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

Handle URI:
http://hdl.handle.net/10754/625930
Title:
Anionic Polymerization of Styrene and 1,3-Butadiene in the Presence of Phosphazene Superbases
Authors:
Ntetsikas, Konstantinos; Alzahrany, Yahya; Polymeropoulos, George; Bilalis, Panayiotis; Gnanou, Yves ( 0000-0001-6253-7856 ) ; Hadjichristidis, Nikolaos ( 0000-0003-1442-1714 )
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.
KAUST Department:
KAUST Catalysis Center (KCC); Physical Sciences and Engineering (PSE) Division; Polymer Synthesis Laboratory
Citation:
Ntetsikas K, Alzahrany Y, Polymeropoulos G, Bilalis P, Gnanou Y, et al. (2017) Anionic Polymerization of Styrene and 1,3-Butadiene in the Presence of Phosphazene Superbases. Polymers 9: 538. Available: http://dx.doi.org/10.3390/polym9100538.
Publisher:
MDPI AG
Journal:
Polymers
Issue Date:
23-Oct-2017
DOI:
10.3390/polym9100538
Type:
Article
ISSN:
2073-4360
Sponsors:
Research reported in this publication supported by King Abdullah University of Science and Technology.
Additional Links:
http://www.mdpi.com/2073-4360/9/10/538
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorNtetsikas, Konstantinosen
dc.contributor.authorAlzahrany, Yahyaen
dc.contributor.authorPolymeropoulos, Georgeen
dc.contributor.authorBilalis, Panayiotisen
dc.contributor.authorGnanou, Yvesen
dc.contributor.authorHadjichristidis, Nikolaosen
dc.date.accessioned2017-10-24T10:45:41Z-
dc.date.available2017-10-24T10:45:41Z-
dc.date.issued2017-10-23en
dc.identifier.citationNtetsikas K, Alzahrany Y, Polymeropoulos G, Bilalis P, Gnanou Y, et al. (2017) Anionic Polymerization of Styrene and 1,3-Butadiene in the Presence of Phosphazene Superbases. Polymers 9: 538. Available: http://dx.doi.org/10.3390/polym9100538.en
dc.identifier.issn2073-4360en
dc.identifier.doi10.3390/polym9100538en
dc.identifier.urihttp://hdl.handle.net/10754/625930-
dc.description.abstractThe 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.en
dc.description.sponsorshipResearch reported in this publication supported by King Abdullah University of Science and Technology.en
dc.publisherMDPI AGen
dc.relation.urlhttp://www.mdpi.com/2073-4360/9/10/538en
dc.rightsThis article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).en
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/en
dc.subjectanionic polymerizationen
dc.subjectphosphazene superbasesen
dc.subjecthigh vacuum techniqueen
dc.subjectkinetic studyen
dc.subjectblock copolymersen
dc.titleAnionic Polymerization of Styrene and 1,3-Butadiene in the Presence of Phosphazene Superbasesen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentPolymer Synthesis Laboratoryen
dc.identifier.journalPolymersen
dc.eprint.versionPublisher's Version/PDFen
kaust.authorNtetsikas, Konstantinosen
kaust.authorAlzahrany, Yahyaen
kaust.authorPolymeropoulos, Georgeen
kaust.authorBilalis, Panayiotisen
kaust.authorGnanou, Yvesen
kaust.authorHadjichristidis, Nikolaosen
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