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Polymers 2017, 9(10), 538; https://doi.org/10.3390/polym9100538

Anionic Polymerization of Styrene and 1,3-Butadiene in the Presence of Phosphazene Superbases

1
Polymer Synthesis Laboratory, KAUST Catalysis Center, Physical Sciences and Engineering Division, King Abdullah University of Science and Technology (KAUST), Thuwal 23955, Saudi Arabia
2
Physical Sciences and Engineering Division, King Abdullah University of Science and Technology (KAUST), Thuwal 23955, Saudi Arabia
*
Author to whom correspondence should be addressed.
Received: 6 October 2017 / Revised: 20 October 2017 / Accepted: 20 October 2017 / Published: 21 October 2017
(This article belongs to the Special Issue Living Polymerization)
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Abstract

The anionic polymerization of styrene and 1,3-butadiene in the presence of phosphazene bases (t-BuP4, t-BuP2 and t-BuP1), in benzene at room temperature, was studied. When t-BuP1 was used, the polymerization proceeded in a controlled manner, whereas the obtained homopolymers exhibited the desired molecular weights and narrow polydispersity (Ð < 1.05). In the case of t-BuP2, homopolymers with higher than the theoretical molecular weights and relatively low polydispersity were obtained. On the other hand, in the presence of t-BuP4, the polymerization of styrene was uncontrolled due to the high reactivity of the formed carbanion. The kinetic studies from the polymerization of both monomers showed that the reaction rate follows the order of [t-BuP4]/[sec-BuLi] >>> [t-BuP2]/[sec-BuLi] >> [t-BuP1]/[sec-BuLi] > sec-BuLi. Furthermore, the addition of t-BuP2 and t-BuP1 prior the polymerization of 1,3-butadiene allowed the synthesis of polybutadiene with a high 1,2-microstructure (~45 wt %), due to the delocalization of the negative charge. Finally, the one pot synthesis of well-defined polyester-based copolymers [PS-b-PCL and PS-b-PLLA, PS: Polystyrene, PCL: Poly(ε-caprolactone) and PLLA: Poly(L-lactide)], with predictable molecular weights and a narrow molecular weight distribution (Ð < 1.2), was achieved by sequential copolymerization in the presence of t-BuP2 and t-BuP1. View Full-Text
Keywords: anionic polymerization; phosphazene superbases; high vacuum technique; kinetic study; block copolymers anionic polymerization; phosphazene superbases; high vacuum technique; kinetic study; block copolymers
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Ntetsikas, K.; Alzahrany, Y.; Polymeropoulos, G.; Bilalis, P.; Gnanou, Y.; Hadjichristidis, N. Anionic Polymerization of Styrene and 1,3-Butadiene in the Presence of Phosphazene Superbases. Polymers 2017, 9, 538.

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