Abstract
Stereoblock polypropylenes bearing isotactic, atactic, and syndiotactic polypropylene segments were successfully prepared by dry methyl aluminoxane activated binary catalysts system, Ph2CFluCpZrCl2 and {Me2Si(2,5-Me2-3-(2-MePh)-cyclopento[2,3-b]thiophen-6-yl)2}ZrCl2, in the presence of iBu3Al as a chain shuttling agent. By studying the catalyst activity, chain transfer efficiency, and reversibility of chain transfer reaction of each catalyst system, as well as the molecular weight and polydispersity of the resulting polymers, the alkyl exchange reactions between the zirconium catalyst and different main-group metal alky were estimated, respectively. Based on the optimized react condition, the chain shuttling polymerization was conducted by binary catalyst system in the presence of iBu3Al under both atmospheric and high pressure. Resultant polymers were identified as stereoblock polypropylenes according to microstructure and physical properties analyses by 13C{1H}-NMR, DSC, and GPC.
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References
Coates, G. W. Precise control of polyolefin stereochemistry using single-site metal catalysts. Chem. Rev.2000, 100, 1223–1252.
Natta, G.; Pino, P.; Corradini, P.; Danusso, F.; Mantica, E.; Mazzanti, G.; Moraglio, G. Crystalline high polymers of α-oefins J. Am. Chem. Soc.1955, 77, 1708–1710.
Chien, J. C. W.; Iwamoto, Y.; Rausch, M. D. Homogeneous binary zirconocenium catalysts for propylene polymerization. II. Mixtures of isospecific and syndiospecific zirconocene systems. J. Polym. Sci., Part A: Polym. Chem.1999, 37, 2439–2445.
Zhang, W.; Sita, L. R. Highly efficient, living coordinative chain-transfer polymerization of propylene with ZnEt2: practical production of ultrahigh to very low molecular weight amorphous atactic polypropylenes of extremely narrow polydispersity. J. Am. Chem. Soc.2008, 130, 442–443.
Harney, M. B.; Zhang, Y. H.; Sita, L. R. Discrete, multiblock isotactic-atactic stereoblock polypropylene microstructures of differing block architectures through programmable stereomodulated living Ziegler-Natta polymerization. Angew. Chem. Int. Ed.2006, 118, 2400–2404.
Coates, G. W.; Waymouth, R. M. Oscillating stereocontrol: a strategy for the synthesis of thermoplastic elastomeric polypropylene. Science1995, 267, 217–219.
Busico, V.; Cipullo, R.; Segre, A. L.; Talarico, G.; Vacatello, M.; Castelli, V. V. A. “Seeing” the stereoblock junctions in polypropylene made with oscillating metallocene catalysts. Macromolecules2001, 34, 8412–8415.
Cohen, A.; Goldberg, I.; Venditto, V.; Kol, M. Oscillating non-metallocenes-from stereoblock-isotactic polypropylene to isotactic polypropylene viazirconium and hafnium dithiodiphenolate catalysts. Eur. J. Inorg. Chem.2011, 2011, 5219–5223.
De Rosa, C.; Auriemma, F.; Circelli, T. Stereoblock polypropylene from a metallocene catalyst with a hapto-flexible naphthyl-indenyl ligand. Macromolecules2003, 36, 3465–3474.
Miller, S. A.; Bercaw, J. E. Isotactic-hemiisotactic polypropylene from C1-symmetric ansa-metallocene catalysts: a new strategy for the synthesis of elastomeric polypropylene. Organometallics2002, 21, 934–945.
Gauthier, W. J.; Collins, S. Elastomeric polypropylene: propagation models and relationship to catalyst structure. Macromolecules1995, 28, 3779–3786.
Cai, Z. G.; Nakayama, Y.; Shiono, T. Synthesis of stereoblock polypropylene by change of temperature in living polymerization. Macromol. Res.2010, 18, 737–741.
Lieber, S.; Brintzinger, H. H. Propylene polymerization with catalyst mixtures containing different ansa-zirconocenes: chain transfer to alkylaluminum cocatalysts and formation of stereoblock polymers. Macromolecules2000, 33, 9192–9199.
Marques, M. D. V.; Chaves, E. G. Polypropylene fractions produced by binary metallocene catalysts. J. Polym. Sci., Part A: Polym. Chem.2003, 41, 1478–1485.
Ye, Z. B.; Zhu, S. P. Synthesis of branched polypropylene with isotactic backbone and atactic side chains by binary iron and zirconium single-site catalysts. J. Polym. Sci., Part A: Polym. Chem.2003, 41, 1152–1159.
Vaezi, J.; Nekoomanesh, M.; Khonakdar, H. A.; Jafari, S. H.; Mojarrad, A. Correlation of microstructure, rheological and morphological characteristics of synthesized polypropylene (PP) reactor blends using homogeneous binary metallocene catalyst. Polymers2017, 9, 75–89.
Chien, J. C. W.; Iwamoto, Y.; Rausch, M. D.; Wedler, W.; Winter, H. H. Homogeneous binary zirconocenium catalyst systems for propylene polymerization. 1. Isotactic/atactic interfacial compatibilized polymers having thermoplastic elastomeric properties. Macromolecules1997, 30, 3447–3458.
Arriola, D. J.; Carnahan, E. M.; Hustad, P. D.; Kuhlman, R. L.; Wenzel, T. T. Catalytic production of olefin block copolymers via chain shuttling polymerization. Science2006, 312, 714–719.
Valente, A.; Mortreux, A.; Visseaux, M.; Zinck, P. Coordinative chain transfer polymerization. Chem. Rev.2013, 113, 3836–3857.
Zintl, M.; Rieger, B. Novel olefin block copolymers through chain-shuttling polymerization. Angew. Chem. Int. Ed.2007, 46, 333–335.
Xiao, A. G.; Wang, L.; Liu, Q. Q.; Yu, H. J.; Wang, J. J.; Huo, J.; Tan, Q. H.; Ding, J. H.; Ding, W. B.; Amin, A. M. Novel linear-hyperbranched multiblock polyethylene produced from ethylene monomer alone viachain walking and chain shuttling polymerization. Macromolecules2009, 42, 1834–1837.
Pan, L.; Zhang, K. Y.; Nishiura, M.; Hou, Z. M. Chain-shuttling polymerization at two different scandium sites: regio- and stereospecific “one-pot” block copolymerization of styrene, isoprene, and butadiene. Angew. Chem. Int. Ed.2011, 50, 12012–12015.
Valente, A.; Stoclet, G.; Bonnet, F.; Mortreux, A.; Visseaux, M.; Zinck, P. Isoprene-styrene chain shuttling copolymerization mediated by a lanthanide half-sandwich complex and a lanthanidocene: straightforward access to a new type of thermoplastic elastomers. Angew. Chem. Int. Ed.2014, 53, 4638–4641.
Liu, B.; Cui, D. M. Regioselective chain shuttling polymerization of isoprene: an approach to access new materials from single monomer. Macromolecules2016, 49, 6226–6231.
Phuphuak, Y.; Bonnet, F.; Stoclet, G.; Bria, M.; Zinck, P. Isoprene chain shuttling polymerisation between cisand transregulating catalysts: straightforward access to a new material. Chem. Commun.2017, 53, 5330–5333.
Dai, Q. Q.; Zhang, X. Q.; Hu, Y. M.; He, J. Y.; Shi, C.; Li, Y. Q.; Bai, C. X. Regulation of the cis-1,4- and trans-1,4-polybutadiene multiblock copolymers viachain shuttling polymerization using a ternary neodymium organic sulfonate catalyst. Macromolecules2017, 50, 7887–7894.
Childers, M. I.; Vitek, A. K.; Morris, L. S.; Coates, G. W.; Widger, P. C. B.; Ahmed, S. M.; Zimmerman, P. M. Isospecific, chain shuttling polymerization of propylene oxide using a bimetallic chromium catalyst: a new route to semicrystalline polyols. J. Am. Chem. Soc.2017, 139, 11048–11054.
Tynys, A.; Eilertsen, J. L.; Seppala, J. V.; Rytter, E. Propylene polymerizations with a binary metallocene system-chain shuttling caused by trimethylaluminium between active catalyst centers. J. Polym. Sci., Part A: Polym. Chem.2007, 45, 1364–1376.
Alfano, F.; Boone, H. W.; Busico, V.; Cipullo, R.; Stevens, J. C. Polypropylene “chain shuttling” at enantiomorphous and enantiopure catalytic species: direct and quantitative evidence from polymer microstructure. Macromolecules2007, 40, 7736–7738.
Descour, C.; Macko, T.; Cavallo, D.; Parkinson, M.; Hubner, G.; Spoelstra, A.; Villani, M.; Duchateau, R. Synthesis and characterization of iPP-sPP stereoblock produced by a binary metallocene system. J. Polym. Sci., Part A: Polym. Chem.2014, 52, 1422–1434.
Hustad, P. D.; Kuhlman, R. L. Carnahan, E. M.; Wenzel, T. T.; Arriola, D. J. A exploration of the effects of reversibility in chain transfer to metal in olefin polymerization. Macromolecules2008, 41, 4081–4089.
Quevedo-Sanchez, B.; Nimmons, J. F.; Coughlin, E. B.; Henson, M. A. Kinetic modeling of the effect of MAO/Zr ratio and chain transfer to aluminum in zirconocene catalyzed propylene polymerization. Macromolecules2006, 39, 4306–4316.
Lin, W.; Niu, H.; Chung, T. C. M.; Dong, J. Y. Borane chain transfer reaction in olefin polymerization using trialkylboranes as chain transfer agents. J. Polym. Sci., Part A: Polym. Chem.2010, 48, 3534–3541.
Zhang, C. H.; Niu, H.; Dong, J. Y. A novel effect of bis(6-heptenyl) zinc on the molecular weight and rheologic performance of polypropylene produced by rac-Me2Si[2-Me-4-Ph-Ind]2ZrCl2/MAO. Polym. Bull.2010, 65, 779–786.
Fan, G. Q.; Dong, J. Y. A. examination of aluminum chain transfer reaction in rac-Me2Si[2-Me-4-Naph-Ind]2ZrCl2 /MAO catalyzed propylene polymerization and synthesis of aluminum-terminated isotactic polypropylene with controlled molecular weight. J. Mol. Catal. A: Chem.2005, 236, 246–252.
Naga, N.; Mizunuma, K. Chain transfer reaction by trialkylaluminum (AlR3) in the stereospecific polymerization of propylene with metallocene-AlR3/Ph3CB(C6F5)4. Polymer1998, 39, 5059–5067.
Ni Bhriain, N.; Brintzinger, H. H.; Ruchatz, D.; Fink, G. Polymeryl exchange between ansa-zirconocene catalysts for norbornene-ethene copolymerization and aluminum or zinc alkyls. Macromolecules2005, 38, 2056–2063.
Ewen, J. A.; Elder, M. J.; Jones, R. L.; Rheingold, A. L.; Liable-Sands, L. M.; Sommer, R. D. Chiral ansametallocenes with Cp ring-fused to thiophenes and pyrroles: syntheses, crystal structures, and isotactic polypropylene catalysts. J. Am. Chem. Soc.2001, 123, 4763–4773.
Tynys, A.; Eilertsen, J. L.; Rytter, E. Zirconocene propylene polymerisation: controlling termination reactions. Macromol. Chem. Phys.2006, 207, 295–303.
Li, Y. L.; Song, D. P.; Pan, L.; Ma, Z.; Li, Y. S. Facile functionalization of isotactic polypropylene viaclick chemistry. J. Polym. Sci., Part A: Polym. Chem.2019, 10, 6368–6378.
Britovsek, G. J. P; Cohen, S. A. Gibson, V. C.; van Meurs, M. Iron catalyzed polyethylene chain growth on zinc: a study of the factors delineating chain transfer versus catalyzed chain growth in zinc and related metal alkyl systems. J. Am. Chem. Soc.2004, 126, 10701–10712.
Cueny, E. S.; Johnson, H. C.; Landis, C. R. Selective quench-labeling of the hafnium-pyridyl amido-catalyzed polymerization of 1-octene in the presence of trialkyl-aluminum chain-transfer reagents. ACS Catal.2018, 8, 11605–11614.
Zhang, C. H.; Dong, J. Y. Dialkylzinc compounds as chain transfer agents in ethylene and propylene polymerizations catalyzed by metallocene catalysts. J. Macromol. Sci., Part A-Pure Appl. Chem.2010, 47, 452–456.
van Meurs, M.; Britovsek, G. J. P.; Gibson, V. C.; Cohen, S. N. Polyethylene chain growth on zinc catalyzed by olefin polymerization catalysts: a comparative investigation of highly active catalyst systems across the transition series. J. Am. Chem. Soc.2005, 127, 9913–9923.
Hue, R. J.; Cibuzar, M. P.; Tonks, I. A. Analysis of polymeryl chain transfer between group 10 metals and main group alkyls during ethylene polymerization. ACS Catal.2014, 4, 4223–4231.
Santamaki, S.; Aitola, E.; Kokko, E.; Repo, T.; Leskela, M.; Seppala, J. Activation of hafnocene catalyzed polymerization of 1-hexene with MAO and borate. Eur. Polym. J.2009, 45, 863–869.
Fryga, J.; Białek, M. Effect of AlR3 (R = Me, Et, iBu) addition on the composition and microstructure of ethylene/1-olefin copolymers made with postmetallocene complexes of group 4 elements. Polym. J.2018, 51, 19–29.
Rouholahnejad, F.; Mathis, D.; Chen, P. Narrowly distributed polyethylene viareversible chain transfer to aluminum by a sterically hindered zirconocene/MAO. Organometallics2010, 29, 294–302.
Jeon, J. Y.; Park, S. H.; Kim, D. H.; Park, S. S.; Park, G. H.; Lee, B. Y. Synthesis of polyolefin-block-polystyrene through sequential coordination and anionic polymerizations. J. Polym. Sci., Part A: Polym. Chem.2016, 54, 3110–3118.
Lee, H. J.; Baek, J. W.; Kim, T. J.; Park, H. S.; Moon, S. H.; Park, K. L.; Bae S. M.; Park, J.; Lee, B. Y. Synthesis of long-chain branched polyolefins by coordinative chain transfer polymerization. Macromolecules2019, 52, 9311–9320.
Zhang, C. H; Huang, H. H.; Niu, H.; Dong, J. Y. Alkyl exchange reaction between dialkylzinc compounds and methylaluminoxane and the effect on propylene polymerization. Appl. Organomet. Chem.2010, 24, 641–645.
Ehm, C.; Cipullo, R.; Budzelaar, P. H. M.; Busico, V. Role(s) of TMA in polymerization. Dalton Trans.2016, 45, 6847–6855.
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This work was financially supported by the National Natural Science Foundation of China (No. 21574097).
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Stereoblock Polypropylenes Prepared by Efficient Chain Shuttling Polymerization of Propylene with Binary Zirconium Catalysts and iBu3Al
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Yin, X., Gao, H., Yang, F. et al. Stereoblock Polypropylenes Prepared by Efficient Chain Shuttling Polymerization of Propylene with Binary Zirconium Catalysts and iBu3Al. Chin J Polym Sci 38, 1192–1201 (2020). https://doi.org/10.1007/s10118-020-2446-2
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DOI: https://doi.org/10.1007/s10118-020-2446-2