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US4855525A
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Process for preparing linear alpha-olefins using zirconium adducts as catalysts
Assignee: ExxonMobil Chemical Patents Inc
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Filing: 1988-05-18
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Granted: 1989-08-08
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Expires: 2008-05-18
Abstract
Abstract Linear alpha-olefins are prepared by the oligomerization of ethylene using a two component catalyst system comprising (a) a soluble adduct of zirconium tetrahalide, the halogen being Br or Cl, with an organic compound selected from the group of esters, ketones, ethers, amines, nitriles, anhydrides, acid chlorides, amides or aldehydes, the organic compound having up to about 30 carbon atoms and (b) an alkyl metal selected from the group R 2 AlX. RalX 2 , R 3 Al 2 X 3 , R 3 Al and R 2 Zn where R is C 1 -C 20 alkyl and X is Cl or Br. ZrCl 4 adducts with organic acetates are the preferred embodiments.
Inventors
- 👤 David A. Young
- 👤 Larry O. Jones
- 👤 Troy J. Campione
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-02 14:08
CPC Classifications
C; C07; C07C; C07C2/00; C07C2/02; C07C2/04; C07C2/06; C07C2/08; C07C2/26; C07C2/30; B; B01; B01J; B01J31/00; B01J31/02; B01J31/12; B01J31/122; B01J31/14; B01J31/143; B01J31/16; B01J31/22; B01J31/2204; B01J31/2208; B01J2231/00; B01J2231/20; B01J2531/00; B01J2531/40; B01J2531/48; B01J31/18; B01J31/1805; B01J31/26; B01J31/38; C07C2527/00; C07C2527/06; C07C2527/125; C07C2531/00; C07C2531/02; C07C2531/04; C07C2531/12; C07C2531/14; C07C2531/26; C07C2531/38
Claims Analysis
Total Claims: 29
Claim 1
Independent Claim
253 words
A process for preparing substantially linear alpha-olefins of Mn 70 to about 700 by oligomerizing ethylene in the presence of a homogeneous two component catalyst, the first component being an adduct of ZrCl a Br b , where a+b=4 and a or b may be 0, 1, 2, 3 or 4, with an organic compound selected from the group consisting of esters, ketones, ethers, amines, nitriles, anhydrides, acid chlorides, amides or aldehydes, said organic compound having up to 30 carbon atoms and the second component being an alkyl metal catalyst selected from the group consisting of R 2 AlX.RAlX 2 , R 3 Al 12 X 3 , R 3 Al and R 2 Zn wherein R is C 1 -C 20 alkyl and X is Cl or Br, the oligomerization being conducted in a reactor vessel at 50° C. to 300° C. at a pressure of about 500 to 5000 psig in a solution of C 2 -C 100 alpha-olefin or a liquid inert solvent which is not reactive with said catalyst and in which said two component catalyst is soluble with the presence of water in the reactor vessel being minimized such that the ratio of moles of zirconium to moles of water is at least 50 to 1 and wherein in said process the Mn of said alpha-olefin is controlled through adjustment of the molar ratio of second component catalyst to first component catalyst, said ratio being within the range of about 1 to 1 to about 50 to 1.
Claim 2
Dependent Claim
253 words
A process for preparing substantially linear alpha-olefins of Mn 70 to about 700 by oligomerizing ethylene in the presence of a homogeneous two component catalyst, the first component being an adduct of ZrCl a Br b , where a+b=4 and a or b may be 0, 1, 2, 3 or 4, with an organic compound selected from the group consisting of esters, ketones, ethers, amines, nitriles, anhydrides, acid chlorides, amides or aldehydes, said organic compound having up to 30 carbon atoms and the second component being an alkyl metal catalyst selected from the group consisting of R 2 AlX.RAlX 2 , R 3 Al 12 X 3 , R 3 Al and R 2 Zn wherein R is C 1 -C 20 alkyl and X is Cl or Br, the oligomerization being conducted in a reactor vessel at 50° C. to 300° C. at a pressure of about 500 to 5000 psig in a solution of C 2 -C 100 alpha-olefin or a liquid inert solvent which is not reactive with said catalyst and in which said two component catalyst is soluble with the presence of water in the reactor vessel being minimized such that the ratio of moles of zirconium to moles of water is at least 50 to 1 and wherein in said process the Mn of said alpha-olefin is controlled through adjustment of the molar ratio of second component catalyst to first component catalyst, said ratio being within the range of about 1 to 1 to about 50 to 1.
Claim 3
Dependent Claim
25 words
The process of claim 1 wherein the weight ratio of ethylene to zirconium is about 10,000 to 120,000 grams of ethylene per gram of zirconium.
Claim 4
Dependent Claim
13 words
The process of claim 2 wherein said ratio is about 25,000 to 35,000.
Claim 5
Dependent Claim
20 words
The process of claim 1 wherein the molar ratio of zirconium to water is about 2,000 to 10,000 to 1.
Claim 6
Dependent Claim
52 words
The process of claims 1, 2, 3 or 4 wherein said organic compound is an ester of the formula R 1 COOR 2 wherein R 1 and R 2 represent alkyl, aryl, alkaryl or aralkyl groups having a total of 1 to 30 carbon atoms and R 1 may be also H.
Claim 7
Dependent Claim
46 words
The process of claim 5 wherein said organic compound is an acetate ester of the formula CH 3 COOR 1 where R 1 has about 6 to 16 carbon atoms and the adduct is of the formula (ZrCl 4 .CH 3 COOR 1 ) 2 .
Claim 8
Dependent Claim
19 words
The process of claims 1, 2, 3 or 4 wherein said adduct is an adduct of ZrCl 4 .
Claim 9
Dependent Claim
17 words
The process of claim 6 wherein the acetate ester is a mixture of isomers of isodecyl acetate.
Claim 10
Dependent Claim
49 words
The process of claim 1 wherein said ketones have the formula R 1 C(:O)R 2 where R 1 and R 2 represent alkyl, aryl, alkaryl or aralkyl groups having a total of 1 to 30 carbon atoms or a cyclo aliphatic hydrocarbyl group having 4 to 16 carbon atoms.
Claim 11
Dependent Claim
49 words
The process of claim 1 wherein said ethers have the formula R 1 OR 2 where R 1 and R 2 represent alkyl, aryl, alkaryl and aralkyl groups having a total of 1 to 30 carbon atoms or a cyclo aliphatic hydrocarbyl group having 4 to 16 carbon atoms.
Claim 12
Dependent Claim
30 words
The process of claim 1 wherein said aldehydes have the formula R 1 C(:O)H where R 1 represents alkyl, aryl, alkaryl and aralkyl groups having 1 to 30 carbon atoms.
Claim 13
Dependent Claim
30 words
The process of claim 1 wherein said nitriles have the formula RC=N wherein R represents alkyl, aryl, alkaryl and aralkyl groups having a total of 1 to 30 carbon atoms.
Claim 14
Dependent Claim
32 words
The process of claim 1 wherein said anhydrides have the formula (R--C(:O)) 2 O wherein R represents alkyl, aryl, alkaryl and aralkyl groups having a total of 1 to 30 carbon atoms.
Claim 15
Dependent Claim
31 words
The process of claim 1 wherein said acid chlorides have the formula RC(:O)Cl where R represents alkyl, aryl, alkaryl and aralkyl groups having a total of 1 to 30 carbon atoms.
Claim 16
Dependent Claim
35 words
The process of claim 1 wherein said amides have the formulas RC(:O)NH 2 , RC(:O)NHR and RC(:O)NR 2 where R represents alkyl, aryl, alkaryl and aralkyl groups having a total of 1 to 30 atoms.
Claim 17
Dependent Claim
22 words
The process of claims 1, 2, 3 or 4 wherein the substantially linear alpha-olefins have at least 90 mole percent linear alpha-olefins.
Claim 18
Dependent Claim
41 words
The process of claims 1, 2, 3 or 4 wherein the solvent comprises a C 2 -C 100 alpha-olefins which is recycled in the process and which becomes substantially branched C 6 -C 100 alpha-olefins as a result of said recycling.
Claim 19
Dependent Claim
53 words
The process of claims 1, 2, 3 or 4 wherein the linear alpha-olefins have a 4 to 18 carbon atoms and the solvent comprises a C 6 -C 30 alpha-olefins, which is recycled to the reactor vessel and which become substantially branched C 6 -C 30 alpha-olefins as a result of said recycling.
Claim 20
Dependent Claim
16 words
The process of claim 18 wherein the recycled alpha-olefin solvent comprises substantially branched C 20 alpha-olefins.
Claim 21
Dependent Claim
13 words
The process of claim 1 wherein the pressure is 1000 to 3500 psig.
Claim 22
Dependent Claim
32 words
The process of claim 1 where there are added minor proportions of hydrogen whereby the formation of high molecular weight polyethylene having a molecular weight (number average) greater than 10,000 is minimized.
Claim 23
Dependent Claim
24 words
The process of claims 1, 2, 3 or 4 wherein the inert solvent is toluene, xylene or a C 3 to C 24 alkane.
Claim 24
Dependent Claim
62 words
The process of claim 22 wherein the inert solvent is xylene in admixture with C 4 , C 8 and C 10 alpha-olefins, said C 8 and C 10 alpha-olefins being present in the amount of about 10% and said C 4 alphaolefins being present in an amount of 0-5%, said percentages being by weight based on the weight of ethylene feedstock.
Claim 25
Dependent Claim
28 words
The process of claims 1, 2, 3 or 4 wherein the alpha-olefins have about 4 to 24 carbon atoms and are at least 90 mole percent linear alpha-olefins.
Claim 26
Dependent Claim
32 words
The process of claim 6 wherein the acetate is a mixture of isomers of isodecyl acetate and the second catalyst component is diethyl aluminum chloride or ethyl aluminum dichloride or mixtures thereof.
Claim 27
Dependent Claim
25 words
The process of claims 1, 2, 3 or 4 wherein the second catalyst component is diethyl aluminum chloride or ethyl aluminum dichloride or mixtures thereof.
Claim 28
Dependent Claim
29 words
The process of claims 1, 2, 3 or 4 wherein the mole ratio of organic component to zirconium is about 0.9 to 1 up to about 2 to 1.
Claim 29
Dependent Claim
30 words
The process of claims 1, 2, 3 or 4 wherein a solvent comprising liquid alpha-olefins is employed to introduce the catalyst components or the ethylene feedstock into the reactor vessel.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
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| 3.5 Years (Year 4) | 1992-08-07 | 1993-02-06 | 1993-08-08 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1996-08-07 | 1997-02-06 | 1997-08-08 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2000-08-07 | 2001-02-06 | 2001-08-08 | $7700.00 | Window Closed / Lapsed |