IP Library Granted Patent US 11,629,215
Granted Patent B2
US 11,629,215 · App. 16/833,789 · Granted Apr 18, 2023

Sulfonated block copolymers and uses thereof

Inventors: Carl L Willis (Houston, TX); Marc D Hein (Houston, TX); Richard I Blackwell (Houston, TX)
Assignee: KRATON CORPORATION
C08F297/042H01B3/307
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Quick Facts
Patent No.
US 11,629,215
App. No.
16/833,789
Granted
Apr 18, 2023
Kind
B2
Abstract

Disclosed herein is a styrenic block copolymer [A1-B1-C1], consisting essentially of polymer blocks A1, B1 and C1. A1 is a poly(para-alkylstyrene) block having a molecular weight from 1,000 to 60,000 g/mol. B1 is a hydrogenated polyisoprene block or a hydrogenated polybutadiene block having a molecular weight from 1,000 to 100,000 g/mol. C1 is a polystyrene block having a molecular weight from 1,000 to 100,000 g/mol; or a polymer block consisting essentially of polymerized styrene units, and hydrogenated butadiene and/or isoprene units, and having a molecular weight from 1,000 to 100,000 g/mol. Prior to hydrogenation, the block B1 has a vinyl content of 5-75 mol %; and the block C1 forms 1-80 wt % of the overall weight of the block copolymer. The selectively sulfonated forms of the copolymers are useful as high dielectric materials.

Claims (38)

1. A styrenic block copolymer consisting essentially of polymer blocks A1, B1 and C1 and having a formula [A1-B1-C1], wherein

A1 is a poly(para-alkylstyrene) block having a molecular weight from 1,000 to 60,000 g/mol;

B1 is a hydrogenated polyisoprene block (E/P) or a hydrogenated polybutadiene block (EB) having a molecular weight from 1,000 to 100,000 g/mol; and

C1 is a polystyrene block having a molecular weight from 1,000 to 100,000 g/mol, or a polymer block consisting essentially of polymerized styrene units, and hydrogenated butadiene and/or isoprene units, and having a molecular weight from 1,000 to 100,000 g/mol;

wherein prior to hydrogenation,

the block B1 has a vinyl content of 5-75 mol %, and

the block C1 forms from 1-80 wt % of the overall weight of the block copolymer.

2. The block copolymer of claim 1 , wherein the poly(para-alkylstyrene) block is selected from a poly(para-methylstyrene) block, a poly(para-tert-butylstyrene) block, and combinations thereof.

3. The block copolymer of claim 1 , wherein the polymerized styrene units in the block C1 are sulfonated to the extent of 1-100 mol percent.

4. The block copolymer of claim 1 , wherein the C1 block forms from 1-10 wt. % of the overall block copolymer.

5. The block copolymer of claim 1 , wherein the B1 block forms 4-25 wt. % of the block copolymer.

6. The block copolymer of claim 1 , wherein

A1 is selected from a [(poly-p-tert-butyl alkylstyrene) block, a [(poly-p-methylstyrene) block, or combinations thereof, and having a molecular weight from 5,000-30,000 g/mol;

B1 is a hydrogenated polyisoprene block (E/P) having a molecular weight from 1000-50000 g/mol; and

C1 is a polystyrene block having a molecular weight from 1,000-20,000 g/mol.

7. The block copolymer of claim 6 , wherein the styrene units in the polymer block C1 are sulfonated to the extent of 1-100 mol percent.

8. The block copolymer of claim 6 , wherein the block B1 forms 4-25 wt. % of the block copolymer.

9. The block copolymer of claim 1 , wherein

A1 is a [(poly-p-tert-butyl alkylstyrene) block, a [(poly-p-methylstyrene) block, or combinations thereof having a molecular weight from 5,000-30,000 g/mol;

B1 is a hydrogenated polybutadiene block (E/B) having a molecular weight from 1000-50000 g/mol;

the block C1 consists essentially of polymerized styrene and hydrogenated butadiene units and has a molecular weight from 1,000-20,000 g/mol;

and prior to hydrogenation, the block C1 forms from 1-10 wt % of the overall weight of the block copolymer.

10. The block copolymer of claim 9 , wherein the block C1 has a controlled distribution of polymerized styrene units.

11. The block copolymer of claim 9 , wherein the block C1 has a random distribution of polymerized styrene units.

12. The block copolymer of claim 10 , wherein 10-100 mol percent of the polymerized styrene units in the block C1 are sulfonated.

13. A sulfonated styrenic block copolymer consisting essentially of polymer blocks A1, B1 and D1 and having a formula [A1-B1-D1], wherein

A1 is a poly(para-alkylstyrene) block having a molecular weight from 1,000 to 60,000 g/mol;

B1 is a hydrogenated polyisoprene block (E/P) or a hydrogenated polybutadiene block (E/B) having a molecular weight from 1,000 to 100,000 g/mol; and

D1 is a sulfonated polystyrene block; or a polymer block consisting essentially of sulfonated styrene units, and hydrogenated butadiene units and/or hydrogenated isoprene units;

wherein prior to hydrogenation,

the block B1 has a vinyl content of 5-75 mol %, and

the block D1 forms from 1-80 wt % of the overall weight of the block copolymer;

and wherein prior to sulfonation,

the block D1 is a polystyrene block having a molecular weight from 1,000 to 100,000 g/mol.

14. The sulfonated block copolymer of claim 13 , wherein the polymerized styrene units in the block D1 has a degree of sulfonation from 1-100 mole %.

15. The block copolymer of claim 13 , having one or more of a dielectric constant from 10 2 -10 8 , a loss angle from 0.05-0.25, a breakdown voltage from 500-1000 volts, and a specific resistance from 10 8 -10 18 ohm/cm, measured according to ASTM D150 test method.

16. A dielectric material comprising the block copolymer of claim 13 .

17. An insulating material comprising the block copolymer of claim 13 .

Assignments (5)
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 →
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 →
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 →
Continuity (2)
Provisional Application 62828272 · Apr 2, 2019
Related Publication 20200317848A1 · Oct 8, 2020