GB2340496A - Compositions and processes for treating subterranean formations - Google Patents

Compositions and processes for treating subterranean formations Download PDF

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Publication number
GB2340496A
GB2340496A GB9930053A GB9930053A GB2340496A GB 2340496 A GB2340496 A GB 2340496A GB 9930053 A GB9930053 A GB 9930053A GB 9930053 A GB9930053 A GB 9930053A GB 2340496 A GB2340496 A GB 2340496A
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amino
chloride
inner salt
vinylbenzyl
ammonium
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GB9930053D0 (en
GB2340496B (en
Inventor
Iqbal Ahmed
Ahmad Moradi-Araghi
Aly-Anis Hamouda
Odd Ivar Eriksen
Bharatkuma Balubhail Patel
Wayne Stephen Stewart
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Phillips Petroleum Co
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Phillips Petroleum Co
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Priority claimed from US08/575,429 external-priority patent/US5708107A/en
Priority claimed from US08/575,928 external-priority patent/US5650633A/en
Priority claimed from US08/575,434 external-priority patent/US6051670A/en
Priority claimed from US08/723,635 external-priority patent/US5922653A/en
Application filed by Phillips Petroleum Co filed Critical Phillips Petroleum Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
    • C07D295/18—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carboxylic acids, or sulfur or nitrogen analogues thereof
    • C07D295/182—Radicals derived from carboxylic acids
    • C07D295/185—Radicals derived from carboxylic acids from aliphatic carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C237/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups
    • C07C237/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C237/04—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
    • C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C309/13—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton
    • C07C309/14—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton containing amino groups bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/52—Amides or imides
    • C08F20/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F20/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F26/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F26/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/02—Well-drilling compositions
    • C09K8/04—Aqueous well-drilling compositions
    • C09K8/06—Clay-free compositions
    • C09K8/12—Clay-free compositions containing synthetic organic macromolecular compounds or their precursors
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/02—Well-drilling compositions
    • C09K8/04—Aqueous well-drilling compositions
    • C09K8/14—Clay-containing compositions
    • C09K8/18—Clay-containing compositions characterised by the organic compounds
    • C09K8/22—Synthetic organic compounds
    • C09K8/24—Polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
    • C09K8/588—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/607—Compositions for stimulating production by acting on the underground formation specially adapted for clay formations
    • C09K8/608—Polymer compositions
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/62—Compositions for forming crevices or fractures
    • C09K8/66—Compositions based on water or polar solvents
    • C09K8/68—Compositions based on water or polar solvents containing organic compounds
    • C09K8/685—Compositions based on water or polar solvents containing organic compounds containing cross-linking agents
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/84—Compositions based on water or polar solvents
    • C09K8/86—Compositions based on water or polar solvents containing organic compounds
    • C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
    • C09K8/887—Compositions based on water or polar solvents containing organic compounds macromolecular compounds containing cross-linking agents
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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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  • Polymers & Plastics (AREA)
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  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
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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-lifting 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

2340496 COMPOSITIONS AND PROCESSES FOR TREATING SUBTERRANEAN FORMATIONS
FIELD OF THE INVENT-ION
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 ftom 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.
BACK(iROUND OF THE INVENTION It is well known to those skilled in the art that polymers and gelled or crosslinked water-soluble polymers are useful in enhanced oil recovery and other oil field operations. They have been used to alter the permeability of underground formations in order to enhance the effectiveness of water flooding operations.
Generally, polymers or polymers along with a gelling agent such as an appropriate crosslinking agent in a liquid are injected into the formation. The polymers then permeate into and gel, in the cases when a polymer and a crosslinking agent are used, in the regions having the highest water permeability.
Polymers have also been used in subterranean formation treatments such as "matrix acidizing" and "fracture acidizing", Because such treatments are well known to one skilled in the art, description of wMeh is omitted herein and can be found in U.S. Pat. No. 4,997,582, description of which is herein incorporated by reference.
Because of environmental concerns as well as cost for disposing of a produced brine which is defined as the brine co-produced with oil and gas and is generally contaminated with some oil, or gas. or both, it is desirable to utilize the produced brine as the liquid used for the polymers and appropriate crosslinking systems. Use of produced brines eliminates not only the cost associated with acquiring and pre-treating fresh water for use as the liquid but also the disposal cost for the produced brine. Most produced brines are known to be hard brines., i.e., those having a divalent cation concentration greater than 1000 ppm.
Many polymers have been developed and used in processes for the recovery of hydrocarbons. Generally a desirable property is that such polymers impart to a liquid an increased viscosity when a relatively small quantity of the polymer is added, and preferably at a minimal cost. Another desirable property is that such polymers form gels, in the presence of a suitable gelling agent such as a crosslinking agent. However, a number of such polymers are not -capable of forming gels having high thermal stability, i.e., the gels formed show high syneresis after a short period, such as for example a few days, at high temperature, such as for example, 12CC in a harsh environment such as sea water.
Various polymers of desired properties such as those disclosed above may be used in the process for recovery of hydrocarbons. For example, multivalent metallic ions crosslink gellable polymers through the interaction with the oxygen atoms of the polymer molecules. Therefore, the gellable polymers generally contain some carboxylate groups. Generally, the gellable polymers used such as, for example, partially hydrolyzed polyacrylamide are of high molecular weight and contain high degrees of hydrolysis, i.e., contain 10-30 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 rend= 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 describcd above.
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 '1ardness ion'S", 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 formulations, compositions and additives to optimize the performance of drilling fluids for various applications have been-developed. For instance, compositions comprising mixtures of carboxylic acid polymers and soluble metal salts with the object of increasing the "yield" (defined as the number of barrels of 15 centipoise mud which can be prepared from one ton of clay) of relatively low-grade clays have been used.
Excessive fluid loss from the drilling fluld 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 Cel and Mg 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, arc 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 recompletign, of the well.
Completion can include cementing the casing, perforating the casing, setting the tubing and pump, etc.
Workover fluids am those fluids used during remedial work in the well.
This can include removing tubing, replacing a pump, cleaning out sand or other deposits, logging, reperforating, etc. Workover also broadly includes steps used in preparing an existing well for secondary or tertiary oil recovery such as polymer additions, micellar flooding, steam injection, etc.
Both workover and completion fluids are used in part to control well pressure, to prevent the collapse of casing from overpressure, and to prevent or reduce corrosion of casing. A drilling fluid may be suitable for completion or workover over applications in some cases, but not in all cases.
Although there has been considerable progress in the field of Workovcr and completion fluids, there is significant room for further improvement. For example, wells are being completed and serviced in increasingly hostile environments involving, e.g., high temperatures and high levels of salinity and/or hardness in the formation water. Thus, new additives for Workover and completion flui& which retain their properties at elevated temperatures and high concentrations of dissolved electrolytes are in demand.
Therefore, a composition which can be used to prepare a more hostile environment-withstanding polymer as well as a hostile environmentwithstanding gelling composition, containing the hostile 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 inAfilling fluids, completion fluids, or Workover fluids.
SUMMARY OF 111E IDMNTION
An object of the invention is to provide a composition which can be used as a monomer to synthesize a hostile envirortment-withstanding, water-soluble polymer. Another object of the invention is to provide a process for synthesizing the composition. Yet another object of the present invention is to provide a water-soluble polymer that can be used to form a gel in a hostile environment in hydrocarbon-beanng 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 hereinbelow.
According to a first embodiment of the present invention, a composition that can be used to prepare a water-soluble polymer which can be used in a hydrocarbon-bearing subterranean formation is provided. The composition comprises a nitrogen-containing olefinic compound.
According to a second embodiment of the present invention, a process for preparing a composition is provided that can be used to prepare a water-soluble polymer which can be used in a hydrocarbon-hearing formation wherein said composition comprises a nitrogen-containing olefinic compound.
According to a third embodiment of the present invention, a water-soluble polymer which can be used in a hydrocarbon-bearing formation is provided. The polymer comprises repeat units derived from at least one 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 pr in drilling fluid, completion fluid, workover fluid, or combinations of any two or more thereof is provided. The composition can comprise, consist essentially of. or consist of a water-soluble polymer. a clay, and a liquid wherein the polymer comprises repeat units derived hom at least one nitrogen-containing olefinic compound.
DETAILED DESCRIFITON OF THE I.NYENMN According to the first embodiment of the present invention, a composition useful as a monomer for synthesizing a water-solublc polymer is provided. The compo sition comprises, or consists essentially of, or consists of a nitrogen-containing olefinic compound having the formula selected from the group consisting of sulfobetaines, vinylic amides, and combinations of any two or more thereof wherein the sulfobetaine has the formula of R,C(R,)=C(R,)-(C=O),n-(Ar).,-Y-N'(R2)(R2)-Y-SO3 and the vinylic amide has the formula of R,-C(R,)=C(R,)-(C=O),,,-(NH).-(Ar),,-Y-N(R2)(R2)-Y-(C--O),-N(R2)(R2)X', RjC(Rj)=C(Rj)-(C0),,,-N N"(R,)-Y-(C=O),,-N(R2)(R2)X-, R,C(Rj)--C(Rj)-(C=O),,,-N N-Y-(C---O),,,-N(R2)(R,)X-, or combinations of any two or more thereof. R, and R2 can be the same or different and are each independently selected from the group consisting of hydrogen, alkyl radicals, aryl radicals, -aralkyl radicals, alkaryl radicals, and combinations of any two or more thereof wherein each radical can contain I to about 30, preferably I to abut 20, more preferably I to about 15, and most preferably I to 10 carbon atoms and can contain functional group(s) such as ammonium, hydroxyl, sulfate, ether, carbonyl groups, amine groups, sulfhydryl groups, or combinations of any two or more thereof which can contribute to water solubility of polymers produced therefrom. Preferably R, is hydrogen and R, is hydrogen, methyl, ethyl, or combinations of two or more thereof. Y is an alkylene radical, a phenyl group, an imidazolium group, a naphthyl group, a biphenyi group, or combinations of any two or more thereof. Each Y is preferably independently an alkylene radical which can have I to about 20, preferably 1 to about 15. and more preferably I to 10 carbon atoms. Most preferably, Y is a short alkylene radical having PcT/US96/18174 1 1 . I to about 5 carbon atoms. Ar is an arylene radical, preferably a phenyl group, which can be substituted or unsubstituted. N is an anion selected fTorn the group consisting of halides, sulfates, phosphates, nitrates, sulfonates, phosphonates, sulfinates, phosphinates, and combinations of any two or more thereof. Each m can be the same or different and is 0 or I - Examples of suitable nitrogen-containing olefinic compounds of the first embodiment of the invention include, but are not limited to, N,N-dimethyl-N-(3-sulfopropyl)-N-(4-vinylbenzyl) ammonium inner salt, N,N-dimethyl-N-(3-sulfobutyl)-N-(4-vinylbenzyl) ammonium inner salt, N.N-diethyl-N-(3-sulfopropyl)-N-(4-vinylb--nzyl) ammonium inner salt, N,N-diethyl-N-(3-sulfobutyl)-N-(4-vinylbenzy]) ammonium inner salt, N,N-dimethyl-N-(") -sulfopropyl)-N-(3-vinylbexizyl) ammonium inner salt, N,N-dimethyl-N-(3-sulfobutyl)-N-(3-vinylbenzyl) ammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-N-(3-vinylbenzy]) ammonium inner salt, N.N-diethyl-N-(3-sulfobutyl)-N-(3-vinylbenzy]) ammonium inner salt, N-acryloyl-N'-methyl-N'-(2-amino-2-oxoethyl) piperazinium chloride, N-acryloyi-N'-methyl-N'-(3-amino-3-oxopropyl) piperaziniurn chloride, N-acryloyl-N'-methyl-N'-(4-amino-4-oxobutyl) piperazinium chloride, N-acryloyi-N'-ethyl-N'-(2-amino-2-oxoethyl) piperazinium chloride, N-acryioyi-N'-ethyl-N'-(3-amino-3-oxopropyl) piperazinium chloride, N-acryloyi-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-arnino-2-oxoethyl)-N-(4-vinylbenzyl) ammonium chloride, N,N-dimethyl-N-(3-amino-3-oxopropyl)-N-(4-vinylbenzy]) ammonium chloride, N,N-diethyl-N-(3-wnino-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-aniino-4-oxobutyl)-N'-vinylimidazolium chloride, and combinations of any two or more thereof.
The nitrogen-containing olefinic compounds of the first embodiment of the invention can be prepared by the process disclosed hereinbclow in the second embodiment of the invention.
In the second embodiment of the present invention, a process for preparing the nitrogen-containing olefinic compounds is provided. The nitrogen-containing olefinic compounds having the formula of R,C(R,)=C(Ri)-(C=O),,,-(NH).-(Ar).-Y-N'(R2)(R,)-Y-SO3- (a sulfobetaine), can be produced by. contacting a vinylic tertiary aminewrith an alkylating agent such as, for example, an alkylsulfonic acid containing a proper leaving group such as halide, hydroxyl, tosylatc, other suitable leaving groups, or combinations of any two or 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 I to about 10 days, preferably about I to about 8 days, and most preferably I to 5 days under any suitable pressures such as, for example, about I atmospheric pressure. A suitable radical inhibitor such as 1.3-dinitrobcnzene can be added to prevent polymerization of the nitrogen- containing olefinic compounds during the contacting. Preferably the production is carried out by using 1,3-propanesultone or 1,4-butanesultone as the alkylating reagent in toluene by heating at 45-50C for 72 hours. The sulfobetainc 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, 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-viri.vibenzyl) amine, N,N-dimethyl-N-(4-vinylbenzyl) amine, NN-diethyl-N-(4-vinylbenzyl) amine, N,N-diethyl-N-(4-vinylbenzyl) arnine, N,N-dimcthyl-N-(3-vinylbenzyl) amine, NN-dimethyl-N-(3-vinylbenzyl) amine, N,N-diethyl-N-(3-vinylbenzyl) amine and NN-diethyl-N-(3-vinylbenzyl) amine, and combinations of any two or more thereoL Examples of suitable alkylating reagents include, but are not limited to, 3-chloro-prapane-l-sulfonic acid4 4-chloro-butane-l-sulfonic acid, 3-hydroxy-propane- I -sulfonic acid, 4-hydroxy-butane- I -sulfonic acid, the corresponding esters of the hydroxy-alkane- I -sulfonic acids such as 1,3-propanesultone and 1,4-butanesultone, and combinations of any two or more thereof The nitrogen-containing olefinic compounds with the arnide functional group of the first embodiment of the invention have general formulae of R,C(R,)=C(Ri)-(C--O),,,-(NH),.-(Ar).-Y-N'(R2)(R2)-Y-(C=O),,-N(R2)(R2)X-, RjC(Rj)=C(Rj)-(C=O).-N N+(R2)-Y-(C=O).-N(R2)(R2)X-, _IZI RjC(R,)=C(Rj)-(C=O),,,-N N±Y-(C--O).-N(R2)(R2)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 vinylsubstituted amine and an alkylating agent can be contacted under a condition including a temperature in the range of from about 10 to about 150'C, preferably about 20 to about 120 "C, and most preferably 30 to 1 OCC for about 1 to abo- ut 15 days, preferably 1 to 8 days under any suitable pressure such as, for example, about 1 atmospheric pressure. A suitable radical inhibitor such as, for example, 1,3-dinitrobenzene can be added to prevent polymerization of the nitrogen-containing olefinic compounds during the contacting.
Preferably the production is carried out by using 2-chloro-acetamide as the 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, NN-dimethyl-N-(4-vinylbenzyl) amine, N,N-dimethyl-N-(4- vinylbenzyl) amine, N,N-diethyPN-(4-vinylbenzyI) amine, N,N-diethyl-N-(4-vinylbenzyI) amine, N,N-dimethy]-N-(3-vinylbenzyl) amine, N,N-dimethyPN-(3-vinylbenzyI) amine, N,NL-diethyl-N-(3-vinylbenzyl) arnine and N,N-diethyl-N-(3-vinylbenzy[) 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-propancamide and 3-bromo-propancamide, and combinations of any two or more thereof.
In the second embodiment of the invention, the molar ratio of the alkylating agent to the amine can be any ratio so long the ratio can effect the production of the nitrogen-containing olefinic compounds. Generally, the molar ratio) can be in the range of from about 1:0.0 1 to about 0.0 1. 1, preferably about 1:0.05 to about 0.05: 1, and most preferably 1:0. 1 to 0. 1: 1. The molar ratio of the radical inhibitor to the amine can be in the range of from about 0. 1: 1 to about 1,000: 1. The molar ratio of the solvent to the amine can be any ratio that is effective in the production of a nitrogen-containing olefinic compound and can be in the range of from about 0. 1: 1 to about 1,000: 1.
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 o or consists of, repeat units derived from at least one nitrogen-containing oleffific 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(R1)--C(R1)-(C=O).-M, R,-C(Rj)=C(R1)-(C=O),,,-N N(R1), R,-C(Rj)=C(R1)-(C=O).-N W(R2)-Y-X'5 R, C(R j)--C(R1)-(C=O).-(NH).-(Ar).-N(R2)(R2)-Y-SO3-, RI-C(Rj)=C(R1)-(C=O).-(NH).-(Ar).-Y-N(R2)(R2)-Y-(C=O),,-N(R2)(R2)X-, R,C(Rj)=C(RJ-(C=0),,-N N(R)-Y-(C--0),,,-N(R(R2)X', RIC(Rj)=C(R1)-(C--0),,,-N N-Y-(C-0).-N(R2)(R2)X-, and combinations of any two or more thereof. R, and R2 can be the same or different and are each independently selected from the group consisting of hydrogen, alkyl radicals, aryl radicals, aralkyl radicals.. alkaryl radicals, and combinations of any two or more thereof wherein each radical can contain 1 to about 30, preferably 1 to abut 20. more preferably 1 to about 15, and most preferably 1 to 10 carbon atoms and can contain functionalities such as, for example, hydroxyl, sulfate, carbonyl, arnine, sulfhydTyl, or combinations of any two or more thereof. Preferably R, is hydrogen, R2is hydrogen, methyl, ethvl, or combinations of any two or more thereof. M is a moTpholine group which can be substituted or unsubstituted. Y is an alkylene radical, a phenyl group, an imidazoliurn group, a naphthyl group, a biphenyl group, or combinations of any two or more thereof which can have I to about 20, preferably I to about 15, and most preferably I to 10 carbon atoms. Most preferably, Y is a short alkylene radical having I to about 5 carbon atoms. Ar is an arylene radical, preferably phenyl, which ran be substituted or unsubstituted. X is an anion selected from the group consisting of halides, sulfate, phosphate, nitrate, sulforiates., phosphonates, suffinates, phosphinates, and combinations of any two or more thereof Each m can be the same or different and is indcpendently 0 or 1.
The watcr-solublc polymeTof the third embodiment of the present invention can be a homopolymer, copolymer, terpolyrner or tetrapolymer. However, if the nitrogen-containing olefinic repeat units contain an amide group, it is preferred that the water-soluble polymer be derived from repeat units comprising at least one of the nitrogen-containing olefinic compounds described above and at least one olefinic comonomer sclected from the group consisting of Rj-C(Rj)=C(Rj)-W, R,-C(R,)=C(Rj)-(C=O),,,-Z, Rj-C(Rj)=C(Rj)-Y-W, R, -C(R,)=C(R,)-(C=O),,,-N(R2)-Y-R2, RI-C(Rj)--C(Rj)-(C=O).-G-Y-Z, RjC(Rj)=C(Rj)-(C=O),,,-G-Y-W, R,-C(R,)=C(Rj)-(C=O),.-Y-Z, and combinations of any two or more thereof wherein Z has a formula selected from the group consisting of N(R2)(R2), N'(R2)(R,)(R2)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 1. G is N(RI) or 0. W is an acid. moiety selected from the group ccnsisting of phosphinic acid, phosphonic acid, sulfinic acid, sulfonic acid, sulfuric acid. sulfurousacid, 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 piperazine, N-acryloyl-W-propyl piperazine, N-acryloyl-N'-(3-sulfopropyl)-N'-methyl piperazinium inner salt, N-acryloyl-N'-(3-sulfopropyl)-N'-ethyl piperazinium inner salt, N-acryloyl-N'-(4-sulfopropyl)-N'-methyl piperazinium inner salt, N-acryloyi,-r'-(4-sulfopropyl)-N'-ethyl piperazinium inner salt, Nacryloyl-N'-(2-amino-2-oxoethyl)-N'-mefflyl piperazinium chloride, Nacryloyl-N'-(3-amino-3-oxopropyl)-N'-methyl piperazinium chloride, N.acryloyi-N-(4-amino-4-oxobutyl)-N'-methyl piperazinium. chloride, Nacryloyl-N'-(2-amino-2-oxoethyl)-N'-ethyl piperaziniurn chloride, 15 Nacryloyi-N'-(3-amino-3-oxopropyl)-N'-ethyi piperaziniurn chloride, Nacryloyl-'N'-(4-amino-4-oxobutyl)-N'-ethyl piperazinium chloride, N, Ndimethyl-N-(3-suifopropyl)-N-(4-vinylbenzyl) ammonium inner salt, N..Ndimethyl-N-(4-suifobutyl)-N-(4-Yinylbenzyl) ammonium inner salt, N,Ndiethyl-N-(3-suifopropyi)-N-(4-vinylbenzyl) ammonium inner salt, 20 N,,Ndiethyl-N-(4-suifobutyl)-N-(4-Yinylbenzyl) ammonium inner salt, N,Ndimethyl-N-(3-sulfopropyl)-N-(3-vinylbenzyl) ammonium inner salt, N,Ndimethy)-N-(4-sulfobutyl)-N-(3-vinylbenzyl) ammonium inner salt, N,Ndiethyl-N-(3-suifopropyi)-N-(3-vinylbenzyl) amnionium inner salt. N,Ndiethyl-N-(4-suifobutyl)-N-(3-Yinylbcnzyl) ammonium inncr salt, 25 N,Ndimethy)-N-(2-amino-2-oxoethyl)-N-(4-vinylbenzyl) ammonium chloride, N,Ndiethyl-N-(2-amino-2-oxoethyl)-N-(4-vinylbenzyl) ammonium chloride, N,Ndimethyl-N-(3-amino-3-oxopopyl)-N-(4-Yinylbenzyl) ammonium chloride, N,Ndiethy]-N-(3-amino-3-oxopropyl)-N-(4-Yinylbenzyl) ammonium chloride, NN-dimethyl-N-(2-ainino-2-oxocthyl)-N-(3-vinylbenzyl) ammonium chloride, N.N-diethyl-N-(2-amino-2-oxoethyl)-N-13-vinylbenzy]) 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 cliloride, N-(2-amino-2-oxoethyl)-N'-vinyl imidazolium chloride, N-(3-amino-3-oxopropyl)-N'-vinyI imidazoliwn chloride, N-(4-amino-4-oxobutyl)-N %vinyl imidazolium chloride, N,N-dimethyl-N-(3-sutfopropyl)-3-(acryloyI amino)- I -propaneammonium inner salt.
N,N-diethyl-N-(3-sulfopropyl)-3-(acryloyI amino)- I -propaneammonium inner salt, N,N-dimethyl-N-(4-sulfobutyl)-3-(acryloyI amino)- I -propaneammoniurn irmer salt, N,N-diethyl-N-(4-sulfobutyl)-3-(acryloyI amino)- I -propaneammonium inner salt, N,N-dimethyl-N-(3-sulfopropyl)-2-(acryloyI an-no)-l-ethaneammonium. inner salt, N,N-diethyl-N-(3-sulfopropyl)-2-(acryloyI arnino)-l-ethaneanunonium inner salt, N,N-dimethyl-N-(4-sulfobutyl)-2-(acryloyI amino)- I -ethaneammonium inner salt, N,N-diethyl-N-(4-sulfobutyl)-2-(acryloyI amino)-l-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, NN-dimethylacryiamide, acrylic acid, salt of acrylic acid.
N-vinylpyrrolidone, methyl acrylate, methacrylate, vinyl sulfonic acid, salt of vinyl sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, salt - 2-acrylunido-2-methylpropanesulfonic acid, and combmations of any two or more thereof. The salt can be an ammonium salt, an alkali metal salt, or combinations of any two or more thereof.
Some of the olefinic. comonomers can be purchased commercially.
The others can be synthesized by the process disclosed in the second embodiment of the present invention or in the Examples section.
I- WO 97122638 PCT/US96118174 17 For example, the olefinic comonomers having the formula of R,-C(Rj)=C(Rj)- (C=O),,,-M in which M is the same as disclosed above can be prepared from R,-C(Rj)=C(R1)-(C--0),,,-X where X is the same as that disclosed above, such as acryloyl chloride, and morpholine or from R,-C(R,)=C(R,)-(C=O),,,- OH, such as acrylic acid, and morpholine. Themolarratio of morpholine to the other reactant can be in the range of fTom about 2:1 to about L2. 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 -SO'C to about 2CC, for about 1 to about 10 hours. The reactants are commercially available.
See Examples section below for details.
The water-soluble polymers of the third embodiment of the present invention can be prepared by mixing the monomer(s) (i.e., the nitrogencontaining olefinic compounds and the olefinic comonomers), in desired molar ratios if copolymers, terpolymers, or tetrapolymers are desired, in an appropriate liquid medium and then initiating the free-radical polymerization in solution, suspension, or emulsion environmentGenerally, any molar ratios can be employed depending on the fmal 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-itnidazolin-2-yl)propane) dihydrochloride, alkali metal persulfates such as K2S.O,, alkali metal perborates, alkali metal perphosphates, and alkali mctal percarbonates. Well known organic peroxide compounds commonly employed to initiate free radical polymerization reactions include lauryl peroxide, 2,5-dimethy]-2,5-bis(2-ethyihexanoylperoxy)hexane, t-butylperoxyprivilate, t-butylperoctoate, p-methane hydroperoxide, and benzoylperoxide. The compound t-butylhyponitrite is a well known Okyl hyponitrite: commonly employed to initiate free radical polymerization reactions. Furthermore, ultraviolet light and gamma 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 0.0 1: 1 to about 100. 1, preferably about 0.05:1 to about 50: 1, and most preferably 0. 1: 1 to 30: L If a combination of the nitrogencontaining olefinic monomers, or the olefuiic comonomers, or both are employed, the molar ratios can be any ratio so long as the molar ratio of total nitrogen-containing olefinic monomers, to the olefinic comonomers is within the range disclosed above.
According to the fourth embodiment of the present invention, a process which can be used in hydrocarbon-bearing subterranean formations Such as water-flooding is provided. The process comprises, or consisting essenrially 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, OTundissolved substances such as salts. The presently preferred liquid is an aqueous liquid such as, for example, fresh water, sea water, salt water, or a produced brine which is defined above.
Examples of salts include metal salts. Generally, the total salts content can vary Widely from, for instance, I to as high as 30 weight percent (%). The typical salts content can be in the range of from, for instance, about 2 to about 25 weight The introduction of the water-soluble composition into a subterranean formation can be carried out by any methods known to one skilled in the art. Generally the water-soluble polymer can be dissolved, or substantially dissolved, in a liquid so that the water-soluble composition is present in the liquid in an amount, or concentration, sufficient to alter the permeability of a subterranean formation. The amount, or concentration, can be in the range of from about 50 to about 100,000, preferably about 100 to about 50,000, and most preferably 200 to 10,000 mg of the water-soluble composition per liter of the liquid.
The water-soluble composition in a liquid medium can theni 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 400F, preferably 75F to 350"F. I 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,..pnd a liquid. The scope of the water-soluble composition is the same as that disclosed in the third embodiment of the present invention. The liquid component is the same as that disclosed in the fourth embodiment of the present invention.
Any crosslinking agents can be used. For example, a multivalent metallic compound that are capable of crosslinking the gellable carboxylate-containing polymer in the hydrocarbon-bearing formations can be used in the process of the present invention. Examples of suitable multivalent metal compounds include, but are not limited to, AI", Cr", Fe-2, Zr', Ti", and combinations of any two or more thereof.
The presently preferred multivalent metal compound is a metal compound selected from the group consisting of a complexed zirconium compound, a complexed titanium compound, a complexed chromium compound, and combinations of any two or more thereof. 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, 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 trietlianolamine, ammonium titanium lactate, aluminum citrate, chromium citrate, chromium acetate, chromium propionate, chromium malonate, and combinations thereof. The presently most preferred crosslinking agent is zirconium lactate, zirconium citratc; 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 ligand useful for the present invention to retard the rate of gelation is generally a carboxylic acid containing one or more hydroxyl groups and salts thereof The complexing ligand can also be an amine that has more than one functional group and contains one or more hydroxyl groups and that can chelate the zirconium or titanium moiety of the zirconium or titanium compounds described above. 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, triethanolarnine, 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 waterdispersible or soluble and can be phenol, substituted phenols, aspirin, p-arninobenzoic acid, resorcinol, catechol, hydroquinone, farfuryl alcohol, WArO (C=O). R',. HOAr (C=O).. OR', HOArOll, TOArOH, W0ArOW, 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 C,-C, alkyl, a phenyl group or combinations of any two or more thereof; and m is 0 or 1. The term "water dispersible" used herein is to describe a component that is truly water soluble or is dispersible in water to form a stable suspension. Examples of suitable first crosslinking components include, but are not limited to, phenol, hydroquinonc, resorcinol, catechol,p-aminasalicylic acid, p-amino benzoic acid, ftufuryl alcohol, phenyl acetate, phenyl propionate, phenyl butyrate, salicylic acid, phenyl salicylate, aspirin, p- hydroxybenzoic acid, methyl p-hydroxybenzoate, rnethyl o-hydfoxybenzoate, 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, catectol, hydroquinone, and combinations of any two or more thereof.
Any water-dispersible or soluble aldehyde, its derivative. or compound that can be converted into aldehyde can be utilized as the second crosslinking component in crosslinking agent. Examples of suitable second crosslink-ing 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 ftorn the group consisting of formaldehyde, paraformaldehyde, acetaidehyde, propionaldehyde, decanal, glutaraldehyde, terephthaidehyde, hexamethylenetetramine, and combinations of any two or more thereof.
The weight ratio of the water-dispersible first crosslinking component to the second crosslinking component can be any ratio so long as the ratio can effect the gelation of the gelling composition. Generally, such ratio can be in the range of ftorn about 0.0 1: 1 to about 100: 1, preferably about 0. 1: 1 to about 10: 1, and most preferably 0.5.1 to 2: 1.
Any suitable procedures for preparing the gelling composition can be used. Some of the polymers can require particular mixing conditions. such as slow addition of finely powdered polymer into a vortex of stirred brine. alcohol prewetting, protection from air (oxygen), preparation of stock solutions frorn fresh rather than salt water, as is known for such polymers.
The concentration or amount of the water soluble polymer in the gelling composition can range widely and be as suitable and convenient for the various polymers, and for the degree of gelation needed for particular reservoirs. Generally, the concentration of the water-soluble polymer in a liquid is made up to a convenient strength of about 100 to 1.00,000 mg/I (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 ing/1 (ppm) to about 10,000 ppm, preferably over the range of about 1 ppm to about 7,500 pprn, and most preferably 1 ppin to 21,500 ppin. 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 fifth 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 gcUble polymer are the same as those described above. The amount of the aqueous gelling composition introduced or injected can vary widely depending on the treatment volume injected. The amount of the gellable polymer injected is also dependent on the gel strength desired, - same as that described for the crosslinking agent.
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 707 to about 3507. Any means known to one skilled in the art such as, for example, a pump means can be used for introducing or injecting the gelling composition and polymer solution.
According to the seventh embodiment of the invention, a composition which can be used as or in drilling fluids, completion fluids, or workover fluids is provided. The composition can comprise, consist essentially of, or consist of a clay, a water-soluble polymer, a liquid. The definition and scope of liquid and water-soluble polymer are the same as those disclosed above, the description of which are omitted herein for the interest of brevity.
According to the seventh embodiment of the invention, the clay useful in the invention can be any clay. Examples of suitable clays include, but are not limited to, kaolinite, halloysite, vermiculite, chlorite, attapulgite, 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 prcsently 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 ftom about 0.25 weight % to about 30 weight %, preferably about 0.5 weight % to about 25 weight %, and most preferably I weight % to 20 weight %. The water-soluble polymer can be present in the composition in the range of from about 0.005 to about 15; preferably about 0.005 to about 10, more preferably about 0.0 1 to about 6, and most preferably 0. 0 1 to 3 weight percent of the composition.
The scope and definition of liquid are the same as those disclosed above. The liquid component generally makes up the rest of the composition.
According to the present invention, a thinner can also be present in the present invention, if desired, in an amount in the range of from about 0. 00 1 to about 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 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 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 0.000 1 to about 70.
Additionally, the composition of the seventh embodiment of the invention can also comprise a variety of other components or additives to obtain a desired property. Examples of thecommonly used components or additives include.
but are not limited to, viscosifiers, fluid loss control agents, salts, lubricants. surface active agents, flocculants, shale inhibitors, corrosion inhibitors, oxygen scavengers, or combinations of any two or more thereof.
The composition can be prepared by any means known to one skilled in the art such as blending, mixing, etc. Because these means are well known in the art, the description of which is omitted herein for the interest of brevity.
Examples provided hereinbelow are intended to assist one skilled in the art to further understand the invention and should not be considered limitative. EXAMPLE I This example illustrates the preparation of nitrogen-containing olefinic monomers N-acryloyl morpholine (NAM) N 0 0 N-acryloyl morpholine 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 3 50 ml of chloroform and cooled to ca.
-15C, Acryloyl chloride (0.42 mole; 37.8 g) was then added from a droping funnel in such a way that the temperature in the reaction flask did not exceed OC. 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 (500 ml), and the precipitated material was filtered from the ether. The organic phase was concentrated on a rotavapour. Hydroquitione (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. 74C/0.01 mbar. The yield was 64%.
N-acilloyl-N'-mcthvi piperazine (AMP) 0 N \-/ N- N-acryloyl-N'-niethyl 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 m] 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 mi 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 CaC12. Distillation under reduced pressure gave the product as a clear liquid.
13.p. 90-95 CIO.5 mbar. The yield was 72%.
N-aclyloyl-N'-(3-sulfoproj2y])-N'-methy1 piperazinium inner salt (AMPPS N N 0 \_j \--\-S 0 03 N-acryloyl-N'-(3-sulthpropyl)-N'-rnethyl piperatnium innersalt was prepared from 0.26 mole (40.1 g) of N-acryloyl-N'-rnethyl piperazine and 0.29 mole (34.9 g) of 1,3 -propanesultone. The reagents were mixed together with 0. 1 g of is 1,3-dinitrobcnzcnc in 260 mI of acetonitrile. The reaction mixture was heated to WC for 2 1/2 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 (12 mm Hg) for 19 hours. The yield was 68%.
1 N-acaloyl-N'-(2-amino-2-oxoethyl)-N'-methyI chloride (AOMPCI "- C? 0 0 \--/ %-' N-acryloyi-N'-methyl piperazine (0. 13 mole; 20.0 g) was dissolved in 260 ml of dry acetonitrile (distilled over P205) together with 0. 1 g 1, 33-dinitrobenzene.
Then 0.16 mole (14.6 g) 2-chloro acetarnide was added to the N-acryloylN'-methyl piperazine, and the mixture was heated to ca. 80"C for 123 hours. A white, precipitated powder was filtered and washed three times with diethyl ether (150 ml).
The product was dried under reduced pressure (12 mm Hg) for 12 hours. The yield was 75%.
N,N-dimethyl-N-(3-sulfoRrog!yl)7N-(4-vinylbenzyl) amrnoniiun inner salt (DMAMSPS) VN S N,N-dimcthyl-N-(4-vinylbenzyl) amine (93.0 mmole, 15 g), 111.6 mmole (13.6 g) of 1,3-propanesultone and 0.1 g of 1,3dinitrobenzene were mixed together and dissolved in 180 ml of toluene. The mixture was heated at 45-50"C for 72 hours. A white, precipitated material was filtered, washed three times with diethyl ether (100 ml), and finally dried under reduced pressure (I I MM Hg) for hours. The yield was 87%.
N.N-dimethyl-N-(2-amino-2-oxoethyl)-N-(4-vinylbel3,iyl) ammoniurn. chloride (AODVAC) C'9-NH2 0 G.
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%.
N-(2-amino-2-oxocthyl)-N'-vinyl imidazolium chloride (AOVC) 1 NC7Y I-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-xflnitrobenzene were mixed together, dissolved in 340 nil 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-dimethvi-N-(3-sulfop=yl):3-(aúaloyI amino)-] -Propaneammoniurn inner salt (APDAPS) 0 0 0 Acryloylchloride (0.70 mole; 63.8 g) and 0. 1 g of hydroquinone were dissolved in 350 mi of acetonitrfle and cooled to -159C. Then 0.59 mole (60.0 g) of 3-dimethylamino- 1 -propylamine was added from a dropping ftmel 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 mI distilledwater, 0.70 mole) was added and the precipitated material was filtered. The filtrate was concentrated on a rotavapour and then distilled under reduced pressure. B.p. 122 C/O. I mbar.. The yield was 55%. Eighty-three mmole (13.0 g) of this product was reacted further with 99.6 mmole (12.2 g) of 1,3-propanesultone in 83 ml of toluene. In the 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 ether (200 ml). Finally the product was dried under reduced pressure (12 mrn Hg) for 17 hours. The yield was 80%. EXAMPLE 11 This example illustrates the production of polymers of the present invention.
Polymerizations were carried out in distilled water or synthetic sea water. For synthetic sea water, one liter distilled water contained 23.83 g NaCl, 0.21 g NaHCO, 10.779 MgC'2-6H,O, 1.65 g CaC'2-2H,O, and 42.9 g anhydrous Na,SO..
The monomer solution was 35 weight % and the initiator concentration was 0.3 mole % with respect to total concentration of monomers. The azo-type initiator VA-044 (2,2'-azobisodihydrochloride) was used to start the polymerizations. The polymerizations were carried out at room temperature. In a typical synthesis, specified quantities of the monomers 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 1yophilized (freeze dried). The term "parts" used hereinafter in defining a polymer denotes mole %. The products were white, amorphous powders.
Copolymer 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 pCTIUS96118174 0.3 mole % VA-044 as a initiator. The polymer was precipitated in acetone. The yield was 34 Coj2olyMer Am / NAM Eighty parts of acrylarnide and 20 parts of N-acryloyl morpholine (NAM) were dissolved in distilled water and the polymerization was carried out with use of 0.3 mol % VA-044 as initiator. The polymerization was stopped after 6 hours.
The polymer was precipitated in acetone. The yield was 69 Terpolymer Am / NAM / AMP The polymer was prepared from 70 parts of acrylamide, 15 parts of N-acryloyl morpholine (NAM) and 15 parts of N-acryloyl-N'-methyl piperazine (AMP) with use of 0.3 mole % VA-044 as initiator. Distilled water was used as solvent. After 5 hours the polymer was precipitated in acetone. Theyieldwas4l%.
CoRglyrner Am / AMPPS Eighty parts of acrylamide and 20 parts of N-acryloyi-N'-(3-sulfopropyl)-N-methyI piperazinium inner salt (AMPPS) were polymerized in synthetic sea water for 2 hours with use of 0.3 mole % VA- 044 as initiator. The polymer was precipitated in methanol. The yield was 62%.
Copolymer Am J DMAMSPS A polymer was prepared from 80 parts of acrylamide and 20 parts of N,N-dimethyl-N-(3-sulfopropyl)-N-(4-vinylbenzyl) ammonium tnner salt (DMAMSPS) dissolved in synthetic sea water. 0.3 mole % VA-044 was used as initiator. After 4 hours the polymer was precipitated in methanol. The yield was 48%.
Copolymer Am / APDAPS Eighty parts of acrylamide and 20 parts of N,N-dimethyl-N-(3-sulfopropyl)-3-(acryloylamino)-t -propaneammonium inner salt (APDAPS) were polymerized in syjithetic sea water for 5 hours with use of 0.3 mole % VA-044 as initiator. The polymer was precipitated in methanol. The yield was 81%. - T=Qlymer Am 1 AMP DMAMSPS Sixty parts of acrylarnide, 20 parts of N-acryloyi-N'-methyl piperazine (AMP) and 20 parts of N,N-dimethyl-N-(3-sulfopropyl)-N-(4-vinylbenzyl) ammonium inner salt (DMAMSPS) were dissolved in synthetic sea water and the polymerization was carried out with use of 0.3 mole % VA-044 as initiator.
The polymerization was stopped after 3 112 hours by precipitation of the polymer in methanol. The yield was 23%.
T=ollmú1 Am 1 AMP) APDAPS Seventy parts of acrylamide, 25 parts of N-acryloyl-N-methyl piperazine (AMP) and 5 parts of N,N-dimethyl-N-(3-sulfopropyl)-3-(acryloylamino)-1- propanearmonium inner salt (APDAPS) were polymerized in synthetic sea water with use of 0.3 mole % VA-044 as initiator. The polymerization was stopped after 3 hours by precipitation of the polymer in methanol. The yield was 59%. Terpolymer Arn / AMP 1 AMPPS Seventy parts of acrylarnide, 15 parts of N-acryloyl-N'-Methyl piperazine (AMP) and 15 parts of N-acryloyi-N'-(3-sulfopropyl)-N-methyl piperazinium inner salt (AMPTS) were dissolved in synthetic sea water and polymerized for 23 hours. VA-044 was used as initiator. The polymer was precipitated in methanol. The yield was 34%. ColpolyMer AOMEC 1 AMPS Fifty parts of 2-acrylamido-2-methylpropanesuifonic acid (AMPS). 51) parts N-acryloyl-lr-(2-amino-2-oxoeffivl)-N'-m ethyl piperazinium chloride (AOMPC) and 50 parts NaOH were dissolved in NaCI-solution and polymerized for 6 hours with use of 0.3 mole % VA-033 as initiator. The polymer was precipitated in methanol. The yield was 54%.
Te=]=er AOVC / ANP / ANTS A polymer was preparqd from 15 parts of N-(2arnino-2-oxoethyl)-N'-vinyI imidazolium chloride (AOVC), 70 parts of Nacryloyi-N'-methyl piperazine (AMP), 15 parts of 2-acrylamido-2-methylpropane-sulfonic acid (AMPS) and 15 parts of NaOH in synthetic sea water. Tbree tenths mole % VA-044 was used as initiator and the polymerization was stopped after 5 hours by precipitation of the polymer in methanol. The yield was 38%. AOMPQ HornopQlymer.
N-acryloyi-N'-(2-amino-2-oxoethyl)-N'-methyI piperazinium chloride (AOMPC) (20.19 mmol) was dissolved in synthetic sea water and 0.3 mole % VA-044 was added. The polymerization was stopped after 6 hours by precipitation of the polymer in acetone. The yield was 57%.
TeWlyrner Am / AMP / AMPS Seventy parts of acrylamide, 15 parts of N-acryloyi-N'-methyl piperazine (AMP) and 15 parts of 2-acrylarnido-2-methyl-propanesulfonic acid (AMPS) were dissolved in distilled water and polymerized for 3 hours. Three tenths mole % VA-044 was used as initiator. The polymer was precipitated in acetone. The yield was 47%.
EXAMPLE III
Mis example illustrates the preparation of gelling compositions from the polymers disclosed above and the stability of gels formed from the gelling compositions.
Preparation of GeHing 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 stip-ing before use.
Stock solutions of phenol, formaldehyde and HMTA each containing 10,000 mg/l (ppm) were used.
For each test 4.0 g of gelling composition were made by adding polymer, phenol and formaldehyde/HMTA solution and diluting with synthetic sea water to the correct concentration. The same pprn concentration of both phenol and formaldehyde/HMTA was used. Magnetic stirring was used to raix 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 ga s for 5 minutes before the vials were closed. The glass vials were weighed before and after adding gelling compositions.
For aging at 120C, the glass vials were placed in stainless steel 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 is visually as weak, strong or rigid- The syneresis of the gels were measured as (weight of gel after exposure) / (initial weight of gel forming solution).
For gels in ampules, the syneresis was measured by measuring 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 urn Millipore filter. The relative viscosity of the 0. 1 weight % polymer solution (relative to synthetic sea water) was measured with an IJbbelhcde viscosimeter with an inner capillary diameteTof 0.69 mm. At least 3 parallel measurements were performed for each solution. T"he temperature of the polymer solution under the viscosity measurement was 25.0 0.05 " C.
Relative viscosity: time for polymer solution through capillary/ time forsynthetic sea water trough capillary Inherent viscosity: ln(rel. visc.) / 0. 1 g/dl The results are shown in the following Tables I-M. These tables show that gels formed from the polymers of the present invention were resistant to high temperature and high salinity environment. Little or no syneresis was observed after prolonged aging at high temperature and high salinity environment.
1 1. 36 Table 1
Polymer Phenol/ Gel height (G) and Am/AMP' Inherent conc. HMTAd Liquid height (L) after aging Run Feed Viscosity (ppm) in (pprn of at 120C in SNSW for No. Ratio' dllg SNSW' each) 30 days 55 days70 days 181 G-25 mm G=2.5 mm G=25 isi L-5 mm L=5 mm L=5 mm 1123 80120 5.4 6200 2500 Rigid Rigid Rigid 181 G=30 inm Cr=25 mm G=25 mra JS1 L-0 mm L=5 min L=5 mm 1123 80120 5.4 10400 2500 Rigid 1 Rigid Rigid 181 1 Cj=26 mm G-24 mm G=24 mm isi L=0 mim L= 1 mm L=2 max 1123 80120 1 5.4 1 20000 1 2500 1 Rigid Rigid 1 Rigid b 4Arn=acrylamide, AMP--N-acryloyl-N'-rnethyl piperazine male % ratio of monomers in the aqueous solution cSNSW=synthetic sea water HMTA=hexamethylenetetramine Table 11
Polymer Phenol/ Weight % gel' Inherent Conc. HMTA' Gel Character Run Ani/AMP' Viscosity (ppm) in (pprn of No. Feed Ratio' dI/g SNSW' each) 5 months 181 HSI so 1123 80/20 5.4 6200 2500 Rigid 181 isl so 1123 80/20 5.4 10400 2500 Rigid 18 1 is] 90 11 80/20 5.4 20000 2500 Rigid 123 Am=acrylamide, AMP--N-acryloyl-N'-methyl piperazine b mole % ratio of monomers in the aqueops solution SNSW=synthetic sea water HMTA=hexamethylenetetramine eWeight % gel of initiai weight of the 5olution after aging at 120C in synthetic sea water Table III -Polyrner Phenol/ Inherent conc. HCHO' Run Am/AMP' Viscosity (Ppm) in (ppm of Weight % geP No. Feed Ratio' dilg SNSWc each) Gel Character days 30 days 154 TOB 100 VII 43 70130 5.1 20000 2500 Strong 168 JS1 55 176 70130 3.8 10000 500 Weak 168 JS1 100 176 70/30 3.8 20000 2500 Rigid TOB 100 VII 52 60140 4.3 20000 2500 Strong TOB 82 VIT 52 60140 4.3 5000 1000 Rigid TOB 100 - - VII 52 60140 4.3 10000 1000 Strong TOB 100 VII 52 60140 4.3 10000 2000 Rigid 156 TOB 100 VII 49 50:50 3.4 20000 7500 Weak 156 TOB 83 VII 49 50/50 3.5 5000 1000 Strong Table 111
Pdlymer Phenol/ Inherent canc. HCHC0 Run Am/AMP Viscosity (ppm) in (ppm of Weight % gelo No. Feed Ratio' d11g SNSW. each) Gel Character 156 TOB 89 V11 49 50150 3.5 10000 1000 Strong 156 TOB 100 V11 49 solso 3.5 10000 2500 Rigid Am=acrylarnide, AMP=N-acryloyl-N'-methyl piperazine hmole % ratio of monomers in the aqueous solution c5NSW=synthetic sea water HCHO--formaidehyde Weight % gel of initial weight of the solution after aging at 120C in synthetic sea water Table TV
Polymer Weight % gel' Inherent conc. Phenol/ Gel Character Run Arn/AMP Viscosity (ppm) in HIVITA No. Feed Ratio' dllg SNSW1 (Ppm) 30 days 154 TOB 96 V11 43 70130 5.1 10000 2000 Strong 154 TOB 100 VII 43 70130 5.1 20000 2000 Strong 168 JS1 176 70:30 3.8 5000 1000 Strong 168 JS1 73 176 70:30 3.8 10000 500 Weak.
1, 39 Table IV -Polymer Weight % gel' Inherent cone. PhenoM/ Get Character Run Am/AMM Viscosity (ppm) in MATA' No. Feed Ratio' dilg SNSWc (ppm) 30 days 168 isi 80 176 70:30 3.8 10000 1000 Weak TOB 92 V11 52 60140 4.3 10000 2000 Weak.
TOB ' 100 VII 52 60140 4.3 20000 2000 Strong 197 JS1 100 1163 60/40 3.8 20000 2500 Rigid 197 isi 90 1163 60140 3.8 10000 2500 Rigid 198 isi 100 1165 60140 3.7 20000 2500 Rigid 156 TOB 100 VII 49 solso 3.5 20000 2000 Weak Am=acrylamide, AMPN-acryloyl-M-methyl piperazinc hmole % ratio of monomers in the aqueous solution SNSW=synthetic sea water d 2500 ppm HMTA=hcxamethylenetetrwnine Weight % gel of initial weight of the solution after aging at 120C in synthetic sea water is Table V
Polymer - PhenoU Gel height (G) Inherent Conc. Hmtad and Liquid height (L) after aging Run Aminam' viscosit (Ppm) in (Pprn of at 120C in SNSW for No. Feed y Snsw, Each) 30 days 55 days 70 days ratio' DI/g 179 G-30 mm G=28 mm G-29 mm is] H L= 5 mm L=7 mm L-7 nun 11 80:20 4.4 5400 2500 1 Rigid Rigid Rigid 179 10-27 mm G-27 mm G=27 mm isl 11 L=5 mtn L= 5 min L=5 mm 11 80:20 4.4 10300 2400 Rigid Rigid Rigid 179 G=26 mm G=34 mm G-24 nun isl 11 L-3 mm L-5 mrn L-5 mm 11 80:20 4.4 20000 1 2400 Rigid Rigid Rigid Arn=acrylamide, NAM=N-acryloyl morpholine bmole % ratio of monomers in the aqueous solution SNSW=synthetic sea water IHMTA=hexamethyleneteb-amine Table VI
Polymer Phenol/ Weight % gel' Inherent conc. HMTA' Gel Character Run AmINAM' Viscosity (ppm) in (ppm of No. Feed Ratio' dllg SNSWI each) 5 months 179 isl 0.8 11 11 80/20 4.4 5400 2500 Rigid 179 isi 0.9 11 11 80120 4.4 10300 2400 Rigid 179 is] 0.9 Il 11 80/20 4-4 20000 2400 Rigid aAm=acrylamide, NAM=N-acryloyl morpholine bmole % ratio of monomers in the aqueous solution SNSW=synthetic sea water HMTA=hexamethylenctetramine eWeight % gel of initial weight of the solation after aging at 120C in synthetic ea water Table VII -Polymer Phenol/ Inherent cone. HCHCY Run Arn/NAW Viscosity (Ppm) in (Ppm of Weight % gele No. Feed Ratio' dllg SN'SWc each) Gel Character isi 30 179 80120 6.2 10000 500 Strong Isi 28 179 80120 6.2 10000 2500 Strong 171.
isi 1 100 181 70130 3.7 10000 1000 Rigid 172 isi 92 183 60140 3.3 20000 1000 Rigid 71 TOB 100 70 v 95 20180 2.5 20000 2500 Strong Strong TOB 42 35 Vil 20180 1.1 30000 4000 Strong 5trong 17 TOB 55 vil 20180 1.1 30000 2000 Strong 17 Arn=acrylarnide, NAM=N-acryloyl morpholine b mole % ratio of monomers in the aqueous solution SNSW=synthetic sea water HCHO--forrnaidehyde eWeight % gel of initial weight of the solution after aging at 120C in synthetic sea water 10.
Table VIII
Polymer Weight % gel' Inherent conc. PhenoV/ Gel Character Run AmfNAM' Viscosity (ppm) in HMTAe No. Feed Ratio' d1/g SNSW' (ppm) 30 days Parallel I I Parallel 29 is[ 93 94 159 70/30 2.2 20000 2000 Rigid Weak isl 100 159 70130 2.2 10000, 2000 Rigid 151 is[ 96 80 161 60/40 2.2 20000 2000 Rigid Weak 152 isl 90 100 163 50/50 2.5 20000 2000 Strong Weak Am=acrylamide, NAM=N-acryloyl morpholine b mole % ratio of monomers in the aqueous solution SNSW=synthetic sea water 2500 ppm HMTA=hexamethylenctetramine Weight % gel of initial weight of the solution after aging at 120C in synthetic sea water zDuplicate Tuns.
1 1 j 43 Table IX - Polymer Phenol/ Weight % gele Inherent conc. HMTAd Gel Character Run Arn1NAM/AMP' Viscosity (ppm) in (ppm of No. Feed Ratio b dVg SNSW' each) 3 0 days 188 JSI 100 1121 70115/15 4.6 10000 2500 Rigid 188 M 95 1121 70/15/15 4.6 20000 2500 Rigid 198 isl 47 1121 70/15/15 4.6 10000 1000 Strong Am=acrylamide, NAM=N-acryloyl morpholine, AM!"-N-acryloyl-M-inethyl piperazine bmole % ratio of monomers in the aqueous solution SNSW=synthetic sea water HMTA=hexamethylenetetramine gWeight % gel of initial weight of the solution after aging at 120C in synthetic sea water Table X
Phlymer Phenol/ Inherent Conc. HCH0d Run Am/AMPPS' Viscosity (ppm) in (ppm of Weight % gele No. Feed Ratio' dllg SN5W' each) Gel Character days 30 days 162 JS1 100 80120 2.2 10000 2500 Strong 162 JS1 100 2.2 20000 1000 Rigid 162 isi 100 80120 2.2 10000 2000 Rigid 132 J51 100 41 128 80120 1.8 30000 4000 Rigid Strong 132 JS1 32 128 70130 1.8 30000 2000 Strong 130.
JS1 100 62 126 60140 1.6 30000 4000 Strong Strong JS1 75 126 60140 1.6 30000 2000 Strong TOB 94 60 VI 68 50150 20000 2500 Weak Weak TOB 100 88 vil 15 50140 1.5 30000 4000 Strong Strong TOB 77 V11 is 50150 1.5 30000 2000 Strong Am=acrylamide, AMPPS=N-acryloyl-N'-(3-sulfopropyl)-J'-methyl piperazinium Table X1
Polymer Phenol/ Weight % gele Inherent conc. HM'fA d Gel Character Run Arn/AMPPS& Viscosity (ppm) in (ppm of No. Feed Ratiob dilg SNSWc each) 30 days 202 ISI Rigid 1167 80120 3.5 10000 2500 90 202 isi Rigid 1167 80120 3.5 20000 2500 70 Arn=acrylarnide, AMPPS=N-acryloy]-M-(3-sulfopropyi)-N'-methyl piperazine inner salt hmolc % ratio of rnonorners in the aqueous solution SNSW=synthetic sea water IHMTA=hexarnethylenetetramine eWeight % gel of initial weight of the solution after aging at 120 C in synthetic sea water Table XII polymer Phenol/ Inherent conc. HCH0d Weight % geP Run Arn/DSPS' Viscosity (ppm) in (ppm of Gel Character No. Feed Ratio' dilg SNSW' each) days 30 days 149 is] 81 90110 1.0 10000 2500 Strong 149 isi 88 90110 1.0 20000 2500 Strong TOB 100 79 V 79 80120 0.9 10000 2500 Weak Weak 137 TOB 93 72 V11 23 80120 2.0 30000 4000 Strong Strong 137 TOB 77 VII 23 80120 2.0 10000 1000 Strong 137 TOB 100 V11 23 80120 2.0 10000 2500 Rigid &Am=acrylamide, DMAMSPS=N,N-dimethyt-N-(3-suifopropyl)-N-(4-vinylben-yi)- ammonium inner salt hmole % ratio of monorners in the aqueous solution SNSW=synthetic sea water IMCHG--formaldehyde eWeight % gel of initial wcight of the solution after aging at 120C in synthctic sca water Table XIII
Polymer Phenol/ Weight % gelc Inherent Conc. HMTA d Gel Character Run Am/DMAMSPS" Viscosity (ppm) in (ppm of No. Feed Ratio' dVg SNSWr each) 3 0 days 137 TOB 81 V11 23 80/20 2.o 10000 2000 Weak gel 137 TOB. 100 VII 23 80/20 2.0 20000 2000 Weak Am=acrylamide, DMAMSPS=N,N-dimethyl-N-(3-sulfopropyl)-N44-vinylbenzyi)- ammonium inner salt b mole % ratio of monomers in the aqueous solution cSNSW=synthetic sea water 4HMTA=hexamethylenetetramine Weight % gel of initial weight of the solution after aging at 120C in synthetic sea water is Table XIV
Polymer Phenol/ Weight % gelt Inherent conc. ffMTA d Gel Character Run Am/APDAPS, Viscosity (ppm) in (ppm of No. Feed Ratiob dl/g SNSWI each) 30 days 193 TOB 80 V11 89 80/20 5.3 5000 2500 Rigid 193 TOB so Vil 89 80/20 5.3 10000 2500 Rigid 193 TOB 90 vil 89 80/20 5.3 20000 2500 Strong Am=acrylamide, APDAPS=N,N-dimethyl-N-(3-sulfopropyl)-3-(acrvloylamino)-1propaneammoniurn inner salt bM ole % ratio of monomers in the aqueous solution SNSW=synthetic sea water HMTA=hexamethylenetetramine eWeight /gel of initial weight of the solution after aging at 120C in synthetic - sea water PCT/U596118174 Table XV
P01jyMer Phene 11 PhenoV Weight % gel' Arn/AMPI Inherent emc, HCH(Y HWA Gel Chara= Run DMAMSPS' Viscosity (ppm) in (ppm of (ppin of No. Feed Ratiob dilg SNSWc each) each) 30 days TOB 100 VII 87 60/20120 2.4 10000 2500 Strong TOB 100 VII 87 60120120 2.4 20000 2500 Rigid TOB 100 VIl 87 60120/20 2.4 20000 2500 Rigid Am=acrylamide, AMP=Nacryloyl-N'-mothyl piperazine, DMAMSPS=N,N-dimethyl-N-(3-sulfopropyi)-N-(4-vinylbcnzyl)-amnionium inner salt bfflole % ratio of monomers in the aqueous solution SNSW=synthetic sea water dHMO=formaidehyde cHMTA=hexamethylenetetramine Weight % gel of initial weight of the solution afler aging at 120 C in synthetic_ sea water so Table XVI
Polymer Phenol/ Weight % gelt Am/AMP/ Inherent cone. HNITA d Gel Character Run APDAPS' Viscosity (ppm) in (Pprn of No. Feed Ratiob dilg SNSWc each) 30 days 196 TOB 100 V11 85 7012515 4.4 5000 2500 Rigid 196 TOB 83 V11 85 7012515 4,4 10000 2500 Rigid 196 TOB 86 V11 85 7012515 4.4 20000 2500 Rigid 203 IBV 85 149 60130110 3.5 10000 2500 Rigid 203 IBV 85 149 60130110 3.5 20000 2500 Rigid Arn=acrylarnide, AMP=N-acryloy]-N'-rnethyl piperazine. APDAPS=KN- dirnethy]-N-(3 sulfopropyl)-3-(acryloylamino)-1propancarnmonium inner salt hmole % ratio of monomcrs in the aqueous solution eSNSW=synthetic sea water HMTA=hexamethylenetetramine Weight % gel of initial weight of the solution after aging at 120C in synthetic sea water Table XVI I
Polymer PhenoU Weight % gel, Am/AMP/ Inherent conc. H1VITA' Gel Character Run APDAPS' Viscosity (ppm) in (ppm of No. Feed Ratio' dilg SNSY each) 30 days 184 isi 70 1125 70115115 1.9 10000 2500 Rigid 184 JS1 100 1125 70115/15 1.9 20000 2500 Rigid Am=acry)amide, AMP--N-acryloyl-M-methyl piperazine, AMPPS=N-acryloyi-N'-(3-sulfopropyi)-N'-methyl piperazinium inner salt b mole % ratio of monomers in the aqueous solution 5NSW--synthetic sea water "HMTA=hexamethylenetetrwnine eWeight % gel of initial weight of the solution after aging at UCC in synthetic sea water is Table XVIII
Polymer Phenol/ Weight % gele AOMPC/ Inherent conc. HCH04 Gel Character Run AMPS' Viscosity (ppm) in (ppm of No. Feed Ratio' dlIg SNSW' each) 30 da ys 189 1BV 100 143 50/50 1.1 10000 2500 Strong a AOMPC=N-acryloyl-N'-(2-wnino-2-oxoethyl)-N'-methyI piperaziniurn chloride, AMPS=2-acrylamido-2-methyl-propanesulfonic acid mole % ratio of monomers in the aqueous solution SNSW=synthetic sea water HCHO--formaldehyde "Weight % gel of initial weight of the solution after aging at 120C in synthetic sea water Table XIX -Polymer Phenol/ Weight % gelc A0VC/AMP1 Inherent conc. HCH01 Gel Character Run AMPS' Viscosity (ppm) in (ppm of No. Feed Ratio' di/g SNSW, each) 30 days 191 JS1 100 1133 15170115 1.6 20000 2500 Rigid AOVC=N-(2-amino-2-oxoethyi)-N'-vinyl imidazolium chloride, AMP=N-acrylovl- N' methyl piperazine, AMPS=2-acrylamido-2-methyi-propanesulfonic acid hmole % ratio of monomers in the aqueous solution cSNSW=synthetic sea water d HCHO=formaidehyde eWeight % gel of initial weight of the solution after aging at 120'C in synthetic sea water Table XX
Inherent Viscosity dllg Polymer Phenol/ Weight % geld conc. HCHO' Gel Character Run AOMPC 0.1 (ppm) in (pprn of No. Hofflopol, weight % SN1SWh each) 30 days 117 TOB 100 vii 8 1.4 30000 4000 Strong AOMPC=N-acryioy]-N'-(2-amino-2-oxoethyl)-N'-rnethyl piperazinium chloride.
homopolymer SNSW=synthetic sea water HCHO=formaidehyde "Weight % gel of initial weight of the solution after aging at 120C in synthetic sea water 1 Table XXI
Polymer Phenol/ Weight % gele Am/AMP/ Inherent conc. HCHO' Gel Character Run AMPS" Viscosity (ppm) in (Ppm of No. Feed Ratio' dI/g SNSW' each) 30 days 157 TOB 100 VII 57 50/25/25 3.4 20000 1000 Strong 157 TOB 100 VII 57 50125/25 3.4 20000 2500 Strong Am=acrylamide, AMP--N-acryloyl-N-methyl piperazine, A MPS=2=acry lam ido-2-m ethyl-propanesulfonic acid bmole % ratio of monomers in the aqueous solution cSNSW=synthetic sea water "HCHO--formaldehyde Weight % gel of initial weight of the solution after aging at 120C in synthetic sea water EXAMPLE IV This example is a comparative example showing that gels formed from a corninonly employed polyacrylamide do not withstand well under a hostile environment condition as compared to the gels formed from the invention polymers.
A 7000 ppm solution of Dowell J333 polyacrylamide in seawater was crosslinked with phenol and formaldehyde at 120C. Table XXII shows a summary of the results.
Table XXII
Polymer Phenol/FormaldehYde Get Height (G) and'Liquid Height (L) Concentration (ppm of each) 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 XXII indicate that much syneresis occurred in gels forTned ftom polyacrylamide only after aging for 6 days.
EXAMPLE V
This example illustrates a fTesh 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 XMII 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 AN RP 1313-1. First Edition, June 1, 1990 procedure. The compositions were then mixed for five minutes and tested for filtration according to the low-temperaturellow-pressure test procedure.
These test results are presented in Table XXIV under 9nitial 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 mixe d for 5 minutes. These test results arc represented in Table =V under "Results After Aging at 75 "C".
Table MIP
Run Materials Used 8-1 345 m] tap water + 10 g bentonite (40) 8-2 325 mi tap water + 10 g bentonite (20) + 20 g of 4% solution of NAMIAM in deionized water (20). 8-3 325 m] tap water - 10 g bentonite (20) + 20 g of 4% solution of NAWAP in deionized water (20). 8-4 325 mi tap water + 10 g bentonite (20) + 20 g of 4% solution of NAM/AA in deionized water (20). 8-5 305 mi tap water + 10 g bentonite (20) + 40 g of 4% solution of NAM/AM in deionized water (20). 8-6 305 mI tap water + 10 g bentonite (20) + 40 g of 4% solution of NAWAP in deionized water (20). 8-7 305 mi tap water + 10 g bentonite (20) + 40 g of 4% solution of NAM/AA in deion ized water (20).
aNAM/AM is a copolymer of 25% (mole %) acryloyl morpholine and 75% acrylamide; NAM/AP is a copolymer of 25% acryloyl morpholine and 75% acryfamide-2-methylpropanesulfonate; NAM/AA is a copolymer of 25% acryloyl rnorpholine and 75% acrylate; these polymers were prepared according to the process disclosed in Example 11.
Table XXJV2
Initial Results Results After Aging at 75 C Run AV PV YP Gels FL AV PV YP Gels FL 8-1 2.5 2 1 1/1 20.4 2.5 2 1 1/2 16.8 8-2 12.0 6 12 3/5 63.7 14.5 5 19 3/6 67.6 &3 8.0 7 2 1/3 15.8 8.5 7 3 2/2 15.4 84 10.5 8 5 1/3 13.5 11.5 10 3 2/3 13.1 8-5 32.5 19 27 14/23 69.1 33.0 19 28 CNM 47.4 8-6 24.0 13 22 3/5 7.8 25.0 15 20 315 9.0 8-7 36.0 21 30 516 8.3 37.0 23 28 516 8.6 AV-apparent viscosity, cps PV-plastic viscosity, cps.
Gels-gel strength, 10 seconds/I Orninutes, lbs/1 00 sq.ft.
FL-fluid loss at low-tempeTature/low-pressure, nil 30 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 thiz fluid composition of run 8-1 that represents a base fluid which did not contain any poiyme7.
Further, these four inventive compositions had higher viscosity than the basc fluid.
High viscosity is desirable. Even though two invcntive compositions (run 8-2 and 8-5) had high fluid loss, their high viscosity is useful in bringing the drilt cuttings to the surface.
EXAMPLE V1
This example illustrates a sea water based composition of the invention that can bc uscd as drilling fluids, completion fluids, or workover fluids.
Four sea water based compositions were prepared by mixing the components shown in Table XXV on7a.Multi-mixer in quart jars. The mixing time, in rn I nutes, 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 mlnuts and after adding 0.0.5 ml of octyl alcohol as a defoamer to each composition, each sample was tested initially for viscosity, gel strength, and filtration at low- temperature/low-pressure according to the API RP 13B- 1, First Edition, June 1, 1190 procedure. These test results are presented in Table XXVI under "Initial Results". The compositions were then kept in capped jars at 75'C for about 16 hours and cooled to about 30C. Next, the compositions were mixed 5 minutes and, after adding 0.05 ml of octyl alcohol as a defoamer to each composition. they were retested. These results are represented in Table XXVI under "Results After Aging at 75'C". The composition of sea water is shown in Example IL Table XW
Run Materials Used 9-1 340 rn 1 tap water + 10 g bcntonite (20) + 2 g Na-lignite (10.1 14.7 g sea salt (30) 9-2 265 mi 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 mi tap water + 10 g bentonite (20) + 2 g Na-lignite (10) + 14.7 g sea salt (10) - 75 g of 4% solution ofNAM/AP in deionized water (20) 9-4 265 m] tap water + 10 g bentonite (20) + 2 g Na-lignite (10) + 14.7 g sea salt (10) + 75 g of 4% solution of NAM/AA in deionized water (20) 4See footnote a in Table XXIII.
1 I Table XXVIO Initial Results Results After Aging at 7 5 C Run AV PV YP Gels FL AV PV YP
Gels FL 9-1 6.5 2 9 819 79.2 7.0 3 8 6/8 62.2 9-2 16.5 10 1 13 518 1 19.4 15.0 10 1 10 4!9 1 18.5 9-3 24,0 15 Is 6/9 8.1 22.5 14 17 4/7 7-6 9-4 1 28. 18 21 4/15 4.8 1 24.5 16 17 3110 4.8 4AV-apparent viscosity, cps PV-plastic viscosity, cps.
Gels-gel strength, 10 seconds/ I Ominutes, lbs/100 sq.ft.
FL-fluid loss at low-temperatureilow- pressure, nil 30 minutes. I 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 viscusity 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 (1)

  1. C THAT WHICH IS CLAIMED:
    I A composition cornprising a nitrogen-containing olefinic compound having the formula selected from the group consisting of R,C(R,)=C(R,)-(C=O)-(NH).-(Ar)-y-W(R2)(R2)-Y-SO3', R,-C(R,)=C(R,)-(C=O),,,-(NH).-(Ar).-Y-N"(R2)(R2)-Y-(C=O),,,-N(R2)(R2)X', RjC(Rj)=C(Rj)-(C=O),-N4 N-(R2)-Y-(C--O),-N(R2)(R2)X', R,C(R,)--C(RI)4C=O).-N N--Y-(C=O).-N(R,)(R2)X,, and combinations of any two or more thereof wherein R, 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 I to about 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, sulfanate, phosphonates, suffinate, phosphinate, and combinations of any two or more thereof, and each m is independently 0 or 1.
    2. A composition according to claim I wherein m is 0.
    3. A composition according to claim I wherein m is 1.
    4. A composition according to claim.1 wherein said olefuiic 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-mcthyl-N'-(4-amino-4-oxobutyl) piperazinium. chloride, N-acryloyi-N'-cthyl-N'-(2-amino-2 oxoethyl) piperazinium chioride, N-acryloyl-N'-cthylN'-(3-amino-3-oxopropyl) pinium chloride, N-acryloylN'-ethyl-N'-(4-amino-4-oxobutyi) piperazinium chloride, N,N-dimethyl-N-(2amino-2-oxoethyl)-N-(4-vinylbenzyl) anunonium chloride, N,N-diethyl-N-(2amino-2-oxoethyl)-N-(4-Yiny[benzyi) 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-Yinylbenzyl) ammonium chloride, N-(2-amino-2-oxoethyl)-N'-vinylimidazolium chloride, N-(3-amino-3oxopropyi)-N'-vinylimidazolimn chloride, N-(4-amino-4-oxabutyl)-N'vinylimidazollum chloride, and combinations of any twe, 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-ainino-2-oxoethyl)-N-(4-vinylbenzyl)arrunonium chloride, N-acryloyl-N'methyl-N'-(2-amino-2-oxoethyl)piperazinium chloride, N-(2-amino-2-oxoethyl)-N'-vinylimidazoliurn 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-arruno-2-oxoethyi)-N-(4vinylbenzyl)ammonium chloride.
    7. A composition according to claim 1 wherein said nitrogen-containing olefinic compound is N-acryloyl-N'-methyl-N'-(2-amino-2oxoethyl)plperazinium 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 arnine with an alkylating agent under conditions sufficient to effect the production of said nitrogcn-containing olefinic compounds wherein said nitrogen-containing olefinic compound has the formula selected from the group consisting of RIC(R,)=C(Ri)-(CO).-(NH),-(Ar),-Y-N-(R(R(R2)-Y- SO3-, RI-C(R,)=C(Ri)-(C=O).-(NH),,,-(Ar).-Y-N(R2XR2)-Y-(C=O).,-N(R2)(R2)X-, RjC(R,)=C(Rj)-(C=O),.-N N-(R2)-Y-(C=O),,,-N(R2XRX-, R,C(R,)=C(R,)-(C=O),,,-N N±Y-(C--O).-N(R2)(R2)X-, and combinations of any two or more thereof wherein R, and R2 are each independently selected ftom 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 I to about 30 carbon atoms; Ar is an arylene group; each Y is independently selected from the group consisting of alkylene radical, phenylene group, imidazolcum group, naphthylcne group, biphenylene group, and combinations of two or more thereof; X is an anion selected from the group consisting of halide. sulfate, phosphate, nitrate, sulfonatc, phosphonates, suffinate, phosphinate, and combinations of any two or more thereof, each in is independently 0 or 1; amine is selected from the group consisting of C N,N-dimethyl-N-(4-vinylbenzyl) amine, NN-dimethyl-N-(4-vinylbenzyl) amine, N,N-diethyl-N-(4-vinylbenzyl) amine, NN-diethyl-N-(4-vinylbenzyl) amine, N,N-dimethyl-N-(3-vinylbenzyl) amine, NN-dimethyl-N-(3-vinylbenzyl) amine, N,N-diethyl-N-(3-vinylbenzyl) amine and N,N-diethyl-N-(3-vinylberizyl) amine, and combinations of any two or more thereof-, and alkylating agent is selected from the group consisting of 3-chloro-propane- I -sulfonic acid, 4chloro-butane- I -sulfonic acid, 3-hydroxy-propane- I -sulfonic acid, 4-hydroxy-butane- I -sulfonic acid, the corresponding esters of the hydroxy-alkane- 1 -sulfonic acids such as 1,3- propanesultone and 1,4-butanesultonr,, and combinations of any two or more thereof.
    10. A process according to claim 11 wherein said nitrogen-containing olefinic compound is selected from the group consisting of N-acryloyl-N'methyi-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, Nacryloyl-N'-ethyl-N'-(2-wnine-2-oxoethyl) piperazinium. chloride, Nacryloyl-N'-ethyl-N'-(3-arnino-3-oxopropyl) piperaziniurn chloride, Nacryloyl-N'-ethyl-N'-(4-amino-4-oxobutyl) piperazinium chloride, N,Ndimethy]-N-(2-amino-2-oxoethyl)-N-(4-Yinylberizyl) ammonium chloride, 10 N,N-diethyl-N-(2-an:tino-2-oxoethyl)-N-(4-vinylbenzyl) ammoruin 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-3oxopropyl)-N'-vinylimidazolium chloride, is N-(4-amino-4-oxobutyl)-N'vinylimidazolium chloride, and combinations of any two or more thereof 11. A process according to claim 11 wherein said nitrogen-containing olefinic compound is selected korn the group consisting 0. N,N-dimethyl-N(2-ainino-2-oxoethyl)-N-(4-vinylbenzyl)ammonium chloride, N-acryloyi-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 composition according to claim 11 wherein said nitrogen-containing olefinic compound is N,N-dimethyl-N-(2-amino-2-oxoethyl)-N-(4vinylbenzyi)ammonium chloride.
    13. A composition according to claim I I wherein said nitrogen-containing olefinic compound.is N-acryloyl-N'-methyl-N'-(2-amino-2oxoethyl)piperazinium chloride.
    14. A composition according to claim I I wherein said nitrogen-containing olefinic compound is N-(2-amino-2-oxoethyl)-N'-vinylimidazolium chloride.
    15. A polymer comprising repeat units derived from a nitrogen-containing olefmic monomer having the formula selected from the group consisting of R,-C(R,)=C(R,)-(C=O),,,-M, R,-C(R,)=C(R,)-(C=O).-N N(R,), R,-C(R,)=C(R,)(C=O).-Nt_,"(R2)-Y-)C,, RIC(R,)-C(R,)-(C==O)M-(''H)M-(Ar).-N(R2)(R2)-YSO3, R,-C(R,)=C(R,)-(C=O),n-(NH) 4Ar).-Y-N(R2)(R2)-Y-(C--O),,,-N(R,)(R,)X, RIC(R,)=C(R,)-(C=O),.-N N'(R)-Y-(C=O),,,-N(R2)(R2)X-, RjC(Rj)=C(Rj)-(C-0),,-N N"-Y-(C=O)m-N(R2)(R2)X, and combinations of any two or more thereof whcrein R, and R2are 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 I to about 30 carbon atoms; M is a substituted or unsubstituted morpholine group; each Y is independently selected from the group consisting of alkylene radical, phenyl group, imidazolium group, naphthyl group, biphenyl group, and combinations of any two or more thereof-, each X is an anion selected from the group consisting of halide, sulfate, phosphatc, nitrate, sulfonate, phosphonates, sulfinate, phosphinate, and combinations of any two or more thereof, Ar is an arylene group, and each rn 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 RI-C(R,)=C(R,)-W, RI-C(R,)=C(R,)-(C=O),,,-Z, Rj-C(RL)=C(Rj)-Y-W, RI-C(R,)=C(R,)-(C=O),,,-N(R2)-Y-R,, Rj-C(Rj)=C(Rj)-(C=O).-G-Y-Z, RIC(Rj)--C(Rj)-(C=0)6-G-Y-W, R,-C(R,)=C(R,)(C=O).,-Y-Z, and combinations of any two or more thereof wherein each R, and R,- 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, 10.-each m is independently 0 or 1; Z has the formula selected from the group consisting of N(R2)(R2), N'(R, )(R,)(R2)X- in which X is an anion selected from the group consisting of halide, sulfate, phosphate, nitrate, sulfonate, phosphonates, sulfinatc, phosphinate, and combinations of any two or more thereof, G is N(R,) or 0; each Y is independently selected from the group consisting of alkylene radical, phenyl group, imidazolium group, naphthyl group, biphenyl 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.
    17. A polymer according to claim 15 fUn"her comprising repeat units derived from at least one olef-mic comonomer having the formula selected from the group consisting of R,-C(Rj)=C(R,)-(C=O),,,-Z, R,-C(Rj)=C(R,)-(C---O),,,- Y-W, Rj-C(Rj)=C(Rj)-W, R,-C(R,)=C(R,)-(C=O)-G-Y-W, and combinationsof any two or more thereof wherein 1.
    k - each R, 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(R,)(R2)(R2)X- in which X is an anion selected from the group consisting of halide, sulfate, phosphate, nitrate, sulfonate, phosphonates, sulfinate, phosphinate, and combinations of any two or more thereof, G is N(RI) or 0; each Y is independently selected from the group consisting of alkylene radical, phenyl group, imidazolium group, naphthyl group, biphenyl group, and combinations of two or more thereof, and W is an acid moiety selected from the group consisting of phosphinic acid, phosphonic acid, suffinic acid, sulfonic acid, sutfiuic 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 morpholine, N-acryloyl-N'-methyl piperazine, N-acryloyl-N'-ethyl piperazine, N-acryloyl-N'-propyl pipcrazine, N-acryloyl-N'-(3-sulfopropyl)-N'-methyI piperazinium inner salt, Nacryloyi-N'-(3-sulfopropyl)-N'-ethyI piperazinium inner salt, N-acryloylN'-(4-sulfopropyl)-N'-methyI piperaziniurii inner salt, N-acryloyl-N'-(4sulfopropyl)-N -ethyl piperazinium inner salt, N-acryloyl-N'-(2-amino-2oxoethyl)-N'-methyI piperazinium chloride, N-acryloyl-N'-(3-amino-3-oxopropyl)-N'-methyI piperaziniurn chloride, Nacryloyl-N'-(4-amino-4-oxobutyp-N'-methyI piperaziniurn chloride, Nacryloyi-N'-(2-wnino-2-oxoethyl)-N'-cthyI piperaziniurn chloride, N-acryloyPN '-(3 -amino- 3 -oxopropyl)-N'-ethyl piperazinium chloride, N-acryloyl-N'-(4-amino-4-oxobutyl)-N'-ethy1 piperazinium chloride, N,N-dimethyl-N-(3-suifopropyl)-N-(4-Yinyibenzyl) ammonium Inner salt, N,N-dimethyl-N-(4-sulfobutyl)-N-(4-vinylbenzyi) ammonium inner salt, N,N-diethyl-N-(3-suifopropyl)-N-(4vinylbenzyl) 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-suifobutyl)-N-(3-vinylben7yl) ammonium inner salt.
    N,N-diethy]-N-(3-suifopropyl)-N-(3-vinylbenzyl) ammonium inner salt, N,N-diethyPN (4-sulfobutyi)-N-(3-vinylbenzyl) ammonium inner salt, N,Ndimethyl-N-(2-amino-2-oxoethyl)-N-(4-vinyibenzyl) ammonium chloride, N,Ndiethyl-N-(2-amino-2-oxoethyl)-N-(4-vinylbenzyl) ammonium chloride, N,Ndimethyl-N-(3-amino-3-oxopropyl)-N-(4-Yinylbenzyl) ammonium chloride, N,Ndiethy]-N-(3-amino-3-oxopropyl)-N-(4-Yinylbcnzyl) ammonium chloride.
    NN-dimethyl-N-(2-wnino-2-oxocthyl)-N-(3-vinylbenzyl) ammonium chloride, N, N-diethyl-N-('--amino-2-oxoethyl)-N-(3-Yinylbenzyl) 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-vinyl benzyl) arrumonium chloride, N-(2-amino-2-oxoethyl)-N'-vinyl imidazolium chloride, 20 N-(3amino-3-oxopropyl)-N'-viny1 imidazolium chloride, N-(4-amino-4-oxobutyl)N'-vinyl imidazolium chloride, N,N-dimethyl-N-(3-suifopropyl)-3-(acryloy1 amino)- 1 -propaneammonium inner salt, N,N-diethyl-N-(3-suifopropyl)-3(acryloy1 amino)- 1 -propaneammonium inner salt, N,N-dimethyl-N-(4suifobutyl)-3-(acryloy1 amino)- 1-propaneammonium inner salt, 25 N,.Ndiethyl-N-(4-sulfobutyl)-3-(acryloy1 amino)-1 -propaneammonium inner salt. N,N-dimethyl-N-(3-suifopropyl)-2-(acryloy1 amino)- 1 -ethaneammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-2-(acryloyl amino)- 1 ethaneammoniurn inner salt, N,N-dimethyl-N-(4-sulfobutyl)-2-(acryloy1 amino)-1-ethaneanimonium inner salt, N,N-diethyl-N-(4-sulfobutyl)-2-(acryloyI aTnino)- I -ethaneamrnonium 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)-N44-vinylbenzyl) ammonium inner salt, N,N-dimcthyl-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-vinylbexizy]) ammonium inner salt, N,N-dimethyl-N-(3-suffopropyl)-N-(3-vinyibcnzyl) ammonium inner salt, N,N-dimethyl-N-(3-sulfobutyl)-N-(3-vinylbenzyl) ammonium inner salt, N,N-di.ethyl-N-(3-sulfopropyl)-N-(3-vinylbenzyl) ammonium inner salt, N,N-diethyl-N-(3-sulfobutyl)-N-(3-vinylbenzy]) ammonium. inner salt, N-acryloyl-N'-methyl-N'-(2-amino-2-oxoethyl) pipera2inium chloride, N-acryloyl-N'-methyl-N'-(3-amino-3-oxopropyl) piperazinium chloride, N-acTyloyi-N'-methyl-N'-(4-amino4-oxobutyl) piperazinium chloride, N-acryloyl-N'-ethyl-N'-(2-amino-2-oxoethyl) pipcrazinium chloride, N-acryloyl-N-ethyl-N'-(3-aminc-3-oxopropyl) piperazinium. chloride, Nacryloyi-N'-ethyl-N'-(4-amino-4-oxobutyl) piperaziniurn chloride, N,Ndimethyl-N-(2-ainino-2-oxoethyl)-N-(4-vinylbenzyl) ammonium chloride, N,Ndiethyl-N-(2-amino-2-oxoethyl)-N-(4-vinylbenzyl) ammoniuzn chloride, N,Ndimethyl-N-(3-amino-3-oxopropyl)-N-(4-vinylbenzyl) ammonium chloride, N,N-diethyl-N-(3-amino-3-oxopmpyl)-N-(4-vinylbenzyl) ammonium chloride, N- (2-amino-2-oxoethyl)-N'-vinylimidazolium chloridi. N-(3-amino-3oxopropyl)-N'-vinylimidazolium chloride, N-(4-ainino-4-oxobutyl)-N'vinytimidazolium chloride, and combinations of any two or more thereof.
    20. A polymer according to claim 17 wherein said nitro gen-containing olefinic monomer is selected from the group consisting of N-acryloyl morpholine, N-acryloyi-N'-methyl piperazine, N-acryloyl-N'-ethyl piperazine, N-acryloyl-N'-propyl piperazine, N-acryloyl-N'-(3-sulfopropyl)-N'-rnethyl piperazinium inner salt, N-acryloyl-N'-(3-suifopropyl)-N'-ethyl piperazinium inner salt, N-acryloyl-N'-(4-suifopropyl)-N -methyl piperazinium inner salt, N-acryloyi-N'-(4-suifopropyl)-N'-ethyI piperazinium inner salt, N-acryloyl-N'-(2-amino-2-oxoethyl)-N'-methyl piperaziniurn chloride, N-acryloyl-N'-(3-amino-3-oxopropyl)-N'-methyI piperazinium chloride, N-acryloyl-N'-(4-amino-4-oxobutyl)-N -methyl piperazinium chloride.
    N-acryloyl-N'-(2-amino-2-oxoethyl)-N'-ethyl piperazinium chloride, N-acryloyl-N'-(3-amino-3-oxopropyl)-N'-ethyI piperazinlurn chloride, N-acryloyl-N'-(4-amino-4-oxobutyl)-N '-ethyl piperazinium chloride, N,N-dimethyl-N-(3-suifopropyl)-N-(4-vinylbenzyl) ammonium inner salt, N,N-dimethyl-N-(4-sulfobutyl)-N-(4-vinylbenzyl) arnmonium inner salt.
    NN-diethyl-N-(3-suifopropyl)-N-(4-Yinylbenzyl) 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-dirnethyi-N-(4-sulfobutyl)-N-(3-vinylbenzyl) ammonium inner salt, N,N-diethyl-N-(3-suifopropyl)-N-(3-vinylbenzyl) ammonium inner salt, N,N-diethyl-N-(4-suifobutyl)-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-viny[benzyl) ammonium chloride, N,N-dimethyl-N-(3-an-dno-3-oxopropyl)-N-(4-Yinylbenzyl) ammonium chloride, N,N -diethyl-N -(3 -amino -3 -oxopropyl)-N-(4-Yiny IbenzyI) ammonium chloride, NN-dimethyl-N(2-amino-2-oxoethyi)-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-oxopropLyl)-N-(3-Yinylbenzyl) ammonium chloride, 1-1\ WO 97f22638 pCTfUS96/18174 69 N,N-diethyl-N-(3-amino-3-oxopropyl)-N-(3-vinylbenzyl) ammonium chloride, N-(2-amino-2-oxoethyl)-N'-vinyI imidazolium chloride, N-(3-amino-3-oxopropyl)-N'-vinyI imidazolium chloride, N-(4-amino-4-oxobutyl)-N'-vinyI imidazolium chloride, N,N-dimethyl-N-(3 -sulfopropyl)-3-(acryloyl amino)- I -propaneammoniurn inner salt, N,N-diethyl-N-(3-sulfopropyl)-3-(acryloyI amino)- I -propaneammoniurn inner salt, N,N-dimethyl-N-(4-sulfobutyl)-3 -(acryloyl amino)- I -propancan-Lmonium inner salt, N,N-diethyl-N-(4-sulfobutyl)-3-(acryloyI amino)- I -propaneammonium inner salt, N,N-dimethyl-N-(3-sulfopropyl)-2-(acryloyI amino)- I -cthaneammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-2-(acryloyI amino)- I -ethaneammonium inner salt, N,N-dimethyl-N-(4-sulfobutyl)-2-(acryloyI amino)- I -ethaneammonium inner salt, N,N-diethyl-N-(4-sulfobutyl)-2-(acryloyI amino)- I - 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-diethvi-N-(3-sulfopropyl)-N-(4-vinylbenzyl) ammonium inner salt, N,N- diethyl-N-(3-sulfobutyl)-N-(4-vinylbenzyi) 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, 10 N,N- diethyl-N-(3-sulfobutyl)-N-(3-vinylbenzyl) arnmohiurn inner salt, N- acryloyl-N'-methyl-N'-(2-amino-2-oxocthyl) pipcrazinium chloride, N- acryloyl-N'-methyl-N'-(3-amino-3-oxopropyl) piperaziniurn chloride, N- acryloyl-N'-methyl-N'-(4-amino-4-oxobutyl) piperazinium chloride, N- acryloyi-N'-ethyl-N'-(2-amino-2-oxocthyl) piperazinium cWoride, 15 N- acryloyi-N'-ethyl-N'-(3-arnino.-3-oxopropyl) piperazinium chloride, N-acryloyl-N'-ethyl-N'-(4-arnino-4-oxobutyl) piperaziniurn chloride, N,N-dimethyl-N-(2-amino-2-oxoethyl)-N,r(4-vinylbenzyi) 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, NN-diethyl-N-(3 -amino -3 -oxopropy I)-N-(4-vinylbenzyl) ammonium chloride, N-(2-amino-2-oxoethyl)-N'-vinylimidazolium chloride, N-(3 -amino-3)-oxopropyl)-N'-vinylirnidazolium chloride, N-(4-amino-4-oxobutyl)-N'-vinylimidazoliuxn 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'-(3-sulfopropyl)-N'- methyI piperaziMum inner salt.
    24. A polymer according to claim 17 wherein said nitrogen-containing olefinic monomer is N-acryloyl-TF-(2-amino-2-oxoethyl)-N'-methyI piperazinium chloride.
    25. A polymer according to claim 3 wherein said nitrogen-containing olefinic monomer is N,N-dirnethyl-N-(3-sulfopropyl)-N-(4-vinylbenzyi) ammonium inner salt.
    26. 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.
    27. A polymer according to claim 17 wherein said nitrogen-containing olefinic monomer is N-(2-amino-2-oxoethyl)-N'-vinyl imidazolium chloride.
    28. A polymer according to claim 17 wherein said nitrogen-containing olefinic monomer is N,N-dimethyl-N-(3-sulfopropyl)-3-(acryloyI amino)- I propaneammonium inner salt 29. A polymer according to claim 17 wherein said nitrogen-containing olefinic monomer is N-acryloylmorpholine.
    30. A polymer according to claim 17 wherein said olefinic comonorner is selected from the group consisting of acrylamide, styrene suffonic acid, salt of styrene sulfonic acid, N-methylacrylamide, N,N-dimethylacrylamide, acryli c acid, salt of acrylic acid, N-vinylpyrrolidone, methyl acrylate, methacrylate, vinyl sulfonic acid, salt of vinyl sulfonic acid, 2-acryimnido-2- methylpropanesulfonic acid, salt of 2-acrylamido-2-methylpropanesulfonic acid, and combinations of any two or more thereof.
    3 1. A polymer according to claim 30 wherein said olefinic comonorner is acrylamide.
    32. 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 Rj-C(Rj)=C(Rj)-(C--O),,,-M, Rj-C(Rj)=C(Rj)-(C=O).-N N(RI), Rj-C(RI)=C(Rj)- (C=O),,,-N' _P(R2)-Y-X-, R,C(R,)=C(Ri)-(C--O),,,-(NH).-(Ar),i-N'(R2)(R,)- y-SO3, R,-C(R,)=C(R,)-(C=O).-("4H).-(Ar)M-Y-N(R2)(R2)-Y-(C=O),,- N(R2)(R2)X', RIC(R,)=C(R,)-(C=O).-TN'(R2)-Y-(C=O),,,-N(R2)(12)X-, RIC(R,)=C(Ri)-(C=O).,-N N-Y-(C=O).,-N(R2)(R2)X-, and combinations of any two or more thereof and said olefinic comonorner has the formula selected from the group consisting of RI-C(R,)=C(R,)-W, Rj-C(Rj)=C(Rj)-(C=O),,,-Z, Rj-C(Rj)=C(Rj)-Y-W, R,-C(R,)--C(R,)-(C=O),,-N(R2)-Y-I:t,, Rj-C(Rj)=C(R,)(C=O),,,-G-Y-Z, R,C(R,)=C(Rj)-(C=O),,-G-Y-W, Rj-C(Rj)=C(Rt)-(C=O),,,-Y-Z wherein R, 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 I to about 30 carbon atoms, M is a substituted or unsubstituted morpholine group; each Y is independently selected from the group consisting of alkylene radical, phenyl group, imidazolium group, naphthyl group, biphenyl group, and combinations of any two or more thereof-, Ar is an arylene group; G is N(RI) or 0; 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, sulforiate, phosphonates, sulfinate, phosphinate, and combinations of any two or more thereof-, each m is independently 0 or 1; and W is an acid moiety selected from 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 33. A polymer according to claim 32 wherein said nitrogen-containing olefinic monomer is selected from the group consisdng of N-acryloyl morpholine, N-acryloyl-N'-methyl piperazine, N-acryloyl-N'-ethyl piperazine, N-acryioyl-N'-propyl piperazine, N-acryloyl-N'-(3-sulfopropyl)-N'-methyI piperazinium inner salt, N- acryloyl-N'-(3-sulfopropyl)-N'-ethyI piperazinium inner salt, N-acryloyl- N'-(4-sulfopropyl)-N'-methyI piperazinium inner salt, N-acryloyl-N'-(4- sulfopropyl)-N'-ethyI piperazinium, inner salt, N-acr-yioyl-N'-(2-amino-2- oxoethyl)-N'-methyI piperaziniurn chloride, N-acr-yloyi-N'-(3-amino-3-oxopropyl)-N'-methyI piperazinium chloride, N-acryloyl-N'-(4-amino-4-oxobutyl)-N'-methyl piperazinium chloride, N-acryloyl-N'-(2-amino-2-oxoethyl)-N'-ethyJ piperazinium phloride, N-acryloyl-N'-3-amino-3-oxopropyl)-N'-ethyl piperazinium chloride, N-acryloyl-N'-(4-ainino-4-oxobutyl)-N'-ethyl piperazinium chloride, N,N-dimethyt-N-(3-sulfopropyl)-N-(4-vinylbenzyl) ammonium inner salt, N,N-dirnethyl-N-(4-sulfobutyl)-N-(4-vinylbenzyl) ammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-N-(4-Yinylbenzyl) ammonium inner salt, N,N-diethyl-N-(4-suifobutyl)-N-(4-Yinylbenzyl) ammonium inner salt, N,N-dimethyl-N-(3-sulfopropyl)-N-(3-Yinylbcnzyl) ammonium inner salt, N,N-dimetiiyl-N-(4-sulfobutyl)-N-(3-vinylbenzyl) ammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-N-(3-Yinylbenzyl) ammonium inner salt, N,N-diethyl-N-(4-sulfobulyl)-N-(3-vinylbenzyl) ammonium inner salt, N,N-dimethyl-N-(2-aniino-2-oxoethyl)-N-(4-vinylbenzyl) ammonium chloride, N,N-diethyl-N-(2-amino-2-oxoethyl)-N-(4-Yinylbenzyl) ammonium chloride, NN-dimethyl-N-(3-amino-3-oxopropyl)-N-(4-vinylbcnzyl) ammonium chloride, N,N-diethyl-N-(3-arnino-3-oxopropyl)-N-(4-Yinylbenzyl) ammonium chloride, N,N-dimethyi-N-(2-amino-2-oxoethyl)-N-(3-vinyIbenzyi) ammonium chloride, N,N-diethyl-N-(2-ainino-2-oxoethyl)-N-(3-vinylbenzyl) ammonium chloride, N,N-dimethyl-N-(3-amino-3-oxopropyl)-N-(3-vinylbenzyl) ammonium chloride, N,N-diethy]-N-(3-amino-3-oxopropyl)-N-(3-Yinylbenzyl) ammonium chloride, N-(2-ainino-2-oxoethyl)-N'-vinyl imidazolium chloride, N-(3-amino-3-oxoPropyl)-N -vinyl imidazolium chloride, N-(4-ainino-4-oxobutyl)-N'-vinyl imidazolium chloride, N,N-dimethyl-N-(3-suifopropyl)-3-(acryloyl arnino)- 1 -propaneammonium inner salt, N,N-diethy]-N-(3-sulfopropyl)-3-(acryloyI amino)- 1 -propaneammonium inner salt, N,N-dimethyl-N-(4-suifobutyl)-3-(acryloyJ amino)- 1 - propaneamrnonium inner salt. N,N-diethyl-N-(4-suifobutyl)-3-(acVloyl amino)- 1 -propaneammonium inner salt, N,N-<iimethyl-N-(3-sulfopropyl)-24acryloyI arnino)-l-ethancammonium inner salt, N,N-diethyl-N-(3-sulfopTopyl)-2-(acryloyI amino)- I -ethaneammonium inner salt, N,N-dimethyl-N-(4-sulfobutyl)-2-(acryloyI amino)- I -ethaneammoniurn inner salt, N,N-diethyl-N-(4-sulfobutyl)-2-(acryloyI amino)- I -ethaneammonium Inner salt, and combinations of any two or more thereof 34. A polymer according to claim 32 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)-N44-vinylbenzy]) 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-aniino-2-oxoethyl) piperazinium chloride, N-acryloyi-N'-methyl-N'-(3-arnino-3-oxopropyl) piperazinium chloride, N-acryioyl-N'-methyl-N'-(4-amino-4-oxobutyl) piperazinium chloride, N-acryloyi-N'-ethyl-N'-(2-amino-2-oxoethyl) piperazinium. chloride, N-acryloyi-N'-ethyl-N'-(3-amino-3-oxopropyl) piperazinium chloride, N-acryloyi-N'-ethyl-N'-(4-ainino-4-oxobutyl) piperaziniurn 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) arrunonium chloride, NN-diethyl-N-(3-amino-3-oxopropyl)-N44-vinylbenzyl) ammonium chloride, N-(2-ainino-2-oxoethyl)-N'-vinylimidazolium chloride, N-(3-aininc-3-oxopropyl)-N'-vinylimidazolium chloride,N-(4-araino-4-oxobutyl)-N'-vinylimidazolium chloride, and combinations of anY two or more thereof 35. A polymer according to claim 32 wherein said nitrogen-containing olefinic monomer is N-acryloyl-N-methyl piperazine.
    36. A polymer according to claim 32 wherein said nitrogen-containing olefinic monomer is N-acryloyl-N'-(3-sulfopropyl)-N'-methyI piperaziniurn inner salt 37. A polymer according to claim 32 wherein said nitrogen-containing olefinic monomer is N-acryloyl N'-(2-amino-2-oxoethyl)-N!-methyI piperazinium chloride.
    38. A polymer according to claim 32 wherein said nitrogen-containing olefinic monomer is N,N-dimethyl-N-(3-sulfopropyl)-N-(4-vinylbenzyl) ammonium inner salt.
    39. A polymer according to claim 32 wherein said nitrogen-containing olefinic monomer is N,N-dimethyl-N-(2-amino-2-oxoethyl)-N-(4-vinylbenzyl) anunonium chloride.
    40. A polymer according to claim 32 wherein said nitrogen-containing olefinic monomer is N-(2-amino-2-oxoethyl)-N'-vinyI imidazolium. chloride.
    41. A polymer according to claim 32 wherein said nitrogen-containing olefinic monomer is NN-dimethyl-N-(3-sulfopropyl)-3-(acryloyI amino)- I propanearnmonium inner salt.
    42. A polymer according to claim 32 wherein said nitrogen-containing olefinic monomer is N-acryloylmorpholine.
    43. A polymer according to claim 32 wherein said olefinic cornonomer is selected from the group consisting of acrylamide, styrene sulfonic acid. salt of styrene sulfonic acid, N-methylacrylainide, N,Ndimethylacrylamide, acrylic acid, salt of acrylic acid, Nvinylpyrrolidone, methyl acrylate, methaerylate. 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 44. A polymer according to claim 43 wherein said olefinic comonomer is acrylamide.
    45. A watcr-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-acryloyi-N'-..(3-sulfopropyl)-N'-methyI piperaziniurn inner salt, N-acryloyi-N'-(3-sulfopropyl)-N'-ethyI piperaziniurn inner salt, N- acryloyl-N'-(4-sulfopropyl)-N'-methyI piperaziniurn inner salt, 10 N- acryloyl-N'-(4-sulfopropyl)-N'-ethyI piperazinium inner salt, N-acryloyl- N'-(2-amino-2-oxocthyl)-N"-methyI piperaziniurn chloride, N-acryloyl-N'- (3-arnino-3-oxopropyl)-N'-methyI piperazinium. chloride, N-acryloyi-N'-(4- amino-4-oxobutyl)-N'-methyI piperazinium chloride, N-acryloyi-N'-(2-amino- 2-oxoethyl)-N'-ethyI piperazinium chloride, 15 N-acryloyl-N'-(3-amino-3- oxopropyl)-N'-ethyI piperazinium chloride, N-acryloyl-N'-(4-amino-4- oxobutyl)-N'-ethyI piperaziniurn 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, 20 NI,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) anunonium 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-vinylbenzyi) arnmoniurn chloride, N,N-diethyl-N-(2-aii3ino-2-oxoethylN-(4-vinylbenzyl) ammonium chloride, N,N-dimeth,vl-N-(3-amino-3-oxopropyl)-N-(4-vinylbenzyl) ammonium chloride, NN-diethyl-N-(3-amino-3-oxopropyl)-N-(4-vinylbenzyl) ammonium chloride, N,N-dimethyl-N-(2-amino-2-oxoethyl)-N-(3-%inylbenzyl) 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'-vinyI imidazolium chloride, N-(4-amino-4-oxobutyl)-N'-vinyl imidazoliurn chloride, N,N-dimethyl-N-(3-sulfopropyl)-3-(acryloyI amino)- I -propaneammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-3-(acryloyI amino)- I -propanearnmoniurn inner salt.
    N,N-dimethyl-N-(4-sulfobutyl)-3-(acrvloyI amino)- I -propaneammonium inner salt., N,N-diethyl-N-(4-sulfobutyl)-3-(acryloyI amino)- I propaneammonium inner salt, N,N-dimethyl-N-(3-sulfopropyl)-2-(acryloyI amino)- I -ethaneammonium 1 nner salt, N,.N-diethyl-N-(3-sulfopropyl)-2(acryloyI amino)- I -ethaneammonium inner salt, N,N-dimethyl-N-(4sulfobutyl)-2-(acryloyI amino)- I -ahanearnmoniurn inner salt, N,N-di ethyl -N-(4-sulfobutyl)-2-(acryloyl amino)-I -ethaneammoriium inner salt, and combinations of any two or more thereof; and said olefinic comonorner is selected from the group consisting of acrylamide, styrene sulfonic acid, salt of styrene sulfonic acid, N- methylacrylamide, N,N-dimethylacrylarnide, acrylic acid, salt of acrylic acid, Nvinylpyrrolidone, mcthyl scrylate, methacrylate, vinylic sulfonic acid, salt of vinylic sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, salt 2-acrylamido-2-methylpropanesulfbnic acid, and combinations of any two or more thereof 46 A polymer according to claim 45 wherein said nitrogen-containing olefmic monomer is N-acryloyi-N'-methyl piperazine.
    47. A polymer according to claim 45 wherein said nitrogen-containing olefirUc monomer is N-acryloyl-N-(3-sulfopropyl)-N-methyI piperaziniurn inner salt.
    48. A polymer according to claim 45 wherein said nitrogen-containing olefinic monomer is N-acryloyl-N'-(2-amino-2-oxoethyl)-N-methyI piperazinium chloride.
    49. A polymer according to claim 45 wherein said nitrogen-containing olefinic monomer is N,N-dimethyl-N-(3-sulfopropyl)-N-(4-vinylbenzy]) ammonium inner salt.
    50. A polymer according to claim 45 wherein said nitrogen-containing olefinic monomer is N,N-dimethyl-N-(2-an-iino-2-oxoethyl)-N-(4vinylbenzyl) arnmonium chloride.
    51. A polymer according to claim 45 wherein said nitrogen-containing olefinic monomer is N-(2-amino-2-oxoethyl)-N'-vinyl imidazolium chloride.
    52. A polymer according to claim 45 wherein said nitrogen-containing olefinic monomer is N,N-dimethyl-N-(3-sulfopropyl)-3-(acryloy'amino)- I propaneamnionium inner salt.
    53. A polymer according to claim 45 wherein said nitrogen-containing olefinic monomer is N-acrylovimorpholine.
    54. A polymer according to claim 45 wherein said olefinic comonomer is acrylamide.
    55. 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 comprising repeat units derived from a nitrogen-containing olefinic monomer having the formula selected from the group consisting of Rj- C(Rj)=C(R,)_(C=O),,,_m, RI-C(R,)=C(Ri)-(C=O),,,-'N(RI), R,-C(Rj)--C(Rj)-(C=O).,-N N(R2)-Y-)C, \__j RIC(Ri)--C(Ri)-(C=O),,,-(W.-(Ar).-N(R2)(R2)-Y-SO3-, RI-C(Ri)--C(R,)-(C--O).-(NH),,,-(Ar).i-Y-N-(R2)(R2)-Y-(C=O),,-N(R2)(R2)X', r--\ RIC(Rl)=C(R,)-(C=O).,-N N(R2)-Y-(C=O).-N(R2)(R2)X-, RIC(R,)=C(R,)-(C=O).-N N -Y-(C--O).-N(R2)(R2)X-, and combinations of any two or more thereof wherein each R, and R2are the sarne 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 I to about 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, phosphonates, suffinate, phosphinate, and combinations of any two or more thereof; each Y is independently selected from the group consisting of alkylene radical, phenyl group, imidazolium group, naphthyl group, biphenyl group, and combinations of any two or more thereof, Ar is an arylene group; and each m is independently 0 or 1.
    56. A process according to claim 55 wherein said polymer further comprises repeat units derived from at least one olefinic corrionomer having the formula selected from the group consisting of R,-C(R,)=C(R,)-W, Rj-C(Rj)--C(Rj)-(C----O).-Z, Rj-C(R,)=C(Rj)-Y-W, R,-C(R,)=C(Ri)-(C=O).-N(Rz)-Y-R-2, Rj-C(Rj)--C(Rj)-(C=)).-G-Y-Z, RjC(Rj)=C(Rj)-(C--O).-G-Y-W, RI-C(R,)=C(R,)-(C--O).-Y-Z, and combinations; of any two or more thereof wherein each R, and R2 are the same or different and are independently selected from the group 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(R.,)(Rz), N'(R2)(R2)(R2)X- in which X is an anion selected from the group consisting of halide. sulfate, phosphate, nitrate, sulfonate, phosphonates, sulfinate, phosphinate. and combinations of any two or more thereof, G is N(R2) or 0; 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 pho-sphinic acid, phosphonic acid. suffinic 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 57. A process according to claim 55 wherein said nitrogen-containing olefimc 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,Ndiethyl-N-(3-sulfobutyl)-N-(4-vinylbenzyl) ammonium inner salt, N,Ndimethyl-N-(3-sulfopropyl)-N-(3'-vinylbenzyl) anunonium inner salt, N,Ndimethyl-N-(3-suffobutyl)-N-(3-vinylbenzy]) ammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-N-(3-vinylbenzyl) ammonium inner salt, N,N-diethyl-N-(3-sulfobutyl)-N-(3-vinylberLzyl) ammonium inner salt, N-acryloyi-N'-methyl-N'-(2-amino-2-oxocthyl) piperazinium chloride, N-acryloyl-N'-methyl-N'-(3-amino-3-oxopropyl) piperaziniurn 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-aniino-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, NN-diethyl-N-(2-amino-2-oxocthyl)-N-(4-vinylbenzyl) ammonium chloride, N,N-dimethyl-N-(3-amino-3-oxopropyl)-N-(4-vinylbenzy]) ammonium chloride, N,N-diethyl-N-(3-amino-3-oxopropyl)-N-(4-vinylbenzy]) ammonium chloride, N-2-amino-2-oxoethyl)-N"-vinylimidazofium chloride, N-(3-ainino-3-oxopropyl)-N'-vinyfimidazolium chloride, N-(4-amino-4-oxobutyl)-N'-vinyhmidazolitun chloride, and combinations of any two or more thereof.
    58. A process according to claim 56 wherein said nitrogen-containing okfinic monomer has the formula selected from the group consisting of N,N-dimethyl-N-(3-sulfopropyl)-N-(4-vinylbenzy]) 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-salfobutyl)-N-(4-vinylbenzyl) ammonium inner salt, N,N-dimethyl-N-(3-sulfopropyl)-N-(3-vinylbenzyl) arnmonium inner salt, N,N-dimethyl-N-(3-sulfobutyl)-N-(3-vinylben,zyl) ammonium inner salt, N,N-diethyl-N-(3-sulfopropyl)-N-(3-vinylbcnzyl) ammonium inner salt, to N,N-diethyl-N-(3-sulfobutyl)-N-(3-vinylbenzyl) ammonium inner salt, N-acryloyi-N'-methyl-N'-(2-arnino-2-oxoethyl) piperazinium. chloride, N-acryloyi-N'-methyl-N'-(3-ainino-3-oxopropyl) piperazinium. chloride, N-acryloyl-N'-methyl-N'-(4-amino-4-oxobutyl) piperazinium chloride, N-acryloyl-N'-ethyl-N'-(2-amirio-2-oxoe!hyl) 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-oxopTopyl)-N-(4-vinylbenzyl) ammonium chloride, N-2-aniino-2-oxoethyl)-N'-vinylimidazolitun 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 56 wherein said olefinic comonomer is acrylamide.
    60. A polymer according to claim 56 wherein said nitrogen-containing olefinic monomer is N-acryloyl-N'-methyl piperazine.
    61. A polymer according to claim 56 wherein said nitrogen-containing olefinic monomcr is N-acryloyl-N'-(3-sulfopropyl)-N'- mcthyI piperazinium inner salt.
    62. A polymer according to claim 56 wherein said nitrogen-containing olefinic monomer is N-acryloyl-N'-(2-amino-2-oxoethyl)-N'-methyI piperazinium. chloride.
    63. A polymer according to claim 56 wherein said nitrogen-containing olefinic monomer is N,N-dimethyl-N-(3-sulfopropyl)-N-(4-vinylbcnzyl) ammorlium inncr salt.
    64. A polymer according to claim 56 wherein said nitro gen-containing olefinic monomer-is N,N-dimethyl-N-(2-amino-2-oxoethyl)-N-(4-vinylbenzyl) ammonium cl-Aoride.
    65. A polymer according to claim 56 wherein said nitrogen-containing olefinic monomer is N-(2-amino-2-oxoe;hyl)-N'-viny[ imidazoliurn chloride.
    66. A polymer according to claim 56 wherein said nitrogen-containing olefinic monomer is NN-41imethyl-N-(3-sulfopropyl)-3-(acryloyI amino)- I propaneammoaium inner salt 67. A polymer according to claim 56 wherein said nitrogen-containing olefinic monomer is N-acryloylmorpholine.
    68. A composition comprising a water-soluble polymer, a crosslinking agent, and a liquid wherein said polymer is recited in any of claims 1567.
    69. A composition according to claim 68 wherein said crossfinking agent is a multivaient 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.
    70. A composition according to claim 68 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 71. A composition according to claim 68 wherein said crosslinking agent is selected from the group consisting of zirconium citrate, zirconium complex of hydroxyethyl glycine, ammonimn zirconium fluoride, zirconium 2- ethylhexanoate, zirconium acetate, zirconium neodecanoate, zirconium acetylacetonate, tetrakis(triethanolaminc)zirconate, zirconium carbonate, ammonium zirconium carbonate, zirconyl ammonium carbonate, zirconium lactate, titanium acetylacetonate, titanium ethylacetoacetate, titanium citrate, titanium triethanolamine, ammonium tiianium. lactate, aluminum citrate, cjiromium citrate, chromium acetate, chromium propionate, chromium malonate, and combinations of any two or more thereof.
    72. A composition according to claim 69 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, WArO (C=O). W. 110Ar (C--0) OT, H0ArOH, TOArOH, W0ArOW, or combinations of any two or more thereof wherein Ar is non-substituted or substituted arylene group; each R can be the same or different and is each independently selected from the group consisting of hydrogen, carboxylic group, a C,-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 73. A composition according to claim 68 wherein said crosslinking agent comprises two components in which the first component is selected from the group consisting of phenol, hydroquinone, resorcinol, catechol,p- aminosalicylic acid, furfuryl alcohol, phenyl acetate, phenyl propionate, phenyl butyrate, salicylic acid, phenyl salicylate, aspirin, p- hydroxybenzoic acid, methyl p-hydroxybenzoate, methyl p-arninobenzoic acid, o-hydroxybenzoate, ethyl p-hydroxybenzoate, o-hydroxybenzoic acid, hexyl p-hydroxybcnzoate, and combinations of any two or more thereof; and the second component is selected from the group consisting of formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, decanal, glutaraldehyde, terephthaldehyde, hexamethylenetetramirie, and combinations of any two or more thereof.
    74. A composition according to claim 68 wherein said liquid is a produced brine.
    76. A process comprising introducing a gelling composition into a subterranean formation wherein said composition is recited in any of claims 68-75.
    77. A composition comprising a clay, a polymer, and a liquid wherein said polymer is recited in any of claims 15-67.
    78. A composition according to claim 77 wherein said olefinic comonomer is selected ftorn the group consisting of acrylamide, styrene sulfonic acid, salt of styrene sulfonic acid, N-methylacrylamide, N,Ndirnethylacrylamide, acrylic acid, salt of acrylic acid, N-vinylpyrrolidone, methyl acrylate, methacrylate, vinyl sulfonic acid, salt of vinyl sufflonic acid, 2-acrylamido-2- methylpropanesulforc acid, salt of2-acrylamido-2-methylpropanesuifonic acid, and combinations of any two or more thereof 79. A composition according to claim 77 wherein said clay is bentonite.
    80. A process comprising introducing a composition into a subterranean formation wherein said composition is recited in claims 77- 79.
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Expiry date: 20161112