Synthesis and Properties of Poly[oxy(arylene)oxy(tetramethyldisilylene)]s via Melt Copolymerization Reaction

Abstract

We carried out the melt copolymerization reactions of 1,2-bis(diethylamino)tetramethyldisilane with several aryldiols such as, 4,4'-biphenol, 4,4'-isopropylidenediphenol, 9H-fluoren-9,9-dimethanol, and 4,4'-(9-fluorenylidene)bis(2-phenoxyethanol) to afford poly[oxy(arylene)oxy(tetramethyldisilylene)]s containing fluorescent aromatic chromophore groups in the polymer main chain: poly[oxy(4,4'-biphenylene)oxy(tetramethyldisilylene)], poly[oxy{(4,4'-isopropylidene) diphenylene}oxy(tetramethyldisilylene)], poly[oxy(9H-fluorene-9,9-dimethylene)oxy(tetramethyldisilylene)], and poly[oxy{4,4'-(9-fluorenylidene)bis(2-phenoxyethylene)}oxy(tetramethyldisilnylene)]. These prepared materials are soluble in common organic solvents such as CHCl 3 and THF. The obtained polymers were characterized by several spectroscopic methods such as . These polymeric materials in THF showed strong maximum absorption peaks at 268-281 nm, strong maximum excitation peaks at 263-291 nm, and strong maximum fluorescence emission bands at 314-362 nm due to the presence of tetramethyldisilylene and several arylene chromophores in the polymer main chain. TGA thermograms indicated that most of the polymers were stable up to 200 °C with a weight loss of 3-16% in nitrogen.

Polymers from Bioderived Resources: Synthesis of Poly(silylether)s from Furan Derivatives Catalyzed by a Salen–Mn(V) Complex

“…PSEs have been synthesized by various methods from several available sources. The most commonly employed method is condensation polymerization of diols with either dihalosilanes, dialkoxysilanes, or diaminosilanes. , Quaternary ammonium salt catalyzed reactions of dichlorosilanes with bis­(oxetane)­s and bis­(epoxide)­s also provide PSEs. , However, chlorosilanes are air/moisture- sensitive and generate undesired side products, such as HCl . Hydrosilanes can be advantageous as they are air-stable, are inexpensive, and produce H 2 as the only byproduct.…”

“…The most commonly employed method is condensation polymerization of diols with either dihalosilanes, dialkoxysilanes, or diaminosilanes. 38,39 Quaternary ammonium salt catalyzed reactions of dichlorosilanes with bis(oxetane)s and bis(epoxide)s also provide PSEs. 40,41 However, chlorosilanes are air/moisture-sensitive and generate undesired side products, such as HCl.…”

Poly(silyl ether)s as Degradable and Sustainable Materials: Synthesis and Applications

“…R 2 SiX 2 with Diols Among this type of silanes, dichlorosilanes are the most common for the synthesis of PSEs. Similar to the synthesis of silyl ethers, reaction of dichlorosilanes with diols via the conventional condensation polymerization protocol leads to the formation of PSEs (Scheme 2) [37][38][39][40][41][42][43]. However, the use of dichlorosilanes has limitations, as the byproduct HCl requires a base to neutralize it and additional methods for its separation [44].…”

Synthesis of Poly(silyl ethers) via Iridium-Catalyzed Dehydrocoupling Polymerization

“…Polycondensation of dichlorosilanes and diols is the most often used method to synthesize PSEs . However, dichlorosilanes are moisture-sensitive, which limits their further use.…”