Abstract
Thermal, mechanical, and viscoelastic properties of polybutadiene-based rubber materials are highly dependent on polybutadiene microstructure. The use of polar modifier in association with alkyllithium is a well-known method to obtain polybutadiene with a high vinyl content. Another approach is to use bimetallic initiating species such as alkyllithium combined to heavier alkali metal alkoxide (RONa, ROK…). The polymerization control is nevertheless not achieved and several parameters were found to influence it. Using bimetallic initiating systems based on alkyllithium and a potassium alkoxide, alkyllithium structure, initiator preformation time, and initiator composition were identified as parameters influencing the anionic polymerization process of butadiene and/or polybutadiene microstructure. In addition, the use of trimetallic systems based on alkyllithium, potassium alkoxide, and alkylaluminum was investigated in order to prevent side reactions regardless of the [K]/[Li] ratio and of the initiator preformation time.
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Aggarwal, S. L.; Hargis, I. G.; Livigni, R. A.; Fabris, H. J.; Marker, L. F. in Advances in elastomers and rubber elasticity, ed. by Lal, J.; Mark, J. E. Springer US, Boston MA, 1986, p. 17.
Ryu, M. S.; Kim, H. G.; Kim, H. Y.; Min, K. S.; Kim, H. J.; Lee, H. M. Prediction of the glass transition temperature and design of phase diagrams of butadiene rubber and styrene-butadiene rubber via molecular dynamics simulations Phys. Chem. Chem. Phys., 2017, 19, 16498–16506.
Kozak, R.; Matlengiewicz, M. Influence of polar modifiers on microstructure of polybutadiene obtained by anionic polymerization. Part 1: Lewis base (a) amine-type polar modifiers Int. J. Polym. Anal. Charact., 2015, 20, 574–588.
Kozak, R.; Matlengiewicz, M. Influence of polar modifiers on microstructure of polybutadiene obtained by anionic polymerization. Part 2: Lewis base (a) amine-ether and ether-type polar modifiers Int. J. Polym. Anal. Charact., 2015, 20, 602–611.
Kozak, R.; Matlengiewicz, M. Influence of polar modifiers on microstructure of polybutadiene obtained by anionic polymerization. Part 3: Lewis acid alkoxide (μ) and Lewis base amine, amine-ether, and ether mixed-type (Σ+μ) polar modifiers Int. J. Polym. Anal. Charact., 2016, 21, 44–45.
Kozak, R.; Matlengiewicz, M. Influence of polar modifiers on microstructure of polybutadiene obtained by anionic polymerization. Part 4: acid-base polar modifiers forming σ-μ complexes: amine-alkoxide, amine-ether-alkoxide, and ether-alkoxide Int. J. Polym. Anal. Charact., 2016, 21, 59–68.
Kozak, R.; Matlengiewicz, M. Influence of polar modifiers on microstructure of polybutadiene obtained by anionic polymerization. Part 5: Comparison of μ, σ, Σ+μ, and Σ−μ complexes Int. J. Polym. Anal. Charact., 2017, 22, 51–61.
Bywater, S.; Firat, Y.; Black, P. E. Microstructures of polybutadienes prepared by anionic polymerization in polar solvents. Ion-pair and solvent effects J. Polym. Sci. Polym. Chem. Ed., 1984, 22, 669–672.
Arest-Yakubovich, A. A.; Basova, R. V.; Nakhmanovich, B. I.; Kristalnyi, E. V. The main special characteristics of anionic polymerization initiated by group II metals Acta Polym., 1984, 35, 1–7.
Salle, R.; Pham, Q. T. Polymérisation anionique des diènes. VI. Microstructure des polybutadiène et polyisoprène par résonance magnétique protonique à 250 MHz et mécanismes de propagation J. Polym. Sci. Polym. Chem. Ed., 1977, 15, 1799–1810.
Lochmann, L. Reaction of organolithium compounds with alkali metal alkoxides — A route to superbases Eur. J. Inorg. Chem., 2000, 6, 1115–1126.
Schlosser, M.; Strunk, S. The “super-basic” butyllithium/potassium tert-butoxide mixture and other lickor-reagents. Tetrahedron Lett.1984, 25, 741–744.
Lochmann, L.; Petránek, J. More efficient metallation of alkylbenzenes by modified superbases from butyllithium and potassium alkoxides. Effect of alkoxide structure and concentration Tetrahedron Lett., 1991, 32, 1483–1488.
Lochmann, L.; Trekoval, J. Lithium-potassium exchange in alkyllithium/potassium t-pentoxide systems: XIV. Interactions of alkoxides J. Organomet. Chem., 1987, 326, 1–7.
Hsieh, H. L.; Wofford, C. F. Alkyllithium and alkali metal tert-butoxide as polymerization initiator J. Polym. Sci. A1, 1969, 7, 449–460.
Maréchal, J. M.; Carlotti, S.; Shcheglova, L.; Deffieux, A. Stereoregulation in the anionic polymerization of styrene initiated by superbases Polymer, 2003, 44, 7601–7607.
Patterson, D. B.; Halasa, A. F. Anionic polymerization of 1,3-butadiene to highly crystalline high trans-1,4-poly(butadiene) with potassium catalysts generated from an alkyllithium and potassium tert-amyloxide Macromolecules, 1991, 24, 4489–4494.
Nakhmanovich, B. I.; Zolotareva, I. V.; Arest-Yakubovich, A. A. Study on the mechanism of anionic polymerization with mixed RLi-R’OK Initiators, 1. Polymerization of butadiene Macromol. Chem. Phys., 1999, 200, 2015–2021.
Wofford, C. F.; Hsieh, H. L. Copolymerization of butadiene and styrene by initiation with alkyllithium and alkali metal tert-butoxides. J. Polym. Sci. A11969, 7(2), 461–469.
Desbois, P.; Fontanille, M.; Deffieux, A.; Warzelhan, V.; Schade, C. Towards the control of the reactivity in high temperature anionic polymerization of styrene: Retarded anionic polymerization. 3 -Influence of triisobutylaluminum on the reactivity of polystyryllithium species Macromol. Symp., 2000, 157, 151–160.
Lochmann, L.; Janata, M. 50 Years of superbases made from organolithium compounds and heavier alkali metal alkoxides Cent. Eur. J. Chem., 2014, 12, 537–548.
Hsieh, H.; Quirk, R. P. Anionic polymerization: Principles and practical applications. Marcel Dekker, New York, 1996
Worsfold, D. J.; Bywater, S. Lithium alkyl initiated polymerization of isoprene. Effect of cis/trans isomerization of organolithium compounds on polymer microstructure Macromolecules, 1978, 11, 582–586.
Halasa, A. F.; Mitchell, G. B.; Stayer, M.; Tate, D. P.; Oberster, A. E.; Koch, R. W. Metalation of unsaturated polymers by using activated organolithium compounds and the formation of graft copolymers. II J. Polym. Sci. Polym. Chem. Ed., 1976, 14, 497–506.
Carlotti, S.; Ménoret, S.; Barabanova, A.; Desbois, P.; Deffieux, A. Effect of aluminum derivatives in the retarded styrene anionic polymerization Polymer, 2005, 46, 6836–6843.
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Anionic Polymerization of Butadiene Using Lithium/Potassium Multi-metallic Systems: Influence on Polymerization Control and Polybutadiene Microstructure
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Forens, A., Roos, K., Dire, C. et al. Anionic Polymerization of Butadiene Using Lithium/Potassium Multi-metallic Systems: Influence on Polymerization Control and Polybutadiene Microstructure. Chin J Polym Sci 38, 357–362 (2020). https://doi.org/10.1007/s10118-020-2355-4
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DOI: https://doi.org/10.1007/s10118-020-2355-4