CA2241362C - Compositions and processes for treating subterranean formations - Google Patents

Compositions and processes for treating subterranean formations Download PDF

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Publication number
CA2241362C
CA2241362C CA002241362A CA2241362A CA2241362C CA 2241362 C CA2241362 C CA 2241362C CA 002241362 A CA002241362 A CA 002241362A CA 2241362 A CA2241362 A CA 2241362A CA 2241362 C CA2241362 C CA 2241362C
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amino
acryloyl
vinylbenzyl
chloride
inner salt
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CA2241362A1 (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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ConocoPhillips Co
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ConocoPhillips Co
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Priority claimed from US08/575,434 external-priority patent/US6051670A/en
Priority claimed from US08/575,429 external-priority patent/US5708107A/en
Priority claimed from US08/575,928 external-priority patent/US5650633A/en
Priority claimed from US08/723,635 external-priority patent/US5922653A/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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/02—Well-drilling compositions
    • C09K8/04—Aqueous well-drilling compositions
    • C09K8/06—Clay-free compositions
    • C09K8/12—Clay-free compositions containing synthetic organic macromolecular compounds or their precursors
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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
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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
    • C09K8/62—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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    • 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
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    • 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

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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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Abstract

Compositions and processes for using the compositions for applications in a subterranean formation are provided. The compositions include a composition which comprises a nitrogen-containing olefinic compound;
a composition comprises a water-soluble polymer prepared from the nitrogen-containing olefinic compound and optionally an olefinic comonomer; a composition which comprises the water-soluble polymer, a cross-linking agent, and a liquid; and a composition which comprises a clay, the water-soluble polymer, and a liquid. These compositions can be used as or in compositions for enhanced oil recovery, drilling fluids, workover fluids, completion fluids, or combinations of any two or more thereof.

Description

WO 97!22638 PCT/US96/18174 COMPOSITIONS AND PROCESSES FOR TREATING
SUBTERRANEAN FORMATIONS
FIEIaD OF THE INVENTION
The present invention relates to compositions which can be used to prepare water-soluble polymers that are useful in oil field applications and processes for producing the compositions; to water-soluble polymers which can be prepared from the compositions and nitrogen-containing olefinic compounds as well as processes for producing and using the water-soluble polymers; and to gelling compositions produced from the water-soluble polymers for applications in a subterranean formation such as, for example, altering permeability and correcting water coning problems and processes for producing and using the gelling compositions.

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 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
2 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.
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 ail, 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. Mast 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 ea;ample a few days, at high temperature, such as for example, 120°C 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 through the interaction with the oxygen atoms of the polymer molecules. 'therefore, tree gellable polymers generally contain
3 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 10-30 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 gelation 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 the 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 described above.
1$ There is therefore an increasing demand 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 and/or 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 that such drilling fluids exhibit a low rate of filtration or water loss, that is, the drilling fluid must prevent excessive amounts of fluid, or "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
4 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 Z 5 centipoise mud S which can be prepared from one ton of clay) of relatively low-grade clays have been used.
Excessive fluid Ioss 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 reduce, 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 and/or lose viscosity as well as effectiveness as water loss additives when exposed to dissolved electrolytes, particularly when divalent metal cations such as Ca+2 and Mg+Z are present. In drilling fluids, the resulting vulnerability to breakdown is exacerbated by the density of drilling mud, which is directly related to weighting agents required for a given formation pressure.
Breakdown of polymers causes a large increase in the fluid loss accompanied by an increase in filter cake thickness. These conditions often result in differential sticking of the drill string. It is, therefore, desirable to develop additives which enable drilling fluids to retain their proper viscosity and fluid content over a broader range of conditions.
Drilling fluids are used in the drilling of various types of wells.
Workover and completion fluids, in contrast, are those fluids used in the completion and servicing of such wells. Completion fluids are those fluids used after drilling is complete and during the steps of completion, or recornpletion, 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.
1 Q 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 Workover 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 environment-withstanding gelling composition, containing the hostile environment-withstanding polymer, that can form stable gels in a liquid such as, for example, produced brines, for near-wellbore as well as in-depth treatments, and preferably that does not require a gelation delaying agent, is highly desirable. It is also highly desirable to develop a composition which can be used in drilling fluids, completion fluids, or Workover fluids.

SUMMARY OF THE INVENTION
An object of the invention is to provide a composition which can be used as a monomer to synthesize a hostile environment-withstanding, water-soluble polymer. Another object of the invention is to provide a process for synthesizing the composition. Yet another object of the present invention is to provide a water-soluble polymer that can be used to form a geI in a hostile environment in hydrocarbon-bearing subterranean formations. Also an object of the invention is to provide a process for altering the permeability of hydrocarbon-bearing subterranean formations using the water-soluble polymer or for other drilling applications.
A
- further object of the invention is to provide a gelling composition which contains the water-soluble polymer and withstands a hostile environment. 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 environmentally suitable for use in subterranean formations. Still a further object of the invention is to provide a process for various drilling applications or for altering the permeability of hydrocarbon-bearing subterranean formations with a gelling composition that does not require a gelation delaying agent.
Yet still another object of the invention is to provide a process for treatment of subterranean formations employing a gelling composition that is environmentally 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 apparent as the invention is more fully disclosed hereinbeiow.
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 WO 97/22638 PCT/US9b/18174 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 Ieast one nitrogen-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 derived 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 derived from at least one nitrogen-containing olefinic compound.
According to a sixth embodiment of the present invention, a process is provided which comprises introducing into a subterranean formation a gelling composition comprising a water-soluble polymer, a crosslinking agent, and a liquid wherein the gelling composition forms gels when introduced into the formation and the water-soluble polymer comprises repeat units derived from at least one nitrogen-containing olefinic compound.
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 g 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.
gETAILED DESCRIPTION OF THE INVENTION
According to the first embodiment of the present invention, a composition useful as a monomer for synthesizing a water-soluble polymer is provided. The composition comprises, or consists essentially of, or consists of a nitrogen-containing oleiinic compound having the formula selected from the group consisting of sulfobetaines, vinylic amides, and combinations of any two or more thereof wherein the sulfobetaine has the formula of RFC(R,)---C(Ry-(C=O)m-~(Ar)m-Y-N'(Rz)(R~)-1'-S03' and the vinylic amide has the formula of RnC(Ri)=C(Rc)-(C'O)~-(NH)m-(~')m-Y-N+(R~(Rz)-Y-(C~)~-N(Rz)~~X' n R~C(RW'C(Rc)-(C=O)m N~ '(Rz)-Y-(C=C)~-N(R2)(Ra~x'~
R,C(R~)=C(R,)-(C=O)~,-~ ~N'-Y-{C=O),~-N(RZ)(R~X~, or combinations of any two or more thereof. R, and Ri can be the same or different and are each independently selected from the group consisting of hydrogen, alkyl radicals, aryl radicals, aralkyl radicals, alkaryl radicals, and combinations of any two or more thereof wherein each radical can contain 1 to about 30, preferably 1 to abut 20, more preferably 1 to about 15, and most preferably 1 to 10 carbon atoms and can contain functional groups) such as ammonium, hydroxyl, sulfate, ether, carbonyl groups, amine groups, sulfhydryI 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 phenylene grout>, an imidazolium group, a naphthylene group, a biphen-ylene group, or combinations of any two or more thereof. Each Y is preferably independ-ently an alkylene radical H~hich 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 to about 5 carbon atoms. Ar is an arylene radical, preferably a phenylene group, which can be substituted or unsubstituted. X is an anion selected from the group consisting of halides, sulfates, phosphates, nitrates, sulfonates, phosphonates, sulfinates, phosphinates, and combinations of any two or more thereof. Each m can be the same or dii~'erent and is 0 or 1.
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-sulfoprapyl)-N-{4-vinylbenzyl) ammonium inner salt, N,N-diethyl-N-(3-sulfobutyl)-N-(4-vinylbenzyl) ammonium inner salt, N,N-dimethyl-N-(3-sulfopropyl}-N-(3-vinylbenzyl) ammonium inner salt, N,N-dimethyl-N-(3-sulfobutyl)-N-(3-vinylbenzyl) ammonium inner salt, N,N-diethyl-N-(3-sulfoprapyl)-N-(3-vinylbenzyl) ammonium inner salt, N,N-diethyl-N-(3-sulfobutyl)-N-(3-vinylbenzyl) ammonium inner salt, N-acryloyl-N'-methyl-N'-(2-amino-2-oxoethyl) piperazinium chloride, N-acryloyl-N'-methyl-N'-(3-amino-3-oxopropyl) piperazinium chloride, N-acryloyl-N'-methyl-N'-{4-amino-4-oxobutyl) piperazinium chloride, N-acryloyl-N'-ethyl-N'-(2-amino-2-oxoethyl) piperazinium chloride, N-acryloyl-N'-ethyl-N'-(3-amino-3-oxopropyl) piperazinium chloride, N-acryloyl-N'-ethyl-N'-(4-amino-9~-oxobutyl) piperazinium chloride, N,N-dimethyl-N-(2-amino-2-oxoetlryl)-N-{4-vxnylbenzyl) ammonium chloride, N,N-diethyl-N-(2-amino-s!-oxoethylrN-(4-vinylbenzyl) ammonium chloride, N,N-dimethyl-N-(3-amino-~-axopropyl)-N-(4-vinylbenzyl) ammonium chloride, N,N-diethyl-N-(3-amino-a-oxopropyl)-N-{4-vinylbenzyl) ammonium chloride, N-(2-amino-2-oxoethyl)-rd'-vinylirnidazolium chloride, N-{3-amino-3-oxopropyl)-N'-vinylimidazolium chloride, N-(4-amino-4-oxobutyl)-N'-vinylimidazoiium chloride, and combinations of any two or more thereof.
The nitrogen-containing olefinic compounds of the f rst embodiment of the invention can be prepared by the process disclosed hereinbelow in the second S embodiment of the invention.
In the second embodiment of the present invention, a process for preparing the nitrogen-containing olefinic compounds is provided. The nitrogen-containing olefinic compounds having the formula of RIC(Rl)=C(Rl)-(C=O)~ (NH)~"-(Ar)m Y-N+(RZ)(RZ)-Y-S03' (a sulfobetaine), can be produced by contacting a vinylic tertiary amine with an alkylating agent such as, for example, an alkylsulfonic acid containing a proper leaving group such as halide, hydroxyl, tosylate, other suitable leaving groups, or combinations of any two or more thereof. 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 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 temperature 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 1 to about 10 days, preferably about 1 to about 8 days, and most preferably 1 to 5 days under any suitable pressures such as, for example, about 1 atmospheric pressure. A suitable radical inhibitor such as 1,3-dinitrobenzene can be added to prevent polymerization of the nitrogen-containing olefinic compounds during the contacting. Preferably the production is carned out by using 1,3-propanesultone or I,4-butanesultone as the alkylating reagent in toluene by heating at 45-50°C for 72 hours. The sulfobetaine generally precipitates from the solvent and can be purified by filtration, repeated washing with any common organic solvent that does not dissolve the sulfobetaine, and finally dried under reduced pressure. Preferably diethyl ether is used to wash the sulfobetaine during filtration, WO 97!22638 PCT/US96/18174 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-vinylbenzyl) amine, N,N-dimethyl-N-(4-vinylbenzyl) amine, N,N-diethyl-N-(4-vinylbenzyl) amine, N,N-diethyl-N-(4-vinylbenzyl) amine, N,N-dimethyl-N-(3-vinylbenzyl) amine, N,N-dimethyl-N-(3-vinylbenzyl) amine, N,N-diethyl-N-(3-vinylbenzyl) amine and N,N-diethyl-N-(3-vinylbenzyl) amine, and combinations of any two or more thereof.
Examples of suitable alkylating reagents include, but are not limited to, 3-chloro-propane-1-sulfonic acid, 4-chloro-butane-1-sulfonic acid, 3-hydroxy-propane-1-sulfonic acid, 4-hydroxy-butane-1-sulfonic acid, the corresponding esters of the hydroxy-aikane-1-sulfonic acids such as 1,3-propanesultone and 1,4-butanesultone, and combinations of any two or more thereof.
1$ The nitrogen-containing olefinic compounds with the amide functional group of the first embodiment of the invention have general formulae of RiCCRF)=CCR~)-(C=O)m ~H)m (~')m Y-N+(Rz)(Rz)-Y-(C=O)m N(Rz)(Ra)X
R,C(Rl)=C(RI)-(C=O)m N +(Rz)-Y-(C=O)m N(Rz)(Rz)X-, n R1C(Rl)=C(R,)-(C=O)m N _ N+-Y-(C=O)m N(Rz)(Rz)X-, and combinations of any two or more thereof. These compounds can be produced by alkylation of a vinyl-substituted amine 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, benzene, pentane, hexane, acetonitrile, methanol, ethanol, any other common organic solvents, or combinations of any two or more thereof. Generally, a vinyl-substituted amine and an alkylating agent can be contacted under a condition including a temperature in the WO 97!22638 PCT/LTS96/18174 range of from about 10 to about i 50 °C, preferably about 20 to about 120 °C, and most preferably 30 to 100°C for about 1 to about IS days, preferably 1 to 8 days under any suitable pressure such as, for example, about I 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 alkylating agent in acetonitrile by heating at 45-80°C for 50-150 hours. The nitrogen-containing olefinic compounds generally precipitate from the solvent and can be purified by filtration, repeated washing with any common organic solvent that does not dissolve the nitrogen-containing olefinic compounds, and finally dried under reduced pressure.
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-(4-vinylbenzyl) amine, N,N-diethyl-N-(4-vinylbenzyl) amine, N,N-diethyl-N-(4-vinylbenzyl) amine, N,N-dimethyl-N-(3-vinylbenzyl) amine, N,N-dimethyl-N-(3-vinylbenzyl) amine, N,N-diethyl-N-(3-vinylbenzyl) amine and N,N-diethyl-N-(3-vinylbenzyl) amine, and combinations of any two or more thereof.
Examples of suitable alkylating agents include, but are not limited to, 2-chloro-acetamide, 2-bromo-acetamide, 3-chloro-propaneamide and 3-bromo-propaneamide, 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 effect 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 0.01:1, preferably about 1:0.05 to about 0.05:1, and most preferably 1:0.1 to 0.I :1. The molar ratio of the radical inhibitor to the amine can be in the range of from about 0.1:1 to about 1,000:1. The WO 97!22638 PCTlUS96/18174 molar ratio of the solvent to the amine can be any ratio that is effective in the production of a nitrogen-containing olefmic 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, repeat units derived from 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 polymerizable ethylenic linkage and being capable of producing a polymer which withstands hostile environment can be used for preparing the water-soluble polymer of the third embodiment of the present invention. Though it is not necessary, it is preferred that the ethylenic linkage be at the terminal end of the nitrogen-containing olefin molecule and that at least one nitrogen be a tertiary amine. The presently preferred repeat units include, but are not limited to R~-C(Rt)=C(R~)-(C=O)m-M, RwC(RO=CW )-(C=O)m ~ (R~)~ Ri-C(RO=CCW )-(C=O)m ~ +(Rz)-Y-X
RiCW )=CW )-(C=O)m ~)m (~')m N+~z)~a)-Z'-SOs RmC(Ri)=CW )-(C=O)m ~m (~')m Y N+(Rz)(R2)-Y-(C=O)m N~zOR2)X-R,C(R,)=C(R,)-(C=O)m ~ +(R)-Y-(C°O)m N(Ra)(R~X-n R1C(R,)=C(Rt)-(C=O)m NVN+-Y-(C=O)m N(Rz)(Rz)X-, and combinations of any two or more thereof. R, and RZ 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 I 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, RZ is hydrogen, methyl, ethyl, or combinations of any two ar mare thereof. M is a morpholine group which can be substituted ~:>r unsubstituted. Y is an alkylene radical, a phenylene group, an imidazolium group, a napht:hylene group, a biphenylene group, or combinations of any two or more thereof which can :have 1 to about 20, preferably I to about 15, and most preferably 1 to 10 carbon atoms. Most preferably, Y is a short alkylene radical having 1 to about 5 carbon atoms. Ar is an arylene radical, preferably phenylene, which can be substituted or unsubstituted" X is an anion selected from the group consisting of halides, sulfate, phosphate, nitrate, sulfonates, phosphonates, sulfinates, phosphinates, and combinations of any two or more thereof. Each m can be the same or different and is independently 0 or 1, The water-soluble polymer of the third embodiment of the present invention can be a homopolymer, copolymer, terpolymer or tetrapolymer.
However, if the nitroen-containing ol.efinic repeat units contain an amide group, it is preferred that the water-soluble polymer be derived from repeat units comprising at least one of the nitrogen-containing olefmic compounds described above and at least one olefinie comonomer selected from the group consisting of R,-C(R,}=C(R,)-w, RnC~n=CW )-(C=O)m Z~ RnCW .)~~nY-W~
R,-C(R,)=C(R~)-(C=O),~ hI(R~-Y-Ri, R,-C(R,~(R,~(C=O)m G-Y-Z, R,C(R,)~(R,~(C=O)~,-r-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(R~(R2), N+(R2)(R~(R~)X', and combinations of any two or more thereof wherein X is an anion selected from the group consisting of halides, sulfate, phosphate, nitrate, sulfonates, phosphonates, sulfinates, phosphinates, and combinations of any two or more thereof. M, Y, R,, and R, are the same as those disclosed above. The letter m is 0 or I. G is N(R,) or O. W is an acid moiety selected from the group consisting of phosphinic acid, phosphonic acid, sulfinic acid, sulfonic acid, sulfuric acid, sulfurous is acid, carboxylic acid, phosphoric acid, ammonium 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 invention include, but are not limited to, N-acryloyl morpholine, N-acryloyl-N'-methyl piperazine, N-acryloyl-N'-ethyl piperaxine, N-acryloyl-N'-propyl piperazine, N-acryloyl-N'-(3-sulfopropyl)-N'-methyl piper~zinium inner salt, N-acryloyl-N'-(3-sulfoprop;yl)-N'-ethyl piperazinium inner salt, N-acryloyl-N'-(4-sulfobutyl)-N'-methyl piperazi:nium inner salt, N-acryloyl-N'-(4-sulfobutyl)-N'-ethyl piperazinium inner salt, N-acryloyl-N'-(2-amino-a7-oxoethyl)-N'-methyl piperazinium chloride, N-acryloyl-N'-(3-amino- 3-oxopropyl)-N'-methyl piperazinium chloride, N-acryloyl-N'-(4-amino-~1-oxobutyl)-N'-methyl piperazinium chloride, N-acryloyl-N'-(2-amino-2-oxoethyl)~-N'-ethyl piperazinium chloride, N-acryloyl-N'-(3-amino-~-oxopropyl)-N'-ethyl piperazinium chloride, N-acryloyl-N'-{4-amino-4-axobutyl)-N'-ethyl piperazinium chloride, N,N-dimethyl-N-(3-sulfopropyl)-N-(4-vinylbenzyl) ammonium inner salt, N,N-dimethyl-N-(4-sulfobutyl)-N-(4-vinylbenzyl) ammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-N-{4-vinylbenzyl) ammonium inner salt, N,N-diethyl-N-(4-sulfobutyl)-N-{4-vinylbenzyl) ammonium inner salt, N,N-dimethyl-N-(3-sulfopropyl)-N-(3-vinylbenzyl) ammonium inner salt, N,N-dimethyl-N-(4-sulfo6utyl)-N-(3-vinylbenzyl) ammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-N-(3-vinylbenzyl) ammonium inner salt, N,N-diethyl-N-(4-sulfobutyl)-N-(3-vinylbenzyl) ammonium inner salt, 2S N,N-dimethyl-N-(2-amino-2-oxoethyl)-N-(4-vinylbenzyl) ammonium chloride, N,N-diethyl-N-(2-amino-2-oxoethyl)-N-(4-vinylbenzyl) ammonium chloride, N,N-dimethyl-N-(3-amino-~3-oxopropyl)-N-(4-vinylbenzyl) ammonium chloride, N,N-diethyl-N-(3-amino-3-oxopropyl)-N-(4-vinylbenzyl) ammonium chloride, WCi 97/22638 PCT/dTS96/18174 N,N-dimethyl-N-(2-amino-2-oxoethyl)-N-(3-vinylbenzyl) ammonium chloride, N,N-diethyl-N-(2-amino-2-oxoethyl)-N-(3-vinylbenzyl) ammonium chloride, N,N-dimethyl-N-(3-amino-3-oxopropyl)-N-(3-vinylbenzyl) ammonium chloride, N,N-diethyl-N-(3-amino-3-oxopropyl)-N-(3-vinylbenzyl) ammonium chloride, N-{2-amino-2-oxoethyl)-N'-vinyl imidazolium chloride, N-(3-amino-3-oxopropyl}-N'-vinyl imidazolium chloride, N-(4-amino-4-oxobutyl)-N'-vinyl imidazolium chloride, N,N-dimethyl-N-(3-sulfopropyl)-3-(acryloyl amino)-1-propaneammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-3-(acryloyl amino)-1-propaneammonium inner salt, N,N-dimethyl-N-{4-sulfobutyl)-3-(acryloyl amino)-1-propaneammonium inner salt, N,N-diethyl-N-(4-sulfobutyl}-3-{acryloyl amino)-1-propaneammonium inner salt, N,N-dimethyl-N-{3-sulfopropyl)-2-(acryloyl amino)-1-ethaneammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-2-(acryloyl amino)-1-ethaneammonium inner salt, N,N-dimethyl-N-(4-sulfobutyl)-2-(acryloyl amino)-i-ethaneammonium inner salt, IS N,N-diethyl-N-(4-sulfobutyl)-2-(acryloyl amino}-1-ethaneammonium 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-dimethyiacrylamide, acrylic acid, salt of acrylic acid, 2Q 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.
25 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 olef nic cornonomers having the formula of R,-C(Rl)=C(Rl)-(C=O)m M in which M is the same as disclosed above can be prepared from Rl-C(RS)=C(RI)-(C=O)m X where X is the same as that disclosed above, such as acryloyl chloride, and morpholine or from R,-C(RS)=C(R,)-(C=O)m 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 1:2.
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 20 ° C, for about 1 to about 10 hours. The reactants are commercially available.
See Examples section below for details.
The water-soluble polymers of the third embodiment of the present invention can be prepared by mixing the monomers) (i.e., the nitrogen-containing olefinic compounds and the olef nic 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 commonly employed to initiate free radical polymerization reactions include hydrogen peroxide, azo compounds such as, for example, 2,2'-azobis(2-(2-imidazolin-2-yl)propane) dihydrochloride, alkali metal persulfates such as K2S208, alkali metal perborates, alkali metal perphosphates, and alkali metal percarbonates. Well known organic peroxide compounds commonly employed to initiate free radical polymerization reactions include lauryl peroxide, 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane, t-butylperoxyprivilate, t-butylperoctoate, p-methane hydroperoxide, and benzoylperoxide. The compound t-butylhyponitrite is a well known alkyl hyponitrite commonly employed to initiate free radical polymerization reactions. Furthermore, ultraviolet light and gamma WO 97!22638 PCT/US96/18174 1g 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 comonomer 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 100:1, preferably about 0.05:1 to about 50:1, and most preferably 0.1:1 to 30:I.
If a combination of the nitrogen-containing oleflnic 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 I5 comonomers is within the range disclosed above.
According to the fourth embodiment of the present invention, a process which can be used in hydrocarbon-bearing subterranean formations such as water-flooding is provided. The process comprises, or consisting essentially of, or consisting of, introducing a water-soluble composition into a subterranean formation.
The water-soluble composition comprises, consists essentially of, or consists of a water-soluble polymer. The scope of the water-soluble polymer is the same as that disclosed in the first embodiment of the present invention, description of which is omitted herein for the interest of brevity.
The term "process" used herein and hereinafter in conjunction with a subterranean formation generally denotes, unless otherwise indicated, a use in drilling fluids, workover fluids, completion fluids, permeability corrections, water or gas coning prevention, fluid loss prevention, matrix acidizing, fracture acidizing, and combinations of any two or more thereof.

The water-soluble composition used in the fourth embodiment of the invention can also comprise a liquid. 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, 1 to as high as 30 weight percent (%). The typical salts content can be in the range of from, for instance, about 2 to about 25 weight %.
The introduction of the water-soluble composition into a subterranean formation can be carried out by any methods known to one skilled in the art.
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, sufFcient to alter the permeability of a subterranean formation. The I S amount, or concentration, can be in the range of from about SO to about 100,000, preferably about 100 to about 50,000, and most preferably 200 to 10,000 mg of the water-soluble composition per liter of the liquid.
The water-soluble composition in a liquid medium can then be introduced, by any means known to one skilled in the art such as pumping, into a subterranean formation so that it can diffuse into the more water-swept portions of the formation. The nature of the formation is not critical to carrying out the process of the present invention. The formation can have a temperature in the range of from about 70°F to about 400°F, preferably 75°F to 350°F.
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
5 carboxylate-containing polymer in the hydrocarbon-bearing formations can be used in the process of the present invention. Examples of suitable multivalent metal compounds include, but are not limited to, AI+3, Cr+3, Fe~3, Zr+4, Ti+4, and combinations of any two or more thereof.
The presently preferred multivalent metal compound is a metal 10 compound selected from the group consisting of a complexed zirconium compound, a complexed titanium compound, a compiexed chromium compound, and combinations of any two or more thereof. Examples of the preferred multivalent metallic compounds include, but are not limited to, zirconium citrate, zirconium complex of hydroxyethyl glycine, ammonium zirconium fluoride, zirconium 2-ethylhexanoate, 15 zirconium acetate, zirconium neodecanoate, zirconium acetylacetonate, tetrakis(triethanolamine)zirconate, zirconium carbonate, ammonium zirconium carbonate, zirconyl ammonium carbonate, zirconium lactate, titanium acetylacetonate, titanium ethylacetoacetate, titanium citrate, titanium triethanolamine, ammonium titanium lactate, aluminum citrate, chromium citrate, chromium acetate, chromium 20 propionate, chromium malonate, and combinations thereof. The presently most preferred crosslinking agent is zirconium lactate, zirconium citrate, tetrakis(triethanolamine)zirconate, or zirconium complex of hydroxyethyl glycine, or combinations thereof. These compounds are commercially available.
According to the fifth embodiment of the present invention, a metallic compound used as a crosslinking agent can also contain a complexing ligand if necessary to further delay the rate of gelation. Preferably, however, the crosslinking agent does not contain such complexing agent. The complexing Iigand useful for the present invention to retard the rate of gelation is generally a carboxylic acid WO 97/22638 PCT/L1S96/18i74 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 sodium tartrate, triethanolamine, malonic acid, ammonium, potassium or sodium malonate, and mixtures thereof. The presently preferred complexing ligands are citric acid, lactic acid, tartaric acid and salts thereof, triethanolamine, and hydroxyethyl glycine because of their ready availability and low cost.
A crosslinking agent can also contain two components. The first crosslinking component useful as crosslinking agent is generally water-dispersible or soluble and can be phenol, substituted phenols, aspirin, p-aminobenzoic acid, resorcinol, catechol, hydroquinone, furfuryl alcohol, R'Ar0 (C=O)m R', HOAr (C=O)m OR', HOArOH, R'OArOH, R'OArOR', or combinations of any two or more thereof where Ar is an arylene group which can be non-substituted or substituted; each R' can be the same or different and is each independently selected from the group consisting of hydrogen, carboxylic group, a CI-C6 alkyl, a phenyl group or combinations of any two or more thereof; and m is 0 or I. 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. Examples of suitable first crosslinking components include, but are not limited to, phenol, hydroquinone, resorcinol, catechol, 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-hydroxybenzoic acid, hexyl p-hydroxybenzoate, and combinations of any two or more thereof. Presently preferred water dispersible 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 crossiinking component in crosslinking agent. Examples of suitable second crossiinking components include, but are not limited to aliphatic monoaldehydes, aromatic monoaldehydes, aliphatic dialdehydes, aromatic dialdehydes, and their precursors.
Preferred aldehydes and their precursors can be selected from the group consisting of formaldehyde, paraformaldehyde, acetaldehyde, propionaidehyde, decanal, glutaraldehyde, terephthaldehyde, hexamethylenetetrarnine, and combinations of any two or more thereof.
The weight ratio of the water-dispersible f rst crosslinking component to the second crosslinking component can be any ratio so long as the ratio can effect the gelation of the gelling composition. Generally, such ratio can be in the range of from about 0.01:1 to about 100:I, preferably about 0.l :l to about 10:I, and most preferably 0.5:1 to 2:1.
Any suitable procedures for preparing the gelling composition can be used. Some of the polymers can require particular mixing conditions, such as slow addition of fnely 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 particulax 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 mg/1 (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 injected slug varies generally over the broad range of about 1 mg/1 (ppm) to about 10,000 ppm, preferably over the range of about 1 ppm to about 7,500 ppm, and most preferably 1 ppm to 2,500 ppm.
The liquid generally makes up the rest of the gelling composition.
The concentration of the complexing ligand, if present, in the gelling composition also depends on the concentrations of the water-soluble polymer in the composition and on the desired rate of gelation. Generally, the lower the concentration of the complexing ligand is, the faster the gelation rate is.
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 f fth embodiment of the invention.
The use of gelled polymers to alter the water permeability 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. The definition and scope of the crosslinking agent and gellable polymer are the same as those described above. The amount of the aqueous gelling composition introduced or injected can WO 97/22638 PC'r/US96/15174 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 composition described above can also be simultaneously or sequentially introduced into a subterranean formation.
The nature of the underground formation treated is not critical to the practice of the present invention. The described gelling composition can be introduced or injected into a formation having a temperature range of from about 70°F to about 350°F. Any means known to one skilled in the art such as, for example, a pump means can be used for introducing or injecting the gelling composition and polymer solution.
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, smectite, montmorillonite, illite, saconite, sepiolite, palygorskite. Fuller's earth, and combinations of any two or more thereof. The presently preferred clay is montmorillonite clay. The presently most preferred clay is sodium montmorillonite, which is also known as bentonite.

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 5 range of from about 0.005 to about 15; preferably about 0.005 to about 10, more preferably about 0.01 to about 6, and most preferably 0.01 to 3 weight percent of the composition.
The scope and definition of liquid are the same as those disclosed above. The liquid component generally makes up the rest of the composition.
10 According to the present invention, a thinner can also be present in the present invention, if desired, in an amount in the range of from about 0.001 to about 10 weight %, preferably about 0.001 to about 5 weight %. 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 15 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 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 20 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 from about 0.0001 to about 70.
25 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 WO 97/22638 PCT/US96/18i74 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 fiu-ther understand the invention and should not be considered limitative.
EXAMPLE I
This example illustrates the preparation of nitrogen-containing olefinic monomers.
N-acrVlovl momhoiine (NAM,) N O
O
N-acryloyl morphoiine was prepared from morpholine and acryloyl chloride. Morpholine (0.35 mole; 30.0 g), 0.42 mole (42.5 g) of triethylamine and 0.1 g of 1,3-dinitrobenzene were dissolved in 350 ml of chloroform and cooled to ca.
-15 °C. Acryloyl chloride (0.42 mole; 37.8 g) was then added from a dropping funnel in such a way that the temperature in the reaction flask did not exceed 0°C. The reaction mixture was then allowed to reach room temperature (about 25°C). After 2 hours at room temperature the solution was poured into an excess of diethyl ether (S00 ml), and the precipitated material was filtered from the ether. The 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 immediately placed in the refrigerator. B.p. 74°C/0.01 mbar. The yield was 64%.

z7 N-acrsr_~yl-N'-methyl ninerazine (AMf1 N~ -O
N-acryloyl-N'-methyl piperazine was prepared by adding 0.44 mole (39.8 g) of acryloyl chloride to a solution of 0.40 mole (40.0 g) N-methyl piperazine and 0.1 g hydroquinone in 200 ml of acetonitrile. The addition was carried out in such a way that the temperature in the reaction flask did not exceed 5 °C. The reaction mixture was allowed to reach room temperature. A 10 M aqueous NaOH-solution (17.6 g NaOH in 44 ml distilled water, 0.44 mole) was then added and the precipitated material was filtered. The two phases were separated and the organic layer was dried with CaCl2. Distillation under reduced pressure gave the product as a clear liquid.
B.p. 90-95°C/0.5 mbar. The yield was 72%.
N-acrvloyl-N'-(3_-sulfQ~ropyll-N~'-rt e_thvl ~inerazinium inner salt~AMPPS) No v.J ~ a N-acryloyl-N'-(3-sulfopropyl)-N'-methyl piperazinium inner salt was prepared from 0.26 mole (40.1 g) of N-acryloyl-N'-methyl piperazine and 0.29 mole (34.9 g) of 1,3-propanesultone. The reagents were mixed together with 0.1 g of 1,3-dinitrobenzene in 260 ml of acetonitrile. The reaction mixture was heated to 90°C for 2 i/2 hours. The precipitated material was then filtered and washed three times with diethyl ether (100 ml) each. The white powder was dried under reduced pressure (I2 mm Hg) for 18 hours. The yield was 68%.

WO 97/22638 PCTlUS96118174 - c 1 '- 2-a -oxo I -N'-m I i er r~Cq O
N-acryloyl-N'-methyl piperazine (0.13 mole; 20.0 g) was dissolved in 260 ml of dry acetonitrile (distilled over PZOS) together with 0.1 g 1,3-dinitrobenzene.
Then 0.16 mole ( 14.6 g} 2-chloro acetamide was added to the N-acryloyl-N'-methyl S piperazine, and the mixture was heated to ca. 80°C for 123 hours. A
white, precipitated powder was filtered and washed three times with diethyl ether (1 SO m1).
The product was dried under reduced pressure (12 mm Hg} for 12 hours. The yield was 75%.
N N~imet~yl-N ~3-sulfo~r_o~vl)-N~4-vi~ylbe~r 5r11 a inner salt IDMAMSPS~
Q N/
o ~'~,so, N,N-dimethyl-N-(4-vinyIbenzyl) amine (93.0 mmole; I 5 g) , 1 I 1.6 mmole (13.6 g} of 1,3-propanesultone and 0.1 g of 1,3-dinitrobenzene were mixed together and dissolved in 180 ml of toluene. The mixture was heated at 45-50°C for 72 hours. A white, precipitated material was filtered, washed three times I S with diethyl ether ( l OG m1), and finally dried under reduced pressure ( 11 mm Hg} for hours. The yield was 87%.
~imeth~(2-amino-2-oxpeth~l-N-(4-vin lb~~_I~~ ~mmnni,~In cht~ri~P
fAODVAC~, C~

N,N-dimethyl-N-(4-vinylbenzyl) amine (62.0 mmole; 10.0 g), 68.0 mmole (6.4 g) of 2-chloro acetamide and 0.1 g of 1,3-dinitrobenzene were dissolved in 125 mI of acetonitrile and heated at ca. 45 °C for 48 hours. The precipitated material was filtered and washed three times with diethyl ether (100 ml).
A white powder was dried under reduced pressure ( 12 mm Hg) for 16 hours. The yield was 88%.
1~- 2-amino-2-oxoethXl)-N'-vinyl imidazolium chloride IAOVC) NHz 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 ml 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 ml). 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-dimethyl-N-f3-sulfoprog~rll-3-(acr_ylovl amino-1-~ropaneammonium inner salt fAPDAPSI
O
' ~ O+ O
~NH'~/~ ~Sp3 Acryloylchloride (0.70 mole; 63.8 g) and 0.1 g of hydroquinone were dissolved in 350 ml of acetonitrile and cooled to -15 °C. Then 0.59 mole (60.0 g) of 3-dimethylamino-1-propylamine was added from a dropping funnel 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 NaOH
in 70 ml distilled water, 0.70 mole) was added and the precipitated material was ~0 filtered. The filtrate was concentrated on a rotavapour and then distilled under reduced pressure. B.p. 122°C/0.1 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 mean 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 etl;~er (200 ml). Finally the product was dried under reduced pressure (12 mm Hg) for 1'7 hours. 'The yield was 80%.
This exanuplle illustrates the production of polymers of the present invention.
Polymerizations were carried out in distilled water or synthetic sea water. For synthetic sea water, one liter distilled water contained 23.83 g NaCI, 0.21 g NaHC03, 10.77 g MgCl2°6H20, 1.65 g CaC1y2H20, and 42.9 g anhydrous NaZSO,.
The monomer solution was. 35 weight % and the initiator concentration was 0.3 mole % with respect to total concentration of monomers. The az~-type initiator VA-044TM (2,2'-azobis()dihydrochloride) was used to start the polymerizations.
The polymerizations were carried out at room temperature. In a typical synthesis, specified quantities of the rnonomers were dissolved in distilled water or synthetic sea 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.
onolvme= Am / AMP
Eighty parts of acrylamide and 20 parts of N-acryloyl-N'-methyl piperazine (AMP) were polymerized in distilled water for 4 hours with use of 0.3 mole % VA-044T"' as a initiator. T'he polymer was precipitated in acetone.
The yield was 34 %.
Eighty parts of acrylamide and 20 parts of N-acryloyl morpholine S (NAM) were dissolved in distilled water and the polymerization was carried out with use of 0.3 mol % VA-044'x"' as initiator. The polymerization was stopped after
6 hours.
The polymer was precipitated in acetone. The yield was 69 %.
Terp~l er / NAM /A~~
The polymer was prepared from 70 parts of acrylamide, 1 S parts of N-acryloyl morpholine (NAM) and 'l S parts of N-acryloyl-N'-methyl piperazine (AMP) with use of 0.3 mole % VA-C144T"' as initiator. Distilled water was used as solvent. After S hours the polymer was precipitated in acetone. The yield was 41 %.
~op~lv~mer Am / AMPPS
Eighty parts of acrylamide and 20 parts of 1 S N-acryloyl-N'-(3-sulfoprop;yl)-N'-methyl piperazinium inner salt {AMPPS) were polymerized in synthetic sea water for 2 hours with use of 0.3 mole % VA-044T"' as initiator. The polymer was precipitated in methanol. The yield was 62%.
A polymer' eras prepared from 80 parts of acrylamide and 20 parts of N,N-dimethyl-N-{3-sulfopropyl)-N-(4-vinylbenzyl) ammonium inner salt (DMAMSPS) dissolved in synthetic sea water. 0.3 mole % VA-044T'" was used as initiator. After 4 hours the polymer was precipitated in methanol. The yield was 48%.
~onolvmer A_r_rr / APDAPS
Eighty parts of acrylamide and 20 parts of N,N-dimethyl-N-(3-sulfopropyl~3-(acryloylamino)-1-propaneammonium inner salt (APDAPS) were polymez~ized in synthetic sea water for S hours with use of 0.3 mole % VA-044TM as initiator. The polymer was precipitated in methanol. The yield was 81%.
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 (Dh~~MSPS) 'were dissolved in synthetic sea water and the polymerization was carried out with use of 0.3 mole % VA-044TM as initiator.
The polymerization was stopped after 3 1/2 hours by precipitation of the polymer in methanol. The yield was 23%.
Te~Q~vmer Am / AMP jAPDAPS
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~l-propaneammonium inner salt (APDAPS) were polymerized in synthetic sea water with use of 0.3 mole % VA-044T"' as initiator. The polymerization was stopped after 3 hours by precipitation of the polymer in methanol. The yield was 59%.
Tr=roolvmer Am / AMP / Ajy~]PP,~
Seventy party of acrylamide, 15 parts of N-acryloyl-N'-methyl piperazine (AMP) and 15 parts of N-,acryloyl-N'-(3-sulfopropyl)-N'-methyl piperazinium inner salt (AM~'PS) were dissolved in synthetic sea water and polymerized for 23 hours. >>A'O~TM was used as initiator. The polymer was precipitated in methanol. The yield was 34%.
~polvmer~OMPC / AMPS
Fifty parts of 2-acrylamido-2-methylpropanesulfonic acid (AMPS), 50 parts N-acryloyl-N'-(2-amino-2-oxoethyl)-N'-methyl piperazinium chloride (AOMPC) and 50 parts NaOH were dissolved in NaC1-solution and polymerized for 6 hours with use of 0.3 mole % VA-033T"" as initiator. The polymer was precipitated in methanol.
The yield was 54%.

T rn~oly~mer AOVC / AMP / AMPS
A polymer 'was prepared from 15 parts of N-(2-amino-2-oxoethyl)-N'-vinyl imidazolium chloride (AOVC), 70 parts of N-acryloyl-N'-methyl piperazine (AMP), 15 parts of 2-acrylamido-2-methylpro~pane-suIfonic acid (AMPS) and 15 parts of NaOH in synthetic sea water. Three tenths mole % VA-044T"' was used as initiator and the polymerization was stopped after 5 hours by precipitation of the polymer in methanol.
The yield was 38%.
AOMPC HomoRo_l, N-acryIoyl-N'-(2-amino-2-oxoethyl)-N'-methyl piperazinium chloride (AOMPC) (20.19 mmol) was dissolved in synthetic sea water and 0.3 mole VA-044T"' was added. Tlye polymerization was.stopped after 6 hours by precipitation of the polymer in acetone. 'fhe yield was 57%.
Tertxzlymer A_m__ l A,MP l AMPS
1$ Seventy parts of acryIamide, 15 parts of N-acryloyI-N'-methyl piperazine (A,MP) and 15 parts of 2-acrylamido-2-methyl-propanesulfonic acid (AMPS) were dissolved in distilled water and polymerized for 3 hours. Three tenths mole % VA-044T"' was used as initiator. The polymer was precipitated in acetone. The yield was 47%.
This example illustrates the preparation of gelling compositions from the polymers disclosed above and ttie 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) with magnetic slitting before use.

Stock solutions of phenol, formaldehyde and HMTA each containing 10,000 mg/1 (ppm) were used.
For each test 4.0 g of gelling composition were made by adding polymer, phenol and fornialdehyde/HMTA solution and diluting with synthetic sea water to the correct concentration. 1'he same ppm concentration of both phenol and formaldehyde/HMTA was used. Magnetic stirring was used to mix the gelling compositions. After mixing the pH of the gelling compositions were registered using pH indicator strips. The pH of the was not adjusted in any way. The gelling compositions were thereafter transferred to glass vials, and the solutions were flushed with argon gas for 5 minutes before 'the vials were closed. The glass vials were weighed before and after adding gelling compositions.
For aging at 120°C, the glass vials were placed in stainless steel containers filled with water. After aging at 120°C, the stainless steel containers were cooled down to room temperature, the gel strength of the samples were characterized visually as weak, strong or Frigid. 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 the gel height and the length of the liquid layer after ageing.
Measurement of Inherent Viscosity Polymer solution (0.1 weight %) in synthetic sea water was made for viscosity measurements. The polymer solution was allowed to stand for 3 days with magnetic stirring. Before viscosity measurement the polymer solution was filtered through a 5 um Millipore filter. The relative viscosity of the 0.1 weight %
polymer solution (relative to synthetic sea water) was measured with an UbbelhodeTM
viscosimeter with an inner capillary diameter of 0.69 mm. At least 3 parallel measurements were performed for each solution. The temperatwe of the polymer solution under the viscosity measurement was 25.0 t 0.05°C.

WO 97/22638 PCTlUS96118174 Relative viscosity: - time for polymer solution through capillary/
time for synthetic sea water trough capillary Inherent viscosity: ln(rel. vise) / 0.1 g/dl The results are shown in the following Tables I-XXI. These tables 5 show that gels formed from the polymers of the present invention were resistant to high temperature and high salinity environment. Little or no syneresis was observed after prolonged aging at high temperature and high salinity environment.

3s Table I

PolymerPhenol/ GeI
height (G) and Am/AMP' Inherentconc. HMTAd Liquid height (L) after aging Run Feed Viscosity(ppm) (ppm at in of 120C
in SNSW
for No. Ratiob dl/g SNSW' each) 30 days days days 181 Cr--25G=25 G=25 mm mm $ JSI L-S L=5 L=5 mm mm mm II23 80120 5.4 6200 2500 R'g=d Rigid Rigid 181 G=30 G=25 G=25 mm mm mm JSI Lg0 L=5 L=5 mm mm mm II23 80/20 5.4 10400 2500 ~gid Rigid Rigid 1 Q I G=26 G-24 Gr=24 8 mm mm mm I

JSI L=0 L= I L=2 mm mm mm Rigid Rigid Rigid II23 80/20 5.4 20000 2500 'Am=acrylamide, AMP=N-acryloyl-N'-methyl piperazine bmole %
ratio of monomers in the aqueous solution 1$ 'SNSW=synthetic sea water dHMTA=hexamethylenetetramine Table II

Polymer Phenol/ Weight %
gel' Inherent conc. HMTAa Gel Character Run Am/AMP' Viscosity(ppm) in (ppm of No. Feed RatiobdI/g SNSW' each) $ months II23 80/20 5.4 6200 2500 Rigid 2$ II23 80/20 5.4 10400 2500 Rigid II23 80/20 5.4 20000 2500 Rigid 'Am=acrylamide, AMP=N-acryloyl-N'-methyl piperazine 30 bmole %
ratio of monomers in the aqueous solution 'SNS
W=synthetic sea water aHMTA=hexamethylenetetramine 'Weight %
geI
of initial weight of the solution after aging at in synthetic sea water Table III

Polymer Phenol/

Inherentconc. HCHOd Run Am/AMP$ Viscosity(ppm) {ppm Weight in of % gels No. Feed Ratiobdl/g SNSW each) Gel Character 5 days 30 days VII43 70/30 5.1 20000 2500 Strong I76 70/30 3.8 10000 500 Weak I76 70/30 3.8 20000 2500 Rigid VII52 60/40 4.3 20000 2500 Strong VII52 60/40 4.3 5000 1000 Rigid VII52 60/40 4.3 10000 1000 Strong VII52 60/40 4.3 10000 2000 Rigid VII49 50:50 3.4 20000 2500 Weak VII49 50/50 3.5 5000 1000 Strong Table III

Polymer Phenol/

Inherentconc. HCHOd Run Am/AMP' Viscosity(ppm) (ppm of Weight in %
gel No. Feed Ratiobdl/g SNSW' each) Gel Character VII49 50!50 3.5 10000 1000 Strong VII49 50/50 3.5 10000 2500 Rigid Am=acrylamide, AMP=N-acryloyl-N'-methyl piperazine hmole % ratio of monomers in the aqueous solution 'SNS
W=synthetic sea water aHCHO=formaldehyde 'Weight % gel of initial weight of the solution after aging at in synthetic sea water Table IV

Polymer Weight %
gelf Inherentconc. Phenols/ Gel Character Run Am/AMP Viscosity(ppm) in HMTA' No. Feed Ratiobdl/g SNSW' (ppm) 30 days VII43 70/30 5.1 10000 2000 Strong VII43 70/30 5.1 20000 2000 Strong I76 70:30 3.8 5000 1000 Strong I76 70:30 3.8 10000 500 Weak Table IV

Polymer Weight % gelf Inherentconc. Phenols/ GeI Character Run Am/AMP$ Viscosity(ppm) in HMTA' No. Feed Ratiobdl/g SNSW' (ppm) 30 days I76 70:30 3.8 10000 1000 Weak VII52 60/40 4.3 10000 2000 Weak VII52 60/40 4.3 20000 2000 Strong II63 60/40 3.8 20000 2500 Rigid II63 60/40 3.8 10000 2500 Rigid II65 60/40 3.7 20000 2500 Rigid i56 VII49 50/50 3.5 20000 2000 Weak aAm=acrylamide, AMP=N-acryloyi-N'-methyl piperazine bmole %
ratio of monomers in the aqueous solution 'SNSW=synthetic sea water ppm 'HMTA=hexamethylenetetramine (Weight %
gel of initial weight of the solution after aging at in synthetic sea water Table V

Polymer Phenol/Gel height (G) InherentConc. Hmta and Liquid height (L) after aging Run Am/namaViscosit(Ppm) (Ppm at in of 120C
in SNSW
for No. Feed y Snsw' Each) 30 days days days ratiob Dl/g 179 G=30 G=28 G=28 mm mm mm JSI L= L=7 mm L=7 II 5 mm mm 11 80:20 4.4 5400 2500 ~8id Rigid Rigid 1 G-27 Ga27 G=27 ?9 mm mm mm JSI L=5 L=5 mm La5 II mm mm i 80:20 4.4 10300 2400 ~g~d Bid Rigid l I 0 179 Cr=26 Gr34 G=24 mm mm mm JSI L=3 L=5 mm L=5 II mm mm Rigid Rigid Rigid 11 80:20 4.4 20000 2400 $Am=acrylamide, NAM=N-acryloyl morpholine bmoie %
ratio of monomers in the aqueous solution I S 'SNSW=synthetic sea water dHMTA=hexamethylenetetramine Table VI

Polymer Phenol! Weight %
gel' Inherent conc. HMTA Get Character Run Am/NAMe Viscosity(ppm) (ppm of in No. Feed Ratiobdl/g SNSW' each) 5 months JSI 0.8 ~

II11 80120 4.4 5400 2500 Rigid JSI 0.9 25 II11 80/20 4.4 10300 2400 Rigid JSI 0.9 IIlI 80/20 4.4 20000 2400 Rigid $Am=acrylamide, NAM=N-acryloyl morpholine 30 mole %
ratio of monomers in the aqueous solution 'SNSW=synthetic sea water HMTA=hexamethylenetetramine 'Weight %
gel of initial weight of the solution after aging at in synthetic sea water Table VII

Polymer Phenol/

Inherent conc. HCHOd Run Am/NAMa Viscosity(ppm) (ppm Weight in of % gel' No. Feed Ratio"dl/g SNSW' each) Gel Character I79 80120 6.2 10000 500 Strong I79 80/20 6.2 10000 2500 Strong I81 70/30 3.7 10000 1000 Rigid I83 60/40 3.3 20000 1000 Rigid V 85 20/80 2.5 20000 2500 Strong Strong VII 20/80 1.1 30000 4000 Strong Strong VII 20/80 1.1 30000 2000 Strong Am=acrylamide, NAM=N-acryloyl morpholine bmole %
ratio of monomers in the aqueous solution 'SNSW=synthetic sea water dHCHO=formaldehyde 'Weight %
gel of initial weight of the solution after aging at C
in synthetic sea water Table VIII

Polymer Weight % gelf Inherentconc. Phenols/Gel Character Run Am/NAM' Viscosity(ppm) HMTA' in No. Feed Ratiobdl/g SNSW (ppm) 30 days Parallel Parallel2B
l8 I59 70/30 2.2 20000 2000 Rigid Weak I59 70/30 2.2 10000 2000 Rigid I61 60/40 2.2 20000 2000 Rigid Weak I63 50150 2.5 20000 2000 Strong Weak 'Am=acrylamide, NAM=N-acryloyl morpholine mole %
ratio of monomers in the aqueous solution 'SNSW=synthetic sea water ppm 'HMTA=hexamethylenetetramine (Weight %
gel of initial weight of the solution after aging at in synthetic sea water sDuplicate runs.

Table IX

Polymer Phenol/ Weight %
gel' Inherentconc. HMTAd Gel Character Run Am/NAM/AMP Viscosity(ppm) (ppm of in No. Feed Ratiob dl/g SNSW' each) 30 days II21 70/15/15 4.6 10000 2500 Rigid II21 70/15/15 4.6 20000 2500 Rigid II21 70/15!15 4.6 10000 1000 Strong aAm=acrylamide, NAM=N-acryloyl morpholine, AMP=N-acryloyl-N'-methyl piperazine bmole %
ratio of monomers in the aqueous solution 1 S 'SNSW=synthetic sea water dHMTA=hexamethylenetetramine 'Weight %
gel of initial weight of the solution after aging at in synthetic sea water WO 97!22638 PCT/US96/18174 Table X

Polymer Phenol/

Inherentcone. HCHOd Run Am/AMPPS' Viscosity(ppm) (ppm Weight in of %
gel No. Feed Ratiobdl/g SNSW each) Gel Character 5 days30 days I65 80/20 2.2 10000 2500 Strong I65 80/20 2.2 20000 1000 Rigid I6S 80/20 2.2 10000 2000 Rigid I28 80/20 1.8 30000 4000 Rigid Strong I28 70/30 1.8 30000 2000 Strong I26 60140 1.6 30000 4000 StrongStrong I 26 60/40 i .6 30000 2000 Strong VI68 50/50 20000 2500 Weak Weak VII15 50/40 1.5 30000 4000 StrongStrong VII15 50/50 1.5 30000 2000 Strong 'Am=acrylamide, S=N-acryloyl-N'-(3-sulfopropyI)-tf-methyl AMPP piperazinium Table XI

Polymer Phenol/ Weight % gele Inherentconc. HMTAd Gel Character Run Am/AMPPS" Viscosity(ppm) (ppm of in No. Feed Ratiobdl/g SNSW each) 30 days 5 JSI Rigid II67 80/20 3.5 10000 2500 90 JSI Rigid II67 80/20 3.5 20000 2500 70 10 Am=acrylamide, AMPPS=N-acryloyl-N'-(3-sulfopropyl)-N'-methyl piperazine inner salt bmole %
ratio of monomers in the aqueous solution SNSW=synthetic sea water dHMTA=hexamethylenetetramine Weight %
gel of initial weight of the solution after aging at in synthetic sea water Table XiI

Polymer Phenol/

Inherentconc. HCHOd Weight %
get' Run AmlDMAMSPS" Viscosity(ppm) (ppm Gel in of Character No. Feed Ratiob dt/g SNSW' each) 5 days30 days I SS 90/10 1.0 10000 2500 Strong I55 90/10 1.0 20000 2500 Strong TOB i 00 79 V 79 80/20 0.9 10000 2500 Weak Weak VII23 80/20 2.0 30000 4000 StrongStrong VII23 80/20 2.0 10000 1000 Strong VII23 80/20 2.0 10000 2500 Rigid gAm=acrytamide, DMAMSPS=N,N-dimethyl-N-(3-sulfopropyl)-N-(4-vinylbenzyl)-ammonium inner salt 'mole %
ratio of monomers in the aqueous solution 'SNSW=synthetic sea water dHCHO=formaldehyde 'Weight %
gel of initial weight of the solution after aging at in synthetic sea water Table XIII

Polymer Phenol/ Weight %
gel' Inherentconc. HMTAd Gel Character Run AmIDMAMSPS Viscosity(ppm) (ppm in of No. Feed Ratiob dl/g SNSW each) 30 days VII 80/20 2.0 10000 2000 Weak gel VII23 80!20 2.0 20000 2000 Weak Am=acrylamide, DMAMSPS=N,N-dimethyl-N-(3-sulfopropyl)-N-(4-vinylbenzyl)-ammonium inner salt bmoie %
ratio of monomers in the aqueous solution 'SNSW=synthetic sea water dHMTA=hexamethylenetetramine 'Weight %
gel of initial weight of the solution after aging at in synthetic sea water WO 97/22638 PCT/US96/i8I74 Table XIV

Polymer Phenol/ Weight % gel' Inherentconc. HMTAd Gel Character Run Am/APDAPSa Viscosity(ppm) (ppm of in No. Feed Ratiobdl/g SNSW~ each) 30 days TOB g0 VII89 80/20 5.3 5000 2500 Rigid VII89 80/20 5.3 10000 2500 Rigid VII89 80/20 5.3 20000 2500 Strong aAm=acrylamide, APDAPS=N,N-dimethyl-N-(3-sulfopropyl)-3-(acryloylamino)-1-propaneammonium inner salt bmole % ratio of monomers in the aqueous solution SNSW=synthetic sea water dHMTA=hexamethylenetetramine 'Weight % gel of initial weight of the solution after aging at C in synthetic sea water Table XV

Polymer Phenol/Phenol/Weight % gelr Am/AMP/ Inherentconc. HCHOd HMTA Gel Character Run DMAMSPS' Viscosity{ppm) (ppm (ppm in of of No. Feed Ratiobdl/g SNSW' each) each) 30 days VII87 60/20/20 2.4 10000 2500 Strong VII87 60/20/20 2.4 20000 2500 Rigid VII87 60/20/20 2.4 20000 2500 Rigid aAm=acrylamide, AMP--N-acryloyl-N'-methyl piperazine, DMAMSPS=N,N-dimethyl-N-(3-sulfopropyl}-N-(4-vinylbenzyl)-ammonium i 5 inner salt mole % ratio of monomers in the aqueous solution 'SNSW=synthetic sea water HCHO=formaldehyde HMTA=hexamethylenetetramine (Weight % gel of initial weight of the solution after aging at in synthetic sea water $0 Table XVI

Polymer Phenol! Weight % get' Am/AMP/ Inherent conc. HMTA Gel Character Run APDAPS' Viscosity(ppm) (ppm of in No. Feed Ratiobdl/g SNSW' each) 30 days VII85 70/25/5 4.4 5000 2500 Rigid VII85 70/25/5 4.4 10000 2500 Rigid VII85 70/25/5 4.4 20000 2500 Rigid I49 60/30/10 3.5 10000 2500 Rigid I49 60/30/10 3.5 20000 2500 Rigid 'Am=acrylamide, AMP=N-acryloyl-N'-methyl piperazine, APDAPS=N,N-dimethyl-N-{3-sulfopropyl)-3-(acryloylamino)-1-propaneammonium inner salt bmole % ratio of monomers in the aqueous solution 'SNSW=synthetic sea water dHMTA=hexamethylenetetramine 'Weight % gel of initial weight of the solution after aging at in synthetic sea water WO 97!22638 PCT/US96/I8174 SI
Table XVII

Polymer Phenol/ Weight %
gel' Am/AMPI Inherentconc. HMTAd Gel Character Run APDAPS Viscosity(ppm) in (ppm of No. Feed Ratiobdl/g SNSW' each) 30 days II25 70/15/15 1.9 10000 2500 Rigid II25 70/15/15 1.9 20000 2500 Rigid Am=acrylamide, AMP=N-acryloyl-N'-methyl piperazine, AMPPS=N-acryloyl-N'-(3-sulfopropyl)-N'-methyl piperazinium inner salt bmole %
ratio of monomers in the aqueous solution 'SNSW=synthetic sea water dHMTA=hexamethylenetetramine 'Weight %
gel of initial weight of the solution after aging at C
in synthetic sea water Table XVIII

Polymer Phenol! Weight % gel' AOMPC/ Inherent conc. HCHOd Gel Character Run AMPS' Viscosity(ppm) (ppm in of No. Feed Ratio"dl/g SNSW' each) 30 days I43 50/50 1.1 10000 2500 Strong AOMPC=N-acryloyl-N'-(2-amino-2-oxoethyl)-N'-methyl piperazinium chloride, AMPS=2-acrylamido-2-methyl-propanesulfonic acid 6moie %
ratio of monomers in the aqueous solution 'SNSW=synthetic sea water dHCHO=formaldehyde 'Weight %
gel of initial weight of the solution after aging at in synthetic sea water WO 97!22638 PCT/US96/18174 Tabte XIX

Polymer Phenol/ Weight %
gel' AOVC/AMP/ Inherent conc. HCHO Gel Character Run AMPS' Viscosity(ppm} (ppm in of - No. Feed Ratiobdllg SNSW' each) 30 days II33 15/70/i5 1.6 20000 2500 Rigid "AOVC=N-(2-amino-2-oxoethyl}-N'-vinyl imidazolium chloride, AMP--N-acryloyl-N'-methyl piperazine, AMPS=2-acrylamido-2-methyl-propanesulfonic acid bmole %
ratio of monomers in the aqueous solution I O 'SNSW=synthetic sea water HCHO=formaldehyde 'Weight %
gel of initial weight of the solution after aging at in synthetic sea water Table XX

Inherent Viscosity dl/g Polymer Phenol/ Weight %
geld conc. HCHO' GeI Character Run AOMPC 0.1 (ppm) (ppm of in No. Homopol weight SNSWb each) 30 days %

VII8 1.4 30000 4000 Strong 'AOMPC=N-acryloyi-N'-(2-amino-2-oxoethyl)-N'-methyl piperazinium chloride, homopolymer bSNSW=synthetic sea water 'HCHO=formaldehyde dWeight %
gel of initial weight of the solution after aging at in synthetic sea water 'Table XXI

Polymer Phenol/ Weight %
gel' Am/AMP/ Inherentconc. HCHO Gel Character Run AMPS' 'Viscosity(ppm) (ppm of in No. Feed Ratiobdl/g SNSW' each) 30 days $ TOB 100 VII57 50/25/25 3.4 20004 1000 Strong VII57 50/25/25 3.4 20000 2500 Strong 'Am=acrylamide, AMP=N-acryloyl-N'-methyl piperaaine, AMPS=2=acrylamido-2-methyl-propanesulfonic acid bmole %
ratio of monomers in the aqueous solution 'SNS
W=synthetic sea water HCHO=formaldehyde 'Weight %
gel of initial weight of the solution after aging at in synthetic sea water This example is a comparative example showing that gels formed from a commonly employed polyacrylamide do not withstand well under a hostile environment condition as compared to the gels formed from the invention polymers.
:ZO A 7000 ppm solution of Dowell J333T~' polyacrylamide in seawater was crosslinked with phenol and formaldehyde at 120°C. Table XXII shows a summary of the results.

Table XXII

Gel Height Polymer PhenoUFormaldehyde(G) and ' Concentration(ppm of each) Liquid Height (L) after 6 days aging at 120C
G(mm) L(mm) 7000 500 22 65 Rigid 7000 1000 20 70 Rigid 7000 2000 30 75 Rigid The results shown in Table XHII indicate that much syneresis 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 fresh water based compositions were prepared by mixing the components shown in Table XXIII on a Multi-mixer in quart jars. The mixing time, in minutes, after the addition of each component is shown in the table. After the mixing was completed, the fluid compositions were transferred into pint jars and then tested initially for viscosity and gel strength according to the API RP 13B-l, First Edition, 3une 1, 1990 procedure. The compositions were then mixed for five minutes and tested for filtration according to the low-temperature/low-pressure test procedure.
These test results are presented in Table XXIV under "Initial Results". The compositions were then kept in capped jars at 75 °C for about 16 hours, cooled to about 30°C, and tested after the compositions were mixed for 5 minutes.
These test results are represented in Table XXIV under "Results After Aging at 75 °C".

5$
Table XXIiI"

Run Materials Used 8-1 345 mi tap water + 10 g bentonite (40) 8-2 325 ml tap water + 10 g bentonite (20) + 20 g of 4% solution of NAM/AM

in deionized water (20).

8-3 325 mi tap water + 10 g bentonite (20) + 20 g of 4% solution of NAM/AP

in deionized water (20).

8-4 325 ml tap water + 10 g bentonite (20) + 20 g of 4% solution of NAM/AA

in deionized water (20).

8-5 305 ml tap water + 10 g bentonite (20) + 40 g of 4% solution of NAM/AM

in deionized water (20).

8-6 305 ml tap water + 10 g bentonite {20) + 40 g of 4% solution of NAMIAP

in deionized water (20).

8-7 305 ml tap water + 10 g bentonite (20) + 40 g of 4% solution of NAM/AA

in deionized water (20).

gNAM/AM
is a copolymer of 25%
(mole %) acryloyl morpholine and 75%

acrylamide;
NAM/AP
is a copolymer of 25%
acryloyl morpholine and 75%

acrylamide-2-methylpropanesulfonate;
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 Run AV PV YP Gels FL AV PV YP Gels FL

8-I 2.5 2 1 1/1 20.4 2.5 2 1 I/2 16.8 8-2 12.0 6 12 3/5 63.7 14.5 5 19 3/6 67.6 8-3 8.0 7 2 1/3 15.8 8.5 7 3 2/2 15.4 8-4 10.5 8 5 1 J3 13.5 1 I 3 2/3 13.1 .5 8-5 32.5 19 27 14/23 68.I 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 5/6 8.3 37.0 23 28 5/6 8.6 sAV-apparent viscosity, cps PV-plastic viscosity, cps.
Gels-gel strength, seconds/lOminutes, lbs/100 sq.ft.
FL-fluid loss at low-temperature/low-pressure, ml minutes.
CNM-can not be measured accurately.

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 polymer.
Further, these four inventive compositions had higher viscosity than the base fluid.
High viscosity is desirable. Even though two inventive compositions (run 8-2 and 8-5) had high fluid loss, their high viscosity is useful in bringing the drill cuttings to the surface.
EXAMPLE VI
This example illustrates a sea water based composition of the invention that can be used as drilling fluids, completion fluids, or workover fluids.
Four sea water based compositions were prepared by mixing the components shown in Table XXV on a Multi-mixer in quart jars. The mixing time, in minutes, after the addition of each component is shown in the table. After the mixing was completed, the fluid compositions were kept at about 75°C for about two hours.
Each composition was mixed 5 minutes and after adding 0.05 ml of octyi alcohol as a defoamer to each composition, each sample was tested initially for viscosity, gel strength, and filtration at low-temperature/iow-pressure according to the API
RP
13B-1, First Edition, June 1, i 190 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 S minutes and, after adding 0.05 ml of octyl alcohol as a defoamer to each composition, they were retested. These results are represented in Table XXVI
under "Results After Aging at 75 °C". The composition of sea water is shown in Example II.
Table XXV"

Run Materials Used 9-1 340 ml tap water + 10 g bentonite (20) + 2 g Na-lignite ( 10 + 14.7 g sea salt (30) 9-2 265 ml tap water + 10 g bentonite (20) + 2 g Na-lignite (10) + 14.7 g sea salt ( 10) + 75 g of 4% solution of NAM/AM in deionized water (20) 9-3 265 ml tap water + 10 g bentonite (20) + 2 g Na-lignite ( 10) + 14.7 g sea salt ( I 0) + 75 g of 4% solution of NAM/AP in deionized water (20) 9-4 265 ml tap water + 10 g bentonite (20) + 2 g Na-lignite (10) + 14.7 g sea salt (10) + 75 g of 4% solution of NAM/AA in deionized water (20) 'See footnote a in Table XXIII.

W~ 97/22638 PCT/US96/18174 Table XXVI

Initial Results Results After Aging at Run AV PV YP Geis FL AV PV YP Gels FL

9-1 6.5 2 9 8/9 79.2 7.0 3 8 6/8 62.2 9-2 16.5 i 13 5/8 19.4 15.0 10 10 4/8 18.5 9-3 24.0 15 18 6/9 8.1 22.5 14 17 4/7 7.6 9-4 28.5 18 21 4/15 4.8 24.5 16 17 3/10 4.8 sAV-apparent viscosity, cps PV-plastic viscosity, cps.
Gels-gel strength, IO
seconds/IOminutes, Ibs/100 sq.ft.
FL-fluid loss at low-temperature/low-pressure, ml minutes.

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 surface.
The results shown in the above examples clearly demonstrate that the present invention is well adapted to carry out the objects and attain the ends 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.

Claims (103)

THAT WHICH IS CLAIMED:
1. A composition comprising a liquid medium and a nitrogen-containing olefinic compound having the formula selected from the group consisting of R1C(R1)=C(R1)-(C=O)-(NH)m-(Ar)-Y-N+(R2)(R2)-Y-SO3-, R1-C(R1)=C(R1)-(C=O)m-CNH)m-(Ar)m-Y-N+(R2)(R2)-Y-(C=O)m-N(R2)(R2)X;

and combinations of any two or more thereof wherein R1 and R2 are each independently selected from the group consisting of hydrogen, alkyl radical, aryl radical, aralkyl radical, alkaryl radical, and combinations of any two or more thereof wherein each radical contains 1 to 30 carbon atoms;
each Y is independently selected from the group consisting of alkylene radical, phenylene group, imidazolium group, naphthylene group, biphenylene group, and combinations of any two or more thereof;
Ar is an arylene group;
X is an anion selected from the group consisting of halide, sulfate, phosphate, nitrate, sulfonate, phosphonate, sulfinate, phosphinate, and combinations of any two or more thereof; and each m is independently 0 or 1.
2. A composition according to claim 1 wherein m is 0.
3. A composition according to claim 1 wherein m is 1.
4. A composition according to claim 1 wherein said olefinic compound is selected from the group consisting of 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-oxobutyl) piperazinium chloride, N-acryloyl-N'-ethyl-N'-(2-amino-2-oxoethyl) piperazinium chloride, N-acryloyl-N'-ethyl-N'-(3-amino-3-oxopropyl) piperazinium chloride, N-acryloyl-N'-ethyl-N'-(4-amino-4-oxobutyl) piperazinium chloride, N,N-dimethyl-N-(2-amino-2-oxoethyl)-N-(4-vinylbenzyl) ammonium chloride, N,N-diethyl-N-(2-amino-2-oxoethyl)-N-(4-vinylbenzyl) ammonium chloride, N,N-dimethyl-N-(3-amino-3-oxopropyl)-N-(4-vinylbenzyl) ammonium chloride, N,N-diethyl-N-(3-amino-3-oxopropyl)-N-(4-vinylbenzyl) ammonium chloride, N-(2-amino-2-oxoethyl)-N'-vinylimidazolium chloride, N-(3-amino-3-oxopropyl)-N'-vinylimidazolium chloride, N-(4-amino-4-oxobutyl)-N'-vinylimidazolium chloride, and combinations of any two or more thereof.
5. A composition according to claim 1 wherein said nitrogen-containing olefinic compound is selected from the group consisting of N,N-dimethyl-N-(2-amino-2-oxoethyl)-N-(4-vinylbenzyl)ammonium chloride, N-acryloyl-N'-methyl-N'-(2-amino-2-oxoethyl)piperazinium chloride, N-(2-amino-2-oxoethyl)-N'-vinylimidazolium chloride, and combinations of any two or more thereof.
6. A composition according to claim 1 wherein said nitrogen-containing olefinic compound is N,N-dimethyl-N-(2-amino-2-oxoethyl)-N-(4-vinylbenzyl)ammonium chloride.
7. A composition according to claim 1 wherein said nitrogen-containing olefinic compound is N-acryloyl-N'-methyl-N'-(2-amino-2-oxoethyl)piperazinium chloride.
8. A composition according to claim 1 wherein said nitrogen-containing olefinic compound is N-(2-amino-2-oxoethyl)-N'-vinylimidazolium chloride.
9. A process for producing a nitrogen-containing olefinic compound comprising contacting a tertiary amine with an alkylating agent under conditions sufficient to effect the production of said nitrogen-containing olefinic compounds wherein said nitrogen-containing olefinic compound has the formula selected from the group consisting of R1C(R1)=C(R1)-(CO)m (NH)m-(Ar)m Y-N+(R2)(R2)(R2)-Y-SO3-, R1-C(R1)=C(R1)-(C=O)m -(NH)m-(Ar)m-Y-N+(R2)(R2)-Y-(C=O)m-N(R2)(R2)X-, and combinations of any two or more thereof wherein R1 and R2 are each independently selected from the group consisting of hydrogen, alkyl radical, aryl radical, aralkyl radical, alkaryl radical, and combinations of any two or more thereof wherein each radical contains 1 to 30 carbon atoms;
Ar is an arylene group;
each Y is independently selected from the group consisting of alkylene radical, phenylene group, imidazolium group, naphthylene group, biphenylene group, and combinations of two or more thereof;

X is an anion selected from the group consisting of halide, sulfate, phosphate, nitrate, sulfonate, phosphonate, sulfinate, phosphinate, and combinations of any two or more thereof;

each m is independently 0 or 1;
amine is selected from the group consisting of N,N-dimethyl-N-(4-vinylbenzyl) amine, N,N-dimethyl-N-(4-vinylbenzyl) amine, N,N-diethyl-N-(4-vinylbenzyl) amine, N,N-diethyl-N-(4-vinylbenzyl) amine, N,N-dimethyl-N-(3-vinylbenzyl) amine, N,N-dimethyl-N-(3-vinylbenzyl) amine, N,N-diethyl-N-(3-vinylbenzyl) amine and N,N-diethyl-N-(3-vinylbenzyl) amine, and combinations of any two or more thereof; and alkylating agent is selected from the group consisting of 3-chloro-propane-1-sulfonic acid, 4-chloro-butane-1-sulfonic acid, 3-hydroxy-propane-1-sulfonic acid, 4-hydroxy-butane-1-sulfonic acid, a corresponding ester of the hydroxy-alkane-1-sulfonic acids, and combinations of any two or more thereof.
10. A process according to claim 9 wherein said nitrogen-containing olefinic compound is selected from the group consisting of N-acryloyl-N'-methyl-N'-(2-amino-2-oxoethyl) piperazinium chloride, N-acryloyl-N'-methyl-N'-(3-amino-3-oxoprapyl) piperazinium chloride, N-acryloyl-N'-methyl-N'-(4-amino-4-oxobutyl) piperazinium chloride, N-acryloyl-N'-ethyl-N'-(2-amino-2-oxoethyl) piperazinium chloride, N-acryloyl-N =ethyl-N'-(3-amino-3-oxopropyl) piperazinium chloride, N-acryloyl-N'-ethyl-N'-(4-amino-4-oxobutyl) piperazinium chloride, N,N-dimethyl-N-(2-amine-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-amine-3-oxopropyl)-N-(4-vinylbenzyl) ammonium chloride, N,N-diethyl-N-(3-amino-3-axopropyl)-N-(4-vinylbenzyl) ammonium chloride, N-(2-amino-2-oxoethyl)-N'-vinylimidazolium chloride, N-(3-amino-3-oxopropyl)-N'-vinylimidazolium chloride, N-(4-amino-4-oxobutyl)-N'-vinylimidazolium chloride, and combinations of any two or more thereof.
11. A process according to claim 9 wherein said nitrogen-containing olefinic compound is selected from the group consisting of N,N-dimethyl-N-(2-amino-2-oxoethyl)-N-(4-vinylbenzyl)ammonium chloride, N-acryloyl-N'-methyl-N'-(2-amino-2-oxoethyl)piperazinium chloride, N-(2-amino-2-oxoethyl)-N'-vinylimidazolium chloride, and combinations of any two or more thereof.
12. A process according to claim 9 wherein said nitrogen-containing olefinic compound is N,N-dimethyl-N-(2-amino-2-oxoethyl)-N-(4-vinylbenzyl)ammonium chloride.
13. A process according to claim 9 wherein said nitrogen-containing olefinic compound is N-acryloyl-N'-methyl-N'-(2-amino-2-oxoethyl)piperazinium chloride.
14. A process according to claim 9 wherein said nitrogen-containing olefinic compound is N-(2-amino-2-axoethyl)-N'-vinylimidazolium chloride.
15. A polymer comprising repeat units derived from a nitrogen-containing olefinic monomer having the formula selected from the group consisting of R1C(R1)=C(R1)-(C=O)-(NH)m-(Ar)m-N+(R2)(R2)-Y-SO3-, R1-C(R1)=C(R1)-(C=O)m-(NH)m-(Ar)m-Y-N+(R2)(R2)-Y-(C=O)m-N(R2)(R2)X-, and combinations of any two or more thereof wherein R1 and R2 are each independently selected from the group consisting of hydrogen, alkyl radical, aryl radical, aralkyl radical, alkaryl radical, and combinations of any two or more thereof wherein each radical contains 1 to 30 carbon atoms;

each Y is independently selected from the group consisting of alkylene radical, phenylene group, imidazolium group, naphthylene group, biphenylene group, and combinations of any two or more thereof;

each X is an anion selected from the group consisting of halide, sulfate, phosphate, nitrate, sulfonate, phosphonate, sulfinate, phosphinate, and combinations of any two or more thereof;

Ar is an arylene group;

and each m is independently 0 or 1.
16. A polymer according to claim 15 further comprising repeat units derived from at least one olefinic comonomer having the formula selected from the group consisting of R1-C(R1)=C(R1)-W, R1C(R1)=C(R1)-(C=O)m-Z, R1-C(R1)=C(R1)-Y-W, R1-C(R1)=C(R1)-(C=O)m-N(R2)-Y-R2, R1(R1)=C(R1)-(C=O)m-G-Y-Z, R1C(R1)=C(R1)-(C=O)m-G-Y-W, R1-C(R1)=C(R1)-(C=O)m- Y-Z, and combinations of any two or more thereof wherein each R1 and R2 are the same or different and are independently selected from the group consisting of hydrogen, alkyl radical, aryl radical, aralkyl radical, alkaryl radical, and combinations of any two or more thereof, wherein each radical contains 1 to 30 carbon atoms;

each m is independently 0 or 1;

Z has the formula selected from the group consisting of N(R2)(R2), N+(R2)(R2)(R2)X- in which X is an anion selected from the group consisting of halide, sulfate, phosphate, nitrate, sulfonate, phosphonate, sulfinate, phosphinate, and combinations of any two or more thereof;

G is N(R2) or O;

each Y is independently selected from the group consisting of alkylene radical, phenylene group, imidazolium 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, phosphoric 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.
17. A polymer according to claim 15 further comprising repeat units derived from at least one olefinic comonomer having the formula selected from the group consisting of R1(R1)=C(R1)-(C=O)m-Z, R1-C(R1)=C(R1)-(C=O)m-Y-W, R1-C(R1)=C(R1-W, R1-C(R1)=C(R1)-(C=O)-G-Y-W, and combinations of any two or more thereof wherein each R1 and R2 is the same or different and is independently selected from the group consisting of hydrogen, alkyl radical, aryl radical, aralkyl radical, alkaryl radical, and combinations of any two or more thereof, wherein each radical contains 1 to 30 carbon atoms, each m is independently 0 or 1;

Z has the formula selected from the group consisting of N(R2)(R2), N+(R2)(R2)(R2)X- in which X is an anion selected from the group consisting of halide, sulfate, phosphate, nitrate, sulfonate, phosphonate, sulfinate, phosphinate, and combinations of any two or more thereof, G is N(R1) or O;
each Y is independently selected from the group consisting of alkylene radical, phenylene group, imidazolium 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.
18. A polymer according to claim 15 wherein said nitrogen-containing olefinic monomer is selected from the group consisting of N-acryloyl-N'-methyl piperazine, N-acryloyl-N'-ethyl piperazine, N-acryloyl-N'-propyl piperazine, N-acryloyl-N'-(2-amino-2-oxoethyl)-N'-methyl piperazinium chloride, N-acryloyl-N'-(3-amino-3-oxopropyl)-N'-methyl piperazinium chloride, N-acryloyl-N'-(4-amino-4-oxobutyl)-N'-methyl piperazinium chloride, N-acryloyl-N'-(2-amino-2-oxoethyl)-N'-ethyl piperazinium chloride, N-acryloyl-N'-(3-amino-3-oxopropyl)-N'-ethyl piperazinium chloride, N-acryloyl-N'-(4-amino-4-oxobutyl)-N'-ethyl piperazinium chloride, N,N-dimethyl-N-(3-sulfopropyl)-N-(4-vinylbenzyl) ammonium inner salt, N,N-dimethyl-N-(4-sulfobutyl)-N-(4-vinylbenzyl) ammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-N-(4-vinylbenzyl) ammonium inner salt, N,N-diethyl-N-(4-sulfobutyl)-N-(4-vinylbenzyl) ammonium inner salt, N,N-dimethyl-N-(3-sulfopropyl)-N-(3-vinylbenzyl) ammonium inner salt, N,N-dimethyl-N-(4-sulfobutyl)-N-(3-vinylbenzyl) ammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-N-(3-vinylbenzyl) ammonium inner salt, N,N-diethyl-N-(4-sulfobutyl)-N-(3-vinylbenzyl) ammonium inner salt, N,N-dimethyl-N-(2-amino-2-oxoethyl)-N-(4-vinylbenzyl) ammonium chloride, N,N-diethyl-N-(2-amino-2-oxoethyl)-N-(4-vinylbenzyl) ammonium chloride, N,N-dimethyl-N-(3-amino-3-oxopropyl)-N-(4-vinylbenzyl) ammonium chloride, N,N-diethyl-N-(3-amino-3-oxopropyl)-N-(4-vinylbenzyl) ammonium chloride, N,N-dimethyl-N-(2-amino-2-oxoethyl)-N-(3-vinylbenzyl) ammonium chloride, N,N-diethyl-N-(2-amino-2-oxoethyl)--N-(3-vinylbenzyl) ammonium chloride, N,N-dimethyl-N-(3-amino-3-oxopropyl)-N-(3-vinylbenzyl) ammonium chloride, N,N-diethyl-N-(3-amino-3-oxopropyl)-N-(3-vinylbenzyl) ammonium chloride, N-(2-amino-2-oxoethyl)-N'-vinyl imidazolium chloride, N-(3-amino-3-oxopropyl)-N'-vinyl imidazolium chloride, N-(4-amino-4-oxobutyl)-N'-vinyl imidazolium chloride, N,N-dimethyl-N-(3-sulfopropyl)-3-(acryloyl amino)-1-propaneammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-3-(acryloyl amino)-1-propaneammonium inner salt, N,N-dimethyl-N-(4-sulfobutyl)-3-(acryloyl amino)-1-propaneammonium inner salt, N,N-diethyl-N-(4-sulfobutyl)-3-(acryloyl amino)-1-propaneammonium inner salt, N,N-dimethyl-N-(3-sulfopropyl)-2-(acryloyl amino)-1-ethaneammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-2-(acryloyl amino)-1-ethaneammonium inner salt, N,N-dimethyl-N-(4-sulfobutyl)-2-(acryloyl amino)-1-ethaneammonium inner salt, N,N-diethyl-N-(4-sulfobutyl)-2-(acryloyl amino)-1-ethaneammonium inner salt, and combinations of any two or more thereof.
19. A polymer according to claim 15 wherein said nitrogen-containing olefinic monomer is selected from the, group consisting of N,N-dimethyl-N-(3-sulfopropyl)-N-(4-vinylbenzyl) ammonium inner salt, N,N-dimethyl-N-(3-sulfobutyl)-N-(4-vinylbenzyl) ammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-N-(4-vinylbenzyl) ammonium inner salt, N,N-diethyl-N-(3-sulfobutyl)-N-(4-vinylbenzyl) ammonium inner salt, N,N-dimethyl-N-(3-sulfopropyl)-N-(3-vinylbenzyl) ammonium inner salt, N,N-dimethyl-N-(3-sulfobutyl)-N-(3-vinylbenzyl) ammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-N-(3-vinylbenzyl) ammonium inner salt, N,N-diethyl-N-(3-sulfobutyl)-N-(3-viinylbenzyl) ammonium inner salt, N-acryloyl-N'-methyl-N'-(2-amino-2-oxoethyl) piperazinium chloride, N-acryloyl-N'-methyl-N'-(3-amino-3-oxopropyl) piperazinium chloride, N-acryloyl-N'-methyl-N'-(4-amino-4-oxobutyl) piperazinium chloride, N-acryloyl-N'-ethyl-N'-(2-amino-2-oxoethyl) piperazinium chloride, N-acryloyl-N'-ethyl-N'-(3-amino-3-oxopropyl) piperazinium chloride, N-acryloyl-N'-ethyl-N'-(4-amino-4-oxobutyl) piperazinium chloride, N,N-dimethyl-N-(2-amine-2.-oxoethyl)-N-(4-vinylbenzyl) ammonium chloride, N,N-diethyl-N-(2-amino-2-oxoethyl)-N-(4-vinylbenzyl)ammonium chloride, N,N-dimethyl-N-(3-amino-3-oxopropyl)-N-(4-vinylbenzyl)ammonium chloride, N,N-diethyl-N-(3-amino-3-oxopropyl)-N-(4-vinylbenzyl)ammonium chloride, N-(2-amino-2-oxoethyl)-N-vinylimidazolium chloride, N-(3-amino-3-oxopropyl)-N'-vinylimidazolium chloride, N-(4-amino-4-oxobutyl)-N'-vinylimidazolium chloride, and combinations of any two or more thereof.
20. A polymer according to claim 17 wherein said nitrogen-containing olefinic monomer is selected from the group consisting of N-acryloyl-morpholine, N-acryloyl-N'-methyl piperazine, N-acryloyl-N'-ethyl piperazine, N-acryloyl-N'-propyl piperazine, N-acryloyl-N'-(2-amino-2-oxoethyl)-N'-methyl piperazinium chloride, N-acryloyl-N'-(3-amino-3-oxopropyl)-N'-methyl piperazinium chloride, N-acryloyl-N'-(4-amino-4-oxobutyl)-N'-methyl piperazinium chloride, N-acryloyl-N'-(2-amino-2-oxoethyl)-N'-ethyl piperazinium chloride, N-acryloyl-N'-(3-amino-3-oxopropyl)-N'-ethyl piperazinium chloride, N-acryloyl-N'-(4-amino-4-oxobutyl)-N'-ethyl piperazinium chloride, N,N-dimethyl-N-(3-sulfopropyl)-N-(4-vinylbenzyl)ammonium inner salt, N,N-dimethyl-N-(4-sulfobutyl)-N-(4-vinylbenzyl)ammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-N-(4-vinylbenzyl)ammonium inner salt, N,N-diethyl-N-(4-sulfobutyl)-N-(4-vinylbenzyl)ammonium inner salt, N,N-dimethyl-N-(3-sulfopropyl)-N-(3-vinylbenzyl)ammonium inner salt, N,N-dimethyl-N-(4-sulfobutyl)-N-(3-vinylbenzyl)ammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-N-(3-vinylbenzyl)ammonium inner salt, N,N-diethyl-N-(4-sulfobutyl)-N-(3-vinylbenzyl)ammonium inner salt, N,N-dimethyl-N-(2-amino-2-oxoethyl)-N-(4-vinylbenzyl)ammonium chloride, N,N-diethyl-N-(2-amino-2-oxoethyl)-N-(4-vinylbenzyl)ammonium chloride, N,N-dimethyl-N-(3-amino-3-oxopropyl)-N-(4-vinylbenzyl)ammonium chloride, N,N-diethyl-N-(3-amino-3-oxopropyl)-N-(4-vinylbenzyl)ammonium chloride, N,N-dimethyl-N-(2-amino-2-oxoethyl)-N-(3-vinylbenzyl)ammonium chloride, N,N-diethyl-N-(2-amino-2-oxoethyl)-N-(3-vinylbenzyl)ammonium chloride, N,N-dimethyl-N-(3-amino-3-oxopropyl)-N-(3-vinylbenzyl)ammonium chloride, N,N-diethyl-N-(3-amino-3-oxopropyl)-N-(3-vinylbenzyl)ammonium chloride, N-(2-amino-2-oxoethyl)-N'-vinyl imidazolium chloride, N-(3-amino-3-oxopropyl)-N'-vinyl imidazolium chloride, N-(4-amino-4-oxobutyl)-N'-vinyl imidazolium chloride, N,N-dimethyl-N-(3-sulfopropyl)-3-(acryloyl amino)-1-propaneammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-3-(acryloyl amino)-1-propaneammonium inner salt, N,N-dimethyl-N-(4-sulfobutyl)-3-(acryloyl amino)-1-propaneammonium inner salt, N,N-diethyl-N-(4-sulfobutyl)-3-(acryloyl amino)-1-propaneammonium inner salt, N,N-dimethyl-N-(3-sulfopropyl)-2-(acryloyl amino)-1-ethaneammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-2-(acryloyl amino)-1-ethaneammonium inner salt, N,N-dimethyl-N-(4-sulfobutyl)-2-(acryloyl amino)-1-ethaneammonium inner salt, N,N-diethyl-N-(4-sulfobutyl)-2-(acryloyl amino)-1-ethaneammonium inner salt, and combinations of any two or more thereof.
21. A polymer according to claim 17 wherein said nitrogen-containing olefinic monomer has the formula selected from the group consisting of N,N-dimethyl-N-(3-sulfopropyl)-N-(4-vinylbenzyl)ammonium inner salt, N,N-dimethyl-N-(3-sulfobutyl)-N-(4-vinylbenzyl)ammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-N-(4-vinylbenzyl)ammonium inner salt, N,N-diethyl-N-(3-sulfobutyl)-N-(4-vinylbenzyl)ammonium inner salt, N,N-dimethyl-N-(3-sulfopropyl)-N-(3-vinylbenzyl)ammonium inner salt, N,N-dimethyl-N-(3-sulfobutyl)-N-(3-vinylbenzyl)ammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-N-(3-vinylbenzyl)ammonium inner salt, N,N-diethyl-N-(3-sulfobutyl)-N-(3-vinylbenzyl)ammonium inner salt, N-acryloyl-N'-methyl-N'-(2-amino-2-oxoethyl)piperazinium chloride, N-acryloyl-N'-methyl-N'-(3-amino-3-oxopropyl)piperazinium chloride, N-acryloyl-N'-methyl-N'-(4-amino-4-oxobutyl)piperazinium chloride, N-acryloyl-N'-ethyl-N'-(2-amino-2-oxoethyl)piperazinium chloride, N-acryloyl-N'-ethyl-N'-(3-amino-3-oxopropyl)piperazinium chloride, N-acryloyl-N'-ethyl-N'-(4-amino-4-oxobutyl)piperazinium chloride, N,N-dimethyl-N-(2-amino-2-oxoethyl)-N-(4-vinylbenzyl)ammonium chloride, N,N-diethyl-N-(2-amino-2-oxoethyl)-N-(4-vinylbenzyl)ammonium chloride, N,N-dimethyl-N-(3-amino-3-oxopropyl)-N-(4-vinylbenzyl)ammonium chloride, N,N-diethyl-N-(3-amino-3-oxopropyl)-N-(4-vinylbenzyl)ammonium chloride, N-(2-amino-2-oxoethyl)-N'-vinylimidazolium chloride, N-(3-amino-3-oxopropyl)-N'-vinylimidazolium chloride, N-(4-amino-4-oxobutyl)-N'-vinylimidazolium chloride, and combinations of any two or more thereof.
22. A polymer according to claim 17 wherein said nitrogen-containing olefinic monomer is N-acryloyl-N'-methyl piperazine.
23. A polymer according to claim 17 wherein said nitrogen-containing olefinic monomer is N-acryloyl-N'-(2-amino-2-oxoethyl)-N'-methyl piperazinium chloride.
24. A polymer according to claim 17 wherein said nitrogen-containing olefinic monomer is N,N-dimethyl-N-(3-sulfropropyl)-N-(4-vinylbenzyl)ammonium inner salt.
25. A polymer according to claim 17 wherein said nitrogen-containing olefinic monomer is N,N-dimethyl-N-(2-amino-2-oxoethyl)-N-(4-vinylbenzyl)ammonium chloride.
26. A polymer according to claim 17 wherein said nitrogen-containing olefinic monomer is N-(2-amino-2-oxoethyl)-N'-vinyl imidazolium chloride.
27. A polymer according to claim 17 wherein said nitrogen-containing olefinic monomer is N,N-dimethyl-N-(3-sulfopropyl)-3-(acryloyl amino)-1-propaneammonium inner salt.
28. A polymer according to claim 17 wherein said nitrogen-containing olefinic monomer is N-acryloylmorpholine.
29. A polymer according to claim 17 wherein said olefinic comonomer is selected from the group consisting of acrylamide, styrene sulfonic acid, salt of styrene sulfonic acid, N-methylacrylamide, N,N-dimethylacrylamide, acrylic acid, salt of acrylic acid, N-vinylpyrrolidone, methyl acrylate, a methacrylate, vinyl sulfonic acid, salt of vinyl sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, salt of 2-acrylamido-2-methylpropanesulfonic acid, and combinations of any two or more thereof.
30. A polymer according to claim 29 wherein said olefinic comonomer is acrylamide.
31. A water-soluble polymer comprising repeat units derived from at least one nitrogen-containing olefinic monomer and at least one olefinic comonomer wherein said nitrogen-containing olefinic monomer has a formula selected from the group consisting of R1-C(R1)=C(R1)-(C=O)m-M, R1C(R1)=C(R1)-(C=O)-(NH)m-(Ar)m-N+(R2)(R2)-Y-SO3-, R1-C(R1)=C(R1)-(C=O)m-(NH)m-(Ar)m-Y-N+(R2)(R2)-Y-(C=O)m-N(R2)(R2)X- and combinations of any two or more thereof and said olefinic comonomer has the formula selected from the group consisting of R1-C(R1)=C(R1)-W, R1-C(R1)=C(R1)-(C=O)m-Z, R1-C(R1)=C(R1)-Y-W, R1-C(R1)=C(R1)-(C=O)m-N(R2)-Y-R2, R1-C(R1)=C(R1)-(C=O)m-G-Y-Z, R1C(R1)=C(R1)-(C=O)m-G-Y-W, R1-C(R1)=C(R1)-(C=O)m-Y-Z wherein R1 and R2 are each independently selected from the group consisting of hydrogen, alkyl radical, aryl radical, aralkyl radical, alkaryl radical, and combinations of any two or more thereof wherein each radical contains 1 to 30 carbon atoms;
M is a substituted or unsubstituted morpholine group;
each Y is independently selected from the group consisting of alkylene radical, phenylene group, imidazolium group, naphthylene group, biphenylene group, and combinations of any two or more thereof;

Ar is an arylene group;
G is N(R1) or O;
Z has the formula selected from the group consisting of N(R2)(R2), N+(R2)(R2)(R2)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, phosphonate, 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 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.
32. A polymer according to claim 31 wherein said nitrogen-containing olefinic monomer is selected from the group consisting of N-acryloyl-morpholine, N-acryloyl-N'-methyl piperazine, N-acryloyl-N'-ethyl piperazine, N-acryloyl-N'-propyl piperazine, N-acryloyl-N'-(2-amino-2-oxoethyl)-N'-methyl piperazinium chloride, N-acryloyl-N'-(3-amino-3-oxopropyl)-N'-methyl piperazinium chloride, N-acryloyl-N'-(4-amino-4-oxobutyl)-N'-methyl piperazinium chloride, N-acryloyl-N'-(2-amino-2-oxoethyl)-N'-ethyl piperazinium chloride, N-acryloyl-N'-(3-amino-3-oxopropyl)-N'-ethyl piperazinium chloride, N-acryloyl-N'-(4-amino-4-oxobutyl)-N'-ethyl piperazinium chloride, N,N-dimethyl-N-(3-sulfopropyl)-N-(4-vinylbenzyl)ammonium inner salt, N,N-dimethyl-N-(4-sulfobutyl)-N-(4-vinylbenzyl)ammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-N-(4-vinylbenzyl)ammonium inner salt, N,N-diethyl-N-(4-sulfobutyl)-N-(4-vinylbenzyl)ammonium inner salt, N,N-dimethyl-N-(3-sulfopropyl)-N-(3-vinylbenzyl)ammonium inner salt, N,N-dimethyl-N-(4-sulfobutyl)-N-(3-vinylbenzyl)ammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-N-(3-vinylbenzyl)ammonium inner salt, N,N-diethyl-N-(4-sulfobutyl)-N-(3-vinylbenzyl)ammonium inner salt, N,N-dimethyl-N-(2-amino-2-oxoethyl)-N-(4-vinylbenzyl)ammonium chloride, N,N-diethyl-N-(2-amino-2-oxoethyl)-N-(4-vinylbenzyl)ammonium chloride, N,N-dimethyl-N-(3-amino-3-oxopropyl)-N-(4-vinylbenzyl)ammonium chloride, N,N-diethyl-N-(3-amino-3-oxopropyl)-N-(4-vinylbenzyl)ammonium chloride, N,N-dimethyl-N-(2-amino-2-oxoethyl)-N-(3-vinylbenzyl)ammonium chloride, N,N-diethyl-N-(2-amino-2-oxoethyl)-N-(3-vinylbenzyl)ammonium chloride, N,N-dimethyl-N-(3-amino-3-oxopropyl)-N-(3-vinylbenzyl)ammonium chloride, N,N-diethyl-N-(3-amino-3-oxopropyl)-N-(3-vinylbenzyl)ammonium chloride.
N-(2-amino-2-oxoethyl)-N'-vinyl imidazolium chloride, N-(3-amino-3-oxopropyl)-N'-vinyl imidazolium chloride, N-(4-amino-4-oxobutyl)-N'-vinyl imidazolium chloride, N,N-dimethyl-N-(3-sulfopropyl)-3-(acryloyl amino)-1-propaneammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-3-(acryloyl amino)-1-propaneammonium inner salt, N,N-dimethyl-N-(4-sulfobutyl)-3-(acryloyl amino)-1-propaneammonium inner salt, N,N-diethyl-N-(4-sulfobutyl)-3-(acryloyl amino)-1-propaneammonium inner salt, N,N-dimethyl-N-(3-sulfopropyl)-2-(acryloyl amino)-1-ethaneammonium inner salt, N,N-diethyl-N-(3-sulfropropyl)-2-(acryloyl amino)-1-ethaneammonium inner salt, N,N-dimethyl-N-(4-sulfobutyl)-2-(acryloyl amino)-1-ethaneammonium inner salt, N,N-diethyl-N-(4-sulfobutyl)-2-(acryloyl amino)ethaneammonium inner salt, and combinations of any two or more thereof.
33. A polymer according to claim 31 wherein said nitrogen-containing olefinic monomer is selected from the group consisting of N,N-dimethyl-N-(3-sulfopropyl)-N-(4-vinylbenzyl)ammonium inner salt, N,N-dimethyl-N-(3-sulfobutyl)-N-(4-vinylbenzyl)ammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-N-(4-vinylbenzyl)ammonium inner salt, N,N-diethyl-N-(3-sulfobutyl)-N-(4-vinylbenzyl)ammonium inner salt, N,N-dimethyl-N-(3-sulfopropyl)-N-(3-vinylbenzyl)ammonium inner salt, N,N-dimethyl-N-(3-sulfobutyl)-N-(3-vinylbenzyl)ammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-N-(3-vinylbenzyl)ammonium inner salt, N,N-diethyl-N-(3-sulfobutyl)-N-(3-vinylbenzyl)ammonium inner salt, N-acryloyl-N'-methyl-N'-(2-amino-2-oxoethyl)piperazinium chloride, N-acryloyl-N'-methyl-N'-(3-amino-3-oxopropyl)piperazinium chloride, N-acryloyl-N'-methyl-N'-(4-amino-4-oxobutyl)piperzinium chloride, N-acryloyl-N'-ethyl-N'-(2-amino-2-oxoethyl)piperazinium chloride, N-acryloyl-N'-ethyl-N'-(3-amino-3-oxopropyl)piperazinium chloride, N-acryloyl-N'-ethyl-N'-(4-amino-4-oxobutyl)piperazinium chloride, N,N-dimethyl-N-(2-amino-2-oxoethyl)-N-(4-vinylbenzyl)ammonium chloride, N,N-diethyl-N-(2-amino-2-oxoethyl)-N-(4-vinylbenzyl)ammonium chloride, N,N-dimethyl-N-(3-amino-3-oxopropyl)-N-(4-vinylbenzyl)ammonium chloride, N,N-diethyl-N-(3-amino-3-oxopropyl)-N-(4-vinylbenzyl)ammonium chloride, N-(2-amino-2-oxoethyl)-N'-vinylimidazolium chloride, N-(3-amino-3-oxopropyl)-N'-vinylimidazolium chloride, N-(4-amino-4-oxobutyl)-N'-vinylimidazolium chloride, and combinations of any two or more thereof.
34. A polymer according to claim 31 wherein said nitrogen-containing olefinic monomer is N-acryloyl-N'-methyl piperazine.
35. A polymer according to claim 31 wherein said nitrogen-containing olefinic monomer is N-acryloyl-N'-(2-amino-2-oxoethyl)-N'-methyl piperazinium chloride.
36. A polymer according to claim 31 wherein said nitrogen-containing olefinic monomer is N,N-dimethyl-N-(3-sulfopropyl)-N-(4-vinylbenzyl)ammonium inner salt.
37. A polymer according to claim 31 wherein said nitrogen-containing olefinic monomer is N,N-dimethyl-N-(2-amino-2-oxoethyl)-N-(4-vinylbenzyl)ammonium chloride.
38. A polymer according to claim 31 wherein said nitrogen-containing olefinic monomer is N-(2-amino-2-oxoethyl)-N'-vinyl imidazolium chloride.
39. A polymer according to claim 31 wherein said nitrogen-containing olefinic monomer is N,N-dimethyl-N-(3-sulfopropyl)-3-(acryloyl amino)-1-propaneammonium inner salt.
40. A polymer according to claim 31 wherein said nitrogen-containing olefinic monomer is N-acryloylmorpholine.
41. A polymer according to claim 31 wherein said olefinic comonomer is selected from the group consisting of acrylamide, styrene sulfonic acid, salt of styrene sulfonic acid, N-methylacrylamide, N,N-dimethylacrylamide, acrylic acid, salt of acrylic acid, N-vinylpyrrolidone, methyl acrylate, a methacrylate, vinylic sulfonic acid, salt of vinylic sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, salt 2-acrylamido-2-methylpropanesulfonic acid, and combinations of any two or more thereof.
42. A polymer according to claim 41 wherein said olefinic comonomer is acrylamide.
43. A water-soluble polymer comprising repeat units derived from at least one nitrogen-containing olefinic monomer and at least one olefinic comonomer wherein said nitrogen-containing olefinic monomer has a formula selected from the group consisting of N-acryloyl-morpholine, N-acryloyl-N'-methyl piperazine, N-acryloyl-N'-ethyl piperazine, N-acryloyl-N'-propyl piperazine, N-acryloyl-N'-(2-amino-2-oxoethyl)-N'-methyl piperazinium chloride, N-acryloyl-N'-(3-amino-3-oxopropyl)-N'-methyl piperazinium chloride, N-acryloyl-N'-(4-amino-4-oxobutyl)-N'-methyl piperazinium chloride, N-acryloyl-N'-(2-amino-2-oxoethyl)-N'-ethyl piperazinium chloride, N-acryloyl-N'-(3-amino-3-oxopropyl)-N'-ethyl piperazinium chloride, N-acryloyl-N'-(4-amino-4-oxobutyl)-N'-ethyl piperazinium chloride, N,N-dimethyl-N-(3-sulfopropyl)-N-(4-vinylbenzyl)ammonium inner salt, N,N-dimethyl-N-(4-sulfobutyl)-N-(4-vinylbenzyl)ammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-N-(4-vinylbenzyl)ammonium inner salt, N,N-diethyl-N-(4-sulfobutyl)-N-(4-vinylbenzyl)ammonium inner salt, N,N-dimethyl-N-(3-sulfopropyl)-N-(3-vinylbenzyl)ammonium inner salt, N,N-dimethyl-N-(4-sulfobutyl)-N-(3-vinylbenzyl)ammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-N-(3-vinylbenzyl)ammonium inner salt, N,N-diethyl-N-(4-sulfobutyl)-N-(3-vinylbenzyl)ammonium inner salt, N,N-dimethyl-N-(2-amino-2-oxoethyl)-N-(4-vinylbenzyl)ammonium chloride, N,N-diethyl-N-(2-amino-2-oxoethyl)-N-(4-vinylbenzyl)ammonium chloride, N,N-dimethyl-N-(3-amino-3-oxopropyl)-N-(4-vinylbenzyl)ammonium chloride, N,N-diethyl-N-(3-amino-3-oxopropyl)-N-(4-vinylbenzyl)ammonium chloride, N,N-dimethyl-N-(2-amino-2-oxoethyl)-N-(3-vinylbenzyl)ammonium chloride, N,N-diethyl-N-(2-amino-2-oxoethyl)-N-(3-vinylbenzyl)ammonium chloride, N,N-dimethyl-N-(3-amino-3-oxopropyl)-N-(3-vinylbenzyl)ammonium chloride, N,N-diethyl-N-(3-amino-3-oxopropyl)-N-(3-vinylbenzyl)ammonium chloride, N-(2-amino-2-oxoethyl)-N'-vinyl imidazolium chloride, N-(3-amino-3-oxopropyl)-N'-vinyl imidazolium chloride, N-(4-amino-4-oxobutyl)-N'-vinyl imidazolium chloride, N,N-dimethyl-N-(3-sulfopropyl)-3-(acryloyl amino)-1-propaneammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-3-(acryloyl amino)-l-propaneammonium inner salt, N,N-dimethyl-N-(4-sulfobutyl)-3-(acryloyl amino)-1-propaneammonium inner salt, N,N-diethyl-N-(4-sulfobutyl)-3-(acryloyl amino)-1-propaneammonium inner salt, N,N-dimethyl-N-(3-sulfopropyl)-2-(acryloyl amino)-1-ethaneammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-2-(acryloyl amino)-1-ethaneammonium inner salt, N,N-dimethyl-N-(4-sulfobutyl)-2-(acryloyl amino)-1-ethaneammonium inner salt, N,N-diethyl-N-(4-sulfobutyl)-2-(acryloyl amino)-1-ethaneammonium inner salt, and combinations of any two or more thereof; and said olefinic comonomer is selected from the group consisting of acrylamide, styrene sulfonic acid, salt of styrene sulfonic acid, N-methylacrylamide, N,N-dimethylacrylamide, acrylic acid, salt of acrylic acid, N-vinylpyrrolidone, methyl acrylate, a methacrylate, vinylic sulfonic acid, salt of vinylic sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, salt of 2-acrylamido-2-methylpropanesulfonic acid, and combinations of any two or more thereof.
44. A polymer according to claim 43 wherein said nitrogen-containing olefinic monomer is N-acryloyl-N'-methyl piperazine.
45. A polymer according to claim 43 wherein said nitrogen-containing olefinic monomer is N-acryloyl-N'-(2-amino-2-oxoethyl)-N'-methyl piperazinium chloride.
46. A polymer according to claim 43 wherein said nitrogen-containing olefinic monomer is N,N-dimethyl-N-(3-sulfopropyl)-N-(4-vinylbenzyl)ammonium inner salt.
47. A polymer according to claim 43 wherein said nitrogen-containing olefinic monomer is N,N-dimethyl-N-(2-amino-2-oxoethyl)-N-(4-vinylbenzyl)ammonium chloride.
48. A polymer according to claim 43 wherein said nitrogen-containing olefinic monomer is N-(2-amino-2-oxoethyl)-N'-vinyl imidazolium chloride.
49. A polymer according to claim 43 wherein said nitrogen-containing olefinic monomer is N,N-dimethyl-N-(3-sulfopropyl)-3-(acryloyl amino)-1-propaneammonium inner salt.
50. A polymer according to claim 43 wherein said nitrogen-containing olefinic monomer is N-acryloylmorpholine.
51. A polymer according to claim 43 wherein said olefinic comonomer is acrylamide.
52. 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 having the formula selected from the group consisting of R1-C(R1)=C(R1)-(C=O)m-M, R1C(R1)=C(R1)-(C=O)m-(NH)m-(Ar)m-N+(R2)(R2)-Y-SO3-, R1-C(R1)=C(R1)-(C=O)m-(NH)m-(Ar)m-Y-N+(R2)(R2)-Y-(C=O)m-N(R2)(R2)X-, and combinations of any two or more thereof wherein each R1 and R2 are the same or different and independently selected from the group consisting of hydrogen, alkyl radical, aryl radical, aralkyl radical, alkaryl radical, and combinations of any two or more thereof wherein each radical contains 1 to 30 carbon atoms;
M is a substituted or unsubstituted morpholine group;
each X is an anion selected from the group consisting of halide, sulfate, phosphate, nitrate, sulfonate, phosphonate, sulfinate, phosphinate, and combinations of any two or more thereof;
each Y is independently selected from the group consisting of alkylene radical, phenylene group, imidazolium group, naphthylene group, biphenylene group, and combinations of any two or more thereof;
Ar is an arylene group;
and each m is independently 0 or 1.
53. A process according to claim 52 wherein said polymer further comprises repeat units derived from at least one olefinic comonomer having the formula selected from the group consisting of R1-C(R1)-C(R1)-W, R1-C(R1)=C(RO-(C-O)m-Z, R1-C(R1)=C(R1)-Y-W, R1-C(R1)=C(R1)-(C=O)m-N(R2)-Y-R2, R1-C(R1)=C(R1)-(C=O)m-G-Y-Z
R1C(R1)=C(R1)-(C=O)m-G-Y-W, R1-C(R1)=C(R1)-(C=O)m-Y-Z, and combinations of any two or more thereof wherein each R1 and R2 are the same or different and are independently selected from the group consisting of hydrogen, alkyl radical, aryl radical, aralkyl radical, alkaryl radical, and combinations of any two or more thereof;
each m is independently 0 or 1, M is a substituted or unsubstituted morpholine;
Z has the formula selected from the group consisting of N(R2)(R2), N+(R2)(R2)(R2)X- in which X is an anion selected from the group consisting of halide, sulfate, phosphate, nitrate, sulfonate, phosphonate, sulfinate, phosphinate, and combinations of any two or more thereof;
G is N(R2) or O;
each Y is independently selected from the group consisting of alkylene radical, phenylene group, imidazolium 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.
54. A process according to claim 52 wherein the polymer further comprises repeat units derived from at least one olefinic comonomer having the formula selected from the group consisting of R1-C(R1)=C(R1)-(C=O)m-Z, R1-C(RO=C(R1)-(C-O)m-Y-W, R1-C(R1)=C(R1)-W, R1-C(R1)=C(R1)-(C=O)-G-Y-W, and combinations of any two or more thereof wherein each R1 is the same or different and is independently selected from the group consisting of 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 the group consisting of N(R2)(R2), N+(R2)(R2)(R2)X- in which X is an anion selected from the group consisting of halide, sulfate, phosphate, nitrate, sulfonate, phosphonate, sulfinate, phosphinate, and combinations of any two or more thereof;
G is N(R1) or O;
each Y is independently selected from the group consisting of alkylene radical, phenylene group, imidazolium 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.
55. A process according to claim 52 wherein said nitrogen-containing olefinic monomer is selected from the group consisting of N-acryloyl morpholine, N-acryloyl-N'-methyl piperazine, N-acryloyl-N'-ethyl piperazine, N-acryloyl-N'-propyl piperazine, N-acryloyl-N'-(3-sulfopropyl)-N'-methyl piperazinium inner salt, N-acryloyl-N'-(3-sulfopropyl)-N'-ethyl piperazinium inner salt, N-acryloyl-N'-(4-sulfobutyl)-N'-methyl piperazinium inner salt, N-acryloyl-N'-(4-sulfobutyl)-N'-ethyl piperazinium inner salt, N-acryloyl-N'-(2-amino-2-oxoethyl)-N'-methyl piperazinium chloride, N-acryloyl-N'-(3-amino-3-oxopropyl)-N'-methyl piperazinium chloride, N-acryloyl-N'-(4-amino-4-oxobutyl)-N'-methyl piperazinium chloride, N-acryloyl-N'-(2-amino-2-oxoethyl)-N'-ethyl piperazinium chloride, N-acryloyl-N'-(3-amino-3-oxopropyl)-N'-ethyl piperazinium chloride, N-acryloyl-N'-(4-amino-4-oxobutyl)-N'-ethyl piperazinium chloride, N,N-dimethyl-N-(3-sulfopropyl)-N-(4-vinylbenzyl) ammonium inner salt, N,N-dimethyl-N-(4-sulfobutyl)-N-(4-vinylbenzyl) ammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-N-(4-vinylbenzyl) ammonium inner salt, N,N-diethyl-N-(4-sulfobutyl)-N-(4-vinylbenzyl) ammonium inner salt, N,N-dimethyl-N-(3-sulfopropyl)-N-(3-vinylbenzyl) ammonium inner salt, N,N-dimethyl-N-(4-sulfobutyl)-N-(3-vinylbenzyl) ammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-N-(3-vinylbenzyl) ammonium inner salt, N,N-diethyl-N-(4-sulfobutyl)-N-(3-vinylbenzyl) ammonium inner salt, N,N-dimethyl-N-(2-amino-2-oxoethyl)-N-(4-vinylbenzyl) ammonium chloride, N,N-diethyl-N-(2-amino-2-oxoethyl)-N-(4-vinylbenzyl) ammonium chloride, N,N-dimethyl-N-(3-amino-3-oxopropyl)-N-(4-vinylbenzyl) ammonium chloride, N,N-diethyl-N-(3-amino-3-oxopropyl)-N-(4-vinylbenzyl) ammonium chloride, N,N-dimethyl-N-(2-amino-2-oxoethyl)-N-(3-vinylbenzyl) ammonium chloride, N,N-diethyl-N-(2-amino-2-oxoethyl)-N-(3-vinylbenzyl) ammonium chloride, N,N-dimethyl-N-(3-amino-3-oxopropyl)-N-(3-vinylbenzyl) ammonium chloride, N,N-diethyl-N-(3-amino-3-oxopropyl)-N-(3-vinylbenzyl) ammonium chloride, N-(2- amino-2-oxoethyl)-N'-vinyl imidazolium chloride, N-(3-amino-3-oxopropyl)-N'-vinyl imidazolium chloride, N-(4-amino-4-oxobutyl)-N'-vinyl imidazolium chloride, N,N-dimethyl-N-(3-sulfopropyl)-3-(acryloyl amino)-1-propaneammonium inner salt, N,N-diethyl-N-(3 -sulfopropyl)-3 -(acryloyl amino)-1-propaneammonium inner salt, N,N-dimethyl-N-(4-sulfobutyl)-3-(acryloyl amino)-1-propaneammonium inner salt, N,N-diethyl-N-(4-sulfobutyl)-3-(acryloyl amino)-1-propaneammonium inner salt, N,N-dimethyl-N-(3-sulfopropyl)-2-(acryloyl amino)-1-ethaneammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-2-(acryloyl amino)-1-ethaneammonium inner salt, N,N-dimethyl-N-(4-sulfobutyl)-2-(acryloyl amino)-1-ethaneammonium inner salt, N,N-diethyl-N-(4-sulfobutyl)-2-(acryloyl amino)-1-ethaneammonium inner salt, and combinations of any two or more thereof.
56. A process according to claim 52 wherein said nitrogen-containing olefinic monomer is selected from the group consisting of N,N-dimethyl-N-(3-sulfopropyl)-N-(4-vinylbenzyl) ammonium inner salt, N,N-dimethyl-N-(3-sulfobutyl)-N-(4-vinylbenzyl) ammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-N-(4-vinylbenzyl) ammonium inner salt, N,N-diethyl-N-(3-sulfobutyl)-N-(4-vinylbenzyl) ammonium inner salt, N,N-dimethyl-N-(3-sulfopropyl)-N-(3-vinylbenzyl) ammonium inner salt, N,N-dimethyl-N-(3-sulfobutyl)-N-(3-vinylbenzyl) ammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-N-(3-vinylbenzyl) ammonium inner salt, N,N-diethyl-N-(3-sulfobutyl)-N-(3-vinylbenzyl) ammonium inner salt;
N-acryloyl-N'-methyl-N'-(2-amino-2-oxoethyl) piperazinium chloride, N-acryloyl-N'-methyl-N'-(3-amino-3-oxopropyl) piperazinium chloride, N-acryloyl-N'-methyl-N'-(4-amino-4-oxobutyl) piperazinium chloride, N-acryloyl-N'-ethyl-N'-(2-amino-2-oxoethyl) piperazinium chloride, N-acryloyl-N'-ethyl-N'-(3-amino-3-oxopropyl) piperazinium chloride, N-acryloyl-N'-ethyl-N'-(4-amino-4-oxobutyl) piperazinium chloride, N,N-dimethyl-N-(2-amino-2-oxoethyl)-N-(4-vinylbenzyl) ammonium chloride, N,N-diethyl-N-(2-amino-2-oxoethyl)-N-(4-vinylbenzyl) ammonium chloride, N,N-dimethyl-N-(3-amino-3-oxopropyl)-N-(4-vinylbenzyl) ammonium chloride, N,N-diethyl-N-(3-amino-3-oxopropyl)-N-(4-vinylbenzyl) ammonium chloride, N-(2-amino-2-oxoethyl)-N'-vinylimidazolium chloride, N-(3-amino-3-oxopropyl)-N'-vinylimidazolium chloride, N-(4-amino-4-oxobutyl)-N'-vinylimidazolium chloride, and combinations of any two or more thereof.
57. 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 selected from the group consisting of N-acryloyl morpholine, N-acryloyl-N'-methyl piperazine, N-acryloyl-N'-ethyl piperazine, N-acryloyl-N'-propyl piperazine, N-acryloyl-N'-(3-sulfopropyl)-N'-methyl piperazinium inner salt, N-acryloyl-N'-(3-sulfopropyl)-N'-ethyl piperazinium inner salt, N-acryloyl-N'-(4-sulfobutyl)-N'-methyl piperazinium inner salt, N-acryloyl-N'-(4-sulfobutyl)-N'-ethyl piperazinium inner salt, N-acryloyl-N'-(2-amino-2-oxoethyl)-N'-methyl piperazinium chloride, N-acryloyl-N'-(3-amino-3-oxopropyl)-N'-methyl piperazinium chloride, N-acryloyl-N'-(4-amino-4-oxobutyl)-N'-methyl piperazinium chloride, N-acryloyl-N'-(2-amino-2-oxoethyl)-N'-ethyl piperazinium chloride, N-acryloyl-N'-(3-amino-3-oxopropyl)-N'-ethyl piperazinium chloride, N-acryloyl-N'-(4-amino-4-oxobutyl)-N'-ethyl piperazinium chloride, N,N-dimethyl-N-(3-sulfopropyl)-N-(4-vinylbenzyl) ammonium inner salt, N,N-dimethyl-N-(4-sulfobutyl)-N-(4-vinylbenzyl) ammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-N-(4-vinylbenzyl) ammonium inner salt, N,N-diethyl-N-(4-sulfobutyl)-N-(4-vinylbenzyl) ammonium inner salt, N,N-dimethyl-N-(3-sulfopropyl)-N-(3-vinylbenzyl) ammonium inner salt, N,N-dimethyl-N-(4-sulfobutyl)-N-(3-vinylbenzyl) ammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-N-(3-vinylbenzyl) ammonium inner salt, N,N-diethyl-N-(4-sulfobutyl)-N-(3-vinylbenzyl) ammonium inner salt, N,N-dimethyl-N-(2-amino-2-oxoethyl)-N-(4-vinylbenzyl) ammonium chloride, N,N-diethyl-N-(2-amino-2-oxoethyl)-N-(4-vinylbenzyl) ammonium chloride, N,N-dimethyl-N-(3-amino-3-oxopropyl)-N-(4-vinylbenzyl) ammonium chloride, N,N-diethyl-N-(3-amino-3-oxopropyl)-N-(4-vinylbenzyl) ammonium chloride, N,N-dimethyl-N-(2-amino-2-oxoethyl)-N-(3-vinylbenzyl) ammonium chloride, N,N-diethyl-N-(2-amino-2-oxoethyl)-N-(3-vinylbenzyl) ammonium chloride, N,N-dimethyl-N-(3-amino-3-oxopropyl)-N-(3-vinylbenzyl) ammonium chloride, N,N-diethyl-N-(3-amino-3-oxopropyl)-N-(3-vinylbenzyl) ammonium chloride, N-(2-amino-2-oxoethyl)-N'-vinyl imidazolium chloride, N-(3-amino-3-oxopropyl)-N'-vinyl imidazolium chloride, N-(4-amino-4-oxobutyl)-N'-vinyl imidazolium chloride, N,N-dimethyl-N-(3-sulfopropyl)-3-(acryloyl amino)-1-propaneammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-3-(acryloyl amino)-1-propaneammonium inner salt, N,N-dimethyl-N-(4-sulfobutyl)-3-(acryloyl amino)-1-propaneammonium inner salt, N,N-diethyl-N-(4-sulfobutyl)-3-(acryloyl amino)-1-propaneammonium inner salt, N,N-dimethyl-N-(3-sulfopropyl)-2-(acryloyl amino)-1-ethaneammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-2-(acryloyl amino)-1-ethaneammonium inner salt, N,N-dimethyl-N-(4-sulfobutyl)-2-(acryloyl amino)-1-ethaneammonium inner salt, N,N-diethyl-N-(4-sulfobutyl)-2-(acryloyl amino)-1-ethaneammonium inner salt, and combinations of any two or more thereof.
58. 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 selected from the group consisting of N,N-dimethyl-N-(3-sulfopropyl)-N-(4-vinylbenzyl) ammonium inner salt, N,N-dimethyl-N-(3-sulfobutyl)-N-(4-vinylbenzyl) ammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-N-(4-vinylbenzyl) ammonium inner salt, N,N-diethyl-N-(3-sulfobutyl)-N-(4-vinylbenzyl) ammonium inner salt, N,N-dimethyl-N-(3-sulfopropyl)-N-(3-vinylbenzyl) ammonium inner salt, N,N-dimethyl-N-(3-sulfobutyl)-N-(3-vinylbenzyl) ammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-N-(3-vinylbenzyl) ammonium inner salt, N,N-diethyl-N-(3-sulfobutyl)-N-(3-vinylbenzyl) ammonium inner salt, N-acryloyl-N'-methyl-N'-(2-amino-2-oxoethyl) piperazinium chloride, N-acryloyl-N'-methyl-N'-(3-amino-3-oxopropyl) piperazinium chloride, N-acryloyl-N'-methyl-N'-(4-amino-4-oxobutyl) piperazinium chloride, N-acryloyl-N'-ethyl-N'-(2-amino-2-oxoethyl) piperazinium chloride, N-acryloyl-N'-ethyl-N'-(3-amino-3-oxopropyl) piperazinium chloride, N-acryloyl-N'-ethyl-N'-(4-amino-4-oxobutyl) piperazinium chloride, N,N-dimethyl-N-(2-amino-2-oxoethyl)-N-(4-vinylbenzyl) ammonium chloride, N,N-diethyl-N-(2-amino-2-oxoethyl)-N-(4-vinylbenzyl) ammonium chloride, N,N-dimethyl-N-(3-amino-3-oxopropyl)-N-(4-vinylbenzyl) ammonium chloride, N,N-diethyl-N-(3-amino-3-oxopropyl)-N-(4-vinylbenzyl) ammonium chloride, N-(2-amino-2-oxoethyl)-N'-vinylimidazolium chloride, N-(3-amino-3-oxopropyl)-N'-vinylimidazolium chloride, N-(4-amino-4-oxobutyl)-N'-vinylimidazolium chloride, and combinations of any two or more thereof.
59. A process according to claim 55 wherein said nitrogen-containing olefinic monomer is N-acryloyl-N'-methyl piperazine.
60. A process according to claim 55 wherein said nitrogen-containing olefinic monomer is N-acryloyl-N'-(3-sulfopropyl)-N'-methyl piperazinium inner salt.
61. A process according to claim 55 wherein said nitrogen-containing olefinic monomer is N-acryloyl-N'-(2-amino-2-oxoethyl)-N'-methyl piperazinium chloride.
62. A process according to claim 55 wherein said nitrogen-containing olefinic monomer is N,N-dimethyl-N-(3-sulfopropyl)-N-(4-vinylbenzyl) ammonium inner salt.
63. A process according to claim 55 wherein said nitrogen-containing olefinic monomer is N,N-dimethyl-N-(2-amino-2-oxoethyl)-N-(4-vinylbenzyl) ammonium chloride.
-84- ~64. A process according to claim 55 wherein said nitrogen-containing olefinic monomer is N-(2-amino-2-oxoethyl)-N'-vinyl imidazolium chloride.
65. A process according to claim 55 wherein said nitrogen-containing olefinic monomer is N,N-dimethyl-N-(3-sulfopropyl)-3-(acryloyl amino)-1-propaneammonium inner salt.
66. A process according to claim 55 wherein said nitrogen-containing olefinic monomer is N-acryloylmorpholine.
67. A process according to claim 53 wherein said olefinic comonomer is selected from the group consisting of acrylamide, styrene sulfonic acid, salt of styrene sulfonic acid, N-methylacrylamide, N,N-dimethylacrylamide, acrylic acid, salt of acrylic acid, N-vinylpyrrolidone, methyl acrylate, a methacrylate, vinyl sulfonic acid, salt of vinyl sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, salt of 2-acrylamido-2-methylpropanesulfonic acid, and combinations of any two or more thereof.
68. A process according to claim 53 wherein said olefinic comonomer is acrylamide.
69. A process comprising introducing into a subterranean formation a water-soluble polymer comprising repeat units derived from at least one nitrogen-containing olefinic monomer and at least one olefinic comonomer wherein said nitrogen-containing olefinic monomer has a formula selected from the group consisting of R1-C(R1)=C(RO-(C=O)m-M, R1C(R1)=C(R1)-(C=O)m-(NH)m-(Ar)m-N+(R2)(R2)-Y-SO3-, R1-C(R1)=C(R1)-(C=O)m-(NH)m-(Ar)m-Y-N+(R2)(R2)-Y-(C=O)m-N(R2)(R2)X-, and combinations of any two or more thereof and said olefinic comonomer has the formula selected from the group consisting of R1-C(R1)=C(R1)-W, R1-C(R1)=C(R1)-(C=O)m-Z, R1-C(R1)=C(R1)-Y-W, R1-C(R1)=C(R1)-(C=O)m-N(R2)-Y-R2, R1-C(R1)=C(R1)-(C=O)m-G-Y-Z, R1C(R1)=C(R1)-(C=O)m-G-Y-W, R1-C(R1)=C(R1)-(C=O)m-Y-Z wherein R1 and R2 are each independently selected from the group consisting of hydrogen, alkyl radical, aryl radical, aralkyl radical, alkaryl radical, and combinations of any two or more thereof wherein each radical contains 1 to 30 carbon atoms;
M is a substituted or unsubstituted morpholine group;
each Y is independently selected from the group consisting of alkylene radical, phenylene group, imidazolium group, naphthylene group, biphenylene group, and combinations of any two or more thereof;
Ar is an arylene group;
G is N(R1) or O;
Z has the formula selected from the group consisting of N(R2)(R2), N+(R2)(R2)(R2)X-, and combinations of any two or more thereof;
X is an anion selected from the group consisting of halide, sulfate, phosphate, nitrate, sulfonate, phosphonate, 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 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.
70. A process according to claim 69 wherein said nitrogen-containing olefinic monomer is selected from the group consisting of N-acryloyl morpholine, N-acryloyl-N'-methyl piperazine, N-acryloyl-N'-ethyl piperazine, N-acryloyl-N'-propyl piperazine, N-acryloyl-N'-(3-sulfopropyl)-N'-methyl piperazinium inner salt, N-acryloyl-N'-(3-sulfopropyl)-N'-ethyl piperazinium inner salt, N-acryloyl-N'-(4-sulfobutyl)-N'-methyl piperazinium inner salt, N-acryloyl-N'-(4-sulfobutyl)-N'-ethyl piperazinium inner salt, N-acryloyl-N'-(2-amino-2-oxoethyl)-N'-methyl piperazinium chloride, N-acryloyl-N'-(3-amino-3-oxopropyl)-N'-methyl piperazinium chloride, N-acryloyl-N'-(4-amino-4-oxobutyl)-N'-methyl piperazinium chloride, N-acryloyl-N'-(2-amino-2-oxoethyl)-N'-ethyl piperazinium chloride, N-acryloyl-N'-(3-amino-3-oxopropyl)-N'-ethyl piperazinium chloride, N-acryloyl-N'-(4-amino-4-oxobutyl)-N'-ethyl piperazinium chloride, N,N-dimethyl-N-(3-sulfopropyl)-N-(4-vinylbenzyl) ammonium inner salt, N,N-dimethyl-N-(4-sulfobutyl)-N-(4-vinylbenzyl) ammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-N-(4-vinylbenzyl) ammonium inner salt, N,N-diethyl-N-(4-sulfobutyl)-N-(4-vinylbenzyl) ammonium inner salt, N,N-dimethyl-N-(3-sulfopropyl)-N-(3-vinylbenzyl) ammonium inner salt, N,N-dimethyl-N-(4-sulfobutyl)-N-(3-vinylbenzyl) ammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-N-(3-vinylbenzyl) ammonium inner salt, N,N-diethyl-N-(4-sulfobutyl)-N-(3-vinylbenzyl) ammonium inner salt, N,N-dimethyl-N-(2-amino-2-oxoethyl)-N-(4-vinylbenzyl) ammonium chloride, N,N-diethyl-N-(2-amino-2-oxoethyl)-N-(4-vinylbenzyl) ammonium chloride, N,N-dimethyl-N-(3-amino-3-oxopropyl)-N-(4-vinylbenzyl) ammonium chloride, N,N-diethyl-N-(3-amino-3-oxopropyl)-N-(4-vinylbenzyl) ammonium chloride, N,N-dimethyl-N-(2-amino-2-oxoethyl)-N-(3-vinylbenzyl) ammonium chloride, N,N-diethyl-N-(2-amino-2-oxoethyl)-N-(3-vinylbenzyl) ammonium chloride, N,N-dimethyl-N-(3-amino-3-oxopropyl)-N-(3-vinylbenzyl) ammonium chloride, N,N-diethyl-N-(3-amino-3-oxopropyl)-N-(3-vinylbenzyl) ammonium chloride, N-(2-amino-2-oxoethyl)-N'-vinyl imidazolium chloride, N-(3-amino-3-oxopropyl)-N'-vinyl imidazolium chloride, N-(4-amino-4-oxobutyl)-N'-vinyl imidazolium chloride, N,N-dimethyl-N-(3-sulfopropyl)-3-(acryloyl amino)-1-propaneammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-3-(acryloyl amino)-1-propaneammonium inner salt, N,N-dimethyl-N-(4-sulfobutyl)-3-(acryloyl amino)-1-propaneammonium inner salt, N,N-diethyl-N-(4-sulfobutyl)-3-(acryloyl amino)-1-propaneammonium inner salt, N,N-dimethyl-N-(3-sulfopropyl)-2-(acryloyl amino)-1-ethaneammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-2-(acryloyl amino)-1-ethaneammonium inner salt, N,N-dimethyl-N-(4-sulfobutyl)-2-(acryloyl amino)-1-ethaneammonium inner salt, N,N-diethyl-N-(4-sulfobutyl)-2-(acryloyl amino)-1-ethaneammonium inner salt, and combinations of any two or more thereof.
71. A process according to claim 69 wherein said nitrogen-containing olefinic monomer is selected from the group consisting of N,N-dimethyl-N-(3-sulfopropyl)-N-(4-vinylbenzyl) ammonium inner salt, N,N-dimethyl-N-(3-sulfobutyl)-N-(4-vinylbenzyl) ammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-N-(4-vinylbenzyl) ammonium inner salt, N,N-diethyl-N-(3-sulfobutyl)-N-(4-vinylbenzyl) ammonium inner salt, N,N-dimethyl-N-(3-sulfopropyl)-N-(3-vinylbenzyl) ammonium inner salt, N,N-dimethyl-N-(3-sulfobutyl)-N-(3-vinylbenzyl) ammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-N-(3-vinylbenzyl) ammonium inner salt, N,N-diethyl-N-(3-sulfobutyl)-N-(3-vinylbenzyl) ammonium inner salt, N-acryloyl-N'-methyl-N'-(2-amino-2-oxoethyl) piperazinium chloride, N-acryloyl-N'-methyl-N'-(3-amino-3-oxopropyl) piperazinium chloride, N-acryloyl-N'-methyl-N'-(4-amino-4-oxobutyl) piperazinium chloride, N-acryloyl-N'-ethyl-N'-(2-amino-2-oxoethyl) piperazinium chloride, N-acryloyl-N'-ethyl-N'-(3-amino-3-oxopropyl) piperazinium chloride, N-acryloyl-N'-ethyl-N'-(4-amino-4-oxobutyl) piperazinium chloride, N,N-dimethyl-N-(2-amino-2-oxoethyl)-N-(4-vinylbenzyl) ammonium chloride, N,N-diethyl-N-(2-amino-2-oxoethyl)-N-(4-vinylbenzyl) ammonium chloride, N,N-dimethyl-N-(3-amino-3-oxopropyl)-N-(4-vinylbenzyl) ammonium chloride, N,N-diethyl-N-(3-amino-3-oxopropyl)-N-(4-vinylbenzyl) ammonium chloride, N-(2-amino-2-oxoethyl)-N'-vinylimidazolium chloride, N-(3-amino-3-oxopropyl)-N'-vinylimidazolium chloride, N-(4-amino-4-oxobutyl)-N'-vinylimidazolium chloride, and combinations of any two or more thereof.
72. A process according to claim 69 wherein said nitrogen-containing olefinic monomer is N-acryloyl-N'-methyl piperazine.
73. A process according to claim 69 wherein said nitrogen-containing olefinic monomer is N-acryloyl-N'-(3-sulfopropyl)-N'-methyl piperazinium inner salt.
74. A process according to claim 69 wherein said nitrogen-containing olefinic monomer is N-acryloyl-N'-(2-amino-2-oxoethyl)-N'-methyl piperazinium chloride.
75. A process according to claim 69 wherein said nitrogen-containing olefinic monomer is N,N-dimethyl-N-(3-sulfopropyl)-N-(4-vinylbenzyl) ammonium inner salt.
76. A process according to claim 69 wherein said nitrogen-containing olefinic monomer is N,N-dimethyl-N-(2-amino-2-oxoethyl)-N-(4-vinylbenzyl) ammonium chloride.
77. A process according to claim 69 wherein said nitrogen-containing olefinic monomer is N-(2-amino-2-oxoethyl)-N'-vinyl imidazolium chloride.
78. A process according to claim 69 wherein said nitrogen-containing olefinic monomer is N,N-dimethyl-N-(3-sulfopropyl)-3-(acryloyl amino)-1-propanammonium inner salt.
79. A process according to claim 69 wherein said nitrogen-containing olefinic monomer is N-acryloylmorpholine.
80. A process according to claim 69 wherein said olefinic comonomer is selected from the group consisting of acrylamide, styrene sulfonic acid, salt of styrene sulfonic acid, N-methylacrylamide, N,N-dimethylacrylamide, acrylic acid, salt of acrylic acid, N-vinylpyrroliclone, methyl acrylate, methacrylate, vinylic sulfonic acid, salt of vinylic sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, salt acrylamido-2-methylpropanesulfonic acid, and combinations of any two or more thereof.
81. A process according to claim 80 wherein said olefinic comonomer is acrylamide.
82. A process comprising introducing into a subterranean formation a water-soluble polymer comprising repeat units derived from at least one nitrogen-containing olefinic monomer and at least one olefinic comonomer wherein said nitrogen-containing olefinic monomer has a formula selected from the group consisting of N-acryloyl morpholine, N-acryloyl-N'-methyl piperazine, N-acryloyl-N'-ethyl piperazine, N-acryloyl-N'-propyl piperazine, N-acryloyl-N'-(3-sulfopropyl)-N'-methyl piperazinium inner salt, N-acryloyl-N'-(3-sulfopropyl)-N'-ethyl piperazinium inner salt, N-acryloyl-N'-(4-sulfobutyl)-N'-methyl piperazinium inner salt, N-acryloyl-N'-(4-sulfobutyl)-N'-ethyl piperazinium inner salt, N-acryloyl-N'-(2-amino-2-oxoethyl)-N'-methyl piperazinium chloride, N-acryloyl-N'-(3-amino-3-oxopropyl)-N'-methyl piperazinium chloride, N-acryloyl-N'-(4-amino-4-oxobutyl)-N'-methyl piperazinium chloride, N-acryloyl-N'-(2-amino-2-oxoethyl)-N'-ethyl piperazinium chloride, N-acryloyl-N'-(3-amino-3-oxopropyl)-N'-ethyl piperazinium chloride, N-acryloyl-N'-(4-amino-4-oxobutyl)-N'-ethyl piperazinium chloride, N,N-dimethyl-N-(3-sulfopropyl)-N-(4-vinylbenzyl) ammonium inner salt, N,N-dimethyl-N-(4-sulfobutyl)-N-(4-vinylbenzyl) ammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-N-(4-vinylbenzyl) ammonium inner salt, N,N-diethyl-N-(4-sulfobutyl)-N-(4-vinylbenzyl) ammonium inner salt, N,N-dimethyl-N-(3-sulfopropyl)-N-(3-vinylbenzyl) ammonium inner salt, N,N-dimethyl-N-(4-sulfobutyl)-N-(3-vinylbenzyl) ammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-N-(3-vinylbenzyl) ammonium inner salt, N,N-diethyl-N-(4-sulfobutyl)-N-(3-vinylbenzyl) ammonium inner salt, N,N-dimethyl-N-(2-amino-2-oxoethyl)-N-(4-vinylbenzyl) ammonium chloride, N,N-diethyl-N-(2-amino-2-oxoethyl)-N-(4-vinylbenzyl) ammonium chloride, N,N-dimethyl-N-(3-amino-3-oxopropyl)-N-(4-vinylbenzyl) ammonium chloride, N,N-diethyl-N-(3-amino-3-oxopropyl)-N-(4-vinylbenzyl) ammonium chloride, N,N-dimethyl-N-(2-amino-2-oxoethyl)-N-(3-vinylbenzyl) ammonium chloride, N,N-diethyl-N-(2-amino-2-oxoethyl)-N-(3-vinylbenzyl) ammonium chloride, N,N-dimethyl-N-(3-amino-3-oxopropyl)-N-(3-vinylbenzyl) ammonium chloride, N,N-diethyl-N-(3-amino-3-oxopropyl)-N-(3-vinylbenzyl) ammonium chloride, N-(2-amino-2-oxoethyl)-N'-vinyl imidazolium chloride, N-(3-amino-3-oxopropyl)-N'-vinyl imidazolium chloride, N-(4-amino-4-oxobutyl)-N'-vinyl imidazolium chloride, N,N-dimethyl-N-(3-sulfopropyl)-3-(acryloyl amino)-1-propaneammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-3-(acryloyl amino)-1-propaneammonium inner salt, N,N-dimethyl-N-(4-sulfobutyl)-3-(acryloyl amino)-1-propaneammonium inner salt, N,N-diethyl-N-(4-sulfobutyl)-3-(acryloyl amino)-1-propaneammonium inner salt, N,N-dimethyl-N-(3-sulfopropyl)-2-(acryloyl amino)-1-ethaneammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-2-(acryloyl amino)-1-ethaneammonium inner salt, N,N-dimethyl-N-(4-sulfobutyl)-2-(acryloyl amino)-1-ethaneammonium inner salt, N,N-diethyl-N-(4-sulfobutyl)-2-(acryloyl amino)-1-ethaneammonium inner salt, and combinations of any two or more thereof;
and said olefinic comonomer is selected from the group consisting of acrylamide, styrene sulfonic acid, salt of styrene sulfonic acid, N-methylacrylamide, N,N-dimethylacrylamide, acrylic acid, salt of acrylic acid, N-vinylpyrrolidone, methyl acrylate, a methacrylate, vinylic sulfonic acid, salt of vinylic sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, salt 2-acrylamido-2-methylpropanesulfonic acid, and combinations of any two or more thereof.
83. A process according to claim 82 wherein said nitrogen-containing olefinic monomer is N-acryloyl-N'-methyl piperazine.
84. A process according to claim 82 wherein said nitrogen-containing olefinic monomer is N-acryloyl-N'-(3-sulfopropyl)-N'-methyl piperazinium inner salt.
85. A process according to claim 82 wherein said nitrogen-containing olefinic monomer is N-acryloyl-N'-(2-amino-2-oxoethyl)-N'-methyl piperazinium chloride.
86. A process according to claim 82 wherein said nitrogen-containing olefinic monomer is N,N-dimethyl-N-(3-sulfopropyl)-N-(4-vinylbenzyl) ammonium inner salt.
87. A process according to claim 82 wherein said nitrogen-containing olefinic monomer is N,N-dimethyl-N-(2-amino-2-oxoethyl)-N-(4-vinylbenzyl) ammonium chloride.
88. A process according to claim 82 wherein said nitrogen-containing olefinic monomer is N-(2-amino-2-oxoethyl)-N'-vinyl imidazolium chloride.
89. A process according to claim 82 wherein said nitrogen-containing olefinic monomer is N,N-dimethyl-N-(3-sulfopropyl)-3-(acryloyl amino)-1-propaneammonium inner salt.
90. A process according to claim 82 wherein said nitrogen-containing olefinic monomer is N-acryloylmorpholine.
91. A process according to claim 82 wherein said olefinic comonomer is acrylamide.
92. A composition comprising a water-soluble polymer, a crosslinking agent, and a liquid wherein said polymer is recited in claim 15.
93. A composition according to claim 92 wherein said crosslinking agent is a multivalent 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.
94. A composition according to claim 92 wherein said crosslinking agent is selected from the group consisting of a zirconium compound, a titanium compound, a chromium compound, an aluminum compound, and combinations of any two or more thereof.
95. A composition according to claim 92 wherein said crosslinking agent is selected from the group consisting of zirconium citrate, zirconium complex of hydroxyethyl glycine, ammonium zirconium fluoride, zirconium 2-ethylhexanoate, zirconium acetate, zirconium neodecanoate, zirconium acetylacetonate, tetrakis(triethanolamine)zirconate, zirconium carbonate, ammonium zirconium carbonate, zirconyl ammonium carbonate, zirconium lactate, titanium acetylaceton ate, 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.
96. A composition according to claim 92 wherein said crosslinking agent comprises two components in which the first component is selected from the group consisting of phenol, substituted phenols, aspirin, p-aminobenzoic acid, resorcinol, catechol, hydroquinone, furfuryl alcohol, R'ArO(C=O)m R', HOAr(C=O)m OR', HOArOH, R'OArOH, R'OArOR', or combinations of any two or more thereof wherein Ar is non-substituted or subsituted arylene group; each R' can be the same or different and is each independently selected from the group consisting of hydrogen, carboxylic group, a C1-C6 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 the group consisting of aldehydes, aldehyde-generating compounds, and combinations of any two or more thereof.
97. A composition according to claim 92 wherein said crosslinking agent comprises two components in which the first component is selected from the group consisting of phenol, hydroquinone, resorcinol, catechol, .rho.-aminosalicylic acid, furfuryl alcohol, phenyl acetate, phenyl propionate, phenyl butyrate, salicylic acid, phenyl salicylate, aspirin, .rho.-hydroxybenzoic acid, methyl .rho.-hydroxybenzoate, methyl .rho.-aminobenzoic acid, .rho.-hydroxybenzoate, ethyl .rho.-hydroxybenzoate, o-hydroxybenzoic acid, hexyl .rho.-hydroxybenzoate, and combinations of any two or more thereof; and the second component is selected from the group consisting of formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, decanal, glutaraldehyde, terephaldehyde, hexamethylenetramine, and combinations of any two or more thereof.
98. A composition according to claim 92 wherein said liquid is a produced brine.
99. A process comprising introducing a gelling composition into a subterranean formation wherein said composition is recited in any one of claims 92-98.
100. A composition comprising a clay, a polymer, and a liquid wherein said polymer is recited in claim 15.
101. A composition according to claim 100 wherein said polymer further comprises repeat units derived from at leant one olefinic comonomer selected from the group consisting of 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 of 2-acrylamido-methylpropanesulfonic acid, and combinations of any two or more thereof.
102. A composition according to claim 100 wherein said clay is bentonite.
103. A process comprising introducing a composition into a subterranean formation wherein said composition is recited in claim 100.
CA002241362A 1995-12-20 1996-11-13 Compositions and processes for treating subterranean formations Expired - Lifetime CA2241362C (en)

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US08/575,429 US5708107A (en) 1995-12-20 1995-12-20 Compositions and processes for treating subterranean formations
US08/575,928 1995-12-20
US08/575,928 US5650633A (en) 1995-12-20 1995-12-20 Compositions and processes for treating subterranean formations
US08/575,429 1995-12-20
US08/723,635 1996-10-03
US08/723,635 US5922653A (en) 1995-12-20 1996-10-03 Compositions and processes for treating subterranean formations
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