Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
  • C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
  • C07D295/18—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carboxylic acids, or sulfur or nitrogen analogues thereof
  • C07D295/182—Radicals derived from carboxylic acids
  • C07D295/185—Radicals derived from carboxylic acids from aliphatic carboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C237/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups
  • C07C237/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton
  • C07C237/04—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
  • C07C309/01—Sulfonic acids
  • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
  • C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
  • C07C309/13—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton
  • C07C309/14—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton containing amino groups bound to the carbon skeleton
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
  • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
  • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
  • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
  • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
  • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
  • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
• • 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
  • C08F20/00—Homopolymers and 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
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/52—Amides or imides
  • C08F20/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
  • C08F20/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
• • 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
  • C08F26/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
  • C08F26/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
• • 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
  • C08F8/00—Chemical modification by after-treatment
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
  • C09K8/02—Well-drilling compositions
  • C09K8/04—Aqueous well-drilling compositions
  • C09K8/06—Clay-free compositions
  • C09K8/12—Clay-free compositions containing synthetic organic macromolecular compounds or their precursors
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
  • C09K8/02—Well-drilling compositions
  • C09K8/04—Aqueous well-drilling compositions
  • C09K8/14—Clay-containing compositions
  • C09K8/18—Clay-containing compositions characterised by the organic compounds
  • C09K8/22—Synthetic organic compounds
  • C09K8/24—Polymers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
  • C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
  • C09K8/588—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific polymers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
  • C09K8/60—Compositions for stimulating production by acting on the underground formation
  • C09K8/607—Compositions for stimulating production by acting on the underground formation specially adapted for clay formations
  • C09K8/608—Polymer compositions
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
  • C09K8/60—Compositions for stimulating production by acting on the underground formation
  • C09K8/62—Compositions for forming crevices or fractures
  • C09K8/66—Compositions based on water or polar solvents
  • C09K8/68—Compositions based on water or polar solvents containing organic compounds
  • C09K8/685—Compositions based on water or polar solvents containing organic compounds containing cross-linking agents
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
  • C09K8/60—Compositions for stimulating production by acting on the underground formation
  • C09K8/84—Compositions based on water or polar solvents
  • C09K8/86—Compositions based on water or polar solvents containing organic compounds
  • C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
  • C09K8/887—Compositions based on water or polar solvents containing organic compounds macromolecular compounds containing cross-linking agents
• • 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
  • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
  • C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
• • 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
  • C08F2810/00—Chemical modification of a polymer
  • C08F2810/20—Chemical modification of a polymer leading to a crosslinking, either explicitly or inherently

Definitions

• the present invention relates to compositions which can be used to prepare water-soluble polymers that are useful in oil field applications and processes for producing the compositions; to water-soluble polymers which can be prepared from the compositions and nitrogen-containing olefinic compounds as well as processes for producing and using the water-soluble polymers; and to gelling compositions produced from the water-soluble polymers for applications in a subterranean formation such as, for example, altering permeability and correcting water coning problems and processes for producing and using the gelling compositions.
• polymers or polymers along with a gelling agent such as an appropriate crosslinking agent in a liquid are injected into the formation.
• the polymers then permeate into and gel, in the cases when a polymer and a crosslinking agent are used, in the regions having the highest water permeability.
• produced brine which is defined as the brine co-produced with oil and gas and is generally contaminated with some oil, or gas, or both
• Use of produced brines eliminates not only the cost associated with acquiring and pre-treating fresh water for use as the liquid but also the disposal cost for the produced brine.
• Most produced brines are known to be hard brines, i.e., those having a divalent cation concentration greater than 1000 ppm.
• polymers have been developed and used in processes for the recovery of hydrocarbons. Generally a desirable property is that such polymers impart to a liquid an increased viscosity when a relatively small quantity of the polymer is added, and preferably at a minimal cost. Another desirable property is that such polymers form gels, in the presence of a suitable gelling agent such as a crosslinking agent. However, a number of such polymers are not capable of forming gels having high thermal stability, i.e., the gels formed show high syneresis after a short period, such as for example a few days, at high temperature, such as for example, 120°C in a harsh environment such as sea water.
• the gellable polymers may be used in the process for recovery of hydrocarbons.
• multivalent metallic ions crosslink gellable polymers through the interaction with the oxygen atoms of the polymer molecules. Therefore, the gellable polymers generally contain some carboxylate groups.
• the gellable polymers used such as, for example, partially hydrolyzed polyacrylamide are of high molecular weight and contain high degrees of hydrolysis, i.e., contain 10-30 mole % carboxylate groups.
• these high molecular weight and/or high mole % carboxylate group-containing polymers gel almost instantly in the presence of the above-described multivalent metallic compounds.
• a hostile environment includes, but is not limited to, high temperatures, high salinity and7or high content of divalent metal cations, commonly known as “hardness ions”, as well as the high acidity, temperature and shear conditions encountered in processes such as acid fracturing.
• drilling fluid In the art of drilling wells to tap subterranean deposits of natural resources, such as gas, geothermal steam or oil, it is well known to use a drilling fluid. In addition to having the desirably rheological properties such as viscosity and gel strength, it is very important that such drilling fluids exhibit a low rate of filtration or water loss, that is, the drilling fluid must prevent excessive amounts of fluid, or
• compositions comprising mixtures of carboxylic acid polymers and soluble metal salts with the object of increasing the “yield” (defined as the number of barrels of 15 centipoise mud which can be prepared from one ton of clay) of relatively low-grade clays have been used.
• Breakdown of polymers causes a large increase in the fluid loss accompanied by an increase in filter cake thickness. These conditions often result in differential sticking of the drill string. It is, therefore, desirable to develop additives which enable drilling fluids to retain their proper viscosity and fluid content over a broader range of conditions.
• Drilling fluids are used in the drilling of various types of wells.
• Workover and completion fluids are those fluids used in the completion and servicing of such wells.
• Completion fluids are those fluids used after drilling is complete and during the steps of completion, or recompletion, of the well. Completion can include cementing the casing, perforating the casing, setting the tubing and pump, etc.
• Workover fluids are those fluids used during remedial work in the well.
• Workover also broadly includes steps used in preparing an existing well for secondary or tertiary oil recovery such as polymer additions, micellar flooding, steam injection, etc. Both workover and completion fluids are used in part to control well pressure, to prevent the collapse of casing from ove ⁇ ressure, and to prevent or reduce corrosion of casing.
• a drilling fluid may be suitable for completion or workover over applications in some cases, but not in all cases.
• a composition which can be used to prepare a more hostile environment-withstanding polymer as well as a hostile environment-withstanding gelling composition, containing the hostile environment-withstanding polymer, that can form stable gels in a liquid such as, for example, produced brines, for near- wellbore as well as in-depth treatments, and preferably that does not require a gelation delaying agent, is highly desirable. It is also highly desirable to develop a composition which can be used in drilling fluids, completion fluids, or Workover fluids.
• An object of the invention is to provide a composition which can be used as a monomer to synthesize a hostile environment-withstanding, water-soluble polymer. Another object of the invention is to provide a process for synthesizing the composition. Yet another object of the present invention is to provide a water-soluble polymer that can be used to form a gel in a hostile environment in hydrocarbon-bearing subterranean formations. Also an object of the invention is to provide a process for altering the permeability of hydrocarbon-bearing subterranean formations using the water-soluble polymer or for other drilling applications. A further object of the invention is to provide a gelling composition which contains the water-soluble polymer and withstands a hostile environment.
• An advantage of the invention is that the gelling compositions of the invention generally withstand a hostile environment and the processes generally do not employ a gelation delaying agent, yet achieve the alteration of permeability of the formations or can be used in other applications.
• Other objects, features, and advantages will become more apparent as the invention is more fully disclosed hereinbelow.
• a composition that can be used to prepare a water-soluble polymer which can be used in a hydrocarbon-bearing subterranean formation.
• the composition comprises a nitrogen-containing olefinic compound.
• a process for preparing a composition is provided that can be used to prepare a water-soluble polymer which can be used in a hydrocarbon-bearing formation wherein said composition comprises a nitrogen-containing olefinic compound.
• a water-soluble polymer which can be used in a hydrocarbon-bearing formation.
• the polymer comprises repeat units derived from at least one nitrogen-containing olefinic compound.
• a process which can be used for treating hydrocarbon-bearing formation comprises introducing into the formation a water-soluble composition wherein the water-soluble composition comprises a water-soluble polymer comprising repeat units derived from at least one nitrogen-containing olefinic compound.
• a gelling composition which comprises a water-soluble polymer, a crosslinking agent, and a liquid wherein the water-soluble polymer comprises repeat units derived from at least one nitrogen-containing olefinic compound.
• a process is provided which comprises introducing into a subterranean formation a gelling composition comprising a water-soluble polymer, a crosslinking agent, and a liquid wherein the gelling composition forms gels when introduced into the formation and the water-soluble polymer comprises repeat units derived from at least one nitrogen- containing olefinic compound.
• a composition which can be used as or in drilling fluid, completion fluid, workover fluid, or combinations of any two or more thereof is provided.
• the composition can comprise, consist essentially of, or consist of a water-soluble polymer, a clay, and a liquid wherein the polymer comprises repeat units derived from at least one nitrogen-containing olefinic compound.
• composition useful as a monomer for synthesizing a water-soluble polymer comprises, or consists essentially of, or consists of a nitrogen-containing olefinic compound having the formula selected from the group consisting of sulfobetaines, vinylic amides, and combinations of any two or more thereof wherein the sulfobetaine has the formula of
• R, and R 2 can be the same or different and are each independently selected from the group consisting of hydrogen, alkyl radicals, aryl radicals, aralkyl radicals, alkaryl radicals, and combinations of any two or more thereof wherein each radical can contain 1 to about 30, preferably 1 to abut 20, more preferably 1 to about 15, and most preferably 1 to 10 carbon atoms and can contain functional group(s) such as ammonium, hydroxyl, sulfate, ether, carbonyl groups, amine gr ups, sulfhydryl groups, or combinations of any two or more thereof which can contribute to water solubility of polymers produced therefrom.
• each radical can contain 1 to about 30, preferably 1 to abut 20, more preferably 1 to about 15, and most preferably 1 to 10 carbon atoms and can contain functional group(s) such as ammonium, hydroxyl, sulfate, ether, carbonyl groups, amine gr ups, sulfhydryl groups, or combinations of any two or more
• R is hydrogen and R 2 is hydrogen, methyl, ethyl, or combinations of two or more thereof.
• Y is an alkylene radical, a phenyl group, an imidazolium group, a naphthyl group, a biphenyl group, or combinations of any two or more thereof.
• Each Y is preferably independently an alkylene radical which can have 1 to about 20, preferably 1 to about 15. and more preferably 1 to 10 carbon atoms.
• Y is a short alkylene radical having 1 to about 5 carbon atoms.
• Ar is an arylene radical, preferably a phenyl group, which can be substituted or unsubstituted.
• X is an anion selected from the group consisting of halides, sulfates, phosphates, nitrates, sulfonates, phosphonates, sulfinates, phosphinates, and combinations of any two or more thereof.
• Each m can be the same or different and is 0 or 1.
• suitable nitrogen-containing olefinic compounds of the first embodiment of the invention include, but are not limited to, N,N-dimethyl-N-(3-sulfopropyl)-N-(4-vinylbenzyl) ammonium inner salt, N,N-dimethyl-N-(3-sulfobutyl)-N-(4-vinylbenzyl) ammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-N-(4-vinylbenzyl) ammonium inner salt,
• N,N-diethyl-N-(3-sulfobutyl)-N-(4-vinylbenzyl) ammonium inner salt N,N-dimethyl-N-(3-sulfopropyl)-N-(3-vinylbenzyl) ammonium inner salt, N,N-dimethyl-N-(3-sulfobutyl)-N-(3-vinylber_zyl) ammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-N-(3-vinylbenzyl) ammonium inner salt, N,N-diethyI-N-(3-sulfobutyl)-N-(3-vinylbenzyl) ammonium inner salt,
• N-acryloyl-N'-methyl-N'-(2-amino-2-oxoethyl) piperazinium chloride N-acryloyl-N'-methyl-N'-(3-amino-3-oxopropyl) piperazinium chloride
• N-acryloyl-N'-ethyl-N'-(4-amino-4-oxobutyl) piperazinium chloride N,N-dimethyl-N-(2-amino-2-oxoethyl)-N-(4-vinylbenzyl) ammonium chloride, N,N-diethyl-N-(2-amino-2-oxoethyl)-N-(4-vinylbenzyl) ammonium chloride, N,N-dimethyl-N-(3-amino-3-oxopropyl)-N-(4-vinylbenzyl) ammonium chloride, N,N-diethyl-N-(3-amino-3-oxopropyI)-N-(4-vinylbenzyl) ammonium chloride,
• the nitrogen-containing olefinic compounds of the first embodiment of the invention can be prepared by the process disclosed hereinbelow in the second embodiment of the invention.
• an alkylating agent such as, for example, an alkylsulfonic acid containing a proper leaving group such as halide, hydroxyl, tosylate, other suitable leaving groups, or combinations of any two or more thereof.
• reagents can be contacted, under any suitable conditions so long as the conditions can effect the production of the nitrogen-containing olefinic compounds, in a solvent such as toluene, benzene, pentane, hexane, acetonitrile, methanol, ethanol, any other common organic solvent or combinations of any two or more solvents.
• a solvent such as toluene, benzene, pentane, hexane, acetonitrile, methanol, ethanol, any other common organic solvent or combinations of any two or more solvents.
• a tertiary amine can be contacted with an alkylating agent at a temperature in the range of from about 10 to about 120°C, preferably about 20 to about 90 C C, and most preferably 35 to 65 °C for about 1 to about 10 days, preferably about 1 to about 8 days, and most preferably 1 to 5 days under any suitable pressures such as, for example, about 1 atmospheric pressure.
• a suitable radical inhibitor such as 1.3-dinitrobenzene can be added to prevent polymerization of the nitrogen-containing olefinic compounds during the contacting.
• the production is carried out by using 1 ,3-propanesultone or 1 ,4-butanesultone as the alkylating reagent in toluene by heating at 45-50 °C for 72 hours.
• the sulfobetaine generally precipitates from the solvent and can be purified by filtration, repeated washing with any common organic solvent that does not dissolve the sulfobetaine, and finally dried under reduced pressure.
• diethyl ether is used to wash the sulfobetaine during filtration, and the product can be dried under a pressure such as, for example, 5 cm Hg for 48 hours.
• Suitable tertiary amines include, but are not limited to,
• N,N-dimethyl-N-(4-vinylbenzyl) amine N,N-dimethyl-N-(4-vinylbenzyl) amine, N,N-diethyl-N-(4-vinylbenzyl) amine, N,N-diethyl-N-(4-vinylbenzyl) amine,
• N,N-dimethyl-N-(3-vinylbenzyl) amine N,N-dimethyl-N-(3-vinylbenzyl) amine
• alkylating reagents include, but are not limited to, 3-chloro-propane-l-sulfonic acid, 4-chloro-butane-l-sulfonic acid,
• the nitrogen-containing olefinic compounds with the amide functional group of the first embodiment of the invention have general formulae of
• alkylating agent such as, for example, an alkyl amide containing a proper leaving group such as halide, hydroxyl, tosylate, other suitable leaving groups, or combinations of any two or more thereof.
• reagents can be contacted, under any conditions so long as the conditions can effect the production of the nitrogen-containing olefinic compounds in a solvent such as toluene, benzene, pentane, hexane, acetonitrile, methanol, ethanol, any other common organic solvents, or combinations of any two or more thereof.
• a vinyl-substituted amine and an alkylating agent can be contacted under a condition including a temperature in the range of from about 10 to about 150°C, preferably about 20 to about 120°C, and most preferably 30 to 100°C for about 1 to about 15 days, preferably 1 to 8 days under any suitable pressure such as, for example, about 1 atmospheric pressure.
• a suitable radical inhibitor such as, for example, 1,3-dinitrobenzene can be added to prevent polymerization of the nitrogen-containing olefinic compounds during the contacting.
• the production is carried out by using 2-chloro-acetamide as Ihe alkylating agent in acetonitrile by heating at 45-80 °C for 50-150 hours.
• the nitrogen-containing olefinic compounds generally precipitate from the solvent and can be purified by filtration, repeated washing with any common organic solvent that does not dissolve the nitrogen-containing olefinic compounds, and finally dried under reduced pressure.
• diethyl ether is used to wash the nitrogen-containing olefinic compounds during filtration, and the nitrogen-containing olefinic compounds generally can be dried under a suitable pressure such as, for example, 5 cm Hg for 48 hours.
• Suitable vinyl-substituted amines include, but are not limited to, N,N-dimethyl-N-(4-vinylbenzyl) amine, N,N-dimethyl-N-(4-vinylbenzyl) amine, N,N-diethyl-N-(4-vinylbenzyl) amine, N,N-diethyl-N-(4-vinylbenzyl) amine, N,N-dimethyl-N-(3-vinylbenzyl) amine, N,N-dimethyl-N-(3-vinylbenzyl) amine, N,N-diethyl-N-(3-vinylbenzyl) amine and N,N-diethyl-N-(3-vinylbenzyl) amine, and combinations of any two or more thereof.
• suitable alkylating agents include, but are not limited to.
• the molar ratio of the alkylating agent to the amine can be any ratio so long the ratio can effect the production of the nitrogen-containing olefinic compounds.
• tlie molar ratio can be in the range of from about 1 :0.01 to about 0.01 :1, preferably about 1 :0.05 to about 0.05 : 1 , and most preferably 1 :0.1 to 0.1 : 1.
• the molar ratio of the radical inhibitor to the amine can be in the range of from about 0.1 : 1 to about 1 ,000: 1.
• the molar ratio of the solvent to the amine can be any ratio that is effective in the production of a nitrogen-containing olefinic compound and can be in the range of from about 0.1 : 1 to about 1 ,000: 1.
• a water-soluble polymer which can withstand a hostile environment and can be used for treating a hydrocarbon-bearing subterranean formation.
• the water-soluble polymer comprises, or consists essentially of, or consists of, repeat units derived from at least one nitrogen-containing olefinic compound.
• polymer as used herein denotes a molecule having at least about 10 repeat units and can be homopolymer, copolymer, te ⁇ olymer, tetrapolymer, or combination of any two or more thereof.
• any nitrogen-containing olefinic compounds having a polymerizable ethylenic linkage and being capable of producing a polymer which withstands hostile environment can be used for preparing the water-soluble polymer of the third embodiment of the present invention.
• the ethylenic linkage be at the terminal end of the nitrogen-containing olefin molecule and that at least one nitrogen be a tertiary amine.
• R, and R 2 can be the same or different and are each independently selected from the group consisting of hydrogen, alkyl radicals, aryl radicals, aralkyl radicals, alkaryl radicals, and combinations of any two or more thereof wherein each radical can contain 1 to about 30, preferably 1 to abut 20, more preferably 1 to about 15, and most preferably 1 to 10 carbon atoms and can contain functionalities such as, for example, hydroxyl, sulfate, carbonyl, amine, sulfhydryl, or combinations of any two or more thereof.
• R is hydrogen
• R 2 is hydrogen, methyl, ethyl, or combinations of any two or more thereof.
• M is a mo ⁇ holine group which can be substituted or unsubstituted.
• Y is an alkylene radical, a phenyl group, an imidazolium group, a naphthyl group, a biphenyl group, or combinations of any two or more thereof which can have 1 to about 20, preferably 1 to about 15, and most preferably 1 to 10 carbon atoms. Most preferably, Y is a short alkylene radical having 1 to about 5 carbon atoms.
• Ar is an arylene radical, preferably phenyl, w hich can be substituted or unsubstituted.
• X is an anion selected from the group consisting of halides, sulfate, phosphate, nitrate, sulfonates, phosphonates, sulfinates, phosphinates, and combinations of any two or more thereof.
• Each m can be the same or different and is independently 0 or 1.
• the water-soluble polymer of the third embodiment of the present invention can be a homopolymer, copolymer, te ⁇ olymer or tetrapolymer.
• the nitrogen-containing olefinic repeat units contain an amide group
• M, Y, R réelle and R 2 are the same as those disclosed above.
• the letter m is 0 or 1.
• G is N(R,) or O.
• W is an acid moiety selected from the group consisting of phosphinic acid, phosphonic acid, sulfinic acid, sulfonic acid, sulfuric acid, sulfurous acid, carboxylic acid, phosphoric acid, ammonium salts or alkali metal salts of these acids, and combinations of any two or more thereof.
• suitable nitrogen-containing olefinic compounds of the third embodiment of the invention include, but are not limited to, N-acryloyl mo ⁇ holine, N-acryloyl-N ' -methyl piperazine,
• N-acryloyl-N ' -ethyl piperazine N-acryloyl-N '-propyl piperazine, N-acryloyl-N'-(3-sulfopropyl)-N '-methyl piperazinium inner salt, N-acryloyl-N '-(3-sulfopropyl)-N '-ethyl piperazinium inner salt, N-acryloyl-N'-(4-sulfopropyl)-N'-methyl piperazinium inner salt, N-acryloyl-N ' -(4-sulfopropyl)-N '-ethyl piperazinium inner salt,
• N-acryloyl-N '-(2-amino-2-oxoethyl)-N '-methyl piperazinium chloride N-acryloyl-N'-(3-amino-3-oxopropyl)-N'-methyl piperazinium chloride, N-acryloyl-N ' -(4-amino-4-oxobutyl)-N'-methyl piperazinium chloride, N-acryloyl-N'-(2-amino-2-oxoethyl)-N'-ethyl piperazinium chloride, N-acryloyl-N '-(3-amino-3-oxopropyl)-N ' -ethyl piperazinium chloride,
• N-acryloyl-N'-(4-amino-4-oxobutyl)-N'-ethyl piperazinium chloride N,N-dimethyl-N-(3-sulfopropyl)-N-(4-vinylbenzyl) ammonium inner salt
• N,N-dimethyl-N-(4-sulfobutyl)-N-(4-vinylbenzyl) ammonium inner salt N,N-diethyl-N-(3-sulfopropyl)-N-(4-vinylbenzyl) ammonium inner salt
• N,N-diethyl-N-(4-sulfobutyl)-N-(4-vinylbenzyl) ammonium inner salt N,N-diethyl-N-(4-sulfobutyl)-N-(4-vinylbenzyl) ammonium inner salt
• N,N-dimethyI-N-(3-sulfopropyl)-N-(3-vinylbenzyl) ammonium inner salt N,N-dimethyl-N-(4-sulfobutyl)-N-(3-vinylbenzyl) ammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-N-(3-vinylbenzyl) ammonium inner salt, N,N-diethyl-N-(4-sulfobutyl)-N-(3-vinylbenzyl) ammonium inner salt, N,N-dimethyl-N-(2-amino-2-oxoethyl)-N-(4-vinylbenzyl) ammonium chloride,
• N,N-diethyl-N-(2-amino-2-oxoethyl)-N-(4-vinylbenzyl) ammonium chloride N.N-dimethyl-N-(3-amino-3-oxopropyl)-N-(4-vinylbenzyl) ammonium chloride, N,N-diethyl-N-(3-amino-3-oxopropyl)-N-(4-vinylbenzyl) ammonium chloride, N,N-dimethyl-N-(2-amino-2-oxoethyl)-N-(3-vinylbenzyl) ammonium chloride, N,N-diethyl-N-(2-amino-2-oxoethyl)-N-(3-vinylbenzyl) ammonium chloride, N,N-dimethyl-N-(3-amino-3-oxopropyl)-N-(3-vin
• N,N-dimethyl-N-(3-sulfopropyl)-3-(acryloyl amino)- 1 -propaneammonium inner salt N,N-diethyl-N-(3-sulfopropyl)-3-(acryloyl amino)- 1 -propaneammonium inner salt, N,N-dimethyl-N-(4-sulfobutyl)-3-(acryloy 1 amino)- 1 -propaneammonium inner salt,
• N,N-diethyl-N-(4-sulfobutyl)-3-(acryloyl amino)- 1 -propaneammonium inner salt N,N-dimethyl-N-(3-sulfopropyl)-2-(acryloyl amino )-l-ethaneammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-2-(acryloyl amino)- 1-ethaneammonium inner salt, N,N-dimethyl-N-(4-sulfobutyl)-2-(acryloyl amino)- 1 -ethaneammonium inner salt, N,N-diethyl-N-(4-sulfobutyl)-2-(acryloyl amino)- 1 -ethaneammonium inner salt, and combinations of any two or more thereof.
• Suitable olefinic comonomers include, but are not limited to, acrylamide, styrene sulfonic acid, salt of styrene sulfonic acid, N-methylacrylamide, N,N-dimethylacrylamide, acrylic acid, salt of acrylic acid, N-vinylpyrrolidone, methyl acrylate, methacrylate, vinyl sulfonic acid, salt of vinyl sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, salt 2-acrylamido-2-methylpropanesulfonic acid, and combinations of any two or more thereof.
• the salt can be an ammonium salt, an alkali metal salt, or combinations of any two or more thereof.
• the molar ratio of mo ⁇ holine to the other reactant can be in the range of from about 2:1 to about 1 :2.
• the reaction can be carried out in an organic solvent such as chloroform or any solvents illustrated above, at a temperature in the range of from about -50 °C to about 20°C, for about 1 to about 10 hours.
• the reactants are commercially available. See Examples section below for details.
• the water-soluble polymers of the third embodiment of the present invention can be prepared by mixing the monomer(s) (i.e., the nitrogen-containing olefinic compounds and the olefinic comonomers), in desired molar ratios if copolymers, te ⁇ olymers, or tetrapolymers are desired, in an appropriate liquid medium and then initiating the free-radical polymerization in solution, suspension, or emulsion environment. Generally, any molar ratios can be employed depending on the final polymer desired.
• the liquid can be an aqueous solution, non-aqueous solution, or mixtures thereof.
• Well known compounds commonly employed to initiate free radical polymerization reactions include hydrogen peroxide, azo compounds such as, for example, 2,2'-azobis(2-(2-imidazolin-2-yl)propane) dihydrochloride, alkali metal persulfates such as K 2 S 2 O 8 , alkali metal perborates, alkali metal pe ⁇ hosphates, and alkali metal percarbonates.
• azo compounds such as, for example, 2,2'-azobis(2-(2-imidazolin-2-yl)propane) dihydrochloride
• alkali metal persulfates such as K 2 S 2 O 8
• alkali metal perborates alkali metal pe ⁇ hosphates
• alkali metal percarbonates alkali metal percarbonates.
• Well known organic peroxide compounds commonly employed to initiate free radical polymerization reactions include lauryl peroxide, 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane, t-butylperoxyprivilate, t-butylperoctoate, p-methane hydroperoxide, and benzoylperoxide.
• the compound t-butylhyponitrite is a well known alkyl hyponitrite commonly employed to initiate free radical polymerization reactions.
• ultraviolet light and gamma irradiation are commonly employed to initiate free radical polymerization reactions.
• the molar ratio of the nitrogen-containing olefinic monomer to the olefinic comonomer can be any ratio so long as the ratio can produce a polymer that can withstand hostile environment.
• the molar ratio can be in the range of from about 0.01 :1 to about 100:1, preferably about 0.05:1 to about 50: 1, and most preferably 0.1 : 1 to 30: 1.
• the molar ratios can be any ratio so long as the molar ratio of total nitrogen-containing olefinic monomers to the olefinic comonomers is within the range disclosed above.
• a process which can be used in hydrocarbon-bearing subterranean formations such as water-flooding comprises, or consisting essentially of, or consisting of, introducing a water-soluble composition into a subterranean formation.
• the water-soluble composition comprises, consists essentially of, or consists of a water-soluble polymer.
• the scope of the water-soluble polymer is the same as that disclosed in the first embodiment of the present invention, description of which is omitted herein for the interest of brevity.
• process used herein and hereinafter in conjunction with a subterranean formation generally denotes, unless otherwise indicated, a use in drilling fluids, workover fluids, completion fluids, permeability corrections, water or gas coning prevention, fluid loss prevention, matrix acidizing, fracture acidizing, and combinations of any two or more thereof.
• the water-soluble composition used in the fourth embodiment of the invention can also comprise a liquid.
• liquid used in the present invention denotes water, a solution, a suspension, or combinations thereof wherein the suspension contains dissolved, partially dissolved, or undissolved substances such as salts.
• the presently preferred liquid is an aqueous liquid such as, for example, fresh water, sea water, salt water, or a produced brine which is defined above.
• salts include metal salts.
• the total salts content can vary widely from, for instance, 1 to as high as 30 weight percent (%).
• the typical salts content can be in the range of from, for instance, about 2 to about 25 weight %.
• the introduction of the water-soluble composition into a subterranean formation can be carried out by any methods known to one skilled in the art.
• the water-soluble polymer can be dissolved, or substantially dissolved, in a liquid so that the water-soluble composition is present in the liquid in an amount, or concentration, sufficient to alter the permeability of a subterranean formation.
• the amount, or concentration can be in the range of from about 50 to about 100,000, preferably about 100 to about 50,000, and most preferably 200 to 10,000 mg of the water-soluble composition per liter of the liquid.
• the water-soluble composition in a liquid medium can then be introduced, by any means known to one skilled in the art such as pumping, into a subterranean formation so that it can diffuse into the more water-swept portions of the formation.
• the nature of the formation is not critical to carrying out the process of the present invention.
• the formation can have a temperature in the range of from about 70 °F to about 400 °F, preferably 75 °F to 350 °F.
• a gelling composition which can be used in oil field applications.
• the gelling composition comprises, consists essentially of, or consists of a water-soluble composition, a crosslinking agent, and a liquid.
• the scope of the water-soluble composition is the same as that disclosed in the third embodiment of the present invention.
• the liquid component is the same as that disclosed in the fourth embodiment of the present invention.
• any crosslinking agents can be used.
• a multivalent metallic compound that are capable of crosslinking the gellable carboxylate-containing polymer in the hydrocarbon-bearing formations can be used in the process of the present invention.
• suitable multivalent metal compounds include, but are not limited to, Al +3 , Cr + ⁇ Fe +3 , Zr + ⁇ Ti +4 , and combinations of any two or more thereof.
• the presently preferred multivalent metal compound is a metal compound selected from the group consisting of a complexed zirconium compound, a complexed titanium compound, a complexed chromium compound, and combinations of any two or more thereof.
• the preferred multivalent metallic compounds include, but are not limited to, zirconium citrate, zirconium complex of hydroxyethyl glycine, ammonium zirconium fluoride, zirconium 2-ethylhexanoate, zirconium acetate, zirconium neodecanoate, zirconium acetylacetonate, tetrakis(triethanolamine)zirconate, zirconium carbonate, ammonium zirconium carbonate, zirconyl ammonium carbonate, zirconium lactate, titanium acetylacetonate, titanium ethylacetoacetate, titanium citrate, titanium triethanolamine, ammonium titanium lactate, aluminum citrate, chromium
• the presently most preferred crosslinking agent is zirconium lactate, zirconium citrate, tetrakis(triethanolamine)zirconate, or zirconium complex of hydroxyethyl glycine, or combinations thereof. These compounds are commercially available.
• a metallic compound used as a crosslinking agent can also contain a complexing ligand if necessary to further delay the rate of gelation.
• the crosslinking agent does not contain such complexing agent.
• the complexing ligand useful for the present invention to retard the rate of gelation is generally a carboxylic acid containing one or more hydroxyl groups and salts thereof.
• the complexing ligand can also be an amine that has more than one functional group and contains one or more hydroxyl groups and that can chelate the zirconium or titanium moiety of the zirconium or titanium compounds described above.
• suitable complexing ligands include, but are not limited to, hydroxyethyl glycine, lactic acid, ammonium lactate, sodium lactate, potassium lactate, citric acid, ammonium, potassium or sodium citrate, isocitric acid, ammonium, potassium or sodium isocitrate, malic acid, ammonium, potassium or sodium malate, tartaric acid, ammonium, potassium or sodium tartrate, triethanolamine, malonic acid, ammonium, potassium or sodium malonate, and mixtures thereof.
• the presently preferred complexing ligands are citric acid, lactic acid, tartaric acid and salts thereof, triethanolamine, and hydroxyethyl glycine because of their ready availability and low cost.
• a crosslinking agent can also contain two components.
• water dispersible used herein is to describe a component that is truly water soluble or is dispersible in water to form a stable suspension.
• suitable first crosslinking components include, but are not limited to, phenol, hydroquinone, resorcinol, catechol, /. -aminosalicylic acid, /. -amino benzoic acid, fiirfuryl alcohol, phenyl acetate, phenyl propionate, phenyl butyrate, salicylic acid, phenyl salicylate, aspirin, /.-hydroxy benzoic acid, methyl .-hydroxy benzoate, methyl o-hydroxybenzoate, ethyl /?
• water dispersible first crosslinking components are phenol, phenyl acetate, phenyl salicylate, methyl /? -hydroxybenzoate, resorcinol, catechol, hydroquinone, and combinations of any two or more thereof.
• any water-dispersible or soluble aldehyde, its derivative, or compound that can be converted into aldehyde can be utilized as the second crosslinking component in crosslinking agent.
• suitable second crosslinking components include, but are not limited to aliphatic monoaldehydes, aromatic monoaldehydes, aliphatic dialdehydes, aromatic dialdehydes, and their precursors.
• Preferred aldehydes and their precursors can be selected from the group consisting of formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, decanal, glutaraldehyde, terephthaldehyde, hexamethylenetetramine, and combinations of any two or more thereof.
• the weight ratio of the water-dispersible first crosslinking component to the second crosslinking component can be any ratio so long as the ratio can effect the gelation of the gelling composition.
• such ratio can be in Ihe range of from about 0.01 : 1 to about 100:1, preferably about 0.1 :1 to about 10:1, and most preferably 0.5: 1 to 2: 1.
• any suitable procedures for preparing the gelling composition can be used.
• Some of the polymers can require particular mixing conditions, such as slow addition of finely powdered polymer into a vortex of stirred brine, alcohol prewetting, protection from air (oxygen), preparation of stock solutions from fresh rather than salt water, as is known for such polymers.
• the concentration or amount of the water-soluble polymer in the gelling composition can range widely and be as suitable and convenient for the various polymers, and for the degree of gelation needed for particular reservoirs.
• the concentration of the water-soluble polymer in a liquid is made up to a convenient strength of about 100 to 100,000 mg/1 (ppm), preferably about 200 to
• the concentration of crosslinking agent used in the present invention depends largely on the concentrations of polymer in the composition. Lower concentrations of polymer, e.g., require lower concentrations of the crosslinking agent. Further, it has been found that for a given concentration of polymer, increasing the concentration of crosslinking agent generally substantially increases the rate of gelation.
• the concentration of crosslinking agent in the injected slug varies generally over the broad range of about 1 mg/1 (ppm) to about 10,000 ppm, preferably over the range of about 1 ppm to about 7,500 ppm, and most preferably 1 ppm to 2,500 ppm.
• the liquid generally makes up the rest of the gelling composition.
• the concentration of the complexing ligand, if present, in the gelling composition also depends on the concentrations of the water-soluble polymer in the composition and on the desired rate of gelation. Generally, the lower the concentration of the complexing ligand is, the faster the gelation rate is.
• a process which can be used to alter the permeability of a subterranean formation is provided.
• the process comprises, or consists essentially of, or consists of introducing a gelling composition into a subterranean formation.
• the scope of the gelling composition is the same as that disclosed in the fifth embodiment of the invention.
• gelled polymers to alter the water permeability of underground formations is well known to those skilled in the art.
• an aqueous solution containing the polymer and a crosslinker is pumped into the formation so that the solution can enter into the more water swept portions of the formation and alter water permeability by gelling therein.
• an aqueous gelling composition comprising a crosslinking agent and a gellable polymer is injected into an injection or production well.
• the definition and scope of the crosslinking agent and gellable polymer are the same as those described above.
• the amount of the aqueous gelling composition introduced or injected can vary widely depending on the treatment volume injected.
• the amount of the gellable polymer injected is also dependent on the gel strength desired, same as that described for the crosslinking agent.
• the gelling can be prepared on the surface followed by introducing the prepared composition into a subterranean formation.
• individual components of the gelling composition described above can also be simultaneously or sequentially introduced into a subterranean formation.
• the nature of the underground formation treated is not critical to the practice of the present invention.
• the described gelling composition can be introduced or injected into a formation having a temperature range of from about 70°F to about 350°F. Any means known to one skilled in the art such as, for example, a pump means can be used for introducing or injecting the gelling composition and polymer solution.
• a composition which can be used as or in drilling fluids, completion fluids, or workover fluids is provided.
• the composition can comprise, consist essentially of, or consist of a clay, a water-soluble polymer, a liquid.
• the definition and scope of liquid and water-soluble polymer are the same as those disclosed above, the description of which are omitted herein for the interest of brevity.
• tlie clay useful in the invention can be any clay.
• suitable clays include, but are not limited to, kaolinite, halloysite, vermiculite, chlorite, attapulgite, smectite, montmorillonite, illite, saconite, sepiolite, palygorskite. Fuller's earth, and combinations of any two or more thereof.
• the presently preferred clay is montmorillonite clay.
• the presently most preferred clay is sodium montmorillonite, which is also known as bentonite.
• the clay can be present in the composition in the range of from about 0.25 weight % to about 30 weight %, preferably about 0.5 weight % to about 25 weight %, and most preferably 1 weight % to 20 weight %.
• the water-soluble polymer can be present in the composition in the range of from about 0.005 to about 15; preferably about 0.005 to about 10, more preferably about 0.01 to about 6, and most preferably 0.01 to 3 weight percent of the composition.
• liquid generally makes up the rest of the composition.
• a thinner can also be present in the present invention, if desired, in an amount in the range of from about 0.001 to about 10 weight %, preferably about 0.001 to about 5 weight %.
• suitable thinners include, but are not limited to, phosphates, tannins, modified tannins, lignites, modified lignites, lignosulfonates, polyacrylate polymers, or combinations of any two or more thereof.
• the composition can also comprise a weighting agent.
• a weighting agent Any known weighting agent that can be suspended in the composition can be used in the present invention.
• suitable weighting agents include, but are not limited to barite, hematite, calcium carbonate, galena, or combinations of any two or more thereof.
• the presently preferred weighting agent is barite for it is readily available and effective.
• the weighting agent if present, can be present in the composition in the range of from about 0.0001 to about 70.
• the composition of the seventh embodiment of the invention can also comprise a variety of other components or additives to obtain a desired property.
• Examples of the commonly used components or additives include, but are not limited to, viscosifiers, fluid loss control agents, salts, lubricants, surface active agents, flocculants, shale inhibitors, corrosion inhibitors, oxygen scavengers, or combinations of any two or more thereof.
• composition can be prepared by any means known to one skilled in the art such as blending, mixing, etc. Because these means are well known in the art, the description of which is omitted herein for the interest of brevity.
• N-acryloyl mo ⁇ holine fNAM N-acryloyl mo ⁇ holine fNAM
• N-acryloyl mo ⁇ holine was prepared from mo ⁇ holine and acryloyl chloride.
• Mo ⁇ holine (0.35 mole; 30.0 g), 0.42 mole (42.5 g) of triethylamine and 0.1 g of 1,3-dinitrobenzene were dissolved in 350 ml of chloroform and cooled to ca. -15 °C.
• Acryloyl chloride (0.42 mole; 37.8 g) was then added from a dropping funnel in such a way that the temperature in the reaction flask did not exceed 0°C. The reaction mixture was then allowed to reach room temperature (about 25 °C).
• N-acryloyl-N'-methyl piperazine was prepared by adding 0.44 mole (39.8 g) of acryloyl chloride to a solution of 0.40 mole (40.0 g) N-methyl piperazine and 0.1 g hydroquinone in 200 ml of acetonitrile. The addition was carried out in such a way that the temperature in the reaction flask did not exceed 5 °C. The reaction mixture was allowed to reach room temperature. A 10 M aqueous NaOH-solution (17.6 g NaOH in 44 ml distilled water, 0.44 mole) was then added and the precipitated material was filtered. The two phases were separated and the organic layer was dried with CaCl 2 . Distillation under reduced pressure gave the product as a clear liquid. B.p. 90-95 °C/0.5 mbar. The yield was 72%.
• N-acryloyl-N'-(3-sulfopropyl)-N'-methyl piperazinium inner salt was prepared from 0.26 mole (40.1 g) of N-acryloyl-N'-methyl piperazine and 0.29 mole (34.9 g) of 1,3-propanesultone.
• the reagents were mixed together with 0.1 g of 1 ,3-dinitrobenzene in 260 ml of acetonitrile. The reaction mixture was heated to
• N-acryloyl-N'-methyl piperazine (0.13 mole; 20.0 g) was dissolved in 260 ml of dry acetonitrile (distilled over P 2 0 5 ) together with 0.1 g 1,3-dinitrobenzene. Then 0.16 mole (14.6 g) 2-chloro acetamide was added to the N-acryloyl-N'-methyl piperazine, and the mixture was heated to ca. 80 °C for 123 hours. A white, precipitated powder was filtered and washed three times with diethyl ether (150 ml). The product was dried under reduced pressure (12 mm Hg) for 12 hours. The yield was 75%..
• N,N-dimethyl-N-(4-vinylbenzyl) amine (93.0 mmole; 15 g) , 1 1 1.6 mmole (13.6 g) of 1 ,3-propanesultone and 0.1 g of 1,3-dinitrobenzene were mixed together and dissolved in 180 ml of toluene. The mixture was heated at 45-50°C for 72 hours. A white, precipitated material was filtered, washed three times with diethyl ether (100 ml), and finally dried under reduced pressure (1 1 mm Hg) for
• N,N-dimethyl-N-(4-vinylbenzyl) amine (62.0 mmole; 10.0 g), 68.0 mmole (6.4 g) of 2-chloro acetamide and 0.1 g of 1,3-dinitrobenzene were dissolved in 125 ml of acetonitrile and heated at ca. 45°C for 48 hours. The precipitated material was filtered and washed three times with diethyl ether (100 ml). A white powder was dried under reduced pressure (12 mm Hg) for 16 hours. The yield was 88%. N-.2-amino-2-oxoethyl)-N'-vinyl imidazolium chloride . AOVC .
• EXAMPLE II This example illustrates the production of polymers of the present invention.
• Polymerizations were carried out in distilled water or synthetic sea water.
• one liter distilled water contained 23.83 g NaCl, 0.21 g NaHCO 3 , 10.77 g MgCl 2 -6H 2 O, 1.65 g CaCl 2 -2H 2 O, and 42.9 g anhydrous Na 2 SO 4 .
• the monomer solution was 35 weight % and the initiator concentration was 0.3 mole % with respect to total concentration of monomers.
• the azo-type initiator VA-044 (2,2'-azobis()dihydrochloride) was used to start the polymerizations.
• the polymerizations were carried out at room temperature.
• the polymer was prepared from 70 parts of acrylamide, 15 parts of N-acryloyl mo ⁇ holine (NAM) and 15 parts of N-acryloyl-N'-methyl piperazine
• a polymer was prepared from 80 parts of acrylamide and 20 parts of N,N-dimethyl-N-(3-sulfopropyl)-N-(4-vinylbenzyl) ammonium inner salt
• DMAMSPS DMAMSPS dissolved in synthetic sea water. 0.3 mole % VA-044 was used as initiator. After 4 hours the polymer was precipitated in methanol. The yield was 48%).
• N,N-dimefhyl-N-(3-sulfopropyl)-3-(acryloylamino)-l -propaneammonium inner salt were polymerized in synthetic sea water for 5 hours with use of 0.3 mole % VA-044 as initiator. The polymer was precipitated in methanol. The yield was 81%.
• acrylamide 20 parts of N-acryloyl-N'-methyl piperazine (AMP) and 20 parts of N,N-dimethyl-N-(3-sulfopropyl)-N-(4-vinylbenzyl) ammonium inner salt (DMAMSPS) were dissolved in synthetic sea water and the polymerization was carried out with use of 0.3 mole % VA-044 as initiator.
• AMP N-acryloyl-N'-methyl piperazine
• DMAMSPS N,N-dimethyl-N-(3-sulfopropyl)-N-(4-vinylbenzyl) ammonium inner salt
• N,N-dimethyl-N-(3-sulfopropyl)-3-(acryloylamino)- 1 -propaneammonium inner salt were polymerized in synthetic sea water with use of 0.3 mole % VA-044 as initiator. The polymerization was stopped after 3 hours by precipitation of the polymer in methanol. The yield was 59%. Te ⁇ olvmer Am / AMP / AMPPS
• AMPS 2-acrylamido-2-methylpropanesulfonic acid
• AOMPC N-acryloyl-N'-(2-amino-2-oxoethyl)-N'-methyl piperazinium chloride
• NaOH sodium sulfonic acid
• a polymer was prepared from 15 parts of
• AMP N-acryloyl-N'-methyl piperazine
• AMPS 2-acrylamido-2-methylpropane-sulfonic acid
• NaOH NaOH in synthetic sea water.
• AOMPC Homopolymer. N-acryloyl-N'-(2-amino-2-oxoethyl)-N'-methyl piperazinium chloride
• VA-044 was added. The polymerization was stopped after 6 hours by precipitation of the polymer in acetone. The yield was 57%.
• Te ⁇ olvmer Am / AMP / AMPS Seventy parts of acrylamide, 15 parts of N-acryloyl-N'-methy 1 piperazine (AMP) and 15 parts of 2-acrylamido-2-methyl-propanesulfonic acid
• This example illustrates the preparation of gelling compositions from the polymers disclosed above and the stability of gels formed from the gelling compositions.
• gelling compositions were made by adding polymer, phenol and formaldehyde/HMTA solution and diluting with synthetic sea water to the correct concentration. The same ppm concentration of both phenol and formaldehyde/HMTA was used. Magnetic stirring was used to mix the gelling compositions. After mixing the pH of the gelling compositions were registered using pH indicator strips. The pH of the was not adjusted in any way. The gelling compositions were thereafter transferred to glass vials, and the solutions were flushed with argon gas for 5 minutes before the vials were closed. The glass vials were weighed before and after adding gelling compositions.
• the glass vials were placed in stainless steel containers filled with water. After aging at 120°C, the stainless steel containers were cooled down to room temperature, the gel strength of the samples were characterized visually as weak, strong or rigid. The syneresis of the gels were measured as
• the syneresis was measured by measuring the gel height and the length of the liquid layer after ageing. Measurement of Inherent Viscosity Polymer solution (0.1 weight %) in synthetic sea water was made for viscosity measurements. The polymer solution was allowed to stand for 3 days with magnetic stirring. Before viscosity measurement the polymer solution was filtered through a 5 ⁇ m Millipore filter. The relative viscosity of the 0.1 weight % polymer solution (relative to synthetic sea water) was measured with an Ubbelhcde viscosimeter with an inner capillary diameter of 0.69 mm. At least 3 parallel measurements were performed for each solution. The temperature of the polymer solution under the viscosity measurement was
• Relative viscosity time for polymer solution through capillary/ time for synthetic sea water trough capillary
• 'HMTA hexamethylenetetramine f Weight % gel of initial weight of the solution after aging at 120°C in synthetic sea water
• This example is a comparative example showing that gels formed from a commonly employed polyacrylamide do not withstand well under a hostile environment condition as compared to the gels formed from the invention polymers.
• EXAMPLE V This example illustrates a fresh water based composition of the invention that can be used as drilling fluids, completion fluids, or workover fluids.
• Seven fresh water based compositions were prepared by mixing the components shown in Table XXIII on a Multi-mixer in quart jars. The mixing time, in minutes, after the addition of each component is shown in the table. After the mixing was completed, the fluid compositions were transferred into pint jars and then tested initially for viscosity and gel strength according to the API RP 13B-1, First Edition, June 1, 1990 procedure. The compositions were then mixed for five minutes and tested for filtration according to the low-temperature/low-pressure test procedure. These test results are presented in Table XXIV under "Initial Results”.
• compositions were then kept in capped jars at 75 °C for about 16 hours, cooled to about 30 °C, and tested after the compositions were mixed for 5 minutes. These test results are represented in Table XXIV under "Results After Aging at 75 °C”. Table XXII
• NAM/AM is a copolymer of 25% (mole %) acryloyl morpholine and 75% acrylamide
• NAM/AP is a copolymer of 25% acryloyl mo ⁇ holine and 75% acrylamide-2-methylpropanesulfonate
• NAM/AA is a copolymer of 25% acryloyl mo ⁇ holine and 75% acrylate; these polymers were prepared according to the process disclosed in Example II.
• PV-plastic viscosity cps.
• Table XXIV show that the four inventive fluid compositions (runs 8-3, 8-4, 8-6, and 8-7) had much lower fluid loss than the fluid composition of run 8-1 that represents a base fluid which did not contain any polymer. Further, these four inventive compositions had higher viscosity than the base fluid. High viscosity is desirable. Even though two inventive compositions (run 8-2 and 8-5) had high fluid loss, their high viscosity is useful in bringing the drill cuttings to the surface.
• EXAMPLE VI This example illustrates a sea water based composition of the invention that can be used as drilling fluids, completion fluids, or workover fluids.
• Four sea water based compositions were prepared by mixing the components shown in Table XXV on a Multi-mixer in quart jars. The mixing time, in minutes, after the addition of each component is shown in the table. After the mixing was completed, the fluid compositions were kept at about 75 °C for about two hours.
• compositions were mixed 5 minutes and after adding 0.05 ml of octyl alcohol as a defoamer to each composition, each sample was tested initially for viscosity, gel strength, and filtration at low-temperature/low-pressure according to the API RP 13B-1, First Edition, June 1, 1190 procedure. These test results are presented in Table XXVI under "Initial Results”.
• the compositions were then kept in capped jars at 75 °C for about 16 hours and cooled to about 30°C. Next, the compositions were mixed 5 minutes and, after adding 0.05 ml of octyl alcohol as a defoamer to each composition, they were retested. These results are represented in Table XXVI under "Results After Aging at 75 °C".
• the composition of sea water is shown in Example II.
• PV-plastic viscosity cps.
• Table XXVI show that three inventive fluid compositions (runs 9-2, 9-3, and 9-4) had much lower fluid loss than the fluid composition of run 9-1 that represents a base fluid which did not contain any polymer. Furthermore, these three inventive compositions also had higher viscosity than the base fluid. High viscosity is useful in bringing the drill cuttings to the surface.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Materials Engineering (AREA)
• Engineering & Computer Science (AREA)
• General Life Sciences & Earth Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Health & Medical Sciences (AREA)
• Dispersion Chemistry (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• General Chemical & Material Sciences (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Soil Conditioners And Soil-Stabilizing Materials (AREA)
• Medicinal Preparation (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Priority Applications (6)

Applications Claiming Priority (8)

Publications (1)

Family

ID=27504912

Family Applications (1)

Country Status (6)

Cited By (7)

Families Citing this family (1)

Citations (3)

Family Cites Families (11)

• 1996
  • 1996-11-13 WO PCT/US1996/018174 patent/WO1997022638A1/en active Application Filing
  • 1996-11-13 AU AU77297/96A patent/AU719976B2/en not_active Expired
  • 1996-11-13 GB GB9930053A patent/GB2340496B/en not_active Expired - Lifetime
  • 1996-11-13 GB GB9926318A patent/GB2340832B/en not_active Expired - Lifetime
  • 1996-11-13 CA CA002241362A patent/CA2241362C/en not_active Expired - Lifetime
  • 1996-11-13 GB GB9813343A patent/GB2324095B/en not_active Expired - Lifetime
• 1998
  • 1998-06-19 NO NO19982888A patent/NO322844B1/no not_active IP Right Cessation
  • 1998-06-19 MX MX9804985A patent/MX9804985A/es active IP Right Grant
• 2005
  • 2005-10-07 NO NO20054619A patent/NO20054619D0/no not_active Application Discontinuation

Patent Citations (3)

Non-Patent Citations (4)

Also Published As

Similar Documents

Legal Events