IP Library Granted Patent US 8,901,236
Granted Patent B2
US 8,901,236 · App. 14/049,037 · Granted Dec 2, 2014

Process for creating an ethylene elastomer

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Quick Facts
Patent No.
US 8,901,236
App. No.
14/049,037
Granted
Dec 2, 2014
Kind
B2
Abstract

A process for continuously making a terpolymer or a tetrapolymer utilizing ethylene, an alpha olefin, and at least one polyene. This process allows for the creation of products with high polyene contents and broad molecular weight distributions while utilizing a continuous flow reactor and a known catalyst. The process allows for these products to be made without gelling, or fouling of the reactor.

Claims (42)

1. A process for continuously making terpolymers and tetrapolymers, comprising ethylene monomers, alpha olefin monomers, and non-conjugated polyene monomers, comprising:

a. introducing a saturated hydrocarbon stream;

b. introducing an alpha olefin monomer to the saturated hydrocarbon stream at a rate sufficient to achieve alpha olefin content in a final product of 14 percent to 50 percent of total weight, wherein the alpha olefin monomer comprises from 3 carbon atoms to 20 carbon atoms;

c. introducing hydrogen gas to the saturated hydrocarbon stream at a rate sufficient to control the molecular weight of the final product;

d. introducing a first non-conjugated polyene to the saturated hydrocarbon stream at a rate sufficient to achieve desired first non-conjugated polyene content in the final product;

e. optionally introducing a second non-conjugated polyene to the saturated hydrocarbon stream at a rate sufficient to achieve desired second non-conjugated polyene content in the final product;

f. introducing an ethylene monomer to the saturated hydrocarbon stream at a rate sufficient to initiate the polymerization reaction and achieve ethylene content in the final product of 35 percent to 80 percent of total weight;

g. cooling the saturated hydrocarbon stream, the alpha olefin monomer, hydrogen gas, the first non-conjugated polyene, the second non-conjugated polyene if used, and the ethylene to below 35 degrees Celsius to create a cooled mixture;

h. concurrently introducing a Ziegler-Natta catalyst, a co-catalyst, and optionally a promoter into a continuous flow reactor, wherein:

(i) the Ziegler-Natta catalyst comprises a transition metal or a transition metal compound;

(ii) the co-catalyst comprises a metal alkyl comprising a halogen element; and

(iii) the promoter if used comprises an oxidizing agent capable of oxidizing the transition metal, and the oxidizing agent is capable of generating at least one halogen free-radical per mole of promoter;

i. reacting the cooled mixture, the Ziegler-Natta catalyst, the co-catalyst, the promoter if used, the first non-conjugated polyene, and the second non-conjugated polyene if used for 30 minutes to 60 minutes, at a temperature from 35 degrees Celsius to 65 degrees Celsius, and a pressure from 190 psig to 230 psig; and

j. forming a resultant terpolymer or a resultant tetrapolymer as the final product with the following characteristics:

(i) polymer chain branching as characterized by a tangent delta ranging from 0.286 to 5.0;

(ii) a non-linear relationship between viscosity and shear as characterized by the tangent delta from 0.286 to 5.0;

(iii) a weight average molecular weight of 80,000 to 2,500,000;

(iv) a Mooney viscosity ranging from (ML 1+4@ 125 degrees Celsius) 9 to (ML 1+4@ 150 degrees Celsius) 160;

(v) an ethylene to alpha olefin ratio ranging from 40:60 to 80:20;

(vi) a molecular weight distribution ranging from 1.8 to 8;

(vii) a combined weight content of ethylene and alpha olefin of 70 percent to 99.98 percent based upon the total weight of the resultant terpolymer or resultant tetrapolymer;

(viii) a first non-conjugated polyene content of 0.01 percent to 25 percent by weight content based upon the total weight of the resultant terpolymer or resultant tetrapolymer; and

(ix) a second non-conjugated polyene content if used of 0.01 percent to 5 percent by weight content based upon the total weight of the resultant terpolymer or the resultant tetrapolymer.

2. The process of claim 1 , wherein the Ziegler-Natta catalyst and the promoter if used are premixed before introduction to the continuous flow reactor.

3. The process of claim 1 , wherein the molar ratio of the co-catalyst to the sum of the catalyst and the promoter if used is from 1 to 50.

4. The process of claim 1 , wherein the saturated hydrocarbon stream is hexane.

5. The process of claim 1 , wherein the alpha olefin monomer is propylene.

6. The process of claim 1 , wherein the alpha olefin monomer is butylene.

7. The process of claim 1 , wherein the first non-conjugated polyene and the second non-conjugated polyene if used are both norbornene derivatives.

8. The process of claim 1 , wherein the Ziegler-Natta catalyst is a vanadium oxytrichloride or a vanadium vanadate.

9. The process of claim 1 , wherein the co-catalyst is Diethylaluminum chloride, Ethylaluminum sesquichloride, or Ethylaluminum dichloride.

10. The process of claim 1 , wherein the oxidizing agent is an ester comprising a halogen element.

11. The process of claim 1 , wherein the oxidizing agent is Butyl-2methyl, 4,4,4-trichlorobut-2-enoate.

12. The process of claim 1 , wherein reacting the cooled mixture, the Ziegler-Natta catalyst, the co-catalyst, the promoter if used, the first non-conjugated polyene, and the second non-conjugated polyene if used occurs in a slurry phase.

13. The process of claim 1 , wherein reacting the cooled mixture, the Ziegler-Natta catalyst, the co-catalyst, the promoter if used, the first non-conjugated polyene, and the second non-conjugated polyene if used occurs in a gas phase.

14. A terpolymer made by the process of claim 1 .

15. A terpolymer made by the process of claim 1 , wherein one of the components is Vinyl Norbornene.

16. A tetrapolymer made by the process of claim 1 .

17. A tetrapolymer made by the process of claim 1 , wherein one of the components is Vinyl Norbornene.

18. A thermoplastic vulcanizate comprising the final product made by the process of claim 1 .

19. The final product of claim 1 , further comprising an extender oil.

20. The process of claim 1 , wherein reacting the cooled mixture, the Ziegler-Natta catalyst, the co-catalyst, the promoter if used, the first non-conjugated polyene, and the second non-conjugated polyene if used occurs in a solution phase.

Assignments (5)
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 →
SECURITY INTEREST Recorded Oct 31, 2017
From: LION COPOLYMER HOLDINGS, LLC
To: CORTLAND CAPITAL MARKET SERVICES LLC, AS COLLATERAL AGENT
Reel/Frame 043996/0218 →
NOTICE OF GRANT OF SECURITY INTEREST IN PATENTS Recorded Feb 17, 2014
From: LION COPOLYMER GEISMAR, LLC
To: BANK OF AMERICA, N.A., AS ADMINISTRATIVE AGENT
Reel/Frame 032268/0387 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Feb 11, 2014
From: LION COPOLYMER, LLC
To: LION COPOLYMER GEISMAR, LLC
Reel/Frame 032198/0571 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Oct 8, 2013
From: BURTON, WILLIE CHARLES; TANG, SOLOMON H. K.; DOUCET, GARRETT
To: LION COPOLYMER, LLC
Reel/Frame 031368/0007 →