Study on the copolymerization of propylene with norbornene using metallocene catalysts

Dougnac, Vivianne N.; Peoples, Brian C.; Rabagliati, Franco M.; Galland, Griselda B.; Quijada, Raúl

doi:10.1007/s00289-012-0771-5

Cited by 6 publications

(2 citation statements)

References 23 publications

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“…The C-C bridged bonds C(26)─C (35) and C(7)─C (36) of Ni1 were formed between trifluoromethyl and 9-fluorenyl, and the C-C bridged bond C(3AA)─C(3AB) of Ni2 was formed between 9-fluorenyl and 9-fluorenyl. In the ORTEP plots of Ni1, the bonds (Å) N(1)─C (7) 1.5086 (18), N(1)─C(37) 1.3281 (19), C(35)─C(36) 1.492 (2) and C(7)─C(36) 1.573(2) form an approximate square structure (angles (°): N(1)─C(7)─C(36) 84.50 (11), C(7)─C(36)─C(37) 86.13 (12)), which is similar to the quadrilateral structure formed by the bonds N(2)─C (26) 1.5086 (18), N(2)─C(38) 1.3281 (19), C(37)─C(38) 1.492 (2) and C(26)─C(35) 1.573(2) (angles C(26)─C(37)─C(38) 86.13 (12), N(2)─C(26)─C(35) 84.50 (11)), and the two quadrilateral structures centered on the nickel atom. But in Ni2, the C-C bridged bond C(3AA)─C(3AB) 1.597 (14) combined with C(3AA)─N(1) 1.488 (9), N(1)─Ni(1) 1.867 (5), N(1A)─Ni(1) 1.867(5) and C(3AB)─N(1A) 1.292(8) constitute a pentagonal structure and this is similar to the structure of the C-C bridged catalyst that we have reported previously.…”

Section: Catalyst and Ligand Crystal Structuresmentioning

confidence: 99%

“…The properties of vinyl‐type PNB can always be improved by employing polar groups and flexible chains . Vinyl‐type PNB can be obtained through the use of Ziegler–Natta catalysts, metallocene catalysts and late transition metal catalysts . Late transition metal catalysts are important for vinyl addition polymerization of norbornene (NB) and can effectively polymerize functional NB monomer due to their low oxophilicity, high catalytic activity and better stability in polar monomer.…”

Section: Introductionmentioning

confidence: 99%

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C–C bridged Ni(II) complexes bearing β‐keto‐9‐fluorenyliminato ligands prepared by different in situ bonding mechanisms and their use in catalytic (co)polymerization of norbornene and styrene

Wang

Yang

et al. 2018

Applied Organom Chemis

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Two C–C bridged Ni(II) complexes bearing β‐keto‐9‐fluorenyliminato ligands with electron‐withdrawing groups (─CF3), Ni{PhC(O)CHC[N(9‐fluorenyl)]CF2}2 (Ni1) and Ni{CF3C(O)CHC[N(9‐fluorenyl)]Ph}2 (Ni2), were synthesized by metal coordination reaction and different in situ bonding mechanisms. The C–C bridged bonds of Ni1 were formed by in situ intramolecular trifluoromethyl and 9‐fluorenyl carbon–carbon cross‐coupling reaction and those of Ni2 were formed by in situ intramolecular 9‐fluorenyl carbon–carbon radical coupling reaction mechanism. The obtained complexes were characterized using 1H NMR spectroscopy and elemental analyses. The crystal and molecular structures of Ni1 and Ni2 with C–C bridged configuration were determined using X‐ray diffraction. Ni1 and Ni2 were used as catalysts for norbornene (NB) polymerization after activation with B(C6F5)3 and the catalytic activities reached 106 gpolymer molNi−1 h−1. The copolymerization of NB and styrene catalyzed by the Ni1/B(C6F5)3 system showed high activity (105 gpolymer molNi−1 h−1) and the catalytic activities decreased with increasing feed content of styrene. All vinyl‐type copolymers exhibited high molecular weight (104 g mol−1), narrow molecular weight distribution (Mw/Mn = 1.71–2.80), high styrene insertion ratios (11.13–50.81%) and high thermal stability (Td > 380°C) and could be made into thin films with high transparency in the visible region (400–800 nm).

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Section: Catalyst and Ligand Crystal Structuresmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

C–C bridged Ni(II) complexes bearing β‐keto‐9‐fluorenyliminato ligands prepared by different in situ bonding mechanisms and their use in catalytic (co)polymerization of norbornene and styrene

Wang

Yang

et al. 2018

Applied Organom Chemis

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Styrene copolymerization using a metallocene-MAO initiator system. Homo- and copolymerization of styrene with some cycloalkenes

et al. 2013

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Artículo de publicación ISIThe copolymerization of styrene with cyclohexene, 1-methyl-1-cyclohexene, and norbornene using ethenylbisindenylzirconium dichloride and methylaluminoxane, Et(Ind)2ZrCl2-MAO, initiating systems has been tested. The results obtained with each styrene-cycloalkene couple, except styrene/norbornene, indicate a less effective polymerization process compared to styrene homopolymerization, in agreement with the electronic and steric effects present in each comonomer. The electronic I? effects of substituent groups, depending on their placement, largely improve the polymerization process, while bulky groups on or near the vinyl carbon double bond of styrene decrease its effectiveness. The present study shows that the copolymers obtained are amorphous and their composition showed a lower abundance of comonomer units with respect to the initial feed. For comparison, the results of the copolymerization of styrene/(1-octadecene) using the same initiator system and polymerization process are included, a polymerization that indicates a more reactive process, and as the proportion of octadecene in the initial feed increases, it showed a crystalline fusion temperature as well as a Tg in the styrene region which can be attributed to the formation of block styrene/octadecene copolymers

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Transition metal complex catalysts promoting copolymers of cycloolefin with propylene/higher olefins

Wang

et al. 2023

Coordination Chemistry Reviews

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Study on the copolymerization of propylene with norbornene using metallocene catalysts

Cited by 6 publications

References 23 publications

C–C bridged Ni(II) complexes bearing β‐keto‐9‐fluorenyliminato ligands prepared by different in situ bonding mechanisms and their use in catalytic (co)polymerization of norbornene and styrene

C–C bridged Ni(II) complexes bearing β‐keto‐9‐fluorenyliminato ligands prepared by different in situ bonding mechanisms and their use in catalytic (co)polymerization of norbornene and styrene

Styrene copolymerization using a metallocene-MAO initiator system. Homo- and copolymerization of styrene with some cycloalkenes

Transition metal complex catalysts promoting copolymers of cycloolefin with propylene/higher olefins

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