Pentamethylcyclopentadienyl) titanium triallyioxide[Cp *Ti(OCH 2-CH[CDS1]CH 2) 3] was used as the catalyst precursor for the synthesis of polybutene 1, methylalumiunoxane(MAO) as cocatalyst. The effects of the ratio o...Pentamethylcyclopentadienyl) titanium triallyioxide[Cp *Ti(OCH 2-CH[CDS1]CH 2) 3] was used as the catalyst precursor for the synthesis of polybutene 1, methylalumiunoxane(MAO) as cocatalyst. The effects of the ratio of n (Al) to n (Ti), polymerization temperature, and concentration of Ti on catalytic activity, molecular weight and chain structure were investigated in detail. The ether soluble fraction of the polybutene 1 was characterized with 13 C NMR, DSC, WAXD, and GPC. The results indicate that the polymers thus obtained are atactic and regioirregular, the weight average molecular weight of these polymers lies in the range of 3 0×10 5 to 7 0×10 5. Increasing the polymerization temperature can result in a decrease in the polymer molecular weight. But the molecular weight varies slightly with the ratio of n (Al) to n (Ti). The catalytic activity tends to decrease with the increase in polymerization temperature. was used as the catalyst precursor for the synthesis of polybutene 1, methylalumiunoxane(MAO) as cocatalyst. The effects of the ratio of n (Al) to n (Ti), polymerization temperature, and concentration of Ti on catalytic activity, molecular weight and chain structure were investigated in detail. The ether soluble fraction of the polybutene 1 was characterized with 13 C NMR, DSC, WAXD, and GPC. The results indicate that the polymers thus obtained are atactic and regioirregular, the weight average molecular weight of these polymers lies in the range of 3 0×10 5 to 7 0×10 5. Increasing the polymerization temperature can result in a decrease in the polymer molecular weight. But the molecular weight varies slightly with the ratio of n (Al) to n (Ti). The catalytic activity tends to decrease with the increase in polymerization temperature.展开更多
Half sandwich titanocenes, e.g . (ind)TiRCl 2 (R—Cl, OMe, OEt; ind—indenyl group) and β diketonate titanium complexes, e.g . (dbm) 3TiL (L—Cl, OPh, OPhMe; dbm—dibenzoylmethane group) were investigated for syndiot...Half sandwich titanocenes, e.g . (ind)TiRCl 2 (R—Cl, OMe, OEt; ind—indenyl group) and β diketonate titanium complexes, e.g . (dbm) 3TiL (L—Cl, OPh, OPhMe; dbm—dibenzoylmethane group) were investigated for syndiotactic polymerization of styrene. The optimum molar ratios of Al to Ti of β diketonate titanium complexes were different from those of mono indenyl titanium complexes. The polymerization activity of (ind)TiRCl 2 was higher than that of (dbm) 3TiL at their own optimum n (Al)/ n (Ti). Compared with (ind)TiRCl 2, the thermostability of (dbm) 3TiL was higher. The polymerization activity of (dbm) 3Ti(OPh) was 6 5×10 5 g/(mol·h) at 363 K, while that of (ind)Ti(OMe)Cl 2 was only 4 9×10 5 g/(mol·h) at the same temperature. After 2 h of polymerization, the reaction activity of the nontitanocene was remained at 6×10 5 g/(mol·h), while that of the half sandwich titanocene was only 0 71×10 5 g/(mol·h). It is indicated that the life time of (dbm) 3TiL was much longer than that of (ind)TiRCl 2. The melting temperatures ( T m) and the syndiotacticity of polystyrene by β diketonate titanium complexes were higher than those of the polymer by mono indenyl titanium complexes as well.展开更多
文摘Pentamethylcyclopentadienyl) titanium triallyioxide[Cp *Ti(OCH 2-CH[CDS1]CH 2) 3] was used as the catalyst precursor for the synthesis of polybutene 1, methylalumiunoxane(MAO) as cocatalyst. The effects of the ratio of n (Al) to n (Ti), polymerization temperature, and concentration of Ti on catalytic activity, molecular weight and chain structure were investigated in detail. The ether soluble fraction of the polybutene 1 was characterized with 13 C NMR, DSC, WAXD, and GPC. The results indicate that the polymers thus obtained are atactic and regioirregular, the weight average molecular weight of these polymers lies in the range of 3 0×10 5 to 7 0×10 5. Increasing the polymerization temperature can result in a decrease in the polymer molecular weight. But the molecular weight varies slightly with the ratio of n (Al) to n (Ti). The catalytic activity tends to decrease with the increase in polymerization temperature. was used as the catalyst precursor for the synthesis of polybutene 1, methylalumiunoxane(MAO) as cocatalyst. The effects of the ratio of n (Al) to n (Ti), polymerization temperature, and concentration of Ti on catalytic activity, molecular weight and chain structure were investigated in detail. The ether soluble fraction of the polybutene 1 was characterized with 13 C NMR, DSC, WAXD, and GPC. The results indicate that the polymers thus obtained are atactic and regioirregular, the weight average molecular weight of these polymers lies in the range of 3 0×10 5 to 7 0×10 5. Increasing the polymerization temperature can result in a decrease in the polymer molecular weight. But the molecular weight varies slightly with the ratio of n (Al) to n (Ti). The catalytic activity tends to decrease with the increase in polymerization temperature.
文摘Half sandwich titanocenes, e.g . (ind)TiRCl 2 (R—Cl, OMe, OEt; ind—indenyl group) and β diketonate titanium complexes, e.g . (dbm) 3TiL (L—Cl, OPh, OPhMe; dbm—dibenzoylmethane group) were investigated for syndiotactic polymerization of styrene. The optimum molar ratios of Al to Ti of β diketonate titanium complexes were different from those of mono indenyl titanium complexes. The polymerization activity of (ind)TiRCl 2 was higher than that of (dbm) 3TiL at their own optimum n (Al)/ n (Ti). Compared with (ind)TiRCl 2, the thermostability of (dbm) 3TiL was higher. The polymerization activity of (dbm) 3Ti(OPh) was 6 5×10 5 g/(mol·h) at 363 K, while that of (ind)Ti(OMe)Cl 2 was only 4 9×10 5 g/(mol·h) at the same temperature. After 2 h of polymerization, the reaction activity of the nontitanocene was remained at 6×10 5 g/(mol·h), while that of the half sandwich titanocene was only 0 71×10 5 g/(mol·h). It is indicated that the life time of (dbm) 3TiL was much longer than that of (ind)TiRCl 2. The melting temperatures ( T m) and the syndiotacticity of polystyrene by β diketonate titanium complexes were higher than those of the polymer by mono indenyl titanium complexes as well.
