US4831000A
Expired / Lapsed
US
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Catalyst composition for preparing high density or linear low density olefin polymers of controlled molecular weight distribution
Assignee: ExxonMobil Oil Corp
•
Filing: 1988-01-15
•
Granted: 1989-05-16
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Expires: 2008-01-15
Abstract
Abstract There is disclosed a catalyst composition for the polymerization of olefins, particularly alpha-olefins. The composition is prepared by synthesizing a catalyst precursor and then combining it with a conventional catalyst activator. The precursor is synthesized by: (a) contacting a solid, porous carrier with an aluminum compound; (b) contacting the resulting product with a mixture of vanadium and titanium compounds; (c) contacting the product with an alkyl ether and, (d) pre-activating the product of step (c) with a mixture of a halogenating agent and an aluminum compound. The catalyst composition is used without a halogenating agent in the polymerization medium to produce narrow molecular weight distribution HDPE and LLDPE products, or with a halogenating agent in the polymerization medium to produce broad molecular weight distribution LLDPE and HDPE products.
Inventors
- 👤 Nemesio D. Miro
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-06 17:34
CPC Classifications
C; C08; C08F; C08F10/00; C08F10/02; C08F110/00; C08F110/02; C08F210/00; C08F210/16
Claims Analysis
Total Claims: 54
Claim 1
Independent Claim
210 words
An olefin polymerization catalyst precursor composition prepared by: (a) contacting a solid, porous carrier with an aluminum compound of the formula R.sub.k AlZ.sub.(3-k) (I) where R is a C 1 -C 10 alkyl group, Z is a halogen and k is 1, 2 or 3; (b) contacting the products of step (a) with a mixture containing a vanadium compound of the formula VO.sub.m X.sub.(n-2m) (II) where X is a halogen, m is 0 or 1, and n is 2, 3, 4 or 5, and a titanium compound of the formula TiX.sub.4 ' (III) where X' is a halogen; (c) contacting the product of step (b) with an ether selected from the group consisting of an alkyl ether having 2 to 18 carbon atoms, an alkyl/aryl ether having 2 to 18 carbon atoms, or a silane ether of the formula R"Si(OR'").sub.m R.sub.(3-m).sup.IV (IV) where R", R'" and R IV are the same or different alkyl or aryl groups and m is 1, 2 or 3; (d) pre-activating the product of step (c) with a mixture of a halogenating agent and an aluminum compound of the formula R.sub.n 'AlX.sub.(3-n) " (V) where R' is a C 1 -C 10 alkyl group, X" is a halogen and n is 1, 2 or 3.
Claim 2
Dependent Claim
210 words
An olefin polymerization catalyst precursor composition prepared by: (a) contacting a solid, porous carrier with an aluminum compound of the formula R.sub.k AlZ.sub.(3-k) (I) where R is a C 1 -C 10 alkyl group, Z is a halogen and k is 1, 2 or 3; (b) contacting the products of step (a) with a mixture containing a vanadium compound of the formula VO.sub.m X.sub.(n-2m) (II) where X is a halogen, m is 0 or 1, and n is 2, 3, 4 or 5, and a titanium compound of the formula TiX.sub.4 ' (III) where X' is a halogen; (c) contacting the product of step (b) with an ether selected from the group consisting of an alkyl ether having 2 to 18 carbon atoms, an alkyl/aryl ether having 2 to 18 carbon atoms, or a silane ether of the formula R"Si(OR'").sub.m R.sub.(3-m).sup.IV (IV) where R", R'" and R IV are the same or different alkyl or aryl groups and m is 1, 2 or 3; (d) pre-activating the product of step (c) with a mixture of a halogenating agent and an aluminum compound of the formula R.sub.n 'AlX.sub.(3-n) " (V) where R' is a C 1 -C 10 alkyl group, X" is a halogen and n is 1, 2 or 3.
Claim 3
Dependent Claim
16 words
A catalyst precursor of claim 1 wherein R is a C 2 -C 5 alkyl group.
Claim 4
Dependent Claim
12 words
A catalyst precursor of claim 2 wherein R is an ethyl group.
Claim 5
Dependent Claim
22 words
A catalyst precursor of claim 3 wherein X and X' are each the same or different and they are bromine or chlorine.
Claim 6
Dependent Claim
13 words
A catalyst precursor of claim 4 wherein X and X' are each chlorine.
Claim 7
Dependent Claim
16 words
A catalyst precursor of claim 5 wherein R' is a C 2 -C 5 alkyl group.
Claim 8
Dependent Claim
12 words
A catalyst precursor of claim 6 wherein R' is an ethyl group.
Claim 9
Dependent Claim
12 words
A catalyst precursor of claim 7 wherein X" is bromine or chlorine.
Claim 10
Dependent Claim
18 words
A catalyst precursor of claim 8 wherein the ether is a cyclic alkyl ether or a silane ether.
Claim 11
Dependent Claim
51 words
A catalyst precursor of claim 9 wherein the ether is a cyclic alkyl ether having 2 to 7 carbon atoms or a silane ether of the formula R"Si(OR'").sub.m R.sup.IV where R", R"', and R IV are the same or different alkyl or aryl groups and m is 1, 2 or 3.
Claim 12
Dependent Claim
28 words
A catalyst precursor of claim 10 wherein R" is an aryl group and R"' and R IV are the same or different C 1 -C 4 alkyl groups.
Claim 13
Dependent Claim
13 words
A catalyst precursor of claim 11 wherein the ether is tetrahydrofuran or phenyltrimethoxysilane.
Claim 14
Dependent Claim
18 words
A catalyst precursor of claim 12 wherein the halogenating agent is a silicon halide or a hydrocarbyl halide.
Claim 15
Dependent Claim
14 words
A catalyst precursor of claim 13 wherein the halogenating agent is a hydrocarbyl halide.
Claim 16
Dependent Claim
18 words
A catalyst precursor of claim 14 wherein the halogenating agent is carbon tetrachloride, chloroform, 1,1,1-trichloroethane, dichloromethane or trichlorofluoromethane.
Claim 17
Dependent Claim
15 words
A catalyst precursor of claim 15 wherein the halogenating agent is carbon tetrachloride or chloroform.
Claim 18
Dependent Claim
12 words
A catalyst precursor of claim 16 wherein the halogenating agent is chloroform.
Claim 19
Independent Claim
215 words
A method of preparing an olefin catalyst precursor composition comprising the steps of: (a) contacting a solid, porous carrier with an aluminum compound of the formula R.sub.k AlZ.sub.(3-k) (I) where R is a C 1 -C 10 alkyl group, Z is a halogen and k is 1, 2 or 3; (b) contacting the product of step (a) with a mixture containing a vanadium compound of the formula VO.sub.m X.sub.(n-2m) (II) where X is a halogen, m is 0 or 1, and n is 2, 3, 4 or 5, and a titanium compound of the formula TiX.sub.4 ' (III) wherein X' is a halogen; (c) contacting the product of step (b) with an ether selected from the group consisting of an alkyl ether having 2 to 18 carbon atoms, an alkyl/aryl ether having 2 to 18 carbon atoms, or a silane ether of the formula R"Si(OR'").sub.m R.sub.(3-m).sup.IV (IV) where R", R'" and R IV are the same or different alkyl or aryl groups and m is 1, 2 or 3; (d) pre-activating the product of step (c) with a mixture of a halogenating agent and an aluminum compound of the formula R.sub.n 'AlX.sub.(3-n) " (V) where R' is a C 1 -C 10 alkyl group, X" is a halogen and n is 1, 2 or 3.
Claim 20
Independent Claim
215 words
A method of preparing an olefin catalyst precursor composition comprising the steps of: (a) contacting a solid, porous carrier with an aluminum compound of the formula R.sub.k AlZ.sub.(3-k) (I) where R is a C 1 -C 10 alkyl group, Z is a halogen and k is 1, 2 or 3; (b) contacting the product of step (a) with a mixture containing a vanadium compound of the formula VO.sub.m X.sub.(n-2m) (II) where X is a halogen, m is 0 or 1, and n is 2, 3, 4 or 5, and a titanium compound of the formula TiX.sub.4 ' (III) wherein X' is a halogen; (c) contacting the product of step (b) with an ether selected from the group consisting of an alkyl ether having 2 to 18 carbon atoms, an alkyl/aryl ether having 2 to 18 carbon atoms, or a silane ether of the formula R"Si(OR'").sub.m R.sub.(3-m).sup.IV (IV) where R", R'" and R IV are the same or different alkyl or aryl groups and m is 1, 2 or 3; (d) pre-activating the product of step (c) with a mixture of a halogenating agent and an aluminum compound of the formula R.sub.n 'AlX.sub.(3-n) " (V) where R' is a C 1 -C 10 alkyl group, X" is a halogen and n is 1, 2 or 3.
Claim 21
Dependent Claim
10 words
A catalyst precursor of claim 3 wherein k is 3.
Claim 22
Dependent Claim
17 words
A catalyst precursor of claim 5 wherein the vanadium compound of the formula (II) is vanadium oxytrichloride.
Claim 23
Dependent Claim
90 words
A catalyst precursor of claim 20 wherein in the mixture used in said step (b), the molar ratio of the elemental vanadium (V), derived from the vanadium compound of the formula (II), per unit weight of the carrier is about 0.3 to about 1.0 mmoles of V per gram of the carrier, and the molar ratio of the element titanium (Ti), derived from the titanium compound of the formula (III), per unit weight of the carrier is about 0.05 to about 0.7 mmoles of Ti per gram of the carrier.
Claim 24
Dependent Claim
58 words
A catalyst precursor of claim 21 wherein the molar ratio of V per unit weight of the carrier is about 0.6 to about 1.0 mmole of V per gram of the carrier and the molar ratio of Ti per unit weight of the carrier is about 0.1 to about 0.25 mmole of Ti per gram of the carrier.
Claim 25
Dependent Claim
16 words
A catalyst precursor of claim 22 wherein the molar ratio of V of Ti is 5:1.
Claim 26
Dependent Claim
11 words
A catalyst precursor of claim 12 wherein the ether is tetrahydrofuran.
Claim 27
Dependent Claim
24 words
A catalyst precursor of claim 24 wherein the amount of the tetrahydrofuran is about 0.5 to about 1.3 mmoles per gram of the carrier.
Claim 28
Dependent Claim
24 words
A catalyst precursor of claim 25 wherein the amount of the tetrahydrofuran is about 0.75 to about 1.0 mmoles per gram of the carrier.
Claim 29
Dependent Claim
18 words
A catalyst precursor of claim 26 wherein the molar ratio of the tetrahydrofuran to V is about 1.0.
Claim 30
Dependent Claim
15 words
A method of claim 18 wherein R is a C 2 -C 5 alkyl group.
Claim 31
Dependent Claim
11 words
A method of claim 28 wherein R is an ethyl group.
Claim 32
Dependent Claim
9 words
A method of claim 29 wherein k is 3.
Claim 33
Dependent Claim
21 words
A method of claim 30 wherein X and X' are each the same or different and they are bromine or chlorine.
Claim 34
Dependent Claim
12 words
A method of claim 31 wherein X and X' are each chlorine.
Claim 35
Dependent Claim
16 words
A method of claim 32 wherein the vanadium compound of the formula (II) is vanadium oxytrichloride.
Claim 36
Dependent Claim
89 words
A method of claim 33 wherein in the mixture used in said step (b), the molar ratio of the elemental vanadium (V), derived from the vanadium compound of the formula (II), per unit weight of the carrier is about 0.3 to about 1.0 mmoles of V per gram of the carrier, and the molar ratio of the elemental titanium (Ti), derived from the titanium compound of the formual (III), per unit weight of the carrier is about 0.05 to about 0.7 mmoles of Ti per gram of the carrier.
Claim 37
Dependent Claim
57 words
A method of claim 34 wherein the molar ratio of V per unit weight of the carrier is about 0.6 to about 1.0 mmole of V per gram of the carrier and the molar ratio of Ti per unit weight of the carrier is about 0.1 to about 0.25 mmole of Ti per gram of the carrier.
Claim 38
Dependent Claim
15 words
A method of claim 35 wherein the molar ratio of V to Ti is 5:1.
Claim 39
Dependent Claim
15 words
A method of claim 36 wherein R' is a C 2 -C 5 alkyl group.
Claim 40
Dependent Claim
11 words
A method of claim 37 wherein R' is an ethyl group.
Claim 41
Dependent Claim
11 words
A method of claim 38 wherein X" is bromine or chlorine.
Claim 42
Dependent Claim
17 words
A method of claim 39 wherein the ether is a cyclic alkyl ether or a silane ether.
Claim 43
Dependent Claim
50 words
A method of claim 40 wherein the ether is a cyclic alkyl ether having 2 to 7 carbon atoms or a silane ether of the formula R"Si(OR'").sub.m R.sup.IV where R", R'", and R IV are the same or different alkyl or aryl groups and m is 1, 2 or 3.
Claim 44
Dependent Claim
27 words
A method of claim 41 wherein R" is an aryl group and R'" and R IV are the same or different C 1 -C 4 alkyl groups.
Claim 45
Dependent Claim
12 words
A method of claim 42 wherein the ether is tetrahydrofuran or phenyltrimethoxysilane.
Claim 46
Dependent Claim
10 words
A method of claim 43 wherein the ether is tetrahydrofuran.
Claim 47
Dependent Claim
23 words
A method of claim 44 wherein the amount of the tetrahydrofuran is about 0.5 to about 1.3 mmoles per gram of the carrier.
Claim 48
Dependent Claim
23 words
A method of claim 45 wherein the amount of the tetrahydrofuran is about 0.75 to about 1.0 mmoles per gram of the carrier.
Claim 49
Dependent Claim
17 words
A method of claim 46 wherein the molar ratio of the tetrahydrofuran to V is about 1.0.
Claim 50
Dependent Claim
17 words
A method of claim 47 wherein the halogenating agent is a silicon halide or a hydrocarbyl halide.
Claim 51
Dependent Claim
13 words
A method of claim 48 wherein the halogenating agent is a hydrocarbyl halide.
Claim 52
Dependent Claim
17 words
A method of claim 49 wherein the halogenating agent is carbon tetrachloride, chloroform, 1,1,1-trichloroethane, dichloromethane or trichlorofluoromethane.
Claim 53
Dependent Claim
14 words
A method of claim 50 wherein the halogenating agent is carbon tetrachloride or chloroform.
Claim 54
Dependent Claim
11 words
A method of claim 51 wherein the halogenating agent is chloroform.
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| 3.5 Years (Year 4) | 1992-05-15 | 1992-11-14 | 1993-05-16 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1996-05-15 | 1996-11-14 | 1997-05-16 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2000-05-15 | 2000-11-14 | 2001-05-16 | $7700.00 | Window Closed / Lapsed |