A NOVEL TITANIUM COMPLEX WITH LINKED β-DIKETONATO-INDENYL LIGAND FOR CATALYTIC SYNDIOSPECIFIC POLYMERIZATION OF STYRENE

A novel ligand (3), in which the indenyl group is linked to a β-diketone moiety through a three-carbon bridge, andits titanium complex (4) were synthesized. The titanium complex was employed as a metallocene analog with co-catalystmethylaluminoxane (MAO) in catalytic syndiospecific polymerization of styrene to give highly syndiotactic polystyrene(s-PS, 96%-97%). Polymerization temperature (T_p) strongly influenced the catalytic activity and syndiotacticity of theproduced PS. The activities of catalyst 4 increase from 1.84×10~6 to 3.26×10~6 gPS/molTi·h with the increase of T_p from60℃ to 80℃ and the syndiotacticities of the produced s-PS also increase slightly. Then, both the catalytic activity and thesyndiotacticity of PS decrease at T_p of 90℃.

Syndiospecific Polymerization of Styrene Catalyzed by Half-titanocenes Containing Monodentate Anionic Nitrogen Ligands

Main observation and conclusion Styrene polymerization catalyzed by the half-titanocenes CpTiCl_(2)[1,3-R_(2)(CH_(2)N)_(2)C=N](6b:R=_(2),6-Me_(2)C_(6)H_(3),T_(4):R=_(2),4,6-Me_(3)C_(6)H_(2);T5:R=_(2),6-iPr_(2)C_(6)H_(3))was carried out in the presence of methylaluminoxane(MAO).Compared to the styrene conversion(31%)and syndiospecific index(45%)using reported 6b as precatalyst,T5 bearing ligand with isopropyl substitutes on the N-aryl-rings exhibits much higher styrene conversion(61%)and syndiospecific index(99%),indicating that the catalytic behavior could be improved obviously by the introduction of electronic donating and steric bulky substituents.One N atom in imidazolin-_(2)-iminato ligand was replaced by O atom,affording half-titanocenes CpTiCl_(_(2))[3-C6H5(CH_(2)N)(CH_(2)O)C=N(T1)and CpTiCl_(_(2))[_(2),6-Me_(2)(C6H3O)(NiPr_(2))C=N](T_(2)).Compared to 6b,both higher styrene conversion and syndiospecific index are afforded by using half-titanocene T1 containing_(2)-imino-3-phenyloxazolidine ligand.All the results illustrate that both the chemical structure and the nature of substituents of the ligand have obvious influence on the styrene conversion and syndiospecific index in the polymerization of styrene.All the resulting syndiotactic polystyrenes(sPSs)are highly syndiospecific(rrr>99%).Correspondingly,the sPS prepared using T5/MAO catalytic system exhibits high melting point and narrow molecular weight distribution.The results might show new light on designing more efficient half-titanocenes for styrene polymerization with both high styrene conversion and high syndiospecific selectivity.