Olefin polymerization by (cyclopentadienyl)(aryloxy)titanium(IV) complexes-cocatalyst systems

Kotohiro Nomura, Naofumi Naga, Misao Miki, Kazunori Yanagi

Research output: Contribution to journalArticle

184 Citations (Scopus)

Abstract

Various titanium(IV) complexes of the type Cp′Ti(OAr)Cl2 (Cp′ = cyclopentadienyl; OAr = aryloxy) could be prepared in high yields from Cp′TiCl3. Cp*Ti(O-2,6-iPr2C6H3)Me 2 (Cp* = C5Me5) could also be prepared from Cp*TiMe3 with 2,6-iPr2C6H3OH in high yield (77%). These complexes showed notable catalytic activities for ethylene polymerization with MAO or AliBu3-Ph3CB(C6F5) 4: Cp*Ti(O-2,6-iPr2C6H3)X 2 [X = Cl (2b), Me (8b), CF3SO3 (9b)] showed the highest activities among these complexes. The effects of substituents on both cyclopentadienyl (pentamethylcyclopentadienyl) and aryloxy (2,6-diisopropylphenoxy) groups are important for the remarkable activity. The crystallographic analyses of CpTi(O-2,6-iPr2C6H3)Cl2 (1b), Cp*Ti(O-2,6-iPr2C6H3)Cl 2 (2b), and (1,3-tBu2C5H3)Ti(O-2,6- iPr2C6H3)Cl2 (6b) could be performed, and the bond angle of Ti-O-C (phenyl group) for 2b (173.0°) was found to be significantly different from those for other complexes (162.3-163.1°), although no significant differences are observed for other bond lengths and angles among these compounds. CpTi(O-2,4,6-Me3C6H2)2Cl (7a) and CpTi(O-2,6-iPr2C6H3)2Cl (7b) could be prepared from CpTiCl3 with the corresponding phenol under the refluxing conditions of toluene, and the structure of 7a could be determined by X-ray crystallography. These complexes also exhibited moderate catalytic activities for ethylene polymerization in the presence of MAO, which was prepared by removing toluene and an excess amount of AlMe3, and the effect of the bulk of phenoxy ligand on the activity was demonstrated. 2b was also found to be an effective catalyst precursor for ethylene/1-butene copolymerization, and the smaller rErB values (0.25-0.36) compared to [Me2Si(C5Me4)(NtBu)]TiCl2 (2.45) were observed by microanalysis of the resultant copolymers.

Original languageEnglish
Pages (from-to)7588-7597
Number of pages10
JournalMacromolecules
Volume31
Issue number22
Publication statusPublished - 1998 Nov 3
Externally publishedYes

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Alkenes
Titanium
Olefins
Large scale systems
Ethylene
Monoamine Oxidase
Polymerization
Toluene
Catalyst activity
X ray crystallography
Microanalysis
Bond length
Phenol
Butenes
Copolymerization
Phenols
Copolymers
Ligands
Catalysts
ethylene

ASJC Scopus subject areas

  • Materials Chemistry

Cite this

Olefin polymerization by (cyclopentadienyl)(aryloxy)titanium(IV) complexes-cocatalyst systems. / Nomura, Kotohiro; Naga, Naofumi; Miki, Misao; Yanagi, Kazunori.

In: Macromolecules, Vol. 31, No. 22, 03.11.1998, p. 7588-7597.

Research output: Contribution to journalArticle

Nomura, Kotohiro ; Naga, Naofumi ; Miki, Misao ; Yanagi, Kazunori. / Olefin polymerization by (cyclopentadienyl)(aryloxy)titanium(IV) complexes-cocatalyst systems. In: Macromolecules. 1998 ; Vol. 31, No. 22. pp. 7588-7597.
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abstract = "Various titanium(IV) complexes of the type Cp′Ti(OAr)Cl2 (Cp′ = cyclopentadienyl; OAr = aryloxy) could be prepared in high yields from Cp′TiCl3. Cp*Ti(O-2,6-iPr2C6H3)Me 2 (Cp* = C5Me5) could also be prepared from Cp*TiMe3 with 2,6-iPr2C6H3OH in high yield (77{\%}). These complexes showed notable catalytic activities for ethylene polymerization with MAO or AliBu3-Ph3CB(C6F5) 4: Cp*Ti(O-2,6-iPr2C6H3)X 2 [X = Cl (2b), Me (8b), CF3SO3 (9b)] showed the highest activities among these complexes. The effects of substituents on both cyclopentadienyl (pentamethylcyclopentadienyl) and aryloxy (2,6-diisopropylphenoxy) groups are important for the remarkable activity. The crystallographic analyses of CpTi(O-2,6-iPr2C6H3)Cl2 (1b), Cp*Ti(O-2,6-iPr2C6H3)Cl 2 (2b), and (1,3-tBu2C5H3)Ti(O-2,6- iPr2C6H3)Cl2 (6b) could be performed, and the bond angle of Ti-O-C (phenyl group) for 2b (173.0°) was found to be significantly different from those for other complexes (162.3-163.1°), although no significant differences are observed for other bond lengths and angles among these compounds. CpTi(O-2,4,6-Me3C6H2)2Cl (7a) and CpTi(O-2,6-iPr2C6H3)2Cl (7b) could be prepared from CpTiCl3 with the corresponding phenol under the refluxing conditions of toluene, and the structure of 7a could be determined by X-ray crystallography. These complexes also exhibited moderate catalytic activities for ethylene polymerization in the presence of MAO, which was prepared by removing toluene and an excess amount of AlMe3, and the effect of the bulk of phenoxy ligand on the activity was demonstrated. 2b was also found to be an effective catalyst precursor for ethylene/1-butene copolymerization, and the smaller rErB values (0.25-0.36) compared to [Me2Si(C5Me4)(NtBu)]TiCl2 (2.45) were observed by microanalysis of the resultant copolymers.",
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N2 - Various titanium(IV) complexes of the type Cp′Ti(OAr)Cl2 (Cp′ = cyclopentadienyl; OAr = aryloxy) could be prepared in high yields from Cp′TiCl3. Cp*Ti(O-2,6-iPr2C6H3)Me 2 (Cp* = C5Me5) could also be prepared from Cp*TiMe3 with 2,6-iPr2C6H3OH in high yield (77%). These complexes showed notable catalytic activities for ethylene polymerization with MAO or AliBu3-Ph3CB(C6F5) 4: Cp*Ti(O-2,6-iPr2C6H3)X 2 [X = Cl (2b), Me (8b), CF3SO3 (9b)] showed the highest activities among these complexes. The effects of substituents on both cyclopentadienyl (pentamethylcyclopentadienyl) and aryloxy (2,6-diisopropylphenoxy) groups are important for the remarkable activity. The crystallographic analyses of CpTi(O-2,6-iPr2C6H3)Cl2 (1b), Cp*Ti(O-2,6-iPr2C6H3)Cl 2 (2b), and (1,3-tBu2C5H3)Ti(O-2,6- iPr2C6H3)Cl2 (6b) could be performed, and the bond angle of Ti-O-C (phenyl group) for 2b (173.0°) was found to be significantly different from those for other complexes (162.3-163.1°), although no significant differences are observed for other bond lengths and angles among these compounds. CpTi(O-2,4,6-Me3C6H2)2Cl (7a) and CpTi(O-2,6-iPr2C6H3)2Cl (7b) could be prepared from CpTiCl3 with the corresponding phenol under the refluxing conditions of toluene, and the structure of 7a could be determined by X-ray crystallography. These complexes also exhibited moderate catalytic activities for ethylene polymerization in the presence of MAO, which was prepared by removing toluene and an excess amount of AlMe3, and the effect of the bulk of phenoxy ligand on the activity was demonstrated. 2b was also found to be an effective catalyst precursor for ethylene/1-butene copolymerization, and the smaller rErB values (0.25-0.36) compared to [Me2Si(C5Me4)(NtBu)]TiCl2 (2.45) were observed by microanalysis of the resultant copolymers.

AB - Various titanium(IV) complexes of the type Cp′Ti(OAr)Cl2 (Cp′ = cyclopentadienyl; OAr = aryloxy) could be prepared in high yields from Cp′TiCl3. Cp*Ti(O-2,6-iPr2C6H3)Me 2 (Cp* = C5Me5) could also be prepared from Cp*TiMe3 with 2,6-iPr2C6H3OH in high yield (77%). These complexes showed notable catalytic activities for ethylene polymerization with MAO or AliBu3-Ph3CB(C6F5) 4: Cp*Ti(O-2,6-iPr2C6H3)X 2 [X = Cl (2b), Me (8b), CF3SO3 (9b)] showed the highest activities among these complexes. The effects of substituents on both cyclopentadienyl (pentamethylcyclopentadienyl) and aryloxy (2,6-diisopropylphenoxy) groups are important for the remarkable activity. The crystallographic analyses of CpTi(O-2,6-iPr2C6H3)Cl2 (1b), Cp*Ti(O-2,6-iPr2C6H3)Cl 2 (2b), and (1,3-tBu2C5H3)Ti(O-2,6- iPr2C6H3)Cl2 (6b) could be performed, and the bond angle of Ti-O-C (phenyl group) for 2b (173.0°) was found to be significantly different from those for other complexes (162.3-163.1°), although no significant differences are observed for other bond lengths and angles among these compounds. CpTi(O-2,4,6-Me3C6H2)2Cl (7a) and CpTi(O-2,6-iPr2C6H3)2Cl (7b) could be prepared from CpTiCl3 with the corresponding phenol under the refluxing conditions of toluene, and the structure of 7a could be determined by X-ray crystallography. These complexes also exhibited moderate catalytic activities for ethylene polymerization in the presence of MAO, which was prepared by removing toluene and an excess amount of AlMe3, and the effect of the bulk of phenoxy ligand on the activity was demonstrated. 2b was also found to be an effective catalyst precursor for ethylene/1-butene copolymerization, and the smaller rErB values (0.25-0.36) compared to [Me2Si(C5Me4)(NtBu)]TiCl2 (2.45) were observed by microanalysis of the resultant copolymers.

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