non-ionic amphiphilic rheology modifier polymer compositions and deformation stress fluid, and hydra

专利摘要:
COMPOSITIONS OF NON-IONIC AMPHYLIC POLYMER AND DEFORMATION TENSION FLUID, AND, HYDRAULIC DRILLING AND FRACTURE FLUIDS A stable, aqueous composition containing a non-ionic, amphiphilic crosslinked polymer capable of forming a deformation stress fluid in the presence of a surfactant is disclosed. The strain strain fluid is capable of suspending insoluble materials in the form of particulates and / or drops that require suspension or stabilization.
公开号:BR112016013854B1
申请号:R112016013854-6
申请日:2014-12-17
公开日:2021-01-26
发明作者:Shui-Jen Raymond Hsu；Krishnan Chari；Sinan Li
申请人:Lubrizol Advanced Materials, Inc.；
IPC主号:

专利说明:

FIELD OF TECHNOLOGY DESCRIBED
[001] The technology described refers to rheology modifiers and, more specifically, to a strain strain fluid comprising a responsive tensile microgel. In addition, the technology described also relates to the formation of a rheologically responsive and stable phase microgel composition that can be used over a wide pH range to suspend particulate and insoluble materials. FUNDAMENTALS OF THE DESCRIBED TECHNOLOGY
[002] We are surrounded in everyday life by stress strain fluids. Simply stated, strain strain fluids remain stationary until sufficient stress is placed on the fluid at the point where the fluid will flow. It can be thought of as the initial resistance to the fluid under tension and is also referred to as the yield point. Strain strain is a measurable amount similar to, but not dependent on, viscosity. Although a certain rheology modifier can thicken or increase the viscosity of a composition in which it is included, it does not necessarily have the desired strain strain properties.
[003] A desirable strain strain 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 suspended, if the strain strain (yield value) of the medium is sufficient to overcome the effect of gravity or fluctuation on these particles. Insoluble liquid droplets can be prevented from rising and coalescence and gas bubbles can be suspended and evenly distributed in a liquid medium using the yield value as a formulation tool. An example of a flow stress fluid is a microgel rheology modifier that is generally used to adjust or modify the rheological properties of aqueous compositions. Such properties include, without limitation, viscosity, flow rate, stability to change in viscosity over time, and the ability to suspend particles for indefinite periods of time. They are useful in a number of industrial and consumer 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, they are useful as underground treatment fluids in the oil and gas industry as a component in drilling and fracturing fluids. Typically, they comprise chemically cross-linked polymers having a pH responsive functionality that is sensitive to acid or base. The 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 a base. Acid-sensitive thickeners are activated by contact with an acid agent, while base-sensitive thickeners are activated by contact with an alkaline agent. After neutralization, the polymers swell significantly to form a randomly closed-packaged ingrown network (CPR) of swollen reticulated microgel particles giving a desired rheological profile, that is, strain strain, modulus of elasticity and viscosity, as well as optical clarity for the formulation.
[004] These types of rheology modifying agents are well known in the art. For example, US Patent Nos. 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. US Patent No. 6,635,702 describes alkaline-swellable crosslinked acrylate copolymers comprising one or more carboxylic acid monomers and one or more non-acidic vinyl monomers. US Patent No. 7,378,479 discloses an acid-swellable crosslinked polymer containing at least one basic amino substituent that is cationic at a low pH, at least one hydrophobically modified polyoxyalkylene substituent derived from an associative vinyl monomer and at least one substituent polyoxyalkylene derivative of a semi-hydrophobic vinyl surfactant monomer. A key feature of these pH-responsive microgels is the large increase in diameter (or size) of individual cross-linked polymer particles upon neutralization. The high swelling efficiency allows formulators to achieve the desired strain and viscosity stress using relatively small amounts of polymer, resulting in low cost of use. Dalmont, Pinprayoon and Saunders (Langmuir vol. 24, page 2834, 2008) show that the individual particles of a microgel dispersion of a copolymer of ethyl acrylate and methacrylic acid cross-linked with butanediol diacrylate increase in diameter by at least one factor of 3 under pH activation or neutralization. The level of swelling causes an increase in the volume fraction of at least 27 (33). An ingrown network is achieved by neutralization (or activation) with a relatively low concentration of polymer (less than 3% by weight).
[005] Although pH-responsive microgels provide fluids with strain strain with high efficiency that is desired by the formulator, they suffer from a major drawback. Rheological properties are not uniform over a wide pH range and show sudden changes as a function of pH. To overcome these difficulties, several nonionic thickeners have been proposed. US 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 is relatively independent of pH, but the polymers are not cross-linked and the purely associative interactions do not create a strain strain.
[006] In addition to pH-responsive microgels, temperature-responsive microgels are known in the art. Senff and Richtering (Journal of Chemical Physics, vol. 111, page 1705, 1999) describe the modification of the chemically cross-linked non-ionic poly (N-isopropylacrylamide) microgel particles (PNIPAM) as a function of temperature. The particles swell by a factor of almost 2.5 in diameter (15 times in terms of fraction by volume) 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 that allows you to switch from a free flow suspension to a strain strain fluid under ambient conditions.
[007] Wu and Zhou (Journal of Polymer Science: Part B: Polymer Physics, vol.34, page 1597, 1996) describe the effect of the surfactant on swelling of chemically cross-linked PNIPAM homopolymer microgel particles in water. The use of surfactants to activate microgels is attractive because many formulations contain surfactants as co-ingredients. However, the swelling efficiency reported by Wu and Zhou is extremely low. The anionic surfactant of sodium dodecyl (lauryl) sulfate increases the size of cross-linked PNIPAM particles only by a factor of 1.4 at room temperature. In addition, Wu and Zhou do not teach how to create a pseudoplasticity strain strain fluid with optical clarity.
[008] Hidi, Napper and Sangster (Macromolecules, vol.28, page 6042, 1995) describe the effect of the surfactant on the swelling of microgels of poly (vinyl acetate) homopolymers in water. For non-crosslinked microgels that report an increase in diameter by a factor of 3 to 4, which corresponds to a change of 30 to 60 times 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, they observe an increase in diameter only by a factor of 1.4. Again, Hidi, Napper and Sangster do not teach how to create a pseudoplasticity strain strain fluid with high optical clarity.
[009] In addition to providing the necessary rheology profiles, the suspension of solid and / or insoluble materials in a stable phase system is equally important for a rheology modifier. In the extraction of oil and gas, underground treatment fluids (for example, drilling and fracture fluids) are typically modified with gelling agents to provide desired rheological properties. Gelling agents include any substance that is capable of increasing the viscosity of a fluid, for example, through the formation of a microgel. These agents must not only have desirable rheological properties in terms of fluid flow and pumping capacity, but they must also have the ability to suspend solids, under dynamic and static conditions. During active drilling operations, the drilling fluid must have sufficient structure to transport the forming chips to the surface and also have the necessary pseudoplasticity properties to be pumpable. During periods of non-drilling, drilling fluid can remain stationary in the hole for hours or even days at a time. During this period, settling of suspended solids can be problematic if the fluid does not have enough structure to support large and small particles.
[0010] The fracture is used to boost the production of hydrocarbons, such as oil or natural gas from underground formations. In this process, a fracture fluid containing a gelling agent is injected through a well hole and forced against the formation of layers by high pressure sufficient to cause the layers to crack and fracture thereby releasing the hydrocarbon trapped in the formation. The fracture fluid also carries a structurant to the fracture site. Structuring particles remain in the fracture, thus "supporting" the open fracture when the well is in production. The structuring material is typically selected from sand, sintered bauxite, glass beads, polystyrene beads and the like. Considering that sufficient rheological properties are important in the treatment fluids used in the fracture, satisfactory suspension capacity is necessary to transport the structuring materials to the fracture site within the formation.
[0011] Conditions are harsh within an underground formation and a gelling agent must be stable to temperature variations, brackish water environments, wide pH ranges and changes in shear forces.
[0012] Several problems have been encountered with underground treatment fluids in applications in the oil field, including the lack of thermal stability of the gel after exposure to different temperatures and pH, as well as high shear conditions. This can result in changes in the rheological properties of the gel that can ultimately affect the fluid's ability to suspend drill cuttings and or structuring materials. If particulate materials are prematurely lost from the treatment fluid, it can have a detrimental effect on drilling and formation development. In addition, the instability of the gel can result in greater loss of fluid for the formation thus decreasing the efficiency of the operation.
[0013] Personal care compositions that can suspend particles and / or other water-insoluble materials are very desirable. These materials confer or contribute to a variety of benefits for the user, including, but not limited to exfoliation, visual aesthetics, and / or the encapsulation and release of beneficial agents as a result of use. The suspension of particulate and insoluble materials as active and aesthetic agents in personal care compositions has become increasingly popular with formulators. Typically, the particles are suspended in personal care compositions using structuring systems, such as acrylate polymers, structuring gums (e.g., xanthan gum), starch, agar, hydroxy alkyl cellulose, etc. However, adding pearls 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 that of the continuous phase of the composition to which they are added. This incompatibility of the density can cause the separation of the particles from the continuous phase and a lack of total stability of the 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 ("creaming"). In another aspect, when the aggregate particles have a higher density than that of the continuous phase, the particles tend to settle at the bottom of that phase ("decantation"). When large particles are desired to be suspended (e.g., polyethylene particles, guar granules, etc.), the level of polymer used is typically increased to provide a greater structure for suspended granules. A consequence of thickening a liquid to provide the suspended granule structure causes a significant increase in the viscosity of the liquid and a corresponding decrease in flow capacity, a property that is not always desirable. Highly viscous products are typically difficult to apply and rinse, especially if the pseudoplasticity profile of the viscosity-forming agent is deficient. High viscosities can also adversely affect the packaging, distribution, dissolution, foaming and sensory properties of the product. In addition, conventionally structured liquids are often opaque or cloudy, thus obscuring the consumer's suspended bills, which adversely affects the product's aesthetic form.
[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 the effectiveness of cationic surfactant. Nonionic thickeners, such as hydroxyethylcellulose (HEC) and hydroxypropylmethylcellulose (HPMC) can provide viscosity in cationic systems, however, very few suspension properties are transmitted to the fluid. Cationic thickeners, such as polyquaternium-10 (cationically modified HEC) and cationic guar provide thickening in cationic systems, but not suspension. Some acrylic polymers are effective in cationic thickening systems, but which can be limited by pH, require high concentrations, have high cost in use, and often have narrow compatibility limits with cationic materials.
[0015] Anionic surfactants are often used as detersive agents in cleaners 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 sulphates and sulphonates are effective detersive agents, they are serious eye irritants and capable of causing mild to moderate, skin irritation for some sensitized people. Therefore, it has become increasingly important for consumers that aqueous cleaning compositions are gentle in that they do not irritate the eyes and skin when in use. Manufacturers are striving to offer mild cleaning products that also incorporate insoluble benefit and / or aesthetic agents that require stable suspension. It is known that the irritation caused by anionic sulphates and sulphonates can be reduced using their ethoxylated forms. Although ethoxylated surfactants can mitigate eye and skin irritations in compositions in which they are included, a major problem in using these surfactants is that it is difficult to obtain desirable strain stress properties in an ethoxylated system.
[0016] US Patent No. 5,139,770 describes the use of cross-linked vinylpyrrolidone homopolymers in formulations containing surfactants, such as conditioning shampoo to obtain relatively high viscosities. However, the patent does not teach how to create a fluid with strain strain with high optical clarity, which is also of pseudoplasticity.
[0017] US Patent No. 5,663,258 describes the preparation of cross-linked vinyl acetate / vinylpyrrolidone copolymers. High viscosities are obtained when the polymer is combined with water, but there is no teaching on using the polymer to create a fluid with strain strain 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 other monomers, including N-vinyl lactams and vinyl acetate. Preferred polymers are cross-linked and are polymerized from hydrophobically modified ethoxylated macromers in combination with neutralized acrylamidolmethylpropanesulfonic acid. The viscosities of the 1% aqueous solutions of the polymer preferably range from 20,000 mPa.s to 100,000 mPa.s. There is no teaching of an activated surfactant polymer devoid of repeating units of hydrophobically modified ethoxylated macromers that provide a fluid with strain strain that exhibit good suspension properties, without a substantial increase in viscosity.
[0019] There is still a challenge, not only to demonstrate the ability to effectively suspend particles within compositions containing stable microgel, but also exhibit desirable smoothness, desirable rheology profiles, clarity and aesthetic characteristics across a wide range of conditions of temperature and pH at low levels of use of polymers. Therefore, there is a need for a strain strain fluid based on polymer microgel particles in which the polymer concentration is not more than 5% by weight based on the weight of the composition in which it is included and having a value deformation stress of at least 1 mPa, or 0.1 Pa, where the deformation stress, modulus of elasticity and optical clarity are substantially independent of pH. There is also a need to provide strain strain fluids formulated with mild surfactants, such as, for example, surfactants containing portions of ethylene oxide. SUMMARY OF THE TECHNOLOGY DESCRIBED
[0020] The present technology provides cross-linked, non-ionic, amphiphilic polymers, or amphiphilic polymers, for short, which can be swelled in the presence of a surfactant. Amphiphilic polymers can be prepared by polymerizing a monomer composition including at least one hydrophilic monomer, at least one hydrophobic monomer and a crosslinking monomer. The crosslinking monomer can be an amphiphilic crosslinking agent, or a mixture of an amphiphilic crosslinking agent and a conventional crosslinking agent.
[0021] In one embodiment, it has been found that amphiphilic crosslinking agents can be easily reacted in the amphiphilic polymer. Amphiphilic crosslinking agents can contain more than one reactive group. In some embodiments, the at least one reactive group may be an allyl group.
[0022] In another aspect, a modality of the described technology refers to a strain strain fluid comprising a non-ionic, amphiphilic cross-linked polymer and a surfactant.
[0023] In yet another aspect, a modality of the technology described refers to a thick aqueous composition, comprising a cross-linked, non-ionic, amphiphilic polymer and at least one surfactant, in which the concentration of the polymer is not more than 5% by weight based on the total weight of the composition, and the at least one surfactant is not more than 70% by weight of the composition, the strain strain of the composition is at least 1 mPa, or 0.1 Pa with a pseudoplasticity index less than 0.5 at shear rates between about 0.1 and about 1 reciprocal second, and where the strain strain, modulus of elasticity and optical clarity of the composition are substantially independent of pH in the range of about 2 to about 14.
[0024] In yet another aspect, a modality of the described technology refers to a thick aqueous composition, comprising, a cross-linked, non-ionic, amphiphilic polymer and at least one surfactant, in which the concentration of the polymer is not more than 5 % by weight based on the total weight of the composition, and the at least one surfactant is not more than 70% by weight of the composition, where the ratio of the standard deviation to the mean of the measured values for the strain strain, modulus of elasticity and optical clarity 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.
[0025] In yet another aspect, a modality of the described technology refers to a thick aqueous composition, comprising, a cross-linked, non-ionic, amphiphilic polymer and at least one surfactant, in which the concentration of the polymer is not more than 5 % by weight based on the total weight of the composition, and at least one surfactant is not more than 70% by weight of the composition, the strain strain of the composition is at least 1mPa, or 0.1 Pa with a pseudoplasticity index of less than 0.5 at shear rates between about 0.1 and about 1 reciprocal second, and where the strain strain, modulus of elasticity and optical clarity of the composition are substantially independent of pH in the range of about 2 to about 14 and where the composition is capable of suspending granules of a size between 0.5 and 1.5 millimeters, where the difference in specific gravity of the granules in relation to water is in the range of 0.2 to 0.5 during a period of at least 4 weeks at room temperature.
[0026] In yet another aspect, a modality of the described technology refers to a thick aqueous composition, comprising, a cross-linked, non-ionic, amphiphilic polymer and one or more surfactants, in which the concentration of the polymer is not more than 5 % by weight based on the total weight of the composition, where the total concentration of surfactant is not more than 70% by weight of the composition, the strain strain of the composition is at least 1 mPa, or 0.1 Pa with an index of pseudoplasticity less than 0.5 at shear rates between about 0.1 and about 1 reciprocal second, and where the strain strain, elasticity modulus and optical clarity of the composition are substantially independent of the pH in the range of about 2 to about 14 and where the composition is capable of suspending the granules of a size between 0.5 and 1.5 mm when the difference in the specific gravity of the granules in relation to water is in the range of 0.2 to 0, 5 for a period of at least 4 weeks at room temperature where one of the surfactants contains portions of ethylene oxide and said surfactant is more than 75% by weight of the total surfactant.
[0027] The cross-linked, non-ionic, amphiphilic polymer compositions as well as the thick aqueous fluid comprising the non-ionic amphiphilic polymer compositions and the at least one surfactant of the technology described may suitably comprise, consist of, or consist essentially of components, elements , and delimitations of the process described here. The technology described illustratively described herein can be practiced properly in the absence of any element that is not specifically disclosed here.
[0028] Unless otherwise indicated, all percentages, parts, and ratios expressed here are based on the total weight of the components contained in the compositions of the technology described.
[0029] As used herein, the term "amphiphilic polymer" means that the polymeric material has distinct hydrophilic and hydrophobic portions. "Hydrophilic" generally means a portion that interacts intramolecularly with water and other polar molecules. "Hydrophobic" typically means a part that preferably interacts with oils, fats and other non-polar molecules instead of aqueous media.
[0030] 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% by weight, in one aspect, and soluble in about 10% by weight, in another aspect (calculated on a water basis plus the weight of monomer).
[0031] As used herein, the term "hydrophobic monomer" means a monomer that is substantially insoluble in water. The term "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 about 2.5% by weight, in another aspect (calculated on a water basis plus the weight of monomer).
[0032] The term "non-ionic", as used herein, encompasses either a monomer, the monomer composition or a polymer polymerized from a monomer composition free of ionic or ionizable ("non-ionizable") moieties, and a "substantially non-ionic" monomer, monomer or polymer composition polymerized from a monomer composition.
[0033] An ionizable unit is a group that can be made ionic by neutralization with an acid or a base.
[0034] An ionic portion or an ionized portion is any portion that has been neutralized by an acid or a base.
[0035] By "substantially non-ionic" is meant that the monomer, monomer or polymer composition polymerized from a monomer composition contains less than 5% by weight, in one aspect, less than 3% by weight in another aspect, less than 1% by weight in an additional aspect, less than 0.5% by weight in yet another aspect, less than 0.1% by weight, in an additional aspect, and less than 0.05% in weight in an additional aspect, of an ionizable and / or ionized portion.
[0036] For the purposes of the specification the prefix "(met) acrylic" includes "acrylic" as well as "methacrylic". For example, the term "(meth) acrylamide" includes both acrylamide and methacrylamide. DESCRIPTION OF EXEMPLIFICATIVE MODALITIES
[0037] Examples of modalities according to the disclosed technology will be described. Various modifications, adaptations or variations in the exemplary embodiments described herein may become apparent to those skilled in the art as described. It should be understood that all such modifications, adaptations or variations that depend on the teachings of the described technology, and through which these teachings have advanced the technique, are considered to be within the scope and spirit of the described technology.
[0038] While the weight ranges for the various components and ingredients that may be contained in the compositions of the described technology overlap have been expressed for selected modalities and aspects of the described technology, it should be readily apparent that the specific quantity of each component in the described compositions they will be selected from their described range such that the quantity of each component is adjusted in such a way that the sum of all components in the composition will total 100 percent by weight. The amounts used can vary with the purpose and character of the desired product and can be readily determined by one skilled in the art.
[0039] It has been unexpectedly discovered that highly efficient strain strain fluids with excellent pseudoplasticity and optical clarity over a wide pH range are obtained if certain chemically cross-linked amphiphilic, non-ionic (or substantially non-ionic) polymers are mixed with surfactants in the water. It has been determined that the crosslinking provides the right balance between the mechanical stiffness of the particles and expansion in aqueous media of the surfactant. The non-ionic (or substantially non-ionic), cross-linked amphiphilic polymers of the present technology exhibit high swelling of activated surfactant in water with an increase in particle diameter of at least a factor of 2.5 in one aspect and at least 2, 7 in another aspect. In addition, swollen polymer-based microgels of the described technology interact with each other in aqueous surfactant media to create soft glassy materials (SGMs) with high strain strain and pseudoplasticity flow that is substantially independent of pH. Amphiphilic polymer
[0040] Amphiphilic, non-ionic, crosslinked polymers useful in the practice of the described technology are polymerized from components of monomers that contain radically free polymerizable unsaturation. In one embodiment, the non-ionic, cross-linked amphiphilic polymers useful in the practice of the described technology are polymerized from a monomer composition comprising at least one unsaturated hydrophilic non-ionic monomer, at least one unsaturated hydrophobic monomer, and at least one unsaturated hydromer. of polyunsaturated crosslinking. In one aspect, the copolymer can be polymerized from a monomer composition that comprises any weight ratio of unsaturated hydrophilic non-ionic monomer to unsaturated hydrophobic monomer.
[0041] In one embodiment, the copolymers can be polymerized from a monomer composition typically having a ratio of hydrophilic monomer to hydrophobic monomer from about 5: 95% by weight to about 95: 5% by weight, 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 an additional aspect, based on the total weight of the hydrophilic and hydrophobic monomers present. The hydrophilic monomer component can be selected from a hydrophilic monomer or a mixture of hydrophilic monomers, and the hydrophobic monomer component can be selected from a single hydrophobic monomer or a mixture of hydrophobic monomers. Hydrophilic monomer
[0042] The hydrophilic monomers suitable for the preparation of cross-linked, nonionic, amphiphilic polymer compositions of the technology described are selected from, but are not limited to, hydroxy-alkyl (C1-C5) acrylates; Open and cyclic N-vinylamides (N-vinyl-lactams containing 4 to 9 atoms in the lactam ring portion, where the ring carbon atoms can be optionally substituted by one or more lower alkyl groups such as methyl, ethyl or propyl); amino group containing vinyl monomers selected from (meth) acrylamide, N- (C1-C5) alkyl (meth) acrylamides, N, N-di (C1-C5) alkyl (meth) acrylamides, N- (C1-C5) alkylamino (C1-C5) alkyl (meth) acrylamides and N, N-di (C1-C5) alkylamino (C1- C5) alkyl (meth) acrylamides, wherein the alkyl moieties in the disubstituted amino groups can be the same or different, and wherein the alkyl moieties in the monosubstituted and disubstituted amino groups can be optionally substituted with a hydroxyl group; other monomers include vinyl alcohol; imidazole vinyl; and (meth) acrylonitrile. Mixtures of the above monomers can also be used.
[0043] The hydroxy (C1-C5) alkyl (meth) acrylates can be structurally represented by the following formula:
where R is hydrogen or methyl and R1 is a divalent alkylene radical containing 1 to 5 carbon atoms, where the alkylene radical can be optionally substituted by one or more methyl groups. Representative monomers include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and mixtures thereof.
Representative open-chain N-vinylamides include N-vinylformamide, N-methyl-N-vinylformamide, N- (hydroxymethyl) -N-vinylformamide, N-vinylacetamide, N-vinylmethylacetamide, N- (hydroxymethyl) - N -vinylacetamide and mixtures thereof.
Representative cyclic N-vinylamides (also known as N-vinyl-lactams) include N-vinyl-2-pyrrolidinone, N- (1-methyl-vinyl) pyrrolidone, N-vinyl-2-piperidone, N-vinyl- 2-caprolactam, N-vinyl-5-methyl pyrrolidinone, N-vinyl-3,3-dimethyl pyrrolidone, N-vinyl-5-ethyl pyrrolidinone and N-vinyl-6-methyl piperidone and mixtures thereof. In addition, monomers containing a pendant N-vinyl lactam radical can also be employed, for example, N-vinyl-2-ethyl-2-pyrrolidone (meth) acrylate.
[0046] The amino group containing vinyl monomers include (meth) acrylamide, diacetone acrylamide and monomers that are structurally represented by the following formulas:

[0047] Formula (II) represents N- (C1-C5) alkyl (met) acrylamide, or N, N-di (C1-C5) alkyl (met) acrylamide in which R2 is hydrogen or methyl, R3 is independently selected from hydrogen, C1 to C5 alkyl and C1 to C5 hydroxyalkyl, and R4 independently is selected from C1 to C5 alkyl or C1 to C5 hydroxyalkyl.
[0048] Formula (III) represents N- (C1-C5) alkylamino (C1-C5) alkylamino (meth) acrylamide, or N, N-di (C1-C5) alkylamino (C1- C5) alkyl (meth) acrylamide where R5 is hydrogen or methyl, R6 is C1 to C5 alkylene, R7 is independently selected from hydrogen or C1 to C5 alkyl, and R8 is independently selected from C1 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 their mixtures. Hydrophobic monomer
[0052] Hydrophobic monomers suitable for the preparation of cross-linked, non-ionic, amphiphilic polymer compositions of the technology described are selected from, but are not limited to, one or more of the (meth) acrylic acid esters with alcohols containing 1 to 30 carbon atoms; vinyl esters of aliphatic carboxylic acids containing 1 to 22 carbon atoms; vinyl alcohol ethers containing 1 to 22 carbon atoms; vinyl aromatics containing 8 and 20 carbon atoms; vinyl halides; vinylidene halides; linear or branched alpha-mono-olefins containing 2 to 8 carbon atoms; an associative monomer containing a hydrophobic terminal group containing 8 to 30 carbon atoms and mixtures thereof. Semi-hydrophobic monomer
[0053] Optionally, at least one semi-hydrophobic monomer can be used in the preparation of the amphiphilic polymers of the technology described. 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 radical containing 1 to 4 carbon atoms.
[0054] In one aspect of the technology described, esters of (meth) acrylic acid with alcohols containing 1 to 30 carbon atoms can be represented by the following formula:
where R9 is hydrogen or methyl and R10 is C1 to C22 alkyl. Representative monomers according to formula (IV) include, but are not limited to (meth) methyl acrylate, (meth) ethyl acrylate, (meth) butyl acrylate, (meth) butyl-acrylate, (met) iso-butyl acrylate, (meth) acrylate), hexyl (met) acrylate, (meth) octyl acrylate, (meth) 2-ethylhexyl acrylate, (meth) decyl acrylate, (meth) acrylate of isodecyl, (meth) lauryl acrylate, (meth) tetradecyl acrylate, (meth) hexadecyl acrylate, (meth) stearyl acrylate, (meth) behenyl acrylate and mixtures thereof.
[0055] Vinyl esters of aliphatic carboxylic acids containing 1 to 22 carbon atoms can be represented by the following formula:
wherein R11 is an aliphatic group C1 to C22 which can be an alkyl or alkenyl group. Representative monomers according to formula (V) include, but are not limited to, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl valerate, vinyl hexanoate, vinyl 2-methylhexanoate, 2 - vinyl ethylhexanoate, vinyl isooctanoate, vinyl nonanoate, vinyl neodecanoate, vinyl decanoate, vinyl versatate, vinyl laurate, vinyl palmitate, vinyl stearate and mixtures thereof.
[0056] In one aspect, vinyl alcohol ethers containing 1 to 22 carbon atoms can be represented by the following formula:
where R13 is C1 to C22 alkyl. Representative monomers of formula (VI) include methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether, vinyl decyl ether, vinyl lauryl ether, vinyl stearyl ether, vinyl behenyl ether and mixtures thereof .
[0057] Representative aromatic vinyl monomers include, but are not limited to styrene, alpha-methyl styrene, 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.
[0058] Representative vinyl and vinylidene halides include, but are not limited to, vinyl chloride and vinylidene chloride and mixtures thereof.
[0059] Representative alpha-olefins include, but are not limited to, ethylene, propylene, 1-butene, iso-butylene, 1-hexene and mixtures thereof.
[0060] The associative monomer of the described technology has a portion of ethylenically unsaturated terminal groups (i) for the addition polymerization with the other monomers of the described technology; a portion of intermediate section polyoxyalkylene (ii) to impart selective hydrophilic and / or hydrophobic properties to the polymeric product, and a portion of hydrophobic end group (iii) to provide selective hydrophobic properties to the polymer.
[0061] The portion (i) providing the ethylenically unsaturated terminal group may be a residue derived from a monocarboxylic acid α, β-ethylenically unsaturated. Alternatively, portion (i) of the associative monomer can be a residue derived from an allyl ether or vinyl ether; a nonionic vinyl substituted urethane monomer, as described in US Patent No. 33,156 or US Patent No. 5,294,692; or a vinyl substituted urea reaction product, as disclosed in US Patent No. 5,011,978; the relevant descriptions of each are hereby incorporated by reference.
[0062] The middle section portion (ii) is a polyoxyalkylene segment of about 2 to about 150, in one aspect, from about 10 to about 120, in another aspect, and about 15 at about 60 in another aspect of C2 - C4 alkylene oxide repeating units. The middle portion of section (ii) includes segments of polyoxyethylene, polyoxypropylene, and polyoxybutylene, and combinations thereof, comprising from about 2 to about 150, in one aspect, from about 5 to about 120, in one another aspect, and from about 10 to about 60 in another aspect of ethylene, propylene and / or butylene oxide units, arranged in random sequences or in a block of ethylene oxide, propylene oxide and / or oxide units butylene.
[0063] The hydrophobic terminal group portion (iii) of the associative monomer is a hydrocarbon radical that belongs to one of the following classes of hydrocarbons: a linear C8-C30 alkyl, a branched C8-C30 alkyl, a carbocyclic C8-C30 alkyl , a phenyl substituted by C2-C30 alkyl, a phenyl substituted by araalkyl, and C2-C30 alkyl groups substituted by aryl.
[0064] Non-limiting examples of suitable hydrophobic end group portions (iii) of the associative monomers are linear or branched alkyl groups having about 8 to about 30 carbon atoms, such as capryl (C8), thaloctyl (branched C8) ), decyl (C10), lauryl (C12), myristyl (C14), cetyl (C16), cetearyl (C16-C18), stearyl (C18), isostearyl (C18 branched), arachidyl (C20), behenila (C22), lignoceril (C24), kerothyl (C26), montanil (C28), melissil (C30), and the like.
[0065] Examples of straight and branched alkyl groups having about 8 to about 30 carbon atoms, which are derived from a natural source include, but are not limited to, alkyl groups derived from hydrogenated peanut oil, oil soy and canola oil (all predominantly C18), hydrogenated tallow oil (C16-C18), and the like; and C10-C30 hydrogenated terpenols, such as hydrogenated geraniol (branched C10), hydrogenated farnesol (branched C15), hydrogenated phytol (C20), and the like.
[0066] Non-limiting examples of suitable C2-C30-substituted phenyl groups include octylphenyl, nonylphenyl, decylphenyl, dodecylphenyl, hexadecylphenyl, octadecylphenyl, isooctylphenyl, sec-butylphenyl and the like.
[0067] Examples of aryl-substituted C2-C40 alkyl groups include, without limitation, styryl (for example, 2-phenylethyl), distyryl (for example, 2,4-diphenylbutyl), tristyryl (for example, 2,4 , 6 triphenylhexyl), 4-phenylbutyl, 2-methyl-2-phenylethyl, tristyrylphenolala and the like.
Suitable carbocyclic C8-C30 alkyl groups include, without limitation, groups derived from sterols from animal sources, such as cholesterol, lanosterol, 7-dehydrocholesterol and the like; from plant sources, such as phytosterol, stigmasterol, campesterol and the like; and from yeast sources, such as ergosterol, mycosterol and the like. Other hydrophobic carbocyclic alkyl end groups useful in the disclosed technology include, but are not limited to, cyclooctyl, cyclododecyl, adamantyl, decahydronaphthyl, and groups derived from natural carbocyclic materials, such as pinene, hydrogenated retinol, camphor, alcohol from isobornyl and the like.
[0069] Useful associative monomers can be prepared by any method known in the art. See, for example, U.S. Patent No. 4,421,902 to Chang et al .; No. 4,384,096 to Sonnabend; No. 4,514,552 to Shay et al .; No. 4,600,761 to Ruffner et al; No. 4,616,074 to Ruffner; No. 5,294,692 to Barron et al .; No. 5,292,843 to Jenkins et al .; No. 5,770,760 to Robinson; and No. 5,412,142 to Wilkerson, III et al .; the permanent descriptions of which are hereby incorporated by reference.
[0070] In one aspect, exemplary associative monomers include those represented by formulas (VII) and (VIIA) as follows:
where R14 is hydrogen or methyl; A is -CH2C (O) O-, -C (O) O-, -O-, -CH2O-, -NHC (O) NH-, -C (O) NH-, Ar- (CE2) z-NHC (O) O-, Ar (CE2) z-NHC (O) NH-, or -CH2CH2NHC (O) -; Air is a divalent arylene (for example, phenylene); E is H or methyl; z is 0 or 1; k is an integer ranging from about 0 to about 30, and m is 0 or 1, with the proviso that when k is 0, m is 0, and when k is in the range of 1 to about 30, m is 1; D represents a vinyl radical or an allyl radical; (R15-O) n is a polyoxyalkylene radical, which can be a homopolymer, a random copolymer, or a block copolymer of C2-C4 oxyalkylene units, R15 is a divalent alkylene radical selected from C2H4, C3H6, or C4H8, and their combinations; and n is an integer in the range of about 2 to about 150, in one aspect, from about 10 to about 120, in another aspect, and from about 15 to about 60, in an additional aspect ; Y is -R15O-, -R15NH-, -C (O) -, -C (O) NH-, R15NHC (O) NH-, or -C (O) NHC (O) -; R16 is a substituted or unsubstituted alkyl selected from a linear C8-C30 alkyl group, a branched C8-C30 alkyl, a carbocyclic C8-C30 alkyl group, a phenyl substituted by C2-C30 alkyl, a phenyl substituted by aralkyl, and an aryl-substituted C2-C30 alkyl group; wherein the R16 alkyl group, aryl group, phenyl group optionally comprises one or more substituents selected from the group consisting of a hydroxyl group, an alkoxy group, phenylethyl group, benzyl group, and a halogen group.
[0071] In one aspect, the hydrophobically modified associative monomer is an alkoxylated (meth) acrylate having a hydrophobic group containing 8 to 30 carbon atoms, represented by the following formula:
where R14 is hydrogen or methyl; R15 is a divalent alkylene radical independently selected from C2H4, 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 one another aspect, and from about 10 to about 60 in an additional aspect, (R15-O) can be arranged in a block configuration or in a random way; R16 is substituted or unsubstituted alkyl selected from a group of linear C8-C30 alkyl, branched C8-C30 alkyl, carbocyclic C8-C30 alkyl, phenyl substituted with C2-C30 alkyl, and C2-C30 alkyl substituted with aryl.
[0072] Representative monomers according to formula (VII) include polyethoxylated lauryl methacrylate (LEM), polyethoxylated cetyl methacrylate (CEM), polyethoxylated cetearyl methacrylate (CSEM), polyethoxylated (meth) acrylate, (meth) polyethoxylated arachidyl acrylate, (meth) polyethoxylated behenyl acrylate (BEM), polyethoxylated cerotyl acrylate, (meth) polyethoxylated montanyl acrylate, (meth) polyethoxylated melissyl acrylate, (methoxylated polyethyl acrylate, (meth) ) polyethoxylated nonylphenyl acrylate, polyoxyethylene w-tristyrylphenyl methacrylate, in which the polyethoxylated portion of the monomer contains about 2 to about 150 units of ethylene oxide, in one aspect, from about 5 to about 120, in another aspect, and from about 10 to about 60, in an additional aspect; (meth) polyethylene glycol acrylate (8) polypropylene glycol (6), (meth) phenoxy polyethylene glycol (6) polypropylene glycol (6), and (meth) nonylphenoxy polyethylene glycol acrylate of polypropylene glycol.
[0073] The semi-hydrophobic monomers of the technology described are structurally similar to the associative monomer described above, but have a terminal radical substantially not a hydrophobic group. The semi-hydrophobic monomer has an ethylenically unsaturated terminal group radical (i) for polymerization in addition to the other monomers of the described technology; a polyoxyalkylene radical from the intermediate section (ii) to impart hydrophilic and / or hydrophobic properties selective for the product polymer and a semi-hydrophobic end group radical (iii). The radical of the unsaturated terminal group (i) providing the vinyl group or other ethylenically unsaturated terminal group for the polymerization in addition is preferably derived from an α, β-ethylenically unsaturated carboxylic acid. Alternatively, the radical of the terminal group (i) can be derived from an allyl ether residue, a vinyl ether residue or a residue from a nonionic urethane monomer.
[0074] The intermediate section of polyoxyalkylene (ii) specifically comprises a segment of polyoxyalkylene, which is substantially similar to the polyoxyalkylene radical of the associative monomers described above. In one aspect, polyoxyalkylene radicals (ii) include polyoxyethylene, polyoxypropylene, and / or polyoxybutylene units that comprise from about 2 to about 150 in one aspect, from about 5 to about 120, in one another aspect, and from about 10 to about 60 in an additional aspect of ethylene oxide, propylene oxide, and / or butylene oxide units, arranged in random sequences or in blocks.
[0075] 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-, Ar- (CE2) z-NHC (O) O-, Ar (CE2) z-NHC (O) NH-, or -CH2CH2NHC (O) -; Air is a divalent arylene (for example, phenylene); E is H or methyl; z is 0 or 1; k is an integer ranging from about 0 to about 30, and m is 0 or 1, with the proviso that when k is 0, m is 0, and when k is in the range of 1 to about 30, m is 1; (R15-O) n is a polyoxyalkylene radical, which can be a homopolymer, a random copolymer, or a block copolymer of C2-C4 oxyalkylene units, R15 is a divalent alkylene radical selected from C2H4, C3H6, or C4H8, and their combinations; and n is an integer in the range of about 2 to about 150, in one aspect, from about 5 to about 120, in another aspect, and from about 10 to about 60, in an additional aspect ; R17 is selected from hydrogen and a straight or branched chain C1-C4 alkyl group (for example, methyl, ethyl, propyl, iso-propyl, butyl, iso-butyl, and tert-butyl); and D represents a vinyl radical or an allyl radical.
[0076] In one aspect, the semi-hydrophobic monomer under formula VIII can be represented by the following formulas: CH2 = C (R14) C (O) O- (C2H4O) to (C3H6O) bH VIIIA CH2 = C (R14) C (O) O- (C2H4O) to (C3H6O) b-CH3 VIIIB where R14 is hydrogen or methyl, and "a" is an integer ranging from 0 or 2 to about 120, in one respect, from from about 5 to about 45, in another aspect, and from about 10 to about 0.25, in an additional aspect, and "b" is an integer ranging from about 0 or 2 to about 120, in one aspect, from about 5 to about 45, in another aspect, and from about 10 to about 0.25, in an additional aspect, subject to the condition that "a" and "b "cannot be 0 at the same time.
[0077] Examples of semi-hydrophobic monomers according to 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 the product names Blemmer® PP-1000 (R14 = methyl, b = 4 to 6, a = 0), PP-500 (R14 = methyl, a = 0, b = 9), PP- 800 (R14 = methyl, a = 0, b = 13); polyethylene glycol methacrylate polypropylene glycol available under the 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 the product names Blemmer® 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 the 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.
[0078] Examples of semi-hydrophobic monomers according to formula VIIIB include methoxy polyethylene 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) 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), PMA-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).
[0079] In one aspect, the semi-hydrophobic monomer shown in formula IX can be represented by the following formulas: CH2 = CH-O- (CH2) dO- (C3H6O) e- (C2H4O) fH IXA CH2 = CH-CH2- O- (C3H6O) g- (C2H4O) hH IXB where d is an integer of 2, 3, or 4; and is an integer in the range of 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 an additional aspect; f is an integer in the range of 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 an additional aspect ; g is an integer in the range of 1 to about 10 in one aspect, from about 2 to about 8 in another aspect, and from about 3 to about 7, in an additional aspect; and h is an integer in the range of 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.
[0080] Monomers in formulas IXA and IXB are commercially available under the trade names EMULSOGEN® R109, R208, R307, RAL109, RAL208 and RAL307 sold by Clariant Corporation; BX-AA-E5P5 sold by Bimax, Inc .; and their combinations. EMULSOGEN® R109 is a 1,4-ethoxylated / propoxylated vinyl butanediol ether that has the empirical formula CH2 = CH (CH2) 4O (C3H6O) 4 (C2H4O) 10H; EMULSOGEN® R208 is a randomly ethoxylated / propoxylated 1,4-butanediol ether that has the empirical formula CH2 = CH (CH2) 4O (C3H6O) 4 (C2H4O) 20H; EMULSOGEN® R307 is a randomly ethoxylated / propoxylated 1,4-butanediol ether that has the empirical formula CH2 = CH (CH2) 4O (C3H6O) 4 (C2H4O) 30H; EMULSOGEN® RAL109 is a 1,4-ethoxylated / propoxylated vinyl butanediol ether that has the empirical formula CH2 = CHCH2O (C3H6O) 4 (C2H4O) 10H; EMULSOGEN® RAL208 is a randomly ethoxylated / propoxylated 1.4 butanediol vinyl ether that has the empirical formula CH2 = CHCH2O (C3H6O) 4 (C2H4O) 20H, EMULSOGEN® RAL307 is a randomly ethoxylated / butylated vinyl butanediol ether that is randomly ethoxylated / propylated. has the empirical formula CH2 = CHCH2O (C3H6O) 4 (C2H4O) 30H; and BX-AA-E5P5 is a randomly ethoxylated / propoxylated allyl ether that has the empirical formula CH2 = CHCH2O (C3H6O) 5 (C2H4O) 5H.
[0081] In the associative and semi-hydrophobic monomers of the technology described, the polyoxyalkylene intermediate section radical contained in these monomers can be used to adjust the hydrophilicity and / or hydrophobicity of the polymers in which they are included. For example, radicals in the middle section rich in ethylene oxide radicals are more hydrophilic while radicals in the middle section rich in propylene oxide radicals are more hydrophobic. By adjusting the relative amounts of ethylene oxide radicals to propylene oxide present in these monomers the hydrophilic and hydrophilic properties of the polymers in which these monomers are included can be adapted as desired.
[0082] The amount of associative and / or semi-hydrophobic monomer used in the preparation of the polymers of the technology described can vary widely and depends, among other things, on the desired final rheological and aesthetic properties of the polymer. When used, the monomer reaction mixture contains one or more monomers selected from the associative and / or semi-hydrophobic monomers disclosed above in amounts ranging 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 an additional aspect, based on the weight of the total monomers. Ionizable monomer
[0083] In one aspect of the disclosed technology, the non-ionic, amphiphilic, crosslinked polymer compositions of the technology described can be polymerized from a monomer composition including 0 to 5% by weight of an ionizable and / or ionized monomer, with based on the weight of the total monomers, provided that the strain strain value of the strain strain fluids, in which the polymers of the described technology are included are not adversely affected (ie the strain strain value of the fluid does not fall below 1 mPa, or 0.001 Pa).
[0084] In another aspect, the amphiphilic polymer compositions of the technology described can be polymerized from a monomer composition comprising less than 3% by weight in one aspect, less than 1% by weight in an additional aspect, less 0.5% by weight in an additional aspect, less than 0.1% in an additional aspect, and less than 0.05% by weight in an additional aspect, of an ionizable and / or ionized radical, based on weight of total monomers.
[0085] Ionizable monomers include monomers that have a neutralizable radical base and monomers having an acid neutralizable radical. Monomers of neutralizable base include olefinically unsaturated monocarboxylic and dicarboxylic acids and their salts containing 3 to 5 carbon atoms and their anhydrides. Examples include (meth) acrylic acid, itaconic acid, maleic acid, maleic anhydride, and combinations thereof. Other acidic monomers include styrene sulfonic acid, acrylamidomethylpropanesulfonic acid (AMPS® monomer), vinylsulfonic acid, vinylphosphonic acid, allylsulfonic acid, metalylsulfonic acid; and its salts.
[0086] Neutralizable acid monomers include olefinically unsaturated monomers that contain a basic nitrogen atom capable of forming a salt or a quaternized radical with the addition of an acid. For example, these monomers include vinylpyridine, vinylpiperidine, vinylimidazole, vinylmethylimidazole, dimethylaminomethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, methacrylate (methyl) dimethylamine and methacrylate (meth) acrylate) , and diethylaminoethyl (meth) acrylate. Crosslinking monomer
[0087] In one embodiment, the non-ionic, cross-linked amphiphilic polymers useful in the practice of the described technology are polymerized from a monomer composition comprising a first monomer comprising at least one nonionic, hydrophilic, unsaturated monomer a nonionic, hydrophobic unsaturated monomer and mixtures thereof, and a third monomer comprising at least one polyunsaturated crosslinking monomer. The crosslinking monomer (s) is used to polymerize covalent crosslinks in the polymer backbone. The crosslinking monomer can be an amphiphilic crosslinking agent or a mixture of an amphiphilic crosslinking agent and a conventional crosslinking agent.
[0088] The crosslinking monomer can be an amphiphilic crosslinking agent. The amphiphilic cross-linking agent is used to polymerize covalent cross-links in the backbone of the amphiphilic polymer. In some cases, conventional crosslinking agents can affect the volume expansion or expansion of microgel particles in fluids that contain surfactants. For example, a high level of conventional crosslinking agent could provide a high strain strain, but limited expansion of microgels would result in undesirably high levels of polymer utilization and low optical clarity. On the other hand, a low level of conventional crosslinking agents could give high optical clarity, but low strain strain. It is desirable that polymeric microgels allow maximum expansion, maintaining a desirable strain strain, and it has been found that the use of amphiphilic crosslinking agents in place of, or in conjunction with conventional crosslinking agents, can provide only these benefits. In addition, it has been found that the amphiphilic crosslinking agent can be easily reacted with the amphiphilic polymer. Often, certain processing techniques, such as phases, may be required with conventional crosslinking agents, to achieve the proper balance of optical clarity and yield stress. In contrast, it has been found that amphiphilic crosslinking agents can simply be added in a single phase with the monomer mixture.
[0089] Amphiphilic crosslinking agents are a subset of compounds known in the art as reactive surfactants. Reactive surfactants are surface agents that contain at least one reactive radical in quality so that they can covalently bond to the surface of the polymeric particles. By bonding to particles, reactive surfactants can improve the colloidal stability of latex particles due to the resistance of the surfactant to desorption from the particle surface. Reactive surfactants in the art commonly only have, or only need, a reactive radical to prevent such desorption.
[0090] As a subset of reactive surfactants, amphiphilic crosslinking agents, as used herein are compounds or mixtures thereof that include more than one reactive radical. Surprisingly, it has been found that such amphiphilic crosslinking agents can not only be used to improve particle stability, but can be efficiently used to prepare strain strain fluids, as described herein.
[0091] The technique is replete with descriptions of various types of reactive surfactants, and one skilled in the art can easily determine which ones include more than one reactive radical in such a way that they can be employed here as amphiphilic crosslinking agents without undue experimentation. Exemplary amphiphilic cross-linking agents can be seen, for example, in US 3,541,138 (granted on November 17, 1970 to Emmons et al.), US 6,262,152 (granted on July 17, 2001 to Fryd et al. ), US 8,354,488 (granted on January 15, 2013 to Li et al.), WO2002 / 100525 (published on December 19, 2002 to Syngenta) and the like.
[0092] The amphiphilic crosslinking agent contains a hydrophobic radical and a hydrophilic radical. The hydrophobic radical will provide solubility in oils, and the hydrophilic radical will provide solubility in water. Hydrophobic and hydrophilic radicals are well known to those skilled in the art.
[0093] Non-limiting examples of hydrophobic radicals of the amphiphilic crosslinking agent can be derived from functional groups, such as alkyl, aryl, and alkyl aryl acrylates or methacrylates with 1 to 12 carbon atoms in the alkyl and / or 6 group to 12 carbons in the aryl group such as methyl, ethyl, butyl, propyl, isobutyl, hexyl, 2-ethyl hexyl, nonyl, lauryl, isobornyl, benzyl and similar acrylates and methacrylates; polymerizable aromatic vinyl monomers, such as styrene, alpha methyl styrene, vinyl toluene and the like; and aliphatic hydrocarbon monomers, such as isoprene and butadiene. Regardless of the functional constituent groups from which the hydrophobic radical of the amphiphilic crosslinking agent is derived, the hydrophobic radical will have a limited solubility in water, which one of ordinary skill in the art easily predicts. Examples of functional groups for the preparation of hydrophobic moieties may include, for example, alkyl phenols, stearyls, lauryls, tri-styryl phenols, groups derived from natural oils and the like.
[0094] Non-limiting examples of hydrophilic radicals of the amphiphilic crosslinking agent can be functional groups, such as ethoxylates, hydroxyls, starches, amines, phosphates, phosphonates, sulfates, sulfonates, carboxylates and the like. Such hydrophilic radicals of the amphiphilic crosslinking agent can be derived from, for example, acid monomers, such as acrylic acid, methacrylic acid, acrylamidomethylpropane sulfonic acid, itaconic acid, maleic acid and styrene sulfonic acid and their esters; amine-containing monomers such as 2-dimethylaminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-diethylaminoethyl methacrylate and 2-diethylaminoethyl acrylate; and monomers having oligoether radicals of the general formula: CH2 = CRC (O) O (C2H4O) nR1 where R = H or methyl; R1 = alkyl of 1 to 4 carbon atoms, aryl of 6 to 12 carbon atoms, or alkyl-aryl, en = 1 to 20, examples of which include ethoxyethyl methacrylate, butoxyethyl methacrylate, ethoxyethyl methacrylate, methoxy methacrylate -polyethylene glycol, and 2-ethoxytriethylene glycol methacrylate.
[0095] In addition, the amphiphilic crosslinking agent contains multiple crosslinking radicals. Non-limiting examples of cross-linking radicals can include those shown in Table I Table I

[0096] Other non-limiting examples of cross-linking radicals may include unsaturated radicals. In one embodiment, the amphiphilic crosslinking agent contains more than one unsaturated radical, or at least two unsaturated radicals. In one aspect, the cross-linking agent is a polyunsaturated amphiphilic compound containing at least 2 unsaturated radicals. In another aspect, the amphiphilic crosslinking agent contains at least 3 unsaturated radicals.
[0097] Mixtures of two or more amphiphilic cross-linking agents can also be used to cross-link non-ionic, amphiphilic polymers. In one aspect, the amphiphilic crosslinking agent mixture contains more than a few unsaturated moieties, or an average of 1.5 or 2 unsaturated radicals. In another aspect, the mixture of amphiphilic crosslinking agents contains an average of 2.5 unsaturated radicals. In yet another aspect, the mixture of amphiphilic crosslinking agents contains an average of about 3 unsaturated radicals. In a further aspect, the mixture of amphiphilic crosslinking agents contains an average of about 3.5 unsaturated radicals.
[0098] In one aspect, exemplary amphiphilic crosslinking agents suitable for use with the present technology may include, but are not limited to, compounds such as those disclosed in US 2013/0047892 (published February 28, 2013 by Palmer, Jr. et al.), Represented by the following formulas:
wherein R = CH3, CH2CH3, C6H5, or C14H29; n = 1, 2, or 3; x is 2 to 10, y is 0 to 200, z is 4 to 200, more preferably, about 5 to 60, and more preferably, about 5 to 40; Z can be either SO3- or PO32-, and M + is Na +, K +, NH4 +, or an alkanolamine such as, for example, monoethanolamine, diethanolamine and triethanolamine;
wherein R = CH3, CH2CH3, C6H5, or C14H29; n = 1, 2, 3; x is 2 to 10, y is 0 to 200, z is 4 to 200, more preferably, about 5 to 60, and more preferably, about 5 to 40; (III)
wherein R1 is a C10-24 alkyl, alkaryl, alkenyl, or cycloalkyl group, R2 = CH3, CH2CH3, C6H5 or C14H29; x is 2 to 10, y is 0 to 200, z is 4 to 200, more preferably, about 5 to 60, and more preferably, about 5 to 40; and R3 is H or Z- M + Z can be either SO3- or PO32-, and M + is Na +, K +, NH4 +, or an alkanolamine such as, for example, monoethanolamine, diethanolamine and triethanolamine.
[0099] The preceding amphiphilic crosslinking agents according to formulas (I), (II), (III), (IV) and (V) are described in US Patent Application Publication No. 2014/0114006, the description of which is incorporated herein by reference, and is commercially available under the RS E-Sperse ™ Series trademark (for example, product names RS-1617, RS-1618, RS-1684) from Ethox Chemicals, LLC.
[00100] In one embodiment, the amphiphilic crosslinking agent can be used in an amount ranging from about 0.01 to about 3% by weight, in one aspect, from about 0.05 to about 0 , 1% by weight in another aspect, and from about 0.1 to about 0.75% by weight, in an additional aspect, based on the dry weight of the nonionic, amphiphilic polymer of the technology described.
[00101] In another embodiment, the amphiphilic crosslinking agent can contain an average of about 1.5 or 2 unsaturated radicals and can be used in an amount ranging from about 0.01 to about 3% by weight, in one aspect, from about 0.02 to about 1% by weight, in another aspect, from about 0.05 to about 0.75% by weight, in an additional aspect, and from about 0.075 to about 0.5% 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 technology described.
[00102] In one aspect, the amphiphilic crosslinking agent is selected from compounds of formulas (III), (IV) or (V).
where n is 1 or 2; z is 4 to 40, in one aspect, 5 to 38 in another aspect, and 10 to 20, in an additional aspect; and R4 is H, SO3-M + or PO3-M +, and M is selected from Na, K, and NH4.

[00103] In one embodiment, the crosslinking monomer can include a combination of an amphiphilic crosslinking agent and a conventional crosslinking agent. In one aspect, the conventional cross-linking agent is a polyunsaturated compound containing at least 2 unsaturated radicals. In another aspect, the conventional crosslinking agent contains at least 3 unsaturated radicals. 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, di (meth) acrylate 1 , 3-butylene glycol, 1,6-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,9- nonanediol, 2,2'-bis (4- (acryloxy-propyloxyphenyl) propane, and 2,2'-bis (4- (acryloxydiethoxy-phenyl) propane, tri (meth) acrylate compounds such as, tri (meth) acrylate trimethylolpropane, trimethylolethane tri (meth) acrylate, and tetramethylolmethane tri (meth) acrylate; tetra (meth) acrylate compounds such as titrramethylolpropane tetra (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, and tetra (meth) acrylate pentaerythritol acrylate; hexa (meth) acrylate compounds such as dipentaerythritol hexa (meth) acrylate; allyl compounds such as allyl (meth) acrylate, diallyl phthalate, dially itaconate, dially fumarate, and diallyl maleate, sucrose polyallyl ethers having 2 to 8 allyl groups per molecule, pentaerythritol polyethyl ethers such as pentaerythritol diallyl ether, pentaerythritol trialyl ether, and pentaerythritol tetraallyl ether, and combinations thereof; trimethylolpropane polyallyl ethers, such as trimethylolpropane diallyl ether, trimethylolpropane trialyl ether, and combinations thereof. Other suitable polyunsaturated compounds include divinyl glycol, divinyl benzene, and methylenebisacrylamide.
[00104] In another aspect, suitable polyunsaturated monomers can be synthesized by means of a polyol esterification reaction made from ethylene oxide or propylene oxide or their combinations 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.
[00105] Mixtures of two or more of the above polyunsaturated compounds can also be used to cross-link non-ionic, amphiphilic polymers. In one aspect, the conventional unsaturated crosslinking monomer mixture contains an average of 2 unsaturated radicals. In another aspect, the mixture of conventional crosslinking agents contains an average of 2.5 unsaturated radicals. In yet another aspect, the mixture of conventional crosslinking agents contains an average of about 3 unsaturated radicals. In a further aspect, the mixture of conventional crosslinking agents contains an average of about 3.5 unsaturated radicals.
[00106] In one embodiment, the conventional cross-linking agent 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 from 0.75% by weight, in another aspect, and from about 0.1 to about 0.5% by weight, in an additional aspect, based on the dry weight of the nonionic, amphiphilic polymer of the technology described.
[00107] In another embodiment of the technology described, the conventional cross-linking agent component contains an average of about 3 unsaturated radicals and can be used in an amount ranging from about 0.01 to about 0.3% in 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 an additional aspect , and from about 0.075 to about 0.175% by weight with 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 described technology.
[00108] In one aspect, the conventional crosslinking agent is selected from trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, tetramethylol methane tri (meth) acrylate, pentaerythritol trialylether and polyallyl ethers having sucrose 3 allyl groups per molecule.
[00109] In another aspect, the nonionic amphiphilic polymer can be cross-linked with a combination of a conventional cross-linking agent and an amphiphilic cross-linking agent. The conventional crosslinking agent and amphiphilic crosslinking agent can be used in a total amount of 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 an additional aspect, based on the dry weight of the nonionic, amphiphilic polymer of the technology described.
[00110] In another embodiment, the combination of the conventional crosslinking agent and amphiphilic crosslinking agent can contain an average of about 2 or 3 unsaturated radicals and can be used in an amount ranging from about 0.01 to about 2% by weight, in one aspect, from about 0.02 to about 0.3% by weight, in another aspect, from about 0.05 to about 0.2% by weight, in one additional aspect, and from about 0.075 to about 0.175% by weight with one more aspect, and from about 0.1 to about 0.15% by weight, in another aspect, based on the total weight of the amphiphilic polymer, non-ionic, of the described technology.
[00111] In one aspect, the combination of the conventional crosslinking agent and amphiphilic crosslinking agent can include conventional crosslinking agents selected from among trimethylolpropane tri (meth) acrylate, trimethyloletane tri (meth) acrylate, tri (meth) ) tetramethylolmethane acrylate, pentaerythritol trialyl ether and sucrose polyallyl ethers having 3 allyl groups per molecule, and their combinations, and amphiphilic crosslinking agents chosen from the compounds of formula (III), (V), and their combinations. Synthesis of amphiphilic polymer
[00112] The non-ionic, amphiphilic crosslinking polymer of the technology described 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. The polymerization can be carried out in a suitable solvent system such as water. Small amounts of a hydrocarbon solvent, organic solvent, as well as their mixtures can be used. Polymerization reactions are initiated by any means that results in the generation of an appropriate free radical. Thermally derived radicals, in which the species of radical is generated from thermal, homolytic dissociation of peroxide compounds, hydroperoxides, persulfates, percarbonates, peroxyesters, hydrogen peroxide and azo can be used. The initiators can be insoluble in water or soluble in water, depending on the solvent system used for the polymerization reaction.
[00113] 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 an additional aspect , based on the total weight of the dry polymer.
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'-azo-bis- (tert-alkyl) compounds that have a water-solubilizing substituent on the alkyl group. Exemplary oil-soluble free radical compounds include, but are not limited to 2,2'-azobisisobutyronitrile, and the like. Peroxides and peracids can optionally be activated with reducing agents, such as sodium bisulfite, sodium formaldehyde, or ascorbic acid, transition metals, hydrazine and the like.
[00115] In one aspect, azo polymerization catalysts include Vazo® free radical polymerization initiators, available from DuPont, such as Vazo® 44 (2,2'-azobis (2- (4,5-di- hydroimidazolyl) propane), Vazo® 56 (2,2'-azobis (2-methylpropionamidine) dihydrochloride), Vazo® 67 (2,2'-azobis (2-methylbutyronitrile)), and Vazo® 68 (4,4'- azobis (4-cyanovaleric acid)).
[00116] Optionally, the use of redox initiator systems known as polymerization initiators can be employed. Such redox initiator systems include an oxidizer (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, phosphoric acid and its salts, 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 the weight of the dry polymer, are used. Suitable reducers include, for example, alkali metal and ammonium salts of sulfur-containing acids, such as sodium sulfite, bisulfite, thiosulfate, hydrosulfite, sulfide, hydrosulfide or dithionite, formadinesulfinic acid, hydroxymethanesulfonic acid, acetone bisulfite, amines , such as ethanolamine, glycolic acid, glyoxylic acid hydrate, ascorbic acid, isoascorbic acid, lactic acid, glycolic acid, malic acid, 2-hydroxy-2-sulfinatoacetic acid, tartaric acid and salts of the preceding acids, typically at a level of 0 , 01% to 3.0% by weight, based on the weight of the dry polymer, is used. In one aspect, combinations of peroxodisulfates with alkali metal or ammonium bisulfites can be used, for example, ammonium peroxodisulfate and ammonium bisulfite. In another aspect, combinations of hydrogen peroxide containing compounds (t-butyl hydroperoxide) as the oxidant with ascorbic or erythorbic acid as the reducer can be used. The ratio of compound containing peroxide to reducer is within the range of 30: 1 to 0.05: 1.
[00117] In emulsion polymerization processes, it may be advantageous to stabilize the monomer / polymer droplets or particles by means of active surface aids. These are typically emulsifiers or protective colloids. The emulsifiers used can be anionic, non-ionic, cationic or amphoteric. Examples of anionic emulsifiers are alkylbenzenesulfonic acids, sulfonated fatty acids, sulfosuccinates, fatty alcohol sulfates, alkylphenol sulfates and fatty alcohol ether sulfates. Examples of usable nonionic emulsifiers are alkylphenol ethoxylates, primary alcohol ethoxylates, fatty acid ethoxylates, alkanolamide ethoxylates, fatty amine ethoxylates, EO / PO block copolymers and alkyl polyglucosides. Examples of cationic and amphoteric emulsifiers used are quaternized amine alkoxylates, alkylbetaines, alkylamidobetaines and sulfobetaines.
[00118] Examples of typical protective colloids are cellulose derivatives, 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 derivatives starch, dextran, polyvinylpyrrolidone, polyvinylpyridine, polyethyleneimine, polyvinylimidazole, polyvinylsuccinimide, polyvinyl-2-methylsuccinimide, polyvinyl-1,3-oxazolid-2-one, polyvinyl-2-methylimidazoline and copolymer. Emulsifiers or protective colloids are usually used in concentrations of 0.05 to 20% by weight, based on the weight of the total monomers.
[00119] 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 an additional aspect.
[00120] Polymerization can be carried out in the presence of chain transfer agents. Suitable chain transfer agents include, but are not limited to, compounds containing thio- and disulfide, such as C1-C18 alkyl mercaptan, such as tert-butyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, hexadecyl mercaptan, octadecyl mercaptan; mercaptoalcohols, such as 2-mercaptoethanol, 2-mercaptopropanol; mercaptocarboxylic acids, such as mercaptocarboxylic acid and 3-mercaptopropionic acid; esters of mercaptocarboxylic acid, such as butyl thioglycolate, isooctyl thioglycolate, dodecyl thioglycolate, iso-octyl 3-mercaptopropionate, and butyl 3-mercaptopropionate; thioesters; C1-C18 alkyl disulfides; aryl disulfides; polyfunctional thiols such as trimethylolpropane-tris (3-mercaptopropionate), pentaerythritol-tetra- (3-mercaptopropionate), pentaerythritol-tetra- (thioglycolate), pentaerythritol-tetra- (thiolactate), dipentaerythritol-hexate (similar); phosphites and hypophosphites; C1-C4 aldehydes, such as formaldehyde, acetaldehyde, propionaldehyde; haloalkyl compounds, such as carbon tetrachloride, bromotrichloromethane and the like; hydroxylammonium salts, such as hydroxylammonium sulfate; formic acid; sodium bisulfite; isopropanol; and catalytic chain transfer agents such as, for example, cobalt complexes (for example, cobalt (II) chelates).
[00121] Chain transfer agents are generally used in amounts ranging from 0.1 to 10% by weight, based on the total weight of the monomers present in the polymerization medium. Emulsion process
[00122] In an exemplary aspect of the technology described, the, non-ionic, amphiphilic, crosslinked polymer is polymerized by means of an emulsion process. The emulsion process can be carried out in a single reactor or in several reactors as is well known in the art. Monomers can be added as a batch mixture or each monomer can be dosed into the reactor in a phased process. A typical emulsion polymerization mixture comprises water, monomer (s), an initiator (usually water-soluble) and an emulsifier. The monomers can be polymerized in a single-phase, two-phase emulsion or a multi-phase polymerization process according to methods well known in the emulsion polymerization technique. In a two-phase polymerization process, the monomers of the first phase are added and polymerized first in the aqueous medium, following the addition and polymerization of the monomers of the second phase. The aqueous medium can optionally contain an organic solvent. If used, the organic solvent is less than about 5% by weight of the aqueous medium. Suitable examples of water-miscible organic solvents include, without limitation, esters, alkylene glycol ethers, alkylene glycol ether esters, low molecular weight aliphatic alcohols and the like.
[00123] To facilitate the emulsification of the monomer mixture, emulsion polymerization is carried out in the presence of at least one stabilizing surfactant. The term "stabilizing surfactant" is used in the context of surfactants used to facilitate emulsification. In one embodiment, emulsion polymerization is carried out in the presence of a stabilizing surfactant (active weight base) that varies in the amount of 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 an additional aspect, based on a total monomer weight basis. The emulsion polymerization reaction mixture also includes one or more free radical initiators that are present in an amount ranging from about 0.01% to about 3% by weight, based on the total weight of monomers. The polymerization can be carried out in an aqueous or hydro-alcoholic medium. Stabilizing surfactants to facilitate emulsion polymerization include anionic, non-ionic, amphoteric and cationic surfactants, as well as their reactive derivatives and mixtures. "Reactive derivatives thereof" means surfactants, or mixtures of surfactants, having on average less than a reactive group. Most commonly, anionic and non-ionic surfactants can be used as stabilizing surfactants, as well as their mixtures.
[00124] Anionic surfactants suitable 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 sulfate (for example, lauryl sulfate) sodium and sodium laureth sulfate), amino and alkali metal salts of dodecylbenzenesulfonic acid, such as sodium dodecylbenzenesulfonate and dimethylethanolamine dodecylbenzenesulfonate, alkyl (C6-C16) phenoxy benzene sulfonate, alkyl (C6-C16) phenon disodium, dialkyl (C6-C16) disodium phenoxy benzene sulfonate, disodium laureth-3 sulfosuccinate, sodium dioctyl sulfosuccinate, sodium di-sec-butyl naphthalene sulfonate, disodium sulfonate dodecyl diphenyl ether, disodium n-octadecyl sulfosuccinate , branched alcohol ethoxylate phosphate esters and the like, as well as reactive derivatives thereof.
[00125] Nonionic surfactants suitable to facilitate 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 block copolymers of polyoxyethylene, polyoxypropylene, and the like, as well as their reactive derivatives. Additional fatty alcohol ethoxylates suitable as non-ionic surfactants are described below. Other useful nonionic surfactants include polyoxyethylene glycol C8-C22 fatty acid esters, ethoxylated mono- and diglycerides, ethoxylated sorbitan esters and sorbitan esters, C8-C22 fatty acid glycol esters, ethylene oxide block copolymers propylene oxide, and their combinations, as well as reactive derivatives thereof. The number of ethylene oxide units in each of the foregoing ethoxylates can vary between 2 and above in one aspect, and from 2 to about 150 in another aspect.
[00126] Optionally, other emulsion polymerization additives and processing aids that are well known in the emulsion polymerization technique, such as auxiliary emulsifiers, protective colloids, solvents, buffering agents, chelating agents, inorganic electrolytes, polymer stabilizing agents, biocides, and pH adjusting agents can be included in the polymerization system.
[00127] In a modality of the technology described, the protective colloid or auxiliary emulsifier is selected from poly (vinyl alcohol) which has a degree of hydrolysis in the range of about 80 to 95% in one aspect, and about 85 90% in another aspect.
[00128] In a typical two-phase emulsion polymerization, a mixture of the monomers is added to a first reactor under an inert atmosphere, to a solution of an emulsifying surfactant (eg anionic surfactant) in water. Optional processing aids can be added as desired (for example, protective colloids, auxiliary emulsifier (s)). The reactor contents are agitated to prepare a monomer emulsion. For a second reactor equipped with an agitator, an inert gas inlet, and feed pumps are added under an inert atmosphere, a desired amount of water and additional anionic surfactant and optional processing aids. The contents of the second reactor are heated with stirring with mixing. After the content of the second reactor reaches a temperature in the range of about 55 to 98 ° C, a free radical initiator is injected into the aqueous surfactant solution thus formed in the second reactor, and the monomer emulsion from the first reactor is gradually dosed in the second reactor over a period that typically ranges from about half to about four hours. The reaction temperature is controlled in the range of about 45 to about 95 ° C. After monomer addition is complete, an additional amount of free radical initiator can optionally be added to the second reactor, and the resulting reaction mixture is typically maintained at a temperature of about 45 to 95 ° C for a period of time enough to complete the polymerization reaction to obtain the polymer emulsion.
[00129] In one aspect, the cross-linked, non-ionic, amphiphilic polymers of the technology described are selected from an emulsion polymer polymerized from a mixture of monomers comprising from about 20 to about 60% by weight of, at least one C1-C4 hydroxyalkyl (meth) acrylate (e.g., hydroxyethyl methacrylate); from about 10 to about 70% by weight of at least one C1C12 alkyl (meth) acrylate in one aspect, or from about 10 to about 70% by weight of at least one C1- (alkyl) acrylate C5 in another aspect; from about 0, 1, 5 or 15 to about 40% by weight of at least one vinyl ester of a C1-C10 carboxylic acid, from about 0, 1 or 15 to about 30% by weight of a lactam vinyl (for example, vinylpyrrolidone); from about 0, 0.1, 1, 5, or 7 to about 15% by weight of at least one associative and / or semi-hydrophobic monomer (where all percentages by weight of the monomer are based on the weight of the total monomers); and from about 0.01 to about 5% by weight, in one aspect, from about 0.1 to about 3 in another aspect, and from about 0.5 to about 1% by weight, in another aspect of at least one crosslinking agent (based on the dry weight of the polymer), wherein the at least one crosslinking agent is selected from an amphiphilic crosslinking agent or a combination of an amphiphilic crosslinking agent and a conventional cross-linking agent as defined herein.
[00130] In another aspect, the cross-linked, non-ionic, amphiphilic polymers of the technology described are selected from an emulsion polymer polymerized from a mixture of monomers comprising from about 20 to about 50% by weight, at least less, a C1-C4 hydroxyalkyl (meth) acrylate (e.g., hydroxyethyl methacrylate); from about 10 to about 30% by weight ethyl acrylate; from about 10 to about 35% by weight of butyl acrylate; from about 0 or 15 to about 25% by weight of a vinyl ester of a C1-C5 carboxylic acid selected from vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, and valerate vinyl; from about 0, 1 or 15 to about 30% by weight of vinylpyrrolidone .; and from about 0, 0.1, 1, 5 or 7 to about 15% by weight of at least one associative monomer and / or semi-hydrophobic monomer (where all percentages by weight of monomers are based on weight total monomers) .; and from about 0.01 to about 5% by weight, in one aspect, from about 0.1 to about 3 in another aspect, and from about 0.5 to about 1 in another aspect at least one cross-linking agent (based on the dry weight of the polymer), wherein the at least one cross-linking agent is selected from an amphiphilic cross-linking agent or a combination of an amphiphilic cross-linking agent and a cross-linking agent. conventional crosslinking, as defined herein.
[00131] In another embodiment, the cross-linked, non-ionic, amphiphilic polymers of the technology described are selected from an emulsion polymer polymerized from a mixture of monomers comprising from about 20 to about 50% by weight of hydroxyethyl methacrylate; from about 10 to about 30% by weight of ethyl acrylate; from about 10 to about 30% by weight of butyl acrylate; from about 0, 1, or 15 to about 25% by weight of vinylpyrrolidone; from about 0 to or 15 to about 25% by weight of vinyl acetate; from about 0, 0.1, 1, 5 or 7 to about 10% by weight of at least one associative and / or semi-hydrophobic monomer (where all monomer weight percentages are based on the weight of the monomers totals); and from about 0.01 to about 5% by weight, in one aspect, from about 0.1 to about 3% by weight in another aspect, and from about 0.5 to about 1% by weight, in another aspect of at least one crosslinking agent (based on the dry weight of the polymer), wherein the at least one crosslinking agent is selected from an amphiphilic crosslinking agent or a combination of a crosslinking agent amphiphilic crosslinking and a conventional crosslinking agent as defined herein.
[00132] In another embodiment, the cross-linked, non-ionic, amphiphilic polymers of the technology described are selected from an emulsion polymer polymerized from a mixture of monomers comprising between 20 to 50% by weight of methacrylate. hydroxyethyl; from about 10 to about 40% by weight of ethyl acrylate; from about 10 to about 20% by weight of butyl acrylate; from about 0.1 to about 10% by weight of at least one associative and / or semi-hydrophobic monomer (where all percentages by weight of monomers are based on the weight of the total monomers); and from about 0.01 to about 5% by weight, in one aspect, from about 0.1 to about 3% by weight in another aspect, and from about 0.5 to about 1% by weight , in another aspect of at least one crosslinking agent (based on the dry weight of the polymer), wherein the at least one crosslinking agent is selected from an amphiphilic crosslinking agent or a combination of an amphiphilic crosslinking agent and a conventional crosslinking agent, as defined herein.
[00133] In one aspect, the cross-linked, non-ionic, amphiphilic polymers of the technology described are selected from an emulsion polymer polymerized from a mixture of monomers comprising from about 20 to 50% by weight of hydroxyethyl methacrylate ; from about 10 to about 30% by weight of ethyl acrylate; from about 10 to about 30% by weight of butyl acrylate; from about 1 to about 10% by weight of at least one associative and / or semi-hydrophobic monomer (where all monomer weight percentages are based on the weight of the total monomers); and from about 0.01 to about 5% by weight, in one aspect, from about 0.1 to about 3% by weight in another aspect, and from about 0.5 to about 1% by weight, in another aspect of at least one crosslinking agent (based on the dry weight of the polymer), wherein the at least one crosslinking agent is selected from an amphiphilic crosslinking agent or a combination of a crosslinking agent amphiphilic crosslinking and a conventional crosslinking agent as defined herein.
[00134] In one aspect, the non-ionic, cross-linked, amphiphilic polymers of the technology described are selected from a polymer emulsion polymerized from a mixture of monomers comprising from about 20 to 35% hydroxyethyl methacrylate, of about from 10 to about 30% by weight of ethyl acrylate, from about 10 to about 30% by weight of butyl acrylate, from about 15 to about 25% by weight of vinylpyrrolidone, from about 15 to about of 25% by weight of vinyl acetate (where all percentages of monomers by weight are based on the weight of the total monomers) and from about 0.01 to about 5% by weight, in one aspect, of about from 0.1 to about 3% by weight in another aspect, and from about 0.5 to about 1% by weight, in an additional aspect of at least one crosslinking agent (based on the dry weight of the polymer) , wherein the at least one crosslinking agent is selected from an amphiphilic crosslinking agent or a combination of a crosslinking agent amphiphilic crosslinking and a conventional crosslinking agent as defined herein.
[00135] In one aspect, the cross-linked, non-ionic, amphiphilic polymers of the technology described are selected from an emulsion polymer polymerized from a mixture of monomers comprising from about 20 to 40% by weight of hydroxyethyl methacrylate , from about 10 to about 30% by weight of ethyl acrylate, from about 10 to about 30% by weight of butyl acrylate, from about 15 to about 25% by weight of vinylpyrrolidone, and about from 1 to about 5% by weight of at least one associative and / or semi-hydrophobic monomer (where all monomer weight percentages are based on the weight of the total monomers), and from about 0.01 to about from 5% by weight in one aspect, from about 0.1 to about 3% by weight in another aspect, and from about 0.5 to about 1% by weight with an additional aspect of at least one agent crosslinking agent (based on the dry weight of the polymer), wherein the at least one crosslinking agent is selected from a crosslinking agent amphiphilic or a combination of an amphiphilic cross-linking agent and a conventional cross-linking agent, as defined herein.
[00136] In one aspect, the cross-linked, nonionic, amphiphilic emulsion polymers of the technology are random copolymers and have average weight molecular weights ranging from above about 500,000 to at least about a billion Daltons or more, in one aspect , and from about 600,000 to about 4.5 billion Daltons in another aspect, and from about 1,000,000 to about 3,000,000 Daltons, in an additional aspect, and from about 1,500,000 to about 2,000,000 Daltons in yet another aspect (see TDS-222, October 15, 2007, Lubrizol Advanced Materials, Inc., which is incorporated by reference). Strain strain fluids
[00137] In an exemplary aspect of the described technology, the strain strain fluid comprises: i) at least one non-ionic, cross-linked, amphiphilic polymer (s) described above; 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 non-ionic surfactant, and combinations thereof; and iii) water.
[00138] In another exemplary aspect of the described technology, the strain strain fluid comprises: i) at least one non-ionic, cross-linked, amphiphilic polymer (s) described above; ii) at least one anionic surfactant; and iii) water.
[00139] In another exemplary aspect of the technology described, the strain strain fluid comprises: i) at least one non-ionic, cross-linked, amphiphilic polymer (s) described above; ii) at least one anionic surfactant and at least one amphoteric surfactant; and iii) water.
[00140] Surprisingly, the present amphiphilic polymers can be activated by a surfactant to provide a stable strain strain fluid, with desirable rheological and aesthetic properties, with the ability to suspend insoluble particles and materials in aqueous medium for indefinite periods of time independently of pH. The strain strain value, modulus of elasticity and optical clarity are substantially independent of pH in the compositions in which they are included. The strain strain fluid of the technology described is useful in the range of from about 2 to about 14, in one aspect, pH, from about 3 to 11, in another aspect, and from about 4 to about 9, in another aspect. Unlike pH-responsive cross-linked polymers (acid or sensitive base) that need neutralization with an acid or a base to provide a desired rheological profile, the nonionic, non-ionic, amphiphilic polymers of the rheological profiles of the technology described are substantially pH-independent . By substantially independent of pH it means that the strain strain fluid within which the polymer of the disclosed technology is included confers a desired rheological profile (for example, a strain strain of at least 1 MPa, or 0.1 Pa in one aspect at least 0.5 Pa, in another aspect, at least 1 Pa, in yet another aspect, and at least 2 Pa, in an additional aspect) across a wide pH range (for example, from about 2 to about 14), where the standard deviation of the strain values across the pH range is less than 1 Pa in one aspect, less than 0.5 Pa in another aspect, and less than 0 , 25 Pa, in an additional aspect of the described technology.
[00141] In an exemplary aspect of the technology described, the strain strain fluid comprises at least one cross-linked, nonionic, amphiphilic polymer, at least one anionic surfactant, an optional non-ionic surfactant, and water.
[00142] In another exemplary aspect, the strain strain fluid comprises at least one cross-linked, non-ionic, amphiphilic polymer, at least one anionic surfactant, at least one amphoteric surfactant, an optional non-ionic surfactant, and water.
[00143] In yet another exemplary aspect, the strain strain fluid comprises at least one cross-linked, non-ionic, amphiphilic polymer, at least one anionic ethoxylated surfactant, an optional non-ionic surfactant, and water. In one aspect, the average degree of ethoxylation in the anionic surfactant can vary between about 1 to about 3. In another aspect, the average degree of ethoxylation is about 2.
[00144] In another exemplary aspect, the strain strain fluid comprises at least one cross-linked, non-ionic, amphiphilic polymer, at least one ethoxylated anionic surfactant, at least one amphoteric surfactant, an optional non-ionic surfactant, and water . In one aspect, the average degree of ethoxylation in the anionic surfactant can vary between about 1 to about 3. In another aspect, the average degree of ethoxylation is about 2.
[00145] In yet another exemplary aspect, the strain strain fluid comprises at least one cross-linked, non-ionic, amphiphilic polymer, at least one anionic non-ethoxylated surfactant, at least one ethoxylated anionic surfactant, an optional non-ionic surfactant, and water. In one aspect, the average degree of ethoxylation in the anionic surfactant can vary between about 1 to about 3. In another aspect, the average degree of ethoxylation is about 2.
[00146] In another exemplary aspect, the strain strain fluid comprises at least one cross-linked, nonionic, amphiphilic polymer, at least one anionic non-ethoxylated surfactant, at least one ethoxylated anionic surfactant, at least one amphoteric surfactant, one optional non-ionic surfactant, and water. In one aspect, the average degree of ethoxylation in the anionic surfactant can vary between about 1 to about 3. In another aspect, the average degree of ethoxylation is about 2.
[00147] The amount of amphiphilic polymer used in the deformation stress fluid formulation of the described technology ranges from about 0.5 to about 5% by weight of polymer solids (100% active polymer) based on the weight of the total composition. 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 stress fluid ranges from about 1 to about 3% by weight. In a further aspect, the amount of amphiphilic polymer used in the flow stress 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 stress fluid ranges from about 2 to about 2.5% by weight. The cross-linked, non-ionic, amphiphilic polymer used in the formulation of flow stress fluids of the technology described is an emulsion polymer.
[00148] Flow stress fluids can be prepared by adding an activation surfactant. The activation surfactants used to formulate the flow stress fluids of the described technology can be selected from anionic surfactants, cationic surfactants, amphoteric surfactants, non-ionic surfactants and their mixtures. The term "activation surfactant" is used in the context of surfactants used to activate the amphiphilic polymer to create the flow stress fluid. Some activation surfactants can also be stabilizing surfactants. Several non-limiting examples of activating surfactants are presented below.
[00149] 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 herein by reference in their entirety. The anionic surfactant can be any of the anionic surfactants known or previously used in the technique of aqueous surfactant compositions. Suitable anionic surfactants include, but are not limited to, alkyl sulfates, alkyl sulfate ether, alkyl sulfonates, alcaryl sulfonates, α-olefin sulfonates, alkylamide sulfonates, alkylpolyether ether sulfates, alkylamide ether sulfates, monoglyceryl ether sulfates , alkyl monoglyceride sulfates, alkyl monoglyceride sulfonates, alkyl succinates, alkyl sulfosuccinates, alkyl sulfosuccinates, alkyl ether sulfosuccinates, alkyl amidosulfosuccinates; alkyl sulfoacetates, alkyl phosphates, alkyl ether phosphates, alkyl carboxylate ether, alkyl starch ethercarboxylates, N-alkylamino acids, N-acyl amino acids, alkyl peptides, N-acyl taurates, alkyl isethionates, salts of carboxylate in which the acyl group is derived from fatty acids; and the alkali metal, alkaline earth metal, ammonium, amine, and triethanolamine salts thereof.
[00150] In one aspect, the cationic radical of the previous salts is selected from sodium, potassium, magnesium, ammonium, mono-, die- triethanolamine salts, and mono-, di-, and tri-isopropylamine salts. The alkyl and acyl groups of the previous surfactants contain from about 6 to about 24 carbon atoms, in one aspect, from 8 to 22 carbon atoms in another aspect, from about 12 to 18 carbon atoms, in an additional aspect and can be saturated or unsaturated. The aryl groups in the surfactants are selected from phenyl or benzyl. The ether-containing surfactants shown above can contain from 1 to 10 units of ethylene oxide and / or propylene oxide per surfactant molecule in one aspect, and from 1 to 3 units of ethylene oxide per surfactant molecule in another aspect .
[00151] Examples of suitable anionic surfactants include, but are not limited to, sodium, potassium, lithium, magnesium, and laureth sulfate, trideceth sulfate, myreth sulfate, pareth sulfate C12-C13, sulfate salts pareth C12-C14, and pareth sulfate C12 -C15, ethoxylated with 1, 2, 3, 4 or 5 moles of ethylene oxide; sodium, potassium, lithium, magnesium, ammonium, and triethanolamine lauryl sulfate, coconut sulfate, tridecyl sulfate, myristyl sulfate, cetyl sulfate, cetearyl sulfate, stearyl sulfate, oleyl sulfate, and tallow sulfate, disodium lauryl sulfosuccinate, disodium laureth sulfosuccinate, sodium cocoyl isethionate, sodium C12-C14 olefin, sodium laureth-6 carboxylate, sodium cocoyl taurate, sodium cocoyl glycinate, sodium myristyl sarcocinate, sodium dodecylbenzene sulfonate, sodium cocoyl sarcosinate, sodium cocoyl glutamate, potassium myristyl glutamate, triethanolamine monolauryl phosphate, and fatty acid soaps, including sodium, potassium, ammonium, and saturated and unsaturated fatty acid salts containing from about 8 to about 22 carbon atoms.
[00152] Cationic surfactants can be any of the cationic surfactants known or previously used in the technique of aqueous surfactant compositions. Useful cationic surfactants may 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. 23, pp. 478-541, the contents of which are hereby incorporated by reference. Suitable classes of cationic surfactants include, but are not limited to alkyl amines, alkyl imidazolines, ethoxylated amines, quaternary compounds, and quaternized esters. In addition, alkyl amine oxides can function as a cationic surfactant at a low pH.
[00153] 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 their salts include dimethyl cocamine, dimethyl palmitamine, dioctylamine, dimethyl stearamine, dimethyl soybeans, soybeans, myristyl amine, tridecyl amine, ethyl stearylamine, N-sebopropane diamine, ethoxylated stearylamine, di- hydroxy ethyl stearylamine, arachidylbehenylamine, dimethyl lauramine, stearylamine hydrochloride, soybean chloride, stearylamine format, N-sebopropane dichloride, and amodimethicone.
Non-limiting examples of amidoamines and their salts include propyl dimethyl amine stearamide, propyl dimethylamine stearamido citrate, propyl diethylamine palmitamide, and cocamido propyl dimethylamine lactate.
Non-limiting examples of alkyl imidazoline surfactants include alkyl hydroxyethyl imidazoline, such as stearyl hydroxyethyl imidazoline, coconut hydroxyethyl imidazoline, ethyl hydroxymethyl oleyl oxazoline, and the like.
Non-limiting examples of ethoxylated amines include PEG-cocopolyamine, tallow amine PEG-15, quaternium-52 and the like.
[00157] Among the quaternary ammonium compounds useful as cationic surfactants, some correspond to the general formula: (R20R21R22R23N +) E-, where R20, R21, R22, and R23 are selected independently from an aliphatic group having from 1 to about of 22 carbon atoms, or an aromatic, alkoxy, polyoxyalkylene, alkyl starch, hydroxyalkyl, aryl or alkylaryl group that has 1 to about 22 carbon atoms in the alkyl chain; and E- is a salt-forming anion, such as those selected from halogen, (e.g., 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-chained aliphatic groups, for example, those with about 12 carbon atoms, or larger, can be saturated or unsaturated. In one respect, the aryl groups are selected from phenyl and benzyl.
[00158] Exemplary quaternary ammonium surfactants include, but are not limited to, cetyl trimethylammonium chloride, cetylpyridinium chloride, dichethyl dimethyl ammonium chloride, dihexadecyl dimethyl ammonium chloride, dimethyl benzyl stearyl ammonium chloride, dioctec chloride dimethyl ammonium, dieicosyl dimethyl ammonium chloride, didocosyl dimethyl ammonium chloride, dihexadecyl dimethyl ammonium chloride, dihexadecyl dimethyl ammonium acetate, behenyl trimethyl ammonium chloride, benzalkonium chloride, benzethonium chloride, and di (coconutalkyl chloride) ) dimethyl ammonium, disebo dimethyl ammonium chloride, di (hydrogenated tallow) dimethyl ammonium chloride, di (hydrogenated tallow) dimethyl ammonium, disebo dimethyl ammonium methyl sulphate, dipropyl ammonium disebo phosphate, and dimethyl ammonium disebo nitrate.
[00159] At a low pH, amine oxides can protonate and behave similarly to N-alkyl amines. Examples include, but are not limited to, dimethyl dodecylamine oxide, oleyldi (2-hydroxyethyl) amine oxide, dimethyltetradecylamine oxide, tetradecylamine di (2-hydroxyethyl) oxide, dimethylhexadecylamine oxide, behenamine oxide, behenamine oxide cocamine, deciltetradecylamine oxide, C12 -C15 dihydroxyethyl oxide alkoxypropylamine, dihydroxyethyl cocamine oxide, dihydroxyethyl lauramine oxide, dihydroxyethyl stearamine oxide, sebumamine dihydroxyethyl oxide, sebumamine oxide ethyl oxide hydrogenated amine, hydrogenated seboamine oxide, hydroxyethyl hydroxypropyl C12-C15 alkoxypropylamine oxide, lauramine oxide, myristamine oxide, ketylamine oxide, oleamidopropylamine oxide, oleamine oxide, palmitamine oxide, oxide oxide, 3 oxide oxide, oxide oxide 3 oxide of dimethyl lauramine, potassium triphosphonomethylamine oxide, soybean propylamine oxide, cocamidopropylamine oxide, stearamine oxide, sebumamine oxide and mixtures thereof.
[00160] The term "amphoteric surfactant" as used herein, is also intended to encompass zwitterionic surfactants, which are well known to formulators specializing 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 in McCutcheon’s, Functional Materials, North American edition, supra; both of which are incorporated herein by reference in their entirety. Suitable examples include, but are not limited to, amino acids (e.g., N-alkyl amino acids and N-acyl amino acids), betaines, sultaines, and alkyl amfocarboxylates.
[00161] Surfactants based on suitable amino acids in the practice of the disclosed technology include surfactants represented by the formula:
where R25 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) O-M +, - (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 R26C (O) -, where R26 is selected from an alkyl group Straight or branched C9 to C22, a straight or branched C9 to C22 alkenyl group. In one respect, M + is a cation selected from sodium, potassium, ammonium and triethanolamine (TEA).
[00162] 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 are not limited to the mono- and di-carboxylate salts (eg sodium, potassium, ammonium and TEA) of N-acylated glutamic acid, eg sodium cocoyl glutamate, sodium lauroyl glutamate, sodium myristoyl glutamate, sodium palmitoyl glutamate, sodium stearoyl glutamate, disodium cocoyl glutamate, sodium disea stearoyl glutamate, potassium cocoyl glutamate, potassium lauryl glutamate, and potassium myristo glutamate; the carboxylate salts (for example, sodium, potassium, ammonium and TEA) of N-acylated alanine, for example, sodium cocoyl alaninate, and TEA lauryl 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 TES) of N-acylated sarcosine, e.g. sodium lauroyl sarcosinate, sodium cocoyl sarcosinate, sodium myristyl sarcosinate, sodium oleoyl sarcosinate, and ammonium lauroyl sarcosinate; and mixtures of the previous surfactants.
[00163] Betaines and sultaines useful in the described technology are selected from alkyl betaines, alkylamino betaines, and alkylamido betaines, as well as the corresponding sulfobetaines (sultaines) represented by the formulas:
where R27 is a C7-C22 alkyl or alkenyl group, each R28, independently, is a C1-C4 alkyl group, R29 is a C1C5 alkylene group, or a substituted C1-C5 alkylene hydroxy group, n represents an integer of 2 to 6, A is a carboxylate or sulfonate group, and M is a cation that forms salt. In one aspect, R27 is a C11-C18 alkyl group or a C11-C18 alkenyl group. In one respect, R28 is methyl. In one aspect, R29 is methylene, ethylene or hydroxy propylene. In one aspect, n represents 3. In another aspect, M is selected from cations of sodium, potassium, magnesium, ammonium, and mono-, di- and triethanolamine.
[00164] Examples of suitable betaines include, but are not limited to, lauryl lauryl betaine, coconut betaine, oleyl betaine, hexadecyl dimethyl betaine, lauryl amidopropyl betaine, cocoamidopropyl betaine (CAPB), and cocamidopropyl hydroxysultin.
[00165] Alkylamfocarboxylates such as alkylamfoacetates and alkylamphopropionates (mono- and disubstituted carboxylates) can be represented by the formula:
where R27 is a C7-C22 alkyl or alkenyl group, R30 is -CH2C (O) O-M +, -CH2CH2C (O) O-M +, or -CH2CH (OH) CH2SO3-H +, R31 is hydrogen or -CH2C ( O) O-M +, and M is a cation selected from sodium, potassium, magnesium, ammonium, and mono-, di- and triethanolamine.
Exemplary alkylamfocarboxylates include, but are not limited to, sodium cocoamfoacetate, sodium lauroamfoacetate, sodium capriloamfoacetate, disodium cocoamfodiacetate, disodium lauroamfodiacetate, disodium caprylamphodihydrate, capriodamodihydrate, disodium caprylamphihydrate, disodium disodium, and disodium capriloamphodipropionate.
[00167] Non-limiting examples of non-ionic surfactants are disclosed in McCutcheon’s Detergents and Emulsifiers, North American edition, 1998, supra; and McCutcheon, Functional Materials, North American, supra; both of which are incorporated herein by reference in their entirety. Additional examples of non-ionic surfactants are described in US Patent No. 4,285,841, Barrat et al., And US Patent No. 4,284,532, Leikhim a et al., Both of which are incorporated herein by reference 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 radical containing varying degrees of ethoxylation and / or propoxylation (for example, 1 to about 50) ethoxy radicals and / or propoxy. Examples of some classes of nonionic surfactants that may be used include, but are not limited to, ethoxylated alkylphenols, ethoxylated and propoxylated fatty alcohols, methyl glucose polyethylene glycol ethers, ethylene oxide polyethylene glycol ethers, ethylene oxide block copolymers -propylene oxide, ethoxylated esters of fatty acids, condensation products of ethylene oxide with long chain amines or amides, condensation products of ethylene oxide with alcohols and mixtures thereof.
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 , dinonylphenol ethoxylates, dodecylphenol ethoxylates, terminal capping ethoxylates, amine ether derivatives, ethoxylated alkanolamides, ethylene glycol esters, fatty acid alkanolamides, fatty alcohol alkoxylates, lauryl alcohol ethoxylates, lauryl alcohol ethoxylates, ethoxylates, lauryl alcohol, ethoxylates, lauryl alcohol, ethoxylates nonylphenol ethoxylates, octylphenol ethoxylates, oleyl amine ethoxylates, random copolymer alkoxylates, sorbitan esters ethoxylates, stearic acid ethoxylates, tallow amine ethoxylates, tallow oil ethoxylates, ethoxylates and ethoxylates, ethoxylates and ethoxylates. , acetylenic diols, polyoxyethylene sorbitol and mixtures thereof. Several specific examples of suitable non-ionic surfactants include, but are not limited to, methyl Gluceth-10, glucose methyl distearate PEG-20, glucose methyl sesquistearate PEG-20, ceteth-8, ceteth-12, dodoxinol- 12, laureth-15, castor oil PEG-20, polysorbate 20, steareth-20, polyoxyethylene-10 of cetyl ether, polyoxyethylene-10 stearyl ether, polyoxyethylene-20 cetyl ether, polyoxyethylene-10 ether of oleyl ether, polyoxyethylene-20 of oleyl ether, an ethoxylated nonylphenol, ethoxylated octylphenol, ethoxylated dodecylphenol, or ethoxylated fatty alcohol (C6-C22), including from 3 to 20 ethylene oxide radicals, 20-polyoxyethylene glycolate iso-hexadecyl ether, lauryl polyoxyethylene-23, polyoxyethylene glyceryl stearate-20, methyl glucose ether PPG-10, methyl glucose ether PPG-20, polyoxyethylene sorbitan-20 monoesters, polyoxyethylene-80 castor oil, tridecyl ether polyoxyethylene-15, tridecyl ether of polyoxyethylene-6, laureth-2, laureth-3, laureth-4, castor oil PEG-3, dioleate PEG 600, dioleate PEG 400, poloxamers such as poloxamer 188, polysorbate 21, polysorbate 40, polysorbate 60, polysorbate 61, polysorbate 65, polysorbate 80, polysorbate 81, polysorbate 85, sorbitan caprilate, sorbitan cocoate, sorbitan diisostearate, sorbitan dioleate, sorbitan distearate, sorbitan fatty acid ester, sorbitan isostearate sorbitan, sorbitan oleate, sorbitan palmitate, sorbitan sesquiisostearate, sorbitan sesquioleate, sorbitan sesquiestearate, sorbitan stearate, sorbitan tri-isostearate, sorbitan trioleate, sorbitan triestearate or sorbitan triestearate or undecilenate.
[00169] Non-ionic alkyl glycoside surfactants can also be employed 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, US Patent Nos. 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, PLANTACARE®, and PLANTAPON®, all of which are available from Cognis Corporation of Ambler, Pennsylvania.
[00170] In another aspect, non-ionic surfactants include, but are not limited to, alkoxylated methyl glucosides, such as, for example, methyl Gluceth-10, methyl Gluceth-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® P10 and Glucam® P20, respectively; and hydrophobically modified alkoxylated methyl glucosides, such as methyl glucose dioleate PEG 120, methyl glucose trioleate PEG-120, and methyl glucose sesquiestearate, available from Lubrizol Advanced Materials, Inc., under the trade names , Glucamate® DOE-120, Glucamato ™ LT, and Glucamate SSE ™ -20, respectively, are also suitable. Other exemplary hydrophobically modified alkoxylated methyl glucosides are described in US Patent Nos. 6,573,375 and 6,727,357, the descriptions of which are incorporated herein by reference in their entirety.
[00171] Other useful non-ionic 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 derivatized / functionalized forms 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.
[00172] The amount of at least one surfactant (based on active weight) used in the deformation stress fluid formulation of the described technology ranges from about 1 to about 70% by weight based on the weight of the total fluid composition strain strain. In another aspect, the amount of at least one surfactant used in the formulation ranges from about 2 to about 50% by weight, or from about 3 to about 25% by weight. In yet another aspect, the amount of at least one surfactant employed in the strain strain fluid ranges from about 5 to about 22% by weight. In a further aspect, the amount of at least one surfactant used varies from about 6 to about 20% by weight. In still a further aspect, the amount of at least one surfactant is about 10, 12, 14, 16, and 18% by weight based on the total weight yield of the tension fluid.
[00173] In a modality of the technology described, the weight ratio (based on the active material) of anionic surfactant (non-ethoxylated and / or ethoxylated) to amphoteric surfactant can vary 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 an ethoxylated anionic surfactant is used in combination with a non-ethoxylated anionic surfactant and an amphoteric surfactant, the weight ratio (based on the active material) of ethoxylated anionic surfactant to non-ethoxylated anionic surfactant for amphoteric surfactant can vary from about 3 , 5: 3,5: 1 in one aspect to about 1: 1: 1 in another aspect.
[00174] In one embodiment, the strain strain value of the fluid is at least about 1mPa, or 0.1 Pa, in one aspect, to about 0.5 Pa, in one aspect, at least about 1 Pa in another aspect and at least about 1.5 Pa in an additional aspect. In another embodiment, the strain strain of the fluid 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 from 1 to about 3 Pa, in an additional aspect, and from about 1.5 to about 3.5 in yet another aspect.
[00175] Optionally, the deformation stress fluids of the described technology 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 sodium bromide calcium, as well as zinc halides, barium chloride and calcium nitrate, monovalent cation salts with monovalent anions, including alkali metal or ammonium halides, such as potassium chloride, sodium chloride, potassium iodide, sodium bromide and ammonium bromide, alkali metal or ammonium nitrates and mixtures thereof. The amount of electrolyte used will generally depend on the amount of the amphiphilic polymer incorporated, but it can be used at concentration levels 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.
[00176] The strain strain fluid must be easily pourable with a pseudoplasticity index of less than 0.5 at shear rates between 0.1 and 1 reciprocal second. The flow voltage fluid can have an optical transmission of at least 10%. In addition, or alternatively, the flow stress fluid may have the value of a nephelometric turbidity unit (NTU) of 50 or less, or 40 or less, or even 30 or 20 or less. The flow tension fluid of the described technology can be used in combination with a rheology modifier (thickener) to increase the yield value of a thickened liquid. In one aspect, the yield stress fluid of the described technology can be combined with a nonionic rheology modifier in which the rheology modifier when used alone does not have a sufficient yield stress value. Any rheology modifier is suitable, as long as it is soluble in water, stable and does not contain ionic or ionizable groups. Suitable rheology modifiers include, but are not limited to, natural gums (eg, polygalactomannan gums selected from fenogrego, cassia, locust bean, tara and guar gum), modified cellulose (eg ethylhexylethylcellulose (EHEC), hydroxybutylmethylcellulose (HBMC), hydroxyethylmethylcellulose (HEMC), hydroxypropylmethylcellulose (HPMC), methylcellulose (MC), hydroxyethylcellulose (HEC), hydroxypropylcellulose (HPC) and cetyl hydroxyethylcellulose); and mixtures of the same methylcellulose, polyethylene glycols (for example, 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, and from about 1 to about 15% by weight, in another aspect, and the from about 2 to about 10% by weight, in an additional aspect, based on the weight of the total weight of the composition.
[00177] Strain strain fluids of the technology described can be used in any application that requires strain strain properties. Deformation stress fluids can be used alone or in combination with other fluids to increase their stress values.
[00178] In one embodiment, the deformation stress fluids of the described technology 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 healthcare industries.
[00179] In the oil and gas industry, the strain strain fluids of the technology described can be used to increase the strain value of drilling and hydraulic fracture fluids, and can be used to suspend bore and structural piles fracture, such as, for example, sand, sintered bauxite, glass beads, ceramic materials, polystyrene beads, and the like.
[00180] In the personal care industry, the strain strain fluids of the technology described can be used to improve the strain strain properties of detergent compositions, hair and skin care compositions, as well as cosmetics, and can be used for suspend insoluble silicones, opacifiers and pearlescent agents (eg mica, coated mica), pigments, exfoliants, anti-dandruff agents, clay, swelling clay, laponite, gas bubbles, liposomes, micro-sponges, cosmetic beads, cosmetic microcapsules and flakes. The strain strain fluids of the described technology can stabilize these suspended materials for at least one month at 23 ° C in one aspect, at least 6 months in another aspect, and at least one year in an additional aspect.
[00181] Stable compositions maintain a smooth and acceptable rheology with good shearing properties without increasing or significantly reducing viscosity, without phase separation, for example, sedimentation or deforestation (rising to the surface), or loss of clarity during long periods of time, such as for at least one month at 45 ° C.
[00182] Exemplary bead components include, but are not limited to agar beads, alginate beads, jojoba beads, gelatin beads, Styrofoam ™ beads, polyacrylate, polymethylmethacrylate (PMMA), polyethylene beads, Unispheres cosmetic beads ™ and Unipearls ™ (Induchem USA, Inc., New York, NY), Lipocapsule ™, Liposphere ™ and Lipopearl ™ microcapsules (Lipo Technologies Inc., Vandalia, OH), and Confetti II ™ dermal release flakes (United-Guardian , Inc., Hauppauge, NY). Beads can be used as aesthetic materials or can be used to encapsulate benefit agents to protect them from the effects of deteriorating the environment or for optimal release, release and performance in the final product.
[00183] In one aspect, cosmetic beads vary 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.
[00184] In one aspect, microcapsules vary in size from about 0.5 to about 300 μm. In another aspect, the specific gravity difference between microcapsules and water is about +/- 0.01 to 0.5. Non-limiting examples of microcapsule beads are disclosed in US Patent No. 7,786,027, the description of which is incorporated herein by reference.
[00185] In one aspect of the described technology, the amount of particulate component and / or insoluble droplets can vary from about 0.1% to about 10% by weight based on the total weight of the composition.
[00186] While the weight ranges for the various components and ingredients that may be contained in the strain fluids of the described technology overlap have been expressed for selected modalities and aspects of the described technology, it should be readily apparent that the specific amount of each component in the compositions will be selected from its described range such that the amount of each component is adjusted so that the sum of all components in the composition will total 100 percent by weight. The amounts used can vary with the purpose and character of the desired product and can be readily determined by one skilled in the art of formulation and literature.
[00187] The technology described is illustrated by the following examples which are for illustrative purposes only and should not be considered as limiting the scope of the technology disclosed or the way in which it can be practiced. Unless specifically stated otherwise, parts and percentages are given by weight.
[00188] The following abbreviations and trade names are used in the examples. Abbreviations


[00189] The following examples illustrate the technology disclosed here. Example 1 (comparative) Monomer composition = EA / n-BA / HEMA / BEM (35/15/45/5) by weight.
[00190] An emulsion polymer was prepared as follows. A premix of the monomer was prepared by mixing 140 grams of DI water, 12.5 grams of 40% aqueous sodium alpha olefin sulfonate (AOS), 175 grams of (EA), 75 grams of (n-BA) , 225 grams of (HEMA) and 33.3 grams of (BEM). Primer A was prepared by mixing 3.57 grams of 70% t-butyl hydrogen peroxide (TBHP) in 40 grams of Dl water. Reducer A was prepared by dissolving 0.13 grams of erythorbic acid in 5 grams of Dl water. Reducer B was prepared by dissolving 2.5 grams of erythorbic acid in 100 grams of DI water. A 3-liter reactor was charged with 825 grams of DI water, 7.5 grams of 40% AOS and 15 grams of Selvol 502 from Sekisui, and was then heated to 70 ° C under a stirred nitrogen blanket proper. After keeping the reactor at 70 ° C for one hour, the reactor was cooled to 65 ° C, and then initiator A was then added to the reactor followed by the addition of reducer A. After about 1 minute, the monomer premix was provided to the reaction vessel over a period of 180 minutes. About 3 minutes after the start of the monomer premix dosage, reducer B was provided to the reactor over a period of 210 minutes. After feeding the reducer B, the reaction vessel temperature was maintained at 65 ° C for 60 minutes. The reactor was then cooled to 60 ° C. A solution of 1.96 grams of 70% TBHP and 0.13 grams of 40% AOS in 15 grams of DI water was added to the reactor. After 5 minutes, a solution of 1.27 grams of erythorbic acid in 15 grams of DI water was added to the reactor. The reactor was maintained at 60 ° C. After 30 minutes, a solution of 1.96 grams of 70% TBHP and 0.13 grams of 40% AOS in 15 grams of DI water was added to the reactor. After 5 minutes, a solution of 1.27 grams of erythorbic acid in 15 grams of DI water was added to the reactor. The reactor was maintained at 60 ° C for about 30 minutes. Then, the reactor was cooled to room temperature and filtered through a 100 micron cloth. The pH of the resulting emulsion was adjusted to 4 to 5 with ammonium hydroxide. The polymer product had a solids content of 29%, a viscosity of 14 cps, and a particle size of 111 nm. Example 2 (comparative) Monomer composition = EA / n-BA / HEMA / BEM (35 / 14.91 / 45/5 / 0.088) by weight.
[00191] An emulsion polymer was prepared as follows. A premix of the monomer was prepared by mixing 140 grams of DI water, 3.75 grams of 40% aqueous solution of alpha olefin sulfonate (AOS), 175 grams of (EA), 70.6 grams of (n- BA), 225 grams of (HEMA) and 33.3 grams of (BEM). Primer A was prepared by mixing 3.57 grams of 70% t-butyl hydrogen peroxide (TBHP) in 40 grams of Dl water. Reducer A was prepared by dissolving 0.13 grams of erythorbic acid in 5 grams of Dl water. Reducer B was prepared by dissolving 2.5 grams of erythorbic acid in 100 grams of DI water. A 3-liter reactor was charged with 800 grams of DI water, 10 grams of 40% AOS and 25 grams of Selvol 502 from Sekisui, and was then heated to 70 ° C under a nitrogen blanket with proper stirring. After maintaining the reactor at 70 ° C for one hour, initiator A was added to the reactor and followed by the addition of a reducer A. After about 1 minute, the monomer premix was provided to the reaction vessel at over a period of 180 minutes. About 3 minutes after starting the monomer premix dosage, reducer B was provided to the reactor over a period of 210 minutes. The reaction temperature was maintained at 65 ° C. At about 115 minutes after the monomer premix dosing, the premix dosing was interrupted for 10 minutes, and then 0.44 grams of 70% APE in 3.94 grams of n-BA was added to the monomer premix. After the 10-minute period, the premix dosage was restarted. After the reducer B charge was completed, the temperature of the reaction vessel was maintained at 65 ° C for 60 minutes. The reactor was then cooled to 60 ° C. A solution of 1.96 grams of 70% TBHP and 0.13 grams of 40% AOS in 15 grams of DI water was added to the reactor. After 5 minutes, a solution of 1.27 grams of erythorbic acid in 15 grams of DI water was added to the reactor. The reactor was maintained at 60 ° C. After 30 minutes, a solution of 1.96 grams of 70% TBHP and 0.13 grams of 40% AOS in 15 grams of DI water was added to the reactor. After 5 minutes, a solution of 1.27 grams of erythorbic acid in 15 grams of DI water was added to the reactor. The reactor was maintained at 60 ° C for about 30 minutes. Then, the reactor was cooled to room temperature and filtered through a 100 micron cloth. The pH of the resulting emulsion was adjusted to 4 to 5 with ammonium hydroxide. The polymer product had a solids content of 31.5%, a viscosity of 20 cps, and a particle size of 145 nm. Example 3 (Illustrative) Monomer composition = EA / n-BA / HEMA / BEM (35/15/45/5) by weight.
[00192] An emulsion polymer was prepared as follows. A monomer premix was prepared by mixing 140 grams of DI water, 5 g of E-Sperse RS-1618 reactive surfactant, 175 grams of (EA), 75 grams of (n-BA), 225 grams of (HEMA) and 33.3 grams of (WELL). Primer A was prepared by mixing 2.86 grams of 70% TBHP in 40 grams of Dl water. Reducer A was prepared by dissolving 0.13 grams of erythorbic acid in 5 grams of Dl water. Reducer B was prepared by dissolving 2.0 grams of erythorbic acid in 100 grams of DI water. A 3 liter reactor was loaded with 800 grams of DI water, 10 grams of 40% AOS and 25 grams of Selvol 502 from Sekisui. The reactor contents were heated to 70 ° C under a nitrogen blanket with adequate agitation. After the reactor was maintained at 70 ° C for one hour, initiator A was added to the reactor and followed by the addition of reducer A. After about 1 minute, the monomer premix was provided to the reaction vessel for a period 180 minutes. About 3 minutes after the start of the monomer premix dosage, reducer B was provided to the reactor over a period of 210 minutes. The reaction temperature was maintained at 65 ° C. After the load of reducer B was completed, the temperature of the reaction vessel was maintained at 65 ° C for 60 minutes. The reactor was then cooled to 60 ° C. A solution of 1.79 grams of 70% TBHP and 0.13 grams of 40% AOS in 15 grams of DI water was added to the reactor. After 5 minutes, a solution of 1.05 grams of erythorbic acid in 15 grams of DI water was added to the reactor. The reactor was maintained at 60 ° C. After 30 minutes, a solution of 1.79 grams of 70% TBHP and 0.13 grams of 40% AOS in 15 grams of deionized water was added to the reactor. After 5 minutes, a solution of 1.05 grams of erythorbic acid in 15 grams of DI water was added to the reactor. The reactor was maintained at 60 ° C for about 30 minutes. Then, the reactor was cooled to room temperature and filtered through a 100 micron cloth. The pH of the resulting emulsion was adjusted to 4 to 4 with ammonium hydroxide. The polymer product had a solids content of 30.4%, a viscosity of 21 cps, and a particle size of 119 nm. Example 4 (Illustrative) Monomer composition = EA / n-BA / HEMA / BEM (35/15/45/5) by weight.
[00193] An emulsion polymer was prepared in the same way as in Comparative Example 1, with the exception of 12.5 grams of 40% aqueous sodium alpha olefin sulfonate (AOS) solution, in the monomer mixture it was replaced with 5 g of E-Sperse RS-1618 reactive surfactant. The polymer product had a solids content of 30.85%, a viscosity of 19 cps, and a particle size of 99 nm. Example 5 (Illustrative) Monomer composition = EA / n-BA / HEMA / BEM / APE (35 / 14.91 / 45/5 / 0.088) by weight.
[00194] An emulsion polymer was prepared the same way as in Comparative Example 2, with the exception of 3.75 grams of 40% sodium alpha-olefin sulfonate (AOS), in aqueous solution to the monomer mixture was replaced by 5 g of E-Sperse RS-1618 reactive surfactant. The polymer product had a solids content of 30.8%, a viscosity of 24 cps and a particle size of 110 nm. Example 6 (comparative) Monomer composition = EA / n-BA / HEMA / BEM (35/15/45/5) by weight.
[00195] An emulsion polymer was prepared as follows. A monomer premix was prepared by mixing 140 grams of DI water, 16.67 grams of 30% aqueous solution of Polystep TSP-16S (from Stepan), 175 grams of ethyl acrylate (EA), 75 grams of acrylate n-butyl (nBA), 225 grams of 2-hydroxy ethyl acrylate (HEMA) and 33.3 grams of Sipomer BEM (MEC). Primer A was prepared by dissolving 5 grams of 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide] (Azo VA-086 from Wako) in 40 grams of Dl water. Primer B was prepared by dissolving 2.5 grams of Azo VA-086 in 100 grams of DI water. A 3 liter reactor was loaded with 800 grams of DI water, 5 grams of 40% AOS and 10 grams of Selvol 203 from Sekisui. The reactor contents were heated to 87 ° C under a nitrogen blanket with adequate agitation. After maintaining the reactor at 87 ° C for one hour, initiator A was added to the reactor. After about 1 minute, the monomer premix was provided to the reaction vessel over a period of 120 minutes. About 3 minutes after the start of the dosage of the monomer premix, initiator B was provided to the reactor over a period of 150 minutes. The reaction temperature was maintained at 87 ° C. After initiator B feeding was completed, the temperature of the reaction vessel was maintained at 87 ° C for 60 minutes. The reactor was then cooled to 49 ° C. A solution of 0.61 grams of 70% TBHP and 0.29 grams of 40% AOS in 15 grams of DI water was added to the reactor. After 5 minutes, a solution of 0.59 grams of erythorbic acid in 15 grams of DI water was added to the reactor. The reactor was maintained at 49 ° C. After 30 minutes, a solution of 0.69 grams of 70% TBHP and 0.29 grams of 40% AOS in 15 grams of deionized water was added to the reactor. After 5 minutes, a solution of 0.59 grams of erythorbic acid in 15 grams of DI water was added to the reactor. The reactor was maintained at 49 ° C for about 30 minutes. The reactor was cooled to room temperature and filtered through a 100 micron cloth. The pH of the resulting emulsion was adjusted from 4 to 5 with ammonium hydroxide. The polymer had a solids content of 29.8%, a viscosity of 18 cps, and a particle size of 84 nm. Example 7 (comparative) Monomer composition = EA / n-BA / HEMA / BEM (35/15/45/5) by weight.
[00196] An emulsion polymer was prepared in the same manner as in Comparative Example 6, except 16.67 grams of 30% Polystep TSP-16S aqueous solution in the monomer mixture was replaced by 5.56 grams of E-Sperse RS -1596 to 90%. The polymer product had a solids content of 30.7%, a viscosity of 28 cps and a particle size of 87 nm. Example 8 (comparative) Monomer composition = EA / n-BA / HEMA / BEM (35/15/45/5) by weight.
[00197] An emulsion polymer was prepared in the same manner as in Comparative Example 6, except 16.67 grams of 30% Polystep TSP-16S aqueous solution in the monomer mixture was replaced by 16.67 grams of E-Sperse RS -1616 to 30%. The polymer product had a solids content of 31.7%, a viscosity of 14 cps and a particle size of 107 nm. Example 9 (Illustrative) Monomer composition = EA / n-BA / HEMA / BEM (35/15/45/5) by weight.
[00198] An emulsion polymer was prepared in the same way as in Comparative Example 6, except 16.67 grams of 30% Polystep TSP-16S aqueous solution in the monomer mixture was replaced by 5 grams of E-Sperse RS-1617 to 100%. The polymer product had a solids content of 31.4%, a viscosity of 14 cps and a particle size of 105 nm. Example 10 (Illustrative) Monomer composition = EA / n-BA / HEMA / BEM (35/15/45/5) by weight.
[00199] An emulsion polymer was prepared in the same way as in Comparative Example 6, except 16.67 grams of 30% Polystep TSP-16S aqueous solution in the monomer mixture was replaced by 10 grams of E-Sperse aqueous solution 50% RS-1684. The polymer product had a solids content of 30%, a viscosity of 29 cps and a particle size of 93 nm. Example 11 (Illustrative) Monomer composition = 30/20/45/5 (30/20/45/5) by weight.
[00200] An emulsion polymer was prepared in the same way as in Comparative Example 6, except 16.67 grams of 30% Polystep TSP-16S aqueous solution in the monomer mixture was replaced by 5 grams of E-Sperse RS-1618 at 100% and monomer compositions were changed to 30 EA / 20 b-BA / 45 HEMA / 5 BEM instead of 35 EA / 15 n-BA / 45 HEMA / 5 BEM. The polymer product had a solids content of 30.8%, a viscosity of 26 cps and a particle size of 83 nm. Example 12 (Illustrative) Monomer composition = EA / n-BA / HEMA / BEM (25/25/45/5) by weight.
[00201] An emulsion polymer was prepared in the same way as in Comparative Example 6, except 16.67 grams of 30% Polystep TSP-16S aqueous solution in the monomer mixture was replaced by 5 grams of E-Sperse RS-1618 at 100% and monomer compositions were changed to EA / 25 n-BA / 45 HEMA / 5 BEM instead of 35 EA / 15 n-BA / 45 HEMA / 5 BEM. The polymer product had a solids content of 30.9%, a viscosity of 39 cps and a particle size of 78 nm. Example 13 (Illustrative) Monomer composition = EA / n-BA / HEMA / BEM (35/20/40/5) by weight.
[00202] An emulsion polymer was prepared in the same manner as in Comparative Example 6, except 16.67 grams of 30% Polystep TSP-16S aqueous solution in the monomer mixture was replaced by 5 grams of E-Sperse RS-1618 at 100% and monomer compositions were changed to 35 EA / 20n-BA / 45 HEMA / 5 BEM instead of 35 EA / 15 n-BA / 45 HEMA / 5 BEM. The polymer product had a solids content of 31.4%, a viscosity of 42 cps and a particle size of 87 nm. Example 14 (Illustrative) Monomer composition = EA / n-BA / BEM / HEMA / AA (35/15/5/43/2) by weight.
[00203] An emulsion polymer was prepared as follows. A monomer premix was prepared by mixing 70 grams of DI water, 2.5 grams of E-Sperse RS-1618, 87.5 grams of ethyl acrylate (EA), 37.5 grams of n-butyl acrylate ( n-BA), 16.67 grams of ethoxylated behenyl methacrylate (Sipomer BEM), 107.5 grams of 2-hydroxyl ethyl methacrylate (HEMA), and 5 grams of acrylic acid (AA). Primer # 1 was made by dispersing 2.5 g of VA-086 in 20 grams of Dl water. Primer # 2 was prepared by dissolving 1.25 grams of VA-086 in 50 grams of Dl water. A 1-liter reactor vessel was charged with 400 grams of DI water, 2.5 grams of 40% AOS and 5 grams of Selvol 203, and then heated to 87 ° C under a blanket of nitrogen and adequate stirring. First, primer # 1 was added to the reaction vessel. The monomer premix was then provided to the reaction vessel for a period of 120 minutes; while at the same time, primer # 2 was provided to the reaction vessel over a period of 150 minutes. After completing the monomer premix feed, 16.5 grams of DI water was added to the drip funnel, which maintained the monomer premix to expel residual monomers in the reaction mixture. Upon completion of the primer # 2 feed, the reaction vessel temperature was maintained at 87 ° C for 60 minutes. The reaction vessel was then cooled to 49 ° C. A solution of 0.3 grams of 70% TBHP and 0.14 grams of 40% AOS in 7.5 grams of DI water was added to the reaction vessel. After 5 minutes, a solution of 0.3 grams of erythorbic acid in 7.5 grams of DI water was added to the reaction vessel. After 30 minutes, another solution of 0.3 grams of 70% TBHP and 0.14 grams of 40% AOS in 7.5 grams of DI water was added to the reaction vessel. A solution of 0.3 grams of erythorbic acid in 7.5 grams of DI water was then added to the reaction vessel after 5 minutes. The reaction vessel was maintained at 60 ° C for an additional 30 minutes. The reaction vessel was cooled to room temperature and filtered through a 100 micron cloth. The pH of the resulting emulsion was adjusted to 3.5 to 4.5 with 28% ammonium hydroxide. The resulting polymer latex had a solids level of 30.7%, and a particle size of 113 nm. Example 15 (illustrative) Monomer composition = EA / n-BA / BEM / HEMA / AMD (35/15/5/43/2) by weight.
[00204] An emulsion polymer was prepared as follows. A monomer premix was prepared by mixing 70 grams of DI water, 2.5 grams of E-Sperse RS-1618, 87.5 grams of ethyl acrylate (EA), 37.5 grams of n-butyl acrylate ( n-BA), 16.67 grams of ethoxylated behenyl methacrylate (Sipomer BEM), 107.5 grams of 2-hydroxyl ethyl methacrylate (HEMA), and 10 grams of 50% acrylamide (AMD). Primer # 1 was made by dispersing 2.5 g of VA-086 in 20 grams of Dl water. Primer # 2 was prepared by dissolving 1.25 grams of VA-086 in 50 grams of Dl water. A 1 liter reactor vessel was loaded with 400 grams of DI water, 2.5 grams of 40% AOS and 5 grams of Selvol 203. The contents of the vessel were heated to 87 ° C under a blanket of nitrogen and stirring proper. First, primer # 1 was added to the reaction vessel. The monomer premix was then provided to the reaction vessel for a period of 120 minutes; while at the same time, primer # 2 was provided to the reaction vessel over a period of 150 minutes. Upon completion of the monomer feed premix, 16.5 grams of DI water was added to the drip funnel, which maintained the monomer premix to expel the residual monomers. Upon completion of the initiator # 2 feed, the temperature of the reaction vessel was maintained at 87 ° C for 60 minutes. The reaction vessel was then cooled to 49 ° C. A solution of 0.3 grams of 70% TBHP and 0.14 grams of 40% AOS in 7.5 grams of DI water was added to the reaction vessel. After 5 minutes, a solution of 0.3 grams of erythorbic acid in 7.5 grams of DI water was added to the reaction vessel. After 30 minutes, another solution of 0.3 grams of 70% TBHP and 0.14 grams of 40% AOS in 7.5 grams of DI water was added to the reaction vessel. A solution of 0.3 grams of erythorbic acid in 7.5 grams of DI water was then added to the reaction vessel after 5 minutes. The reaction vessel was maintained at 60 ° C for an additional 30 minutes. Then, the reaction vessel was cooled to room temperature and filtered through a 100 micron cloth. The pH of the resulting emulsion was adjusted to 3.5 to 4.5 with 28% ammonium hydroxide. The resulting polymer latex had a solids level of 30.4%, and a particle size of 90.4 nm. Example 16 (Illustrative) Monomer composition = EA / n-BA / BEM / HEMA / MAMD (35/15/5/43/2) by weight.
[00205] An emulsion polymer was prepared as follows. A monomer premix was prepared by mixing 70 grams of DI water, 2.5 grams of E-Sperse-1618, 87.5 grams of ethyl acrylate (EA), 37.5 grams of n-butyl acrylate (n -BA), 16.67 grams of (BEM), 107.5 grams of (HEMA), and 20 grams of 25% methacrylamide (MAMD). Primer # 1 was made by dispersing 2.5 g of VA-086 in 20 grams of Dl water. Primer # 2 was prepared by dissolving 1.25 grams of VA-086 in 50 grams of Dl water. A 1-liter reactor vessel was charged with 400 grams of DI water, 2.5 grams of 40% AOS and 5 grams of Selvol 203, and then heated to 87 ° C under a blanket of nitrogen and adequate stirring. First, primer # 1 was added to the reaction vessel. The monomer premix was then provided to the reaction vessel for a period of 120 minutes; while at the same time, primer # 2 was provided to the reaction vessel over a period of 150 minutes. Upon completion of the monomer feed premix, 16.5 grams of DI water was added to the drip funnel, which maintained the monomer premix to expel the residual monomers. Upon completion of the initiator # 2 feed, the temperature of the reaction vessel was maintained at 87 ° C for 60 minutes. The reaction vessel was then cooled to 49 ° C. A solution of 0.3 grams of 70% TBHP and 0.14 grams of 40% AOS in 7.5 grams of DI water was added to the reaction vessel. After 5 minutes, a solution of 0.3 grams of erythorbic acid in 7.5 grams of DI water was added to the reaction vessel. After 30 minutes, another solution of 0.3 grams of 70% TBHP and 0.14 grams of 40% AOS in 7.5 grams of DI water was added to the reaction vessel. A solution of 0.3 grams of erythorbic acid in 7.5 grams of DI water was added to the reaction vessel after 5 minutes. The reaction vessel was maintained at 60 ° C for an additional 30 minutes. The reaction vessel was cooled to room temperature and filtered through a 100 micron cloth. The pH of the resulting emulsion was adjusted to 3.5 to 4.5 with 28% ammonium hydroxide. The resulting polymer latex had a solids level of 26.2%, and a particle size of 100 nm. Example 17 (Illustrative) Monomer composition = EA / n-BA / BEM / HEMA / BEM (20.5 / 27.5 / 45/7) by weight.
[00206] An emulsion polymer was prepared as follows. A monomer premix was prepared by mixing 140 grams of DI water, 5 g of E-Sperse RS-1618 reactive surfactant, 102.5 grams of (EA), 137.5 grams of (n-BA), 175 grams of (HEMA), 46.67 grams of (BEM). Primer A was prepared by dissolving 5 grams of Azo VA-086 in 40 grams of Dl water. Primer B was prepared by dissolving 2.5 grams of Azo VA-086 in 100 grams of DI water. A 3-liter reactor was charged with 800 grams of DI water, 5 grams of 40% alpha alpha olefin (AOS) sulfonate and 10 grams of Selvol 203, and then the contents were heated to 87 ° C under a mantle of nitrogen with agitation. After maintaining the reactor at 87 ° C for one hour, initiator A was then added to the reactor. After about 2 to 3 minutes, the monomer premix was dosed into the reaction vessel over a period of 120 minutes. About 1 minute after the start of the measurement of the monomer premix, initiator B was dosed into the reactor over a period of 150 minutes. The reaction temperature was maintained at 87 ° C. Upon completion of initiator B feed, the temperature of the reaction vessel was maintained at 87 ° C for 60 minutes. The reactor was then cooled to 49 ° C. A solution of 0.61 grams of 70% TBHP and 0.29 grams of 40% AOS in 15 grams of DI water was added to the reactor. After 5 minutes, a solution of 0.59 grams of erythorbic acid in 15 grams of DI water was added to the reactor. The reactor was maintained at 49 ° C. After 30 minutes, a solution of 0.69 grams of 70% TBHP and 0.29 grams of 40% AOS in 15 grams of DI water was added to the reactor. After 5 minutes, a solution of 0.59 grams of erythorbic acid in 15 grams of DI water was added to the reactor. The reactor was maintained at 49 ° C for about 30 minutes. The reactor contents were cooled to room temperature and filtered through a 100 micron cloth filter. The pH of the resulting emulsion was adjusted to 4 to 5 with ammonium hydroxide. The polymer was diluted with 340 grams of DI water to achieve a solids content of 25.1%, a viscosity of 13 cps, and a particle size of 82 nm. Example 18 (Illustrative) Monomer composition = n-VP / EA / BA / VAC / HEMA (20/15/20/20/25) by weight.
[00207] An emulsion polymer was prepared as follows. A premix of the monomers was prepared by mixing 70 grams of DI water, 2.5 grams of E-Sperse ™ RS-1618, 50 grams of (n-VP), 37.5 grams of (EA), 50 grams of ( n-BA), 50 grams of vinyl acetate (VAc), and 62.5 grams of (HEMA). Primer 1 was prepared by mixing 1.07 grams to 70% of 70% TBHP (Alfa Aesar) in 20 grams of Dl water. Reducer 2 was prepared by dissolving 0.83 grams of erythorbic acid in 50 grams of Dl water. A one-liter reaction vessel was loaded with 400 grams of DI water, 2.5 grams of 40% AOS and 12.5 grams of SelvolTM 502, and was then heated to 65 ° C under a blanket of nitrogen and a gentle shake. Primer 1 was added to the reaction vessel. After about 1 minute, the monomer premix was dosed into the reaction vessel over a period of 120 minutes; while at the same time Reducer 2 was dosed into the reaction vessel over a period of 150 minutes. After completing the monomer pre-mix feed, 16.5 grams of DI water was added to wash the residual monomers from the pre-mix vessel into the reaction vessel. After completing the Reducer 2 feeding, the temperature of the reaction vessel was maintained at 65 ° C for 60 minutes. The reaction vessel was then cooled to 50 ° C. A solution of 0.3 grams of 70% TBHP and 7.5 grams of DI water was added to the reaction vessel. After 5 minutes, a solution of 0.29 grams of erythorbic acid in 7.5 grams of DI water was added to the reaction vessel. After 30 minutes, a solution of 0.32 grams of 70% TBHP and 7.5 grams of deionized water was added to the reaction vessel. After 5 minutes, a solution of 0.29 grams of erythorbic acid in 7.5 grams of DI water was added to the reaction vessel. The reaction vessel was maintained at 50 ° C for about 30 minutes. Then, the reaction vessel was cooled to room temperature (22 ° C) and filtered through a 100 micron cloth. The resulting polymer latex had a solids level of 30.8%, and a particle size of 100 nm (Nicomp 380 nanoparticle size analyzer). Example 19 (Illustrative) Monomer composition = EA / n-BA / HEMA / n-VP / CSEM (23/20/35/20/2) by weight.
[00208] An emulsion polymer was prepared as follows. A premix of the monomers was prepared by mixing 140 grams of DI water, 5 g of E-Sperse ™ RS-1618, 115 grams of (EA), 100 grams of (n-BA), 175 grams of (HEMA), 12 , 5 grams (CSEM), and 100 g (n-VP). Primer A was prepared by dissolving 4 grams of Azo VA-086 in 40 grams of Dl water. Primer B was prepared by dissolving 0.75 grams of Azo VA-086 in 100 grams of DI water. A 3-liter reactor was charged with 800 grams of DI water, 5 g of 40% AOS and 20 grams of SelvolTM 203, and was then heated to 87 ° C under a gently stirred nitrogen blanket. After the reactor was maintained at 87 ° C for one hour, initiator A was then added to the reactor. After about 1 minute, the monomer premix was dosed into the reaction vessel for more than 120 minutes. About 3 minutes after the introduction of the monomer premix, initiator B was dosed into the reactor over a period of 150 minutes. The reaction temperature was maintained at 87 ° C. After initiator B feeding was completed, the temperature of the reaction vessel was maintained at 87 ° C for an additional 60 minutes. The reactor was then cooled to 49 ° C. A solution of 0.61 grams of 70% t-BHP (Alpha Aesar) and 0.29 grams of 40% AOS in 15 grams of deionized water was added to the reactor. After 5 minutes, a solution of 0.59 grams of erythorbic acid in 15 grams of DI water was added to the reactor. The reactor was maintained at 49 ° C. After 30 minutes, a solution of 0.69 grams of 70% t-BHP and 0.29 grams of 40% AOS in 15 grams of DI water was added to the reactor. After 5 minutes, a solution of 0.59 grams of erythorbic acid in 15 grams of DI water was added to the reactor. The reactor was maintained at 49 ° C for about 30 minutes. The reactor was then cooled to room temperature (22 ° C) and filtered through a 100 micron cloth. The pH of the resulting emulsion was adjusted to 4.5 with 10% ammonium hydroxide in water. The polymer emulsion had a solids content of 30.9%, a Brookfield viscosity of 36 cps, and a particle size of 113 nm (Nicomp 380 nanoparticle size analyzer). Examples 20 and 21
[00209] The following two Examples (20 and 21) compare the effectiveness of a polymer prepared according to the present technology of using a reactive surfactant containing two allyl groups in comparison with a polymer containing no crosslinking agent in the creation of fluids strain strain with high optical transparency in surfactants.
[00210] Samples containing 2.5% by weight of polymer solids, 14% by weight of SLES2 and 3% by weight of CAPB in Dl water were prepared using each of the polymers in Examples 1 and 4. The strain strain of these samples was determined by oscillatory shear measurements on a tension controlled rheometer (rheometer AR2000EX instruments TA, New Castle, DE) with cone and plate geometry (60 mm cone with a cone angle of 2 degrees and 56 μm aperture ) at 25 ° C. Oscillatory measurements are carried out at a frequency of 1 Hz. The elastic and viscous modules (G 'and G ", respectively) are obtained as a function of the increase in stress amplitude. In cases where the swollen polymer particles have created a network jammed, G 'is greater than G "at low voltage amplitudes, but decreases at greater amplitudes that cross G" because of the network break. The voltage corresponding to the crossing of G' and G "is noted as the voltage of deformation. The optical clarity of the samples (expressed in terms of the nephelometric turbidity unit (NTU)) was measured using a laboratory turbidimeter (HF Scientific Micro 100 Laboratory Turbidimeter, Fort Myers, FL). The results of these measurements are shown in Table 1. TABLE 1

[00211] The technology provides a sample with the improved strain strain and acceptable optical clarity. The sample was prepared using the comparative polymer (without crosslinking) has a high optical clarity, but does not have a strain strain. Examples 22 to 24
[00212] The following examples (22 to 24) compare the effectiveness of polymers prepared according to the present technology using an amphiphilic crosslinking agent containing two allyl groups, or a combination of an amphiphilic crosslinking agent containing two allyl groups and a conventional crosslinking agent compared to a polymer prepared using a conventional crosslinking agent only in terms of creating fluids with strain strain with high optical clarity in surfactants.
[00213] Samples containing 2.5% by weight of polymer solids, 14% by weight of SLES2 and 3% by weight of CAPB in Dl water were prepared using each of the polymers of Examples 2, 3 and 5. The tension of strain and optical clarity of these samples were measured using the same procedures as described in Examples 20 and 21. The results are shown in Table 2.

[00214] The technology provides a desirable combination of strain strain and optical clarity (lower NTU) compared to the comparative example. Examples 25 to 32
[00215] The following examples (25 to 32) compare the effectiveness of polymers prepared according to the present technology using an amphiphilic crosslinking agent containing two allyl groups against polymers prepared using amphiphilic crosslinking agents containing both one and only an allyl group or amphiphilic agents without cross-linking groups. Samples containing 2.5% by weight of polymer, 14% by weight of SELS2 and 3% by weight of CAPB in Dl water were prepared and the strain strain and optical clarity were determined using the techniques described in examples 20 and 21. TABLE 3


[00216] Current technology provides examples that show both strain strain and optical clarity. In contrast, control samples have optical clarity (low NTU), but do not have a strain strain. Examples 33 to 35
[00217] Additional samples containing 2.5% by weight of polymer, 14% by weight of SLES2 and 3% by weight of CAPB were prepared (Examples 33 to 35) and the strain strain and optical clarity were determined by the methods described previously. The results are shown in Table 4. TABLE 4

[00218] Again, the present technology provides samples that have the combined properties of strain strain and good optical clarity.
[00219] Each of the aforementioned documents is hereby incorporated by reference, including any previous requests, whether or not listed above, whose priority is claimed. The mention of any document is not an admission that such a document qualifies as prior art or constitutes the general knowledge of the person skilled in the art in any jurisdiction. Except in the examples, or where otherwise explicitly indicated, all numerical quantities in this description specifying quantities of materials, reaction conditions, molecular weights, number of carbon atoms and the like, are to be understood as modified by the word "about" . It is to be understood that the quantity, range and ratios of the upper and lower limits set out in this document can be combined independently. Likewise, the ranges and quantities for each element of the technology described can be used in conjunction with ranges or quantities for any of the other elements.
[00220] As used herein, the transition term "comprising", which is synonymous with "including", "containing", or "characterized by", is inclusive or open and does not exclude elements or stages of the methods not recited additional. However, in each recitation of "comprising" here, it is intended that the term also encompasses, as alternative modalities, the phrases "consisting essentially of" and "consists of", where "consists of" excludes any element or stage unspecified and "consisting essentially of" allows the inclusion of additional non-recited elements or steps that do not materially affect the essential or basic and new characteristics of the composition or method in question.
[00221] While certain representative modalities and details have been shown for the purpose of illustrating the technology of the object, it will be evident to those skilled in the art that various changes and modifications can be made without departing from the scope of the revealed technology of the object. In this regard, the scope of the disclosed technology is only to be limited by the following claims.

权利要求:
Claims (10)
[0001]
1. Composition of cross-linked nonionic amphiphilic rheology modifying polymer, characterized by the fact that said polymer is polymerized from a monomer composition comprising: a) from 20 to 60% by weight of at least one (met ) C1-C4 hydroxyalkyl acrylate; b) from 10 to 70% by weight of at least one C1-C12 alkyl (meth) acrylate or from 10 to 70% by weight of at least one C1-C5 alkyl (meth) acrylate; c) from 0, 1, 5 or 15 to 40% by weight of at least one vinyl ester of a C1-C10 carboxylic acid; d) 0, 1, 5 or 15 to 30% by weight of a lactam vinyl (for example, vinylpyrrolidone); e) from 0.1, 1, 5, or 7 to 15% by weight of at least one associative and / or semi-hydrophobic monomer (where all percentages by weight of monomers are based on the weight of the total monomers); and f) from 0.01 to 5% by weight in one aspect, from 0.1 to 3% by weight in another aspect, and from 0.5 to 1% in another aspect of at least one crosslinking agent (based on in the dry weight of the polymer) selected from an amphiphilic crosslinking agent or a combination of an amphiphilic crosslinking agent and said conventional crosslinking agent; g) or wherein said polymer is polymerized from a monomer composition comprising: a) from 20 to 60% by weight of at least one C1-C4 hydroxyalkyl (meth) acrylate; b) 10 to 30% by weight of ethyl acrylate; c) from 10 to 35% by weight of butyl acrylate; d) from 0, 1, 5 or 15 to 25% by weight of a vinyl ester of a carboxylic acid selected from vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, and vinyl valerate; e) from 0, 1 or 15 to 30% by weight of vinylpyrrolidone; f) 0.1, 1, 5 or 7 to 15% by weight of at least one associative monomer and / or semi-hydrophobic monomer (where all percentages by weight of monomers are based on the weight of the total monomers); and g) from 0.01 to 5% by weight in one aspect, from 0.1 to 3% by weight in another aspect, and from 0.5 to 1% by weight in an additional aspect of at least one crosslinking agent ( based on the dry weight of the polymer) selected from an amphiphilic crosslinking agent or a combination of an amphiphilic crosslinking agent and said conventional crosslinking agent; h) or wherein said polymer is polymerized from a monomer composition comprising: a) from 20 to 50% by weight of hydroxyethyl methacrylate; b) 10 to 30% by weight of ethyl acrylate; c) 10 to 30% by weight of butyl acrylate; d) from 0, 1, or 15 to 25% by weight of vinylpyrrolidone; e) from 0 to 15 or 25% by weight of vinyl acetate; f) 0.1, 1, 5 or 7 to 10% by weight of at least one associative and / or semi-hydrophobic monomer (where all percentages by weight of monomers are based on the weight of the total monomers); and g) from 0.01 to 5% by weight in one aspect, from 0.1 to 3% by weight in another aspect, and from 0.5 to 1% by weight in an additional aspect of at least one crosslinking agent ( based on the dry weight of the polymer) selected from an amphiphilic crosslinking agent or a combination of an amphiphilic crosslinking agent and said conventional crosslinking agent; h) or wherein said polymer is polymerized from a monomer composition comprising: a) from 20 to 50% by weight of hydroxyethyl methacrylate; b) from 10 to 40% by weight of ethyl acrylate; c) 10 to 20% by weight of butyl acrylate; d) 0.1 to 10% by weight of at least one associative and / or semi-hydrophobic monomer (where all percentages of the monomer by weight are based on the total weight of the monomers); e) from 0.01 to 5% by weight in one aspect, from 0.1 to 3% by weight in another aspect, and from 0.5 to 1% by weight in an additional aspect of at least one crosslinking agent ( based on the dry weight of the polymer) selected from an amphiphilic crosslinking agent or a combination of an amphiphilic crosslinking agent and said conventional crosslinking agent; - or wherein said polymer is polymerized from a monomer composition comprising: a) from 20 to 50% by weight of hydroxyethyl methacrylate; b) 10 to 30% by weight of ethyl acrylate; c) 10 to 30% by weight of butyl acrylate; d) from 1 to 10% by weight of at least one associative and / or semi-hydrophobic monomer (where all percentages by weight of monomers are based on the weight of the total monomers); ee) from 0.01 to 5% by weight in one aspect, from 0.1 to 3% by weight in another aspect, and from 0.5 to 1% by weight in an additional aspect of at least one crosslinking agent ( based on the dry weight of the polymer) selected from an amphiphilic crosslinking agent or a combination of an amphiphilic crosslinking agent and said conventional crosslinking agent; - or wherein said polymer is polymerized from a monomer composition comprising: a) from 20 to 40% by weight of hydroxyethyl methacrylate; b) 10 to 30% by weight of ethyl acrylate; c) 10 to 30% by weight of butyl acrylate; d) from 15 to 25% by weight of vinylpyrrolidone; e) from 1 to 5% by weight of at least one associative and / or semi-hydrophobic monomer (where all percentages by weight of monomers are based on the weight of the total monomers); and f) from 0.01 to 5% by weight in one aspect, from 0.1 to 3% by weight in another aspect, and from 0.5 to 1% by weight in an additional aspect of at least one crosslinking agent ( based on the dry weight of the polymer) selected from an amphiphilic crosslinking agent or a combination of an amphiphilic crosslinking agent and said conventional crosslinking agent; wherein said amphiphilic crosslinking agent is selected from a compound of formula (III):
[0002]
2. Fluid strain strain, characterized by the fact that it comprises (A) water; (B) 0.1 to 5% by weight of at least one nonionic amphiphilic polymer as defined in claim 1; and (C) from 1 to 70% by weight based on the total weight of the strain strain fluid of at least one surfactant, in which at least one surfactant is selected from anionic, cationic, amphoteric, non-ionic or mixtures thereof.
[0003]
3. Composition according to claim 2, characterized by the fact that at least one surfactant is selected from an anionic surfactant and an amphoteric surfactant.
[0004]
Composition according to claim 2 or 3, characterized by the fact that the concentration of surfactant is less than 25% by weight (active), based on the weight of the strain strain fluid, preferably in which the concentration of surfactant ranges from 6 to 20% by weight (active material), based on the weight of the total composition.
[0005]
5. Composition according to claim 3, characterized by the fact that the ratio of anionic surfactant to amphoteric surfactant (active material) is 10: 1 to 2: 1 in one aspect, and 9: 1, 8: 1, 7 : 1, 6: 1, 5: 1, 4,5: 1, 4: 1, or 3: 1 in another aspect.
[0006]
Composition according to any one of claims 2 to 5, characterized in that it additionally comprises an electrolyte, preferably wherein said electrolyte is selected from potassium pyrophosphate, potassium tripolyphosphate, sodium or potassium citrate, chloride calcium and calcium bromide, zinc halide, barium nitrate, calcium chloride, potassium chloride, sodium chloride, potassium iodide, sodium bromide and ammonium bromide, alkali metal or ammonium nitrates and mixtures thereof , more preferably in that the amount of the electrolyte ranges from 0.1 to 4% by weight, based on the weight of the total composition.
[0007]
Composition according to any one of claims 2 to 6, characterized in that it additionally comprises an insoluble material, a particulate material or combinations thereof, preferably wherein said particulate material is selected from mica, coated mica, pigments, exfoliants, anti-dandruff agents, clay, intumescent clay, laponite, micro-sponges, cosmetic spheres, microcapsules, flakes or mixtures thereof.
[0008]
8. Drilling fluid for use in the extraction of underground formations, characterized by the fact that it comprises a strain strain fluid as defined in any of claims 2 to 7.
[0009]
9. Hydraulic fracture fluid for use in underground formations, characterized in that it comprises a strain strain fluid as defined in any of claims 2 to 7.
[0010]
10. Hydraulic fracturing fluid according to claim 9, characterized in that it additionally comprises a structuring agent.

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优先权:

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申请号 | 申请日 | 专利标题

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US201361917069P| true| 2013-12-17|2013-12-17|

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US61/917,069|2013-12-17|

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PCT/US2014/070769|WO2015095286A1|2013-12-17|2014-12-17|Surfactant responsive emulsion polymerization micro-gels|

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