聚乙烯共聚物的制备.pdfVIP

聚乙烯共聚物的制备 徐志贤, 李伯耿, 介素云 (湖南理工大学材料科学系，长沙 561231) Abstract： Catalyzed by a phenoxycyclopentylimine ligated zirconium complex/dried methylaluminoxane (dMAO) system at 40℃ under 1 atm of ethylene pressure, linear vinyl-terminated polyethylene (PE-ene) with nearly 100% of end-functionality was produced via ethylene polymerization. With high efficiency, hydroxyl-terminated polyethylene (PE-OH) was subsequently prepared via the radical initiated thiol-ene click chemistry between the PE-ene and 2- mercaptoethanol. The PE-OH was then used to react with norbornene-5-carbonyl chloride to synthesize the norbornene-terminated polyethylene macromonomer (PE-NB) through the esterification reaction. The ring-opening metathesis copolymerization (ROMP) of PE-NB and norbornene (NB) with the different feed ratio was conducted in the presence of Grubbs Ⅱ generation catalyst to produce the polyethylene-based graft copolymers. Both random and block polynorbornene-g-polyethylene graft copolymers (PNB-g-PE) were then obtained with different feeding mode, i.e., the one-batch feeding mode and the sequential feeding mode, respectively. The structures of the graft copolymers were characterized by Fourier transform-infrared and proton nuclear magnetic resonance spectroscopy. The molecular weight and molecular weight distribution of PNB-g-PE were determined by high-temperature gel permeation chromatography; the thermal properties of PNB-g-PE were also tested by differential scanning calorimetry. The conversion of macromonomer was found to be nearly 100% in the random copolymerization of macromonomer and norbornene. The random graft copolymers were obtained with the molecular 4 4 weight of 1.79×10 -3.14×10 with relatively narrow molecular weight distribution (2.09- 2.60). The molecular weight of the copolym