Patent US4912074A successfully refreshed from Google Patents.
US4912074A
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Catalyst composition for preparing high density or medium density olefin polymers
Assignee: Mobil Oil AS
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Filing: 1988-10-05
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Granted: 1990-03-27
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Expires: 2008-10-05
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; and, (c) contacting the product with an ether. The catalyst composition is used with a conventional activator and, preferably, a halogenating agent in the polymerization medium to produce broad molecular weight distribution, high molecular weight HDPE or medium density, broad molecular weight distribution, high molecular weight resins which can be made into high strength films.
Inventors
- 👤 Nemesio D. Miro
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-09 04:57
CPC Classifications
C; C08; C08F; C08F10/00; C08F10/02; C08F110/00; C08F110/02; C08F210/00; C08F210/16
Claims Analysis
Total Claims: 70
Claim 1
Independent Claim
173 words
An olefin polymerization catalyst precursor composition prepared by a process comprising the steps of: (a) contacting a solid, porous carrier with an aluminum compound of the formula R.sub.k Al Z.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 Ti X'.sub.4 (III) where X' is a halogen; and (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.sup.IV.sub.(3-m) (IV) where R", R'" and R IV are the same or different alkyl or aryl groups and m is 1, 2 or 3.
Claim 2
Dependent Claim
173 words
An olefin polymerization catalyst precursor composition prepared by a process comprising the steps of: (a) contacting a solid, porous carrier with an aluminum compound of the formula R.sub.k Al Z.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 Ti X'.sub.4 (III) where X' is a halogen; and (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.sup.IV.sub.(3-m) (IV) where R", R'" and R IV are the same or different alkyl or aryl groups and m is 1, 2 or 3.
Claim 3
Dependent Claim
16 words
A catalyst precursor of claim 1 where 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
10 words
A catalyst precursor of claim 3 wherein k is 3.
Claim 6
Dependent Claim
22 words
A catalyst precursor of claim 4 wherein X and X' are each the same or different and they are bromine or chlorine.
Claim 7
Dependent Claim
13 words
A catalyst precursor of claim 5 wherein X and X' are each chlorine.
Claim 8
Dependent Claim
17 words
A catalyst precursor of claim 5 wherein the vanadium compound of the formula (II) is vanadium oxytrichloride.
Claim 9
Dependent Claim
18 words
A catalyst precursor of claim 7 wherein the ether is a cyclic alkyl ether or a silane ether.
Claim 10
Dependent Claim
50 words
A catalyst precursor of claim 8 wherein the ether is a cyclic alkyl ether having 2 to 7 carbon atoms or a silane ether of the formula R" Si(OR'")R.sup.IV.sub.(3-m) where R", R'", and R IV are the same or different alkyl or aryl groups and m is 1,2, or 3.
Claim 11
Dependent Claim
28 words
A catalyst precursor of claim 9 wherein R" is an aryl group and R'" and R IV are the same or different C 1 -C 4 alkyl groups.
Claim 12
Dependent Claim
13 words
A catalyst precursor of claim 10 wherein the ether is tetrahydrofuran or phenyltrimethoxysilane.
Claim 13
Dependent Claim
11 words
A catalyst precursor of claim 11 wherein the ether is tetrahydrofuran.
Claim 14
Dependent Claim
22 words
A catalyst precursor of claim 12 wherein the amount of the tetrahydrofuran is about 0.1 to about 2.0 mmoles/gram of the carrier.
Claim 15
Dependent Claim
22 words
A catalyst precursor of claim 13 wherein the amount of the tetrahydrofuran is about 0.5 to about 1.5 mmoles/gram of the carrier.
Claim 16
Dependent Claim
19 words
A catalyst precursor of claim 14 wherein the amount of the tetrahydrofuran is about 1.0 mmole/gram of the carrier.
Claim 17
Dependent Claim
28 words
A catalyst precursor of claim 15 wherein the molar ratio of V per weight unit of the carrier is about 0.3 to about 2.0 mmole/gram of the carrier.
Claim 18
Dependent Claim
28 words
A catalyst precursor of claim 16 wherein the molar ratio of V per weight unit of the carrier is about 0.7 to about 1.3 mmole/gram of the carrier.
Claim 19
Dependent Claim
25 words
A catalyst precursor of claim 17 wherein the molar ratio of V per weight unit of the carrier is about 1.0 mmole/gram of the carrier.
Claim 20
Dependent Claim
28 words
A catalyst precursor of claim 18 wherein the molar ratio of Ti per unit weight of the carrier is about 0.05 to about 1.0 mmoles/gram of the carrier.
Claim 21
Dependent Claim
28 words
A catalyst precursor of claim 19 wherein the molar ratio of Ti per unit weight of the carrier is about 0.1 to about 0.4 mmoles/gram of the carrier.
Claim 22
Dependent Claim
25 words
A catalyst precursor of claim 20 wherein the molar ratio of Ti per unit weight of the carrier is about 0.2 mmoles/gram of the carrier.
Claim 23
Dependent Claim
21 words
A catalyst precursor of claim 21 wherein the steps (a), (b) and (c) are conducted in the presence of a solvent.
Claim 24
Dependent Claim
12 words
A catalyst precursor of claim 22 wherein the solvent is an alkane.
Claim 25
Dependent Claim
16 words
A catalyst precursor of claim 23 wherein the alkane is hexane, n-heptane, octane, nonane or decane.
Claim 26
Dependent Claim
11 words
A catalyst precursor of claim 24 wherein the alkane is hexane.
Claim 27
Dependent Claim
15 words
A catalyst precursor of claim 23 wherein the carrier is silica, alumina or combinations thereof.
Claim 28
Dependent Claim
29 words
A catalyst precursor of claim 26 wherein the carrier is silica dehydrated by fluidizing it with air and heating at about 600° C. for about 8 to 16 hours.
Claim 29
Dependent Claim
26 words
A catalyst precursor of claim 21 wherein the aluminum compound is trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tributylaluminum, triisobutylaluminum, tripentylaluminum, tri-n-hexylaluminum, triheptyl aluminum, diethylaluminum chloride or ethylaluminum dichloride.
Claim 30
Dependent Claim
12 words
A catalyst precursor of claim 28 wherein the aluminum compound is triethylaluminum.
Claim 31
Dependent Claim
46 words
A catalyst precursor of claim 28 wherein the amount of the aluminum compound is such that the ratio of Al, derived from the aluminum compound, per weight unit of the carrier is about 0.5 to about 2.0 mmoles of the Al per gram of the carrier.
Claim 32
Dependent Claim
33 words
A catalyst precursor of claim 30 wherein the ratio of the Al per weight unit of the carrier is about 0.8 to about 1.3 mmoles of the Al per gram of the carrier.
Claim 33
Dependent Claim
30 words
A catalyst precursor of claim 31 wherein the ratio of the Al per weight unit of the carrier is about 1.0 mmoles of the Al per gram of the carrier.
Claim 34
Dependent Claim
36 words
A catalyst precursor of claim 29 wherein the ratio of Al, derived from the triethylaluminum, per weight unit of the carrier is about 0.5 to about 2.0 mmoles of the Al per gram of the carrier.
Claim 35
Dependent Claim
36 words
A catalyst precursor of claim 33 wherein the ratio of Al, derived from the triethylaluminum, per weight unit of the carrier is about 0.8 to about 1.3 mmoles of the Al per gram of the carrier.
Claim 36
Dependent Claim
33 words
A catalyst precursor of claim 34 wherein the ratio of Al, derived from the triethylaluminum, per weight unit of the carrier is about 1.0 mmoles of the Al per gram of the carrier.
Claim 37
Dependent Claim
34 words
An activated olefin polymerization catalyst composition comprising the precursor of claim 1 and a catalyst activator containing a compound of Group IB, IIA, IIB, IIIB or IVB of the Periodic Chart of the Elements.
Claim 38
Dependent Claim
27 words
A catalyst composition of claim 36 wherein the activator is a Group IIIB metal alkyl or a dialkylhalide having 1 to 20 carbon atoms per alkyl radical.
Claim 39
Dependent Claim
22 words
A catalyst composition of claim 37 wherein the activator is a trialkylaluminum compound having 1 to 6 carbon atoms per alkyl radical.
Claim 40
Dependent Claim
11 words
A catalyst composition of claim 60 wherein the activator is triethylaluminum.
Claim 41
Dependent Claim
34 words
An activated olefin polymerization catalyst composition comprising the precursor of claim 35 and a catalyst activator containing a compound of Group IB, IIA, IIB, IIIB or IVB of the Periodic Chart of the Elements.
Claim 42
Dependent Claim
27 words
A catalyst composition of claim 40 wherein the activator is a group IIIB metal alkyl or a dialkylhalide having 1 to 20 carbon atoms per alkyl radical.
Claim 43
Dependent Claim
22 words
A catalyst composition of claim 41 wherein the activator is a trialkylaluminum compound having 1 to 6 carbon atoms per alkyl radical.
Claim 44
Dependent Claim
11 words
A catalyst composition of claim 42 wherein the activator is triethylaluminum.
Claim 45
Independent Claim
173 words
A method of preparing an olefin polymerization catalyst precursor composition comprising the steps or: (a) contacting a solid, porous carrier with an aluminum compound of the formula R.sub.k Al Z.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 Ti X'.sub.4 (III) where X' is a halogen; and (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.sup.IV.sub.(3-m) (IV) where R", R'" or R IV are the same or different alkyl or aryl groups and m is 1, 2 or 3.
Claim 46
Independent Claim
173 words
A method of preparing an olefin polymerization catalyst precursor composition comprising the steps or: (a) contacting a solid, porous carrier with an aluminum compound of the formula R.sub.k Al Z.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 Ti X'.sub.4 (III) where X' is a halogen; and (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.sup.IV.sub.(3-m) (IV) where R", R'" or R IV are the same or different alkyl or aryl groups and m is 1, 2 or 3.
Claim 47
Dependent Claim
15 words
A method of claim 44 wherein R is a C 2 -C 5 alkyl group.
Claim 48
Dependent Claim
11 words
A method of claim 45 wherein R is an ethyl group.
Claim 49
Dependent Claim
9 words
A method of claim 46 wherein k is 3.
Claim 50
Dependent Claim
21 words
A method of claim 47 wherein X and X' are each the same or different and they are bromine or chlorine.
Claim 51
Dependent Claim
12 words
A method of claim 48 wherein X and X' are each chlorine.
Claim 52
Dependent Claim
16 words
A method of claim 49 wherein the vanadium compound of the formula (II) is vanadium oxytrichloride.
Claim 53
Dependent Claim
17 words
A method of claim 50 wherein the ether is a cyclic alkyl ether or a silane ether.
Claim 54
Dependent Claim
49 words
A method of claim 51 wherein the ether is a cyclic alkyl ether having 2 to 7 carbon atoms or a silane ether of the formula R" Si(OR'")R.sup.IV.sub.(3-m) where R", R'", and R IV are the same or different alkyl or aryl groups and m is 1,2, or 3.
Claim 55
Dependent Claim
27 words
A method of claim 52 wherein R" is an aryl group and R'" and R IV are the same of different C 1 -C 4 alkyl groups.
Claim 56
Dependent Claim
12 words
A method of claim 53 wherein the ether is tetrahydrofuran or phenyltrimethoxysilane.
Claim 57
Dependent Claim
10 words
A method of claim 54 wherein the ether is tetrahydrofuran.
Claim 58
Dependent Claim
21 words
A method of claim 55 wherein the amount of the tetrahydrofuran is about 0.1 to about 2.0 mmoles/gram of the carrier.
Claim 59
Dependent Claim
21 words
A method of claim 56 wherein the amount of the tetrahydrofuran is about 0.5 to about 1.5 mmoles/gram of the carrier.
Claim 60
Dependent Claim
18 words
A method of claim 57 wherein the amount of the tetrahydrofuran is about 1.0 mmole/gram of the carrier.
Claim 61
Dependent Claim
27 words
A method of claim 58 wherein the molar ratio of V per weight unit of the carrier is about 0.3 to about 2.0 mmmole/gram of the carrier.
Claim 62
Dependent Claim
27 words
A method of claim 59 wherein the molar ratio of V per weight unit of the carrier is about 0.7 to about 1.3 mmole/gram of the carrier.
Claim 63
Dependent Claim
24 words
A method of claim 60 wherein the molar ratio of V per weight unit of the carrier is about 1.0 mmole/gram of the carrier.
Claim 64
Dependent Claim
27 words
A method of claim 61 wherein the molar ratio of Ti per unit weight of the carrier is about 0.05 to about 0.1 mmoles/gram of the carrier.
Claim 65
Dependent Claim
27 words
A method of claim 62 wherein the molar ratio of Ti per unit weight of the carrier is about 0.1 to about 0.4 mmoles/gram of the carrier.
Claim 66
Dependent Claim
24 words
A method of claim 63 wherein the molar ratio of Ti per unit weight of the carrier is about 0.2 mmoles/gram of the carrier.
Claim 67
Dependent Claim
20 words
A method of claim 64 wherein the steps (a), (b) and (c) are conducted in the presence of a solvent.
Claim 68
Dependent Claim
11 words
A method of claim 65 wherein the solvent is an alkane.
Claim 69
Dependent Claim
15 words
A method of claim 66 wherein the alkane is hexane, n-heptane, octane, nonane or decane.
Claim 70
Dependent Claim
10 words
A method of claim 67 wherein the alkane is hexane.
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