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.
Review
Chemistry, Multidisciplinary
A. Gaston Orrillo, Ricardo L. E. Furlan
Summary: Sulfur plays an important role in dynamic covalent chemistry, especially as part of dynamic sulfur-based bonds (DSBs). DSBs have ideal properties such as high reactivity and good reversibility, which make them highly suitable for the preparation of dynamic covalent systems. They also offer chemical flexibility, opening up multiple applications.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Xiao-Lian Wang, Li-Tian Zhang, Shan He, Xiao-Xian Chen, Xiao-Chun Huang, Hao-Long Zhou
Summary: Covalent organic frameworks (COFs) are a class of crystalline porous materials with promising applications. However, the lack of an efficient and scalable synthesis protocol hinders their further application. This study proposes a synthesis method based on dynamic covalent chemistry, using imine exchange reactions, to rapidly prepare high-quality COFs with desirable structures.
CHEMISTRY OF MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Yang Chao, Akash Krishna, Muthusamy Subramaniam, Dong-Dong Liang, Sidharam P. Pujari, Andrew C-H Sue, Guanna Li, Fedor M. Miloserdov, Han Zuilhof
Summary: The SuFEx reaction between sulfonimidoyl fluorides and phenols, sulfonimidates, exhibits dynamic covalent chemistry with other phenols. This enantiospecific reaction can be completed at room temperature within minutes and with high yields, making it useful for asymmetric synthesis and sustainable polymer production. Its broad scope further extends the applications of SuFEx and related click chemistries.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Bo Yang, Wusha Miao, Haijun Feng, Qian Zhao, Tao Xie, Ning Zheng
Summary: Typical dynamic covalent polymer networks can achieve self-healing, reprocessing, and shape reconfigurability, while topology isomerizable networks enable programmable physical properties. Combining these two transformation mechanisms into one network is challenging but can greatly enhance material versatility. In this study, researchers successfully regulated the bond exchange kinetics in a dynamic covalent network using an on-demand catalyst. The network demonstrated thermal healing, reprocessing, and shape reconfiguration without changing the polymer properties, and upon UV activation, significant network isomerization occurred. Further control of the switchable catalyst allowed selective programming of both the shapes and properties, offering potential benefits for flexible electronics and soft robotics.
JOURNAL OF MATERIALS CHEMISTRY A
(2022)
Article
Polymer Science
Zhi Rong Ou, Wei Li Peng, Min Zhi Rong, Ming Qiu Zhang
Summary: A novel strategy utilizing reversible boronic ester bonds and imine bonds has been proposed for controllable depolymerization and recovery of polymer blends. Through the preparation of reversibly interlocked polymer networks (RILNs) from two preformed crosslinked polymers, a cascading effect between boronic ester bonds and imine bonds is enabled, allowing controlled depolymerization and recovery.
Review
Polymer Science
Li-Han Rong, Eugene B. Caldona, Rigoberto C. Advincula
Summary: This review provides an overview of the fundamentals, applications, and future possibilities of photoinduced electron/energy transfer reversible addition-fragmentation chain transfer (PET-RAFT) polymerization. It highlights the compatibility of PET-RAFT with ambient conditions and green solvents, as well as its potential as an alternative to conventional RAFT techniques for producing well-defined polymers.
POLYMER INTERNATIONAL
(2023)
Article
Chemistry, Multidisciplinary
Alex E. Crolais, Neil D. Dolinski, Nicholas R. Boynton, Julia M. Radhakrishnan, Scott A. Snyder, Stuart J. Rowan
Summary: A new series of catalyst-free, room-temperature dynamic thia-Michael acceptors bearing an isoxazolone motif were developed and utilized to access both dynamic covalent networks and linear polymers. By leveraging the generation of aromaticity upon thiol addition and tuning the electronic-withdrawing/donating nature of the acceptor at two different sites, a wide range of equilibrium constants were obtained. Integration into a ditopic isoxazolone-based Michael acceptor allowed access to both bulk dynamic networks and linear polymers with tailored thermomechanical properties.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Polymer Science
David S. Rivero, Rafael E. Paiva-Feener, Tanausu Santos, Endika Martin-Encinas, Romen Carrillo
Summary: Dynamic nucleophilic aromatic substitution of tetrazines has been used to synthesize dynamic covalent polymer networks that are recyclable and can be degraded by UV irradiation or chemical stimulus, allowing for efficient recovery of the original monomer. Additionally, the polymers can be converted into different ones by irreversible monomer exchange, and their properties can be modulated by postfunctionalization with polar groups through the inverse electron demand Diels-Alder reaction.
Article
Polymer Science
Lewis C. Chambers, Christopher Barner-Kowollik, Leonie Barner, Lukas Michalek, Hendrik Frisch
Summary: In this study, we investigate a cross-linked polymer network formed through a visible light photodynamic [2 + 2] cycloaddition driven by styrylpyrene chemistry. By using irradiation of different wavelengths, the network can be generated with varying degrees of openness. The network retains its mechanical properties even at the photostationary state, and we hypothesize that applying an additional stimulus can induce disintegration of the network by spacing the [2 + 2] units during ultraviolet irradiation.
Review
Biochemistry & Molecular Biology
Shuyuan Zheng, Guofeng Liu
Summary: Dynamic covalent polymers with adaptive and reversible properties have attracted increasing attention. However, the emissive ability of such polymers has not been widely reviewed. This review summarizes emissive polymeric materials based on different types of dynamic covalent bonds and discusses their chemical reactions, stimuli-responsive behaviors, and potential applications.
Article
Polymer Science
Grayson L. Jackson, Joseph M. Dennis, Neil D. Dolinski, Michael van der Naald, Hojin Kim, Christopher Eom, Stuart J. Rowan, Heinrich M. Jaeger
Summary: This study investigates the use of dynamic covalent chemistry to tailor the rheological behaviors of dense suspensions. The results demonstrate that the equilibrium constant of the polymeric solvent to the particle interface can be controlled through dynamic thia-Michael bonds, leading to shear thinning or antithixotropy. The implementation of dynamic covalent chemistry provides a new approach to tailor the macroscopic rheology of suspensions.
Article
Chemistry, Multidisciplinary
Guoshan Jiang, Lifeng Wang, Hebo Ye, Hanxun Zou, Lei You
Summary: This article reports a facile method for chirality sensing of monoalcohols by combining dynamic covalent chemistry with helical chirality. The authors constructed four diphenylethene (DPE) derived cyclic hemiaminals and achieved efficient incorporation of a broad range of alcohols and thiols. The reversibility was verified by dynamic component exchange. The results lay a foundation for future endeavors in chemical sensing, asymmetric synthesis, and chiroptical materials.
Article
Chemistry, Multidisciplinary
Filip Van Lijsebetten, Kevin De Bruycker, Evelyne Van Ruymbeke, Johan M. Winne, Filip E. Du Prez
Summary: Dynamic covalent networks provide a unique way of controlling macroscopic material properties by linking them to the underlying chemistry. Researchers have developed a rheological paradigm that correlates the composition of a reactive polymer segment to the rate of network rearrangement. They discovered that a generalised Maxwell model can separate and quantify the dynamic behavior of each type of reactive segment individually, which is crucial for understanding the mechanics of the final material. By combining statistical modeling and rheology measurements, possible bond catalysis and dissociation were related to structural changes.
Article
Chemistry, Organic
Ziyi Li, Ling Zhang, Yuntao Zhou, Daijun Zha, Yu Hai, Lei You
Summary: Dynamic covalent chemistry plays an important role in the creation of molecular assemblies, complex systems, and ordered frameworks. By controlling the ring-chain tautomerism of 2-formylbenzoic acid, dynamic covalent reactions (DCRs) of common N-, O-, and S-mononucleophiles are achieved. The dual reactivity of open aldehyde and cyclic hemiacetal forms, combined with thermodynamic stabilization and kinetic effect, enables efficient reactions of a wide range of alcohols, thiols, and amines. The dynamic nature of the system is verified through component exchange and switch of reactions can be achieved by manipulating substrate selectivity. Mechanistic investigation provides insights for future design and applications.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Takuma Watabe, Hideyuki Otsuka
Summary: We present a new method for achieving swelling-induced mechanochemistry using a multinetwork (MN) strategy, which allows polymer networks to repeatedly swell with monomers and solvents. The isotropic expansion of the first network (FN) provides sufficient force to drive the mechanochemical scission of a radical-based mechanophore, difluorenylsuccinonitrile (DFSN). The MN polymers not only demonstrate the ability to modify networks through swelling force, but also show tunable reactivity of the dissociative unit through hierarchical network architecture design.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Hajime Sugita, Yi Lu, Daisuke Aoki, Hideyuki Otsuka, Koichiro Mikami
Summary: Radical-type mechanophores (RMs) can undergo homolytic cleavage of their central C-C bonds upon exposure to mechanical forces, which affords radical species. Understanding the characteristics of these radical species allows bespoke mechanoresponsive materials to be designed and developed. In this paper, the synthesis and characterization of arylfluorene-based RM derivatives, and the importance of thermodynamic stability and oxygen tolerance for their functions and applicability, are reported. Furthermore, the mechanochromism of a BTAF-centered polymer synthesized by ATRP was demonstrated.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Polymer Science
Yuji Higaki, Masaya Takahashi, Takumi Masuda
Summary: The phase behavior of double zwitterionic diblock copolymers composed of PCB2 and PSB4 has been investigated in aqueous solutions. Phase diagrams were constructed for different polymer concentrations and PSB4 volume fractions, showing symmetric characteristics above a certain concentration. The morphology transitions from columnar to lamellar to columnar with decreasing polymer concentration, and the phase boundaries exhibit a negative slope below a certain concentration. The unique molecular compartment formed by the lyotropic mesophase of double hydrophilic block copolymers provides a low interfacial tension environment for hydrophilic molecules.
MACROMOLECULAR CHEMISTRY AND PHYSICS
(2023)
Article
Chemistry, Multidisciplinary
Hajime Sugita, Yi Lu, Daisuke Aoki, Hideyuki Otsuka, Koichiro Mikami
Summary: In this study, the synthesis and characterization of two series of arylfluorene-based mechanophores were reported. Density functional theory (DFT) calculations revealed the importance of thermodynamic stability and oxygen tolerance for the functions and applicability of these materials. Furthermore, the mechanochromism of a polymer containing one of the mechanophores was demonstrated through ball-milling.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Polymer Science
Yuji Higaki, Naoki Kuraoka, Takumi Masuda, Mai Nakamura, Emi Hifumi
Summary: English Summary: Cononsolvency refers to the phenomenon where a polymer collapses in specific compositions of good solvent mixtures. In this study, the coil-globule-coil transitions of two zwitterionic polymers, PCB2 and PMPC, were investigated and compared in water, ethanol, and water-ethanol mixed solvents. PCB2 exhibited cononsolvency in water-ethanol mixed solvents with specific ethanol volume fractions. A statistical mechanical model involving competitive hydrogen bonding and cooperative hydration explained the reentrant square well-type sharp coil-globule transition observed in PCB2. PCB2 showed a broader cononsolvency range than PMPC due to its lower association constants of water and ethanol and stronger competition for hydrogen bonding. The zwitterion-specific cononsolvency characteristics were explained based on electrostatic potentials and van der Waals energies.
Article
Chemistry, Multidisciplinary
Hirogi Yokochi, Robert T. O'Neill, Takumi Abe, Daisuke Aoki, Roman Boulatov, Hideyuki Otsuka
Summary: Sacrificial chemical bonds are effective in increasing the toughness of elastomers. Mechanical bonds, such as rotaxanes or catenanes, have similar effects on the fracture strain, stress, and energy of elastomers as covalent bonds.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Editorial Material
Chemistry, Multidisciplinary
Hendrik Heinz, Yogesh M. Joshi, Hongbo Zeng, Heng-Kwong Tsao, Sissi J. A. de Beer, Erin Koos, Atsushi Takahara, Gilbert C. Walker
Article
Polymer Science
Yuji Higaki, Takumi Masuda, Mai Nakamura, Masaya Takahashi
Summary: The cononsolvency-induced solvent composition-specific self-assembly of a double hydrophilic diblock copolymer was studied. The copolymer dissolved in water and ethanol but aggregated in mixtures with a specific ethanol volume fraction range due to the cononsolvency of one of its components. The copolymer produced well-ordered mesoscopic lattice structures in water-ethanol mixed solvents, and the morphology depended on the ethanol fraction and polymer concentration.
Article
Polymer Science
Yuji Higaki, Honoka Toyama, Takumi Masuda, Shingo Kobayashi, Masaru Tanaka
Summary: This study synthesized double-hydrophilic block copolymers composed of a water-soluble zwitterionic polymer and a water-insoluble nonionic polymer. The assembly characteristics of these copolymers in water were investigated, and it was found that the size of particles and microphase-separated structures depended on the composition and degree of polymerization of the copolymer. Furthermore, the assembly behavior was not affected by the concentration of salt.
Article
Materials Science, Multidisciplinary
Yucheng Zhang, Koichi Hasegawa, Sota Kamo, Kiyoka Takagi, Atsushi Takahara
Summary: Epoxy adhesives are crucial in the manufacturing of various components and products in industrial and daily use. Modifying the surface of adherents with PGMA greatly improves the lap shear strength of epoxy adhesive-bonded joints. The effect of PGMA layer thickness on reinforcement is still uncertain.
ACS APPLIED POLYMER MATERIALS
(2023)
Article
Polymer Science
Rikito Takashima, Daisuke Aoki, Hideyuki Otsuka
Summary: In this study, various maleimides were prepared using p-maleimidophenylisocyanate (PMPI) and used to modify biobased furan polymers (BFPs) through the Diels-Alder reaction. The reactive sites in PMPI exhibited orthogonal reactivity, allowing for the preparation of tailor-made modification agents. The T-g values and rheological properties of the modified polymers could be tuned by adjusting the structure of the maleimide and its reaction conversion, demonstrating the practical usability of BFP derived from furfural. This strategy can be applied to obtain biobased materials with desirable functions and physical properties.
JOURNAL OF POLYMER SCIENCE
(2023)
Article
Chemistry, Multidisciplinary
Yi Lu, Hajime Sugita, Koichiro Mikami, Daisuke Aoki, Hideyuki Otsuka
Summary: A rational design strategy for Radical-type mechanophores (RMs) with high thermal tolerance and mechanoresponsiveness is proposed. Experimental and theoretical analysis reveals that the high thermal tolerance of these RMs is related to the radical-stabilization energy (RSE) and the Hammett and modified Swain-Lupton constants at the para-position (& sigma;(p)). The trend of the RSE values is in good agreement with the experimentally evaluated thermal tolerance of a series of mechanoresponsive RMs based on the bisarylcyanoacetate motif.
Article
Polymer Science
Takumi Abe, Takehiro Kamiya, Hideyuki Otsuka, Daisuke Aoki
Summary: Commodity polymers are increasingly required to be environmentally friendly. Poly(isosorbide carbonates) (PICs), synthesized from non-toxic and biodegradable isosorbide (ISB), have attracted interest as an alternative to petroleum-based polymers due to their superior thermal stability and transparency. In this study, a novel concept was established in which PICs are used as a source of fertilizer, providing innovative chemical recycling systems to address the global food-production problem.
Article
Chemistry, Multidisciplinary
Sinan Feng, Yokajaksusri Nutthon, Hiroyasu Masunaga, Sono Sasaki, Roman Selyanchyn, Shigenori Fujikawa, Shinichi Murata, Atsushi Takahara
Summary: This study investigated the impact of morphology on the gas transport properties of a poly-(ether-block-amide) (PEBA) multiblock copolymer. Annealing temperature was varied to evaluate changes in microstructure and gas transport properties of PEBA. Time-resolved attenuated total reflection Fourier transform infrared spectroscopy was used to determine the diffusion coefficient of CO2 in PEBA. The findings revealed a 38% increase in CO2 permeability in the annealed sample, while maintaining a high CO2/N-2 permselectivity.
Article
Chemistry, Organic
Rikito Takashima, Daisuke Aoki, Akira Takahashi, Hideyuki Otsuka
Summary: We have developed a versatile and simple synthetic method for producing a [3]catenane. By heating a rotaxane containing bis(hindered amino) disulfide groups, the [3]catenane is spontaneously and selectively produced. The obtained [3]catenane can be successfully polymerized, providing a platform for the synthesis of various interlocking polymers. A thermally driven interconversion between the rotaxane and catenane is achieved using a dynamic bis(hindered amino) disulfide.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Polymer Science
Yuanzhang Jiang, Xuyi Wang, Yanting Han, Dakai Gong, Yingchun Gu, Lin Tan
Summary: In this study, FeCl3 and poly(acrylic acid) (PAA) were doped into waterborne polyurethanes (WPUs) to create multifunctional materials with self-healing and antimicrobial properties. WPU/Fe/PAA-5.5, containing 5.5 wt % PAA, exhibited excellent mechanical properties, strong self-healing capabilities, and an impressive antimicrobial rate of over 90%. These supramolecular films were also highly recyclable through hot-pressing.
Article
Polymer Science
Longyu Tian, Min Wang, Guangming Liao, Baoliang Liu, Sujuan Zhang, Yucheng Sun, Zhen Meng, Jintao Zhang, Zaijun Lu
Summary: Two kinds of benzoxazine monomers were synthesized and used to prepare polybenzoxazine anion exchange membranes (AEMs) with quaternary ammonium functionalization. The LQPBZ AEM exhibited better ion conductivity and alkaline stability.
Article
Polymer Science
Claire A. Lemarchand
Summary: This study investigates the shock behavior of three different polymers through molecular dynamics simulations. The results reveal specificities in the shock behavior of polymers, including deviations from the linear relation between shock velocity and particle velocity, as well as differences in shear stress relaxation behind the shock front. It is found that the deviation of the Hugoniot locus is related to the change in the relative contribution of bonding and non-bonding potential energies, while polymers with higher glass transition temperatures exhibit slower shear stress relaxation.
Article
Polymer Science
Zengquan Liu, Xiaochun Yin, He Zhang, Shuo Gao, Qinglin Kuang, Yanhong Feng
Summary: A powder solid-state extension (PSSE) technology was proposed to address the high melt viscosity issue of UHMWPE. By uniaxial extension and sintering in the solid state, a highly self-reinforced material was prepared. X-ray diffraction and scattering techniques were used to study the structural evolution during the PSSE process, and a solid-phase induced transformation model was established.
Article
Polymer Science
Zhike Li, Anyu Luo, Rui Zhou, Xin Li, Haiyan Li
Summary: A novel high temperature resistance IL@SiO2 nanocapsules were successfully prepared and their friction and wear properties in PA6 composites were studied. The addition of IL@SiO2 nanocapsules reduced the friction coefficient and wear rate without affecting the mechanical properties of PA6. The synergy between the IL core and SiO2 wall in the nanocapsules improved the self-lubricating performance of the PA6 composites.
Article
Polymer Science
Xin Liu, Xuhong Guo, Qi Liao
Summary: In this study, an algorithm for accurately estimating viscosity is developed using molecular dynamics simulations and the Green-Kubo formula. This algorithm can be applied to complex systems with long correlations, such as macromolecular and biological simulation systems.
Article
Polymer Science
Hao Pu, Yun-Lei Hou, Jing -Zhou Chen, Dong -Lin Zhao
Summary: The use of modified graphene improves the interfacial adherence of carbon fibers to epoxy resin, resulting in enhanced interfacial and bending properties of CF and matrix in CF/EP composites, as well as increased interlaminar shear strength and flexural strength.
Article
Polymer Science
Wei-Chung Ke, Jin-Wei Lin, Manohar Reddy Busireddy, Yueh-Hsing Lee, Jiun-Tai Chen, Chain-Shu Hsu
Summary: This study introduces a crosslinkable monomer, TAIC, to synthesize three crosslinked polyimide films, which exhibit improved thermal, mechanical, and dielectric properties. The introduction of TAIC enhances the tensile strength, reduces the dielectric constant and dielectric loss, and decreases the coefficient of thermal expansion of the polyimide films.
Article
Polymer Science
Alex Kwasi Kumi, Ruiling Fan, Ye Chen, Yumei Zhang
Summary: The difference in leaching of amylopectin from cellulose/amylopectin/1-butyl-3-methylimidazolium chloride ([Bmim][Cl]) blends during regeneration in water and aqueous ethanol has been studied. Molecular dynamics simulations showed that the dissolution and regeneration mechanisms of amylopectin in [Bmim][Cl] are similar to cellulose in ionic liquids. Water regeneration leads to weak electrostatic interactions, resulting in high leaching of amylopectin. In contrast, ethanol-water interactions enhance electrostatic interactions among amylopectin chains, limiting amylopectin leaching in aqueous ethanol.
Article
Polymer Science
Xi Zeng, Junwei Zhou, Junbiao Peng, Chunsheng Zhang, Danling Wang, Yihu Song, Qiang Zheng
Summary: This study utilizes an oligomer deep eutectic solvent (DES) based on polyethylene glycol to regulate the vulcanization kinetics of rubber. The results show that the DES can accelerate vulcanization at low temperatures without affecting the crosslinking density and Mullins effect.
Article
Polymer Science
Qianqian Yue, Yongfei Peng, Xingjian Liu, Aihua He, Huarong Nie
Summary: The addition of metal deactivators can effectively suppress the aging of TBIR, prolong its lifespan, and have no negative effects on its physical and processing properties. These research findings are of great importance for improving the stability and aging resistance of polymers.
Article
Polymer Science
J. Gomez-Caturla, J. Ivorra-Martinez, R. Tejada-Oliveros, V Moreno, D. Garcia-Garcia, R. Balart
Summary: This work focuses on the development of environmentally friendly PLA formulations by using different esters derived from geraniol as plasticizers. The results show that these esters have good compatibility with PLA, and they can effectively enhance the elongation and plasticity of PLA, reduce its glass transition temperature, and slightly improve its water absorption capabilities.
Article
Polymer Science
Dandan Li, Zhaohui Lu, Zhao Ke, Ke Xu, Fengna Dai, Youhai Yu, Guangtao Qian, Chunhai Chen
Summary: In this study, cross-linked PI aerogel membranes with low dielectric constant and high moisture resistance were prepared by co-polymerization and scraping coating technology. The incorporation of fluorinated blocks and benzimidazole ring structures resulted in novel PI aerogel membranes with fascinating dielectric properties and outstanding moisture resistance.
Article
Polymer Science
Zhaoyang Chu, Qing Zhang, Haihua Luo, Han Zhou, Fapei Zhang, Wei Chen, Wenhua Zhang
Summary: Multi-physical fields solution processing strategy is a universal and facile method for preparing various conjugated polymer films and high-performance devices. In this study, we employed a combined microfluidic flow and ultrasonication strategy (FU) for processing CP solutions, and found a pronounced synergetic effect in promoting the pre-ordering of chains in solution. The conformation order and anisotropy of the solution were revealed through various characterizations. A non-classical nucleation model for polymer crystallization in non-equilibrium solution processing was confirmed. The roles of microfluidic flow and ultrasonication in chain aggregation and crystallization were addressed through multi-physical simulations. Compared to pristine solutions, the FU strategy showed improved solution anisotropy and crystallization kinetics, resulting in higher crystallinity in films and increased mobilities in OFET devices. The FU processing strategy provides a universal approach for regulating chain conformation and aggregation in conjugated polymer solutions.
