Postpolymerization Modification of Poly(dihydropyrimidin-2(1H)-thione)s via the Thiourea-Haloalkane Reaction to Prepare Functional Polymers.

A highly reactive thiourea-contained polycondensate, poly(dihydropyrimidin-2(1H)-thione) (poly(DHPMT)) has been facilely synthesized via the Biginelli polycondensation using thiourea and a difunctional compound containing benzaldehyde and β-keto ester groups as monomers. The thiourea moiety in the polymer structure has similar reactivity as the thiourea, thus the poly(DHPMT) is an excellent polymer precusor for preparing new functional polymers through the postpolymerization modification (PPM) strategy. After simple reaction with functional haloalkanes, the parent poly(DHPMT) could be almost completely converted (>99%) to daughter polymers containing alkene or alkyne side groups. Then, the daughter polymers have been further transferred to granddaughter polymers through another PPM via thiol-ene or Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC) reactions. Besides, when 3-phenylpropargyl chloride was used as the reactant, a bright yellow fluorescent polymer could be simply achieved due to the in situ formed conjugated heterocycle in the polymer structure, further demonstrating the diversity of the functional polymers through PPM. Considering the easily available monomers, simple polycondensation, and the excellent reactivity of the thiourea moiety in the polymer structure, this thiourea-contained Biginilli polycondensate might be a versatile platform for new functional polymer preparation.