New Hybrid Materials by Controlled Polymerization of Monomers with Bulky Functional Substituents

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NON-TECHNICAL SUMMARYThis research project is focused on synthesis, characterization and potential applications of well-defined polymers containing bulky functional substituents (BFS). Until recently many polymers with precisely controlled architectures were prepared, yet essentially with small chemical substituents attached onto their molecules. The main aim of this project is to enlarge the range of these substituents to include various BFS such as inorganics, biomolecules or short polymer chains in the form of macromonomers. The resulting polymers will have a very high local concentration of functional groups and consequently could provide new materials with unusual thermal, mechanical, optoelectronic or biological properties. Unfortunately, direct polymerization of monomers with BFS is very challenging and therefore this research will explore new pathways to overcome these challenges. This project should impact not only science, but also education and our society. Undergraduate and graduate students, a postdoctoral fellow, and visitors from collaborative groups will work together in the PI's group and with industrial members of a consortium on specialized novel polymerization techniques. Some hybrid functional materials resulting from the proposed activities may be of commercial importance and should benefit our society. Dissemination of information will be accomplished by publications, presentations at national and international meetings and at the PI's web site. TECHNICAL SUMMARYThis main aim of this research is synthesis, characterization and potential applications of polymers with bulky functional substituents (BFS) such as inorganic nanoparticles, short polymer chains, or biomolecules. BFS reduce thermodynamic and kinetic polymerizability of such monomers, and new pathways and reaction conditions to overcome these challenges will be explored. Three classes of monomers with BSF will be investigated: (i) inorganic systems with polyhedral oligomeric silsesquioxanes (POSS) with various substituents as well as gold nanoclusters with spacers linking them to polymerizable (meth)acrylate group; (ii) macromonomers based on poly(ethylene oxide) and poly(n-butyl acrylate) with (meth)acrylate function; (iii) biomolecules (proteins or oligonucleotides) linked to (meth)acrylamide polymerizable groups. They will be polymerized under the range of conditions (solvent, concentrations, pressure, chemical or physical activators, pre-assembly) to generate novel hybrid materials with high local concentration of bulky functional groups. Their properties (thermomechanical, catalytic, bio-relevant) will be thoroughly characterized and their potential applications will be explored. The generated information will be disseminated through the PI's website, timely publications, student presentations at national and international conferences, and also to industry through the industrial consortium at Carnegie Mellon. Some hybrid functional materials resulting from the proposed activities may be of commercial importance and should benefit our society.