Article
Polymer Science
Lindsay L. Robinson, Eden S. Taddese, Jeffrey L. Self, Christopher M. Bates, Javier Read de Alaniz, Zhishuai Geng, Craig J. Hawker
Summary: In this study, a catalyst-free covalent adaptable network (CAN) was developed by using a cross-linker with sulfur-atom neighboring group participation (NGP) to increase the rate of bond exchange. The network exhibited thermally mediated cross-link interchange and associated flow behavior, enabling reprocessing over multiple damage and repair cycles. Additionally, the NGP-based CANs were chemically recyclable.
Article
Chemistry, Multidisciplinary
Wenbin Niu, Xianfei Cao, Yunpeng Wang, Bowen Yao, Yusen Zhao, Jie Cheng, Suli Wu, Shufen Zhang, Ximin He
Summary: Vitrimers with dynamic covalent bonds show self-healability and mechanical robustness, but their potential for optical function recovery is underexplored. A novel photonic vitrimer combining photonic crystals and vitrimers exhibits high mechanical stability, creep-resistance, and self-healing ability, making it suitable for sensory applications and interactive devices. This material design provides a general strategy for functionalizing vitrimers optically, showing promise for soft robotics, wearable devices, and human-machine interaction.
ADVANCED FUNCTIONAL MATERIALS
(2021)
Article
Chemistry, Multidisciplinary
Filip Van Lijsebetten, Yann Spiesschaert, Johan M. Winne, Filip E. Du Prez
Summary: Internally catalyzed amide bonds were introduced to obtain covalent adaptable polyamide networks, showing that their dynamic character can be activated without external catalysts. Various polyamide-based dynamic networks with variable mechanical and viscoelastic properties were obtained using a straightforward curing process, demonstrating a marked temperature response and high resistance to irreversible deformation.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Materials Science, Characterization & Testing
Xin Dong, Dezheng Hu, Huaqing Wang, Yiwan Huang, Shijun Long, Gaowen Zhang, Xuefeng Li
Summary: Polyethylene (PE) is the most widely used polymer. Enhancing the properties of PE, such as increasing molecular weight or moderate cross-linking, can lead to processing difficulties and hinder recycling. This study presents a new approach to improve the tensile strength and heat resistance of PE through reversible boronic esters bonds.
Article
Polymer Science
Qiong Li, Songqi Ma, Pengyun Li, Binbo Wang, Zhen Yu, Hongzhi Feng, Yanlin Liu, Jin Zhu
Summary: The study designed catechol-based acetal CANs with accelerated acetal exchange through neighboring group participation (NGP). These CANs were prepared from bio-based epigallocatechin gallate (EGCG) and tri(ethylene glycol) divinyl ether (TEGVE) via one-step click cross-linking without catalysts. The dynamic covalent polymer networks showed excellent solvent resistance and mechanical properties due to dense cross-link density and high rigidity.
Article
Biochemistry & Molecular Biology
Liang Yang, Christian Marcus Pedersen
Summary: Protected 2-O-benzyolated glycosyl formates were synthesized in one-step from the corresponding orthoester using formic acid as the sole reagent. Glucopyranosyl, mannopyranosyl and galactopyranosyl donors were synthesized and their glycosylation properties were studied. Bismuth triflate was the preferred catalyst and KPF6 was used as an additive. The glycosylations showed excellent 1,2-trans-selectivities and high yields.
Article
Chemistry, Multidisciplinary
Chumeng Luo, Weichao Wang, Wei Yang, Xingyu Liu, Jun Lin, Liqun Zhang, Shaojian He
Summary: In this study, a novel hardener was designed to prepare an epoxy vitrimer with dual-dynamic covalent bonds. The experimental results showed that EPV-4-AFD-VAN outperformed the single-disulfide-containing vitrimer in terms of performance, and it maintained good recovery properties and solvent resistance.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2023)
Article
Polymer Science
Loc Tan Nguyen, Francesca Portone, Filip E. Du Prez
Summary: In this study, a scalable synthesis of catalyst-free, covalent adaptable networks (CANs) based on beta-amino amides was reported. The materials showed high activation energy and superior hydrolytic resistance.
Article
Engineering, Environmental
Yi Tan, Kaili Wang, Youming Dong, Shanshan Gong, Sheldon Q. Shi, Jianzhang Li
Summary: Transparent wood (TW) with unique anisotropic structures and advantageous properties has great potential in advanced building fields. However, achieving shape manipulatable TW with high-performance remains a challenge. In this study, a high-performance shape manipulatable TW with exchangeable dynamic thiocarbamate bonds (TCBs) was successfully fabricated, exhibiting impressive optical transparency, low thermal conductivity, excellent mechanical properties, and fascinating shape manipulation ability. This research provides a promising avenue for the application of TW as energy efficient and intelligent building materials.
CHEMICAL ENGINEERING JOURNAL
(2022)
Article
Polymer Science
Roy Wink, Soumabrata Majumdar, Rolf A. T. M. van Benthem, Johan P. A. Heuts, Rint P. Sijbesma
Summary: Neighboring group assisted rearrangement increases relaxation rates in dynamic covalent networks for easier (re)processing. The introduction of anionic phosphate diesters as the sole dynamic group and β-hydroxy groups as a neighboring group mimics the self-cleaving backbone structure of RNA. The diester-based networks show slower dynamics but better hydrolytic and thermal stability compared to phosphate triester-based networks.
Article
Chemistry, Organic
Shuaipeng Jia, Hebo Ye, Lei You
Summary: Chalcogen bonds play an important role in modulating the conformation and dynamics of imine systems. This study reveals the interplay between chalcogen bonds and dynamic covalent chemistry, showing that chalcogen bonding can significantly influence the kinetics and thermodynamics of imine exchange. The computational studies provide mechanistic insights and demonstrate the strongest interaction with tellurium. The findings have potential implications in molecular recognition, dynamic assemblies, catalysis, and related fields.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Multidisciplinary Sciences
Mengqi Du, Hannes A. Houck, Qiang Yin, Yewei Xu, Ying Huang, Yang Lan, Li Yang, Filip E. Du Prez, Guanjun Chang
Summary: The click chemistry reaction between triazolinedione (TAD) and indole derivatives was used to create force-reversible C-N bonds, which enable materials to display reversible stress-responsiveness in real time. This method provides a general strategy to enhance mechanical strength and ductility in covalently crosslinked polymer materials.
NATURE COMMUNICATIONS
(2022)
Article
Polymer Science
Erez Cohen, Liat Avram, Elena Poverenov
Summary: This study suggests using non-covalent supramolecular interactions to improve the mechanical and barrier properties of nature-sourced polymers. By controlling the modification of chitosan, biopolymers with tailored thermal, mechanical, and surface properties can be obtained. These findings have the potential to become a method for the formation of high-performance biodegradable alternatives to petroleum-based polymers, with applications in packaging, food, agriculture, and medicine.
MACROMOLECULAR RAPID COMMUNICATIONS
(2023)
Article
Polymer Science
Stephan Maes, Filip Van Lijsebetten, Johan M. Winne, Filip E. Du Prez
Summary: In this study, it was shown that the introduction of N-sulfonyl urethane bonds leads to dynamic covalent exchange reactions under milder conditions. These exchangeable N-sulfonyl urethane motifs were then incorporated into a cross-linked PU matrix to facilitate plastic flow at lower temperatures. The resulting materials demonstrated good (re)processability and retained their thermal properties.
Article
Chemistry, Multidisciplinary
Fangfang Peng, Junfeng Xiang, Huisheng Qin, Bingfeng Chen, Ran Duan, Wenling Zhao, Shiqiang Liu, Tianbin Wu, Wenli Yuan, Qian Li, Jikun Li, Xinchen Kang, Buxing Han
Summary: This study reports a highly selective electro-oxidation method for the synthesis of benzylic alcohols from benzylic C-H in an ionic liquid-based solution. Under specific conditions, the selectivity of the reaction can reach 95.7%. Mechanistic investigation reveals the crucial roles of proton-coupled electron transfer and low-barrier hydrogen bonds in the reaction.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Dimitri Berne, Sebastien Lemouzy, Pascale Guiffrey, Sylvain Caillol, Vincent Ladmiral, Eric Manoury, Rinaldo Poli, Eric Leclerc
Summary: This study describes a spontaneous (uncatalyzed) Michael addition of thiols to alpha-trifluoromethyl acrylates and its efficient application in the preparation of a thermoset. Mechanistic investigation reveals a probable solvent-assisted proton transfer in the rate-determining step and a considerable lowering of the energy barrier induced by the CF3 group in the addition of arene- and alkanethiols to tert-butyl trifluoromethyl acrylate in polar aprotic solvents.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Polymer Science
Florian Cuminet, Sylvain Caillol, Eric Dantras, Eric Leclerc, Sebastien Lemouzy, Cedric Totee, Olivier Guille, Vincent Ladmiral
Summary: In this study, a novel dynamic material was synthesized from α,α-difluorodicarboxylic acid (P-DAF) and a commercial diepoxy (BDGE). The material showed a high gel content, flowability when heated, and successful reshaping under mild conditions.
EUROPEAN POLYMER JOURNAL
(2023)
Article
Polymer Science
Sylvain Caillol, Remi Auvergne, Abdelatif Manseri, Gilles Boutevin, Bernard Boutevin, Marina Grimaldi, Patrick Balaguer
Summary: In this article, selective synthesis methods that avoid the formation of by-products were proposed, allowing for the industrialization of these synthetic routes. By utilizing the difference in reactivity and basicity of catalysts, a two-step synthesis of mono-epoxy vanillin or a single-step epoxidation of the two hydroxyl groups to obtain the diepoxy was achieved. Furthermore, a toxicology study demonstrated the potential of vanillin as a substitute for bisphenol A.
JOURNAL OF APPLIED POLYMER SCIENCE
(2023)
Article
Biochemistry & Molecular Biology
Leo Bricotte, Kamel Chougrani, Valerie Alard, Vincent Ladmiral, Sylvain Caillol
Summary: 1,3-dihydroxyacetone (DHA) is a versatile bio-based synthon derived from glycerol, primarily used as a self-tanning agent in cosmetics. This review explores the physical and chemical properties of DHA and its industrial production routes, with a focus on its potential as a bio-based building block for specialty polymers. The delicate reactivity of DHA, including dimerization and isomerization reactions, offers opportunities for the synthesis of innovative and biodegradable polymers, addressing sustainability challenges.
Editorial Material
Biochemistry & Molecular Biology
Sylvain Caillol
Article
Biochemistry & Molecular Biology
Mathilde Grosjean, Dimitri Berne, Sylvain Caillol, Vincent Ladmiral, Benjamin Nottelet
Summary: The development of dynamic covalent chemistry enables the design of materials that can be reprocessed through internal exchange reactions under thermal stimulus. This study produced PEG-PLA/hydroxyurethane networks incorporating imine bonds, which showed dynamic behavior at moderate temperatures and good reprocessability. This work opens up the possibility of developing a new generation of dynamic materials that combine degradable PEG-PLA copolymers and hydroxyurethane modifiers for on-demand medical devices.
Article
Polymer Science
Sylvain Caillol
Summary: Cashew nut shell liquid (CNSL) is an important renewable resource material with unique structural features, abundant availability and low cost. The three reactive sites in CNSL, namely phenolic hydroxyl, aromatic ring and unsaturation(s) in the alkenyl side chain, have been utilized to develop a wide range of chemicals and products. Promising cardanol-based products, such as epoxy and acrylic monomers, plasticizers and surfactants, have attracted increasing attention for their potential industrial applications.
EUROPEAN POLYMER JOURNAL
(2023)
Article
Polymer Science
Christine Elian, Baptiste Quienne, Sonia Lajnef, Fabienne Peyrot, Regis Moilleron, Samir Abbad Andaloussi, Sylvain Caillol, Davy-Louis Versace
Summary: We designed a new visible-light epoxy-based alizarin photosensitizer for the cationic polymerization process under visible light irradiation. The combination of the photosensitizer and the iodonium salt demonstrated highly efficient photoinitiating properties and the ability to produce protonic acids and singlet oxygen under light exposure, which can initiate the polymerization process and act as a biocide against bacteria. By adjusting the proportion of monomers, the thermal and mechanical properties of the resulting materials were modulated.
EUROPEAN POLYMER JOURNAL
(2023)
Article
Polymer Science
Dimitri Berne, Rinaldo Poli, Sylvain Caillol, Vincent Ladmiral, Eric Leclerc
Summary: This study develops a series of catalyst-free covalent adaptable networks (CANs) using a reversible thia-Michael reaction. By modulating the structure and functionality of the thiol monomers, a wide range of mechanical and thermal properties are achieved. The study also highlights the relationship between monomer structure and dynamic properties, and evaluates the reprocessing capability of the materials.
Article
Chemistry, Applied
Maxinne Denis, Alan Pare, Damien Le Borgne, Sylvain Caillol, Claire Negrell
Summary: This article reports the first synthesis of HydroxyUrethane modified alkyd resins by polycondensation reaction. Two new hydroxyurethane modifiers were synthesized from renewable resources and copolymerized with alcohols and acid derivatives to yield HydroxyUrethane modified alkyd resins. The chemical resistance analysis showed that HUM increased the alkali resistance of alkyd resins up to 44%. Film properties such as gloss or drying time remained equivalent with the exception of color.
PROGRESS IN ORGANIC COATINGS
(2023)
Article
Chemistry, Multidisciplinary
Sebastien Lemouzy, Alienor Delavarde, Frederic Lamaty, Xavier Bantreil, Julien Pinaud, Sylvain Caillol
Summary: The synthesis of a new biobased aromatic diisocyanate from lignocellulosic raw material offers a greener approach for isocyanate production and the polyurethane industry. The conversion of bisguaiacol F into bisguaiacol F diamine was successfully achieved under mechanochemical and microwave conditions. The resulting diisocyanate was synthesized using a phosgene-free/room temperature protocol and showed potential as a biobased alternative to petrochemical-based diisocyanates.
Article
Chemistry, Multidisciplinary
Ali Alaaeddine, Vincent Ladmiral, Wassim El Malti, Lolwa Haydar, Sylvain Caillol, Bruno Ameduri
Summary: Efficient methods for the cycloaddition of CX2 with fluorinated epoxides to produce cyclic carbonates or cyclic xanthates were developed. By optimizing the reaction conditions, high yields of the desired products were obtained. The reaction was proven to be reproducible with different substrates and two new fluorinated five-membered bis-CCs and bis-XAs were synthesized with high yields.
COMPTES RENDUS CHIMIE
(2023)
Article
Polymer Science
Florian Cuminet, Sebastien Lemouzy, Eric Dantras, Eric Leclerc, Vincent Ladmiral, Sylvain Caillol
Summary: Vitrimers are polymers that can bridge the gap between crosslinked thermosets and recyclable linear thermoplastics. Recently, catalyst-free reshapable vitrimers have been developed using strategies like inductive effects or neighboring group participation. These vitrimers, such as polyester vitrimers, feature highly crosslinked networks without the need for a catalyst.