@article {46838,
	title = {Palladium-catalyzed insertion of ethylene and 1,1-disubstituted difunctional olefins: an experimental and computational study},
	journal = {ChemPlusChem},
	volume = {85},
	year = {2020},
	month = {JUN},
	pages = {1200-1209},
	type = {Article},
	abstract = {<p>Insertion or coordination copolymerization of ethylene with di-substituted olefins is challenging and the choice of di-substituted mono-functional olefin versus di-substituted di-functional olefin (DDO) appears to be decisive. Here we show that DDO-inserted species are amenable to ethylene insertion and polymerization. DDOs such as 2-acetamidoacrylic acid (AAA), methyl 2-acetamidoacrylate (MAAA), and ethyl 2-cyanoacrylate (ECA) were treated with palladium complex [{P perpendicular to O}PdMe(L)] (P perpendicular to O=kappa(2)-P,O-Ar2PC6H4SO2O with Ar=2-MeOC6H4; L=C2H6OS) and the existence of respective insertion intermediates in moderate yield (up to 37 \%) was established. These intermediates were exposed to ethylene and corresponding ethylene-inserted products were isolated and characterized. A careful comparison with three model compounds confirmed ethylene insertion and polymerization. Thus, the combined experimental and computational investigations show that DDO-inserted species can undergo ethylene insertion and polymerization.</p>
},
	keywords = {Homogeneous catalysis, insertion copolymerization, Olefins, Palladium, Polyethylene},
	issn = {2192-6506},
	doi = {10.1002/cplu.202000309},
	author = {Gaikwad, Shahaji R. and Patel, Ketan and Deshmukh, Satej S. and Mote, Nilesh R. and Birajdar, Rajkumar S. and Pandole, Satish P. and Chugh, Jeetender and Chikkali, Samir H.}
}
@article {47107,
	title = {Insertion copolymerization of functional olefins: Quo Vadis?},
	journal = {European Polymer Journal},
	volume = {143},
	year = {2021},
	month = {JAN },
	pages = {110183},
	type = {Article},
	abstract = {<p>Functional polyethylene is a specialty polymer with unique set of properties and caters to a niche market. Currently, it is manufactured using high-pressure, high-temperature radical polymerization, or post-reactor (indirect) modification methods. Insertion copolymerization of functional olefins with ethylene provides a low pressure, direct route to prepare functional polyethylenes. However, insertion copolymerization of functional olefins with ethylene poses several impediments and requires special considerations. This review presents the current strategies, examines the progress, and attempts to gauge the commercial potential of direct synthesis of functional polyethylene. The performance of late transition metal catalysts derived from a-diimine, imine-phenolate, phosphine-sulfonate, bis-phosphine-mono-oxide, carbene-phenolate, phosphine-phenolate and their derivatives in the insertion copolymerization of functional olefins with ethylene is evaluated. While catalyst designing is crucial, incorporation of polar olefins that can serve an additional purpose is equally important. Therefore, we have organized the review in the following sections, polar alkenes with- acrylates, acrylic acids, acetates, nitriles, ethers, halides, two functional groups, cross-linking groups, dynamic interactions/self-healing properties, additional function/purpose, renewable functional olefins, and examine the progress. Among these, acrylates have been most intensively investigated and have been successfully incorporated in the polyethylene main-chain. Ethylene, methyl acrylate copolymers prepared by direct copolymerization reveal comparable melting temperature to that of LLDPE (at similar co-monomer content) and unfold the commercial potential of these materials. Recent developments on the insertion copolymerization of renewable functional olefins and di-functional olefins have elicited significant interest. This strategy is being viewed as a means of reducing environmental impact and enabling high functional group density at the same extent of incorporation. The overview thus offers a succinct account of insertion copolymerization of functional olefins, sheds light on the copolymer microstructure/material properties, and initiates a discussion on the commercial potential of functional polyethylene.</p>
},
	keywords = {Catalyst, Functional polyethylene, functional polyolefins, Hydrophilic polyethylene, insertion copolymerization, Polyethylene},
	issn = {0014-3057},
	doi = {10.1016/j.eurpolymj.2020.110183},
	author = {Birajdar, Rajkumar S. and Chikkali, Samir H.}
}
