Chain-end modification of living anionic polybutadiene with diphenylethylenes and styrenes

• Published in: Journal of polymer science. Part A, Polymer chemistry Vol. 43; no. 12; pp. 2536 - 2545
• Main Authors: Donkers, Ellen H. D., Willemse, Robin X. E., Klumperman, Bert
• Format: Journal Article
• Language: English
• Published: Hoboken Wiley Subscription Services, Inc., A Wiley Company 15-06-2005; Wiley
• Subjects: anionic polymerization; Applied sciences; Exact sciences and technology; MALDI; mass spectroscopy; Organic polymers; Physicochemistry of polymers; polybutadiene; Polymerization; Preparation, kinetics, thermodynamics, mechanism and catalysts; Butadiene copolymer; End group; MALDI; Asymmetric molecule; Living polymer; Experimental study; mass spectroscopy; Solution polymerization; Chemical coupling; Butadiene polymer; Preparation; Styrene derivatives; Styrene; Diblock copolymer; Anionic polymerization; polybutadiene; Chemical reactivity; Stilbene; Styrene copolymer
• ISSN: 0887-624X; 1099-0518
• DOI: 10.1002/pola.20725

The first step in the transformation of poly(butadienyl)lithium into a macromolecular atom transfer radical polymerization initiator or reversible addition–fragmentation chain transfer agent is the modification of the anionic chain end into a suitable leaving/reinitiating group. We have investigated three different modification reactions to obtain a styrenic end group at the chain end of poly(butadienyl)lithium. In all cases, we have looked at the influence of a Lewis base on the progress of the reaction. The first modification reaction with α‐methylstyrene leads to partial functionalization and oligomerization. The second reaction with 1,2‐diphenylethylenes, particularly trans‐stilbene, results in monoaddition to the poly(butadienyl)lithium chain ends. Quantitative functionalization is not obtained, possibly because of a hydrogen ion reaction, which causes termination. In the third modification reaction, a small polystyrene block is successfully added to the chain ends, as shown by a detailed matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry analysis of the block copolymers. Nearly quantitative block copolymer formation is achieved, with an average styrene block size of four monomer units and a polydispersity index of 1.19 for the polystyrene block. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2536–2545, 2005
Three different modification reactions at the chain end of poly(butadienyl)lithium have been investigated. In all cases, the influence of a Lewis base on the progress of the reaction has been examined. The first modification reaction with α‐methylstyrene leads to partial functionalization and oligomerization. The second reaction with 1,2‐diphenylethylenes results in monoaddition to the poly(butadienyl)‐lithium chain ends. Quantitative functionalization is not obtained. In the third modification reaction, a small polystyrene block is successfully added to the chain ends, as shown by a detailed matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry analysis. Nearly quantitative block copolymer formation is achieved, with an average styrene block size of four monomer units and a polydispersity index of 1.19 for the polystyrene block.