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Materials 2018, 11(9), 1608; https://doi.org/10.3390/ma11091608

Supramolecular Networks from Block Copolymers Based on Styrene and Isoprene Using Hydrogen Bonding Motifs—Part 1: Synthesis and Characterization

1
Institute of Physical Chemistry, University of Hamburg, Grindelallee 117, 20146 Hamburg, Germany
2
Institute of Polymer Research, Helmholtz-Zentrum Geesthacht, Max-Planck-Straße 1, 21502 Geesthacht, Germany
*
Author to whom correspondence should be addressed.
Received: 6 August 2018 / Revised: 24 August 2018 / Accepted: 31 August 2018 / Published: 4 September 2018
(This article belongs to the Special Issue Synthesis Characterization and Applications of Block Copolymers)
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Abstract

The combination of controlled anionic polymerization and subsequent introduction of hydrogen bonding groups was established to form thermo-reversible, supramolecular networks. Several polyisoprene-block-polystyrene-block-polyisoprene (ISI) copolymers—with polystyrene (PS) as the main block, and consequently giving the decisive material characteristics—were synthesized. The novel modification approach to post-functionalize the polyisoprene (PI) end-blocks and to introduce different motifs, which are able to form self-complementary hydrogen bonds, was attained. In the first step, hydroxylation was accomplished using 9-borabicyclo[3.3.1]nonane. Starting from the hydroxylated polymer, esterification with succinic anhydride was implemented to form an ester group with carboxylic end-group (-O-CO-CH2-CH2-COOH). In a second approach, 1,1’-carbonyldiimidazole was used as coupling agent to introduce various types of diamines (diethylenetriamine, triethylentetramine, and 2,6-diaminopyridine) to prepare urethane groups with amine end-group (-O-CO-NH-R-NH2). 1H NMR spectroscopy was used to confirm the successful synthesis and to calculate the degree of functionalization Df. Differential scanning calorimetry (DSC) showed a difference of the glass transition temperature Tg between unfunctionalized and functionalized block copolymers, but no greater influence between the different types of modification, and thus, on the Tg of the PS block. In temperature dependent FTIR spectroscopy, reversible processes were observed. View Full-Text
Keywords: anionic polymerization; triblock copolymer; modification; self-complementary hydrogen bonding; supramolecular polymers; amphiphilic polymers; temperature responsiveness anionic polymerization; triblock copolymer; modification; self-complementary hydrogen bonding; supramolecular polymers; amphiphilic polymers; temperature responsiveness
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Rahmstorf, E.; Abetz, V. Supramolecular Networks from Block Copolymers Based on Styrene and Isoprene Using Hydrogen Bonding Motifs—Part 1: Synthesis and Characterization. Materials 2018, 11, 1608.

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