Synthesis of novel styrene-olefin triblock copolymer via living anionic polymerization

Document Type : Original research

Authors

Department of Polymer Science, Iran Polymer and Petrochemical Institute, Tehran, Iran

Abstract

Innovative strides in polymer synthesis have led to the successful living anionic polymerization of styrene-olefin triblock copolymers, yielding varying molecular weights and a remarkably narrow dispersity (Đ) in cyclohexane solvent at 45°C, initiated by n-butyllithium. The novel approach employs anionic polymerization, augmented by the aid of a coupling agent known as 1,12-dibromododecane. Unlike traditional alcohol-based methods employed in polystyrene synthesis, this coupling agent, introduced at the end of the reaction, grafts two living macro-styrene chains with the dodecane chain, effectively acting as the pivotal second component in the formation of the triblock copolymer. Extensive experimentation pinpointed 45°C as the optimal temperature for anionic copolymerization in cyclohexane solvent. The comprehensive analysis, encompassing 13C NMR, 1H NMR, FTIR spectroscopy, and GPC, confirms the successful synthesis of styrene-dodecane-styrene triblock copolymer. The NMR results illustrate successful molecular structures, while GPC attests to the precision, showing a narrow Đ of below 1.2. This pioneering approach not only underscores the efficiency of anionic polymerization in the synthesis of styrene-olefin-styrene triblock copolymer using termination strategy but also promises extensive implications in material science and industrial applications.

Graphical Abstract

Synthesis of novel styrene-olefin triblock copolymer via living anionic polymerization

Keywords

Main Subjects


  1. Su M, Sheng YJ, Chen YJ, Li T, Shi QX, Xiao H, Pu MQ, Bao, H, Wan WM (2022) Living covalent-anionic-radical polymerization via a barbier strategy. ACS Macro Lett 11: 354-361 [CrossRef]
  2. Fontanille M, Gnanou Y (2022) Anionic polymerization of vinyl and related monomers, In: Macromolecular engineering: From precise synthesis to macroscopic materials and applications. Eds: Matyjaszewski K, Gnanou Y, Hadjichristidis N, Muthukumar M, Wiley‐VCH GmbH, 1-51 [CrossRef]
  3. Maji P, Naskar K (2022) Styrenic block copolymer-based thermoplastic elastomers in smart applications: Advances in synthesis, microstructure, and structure–property relationships-A review. J Appl Polym Sci 139: e52942 [CrossRef]
  4. Kang BG, Kang NG, Lee JS (2010) Living anionic polymerization of styrene derivatives containing triphenylamine moieties through introduction of protecting group. Macromolecules 43: 8400-8408 [CrossRef]
  5. Sugiyama K, Watanabe K, Hirao A, Hayashi M (2008) Living anionic polymerization of 4-(α-alkylvinyl) styrene derivatives. Macromolecules 41: 4235-4244 [CrossRef]
  6. Bai H, Zhang Z, Ma H, Han L, Mu X, Huang W, Liu P, Wu Y (2019) Investigation of the features in living anionic polymerization with styrene derivatives containing annular substituents. Polym Chem 10: 1140-1149 [CrossRef]
  7. Zhou C, Wang J, Zhou P, Wang G (2020) A polymerization-induced self-assembly process for all-styrenic nano-objects using the living anionic polymerization mechanism. Polym Chem 11: 2635-2639 [CrossRef]
  8. Zhang T, Conrad ED, Gates DP (2022) Di-and tri-block copolymers from the sequential living anionic copolymerization a phosphaalkene with styrene. Polymer 249: 124831 [CrossRef]
  9. Yang L, Shen H, Han L, Ma H, Li C, Lei L, Zhang S, Liu P, Li Y (2020) Sequence regulation in living anionic terpolymerization of styrene and two categories of 1, 1-diphenylethylene (DPE) derivatives. Polym Chem 11: 5163-5172 [CrossRef]
  10. Jozaghkar MR, Ziaee F, Azar AS (2021) Investigation of poly (α-methyl styrene) tacticity synthesized by photo-polymerization. Polym Bull 78: 5303-5314 [CrossRef]
  11. Hadjichristidis N, Pitsikalis M, Pispas S, Iatrou H (2001) Polymers with complex architecture by living anionic polymerization. Chem rev 101: 3747-3792 [CrossRef]
  12. Hirao, A, Goseki R, Ishizone T (2014) Advances in living anionic polymerization: From functional monomers, polymerization systems, to macromolecular architectures. Macromolecules, 47: 1883-1905 [CrossRef]
  13. Jozaghkar MR, Ziaee F, Jalilian S (2022) Synthesis, kinetic study and characterization of living anionic polymerized polystyrene in cyclohexane. Iran Polym J 31: 399-412 [CrossRef]
  14. Yang J, Yang W, Wang X, Dong M, Liu H, Wujcik EK, Shao Q, Wu S, Ding T, Guo Z (2019) Synergistically toughening polyoxymethylene by methyl methacrylate–butadiene–styrene copolymer and thermoplastic polyurethane. Macromol Chem Phys 220: 1800567 [CrossRef]
  15. Liang M, Liang P, Fan W, Qian C, Xin X, Shi J, Nan G (2015) Thermo-rheological behavior and compatibility of modified asphalt with various styrene–butadiene structures in SBS copolymers. Mater Des 88: 177-185 [CrossRef]
  16. Mirmohseni A, Zavareh S (2010) Epoxy/acrylonitrile-butadiene-styrene copolymer/clay ternary nanocomposite as impact toughened epoxy. J Polym Res 17: 191-201 [CrossRef]
  17. Suleiman D, Carreras G, Soto Y (2013) Effect of block composition, size and functionality of poly (styrene-isobutylene-styrene) copolymers. J Appl Polym Sci 128: 2297-2306 [CrossRef]
  18. Suman SK, Sharma R, Kaul BN, Mondal RK, Dubey KA, Sharma SD, Bhardwaj YK and Kulkarni MS (2023) Stress relaxation and thermal management in highly filled flexible styrene butadiene styrene copolymer-tungsten composites for high-energy radiation attenuation. Polym Compos 44: 5819-5829 [CrossRef]
  19. Bulanov P, Vdovin E, Stroganov V, Mavliev L, Juravlev I (2022) Complex modification of bituminous binders by linear styrene-butadiene-styrene copolymer and sulfur. In: Proceedings of STCCE 2022, pp. 405-413 [CrossRef]
  20. Wei R, Luo Y, Zeng W, Wang F, Xu S (2012) Styrene–Butadiene–Styrene triblock copolymer latex via reversible addition–fragmentation chain transfer miniemulsion polymerization. Ind Eng Chem Res 51:15530-15535 [CrossRef]
  21. Wu L, Ma H, Wang Q, Li L, Wang Y, Li Y (2014) In-chain multi-functionalized random butadiene–styrene copolymer via anionic copolymerization with 1, 1-bis (4-dimethylaminophenyl) ethylene: Synthesis and its application as a rubber matrix of carbon black-based composite. J Mater Sci 49: 5171-5181 [CrossRef]
  22. Holden G (2011) Thermoplastic elastomers. In: Applied plastics engineering handbook, William Andrew Publishing, pp. 77-91
  23. Jozaghkar MR, Jahani Y, Arabi H, Ziaee F (2019) Effect of polyethylene molecular architecture on the dynamic viscoelastic behavior of polyethylene/polyhexene-1 blends and its correlation with morphology. Polym-Plast Technol Mater 58: 560-572 [CrossRef]
  24. Burns AB, Register RA (2016) Strategies for the synthesis of well-defined star polymers by anionic polymerization with chlorosilane coupling and preservation of the star architecture during catalytic hydrogenation. Macromolecules 49: 2063-2070 [CrossRef]
  25. Zheng K, He JP (2019) Amphiphilic dendrimer-like copolymers with high chain density by living anionic polymerization. Chinese J Polym Sci 37: 875-883 [CrossRef]
  26. Takahata K, Uchida S, Goseki R, Ishizone T (2019) Synthesis of chain end acyl-functionalized polymers by living anionic polymerization: Versatile precursors for H-shaped polymers. Polym Chem 10: 3951-3959 [CrossRef]
  27. Jozaghkar MR, Ziaee F, Azar AS, Mehdipour-Ataei S (2022) Effect of reaction temperature on tacticity in polymerization of methyl methacrylate: A study by nuclear magnetic resonance spectroscopy. Iran J Polym Sci Technol 35: 393-404 [CrossRef]