Surfactant Responsive Emulsion Polymerized Micro-Gels
AssigneeLubrizol Advanced Materials, Inc.
InventorsShui-Jen Raymond Hsu, Krishnan Chari, Wei-Yeih Yang, Prachur Bhargava, Murat Kadir
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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.
Claims98
A yield stress fluid composition comprising water, at least one nonionic amphiphilic polymer and at least one surfactant wherein the concentration of said polymer is 5 wt. % or less and the concentration of said surfactant is 30 wt. % or less, based on the total weight of the composition, wherein said polymer is polymerized from a monomer composition comprising at least one hydrophilic monomer at least one hydrophobic monomer, wherein said hydrophilic monomer is selected from hydroxy(C1-C5)alkyl (meth)acrylates, N-vinyl amides, amino group containing monomers, or mixtures thereof;
- wherein said hydrophobic monomer is selected from esters of (meth)acrylic acid with alcohols containing 1 to 30 carbon atoms, vinyl esters of aliphatic carboxylic acids containing 1 to 22 carbon atoms, vinyl ethers of alcohols containing 1 to 22 carbon atoms, vinyl aromatic monomers, vinyl halides, vinylidene halides, associative monomers, semi-hydrophobic monomers, or mixtures thereof.
A composition according to any of the preceding claims wherein said hydroxy(C1-C5)alkyl (meth)acrylate is selected from at least one compound represented by the formula:
- wherein R is hydrogen or methyl and R1 is an divalent alkylene moiety containing 1 to 5 carbon atoms, wherein the alkylene moiety optionally can be substituted by one or more methyl groups.
A composition according to of any of the preceding claims wherein said amino group containing monomer is selected from (meth)acrylamide, diacetone acrylamide and at least one monomer structurally represented by the following formulas:
- wherein R2 is hydrogen or methyl, R3 independently is selected from hydrogen, C1 to C5 alkyl and C1 to C5 hydroxyalkyl, and R4 independently is selected from is C1 to C5 alkyl or C1 to C5 hydroxyalkyl, R5 is hydrogen or methyl, R6 is C1 to C5 alkylene, R7 independently is selected from hydrogen or C1 to C5 alkyl, and R8 independently is selected from C1 to C5 alkyl;
- or mixtures thereof.
A composition according to any of the preceding claims wherein said N-vinyl amide is selected from a N-vinyllactam containing 4 to 9 atoms in the lactam ring moiety, wherein the ring carbon atoms, optionally, can be substituted by one or more C1-C3 lower alkyl group.
A composition according to any of the preceding claims wherein said ester of (meth)acrylic acid with alcohols containing 1 to 30 carbon is selected from at least one compound represented by the formula:
- wherein R9 is hydrogen or methyl and R10 is C1 to C22 alkyl.
A composition according to any of the preceding claims wherein said vinyl ester of aliphatic carboxylic acids containing 1 to 22 carbon atoms is selected from at least one compound represented by the formula:
- wherein R11 is a C1 to C22 aliphatic group which can be an alkyl or alkenyl.
A composition according to any of the preceding claims wherein said vinyl ether of alcohols containing 1 to 22 carbon atoms is selected from at least one compound represented by the formula:
- wherein R13 is a C1 to C22 alkyl.
A composition according to any of the preceding claims wherein said associative monomer comprises (i) an ethylenically unsaturated end group portion;
- (ii) a polyoxyalkylene mid-section portion, and (iii) a hydrophobic end group portion containing 8 to 30 carbon atoms.
A composition according to any of the preceding claims wherein said associative monomer is represented by formulas VII and/or VIIA:
- wherein R14 is hydrogen or methyl;
- A
- is —CH2C(O)O—, —C(O)O—, —O—, —CH2O—, —NHC(O)NH—, —C(O)NH—, —Ar—(CE2)z-NHC(O)O—, —Ar—(CE2)z-NHC(O)NH—, or —CH2CH2NHC(O)—;
- Ar is a divalent arylene (e.g., phenylene);
- 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;
- D represents a vinyl or an allyl moiety;
- (R15—O)n is a polyoxyalkylene moiety, which can be a homopolymer, a random copolymer, or a block copolymer of C2-C4 oxyalkylene units, R15 is a divalent alkylene moiety selected from C2H4, C3H6, or C4H8, and combinations thereof;
- and n is an integer in the range of about 2 to about 150 in one aspect, from about 10 to about 120 in another aspect, and from about 15 to about 60 in a further aspect;
- Y is
- R15O—, —R15NH—, —C(O)—, —C(O)NH—, —R15NHC(O)NH—, or —C(O)NHC(O)—;
- R16 is a substituted or unsubstituted alkyl selected from a C8-C30 linear alkyl, a C8-C30 branched alkyl, a C8-C30 carbocyclic alkyl, a C2-C30 alkyl-substituted phenyl, an araalkyl substituted phenyl, and an aryl-substituted C2-C30 alkyl;
- wherein the R16 alkyl group, aryl group, phenyl group optionally comprises one or more substituents selected from the group consisting of a hydroxyl group, an alkoxyl group, benzyl group styryl group, and a halogen group.
A composition according to any of the preceding claims wherein said associative monomer is represented by formula VIIB:
- wherein R14 is hydrogen or methyl;
- R15 is a divalent alkylene moiety independently selected from C2H4, C3H6, and C4H8, and n represents an integer ranging from about 10 to about 60, (R15—O) can be arranged in a random or a block configuration;
- R16 is a substituted or unsubstituted alkyl selected from a C8-C30 linear alkyl, a C8-C30 branched alkyl, a C8-C30 carbocyclic alkyl, a C2-C30 alkyl-substituted phenyl, an araalkyl substituted phenyl, and an aryl-substituted C2-C30 alkyl, wherein the R16 alkyl group, aryl group, phenyl group optionally comprises one or more substituents selected from the group consisting of a hydroxyl group, an alkoxyl group, benzyl group styryl group, and a halogen group.
A composition according to any of the preceding claims wherein said semi-hydrophobic monomer comprises (i) an ethylenically unsaturated end group portion;
- (ii) a polyoxyalkylene mid-section portion, and (iii) an end group portion selected from hydrogen or an alkyl group containing 1 to 4 carbon atoms.
A composition according to any of the preceding claims wherein said semi-hydrophobic monomer is selected from at least one monomer represented by formulas VIII and IX:
- wherein R14 is hydrogen or methyl;
- A
- is —CH2C(O)O—, —C(O)O—, —O—, —CH2O—, —NHC(O)NH—, —C(O)NH—, —Ar—(CE2)z-NHC(O)O—, —Ar—(CE2)z-NHC(O)NH—, or —CH2CH2NHC(O)—;
- Ar is a divalent arylene (e.g., phenylene);
- 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;
- (R15—O)n is a polyoxyalkylene moiety, which can be a homopolymer, a random copolymer, or a block copolymer of C2-C4 oxyalkylene units, R15 is a divalent alkylene moiety selected from C2H4, C3H6, or C4H8, and combinations thereof;
- and n is an integer in the range of about 2 to about 150 in one aspect, from about 5 to about 120 in another aspect, and from about 10 to about 60 in a further aspect;
- R17 is selected from hydrogen and a linear or branched C1-C4 alkyl group;
- and D represents a vinyl or an allyl moiety.
A composition according to any of the preceding claims wherein said semi-hydrophobic monomer is selected from at least one monomer represented by formulas VIIIA and VIIIB:
- CH2═C(R14)C(O)O—(C2H4O),(C3H6O)b—H VIIIA
- CH2═C(R14)C(O)O—(C2H4O)a(C3H6O)b—CH3 VIIIB
- wherein R14 is hydrogen or methyl, and “a” is an integer ranging from 0 or 2 to about 120 in one aspect, from about 5 to about 45 in another aspect, and from about 10 to about 0.25 in a further aspect, and “b” is an integer ranging from about 0 or 2 to about 120 in one aspect, from about 5 to about 45 in another aspect, and from about 10 to about 0.25 in a further aspect, subject to the proviso that “a” and “b” cannot be 0 at the same time.
A composition according to any of the preceding claims wherein said polymer is polymerized from a monomer mixture comprising at least 30 wt. % of said hydrophilic monomer(s) and at least 5 wt. % of said hydrophobic monomers.
A composition according to any of the preceding claims wherein said monomer mixture comprises a crosslinking monomer 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.
A composition according to any of the preceding claims wherein said crosslinking monomer contains an average of about 3 crosslinkable unsaturated moieties.
A composition according to any of the preceding claims wherein said monomer mixture comprises a crosslinking monomer which is present in an amount sufficient to be incorporated into said polymer from about 0.01 to about 0.3 wt. %, based on the dry weight of the polymer.
A composition according to any of the preceding claims wherein the at least one crosslinking monomer is selected from polyallyl ethers of trimethylolpropane, polyallyl ethers of pentaerythritol, polyallyl ethers of sucrose, or mixtures thereof.
A composition according to any of the preceding claims wherein the at least one crosslinking monomer is selected from pentaerythritol diallyl ether, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether;
- or mixtures thereof.
A composition of any of the preceding claims wherein said polymer is in the form of particles that exhibit plateau swelling of at least a factor of 2.5 in linear dimension in the presence of sodium lauryl sulfate and 0.1 wt. % sodium chloride.
A composition according to any of the preceding claims wherein the at least one surfactant is selected from an anionic, cationic, amphoteric, nonionic, or mixtures thereof.
A composition according to any of the preceding claims wherein the at least one surfactant is selected from an anionic surfactant.
A composition according to any of the preceding claims wherein the at least one surfactant is selected from an anionic surfactant and an amphoteric surfactant.
A composition according to any of the preceding claims wherein the at least one anionic surfactant is ethoxylated.
A composition according to any of the preceding claims wherein the at least one anionic surfactant contains an average of 1 to 3 moles of ethoxylation.
A composition according to any of the preceding claims wherein the at least one anionic surfactant contains an average of 1 to 2 moles of ethoxylation.
A composition according to any of the preceding claims wherein the at least one anionic surfactant is selected from sodium dodecyl sulfate, sodium lauryl sulfate, sodium laureth sulfate, or mixtures thereof.
A composition according to any of the preceding claims wherein the at least one amphoteric surfactant is cocamidopropyl betaine.
A composition according to any of the preceding claims wherein the at least polymer and the at least one surfactant are substantially free of ethylene oxide moieties.
A composition according to any of the preceding claims wherein the concentration of surfactant is less than 25 wt. % (active), based on the weight of the yield stress fluid.
A composition according to any of the preceding claims wherein the concentration of surfactant ranges from about 6 to about 20 wt. % (active material), based on the weight of the total composition.
A composition according to any of the preceding claims wherein the ratio of anionic surfactant to amphoteric surfactant (active material) is 10:1 to about 2:1 in one aspect, and 9:1, 8:1, 7:1 6:1, 5:1, 4.5:1, 4:1, or 3:1 in another aspect.
A composition according to any of the preceding claims wherein the amount of polymer solids ranges from about 1 to about 3 wt. %, based on the weight of the total composition.
A composition according to any of the preceding claims wherein said yield stress of said yield stress fluid is at least 0.1 Pa.
A composition according to any of the preceding claims wherein said yield stress of said yield stress fluid is at least 0.5 Pa.
A composition according to any of the preceding claims wherein said yield stress of said yield stress fluid is at least 1 Pa.
A composition according to any of the preceding claims wherein said yield stress fluid is able to suspend beads of a size between 0.5 and 1.5 mm for at least one month at 23° C. wherein the difference in specific gravity between the bead material and water is between +/−0.01 and 0.5.
A composition according to any of the preceding claims wherein said composition is able to suspend microcapsules of a size between 0.5 and 300 μm for at least one month at 23° C. wherein the difference in specific gravity between the microcapsule beads and water is between +/−0.2 and 0.5.
A composition according to any of the preceding claims wherein said yield stress is substantially independent of pH in the pH range 2 to 14.
A composition according to any of the preceding claims wherein said yield stress is substantially independent of pH in the pH range 3 to 10.
A composition according to any of the preceding claims wherein the percent optical transmission is at least 10%.
A composition according to any of the preceding claims wherein the percent optical transmission is at least 20%.
A composition according to any of the preceding claims further comprising mica particles.
A composition according to any of the preceding claims that is pearlescent in appearance.
A composition according to any of the preceding claims wherein the viscosity is less than 2 Pa·s at a shear rate of 3 reciprocal seconds.
A composition according to any of the preceding claims that has a shear thinning index less than 0.5 at shear rates between 0.1 and 1 reciprocal second.
A composition according to any of the preceding claims wherein the elastic modulus is greater than the viscous modulus at oscillatory stress below a critical stress at a fixed frequency.
A composition according to any of the preceding claims wherein said polymer is an emulsion polymer.
A composition according to any of the preceding claims wherein said polymer is an emulsion polymer.
A composition in any of the preceding claims further comprising an electrolyte.
A hydraulic fracturing fluid according to claim 109 further comprising a proppant.
Dependencies are inferred from the claim text.