o-Phenylene-bridged Cp/amido titanium and zirconium complexes and their polymerization reactivity

Lee, Sang Hoon; Wu, Chun Ji; Yoo, Jina; Kwak, Jung-Eun; Yun, Hoseop; Lee, Hyun Ju

doi:10.1016/j.jorganchem.2007.11.021

Cited by 8 publications

(3 citation statements)

References 35 publications

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“…A key to the success in the preparation of HDCPD/ethylene copolymers is development of catalyst 6 that is better than CGC in terms of comonomer incorporation and activity . We developed a series of o -phenylene-bridged analogues of CGC . HDCPD/ethylene copolymer is attractive because the polymer structure of the alternating copolymer resembles that of polymer 4 that is obtained through the ROMP of DMON and subsequent hydrogenation.…”

Section: Introductionmentioning

confidence: 99%

Preparation of a Bulky Cycloolefin/Ethylene Copolymer and Its Tensile Properties

Lim

et al. 2009

Macromolecules

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Regioselective partial hydrogenation of tricyclopentadiene (TCPD) was achieved with a high turnover number of 10 000 by catalysis with a N-heterocyclic carbene-palladium complex. Copolymerization of ethylene and the partially hydrogenated product, dihydrotricyclopentadiene (HTCPD), was realized using a catalytic system of [8-The copolymer was unambiguously characterized through the analysis of one-and two-dimensional NMR spectra. The monomer reactivity ratios, r ethylene and r HTCPD , determined through the Fineman-Ross plot, were 2.8 and 0.025, respectively, indicating negligible successive insertion of two HTCPD. A nearly alternating copolymer with a HTCPD content of 45 mol % was obtained with a satisfactory activity (4.7 Â 10 6 g/(mol Ti h)), of which T g was 177 °C, significantly higher than that of norbornene/ethylene copolymer at the same cycloolefin content. Tensile stress-strain curves indicated that the brittleness observed for a high-T g norbornene/ethylene copolymer was relieved to show some ductile property for the HTCPD/ethylene copolymer of the same level of high T g .

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Section: Introductionmentioning

confidence: 99%

Preparation of a Bulky Cycloolefin/Ethylene Copolymer and Its Tensile Properties

Lim

et al. 2009

Macromolecules

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“…The homopolymerization of HDCPD was reported with a metathesis catalyst, WCl 5 /Et 2 AlCl, but a low-molecular-weight oligomer ( M n = 3000) was obtained . Recently, we reported the preparation and polymerization reactivity of a series of o -phenylene-bridged analogues of CGC . One of them, complex 1 as shown in eq 3, shows better comonomer incorporation and activity than CGC ([Me 2 Si(η 5 -Me 4 C 5 )(N t Bu)]TiCl 2 ) in ethylene/1-octene copolymerization .…”

Section: Introductionmentioning

confidence: 99%

Copolymerization of 5,6-Dihydrodicyclopentadiene and Ethylene

Yoo

et al. 2008

Macromolecules

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Supporting InformationGeneral Remarks. All manipulations were performed under an inert atmosphere using standard glove box and Schlenk techniques. 5,6-Dihydrodicyclopentadiene (HDCPD) was purchased from TCI. Toluene (anhydrous grade, Aldrich), norbornene and HDCPD were distilled over Na/K alloy. Ethylene was purchased from Conley gas (99.0%) and purified by contacting with molecular sieves and copper for several days under the pressure of 200 psig. The 1 H NMR (600 MHz) and 13 C NMR (150 MHz) spectra of the copolymers were recorded on a Bruker Avance 600 at 25 o C. Gel permeation chromatograms (GPC) were obtained at 30 o C in THF using Waters Model 150-C+ GPC and the data were analyzed using a polystyrene analyzing curve. Differential scanning calorimetry (DSC) was performed on a Thermal Analysis Q10. Glass transition Temperatures (T g ) were determined with DSC on a second heating at a heating rate of 15 o C/min. Ethylene/HDCPD copolymerization. In a glove box, 28 mL of toluene solution of HDCPD (5.37 g, 40 mmol) was added to a dried 60 mL glass reactor with a magnetic bar. The reactor was assembled and brought out from the glove box. The reactor was then heated to 70 o C with a mantle. After an activated

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“…The design and preparation of new metal complexes are an issue in the field of homogeneous polymerization catalysts. , In this paper, we report an expansion of the new ortho -lithiation method to various N -alkylanilines and its utilization to construct various ortho -phenylene-bridged (tetramethylcyclopentadienyl, indenyl, or fluorenyl)/amido titanium complexes, which are screened as catalysts in ethylene/1-octene copolymerization. The syntheses of ortho -phenylene-bridged (Me 3 C 5 H or Me 2 C 5 H 2 )/amido titanium or zirconium complexes were disclosed, but the synthetic route was rather lengthy (eq 2) . Furthermore, the variation on the π-ligand was limited only to dimethylcyclopentadienyl and trimethylcyclopentadienyl in the route.…”

Section: Introductionmentioning

confidence: 99%

CO₂-Mediated ortho-Lithiation of N-Alkylanilines and Its Use for the Construction of Polymerization Catalysts

Lee

et al. 2008

Organometallics

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The ortho-lithiation of N-alkylanilines is accomplished by the treatment of t BuLi with the lithium carbamate compounds generated in situ from N-alkylanilines. The lithiated compounds attack the carbonylcarbon on 2,3,4,5-tetramethylcyclopentenone, 1-indanone, or 9-fluorenone to yield tertiary alcohols, which are transformed to N-alkylanilines attaching a Me 4 C 5 , indenyl, or fluorenyl unit at an ortho-position. From the compounds, various o-phenylene-bridged (Me 4 C 5 , indenyl, or fluorenyl)/amido titanium complexes are prepared in one step. The Me 4 C 5 /ethylamido titanium complex exhibits a similar catalytic performance to the CGC [Me 2 Si(η 5 -Me 4 C 5 )(N t Bu)]TiCl 2 in ethylene/1-octene copolymerization in terms of activity, molecular weight of the obtained polymer, and 1-octene incorporation.

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o-Phenylene-bridged Cp/amido titanium and zirconium complexes and their polymerization reactivity

Cited by 8 publications

References 35 publications

Preparation of a Bulky Cycloolefin/Ethylene Copolymer and Its Tensile Properties

Preparation of a Bulky Cycloolefin/Ethylene Copolymer and Its Tensile Properties

Copolymerization of 5,6-Dihydrodicyclopentadiene and Ethylene

CO₂-Mediated ortho-Lithiation of N-Alkylanilines and Its Use for the Construction of Polymerization Catalysts

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o-Phenylene-bridged Cp/amido titanium and zirconium complexes and their polymerization reactivity

Cited by 8 publications

References 35 publications

Preparation of a Bulky Cycloolefin/Ethylene Copolymer and Its Tensile Properties

Preparation of a Bulky Cycloolefin/Ethylene Copolymer and Its Tensile Properties

Copolymerization of 5,6-Dihydrodicyclopentadiene and Ethylene

CO2-Mediated ortho-Lithiation of N-Alkylanilines and Its Use for the Construction of Polymerization Catalysts

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CO₂-Mediated ortho-Lithiation of N-Alkylanilines and Its Use for the Construction of Polymerization Catalysts