Exxon Research and Engineering Company

Ciba-geigy Ag

Ciba-geigy Corporation

Other

Paul L Valint

Jan Bock

Alexis A Oswald

Donald F Jacques

Ralph Martin Kowalik

Henry W Yang

Salvatore James Pace

Thomas J Pacansky

This invention provides a process for preparing novel hydrophobically associating polymers containing cationic functionality which are useful for clean-up of waste waters containing organic contaminants. These water soluble polymers contain both water soluble and water insoluble monomers. The water soluble monomers are acrylamide (AM) and a salt of an unsaturated amine base (C), and the water insoluble monomer is a higher alkyl(meth)acrylamide or alkyl(meth)acrylate (R). These polymers are referred to as CRAM. The process relies on the dissolution of the water insoluble monomer(s) into an aqueous solution of water soluble monomers by means of a water miscible mutual cosolvent. The type and concentration of miscible solvents are chosen to produce a clear, uniform, homogeneous aqueous solution of the hydrophobic monomers in the presence of both nonionic and cationic water soluble monomers and, in addition, the reaction medium remains a clear, uniform, homogeneous mixture with no phase separation as the reaction proceeds to completion. Redox or free radical initiators are used to copolymerize both the water soluble and water insoluble monomers, forming terpolymers of ethylenically unsaturated amine base salts, alkyl(meth)acrylamides of alkyl(meth)acrylates and acrylamide. These polymers provide exceptional clean-up of waste waters containing organic contaminants. Also they are very effective for resolving oil-in-water emulsion, as such as those found in oil production.

Solution process for preparation hydrophobically functionalized cationic

This invention describes novel hydrophobically associating ter or tetra polymers which can contain sulfonate functionality which are useful as aqueous fluid rheology or flow modifiers. These high molecular weight water soluble polymers contain both water soluble and water insoluble monomers. The water soluble monomers are N, N dimethylacrylamide acrylamide (DMA) and optionally a salt of an ethylenically unsaturated sulfonic acid (s) or N-vinylpyrrolidinone or a metal acrylate and the water insoluble monomer is a higher alkyl acrylamide (R). The process for their preparation relies on solubilizing the water insoluble monomer into an aqueous micellar solution containing one or more surfactants and the water soluble monomers. The surfactants are specifically selected to enable homogeneous dispersion of the hydrophobic monomer(s) in the presence of anionic sulfonate containing monomers. Redox or free radical initiators are used to copolymerize both the water soluble and water insoluble monomers, forming terpolymers of dimethylacrylamide, alkylacrylamides and acrylamide, and optionally an anionic sulfonate or carboxylate monomer. Aqueous solutions of these hydrophobically associating polymers exhibit enhanced viscosification, reduced salt sensitivity and other desirable rheological properties found useful in a variety of applications.

Hydrophobically associating polymers containing dimethyl acrylamide

This invention describes novel hydrophobically associating terpolymers containing sulfonate functionality which are useful as aqueous fluid rheology or flow modifiers. These high molecular weight water soluble polymers contain both water soluble and water insoluble monomers. The water soluble monomers are acrylamide (AM) and a salt of an ethylenically unsaturated sulfonic acid (S) and the water insoluble monomer is a higher alkyl acrylamide (R). These polymers are referred referred to as SRAM. The process for their preparation relies on solubilizing the water insoluble monomer into an aqueous micellar solution containing one or more surfactants and the water soluble monomers. The surfactants are specifically selected to enable homogeneous dispersion of the hydrophobic monomer(s) in the presence of anionic sulfonate containing monomers. Redox or free radical initiators are used to copolymerize both the water soluble and water insoluble monomers, forming terpolymers of ethylenically unsaturated sulfonic acids, alkylacrylamides and acrylamide. Aqueous solutions of these hydrophobically associating polymers exhibit enhanced viscosification, reduced salt sensitivity and other desirable rheological properties found useful in a variety of applications.

Solutions of hydrophobically associating terpolymers containing

This invention describes novel hydrophobically associating terpolymers containing sulfonate functionality which are useful as aqueous fluid rheology or flow modifiers. These high molecular weight water soluble polymers contain both water soluble and water insoluble monomers. The water soluble monomers are acrylamide (AM) and a salt of an ethylenically unsaturated sulfonic acid (S) and the water insoluble monomer is a higher alkyl acrylamide (R). These polymers are referred to as SRAM. The process for their preparation relies on solubilizing the water insoluble monomer into an aqueous micellar solution containing one or more surfactants and the water soluble monomers. The surfactants are specifically selected to enable homogenous dispersion of the hydrophobic monomer(s) in the presence of anionic sulfonate containing monomers. Redox or free radical initiators are used to copolymerize both the water soluble and water insoluble monomers, forming terpolymers of ethylenically unsaturated sulfonic acids, alkylacrylamides and acrylamide. Aqueous solutions of these hydrophically associating polymers exhibit enhanced viscosification, reduced salt sensitivity and other desirable rheological properties found useful in a variety of applications.

Hydrophobically associating terpolymers containing sulfonate

This invention describes novel hydrophobically associating ter or tetra polymers which can contain sulfonate functionality which are useful as aqueous fluid rheology or flow modifiers. These high molecular weight water soluble polymers contain both water soluble and water insoluble monomers. The water soluble monomers are N, N dimethylacrylamide acrylamide (DMA) and optionally a salt of an ethylenically unsaturated sulfonic acid (s) or N-vinylpyrrolidinone or a metal acrylate and the water insoluble monomer is a higher alkyl acrylamide (R). The process for their preparation relies on solubilizing the water insoluble monomer into an aqueous micellar solution containing one or more surfactants and the water soluble monomers. The surfactants are specifically selected to enable homogeneous dispersion of the hydrophobic monomer(s) in the presence of anionic sulfonate containing monomers. Redox or free radical initiators are used to compolymerize both the water soluble and water insoluble monomers, forming terpolymers of dimethylacrylamide, alkylacrylamides and acrylamide, and optionally an anionic sulfonate or carboxylate monomer. Aqueous solutions of these hydrophobically associating polymers exhibit enhanced viscosification, reduced salt sensitivity and other desirable rheological properties found useful in a variety of applications.

A homogeneous micellar free radical polymerization process for the formation of a terpolymer having the structure of: ##STR1## wherein S is selected from the group consisting of SO.sub.3 M, phenyl SO.sub.3 M, CONHC(CH.sub.3).sub.2 CH.sub.2 SO.sub.3 M or COOM; M is selected from the group consisting of Groups IA, 1B, IIA and IIB of the Periodic Table of Elements, R.sub.1 is a C.sub.1 to C.sub.10 alkyl, cycloalkyl or aralkyl group, R.sub.2 is hydrogen or a C.sub.4 to C.sub.18 alkyl, cycloalkyl or aralkyl group, x is about 10 to about 90 mole %, y is about 0.1 to about 60 mole %, and z is about 0.2 to about 10 mole % which comprises the steps of forming a mixture of an anionic surfactant, a nonionic surfactant, ##STR2## under a nitrogen atmosphere; adding deoxygenated water to said mixture to form a homogeneous reaction solution; adding free radical initiator to said homogeneous reaction solution to initiate polymerization of said monomers; terpolymerizing said monomers at a sufficient temperature and for a sufficient period of time to form said terpolymer and without the formation of substantial amounts of particulates or phase separation occurring.

Mixed micellar process for preparing hydrophobically associating polymers

Novel hydrophobically associating terpolymer compositions containing cationic functionality are described. These water soluble or water dispersible polymers contain both water soluble and water insoluble monomers. The water soluble monomers are ethylenically unsaturated nonionic monomers, such as acrylamide (AM), and cationic monomers, such as a salt of an amine base (C), such as 3-methacrylamidopropyltrimethylammonium chloride (MAPTAC), 2-methacrylatoethyltrimethylammonium chloride (METAC) and diallyldimethylammonium chloride (DMDAAC). The hydrophobic or water insoluble monomer is a higher alkyl(meth)acrylamide or alkyl (meth)acrylate (R). These polymers are referred to as CRAM. While the novel compositions of this invention impart unusual properties to water based fluids, they are extremely efficient for clean-up of waste waters containing organic contaminants and for breaking oil-in-water emulsions.

Hydrophobically functionalized cationic polymers

This invention provides a process for preparing novel hydrophobically associating terpolymers containing cationic functionality which are useful for clean-up of waste waters containing organic contaminants. These water soluble polymers contain both water soluble and water insoluble monomers. The water soluble monomers are acrylamide (AM) and a salt of an unsaturated amine base (C) and the water insoluble monomer is a higher alkyl(meth)acrylamide or alkyl(meth)acrylate (R). These polymers are referred to as CRAM. The process for their preparation relies on solubilizing the water insoluble monomer into an aqueous micellar solution containing one or more surfactants and the water soluble monomers. The surfactants are specifically selected to enable homogeneous dispersion of the hydrophobic monomer(s) in the presence of cationic monomers, such as 3-methacrylamidopropyltrimethylammonium chloride (MAPTAC), 2-methylacrylatoethyltrimethylammonium chloride (METAC), or diallyl dimethylammonium chloride (DMDAAC). Redox or free radical initiators are used to copolymerize both the water soluble and water insoluble monomers forming terpolymers of ethylenically unsaturated amine base salts, alkyl(meth)acrylamides or alkyl(meth)acrylates and acrylamide. These polymers provide exceptional clean-up of waste waters containing organic contaminants. Also, they are very effective for resolving oil-in-water emulsions, such as those found in oil production.

Micellar process for preparing hydrophobically functionalized cationic

A method of breaking an oil-in-water emulsion which comprises the steps of treating said oil-in-water emulsion with at least a de-emulsifying amount of a water dispersible terpolymer formed by polymerization from an acrylamide monomer, a water soluble cationic monomer and a water insoluble, hydrophobic monomer, and separating the formed water phase from the formed phase of terpolymer and the oil.

Oil-in-water emulsion breaking with hydrophobically functionalized

A process is described for producing unique and novel sulfonate-containing terpolymers of water soluble monomers with water insoluble monomers which are efficient viscosifiers of aqueous and brine media. The process relies on the complete solubilization of the water insoluble monomer by means of a dilute solution of a suitable water soluble surfactant. The type and concentration of surfactant are chosen to produce a clear, uniform, homogeneous aqueous dispersion of the hydrophobic monomers in the presence of both nonionic and anionic water soluble monomers, and, in addition, the reaction medium remains a clear, uniform, homogeneous mixture with no phase separation as the reaction proceeds to completion. Thus, the terpolymerization is effected without the formation of latexes or fine particulates of water insoluble polymer. The terpolymers, which may be isolated from the reaction mixture, provide efficient viscosification of water or brine solutions. The anionic sulfonate groups improve polymer solubility in water and brine, particularly in the presence of salts containing divalent cations, and impart some chain stiffness due to charge repulsion, particularly in water containing low electrolyte concentration. The hydrophobic N-alkylacrylamide groups associate in solution to create a structure with an apparent increase in molecular weight, resulting in enhanced thickening efficiency.

Process for preparing hydrophobically associating terpolymers containing

This invention relates to a method for enhanced recovery of petroleum from a subterranean oil-bearing formation. More particularly, this invention relates to secondary or tertiary recovery of oil employing a polymer thickened aqueous drive fluid. The polymeric viscosifier for the drive fluid is selected from a class of hydrophobically associating water soluble polymers containing one or more water soluble monomers and a water insoluble monomer or group. The water soluble groups are acrylamide and a salt of an ethylenically unsaturated sulfonic acid and the water insoluble group is a higher alkyl acrylamide. These polymers, when dissolved in an aqueous brine solution, have the ability to substantially increase the viscosity of the solution. The control of displacement fluid mobility results in more uniform sweep efficiency and improved oil recovery. In addition, aqueous solutions of these hydrophobically associating polymers exhibit enhanced viscosification, reduced salt sensitivity and other desirable rheological properties found useful in chemically enhanced oil recovery processes.

Enhanced oil recovery with hydrophobically associating polymers

The present invention relates to drag reduction agents for water which are diblock polymers of t-butylstyrene/metal styrene sulfonate and triblock polymers of t-butylstyrene/metal styrene sulfonate/t-butylstyrene.

Drag reduction agent

The present invention relates to oil solubilization agents for solubilizing oil into an aqueous solution in which the oil solubilization agents are diblock polymers of t-butylstyrene/metal styrene sulfonate and triblock polymers of t-butylstyrene/metal styrene sulfonate/t-butylstyrene.

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Asbury, NJ, United States of America

Paul L Valint