CA2136632C - Aircraft anti-icing fluids thickened by associative polymers - Google Patents

Abstract

An anti-icing fluid suitable for ground treatment of aircraft, being a glycol-based, aqueous solution containing a hydrophobe-bearing, macromonomer-containing polymer thickener in an amount of less than about 5 weight %. Thickening occurs predominantly by association among hydrophobe groups. Thickening may be enhanced by addition of a surfactant or other materials which act as co-thickeners. Use of this thickened fluid does not adversely affect airfoil lift characteristics during takeoff, because the fluid exhibits shear thinning and readily flows off the aircraft surfaces when exposed to wind shear during the air-craft's takeoff run.

Description

F3rief Summary of the Invention ~'echnical Field This invention relates to glycol-based aircraft anti-icing fluids (AAFs) which are thickened with certain polymers containing hydrophobe-bearing macromonomers which thicken the A.AF via an associative mechanism.
3ackgLound of the Invention Aircraft that are either parked on the ground or are on the ground between flights can accumulate snov~~, ice, freezing rain or frost on the aircraft surfaces in cold winter weather. The presence of such deposits, particularly on airfoil surfaces, is a generally unsafe airfoil condition in that it hampers and can thwart liftoff, or at least is highly undesirable during takeoff' and early flight periods since even small accumulations can result in severe deterioration of the airfoil aero-dynamic performance WO 93/24543 ~~g PCT/US93/04865 ,..,"
~~~~~e)~

characteristics, occasionally causing crashes on takeoff/liftoff resulting in loss of life.
Glycols have long been used in aqueous solutions of ' various strengths that are sprayed onto the aircxaft, as a deicing agent, to remove snow,' ice, freezing rain and frost deposits from aircraft surfaces. After this treatment, the glycol fluid desirably remains as a film coating on the aircraft surfaces, to serve as an anti-icing agent that provides continued antifreeze protection and delays the further formation or accretion of snow, ice, freezing rain or frost deposits on the aircraft surfaces. The same glycol-based fluid, in various concentrations, may be used for both deicing and anti-icing functions.
Glycol-based fluids for anti-icing, however, typically contain a thickening agent and desirably possess the following attributes (none of which preclude its use as a deicer):
(i) formation of an essentially continuous film coating, after its application by conventional spraying devices, even on non-horizontal aircraft surfaces critical to the aircraft's sero-dynamic performance during takeoff/liftoff such as the vertical tail fin and the smoothness of the fuselage surfaces;
(ii) extended, long-term protective anti-icing action;
and (iii) viscosity and rheology characteristics that promote formation of an effective tenacious protective film coating, yet enable the fluid coating to flow off the aircraft . airfoil surfaces during takeoff, prior to aircraft rotation.
AAFs of the prior art are thickened typically with very ' large molecules (e.g., zanthan gum or various organic polymers) which thicken by molecular entanglement and intermolecular "
friction. Such thickeners are deficient in that they do not provide optimal non-Newtonian behavior (i.e., their viscosity may not .~-,. WO 93/24543 PCT/US93/04865 ~1356~~

decrease suffciently rapidly and/or extensively under wind-shear forces) for use under all weather conditions and on relatively slow-moving turboprop aircraft. Moreover, such thickeners are subject to undue degradation of viscosity as a result of severe shear forces imposed by the spraying nozzles used to apply the AAF to the aircraft.
This invention is based on the unexpected discovery that certain macromonomer-containing polymeric thickeners which thicken by association among hydrophobes possess particular effcacy as thickeners for glycol-based aircraft anti-icing fluids.
j?isclos~~re of the Tn_vention In accordance with this invention, an anti-icing fluid suitable for ground treatment of aircraft is provided which is a glycol-based solution thickened essentially with a hydrophobe-bearing, macromonomer-containing polymer in an amount of less than about 5 weight °.~. The macromonomer-containing polymer is present in the anti-icing fluid in an amount cuff dent to thicken the fluid to promote its adherence to aircraft surfaces when applied to a stationary aircraft but also allow for its wind shear-induced removal during the takeoff run prior to rotation.
Accordingly, the present invention provides an aircraft anti-icing fluid comprising, in admixture, a glycol, water, and a hydrophobe-bearing, alkali-ewellable, polymeric thickener which thickens principally by an inter-molecular associative mechanism among hydrophobe groups, said fluid being sufficiently viscous to adhere to the airfoil surfaces of an aircraft at rest, but becoming sufficiently fluid under the influence of wind shear forces to flow off the airfoil surfaces when they are at or near take-off speed.
Preferably, the thickener comprises a carboxylic backbone to which the hydrophobes are attached by flexible, pendant chains, WO 93/24543 ~ PCT/US93/04865 -~13~~~'~

particularly wherein the flezible, pendant chains comprise one or more hydrophilic polymers. It is also desirable that the fle~dble, pendant chains are su~csently long to place the hydrophobes beyond the carbonyl environment of the backbone. While the thickeners of this invention are capable of considerable variation in molecular weight, depending upon their molecular constituency (and indeed that is one of their advantages), it is preferred that each repeating unit have a molecular weight of no more than about 6,000, preferably no more than about 3,000.
The properties of the present AAF may also be advantageously expressed in accordance with airline standard tests for performance: Water spray encurance time, and boundary layer displacement thickness. Accordingly, the present invention provides an AAF wherein the water spray endurance time is at least about 30 minutes, preferably at least about 40 minutes, but wherein the boundary layer displacement thickness is less than about 8 mm, preferably less than about 6 mm, at -20 C.
The invention further provides a method for thickening a glycol/water anti-icing fluid comprising admixing with said fluid a thickener of this invention. In addition, the invention includes a method for providing anti-icing protection to aircraft comprising applying to the airfoil surfaces of the aircraft an AAF containing a thickener of this invention.
The thickeners of this invention are preferably derived from polymerizable carboxylic acids with which have been co-polymerized hydrophobe-bearing macromonomers. Thus, the preferred macromonomer-containing polymers useful in this invention comprise:
(A) about 1-99.9, preferably about 10-70, weight percent of one or more alpha, beta-mono- ethylenically unsaturated carboxylic acids, typically methacrylic acid;

-- WO 93/24543 ~ ~ ~ ~ ~ ~ ~ PGT/U893/04865 B) about 0-98.9, preferably about 30-85, weight percent of one or more monoethylenically unsaturated monomers, typically ethyl acrylate;
(C) about 0.1-99, preferably about 5-60, weight percent of one or more monoethylenically .saturated macromonomers; and (D) about 0-20, preferably about 0-10, weight percent or greater of one or more polyethylenically unsaturated monomers, typically trimethylol propane triacrylate.
The macromonomer portion preferably comprises at least about 5°k weight percent of the polymer.
The anti-icing fluid is preferably an Association of European Airlines AEA-Type II de/anti-icing fluid, thickened with a macromonomer- containing polymer in an amount of less than about weight °k. The macromonomer-containing polymer thickener is desirably present in an amount of from about 0.05 to 3 weight °k, more preferably from about 0.1 to 1 weight °6.
The glycol component of the glycol-based fluid is preferably ethylene glycol, either alone or in combination with other glycols like diethylene glycol or propylene glycol. The glycol component of the aqueous anti-icing fluid is desirably present in an amount of at least about 40 weight °~o, preferably from about 50-95 weight °k.
~et~led l~escri,yti~
. . Aircraft Anti-Icing Fluids (AAFs) prevent ice, snow, freezing rain and the like forms of frozen precipitationslaccumulations from adhering to clean planes after de-icing. A typical aircraft anti-icing fluid is composed of an alkaline ethylene glycol and water solvent miztures (roughly equal parts on a weight basis; the pH is about 8.5) that contains ionic corrosion ~~ ~ ~ ~'~ PGT/US93/04865 inhibitors, rheology modifiers, and surfactants that promote wetting of the fluid on the aircraft during spray application. Common rheology modifiers used in aircraft anti-icing fluids include cross-linked polyacrylates, carboaypolymethy-lene, and polysaccharides (ganthan gum and Carrageenan). Airlines that operate in Europe and Canada, where hoary-frost hinders wintertime airline operations, use these fluids.
The ideal thickener gels the AAF at rest to prevent the accumulation of rain water and ice on the bare airfoil after de-icing, and to promote the adhesion of the fluid to vertical surfaces. To minimize lift loss, the AAF dramatically thins under shear so that it flows readily off the aircraft wing during the takeoff run prior to rotation -- rotation is the point at which the airfoil lift is sufficient for the pilot to take-off - which corresponds to a shear stress of on the order of about 10 Pa. AAF viscosity should not vary significantly with temperature change or water dilution: a viscosity that doesn't change, or that increases slightly, with water dilution correlates with hold-over time -- the length that the plane can last in bad weather needing another de-icing treatment.
The glycol-based anti-icing fluid of this invention, along with its desirable performance characteristics, may be obtained with most conventional glycol-based fluids via use of the macromonomer-containing polymer as a fluid thickener. The macromonomer-containing polymer is intended for use as the primary thickener in conventional glycol-based anti-icing fluids for aircraft usage.
Aircraft anti-icing fluids referred to as Association of European Airlines (AEA) Type II fluids contain a thickener, and the macromonomer-containing polymers described herein are especially well suited for use as thickeners in these fluids. _ Glycol-based deicing and anti-icing fluids are well known having been used for aircraft deicing and anti-icing applications for decades. The primary component of the fluid, which provides its deicing and anti-icing properties, is a water-soluble glycol compound. The glycol-based fluids typically contain one or more glycols selected from ethylene glycol, propylene glycol, and diethylene glycol, including mixtures thereof. Other glycols or polyols with freezing point depressant properties may also be used, along with the above-noted glycols or in lieu of them.
A preferred fluid formulation contains ethylene glycol as the major glycol component, desirably at least about 80 weight %
ethylene glycol. Propylene glycol and/or diethylene glycol may also be present in the glycol-based fluid. Diethylene glycol, in combination with propylene glycol, is another glycol formulation that is suitable for use in this invention. The choice and relative amounts of specific glycols present in the glycol-based fluid will depend on the particular anti-icing, antifreeze properties desired for the fluid, e.g., freezing point characteristics, pour point, etc.
The anti-icing fluid is an aqueous solution, i.e., ethylene glycol or other suitable glycol that is diluted with water. The glycol should be present in the aqueous solution in an amount of at least about 40 weight %, and preferably is present in an amount of at least about 50 weight %, up to about 95 weight %. The combined glycol and water components of the fluid preferably constitute at least about 90 weight % of the total composition and more preferably at least about 95 weight % of the total composition.
The amount of glycol is desirably su~cient to yield a freezing point for the fluid that is less than about -10°C, more preferably, less than about -30°C.
Illustrative macromonomer-containing polymers useful in this invention and processes for preparation thereof are disclosed in U.S. Patent No. 5,292,843.
A large proportion of one or more alpha, beta-monoethylenically unsaturated carboxylic acid monomers can be WO 93/24543 ~- PGT/US93/04865 ..-~1~6~~
_g_ present in the polymers useful in this invention. Various carboxylic acid monomers can be used, such as acrylic acid, methacrylic acid, ethacrylic acid, alpha-chloroacrylic acid, crotonic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, malefic acid and the like, including mixtures thereof. Methacrylic acid is preferred, particularly in concentrations of at least about 40°k by weight of the polymer. A large proportion of carboxylic acid monomer is desirable to provide a polymeric structure which will swell or dissolve and provide a thickener when reacted with an alkali, e.g., sodium hydroxide.
The polymers useful in this invention can also contain a significant proportion of one or more monoethylenically unsaturated monomers. The preferred monomers provide water-insoluble polymers when homopolymerized and are illustrated by acrylate and methacsylate esters, such as ethyl acrylate, butyl acrylate or the corresponding methacrylate. Other monomers which can be used are styrene, alkyl styrenes, vinyl toluene, vinyl acetate, vinyl alcohol, acrylonitrile, vinylidene chloride, vinyl ketones and the like.
Nonreactive monomers are preferred, those being monomers in which the single ethylenic group is the only group reactive under the conditions of polymerization. However, monomers which include groups reactive under baking conditions or with divalent anetal ions such as zinc ozide may be used in some situations, like hydroxyethyl acrylate.
Other illustrative monoethylenically unsaturated monomers useful in this invention include, for example, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, n-amyl , methacrylate, sec-amyl methacrylate, hexyl methacrylate, lauryl methacrylate, stearyl methacrylate, ethyl hexyl methacrylate, crotyl .
methaciylate, cinasmyl methacrylate, oleyl methacrylate, ricinoleyl methacrylate, hydroiy ethyl methacrylate, hydroay propyl methacrylate, vinyl propionate, vinyl butyrate, vinyl tent-butyrate, vinyl caprate, vinyl stearate, vinyl laurate, vinyl oleate, vinyl methyl ether, vinyl ethyl ether, vinyl n-propyl ether, vinyl iso-propyl ether, vinyl n-butyl ether, vinyl iso-butyl ether, vinyl iso-octyl ether, vinyl phenyl ether, a-chlorovinyl phenyl ether, vinyl ~-naphthyl ether, methacryonitrile, acrylamide, methaerylamide, N-alkyl acrylamides, N-aryl acrylamides, N-vinyl pyrrolidone, N-vinyl-3-morpholinones, N-vinyl-oxazolidone, N-vinyl-imidazole and the like including mixtures thereof.
The macromonomers useful in this invention can be represented by the formula:

R1-(OR2 )z R3-C=CR5R6 ( I ) wherein:
Rl is a monovalent residue of a substituted or unsubstituted complex hydrophobe compound;
each R2 is the same or different and is a substituted or unsubstituted divalent hydrocarbon residue;
R3 is a substituted or unsubstituted divalent hydrocarbon residue;
R4, R5 and R6 are the same or different and are hydrogen or a substituted or unsubstituted monovalent hydrocarbon residue; and z is a value of 0 or greater.
The macromonomer compounds useful in this invention can be prepared by a number of conventional processes, except for inclusion of the complez hydrophobe compounds described herein.
' Illustrative processes are described, for example, in U.S. Patent Nos.
4,514,552, 4,600,761, 4,569,965, 4,384,096, 4,268,641, 4,138,381, 3,894,980, 3,896,161, 3,652,49?, 4,509,949, 4,226,754, 3,915,921, 3,940,351, 3,035,004, 4,429,097, 4,421,902, 4,167,502, 4,764,554, 4,616,074, 4,464,524, 3,657,175, 4,008,202, 3,190,925, 3,794,608, 4,338,239, 4,939,283 and 3,499,876. Other macromonomer compounds which may be useful in this invention include complex hydrophobe-bearing oligomers disclosed in U.S.
Patent No. 5,739,378.
Illustrative substituted and unsubstituted divalent hydrocarbon residues represented by R2 in formula I above include those described for the same type of substituents in formulae (i) and (ii) below. Illustrative substituted and unsubstituted monovalent hydrocarbon residues represented by R4, R5 and R6 in formula I
above include those described for the same type of substituents in formulae (i) and (ii) below.
nlustrative R3 substituents include, for example, the organic residue of ethers, esters, urethanes, amides, areas, urethanes, anhydrides and the like including mixtures thereof. The R3 substituent can be generally described as a 'linkage" between the complex hydrophobe-bearing surfactant or alcohol, and the unsaturation portion of the macromonomer compound. Preferred linkages include the following: urethane linkages from the reaction of an isocyanate with a hydroxyl-bearing surfactant; urea linkages from the reaction of an isocyanate with an amine-bearing surfactant;
unsaturated esters of surfactants such as the esterification product of a surfactant with an unsaturated carboxylic acid or an unsaturated anhydride; unsaturated esters of alcohols; esters of - ethyl acrylate oligomers, acrylic acid oligomers, and allyl-containing oligomers; half esters of surfactants such as those made by the reaction of a surfactant with malefic anhydride; unsaturated ethers prepared by reacting vinyl benzyl chloride and a surfactant or by ,,,.-. WO 93/24543 PGT/US93/04865 reacting an allyl glycidyl ether with a surfactant, alcohol, or carborylic acid.
The oryalkylene moieties included in the macromonomer compounds (I) may be homopolymers or block or random copolymers of straight or branched alkylene odes.
Mixtures of alkylene odes such as ethylene oxide and propylene ogde may be employed. It is understood that each R2 group in a particular substituent for all positive values of z can be the same or different. While ethylene oride is preferred, it has been observed that large amounts of ethylene ode may have a detrimental effect on the thermal and/or dilution stability of the thickened AAF.
The complex hydrophobe compounds having at least one active hydrogen useful in preparing the macromonomer compounds useful in this invention can be represented by the formula:
Rl_(O-CH2)a R3-(OR4)x-(OR5)y OR6 R2-(O-CHZ )b (i) wherein Rl and R2 are the same or different and are hydrogen or a substituted or unsubstituted monovalent hydrocarbon residue, Rg is a substituted or unsubstituted divalent or trivalent hydrocarbon residue, each Rel is the same or different and is a substituted or unsubstituted divalent hydrocarbon residue, each R5 is the same or different and is a substituted or unsubstituted divalent hydrocarbon residue, R6 is hydrogen, a substituted or unsubstituted monovalent hydrocarbon residue or an ionic substituent, a and b are the same or different and are a value of 0 or 1, and a and y are the same or different and are a value of 0 or greater; provided at least two of Rl, ~~1~~ 33~
R2, R3, R4, R5 and R6 are a hydrocarbon residue having greater than 2 carbon atoms in the case of R1, R2 and R6 or having greater than 2 pendant carbon atoms in the case of R3, R4 and R5.
Other complex hydrophobe compounds having at least one active hydrogen useful in preparing the macromonomer compounds useful in this invention can be represented by the formula:
R7-(OCH2)d-R~-(OR10)i-OR11 I
R'15 (ii ) I
R8-(OCHZ)e R,12-(OR13)g OR14 wherein R7 and Rg are the same or different and are hydrogen or a substituted or unsubstituted monovalent hydrocarbon residue, R11 and R14 are the same or different and are hydrogen, a substituted or unsubstituted monovalent hydrocarbon residue or an ionic substituent, Rg and R12 are the same or different and are a substituted or unsubstituted divalent or trivalent hydrocarbon residue, each R10 is the same or different and is a substituted or unsubstituted divalent hydrocarbon residue, each R13 is the same or different and is a substituted or unsubstituted divalent hydrncarbon residue, R15 is a substituted or unsubstituted divalent hydrocarbon residue, d snd a are the same or different and are a value of 0 or 1, and f and g are the same or different and are a value of 0 or greater;
provided at least two of R7, Rg, Rg, R10~ R11~ R12~ R13~ R14 ~d R15 are a hydrocarbon residue having greater than 2 carbon atoms in the case of R7, Rg, R11 and R14 or having greater than 2 pendant carbon atoms in the case of Rg, R10, R12~ R13 ~d R15.
Illustrative substituted and unsubstituted monovalent hydrocarbon residues contain from 1 to about 50 carbon atoms or ,..,, WO 93/24543 PGT/US93/04865 ~I3~~i~~

greater and are selected from alkyl radicals including linear or branched primary, secondary or tertiary alkyl radicals, such as methyl, ethyl, n-propyl, isopropyl, amyl, sec-amyl, t-amyl, 2-ethylheayl and the like; aryl radicals such as phenyl, naphthyl and the like; arylalkyl radicals such as benzyl, phenylethyl, tri-phenylmethylethane and the like; alkylaryl radicals such as octylphenyl, nonylphenyl, dodecylphenyl, tolyl, gylyl and the like; and cycloalkyl radicals such as cyclopentyl, cyclohezyl, cyclohexylethyl and the like. The permissible hydrocarbon residues may contain fluorine, silicon, or other non-carbon atoms.
Preferably, the substituted and unsubstituted hydrocarbon residues are selected from alkyl and aryl radicals which contain from about 1 to 30 carbon atoms or greater. More preferably, the alkyl radicals contain from 1 to 18 carbon atoms, while the aryl, arylalkyl, alkylaryl and cycloslkyl radicals preferably contain from 6 to 18 carbon atoms or greater.
In a preferred embodiment of this invention, Rl, R2, R7 and R8 can individually be a hydrocarbon radical represented by the formula:
Rls-(OCH2)h R18- (iii) R17-(OCH2)i wherein Rlg and R17 are as defined for Rl, R2, R7 and Rg above, h and i are the same or different and are a value of 0 or 1, and Rlg is as defined for R3 above. For compounds represented by formulae (i) and (ii), it is understood that each formula (iii) radical in a given compound may be the same or different and the Rlg and/or R17 groups may themselves be a formula (iii) radical to provide complex PGT/US93/04865 ..~

hydrophobes of a dendritic or of a cascading nature as described below. Further, R.~, R5, Rl0 and R13 can individually be a hydrocarbon radical represented by the formula:
-CIi[(ORlg)jOR20]- (iv) wherein Rlg is as defined for R4, R5, R,10 and R13 above, R20 is as defined for R6, Rll a~ R14 above, and j is a value of 0 or greater.
Illustrative ionic substituents for fts, Rll, R14 ~d R20 include cationic and anionic substituents such as sulfates, sulfonates, phosphates and the like. R6, Rll, R14 and R2p may preferably be an organic residue containing 1 or more hydroxyls or nitrogen derivatives or epodes or other reactive groups which may or may not contain unsaturation.
Other illustrative terminal groups which are described by R6, Rll, R14 ~d R20 ~~ude, for example, hydrocarbon residues which may contain allylic or vinylic unsaturation, acrylic or methacxylic functionality, styryl or alpha-methylstyryl functionality, and the like, such as the reaction product between the terminal alcohol (R~, Rll, R14 ~d R20 = H) ~d glycidyl methacrylate, isocyanatoethyl methacrylate, alpha, alpha-dimethyl-m-isopropenyl benzyl .isocyanate (m-TMI), and the like. Other examples of terminal groups may include hydrocarbon residues of alkyl, aryl, aralkyl, alkaryl, and cycloalkyl radicals which may or may not be substituted with one or more of the following: hydroxyl, carboxyl, isocyanato, amino, mono- or disubstituted amino, quaternary ammonium, sulfate, sulfonate, phosphate, epoxy, and the like and may or may not contain other non-carbon atoms including silicon or fluorine. Also included can be divalent silozy radicals. Other nonhydrocarbon terminal groups may include sulfates, phosphates, and the like.
Illustrative divalent hydrocarbon residues represented by R3, R4, R5, Rg, R10, R12~ R13~ R15~ R18 ~d R19 in the above ,.-, WO 93/24543 PGT/US93/04865 2~.3~~32 formulae include substituted and unsubstituted radicals selected from alkylene, -alkylene-oay-alkylene-, -arylene-oay-arylene-, arylene, alicyclic radicals, phenylene, naphthylene, -phenylene-(CH2)m(Q~(CH2)m-phenylene- and -naphthylene-(CH2)m(Q)n(CH2~-naphthylene- radicals, wherein fa individually represents a substituted or unsubstituted divalent bridging group selected from -CR21R22-. -O-. -S-. -NR23-~ -~24R25- ~d -CO-, wherein R21 and R22 individually represent a radical selected from hydrogen, alkyl of 1 to 12 carbon atoms, phenyl, tolyl and anisyl; R23, R24 and R25 individually represent a radical selected from hydrogen and methyl, and each m and n individually have a value of 0 or 1.
More specific illustrative divalent radicals represented by R3, R4, R5, R9~ R10~ R12~ R13~ R15, R18 and Rlg include, e.g., 1,1-methylene, 1,2-ethylene, 1,3-propylene, 1,6-herylene, 1,8-octylene, 1,12-dodecylene, 1,4-phenylene, 1,8-aapthylene, 1,1'-biphenyl-2,2'-diyl, 1,1'-binaphthyl-2,2'-diyl, 2,2'-binaphthyl-1,1'-diyl and the like. The alkylene radicals may contain from 2 to 12 carbon atoms or greater, while the arylene radicals may contain from 6 to 18 carbon atoms or greater. Preferably, R3, R4, R5, Rg, R10, R12~ R13~ R15~ R18 ~d R19 are an alkylene or arylene radical. The permissible divalent hydrocarbon residues may contain fluorine, silicon, or other non-carbon atoms.
Illustrative trivalent hydrncarbon residues represented by R3, Rg, R12 and Rlg in the above formulae include substituted and unsubstituted radicals selected from \ \ \
CH-, C(R2g~-, CR27-/ / /
and the like, wherein R2g is a substituted or unsubstituted monovalent hydrocarbon residue as described herein and R27 is a substituted or unsubstituted divalent hydrocarbon re~due as described herein.

WO 93/24543 PGT/US93/04865 ._ ~13~6~~
- is -Of course, it is to be further understood that the hydrocarbon residues in the above formulae may also be substituted with any permissible subatituent. Illustrative aubstituents include radicals containing from 1 to 18 carbon atoms such as alkyl, aryl, aralkyl, slkaryl and cycloalkyl radicals; alkoxy radicals; silyl radicals such as -Si(R2g)3 and -Si(OR2g)3, amino radicals such as -N(R28)2; aryl radicals such as -C(O)R28; acyloxy radicals such as -OC(O)R2g; carbonyloay radicals such as -COOR2g; amido radicals such as -C(O)N(R2g)2 and -N(R2g)COR2g; sulfonyl radicals such as -S02R2g; sulfinyl radicals such as -SO(R2g)2; thionyl radicals such as -SR2g; phosphonyl radicals such as -P(O)(ft2g)2; as well as halogen, nitro, cyano, trifluoromethyl and hydroxy radicals and the like, wherein each R2g can be a monovalent hydrocarbon radical such as alkyl, aryl, alkaryl, aralkyl and cycloalkyl radicals, with the provisos that in amino substituents such as -N(R2g)2, each R2g taken together can also compromise a divalent bridging group that forms a heterocyclic radical with the nitrogen atom, in amido aubstituents such as -C(O)N(R,28)2 ~d -N(R2g>COR2g, each R2g bonded to N can also be hydrogen, and in phosphonyl substituents such as -P(O)(R2g)2, one R2g can by hydrogen. It is to be understood that each R2g group in a particular aubstituent may be the same or different.
Such hydrocarbon substituent radicals could possibly in turn be substituted with a permissible aubatituent such as already herein outlined above.
Preferred slkylene ozides which can provide random or block oayalkylene units in the complex hydrophobe compounds represented by formulae (i) and (ii) include alkylene o~ddes such as ethylene oxide, propylene o~de,1,2-butylene ode, 2,3-butylene ode, 1,2- and 2,3-pentylene oride, cycloheaylene o~de,1,2-hexylene o~dde, 1,2-octylene oride, 1,2-decylene oxide, and higher alpha-olefin epoxides; epozidized fatty alcohols such as epo~dized soybean fatty alcohols and epo~dized linseed fatty alcohols; aromatic epo~ddes such as styrene oxide and 2-methyl styrene oxide; and hydroxy- and halogen-substituted alkylene odes such as glycidol, epichlorohydrin and epibromohydrin. The preferred alkylene oxides are ethylene oxide and propylene oxide. Also included can be hydrocarbon residues from substituted and unsubstituted cyclic esters or ethers such as oxetane and tetrahydrofuran. It is understood that the compounds represented by formulae (i) and (ii) herein can contain random and/or block oxyalkylene units as well as mixtures of oxyalkylene units. It is further understood that each R.4, R5~ R10~ R13 ~d R19 ~'oup in a particular substituent for all positive values of x, y, z, f, g and j respectively can be the same or different.
The values of x, y, z, f, g and j are not narrowly critical and can vary over a wide range. For example, the values of x, y, z, f, g and j can range from 0 to about 200 or greater, preferably from about 0 to about 100 or greater, and more preferably from about 0 to about 50 or greater. Any desired amount of alkylene oxide can be employed, for example, from 0 to about 90 weight percent or greater based on the weight of the complex hydrophobe compound.
Referring to the general formulae (i) and (ii) above, it is appreciated that when R1, R2, R7 andlor R8 are a hydrocarbon residue of formulae (iii) above, the resulting compound may include any permissible number and combination of hydrophobic groups of the dendritic or cascading type. Such compounds included in the above general formulae should be easily ascertainable by one skilled in the art. Illustrative complex hydrophobe compounds having at least one active hydrogen useful in this invention and processes for preparation thereof are disclosed in U.S. Patent No. 5,292,843.
In a preferred embodiment of this invention, the structure shown in formula (iii) can be a residue of the reaction product between epichlorohydrin and an alcohol, including those VI~O 93/24543 PCT/US93/04865 ,.., alcohols whose residues can be described by formula (iii), or a phenolic, or a mixture thereof. The structures which result can be described as complex hydrophobes of a dendritic or of a cascading nature. Pictorially, they can be described as shown below:
Preferred macromonomer compounds useful in this invention include those represented by the formulae:
R1- (OR2)z-OC(O~-NH C(CH3)2 C(CH3) =CH2 R°
R1- (OR2)z- CH CHCH OCH C= CH

(OR19)jOH
Ra R1-(OR2)z ~(O~ C= ~2 wherein Rl, R2, R4~ R19~ Z ~d j are as defined herein.
A preferred polymeric thickener of this invention conforms to the formula WO 93/24543 PGT/US93/0~4865 CH3 i H3 (~M
I
CHZ - C CH2 - i H CH2-C
C O C O
OH O
CH2 Y ~3- i -CH3 NH

C= O
O
iH2 i H2 P
R
Z
The preferred ranges are as follows: acid monomer X is 10-40°!0, co-polymerizable non-associative monomer Y is 10-50°!0, associative monomer Z is 5-30°k with p equal to 20-80 moles of ethozylation (or propoaylation). The hydrophobe ft can be an alkaryl, such as nonylphenol or dinonylphenol or may have the following structure:

Rl-O-CH2 I
CH -I

where Rl and RZ are as previously defined.
The macromonomer compounds useful in this invention can undergo further reactions) to afford desired derivatives thereof.
Such permissible derivatization reactions can be carried out in accordance with conventional procedures known in the art.
Illustrative derivatization reactions include, for example, esterification, etherification, alkogylation, amination, alkylation, hydrogenation, dehydrogenation, reduction, acylation, condensation, carboaylation, oxidation, silylation and the like, including permissible combinations thereof. This invention is not intended to be limited in any manner by the permissible derivatization reactions or permissible derivatives of macromonomer compounds.
More particularly, the hydroxyl-terminated macromonomer compounds of this invention can undergo any of the known reactions of hydroxyl groups illustrative of which are reactions with acyl halides to form esters; with ammonia, a nitrite, or hydrogen cyanide to form amines; with alkyl acid sulfates to form disulfates; with carborylic acids and acid anhydrides to form esters and polyesters; with alkali metals to form salts; with ketenes to form esters; with acid anhydrides to form carbo~cylic acids; with oxygen to form aldehydes and carboxylic acids; ring-opening reactions with lactones, tetrahydrofuran; dehydrogenation to form aldehydes, isocyanates to form urethanes, and the like.
The monoethylenically unsaturated macromonomer component is subject to considerable variation within the formula presented previously. The essence of the maromonomer is a complex hydrophobe carrying a polyethoxylate chain (which may include some polypropoaylate groups) and which is terminated with at least one hydroay group. When the hydroay-terminated polyethoxylate complex hydrophobe used herein is reacted with a monoethylenically unsaturated monoisocyanate, for example, the result is a monoethylenically unsaturated urethane in which a complex hydrophobe polyethoxylate structure is associated with a copolymerizable monoethylenic group via a urethane linkage.
The monoethylenically unsaturated compound used to prnvide the monoethylenically unsaturated macromonomer is subject to wide variation. Any copolymerizable unsaturation may be employed, such as acrylate and methacrylate unsaturation. One may also use allylic unsaturation, as provided by allyl alcohol.
These, preferably in the form of a hydroay-functional derivative, as is obtained by reacting a C2-C4 monoepogde, like ethylene o~dde, propylene ode or butylene oride, with acrylic or methacrylic acid to form an hydrory ester, are reacted in equimolar proportions with an organic compound, such as toluene diisocyanate or isophorone diisocyanate. The preferred monoethylenic monoisocyanate is styryl, as in alpha, alpha-dimethyl-m-isopropenyl benzyl isocyanate. Other suitable organic compounds include, for example, monoethylenically unsaturated esters, ethers, amides, areas, anhydrides, other urethanes and the like.
The polymers useful in this invention can be prepared via a variety of polymerization techniques known to those skilled in the art. The technique of polymerization influences the microstructure, monomer sequence distribution in the polymer backbone and its molecular weight to influence the performance of the polymer. Illustrative polymerization techniques include, for example, conventsonal and staged emulsion polymerization via batch, semi-continuous, or continuous processes, micellar polymerization, inverse emulsion polymerization, solution polymerization, non-aqueous dispersion polymerization, interfacial ~~.3~~'~
WO 93/?A543 PGT/US93/04865 polymerization, emulsion polymerization, suspension polymerization, precipitation polymerization, addition polymerizations such as free radical, anionic, cationic or metal coordination methods, and the like.
The thickeners useful in this invention possess structural attributes of two entirely different types of thickeners (those which thicken by alkali swelling or solubilization of a polymeric entity, and those which thicken due to association), and this may account for the superior thickening properties which are obtained herein. It is believed, however, that for purposes of . providing the non-Newtonian rheology which is critical to the performance of these thickeners in AAFs, it is the association among hydrophobe groups (and the wind shear-induced disassociation) which is the predominant mechanism.
The aqueous emulsion copolymerization is entirely conventional. To obtain an estimate of thickening e~ciency, the product can be diluted with water to about 1°6 solids content and then neutralized with alkali. The usual alkali is ammonium hydroxide, but sodium and potassium hydroxide, and even amines, like triethylamine, may be used for neutralization. The neutralized product dissolves in the water to provide an increase in the viscosity.
In the normal mode of addition, the unneutralized thickener is added to a fluid and then neutralized. This facilitates handling the thickener because it has a lower viscosity before neutralization. This procedure also makes more water available for formulation.
The polymers useful in this invention are typically produced by conventional aqueous emulsion polymerization techniques, using appropriate emulsifiers for emulsifying the monomers and for maintaining the polymer obtained in a suitable, dispersed condition. Commonly used anionic surfactants such as sodium lauryl sulfate, dodecylbenzene sulfonate and ethorylated fatty ~"" WO 93/24543 PCT/US93/04865 ~~~ss~~
alcohol sulfate can be used as emulsifiers. The emulsifier may be used in a proportion of 0.5 to 69b of the weight monomers.
Preferably, water-soluble initiators such as alkali metal or ammonium persulfate are used in amounts from 0.01 to 1.0°l0 on the weight of monomers. A gradual addition thermal process employed at temperatures between 60°C to 100°C is preferred over redoz systems.
The polymerization system may contain small amounts (0.01 to 5°b by weight, based on monomer weight) of the chain transfer agent mercaptans such as hydroayethyl mercaptan, 8-mercaptopropionic a~d and alkyl mercaptans containing from about 4 to 22 carbon atoms, and the like. The use of mercaptan modifier reduces the molecular weight of the polymer and therefore its thickening efficiency.
The polymers useful in this invention may further be modified by introducing an amount of component (D), namely, one or more polyethylenically unsaturated copolymerizable monomers effective for crosslinking, such as diallylphthalate, divinylbenzene, allyl methacrylate, trimethylol propane triacrylate, ethyleneglycol diacrylate or dimethacrylate, 1,&heaanediol diacrylate or dimethylacrylate, diallyl benzene, and the like. Thus, from about 0.05 or less to about 20~ or greater of such polyethylenically unsaturated compound based on total weight of monomer may be included in the composition forming the polymer. The resulting polymers are either highly branched or in the form of three-dimensional networks. In the neutralized salt form, those networks swell in an aqueous system to act as a highly e~cient thickener.
Other illustrative polyethylenically unsaturated monomers useful in this invention include, for euample, any copolymerizable compound which contains two or more nonconjugated points of ethylenic unsaturation or two or more nonconjugated vinylidene groups of the structure, CH2=C=, such as divinyltoluene, trivinylbenzene, divinylnaphthalene, trimethylene glycol diacrylate or dimethacrylate, 2-ethylhexane-1,3-dimethyacrylate, divinylxylene, divinylethylbenzene, divinyl ether, divinyl sulfone, allyl ethers of polyhdric compounds such as of glycerol, pentaerythritol, sorbitol, sucrose and resorcinol, divinylketone, divinylsulfide, allyl acrylate, diallyl maleate, diallyl fumarate, diallyl phthalate, diallyl succinate, diallyl carbonate, diallyl malonate, diallyl oxalate, diallyl adipate, diallyl sebacate, diallyl tartrate, diallyl silicate, triallyl tricarbaliylate, triallyl aconitate, triallyl citrate, triallyl phosphate, N,N-methylenediacrylamide, N,N'-methylenedimethacrylamide, N,N'-ethylidenediacrylamide and 1,2-di-(a-methyl-methylenesulfonamide)-ethylene.
Other polymers which may be useful in this invention include those polymers disclosed in U.S. Patent Nos. 5,426,182, 5,461,100, 5,292,828 and 5,739,378. Polymers having a backbone containing urethane units are within the scope of the invention.
The polymer may be utilized in a variety of ways to provide the thickener or thickened compositions of this invention.
For example, the polymer, while in aqueous dispersion or dry form, may be blended into an aqueous system to be thickened followed by addition of a neutralizing agent. Alternatively, the polymer may first be neutralized in aqueous dispersion form and then blended with the _ aqueous system. Preferably, if co-thickening by a surfactant (as discussed below) is desired, the components are separately blended (as dry components or as dispersions or slurries) into an aqueous dispersion to be thickened, followed by the neutralization step.

~~ WO 93/24543 PGT/US93/04865 Although aqueous concentrates of the polymer in acid form and the surfactant may be formed and added to an aqueous dispersion to be thickened as needed, followed by neutralization, such concentrates tend to be too viscous for easy handling. It is nevertheless possible to prepare either a dry blend or an aqueous, high solids composition which is sufficiently low in viscosity as to be pumpable or pourable, and then to further thicken the admixture by addition of an alkaline material.
The polymer thickener may be provided in a dry state in number of ways. For ezample, the unneutralized polymer may be spray or drum dried and, if desired, blended with a surfactant co-thickener. However, it is also possible to spray dry or otherwise dehydrate the neutralized polymer thickener, and then reconstitute the aqueous thickener dispersion at a future time and place by agitation in a aqueous medium, provided the pH of the dispersion is maintained at pH 7 or higher.
The more usual method of application of the dispersion of this invention for aqueous thickening is to add the aqueous dispersion of the polymer to the medium to be thickened and, after miring, to introduce an alkaline material to neutralize the acid. The major portion of the thickening effect is obtained in a few minutes upon neutralization. In the presence of high concentrations of electrolytes, the viscosity development may take much longer. This method of applying a polymer to an aqueous system before neutralization enables one to handle a high solids thickener in a non-viscous state, to obtain a uniform blend, and then to convert to a highly viscous condition by the simple addition of an alkaline material to bring the pH of the system to 7 or above.
The aqueous solutions thickened with the neutralized polymers of this invention ezhibit good viscosity stability even at a pH
as high as 13.

The polymer may be used to thicken compositions under acidic conditions in the presence of a relatively large amount of surfactants wherein the thickened composition, for example, an aqueous system, has a pH below ?, even as low as 1.
An enhancement of thickening (herein termed "co-thickening") can result upon the addition of a surfactant to an aqueous system containing the polymer of this invention, when the polymer is neutralized. In some cases the thickening can be enhanced up to about 40 times the viscosity afforded by the neutralized polymer alone. A wide range of surfactants may be used. Although trace amounts of surfactant may be residually present from the polymerization of the monomers comprising the polymer (for ezample, whatever may remain of the about 1.5 weight percent surfactant on monomers), such amounts of surfactant are not alone believed to result in any significant co-thickening.
On the basis of an aqueous system containing about 0.1 to 5gb by weight of polymer solids, a useful amount of surfactant for optimum co-thickening is about 0.1 to l.Oqb by weight of the total system. As indicated, the amounts of polymer and surfactant cothickener may vary widely, even outside these ranges, depending on polymer and surfactant type and other components of the aqueous system to be thickened. However, the co-thickening can reach a ma~mum as surfactant is added and then decreases as more surfactant is added. Hence, it may be uneconomical to employ surfactant in amounts outside the stated concentrations and polymer/surfactant ratios, but this can be determined in a routine manner in each case.
The preferred method of application of the polymer and the surfactant for aqueous thickening is to add in any sequence the polymer and the surfactant to the medium to be thickened and, after mining, to introduce an alkaline material to neutralize the acid.
This method of applying polymer and surfactant to an aqueous system before neutralization enables one to handle a high solids thickener in a non-viscous state, to obtain a uniform blend, and then to convert to a highly viscous condition by the simple addition of an alkaline material to bring the pH of the system to 7 or above.
However, the polymer in the aqueous system may also be neutralized before addition of the surfactant.
The surfactants which may be used preferably include nonionics and anionics, singly or in combination, the selection necessarily depending upon compatibility with other ingredients of the thickened or thickenable dispersions of this invention. Cationic and amphoteric surfactants may also be used provided they are compatible with the polymer and other ingredients of the aqueous system, or are used in such small amounts as not to cause incompatibility.
Suitable anionic surfactants that may be used include the higher fatty alcohol sulfates such as the sodium or potassium salt of the sulfates of alcohols having from 8 to 18 carbon atoms, alkali metal salts or amine salts of high fatty acid having 8 to 18 carbon atoms, and sulfonated alkyl aryl compounds such as sodium dodecyl benzene sulfonate.
Examples of nonionic surfactants include alkylphenoaypolyethoayethanols having alkyl groups of about 7 to 18 carbon atoms and about 9 to 40 or more oayethylene units such as octylphenoay- polyethoayethanols, dodecylphenoaypolyethory-ethanols; ethylene oride derivatives of long-chain carboxylic acids, such as lauric, myristic, palmitic, oleic; ethylene oxide condensates of long-chain alcohols such as lauryl or cetyl alcohol, and the like.
Easmples of cationic surfactants include lauryl pyridinium chloride, octylbenzyltrimethyl- ammonium chloride, dodecyltrimethylammonium chloride condensates of primary fatty amines and ethylene oxide, and the like.

The foregoing and numerous other useful nonionic, anionic, cationic, and amphoteric surfactants are described in the literature, such as McCutcheon's Detergents & Emulsifiers 1981 Annual, North America Edition, MC Publishing Company, Glen Rock, NJ 07452, U.S.A.
In general, solvents (or mixtures of solvents, other organics and volatiles) can be used to manipulate the viscosity of polymer-containing systems. In the examples herein, it is interesting to note how mineral spirits act like co-thickener, and how the water solubility of the other solvent influences how much mineral spirits can be added before the solution separates into a two phase system.
The amount of the polymer that may be dissolved in any given aqueous composition may fall within a wide range depending on the particular viscosity desired.
Thus, although any effective amount of the polymer may be employed for dissolution, typically from about 0.05 to about 20%, preferably from about 0.1 to about 5%, and most preferably from about 0.1 to about 3% by weight, based on the weight of the final aqueous composition including polymer is used.
In addition to the macromonomer-containing polymer that functions as a thickener for the fluid, the glycol-based fluid may also contain small amounts of other functional ingredients, such as corrosion inhibitors, surfactants, anti-oxidants, stabilizers and the like. These components are ordinarily present in individual amounts of less than about 2 weight %, typically in the range of about 0.01-1 weight %a for each component.
The macromonomer-containing polymer used as a thickener in the glycol-based fluids of this invention is responsible for their advantageous properties as aircraft anti-icing fluids. The macromonomer-containing polymer is employed in amounts that effect a significant modification in the rheological properties of the ~I3663~

glycol-based fluids. The anti-icing glycol-based fluids of this invention do not exhibit Theological properties associated with conventional Newtonian fluids.
The anti-icing fluids of this invention, furthermore, should be distinguished from conventionally thickened anti-icing fluids because they operate by an associative mechanism. The glycol-based deicingJanti-icing fluid of U.S. Pat. No. 4,358,389, thickened with a crosslinked polyacrylate and optionally aanthan gum, is exemplary of such prior art fluids.
When applied to exposed aircraft surfaces, the fluid is su~ciently viscous and/or tacky and has suffcient structure, i.e., gel-like structure, that it tends to cling or adhere to the surfaces, even non-horizontal surfaces. A coating of suffcient thickness is formed to prevent the adherence or accretion of ice, snow, sleet, freezing rain, frost or the like on such surfaces while the aircraft is stationary or ta~ding on the ground. Once the aircraft begins its takeoff run, however, the fluid readily flows off the aircraft surfaces under the influence of wind shear, before lift-off occurs.
Consequently, there are no appreciable amounts of fluid present on the aircraft surfaces prior to the pilot's rotation of the aircraft to initiate liftoff from the runway and subsequently when the aircraft has become airborne. This result is highly desirable since a residual layer of anti-icing fluid on the airfoil surfaces, like traces of snow, ice, freezing rain or frost, can adversely affect the lift performance characteristics of the airfoil.
It should be noted that without the presence of the macromonomer-containing polymer thickener employed in this invention, the aqueous glycol fluid would exhibit relatively low viscosity and would tend to drain off any non-horizontal surfaces under the influence of gravity, leaving an insu~cient film behind to function effectively as as anti-icing agent over an extended period of time.

The macromonomer-containing polymer thickener is employed in this invention in an amount that increases the viscosity and/or tackiness of the glycol-based fluid and, moreover, gives it a gel-like physical structure under zero shear or very low shear conditions.
The amount of macromonomer-containing polymer thickener in the aqueous glycol-based fluid should be less than about weight °k, based on the weight of the fluid. The amount of thickener is preferably within the range of about 0.05-3 weight °!o, and more preferably within the range of from about 0.1-1 weight %.
When the glycol-based fluid containing these amounts of macromonomer-containing polymer thickener is applied to the ezposed surfaces of a stationary aircraft, the gravity-induced flow of the fluid coating from non-horizontal surfaces (i.e., inclined, vertical, or the like) is greatly retarded or stopped for appreciable periods of time.
The thickened anti-icing fluid produces a coating, when applied to aircraft surfaces by conventional methods, that imparts anti-icing or antifreeze characteristics to the treated aircraft surface and minimizes the adherence or accretion of ice, snow, sleet, etc., on or to the exposed aircraft surfaces.
The apparent viscosity produced by the macromonomer-containing polymer thickener in the glycol-based fluids of this invention is desirably in the range of about 1,000-20,000 mPa.s, preferably 2,000-8,000 mPa.s, as measured with a Brookfield LVT
viscometer at 0.3 rpm and 0°t 1°C using a ~#31 spindle.
Once the aircraft begins its takeoff run, but prior to rntation and liilr-off, the impact of the relative wind on the airfoils and other exposed surfaces treated with anti-icing fluid and also mechanical vibration in the wings and other aircraft surfaces causes sufficient shear force on the anti-icing fluid to thin it so that it .f~ WO 93/24543 PGT/US93/04865 behaves like a relatively non-viscous material. It then readily drains off the airfoils and other treated aircraft surfaces.
During the aircraft's takeoff run and prior to rotation (the point at which airfoil lift is suffi~ent for the pilot to effect lift-off and fly the aircraft off the ground), the wind shear from the relative wind changes the rheological behavior of the fluid of this invention, causing substantial shear thinning and an appreciable decrease in its apparent viscosity that allows it to flow freely off the airfoil surfaces. The airfoil surfaces are thus not only kept free of any adhering i.e., snow or the like, but also free of thickened fluid, both of which could have a deleterious effect on the airfoil lift performance.
The macromonomer-containing polymer is used as the primacy thickener in the anti-icing fluid of this invention. As noted above, however, minor amounts of other ingredients, including other thickeners, may also be present to provide additional thickening or gelling functionality or modify rheological behavior. The macromonomer-containing polymer used as the essential thickening component desirably represents at least about 80 weight °k of the thickening components present; preferably, it represents in excess of about 90 weight Rto of the thickener employed.
The gel-forming macromonomer-containing polymers employed as thickeners in this invention exhibit the desired shear thinning characteristics described above, yet are resistant to pump and nozzle shear-induced degradation. This particular characteristic is important since anti icing fluids are typically applied using conventional ground-based deicing equipment which incorporates a pump driven spraying system. The macromonomer-containing polymer thickened aqueous glycol-based anti-icing fluids of this invention exhibit su~cient shear thinning to be readily pumpable in conveational aircraft ground deicing equipment.
The aqueous glycol-based fluids of this invention are primarily intended for use as anti-icing fluids for treating stationary 1 !

aircraft but may be used for aircraft and general deicing purposes as well, e.g., treating automobile or vehicle windshields and other exposed surfaces.
The following are rheology modifier design variables:
(i) the structure and concentration of the associative macromonomer, including: a) the size and structure of the hydrophobe; b) the moles of alkoxylation between hydrophobe and the double bond; c) the chemical nature of the bond between the alkoxylated portion and the reactive double bond (e.g., ester, ether, or urethane linkages);
and d) the structure of the double bond itself (acrylic, methacrylic, crotonic, styrenic, etc.);
(ii) the structure and concentration of acid monomer in the polymer (e.g., acrylic, methacrylic, crotonic, itaconic, etc.);
(iii) the structure and concentration of the non-associative monomer, including monomers that cross-link the polymer during polymerization (e.g., trimethylol propane triacrylate), and those that leave cross-linkable functionality in the associative polymer without crosslinking during polymerization (e.g., 2-hydroayethylacrylate); and (iv) the molecular weight of the polymer, as controlled by mercaptans during polymerization.
All of these parameters influence the fluid's steady shear viscosity profile, viscoelastic and eztensional properties, and thickening e~ciency. Parameters (ia) and (ib) control rheology by regulating the morphology, thermodynamics, and kinetics of the association junctions. Parameter (ic) controls the hydrolytic stability of the bond that connects the surfactants to the polymer backbone, as well as the ease (and cost) of the synthesis of the associative macromonomer. Parameter (id) controls the sequence of incorporation into polymer for the macromonomer, and controls the r- WO 93/Z4543 PCT/US93/04865 amount of reactor coagulum produced during polymerization, which determines the production viability of the polymer. Parameters (ii) and (iii) control the transition temperature (i.e., chain stiffness), hydrophobicity, and water solubility of the polymer backbone.
Because the viscosity of the fluid should not decrease significantly as water dilutes it (for improved hold-over time and water spray endurance), the association activity of the polymer should balance the loss in viscosity due to polymer dilution. Because the viscosity of the fluid should not increase significantly with drop in temperature, the hydrodynamic size of the polymer should decrease enough to compensate for the increase in viscosity of the ethylene glycol and water solvent mixture. (~iydrogen bonding among water molecules and ethylene glycol molecules doubles the viscosity of a 50/50 mixture of ethylene glycol and water as the temperature decreases from 20°C to 0°C.) The influence of water dilution and temperature change on the viscosity of model AAF's composed of 0.5°k polymer solutions in equal weight mixtures ethylene glycol and water was tested. The results are given in Table Q below.
The water dilution experiment is essentially a titration of the polymer containing glycol solution with water that is constructed such that concentration of polymer is 0.5~'o when the glycol concentration reaches 50°0. Compositions that contain less than 50°b water by weight correspond to the "dry-out experiment,"
that simulates the evaporation of water; compositions that contain more than 50°~b water ~rrespond to the water spray endurance test that simulates the e~'ect of freezing rain impinging on a treated aircraft waiting on the runway. The viscosity of the solution was measured as water was added to it. Whether or not the fluid viscosity is invariant to dilution depends on the moles of ethylene oxide in the macromonomer, the concentrations of associative macromonomer, and methacrylic acid in the polymer.

_g,ø_ The degree to which the viscosity of the model AAF
depends on temperature depends also on the structure of the associative polymer. The dependence of solution viscosity on polymer coil size and concentration are often expressed in terms of empirical master correlations of the form ~/~. _ ~c[~]), such as the Huggins equation:
~=1+c[~l+K'c2[r~)2+...
(1) where ~ is the viscosity of the polymer solution, ~ is the viscosity of the solvent, c[~J is a dimensionless coil volume, and the constant K' characterizes the first effects of polymer interaction on the viscosity.
The Huggins parameter K' is usually independent of polymer molecular weight for long polymer chains, and has a value of about 0.4 for polymers in good solvents without interaction effects, and a value of about 0.8 for polymers in theta solvents. Equations like Equation (1) often unify viscosity data over a broad range of molecular weights and concentration for a given dilute polymer-solvent system.
Because the solvent mixture of ethylene glycol and water increases in viscosity as temperature decreases, the contribution of the solvent to the overall viscosity of the solution can be excluded, and only the increment that the polymer contributes through its specific viscosity need be examined:

WO 93/24543 ~ ~ ~ PGT/US93/04865 w T LT1J T
' ~,~~ (2) - 1 Tref Tref The instrinsic viscosity [r~] depends on the hydrodynamic size of the polymer coil, which depends on polymer molecular weight, solvent quality, and temperature. Taking a ratio of intrinsic viscosity relative to that obtained at an arbitrary reference temperature Tref allows one to isolate the influence of temperature for a given molecular weight of polymer.
Temperature correlations for viscosity usually take the form of an Arrehnius type equation:

(3) R
T T~ f Tref where R, is the ordinary gas constant and AH the activation energy for a change in viscosity with respect to temperature. The activation energy for change provides a quantitative number to compare the influence of temperature to change the viscosity of an anti-icing fluid: if AH is zero, the viscosity of the solution changes exactly in the same way as the solvent does; if AH is greater than zero, then the polymer coil expands, and the solution viscosity increases as temperature increases; if AH ie less than zero, then the polymer coil WO 93/24543 ,~ PCT/US93/04865 --~-> ~~ ~ ~~3~3 contracts, and the solution viscosity decreases as temperature decreases. AH is determined by fitting the temperature dependence of the specific viscosity for 0.5°fo polymer solutions in a 50/50 ethylene glycol/water solvent mixture to equation (3) by a standard least squares method.
Whether or not the fluid viscosity is invariant to temperature depends on the concentration of associative macxomonomer in the polymer, the moles of ethylene oxide in the macromonomer, and the concentration of carboxylic moieties in the polymer. If a particular macromonomer-containing polymer structure is found to be unacceptably sensitive to dilution and/or thermal effects (which tend to be inversely related to each other), compensation may be attempted by altering the water solubility and glass transition temperature of the polymer backbone. Thus, for instance, ethyl acrylate may be partially replaced with methyl acrylate.
The co-thickening interaction of polymer thickener with nonionic surfactant can provide shear-thirming, yet nearly temperature invariant viscosity profile. In the past, this effect was achieved through formulation with anionic surfactants. Nonionic surfactant systems have the advantage of being able to use carbon steel tanks for storage purposes.
As used herein, the term "complex hydrophobe" is contemplated to include all permissible hydrocarbon compounds having 2 or more hydrophobe groups, e.g., bis-dodecylphenyl, bis-nonylphenyl, bis-octylphenyl and the like.
. For purposes of this invention, the term "hydrocarbon' is contemplated to include all permissible compounds having at least one hydrogen and one carbon atom. In a broad aspect, the permissible hydrocarbons include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and nonaromatic organic compounds, which can be substituted or unsubstituted.
As used herein, the term "substituted" is contemplated to include all permissible substituents of organic compounds unless otherwise indicated. In a broad aspect, the permissible substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and nonaromatic substituents of organic compounds. Illustrative substituents include, for example, alkyl, alkylosy, aryl, aryloay, hydrozy, hydroayalkyl, amino, aminoalkyl, halogen and the like in which the number of carbons can range from 1 to about 20 or more, preferably from 1 to about 12. The permissible substituents can be one or more and the same or different for appropriate organic compounds. This invention is not intended to be limited in any manner by the permissible substituents of organic compounds.
The invention is illustrated by certain of the following examples.
Preparation of 1.3-Bis(nonylnh~ enoay~-2-yronanol To a five neck, two liter, round bottom flask equipped with an addition funnel, thermometer, nitrogen dispersant tube, mechanical stirrer, and a decanting head with a water-cooled condenser were added 220 grams (1.00 mole) of nonylphenol and 250 milliliters of cycloheaane. The solution was then heated to refluz and 2.8 grams (1.3 weight °b based on nonylphenol) of potassium hydroxide in 10 milliliters of water was slowly added to the flask.
After essentially all the water was recovered in the decanting head (10 milliliters + 1 milliliter formed), 250.7 grams (0.91 mole) of nonylphenyl glycidyl ether was added dropwise. During the addition of the glycidyl ether, the reaction temperature was maintained between 60 and 80°C. After the addition was complete, the solution i a WO 93/?A543 ~z ~ 3 ~ ~ ~ ~ PGT/US93/04865 -...

was refluaed for four hours. The contents of the flask were then washed with a five percent aqueous solution of phosphoric acid, and the organic layer was separated from the water layer and washed twice with deionized water. The reaction mixture was then placed in a one liter round bottom flask, and the remaining cycloheaane and unreacted nonylphenol were recovered by distillation, first at atmospheric pressure, then under vacuum at 0.2 mm Hg. The kettle temperature was not allowed to exceed 180°C during the distillation to prevent discoloration of the product. The concentrated solution was then refiltered to give 425 grams of a pale-yellow liquid. End-group MW analysis gave a molecular weight of 506.8 (theoretical MW = 496.8). Ir and nmr spectra were identical to previously recorded spectra for the compound.
Ii~smpl~
~~~ration of ~ 3-Bis(nonvlnhprnxvl-2-~~ro~anol To a five neck, two liter round bottom flask, equipped with an addition funnel, thermometer, nitrogen dispersant tube, mechanical stirrer, and a decanting head with a water-cooled condenser, were added 300 milliliters of cycloheaane and 451.7 grams (2.05 mole) of nonylphenol. The solution was then heated to reflua and 58.9 grams (1.05 mole) of potassium hydrogde in 60 milliliters of water was slowly added via the addition funnel. After essentially all the water was recovered in the decanting head (60 milliliter + 19 milliliters formed), the reaction was cooled to 40°C, and 92.5 grams (1.00 mole) of epichlorohydrin was slowly added.
During the addition, the reaction temperature was maintained below 60°C by controlling the rate of epichlorohydrin addition. After all the epichlorohydrin was added, the solution was allowed to stir for one hour, and then brought to reflua for an additional three hours. The reaction mixture was then filtered under vacuum through a steam-jacketed Buchner funnel to remove the potassium chloride formed as a by-product. The filtration process was performed a total of three times to remove the majority of the salts. The reaction mixture was then placed in a one liter, round bottom flask, and the remaining cyclohexane and unreacted nonylphenol were recovered by distillation, first at atmospheric pressure, then under vacuum at 0.2 mm Hg. The kettle temperature was not allowed to exceed 180°C
during the distillation to prevent discoloration of the product. The concentrated solution was then refiltered to give 275 grams of a pale-yellow liquid. End-group MW analysis gave a molecular weight of 459.7 (theoretical MW = 496.8). Ir and nmr spectra were identical to previously recorded spectra for the compound.
To a 500 milliliter, stainless steel, high pressure autoclave was charged 200 grams (0.40 mole) of 1,3-bis(nonylphenoxy)-2-propanol, which contained a catalytic amount of the potassium salt of the alcohol as described in Example 1. After purging the reactor with nitrogen, the alcohol was heated to 130°C
with stirring, and 86.9 grams (2.0 moles of ethylene o~dde was added over a two hour period. The reaction temperature and pressure were maintained from 130°C to 140°C and 60 psig during the course of the reaction. After the addition of ethylene ode was complete, the reaction mv~ture was held at 140°C for an additional hour to allow all the ethylene ozide to cook out. The reaction nnizture was dumped while hot, under nitrogen, and neutralized with acetic acid to yield 285 grams of a pale-yellow liquid.

i a _40-~.~:"., "r eaa~ .,~1"hPnvl C'=lvcidvl ~~t,o,. fl..~i 5 Mole Fthoxvlatp of is(nony~g~y~-~~~anol To a five neck, one liter, round bottom flask equipped as in Example 1 was added 119.8 grams (0.17 mole) of the 5 mole ethozylate of 1,3 bis(nonylphenoay~2-propanol and 100 milliliters of cyclohezane. The mixture was refluxed (100°C) for one hour to remove residual water, and then cooled to 50°C under nitrogen to add 0.5 grams of BF3/Et20. Nonylphenyl glycidyl ether (46.0 grams, 0.17 mole) was then added to the flask over a one hour period, and the reaction was heated to reflux. After three hours at reflux, the reaction nnizture was transferred to a separatory funnel, while hot, and washed with a saturated aqueous solution of sodium bicarbonate. The organic layer was separated from the water layer, and washed twice with hot, deionized water. The washes were performed at 50°C to facilitate the separation of the two layers. The water and cyclohexane were then evaporated from the organic layer, under vacuum, to yield 145 grams of a pale-yellow, viscous liquid.
End-group molecular weight analysis gave a molecular weight of 880 (theoretical molecular weight = 993).
P~raration of Pol~ylrhpnol elvcidvl ether) To a 500 milliliter round bottom equipped with an overhead stirrer, nitrogen inlet, reflua condenser, additional funnel, and temperature controller was charged 1.9 grams of ethanol (22 mmoles) and 200 grams of cyclohexane. The solution was brought to 50°C. Once heated, 0.5 milliliters (4 mmoles) of BF3/Et20 was added using a 2 nn~7liliter syringe. Once the acid was added, 100.0 grams of nonylphenol glycidyl ether (362 mmoles) was added dropwise so as to ~~ WO 93/?A543 PGT/US93/04865 213~~32 maintain a reaction temperature of 45°C to 55°C. Once the glycidyl ether was added, the solution is refluaed for 3 hours, then cooled to about 50°C.
While hot (<60°C) the organic was transferred to a separatory funnel and was washed once with 100 milliliters of 5%
sodium bicarbonate solution. The aqueous layer was drained and the organic was washed two more times with 100 milliliter portions of deionized water. The aqueous layers were decanted and the organic was dried for at least 1 hour over magnesium sulfate. Once dry, the magnesium sulfate was filtered from the organic layer, which was stripped of solvent using a rotary evaporator. The final yield of viscous polymer was 100 grams. The GPC molecular weight was Mw = 2600 and the Mn =1700 based on monodisperse polystyrene standards.
To a 500 milliliter stainless steel Zipperclave was added 60.0 grams (0.035 moles based on an approximate molecular weight of 1700 gramlmole) of the resin prepared in Example 5 along with 0.5 gram of potassium hydrouide. The vessel was attached to an automated ethoaylation unit and was heated to 50°C. The vessel was continuously purged with nitrogen for 15 minu~,es and was then heated to 100°C where it was again continuously purged with nitrogen for another 15 minutes. The vessel was then heated to 140°C
and was given a series of 6 purges by pressuring the vessel up to 80 psi, and then venting. Once the venting process was complete, the vessel was pressured to 20 psi with nitrogen.
The ethylene oxide lines were opened to a pair of motor-controlled valves along with the main feed line on the Zipperclave.
The feed was continued and the vessel pressure was regulated at 55 psi and a temperature of 140°C. The automation was designed to i s 2'1~6~~2 _, hold the temperature and the pressure within safe operating limits while addition of ethylene o~dde proceeded through the motor-controlled valves. The feed was allowed to continue until 60.0 grams of ethylene ode (1.362 moles) was added based on a difference weight of the feed cylinder. After the feed was complete, the reaction was allowed to continue for 1 hour, after which the vessel was cooled to 60°C, purged 4 times with nitrogen to 80 psi and was dumped to a container. The final product yield was 115 grams with a theoretical yield of 120 grams. The GPC molecular weight of the product was Mw = 3550 and the MN = 2930 based on monodisperse polystyrene standards.
Pr'~n-soon of Polv(n nvl glvcidvl ether) To a 500 milliliter, round bottom flask equipped with an overhead stirrer, nitrogen inlet, reflua condenser, addition funnel, and temperature controller was charged 47.06 grams of phenol (500 mmoles) and 100 grams of toluene. The solution was brought to 50°C. Once heated,1.0 milliliter (8 mmoles) of BF3/Et20 was added using a 2 milliliter syringe. Once the acid was added, 68.18 grams of phenyl glycidyl ether (454 mmoles) was added dropwise so as to maintain a reaction temperature of 45°C to 55°C. Once the glycidyl ether was added, the solution was refluaed for 3 hours, then cooled to about 50°C.
While hot (<60°C) the organic was transferred to a separatory funnel and was washed once with 100 milliliters of 5°k sodium bicarbonate solution. The aqueous layer was drained and the organic was washed two more times with 100 milliliter portions of deionized water. The aqueous layers were decanted and the organic was dried for at least 1 hour over magnesium sulfate.
Once dry, the magnesium sulfate was filtered from the organic layer which was stripped of solvent using a rotary evaporator. The final ,.1.~~~~~1~~

yield of viscous polymer was 90.3 grams (with 11'gb unreacted phenol). The GPC molecular weight was Mw = 470 and the Mn = 310 (on average a trimer) based on monodisperse polystyrene standards.
Eaam~l~
Per of 1.3-Bis( eno )-2-~ron ~si g the Cascading Polvol ~'eclLn_iaue To a 1 liter, round bottom flask equipped with an overhead stirrer, nitrogen inlet, reflua condenser, addition funnel, and temperature controller was charged 94.11 grams of phenol ( 1 mole), 12.86 grams of tetraethylammonium iodide (0.05 moles), 3.00 grams of water (0.1? moles), 42.08 grams of potassium hydroxide (0.75 moles), and 250 granns of toluene. To a 100 anilliliter additional funnel was charged 23.13 grams of epichlorohydrin (0.25 moles) and 50 grams of toluene. The solution was brought to 65°C, at which time the epichlorohydrin solution was added over a period of 15 minutes while maintaining a reaction temperature of 65°C t 5°C. The reaction was allowed to proceed for 48 hours.
After 48 hours, the solution was cooled down to room temperature. The toluene solution was washed with two 250 milliliters portions of deionized water: The aqueous layers were drained ofl', and the toluene was removed along with unreacted phenol using a rotary evaporator. The final yield of product was 64.5 grams which was 10696 of theory (residual is phenol). Final product purity was about 959b as shown by GPC.
,~ine,t_he Casc~din,g Polvol Techn~q~g To a 250 milliliter round bottom flask equipped with an overhead stirrer, nitrogen inlet, reflua condenser, additional funnel, and temperature controller was charged 20.03 grams of 1,3-bis-(phenoxy>-2-propanol prepared in Ezample 8 (82 mmoles), 2.06 WO 93/24543 '~,1 ~ ~ ~ ~ ~ PGT/US93/04865 _øø_ grams of tetraethylammonium iodide (8 mmoles), 0.49 grams of water (27 mmoles), 6.51 grams of potassium hydro~de (116 mmoles), and 125 grams of toluene. To a 100 milliliter addition funnel was charged 3.61 grams of epichlorohydrin (39 mmoles) and 25 grams of toluene. The solution was brought to 65°C, at which time the epichlorohydrin solution was added over a period of 15 minutes while maintaining a reaction temperature of 65°C f 5°C.
The reaction was allowed to proceed for 48 hours.
After 48 hours, the solution was cooled down to room temperature. The toluene solution was washed with two 250 milliliter porlaons of deionized water. The aqueous layers were drained off, and the toluene was removed using a rotary evaporator.
The final yield of product was 21.6 grams which was 101°r6 of theory.
GPC showed two major components of the product. The first was the startsng material at about 41°Xo (Mn = 220) and the second was the coupled product at about 59°10 (Mn = 520 ).
~nnarntinn of 1 Riafhvloxv~2-urouanol gs'ne t_he Casey lne Polvol Techniaue To a 500 milliliter, round bottom flask equipped with an overhead stirrer, nitrogen inlet, refluz condenser, additional funnel, and temperature controller was charged 60.61 grams of hexadecanol (0.25 moles), 6.18 g~ranas of tetraethylammonium iodide (0.024 moles), 1.44 grams of water (0.082 moles), 20.20 grams of potassium hydro~de (0.36 moles), and 125 grams of toluene. To a 100 milliliter addition funnel was charged 11.10 grams of epichlorohydrin (0.12 moles) and 25 grams of toluene. The solution was brought to 65°C at which time the epichlorohydrin solution was added over a period of 15 minutes while maintaining a reaction temperature of 65°C t 5°C.
The reaction was allowed to proceed for 48 hours.

After 48 hours, the solution was cooled down to room temperature. The toluene solution was washed with two 250 milliliter portions of deionized water. The aqueous layers were drained off, and the toluene was removed using a rotary evaporator.
The final yield of product' was 70.9 grams which is 109°b of theory (residual is heyadecanol).
ale 11 S1 lfation of 1.3-Bis(nonylphenoxv)-2-yron block-(yro~,vlene mddel.~~k-(ethylene oade)~
To a 250 milliliter, round bottom flask equipped with an overhead stirrer, a temperature controller, and a vacuum adapter was added ?5.0 grams of the material from Example 13 (49 mmoles).
The kettle was then evacuated to <20 mmHg and heated to 100°C to remove any water. After 1 hour, the kettle was cooled to 60°C while under vacuum. When reaching 60°C, vacuum was broken with nitrogen and 5.3 grams of sulfamic acid (54 mmoles) was added.
After charging the suIfamic acid, the kettle was heated to 110°C
and evacuated to <20 mmHg. The reaction was allowed to proceed' for 3 hours.
At the end of the hold period, the kettle was cooled to 85°C _and vacuum was broken with nitrogen. 1.2 grams of diethanolamine (11 mmoles) was slowly added under a blanket of nitrogen. This solution was stirred for 30 minutes. 10 grams of ethanol was added to the kettle and the temperature was regulated to 55°C. This solution was stirred for 30 minutes. The heat was removed from the kettle and 30 grams of water along with 20 grams of ethanol were added while maintaining good agitation. The solutaon was stirred for 15 minutes or until cooled to room temperature (<35°C).
The pH was checked by dissolving 2 grams of the product solution in 18 grams of deionized water. If the pH was below ~13G632.
s-6.5, 0.2 gram increments of diethanolamine was added until the pH
is between 6.5 and ?.5.
~gparation of 1.3-Bis(nonyl~ enoxvl-2 yrona_nol-block-(yrowlene o~de)~
To a 500 nnilliliter stainless steel Zipperclave was added 100.0 grams (0.202 mole) of 1,3 bis(nonylphenoxy)-2-propanol prepared in Example 1 along with 0.7 grams of potassium hydroxide.
The vessel was attached to an automated unit and was heated to 50°C. The vessel was continuously purged with nitrogen for 15 minutes and was then heated to 100°C where it was again continuously purged with nitrogen for another 15 minutes. The vessel was then heated to 140°C and is given a series of 6 purges by pressuring the vessel up to 80 psi, and then venting. Once the venting process was completed, the vessel was pressured to 20 psi with nitrogen.
Lines connected to a cylinder, which had been precharged with 117.0 grams of propylene ode (2.02 moles), were opened to the motor valves along with the main feed line on the Zipperclave. The feed was continued and the vessel pressure was regulated at 55 psi and a temperature of 140°C. The automation was designed to hold the temperature and the pressure within safe operating limits while addition of ethylene oxide proceeded through a pair of motor-controlled valves. The feed was allowed to continue until all of the propylene ode had been fed. After the feed was complete, the reaction was allowed to continue for 1 hour after which the vessel was cooled to 60°C, purged 4 times with nitrogen to 80 psi and was dumped to a container. The final product yield was 211 grams with a theoretical yield of 277 grams. The GPC molecular weight of the product was Mw = 650 and the Mn = 490 based on monodisperse polystyrene standards.

.~ WO 93/24543 PGT/US93/04865 ~l~~~i~2 ~g~ple 13 prpn~rgtien ef 1.S-Eis(non~phenoxv)-2-- ron~nol_-bloc~p_~lene o~dde)~ -block-(ethvlen~oride)~
To a 500 milliliter stainless steel Zipperclave was added 75.0 grams of the prnporylate prepared in Example 12 (0.070 mole) along with 0.3 gram of potassium hydrozide. The vessel was attached to an automated ethoaylation unit and was heated to 50°C.
The vessel was continuously purged with nitrogen for 15 minutes and was then heated to 100°C where it was again continuously purged with nitrogen for another 15 minutes. The vessel was then heated to 140°C and was given a series of 6 purges by pressuring the vessel up to 80 psi, and then venting. Once the venting process was completed, the vessel was pressured to 20 psi with nitrogen.
The ethylene ozide lines were opened to the motor valves along with the main feed line on the Zipperclave. The feed was continued and the vessel pressure was regulated at 55 psi and a temperature of 140°C. The automation was designed to hold the temperature and the pressure within safe operating limits while addition of ethylene oxide proceeded through a pair of motor control valves. The feed was allowed to continue until 30.7 grams ethylene oxide (0.696 mole) was added based on a difference weight of the feed cylinder. After the feed was complete, the reaction is allowed to continue for 1 hour, after which the vessel was cooled to 60°C, purged 4 times with nitrogen to 80 psi and was dumped to a container. The final product yield was 99 grams with a theoretical yield of 106 grams.

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s-~ ~oxv) Adduct of 'glvcidvl Ether To a five neck, two liter, round bottom flask equipped with an addition funnel, thermometer, nitrogen dispersant tube, mechanical stirrer, and a decanting head with a water-cooled condenser were added 506.8 grams (2.30 moles) of nonylphenol and 350 nnilliliters of cyclohezane. The solution was heated to reflug, and 6.5 grams (1.3 weight percent based on nonylphenol) of potassium hydro~de in 15 milliliters of water was slowly added to the round bottom flask. After all the water was recovered in the decanting head (15 milliliters + 2 milliliters formed), 220 grams (1.09 moles) of 1,4-butanediol diglycidyl ether was added dropwise between 60 and 80°C.
Ailer the addition was complete, the solution was refluzed for four hours. The contents of the flask were then washed with a five percent aqueous solution of phosphoric acid, and the organic layer was separated from the water layer and washed twice with deionized water. The reaction mixture was then placed in a one liter, round bottom flask, and the remaining cycloheaane and unreacted nonylphenol were recovered by distillation, first at atmospheric pressure, then under vacuum at 0.2 mm Hg. The kettle temperature was not allowed to exceed 180'C during the distillation to prevent discoloration of the product. The concentrated solution was then refiltered to give ?10 grams of a pale-yellow liquid. Molecular weight by end-group MW analysis was 689.9 (theoretical MW = 643.0). Ir and nmr spectra were consistent with the expected structure of the product.
~praratinn of R-MOle,~' 1,3-Bi- s(nonvlflhenoxv>-2-nrouanol To a five hundred milliliter, Zipperclave reactor were charged, under nitrogen, 200.1 grams (0.43 mole) of 1,3-~ WO 93/24543 PCT/US93/04865 bis(nonylphenory~2-propanol prepared in Example 2 and 0.20 gram (0.1 weight percent) of BFg~Et20. The reaction mixture was heated to 80°C, and 55.1 grams (1.25 mole) of ethylene ode was fed to the reactor over a two hour period. After all the ethylene ozide was fed, the reaction mixture was allowed to cook out for one hour and then dumped hot, under nitrogen, into a jar containing 160 milliliters of a one percent aqueous solution of sodium hydroxide. The organic layer was separated from the water layer and washed twice with deionized water. The washes were performed at 90°C to facilitate the separation of the two layers. The product was then dried by azeotropic removal of the water, using cyclohexane (S00 milliliters) as the entrainer. The cycloheaane was stripped off under vacuum to give a pale-yellow liquid with a molecular weight by end-group MW
analysis of 601.? (theoretical MW = 629). Ir and amr spectra were consistent with the expected structure of the product.
EaamD
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To a five hundred milliliter Zipperclave reactor were charged, under nitrogen, 150.2 grams (0.22 mole) of bis(nonylphenoay) adduct of 1,4-butanediol diglycidyl ether prepared in Ezample 14 and 0.30 grams (0.2 weight percent) of BFg ~Et20. The reaction mizture was heated to 80°C, and 77.5 grams (1.76 mole) of ethylene ozide was fed to the reactor over a two hour period. After all the ethylene ozide was fed, the reaction mizture was allowed to cook out for one hour and then dumped hot, under nitrogen, into a jar containing 160 milliliters of a one percent aqueous solution of sodium hydrozide. The organic layer was separated from the water layer and washed twice with deionized water. The washes were performed at 90°C to facilitate the separation of the two layers. The product was then dried by azeotropic removal of the water, using _ cyclohexane (300 milliliters) as the entrainer. The cyclohexane was stripped ofl' under vacuum to give a pale-yellow liquid with a molecular weight by end-group MW analysis of 1047 (theoretical MW
= 995). Ir and nmr spectra were consistent with the expected structure of the product.
Example 17 Preparation of Macromonomer Comyound Into a 1 liter, round bottom reaction flask equipped with a heating mantle, dean stark trap, condenser, thermometer, nitrogen bubbler, nitrogen purge line and stirrer was charged 300 grams of toluene and 63 grams of a surfactant identified as S-1 in Table A below. With nitrogen purge, the resulting solution was heated to reflux at approximately 110°C and azeotroped to remove trace water to dryness. The solution was subsequently cooled to 90°C, and 1.5 grams of bismuth hex them 28% bismuth octoate catalyst (Mooney Chemical, Inc., Cleveland, Ohio) was charged and allowed to mix well, after which a stoichiometric amount of 95% m-TMI
aliphatic isocyanate (American Cyanamid, Stanford, Connecticut) was charged. After the reaction proceeded at 90°C for 1.3 hours, the resulting product was cooled to 70°C and 0.03 gram of 2,6-di-tert-4-butyl phenol (BHT) preservative was added. The mixture was poured into a stainless steel pan with large surface area to facilitate drying. The final product was a waxy material, and is designated herein as macromonomer M-1.

-sl-..
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CH-(OCH2CH2)zOCH2CH2OH
I
g2 R2 = hydrogen or a R3-O-CH2- residue.
Moles of -~~ ~ ~h~rla~iQn S~1 Nonylphenol Hydrogen (R2) 90 S~2 Nonylphenol Nonylphenol (R3) 40 S.3 Nonylphenol Nonylphenol (R3) 20 S-4 Nonylphenol Octylphenol (R3) 20 S~5 Nonylphenol Octylphenol (R3) 40 ~6 Nonylphenol Nonylphenol (R3) 80 S-? Nonylphenol Nonylphenol (R,3) ~ 120 F~ale~18-34 In a manner similar to that described in Example 17, other macromonomers were prepared using stoichiometric amounts of the surfactants and unsaturated compounds identified in Table B
below.

~~~ss32 Eaample Unsaturated Macromonomer (Jom~~ound 18 S-2 ~ m-TMI M-2 19 S-3 m-TMI M-3 20 S.4 m-TMI M-4 21 S-5 m-TMI M-5 22 S-6 m-TMI M-6 23 S-? m-TMI M-7 24 S-2 Isocyanato Ethyl M-8 Methacxylate 25 S-5 isocyanato Ethyi M-9 Methacrylate 26 S-1 Methacrylic Anhydride M-10 27 S-2 Methacrylic Anhydride M-11 28 S-5 Methacrylic Anhydride M-12 29 S-6 Methacrylic Anhydride M-13 30 S-2 Acrylic Anhydride M-14 31 S-5 Acrylic Anhydride M-15 32 S-6 Acrylic Anhydride M-16 ~2 Crotonic Anhydride M-17 34 S5 Malefic Anhydride M-18 ~naratinn of Alkali-SolLble Th,'_ckener .
A monomer nnizture (300 grams) was prepared by charging ethyl acrylate (Aldrich), methacrylic acid (Aldrich), macromonomer M-1, 13 grams of a ?5~ solution of Aerosol~ OT
surfactant (American Cyanamid, Stanford, Connecticut), and 3 grams of distilled deionized water to a bottle; and dispersing the coatents with vigorous shaking. The ethyl acrylate, methacrylic acid and macromonomer M-1 were added in amounts identified in Table C below. A catalyst feed miztiu~e comprised of 0.53 gram of sodium persulfate (Aldrich) and 52.47 grams of water was prepared in another container. To a 2 liter resin flask that had been immersed in a thermostated water bath and equipped with a 4-bladed stainless steel mechanical stirrer, Claisen connecting tube, water condenser, nitrogen sparge and bubble trap, thermometer and monomer and catalyst addition inlets, 1.20 grams of the sodium salt of vinyl sulfonic acid and 658.5 grams of water were charged. The monomer mixture was charged to a 1-liter graduated monomer feed cylinder, and the catalyst solution was charged to a 125 milliliter graduated catalyst feed cylinder. Under nitrogen purge, the reactor was heated to 70°C, whereupon 33 nnilliliters of the monomer mixture and 3 milliliters of the catalyst feed mixture were charged to the reaction vessel. The reaction vessel was subsequently heated to 80°C. After allowing the monomers to react for 20 minutes to form a seed product, the monomer and catalyst feed mixtures were conveyed to the reaction vessel by FMI pumps via 1/8" Teflon tubing at a rate of 1.94 and 0.2? milliliters/minute, respectively, under continuous storing at a reaction temperature held between ?6-82°C. The reaction was allowed to proceed for another hour, after which the product was cooled and filtered with a 200 mesh nylon cloth. The coagulum was collected from the reaction vessel and filter cloth.
Thickening ability of the resulting product was monitored by Brookfield viscosity at 6 rpm by diluting the latex to 0.25%, 0.50% and 0.75% solids, and subsequently neutralizing the product to pH=9.0 with a 95°b solution of 2-amino-2-methyl-1-propanol (AMP-95, Angus Chemical Company). The results are given in Table C.
mules 36-131 P~~aration of A_lkal_i-soluble Thickeners In a manner similar to that described in Example 35, other alkali-soluble thickeners were prepared using the monomers identified in Tables C-J below in the amounts identified in Tables C-J. Table C illustrates the influence of m-TMI-containing macromonomer concentration and ethoxylation on thickening e~ciency. Table D illustrates the influence of mi~dag m-TMI-i r containing macromonomers of various ethogylations on thickening efficiency. Table E illustrates the influence of unsaturation type of urethane-containing macromonomers on thickening efficiency.
Table F illustrates the influence of macromonomer ester structure and ethoxylation on thickening efficiency. Table G illustrates the influence of acid type and concentration on thickening efficiency.
Table H illustrates the influence of polymer glass transition temperature and water solubility on thickening efficiency. Table I
illustrates the influence of cxoss-linkable monomer concentration on thickening efficiency. Table J illustrates the influence of mercaptan on thickening efficiency. As used in Tables C-J below, the following abbreviations have the indicated meanings: MM = Macromonomer;
EA = Ethyl Acrylate; MAA = Methacrylic Acid; AA = Acrylic Acid;
MA = Methyl Acrylate; t-BA = t-Butyl Acrylate; n-BA = n-Butyl Acxylate; MMA = Methyl Methacrylate; 2-EHP = 2-Ethylhexyl Propionate Mercaptan; and 2-HEA = 2-Hydroxy Ethyl Acrylate.

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.-. WO 93/24543 ~ ~ ~ ~ ~ ~ ~ PGT/US93104865 Co-Thickening with Su_r_factants The addition of certain surfactants to an associative polymer solution produces a co-thickening effect. The results in Table L below show the.co-thickening effect produced by the addition with thorough mi~dng of certain surfactants identified in Table K
below in the amounts identified in Table L to a 0.5°!o alkaline solution of an alkali soluble thickener identified in Table L as measured with a Brookfield Viscometer at 6 rpm at pH = 9Ø
R'1-O-CH2 I
CH-(OCH2CH2)ROCHZCH20H
I
RZ = hydrogen or a R3-O-CH2- residue.
Moles of Ethoxvlation S-8 Nonylphenol Nonylphenol (R3) 20 S-9 Nonylphenol Nonylphenol (R3) 90 S-10 Nonylphenol Nonylphenol (R3) 80 S-11 Nonylphenol Hydrogen (R2) 25 S-12 Nonylphenol Hydrogen (R,2) 40 S-13 Nonylphenol Octylphenol (R,3) 20 S-14 Nonylphenol Octylphenol (R3) 40 S-15* Nonylphenol Nonylphenol (R3 40 ) S-16 Octylphenol Hydrogen (R,2) 25 * Sulfated derivative.

i WO 93/24543 . PCT/US93/04865 ,..
~~~~~3~

.Table L
Surfactant Concentration Brookfield Viscosity (weisrht_Rb) Thickener(cns) ~ n~I=9.0 132 S.8 0.0 P-3 3100 S-8 0.2 P-3 3~~

S-8 0.4 P-3 45700 S-8 0.8 P-3 S-8 1.0 P-3 S-8 2.0 P-3 >100000 133 S-9 0.2 P-3 ~9 0.4 P-3 1~~

~9 0.8 P-3 6600 S-9 1.0 P-3 4~

2.0 P-3 134 S-10 0.2 P-3 S-10 0.4 P-3 17300 S-10 0.8 P-3 8500 X10 1.0 P-3 X10 2.0 P-3 1~

135 X11 0.2 P-3 1~

X11 0.4 P-3 3160 X11 0.8 P-3 700 X11 1.0 P-3 4~

S-11 2.0 P-3 480 136 S-12 0.2 P-3 9200 X12 0.4 P-3 4500 X12 0.8 P-3 1000 S-12 1.0 P-3 875 X12 2.0 P-3 565 137 S-13 0.2 P-3 34300 X13 0.4 P-3 26700 3r13 0.8 P-3 11500 S-13 1.0 P-3 8600 X13 2.0 P-3 -... WO 93/Z4543 ~ ~, 3 ~ ~ ~ ~ PCT/US93/04865 fable L (Continued) Surfactant Concentration Brookfield Viscosity Example y~y~~ (we' t.96) thickenerOCDE~~) ~ pfI=9.0 138 X14 . 0.2 P-3 ZZ200 S-14 0.4 P-3 17200 X14 0.8 P-3 6900 X14 1.0 P-3 4500 X14 2.0 P-3 1500 139 S-15 0.2 P-3 10500 S-15 0.4 P-3 4940 S-15 0.8 P-3 2160 S-15 1.0 P-3 1450 S-15 2.0 P-3 355 140 S~16 0.2 P-3 14300 X16 0.4 P-3 4080 S-16 0.8 P-3 1075 X16 1.0 P-3 ?35 S.16 2.0 P-3 485 141 S$ 0.0 P-2 11400 S8 0.2 P-2 23500 ~8 0.4 P-2 34000 S.8 0.8 P-2 64000 S$ 1.0 P-2 71000 S-8 2.0 P-2 93000 142 S~9 0.2 P-2 11000 S-9 0.4 P-2 4000 ~9 0.8 P-2 2000 S~9 1.0 P-2 1400 ~9 2.0 P-2 850 143 S-10 0.2 P-2 10500 S-10 0.4 P-2 x000 S-10 0.8 P-2 2000 S-10 1.0 P-2 1600 S-10 2.0 P-2 950 i a Table L (Continued) Surfactant Concentration Brookfield Viscosity (weiQht.96) thickener~~W ~ nH=9.0 144 &.11 _ P-2 ~ 0.2 8r11 0.4 P-2 1000 S11 0.8 P-2 S-11 1.0 P-2 S-11 2.0 P-2 1~5 S-12 0.2 P-2 S-12 0.4 P-2 10x1 X12 0.8 P-2 S-12 1.0 P-2 X12 2.0 P-2 146 ~8 0.0 P-4 2150 S-8 0.2 P-4 S.g 0.4 P-4 31000 S-8 0.8 P-4 r' ~.8 1.0 P-4 61000 S-8 2.0 P-4 147 ~9 0.2 P-4 191 ~9 0.4 P-4 21500 8r9 0.8 P-4 11500 ~9 1.0 P-4 7400 2.0 P-4 2250 148 8r10 0.2 P-4 12~

S-10 0.4 P-4 17400 S-10 0.8 P-4 12~

S.10 1.0 P-4 S-10 2.0 P-4 149 X11 0.2 P-4 1?400 S-11 0.4 P-4 7804 S11 0.8 P-4 1650 S-il 1.0 P-4 860 X11 2.0 P-4 5~

,.-.. WO 93/24543 Z ~ ~ ~, ~ ~ ~ PCT/US93/04865 Table L (Continued) ' Surfactant Concentration Brookfield Viscosity ,~g~ (wee t.96) ~' icl~enerIcnS) ~ D -_9.O

>50 S-12 ~ 0.2 P-4 14600 S~12 0.4 P-4 ?800 S-12 0.8 P-4 1500 8r.12 1.0 P-4 960 5.12 2.0 P-4 450 7,51 ~8 0.0 P-5 ?90 S-8 0.2 P-5 4600 S-8 0.4 P-5 19600 S-8 0.8 P-5 42000 S8 1.0 P-5 50000 S-8 2.0 P-5 90000 152 S9 0.2 P-5 b800 ~9 0.4 P-5 13200 S-9 0.8 P-5 9200 ~9 1.0 P-5 5200 S9 2.0 P-5 1600 153 S-10 0.2 P-5 4050 S~10 0.4 P-5 10400 S~10 0.8 P-5 9400 S-10 1.0 P-5 5000 S-10 2.0 P-5 1600 154 S-11 0.2 P-5 10600 ill 0.4 P-5 4200 511 0.8 P-5 1400 S-11 1.0 P-5 970 S~11 2.0 P-5 410 155 S-12 0.2 P-5 6000 S-12 0.4 P-5 4200 S~12 0.8 P-5 1150 X12 1.0 P-5 600 X12 2.0 P-5 340 i E

~~.~~i~a:~~
-ss-fable L (Continued) Surfactant Concentration Brookfield Viscosity (weigh _~ Thickenerys) ~ nH=9.0 156 S-8 , 0 P-7 1200 S.g 0.2 P-7 9000 S.g 0.4 P-? 21000 S.8 0.8 P-7 37000 S.g 1.0 P-7 49000 ~8 2.0 P-7 78000 15? ~9 0.2 P-7 1~

9 0.4 P-7 9 0.8 P-7 900 1.0 P-7 762 S-9 2.0 P-7 565 158 S-10 0.2 P-7 1100 X10 0.4 P-7 1~

X10 0.8 P-7 S-10 1.0 P-7 823 S-10 2.0 P-7 650 15.9 S-11 0.2 P-? 1175 S-11 0.4 P-7 S-11 0.8 P-7 5~

S11 1.0 P-7 4~

X11 2.0 P-? ~2 160 X12 0.2 P-7 950 8.12 0.4 P-7 675 S-12 0.8 P-7 525 5.12 1.0 P-7 500 X12 2.0 P-7 480 161 S-8 0.0 P-13 25500 S.g 0.2 P 13 3150() ~.8 0.4 P 13 46500 ~8 0.8 P 13 60000 S.g 1.0 P-13 S8 2.0 P-13 .-. WO 93/Z4543 ~ ~ ~ ~ ~ ~ ~ PGT/US93/04865 ~~ (Continued) Surfactant Concentration Brookfield Viscosity ]g ~, (weieht.~) Thickener_(yys) ~ nIic9.0 162 S~9 0.2 P 13 8640 S~9 0.4 P-13 2940 S-9 0.8 P-13 1200 S~9 1.0 P-13 1000 S-9 2.0 P 13 ?50 163 S-10 0.2 P 13 10100 8r10 0.4 P 13 4200 S~10 0.8 P 13 1450 S10 1.0 P 13 1300 8r10 2.0 P 13 900 1fi4 S-12 0.2 P 13 2540 S~12 0.4 P 13 1125 X12 0.8 P 13 750 X12 1.0 P 13 670 S~12 2.0 P 13 610 165 S-8 0.0 P 14 39000 S~8 0.2 P 14 61000 ~8 0.4 P 14 73500 S-8 0.8 P 14 87000 S-8 1.0 P 14 93500 S-8 2.0 P 14 122000 166 S-9 0.2 P 14 41000 S-9 0.4 P 14 13700 S-9 0.8 P 14 fia00 8r9 1.0 P 14 3500 S~9 2.0 P 14 1200 167 S ~:.:: 0.2 P 14 38200 X10 0.4 P 14 20500 S-10 0.8 P-14 ?300 S10 1.0 P-14 5400 X10 2.0 P-14 1950 I
WO 93/24543 PGT/US93/04865 ,..
_gg-(Contin ued) Surfactant Concentration Brookfield Viscosity g ~ (we' t.~o) Thi ckener(cnls) ~ nHo9.0 168 Sl2 0.2 P-14 13000 5.12 0.4 P-14 430() S-12 0.8 P-14 975 S-12 1.0 P 950 S-12 2.0 P-14 660 169 S-8 0.0 P 52500 S-8 0.2 P 95000 S-8 0.4 P 92000 S-8 0.8 P 122000 S-8 1.0 P 125000 ~8 2.0 P-16 138000 170 PS-9 0.2 P-16 73500 PS-9 0.4 P 53000 PS-9 0.8 P-16 25000 PS-9 1.0 P 21000 PS-9 2.0 P-16 5400 1?1 S-10 0.2 P 52800 S-10 0.4 P-16 34500 S-10 0.8 P-16 5400 S-10 1.0 P-16 2925 S-10 2.0 P-16 775 172 S-13 0.2 P-16 45800 S-13 0.4 P-16 54000 S-13 0.8 P-16 50800 S-13 1.0 P 54500 S-13 2.0 P 63000 173 S-14 0.2 P 22700 S-14 0.4 P 2480 S-14 0.8 P ?10 S-14 1.0 P-16 532 S-14 2.0 P 415 WO 93/24543 '~ ~ ~ ~ ~ ~ ~ PGT/US93/04865 Table LL (Continued) Surfactant Concentration Brookfield Viscosity F,~g ,~ (we' t.Rb) $I ~,( 'pas) ~ yH=9.0 174 S-8 ~ 0.0 P-29 285 ~.8 0.2 P-29 285 S-8 0.4 P 29 360 S-8 0.8 P-29 4?7 ~8 1.0 P 29 505 S-8 2.0 P 29 837 175 ~9 0.2 P-29 2B2 S-9 0.4 P-29 285 ~9 0.8 P 29 284 S-9 1.0 P 29 298 S-9 2.0 P 29 322 176 S-10 0.2 P 29 272 S~10 0.4 P 29 278 S-10 0.8 P 29 285 X10 1.0 P 29 297 6r10 2.0 P-29 315 177 S-12 0.2 P-29 267 S-12 0.4 P 29 279 X12 0.8 P 29 298 S-12 1.0 P 29 311 S-12 2.0 P-29 320 178 S~8 0.0 P-30 19500 S$ 0.2 P-30 79000 S-8 0.4 P-30 71200 S-8 O.B P 30 81000 S.8 1.0 P 30 89500 ~.8 2.0 P-30 175000 179 ~9 0.2 P-30 52000 ~9 0.4 P 30 35500 ~9 0.8 P-30 16600 ~9 1.0 P-30 15600 ~9 2.0 P-30 5620 i r WO 93/24543 PCT/US93/04865 .-.
~.:~~~~3~

Table L (Continued) Surfactant Concentration Brookfield Viscosity (wei t.96) T]Z.ckener_ (cos) ~ nH=9.0 180 X10 ~ 0.2 P-30 X10 0.4 P-30 263 X10 0.8 P 30 S-10 1.0 P-30 X10 2.0 P 30 4700 181 X12 0.2 P-30 23000 S-12 0.4 P-30 6840 X12 0.8 P-30 3125 5.12 1.0 P-30 1750 5.12 2.0 P 30 1~

182 ~8 0.0 P-46 24500 S-8 0.2 P-46 79000 S.8 0.4 P~6 7~

S.8 0.8 PEG 86000 S-8 1.0 P-46 S.8 2.0 P-46 150000 183 ~9 0.2 P-46 40500 S-9 0.4 P-46 31000 S-9 0.8 P-46 ~9 1.0 P-46 S-9 2.0 P-46 2300 184 S-11 0.2 P-46 S-11 0.4 P-46 7300 X11 0.8 P-46 1350 X11 1.0 P-46 900 S11 2.0 P-46 3~

185 S-13 0.2 P-46 S-13 0.4 P-46 42000 S-13 0.8 P-46 X13 1.0 P-46 16000 erl3 2.0 P-46 4850 ,..,. WO 93/24543 -?1-Table L (Continued) Surfactant Concentration Brookfield Viscosity ~p~g ~,~ (we' t.Rfo) ~lickener ~ s~ 1 ~ nHc9.0 186 X14 0.2 P-46 36000 S-14 0.4 P-46 25000 X14 0.8 P-46 11000 X14 1.0 P-46 9300 S-14 2.0 P-46 1900 187 S-16 0.2 P-46 19000 S-16 0.4 P-46 9300 X16 0.8 P-46 125() X16 1.0 P-46 750 X16 2.0 P-46 290 ~~,~,188-232 Co-Thieke~ine with ~L~~faeta_n_ts The degree of ethoaylation of a surfactant added to an associative polymer solution influences the co-thickening effect. The results in Table N below show the co-thickening effect produced by the addition with thorough mi~dng of certain surfactants identified in Table M below in the amounts identified in Table N to a 0.3%
(Examples 172-189), 0.5qb (Ezamples 190-215) or 0.75% (Example 216) alkaline solution of an alkali soluble thickener identified in Table N
as measured with a Brookfield Viscometer at 6 rpm at pH = 9Ø
Rl-D-CH2 I
CH-(OCH2CH2)gOCH2CH20H
I

R2 = hydrogen or a R3-O-CH2- residue.

i a ~~;1.3~~~2 - ?2 -Moles of B

y , .-X17 Nonylphenol Hydrogen (R2) 4 S18 Nonylphenol Hydrogen (R2) 6 S-19 Nonylphenol Hydrogen (R2) 7 S-20 Nonylphenol Hydrogen (R2) 8 S-21 Nonylphenol Hydrogen (R2) 9 S-22 Nonylphenol Hydrogen (R,2) 10 S-23 Nonylphenol Hydrogen (R2) 15 S-24 Nonylphenol Hydrogen (R,2) S~25 Nonylphenol Hydrogen (R2) 40 X26 Octylphenol Hydrogen (R2) 1 X27 Octylphenol Hydrogen (R2) 3 X28 Octylphenol Hydrogen (R2) 5 X29 Octylphenol Hydrogen (R2) 7 S-30 Octylphenol Hydrogen (R2) 9 x.31 Octylphenol Hydrogen (R2) 12 S-32 Octylphenol Hydrogen (R2) 16 S.33 Cll-C15 Secondary Hydrogen (R2) 5 Alcohol S34 Cll-C15 Secondary Hydrogen (R2) 9 Alcohol .-... WO 93/24543 PCT/US93/04865 -?3-Surfactant Concentration Brookfield Viscosity y~ (wei t.961 thickenerysl ~ nH=9.0 188 S-17 0.8 P-1 890 189 S-18 0.8 P-1 1340 190 8r19 0.8 P-1 630 191 5.20 0.8 P-1 205 192 S-21 0.8 P-1 143 yg3 5,.~ p,8 P-1 113 194 x.23 0.8 P-1 85 195 5r24 0.8 P-1 57 196 X25 0.8 P-1 68 197 S-17 0.8 P-3 17800 198 S-18 0.8 P-3 35800 199 S~19 0.8 P-3 21300 200 X20 0.8 P-3 820 201 X21 0.8 P-3 230 202 X22 0.8 P-3 147 203 5.23 0.8 P-3 118 204 5.24 0.8 P-3 82 205 X25 0.8 P-3 'T7 206 X17 0.8 P-42 57000 207 S18 0.8 P-42 134000 208 519 0.8 P-42 112000 209 S-21 0.8 P-42 2450 210 S-22 0.8 P-42 800 211 523 0.8 P-42 3250 212 X26 0.8 P-42 43000 213 S-27 0.8 P-42 37000 214 X28 0.8 P-42 71000 215 5.29 0.8 P-42 5800 216 X30 0.8 P-42 375 217 X31 0.8 P-42 650 218 S32 0.8 P-42 2400 219 S-1? 0.8 P-46 68000 220 S18 0.8 P-46 13000 221 5.19 0.8 P-46 88000 222 X21 0.8 P-46 2900 223 5.22 0.8 P-46 1400 224 S23 0.8 P-46 s~~~~~~
-?4-Table NN (Coot.) Surfactant Concentration Brookfield Viscosity (weipht.R6) Thickener (cns) ~ nH=9.0 225 5.26 0.8 P-46 25000 226 S-27 0.8 P-~

227 S-28 0.8 P-46 77000 ~g X29 0.8 P-46 72~

~g 5.3p 0.8 P-46 550 230 S.,31 0.8 P-46 231 5-32 0.8 P-46 1775 232 Aerosol~ OT 0.0 P-4 50500 Aerosol~ OT 0.1 P-4 93500 Aerosol~ OT 0.2 P-4 42000 Aerosol~ OT 0.4 P-4 11200 Aerosol~ OT 0.8 P-4 3700 Aerosol~ OT 1.0 P-4 7204 Aerosol~ OT 2.0 P-4 10600 ('o-Tlicke~ng with Solvents nd Non-Solvents Solvents and non-solvents added to an associative polymer solution influence the co-thickening effect. The results in Table P below show the co-thickening effect produced by the addition with thorough mi~ng of certain solvents and non-solvents identified in Table O below in the amounts identified in Table P to a 0.75 alkaline solution of an alkali-soluble thickener identified in Table P
as measured with a Brookfield Viscometer at 6 rpm at pH = 9Ø

-.. WO 93/Z4543 ~ ~ ~ s ~j 3 ~ PGT/US93/04865 ' Solvent Solvent p-1 ~ mineral spirits O-2 butanol O-3 Isobutanol O-4 Isopropanol p.5 2-Ethylhezanol p-6 Butyl Carbitol O-7 Butyl DiPropasol p-8 Butyl Propasol O-9 Propyl DiPropasol O-10 Propyl Propasol O-11 Methyl DiPropasol O-12 Methyl Propasol bl P

- a Brookfield e Solvent Solvent 0-1 Concentration ConcentrationViscosity finer (wei t.Rb) (weiQht.%) lens) ~
nH c 9.0 P-3 O-6 X10 0 ?20 P-3 O-6 2D 5 ?35 P-3 O-6 b 10 56500 ' P-3 O-9 6 0 2150 P-3 O-? 10 0 3'100 P-3 O-'720 0 2000 P-3 O-? 0 5 8.9000 i r ~~~6s3~
Fable P ccont.~
Solvent Solvent O-1 Brookfield ConcentrationConcentrationViscosity E~ Thickenery~olvent(wei t.qb) (wei t.%) ~~H = 9.0 p]g , P-3 O-? 5 5 P-3 0-? 10 5 50000 P-3 O-? 20 5 46500 P-3 O-7 0 10 lOQA00 P-3 O-? 5 10 122000 P-3 O-7 10 10 ?2000 P-3 0-? 10 20 138000 P-3 O-8 40 0 6'x00 P-3 O-9 20 0 4!0 23? P-3 O-10 5 0 13?5 P-3 O-il 40 0 550 239 P-3 O-12 0 0 ?6000 P-3 O-12 20 5 ?100 ,..,., WO 93/24543 ~ 1 ~ 6 fi 3 2 -?7 -(Cont.) Solvent Solvent Brookfield ConcentrationConcentrationViscosity Thickener (weieht.Rf~)(wei t.R'o)mss) ~ yH
= 9.0 240 P-14 O-? 0 0 160000 P-14 O-? 5 0 1350 P-14 O-? 10 0 4500 P-14 O-? 20 0 '7000 P-14 O-? 0 5 140000 P-14 O-? 10 5 ?6000 P-14 O-? 0 5 140000 P-14 O-? 5 10 158000 P-14 O-? 10 10 124000 241 P-3a O-2 0 0 13'600 P-3a 0-2 5 0 1?300 P-3a O-2 10 0 850 P-3s O-2 20 0 1425 P-3a O-2 40 0 4750 P-3a O-2 0 5 140000 P-3a O-2 5 5 6?000 P-3a O-2 10 5 2500 P-3a 0-2 20 5 3000 P-3a 0-2 0 10 134000 P-3a O-2 5 10 33000 P-3a O-2 10 10 4000 P-3a O-2 20 10 4900 P-3a O-2 0 20 144000 P-3a O-2 5 20 49000 P-3a O-2 10 20 6000 i r ~1~6s~z Fable P (Cont.) Solvent Solvent Brookfield ConcentrationConcentrationViscosity l 96) (wei' fens) ~
ieht nH - 9.0 ( g dig ever vent .
w we 242 P-3s O-3 5 0 P-3a O-3 10 0 P-3a O-3 20 0 1425 P-3a O-3 40 0 P-3a O-3 5 5 P-3a O-3 10 5 P-3a O-3 ~ 5 P-3a O-3 40 5 P-3s O-3 5 10 ?8000 P-3a O-3 10 10 P-3a O3 20 10 P-3a O-3 5 P-3a O-3 10 P-3a O-4 5 0 P-3a O-4 10 0 P-3a O-4 20 0 1060 P-Sa O-4 '~ 0 P-3a O-4 5 5 10?400 P-3a O-4 10 5 39000 P-3a O-4 ~ 5 P-3 a O-4 40 5 P-3a O-4 5 10 1~

P-3a O-4 10 10 41000 P-3s O-4 20 10 1~

P-3a O-4 '10 10 1060 P-3s 0-4 5 20 l~

P-3a O-4 10 P-3a O-4 20 P-3a O-4 40 244 P-3a O-5 5 0 P-3a O-5 10 0 P-3a O-5 20 0 178000 245 P-3a O-? 5 0 P-3a O-? 10 0 6100 P-3a O-7 20 0 11900 .~.. WO 93/24543 PGT/US93/04865 -?9-a 246 Polymer ~olLtion ha_racterization For Aircraft anti-Icing FlLids Polymer solutions were titrated with water, and 30 RPM
Brookfield viscosities (centipoise) were measured at room temperature (20°C) and at 0°C in a thermostated bath. The results are given in Table Q below. The polymer solutions at 0 grams added water contained 0.5°!o polymer solids identified in Table Q, 1:1 ethylene glycol: water solvent mixture and a pH = 9Ø Negative grams water added simulates water evaporation (the "dry-out"
phenomenon).
Grams Viscosity Viscosity Added Water at _2QS'c g25 1750 lp g~,5 1505 7gp 1400 Grams Viscosity Viscosity Added Water ~Q~ at ~°C

1~0 4240 y5 g,2~5 2100 i ~~.3~~3~

~jymer P-4 Grams Viscosity Viscosity Added Water - t,~ U-C

p g~ 3000 lp 705 ~,~rmer P- 5 Grams Viscosity Viscosity Added Water at -20'C

wr 45g 1415 lp ~p 865 ygl 760 Polymer P-6 Grams Viscosity Viscosity Added Water at ~~~

gg7 1'~0 p 853 1700 5 7~ 1475 lp 723 1365 yr 6pp 1215 ~~~~~a~

PQ13~L.~:~.
Grams Viscosity Visco sity Added Water ~,t -20-C _ t~ 0C

0 1060 1.960 lp g55 1490 P~ vmer P-9 Grams Viscosity Viscosity Added Water at =?,~''' c 2g20 5100 yp lssp 2770 ~ymer P-13 Grams Viscosity Viscosity Added Water at- at ~C

-lp 475 2375 .,5 850 2260 . 5 760 2025 lp 685 1990 Pnlvmer P-14 Grams Viscosity Viscosity 8dded Water .. -~-_lp ~ 1190 0 g75 4050 g8p 4225 y5 g15 3975 Polymer P-16 Grams Viscosity Viscosity Added Water ~-~.r~r 11540 3p2,5 11400 Polvme~l7 Grams Viscosity Viscosity Added Water .~.,~Z~S - t _10 3575 lp 3675 yr 35pp 1130() '"' WO 93/24543 ,~, v PGT/US93/04865 Pnlvmer P-65 Grams Viscosity Viscosity Added Water t~ ~.

6,50 1490 yr 3g~ 1050 Pslxm~P~
Grams Viscosity Viscosity Added Water at-20-C _at ~°C

0 y~0 ?800 5 1~,5 8140 lp y52,5 7200 y5 y5,50 7000 Grams Viscosity Viscosity Added Water ~~ _ to 0°C
-10 9?5 ?~5 1720 lp ~ 1365 y,5 570 WO 93/24543 ~~ ~'~ ~ ~ ~ ~, PGT/US93/04865 _g4_ Grams Viscosity Viscosity Added Water - at ~~C
_l0 ~ 21.30 y~ 4160 Grams Viscosity Viscosity Added Water ~t -20'C ~°.~..

lp ~ 175 y5 q4 165 FB~DI
Temgpratu_re Sensitivity of Polymers In Airy n i-Tcin~ Fi_uids Polymer solutions were heated and 30 RPM Brookfield viscosities were measured at various temperatures in a thermostated bath. The activation energy was measured for a change in viscosity with respect to temperature. AH was determined by fitting the temperature dependence of the specific viscosity for 0.5°k polymer solutions identified in Table R below in a 50/50 ethylene glycoUwater solvent nniature to equation (3) herein by a standard least squares method. The results are given in Table R.

P-3a O-7 20 0 11900 WO 93/Z4543 ~ PGT/US93/04865 P-2 ~ -3.3 P-3b 9.5 P-4 14.2 P-5 13.4 P-6 -2.1 P-8 -4.6 P-9 -3.6 P-13 3.3 P-14 22.5 P-16 15.1 P-17 15.7 P-65 3.4 P-68 28.8 P-71 2.0 P-81 10.8 P-91 5.1 Ea4~
Co-Thickening in Polvmer Solution Polymer solutions were titrated with water and 30 RPM
Brookfield viscosities (centipoise) were measured at room temperature (20°C) and at 0°C in a thermostated bath. The results are given in Table S
below. The polymer solutions at 0 grams added water contained 0.5%
polymer solids identified in Table S, an amount (weight percent based on total solution) of Tergitol~ 15-S-5 nonionic surfactant identified in Table S, - 1:1 ethylene glycol: water solvent mixture and a pH = 9Ø Negative grams water added simulated water evaporation (the "dry-out" phenomenon).

i x Pnl~~er P-24 with actAnt No Surf Grams , Viscosity Viscosity Added Water . = t 0 l6pp 5260 lp 1175 ~5 1075 P nlvmer p-24 with 0.25%rfactant Su Grams Viscosity Viscosity Added Water .~Z~

-10 15,700 15,360 57,200 0 14,900 57,800 14,500 57,600 lp 13,920 56,000 yc ~,2p0 52,500 P ol~~er P-24 with 0.5%~factant Grams SL Viscosity Viscosity Added Water " at ~~C

_10 22,500 90,500 2,5~,5p0 91,800 0 X5,700 91,000 lp 22,500 74,000 y5 ~~pp 67,000 -8?-Grams Viscosity Viscosity Bdded Water .~, ~20'C at ~°C
-10 52,000 85,000 -5 52,?00 92,500 p 49,000 84,500 46,600 90,500 lp 40,800 ?5,600 y5 40,000 69,700 TnflLpnce of Added SLrfacta_nt on the '~'emnera ~r ~en'sitivity of Aircraft Anti-Icing aids Polymer solutions were heated and 30 RPM Brookfield viscosities (centipoise) were measured at various temperatures in a thermostated bath. The activation energy was measured for a change in viscosity with respect to temperature. AH was determined by fitting the temperature dependence of the specific viscosity for 0.5% polymer solutions identified in Table T below and an amount (weight percent based on total solution) of Tergitol~ 15-S-5 nonionic surfactant identified in Table T in a 50/50 ethylene glycol/water solvent mixture to equation (3) herein by a standard least squares method. The results are given in Table T.
p ~ p 14.6 p ~ 0.25 20.1 p ~ 0.5 17.1 p ~ 1.0 -6.91 WO 93/24543 PCT/US93/04865 --~
_88_ The surfactant influences not only the magnitude of viscosity but also how sensitive viscosity is to temperature change.
EaamDhe 2~0 In_flLence of TemneratLre and ~L1'facta_n_t on. the ~,g,~y Sh a_r Viscosity profile of Aircraft n i-Icing Fluids A steady shear viscosity profile was obtained with a standard Bohlin VOft rheolometer equipped with a temperature control and Mooney-Couette shearing geometry. The polymer solutions contained 0.4°k polymer solids identified in Table U below, a amount (weight percent based on total solution) of Tergitol~ 15-S-5 nonionic surfactant identified in Table U and a 1:1 ethylene glycol:
water solvent mixture. The results are given in Table U. The viscosity is given in centipoise (cps).
Shear Rate Viscosity at Temperature ( /secl ~0°C Q°~ =10~C
0.2 ?ADD
1.0 1~
10.0 4~
Shear Rate Viscosity at Temperature ~Wse~i r_.1~ -20°C Q~. .'10-C
0.2 90~ ~ 1~
1.0 2300 4100 10.0 600 1~

~~.~ss~~

Eaa~l~.Z~.
In_flLer~p ~f ~IJat.~r 1'l,lLtion '~'em~gratLre. ~hea_r ~tp .~~~hea_r Viscosity Profile of ~ircra_ft Anti-Icing Fluids A steady shear viscosity profile was obtained with a standard Bohlin VOR, rheolometer equipped with temperature control and Mooney-Couette shearing geometry. The initial fluids contained 49.75 grams of ethylene glycol (polyester grade), 38.90 grams of distilled water, 0.85 grams of latez containing 30 weight percent of P-8 polymer solids and an amount of Tergitol~ NP-6 nonionic surfactant identified in Table V below. The fluids were adjusted to a pH of about 8.5 with a 45 percent aqueous solution of potassium hydro~dde. The results are given in Table V. The viscosity is given in centipoise (cps).
Viscosity m~rp~~Tp r Rate to Te And Shea Added Water,Viscosity Viscosity Viscosity at at at erams 20C_ 1.0 aec-10C_ 0.1 sec'1-20C. 10 sec'1 Ip ?81 4582 864 y5 595 3553 ?35 is35 s~9 i ~ .
WO 93/24543 b ~ ~ ~ ~ ~~ ~~ PCT/US93/04865 .
_g0_ ~ig~~~ wa w~waralmra T ~,Ste Te ent~ ~~1PA

Added WaterViscosity Viscosity Viscosity at at at , 20 .- l.O.sec'10r_~ 1 Z0G_ 10 sec 1 4094 _' 3~p 42500 y5 34?2 26800 1182 fir, 1g25 21190 Added Water,Viscosity Viscosity Viscosity at at at 1 10 cec-1 ' 20 ~.~s ~0 ._ 1.0 (1 ..
sec- C _ .~

0 ~1 ?61 -' ~,g 337g 871 r~ ~Og 815 gr 370 1778 614 Added WaterViscosity Viscosity Viscosity at at at , 20, 1 Q ._ 0.1 sec'1-20~ 1 0 ?373 _ _ lp 1948 21490 y5 21?1 18340 1217 1880 20360 1(~J5 25 1707 1?230 s"" WO 93/24543 ~ ~ ~ ~ ~ ~ ~ PGT/US93/04865 ~agg of Polymer ~~~d3LShear ~~~ Profile of ~rcraf~ t~nti-Tcing Fluids.
A steady shear viscosity profile was obtained with a .
standard Bohlin VOR, ~rheolometer equipped with temperature control and Mooney-Couette shearing geometry. The fluids contained 54.0 grams of ethylene glycol (polyester grade), 46.0 grams of distilled water, an amount of latex containing 30 weight percent of P-8 or P-31 polymer solids identified in Table W below, an amount of Tergitol~ 15-S-5 nonionic surfactant identified in Table W, 0.25 grams of Sandocarin 8132C corrosion inhibitor and 0.01 grams of Sag 7133 corrosion inhibitor. The fluids were adjusted to a pH of about 8.5 with a 45 percent aqueous solution of potassium hydro~de. The results are given in Table W. The viscosity is given in centipoise (cps).
pol~~er p-8 with 0 3 (Trams Ter~itol~_ ~~S-5 Noiio is Surfactant Latex, Viscosity at Viscosity at Q° . 0.1 sec-1 ?0°C.~10 sec-1 vr~--ams .
O,gS 3179 ?Ol 0.75 1~
Eolvm r P-31 with 0.~ crams Ter~itol~
15-S-5 Norioric Su_r_fa .ant Latez, Viscosity at Viscosity at 0°C. 0.1 sec-1 ~0°C. lO sec'1 0.85 WO 93/24543 PCT/US93/04865 '-~-fi~ ~~~~~;~~z Pol~pr p-31 with 0.5 C=rams Tergitol~
15-S-5 Nonionic Surfactant Latez, . Viscosity at Viscosity at 0°C. 0.1 sec-1 -20°C. 10 sec-1 0.85 Eggn,~~le 253 Shear Stahilitv and Water Sg;av Endurance of A;rcra_ft ~n_ti-Icing FlLds A shear stability test and water spray endurance test were performed by following the Association of European Airlines Anti-Icing Performance Test Specification for shear stability and water spray endurance as set forth in AEA Material Specification of De-/Anti-Icing Fluid for Aircraft, 6680?/R,. The fluid contained 49.75 grams of ethylene glycol (polyester grade), 38.90 grams of distilled water, 0.85 grams of latez containing 30 weight percent of P-8 polymer solids and 0.4 grams of Tergitol~ 15-S-5 nonionic surfactant. The fluid was adjusted to a pH of about 8.5 with a 45 percent aqueous solution of potassium hydro~de. The results showed less than 5 percent change in viscosity and ?0 minutes for water spray endurance. For the shear stability test, the rotation speed and mizing time were twice the specification value (7000 rpm rotation speed and 10 minutes mi~ag time).
Although the invention has been illustrated by certain of the preceding ezamples, it is not to be construed as being limited thereby; but rather, the invention encompasses the generic area as hereinbefore disclosed. Various modifications and embodiments can be made without departing from the spirit and scope thereof.

Claims (20)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. An aircraft anti-icing fluid comprising, in admixture, a glycol, water, and a hydrophobe-bearing, alkali-swellable, macromonomer-containing polymeric thickener being present in said anti-icing fluid in an amount less than 5 wt% and which thickens by an inter-molecular associative mechanism among hydrophobe groups, said fluid being sufficiently viscous to adhere to the airfoil surfaces of an aircraft at rest, but becoming sufficiently fluid under the influence of wind shear forces to flow off the airfoil surfaces when they are at or near take-off speed.

2. A fluid of claim 1 wherein the thickener comprises a carboxylic backbone to which the hydrophobes are attached by flexible, pendant chains.

3. A fluid of claim 2 in which the flexible pendant chain comprises a hydrophilic polymer.

4. A fluid of claim 1 in which the thickener is alkali-soluble.

5. A fluid of claim 2 in which two or more hydrophobe groups are attached to each flexible, pendant chain.

6. A fluid of claim 2 in which the flexible, pendant chain is sufficiently long to place the hydrophobes beyond the carboxyl environment of the backbone.

7. A fluid of claim 1 further comprising a surfactant, solvent, or non-solvent which increases the viscosity of the fluid when the aircraft is at rest, but does not significantly increase the viscosity of the fluid when the aircraft is at or near take-off speed.

8. A fluid of claim 1 wherein the water spray endurance time is at least about 30 minutes but wherein the boundary layer displacement thickness is less than about 8 mm at -20°C.

9. A fluid of claim 1 wherein each repeating unit of the thickener has a molecular weight of no more than about 6,000.

10. A composition comprising an anti-icing fluid suitable for ground treatment of aircraft which comprises an admixture of glycol, water and less than about 5 wt% of a macromonomer-containing polymer thickener which is a hydrophobe-bearing, alkali-swellable, polymeric thickener which thickens by an inter-molecular associative mechanism among hydrophobe groups, said macromonomer-containing polymer thickener being present in an amount sufficient to thicken the fluid to promote its adherence to aircraft surfaces when applied to a stationary aircraft but also allow for its wind shear-induced removal during the takeoff run prior to rotation, wherein the macromonomer-containing polymer comprises:
(A) about 1-99.9 weight percent of one or more alpha, beta-monoethylenically unsaturated carboxylic acids;

(B) about 0-98.9 weight percent of one or more monoethylenically unsaturated monomers;
(C) about 0.1-99 weight percent of one or more monoethylenically unsaturated macromonomers; and (D) about 0-20 weight percent or greater of one or more polyethylenically unsaturated monomers.

11. The composition of claim 10 wherein said monoethylenically unsaturated macromonomer is represented by the formula:
wherein:
R1 is a monovalent residue of a substituted or unsubstituted complex hydrophobe compound;
each R2 is the same or different and is a substituted or unsubstituted divalent hydrocarbon residue;
R3 is a substituted or unsubstituted divalent hydrocarbon residue;
R4, R5 and R6 are the same or different and are hydrogen or a substituted or unsubstituted monovalent hydrocarbon residue; and z is a value of 0 or greater.

12. The composition of claim 11 wherein the substituted or unsubstituted complex hydrophobe compound is represented by the formula selected from:
wherein R1 and R2 are the same or different and are hydrogen or a substituted or unsubstituted monovalent hydrocarbon residue. R3 is a substituted or unsubstituted divalent or trivalent hydrocarbon residue, each R4 is the same or different and is a substituted or unsubstituted divalent hydrocarbon residue, each R5 is the same or different and is a substituted or unsubstituted divalent hydrocarbon residue, R6 is hydrogen, a substituted or unsubstituted monovalent hydrocarbon residue or an ionic substituent, a and b are the same or different and are a value of 0 or 1, and x and y are the same or different and are a value of 0 or greater; provided at least two of R1, R2, R3, R4, R5 and R6 are a hydrocarbon residue having greater than 2 carbon atoms in the case of R1, R2 and R6 or having greater than 2 pendant carbon atoms in the case of R3, R4 and R5; and wherein R7 and R8 are the same or different and are hydrogen or a substituted or unsubstituted monovalent hydrocarbon residue, R9 and R12 are the same or different and are a substituted or unsubstituted divalent or trivalent hydrocarbon residue, each R10 is the same or different and is a substituted or unsubstituted divalent hydrocarbon residue, each R13 is the same or different and is a substituted or unsubstituted divalent hydrocarbon residue, R11 and R14 are the same or different and are hydrogen, a substituted or unsubstituted monovalent hydrocarbon residue or an ionic substituent, R15 is a substituted or unsubstituted divalent hydrocarbon residue, d and a are the same or different and are a value of 0 or 1, and f and g are the same or different and are a value of 0 or greater; provided at least two of R7, R8, R9, R10, R11, R12, R13, R14 and R15 are a hydrocarbon residue having greater than 2 carbon atoms in the case of R7, R8, R11 an R14 or having greater than 2 pendant carbon atoms in the case of R9, R10, R12, R13 and R15.

13. The composition of claim 12 wherein at least one of R4, R5, R10 and R13 is a hydrocarbon radical represented by the formula:
-CH[(OR19)j OR20]-wherein each R19 is the same or different and is a substituted or unsubstituted divalent hydrocarbon residue, R20 is hydrogen, a substituted or unsubstituted monovalent hydrocarbon residue or an ionic substituent, and j is a value of 0 or greater.

14. The composition of claim 12 wherein each R4, R5, R10 and R13 is selected from -CH2CH2-, -CH2CH(CH3)-, or mixtures thereof, and wherein R15 is selected from -phenylene-(CH2)m(Q)n(CH2)m- phenylene- and -naphthylene-(CH2)m(Q)n(CH2)m- naphthylene-, wherein Q individually represents a substituted or unsubstituted divalent bridging group selected from -CR21R22-, -O-, -S-, -NR23-, -SiR24R25- and -CO-, wherein R21 and R22 individually represent a radical selected from hydrogen, alkyl of 1 to 12 carbon atoms, phenyl, tolyl and anisyl; R23, R24 and R25 individually represent a radical selected from hydrogen and methyl, and each m and n individually have a value of 0 or 1.

15. The composition of claim 11 in which said monoethylenically unsaturated macromonomer is represented by the formula:
wherein R1, R2, R4, and z are as defined in claim 5, each R19 is the same or different and is a substituted or unsubstituted divalent hydrocarbon residue and j is a value of 0 or greater.

16. The composition of claim 11 in which said monoethylenically unsaturated macromonomer is represented by the formula:
wherein R1, R2, and z are as defined in claim 11.

17. The composition of claim 11 in which said monoethylenically unsaturated macromonomer is represented by the formula:
wherein R1, R2, R4, and z are as defined in claim 11.

18. The composition of claim 10 in which said component (A) is methacrylic acid, said component (B) is ethyl acrylate, and said component (C) contains styryl, acrylic, allylic, methacrylic or crotonic unsaturation.

19. The composition of claim 10 in which said component (C) is a urethane of said complex hydrophobe compound with alpha, alpha-dimethyl-m-isopropenyl benzyl isocyanate.

20. The composition of claim 10 which is thickened further by an effective amount of a surfactant, solvent or non-solvent.