IP Library Granted Patent US 7,129,306
Granted Patent B2
US 7,129,306 · App. 10/761,515 · Granted Oct 31, 2006

Process for the oligomerization of α-olefins having low unsaturation

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Quick Facts
Patent No.
US 7,129,306
App. No.
10/761,515
Granted
Oct 31, 2006
Kind
B2
Abstract

A process is disclosed for the preparation of a poly(α-olefin) polymer wherein the process comprises polymerizing at least one α-olefin in the presence of hydrogen and a catalytically effective amount of catalyst comprising the product obtained by combining a metallocene catalyst with a cocatalyst, the metallocene catalyst being at least one meso compound of general formula: wherein: A 1 and A 2 are independently selected from the group consisting of mononuclear and polynuclear hydrocarbons; M 1 is a metal from group IVb, Vb, or VIb of the Periodic Table; R 1 and R 2 are independently selected from the group consisting of hydrogen, C 1 –C 10 alkyl, C 1 –C 10 -alkoxy, C 6 –C 10 aryl, C 6 –C 10 aryloxy, C 2 –C 10 alkenyl, C 7 –C 40 arylalkyl, C 7 –C 40 alkylaryl, C 8 –C 40 arylalkenyl and halogen; R 7 is selected from the group consisting of: ═BR 11 , ═AlR 11 , —Ge—, —Sn—, —O—, —S—, ═SO, ═SO 2 , ═NR 11 , ═CO, ═PR 11 and ═P(O)R 11 , where R 11 , R 12 , and R 13 are independently selected from the group consisting of hydrogen, halogen, C 1 –C 10 alkyl, C 1 –C 10 fluoroalkyl, C 6 –C 10 aryl, C 6 –C 10 fluoroaryl, C 1 –C 10 alkoxy, C 2 –C 10 alkenyl, C 7 –C 40 arylalkyl, C 8 –C 40 arylalkenyl, and C 7 –C 40 alkylaryl, or R 11 and R 12 or R 11 and R 13 , in each case with the atoms connecting them, form a ring; and M 2 is selected from the group consisting of silicon, germanium, and tin; R 8 and R 9 are independently selected from the group consisting of hydrogen, halogen, C 1 –C 10 alkyl, C 1 –C 10 fluoroalkyl, C 6 –C 10 aryl, C 6 –C 10 fluoroaryl, C 1 –C 10 alkoxy, C 2 –C 10 alkenyl, C 7 –C 40 arylalkyl, C 8 –C 40 arylalkenyl, and C 7 –C 40 alkylaryl; m and n are identical or different and are zero, 1, or 2, with m plus n being zero, 1 or 2.

Claims (31)

1. A substantially amorphous poly(α-olefin) possessing a M w of from about 500 to about 50,000, a M w /M n of from about 1.0 to about 10, a Kv 100 of from about 10 to about 10,000, an iodine number of from about 0.0 to about 10, and a T g of below about −60° C., obtained from the polymerization of at least one α-olefin having from 2 to about 20 carbon atoms and prepared by a process comprising polymerizing the monomer in the presence of hydrogen and a catalytically effective amount of a catalyst, wherein the catalyst comprises the product obtained by combining a metallocene catalyst with a cocatalyst, the metallocene catalyst being at least one meso compound of general formula:

wherein:

A 1 and A 2 are independently selected from the group consisting of mononuclear and polynuclear hydrocarbons;

M 1 is a metal from group IVb, Vb, or VIb of the Periodic Table;

R 1 and R 2 are independently selected from the group consisting of hydrogen, C 1 –C 10 alkyl, C 1 –C 10 -alkoxy, C 6 –C 10 aryl, C 6 –C 10 aryloxy, C 2 –C 10 alkenyl, C 7 –C 40 arylalkyl, C 7 –C 40 alkylaryl, C 8 –C 40 arylalkenyl and halogen;

R 7 is selected from the group consisting of:

═BR 11 , ═AlR 11 , —Ge—, —Sn—, —O—, —S—, ═SO, ═SO 2 , ═NR 11 , ═CO, ═PR 11 and ═P(O)R 11 , where R 11 , R 12 , and R 13 are independently selected from the group consisting of hydrogen, halogen, C 1 –C 10 alkyl, C 1 –C 10 fluoroalkyl, C 6 –C 10 aryl, C 6 –C 10 fluoroaryl, C 1 –C 10 alkoxy, C 2 –C 10 alkenyl, C 7 –C 40 arylalkyl, C 8 –C 40 arylalkenyl, and C 7 –C 40 alkylaryl, or, alternatively, R 11 can be combined with R 12 or R 11 can be combined with R 13 , in each case with the atoms connecting them, to form a ring; and M 2 is selected from the group consisting of silicon, germanium, and tin;

R 8 and R 9 are independently selected from the group consisting of hydrogen, halogen, C 1 –C 10 alkyl, C 1 –C 10 fluoroalkyl, C 6 –C 10 aryl, C 6 –C 10 fluoroaryl, C 1 –C 10 alkoxy, C 2 –C 10 alkenyl, C 7 –C 40 arylalkyl, C 8 –C 40 arylalkenyl, and C 7 –C 40 alkylaryl;

m and n are identical or different and are zero, 1, or 2, with m plus n being zero, 1 or 2.

2. The poly(α-olefin) of claim 1 wherein the cocatalyst is an aluminoxane.

3. The poly(α-olefin) of claim 2 wherein the metallocene catalyst is combined with hydrogen and the aluminoxane cocatalyst in any order thereof in the presence or absence of monomer.

4. The poly(α-olefin) of claim 1 wherein the α-olefin is 1-decene.

5. The poly(α-olefin) of claim 1 wherein the metallocene catalyst based in terms of the transition metal M 1 , is present in an amount from 0.0001 to about 0.02 millimole/liter and the cocatalyst is present in an amount from 0.01 to about 100 millimoles/liter.

6. The poly(α-olefin) of claim 1 wherein the catalyst is selected from the group consisting of meso-Me 2 Si(2-Et-Ind) 2 ZrCl 2 , meso-Et(Ind) 2 ZrCl 2 , meso-Et(IndH 4 ) 2 ZrCl 2 , meso-Me 2 Si(Ind) 2 ZrCl 2 , meso-Me 2 Si(IndH 4 ) 2 ZrCl 2 , meso-Me 2 Si(2-Me-Ind) 2 ZrCl 2 , and meso-Me 2 Si(2-Me-4-Ph-Ind) 2 ZrCl 2 .

7. A lubricant composition comprising a lubricant and a viscosity-modifying amount of a poly(α-olefin) wherein said poly(α-olefin) is substantially amorphous and possesses a M w of from about 500 to about 50,000, a M w /M n of from about 1.0 to about 10, a Kv 100 of from about 10 to about 10,000, an iodine number of from about 0.0 to about 10, and a T g of below about −60° C., and wherein the poly(α-olefin) is obtained from the polymerization of at least one α-olefin having from 2 to about 20 carbon atoms and prepared by a process comprising polymerizing the monomer in the presence of hydrogen and a catalytically effective amount of a catalyst, wherein the catalyst comprises the product obtained by combining a metallocene catalyst with a cocatalyst, the metallocene catalyst being at least one meso compound of general formula:

wherein:

A 1 and A 2 are independently selected from the group consisting of mononuclear and polynuclear hydrocarbons;

M 1 is a metal from group IVb, Vb, or VIb of the Periodic Table;

R 1 and R 2 are independently selected from the group consisting of hydrogen, C 1 –C 10 alkyl, C 1 –C 10 -alkoxy, C 6 –C 10 aryl, C 6 –C 10 aryloxy, C 2 –C 10 alkenyl, C 7 –C 40 arylalkyl, C 7 –C 40 alkylaryl, C 8 –C 40 arylalkenyl and halogen;

R 7 is selected from the group consisting of:

═BR 11 , ═AlR 11 , —Ge—, —Sn—, —O—, —S—, ═SO, ═SO 2 , ═NR 11 , ═CO, ═PR 11 and ═P(O)R 11 , where

R 11 , R 12 , and R 13 are independently selected from the group consisting of hydrogen, halogen, C 1 –C 10 alkyl, C 1 –C 10 fluoroalkyl, C 6 –C 10 aryl, C 6 –C 10 fluoroaryl, C 1 –C 10 alkoxy, C 2 –C 10 alkenyl, C 7 –C 40 arylalkyl, C 8 –C 40 arylalkenyl, and C 7 –C 40 alkylaryl, or, alternatively, R 11 can be combined with R 12 or R 11 can be combined with R 13 , in each case with the atoms connecting them, to form a ring; and M 2 is selected from the group consisting of silicon, germanium, and tin;

R 8 and R 9 are independently selected from the group consisting of hydrogen, halogen, C 1 –C 10 alkyl, C 1 –C 10 fluoroalkyl, C 6 –C 10 aryl, C 6 –C 10 fluoroaryl, C 1 –C 10 alkoxy, C 2 –C 10 alkenyl, C 7 –C 40 arylalkyl, C 8 –C 40 arylalkenyl, and C 7 –C 40 alkylaryl;

m and n are identical or different and are zero, 1, or 2, with m plus n being zero, 1 or 2.

8. The lubricant composition of claim 7 wherein the α-olefin is 1-decene.

9. The lubricant composition of claim 7 wherein the metallocene catalyst based in terms of the transition metal M 1 , is present in an amount from 0.0001 to about 0.02 millimole/liter and the cocatalyst is present in an amount from 0.01 to about 100 millimoles/liter.

10. The lubricant composition of claim 7 wherein the catalyst is selected from the group consisting of meso-Me 2 Si(2-Et-Ind) 2 ZrCl 2 , meso-Et(Ind) 2 ZrCl 2 , meso-Et(IndH 4 ) 2 ZrCl 2 , meso-Me 2 Si(Ind) 2 ZrCl 2 , meso-Me 2 Si(IndH 4 ) 2 ZrCl 2 , meso-Me 2 Si(2-Me-Ind) 2 ZrCl 2 , and meso-Me 2 Si(2-Me-4-Ph-Ind) 2 ZrCl 2 .

11. A lubricant composition comprising a lubricant and a viscosity-modifying amount of a poly(α-olefin) wherein said poly(α-olefin) is substantially amorphous and possesses a M w of from about 500 to about 50,000, a M w /M n of from about 1.0 to about 10, a Kv 100 of from about 10 to about 10,000, an iodine number of from about 0.0 to about 10, and a T g of below about −60°C., and wherein the poly(α-olefin) is obtained from the polymerization of at least one α-olefin having from 2 to about 20 carbon atoms and prepared by a process comprising polymerizing the monomer in the presence of hydrogen and a catalytically effective amount of a catalyst, wherein the catalyst comprises the product obtained by combining a metallocene catalyst with an aluminoxane cocatalyst, the metallocene catalyst being selected from the group consisting of meso-Me 2 Si(2-Et-Ind) 2 ZrCl 2 , meso-Et(Ind) 2 ZrCl 2 , meso-Et(IndH 4 ) 2 ZrCl 2 , meso-Me 2 Si(Ind) 2 ZrCl 2 , meso-Me 2 Si(IndH 4 ) 2 ZrCl 2 , meso-Me 2 Si(2-Me-Ind) 2 ZrCl 2 , and meso-Me 2 Si(2-Me-4-Ph-Ind) 2 ZrCl 2 , and wherein the metallocene catalyst based in terms of the ziconium is present in an amount from 0.0001 to about 0.02 millimole/liter and the aluminoxane cocatalyst is present in an amount from 0.01 to about 100 millimoles/liter.

12. The lubricant composition of claim 11 wherein the poly(α-olefin) possesses a M w of from about 1,500 to about 20,000, a M w /M n of from about 1.75 to about 3, a Kv 100 of from about 20 to about 500, an iodine number of from about 0.2 to about 4, and a T g of below about −70°C. and wherein the metallocene catalyst based in terms of the ziconium is present in an amount from 0.00025 to about 0.01 millimole/liter and the aluminoxane cocatalyst is present in an amount from 0.025 to about 50 millimoles/liter.

13. The lubricant composition of claim 11 wherein the α-olefin is 1-decene.

14. The lubricant composition of claim 12 wherein the α-olefin is 1-decene.

Assignments (10)
CHANGE OF NAME Recorded Sep 25, 2018
From: CROMPTON CORPORATION
To: CHEMTURA CORPORATION
Reel/Frame 047141/0152 →
RELEASE OF FIRST LIEN INTELLECTUAL PROPERTY SECURITY AGREEMENT Recorded May 11, 2017
From: BANK OF AMERICA, N.A.
To: CHEMTURA CORPORATION; BIOLAB FRANCHISE COMPANY, LLC; BIO-LAB, INC.; CROMPTON COLORS INCORPORATED; CROMPTON HOLDING CORPORATION; GLCC LAUREL, LLC; GREAT LAKES CHEMICAL CORPORATION; GREAT LAKES CHEMICAL GLOBAL, INC.; GT SEED TREATMENT, INC.; HOMECARE LABS, INC.; LAUREL INDUSTRIES HOLDINGS, INC.; RECREATIONAL WATER PRODUCTS, INC.; WEBER CITY ROAD LLC
Reel/Frame 042447/0508 →
RELEASE OF SECOND LIEN INTELLECTUAL PROPERTY SECURITY AGREEMENT Recorded May 11, 2017
From: BANK OF AMERICA, N.A.
To: CHEMTURA CORPORATION; BIOLAB FRANCHISE COMPANY, LLC; BIO-LAB, INC.; CROMPTON COLORS INCORPORATED; CROMPTON HOLDING CORPORATION; GLCC LAUREL, LLC; GREAT LAKES CHEMICAL CORPORATION; GREAT LAKES CHEMICAL GLOBAL, INC.; GT SEED TREATMENT, INC.; HOMECARE LABS, INC.; LAUREL INDUSTRIES HOLDINGS, INC.; RECREATIONAL WATER PRODUCTS, INC.; WEBER CITY ROAD LLC
Reel/Frame 042449/0001 →
FIRST LIEN INTELLECTUAL PROPERTY SECURITY AGREEMENT. Recorded Mar 21, 2011
From: CHEMTURA CORPORATION; BIOLAB FRANCHISE COMPANY, LLC; BIO-LAB, INC.; CROMPTON COLORS INCORPORATED; CROMPTON HOLDING CORPORATION; GLCC LAUREL, LLC; GREAT LAKES CHEMICAL CORPORATION; GREAT LAKES CHEMICAL GLOBAL, INC.; GT SEED TREATMENT, INC.; HOMECARE LABS, INC.; LAUREL INDUSTRIES HOLDINGS, INC.; RECREATIONAL WATER PRODUCTS, INC.; WEBER CITY ROAD LLC
To: BANK OF AMERICA, N.A.
Reel/Frame 026028/0622 →
INTELLECTUAL PROPERTY SECURITY RELEASE AGREEMENT Recorded Mar 21, 2011
From: CITIBANK, N.A.
To: CHEMTURA CORPORATION; A & M CLEANING PRODUCTS, LLC; ASCK, INC; BIOLAB COMPANY STORE, LLC; AQUA CLEAR INDUSTRIES, LLC; ASEPSIS, INC.; BIOLAB TEXTILES ADDITIVES, LLC; BIOLAB, INC.; CROMPTON COLORS INCORPORATED; CROMPTON MONOCHEM, INC.; CNK CHEMICAL REALTY CORPORATION; CROMPTON HOLDING CORPORATION; GLCC LAUREL, LLC; GREAT LAKES CHEMICAL CORPORATION; GT SEED TREATMENT, INC.; ISCI, INC; GREAT LAKES CHEMICAL GLOBAL, INC.; HOMECARE LABS, INC.; KEM MANUFACTURING CORPORATION; LAUREL INDUSTRIES HOLDINGS, INC.; NAUGATUCK TREATMENT COMPANY; UNIROYAL CHEMICAL COMPANY LIMITED (DELAWARE); MONOCHEM, INC.; RECREATIONAL WATER PRODUCTS, INC.; WEBER CITY ROAD LLC; WRL OF INDIANA, INC.; BIOLAB FRANCHISE COMPANY, LLC
Reel/Frame 026039/0142 →
SECDOND LIEN INTELLECTUAL PROPERTY SECURITY AGREEMENT Recorded Mar 21, 2011
From: CHEMTURA CORPORATION; BIOLAB FRANCHISE COMPANY, LLC; BIO-LAB, INC.; CROMPTON COLORS INCORORATED; CROMPTON HOLDING CORPORATION; CLCC LAUREL, LLC; GREAT LAKES CHEMICAL CORPORATION; GREAT LAKES CHEMICAL GLOBAL, INC.; GT SEED TREATMENT, INC.; HOMECARE LABS, INC.; HAOMECARE LABS, INC.; LAUREL INDUSTRIES HOLDINGS, INC.; RECREATIONAL WATER PRODUCTS, INC.; WEBER CITY ROAD LLC
To: BANK OF AMERICA, N. A.
Reel/Frame 027881/0347 →
AMENDED AND RESTATED INTELLECTUAL PROPERTY SECURITY AGREEMENT Recorded Feb 22, 2010
From: CHEMTURA CORPORATION; A & M CLEANING PRODUCTS, LLC; AQUA CLEAR INDUSTRIES, LLC; ASCK, INC.; ASEPSIS, INC.; BIOLAB COMPANY STORE, LLC; BIOLAB FRANCHISE COMPANY, LLC; BIOLAB TEXTILE ADDITIVES, LLC; BIO-LAB, INC.; CNK CHEMICAL REALTY CORPORATION; CROMPTON COLORS INCORPORATED; CROMPTON HOLDING CORPORATION; CROMPTON MONOCHEM, INC.; GLCC LAUREL, LLC; GREAT LAKES CHEMICAL CORPORATION; GREAT LAKES CHEMICAL GLOBAL, INC.; GT SEED TREATMENT, INC.; HOMECARE LABS, INC.; ISCI, INC.; KEM MANUFACTURING CORPORATION; LAUREL INDUSTRIES HOLDINGS, INC.; MONOCHEM, INC.; NAUGATUCK TREATMENT COMPANY; RECREATIONAL WATER PRODUCTS, INC.; UNIROYAL CHEMICAL COMPANY LIMITED (DELAWARE); WEBER CITY ROAD LLC; WRL OF INDIANA, INC.
To: CITIBANK, N.A.
Reel/Frame 023998/0001 →
SECURITY AGREEMENT Recorded May 12, 2009
From: CHEMTURA CORPORATION; A & M CLEANING PRODUCTS, LLC; AQUA CLEAR INDUSTRIES, LLC; ASCK, INC.; ASEPSIS, INC.; BIOLAB TEXTILE ADDITIVES, LLC; BIO-LAB, INC.; CNK CHEMICAL REALTY CORPORATION; CROMPTON HOLDING CORPORATION; CROMPTON COLORS INCORPORATED; CROMPTON MONOCHEM, INC.; GREAT LAKES CHEMICAL CORPORATION; GREAT LAKES CHEMICAL GLOBAL, INC.; GT SEED TREATMENT, INC.; HOMECARE LABS, INC.; ISCI, INC.; KEM MANUFACTURING CORPORATION; LAUREL INDUSTRIES HOLDINGS, INC.; MONOCHEM, INC.; NAUGATUCK TREATMENT COMPANY; RECREATIONAL WATER PRODUCTS, INC.; UNIROYAL CHEMICAL COMPANY LIMITED (DELAWARE); WEBER CITY ROAD LLC; WRL OF INDIANA, INC.; BIOLAB COMPANY STORE, LLC; BIOLAB FRANCHISE COMPANY, LLC; GLCC LAUREL, LLC
To: CITIBANK, N.A.
Reel/Frame 022668/0658 →
RELEASE OF LIEN IN PATENTS Recorded Jul 13, 2005
From: DEUTSCHE BANK AG, NEW YORK BRANCH
To: CROMPTON CORPORATION
Reel/Frame 016513/0745 →
SECURITY AGREEMENT Recorded Nov 10, 2004
From: CROMPTON CORPORATION
To: DEUTSCHE BANK AG NEW YORK BRANCH
Reel/Frame 015370/0467 →