Synthesis of First- and Second-Generation Poly(amide)-Dendronized Polymers via Ring-Opening Metathesis Polymerization

Abstract

First-and second-generation Newkome-type dendronized norbornene macromonomers were synthesized and polymerized by ringopening metathesis polymerization (ROMP). In the case of the second-generation macromonomer, the rate of polymerization was highly dependent on the initial concentration of the macromonomer; quasi-quantitative polymerization was only achieved when the concentration was higher than 50 mM. Adding a linker between the polymerizable group and the dendron increased the rate of polymerization and it was possible to reach quantitative conversions at lower concentration. Doubling the length of the linker further improved the polymerization to a rate comparable with the polymerization of the first-generation dendronized macromonomer. The dendronized polymers presented herein consist of a poly(amide)-based dendron attached to the poly(norbornene) backbone. Because of the properties of these components such as biocompatibility, we foresee these polymers having possible applications in therapeutics.

Synthesis and characterization of linear dendritic homo and copolymers acrylated behera amine

“…[10,11] Newkome-type dendronized norbornene macromonomers were synthesized and polymerized by ring-opening metathesis polymerization to obtain biocompatible polymers. [12] This dendron was also used in synthesis of protein cages to construct synthetic DNAbinding domains, [13] redox active hybrid dendrimers building blocks for nonviral vectors for gene therapies, [14] stabilization of gold particles, [15,16] and catalyst in transfer hydrogenation [17] as well as micelles [18] and ion selective gels after hydrolysis. [19] A possible application field of hydrolyzed ACTES co-polymers obtained from polymerizable Newkome-type dendron is reduction catalyst of hydrogen.…”

New ROMP Synthesis of Ferrocenyl Dendronized Polymers

“…The long linker was expected to alleviate the shell effect occurring in the polymerization process of bulky dendronized macromonomers. In such cases, uncompleted polymerization is caused by the steric crowding of the large dendron around the polymerizable unit, forming a shell around the active chain end . The dendron 6 containing three‐terminal Fc moieties was synthesized following the route shown in Scheme and coupled to the norbornene azide 2 via click CuAAC reaction using as catalyst CuSO 4 ·5H 2 O and sodium ascorbate to provide 7 .…”

“…The macromonomer route describes the polymerization of a fully synthesized dendron equipped with a polymerizable group at their focal point . This method is attractive, because all the dendrons on the polymer backbone are perfectly incorporated, but a powerful polymerization technique is necessary in order to obtain large dendronized polymers with a high degree of polymerization, especially in the case of a high‐generation macromonomer …”

Combining Ring‐Opening Metathesis Polymerization and Thiol‐Ene Coupling Chemistries: Facile Access to Novel Functional Linear and Nonlinear Macromolecules

“…The “grafting‐to” and “grafting‐from” approaches can facilitate access to dendronized (co)polymers bearing higher generations of bound dendrons but can also give poorly defined materials and or a low density of bound dendrons. Many polymerization techniques have been employed in the preparation of dendronized (co)polymers including ROMP …”