Macromolecular Rapid Communications最新文献

Polyallenes with appropriate pendants can form stable helices and exhibit significant optical activity. These helical polyallenes contain reactive double bonds that allow for further functionalization, making them a class of chiral functional materials with broad application prospects. This review article delves into the intricacies of synthesizing well-defined helical polyallenes through controlled synthetic methodologies, including helix-sense selective living polymerization, regioselective and asymmetric living polymerization, and one-pot block copolymerization of allenes with aryl monomers. The systemically outlined characteristics of the resulting helical polyallenes and related copolymers are summarized include their unique chiroptical properties, stimuli-responsiveness, helix-induced chiral self-assembly, and circularly polarized luminescence (CPL). Additionally, current challenges and future perspectives in the research of controlled synthesis, functionalities, and applications of helical polyallenes are discussed in detail.

Bisfunctional benzoxazine and polyether diamine-based polymers show Arrhenius-like stress-relaxation varying with stoichiometry and polymerization temperatures proving vitrimeric behavior. Molecular structural investigations reveal the presence of different aminoalkylated phenols occurring at varying ratios depending on polymer composition and polymerization conditions. The vitrimeric mechanism is found to involve an amine exchange reaction of aminoalkylated phenols in an equilibrium reaction like a nucleophilic substitution reaction. As determined by molecular studies and dissolution experiments in reactive solvents, aliphatic and aromatic primary as well as aliphatic secondary amines in the polybenzoxazine structure can act as nucleophiles in reaction with electrophilic methylene bridges. Thus, aminoalkylated phenols proved to be a relevant structural motif resulting in a vitrimeric polybenzoxazine due to amine exchange reaction.

Ultrahigh molecular weight polyethylene (UHMWPE) fibers possess excellent mechanical properties, yet their applications are severely limited by surface inertness and low melting points. To enhance surface activity and temperature resistance, soluble polyimide (PI) is applied to the surface of UHMWPE fibers. A mussel-inspired biomimetic polycatechol/polyamine (PA) coating is initially constructed on the UHMWPE fiber surface by oxidative self-polymerization, serving as a secondary reaction platform. Subsequently, multifunctional UHMWPE-PA-PI fibers are prepared by depositing soluble PI on the fiber surface via impregnation. The PA and PI layers are firmly bonded by hydrogen bonding interactions and physical adhesion. The results show that the PI-coated UHMWPE fiber surface exhibits enhanced chemical activity, hydrophilicity, and thermal stability, with an increased thermal decomposition temperature of approximately 30 °C. Compared to pristine UHMWPE, the breaking force of UHMWPE-PA-PI fibers increases by 14.9%, and the interfacial adhesion strength between the fiber and rubber improves by 65.5%. The PI coatings also provide thermal insulation, acid resistance, and erasability functionalities. This modification strategy is highly efficient, simple, and less damaging, offering a novel solution to address UHMWPE fibers' surface inertness and temperature intolerance.

Self-assembled networks of bottlebrush copolymers are promising materials for biomedical applications due to a unique combination of ultra-softness and strain-adaptive stiffening, characteristic of soft biological tissues. Transitioning from ABA linear-brush-linear triblock copolymers to A-g-B bottlebrush graft copolymer architectures allows significant increasing the mechanical strength of thermoplastic elastomers. Using real-time synchrotron small-angle X-ray scattering, it is shown that annealing of A-g-B elastomers in a selective solvent for the linear A blocks allows for substantial network reconfiguration, resulting in an increase of both the A domain size and the distance between the domains. The corresponding increases in the aggregation number and extension of bottlebrush strands lead to a significant increase of the strain-stiffening parameter up to 0.7, approaching values characteristic of the brain and skin tissues. Network reconfiguration without disassembly is an efficient approach to adjusting the mechanical performance of tissue-mimetic materials to meet the needs of diverse biomedical applications.

This study presents an organocatalytic C-H functionalization approach for postpolymerization modification (PPM) of poly(ethylene oxide) (PEO). Most of PEO PPM is previously processed at the end hydroxy group, but recent advances in C-H functionalization open a way to modify the backbone position. Structurally diverse carboxylic acids are attached to PEO through a cascade process of radical generation by peroxide and oxidation to oxocarbenium by tertiary butylammonium iodide. Attaching carboxylic acids yields a series of functionalize PEO with acetal units (2-5 mol%) in a backbone, which is not accessible via conventional copolymerization of epoxides. The optimized conditions minimizes the uncontrolled degradation or crosslinking from the highly reactive radical and oxocarbenium intermediate. The newly introduced acetal units bring degradability of PEO as well as delivery of carboxylic acid molecules. Hydrolysis studies with high molecular weight functionalization PEO (M_n = 13.0 kg mol^-1) confirm the steady release of fragmented PEO (M_n ∼ 2.0 kg mol^-1) and carboxylic acid over days and the process rate is not sensitive to pH variation between pH 5 and 9. The presented method offers a versatile and efficient way to modify PEO with potential energy and medical applications.

Diglycidyl ether of bisphenol A crosslinking with glutaric anhydride is used to form the conventional "covalent adaptive network", polyether sulfone (PES) by coiling and aggregating on the adaptive network is used to significantly increase the uncured resin viscosity for improving the processability of epoxy resin, but inevitably affecting the curing reaction and dynamic transesterification reaction. This study investigates the crucial roles of PES in curing dynamics and stress relaxation behavior. The results indicate that although PES does not directly participate in the crosslinking reaction of polyester-based epoxy vitrimers. Moreover, the isothermal curing studies reveal that the addition of PES can greatly bring forward the reaction rate peak from conversion α = 0.6 to α = 0.2, meaning that the curing mechanism transfers from chemical control to diffusion control. Dynamic property analysis shows that the addition of PES significantly accelerates stress relaxation, especially at lower temperatures, leading to low viscous flow activation energy E_τ and relatively insensitive stress relaxation behavior to temperature. Introducing PES into vitrimer resin greatly improves crosslinking density (2.31 × 10⁴ mol m^{- 3}), enhancing glass transition temperature (82.68 °C), tensile strength (68.66 MPa), and fracture toughness (6.25%). Additionally, the modified vitrimer resin exhibits satisfying shape memory performance and reprocessing capability.

Front Cover: In the cover image of article 2400343, Levent Kamil Toppare, Ali Cirpan, and co-workers basically bridge the nature of chemistry and renewable energy. The round-bottomed flask encapsulates a solar cell, symbolizing the bond of energy with wet lab chemistry. The molecular orbitals surrounding showcase the synergy between molecular design and computational chemistry.

Front Cover: Due to the advantages of low energy consumption, no air and water pollutions, the reactive polyurethane films (RPUFs) are replacing the solvated and waterborne PUFs nowadays. In article 2400284, Dongming Qi, Zhichao Huang, Qi Zhong, and co-workers explore the microstructure evolution of RPUFs. The polyaddition and film-formation processes can be divided into three stages as chain extension, gelation and microphase separation. The obtained film-formation mechanism can be used as the theoretical guidance for the controllable preparation of high-performance products based on RPUFs.

In recent years, fatty acids have garnered significant attention as a natural phase-change material and a hydrophobizer due to their biocompatibility and biodegradability. In this study, the utilization of fatty acid is proposed as a polymerization medium for the first time. As a specific reaction, chemical oxidative polymerizations of pyrrole is conducted using ferric chloride as an oxidant in a stearic acid medium. The polymerizations resulted in the production of micrometer-sized polypyrrole (PPy) grains, which are aggregates of atypical primary particles with submicrometer size. The PPy grains are doped with stearic acid, suggesting that the stearic acid functioned as a dopant and a hydrophobizing agent as well as a polymerization medium. The dried PPy grains can adsorb at the air-water interface and function as a liquid marble stabilizer with light-to-heat photothermal properties. The liquid marble can move on a planar air-water interface by Marangoni flow induced by NIR laser light irradiation.