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

非技术总结本研究项目致力于合成、表征和潜在应用于含有大体积功能取代基(BFS)的定义明确的聚合物。直到最近，许多具有精确控制结构的聚合物被制备出来，但基本上它们的分子上都附着着小的化学取代基。该项目的主要目的是扩大这些取代基的范围，以包括各种BF，如无机物、生物分子或以大单体形式存在的短聚合物链。由此产生的聚合物将具有非常高的局部官能团浓度，因此可以提供具有不寻常的热、机械、光电或生物性能的新材料。不幸的是，单体与BFS的直接聚合是非常具有挑战性的，因此本研究将探索克服这些挑战的新途径。这个项目不仅应该影响科学，而且应该影响教育和我们的社会。本科生和研究生、博士后研究员和合作小组的参观者将在PI的小组中一起工作，并与一个联盟的行业成员一起研究专业的新颖聚合技术。拟议活动产生的一些混合功能材料可能具有商业价值，应该会造福于我们的社会。信息的传播将通过出版物、在国家和国际会议上的发言以及在国际和平协会的网站上进行。技术综述这项研究的主要目的是合成、表征具有大体积取代基的聚合物，如无机纳米颗粒、短聚合物链或生物分子。BFS降低了此类单体的热力学和动力学聚合性，将探索克服这些挑战的新途径和反应条件。具有BSF的三类单体将被研究：(I)具有不同取代基的多面体低聚倍半硅氧烷(POSS)的无机体系以及带有间隔物将其连接到可聚合(甲基)丙烯酸酯基团的金纳米簇；(Ii)基于聚环氧乙烷和具有(甲基)丙烯酸酯功能的聚丙烯酸丁酯的大单体；(Iii)连接(甲基)丙烯酰胺可聚合基团的生物分子(蛋白质或寡核苷酸)。它们将在一定的条件下(溶剂、浓度、压力、化学或物理活化剂、预组装)聚合，生成具有高局部浓度的大体积官能团的新型杂化材料。将对它们的性质(热机械、催化、生物相关)进行彻底的表征，并探索其潜在的应用。产生的信息将通过国际和平协会的网站、及时的出版物、在国内和国际会议上的学生陈述以及通过卡内基梅隆大学的工业联盟向工业界传播。拟议活动产生的一些混合功能材料可能具有商业价值，应该会造福于我们的社会。

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.