Comprehensive structural characterization of polyisoprene synthesized via cationic mechanism |
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| Authors: | Victor A Rozentsvet Nelly A Korovina Olesya A Stotskaya Marianna G Kuznetsova Frederic Peruch Sergei V Kostjuk |
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| Affiliation: | 1. Institute of Ecology of the Volga River Basin, Russian Academy of Science, Togliatti, Russia;2. State Research Institute of Chemistry and Technology of Organoelement Compounds, Moscow, Russia;3. Laboratoire de Chimie des Polymères Organiques, UMR 5629, CNRS/UB1/IPB, University of Bordeaux, Pessac Cedex, France;4. Research Institute for Physical Chemical Problems of the Belarusian State University, Minsk, Belarus |
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| Abstract: | The microstructure of polyisoprene synthesized with tBuCl/TiCl4 initiating system is investigated using 1D and 2D (HSQC and HMBC) NMR spectroscopy. It is found that trans‐1,4‐units with regular (head‐to‐tail) and inverse (tail‐to‐tail) and (head‐to‐head) enchainments are predominant structures of unsaturated part of polymer chain, while 1,2‐ and 3,4‐units are presented in minor amounts. The new methodology for the quantitative calculation of the content of different structural units in polyisoprene chain including both types of inverse trans‐1,4‐addition (tail‐to‐tail and head‐to‐head) is proposed. It is shown that head groups consist of tert‐butyl group connected to trans‐1,4‐unit of polyisoprene chain. In addition, two types of chlorine‐containing end groups are found (trans‐4,1‐Cl and 4,3‐Cl), while conjugated double bonds at the chain end are totally absent. The methodology for the calculation of number‐average functionality by tert‐butyl head and chlorine end groups, respectively, is developed. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2430–2442 |
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| Keywords: | cationic polymerization polyisoprene microstructure |
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