IP Library Granted Patent US 7,282,536
Granted Patent B2
US 7,282,536 · App. 11/055,349 · Granted Oct 16, 2007

Block copolymers and method for making same

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Quick Facts
Patent No.
US 7,282,536
App. No.
11/055,349
Granted
Oct 16, 2007
Kind
B2
Abstract

The present invention is a novel block copolymer containing a controlled distribution copolymer block of a conjugated diene and a mono alkenyl arene, where the controlled distribution copolymer block has terminal regions that are rich in conjugated diene units and a center region that is rich in mono alkenyl arene units. Also disclosed is a method for manufacture of the block copolymer.

Claims (21)

1. A process for preparing sulfonated hydrogenated block copolymers comprising reacting a block copolymer with a sulfonation reagent that selectively sulfonates the alkenyl arene blocks wherein the hydrogenated block copolymer has the general configuration A-B, A-B-A, (A-B) n , (A-B-A) n , (A-B-A) n X, (A-B) n X or mixtures thereof, where n is an integer from 2 to about 30, and X is a coupling agent residue and wherein:

a. prior to hydrogenation each A block is a mono alkenyl arene polymer block and each B block is a controlled distribution copolymer block of at least one conjugated diene and at least one mono alkenyl arene;

b. subsequent to hydrogenation about 0–10% of the arene double bonds have been reduced, and at least about 90% of the conjugated diene double bonds have been reduced;

c. each A block having a number average molecular weight between about 3,000 and about 60,000 and each B block having a number average molecular weight between about 30,000 and 300,000;

d. each B block comprises terminal regions adjacent to the A block that are rich in conjugated diene units and one or more regions not adjacent to the A block that are rich in mono alkenyl arene units;

e. the total amount of mono alkenyl arene in the hydrogenated block copolymer is about 20 percent weight to about 80 percent weight; and

f. the weight percent of mono alkenyl arene in each B block is between about 10 percent and about 75 percent,

g. wherein the styrene blockiness index of the block B is less than about 40 percent.

2. The process of claim 1 wherein the sulfonation reagent is an acyl sulfate.

3. The process of claim 2 wherein the acyl sulfate is acetyl sulfate.

4. The process of claim 3 additionally comprising reacting the sulfonated block copolymer with an ionizable metal compound to obtain a metal salt.

5. The process of claim 4 wherein the ionizable metal compound is a Zn 2+ compound.

6. The process of claim 5 wherein the Zn 2+ compound is a zinc acetate.

7. The process of claim 1 wherein said mono alkenyl arene is styrene and said conjugated diene is selected from the group consisting of isoprene and butadiene.

8. The process of claim 1 wherein said conjugated diene is butadiene, and wherein about 20 to about 80 mol percent of the condensed butadiene units in block B have 1,2-configuration prior to hydrogenation.

9. The process of claim 1 wherein the weight percentage of styrene in the B block is between about 10 percent and about 40 percent, and the styrene blookiness index of the B block is less than about 10 percent, said styrene blockiness index being the proportion of styrene units in the block B having two styrene neighbors on the polymer chain.

10. The process of claim 1 wherein before functionaliziation said A block has a glass transition temperature of plus 80° C. to plus 110° C. and said B block has a glass transition temperature of at least above about minus 60° C.

11. The process of claim 10 wherein before functionalization said B block has a glass transition temperature of between minus 40° C. and plus 30° C.

12. The process of claim 4 wherein the ionizable metal compound comprises Na + , K + , Li + , Cs + , Ag + , Hg + , Cu + , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Cu 2+ , Cd 2+ , Hg 2+ , Sn 2+ , Pb 2+ , Fe 2+ , Co 2+ , Ni 2+ , Zn 2+ , Al 3+ , Sc 3+ , Fe 3+ , La 3+ or Y 3+ .

13. The process of claim 4 wherein the ionizable metal compound comprises a hydroxide, an oxide, an alcoholate, a carboxylate, a formate, an acetate, a methoxide, an ethoxide, a nitrate, a carbonate or a bicarbonate.

14. The process of claim 1 wherein the styrene blockiness index of the block B is less than about 10 percent.

Assignments (15)
RELEASE OF SECURITY INTEREST IN PATENTS Recorded Jul 24, 2024
From: GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT
To: KRATON CHEMICAL, LLC; KRATON CORPORATION
Reel/Frame 068671/0836 →
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 →
SECURITY INTEREST Recorded Mar 18, 2022
From: KRATON CHEMICAL, LLC; KRATON POLYMERS LLC; KRATON POLYMERS U.S. LLC
To: GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT
Reel/Frame 059525/0804 →
SECURITY INTEREST Recorded Mar 18, 2022
From: KRATON CHEMICAL, LLC; KRATON POLYMERS LLC; KRATON POLYMERS U.S. LLC
To: GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT
Reel/Frame 059864/0455 →
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 Mar 28, 2013
From: BANK OF AMERICA, N.A.
To: KRATON POLYMERS U.S. LLC
Reel/Frame 030108/0288 →
NOTICE OF GRANT OF SECURITY INTEREST IN PATENTS Recorded Mar 4, 2011
From: KRATON POLYMERS U.S. LLC
To: BANK OF AMERICA N.A., AS COLLATERAL AGENT
Reel/Frame 025899/0176 →
RELEASE OF SECURITY INTEREST Recorded Feb 24, 2011
From: UBS AG, STAMFORD BRANCH
To: KRATON POLYMERS U.S. LLC
Reel/Frame 025845/0795 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jan 8, 2007
From: HANDLIN, JR., DALE L.; BENING, ROBERT C.; STERNA, LARRY L.; WILLIS, CARL L.
To: KRATON POLYMERS U.S. LLC
Reel/Frame 018775/0644 →
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 →