GB2340832A - Compositions and processes for treating subterranean formations - Google Patents

Compositions and processes for treating subterranean formations Download PDF

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Publication number
GB2340832A
GB2340832A GB9926318A GB9926318A GB2340832A GB 2340832 A GB2340832 A GB 2340832A GB 9926318 A GB9926318 A GB 9926318A GB 9926318 A GB9926318 A GB 9926318A GB 2340832 A GB2340832 A GB 2340832A
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amino
chloride
inner salt
ammonium
vinylbenzyl
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GB9926318D0 (en
GB2340832B (en
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Iqbal Ahmed
Ahmad Moradi-Araghi
Aly-Anis Hamouda
Odd Ivar Eriksen
Bharatkuma Balubhail Patel
Wayne Stephen Stewart
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Phillips Petroleum Co
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Phillips Petroleum Co
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Priority claimed from US08/575,928 external-priority patent/US5650633A/en
Priority claimed from US08/575,429 external-priority patent/US5708107A/en
Priority claimed from US08/575,434 external-priority patent/US6051670A/en
Priority claimed from US08/723,635 external-priority patent/US5922653A/en
Application filed by Phillips Petroleum Co filed Critical Phillips Petroleum Co
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Publication of GB2340832A publication Critical patent/GB2340832A/en
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    • 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
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    • 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
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    • 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
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • 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
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    • 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
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • 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

Abstract

Compositions compounds and processes for using the compositions for applications in a subterranean formation are provided, include a composition which comprises a nitrogen-containing olefinic compound having the formula <EMI ID=1.1 HE=11 WI=73 LX=366 LY=1165 TI=CF> <PC>```wherein R<SB>1</SB> and R<SB>2</SB> are each independently selected from hydrogen, alkyl radical, aryl radical, aralkyl radical, alkaryl radical, and combinations of any two or more thereof wherein each radical contains 1 to about 30 carbon atoms;<BR> ```each Y is independently selected from the group consisting of alkylene radical, phenyl group, imidazolium group, naphthyl group, biphenyl group, and combinations of any two or more thereof;<BR> ```X is an anion selected from the group consisting of halide, sulfate, phosphate, nitrate, sulfonate, phosphonates, sulfinate, phosphinate, and combinations of any two or more thereof; and<BR> ```each m is independently 0 or 1. Specific compounds are N-acryloyl-N'-(3-sulfopropyl)-N'-methyl piperazinium inner salt, N-acryloyl-N'-(3-sulfopropyl)-N'-ethyl piperazinium inner salt.

Description

1 2340832 COMPOSITIONS AND PROCESSES FOR TREATING SUBTERRANEAN FORMATIONS
FIELD OF THE INVENTION
The present invention relates to compositions which can be used to prepaic 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.
BACKC ROUND OF THE INVENTION It is well known to those skilled in the art that polymers and gelled or crosslinked water-soluble polymers are useful in enhanced oil recovery and other oil field operations. They have been used to alter the permeability of underground
1 formations in order to enhance the effectiveness of water flooding operations, Generally, 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.
Polymers have also been used in subterranean formation treatments such as "matrix acidizing" and "fracture acidizing". Because such treatments are well known to one skilled in the art, description of which is omitted herein and can be found in U.S. Pat. No. 4,997,582, description of which is herein incorporated by reference.
Because of environmental concerns as well as cost for disposing of a 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, it is desirable to utilize the produced brine as the liquid used for the polymers and appropriate crosslinking systems. 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.
Many 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, 12CC in a harsh environment such as sea water.
Various polymers of desired properties such as those disclosed above may be used in the process for recovery of hydrocarbons. For example,multivalent metallic ions crosslink gellable polymers duough the interaction with the oxygen atoms of the polymer molecules. Therefore, the gellable polymers generally contain some carboxylate groups. Generally, 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 10-3) 0 mole % carboxylate groups. However, 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. Such fast gelat;on rate renders the application of gelling compositions containing these polymers and multivalent metallic compounds not useful in many oil-field applications such as, for example, water shut-offs and permeability reductions.
Many processes have been developed to delay,.he gelation of gelling compositions by adding a gelation delaying agent to the gelling compositions.
However, a gelation delaying agent is not inexpensive and a gelation delaying agent often adds appreciable costs to oil field operation. Furthermore, many gellable polymers cannot withstand a hostile environment as descnbcd abovc.
There is therefore an increasing dcmand for water-soluble polymers that can be used to prepare gels which withstand hostile environments. A hostile environment includes, but is not limited to, high temperatures, high salinity andlor 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.
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 thai such drilling fluids exhibit a low rate of filtration or water loss, that is, the drilling fluid must prevent excessive amounts of fluid, or "filtrate", flowing from the bore hole into the surrounding formation. The loss of water or other fluid from the drilling hole is prevented by the formation of a filter cake which deposits from the drilling fluid and seals the wall of the bore hole. Numerous formulations, compositions and additives to optimize the performance of drilling fluids for various applications have been developed. For instance, 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.
Excessive fluid loss from the drilling fluid may contaminate the producing formation, permanently displacing oil and blocking production. The adverse consequences of excessive fluid loss in the drilling of very deep wells are more severe due to the high temperatures and pressures encountered in such drilling operations. The viscosity of a fluid normally decreases with an increase in temperature, but certain polymer additive or deflocculating agents may -educe, or even reverse, this tendency. However, the polymers which are most effective in achieving this effect are the most vulnerable to breakdown through oxidation, shear and thermal effects, i.e.., the duration of exposure to high temperature drilling operations. Also, many such polymers tend to precipitate andlor lose viscosity as well as effectiveness as water loss additives when exposed to dissolved elect-olytes, particularly when divalent metal cations such as Ca' and Mg-2 are present. In drilling fluids, the resulting vulnerability to breakdown is exacerbated by the density of drilling mud, which is directly related to weiginting agents required for a given formation pressure.
Breakdown of polymers causes a large increase in the fiLid 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, in contrast, arc those fluids used in the completion I 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.
This can include removing tubing, replacing a pump, cleaning out sand or other deposits, logging, reperforating, etc. 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 overpressure, 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.
Although there has been considerable progress in the field of Workovcr and completion fluids, there is significant room for further improvement. For example, wells are being completed and serviced in increasingly hostile environments involving, e.g., high temperatures and high levels of salinity and/or hardness in the formation water. Thus, new additives for Workover and completion fluids which retain their properties at elevated temperatures and high concentrations of dissolved electrolytes are in demand.
Therefore, a composition which can be used to prepare a more hostile environment-withstanding polymer as well as a hostile environmentwithstanding gelling composition, containing the hostile environmentwithstandingpOlYMCT, &at 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.
SUMMARY Q1F IHE INVENTION
An object of the invention is to provide a composition which can be used as a monomer to synthesize a hostile environment-withstanding, watersoluble 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-solublepOlyMeTand withstands a hostile environment. Still another object of the present invention is to provide a process for various drilling applications or for altering the permeability of hydrocarbon-bearing subterranean formations by using a gelling composition that contains the water-soluble polymer, withstands hostile environment, and is envirorunentally suitable for use in subterranean formations. Still a further object of the invention is to provide a process for various drilling applications or for al.ering the permeability of hydrocarbonbearing subterranean formations with a gelling composition that does not require a gelation delaying agcnt.
Yet still another object of the invention is to provide a process for treatment of subterranean formations employing a gelling composition that is envirenmentally suitable for subterranean formation operations. 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 appasent as the invention is more fully disclosed hereinbelow.
According to a first embodiment of the present invention. a composition that can be used to prepare a water-soluble polymer which can be used in a hydrocarbon-bearing subterranean formation is provided. The composition comprises a nitrogen-containing olefinic compound.
According to a second embodiment of the present invention, 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.
According to a third embodiment of the present invention, a water-soluble polymer which can be used in a hydrocarbon-bearing formation is provided. The polymer comprises repeat units derived from at least one rutrogen-containing olefinic compound.
According to a fourth embodiment of the present invention, a process which can be used for treating hydrocarbon-bearing formation is provided comprises introducing into the formation a water-soluble composition wherein the water-soluble composition comprises a water-soluble polymer comprising repeat units denved from at least one nitrogen-containing olefinic compound.
According to a fifth embodiment of the present invention, a gelling composition is provided which comprises a water-soluble polymer, a crosslinking agent, and a liquid wherein the water-soluble polymer comprises repeat units deriveJ from at least one nitrogen-containing olefinic compound.
According to a sixth embodiment of the present invention, a process is providcd 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.
According to a seventh embodiment of the present invention 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 ---WO 97122638 PCT.T596118174 8 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.
DFJAILED DESCRITTI N According to the first embodiment of the present invention, a composition useful as a monomer for synthesdng a water-soluble polymer is provided. The composition 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 suifobetaine has the formula of R,C(R,)=C(R,)-(C=O),,,-(Ar),,-Y-N-(R2)(R,.)-Y-SO,- and the vinylic am:"de has the formula of RI-C(Rj)=C(R1)-(C=O),,,-(NH),,,-(Ar),,-Y-N'(R,)(R2)-Y-(C=O),,,N(R2)(R2)X', RIC(Rj)=C(R,,)(C0),,,-N N'(R2)-Y-(C=O),,,-N(R2)(R2)X-, R,C(Rj)=C(R)-(C=0),,-N N'-Y-(C=O),,,-N(R2)(R,)X-, or combinations of any two or more thereof. R, and R2 can be the same or different and are each independently selected from the group cunsisting 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 groups, sulfhydryl groups, or combinations of any two or more thereof which can contribute to water solubility of polymers produced therefrom. Preferably R, is hydrogen and R, 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 blphenyl 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, Most preferably, Y is a short alkylene radical having -1, WO 97122638 PCT/US96118174 9 I 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, phospbates, 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 I - Examples of 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) anunonium 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-(-')-sulfobutyl)-N-(3-vinylbenzyl) ammonium inner salt, N,N -diethy I -N-(3 -sul fopropyl)-N-(')-vinyl benzy 1) ammonium inner salt, N,N-diethyl-N-(3-sulfobutyl)-N-(3-vinylbenzy]) ammonium inner salt, N-acryloyl-N'-methyl-N'-(2-amino-2-oxoethyl) piperazinium chloride, N-acryloyl-N'-methyl-N'-(-'i-amino-3-oxopropyl) pipera.7inium chloride, N--acryloyi-N'-methyl-N'-(4-amino-4-oxobutyl) p1perazinium chloride, iN-acryloyl-',N"-ethyl-N'-(2-aniino-2-oxoethyl) piperazinium chloride, N-acr-,vloyi-N'-ethyl-N'-(3-amino-3-oxopropyl) piperaziniurn 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-(-')-amino-3-OXOPTOPYI)-N-(4-vinylbenzyi) ammonium chlonde, N-(2-amino-2-oxoethyl)-N'-vinylimidazolium chloride, N-(3-amino-3-oxopropyl)-N'-vinylimidazolium chloride, N-(4-aniino-4-oxobutyl)-N'-vinylimidazolium chloride, and combinations of any two or more thereof The nitrogen-containing olefinic compounds of the first embodiment of the invention can be prepared by the process disclosed hereinbclow in the second embodiment of the invention.
In the second embodiment of the present invention, a process for preparing the nitro gen-containing olefinic compounds is provided. The nitrogen-containing olefinic compounds having the formula of R,C(R,)=C(Ri)-(C=O),,,-(NH),,,-(Ar),.-Y-N(R2)(R,)-Y-SO3- (a sulfobetaine), can be produced by contacting a vinylic tertiary arnine with an alkylating agent such as, for example, an alkylsulfonic acid containing a proper leaving group such as halide, hydroxyl, tosylatc, other suitable leaving groups, or combinations of any two or moro thereof. These reagents can be contacted, under any suitable conditions so long as the conditions can effect the production of the nitrogen-containing olefinic compounds, in 4 a solvent such as toluene, benzene, pentane, hexane, acetonitrile, methanol, ethanol.
any other common organic solvent or combinations of any two or more solvents.
Generally, a tertiary amine can be contacted with an alkylating agent at a tempera=e in the range of from about 10 to about 120'C, preferably about 20 to about 90"C, and most preferably 35 to 65 "C for about I to about 10 days, preferably about I to about 8 days, and most preferably I to 5 days under any suitable pressures such as, for example, about I 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. Preferably the production is cal-ried out by using 1,3-propanesultone or 1.4-butanesultone as the alkylating reagent in toluene b heating at 45-50C for 72 hours. The sulfobetaine generaliy precipitates from the solvent and can be purified by filtration, repeated washing with any conunon organiC solvent that does not dissolve the sulfobetaine, and finally dried under reduced pressure. Preferably 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.
Examples of suitable tertiary amines include, but are not limited to, N,N-dimethyl-N-(4-vinylbenzyi) amine, N,Ndimethyl-N-(4-vinylbenzyl) amine, N.N-diethyl-N-(4-vinylbenzyl) arnine, N,N-diethyPN-(4-vinylbenzyI) amine, N,N-dirnethyl-N-(3-vinylbcnzyl) amine, N,N-dimethyl-N-(3-Yinylbenzyl) amine, N,N-diethyl-N-(3-Yinylbenzyl) arnine and N,N-diethyl-N-(3 -vinyl benzyl) amine, ard combinations of any two or more thereof.
Examples of suitable alkylating reagents include, but are not limited to, 3-chloro-propane-l-sulfonic acid, 4-chloro-butane-l-sulfonic acid, 3-hydroxy-propane- 1 -sulfonic acid, 4-hydroxy-butane- 1 -sulfonic acid, the corresponding esters of the hydroxy-alkane- 1 -sulfonic acids such as 1,3-propanesultone and 1,4-butanesultone, and combinations of any two or more thereof.
The nitrogen-containing olefinic compounds with the amide functional group of the first embodiment of the invention have general formulae of RIC(Rj)=C(Rj)-(C=O),,,-(NH),,-(Ar),,-Y-N'(R2)(R2)-Y-(C=O),,-N(R2)(R2)X-, R,C(R,)=C(R,)-(C=O),,-N N(R,,)-Y-(C=O),,,-N(R2)(R2)X", R,C(R,)=C(R)-(C=O),-N N±Y-(C=O),.-N(R2)(R,)X-, and combinations of any two or more thereof. These compounds can be produced by alkylation of a vinyl-substituted arnine with an 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. These 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, ben7Cne, pentane, hexane, acetonitrile, methanol, ethanol. any other common organic solvents.
or combinations of any two or more thereof. Generally, a vinyl substituted arnine 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 3 30 to 1 OCC 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.
Preferably the production is carried out by using 2-chloro-acetamide as the alkylatine agent in acetonitrile by heating at 45-80C for 50-150 hours. The nitrogen- containing olefinic compounds generally precipitate frori 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 pressurc.
Preferably 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.
Examples of suitable vinyl -substituted amines include, but are not limited to, N.N-dimethyl-N-(4-vinylbenzyl) amine, N,N-dimethyl-N-(4vinylbenzyi) arnine, N,N-diethyl-N-(4-vinylbenzyI) amine, N,N-diethyl-N-(4- vinylbenzyl) arnine, N,N-dirnethy]-N-(3-vinylbenzyl) amine, NN-dimethyl-N-(3-vinylbenzvl) amine, N,N-diethy',-N-(3-vinylbenzyi) amine and N,N-diethyl-N-(3-vinvlbenzy[) amine, and combinations of any two or more thereof.
Examples of suitable alkylating agents include, but are not limited to.
2-chloro-acetarnide, 2-bromo-acetarnide, 3-chloro-propaneamide and 3-bromo-propancamide, and combinations of any two or more thereof.
In the second embodiment of the invention, the molar ratio of the alkylating agent to the amine can be any ratio so long the ratio can effecc the production of the nitrogen-containing olefinic compounds. Generally, the molar ratio can be in the range of from about 1:0.01 to about 0.0LI, 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 arnine can be in the range of ftom 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.
According to the third embodiment of the present invention, a water-soluble polymer is provided 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, repcai ' units derived ftom at least one nitrogen-containing olefinic compound. The term "polymer" as used herein denotes a molecule having at least about 10 repeat units and can be homopolymer, copolymer, terpolymer, tetrapolymer, or combination of any two or more thereof Any nitrogen-containing olefinic compounds having a polyrnerizable 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. Though it is not necessary, it is preferred that the ethylerlic linkage be at the terminal end of the nitrogen-coniaining olerin molecule and that at least one nitrogen be a tertiary amine. The presently preferred repeat units include, but are not limited to R,-C(Rj)=C(R1)-(C=O),,,-M, R,-C(Rj)=C(R,)-(C=O),,,-N N(R), R,-C(Rj)=C(R,)-(C=O),,-N N-(R,)-Y-X-, RC(R,)--C(R1)-(C=O),,,-(NH),-(Ar),,,-N(R2)(R2)-Y-S03", RI-C(Rj)=C(R1)-(C=O),,-(NH),,-(Ar),,-Y-N(R,)(R.)-Y-(C=O),-N(R,)(R,)X-, R, C(Rj)=C(RJ-(C=0),,-N N-(R)-Y-(C=O),,,-N(R,)(R2)X, R, C(Rj)=C(R I)-(C=O),,-N N'-'-(C=O),,,-N(R2)(R,)X-, and combinations of any two or more thereof. R, and R2 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. Preferably R, is hydrogen, R, is hydrogen, methyl, ethyl, or combinations of any two or more thereof. M i s a morpholine group which can be substituted or unsubstituted. Y is an alkylene radical, a phenyl group, an imidazoliurn group, a naphthyl group, a bipherlyl group, or combinations of any two or more thereof which can have I to about 20, preferably I to about 15, and most preferably I to 10 carbon atoms. Most preferably, Y is a short alkylene radical having I to about 5 carbon atoms. Ar is an arylene radical, preferably phenyl, which can be substituted or unsubstituted. X is an anion selected from the group cons 'Asting 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 I - The water-soluble polymer of the third embodiment of the present invention can be a homopolymer, copolymer, terpolymer or tetrapolymer. However, if the nitrogen-containing olefinic repeat units contain an amide group, it is preferred that the water-soluble polymer be derived from repeat units comprising at least one o F the nitrogen-containing olefinic compounds described above and at least one olefinic comonomer selected from the group consisting of RI-C(Rl)=C(R,)-W, R,-C(Rj)=C(Rj)-(C=O),-Z, R, -C(Rj)=C(Rj)-Y-W, R,-C(R,)=C(R,)-(C=O),,,-N(R,)-Y-R2, R,-C(Rj)=C(Rj)-(C=O),.-G-Y-Z, RjC(Rj)=C(Rj)-(C=O),,,-G-Y-W, R,-C(R,)=C(R,)-(C=O),-Y-Z, and combinations of any two or more thereof wherein Z has a formula selected from the group consisting of N(R2)(R2), N'(R,)(R2)(R2)X-, and combinations of any two or more thereof wherein X is an anion selected from the group consisting of halides, sulfate, phosphate, nitratc, sulfonates, phosphonates, sulfinates, phosphinates, and combinations of a:ny two or more thereof. M, Y, R,, and R, are the same as those disclosed above. The letter m is 0 or 1. G is N(Rj) or 0. W is an acid moiety selected from the group ccrisisting of phosphinic acid,phosphonic acid, sulfinic acid, sulfonic acid, sulfuric acid. sulfurous acid, carboxylic acid, phosphoric acid, anunanium salts or alkali metal salts of these acids, and combinations of any two or more thereof.
Examples of suitable nitrogen-containing olefinic compounds of the third embodiment of the invenfion include, but are not limited to, N-acryloyl morpholine, N-acry loyPN'-m ethyl piperazine, N-acryloyl-N'-ethy[ piperazine, N-acryloyl-W-propyl piperazine, N-acryloyl-N'-(3-sulfopropyl)-N'-methyI piperazinium inner salt, N-acryloyl-N'-(3-sulfopropyl)-N'-ethyl piperazinium inner salt, N-acryloyl-N'-(4-sulfopropyl)-N'-rnethyl piperazinium inner salt, N-acryloyl-N'-(4-sulfopropyl)-N'-ethyl piperazinium inner salt,,,acryloyl-N'-(2-a.mino-2-oxoethyl)-N'-methyl piperazinium chloride, Nacryloyl-N'-(3-amino-3-oxopropyl)-N'-methyl piperazinium chloride, Nacryloyl-N'-(4-amino-4-oxobutyl)-N'-methyl piperazinium chloride, Nacryloyi-N'-(2-amino2-oxoethyl)-N'-ethyI piperazinium chloride, 15 Nacryloyl-N'-(3-arnino-3-oxopropyl)-N'-ethyl piperaziniurn chloride, Nacryloyl-N'-(4-amino-4-oxobutyl)-N'-cthyl piperazinium chloride, N,Ndimethyl-N-(")-sulfopropyl)-N-(4-vinylbenzyl) ammonium inner salt. N.Ndimethyl-N-(4-suifobutyl)-N-(4-vinylbenzyl) ammonium inner salt, N,Ndiethyl-N-(3-sulfopropyl)-N-(4-vinylbenzyl) ammonium inner salt, 20 N,Ndiethyl-N-(4-sulfobutyl)-N-(4-vinylbenzyl) ammonium inner salt, N,Ndimethyl-N-(3sulfopropyl)-N-(3-vinylbenzyl) ammonium inner salt, N,Ndimethyl-N-(4-suifobutyl)-N-(3-vinylbenzyl) ammonium inner salt, N,Ndiethyl-N-(3-suifopropyl)-N-(3-vinylhenzyl) ammonium inner salt, N,Ndiethyl-N-(4-suifobutyl)-N-(3-vinylbenzyl) ammonium irincr salt, 25 N,Ndimetbyl-N-(2-amino-2-oxoethyl)-N-(4-Yinylbenzyl) ammonium chloride, N,Ndiethyl-N-(2-arnino-2-oxoethyi)-N-(4-vinylbenzyl) ammonium chloride, N.Ndimethyl-N-(3-amino-3-oxopropyl)-N-(4-vinylbenzyl) ammonium chloride, N,N- diethyl-N-(3-arnino-3-oxopropyl)-N-(4-vinylbenzyl) ammonium chloride, 2 WO 97122638 PCT/US96/18174 16 N,N-dimethyl-N-(2-amino-2-oxcethyl)-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-vinylbenzyl) ammonium chloride..
N,N-diethyl-N-(3-amino-3-oxopropyl)-N-(-')-vinylbenzyl) ammonium ciloride, N-(2-arnino-2-oxoethyl)-N'-vinyt imidazolium chloride, N-(3-amino-3-oxopropyl)-N'-vinyI imidazoliurn chloride, N-(4-amino-4-oxobutyl)-N'-vinyI imidazolium chloride, N,N-dimethyl-N-(3-sulfopropyl)-3-(acryloyI amino)- I -propanearnmonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-3-(acryloyI amino)- I -propaneammonium inner salt, N,N-dimethyl-N-(4-sulfobutyl)-3-(acryloyI arnino)- I -propaneammonium inner salt. N,N-diethyl-N-(4-sulfobutyl)-3-(acryloyI amino)- I - propaneammonium inner salt, N,N-dimethyl-N-(3-sulfopropyl)-2-(acryloyI amino)-l -ethaneammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-2- (acryloyI ainirio)-l-ethaneanu-nonium inner salt, N,N-dimethyl-N-(4sulfobutyl)-2-(acryloyI amino)- I -ethaneammonium inner salt, N,N-diethyl-N-(4-sulfobutyl)-2-(acTyloyI amino)- I -ethaneammoniurn inner salt, and combinations of any two or more thereof Examples of 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.
Some of the olefinic comonomers can be purchased commercially.
The others can be synthesized by the process disclosed in the second embodiment of' the present invention or in the Examples section.
For example, the olefinic comonomers having the formula of R,-C(R,)=C(R,)(C=O),,,-M in which M is the same as disclosed above can be prepared from R,-C(Rj)=C(R,)-(C=O),,,-X where X is the same as that disclosed above, such as acryloyl chloride, and morpholine or from R,-C(R,)--C(R,)-(C=O),,,-OH, such as acrylic acid, and morpholine. The molar ratio of morpholine to the other reactant can be in the range of from about 2:1 to about 1:1 Generally, 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 2CC, for about 1 to about 10 hours. The reactants are conunercially available. 10 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 nitrogencontaining olefinic compounds and the olefinic comonomers), in desired molar ratios if copolymers, terpolymers, 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 conunonly employed to initiate free radical, polymerization reactions include hydrogen peroxide, azo compounds such as, for example, 2,2'-azobis(2-(2-lmidazolin-2-yl)propane) dihydrochloride, alkali metal persulfates such as K2S,Q, alkali metal perborates, alkali metal perphosphates, and alkali metal perewbonates. Well known organic peroxide compounds commonly employed to initiate free radical polymerization reactions include lauryl peroxide, 2,5-dirnethyl-2,5-bis(2-ethylhexanoylperoxy)hexane, t-butylperoxyprivil ate, 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. Furthermore, ultraviolet light and garruna N I WO 97122638 PCT/US96/18174 irradiation are commonly employed to initiate free radical polymerization reactions. In addition, such other method of polymerization as would have occurred to one skilled in the art may be employed, and the present invention is not limited to the particular method of preparing the polymer set out herein. Because the polymerization techniques are well known to one skilled in the art, the description of which is omitted herein for the interest of brevity.
If copolymers, terpolymers, or tetrapolymers are desired, the molar ratio of the nitrogen-containing olefinic monomer to the olefinic comonorner can be any ratio so long as the ratio can produce a polymer that can withstand hostile environment. Generally, the molar ratio can be in the range of from about 0.01: 1 to about 100:11, prefer-ably about 0.05:1 to about 50: 1, and most preferably 0. 1: 1 to 30: 1. If a combination of the nitrogencontaining olefinic monomers, or the olefinic comonomers, or both are employed, 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.
According to the fourth embodiment of the present invertion, a process which can be used in hydrocarbon-bearing subterranean formations such as water-flooding is provided. The process comprises, or consisting essenially 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 cf which is omitted herein for the interest of brevity.
The term "process" used herein and hereinafter in conjuncion 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 acid!,zing, 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. The term "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.
Examples of salts include metal salts. Generally, the total salts content can vary widely from, for instance, I 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. Generally 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 5 0 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 707 to about 4007, preferably 75"F to 3507.
According to the fifth embodiment of the present invention, a gelling composition which can be used in oil field applications is provided. 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. For example, 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. Examples of suitable multivalent tnetal compounds include, but are not limited to, Al', Cr', Fe', Zr', Tt', 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 combinatiolls of any two or more thereof. Examples of the preferred multivalent met,-dlic compounds include, but are not limited to, zirconium citrate, zirconium complex of hydroxyethyl glycine. ammonium zirconium fluoride, zirconium 2-ethylhexanoate.
zirconium acetate, zirconium ricodecanoate, zirconium acetylacetonate, tetrakis(triethanolamine)zirconate, zirconium carbonate, a=onium zirconium carbonate, zircoriyl ammonium carbonate, zirconium lactate, titanium acetylacetonatc, titanium ethylacetoacetate, titanium citrate, titanium triethanolamine, arnmoni= titanium lactate, aluminum citrate, chromium citrate, chromium acetate, chromium propionate. chromium malonate, and combinations thereof The presently most preferred crosslinking agent is zirconium lactate, zirconium citratc, t-,trakis(triethanolamine)zirconate, or zirconium complex of hydroxye&. yl glycine, or combinations thereof. These compounds are commercially available.
According to the fiflh embodiment of the present invention, a metalli,-compound used as a crosslinking agent can also contain a complexing ligand if necessary to fi=ther delay the rate of gelation. Preferably, however, the crosslinking agent does not contain such complexing agent. The complexing ligand us-eful 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. Examples of 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 sodiwn 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, triethanolarnine, and hycl-oxyethyl glycine because of their ready availability and low cost.
A crosslinking agent can also contain two components. The first crosslinking component useful as crosslinking agent is generally waterdispersible or soluble and car, be phenol, substituted phenols, aspirin, p-arninobenzoic acid, resorcinol, catechol, hydroquinone, fin-fury] alcohol, R'ArO (C=O)., , R', HOAr (C=O) OR', HOArOll, WO.ArOH, R'OArM, or combinations of any two or more thereof where Ar is an arylene group which can be non- substituted or substiruted; each R' can be the same or different and is each independently selected from the group consisting of hydrogen, carboxylic group, a Cl-C, alkyl, a phenyl group or combinations of any two or more thereof, and m is 0 or 1. The term "water dispersible" used herein is to describe a component that is truly water soluble or is dispersible in water to form a stable suspension. Exaniples of suitable first crosslinking components include, but are not limited to, phenol, hydroquinone, re-sorcinol, catcehol, p-aminosalicylic acid, p-amino benzoic acid, furfuryl alcohol, phenyl acetate, phenyl propionate, phenyl butyrate, salicylic acid, phenyl salicylate, aspirin, p- hydroxybenzoic acid, methyl p-hydroxybenzoate, methyl o-hydroxybenzoate, ethyl p-hydroxybenzoate, o-hydroxyberizoic acid, hexyl p-hydroxybenzoate, and combinations of any two or ; WO 97f22638 PCT/US96118174 22 more thereof. Presently preferred water dispersibIe first crosslinking components are phenol, phenyl acetate, phenyl salicylate, methyl p- 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. Examples of suitable second crosslinlaing 0 components include, but are not limited to aliphatic monoaldehydes, arematic monoaldehydes, aliphatic dialdehydes, aromatic dialdehydes, and their precursors. Preferred aldehydes and their precursors can be selected from the group consisting of formaldehyde, paraformaldehyde, acetaldehyde, prop ionaldehyde, 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 rat-.-o can effecl the gelation of the gelling composition. Generally, such ratio can be in the range of from about 0.0 1: 1 to about 100: 1, preferably about 0. 1: 1 to about 10: 1, and most preferably 03:1 to 2A.
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. Generally, the concentration of the water-soluble polymer in a liquid is made up to a convenient strength of about 100 to 100,000 mgll (ppm), preferably about 200 to 70,000 ppm, and most preferably 500 to 50, 000 ppm.
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 i jected slug varies generally nj c, 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 21,500 ppm. The liquid generally makes up the rest of the gelling composition.
The concentration of the complexing ligand, if presen 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.
According to the sixth embodiment of the present invention, 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.
The use of gelled polymers to alter the water permeabiliry of underground formations is well known to those skilled in the art. Generally, 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.
According to the process of the sixth embodiment of the present invention, an aqueous gelling composition comprising a crosslinking agent and a gellable polymer is injected into an injection or production well. 71e 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 _ WO 97/22638 PCT.US96/18174 24 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.
According to the sixth embodiment of the invention, the gelling can be prepared on the surface followed by introducing the prepared composition into a subterranean formation. Alternatively, individual components of the gelling cc)mposition 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 70F to about 3507. 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.
According to the seventh embodiment of the invention, 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.
According to the seventh embodiment of the invention, the clay useful in the invention can be any clay. Examples of suitable clays include, but are not limited to, kaolinite, halloysite, vermiculite, chlorite, attapulgite, smectie, montmorillonite, illite, saconite, sepiolite, palygorskite. Fuller's earth, and combinations of any two or more thereof. The presently preferred clay is montmorillonite clay. The prcsently most preferred clay is sodium montmorillorute, which is also known as bentonite.
N I; WO 97122638 PCT/US96/18174 Based on the total weight % of the composition, 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 I weight % to 20 weight %. The water-soluble polymer can be present in the composition in the range of from about 0.005 to about IS; 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.
The scope and definition of liquid are the same as those disclosed above. The liquid component generally makes up the rest of the composition.
According to the present invention, a thinner can also be present in the presert invention, if desired, in an amount in the range of from about 0. 001 to about weight %, preferably about 0.00 1 to about 5 weight %. Examples of 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.
According to the seventh embodiment of the invention, if the composition needs to be weighted, the composition can also comprise a weighting M agent. Any known weighting agent that can be suspended in the composition can be used in the present invention. Examples of 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. Depending on the desired density of the composition, the weighting agent, if present, can be present in the composition in the range of fTom about 0.000 1 to about 70.
Additionally, 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 The 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.
Examples provided hereinbelow are intended to assist one skilled in the art to further understand the invention and should not be considered limilative. EXAMPLE I This example illustrates the preparation of nitrogen-containing clefinic monomers.
N-ac:,ylQvl morpholine ChjAM) N 0 0 N-acryloyl morpholine was prepared from morpholine and acryioyl chloride. Morpholine (0.335 mole; 30.0 g), 0.421 mole (421.5 g) of triethylamine and 0. 1 g of 1,3-dinitrobenzene were dissolved in 3 50 ml of chloroform and cooled to ca.
-1 5C. Acryloyl chloride (0.42 mole; 37.8 g) was then added from a dropping funnel 0 in such a way that the temperature in the reaction flask did not exceed O'C. The reaction mixture was then allowed to reach room temperature (about 25C). After 2 hours at room temperature the solution was poured into an excess of diethyi ether (500 ml), and the precipitated material was filtered from the ether. Th-- organic phase was concentrated on a rotavapour. Hydroquinone (0. 1 g) was added -in order to prevent polymerization and then distilled under reduced pressure. The product was irm-nediately placed in the refrigerator. B.p. 74C/0.01 rnbar. The yield was 64%.
N-af lloyl-N'-mcthvl piperazine (AMP) 0 N \-i N- N-acryloyl-N'-rnethyl 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 mI 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 orgarc layer was dried with CaCI,. Distillation under reduced pressure gave the product as a cear liquid.
13.p. 90-95CIO.5 mbar. The yield was'12%.
N-acryloyl-N'-(3-sulfoWo- Y1)-N'-rnethyl piperazinium inner salt (AMPPS) r--\ 1 N NO \--/ \_---'\_ g 0 S03 N- acryl oy I-N'-(3 - sul top ropyl)N'- methy 1 pip-Crazinium inner salt was prepared from 0.26 mole (40.1 g) of N-acryloyl-N'-rnethyl piperazine and 0.29 mole (34,9 g) of 1,3-propanesultone. The reagents were mixed together with 0. 1 g of is 1,3-dinitrobenzcne in 260 mi of acetonitrile. The reaction mixture was heated to 9WC for 2 1/2 hours. The precipitated material was then filtered and washed thice times with diethyl ether (100 ml) each. The white powder was dried under reduced pressure (12 mm Hg) for 18 hours. The yield was 68%.
N-aQrylovl-N'-(2-amino-2-oxoethyl)-N'-mlhvl.pI r"nium chlorid.AOMPC) c? 0 0 \--/ N-acry loyl-N'- methyl piperazine (0. 13 mole; 20.0 g) was dissolved in 260 mI of dry acetonitrile (distilled over P,05) together with 0. 1 g 1,-- ,-dinitroberizene.
Then 0. 16 mole (14.6 g) 2-chloro ac--tamide was added to the N-acryoylN'-methyl piperazine, and the mixture was heated to ca. 8WC for 123 hours. A white, precipitated powder was filtered and washed three times with diethyl ether (150 m[).
The product was dried under reduced pressure (12 rrm Hg) for 12 hours. The yield was75%.
N,N-dimethvl-N-(3-sulfopropvl)-N-(4-vinvIbenZyvl) ammonium inner salt (DMAMSPS) N N,N-dimethyl-N-(4-Yinylben-,,,,,1) amine (93.0 mmolle, 15 g), 111.6 mmole (13.6 g) of 1,3-propanesul tone and 0. 1 g of 1,3dinitrobcn2cne were mixed together and dissolved in 190 m] of toluene. The mixture was heated at 45-50C for 72 hours. A white, precipitated matenal was filtered, washed three times is with diethyl ether (100 ml), and finally dried under reduced pressure (11 rrun Hg) for hours. The yield was 87%.
N.N-dirnethyl-l.,'-(2-amino-2-o,xoethvl)-N-(4--,?inylbe=l) a=oniun.. chloride fAQLWAC C 0 N,N-di methyl -N-(4-vinylbenzy 1) amine (62.0 mmole; 10.0 g), 68.0 nunole (6.4 g) of 2-chloro acetamide and 0. 1 g of 1,3 -dinitrobenzene were dissolved in 125 mI of acetonitrile and heated at ca. 45'C for 48 hours. The precipitated rnaterial 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-oxocthyl)-N'- vinyl imidazolium chloride (AOM N', /c CT Nj 1 -Vinyl imidazole (0. 17 mole; 15.8 g), 0.20 mole (19.1 g) of 2- chloro acetamide and 0.1 g of 1,3-dinitrobenzene were mixed together, dissolved in 340 rril of acetonitrile and heated at 70-75 C for three nights (about 64 hours). The precipitated material was then filtered and washed three times with acetonitrile (150 m]). The product was dried under reduced pressure (12 mm Hg) for 15 hours. The product was a white powder, and the yield was 65%. N.N-diinethvi-N-(3-sul [o12rQpvl)-3-(aciv_lovl amino)-] propancammgni inner salt (APDAPS) 0 G) S 0, Acryloylchloride (0.70 mole; 63.8 g) and 0. 1 g of hydroquinone were dissolved in350m] ofacctonitrile and cooled to -15'C. Then 0.59 mole(60.0 g)of 3-dimethyl amino- 1-propylamine was added from a dropping fi=el 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 (28.0 g Na0H in 70 rnl distilled water, 0.70 mole) was added and the precipitated material was filtered. The filtrate was concentrated on a rotavapour and then distilled under reduccd pressure. B.p. 122'C/0. I mbar. The yield was 55%.
Eighty-three mmole (13.0 g) of this product was reacted further with 99.6 mmole (12.2 g) of 1,3-propanesultone in 83 ml of toluene. In the rn.ean time, 0. 1 g 1,3-dinitrobenzene was added to prevent polymerization. The reaction mixture was heated at ca- 55'C for 3 hours. A white, precipitated powder was filtered and washed three times with diethyl ether (200 ml). Finally the product was dried under reduced pressure (12 mrn Hg) for 17 hours. The yield was 80%.
EXAMPLE 11
This example illustrates the production of polymers of the present invention.
Polymerizations were carried out in distilled water or syrthetic sea water. For synthetic sea water, one liter distilled water contained 23.83 g NaCl, 0.211 g NaHC03, 10.779 MgC'2-6H,O, 1.65 g CaCl,-2H.0, and 42-9 g anhydrous Na,SO..
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'-azobisodihydrochloride) was used to start the polymerizations. The polymerizations were carried out at room temperature. In a typical syndiesis, specified quantities of the monomers were dissolved in distilled water o-- syntheic sca water and the mixture was purged with nitrogen for 50 minutes. Initiator was then added. The polymers were precipitated in methanol or acetone, redissolved in distilled water or synthetic sea water and finally lyophilized (freeze dried). The term "parts" used hereinafter in defining a polymer denotes mole %. The products were white, amorphous powders.
Copolymer Arn-LAME Eighty parts of acrylamide and 20 parts of N-acryloyl-N-methyl piperazine (ANIP) were polymerized in distilled water for 4 hours with use of 0.3 mole % VA-044 as a initiator. The polymer was precipitated in acetone. The yield was 34 Copolymer Am / NAM Eighty parts of acrylamide and 20 parts of N-acryloyl morpholine were dissolved in distilled water and the polymerization was carried out with use of 0.3 mol % VA-044 as initiator. The polymerization was stopped after 6 hours.
The polymer was precipitated in acetone. The yield was 69 %.
Terwlvrrier Am /-NAM / AMP The polymer was prepared from 70 parts of acrlvlamide, 15 parts of N-acryloyl morpholine CINAM) and 15 parts of N-acryloyl-N'-methyl piperazine (AMP) with use of 0.3 mole % VA-044 as initiator. Distilled water was used as solvent. After 5 hours the polymer was precipitated in acetone. The yield was 41%.
Coi2olvmer Am / AMPPS Eighty parts of acrylamide and 20 parts of N-acryloyl-N'-(3-sulfopropyl)-N'-methyI piperazinium inner salt (AMPPS) were polymerized in synthetic sea water for 2 hours with use of 0.3 mole % VA- 044 as initiator. The polymer was precipitated in methanol. The yield was 62%.
Copolymer Am / DMAMSPS A polymer was prepared from 80 parts of acryiamide and 20 parts of N,N-dimethyl -N- Q -sulfbpropy I)-N-(4- vinyl benzy 1) ammoniin-n inner salt (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%.
Copolymer Am / APDAPS Eighty parts of acrylamide and 20 parts of N,N-dimethyl-N-(3-sulfopropyl)-3-(acryloylarnino)- I -propanearnmonium inner salt (APDAPS) were polymerized in synthetic sea water for 5 hours with use of 0-3 1\ mole % VA-044 as initiator. The polymer was precipitated in methanol. The yield was 81%. Terpplymer Am / AMP / DMAMSES Sixty parts of 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 (DMAiMSPS) were dissolved in synthetic sea water and the polymerization was carried out with use of 0.3 mole % VA-044 as initiator.
The polymerization was stopped after 3 U2 hours by precipitation of the polymer in methanol. The yield was 23%.
Temoljmcr Arn 1 AMP / APDAPS Seventy parts of acrylamide, 25 parts of N-acryloyl-N'-methyl piperazine (AMP) and 5 parts of N,N-dimethyl-N-(3-sulfopropyl)-3-(acryloylamino)-1- propanearnrnonium inner salt (APDAPS) were polymerized in synthetic sea waterwith use of 0.3 mole % VA-04-1 as initiator. The polymenzation was stopped after 3 hours by precipitation of the polymer in methanol. The yield was 59%. Terpolymer Am! AMP 1 AMPPS Seventy parts of acrylarnide, 15 parts of N-acryloyl-N'-rnethyl piperazine (AMP) and 15 parts of N-ac ryloy I-N'-(3 -sul fopropy 1) -N'-m ethyl piperazinium inner salt (AMPPS) were dissolved in synthetic sea water and polymerized for 23 hours. VA-044 was used as initiator. The polymer was precipitated in methanol. The yield was 34%.
Copolvmer OMPC 1 AMPS Fifty par.s of 2-acrylarnido-2-methylpropanesuifonic acid (AMPS). -51) parts N-acryloyl-T-(2-amino-2-oxoethyl)-N'-methyI piperazinium chloride (A0INIPC) and 50 parts NaOH were dissolved in NaCI-solution and polymerized.,','or 6 hours Wlh use of 0.3 mole % VA-033 as initiator. The polymer was precipitated iii methanol.
The yield was 54%.
TeMQlymer A0W ANT / AMPS A polymer was prepared ftom 15 parts of N-(2 amino -2-oxoethyl)-N'-vinyl Imidazollum chloride (AOVC), 70 pails of Nacryloyl-N'-rnethyl piperazine (AMP), 15 parts of 2-acrylarnido-2-methylpropane-sulfonic acid (A.MPS) and 15 parts of NaOH in synthetic sea water. Three tenths mole % VA-044 was used as initiator and the polymerization was stopped after 5 hours by precipitation of the polymer in methanol. The yield was 38%. A0,14PC H--mopolynitrN-acryloyi-N'-(2-amino-2-oxoethyl)-N'-methyl piperazinium, chlonide (A0NIPC) (20.19 mmol) was dissolved in synthetic sea water and 0.3 mole % VA-044 was added. The polymerization was stopped after 6 hours by precipitation of the polymer in acetone. The yield was 57%.
TerpQ1vrner Am / AMP / AMPS Seventy parts of acrylamide. 15 parts of N-acryloyl-N'-methyl piperazine (AMP) and 15 parts of 2- acrylami do-2 -methyl -propanesul fonic acid (AMPS) were dissolved in distilled water and polymerized for 3 hours. Three tenths mole % VA-044 was used as initiator. The polymer was precipitated in acetone. The yield was 47%.
EXAMPLE 111
This example illustrates the preparation of gelling compositions from, the polymers disclosed above and the stability of gels formed from the gelling compositions, Preparation of Gelling Compositions Stock solutions of a polymer contained 4 weight % of the polymer in synthetic sea water. The polymer solution was allowed to stand at least three nights (about 64 hours) ikith, magnetic stirring before use.
11; WO 97/22638 PCT!US96/18174 34 Stock solutions of phenol, formaldehyde and HMTA each containing 10,000 mg/l (ppm) were used.
For each test 4.0 g of gelling composition were made by adding polymer, phenol and formaldehyde/HMTA solution and diluting with synthetic sea water to the correct concentration. The same pprn concentration of both phenol and fortnaidehyde/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.
For aging at 120C, the glass vials were placed in stainless steel C, 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 (weight of gel after exposure) / (initial weight of gel forming solution).
For gels in ampules, the syneresis was measured by measuring &.e 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 urn 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 25.0 0-05'C.
Relative viscosity: time for polymer solution through capillary/ time for synthetic sea water trough capillary Inherent viscosity: In(rel. visc.) 10. 1 g/di The results are shown in the following Tables PKKI. These tables show that gels formed from the polymers of the present invention were resistant to high temperature and high salinity environment. Little or no synercsis was observed after prolonged aging at high temperature and high salinity environment.
1 11 WO 97a2638 PCTj'US96118174 36 Table I
Polymer Phenol/ Gel height (G) and Am/AMP' Inherent conc. HMTAd Liquid height (L) aftev aging Run Feed Viscosity (ppm) in (ppm of at 120T in SNSW for No. Ratio' dUg SNSW' each) 30 days 55 da-vs 70 days 181 G--25 mm G=25 mm Cj--25 isl L-5 mm L=5 mm L=5 mm 1123 80!20 5.4 6200 250U Rigid Rigid Rigid 181 G=30 mm Cj--25 mm G=25 mm Jsl L=O mm L=5 mr-, L=5 mm Rigid Rigid Rigid 1123 8014-0 5.44 10400 2500 181 G=26 mm G-24 min G--24 mm isi L=O mm L= I min L=2 mm Rigid Rigid Ris!id I 123 80/20 5.4 20000 2500 Am=acrylamide, AtMP=N-ac:ryloy1-N'-methyl piperazine bmole % ratio of monomers in the aqueous solution SNSW=svnthetic sea water IHMTA=hexamethylenetetramine Table 11
Polymer Phenol/ Wtlzht % gel' Inherent conc, HIMTA" Gel Character Run Am/AMF' Viscosity (ppm) in (ppm of No. Feed Ratio' dUg SNSWc each) 5 months HSI 80 1123 80/20 5.4 6200 2500 Rip-id 181 isl 80 1123 80/20 5.4 10400 2500 Rigid 181 is] 90 1123 80/20 5.4 20000 2500 Rip-ld Am=acrylamide, AMP--N-acryloyi-N'-methyl pipeTazine t'mole % ratio of monomers in the aqueous solution SNSW=synthetic sea water d HMTA=hexamethylenetetramine Weight % gel of initial weight of the solution after aging aL 120'C in synthetic sea wate:- 37 Table Ill
Polymer Phenol Inherent conc. HCHO Run Am/AMP' Viscosity (ppm) in (ppm of Weight % gel' No. Feed Ratio' dlig SNSWc each) Gel Character days 30 days 154 TOB 100 VII 43 70130 5.1 20000 2500 Strong 168 isi 55 176 70130 3.8 10000 500 Weak 16 8 JS1 100 176 70/30 3.8 20000 2500 Rigid TOB 100 VII 52 60/40 4.33 20000 2500 Strong TOB 82 VIT 52 60/40 4.3 5000 1000 Rigid TOB 100 2 60/40 4.3 10000 1000 Strong VII 5.
TOB 100 VII 52 60/40 4.3 10000 2000 Rigid 156 TOB 100 VII 49 50:50 3.4 20000 2500 Weak 156 TOB 83 VII 49 50/50 3.5 5000 1000 Strong Table III
Polymer Phenol/ Inherent conc. HCHO' Run Arn/AMP' Viscosity (ppm) in (ppm of Weigh,, % gel- No. Feed Ratio' dl/g SNSWI each) Gel Character 156 TOB 89 VII 49 50/50 3.5 10000 1000 Strona 156 TOB 100 VII 49 50/50 3.5 10000 2500 Rigid aAm=acrylarnide, A,\4P--N-acryloy1-N'-methyl piperazine b mole % ratio of monomers in the aqueous solution cSNSW=synthetic sea water IHCHO=formaldehyde eWeight % gel of initial weight of the solution after aging at 120C in synthetic s.:a water Table TV
Potymer Weight 0/0 gel' Inherent conc. PhenoPI Gel Character Run Am/AMP Viscosity (ppm) in HMTA' No. Feed Ratio' dlfg SNSW (Ppm) 30 days 154 TOB 96 VII 43 70/30 5.1 10000 2000 Strong 154 TOB 100 VI1 43 70/30 5.1 20000 2000 Sti.ong 168 J51 176 70:30 3.8 5000 1000 Strong 168 isi 73 176 70:30 3.8 10000 500 W eak.
Table TV
Polymer Weight '.'/o i2ei' Inherent conc. Phenol'/ Gel Character Run Am/AMP' Viscosity (ppm) in HMTA' No. Feed Ratio' di/g 5NSW, (pprn) 30 days 168 isi 80 1 76 70:30 3.8 10000 1000 Weak TOB 92 VII 52 60140 4,3 10000 2000 Weak 1 TOB 100 VII 52 60140 4,3 20000 2000 Stronp- 197 JS1 100 1163 60140 3.8 20000 2500 Rigid 19-, J51 90 1163 60140 3.8 10000 2500 Rigid 198 JS1 100 11 65 60140 3.7 20000 2500 Rigid 156 TOB 100 V11 49 50150 3.5 20000 2000 Weak Am=acrylarnide, AM.FN-acryloyl-N'-methyl piperazine bmole % ratio of monorners, in the aqueous solution SNSW=synthetic sea water 2500 ppm HMTA=hexamethylenetetramine Weight % gel of initial weight of the solution after aging at 12WC in sy, nthetic sea water is ^5 0 Table V
Polvmer Phenol/ Gel height (G) Inherent dne. Hmta and Liquid height (L) after ag, ing Run AmInarn' Viscosit (Ppm) in (Pprn of at 120T in SNSW for No. Feed y Snsw' Each) 30 days 55 days 70 days ratio' D11g 179 Cj=30 mm G=28 mm C-28 rnm isi 11 L= 5 MTr. 1=7 mm L=7 mm 11 80:20 4.4 5400 2500 Rigid Rigid Rigid 179 G-27 mm G=27 mm G=27 mm is] 1 1 Lj mm L, 5 MM L=5 inm 11 80:20 4.4 10300 2400 Rigid Rigid Rigid 179 G=26 rnm G=34 rnm G=24 isi 11 L=3 mm L-5 rnm L-5 mm 11 80:20 4.4 20000 2400 Rigid Rigid Rigid Am--acrylamide, NAM=N-acryloyl morpholine bmole % ratio of monorners in the aqueous solution ^SNSW=synthelic sea water IHMTA=hexamethylenetetramine Table VI
Polymer Phenol/ Weight % gel' Inherent conc. HMTA' Gel Character Run AmINAM' Viscosity (ppm) in (ppm of No. Feed Ratie dlig SNSW' each) 5 months 179 JSI 0.8 11 80r20 4.4 5400 2500 Rigid 179 isl 0.9 11 11 90/20 4.4 10300 2400 Rigid 179 isi 0.9 11 11 80120 4-4 20000 1 2400 Figid Am=acrylamide, NAM=N-acryloyl morpholine b mole % ratio of monomers in the aqueous solution SNSW=synthetic sea water HM.TA=hexarnethylenetetramine cWeight % gel of initial weight of the solution after aging at 120C in syntheV,-. sea water 41 Table V11
Polymer Phenol/ Inherent cone. HCH00 Run Arn/NAM' Viscosity (Ppm) in (ppm of Weight % gel' No. Feed Ratio' dllg 5NSWc each) Gel Character J51 30 179 80/20 6.2 10000 500 Strong J51 23 179 80/20 6.2 10000 2500 Strong 17 1 isi 100 181 70/30 3.7 10000 1000 Rigid 172 JS1 183 60/40 3.3 20000 1000 Rigid 7 1 TOB 100 70 V85 20180 2.5 20000 2500 Strong Strong TOB 42 35 vii 20/80 1.1 30000 4000 Stron- Strong 17 TOB 55 vil 20180 1.1 30000 2000 Strong 17 Arn=acrylarnide, NAM=N-acryloyl rnorpholine b mole % ratio of monomers in the aqueous solution SNSW=synthetic sea water d HC'40=form aldehyde Weight % gel of initial weight of the solution after aging at 12CC in synthetic sea water 1 1 WO 97122638 PCTrUS96118174 42 Table VIII
Polymer Weight gel' Inherent conc. PhcnoV/ Gel Character Run Am/NAM' Viscosity (ppm) in HMTA' No. Feed Ratio' dl/g SNSW' (ppm) 30 days Parallel 19 Parallel 29 is[ 93 94 159 70/30 2.2 20000 2000 Rigid Weak isl 100 159 70/30 2-1 10000 2000 Rigid 151 is[ 96 80 161 60/40 2.2 20000 2000 Rigid Weak 152 isl 90 100 163 50/50 2.5 20000 2000 Strong Weak Am=acrylarnide, NAM=N-acryloyi morpholine b mole % ratio of monomers in the aqueous solution SNSW=synthetic sea water 2500 ppm HMTA=hcxamethylcnetctrwnine Weight % gel of initial weight of the solution after aging at 120C in synth.etic sza water 6Duplicate runs.
z 1 43 Table IX
Polymer Phenol/ Weight % gel' Inherent conc. HMTA d Gel Character Run Am/NAMIAMP' Viscosity (ppm) in (ppm of No. Feed Ratio' dI/g SNSWc each) 30 days 188 is] 100 1121 7 0/ 15/15 4.6 10000 2500 Rigid 188 isl 95 1121 70/15/15 4.6 20000 2500 Rigid 198 is] 47 1121 70115115 4.6 10000 1000 Strong Am=acrylamide, NAM=N-acryloyl morpholine, AN1P=N-acryloy1-N'-methyl pipera7inC b mole % ratio of monomers in the aqueous solution cSNSW=synthetic sea water HMTA=hexamethylenetetramine eWeight % gel of initial weight of the solution after aging at 120C in synthetic sea water Z Table X
Polymer Phenol/ Inherent conc. HCH0d Run Arn/ANIPPS' Viscosity (ppm) in (ppm of Weight % gele No. Feed Ratio' dIlg SNSW' each) Gel Character days '30 days 162 is] 100 80120 10000 1500 Strong 162 isi 100 80/20 2.2 20000 1000 Rigid 162 isi 100 80120 2.2 10000 2000 Rigid 132 isi 100 41 128 80120 1.8 30000 4000 Rigid Strong 132 isi 32 128 70/30 1.8 30000 2000 Stroniz 13 0 isi 100 (52 126 60140 1.6 30000 4000 Strong Strong JS1 75 126 60140 1.6 30000 2000 Strong TOB 94 60 VI 68 50150 20000 2500 Weak Weak TOB 1 V11 15 50140 1.5 30000 4000 Strong Strong TOB 77 vII 15 solso 1.5 30000 2000 Strong r&Arn=acrylarnide, AMPPS=N-acryloy]-N'-(3-suifopropyl)-'!']'-methy1 piperainium Table X1
Polymer Phenol/ Weight % gel' Inherent conc. HNITA' Gel Character Run Am/AMPPS' Viscosity (ppm) in (ppm of No. Feed Ratiob dUg SNSWI each) 30 days 202 jSI Rigid 1167 80/20 3.5 10000 2500 90 202 JSI Rigid 1167 80/20 3.5 20000 2500 70 Am=acrylamide, AMPPS=N-acr-vioyi-N'-(3-sulfopropyl)-N'-methyI pipeTazine inner salt b mole % ratio of monomers in the aqueous solution SNSW=synthctic sea water HMTA=hexarnethylenetetramine Weight % gel of initial weight of the solution after aging a-, 120C in synthetic sea water Table XII
Polvmer Phenol/ Inherent conc. HCHO' Weight % gel' Run Am/DMAMSPS' Viscosity (ppm) in (ppm of Gel Character No. Feed Ratio' d1/g SNSWI each) days 30 days 149 is] 81 90/10 1.0 10000 2500 Strom! 149 is] 88 90/10 1.0 20000 2500 Strong TOB 100 79 V 79 8Oi2O 0.9 10000 2500 Weak Weak 137 TOB 93 72 VII 23 1 2.0 30000 4000 Strong Strong 90/20 137 TOB 7 7 VII 23 1 2.0 10000 1000 Strong 80120 137 TOB 100 V11 '13 80/20 2.0 10000 22500 Rigid Am=acrylamide, DMAMSPS=N,N-dimethyl-N-(3-sulfopropyl)-N-(4-vinylben,71)ammonium inner salt b - mole % ratio of monomers in the aqueous solution SNSW=synthetic sea water IHC140=forrnaldehyde Weight % gel of initial w6ght of the solution after aging at 120C in synthct1c.;ca watcr Table XIII
Polymer Phencl/ Weight % gel Inherent conc. HMTAd Gel Character Run ArrilDMAMSPS' Viscosity (ppm) in (ppm of No. Feed Ratio' d Llg SNSW' each) 30 days 137 TOB VII 23 80120 2.0 10000 2000 Weak gel 137 TOB 100 VII 23 80120 2.0 20000 2000 Weak Am=acrylarnide, DtvtAMSPS=11.I,N-dimethyl-N-(3-suffopropyi)-N-(4- Yinyibenzvi)- ammonium inner salt b mole % ratio of monomers in the aqueous solution ISNSW=synthetic sea water IWATA=hexamethylenetetramine Weight % gel of initial weight of the solution after aging at 12WC in synthetic sea water 1.1 Table 3CIV [No. Polymer Phenol/ Weight % gelE Inherent cone. FUvITA' Get Character Run Am/APDAPS' Viscosity (ppm) in (ppm of F eed Ratio' dl/g SNSWc each) 30 days 193 TOB so V11 89 90120 5.3 5000 2500 Rigid Ta, 90 TOB L193 80120 5.3 10000 2500 Rigid 1 """"8 9 VII 93 TOB 90 V11 89 80/20 5,3 20000 2500 Strong Am=acrylamide, APDAPS=N,N-dimethyl-N-(3-sulfopropyl)-3-(acryloylamino)-1propaneammoniurn inner salt b mole % ratio of monorners in the aqueous solution cSNSW=synthetic sea water IHMTA=hexamethylenetetramine Weight % gel of initial weight of the solution after aging ai 1200C in synthefic sea water Table XV polymer Phenol/ Phenov Weight % gel( ArnIAMPI Inherent mne. HCH011 HMTA' Gel Charaetc., Run DNUMSPS Viscosity (Ppm) in (ppm of (pprn of No Feed Ratio' dVg SNSW, each) each) 30 days TOB 100 VIT 87 60120120 2.4 10000 2500 Strong TOB 100 VII 87 60120120 2-4 20000 2500 Rigid TOB 100 VII 87 60120/20 2.4 20000 2500 Rigid Arn=acryfamide, AMP=Nacryloyl -N"-m ethyl piperazine, D MAM S P S=N,N-d im ethyl-N-(3 -su 1 fop ropy 1)-N-(4-v inylbenzyl)-amn on i urn inner salt b mole % ratio of monomers in the aqueous solution SNSW=synthetic sea water IHCHO=forrnaldehyde IHMTA=hexamethylenetetramine Weight % gel of initial weight of the solution after aging at 12CC in synthetic sea water :. WO 97122638 PCT,'U596118174 Table XVI,
Polymer Phenol/ Weieht % gelc Arn/AMP1 Inherent cone. HNITAI Gei Character Run APDAPS' Viscosity (ppni) in (ppm of No. Feed Ratio' di/g SNSW' each) 30 days 196 TOB 100 V11 85 70P25,'5 4.4 5000 2500 Rigid 196 TOB 33 V11 85 701253 4.4 10000 2500 Rigid 196 TOB 36 V11 85 70P253 4.4 20000 2500 Rigid 203 lBV 1 49 60/30110 3.5 10000 2500 Rigid 20-1 IBV 35 149 60130110 3.5 20000 2500 Rip-1d Am=acryiamide, AivlP=N-acryloy]-N'-methyl piperazine. APDAPS=N,N-dimethy]- N-(3 -sulfopropyl)-3-(acryloylarnino)-1propaneammonium inner salt hmolc % ratio of monomm in the aqueous solution cSNSW=synthetic sea water HMTA=hexarnethylenetetramine Weight % ael of initial weight of the solLilion after aging at 12CC in synthetic sea waier 1 Table XVI I
Polymer Phenol/ Weight % gel' Am/A,MP/ Inherent conc. HMTA' Gel Character Run APDAPS' Viscosity (ppm) in (ppm of No. Feed Ratio' dl/g SNSW- each) 30 days 184 isl 70 1125 70/15/15 1.9 10000 1 Rigid 2500 184 isl 100 1125 70/15/15 1.9 20000 2500 Rigid Am=acrylamide, AMP=N-acry[oyl-N'-methy1 piperazine, AMPPS=N-acryloyi-N'-(3-sulfopropyl)-N'-methyI piperazinium inner salt b mole % ratio of monomers in the aqueous solution ISNSW=synthetic sea water IH,NITA=hexamethylenetetramine eWeight % gel of initial weight of the solution after aging at 120C in synthetic sea water is Table XVIII
Polymer Phenol! Weight % gel, AOMPC/ Inherent conc. HCH01 Gel Character Run AMPS' Viscosity (ppm) in (pprn of No. Feed Ratio' dt/g SNSW' each) 30 days 189 1BV 100 143 50/50 1.1 10000 2500 Strong AOMPC=N-acryloyl-N'-(2-amino-2-oxoethyl)-N'-methyI piperazinium Chloride, AMPS=2-acrylamido-''-methyl-propanesulfonic acid b mole % ratio of monomers in the aqueous solution SNSW=synthelic sea water d HCH0--formaldehyde eWeight % gel of initial weight of the solution after aging at 120C in synthetic sea water Table XIX
Polymer Phenol/ Weight % gele AMCIAMP,' Inherent conc. FICHO' Gel Character Run AMPS' Viscosity (Ppm) in (ppm of No. Feed Ratio' dilg SNSWe each) 30 days 191 isi 00 1133 15170/15 1.6 20000 2500 Rigid AOVC=N-(2-arnino-2-oxoethyt)-N'-vinyl imidazolium chloride, AMP=Nacryloyl-N'methyl piperazine, A MPS=2 - acry km ido-2-methy 1-propanesu 1 fonic acid b mole 0Kb ratio of monomers in the aqueous solution cSNSW=synthetic sea water IHCHO=forTnaldehyde eWeight % gel of initial weight of the solution after aging at 12WC in synthetic sea water Table XX
Inherent Viscosity dVg Polymer Phenol/ Wei7ht % geld conc. HCHO' Gel Character Run A0NIPC 0.1 (ppm) in (ppm of No. Hornopol' weight 0/0 SN SWb each) 3 0 days 117 TOB 100 V11 8 1.4 30000 4000 Strong AOMPC=N-acryloyl-N'-(2-amino-2-oxoethyl)-N'-methyl pipeTazinium chloride.
hornopoiymer b SNSW=synthetic sea water HCHO=forTnaldehyde dWei ght % gel of initial weight of the solution after aging at 12WC in synthetic sea water I Table XXI
Polymer Phenoll Weight % gel' Am/AMP/ Inhercnt conc. HCHO' Gel Character Run AMPS' Viscosity (ppm) in (Ppm of No. Feed Ratio' dI/g SNSW' each) 30 days 157 TOB 100 VII 57 50/25/25 3.4 20000 1000 Strom g 157 TOB 100 VII 57 50/25/25 3.4 20000 2500 Scron, Am=acrylair,ide, AMP=N-acryloyl-N'-methyl piperazine, AMPS=2=acrylamido-2-methyl-propanesulfonic acid b mole % ratio of monomers in the aqueous solution cSNSW=synthetic sea water dHCHO--formaldehyde Weight % gel of initial weight of the solution after aging at I 20C in synthetic sea water EKAMPLE TV 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.
A 7000 ppm solution of Dowell J333 polyacrylamide in seawater was crosslinked with phenol and formaldehyde at 120'C. Table XXII shows a summary of the results.
Table XXII
Polymer Phenol/FormaIdehyde Gel Height (G) and Liquid Height (L) Concentration (ppm of each) after 6 days aging at 120'C G(mm) L(mrn) 7000 500 22 65 Rigid 7000 1000 20 70 Rigid 7000 2000 30 75 Rigid The results shown in Table XXII indicate that much synere-sis occurred in gels formed from polyacrylamide only after aging for 6 days.
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 ftesh water based compositions were prcparcd by mixing the components shown in Table =11 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 theil 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 1nitial Results". The compositions were then kept in capped j ars 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 XXIII'
Run Materials Used 8-1 345 mI tap water + 10 g bentonite (40) 8-2 325 mi tap water + 10 g bentonite (20) + 20 g of4% solution of NAIWAM in deionized water (20).
8-3 325 m] tap water -- 10 g bentonite (20) + 20 g of 4'1/6 solution of NANI/AP in deionized water (20).
8-4 325 mi tap water - 10 g bentonite (20) + 20 g oF4% solution of NANI/AA in deionized water (20).
8-5 305 m 1 tap water - 10 g benton ite (20) + 40 g of 4% solution of NANI/AM 1. n deionized water (20).
8-6 305 mI tap water - 10 g bentonite (20) + 40 g of 4% solution of NAI'vt/AP in deionized water (20).
8-7 305 mi tap water - 10 g bentonite (20) + 40 g of 4% solution of NAM/AA in deionized water (20).
INAMAM is a copolymer of 25% (mole %) acryloyl morpholinc and 75% acrylamide; NAINI/AP is a copolymer of 25% acryloyl morpholine and 75% ac ry lam ide-2-methy lpropanesu Ifonate; NAM/AA is a copolymer of 25% acryloyl morpholine and 75% acrylate; these polymers were prepared according to the process disclosed in Example II.
Table XXIV' initial Results Results After Aging at 75 C Run AV PV YP Gels FL AV PV YP Gels FL 9-1 2.5 2 1 1/1 20.4 2.5 2 1 1/2 16.8 9-2 12.0 6 12 3/5 63.7 14.5 1 5 19 3/6 67.6 8-3 8.0 7 2 113 15.8 8.5 7 3 2/2 15.4 8-4 10.5 8 5 1/3 13.5 11.5 '10 3 2/3 13.1 8-5 32.5 19 27 14 /2 3 68.1 33.0 19 28 CNM 47.4 8-6 24.0 13 22 3/5 7.8 25.0 15 20 3/5 9.0 8-7 36.0 21 30 516 8.3 37.0 23 28 5i6 8.6 AV-apparent viscosity, cps PV-plastic viscosity, cps.
Gels-gcl suength, 10 seconds/I Orninutes, lbs/I 00 sq-ft.
FL-fluid loss at low-temperature/low-pressure, nil 30 minutes.
CNM-can not be measured accurately.
L_ The results in 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 p0lyrne7.
Further, these four inventive compositions had higher viscosity than the base fluid.
High viscosity is desirable. Even though t-wo invcntive compositions (run 8-2 and 8-5) had high fluid loss, their high viscosity is useful in bringing the drih cuttings to the surface.
EXAMPLE VI
This example illustrates a sea water based composition ofthe invention that can be used as drilling fluids, completion fluids, or workover fluids.
Four sea water based compositions were prepared by ml-<;ng the components shown in Table XXV on aNtulti-mixer in quartjars. The -nixing time, in minutes, after the addition of each component is shown in the table. Afiethe mixing was completed, the fluid compositions were kept at about 75 " C for about two hours. Each composition was 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 lowtemperature/low-pressure according to the API RP 1313- 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 11.
Table XW
Run Materials Used 9-1 340 rril tap water + 10 g bcnionite (20) + 2 gNa-lignite (10 1 14.7 g sea salt (30) 9_.7 265 m[ tap water + 10 g bentonite (20) + 2 g Na-lignite (10) + 14.7 g sea salt CY (10) + 75 g of 4% solution of NAWAM in deionized water (20) 9-3 265 m] tap water + 10 g bentonite (20) + 2 g Na-lignite (10) + 14.7 g sea salt (10) - 75 g of 4% solution of NAM/AP in deionized water (20) 9-4 265 iril tap water + 10 g bentonite (20) + 2 g Na-lignite (10) - 14.7 g sea salt (10) + 75 g of 4% solution of NAMAA in deion ized water (20) See footnote a in Table XXITI.
Table XXVI'
Initial Results Results After Aging at 75 "C Run AV PV YP Gels FL AV PV YP Gels FL 9-1 6.5 2 9 8/9 79.2 7.0 1 8 6/8 62.2 3 9-2 16.5 10 13 5/8 19.4 15.0- 10 to 4!8 18.5 9-3 24,0 15 18 6/9 8.1 22.5 14 17 4!7 7.
9-4 28.5 18 21 4/15 4.8 24.5 16 17 3/10 4.8 "AV-apparent viscosity, cps PV-plastic viscosity, cps.
Gels-gel strength, 10 seconds/ I Ominutes, lbs/100 sq.ft.
FL-fluid loss at I ow-temperatureil ow- pressure, ml 30 minutes.
10 The results in 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 su.-face.
-ne results shown in the above examples clearly demonstrate that the present invention is well adapted to carry out the objects and attain the erds and advantages mentioned as well as those inherent therein. While modifications may be made by those skilled in the art, such modifications are encompassed within the spirit of the present invention as defined by the disclosure and the claims.
1 59

Claims (1)

  1. CLAINIS
    1. A nitrogen-containing olefinic compound having the formula R,-C(Rj)=C(R1)-ffl=0).-N wherein R, and R2 are each independently selected from hydrogen, alkyl radical, aryl radical, aralkyl radical, alkaryl radical, and combinations of any two or more thereof wherein each radical contains 1 to about 30 carbon atoms; each Y is independently selected from the group consisting of alkylene radical, phenyl group, imidazolium group, naphthyl group, biphenyl group, and 0 0 combinations of any two or more thereof; X is an anion selected from the group consisting of halide, sulfate, 0 phosphate, nitrate, sulfonate, phosphonates, sulfinate, phosphinate, and combinations of any two or more thereof; and each m is independently 0 or 1.
    2. An olefinic compound according to claim 1 wherein m is 0.
    0 3. An oleflinic compound according to claim 1 wherein m is 1.
    tP 4. An olefinic compound according to claim 3 wherein the compound is 0 N-acTyloyl-N'-(3-sulfopropyl)-N'-methyI piperazini= inner salt, Nacryloyl-N'-(3-sulfopropyl)-N'-cthyl piperazinium inner salt, N-acryloylN'-(4-sulfopropyl)-N'-methyl piperazinium inner salt, N-acryloyl-N'-(4sWfopropyl)-N'-cthyI piperazini= inner s&t.
    5. A composition comprising the olefinic compound of any one of claims 0 1-4 in combination with a further nitrogen-containing olefinic compound having the formula selected from R,C(R,)=C(R1)-C=0)-(M)M-(Ar)-Y-"+(R2XRJ-Y-S03'. R,-C(R,)=C(R1)-(C=O).(NH).-(Ar).-Y-N(R2)-Y-(C=O).-N(R2)(RX', r-\ R,C(R,)=C(R1)-(C=O),-N N-(Rz)Y-(C=O).,-N(R2)(R.)X-, R,C(Rj)=C(R1)-(C=O).-N N--Y-(C=O),,,-N(R2)(R2)X-, wherein R,, R2, Y, X and m are as defined in claim 1 and Ar is an arylene group. 6. A composition according to claim 5 wherein said further olefinic compound is selected from 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'-methyl-N'-(4-amino-4-oxobutyi) piperazinium chloride, N-acryloyi-N'-ethyl-N'-(2-amino-2-exoethyl) piperazinium chloride, N-acryloyl-N'-cthyl-N'-3-arnino-3-oxopropyl) pinium chloride, N-acryloyi-N-cthyl-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-oxocthyl)-N-(4-Yinylbenzyl) ammonium chloride, N,N-dimethyl-N-(3-amino-3-oxopropyi)-N-(4-vinyibenzyl) ammonium chloride, N,N-dieihyl-N-(3-amine-3-oxopropyl)-N-(4-Yinylbcnzyl) ammonium chloride, N-(2-amino-2-oxoethyl)-N'-vinylimidawlium chloride, N-(3-amino3-oxopropyl)-N'-vinylimidazolium chloride, N-(4-amino-4-oxabutyl)-N'vinylimidazolium chloride, and combinations of any two or more thereof.
    61 7. A composition according to claim 5 wherein said further nitrogencontaining olefinic compound is selected from N,N-dimethyl-N-(2amino-2-oxoethyl)-N-(4-vinylbenzyl)ammonium chloride, N-acryloyl-N'mcthyl-N'-(2-amino-2-oxocthyl)pipcrazinium chloride, N-(2-amino-2oxocthyl)-N'-vinytimidazoliurn chloride, and combinations of any two or more thereof 8. A composition according to claim 5 wherein said further nitrogencontaining olefinic compound is N,N-dimethyl-N-(2-arnino-2oxoethyi)-N-(4-Yinylbenzyl)ammonimn chloride.
    9. A composition according to claim 5 wherein said further nitrogencontaining olefinic compound is N-acryloyl-N'-mcthyl-N'-(2-amino2-oxocthyl)piperazinimn chloride.
    10. A composition according to claim 5 wherein said further nitrogencontaining olefinic compound is N-(2-amine-2-oxoethyl)-N'vinylimidazolium chloride.
    11. A process for producing a nitrogen-containing olefinic compound 4n 0 comprising contacting a tertiary amine with an alkylating agent under 1= 0 In conditions sufficient to effect the production of said nitrogencontaining olefinic compounds wherein said nitrogen-containing olefinic compound has the formula r-\ RI-C(Rj)=C(R1)- (C=O).-?__.,N(R1)-Y-X-p I 1 62 wherein R, and R2 are each independently selected from hydrogen, alkyl radical, aryl radical, aralkyl radical, alkaryl radical, and combinations of any two or more thereof wherein each radical contains 1 to about 30 carbon atom; each Y is independently selected from alkylene radical, phenyl group, imidazoliurn group, naphthyl group, biphenyl group, and combinations of two 0 or more thereof, X is an anion selected from halide, sulfate, phosphate, nitrate, sulfonate, phosphonates, sulfinate, phosphinate, and combinations of any two or more thereof; and each m is independently 0 or 1; amine is selected from N,N-dimethyl-N-(4-vinylbenzyl) amine, NN- dimethyl-N-(4-vinylbenzyl) amine, N,N-diethyl-N-(4-vinylbenzyl) amine, NN- diethyI-N-(4-vinylbenzyI) amine, N,N-dimethyl-N-(3-vinylbenzyl) amine, NNdimethyl-N-(3-vinylbenzyl) amine, N,N-diethyl-N-(3-vinylbenzyl) arnine and N,N-diethyl-N-(3-vinylbenzyl) amine, and combinations of any two or mom thereof, and alkylating agent is selected from 3 -chl oro-propane- I sulfonic acid, 4-chloro-butanc- I -sulfonic acid, 3-hydroxy-propane- I sulfonic acid, 4-hydroxy-butane- I -sulfonic acid, the corresponding esters of the hydroxy-alkane- I -sulfonic acids smch as 1,3propanesultonc and 1,4-butanesultone, and combinations of any two or more thereof 12. A process for the preparation of a composition according to claim 5 comprising, admixing the olefinic compound of any one of claims I to 4 with a further olefinic compound as defined in any of claims 6 to 10.
    63 13. A polymer comprising repeat units derived from a nitrogencontaining olefinic monomer having the formula r-% RI-C(R,)=C(Ri)-(C=O),,-N,_(R2)-Y-X-, wherein R, and R2 are each independently selected from hydrogen, alkyl radical, aryl radical, aralkyl radical, alkaryl radical, and combinations of any two or more thereof wherein each radical contains 1 to about 30 carbon atoms; each Y is independently selected from alkylene radical, phenyl group, imidazolium group, naphthyl group, biphenyl group, and combinations of any two or more thereof; each X is an anion selected from halide, sulfate, phosphate, nitrate, sulfonate, phosphonates, suffinate, phosphinate, and combinations of any two or more thereof; and each m is independently 0 or 1.
    14. A polymer according to claim 13 which further comprises repeat units derived from a nitrogen-containin olefinic comonomer having a formula C 9 ID selected from R,C(R)--C(Ri)-(C=O),.-(NH),,-(Ar).-N(Rz)(R,,)-y-SO3', R,C(R,)=C(R,)-(C--O),,,-(NH),,-(Ar),,,-Y-N(R,)(R,)-Y-(C=O),,,-N(R,D(R,)X-, R,C(Rj)=C(Rj)-(C=O),,,-N N"(R)-Y-(C=O),,I-N(R2)(R2)X-, RjC(Rj)=C(Rj)-(C-o),n-N N-Y-(C=O)m-N(R2)(R2)X, and combinations of any two or more thereof wherein RI, R2, Y, X and m are as def"Ined in claim 13, M is a substituted or unsubstituted morpholine group, and Ar is an arylene group.
    15. A polymer according to claim 14 wherein the nitrogen-containing olefinic cornonomer is selected from 64 N-acryloyl morpholine, N-acryloyl-N'-methyl piperwine, N-acryloyPN - ethyl piperazine, N-acryloyM'_propyl pine, N-acryloyl-N'-(2-amino-2- oxocthyl)-N'-methyI piperdznium chlorice, N-aicryloyl-N'-(3-aniino-3- oxopropyl)-N'-methyI piperazinium chloride. N-acryloyl-N'-(4-amino-4- oxobutyl)-N'-methyl piperazinium chloride, N-acryloyl-N'-(2-amino-2. oxoethyl)-N'-cthyl piverazinium chloride. N-acryloyl-N'-(3-amino--'1- oxopropyl)-N'-ethyl piperazinium: chloride, N-acryloyl-N'-(4-amino-4- oxobutyl)-N'-ethyI piperazinium chloride, N,N-dimethyl-N-(3-sulfopropyl)- N-(4-vinylbenzyl) ammonium inner salt N,N-dimethyl-N-(4-suifobutyl)-N-(4- vinylbenzyl) ammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-N-(4- vinylbenzyl) ammonium inner salt, N,N-diethyI-N-(4-sulfobutyl)-N-(4- vinylbenzyl) ammonium inner salt, N,N-dimethyl-N-(3-suIfopropyl)-N-(3- vinylbenzyl) ammonium inner salt, N,N-dimethyl-N-(4-sulfobutyl)-N-(3- vinylben2yl) ammonium inner salt, N,N-diethy]-N-(3-sulfopropyl)-N-(3- vinylbenzyl) ammonium inner salt, N,N-diethy]-N-(4-sulfobutyl)-N-(3 - vinyl benzy 1) ammonium inner salt, N,N-dimethyl-N-(2-amino-2-oxocthyl)-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-vinylbcnzyl) ammonium chloride, N-N-diethyl-N-(3-amino-3-exopropyi)-N(4-Yinylbcnzyl) ammonium chloride. N,N-dimethyl-N-(2-amino-2-oxocthyl)-N(3-vinylbcnzyl) 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-vinylbenzyl) ammonium chloride, N,N-diethyl -N-(3 -arnino-3 -oxopropy 1)-N-(3 -vinyl benZY1) ammonium chloride, N-(2-amino-2-oxoethyl)-N'-vinyl imidazolium, chloride, N-(3-amino-3-oxopropyl)-N'-vinyl imidazolium chloride, N-(4-amino-4-oxabutyl)-N'-vinyl imidazolium chloride, N,Ndimethyl-N-(3-sulfopropyl)-3-(acryloyl amino)- 1 -propaneammoniurn inner salt, N.N-diethyl-N-(3-sulfopropyl)-3-(acryloyI amino)- I -propanearnmonium inner salt, N,N-dimethyl-N-(4-sulfobutyl)-3-(acryloyI amino,)- I - propancammonium inner salt, N,N-diethyl-,N-(4-sulfobutyl)-3-(acryloyI arnino)- I -propaneammonium inner salt. N,N-dimethyl-N-(3-sulfopropyl)-2- (acryloyI amino)- I -ethaneammonium inner salt. N,N-diethyl-N-(3- sulfopropyl)-2-(acryloyI amino)- I -ethancammonium inner salt. N,Ndimethyl-N-(4-sulfoburyI)-2-(acryloyI amino)- I -ethaneammonium inner salt. N,N-diethyl-N-(4-sulfobutyl)-2-(acryloyI amino)- I -cdmcammonium inner salt, and combinations of any two or more thereof 16. A polymer according to any one of claims 13-15 further comprising repeat units derived from at least one olefinic comonomer having the formula selected from Rj-C(Rj)=C(Rj)-W, Rj-C(Rj)=C(Rj)-(C=O).-Z, Rj-C(R,)=C(Rj)-Y-W, RI-C(R,)=C(R,)-(C=O).-N(R,)-Y-R,, RI-C(R,)=C(R,)-(C=O).-G-Y-Z, RjC(R1)--C(Rj)-(C=O).-G-Y-W, R,-C(R,)=C(Rj)-(C--O).,-Y-7, and combinations of any two or more thereof wherein each R, and R2 are the same or different and are independently selected from hydrogen, alkyl radical, aryl radical, aralkyl radical, alkaryl radical, and combinations of any two or more thereof; each m is independently 0 or 1; Z has the formula selected from N(R2)(R2), N'(R2)(R2XR,)X- in which X is an anion sclected from halide sulfate, phosphate, nitrate, sulfonatc, phosphonates, sulfinatc, phosphinatc, and combinations of any two or more thereof, G is N(R,) or 0; each Y is independently selected from alkylene radical, phenyl group, imidazoliurn group, naphthyi group, biphcnyl group, and combinations of two or more thereof, and 66 W is an acid moiety selected from phosphinic acid, phosphonic acid, sulfinic acid, sulfonic acid, sulturic acid, sulfurous acid, carboxylic acid, phosphoric acid, ammonium salt or alkali metal salt of any of these acids, and combinations of any two or more thereof 17. A polymer according to any one of claims 13-15 further comprising ZD repeat units derived from at least one olefinic comonomer having the formula 0 selected from Rj-C(Rj)=C(Rj)-(C--O).,-Z, RI-C(R,)=C(R,)-(C=O).-Y-W, Rj-C(Rj)=C(Rj)-W, R,-C(R,)=C(Ri)-(C=O)-G-Y-W, and combinations of any two or more thereof wherein - each R, is the same or different and is independently selected from hydrogen, allql radical, aryl radical, aralkyl radical, alkaryl radical, and combinations of any two or more thereof, each m is independently 0 or 1; Z has the formula selected from N(R2)(R2), N'(R.)(R2)(Rz)X- in which X is an anion selected from halide sulfate, phosphate, nit-ate, sulfonate, phosphonates, sulfinatee, phosphinate, and combinations of any two or more thereof; G is N(R,) or 0; each Y is independently selected fmm &lkylene radical, phenyl group, imidazolium group, naphthyl group, biphenyI group, and combinations of two or more thereof; and W is an acid moiety selected from phosphinic acid, phosphonic acid, sulfinic acid, sulfonic acid, sulfuric acid, sulfurous acid, carboxylic acid, phosphoric acid. ammonium salt or alkali metal salt of any of these acids, and combinations of any two or more thereof 67 18. A polymer according to any one of claims 13-17 wherein said nitrogencontaininc, g.olefinic monomer is selected from N-acryloyl-N'-(3-sulfopropyl)-N'-methyI piperazinium inner salt, Nacryloyi-N'-(3-sulfopropyl)-N'-ethyI piperazinium inner salt, N-acryloylN'-(4-sulfopropyl)-N'-methyI piperazinium inner salt, N-acryloyi-N'-(4sulfopropyl)-N'-ethyI piperazinium inner salt.
    19. A polymer according to claim 17 wherein said nitrogen-containing I I I= olefinic monomer is N-acryloyl-N'-(3-sulfopropyl)-N-methyI piperazinium inner salt.
    20. A polymer according to claim 17 wherein said olefirlic comonomer is t) selected from acrylamide, styrene sulfonic acid, salt of styrene sulfonic acid, Nmethylacrylamide, N,N-dimethylacrylamide, acrylic acid, salt of acrylic acid, N-vinylpyrrolidone, methyl acrylate, methacryIate, vinyl sulfonic acid, salt of vinyl sulfonic acid, 2-acrylamido-2methylpropanesulfonic acid, salt of 2acrylamido-2-methylpropanesulfonic acid, and combinations of any two or more thereof 21. A polymer according to claim 20 wherein said olefinic comonomer is acrylamide.
    22, A water-soluble polymer comprising repeat units derived from at least one nitro ge n-containing olefinic monomer and at least one olefinic comonomer I C wherein said nitrogen-containing olefinic monomer has a formula r--\ -R,-C(R,)=C(R,)-(C=O),.-N,._,N'(RO-Y-X-, 68 gen-containing olefinic or a combination thereof with at least one further nitro, compound having the formula R,-C(Rj)=C(R,)-(C=O),,-M, Rj-C(Rj)=C(Rj)-(C=O),-N N(RI), RIC(Ri)--C(R,)-(C--O),,-(NH),,-(Ar).-N(RD(R,,)-Y-SO3, R,-C(P,,)=C(R,.)(C=O)m-(,NH),-(Ar),,-Y-N'(R2)(R2)-Y-(C=O),,,-N(RD(R,)X-, RIC(R,)=C(Ri)(C=O),,,-I,IN'(R2)-Y-(C=O),,-N(R2)(Rz)X-, RjC(Rj)=C(Rj)-(C=O).-N N-Y-(C=O),,-N(R,)(R,)X-.
    and said olefinic comonomer has the formula selected from RI-C(R,)=C(R,)-W, R,-C(R,)=C(R,)-(C=O),,-Z, R,-C(R,)=C(R,)-Y-W, R!-C(R, )=C(R,)-(C=O),,,-N(R,)-Y-R,, R,-C(R,)--C(R,)-(C=O),,-G-Y-Z, R,C(R,)=C(R,)(C=O),-G-Y-%N', R,-C(Rj)=C(R,.)-(C=O)-Y-Z wherein R, and R,. are each independently selected from hydrogen, alkyl radical, aryl radical, aralky-I radical. alkar-yl radical, and combinations of any two or more thereof wherein each radical contains I to about 30 carbon atoms, M is a substituted or unsubstituted morpholine group; eac Y is independently selected from -alkylene radical, phenyl group, imidazolium. group, naphthyl goup, biphenyl gmup, and combinations of any two or more thereof-, Ar is an arylene group; G is N(R) or 0; Z has the formula selected from N(R2)(Rz).
    N'(R,)(R2)(R,)X-, and combinations of any two or more thereof wherein X is an anion selected from the group consisting of halide, sulfate, phosphate, nitrate, sulfonate, phosphonates, sulfinate, phosphinate, and combinations of any two or more thereof, each m is independently 0 or 1; and W is an acid moiety selected from phosphinic acid, phosphonic acid, sulfinic acid, sulfonic acid, sulfuric acid, sulfurous acid. carboxylic acid, phosphoric acid, ammonium salt or alkali metal salt of an), of these acids, and combinations of any two or more thereof.
    69 23. A polymer according to claim 22 wherein said nitrogen-containing olefinic monomer is selected from N-acryloyl-N'-(3-sulfopropyl)-N-methyI piperazinimn inner salt, N- acryloyl-N'-(3-sulfopropyl)-N'-ethyI piperazinium inner salt, N-acryloyl- N'-(4-sulfopropyl)-N'-methyI piperamnium inner salt, N-acryloyl-N'-(4- sulfopropyl)-N'-ethyI pipemzinium inner salt.
    or a combination thereof with at least one further nitrogen-containing olefinic compound having the formula N-acryloyl morpholine. N-acryloyl-N'methyl piperazine, N-acryloyl-N'-ethyl piperazine, N-acryloyl-N'-propyl piperazine, N-acryloyl-N'-(2-amino-2-oxocthyl)-N'-methyI pipemzinium chloridc, N- acry toy I-N'-(3-amino-3 -oxopropyl)-N'-rnethyl piperazinium chloride, N-acryloyl-N'-(4-amino-4-oxobutyl)-N'-methyj Pipera2jldurn chloride, N-acryloyi-N'-(2-amino-2-oxoethyl)-N'-ethyl piperazinium chloride, N-acryloyl-N'-(3-amino-3-oxopropyl)-N'-ethyI PiPerazinium chloride, N-acryloyi-N'-(4-amino-4-oxobutyl)-N'-ethyl piperazinium chloride, N,N-dimethyl-N-(3-sulfopropyl)-N-(4-Yinylbenzyl) ammonium inner salt, N,N-d i methyl -N-(4-sulfobutyl)-N-(4-vinylbenzyl) ammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-N-(4-Yinylbenzyl) ammonium inner salt, N,N-dieth y 1 -N-(4 -sul fob utyl)-N-(4-viny IbenzyI) ammonium inner salt, N,N-dimethyl-N-(3-sulfopropyl)-N-(^)-viny[benzyl) ammonium inner &-dt, N,N-dimethyl-N-(4-suifobutyl)-N-(3-vinylbenzyl) ammonium inner salt, N,N-diethyPN-Q -sulfopropyl)-N-(3 -vinyl benzyl) 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-oxoethyi)-N-(4-vinylbenzyl) ammonium chloride, N,N-dimethyl-N-(3-amino-3-oxopropyl)-N-(4-vinylbenzyl) ammonium chloride.
    N,N-diethy]-N-(3-amino-3-oxopropyl)-N-(4-vinylbenzyl) ammonium chloride, N,N-dimethyi-N-(2-aminc-2-oxocthyl)-N-(3-vinylbenzyl) ammonium chloride, N,N-diethy]-N-(2-amino-2-oxoethyl)-N-(3-vinylbenzyl) ammonium chloride, N,N-dimethyl-N-(3-amino-3-oxopropyl)-N-(3-vinylbenzyl) ammonium chloride.
    N,N-diethyl-N-(3-arnino-3-oxopropyl)-N-(3-viny[benzyl) ammonium chloride, N-(2-amino-2-oxocthyl)-N'-vinyl imidazolium chloride, N-(3-amino-3-oxopropyl)-N -vinyl imidazolium chloride, N-(4-amincy-4-oxobutyl)-N'-vinyl imidazolium chloride, N,N-dimethyl-N-(3-sulfopropyl)-3-(acryloyl amino)- 1 -propaneammoniwn inner salt, N,N-diethyl-N-(3-suifopropyl)-3-(acryloyl amino)- 1 -propanearnmonium inner salt.
    N,N-dirnethyi-N-(4-suffobutyi)-3-(acryloyl arnino)-1-propaneammonium inner salt.
    N,N-diethyl-N-(4-sulfabutyl)-3-(acryloyI arnino)-1-propancammonium inner salt, zl 71 N,N-dimethyl-N-(3-suifopropyl)-2-(acryloyl amino)- 1 -Cthancammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-2-(acryloyl amino)- 1 -. ethaneammonium inner salt, N,N-dimethyl-N-(4-sulfobuty 1)-2-(acryloyl amino)- 1 -ethancarnmonium inner salt, N,N-diethyl-N-(4-sulfobutyl)-2- (acryloyI amino)-1-ethaneammonium inner salt, and combinations of any two or more thereof.
    24. A polymer according to claim 22 wherein said further nitroYen- 1 C1 containing olefinic comonomer is selected from 0 N,N-dimethyl-N-(3-sulfopropyl)-N-(4-vinylbenzyi) ammonium inner salt. N,Ndimethyl-N-(3-sulfobutyl)-N-(4-vinylbenzyl) ammonium inner sal., N,Ndiethyl-N-(3-sulfopropyl)-N-(4-Yinylbenzyl) ammonium inner salt, N,Ndiethy]-N-(3-suifobutyl)-N-(4-vinylbenzyl) ammonium inner salt, N,Ndimethyl-N-(3-sulfopropyl)-N-(3-vinylbenzyl) ammonium inner sal-, N,Ndimethyl-N-(3-sulfobut.vl)-N-(3-vinylbenzyl) ammonium inner sal N,Ndiethyl-N-(3-sWfopropyl)-N-(3-vinylbenzyl) ammonium inner salt, N.Ndiethyl-N-(3-sulfobutyl)-N-(3-vinylbenzyl) ammonium inner salt, Nacryloyl-N-rnethyl-N'-(2-arnino-2-oxoethyl) piperazinium chloride, Nacryloyl-N'-methyl-N'-(3-amino-3-,oxopropyl) piperazinium chloride, Nacryloyl-N'-methyl-N'-(4-arnino-4-oxobutyl) piperazinium chloride, Nacryloyl-N'-ethyl-N-(2-amino-2-oxoethyl) piperazinium chloride, Nacryloyl -N'-ethyl-N'-(3 -amino- 3-oxopropyl) piperazinium chloride, Nacryloyi-N'-.ethyl-N'-(4-amino-4-oxobutyl) piperazinium chloride, N,'Ndimethyl-N-(2-amino-2-oxoethyl)-N-(4-Yinylbenzyl) ammonium chloride, N,Ndiethyl-N-(2-amino-2-oxoethyl)-N-(4-vinylbenzyl) ammonium chloride. N,Ndimethyl-N-(3-amino-3-oxopropyl)-N-(4-vinylbenzyl) ammonium chloride, N,Ndiethyl-N-(3-amino-3-oxopropyl)-N-(4-vinylbenzyl) ammonium chloride, N-(2amino-2-oxoethyl)-N'-,vinylimidazolium chloride, N-(3-amino-3-oxopropyl)N'-vinylirnidazolium chloride, 72 N-(4-amino-4-oxobutyl)-N'-vinylimidazolium chlofide, and combinations of any two or more thereof.
    - A polymer according to claim 22 wherein said f urther nitrogencontaining olefinic monomer is N-acryloyl-N'-methyl piperazine.
    26. A polymer according to claim 22 wherein said nitrogen-containing olefinic monomer is N -a cry I oyl-N'-(3 -su I fopropyl)-N'-methy I piperazinium. inner salt.
    27. A polymer according to claim 22 wherein said f urther nitrogencontaining olefinic monomer is N-acryioyl-N'-(2-amino-2-oxoethyl)-N'methyI piperazinium chloride.
    28. A polymer according to claim 22 wherein said f urther nitro gencontaining olefinic monomer is 'N,N-dimethyl-N-(')-sulfopropyl)-N-(4vinylbenzyl) arnmonium inner salt.
    29. A polymer according to claim 22 wherein said f urther nitro gencontaining olefinic monomer is N,N-dimeth.vl-N-(2-amino-2-oxoethyl)-N-(4vinylbenzyl) ammonium chloride.
    30. A polymer according to claim 22 wherein said f urther nitrogencontaining olefinic monomer is N-(2-amino-2-oxoethyl)-N-vInyl imidazolium chloride.
    31. A polymer according to claim 22 wherein said f urther nitrogencontaining olefinic monomer is N,N-dimethyl-N-(3-sulfopropyl)-3-(acryloyI arnino)- I -propaneammonium inner salt.
    32. A polymer according to claim 22 wherein said f urther nitrogencontaining olefinic monomer is N-acrylovimorpholine.
    33. A polymer according to claim 22 wherein said olefinic comonorner is selected from - acrylamide, styrene sulfonic acid.
    salt of styrene sulfonic acid, N-methylacrylamide, N,N-dimethylacrylamide. acrylic acid, salt of acrylic acid, N-vinylpyrrolidone, methyl acrylate, me-thacrylate, vinylic 73 sulfonic acid, salt of vinylic sulfonic acid, 2-acrylamido-2- methylpropanesulfanic acid. salt 2-acrylamido-2-methylpropanesulfonic acid, and combinations of any two or more thereof 34. A polymer accordin-g to claim 33 wherein said olefinic comonomer is acrylarnide.
    3 )5. A water-soluble polymer comprising repeat units derived from at least one nitro gen-containing olefinic monomer and at least one olefinic comonomer wherein said nitrogen-containing olefinic monomer is selected from N-acryloyl-N'-(.3)-sulfopropyl)-N'-methyl piperazinium inner salt, ,N-acryloyi-N'-(3-sulfopropyl)-N'-ethyI piperazinium inner salt, \-acryloyl-N'-(4-sulfopropyl)-N'-methyI piperazinium inner salt, N-acryloyl-N'-(4-sulfopropyl)-N'-ethyI piperazinium inner salt, or a combination thereof with at least one further nitrogen-contatrung compound selected from the group consisting of N-acryloyl morpholine, Nacryloyl-N'-methyl piperazine, N-acryloyi-N'-ethyl piperazine, N-acryloylN'-propyl piperazine, N-acryloyl-N'-(2-amino-2-oxocthyl)-N'-methyI piperazinium chloride, N-acryloyi-N'-(3-amino-3-oxopropyl)-N'-methyI piperazinium chloride,,,4-acr-yloyi-N'-(4-amino-4-oxobutyl)-N'-methyI piperazinium chloride, N-acryloyl-N'-(2-amino-2-oxoethyl)-N'-ethyI piperazinium chloride, N -acry loyl-N'-(3 -amino- 3 -o xopropy 1) -N'ethyl piperaziniurn chloride, N-acryloyl-N'-(4-amino-4-oxobutyl)-N'-ethyI piperazinium chloride, N,N-dimethyl-N-(3-sulfopropyl)-N-(4-vinylbenzyl) arnrrionium inner salt, 'N,N-dimethyl-N-(4-sulfobutyl)-N-(4-vinylbenzy]) ammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-N-(4-vinylbenzy]) ammonium inner salt, N,N-diethyl-N-(4-sulfobutyl)-N-(4-vinylbenzy)) ammonium inner salt, N,N-dimeLhyl-N-(3-sulfopropyl)-N-(3-vinylbenzyl) ammonium inner salt, N,N-dimethyl-N-(4-sulfobutyl)-N'-(3-vinylbenzyl) ammonium inner salt,,,;,N-diethyl-N-(3-sulfopropyl)-N-(3-vinylbenzyl) ammonium inner salt, 74 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-arnino-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.
    T\I.N-dimethyl-N-(3-amino--'3-oxopropyl)-N-(3-vinylbenzyl) ammonium chloride, N,N-diethyl-N-(3-amino-3-oxopropyl)-N-(3-vinylbenzyl) ammonium chloride, N-(2-arnino-2-oxoethyI)-N'-vinyI imidazolium chloride, N-(3-amino-3-oxopropyl)-N'-vinyI imidazolium chloride, N-(4-amino-4-oxobutyl)-N'-vinyl imidazoliurn chloride, N,N-dimethyl-N-(3-sulfopropyl)-3-(acryloyI amino)-1-propaneammonium inner sall., N,N-diethyl-N-(3-sulfopropyl)-3-(acryloyI amino)- I -propaneammoniurn inner salt.
    N,N-dimethyl-N-(4-sulfobutyl)-3-(acryloyI arnino)-l-propaneammonium inner salt, N,N-diethyl-N-(4-sulfobutyl)-3-(acryloyI amino)- I -propaneammonium inner salt, N,N-dimethyl-N-(3-sulfopropyl)-2-(acryloyI amino)- I -ethaneammonium inner salt, N,,N-diethyl-N-(3-sulfopropyl)-2-(acryloyI amino)- I -ethaneammonium inner salt.
    N,N-dimethyl-N-(4-sulfobutyl)-2-(acryloyI amino)- I -ethaneammonium inner salt.
    N,N-di ethyl -'-,N-(4-sulfobutyl)-2-(acryloyI amino)- I -ethaneammonium inner salt. And said olefinic cornonomer is selected from acrylarnide, styrene sulfonic acid, salt of styrene sulfonic acid, N- methylacrylamide.
    N,,N-dimethylacrylamide, acrylic acid, salt of acrylic acid, N-vinylpyrro I i done, mcthyl 2crylate, methacrylate, vinylic. sulfonic acid, salt of vinylic sulfonic acid.
    2-acrylamido-2-methylpropanesulfonic acid, salt 2-acrylaTnido-2-methylpropanesulfonic acid, and combinations of any two or more thereof 36. A polymer according to claim 35 wherein said further nitrogen- containing olefinic monomer is N-acryloyl-N'-rnethyl piperazine.
    37. A polymer according to claim 35 wherein said nitrogen-containing olefinic monomer is N-acryloyi-N'-(3-sulfopropyl)-N'-methyI piperazinium inner salt.
    38. A polymer according to claim 35 wherein said further nitrogencontaining olcfinic monomer is N-acryloyl-N'-(2-amino-2-oxoethyl)-N'-methyI piperazinium chloride.
    39. A polymer according to claim 35 wherein said further nitrogencontaining olefinic monomer is N,N-dimethyl-N-(3-sulfopropyl)-N-(4-vinylbenzy]) arnmonium inner sat- 40. A polymer according to claim 35 wherein said further nitrogen- containing olefinic monomer is N,N-dimethyl-N-(2-aaiino-2-oxocthyl)-N-(4-vinylbenzyl) an-Lmoniurn chloride.
    41. A polymer according to claim 35 wherein said further nitrogencontaining olefinic monomer is N-(2-amino-2-oxoethyl)-N'-vinyl imidazolium chloride.
    42. A polymer according to claim 5 wherein said further -dimethyl-N-("-sulfopropyt')-3-(acryloI nitrogen-containing olefinic monomer is N,N ami-io)- I -propaneammonjum inner salt.
    43. A polymer according to claim35 wherein said further nitro gencontaining olefinic monomer is N-acryloylmorpholine.
    44. A polymer according to cWm35 wherein said olefinic comonomer is acrylamide.
    45- A process comprising introducing a water-soluble composition into a subterranean formation wherein said composition comprises a polymer comprising repeat units derived from a nitrogen-containing olefinic monomer 76 comprising repeat units derived from a nitrogen-containing olefinic monomer I I having the formula R,-C(Rj)=CRj)-(C=O).,-N N'(R2)-Y-X-.
    or a combination thereof with at least one further nitrogen-containing olefinic compound having the formula Rj-C(R,)=C(Rj)-(C=O),-M, R,-C(R,)=C(R,)-(C=O),,-NF N(R), R,C(R,)=C(R,)- (C=O),,-(NH),,-(A.r),,,-N(R )(R2)_Y_SO3 R,-C(R,)=C(R,)-(C=O),,-(NH),,-(Ar),,-Y-N-(R2)(R,)-Y-(C=O),-N(R,)(R,)X-, r_I\ R,C(Rj)=C(Rj)-(C=O),,-N N(R,)-Y-(C=O),,,-N(R2)(R2)X', R,C(R,)=C(R,)-(C=O),,,-N N-Y-(C=O),,-N(R,)(R2)X %fy-,re:Ln each R, and R, arc the same or different and independently selected ftom hydrogen, alkyl radical, aryl radical, aralkyl radical.
    alkaryl radical, and combinations of any two or more thereof wherein each radical contains I to about 30 carbon atoms; M is a substituted or unsubstituted morpholine group; each X is an anion selected from halide, sulfate, phosphate, nitrate, sulfonate, phosphonates, sulfinate, phosphinate, and combinations of any two or more thereof, each Y is independently selected from alkylene radical, phenyl group, imidazolium group, naphthyl group, biphenyl group, and combinations of any two or more thereof, Ar is an arylene group; and each m is independently 0 or 1.
    46. A process according to claim 45 wherein said polymer further comprises repeat units derived from at least one olefinic comonorner having the formula selected from R,-C(R,)=C(R,)-W, R,-C(R,)=C(R,)-(C--O),, -Z. R,-C(R,)=C(R,)-Y-W, 77 RI-C(Rl)=C(R,)-(C=O),.,:..N(R2)-Y-R2, Rj-C(RI)=C(Rj)-(C=O),,,-G-Y-Z, RjC(Rj)=C(Rj)-(C=O),,,-G-Y-W, Rj-C(Rj)=C(R0-(C=O).-Y-Z, and combinations of any two or more thereof wherein each R, and R2 are the same or different and are independently selected from the group consistmg of hydrogen, alkyl radical, aryl radical, aralkyl radical, alkaryl radical, and combinations of any two ormore thereof, each m is independently 0 or 1. M is a substituted or unsubstituted morpholine; 7 has the formula selected from the group consisting of N(R,)(R-,), N'(R,)(R2)(R,)X- in which X is an anion selected from the group consisting of halide. sulfate, phosphate, nitrate, suffonate, phosphonates, sulfinate, phosphinate. and combinations of any two or more thereof-, G is N(R) or 0; each Y is independently selected from the group consisting of alkylene radical, phenylene group, imidazoliurn group, naphthylene group, biphenylene group. and combinations of two or more thereof, and 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 salt or alkali metal salt of any of these acids, and combinations of any two or more thereof.
    47. A process according to claim 45 or 46 wherein said nitrogencontaining olefinic monomer is in combination with at least one further nitrogen- containing olefi.nic compound selected from N,N-di.methyl-N-(3-sulfopropyl)-N-(4- vinylbenzyl) ammonium inner salt, N,N-dimethyl-N-(3-sulfobutyl)-N-(4- vinylbenzyl) ammonium irmer salt, N,N-diethyl-N-(3-sulfopropyl)-N-(4- vinylbenzyl) ammonium inner salt, N,N-diethyl-N-(3-sWfobutyl)-N-(4- viriylbenzyl) ammonium inner salt, N.N-dimethyl-N-(3-sulfopropyl)-,N-(3-, vinylbenzyl) ammonium inner salt,,N.,,,-dimethyl-,N47-(3-sulfobutyl)-N-(3- vinylbenzyl) ammonium inner salt, 73 N,N-diethyl-N-(3-sulopropyl)-N-(3-vinylbenzyl) ammonium inner salt, N, N-diethyl-N-(3-sulfobutyl)-N-(3-vinylbenzyl) ammonium inner salt, N- acryloyi-N-mcthyl-N'-(2-amino-2--oxoethyl) piperazinium chloride, Nacryloyl-N'-methyl-N'-(3-amino-3-oxopropyl) piperazinium chloride, Nacryloyl-N'-methyl-N'-(4-amino-4-oxobutyl) piperazinium chloride, Nacryloyl-N'-ethyl-N'-(2-amino-2-oxoethyl) piperazinium chloride, Nacryloyl-N'-ethyl-N'-(3-amino-3-oxopropyl) piperazinium chloride, Nacryloyl-N'-ethyl-N'-(4-amino-4-oxobut,vl) piperazinium chloride, N,Ndimethyl-N-(2-amino-2-oxoethyl)-N-(4-vinylbenzy]) ammonium chloride, N,Ndiethyl-N-(2-amino-2-oxcethyl)-N-(4-vinylbenzy]) ammonium chloride, N,Ndimethyl-N-(3-amino-3-oxopropyl)-N-(4-vinylbenzy]) ammonium chloride. N,Ndiethyl-N-(-')-amino-3-oxopropyl)-N-(4-vinylbenzyl) amrrionium chioride. N-2-amino-2-oxoethyl)-N'-vinylimidazolium chloride, N-(3-amino-3oxopropyl)-N'-vinylimidazollum chloride, N-(4-amino-4-oxobutyl)-N'vinylimidazollum chloride, and combinations of any two or more thereof.
    48. A process according to claim 46 wherein said olefinic corrionomer is acrylamide.
    49. A process according to claim46 wherein said further - -methyl piperazine.
    nitrogen-containing olefinic monomer is N-acryloyl-N' 50. A process according to claim46 wherein said rutrogen-containing olefinic monomcr is N-acryloyl-N'-(3-sulf6propyl)-N -methyl piperazinium inner salt.
    51. A process according to claim 46 wherein said further nitrogencontaining olefinic monomer is N-acryloyl-N'-(2-amino-2-oxoethyl)-N'methyi piperazinium chloride.
    52. A pol= according to claim 4-6 wherein said further nitrogencontaining olefinic monomer is N,N-dimethyl-N-(')-sulfopropyl)-N-(4vinylbenzyl) ammonium inncr salt.
    53. A polyrrer according to claim 46 wherein said further nitro gencontaining olefinic monomer is N,N-dimethyl-N-(2-amino-2-oxoethyl)-N-(4vinylbenzyl) arnmoniurn cl-donde.
    79 54. A process according to claim 46 wUrein said nitro gen-containing olefinic monomer is N-(2-amino-2-oxoethyl)-N'-Vinyl imidazolium chloride.
    55. A process according to claim 46 wherein said fur-d-yar nitrogencontaining olefinic monomer is NN-dimethyl-N-(3-sulfopropyl)-3-(acrvloyI amino)- I -PTOpaneammoniurn inner salt.
    56. A process according to claim 46 wherein said further nitrogencontaining olefinic monomer is N-acryloylmorpholine.
    57- A composition comprising a water-soluble polymer, a crosslinking agent, and a liquid wherein said polymer is recited in any of claims 1344.
    58- A composition according to claim'.S7 wherein said crosslinking 0 agent is a multivallent metal compound in which the metal of said metal compound is selected from the group consisting of Al, Cr, Fe, Ti, and combinations of any two or more thereof.
    59. A composition according to claim 57 wherein said crosslinking agent is selected from a zirconium compound, a titanium compound, a chromium compound, an aluminum compound, and combinations of any rwo or more thereof.
    60. A composition according to claim 57 wherein said crosslinking agent is selected from. zirconium citrate, zirconium complex of hydroxyethyl glycine, ammonium zirconium fluoride, zirconium 2- ethylhexanoate, zirconium acetate, zirconium neodecanoate, zirconium acetylacetonate, ceirakis(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 citrate, chromium acetate, chromium propionate, chromium malonate, and combinations of any two or more thereof 61. A composition according to claim 57 wherein said crosslinking agent comprises two components in which the first component is selected from phenol, substituted phenols, aspirin, p-aminobenzoic acid, resorcinol, catechol, hydroquinone, furfuryl alcohol, RArO (C=O),, W, 110Ar (C=O) OT, HOArOH, TOArOH, R'OArOR', or combinations of any two or more thereof wherein Ar is non-substituted or substituted arylene group; each R' can be the same or different and is each independently selected ftom. hydrogen, carboxylic group, a C,-C, alkyl, a phenyl group or combinations of any two or more thereof., and each m is independently 0 or 1; and the second component is selected from aldehydes, aldehyde-generating compounds, and combinations of any two or more thereof 62. A composition according to claim 57 wherein said crosslinking agent comprises two components in which the first component is selected from phenol, hydroquinone, resorcinol, catechol,p-aminesalicylic acid, furfuryl alcohol, phenyl acetate, phenyl propionate, phenyl butyrate, salicylic acid, phenyl salicylate, aspirin, p-hydroxybenzoic acid, methyl p-hydroxybew.oate, methyl p-aminoberizoic acid, o-hydroxybenzoate, ethyl p-hydroxybenzoate, o-hydroxybenzoic acid, hexyl p-hydroxybcnzoate, and combinations of any two or more thereof, and the second component is selected from, formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, decanal, glutaraldehyde, terephthaldehyde, hexamethylenetetramine, and combinations of any two or more thereof.
    63. A composition according to claim 57 wherein said liquid is a produced brine- 64. A process comprising introducing a gelling composition into a subterranean formation wherein said composition is recited in any of claims SIT-63.
    81 65. A composition comprising a clay, a polymer, and a liquid wherein said polymer is recited in any of claims 13-44.
    66. A composition according to claim 65 wherein said olefinic comonomer is selected from the group consisting of acrylamide, styrene sulfonic acid, salt of styrene sulfonic acid, N-methylacrylamide, N,Ndimethylacrylamide, acrylic ac](L salt of acrylic acid, Nvinylpyrrolidone, methyl acrylate, methacrylate, vinyl sulfonic acid, salt of vinyl sulfortic: acid, 2-acrylamido-2-methylpropanesulforc acid, salt of 2-acrylamido-2-methylpropanesulfonic acid, and combinations of any two or more thereof.
    67. A composition according to claim 65 wherein said clay is bentonite.
    68. A process comprising introducing a composition into a subterranean formation wherein said composition is recited in claims 65-67.
GB9926318A 1995-12-20 1996-11-13 Compositions and processes for treating subterranean formations Expired - Lifetime GB2340832B (en)

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US08/575,429 US5708107A (en) 1995-12-20 1995-12-20 Compositions and processes for treating subterranean formations
US08/575,434 US6051670A (en) 1995-12-20 1995-12-20 Compositions and processes for treating subterranean formations
US08/723,635 US5922653A (en) 1995-12-20 1996-10-03 Compositions and processes for treating subterranean formations
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