Fluorinated bis(phenoxy–imine) Ti complexes with MAO: Remarkable catalysts for living ethylene and syndioselective living propylene polymerization

Furuyama, Rieko; Saito, Junji; Ishii, Seiichi; Makio, Haruyuki; Mitani, Makoto; Tanaka, Hidetsugu; Fujita, Terunori

doi:10.1016/j.jorganchem.2005.03.060

Cited by 95 publications

(69 citation statements)

References 152 publications

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“…Living, partially syndiotactic PP was first reported by Doi (11) using vanadium complexes. Coates (12) and Fujita (13) independently reported that fluorinated bis(phenoxyimine) titanium catalysts (14) are capable of the living, syndiospecific polymerization of propylene, including the synthesis of polymers with PEP blocks. Busico (15), Coates (16), and Sita (17) have reported group IV catalysts with varying degrees of isospecificity and livingness for the synthesis of iPP block copolymers.…”

Section: Block Polyolefinsmentioning

confidence: 99%

Semicrystalline thermoplastic elastomeric polyolefins: Advances through catalyst development and macromolecular design

Hotta

Cochran

Ruokolainen

et al. 2006

Proc. Natl. Acad. Sci. U.S.A.

125

116

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We report the design, synthesis, morphology, phase behavior, and mechanical properties of semicrystalline, polyolefin-based block copolymers. By using living, stereoselective insertion polymerization catalysts, syndiotactic polypropylene-blockpoly(ethylene-co-propylene)-block-syndiotactic polypropylene and isotactic polypropylene-block-regioirregular polypropyleneblock-isotactic polypropylene triblock copolymers were synthesized. The volume fraction and composition of the blocks, as well as the overall size of the macromolecules, were controlled by sequential synthesis of each block of the polymers. These triblock copolymers, with semicrystalline end-blocks and mid-segments with low glass-transition temperatures, show significant potential as thermoplastic elastomers. They have low Young's moduli, large strains at break, and better than 90% elastic recovery at strains of 100% or less. An isotactic polypropylene-block-regioirregular polypropylene-block-isotactic polypropylene-block-regioirregular polypropylene-block-isotactic polypropylene pentablock copolymer was synthesized that also shows exceptional elastomeric properties. Notably, microphase separation is not necessary in the semicrystalline isotactic polypropylenes to achieve good mechanical performance, unlike commercial styrenic thermoplastic elastomers.block copolymer ͉ polypropylene T he applications of a polymer are largely determined by its chemical, physical, and mechanical properties. These properties are in turn determined by polymer morphology, which is dictated by polymer structure and composition. Thermoplastic elastomers are a classic example where polymer architecture engenders unique properties. Block copolymers that contain at least two blocks that are hard at room temperature, separated by blocks with a glass transition temperature (T g ) below room temperature, typically exhibit elastomeric properties if the low T g block volume is large (1-5). The most well known elastomers of this type are the polystyrene (PS)-block (b)-polybutadiene-b-PS triblock copolymers, sold commercially by Kraton Polymers. Such materials normally possess a microphase-separated morphology in which 10-nm-scale domains of the hard blocks (e.g., PS) are embedded as spheres or cylinders within a continuous phase of the low T g soft blocks. The hard domains serve as thermally reversible crosslinks that at room temperature produce high levels of recoverable elasticity in the soft phase.Sequence control of a synthetic polymer is most easily accomplished by using a synthetic technique that allows the sequential addition of one or more monomers to the macromolecule in a chain growth process without spontaneous termination. These techniques are collectively called living polymerizations, and despite many successes over the last half century, their further development remains one of the most important frontiers in polymer science. In the case of the Kraton triblock copolymers, a living anionic polymerization process is used to synthesize the materials. Because approximately t...

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Section: Block Polyolefinsmentioning

confidence: 99%

Semicrystalline thermoplastic elastomeric polyolefins: Advances through catalyst development and macromolecular design

Hotta

Cochran

Ruokolainen

et al. 2006

Proc. Natl. Acad. Sci. U.S.A.

125

116

View full text Add to dashboard Cite

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“…The polymeriza- tion behavior bears a resemblance to related phenyl and alkylphenyl substituted FI-catalysts [49,50]. The remarkable increase in activity can be possibly observed when the ligand environment of complex 3-Ti is modified by using fluorinated phenyl substituent instead of plain phenyl ring [28,51].…”

Section: Discussionmentioning

confidence: 83%

Titanium complexes with modifiable pyrazolonato and pyrazolonato-ketimine ligands: Synthesis, characterization and ethylene polymerization behavior

Elo

Pärssinen

Rautiainen

et al. 2010

Journal of Organometallic Chemistry

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“…In this case, the ring contains a newly formed chirality center. Consequently we have observed a pair of 1 …”

Section: Metallation Reactionsmentioning

confidence: 91%

“…Important examples include the various salicylaldiminato systems (A), derivatives of which have found many practical catalytic applications ranging from polymerization reactions [1,2] to asymmetric organic synthesis [3]. In a way the (amidomethyl)pyridine-N-oxides (B) represent complementary systems to the ubiquitous salicylaldiminates, where formally the negatively charged center was moved from the oxy-arene site to a side-chain nitrogen (see Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

(N-Arylaminomethyl)pyridine-N-oxides: Synthesis and characterization of potential ligand systems and the formation of their N,O-chelate aluminum complexes

Nienkemper

Kehr

et al. 2008

Journal of Organometallic Chemistry

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Fluorinated bis(phenoxy–imine) Ti complexes with MAO: Remarkable catalysts for living ethylene and syndioselective living propylene polymerization

Cited by 95 publications

References 152 publications

Semicrystalline thermoplastic elastomeric polyolefins: Advances through catalyst development and macromolecular design

Semicrystalline thermoplastic elastomeric polyolefins: Advances through catalyst development and macromolecular design

Titanium complexes with modifiable pyrazolonato and pyrazolonato-ketimine ligands: Synthesis, characterization and ethylene polymerization behavior

(N-Arylaminomethyl)pyridine-N-oxides: Synthesis and characterization of potential ligand systems and the formation of their N,O-chelate aluminum complexes

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