Rare Earth Metal‐Mediated Group Transfer Polymerization of Vinylphosphonates

Abstract

Recent studies have shown that poly(vinylphosphonate)s are readily accessible by rare earth metal-mediated group transfer polymerization (GTP). This article highlights the progress in this new field and advantages of GTP in comparison to classical anionic and radical polymerization approaches. Late lanthanide metallocenes proved to be efficient initiators and highly active catalysts for vinylphosphonate polymerization yielding polymers of precise molecular weight and low polydispersity. Using this method, our group has developed a surface-initiated GTP to prepare poly(vinylphosphonate) brushes. In combination with different ester cleavage strategies, rare earth metal-mediated GTP is an efficient way to create well-defined high-molecular-weight poly(vinylphosphonic acid).

Fluorescent Polyvinylphosphonate Bioconjugates for Selective Cellular Delivery

“…Herein, we present the fluorescent labeling of the conjugates via the partial transesterification of the polymer side chains. To accomplish this complex task, a strategy employed by our group for the hydrolysis of poly(diethyl vinylphosphonate) (PDEVP) was adapted . The functionalization proceeds via the trimethylsilyl ether intermediate.…”

Poly(vinylphosphonate)s functionalized polymer microspheres via rare earth metal-mediated group transfer polymerization

“…After SIPGP of EGDM, Cp 2 YbMe was added to react with the preserved methacrylate functionalities on PS microsphere to give highly active enolate initiating species for the successive SI‐GTP. (Scheme ) The mechanism for GTP of (meth)acrylates and DAVP has been outlined previously . The surface‐bound enolate attacks a monomer coordinating to the Yb‐catalyst and successive chain growth occurs via repeated conjugate addition over an eight‐membered ring intermediate …”

“…Over the past decades, phosphorus‐containing polymers, especially those comprising phosphonate moieties have attracted great interest in diverse application area, ranging from halogen‐free flame retardants, fuel cells based on proton‐conducting films, and biomedical fields . Nevertheless, polymerization of vinylphosphonates by radical and anionic approaches usually affords only low yields and degrees of polymerization, hindering its application in a variety of intriguing area . Recently, it was shown that poly(dialkyl vinyl phosphonate) (PDAVP) with high molar mass and low polydispersity could be synthesized both in bulk and on silicon substrates using rare earth metallocenes (REM) as catalyst, following a so‐called group transfer polymerization (GTP) mechanism .…”

Single‐Site, Organometallic Aluminum Catalysts for the Precise Group Transfer Polymerization of Michael‐Type Monomers

“…Modern polymeric materials are developed with respect to targeting specific functions, like self‐assembly or stimuli‐responsivity. Precise control of the macromolecular architecture is a major requirement for producing identical polymer chains . One successful synthetic strategy is based on living and controlled radical polymerization methods .…”