US5332706A — Process and a catalyst for preventing reactor fou…

Claim 1

Independent Claim 234 words

A process for forming a carrier material impregnated with alumoxane and derivatives thereof comprising (1) providing silica which is porous and has a particle size of 1 to 250 microns, having pores which have an average diameter of 50 to 500 Angstroms and having a pore volume of 0.5 to 5.0 cc/g; (2) providing a volume of a solution comprising alumoxane of formula (a) or (b) wherein (a) is R--(Al(R)--O) x --AlR 2 for oligomeric, linear alumoxanes and (b) is (--Al(R)--O--) y for oligomeric cyclic alumoxane wherein x is 1-40, y is 3-40, and R is a C 1 -C 8 alkyl group and a solvent for said alumoxane, wherein the volume of solution ranges from less than the pore volume of the silica up to a maximum volume of solution which is equal to the total pore volume of the silica, wherein the concentration of alumoxane, expressed as Al weight percent is 5 to 20; wherein the alumoxane provides aluminum in an amount sufficient to provide a ratio of Al to silica (wt/wt) from 0.10 to 0.40; (3) contacting the silica with said volume of said solution and allowing the solution to impregnate the pores of silica, having a pore volume of 0.5 to 5.0 cc/g, containing alumoxane within said pores, without forming a slurry of the silica in the solvent, (4) after said contacting, recovering dry particles of silica impregnated with alumoxane.

Claim 2

Dependent Claim 234 words

A process for forming a carrier material impregnated with alumoxane and derivatives thereof comprising (1) providing silica which is porous and has a particle size of 1 to 250 microns, having pores which have an average diameter of 50 to 500 Angstroms and having a pore volume of 0.5 to 5.0 cc/g; (2) providing a volume of a solution comprising alumoxane of formula (a) or (b) wherein (a) is R--(Al(R)--O) x --AlR 2 for oligomeric, linear alumoxanes and (b) is (--Al(R)--O--) y for oligomeric cyclic alumoxane wherein x is 1-40, y is 3-40, and R is a C 1 -C 8 alkyl group and a solvent for said alumoxane, wherein the volume of solution ranges from less than the pore volume of the silica up to a maximum volume of solution which is equal to the total pore volume of the silica, wherein the concentration of alumoxane, expressed as Al weight percent is 5 to 20; wherein the alumoxane provides aluminum in an amount sufficient to provide a ratio of Al to silica (wt/wt) from 0.10 to 0.40; (3) contacting the silica with said volume of said solution and allowing the solution to impregnate the pores of silica, having a pore volume of 0.5 to 5.0 cc/g, containing alumoxane within said pores, without forming a slurry of the silica in the solvent, (4) after said contacting, recovering dry particles of silica impregnated with alumoxane.

Claim 3

Dependent Claim 10 words

The process of claim 1, wherein the alumoxane is methylalumoxane.

Claim 4

Dependent Claim 28 words

The process of claim 1, which further comprises heating the dry particles to remove solvent from the pores, under temperature conditions effective to prevent crosslinking of the alumoxane.

Claim 5

Dependent Claim 28 words

The process of claim 2, which further comprises heating the dry particles to remove solvent from the pores, under temperature conditions effective to prevent crosslinking of the alumoxane.

Claim 6

Dependent Claim 17 words

The process of claim 3, wherein the temperature ranges from above 30° and below about 60° C.

Claim 7

Dependent Claim 17 words

The process of claim 4, wherein the temperature ranges from above 30° and below about 60° C.

Claim 8

Dependent Claim 104 words

The process of claim 1, which further comprises adding, to said volume of solution prior to said contacting, at least one metallocene compound of the formula: Cp m MA n B p wherein Cp is a cyclopentadienyl or a substituted cyclopentadienyl group; m is 1 or 2; M is zirconium or hafnium; and each of A and B is selected from the group consisting of a halogen atom, a hydrogen atom and an alkyl group, providing that m+n+p is equal to the valence of the metal M; wherein the metallocene compound is admixed with an amount of alumoxane effective to activate the metallocene compound.

Claim 9

Dependent Claim 44 words

The process of claim 7, wherein the metallocene compound is selected from the group consisting of bis(cyclopentadienyl)metal dihalides, bis(cyclopentadienyl)metal hydridohalides, bis(cyclopentadienyl)metal monoalkyl monohalides, bis(cyclopentadienyl)metal dialkyls and bis(indenyl)metal dihalides wherein the metal is zirconium or hafnium, is and alkyl is C 1 -C 6 alkyls.

Claim 10

Dependent Claim 44 words

The process of claim 8, wherein the metallocene compound is selected from the group consisting of bis(cyclopentadienyl)zirconium dichloride, bis(cyclopentadienyl)hafnium dichloride, bis(cyclopentadienyl)zirconium dimethyl, bis(cyclopentadienyl)hafnium dimethyl, bis(cyclopentadienyl)zirconium hydridochloride, bis(cyclopentadienyl)hafnium hydridochloride, bis(pentamethylcyclopentadienyl)zirconium dichloride, bis(pentamethylcyclopentadienyl)hafnium dichloride, bis(n-butylcyclopentadienyl)zirconium dichloride, cyclopentadienyl-zirconium trichloride, bis(indenyl)zirconium dichloride, bis(4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride, and ethylene-[bis(4,5,6,7-tetrahydro-1-indenyl)] zirconium dichloride.

Claim 11

Dependent Claim 27 words

The process of claim 9, wherein solution has a composition which provides a molar ratio of alumoxane, expressed as aluminum, to metallocene ranging from 50 to 500.

Claim 12

Dependent Claim 16 words

The process of claim 1, wherein the dry particles exceed a particle size of 1 micron.

Claim 13

Dependent Claim 24 words

The process of claim 11, which further comprises sieving the dry particles to isolate dry particles characterized by a particle size of 1-250 microns.

Claim 14

Dependent Claim 9 words

The composition produced by the process of claim 1.

Claim 15

Dependent Claim 9 words

The composition produced by the process of claim 11.

Claim 16

Dependent Claim 9 words

The composition produced by the process of claim 7.

Claim 17

Dependent Claim 121 words

The process of claim 7 wherein the silica contains reactive hydroxyl groups (OH), in an amount ranging from 0.1 to 3.0 mmols/g carrier, and wherein the reactive hydroxyl groups are reacted, prior to said contacting of (3), with an organomagnesium compound, so that the Mg:OH molar ratio ranges from 0.5:1 to 4:1 wherein the organomagnesium compound has the formula R.sub.a Mg R'.sub.b where R and R' are the same or different C 2 -C 8 alkyl groups, and a and b are each 0, 1 or 2, providing that a+b is equal to the valence of Mg; and, after the reactive hydroxyl groups are reacted but prior to said contacting of 3, adding a non-metallocene transition metal compound to the slurry.

Claim 18

Dependent Claim 13 words

The process of claim 16, wherein both R and R' are n-butyl groups.

Claim 19

Dependent Claim 14 words

The process of claim 17, wherein the non-metallocene compound is a tetravalent titanium compound.

Claim 20

Dependent Claim 27 words

The process of claim 18, wherein the tetravalent titanium compound is provided in an amount which is sufficient to provide a metallocene:Ti ratio of 0.01 to 0.50.

Claim 21

Dependent Claim 9 words

A product produced by the process of claim 12.

Claim 22

Dependent Claim 9 words

A product produced by the process of claim 17.

Claim 23

Dependent Claim 9 words

A product produced by the process of claim 18.

Claim 24

Dependent Claim 9 words

A product produced by the process of claim 19.

Claim 25

Dependent Claim 24 words

The process of claim 19, which further comprises sieving the dry particles to isolate dry particles characterized by a particle size of 1-250 microns.

Claim 26

Dependent Claim 9 words

A product produced by the process of claim 24.

Claim 27

Dependent Claim 10 words

The process of claim 8, wherein the halide is chlorine.

Claim 28

Dependent Claim 240 words

In a catalyst composition which comprises a catalyst precursor and a cocatalyst free of alumoxane, which catalyst is effective to produce polymers and copolymers of ethylene, the improvement comprising a precursor, effective to produce bimodal molecular weight distribution product with said cocatalyst, wherein said precursor comprises particles wherein the particles comprise silica, having a pore volume of 0.5 to 5.0 cc/gram; containing reactive hydroxyl groups, (OH), ranging form 0.1 to 3.0 mmols/gram silica; and Mg, provided as an organomagnesium compound, in an amount to provide a Mg:OH molar ratio of from 0.5:1 to 4:1, wherein the organomagnesium compound has the formula R.sub.a Mg R'.sub.b where R and R' are the same or different C 2 -C 8 alkyl groups, and a and b are each 0, 1 or 2, providing that a+b is equal to the valence of Mg; and wherein the organomagnesium compound is reacted with said hydroxyl groups, and thereafter contacted with a non-metallocene transition metal compound, which is supported on said silica; wherein the silica is impregnated with an activated metallocene compound, wherein the metallocene compound has the formula Cp.sub.m Ma.sub.n B.sub.p wherein Cp is a cyclopentadienyl or a substituted cyclopentadienyl group; m is 1 or 2; M is zirconium or hafnium; and each of A and B is selected from the group consisting of a halogen atom, a hydrogen atom and an alkyl group, providing that m+n+p is equal to the valence of the metal M.

Claim 29

Dependent Claim 240 words

In a catalyst composition which comprises a catalyst precursor and a cocatalyst free of alumoxane, which catalyst is effective to produce polymers and copolymers of ethylene, the improvement comprising a precursor, effective to produce bimodal molecular weight distribution product with said cocatalyst, wherein said precursor comprises particles wherein the particles comprise silica, having a pore volume of 0.5 to 5.0 cc/gram; containing reactive hydroxyl groups, (OH), ranging form 0.1 to 3.0 mmols/gram silica; and Mg, provided as an organomagnesium compound, in an amount to provide a Mg:OH molar ratio of from 0.5:1 to 4:1, wherein the organomagnesium compound has the formula R.sub.a Mg R'.sub.b where R and R' are the same or different C 2 -C 8 alkyl groups, and a and b are each 0, 1 or 2, providing that a+b is equal to the valence of Mg; and wherein the organomagnesium compound is reacted with said hydroxyl groups, and thereafter contacted with a non-metallocene transition metal compound, which is supported on said silica; wherein the silica is impregnated with an activated metallocene compound, wherein the metallocene compound has the formula Cp.sub.m Ma.sub.n B.sub.p wherein Cp is a cyclopentadienyl or a substituted cyclopentadienyl group; m is 1 or 2; M is zirconium or hafnium; and each of A and B is selected from the group consisting of a halogen atom, a hydrogen atom and an alkyl group, providing that m+n+p is equal to the valence of the metal M.

Claim 30

Dependent Claim 73 words

The catalyst of claim 27, wherein the metallocene is activated with an alumoxane of the formula (a) or (b) wherein (a) is R--(Al(R)--O) x --AlR 2 for oligomeric, linear alumoxanes and (b) is (--Al(R)--O--) y for oligomeric cyclic alumoxane wherein x is 1-40, y is 3-40, and R is a C 1 -C 8 alkyl group and wherein the molar ratio of alumoxane, expressed as aluminum, to metallocene ranges from 50 to 500.

Claim 31

Dependent Claim 10 words

The catalyst of claim 27, wherein the cocatalyst is trialkylaluminum.

Claim 32

Dependent Claim 10 words

The catalyst of claim 29, wherein the cocatalyst is trimethylaluminum.

Claim 33

Dependent Claim 10 words

The catalyst of claim 28, wherein the cocatalyst is trialkylaluminum.

Claim 34

Dependent Claim 10 words

The catalyst of claim 31, wherein the cocatalyst is trimethylaluminum.

Claim 35

Dependent Claim 16 words

The catalyst of claim 27, wherein the non-metallocene transition metal compound is a tetravalent titanium compound.

Claim 36

Dependent Claim 26 words

The catalyst of claim 33, wherein the tetravalent titanium compound is provided in an amount sufficient to provide a metallocene :Ti ratio of 0.01 to 0.50.

Claim 37

Dependent Claim 11 words

The catalyst of claim 34, wherein the organomagnesium compound is dibutylmagnesium.

Claim 38

Dependent Claim 44 words

The catalyst of claim 35, wherein the metallocene is selected from the group consisting of bis(cyclopentadienyl)metal dihalides, bis(cyclopentadienyl)metal hydridohalides, bis(cyclopentadienyl)metal monoalkyl monohalides, bis(cyclopentadienyl)metal dialkyls and bis(indenyl)metal dihalides wherein the metal is zirconium or hafnium, and the alkyl groups are C 1 -C 6 alkyls.

Claim 39

Dependent Claim 43 words

The process of claim 36, wherein the metallocene is selected from the group consisting of bis(cyclopentadienyl)zirconium dichloride, bis(cyclopentadienyl)hafnium dichloride, bis(cyclopentadienyl)zirconium dimethyl, bis(cyclopentadienyl)hafnium dimethyl, bis(cyclopentadienyl)zirconium hydridochloride, bis(cyclopentadienyl)hafnium hydridochloride, bis(pentamethylcyclopentadienyl)zirconium dichloride, bis(pentamethylcyclopentadienyl)hafnium dichloride, bis(n-butylcyclopentadienyl)zirconium dichloride, cyclopentadienylzirconium trichloride, bis(indenyl)zirconium dichloride, bis(4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride, and ethylene-[bis(4,5,6,7-tetrahydro-1-indenyl)] zirconium dichloride.

Claim 40

Dependent Claim 10 words

The catalyst of claim 37, wherein the alumoxane is methylalumoxane.

Claim 41

Dependent Claim 250 words

A catalyst compound, which contains activated metallocene compound, and which obviates feeding alumoxane solutions to a polymerization reactor, wherein the catalyst composition comprises a cocatalyst which is a monomeric trialkylaluminum, free of oligomeric or polymeric reaction products of trialkylaluminum and water, and a catalyst precursor, wherein the catalyst precursor comprises particles wherein the particles comprise silica, having a pore volume of 0.5 to 5.0 cc/gram; containing reactive hydroxyl groups, (OH), ranging from 0.1 to 3. 0 mmols/gram silica; and Mg, provided as an organomagnesium compound, in an amount to provide a Mg:OH molar ratio of from 0.5:1 to 4:1, wherein the organomagnesium compound has the formula R a Mg R' b where R and R' are the same or different C 2 -C 8 alkyl groups, and a and b are each 0, 1 or 2, providing that a+b is equal to the valence of Mg; and wherein the organomagnesium compound is reacted with said hydroxy groups, and thereafter contacted with a non-metallocene transition metal compound, which is supported on said silica; wherein the silica is impregnated with an activated metallocene compound, wherein the metallocene compound has the formula Cp m MA n B p wherein Cp is a cyclopentadienyl or a substituted cyclopentadienyl group; m is 1 or 2; M is zirconium or hafnium; and each of A and B is selected from the group consisting of a halogen atom, a hydrogen atom and an alkyl group, providing that m+n+p is equal to the valence of the metal M.

Claim 42

Dependent Claim 250 words

A catalyst compound, which contains activated metallocene compound, and which obviates feeding alumoxane solutions to a polymerization reactor, wherein the catalyst composition comprises a cocatalyst which is a monomeric trialkylaluminum, free of oligomeric or polymeric reaction products of trialkylaluminum and water, and a catalyst precursor, wherein the catalyst precursor comprises particles wherein the particles comprise silica, having a pore volume of 0.5 to 5.0 cc/gram; containing reactive hydroxyl groups, (OH), ranging from 0.1 to 3. 0 mmols/gram silica; and Mg, provided as an organomagnesium compound, in an amount to provide a Mg:OH molar ratio of from 0.5:1 to 4:1, wherein the organomagnesium compound has the formula R a Mg R' b where R and R' are the same or different C 2 -C 8 alkyl groups, and a and b are each 0, 1 or 2, providing that a+b is equal to the valence of Mg; and wherein the organomagnesium compound is reacted with said hydroxy groups, and thereafter contacted with a non-metallocene transition metal compound, which is supported on said silica; wherein the silica is impregnated with an activated metallocene compound, wherein the metallocene compound has the formula Cp m MA n B p wherein Cp is a cyclopentadienyl or a substituted cyclopentadienyl group; m is 1 or 2; M is zirconium or hafnium; and each of A and B is selected from the group consisting of a halogen atom, a hydrogen atom and an alkyl group, providing that m+n+p is equal to the valence of the metal M.

Claim 43

Dependent Claim 73 words

The catalyst of claim 39, wherein the metallocene is activated with an alumoxane of the formula (a) or (b) wherein (a) is R--(Al(R)--O) x --AlR 2 for oligomeric, linear alumoxanes and (b) is (--Al(R)--O--) y for oligomeric cyclic alumoxane wherein x is 1-40, y is 3-40, and R is a C 1 -C 8 alkyl group and wherein the molar ratio of alumoxane, expressed as aluminum, to metallocene ranges from 50 to 500.

Claim 44

Dependent Claim 10 words

The catalyst of claim 39, wherein the cocatalyst is trialkylaluminum.

Claim 45

Dependent Claim 10 words

The catalyst of claim 41, wherein the cocatalyst is trimethylaluminum.

Claim 46

Dependent Claim 10 words

The catalyst of claim 40, wherein the cocatalyst is trialkylaluminum.

Claim 47

Dependent Claim 10 words

The catalyst of claim 43, wherein the cocatalyst is trimethylaluminum.

Claim 48

Dependent Claim 16 words

The catalyst of claim 39, wherein the non-metallocene transition metal compound is a tetravalent titanium compound.

Claim 49

Dependent Claim 25 words

The catalyst of claim 45, wherein the tetravalent titanium compound is provided in an amount sufficient to provide a metallocene:Ti ratio of 0.01 to 0.50.

Claim 50

Dependent Claim 11 words

The catalyst of claim 46, wherein the organomagnesium compound is dibutylmagnesium.

Claim 51

Dependent Claim 42 words

The catalyst of claim 47, wherein the metallocene is selected from the group consisting of bis(cyclopentadienyl)metal dihalides, bis(cyclopentadienyl)metal hydridohalides, bis(cyclopentadienyl)metal monoalkyl monohalides, bis(cyclopentadienyl)metal dialkyls and bis(indenyl)metal dihalides wherein the metal is zirconium or hafnium, and alkyl contains 1 to 6 carbon atoms.

Claim 52

Dependent Claim 43 words

The catalyst of claim 48, wherein the metallocene is selected from the group consisting of bis(cyclopentadienyl)zirconium dichloride, bis(cyclopentadienyl)hafnium dichloride, bis(cyclopentadienyl)zirconium dimethyl, bis(cyclopentadienyl)hafnium dimethyl, bis(cyclopentadienyl)zirconium hydridochloride, bis(cyclopentadienyl)hafnium hydridochloride, bis(pentamethylcyclopentadienyl)zirconium dichloride, bis(pentamethylcyclopentadienyl)hafnium dichloride, bis(n-butylcyclopentadienyl)zirconium dichloride, cyclopentadienylzirconium trichloride, bis(indenyl)zirconium dichloride, bis(4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride, and ethylene-[bis(4,5,6,7-tetrahydro-1-indenyl)] zirconium dichloride.

Claim 53

Dependent Claim 10 words

The catalyst of claim 40, wherein the alumoxane is methylalumoxane.

Claim 54

Dependent Claim 20 words

The catalyst of claim 45, wherein the metallocene is selected from the group consisting of bis(cyclopentadienyl)zirconium dichloride and bis-(butylcyclopentadienyl)zirconium dichloride.

Claim 55

Dependent Claim 40 words

The catalyst of claim 39 wherein the activated metallocene compound is formed in a solution of an alumoxane and said metallocene compound, wherein the solution has a maximum volume which is equal to the total pore volume of said silica.

Claim 56

Dependent Claim 40 words

The catalyst of claim 40 wherein the activated metallocene compound is formed in a solution of an alumoxane and said metallocene compound, wherein the solution has a maximum volume which is equal to the total pore volume of said silica.

Claim 57

Dependent Claim 40 words

The catalyst of claim 43 wherein the activated metallocene compound is formed in a solution of an alumoxane and said metallocene compound, wherein the solution has a maximum volume which is equal to the total pore volume of said silica.

Claim 58

Dependent Claim 40 words

The catalyst of claim 44 wherein the activated metallocene compound is formed in a solution of an alumoxane and said metallocene compound, wherein the solution has a maximum volume which is equal to the total pore volume of said silica.

Claim 59

Dependent Claim 40 words

The catalyst of claim 46 wherein the activated metallocene compound is formed in a solution of an alumoxane and said metallocene compound, wherein the solution has a maximum volume which is equal to the total pore volume of said silica.

Claim 60

Dependent Claim 40 words

The catalyst of claim 51 wherein the activated metallocene compound is formed in a solution of an alumoxane and said metallocene compound, wherein the solution has a maximum volume which is equal to the total pore volume of said silica.

Annuity Stage	Window Opens	Payment Deadline	Surcharge Period Until	Estimated Fee	Status
3.5 Years (Year 4)	1997-07-25	1998-01-24	1998-07-26	$2000.00	Window Closed / Lapsed
7.5 Years (Year 8)	2001-07-25	2002-01-24	2002-07-26	$3760.00	Window Closed / Lapsed
11.5 Years (Year 12)	2005-07-25	2006-01-24	2006-07-26	$7700.00	Window Closed / Lapsed

Process and a catalyst for preventing reactor fouling

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