Heterogeneous catalysts have long dominated polyethylene and polypropylene production, but understanding their catalysis is challenged by uncertainties in active site structures and percentages. Surface-bound organometallic catalysts are an emerging strategy to combine successful homogeneous catalysts having well-understood structures, relatively high percentages of active sites, and exceptional control of selectivity, with the attractions of surface catalysts, to transition promising homogeneous systems to large-scale heterogeneous ones. Nevertheless, surface-bound olefin polymerization catalysts typically produce ultrahigh Mw’s but with low activity and comonomer selectivity. Here, we report the systematic synthesis and characterization of a series of pyridylamido-Hf complexes and their corresponding surface catalysts chemisorbed on sulfated alumina (AlS) and zirconia (ZrS). Comparative ethylene homo- and 1-octene copolymerizations reveal similar activity and 1-octene selectivity trends in the homogeneous and heterogeneous systems. For the surface pyridylamido-Hf catalyst series, large variations in activity (up to 10×) and 1-octene incorporation (up to 28×) are achieved by ligand and support manipulation. Interestingly, while the homogeneous catalysts exhibit positive comonomer effects in ethylene/1-octene copolymerization, the surface catalysts behave oppositely. Extended X-ray absorption fine structure (EXAFS) reveals significantly elongated Hf···O bond distances vs typical Hf-O covalent bonds (2.06 vs 1.97 Å). Density functional theory (DFT) analysis of the heterolytic ion pair separation enthalpies, olefin insertion energetics, and NBO/Bader charges also suggest electrostatic Hf cation-anionic support binding and catalytic patterns, which are modulated by the ion-pairing energetics and ligand architecture.
Surface vs homogeneous organo-hafnium catalyst ion-pairing and ligand effects on ethylene homo- and copolymerizations / Zhang, Jialong; Mason, Alexander H.; Motta, Alessandro; Cesar, Laryssa G.; Kratish, Yosi; Lohr, Tracy L.; Miller, Jeffrey T.; Gao, Yanshan; Marks, Tobin J.. - In: ACS CATALYSIS. - ISSN 2155-5435. - 11:6(2021), pp. 3239-3250. [10.1021/acscatal.0c04678]
Surface vs homogeneous organo-hafnium catalyst ion-pairing and ligand effects on ethylene homo- and copolymerizations
Motta, Alessandro
;
2021
Abstract
Heterogeneous catalysts have long dominated polyethylene and polypropylene production, but understanding their catalysis is challenged by uncertainties in active site structures and percentages. Surface-bound organometallic catalysts are an emerging strategy to combine successful homogeneous catalysts having well-understood structures, relatively high percentages of active sites, and exceptional control of selectivity, with the attractions of surface catalysts, to transition promising homogeneous systems to large-scale heterogeneous ones. Nevertheless, surface-bound olefin polymerization catalysts typically produce ultrahigh Mw’s but with low activity and comonomer selectivity. Here, we report the systematic synthesis and characterization of a series of pyridylamido-Hf complexes and their corresponding surface catalysts chemisorbed on sulfated alumina (AlS) and zirconia (ZrS). Comparative ethylene homo- and 1-octene copolymerizations reveal similar activity and 1-octene selectivity trends in the homogeneous and heterogeneous systems. For the surface pyridylamido-Hf catalyst series, large variations in activity (up to 10×) and 1-octene incorporation (up to 28×) are achieved by ligand and support manipulation. Interestingly, while the homogeneous catalysts exhibit positive comonomer effects in ethylene/1-octene copolymerization, the surface catalysts behave oppositely. Extended X-ray absorption fine structure (EXAFS) reveals significantly elongated Hf···O bond distances vs typical Hf-O covalent bonds (2.06 vs 1.97 Å). Density functional theory (DFT) analysis of the heterolytic ion pair separation enthalpies, olefin insertion energetics, and NBO/Bader charges also suggest electrostatic Hf cation-anionic support binding and catalytic patterns, which are modulated by the ion-pairing energetics and ligand architecture.File | Dimensione | Formato | |
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