Back to results
US 5,324,800 AGranted
Process and catalyst for polyolefin density and molecular weight control
AssigneeExxon Chemical Patents Inc.
InventorsHoward C. Welborn, Jr., John A. Ewen
Life of this patent
Estimating the term…
Abstract
Catalysts comprising (a) derivatives of mono, bi and tricyclopentadienyl coordination complexes with a transition metal and (b) and an alumoxane are employed in a process of producing polyolefins of controlled molecular weight.
Claims33
A catalyst system for the polymerization of olefins comprising (a) a metallocene catalyst component represented by the formulas
- (C.sub.5 R'.sub.m).sub.p R".sub.s (C.sub.5 R'.sub.m)MeQ.sub.3-p and
- R".sub.s (C.sub.5 R'.sub.m).sub.2 MeQ'
- wherein Me is a Group 4B, 5B, 6B metal, (C.sub.5 R'.sub.m) is a substituted cyclopentadienyl, each R', which can be the same or different, is hydrogen, ethyl, propyl, butyl, amyl, isoamyl, hexyl, isobutyl, heptyl, octyl, nonyl, decyl, cetyl, alkenyl, aryl, alkylaryl or arylalkyl radical having from 1 to 20 carbon atoms or two adjacent carbon atoms are joined together to form a C.sub.4 -C.sub.6 ring, R" is a C.sub.1 -C.sub.4 alkylene radical, a dialkyl germanium or silicon, or an alkyl phosphine or amine radical substituting on and bridging two (C.sub.5 R'.sub.m) rings, each Q which can be the same or different is an aryl, alkyl, alkenyl, alkylaryl, or arylalkyl radical having from 1 to 20 carbon atoms or halogen, Q' is an alkylidene radical having from 1-20 carbon atoms, s is 0 or 1 and when s is 0, m is 5 and p is 0, 1 or 2 and when s is 1, m is 4 and p is 1;
- at least one R' is a hydrocarbyl radical when at least one Q is an alkyl radical and (b) an alumoxane.
1 more element
A catalyst system for the polymerization of olefins comprising (a) a single metallocene catalyst component represented by the formulas
- (C.sub.5 R'.sub.m).sub.p R".sub.s (C.sub.5 R'.sub.m)MeQ.sub.3-p and
- R".sub.s (C.sub.5 R'.sub.m).sub.2 MeQ'
- wherein Me is a Group 4B, 5B, 6B metal, (C.sub.5 R'.sub.m) is a substituted cyclopentadienyl, each R', which can be the same or different, is hydrogen, an alkyl, alkenyl, aryl, alkylaryl or arylalkyl radical having from 1 to 20 carbon atoms or two adjacent carbon atoms are joined together to form a C.sub.4 -C.sub.6 ring, R" is a C.sub.1 -C.sub.4 alkylene radical, a dialkyl germanium or silicon, or an alkyl phosphine or amine radical substituting on and bridging two (C.sub.5 R'.sub.m) rings, each Q which can be the same or different is an aryl, alkenyl, alkylaryl, or arylalkyl radical having from 1 to 20 carbon atoms or halogen, Q' is an alkylidene radical having from 1-20 carbon atoms, s is 0 or 1 and when s is 0, m is 5 and p is 0, 1 or 2 and when s is 1, m is 4 and p is 1;
- at least one R' is a hydrocarbyl radical when at least one Q is an alkyl radical;
- and (b) an alumoxane.
2 more elements
A catalyst system for the polymerization of olefins to a polyolefin having a molecular weight which can be dependent on a choice of metallocene catalyst component comprising (a) a metallocene catalyst component represented by the formulas
- (C.sub.5 R'.sub.m).sub.p R".sub.s (C.sub.5 R'.sub.m)MeQ.sub.3-p and
- R".sub.s (C.sub.5 R'.sub.m).sub.2 MeQ'
- wherein Me is a Group 4B metal, (C.sub.5 R'.sub.m) is a dialkyl, tri-alkyl, tetra-alkyl or penta-alkyl cyclopentadienyl or (C.sub.5 R'.sub.m) is a substituted cyclopentadienyl, each R', which can be the same or different, is hydrogen, an alkenyl, aryl, alkylaryl or arylalkyl radical having from 1 to 20 carbon atoms or two adjacent carbon atoms are joined together to form a C.sub.4 -C.sub.6 ring, R" is a C.sub.1 -C.sub.4 alkylene radical, a dialkyl germanium or silicon, or an alkyl phosphine or amine radical substituting on and bridging two (C.sub.5 R'.sub.m) rings, each Q which can be the same or different is an aryl, alkyl, alkenyl, alkylaryl, or arylalkyl radical having from 1 to 20 carbon atoms or halogen, Q' is an alkylidene radical having from 1 to 20 carbon atoms, s is 0 or 1 and when s is 0, m is 5 and p is 0, 1 or 2 and when s is 1, m is 4 and p is 1;
- at least one R' is a hydrocarbyl radical when at least one Q is an alkyl radical;
- and (b) an alumoxane.
2 more elements
A catalyst system comprising a metallocene catalyst component and an alumoxane, which polymerizes olefins to polymers of a molecular weight distribution expressed as M.sub.w /M.sub.n of from 1.5 to 4.0, in which the metallocene catalyst component consists essentially of a metallocene represented by the formulas
- (C.sub.5 R'.sub.m).sub.p R".sub.s (C.sub.5 R'.sub.m)MeQ.sub.3-p and
- R".sub.s (C.sub.5 R'.sub.m).sub.2 MeQ'
- wherein Me is zirconium, a (C.sub.5 R'.sub.m) is a substituted cyclopentadienyl, each R', which can be the same or different, is hydrogen, an alkyl, alkenyl, aryl, alkylaryl or arylalkyl radical having from 1 to 20 carbon atoms or two adjacent carbon atoms are joined together to form a C.sub.4 -C.sub.6 ring, R" is a C.sub.1 -C.sub.4 alkylene radical, a dialkyl germanium or silicon, or an alkyl phosphine or amine radical substituting on and bridging two (C.sub.5 R'.sub.m) rings, each Q which can be the same or different is an aryl, alkyl, alkenyl, alkylaryl, or arylalkyl radical having from 1 to 20 carbon atoms or halogen, Q' is an alkylidene radical having from 1-20 carbon atoms, s is 0 or 1 and when s is 0, m is 5 and p is 0, 1 or 2 and when s is 1, m is 4 and p is 1, at least one R' is a hydrocarbyl radical when at least one Q is an alkyl radical.
A catalyst system for the polymerization of olefins comprising (a) a metallocene catalyst component consisting of metallocenes represented by the formulas
- (C.sub.5 R'.sub.m).sub.p R".sub.s (C.sub.5 R'.sub.m)MeQ.sub.3-p and
- R".sub.s (C.sub.5 R'.sub.m).sub.2 MeQ'
- wherein Me is a Group 4B metal, a (C.sub.5 R'.sub.m) is a dialkyl, tri-alkyl, tetra-alkyl or penta-alkyl cyclopentadienyl or a (C.sub.5 R'.sub.m) is a substituted cyclopentadienyl, each R', which can be the same or different, is hydrogen, an alkenyl, aryl, alkylaryl or arylalkyl radical having from 1 to 20 carbon atoms or two adjacent carbon atoms are joined together to form a C.sub.4 -C.sub.6 ring, R" is a C.sub.1 -C.sub.4 alkylene radical, a dialkyl germanium or silicon, or an alkyl phosphine or amine radical substituting on and bridging two (C.sub.5 R'.sub.m) rings, each Q which can be the same or different is an aryl, alkyl, alkenyl, alkylaryl, or arylalkyl radical having from 1 to 20 carbon atoms or halogen, Q' is an alkylidene radical having from 1-20 carbon atoms, s is 0 or 1 and when s is 0, m is 5 and p is 0, 1 or 2 and when s is 1, m is 4 and p is 1;
- at least one R' is a hydrocarbyl radical when at least one Q is an alkyl radical;
- and (b) an alumoxane.
2 more elements
A catalyst system comprising a metallocene catalyst component and an alumoxane, which polymerizes olefins to polymers of a molecular weight distribution expressed as M.sub.w /M.sub.n of from 1.5 to 4.0, in which the metallocene catalyst component is represented by the formula
- (C.sub.5 R'.sub.m).sub.p R".sub.s (C.sub.5 R'.sub.m)MeQ.sub.3-p and
- R".sub.s (C.sub.5 R'.sub.m).sub.2 MeQ'
- wherein Me is titanium, (C.sub.5 R'.sub.m) is a substituted cyclopentadienyl, each R', which can be the same or different, is hydrogen, an alkyl, alkenyl, aryl, alkylaryl or arylalkyl radical having from 1 to 20 carbon atoms or two adjacent carbon atoms are joined together to form a C.sub.4 -C.sub.6 ring, R" is a C.sub.1 -C.sub.4 alkylene radical, a dialkyl germanium or silicon, or an alkyl phosphine or amine radical substituting on and bridging two (C.sub.5 R'.sub.m) rings, each Q which can be the same or different is an aryl, alkenyl, alkylaryl, or arylalkyl radical having from 1 to 20 carbon atoms or halogen, Q' is an alkylidene radical having from 1-20 carbon atoms, s is 0 or 1 and when s is 0, m is 5 and p is 0,1 or 2 and when s is 1, m is 4 and p is 1.
A catalyst system for the polymerization of olefins comprising (a) a metallocene catalyst component represented by the formulas
- (C.sub.5 R'.sub.m).sub.p R".sub.s (C.sub.5 R'.sub.m)MeQ.sub.3-p and
- R".sub.s (C.sub.5 R'.sub.m).sub.2 MeQ'
- wherein Me is a Group 4B metal, at least one (C.sub.5 R'.sub.m) is a di-alkyl, tri-alkyl, tetra-alkyl or penta-alkyl cyclopentadienyl or (C.sub.5 R'.sub.m) is a substituted cyclopentadienyl, each R', which can be the same or different, is hydrogen, an alkenyl, aryl, alkylaryl or arylalkyl radical having from 1 to 20 carbon atoms or two adjacent carbon atoms are joined together to form a C.sub.4 -C.sub.6 ring, R" is a C.sub.1 -C.sub.4 alkylene radical, a dialkyl germanium or silicon, or an alkyl phosphine or amine radical substituting on and bridging two (C.sub.5 R'.sub.m) rings, each Q which can be the same or different is an alkyl or arylalkyl radical having from 1 to 20 carbon atoms, Q' is an alkylidene radical having from 1-20 carbon atoms, s is 0 or 1 and when s is 0, m is 5 and p is 0, 1 or 2 and when s is 1, m is 4 and p is 1;
- at least one R' is a hydrocarbyl radical when at least one Q is an alkyl radical;
- and (b) an alumoxane.
2 more elements
A catalyst system for the polymerization of olefins comprising (a) a metallocene catalyst component represented by the formulas
- (C.sub.5 R'.sub.m).sub.p R".sub.s (C.sub.5 R'.sub.m)MeQ.sub.3-p and
- R".sub.s (C.sub.5 R'.sub.m).sub.2 MeQ'
- wherein Me is a Group 4B metal, a (C.sub.5 R'.sub.m) is a dialkyl, tri-alkyl, tetra-alkyl or penta-alkyl cyclopentadienyl (C.sub.5 R'.sub.m) is a substituted cyclopentadienyl, each R', which can be the same or different, is hydrogen, an alkenyl, aryl, alkylaryl or arylalky radical having from 1 to 20 carbon atoms or two adjacent carbon atoms are joined together to form a C.sub.4 -C.sub.6 ring, R" is an alkylene, germanium, silicon, phosphine or amine radical substituting on and bridging two (C.sub.5 R'.sub.m) rings, each Q which can be the same or different is an aryl, alkyl, alkenyl, alkylaryl, or arylalkyl radical having from 1 to 20 carbon atoms or halogen, Q' is an alkylidene radical having from 1-20 carbon atoms, s is 0 or 1 and when s is 0, m is 5 and p is 0,1 or 2 and when s is 1, m is 4 and p is 1 ;
- at least one R' is a hydrocarbyl radical when at least one O is an alkyl radical;
- and (b) an alumoxane.
2 more elements
A catalyst system for the polymerization of olefins comprising (a) a metallocene catalyst component represented by the formulas
- (C.sub.5 R'.sub.m).sub.p R".sub.s (C.sub.5 R'.sub.m)MeQ.sub.3-p and
- R".sub.s (C.sub.5 R'.sub.m).sub.2 MeQ'
- wherein Me is a Group 4B metal, (C.sub.5 R'.sub.m) is a substituted cyclopentadienyl, each R', which can be the same or different, is hydrogen, alkenyl, aryl, alkylaryl or arylalkyl radical having from 1 to 20 carbon atoms or two adjacent carbon atoms are joined together to form a C.sub.4 -C.sub.6 ring, R" is a C.sub.1 -C.sub.4 alkylene radical, a dialkyl germanium or silicon, or an alkyl phosphine or amine radical substituting on and bridging two (C.sub.5 R'.sub.m) rings, each Q which can be the same or different is an aryl, alkyl, alkenyl, alkylaryl, or arylalkyl radical having from 1 to 20 carbon atoms or halogen, Q' is an alkylidene radical having from 1-20 carbon atoms, s is 0 or 1 and when s is 0, m is 5 and p is 0, 1 or 2 and when s is 1, m is 4 and p is 1;
- at least one R' is a hydrocarbyl radical when at least one Q is an alkyl radical;
- and (b) an alumoxane.
2 more elements
A catalyst system for the polymerization of olefins comprising (a) a single metallocene catalyst component represented by the formulas
- (C.sub.5 R'.sub.m).sub.p R".sub.s (C.sub.5 R'.sub.m)MeQ.sub.3-p and
- R".sub.s (C.sub.5 R'.sub.m).sub.2 MeQ'
- wherein Me is a Group 4B metal, (C.sub.5 R'.sub.m) is a substituted cyclopentadienyl, each R', which can be the same or different, is hydrogen, an alkyl, alkenyl, aryl, alkylaryl or arylalkyl radical having from 1 to 20 carbon atoms or two adjacent carbon atoms are joined together to form a C.sub.4 -C.sub.6 ring, R" is a C.sub.1 -C.sub.4 alkylene radical, a dialkyl germanium or silicon, or an alkyl phosphine or amine radical substituting on and bridging two (C.sub.5 R'.sub.m) rings, each Q which can be the same or different is an aryl, alkenyl, alkylaryl, or arylalkyl radical having from 1 to 20 carbon atoms or halogen, Q' is an alkylidene radical having from 1-20 carbon atoms, s is 0 or 1 and when s is 0, m is 5 and p is 0, 1 or 2 and when s is 1, m is 4 and p is 1;
- and (b) an alumoxane.
1 more element
A catalyst system for the polymerization of olefins comprising (a) a metallocene catalyst component represented by the formulas
- (C.sub.5 R'.sub.m).sub.p R".sub.s (C.sub.5 R'.sub.m)TiQ.sub.3-p and
- R".sub.s (C.sub.5 R'.sub.m).sub.2 TiQ'
- wherein (C.sub.5 R'.sub.m) is a substituted cyclopentadienyl, each R', which can be the same or different, is hydrogen, an alkenyl, aryl, alkylaryl or arylalkyl radical having from 1 to 20 carbon atoms or two adjacent carbon atoms are joined together to form a C.sub.4 -C.sub.6 ring, R" is a C.sub.1 -C.sub.4 alkylene radical, a dialkyl germanium or silicon, or an alkyl phosphine or amine radical substituting on and bridging two (C.sub.5 R'.sub.m) rings, each Q which can be the same or different is an aryl, alkyl, alkenyl, alkylaryl, or arylalkyl radical having from 1 to 20 carbon atoms or halogen, Q' is an alkylidene radical having from 1-20 carbon atoms, s is 0 or 1 and when s is 0, m is 5 and p is 0, 1 or 2 and when s is 1, m is 4 and p is 1;
- at least one R' is a hydrocarbyl radical when at least one Q is an alkyl radical;
- and (b) an alumoxane.
2 more elements
A catalyst system for the polymerization of olefins comprising (a) a metallocene catalyst component represented by the formulas
- (C.sub.5 R'.sub.m).sub.p R".sub.s (C.sub.5 R'.sub.m)TiQ.sub.3-p and
- R".sub.s (C.sub.5 R'.sub.m).sub.2 TiQ'
- wherein (C.sub.5 R'.sub.m) is a substituted cyclopentadienyl, each R', which can be the same or different, is hydrogen, an alkyl, alkenyl, aryl, alkylaryl or arylalkyl radical having from 1 to 20 carbon atoms or two adjacent carbon atoms are joined together to form a C.sub.4 -C.sub.6 ring, R" is a C.sub.1 -C.sub.4 alkylene radical, a dialkyl germanium or silicon, or an alkyl phosphine or amine radical substituting on and bridging two (C.sub.5 R'.sub.m) rings, each Q which can be the same or different is an aryl, alkenyl, alkylaryl, or arylalkyl radical having from 1 to 20 carbon atoms or halogen, Q' is an alkylidene radical having from 1-20 carbon atoms, s is 0 or 1 and when s is 0, m is 5 and p is 0, 1 or 2 and when s is 1, m is 4 and p is 1;
- and (b) an alumoxane.
1 more element
A catalyst system for the polymerization of olefins comprising (a) a metallocene catalyst component represented by the formulas
- (C.sub.5 R'.sub.m).sub.p R".sub.s (C.sub.5 R'.sub.m) ZrQ.sub.3-p and
- R".sub.s (C.sub.5 R'.sub.m).sub.2 ZrQ'
- wherein (C.sub.5 R'.sub.m) is a substituted cyclopentadienyl, each R', which can be the same or different, is hydrogen, an alkyl, alkenyl, aryl, alkylaryl or arylalkyl radical having from 1 to 20 carbon atoms or two adjacent carbon atoms are joined together to form a C.sub.4 -C.sub.6 ring, R" is a C.sub.1 -C.sub.4 alkylene radical, a dialkyl germanium or silicon, or an alkyl phosphine or amine radical substituting on and bridging two (C.sub.5 R'.sub.m) rings, each Q which can be the same or different is an aryl, alkyl, alkenyl, alkylaryl, or arylalkyl radical having from 1 to 20 carbon atoms or halogen, Q' is an alkylidene radical having from 1 to 20 carbon atoms, s is 0 or 1 and when s is 0, m is 5 and p is 0, 1 or 2 and when s is 1, m is 4 and p is 1;
- at least one R' is a hydrocarbyl radical when at least one Q is an alkyl radical;
- and (b) an alumoxane.
2 more elements
A catalyst system for the polymerization of olefins comprising (a) a metallocene catalyst component represented by the formulas
- (C.sub.5 R'.sub.m).sub.p R".sub.s (C.sub.5 R'.sub.m)MeQ.sub.3-p and
- R".sub.s (C.sub.5 R'.sub.m).sub.2 MeQ'
- wherein Me is a Group 4B, 5B, 6B metal, (C.sub.5 R'.sub.m) is a substituted cyclopentadienyl, each R', which can be the same or different, is hydrogen, an alkyl, alkenyl, aryl, alkylaryl or arylalkyl radical having from 1 to 20 carbon atoms or two adjacent carbon atoms are joined together to form a C.sub.4 -C.sub.6 ring, R" is a C.sub.1 -C.sub.4 alkylene radical, a dialkyl germanium or silicon, or an alkyl phosphine or amine radical substituting on and bridging two (C.sub.5 R'.sub.m) rings, each Q which can be the same or different is an aryl, alkyl, alkenyl, alkylaryl, or arylalkyl radical having from 1 to 20 carbon atoms or halogen, Q' is an alkylidene radical having from 1-20 carbon atoms, s is 1 and m is 4 and p is 1;
- at least one R' is a hydrocarbyl radical when at least one Q is an alkyl radical;
- and (b) an alumoxane.
2 more elements
A catalyst system for the polymerization of olefins comprising (a) a metallocene catalyst component represented by the formulas
- (C.sub.5 R'.sub.m).sub.p R".sub.s (C.sub.5 R'.sub.m)MeQ.sub.3-p and
- R".sub.s (C.sub.5 R'.sub.m).sub.2 MeQ'
- wherein Me is a Group 4B metal, (C.sub.5 R'.sub.m) is a substituted cyclopentadienyl, each R', which can be the same or different, is hydrogen, an alkyl, alkenyl, aryl, alkylaryl or arylalkyl radical having from 1 to 20 carbon atoms or two adjacent carbon atoms are joined together to form a C.sub.4 -C.sub.6 ring, R" is a C.sub.1 -C.sub.4 alkylene radical, a dialkyl germanium or silicon, or an alkyl phosphine or amine radical substituting on and bridging two (C.sub.5 R'.sub.m) rings, each Q which can be the same or different is an aryl, alkenyl, alkylaryl, or arylalkyl radical having from 1 to 20 carbon atoms or halogen, Q' is an alkylidene radical having from 1-20 carbon atoms, s is 0 or 1 and when s is 0, m is 5 and p is 0, 1 or 2 and when s is 1, m is 4 and p is 1;
- and (b) an alumoxane.
1 more element
A catalyst system for the polymerization of olefins comprising (a) a metallocene catalyst component represented by the formulas
- (C.sub.5 R'.sub.m).sub.p R".sub.s (C.sub.5 R'.sub.m)MeQ.sub.3-p and
- R".sub.s (C.sub.5 R'.sub.m).sub.2 MeQ'
- wherein Me is a Group 4B, 5B, 6B metal, (C.sub.5 R'.sub.m) is a substituted cyclopentadienyl, each R', which can be the same or different, is hydrogen, alkyl, alkenyl, aryl, alkylaryl or arylalkyl radical having from 1 to 20 carbon atoms or two adjacent carbon atoms are joined together to form a C.sub.4 -C.sub.6 ring, R" is a C.sub.1 -C.sub.4 alkylene radical, a dialkyl germanium or silicon, or an alkyl phosphine or amine radical substituting on and bridging two (C.sub.5 R'.sub.m) rings, each Q which can be the same or different is an ethyl, propyl, butyl, amyl, isoamyl, hexyl, isobutyl, heptyl, octyl, nonyl, decyl, cetyl, alkyl, aryl, alkyl, alkenyl, alkylaryl, or arylalkyl radical having from 1 to 20 carbon atoms or halogen, Q' is an alkylidene radical having from 1-20 carbon atoms, s is 0 or 1 and when s is 0, m is 5 and p is 0, 1 or 2 and when s is 1, m is 4 and p is 1;
- at least one R' is a hydrocarbyl radical when at least one Q is an alkyl radical and (b) an alumoxane.
1 more element
Dependencies are inferred from the claim text.