Recent Advances in Anionic Synthesis of Functionalized Polymers

作者：Roderic P. Quirk, Jian Yin, Shao‐Hua Guo, Xiao‐Wei Hu, Gabriel J. Summers, Jungahn Kim, Linfang Zhu, Jingjing Ma, Toshiki Takizawa, Thomas J. Lynch · 发表于：Rubber Chemistry and Technology · 年份：1991 · DOI：10.5254/1.3538580 · 被引用次数：27 · 研究领域：Synthetic Organic Chemistry Methods、Coordination Chemistry and Organometallics、Organometallic Complex Synthesis and Catalysis

Abstract There has been growing interest and research on new synthetic methods for the preparation of well-defined polymers with in-chain and chain-end functional groups. These functional groups in polymers can participate in (a) reversible ionic association; (b) chain extension, branching or crosslinking reactions with polyfunctional reagents; (c) coupling and linking with reactive groups on other oligomer or polymer chains; and (d) initiation of polymerization of other monomers. It is noteworthy that the use of end-functionalized polybutadienes formed by reaction of poly(butadienyl)lithium with 4,4′-bis(diethylamino)-benzophenone has been reported to provide marked improvements in the wear and traction properties of tires. In order to exploit the unique potential of functionalized polymers, it is important to consider the scope and limitations of current functionalization methodology using anionic polymerization. Anionic polymerization approaches the goal of synthesizing polymers with predictable, well-defined structures in certain systems such as diene, styrene, methacrylate, and heterocyclic monomers, which proceed in the absence of chain termination and chain transfer reactions. These living polymerizations generate stable, anionic polymer chain ends when all of the monomer has been consumed. In principle, these anionic chain ends can react with a variety of electrophilic species to generate a diverse array of functional groups. Unfortunately, many of the reported functi...