, carboxylic acid, and an unsaturated long alkenyl side chain. Their peculiar structures induce some pertinent properties, allowing a good compromise between flexibility and thermal stability. Several platform molecules for the synthesis of additives or monomers have been made by chemical transformation respecting the principles of green chemistry as far as possible. surfactants, plasticizers, paint binder, hardening agents and polymers have been developed from this multi-skilled natural resource.

Surfactants are crystallizing a certain focus for consumer interest, and their market is still expected to grow by 4 to 5% each year. Most of the time these surfactants are of petroleum origin and are not often biodegradable. Cashew Nut Shell Liquid (CNSL) is a promising non-edible renewable resource, directly extracted from the shell of the cashew nut. The interesting structure of CNSL and its components (cardanol, anacardic acid and cardol) lead to the synthesis of biobased surfactants. Indeed, non-ionic, anionic, cationic and zwitterionic surfactants based on CNSL have been reported in the literature. Even now, CNSL is absent or barely mentioned in specialized review or chapters talking about synthetic biobased surfactants. Thus, this review focuses on CNSL as a building block for the synthesis of surfactants. In the first part, it describes and criticizes the synthesis of molecules and in the second part, it compares the efficiency and the properties (CMC, surface tension, kraft temperature, biodegradability) of the obtained products with each other and with commercial ones.

SummaryAgriculture must reduce green-house gas emission and pollution, produce safer and healthier food, closer to home, reducing waste whilst delivering more diverse diets to a growing world population. Soils could enable this transformation, but unfortunately, they have a hugely complex and opaque structure and studies of its myriad of mechanisms are difficult. Here, the fabrication of smart soils for the screening of below-ground bio-processes is demonstrated. Particles were generated from fluoropolymer waste with functionalisation converting them into sensors able to report on key chemical dynamics. Tailored functionalization was obtained by radical terpolymerisation to improve growth conditions and sensing capabilities. The study demonstrates the potential for the development of accelerated genetic or agrochemical screens and could pave the way for improved models for rhizosphere dynamics.

This article describes a part of the results obtained from the cooperation between the University of Lyon1 (France) and the University of Antananarivo (Madagascar). It shows (among others) that useful research can be carried out in developing countries of the tropics if their social, technical, and economic conditions are taken into account. The concepts and methods associated with so-called "green chemistry" are particularly appropriated for this purpose. To illustrate this approach, two examples are shown. The first deals with industrial ecology and concerns waste transformation from the production of cashew nut into an amphiphilic product, oxyacetic derivatives. This product was obtained with a high yield and in a single step reaction. It exhibited an important surfactant property similar to those of the main fossil-based ones but with a much lower ecological impact. The second talks about chemical ecology as an alternative to insecticides and used to control dangerous mosquito populations. New substituted chromones were synthesized and showed biological activities toward Aedes albopictus mosquito species. Strong repellent properties were recorded for some alkoxylated products if others had a significant attractant effect (Kairomone) depending on their stereochemistry and the length of the alkyl chain.

The Diels-Alder (DA) reaction is regarded as quite a useful strategy in organic and macromolecular syntheses. The reversibility of this reaction and the advent of self-repair technology, as well as other applications in controlled macromolecular architectures and crosslinking, have strongly boosted the research activity, which is still attracting a huge interest in both academic and industrial research. The DA reaction is a simple and scalable toolbox. Though it is well-established that furan/maleimide is the most studied diene/dienophile couple, this perspective article reports strategies using other reversible systems with deeper features on other types of diene/dienophile pairs being either petro-sourced (cyclopentadiene, anthracene) or bio-sourced (muconic and sorbic acids, myrcene and farnesene derivatives, eugenol, cardanol). This review is composed of four sections. The first one briefly recalls the background on the DA reactions involving cyclodimerizations, dienes, and dienophiles, parameters affecting the reaction, while the second part deals with the furan/maleimide reaction. The third one deals with petro-sourced and bio-sourced (or products becoming bio-sourced) reactants involved in DA reactions are also listed and discussed. Finally, the authors' opinion is given on the potential future of the crosslinking-decrosslinking reaction, especially regarding the process (e.g., key temperatures of decrosslinking) or possibly monocomponents. It presents both fundamental and applied research on the DA reaction and its applications.

Lipidic polyols based on alpha-hydroxyketone reactive groups were investigated for polyurethane thermosets. The reactivity of this peculiar secondary alcohol group in triacylglycerol structure was compared, without use of catalyst, to that of poly(1,2-diol) triacylglycerol and castor oil to demonstrate the influence of ketone in the alpha position of the alcohol group in the presence of HDI for the urethanization rate. The kinetic effect of the ketone group was also studied on various lipidic architectures: mono(alpha-hydroxyketone) ester, di(alpha-hydroxyketone) diester and tri(alpha-hydroxyketone) triacylglycerol. The presence of hydrogen bonds in the network coming from urethane, residual alcohol, and ketone in hard segments of PU was discussed and correlated with the thermal stability and the soft mechanical properties of the resulting polyurethane thermosets.

The radical polymerization of styrene (St) initiated by a trifluoromethyl radical generated from a perfluorinated highly branched persistent radical (PPFR) is presented with an isolated yield above 70 %. The release of (CF3)-C-. radical occurred from a temperature above 85 degrees C. Deeper H-1 and F-19 NMR spectroscopies of the resulting fluorinated polystyrenes (CF3-PSts) evidenced the presence of both CF3 end-group of the PSt chain and the trifluoromethylation of the phenyl ring (in meta-position mainly). [PPFR](0)/[St](0) initial molar ratios of 3:1, 3:10 and 3:100 led to various molar masses ranging from 1750 to 5400 g mol(-1) in 70-86 % yields. MALDI-TOF spectrometry of such CF3-PSts highlighted polymeric distributions which evidenced differences between m/z fragments of 104 and 172 corresponding to styrene and trifluoromethyl styrene units, respectively. Such CF3-PSt polymers were also compared to conventional PSts produced from the radical polymerization of St initiated by a peroxydicarbonate initiator. A mechanism of the polymerization is presented showing the formation of a trifluoromethyl styrene first, followed by its radical (co)polymerization with styrene. The thermal properties (thermal stability and glass transition temperature, T-g) of these polymers were also compared and revealed a much better thermal stability of the CF3-PSt (10 % weight loss at 356-376 degrees C) and a T-g of around 70 degrees C.

Well-defined linear alkyl benzene surfactants (COx(n)) were successfully synthesized using cardanol as a green phenolic alternative and initiator for polyoxazoline (POx), the hydrophilic block of nonionic surfactants. Various hydrophilic lipophilic balance values were investigated by varying the POx length according to the [monomer]/[initiator] ratio. The chemical structure of the surfactants, in particular the terminal groups, was well identified by matrix assisted laser desorption ionization time of flight mass spectrometry demonstrating the good progress of the cationic ring-opening polymerization. The COx(n) surfactants spontaneously self-assembled in water at a critical aggregation concentration of 1-2 mu mol L-1 into nano-objects characterized by a hydrodynamic diameter of 11-24 nm and a number of aggregations ranging from 30 to 60 according to the worm-like micelle model. (c) 2019 Society of Chemical Industry

A series of bio-based epoxidized plasticizers (CExEp) for soft PVC was synthesized from cardanol and various fatty acids by esterification and epoxidation of the fatty and cardanol unsaturations. The plasticizing properties of these additives for PVC films were proved considering thermal and mechanical data. They seem to be a potential bio-based alternative plasticizer to diisononyl phthalate (DINP), one of the most widespread phthalate plasticizers, with less rigid and stable films. The synergy between epoxy groups, cardanol ring and fatty chains to elaborate efficient primary plasticizers was demonstrated. Moreover, the eco-toxicity using daphnies, algae, and plants as model organisms and endocrinal disruptor tests (YES/YAS) were realized. Our results revealed that the fatty cardanol plasticizer causes a global decrease in toxicity compared to DIN? and no harm for environment and human health were detected without endocrine perturbation effect. These positive results of toxicology allow to consider these cardanol plasticizers in industrial applications as alternative to DINP.

Commercial novolac‐type phenolic thermosets are mainly synthesized from highly toxic precursors such as phenol and formaldehyde. Herein, the phenolic chemistry is renewed with bio‐based and non‐toxic precursors such as cardanol and nonanal to elaborate flexible phenolic thermosets. The two‐step novolac strategy involves the synthesis of a cardanol nonanal pre‐polymer (PCN) prior to its cross‐linking in presence of a supplementary amount of nonanal hardener. The curing process is optimized by rheology measurement and thermogravimetry analysis. The alkyl chains of this phenolic network induces soft mechanical properties acting as internal plasticizers. The softening of the resulting networks do not induce a loss of thermal stability. Showing a good compromise between softness and high thermal resistance, cardanol‐nonanal networks (RCN) seem to be relevant examples of an innovative and biobased approach for phenolic chemistry to design bio‐sourced materials without any petro‐based or hazardous molecules. Practical Applications : Various practical applications where smooth and soft coatings are employed can be considered. Novolac chemistry for bio‐based and notoxic resources : cardanol and nonanal. Softness and high thermal resistance phenolic resins are elaborated. These materials are based on internal plasticized cross‐linked materials.

L’un des defis majeurs dans le domaine des polymeres est la substitution des molecules petro-sourcees en vue de l’elaboration de monomeres, polymeres et d'additifs pour polymeres. Le travail de cette these s’axe sur la valorisation de molecules bio-sourcees et plus particulierement, du cardanol et de derives d'huiles vegetales. Le champ d’application des polymeres etant large, nous avons choisi de nous centrer sur trois grandes problematiques.Dans un premier temps, nous nous sommes interesses a la plastification du PVC qui, actuellement, est majoritairement realisee par des phtalates, famille d’esters petro-sources vivement suspectes d’etre des perturbateurs endocriniens. Des additifs de substitution ont ainsi ete synthetises par une chimie simple a partir du cardanol et d’esters gras. Des stabilites thermiques et des proprietes plastifiantes tres satisfaisantes ont ete obtenues. Enfin, des tests de toxicite et d’ecotoxicite ont demontre l’absence d'impact perturbateur sur la secretion d'hormones sexuelles et la non toxicite vis-a-vis de l'environnement de ces plastifiants bio-sources.Dans un second temps, nous avons revisite la chimie des resines phenoplastes habituellement preparees a partir du phenol et du formaldehyde, deux molecules classees CMR. Nous avons adapte cette chimie robuste a un phenol bio-source, le cardanol, et a un aldehyde bio-source, le nonanal, pour obtenir des resines phenoliques souples. Cette propriete recherchee est le resultat d’une plastification interne des chaines lipidiques pendantes au sein du reseau polymere. Par cet exemple, l’interet des derives d’huiles vegetales pour l’elaboration de materiaux souples a ete demontre. Un compromis entre la souplesse des resines phenoliques et leurs resistances chimique et thermique a ete atteint.Enfin, nous nous sommes tournes vers l’elaboration de polyurethanes reticules a partir d’un ester gras, d’un diester gras et d’un triglyceride porteurs de fonctions alpha-hydroxycetone (collaboration avec l’equipe CASYEN de l’ICBMS). L’apport de la fonction alpha-cetone sur la reactivite du polyol vis-a-vis du reactif isocyanate n’est que modeste par rapport a des derives presentant un groupement alcool isole sur la chaine (huile de ricin) et alcool associe a une autre fonction alcool (triglyceride 1,2-diol). Neanmoins, la presence d’interactions intramoleculaires provenant des groupements cetone a permis d’exacerber la stabilite thermique des materiaux PU et d’elaborer des PU reticules souples par plastification interne comme dans le cas des resines phenoliques.Cette these a ainsi demontre l’apport des phenols lipidiques tels que le cardanol et des chaines grasses dans l’amelioration de la stabilite thermique et de la souplesse au sein de materiaux polymeres.