In this study, we examined various alkylaluminums, including triethylaluminum (TEA), triisobutylaluminum (TIBA), and diethylaluminum chloride (DEAC), as cocatalysts for the activation of ethylene polymerizations in the presence of a fluorinated Fujita group invented titanium (FI-Ti) catalyst, bis[N-(3-tert-butylsalicylidene)-2,3,4,5,6-pentafluoroanilinato] titanium(IV) dichloride (complex 1). DEAC, because of the strong Lewis acidity, was an efficient cocatalyst for activating complex 1 for the ethylene polymerizations, whereas TEA and TIBA as cocatalysts could hardly polymerize ethylene. The effects of the polymerization temperature and Al/Ti molar ratio on the formation of active species, properties, and molecular weight of the resulting polyethylene were investigated. In the complex 1/ DEAC catalyst system, the oxidation states of Ti active species were determined by electron paramagnetic resonance. The results demonstrated that Ti(IV) active species were inclined to polymerize ethylene and yielded high-molecular-weight polyethylene. Comparatively, Ti(III) active species resulted from the reduction of Ti(IV) by DEAC and afforded oligomers. Moreover, the bigger steric bulk for the cocatalysts was necessary to achieve ethylene living polymerization with the fluorinated FI-Ti catalyst.

We report on the synthesis and self-assembly in water of well-defined amphiphilic star-block copolymers with a linear crystalline polyethylene (PE) segment and two or three poly(ethylene glycol) (PEG) segments as the building blocks. Initially, alkynyl-terminated PE (PE-B) is synthesized via esterification of pentynoic acid with hydroxyl-terminated PE, which is prepared using chain shuttling ethylene polymerization with 2,6-bis[1-(2,6-dimethylphenyl) imino ethyl] pyridine iron (II) dichloride/methylaluminoxane/diethyl zinc and subsequent in situ oxidation with oxygen. Then diazido-and triazido-terminated PE (PE-(N 3 ) 2 and PE-(N 3 ) 3 ) are obtained by the click reactions between PE-B and coupling agents containing triazido or tetraazido, respectively. Finally, the three-arm and four-arm star-block copolymers, PE-b-(PEG) 2 and PE-b-(PEG) 3 , are prepared by click reactions between PE-(N 3 ) 2 or PE-(N 3 ) 3 and alkynyl-terminated PEG. The self-assembly of the resultant amphiphilic star-block copolymers in water was investigated by dynamic light scattering, transmission electron microscopy, and atomic force microscopy. It is found that, in water, a solvent selectively good for PEG blocks; these star-block copolymer chains could self-assemble to form platelet-like micelles with insoluble PE blocks as crystalline core and soluble PEG blocks as shell. The confined crystallization of PE blocks in self-assembled structure formed in aqueous solution is investigated by differential scanning calorimetry.