Ethylene polymerization and copolymerization with a polar monomer using an α‐iminocarboxamide nickel complex activated by trimethylaluminum

Abstract

An α‐iminocarboxamide nickel complex was activated by trimethylaluminum (TMA) and used in the polymerization of ethylene and its copolymerization with 10‐undecen‐1‐ol. The best activity was observed upon activation with 9 equiv of TMA at a temperature of 26 °C. NMR spectroscopic studies did not show 10‐undecen‐1‐ol incorporation. However, FTIR analyses suggest the incorporation of a very small amount of comonomer, which affects the glass transition temperature, the degree of branching, and the mechanical properties of the materials. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 54–59, 2008

2-Phosphinophenolate Nickel Catalysts: Formation of Ethylene Copolymers with Isolated sec-Alkyl, Aryl, and Functionally Substituted Alkyl Groups

“…Finally, it was of interest to check if OH functionally substituted olefins can be used for copolymerization with ethylene by phosphinophenolate nickel catalysts. Recently, copolymerization of ethylene with 1-decen-9-ol as well as 5- and 1-undecen-9-ol was studied using α-iminocarboxamide or bulky N , N ′-disubstituted diimino−acenaphthene nickel complexes. In both systems, protection of the OH group by metalation with Me 3 Al was required.…”

“…The microstructure of the copolymers, determined by 13 C NMR measurements, is the same as detected for the other copolymers, a linear polyethylene main chain with isolated side groups. The CH 2 OH end of the side groups gives a strong, slightly broadened 13 C NMR signal at 63.2 ppm with about the same intensity as the branching carbon (C br ) and triple intensities of the α-, β-, and γ-CH 2 signals, each superimposed by the α-, β-, and γ-CH 2 signals (8B 8 , 7B 8 , 6B 8 ) of the long side group (Figure ), whereas the incorporation of 1-(un)decenol into the ethylene/hydroxyolefin copolymers, obtained with Me 3 Al activated α-iminocarboxamide or diimino−acenaphthene nickel complexes, , was not detected by 13 C NMR. The free OH group in the polymer side groups was of interest to us as it allows for the introduction of a wide variety of functional groups.…”

α‐Diimine nickel catalyst for copolymerization of hexene and acrylate monomers activated by different cocatalysts

“…These catalysts are able to produce highly branched PE by the chain‐walking mechanism . Several attempts have been made to incorporate polar monomers into the polyolefins chain . ε‐caprolactam and tetrahydrofuran were copolymerized with ethylene using a late transition metal catalyst precursor .…”

“…ε‐caprolactam and tetrahydrofuran were copolymerized with ethylene using a late transition metal catalyst precursor . An α‐iminocarboxamide nickel complex was used in the polymerization of ethylene and its copolymerization with 10‐undecen‐1‐ol by Galland et al . New polymers with polar side groups prepared by Takeuchi through cyclopolymerization of alkyl‐substituted diallyl monomers using Pd diimine complexes exhibited superior adhesion, dyeability, and compatibility compared to polyethylene or polyolefins .…”

Syndiospecific Living Copolymerization of Styrene with ε-Caprolactone by Scandium Catalysts

“…So far, extensive studies on the copolymerization of two monomers with similar properties (e.g., olefins) have been carried out, whereas the copolymerization of monomers with distinctly different properties (such as polar and nonpolar monomers) remained limited . Several catalyst systems based on lanthanide or transition metals such as Sm, Zr, Ni, Pd, etc., were reported to copolymerize ethylene or propylene with polar monomers such as alkyl acrylates or functionalized vinyl monomers. However, the copolymerization of styrene with a polar monomer was limited mostly to anion or radical initiators, which usually show poor stereoselectivity.…”