IP Library Granted Patent US 7,402,619
Granted Patent B2
US 7,402,619 · App. 11/095,368 · Granted Jul 22, 2008

Cross-linking compositions for polymer-modified asphalt compositions

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Quick Facts
Patent No.
US 7,402,619
App. No.
11/095,368
Granted
Jul 22, 2008
Kind
B2
Abstract

The present invention relates to a bituminous composition comprising a bituminous component, an elastomeric polymer component, and a specific cross-linking composition component comprising elemental sulfur, a sulfur-containing derivative, a sulfur activator, a fatty acid or fatty acid derivative and a polymeric carrier. Compositions according to the invention are particularly useful in preparing polymer-modified asphalt (“PMA”) for road applications.

Claims (41)

1. A method for preparing bitumen/elastomeric polymer compositions comprising:

a. heating the bitumen in a stirred tank to a temperature of between 220 and 430° F.;

b. adding the elastomeric polymer to the tank in an amount of between 2 and 30 weight percent, to form a mixture of bitumen and elastomeric polymer;

c. adding 0.01 to 5 weight percent of a cross-linking composition to the mixture and continuing stirring while maintaining the temperature of the mixture at between 275 and 430° F. for a time period of between 20 and 120 minutes;

wherein said cross-linking composition comprises:

a. 5 to 50 percent by weight of elemental sulfur:

b. 0.5 to 10 percent by weight of a sulfur-containing derivative selected from the group consisting of compounds having the formula

where R 1 and R 2 are like or different alky radicals having 1 to 4 carbon atoms and wherein M is selected from the group consisting of zinc, barium, copper, cadmium and thallium;

c. 5 to 50 percent by weight of a sulfur activator selected from zinc compounds;

d. 5 to 50 percent by weight of a solubilizing agent selected from fatty acids and fatty acid derivatives; and

e. 10 to 85 percent by weight of a polymeric carrier,

said cross-linking composition having a zinc content of at least 2 weight percent, based on the total weight of the cross-linking composition and a zinc to sulfur content weight ratio of 0.5:1 to 2:1.

2. The method according to claim 1 wherein said bitumen is selected from the group consisting of straight-run bitumens and fluxed bitumens.

3. The method according to claim 2 wherein said elastomeric polymer is selected from the group consisting of butyl rubber, polybutadiene, polyisoprene, ethylene/propylene/diene (EPDM) terpolymers, and styrene/conjugated diene block copolymers.

4. The method according to claim 3 wherein said elastomeric polymer is a styrene/conjugated diene block copolymer having a structure represented by the following general formulae

S—B—S, (S—B) n —-X, (S—B) or a mixture thereof,

wherein each S independently is a poly(vinyl aromatic) block and each B independently is a poly(conjugated diene) block, n is an integer equal to or greater than 2 and X is the residue of a coupling agent.

5. The method according to claim 4 wherein said styrene/conjugated diene block copolymer is a radial styrene/butadiene block copolymer having a diblock content of between 65 and 85 mole percent.

6. The method according to claim 4 wherein said styrene/conjugated diene block copolymer is a styrene-butadiene diblock copolymer.

7. The method according to claim 4 wherein said sulfur-containing derivative is zinc dimethyl dithio carbamate.

8. The method according to claim 7 wherein said sulfur activator is zinc oxide and said solubilizing agent is calcium stearate.

9. The method according to claim 8 wherein said polymeric carrier is selected from the group consisting of ethylene/propylene rubber, and ethylene/vinyl acetate copolymers.

10. The method according to claim 8 wherein the polymeric carrier is a polyethylene having a number average molecular weight of 7700.

11. A method for preparing bitumen/elastomeric polymer compositions comprising:

a. heating the bitumen in a stirred tank to a temperature of between 220 and 430° F.;

b. adding the elastomeric polymer to the tank in an amount of between 2 and 30 weight percent, to form a mixture of bitumen and elastomeric polymer;

c. adding 0.01 to 5 weight percent of a cross-linking composition to the mixture and continuing stirring while maintaining the temperature of the mixture at between 275 and 430° F. for a time period of between 20 and 120 minutes;

wherein said cross-linking composition comprises:

a. 5 to 50 percent by weight of elemental sulfur:

b. 0.5 to 10 percent by weight of a sulfur-containing derivative selected from the group consisting of compounds having the formula

where R 1 and R 2 are like or different alky radicals having 1 to 4 carbon atoms and wherein M is selected from the group consisting of zinc, barium, copper, cadmium and thallium;

c. 5 to 50 percent by weight of a component selected from fatty acid derivatives of zinc; and

d. 10 to 85 percent by weight of a polymeric carrier, said cross-linking composition having a zinc content of at least 2 weight percent, based on the total weight of the cross-linking composition and a zinc to sulfur content weight ratio of 0.5:1 to 2:1.

12. The method according to claim 1 wherein said bitumen is selected from the group consisting of straight-run bitumens and fluxed bitumens.

13. The method according to claim 2 wherein said elastomeric polymer is selected from the group consisting of butyl rubber, polybutadiene, polyisoprene, ethylene/propylene/diene (EPDM) terpolymers, and styrene/conjugated diene block copolymers.

14. The method according to claim 3 wherein said elastomeric polymer is a styrene/conjugated diene block copolymer having a structure represented by the following general formulae

S—B—S, (S—B) n —X, (S—B) or a mixture thereof,

wherein each S independently is a poly(vinyl aromatic) block and each B independently is a poly(conjugated diene) block, n is an integer equal to or greater than 2 and X is the residue of a coupling agent.

15. The method according to claim 4 wherein said styrene/conjugated diene block copolymer is a radial styrene/butadiene block copolymer having a diblock content of between 65 and 85 mole percent.

16. The method according to claim 4 wherein said styrene/conjugated diene block copolymer is a styrene-butadiene diblock copolymer.

17. The method according to claim 8 wherein said polymeric carrier is selected from the group consisting of ethylene/propylene rubber, and ethylene/vinyl acetate copolymers.

Assignments (9)
CORRECTIVE ASSIGNMENT TO CORRECT THE PATENT NO. 8837224 TO PATENT NO. 7737224 PREVIOUSLY RECORDED AT REEL: 037448 FRAME: 0453. ASSIGNOR(S) HEREBY CONFIRMS THE ASSIGNMENT. Recorded Jun 11, 2022
From: KRATON POLYMERS U.S. LLC; ARIZONA CHEMICAL COMPANY, LLC
To: BANK OF AMERICA, N.A.
Reel/Frame 060344/0919 →
RELEASE OF SECURITY INTEREST Recorded Mar 16, 2022
From: BANK OF AMERICA, N.A.
To: KRATON POLYMERS U.S. LLC; KRATON CHEMICAL, LLC F/K/A ARIZONA CHEMICAL COMPANY, LLC; KRATON POLYMERS LLC; KRATON CORPORATION; KRATON CHEMICAL B.V.
Reel/Frame 059910/0017 →
RELEASE OF SECURITY INTEREST Recorded Mar 15, 2022
From: CREDIT SUISSE AG, CAYMAN ISLANDS BRANCH, AS COLLATERAL AGENT
To: KRATON POLYMERS U.S. LLC
Reel/Frame 059366/0611 →
SECURITY INTEREST Recorded Apr 16, 2020
From: KRATON POLYMERS U.S. LLC; KRATON CHEMICAL, LLC F/K/A ARIZONA CHEMICAL COMPANY, LLC; KRATON POLYMERS LLC; KRATON CORPORATION
To: BANK OF AMERICA, N.A.
Reel/Frame 053020/0101 →
PATENT SECURITY AGREEMENT Recorded Jan 7, 2016
From: KRATON POLYMERS U.S. LLC
To: CREDIT SUISSE AG, CAYMAN ISLANDS BRANCH, AS COLLATERAL AGENT
Reel/Frame 037457/0843 →
CORRECTIVE ASSIGNMENT TO CORRECT THE PATENT NUMBER 8837224 TO PATENT NUMBER 7737224 PREVIOUSLY RECORDED AT REEL: 037448 FRAME: 0453. ASSIGNOR(S) HEREBY CONFIRMS THE SECURITY INTEREST. Recorded Jan 6, 2016
From: KRATON POLYMERS U.S. LLC; ARIZONA CHEMICAL COMPANY, LLC
To: BANK OF AMERICA, N.A.
Reel/Frame 037448/0453 →
CORRECTIVE ASSIGNMENT TO CORRECT THE INCORRECT PATENT NUMBER 7720798 AND REPLACE WITH PATENT NUMBER 7220798 PREVIOUSLY RECORDED ON REEL 025845 FRAME 0795. ASSIGNOR(S) HEREBY CONFIRMS THE RELEASE BY SECURED PARTY. Recorded Dec 16, 2015
From: USB AG, STAMFORD BRANCH
To: KRATON POLYMERS U.S. LLC
Reel/Frame 037312/0070 →
RELEASE OF SECURITY INTEREST Recorded Feb 24, 2011
From: UBS AG, STAMFORD BRANCH
To: KRATON POLYMERS U.S. LLC
Reel/Frame 025845/0795 →
SUPPLEMENT TO PATENT SECURITY AGREEMENT Recorded May 18, 2006
From: KRATON POLYMERS U.S. LLC
To: UBS AG, STAMFORD BRANCH, AS COLLATERAL AGENT
Reel/Frame 017892/0158 →