Abstract

Star-shaped polymers with arms of block and gradient copolymers of 2-ethyl- and 2-isopropyl-2-oxazolines grafted to the upper rim of calix[8]arene were synthesized by the “grafting from” method. The ratio of 2-ethyl- and 2-isopropyl-2-oxazoline units was 1:1. Molar masses and hydrodynamic characteristics were measured using molecular hydrodynamics and optics methods in 2-nitropropane. The arms of the synthesized stars were short and the star-shaped macromolecules were characterized by compact dimensions and heightened intramolecular density. The influence of the arm structure on the conformation of star molecules was not observed. At low temperatures, the aqueous solutions of the studied stars were not molecular dispersed but individual molecules prevailed. One phase transition was detected for all solutions. The phase separation temperatures decreased with a growth of the content of more hydrophobic 2-isopropyl-2-oxazoline units. It was shown that the way of arms grafting to the calix[8]arene core affects the behavior of aqueous solutions of star-shaped poly-2-alkyl-2-oxazoline copolymers. In the case of upper rim functionalization, the shape of calix[8]arene resembles a plate. Accordingly, the core is less shielded from the solvent and the phase separation temperatures are lower than those for star-shaped poly-2-alkyl-2-oxazolines with lower rim functionalization of the calix[8]arene.

Highlights

  • New synthetic routes make it possible to obtain well-defined polymers with complex architecture [1,2,3,4] including multiarm stars [5,6,7,8,9,10]

  • Star-shaped polymers with arms of block and gradient copolymers of 2-ethyl- and 2isopropyl-2-oxazolines grafted to the upper rim of calix[8]arene were synthesized by the “grafting from” method

  • The phase separation temperatures decreased with a growth of the content of more hydrophobic 2-isopropyl-2-oxazoline units

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Summary

Introduction

New synthetic routes make it possible to obtain well-defined polymers with complex architecture [1,2,3,4] including multiarm stars [5,6,7,8,9,10]. The study star-shaped block PAlOx copolymers revealed that a different sequence of block attachment to the core does not influence the phase separation temperatures, it determines the set and dimensions of scattering objects [13]. The present work was aimed at the analysis of the influence of the arm structure and the configuration of the calix[8]arene (C8A) core on the molecular conformation, the solution behavior, and the self-organization of star-shaped PAlOx copolymers in aqueous solutions upon heating. To solve this problem, eight-arm polymer stars were synthesized and studied. It is important that the synthesized star-shaped samples should have a similar arm length in order to avoid the influence of molar mass on the obtained characteristics

Materials and Reagents
Synthesis of Multicenter Macroiniciater
Hydrolysis of Star-Shaped Polymers
Characterization of Prepared Star Samples
Investigation of Molecular-Dispersed Polymer Solutions
Investigation of Self-Organization in Aqueous Solutions
Polymer Synthesis
Hydrodynamic Characteristics and Conformation of Star-Shaped CA8-PAlOx-UR
Findings
Self-Organization of C8A-PAlOx-UR Molecules in Aqueous Solutions
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