Abstract
The efficient copolymerization of olefin with polar monomers using nickel-based catalysts presents a longstanding challenge. In this contribution, three phosphine-benzocyclone ligands and corresponding neutral nickel catalysts (Ni1: Ar = Ph; Ni2: Ar = 2-(C6H5)C6H4; Ni3: Ar = 2-[2′,6′-(MeO)2-C6H3]C6H4) were prepared and applied for the ethylene polymerization and copolymerization with polar monomers without any cocatalyst. The bulky substituent groups in complexes Ni2 and Ni3 contributed to high catalytic activities (up to 7.24×106 and 9.04×106 g·molNi−1·h−1, respectively), and produced high-molecular-weight polyethylene (Mw up to 545.7 kDa). Complex Ni3 exhibited high activities for ethylene polymerization at the level of 106 g·molNi−1·h−1 across a wide range from 30 °C to 120 °C, exhibiting excellent high temperature tolerance. These nickel complexes were also effectively employed in the copolymerization of ethylene with methyl acrylate, ethyl acrylate, butyl acrylate and lauryl acrylate, producing copolymers with high molecular weights (Mw up to 80.5 kDa) and high polar monomer incorporation (up to 8.2 mol%). Microstructure analyses revealed that the introduction of large sterically hindered substituents facilitated the incorporation of polar functional units into the polymer backbone. This study demonstrates the potential of these nickel-based catalysts for efficient copolymerization of olefin with polar monomers.
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References
Dong, J. Y.; Hu, Y. L. Design and synthesis of structurally well-defined functional polyolefins via transition metal-mediated olefin polymerization chemistry. Coord. Chem. Rev. 2006, 250, 47–65.
Nakamura, A.; Anselment, T. M.; Claverie, J.; Goodall, B.; Jordan, R. F.; Mecking, S.; Rieger, B.; Sen, A.; van Leeuwen, P. W.; Nozaki, K. Ortho-phosphinobenzenesulfonate: a superb ligand for palladium-catalyzed coordination-insertion copolymerization of polar vinyl monomers. Acc. Chem. Res. 2013, 46, 1438–1449.
Chen, E. Y. X. Coordination polymerization of polar vinyl monomers by single-site metal catalysts. Chem. Rev. 2009, 109, 5157–5214.
Chung, T. C. M. Functional polyolefins for energy applications. Macromolecules 2013, 46, 6671–6698.
Tan, C.; Zou, C.; Chen, C. L. Material properties of functional polyethylenes from transition-metal-catalyzed ethylene-polar monomer copolymerization. Macromolecules 2022, 55, 1910–1922.
Huang, M. L.; Chen, J. Z.; Wang, B. H.; Huang, W.; Chen, H. B.; Gao, Y. S.; Marks, T. J. Polar isotactic and syndiotactic polypropylenes by organozirconium-catalyzed masking-reagent-free propylene and amino-olefin copolymerization. Angew. Chem. Int. Ed. 2020, 59, 20522–20528.
Keyes, A.; Basbug Alhan, H. E.; Ordonez, E.; Ha, U.; Beezer, D. B.; Dau, H.; Liu Y. S.; Tsogtgerel, E.; Jones, G. R.; Harth, E. Olefins and vinyl polar monomers: bridging the gap for next generation materials. Angew. Chem. Int. Ed. 2019, 58, 12370–12391.
Chen, J. Z.; Gao, Y. S.; Marks, T. J. Early transition metal catalysis for olefin-polar monomer copolymerization. Angew. Chem. Int. Ed. 2020, 59, 14726–14735.
Cui, D. M. Studies on homo- and co-polymerizations of polar and non-polar monomers using rare-earth metal catalysts. Acta Polymerica Sinica (in Chinese) 2020, 51, 12–29.
Ittel, S. D.; Johnson, L. K.; Brookhart, M. Late-metal catalysts for ethylene homo-and copolymerization. Chem. Rev. 2000, 100, 1169–1204.
Chen, Z.; Brookhart, M. Exploring ethylene/polar vinyl monomer copolymerizations using Ni and Pd a-diimine catalysts. Acc. Chem. Res. 2018, 51, 1831–1839.
Nakamura, A.; Ito, S.; Nozaki, K. Coordination-insertion copolymerization of fundamental polar monomers. Chem. Rev. 2009, 109, 5215–5244.
Chu, Y. K.; Hu, X. Q.; Zhang, Y.; Liu, D. J.; Zhang, Y. X.; Jian, Z. B. Influence of backbone and axial substituent of catalyst on a-imino-ketone nickel mediated ethylene (co)polymerization. Chinese J. Polym. Sci. 2022, 40, 469–477.
Wang, F.; Wang, X. L.; Pan, L.; Wang, B.; Li, Y. S. Efficient copolymerization of ethylene with polar divinyl monomer by phosphino-phenolate nickel catalyst. Chin. J. Chem. 2023, 41, 1037–1044.
Cui, L.; Chu, Y. K.; Liu, D. J.; Han, Y. F.; Mu, H. L.; Jian, Z. B. Enhancement on hemilabile phosphine-amide palladium and nickel catalysts for ethylene (co)polymerization with polar monomers using a cyclizing strategy. Chinese J. Polym. Sci. 2022, 40, 241–247.
Zhang, R. D.; Gao, R.; Gou, Q. Q.; Lai, J. J.; Li, X. Y. Recent advances in the copolymerization of ethylene with polar comonomers by nickel catalysts. Polymers 2022, 14, 3809.
Karimi, M.; Arabi, H.; Sadjadi, S. New advances in olefin homo and copolymerization using neutral, single component palladium/nickel complexes ligated by a phosphinesulfonate. J. Catal. 2022, 412, 59–70.
Wu, R. K.; Klingler Wu W. Y.; Stieglitz, L.; Gaan, S.; Rieger, B.; Heuberger, M. Recent advances on a-diimine Ni and Pd complexes for catalyzed ethylene (co)polymerization: a comprehensive review. Coord. Chem. Rev. 2023, 474, 214844.
Cui, L.; Chen, M.; Chen, C. L.; Liu, D. T.; Jian, Z. B. Systematic studies on (co) polymerization of polar styrene monomers with palladium catalysts. Macromolecules 2019, 52, 7197–7206.
Liu, G. X.; Huang, Z. Recent advances in coordination-insertion copolymerization of ethylene with polar functionalized comonomers. Chin. J. Chem. 2020, 38, 1445–1448.
Qasim, M.; Bashir, M. S.; Iqbal, S.; Mahmood, Q. Recent advancements in a-diimine- nickel and - palladium catalysts for ethylene polymerization. Eur. Polym. J. 2021, 160, 110783.
Odenwald, L.; Wimmer, F. P.; Mast, N. K.; Schußmann, M. G.; Wilhelm, M.; Mecking, S. Molecularly defined polyolefin vitrimers from catalytic insertion polymerization. J. Am. Chem. Soc. 2022, 144, 13226–13233.
Peng, D.; Chen, C. L. Photoresponsive palladium and nickel catalysts for ethylene polymerization and copolymerization. Angew. Chem. Int. Ed. 2021, 60, 22195–22200.
Xu, M. H.; Chen, C. L. A disubstituted-norbornene-based comonomer strategy to address polar monomer problem. Sci. Bull. 2021, 66, 1429–1436.
Johnson, L. K.; Mecking, S., Brookhart, M. Copolymerization of ethylene and propylene with functionalized vinyl monomers by palladium(II) catalysts. J. Am. Chem. Soc. 1996, 118, 267–268.
Behzadi, S.; Zou, C.; Yang, B. P.; Tan, C.; Chen, C. L. Styrene-containing phosphine-sulfonate ligands for nickel- and palladium-catalyzed ethylene polymerization. Chinese J. Polym. Sci. 2021, 39, 447–454.
Mecking, S.; Schnitte, M. Neutral nickel(II) catalysts: from hyperbranched oligomers to nanocrystal-based materials. Acc. Chem. Res. 2020, 53, 2738–2752.
Mu, H. L.; Pan, L.; Song, D. P.; Li, Y. S. Neutral nickel catalysts for olefin homo- and copolymerization: relationships between catalyst structures and catalytic properties. Chem. Rev. 2015, 115, 12091–12137.
Mu, H. L.; Zhou, G. L.; Hu, X. Q.; Jian, Z. B. Recent advances in nickel mediated copolymerization of olefin with polar monomers. Coord. Chem. Rev. 2021, 435, 213802.
Yang, B. P.; Xiong, S. Y.; Chen, C. L. Manipulation of polymer branching density in phosphine-sulfonate palladium and nickel catalyzed ethylene polymerization. Polym. Chem. 2017, 8, 6272–6276.
Xia, J.; Zhang, Y. X.; Zhang, J. F.; Jian, Z. B. High-performance neutral phosphinesulfonate nickel(II) catalysts for efficient ethylene polymerization and copolymerization with polar monomers. Organometallics 2019, 38, 1118–1126.
Xia, J.; Han, Y. F.; Kou, S. Q.; Zhang, Y. X.; Jian, Z. B. Exploring steric effect of electron-donating group in palladium and nickel mediated ethylene polymerization and copolymerization with polar monomers. Eur. Polym. J. 2021, 160, 110781.
Tao, W. J.; Nakano, R.; Ito, S.; Nozaki, K. Copolymerization of ethylene and polar monomers by using Ni/IzQO catalysts. Angew. Chem. Int. Ed. 2016, 55, 2835–2839.
Younkin, T. R.; Connor, E. F.; Henderson, J. I.; Friedrich, S. K.; Grubbs, R. H.; Bansleben, D. A. Neutral, single-component nickel(II) polyolefin catalysts that tolerate heteroatoms. Science 2000, 287, 460–462.
Cheng, H. L.; Wang, H. J.; Li, Y. Q.; Hu, Y. M.; Zhang, X. Q.; Cai, Z. G. Structurally simple dinuclear nickel catalyzed olefin copolymerization with polar monomers. J. Catal. 2018, 368, 291–297.
Cheng, H. L.; Cai, Z. G. (Anilino)anthraquinone nickel-catalyzed random copolymerization of norbornene and ethylene. ChemCatChem 2018, 10, 497–500.
Fu, X.; Zhang, L. J.; Tanaka, R.; Shiono, T.; Cai, Z. G. Highly robust nickel catalysts containing anilinonaphthoquinone ligand for copolymerization of ethylene and polar monomers. Macromolecules 2017, 50, 9216–9221.
Jung, J.; Yasuda, H.; Nozaki, K. Copolymerization of nonpolar olefins and allyl acetate using nickel catalysts bearing a methylene-bridged bisphosphine monoxide ligand. Macromolecules 2020, 53, 2547–2556.
Cao, L. X.; Cai, Z. G.; Li, M. Y. Phosphinobenzenamine nickel catalyzed efficient copolymerization of methyl acrylate with ethylene and norbornene. Macromolecules 2022, 55, 3513–3521.
Ji, G.; Chen, Z.; Wang, X. Y.; Ning, X. S.; Xu, C. J.; Zhang, X. M.; Tao, W. J.; Li, J. F.; Gao, Y. S.; Shen, Q.; Sun, X. L.; Wang, H. Y.; Zhao, J. B.; Zhang, B.; Guo, Y. L.; Zhao, Y. N.; Sun, J. J.; Luo, Y.; Tang, Y. Direct copolymerization of ethylene with protic comonomers enabled by multinuclear Ni catalysts. Nat. Commun. 2021, 12, 6283.
Li, Y. Q.; Cheng, H. L.; Xiao, R.; Cai, Z. G. Rational design of nickel catalysts containing N-acylated imidazoline-2-imine ligand for ethylene copolymerization with polar monomer. J. Catal. 2020, 383, 117–123.
Song, D. P.; Wang, Y. X.; Mu, H. L.; Li, B. X.; Li, Y. S. Observations and mechanistic insights on unusual stability of neutral nickel complexes with a sterically crowded metal center. Organometallics 2011, 30, 925–934.
Zou, C.; Zhang, H.; Tan, C.; Cai, Z. G. Polyolefins with intrinsic antimicrobial properties. Macromolecules 2021, 54, 64–70.
Tan, C.; Qasim, M.; Pang, W. M.; Chen, C. L. Ligand-metal secondary interactions in phosphine-sulfonate palladium and nickel catalyzed ethylene (co)polymerization. Polym. Chem. 2020, 11, 411–416.
Wang, Q.; Wang, W. B.; Qu, W. C.; Pang, W. M.; Qasim, M.; Zou, C. Ethylene homo and copolymerization by phosphorus-benzoquinone based homogeneous and heterogeneous nickel catalysts. J. Polym. Sci. 2022, 61, 115–122.
Zhang, H.; Zou, C.; Zhao, H. P.; Cai, Z. G.; Chen, C. L. Hydrogen-bonding-induced heterogenization of nickel and palladium catalysts for copolymerization of ethylene with polar monomers. Angew. Chem. Int. Ed. 2021, 60, 17446–17451.
Baur, M.; Mecking, S. Polyethylenes with combined in-chain and side-chain functional groups from catalytic terpolymerization of carbon monoxide and acrylate. ACS Macro Lett. 2022, 11, 1207–1211.
Zou, C.; Si, G. F.; Chen, C. L. A general strategy for heterogenizing olefin polymerization catalysts and the synthesis of polyolefins and composites. Nat. Commun. 2022, 13, 1954.
Baur, M.; Lin, F.; Morgen, T. O.; Odenwald, L.; Mecking, S. Polyethylene materials with in-chain ketones from nonalternating catalytic copolymerization. Science 2021, 374, 604–607.
Xiong, S. Y.; Shoshani, M. M.; Zhang, X. L.; Spinney, H. A.; Nett, A. J.; Henderson, B. H.; Miller, T. F.; Agapie, T. Efficient copolymerization of acrylate and ethylene with neutral P, O-chelated nickel catalysts: mechanistic investigations of monomer insertion and chelate formation. J. Am. Chem. Soc. 2021, 143, 6516–6527.
Lin, F.; Morgen, T. O.; Mecking, S. Living aqueous microemulsion polymerization of ethylene with robust Ni(II) phosphinophenolato catalysts. J. Am. Chem. Soc. 2021, 143, 20605–20608.
Zhang, Y. P.; Mu, H. L.; Pan, L.; Wang, X. L.; Li, Y. S. Robust bulky [P,O] neutral nickel catalysts for copolymerization of ethylene with polar vinyl monomers. ACS Catal. 2018, 8, 5963–5976.
Zhang, Y. P.; Mu, H. L.; Wang, X.; Pan, L.; Li, Y. S. Elaborate tuning in ligand makes a big difference in catalytic performance: bulky nickel catalysts for (co)polymerization of ethylene with promising vinyl polar monomers. ChemCatChem 2019, 11, 2329–2340.
Xin, B. S.; Sato, N.; Tanna, A.; Oishi, Y.; Konishi, Y.; Shimizu, F. Nickel catalyzed copolymerization of ethylene and alkyl acrylates. J. Am. Chem. Soc. 2017, 139, 3611–3614.
Wang, X. L.; Zhang, Y. P.; Wang, F.; Pan, L.; Wang, B.; Li Y. S. Robust and reactive neutral nickel catalysts for ethylene polymerization and copolymerization with a challenging 1,1-disubstituted difunctional polar monomer. ACS Catal. 2021, 11, 2902–2911.
Wang, X. L.; Zhang, Y. P.; Pan, L.; Wang, F.; Luo, S.; Li, Y. S. Reactivity of phosphino-naphtholate nickel complexes and their catalysis of copolymerization with polar monomers. ChemCatChem 2022, 14, e202101736.
Tanemura, K.; Suzuki, T.; Nishida, Y.; Satsumabayashi, K.; Horaguchi, T. A mild and efficient procedure for a-bromination of ketones using N-bromosuccinimide catalysed by ammonium acetate. Chem. Commun. 2004, 470–471.
Nakamura, A.; Anselment, T. M. J.; Claverie, J.; Goodall, B.; Jordan, R. F.; Mecking, S.; Rieger, B.; Sen, A.; van Leeuwen, P. W. N. M.; Nozaki, K. Ortho- phosphinobenzenesulfonate: A superb ligand for palladium-catalyzed coordination-insertion copolymerization of polar vinyl monomers. Acc. Chem. Res. 2013, 46, 1438–1449.
Drent, E.; van Dijk, R.; van Ginkel, R.; van Oort, B.; Pugh, R. I. Palladium catalysed copolymerisation of ethene with alkylacrylates: polar comonomer built into the linear polymer chain. Chem. Commun. 2002, 744–745.
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This work was financially supported by the National Natural Science Foundation of China (No. 52130307).
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Phosphine/Benzocyclone-based Neutral Nickel Catalysts for Ethylene Polymerization and Copolymerization with Polar Monomers
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Wang, F., Pan, L., Tuskaev, V.A. et al. Phosphine/Benzocyclone-based Neutral Nickel Catalysts for Ethylene Polymerization and Copolymerization with Polar Monomers. Chin J Polym Sci 42, 202–212 (2024). https://doi.org/10.1007/s10118-023-3044-x
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DOI: https://doi.org/10.1007/s10118-023-3044-x