Investigation of ring‐opening polymerization of 5‐[2‐{2‐(2‐methoxyethoxy)ethoxy}‐ethoxymethyl]‐5‐methyl‐1,3‐dioxa‐2‐one by organometallic catalysts

ABSTRACT To develop new polymer‐based materials, the design of aliphatic carbonate has received attention and become a well‐known cyclic monomer. In view of carbonate ring polymer scope, poly(trimethylene carbonate) (PTMC) has been continuously developed for further applications due to its unique degradability. PTMC bearing oligo ethylene glycol units, PTMCM‐MOE3OM, were typically prepared via ring‐opening polymerization (ROP) using amidine‐based catalysts such as 1,8‐diazabicyclo[5.4.0] undec‐7‐ene (DBU) and benzyl alcohol (BnOH) as an initiator. To improve the polymer molecular weight or other properties, several know‐how synthetic catalysts based on organometallic complexes are under consideration as potential catalysts. With the existence of diverse classes of metallic complexes, the inorganic complexes were investigated for their catalytic activity based on tris(dimethylsilyl)amido chelating, bis(phenolate) chelating, and macrocyclic tetradentate (NNNN)‐type cyclen chelating with a metal‐core of tin (II), scandium (III), lutetium (III), and zinc (II). In this study, we found that involving a Zn(II) dimethylcyclen/alkoxide ligand and Mg complexes could accelerate the reaction and finish the polymerization under ambient conditions within 2 hr. Molecular weight reached 11,000 g/mol (40%) and 8,100 g/mol (> 96%). Subsequently, we concluded that Zn and Mg complexes were high reactivity for initiating the ROP of TMCM‐MOE3OM upon steadily degree of polymerization. Rare earth silyloamido complexes, metal bis(phenolato) complexes (OSSO), and tetradentate complexes were used as catalysts within 2 hr polymerization.