Surfactant responsive emulsion polymerization micro-gels

Patent metadata

Field	Value
Publication number	US-11274173-B2
Application number	US-201916552250-A
Country	US
Kind code	B2
Filing date	Aug 27, 2019
Priority date	Dec 17, 2013
Publication date	Mar 15, 2022
Grant date	Mar 15, 2022

Abstract

A stable, aqueous composition containing a crosslinked, nonionic, amphiphilic polymer capable of forming a yield stress fluid in the presence of a surfactant is disclosed. The yield stress fluid is capable of suspending insoluble materials in the form of particulates and/or droplets requiring suspension or stabilization.

First claim

What is claimed is:

1. A yield stress composition comprising:
(A) water;
(B) about 0.1 to about 5 wt. % of at least one nonionic amphiphilic polymer polymerized from a monomer composition:
(i) from about 20 to about 50 wt. % of hydroxyethyl methacrylate;
(ii) from about 20 to about 50 wt. % of hydroxyethyl methacrylate;
(iii) from about 10 to about 30 wt. % ethyl acrylate;
(iv) from about 10 to about 30 wt. % butyl acrylate;
(v) from about 1 to about 10 wt. % of at least one associative and/or semi-hydrophobic monomer (wherein all monomer weight percentages are based on the weight of the total monomers);
(vi) from about 0.01 to about 5 wt. % of at least one amphiphilic crosslinking agent containing at least two allyl groups selected from formulas (III) and (IV):

where:
R1 is a C 10-24 alkyl, alkaryl, alkenyl, or cycloalkyl;
R2 is CH 3 , CH 2 CH 3 , C 6 H 5 , or C 14 H 29 ;
R3 is H or Z − M +
Z − is SO 3 − , or PO 3 2 ;
M + is Na + , K + , NH 4 + , or an alkanolamine;
x is 2-10;
y is 0-200; and
z is 4-200;

where:
n is 1 or 2;
z is 4 to 40; and
R 4 is H, SO 3 − M + or PO 3 − M + , and M is selected from Na + , K + , NH 4 + or an alkanolamine; and
(C) from about 1 to about 70 wt % based on the total weight of the yield stress fluid of at least one surfactant.

2. A yield stress composition according to claim 1 wherein the concentration of said polymer ranges from about 0.5 to about 3 wt. %.

3. A yield stress composition of claim 1 wherein the at least one surfactant is selected from an anionic, cationic, nonionic, or mixtures thereof.

4. A yield stress composition according to claim 3 wherein the at least one surfactant is selected from an anionic surfactant.

5. A yield stress composition according to claim 3 wherein the at least one surfactant is selected from an anionic surfactant and an amphoteric surfactant.

6. A yield stress composition according to claim 5 wherein the at least one anionic surfactant is selected from sodium dodecyl sulfate, sodium lauryl sulfate, sodium laureth sulfate, or mixtures thereof.

7. A yield stress composition according to claim 5 wherein the at least one amphoteric surfactant is cocamidopropyl betaine.

8. A yield stress composition according to claim 5 wherein the ratio of anionic surfactant to amphoteric surfactant (active material) is 10:1 to about 2:1.

9. A yield stress composition according to claim 1 wherein the concentration of surfactant is less than 25 wt. % (active), based on the weight of the yield stress fluid.

10. A yield stress composition according to claim 9 wherein the concentration of surfactant ranges from about 6 to about 20 wt. % (active material), based on the weight of the total composition.

11. A yield stress composition according to claim 1 wherein said yield stress fluid has properties that are substantially independent of pH when in the pH range 2 to 14.

12. A yield stress yield stress composition of claim 1 having a nephelometric turbidity unit (NTU) value of 50 or less.

13. A yield stress composition of claim 1 further comprising an electrolyte.

14. A yield stress composition according to claim 13 wherein said electrolyte is selected from potassium pyrophosphate, potassium tripolyphosphate, sodium or potassium citrate, calcium chloride and calcium bromide, zinc halides, barium chloride calcium nitrate, potassium chloride, sodium chloride, potassium iodide, sodium bromide, and ammonium bromide, alkali metal or ammonium nitrates, and blends thereof.

15. A yield stress composition according to claim 14 wherein the amount of the electrolyte ranges from about 0.1 to about 4 wt. %, based on the weight of the total composition.

16. A yield stress composition according of claim 15 further comprising an insoluble material, a particulate material, or combinations thereof.

17. A yield stress composition according to claim 16 wherein said particulate material is selected from mica, coated mica, pigments, exfoliants, anti-dandruff agents, clay, swellable clay, laponite, microsponges, cosmetic beads, cosmetic microcapsules, flakes, or mixtures thereof.

18. A yield stress composition according to claim 16 wherein said particulate material is selected from sand, sintered bauxite, glass balls, ceramic materials, polystyrene beads, or mixtures thereof.

19. A yield stress composition according to claim 16 wherein said insoluble material is selected from gas bubbles, liposomes, silicones, or mixtures thereof.

20. A drilling fluid for use in drilling subterranean formations comprising a yield stress composition according claim 1 .

21. A hydraulic fracturing fluid for use in fracturing subterranean formations comprising a yield stress composition according claim 1 .

22. A hydraulic fracturing fluid according to claim 21 further comprising a proppant.

23. A yield stress composition according to claim 1 wherein said semi-hydrophobic monomer is selected from at least one monomer represented by formulas VIII and IX:

wherein R 14 is hydrogen or methyl; A is —CH 2 C(O)O—, —C(O)O—, —O—, —CH 2 O—, —NHC(O)NH—, —C(O)NH—, —Ar—(CE 2 ) z -NHC(O)O—, —Ar—(CE 2 ) z -NHC(O)NH—, or —CH 2 CH 2 NHC(O)—; Ar is a divalent arylene; E is H or methyl; z is 0 or 1; k is an integer ranging from about 0 to about 30, and m is 0 or 1, with the proviso that when k is 0, m is 0, and when k is in the range of 1 to about 30, m is 1; (R 15 —O) n is a polyoxyalkylene moiety, which can be a homopolymer, a random copolymer, or a block copolymer of C 2 -C 4 oxyalkylene units, R 15 is a divalent alkylene moiety selected from C 2 H 4 , C 3 H 6 , or C 4 H 8 , and combinations thereof; and n is an integer in the range of about 2 to about 150; R 17 is selected from hydrogen and a linear or branched C 1 -C 4 alkyl group; and D represents a vinyl or an allyl moiety.

24. A yield stress composition according to claim 23 wherein said semi-hydrophobic monomer is selected from at least one monomer represented by formulas VIIIA and VIIIB:
CH 2 ═C(R 14 )C(O)O—(C 2 H 4 O) a (C 3 H 6 O) b —H  VIIIA

CH 2 ═C(R 14 )C(O)O—(C 2 H 4 O) a (C 3 H 6 O) b —CH 3   VIIIB

wherein R 14 is hydrogen or methyl, and “a” is an integer ranging from 0 or 2 to about 120, and “b” is an integer ranging from about 0 or 2 to about 120, subject to the proviso that “a” and “b” cannot be 0 at the same time.

25. A yield stress composition according to claim 1 wherein said amphiphilic polymer comprises a conventional crosslinking agent which is present in an amount sufficient to be incorporated into said polymer from about 0.01 to about 1 wt. %, based on the dry weight of the polymer.

26. A yield stress composition according to claim 25 wherein said conventional crosslinking agent contains an average of about 3 crosslinkable unsaturated moieties.

27. A yield stress composition according to claim 25 wherein said monomer mixture comprises a conventional crosslinking agent which is present in an amount sufficient to be incorporated into said polymer from about 0.01 to about 0.3 wt. %, based on

Assignees

• Lubrizol Advanced Mat Inc

Inventors

• Hsu Shui-Jen Raymond
• Chari Krishnan
• Li Sinan

Classifications

• C09K8/602

  containing surfactants · CPC title

• C09K8/12

  containing synthetic organic macromolecular compounds or their precursors · CPC title

• C08J3/075

  Macromolecular gels · CPC title

• C08F220/20 Primary

  of polyhydric alcohols or phenols {, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate} · CPC title

• C08F220/1802

  C2-(meth)acrylate, e.g. ethyl (meth)acrylate · CPC title