Living Transition Metal‐Catalyzed Alkene Polymerization: Polyolefin Synthesis and New Polymer Architectures

Living polymerization of olefins with ansa-dimethylsilylene(fluorenyl)(amido)dimethyltitanium-based catalysts

“…8,9 We have also developed a living polymerization system using ansa-dimethysilylene(fluorenyl)(amido)dimethyltitanium, Me 2 Si(Z 3 -C 13 H 8 )(Z 1 -N t Bu)TiMe 2 (1), combined with a suitable cocatalyst. The catalytic system allows not only a syndiospecific living polymerization of propene and a 1-alkene but also a living homopolymerization and copolymerization of norbornene with a 1-alkene.…”

“…1,2 The development of metallocene catalysts has enabled us to produce a variety of uniform olefin copolymers and to control the stereoregularity of poly(1-alkene)s. 3,4 The success of metallocene catalysts has stimulated research on transition metal complexes for olefin polymerization, [5][6][7] so-called single-site catalysts, which has also resulted in various transition metal complexes for the living polymerization of olefins. 8,9 We have also developed a living polymerization system using ansa-dimethysilylene(fluorenyl)(amido)dimethyltitanium, Me 2 Si(Z 3 -C 13 H 8 )(Z 1 -N t Bu)TiMe 2 (1), combined with a suitable cocatalyst. The catalytic system allows not only a syndiospecific living polymerization of propene and a 1-alkene but also a living homopolymerization and copolymerization of norbornene with a 1-alkene.…”

Quasi-Living Polymerization of Propene with an Isotactic-Specific Zirconocene Catalyst

“…Living polymerization enables us to produce block copolymers by switching the monomer from one to the other during the polymerization [3,4,5,6,7,8]. The simplest and most widely studied type of block copolymer is diblock, where two building blocks of different natures are joined together by a single covalent bond.…”

“…The simplest and most widely studied type of block copolymer is diblock, where two building blocks of different natures are joined together by a single covalent bond. In the past decade, several noteworthy systems were introduced that led to the living and iso -specific polymerization and copolymerization of α-olefins [2,3,4,5]. For example, Coates et al reported that the pyridylamidohafnium catalyst system produced iso -PP- block -PE (polyethylene) diblock and multiblock copolymers with precise control of block length ( M n = 208,000, mmmm = 91%, T m = 133 °C) [8].…”

Facile Synthesis of Hydroxyl‐Terminated Oligoethylenes

“…Hydroformylation and hydrogenation of α ‐olefins from the SHOP give access to the distribution of fatty alcohols with a typical carbon count of 9–23 . The ZIEGLER process is attractive in that it yields a POISSON ‐distributed mixture of higher alkyls as the result of a living ethylene oligomerization reaction . Consecutive insertion of ethylene into the aluminum carbon bonds of a starting compound like triethyl aluminum in a living polymerization is the underlying principle.…”