Multicomponent Combinatorial Polymerization via the Biginelli Reaction

Abstract

A multicomponent combinatorial polymerization method has been exploited as a new intersection between combinatorial chemistry, polymer chemistry, and organic chemistry. The tricomponent Biginelli reaction has been employed as a model multicomponent reaction (MCR) to efficiently prepare a library of polycondensates with continuously changed chain structure but different physical properties. The naturally increased reaction modules (monomers) directly doubled the number of polymers in the library, effectively improving the efficiency of polymer preparation. The glass transition temperatures (Tg) of those homologous polymers have been mapped for the first time to predict the Tg values of absent polymer homologues with good to excellent accuracy. Meanwhile, the Tg maps have also been used to reveal the regular change in Tg according to the polymer structure (linking group, monomer chain length, etc.), initially suggesting the academic significance of the multicomponent combinatorial polymerization system. We believe that the current research paves a straightforward way to synthesize new libraries of polymers via MCRs and might prompt the broader study of MCRs in interdisciplinary fields.

Click and Multicomponent Reactions Work Together for Polymer Chemistry

“…Later, Tao and coworkers extended the Biginelli protocol to prepare a library of polycondensates combining a variety of dibenzaldehydes, di‐1,3‐diones with urea (or thiourea). The polycondensations reached a 100% conversion within almost 2 h in acetic acid catalyzed by MgCl 2 at 100 °C, while affording M n values of 7.4–29.8 kDa …”

Phthalhydrazide immobilized on MCM‐41 as a potent and recoverable catalyst for the synthesis of pyrrolo[2,1‐a]isoquinolines

“…This strategy offers the advantages of simplicity, atom economy, and synthetic efficiency for the preparation of complex target molecules . So, combinatorial synthesis has gained popularity in many fields such as drug discovery, peptide synthesis, materials, catalyst research, and medicinal chemistry . However, developing new MCRs to obtain the ideal chemical reaction with more molecular diversity is still forms cutting‐edge techniques in synthesis and has practical value …”

Multicomponent Reactions and Multicomponent Cascade Reactions for the Synthesis of Sequence‐Controlled Polymers

“…Therefore, multicomponent reactions have become one of the most powerful tools for natural product synthesis and drug discovery from diversity‐oriented synthesis strategy . The applications of multicomponent reactions have also been extended to the field of polymer science, including polymer conjugation, post‐modification, and combination with living/controlled polymerization to produce novel materials with various macromolecular architectures and properties …”