Metal catalysts for the vinyl/addition polymerization of norbornene

Blank, Frederik; Janiak, Christoph

doi:10.1016/j.ccr.2008.05.010

Cited by 329 publications

(213 citation statements)

References 195 publications

(313 reference statements)

Supporting

Mentioning

211

Contrasting

Order By: Relevance

“…Coordination-insertion polymerization of norbornene was studied with TiCl 4 /R 3 Al in the early 1960s, and a number of zirconocenes have been studied since the 1980s. 53,54 All of these catalysts, except for (Z 5 -C 5 H 5 )Ti(OBz) 3 -MAO, have shown very low catalytic activity, and the products produced are insoluble in common organic solvents.…”

Section: Polymerization Of Norbornenementioning

confidence: 99%

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

Shiono

2011

Polym J

View full text Add to dashboard Cite

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...

show abstract

Section: Polymerization Of Norbornenementioning

confidence: 99%

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

Shiono

2011

Polym J

View full text Add to dashboard Cite

show abstract

“…X-Ray diffraction analysis has revealed that complex 2 is a 3D supramolecular network based on coordination polymeric layers formed by tetranuclear copper clusters [Cu 4 (µ 3 -OH) 2 4 ], ligands L with µ 6 -bridging mode and SIP anions. As shown in Fig.…”

Section: Crystal and Molecular Structure Of [Cu 2 (L) 05 (Sip)(oh)(hmentioning

confidence: 99%

“…Cu1 is six-coordinated by two oxygen atoms from the carboxyl groups of two SIP ligands with distances of 1.971(2) (Cu1-O3) and 1.982(3)Å (Cu1-O7#1), one oxygen atom from a coordinated water molecule (Cu1-O2 2.285(2)Å), one oxygen atom from a carbonyl group of L (Cu1-O1 2.542(3)Å), one hydroxyl oxygen atom O5#1 (Cu1-O5#1 1.980(2)Å), and one nitrogen atom from a pyridyl group (Cu1-N1 2.045(3)Å), showing a distorted octahedral geometry. The other Cu(II) ion (Cu2) is five-coordinated by two oxygen atoms belonging to two SIP ligands (Cu2-O4 1.922(3), Cu2-O6 1.933(2)Å), two hydroxyl oxygen atoms with the distances 1.961(2) (Cu2-O5) The Cu1 and Cu2 ions are connected by four carboxylic groups with bidentate coordination fashion to form a tetranuclear copper cluster [Cu 4 (µ 3 -OH) 2 4 ], as shown in Fig. 5a.…”

Section: Crystal and Molecular Structure Of [Cu 2 (L) 05 (Sip)(oh)(hmentioning

confidence: 99%

“…In order to simplify the 2D network of complex 2, the [Cu 4 (µ 3 -OH) 2 4 ] tetranuclear cluster is surrounded by four SIP ligands and four L ligands, acting as an 8-connected node. Each L ligand serves as a 4-connected node, joining together four adjacent tetranuclear clusters (via two pyridyl nitrogen atoms and two carbonyl oxygen atoms).…”

Section: Crystal and Molecular Structure Of [Cu 2 (L) 05 (Sip)(oh)(hmentioning

confidence: 99%

See 1 more Smart Citation

The Role of the Coordination Modes of a Flexible Bis(pyridylamide) Ligand in the Topology of 2D Copper(II) Complexes

Wang¹,

Liu²,

Luan³

et al. 2012

Zeitschrift Für Naturforschung B

View full text Add to dashboard Cite

(4,8)-connected network with {4 14 .6 10 .8 4 }{4 4 .6 2 } topology, in which the L ligands adopt a µ 6 -bridging coordination mode (via ligation of the pyridyl nitrogen and carbonyl oxygen atoms). Adjacent layers in 1 and 2 are further linked by hydrogen bonding interactions to form three-dimensional supramolecular frameworks. The electrochemical behavior of the two complexes in bulk-modified carbon paste electrodes has been investigated.

show abstract

“…The synthesis of poly(ethylene-co-norbornene)s with a number of single-site catalysts have attracted great industrial and academic interest [12][13][14][15][16][17][18][19][20][21][22][23][24][25][26][27]…”

Section: Introductionmentioning

confidence: 99%

Terpolymerization of Substituted Cycloolefin with Ethylene and Norbornene by Transition Metal Catalyst

et al. 2016

View full text Add to dashboard Cite

Abstract:Ethylene-norbornene terpolymerization experiments using 5-alkyl-substituted norbornenes (5-pentyl-2-norbornene (C 5 N) and 5-octyl-2-norbornene (C 8 N)) or dicyclopentadiene (DCPD) were conducted with two ansa-metallocenes, [Zr{(η 5 -C 9 H 6 ) 2 C 2 H 4 }Cl2] (1) and [Zr{(η 5 -2,5-Me 2 C 5 H 2 ) 2 CHEt}Cl 2 ] (2), activated by methylaluminoxane (MAO). The terpolymers obtained were investigated in detail by determining the microstructure and termonomer contents by 13 C NMR, molar masses and thermal properties. Results were compared to those of ethylene (E)-norbornene (N) terpolymerizations with 1-octene. 2, with lower steric hindrance and a shorter bridge, gave the best activities, termonomer incorporation and molar masses. The size of the substituent in 5-alkyl substituted norbornene also plays a role. C 8 N gives the highest activities and molar masses, while DCPD terpolymers have the highest cycloolefin content. Terpolymers are random; their molar masses, much higher than those in 1-octene terpolymers, are in a range useful for industrial applications. Finally, T g values up to 152˝C were obtained. For similar N content, poly(E-ter-N-ter-C 8 N)s and poly(E-ter-N-ter-DCPD)s have the lowest and the highest T g values, respectively. Thus, the presence of an eight-carbon atom pendant chain in C 8 N increases the flexibility of the polymer chain more than a five-carbon atom pendant chain in C 5 N. The higher rigidity of C 5 N may lead to lower activities and to increasing probability of σ-bond metathesis and chain termination, as evidenced by chain-end group analysis.

show abstract

Metal catalysts for the vinyl/addition polymerization of norbornene

Cited by 329 publications

References 195 publications

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

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

The Role of the Coordination Modes of a Flexible Bis(pyridylamide) Ligand in the Topology of 2D Copper(II) Complexes

Terpolymerization of Substituted Cycloolefin with Ethylene and Norbornene by Transition Metal Catalyst

Contact Info

Product

Resources

About