Synthesis of half metallocene complexes ([O,N]CpTiCl 2) containing 8 hydroxy quinoline ligand is described.The results indicate that [O,N]CpTiCl 2 is active for ethylene polymerization at 30℃ and 0.1?mPa with MAO act...Synthesis of half metallocene complexes ([O,N]CpTiCl 2) containing 8 hydroxy quinoline ligand is described.The results indicate that [O,N]CpTiCl 2 is active for ethylene polymerization at 30℃ and 0.1?mPa with MAO activation,and exhibits much higher activity than CpTiCl\-3.The results show that when there is an electron donor substituent next to N,such as a methyl,the activity of [O,N]CpTiCl 2 increases greatly; however,if there is an electron acceptor substituent,such as nitro in the benzene ring,it is inactive.For the [O,N]CpTiCl 2/MAO system,the polymerization rate is “up and down” type with increasing the Al/Ti molar ratio.The activity reaches its maximum at molar ratio of Al/Ti = 500,which is over 1×10 5?gPE/molTi·h.The activity decreases as the polymerization time is longer.The polyethylene obtained is characteristic of narrow molecular distribution with molecular weight M w around 40×10 4 and molecular weight ratio M w/ M n=2 8.展开更多
Synthesis and elemental analysis of metallocene analogic complexes (NpCpTiCl 2) containing the azole ligand (Np) are described,in which Np is Pr=Pyrolyl (C 4H 4N)(1); Id=Indolyl (C 8H 6N)(2); Ai=7 Azaindolyl (C 7H 5N ...Synthesis and elemental analysis of metallocene analogic complexes (NpCpTiCl 2) containing the azole ligand (Np) are described,in which Np is Pr=Pyrolyl (C 4H 4N)(1); Id=Indolyl (C 8H 6N)(2); Ai=7 Azaindolyl (C 7H 5N 2)(3); Iz=Indazolyl (C 7H 5N 2)(4); Bi=Benzimidazolyl (C 7H 5N 2)(5),respectively.It is proved by the experiments that NpCpTiCl 2 is active for ethylene polymerization at 30℃ and 0.1?mPa with MAO activation,and the results show that the activity of 1 and 2 which contain one nitrogen in the azole ring is higher than 4 and 5 which contain two nitrogens,while 3 is inactive.For the NpCpTiCl 2/MAO system,the activity is “up and down” type with increase in the Al/Ti molar ratio,and up to the highest when the Al/Ti molar ratio is about 500.The polyethylene obtained is characteristic of narrow distribution with molecular weight M w around 35×10 4 and molecular weight ratio M w/ M n less than 3.展开更多
A novel non metallocene supported catalyst,CpTi(dbm) Cl 2/MgCl 2 was synthesized in situ via reaction between CpTi(dbm)Cl 2 an d BuMgCl in heptane.The surface area,pore volume and crystal structure of the su pported c...A novel non metallocene supported catalyst,CpTi(dbm) Cl 2/MgCl 2 was synthesized in situ via reaction between CpTi(dbm)Cl 2 an d BuMgCl in heptane.The surface area,pore volume and crystal structure of the su pported catalyst and MgCl 2(in situ) which was obtained by reaction of Mg a nd BuCl were characterized by BET and XRD methods,respectively.The surface area and pore volume of MgCl 2(in situ) are higher than those of normal MgCl 2,and the s urface area and pore volume of the supported catalyst are also high.The crystal structure of the supported catalyst is amorphous,which is similar to that of MgC l 2(in situ).Ethylene polymerization with MAO or AlR 3 was investigated,w hich indicates that the activity does not decrease while AlR 3 was used as co catalyst instead of MAO,so MAO can be absent in both the catalyst preparation an d et hylene polymerization processes.The catalytic activity can be as high as 3 06× 10\+6gPE/molTi·h with triisobutyl aluminium(Ti BA) as co\|catalyst when polymerization tem perature is 80℃,and Al/Ti molar ratio is 200.展开更多
文摘Synthesis of half metallocene complexes ([O,N]CpTiCl 2) containing 8 hydroxy quinoline ligand is described.The results indicate that [O,N]CpTiCl 2 is active for ethylene polymerization at 30℃ and 0.1?mPa with MAO activation,and exhibits much higher activity than CpTiCl\-3.The results show that when there is an electron donor substituent next to N,such as a methyl,the activity of [O,N]CpTiCl 2 increases greatly; however,if there is an electron acceptor substituent,such as nitro in the benzene ring,it is inactive.For the [O,N]CpTiCl 2/MAO system,the polymerization rate is “up and down” type with increasing the Al/Ti molar ratio.The activity reaches its maximum at molar ratio of Al/Ti = 500,which is over 1×10 5?gPE/molTi·h.The activity decreases as the polymerization time is longer.The polyethylene obtained is characteristic of narrow molecular distribution with molecular weight M w around 40×10 4 and molecular weight ratio M w/ M n=2 8.
文摘Synthesis and elemental analysis of metallocene analogic complexes (NpCpTiCl 2) containing the azole ligand (Np) are described,in which Np is Pr=Pyrolyl (C 4H 4N)(1); Id=Indolyl (C 8H 6N)(2); Ai=7 Azaindolyl (C 7H 5N 2)(3); Iz=Indazolyl (C 7H 5N 2)(4); Bi=Benzimidazolyl (C 7H 5N 2)(5),respectively.It is proved by the experiments that NpCpTiCl 2 is active for ethylene polymerization at 30℃ and 0.1?mPa with MAO activation,and the results show that the activity of 1 and 2 which contain one nitrogen in the azole ring is higher than 4 and 5 which contain two nitrogens,while 3 is inactive.For the NpCpTiCl 2/MAO system,the activity is “up and down” type with increase in the Al/Ti molar ratio,and up to the highest when the Al/Ti molar ratio is about 500.The polyethylene obtained is characteristic of narrow distribution with molecular weight M w around 35×10 4 and molecular weight ratio M w/ M n less than 3.
文摘A novel non metallocene supported catalyst,CpTi(dbm) Cl 2/MgCl 2 was synthesized in situ via reaction between CpTi(dbm)Cl 2 an d BuMgCl in heptane.The surface area,pore volume and crystal structure of the su pported catalyst and MgCl 2(in situ) which was obtained by reaction of Mg a nd BuCl were characterized by BET and XRD methods,respectively.The surface area and pore volume of MgCl 2(in situ) are higher than those of normal MgCl 2,and the s urface area and pore volume of the supported catalyst are also high.The crystal structure of the supported catalyst is amorphous,which is similar to that of MgC l 2(in situ).Ethylene polymerization with MAO or AlR 3 was investigated,w hich indicates that the activity does not decrease while AlR 3 was used as co catalyst instead of MAO,so MAO can be absent in both the catalyst preparation an d et hylene polymerization processes.The catalytic activity can be as high as 3 06× 10\+6gPE/molTi·h with triisobutyl aluminium(Ti BA) as co\|catalyst when polymerization tem perature is 80℃,and Al/Ti molar ratio is 200.
