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Well-Defined Metal Complex Catalysts for Olefin Polymerization

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Organometallic Chemistry".

Deadline for manuscript submissions: closed (15 May 2019) | Viewed by 28393

Special Issue Editor


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Guest Editor
CNR - Istituto di Scienze e Tecnologie Chimiche “Giulio Natta“ (SCITEC), via A. Corti 12, I-20133 Milano, Italy
Interests: organometallic chemistry; transition metals; lanthanides; stereospecific polymerization; olefins/cycloolefins/conjugated diolefins; polydienes; polybutadiene; diene polymerization mechanism

Special Issue Information

Dear Colleagues,

Starting in the 2000s, a new generation of catalysts based on well-defined transition metal and lanthanide complexes with different ligands containing N and/or P and/or O as donor atoms began to be introduced. These new catalytic systems proved to be extremely active and able to exert precise control of the regio- and stereo-selectivity in the homo- and co-polymerization of olefins, cycloolefins, and conjugated diolefins, providing polymers with different structures and properties.

The objective of this Special Issue is to report on the most recent results obtained in this field, in particular as regards: i) the synthesis and characterization of novel organometallic complexes for the stereospecific polymerization of olefins, cycloolefins, and conjugated diolefins; ii) the elucidation of the fundamental role played by the ligand’s nature in determining the polymerization regio- and stereoselectivity, in controlling the molecular weight and molecular weight distribution, and in conferring in some cases a living character to the catalyst itself.

All researchers working in this field are warmly invited to join this initiative by sending their contributions.

Dr. Giovanni Ricci
Guest Editor

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Keywords

  • organometallic complexes
  • transition metals
  • lanthanides
  • stereospecific polymerization
  • regioselectivity
  • stereoselectivity
  • olefins
  • cycloolefins
  • conjugated diolefins
  • polyolefins/polydiolefins
  • polymerization mechanism

Published Papers (9 papers)

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Research

27 pages, 6258 KiB  
Article
C–H-Bond Activation and Isoprene Polymerization Studies Applying Pentamethylcyclopentadienyl-Supported Rare-Earth-Metal Bis(Tetramethylaluminate) and Dimethyl Complexes
by Christoph O. Hollfelder, Melanie Meermann-Zimmermann, Georgios Spiridopoulos, Daniel Werner, Karl W. Törnroos, Cäcilia Maichle-Mössmer and Reiner Anwander
Molecules 2019, 24(20), 3703; https://doi.org/10.3390/molecules24203703 - 15 Oct 2019
Cited by 6 | Viewed by 2797
Abstract
As previously shown for lutetium and yttrium, 1,2,3,4,5-pentamethylcyclopentadienyl (C5Me5 = Cp*)-bearing rare-earth metal dimethyl half-sandwich complexes [Cp*LnMe2]3 are now also accessible for holmium, dysprosium, and terbium via tetramethylaluminato cleavage of [Cp*Ln(AlMe4)2] with diethyl [...] Read more.
As previously shown for lutetium and yttrium, 1,2,3,4,5-pentamethylcyclopentadienyl (C5Me5 = Cp*)-bearing rare-earth metal dimethyl half-sandwich complexes [Cp*LnMe2]3 are now also accessible for holmium, dysprosium, and terbium via tetramethylaluminato cleavage of [Cp*Ln(AlMe4)2] with diethyl ether (Ho, Dy) and tert-butyl methyl ether (TBME) (Tb). C–H-bond activation and ligand redistribution reactions are observed in case of terbium and are dominant for the next larger-sized gadolinium, as evidenced by the formation of mixed methyl/methylidene clusters [(Cp*Ln)5(CH2)(Me)8] and metallocene dimers [Cp*2Ln(AlMe4)]2 (Ln = Tb, Gd). Applying TBME as a “cleaving” reagent can result in both TBME deprotonation and ether cleavage, as shown for the formation of the 24-membered macrocycle [(Cp*Gd)2(Me)(CH2OtBu)2(AlMe4)]4 or monolanthanum complex [Cp*La(AlMe4){Me3Al(CH2)OtBu}] and monoyttrium complex [Cp*Y(AlMe4)(Me3AlOtBu)], respectively. Complexes [Cp*Ln(AlMe4)2] (Ln = Ho, Dy, Tb, Gd) and [Cp*LnMe2]3 (Ln = Ho, Dy) are applied in isoprene and 1,3-butadiene polymerization, upon activation with borates [Ph3C][B(C6F5)4] and [PhNHMe2][B(C6F5)4], as well as borane B(C6F5)3. The trans-directing effect of AlMe3 in the binary systems [Cp*Ln(AlMe4)2]/borate is revealed and further corroborated by the fabrication of high-cis-1,4 polybutadiene (97%) with “aluminum-free” [Cp*DyMe2]3/[Ph3C][B(C6F5)4]. The formation of multimetallic active species is supported by the polymerization activity of pre-isolated cluster [(Cp*Ho)3Me4(CH2)(thf)2]. Full article
(This article belongs to the Special Issue Well-Defined Metal Complex Catalysts for Olefin Polymerization)
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17 pages, 3098 KiB  
Article
Highly Active Iminopyridyl Iron-Based Catalysts for the Polymerization of Isoprene
by Obaid H. Hashmi, Yohan Champouret and Marc Visseaux
Molecules 2019, 24(17), 3024; https://doi.org/10.3390/molecules24173024 - 21 Aug 2019
Cited by 21 | Viewed by 3546
Abstract
A series of iminopyridyl-based ligands, 6-[(Ar)N=C(R)]-2-C6H5N [(Ar = 2,6-Me2-C6H3, R = Me (L1); Ar = 2,6-iPr2-C6H3, R = Me (L2); Ar [...] Read more.
A series of iminopyridyl-based ligands, 6-[(Ar)N=C(R)]-2-C6H5N [(Ar = 2,6-Me2-C6H3, R = Me (L1); Ar = 2,6-iPr2-C6H3, R = Me (L2); Ar = 2,6-Me2-C6H3, R = H (L3); Ar = 2,6-iPr2-C6H3, R = H (L4); Ar = 3,5-(CF3)2-C6H3, R = Me (L5); Ar = C6F5, R = Me (L6)], and their corresponding iron (II) complexes were developed to investigate their application in the controlled coordinative polymerization of isoprene. The modulation of steric and electronic properties within this family of ligands/pre-catalysts has shown to influence the stereo-selectivity and activity of the polymerization of isoprene after activation. Upon activation with various co-catalysts such as AliBu3/[Ph3C][B(C6F5)4], AlEt3/[Ph3C][B(C6F5)4] or MAO, the resulting catalysts produced polyisoprenes with an excellent conversion (>99% of 500–5000 equiv.) within less than 1 h (TOF > 500 h−1) and having a variety of stereo-/regio-regularities. The presence of electron-donating and withdrawing groups drastically impacted the activity and the stereoselectivity of the catalysts during the course of the polymerization of isoprene. When activated with AliBu3/[Ph3C][B(C6F5)4], the complexes {6-[(2,6-Me2-C6H3)N=C(Me)]-2-C6H5N}FeCl2 (C1) and {6-[(2,6-iPr2-C6H3)N=C(Me)]-2-C6H5N}FeCl2 (C2) exhibited moderate trans-1,4 selectivity (>67%) while the iron-based systems bearing related aldiminopyridyl ligands {6-[(2,6-Me2-C6H3)N=C(H)]-2-C6H5N}FeCl2 (C3) and {6-[(2,6-iPr2-C6H3)N=C(H)]-2-C6H5N}FeCl2 (C4) were found to afford significant cis-1,4 selectivity at low temperature (>86% at −40 °C). On the other hand, the ternary {6-[(3,5-(CF3)2-C6H3)N=C(Me)]-2-C6H5N}FeCl2 (C5) or {6-[(C6F5)N=C(Me)]-2-C6H5N}FeCl2 (C6)/AliBu3/[Ph3C][B(C6F5)4] catalytic combinations showed exceptional activity for the polymerization of isoprene (TOF > 1,000,000 h−1), albeit providing less stereoselectivity. Full article
(This article belongs to the Special Issue Well-Defined Metal Complex Catalysts for Olefin Polymerization)
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8 pages, 985 KiB  
Article
Novel Cobalt Dichloride Complexes with Hindered Diphenylphosphine Ligands: Synthesis, Characterization, and Behavior in the Polymerization of Butadiene
by Giovanni Ricci, Giuseppe Leone, Ivana Pierro, Giorgia Zanchin and Alessandra Forni
Molecules 2019, 24(12), 2308; https://doi.org/10.3390/molecules24122308 - 21 Jun 2019
Cited by 8 | Viewed by 2303
Abstract
Two novel cobalt diphenylphosphine complexes were synthesized by reacting cobalt(II) chloride with tert-butyl(diphenyl)phosphine (PtBuPh2) and (S)-(+)neomenthyldiphenylphosphine [(S)-NMDPP]. The crystal structure of the former was determined by single-crystal X-ray diffraction studies. The two complexes were [...] Read more.
Two novel cobalt diphenylphosphine complexes were synthesized by reacting cobalt(II) chloride with tert-butyl(diphenyl)phosphine (PtBuPh2) and (S)-(+)neomenthyldiphenylphosphine [(S)-NMDPP]. The crystal structure of the former was determined by single-crystal X-ray diffraction studies. The two complexes were then used in combination with methylaluminoxane (MAO) for the polymerization of 1,3-butadiene: crystalline highly syndiotactic 1,2 poly(1,3-butadiene)s were obtained, with a 1,2 content and a syndiotactic index (percentage of syndiotactic triads [rr]) up to 95% and 85%, respectively. The results obtained further support and confirm what was already observed in the polymerization of 1,3-butadiene with CoCl2(PRPh2)2−MAO (R = methyl, ethyl, normal-propyl, iso-propyl, and cyclohexyl): the nature of the phosphine ligand strongly affects the polymerization stereoselectivity, the polymer syndiotacticity increasing with increasing phosphine ligand steric hindrance. Full article
(This article belongs to the Special Issue Well-Defined Metal Complex Catalysts for Olefin Polymerization)
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10 pages, 955 KiB  
Article
Homo- and Copolymerization of Ethylene with Norbornene Catalyzed by Vanadium(III) Phosphine Complexes
by Giorgia Zanchin, Alessia Gavezzoli, Fabio Bertini, Giovanni Ricci and Giuseppe Leone
Molecules 2019, 24(11), 2088; https://doi.org/10.3390/molecules24112088 - 31 May 2019
Cited by 7 | Viewed by 2824
Abstract
Herein, we report the homo- and co-polymerization of ethylene (E) with norbornene (NB) catalyzed by vanadium(III) phosphine complexes of the type VCl3(PMenPh3-n)2 [n = 2 (1a), 1 (1b)] and VCl3(PR [...] Read more.
Herein, we report the homo- and co-polymerization of ethylene (E) with norbornene (NB) catalyzed by vanadium(III) phosphine complexes of the type VCl3(PMenPh3-n)2 [n = 2 (1a), 1 (1b)] and VCl3(PR3)2 [R = phenyl (Ph, 1c), cyclohexyl (Cy, 1d), tert-butyl (tBu, 1e)]. In the presence of Et2AlCl and Cl3CCOOEt (ETA), 1a1e exhibit good activities for the polymerization of ethylene, affording linear, semicrystalline PEs with a melting temperature of approximately 130 °C. Mainly alternating copolymers with high comonomer incorporation were obtained in the E/NB copolymerization. A relationship was found between the electronic and steric properties of the phosphine ligands and the catalytic performance. Overall, the presence of electron-withdrawing ligand substituents increases the productivity, complexes with aryl phosphine (weaker σ–donor character) exhibiting a higher (co)polymerization initiation rate than those with alkyl phosphines (stronger σ–donor character). Steric effects also seem to play a key role since 1d and 1e, having large size phosphines (PCy3 θ = 170° and PtBu3 θ = 182°, respectively) are more active than 1a (PMe2Ph θ = 122°). In this case, the larger size of PtBu3 and PCy3 likely compensates for their higher donor strength compared to PMe2Ph. Full article
(This article belongs to the Special Issue Well-Defined Metal Complex Catalysts for Olefin Polymerization)
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22 pages, 2984 KiB  
Article
Activity and Thermal Stability of Cobalt(II)-Based Olefin Polymerization Catalysts Adorned with Sterically Hindered Dibenzocycloheptyl Groups
by Muhammad Zada, Liwei Guo, Yanping Ma, Wenjuan Zhang, Zygmunt Flisak, Yang Sun and Wen-Hua Sun
Molecules 2019, 24(10), 2007; https://doi.org/10.3390/molecules24102007 - 25 May 2019
Cited by 24 | Viewed by 2753
Abstract
Five examples of unsymmetrical 2-(2,4-bis(dibenzocycloheptyl)-6-methylphenyl- imino)ethyl)-6-(1-(arylyimino)ethyl)pyridine derivatives (aryl = 2,6-Me2C6H3 in L1; 2,6-Et2C6H3 in L2; 2,6-i-Pr2C6H3 in L3; 2,4,6-Me3C6H2 in [...] Read more.
Five examples of unsymmetrical 2-(2,4-bis(dibenzocycloheptyl)-6-methylphenyl- imino)ethyl)-6-(1-(arylyimino)ethyl)pyridine derivatives (aryl = 2,6-Me2C6H3 in L1; 2,6-Et2C6H3 in L2; 2,6-i-Pr2C6H3 in L3; 2,4,6-Me3C6H2 in L4 and 2,6-Et2-4-MeC6H2 in L5) were prepared and characterized. Treatment with CoCl2 offered the corresponding cobalt precatalysts Co1Co5, which were characterized by FT-IR and NMR spectroscopy as well as elemental analysis. The molecular structures of Co3 and Co4 determined by single crystal X-ray diffraction revealed distorted square pyramidal geometries with τ5 values of 0.052–0.215. Activated with either MAO or MMAO, the precatalysts displayed high activities in ethylene polymerization, where Co1 with the least bulky substituents exhibited a peak activity of 1.00 × 107 g PE mol−1 (Co) h−1 at 60 °C. With MAO as a cocatalyst, the activity was reduced only by one order of magnitude at 90 °C, which implies thermally stable active sites. The polymerization product was highly linear polyethylene with vinyl end groups. Co3 with the most sterically hindered active sites was capable of generating polyethylene of high molecular weight, reaching 6.46 × 105 g mol−1. Furthermore, high melting point and unimodal molecular weight distribution were observed in the resulting polyethylene. It must be stressed that the thermal stability of the catalyst and the molecular weight of the obtained polyethylene attain the highest values reported for the unsymmetrical 2,6-bis(imino)pyridylcobalt (II) chloride precatalysts. Full article
(This article belongs to the Special Issue Well-Defined Metal Complex Catalysts for Olefin Polymerization)
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18 pages, 2328 KiB  
Article
Preparation of Pincer Hafnium Complexes for Olefin Polymerization
by Su Jin Kwon, Jun Won Baek, Hyun Ju Lee, Tae Jin Kim, Ji Yeon Ryu, Junseong Lee, Eun Ji Shin, Ki Soo Lee and Bun Yeoul Lee
Molecules 2019, 24(9), 1676; https://doi.org/10.3390/molecules24091676 - 29 Apr 2019
Cited by 6 | Viewed by 3162
Abstract
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 [...] Read more.
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. Full article
(This article belongs to the Special Issue Well-Defined Metal Complex Catalysts for Olefin Polymerization)
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10 pages, 1483 KiB  
Article
Synthesis of Ultrahigh Molecular Weight Polymers with Low PDIs by Polymerizations of 1-Decene, 1-Dodecene, and 1-Tetradecene by Cp*TiMe2(O-2,6-iPr2C6H3)–Borate Catalyst
by Kotohiro Nomura, Sarntamon Pengoubol and Wannida Apisuk
Molecules 2019, 24(8), 1634; https://doi.org/10.3390/molecules24081634 - 25 Apr 2019
Cited by 11 | Viewed by 3922
Abstract
Polymerizations of 1-decene (DC), 1-dodecene (DD), and 1-tetradecene (TD) by Cp*TiMe2(O-2,6-iPr2C6H3) (1)–[Ph3C][B(C6F5)4] (borate) catalyst have been explored in the presence of Al cocatalyst. [...] Read more.
Polymerizations of 1-decene (DC), 1-dodecene (DD), and 1-tetradecene (TD) by Cp*TiMe2(O-2,6-iPr2C6H3) (1)–[Ph3C][B(C6F5)4] (borate) catalyst have been explored in the presence of Al cocatalyst. The polymerizations of DC and DD, in n-hexane containing a mixture of AliBu3 and Al(n-C8H17)3, proceeded with high catalytic activities in a quasi-living manner, affording high molecular weight polymers (activity 4120–5860 kg-poly(DC)/mol-Ti·h, Mn for poly(DC) = 7.04–7.82 × 105, after 20 min at −30 °C). The PDI (Mw/Mn) values in the resultant polymers decreased upon increasing the ratio of Al(n-C8H17)3/AliBu3 with decreasing the activities at −30 °C. The PDI values also became low when these polymerizations were conducted at low temperatures (−40 or −50 °C); high molecular weight poly(DD) with low PDI (Mn = 5.26 × 105, Mw/Mn = 1.16) was obtained at −50 °C. The TD polymerization using 1–borate–AliBu3 catalyst (conducted in n-hexane at −30 °C) afforded ultrahigh molecular weight poly(TD) (Mn = 1.02 × 106, Mw/Mn = 1.38), and the PDI values also decreased with increasing the Al(n-C8H17)3/AliBu3 ratio. Full article
(This article belongs to the Special Issue Well-Defined Metal Complex Catalysts for Olefin Polymerization)
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14 pages, 18917 KiB  
Article
Propylene Polymerization Catalyzed by Metallocene/Methylaluminoxane Systems on Rice Husk Ash
by Kuo-Tseng Li and Cheng-Ni Yang
Molecules 2019, 24(8), 1467; https://doi.org/10.3390/molecules24081467 - 13 Apr 2019
Cited by 4 | Viewed by 2980
Abstract
Silica generated from agricultural waste is more cost effective and environmentally friendly than silica from traditional commercial processes. In this study, spherical silica particles with a diameter of around 120 nm were fabricated from rice husk ash (RHA), and were used to support [...] Read more.
Silica generated from agricultural waste is more cost effective and environmentally friendly than silica from traditional commercial processes. In this study, spherical silica particles with a diameter of around 120 nm were fabricated from rice husk ash (RHA), and were used to support two bridged zirconcene complexes ((I) Me2Si(Ind)2ZrCl2 and (II) C2H4(Ind)2ZrCl2) for catalyzing propylene polymerization to produce polypropylene (PP) in a temperature range of 40–70 °C and in a solution methylaluminoxane (MAO) range of 0.1–0.6 wt%. Due to its small particle size, RHA-supported catalyst exhibited much higher activity than micro-sized commercial silica-supported catalyst. At the optimum polymerization temperature of 55 °C and with increasing MAO concentration, polymer yield increased proportionally with the increase of number average molecular weight. Compared to (I), (II) produced more polymer molecules but with much shorter chain length, ascribed to the differences of Zr loading and bridge structure. With increasing polymerization temperature, polymer molecular weight decreased rapidly and resulted in a significant change of PP assembly morphology (shape and size). At 55 °C, (I) produced uniform PP assemblies which had dumbbell-like structure with a smooth middle section and two fibrillar ends, while (II) produced spherical PP particles. The dumbbell middle part width was essentially identical to the Batchelor microscale proposed in turbulent mixing theory. Full article
(This article belongs to the Special Issue Well-Defined Metal Complex Catalysts for Olefin Polymerization)
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20 pages, 4127 KiB  
Article
Highly Linear Polyethylenes Achieved Using Thermo-Stable and Efficient Cobalt Precatalysts Bearing Carbocyclic-Fused NNN-Pincer Ligand
by Jingjing Guo, Zheng Wang, Wenjuan Zhang, Ivan I. Oleynik, Arumugam Vignesh, Irina V. Oleynik, Xinquan Hu, Yang Sun and Wen-Hua Sun
Molecules 2019, 24(6), 1176; https://doi.org/10.3390/molecules24061176 - 25 Mar 2019
Cited by 30 | Viewed by 3590
Abstract
Six examples of 2-(1-arylimino)ethyl-9-arylimino-5,6,7,8-tetrahydrocycloheptapyridine-cobalt(II) chloride complexes, [2-(1-ArN)C2H3-9-ArN-5,6,7,8-C5H8C5H3N]CoCl2, (Ar = 2-(C5H9)-6-MeC6H3 Co1, 2-(C6H11)-6-MeC6H3 Co2, [...] Read more.
Six examples of 2-(1-arylimino)ethyl-9-arylimino-5,6,7,8-tetrahydrocycloheptapyridine-cobalt(II) chloride complexes, [2-(1-ArN)C2H3-9-ArN-5,6,7,8-C5H8C5H3N]CoCl2, (Ar = 2-(C5H9)-6-MeC6H3 Co1, 2-(C6H11)-6-MeC6H3 Co2, 2-(C8H15)-6-MeC6H3 Co3, 2-(C5H9)-4,6-Me2C6H2 Co4, 2-(C6H11)-4,6-Me2C6H2 Co5, and 2-(C8H15)-4,6-Me2C6H2 Co6), were synthesized by the direct reaction of the corresponding ortho-cycloalkyl substituted carbocyclic-fused bis(arylimino)pyridines (L1L6) and cobalt(II) chloride in ethanol with good yields. All the synthesized ligands (L1L6) and their corresponding cobalt complexes (Co1Co6) were fully characterized by FT-IR, 1H/13C-NMR spectroscopy and elemental analysis. The crystal structure of Co2 and Co3 revealed that the ring puckering of both the ortho-cyclohexyl/cyclooctyl substituents and the one pyridine-fused seven-membered ring; a square-based pyramidal geometry is conferred around the metal center. On treatment with either methylaluminoxane (MAO) or modified methylaluminoxane (MMAO), all the six complexes showed high activities (up to 4.09 × 106 g of PE mol−1 (Co) h−1) toward ethylene polymerization at temperatures between 20 °C and 70 °C with the catalytic activities correlating with the type of ortho-cycloalkyl substituent: Cyclopentyl (Co1 and Co4) > cyclohexyl (Co2 and Co5) > cyclooctyl (Co3 and Co6) for either R = H or Me and afforded strictly linear polyethylene (Tm > 130 °C). The narrow unimodal distributions of the resulting polymers are consistent with single-site active species for the precatalyst. Furthermore, compared to the previously reported cobalt analogues, the titled precatalysts exhibited good thermo-stability (up to 70 °C) and possessed longer lifetime along with a higher molecular weight of PE (Mw: 9.2~25.3 kg mol−1). Full article
(This article belongs to the Special Issue Well-Defined Metal Complex Catalysts for Olefin Polymerization)
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