Anionic Polymerization of Butadiene Using Lithium/Potassium Multi-metallic Systems: Influence on Polymerization Control and Polybutadiene Microstructure

Antoine Forens; Kevin Roos; Charlotte Dire; Benoit Gadenne; Stéphane Carlotti

doi:10.1007/s10118-020-2355-4

Your Location：

Home >

Browse articles >

Anionic Polymerization of Butadiene Using Lithium/Potassium Multi-metallic Systems: Influence on Polymerization Control and Polybutadiene Microstructure

ARTICLE | Updated：2019-11-18

- Anionic Polymerization of Butadiene Using Lithium/Potassium Multi-metallic Systems: Influence on Polymerization Control and Polybutadiene Microstructure
- Chinese Journal of Polymer Science Vol. 38, Issue 4, Pages: 357-362(2020)
- Affiliations：
  
  a.Univ. Bordeaux, CNRS, Bordeaux INP, LCPO, UMR 5629, F-33600, Pessac, France
  b.MFP Michelin, Centre de Technologie/Ladoux, 23 Place des Carmes Déchaux, 63040 Clermont-Ferrand cedex 9, France
- Author bio：
  
  carlotti@enscbp.fr
- Funds：
- DOI：10.1007/s10118-020-2355-4
  CLC：
- Received：15 July 2019，
  
  Revised：2019-9-2，
  
  Accepted：06 September 2019，
  
  Online First：18 November 2019，
  
  Published：2020-04
- Accepted：
Scan QR Code
Forens, A.; Roos, K.; Dire, C.; Gadenne, B.; Carlotti, S. Anionic polymerization of butadiene using lithium/potassium multi-metallic systems: influence on polymerization control and polybutadiene microstructure. Chinese J. Polym. Sci. 2020, 38, 357–362

Antoine Forens, Kevin Roos, Charlotte Dire, et al. Anionic Polymerization of Butadiene Using Lithium/Potassium Multi-metallic Systems: Influence on Polymerization Control and Polybutadiene Microstructure[J]. Chinese Journal of Polymer Science, 2020, 38(4): 357-362.
Forens, A.; Roos, K.; Dire, C.; Gadenne, B.; Carlotti, S. Anionic polymerization of butadiene using lithium/potassium multi-metallic systems: influence on polymerization control and polybutadiene microstructure. Chinese J. Polym. Sci. 2020, 38, 357–362 DOI： 10.1007/s10118-020-2355-4.

Antoine Forens, Kevin Roos, Charlotte Dire, et al. Anionic Polymerization of Butadiene Using Lithium/Potassium Multi-metallic Systems: Influence on Polymerization Control and Polybutadiene Microstructure[J]. Chinese Journal of Polymer Science, 2020, 38(4): 357-362. DOI： 10.1007/s10118-020-2355-4.

摘要

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.

关键词

Keywords

references

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 . DOI: 10.1039/C7CP00080D http://doi.org/10.1039/C7CP00080D .

Kozak, R.; Matlengiewicz, M . Influence of polar modifiers on microstructure of polybutadiene obtained by anionic polymerization. Part 1: Lewis base ( σ ) amine-type polar modifiers . Int. J. Polym. Anal. Charact. , 2015 . 20 574 - 588 . DOI: 10.1080/1023666X.2015.1053599 http://doi.org/10.1080/1023666X.2015.1053599 .

Kozak, R.; Matlengiewicz, M . Influence of polar modifiers on microstructure of polybutadiene obtained by anionic polymerization. Part 2: Lewis base ( σ ) amine-ether and ether-type polar modifiers . Int. J. Polym. Anal. Charact. , 2015 . 20 602 - 611 . DOI: 10.1080/1023666X.2015.1054079 http://doi.org/10.1080/1023666X.2015.1054079 .

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 . DOI: 10.1080/1023666X.2015.1091906 http://doi.org/10.1080/1023666X.2015.1091906 .

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 . DOI: 10.1080/1023666X.2016.1092655 http://doi.org/10.1080/1023666X.2016.1092655 .

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 . DOI: 10.1080/1023666X.2016.1230264 http://doi.org/10.1080/1023666X.2016.1230264 .

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 . DOI: 10.1002/pol.1984.170220316 http://doi.org/10.1002/pol.1984.170220316 .

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 . DOI: 10.1002/actp.1984.010350101 http://doi.org/10.1002/actp.1984.010350101 .

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 . DOI: 10.1002/pol.1977.170150802 http://doi.org/10.1002/pol.1977.170150802 .

Lochmann, L . Reaction of organolithium compounds with alkali metal alkoxides—a route to superbases . Eur. J. Inorg. Chem. , 2000 . 6 1115 - 1126 . DOI: 10.1002/(SICI)1099-0682(200006)2000:6<1115::AID-EJIC1115>3.0.CO;2-K http://doi.org/10.1002/(SICI)1099-0682(200006)2000:6<1115::AID-EJIC1115>3.0.CO;2-K .

Schlosser, M.; Strunk, S . The “super-basic” butyllithium/potassium tert -butoxide mixture and other lickor-reagents . Tetrahedron Lett. , 1984 . 25 741 - 744 . DOI: 10.1016/S0040-4039(01)80014-9 http://doi.org/10.1016/S0040-4039(01)80014-9 .

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 . DOI: 10.1016/0040-4039(91)80364-C http://doi.org/10.1016/0040-4039(91)80364-C .

Lochmann, L.; Trekoval, J . Lithium-potassium exchange in alkyllithium/potassium t -pentoxide systems: XIV. Interactions of alkoxides . J. Organomet. Chem. , 1987 . 326 1 - 7 . DOI: 10.1016/0022-328X(87)80117-1 http://doi.org/10.1016/0022-328X(87)80117-1 .

Hsieh, H. L.; Wofford, C. F . Alkyllithium and alkali metal tert -butoxide as polymerization initiator . J. Polym. Sci. A1 , 1969 . 7 449 - 460 . DOI: 10.1002/pol.1969.150070204 http://doi.org/10.1002/pol.1969.150070204 .

Maréchal, J. M.; Carlotti, S.; Shcheglova, L.; Deffieux, A . Stereoregulation in the anionic polymerization of styrene initiated by superbases . Polymer , 2003 . 44 7601 - 7607 . DOI: 10.1016/j.polymer.2003.09.051 http://doi.org/10.1016/j.polymer.2003.09.051 .

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 . DOI: 10.1021/ma00016a002 http://doi.org/10.1021/ma00016a002 .

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 . DOI: 10.1002/(SICI)1521-3935(19990901)200:9<2015::AID-MACP2015>3.0.CO;2-I http://doi.org/10.1002/(SICI)1521-3935(19990901)200:9<2015::AID-MACP2015>3.0.CO;2-I .

Wofford, C. F.; Hsieh, H. L . Copolymerization of butadiene and styrene by initiation with alkyllithium and alkali metal tert-butoxides . J. Polym. Sci. A1 , 1969 . 7 ( 2 ): 461 - 469 . DOI: 10.1002/pol.1969.150070205 http://doi.org/10.1002/pol.1969.150070205 .

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 . DOI: 10.1002/1521-3900(200007)157:1<151::AID-MASY151>3.0.CO;2-9 http://doi.org/10.1002/1521-3900(200007)157:1<151::AID-MASY151>3.0.CO;2-9 .

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 . DOI: 10.2478/s11532-014-0528-0 http://doi.org/10.2478/s11532-014-0528-0 .

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 . DOI: 10.1021/ma60063a030 http://doi.org/10.1021/ma60063a030 .

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 . DOI: 10.1002/pol.1976.170140220 http://doi.org/10.1002/pol.1976.170140220 .

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 . DOI: 10.1016/j.polymer.2005.05.124 http://doi.org/10.1016/j.polymer.2005.05.124 .

Views

Downloads

CSCD

Alert me when the article has been cited

Submit

Tools

Publicity Resources

Ring-closing-opening Copolymerization of Phthalaldehyde and Epoxide towards Acid-degradable Polyether and Polyurethane

Iminopyridine Manganese and Nickel Complexes: Synthesis, Characterization and Behavior in the Polymerization of 1,3-Butadiene

Rapid Self-healing and Strong Adhesive Elastomer via Supramolecular Aggregates from Core-shell Micelles of Silicon Hydroxyl-functionalized cis-Polybutadiene

Squaramide-directed Cooperative One-dimensional Assembly in Telechelic Polydimethylsiloxane for Hierarchical Network Formation

End-to-End Neuron-inspired Signal Transduction Using Organic Electrochemical Transistors

Related Author

Ji-qin Wen

Xue-quan Zhang

Quan-quan Dai

Jie Pang

Yu-Bo Zhou

Li-Jun Liu

Hong-Xin Zhang

Jun-Peng Zhao

Related Institution

Key Laboratory of Synthetic Rubber, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences

Jiangsu Province Institute for Medical Equipment Testing

Faculty of Materials Science and Engineering, Qinghai University

Faculty of Materials Science and Engineering, South China University of Technology

Centro per l'Integrazione della Strumentazione Scientifica dell'Università di Pisa (C.I.S.U.P.), Università di Pisa,- Pisa

⁰