WO2015042028A1 - Polymères réticulés stables à hautes températures - Google Patents

Polymères réticulés stables à hautes températures Download PDF

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Publication number
WO2015042028A1
WO2015042028A1 PCT/US2014/055815 US2014055815W WO2015042028A1 WO 2015042028 A1 WO2015042028 A1 WO 2015042028A1 US 2014055815 W US2014055815 W US 2014055815W WO 2015042028 A1 WO2015042028 A1 WO 2015042028A1
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polymer
monomers
sulfonic acid
carbon atoms
acid
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PCT/US2014/055815
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English (en)
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Krishnan Tamareselvy
Cory G. Miller
Hyungsoo KIM
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The Lubrizol Corporation
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Publication of WO2015042028A1 publication Critical patent/WO2015042028A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
    • C08F220/585—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine and containing other heteroatoms, e.g. 2-acrylamido-2-methylpropane sulfonic acid [AMPS]

Definitions

  • This disclosed technology relates to a viscosifying agent for use in a composition and/or process for drilling, cementing, hydraulic fracturing, and/or enhanced oil recovery.
  • the viscosifying agent is a cross-linked polymer made up of units derived from a unique mixture of monomers. The polymer has good effectiveness as a viscosifying agent while also having good high temperature stability.
  • Water based drilling fluids often contain viscosifying agents such as starches, guar gum, guschleroglucans, polyacrylates, and a wide variety of synthetic and natural polymers to establish and control the theological properties of the drilling fluid.
  • viscosifying agents such as starches, guar gum, guschleroglucans, polyacrylates, and a wide variety of synthetic and natural polymers to establish and control the theological properties of the drilling fluid.
  • temperatures can be in excess of 300°F (149°C). Exposure to such temperatures can have a detrimental effect on viscosifying agents, resulting in a loss in viscosity of the fluid at high temperatures.
  • a breakdown of the rheology i.e., loss in viscosity, can result in the drilling fluid being unable to suspend the solids dispersed within it such as the weighting or bridging agent or even the drill cuttings which can lead to severe problems such as settlement, loss in fluid density and possibly a blowout of the well.
  • the disclosed technology seeks to provide a thermally stable viscosifying agent for use in aqueous wellbore fluids.
  • the disclosed technology provides a polymer that includes units derived from: (A) a first monomer composition including an ethylenically unsaturated hydrocarbylamidoalkanesulfonic acid monomer, where the monomer includes at least one alkyl group containing 5 to 30 carbon atoms, or salts thereof; (B) a second monomer composition including one or more ethylenically unsaturated polymerizable monomers, or salts thereof; and (C) a third composition comprising one more crosslinking agents; wherein the second monomer of (B) is different from the first monomer of (A).
  • the second monomer composition comprises at least one of: (i) one or more ethylenically unsaturated hydrocarbylamidoalkanesulfonic acid monomers where the monomers of free of any alkyl groups containing more than 4 carbon atoms or salts thereof; (ii) one or more carboxylic acid monomers or partial esters, or salts thereof; (iii) one or more amide monomers; (iv) one or more alkoxylated hydrophobically modified associative monomers; (v) one or more phosphonic acid monomers or partial esters, or salts thereof; (vi) one or more vinyl monomers; or (vii) any combination thereof.
  • (B) comprises one or more ethylenically unsaturated hydrocarbylamidoalkanesulfonic acid monomers where the monomers are free of any alkyl groups containing more than 4 carbon atoms.
  • (B) comprises a compound having the structure:
  • R 4 is an alkyl group containing 1 to 4 carbon atoms
  • R 5 is hydrogen or an alkyl group containing from 1 to 4 carbon atoms
  • R 6 is an alkyl group containing 1 to 4 carbon atoms
  • R 7 is hydrogen or a methyl group; or a metal, ammonium, or alkylamine salt thereof.
  • (B) comprises 2-acrylamido-2-methypropane-l -sulfonic acid, a mono or multivalent metal of one or more thereof, an ammonium salt or one or more thereof, an alkylamine salt of one or more thereof or a combination thereof.
  • (B) comprises one or more ethylenically unsaturated polymerizable carboxylic acid monomers, or salts and/or esters or partial esters thereof.
  • (B) comprises acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid or salts and/or esters or partial esters thereof.
  • (B) comprises one or more ethylenically unsaturated amido functional monomers selected from acrylamide, methyl acrylamide, methyl methacrylamide, N-alkylmethacrylamide, ⁇ , ⁇ -dialkylmethacrylamide, N-alkylacrylamide, and N,N-dialkylacrylamide.
  • (C) includes ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 1 ,3-butylene glycol di(meth)acrylate, 1 ,4-butylene glycol di(meth)acrylate, 1 ,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1 ,9-nonanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate; dipentaerythritol hexa
  • (C) includes a borate or one or more polyvalent metal ions selected from the group consisting of zirconium, chromium, titanium, aluminum, and mixtures thereof.
  • crosslinking agents examples include, but are not limited to the following: boron compounds such as boric acid, disodium octaborate tetrahydrate, sodium diborate, pentaborate, or combinations thereof; compound that can supply chromium (III) ions such as chromium acetate, chromium lactate, chromium citrate or combinations thereof; compounds that can supply zirconium (IV) ions such as zirconium diethanolamine complex, zirconium triethanolamine complex, zirconium lactate, zirconium ethylene glycolate, zirconium acetylacetonate, tetrakis(triethanolaminato)zirconium, zirconium ammonium lactate, zirconium diethanol lactate, zirconium triethanolamine lactate, zirconium diisopropylamine lactate, zirconium sodium lactate salts, zirconium glycerol complex, zirconium sorb
  • the polymer further comprises units derived from: (D) a fourth monomer composition comprising one or more monomers that include an alkyl group containing 1 to 18 carbon atoms comprising a simple ester, a vinyl ester, an mono-allyl ether, or salts thereof, or any combination thereof.
  • R 1 is an alkyl group containing from 5 to 30 carbon atoms
  • R 2 is hydrogen or an alkyl group containing from 1 to 30 carbon atoms
  • R is an alkyl group containing 1 to 4 carbon atoms
  • R 7 is hydrogen or a methyl group; or a metal, ammonium, or alkylamine salt thereof.
  • (A) comprises 2- acrylamido-2-dodecane sulfonic acid, 2-acrylamido-2-hexadecane sulfonic acid, 2- acrylamido-2-octadecane sulfonic acid, 2-acrylamido-2-decane sulfonic acid, 2- acrylamido-2-octane sulfonic acid, 2-acrylamido-2-diisobutane sulfonic acid, 2- acrylamido-2-heptadecane sulfonic acid, 2-acrylamido-2-pentadecane sulfonic acid, 2- acrylamido-2-decane-2-octane sulfonic acid, 2-acrylamido-2-hexane sulfonic acid, 2- acrylamido-2-heptane sulfonic acid, 2-methacrylamido-2-dodecane s
  • the disclosed technology provides for embodiments where the polymer is made up of: 0.1 to 50, or 0.1 to 30, or even 0.1 to 10 percent by weight of monomer units derived from (A); and 1 to 99.89 or 30 to 99.89, or 50 to 99.89, or even 70 to 99.89 percent by weight of monomer units derived from (B); and 0.01 to 50 or even 0.01 to 20 percent by weight units derived from (C).
  • the disclosed technology provides for embodiments where the polymer is made up of: 0.1 to 50, or 0.1 to 30, or even 0.1 to 10 percent of monomer units derived from (A); 25 to 99.88 or from 45 to 99.88, or from 65 to 99.88 percent by weight units derived from (B); and 0.01 to 50 or even 0.01 to 20 percent by weight units derived from (C), and 0.01 to 49 or even 1 to 49 or even 0.01 to 5 percent by weight units derived from (D).
  • the disclosed technology provides for embodiments where the polymer is free of units derived from an alkylene glycol monomer.
  • R 1 is an alkyl group containing from 5 to 24 carbon atoms
  • R 2 is hydrogen or an alkyl group containing from 1 to 10 carbon atoms
  • R is an alkyl group containing 1 to 4 carbon atoms
  • R 7 is hydrogen or a hydrocarbyl group.
  • the disclosed technology provides for a process of making a polymer comprising the steps of: (I) reacting: (A) a first monomer composition comprising an ethylenically unsaturated hydrocarbylamidoalkanesulfonic acid monomer, where the monomer includes at least one alkyl group containing 5 to 30 carbon atoms, or salts thereof; (B) a second monomer composition comprising one or more ethylenically unsaturated polymerizable monomers, or salts thereof; and (C) a third composition comprising one more crosslinking agents; wherein the second monomer composition (B) is different from the first monomer composition (A).
  • the disclosed technology provides for embodiments where the process is a solution polymerization, a precipitation polymerization, a gel polymerization, or an inverse emulsion polymerization.
  • step (I) of the process further comprises reacting: (D) a fourth monomer composition comprising one or more monomers that include an alkyl group containing 1 to 18 carbon atoms comprising a simple ester, a vinyl ester, an mono-allyl ether, or any combination thereof; with (A), (B), and (C).
  • the disclosed technology provides for the use of the described polymer as a viscosifying agent and/or fluid loss control agent in a cement composition and/or in a cementing process.
  • the disclosed technology provides for the use of the described polymer as a friction reducer, viscosifying agent, fluid loss control agent, and/or a gelling agent in a hydraulic fracturing process.
  • the disclosed technology provides for methods that include the use of the described polymer as a viscosifying agent and/or fluid loss control agent in a drilling composition and/or in a drilling process.
  • the disclosed technology provides for methods that include the use of the described polymer as a viscosifying agent or a gelling agent in an enhanced oil recovery process.
  • the disclosed technology provides a polymer including units derived from: (A) a first monomer composition comprising an ethylenically unsaturated hydrocarbylamidoalkanesulfonic acid monomer, where the monomer includes at least one alkyl group containing 5 to 30 carbon atoms, or salts thereof; (B) a second monomer composition comprising one or more ethylenically unsaturated polymerizable monomers, or salts thereof; and (C) a third composition comprising one more crosslinking agents; wherein the second monomer composition (B) is different from the first monomer composition (A).
  • (A) and (B) differ in that the monomers of (B) do not contain a pendant alkyl group that includes more than 4 carbon atoms, while the monomers of (A) must include a pendant alkyl group containing from 5 to 30 carbon atoms.
  • (A) and (B) differ in that the monomers of (A) have a higher number average molecular weight than the monomers of (B).
  • (A) and (B) differ in that the monomers of (A) have the specific structure defined below for it, and the monomers of (B) have the specific structure defined below for it.
  • the monomer of (B) are ethylenically unsaturated amidoalkanesulfonic acids, partial esters thereof, or full esters thereof.
  • more than 50%, on a molar basis, of the monomers that become part of the described polymers are ionic.
  • the described polymer is made up of units where more than 50% of the units are ionic, such that the polymer may be described as ionic.
  • the monomers of (A) may include ethylenically unsaturated, water- soluble sulfonic acid monomers that have been hydrophobically modified and include polymerizable sulfonic acids such as unsaturated hydrocarbylamidoalkanesulfonic acids that have been hydrophobically modified, for example, acrylamido- or methacrylamidosulfonic acids hydrophobically modified by the addition of a long hydrocarbyl or alkyl substituent group.
  • the ethylenically unsaturated water-soluble polymerizable sulfonic acid can be an unsaturated-hydrocarbylamido-alkanesulfonic acid.
  • the monomers of (A) may include a compound having the structure:
  • R 1 is an alkyl group containing from 5 to 30 carbon atoms
  • R 2 is hydrogen or an alkyl group containing from 1 to 30 carbon atoms
  • R is an alkyl group containing 1 to 4 carbon atoms
  • R 7 is hydrogen or a methyl group; or a metal, ammonium, or alkylamine salt thereof.
  • R 1 is an alkyl group containing from 5 to 30 carbon atoms, or from 5 to 24, or from 6 to 24, or from 8 to 22, or from 6 to 18, or from 10 to 16 carbon atoms, or even 10, 14 or 16 carbon atoms.
  • R is hydrogen or an alkyl group containing from 1 to 30 carbon atoms, or even from 1 to
  • R is an alkyl group containing 1 to 4 carbon atoms, or even just 1 carbon atom.
  • R 7 is hydrogen or a methyl group.
  • Suitable examples for the monomers of (A) include 2-acrylamido-2- dodecane sulfonic acid, 2-acrylamido-2-hexadecane sulfonic acid, 2-acrylamido-2- octadecane sulfonic acid, 2-acrylamido-2-decane sulfonic acid, 2-acrylamido-2- octane sulfonic acid, 2-acrylamido-2-hexane sulfonic acid, 2-acrylamido-2-heptane sulfonic acid, 2-acrylamido-2-diisobutane sulfonic acid, 2-acrylamido-2- heptadecane sulfonic acid, 2-acrylamido-2-pentadecane sulfonic acid, 2- acrylamido-2-decane-2-octane sulfonic acid, 2-methacrylamido-2-dodecane sulfonic
  • the monomers of (B) may include at least one of: (i) one or more ethylenically unsaturated hydrocarbylamidoalkanesulfonic acid monomers where the monomers of free of any alkyl groups containing more than 4 carbon atoms or salts thereof; (ii) one or more carboxylic acid monomers or partial esters, or salts thereof; (iii) one or more amide monomers; (iv) one or more alkoxylated hydrophobically modified associative monomers; (v) one or more phosphonic acid monomers or partial esters, or salts thereof; (vi) one or more vinyl monomers; or (vii) any combination thereof.
  • the monomers of (B) include: (i) one or more ethylenically unsaturated hydrocarbylamidoalkanesulfonic acid monomers where the monomers of free of any alkyl groups containing more than 4 carbon atoms or salts thereof.
  • the monomers of (B) may include ethylenically unsaturated, water-soluble sulfonic acid monomers and include polymerizable sulfonic acids such as unsaturated hydrocarbylamidoalkanesulfonic acids, for example, acrylamido- or methacrylamidosulfonic acids, where the monomers are free of any alkyl groups containing more than 4 carbon atoms.
  • the monomers of (B) may include ethylenically unsaturated, water-soluble sulfonic acid monomers and include polymerizable sulfonic acids such as unsaturated hydrocarbylamidoalkanesulfonic acids, for example, acrylamido- or methacrylamidosulfonic acids.
  • the ethylenically unsaturated water-soluble polymerizable sulfonic acid can be an unsaturated-hydrocarbylamido-alkanesulfonic acid.
  • the pendent group can also include phenyl groups, alkyl substituted phenyl groups and cycloaliphatic groups.
  • the monomers of (B) may include a compound having the structure:
  • R 4 is an alkyl group containing 1 to 4 carbon atoms
  • R 5 is hydrogen or an alkyl group containing from 1 to 4 carbon atoms
  • R 6 is an alkyl group containing 1 to 4 carbon atoms
  • R 7 is hydrogen or a methyl group; or a metal, ammonium, or alkylamine salt thereof.
  • R 4 is an alkyl group containing less than 4 carbon atoms, 1 to 4 carbon atoms, or even just 1 carbon atom.
  • R 5 is hydrogen or an alkyl group containing less than 4 carbon atoms, from 1 to 4 carbon atoms or even just 1 carbon atom.
  • R 5 is hydrogen or a methyl group.
  • R 6 is an alkyl group containing 1 to 4 carbon atoms or even just 1 carbon atom.
  • R 7 is hydrogen or a methyl group. Any of these embodiments may also include a metal, ammonium, or alkylamine salt thereof.
  • suitable metals include either alkali or alkaline metals. In some embodiments, the metal is calcium.
  • suitable alkylamines include lipophilic amines and/or lipophilic amine salts.
  • the amine ion that is, the amine in its cationic form, can be represented by:
  • R 8 , R 9 , R 10 and R 11 are independently hydrogen or hydrocarbyl groups, provided that at least one of R 8 , R 9 , R 10 and R 11 is a hydrocarbyl group of sufficient length suitable to impart lipophilic properties.
  • the term "amine salt” or "amine ions” includes ions or salts, where up to three of the R groups are hydrocarbyl groups, and quaternary amine ions or salts, where each of the R groups is a hydrocarbyl group.
  • the total carbon atoms in the amine ion should be at least 6, and in one embodiment at least 10, or at least 14.
  • the total number of carbon atoms in an amine cation does not exceed 36 carbon atoms; thus the total number of carbon atoms may be, e. g., 6 to 36.
  • suitable amines include N, N- dimethyl -n- dodecylamine, 2-ethylhexylamine, tri-n-butylamine, triisobutylamine, triisooctylamine, tripropylamine, trihexylamine, trioctylamine, decylamine, dodecylamine, tridecylamine, tridodecylamine, hexadecylamine, octadecylamine, oleylamine, higher tert-alkyl primary amines such as Primene 81RTM and Primene JMTTM from Rohm and Haas, and aromatic amines such as pyridines, benzylamine, N-methylbenzylamine, 2-phene
  • lipophilic is given its conventional meaning that is, interacting favorably with or being soluble in non-polar or fatty solvents.
  • a synonym for “lipophilic” is “hydrophobic,” which may be contrasted with “hydrophilic.”
  • Hydrophobic materials exhibit little or no favorable interaction with water and are generally not appreciably soluble in water or similarly polar solvents.
  • the hydrophobic or hydrophilic character of a material can also be understood to approximately correlate with results derived from the octanol/water partition test.
  • the monomers of (B) include 2-acrylamido-2- methypropane-1 -sulfonic acid, a mono or multivalent metal of one or more thereof, an ammonium salt or one or more thereof, an alkylamine salt of one or more thereof or a combination thereof.
  • the monomers of (B) include: (ii) one or more carboxylic acid monomers or partial esters, or salts thereof.
  • the monomers of (B) may comprise one or more ethylenically unsaturated polymerizable carboxylic acid monomers, or salts and/or esters or partial esters thereof. Suitable examples include what are often referred to as carboxylic monomers or aery late monomers.
  • Suitable carboxylic acid monomers include: Sipomer COPS ® -I, commercially available from Rhodia, which is a 40% aqueous solution of sodium allyl ether sulfonate and sodium l-allyloxy-2-hydroxypropyl sulfonate, having a molecular weight of about 218; vinyl benzene sulfonic acids, vinyl benzene sulfonates, alkyl vinyl benzene sulfonic acids, alkyl vinyl benzene sulfonates for example SPINOMAR ® NaSS, commercially available from Tosoh, which is a sodium p- styrene sulfonate having a molecular weight of about 206; 2- sulfoethylmetahcrylate; alkylvinyl sulfonic acids, alkyl vinyl sulfonates for example sodium vinyl sulfonates
  • the monomers of (B) are essentially free of any acrylate monomers. In some embodiments, the monomers of (B) are free of any acrylate monomers. In some embodiments, the polymers described herein are essentially free of any acrylate monomers. In some embodiments, the polymers described herein are free of any acrylate monomers.
  • the monomers of (B) include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid or salts and/or esters thereof.
  • the esters thereof include full and partial esters thereof.
  • the monomers of (B) include one or more compounds having the structural formula:
  • R 12 is H or CH 3 ;
  • R 13 is H or COOH;
  • R 14 is H or COOH; and
  • R 15 is H,
  • R 12 is H and R 13 is COOH, R 14 and R 15 are different and are either H or COOH; when R 12 and R 13 are both H, R 14 is COOH and R 15 is CH 2 COOH; and when R 12 is CH 3 , R 13 is COOH and R 14 and R 15 are different and are either H or COOH.
  • Suitable examples include maleic acid, itaconic acid, fumaric acid, citraconic acid and mesaconic acid.
  • the monomers of (B) include: (iii) one or more amide monomers.
  • the monomers of (B) may include one or more acrylamide monomers, which may also be described as ethylenically unsaturated ami do functional monomers.
  • Suitable examples include acrylamide, methyl acrylamide, methyl methacrylamide, N-alkylmethacrylamide, ⁇ , ⁇ '-dialkylmethacrylamide, N- alkylacrylamide, ⁇ , ⁇ '-dialkylacrylamide, and any combination thereof.
  • the monomers of (B) include ⁇ , ⁇ '- dimethylacrylamide, t-butylacrylamide, t-octylacrylamide, or a combination thereof.
  • the monomers of (B) include: (iv) one or more alkoxylated hydrophobically modified associative monomers.
  • the polymer is free of units derived from alkoxylated hydrophobically modified associative monomers.
  • the monomers of (B) include: (v) one or more phosphonic acid monomers or partial esters, or salts thereof.
  • the polymer is free of units derived from phosphonic acid monomers or partial esters, or salts thereof.
  • the monomers of (B) include: (vi) one or more vinyl monomers. In other embodiments the polymer is free of units derived from more vinyl monomers.
  • the polymer described herein includes units derived from (C) a third composition comprising one or more crosslinking agents.
  • Suitable crosslinking agents include polyfunctional acrylates, polyalkenyl polyethers, or a combination thereof.
  • Polyfunctional acrylates have at least two polymerizable ethylenically unsaturated double bonds.
  • polyfunctional acrylate refers to acrylate esters of organic polyols wherein the organic polyol is esterified by reacting it with (meth)acrylic acid.
  • the polyfunctional acrylate can contain 2 to 6 polymerizable ethylenically unsaturated double bonds.
  • Suitable polyols for the esterification reaction can contain 2 to 12 carbon atoms and have at least two hydroxyl groups.
  • the polyol can be linear and branched or cyclic.
  • Exemplary polyols suitable for esterification include, but are not limited to, alkylene glycols containing 2 to 5 carbon atoms , polyalkylene glycol dimers and trimers, trimethylolethane and dimers thereof, trimethylolpropane and dimers thereof, triethylolpropane and dimers thereof, tetramethylolmethane (pentaerythritol), dipentaerythritol, and 1 ,4- cyclohexanediol.
  • Useful polyfunctional acrylates include, but are not limited to, ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 1 ,3-butylene glycol di(meth)acrylate, 1 ,4-butylene glycol di(meth)acrylate, 1 ,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1 ,9-nonanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate; dipentaerythritol tetra
  • the polyalkenyl polyether has at least two polymerizable ethylenically unsaturated double bonds.
  • polyalkenyl polyether refers to alkenyl ethers of organic polyols wherein the organic polyol is etherified by reacting it with alkenyl halide, such as allyl chloride or allyl bromide.
  • alkenyl halide such as allyl chloride or allyl bromide.
  • the polyalkenyl polyether e.g., polyallyl polyether
  • Suitable polyols for the etherification reaction can contain 2 to 12 carbon atoms and have at least two hydroxyl groups.
  • the polyol can be linear and branched or cyclic (e.g., monosaccharides and polysaccharides containing 1 to 4 saccharide units).
  • Exemplary polyols suitable for etherification include, but are not limited to, glucose, galactose, fructose, sorbose, rhamnose, sucrose, arabinose, maltose, lactose, raffinose, pentaerythritol, dipentaerythritol, trimethylolethane and dimers thereof, trimethylolpropane and dimers thereof, and triethylolpropane and dimers thereof. Additional polyols suitable for the etherification are disclosed in U.S. Patent No.
  • Useful polyalkenyl polyethers include, but are not limited to, polyallyl ethers of sucrose having from 2 to 8 allyl groups per molecule, pentaerythritol diallyl ether, pentaerythritol triallyl ether, and pentaerythritol tetraallyl ether; trimethylolpropane diallyl ether, trimethylolpropane triallyl ether, and mixtures thereof.
  • (C) includes ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 1 ,3-butylene glycol di(meth)acrylate, 1 ,4- butylene glycol di(meth)acrylate, 1 ,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1 ,9-nonanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate; dipentaerythritol hexa(meth)acrylate;
  • (C) includes a borate or one or more polyvalent metal ions selected from the group consisting of zirconium, chromium, titanium, aluminum, and mixtures thereof.
  • Such crosslinking agents generally comprise a borate, a metal, transition metal, or metalloid, collectively referred to herein as "metal(s).” Examples include boron, aluminum, antimony, zirconium, magnesium, or titanium. Generally, the metal of a crosslinking agent interacts with at least two functional groups to form a crosslink to generate the polymer network. Under the appropriate conditions (e.g., pH and temperature), the crosslinks that form between polymer molecules may increase the viscosity of a viscosified treatment fluid.
  • metal(s) include boron, aluminum, antimony, zirconium, magnesium, or titanium.
  • the metal of a crosslinking agent interacts with at least two functional groups to form a crosslink to generate the polymer network. Under the appropriate conditions (e.g., pH and temperature), the crosslinks that form between polymer molecules may increase the viscosity of a viscosified treatment fluid.
  • crosslinking agents examples include, but not are not limited to the following: boron compounds such as boric acid, disodium octaborate tetrahydrate, sodium diborate, pentaborate, or combinations thereof; compound that can supply chromium (III) ions such as chromium acetate, chromium lactate, chromium citrate or combinations thereof; compounds that can supply zirconium (IV) ions such as zirconium diethanolamine complex, zirconium triethanolamine complex, zirconium lactate, zirconium ethylene glycolate, zirconium acetylacetonate, tetrakis(triethanolaminato)zirconium, zirconium ammonium lactate, zirconium diethanol lactate, zirconium triethanolamine lactate, zirconium diisopropylamine lactate, zirconium sodium lactate salts, zirconium glycerol complex, zirconium
  • (C) includes only organic crosslinkers and is free of the borate and/or polyvalent metal ions described above.
  • the crosslinker may be added during the polymerization reaction.
  • the polymer may contain from 0.01 to 50 or 0.01 to 20, 0.01 to 10, 0.1 to 5, or 0.1 to 3, or even 0.5 to 1.0 percent by weight units derived from (C).
  • (C) includes only borate and/or polyvalent metal ions crosslinkers and is free of the organic crosslinkers described above.
  • the crosslinker may be added after the polymerization reaction.
  • the crosslinker may be added to the polymer such that the weight ratio of polymer to crosslinker used is from 1 :99 to 99: 1 or from 1 :50 to 50: 1 or from 1 : 10 to 10: 1 or from 1 :5 to 5 : 1 or evem from 1 : 1.5 to 1.5 : 1.
  • the crosslinker may be added to the polymer such that the weight ratio of polymer to crosslinker used is from 1 : 1 to 1 :99 or from 1 : 1 to 1 : 10 or from 1 : 1 to 1 :5 or even from 1 : 1 to 1 : 1.5.
  • the polymer further comprises units derived from: (D) a third monomer composition comprising one or more monomer that includes an alkyl group containing 1 to 18 carbon atoms comprising a simple ester, a vinyl ester, an mono-allyl ether, or salts thereof, or any combination thereof.
  • the monomers of (D) can include acrylamides, methacrylamides, diacetone acrylamides, acrylic or methacrylic acids or their esters, vinyllactams such as vinyl pyrrolidone or vinyl caprolactam, and vinyl esters.
  • the monomers of (D) include acrylamide, dimethyl amino ethyl methacrylate quaternized with dimethyl sulfate or with an alkyl halide, methacryloyl oxyethyl trimethyl ammonium chloride; methacryloyl oxyethyl trimethyl ammonium methosulfate; or any combination thereof.
  • the monomers of (D) may include: vinyl pyrrolidone/dialkylaminoalkyl acrylate or methacrylate, optionally quaternized; dimethyl amino ethyl methacrylate, vinyl caprolactam, and vinyl pyrrolidone; vinyl pyrrolidone and methacrylamidopropyl dimethyl amine; vinyl pyrrolidone and quaternized dimethyl amino propyl methacrylamide; and quaternary ammonium salts formed by the reaction of diethyl sulfate and a copolymer of vinyl pyrrolidone and dimethyl aminoethylmethacrylate.
  • the monomers of (D) may include vinyl pyrrolidone and/or vinyl imidazole, optionally quaternized; vinyl pyrrolidone, acrylamide and vinyl imidazole, optionally quaternized; vinyl caprolactam, vinyl pyrrolidone and vinyl imidazole, optionally quaternized; vinyl pyrrolidone, vinyl imidazole, and diallyldimethyl ammonium chloride, optionally quaternized; or any combination thereof.
  • the monomers of (D) may include compounds selected form the group consisting of alkyvinyl sulfonic acids, alkyl vinyl sulfonates, vinyl benzene sulfonic acids, vinyl benzene sulfonates, alkyl vinyl benzene sulfonic acids, alkyl vinyl benzene sulfonates, and combinations of two or more thereof.
  • Suitable examples include but are not limited to compounds selected from the group consisting of N-vinyl acetamide, N-vinyl-N-methyl acetamide, N,N- dimethyl acetamide, N-vinyl-2-pyrrolidone, N-ethenyl-N-alkyl acetamide, and combinations of two or more thereof.
  • Suitable examples include but are not limited to compounds selected from the group consisting of ethylenically unsaturated N-substituted carboxylic acids selected from the group consisting of acrylamide, methyl acrylamide methylmethacry amide, N-alkylmethacrylamide, ⁇ , ⁇ -dialkylmethacrylamide, N- alkylacrylamide, ⁇ , ⁇ -dialkylacrylamide, and combinations of any two or more thereof.
  • Suitable examples include but are not limited to compounds selected from the group consisting of acrylic acid, salts of acrylic acid, methacrylic acid, salts of methacrylic acid, itaconic acid, salts of itaconic acid, acrylonitrile, alkoxy esters of acrylic acid, alkoxy esters of methacrylic acid, vinyl sulfonate, vinyl sulfonic acid and combinations of any two or more thereof.
  • the monomers of (D) include one or more vinyl esters selected from vinyl acetate, vinyl propionate, vinyl butanoate, vinyl valerate, vinyl hexanoate, vinyl octanoate, vinyl nonanoate, vinyl decanoate, vinyl neodecanoate, vinyl undecanoate, vinyl laurate, or any combination thereof.
  • the monomers of (D) include one or more mono- allyl ethers selected from mono-allyl ethers of sucrose, mono-allyl ethers of pentaerythritol, or any combination thereof.
  • the monomers of (D) are essentially free of, or even completely free of, vinyl esters. In other embodiments, the monomers of (D) are essentially free of, or even completely free of, mono-allyl ethers. In other embodiments, the monomers of (D) are essentially free of, or even completely free of, acrylamides, methacrylamides, diacetone acrylamides, acrylic or methacrylic acids or their esters. In other embodiments, the monomers of (D) are essentially free of, or even completely free of, vinyllactams such as vinyl pyrrolidone or vinyl caprolactam, and vinyl esters.
  • the monomers of (D) are essentially free of, or even completely free of, alkyvinyl sulfonic acids, alkyl vinyl sulfonates, vinyl benzene sulfonic acids, vinyl benzene sulfonates, alkyl vinyl benzene sulfonic acids, and alkyl vinyl benzene sulfonates.
  • the polymer described herein is essentially free of, or even completely free of, units derived from an alkylene glycol monomer.
  • the polymer described herein is made up of: 0.1 to 50, or 0.1 to 30, or even 0.1 to 10 percent by weight of monomer units derived from (A); and 1 to 99.89 or 30 to 99.89, or 50 to 99.89, or even 70 to 99.89 percent by weight of monomer units derived from (B); and 0.01 to 50 or 0.01 to 20, 0.01 to 10, 0.1 to 5, or 0.1 to 3, or even 0.5 to 1.0 percent by weight units derived from (C).
  • the polymer described herein is made up of: 0.1 to 50, or 0.1 to 30, or even 0.1 to 10 percent of monomer units derived from (A); 25 to 99.88 or from 45 to 99.88, or from 65 to 99.88 percent by weight units derived from (B); 0.01 to 50 or 0.01 to 20, 0.01 to 10, 0.1 to 5, or 0.1 to 3, or even 0.5 to 1.0 percent by weight units derived from (C); and 0.01 to 49 or even 1 to 49 or even 0.01 to 5 percent by weight units derived from (D).
  • the polymer described herein includes units derived from the compounds of (A) that have the following structure:
  • R 1 is an alkyl group containing from 5 to 24 carbon atoms
  • R 2 is hydrogen or an alkyl group containing from 1 to 10 carbon atoms
  • R is an alkyl group containing 1 to 4 carbon atoms
  • R 7 is hydrogen or a hydrocarbyl group; or an alkali metal or ammonium salt thereof.
  • R 1 is an alkyl group containing from 5 to 24 carbon atoms or from 6 to 24, or from 8 to 22, or from 6 to 18, or from 10 to 16, or even 10, 14 or 16 carbon atoms.
  • R is hydrogen or an alkyl group containing from 1 to 10 carbon atoms, or from 1 to 8, or even just 8 carbon atoms.
  • R is an alkyl group containing 1 to 4 carbon atoms, or even just 1 carbon atom.
  • R 7 is hydrogen or a hydrocarbyl group, or even just hydrogen or a methyl group.
  • the disclosed technology includes process of making the described polymers.
  • Such processes include the step of reacting: (A) a first monomer composition comprising an ethylenically unsaturated hydrocarbylamidoalkanesulfonic acid monomer, where the monomer includes at least one alkyl group containing 5 to 30 carbon atoms, or salts thereof; and (B) a second monomer composition comprising one or more ethylenically unsaturated polymerizable monomers, or salts thereof; wherein the second monomer composition (B) is different from the first monomer composition (A).
  • any of the monomers of (B) described above may be used in the process.
  • the process may be carried out as a solution polymerization, a precipitation polymerization, a gel polymerization, or an inverse emulsion polymerization.
  • the process is carried out as a solution polymerization. In some embodiments, the process is carried out as a precipitation polymerization. In some embodiments, the process is carried out as a gel polymerization. In some embodiments, the process is carried out as an inverse emulsion polymerization.
  • the reaction step of the process further comprises reacting: (D) a fourth monomer composition comprising one or more monomers that include an alkyl group containing 1 to 18 carbon atoms comprising a simple ester, a vinyl ester, an mono-allyl ether, or any combination thereof; with (A) and (B).
  • the disclosed technology includes the use of the polymer described herein as a viscosifying agent.
  • the disclosed technology also includes methods of using the polymer described herein as a viscosifying agent.
  • the viscosifying agent disclosed here can have a number average molecule weight even above one million Dalton after crosslinking and such high molecular weight polymers can act as a fluid loss control agent, a shale inhibitor agent, a friction reducer, a gelling agent, or any combination thereof.
  • the viscosifying agent described herein may be used in drilling fluids.
  • drilling fluids are characterized by the characteristics of the compound or mixture of compounds that make up the continuous phase of the drilling fluids.
  • an aqueous-based drilling fluid is principally composed of an aqueous solution as the continuous phase.
  • the aqueous based continuous phase may generally be any water based fluid phase that is compatible with the formulation of a drilling fluid and is compatible with the shale hydration inhibition agents disclosed herein.
  • the aqueous based continuous phase is selected from: fresh water, sea water, brine, mixtures of water and water soluble organic compounds and mixtures thereof.
  • the amount of the aqueous based continuous phase should be sufficient to form a water based drilling fluid. This amount may range from nearly 100% of the drilling fluid to less than 30% of the drilling fluid by volume.
  • the aqueous based continuous phase is from about 95 to about 30% by volume water or even from about 90 to about 40%) by volume of the drilling fluid.
  • the aqueous based drilling fluid typically includes polymeric viscosifying agent and a fluid loss control agent or simply a fluid loss agent.
  • the drilling fluids of the disclosed technology include the viscosifying agent described herein, present in an amount sufficient to alter or maintain the rheological properties of the fluid.
  • the drilling fluids described herein may also include a weight material in order to increase the density of the fluid.
  • the primary purpose for such weighting materials is to increase the density of the drilling fluid so as to prevent kick-backs and blow-outs.
  • One of skill in the art should know and understand that the prevention of kick-backs and blow-outs is important to the safe day to day operations of a drilling rig.
  • the weight material is added to the drilling fluid in a functionally effective amount largely dependent on the nature of the formation being drilled.
  • Weight materials suitable for use in the formulation of the drilling fluids of the claimed subject matter may be generally selected from any type of weighting materials be it in solid, particulate form, suspended in solution, dissolved in the aqueous phase as part of the preparation process or added afterward during drilling. It is preferred that the weight material be selected from the group including barite, hematite, iron oxide, calcium carbonate, alkali halides, alkaline earth halides, magnesium carbonate, zinc halides, zinc formates, zinc acetates, cesium halides, cesium formates, cesium acetates, as well as other well-known organic and inorganic salts, and mixtures and combinations of these compounds and similar such weight materials that may be utilized in the formulation of drilling fluids.
  • the described drilling fluids may also be formulated to include materials generically referred to as gelling materials, thinners, and fluid loss control agents, as well as other compounds and materials which are optionally added to water base drilling fluid formulations. Of these additional materials, each can be added to the formulation in a concentration as Theologically and functionally required by drilling conditions.
  • Typical fluid loss control agents and gelling materials used in aqueous based drilling fluids are polyanionic carboxymethylcellulose (AC or CMC), chemically modified starches, bentonite, sepiolite, clay, attapulgite clay, anionic high-molecular weight polymers and biopolymers.
  • Thinners such as lignosulfonates are also often added to water- base drilling fluids. Typically lignosulfonates, modified lignosulfonates, polyphosphates and tannins are added. In other embodiments, low molecular weight polyacrylates can also be added as thinners. Thinners are added to a drilling fluid to reduce flow resistance and control gelation tendencies. Other functions performed by thinners include reducing filtration and filter cake thickness, counteracting the effects of salts, minimizing the effects of water on the formations drilled, emulsifying oil in water, and stabilizing mud properties at elevated temperatures.
  • additives that could be present in the drilling fluids described herein include products such as shale inhibition agents, shale encapsulation agents, such as polyamides and glycols, lubricants, penetration rate enhancers, defoamers, corrosion inhibitors and loss circulation products. Such compounds should be known to one of ordinary skill in the art of formulating aqueous based drilling fluids.
  • the described technology may also be useful as thermally stable and salt tolerant gelling agent.
  • the compositions described here may be used as associative hydrophobic thickeners, and the compositions can demonstrate good thermal stability and good salt tolerances, properties needed in hydraulic fracturing and other applications where one needs to transport a proppant.
  • Various gelling agents have been used along with a crosslinking agent to thicken aqueous solutions in order to transport a proppant in hydraulic fracturing applications.
  • many gelling agents contain significant amounts of water insoluble material which can cause issues in fracturing jobs due to a loss of formation permeability as well as degradation at high temperature resulting in viscosity loss.
  • compositions are useful for hydraulic fracturing applications and similar uses.
  • each chemical component described is presented exclusive of any solvent or diluent oil, which may be customarily present in the commercial material, that is, on an active chemical basis, unless otherwise indicated.
  • each chemical or composition referred to herein should be interpreted as being a commercial grade material which may contain the isomers, by- products, derivatives, and other such materials which are normally understood to be present in the commercial grade.
  • hydrocarbyl substituent or “hydrocarbyl group” is used in its ordinary sense, which is well-known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character.
  • hydrocarbyl groups include: (i) hydrocarbon substituents, that is, aliphatic (e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, and aromatic-, aliphatic-, and alicyclic-substituted aromatic substituents, as well as cyclic substituents wherein the ring is completed through another portion of the molecule (e.g., two substituents together form a ring); (ii) substituted hydrocarbon substituents, that is, substituents containing non-hydrocarbon groups which, in the context of this invention, do not alter the predominantly hydrocarbon nature of the substituent (e.g., halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, and sulfoxy); (iii) hetero substituents, that is, substituents which, while having
  • Heteroatoms include sulfur, oxygen, and nitrogen.
  • no more than two, or no more than one, non-hydrocarbon substituent will be present for every ten carbon atoms in the hydrocarbyl group; alternatively, there may be no non- hydrocarbon substituents in the hydrocarbyl group.
  • the hydrocarbyl groups described herein are alkyl groups.
  • Comparative copolymers as well as inventive polymers were prepared using a four neck flask fitted with a nitrogen inlet and thermocouple on one neck and a half moon stirrer on another, a condenser on another, and a stopper on another.
  • the total monomer amount is 60.5g.
  • Tertiary butanol (350g) and ammonium hydroxide 30 wt% aqueous solution (15.4g) were added to the reactor.
  • the mixture was placed under nitrogen at about 0.5 CFH and the slurry heated in a water bath set at about 60°C under stirring. The mixture began clearing then slowly became hazy then milky. After 30 min, dilauryl peroxide (0.75 g) was added. The reaction was held at about 60°C for about an hour and refluxed at about 75°C for about three hours. Dilauryl peroxide (0.75g) was added and the reaction was held at 75 °C for three more hours. The mixture was then cooled to room temperature and the solid was filtered off with vacuum. The wet cake was dried at about 80°C in a vacuum drying oven for about 24 hrs giving a white powder.
  • the compositions prepared by the foregoing method are shown in the tables below.
  • Viscosity was measured at 1.0 wt% of total solids at 100 s " using a corn and plate rheometer.
  • Comparative copolymers as well as inventive polymers were prepared in the same way described in Example 2. Crosslinking monomers were not added during the polymerization process; and instead, the dried polymer powders were dissolved in water (1 wt%) and the equal amount by weight of Zr (IV) acetylacetonate were dissolved under stirring. Then, the viscosities and pH of polymer solution were measured after cooling.
  • the viscosity was measured using a Brookfie d RV viscometer at 20 rpm
  • the formation of the gel was monitored systematically using an AR G2, controlled-stress rheometer with a pressure cell chamber containing a concentric cylinder geometry from TA Instruments. A positive pressure between 50-100 psi was maintained using pure nitrogen. A two-step procedure was used to test the gels. During the first step, the temperature was increased from 25 to 150°C over 30 minutes at a constant shear rate of 100 s "1 . During the second step, the temperature was held at 150°C for 1 hour at the same shear rate. Table 3-B Viscosity (cP) and varying temperature
  • the monomer emulsion from the feed reactor is gradually metered (8.44 g/min.) into the second reactor over a period of about 120 minutes at a reaction temperature maintained at approximately 88°C and allowed to react in a first stage polymerization reaction to form an ASE (Alkali swellable emulsion) core polymer particles of crosslinked n- butyl acrylate/ethyl acrylate/methacrylic acid/ trimethylolpropane triacrylate copolymer.
  • ASE Alkali swellable emulsion
  • the second stage monomer emulsion is prepared in the feed reactor by adding 56 g of deionized water , 1.6 g of sodium lauryl sulfate (30% in water by weight), 1.6 g of Calfax DB45, 60 g of n-butyl acrylate, 34 g of ethyl acrylate, 150 g of C H AMPS solution (20 % in water by weight), 74.6 g of methacrylic acid, and 0.75 g of trimethylolpropane triacrylate.
  • the monomer emulsion containing C H AMPS is then metered into the second reactor over a period of 30 minutes at a controlled rate (15.54 g/min.) at a temperature maintained at approximately 88°C and polymerized in the presence of the ASE core polymer particles in a second stage reaction to form a crosslinked polymer shell rich in associative hydrophobes (over the ASE core polymer particles) comprising polymerized n-butyl acrylate/ ethyl acrylate/Ci 6 AMPS/methacrylic acid/trimethylolpropane triacrylate copolymer.
  • a single stage emulsion polymer is polymerized from the components set forth in Table 5 -A.
  • the polymer is synthesized as set forth in Example 4 above, except that the polymerization is terminated following the first stage reaction and recovered.
  • This example describes gel properties made from the emulsion polymers of Examples 4 and 5. These gels are made as mucilages of 1 and 2.5 wt.% total polymer solids in water and neutralized to pH values ranging from 6.8 to 7.5 with
  • the transitional term "comprising,” which is synonymous with “including,” “containing,” or “characterized by,” is inclusive or open-ended and does not exclude additional, un-recited elements or method steps.
  • the term also encompass, as alternative embodiments, the phrases “consisting essentially of and “consisting of,” where “consisting of excludes any element or step not specified and “consisting essentially of permits the inclusion of additional un-recited elements or steps that do not materially affect the basic and novel characteristics of the composition or method under consideration.

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Abstract

La technologie décrite par la présente invention concerne un agent viscosifiant destiné à être utilisé dans une composition et/ou un procédé de forage et de cémentation, comprenant l'utilisation dudit agent à titre de gélifiant pour la fracturation hydraulique et/ou une récupération améliorée du pétrole. L'agent viscosifiant est un polymère réticulé constitué de motifs dérivés d'un mélange unique de monomères. Le polymère affiche une bonne efficacité en tant que viscosifiant tout en présentant également une bonne stabilité à hautes températures.
PCT/US2014/055815 2013-09-18 2014-09-16 Polymères réticulés stables à hautes températures WO2015042028A1 (fr)

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EP3420047B1 (fr) * 2016-02-23 2023-01-11 Ecolab USA Inc. Émulsions de polymères réticulées avec de l'hydrazide destinées à être utilisées dans la récupération de pétrole brut
WO2019027710A1 (fr) * 2017-08-01 2019-02-07 Weatherford Technology Holdings, Llc Procédé de fracturation à l'aide d'un fluide de faible viscosité à faible taux de sédimentation d'agent de soutènement
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US11566504B2 (en) 2019-07-17 2023-01-31 Weatherford Technology Holdings, Llc Application of elastic fluids in hydraulic fracturing implementing a physics-based analytical tool
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CN115536777B (zh) * 2022-11-08 2023-08-04 中国石油大学(华东) 一种小分子疏水缔合抗高温页岩抑制剂及其制备方法与应用

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