Living Chain-Walking (Co)Polymerization of Propylene and 1-Decene by Nickel α-Diimine Catalysts

Abstract

Homo- and copolymers of propylene and 1-decene were synthesized by controlled chain-walking (co)polymerization using phenyl substituted α-diimine nickel complexes activated with modified methylaluminoxane (MMAO). This catalytic system was found to polymerize propylene in a living fashion to furnish high molecular weight ethylene-propylene (EP) copolymers. The copolymerizations proceeded to give high molecular weight P/1-decene copolymers with narrow molecular weight distribution (Mw/Mn ≈ 1.2), which indicated a living nature of copolymerization at room temperature. The random copolymerization results indicated the possibility of precise branched structure control, depending on the polymerization temperature and time.

Microstructural, Thermal and Electrical Properties of Methyl Methacrylate and 1‐Hexene Copolymers Made by Dinuclear Ni‐Based Catalysts

“…This feature even was greater for catalyst N 1 . These results are in agreement with previous reports where for most cases, 1H is less reactive than MM monomer [42,49,67,68,72,73] . Based on this (r 1 >r 2 ), the microstructure of the copolymer is MM rich and 1H units are randomly distributed at the end of the polymer chains [73] …”

“…Despite a slew of literature on multinuclear LTM catalysts used to homopolymerization olefins, there are few reports on the copolymerization of olefins and polar monomers [2,28–43] . As an example, Khoshsefat and his coworkers synthesized polyolefins using dinuclear α‐diimine Ni‐, Co‐, and Fe‐based catalysts bearing different backbones, ortho‐substituents, and spacers between the active centers and investigated the steric effect, nuclearity and electronic features of ligands and their effect on the catalyst activity [2,28,29,33,34,41–43] . Cheng and coworkers employed a dinuclear Ni‐based catalyst with greater polar monomer incorporation than its mononuclear counterpart [44] .…”

Revisiting the Potential of Group VI Inorganic Precatalysts for the Ethenolysis of Fatty Acids through a Mechanochemical Approach

“…Recent years have seen a growing interest in the development of a broad portfolio of bioderived compounds as alternatives to the traditional fossil fuel-derived chemicals. − Naturally available vegetable oils (VOs) are a major feedstock for biorefineries, , leading to a variety of so-called oleochemicals with ramifications in the synthesis of surfactants, , lubricants, polymers, − and other useful compounds such as carbonated vegetable oils. ,− An important class of oleochemicals is represented by functional olefins such as 9-decenoic acid methyl ester (9-DAME), which is a valuable fine chemical with potential application for the preparation of biodiesel surrogates, , bioaviation fuel, and as a starting material for the preparation of diverse functional compounds. − 9-DAME can be obtained from the ethenolysis (metathetic cleavage with ethene) of oleic fatty acid ester chains derived from VO transesterification leading to the formation of an equivalent of 1-decene, a valuable α-olefin used for the synthesis of polymers and food additives just to cite some applications. The catalytic ethenolysis of oleic fatty acids to produce 9-DAME and 1-decene has been studied in the past. ,, Homogeneous ruthenium alkylidene complexes are powerful catalysts for the ethenolysis of methyl oleate, showing high catalytic turnover at moderate methyl oleate conversion under 10 bar ethylene. , However, given the high cost of ruthenium-based catalysts and the geographically restricted availability and critical resource status of ruthenium, there has been an increasing interest toward alkylidene complexes of inexpensive and ubiquitously available metals such as molybdenum. , A homogeneous molybdenum imido alkylidene monoaryloxide monopyrrolide complex was reported to carry out the ethenolysis of methyl oleate with high yields and selectivity at room temperature under 10 bar ethylene .…”

“… 12 , 14 − 17 An important class of oleochemicals is represented by functional olefins such as 9-decenoic acid methyl ester (9-DAME), which is a valuable fine chemical with potential application for the preparation of biodiesel surrogates, 18 , 19 bioaviation fuel, 20 and as a starting material for the preparation of diverse functional compounds. 21 − 23 9-DAME can be obtained from the ethenolysis (metathetic cleavage with ethene) 24 of oleic fatty acid ester chains derived from VO transesterification leading to the formation of an equivalent of 1-decene, a valuable α-olefin used for the synthesis of polymers 25 and food additives 26 just to cite some applications. The catalytic ethenolysis of oleic fatty acids to produce 9-DAME and 1-decene has been studied in the past.…”

Ortho-Functionalized Dibenzhydryl Substituents in α-Diimine Pd Catalyzed Ethylene Polymerization and Copolymerization

“…In the 1990s, Brookhart et al reported the studies of α-diimine Pd catalysts for olefin polymerization and copolymerization with polar monomers (Chart 1A) [32][33][34]. These α-diimine Pd catalysts can produce polyolefins with branched even branch-on-branch structures while using ethylene as the only monomer via the "chain-walking" polymerization mechanism [35][36][37][38][39][40], providing a unique approach for modulating the polyolefin microstructures [41]. However, most α-diimine Pd catalysts exhibit poor thermal stability at high temperatures (>60 • C) due to decomposition reactions that are associated with C-H activation of ligand, associative chain transfer, and bisligation of M-H species, which has limited their practical applications [42][43][44][45][46][47][48][49][50].…”