Novel Amphiphilic Polyfluorene-Graft-(Polymethacrylic Acid) Brushes: Synthesis, Conformation, and Self-Assembly.

Maria Simonova,Alexander Yakimansky,Larisa Litvinova,Dmitry Ilgach,Alexander Filippov,Maria Nepomnyashaya,Ksenia Kaskevich

doi:10.3390/polym13244429

Maria Simonova, Alexander Yakimansky + Show 5 more

Open Access

https://doi.org/10.3390/polym13244429

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Journal: Polymers	Publication Date: Dec 17, 2021
Citations: 5	License type: CC BY 4.0

Affiliation: Institute of Macromolecular Compounds

Abstract

Novel polyfluorene polymer brushes with polymethacrylic acid side chains were obtained by atom transfer radical polymerization (ATRP) and activator generated by electron transfer (AGET) ATRP of tert-butyl methacrylate on polyfluorene multifunctional macroinitiator, followed by protonolysis of the tert-butyl groups of the side chains. Kinetics of polymerization and molecular weights were fully characterized. These polymer brushes luminesce in the blue region of the spectrum with high quantum yields (0.64–0.77). It was shown that the luminescence intensity of polymer brushes is higher than the luminescence intensity of the macroinitiator (0.61). Moreover, due to their amphiphilic nature, they can form unimolecular micelles when an alcohol solution of the polymer brush is injected into water. These properties can potentially be used in drug delivery and bioimaging.

Highlights

The modern synthetic approaches make it possible to prepare grafted copolymers with a controlled molecular architecture and molar mass
Novel polyfluorene polymer brushes with polymethacrylic acid side chains were obtained by atom transfer radical polymerization (ATRP) and activator generated by electron transfer (AGET) ATRP of tert-butyl methacrylate on polyfluorene multifunctional macroinitiator, followed by protonolysis of the tert-butyl groups of the side chains
PtBMA and polymethacrylic acid (PMAA) side chains were synthesized by radical polymerization

Summary

Introduction

The modern synthetic approaches make it possible to prepare grafted copolymers with a controlled molecular architecture and molar mass. Amphiphilic molecular brushes structure of backbone and side chains which differ strongly have been studied for a long time [1,2,3,4,5,6,7,8,9]. Polymer brushes with a polyimide backbone and side chains of polymethylmethacrylate [10,11,12] or polymethacrylic acid (PMAA) [4,13] have been synthesized and studied in solutions and films. To close polymers end groups, a solution of phenylboronic acid pinacoline ester (0.012 g, 3 mol%) in anisole (1 mL) was added to the system using a syringe, and the reaction was continued at 100 ◦C for an hour.

Synthesis of Macroinitiator MI

Synthes of Polymer Brushes

Study of the Thermal Characteristics of Polymer Brushes

Conclusions