Vinyl ether‐based polyacetal polyols with various main‐chain structures and polyurethane elastomers prepared therefrom: Synthesis, structure, and functional properties

Abstract

ABSTRACTNovel acid degradable polyacetal polyols and polyacetal polyurethanes able to controlled acid degradation were developed. Polyacetal polyols with various main‐chain structures were synthesized by polyaddition of various vinyl ethers with a hydroxyl group [4‐hydroxy butyl vinyl ether (CH2CHOCH2CH2CH2CH2OH), 2‐hydroxy ethyl vinyl ether (CH2CHOCH2CH2OH), diethylene glycol monovinyl ether (CH2CHOCH2CH2OCH2CH2OH), and cyclohexanedimethanol monovinyl ether (CH2CHOCH2C6H10CH2OH)] with p‐toluenesulfonic acid monohydrate (TSAM) as a catalyst in the presence of the corresponding diols [1,4‐butandiol (HOCH2CH2CH2CH2OH), ethylene glycol (HOCH2CH2OH), diethylene glycol (HOCH2CH2OCH2CH2OH), and 1,4‐cyclohexanedimethanol (HOCH2C6H10CH2OH)], respectively. Polyacetal polyurethanes were prepared by a two‐step polymerization, using the synthesized polyacetal polyols, 4,4′‐diphenylmethane diisocyanate (MDI), and 1,4‐butandiol (BD) as a chain extender. Depending on the main‐chain structures, these polyurethanes had different glass transition temperature (from −44 to 19 °C) and properties such as hydrophobic or hydrophilic. Polyurethanes containing the hydrophilic main‐chain exhibited the thermoresponsiveness and had the certain volume phase transition temperature (VPTT). The polyacetal polyurethanes were flexible elastomers around room temperature (∼25 °C) and thermally stable (Td ≥ 310 °C) and additionally exhibited smooth degradation with a treatment of aqueous acid in THF at room temperature to give the corresponding raw material diols. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 44088.