Structure of terminal units of polybutadiene synthesized via anionic mechanism


The structure of head and end groups of the polybutadiene synthesized by anionic polymerization of butadiene using tert-butyllithium as an initiator has been established using methods of NMR spectroscopy with T2-filter as well as 2D 1H, 13C HMBC and HSQC NMR spectroscopy. The spectral signals of head groups, which consist of tert-butyl groups connected with cis-1,4, trans-1,4 or 1,2-units of polybutadiene chain, were identified for the first time. A new method for the quantitative calculation of the content of head and end groups with different microstructures was proposed. It was shown that the total content of 1,4-units (both cis-1,4 and trans-1,4) in terminal groups is considerably higher than that in a main chain of polybutadiene.

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  1. 1.

    Quirk RP, Jang SH, Kim J (1996) Recent advances in anionic synthesis of functionalized elastomers using functionalized alkyllithium initiators. Rubber Chem Technol 69(3):444–461.

    CAS  Article  Google Scholar 

  2. 2.

    Ziaee F, Ronagh-Baghbani M, Jozaghkar MR (2020) Microstructure characterization of low molecular weight polybutadiene using the chain end groups by nuclear magnetic resonance spectroscopy. Polym Bull 77(5):2345–2365.

    CAS  Article  Google Scholar 

  3. 3.

    Mogilevich MM, Turov BS, Morozov YL (1983) Liquid hydrocarbon rubbers. Khimia, Moscow

    Google Scholar 

  4. 4.

    Sekkar V, Gopalakrishnan S, Ambika Devi K (2003) Studies on allophanate–urethane networks based on hydroxyl terminated polybutadiene: effect of isocyanate type on the network characteristics. Eur Polym J 39(6):1281–1290.

    CAS  Article  Google Scholar 

  5. 5.

    Monakov YB, Tolstikov GA (1990) Catalytic polymerization of 1,3-dienes. Nauka, Moscow

    Google Scholar 

  6. 6.

    Makhiyanov N, Temnikova EV (2010) Glass-transition temperature and microstructure of polybutadienes. Polym Sci Ser A 52(12):1292–1300.

    Article  Google Scholar 

  7. 7.

    Elgert KF, Quack G, Stutzel B (1975) On the structure of polybutadiene: 4. 13C n.m.r. spectrum of polybutadienes with cis-1,4-, trans-1,4- and 1,2-units. Polymer 16(3):154–156.

    CAS  Article  Google Scholar 

  8. 8.

    Khachaturov AS (1981) Investigation of the structure of elastomers by proton and carbon NMR spectroscopy Zh. Vses. Khim. O-va im. D.I. Mendeleeva 26(3):288–296

  9. 9.

    Sato H, Takebayashi K, Tanaka Y (1987) Analysis of carbon-13 NMR of polybutadiene by means of low molecular weight model compounds. Macromolecules 20(10):2418–2423.

    CAS  Article  Google Scholar 

  10. 10.

    Khachaturov AS, Ivanova VP, Podkorytov IS, Osetrova LV (1998) Assignment of 13C NMR resonances to aliphatic carbon atoms of polybutadiene. Polym Sci Ser A 40(6):969–974

    Google Scholar 

  11. 11.

    Makhiyanov N (2012) Determination of configurational isomers in polybutadienes by 1H and 13C NMR spectroscopy. Polym Sci Ser A 54(2):69–80.

    CAS  Article  Google Scholar 

  12. 12.

    Skuratov KD, Lobach MI, Shibaeva AN, Churlyaeva LA, Erokhina TV, Osetrova LV, Kormer VA (1992) Structure of initial, ultimate and inner chain units of polybutadiene obtained with a rare-earth catalyst as revealed by 13C nuclear magnetic resonance spectroscopy. Polymer 33(24):5202–5207.

    CAS  Article  Google Scholar 

  13. 13.

    Rozentsvet VA, Kozlov VG, Stotskaya OA, Smirnov SN, Tolstoy PM (2019) A new approach to the study of the structure of polyisoprene obtained by cationic polymerization. Russ Chem Bull 68(1):116–120.

    CAS  Article  Google Scholar 

  14. 14.

    Rozentsvet VA, Sablina NA, Ulyanova DM, Tolstoy PM, Smirnov SN, Novakov IA (2020) Identification of the structure of polybutadiene terminal units by NMR spectroscopy with T2-filter. Dokl Phys Chem 491:40–42.

    CAS  Article  Google Scholar 

  15. 15.

    Rozentsvet VA, Sablina NA, Ulyanova DM, Kuznetsova MG, Kostjuk SV, Tolstoy PM (2020) A new approach toward investigation of structure of terminal units of poly(1,3-pentadiene) using T2-filtered NMR spectroscopy. Macromol Chem Phys 221(17):2000168.

    CAS  Article  Google Scholar 

  16. 16.

    Rozentsvet VA, Kozlov VG, Sablina NA, Stotskaya OA (2018) Cationic polymerization of butadiene using a titanium tetrachloride—tert-butyl chloride catalytic system. Russ Chem Bull 67(8):1419–1425.

    CAS  Article  Google Scholar 

  17. 17.

    Benoit H, Grubisic Z, Rempp P, Decker D, Zilliox JG (1966) Étude par chromatographie en phase liquide de polystyrènes linéaires et ramifiés de structures connues. J Chim Phys 63:1507–1514.

    CAS  Article  Google Scholar 

  18. 18.

    Rozentsvet VA, Stotskaya OA, Ivanova VP, Kuznetsova MG, Tolstoy PM, Kostjuk SV (2018) Structural characterization of polybutadiene synthesized via cationic mechanism. J Polym Sci Polym Chem 56(4):387–398.

    CAS  Article  Google Scholar 

  19. 19.

    Grant DM, Paul EG (1964) Carbon-13 magnetic resonance. II. Chemical shift data for the alkanes. J Am Chem Soc 86(15):2984–2990.

    CAS  Article  Google Scholar 

  20. 20.

    Rozentsvet VA, Kozlov VG, Monakov YB (2011) Cationic polymerization of conjugated dienes. Nauka, Moscow

    Google Scholar 

  21. 21.

    Podkorytov IS, Lubnin AV (1991) 13C NMR spectra of the models for the end-group analysis of polybutadiene. Magn Reson Chem 29(6):561–565.

    CAS  Article  Google Scholar 

  22. 22.

    Ventura A, Chenal T, Bria M, Bonnet F, Zinck P, Ngono-Ravache Y, Balanzat E, Visseaux M (2013) Trans-stereospecific polymerization of butadiene and random copolymerization with styrene using borohydrido neodymium/magnesium dialkyl catalysts. Eur Polym J 49(12):4130–4140.

    CAS  Article  Google Scholar 

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Rozentsvet, V.A., Sablina, N.A., Ulyanova, D.M. et al. Structure of terminal units of polybutadiene synthesized via anionic mechanism. Polym. Bull. (2021).

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