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US5086135A
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Zirconium-based catalyst composition for polymerizing olefins and polymerization therewith
Assignee: Univation Technologies LLC
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Filing: 1989-12-26
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Granted: 1992-02-04
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Expires: 2009-12-26
Abstract
Abstract An olefin polymerization catalyst composition contains: (1) a zirconium compound, containing pi-bonded organic ligands of the formula: Cp.sub.m ZrA.sub.n X.sub.q wherein Cp is unsubstituted or substituted cyclopentadienyl, m is 1, 2 or 3, A is a halogen, hydrogen, a C 1 -C 6 alkyl group, a metalloalkyl or a group of the following general formula: ##STR1## where R is a C 1 -C 10 alkyl group, hydrogen, a halogen or a metalloalkyl group and n is 0, 1 or 2, X is a halogen, hydrogen or a C 1 -C 6 alkyl group, providing that q+m+n=valence or Zr; and (2) a catalyst activator which contains a mixture of (i) an organoaluminum compound having the formula: R.sub.p 'AlX.sub.(k-p) ' or R.sub.3 'Al.sub.2 X.sub.3 ' where R' is a C 1 -C 6 alkyl group, p is 1 or 2, X' is a halogen and k is the valence of aluminum; and (ii) a dialkylmagnesium compound, preferably soluble in hydrocarbons, having the formula: MgR.sub.t " or MgR.sub.r "R.sub.(t-r) " where R" is a C 2 -C 8 alkyl group, R"' is different than R" and it is a C 2 -C 8 alkyl group, t is the valence of magnesium, and r is about 0.01 to about 1.0. There is also disclosed a process for polymerizing olefins in the presence of the catalyst composition.
Inventors
- 👤 Yury V. Kissin
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-30 07:55
CPC Classifications
C; C08; C08F; C08F10/00; C08F4/00; C08F4/42; C08F4/44; C08F4/60; C08F4/62; C08F4/64; C08F4/659; C08F4/65912; C08F4/6592
Claims Analysis
Total Claims: 27
Claim 1
Independent Claim
199 words
A process for polymerizing ethylene alone or in admixture with at least one C 3 -C 10 alpha olefin comprising contacting the ethylene or said admixture under olefin polymerization condition with a catalyst composition comprising: a zirconium compound, containing pi-bonded organic ligands and having the formula: Cp.sub.m ZrA.sub.n X.sub.q wherein Cp is unsubstituted or substituted cyclopentadienyl, m is 1 or 2 or 3, A is a halogen, X is a halogen, hydrogen or C 1 -C 6 alkyl group, providing that q+m+n is equal to the valence of zirconium; in combination with (1) dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum fluoride or mixtures thereof; and (2) a dialkylmagnesium compound having the formula: Mg R.sub.t " or Mg R.sub.r "R.sub.(t-r) "' where R" is a C 2 -C 8 alkyl group, R"' is different than R" and it is a C 2 -C 8 alkyl group, t is the valence of magnesium and r is about 0.01 to about 1, wherein said dimethylaluminum chloride, diethylaluminum chloride or said diethyl aluminum fluoride and said dialkyl magnesium is present in an amount to provide an Al:Mg molar ratio of at least 1:1 and up to about 10:1; and recovering polyolefin product.
Claim 2
Dependent Claim
199 words
A process for polymerizing ethylene alone or in admixture with at least one C 3 -C 10 alpha olefin comprising contacting the ethylene or said admixture under olefin polymerization condition with a catalyst composition comprising: a zirconium compound, containing pi-bonded organic ligands and having the formula: Cp.sub.m ZrA.sub.n X.sub.q wherein Cp is unsubstituted or substituted cyclopentadienyl, m is 1 or 2 or 3, A is a halogen, X is a halogen, hydrogen or C 1 -C 6 alkyl group, providing that q+m+n is equal to the valence of zirconium; in combination with (1) dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum fluoride or mixtures thereof; and (2) a dialkylmagnesium compound having the formula: Mg R.sub.t " or Mg R.sub.r "R.sub.(t-r) "' where R" is a C 2 -C 8 alkyl group, R"' is different than R" and it is a C 2 -C 8 alkyl group, t is the valence of magnesium and r is about 0.01 to about 1, wherein said dimethylaluminum chloride, diethylaluminum chloride or said diethyl aluminum fluoride and said dialkyl magnesium is present in an amount to provide an Al:Mg molar ratio of at least 1:1 and up to about 10:1; and recovering polyolefin product.
Claim 3
Dependent Claim
65 words
The process of claim 1 wherein the catalyst comprises bis(cyclopentadienyl)zirconium dichloride; in combination with (1) dimethyl aluminum chloride, diethyl aluminum chloride diethyl aluminum fluoride or mixtures thereof; and (2) dibutyl magnesium, wherein said dimethylaluminum, diethylaluminum chloride or said diethyl aluminum fluoride and said dibutyl magnesium is present in an amount to provide an Al:Mg molar ratio of at least 1 and up to about 10:1.
Claim 4
Dependent Claim
16 words
The process of claim 1, wherein the molar ratio ranges from about 3:1 to about 5:1.
Claim 5
Dependent Claim
31 words
The process of claim 1, wherein the catalyst is prepared by heating (1) to a temperature of at least 60° C. and then combining it with said zirconium compound and (2).
Claim 6
Dependent Claim
16 words
The process of claim 2, wherein the molar ratio ranges from about 3:1 to about 5:1.
Claim 7
Dependent Claim
31 words
The process of claim 2, wherein the catalyst is prepared by heating (1) to a temperature of at least 60° C. and then combining it with said zirconium compound and (2).
Claim 8
Dependent Claim
18 words
The process of claim 1, wherein the ethylene is admixed with said C 3 -C 10 alpha olefin.
Claim 9
Dependent Claim
18 words
The process of claim 2, wherein the ethylene is admixed with said C 3 -C 10 alpha olefin.
Claim 10
Dependent Claim
13 words
The process of claim 7, wherein the process is a slurry polymerization process.
Claim 11
Dependent Claim
13 words
The process of claim 8, wherein the process is a slurry polymerization process.
Claim 12
Dependent Claim
13 words
The process of claim 1, wherein the process is a slurry polymerization process.
Claim 13
Dependent Claim
13 words
The process of claim 2, wherein the process is a slurry polymerization process.
Claim 14
Dependent Claim
167 words
An ethylene polymerization or copolymerization catalyst comprising: a zirconium compound, containing pi-bonded organic ligands and having the formula: Cp.sub.m ZrA.sub.n X.sub.q wherein Cp is unsubstituted or substituted cyclopentadienyl, m is 1 or 2 or 3, A is a halogen, X is a halogen, hydrogen or C 1 -C 6 alkyl group, providing that q+m+n is equal to the valence of zirconium; in combination with (1) dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum fluoride or mixtures thereof; and (2) a dialkylmagnesium compound having the formula: Mg R.sub.t ' or Mg R.sub.r "R.sub.(t-r) "' where R" is a C 2 -C 8 alkyl group, R"' is different than R" and it is a C 2 -C 8 alkyl group, t is the valence of magnesium and r is about 0.01 to about 1, wherein said dimethylaluminum chloride, diethylaluminum chloride or said diethyl aluminum fluoride and said dialkyl magnesium is present in an amount to provide an Al:Mg molar ratio of at least 1:1 and up to about 10:1.
Claim 15
Dependent Claim
167 words
An ethylene polymerization or copolymerization catalyst comprising: a zirconium compound, containing pi-bonded organic ligands and having the formula: Cp.sub.m ZrA.sub.n X.sub.q wherein Cp is unsubstituted or substituted cyclopentadienyl, m is 1 or 2 or 3, A is a halogen, X is a halogen, hydrogen or C 1 -C 6 alkyl group, providing that q+m+n is equal to the valence of zirconium; in combination with (1) dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum fluoride or mixtures thereof; and (2) a dialkylmagnesium compound having the formula: Mg R.sub.t ' or Mg R.sub.r "R.sub.(t-r) "' where R" is a C 2 -C 8 alkyl group, R"' is different than R" and it is a C 2 -C 8 alkyl group, t is the valence of magnesium and r is about 0.01 to about 1, wherein said dimethylaluminum chloride, diethylaluminum chloride or said diethyl aluminum fluoride and said dialkyl magnesium is present in an amount to provide an Al:Mg molar ratio of at least 1:1 and up to about 10:1.
Claim 16
Dependent Claim
16 words
The catalyst of claim 13, wherein the molar ratio ranges from about 3:1 to about 5:1.
Claim 17
Dependent Claim
31 words
The catalyst of claim 13, wherein the catalyst is prepared by heating (1) to a temperature of at least 60° C. and then combining it with said zirconium compound and (2).
Claim 18
Dependent Claim
15 words
The catalyst of claim 13, wherein R"' and R"' are methyl, ethyl, n-propyl or n-butyl.
Claim 19
Dependent Claim
12 words
The catalyst of claim 13, wherein the magnesium compound is n-butyl, sec-butylmagnesium.
Claim 20
Dependent Claim
116 words
An ethylene polymerization or copolymerization catalyst comprising: a zirconium compound, containing pi-bonded organic ligands and having the formula: Cp.sub.m ZrA.sub.n X.sub.q wherein Cp is unsubstituted or substituted cyclopentadienyl, m is 1 or 2 or 3, A is a halogen, X is a halogen, hydrogen or C 1 -C 6 alkyl group, providing that q+m+n is equal to the valence of zirconium; in combination with (1) dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum fluoride or mixtures thereof; and (2) dibutyl magnesium, wherein said dimethylaluminum chloride, diethylaluminum chloride or said diethyl aluminum fluoride and said dialkyl magnesium is present in an amount to provide an Al:Mg molar ratio of at least 1:1 and up to about 10:1.
Claim 21
Dependent Claim
116 words
An ethylene polymerization or copolymerization catalyst comprising: a zirconium compound, containing pi-bonded organic ligands and having the formula: Cp.sub.m ZrA.sub.n X.sub.q wherein Cp is unsubstituted or substituted cyclopentadienyl, m is 1 or 2 or 3, A is a halogen, X is a halogen, hydrogen or C 1 -C 6 alkyl group, providing that q+m+n is equal to the valence of zirconium; in combination with (1) dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum fluoride or mixtures thereof; and (2) dibutyl magnesium, wherein said dimethylaluminum chloride, diethylaluminum chloride or said diethyl aluminum fluoride and said dialkyl magnesium is present in an amount to provide an Al:Mg molar ratio of at least 1:1 and up to about 10:1.
Claim 22
Dependent Claim
14 words
The catalyst of claim 18, wherein the molar ratio ranges from 3:1 to 5:1.
Claim 23
Dependent Claim
31 words
The catalyst of claim 18, wherein the catalyst is prepared by heating (1) to a temperature of at least 60° C. and then combining it with said zirconium compound and (2).
Claim 24
Dependent Claim
12 words
The catalyst of claim 18, wherein the zirconium compound is bis(cyclopentadienyl)zirconium dichloride.
Claim 25
Dependent Claim
64 words
An ethylene polymerization or copolymerization catalyst comprising bis(cyclopentadienyl)zirconium dichloride in combination with (1) dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum fluoride or mixtures thereof; and (2) dibutyl magnesium, wherein said dimethylaluminum chloride diethylaluminum chloride or said diethyl aluminum fluoride and said dibutyl magnesium is present in an amount to provide an Al:Mg molar ratio of at least 1 and up to about 10:1.
Claim 26
Dependent Claim
64 words
An ethylene polymerization or copolymerization catalyst comprising bis(cyclopentadienyl)zirconium dichloride in combination with (1) dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum fluoride or mixtures thereof; and (2) dibutyl magnesium, wherein said dimethylaluminum chloride diethylaluminum chloride or said diethyl aluminum fluoride and said dibutyl magnesium is present in an amount to provide an Al:Mg molar ratio of at least 1 and up to about 10:1.
Claim 27
Dependent Claim
16 words
The catalyst of claim 22, wherein the molar ratio ranges from about 3 to about 5.
References Cited (Backward Citations)
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