A New Catalyst for Highly Syndiospecific Living Olefin Polymerization:  Homopolymers and Block Copolymers from Ethylene and Propylene

Tian, Jinfeng; Hustad, Phillip D.; Coates, Geoffrey W.

doi:10.1021/ja0157189

Cited by 416 publications

(291 citation statements)

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“…The syndiospecific living polymerization of propene was also achieved by Fujita and colleagues 42,43 and Coates and colleagues 44 using bis(phenoxyimine)titanium derivatives activated with MAO. The active species of this catalyst is an octahedral Ti with a 2, 1-inserted propagation chain in which the chain-end chiral carbon Living polymerization of olefins T Shiono isomerizes the chirality of the Ti species from one to the other in each monomer insertion to produce the syndiotactic polymers.…”

Section: Substituent Effects On the Fluorenyl Ligandmentioning

confidence: 92%

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

Shiono

2011

Polym J

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This article reviews the living homopolymerization and copolymerization of propene, 1-alkene and norbornene with ansadimethysilylene(fluorenyl)(amido)dimethyltitanium, Me 2 Si(g 3 -C 13 H 8 )(g 1 -N t Bu)TiMe 2 and its derivatives, correlating the effects of cocatalysts, solvents, polymerization conditions and the substituents of the fluorenyl ligand with catalytic features, such as livingness, initiation efficiency, propagation rate, syndiospecificity and copolymerization ability. The synthesis of novel olefin block copolymers and their catalytic synthesis are also introduced using this living system. Polymer Journal (2011) 43, 331-351; doi:10.1038/pj.2011 Keywords: cycloolefin copolymer; living polymerization; norbornene; propene; single-site catalyst; syndiospecific polymerization; 1-alkene A living polymerization system, in which neither chain transfer nor deactivation occurs, affords polymers with predictable molecular weights and narrow molecular weight distributions (MWDs). Living polymerization techniques are utilized for the synthesis of terminally functionalized polymers and block copolymers. Another feature of living polymerization is its simple kinetics. Because neither chain transfer nor deactivation occurs in living polymerization, the number of polymer chains (N) is equal to the number of active centers ([C*]), and the number-average molecular weight (M n ) directly reflects the propagation rate. In living polymerization, the propagation rate can be evaluated from the M n value and the polymerization time. As chain transfer via b-elimination and/or transmetalation with trialkylaluminum as a cocatalyst is inevitable in conventional Ziegler-Natta catalytic systems; homogeneous V(acac) 3 /Et 2 AlCl (where acac is acetylacetonate or its analog) had previously been the only catalytic system that produced syndiotactic-rich living polypropylene (PP) atThe 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, 5-7 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. We investigated the effect of cocatalyst, solvent and the ligand of the titanium complex on propene polymerization in terms of the livingness of the system. We also synthesized novel olefin block copolymers with the living system. This article reviews the characteristics of 1-based catalysts for tailor-made polyolefins. SYNTHESIS AND STRUCTURES OF TIT...

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Section: Substituent Effects On the Fluorenyl Ligandmentioning

confidence: 92%

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

Shiono

2011

Polym J

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“…7) [59]. Finally, another recent example for the living polymerization of propylene was reported by Coates and co-workers [60]. Thus, the bis(salicylaldiminato)titanium(IV) complex shown in Fig.…”

Section: Group Iv-and V-based Systems (Ti Zr Hf)mentioning

confidence: 85%

Transition metal-based polymer chemistry: a critical micro-review

Buchmeiser¹

2002

Designed Monomers and Polymers

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Abstract-This micro-review summarizes mainly recent (i.e. mostly later than 1995) and important developments in transition metal-catalyzed polymerization and their impact on polymer synthesis. It is not intended to be entirely comprehensive, yet will focus on signi cant improvements or interesting aspects in certain areas of polymer chemistry. For this particular reason, not all transition metal-based polymerizations will be fully covered. Instead, besides providing a 'snapshot' of the state of the art, it was a major intention to outline the main advantages and disadvantages of certain important polymerizations in a critical, yet hopefully objective way.

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“…Catalyst systems based on bis(phenoxy-imine) complexes of Ti(IV), Zr(IV) and MAO are effective catalysts for polymerization of ethylene and propylene [19,33,34,38,50,[51][52][53][54]. Detailed 13 C NMR analysis of end-groups in polypropylene prepared with several catalysts of this type showed unusual chemical and regio-effects [52,55].…”

Section: Polymerization Of Higher α-Olefin With Fi Catalystmentioning

confidence: 99%