Chain-walking polymerization of 3-heptene with phenyl substituted α-diimine nickel catalysts

The first example of a 3-alkene polymerization has been successfully achieved with 3-heptene in the presence of phenyl-substituted α- diimine nickel precatalysts activated by dMMAO, and compared with the corresponding linear alkenes, i.e., 1-pentene, 2-hexene and 4-octene polymerizations. The microstructures of the produced poly(3-heptene), which consists of ethyl , propyl and butyl branches indicated the 3,4- and 4,3-insertion, followed by chain-walking, with incorporation of a small fraction of long methylene sequences of 1,7-enchainment via monomer-isomerization. Late-transition metal catalyzed polymerization reactions of internal alkenes to synthesize novel polyolefin materials are highly important and also highly challenging. Upon activation with dried modified methylaluminoxane (dMMAO), the first example of a 3-alkene polymerization has been successfully achieved for 3-heptene catalyzed by phenyl-substituted α- diimine nickel complexes in comparison, and compared with the polymerizations of the corresponding linear alkenes, i.e., 1-pentene, 2-hexene and 4-octene. The results indicate that the polymerization of 3-heptene was achieved via chain-walking to generate branched amorphous polymers with glass transition temperature of ca. −68 °C. The microstructures of the produced poly(3-heptene) indicated the 3,4- and 4,3-insertion followed by chain-walking, the latter being predominant. The NMR analyses of the polymers showed that the obtained poly(3-heptene) possessed ethyl, propyl and butyl branches and a small amount of the long methylene sequence of 1,7-enchainment via monomer-isomerization. The branches structures were significantly dependent on the polymerization temperature, and the content of propyl branches derived from 3,4-insertion decreased with an increase in the polymerization temperature.