Titanium pyridyl-phosphinimide complexes — Synthesis, structure, and ethylene polymerization catalysis

2006 ◽  
Vol 84 (5) ◽  
pp. 755-761 ◽  
Author(s):  
Chad Beddie ◽  
Pingrong Wei ◽  
Douglas W Stephan
Keyword(s):  
Molecular Weight ◽  
Key Words ◽  
Ethylene Polymerization ◽  
Olefin Polymerization ◽  
Polymerization Catalysts ◽  
Pyridyl Group ◽  
Molecular Weight Distributions ◽  
Polymerization Catalysis ◽  
Weight Distributions

A series of Ti–pyridyl-phosphinimide complexes of the form Cp′TiX2[NPR2(2-CH2Py)] (Cp′ = Cp, Cp*, R = i-Pr, t-Bu, X = Cl, Me) have been prepared and characterized. These complexes generate ethylene polymerization catalysts upon activation with MAO or B(C6F5)3. The resulting polymers exhibit broad molecular weight distributions. The role of the pyridyl group is discussed in light of stoichiometric reactions of CpTiCl2[NPR2(2-CH2Py)] with B(C6F5)3.Key words: phosphinimide complexes, pyridyl-phosphinimides, olefin polymerization.

Altering molecular weight distributions: Benzyl–phosphinimide titanium complexes as ethylene polymerization catalysts

2004 ◽  
Vol 82 (8) ◽  
pp. 1304-1313 ◽  
Author(s):  
Emily Hollink ◽  
Pingrong Wei ◽  
Douglas W Stephan
Keyword(s):  
Molecular Weight ◽  
Ethylene Polymerization ◽  
Active Species ◽  
Polymerization Catalysts ◽  
Subsequent Reaction ◽  
X Ray ◽  
Molecular Weight Distributions ◽  
Polymerization Catalysis ◽  
Weight Distributions ◽  
High Yields

The phosphines and corresponding phosphinimines R2BnPNSiMe3 (R = t-Bu, Cy), p-C6H4(CH2PR2)2 (R = t-Bu (1), Cy (2)), and p-C6H4(CH2PR2NSiMe3)2 (R = t-Bu (3), Cy (4)) were prepared in high yields. Subsequent reaction with Ti precursors afforded (R2BnPN)TiCp*Cl2 (Cp* = η-C5Me5; R = t-Bu (5), Cy (6)), (R2BnPN)TiCpCl2 (Cp = η-C5H5; R = t-Bu (7), Cy (8)), p-C6H4(CH2PR2NTiCp*Cl2)2 (R = t-Bu (9), Cy (10)), and p-C6H4(CH2PR2NTiCpCl2)2 (R = t-Bu (11), Cy (12)). Methylation of the above complexes gave (R2BnPN)TiCp*Me2 (R = t-Bu (13), Cy (14)), (R2BnPN)TiCpMe2 (R = t-Bu (15), Cy (16)), p-C6H4(CH2PR2NTiCp*Me2)2 (R = t-Bu (17), Cy (18)), and p-C6H4(CH2PR2NTiCpMe2)2 (R = t-Bu (19), Cy (20)). The activity of these species as catalyst precursors in ethylene polymerization catalysis was evaluated using Schlenk line and Buchi reactor techniques using activation by methylaluminoxane (MAO) or [Ph3C][B(C6F5)4]. All these catalysts showed good activities and yield polymers with relatively broad molecular weight distributions. The bimodal polymers derived from catalysts generated using MAO are proposed to result from additional active species, possibly as a result of reaction of MAO with the benzylic fragments. X-ray data are reported for 1, 4–8, 10, 12–14, 16, and 18–20.Key words: phosphinimides, polymerization, catalysis, polyethylene, titanium, polymer molecular weight distributions.

Molecular Weight Dependence of Relaxation Spectra of Amorphous Polymers in the Rubbery Region. VIII. Comparisons of Experimental Relaxation Spectra of Commercial Synthetic Rubbers with those Estimated from Molecular Weight Distributions

1967 ◽  
Vol 40 (2) ◽  
pp. 484-492 ◽  
Author(s):  
Genichi Yasuda
Keyword(s):  
Molecular Weight ◽  
Molecular Weight Distribution ◽  
Weight Distribution ◽  
Mechanical Relaxation ◽  
General Validity ◽  
Relaxation Spectra ◽  
Molecular Weight Distributions ◽  
Synthetic Rubber ◽  
Weight Distributions

Abstract Synthetic rubber of different species, types, and degrees of mastication were used to examine the general validity of the proposed relationship between mechanical relaxation spectra in the rubbery region and molecular weight distribution. Results show that the proposed relationship can be well used to discuss quantitatively the role of molecular weight distribution in the theoretical behavior of a raw rubber while being processed.

Boryl-substituted Zirconocene Dichloride Complexes as Catalyst Precursors for Homogeneous Ethylene Polymerization

2007 ◽  
Vol 62 (3) ◽  
pp. 314-322 ◽  
Author(s):  
Alexandra Kestel-Jakob ◽  
Helmut G. Alt
Keyword(s):  
Molecular Weight ◽  
Ethylene Polymerization ◽  
Nickel Catalysts ◽  
Synthesis And Characterization ◽  
Zirconocene Dichloride ◽  
Molecular Weight Distributions ◽  
Weight Distributions ◽  
Methyl Aluminoxane

The synthesis and characterization of 16 new boryl-substituted zirconocene dichloride complexes are reported. After activation with methyl aluminoxane (MAO) these complexes are catalysts for homogeneous ethylene polymerization. The combination of these complexes with nickel catalysts containing Lewis basic substituents produces polymers with bimodal molecular weight distributions.

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