Synthesis of degradable and chemically recyclable polymers using 4,4-disubstituted five-membered cyclic ketene hemiacetal ester (CKHE) monomers

Abstract

Novel degradable and chemically recyclable polymers were synthesized using five-membered cyclic ketene hemiacetal ester (CKHE) monomers. The studied monomers were 4,4-dimethyl-2-methylene-1,3-dioxolan-5-one (DMDL) and 5-methyl-2-methylene-5-phenyl-1,3-dioxolan-4-one (PhDL). The two monomers were synthesized in high yields (80–90%), which is an attractive feature. DMDL afforded its homopolymer with a relatively high molecular weight (M_n >100 000, where M_n is the number-average molecular weight). DMDL and PhDL were copolymerized with various families of vinyl monomers, i.e., methacrylates, acrylates, styrene, acrylonitrile, vinyl pyrrolidinone, and acrylamide, and various functional methacrylates and acrylate. Such a wide scope of the accessible polymers is highly useful for material design. The obtained homopolymers and random copolymers of DMDL degraded in basic conditions (in the presence of a hydroxide or an amine) at relatively mild temperatures (room temperature to 65 °C). The degradation of the DMDL homopolymer generated 2-hydroxyisobutyric acid (HIBA). The generated HIBA was recovered and used as an ingredient to re-synthesize DMDL monomer, and this monomer was further used to re-synthesize the DMDL polymer, demonstrating the chemical recycling of the DMDL polymer. Such degradability and chemical recyclability of the DMDL polymer may contribute to the circular materials economy.