IP Library Granted Patent US 10,017,611
Granted Patent B2
US 10,017,611 · App. 15/300,860 · Granted Jul 10, 2018

Process for the preparation of an aqueous emulsion of a midblock sulfonated block copolymer

Inventors: Bert Krutzer (Duiven, NL); Coen De Oude (Houston, TX)
Assignee: Kraton Polymers U.S. LLC
C08J3/07C08J2353/00
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Quick Facts
Patent No.
US 10,017,611
App. No.
15/300,860
Granted
Jul 10, 2018
Kind
B2
Abstract

The present invention provides an aqueous emulsion and a process for preparing an aqueous emulsion of a midblock sulfonated styrenic block copolymer comprising at least two non-sulfonated polymer end-blocks A and at least one 5 sulfonated block B comprising the steps of providing a cement of a midblock sulfonated styrenic block copolymer in a non-polar solvent wherein the non-polar solvent is a hydrocarbon compound comprising from 5 to 12 carbon atoms with a boiling point of less than 100 degree Celsius or mixture of such compounds, mixing the cement with a co-solvent to form a mixture, emulsifying the mixture optionally in the 10 presence of an emulsifier with water to produce an emulsion, and removing the hydrocarbon solvent and optionally the co-solvent from the emulsion to produce the aqueous emulsion. The resulting emulsion of the midblock sulfonated styrenic block copolymer has relatively small particle diameters.

Claims (19)

1. A process for preparing an aqueous emulsion of a midblock sulfonated styrenic block copolymer comprising at least two non-sulfonated polymer end-blocks A and at least one sulfonated block B, comprising the following steps:

a) providing a cement of said midblock sulfonated styrenic block copolymer in a non-polar solvent, wherein the non-polar solvent is a hydrocarbon compound comprising from 5 to 12 carbon atoms with a boiling point of less than 100° C. or mixture of such compounds;

b) mixing the cement of step a) with a co-solvent to form a mixture;

c) emulsifying the mixture of step b), optionally in the presence of an emulsifier, with water to produce an emulsion;

d) removing the hydrocarbon solvent and optionally the co-solvent from the emulsion to produce the aqueous emulsion,

wherein

the non-polar solvent has a Hansen polarity parameter (δp) smaller than 2.0 (expressed in √MPa), and the co-solvent is a polar aprotic solvent or polar protic solvent with a Hansen polarity parameter (δp) in the range of 2.8 to 15, and a Hansen hydrogen bonding parameter (δh) in the range of 4.0 to 27 (expressed in √MPa).

2. The process of claim 1 , wherein the co-solvent has a Hansen polarity parameter (δP) in the range of 5.0 to 12 (expressed in √MPa).

3. The process of claim 1 , wherein the co-solvent is selected from acetone, tetrahydrofuran, methyl ethyl ketone, and 1-propanol.

4. The process of claim 1 , wherein the co-solvent has a boiling point of less than 100° C.

5. The process of claim 1 , wherein the midblock sulfonated block copolymers are either linear or branched, and preferably have the general configuration A-B-A, (A-B)n(A), (A-B-A)n, (A-B-A)nX, (A-B)nX, A-B-D-B-A, A-D-B-D-A, (A-D-B)n(A), (A-B-D)n(A), (A-B-D)nX, (A-D-B)nX or mixtures thereof, where n is an integer from 2 to about 30, X is a coupling agent residue, wherein A represents the non-sulfonated styrenic polymer end-block, B represents the interior styrenic polymer block carrying sulfonyl groups and/or derivatives thereof, and D represents an interior polymer block D that has a glass transition temperature of less than 20° C.

6. The process of claim 5 , wherein the midblock sulfonated block copolymer is linear and has the structures A-B-A, (A-B)2X, (A-B-D)2X and (A-D-B)2X structures or is radial and has the structures (A-B)nX or (A-D-B)nX where n is 3 to 6.

7. The process of claim 5 , wherein

a) each A block independently is a polymer block having an apparent number average molar mass between 1,000 and 60,000; and/or

b) each D block, if present, independently is a polymer block having an apparent number average molar mass between 1,000 and 60,000, and/or

c) each B block independently is a polymer block having an apparent number average molar mass between 10,000 and 300,000.

8. The process of claim 1 , wherein the mass ratio between the hydrocarbon solvent and the co-solvent is in the range of 10:1 to 1:2.

9. The process of claim 1 , wherein the cement has a solids content between 5 to 60% by mass.

10. The process of claim 1 , wherein in step (a) a homogenizer is used.

Assignments (6)
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 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jul 12, 2017
From: KRUTZER, BERT; DE OUDE, COEN
To: KRATON POLYMERS U.S. LLC
Reel/Frame 042987/0128 →
Priority Claims (1)
NL 2012551 · Apr 2, 2014 · national
Continuity (1)
Related Publication 20170022328A1 · Jan 26, 2017