composition of flow limit fluid, drilling fluid, and hydraulic fracturing fluid

专利摘要:
FLOW LIMIT FLUID COMPOSITION, DRILLING FLUID, HYDRAULIC FRACTURE FLUID, AND, USE OF FLOW LIMIT FLUID COMPOSITION A stable aqueous composition containing a cross-linked, nonionic, amphiphilic polymer capable of forming a flow limit fluid in the presence of a surfactant is described. The flow-limit fluid is capable of suspending insoluble materials in the form of particulates and/or droplets that require suspension or stabilization.
公开号:BR112014005919B1
申请号:R112014005919-5
申请日:2012-09-13
公开日:2021-06-08
发明作者:Shui-Jen Raymond Hsu；Krishnan Chari；Wei-Yeih Yang；Prachur Bhargava；Murat Kadir
申请人:Lubrizol Advanced Materials, Inc；
IPC主号:

专利说明:

FIELD OF THE INVENTION
[0001] The present invention relates to rheology modifiers and more specifically to a flow limit fluid comprising the responsive surfactant microgel. Additionally, this invention is also concerned with forming a phase-stable, rheological microgel-responsive surfactant compositions that can be used over a wide pH range to suspended particulates and insoluble materials. FUNDAMENTALS OF THE INVENTION
[0002] We are surrounded in daily life by flow-limit fluids. Simply stated, boundary fluid flows remain stationary until sufficient tension is placed on the fluid at the point at which the fluid will flow. This can be thought of as the initial resistance to flow under stress and is also referred to as the yield value. The yield point is a measurable amount similar to, but not dependent on, viscosity. While certain rheology modifiers can thicken or enhance the viscosity of a composition in which it is included, this does not necessarily have desirable yield-limiting properties.
[0003] A desirable flow limit property is critical to achieving certain physical and aesthetic characteristics in a liquid medium, such as the indefinite suspension of particles, insoluble liquid droplets or the stabilization of gas bubbles within a liquid medium. Particles dispersed in a liquid medium will remain in suspension if the flow limit (flow value) of the medium is sufficient to overcome the effect of gravity or fluctuation on those particles. Insoluble liquid droplets can be prevented from swelling and coalescing and gas bubbles can be suspended and evenly distributed in a liquid medium using the flow rate as a formulation tool. An example of a flow-limit fluid is a rheology modifier microgel that is used, in general, to adjust or modify the rheological properties of aqueous compositions. Such properties include, without limitation, viscosity, flow rate, stability to change viscosity over time, and the ability to suspend particles for indefinite periods of time. These are useful in many consumer and industrial applications. An important consumer application includes its use in the formulation of personal care products such as body washes, skin creams, toothpastes, shampoos, hair gels and other cosmetics. In industrial applications these are useful as underground treatment fluids in the oil and gas industry as a component in drilling and fracturing fluids. Typically, these comprise chemically crosslinked polymers have a pH responsive functionality that is sensitive to base or acid. Polymers can be mixed with other ingredients in a formulation and then neutralized by the addition of a neutralizing agent, such as an acid or base. Acid sensitive thickeners are activated on contact with an acidic agent, while base sensitive thickeners are activated on contact with an alkaline agent. On neutralization, the polymers swell significantly to form a randomly packed close-packed accumulation network (RCP) of swollen crosslinked microgel particles that communicate a desired rheological profile, i.e., flow limit, elastic modulus, and viscosity, as well as optical clarity for the formulation.
[0004] These types of rheology modifiers are well known in the art. For example, U.S. Patent No. 2,798,053; 2,858,281; 3,032,538 and 4,758,641 describe cross-linked carboxylic acid polymers based on acrylic acid, maleic acid, itaconic acid or methacrylic acid monomers. U.S. Patent No. 6,635,702 describes crosslinked alkali swellable acrylate copolymers comprising one or more carboxylic acid monomers and one or more non-acidic vinylic monomers. US Patent No. 7,378,479 describes a crosslinkable acid swellable polymer containing at least one basic amino substituent that is cationic at low pH, at least one hydrophobically modified polyoxyalkylene substituent derived from an associative vinylic monomer, and at least one polyoxyalkylene derivative derived from a semi-hydrophobic vinyl surfactant monomer. A key feature of these pH-responsive microgels is the very large increase in diameter (or size) of individual crosslinked polymer particles upon neutralization. The high swelling efficiency allows formulators to achieve the desired flow limit and viscosity using relatively small amounts of polymer resulting in low cost in use. Dalmont, Pinprayoon and Saunders (Langmuir vol. 24, page 2834, 2008) show that individual particles in a microgel dispersion of a copolymer of ethyl acrylate and methacrylic acid crosslinked with butanediol diacrylate increase in diameter by at least a factor of 3 on pH activation or neutralization. The level of swelling causes an increase in the volume fraction of at least 27 (33). A compressed network is achieved on neutralization (or activation) with a relatively low concentration of polymer (less than 3% by weight).
[0005] Although pH-responsive microgels provide flow-limit fluid with the high efficiency that is desired by the formulator, they suffer from a major disadvantage. Rheological properties are not uniform across a wide pH range and show marked changes as a function of pH. To overcome these difficulties, several non-ionic thickeners have been proposed. U.S. Patent No. 4,722,962 describes nonionic associative thickeners comprising a water-soluble monoethylenically unsaturated monomer and a nonionic urethane monomer. These polymers provide increases in viscosity or thickening of aqueous formulations that are relatively independent of pH but the polymers are not cross-linked and purely associative interactions do not create a yield point.
[0006] In addition to pH-responsive microgels, temperature-responsive microgels are known in the art. Senff and Richtering {Journal of Chemical Physics, vol. III, page 1705, 1999) describe the change in size of chemically crosslinked nonionic poly(N-isopropylacrylamide) (PNIPAM) microgel particles as a function of temperature. The particles mostly swell by a factor of 2.5 in diameter (15 times in terms of volume fraction) when the temperature is reduced from 35°C to 10°C. Although this represents a significant degree of swelling , the use of temperature to activate microgels is undesirable. An activation method is required allowing the exchange of a free-flowing suspension to a flow-limit fluid accumulated under ambient conditions.
[0007] Wu and Zhou {Journal of Polymer Science'. Part B: Polymer Physics, vol.34, page 1597, 1996) describes the effect of the surfactant on the swelling of chemically crosslinked PNIPAM homopolymer microgel particles in water. The use of surfactant to activate microgels is attractive because many formulations contain surfactants as coingredients. However, the swelling efficiency reported by Wu and Zhou is extremely low. The anionic surfactant dodecyl (lauryl) sodium sulfate increases the size of crosslinked PNIPAM particles by only a factor of 1.4 at room temperature. Furthermore, Wu and Zhou do not explain how to create a shear affination flow boundary fluid with high optical clarity.
[0008] Hidi, Napper and Sangster (Macromolecules, vol.28, page 6042, 1995) describe the effect of the surfactant on the swelling of poly(vinyl acetate) homopolymer microgels in water. For microgels that are not crosslinked, an increase in diameter by a factor of 3 to 4 is reported, which corresponds to a 30 to 60 fold change in volume of the original particles in the presence of sodium dodecyl (lauryl) sulfate. However, swelling is drastically reduced for cross-linked particles. In this case, an increase in diameter by only a factor of 1.4 is observed. Again, Hidi, Napper and Sangster do not explain how to create a shear thinning flow boundary fluid with high optical clarity.
[0009] The part of providing the necessary rheology profiles, the suspension of solid and/or insoluble materials in a stable phase system is equally important to a rheology modifier. In oil and gas drilling, underground treatment fluids (eg, drilling and fracturing fluids) are typically modified with gel-forming agents to provide desired rheological properties. Gel forming agents include any substance that is capable of increasing the viscosity of a fluid, for example, by forming a microgel. The agents must not only have desired rheological properties in terms of fluid flow and pumpability, but they must also have the ability to suspend solids under both dynamic and static conditions. During active drilling operations, the drilling fluid must have sufficient structure to perform the surface forming shears and also have the necessary shear thinning properties to be pumpable. During periods without drilling, the drilling fluid can remain stationary in the wellbore for hours or even for a period. During this period, sedimentation of included solids can be problematic if the fluid does not have enough structure to support both large and small particulate matter.
[0010] Fracture is used to intensify the production of hydrocarbons such as oil or natural gas from underground formations. In this process, a fracture fluid containing a gel-forming agent is injected through a wellbore and forced against the forming layers by high enough pressure to cause the layer to break and fracture in this way, releasing hydrocarbon trapped in the formation. . Fracture fluid also carries a builder to the fracture site. Fluid particles remain in the fracture, thereby “braiding” the open fracture when the well is in production. The structuring material is typically selected from sand, sintered bauxite, glass spheres, polystyrene beads and others. Since sufficient rheological properties are important in treatment fluids used in fracture, satisfactory suspendability is required to transport the propellant materials to the fracture site within the formation.
[0011] Conditions are harsh within an underground formation and a gel-forming agent must be stable in variations in temperature, brackish environments, widening pH range and changes in shear forces.
[0012] Several problems have been encountered with underground treatment fluids in oil field applications, including loss of thermal stability of the gel on exposure to varying temperatures and pH, as well as high shear conditions. This can result in changes in the gel's rheological properties which can ultimately affect the fluid's ability to suspend the wellbore and/or structuring materials. If particulate materials are prematurely lost from fluid treatment, this can have a detrimental effect on perforation and formation development. In addition, gel instability can result in higher fluid loss in formation in this way, decreasing the efficiency of the operation.
Personal care compositions which can put particles and/or other insoluble materials into suspension are very desirable. These materials communicate or contribute to a variety of user benefits including, but not limited to, exfoliation, visual aesthetics, and/or encapsulation and release of beneficial agents in use. Suspension of particulate and insoluble materials as active and aesthetic agents in personal care compositions are becoming increasingly popular with formulators. Typically, the particles are suspended in personal care compositions using builder systems such as acrylate polymers, builder gums (e.g. xanthan gum), starch, agar, hydroxy alkyl cellulose, etc. However, adding beads or particles to personal care compositions tends to be problematic. For example, one problem is that insoluble particles or materials very often tend to be of a different density than the continuous phase of the composition to which they are added. This disagreement in density can lead to separation of particles from the continuous phase and a loss of stability of the total product. In one aspect, when the added particles are less dense than that of the continuous phase of the composition, the particles tend to rise to the top of that phase (“skimming”). In another aspect, when the added particles have a density greater than that of the continuous phase, the particles tend to settle at the bottom of that phase (“sedimentation”). When large particles are desired to be suspended (e.g. polyethylene particles, guar beads, etc.), the level of polymer used is typically increased to provide increased structure for suspended beads. The consequences of thickening a liquid to provide structure for suspended beads cause a significant increase in liquid viscosity and a corresponding decrease in flowability, a property that is not always desired. Highly viscous products are typically difficult to apply and rinse off, especially the shear thinning profile of the viscosity building agent is deficient. High viscosities can also adversely affect the packaging, dispensing, dissolving and foaming and sensory properties of the product. Furthermore, conventionally structured liquids are often opaque or cloudy thereby obscuring the suspended beads from the consumer, which adversely affect the aesthetic appeal of the product.
[0014] Many common thickeners such as xanthan gum, carboxymethylcellulose (CMC), carrageenan and acrylic acid homopolymers and copolymers are anionic and therefore can react with cationic surfactants and cause precipitation of the cationic and thickener or reduce effectiveness of the cationic surfactant. Nonionic thickeners such as hydroxyethylcellulose (HEC) and hydroxypropylmethylcellulose (HPMC) can provide viscosity in cationic systems, however very few suspension properties are communicated to the fluid. Cationic thickeners such as Polyquathemium-10 (cationically modified HEC) and cationic guar provide thickening in cationic systems but not suspension. Some acrylic polymers are effective in cationic thickener systems, but these can be limited by pH, require high concentrations, are costly in use, and often have narrow compatibility limits with cationic materials.
[0015] Anionic surfactants are often used as detersive agents in purifiers and cleaning products because of their excellent cleaning and foaming properties. Exemplary anionic surfactants traditionally used in these formulations include, for example, alkyl sulfates and alkyl benzene sulfonates. While anionic surfactants and, in particular, anionic sulfates and sulfonates are effective detersive agents, they are severe eye irritants and capable of causing mild to moderate skin irritation to some sensitized persons. Consequently, it has become increasingly important to consumers that aqueous cleansing compositions be mild in that they do not irritate the eyes and skin when in use. Manufacturers are striving to provide mild purifying products that also incorporate the insoluble benefit and/or esthetic agents that require stable suspension. It is known that irritation caused by anionic sulphates and sulphonates can be reduced by using their ethoxylated forms. While ethoxylated surfactants can alleviate eye and skin irritation in compositions in which they are included, a major problem in using these surfactants is that it is difficult to obtain desirable flow-limiting properties in an ethoxylated system.
[0016] U.S. Patent No. 5,139,770 describes the use of crosslinked vinyl pyrrolidone homopolymers in surfactants containing formulations such as conditioner shampoo to obtain relatively high viscosity. However, the patent does not explain how to create a yield-limit fluid with high optical clarity that is also shear thinning.
[0017] U.S. Patent No. 5,663,258 describes the preparation of crosslinked vinyl pyrrolidone/vinyl acetate copolymers. High viscosities are obtained when the polymer is combined with water but there is no explanation for using the polymer to create a yield point fluid that is activated by the surfactant.
[0018] US Patent No. 6,645,476 describes a water-soluble polymer prepared from the free radical polymerization of a hydrophobically modified ethoxylated macromer in combination with a second copolymerizable monomer selected from unsaturated acids and their salts and/or a myriad of others monomers including N-vinyl lactams and vinyl acetate. Preferred polymers are cross-linked and are polymerized from the hydrophobically modified ethoxylated macromers in combination with acrylamidolmethypropanesulfonic acid. The viscosities of 1% aqueous solutions of the polymer preferably range from 20,000 mPa-s to 100,000 mPa-s. There is no explanation of a surfactant activated polymer devoid of hydrophobically modified ethoxylated macromer repeating units providing a flow-limit fluid that exhibits good suspension properties without a substantial increase in viscosity.
[0019] It remains a challenge to not only demonstrate the ability to effectively suspend particles within stable microgel-containing compositions, but also exhibit desirable softness, desirable rheology profiles, clarity and aesthetic characteristics across a wide range of temperature and conditions of pH at low polymer usage levels. Consequently, there is a need for a flow-limit fluid based on polymeric microgel particles wherein the polymer concentration is not greater than 5% by weight based on the weight of the composition in which it is included and having a threshold value. of at least 0.1 Pa, wherein the yield point, elastic modulus and optical clarity are substantially independent of pH. There is a need to supply flow-limit fluid formulated with mild surfactants, such as, for example, surfactants containing moieties of ethylene oxide. SUMMARY OF THE INVENTION
[0020] In one aspect, embodiments of the present invention relate to cross-linked, non-ionic, amphiphilic polymers that are swollen in the presence of a surfactant. In another aspect, an embodiment of the invention concerns a flow-limiting fluid comprising a cross-linked nonionic amphiphilic polymer and a surfactant.
[0021] In yet another aspect, an embodiment of the invention concerns a thickened aqueous composition comprising a cross-linked, nonionic, amphiphilic polymer and at least one surfactant, in which the polymer concentration is not greater than 5% by weight based on the total weight of the composition and the at least one surfactant is not greater than 30% by weight of the composition, the yield point of the composition is at least 0.1 Pa with a shear thinning index less than that 0.5 at shear rates between about 0.1 and about 1 second reciprocal and where the yield point, elastic modulus and optical clarity of the composition are substantially independent of pH in the range of about 2 to about 14 .
[0022] In yet another aspect, an embodiment of the invention concerns a thickened aqueous composition comprising a cross-linked, nonionic, amphiphilic polymer and at least one surfactant, wherein the polymer concentration is not greater than 5 % by weight based on the total weight of the composition and the at least one surfactant is not greater than 30% by weight of the composition, wherein the ratio of the standard deviation to the mean of the measured values for flow limit, elastic modulus and clarity optical is less than 0.3 in one aspect and less than 0.2 in another aspect in the pH range of about 2 to about 14.
[0023] In yet another aspect, an embodiment of the invention concerns a thickened aqueous composition comprising a cross-linked, nonionic, amphiphilic polymer and at least one surfactant, wherein the polymer concentration is not greater than 5 % by weight based on the total weight of the composition, and at least one surfactant is not greater than 30% by weight of the composition, the yield point of the composition is at least 0.1 Pa with a lower shear thinning index than 0.5 at shear rates between about 0.1 and about 1 second reciprocal and wherein the yield point, elastic modulus and optical clarity of the composition are substantially independent of pH in the range of from about 2 to about 14 and wherein the composition is capable of placing suspended beads of a size between 0.5 and 1.5 mm wherein the difference in specific gravity of the beads with respect to water is in the range of 0.2 to 0. 5 for a period of at least 4 weeks in temperature environment.
[0024] In yet another aspect, an embodiment of the invention concerns a thickened aqueous composition comprising a crosslinked nonionic amphiphilic polymer and one or more surfactants, wherein the polymer concentration is not greater than 5% in weight based on the total weight of the composition, wherein the total concentration of the surfactant is not greater than 30% by weight of the composition, the yield point of the composition is at least 0.1 Pa with a lower shear thinning index than 0.5 at shear rates between about 0.1 and about 1 second reciprocal and wherein the yield point, elastic modulus and optical clarity of the composition are substantially independent of pH in the range of from about 2 to about 14 and wherein the composition is capable of putting suspended beads of a size between 0.5 and 1.5 mm where the difference in specific gravity of the beads with respect to water is in the range of 0.2 to 0.5 for a period of at least 4 weeks in t. ambient temperature and one of the surfactants contains portions of ethylene oxide and said surfactant is greater than 75% by weight of the total surfactant.
[0025] The crosslinked, nonionic, amphiphilic polymer compositions as well as the thickened aqueous fluid comprising nonionic amphiphilic polymeric compositions and the at least one surfactant of the present invention may suitably comprise, consist of or consist essentially of the components, elements and delineations processes described here. The invention illustratively described herein suitably may be practiced in the absence of any element that is not specifically described herein.
[0026] Unless otherwise stated, all percentages, parts and ratios expressed herein are based on the total weight of the components contained in the compositions of the present invention.
[0027] As used herein, the term "amphiphilic polymer" means that the polymeric material has distinct hydrophilic and hydrophobic portions. “Hydrophilic” typically means a moiety that interacts intramolecularly with water and other polar molecules. "Hydrophobic" typically means a moiety that preferentially interacts with oils, fats or other non-polar molecules rather than aqueous media.
[0028] As used herein, the term "hydrophilic monomer" means a monomer that is substantially soluble in water, "substantially soluble in water" refers to a material that is soluble in distilled water (or equivalent) at 25°C , at a concentration of about 3.5 wt% in one aspect and soluble about 10 wt% in another aspect (calculated on a weight basis of water plus monomer).
[0029] As used herein, the term "hydrophobic monomer" means a monomer that is substantially insoluble in water, "substantially insoluble in water" refers to a material that is not soluble in distilled water (or equivalent), at 25° C, at a concentration of about 3% by weight in one aspect and is not soluble in about 2.5% by weight in another aspect (calculated on a weight basis of water plus monomer).
[0030] By "non-ionic" it is understood that a monomer, polymeric composition or a polymer polymerized from the polymeric composition is devoid of ionic or ionizable ("non-ionizable") portions.
[0031] An ionizable moiety is any group that can be made ionic by neutralization with an acid or a base.
[0032] An ionic or ionized moiety and any moiety that has been neutralized by an acid or a base.
[0033] By "substantially non-ionic" is meant that the monomer, polymeric composition or polymerized polymer from the polymeric composition contains less than 5% by weight in one aspect, less than 3% by weight in another aspect, less than that 1% by weight in another aspect, less than 0.5% by weight in yet another aspect, less than 0.1% by weight in a further aspect and less than 0.05% by weight in another aspect, of an ionizable and/or an ionized portion.
[0034] For the purpose of the descriptive report the prefix "(meth)acryl" includes "acryl" as well as "methacryl". For example, the term "(meth)acrylamide" includes both acrylamide and methacrylamide. BRIEF DESCRIPTION OF THE DRAWINGS
[0035] Fig. 1 is a plot of the average particle size of a cross-linked, nonionic, amphiphilic polymer in the yield point fluid of Example 12 formulated with sodium dodecyl sulfate (SDS) at various concentrations.
[0036] Fig. 2 is a plot of the elastic moduli (G') and viscous modulus (G”) as a function of increasing the oscillating stress amplitude (Pa) for the yield-limit fluid formulation of Example 13. A plot shows the crossing point of G' and G” that corresponds to the yield limit value of the formulation.
[0037] Fig. 3 is a plot of the elastic moduli (G') and viscous modulus (G”) as a function of increasing the oscillating voltage amplitude for a flow-limit fluid formulated from the cross-linked, non-ionic polymer, amphiphile from Example 9. DESCRIPTION OF EXEMPLARY EMBODIMENTS
[0038] Exemplary embodiments according to the present invention will be described. Various modifications, adaptations or variations of the exemplary embodiments described herein may become apparent to those skilled in the art as described. It will be understood that all such modifications, adaptations or variations which rely on the explanations of the present invention and by which these explanations have advanced in the art, are considered to be within the scope and spirit of the present invention.
[0039] While the overlapping weight varies for the various components and ingredients that may be contained in the compositions of the invention have been expressed for selected embodiments and aspects of the invention, it should be readily apparent that the specific amount of each component in the described compositions will be selected from their described ranges, such that the amount of each component is adjusted such that the sum of all components in the composition will total 100 percent by weight. The quantities used will vary with the purpose and character of the desired product and can be easily determined by a person skilled in the art.
[0040] It has been unexpectedly found that highly efficient yield point fluids with excellent shear thinning and optical clarity over a wide pH range are obtained if certain chemically crosslinked, nonionic, amphiphilic polymers are mixed with surfactants in water. Crosslinking has been determined to provide the exact balance between particle mechanical stiffness and expansion in aqueous surfactant media. The cross-linked, nonionic, amphiphilic polymers of the invention exhibit high surfactant activated swell in water that increases particle diameter by at least a factor of 2.5 in one aspect and at least 2.7 in another aspect. Furthermore, the swollen microgels based on the polymers of the invention interact with one another in aqueous surfactant media to create soft vitreous materials (SGMs) with high flow yield and shear thinning flow that is substantially independent of pH. Amphiphilic Polymer
[0041] The crosslinked, nonionic, amphiphilic polymers useful in the practice of the invention are polymerized from the monomeric components that contain unsaturation free radical polymerization. In one embodiment, the crosslinked, nonionic, amphiphilic polymers useful in the practice of the invention are polymerized from the polymeric composition comprising at least one nonionic hydrophilic unsaturated monomer, at least one unsaturated hydrophobic monomer, and at least one crosslinking monomer polyunsaturated. In one aspect, the copolymer can be polymerized from the polymeric composition comprising any weight ratio of non-ionic hydrophilic unsaturated monomer to hydrophobic unsaturated monomer.
[0042] In one embodiment, the copolymers can be polymerized from the polymer composition typically have a ratio of hydrophilic monomer to hydrophobic monomer of about 5:95% by weight to about 95:5% by weight, of about from 15:85% by weight to about 85:15% by weight in another aspect and from about 30:70% by weight to about 70:30% by weight in another aspect, based on the total weight of the hydrophilic monomers and hydrophobics present. The hydrophilic monomer component can be selected from a simple hydrophilic monomer or a mixture of hydrophilic monomers and the hydrophobic monomer component can be selected from a simple hydrophobic monomer or a mixture of hydrophobic monomers. hydrophilic monomer
[0043] Suitable hydrophilic monomers for the preparation of the crosslinked, nonionic, amphiphilic polymer compositions of the invention are selected from, but not limited to, alkyl hydroxy(meth)acrylates (Cr C5); Open-chain and cyclic N-vinylamides (N-vinyllactams containing from 4 to 9 atoms in the lactam ring portion, wherein the ring carbon atoms may be optionally substituted by one or more lower alkyl groups such as methyl, ethyl or propellae); amino group containing vinyl monomers selected from (meth)acrylamide, N-alkyl (C1-C5) (meth)acrylamides, N,N-dialkyl (C1-C5) (meth)acrylamides, N-alkyl (C1-C5) aminoalkyl (C1-C5) (meth)acrylamides and N,N-dialkyl (C1-C5)aminoalkyl (C1-Cs) (meth)acrylamides, wherein the alkyl moieties on the disubstituted amino groups may be the same or different and wherein the alkyl moieties on mono- and di-substituted amino groups may be optionally substituted by a hydroxy group; other monomers include vinyl alcohol; vinyl imidazole and (meth)acrylonitrile. Mixtures of the preceding monomers can also be used.
[0044] The (C[-C5) alkyl hydroxy(meth)acrylates can be structurally represented by the following formula:
wherein R is hydrogen or methyl and R1 is a divalent alkylene moiety containing from 1 to 5 carbon atoms, wherein the alkylene moiety may optionally be substituted by one or more methyl groups. Hydroxypropyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate and mixtures thereof.
Representative open chain N-vinylamides include N-vinylformamide, N-methyl-N-vinylformamide, N-(hydroxymethyl)-Nvinylformamide, N-vinylacetamide, N-vinylmethylacetamide, N-(hydroxymethyl)-N-vinylacetamide and mixtures thereof.
Representative cyclic N-vinylamides (also known as N-vinyllactams) include N-vinyl-2-pyrrolidinone, N-(1-methyl vinyl)pyrrolidinone, N-vinyl-2-piperidone, N-vinyl-2-caprolactam, N-vinyl-5-methylpyrrolidinone, N-vinyl-3,3-dimethyl pyrrolidinone, N-vinyl-5-ethyl pyrrolidinone and N-vinyl-6-methyl piperidone and mixtures thereof. Additionally, monomers containing a portion of a pendant N-vinyl lactam can also be used, for example, N-vinyl-2-ethyl-2-pyrrolidone (meth)acrylate.
[0047] The amino group containing vinyl monomers include (meth)acrylamide, diacetone acrylamide and monomers that are structurally represented by the following formulas:

[0048] Formula (II) represents N-alkyl (C1-C5) (meth)acrylamide or N,N-dialkyl (C1-C5) (meth)acrylamide wherein R" is hydrogen or methyl, R1 independently is selected from hydrogen, alkyl Q to C5 and hydroxyalkyl C, to C5 and R4 independently is selected from is alkyl C to C5 or hydroxyalkyl Q to C5.
Formula (III) represents N-alkyl(CrC5)aminoalkyl(CrC5)(meth)acrylamide or N,N-dialkyl(C1-C5)aminoalkyl(C1-C5)(meth)acrylamide wherein R is hydrogen or methyl, R6 is Q to C5 alkylene, R7 independently is selected from hydrogen or C1 to C5 alkyl, and R' independently is selected from Q to C5 alkyl.
Representative N-alkyl(meth)acrylamides include but are not limited to N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-propyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N -tert-butyl(meth)acrylamide, N-(2-hydroxyethyl)(meth)acrylamide, N-(3-hydroxypropyl)(meth)acrylamide and mixtures thereof.
Representative N,N-dialkyl(meth)acrylamides include but are not limited to N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-(di-2-hydroxyethyl) )(meth)acrylamide, N,N-(di-3-hydroxypropyl)(meth)acrylamide, N-methyl, N-ethyl(meth)acrylamide and mixtures thereof.
Representative N,N-dialkylaminoalkyl(meth)acrylamides include but are not limited to N,N-dimethylaminoethyl(meth)acrylamide, N,N-diethylaminoethyl(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide and mixtures of these. hydrophobic monomer
[0053] Suitable hydrophobic monomers for the preparation of the crosslinked, nonionic, amphiphilic polymer compositions of the invention are selected from, but not limited to, one or more of (meth)acrylic acid esters with alcohols containing from 1 to 30 atoms of carbon; vinyl esters of aliphatic carboxylic acids containing 1 to 22 carbon atoms; vinyl esters of alcohols containing 1 to 22 carbon atoms; vinyl aromatics containing 8 to 20 carbon atoms; vinyl halides; vinylidene halides; linear or branched alpha-monoolefins containing from 2 to 8 carbon atoms; an associative monomer has a hydrophobic end group containing 8 to 30 carbon atoms and mixtures thereof. Semi-hydrophobic monomer
[0054] Optionally, at least one semi-hydrophobic monomer can be used in preparing the amphiphilic polymers of the invention. A semi-hydrophobic monomer is similar in structure to an associative monomer, but has a substantially non-hydrophobic end group selected from hydroxyl or a moiety containing 1 to 4 carbon atoms.
[0055] In one aspect of the invention, (meth)acrylic acid esters with alcohols containing from 1 to 30 carbon atoms can be represented by the following formula:
where R9 is hydrogen or methyl and R1() is C1 to C52 alkyl. Representative monomers under formula (IV) include but are not limited to methyl(meth)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate, sec-butyl(meth)acrylate, iso-butyl(meth)acrylate, hexyl(meth)acrylate), heptyl(meth)acrylate, octyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, decyl(meth)acrylate, isodecyl(meth)acrylate, lauryl(meth)acrylate, tetradecyl(meth)acrylate , hexadecyl (meth)acrylate, stearyl (meth)acrylate, behenyl (meth)acrylate and mixtures thereof.
[0056] Vinyl esters of aliphatic carboxylic acids containing from 1 to 22 carbon atoms can be represented by the following formula:
wherein R." is a C1 to C52 aliphatic group which may be an alkyl or alkenyl. Representative monomers under formula (V) include but are not limited to vinyl acetate, vinyl propionate, vinyl butyrate, isobutyrate. vinyl, vinyl valerate, vinyl hexanoate, vinyl 2-methylhexanoate, vinyl 2-ethylhexanoate, vinyl isooctanoate, vinyl nonanoate, vinyl neodecanoate, vinyl decanoate, vinyl versatate, vinyl laurate, palmitate vinyl, vinyl stearate and mixtures thereof.
[0057] In one aspect, vinyl esters of alcohols containing from 1 to 22 carbon atoms can be represented by the following formula:
where RH is a C1 to C52 alkyl. Representative monomers of formula (VI) include methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, decyl vinyl ether, lauryl vinyl ether, stearyl vinyl ether, behenyl vinyl ether, and mixtures thereof.
Representative vinyl aromatic monomers include but are not limited to styrene, alpha-methylstyrene, 3-methyl styrene, 4-methyl styrene, 4-propyl styrene, 4-tert-butyl styrene, 4-n-butyl styrene , 4-n-decyl styrene, vinyl naphthalene and mixtures thereof.
Representative vinyl and vinylidene halides include but are not limited to vinyl chloride and vinylidene chloride and mixtures thereof.
Representative alpha-olefins include, but are not limited to, ethylene, propylene, 1-butene, iso-butylene, 1-hexene, and mixtures thereof.
[0061] The associative monomer of the invention has an ethylenically unsaturated end-group portion (i) for addition polymerization with the other monomers of the invention; a polyoxyalkylene midsection portion (ii) to impart selective hydrophilic and/or hydrophobic properties to the product polymer and a hydrophobic endgroup portion (iii) to impart selective hydrophobic properties to the polymer.
[0062] The portion (i) that provides the end group ethylenically unsaturated may be a residue derived from an α,β-ethylenically unsaturated monocarboxylic acid. Alternatively, portion (i) of the associative monomer may be a residue derived from an allylic ether or vinyl ether; a nonionic vinyl-substituted urethane monomer, such as described in U.S. Patent Reissue No. 33,156 or U.S. Patent No. 5,294,692; or a vinyl substituted urea reaction product as described in U.S. Patent No. 5,011,978; the relevant descriptions of each are incorporated herein by reference.
[0063] The mid-section portion (ii) is a polyalkylene segment 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 another aspect. aspect of repeating C5-C4 alkylene oxide units. The mid-section portion (ii) includes polyoxyethylene, polyoxypropylene and polyoxybutylene segments and combinations thereof comprising from 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 another aspect of ethylene oxide, propylene and/or butylene oxide units arranged in random or block sequences of ethylene oxide, propylene oxide and/or butylene oxide units.
[0064] The hydrophobic end group moiety (iii) of the associative monomer is a hydrocarbon moiety that belongs to one of the following hydrocarbon classes: the linear C8-C30 alkyl, a branched C8-C30 alkyl, the C8-carbocyclic alkyl C30, a phenyl substituted by C5-C30 alkyl, a phenyl substituted by aralkyl and C5-C30 alkyl substituted by aryl groups.
[0065] Non-limiting examples of suitable hydrophobic end group moieties (iii) of the associative monomers are linear or branched alkyl groups having from about 8 to about 30 carbon atoms, such as capryla (C8), iso-octyl ( branched C8), decyl (Ci0), lauryl (C)2), myristyl (C]4), cetyl (C]6), cetearyl (C]6-Ci8), stearyl (Ci8), isostearyl (branched Ci8), arachidyl ( C50), behenyl (C52), lignoceryl (C54), cerotile (C56), montanyl (C58), melissyl (C30) and others.
[0066] Examples of linear and branched alkyl groups having from about 8 to about 30 carbon atoms that are derived from a natural source include, but are not limited to, alkyl groups derived from hydrogenated peanut oil, soybean oil and canola oil (all predominantly C18), hydrogenated tallow oil (C16-C18) and others; and C10-C30 hydrogenated terpenols, such as hydrogenated geraniol (C10 branch), hydrogenated famesol (C15 branch), hydrogenated phytol (C50 branch) and others.
Non-limiting examples of suitable C5-C30 alkyl substituted phenyl groups include octylphenyl, nonylphenyl, decylphenyl, dodecylphenyl, hexadecylphenyl, octadecylphenyl, isooctylphenyl, sec-butylphenyl and others.
Exemplary aryl-substituted C5-C40 alkyl groups include, without limitation, styryl (e.g., 2-phenylethyl), distyryl (e.g., 2,4-diphenylbutyl), tristyryl (e.g., 2,4 ,6-triphenylhexyl), 4-phenylbutyl, 2-methyl-2-phenylethyl, tristyrylphenolyl and others.
[0069] Suitable C8-C30 carbocyclic alkyl groups include, but are not limited to, groups derived from sterols from animal sources, such as cholesterol, lanosterol, 7-dehydrocholesterol and others; from plant sources such as phytosterol, stigmasterol, campesterol and others and from yeast sources such as ergosterol, mycosterol and others. Other hydrophobic carbocyclic alkyl end groups useful in the present invention include, but are not limited to, cyclooctyl, cyclododecyl, adamantyl, decahydronaphthyl, and groups derived from natural carbocyclic materials such as pinene, hydrogenated retinol, camphor, isobomyl alcohol and others.
Useful associative monomers can be prepared by any method known in the art. See, for example, U.S. Patents No. 4,421,902 issued to Chang et al.; No. 4,384,096 issued to Sonnabend; No. 4,514,552 issued to Shay et al.; No. 4,600,761 issued to Ruffner et al.; No. 4,616,074 issued to Ruffner; No. 5,294,692 to Barron et al.; No. 5,292,843 to Jenkins et al.; No. 5,770,760 issued to Robinson; and No. 5,412,142 to Wilkerson, III et al.; which pertinent descriptions are incorporated herein by reference.
[0071] In one aspect, exemplary associative monomers include those represented by formulas (VII) and (VIIA) as follows:
-0-, -CH20-, -NHC(O)NH-, -C(O)NH-, -Ar-(CE2)2-NHC(O)O-, -Ar-(CE2)2-NHC(O )NH- or -CH2CH2NHC(O)-; Ar is a divalent arylene (eg 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 O, m is O and when k is in the range of 1 to about 3 O, m is 1; D represents a vinyl portion or an allyl; (R15-0)0 is a polyoxyalkylene moiety, bivalent selected from C5~, C3H6 or C~8 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 from 120 in another aspect and from about 15 to about 60 in another aspect; Y is -R150-, -R15NH-, -C(O)-, -C(O)NH-, -R15NHC(O)NH- or -C(O)NHC(O)-; R16 is a substituted or unsubstituted alkyl selected from linear C8-C30 alkyl, a branched C8-C30 alkyl, a C8-C30 carbocyclic alkyl, a phenyl substituted by C5-C30 alkyl, a phenyl substituted by aralkyl and a C5-C30 alkyl substituted by aryl; wherein the alkylR16 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, phenethyl group and a halogen group.
[0072] In one aspect, the hydrophobically modified associative monomer is an alkoxylated (meth)acrylate having a hydrophobic group containing from 8 to 30 carbon atoms represented by the following formula:
where R14 is hydrogen or methyl; R13 is a bivalent alkylene moiety independently selected from C5H4, C3H6 and C4H8 and n represents an integer ranging from 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 another aspect, (R13-O) may be arranged in a random or block configuration; R16 is a substituted or unsubstituted alkyl selected from linear C8-C30 alkyl, branched C8-C30 alkyl, C8-C3o carbocyclic alkyl, C5-C3o alkyl substituted phenyl and aryl substituted C8-C3 alkyl.
[0073] Representative monomers under formula (VII) include polyethoxylated lauryl methacrylate (LEM), polyethoxylated cetyl methacrylate (CEM), polyethoxylated cetearyl methacrylate (CSEM), polyethoxylated stearyl (meth)methacrylate, polyethoxylated (meth)methacrylate of arachidyl, polyethoxylated behenyl methacrylate (BEM), polyethoxylated cerotyl (meth)methacrylate, polyethoxylated montanyl (meth)methacrylate, polyethoxylated melissyl (meth)methacrylate, polyethoxylated phenyl (meth)methacrylate, polyethoxylated nonylphenyl (meth)methacrylate , polyoxyethylene co-tristyrylphenyl methacrylate, wherein the polyethoxylated portion of the monomer contains from about 2 to about 150 ethylene oxide units in one aspect, from about 5 to about 120 in another aspect, and from about 10 to about 10 to about 60 in another aspect; octyloxy polyethylene glycol (8) polypropylene glycol (6) (meth)acrylate, phenoxy polyethylene glycol (6) polypropylene glycol (6) (meth)acrylate and nonylphenoxy polyethylene glycol polypropylene glycol (meth)acrylate.
[0074] The semi-hydrophobic monomers of the invention are structurally similar to the associative monomer described above, but have a substantially non-hydrophobic end-group portion. The semi-hydrophobic monomer has an ethylenically unsaturated end-group moiety (i) for addition polymerization with the other monomers of the invention; a polyoxyalkylene midsection portion (ii) to impart selective hydrophilic and/or hydrophobic properties to the product polymer and a semi-hydrophobic endgroup portion (iii). The unsaturated end group moiety (i) providing the vinyl or other ethylenically unsaturated end group for the addition polymerization is preferably derived from an α,β-ethylenically unsaturated monocarboxylic acid. Alternatively, the end group moiety (i) can be derived from an allyl ether residue, a vinyl ether residue or a residue of a nonionic urethane monomer.
[0075] The polyoxyalkylene middle section (ii) specifically comprises a polyoxyalkylene segment, which is substantially similar to the polyoxyalkylene portion of the associative monomers described above. In one aspect, the polyoxyalkylene (ii) moieties include polyoxyethylene, polyoxypropylene and/or polyoxybutylene units comprising from 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 another aspect of ethylene oxide, propylene oxide and/or butylene oxide units, arranged in random or block sequences.
[0076] In one aspect, the semi-hydrophobic monomer can be represented by the following formulas:
where R14 is hydrogen or methyl; A is -CH2C(O)O-, -C(O)O-, -O-, -CH2O-, -NHC(O)NH-, -C(O)NH-, -AT-(CE2)Z- NHC(O)O-, -AT-(CE2)Z- NHC(O)NH- or -CH2CH2NHC(O)-; Ar is a divalent arylene (eg 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 ; (Rb-O)n is a polyoxyalkylene moiety, which can be a homopolymer, a random copolymer or a block copolymer of C5-C4 oxyalkylene units, Rb is a divalent alkylene moiety selected from CsEU, C3H6 or C4H8 and combinations of these and en is an integer ranging from 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 another aspect; R is selected from hydrogen and a linear or branched C1-C4 alkyl group (for example, methyl, ethyl, propyl, iso-propyl, butyl, iso-butyl and tert-butyl); and D represents a vinyl portion or an allyl.
[0077] In one aspect, the semi-hydrophobic monomer under the formula VIII can be represented by the following formulas: CH2=C(R14)C(O)O-(C5H4O)a(C3H6O)bH VIIIACH2=C(R14)C (O)O-(C5H4O)a(C3H6O)b-CH3 VIIIWhile 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 from 45 in another aspect and from about 10 to about.25 in another 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.25 in another aspect, subject to the condition that “a” and “b” cannot be 0 at the same time.
[0078] Examples of semi-hydrophobic monomers under the formula VIIIA include polyethylene glycol methacrylate available under the product names Blemmer* PE-90 (R14 = methyl, a = 2, b = 0), PE-200 (R14 = methyl , a = 4.5, b = 0) and PE-350 (R14 = methyl a = 8, b = 0,); polypropylene glycol methacrylate available under product names Blemmer PP-1000 (R14 = methyl, b = 4-6, a = 0), PP-500 (R14 = methyl, a = 0, b = 9), PP-800 (R14 = methyl, a = 0, b = 13); polyethylene glycol polypropylene glycol methacrylate available under product names Blemmer* 50PEP-300 (R14 = methyl, a = 3.5, b = 2.5), 70PEP-350B (R14 = methyl, a = 5, b = 2) ; polyethylene glycol acrylate available under product names BlemmerK AE-90 (R14 = hydrogen, a = 2, b = 0), AE-200 (R14 = hydrogen, a = 2, b = 4.5), AE-400 ( R14 = hydrogen, a = 10, b = 0); polypropylene glycol acrylate available under product names Blemmer* AP-150 (R14 = hydrogen, a = 0, b = 3), AP-400 (R14 = hydrogen, a = 0, b = 6), AP-550 (R14 = hydrogen, a = 0, b = 9). Blemmer* is a trademark of NOF Corporation, Tokyo, Japan.
[0079] Examples of semi-hydrophobic monomers under the formula VIIIB include methoxypolyethylene glycol methacrylate available under the product names Visiomer® MPEG 750 MA W (R14 = methyl, a = 17, b = 0), MPEG 1005 MA W (R14 = methyl, a = 22, b = 0), MPEG 2005 MA W (R14 = methyl, a = 45, b = 0) and MPEG 5005 MA W (R14 = methyl, a = 113, b = 0) from Evonik Rohm GmbH, Darmstadt, Germany); Bisomer* MPEG 350 MA (R14 = methyl, a = 8, b = 0) and MPEG 550 MA (R14 = methyl, a = 12, b = 0) from GEO Specialty Chemicals, Ambler PA; Blemmer PME-100 (R14 = methyl, a = 2, b = 0), PME-200 (R14 = methyl, a = 4, b = 0), PME400 (R14 = methyl, a = 9, b = 0), PME-1000 (R14 = methyl, a = 23, b = 0), PME-4000 (R14 = methyl, a = 90, b = 0).
[0080] In one aspect, the semi-hydrophobic monomer shown in formula IX can be represented by the following formulas: CH2=CH-O-(CH2)dO-(C3H6O)and-(C5H4O)rH IXACH2=CH-CH2-O -(C3H6O)g-(C5H4O)hH IXWhere d is an integer of 2, 3 or 4; and is an integer ranging from about 1 to about 10 in one aspect, from about 2 to about 8 in another aspect, and from about 3 to about 7 in another aspect; f is an integer ranging from about 5 to about 50 in one aspect, from about 8 to about 40 in another aspect, and from about 10 to about 30 in another aspect; g is an integer ranging from 1 to about 10 in one aspect, from about 2 to about 8 in another aspect, and from about 3 to about 7 in another aspect; and h is an integer ranging from about 5 to about 50 in one aspect and from about 8 to about 40 in another aspect; e, f, g and h can be 0 subject to the condition that e and f cannot be 0 at the same time and g and h cannot be 0 at the same time.
Monomers under the formulas IXA and IXB are commercially available under the trade names Emulsogen* RI09, R208, R307, RALI09, RAL208, and RAL307 sold by Clariant Corporation; BX-AA-E5P5 sold by Bimax, Inc. and combinations thereof. EMULSOGEN7 RI 09 is a randomly ethoxylated/propoxylated 1,4-butanediol vinyl ether having the empirical formula CH2=CH- 0(CH2)40(C3H60)4(C5H40)IOH; Emulsogen* R208 is a randomly ethoxylated/propoxylated 1,4-butanediol vinyl ether having the empirical formula CH2=CH- 0(CH2)40(C3H60)4(C5H40)2OH; Emulsogen* R307 is a randomly ethoxylated/propoxylated 1,4-butanediol vinyl ether having the empirical formula CH2=CH- 0(CH2)40(C3H60)4(C5H40)3OH; Emulsogen* RALI09 is a randomly ethoxylated/propoxylated allyl ether having the empirical formula CH2=CHCH2O(C3H6O)4(C5H4O)10H; Emulsogen® RAL208 is a randomly ethoxylated/propoxylated allyl ether having the empirical formula CH2=CHCH20(C3H60)4(C5H40)2OH; Emulsogen* RAL307 is a randomly ethoxylated/propoxylated allyl ether having the empirical formula CH2=CHCH20(C3H60)4(C5H40)3OH; and BX-AA-E5P5 is a randomly ethoxylated/propoxylated allyl ether having the empirical formula CH2=CHCH2O(C3H6O)5(C5H4O)5H.
[0082] In the associative and semi-hydrophobic monomers of the invention, the polyoxyalkylene mid-section portion contained in these monomers can be used to adapt the hydrophilicity and/or hydrophobicity of the polymers in which they are included. For example, mid-section portions rich in ethylene oxide portions are more hydrophilic while mid-section portions rich in propylene oxide portions are more hydrophobic. By adjusting the relative amounts of ethylene oxide moieties to propylene oxide present in these monomers the hydrophilic and hydrophobic properties of the polymers in which these monomers are included can be adapted as desired.
[0083] The amount of associative and/or semi-hydrophobic monomer used in the preparation of the polymers of the present invention can vary widely and depends, among other things, on the final desired rheological and aesthetic properties of the polymer. When used, the monomeric reaction mixture contains one or more monomers selected from the associative and/or semi-hydrophobic monomers described above in varying amounts from about 0.01 to about 15% by weight in one aspect, from about 0. 1% by weight to about 10% by weight in another aspect, from about 0.5 to about 8% by weight in yet another aspect, and from about 1, 2 or 3 to about 5% by weight in another aspect, based on the weight of the total monomers. ionizable monomer
[0084] In one aspect of the invention, the crosslinked, nonionic, amphiphilic polymer compositions of the invention may be polymerized from the polymeric composition including from 0 to 5% by weight of an ionizable and/or ionized monomer, based on weight of the total monomers, as long as the flow limit value of the flow limit fluid in which the polymers of the invention are included are not adversely affected (i.e., the flow limit value of the fluid does not fall below 0.1 Pan).
[0085] In another aspect, the amphiphilic polymeric compositions of the invention can be polymerized from the polymeric composition comprising less than 3% by weight in one aspect, less than 1% by weight in another aspect, less than 0. 5% by weight in yet another aspect, less than 0.1% by weight in a further aspect and less than 0.05% by weight in another aspect, of an ionizable and/or an ionized portion, based on weight of the total of monomers.
[0086] Ionizable monomers include monomers having a base neutralizable portion and monomers having an acid neutralizable portion. Base neutralizable monomers include olefinically unsaturated monocarboxylic and dicarboxylic acids and their salts containing 3 to 5 carbon atoms and anhydrides thereof. Examples include (meth)acrylic acid, itaconic acid, maleic acid, maleic anhydride and combinations thereof. Other acidic monomers include styrenesulfonic acid, acrylamidoethylpropanesulfonic acid (AMPS® Monomer), vinylsulfonic acid, vinylphosphonic acid, allylsulfonic acid, methallylsulfonic acid and its salts.
[0087] Acid neutralizable monomers include olefinically unsaturated monomers that contain a basic nitrogen atom capable of forming a salt or quatemized moiety upon addition of an acid. For example, these monomers include vinylpyridine, vinylpiperidine, vinylimidazole, vinylmethylimidazole, dimethylaminomethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminomethyl (meth)acrylate and methacrylate, dimethylaminonepentyl (meth)acrylate, dimethylaminopropyl (meth)acrylate and diethylaminoethyl (meth) acrylate. Crosslinking Monomer
[0088] In one embodiment, the crosslinked, nonionic, amphiphilic polymers useful in the practice of the invention are polymerized from the polymeric composition comprising the first monomer comprising at least one nonionic hydrophilic unsaturated monomer, at least one hydrophobic monomer nonionic unsaturated and mixtures thereof and a third monomer comprising at least one polyunsaturated crosslinking monomer. Crosslinking monomers are used to polymerize covalent crosslinks in the polymer backbone. In one aspect, the crosslinking monomer is a polyunsaturated compound containing at least 2 unsaturated moieties. In another aspect, the crosslinking monomer contains at least 3 unsaturated moieties. Exemplary polyunsaturated compounds include di(meth)acrylate compounds such as ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate , 1,6-butylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 2,2'-bis( 4-(acryloxypropyloxyphenyl)propane and 2,2'-bis(4-(acryloxydiethoxyphenyl)propane; tri(meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate and tetramethylolmethane tri(meth)acrylate; tetra(meth)acrylate compounds such as ditrimethylolpropane tetra(meth)acrylate, tetramethylolmethane tetra(meth)acrylate and pentaerythritol tetra(meth)acrylate; hexa(meth)acrylate compounds such as dipentaerythritol hexa (meth)acrylate; allyl compounds such as allyl (meth)acrylate, diallylphthalate, diallyl itaconate, diallyl fumarate and diallyl maleate; sucrose polyallyl ethers having 2 to 8 allyl groups per molecule, pentaerythritol polyallyl ethers such as pentaerythritol diallyl ether, pentaerythritol triallyl ether and pentaerythritol tetralyl ether and combinations thereof; trimethylolpropane polyallyl ethers such as diallyl trimethylolpropane, trimethylolpropane ether, triallyl ether and combinations thereof. Other suitable polyunsaturated compounds include divinyl glycol, divinyl benzene and methylenebisacrylamide.
[0089] In another aspect, suitable polyunsaturated monomers can be synthesized through an esterification reaction of a polyol made from ethylene oxide or propylene oxide or combinations thereof with unsaturated anhydride, such as maleic anhydride, citraconic anhydride, itaconic anhydride or an addition reaction with unsaturated isocyanate, such as 3-isopropenyl-α-α-dimethylbenzene isocyanate.
[0090] Mixtures of two or more of the foregoing polyunsaturated compounds can also be used to crosslink the nonionic amphiphilic polymers of the invention. In one aspect, the unsaturated crosslinking monomer mixture contains an average of 2 unsaturated portions. In another aspect, the crosslinking monomer mixture contains an average of 2.5 unsaturated portions. In yet another aspect, the crosslinking monomer mixture contains an average of about 3 unsaturated moieties. In another aspect, the crosslinking monomer mixture contains an average of about 3.5 unsaturated moieties.
[0091] In one embodiment of the invention, the crosslinking monomer component can be used in an amount ranging from about 0.01 to about 1% by weight in one aspect, from about 0.05 to about 0.75% by weight in another aspect and from about 0.1 to about 0.5% by weight in another aspect, based on the dry weight of the nonionic amphiphilic polymer of the invention.
[0092] In another embodiment of the invention, the crosslinking monomer component contains an average of about 3 unsaturated portions and can be used in an amount ranging from about 0.01 to about 0.3% by weight in one aspect, from about 0.02 to about 0.25% by weight in another aspect, from about 0.05 to about 0.2% by weight in another aspect and from about 0.075 to about 0.175 % by weight in yet another aspect and from about 0.1 to about 0.15 % by weight in another aspect, based on the total weight of the nonionic amphiphilic polymer of the invention.
[0093] In one aspect, the crosslinking monomer is selected from trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, pentaerythritol triallyl ether and sucrose polyallyl ethers having 3 allyl groups per molecule . Amphiphilic Polymer Synthesis
[0094] The nonionic, cross-linked amphiphilic polymer of the present invention can be made using conventional free radical emulsion polymerization techniques. Polymerization processes are carried out in the absence of oxygen under an inert atmosphere such as nitrogen. Polymerization can be carried out in a suitable solvent system such as water. Smaller amounts of a hydrocarbon solvent, organic solvent as well as mixtures thereof can be used. Polymerization reactions are initiated by any means that result in the generation of a suitable free radical. Thermally derived radicals, in which the radical species are generated from homolytic, thermal dissociation of peroxides, hydroperoxides, persulfates, percarbonates, peroxyesters, hydrogen peroxide and azo compounds can be used. Initiators can be water soluble or water insoluble depending on the solvent system used by a polymerization reaction.
The starter compounds can be used in an amount of up to 30% by weight in one aspect, 0.01 to 10% by weight in another aspect and 0.2 to 3% by weight in another aspect, based on weight total dry polymer.
[0096] Exemplary free radical water-soluble initiators include, but are not limited to, inorganic persulfate compounds, such as ammonium persulfate, potassium persulfate, and sodium persulfate; peroxides such as hydrogen peroxide, benzoyl peroxide, acetyl peroxide and lauryl peroxide; organic hydroperoxides such as cumene hydroperoxide and t-butyl hydroperoxide; organic peracids such as peracetic acid and water soluble azo compounds such as 2,2'-azobis(tert-alkyl) compounds having a water solubilizing substituent on the alkyl group. Exemplary free radical water-soluble compounds include, but are not limited to, 2,2'-azobisisobutyronitrile and others. Peroxides and peracids can optionally be activated with reducing agents such as sodium bisulfide, sodium formaldehyde or ascorbic acid, transition metals, hydrazine and others.
[0097] In one aspect, azo polymerization catalysts include the Vazok free radical polymerization initiators, available from DuPont, such as Vazo" 44 (2,2'-azobis(2-(4,5-dihydroimidazolyl)propane), Vazo* 56 dihydrochloride (2,2'-azobis(2-methylpropionamidine)), Vazo* 67 (2,2'-azobis(2-methylbutyronitrile)) and Vazo* 68 (4,4'-azobis(4-cyanovaleric acid) )).
[0098] Optionally, the use of redox initiator systems known as polymerization initiators can be used. Such redox initiator systems include an antioxidant (initiator) and a reducer. Suitable oxidants include, for example, hydrogen peroxide, sodium peroxide, potassium peroxide, t-butyl hydroperoxide, t-amyl hydroperoxide, cumene hydroperoxide, sodium perborate, perphosphoric acid and salts thereof, potassium permanganate and ammonium or alkali metal salts of peroxydisulfuric acid, typically at a level of 0.01% to 3.0% by weight, based on dry polymer weight, are used. Suitable reductants include, for example, ammonium and alkali metal salts of sulfur-containing acids such as sodium sulfide, bisulfide, thiosulfate, hydrosulfide, sulfide, hydrosulfide or dithionite, formadinosulfinic acid, hydroxymethanesulfonic acid, acetone bisulfide, amines such as ethanolamine , glycolic acid, glyoxylic acid hydrate, ascorbic acid, isoascorbic acid, lactic acid, glyceric acid, malic acid, 2-hydroxy-2-sulfmatoacetic acid, tartaric acid and salts of the preceding acids typically at a level of 0.01% a 3.0% by weight, based on dry polymer weight, is used. In one aspect, combinations of peroxodisulfates with ammonium disulfides or alkali metals can be used, for example, ammonium peroxodisulfate and ammonium disulfide. In another aspect, combinations of hydrogen peroxide containing compounds (t-butyl hydroperoxide) as the oxidant with ascorbic or erythorbic acid as the reductant can be used. The ratio of the containing compound to the reducer is within the range of 30:1 to 0.05:1.
[0099] In emulsion polymerization processes it may be advantageous to stabilize the polymer/monomer droplets or particles by means of surface active auxiliaries. Typically these are emulsifiers or protective colloids. Emulsifiers used can be anionic, non-ionic, cationic or amphoteric. Examples of anionic emulsifiers are alkylbenzenesulfonic acids, sulfonated fatty acids, sulfosuccinates, fatty acid sulfates, alkylphenol sulfates, and fatty alcohol ether sulfates. Examples of usable nonionic emulsifiers are alkylphenol ethoxylates, primary alcohol ethoxylates, fatty acid ethoxylates, alkalamide ethoxylates, fatty amine ethoxylates, EO/PO block copolymers and alkylpolyglycosides. Examples of cationic and amphoteric emulsifiers used are quartenized amine alkoxylates, alkylbetaines, alkylamidobetaines and sulfobetaines.
[0100] Examples of typical protective colloids are derivatives of cellulose, polyethylene glycol, polypropylene glycol, copolymers of ethylene glycol and propylene glycol, polyvinyl acetate, poly(vinyl alcohol), partially hydrolyzed poly(vinyl alcohol), polyvinyl ether, starch and starch derivatives, dextran, polyvinylpyrrolidone, polyvinylpyridine, polyethyleneimine, polyvinylimidazole, polyvinylsuccinimide, polyvinyl-2-methylsuccinimide, polyvinyl-1,3-oxazolid-2-one, polyvinyl-2-methylimidazoline and maleic acid or anhydride copolymers. Emulsifiers or protective colloids are commonly used in concentrations of 0.05 to 20% by weight, based on the weight of total monomers.
[0101] The polymerization reaction can be carried out at temperatures ranging from 20 to 200° C in one aspect, from 50 to 150° C in another aspect and from 60 to 100° C in another aspect.
[0102] Polymerization can be carried out in the presence of chain transfer agents. Suitable chain transfer agents include, but are not limited to, tritium and disulfide containing compounds, such as C1 -C18 alkyl mercaptans, such as tert-butyl mercaptans, n-octyl mercaptan, n-dodecyl mercaptan, aryl mercaptan tert-dodecyl hexadecyl mercaptan, octadecyl mercaptan; mercaptoalcohols such as 2-mercaptoethanol, 2-mercaptopropanol; mercaptocarboxylic acids such as mercaptoacetic acid and 3-mercaptopropionic acid; mercaptocarboxylic acid esters such as butyl thioglycolate, isooctyl thioglycolate, dodecyl thioglycolate, isooctyl 3-mercaptopropionate and butyl 3-mercaptopropionate; thioesters; C 1 -C 18 alkyl disulfides; aryldisulfides; polyfunctional thiols such as trimethylolpropane-tris-(3-mercaptopropionate), pentaerythritol-tetra-(3-mercaptopropionate), pentaerythritol-tetra-(thioglycolate), pentaerythritol-tetra-(thiolactate), dipentaerythritol-hexa-(thioglycolate) and others; phosphites and hypophosphites; C1-C4 aldehydes such as formaldehyde, acetaldehyde, propionaldehyde; haloalkyl compounds such as carbon tetrachloride, bromotrichloromethane and others; hydroxylammonium salts such as hydroxylammonium sulfate; formic acid; sodium bisulfide; isopropanol and catalytic chain transfer agents such as, for example, cobalt complexes (for example, cobalt(II) chelates).
[0103] Chain transfer agents are generally used in amounts ranging from 0.1 to 10% by weight, based on the total weight of monomers present in a polymerization medium. Emulsion process
[0104] In an exemplary aspect of the invention, the nonionic, cross-linked amphiphilic polymer is polymerized through an emulsion process. The emulsion process can be conducted in a single reactor or in multiple reactors as is well known in the art. Monomers can be added as a batch mixture or each monomer can be measured in the reactor in a staged process. A typical mixture in emulsion polymerization comprises water, monomers, an initiator (usually water soluble) and an emulsifier. The "monomers can be emulsion polymerized in a single-stage, two-stage, or multiple-stage polymerization process according to methods well known in the emulsion polymerization art. In a two-stage polymerization process, the first-stage monomers are added and polymerized first in the aqueous medium, followed by the addition and polymerization of the second stage monomers. The aqueous medium optionally may contain an organic solvent. If used the organic solvent is less than about 5% by weight of the aqueous medium. Suitable water miscible organic solvents include, without limitation, esters, alkylene glycol ethers, alkylene glycol ether esters, lower molecular weight aliphatic alcohols and others.
[0105] To facilitate emulsification of the monomeric mixture, emulsion polymerization is carried out in the presence of at least one surfactant. In one embodiment, the emulsion polymerization is carried out in the presence of surfactant (active weight basis) ranging in amount from about 0.2% to about 5% by weight in one aspect, from about 0.5% to about 3% in another aspect and from about 1% to about 2% by weight in another aspect, based on a total monomer weight basis. The emulsion polymerization reaction mixture also includes one or more free radical initiators which are present in an amount ranging from about 0.01% to about 3% by weight based on the weight of total monomer. The polymerization can be carried out in an aqueous or aqueous alcohol medium. Surfactants to facilitate an emulsion polymerization include anionic, nonionic, amphoteric and cationic surfactants, as well as mixtures of these. The most commonly anionic and nonionic surfactants can be used as well as mixtures of these.
[0106] Suitable anionic surfactants for facilitating emulsion polymerizations are well known in the art and include, but are not limited to (C6-C18) alkyl sulfates, (C6-C18) alkyl ether sulfates (eg, C6-C18 sulfate). sodium lauryl and sodium laureth sulfate), alkali metal and amino salts of dodecylbenzenesulfonic acid, such as sodium dodecyl benzene sulfonate and dimethylethanolamine dodecylbenzenesulfonate, sodium alkyl phenoxy benzene sulfonate (CO-CIÔ), sodium disulfonate sodium (C6-C18) alkyl phenoxy benzene, sodium (C6-C16) phenoxy dialkyl benzene sulfonate, disodium lauret-3 sulfosuccinate, sodium dioctyl sulfosuccinate, sec-butyl naphthalene sulphonate, disodium dodecyl diphenyl ether sulfonate, disodium n-octadecyl sulfosuccinate, alcohol phosphate esters, branched ethoxylates and others.
[0107] Nonionic surfactants suitable for facilitating emulsion polymerizations are well known in the polymer art and include, without limitation, linear or branched C8-C30 fatty alcohol ethoxylates such as caprylic alcohol ethoxylate, lauryl alcohol ethoxylate, ethoxylate myristyl alcohol, cetyl alcohol ethoxylate, stearyl alcohol ethoxylate, cetearyl alcohol ethoxylate, sterol ethoxylate, oleyl alcohol ethoxylate, and behenyl alcohol ethoxylate; alkylphenol alkoxylates such as octylphenol ethoxylates and polyoxyethylene polyoxypropylene block copolymers and others. Additional fatty alcohol ethoxylates suitable as nonionic surfactants are described below. Other useful nonionic surfactants include polyoxyethylene glycol C8-C22 fatty acid esters, mono- and diglycerides ethoxylates, sorbitan esters and ethoxylate sorbitan esters, C8-C22 fatty acid glycol esters, ethylene oxide block copolymers. propylene and combinations thereof. The number of ethylene oxide units in each of the foregoing ethoxylates can range from 2 and above in one aspect and from 2 to about 150 in another aspect.
[0108] Optionally, other emulsion polymerization additives and processing aids that are well known in the emulsion polymerization art, such as auxiliary emulsifiers, protective colloids, solvents, buffering agents, chelating agents, inorganic electrolytes, polymeric stabilizers, biocides and pH adjusting agents can be included in a polymerization system.
[0109] In one embodiment of the invention, the protective colloid or auxiliary emulsifier is selected from poly(vinyl alcohol) which has a degree of hydrolysis ranging from about 80 to 95% in one aspect and from about 85 to 90% in another aspect.
[0110] In a typical two-stage emulsion polymerization, a mixture of the monomers is added in a first reactor under an inert atmosphere to an emulsifying solution of the surfactant (eg, anionic surfactant) in water. Optional processing aids can be added as desired (eg protective colloids, auxiliary emulsifiers). The reactor contents are stirred to prepare a monomer emulsion. A second reactor equipped with an agitator, an inert gas inlet and feed pumps are added under inert atmosphere the desired amount of water and additional anionic surfactant and optional processing aids. The contents of the second reactor are heated with mixing by stirring. After the contents of the second reactor reach a temperature in the range of about 55 to 98°C, a free radical initiator is injected so that the solution of the aqueous surfactant formed in the second reactor and the monomer emulsion from the first reactor is gradually measured in the second reactor over a period typically ranging from about a half to about four hours. The reaction temperature is controlled in the range of about 45 to about 95°C. After completion of the monomer addition, an additional amount of the free radical initiator can optionally be added to the second reactor and the resulting reaction mixture is typically kept at a temperature of about 45 to 95°C for a period of time sufficient to complete the polymerization reaction to obtain the polymer emulsion.
[0111] In one embodiment, the nonionic, crosslinked amphiphilic polymer of the invention are selected from an emulsion polymer polymerized from the monomeric mixture comprising at least 30% by weight of at least one C-hydroxyalkyl (meth)acrylate ]-C4 (eg hydroxyethyl methacrylate), 15 to 70% by weight of at least one C1-C12 alkyl acrylate, 5 to 40% by weight of at least one CpC10 carboxylic acid vinyl ester (based on weight of total monomers) and 0.01 to 1% by weight of at least one crosslinker (based on dry weight of polymer).
[0112] In another aspect, the cross-linked, nonionic amphiphilic polymer of the invention is selected from an emulsion polymer polymerized from the monomeric mixture comprising at least 30% by weight hydroxyethyl methacrylate, 15 to 35% by weight ethyl acrylate , 5 to 25% by weight of butyl acrylate, 10 to 25% by weight of a vinyl ester of a C1 -C5 carboxylic acid selected from vinyl, acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate and vinyl valerate (said percentage by weight is based on the weight of total monomers) and from about 0.01 to about 0.3 % by weight of a crosslinking monomer having an average of at least 3 crosslinkable unsaturated groups (based on polymer dry weight).
[0113] In another embodiment, the cross-linked, nonionic amphiphilic polymer of the invention is selected from an emulsion polymer polymerized from the monomeric mixture comprising from about 30 to 60% by weight of at least one (meth)acrylate of C 1 -C 4 hydroxyalkyl (e.g., hydroxyethyl methacrylate), 15 to 70% by weight of at least one C 1 -C 2 alkyl acrylate (at least one C 1 -C 5 alkyl acrylate in another aspect), from about 0.1 to about 10 by weight of at least one associative and/or semi-hydrophobic monomer (based on weight of total monomers) and from 0.01 to about 1% by weight of at least one crosslinker (based on dry weight of the polymer).
[0114] In another embodiment, the cross-linked, nonionic amphiphilic polymer of the invention is selected from an emulsion polymer polymerized from the monomeric mixture comprising from about 35 to 50% by weight of at least one (meth)acrylate of C1-C4 hydroxyalkyl (for example, hydroxyethyl methacrylate), 15 to 60% by weight of at least one C1-C12 alkyl acrylate (at least one C1-C5 alkyl acrylate in another aspect), of about 0. 1 to about 10% by weight of at least one associative and/or semi-hydrophobic monomer (based on the weight of total monomers) and from 0.01 to about 1% by weight of at least one crosslinker (based on the polymer dry weight).
[0115] In another embodiment, the cross-linked, nonionic amphiphilic polymer of the invention is selected from an emulsion polymer polymerized from the monomeric mixture comprising from about 40 to 45% by weight of at least one (meth)acrylate of C1 -C4 hydroxyalkyl (eg hydroxyethyl methacrylate), 15 to 60% by weight of at least two different C1 -C5 alkyl acrylate monomers, from about 1 to about 5% by weight of at least one associative monomer and/or semi-hydrophobic (based on weight of total monomers) and from 0.01 to about 1% by weight of at least one crosslinker (based on dry weight of polymer).
[0116] In another embodiment, the nonionic, crosslinked amphiphilic polymer of the invention is selected from an emulsion polymer polymerized from the monomeric mixture comprising from about 40 to 45 % by weight of hydroxyethyl acrylate, 30 to 50 % by weight of ethyl acrylate, 10 to 20% by weight of butyl acrylate and from about 1 to about 5% by weight of at least one associative and/or semi-hydrophobic monomer (based on weight of total monomers ) and from 0.01 to about 1% by weight of at least one crosslinker (based on dry polymer weight).
[0117] In an exemplary aspect of the invention, the flow-limit fluid of the invention comprises: i) at least one nonionic, crosslinked, amphiphilic polymer previously described; ii) at least one surfactant selected from at least one anionic surfactant, at least one cationic surfactant, at least one amphoteric surfactant, at least one nonionic surfactant and combinations thereof and iii) water.
[0118] In another exemplary aspect of the invention, the flow-limit fluid of the invention comprises: i) at least one nonionic, crosslinked, amphiphilic polymer previously described; ii) at least one anionic surfactant and iii) water.
[0119] In another exemplary aspect of the invention, the flow-limit fluid of the invention comprises: i) at least one nonionic, crosslinked amphiphilic polymer previously described; ii) at least one anionic surfactant and at least one amphoteric surfactant and iii) water.
[0120] Surprisingly, the present amphiphilic polymers can be activated by a surfactant to provide a stable flow-limit fluid with desired aesthetic and rheological properties with the ability to suspend insoluble materials and particulates in an aqueous medium for indefinite periods of time independent of pH. The yield point value, elastic modulus and optical clarity are substantially independent of pH in the compositions in which they are included. The flow limit fluid of the invention is useful in the pH range of about 2 to about 14 in one aspect, from about 3 to 11 in another aspect, and from about 4 to about 9 in another aspect. Unlike cross-linked pH-responsive polymers (acidic or base-sensitive) which require neutralization with an acid or a base to impart a desired rheological profile, the nonionic, crosslinked amphiphilic polymer of the rheological profiles of the invention are substantially pH-independent. Substantially pH-independent is meant that the flow-limit fluid within which the polymer of the invention is included imparts a desired rheological profile (e.g., a flow-limit of at least 0.1 Pa in one aspect, at least at least 0.5 Pa in another aspect, at least 1 Pa in yet another aspect and at least 2 Pa in another aspect) across a wide pH range (eg, from about 2 to about 14) where the standard deviation at flow stress values across the pH range it is less than 1 Pa in one aspect, less than 0.5 Pa in another aspect, and less than 0.25 Pa in another aspect of the invention.
[0121] In an exemplary aspect of the invention, the flow-limit fluid comprises at least one nonionic, cross-linked amphiphilic polymer, at least one anionic surfactant, an optional nonionic surfactant and water.
[0122] In another exemplary aspect, the flow-limit fluid comprises at least one nonionic, cross-linked amphiphilic polymer, at least one anionic surfactant, at least one amphoteric surfactant, an optional nonionic surfactant and water.
[0123] Still in an exemplary aspect, the flow-limit fluid comprises at least one nonionic, cross-linked amphiphilic polymer, at least one anionic ethoxylated surfactant, an optional nonionic surfactant and water. In one aspect, the average degree of ethoxylation in the anionic surfactant can range from about 1 to about 3. In another aspect, the average degree of ethoxylation is about 2.
[0124] Still in an exemplary aspect, the flow-limit fluid comprises at least one nonionic, cross-linked amphiphilic polymer, at least one anionic ethoxylated surfactant, at least one amphoteric surfactant, an optional nonionic surfactant and water. In one aspect, the average degree of ethoxylation in the anionic surfactant can range from about 1 to about 3. In another aspect, the average degree of ethoxylation is about 2.
[0125] Still in an exemplary aspect, the yield-limit fluid comprises at least one nonionic, cross-linked amphiphilic polymer, at least one anionic non-ethoxylated surfactant, at least one anionic ethoxylated surfactant, an optional nonionic surfactant, and water. In one aspect, the average degree of ethoxylation in the anionic surfactant can range from about 1 to about 3. In another aspect, the average degree of ethoxylation is about 2.
[0126] In another exemplary aspect, the flow-limit fluid comprises at least one nonionic, crosslinked amphiphilic polymer, at least one non-ethoxylated anionic surfactant, at least one anionic ethoxylated surfactant, at least one amphoteric surfactant, an optional non-ethoxylated surfactant. ionic and water. In one aspect, the average degree of ethoxylation in the anionic surfactant can range from about 1 to about 3. In another aspect, the average degree of ethoxylation is about 2.
[0127] The amount of amphiphilic polymer used in the formulation of the flow-limit fluids of the invention ranges from about 0.5 to about 5% by weight of polymer solids (100% active polymer) based on the weight of the composition total. In another aspect, the amount of amphiphilic polymer used in the formulation ranges from about 0.75% by weight to about 3.5% by weight. In yet another aspect, the amount of amphiphilic polymer used in the flow-limit fluid ranges from about 1 to about 3% by weight. In a further aspect, the amount of amphiphilic polymer used in the flow-limit fluid ranges from about 1.5% by weight to about 2.75% by weight. In a still further aspect, the amount of amphiphilic polymer used in the flow-limit fluid ranges from about 2 to about 2.5% by weight. The nonionic, cross-linked amphiphilic polymer used in the formulation of the flow-limit fluids of the invention is an emulsion polymer.
[0128] The surfactants used to formulate the flow limit fluids of the invention can be selected from anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants and mixtures of these.
[0129] Non-limiting examples of anionic surfactants are described in McCutcheon's Detergents and Emulsifiers, North American Edition, 1998, published by Allured Publishing Corporation and McCutcheon's, Functional Materials, North American Edition (1992); both of which are incorporated by reference herein in their entirety. The anionic surfactant can be any of the anionic surfactants known or previously used in the art of aqueous surfactant compositions. Suitable anionic surfactants include but are not limited to alkyl sulfates, alkyl ether sulfates, alkyl sulfonates, alkaryl sulfonates, o-olefin sulfonates, alkylamide sulfonates, alkarylpolyether sulfates, alkylamidoether sulfates, alkyl monoglyceryl ether sulfates, alkyl monoglyceride, alkyl monoglyceride sulfonates, alkyl succinates, alkyl sulfosuccinates, alkyl sulfosuccinates, alkyl ether sulfosuccinates, alkyl amidosulfosuccinates; alkyl sulfoacetates, alkyl phosphates, alkyl ether phosphates, alkyl ether carboxylates, alkyl amidoether carboxylates, N-alkylamino acids, N-acyl amino acids, alkyl peptides, N-acyl taurates, alkyl isethionates, carboxylate salts wherein the acyl group is derived from the fatty acids and the alkali metal, alkaline earth metal, ammonium, amine and triethanolamine salts thereof.
[0130] In one aspect, the cation portion of the foregoing salts is selected from sodium, potassium, magnesium, ammonium, mono-, di- and triethanolamine salts and mono-, di- and tri-isopropylamine salts. the alkyl and acyl groups of the foregoing surfactants contain from about 6 to about 24 carbon atoms in one aspect, from 8 to 22 carbon atoms in another aspect, and from about 12 to 18 carbon atoms in another aspect, and may be saturated or unsaturated. Aryl groups in surfactants are selected from phenyl or benzyl. The ether-containing surfactants presented above may contain 1 to 10 units of ethylene oxide and/or propylene oxide per surfactant molecule in one aspect and 1 to 3 units of ethylene oxide per surfactant molecule in another aspect.
[0131] Examples of suitable anionic surfactants include but are not limited to sodium, potassium, lithium, magnesium and ammonium salts of lauret sulphate, tridecet sulphate, miret sulphate, C12-C13 paret sulphate, C12-C14 lauret sulphate. paret and C12-C15 paret sulfate, ethoxylated with 1, 2, 3, 4 or 5 moles of ethylene oxide; sodium, potassium, lithium, magnesium, ammonium and lauryl sulphate triethanolamine, coconut sulphate, tridecyl sulphate, myrtile sulphate, cetyl sulphate, cetearyl sulphate, stearyl sulphate, oleyl sulphate and tallow sulphate, lauryl sulfosuccinate of disodium, disodium lauret sulfosuccinate, sodium cocoyl isethionate, C12 -C14 sodium olefin sulfonate, sodium lauret-6 carboxylate, sodium methyl cocoyl taurate, sodium cocoyl glycinate, sodium myristyl sarcocinate, sodium dodecylbenzene sulfonate, sodium cocoyl sarcosinate, sodium cocoyl glutamate, potassium myristoyl glutamate, monolauryl triethanolamine phosphate and fatty acid soaps, including the sodium, potassium, ammonium and triethanolamine salts of saturated or saturated fatty acids unsaturated compounds containing from about 8 to about 22 carbon atoms.
[0132] Cationic surfactants can be any of the cationic surfactants known or previously used in the techniques of aqueous surfactant compositions. Useful cationic surfactants can be one or more of those described, for example, in McCutcheon's Detergents and Emulsifiers, North American Edition, 1998, supra and Kirk-Othmer, Encyclopedia of Chemical Technology, 4th Ed., Vol. 478-541, the contents of which are incorporated herein by reference. Suitable classes of cationic surfactants include but are not limited to alkyl amines, alkyl imidazolines, ethoxylated amines, quaternary compounds and quaternized esters. Also, alkyl amine oxides can function as a cationic surfactant at low pH.
[0133] Alkylamine surfactants can be salts of C12-C22 alkylamines, primary, secondary and tertiary greases, substituted or unsubstituted, and substances sometimes referred to as "amidoamines". Non-limiting examples of alkylamines and salts thereof include dimethyl cocamine, dimethyl palmitamin, dioctylamine, dimethyl stearamine, dimethyl soyamine, soyamine, myristyl amine, tridecyl amine, ethyl stearylamine, N-tallowpropane diamine, ethoxylated stearylamine, dihydroxy ethyl stearylamine, arachidylbene amine , stearylamine hydrochloride, soyamine chloride, stearylamine formate, N-tallowpropane diamine dichloride and amodimethicone.
[0134] Non-limiting examples of amidoamines and salts thereof include stearamido propyl dimethyl amine, stearamidopropyl dimethyl amine citrate, palmitamidopropyl diethyl amine and cocamidopropyl dimethyl amine lactate.
[0135] Non-limiting examples of alkyl imidazoline surfactants include alkyl hydroxyethyl imidazoline such as stearyl hydroxyethyl imidazoline, coco hydroxyethyl imidazoline, ethyl hydroxymethyl oleyl oxazoline and others.
[0136] Non-limiting examples of ethoxylated amines include PEG-cocopolyamine, PEG-15 tallow amine, quaternary-52 and others.
[0137] Among the quaternary ammonium compounds useful as cationic surfactants, some correspond to the general formula: (R20R21R22R23N+) E', where R20, R21, R22, and R23 are independently selected from an aliphatic group having from 1 to about 22 carbon atoms or an aromatic, alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, aryl or alkylaryl group having 1 to about 22 carbon atoms in the alkyl chain and E' is a salt-forming anion such as those selected from halogen, (for example , chloride, bromide), acetate, citrate, lactate, glycolate, phosphate, nitrate, sulfate and alkyl sulfate. Aliphatic groups may contain, in addition to carbon and hydrogen atoms, ether bonds, ester bonds and other groups such as amino groups. Longer chain aliphatic groups, for example those of about 12 carbons or more, can be saturated or unsaturated. In one aspect, aryl groups are selected from phenyl and benzyl.
Exemplary quaternary ammonium surfactants include, but are not limited to cetyl trimethylammonium chloride, cetylpyridinium chloride, dicetyl dimethyl ammonium chloride, diexadecyl dimethyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride, dioctadecyl dimethyl ammonium chloride, dieicosyl dimethyl ammonium chloride, didocosyl dimethyl ammonium chloride, diexadecyl dimethyl ammonium chloride, diexadecyl dimethyl ammonium acetate, behenyl trimethyl ammonium chloride, benzalkonium chloride, benzethonium chloride and di(coconutalkyl) dimethyl ammonium chloride, ditallowdimethyl chloride ammonium, di(hydrogenated tallow) dimethyl ammonium chloride, di(hydrogenated tallow) dimethyl ammonium acetate, ditallowdimethyl ammonium methyl sulfate, ditallow dipropyl ammonium phosphate and ditallow dimethyl ammonium nitrate.
[0139] At low pH, amine oxides can protonate and behave similarly to N-alkyl amines. Examples include, but are not limited to, dimethyldodecylamine oxide, oleyldi(2-hydroxyethyl)amine oxide, dimethyltetradecylamine oxide, di(2-hydroxyethyl)tetradecylamine oxide, dimethylhexadecylamine oxide, behenamine oxide, cocamine oxide , decyltetradecylamine oxide, C12 -C15 dihydroxyethyl alkoxypropylamine, dihydroxyethyl cocamine oxide, dihydroxyethyl lauramine oxide, dihydroxyethyl stearamine oxide, dihydroxyethyl tallowamine oxide, hydrogenated palm seed amine oxide, hydrogenated hydroxypropyl hydroxyethylamine oxide C12-C15, lauramine oxide, myristamine oxide, cetylamine oxide, oleamidopropylamine oxide, oleamine oxide, palmitamine oxide, PEG-3 lauramine oxide, dimethyl lauramine oxide, potassium trisphosphonomethylamine oxide, soyamidopropylamine oxide, oxide of cocamidopropylamine, stearamine oxide, tallowamine oxide and mixtures thereof.
[0140] The term "amphoteric surfactant" as used herein is also intended to encompass zwitterionic surfactants, which are well known to skilled formulators in the art as a subset of amphoteric surfactants. Non-limiting examples of amphoteric surfactants are described McCutcheon's Detergents and Emulsifiers, North American Edition, supra and McCutcheon's, Functional Materials, North American Edition, supra; both of which are incorporated by reference herein in their entirety. Suitable examples include but are not limited to amino acids (for example N-alkyl amino acids and N-acyl amino acids), betaines, sultains and alkyl amphocarboxylates.
[0141] Amino acid-based surfactants suitable in the practice of the present invention include surfactants represented by the formula:
wherein R~ represents a saturated or unsaturated hydrocarbon group having 10 to 22 carbon atoms or an acyl group containing a saturated or unsaturated hydrocarbon group having 9 to 22 carbon atoms, Y is hydrogen or methyl, Z is selected from hydrogen , -CH3, -CH(CH3)2, -CH2CH(CH3)2, -CH(CH3)CH2CH3, -CH2C6H5, -CH2C6H4OH, -CH2OH, -CH(OH)CH3, -(CH2)4NH2, -(CH2 )3NHC(NH)NH2, -CH2C(O)OM+, -(CH2)2C(O)O'M+. M is a cation that forms salt. In one aspect, R25 represents a radical selected from a linear or branched C10 to C22 alkyl group, a linear or branched C10 to C22 alkenyl group, an acyl group represented by R"C(O)-, wherein R " a linear or branched C9 to C22 alkyl group, a linear or branched C9 to C22 alkenyl group is selected. In one aspect, M+ is a cation selected from sodium, potassium, ammonium, and triethanolamine (TEA).
[0142] Amino acid surfactants can be derived from the alkylation and acylation of α-amino acids such as, for example, alanine, arginine, aspartic acid, glutamic acid, glycine, isoleucine, leucine, lysine, phenylalanine, serine, tyrosine and valine. Representative N-acyl amino acid surfactants are, but not limited to, the carboxylate mono- and di-salts (eg, sodium, potassium, ammonium and TEA) of N-acylated glutamic acid, e.g., sodium cocoyl glutamate , sodium lauroyl glutamate, sodium myristoyl glutamate, sodium palmitoyl glutamate, sodium stearoyl glutamate, sodium cocoyl diglutamate, sodium stearoyl diglutamate, potassium cocoyl glutamate, potassium lauroyl glutamate and myoyl glutamate potassium; the carboxylate salts (for example, sodium, potassium, ammonium and TEA) of N-acylated alanine, for example, sodium cocoyl alaninate and lauroyl TEA alaninate; the carboxylate salts (for example, sodium, potassium, ammonium and TEA) of N-acylated glycine, for example, sodium cocoyl glycinate and potassium cocoyl glycinate; the carboxylate salts (e.g. sodium, potassium, ammonium and TEA) of N-acylated sacrosin, e.g. sodium lauroyl sarcosinate, sodium cocoyl sarcosinate, sodium myristoyl sarcosinate, sodium oleoyl sarcosinate and sarcosinate of lauroyl ammonium and mixtures of the preceding surfactants.
[0143] The betaines and sultains useful in the present invention are selected from alkyl betaines, alkylamino betaines and alkylamido betaines, as well as the corresponding sulfobetaines (sultaines) represented by the formulas:
wherein R" is a C7-C22 alkyl or alkenyl group, each R" independently is a C1-C4 alkyl group, R is a C1-C5 alkylene group or a hydroxy substituted C1-C5 alkylene group, n is an integer from 2 to 6, A is a carboxylate or sulfonate group and M is a salt-forming cation. In one aspect, R~ is a C11-C18 alkyl group or a C11-C18 alkenyl group. " is methyl. In one aspect, R' is methylene, ethylene or hydroxy propylene. In one aspect, n is 3. In a further aspect, M is selected from sodium, potassium, magnesium, ammonium and triethanolamine mono-, diand and cations.
[0144] Examples of suitable betaines include, but are not limited to, lauryl betaine, coco betaine, oleyl betaine, cocoexadecyl dimethyl betaine, lauryl amidopropyl betaine, cocoamidopropyl betaine (CAPB) and cocamidopropyl hydroxysultaine.
[0145] Alkylamphocarboxylates such as alkylamphoacetates and alkylamphopropionates (mono- and disubstituted carboxylates) can be represented by the formula:
wherein R- is a C7-C22 alkyl or alkenyl group, R is -CH2C(O)O'NT, -CH2CH2C(O)O'M+ OR -CH2CH(OH)CH2SO3'M+, R31 is hydrogen or -CH2C( O)O' NT and M is a cation selected from sodium, potassium, magnesium, ammonium and mono-, di- and triethanolamine.
[0146] Exemplary alkylamphocarboxylates include, but are not
[0147] Non-limiting examples of nonionic surfactants are described in McCutcheon's Detergents and Emulsifiers, North American Edition, 1998, supra and McCutcheon's, Functional Materials, North American, supra; both of which are incorporated by reference herein in their entirety. Additional examples of nonionic surfactants are described in U.S. Patent No. 4,285,841, to Barrat et al. and U.S. Patent No. 4,284,532, to Leikhim et al., both of which are incorporated by reference herein in their entirety. Nonionic surfactants typically have a hydrophobic moiety such as a long chain alkyl group or an alkylated aryl group and a hydrophilic moiety containing varying degrees of ethoxy and/or propoxy moieties of ethoxylation and/or propoxylation (eg, 1 to about 50). Examples of some classes of nonionic surfactants that can be used include, but are not limited to, ethoxylated alkylphenols, ethoxylated and propoxylated fatty alcohols, methyl glucose polyethylene glycol ethers, sorbitol polyethylene glycol ethers, oxide block copolymers. ethylene-propylene oxide, ethoxylated fatty acid esters, condensation products of ethylene oxide with long chain amines or amides, condensation products of ethylene oxide with alcohols and mixtures thereof.
[0148] Suitable nonionic surfactants include, for example, alkyl polysaccharides, alcohol ethoxylates, block copolymers, castor oil ethoxylates, keto/oleyl alcohol ethoxylates, cetearyl alcohol ethoxylates, decyl alcohol ethoxylates, dinonyl phenol ethoxylates , dodecyl phenol ethoxylates, end capped ethoxylates, ether amine derivatives, ethoxylated alkanolamides, ethylene glycol esters, fatty acid alkanolamides, fatty alcohol alkoxylates, lauryl alcohol ethoxylates, mono-branched alcohol ethoxylates, nonyl phenol ethoxylates , octyl phenol ethoxylates, oleyl amine ethoxylates, random copolymer alkoxylates, sorbitan ester ethoxylates, stearic acid ethoxylates, stearyl amine ethoxylates, fatty acid tallow oil ethoxylates, tallow amine ethoxylates, tricanoyl ethoxylates acetylenic diols, polyoxyethylene sorbitol and mixtures thereof. Several specific examples of suitable nonionic surfactants include, but are not limited to, methyl glucet-10, PEG-20 methyl glucose distearate, PEG-20 methyl glucose sesquistearate, cetet-8, cetet-12, dodoxinol-12, lauret-15 , PEG-20 castor oil, polysorbate 20, stearet-20, polyoxyethylene-10 cetyl ether, polyoxyethylene-10 stearyl ether, polyoxyethylene-20 cetyl ether, polyoxyethylene-10 oleyl ether, polyoxyethylene-20 oleyl ether, an ethoxylated nonylphenol, octylphenol ethoxylated, ethoxylated dodecylphenol or ethoxylated fatty alcohol (C6-C22), including 3 to 20 portions of ethylene oxide, polyoxyethylene-20 isohexadecyl ether, polyoxyethylene-23 glycerol laurate, polyoxyethylene-20 glyceryl stearate, PPG-10 methyl glucose ether , PPG-20 methyl glucose ether, polyoxyethylene-20 sorbitan monoesters, polyoxyethylene-80 castor oil, polyoxyethylene-15 tridecyl ether, polyoxyethylene-6 tridecyl ether, lauret-2, lauret-3, lauret-4, PEG-3 oil of castor bean, PEG 600 dioleate, PEG 400 dioleate, poloxamers such as poloxamer 188, polysorbate 21, polysorbate 40, polysorbate 60, polysorbate 61, polysorbate 65, polysorbate 80, polysorbate 81, polysorbate 85, sorbitan caprylate, cocoate sorbitan, sorbitan diisostearate, sorbitan dioleate, sorbitan ester sorbitan fatty acid, sorbitan isostearate, sorbitan laurate, sorbitan oleate, sorbitan palmitate, sorbitan sesquiisostearate, sorbitan sesquioleate, sorbitan sesquistearate, sorbitan stearate, sorbitan triisostearate, sorbitan triisostearate, sorbitan tristearate, sorbitan trioleate mixture of these.
[0149] Alkyl glycoside nonionic surfactants can also be used and are generally prepared by reacting a monosaccharide or a hydrolyzable compound to a monosaccharide, with an alcohol such as a fatty alcohol in an acidic medium. For example, U.S. Patent No. 5,527,892 and 5,770,543 describe alkyl glycosides and/or methods for their preparation. Suitable examples are commercially available under the names Glucopon™ 220, 225, 425, 600 and 625, PLANT AC ARE® and PLANTAPON®, all of which are available from the Cognis Corporation of Ambler, Pennsylvania.
[0150] In another aspect, nonionic surfactants include, but are not limited to, alkoxylated methyl glycosides such as, for example, methyl glucet-10, methyl glucet-20, PPG-10 methyl glucose ether and PPG-20 methyl glucose ether , available from Lubrizol Advanced Materials, Inc., under the trade names, Glucam® E10, Glucam® E20, Glucam® PIO and Glucam® P20, respectively, and hydrophobically modified alkoxylated methyl glycosides such as PEG 120 methyl glucose dioleate, PEG-120 methyl glucose trioleate and PEG-20 methyl glucose sesquistearate, available from Lubrizol Advanced Materials, Inc., under the trade names, GlucamateR DOE-120, Glucamate™ LT and Glucamate™ SSE-20, respectively, are also suitable. Other exemplary hydrophobically modified alkoxylated methyl glycosides are described in U.S. Patent No. 6,573,375 and 6,727,357, the discoveries of which are incorporated herein by reference in their entirety.
[0151] Other useful nonionic surfactants include water soluble silicones such as PEG-10 Dimethicone, PEG-12 Dimethicone, PEG-14 Dimethicone, PEG-17 Dimethicone, PPG-12 Dimethicone, PPG-17 Dimethicone and derivative/functionalized forms thereof such as Bis-PEG/PPG-20/20 Dimethicone Bis-PEG/PPG-16/16 PEG/PPG-16/16 Dimethicone, PEG/PPG-14/4 Dimethicone, PEG/PPG-20/20 Dimethicone, PEG/ PPG-20/23 Dimethicone and Perfluorononylethyl Carboxidecyl PEG-10 Dimethicone.
[0152] The amount of at least one surfactant (active weight basis) used in the formulation of the flow-limit fluids of the invention ranges from about 1 to about 30% by weight based on the total flow-limit fluid weight composition. In another aspect, the amount of at least one surfactant used in the formulation ranges from about 3 to about 25% by weight. In yet another aspect, the amount of at least one surfactant used in the flow-limit fluid ranges from about 5 to about 22% by weight. In a further aspect, the amount of at least one surfactant used ranges from about 6 to about 20% by weight. In a still further aspect, the amount of at least one surfactant is about 10, 12, 14, 16 and 18% by weight based on the total weight of flow-limit fluid.
[0153] In one embodiment of the invention, the weight ratio (based on active material) of anionic surfactant (non-ethoxylated and/or ethoxylated) to amphoteric surfactant can range from about 10:1 to about 2:1 in one aspect and can be 9:1, 8:1, 7:1 6:1, 5:1, 4.5:1, 4:1 or 3:1 in another aspect. When using an ethoxylated anionic surfactant in combination with an ethoxylated nonionic surfactant and an amphoteric surfactant, the weight ratio (based on active material) of ethoxylated anionic surfactant to ethoxylated nonionic surfactant to amphoteric surfactant can range from about 3.5 :3,5:1 in one aspect to about 1:1:1 in another aspect.
[0154] In one embodiment, the fluid flow limit value is at least about 0.1 Pa in one aspect, about 0.5 Pa in one aspect, at least about 1 Pa in another aspect and at least about 1.5 Pa in another aspect. In another embodiment, the fluid flow tension ranges from about 0.1 to about 20 Pa in one aspect, from about 0.5 Pa to about 10 Pa in another aspect, from about 1 to about from 3 Pa in another aspect and from about 1.5 to about 3.5 in a further aspect.
[0155] Optionally, the flow limit fluid of the invention can contain an electrolyte. Suitable electrolytes are known compounds and include multivalent anion salts such as potassium pyrophosphate, potassium tripolyphosphate and sodium or potassium citrate, multivalent cation salts including alkaline earth metal salts such as calcium chloride and calcium bromide as well. such as zinc halides, barium chloride and calcium nitrate, salts of monovalent cations with monovalent anions, including alkali metals or ammonium halides, such as potassium chloride, sodium chloride, potassium iodide, sodium bromide and ammonium bromide , alkali metals or ammonium nitrates and combinations thereof. The amount of electrolyte used will generally depend on an amount of the amphiphilic polymer incorporated, but it can be used at concentration levels of from about 0.1 to about 4% by weight in one aspect and from about 0.2 to about 2 % by weight in another aspect, based on the weight of the total composition.
[0156] The yield point fluid must be easily pourable with a shear thinning index of less than 0.5 at shear rates between 0.1 and 1 second reciprocal and an optical transmission of at least 10%. The flow limit fluid of the invention can be used in combination with a rheology modifier (thickener) to enhance the flow value of a thick liquid. In one aspect, the yield point fluid of the invention can be combined with a non-ionic rheology modifier in which the rheology modifier when used alone does not have a sufficient yield point value. Any rheology modifier is suitable, as long as it is water soluble, stable, and does not contain ionic or non-nonizable groups. Suitable rheology modifiers include, but are not limited to, natural gums (for example, polygalactomannan gums selected from fenugreek, cassia, locust bean, tara and guar), modified cellulose (for example, ethyloxyethylcellulose (EHEC), hydroxybutylmethylcellulose (HBMC) , hydroxyethylmethylcellulose (HEMC), hydroxypropylmethylcellulose (HPMC), methylcellulose (MC), hydroxyethylcellulose (HEC), hydroxypropylcellulose (HPC) and cetyl hydroxyethylcellulose) and mixtures of these methylcellulose, polyethylene glycols (eg, PEG 4000, PEG 6000, PEG 8000, PEG 10000, PEG 20000), polyvinyl alcohol, polyacrylamides (homopolymers and copolymers) and hydrophobically modified ethoxylated urethanes (HEUR). The rheology modifier can be used in an amount ranging from about 0.5 to about 25% by weight in one aspect, from about 1 to about 15% by weight in another aspect, and from about 2 to about 10% by weight in another aspect, based on the total weight of the composition.
[0157] The flow-limit fluids of the invention can be used in any application that requires flow-limit properties. Flow limit fluids can be used alone or in combination with other fluids to enhance the flow limit values of these.
[0158] In one embodiment, the flow-limit fluids of the invention can be used to suspend particulate materials and insoluble droplets within an aqueous composition. Such fluids are useful in the oil and gas, personal care and home care industries.
[0159] In the oil and gas industry, the flow limit fluids of the invention can be used to increase the flow limit value of drilling and hydraulic fracture fluids and can be used to resuspend shear and fracture structurants of wellbore, such as, for example, sand, sintered bauxite, glass spheres, ceramic materials, polystyrene beads and others.
[0160] In the personal care industry, the flow-limiting fluids of the invention can be used to improve the flow-limiting properties of detersive compositions, skin and hair care compositions, as well as cosmetics and can be used to replenish in suspension insoluble silicones, opacifiers and pearlescent agents (eg mica, coated mica), pigments, exfoliants, anti-dandruff agents, clay, swellable clay, laponite, gas bubbles, liposomes, microsponges, cosmetic beads, cosmetic microcapsules and flakes. The flow-limit fluids of the invention can stabilize these materials in the suspension for at least one month at 23°C in one aspect, at least 6 months in another aspect, and at least one year in another aspect.
[0161] Stable compositions maintain an acceptable, smooth rheology with good shear thinning properties without significant increase or decrease in viscosity, with no phase separation, for example, sedimentation or skimming (rising to the surface) or loss of clarity over periods of extended times, such as for at least one month at 45°C.
[0162] Exemplary bead components include, but are not limited to, agar beads, alginate beads, jojoba beads, gelatin beads, Styrofoam™ beads, polyacrylate, polymethylmethacrylate (PMMA), polyethylene cosmetic beads, polyethylene beads Unispheres™ and Unipearls™ microcapsules (Induchem USA, Inc., New York, NY), Lipocapsule™, Liposphere™ and Lipopearl™ (Lipo Technologies Inc., Vandalia, OH) and Confetti II™ dermal release flakes (United-Guardian, Inc., Hauppauge, NY). Pearls can be used as aesthetic materials or they can be used to encapsulate beneficial agents to protect from the deteriorating effects of the environment or for optimal release and performance of the final product.
[0163] In one aspect, cosmetic pearls range in size from about 0.5 to about 1.5 mm. In another aspect, the difference in specific gravity of the bead and water is between about +/- 0.01 and 0.5 in one aspect and about +/- 0.2 to 0.3 g/ml in another aspect.
[0164] In one aspect, microcapsules range in size from about 0.5 to about 300 µm. In another aspect, the difference in specific gravity between the microcapsules and water is about +/- 0.01 to 0.5. Non-limiting examples of microcapsule beads are described in U.S. Patent No. 7,786,027, the discovery that is incorporated herein by reference.
[0165] In one aspect of the invention, the amount of the particulate component and/or insoluble droplets can range from about 0.1% to about 10% by weight based on the total weight of the composition.
[0166] While the weight overlap varies by various components and ingredients that may be contained in the flow-limit fluids of the invention have been expressed by selected embodiments and aspects of the invention, it should be readily apparent that the specific amount of each component in the compositions will be selected from their described range such that the amount of each component is adjusted so that the sum of all components in the composition will determine the total 100 percent by weight. The amounts used will vary with the purpose and character of the product desired and can be readily determined by a person skilled in the art of formulation and from the literature.
[0167] This invention is illustrated by the following examples which are merely for the purpose of illustration and are not to be considered as limiting the scope of the invention or the manner in which it may be practiced. Unless specifically stated otherwise, parts and percentages are given by weight.
[0168] The following abbreviations and trade names are used in the examples.


Example 1
[0169] An emulsion polymer polymerized from the monomeric mixture comprising 50% by weight of EA, 10% by weight of n-BA, 10% by weight of MM A, 30% by weight of HEMA and crosslinked with APE ( 0.08% by weight based on dry polymer weight) is synthesized as follows.
[0170] A monomer premix is made by mixing 140 grams of water, 16.67 grams of Sulfochem™ surfactant SLS (then SLS), 250 grams of EA, 50 grams of n-BA, 50 grams of MMA , 0.57 grams of 70% APE and 150 grams of HEMA. Initiator A is made by mixing 2.86 grams of 70% TBHP in 40 grams of water. Reducer A is prepared to dissolve 0.13 grams of erythorbic acid in 5 grams of water. Reducer B is prepared to dissolve 2.0 grams of erythorbic acid in 100 grams of water. A 3-liter reactor vessel is charged with 800 grams of water and 1.58 grams of SLS surfactant and then heated to 60°C under a blanket of nitrogen and self-stirring. Initiator A is then added to the reaction vessel and followed by the addition of reductant A. After about 1 minute, the monomer premix is metered into the reaction vessel over a period of 150 minutes. About 3 minutes after the start of the monomer premix ratio, reducer B is metered into the reaction vessel over a period of 180 minutes. After completion of feed to reducer B, the temperature of the reaction vessel is maintained at 60°C for 60 minutes. The reaction vessel is then cooled to 55°C. A solution of 1.79 grams of 70% TBHP and 0.58 grams of SLS in 25 grams of water is added to the reaction vessel. After 5 minutes, a solution of 1.05 grams of erythorbic acid and 0.1 grams of SLS in 25 grams of water is added to the reaction vessel. The reaction vessel is held at 55°C. After 30 minutes, a solution of 1.79 grams of 70% TBHP and 0.3 grams of SLS in 25 grams of water is added to the reaction vessel. After 5 minutes, a solution of 1.0 grams of erythorbic acid and 0.17 grams of SLS in 25 grams of water is added to the reaction vessel. The reaction vessel is kept at 55°C for about 30 minutes. Then, the reaction vessel is cooled to room temperature and its contents are filtered through 100 µm of tissue. The pH of the resulting emulsion is adjusted to 5 to 6 with ammonium hydroxide. The polymer emulsion has 30% by weight polymer solids, viscosity 15 cps and a particle size of 209 nm.
[0171] An emulsion polymer polymerized from the monomeric mixture comprising 35% by weight of EA, 20% by weight of n-BA, 45% by weight of HEMA and crosslinked with APE (0.08% by weight based by weight of dry polymer) is prepared as follows.
[0172] A monomer premix is made by mixing 140 grams of water, 5 grams of SLS, 175 grams of EA, 100 grams of n-BA, 0.57 grams of 70% APE and 225 grams of HEMA . Initiator A is made by mixing 2.86 grams of 70% TBHP in 40 grams of water. Reducer A is prepared to dissolve 0.13 grams of erythorbic acid in 5 grams of water. Reducer B is prepared to dissolve 2.0 grams of erythorbic acid in 100 grams of water. A 3 liter reactor vessel is loaded with 800 grams of water, 13.3 grams of SLS and 25 grams of poly(vinyl alcohol) (having an average molecular weight of 13,000-23,000 Daltons and 87-89% hydrolyzed from Sigma-Aldrich Co. .). The reactor vessel is heated to 60°C under a blanket of nitrogen and its own agitation. Initiator A is then added to the reaction vessel and followed by the addition of reductant A. After about 1 minute, the monomer premix is measured into the reaction vessel over a period of 150 minutes. About 3 minutes after starting the measurement of the monomer premix, reducer B is measured in the reaction vessel over a period of 180 minutes. After completion of feed to reducer B, the temperature of the reaction vessel is maintained at 60°C for 60 minutes. The reaction vessel is then cooled to 55°C. A solution of 1.79 grams of 70% TBHP and 0.58 grams of 30% SLS in 25 grams of water is added to the reaction vessel. After 5 minutes, a solution of 1.05 grams of erythorbic acid and 0.1 grams of SLS in 25 grams of water is added to the reaction vessel. The reaction vessel is held at 55°C. After 30 minutes, a solution of 1.79 grams of 70% TBHP and 0.3 grams of SLS in 25 grams of water is added to the reaction vessel. After 5 minutes, a solution of 1.0 grams of erythorbic acid solution and 0.17 grams of SLS in 25 grams of water is added to the reaction vessel. The reaction vessel was kept at 55°C for about 30 minutes. Then, the reaction vessel is cooled to room temperature and its contents are filtered through 100 µm of tissue. The pH of the resulting emulsion is adjusted to between 5 and 6 with ammonium hydroxide. The polymer emulsion has 29.74% by weight polymer solids, a viscosity of 21 cps and a particle size of 109 nm.
[0173] An emulsion polymer polymerized from the monomeric mixture comprising 45 wt% EA, 15 wt% n-BA, 45 wt% HEMA and crosslinked with APE (0.08 wt% based on in dry polymer weight) is prepared by a method similar to Example 2 except that 200 grams of EA and 75 grams of n-BA are used. The polymer emulsion has 29.43 wt% polymer solids, a viscosity of 26 cps and a particle size of 101 nm. Example 4 (comparative)
[0174] An emulsion polymer polymerized from the monomer mixture comprising 50% by weight of EA, 20% by weight of MMA, 30% by weight of HEMA and crosslinked with APE (0.35% by weight based on weight of the dry polymer) is prepared as follows.
[0175] A monomer premix is made by mixing 140 grams of water, 16.67 grams of SLS, 250 grams of EA, 75 grams of MMA, 1.75 grams of APE and 150 grams of HEMA. Initiator A is made by mixing 2.86 grams of 70% TB HP in 40 grams of water. Reducer A is prepared to dissolve 0.13 grams of erythorbic acid in 5 grams of water. Reducer B is prepared to dissolve 2.0 grams of erythorbic acid in 100 grams of water. A 3-liter reactor vessel is charged with 800 grams of water and 1.58 grams of SLS and then heated to 60°C under a blanket of nitrogen and its own agitation. Initiator A is then added to the reaction vessel and followed by the addition of reductant A. After about 1 minute, the monomer premix is metered into the reaction vessel over a period of 144 minutes. About 3 minutes after starting the measurement of the monomer premix, reducer B is delivered to the reaction vessel over a period of 180 minutes. After completion of the monomer premix feed, 25 grams of MMA is metered into the reaction vessel over a period of 6 minutes. After completion of feed to reducer B, the temperature of the reaction vessel is maintained at 60°C for 60 minutes. The reaction vessel is then cooled to 55°C. A solution of 1.79 grams of 70% TBHP and 0.58 grams of SLS in 25 grams of water is added to the reaction vessel. After 5 minutes, a solution of 1.05 grams of erythorbic acid and 0.1 grams of 30% SLS in 25 grams of water is added to the reaction vessel. The reaction vessel is held at 55°C. After 30 minutes, a solution of 1.79 grams of 70% TBHP and 0.3 grams of 30% SLS in 25 grams of water is added to the reaction vessel. After 5 minutes, a solution of 1.0 grams of erythorbic acid solution and 0.17 grams of SLS in 25 grams of water is added to the reaction vessel. The reaction vessel is kept at 55°C for about 30 minutes. Then, the reaction vessel is cooled to room temperature and filtered through 100 µm of tissue. The pH of the resulting emulsion is adjusted to between 5 and 6 with ammonium hydroxide. The polymer emulsion has 28.65% by weight polymer solids, viscosity 6 cps and a particle size of 94 nm. This polymer contains a relatively high level of a crosslinker (APE).Example 5 (comparative)
[0176] An emulsion polymer polymerized from the monomer mixture comprising 50% by weight of EA, 20% by weight of MM A, 30% by weight of HEMA and crosslinked with APE (0.53% by weight based on polymer dry weight) is prepared by a method similar to Example 4 except that 2.65 grams of APE is used. The polymer emulsion has 26.31% by weight polymer solids, a viscosity of 5 cps and a particle size of 94 nm. This polymer contains a relatively high level of crosslinker (APE). Example 6 (comparative)
[0177] An emulsion polymer polymerized from the monomeric mixture comprising 35% by weight of EA, 20% by weight of n-BA, 45% by weight of HEMA and no crosslinker is prepared by a method similar to Example 2 except that no APE is used. The polymer emulsion has 29.55 wt% polymer solids, a viscosity of 26 cps and a particle size of 93 nm. Example 7 (comparative)
[0178] An emulsion polymer polymerized from the monomer mixture comprising 70% by weight EA, 20% by weight n-BA, 10% by weight HEMA and crosslinked with APE (0.08% by weight based in dry polymer weight) is synthesized by a method similar to Example 2. The polymer emulsion has 29.73 wt% polymer solids, a viscosity of 26 cps and a particle size of 93 nm.
[0179] An emulsion polymer polymerized from the monomeric mixture comprising 40% by weight of EA, 15% by weight of n-BA, 10% by weight of HE A, 35% by weight of HEMA and crosslinked with APE (0 .06% by weight based on dry polymer weight) is prepared as follows.
[0180] A monomer premix is made by mixing 140 grams of water, 5 grams of SLS, 200 grams of EA, 75 grams of n-BA, 50 grams of 2-hydroxyethyl acrylate (HEA) and 175 grams of HEMA. Initiator A is made by mixing 2.86 grams of 70% TBHP in 40 grams of water. Reducer A is prepared to dissolve 0.13 grams of erythorbic acid in 5 grams of water. Reducer B is prepared to dissolve 2.0 grams of erythorbic acid in 100 grams of water. A 3 liter reactor vessel is loaded with 800 grams of water, 13.3 grams of 30% SLS and 25 grams of poly(vinyl alcohol) (having an average molecular weight of 13,000-23,000 Daltons and 87-89% hydrolyzed). The reactor vessel is heated to 60°C under a blanket of nitrogen and its own agitation. Initiator A is then added to the reaction vessel and followed by the addition of reductant A. After about 1 minute, the monomer premix is measured into the reaction vessel over a period of 150 minutes. About 3 minutes after starting the measurement of the monomer premix, reducer B is metered into the reaction vessel over a period of 180 minutes. About 60 minutes after starting the monomer premix measurement, 0.43 grams of 70% APE is added to a monomer premix. After completion of feed to reducer B, the temperature of the reaction vessel is maintained at 60°C for 60 minutes. The reaction vessel is then cooled to 55°C. A solution of 1.79 grams of 70% TBHP and 0.58 grams of SLS in 25 grams of water is added to the reaction vessel. After 5 minutes, a solution of 1.05 grams of erythorbic acid and 0.1 grams of SLS in 25 grams of water is added to the reaction vessel. The reaction vessel is held at 55°C. After 30 minutes, a solution of 1.79 grams of 70% TBHP and 0.3 grams of SLS in 25 grams of water is added to the reaction vessel. After 5 minutes, a solution of 1.0 grams of erythorbic acid solution and 0.17 grams of SLS in 25 grams of water is added to the reaction vessel. The reaction vessel is kept at 55°C for about 30 minutes. Then, the reaction vessel is cooled to room temperature and the contents are filtered through 100-μm of tissue. The pH of the resulting emulsion is adjusted to between 5 and 6 with ammonium hydroxide. The polymer emulsion has 30.44% polymer solids, a viscosity of 17 cps and a particle size of 99 nm. Example 9
[0181] An emulsion polymer polymerized from the monomeric mixture comprising 20% by weight of EA, 15% by weight of n-BA, 20% by weight of VA, 45% by weight of HEMA and crosslinked with APE (0, 06% by weight based on dry polymer weight) is synthesized in a manner similar to that of Example 8. The monomeric mixture contains 20 grams VA, 20 grams EA, 75 grams n-BA and 225 grams HEMA. The poly(vinyl alcohol) in the reactor is exchanged for one with an average molecular weight of about 9,000-1,000 Daltons and 80% hydrolyzed. The polymer emulsion has 30.1 wt% polymer solids, a viscosity of 14 cps and a particle size of 135 nm.
[0182] An emulsion polymer polymerized from the monomeric mixture comprising 20% by weight of EA, 15% by weight of n-BA, 20% by weight VA, 45% by weight of HEMA and crosslinked with APE (0, 06% by weight based on dry polymer weight) is synthesized in a manner similar to that of Example 9 except APE is added to a monomer premix at about 90 minutes after the start of the monomer premix measurement. The resulting polymer emulsion has 29.94% by weight polymer solids and a viscosity of 16 cps, a particle size of 130 nm. Examples 11 to 17
[0183] The swelling of the individual polymer particles in the emulsions of Examples 1 to 7 by the anionic surfactant, sodium dodecyl sulfate (SDS), is determined by preparing the tested samples containing 0.01% by weight of the polymer (total polymer solids ), 20 mM sodium chloride in surfactant concentrations ranging from 0 to 6 mM in water. In the case where there is swelling, the particle size, as measured by dynamic light scattering (DLS), remains constant up to a critical surfactant concentration, but monotonically increased above this concentration by a plateau value at the highest surfactant concentrations. Referring to Figure 1 a swelling or expansion ratio is obtained by the polymer of Example 12 by dividing the plateau value (250 nm) by the particle size below the critical concentration threshold (93.5 nm) (polymer expansion ratio : 250 nm/93.5 nm = 2.7).
[0184] Samples containing 3% by weight polymer solids and 5% by weight SLS in water are prepared using each of the polymers prepared in examples 1 to 7. The yield strength, viscosity and shear thinning index of these samples were determined by fixed or oscillatory shear measurements in a tension-controlled rheometer (TA Instruments AR1000N rheometer, New Castle, DE) with cone and plate geometry (40 mm cone with a 2 degree cone angle and 56 μm gap ) at 25°C. Oscillatory measurements are performed at a fixed frequency ranging from 1 Hz to 0.001 Hz. The elastic and viscous moduli (G' and G” respectively) are obtained as a function of increasing the voltage amplitude. In cases where the swollen polymer particles create a crushed network, G' is greater than G" at low voltage amplitudes but decreases at higher amplitudes crossing G" because of network disruption. The stress corresponding to the passage of G' and G” is noted as a yield point. Figure 2 illustrates the crossing point G' (solid fill) and G” (no fill) (flow limit value) by the flow limit fluid of example 13. A plot of viscosity versus shear rate is obtained from of the fixed shear measurements. Viscosity at a shear rate of 3s-1 is noted. The shear thinning index is obtained from an energy law fit (r| = Ky11'1) in the range of shear rate 0.1 to Is'1 where r| is viscosity, y is shear rate, n is shear thinning index, and K is a constant. The optical clarity (expressed as percentage transmission or % T) of the samples is measured using a Brinkmann PC 910 Colorimeter with a 420 nm filter. The results of these measurements are shown in Table 1, along with the polymer expansion ratio.

[0185] It is clear that the compositions of examples 11 to 13 (prepared with cross-linked amphiphilic polymers having expansion ratios greater than 2.5) have a high yield limit (greater than 0.5 Pa), excellent shear thinning and good optical clarity. The comparative formulations of examples 14 and 15 are formulated with polymers having a relatively high level of crosslinker and these are not able to adequately swell in the surfactant medium. These compositions do not exhibit a yield point or shear thinning and have extremely low viscosity and optical clarity.
[0186] Comparative example 16 is formulated with a polymer that does not contain crosslinking. In this case there is high optical clarity but no yield threshold or shear thinning attributes. Comparative Example 17 is formulated with a polymer having the right level of crosslinker but such a low level of hydrophilic monomer. This polymer also does not exhibit adequate swelling in the surfactant medium and has no yield strength or shear thinning attributes bonded with poor optical clarity and low viscosities.
[0187] The ability of a polymer system to resuspend esthetically pleasing and/or gaseous active and oily particulate materials is important from the point of view of effectiveness and attraction of the product. Long term suspension of 1.2 mm sized beads with a specific gravity of approximately 1.4 (Unisphere™ REL 552 from Induchem AG, Switzerland) is examined in Examples 12 to 17. A six drachma vial (approximately 70 mm high x 25 mm in diameter) is filled to the 50 mm point with each formulation. The pearls are weighed into each sample (0.6% by weight based on the weight of the total formulation) and gently agitated with a wooden spatula until it is evenly dispersed throughout each sample. The vials are placed on a laboratory bench at room temperature to age for a period of 16 weeks. The pearl suspension property of each sample is monitored on a daily basis. Suspension results are visually observed over the 16 week test period. The beads remain resuspended (does not lift or sediment) in the formulations of the invention. The formulations of comparative examples 14 to 17 failed on those beads that were sedimented to the bottom of the vials in 2 weeks. Example 18
[0188] This example illustrates the effect of alternative anionic surfactants containing different salts on the rheology and optical clarity of yield-limit fluids. Aqueous compositions containing 3 wt% (total polymer solids) of the polymer of Example 2 and 5 wt% of the surfactant (active material) listed in the table below are prepared and the yield point, viscosity, shear thinning index and optical clarity are measured as in Examples 11 to 17. The results are shown in Table 2.

[0189] It is clear that yield-limit fluids exhibit high yield limits, excellent shear thinning, and acceptable optical clarity are obtained with various anionic surfactants.
[0190] This example illustrates a combination of anionic and amphoteric surfactant ethoxylated surfactant in the rheology and optical clarity of flow-limit fluids containing the polymers of the invention. Aqueous compositions containing 3% by weight polymer solids and 14% by weight of a surfactant combination (12% by weight anionic surfactant (active), Sulfochem™ ES-2 and 2% by weight amphoteric surfactant (active) , Chembetain IM CAD, are prepared by mixing the polymer and the combination of surfactant.The yield point, viscosity, shear thinning index and optical clarity are measured as in Examples 11 to 17. The results are shown in Table 3.

[0191] Flow stress fluids exhibiting high flow limits, excellent shear thinning and acceptable optical clarity are obtained by using the polymers of the invention in combination with the mixture of anionic and amphoteric surfactant.
[0192] Figure 3 is a plot showing oscillatory rheology measurements in the flow-limit fluid formulated above the polymer of example 9. The vertical line taken through the crossing point of G' (no fill) and G” (solid fill ) in the plot indicates the boundary between a crushed network of microgels at low tensions and fluid above a tension threshold (flow). The plot of G” versus stress shows a maximum that is characteristic of a soft vitreous material (SGM).Example 20
[0193] Long term suspension of 1.2 mm sized beads with a specific gravity of approximately 1.4 (Unisphere™ REL 552 from Induchem AG, Switzerland) is examined by the flow limit fluids exemplified in Table 4 (which include the polymers of examples 8, 9 and 10) according to the methods of examples 11 to 17. The beads remain resuspended in the flow-limiting fluid formulations shown in this example for 4 months at room temperature (approximately 23°C). Example 21 (comparative)
[0194] This example illustrates the behavior of non-ionic hydrophobically modified associative thickeners in combination with an anionic surfactant in water.
[0195] A hydrophobic ethoxylated urethane polymer (HEUR) (AculynK 44 from Dow Chemical) and a hydrophobically modified hydroxyethylcellulose polymer (HMHEC) (NatrosoU Plus 330 PA from Ashland Chemical) are combined with SDS surfactant to prepare compositions containing 3% by weight of polymer (solids of the total polymer) and 5% by weight of the surfactant (active material) in water. The rheology of the compositions is determined using the procedure described in Example 1. In both cases, it is observed that the samples do not exhibit a yield point value. Example 22
[0196] This example compares the effect of pH on a yield point of fluid compositions containing a mixture of surfactant and polymer of the invention versus compositions containing a pH responsive polymer formulated in the same surfactant system. The comparative polymer is crosspolymer-4 acrylates (INCI) (marked as Carbopol® Aqua SF-2, Lubrizol Advanced Materials, Inc.), an anionic acrylic emulsion polymer, crosslinked (meth)acrylic acid, or one or more of its Ct to C4 alkyl ester.
[0197] Miscellaneous examples containing 2.5 wt% (total polymer solids) of the polymer of example 10 and 14 wt% of a surfactant combination (12 wt% (active material) anionic ethoxylated surfactant, Sulfochem1 M ES- 2 and 2 wt% (active material) amphoteric surfactant Chemcetaine IM CAD) and 10 mM sodium chloride in water are prepared. Identical samples are formulated with the comparative crosspolymer-4 acrylates. The pH of these samples is adjusted to values ranging from 3 to 12 using dilute aqueous solutions of sodium hydroxide (18% by weight/by weight) or citric acid (50% by weight/by weight). The yield point at a frequency of 1Hz is measured using the methods of examples 11 to 17. The results for the compositions formulated with the polymer of example 10 are shown in Table 4 and the results for the compositions formulated with the responsive comparative polymer. pH are shown in Table 5.

[0198] The yield limit values listed in Table 4 have a mean value of 2.56 Pa and standard deviation of 0.19 Pa whereas the yield limit values listed in Table 5 have a mean value of 1.58 Pa and a standard deviation of 2.07 Pa. It is clear that the polymer of the invention provides significantly more uniform yield point over a wide pH range compared to the control polymer.

[0199] The long term suspension of 1.4 mm sized beads with a specific gravity of approximately 1.3 (Unisphere™ REL 551 from Induchem AG, Switzerland) is examined according to the methods of examples 11 to 17. It is noted that the beads remain resuspended in all samples exemplified in Table 4 for 4 months at room temperature (approximately 23°C) but the beads failed to remain in suspension in the last five samples listed in Table 5.Example 23
[0200] This example illustrates the effect of the compositions of the invention on the alignment of mica and pearlescence.
[0201] Samples containing 3 wt% polymer and 5 wt% sodium dodecyl sulfate (SDS) in water are prepared using the polymers of example 1 and example 2. Iron oxide coated mica platelets (Colorona Copper Cosmetic Pigment, product # 017378 from EM Industries, Inc.) are added to those samples at a concentration of 0.7 mg per ml. A drop of sample containing mica is placed on a microscope slide, coated with a covered slide and allowed to equilibrate for 5 minutes. The slide is then placed in the stage of a microscope (Olympus BX51TRF) equipped with a polarizer, analyzer and a color camera. After focusing on the brightfield, the polarizer and analyzer are crossed and an image is captured with the color camera. The image is then broken down into its three component color channels: red, green, and blue. Using image analysis software (Image J software, National Institutes of Health), the total number of platelets darker than ground in the blue channel and the total number of platelets brighter than ground in the red channel are counted. Platelets not aligned under shear appear luminous in the red channel when summarized with crossed polarizers. The fraction of unaligned platelets under shear is calculated as the total number of platelets counted in the red channel divided by the total number of platelets counted in the blue channel. The fraction of aligned platelets is calculated as 1 minus the fraction of unaligned platelets. Samples containing polymers from Example 1 and Example 2 show 88.8% and 87.4% alignment of the mica platelets with standard deviations of 5.2 and 5.3, respectively. Alignment greater than 80% provides the extremely pleasing visual appearance of pearlescent.Example 24
[0202] An emulsion polymer is polymerized from a monomeric mixture comprising 45% by weight HEMA, 35% by weight EA, 15% by weight n-BA, 5% by weight WEM and cross-linked with APE (0.08 % by weight based on dry polymer weight) is prepared as follows.
[0203] A monomer premix is made by mixing 140 grams of water, 3.75 grams of 40% aqueous alpha olefin sulfonate (AOS) solution, 175 grams of EA, 71 grams of n-BA, 33.33 grams of BEM and 225 grams of HEMA. Initiator A was made by mixing 2.86 grams of 70% TBHP in 40 grams of water. Reducer A is prepared to dissolve 0.13 grams of erythorbic acid in 5 grams of water. Reducer B is prepared to dissolve 2.0 grams of erythorbic acid in 100 grams of water. A 3-liter reactor vessel is charged with 800 grams of water, 10 grams of 40% AOS and 25 grams of CelvoU 502 PVA and then heated to 65°C under a blanket of nitrogen and its own agitation. Initiator A is then added to the reaction vessel and followed by the addition of reductant A. After about 1 minute, the monomer premix is measured in the reaction vessel over a period of 150 minutes; simultaneously, reducer B is measured in the reaction vessel over a period of 180 minutes. After the addition of the monomer premix, a solution of 0.40 grams of 70% APE and 3.6 grams of n-BA is added to a monomer premixer. Upon completion of the monomer premix feed, 33 grams of water is added to flow the residual monomers from the premixer. After completion of feed to reducer B, the temperature of the reaction vessel is maintained at 65°C for 65 minutes. The reaction vessel is then cooled to 60°C. A solution of 1.79 grams of 70% TBHP and 0.13 grams of 40% AOS in 25 grams of water is added to the reaction vessel. After 5 minutes, a solution of 1.05 grams of erythorbic acid in 25 grams of water is added to the reaction vessel. After 30 minutes, a solution of 1.79 grams of 70% TBHP and 0.13 grams of 40% AOS in 25 grams of water is added to the reaction vessel. After 5 minutes, a solution of 1.05 grams of erythorbic acid in 25 grams of water is added to the reaction vessel. The reaction vessel is kept at 60°C for about 30 minutes. Then, the contents of the reaction vessel are cooled to room temperature and filtered through 100 µm of tissue. The pH of the resulting emulsion is adjusted to 3.5-4.5 with 28% ammonium hydroxide.
[0204] An emulsion polymer polymerized from the monomeric mixture comprising 45% HEMA 35% by weight EA, 15% by weight n-BA, 5% by weight MPEG 350 and crosslinked with APE (0.08 % based on dry polymer weight) is prepared as follows.
[0205] A monomer premix is made by mixing 140 grams of water, 5 grams of 30% aqueous solution of sodium lauryl sulfate (SLS), 175 grams of EA, 71 grams of n-BA, 25 grams of Bisomer MPEG 350 MA and 225 grams of HEMA. Initiator A is made by mixing 2.86 grams of 70% TBHP in 40 grams of water. Reducer A is prepared to dissolve 0.13 grams of erythorbic acid in 5 grams of water. Reducer B is prepared to dissolve 2.0 grams of erythorbic acid in 100 grams of water. A 3-liter reactor vessel is charged with 800 grams of water, 13.33 grams of 30% SLS and 25 grams of CelvolK 502 PVA and the contents are heated to 65°C under a blanket of nitrogen and self-stirring. Initiator A is added to the reaction vessel and followed by the addition of reducer A. After about 1 minute, the monomer premix is measured in the reaction vessel over a period of 150 minutes; simultaneously, reducer B is measured in the reaction vessel over a period of 180 minutes. After the addition of the monomer premix, a solution of 0.40 grams of 70% APE and 3.6 grams of n-BA is added to a monomer premix. Upon completion of the monomer premix feed, 33 grams of water is added to flow the residual monomers into the premixer. After completion of feed to reducer B, the temperature of the reaction vessel is maintained at 65°C for 65 minutes. The reaction vessel is then cooled to 60°C. A solution of 1.79 grams of 70% TBHP and 0.17 grams of 30% SLS in 25 grams of water is added to the reaction vessel. After 5 minutes, a solution of 1.05 grams of erythorbic acid in 25 grams of water is added to the reaction vessel. After 30 minutes, a solution of 1.79 grams of 70% TBHP and 0.17 grams of 30% SLS in 25 grams of water is added to the reaction vessel. After 5 minutes, a solution of 1.05 grams of erythorbic acid in 25 grams of water is added to the reaction vessel. The reaction vessel is kept at 60°C for about 30 minutes. Then, the reaction vessel is cooled to room temperature and filtered through 100 µm of tissue. The pH of the resulting emulsion is adjusted to 3.5-4.5 with 28% ammonium hydroxide. The resulting polymer latex has a solids level of 30%, a viscosity of 16 cps and a particle size of 125 nm.
[0206] Samples containing 2.5% (total polymer solids) of the polymer of example 33 and 17% by weight of a surfactant combination (14% by weight (active material) Sulfochem™ ES-2 anionic surfactant and 3% by weight (active material) amphoteric surfactant Chemetaine IM CAD) and 0.1% by weight of sodium chloride in water are prepared. The pH of these samples is adjusted to values ranging from 3 to 12 using dilute aqueous solutions of sodium hydroxide (18% by weight/by weight) or citric acid (50% by weight/by weight). The yield point and optical clarity for each sample is measured and recorded in Table 12. The yield point at a frequency of 1Hz is measured on a voltage controlled rheometer (TA instruments AR2000EX rheometer, New Castle, DE) with cone geometry and plate (60 mm cone with a 2 degree cone angle and 56 µm slit) at 25°C using the method described in Examples 15 to 21. The optical clarity (expressed as percentage of transmission or % of T) of each sample is measured using a Brinkmann PC 910 colorimeter with a 420 nm filter. The results are shown in Table 6.

[0207] The yield point values have a mean value of 6.3 with a standard deviation of 0.7. The mean standard deviation ratio is 0.11 over the pH range of 3 to 12. The optical clarity values have a mean value of 76.9 and a standard deviation of 2.1. The mean standard deviation ratio is 0.03 in the pH range of 3 to 12.Example 27
[0208] Samples containing 2.5% (total polymer solids) of the polymer of example 34 are prepared and evaluated for the yield point and optical clarity properties as described in Example 35. The results are given in Table 7.

[0209] The yield point values have a mean value of 8.8 with a standard deviation of 0.8. The mean standard deviation ratio is 0.09 over the pH range of 3 to 12. The optical clarity values have a mean value of 37.4 and a standard deviation of 2.0. The mean standard deviation ratio is 0.05 over the pH range of 3 to 12.Examples 28 to 45
[0210] The emulsion polymers of the invention are prepared from the monomer components and amounts (% by weight based on total monomer weight) shown in Table 14 according to the procedures and conditions of example 24. A crosslinking monomer (APE) is used at 0.1% by weight (based on total dry polymer weight) in all examples.

Examples 46 to 55
[0211] The emulsion polymers of the invention are prepared from the monomer components and amounts (% by weight based on total monomer weight) shown in Table 9 according to the procedures and conditions of example 24. A crosslinking monomer (APE) is used at 0.9% by weight (based on total dry polymer weight) in all examples.

权利要求:
Claims (24)
[0001]
1. Composition of the flow-limit fluid, characterized in that it comprises water, at least one cross-linked nonionic amphiphilic polymer and at least one anionic surfactant, wherein the concentration of said polymer varies from 0.5 to 5% by weight and the concentration of said surfactant ranges from 1 to 30% by weight (active weight basis), based on the total weight of the composition, wherein said polymer is polymerized from a monomeric composition comprising at least 30% by weight of at least one hydrophilic monomer and at least 5% by weight of at least one hydrophobic monomer, wherein said hydrophilic monomer is selected from (C 1 -C 5 )alkyl hydroxy (meth)acrylate monomers or mixtures thereof; wherein said hydrophobic monomer is selected from (meth)acrylic acid esters with alcohols containing from 1 to 30 carbon atoms, vinyl esters of aliphatic carboxylic acids containing from 1 to 22 carbon atoms, vinyl esters of alcohols containing from 1 to 22 carbon atoms, vinyl aromatic monomers, vinyl halides, vinylidene halides, associative monomers, semi-hydrophobic monomers or mixtures thereof, wherein said monomeric composition comprises a crosslinked monomer which is present to be incorporated in said polymer, of 0 0.01 to 0.3% by weight, based on the dry weight of said polymer, wherein said associative monomer comprises (i) an ethylenically unsaturated end group portion, (ii) polyoxyalkylene midsection portion, and (iii) portion of hydrophobic end-group containing 8 to 30 carbon atoms, and wherein said semi-hydrophobic monomer comprises (i) an ethylenically unsaturated end-group portion, (ii) polyoxyalkylene mid-section portion, and (i) ii) an end group moiety selected from hydrogen or an alkyl group containing from 1 to 4 carbon atoms.
[0002]
2. Composition according to claim 1, characterized in that said (C1-C5) hydroxy alkyl (meth)acrylate is selected from at least one compound represented by the formula:
[0003]
3. Composition according to claim 1 or 2, characterized in that said ester of (meth)acrylic acid with alcohols containing from 1 to 30 carbons is selected from at least one compound represented by the formula:
[0004]
4. Composition according to any one of the preceding claims, characterized in that said vinyl ester of aliphatic carboxylic acids containing from 1 to 22 carbon atoms is selected from at least one compound represented by the formula:
[0005]
5. Composition according to any one of the preceding claims, characterized in that said vinyl ether of alcohols containing from 1 to 22 carbon atoms is selected from at least one compound represented by the formula:
[0006]
6. Composition according to any one of the preceding claims, characterized in that said associative monomer is represented by formulas VII and/or VIIA:
[0007]
7. Composition according to any of the preceding claims, characterized in that said semi-hydrophobic monomer is selected from at least one monomer represented by formulas VIII and IX:
[0008]
8. Composition according to any one of the preceding claims, characterized in that the at least one crosslinking monomer is selected from polyallyl ethers of trimethylolpropane, polyallyl ethers of pentaerythritol, polyallyl ethers of sucrose or mixtures thereof, or in which the hair at least one crosslinking monomer is selected from pentaerythritol diallyl ether, pentaerythritol triallyl ether, pentaerythritol tetralyl ether, or mixtures thereof.
[0009]
9. Composition according to any one of the preceding claims, characterized in that said flow limit of said flow limit fluid is at least 0.1 Pa, or at least 0.5 Pa, or at least 1 Pan.
[0010]
10. Composition according to any one of the preceding claims, characterized in that said polymer is an emulsion polymer.
[0011]
11. Composition according to claim 10, characterized in that said flow limit is at least 0.1 Pa, wherein said flow limit is measured at a fixed frequency selected from a frequency range of 1 Hz to 0.001 Hz.
[0012]
12. Composition according to claim 10 or 11, characterized in that said emulsion polymer is polymerized from a monomeric mixture comprising at least 30% by weight of at least one C1-hydroxyalkyl (meth)acrylate C4, 15 to 70% by weight of at least one C1-C12 alkyl (meth)acrylate, 5 to 40% by weight of at least one vinyl ester of a C1-C10 carboxylic acid (based on weight of total monomers ) and 0.01 to 0.3% by weight of at least one crosslinker (based on the dry weight of the polymer), or wherein said emulsion polymer is polymerized from a monomeric mixture comprising at least 30% by weight. weight of at least one C1-C4 alkyl (meth)acrylate, 15 to 70% by weight of at least one C1-C12 alkyl (meth)acrylate, 1 to 10% by weight of at least one monomer selected from a monomer associative, a semi-hydrophobic monomer or mixtures thereof (based on the weight of the total monomers) and 0.01 to 0.3 % by weight of at least one ret iculant (based on dry weight of polymer).
[0013]
13. Composition according to claim 12, characterized in that said emulsion polymer is polymerized from a monomeric mixture comprising hydroxyethyl methacrylate and a monomer selected from methyl methacrylate, ethyl acrylate, butyl acrylate, vinyl acetate, vinyl neodecanoate, vinyl decanoate, an associative monomer, a semi-hydrophobic monomer or mixtures thereof, or wherein said emulsion polymer is polymerized from a monomeric mixture comprising hydroxyethyl methacrylate, ethyl acrylate , butyl acrylate and a monomer selected from an associative and/or semi-hydrophobic monomer, or wherein said emulsion polymer is polymerized from a monomeric mixture comprising hydroxyethyl methacrylate, ethyl acrylate, butyl acrylate and acetate. vinyl, or wherein said emulsion polymer is polymerized from a monomeric mixture comprising hydroxyethyl methacrylate, acrylate ethyl, butyl acrylate and a monomer selected from an associative and/or semi-hydrophobic monomer.
[0014]
14. Composition according to claim 13, characterized in that said associative monomer comprises (i) a portion of end group ethylenically unsaturated; (ii) a polyoxyalkylene middle section moiety and (iii) a hydrophobic endgroup moiety containing from 8 to 30 carbon atoms.
[0015]
15. Composition according to claim 14, characterized in that said associative monomer is represented by formulas VII and/or VIIA:
[0016]
16. Composition according to any one of claims 13 to 15, characterized in that said semi-hydrophobic monomer comprises (i) a portion of an ethylenically unsaturated end group; (ii) a middle section portion of polyoxyalkylene and (iii) an end group portion selected from hydrogen or an alkyl group containing from 1 to 4 carbon atoms.
[0017]
17. Composition according to claim 16, characterized in that said semi-hydrophobic monomer is selected from at least one monomer represented by formulas VIII and IX:
[0018]
18. Composition according to any one of claims 10 to 17, characterized in that said crosslinker is selected from a monomer having an average of 3 crosslinkable unsaturated functional groups.
[0019]
19. Composition according to any one of claims 10 to 18, characterized in that said monomeric mixture is polymerized in the presence of a protective colloid.
[0020]
20. Composition according to any one of claims 10 to 19, characterized in that said emulsion polymer is polymerized from a monomeric mixture comprising 40 to 45 % by weight of hydroxyethyl acrylate, 30 to 50 % by weight of ethyl acrylate, 10 to 20% by weight of butyl acrylate and 1 to 5% by weight of at least one associative and/or semi-hydrophobic monomer (based on the weight of the total monomers) and at least a crosslinker.
[0021]
21. Flow-limit fluid composition according to any one of claims 10 to 20, characterized in that it comprises: a) water; b) 1 to 5% by weight of at least one prepared non-ionic amphiphilic emulsion polymer from the monomeric mixture comprising: i) 40 to 50% by weight of at least one (C 1 -C 5 )alkyl hydroxy(meth)acrylate monomer (based on the weight of the total monomer); ii) 15 to 70% by weight of at least two different monomers selected from a (C1-C5) alkyl (meth)acrylate monomer (based on the weight of the total monomer);iii) 0.5 to 5% by weight of an associative monomer and/ or semi-hydrophobic, eiv) 0.01 to 0.3 wt% of at least one crosslinker (based on dry weight of polymer), and c) 6 to 20 wt% of a surfactant blend containing an anionic surfactant and an amphoteric surfactant.
[0022]
22. Flow limit fluid composition according to any one of claims 10 to 21, characterized in that it further comprises an insoluble material, a particulate material or combinations thereof.
[0023]
23. Drilling fluid for use in drilling underground formations, characterized in that it comprises the flow boundary fluid composition as defined in any one of claims 1 to 22.
[0024]
24. Hydraulic fracturing fluid for use in fracturing underground formations, characterized in that it comprises the flow boundary fluid composition as defined in any one of claims 1 to 22.

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法律状态:
2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-08-06| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-12-08| B07A| Technical examination (opinion): publication of technical examination (opinion) [chapter 7.1 patent gazette]|

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2021-03-30| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-06-08| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 13/09/2012, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US201161533887P| true| 2011-09-13|2011-09-13|

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US61/533887|2011-09-13|

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PCT/US2012/055105|WO2013040174A1|2011-09-13|2012-09-13|Surfactant responsive emulsion polymerized micro-gels|

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