Crosslinked polymers derived from monomers having acryloyl and lactam moieties and sulfonic acid/sulfonate comonomers, compositions thereof, and applications thereof

Abstract

The invention provides polymers comprising repeating units derived from at least one monomer comprising at least one functionalized or unfunctionalized acryloyl moiety and at least one lactam moiety; at least one monomer comprising at least one sulfonic acid moiety or a salt thereof; and at least one crosslinker. The invention further provides various compositions comprising the polymers. The invention furthermore provides applications of these compositions in various industrial arts, particularly in oilfield operations such as drilling and cementing.

Claims

1. An oilfield composition comprising a polymer, wherein the composition is a cementing fluid, a fracturing fluid, a servicing fluid, a gravel packing mud, a completion fluid, a workover fluid, or a spacer fluid; wherein said polymer is present in an amount from about 0.01% by weight to about 20% by weight of said composition; said polymer having repeating units derived from (a) at least one monomer comprising at least one functionalized or unfunctionalized acryloyl moiety and at least one lactam moiety having a structure selected from the group consisting of: ##STR00016## ##STR00017## ##STR00018## ##STR00019## ##STR00020## ##STR00021## ##STR00022## ##STR00023## ##STR00024## (b) at least one monomer comprising at least one sulfonic acid moiety or a salt thereof; and (c) at least one crosslinker, said oilfield composition further comprising at least one additive selected from the group consisting of secondary fluid loss control agents, secondary cement anti-settling agents, agents for delayed crosslinking, weighting agents, silica flour, strength enhancers, rheology modifiers, friction reducers, dispersing agents, surfactants, clathrate hydrate inhibitors, shale swelling inhibitors, gelation inhibitors, gas migration control additives, set retarding agents, accelerants, activators, defoaming agents, lost circulation materials, corrosion inhibitors, salts, strength retrogression additives, vitrified shale, thixotropic additives, and combinations thereof.

Description

DETAILED DESCRIPTION

(1) Before explaining at least one aspect of the disclosed and/or claimed inventive concept(s) in detail, it is to be understood that the disclosed and/or claimed inventive concept(s) is not limited in its application to the details of construction and the arrangement of the components or steps or methodologies set forth in the following description. The disclosed and/or claimed inventive concept(s) is capable of other aspects or of being practiced or carried out in various ways. Also, it is to be understood that the phraseology and terminology employed herein is for the purpose of description and should not be regarded as limiting.

(2) Unless otherwise defined herein, technical terms used in connection with the disclosed and/or claimed inventive concept(s) shall have the meanings that are commonly understood by those of ordinary skill in the art. Further, unless otherwise required by context, singular terms shall include pluralities and plural terms shall include the singular.

(3) All patents, published patent applications, and non-patent publications referenced in any portion of this application are herein expressly incorporated by reference herein their entirety to the same extent as if each individual patent or publication was specifically and individually indicated to be incorporated by reference.

(4) All of the articles and/or methods disclosed herein can be made and executed without undue experimentation in light of the present disclosure. While the articles and methods of the disclosed and/or claimed inventive concept(s) have been described in terms of particular aspects, it will be apparent to those of ordinary skill in the art that variations may be applied to the articles and/or methods and in the steps or in the sequence of steps of the method described herein without departing from the concept, spirit and scope of the disclosed and/or claimed inventive concept(s).

(5) All such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and concept of the disclosed and/or claimed inventive concept(s).

(6) As utilized in accordance with the disclosure, the following terms, unless otherwise indicated, shall be understood to have the following meanings.

(7) The use of the word a or an when used in conjunction with the term comprising may mean one, but it is also consistent with the meaning of one or more, at least one, and one or more than one. The use of the term or is used to mean and/or unless explicitly indicated to refer to alternatives only if the alternatives are mutually exclusive, although the disclosure supports a definition that refers to only alternatives and and/or.

(8) Throughout this application, the term about is used to indicate that a value includes the inherent variation of error for the quantifying device, the method being employed to determine the value, or the variation that exists among the study subjects. For example, but not by way of limitation, when the term about is utilized, the designated value may vary by plus or minus twelve percent, or eleven percent, or ten percent, or nine percent, or eight percent, or seven percent, or six percent, or five percent, or four percent, or three percent, or two percent, or one percent.

(9) The use of the term at least one will be understood to include one as well as any quantity more than one, including but not limited to, 1, 2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 100, etc. The term at least one may extend up to 100 or 1000 or more depending on the term to which it is attached. In addition, the quantities of 100/1000 are not to be considered limiting as lower or higher limits may also produce satisfactory results. In addition, the use of the term at least one of X, Y, and Z will be understood to include X alone, Y alone, and Z alone, as well as any combination of X, Y, and Z. The use of ordinal number terminology (i.e., first, second, third, fourth, etc.) is solely for the purpose of differentiating between two or more items and, unless otherwise stated, is not meant to imply any sequence or order or importance to one item over another or any order of addition.

(10) As used herein, the words comprising (and any form of comprising, such as comprise and comprises), having (and any form of having, such as have and has), including (and any form of including, such as includes and include) or containing (and any form of containing, such as contains and contain) are inclusive or open-ended and do not exclude additional, unrecited elements or method steps. The term or combinations thereof as used herein refers to all permutations and combinations of the listed items preceding the term. For example, A, B.sub.Xn, B.sub.Xn+1, or combinations thereof is intended to include at least one of: A, B.sub.Xn, B.sub.Xn+1, AB.sub.Xn, A B.sub.Xn+1, B.sub.XnB.sub.Xn+1, or AB.sub.XnB.sub.Xn+1 and, if order is important in a particular context, also B.sub.XnA, B.sub.Xn+1A, B.sub.Xn+1B.sub.Xn, B.sub.Xn+1B.sub.XnA, B.sub.XnB.sub.Xn+1A, AB.sub.Xn+1B.sub.Xn, B.sub.XnAB.sub.Xn+1, or B.sub.Xn+1AB.sub.Xn. Continuing with this example, expressly included are combinations that contain repeats of one or more item or term, such as B.sub.XnB.sub.Xn, AAA, MB.sub.Xn, B.sub.XnB.sub.XnB.sub.Xn+1, AAAB.sub.XnB.sub.Xn+1B.sub.Xn+1B.sub.Xn+1B.sub.Xn+1, B.sub.Xn+1B.sub.XnB.sub.XnAAA, B.sub.Xn+1A B.sub.XnAB.sub.XnB.sub.Xn, and so forth. The skilled artisan will understand that typically there is no limit on the number of items or terms in any combination, unless otherwise apparent from the context.

(11) The term each independently selected from the group consisting of means when a group appears more than once in a structure, that group may be selected independently each time it appears.

(12) The term hydrocarbyl includes straight-chain and branched-chain alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl groups, and combinations thereof with optional heteroatom(s). A hydrocarbyl group may be mono-, di- or polyvalent.

(13) The term alkyl refers to a functionalized or unfunctionalized monovalent straight-chain or branched-chain C.sub.1-C.sub.60 group optionally having one or more heteroatoms. Particularly, an alkyl is a C.sub.1-C.sub.45 group and more particularly, a C.sub.1-C.sub.30 group. Non-limiting examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, tert-octyl, iso-norbornyl, n-dodecyl, tert-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, and n-eicosyl.

(14) The term aryl refers to a functionalized or unfunctionalized monovalent aromatic hydrocarbyl group optionally having one or more heteroatoms. The definition of aryl also includes heteroaryl groups. Non-limiting examples of aryl groups include phenyl, naphthyl, pyrrolyl, furanyl, thienyl, pyridyl, indolyl, benzofuranyl, benzothiophenyl, quinolinyl, isoquinolinyl, and the like.

(15) The term alkylene refers to a functionalized or unfunctionalized divalent straight-chain, branched-chain or cyclic C.sub.1-C.sub.40 group optionally having one or more heteroatoms. Particularly, an alkylene is a C.sub.1-C.sub.30 group and more particularly, a C.sub.1-C.sub.20 group. Non-limiting examples of alkylene groups include CH.sub.2. CH.sub.2CH.sub.2, CH(CH.sub.3)CH.sub.2, CH.sub.2CH(CH.sub.3), C(CH.sub.3).sub.2CH.sub.2, CH.sub.2C(CH.sub.3).sub.2, CH(CH.sub.3)CH(CH.sub.3), C(CH.sub.3).sub.2C(CH.sub.3).sub.2, CH.sub.2CH.sub.2CH.sub.2, CH(CH.sub.3)CH.sub.2CH.sub.2, CH.sub.2CH(CH.sub.3)CH.sub.2, CH.sub.2CH.sub.2CH(CH.sub.3), CH.sub.2CH.sub.2CH.sub.2CH.sub.2, CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2, CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2, CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2, cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene groups, and the like.

(16) The term arylene refers to a functionalized or unfunctionalized divalent aromatic hydrocarbyl group optionally having one or more heteroatoms. The definition of arylene also includes heteroarylene groups. Non-limiting examples of arylene groups include phenylene, naphthylene, pyridinylene, and the like.

(17) The term heteroatom refers to oxygen, nitrogen, sulfur, silicon, phosphorous, and/or halogen. The heteroatom(s) may be present as a part of one or more heteroatom-containing functional groups. Non-limiting examples of heteroatom-containing functional groups include ether, hydroxy, epoxy, carbonyl, carboxamide, carboxylic ester, carboxylic acid, imine, imide, amine, sulfonic, sulfonamide, phosphonic, and silane groups. The heteroatom(s) may also be present as a part of a ring such as in heteroaryl and heteroarylene groups.

(18) The term halogen refers to chloro, bromo, iodo and/or fluoro.

(19) The term ammonium includes protonated NH.sub.3 and protonated primary, secondary, and tertiary organic amines.

(20) The term functionalized refers to the state of a moiety that has one or more functional groups introduced to it by way of one or more functionalization reactions known to a person having ordinary skill in the art. Non-limiting examples of functionalization reactions include epoxidation, sulfonation, hydrolysis, amidation, esterification, hydroxylation, dihydroxylation, amination, ammonolysis, acylation, nitration, oxidation, dehydration, elimination, hydration, dehydrogenation, hydrogenation, acetalization, halogenation, dehydrohalogenation, Michael addition, aldol condensation, Canizzaro reaction, Mannich reaction, Clasien condensation, Suzuki coupling, and the like.

(21) The term residue of refers to a fragment of a reactant that remains after a reaction with another reactant(s). The residue may be mono-, di- or polyvalent.

(22) The term monomer refers to a small molecule that chemically bonds during polymerization to one or more monomers of the same or different kind to form a polymer.

(23) The term polymer refers to a large molecule comprising one or more types of monomer residues (repeating units) connected by covalent chemical bonds. By this definition, polymer encompasses compounds wherein the number of monomer units may range from very few, which more commonly may be called as oligomers, to very many. Non-limiting examples of polymers include homopolymers, and non-homopolymers such as copolymers, terpolymers, tetrapolymers and the higher analogues. The polymer may have a random, block, and/or alternating architecture.

(24) The term homopolymer refers to a polymer that consists essentially of a single monomer type.

(25) The term non-homopolymer refers to a polymer that comprises more than one monomer types.

(26) The term copolymer refers to a non-homopolymer that comprises two different monomer types.

(27) The term terpolymer refers to a non-homopolymer that comprises three different monomer types.

(28) The term branched refers to any non-linear molecular structure. The term includes both branched and hyper-branched structures.

(29) The term free radical addition polymerization initiator refers to a compound used in a catalytic amount to initiate a free radical addition polymerization. The choice of initiator depends mainly upon its solubility and its decomposition temperature.

(30) The term alkyl (alk) acrylate refers to an alkyl ester of an acrylic acid or an alkyl acrylic acid.

(31) The term alkyl (alk) acrylamide refers to an alkyl amide of an acrylic acid or an alkyl acrylic acid.

(32) The term oilfield composition refers to a composition that may be used in the exploration, extraction, recovery, and/or completion of any hydrocarbon. Non-limiting examples of oilfield compositions include drilling fluids, cementing fluids, anti-agglomerants, kinetic hydrate inhibitors, shale swelling inhibitors, drilling muds, servicing fluids, gravel packing muds, friction reducers, fracturing fluids, completion fluids, and work over fluids.

(33) The term fluid loss refers primarily to water loss, but also may include minor amounts of other fluids which are subject to loss.

(34) The term fracturing refers to the process and methods of breaking down a geological formation, i.e. the rock formation around a well bore, by pumping a fluid at very high pressures, in order to increase production rates from a hydrocarbon reservoir.

(35) The term drilling fluid refers to compositions such as fluids, slurries, or muds used during oil and/or gas well drilling operations.

(36) The term cementing fluid refers to compositions such as fluids or slurries used during cementing operations of a well. For example, a cementing fluid may comprise an aqueous fluid and at least one cementitious material.

(37) The term fracturing fluid refers to fluids or slurries used downhole during fracturing operations.

(38) The term servicing fluid refers to a fluid used to drill, complete, work over, fracture, or in any way prepare a well bore for the recovery of materials residing in a subterranean formation penetrated by the well bore. It is understood that subterranean formation encompasses both areas below exposed earth or areas below earth covered by water such as sea or ocean water. Examples of servicing fluids include, but are not limited to, a drilling fluid or mud, a cement slurry, a gravel packing fluid, a fracturing fluid, a completion fluid, and a work-over fluid, all of which are well known in the art.

(39) The terms personal care composition and cosmetics refer to compositions intended for use on or in the human body, such as skin, sun, hair, oral, cosmetic, and preservative compositions, including those to alter the color and appearance of the skin and hair.

(40) The term pharmaceutical composition refers to any composition comprising at least one pharmaceutically active ingredient, as well as any product which results, directly or indirectly, from combination, complexation, or aggregation of any two or more of the ingredients, from dissociation of one or more of the ingredients, or from other types of reactions or interactions of one or more of the ingredients.

(41) All percentages, ratio, and proportions used herein are based on a weight basis unless other specified.

(42) In a first aspect, the invention provides a polymer comprising repeating units derived from at least one monomer comprising at least one functionalized or unfunctionalized acryloyl moiety and at least one lactam moiety (monomer A); at least one monomer comprising at least one sulfonic acid moiety or a salt thereof (monomer B.sub.X1); and at least one crosslinker (monomer B.sub.X2).

(43) In particular embodiments, the monomer (monomer A) comprising at least one functionalized or unfunctionalized acryloyl moiety and at least one lactam moiety has the structure:

(44) ##STR00001##
wherein each R.sub.1, R.sub.2 and R.sub.3 is independently selected from the group consisting of hydrogen, halogens, functionalized and unfunctionalized C.sub.1-C.sub.4 alkyl, and

(45) ##STR00002##
each X is independently selected from the group consisting of OR.sub.4, OM, halogen, N(R.sub.5)(R.sub.6),

(46) ##STR00003##
and combinations thereof; each Y is independently oxygen, NR.sub.7 or sulfur; each R.sub.4, R.sub.5, R.sub.6 and R.sub.7 is independently selected from the group consisting of hydrogen and functionalized and unfunctionalized alkyl; each M is independently selected from the group consisting of metal ions, ammonium ions, organic ammonium cations, and combinations thereof; and each Q.sub.1, Q.sub.2, Q.sub.3, and Q.sub.4 is independently selected from the group consisting of functionalized and unfunctionalized alkylene.

(47) Particularly, each Q.sub.1, Q.sub.2, Q.sub.3, and Q.sub.4 is independently selected from the group consisting of functionalized and unfunctionalized C.sub.1-C.sub.12 alkylene. Particular, yet non-limiting examples of alkylene groups include CH.sub.2. CH.sub.2CH.sub.2, CH(CH.sub.3)CH.sub.2, CH.sub.2CH(CH.sub.3), C(CH.sub.3).sub.2CH.sub.2, CH.sub.2C(CH.sub.3).sub.2, CH(CH.sub.3)CH(CH.sub.3), C(CH.sub.3).sub.2C(CH.sub.3).sub.2, CH.sub.2CH.sub.2CH.sub.2, CH(CH.sub.3)CH.sub.2CH.sub.2, CH.sub.2CH(CH.sub.3)CH.sub.2, CH.sub.2CH.sub.2CH(CH.sub.3), CH.sub.2CH.sub.2CH.sub.2CH.sub.2, CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2, CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2, and CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2.

(48) In one non-limiting embodiment, each R.sub.1, R.sub.2 and R.sub.3 is independently selected from the group consisting of hydrogen, methyl and combinations thereof. Particularly, R.sub.1 and R.sub.2 are hydrogens and R.sub.3 is hydrogen or methyl.

(49) In another non-limiting embodiment, each R.sub.1 and R.sub.3 is independently hydrogen or methyl; R.sub.2 is

(50) ##STR00004##
X is selected from the group consisting of OR.sub.4, OM, halogens, and N(R.sub.5)(R.sub.6); each R.sub.4, R.sub.5, and R.sub.6 is independently selected from the group consisting of hydrogen and functionalized and unfunctionalized alkyl; and each M is independently selected from the group consisting of metal ions, ammonium ions, organic ammonium cations, and combinations thereof. Particularly, R.sub.1 and R.sub.3 are hydrogens and R.sub.2 is

(51) ##STR00005##
X is selected from the group consisting of OR.sub.4, OM and N(R.sub.5)(R.sub.6); each R.sub.4, R.sub.5, and R.sub.6 is independently selected from the group consisting of hydrogen and functionalized and unfunctionalized C.sub.1-C.sub.4 alkyl; and each M is independently selected from the group consisting of metal ions, ammonium ions, organic ammonium cations, and combinations thereof.

(52) The first polymerizable unit, defined by structure (1), may be synthesized using methods recorded in the art, e.g., by reaction of an N-hydroxylalkyl lactam with an acrylate, (meth)acrylate, anhydride, or similar compounds. Production methods include those described in U.S. Pat. Nos. 2,882,262; 5,523,340; 6,369,163; U.S. Patent Application Publication 2007/123673; GB 924,623; 930,668; and 1,404,989; WO 03/006569; and EP 385918. Each of the previous disclosures are hereby incorporated herein by reference in its entirety.

(53) The lactam-containing monomers shown in structures (2)-(57) can be obtained from condensation reactions that include an N-hydroxyalkyl lactam and an unsaturated carboxylic acid, an acrylate, a (meth)acrylate, or an anhydride. Suitable N-hydroxyalkyl lactams include N-hydroxymethyl pyrrolidone and caprolactam, N-hydroxyethyl pyrrolidone and caprolactam, and N-hydroxypropyl pyrrolidone and caprolactam. Non-limiting examples of carboxylic acids that can be used include: acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, succinic acid, and maleic acid. Similarly, acrylates and (meth)acrylates include (without limitation) methyl, ethyl, butyl, octyl, ethyl hexyl acrylates and their (meth)acrylate analogues. Representative anhydrides include formic anhydride, succinic anhydride, maleic anhydride and acetic anhydride.

(54) In particular embodiments, the monomer having at least one functionalized or unfunctionalized acryloyl moiety and at least one lactam moiety (monomer A) has a structure selected from the group consisting of:

(55) ##STR00006## ##STR00007## ##STR00008## ##STR00009## ##STR00010## ##STR00011## ##STR00012## ##STR00013##

(56) Other suitable examples of can be found in WO 2011/063208, the disclosure of which is hereby incorporated herein by reference in its entirety.

(57) In particular embodiments, the monomer comprising at least one sulfonic acid moiety or a salt thereof (monomer B.sub.X1) has a structure selected from the group consisting of:

(58) ##STR00014##
and combinations thereof, wherein each R.sub.1 R.sub.2 and R.sub.3 is independently selected from the group consisting of hydrogen, halogens, functionalized and unfunctionalized C.sub.1-C.sub.4 alkyl, and combinations thereof; Y is oxygen or NR.sub.4; R.sub.4 is hydrogen or functionalized and unfunctionalized alkyl; Q.sub.1 is a functionalized or unfunctionalized alkylene; Q.sub.2 is a direct bond or is selected from the group consisting of functionalized and unfunctionalized alkylenes, arylenes, and combinations thereof; and each M is independently selected from the group consisting of hydrogen, alkali metal ions, alkaline earth metal ions, transition metal ions, ammonium ions, organic ammonium cations, and combinations thereof.

(59) Particular, yet non-limiting examples of monomers comprising at least one sulfonic acid moiety or a salt thereof (monomer B.sub.X1) are selected from the group consisting of 2-acrylamido-2-methyl propane sulfonic acid, 2-acrylamido-2-ethyl propane sulfonic acid, 2-acrylamido-2-propyl propane sulfonic acid, 2-methacrylamido-2-methyl propane sulfonic acid, 2-methacrylamido-2-ethyl propane sulfonic acid, 3-methacrylamido-2-hydroxy-1-propanesulfonic acid, 2-methacrylamido-2-propyl propane sulfonic acid, N-methyl-2-acrylamido-2-methyl propane sulfonic acid, N-methyl-2-acrylamido-2-ethyl propane sulfonic acid, N-methyl-2-acrylamido-2-propyl propane sulfonic acid, N-methyl-2-methacrylamido-2-methyl propane sulfonic acid, N-methyl-2-methacrylamido-2-ethyl propane sulfonic acid, N-methyl-2-methacrylamido-2-propyl propane sulfonic acid, 2-acrylamido-1-butane sulfonic acid, 2-acrylamido-1-pentane sulfonic acid, 2-acrylamido-1-hexane sulfonic acid, 2-methacrylamido-1-butane sulfonic acid, 2-methacrylamido-1-pentane sulfonic acid, 2-methacrylamido-1-hexane sulfonic acid, 2-acrylamido-1-heptane sulfonic acid, 2-methacrylamido-1-heptane sulfonic acid, N-methyl-2-acrylamido-1-butane sulfonic acid, N-methyl-2-methacrylamido-1-butane sulfonic acid, N-methyl-2-acrylamido-1-pentane sulfonic acid, N-methyl-2-methacrylamido-1-pentane sulfonic acid, N-methyl-2-acrylamido-1-hexane sulfonic acid, N-methyl-2-methacrylamido-1-hexane sulfonic acid, N-methyl-2-acrylamido-1-heptane sulfonic acid, N-methyl-2-methacrylamido-1-heptane sulfonic acid, vinyl sulfonic acid, allyl sulfonic acid, allyloxybenzenesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, methallylsulfonic acid, styrenesulfonic acid, salts thereof, and combinations thereof. Particularly, the monomer comprising at least one sulfonic acid moiety or a salt thereof is selected from the group consisting of 2-acrylamido-2-methyl propane sulfonic acid, 2-methacrylamido-2-methyl propane sulfonic acid, vinyl sulfonic acid, allyl sulfonic acid, methallylsulfonic acid, styrenesulfonic acid, and combinations thereof.

(60) Particular, yet non limiting examples of crosslinkers (monomer B.sub.X2) include: divinyl ethers of compounds selected from the group consisting of ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-unidecanediol, 1,12-dodecanediol, and combinations thereof; divinyl ethers of diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, heptaethylene glycol, octaethylene glycol, nonaethylene glycol, decaethylene glycol, and polyalkylene glycols; methylenebis(meth)acrylamide; ethylene glycol di(meth)acrylate; butanediol di(meth)acrylate; tetraethylene glycol di(meth)acrylate; polyethylene glycol di(meth)acrylate; polyethylene glycol di(meth)acrylamide; dipropylene glycol diallyl ether; polyglycol diallyl ether; hydroquinone diallyl ether; trimethylolpropane tri(meth)acrylate; trimethylolpropane diallyl ether; pentaerythritol triallyl ether; allyl(meth)acrylate; triallyl cyanurate; diallyl maleate; polyallyl esters; tetraallyloxyethane; triallylamine; tetraallylethylenediamine; divinyl benzene; glycidyl (meth)acrylate; 1,7-octadiene; 1,9-decadiene; 1,13-tetradecadiene; divinylbenzene; diallyl phthalate; triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione; N,N-divinylimidazolidone; 1-vinyl-3(E)-ethylidene pyrrolidone; 2,4,6-triallyloxy-1,3,5-triazine; and combinations thereof. More particularly, the crosslinker is selected from the group consisting of: pentaerythritol triallyl ether, trimethylolpropane diallyl ether, trimethylolpropane tri(meth)acrylate, methylenebis(meth)acrylamide, ethylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylamide, butanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylamide, and combinations thereof. Even more particularly, the crosslinker is selected from the group consisting of: pentaerythritol triallyl ether, trimethylolpropane diallyl ether, trimethylolpropane tri(meth)acrylate, methylenebis(meth)acrylamide, and combinations thereof.

(61) Particularly, the crosslinker(s) may be present in an amount from about 0.001% by weight to about 20% by weight of the polymer. More particularly, the crosslinker(s) may be present in an amount from about 0.001% by weight to about 10% by weight of the polymer. Even more particularly, the crosslinker(s) may be present in an amount from about 0.001% by weight to about 5% by weight of the polymer.

(62) In a particular, yet non-limiting embodiment, the polymer according to the invention comprises repeating units derived from: from about 0.1 to about 99.9 percent by weight of the polymer of at least one monomer comprising at least one functionalized or unfunctionalized acryloyl moiety and at least one lactam moiety (monomer A); (b) from about 0.1 to about 99.9 percent by weight of the polymer of at least one monomer comprising at least one sulfonic acid moiety or a salt thereof (monomer Bx.sub.1); and (c) from about 0.01 to about 20 percent by weight of the polymer of at least one crosslinker (monomer B.sub.X2), with the proviso that the sum of the percent by weight values of the monomers and the crosslinker(s) is equal to 100.

(63) More particularly, the polymer comprises repeating units derived from: from about 0.1 to about 20 percent by weight of the polymer of at least one monomer (monomer A) having a structure selected from the group consisting of

(64) ##STR00015##
and combinations thereof; (b) from about 80 to about 99.9 percent by weight of the polymer of at least one monomer (monomer B.sub.X1) selected from the group consisting of 2-acrylamido-2-methyl propane sulfonic acid, 2-methacrylamido-2-methyl propane sulfonic acid, vinyl sulfonic acid, salts thereof, and combinations thereof; and (c) from about 0.01 to about 20 percent by weight of the polymer of at least one crosslinker (monomer B.sub.X2) selected from the group consisting of pentaerythritol triallyl ether, methylenebis(meth)acrylamide, and combinations thereof, with the proviso that the sum of the percent by weight values of the monomers and the crosslinker(s) is equal to 100.

(65) In particular embodiments, the polymer according to the invention (inventive polymer) further comprises repeating units derived from at least one monomer selected from the group consisting of functionalized and unfunctionalized N-vinyl lactams, N-vinyl-2-pyrrolidone, N-vinylcaprolactam, alkyl vinyl ethers, methyl vinyl ether, isobutyl vinyl ether, vinyl alkanoates, vinyl acetate, vinyl alkanamides, vinyl alcohols, vinyl carbonates, vinyl carbamates, vinyl thiocarbamates, vinyl ureas, vinyl halides, vinyl imidazoles, vinyl pyridines, vinyl silanes, vinyl siloxanes, vinyl sulfones, maleic anhydride, maleates, fumarates, maleimides, maleamic acids, alpha-olefins, isobutylene, vinyl triazoles, alpha, beta-olefinically unsaturated carboxylic nitriles, acrylonitrile, styrenes, and combinations thereof.

(66) The polymers according to the invention may be used alone or in combination with other ingredient(s) in various compositions and product forms.

(67) In a second aspect, the invention provides a composition comprising a polymer comprising repeating units derived from at least one monomer comprising at least one functionalized or unfunctionalized acryloyl moiety and at least one lactam moiety (monomer A); at least one monomer comprising at least one sulfonic acid moiety or a salt thereof (monomer B.sub.X1); and at least one crosslinker. Particular, yet non-limiting examples of such compositions include oilfield compositions, drilling fluids, drilling muds, cementing fluids, servicing fluids, gravel packing muds, fracturing fluids, completion fluids, workover fluids, spacer fluids, personal care compositions, coating compositions, household, industrial and institutional compositions, pharmaceutical compositions, food compositions, construction compositions, biocides, adhesives, inks, papers, polishes, membranes, metal working fluids, plastics, textiles, printing compositions, lubricants, preservatives, agrochemicals, and wood-care compositions.

(68) In a third aspect, the invention provides an oilfield composition comprising a polymer comprising repeating units derived from at least one monomer comprising at least one functionalized or unfunctionalized acryloyl moiety and at least one lactam moiety (monomer A); at least one monomer comprising at least one sulfonic acid moiety or a salt thereof (monomer B.sub.X1); and at least one crosslinker (monomer B.sub.X2). Particularly, the oilfield composition is a drilling fluid, fracturing fluid, cementing fluid, servicing fluid, gravel packing mud, completion fluid, workover fluid, or spacer fluid.

(69) In particular embodiments, the polymer according to the invention is present in an amount from about 0.01 percent to about 20 percent by weight of the oilfield composition. More particularly, the polymer is present in an amount from about 0.05 percent to about 10 percent by weight of the oilfield composition. Even more particularly, the polymer is present in an amount from about 0.1 percent to about 5 percent by weight of the oilfield composition.

(70) In particular embodiments, the oilfield compositions may further comprise one or more additives. Particular, yet non-limiting examples of such additives include secondary fluid loss control agents, secondary cement anti-settling agents, agents for delayed crosslinking, weighting agents, silica flour, strength enhancers, rheology modifiers, friction reducers, dispersing agents, surfactants, clathrate hydrate inhibitors, shale swelling inhibitors, gelation inhibitors, gas migration control additives, set retarding agents, accelerants, activators, defoaming agents, lost circulation materials, corrosion inhibitors, salts, strength retrogression additives, vitrified shale, thixotropic additives, and combinations thereof.

(71) In a forth aspect, the invention provides a drilling fluid comprising a polymer comprising repeating units derived from at least one monomer comprising at least one functionalized or unfunctionalized acryloyl moiety and at least one lactam moiety (monomer A); at least one monomer comprising at least one sulfonic acid moiety or a salt thereof (monomer Bx.sub.1); and at least one crosslinker (monomer B.sub.X2).

(72) In particular embodiments, the polymer according to the invention is present in an amount from about 0.01 percent to about 20 percent by weight of the drilling fluid. More particularly, the polymer is present in an amount from about 0.05 percent to about 10 percent by weight of the drilling fluid. Even more particularly, the polymer is present in an amount from about 0.1 percent to about 5 percent by weight of the drilling fluid.

(73) In a fifth aspect, the invention provides a cementing fluid comprising a polymer comprising repeating units derived from at least one monomer comprising at least one functionalized or unfunctionalized acryloyl moiety and at least one lactam moiety (monomer A); at least one monomer comprising at least one sulfonic acid moiety or a salt thereof (monomer B.sub.X1); and at least one crosslinker (monomer B.sub.X2).

(74) In particular embodiments, the polymer according to the invention is present in an amount from about 0.01 percent to about 20 percent by weight of the cementing fluid. More particularly, the polymer is present in an amount from about 0.05 percent to about 10 percent by weight of the cementing fluid. Even more particularly, the polymer is present in an amount from about 0.1 percent to about 5 percent by weight of the cementing fluid.

(75) In particular embodiments, the cementing fluids may further comprise at least one additive selected from the group consisting of: weighting agents, silica flour, strength enhancers, fluid loss control agents, surface rheology control additives, friction reducers, dispersing agents, gelation inhibitors, gas migration control additives, set retarding agents, accelerants, defoaming agents, lost circulation materials, corrosion inhibitors, salts, fly ash, fiber, strength retrogression additives, vitrified shale, lightweight additives, thixotropic additives, secondary cement anti-settling additives, and combinations thereof.

(76) The amount of each additive in the cementing fluid, when present, may vary depending on the type of composition, the function and/or physicochemical property of the additive, and the amount of other co-ingredients.

(77) Any of a variety of cementitious materials suitable for use in subterranean cementing operations may be used in accordance with particular aspects of the invention. Suitable non-limiting examples include hydraulic cements that comprise calcium, aluminum, silicon, oxygen, and/or sulfur, which set and harden by reaction with water. Such hydraulic cements, include, but are not limited to, Portland cements, pozzolana cements, gypsum cements, high alumina content cements, slag cements, and silica cements, and combinations thereof. Particularly, the cementitious material is a hydraulic cement. More particularly, the cementitious material is Portland cement.

(78) In a sixth aspect, the invention provides a fracturing fluid comprising a polymer comprising repeating units derived from at least one monomer comprising at least one functionalized or unfunctionalized acryloyl moiety and at least one lactam moiety (monomer A); at least one monomer comprising at least one sulfonic acid moiety or a salt thereof (monomer B.sub.X1); and at least one crosslinker (monomer B.sub.X2).

(79) In particular embodiments, the polymer according to the invention is present in an amount from about 0.01 percent to about 20 percent by weight of the fracturing fluid. More particularly, the polymer is present in an amount from about 0.05 percent to about 10 percent by weight of the fracturing fluid. Even more particularly, the polymer is present in an amount from about 0.1 percent to about 5 percent by weight of the fracturing fluid.

(80) In a seventh aspect, the invention provides a servicing fluid comprising a polymer comprising repeating units derived from at least one monomer comprising at least one functionalized or unfunctionalized acryloyl moiety and at least one lactam moiety (monomer A); at least one monomer comprising at least one sulfonic acid moiety or a salt thereof (monomer B.sub.X1); and at least one crosslinker (monomer B.sub.X2).

(81) In particular embodiments, the polymer according to the invention is present in an amount from about 0.01 percent to about 20 percent by weight of the servicing fluid. More particularly, the polymer is present in an amount from about 0.05 percent to about 10 percent by weight of the servicing fluid. Even more particularly, the polymer is present in an amount from about 0.1 percent to about 5 percent by weight of the servicing fluid.

(82) In an eighth aspect, the invention provides a method of cementing a subterranean zone penetrated by a well bore, comprising (A) providing a cementing fluid comprising a polymer comprising repeating units derived from at least one monomer comprising at least one functionalized or unfunctionalized acryloyl moiety and at least one lactam moiety (monomer A); at least one monomer comprising at least one sulfonic acid moiety or a salt thereof (monomer B.sub.X1); and at least one crosslinker (monomer B.sub.X2); (B) placing the cementing fluid into the subterranean zone; and (C) allowing the cementing fluid to set.

(83) In a ninth aspect, the invention provides a method of controlling fluid loss from a well bore into a subterranean zone, comprising (A) providing a drilling fluid comprising a polymer comprising repeating units derived from at least one monomer comprising at least one functionalized or unfunctionalized acryloyl moiety and at least one lactam moiety; at least one monomer comprising at least one sulfonic acid moiety or a salt thereof; and at least one crosslinker; and (B) placing the drilling fluid into the subterranean zone.

Methods of Synthesis

(84) The polymers according to the invention may be readily synthesized by procedures known by those skilled in the art, non-limiting examples of which include free radical polymerization, dispersion polymerization, emulsion polymerization, ionic chain polymerization, living polymerization, and precipitation polymerization.

(85) Free radical polymerization may be used, especially when using water-dispersible and/or water-soluble reaction solvent(s). This type of polymerization method is described in Decomposition Rate of Organic Free Radical Polymerization by K. W. Dixon (section II in Polymer Handbook, volume 1, 4th edition, Wiley-Interscience, 1999), the disclosure of which is hereby incorporated herein by reference in its entirety.

(86) Compounds capable of initiating the free-radical polymerization include those materials known to function in the prescribed manner, and include the peroxo and azo classes of materials. Peroxo and azo compounds include, but are not limited to: acetyl peroxide; azo bis-(2-amidinopropane) dihydrochloride; azo bis-isobutyronitrile; 2,2-azo bis-(2-methylbutyronitrile); benzoyl peroxide; di-tert-amyl peroxide; di-tert-butyl diperphthalate; butyl peroctoate; tert-butyl dicumyl peroxide; tert-butyl hydroperoxide; tert-butyl perbenzoate; tert-butyl permaleate; tert-butyl perisobutylrate; tert-butyl peracetate; tert-butyl perpivalate; para-chlorobenzoyl peroxide; cumene hydroperoxide; diacetyl peroxide; dibenzoyl peroxide; dicumyl peroxide; didecanoyl peroxide; dilauroyl peroxide; diisopropyl peroxodicarbamate; dioctanoyl peroxide; lauroyl peroxide; octanoyl peroxide; succinyl peroxide; and bis-(ortho-toluoyl) peroxide. Also suitable to initiate the free-radical polymerization are initiator mixtures or redox initiator systems, including: ascorbic acid/iron (II) sulfate/sodium peroxodisulfate, tert-butyl hydroperoxide/sodium disulfite, and tert-butyl hydroperoxide/sodium hydroxymethanesulfinate.

(87) The polymerization reactions may be carried out in the presence of solvent(s). The polymers may be synthesized in a solvent and maintained therein, or the synthesis solvent separated from the polymer by methods known in the art and replaced by a solvent beneficial for formulary development and/or end-use. The polymerization temperature may vary from about 5 C. to about 200 C. The polymerization reaction may be carried out at ambient pressure, sub-atmospheric pressure, or super-atmospheric pressure. The polymerization reaction may be carried out in a batch, continuous or semi-continuous manner.

Characterization of Polymers

(88) The polymers and compositions according to the invention may be analyzed by known techniques. Especially preferred are the techniques of .sup.13C nuclear magnetic resonance (NMR) spectroscopy, gas chromatography (GC), and gel permeation chromatography (GPC) in order to decipher polymer identity, residual monomer concentrations, polymer molecular weight, and polymer molecular weight distribution.

(89) Nuclear magnetic resonance (NMR) spectroscopy is an especially preferred method to probe the polymerization product in terms of chemical properties such as monomeric composition, sequencing and tacticity. Analytical equipment suitable for these analyses includes the Inova 400-MR NMR System by Varian Inc. (Palo Alto, Calif.). References broadly describing NMR include: Yoder, C. H. and Schaeffer Jr., C. D., Introduction to Multinuclear NMR, The Benjamin/Cummings Publishing Company, Inc., 1987; and Silverstein, R. M., et al., Spectrometric Identification of Organic Compounds, John Wiley & Sons, 1981, the disclosure of which is hereby incorporated herein by reference in its entirety.

(90) Residual monomer levels can be measured by GC, which can be used to indicate the extent of reactant conversion by the polymerization process. GC analytical equipment to perform these tests are commercially available, and include the following units: Series 5880, 5890, and 6890 GC-FID and GC-TCD by Agilent Technologies, Inc. (Santa Clara, Calif.). GC principles are described in Modern Practice of Gas Chromatography, third edition (John Wiley & Sons, 1995) by Robert L. Grob and Eugene F. Barry, the disclosure of which is hereby incorporated herein by reference in its entirety.

(91) GPC is an analytical method that separates molecules based on their hydrodynamic volume (or size) in solution of the mobile phase, such as hydroalcoholic solutions with surfactants. GPC is a preferred method for measuring polymer molecular weight distributions. This technique can be performed on known analytical equipment sold for this purpose, and include the TDAmax Elevated Temperature GPC System and the RImax Conventional Calibration System by Viscotek Corp. (Houston, Tex.). In addition, GPC employs analytical standards as a reference, of which a plurality of narrow-distribution polyethylene glycol and polyethylene oxide standards representing a wide range in molecular weight is the preferred. These analytical standards are available for purchase from Rohm & Haas Company (Philadelphia, Pa.) and Varian Inc. (Palo Alto, Calif.). GPC is described in the following texts, the disclosure of which is hereby incorporated herein by reference in its entirety: Schroder, E., et al., Polymer Characterization, Hanser Publishers, 1989; Billingham, N.C., Molar Mass Measurements in Polymer Science, Halsted Press, 1979; and Billmeyer, F., Textbook of Polymer Science, Wiley Interscience, 1984.

(92) The polymers according to the invention may be prepared according to the procedures set out below. The examples are presented for purposes of demonstrating, but not limiting, the preparation of the polymers. Therein, the following abbreviations are used:

(93) PyEMA: Pyrrolidonylethyl methacrylate

(94) AMPS: 2-acrylamido-2-methyl-1-propanesulfonic acid

(95) NaAMPS: Sodium salt of 2-acrylamido-2-methyl-1-propanesulfonic acid

(96) MBA: Methylenebisacrylamide

(97) PAE: Pentaerythritol allyl ether

(98) HTHP: High Temperature/High Pressure

(99) HT: High Temperature

(100) PV: Plastic Viscosity

(101) YP: Yield Point

(102) API: American Petroleum Institute

(103) RT: Room Temperature

EXAMPLES

Example 1

(104) An amount of 74.9 g of AMPS and 510 g of tert-butanol was added to a 1 liter four-necked reactor. The reaction mixture was neutralized with 25.2 g of ammonium hydroxide (28-30% in H.sub.2O). The reaction vessel was then equipped with thermocouple, cold water condenser, and anchor agitator before heating reaction to 68 C. Once all pellets of AMPS were dissolved, pH value of the mixture was tested and kept in the range of 6.5 to 7.5. The reactor was then charged with 0.82 g of MBA that has been fully solubilized in 5 g and 5 g tert-butanol. An amount of 7.5 g of PAE and 7.7 g PyEMA were then charged into reactor. Subsurface N.sub.2 sparge was then introduced to reactor. An amount of 0.2828 g of Trigonox 25C75/2 g tert-butanol was charged into reactor (time t=0). Within 30 minutes, white precipitated particles were visible. An additional shot of 0.2828 g Trigonox 25C75/2 g tert-butanol was added 2 hours later (t=2). At t=3 hours, the reaction temperature was then increased to 80 C. One hour later (t=4), a final shot of 0.15 g Trigonox 25C75/2 g tert-butanol was added. The reaction was held for 2 additional hours (t=6), then cooled and discharged. The resultant polymer powder was filtered using Buchner funnel and washed three times with approximately 50 mL of hot tert-butanol. The polymer was transferred to a baking dish to dry further in an 80 C. vacuum oven with a vacuum of approximately 20 torr overnight.

Example 2

(105) An amount of 78.5 g of AMPS and 510 g of tert-butanol was added to a 1 liter four-necked reactor. The reaction mixture was neutralized with 26.6 g of ammonium hydroxide (28-30% in H.sub.2O). The reaction vessel was then equipped with thermocouple, cold water condenser, and anchor agitator before heating reaction to 68 C. Once all pellets of AMPS were dissolved, pH value of the mixture was tested and kept in the range of 6.5 to 7.5. The reactor was then charged with 0.82 g of MBA that has been fully solubilized in 5 g and 5 g tert-butanol. An amount of 7.5 g of PAE and 4.13 g PyEMA were then charged into reactor. Subsurface N.sub.2 sparge was then introduced to reactor. An amount of 0.2828 g of Trigonox 25C75/2 g tert-butanol was charged into reactor (time t=0). Within 30 minutes, white precipitated particles were visible. An additional shot of 0.2828 g Trigonox 25C75/2 g tert-butanol was added 2 hours later (t=2). At t=3 hours, the reaction temperature was then increased to 80 C. One hour later (t=4), a final shot of 0.15 g Trigonox 25C75/2 g tert-butanol was added. The reaction was held for 2 additional hours (t=6), then cooled and discharged. The resultant polymer powder was filtered using Buchner funnel and washed three times with approximately 50 mL of hot tert-butanol. The polymer was transferred to a baking dish to dry further in an 80 C. vacuum oven with a vacuum of approximately 20 torr overnight.

Example 3

(106) An amount of 80.9 g of AMPS and 510 g of tert-butanol was added to a 1 liter four-necked reactor. The reaction mixture was neutralized with 27.3 g of ammonium hydroxide (28-30% in H.sub.2O). The reaction vessel was then equipped with thermocouple, cold water condenser, and anchor agitator before heating reaction to 68 C. Once all pellets of AMPS were dissolved, pH value of the mixture was tested and kept in the range of 6.5 to 7.5. The reactor was then charged with 0.82 g of MBA that has been fully solubilized in 5 g and 5 g tert-butanol. An amount of 7.5 g of PAE and 1.7 g PyEMA were then charged into reactor. Subsurface N.sub.2 sparge was then introduced to reactor. An amount of 0.2828 g of Trigonox 25C75/2 g tert-butanol was charged into reactor (time t=0). Within 30 minutes, white precipitated particles were visible. An additional shot of 0.2828 g Trigonox 25C75/2 g tert-butanol was added 2 hours later (t=2). At t=3 hours, the reaction temperature was then increased to 80 C. One hour later (t=4), a final shot of 0.15 g Trigonox 25C75/2 g tert-butanol was added. The reaction was held for 2 additional hours (t=6), then cooled and discharged. The resultant polymer powder was filtered using Buchner funnel and washed three times with approximately 50 mL of hot tert-butanol. The polymer was transferred to a baking dish to dry further in an 80 C. vacuum oven with a vacuum of approximately 20 torr overnight.

Example 4

(107) An amount of 74.9 g of AMPS and 510 g of tert-butanol was added to a 1 liter four-necked reactor. The reaction mixture was neutralized with 25.2 g of ammonium hydroxide (28-30% in H.sub.2O). The reaction vessel was then equipped with thermocouple, cold water condenser, and anchor agitator before heating reaction to 68 C. Once all pellets of AMPS were dissolved, pH value of the mixture was tested and kept in the range of 6.5 to 7.5. The reactor was then charged with 0.41 g of MBA that has been fully solubilized in 5 g and 5 g tert-butanol. An amount of 3.3 g of PAE and 7.7 g PyEMA were then charged into reactor. Subsurface N.sub.2 sparge was then introduced to reactor. An amount of 0.2828 g of Trigonox 25C75/2 g tert-butanol was charged into reactor (time t=0). Within 30 minutes, white precipitated particles were visible. An additional shot of 0.2828 g Trigonox 25C75/2 g tert-butanol was added 2 hours later (t=2). At t=3 hours, the reaction temperature was then increased to 80 C. One hour later (t=4), a final shot of 0.15 g Trigonox 25C75/2 g tert-butanol was added. The reaction was held for 2 additional hours (t=6), then cooled and discharged. The resultant polymer powder was filtered using Buchner funnel and washed three times with approximately 50 mL of hot tert-butanol. The polymer was transferred to a baking dish to dry further in an 80 C. vacuum oven with a vacuum of approximately 20 torr overnight.

Example 5

(108) An amount of 74.9 g of AMPS and 510 g of tert-butanol was added to a 1 liter four-necked reactor. The reaction mixture was neutralized with 25.2 g of ammonium hydroxide (28-30% in H.sub.2O). The reaction vessel was then equipped with thermocouple, cold water condenser, and anchor agitator before heating reaction to 68 C. Once all pellets of AMPS were dissolved, pH value of the mixture was tested and kept in the range of 6.5 to 7.5. The reactor was then charged with 0.41 g of MBA that has been fully solubilized in 5 g and 5 g tert-butanol. An amount of 3.3 g of PAE and 7.7 g PyEMA were then charged into reactor. Subsurface N.sub.2 sparge was then introduced to reactor. An amount of 0.2828 g of Trigonox 25C75/2 g tert-butanol was charged into reactor (time t=0). Within 30 minutes, white precipitated particles were visible. An additional shot of 0.2828 g Trigonox 25C75/2 g tert-butanol was added 2 hours later (t=2). At t=3 hours, the reaction temperature was then increased to 80 C. One hour later (t=4), a final shot of 0.15 g Trigonox 25C75/2 g tert-butanol was added. The reaction was held for 2 additional hours (t=6), then cooled and discharged. The resultant polymer powder was filtered using Buchner funnel and washed three times with approximately 50 mL of hot tert-butanol. The polymer was transferred to a baking dish to dry further in an 80 C. vacuum oven with a vacuum of approximately 20 torr overnight.

(109) Table 1 shows a summary of reaction conditions for crosslinked polymers of AMPS and PyEMA prepared by precipitation polymerization in tert-butanol

(110) TABLE-US-00001 TABLE 1 Reaction Conditions Summary Reaction Temperature/ Chasing Reaction Reactant Weight Ratio (%) Example Temperature Time AMPS PyEMA PAE MBA 1 68 C./80 C. 6 hours 90 10 9 1 2 68 C./80 C. 6 hours 95 5 9 1 3 68 C./80 C. 6 hours 98 2 9 1 4 68 C./80 C. 6 hours 90 10 4 0.5 5 68 C./80 C. 6 hours 90 10 7 0.5

Drilling Fluids

Example 6

(111) Five drilling fluid (mud) Formulations numbered 1-5 as shown in Table 2 were prepared on a 600 g scale incorporating polymers from aforementioned synthetic examples. Sufficient mixing was conducted to facilitate dissolving all the ingredients. The drilling fluids were allowed to agitate for 5 to 15 minutes between the addition of each component and with 20 to 40 minutes total for complete and homogenous mixing. Rheological properties were then measured on a Fann 35 before hot rolling (BHR) and after hot rolling (AHR), or before static aging (BSA) and after static aging (ASA). The testing results are shown in Table 2.

(112) TABLE-US-00002 TABLE 2 Study of Exemplary Polymers in 12 ppg Drilling Muds Containing 8.6 bl/gal KCl Mixing Ingredients time Formulation 1 Formulation 2 Formulation 3 Formulation 4 Formulation 5 8.6 ppg 289 289 289 289 289 KCl, ml Polymer of 10 min 6 Example 1, ppb Polymer of 10 min 5 Example 2, ppb Polymer of 10 min 6 Example 3, ppb Polymer of 10 min 6 Example 4, ppb Polymer of 10 min 6 Example 5, ppb NaOH, 50% 30 sec 1 drop 1 drop 1 drop 1 drop 1 drop API Barite, 10 min 180 180 180 180 180 ppb Aging 350 F. hot 375 F. static aging/16 hours condition rolling/ 16 hours Fann Data @ RT BHR AHR BSA ASA BSA ASA BSA ASA BSA ASA 600 rpm 55 89 52 19 66 73 36 53 44 54 300 rpm 38 66 36 12 48 48 26 34 34 36 200 rpm 31 55 29 9 37 37 21 26 26 27 100 rpm 24 44 22 6 26 25 16 18 20 17 6 rpm 13 20 12 3 10 8 7 4 10 4 3 rpm 12. 18 11 2 9 7 6 3 9 3 PV, cps 17 23 16 7 18 25 10 19 10 18 YP, lb/100 ft.sup.2 21 43 20 5 30 23 16 15 24 18 HTHP N/A 10 13.6 19.2 filtration, 350 F./500 psi, ml/30 min

(113) Table 2 demonstrates that polymers according to the invention are thermally stable up to 375 F. They are effective as HTHP fluid loss control additives and have utility as HT rheology modifiers up to 375 F.

Cementing Fluids

Example 7

(114) 15.8 ppg of H class cement slurries were formulated using components and mixing/formulation techniques commonly employed in the industry as recommended by American Petroleum Institute. Their rheologies were recorded on an Ofite viscometer before and after conditioning at 190 F. as shown in Table 3.

(115) TABLE-US-00003 TABLE 3 Study of Exemplary Polymers in 15.8 ppg H Cement Containing 35% Silica Flour Test Sample Polymer of Example 2, Polymer of Example 3, Polymer of Example 4, 0.5 bwoc %* 0.5 bwoc % 0.5 bwoc % Temp. Ambient 190 F. Ambient 190 F. Ambient 190 F. 300 rpm 130.3 307.8 100.9 195.7 125.7 228.5 200 rpm 96.1 93.6 260.1 242.8 66.6 70.7 154.6 151.8 82.4 91.3 180.4 173.9 100 rpm 55.9 51.8 190.9 173.8 33.9 34.8 101.6 97.9 42.9 47.2 117.1 110.1 60 rpm 38.8 33.7 157.9 140.9 20.2 20.5 74.5 70.8 25.3 27.9 85.4 78.1 30 rpm 25.1 19.7 125.7 110.3 9.3 9.3 47.9 45.8 11.5 12.5 55.7 48.5 6 rpm 11.6 9.8 74.2 64.8 1.6 1.4 22.8 20.5 1.4 1.6 18.1 16.9 3 rpm 8.1 7.8 69.6 49.9 0.6 0.7 17.9 16.9 0.7 0.7 11.7 10.7 600 rpm 213 320.2+ 187.1 294.6 221.6 320.1+ PV, cps 114.7 188.2 99.8 143.9 121.0 172.3 YP, lb/ 15.6 119.6 1.1 51.8 4.7 56.1 100 ft2 *bwoc: based on weight of cement

(116) Table 3 demonstrates that polymers according to the invention are hydrated at 190 F. and have utility as antisettling agent in cement slurries.