CA1171188A - Water-dispersible hydrophobic thickening agent - Google Patents

Water-dispersible hydrophobic thickening agent

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Publication number
CA1171188A
CA1171188A CA000394913A CA394913A CA1171188A CA 1171188 A CA1171188 A CA 1171188A CA 000394913 A CA000394913 A CA 000394913A CA 394913 A CA394913 A CA 394913A CA 1171188 A CA1171188 A CA 1171188A
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Canada
Prior art keywords
composition
water
soluble
alkyl
surfactant
Prior art date
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Expired
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CA000394913A
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French (fr)
Inventor
Syamalarao Evani
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Dow Chemical Co
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Dow Chemical Co
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    • C09K8/60Compositions for stimulating production by acting on the underground formation
    • C09K8/62Compositions for forming crevices or fractures
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10S507/00Earth boring, well treating, and oil field chemistry
    • Y10S507/926Packer fluid
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10S507/00Earth boring, well treating, and oil field chemistry
    • Y10S507/935Enhanced oil recovery
    • Y10S507/936Flooding the formation

Abstract

ABSTRACT

An aqueous liquid medium having increased low shear viscosity as provided by dispersing into the aqueous medium (1) a water-soluble polymer having pen-dant hydrophobic groups, e.g., an acrylamide/dodecyl acrylate copolymer, and (2) a water-dispersible surfac-tant, e.g., sodium oleate, or dodecyl polyethyleneoxy glycol monoether. The thickened aqueous medium is suitably employed in application requiring viscous liquids which retain their viscosity when subjected to shear, heat or high electrolyte (salt) concentrations.
Such applications include uses in enhanced oil recovery processes, as fluid mobility control agents, fracturing fluids and drilling muds, as well as hydraulic fluids and lubricants in many applications.

Description

WATER-~DISPERSIBL~ HYDROPHOBIC
T~II CKE~ING AGENT

This invention relates to thickening agents containing water-dispersible polymers which agents are used to ~ncrease the viscosity of agueous media.

~ s taught in Encyclopedia of PolYmer Science S and Technology, Interscience Publishers, Vol. I, 192 ~1964~, it is known that the viscosity of an agueous medium is increased by the addition of a water soluble polymer. Such water-soluble pol~mers include poly-~crylamide, acrylamide/acrylic acid copolymer, sodium polyacrylate, carbo~ymethyI cellulose, hydroxyethyl cellulose, methyl cellulose, polysaccharide as well as naturally occurring gums such as guar gum and chemically modified gums such as hydroxypropyl suar gum. As a result of this thickening capability, ~here are many existing, as well as potential, industrial applications for aqueous media ~hickened with such water-soluble ~: pol~mers.

Unfortunately, however, ~he aforementioned conventional water-soluble pol~mers suffer from many serious deficiencies or limitations in actual use in such industrial applicatio~s. For example, for reasons ; 26,810-F

:~t7~:~8~

of efficiency and economical considerations, it is common to employ very high molecular weight versions of such polymers. However, during many industrial applica-tions, the conditions present during the practice of the application involve expo~ing an aqueous medium containing the high molecular weight water-soluble polymer to high shear. Such shear often causes mechani-cal degradation of the polymer and thus reduces the viscosity of the aqueous medium. While lower molecular weight polymers are less sensitive to shear degradation, they must be used in much higher concentrations in order to achieve the desired level of viscosity.

Secondly, while ionic water-soluble polymers such as neutralized acrylamide/acrylic acid copolymer, sodium polyacrylate, polystyrene sulfonate and the like are more efficient thickeners in deionized water than their nonionic counterparts, their thickening ability is greatly reduced by the presence of electrolytes such as sodium chloride, calcium chloride and magnesium sulfate in the aqueous medium. Such electrolytes are present in the aqueous media employed in most industrial applications, particularly those requiring the use of ground waters in subterranean formations as in enhanced oil reco~ery.

Finally, in many applications, the aqueous medium thickened with a water-soluble polymer is exposed to temperatures in the range of from 3Q to 100C which normally causes reduction of viscosity. Such high tempexatures are particularly common in enhanced oil recovery applications wherein the aqueous medium i5 pumped underground to depths of 5000 to 20,000 feet (1525 to 6100 met.), a~ is common for mobili~y control fluids and packing fluids.

26,810-F -2-~L~'7~

In attempts to overcome some of the aforemen-tioned deficiencies of the conventional water-soluble polymers, it has been a common practice to cross-link the polymer in order to improve resistances to thermal as well as shear degradation. see, for example, U.S.
Patent No. 3,247,171. Such attempts have generally not been successful. More recently, as taught in U.S.
Patent No. 3,984,333, an aqueous medium has been thickened by dissolving a water-soluble block copolymer having water-soluble blocks and water-insoluble blocks in the agueous medium. While such water-soluble block copol~mers apparently exhibit reasonably good resistance to shear degradation, such polymers are difficult and often impractical to prepare. More importa~tly, such polymers do not ex~ibit significant tolerance o electrolytes normally present in the aqueous media ~o be thickened.

While the cellulosic derivatives such as hydroxyethyl cellulose and biopolymers exhibit accept-able tolerance to the presence of electrolytes, cellu~
losic derivatives are generally ineffective at the low concen~rations that are economical and exhibit poor thermal ~tability. The biopolymers such as xantham gums exhibit acceptable thermal stability, resistance to shear degradation and electrolytic tolerance.
Unfortunately, such biopol~mers are generally very expensive and are susceptible to biodegradation.

In view of the aforementioned deficiencies of conventional water-soluble polymers as thickening agents, it is hi~hly desirable to provide a relatively inexpensive thickening agent which exhibits the~mal stability, electrolytic tolerance and good resistance to shear and biological degradation.

26,810-F -3-~:~ 7~

The csmposition of the invention also contains sufficient amounts of ing.redients common to a fractur.ing fluid used in enhanced oil recovery; drilling mud used in the recovery of oil; paint formulation; lubricant;
friction -reducing agent; fluid mobility control agent in enhanced oil recovery, or hydraulic fluid.

The present invention is such a thickening composition for aqueous liquids comprising a water-soluble polymer having pendant hydrophobic groups and a water--dispersible nonionic surfactant having hydrophobic groups that are capable of associating with the hydro~
phobic groups o~ the polymer wherein the proportion of water-soluble polymer and surfactant is such that at ambient conditions, water containing 0.5 weight percent of the thickening composition has a viscosity at least twice the viscosity of water.

The present invention more specifically resides in a water-soluble composition for thickening aqueous liquids comprising (A) a water-soluble thickening agent which agent comprises (1) a water~soluble polymer having pendant hydrophobic groups, said polymer being a copolymer of a water-soluble ethylenically unsaturated monomer-and water-insoluble ethyleni-cally unsatuxated monomer having a hydrophobic group having at least 8 carbon atoms, wherein (a~ the water-soluble monomer is an ethylenically unsaturated amide or an N-substituted derivative thereof, an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated quaternary ammonium compound, a sulfoalkyl ester of an unsaturated 26,810-F -4--..
- ' ' ' ' .

~.3L7~
, ... .

carboxylic acid, an aminoalkyl ester of an unsaturated carboxylic acid, a diallylamine, a diallylammonium compound or a vinylaryl sulfonate, and (b) the water-insoluble monomer is a higher alkyl ester of an ~ ethylenically unsaturated carboxylic acid, an alkylaryl ester of an ethylenically unsaturated carboxylic acid, an N-alkyl ethylenically unsaturated amide, a vinyl alkyl ether or an ar-alkyl styene; and
(2) a water-dispersible nonionic surfactant having hydrophobic groups that are capable of associating with the hydrophobic groups of the copolym~r such that at ambient conditions, water containing 0.5 weight percent of ~he t.hickening a~en~ has a viscosity at least twice ~he viscosity of water, said thickening agent having a weight ratio of the copolymar to the surfactant in the range from about 20:1 to about 0.5:1; and (B) a water-soluble inorganic salt in an amount such that at a temperature in ~he range up to about 80C, an aqueous medium containing a viscosity increasing amount of the thickening agent exhibits a furthex increase in viscosity when the water-soLuble salt is added to the medium.

Still more specifically, the invention resides in a water-solubLe composition for thickening aqueous liquids which composition comprises (A) water-soluble thickening agent comprising (1) :a water-soluble polymer having pendant hydrophobic groups, said polymer being a copolymer of a water-soluble ethylenically unsaturated monomer and water-insoluble ethylenically unsatura-ted monomer having a hydrophobic group, wherein (a~ the water-soluble monomer is acrylamide, methacrylamide and fumaramide;
;~. ~ ~.
~ 26,810-F -5-~ -,~

2-acrylamide-2-methylpropane sulfonic acid, M-(dimethylaminomethyl)acrylamide, N-(tri-methyammoniummethyl)acxylamide chloride, ~-~trimethylammoniumpropyl)methacrylamide chloride, acrylic ac.id, methacrylic acid, itaconic acid and fumaric acld, vinylbenzyl trimethyl ammonium chloride, 2-sulfoethyl metha~rylatP, 2-aminoethyl methacrylate, vinyl pyridine, vinyl morpholine, diallyl dimethyl ammonium chloride, vinyl pyrrolidQne or a salt of vinylbenzyl sulfonate and (b) the water-insoluble monomex is 2-ethylhexyl methacrylate, dodecyl acrylate, dodecyl methacrylate, tridecyl acrylate, trid~cyl metha?~rylate, tetradecyl acrylate, tetradecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, ethyl half ester of malel~ anhydrid2, diethyl maleate, and other alkyl esters derived rom the reactions of alkanols ha~ing from 8 to 20 carbon atoms with ethylenically u~sa~urated car~oxy~ic acids selected from the group consisting of acrylic acid, methacrylic acid, maleic anhydride, fl~aric acid, itaconic acid and aconitic acid, nonyl-a-phenyl ac.rylate, nonyl-~-phenyl methacxylate, dodecyl a-phenyl acrylate, dodecyl-~-phenyl me~hacrylate, N-oc~adecyl acrylamide, N-octadecyl meth-acrylamide, N,N-dioc~yl acrylamide; octene-l, decene~l, dodecene-l, he~adecene-1, vinyl laurat~, vinyl s~earate, dodecyi vinyl ether, hexadecyl vinyl ether, N-vlnyl lauramide, N-vinyl stearamide or t-butyl styrene;
.

~ 26,810-F -5a-``b ~?~ ,1 ~?

8 ~

(2) a water-dispersible n~nionic surfacta~t having hydrophobic groups that are capable of associating with the hydrophobic groups of the copolymer such that at ambient conditions, water cont ining 0.5 weight percent of the thickening agent has a viscosi~y at least twice the viscosity of water, said thickening agent having a weight ratio of the copolyme~ to the surfactant in the range from about 20:1 to about 0.5:1; a~d (B~ a water-soluble inorganic salt of a metal in an amount such that at a tempexature in the range up to about 80C, a~ aqueous medium containing a viscosity increasing amount of the th-ickening agent -exhibits a further increase in viscosity when the water-soluble salt is added to the medium, said amount of salt being in the r~nye ~rom about 0.01 to about 20 weight percen~ based on ~he m~dium.

The invention also resides in a thickened aqueous composition which composition comprises (A) water having dispersed therein (1) a viscosity increasing amount of a watex-soluble copolyme~ of from about 40 to about 99.9 mole percent of acrylamide, from 0 to about S0 mole parcent of acrylic acid and from about 0.1 to about 10 mole percent of an alkyl methacryla~e or acrylate wherein alkyl has from 8 to 12 carbon atoms;
(2) and a surfactant comprising an alkyl polye~hyleneoxy glycol monoether wherein alkyl has from 8 to 20 carbon atoms and there are from l to 12 ethyleneoxy groups per molecule of th~ monoether, and
(3) from about 0.01 to about 20 weighk pexcent of a salt of an alkali metal or an alkaline earth meta~;
in said composition the weiyh~ ra~io of copolymer ~o monoether being in the range from about 20:1 to about 0.5:1.
-5b-~ .

- ,:

The invention further rèsides in ~ thickened aqueous composition comprising (A) an aqueous medium havi~g dissolved thereln;
(B) a viscosi~y increasing amount in ~he range from about 0.025 to about 5 weight percent of a thickening agent comprising (1) a copolymer of from about 98 to ~bout 99.995 mole percent o~ one or more water-soluble - ethylenically unsaturated monomers and from about 0.005 to about 2 mole percent of one or more water-insoluble e~hylenically unsatu~ated monomers having hydrophobic groups having at least 8 carbon atoms wherein the water-insoluble monomer is a higher alkyl ester of an a,~-ethylenically unsaturated carboxylic acid, an alkylaryl ester of an ethylenically unsa~urated carboxylic acid, an N-alkyl ethylenically unsaturated amide or an ar-alkyl styrene, and (2) a water-dispersible, nonionic surfacta~t having ~ydrophobic groups that are capable of associating with the hydrophobic groups of ~he copol~mer wher~in ~h~ weight ratio of copolymer to surfactant is lnbthe range from about 20:1.to about 0.5:1; and (C~ a~ amount of a water-soluble inoryanic salt in the range from abou~ 0.01 to about 20 weight perc~nt based on the medium which is suffici~nt to increase the viscosity of the aqueous medi~ containing the thickening agent.

- Surprisingly, aqueous media c~ntaining the thickening agent of this invention can be subjected to substantial mechanical shear without a significant loss of viscosity. Moreover, such thickening agents provide a substantial viscosity increase even when the aqueous 26,810-F -5c-~' >R ' ,, ~ ' : ' . . .

media contains significant concentrations of electrolyte as in the case of hard water or brine and even when exposed to temperatures up to 80C. Consequently, such thickening agents can be used for a variety of applications wherein high temperatures, substantial e~ectrolyte concentrations and conditions of high mechanical shear such as in high shear pumping of ~he aqueous medium i~
required. Unlike high molecular weight po.lymers currently available which thicken an aqueous media but which also give solutions which are stringy, the thicke~ing agents of the invention when dispersed in an aqueous medium, exhibit suitable plastic rheoLogy and short solution characteristics. 3y 'ishort ~olution ::harac:teristics"
is meant that a~ aqueous m~dium cor~taining the thiclcening ag~nt does not produce ~hreads or striIlgs o such aqueous medium when surfaces we~ted wit~ the medium are co~tac:ted aIld pulled apart. As a result of these and oth~r thic~er~ins~ characteristics of the present in~rention, ~se thicke~ing agents are useful in all applica~ions which r~guir~ aqu~ous media ha~ g in::rea ed viscosity such as drilli:;Lg mud formulations, fracturing fluids, liquid mobility con~xol ag~r~ts, aqueous solutions of inorga2lic salts, hydx aulic fluids, lu~ricarlts, friction reduci~g agents, sus~ending ageIlts, aqueous suspensions of i~soluble par~iculates such as pain~ formuLations aIld the like.

Accordingly, i~ another aspect, the present inventiQn is an aqueous medium containing an amount of the thicXe~ng agent which is effective to incre~se the viscosity of the aque~us medium. In a preferred embodi-ment in ~s aspect of the in~tion, the a~ueous medium containi2lg the thic}~e~n~ ag~nt is a m~bility control fluid usaful in enhanced oil re::overy opera-tio~s. In the practice of this embo~iment of the in~e~tion, the thicke~ed aqueous medlium is i~roduced throu~h a~ inj e :tiorl well into a porous subterranean fo~mation p~etrated by said well and driverl through the formation t}~ough the producing well.
5d--.

More particularly, the invention also resides in a mobility control agent which is soluble in an aqueous flooding medium comprising a hydrophilic/-hydrophobic polymer having hydrophobic moietles and a water-dispersible, nonionic surfactant havlng hydrophobic groups that.are capable of associating with the hydxophobic moleties of the polymer wherein the proportion of the polymer a~d the suxfactant is such that, at ambient co~ditions, water containing 0.5 weight percen~ of the agent has a viscosity at least twice the viscosity of water, said agent having been prepared by carrying out the polymerization to for~ the polymer in ~he presence of the nonionic surfactant.

In further aspects of this invention, ~he thickening agent is employed in a drilling mud formu-lation or a fracturing fluid wherein the thickening agent is present in an amount sufficient to increase the viscosity of the formulation or fluid as desired.

. .
I ~ -5e-.
`. . ~, The thickeniny agent of ~his invention con-tains (1) a water-soluble poly~er having pendant hydro-phobic groups and (2) a water-soluble dispersible surfactant. The hydrophobic groups of the polymer are solvated by the surfactant such ~hat the thic~ening agent forms a solution in water.

For the purposes of this invention, the water~soluble polymer is one which forms a thermo-dynamically stable mixture when combined with water.
These mixtures form spontaneously and include true solutions in which the individual polymer molecules are dispersed as well as micellular or colloidal solutions wherein the polymer molecules are a~gregated to some extent, but wherein such aggregates are no larger than colloidal size.

The molecular weight of ~he water-soluble polymer is low enough such that an aqueous medium containing 0.1 weight percent of the polymer can be subjected to a degree of shear on the order of 10,000 sec 1 without causing the polymer to degrade signifi-cantly. Moreover, the polymer has a molecular weight such ~hat, whe~ 0.5 weight part of the polymer is dissolve~ in 100 weight parts of water, the Brookfield viscosity of the water is increased to at least 2 centipoises (as measured using a Brookfield LVT visco-meter equipped with a UL adaptor and operated at 6 rpm and 2~C). While polymers having vexy high molecular weigh~, e.g., weight average molec~lar weight (~ ) greater than 5 million, can be suitably employed, such polymers tend to degrade when subjected to high shear, e.g., in excess of 10,000 sec 1. Accordingly such 26,810-F -6~

~7~ 8 polymers are less preferred for some applications.
Preferably, the water-soluble polymers used in this invention have weight average molecular weights (Mw) as determined by gel permeation chromatography in the S range from 200,000 to 5 million, most preferably from 800,000 to 2.5 million.

The pendant hydrophobic groups of the water-soluble polymer are organic groups having hydrophobici-ties comparable to one of the following: aliphatic hydrocar~on groups having at least four carbons such as C4 to C20 alkyls and cycloalkyls; polynuclear aromatic hydrocarbon groups such as naphthyls; alkylaryls wherein alkyl has one or more carbons; haloalkyls of four or more caLbons, preferably per~luoroalkyls; polyalkylene-oxy groups wherein alkylene i5 propylene or higheralkylene and there are at least l alkyleneoxy unit per hydrophobic moiety. The concentration of hydrophobic moieties in the water-soluble pol~mer is ~hat which is sufficient to increase the viscosity of an aqueous medium containing the water dispersible sur~actant.
Preferably, the concentration of hydrophobic groups in the polymer is such that, when one weight part o~ the polymer is dissolved in 100 weight parts of the aqueous medium containing one weight part of the surfactant, the Brookfield viscosity (as defined hereinbefore) o~
the aqueous medium is twice that of an aqueous medium containing 1 weight percent of the surfactant and 1 weight percent of a hydrophilic polymer that is identical in all resp~cts to the hydrophobic polymer except that the hydxophilic polymer contains no hydrophobic groups.
For example, if an aqueous solution containing 1 weight percent of a surfactant and 1 weight percent o polyacryl-amide (hydrophilic polymer) has a Brookfield viscosity 26,810-F -7~

, :

of 10 cps, the aqueous solution containing 1 weight percent of the same surfactant and 1 weight percent of a suitable hydrophobic polyacrylamide, e:g., an acryl-amide/dodecyl acrylate copolymer having a ~ equivalent to the polyacrylamide, will have a Brookfield ~iscosity of at least 20 cps.

Exemplary water-soluble polymers include the copolymers of water-soluble ethylenically unsaturated monomers with hydrophobic e~hylenically unsaturated monomers wherein the concentration of hydrophobic monomer is sufficient to provide the reguisite concen-tration of hydrophobic moieties. Preferably, the water-soluble polymer is a copolymer from 48 to 99.995 mole percent of one or more water-soluble monomers with from 0.005 to 2 mole percent of one or more hydrophobic monomers. For the water-solubla polymers, it is found that preferred amounts of hydrvphobic monomers will vary with the molecular weight of the polymer. For example, a water-soluble polymer having a weight average molecular weight near 200,000, preferably contains from 1 to 2 mole percent of hydrophobic monomer. Alterna-tively, the water-soluble polymer having a weight a~erage molecular weight of 2 mi.llion preferably contains from 0.05 to 0.25 mole percent of hydrophobic moncmer.

Suitable waterwsoluble monomers include those which axe sufficiently water-soluble to form at least a 10 weight percent solution when dissolved in water and readily underyo addition polymerization to form polymers which are water~sol~ble. Exemplary water-soluble monomers include ethylenically unsaturated amides such as acrylamide, methacrylamide and fumaramide; their 26,810-F -3-.

, ~17~

N-substituted derivatives such as 2-acrylamide-2-methylpropane sul~onic acid ~MPS~, N-(dimethylamino-methyl)acrylamide as well as N-(trimethylammoniummethyl)-acrylamide chloride and N-(trimethylammoniumpropyl)-methacrylamide chloride; ethylenically unsaturated car-boxylic acids such as acrylic acid, methacrylic acid, itaconic acid a~d fumaric acid. Ethylenically unsat-urated quaternary ammonium compounds such as vinylbenzyl trimethyl ammonium chloride, sulfoalkyl este~s of unsaturated carboxylic acids such as 2-sulfoethyl methacrylate; aminoalkyl esters of unsaturated carboxylic acids such as 2-aminoethyl methacrylate; vinyl amines such as vinyl pyridine and vinyl morpholine, diallyl amines and diallyl ammonlum compounds such as diallyl dimethyl ammonium chloride; vinyl heterocyclic amides such as vinyl pyrrolidone; vinylaryl sulfonates such as vinylbenzyl sulfonate as well as the salts of the foregoing monomers. Of the foregoing water-soluble monomers, acrylamide and combinations of acrylamide and acrylic acid are preferred. Acrylamide and combina-tions thereof with up to 75 mole percent of acrylic acid, based on total water-soluble monomer, are more preferred. Most pre~erred are polymers wherein the water-soluble monomer i~ a mixture of acrylamide with from 5 to 50 mole percent, especially from 15 to 30 mole percent of acryli~ acid.

Suitable hydrophobic monomers are those which are water-insoluble, i.e., less than 0.2 weight part of the hydrophobic monomer will dissolve in 100 weiyht parts water. Exemplary hydrophobic monomers include the higher alkyl esters of a,~-ethylenically u~saturated carboxylic acids such as dodecyl acryla~e, dodecyl ":

~ 26,810-F ~9-.

-methacrylate, tridecyl acrylate, tridecyl methacrylate, tetradecyl acrylate, tetradecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, ethyl half ester of maleic anhydride, diethyl maleate, and other alkyl esters derived from the reactions of alkanols having from 8 to 20 carbon atoms with ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, itaconic acid and aconitic acid; alkylaryl esters of ethylenically unsatu-rated carboxylic acids such as nonyl-a-phenyl acrylate, nonyl-a-phenyl methacrylate, dodecyl-~-phenyl acrylate and dodecyl-a-phenyl methacrylate; N-alkyl, ethylenically unsaturated amides such as N-octadecyl acrylamide, N-octadecyl methacrylamide, N,N-dioctyl acrylamide and similar derivatives thereof; a-olefins such as octene-l, de~ene-1, dodecene-1 and hexadecene-1; vinyl alkylates wherein alkyl has at least 8 carbons such as vinyl laurate and vinyl stearate; vinyl alkyl ethers such as dodecyl vinyl ether and hexadecyl vinyl ether; N-vinyl amides such as N-vinyl lauramide and N-vinyl stearamide;
and ar-alkylstyrenes such as t-butyl styrene. Of the foregoing hydrophobic monomers, the alkyl esters of acrylic acid and methacrylic acid wherein alkyl has from 8 to 20 carbon atoms, are preferred. The alkyl methacrylates wherein alkyl has from 10 to 20 carbon atoms are more preferred. Dodecyl methacrylate is the most preferxed.

_ The aforementioned water-soluble polymers containing hydrophobic moieties are ad~antageously prepared by copolymerizing ~he water-soluble monomers wi~h hydrophohic monomers by any of the co~ventional polymeri~ation technigues wherein the hydrophobic monomer or mixture of hydrophohic monomers is added 26,810-F -10~

~L7~ 8 with vigorous agi~ation ~o an aqueous solution of the water-soluble monomer or mixture of water-soluble monomers. In the instances wherein the wa~er-soluble monomer, as well as the hydrophobic monomer, are soluble in a neutral organic solvent, the water-soluble polymer can be prepared by any desired solution polymerization method wherein the neutral organic solvent is employed as ~he polymerization diluent. The most ef~ective water-soluble polymers are prepared by copolymerizing the water~soluble monomers with hydrophobic monomers in a molar ratio of water-soluble monomer:hydrophobic monomer in the range from 98:2 to 99.995:0.005, pref-erably from 99:1 to 99.9:0.1.

Polymerization of the water-soluble and hydrophobic monomers is advantageously effected in an aqueous medium containing an emulsifier for the hydro-phobic monomer and a polymerization initiator capable of generating free-radicals. The emulsifiex is required in most instances to suitably disperse the hydrophobic monomer and to subsequently obtain a copolymer having a uniform composition. Op~ionally a chain transfer agent may be included in the polymerization reaction mixture.
Accordingly, it is desirable to employ from 0.01 to 0.1 weight percent of an initiator based on the monom~rs and from 0.1 to 1 weight percent of an emulsifier based on the monomers.

Exemplaxy suitable polymerization initiators include the inorganic persulfate~ such as potassium persulfate, ammonium persulfate and sodium persulfatP, azo catalysts such as azobisisobutyronitrile and dimethyl azoi~obutyrate; organic peroxygen compounds such as benzyl pero~ide, t-butyl peroxide, diisopropyl benzene 26,810-F -11-hydroperoxide and t-butyl hydroperoxide. Of these initiators, the oil-soluble types such as the organic peroxides and azo compounds are preferred.

Suitable emulsifiers include anionic agents such as alkali metal salts of alkyl sulfates and alkyl and aryl sulfates, e.g., dodecyl alkyl sulfosuccinates and sodium dodecylbenzene sulfate; fatty acid soaps, e.g., sodi~m oleate, sodium stearate and potassium oleate; alkali metal salts of sulfo~ated fatty alcohols, lQ e.g., sodium dodecyl sulfate; sulfa~es of ethoxylated alcohols; alkyl phosphate esters, e.g., dodecyl hydrogen phosphate; fluoro emulsifiers, e.g., perfluoroalkyl sulfates; and the like. Also included are cationic emulsifiers such as alkylamine hydrochlorides, e.g., dodecylamine hydrochloride and tridecylamine hydro chloride; quaternary alkyl or aryl ammonium halides such as dodecyl trimethyl ammonium chloride; ethoxylated fatty amines and other e~ulsifiers as described in McCutcheon's Deterqents and Emulsifiers, North American Edition, 1980 Annual. In general, when the water-soluble polymer is anionic or nonionic, an anionic emulsifier such as an alkali metal alkyl sulfate is pre~erably employed as the emulsifier. When the water-- soluble polymer is cationic, a cationic emulsifier such as dodecylamine hydrochloride is employed. When the water-soluble polymer is nonionic, anionic or cationic, a nonionic emulsifier such as nonylphenoxy polyethylene glycol having 10 ethyleneoxy units per molecule is suitably employed.

The watex-soluble polymers a~e readily re covered from the agueous medium when such is desired by removal of water under vacuum or by azaotropic distilla-tion. Alternatively, such polymers may be separated by 26,810-F -12-the addition of methanol or anhydrous acetone to cause the water-soluble polymer to form a phase separate from the aqueous medium. As a further alternative, the aqueous medium containing the water-soluble polymer can be used as such.

It is also understood that water-soluble polymers of acrylamide, acrylic acid and hydrophobic monomer can be prepared by copolymerizing all three of these monomers or by copolymerizing acrylamide with the hydrophobic monomer and subsequently hydrolyzing a portion of the copolymerized acrylamide hy contacting the copolymer with a base such as sodium hydroxide and/
or sodium carbonate. Suitable copolymers may comprise from 40 to 99.9 mole percent of acrylamide, from 0 to 5 mole percent of acrylic acid, and f~om 0.1 to 10 mole percent of an alkyl methacrylate or acrylate wherein the alkyl has from 8 to 12 carbon atoms. Such a copolymer having a weight average molecular weight in the range of from 800,000 to 3 million and the invention also contemplates an aqueous composition comprising an aqueous medium comprising a thickening composition in which the copolymer is preferably present in an amount of from 0.01 to 1 weight percent and the monoether is present in an amount of from 0.0015 to 0.5 weight percent. Additionally, the aqueous composition may include an alkali metal salt or an alkaline earth metal salt in an amount of from 0.01 to 20 weight percent.

Surfactants suitably employed as a second component of the thickening agents of this invention are those micelle forming surface active agents which will disperse in an aqueous medium containing an effec-tive amount of the aforementioned water-soluble polymer 26,810-F -13- --$~

and which have sufficient hydrophobic moieties to combine with the water-soluble polymer to increase the viscosity of an aqueous medium containing said water-soluble polymer. Preferably, the surfactant is present in the thickening agen-t in an amount of from 0.0015 to 0.5 weight percent. Accordingly, such surfactants can be nonionic, anionic, cationic or amphoteric, with the nonionic surfactants being preferred due to their ability to remain hydrated in the presence of signi-ficant electrolyte concentration. The surfactant pre-ferably is a nonionic surfactant selected from an alkyl polyethyleneoxy glycol monoether or alkylaryl polyethyleneoxy glycol monoether wherein the alkyl has from 8 to 20 carbon atoms and from about 1 to 20 ethyleneoxy groups per polymer molecule. Preferred nonionic surfactants have hydrophilic-lipophilic balances (HLB) in the range from 2 to 15, most preferably from 5 to 13. Exemplary surfactants include nonionic surfactants such as alkyl polyethyleneoxy compounds represented by the formula:

R-(EO)n-H

26,810-F -13a-'.~

. ' . ~ ~, . ~

- - -~1 ~ 7~

wherein R is C8-C18, EO is ethyleneoxy and n is a number from 1 to 10. Exemplary nonionic surfactants are the reaction products of ethylene oxide or mixtures of ethylene oxide and higher alkylene o~ide with active hydrogen compounds such as phenols, alcohols, carboxylic a~ids and amines, e.g., alkylphenoxyethyleneoxy ethanols.

Also suitable are anionic substituted poly-ethyleneoxy compounds represented by the formula:

R-(EO) -X

wherein R and n are as defined hereinbefore, EO is ethyleneo~y and X is SO3H or CO2H or PO3H; salts o~
long chain carboxyla~es such as potassium oleate, sodium laurate, potassium stearate, potassium capro late, sodium palmatate and the like; alkali metal alkylbenzene sulfonates such as sodium nonylbenzene sulfonate and potassium dodecylbenzene sulfonate;
alkali metal alkyl sulfates such as sodium dodecyl sulfate and alkali metal dialkyl sulfosuccinates such as sodium dihexyl sulfosuccinate and sodium dioctyl sulfosuccinate; salts of resin acids such as abietic : acid and dihydroabietic acid.

Also suitable are cationic surfactants such as alkyl ammonium or quaternary ammonium salts, e.g., dodecyl ammonium hydrochloride, dodecyl trime~hyl qua~ernary ammonium chloride and the like, and eth-oxylated fatty amines. Other sui~able suractants are described in McCutcheon's, supra. Also included in the aforementioned surfactants are oligomeric and polymerizable surfactants described at pages 319-322 of Blackley, supra. Examples of such oligomers include 26,810-F -14-' `: ' ` , ' . ~ ~ ' :, :
.

ammonium and alkali metal salts of functionalized oligomer~ sold by Uniroyal Chemical under ~he trade name "Polywet" and copolymers of acrylonitrile and acrylic acid having molecular weights less ~han 2000 which are prepared in the presence of chain terminating agents such as n-octyl mercaptan. Examples of poly-merizable surfactants include sodium salts of 9- and 10-(acrylylamido)stearic acid and ~he like. Of the foregoing surfactants, the nonionic types are pre-ferred, with ethoxylated alkyl phenol and ethoxylatedfatty alcohols being most pre~erred. However, when the water soluble polymer is cationic, it is desirable to use a cationic or nonionic surfactant. When the water ~ soluble polymer is anionic, it is desirable to employ an anionic or nonionic surfactant.

The thickening agent o the present in~ention is advantageously prepaxed by dispersing the water-soluble polymer and the surfactant in an aqueous medium under conditions such that the components ~are uniformly distributed throughout the aqueous medium. Alterna-tively and preferably, the surfactallt is added to the polymerization recipe used to prepare the water-soluble polymer, and the recipe is then subjected to polymeriza-tion condi~ions. In su~h preferred embodiments, the surfacta~t is one which emulsifies the hydrophobic monomer in the aqueous pol~merization medium and which increases the viscosity of an aqueou~ solution of the copolymer. While the relative proportions of the water soluble polymer and the surfac~ant are no~ particularly critical, i~ is generally desirable to employ proportions such that associations between the hydrophobic moieties of the water~soluble polymer and the hydrophobic moieties of the surfactant are maximiæed. Accordingly, the 26,810--F -15-critical micelle concentration of the surfactant and the number and size of the water-soluble polymer mole-cules are advantag~ously correlated such ~hat the hydrophobic moieties of at least two molecules of the water-soluble polymer can associate with the hydrophobic moieties of each particle (micelle) of the surfactant.
Usually, the ratio of surfactant to water-soluble polymer is one that produces a viscosity at least twice that of a solution containing only the water-soluble polymer. Preferably, the weigh~ ratio of water-soluble pol~mer ~o surfactant is from 20:1 to 0.5:1, mos-t pre-ferably from 10:1 to 1:1.

The amount of total thickening agent in the aqueous medium being thickened is sufficient to provide the desired increase in viscosity of the agueous medium.
Preferably, such amounts of thickening agent range from 0.025 to 5 weight percent, most preferably from 0.5 to 2.5 weight percent, based on the aqueous medium. In addi~ion, to the thickening agent, the aqueous medium - 20 may cont~in a variety of other ingredients common to brines, fracturing fluids, drilling muds, paint formu-lations, lubricants, friction-redu~ing agents, sus-pending agents, liquid mobility control agents, hydraulic - fluids and the like.

of particular interest are the brines and other agueous media containing salts of various metals.
Such aqueous media of-ten contain from 0.01 to 20 weiyht percent of salts of alkali metals and alkaline earth metals.

To increase the viscosity of an aqueous medium containing substantial amoun-ts, eOg., up to 26,810-F ~16-~ 8 ~

about 5 weight percent based on the aqueous medium, of monovalent inorganic salts such as sodium chloride and up to 1 weight percent, usually from 0.0015 to 0.5 weight pexcent, of salts of polyvalent cations such as calcium and magnesium, it is preferred to employ (1) as the water-soluble polymer, (a) a nonionic copolymer of a water-soluble ethylenically unsaturated carbo~amide such as acrylamide and a higher alkyl acrylate or methacrylate such as dodecyl methacrylate or (b) an anionic copolymer of sodium acrylate and higher alkyl acrylate or methacrylate, and (2) any suitable surface active agent as the surfac~ant. The viscosity increase in this aqueous medium is retained at temperatures over the range from 30 to 80C. I~ many ins~ances, ~his viscosity increase is retained at tempexatures sub-stantially hisher than 80~C, e.g., 275C and higher.
To increase the viscosity of an aqueous m dium at a temperature of 60 to 80C and containing from 10 to 15 weight percent of a monovalent salt, it is preferred to use one of the aforementioned nonionic or anionic copolymers with a nonionic surfactant having an ~LB
greatex than 10, e.g., a dodecyl ether of polyethylene glycol containing 10 ethyleneoxy units per surfactant molecule. In contras~, to increase the viscosity of an aqueous medium at an ambient temperature and containing from 0.1 to 0.5 weight percent of monovalent salt, it is preferred ko employ one of the aforementioned nonionic or anionic copolymers with a nonionic surfactant having an HLB less than 10 such as ~he dodecyl ether of a polyethylene glycol having 2 ethyleneoxy groups per sur-factant molecule. Finally, to increase the viscosity of an aqueous medium containing ~rom 1 to 5 weight per-cent of salts of polyvalent cations, e.g., calcium and/or magnesium in the form of salts such as calcium -26,81Q-F -17~

i38 bromide, calcium chloride or magnesium sul~ate, it is preferable to employ one of the aforementioned nonionic copolymers in combination with a nonionic surfactant, especially a surfactant having an HLB
greater than 10, e.g., the dodecyl ether of a poly-ethylene glycol having 5 ethyleneoxy groups per surfactant molecule.

In general, the type of application and the conditions characteristic of the application will determine the ~ype and amount of surfactant employed, to give the desired viscosity response. For example, it is found that a nonionic surfactant having a low HLB, e~g., an HLB of 4 to 8, is advantageously employad in an aqueous medium having a relatively low salt concen-tration and moderate temperature. On the other hand, a nonionic surfactant having a high HLB, e.g., an HLB of 10-14, is advantageously employed in an aqueous medium having a relatively high salk concentration and high temperature. ~oreo~er, the desired viscosity - 20 response for a given set of conditions can be achieved by adding a single surfactant having the desired HLB
value or by adding a mixture of surfactants haviny di~ferent HLB values which combine to provide the de~ired Hl,B value.

The following examples are given to illus trate the invention and should not be construed as limiting its scope. Unless otherwise indicated, all parts and percentages are by weight.
:
I. General Procedure for Preparing Water-Soluble Polvmers --A 2g5 ml citrate bottle is charged with 25 g of an a~leous solution containing 10 percent of sodium 26,810-F la-~31 7~

dodecyl sulfate. A specified higher alkyl methacrylate monomer is then dispersed into the aqueous solution by adding the monomer to the bottle and agitating the contents until emulsification of the monomer is achieved.
Approximately 100 ml of deionized water is added with stirring followed by the addition of an aqueous solution containi~g the specified water-soluble monomer. Aqueous solutions of a specified chelating agent and acetic acid are then added followed by th~ addition of isopropyl alcohol as a chain transfer agent. A solution of azobisisobu~yronitrile (initiator) iIl tertiary butyl alcohol is added followed by addition of sufficient deionized water to increase the total contents (reaction mixture) of the bottle to 250 g. The con-tents of the bottle are degassed by alternate cycles(5-10 cycles) of vacuum and nitrogen gas purge. The bottle is then capped and heated in a wa~er bath at 60C for 16 hours in an end-over-end apparatus thereby - effecting copolymerization of the monomers. Following polymerization, the contents of the bottles are cooled to room temperature aIld the polymer is removed from the bottle as a thick aqueous solution.

For purposes of comparison, water-soluble polymers of the water-soluble monomers which polymers do not contain ~he higher alkyl methacrylate are pre-pared according to the foregoing procedure except that the higher alkyl methacrylate is omitted. Also for comparison water soluble polymers which contain lower alkyl acrylates are similarly prepared.

~olecular weights of the afoxe~entioned water-soluble polymers are calculated from intrinsic viscosity measurements of aqueous ~olutions of such 26,810~F -19-, : i polymers. In such calculations, the following relation-ship is employed:

[~] = (6.31 x 10-5) ~ 008 wherein ~] is intrinsic viscosity and Mw is the weight average molecular weight of the pol~mer.

II. General Procedure for Preparing Thlckenln~ Agent -An aqueous solu~ion of water-soluble polymer - obtained in the foregoing manner is combined with a specified nonionic suractant. The resulting solution is diluted with deionized water and slowly agitated overnight to obtain a uniform solution o~ the two component thickening agent of this invention.

Alternatively, the specified nonionic surfac-tant is added to the citrate bottle with the~aqueous solution of sodium dodecyl sulfate and the aforemen~
tioned polymerization procedure is carried out as described. Following this procedure, an aqueous solu-tion of the ~wo component thickening agent is recovered from the citrate bottle after polymerizatio~ is complete.

Example Several polymers (Polymer Designation A, C, F, G, H, I, K, Q, R, S, T, U, V, AA, CC, DD, EE, a~d - FF) are prepared according to the aorementioned general procedure using di~ferent polymerization formulations set forth in Table I. Thickening agents are then prepared by one of ~he two alternative procedures described hereinbefore and tested for ViSCoSl~y in the presence of different salts and various concentrations as well as under different conditions such a temperature.
The results of ~hese tests are reported in Table II.

~6,810~F -20-~7~

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p ~ _ _ _ 26, 810-F -34~

-~7~8~

As shown by Sample Nos. 1-6, the addition of NaCl to an aqueous solution of a preferred thickening agent of this invention wherein the surfactant (C12(E0)5) is added to the water-soluble copolymer having hydrophobic ( /C12MA 99.9/0.1) (Polymer A) increases the viscosity of -the solution several times. In contrast, as shown by Sample Nos. Cl-C2, similar addition of NaCl to an aqueous solution of polyacrylamide (Polymer AA) and the same surfactant (C12~EO)5) does not increase viscosity. Similarly, as shown by Sample ~QS. 7-11, increase of temperature to 70C of solutions containing the thickening agent used in Sample Nos. 1-6 actually increases viscosity of the solution, whereas as shown in Sample Nos. C3-C6, a similar temperature increase in solutions containing polyacrylamide and C12(EO)5 sur~
factant actually decreases the viscosity of the solution.

As shown by Sample Nos. 12-15, addition of NaCl to an aqueous solution of C12(E0~5 surfactant and an AAM/C12MA (99.9/0.1) copolymer (Polymer G) having a lower molecular weight (MW=800,000) than the copolymer (MW=2.5-3 million) of Sample Nos. 1 6 causes a similar increase in viscosity. Sample Nos. 16-20 show that an increase of C12MA from 0.1 to 0.25 (Polymer H) causas a substantial increase in viscosity of solutio~s containing relatively low electrolyte concentrations. In contrast, Sample Nos. C7-C12 show that addition of sal~ does not increase viscosity o aqueous solutions containing C12(EO)5 surfacta~t and a polyacrylamide having an Mw of about 800,000 (Polymer DD).

As shown by Sample Nos. 21~28, aqueous solu-tions of AAM/C12MA (99.5/0.5~ copolymer (Polymer ~ a~d .

26,810-F ~35-C12(E0)5 surfactant retains much o~ its viscosity in the presence of significant sal~ concentrations and increase of temperature to 70C. In fact, the ability of such solutions to undergo temperature increase S without significant loss of viscosity is enhanced by increased concen~rations of salt. In contrast, as shown by Sample Nos. C13-C14, an aqueous solution of polyacrylamide (Polymer DD) and the C12(EO)5 surfactant undergoes a loss of viscosity when subjected to an increase in temperature.

As shown by Sample Nos. 29-33, aqueous solu--tions of C12(EO)5 surfactant and AAM/C4MA (99/1) co-polymer (Polymers Q and R) do not exhibit significant viscosity increases upon addition of sal~. This is believed to be due to the fact that there is not suf-ficient association between the hydrophobic dodecyl group of the C12(E0)5 surfactant and the butyl group of tha butyl acrylate of the AAM/C4MA copol~mer (Polymers Q
and R~. In contrast, as shown by Sample Nos. 34~35, aqueous solutions of C12(E0~5 surfactant and AAM/C8MA
copolymer having an ~ of 2.5-3.5 million (Polymer S) do exhibit an increase in viscosity upon addition of salt. Similar solutions ~Sample Nos. 36-37) wherein the AAM/C8MA copol~mer contains only 0.1 mol~ percent of octyl methacrylate (C8MA) and has an Mw f 800,000 (Polymer T) do not exhibit an increase in viscosity upon addition of salt. This data indicates that suf-ficient association b~tween the octyl groups of C8MA
and the dodecyl groups Qf C1~EO)5 will occur if the AP~VC8MA contains a sufficient mole percent of C8MA
and/or has sufficient molecular weight.

26,810-F -36 ~L~7~38 As shown by Sample Nos. 38-44, aqueous solu-tions of an AAM/C12MA (99.5/0.5) copoly~er having an ~
of only 200,000 (Polymer K~ exhibit significant incréases in viscosity when small amounts of C12(EO)l surfactant are added. Accordingly, it is shown that aqueous solutions of substantial viscosity can be prepared in the absence of an electrolyte. In contrast, as shown in Sample Nos. C15-C17, aqueous solutions of low molecu-lar weight polyacrylamide (MW=200,000~ (Polymer EE) do not exhibit any increase in viscosity when combined with the C12~EO~l surfactant.

As sh~wn by Sample Nos. 45-56, aqueous solu-tions of AAM/C12MA (99~9/1) copolymer (Polymer C) or AAM/C12MA (99.75/0.25) copolymer (Polymer F) and C12(E0~5 surfactant which is present during polymerization exhibit increased viscosities when KCl is added to the solutions. Accordingly, it is shown that the surfactant c~n be added prior to polymerization. In contrast, as shown in Sample Nos. C18-C21, aqueous solutions of polyacrylamide and C12(E0)5 surfactant which is present during polymerization do not exhibit increased viscosity where KCl is added to the solution~.

As shown by Sample Nos. 57-67, aqueous solu~
tions of AAM/C12MA (99.75/0.25) copolymer (Polymer F) and C12tEO)5 surfac~nt which is present during polymeri-zation exhibit substantial viscosity increases when salts of divalent cations such as CaC12 or MgSO4 are added to the solutions. Such increases in viscosity are no~ obtained when such sal~s are added to aqueous solutions of polyacrylamide and C12(~0~5 surfactant (Sample Nos. C22 C~6).

26,810-F =37-~ ' ~
, As shown in Sample Nos. 68-77, aqueous solu-tions of AAM/C12MA/AA (49.9/0.1/50) copolymer (Pol~mer U~
or AAM/C12MA/AA (74.9/0.1/25) copolymer ~Polymer V~ and C12(E0)5 surfactant exhibit good retention of viscosity even upon addition of substantial amounts of KCl. In contrast, as shown by Sample Nos. C27-C3~ aqueous solutions of AAM/AA ~80/20) copolymer (Polymer FF) and Cl~(E0)5 surfactant exhibit almost a total loss of viscosity as KCl is added to the solution.

26,810-F -38-

Claims (61)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A thickening composition for aqueous liquids comprising a water-soluble polymer having pendant hydrophobic groups and a water-dispersible nonionic surfactant having hydrophobic groups that are capable of associating with the hydrophobic groups of the polymer wherein the proportion of water-soluble polymer and surfactant is such that at ambient conditions, water containing 0.5 weight percent of the thickening composition has a viscosity at least twice the viscosity of water.
2. A thickened aqueous composition comprising an aqueous medium having dispersed therein the thickening composition of Claim 1 in an amount sufficient to increase the viscosity of said aqueous medium.
3. The composition of Claim 2 which also contains an amount of a water-soluble electrolyte which is sufficient to increase the viscosity of the thickened aqueous composition.
4. The composition of Claim 1 wherein the water-soluble polymer is a copolymer of a water-soluble monomer and a hydrophobic monomer having a hydrophobic moiety of at least 8 carbon atoms.

26,810-F -39-
5. The composition of Claim 4 wherein the surfactant is a nonionic surfactant selected from an alkyl polyethyleneoxy glycol monoether or alkylaryl polyethyleneoxy glycol monoether wherein alkyl has from 8 to 20 carbon atoms and from about 1 to 20 ethyleneoxy groups per polymer molecule.
6. The composition of Claim 1 wherein the water-soluble polymer is a copolymer. of from 40 to 99.9 mole percent of acrylamide, from 0 to 50 mole percent of acrylic acid and from 0.1 to 10 mole percent of an alkyl methacrylate or acrylate wherein alkyl has from 8 to 12 carbon atoms, said polymer having a weight average molecular weight in the range from 800,000 to 3 million and the surfactant is an alkyl polyethyleneoxy glycol monoether wherein alkyl has from 8 to 20 carbon atoms and there are from 1 to 12 ethyleneoxy groups per molecule of surfactant.
7. An aqueous composition comprising an aqueous medium and the thickening composition of Claim 6 in an amount from 0.01 to 1 weight percent of the copolymer and from 0.0015 to 0.5 weight percent of the monoether and from 0.01 to 20 weight percent of an alkali metal salt or an alkaline earth metal salt.
8. The composition of Claim 6 wherein the polymer is a copolymer of from 60 to 99.9 mole percent of acrylamide, from 0 to 30 mole percent of acrylic acid and from 0.1 to 10 weight percent of dodecyl methacrylate, and the surfactant is a dodecyl poly-ethyleneoxy glycol monoether wherein the monoether has from 1 to 10 ethyleneoxy groups per molecule.

26,810-F -40-
9. The composition of Claim 8 wherein the copolymer comprises from 99 to 99.9 mole percent of acrylamide and from 0.1 to 1 mole percent of dodecyl methacrylate and the monoether has 5 ethyleneoxy groups per molecule.
10. The composition of Claim 3 wherein the electrolyte is a salt of a mono- or divalent metal in an amount from 0.01 to 15 weight percent based on the aqueous composition.
11. The composition of Claim 1 which contains from 0.01 to 1 weight percent of the polymer and from 0.0015 to 0.5 weight percent of the surfactant.
12. The composition of Claim 2 which contains from 0.025 to 5 weight percent of the thickening agent.
13. A water-soluble composition for thickening aqueous liquids comprising (A) a water-soluble thickening agent which agent comprises (1) a water-soluble polymer having pendant hydrophobic groups, said polymer being a copolymer of a water-soluble ethylenically unsaturated monomer and water-insoluble ethyleni-cally unsaturated monomer having a hydrophobic group having a least 8 carbon atoms, wherein (a) the water-soluble monomer is an ethylenically unsaturated amide or an N-substituted derivative thereof, an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated quaternary ammonium compound, a sulfoalkyl ester of an unsaturated 26,810-F -41-carboxylic acid, an aminoalkyl ester of an unsaturated carboxylic acid, a diallylamine, a diallylammonium compound or a vinylaryl sulfonate, and (b) the water-insoluble monomer is a higher alkyl ester of an .alpha.,.beta.-ethylenically unsaturated carboxylic acid, an alkylaryl ester of an ethylenically unsaturated carboxylic acid, an N-alkyl ethylenically unsaturated amide, a vinyl alkyl ether or an ar-alkyl styene; and (2) a water-dispersible nonionic surfactant having hydrophobic groups that are capable of associating with the hydrophobic groups of the copolymer such that at ambient conditions, water containing 0.5 weight percent of the thickening agent has a viscosity at least twice the viscosity of water, said thickening agent having a weight ratio of the copolymer to the surfactant in the range from about 20:1 to about 0.5:1; and (B) a water-soluble inorganic salt in an amount such that at a temperature in the range up to about 80°C, an aqueous medium containing a viscosity increasing amount of the thickening agent exhibits a further increase in viscosity when the water-soluble salt is added to the medium.
14. The composition of Claim 13 wherein the polymer has a weight average molecular weigh-t in the range from about 200,000 to about 5 million.
15. The composition of Claim 13, wherein the water-soluble polymer contains from about 98 to about 99.995 mole percent of one or more of the water-soluble 26,810-F -42-monomers and from about 0.005 to about 2 mole percent of one or more hydrophobic monomers.
16. The composition of Claim 13 wherein the nonionic surfactant has an HLB in the range from about 2 to about 15.
17. The composition of Claim 13 wherein the surfactant has an HLB in the range from about 5 to about 13.
18. The composition of Claim 13 wherein the surfactant is an alkyl polyethyleneoxy compound represented by the formula: RO(EO)nH wherein R is a C8-C18 alkyl, EO is ethyleneoxy, and n is a number from 1 to 10, said surfactant having an HLB in the range from about 5 to about 13.
19. The composition of Claim 13 wherein the surfactant is a reaction product of ethylene oxide or mixture of ethylene oxide and a higher alkylene oxide with an active hydrogen compound, said surfactant having an HLB in the range from about 2 to about 15.
20. The composition of Claim 13 wherein the surfactant is a dodecyl polyethyleneoxy glycol monoether wherein the monoether has about 1 to about 10 ethyleneoxy groups per molecule.
21. The composition of Claim 20 wherein the monoether has 5 ethyleneoxy groups per molecule.
22. The composition of Claim 20 wherein the surfactant comprises a mixture of surfactants having different HLB values.

26,810-F -43-
23. An aqueous composition comprising an aqueous phase having dispersed therein the thickening composition of Claim 13 in an amount sufficient to increase the viscosity of said aqueous phase.
24. The composition of Claim 23 which contains from about 0.025 to about 5 weight percent of the thickening agent.
25. The composition of Claim 23 which also contains sufficient amounts of ingredients common to a fracturing fluid used in oil recovery to be useful as such a fracturing fluid.
26. The composition of Claim 23 which also contains sufficient amounts of ingredients common to a drilling mud formulation to be useful as a drilling mud.
27. The composition of Claim 23 which also contains sufficient amounts of ingredients common to a fluid mobility control agent useful in enhanced oil recovery.
28. A water-soluble composition for thickening aqueous liquids which composition comprises (A) water-soluble thickening agent comprising (1) a water-soluble polymer having pendant hydrophobic groups, said polymer being a copolymer of a water-soluble ethylenically unsaturated monomer and water-insoluble ethylenically unsaturated monomer having a hydrophobic group, wherein (a) the water-soluble monomer is acrylamide, methacrylamide and fumaramide;

26,810-F -44-2-acrylamide-2-methylpropane sulfonic acid, N-(dimethylaminomethyl)acrylamide, N- (tri-methyammoniummethyl)acrylamide chloride, N-(trimethylammoniumpropyl)methacrylamide chloride, acrylic acid, methacrylic acid, itaconic acid and fumaric acid, vinylbenzyl trimethyl ammonium chloride, 2-sulfoethyl methacrylate, 2-aminoethyl methacrylate, vinyl pyridine, vinyl morpholine, diallyl dimethyl ammonium chloride, vinyl pyrrolidone or a salt of vinylbenzyl sulfonate and (b) the water-insoluble monomer is 2-ethylhexyl methacrylate, dodecyl acrylate, dodecyl methacrylate, tridecyl acrylate, tridecyl methacrylate, tetradecyl acrylate, tetradecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, ethyl half ester of maleic anhydride, diethyl maleate, and other alkyl esters derived from the reactions of alkanols having from 8 to 20 carbon atoms with ethylenically unsaturated carboxylic acids selected from the group consisting of acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, itaconic acid and aconitic acid, nonyl-.alpha.-phenyl acrylate, nonyl-.alpha.-phenyl methacrylate, dodecyl-.alpha.-phenyl acrylate, dodecyl-.alpha.-phenyl methacrylate, N-octadecyl acrylamide, N-octadecyl meth-acrylamide, N,N-dioctyl acrylamide; octene-1, decene-1, dodecene-1, hexadecene-1, vinyl laurate, vinyl stearate, dodecyl vinyl ether, hexadecyl vinyl ether, N-vinyl lauramide, N-vinyl stearamide or t-butyl styrene;

26,810-F -45-(2) a water-dispersible nonionic surfactant having hydrophobic groups that are capable of associating with the hydrophobic groups of the copolymer such that at ambient conditions, water containing 0.5 weight percent of the thickening agent has a viscosity at least twice the viscosity of water, said thickening agent having a weight ratio of the copolymer to the surfactant in the range from about 20:1 to about 0.5:1; and (B) a water-soluble inorganic salt of a metal in an amount such that at a temperature in the range up to about 80°C, an aqueous medium containing a viscosity increasing amount of the thickening agent exhibits a further increase in viscosity when the water-soluble salt is added to the medium, said amount of salt being in the range from about 0.01 to about 20 weight percent based on the medium.
29. The composition of Claim 28 wherein the water-soluble monomer is acrylamide, acrylic acid or a mixture of acrylamide and acrylic acid and the hydro-phobic monomer is dodecyl methacrylate or t-butyl styrene.
30. The composition of Claim 28 wherein the water-soluble polymer is a copolymer of acrylamide and dodecyl methacrylate or a copolymer of acrylamide, acrylic acid and dodecyl methacrylate.
31. A thickened aqueous composition which composition comprises (A) water having dispersed therein (1) a viscosity increasing amount of a water-soluble copolymer of from about 40 to about 26,810-F -46-99.9 mole percent of acrylamide, from 0 to about 50 mole percent of acrylic acid and from about 0.1 to about 19 mole percent of an alkyl methacrylate or acrylate wherein alkyl has from 8 to 12 carbon atoms;
(2) and a surfactant comprising an alkyl polyethyleneoxy glycol monoether wherein alkyl has from 8 to 20 carbon atoms and there are from l to 12 ethyleneoxy groups per molecule of the monoether; and (3) from about 0.01 to about 20 weight percent of a salt of an alkali metal or an alkaline earth metal;
in said composition the weight ratio of copolymer to monoether being in the range from about 20:1 to about 0.5:1.
32. The composition of Claim 31 comprising (1) from about 0.1 to about 1 weight percent of said water-soluble copolymer having a weight average molecular weight in the range from about 800,000 to about 3 million;
(2) from about 0.0015 to about 0.5 weight percent of said alkyl polyethyleneoxy glycol monoether;
and (3) from about 0.01 to about 20 weight percent of said salt of an alkali metal or an alkaline earth metal, said alkyl groups of the monoether being capable of associating with the alkyl groups of the copolymer in the thickened aqueous composition, and said copolymer, monoether and salt being present in amounts sufficient to increase the viscosity of the aqueous medium.

26,810-F -47-
33. The composition of Claim 31 wherein the copolymer comprises from about 60 to about 99.9 mole percent of acrylamide, from 0 to about 30 mole percent of acrylic acid and from about 0.1 to about 10 weight percent of dodecyl methacrylate, and the surfactant is a dodecyl polyethyleneoxy glycol monoether wherein the monoether has about 1 to 10 ethyleneoxy groups per molecule.
34. The composition of Claim 33 wherein the copolymer is a copolymer from about 99 to about 99.9 mole percent of acrylamide and from about 0.1 to about 1 weight percent of dodecyl methacrylate and the monoether has 5 ethyleneoxy groups per molecule.
35. The composition of Claim 31 wherein the salt is sodium chloride or potassium chloride or a mixture thereof and is present in an amount from about 0.1 to about 15 weight percent based on the aqueous composition.
36. The composition of Claim 31 wherein the salt is a divalent metal of Ca, Mg, or mixtures thereof and is present in an amount from about 0.01 to about 10 weight percent based on the composition.
37. A fracturing fluid useful in oil recovery containing a viscosity increasing amount of the composition of Claim 31.
38. A fluid mobility control agent useful in enhanced oil recovery containing a viscosity increasing amount of the composition of Claim 31.

26,810-F -48-
39. A thickened aqueous composition comprising (A) an aqueous medium having dissolved therein;
(B) a viscosity increasing amount in the range from about 0.025 to about 5 weight percent of a thickening agent comprising (1) a copolymer of from about 98 to about 99.995 mole percent of one or more water-soluble ethylenically unsaturated monomers and from about 0.005 to about 2 mole percent of one or more water-insoluble ethylenically unsaturated monomers having hydrophobic groups having at least 8 carbon atoms wherein the water-insoluble monomer is a higher alkyl ester of an .alpha.,.beta.-ethylenically unsaturated carboxylic acid, an alkylaryl ester of an ethylenically unsaturated carboxylic acid, an N-alkyl ethylenically unsaturated amide or an ar-alkyl styrene, and (2) a water-dispersible, nonionic surfactant having hydrophobic groups that are capable of associating with the hydrophobic groups of the copolymer wherein the weight ratio of copolymer to surfactant is in the range from about 20:1 to about 0.5:1; and (C) an amount of a water-soluble inorganic salt in the range from about 0.01 to about 20 weight percent based on the medium which is sufficient to increase the viscosity of the aqueous medium containing the thickening agent.
40. The composition of Claim 39 wherein the water-soluble monomer is acrylamide, acrylic acid or a mixture of acrylamide and acrylic acid; the water-insoluble monomer is (a) an alkyl ester of an ethylenically unsaturated carboxylic acid wherein alkyl has from 8 to 26,810-F -49-20 carbons or (b) an ar-alkylstyrene; the surfactant is an alkyl polyethyleneoxy compound represented by the formula: RO(EO)n-H wherein R is a C8-C18 alkyl, EO is ethyleneoxy and n is a number from 1 to 10, and the inorganic salt is a salt of an alkali metal or an alkaline earth metal or a combination of two or more of such salts and is present in the composition in an amount in the range from about 0.01 to about 20 weight percent.
41. The composition of Claim 40 wherein the water-soluble monomer is a mixture of acrylamide and from about 5 to about 50 mole percent of acrylic acid, the water-insoluble monomer is dodecyl methacrylate or t-butyl styrene and the salt is a mixture of sodium chloride and salts of calcium and magnesium.
42. A mobility control agent which is soluble in an aqueous flooding medium comprising a hydrophilic/-hydrophobic polymer having hydrophobic moieties and a water-dispersible, nonionic surfactant having hydrophobic groups that are capable of associating with the hydrophobic moieties of the polymer wherein the proportion of the polymer and the surfactant is such that, at ambient conditions, water containing 0.5 weight percent of the agent has a viscosity at least twice the viscosity of water, said agent having been prepared by carrying out the polymerization to form the polymer in the presence of the nonionic surfactant.
43. A composition comprising the agent of Claim 42 and a water-soluble, non-polymeric electrolyte which can reduce the critical micelle concentration of the surfactant when the electrolyte is added to an aqueous solution of the surfactant.

26,810-F -50-
44. An aqueous composition having increased viscosity comprising an aqueous medium having dispersed therein the agent of Claim 42 in an amount sufficient to increase the viscosity of said aqueous medium.
45. The composition of Claim 44 which also contains an amount of a water-soluble, non-polymeric electrolyte which is sufficient to increase -the viscosity of the thickened aqueous composition.
46. The composition of Claim 45 wherein the polymer is a copolymer of a water-soluble monomer and a hydrophobic monomer having a hydrophobic moiety of a-t least 8 carbon atoms.
47. The composition of Claim 46 wherein the nonionic surfactant is an alkyl polyethyleneoxy glycol monoether or alkyaryl polyethyleneoxy glycol monoether wherein alkyl has from 8 to 20 carbon atoms and from about 1 to 20 ethyleneoxy groups per polymer molecule.
48. The composition of Claim 42 wherein the water-soluble polymer is a copolymer of from about 40 to about 99.9 mole percent of acrylamide, from 0 to about 50 mole percent of acrylic acid, and from about 0.1 to about 10 mole percent of an alkyl methacrylate or acrylate wherein alkyl has from 8 to 12 carbon atoms or an ar-alkyl styrene wherein alkyl has from 4 to 8 carbons, said polymer having a weight average molecular weight in the range from about 800,000 to about 3 million and the surfactant is an alkyl polyethyleneoxy glycol monoether wherein alkyl has from 8 to 20 carbon atoms and there are from 1 to 12 ethyleneoxy groups per molecule of surfactant.

26,810-F -51-
49. An aqueous composition comprising an aqueous medium and the thickening composition of Claim 48 in an amount sufficient to increase the viscosity of the aqueous medium.
50. The aqueous composition of Claim 49 comprising the aqueous medium and from about 0.01 to about 1 weight percent of the copolymer and from about 0.0015 to about 0.5 weight percent of the monoether and from about 0.01 to about 20 weight percent of an alkali metal salt or an alkaline earth metal salt.
51. The composition of Claim 42 wherein the polymer is a copolymer of from about 60 to about 99.9 mole percent of acrylamide, from 0 to about 30 mole percent of acrylic acid and from about 0.1 to about 10 weight percent of dodecyl methacrylate and the surfactant is a dodecyl polyethyleneoxy glycol monoether wherein the monoether has about 1 to 10 ethyleneoxy groups per molecule.
52. The composition of Claim 51 wherein the copolymer is a copolymer from about 99 to about 99.9 mole percent of acrylamide and from about 0.1 to about 1 weight percent of dodecyl methacrylate and the monoether has 5 ethyleneoxy groups per molecule.
53. The composition of Claim 45 wherein the electrolyte is a salt of a monovalent cation which salt is present in an amount from about 0.1 to about 15 weight percent based on the aqueous composition.
54. The composition of Claim 53 wherein the salt is sodium chloride or potassium chloride or a mixture thereof.

26,810-F -52-
55. The composition of Claim 45 wherein the electrolyte is a salt of a divalent metal which salt is present in an amount from about 0.01 to about 10 weight percent based on the composition.
56. The composition of Claim 55 wherein the divalent cation is calcium, magnesium or a mixture thereof.
57. The composition of Claim 42 which contains from about 0.01 to about 1 weight percent of the polymer and from about 0.0015 to about 0.5 weight percent of the surfactant.
58. The composition of Claim 44 which contains from about 0.025 to about 5 weight percent of the thickening agent.
59. The composition of Claim 42 wherein the polymer is a copolymer of from about 60 to about 99.75 mole percent of acrylamide, from about 0 to about 30 mole percent of acrylic acid and from about 0.25 to about 10 mole percent of t-butyl styrene.
60. The composition of Claim 45 wherein the electrolyte is an acid or a base.
61. An enhanced oil recovery process which comprises forcing an aqueous flooding medium from and injection well through a subterranean formation toward.
a producing well wherein the flooding medium contains the mobility control agent of Claim 42.

26,810-F - 53 -
CA000394913A 1981-02-06 1982-01-26 Water-dispersible hydrophobic thickening agent Expired CA1171188A (en)

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