SYNTHESIS OF NOVEL THIOPHENEDIMETHYLENE BRIDGED HOMOBINUCLEAR METALLOCENES AND THEIR CATALYTIC PROPERTIES FOR ETHYLENE POLYMERIZATION
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SYNTHESIS OF NOVEL THIOPHENEDIMETHYLENE BRIDGED HOMOBINUCLEAR METALLOCENES AND THEIR CATALYTIC PROPERTIES FOR ETHYLENE POLYMERIZATION
Issue 1, Pages: 21-27(2006)
Affiliations:
Author bio:
Funds:
This work was financially supported by the National Natural Science Foundation of China(Nos.20374043,20074028)China Petroleum & Chemical Corporation(No.X503027).()
DOI:
CLC:O631.5
Published:2006
Accepted:
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[1].SYNTHESIS OF NOVEL THIOPHENEDIMETHYLENE BRIDGED HOMOBINUCLEAR METALLOCENES AND THEIR CATALYTIC PROPERTIES FOR ETHYLENE POLYMERIZATION[J].Chinese Journal of Polymer Science,2006(01):21-27.
SYNTHESIS OF NOVEL THIOPHENEDIMETHYLENE BRIDGED HOMOBINUCLEAR METALLOCENES AND THEIR CATALYTIC PROPERTIES FOR ETHYLENE POLYMERIZATION[J]. 2006, (1): 21-27.
[1].SYNTHESIS OF NOVEL THIOPHENEDIMETHYLENE BRIDGED HOMOBINUCLEAR METALLOCENES AND THEIR CATALYTIC PROPERTIES FOR ETHYLENE POLYMERIZATION[J].Chinese Journal of Polymer Science,2006(01):21-27.DOI:
SYNTHESIS OF NOVEL THIOPHENEDIMETHYLENE BRIDGED HOMOBINUCLEAR METALLOCENES AND THEIR CATALYTIC PROPERTIES FOR ETHYLENE POLYMERIZATION[J]. 2006, (1): 21-27.DOI:
SYNTHESIS OF NOVEL THIOPHENEDIMETHYLENE BRIDGED HOMOBINUCLEAR METALLOCENES AND THEIR CATALYTIC PROPERTIES FOR ETHYLENE POLYMERIZATION
By treating disodium(thiophenedirnethylene)dicyclopentadienide C
4
H
2
S(CH
2
C
5
H
4
Na)
2
with two equivalent of CpTiCl
3
or CpZrCl
3
DME at 0℃ in THF
two new thiophenedimethylene bridged binuclear metallocenes [Cl
2
MC
5
H
5
][C
5
H
4
CH
2
C
4
H
2
SCH
2
C
5
H
4
][C
5
H
5
MCl
2
](M=Ti 3
M=Zr 4)were synthesized in high yield and their structures were characterized by
1
H-NMR.These complexes were used as catalysts for ethylene polymerization in the presence of methylaluminoxane(MAO).The effects of polymerization temperature
time
concentration of catalyst
molar ratio of MAO/Cat on polymerization were studied in detail.The catalytic activities of thiophenedimethylene bridged binuclear metallocene catalysts(3
4)reached 2.44×10
5
g PE mol
-1
·cat
-1
·h
-1
9.61×10
5
g PE mol
-1
·cat
-1
·h
-1
respectively
which are higher than that of pheneyldimethylene bridged binuclear metallocene catalysts and much higher than that of corresponding mononuclear metallocenes(Cp
2
TiCl
2
and Cp
2
ZrCl
2
).The molecular weight distribution curves of polyethylenes produced by binuclear metallocene catalysts(3
4)and by mononuclear metallocene catalyst have only single peak
but the former(MWD=3.5-4.7)is obviously broader than the latter(MWD=2.0-2.2).
Abstract
By treating disodium(thiophenedirnethylene)dicyclopentadienide C
4
H
2
S(CH
2
C
5
H
4
Na)
2
with two equivalent of CpTiCl
3
or CpZrCl
3
DME at 0℃ in THF
two new thiophenedimethylene bridged binuclear metallocenes [Cl
2
MC
5
H
5
][C
5
H
4
CH
2
C
4
H
2
SCH
2
C
5
H
4
][C
5
H
5
MCl
2
](M=Ti 3
M=Zr 4)were synthesized in high yield and their structures were characterized by
1
H-NMR.These complexes were used as catalysts for ethylene polymerization in the presence of methylaluminoxane(MAO).The effects of polymerization temperature
time
concentration of catalyst
molar ratio of MAO/Cat on polymerization were studied in detail.The catalytic activities of thiophenedimethylene bridged binuclear metallocene catalysts(3
4)reached 2.44×10
5
g PE mol
-1
·cat
-1
·h
-1
9.61×10
5
g PE mol
-1
·cat
-1
·h
-1
respectively
which are higher than that of pheneyldimethylene bridged binuclear metallocene catalysts and much higher than that of corresponding mononuclear metallocenes(Cp
2
TiCl
2
and Cp
2
ZrCl
2
).The molecular weight distribution curves of polyethylenes produced by binuclear metallocene catalysts(3
4)and by mononuclear metallocene catalyst have only single peak
but the former(MWD=3.5-4.7)is obviously broader than the latter(MWD=2.0-2.2).
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