Recent Progress in the Vinylic Polymerization and Copolymerization of Norbornene Catalyzed by Transition Metal Catalysts

Ma, Rui; Hou, Yubang; Gao, Jie; Bao, Feng

doi:10.1080/15583720903048276

Cited by 55 publications

(22 citation statements)

References 118 publications

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“…, and the crystallographic data and refinement parameters for the cobalt complex are presented in Table . Similar structure of ligands and complexes has been reported in our previous work . The four‐coordinate environment in which the two L ligands act as monoanionic bidentate N,O chelators and lie in the trans conformation creates two stable delocalized six‐membered chelating rings (CoOCCCN).…”

Section: Resultssupporting

confidence: 74%

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Cobalt complex bearing β‐ketoamine ligand: syntheses, structure, catalytic behavior for styrene and methyl methacrylate polymerization

Gao

Bao

Chen

et al. 2014

Applied Organom Chemis

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Cobalt complex based on β-ketoamine ligand [(Z)-4-((2,5-dimethylphenylamino) (phenyl)methylene)-3-methyl-1-phenyl-1 H-pyrazol-5(4H)-one] was successfully synthesized. The produced catalyst showed satisfactory activities in the cobalt-mediated radical polymerization of styrene and methyl methacrylate with the common initiator of AIBN. The resulting polymerizations have the characteristics of living radical polymerization and displayed a nearly linear correlation between the number-average molecular weight and monomer conversion. Low polydispersity was obtained for all polymerizations, and the polydispersity index decreased with the increase of conversion. These improvements facilitate the implementation of styrene and methacrylate cobalt-mediated radical polymerization, and open the door to the scale-up of the process.

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Section: Resultssupporting

confidence: 74%

“…The cobalt complex was obtained as follows . An ethanol solution (5 ml) containing L (39 mg, 0.1 mmol) and triethylamine (14 μl, 0.1 mmol) was stirred for 10 min at 60 °C.…”

Section: Methodsmentioning

confidence: 99%

Cobalt complex bearing β‐ketoamine ligand: syntheses, structure, catalytic behavior for styrene and methyl methacrylate polymerization

Gao

Bao

Chen

et al. 2014

Applied Organom Chemis

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“…The development of early transition metal single-site catalysts enables us to synthesize poly(norborneneÀaltÀethene) as well as poly(norborneneÀ ranÀethene), the T g value of which can be controlled over a wide range. 57 A number of late transition metal-based catalysts have been reported to produce polynorbornene via coordination insertion with good activity, but they do not produce a copolymer with ethene because of the facile b-hydrogen transfer after ethene insertion.…”

Section: Copolymerization Of Norbornene With 1-alkenementioning

confidence: 99%

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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“… 1 Among those, polynorbornene (PNBE) prepared by 1,2-insertion catalytic polymerization is particularly interesting as it has excellent thermal and chemical stability (degradation above 400 °C), high Tg (>300 °C), low dielectric constant and low birefringence. 2 , 3 Furthermore, when disyndiotactic, this rigid polymer adopts a distinctive tubular helical molecular crystalline structure. 4 Polar norbornenes (NBEs) can be prepared from straightforward Diels–Alder reactions between cyclopentadiene and simple dienophiles.…”

Section: Introductionmentioning

confidence: 99%

Bypassing the lack of reactivity of endo-substituted norbornenes with the catalytic rectification–insertion mechanism

Commarieu¹,

Claverie²

2015

Chem. Sci.

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Recent Progress in the Vinylic Polymerization and Copolymerization of Norbornene Catalyzed by Transition Metal Catalysts

Cited by 55 publications

References 118 publications

Cobalt complex bearing β‐ketoamine ligand: syntheses, structure, catalytic behavior for styrene and methyl methacrylate polymerization

Cobalt complex bearing β‐ketoamine ligand: syntheses, structure, catalytic behavior for styrene and methyl methacrylate polymerization

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

Bypassing the lack of reactivity of endo-substituted norbornenes with the catalytic rectification–insertion mechanism

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