Qingdao Energy has proposed a new strategy for the preparation of chiral polymers by asymmetric resolution polymerization
Chiral science is closely related to life sciences, human health, materials technology and national economy. Inspired by biological macromolecules (DNA, proteins, etc.), scientists have discovered that chiral phenomena are also one of the basic characteristics of polymer materials. Chiral polymers are a special kind of polymer materials, which have special properties different from traditional polymer materials, such as space arrangement, material strength, dielectric properties and plasticity. These special properties endow chiral polymers with unique functions and applications, such as chiral separation materials, chiral liquid crystal materials, chiral sensing materials, and chiral electromagnetic materials (Figure 1). Therefore, the synthesis and application of chiral polymer materials have important scientific significance and market value.
So far, the research on chiral polymer materials is often limited to natural chiral polymer materials and very few synthetic chiral polymer materials, and its design, synthesis and application research are just at the initial stage. The development of the field of chiral polymer materials is facing many problems and challenges, among which "difficult to synthesize" and "difficult to characterize" are one of its core bottleneck problems, which also directly restricts the mechanism of chiral catalytic polymerization, the structure-activity relationship of polymer materials Development in areas such as functional applications.
The research group Wang Qinggang of Qingdao Institute of Bioenergy and Process, Chinese Academy of Sciences proposed a new strategy of “asymmetric resolution polymerization†for the design and synthesis of chiral polymers, which provides a new method for the efficient synthesis and direct characterization of chiral polymer materials. The study of the mechanism of sexually catalyzed polymerization provides a new way (Figure 2). The "asymmetric resolution polymerization" strategy is to combine the asymmetric resolution reaction with the synthesis of polymer materials, and use chiral catalysts to identify the racemic monomers with poor reaction rate to achieve efficient synthesis of chiral polymer materials; The conversion rate of the reaction and the enantiomeric excess value of the remaining monomers are used to characterize the overall optical properties of the chiral polymer; at the same time, the change rule of the resolution constant during the asymmetric polymerization process is used to study the possible chiral amplification or the chiral polymerization process. Chirality reduction and other reaction mechanisms.
The strategy was recently published in the chemistry field journal Coordination Chemistry Reviews (2020, 414, 213296) under the title of Asymmetric Kinetic Resolution Polymerization (AKRP). The paper comprehensively summarizes the research results of asymmetric split polymerization in the fields of transition metal catalysis, organic small molecule catalysis, and enzyme catalysis, and discusses the development history, research status, and possible development directions and trends in the field for chiral functions. Research and development in the field of materials provide methods and theoretical guidance. The paper also showed the series of achievements of the catalytic polymerization and engineering research group in the preparation of chiral polyester resolution polymerization, as well as other chiral polymer design and synthesis (New J. Chem., 2020, 44, 1648; Polym . Chem., 2019, 10, 1832; Mater. Today Commun ,. 2020,22, 100747). Researchers will explore the reaction mechanism and control mechanism of chiral catalytic polymerization by optimizing the design of new polymerization monomers and developing asymmetric catalytic polymerization systems to achieve catalytic resolution polymerization of different racemic monomers and create new chiral polymer materials. , Expect innovation and breakthroughs in concepts and methods.
Xu Guangqiang, associate researcher of the research group, is the first author of the paper, and Wang Qinggang is the corresponding author of the paper. The work was supported by the National Natural Science Foundation of China, Shandong Provincial Talent Engineering Fund, Qingdao Energy Research Institute's "One Three Five" Key Cultivation Fund and two integration funds.
Figure 1. Application fields and synthesis strategies of chiral materials
Figure 2. Asymmetric resolution polymerization (AKRP)
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