Systematic investigations of ortho-aryl substitution effect on chain microstructure in nickel-catalyzed long chain α-olefin polymerization and copolymerization with methyl undecenoate

Guo, Lihua; Li, Jiaxing; Li, Pengwei; Zhao, Wei; Li, Xiaoyuan; Luo, Mingling; Xing, Yufen; Liu, Zhe

doi:10.1016/j.eurpolymj.2023.112664

Cited by 4 publications

(1 citation statement)

References 63 publications

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“…For coordination polymerization of α-olefin, 1,2-insertion and chain walking will result in 2,ω-enchainment and generate methyl-branched polyolefin, while 2,1-insertion followed by chain walking can lead to 1,ω-enchainment, so-called “chain straightening” (Scheme 1c), to form a long linear polymer. 1,40,45,47,59–63 The different regioselectivity of 1,2- or 2,1-insertion can also be effectively adjusted by changing the late-transition-metal catalyst structures or the polymerization conditions. Due to these fascinating processes, TPEs with varying microstructures can be easily obtained.…”

Section: Introductionmentioning

confidence: 99%

Direct synthesis of poly(α-olefin) thermoplastic elastomers via controlled chain straightening using bulky α-diimine palladium complexes

Wang,

Cai,

Dai

2024

Polym. Chem.

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Section: Introductionmentioning

confidence: 99%

Direct synthesis of poly(α-olefin) thermoplastic elastomers via controlled chain straightening using bulky α-diimine palladium complexes

Wang,

Cai,

Dai

2024

Polym. Chem.

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Steric and temperature effects in unsymmetrical α‐diimine nickel‐catalyzed ethylene and 1‐octene polymerization

Shou,

Li,

Tian

et al. 2024

Applied Organom Chemis

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In this contribution, a series of unsymmetric α‐diimine nickel complexes are synthesized. One side of these nickel complexes is the 2,4‐dimethyl‐6‐diphenylmethylaniline unit, and the steric effects are tuned by changing another aniline unit. These nickel complexes have high catalytic activities in ethylene (>106 g mol−1 h−1) and 1‐octene (104–105 g mol−1 h−1) polymerization, generating high‐molecular‐weight polyolefins (Mn > 104 g mol−1) with tunable branching densities (59–91/1000C). Steric effects and polymerization temperature can significantly affect the catalytic performance of the catalyst. Most importantly, catalysts with different steric hindrances have different temperature sensitivity. In general, catalysts with larger steric hindrances are more sensitive to temperature. This may be due to the fact that the rotation of some chemical bonds is blocked at low temperatures due to the larger volume of the substituents, resulting in more significant temperature sensitivity.

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Accessing Functionalized Ultra‐High Molecular Weight Poly(α‐olefin)s via Hafnium‐Mediated Highly Isospecific Copolymerization

Zhou,

Mu,

Jian

2024

Macromol. Rapid Commun.

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Inspired by the favorable impact of heteroatom‐containing groups in phenoxy‐imine titanium and late transition metal catalysts, we design and synthesize a series of novel pyridylamido hafnium catalysts bearing –OMe (Cat‐OMe), –CF3 (Cat‐CF3), and –C6F5 (Cat‐C6F5) substituents. Together with the established hafnium catalysts Cat‐H and Cat‐iPr by Dow/Symyx, these catalysts are applied in the polymerization of α‐olefins, including 1‐hexene, 1‐octene, and 4M1P, as well as in the copolymerization of these α‐olefins with a specifically designed polar monomer. The enhancement of polymer molecular weight derived from catalyst modification and the incorporation of polar monomers is discussed in detail. Notably, the new catalysts are all highly active for α‐olefins polymerization, with catalyst Cat‐CF3 producing isotactic polymers with the highest molecular weight (Mw = 1,649 kg mol−1); in copolymerization with polar monomers, catalyst Cat‐OMe yields isotactic copolymer with the highest molecular weight (Mw = 2,990 kg mol−1). Interestingly, catalyst Cat‐C6F5 bearing a ‐C6F5 group in the N‐aryl moiety gives rise to poly(α‐olefin) with reduced stereoselectivity. The findings of this study underscore the potential of heteroatom‐containing groups in the development of early transition metal catalysts and the synthesis of polymer with novel structures.This article is protected by copyright. All rights reserved

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Systematic investigations of ortho-aryl substitution effect on chain microstructure in nickel-catalyzed long chain α-olefin polymerization and copolymerization with methyl undecenoate

Cited by 4 publications

References 63 publications

Direct synthesis of poly(α-olefin) thermoplastic elastomers via controlled chain straightening using bulky α-diimine palladium complexes

Direct synthesis of poly(α-olefin) thermoplastic elastomers via controlled chain straightening using bulky α-diimine palladium complexes

Steric and temperature effects in unsymmetrical α‐diimine nickel‐catalyzed ethylene and 1‐octene polymerization

Accessing Functionalized Ultra‐High Molecular Weight Poly(α‐olefin)s via Hafnium‐Mediated Highly Isospecific Copolymerization

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