Preparation of [bis(amido)-phosphine] and [amido-phosphine sulfide or oxide] hafnium and zirconium complexes for olefin polymerization

Lee, Chun Sun; Park, Ji Hae; Hwang, Eun Yeong; Park, Geun Ho; Go, Min Jeong; Lee, Junseong; Lee, Hyun Ju

doi:10.1016/j.jorganchem.2014.09.009

Cited by 15 publications

(3 citation statements)

References 42 publications

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“…The prototype Hf catalyst I was exceptional in terms of the activity and α-olefin incorporation capability. We also reported various types of Hf-complexes ([N,P]Hf(CH 2 Ph) 3 , [N,P,N]HfMe 2 , and [N,N]Hf(CH 2 Ph) 3 -type) with tetrahydroquinoline and tetrahydrophenanthroline framework, which were also inferior to I in terms of both activity and α-olefin incorporation capability [45,46,47]. The Hf-C bonding character was significantly ionic when compared to those of Zr-C and Ti-C bonding, and steric congestion around Hf-center might be crucial for the high activity [48].…”

Section: Resultsmentioning

confidence: 99%

Preparation of Pincer Hafnium Complexes for Olefin Polymerization

et al. 2019

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Pincer-type [Cnaphthyl, Npyridine, Namido]HfMe2 complex is a flagship among the post-metallocene catalysts. In this work, various pincer-type Hf-complexes were prepared for olefin polymerization. Pincer-type [Namido, Npyridine, Namido]HfMe2 complexes were prepared by reacting in situ generated HfMe4 with the corresponding ligand precursors, and the structure of a complex bearing 2,6-Et2C6H3Namido moieties was confirmed by X-ray crystallography. When the ligand precursors of [(CH3)R2Si-C5H3N-C(H)PhN(H)Ar (R = Me or Ph, Ar = 2,6-diisopropylphenyl) were treated with in situ generated HfMe4, pincer-type [Csilylmethyl, Npyridine, Namido]HfMe2 complexes were afforded by formation of Hf-CH2Si bond. Pincer-type [Cnaphthyl, Sthiophene, Namido]HfMe2 complex, where the pyridine moiety in the flagship catalyst was replaced with a thiophene unit, was not generated when the corresponding ligand precursor was treated with HfMe4. Instead, the [Sthiophene, Namido]HfMe3-type complex was obtained with no formation of the Hf-Cnaphthyl bond. A series of pincer-type [Cnaphthyl, Npyridine, Nalkylamido]HfMe2 complexes was prepared where the arylamido moiety in the flagship catalyst was replaced with alkylamido moieties (alkyl = iPr, cyclohexyl, tBu, adamantyl). Structures of the complexes bearing isopropylamido and adamantylamido moieties were confirmed by X-ray crystallography. Most of the complexes cleanly generated the desired ion-pair complexes when treated with an equivalent amount of [(C18H37)2N(H)Me]+[B(C6F5)4]−, which showed negligible activity in olefin polymerization. Some complexes bearing bulky substituents showed moderate activities, even though the desired ion-pair complexes were not cleanly afforded.

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Section: Resultsmentioning

confidence: 99%

Preparation of Pincer Hafnium Complexes for Olefin Polymerization

et al. 2019

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“…Accordingly, the polymers generated by III are amorphous, while the polymers generated by 10 – 12 and 16 exhibited melting signals around 100 °C. We also reported various type of Hf complexes ([N,P]Hf(CH 2 Ph) 3 , [N,P,N]HfMe 2 , and [N,N]Hf(CH 2 Ph) 3 -type) with tetrahydroquinoline and tetrahydrophenanthroline frameworks, which were also inferior to III in terms of the α-olefin incorporation capability as well as the activity [50,51,52].…”

Section: Resultsmentioning

confidence: 99%

Preparation of Half- and Post-Metallocene Hafnium Complexes with Tetrahydroquinoline and Tetrahydrophenanthroline Frameworks for Olefin Polymerization

et al. 2019

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Hafnium complexes have drawn attention for their application as post-metallocene catalysts with unique performance in olefin polymerization. In this work, a series of half-metallocene HfMe2 complexes, bearing a tetrahydroquinoline framework, as well as a series of [Namido,N,Caryl]HfMe2-type post-metallocene complexes, bearing a tetrahydrophenanthroline framework, were prepared; the structures of the prepared Hf complexes were unambiguously confirmed by X-ray crystallography. When the prepared complexes were reacted with anhydrous [(C18H37)2N(H)Me]+[B(C6F5)4]−, desired ion-pair complexes, in which (C18H37)2NMe coordinated to the Hf center, were cleanly afforded. The activated complexes generated from the half-metallocene complexes were inactive for the copolymerization of ethylene/propylene, while those generated from post-metallocene complexes were active. Complex bearing bulky isopropyl substituents (12) exhibited the highest activity. However, the activity was approximately half that of the prototype pyridylamido-Hf Dow catalyst. The comonomer incorporation capability was also inferior to that of the pyridylamido-Hf Dow catalyst. However, 12 performed well in the coordinative chain transfer polymerization performed in the presence of (octyl)2Zn, converting all the fed (octyl)2Zn to (polyolefinyl)2Zn with controlled lengths of the polyolefinyl chain.

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“…At present, the ammonium tetrakis(pentafluorophenyl)borate cocatalyst as a substitute for MAO can be applied to the polymerization of ethylene and 1-octene, as shown in Table 4 . Lee et al [ 68 ] showed the catalytic performance of group-4 metal complexes with the phosphine-amido ligand derivatives in the copolymerization of ethylene and 1-octene. In the catalytic system, MDOAB is used as the cocatalyst to efficiently achieve copolymerization.…”

Section: Research Progress Of Ammonium Tetrakis(pentafluorophenyl)boratementioning

confidence: 99%

Ammonium Tetrakis(pentafluorophenyl)borate: Preparation and Application in Olefin Coordination Polymerization as the Cocatalyst Compound

Wei,

Qu,

et al. 2024

Polymers

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Metallocene catalysts have attracted much attention from academia and industry for their excellent catalytic activity in the field of olefin polymerization. Cocatalysts play a key role in metallocene catalytic systems, which can not only affect the overall catalytic activity, but also have an obvious influence on the structure and properties of the polymer. Although methylaluminoxane (MAO) is currently the most widely used cocatalyst, its price increases the production cost of polyolefin materials. Ammonium tetrakis(pentafluorophenyl)borate has shown excellent performance in polymerization, being one of the best substitutes for the traditional cocatalyst MAO. Compared with the main catalyst, whose composition and structure are relatively complex, the research on cocatalyst is very limited. This review mainly introduces the research history, preparation methods, and application progress in polymerization of ammonium tetrakis(pentafluorophenyl)borate, deepening our understanding of the role of cocatalyst in polymerization, with the hope of inspiring brand-new thinking on improving and enhancing the overall performance of catalyst systems.

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Preparation of [bis(amido)-phosphine] and [amido-phosphine sulfide or oxide] hafnium and zirconium complexes for olefin polymerization

Cited by 15 publications

References 42 publications

Preparation of Pincer Hafnium Complexes for Olefin Polymerization

Preparation of Pincer Hafnium Complexes for Olefin Polymerization

Preparation of Half- and Post-Metallocene Hafnium Complexes with Tetrahydroquinoline and Tetrahydrophenanthroline Frameworks for Olefin Polymerization

Ammonium Tetrakis(pentafluorophenyl)borate: Preparation and Application in Olefin Coordination Polymerization as the Cocatalyst Compound

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