Water-in-oil polymer emulsion containing microparticles

• US 7,531,600 B1
• Filed: 11/12/2004
• Issued: 05/12/2009
• Est. Priority Date: 11/12/2003
• Status: Expired due to Fees

• Current Assignee: Kroff Chemical Company Incorporated
• Original Assignee: Kroff Chemical Company Incorporated
• Inventors: Rey, Paul
• Primary Examiner(s): EGWIM, KELECHI CHIDI
• Application Number:
  US10/988,424
• Time in Patent Office: 1,642 Days
• Field of Search: 524/801, 524/727, 210/698, 210/701
• US Class Current: 524/801
• CPC Class Codes: C02F 1/56 Macromolecular compounds
• CPC Class Codes: C02F 11/148 Combined use of inorganic and organic substances, being added in the same treatment step
• CPC Class Codes: C02F 2305/04 Surfactants, used as part of a formulation or alone
• CPC Class Codes: C08F 2/32 Polymerisation in water-in-oil emulsions

Abstract

A storage stable water-in-oil emulsion composition that includes 5% to 99% by weight of a water-in-oil emulsion polymer including a polymer or copolymer containing repeat units from an acrylamide monomer; 0.1% to 10% by weight of one or more inorganic microparticles; 0.5% to 90% by weight of a carrier solvent; and 0 to 90% by weight of a fluidizing agent. The compositions can be used to treat aqueous systems including paper processing, sludge dewatering and for fracturing fluids for subterranean formations.

Claims

1. A water-in-oil emulsion composition comprising:

(a) 5% to 99% by weight of a water-in-oil emulsion comprising;

(i) 10% to 90% by weight of a hydrophobic oil phase;

(ii) 0.5% to 10% by weight of a surfactant system; and

(iii) 5% to 90% by weight of a polymer-containing aqueous phase comprising water and a polymer or copolymer containing repeat units from an acrylamide monomer, wherein the polymer or copolymer comprises from 2% by weight to 89.5% by weight of the water-in-oil emulsion;

(b) 0.1% to 10% by weight of one or more inorganic microparticles;

(c) 0.5% to 90% by weight of a carrier solvent; and

(d) 0 to 90% by weight of a fluidizing agent,

wherein each of the above weight percentages is based upon the total weight of the composition.

2. The composition of claim 1, wherein the oil phase comprises one or more oils selected from the group consisting of mineral oil, synthetic oil, modified oil, paraffinic oil, benzene, xylene, toluene, mineral oils, kerosene, naphthas, petroleums, blends of aromatic and aliphatic hydrocarbons containing 4 or greater carbon atoms, and vegetable oil.

3. The composition of claim 1, wherein the surfactant system comprises one or more surfactants selected from the group consisting of alkanolamides, polyoxyethylene derivatives of sorbitan esters, sorbitan monooleate, sorbitan monostearate, C₆-C₂₂ linear or branched alkyl ethoxylates with 1 to 30 oxyethylene units, C₆-C₂₂ linear or branched alkyl propoxylates with 1 to 30 oxypropylene units, C₆-C₂₂ linear or branched alkyl ethoxylates/propoxylates with 1 to 30 combined oxyethylene and propoxylate units, alkylaryl ethoxylates containing a C₆-C₂₂ aryl group with 1 to 30 oxyethylene units, hexadecyl sodium phthalate, cetyl sodium phthalate, stearyl sodium phthalate, and ethylene oxide condensates of fatty acid amides.

4. The composition of claim 1, wherein the polymer or copolymer of the aqueous phase is selected from non-ionic poly(acrylamide) homopolymer, non-ionic copolymers, anionic copolymers, cationic copolymers, amphoteric copolymers and ampholytic copolymers.

5. The composition of claim 1, wherein the repeat units from an acrylamide monomer comprise one or more repeat units according to Formula I:

6. The composition of claim 1, wherein the copolymer of the aqueous phase further comprises repeat units derived from acrylamidopropyl trimethyl ammonium chloride (APTAC), methacrylamidopropyltrimethyl ammonium chloride (MAPTAC), methacryloyloxyethyl trimethyl ammonium chloride (METAC) methacryloyloxyethyl trimethyl ammonium methylsulfate (METAMS), acryloyloxyethyl trimethyl ammonium chloride (AETAC), dimethyl diallyl ammonium chloride (DMDAAC), acrylic acid (AA), methacrylic acid (MAA), 2-acrylamido-2-methylpropane sulfonic acid (AMPSA), 2-methacrylamido-2-methylpropane sulfonic acid (MAMPSA), C₁-C₃ alkyl acrylate, C₁-C₃ alkyl methacrylate, n-alkyl acrylamide, methacrylamide, n-alkylmethacrylamide, and diacetone acrylamide.

7. The composition of claim 1, wherein the polymer or copolymer of the aqueous phase has a reduced viscosity, measured using a Ubbelohde Capillary Viscometer at 0.05 g/dl in 1N NaCl at 30°

C. and pH of 7 of from 5 to 50 dl/g.

8. The composition of claim 1, wherein the inorganic microparticles include one or more microparticles selected from the group consisting of fumed silica, precipitated silica, colloidal silica, alumina silicates, treated silica, calcium carbonate, silica flour, diatomites, talc, and borosilicates.

9. The composition of claim 1, wherein the inorganic microparticles have an average particle size of less than 100 μ

m.

10. The composition of claim 1, wherein the inorganic microparticles include one or more microparticles selected from the group consisting of fumed silica, precipitated silica, and colloidal silica.

11. The composition of claim 1, wherein the carrier solvent is one or more selected from the group consisting of mineral oil, synthetic oil, modified oil, paraffinic oil, vegetable oil, ethylene carbonate, propylene carbonate, glycols, polyglycols and glycol ethers.

12. The composition of claim 1, wherein the carrier solvent is a solvent characterized as having Hansen Solubility parameters at 25°

C. of;

δ

_d of from 13 to 18;

δ

_p of from 6 to 12;

δ

_h of at least 20; and

δ

_t of at least 20.

13. The composition of claim 1, wherein the fluidizing agent is selected from the group consisting of mineral spirits, diesel, turpentine, hydrotreated naphtha, Stoddard solvent and kerosene.

28. The composition of claim 1, wherein the polymer or copolymer containing repeat units from an acrylamide monomer further comprises one or more repeat units according to Formula I:

14. A water-in-oil emulsion composition comprising:

(a) 5% to 99% by weight of a water-in-oil emulsion comprising;

(1) 10% to 90% by weight of a hydrophobic oil phase;

(2) 0.5% to 10% by weight of a surfactant system; and

(3) 5% to 90% by weight of a polymer-containing aqueous phase comprising water and the polymer or copolymer containing repeat units from an acrylamide monomer, wherein the polymer or copolymer comprises from 2% by weight to 89.5% by weight of the water-in-oil emulsion,

wherein each of the weight percentages (1)-(3) is based upon total weight of the water-in-oil emulsion;

(b) 0.1% to 5% by weight of one or more inorganic microparticles selected from the group consisting of fumed silica, precipitated silica, colloidal silica, alumina silicates, treated silica, calcium carbonate, talc, and borosilicates;

(c) 0.5% to 90% by weight of a carrier solvent selected from the group consisting of mineral oil, synthetic oil, modified oil, paraffinic oil, vegetable oil, ethylene glycol, propylene glycol, ethylene carbonate, propylene carbonate glycol ethers and mixtures thereof; and

(d) 0 to 90% by weight of a fluidizing agent,

wherein each of the above weight percentages of (a)-(d) is based upon the total weight of the composition.

15. The composition of claim 14, wherein the surfactant system comprises of one or more surfactants selected from the group consisting of alkanolamides, polyoxyethylene derivatives of sorbitan esters, sorbitan monooleate, sorbitan monostearate, C₆-C₂₂ linear or branched alkyl ethoxylates with 1 to 30 oxyethylene units, C₆-C₂₂ linear or branched alkyl propoxylate with 1 to 30 oxypropylene units, C₆-C₂₂ linear or branched alkyl ethoxylate/propoxylate with 1 to 30 combined oxyethylene and propoxylate units, alkylaryl ethoxylates containing a C₆-C₂₂ aryl group with 1 to 30 oxyethylene units, hexadecyl sodium phthalate, cetyl sodium phthalate, stearyl sodium phthalate, and ethylene oxide condensates of fatty acid amides.

16. The composition of claim 14, wherein the polymer or copolymer of the aqueous phase is selected from non-ionic poly(acrylamide) homopolymer, non-ionic copolymers, anionic copolymers, cationic copolymers, amphoteric copolymers and ampholytic copolymers.

17. The composition of claim 14, wherein the repeat units from an acrylamide monomer comprise one or more repeat units according to Formula I:

18. The composition of claim 14, wherein the oil phase comprises one or more oils selected from the group consisting of mineral oil, synthetic oil, modified oil, paraffinic oil, benzene, xylene, toluene, mineral oils, kerosene, naphthas, petroleums, blends of aromatic and aliphatic hydrocarbons containing 4 or greater carbon atoms, and vegetable oil.

19. The composition of claim 14, wherein the polymer or copolymer of the aqueous phase is selected from non-ionic poly(acrylamide) homopolymer, non-ionic copolymers, anionic copolymers, cationic copolymers, amphoteric copolymers and ampholytic copolymers.

20. The composition of claim 14, wherein the copolymer of the aqueous phase further comprises repeat units derived from acrylamidopropyltrimethyl ammonium chloride (APTAC), methacrylamidopropyltrimethyl ammonium chloride (MAPTAC), methacryloyloxyethyl trimethyl ammonium chloride (METAC) methacryloyloxyethyl trimethyl ammonium methylsulfate (METAMS), acryloyloxyethyl trimethyl ammonium chloride (AETAC), dimethyl diallyl ammonium chloride (DMDAAC), acrylic acid (AA), methacrylic acid (MAA), 2-acrylamido-2-methylpropane sulfonic acid (AMPSA), 2-methacrylamido-2-methylpropane sulfonic acid (MAMPSA), C₁-C₃ alkyl acrylate, C₁-C₃ alkyl methacrylate, n-alkyl acrylamide, methacrylamide, n-alkylmethacrylamide, and diacetone acrylamide.

21. The composition of claim 14, wherein the polymer or copolymer of the aqueous phase has a reduced viscosity, measured using a Ubbelohde Capillary Viscometer at 0.05 g/dl in 1N NaCl at 30°

C. and pH of 7 of from 5 to 50 dl/g.

22. The composition of claim 14, wherein the inorganic microparticles include one or more microparticles selected from the group consisting of fumed silica, precipitated silica, and colloidal silica.

23. The composition of claim 14, wherein the inorganic microparticles have an average particle size of less than 100 μ

m.

24. The composition of claim 14, wherein the carrier solvent is a solvent characterized as having Hansen Solubility parameters at 25°

C. of;

δ

_d of from 13 to 18;

δ

_p of from 6 to 12;

δ

_h of at least 20; and

δ

_t of at least 20.

29. The composition of claim 14, wherein the polymer or copolymer containing repeat units from an acrylamide monomer further comprises one or more repeat units according to Formula I:

25. A water-in-oil emulsion composition comprising:

(a) 5% to 99% by weight of a water-in-oil emulsion comprising;

(1) 10% to 90% by weight of a hydrophobic oil phase consisting essentially of one or more oils selected from the group consisting of mineral oil, synthetic oil, modified oil, paraffinic oil, and vegetable oil;

(2) 0.5% to 10% by weight of a surfactant system consisting essentially of one or more surfactants selected from the group consisting of alkanolamides, polyoxyethylene derivatives of sorbitan esters, sorbitan monooleate, sorbitan monostearate, C₆-C₂₂ linear or branched alkyl ethoxylates with 1 to 30 oxyethylene units, C₆-C₂₂ linear or branched alkyl propoxylate with 1 to 30 oxypropylene units, C₆-C₂₂ linear or branched alkyl ethoxylate/propoxylate with 1 to 30 combined oxyethylene and propoxylate units, alkylaryl ethoxylates containing a C₆-C₂₂ aryl group with 1 to 30 oxyethylene units, hexadecyl sodium phthalate, cetyl sodium phthalate, stearyl sodium phthalate, and ethylene oxide condensates of fatty acid amides; and

(3) 5% to 90% by weight of a polymer-containing aqueous phase consisting essentially of water, catalyst and initiator residues, optionally salts, and polymers consisting essentially of repeat units from one or more repeat units according to Formula I;

26. The composition of claim 25, wherein the polymer or copolymer of the aqueous phase has a reduced viscosity, measured using a Ubbelohde Capillary Viscometer at 0.05 g/dl in 1N NaCl at 30°

C. and pH of 7 of from 5 to 50 dl/g.

27. The composition of claim 25, wherein the inorganic microparticles include one or more microparticles selected from the group consisting of fumed silica, precipitated silica, and colloidal silica.

30. A fracturing fluid comprising the mixture provided by adding a water-in-oil emulsion composition to water, wherein the water-in-oil emulsion composition comprises:

(i) 5% to 99% by weight of a water-in-oil emulsion comprising

(i) 10% to 90% by weight of a hydrophobic oil phase;

(ii) 0.5% to 10% by weight of a surfactant system; and

(iii) 5% to 90% by weight of a polymer-containing aqueous phase comprising water and a polymer or copolymer containing repeat units from an acrylamide monomer, wherein the polymer or copolymer comprises from 2% by weight to 89.5% by weight of the water-in-oil emulsion;

(ii) 0.1% to 10% by weight of one or more inorganic microparticles;

(iii) 0.5% to 90% by weight of a carrier solvent; and

(iv) 0 to 90% by weight of a fluidizing agent,

wherein each of the above weight percentages is based upon the total weight of the composition.

31. The fracturing fluid of claim 30, further comprising (v) 0.5% to 50% by weight of a proppant material.

32. The fracturing fluid of claim 30, wherein the oil phase comprises one or more oils selected from the group consisting of mineral oil, synthetic oil, modified oil, paraffinic oil, benzene, xylene, toluene, mineral oils, kerosene, naphthas, petroleums, blends of aromatic and aliphatic hydrocarbons containing 4 or greater carbon atoms, and vegetable oil.

33. The fracturing fluid of claim 30, wherein the surfactant system comprises of one or more surfactants selected from the group consisting of alkanolamides, polyoxyethylene derivatives of sorbitan esters, sorbitan monooleate, sorbitan monostearate, C₆-C₂₂ linear or branched alkyl ethoxylates with 1 to 30 oxyethylene units, C₆-C₂₂ linear or branched alkyl propoxylate with 1 to 30 oxypropylene units, C₆-C₂₂ linear or branched alkyl ethoxylate/propoxylate with 1 to 30 combined oxyethylene and propoxylate units, alkylaryl ethoxylates containing a C₆-C₂₂ aryl group with 1 to 30 oxyethylene units, hexadecyl sodium phthalate, cetyl sodium phthalate, stearyl sodium phthalate, and ethylene oxide condensates of fatty acid amides.

34. The fracturing fluid of claim 30, wherein the polymer or copolymer of the aqueous phase is selected from non-ionic poly(acrylamide) homopolymer, non-ionic copolymers, anionic copolymers, cationic copolymers, amphoteric copolymers and ampholytic copolymers.

35. The fracturing fluid of claim 30, wherein the repeat units from the acrylamide monomer comprise one or more repeat units according to Formula I:

36. The fracturing fluid of claim 30, wherein the copolymer of the aqueous phase further comprises repeat units derived from acrylamidopropyltrimethyl ammonium chloride (APTAC), methacrylamidopropyltrimethyl ammonium chloride (MAPTAC), methacryloyloxyethyl trimethyl ammonium chloride (METAC) methacryloyloxyethyl trimethyl ammonium methylsulfate (METAMS), acryloyloxyethyl trimethyl ammonium chloride (AETAC), dimethyl diallyl ammonium chloride (DMDAAC), acrylic acid (AA), methacrylic acid (MAA), 2-acrylamido-2-methylpropane sulfonic acid (AMPSA), 2-methacrylamido-2-methylpropane sulfonic acid (MAMPSA), C₁-C₃ alkyl acrylate, C₁-C₃ alkyl methacrylate, n-alkyl acrylamide, methacrylamide, n-alkylmethacrylamide, and diacetone acrylamide.

37. The fracturing fluid of claim 30, wherein the polymer or copolymer of the aqueous phase has a reduced viscosity, measured using a Ubbelohde Capillary Viscometer at 0.05 g/dl in 1N NaCl at 30°

C. and pH of 7 of from 5 to 50 dl/g.

38. The fracturing fluid of claim 30, wherein the inorganic microparticles (ii) include one or more microparticles selected from the group consisting of fumed silica, precipitated silica, colloidal silica, alumina silicates, treated silica, calcium carbonate, talc, and borosilicates.

39. The fracturing fluid of claim 30, wherein the inorganic microparticles (ii) include one or more microparticles selected from the group consisting of fumed silica, precipitated silica, and colloidal silica.

40. The fracturing fluid of claim 30, wherein the carrier solvent (iii) is one or more selected from the group consisting of mineral oil, synthetic oil, modified oil, paraffinic oil, vegetable oil, ethylene glycol, propylene glycol, ethylene carbonate, propylene carbonate and glycol ethers.

41. The fracturing fluid of claim 30, wherein the carrier solvent (iii) is a solvent characterized as having Hansen Solubility parameters at 25°

C. of;

δ

_d of from 13 to 18;

δ

_p of from 6 to 12;

δ

_h of at least 20; and

δ

_t of at least 20.

42. The fracturing fluid of claim 30, wherein the water is selected from the group consisting of fresh water, unsaturated brine and saturated brine.

43. The fracturing fluid of claim 30, further comprising one or more polymers selected from the group consisting of hydroxypropylguar, carboxymethylhydroxypropylguar, carboxymethylguar, hydroxyethyl cellulose, grafted hydroxyethyl cellulose, carboxymethyl cellulose and carboxymethylhydroxyethyl cellulose.

44. The fracturing fluid of claim 30, wherein the water-in-oil emulsion composition substantially is present in the treating fluid in an amount in the range of from about 0.01% to about 10% by weight of the fracturing fluid.

45. The fracturing fluid of claim 30, further comprising 0.01% to 0.3% by weight of a pH adjusting compound for elevating the pH of the treating fluid selected from the group consisting of sodium hydroxide, potassium hydroxide, lithium hydroxide sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium diacetate, potassium diacetate, sodium phosphate, potassium phosphate, sodium dihydrogen phosphate and potassium dihydrogen phosphate.

46. The fracturing fluid of claim 30, further comprising from 0.01% to 0.3 percent by weight of a buffer selected from the group consisting of sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium diacetate, potassium diacetate, sodium phosphate, potassium phosphate, sodium dihydrogen phosphate and potassium dihydrogen phosphate.

47. The fracturing fluid of claim 30, further comprising from 0.01% to 0.1% by weight of a surfactant selected from the group consisting of C₂-C₂₄ linear, branched and cyclic alkyl phenol ethoxylates, C₂-C₂₄ linear, branched and cyclic alkyl ethoxylates, alkyl sulfonates, alkyl aryl sulfonates such as the salts of dodecylbenzene sulfonic acid, alkyltrimethylammonium chloride, branched alkyl ethoxylated alcohols, phenol-formaldehyde nonionic resin blends, cocobetaines, dioctyl sodium sulfosuccinate, imidazolines, alpha olefin sulfonates, linear alkyl ethoxylated alcohols and trialkyl benzylammonium chloride.

48. The fracturing fluid of claim 30, further comprising from 0.1% to 10% by weight of a clay stabilizer selected from the group consisting of potassium chloride, sodium chloride, ammonium chloride, tetramethyl ammonium chloride and temporary clay stabilizers.

49. The fracturing fluid of claim 30, further comprising from 0.01% to 1% by weight of a fluid loss control agent selected from the group consisting of silica flour, starches, waxes and resins.

50. The fracturing fluid of claim 30, further comprising from 0.01 to 2 percent by weight of a delayed breaker for causing the treating fluid to revert to a thin fluid selected from the group of oxidizers, encapsulated oxidizers and enzyme breakers consisting of sodium persulfate, potassium persulfate, ammonium persulfate, magnesium peroxide, sodium chlorite, sodium bromate, alpha and beta amylases, amyloglucosidase, invertase, maltase, cellulose, halogenated isocyanurate, hypochlorites, and hemicellulase.

51. The fracturing fluid of claim 30, wherein the proppant material is selected from the group consisting of resin coated or uncoated sand, sintered bauxite, ceramic materials and glass beads.

52. The fracturing fluid of claim 30, wherein the proppant material is present in the treating fluid in an amount in the range of from about 1 to about 30 pounds of proppant material per gallon of the fracturing fluid.

53. The fracturing fluid of claim 30, wherein the polymer or copolymer containing repeat units from an acrylamide monomer further comprises one or more repeat units according to Formula I:

54. A method for making paper or paper board comprising:

forming a cellulosic suspension;

flocculating the suspension;

draining the suspension on a screen to form a sheet; and

drying the sheet;

wherein the cellulosic suspension is flocculated by the addition of a water-in-oil emulsion composition comprising;

(a) 5% to 99% by weight of a water-in-oil emulsion polymer comprising;

(i) 10% to 90% by weight of a hydrophobic oil phase;

(ii) 0.5% to 10% by weight of a surfactant system; and

(iii) 5% to 90% by weight of a polymer-containing aqueous phase comprising water and a polymer or copolymer containing repeat units from an acrylamide monomer, wherein the polymer or copolymer comprises from 2% by weight to 89.5% by weight of the water-in-oil emulsion;

(b) 0.1% to 10% by weight of one or more inorganic microparticles;

(c) 0.5% to 90% by weight of a carrier solvent; and

(d) 0 to 90% by weight of a fluidizing agent.

55. The method of claim 54, wherein the oil phase comprises one or more oils selected from the group consisting of mineral oil, synthetic oil, modified oil, paraffinic oil, benzene, xylene, toluene, mineral oils, kerosene, naphthas, petroleums, blends of aromatic and aliphatic hydrocarbons containing 4 or greater carbon atoms, and vegetable oil.

56. The method claim 54, wherein the surfactant system comprises one or more surfactants selected from the group consisting of alkanolamides, polyoxyethylene derivatives of sorbitan esters, sorbitan monooleate, sorbitan monostearate, C₆-C₂₂ linear or branched alkyl ethoxylates with 1 to 30 oxyethylene units, C₆-C₂₂ linear or branched alkyl propoxylates with 1 to 30 oxypropylene units, C₆-C₂₂ linear or branched alkyl ethoxylates/propoxylates with 1 to 30 combined oxyethylene and propoxylate units, alkylaryl ethoxylates containing a C₆-C₂₂ aryl group with 1 to 30 oxyethylene units, hexadecyl sodium phthalate, cetyl sodium phthalate, stearyl sodium phthalate, and ethylene oxide condensates of fatty acid amides.

57. The method of claim 54, wherein the repeat units from an acrylamide monomer comprise one or more repeat units according to Formula I:

58. A method of dewatering sludge, wherein the sludge comprises solids and water, comprising the steps of:

adding a water-in-oil emulsion composition to the sludge; and

physically separating the solids from the water;

wherein the water-in-oil emulsion composition comprises;

(a) 5% to 99% by weight of a water-in-oil emulsion polymer comprising;

(i) 10% to 90% by weight of a hydrophobic oil phase;

(ii) 0.5% to 10% by weight of a surfactant system; and

(iii) 5% to 90% by weight of a polymer-containing aqueous phase comprising water and a polymer or copolymer containing repeat units from an acrylamide monomer, wherein the polymer or copolymer comprises from 2% by weight to 89.5% by weight of the water-in-oil emulsion;

(b) 0.1% to 10% by weight of one or more inorganic microparticles;

(c) 0.5% to 90% by weight of a carrier solvent; and

(d) 0 to 90% by weight of a fluidizing agent.

59. The method of claim 58, wherein the oil phase comprises one or more oils selected from the group consisting of mineral oil, synthetic oil, modified oil, paraffinic oil, benzene, xylene, toluene, mineral oils, kerosene, naphthas, petroleums, blends of aromatic and aliphatic hydrocarbons containing 4 or greater carbon atoms, and vegetable oil.

60. The method claim 58, wherein the surfactant system comprises one or more surfactants selected from the group consisting of alkanolamides, polyoxyethylene derivatives of sorbitan esters, sorbitan monooleate, sorbitan monostearate, C₆-C₂₂ linear or branched alkyl ethoxylates with 1 to 30 oxyethylene units, C₆-C₂₂ linear or branched alkyl propoxylates with 1 to 30 oxypropylene units, C₆-C₂₂ linear or branched alkyl ethoxylates/propoxylates with 1 to 30 combined oxyethylene and propoxylate units, alkylaryl ethoxylates containing a C₆-C₂₂ aryl group with 1 to 30 oxyethylene units, hexadecyl sodium phthalate, cetyl sodium phthalate, stearyl sodium phthalate, and ethylene oxide condensates of fatty acid amides.

61. The method of claim 58, wherein the repeat units from an acrylamide monomer comprise one or more repeat units according to Formula I:

62. A water-in-oil emulsion composition consisting essentially of:

(a) 5% to 99% by weight of a water-in-oil emulsion consisting essentially of;

(i) 10% to 90% by weight of a hydrophobic oil phase;

(ii) 0.5% to 10% by weight of a surfactant system; and

(iii) 5% to 90% by weight of a polymer-containing aqueous phase comprising water and a polymer or copolymer containing repeat units from an acrylamide monomer, wherein the polymer or copolymer comprises from 2% by weight to 89.5% by weight of the water-in-oil emulsion;

(b) 0.1% to 10% by weight of one or more inorganic microparticles;

(c) 0.5% to 90% by weight of a carrier solvent; and

(d) 0 to 90% by weight of a fluidizing agent,

wherein each of the above weight percentages is based upon the total weight of the composition.

63. A fracturing fluid consisting essentially of the mixture provided by adding a water-in-oil emulsion composition to water, wherein the water-in-oil emulsion composition consists essentially of:

(i) 5% to 99% by weight of a water-in-oil emulsion consisting essentially of;

(i) 10% to 90% by weight of a hydrophobic oil phase;

(ii) 0.5% to 10% by weight of a surfactant system; and

(iii) 5% to 90% by weight of a polymer-containing aqueous phase comprising water and a polymer or copolymer containing repeat units from an acrylamide monomer, wherein the polymer or copolymer comprises from 2% by weight to 89.5% by weight of the water-in-oil emulsion;

(ii) 0.1% to 10% by weight of one or more inorganic microparticles;

(iii) 0.5% to 90% by weight of a carrier solvent; and

(iv) 0 to 90% by weight of a fluidizing agent,

wherein each of the above weight percentages is based upon the total weight of the composition.