Multicomponent Polymerization of Carbamates, Chlorodiphenylphosphine, and Aromatic Aldehyde toward Poly(α-carbamatephosphineoxide)s

The exploration of phosphorus-containing polymer structures and development of their facile and efficient synthetic approaches are of great challenge and significance in polymer science. In this work, an efficient multicomponent polymerization of carbamates, chlorodiphenylphosphine, and aromatic aldehyde was developed for the facile access to a new group of phosphorus-containing polymers—poly(α-carbamatephosphineoxide)s. The polymerization went efficiently in 1,4-dioxane at 70 °C, without any catalyst or additive, producing poly(α-carbamatephosphineoxide)s with well-defined chemical structures, satisfying molecular weights (Mns up to 17,500 g/mol), and high yields (up to 91%). These poly(α-carbamatephosphineoxide)s possess abundant intermolecular hydrogen bonds, good thermal stability, and aggregation-induced emission property. The chlorophosphine-involving multicomponent polymerization could hence provide facile access to new phosphorus-containing polymer structures, promoting the advancement of phosphorus-containing polymer materials.