Macromolecular Rapid Communications最新文献

Inside Front Cover: On the bottom left-hand side of the cover, three people are sitting in front of a movie screen watching the film “FOIM”, a neologism from “FOIl” and “foaM”. This film is shown in five individual images on the right-hand side of the cover. It shows the gradual transformation of a foil of shape memory polymer into a foam, triggered by the application of heat. To illustrate the required temperature increase, the images contain a color gradient from cold (blue) to warm (red). The background of the cover exhibits a microscopic image of the foam, which is also colored using the same gradient. More details can be found in article 2401103 by Anna-Lisa Poser and Thorsten Pretsch.

Back Cover: Fee volume space of conventional polymers is applied as a nanospace. No previous works have focused on such tiny space enclosed by polymer chains for the functionalization. In article 2400980, Yuya Oaki and co-workers show synthesis of conductive polymers in the nanospace from the guest monomer molecules in vapor phase.

Front Cover: In article 2401154, Jianbo Yin and co-workers report the preparation of anisotropic trimeric poly(ionic liquid) microspheres via microwave-assisted dual-crosslinked seed emulsion polymerization. The formation trimeric morphology depends on the multiple local contraction forces in dual-crosslinked poly(ionic liquid)microspheres having a lowly crosslinked core and a highly crosslinked shell during swelling and the re-absorption of core for bulges during microwave polymerization.

Data-driven polymer research has experienced a dramatic upswing in recent years owing to the emergence of artificial intelligence (AI) alongside automated laboratory synthesis. However, the chemical complexity of polymers employed in automated synthesis still lacks in terms of defined functionality to meet the need of next-generation high-performance polymer materials. In this work, the automated self-optimization of the reversible addition-fragmentation chain-transfer (RAFT) polymerization of pentafluorophenyl acrylate (PFPA) is presented, a versatile polymer building-block enabling efficient post-polymerization modifications (PPM). The polymerization system consisted of a computer-operated flow reactor with orthogonal analytics comprising an inline benchtop nuclear magnetic resonance (NMR) spectrometer, and an online size exclusion chromatography (SEC). This setup enabled the automatic determination of optimal polymerization conditions by implementation of a multi-objective Bayesian self-optimization algorithm. The obtained poly(PFPA) is precisely modified by amidation taking advantage of the active pentafluorophenyl (PFP) ester. By controlling the feed ratios of solutions containing different amines, their incorporation ratio into the polymer, and therefore its resulting properties, can be tuned and predicted, which is shown using NMR, differential scanning calorimetry (DSC), and infrared (IR) analysis. The described strategy represents a versatile method to synthesize and modify reactive polymers in continuous flow, expanding the range of functional polymer materials accessible by continuous, high-throughput synthesis.

Block copolymers (BCPs), capable of self-assembling into various nanoscale structures, are widely used in adhesives owing to their versatile properties. However, conventional BCP-based adhesives pose environmental concerns: they are petroleum-derived, non-degradable, and have a non-tunable adhesion strength. To address these challenges, a novel BCP is designed comprising a conventional hard segment, polystyrene (PS), and a green rubbery segment, poly(ethyl lipoate) (PEtLp), derived from the bio-based molecule α-lipoic acid. The PS-b-PEtLp is synthesized via the base-catalyzed ring-opening polymerization from thiol-terminated PS. Adhesion tests showed that PS-b-PEtLp with cylindrical nanostructures exhibited higher adhesion strength than that with lamellar structures. Importantly, the dynamic disulfide bonds in PEtLp enable a reversible and adjustable adhesion strength under UV light. Upon UV irradiation, the adhesion strength decreases by approximately half, facilitating easy separation from the adherends. Additionally, the selective depolymerization of the PEtLp block achieves 100% conversion, enabling the recovery of the monomer (EtLp) and macroinitiator (thiol-terminated PS). This study introduces a sustainable, degradable, and reusable adhesive derived from renewable resources, providing a promising solution to the environmental challenges associated with traditional petroleum-based adhesives.

Ethylene-vinyl acetate (EVA) is widely used in shoe soles due to its foamability, affordability, and resilience. However, rising consumer demands for greater durability and energy rebound drive the need for performance enhancements. This study presents a novel approach by introducing a silicone-based masterbatch (MB), developed by incorporating a silicone-based shear-stiffening gel (SSG) (polyborosiloxane) with EVA through a reactive extrusion process. Two types of SSG/EVA are produced, i.e., crosslinked SSG/EVA (abbreviated as SSG/EVA-X) and non-crosslinked SSG/EVA (abbreviated as SSG/EVA-NX). The SSG/EVA-X reveals interconnected phases, including crosslinked and uncrosslinked SSG and EVA, and mixed regions. The developed SSG/EVA are further utilized as MB to modify and enhance EVA foam properties. Incorporating SSG/EVA MB into EVA foam significantly enhances its physico-mechanical properties. These improvements are pronounced in EVA foams incorporating with the SSG/EVA-X MB (abbreviated as EVA/MB-X), which outperforms the SSG/EVA-NX MB, (abbreviated as EVA/MB-NX) due to superior material integration. Dynamic impact energy return of EVA foam increases by over 10%, while abrasion resistance shows an improvement of more than 50% at the optimal SSG/EVA MB content. These findings suggest that crosslinking silicone MB with EVA presents a promising strategy for EVA foam modification, offering a pathway to enhance its performance.

Despite decades of extensive efforts in the engineering and molecular design of organic semiconductors (OSCs), the transistor performance and stability of n-type OSCs remain lower than those of their p-type counterparts. In recent years, incorporating ionic liquids (ILs) into electronic and optoelectronic devices has enabled exceptional performance and environmental stability through doping, film crystallization processes, and energetic alignment because of their unique physicochemical properties. This paper reports on bias-stable n-type organic field-effect transistors (OFETs) based on an n-type fullerene-based semiconductor ([6,6]-phenyl-C-61-butyric acid methyl ester (PCBM)) with a solid-state IL additive. The optimized PCBM-IL OFETs exhibits a more than fivefold increase in electron mobility, excellent continuous bias-stress stability for over 1 h, and a remarkable increase in current output under ambient conditions due to synergistic PCBM-IL interactions and robust interfacial properties, which reduces resistance and minimized interface traps.

Owing to their low dielectric constant (D_k), processability, and mechanical properties, siloxane-based polymers have attracted attention as insulating materials for next-generation communication. However, a major challenge regarding siloxane-containing materials is their high dielectric loss tangent (dissipation factor) (D_f). A polymer is designed and synthesized by combining polysiloxanes with phenyl side groups on the main chain and a polyimide structure (polysiloxane-imide) to improve the D_f value. Compared with conventional dimethylsiloxane-based polymers, the resulting polysiloxane-imide, obtained as a bendable, self-supporting film, exhibits a significantly reduced D_f value. The rigidity of the phenyl group-containing polysiloxane presumably contributes to the improvement in the D_f value. Furthermore, polysiloxane-imides exhibit excellent hydrophobicity and high heat resistance with their 5% weight loss temperature of over 400 °C. The synthesized polysiloxane-imides with phenyl side groups, which possess various properties, including low D_k, low D_f, and excellent hydrophobicity, are expected to contribute to the future practical application of siloxane-based insulating materials.