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Open AccessArticle

Synthesis and Characterization of Phosphorus- and Carborane-Containing Polyoxanorbornene Block Copolymers

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Chemistry Department, Yildiz Technical University, 34220 Istanbul, Turkey
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IMDEA Materials Institute, C/Eric Kandel, 2, Getafe, 28906 Madrid, Spain
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Macromolecular Chemistry Department, Technische Universität Darmstadt, 64287 Darmstadt, Germany
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Organic Macromolecular Chemistry, Saarland University, Campus Saarbrücken C4 2, 66123 Saarbrücken, Germany
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Institute of Inorganic Chemistry, Leipzig University, 04103 Leipzig, Germany
*
Authors to whom correspondence should be addressed.
Polymers 2019, 11(4), 613; https://doi.org/10.3390/polym11040613
Received: 19 February 2019 / Revised: 24 March 2019 / Accepted: 26 March 2019 / Published: 3 April 2019
Grubbs-catalyzed ring-opening metathesis polymerization (ROMP) of carborane- and phosphonate-containing monomers has been used for the generation of hybrid block copolymers. Molecular weights with Mn of 50,000 g/mol were readily obtained with polydispersity index values, Đ, between 1.03–1.08. Reaction of the phospha ester and carborane substituted oxanorbornene block copolymer with trimethylsilyl bromide led to a new polymer with phosphonic acid functionalities. In application studies, the phospha-carborane functionalized block polymer was tested as heat resistance material. Thermal stability was investigated by thermal gravimetric analysis (TGA) and microscale combustion calorimetry (MCC) analysis. Thermal treatment and ceramic yield under air were directly correlated to the carborane content of the block copolymer. However, phosphorus content in the polymer was more crucial for the char residues when heated under nitrogen atmosphere. The peak heat release rate (PHRR) increased as the number of phosphonate functionalities increased. However, corresponding phosphonic acid derivatives featured a lower heat release rate and total heat release. Moreover, the phosphonic acid functionalities of the block copolymer offer efficient chelating capabilities for iron nanoparticles, which is of interest for applications in biomedicine in the future. The complexation with iron oxide nanoparticles was studied by transmission electron microscopy (TEM) and inductively coupled plasma mass spectrometry (ICP–MS). View Full-Text
Keywords: carboranes; phosphonate esters; block copolymers; ROMP; hybrid materials carboranes; phosphonate esters; block copolymers; ROMP; hybrid materials
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Kahraman, G.; Wang, D.-Y.; von Irmer, J.; Gallei, M.; Hey-Hawkins, E.; Eren, T. Synthesis and Characterization of Phosphorus- and Carborane-Containing Polyoxanorbornene Block Copolymers. Polymers 2019, 11, 613.

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