A polyester containing electron deficient internal alkyne units derived from acetylene dicarboxylic acid in the main backbone was employed as a polymeric platform in copper free cycloaddition reactions.
Conductive polymers find key applications ranging from optoelectronics and OLEDs to conductive composite materials. The synthesis of conductive polymers from monomers, such as thiophene derivatives, pyrroles and aniline, mainly relies on oxidative polymerization, and the processing of so‐formed (insoluble) polymers is a major issue that needs to be addressed. In the present work, oxidative photopolymerization of 3,4‐ethylenedioxythiophene (EDOT) by visible light employing the metal‐free semiconductor graphitic carbon nitride (g‐CN) is presented. Two main reaction pathways based on g‐CN content are described, and the formation of processable oligo‐EDOT is demonstrated.
The utilization of sunlight to conduct chemistry has been on a stark rise in the era of sustainability. A similar trend is observed in polymer science, mainly to initiate polymerization and modify polymer materials, but mostly relying on the utilization of soluble initiator/activator molecules. Semiconductors, on the other hand, grant a platform for "photoredox" induced chemical pathways, so that reductive and oxidative reactions (as well as radical formation) can be tailored according to band positions. Despite their utilization as dispersed or dissolved phases, immobilization of semiconductors on macroscale solid surfaces is attractive to entail scale-up options. In this Review, semiconductors incorporated in cross-linked porous polymer networks will be summarized both from synthesis and application perspectives.
The inclusion of the metal free semiconductor graphitic carbon nitride (g‐CN) into polymer systems brings a variety of new options, for instance as a heterogeneous photoredox polymer initiator. In this context, we present here the decoration of the inner surface of poly(styrene‐co‐divinylbenzene) beads with organomodified g‐CN via one pot suspension photopolymerization. The resulting beads are varied by changing reaction parameters, such as, crosslinking ratio, presence of porogens, and mechanical agitation. The photocatalytic activity of so‐formed beads was tested by aqueous rhodamine B dye photodegradation experiments. Additionally, dye adsorption/desorption properties were examined in aqueous as well as in organic solvents. Photoinduced surface modification with vinylsulfonic acid and 4‐vinyl pyridine is introduced. Overall, metal‐free semiconductor g‐CN donates photoactivity to polymer networks that can be employed for dye photodegradation and acid–base catalyst transformation through facile photoinduced surface modifications.
Polymerization of multifunctional thiol-ene molecules are attractive as a proof of concept in photopolymerization, yet formation of bead structure is highly restricted. This manuscript will exhibit graphitic carbon nitride based...
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