FOLLOWUS
a.School of Polymer Science and Engineering, Qingdao University of Science & Technology, Qingdao 266042, China
b.Shandong Provincial College Laboratory of Rubber Material and Engineering, School of Polymer Science and Engineering, Qingdao University of Science & Technology, Qingdao 266042, China
c.Key Lab of Rubber-Plastics, Ministry of Education/Shandong Provincial Key Lab of Rubber-plastics, School of Polymer Science and Engineering, Qingdao University of Science & Technology, Qingdao 266042, China
cyzhang@qust.edu.cn
Received:06 March 2025,
Revised:28 March 2025,
Accepted:02 April 2025,
Published Online:20 June 2025,
Published:2025-04
Scan QR Code
Sun, Y. F.; Zhao, Y. N.; Xu, S. L.; Yu, Y.; Fang, L.; Na, L. H.; Yang, Q.; Wang, F.; Liu, H.; Zhang, C. Y.; Zhang, X. Q. Synthesis and characterization of α-end functionalized 3,4-polyisoprene using Fe(acac)3/IITP/Al
Yu-Fan Sun, Ying-Nan Zhao, Shi-Liang Xu, et al. Synthesis and Characterization of
Sun, Y. F.; Zhao, Y. N.; Xu, S. L.; Yu, Y.; Fang, L.; Na, L. H.; Yang, Q.; Wang, F.; Liu, H.; Zhang, C. Y.; Zhang, X. Q. Synthesis and characterization of α-end functionalized 3,4-polyisoprene using Fe(acac)3/IITP/Al
Yu-Fan Sun, Ying-Nan Zhao, Shi-Liang Xu, et al. Synthesis and Characterization of
The synthesis of functionalized rubber copolymers is a topic of great research interest. In this study
we present a novel approach for the direct construction of
α
-functionalized 3
4-polyisoprene through polymerization of polar monomers and isoprene monomer. The
α
-functionalized 3
4-polyisoprene was successfully synthesized
via
in situ
sequential polymerization using the iron-based catalytic system (Fe(acac)
3
/IITP/Al
i
Bu
3
)
exhibiting high activity and resistance to polar monomers without requiring protection of polar groups. The structure of
α
-functionalized 3
4-polyisoprene was confirmed by proton nuclear magnetic resonance spectroscopy (
1
H-NMR) and two-dimensional diffusion-ordered spectroscopy (2D DOSY) spectra analysis. The introduction of polar groups
particularly hydroxyl groups
enhanced the hydrophilicity of the copolymer. This was evidenced by a decrease in the water contact angle from 106.9° to 96.4° with increasing hydroxyl content in the copolymer.
Le Cam, J. B. Energy storag e due to strain-induced crystallization in natural rubber: the physical origin of the mechanical hysteresis. Polymer 2017 , 127 , 166−173..
Albouy, P. A.; Guillier, G.; Petermann, D.; Vieyres, A.; Sanseau, O.; Sotta, P. A stroboscopic X-ray apparatus for the study of the kinetics of strain-induced crystallization in natural rubber. Polymer 2012 , 53 , 3313−3324..
Kohjiya, S.; Tosaka, M.; Furutani, M.; Ikeda, Y.; Toki, S.; Hsiao, B. S. Role of stearic acid in the strain-induced crystallization of crosslinked natural rubber and synthetic cis -1,4-polyisoprene. Polymer 2007 , 48 , 3801−3808..
Kitaura, T.; Kobayashi, M.; Tarachiwin, L.; Kum-ourm, H.; Matsuura, A.; Fushihara, K.; Ute, K. Characterization of natural rubber end groups using high-densitivity-NMR. Macromol. Chem. Phys. 2018 , 219 , 201700331..
Tang, M.; Zhang, R.; Li, S.; Zeng, J.; Luo, M.; Xu, Y. X.; Huang, G. Towards a supertough thermoplastic polyisoprene elastomer based on a biomimic strategy. Angew. Chem. Int. Ed. 2018 , 57 , 15836−15840..
Zhou, Y.; Kosugi, K.; Yamamoto, Y.; Kawahara, S. Effect of non-rubber components on the mechanical properties of natural rubber. Polym. Adv. Technol. 2017 , 28 , 159−165..
Dixit, M.; Taniguchi, T. Role of terminal groups of cis -1,4-polyisoprene chains in the formation of physical junction points in natural rubber. Biomacromolecules 2023 , 24 , 3589−3602..
Liu, P.; Yang, X.; Li, H.; Zhang, S.; Hu, Y.; Zhou, G.; Hadjichristidis, N. Synthesis of α,ω -end functionalized polydienes: allylic-bearing heteroleptic aluminums for selective alkylation and transalkylation in coordinative chain transfer polymerization. Angew. Chem. Int. Ed. 2023 , 63 , 202317494..
Yao, C.; Liu, N.; Long, S.; Wu, C.; Cui, D. Highly cis -1,4-selective coordination polymerization of polar 2-(4-methoxyphenyl)-1,3-butadiene and copolymerization with isoprene using a β -diketiminato yttrium bis(alkyl) complex. Polym. Chem. 2016 , 7 , 1264−1270..
Nuyken, O.; Anwander, R. Neodymium based ziegler catalysts-fundamental chemistry. Springer Berl. Heid. 2006 , 204 , 1-154..
Chen, M. K.; Zhao, Y. H.; Zhang, R.; Yang, Y.; Cao, J.; Tang, M. Z.; Huang, G.; Xu, Y. X. Carbonate nanophase guided by terminally functionalized polyisoprene leading to a super tough, recyclable and transparent rubber. Chem. Eng. J. 2023 , 452 , 139130..
Yao, T.; Huang, B.; Yao, W.; Ding, H. Research and development of 3,4-polyisoprene rubber. Chin. Synth. Rubber. Ind. (in Chinese) 2004 , 27 , 122−126..
Li, D.; Johnny, W.; Hsu, A.; Halasa, P. Tire tread compound made with strain crystallizable 3,4-polyisoprene. 1994 , US5356997A.
Wang, Q.; Sun, T.; Wei, C.; Sun, N.; Zhao, W.; Liu, L.; Wei, L.; Liu, H.; Zhang, C.; Zhang, X.; Sun, Y. Liquid 3,4-polyisoprene: a novel processing aid to achieve tire tread SBR composites with high wet grip and low energy consumption. Polym. Test. 2022 , 115 , 107713..
Nakayama, Y.; Baba, Y.; Yasuda, H.; Kawakita, K.; Ueyama, N. Stereospecific polymerizations of conjugated dienes by single site iron complexes having chelating N,N,N -donor ligands. Macromolecules 2003 , 36 , 7953−7958..
Ayano, S.; Yabe, S. Anionic polymerization of isoprene. I. polymerization of isoprene by oligomeric dilithium initiator. Polym. J . 1970 , 1 , 700−705..
Chen, W.; Wang, F. Synthetic rubbers prepared by lanthanide coordination catalysts. Sci. Chin. (B, Chem). 2009 , 39 , 1006−1027..
Guo, J.; Zhang, S.; Ren, J.; Li, H.; Wang, S.; Hu, Y.; Zhou, G. Highly active and thermally robust pyridylbenzotriazole iron-based catalysts for preparation of polyisoprenes that feature high wet traction and low rolling resistance. Mol. Catal. 2023 , 549 , 113481..
Natta, G.; Porri, L.; Carbonaro, A. Polymerization of conjugated diolefins by homogeneous aluminum alkyl-titanium alkoxide catalyst systems. Ii. 1,2-polybutadiene and 3,4-polyisoprene. Macromol. Chem. Phys. 1964 , 77 , 126−138..
Ricci, G.; Leone, G.; Boglia, A.; Boccia, A.C.; Zetta, L. Cis -1,4- alt -3,4 polyisoprene: synthesi s and characterization. Macromolecules 2009 , 42 , 9263−9267..
Zhao, J.; Chen, H.; Li, W.; Jia, X.; Zhang, X.; Gong, D. Polymerization of isoprene promoted by aminophosphine(ory)-fused bipyridine cobalt complexes: precise control of molecular weight and cis -1,4- alt -3,4 sequence. Inorg. Chem. 2018 , 57 , 4088−4097..
Fang, L.; Zhao, W.; Han, C.; Liu, H.; Hu, Y.; Zhang, X. Isoprene polymerization with pyrazolylimine cobalt(II) complexes: manipulation of 3,4-selectivities by ligand design and use of triphenylphosphine. Eur. J. Inorg. Chem. 2019 , 2019 , 609−616..
Zhang, L.; Luo, Y.; Hou, Z. Unprecedented isospecific 3,4-polymerization of isoprene by cationic rare earth metal alkyl species resulting from a binuclear precursor. J. Am. Chem. Soc. 2005 , 127 , 14562−14574..
Shao, F.; Ni,X.; Shen, Z. Preparation of amphiphilic graft copolymer with polyisoprene backbone by combination of anionic polymerization and “click” reaction. Chin. Chem. Lett. 2012 , 23 , 347−350..
Li, L.; Li, S.; Cui, D. Highly cis -1,4-selective living polymerization of 3-methylenehepta-1,6-diene and its subsequent thiol-ene reaction: an efficient approach to functionalized diene-based elastomer. Macromolecules 2016 , 49 , 1242−1251..
Georges, S.; Hashmi, O.; Zinck, M.; Champouret, Y.; Visseaux, M. Efficient one-pot synthesis of end-functionalized trans -stereoregular polydiene macromonomers. Macromolecules 2019 , 52 , 1210−1219..
Leicht, H.; Bauer, J.; Göttker-Schnetmann, I.; Mecking, S. Heterotelechelic and in-chain polar functionalized stereoregular poly(dienes). Macromolecules 2018 , 51 , 763−770..
Leicht, H.; Göttker-Schnetmann, I.; Mecking, S. Synergetic effect of monomer functional group coordination in catalytic insertion polymerization. J. Am. Chem. Soc. 2017 , 139 , 6823−6826..
Kularatne, R.N.; Yang, A.; Nguyen, H.Q.; McCandless, G.T.; Stefan, M.C. Neodymium catalyst for the polymerization of dienes and polar vinyl monomers. Macromol. Rapid Commun. 2017 , 38 , 427−432..
Yao, C.; Liu, D.; Li, P.; Wu, C.; Li, S.; Liu, B.; Cui, D. Highly 3,4-selective living polymerization of isoprene and copolymerization with ε -caprolactone by an amidino N -heterocyclic carbene ligated lutetium bis(alkyl) complex. Organometallics. 2014 , 33 , 684−691..
Leicht, H.; Göttker-Schnetmann, I.; Mecking, S. Stereoselective copolymerization of butadiene and functionalized 1,3-dienes. A CS Macro. Lett . 2016 , 5 , 777−780..
Wang, W. X.; Zhao, W. P.; Dong, J.; Zhang, H. Q.; Wang, F.; Liu, H.; Zhang, X.Q. Polyisoprene bearing dual functionalized mini-blocky chain-ends prepared from neodymium-mediated coordinative chain transfer polymerizations. Chinese J. Polym. Sci. 2023 , 41 , 720−727..
Zhang, X. H.; Ma, L.; Dong, J.; Li, W.; Li, X.; Liu, H.; Zhang, X. Q.; Wang, F. Facile and efficient in-situ end-functionalization of neodymium-based polybutadiene by isocyanate via a coordinative chain transfer polymerization strategy. Polymer 2024 , 305 , 166−179..
Li, S.; Tang, M.; Huang, C.; Zhang, R.; Wu, J.; Ling, F.; Xu, Y.X.; Huang, G . Branching function of terminal phosphate groups of polyisoprene chain. Polymer 2019 , 174 , 18−24..
He, Y.; Xu, R.; Zhang, R.; Wang, C. C.; Li, S. Q.; Cao, J.; Tang, M. Z.; Xu, Y. X. Promoted comprehensive properties of polyisoprene rubber with extremely high fatigue resistance enabled by oligopeptide aggregates. Chinese J. Polym. Sci. 2023 , 41 , 1250−1260..
Guo, F.; Nishiura, M.; Li, Y.; Hou, Z. Copolymerization of isoprene and nonconjugated α,ω -dienes by half-sandwich scandium catalysts with and without a coordinative side arm. Chem. Asian J. 2013 , 8 , 2471−2482..
Wang, F.; Liu, H.; Hu, Y. M.; Zhang, X. Q. Lanthanide complexes mediated coordinative chain transfer polymerization of conjugated dienes. Sci. Chin. Technol. 2018 , 61 , 1286−1294..
Tang, M.; Bai, S. J.; Xu, R.; Zhang, R.; Li, S. Q.; Xu, Y. X. Oligopeptide binding guided by spacer length lead to remarkably strong and stable network of polyisoprene elastomers. Polymer 2021 , 233 , 124185..
Wang, C. C.; Yin, H. B.; Bai, S. J.; Zhang, R.; Li, C. H.; Tang, M. Z.; Xu, Y.X. Probe the terminal interactions and their synergistic effects on polyisoprene properties by mimicking the structure of natural rubber. Polymer 2021 , 237 , 124362..
Gong, D.; Tang, F.; Xu, Y.; Hu, Z.; Luo, W. Cobalt catalysed controlled copolymerization: an efficient approach to bifunctional polyisoprene with enhanced properties. Polym. Chem. 2021 , 12 , 1653−1660..
Han, Z.; Zhang, Y.; Wang, L.; Zhu, G.; Kuang, J.; Zhu, G.; Xu, G.; Wang, Q. 3,4-Enhanced polymerization of isoprene catalyzed by side-arm tridentate iminopyridine iron complex with high activity: optimization via response surface methodology. Polymers 2023 , 15 , 1231-1246..
Zhao, M.; Wang, L.; Mahmood, Q.; Jing, C.; Zhu, G.; Zhang, X.; Wang, X.; Wang, Q. Controlled isoprene polymerization mediated by iminopyridine-iron(II) acetylacetonate pre-catalysts. Appl. Organ.Chem. 2019 , 33 , 4836−4846..
Zhao, Y. N.; Xu, S. L.; Yu, Y.; Liu, H.; Wang, F.; Na, L.; Yang, Q.; Zhang, C. Y.; Zhang, X. Q. Preparation and characterization of soft-hard block copolymer of 3,4-IP- b - s -1,2-PBD using a robust iron-based catalyst system. Polymers 2024 , 16 , 1172−1186..
Xu, S. L.; Zhao, Y. N.; Yu, Y. Yang, Q.; Na, L. H.; Liu, H.; Zhang, C. Y.; Zhang, X. Q. Study on catalytic behavior of iron-based catalyst with IITP as electron donor in the polymerization of butadiene. Chinese J. Polym. Sci. 2024 , 42 , 612−619..
Liu, X. J.; Zheng, H.; Wang, X.; Jiang, Z.; Gu, J.; Liu, H.; Zhang, C. Y.; Yang, Q.; Zhang, X. Q. Novel butadiene/isoprene copolymer with predominant 1,2/3,4-units: a tough thermoplastic elastomer material with superior dynamic mechanical properties. Eur. Polym. J. 2023 , 196 , 112333..
Liang, S.; Zhang, H.; Cong, R.; Liu, H.; Wang, F.; Hu, Y.; Zhang, X. In-chain functionalized syndiotactic 1,2-polybutadiene by a ziegler–natta iron(Ⅲ) catalytic system. RSC Adv. 2019 , 9 , 33465−33471..
Cabaret, O. D.; Vaca, B. M.; Bourissou, D. Controlled ring-opening polymerization of lactide and glycolide. Chem. Rev. 2004 , 36 , 6147−6176..
Andrea, K. A.; Kert on, F. M. Functionalized polycarbonates via triphenylborane catalyzed polymerization-hydrosilylation. RSC Adv. 2019 , 9 , 26542−26546..
Kaneyoshi, H.; Inoue, Y.; Matyjaszewski, K. Synthesis of block and graft copolymers with linear polyethylene segments by combination of degenerative transfer coordination polymerization and atom transfer radical polymerization. Macromolecules 2005 , 38 , 5425−5435..
Wu, Q.; Hu, J.; Ren, X.; Zhou, J. An Efficient, overall [4+1 ] cycloadditon of 1,3-dienes and nitrene precursors. Chem-A. Eur. J. 2011 , 17 , 11553−11558..
Wang, Q. Y.; Huang, J.; Li, S.; Cui, D. Synthesis of hydroxyl functionalized high cis -1,4-conjugated diene rubber. Acta Polymerica Sinica (in Chinese) 2022 , 53 , 474−481..
Zhang, J.; Pointer, W.; Patias, G.; Al-Shok, L.; Hand, R. A.; Smith, T.; Haddleton, D. M. End functionalization of polyisoprene and polymyrcene obtained by anionic polymerization via one-pot ring-opening mono-addition of epoxides. Eur. Polym. J. 2023 , 183 , 111755..
0
Views
0
Downloads
0
CSCD
Publicity Resources
Related Articles
Related Author
Related Institution