Construction of Fluorescent Conjugated Polytriazole Containing Double-Decker Silsesquioxane: Click Polymerization and Thermal Stability

Abstract

This study synthesized two azide-functionalized monomers through p-dichloro xylene and double-decker silsesquioxane (DDSQ) units with NaN3 to form DB-N3 and DDSQ-N3 monomers, respectively. In addition, five different propargyl-functionalized monomers were also prepared from hydroquinone, bisphenol A, bis(4-hydroxyphenyl)methanone, 2,4-dihydroxybenzaldehyde (then reacted with hydrazine hydrate solution) and 1,2-bis(4-hydroxyphenyl)-1,2-diphenylethene with propargyl bromide to form P-B, P-BPA, P-CO, P-NP, and P-TPE monomers, respectively. As a result, various DDSQ-based main chain copolymers could be synthesized using Cu(I)-catalyzed click polymerization through DDSQ-N3 with different propargyl-functionalized monomers, of which the chemical structure and molecular weight could be confirmed by using Fourier-transform infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR), and gel permeation chromatography (GPC) analyses. Differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), scanning electron microscope (SEM), transmission electron microscopy (TEM), and photoluminescence (PL) spectroscopy analyses also could characterize the thermal stability, morphology, and optical behaviors of these DDSQ-based copolymers. All results indicate that the incorporation of an inorganic DDSQ cage could improve the thermal stability such as thermal decomposition temperature and char yield, because of the DDSQ dispersion homogeneously in the copolymer matrix, and this would then affect the optical properties of NP and TPE units in this work.

Hybrid Porous Polymers Combination of Octavinylsilsesquioxane/Pyrene with Benzothiadiazole Units for Robust Energy Storage and Efficient Photocatalytic Hydrogen Production from Water

“…These organic−inorganic hybrid materials showcase a diverse range of fascinating physicochemical properties, including alterations in solubility, enhanced dielectric characteristics, improved resistance to oxidation and fire, elevated decomposition and glass transition temperatures, reduced heat transfer rates, and an impact on the hardness of the resulting materials. 1−5 This article is licensed under CC-BY 4 Octavinylsilsesquioxane (OVS), a derivative of cage silsesquioxanes (SQs), proves to be a highly valuable component in the creation of porous materials through diverse methods such as click reactions, Heck reactions, hydrosilylation, and Friedel−Crafts processes. The exceptional optical and electrical properties inherent to OVS are seamlessly transferred to these materials.…”

“…A developed porous material, based on polyhedral oligomeric silsesquioxanes (POSS), demonstrates variable properties and a highly symmetrical three-dimensional structure with specified nanometer-sized dimensions. − Its potential lies in the combination of versatile and flexible organic shells surrounding a rigid silica core. It is a promising candidate for synthesizing hybrid nanocomposites that exhibit properties midway between organics and ceramics, − The increasing demand for POSS in scientific research and industry is attributed to their customizable physical and chemical properties. − Another crucial aspect of functionalized silsesquioxanes is their physicochemical properties arising from their hybrid (organic–inorganic) nature. − The Si–O–Si framework, corresponding to silica with a well-defined structure, could serve as an intriguing material for modifying polymers and acting as fillers (nanofillers). − The precise control of molecule sizes and the variation in functional groups within the POSS core allow for their accurate deposition and embedding in a polymer matrix. − This, in turn, results in the creation of composite materials with unique characteristics. These organic–inorganic hybrid materials showcase a diverse range of fascinating physicochemical properties, including alterations in solubility, enhanced dielectric characteristics, improved resistance to oxidation and fire, elevated decomposition and glass transition temperatures, reduced heat transfer rates, and an impact on the hardness of the resulting materials. − …”

Nickel-Catalyzed Azide–Alkyne Click Polymerization toward 1,5-Regioregular Polytriazoles

“…A turnaround took place in 2002 when the Cu­(I)-catalyzed azide–alkyne cycloaddition (CuAAC) was reported independently by Sharpless et al and Meldal et al , As a typical click reaction, CuAAC could produce sole 1,4-disubstituted 1,2,3-triazoles in excellent yields under mild conditions, which has been developed into a useful polymerization technique, i.e., Cu­(I)-catalyzed azide–alkyne click polymerization (CuAACP) . Thanks to its remarkable click features, CuAACP has been widely used for the preparation of 1,4-regioregular polytriazoles (PTAs) with advanced structures and desired functional properties, which could serve as biomaterials, photoelectric materials, nonlinear optical materials, shape memory materials, self-healing materials, − and so on. To avoid the detriment of the residue metallic species to the optoelectronic and bioapplication of the product, metal-free click polymerization (MFCP) of azides and alkynes was also reported by our groups for the preparation of 1,4-regioregular PTAs …”