Synthesis and properties of σ‐π conjugated porous polymers obtained withMizoroki–Heckreaction of tetra vinyl cyclic siloxane with dibromo fluorene

Abstract

σ‐π Conjugated porous polymers were synthesized by the Mizoroki–Heck reaction of cyclic siloxane with vinyl groups, 1,3,5,7‐tetravinyltetramethylcyclotetrasiloxane (TVMCTS), and 2,7‐dibromo‐9,9‐dialkylfluorene (RFl) compounds, using a Pd catalyst in N,N‐dimethylformamide (DMF) at 100°C. The reactions of TVMCTS in combination with 2,7‐dibromo‐9,9‐dihexylfluorene (HFl), 2,7‐dibromo‐9,9‐dioctylfluorene (OFl), and 2,7‐dibromo‐9,9‐ethylhexylfluorene (EHFl) yielded porous polymers whose morphologies were induced by phase separation during the network formation. The reactions in combination with binary RFl systems, TVMCTS‐HFl/OFl, and HFl/EHFl systems, also yielded porous polymers. Scanning electron microscope images showed porous structures, which were composed by connected globules and/or isolated‐deformed holes. The long and branching structure of the alkyl side chains in RFl decreased Young's modulus of porous polymers in compression test. The porous polymers showed emission derived from σ‐π conjugated fluorene units on photo excitation. An increase in monomer concentration in the reaction induced red shifts of the emission bands of the porous polymer due to π‐stacking of the fluorene units. The porous polymers showed relatively high fluorescence quantum yields of about 0.2–0.3. Quantum yield of the porous polymers with HFl decreased with increasing monomer concentration in the reaction systems.

The first space-filling polyhedrons of polymer cubic cells originated from Weaire-Phelan structure created by polymerization induced phase separation

“…The synthetic methodology employed in this work is based on the "joint-and-linker" concept. The addition reaction between a multi-functional monomer as a source of "joint" ("joint"-source monomer) and α,ωbifunctional monomer as a source of "linker" ("linker-source monomer) forms polymer network [16][17][18][19][20][21][22][23][24] . The joint-and-linker synthesis so far reported often preferentially yielded porous polymers by polymerizationinduced phase separation via spinodal decomposition.…”

Synthesis of porous polymers by polymerization‐induced phase separation in the addition reaction of multifunctional isocyanates and dithiol compounds

“…We have been developing several types of porous polymers prepared by addition reactions between a multi‐functional monomer, as a source of joint parts, and a α,ω‐bifunctional monomer, as a source of linker parts, the so‐called joint and linker concept, in some solvents via polymerization induced phase separation. Several combinations of multi‐functional thiol, polyol, acrylate, acrylamide, and amine as the joint‐source monomer, and diisocyanate, divinylether, dithiol, diamine and diacrylate as the linker‐source monomer successfully yielded porous polymers under specific reaction conditions 15–22 . The surface morphology of the porous polymers was composed by co‐continuous monolithic structures or connected (aggregated) particles generated by phase separation via spinodal decomposition or highly internal phase separation.…”

“…Several combinations of multi-functional thiol, polyol, acrylate, acrylamide, and amine as the joint-source monomer, and diisocyanate, divinylether, dithiol, diamine and diacrylate as the linker-source monomer successfully yielded porous polymers under specific reaction conditions. [15][16][17][18][19][20][21][22] The surface morphology of the porous polymers was composed by co-continuous monolithic structures or connected (aggregated) particles generated by phase separation via spinodal decomposition or highly internal phase separation. The porous polymers could be prepared without additional pore-generators, such as polymeric compounds or surfactants.…”

Morphology Control and Metallization of Porous Polymers Synthesized by Michael Addition Reactions of a Multi-Functional Acrylamide with a Diamine

“…We have been developing several types of porous polymers synthesized by addition reactions between a multi-functional monomer, as a source of joint parts (“joint-source monomer”), and a α,ω-bifunctional monomer, as a source of linker parts (“linker-source monomer)”, in some solvents via polymerization-induced phase separation. In our previous studies, combinations of multi-functional thiol, polyol, acrylate, and amine as the joint-source monomer and diisocyanate, divinyl ether, dithiol, diamine and diacrylate compounds as the linker-source monomer could yield porous polymers under specific reaction conditions [ 77 , 78 , 79 , 80 , 81 , 82 , 83 ]. The porous polymers showed surface morphology formed by co-continuous monolithic structures or connected spheres.…”