AQUEOUS VISCOELASTIC COMPOSITION AND METHOD FOR FRACTURING A ROCK FORMATION

专利摘要:
a viscoelastic composition is provided, comprising at least one viscoelastic surfactant, and at least one hydrophobically modified polymer, which is formed from the polymerization of ethylenically unsaturated monomers; has a weight average molecular weight of 1,000 to 100,000 da; and at a level of at least 0.1 mol%, based on the amount of monomeric units in the polymer, contains monomeric units, each covalently attached to a pendant, optionally alkoxylated hydrocarbyl group having from 6 to 40 carbon atoms, the said pendant, optionally alkoxylated hydrocarbyl group being connected to the backbone of said hydrophobically modified polymer through a linking group that does not contain ester.
公开号:BR112013014234B1
申请号:R112013014234-0
申请日:2011-12-15
公开日:2021-06-22
发明作者:Qingwen Wendy Yuan-Huffman；Klin A. Rodrigues；Jian Zhou；Stuart Peter Robert Holt；Elliot Isaac Band
申请人:Akzo Nobel Chemicals International B.V.；
IPC主号:

专利说明:

FIELD OF THE INVENTION
[001] The present invention relates to a viscoelastic composition comprising at least one viscoelastic surfactant, and at least one hydrophobically modified polymer, and the use of such viscoelastic compositions. HISTORY OF THE INVENTION
[002] For several applications, it is desired to use liquid compositions with viscoelastic properties. Such compositions, for example, can be used to stimulate oil wells, where impeded flow paths lead to insufficient hydrocarbon production, a technique known as (hydraulic) fracturing, and the specialized fluids used in said technique are called fluids. of fracturing. For such a fracturing process, compositions are typically injected through the well into the formation at sufficient pressures to create fractures in the rocks of the formation, thus creating channels through which hydrocarbons can more readily flow into the well.
[003] Ideally, the fracturing fluids should transmit a minimum pressure drop in the pipe within the well during positioning, and have an adequate viscosity to load the proppant material that prevents the fracture from closing. Furthermore, said fracturing fluids should have a minimum leakage rate to prevent the fluid from migrating into the formation rocks, so that, remarkably, the fracture can be created and propagated. Said fracturing fluid should also degrade so as not to leave residual material that could prevent hydrocarbons from flowing into the well.
[004] The first fracturing fluids were constituted of viscous oil or gel, however, more recently, aqueous fracturing fluids mainly comprising linear or cross-linked polymeric gels, such as guar, guar derivatives or hydroxyethyl cellulose, have been introduced. In addition, polymer-free aqueous fracturing fluids based on viscoelastic surfactants have been developed. The main advantages of viscoelastic surfactant fluids are ease of preparation, minimal formation damage and high permeability retained in the proppant package, being the conventional proppant additives in fracturing fluids. Many viscoelastic fluids, including fracturing fluids, are known comprising a viscoelastic surfactant. According to a conventional theory, viscoelastic surfactant molecules, present in a sufficient concentration, aggregate into overlapping worm-like micelles or rods, which provide the necessary viscosity for the fluid to carry the proppant during fracturing. In addition, viscoelastic surfactant-based fluids are “responsive,” in that they degrade to low-viscosity fluid by contacting and interacting with forming fluids, in particular hydrocarbons, during backflow from the reservoir to the well.
[005] It is observed that the document WO 2003/056130 proposes an improvement on such existing systems, and proposes the use of a combination of viscoelastic surfactants and a hydrophobically modified polymer, in which the concentration of hydrophobically modified polymer is comprised between its concentration of overlap c* and its entanglement concentration ce. Although the viscoelastic fluids of WO 2003/056130 have some commercial value, they contain high amounts of both surfactant and hydrophobically modified polymer to achieve aqueous compositions with the desired viscosity. Furthermore, in the polymer, hydrophobes are connected to the polymer backbone through a degradable group.
[006] It is also observed that, in US 4,432,881, liquids are used, in which a water-soluble polymer with hydrophobic groups is used. Polymers which are taught to be used have a weight average molecular weight of 200,000 to 5 million Daltons.
[007] High molecular weight polymers are difficult to dissolve and difficult to distribute homogeneously in aqueous formulations. They also tend to leave residue in the rock formation and damage the formation.
[008] There is a need in the art for viscoelastic surfactant-based fluids with a lower acidic amount of chemicals, to obtain a certain viscosity, or compositions with a higher viscosity when the same amount of chemicals is used, the amounts being based on the weight of the chemicals in the final composition, thus further reducing the costs involved in using said fluid and/or expanding the applications in which the compositions can be used. Furthermore, there is a need to be able to use polymers that are more easily dispersible in aqueous formulations. SUMMARY OF THE INVENTION
[009] It is an object of the present invention to at least meet the aforementioned needs in the art.
[010] Surprisingly, the present inventors have found that viscoelastic compositions can be produced which do not suffer from the disadvantages of prior art compositions by using one or more viscoelastic surfactants and one or more specific hydrophobically modified polymers.
[011] In a first aspect, the present invention thus provides an aqueous viscoelastic composition comprising
[012] at least one viscoelastic surfactant, and
[013] at least one hydrophobically modified polymer, which:
[014] is formed from the polymerization of ethylenically unsaturated monomers;
[015] It has a weight average molecular weight (Mn) of 1,000 to 100,000 Dalton (Da); and
[016] to at least 0.1% by mol, based on the amount of monomeric units in the polymer, comprises monomeric units, each covalently linked to a pendant hydrocarbyl group, optionally alkoxylated, linear, branched or cyclic, saturated or unsaturated, having from 6 to 40 carbon atoms, said pendant, optionally alkoxylated hydrocarbyl group being connected to the backbone of said hydrophobically modified polymer through a linking group that does not contain ester.
[017] In a second aspect, the present invention relates to the use of the hydrophobically modified polymer, as described in this document, as a thickener for a viscoelastic composition comprising a viscoelastic surfactant.
[018] In a third aspect, the present invention relates to different uses of an aqueous viscoelastic composition of the present invention, such as a fracturing fluid for fracturing rock formations and as a thickener in different applications.
[019] In a fourth aspect, the present invention relates to a method for fracturing a rock formation, using an aqueous viscoelastic fluid of the present invention as a fracturing fluid.
[020] These and other aspects of the present invention will now be described in greater detail. BRIEF DESCRIPTION OF THE DRAWINGS
[021] Figures 1 to 10 graphically show the results of several experiments as described in this document. DETAILED DESCRIPTION
[022] The present invention relates to aqueous viscoelastic fluids, preferably aqueous fracturing fluids for, among others, use in the recovery of hydrocarbons, such as oil and gas. The viscoelastic fluid of the invention comprises a special combination of one or more viscoelastic surfactants and one or more specific hydrophobically modified polymers.
[023] The property of viscoelasticity, in general, is well known, and reference is made to the document Hoffmann et al., "Influence of Ionic Surfactants on the Viscoelastic Properties of Zwitterionic Surfactant Solutions", Langmuir, 8, 2140-2146, ( 1992).
[024] Here, a test method for viscoelasticity is to apply sinusoidal shear strain to the composition and measure the storage shear modulus (G') and the loss shear modulus (G' ‘) at a given temperature. If the elastic component (storage shear modulus G') is at least as large as the viscous component (loss shear modulus G"), i.e., G'^G", at a certain point or along a dot range below a frequency of about 10 rad/sec, typically about 0.001 to about 10 rad/sec, more typically between 0.1 to 10 rad/sec, at a given temperature, and if G' > 10 -2 Pascals, preferably more than 101 Pascals, the fluid is considered viscoelastic at that temperature. The definition and rheological measurement of G' and G” are generally described in Barnes H.A. et al., An Introduction to Rheology, pp. 45-54, Elsevier, Amsterdam (1997).
[025] The viscoelastic surfactant is of the conventional type and can, among others, be selected from amine oxide surfactants, including amidoamine oxide surfactants, amphoteric surfactants, zwitterionic surfactants, anionic surfactants, cationic surfactants, and mixtures of two or more of the same.
[026] It is well known that viscoelastic surfactants provide viscoelasticity by forming a different type of micelle than common spherical micelles formed by most surfactants. Viscoelastic surfactants form elongated, often cylindrical, micelles which can be described as worm-like, wire-like, or rod-like micelles. In the context of the present invention, a viscoelastic surfactant is thus a surfactant which can form micelles in a fluid, which impart viscoelasticity to the fluid. It is generally said that the shape and size of a micelle is a function of the molecular geometry of its surfactant molecules and solution conditions such as surfactant concentration, temperature, pH, and ionic strength. The formation of long cylindrical micelles creates useful rheological properties. The viscoelastic surfactant exhibits pseudoplastic behavior, and remains stable despite repeated shear applications, as the micelles spontaneously reform when shear is reduced. In comparison, a typical polymeric thickener will irreversibly degrade when subjected to high-shear applications.
[027] The amine oxide surfactants contemplated for use as viscoelastic surfactants in the present invention include those of the following structural formula (I):

[028] where RI is a hydrophobic moiety of alkyl, alkenyl, cycloalkyl, alkylarylalkyl, alkoxyalkyl, alkylaminoalkyl or alkylamidoalkyl. R1 has from about 8 to about 30 carbon atoms and can be straight-chain or branched and be saturated or unsaturated. Examples of long-chain alkyl groups include, among others, octadecenyl (oleyl), octadecyl (stearyl), docosenoic (erucil), and oil derivatives of tallow, coconut, soybean, and rapeseed.
[029] R2 and R3 are independently hydrogen or at least partially aliphatic groups having from 1 to about 30 carbon atoms, preferably from about 1 to about 20 carbon atoms, more preferably from about 1 to about 10 carbon atoms, and more preferably from about 1 to about 6 carbon atoms. Representative at least partially aliphatic groups include alkyl, alkenyl, cycloalkyl, alkylaryl, hydroxyalkyl, carboxyalkyl, and hydroxyalkyl-polyoxyalkylene. The aliphatic group can be straight-chain or branched and be saturated or unsaturated.
[030] The amidoamine oxide surfactants contemplated for use as viscoelastic surfactants in the present invention include those of the following structural formula (II):

[031] where RI is a straight-chain or branched and saturated or unsaturated aliphatic group of about 8 to 30 carbon atoms, preferably of about 14 to about 21 carbon atoms. More preferably, RI is a fatty aliphatic derived from natural fats and oils having an iodine number from about 1 to about 140, preferably from about 30 to about 90, and more preferably from about 40 to about 70. RI can be restricted to a single chain length, or it can be of mixed chain length, such as groups derived from natural fats and oils or from petroleum reserves. Preferred are tallow alkyl, hardened tallow alkyl, rapeseed alkyl, hardened rapeseed alkyl, tall oil alkyl, coconut alkyl, oleyl, or soybean alkyl;
[032] R2 is a substituted or unsubstituted, substituted or unsubstituted, straight or branched chain alkylene group of about 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, and more preferably 3 carbon atoms;
[033] R3 and R4 are the same or different, and are selected from alkyl or hydroxyl groups of 1 to about 4 carbon atoms, and are preferably hydroxyethyl or methyl. Alternatively, R3 and R4 in the amidoamine oxide of formula (II) with “the nitrogen atom to which these groups are attached, form a heterocyclic ring of up to 6 members; and
[034] R5 is hydrogen or an alkyl or hydroxyl group CI to C4.
[035] Examples of amidoamine oxide contemplated by the present invention include, among others, those selected from the group consisting of tallow amidoalkylamine oxide, hardened tallow amidoalkylamine oxide, rapeseed amidoalkylamine oxide, hardened rapeseed amidoalkylamine oxide, tall oil amidoalkylamine oxide, hardened starchalkylamine oxide, coconut amidoalkylamine oxide, stearyl amidoalkylamine oxide, oleyl amidoalkylamine oxide, soybean amidoalkylamine oxide, and mixtures thereof. Specific preferred examples of the amidoamine oxides of the present invention include, but are not limited to, the following: tallow amidopropyl dimethylamine oxide, hydrogenated tallow amidopropyl dimethylamine oxide, soybean amidopropyl dimethylamine oxide, oleyl amidopropyl dimethylamine oxide, amidopropyl oxide erucile dimethylamine, rapeseed amidopropyl dimethylamine oxide, hydrogenated rapeseed amidopropyl dimethylamine oxide, tall oil amidopropyl dimethylamine oxide, hydrogenated tall oil amidopropyl dimethylamine oxide, saturated or unsaturated C14 to C22 fatty acid amidopropyl dimethylamine oxide, and mixtures of the same.
[036] A cationic surfactant has a positively charged fraction, regardless of pH. Cationic surfactants contemplated for use as the viscoelastic surfactant in the present invention include those selected from quaternary salts, certain amines, and combinations thereof.
[037] Quaternary salts have the structural formula (III)

[038]where RI is a hydrophobic moiety of alkyl, alkenyl, cycloalkyl, alkylarylalkyl, alkoxyalkyl, alkylaminoalkyl or alkylamidoalkyl. R1 has from about 8 to about 30 carbon atoms and can be straight-chain or branched and be saturated or unsaturated. Examples of long-chain alkyl groups include, but are not limited to, octadecenyl (oleyl), octadecyl (stearyl), docosenoic (erucil), and oil derivatives of tallow, coconut, soybean, and rapeseed;
[039] R2 and R4 are independently at least partially aliphatic groups having from 1 to about 30 carbon atoms, preferably from about 1 to about 20 carbon atoms, more preferably from about 1 to about 10 atoms of carbon, and more preferably from about 1 to about 6 carbon atoms. Representative at least partially aliphatic groups include alkyl, alkenyl, alkylaryl, alkoxyalkyl, hydroxyalkyl, carboxyalkyl, and hydroxyalkyl-polyoxyalkylene. The aliphatic group can be straight-chain or branched and saturated or unsaturated, and;
[040] X- is a suitable counteranion. The counteranion is typically an inorganic anion such as a sulfate such as (CH3)2SO4-, a nitrate, a perchlorate or a halide such as Cl-, Br-, or an aromatic organic anion such as salicylate, naphthalene sulfonate , p- and m-chlorobenzoates, 3,5-, 3,4-, and 2,4-dichlorobenzoates, t-butyl and ethyl phenate, 2,6- and 2,5-dichlorophenates, 2,4,5- trichlorophenate, 2,3,5,6-tetrachlorophenate, p-methyl phenate, m-chlorophenate, 3,5,6-trichloropicolinate, 4-amino-3amino-3,5,6-trichloropicolinate, 2,4-dichlorophenoxyacetate.
[041] Amines have the following structural formula (IV):

[042] where R1, R2, and R3 have the meaning defined above for the quaternary salt residues R1, R2, and R3, respectively.
[043] The zwitterionic surfactant has a permanently positively charged fraction in the molecule, regardless of pH, and a negatively charged fraction at alkaline pH. The zwitterionic surfactants that are useful as viscoelastic surfactants in the present invention include those of the following structural formula (V):

[044] where RI is a hydrophobic moiety of alkyl, alkenyl, cycloalkyl, alkylarylalkyl, alkoxyalkyl, alkylaminoalkyl or alkylamidoalkyl. R1 has from about 8 to about 30 carbon atoms and can be straight-chain or branched and be saturated or unsaturated. Examples of long-chain alkyl groups include, but are not limited to, octadecenyl (oleyl), octadecyl (stearyl), docosenoic (erucil), and oil derivatives of tallow, coconut, soybean, and rapeseed;
[045] R2 and R3 are independently at least partially aliphatic groups having from about 1 to about 30 carbon atoms, preferably from about 1 to about 20 carbon atoms, more preferably from about 1 to about 10 carbon atoms, and more preferably from about 1 to about 6 carbon atoms. Representative at least partially aliphatic groups include alkyl, alkenyl, alkylaryl, alkoxyalkyl, hydroxyalkyl, carboxyalkyl, and hydroxyalkyl-polyoxyalkylene. The aliphatic group can be straight-chain or branched and saturated or unsaturated, and;
[046] R4 is a hydrocarbyl (eg alkylene) radical with a chain length of 1 to 4 carbon atoms. Methylene or ethylene groups are preferred.
[047] When it is zwitterionic, the surfactant is associated with both negative and positive counterions. Anions are typically as defined above for X- for the cationic surfactant. In one embodiment, any cation is suitably selected from Na+, K+, NH4+, and amine salts such as (CH3)2NH2+.
[048] An amphoteric surfactant has both a positively charged fraction and a negatively charged fraction over a certain pH range (eg, typically somewhat acidic), only one . negatively charged fraction over a certain pH range (eg slightly alkaline), and only a positively charged fraction over a different pH (eg typically moderately acidic).
[049] Amphoteric surfactants contemplated for use as a viscoelastic surfactant in the present invention include those represented by the following structural formula (VI):
[050] where RI is a hydrophobic moiety of alkyl, alkenyl, cycloalkyl, alkylarylalkyl, alkoxyalkyl, alkylaminoalkyl or alkylamidoalkyl. R1 has from about 8 to about 30 carbon atoms and can be straight-chain or branched and be saturated or unsaturated. Examples of long-chain alkyl groups include, but are not limited to, octadecenyl (oleyl), octadecyl (stearyl), docosenoic (erucil), and oil derivatives of tallow, coconut, soybean, and rapeseed;
[051] R2 has the meaning defined above for the residue R2 of the zwitterionic surfactant;
[052] R3 is a hydrocarbyl (eg alkylene) radical with a chain length of 1 to 4 carbon atoms. Methylene or ethylene groups are preferred.
[053] An anionic surfactant has a negatively charged fraction, regardless of pH. The anionic surfactants contemplated for use as the viscoelastic surfactant in the present invention include those of the following structural formulas (VII) and (VIII).
[054] where R is the hydrophobic moiety of alkyl, alkenyl, cycloalkyl, alkylarylalkyl, alkoxyalkyl, alkylaminoalkyl or alkylamidoalkyl. Preferably, R is a straight or branched, saturated or unsaturated alkyl chain of 8 to 30 carbon atoms. Examples of long chain alkyl groups include, but are not limited to, octadecenyl (oleyl), lauryl, octadecyl (stearyl), docosenoic (erucil), and oil derivatives of tallow, coconut, soybean, and rapeseed.
[055] Z is the negatively charged head of the surfactant. Z is suitably selected from the group consisting of carboxylate COO-, sulfonate SO3-, sulfate SO4-phosphonate, phosphate, and combinations thereof. In one embodiment, Z is a carboxylate group COO- or a sulfonate group SO3- or a sulfate group SO4-.
[056] X is a stabilizing group. X is preferably a cleavable bond. Preferably X is an ester, amide, reverse ester or reverse amide group.
[057] Y is a space group that separates the cleavable group X and the hydrophilic head of the surfactant. Y is preferably a straight, saturated or unsaturated hydrocarbon chain of 1, 2 or 3 carbon atoms or a branched, saturated or unsaturated hydrocarbon chain where the main chain is 1, 2 or 3 carbon atoms, possibly incorporating a ring aromatic.
[058] The surfactant of the invention can be dimeric or oligomeric. In this case, the formula of the surfactant is [RZ]n or [RXYZ]n, where n is 2 to 10, preferably 2 or 3. An example of an oligomeric anionic surfactant is oligomerized oleic acid, which generally leads to complex mixtures of dimeric and trimeric products. Commercially available oligomers, such as the Empol™ series of dimers and trimers, are suitable for use in accordance with the present invention.
[059] When the surfactant is anionic, the counterion is typically Na+, K+, NH4+, or amine salt such as (CH3)2NH2+. These mono-, di-, or oligomeric carboxylates or sulfonates form aqueous viscoelastic compositions in the presence of salt.
[060] Preferably, the surfactants that are used are biodegradable, more preferably readily biodegradable, when tested using conventional tests such as OECD 306 A-F.
[061] The hydrophobically modified polymers can be anionic hydrophobically modified polymer or cationic hydrophobically modified polymer or non-ionic hydrophobically modified polymer or zwitterionic hydrophobically modified polymer.
[062] The at least one hydrophobically modified polymer is formed from the polymerization of ethylenically unsaturated monomers using polymerization conditions known to those skilled in the art.
[063] The hydrophobically modified polymer has a number average molecular weight from 1000, such as from 1500, for example, from 2500, up to 100000, such as up to 90000, for example, up to 50000, such as up 25,000 Da. In the context of this invention, the weight average and number average molecular weights are as determined with size exclusion chromatography. Size exclusion chromatography was performed using HPLC grade water comprising 0.025M NaH2PO4, 0.025M Na2HPO4, and 0.01M sodium azide, which was filtered through a 0.2 µm filter as the eluent and four separation columns, G6000PWxl 7.8mm x 30cm, G4000PWxl 7.8mm x 30cm, G3000PWxl 7.8mm x 30cm, and TSKgel Guard PWxl 6.0mm x 4cm as the G2500 Guard column (all from Tosoh Bioscience). Polyacrylic acid standard sodium salts (from American Polymer Standards Corporation) were used for calibration. Polymers are prepared in water at a concentration of 0.1% w/w. The weight average molecular weight (Mw) and number average molecular weight (Mn) of the standards are: 1. Mw 1300 Dalton Mn 830 Dalton 2 . Mw 8300 Dalton Mn 6200 Dalton 3 . Mw 83,400 Dalton Mn 47,900 Dalton 4. Mw 495,000 Dalton Mn 311,300 Dalton 5. Mw 1,700,000 Dalton Mn 1,100,000 Dalton
[064] The injection column was 450 μL for the standard and for the sample. Inject the standards and build a first-order or second-order calibration curve. Choose the curve with the best fit and within the molecular weight range of the sample. Run time was 60 minutes per injection for both the standard and the sample.
[065] At a level of at least 0.1 mol%, based on the amount of monomeric units in the polymer, the hydrophobically modified polymer comprises monomeric units, each covalently linked to a pendant, optionally alkoxylated hydrocarbyl group having from 6 to 40 carbon atoms, said pendant, optionally alkoxylated hydrocarbyl group being connected to the backbone of said hydrophobically modified polymer through a linking group that does not contain ester.
[066] The optionally alkoxylated pendant hydrocarbyl group has from 6, preferably from 8, more preferably from 11, for example from 14, to 40, preferably to 32, most preferably to 24 carbon atoms.
[067] The hydrocarbyl group is typically a linear, branched or cyclic, saturated or unsaturated hydrocarbyl, such as a linear or branched alkyl, alkenyl, cycloalkyl, aryl, alkylaryl, alkenylaryl or an alkoxylated derivative thereof. The hydrocarbyl group may optionally be alkoxylated, such as obtained by ethoxylation, propoxylation and/or butoxylation of the alcohol or acid corresponding to the hydrocarbyl group. If alkoxylated, the alkyleneoxy group(s) will be located between the hydrocarbyl group and the polymer backbone. Examples of pendant hydrocarbyl groups include behenyl, stearyl, lauryl, 2-ethylhexyl, 2-propylheptyl, 2-butyloctyl, 2-hexyldecyl, 2-octyldodecyl, 2-decyltetradecyl, 2-dodecylhexadecyl, 2-tetradecyl octadecyl or its alkoxylated derivatives, or the alkyl group of oleyl, coconut, soy, erucil or tallow acids or alcohols or amines and their alkoxylated derivatives. When hydrocarbyl is alkoxylated, the carbon atoms in the alkyleneoxy groups are included in the carbon atom count of the hydrocarbyl group, except the carbon atoms of any ethyleneoxy group, which are not included in the carbon atom count of the hydrocarbyl group because of to the hydrophobicity of the ethyleneoxy group. To illustrate, an ethoxylated dodecyl group is an alkoxylated hydrocarbyl group having 12 carbon atoms, while propoxylated hexyl having 3 propoxylenoxy groups is an alkoxylated hydrocarbyl group having 15 (6 + 9) carbon atoms.
[068] In one embodiment of the invention, the optionally alkoxylated pendant hydrocarbyl group contains 12 or more carbons, and the hydrophobically modified polymer contains at a level of 0.1, such as 0.5, for example 1, a 20, such as 10, for example 5% by mol, based on the amount of monomeric units in the polymer, monomeric units connected to such an optionally alkoxylated pendant hydrocarbyl group.
[069] In another embodiment of the invention, the pendant hydrocarbyl group, optionally alkoxylated, comprises an alkyl function with a maximum of 11 carbon atoms, and the hydrophobically modified polymer contains at a level of 0.1, such as 0.5 , for example from 1, to 20, such as 10, for example to 5% by mol, based on the amount of monomeric units in the polymer, monomeric units connected to such an optionally alkoxylated pendant hydrocarbyl group.
[070] The pendant, optionally alkoxylated hydrocarbyl group is connected to the backbone of the hydrophobically modified polymer through a linking group that does not contain ester, such as direct linkage or linking groups containing urea, urethane, imide or amide. Link groups that do not contain exemplary esters include a direct link or:
[071] wherein R4 is a hydrocarbylene group having 1 to 10 carbon atoms, preferably CH2, and the upper bond of the linking group is connected to the polymer backbone and the lower bond is connected to the pendant, optionally alkoxylated hydrocarbyl group. Preferably, the non-ester containing linking group is a direct link or a linking group containing urea, urethane, imide or amide, more preferably a linking group containing urea or urethane.
[072] The hydrophobically modified polymers used in the invention can be produced by copolymerizing suitable ethylenically unsaturated monomers to directly achieve the desired polymer, or they can also be produced by modifying an existing polymer, through the reaction of a hydrophobically modified polymer with additional hydrophobic modifying agents, such as reacting a maleic anhydride copolymer, including polyisobutylene succinic acid (PIBSA) copolymers, with a fatty amine.
[073] Alternatively, hydrophobically modified polymer can be produced by reacting a functional polymer with a hydrophobic modifying agent.
[074] The hydrophobically modified polymer is suitably free of, or contains at most 1, preferably at most 0.1, more preferably at most 0.01% by mol, based on the amount of monomeric units in the polymer, of connected monomeric units to the pendant, optionally alkoxylated hydrocarbyl group having at least 10, preferably at least 8, more preferably at least 6 carbon atoms connected to the backbone of said hydrophobically modified polymer via an ester-containing linking group.
[075] The hydrophobically modified polymer can be obtained by copolymerizing at least one first and at least one second ethylenically unsaturated monomer, wherein said first monomer is an ethylenically unsaturated monomer with an optionally alkoxylated hydrocarbyl group having of 6, preferably of 8, more preferably from 11, to 40, preferably to 32, more preferably to 24 carbon atoms being connected to the unsaturated function of said monomer via a linking group that does not contain an ester, preferably a direct bond or a linking group containing urea, urethane, imide or amide, more preferably a linking group containing urea or urethane; and said second monomer is an ethylenically unsaturated monomer free of hydrocarbyl groups having at least 11, preferably at least 8, more preferably at least 6 carbon atoms connected to the unsaturated function of the monomer. The first and second monomers are present in a molar ratio of 0.1:99.9 to 90:10.
[076] When the optionally alkoxylated hydrocarbyl group has at least 12 carbon atoms, the first and second monomers are generally present in a molar ratio of 0.1:99.9 to 20:80; preferably from 0.5:99.5 to 10:90, more preferably from 1:99 to 5:95.
[077] When the optionally alkoxylated hydrocarbyl group has a maximum of 11 carbon atoms, the first and second monomers are generally present in a mutual molar ratio of 1:99 to 90:10; preferably from 5:95 to 70:30, more preferably from 10:90 to 50:50.
[078] Monomers with an optionally alkoxylated hydrocarbyl group having from 6 to 40 carbon atoms connected to the unsaturated function thereof through a hydrocarbyl group (herein also called hydrophobe bearing monomers) include those with the following structure (VIIII)
[079] where R1, R2, and R3 are independently selected from H, CH3, COOH, and CH2COOH,
[080] X (ie the linking group) is a direct link or
[081] wherein R4 is a hydrocarbylene group having 1 to 10 carbon atoms, preferably CH2, the upper bond of X is connected to the double bond in (VIIII), and the lower bond of X is connected to Rhy, and
[082] Rhy is the optionally alkoxylated hydrocarbyl group having from 6, preferably from 8, more preferably from 11, to 40, preferably to 32, most preferably to 24 carbon atoms.
[083] Hydrophobe-bearing monomers of the above type are commercially available or can be obtained by methods well known in the art, for example, by reacting an ethylenically unsaturated isocyanate such as allyl-isocyanate or 3-isopropyl-benzyl-α,α -dimethyl-isocyanate, with an alcohol or amine containing a hydrocarbyl group (optionally alkoxylated) having from 6 to 40 carbon atoms, by reacting an ethylenically unsaturated acid monomer, such as acrylic acid, with an amine containing a hydrocarbyl group (optionally alkoxylated) having from 6 to 40 carbon atoms. Other methods for synthesizing such monomers are well known to those skilled in the art of organic synthesis.
[084] Examples of hydrophobe-bearing monomers, where the hydrophobe is attached to the double bond of the monomer include t-octyl acrylamide, n-octyl acrylamide, lauryl acrylamide, stearyl acrylamide, behenyl acrylamide, 1-allyl naphthalene, 2-allyl naphthalene, 1-vinyl naphthalene, 2-vinyl naphthalene, styrene, α-methyl styrene, 3-methyl styrene, 4-propyl styrene, t-butyl styrene, 4-cyclohexyl styrene, 4-dodecyl styrene, 2-ethyl-4-benzyl styrene and 4-(phenyl butyl) styrene.
[085] The ethylenically unsaturated monomer free from hydrocarbyl groups having 11 or more, preferably 8 or more, more preferably 6 or more, carbon atoms connected to the unsaturated function of the monomer, i.e., the second monomer, may be anionic ethylenically unsaturated monomers , cationic ethylenically unsaturated, non-ionic ethylenically unsaturated, zwitterionic ethylenically unsaturated, mixtures thereof and salts thereof.
[086] In one embodiment, the hydrophobically modified polymer is anionic and is synthesized from at least one first ethylenically unsaturated hydrophobe-bearing monomer and at least one second ethylenically unsaturated monomer that is anionic and called an anionic ethylenically unsaturated monomer hereafter against. In another embodiment, the hydrophobically modified polymer is cationic and is synthesized from at least one first ethylenically unsaturated hydrophobe-bearing monomer and at least one second ethylenically unsaturated monomer which is cationic and is called a cationic ethylenically unsaturated monomer hereinafter. In yet another embodiment, the hydrophobically modified polymer is non-ionic and is synthesized from at least one first ethylenically unsaturated hydrophobe-bearing monomer and at least one second ethylenically unsaturated monomer that is non-ionic and is called an ethylenically unsaturated monomer non-ionic from here on out. In a further embodiment, the hydrophobically modified polymer is zwitterionic and is synthesized from at least one first ethylenically unsaturated hydrophobe-bearing monomer and at least one second ethylenically unsaturated monomer which is zwitterionic and is hereinafter called a zwitterionic ethylenically unsaturated monomer . In this embodiment, the polymer contains positive and negative charges, which are on the same monomeric repeating unit. In yet another embodiment, the hydrophobically modified polymer is zwitterionic and is synthesized from at least one first ethylenically unsaturated hydrophobe-bearing monomer and at least one second anionic ethylenically unsaturated monomer and at least one second cationic ethylenically unsaturated monomer. In this embodiment, the polymer contains positive and negative charges, which are in different monomeric repeating units.
[087] In this document, an ethylenically unsaturated monomer is defined as any monomer that is capable of introducing a negative charge to the hydrophobically modified polymer. These ethylenically unsaturated monomers include acrylic acid, methacrylic acid, ethacrylic acid, a-chloro-acrylic acid, a-cyanoacrylic acid, β-methyl-acrylic acid (crotonic acid), a-phenyl acrylic acid, β-acryloxy propionic acid, sorbic acid, α-chlorine sorbic acid, angelic acid, cinnamic acid, p-chloro cinnamic acid, β-styryl acrylic acid (1-carboxy-4-phenyl butadiene-1,3), itaconic acid, maleic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, fumaric acid, tricarboxy ethylene, 2-acryloxypropionic acid, 2-acrylamido-2-methyl propane sulfonic acid (AMPS), vinyl sulfonic acid, sodium methylyl sulfonate, sulfonated styrene, allyloxybenzene sulfonic acid, and its salts. Preferred salts of hydrophilic acid monomers are sodium, potassium, or ammonium salts. Fractions, such as maleic anhydride or acrylamide, which can be derivatized to an acid-containing group can be used. Combinations of ethylenically unsaturated monomers can also be used. In one aspect, the ethylenically unsaturated monomer is acrylic acid, maleic acid, itaconic acid, methacrylic acid, 2-acrylamido-2-methyl propane sulfonic acid, vinyl sulfonic acid, sodium methallyl sulfonate, sulfonated styrene, allyloxybenzene sulfonic acid or mixtures of the themselves and their salts.
[088] Cationic ethylenically unsaturated monomers are defined in this document as ethylenically unsaturated monomers, which are capable of introducing a positive charge to the hydrophobically modified copolymer. In one embodiment of the present invention, the cationic ethylenically unsaturated monomer has at least one amine functionality. The cations in the polymer can be obtained by forming amine salts of all or a portion of the amine functionality, and/or by quaternizing all or a portion of the amine functionality to form quaternary ammonium salts. As used in this document, the term "amine salt" means that the nitrogen atom of the amine functionality is covalently bonded to one to three organic groups and three to 1 protons, so that there are 4 bonds to the nitrogen and it is associated to an anion. As used herein, the term "quaternary ammonium salt" means that a nitrogen atom of the amine functionality is covalently bonded to four organic groups and is associated with an anion.
[089] Cationic ethylenically unsaturated monomers that can form cations include N,N-dialkylaminoalkyl (meth)acrylate, N-alkylaminoalkyl (meth)acrylate, N,N-dialkylaminoalkyl (meth)acrylamide, and N-alkylaminoalkyl (meth)acrylamide, where alkyl groups are independently C1-18 cyclic compounds such as 1-vinyl imidazole and the like. Aromatic amine-containing monomers, such as vinyl pyridine, can also be used. In addition, monomers such as vinyl formamide, vinyl acetamide, and the like, which generate amine fractions on hydrolysis, can also be used. Preferably, the cationic ethylenically unsaturated monomer is N,N-dimethylaminoethyl methacrylate, tert-butyl aminoethyl methacrylate, and N,N-dimethylaminopropyl methacrylamide.
[090] Cationic ethylenically unsaturated monomers that can be used include the quaternized derivatives of the above monomers, as well as diallyldimethylammonium chloride, also known as dimethyldiallylammonium chloride, (meth)acrylamidopropyl trimethylammonium chloride, 2-(meth)acryloyloxy ethyl trimethyl chloride ammonium, 2-(meth)acryloyloxy ethyl trimethyl ammonium methyl sulfate, 2-(meth)acryloyloxyethyltrimethyl ammonium chloride, N,N-dimethylaminoethyl (meth)acrylate methyl quaternary chloride, methacryloyloxy ethyl betaine, as well as other betaines and sulfobetaines, hydrochloride 2-(meth)acryloyloxy ethyl dimethyl ammonium, 3-(meth)acryloyloxy ethyl dimethyl ammonium hydroacetate, 2-(meth)acryloyloxy ethyl dimethyl cetyl ammonium chloride, 2-(meth)acryloyloxy ethyl diphenyl ammonium chloride, and others.
[091] As used herein, the term "non-ionic ethylenically unsaturated monomer" means an ethylenically unsaturated monomer that does not introduce a charge to the hydrophobically modified copolymer. These non-ionic ethylenically unsaturated monomers include acrylamide, methacrylamide, N-alkyl(meth)acrylamide, N,N-dialkyl(meth)acrylamide such as N,N-dimethylacrylamide, hydroxyalkyl(meth)acrylates, alkyl(meth)acrylates such as methylacrylate and methylmethacrylate, vinyl acetate, acrylonitrile, vinyl morpholine, vinyl pyrrolidone, vinyl caprolactam, ethoxylated alkyl, alkaryl or aryl monomers such as methoxypolyethylene glycol (meth)acrylate, allyl glycidyl ether, allyl alcohol, glycerol monomer (meth)acrylate containing silane, silanol, and siloxane functionalities, and others. In one embodiment, the non-ionic hydrophobically modified polymer contains vinyl alcohol, which is typically generated by the hydrolysis of vinyl acetate after the hydrophobically modified polymer has been formed. The non-ionic ethylenically unsaturated monomer is preferably soluble in water.
[092] As used herein, the term "zwitterionic ethylenically unsaturated monomer" means an ethylenically unsaturated monomer that introduces both a positive charge and a negative charge on the same monomeric repeat of the hydrophobically modified copolymer. Zwitterionic ethylenically unsaturated monomers include the amine oxides carboxybetaine, sulfobetaine, and phosphobetaine monomers. Examples of amine oxides include, among others, vinyl pyridine oxide-N- and tert-butylaminoethylmethacrylate-N oxide. It is understood that the monomer, eg N-vinyl pyridine, can be copolymerized and then the pyridine fraction is oxidized to the amine oxide. Examples of carboxybetaine monomers include, among others, N,N'-dimethyl-N-methacryloyloxyethyl-N-(2-carboxyethyl)ammonium, (2-(2-acrylamido-2-methylpropyldimethylammonium) ethanoate, 6-(2-acrylamido -2-methylpropyl dimethylammonium)hexanoate, 4-(N,N-dialyl-N-methylammonium)butanoate, and others.
[093] Examples of sulfobetaine monomers include, among others, sulfopropyldimethylammonioethyl methacrylate, sulfoethyldimethylammonioethyl methacrylate, sulfobutyldimethylammonioethyl methacrylate, sulfohydroxypropyldimethylammonioethyl methacrylate, sulfopropyldimethylammoniopropylacrylamide, sulfopropyldimethylammonioethyl methacrylamide, sulfopropyldimethylammonioethyl methacrylamide, sulfopropyldimethylammonioethyl methacrylamide, 2-hydroxypropylammonioethyl methacrylamide, sulfopropyldimethylammoniopropylammonioethylmethacrylamide, sulfopropyldimethylammoniopropylaminomethacrylamide, 3-sulfopropyl) pyridinium betaine, 4-vinyl-I-(3-sulfopropyl) pyridinium betaine, 1-vinyl-3-(3sulfopropyl) imidazolium betaine, sulfopropylmethyldiallylammonium betaine, 3-(N,N-dialyl-N-methylammonium) propanesulfonate , between others.
[094] As mentioned above, a zwitterionic hydrophobically modified polymer can be synthesized by copolymerizing an anionic ethylenically unsaturated monomer and a cationic ethylenically unsaturated monomer with a hydrophobe-bearing monomer. Any combination of anionic and cationic monomers can be used. However, the preferred anionic monomer will introduce a sulfonate group to the copolymer.
[095] A polymer of the present invention may comprise more monomers than those mentioned above.
[096] The hydrophobically modified polymers of the invention are not conventional thickeners, due to their low molecular weight. Therefore, the molecular weight of said polymers, neutralized or not, can be, for example, chosen so that they do not thicken a 4% by weight KCl solution in water when used in concentrations of 2% by weight in said solution of KCl, at a temperature of 25°C. The molecular weight of the polymer can be chosen so that an aqueous solution of 2 wt% polymer and 4 wt% KCl has a viscosity of 100 or less, preferably 50 or less, more preferably 16 mPa*s or less in a shear rate of 100 sec-1 and a temperature of 25°C. For comparison, a polymer that is conventionally used in fracturing fluids typically gives a viscosity well above 100 mPa*s when tested in this way.
[097] Due to the exceptional properties observed for the compositions of the invention with the viscoelastic surfactant and the specific polymer, it is possible to reduce the amount of surfactant and/or polymer. Therefore, it may be desired, for economic and environmental reasons, to use the polymers of the invention at a polymeric concentration that is below the overlapping concentration c*. Furthermore, it is observed that the polymers of the invention were found to interact with viscoelastic surfactants in such a way that combined use leads to higher viscosities at high temperature (tested up to 100°C) and pressures (tested up to 25 bara).
[098] Another embodiment of the invention relates to a method for recovering hydrocarbons from an oil well using viscoelastic compositions of the invention, preferably injecting said compositions into rock formations to fracture said rocks.
[099] Preferably, the viscoelastic surfactants, or mixtures of viscoelastic surfactants, of the invention are selected so that they are biodegradable. Most preferably, they are selected so that they are readily biodegradable.
[100] Surprisingly, it has been found that such low molecular weight polymers, which themselves are typically non-thickening, interact with viscoelastic surfactants in a way that has led to a higher solution viscosity of pure viscoelastic surfactant of the same concentration. It has also surprisingly been found that said higher viscosity can be obtained at a polymeric concentration which is less than its overlapping concentration c*. For economic and environmental reasons, it may be desirable to use the polymers of the invention at a polymer concentration that is below the c* overlap concentration.
[101] The polymer overlap concentration c* is a threshold concentration when polymer coils begin to clump together densely in a solvent. In a dilute polymer solution, where the polymer concentration is below c*, the polymer coils are separated. In a polymer solution in which the polymer concentration is above c*, the polymer coils are densely agglomerated. The detailed definition of c* is described by Pierre-Gilles de Gennes in "Scaling Concept on Polymer Physics", pp. 176-177. 76-77, Cornell University Press, Ithaca and London (1979). c* is measured by the graph of viscosity versus concentration. At low concentrations, the graph will follow a linear path, and once c* is reached, the slope of the line increases dramatically. For the purposes of this document, the overlap concentration c* is measured at 25°C at atmospheric pressure in the solvent.
[102] According to a non-binding theory, the hydrophobically modified polymers of the invention, notably their pendant hydrophobic chains, interact in an improved manner with surfactant micelles. The interaction possibly increases the size of the worm-like or rod-like micelles, and/or crosslinks the micelles so that a higher viscosity is achieved. As a result, an aqueous viscoelastic structure that satisfies the required rheology profile is obtained using fewer chemicals than previously possible. At the same time, the lower molecular weight polymers allowed easier handling of the polymer itself, and faster preparation of the compositions of the invention.
[103] If the combination of viscoelastic surfactant and polymer of the invention is provided in a concentrated form, it is preferably an aqueous form, essentially free of salts. Such aqueous concentrate has the advantage of having a low viscosity and related easy dilution. Typical aqueous concentrates comprise one or more glycols, such as propylene glycol, so that the viscoelastic surfactant is more easily dissolved in the concentrate. Typically, the amount of viscoelastic surfactant in such a concentrate is within the range of 10 to 60%w/w, while the amount of polymer varies from 5 to 30%w/w, based on the weight of the concentrate. It is understood by the term essentially free of salts that the concentration of salts is less than 0.01% w/w, otherwise the viscosity becomes unacceptably high.
[104] For aqueous oilfield fracturing fluids, viscoelastic surfactant is used in an amount of 10%w/w or less. In one embodiment of the invention, it is 5%w/w or less. For applications outside of oilfield fracturing fluids, the viscoelastic surfactant is used in an amount below 50%w/w, preferably below 40%w/w of the final aqueous composition. Furthermore, the viscoelastic surfactant is suitably used in an amount of 0.1%w/w or more. In one embodiment, it is 0.2%w/w or more, while in another embodiment, it is 0.3%w/w or more, all being based on the total viscoelastic fluid.
[105] In general, the hydrophobically modified polymer is used in an amount of 10%w/w or less. In one embodiment of the invention, it is 5%w/w or less. In another embodiment, it is 2% or less, while in an additional embodiment, it is 1%w/w or less. The polymer should be used in an amount of at least 0.01%w/w.
[106] The weight ratio of hydrophobically modified polymer to viscoelastic surfactant is generally 0.1:100, preferably 1:100, more preferably 3:100, to 100:50, preferably to 100:100, most preferably to 50:100.
[107] In addition to the surfactant and the specific hydrophobically modified polymer, a fluid of the invention may comprise additional components. Typically, an electrolyte is present in the fluid. For fracturing fluids typically one or more salts are present as the electrolyte, for example inorganic salts such as ammonium, sodium and potassium chlorides, and/or organic salts such as sodium salicylate are used. If used, the salts are typically present at a concentration of 1 to 10%w/w, more preferably at a level of 3 to 4%w/w, based on the weight of the fracturing fluid. Alternatively, especially if the soil formation in which the fracturing fluid is used contains many of these salts, the salt is not incorporated into the fluid when used, but rather obtained from said soil formation during application.
[108] The viscoelastic compositions of this invention can be used in other applications such as fabric cleaning, personal care, and agricultural applications. In these applications, the electrolyte will be different. For example, in liquid laundry detergents and automatic dishwashing, the electrolyte will take the form of boosters. These builders include, among others, materials such as sodium carbonate, sodium sulfate, phosphate, silicate, citrate, and mixtures thereof. Electrolytes in agricultural applications can be water-soluble electrolytes used in pest control. Examples of such water-soluble electrolytes used in pest control include, among others, 2,4D salts, namely, salts of 2,4-dichlorophenoxy acetic acid with dimethylamine, glycolamine, and other amines, monochlorophenoxyacetic acid (MCPA); sodium, potassium, and amine salts, 3,6-dichloro-2-methoxybenzoic acid (Dicamba); sodium, potassium and amine based salts, (hydroxymethylphosphinyl) butanoic acid, ammonium salt (Gluphosinate ammonium), sodium 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoate (Acifluorophen-sodium), 2-chloro-N,N,N-trimethylethanaminium chloride (Chlormequat chloride), acid dichlorprop-2-(2,4-dichlorophenoxy)propanoate; sodium, potassium, and amine salts, and others. In these applications, the electrolyte can be at least 1% by weight, more preferably at least 5% by weight, and most preferably at least 10% by weight of the formulation. Furthermore, in these applications, the electrolyte can be at a maximum of 90% by weight, or more preferably a maximum of 60% by weight, and more preferably a maximum of 40% by weight of the formulation.
[109] The viscoelastic compositions of the invention may also comprise one or more chelating agents. In particular, when there are many hardness ions in aqueous formulations, or in the area where the compositions are used, it has been found that the use of chelating agents for such ions is beneficial. Without being bound by theory, these hardness ions are thought to tend to precipitate the hydrophobically modified polymer into the aqueous solution. The addition of chelating agents, according to said theory, prevents the precipitation of these hydrophobically modified polymers and preserves the mixing performance of these polymers and viscoelastic surfactants in high hardness aqueous solutions. For purposes of this invention, a chelating agent is described as any material that will chelate hardness ions, such as calcium and magnesium, in aqueous solutions. Chelating agents include, among others, (S,S)-ethylenediaminesuccinic acid trisodium salt, N,N-bis(carboxymethyl)-L-glutamic acid tetrasodium salt, L-aspartate-(N,N)-acid tetrasodium salt diacetic acid, N-2-hydroxyethyliminodiacetic acid disodium salt, methylglycinediacetic acid trisodium salt, nitroryltriacetic acid, diethylenetriaminepentaacetic acid, hydroxyethylenediaminetriacetic acid, triethylenetetraminehexaacetic acid, 1,3-propanediaminetetraacetic acid, 1,3-propanediaminetetraacetic acid, 1,3-dihydroxyethylaminoglycine-diacetic acid, 1,3-diaminediacetic acid glycol ether diaminetetraacetic acid, hydroxyethanediphosphonic acid, aminotrimethylenephosphonic acid, 1,2,4-butanetricarboxylic acid, dihydroxy-ethylethylenediaminediacetic acid, sodium gluconate, sodium glucoheptonate, inositol hexaphosphonate, hydroxyethanoic acid, 2-dihydroxybutanedioic acid, and 2-dihydroxybutanedioic acid -1,2,3-propanetricarboxylic, and its salts. Preferred chelating agents are aminocarboxylates such as (S,S)-ethylenediaminesuccinic acid trisodium salt, N,N-bis(carboxymethyl)-L-glutamic acid tetrasodium salt, L-aspartate-(N,) acid tetrasodium salt N)-diacetic acid, N-2-hydroxyethyliminodiacetic acid disodium salt, methylglycinediacetic acid trisodium salt, ethylenediaminetetraacetic acid, nitrilotriacetic acid, and salts thereof. For purposes of this invention, a high hardness aqueous solution is defined as a solution with a hardness greater than 100 ppm expressed as CaCO3, more preferably greater than 250 ppm as CaCO3, and more preferably greater than 500 ppm as CaCO3.
[110] The fluid may also contain an organic solvent, such as, for example, isopropanol, glycol, which can be used to help dissolve the viscoelastic surfactant component. The fluid may also contain additives, including loss additives such as a mixture of starch and mica.
[111] Due to the fact that a surfactant is used to form micelles, the fluid of the invention is responsive to hydrocarbons, such that the structure breaks on contact or mixture with hydrocarbons. Typically, after contact with hydrocarbons, spherical micelles are formed, which no longer show viscoelastic properties.
[112] Practically all compounds of the fluid of the invention are mixed together. If a lower viscosity is required, the fluid is subjected to a high shear rate, allowing, for example, the pumping of the fluid into a hole/wellbore.
[113] With the exception of information in the examples, or where otherwise indicated, all numbers or expressions referring to amounts of ingredients, reaction conditions, and the like, used in the specification and claims, shall be understood as modified in all cases by the term “about”. Also, where numerical ranges are revealed, they are intended to be continuous ranges that include each value between the minimum value and the maximum value as presented. % by weight and %w/w mean percentage by weight.
[114] The invention will now be further described in connection with the following Examples, which, however, are not intended to limit the scope of the invention. Unless otherwise indicated, all parts and percentages refer to parts and percentages by weight. All numbers given refer to the quantity of active material. So, if, in the Examples, 10%w/w of a chemical is specified, then the quantity to be used of the supplied product must be increased if the product is supplied in a diluted form. EXAMPLES
[115] Except where otherwise noted, the viscosity of the samples was determined over a wide shear rate using an SR-5000 tension-controlled rheometer (from Rheometric Scientific, which is now TA Instruments). The sample was placed between two parallel circular plates of 25 mm or 40 mm in diameter and evaluated at a temperature of 25°C. Typically, the initial stress was 0.5 Pa, and the final stress was in the range 140 to 400 Pa, depending on the sample viscosity, with the lower final stress selected for samples with lower viscosity. In linear scan mode, a voltage increment of 0.5 to 2 Pa was applied.
[116] Aromox® APA-TW is a tallow-alkylamidopropyl dimethyl amine oxide supplied by AkzoNobel.
[117] POLYFLOS® HM 21 is a hydrophobically modified hydroxypropyl guar gum supplied by Lamberti spa, and was used as received. This polymer was used as a comparison to the polymers of the invention. PREPARATION OF R7-33-43 ANION HYDROPHOBICALLY MODIFIED POLYMER SYNTHESIS OF M-TMI BEENYLIC ALCOHOL MONOMER:
[118] 75 g of behenyl alcohol (available from Cognis) was melted and added to a reactor and heated to 95°C and sparged with nitrogen for 4 hours to remove any water. Nitrogen sparging was discontinued and the reaction temperature was reduced to 78°C. 0.3 g of monomethyl ether hydroquinone inhibitor (MEHQ) and 0.3 g of stannous 2-ethylhexanoate (FASCAT® 2003 available from Arkema Inc, Philadelphia, PA) were then added to the reactor. 47.6 g of 3-isopropenyl-α,α-dimethylbenzyl isocyanate (m-TMI available from Cytec, Stamford, CT) was then slowly added to the reactor over a 30 minute period. A slight exothermic reaction was observed, which raised the temperature from 78 to 83°C. After addition, the reactor was kept at 80°C for a further 30 minutes. The final product was a liquid that cooled to a solid at room temperature. R7-33-43 POLYMER SYNTHESIS:
[119] An initial charge of 40.8 g of water and 153.5 g of isopropyl alcohol were added to a 1 liter glass reactor. The reactor contents were heated to reflux (approximately 82 to 84°C). In a separate beaker, 142 g of acrylic acid was heated to 55°C, and then 60 g of the m-TMI behenyl alcohol urethane from the previous step was added with stirring. This hot mixture was added to the refluxing reactor over a period of 2.5 hours. A solution of 1.9 g of sodium persulfate dissolved in 60 g of water was added simultaneously, but over said period of 2.5 hours. The reaction temperature was maintained at about 85°C for one hour. A cleaning feed (to minimize residual monomers) containing 0.175 g of sodium persulfate dissolved in 10 of water was then added to the reactor over 30 minutes at 85°C. The reactor was then configured for distillation, which was carried out at a higher temperature and/or reduced pressure, to ensure controlled distillation without polymer degradation. A small amount of ANTIFOAM® 1400 (0.12 g) (from Dow Chemical) was added to suppress any foam generated during the distillation. Alcohol (the co-solvent) was removed from the polymer solution by azeotropic distillation. During the distillation, about 1350 g of water were added. Approximately 263 g of a mixture of water and isopropyl alcohol was distilled. After the distillation was completed, the reaction mixture was cooled, and 21.8 g of 50% NaOH was added. The final product had a pH of 2.2 and solids of 13.3 percent. PREPARATION OF HYDROPHOBICALLY MODIFIED ANIONIC POLYMER R7-33-61 M-TMI ARMEEN MONOMER SYNTHESIS:
[120] 70 g of octadecylamine (Armeen® 18D, available from AkzoNobel Surface Chemistry) was melted and added to a reactor and heated to 90°C. Liquid octadecylamine was sparged with nitrogen for 4 hours to remove any water in the material. Nitrogen sparging was discontinued and the reaction temperature was reduced to 78°C. 0.3 g of monomethyl ether hydroquinone inhibitor (MEHQ) and 0.3 g of stannous 2-ethylhexanoate (FASCAT® 2003 available from Arkema Inc, Philadelphia, PA) were then added to the reactor. 52.2 g of 3-isopropenyl-α,α-dimethylbenzyl isocyanate (m-TMI available from Cytec, Stamford, CT) was then slowly added to the reactor over a period of 45 minutes. A slight exothermic reaction was observed, which raised the temperature from 80 to 83°C. After addition, the reactor was kept at 80°C for a further 30 minutes. The final product was a liquid that cooled to a solid at room temperature. SYNTHESIS OF R7-33-61 POLYMER:
[121] An initial charge of 38 g of water and 150 g of isopropyl alcohol was added to a 1 liter glass reactor. The reactor contents were heated to reflux (approximately 82 to 84°C). In a separate beaker, 142 g of acrylic acid was heated to 55°C, and then 58.4 g of Armeen 18D m-TMI monomer was added with stirring. This hot mixture was added to the refluxing reactor over a period of 2.5 hours. A solution of 1.9 g of sodium persulfate dissolved in 61 g of water was added simultaneously, but over a period of 2.5 hours. The reaction temperature was maintained at about 85°C for one hour. A cleaning feed containing 0.17 g of sodium persulfate dissolved in 10 of water was then added to the reactor over 30 minutes at 85°C. The reactor was then set up for distillation. A small amount of ANTIFOAM® 1400 (0.12 g) (from Dow Chemical) was added to suppress any foam generated during the distillation. Alcohol co-solvent was removed from the polymer solution by azeotropic distillation. During the distillation, about 1080 g of water was added. Approximately 251 g of a mixture of water and isopropyl alcohol was distilled. After the distillation was completed, the reaction mixture was cooled. The final product had a pH of 2.5 and solids of 15.7 percent. PREPARATION OF HYDROPHOBICALLY MODIFIED ANIONIC POLYMER R7-33-72 M-TMI 2-DECYL-TETRADECANOL MONOMER SYNTHESIS:
[122] 150 g of 2-decyl-tetradecanol (branched alcohol) [Isofol® 24 (97.5%) (available from Sasol, Houston, TX)] was added to a 500 ml reactor and heated to 80°C. The reactor contents were sparged with nitrogen for 4 hours to remove any water in the material. Nitrogen sparging was discontinued and the reaction temperature was reduced to 68°C. 0.33 g of monomethyl ether hydroquinone inhibitor (MEHQ) and 0.33 g of stannous 2-ethylhexanoate (FASCAT 2003 available from Arkema Inc, Philadelphia, PA) were then added to the reactor. 82.5 g of 3-isopropenyl-α,α-dimethylbenzyl isocyanate (m-TMI available from Cytec, Stamford, CT) was then slowly added to the reactor over a 30 minute period. A slight exothermic reaction was observed, which raised the temperature from 70 to 71°C. After addition, the reactor was held at 72°C for a further 60 minutes. The final product was a liquid. SYNTHESIS OF R7-33-72 POLYMER:
[123] An initial charge of 43 g of water and 133 g of isopropyl alcohol were added to a 1 liter glass reactor. The reactor contents were heated to reflux (approximately 82 to 84°C). A first monomeric solution of 33 g acrylic acid, 20.11 g m-TMI 2-decyl-tetradecanol monomer (synthesized above), 9.9 g isopropyl alcohol, and 4.1 g hydroxypropyl methacrylate were added to the reactor at reflux over a period of 75 minutes. A second monomeric solution containing 12.8 g of 50% 2-acrylamido-2-methyl propane sulfonic acid, sodium salt in 20 g of water was added concurrently over a period of 75 minutes. An initiator solution of 0.97 g of sodium persulfate dissolved in 28.3 g of water was added simultaneously, but over a period of 90 minutes. The reaction temperature was maintained at about 85°C for one hour. A cleaning feed containing 0.15 g of sodium persulfate dissolved in 10 of water was then added to the reactor over 30 minutes at 85°C. The reactor was then set up for distillation, and a small amount of ANTIFOAM® 1400 (0.12 g) (from Dow Chemical) was added to suppress any foam generated during the distillation. Alcohol co-solvent was removed from the polymer solution by azeotropic distillation. Approximately 185 g of a mixture of water and isopropyl alcohol was distilled. During the distillation, about 242 g of water was added to replace the distillate and keep the viscosity at a manageable level. After the distillation was completed, the reaction mixture was cooled, and 7 g of 50% NaOH in 15 g of water was added. The final product had a pH of 4.2 and solids of 16.9 percent. PREPARATION OF POLYMER R7-33-158
[124] An initial charge of 77 g of water and 100 g of isopropanol was added to a 1 liter glass reactor. The reactor contents were heated to 82°C. A first solution which is a mixture of 72.7 g of acrylic acid and 21.6 g of an N-octadecyl acrylamide dissolved in 50 g of isopropanol was added to the reactor over a period of 80 minutes. A second initiator solution of 0.97 g of sodium persulfate dissolved in 46 g of water was added simultaneously at the same time, but over a period of 90 minutes. After the addition of the second solution was complete, an initiator solution of 0.09 g of sodium persulfate dissolved in 14 g of water was then added, over a period of 10 minutes. The reactor was then set up for distillation. Alcohol co-solvent was removed from the polymer solution by azeotropic distillation. During the distillation, 450 g of water was dropped, and approximately 303 g of a mixture of water and alcohol was distilled. The final product was a colorless viscous solution with a pH of 2.6 and a solids content of 19.9%. PREPARATION OF POLYMER R7-33—28
[125] An initial charge of 72.9 g of water and 50.9 g of ethanol was added to a 500 ml glass reactor. The reactor contents were heated to reflux (approximately 82 to 84°C). A mixture of 38.1 g acrylic acid and 5.55 g lauryl methacrylate was added to the refluxing reactor over a period of 3 hours. A solution of 0.6 g of sodium persulfate dissolved in 32 g of water was added simultaneously, but over a period of 4 hours. The reaction temperature was maintained at about 85°C for 30 minutes. The reactor was then set up for distillation. Alcohol co-solvent was removed from the polymer solution by azeotropic distillation. During the distillation, 38.8 g of 50% NaOH dissolved in 70 g of water were added dropwise. Approximately 99.3 g of a mixture of water and ethanol was distilled. The final product has 25.25% solids and pH = 7.5. PREPARATION OF POLYMER J3—9—46
[126] An initial charge of 150 g of diallyldimethylammonium chloride (commercial material from Aldrich 65% further concentrated to 88% by removal of water), 150 g of isopropyl alcohol, and 32.2 g of m-TMI 2- monomer decyl tetradecanol (synthesized above) were added to a 1 liter reactor equipped with a reflux condenser. An initiator feed consisting of Esperax 28 in isopropyl alcohol (16.4 g in a total volume of 100 ml) was prepared. The reaction was maintained in the 83 to 87°C range to allow reflux of IPA while the initiator solution was added over a 2 hour period. Following the slow addition of initiator, the reaction was held at 83°C (refluxing IPA) for 2.5 hours. The reaction was cooled below reflux temperature, and the reactor was then equipped with a Dean-Stark apparatus to allow for the collection and removal of distillate. IPA/water was removed at 81 to 86°C while the reaction volume was replenished with water from an additional funnel to maintain an acceptable viscosity. The total distillate collection up to this point was 194 g, while the added water was 350 g. Due to the intense foaming, an additional 195 g of water was added to the reaction, and the reaction mixture was then transferred to a rotary evaporator, where an additional 110 g of distillate was removed under vacuum at 55°C. The weight of the final material after being subjected to distillation was 690 g. This was a slightly cloudy, pink liquid with a pH of 4 and consisting of 23% active polymer by weight.
[127] The following Table 1 shows the molecular weights of some of the polymers tested in the experiments below. Molecular weights were measured as described in this document.
Exemplo 1 e Exemplos comparativos A-B: Reologia de Aromox APA-TW e polímero hidrofobicamente modificado R7-33-43 As amostras A, B, e 1 foram feitas com base na quantidade mostrada na Tabela 2. Tabela 2: Preparação de Amostras de Aromox APA-TW + [128] Table 1: Analysis of hydrophobically modified polymers compared to conventional POLYFLOS® HM 21. Example 1 and Comparative Examples AB: Rheology of Aromox APA-TW and hydrophobically modified polymer R7-33-43 Samples A, B, and 1 were made based on the quantity shown in Table 2. Table 2: Preparation of Aromox APA Samples -TW+
[129] For samples A, B, and 1, an ARES tension-controlled rheometer (from Rheometric Scientific, which is now TA Instruments) was used to conduct the strain-rate scan stable at 25°C, with a rate of an initial voltage of 0.01 s-1 and a final voltage rating of 100 s-1. Data were collected, 10 data points per decade of voltage rate. 25 mm diameter parallel plates were used, and the temperature was controlled by Peltier heating.
[130] The rheology profile is graphically represented in Figure 1. Clearly, Sample 1 shows significantly higher viscosity than Sample A and Sample B, indicating a synergistic viscosity increase achieved by a combination of Aromox APA-TW and R7- polymer 33-43 (a polymer with a urethane bond) in 4% KCl. The same synergistic viscosity increase was also found at 50°C and at 80°C.
[131] In a separate rheology test at 25°C, a dynamic frequency of 10-1 to 102 rad/s was used, and, for the Example 1 solution, G' was higher than G” throughout. the range, indicating that the solution showed viscosity behavior. EXAMPLE 2 AND COMPARATIVE EXAMPLES C-D
[132] Rheology of Aromox APA-TW and hydrophobically modified polymer R7-33-61
[133] Samples C, D, and 2 were made based on the quantity shown in Table 3. Table 3: Aromox APA-TW + R7-33-61 Sample Preparation
[134] For samples C, D, and 2, an ARES stress-controlled rheometer (from Rheometric Scientific, which is now TA Instruments) was used to conduct the scan at a stable stress rate at 25°C, with a rate of an initial voltage of 0.01 s-1 and a final voltage rating of 100 s-1. Data were collected, 10 data points per decade of voltage rate. 25 mm diameter parallel plates were used, and the temperature was controlled by Peltier heating.
[135] The rheology profile is graphically represented in Figure 2. Again, sample 2 shows significantly higher viscosity than sample C and sample D, indicating a synergistic viscosity increase achieved by a combination of Aromox APA-TW and polymer R7- 33-61 (a polymer with a urea bond) in 4% KCl. The same synergistic viscosity increase was also found at 50°C and at 80°C.
[136] In a separate rheology test at 25°C, a dynamic frequency of 10-1 to 102 rad/s was used, and, for the Example 2 solution, G' was higher than G” throughout. the range, indicating that the solution showed viscosity behavior. COMPARATIVE EXAMPLES E AND F: RHEOLOGY OF AROMOX® APA-TW AND POLYFLOS® HM 21.
[137] Samples E and F were formulated as shown in Table 4. Table 4: Sample Preparation of 21Aromox APA-TW + POLYFLOS® HM 21
[138] The rheology profile is graphically represented in Figure 3. The result shows that samples E and F overlap very well with each other, indicating no rheological synergy after combining POLYFLOS® HM 21 with Aromox APA-TW in KCl 4 %.
[139] It is highlighted that the polymer according to the invention (R7-33-43 of Example 1) has a much lower molecular weight than the conventional thickener POLYFLOS® HM 21 of Comparative Example F, see Table 1 above. Thus, it is surprising to see that the use of conventional hydrophobic polymers does not lead to the viscosities observed when using the polymers of the invention. EXAMPLES 3 AND 4 AND COMPARATIVE EXAMPLE G - RHEOLOGY OF AROMOX APA-TW, R7-33-43 POLYMER AND R7-33-61 POLYMER.
[140] Here, the performance of an amine oxide viscoelastic surfactant in combination with the hydrophobically modified polymers R7-33-43 and R7-33-61 was investigated for an aqueous environment containing 4% KCl at elevated temperature (93 °C). (200oF)) and at a high pressure (27.5 bar (400psi)), to mimic oil well stimulation conditions. The amounts of surfactant and polymer used, as well as the results obtained, are shown in the following Table 5, with the viscosity being determined after two hours at a shear rate of 100 s-1, using a Grace M5600 rheometer at said pressure and temperature with rotor R1 and bob B5. Table 5 - sample preparation of samples G, 3
[141] Clearly, also in an aqueous formulation containing KCl and at high temperature and pressure, the combination of viscoelastic surfactant and hydrophobically modified polymer according to the invention provided a very high viscosity, even when the polymer was used in a small amount, and despite the low molecular weight of the polymer. EXAMPLE 5 AND COMPARATIVE EXAMPLES H AND I - RHEOLOGY OF AROMOX APA-TW AND R-36-72 POLYMER
[142] Here, the performance of an amine oxide viscoelastic surfactant in combination with the hydrophobically modified polymer R7-36-72 was investigated for an aqueous environment containing 4% w/p KCl and a CaCl2 amount of 2,776 ppm (0.2776 %w/w) at 25°C. The amounts of surfactant and polymer used, as well as the results obtained, are shown in Table 6. Table 6 - sample preparation of samples H, I
[143] The combination according to the invention provided a higher viscosity than the use of the surfactant or polymer alone, showing the synergistic behavior despite the low molecular weight of the polymer and the small amount in which it was used, as shown in Figure 4 Polymer R7-36-72 contained AMPS monomer which provided tolerance to calcium brine. EXAMPLE 6 AND COMPARATIVE EXAMPLE J - RHEOLOGY OF AROMOX APA-TW AND R-22-43 POLYMER WITH EDTA
[144] In these examples, the experiment of Example 5 was repeated, except that the hydrophobically modified polymer R7-33-43 was used, while also using the well-known EDTA chelate (Dissolvine NA) in the composition. Samples 6 and J were prepared according to the quantity shown in Table 7. Table 7 - sample preparation, samples 6 and J
[145] Figure 5 shows the viscosity of these formulations.
[146] The results show that the combination of viscoelastic surfactant and low molecular weight hydrophobically modified polymer provides exceptionally high viscosity at low concentrations also in the presence of a chelate. EXAMPLE 7 AND COMPARATIVE EXAMPLE K — RHEOLOGY OF AROMOX APA-TW AND R7-33—158 POLYMER
[147] Samples 7 and K were prepared according to the quantities indicated in Table 8 Table 8 - Preparation of Samples 7 and K
[148] For sample K, a strain-controlled rheometer ARES (from Rheometric Scientific, which is now TA Instruments) was used to conduct the scan at stable strain rate at 25°C, with an initial strain rate of 0 .01 s-1 and a final voltage rating of 100 s-1. Data were collected, 10 data points per decade of voltage rate. 25 mm diameter parallel plates were used, and the temperature was controlled by Peltier heating.
[149] Figure 6 shows the viscosity of these samples. It can be seen from the superimposed rheology profiles that the viscosity of sample 7 is greater than that of sample K in the tested shear rate range. The blend of Aromox APA-TW and R7-33-158 polymer (a polymer with an amide bond between the pendant hydrophobe and the backbone) has a higher viscosity than Aromox APA-TW alone. COMPARATIVE EXAMPLES L AND M - RHEOLOGY OF AROMOX APA-TW AND R-33-28 POLYMER
[150] Samples L and M were prepared according to the quantities indicated in Table 9. Table 9 - Preparation of samples L and M
[151] For samples L and M, a stress-controlled rheometer ARES (from Rheometric Scientific, which is now TA Instruments) was used to conduct the scan at a stable stress rate at 25°C, with an initial stress rate of 0.01 s-1 and a final voltage rating of 100 s-1. Data were collected, 10 data points per decade of voltage rate. 25 mm diameter parallel plates were used, and the temperature was controlled by Peltier heating.
[152] Figure 7 shows the viscosity of these samples. It can be seen from the superimposed rheology profiles that the viscosity of sample M is less than that of sample L. A blend of Aromox APA-TW and polymer R7-33-28 (a polymer with an ester bond between the pendant hydrophobe and backbone) has lower viscosity than Aromox APA-TW alone. In this case, the blend between VES and polymer showed a “negative” rheology synergy. EXAMPLE 8 AND COMPARATIVE EXAMPLE N - VISCOELASTICITY OF AROMOX APA-TW AND R7-33-43 POLYMER
[153] Samples 8 and N were prepared according to the quantities indicated in the following Table 10. Table 10 - Preparation of samples 8 and N
[154] Dynamic Frequency Scan was tested using an SR-5000 voltage-controlled rheometer (originally made by Rheometrics) at 25°C, with initial frequency of 0.01 rad/s and final frequency of 100 rad/s, and voltage = 1 Pa. Parallel plates 40 mm in diameter were used, and the temperature was controlled by Peltier heating. 10 data points were collected within each frequency decade.
[155] Results are shown in Figures 8 and 9
[156] From Figure 8, one can see the significant difference in the G' and G” profiles between the two samples. Sample N had no polymer, and its G', G” crossover frequency was approximately 3 rad/s. The sample showed viscoelasticity, or G’ > G”, only at frequencies that are greater than 3 rad/s. Sample 8 was the mixture between Aromox APA-TW and polymer R7-33-43, and its G',G” crossover frequency was approximately 0.02 rad/s. The sample showed viscoelasticity, or G’ > G”, at frequencies that are greater than 0.02 rad/s. Therefore, the VES-polymer blend showed a much wider frequency range where viscoelasticity was demonstrated.
[157] From Figure 9, one can see the significant difference in phase angle between these two samples. Sample N had no polymer, and its phase angle is generally greater than 45 degrees. Its phase angle was only below 45 degrees at frequencies greater than 3 rad/s, indicating that it only has viscoelastic characteristics at frequencies greater than 3 rad/s. Sample 8 was the mixture between Aromox APA-TW and polymer R7-33-43, and its phase angle was below 45 degrees at frequencies greater than 0.02 rad/s. These are further data to support that the VES-polymer blend is more viscoelastic than VES alone. EXAMPLE 9 AND COMPARATIVE EXAMPLE O - VISCOELASTICITY OF AROMOX APA-TW AND POLYMER J3-9-46
[158] Samples 9 and O were prepared according to the quantities indicated in the following Table 11. Table 11 - Preparation of samples 9 and O

[159] For sample O, a stress-controlled rheometer ARES (from Rheometric Scientific, which is now TA Instruments) was used to conduct the scan at a stable stress rate at 25°C, with an initial stress rate of 0 .01 s-1 and a final voltage rating of 100 s-1. Data were collected, 10 data points per decade of voltage rate. 25 mm diameter parallel plates were used, and the temperature was controlled by Peltier heating.
[160] Figure 10 shows the results of these experiments. For sample O, an ARES strain-controlled rheometer (from Rheometrics, which is now TA Instrument) was used to conduct the scan at a stable strain rate at 25°C, with an initial strain rate of 0.01 s- 1 and a final voltage rating of 100 s-1. Data were collected, 10 data points per decade of voltage rate. 25 mm diameter parallel plates were used, and the temperature was controlled by Peltier heating. For sample 9, a voltage-controlled rheometer SR-5000 (from Rheometrics, which is now TA Instrument) was used to conduct the scan at stable voltage at 25°C, with an initial voltage of 0.1 Pa, a voltage 40 Pa final, and a linear tension increment of 0.5 Pa. Parallel plates 40 mm in diameter were used, and the temperature was controlled by Peltier heating.
[161] It can be seen from the superimposed rheology profiles that the viscosity of sample 9 is greater than that of sample O in the tested shear rate range. The blend of Aromox APA-TW and polymer J3-9-46 (a hydrophobically modified cationic polymer) has a higher viscosity than Aromox APA-TW alone. EXAMPLE 10: ANION/BETAINE AND POLYMER DILUTION EXPERIMENTS
[162] Sodium lauryl ether sulfate and cocoamidopropyl betaine were chosen as exemplary surfactants. They were used in a constant ratio to each other of 4:1, respectively. A series of eight dilution experiments was conducted. The compositions of the two series of experiments are found in Table 12 shown below. Sodium chloride was the salt used in all samples in Example 10. The first four dilution experiments (labeled 1 to 4) represent “polymer-free controls”. The last four dilution experiments (labeled 5 to 8) contain different levels of an R7-36-72 polymer of the current invention. Columns A through D represent fixed levels of surfactant (column A for 15% surfactant, B for 10% surfactant, C for 7.5% surfactant, and D for 6% surfactant). In Table 13, it is shown that zero shear viscosities are related to dilution experiments described in Table 12. Table 12
[163] Comparisons to determine the influence of polymer on different salt levels can be made between the dilution experiment pairs of 1 and 5, 2 and 6, 3 and 7 and 4 and 8. Zero Shear Viscosity
[164]Zero shear viscosities were obtained from a graph of viscosity vs. shear rate or fitting the data to the cross model. Viscosities were measured using a stress-controlled rheometer SR-5000 (from Rheometric Scientific, which is now TA Instruments), a stress-controlled rheometer using a 25 mm diameter parallel plate configuration and 1 mm spacing. Steady-state stress scan measurements were performed at 25°C, and data at different shear rates were obtained.
n0=viscosidade em taxa muito alta, y = taxa de Dcisalhamento, C e m são constantes.[165]The zero shear viscosity was obtained by averaging the values at the plateau at the lower end of the shear rate range. For cases where the value does not reach the plateau, the data were fitted to the cross model. The adjustment was performed using the Microsoft Excel software resolution module and defining the criterion to minimize the sum of percentage differences between the observed and adjusted data. According to the cross model, viscosity is related to shear rate through the following equation: n0=viscosity at very high rate, y = shear rate, C and m are constant.
[166] In one experiment, where n was measured in 0.0404 Pa*s, C was determined to be 0.01, and m was determined to be 0.97, resulting in n0 being 0.41 Pa*s.
[167]The graph in Figure 11 displays the results for viscosity at zero vs. % w/w salt (NaCl) for the 8 dilution experiments of example 10. In this case, experiments no. 5 to 8 refer to experiments employing R7-36-72 as the polymer of the present invention.
[168] These data demonstrate that R7-36-72 can effectively increase the zero-shear viscosity for the sodium lauryl ether sulfate/cocamidopropyl betaine mixture across all surfactant levels, higher than it can be. be achieved without polymer. Additionally, it can generally be seen that the peak viscosity of the system can be reached with lower salt levels than in the absence of the polymer of the present invention. Furthermore, it can be seen that the zero shear viscosity of a system containing a high level of surfactant can be achieved at a substantially lower surfactant content by adding the polymer of the present invention with the appropriate level of salt.
[169] The peak viscosity achieved for each level of surfactant is provided in Table 14 below. Peak viscosity refers to the highest viscosity achieved over the entire range of salt that was tested. Table 14
[170] The comparison between samples with and without polymer shows that in all cases, the addition of polymer allows for higher viscosities at zero shear. Additionally, the comparison between 15% polymer-free surfactant (130 Pa*s) with 10% polymer-free surfactant (173 Pa*s) and 10% polymer-free surfactant (429 Pa*s) shows that it is possible to achieve higher viscosities at zero shear with lower levels of surfactant through addition of the polymer of the present invention and the appropriate level of salt.

权利要求:
Claims (13)
[0001]
1. AQUEOUS VISCOELASTIC COMPOSITION, characterized by comprising a. at least one viscoelastic surfactant selected from the group consisting of amine oxide and amidoamine oxide surfactants, and b. at least one hydrophobically modified polymer which: i. is obtainable by copolymerizing at least one first and at least one second ethylenically unsaturated monomer, wherein a. said first monomer is an ethylenically unsaturated monomer with an optionally alkoxylated hydrocarbyl group having from 6 to 40 carbon atoms, being connected to the unsaturated function of said monomer through a non-ester containing bond selected from the group consisting of a bond group containing urea, urethane and imide, more preferably a linking group containing urea or urethane; and b. said second monomer is an ethylenically unsaturated monomer free of hydrocarbyl groups having 6 or more carbon atoms connected to the unsaturated function of said monomer; i. said first and second monomers being present in a mutual molar ratio of 0.1:99.9 to 90:10; ii. It has a weight average molecular weight of 1,000 to 90,000 Da; iii. at a level of at least 0.1 mol%, based on the amount of monomeric units in the polymer, contains monomeric units, each covalently attached to a pendant, optionally alkoxylated hydrocarbyl group having from 6 to 40 carbon atoms, said optionally alkoxylated pendant hydrocarbyl group being connected to the backbone of said hydrophobically modified polymer through a linking group containing urea, urethane or imide, and c. a member selected from the group consisting of organic salts and inorganic salts.
[0002]
A COMPOSITION according to claim 1, characterized in that said pendant hydrocarbyl group, optionally alkoxylated, has at least 12 carbon atoms, and said hydrophobically modified polymer, at a level of 0.1 to 20% by mol, preferably of 0.5 to 10 mol%, more preferably 1 to 5 mol%, based on the amount of monomeric units in the polymer, will contain monomeric units connected to said optionally alkoxylated pendant hydrocarbyl group.
[0003]
A COMPOSITION according to claim 1, characterized in that said pendant hydrocarbyl group, optionally alkoxylated, has at most 11 carbon atoms, and said hydrophobically modified polymer, at a level of 1 to 50% by mol, preferably from 5 to 40% by mol, more preferably 10 to 30% by mol, based on the amount of monomeric units in the polymer, will contain monomeric units connected to said optionally alkoxylated pendant hydrocarbyl group.
[0004]
A COMPOSITION according to any one of claims 1 to 3, characterized in that said optionally alkoxylated pendant hydrocarbyl group contains at least 8, preferably at least 11 carbon atoms.
[0005]
A COMPOSITION according to any one of claims 1 to 4, characterized in that said pendant hydrocarbyl group, optionally alkoxylated, contains at most 32, preferably at most 24 carbon atoms.
[0006]
6. COMPOSITION according to claim 1, characterized in that said optionally alkoxylated hydrocarbyl group has at least 12 carbon atoms, and said first and second monomers are present in a molar ratio of 0.1:99.9 to 20: 80; preferably from 0.5:99.5 to 10:90, more preferably from 1:99 to 5:95.
[0007]
7. COMPOSITION according to claim 1, characterized in that said optionally alkoxylated hydrocarbyl group has at most 11 carbon atoms, and said first and second monomers are present in a mutual molar ratio of 1:99 to 90:10; preferably from 5:95 to 70:30, more preferably from 10:90 to 50:50.
[0008]
R2 X Rhy onde R1, R2, e R3 são independentemente selecionados dentre H, CH3, COOH, e CH2COOH, Rhy é um grupo hidrocarbila linear ou ramificado, saturado ou insaturado possuindo de 6, preferivelmente de 8, mais preferivelmente de 11, a 40, preferivelmente a 32, mais preferivelmente a 24 átomos de carbono, cujo grupo opcionalmente é alcoxilado, X é um grupo de ligação contendo ureia, uretano ou imida.8. COMPOSITION according to any one of claims 6 to 7, characterized in that said first ethylenically unsaturated monomer has the formula: R2 X Rhy where R1, R2, and R3 are independently selected from H, CH3, COOH, and CH2COOH, Rhy is a linear or branched, saturated or unsaturated hydrocarbyl group having from 6, preferably from 8, more preferably from 11, to 40 , preferably at 32, more preferably at 24 carbon atoms, which group is optionally alkoxylated, X is a linking group containing urea, urethane or imide.
[0009]
A COMPOSITION according to any one of claims 1 to 8, characterized in that the weight ratio of hydrophobically modified polymer to viscoelastic surfactant is 0.1:100, preferably 1:100, more preferably 3:100, to 100 :50, preferably at 100:100, more preferably at 50:100.
[0010]
A COMPOSITION according to any one of claims 1 to 9, characterized in that the concentration of said viscoelastic surfactant is 0.1, preferably 0.2, more preferably 0.3, to 50, preferably to 40, more preferably to 10 % by weight of the total composition.
[0011]
11. COMPOSITION according to any one of claims 1 to 10, characterized in that the hydrophobically modified polymer is used as a thickener.
[0012]
12. METHOD FOR FRACTURING A ROCK FORMATION, characterized in that it comprises the steps of injecting a viscoelastic composition, as defined in any one of claims 1 to 10, through a hole into said rock formation at a pressure sufficient to fracture said rock .
[0013]
13. METHOD, according to claim 12, characterized in that said rock formation is an underground formation, and said hole is a well hole.

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法律状态:
2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-07-02| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|

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2019-10-08| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2020-12-08| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2021-04-06| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-06-22| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 15/12/2011, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US42371010P| true| 2010-12-16|2010-12-16|

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US61/423,710|2010-12-16|

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EP11161261|2011-04-06|

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EP11161261.0|2011-04-06|

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PCT/EP2011/072861|WO2012080382A1|2010-12-16|2011-12-15|Compositions of viscoelastic surfactant and hydrophobically modified polymer as aqueous thickeners|

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