Synthesis and Characterization of Functional Amphiphilic Gradient Copolymers by Atom Transfer Radical Polymerization

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Title: Synthesis and Characterization of Functional Amphiphilic Gradient Copolymers by Atom Transfer Radical Polymerization
Authors: Schwitke, Sandra
Thesis advisor: Prof. Dr. Uwe Beginn
Thesis referee: Prof. Dr. Heinz-Jürgen Steinhoff
Abstract: The purpose of this work was the synthesis of functional amphiphilic gradient copolymers by means of controlled radical polymerizations, more precisely Atom Transfer Radical Polymerization. Two different monomer combinations, tert- and n-butyl methacrylate and tert-butyl and benzyl methacrylate, were copolymerized. In a first step seven different linear statistical copolymers were synthesized by means of batch polymerization. They were used as comparative material and the analysis of the reaction kinetic yielded the effective rate constants and the copolymerization parameters of the monomers in the particular monomer systems. Furthermore required for gradient polymer syntheses AB-di-block copolymers were synthesized as a second kind of comparative material. With the results of the kinetic analysis the monomer addition programs for the semibatch polymerizations were calculated to prepare gradient copolymers. Four different gradient copolymers with different compositions of tBMA and nBMA (ftBMA= 0.5, 0.65, 0.75, 0.85) and one gradient copolymer of tBMA and BzMA (ftBMA= 0.5) were synthesized. All semibatch reactions proceeded controlled, i. e. with mostly suppressed termination reactions. The compositions of the resulting copolymers exhibited ''double-gradients''. The point of change of the compositions were located at 16%, respectively 11% of conversion. The effective compositional gradients φ = dF1/dp were φ = 0.53, 0.46, 0.28, 0.15 and 0.43. A systematic correlation between the thermal behavior of the gradient copolymers and their composition was not found, as opposed to the statistical and the di-block copolymers. Semibatch synthesis with online infrared-spectroscopy observation to control the monomer feed during the synthesis were used for the polymerization of gradient copolymers. It was not possible to calculate the change of compositions of the polymers because it was not known how much monomer was injected at a certain time of the polymerization. A second problem was that the experimental set-up was not gas-tight. Hence, oxygen led to termination reactions. Three different kinds of hydrolysis were investigated for the cleavage of the tert-butyl groups on the polymer chains. The obtained gradient copolymers were hydrolyzed with methanesulfonic acid to obtain the intended amphiphilic polymer chains. All reactions proceeded with quantitative conversion. Hence, functional amphiphilic copolymers were obtained.
Subject Keywords: Gradient Copolymer; Atom Transfer Radical Polymerization; Semibatch Copolymerization; Methacrylate
Issue Date: 30-Oct-2014
License name: Namensnennung-NichtKommerziell-KeineBearbeitung 3.0 Unported
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Type of publication: Dissertation oder Habilitation [doctoralThesis]
Appears in Collections:FB05 - E-Dissertationen

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