IP Library Granted Patent US 9,718,897
Granted Patent B1
US 9,718,897 · App. 15/365,806 · Granted Aug 1, 2017

Process for the polymerization or copolymerization of an alpha olefin

Inventors: Willie Charles Burton (Geismar, LA); David G. Ward (Geismar, LA)
Assignee: Lion Copolymer Geismar, LLC
C08F4/6592C08F2/06C08F4/65908C08F4/65912C08F10/14
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Quick Facts
Patent No.
US 9,718,897
App. No.
15/365,806
Granted
Aug 1, 2017
Kind
B1
Abstract

A solution process for the polymerization or copolymerization of at least one alpha olefin can include adding a Lewis acid to an alkyl aluminum in a hexane or heptane to form a coordination complex, stirring the coordination complex continuously forming a near homogeneous solution in an inert anhydrous environment, adding at least one dry metallocene to the near homogenous solution forming a soluble polymerization initiator, then stirring to form a near homogenous metallocene enriched polymerization initiator, and polymerizing an alpha olefin with the metallocene enriched polymerization initiator and optionally adding additional alkyl aluminum as a moisture scavenger or an impurities scavenger to yield a poly alpha olefin. The at least one dry metallocene can have a transition metal compound. The Lewis acid is capable of forming an ion pair with the at least one dry metallocene.

Claims (17)

1. A solution process for the polymerization or copolymerization of at least one alpha olefin comprising:

a. adding a coordination complex (B) selected from the group consisting of triethylammonium tetraphenylborate, tri(n-butyl)ammonium tetraphenylborate, trimethylammonium tetraphenylborate, triethylammonium tetrakis(pentafluorophenyl)borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, triethylammonium hexafluoroarsenate, pyridinium tetrakis(pentafluorophenyl)borate, pyrrolinium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, and methyldiphenylammonium tetrakis(pentafluorophenyl)borate and ferrocenium tetraphenylborate, dimethylferrocenium tetrakis(pentafluorophenyl)borate, ferrocenium tetrakis(pentafluorophenyl)borate, decamethylferrocenium tetrakis(pentafluorophenyl)borate, acetylferrocenium tetrakis(pentafluorophenyl)borate, formylferrocenium tetrakis(pentafluorophenyl)borate, cyanoferrocenium tetrakis(pentafluorophenyl)borate, silver tetraphenylborate, silver tetrakis(pentafluorophenyl)borate, trityl tetraphenylborate, trityl tetrakis(pentafluorophenyl)borate, and silver tetrafluoroborate to an alkyl aluminum (C) in hexane or heptane (D) to form a mixture;

b. stirring the mixture continuously forming a homogeneous solution in an inert anhydrous environment;

c. adding at least one dry metallocene (A) to the homogenous solution of the coordination complex and alkyl aluminum (C) forming a metallocene catalyst solution, wherein the mole ratio of the metallocene to the coordination complex is from 1:1.5 to 1:3 and the mole ratio of the metallocene to the alkyl aluminum is from 1:15 to 1:500 to form a homogenous metallocene enriched catalyst solution; and

d. polymerizing an alpha olefin with the homogenous metallocene enriched catalyst solution and optionally adding additional alkyl aluminum as a moisture scavenger or an impurities scavenger to yield a polyalpha-olefin with a molecular weight from 250 to 20,000 and a kinematic viscosity at 100 degrees Celsius ranging from 1 cSt to 1000 cSt wherein the metallocene is capable of forming an ion pair with coordination complex (B), and wherein the amounts of coordination complex (B) and alkyl aluminum (C) are 1 mol to 3.0 mol and 15.0 mol to 500 mol, respectively, based on 1 mol of metallocene (A), and the amount of hexane or heptane (D) is 100 parts by mass to 100,000 parts by mass, based on 1 part by mass of the coordination complex.

2. The process of claim 1 , wherein the stirring is from 2 minutes to 60 minutes to form the homogeneous solution.

3. The process of claim 1 , wherein the stirring is from 2 minutes to 60 minutes to form the homogeneous metallocene enriched catalyst solution.

4. The process of claim 1 , wherein the alpha olefin has from 8 carbon atoms to 20 carbon atoms.

5. The process of claim 4 , wherein the alpha olefin is selected from the group consisting of: 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, and 1-undecene.

6. The process of claim 1 , wherein a temperature of polymerization is maintained in a range from 40 degrees Celsius to 120 degrees Celsius.

7. The process of claim 1 , wherein a pressure for the polymerization is maintained from 2 psig to 200 psig.

8. The process of claim 1 , comprising a Zeigler-Natta catalyst blended with the homogenous catalyst solution in a molar ratio of vanadium of the Zeigler-Natty catalyst to metallocene from 0.1:1 to 1:1.

9. The process of claim 1 , wherein the metallocene is a metallocene complex comprising a bridged or unbridged metallocene complex.

10. The process of claim 9 , wherein the metallocene complex comprising an unbridged metallocene complex selected from the group consisting of: biscyclopentadienylzirconium dichloride, bis(n-butylcyclopentadienyl)zirconium dichloride, bis(pentamethylcyclopentadienyl)zirconium dichloride, bisindenylzirconium dichloride, and bis(tetramethylcyclopentadienyl)zirconium dichloride.

11. The process of claim 9 , wherein the metallocene complex comprising the bridged metallocene complex is selected from the group consisting of: dimethylsilylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)zirconium dichloride, dimethylsilylene(tetramethylcyclopentadienyl)(tert-butylamido)zirconium dichloride, dimethylsilylenebis(2-methyl-4,5-benzoindenyl)zirconium dichloride, dimethylsilylenebis(2-methyl-4-phenylindenyl)zirconium dichloride, dimethylsilylenebis(2-methyl-4-naphthylindenyl1)zirconium dichloride, dimethylsilylenebis(2-methylindenyl)zirconium dichloride, ethylenebis(2-methylindenyl)zirconium dichloride, and ethylenebisindenylzirconium dichloride.

12. The process of claim 1 , wherein the alkyl aluminum is selected from the group consisting of: trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum fluoride, diisobutylaluminum hydride, diethylaluminum hydride, and ethylaluminum sesquichloride.

13. The process of claim 1 , wherein the alkyl aluminum is selected from the group consisting of: tetramethyldialuminoxane, tetraisobutyldialuminoxane, methylaluminoxane, ethylalumin oxane, butylaluminoxane, and isobutylaluminoxane.

Assignments (4)
RELEASE OF SECURITY INTEREST Recorded Oct 3, 2023
From: CORTLAND CAPITAL MARKET SERVICES LLC
To: LION COPOLYMER HOLDINGS, LLC; LION COPOLYMER GEISMAR, LLC
Reel/Frame 065109/0547 →
NOTICE OF GRANT OF SECURITY INTEREST IN PATENTS Recorded Nov 7, 2017
From: LION COPOLYMER GEISMAR, LLC
To: BANK OF AMERICA, N.A., AS ADMINISTRATIVE AGENT
Reel/Frame 044387/0654 →
SECURITY INTEREST Recorded Oct 31, 2017
From: LION COPOLYMER HOLDINGS, LLC
To: CORTLAND CAPITAL MARKET SERVICES LLC, AS COLLATERAL AGENT
Reel/Frame 043996/0218 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Nov 30, 2016
From: BURTON, WILLIE CHARLES; WARD, DAVID G.
To: LION COPOLYMER GEISMAR, LLC
Reel/Frame 040472/0279 →
Continuity (3)
Continuation In Part 15247630 · Aug 25, 2016
Continuation In Part 14081937 · Nov 15, 2013
Provisional Application 61728607 · Nov 20, 2012