Deciphering the Self-Catalytic Mechanisms of Polymerization and Transesterification in Polybenzoxazine Vitrimers.

The use of internal catalysts has emerged as a pivotal design principle to facilitate dynamic exchanges within covalent adaptable networks (CANs). Polybenzoxazines, specifically, have shown considerable potential in generating vitrimers through thermally induced transesterification reactions catalyzed internally by tertiary amines. This study aims to investigate the chemical complexities of transesterification reactions within benzoxazine vitrimers. To achieve this, model molecules using various phenolic acids and amino-alcohol derivatives were synthesized as precursors. The structure of these model molecules was fully elucidated by using nuclear magnetic resonance (NMR). Differential scanning calorimetry (DSC) and rheology experiments evidenced the accelerated network formation of the precursors due to the presence of aliphatic -OH groups. Thermogravimetric analysis coupled with microcomputed gas chromatography (TGA-µGC) was used to provide evidence of transesterification reactions. The results showed that the spatial proximity between tertiary amine and hydroxyl groups significantly enhances the rate exchange, attributed to a neighboring group participation (NGP) effect. Interestingly, kinetic experiments using complementary NMR techniques revealed the thermal latency of the tertiary amine of benzoxazine toward transesterification reactions as its opening is needed to trigger the dynamic exchange. The study highlights the crucial role of steric hindrance and tertiary amine basicity in promoting the dynamic exchange in an internally catalyzed system.

Semiquantitative Solid-State NMR Study of the Adsorption of Soybean Oils on Silica and Its Significance for Rubber Processing.

Soybean oil (SBO) is a renewable material used as an alternative to conventional petroleum-derived oils in the processing of rubber composites. Upon chemical modifications, such as epoxidation, its performance in the processing of rubber can be significantly improved, as indicated by a considerable reduction of the mixing energy. Although it has been hypothesized that hydrogen bonding between functional groups (e.g., epoxy) of SBOs and silanols present on the silica surface plays a key role, there is still a lack of direct evidence supporting this hypothesis. In this work, it is demonstrated that there is an overall correlation between the epoxy concentration of SBOs and the mixing energy, consistent with the long-held hypothesis. In particular, a correlation between the SBO-silica adsorption affinity and the degree of epoxidation is revealed by a set of surface-selective solid-state nuclear magnetic resonance (ssNMR) experiments. In addition, the surface-selective ssNMR technique demonstrated in this work could also be used to evaluate the adsorption affinity of other oils and/or additives more broadly.

Design of cross-linked semicrystalline poly(ε-caprolactone)-based networks with one-way and two-way shape-memory properties through Diels-Alder reactions.

Cross-linked poly(ε-caprolactone) (PCL)-based polyesterurethane (PUR) systems have been synthesized through Diels-Alder reactions by reactive extrusion. The Diels-Alder and retro-Diels-Alder reactions proved to be useful for enhancing the molecular motion of PCL-based systems, and therefore their crystallization ability, in the design of cross-linked semicrystalline polymers with one-way and two-way shape-memory properties. Successive reactions between α,ω-diol PCL (PCL(2) ), furfuryl alcohol, and methylene diphenyl 4,4'-diisocyanate straightforwardly afforded the α,ω-furfuryl PCL-based PUR systems, and subsequent Diels-Alder reactions with N,N-phenylenedimaleimide afforded the thermoreversible cycloadducts. The cross-linking density could be modulated by partially replacing PCL-diol with PCL-tetraol. Interestingly, the resulting PUR systems proved to be semicrystalline cross-linked polymers, the melting temperature of which (close to 45 °C) represented the switching temperature for their shape-memory properties. Qualitative and quantitative measurements demonstrated that these PUR systems exhibited one-way and two-way shape-memory properties depending on their cross-linking density.

Poly(ethylene oxide)-b-poly(L-lactide) diblock copolymer/carbon nanotube-based nanocomposites: LiCl as supramolecular structure-directing agent.

This work relies on the CNT dispersion in either solution or a polymer matrix through the formation of a three-component supramolecular system composed of PEO-b-PLLA diblock copolymer, carbon nanotubes (CNTs), and lithium chloride. According to a one-pot procedure in solution, the "self-assembly" concept has demonstrated its efficiency using suspension tests of CNTs. Characterizations of the supramolecular system by photon correlation spectroscopy, Raman spectroscopy, and molecular dynamics simulations highlight the charge transfer interaction from the CNTs toward the PEO-b-PLLA/LiCl complex. Finally, this concept was successfully extended in bulk (absence of solvent) via melt-processing techniques by dispersing these complexes in a commercial polylactide (PLA) matrix. Electrical conductivity measurements and transmission electron microscopy attested for the remarkable dispersion of CNTs, confirming the design of high-performance PLA-based materials.

Synthesis of clicked imidazolium-containing biosourced copolymers and application in carbon nanotube dispersion.

New polyesters incorporating a variable quantity of imidazolium rings along the backbone are synthesized by Huisgen 1,3-dipolar cycloaddition ("click" reaction). Subsequently, the imidazolium-grafted copolymers reveal an efficient dispersing ability toward the carbon nanotubes (CNTs) through supramolecular interactions in organic media. Interestingly, these compounds offer a simple and reliable strategy to control the quantity of dispersed CNTs as a function of imidazolium content. This approach is particularly suitable for the elaboration of biosourced and biodegradable materials based on poly(butylene succinate) with high-performance properties.

Sustainable Esterification of a Soda Lignin with Phloretic Acid.

In this work, a sustainable chemical process was developed through the Fischer esterification of Protobind® lignin, a wheat straw soda lignin, and phloretic acid, a naturally occurring phenolic acid. It aimed at increasing the reactivity of lignin by enhancing the number of unsubstituted phenolic groups via a green and solvent-free chemical pathway. The structural features of the technical and esterified lignins were characterized by complementary spectroscopic techniques, including 1H, 13C, 31P, and two-dimensional analysis. A substantial increase in p-hydroxyphenyl units was measured (+64%, corresponding to an increase of +1.3 mmol g-1). A full factorial design of the experiment was employed to quantify the impact of critical variables on the conversion yield. The subsequent statistical analysis suggested that the initial molar ratio between the two precursors was the factor predominating the yield of the reaction. Hansen solubility parameters of both the technical and esterified lignins were determined by solubility assays in multiple solvents, evidencing their high solubility in common organic solvents. The esterified lignin demonstrated a better thermal stability as the onset of thermal degradation shifted from 157 to 220 °C, concomitantly to the shift of the glass transition from 92 to 112 °C. In conclusion, the esterified lignin showed potential for being used as sustainable building blocks for composite and thermoset applications.

Bio-Based Bisbenzoxazines with Flame Retardant Linker.

This work explores the strategy of incorporating a highly substituted reactive flame retardant into a benzoxazine moiety. For this purpose, a DOPO-based flame retardant received a chain extension via reaction with ethylene carbonate. It was then reacted with phloretic acid to obtain a diphenol end-capped molecule, and further reacted with furfurylamine and paraformaldehyde to obtain a benzoxazine monomer via a Mannich-like ring closure reaction. This four-step synthesis yielded a partly bio-based halogen-free flame retardant benzoxazine monomer (DOPO-PA-fa). The successful synthesis was proven via NMR, IR and MS analysis. The polymerization behavior was monitored by DSC and rheological analysis both showing the polymerization starts at 200 °C to yield pDOPO-PA-fa. pDOPO-PA-fa has a significant thermal stability with a residual mass of 30% at 800 °C under ambient atmosphere. Furthermore, it reached a V-0 rating against small flames and an OI of 35%. Blended with other benzoxazines, it significantly improves their thermal stability and fire resistance. It emphasizes its potential as flame retardant agent.

Unique Carbonate-Based Single Ion Conducting Block Copolymers Enabling High-Voltage, All-Solid-State Lithium Metal Batteries.

Safety and high-voltage operation are key metrics for advanced, solid-state energy storage devices to power low- or zero-emission HEV or EV vehicles. In this study, we propose the modification of single-ion conducting polyelectrolytes by designing novel block copolymers, which combine one block responsible for high ionic conductivity and the second block for improved mechanical properties and outstanding electrochemical stability. To synthesize such block copolymers, the ring opening polymerization (ROP) of trimethylene carbonate (TMC) monomer by the RAFT-agent having a terminal hydroxyl group is used. It allows for the preparation of a poly(carbonate) macro-RAFT precursor that is subsequently applied in RAFT copolymerization of lithium 1-[3-(methacryloyloxy)propylsulfonyl]-1-(trifluoromethylsulfonyl)imide and poly(ethylene glycol) methyl ether methacrylate. The resulting single-ion conducting block copolymers show improved viscoelastic properties, good thermal stability (T onset up to 155 °C), sufficient ionic conductivity (up to 3.7 × 10-6 S cm-1 at 70 °C), and high lithium-ion transference number (0.91) to enable high power. Excellent plating/stripping ability with resistance to dendrite growth and outstanding electrochemical stability window (exceeding 4.8 V vs Li+/Li at 70 °C) are also achieved, along with enhanced compatibility with composite cathodes, both LiNiMnCoO2 - NMC and LiFePO4 - LFP, as well as the lithium metal anode. Lab-scale truly solid-state Li/LFP and Li/NMC lithium-metal cells assembled with the single-ion copolymer electrolyte demonstrate reversible and very stable cycling at 70 °C delivering high specific capacity (up to 145 and 118 mAh g-1, respectively, at a C/20 rate) and proper operation even at a higher current regime. Remarkably, the addition of a little amount of propylene carbonate (∼8 wt %) allows for stable, highly reversible cycling at a higher C-rate. These results represent an excellent achievement for a truly single-ion conducting solid-state polymer electrolyte, placing the obtained ionic block copolymers on top of polyelectrolytes with highest electrochemical stability and potentially enabling safe, practical Li-metal cells operating at high-voltage.

Multipurpose Processing Additives for Silica/Rubber Composites: Synthesis, Characterization, and Application.

Processing additives are a special group of chemicals included in rubber formulations to facilitate the flowability of the resultant compounds. Their addition generally affects the cured properties of the subsequent rubber composites, and fine-tuning of the compound formulation is therefore required. In this work, an attempt has been made to address this issue through the preparation of new bio-based processing additives capable of promoting the mixing of the rubber compound while at the same time enhancing mechanical properties following curing. A significant decrease in the mixing energy at the first stage of mixing (~10%) has been observed by substituting only a small percentage of the conventional petroleum-derived process oil with aminated epoxidized soybean oil. Concomitantly, it is found that this aminated epoxidized soybean oil promotes rubber curing and increases the tensile strength of the final composite by ~20% compared to the control.

Synthesis of Novel Benzoxazines Containing Sulfur and Their Application in Rubber Compounds.

This work reports the synthesis and successful use of novel benzoxazines as reinforcing resins in polyisoprene rubber compounds. For this purpose, three new dibenzoxazines containing one (4DTP-fa) or two heteroatoms of sulfur (3DPDS-fa and 4DPDS-fa) were synthesized following a Mannich condensation reaction. The structural features of each benzoxazine precursor were characterized by 1H and 13C nuclear magnetic resonance (NMR), Fourier transform infrared (FTIR) and Raman. The new precursors showed well suited reactivity as characterized by differential scanning calorimetry (DSC) and rheology and were incorporated in rubber compounds. After the mixing, the curing profiles, morphologies and mechanical properties of the materials were tested. These results show that the structural feature of each isomer was significantly affecting its behavior during the curing of the rubber compounds. Among the tested benzoxazines, 3DPDS-fa exhibited the best ability to reinforce the rubber compound even compared to common phenolic resin. These results prove the feasibility to reinforce rubber compounds with benzoxazine resins as a possible alternative to replace conventional phenolic resins. This paper provides the first guide to use benzoxazines as reinforcing resins for rubber applications, based on their curing kinetics.

An Investigation on the Thermally Induced Compatibilization of SBR and α-Methylstyrene/Styrene Resin.

The miscibility between two polymers such as rubbers and performance resins is crucial to achieve given targeted properties in terms of tire performances. To this aim, α-methylstyrene/styrene resin (poly(αMSt-co-St)) are used to modify the viscoelastic behavior of rubbers and to fulfill the requirements of the final applications. The initial aim of this work was to understand the influence of poly(αMSt-co-St) resins blended at different concentrations in a commercial styrene-butadiene rubber (SBR). Interestingly, while studying the viscoelastic properties of SBR blends with poly(αMSt-co-St), crosslinking of the rubber was observed under conditions where it was not expected to happen. Surprisingly, after the crosslinking reactions, the poly(αMSt-co-St) resin was irreversibly miscible with SBR at concentrations far above its immiscibility threshold. A detailed investigation involving characterization technics including solid state nuclear magnetic resonance led to the conclusion that poly(αMSt-co-St) is depolymerizing under heating and can graft onto the chains of SBR. It results in an irreversible compatibilization mechanism between the rubber and the resin.

Development of plasticized edible films from Opuntia ficus-indica mucilage: A comparative study of various polyol plasticizers.

Mucilage polysaccharide was extracted from Opuntia ficus-indica cladodes (Cactaceae) and its composition was determined by sugar analysis using HPLC-RID and its structural features were elucidated by FTIR and 1H and 13C NMR. Films from the extracted mucilage were loaded at 40% (w/w) with glycerol, sorbitol, PEG 200 or PEG 400. The physical, thermal, mechanical and barrier properties of the obtained films were investigated. The highest water vapor barrier properties of plasticized mucilage films were obtained with sorbitol reaching water vapor permeability (WVP) values up to 3 times lower than the other films. The tensile strength (TS) values of films plasticized with PEG 200 and sorbitol were about 2 times higher than those of glycerol-plasticized films. The significant effect of polyol type plasticizers on the different properties of mucilage edible films was related to their structural features that promote different interactions with mucilage polysaccharides as demonstrated by FTIR and thermal properties.

Exploration of cardanol-based phenolated and epoxidized resins by size exclusion chromatography and MALDI mass spectrometry.

Cardanol and cardanol derivatives are among the most important biobased materials currently investigated in green chemistry, as renewable and promising building blocks in lieu of traditional raw materials from non renewable resources, in particular owing to the olefinic linkages on the C15 alkyl side-chain. Despite the increasing interest they arouse, analytical chemistry dedicated to cardanol and associated resins has been rarely reported in the literature, found even poorer when dealing with chromatography and mass spectrometry. In this work, a thorough molecular characterization was conducted using matrix assisted laser desorption ionization (MALDI) mass spectrometry, size exclusion chromatography (SEC), and SEC-MALDI coupling to gain insights into the composition of phenolated, epoxidized, and epoxidized phenolated cardanol. A nomenclature was proposed to properly describe the numerous species found in these materials, while simulations of the unsaturation patterns and their comparison with the detected patterns in MALDI-MS gave useful details about the phenolation treatment expected to occur on the polyunsaturated C15 side chain. Finally, the SEC-MALDI off-line coupling allowed SEC peaks to be deconvoluted by mass spectrometry and MALDI artefacts related to matrix adduction to be pointed out.

Reversible positioning at submicrometre scale of carbon nanotubes mediated by pH-sensitive poly(amino-methacrylate) patterns.

The selective adsorption of carbon nanotubes (CNTs) on a pH-reversible PDMAEMA patterned gold surface is presented. In acidic conditions, a selective CNTs adsorption onto the polymer brushes is obtained due to ammonium-π interactions. The reversible behavior was shown by successive treatments in both alkaline and acidic solutions with CNTs.