Synthesis of degradable polymers from renewable resources has been a promising way to replace nonrenewable fossil fuel derived polymers motivated by environmental sustainability. Poly­(silylether)­s (PSEs) are a specific type of environmentally degradable polymer with many potential applications. A series of PSEs have been synthesized (M n up to 25 000 g/mol) from biorenewable feedstocks, such as 5-hydroxymethylfurfural and its derivatives 2,5-bis­(hydroxymethyl)­furan, 2,5-diformylfuran, and 5,5′-[oxybis­(methylene)]­di­(2-furaldehyde). The polymerization reactions employ a versatile, air-stable manganese salen complex, which catalyzes both the dehydrogenative cross-coupling of hydroxyls with hydrosilanes and the hydrosilylation of carbonyls. The chemical and thermal characterization of PSEs was carried out by 1H NMR, 13C NMR, Fourier transform infrared spectroscopy, gel permeation chromatography, differential scanning calorimetry, and thermogravimetric analysis.

A manganese–salen complex is shown to be effective in catalyzing the dehydrogenative coupling of hydroxyl groups with hydrosilane.

Poly(silylether)s are interesting materials because of their degradation property under hydrolytic conditions and have been prepared via hydrosilylation polymerization from dicarbonyl and hydrosilanes, and via dehydrogenative cross-coupling of diols and hydrosilanes under catalytic conditions. Here, we present a manganese–salen compound based on an inexpensive and nontoxic metal that could effectively catalyze both polymerization reactions with hydrosilane. A series of poly(silylether)s containing various aliphatic and aromatic backbones have been synthesized from diol and dicarbonyl substrates. Moderate to high yields of polymers with number-average molecular weights up to 15 kg/mol are obtained. Because of the dual activity of the manganese catalyst, unsymmetrical substrates with mixed functional groups, such as p -hydroxybenzaldehyde, p -hydroxy benzylalcohol, and 3-(4-hydroxyphenyl)-1-propanol, have been employed to afford poly(silylether)s with multiple silicon connectivity in the main chain.