Silicon-containing hyperbranched polymers (Si-HBPs) have drawn much attention due to their promising applications. However, the construction of Si-HBPs, especially those containing functional aromatic units in the branched backbones by the simple and efficient Piers-Rubinsztajn (P–R) reaction, has been rarely developed. Herein, a series of novel hyperbranched polycarbosiloxanes were prepared by the P–R reactions of methyl-, or phenyl-triethoxylsilane and three Si–H containing aromatic monomers, including 1,4-bis(dimethylsilyl)benzene, 4,4′-bis(dimethylsilyl)-1,1′-biphenyl and 1,1′-bis(dimethylsilyl)ferrocene, using B(C₆F₅)₃ as the catalyst for 0.5 h at room temperature. Their structures were fully characterized by Fourier transform infrared spectroscopy, ¹H NMR, ¹³C NMR, and ²⁹Si NMR. The molecular weights were determined by gel permeation chromatography. The degrees of branching of these polymers were 0.69–0.89, which were calculated based on the quantitative ²⁹Si NMR spectroscopy. For applications, the ferrocene-linked Si-HBP can be used as precursors to produce functional ceramics with good magnetizability after pyrolysis at elevated temperature.

The water sensitivity of metal-organic frameworks (MOFs) as a common and crucial issue has greatly hindered their practical applications. Here, we present a facile and general approach to improve the water resistance of a typical MOF, i.e., CuBTC [Cu₃(BTC)₂(H₂O)₃]_n (BTC = benzene-1,3,5-tricarboxylate) using a post-modification reaction with aminopropyltriethoxylsilane (APTES) at room temperature. The afforded material is denoted as CuBTC@APTES. Various spectroscopic methods reveal that the organosilicon linkers have been successfully grafted onto CuBTC by electrostatic attraction between acid and base groups and without affecting the original coordination mode and basic structure. Compared with CuBTC, the water stability of CuBTC@APTES was significantly improved. The pristine CuBTC almost lost all its crystallinity, morphology and pore structure after 3-day treatment in water, while CuBTC@APTES is able to retain its main crystal structure and basic porosity after the same treatment. This finding can be explained by the successful introduction of the organosilicon molecular overlayer on the periphery of CuBTC to slow down the destruction of weak metal coordination bonds by water molecules, thus improving the water stability of CuBTC. The solution of water sensitivity provides more opportunities for the practical applications of CuBTC, such as aqueous phase catalysis and gas separation in humid environments. This simple approach can certainly be expanded to improve the water resistance of other carboxylate-containing ligand-based MOFs.

Herein, we present two novel ferrocene-containing porous organic polymers, FPOP-1 and FPOP-2, by the Heck reactions of 1,1′-divinylferrocene with two tetrahedral silicon-centered units, i.e., tetrakis(4-bromophenyl)silane and tetrakis(4′-bromo-[1,1′-biphenyl]-4-yl)silane. The resulting materials possess high thermal stability and moderate porosity with the Brunauer–Emmer–Teller (BET) surface areas of 499 m² g⁻¹ (FPOP-1) and 354 m² g⁻¹ (FPOP-2) and total pore volumes of 0.43 cm³ g⁻¹ (FPOP-1) and 0.49 cm³ g⁻¹ (FPOP-2). The porosity is comparable to previously reported ferrocene-containing porous polymers. These materials possess comparable CO₂ capacities of 1.16 mmol g⁻¹ (5.10 wt%) at 273 K and 1.0 bar, and 0.54 mmol g⁻¹ (2.38 wt%) at 298 K and 1.0 bar (FPOP-1). The found capacities are comparable to, or higher than many porous polymers having similar or higher surface areas. They have high isosteric heats of up to 32.9 kJ mol⁻¹, proving that the affinity between the polymer network and CO₂ is high, which can be explained by the presence of ferrocene units in the porous networks. These results indicate that these materials can be promisingly utilized as candidates for the storage or capture of CO₂. More ferrocene-containing porous polymers can be designed and synthesized by combining ferrocene units with various aromatic monomers under this strategy and their applications could be explored.

This study addresses the poor compatibility between resin and reinforcement and the weak interfacial bonding in poly(ether ether ketone) (PEEK)-based composites by preparing several macromolecular silane coupling agents. Three types of coupling agents with different structures were synthesized using hydroxyl-terminated PEEK oligomers, and their structures were confirmed by FT-IR, NMR, and XPS analyses. The molecular weights were determined by GPC, and TG analysis showed that all three coupling agents exhibited good thermal stability. Glass fibers and carbon fibers were surface-modified with these coupling agents. SEM and EDS analyses revealed uniform coatings on the fiber surfaces, accompanied by increases in the characteristic elements of the coupling agents. Mechanical tests showed that the tensile and flexural strengths of the treated composites were higher than those of the untreated ones. DSC and TG results indicated significant improvements in crystallinity and thermal properties. These enhancements are attributed to improved fiber–matrix compatibility and interfacial bonding. Overall, this work establishes a structure-tailored macromolecular silane coupling strategy, providing new insights into structure–property relationships and offering an effective approach to enhance the performance of PEEK-based composites.

This study presents targeted contributions to the development of macromolecular silane coupling agents (MSCAs) and high-performance fiber-reinforced polyimide (PI) composites. Three novel MSCAs were synthesized via chemical imidation and transamidation reactions, using hexafluoroisopropylidene diphthalic anhydride and 2,3,3′,4′-diphenyl ether tetracarboxylic acid as dianhydride monomers, 4,4′-diaminodiphenyl ether and 1,3-bis(4′-aminophenoxy)benzene as diamine monomers, and aminopropyltriethoxysilane (KH550) as the capping agent. Structural characterization by FTIR, ¹H NMR, and XPS confirmed the successful synthesis of the target products, with silicon contents of 3.29%, 3.37%, and 3.66%, respectively. The MSCAs exhibited excellent thermal stability, with 10% weight loss temperatures ranging from 462 °C to 543.3 °C, and good solubility in most polar organic solvents, addressing the poor processability of conventional macromolecular coupling agents. Compared with small-molecule KH550, the MSCAs significantly enhanced interfacial properties: the average tensile and flexural strengths of the composites increased by 11.0% and 9.8%, respectively, compared to 3.9% and 4.0% for KH550. SEM analysis demonstrated that MSCAs improved resin adhesion to fibers and fiber–resin compatibility. Additionally, the T5, T10, and glass transition temperatures of the composites were further optimized due to polymer chain diffusion and entanglement. This work provides a feasible strategy for interfacial design in high-performance polyimide composites.