Process for the preparation of an aqueous emulsion of a midblock sulfonated block copolymer
The present invention concerns aqueous emulsions and a process for preparing aqueous emulsions 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 steps of providing a cement of a midblock sulfonated styrenic block copolymer in the apolar solvent, mixing the cement with a co-solvent to form a mixture, emulsifying the mixture in the absence of a surfactant with water to produce an emulsion, and removing the hydrocarbon solvent and any optional 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.
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 an apolar solvent, wherein the apolar solvent is a hydrocarbon compound with a boiling point in the range of 49 to 99° 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), in the absence of a surfactant, 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 apolar 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 MEK, 1-propanol, or THF.
4. The process of claim 1 , wherein the co-solvent has a boiling point of at most 99° C.
5. The process of claim 1 , wherein the midblock sulfonated block copolymers are either linear or branched, optionally having the general configuration A-B-A, (A-B) n (A), (A-B-A) n , (A-B-A) n X, (A-B) n X, A-B-D-B-A, A-D-B-D-A, (A-D-B) n (A), (A-B-D) n (A), (A-B-D) n X, (A-D-B) n X 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) 2 X, (A-B-D)X, (A-D-B) 2 X, or a mixture thereof structures or is radial and has the structures (A-B) n X, (A-D-B) n X, or a mixture thereof, 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,
wherein the term “molar mass” refers to polystyrene equivalent, or apparent, molar mass of the polymer or block of the copolymer, measured with gel permeation chromatography (GPC) using polystyrene calibration standards, according to ASTM D5296-11.
8. The process of claim 1 , wherein the midblock sulfonated block copolymers has an Ion Exchange Capacity (IEC) in the range of 0.2 to 2.0.
9. 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.
10. The process of claim 1 , wherein the cement has a solids content between 5 to 60% by mass.
11. The process of claim 1 , wherein in step (a) a homogenizer is used.
12. 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, having a solids content in the range of from 10-30% by mass calculated on the mass of the emulsion, wherein the average particle size of the particles of the midblock sulfonated styrenic block copolymer as determined by laser diffraction spectroscopy is at most 2.0 μm, containing up to 1500 ppm calculated on the mass of the emulsion of a co-solvent, wherein the co-solvent is a polar aprotic solvent or polar protic solvent with a Hansen polarity parameter (δp) in the range of 2.8-15, and a Hansen hydrogen bonding parameter (δp) in the range of 4.0 to 27 (calculated in √MPa).