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Communication

In Situ Efficient End Functionalization of Polyisoprene by Epoxide Compounds via Neodymium-Mediated Coordinative Chain Transfer Polymerization

1
Shandong Provincial College Laboratory of Rubber Material and Engineering/Key Laboratory of Rubber-Plastics, Ministry of Education, School of Polymer Science and Engineering, Qingdao University of Science & Technology, Qingdao 266042, China
2
Petrochemical Research Institute, PetroChina, Beijing 102206, China
*
Author to whom correspondence should be addressed.
Polymers 2024, 16(18), 2672; https://doi.org/10.3390/polym16182672
Submission received: 10 August 2024 / Revised: 4 September 2024 / Accepted: 19 September 2024 / Published: 22 September 2024
(This article belongs to the Section Polymer Chemistry)

Abstract

The Nd-mediated coordinative chain transfer polymerization (CCTP) of dienes represents one of the state-of-the-art techniques in the current synthetic rubber field. Besides having well-controlled polymerization behaviors as well as high atom economies, it also allows for the generation of highly reactive Al-capped polydienyl chain-ends, which hold great potential, yet much less explored up to date, in achieving end functionalization to mimic the structure of natural rubber. In this study, we demonstrate an efficient in situ method to realize end-functionalizing polyisoprene by introducing epoxide compounds into a CCTP system. The end functionalization efficiency was 92.7%, and the obtained polymers were systematically characterized by 1H NMR, 1H,1H-COSY NMR, DOSY NMR, and MALDI TOF. NMR studies revealed that a maximum of two EO units were introduced to the chain ends, and based on density functional theory (DFT) studies, an energy barrier of 33.3 kcal/mol was required to be overcome to open the ring of the EO monomer. Increasing the ratio of [Ip]/[Nd] resulted in gradually increased viscosities for the reaction medium and therefore gave rise to an end functionalization efficiency that decreased from 92.7% to 74.2%. The end hydroxyl group can also be readily converted to other functionalities, as confirmed by NMR spectroscopy.
Keywords: neodymium; polyisoprene; functionalization; coordinative chain transfer polymerization neodymium; polyisoprene; functionalization; coordinative chain transfer polymerization
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MDPI and ACS Style

Zhang, X.; Dong, J.; Wang, F.; Zhang, X.; Liu, H. In Situ Efficient End Functionalization of Polyisoprene by Epoxide Compounds via Neodymium-Mediated Coordinative Chain Transfer Polymerization. Polymers 2024, 16, 2672. https://doi.org/10.3390/polym16182672

AMA Style

Zhang X, Dong J, Wang F, Zhang X, Liu H. In Situ Efficient End Functionalization of Polyisoprene by Epoxide Compounds via Neodymium-Mediated Coordinative Chain Transfer Polymerization. Polymers. 2024; 16(18):2672. https://doi.org/10.3390/polym16182672

Chicago/Turabian Style

Zhang, Xiuhui, Jing Dong, Feng Wang, Xuequan Zhang, and Heng Liu. 2024. "In Situ Efficient End Functionalization of Polyisoprene by Epoxide Compounds via Neodymium-Mediated Coordinative Chain Transfer Polymerization" Polymers 16, no. 18: 2672. https://doi.org/10.3390/polym16182672

APA Style

Zhang, X., Dong, J., Wang, F., Zhang, X., & Liu, H. (2024). In Situ Efficient End Functionalization of Polyisoprene by Epoxide Compounds via Neodymium-Mediated Coordinative Chain Transfer Polymerization. Polymers, 16(18), 2672. https://doi.org/10.3390/polym16182672

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