Synthesis of 1,2-bis(imidazolidin-2-imine)benzene nickel complexes and their application for norbornene (co)polymerization with styrene

Wang, Wenwen; Shu, Xin; Zhang, Hu; Cao, Lixin; Li, Yanqing; Cai, Zhengguo

doi:10.1016/j.eurpolymj.2021.110426

Cited by 13 publications

(2 citation statements)

References 66 publications

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“…Norbornene (NB) can be polymerized through three different catalytic approaches: ring-opening metathesis polymerization, cationic/radical polymerization, and vinyl-type addition polymerization. − Among them, the vinyl-type polynorbornene (PNB) obtained by the transition-metal-catalyzed coordination polymerization of NB exhibits unique properties, such as high thermal stability, good chemical resistance, and excellent transparency, owing to its rigid structure. The development of NB-based copolymers through the copolymerization of NB with substituted NB derivatives, ethylene, − propylene, , higher α-olefins, − styrenes, − and dienes , achieved further improvements to the polymer properties, such as toughness, solubility, and surface properties. Moreover, the structure and properties of these copolymers can be further tailored by the appropriate choice of catalyst together with a variation of the comonomer contents, structures, and sequence distributions.…”

Section: Introductionmentioning

confidence: 99%

Norbornene Copolymerization with Polar Monomers Catalyzed by Palladium Catalysts Containing Imidazolidin-2-imine/Guanidine Ligands

Li,

Cai,

Eisen

2023

Inorg. Chem.

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The development of a palladium catalyst that has enhanced catalytic performance, such as low aluminum cocatalyst loading, good copolymerization ability, high molecular weight, and excellent solubility of the (co)polymers, is still a challenge in norbornene copolymerizations. Here, a series of PdCl 2 and PdMeCl complexes containing differently substituted anilines and imidazolidin-2-imine/guanidine ligands was successfully synthesized and characterized. X-ray diffraction analysis results revealed that these Pd complexes adopted an almost square-planar geometry, and the six-membered chelate ring showed structural distinctions as compared to traditional N^N-based α-diimine and β-diimine Pd complexes. These Pd complexes were activated by EtAlCl 2 and then exhibited moderate activity (10 4 −10 5 g mol −1 h −1 ) and good thermal stability (up to 90 °C) for norbornene polymerization to produce high-molecular-weight PNBs (M n up to 96.4 kg mol −1 ) with narrow polydispersities (PDI as low as 1.39). These Pd complexes also exhibited good polar group tolerance in the copolymerization of norbornene with methyl 5-norbornene-2carboxylate and methyl 10-undecenoate, in which the activity was achieved up to 7.04 × 10 4 g mol −1 h −1 . It furnished polar functionalized norbornene-based copolymers with high molecular weight (M n up to 63.1 kg mol −1 ), narrow PDI, reasonable polar monomer incorporation, and good solubility. These Pd catalysts exhibited an enhanced copolymerization ability to produce PNB or NB-based copolymers, representing significant progress in this field.

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Section: Introductionmentioning

confidence: 99%

Norbornene Copolymerization with Polar Monomers Catalyzed by Palladium Catalysts Containing Imidazolidin-2-imine/Guanidine Ligands

Li,

Cai,

Eisen

2023

Inorg. Chem.

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“…These polymers possessed refractive indexes over 1.6. In addition to the vast amount of previous advances on the effective copolymerization of cycloolefins and styrene, − we have already succeeded in the copolymerization of NB and alkenyl monomers possessing aromatic structures using Me 2 Si(Flu)(N t Bu)TiMe 2 ( 1 ) as a catalyst and revealed that some copolymers showed much lower birefringence than the copolymers of NB and 1-alkenes. , Recent investigation with the aid of computational prediction showed that polymers containing a fluorene skeleton in their main chain are promising materials realizing both low birefringence and high refractive index . We, therefore, got interested in the impact of the incorporation of fluorenyl moieties as pendant groups on the COC.…”

Section: Introductionmentioning

confidence: 99%

Cyclic Olefin Copolymer Bearing Pendant Fluorenyl Groups with High Refractive Index and Low Chromatic Dispersion

et al. 2021

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Copolymerization of norbornene (NB) and fluorene-containing alkene comonomers using the Me 2 Si(Flu)(N t Bu)-TiMe 2 complex as a catalyst was investigated. The copolymerization successfully proceeded at any monomer feed ratio in high activity and gave copolymers with various comonomer contents. The structure of these copolymers would be gradient because NB was preferentially consumed in a quasi-living polymerization system. Two relaxation processes at 100−150 and 270−300 °C in dynamic mechanical analysis, which show phase-separation of the copolymer, supported the formation of the gradient structure. The obtained copolymers showed a high refractive index as hydrocarbons and extremely low photoelasticity (<10 −11 Pa −1 ). For reducing the photoelasticity, a monomer design free from reactive tertiary carbons would be important.

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Mesoionische Imine (MIIs): Starke Donoren und vielseitige Liganden für Übergangsmetalle und Hauptgruppensubstrate

et al. 2022

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Wir berichten über die Synthese und die Reaktivität mesoionischer Imine (MIIs) des 1,2,3‐Triazolin‐5‐imin Typs. Die MIIs sind über eine Basen‐mediierte Cycloaddition eines substituierten Acetonitrils mit einem aromatischen Azid, Methylierung nach etablierten Methylierungsrouten und anschließender Deprotonierung zugänglich. C=O‐Streckschwingungen in MII−CO2− und −Rh(CO)2Cl‐Komplexen wurden bemüht um die Gesamtdonorstärke zu bestimmen. Die MIIs sind stärkere Donoren als N‐Heterocyclische Imine (NHIs). MIIs sind exzellente Liganden für Hauptgruppenelemente und Übergangsmetalle, in welchen sie Substituenten‐induzierte Fluor‐spezifische Wechselwirkungen zeigen oder C−H‐Aktvierungen eingehen. DFT‐Berechnungen haben Einblicke in die Grenzorbitale der MIIs gegeben. Die Rechnungen sagen im Vergleich zu verwandten Liganden eine relative kleine HOMO–LUMO Lücke vorraus. MIIs können potentiell sowohl als π‐Donor‐ als auch π‐Akzeptorliganden wirken. Dieser Bericht demonstiert das Potential von MIIs spannende Eigenschaften mit einem gewaltigen Zukunftspotential zu entwickeln.

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Synthesis of 1,2-bis(imidazolidin-2-imine)benzene nickel complexes and their application for norbornene (co)polymerization with styrene

Cited by 13 publications

References 66 publications

Norbornene Copolymerization with Polar Monomers Catalyzed by Palladium Catalysts Containing Imidazolidin-2-imine/Guanidine Ligands

Norbornene Copolymerization with Polar Monomers Catalyzed by Palladium Catalysts Containing Imidazolidin-2-imine/Guanidine Ligands

Cyclic Olefin Copolymer Bearing Pendant Fluorenyl Groups with High Refractive Index and Low Chromatic Dispersion

Mesoionische Imine (MIIs): Starke Donoren und vielseitige Liganden für Übergangsmetalle und Hauptgruppensubstrate

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