Regulating the polyethylene microstructure by increasing steric crowding in naphthoxy imine-ligated Ni(<scp>ii</scp>) complexes

Birajdar, Rajkumar S.; Gonnade, Rajesh G.; Chikkali, Samir H.

doi:10.1039/d3py01010d

Polym. Chem.

2024

DOI: 10.1039/d3py01010d

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Regulating the polyethylene microstructure by increasing steric crowding in naphthoxy imine-ligated Ni(ii) complexes

Rajkumar S. Birajdar,

Rajesh G. Gonnade,

Samir H. Chikkali

Abstract: Here we report the syntheses of systematically sterically tailored naphthoxy imine-ligated nickel complexes and, their performance in ethylene polymerization. Sterically less bulky Ni1 and Ni2 produced highly branched (43–54) PE, while the bulkiest Ni3 suppressed branching (only 28).

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Cited by 2 publications

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Ethylene homo and co‐polymerization catalyzed by extensively bulky nickel catalysts with shielding wings of chlorine atoms

Ahmad,

Wang,

Tian

et al. 2024

Journal of Polymer Science

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Designing the catalysts to get high molecular weight polyethylene is an art. The catalysts bearing imine functionality derived from 8‐arylnaphthyl amines are more impressive and attractive in this regard. In this work, we synthesize 2,4‐dibenzhydryl‐8‐(3,5‐dichlorophenyl)naphthalen‐1‐amine to condense with picolinaldehyde, pyridine‐N‐oxide‐2‐carbaldehyde and 3,4‐dibutanone and then subsequently the treatment of resulting ligands with nickel precursors to get the corresponding catalysts. It was hypothesized that 3,5‐dichlorophenyl having extended wings of chlorine atoms along with bulky dibenzhydryl groups can provide good shielding on both apical positions of metal in response to slow down the chain transfer. More interestingly, the polymerization was done in industrially claimed n‐heptane solvent. All the catalysts showed activity in an order of 106, whereas a value of 1.04 × 107 g mol−1 h−1 has been recorded from keto‐imine based Ni‐3 catalyst. All catalysts generates polymer with high molecular weight with maximum value was recorded by Ni‐2 up to 37.4 × 104 g mol−1. Ni‐3 can also incorporate methyl 10‐undecenoate up to 2.6% in polyethylene backbone.

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Ethylene homo and co‐polymerization catalyzed by extensively bulky nickel catalysts with shielding wings of chlorine atoms

Ahmad,

Wang,

Tian

et al. 2024

Journal of Polymer Science

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Steric Influences on Chain Microstructure in Palladium-Catalyzed α-Olefin (Co)polymerization: Unveiling the Steric-Deficient Effect

Guo,

Li,

Zhao

et al. 2024

Inorg. Chem.

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This study addresses the challenge of controlling branching density and branch-type distribution in late-transition-metal-catalyzed chain walking polymerizations. We explored α-diimine Pd(II) complexes with incrementally increased ortho-aryl sterics for long-chain α-olefin (co)polymerization. Pd0−Pd3 catalysts, which feature gradually increased orthoaryl sterics and at least one small CH 3 substituent, exhibited similar 2,1insertion fractions (44−50%), polymer branching densities (55−63/1000C), and melting temperatures (26−28 °C). In contrast, Pd4 with bulky ortho-aryl sterics covering all sides demonstrated a significant increase in 2,1-insertion fractions up to 82%, leading to "PE-like" polymers with high melting temperatures (T m > 111 °C). This abrupt change in polymerization behavior, termed the "steric-deficient effect", contrasts with the gradual changes observed in similar Ni(II) systems that we reported previously. Furthermore, due to the rapid chain walking ability of Pd(II) catalysts in long-chain α-olefin (co)polymerization, these catalysts favor the production of polyolefins with higher proportions of methyl branches compared to those produced by Ni(II) catalysts. Particularly, these Pd(II) catalysts are capable of synthesizing functionalized semicrystalline copolymers by copolymerizing 1-octene with a variety of polar comonomers, thereby significantly altering the surface properties of the materials.

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Regulating the polyethylene microstructure by increasing steric crowding in naphthoxy imine-ligated Ni(ii) complexes

Abstract: Here we report the syntheses of systematically sterically tailored naphthoxy imine-ligated nickel complexes and, their performance in ethylene polymerization. Sterically less bulky Ni1 and Ni2 produced highly branched (43–54) PE, while the bulkiest Ni3 suppressed branching (only 28).

Cited by 2 publications

References 71 publications

Ethylene homo and co‐polymerization catalyzed by extensively bulky nickel catalysts with shielding wings of chlorine atoms

Ethylene homo and co‐polymerization catalyzed by extensively bulky nickel catalysts with shielding wings of chlorine atoms

Steric Influences on Chain Microstructure in Palladium-Catalyzed α-Olefin (Co)polymerization: Unveiling the Steric-Deficient Effect

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