Anionic Polymerization of Styrene and 1,3-Butadiene in the Presence of Phosphazene Superbases
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 mo...
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| Format: | Article |
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MDPI AG
2017-10-01
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| Series: | Polymers |
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| Online Access: | https://www.mdpi.com/2073-4360/9/10/538 |
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| author | Konstantinos Ntetsikas Yahya Alzahrany George Polymeropoulos Panayiotis Bilalis Yves Gnanou Nikos Hadjichristidis |
| author_facet | Konstantinos Ntetsikas Yahya Alzahrany George Polymeropoulos Panayiotis Bilalis Yves Gnanou Nikos Hadjichristidis |
| author_sort | Konstantinos Ntetsikas |
| collection | DOAJ |
| description | 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. |
| first_indexed | 2024-04-12T21:19:46Z |
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| id | doaj.art-da93a72b64a64a2d9cae6f53a8903426 |
| institution | Directory Open Access Journal |
| issn | 2073-4360 |
| language | English |
| last_indexed | 2024-04-12T21:19:46Z |
| publishDate | 2017-10-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Polymers |
| spelling | doaj.art-da93a72b64a64a2d9cae6f53a89034262022-12-22T03:16:20ZengMDPI AGPolymers2073-43602017-10-0191053810.3390/polym9100538polym9100538Anionic Polymerization of Styrene and 1,3-Butadiene in the Presence of Phosphazene SuperbasesKonstantinos Ntetsikas0Yahya Alzahrany1George Polymeropoulos2Panayiotis Bilalis3Yves Gnanou4Nikos Hadjichristidis5Polymer Synthesis Laboratory, KAUST Catalysis Center, Physical Sciences and Engineering Division, King Abdullah University of Science and Technology (KAUST), Thuwal 23955, Saudi ArabiaPolymer Synthesis Laboratory, KAUST Catalysis Center, Physical Sciences and Engineering Division, King Abdullah University of Science and Technology (KAUST), Thuwal 23955, Saudi ArabiaPolymer Synthesis Laboratory, KAUST Catalysis Center, Physical Sciences and Engineering Division, King Abdullah University of Science and Technology (KAUST), Thuwal 23955, Saudi ArabiaPolymer Synthesis Laboratory, KAUST Catalysis Center, Physical Sciences and Engineering Division, King Abdullah University of Science and Technology (KAUST), Thuwal 23955, Saudi ArabiaPhysical Sciences and Engineering Division, King Abdullah University of Science and Technology (KAUST), Thuwal 23955, Saudi ArabiaPolymer Synthesis Laboratory, KAUST Catalysis Center, Physical Sciences and Engineering Division, King Abdullah University of Science and Technology (KAUST), Thuwal 23955, Saudi ArabiaThe 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.https://www.mdpi.com/2073-4360/9/10/538anionic polymerizationphosphazene superbaseshigh vacuum techniquekinetic studyblock copolymers |
| spellingShingle | Konstantinos Ntetsikas Yahya Alzahrany George Polymeropoulos Panayiotis Bilalis Yves Gnanou Nikos Hadjichristidis Anionic Polymerization of Styrene and 1,3-Butadiene in the Presence of Phosphazene Superbases Polymers anionic polymerization phosphazene superbases high vacuum technique kinetic study block copolymers |
| title | Anionic Polymerization of Styrene and 1,3-Butadiene in the Presence of Phosphazene Superbases |
| title_full | Anionic Polymerization of Styrene and 1,3-Butadiene in the Presence of Phosphazene Superbases |
| title_fullStr | Anionic Polymerization of Styrene and 1,3-Butadiene in the Presence of Phosphazene Superbases |
| title_full_unstemmed | Anionic Polymerization of Styrene and 1,3-Butadiene in the Presence of Phosphazene Superbases |
| title_short | Anionic Polymerization of Styrene and 1,3-Butadiene in the Presence of Phosphazene Superbases |
| title_sort | anionic polymerization of styrene and 1 3 butadiene in the presence of phosphazene superbases |
| topic | anionic polymerization phosphazene superbases high vacuum technique kinetic study block copolymers |
| url | https://www.mdpi.com/2073-4360/9/10/538 |
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