A new insight into the mechanism of 1,3‐dienes cationic polymerization. II. Structure of poly(1,3‐pentadiene) synthesized with tBuCl/TiCl4 initiating system |
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| Authors: | Victor A Rozentsvet Nelly A Korovina Valentina P Ivanova Marianna G Kuznetsova Sergei V Kostjuk |
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| Institution: | 1. Institute of Ecology of the Volga River Basin, Russian Academy of Science, , Togliatti, 445003 Russia;2. Lebedev Research Institute of Synthetic Rubber, , St. Petersburg, 198035 Russia;3. State Research Institute of Chemistry and Technology of Organoelement Compounds, , Moscow, 111123 Russia;4. Research Institute for Physical Chemical Problems of the Belarusian State University, , Minsk, 220030 Belarus |
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| Abstract: | The microstructure of poly(1,3‐pentadiene) synthesized by cationic polymerization of 1,3‐pentadiene with tBuCl/TiCl4 initiating system is analyzed using one‐dimensional‐ and two‐dimensional‐NMR spectroscopy. It is shown that unsaturated part of chain contains only homo and mixed dyads with trans?1,4‐, trans?1,2‐, and cis?1,2‐structures with regular and inverse (head‐to‐head or tail‐to‐tail) enchainment, whereas cis?1,4‐ and 3,4‐units are totally absent. The new quantitative method for the calculation of content of different structural units in poly(1,3‐pentadiene)s based on the comparison of methyl region of 13C NMR spectra of original and hydrogenated polymer is proposed. The signals of tert‐butyl head and chloromethyl end groups are identified in a structure of poly(1,3‐pentadiene) chain and the new approaches for the quantitative calculation of number‐average functionality at the α‐ and ω‐end are proposed. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3297–3307 |
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| Keywords: | microstructure poly(1 3‐pentadiene) 2D‐NMR cationic polymerization |
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