Title of Invention	A COMPOSITIONN COMPRISING A WATER SOLUBLE OR WATER DISPERSIBLE POLYMER
Abstract	A composition suitable for inhibiting the formation and deposition of scale imparting species, comprising a water-soluble or water dispersible polymer of the formula: wherein E is the repeat unit remaining after polymerization of an ethylenically unsaturated compound said ethylenically unsaturated compound is one or more of: carboxylic acid, sulfonic acid, phosphonic acid or amide form thereof or mixtures thereof; R1 is H or lower (C1-C4) alkyl; G is - CH2- or CHCH3-; R2 is - (CH2-CH2-0-)n; wherein n ranges from 1 to 20; X is S03, P03 or COO; Z is H or a water soluble cationic moiety; F is a repeat u nit of the formula: wherein R4 is H or lower (C1-C4) alkyl, R5 is hydroxy substituted alkyl or alkylene having from 1 to 6 carbon atoms; and c, d and e are positive integers.

Title of Invention

A COMPOSITIONN COMPRISING A WATER SOLUBLE OR WATER DISPERSIBLE POLYMER

Abstract

A composition suitable for inhibiting the formation and deposition of scale imparting species, comprising a water-soluble or water dispersible polymer of the formula: wherein E is the repeat unit remaining after polymerization of an ethylenically unsaturated compound said ethylenically unsaturated compound is one or more of: carboxylic acid, sulfonic acid, phosphonic acid or amide form thereof or mixtures thereof; R1 is H or lower (C1-C4) alkyl; G is - CH2- or CHCH3-; R2 is - (CH2-CH2-0-)n; wherein n ranges from 1 to 20; X is S03, P03 or COO; Z is H or a water soluble cationic moiety; F is a repeat u nit of the formula: wherein R4 is H or lower (C1-C4) alkyl, R5 is hydroxy substituted alkyl or alkylene having from 1 to 6 carbon atoms; and c, d and e are positive integers.

Full Text	FIELD OF THE INVENTION The present invention relates to novel polymeric compositions and their use in methods of inhibiting corrosion and controlling the formation and deposition of scale imparting compounds in aqueous systems such as cooling, boiler and gas scrubbing systems; pulp and paper manufacturing processes; in the pretreatment of metals; as rheology modifiers for concrete and cement additives; as cleaning agents for membranes; and as hydrophilic modifier components in personal care,cosmotic and pharmaceutical formulations. The novel polymeric compositions which are useful in accordance with the present invention comprise water-soluble or water-dispersible copolymers of ethylenically unsaturated monomers with sulfate, phosphate, phosphite or carboxylic terminated polyalkylene oxide allyl ethers. BACKGROUND OF THE INVENTION The problems of corrosion and scale formation and the attendant effects have troubled water systems for years. For instance, scale tends to accumulate on internal walls of various water systems, such as boiler and cooling systems, and thereby materially lessen the operational efficiency of the system. Deposits in lines, heat exchange equipment, etc., may originate from several causes. For example, precipitation of calcium carbonate, calcium sulfate and calcium phosphate in the water system leads to an accumulation of these scale-imparting compounds along or around the metals' surfaces which contact the flowing water circulating through the system. In this manner, heat transfer functions of the particular system are severely impeded. Corrosion, on the other hand, is a degradative electrochemical reaction of a metal with its environment. Simply stated, it is the reversion of refined metals to their natural state. For example, iron ore is iron oxide. Iron ore is refined into steel. When steel corrodes, it forms iron oxide which, if unattended, may result in failure or destruction of the metal, causing the particular water system to shut down until the necessary repairs can be made. Typically, in cooling water systems, the formation of calcium sulfate, calcium phosphate and calcium carbonate, among others, has proven deleterious to the overall efficiency of the cooling water system. Recently, due to the popularity of cooling treatments using high levels of orthophosphate to promote passivation of the metal surfaces in contact with the system water, it has become critically important to control calcium phosphate crystallization so that relatively high levels of orthophosphate may be maintained in the system to achieve the desired passivation without resulting in fouling or impeded heat transfer functions which would normally be caused by calcium phosphate deposition. Silica (SiO2) is present in most natural waters. When these waters are cycled in a cooling tower, the silica level increases and often a level is reached where precipitation of a silica species occurs. Sometimes the precipitation proceeds by the polymerization of silica itself, resulting in a silica gel. For this to occur, a relatively high SiO2 concentration is required, usually greater than approximately 200 ppm. However, when certain cations are present, silica species can precipitate at much lower concentrations. Cations that promote silica precipitation include, but are not limited to, Al3+, Mg2+, Zn2+ and Fe3+. Aluminum is very insoluble in water and readily precipitates under cooling water conditions. When aluminum gets into a cooling system (such as by carryover) it can cause serious precipitation problems. One such problem is the precipitation of phosphate species which may be present as a corrosion inhibitor. Such precipitates can be problematic due to both deposition and corrosion effects. Although steam generating systems are somewhat different from cooling systems, they share a common problem in regard to deposit formation. As detailed in the Betz Handbook of Industrial Water Conditioning, 9th Edition, 1991, Betz Laboratories Inc., Trevose, Pa, Pages 96-104, the formation of scale and sludge deposits on boiler heating surfaces is a serious problem encountered in steam generation. Although current industrial steam producing systems make use of sophisticated external treatments of the boiler feedwater, e.g., coagulation, filtration, softening of water prior to its feed into the boiler system, these operations are only moderately effective. In all cases, external treatment does not in itself provide adequate treatment since muds, sludge and hardness-imparting ions escape the treatment, and eventually are introduced into the steam generating system. In addition to the problems caused by mud, sludge or silt, the industry has also had to contend with boiler scale. Although external treatment is utilized specifically in an attempt to remove calcium and magnesium from the feedwater, scale formation due to residual hardness, i.e., calcium and magnesium salts, is always experienced. Accordingly, internal treatment, i.e., treatment of the water fed to the system, is necessary to prevent, reduce and/or retard formation of scale imparting compounds and their resultant deposition. In addition to carbonates of magnesium and calcium being a problem as regards scale, having high concentrations of phosphate, sulfate and silicate ions either occurring naturally or added for other purposes cause problems since calcium and magnesium, and any iron or copper present, react and deposit as boiler scale. As is obvious, the deposition of scale on the structural parts of a steam generating system causes poorer circulation and lower heat transfer capacity, resulting in an overall loss in efficiency. RELATED ART U. S. Patent No. 4,471,100 to Tsubakimoto et al. discloses a copolymer consisting of maleic acid and polyalkyleneglycol monoallyl ether repeat units useful as a dispersant for cement and paint and as a scale inhibitor for calcium carbonate. U. S. Patents Nos. 5,180,498; 5,292,379; and 5,391,238 to Chen et al., disclose copolymers of acrylic acid and polyethyleneglycol allyl ether for boiler water treatment and metal pretreating applications. U. S. Patent No. 5, 362,324 describes terpolymers of (meth) acrylic acid and polyethyleneglycol-monomethylether-(meth) acrylate and polypropyleneglycol di(meth)acrylate for superplasticizer applications. U. S. Patent No. 5,661,206 and EP448717 disclose similar technology but using diepoxy based compounds as crosslinking agents. Japanese Patents 93660, 226757 and 212152 disclose acrylic acid terpolymers with sodium methallylsulfonate and methoxy polyethylene glycol-monomethacrylate for superplasticizer applications. U. S. Patent No. 5,575,920 to Freese et al. discloses terpolymers of acrylic acid, allyloxy-2-hydroxypropylsulfonic ester (AHPS) and polyethyleneglycol allyl ether for cooling water treatment as calcium phosphate inhibitors. U. S. Patent No. 3,875,202 to Steckler discloses polymerizable ammonium and alkali metal salts of sulfated monoethylenically unsaturated alcohols of from 3 to 12 carbon atoms and of the alkenoxylated adducts of such alcohols. The polymerizable monomers are useful as co-polymerizable surfactants for self-stabilizing latexes and as comonomers in the copolymerization with otter monomers in the preparation of co- or ter-polymeric films and fibers, especially as receptors for basic dyes and to build in anti-static properties. Monomers such as vinyl chloride, ethyl acrylate, 2-ethylhexyl acrylate, vinyl acetate and N-methyl acrylamide are disclosed in the patent to be copolymerizable with the ammonium salt of sulfated monoethylenically unsaturated alcohols. The copolymers disclosed are not water-soluble. U. S. Patent No. 5,705,665 to Ichinohe et al. relates to organic silicon compounds having as one of the components ethoxylated allyl alcohol with alkali metal salt of sulfonate group in the molecule. The resulting compound is useful as a surface treating agent and modifier for inorganic material. The copolymers disclosed are not water-soluble or dispersible. DETAILED DESCRIPTION OF THE INVENTION The present invention pertains to novel water-soluble or water dispersible polymers, which contain pendant functional groups and their use in controlling the formation and deposition of mineral deposits and in inhibiting corrosion in various aqueous systems. The novel polymers useful in the present invention are copolymers or terpolymers having the structure of Formula I. Wherein E is the repeat unit remaining after polymerization of an ethylenically unsaturated compound; preferably, a carboxylic acid, sulfonic acid, phosphonic acid, or amide form thereof or mixtures thereof. R1 is H or lower (C1-C4) alkyl. G is -CH2- or -CHCH3-; R2 is (CH2-CH2-O)n or ( CH2- CHCH3-O)m where n and m range from about 1 to 100, preferably n is greater than 10 and m ranges from about 1 to 20. X is an anionic radical selected from the group consisting of SO3, P03, or COO; Z is H or hydrogens or any water soluble cationic moiety which counterbalances the valence of the anionic radical X, including but not limited to Na, K, Ca, or NH4. F, when present, is a repeat unit having the structure of Formula II. In Formula II, X and Z are the same as in Formula I. R4 is H or lower (C1-C4) alkyl. R5 is hydroxy substituted alkyl or alkylene having from about 1 to 6 carbon atoms. With respect to E of Formula I, it may comprise the repeat unit obtained after polymerization of acarboxylic acid, sulfonic acid, phosphonic acid, or amide form thereof or mixtures thereof. Exemplary compounds include but are not limited to the repeat unit remaining after polymerization of acrylic acid, methacrylic acid, acrylamide, methacrylamide, N-methyl acrylamide, N, N- dimethyl acrylamide, N-isopropylacrylamide, maleic acid or anhydride, fumaric acid, itaconic acid, styrene sulfonic acid, vinyl sulfonic acid, isopropenyl phosphonic acid, vinyl phosphonic acid, vinylidene di-phosphonic acid, 2- acrylamido-2-methyIpropane sulfonic acid and the like and mixtures thereof. Water—soluble salt forms of these acids are also within the purview of the present invention. More man one type of monomer unit E may be present in the polymer of the present invention. Subscripts c, d, and e in Formula I are the molar ratio of the monomer repeating unit. The ratio is not critical to the present invention providing that the resulting copolymer is water-soluble or water-dispersible. Subscripts c and d are positive integers while subscript e is a non-negative integer. That is, c and d are integers of 1 or more while e can be 0, 1,2.. .etc. A preferred copolymer of the present invention, that is where e = 0, is acrylic acid/polyethyleneglycol monoallyl ether sulfate of the structure: Wherein n is greater than 10. Z is hydrogen or a water-soluble cation such as Na, K, Ca or NH4. Molar ratio c:d ranges from 30:1 to 1:20. Preferably, the molar ratio of c:d ranges from about 15:1 to 1:10. The ratio of c to d is not critical to the present invention providing that the resulting polymer is water-soluble or water- dispersible. A preferred terpolymer of the present invention, that is where e is a positive integer, is acrylic acid/polyethyleneglycol monoallyl ether sulfate/1- allyloxy-2-hydroxypropylsulfonic acid of the structure. Wherein n ranges from about 1-100, preferably n is greater than 10. Z is hydrogen or a water-soluble cation such as, Na, K, Ca or NH4. Z may be the same or different in c, d and e. The mole ratio of c:d:e is not critical so long as the terpolymer is water-soluble or water-dispersible. Preferably the mole ratio c:d:e ranges from about 20:10:1 to 1:1:20. The polymerization of the copolymer and/or terpolymer of the present invention may proceed in accordance with solution, emulsion, micelle or dispersion polymerization techniques. Conventional polymerization initiators such as persulfates, peroxides, and azo type initiators may be used. Polymerization may also be initiated by radiation or ultraviolet mechanisms. Chain transfer agents such as alcohols, preferably isopropanol or allyl alcohol, amines or mercapto compounds may be used to regulate the molecular weight of the polymer. Branching agents such as methylene bisacrylamide, or polyethylene glycol diacrylate and other multifunctional crosslinking agents may be added. The resulting polymer may be isolated by precipitation or other well-known techniques. If polymerization is in an aqueous solution, the polymer may simply be used in the aqueous solution form. The molecular weight of the water-soluble copolymer of Formula I is not critical but preferably falls within the range Mw of about 1,000 to 1,000,000. More preferably from about 1,000 to 50,000 and most preferably from about 1,500 to 25,000. The essential criteria is that the polymer be water-soluble or water-dispersible. USE OF THE POLYMERS The polymers of the invention are effective for water treatment in cooling water, boiler and steam generating systems as deposit control and/or corrosion inhibition agents. The appropriate treatment concentration will vary depending upon the particular system for which treatment is desired and will be influenced by factors such as the area subjected to corrosion, pH, temperature, water quantity and the respective concentrations in the water of the potential scale and deposit forming species. For the most part, the polymers of the present invention will be effective when used at levels of from about 0.1-500 parts permillion parts of water, and preferably from 1 about to 100 parts per million of water contained in the aqueous system to be treated. The polymers may be added directly into the desired water system in an aqueous solution, continuously or intermittently. The polymers of the present invention are not limited to use in any specific category of aqueous system. They would be expected to inhibit the formation and deposition of scale forming salts in any aqueous system prone to that problem. For instance, in addition to boiler and cooling water systems, the polymers may also be effectively utilized in scrubber systems and the like wherein corrosion and/or the formation and deposition of scale forming salts is a problem. Other possible environments in which the polymers of the present invention may be used include heat distribution type seawater desalting apparatus, dust collection systems in iron and steel manufacturing industries, mining operations and geothermal systems. The polymers of the present invention are also efficacious as deposit and pitch control agents in the paper and pulp manufacturing processes for preventing deposit of pitch, calcium oxalate and barium sulfate. They can also be used as viscosity modifiers in mining and mineral processing applications to reduce the viscosity of slurries. The water-soluble or dispersible polymers of the present invention may be used in combination with topping agents in order to enhance the corrosion inhibition and scale controlling properties thereof. For instance, the polymers of the present invention may be used in combination with one or more compounds selected from the group consisting of inorganic phosphoric acids or salts thereof, phosphonic acid salts, organic phosphoric acid esters, and polyvalent metal salts or mixtures thereof. Such topping agents may be added to the system being treated in an amount of from about 1 to 500 ppm. Examples of inorganic phosphoric acids include condensed phosphoric acids and water-soluble salts thereof. Examples of phosphoric acids include orthophosphoric acids, primary phosphoric acids and secondary phosphoric acids and salts thereof. Examples of inorganic condensed phosphoric acids include polyphosphoric acids such as pyrophosphoric acid, tripolyphosphoric acid and the like, metaphosphoric acids such as trimetaphosphoric acid and tetrametaphosphoric acid and salts thereof. Examples of other phosphoric acid derivatives, which can be combined with the polymers of the present invention include aminopolyphosphonic acids such as aminotrimethylene phosphonic acid, ethylene diaminotetramethylene phosphonic acid and the like, methylene diphosphonic acid, hydroxyethylidene diphosphonic acid, 2-phosphonobutane 1,2,4, tricarboxylic acid, etc and salts thereof. Exemplary organic phosphoric acid esters which may be combined with the polymers of the present invention include phosphoric acid esters of alkyl alcohols such as methyl phosphoric acid ester, ethyl phosphoric acid ester, etc., phosphoric acid esters of methyl cellosolve and ethyl cellosolve, and phosphoric acid esters of polyoxyalkylated polyhydroxy compounds obtained by adding ethylene oxide to polyhydroxy compounds such as glycerol, mannitol, sorbitol, etc. Other suitable organic phosphoric esters are the phosphoric acid esters of amino alcohols such as mono, di, and tri-ethanol amines. The water-soluble polymers may also be used in conjunction with molybdates such as, sodium molybdate, potassium molybdate, lithium molybdate, ammonium molybdate, etc. The polymers of the present invention may be used in combination with yet other topping agents including corrosion inhibitors for iron, steel, copper, and copper alloys or other metals, conventional scale and contamination inhibitors, metal ion sequestering agents, and other conventional water treating agents. Examples of other corrosion inhibitors include tungstate, nitrites, borates, silicates, oxycarboxylic acids, amino acids, catechols, aliphatic amino surface active agents, benzotriazole, halogenated triazoles and mercaptobenzothiazole. Other scale and contamination inhibitors include lignin derivatives, tannic acids, starches, polyacrylic acids and their copolymers including but not limited to acrylic acid/2-acrylamido-2-methylpropanesulfonic acid copolymers and acrylic acid/allyloxy-2-hydroxypropane-3-sulfonic acid copolymers, maleic acids and their copolymers, polyepoxysuccinic acids and polyacrylamides, etc. Examples of metal ion sequestering agents include polyamines, such as ethylene diamine, diethylene triamine and the like and polyamino carboxylic acids, such as nitrilo triacetic acid, ethylene diamine tetraacetic acid, and diethylenetriamine pentaacetic acid. U.S Patents Nos. 4,659,481; 4,717,499; 4,759,851; 4,913,822; and 4,872,995 disclose the use of specific copolymers in treating cooling, boiler, steam generating and other aqueous heat transfer systems to inhibit deposition of scales such as calcium phosphate, calcium phosphonate, calcium oxalate, iron oxide, zinc oxide and silica. Based upon the deposit control efficacy exhibited by the polymers of the present invention, it is believed that they could be substituted for the polymers disclosed in the above and other similar patents to provide improved performance in a wide variety of water based treatment applications. The copolymers of the present invention can be used alone or in combination with conventional cleaning agents such as surfactants, chelating agents, citric acid, phosphoric acid and other common reagents to remove deposit and prevent fouling on membranes used in the micro filtration, ultra filtration and reverse osmosis applications. The copolymers of the present invention can also be used as superplasticizers or retarders with cementitious materials in the construction industry applications. In addition, the polymers of the present invention are useful as viscosity modifiers to slurry viscosity in the mining and mineral processing and oil field operations. The present invention will now be further described with reference to a number of specific examples which are to be regarded solely as illustrative and not as restricting the scope of the present invention. EXAMPLES Example 1. Preparation of Acrylic Acid/ Ammonium Allylpolyethoxy (10) Sulfate Copolymer A suitable reaction flask was equipped with a mechanical agitator, a thermometer, a reflux condenser, a nitrogen inlet and two addition inlets for the initiator and monomer solutions. The flask was charged with 73.5 g of deionized water and 58.5 g (0.1 mol) of ammonium allyl polyethoxy(10) sulfate. While sparging with nitrogen, the solution was heated to 85 °C. An initiator solution containing 2.2 g of 2,2'-azobis(2-amidinopropane) hydrochloride (Wako V-50, from Wako Chemical Company) was sparged with nitrogen for ten minutes. The initiator solution and 21.6 g. (0.3 mol) of acrylic acid were added gradually to the reaction flask over a two-hour period. Following the addition, the solution was heated to 95 °C and held for 90 minutes. The reaction was then cooled to lower than 40 °C and 50% caustic solution was added until the pH measured 8-9. The structure of the resulting copolymer was verified by Carbon 13 NMR. The polymer solution was diluted to 30% solids and had a Brookfield viscosity of 48.6 cps at 25 °C. Example 2 Preparation of Acrylic Acid/ Ammonium Allylpolyethoxy (10) Sulfate Copolymer Utilizing the procedure and apparatus similar to the prior example, 147 g of deionized water and 61.9 g (0.11 mol) of ammonium allyl polyethoxy(l0) sulfate (DVP-010, from Bimax Inc.) were charged to the reaction flask. The solution was heated to 85 °C. An initiator solution containing sodium persulfate 1.9 g in water was sparged with nitrogen for ten minutes. The initiator .solution and 22.9 g (0.32 mol) of acrylic acid were gradually added to the reaction flask over a two-hour period. Following the addition, the solution was heated to 95 °C and held for 90 minutes. The reaction was cooled to lower than 40 °C and 50% caustic solution was added until the pH measured 4-5. The structure of the resulting copolymer was verified by Carbon 13 NMR. The polymer solution was diluted to 30% solids and had a Brookfield viscosity of 13.0 cps at 25 °C. Example 3 Preparation of Acrylic Acid/ Ammonium Allylpolyethoxy (10) Sulfate/Allyloxy-2-hydroxypropane-3-sulfonic Acid Terpolymer Utilizing the procedure and apparatus similar to Example 1,84.7 g of deionized water, 21.8 g (0.1 mol) of allyloxy-2-hydroxypropane-3-sulfonic acid and 58.5 g (0.1 mol) of the ammonium allyl polyethoxy-(10)-sulfate monomer were charged to the reaction flask. While sparging with nitrogen, the solution was heated to 85 °C. An initiator solution of 2,2'-azobis(2- amidinopropane)hydrochloride and 21.6 g (0.3 mol) of acrylic acid were added to the reaction flask over a 3.5 hour period. Following the addition, the solution was heated to 95 °C and held for two hours. The reaction was cooled and a 50% caustic solution was added for pH adjustment. The structure of the resulting copolymer was verified by Carbon 13 NMR. The polymer solution was diluted to 30% solids and had a Brookfield viscosity of 27.2 cps at 25 °C. Example 4 Preparation of Acrylic Acid/Methacrylic Acid/Ammonium Allylpolyerhoxy (10) Sulfate Terpolymer Utilizing the procedure and apparatus similar to Example 1, 109.7 g of deionized water, 20.6g of isopropyl alcohol and 58.5 g (0.1 mol) of ammonium allyl polyethoxy-(10)-sulfate monomer mixture were charged to the reaction flask. While sparging with nitrogen, the solution was heated to 85 °C. A solution of sodium persulfate and 21.6 g (0.3 mol) of acrylic acid and 8.6 g (0.1 mol) of methacrylic acid were added separately to the reaction flask over a two- hour period. Following the addition, the solution was heated to 95 °C and held for two hours. After the reaction, isopropyl alcohol was removed from the solution before cooling down and pH adjustment. The structure of the resulting copolymer was verified by Carbon 13 NMR. The polymer solution was diluted to 25% solids and had a Brookfield viscosity of 21.0 cps at 25 °C. Example 5 Preparation of Acrylic Acid/2-Acrylamido-2-methylpropanesulfonic acid /Ammonium Allylpolyethoxy (10) Sulfate Terpolymer Utilizing the procedure and apparatus similar to Example 4,127.9 g of deionized water, 20.5 g of isopropyl alcohol and 58.5 g (0.1 mol) of ammonium allyl polyethoxy-(10)-sulfate monomer were charged to the reaction flask. While sparging with nitrogen, the solution was heated to 85 °C. Sodium persulfate solution and a solution containing 21.6 g (0.3 mol) of acrylic acid and 20.7 g (0.1 mol) of 2-acrylamido-2-methylpropane sulfonic acid (AMPS ®, from Lubrizol Inc.) were added separately to the reaction flask over a two-hour period. Following the addition, the solution was heated to 95 °C and held for two hours before cooling down and pH adjustment. The structure of the resulting copolymer was verified by Carbon 13 NMR. The polymer solution was diluted to 25% solids and had a Brookfield viscosity of 17.0 cps at 25 °C. Example 6 Preparation of Allylpolyethoxy (10) Phosphate A suitable reaction flask was equipped with a mechanical agitator, a thermometer, and a reflux condenser. 20 g of hydroxypolyethoxy-(10)-allyl ether (0.04 mol., AAE-10, from Bimax Inc.) were charged to the reactor. 6.16 g of phosphorous oxychloride (0.04 mol) was added drop-wise to the reactor. The mixture was stirred vigorously for one hour followed by heating to 50 °C and holding for 4.5 hours. After cooling to ambient temperature, the reaction was quenched by slow addition to water. The pH was adjusted to 4 with caustic solution. Carbon 13 NMR analysis indicated the presence of phosphate ester. Example 7 Preparation of Acrylic Acid/ Allylpolyethoxy (10) Phosphate Copolymer Utilizing the procedure and apparatus similar to Example 1, 41.3 g of deionized water and 60.3 g (0.05 mol) of 49.8% allylpolyethoxy (10) phosphate from Example 6 were charged to the reaction flask. While sparging with nitrogen, the solution was heated to 85 °C. A solution of 2,2,-azobis(2- amidinopropane)hydrochloride (1.07 g) and 10.7 g (0.147 mol) of acrylic acid were added gradually to the reaction flask over a two-hour period. Following the addition, the solution was heated to 95 °C and held for 90 minutes before cooling down and pH adjustment. The structure of the resulting copolymer was verified by Carbon 13 NMR. The polymer solution was diluted to 25% solids and had a Brookfield viscosity of 221.0 cps at 25 °C. Example 8 Preparation of Acrylic Acid/ Allylpolyethoxy (10) Sulfate Copolymer Utilizing the procedure and apparatus similar to Example 1,58.6 g of deionized water, 58.6 g (0.1 mol) of allylpolyethoxy (10) sulfate and 0.8 g of allyl alcohol were charged to the reaction flask. While sparging with nitrogen, the solution was heated to 85 °C. A solution of sodium persulfate (1.92 g) in 6.0 g of water and 21.6 g (0.147 mol) of acrylic acid were added gradually to the reaction flask over a two-hour period. Following the addition, the solution was heated to 95 °C and held for 90 minutes before cooling down and pH adjustment. The structure of the resulting copolymer was verified by Carbon 13 NMR. The polymer solution was diluted to 25% solids and had a Brookfield viscosity of 65.0 cps at 25 °C. Table 1 summarizes the composition and physical properties of the copolymers prepared in accordance to the procedure described above. In Table 1, Examples 1-8 were prepared in accordance with the above correspondingly numbered descriptions. Example 9 was prepared in accordance with the description above for Examples 3-5 with a modified comonomer molar ratio. Examples 10-20 were prepared in accordance with the descriptions of Examples 1 and 2 with modified comonomer molar ratios and molecular weights. The molecular weights were obtained by Size Exclusion Chromatography analysis using polyacrylic acid as standards. MAA = methacrylic acid APES = ammonium allylpolyethoxy(l0) sulfate, containing 10 moles of ethylene oxide, DVP-0I0, from Bimax Inc. AHPS = l-allyloxy-2-hydroxypropyl-3 -sulfonic ether, from BetzDearborn Inc. AAE-10 Phosphate = polyethyleneglycol (10 moles of ethylene oxide) allyl ether phosphate AMPS ®= 2-acrylamido-2-methylpropanesulfonic acid, from Lubrizol Inc. Example 9 Phosphate Scale Inhibition - Bottle Test Protocol The testing of phosphate scale inhibition was undertaken in a static beaker test at varying treatment levels. The test protocol involved adding the treatment to a 100 ml solution containing calcium and phosphate ions and having a pH of 8.2 at 70° C. After 18 hours, a portion was filtered hot and the pH adjusted to determination of phosphate concentrations in the treated, stock and control solutions. The solution appearance was evaluated by visual inspection and compared to stock solutions. The conditions of the tests were: 400 ppm Ca, 100 ppm Mg and 35 ppm M-alkalinity all as CaCC3. Table 2 summarizes the percent inhibition of a known polymeric inhibitor/dispersant and polymers in accordance with the present invention over a broad range of treatment dosages. Table 3 summarizes the percent inhibition of a known polymeric inhibitor/dispersant and polymers in accordance with the present invention over a broad range of treatment dosages in the presence of 3 ppm FeCl2 .The data in tables 2 and 3 show the efficacy of the polymeric treatments of the present invention compared to a known treatment. Example 10 Phosphate Scale Inhibition - Dynamic Heat Transfer Simulations Developmental testing was also initiated with the AA/APES (3:1), Mw about 18,000, chemistry under dynamic heat transfer conditions in a laboratory scale cooling test rig. The water matrix contained 600 ppm Ca, 300 ppm Mg, 50 ppm M-alkalinity (all asCaCC3), 15 ppm orthophosphate, 3 ppm pyrophosphate, 1.2 ppm halogen substituted azole corrosion inhibitor, and either the AA/APES (Mw about 18,000), AA/AHPS (Mw about 15,000) or AA/AHPS/APES (Mw about 13,000) polymer. Operating parameters included a bulk temperature of 120° heat transfer rate of 8,00Q(BTU/(ft2hr)across a mild steel heat transfer tube, a water velocity of 2.8 ft/se, a retention time of 1.4 days (to 75% depletion) and a test duration of 7 days. Both mild steel and admiralty brass coupons were also inserted into the test rig. A summary of the polymer comparison is shown below. In this simulation, three parameters are monitored which are indicative of polymer performance. They are 1) the bulk turbidity values which develop in the cooling water, 2) the average delta phosphate values (the difference between filtered and unfiltered phosphate concentrations), and 3) the amount of deposition which is observed on the heat transfer tube. Under this recirculating rig condition, 5 ppm AA/AHPS is necessary to maintain acceptable heat transfer deposit control. A lower dosage of 4 ppm AA/AHPS results in a failure as indicated by slight deposition having been observed on the tube surface. In contrast, 2 ppm of the AA/APES chemistry not only keeps bulk turbidity and delta phosphate values low but also keeps the heat transfer surface free of deposition. This is a significant reduction (60%) in the amount of polymer necessary to control deposition in this cooling water. Additional testing was conducted under two upset conditions, i.e. elevated temperature/heat flux and 3 ppm iron contamination. These results are shown below The high temperature/flux evaluations were conducted using a bulk temperature of l40o F and a heat flux of 16,00 across the mild steel heat transfer tube. Again, the AA/AHPS simulation, at a dosage of 5 ppm, resulted in a test failure with significant heat transfer deposition having been observed. During the 2 ppm AA/APES evaluation, only a very slight amount of deposit was observed under this stressed condition. The iron contamination studies were conducted by adding 0.5 ppm iron (Fe+2) to the cooling water after the initial 24 hours of the evaluation. At this point, continuous feed of an iron solution was initiated into the test rig targeting a 3 ppm iron level, i.e. a 100 ppm Fe+2 solution was now fed to the rig at a rate of 0.24 Under this condition, AA/AHPS was shown to be ineffective at both a 9 ppm and a 12 ppm dosage. Elevated turbidity (7-13 NTU) and delta phosphate values (1-3.7 ppm) were observed, in addition to unacceptable deposition having formed on the heat transfer surface. The AA/APES chemistry, at a lower dosage of 6 ppm, maintained a lower bulk turbidity (5.3 ntu), a lower delta phosphate value (0.6 ppm) and, most importantly, prevented deposition on the heat transfer tube surface. Example 11 Silica Polymerization Inhibition Testing of silica polymerization inhibition was undertaken. The testing involved preparing 100 ml of a 500 ppm silica solution adjusted to pH 7.4, and adding 30 ppm of a treatment This solution was placed in a 30° C water bath and monomeric silica determinations were initiated and repeated every 30 minutes. The Hach Molybdate Reactive Silica test was utilized to determine the polymerization of silica. As polymerization occurs, the monomeric silica levels decrease. If the treatment is effective, elevated monomeric concentrations are realized relative to the untreated control. Tables 4 and 5 summarize the results of testing of several conventional treatments as well as a polymer in accordance with the present invention. At each time interval, the AA/APES chemistry maintains higher monomeric silica levels i.e. inhibits polymerization, than the other treatments. Acumer 1100 is polyacrylic acid available from Rohm & Haas. Belclene 400 is available from FMC Corp. PESA is polyepoxysuccininc acid Example 12 Silica Deposition Inhibition Bottle tests were conducted to evaluate the effects of treatments of the present invention on the solubility of silica and phosphate in the presence of aluminum. The test waters contained 700 ppm calcium, 185 ppm magnesium and 35 ppm M Alkalinity (all as CaCO3), 90 ppm S1O2, 14 ppm orthophosphate, 2 ppm pyrophosphate + a specific treatment. Treatments included a copolymer of AA/AHPS (Mw about 15,000), a second copolymer of AA/AHPS with a higher molecular weight (Mw about 55,000), and HEDP (hydroxyethylidene diphosphonic acid). The test waters were placed in 100 ml aliquots. A dosage of 5.0 ppm Al3+ was added to each aliquot, the pH adjusted to 8.0 and the aliquots held at 130 °F overnight. Filtered/unfiltered (FAJF) analyses of the water constituents were then conducted. The following table shows the results. As the table shows, AA/AHPS 1 (Mw about 15,000), AA/AHPS-2 (Mw about 55,000), and AA/AHPS-2 + HEDP, were ineffective in maintaining solubility, even at very high dosages. In striking contrast, the AA/APES (Mw about 13,000) polymer kept all the species soluble, even when fed at lower dosages. While this invention has been described with respect to particular embodiments thereof, it is apparent that numerous other forms and modifications of this invention will be obvious to those skilled in the art. The appended claims and this invention generally should be construed to cover all such obvious forms and modifications which are within the true spirit and scope of the present invention. WE CLAIM: 1. A composition suitable for inhibiting the formation and deposition of scale imparting species, comprising a water-soluble or water dispersible polymer of the formula: wherein E is the repeat unit remaining after polymerization of an ethylenically unsaturated compound said ethylenically unsaturated compound is one or more of: carboxylic acid, sulfonic acid, phosphonic acid or amide form thereof or mixtures thereof; R1 is H or lower (C1-C4) alkyl; G is - CH2- or CHCH3-; R2 is -(CH2-CH2-0-)n; wherein n ranges from 1 to 20; X is SO3, PO3 or COO ; Z is H or a water soluble cationic moiety; F is a repeat u nit of the formula: wherein R4 is H or lower (C1-C4) alkyl, R5 is hydroxy substituted alkyl or alkylene having from 1 to 6 carbon atoms; and c, d and e are positive integers. 2. The polymer as claimed in claim 1, wherein said ethylenically unsaturated compound is one or more of : acrylic acid , methacrylic acid, acrylamide, methacrylamide, N-methylacrylamide, N,N-dimethyl acrylamide, N-isopropyl acrylamide, maleic acid or anhydride , fumaric acid, itaconic acid, styrene sulfonic acid, vinyl sulfonic acid, isopropenyl phosphonic acid, vinyl phosphonic acid, vinylidene diphosphonic acid, 2-acrylamido-2-methylpropane sulfonic acid or mixtures thereof. 3. The composition as claimed in claim 1 wherein said water soluble cationic moiety is selected from the group consisting of Na+, K+, Ca+2 and NH4+. 4. The composition as claimed in claim 1, wherein the molecular weight Mw ranges from 1,000 to 50,000. 5. The composition as claimed in claim 1, wherein the molecular weight Mw ranges from 1,500 to 25,000. 6. The composition as claimed in claim 1, wherein the ratio c:d:e ranges from 20:10:1 to 1:1:20. 7. A composition comprising a water-soluble or water dispersible polymer of the formula wherein n ranges from 1-20; Z is hydrogen or a water soluble cation; and c, d and e are positive integers. S. The composition as claimed in claim 7, wherein said water soluble cation is selected from the group consisting of Na+, K+, Ca+2, NH4+ and mixtures thereof. 9 . The composition as claimed in claim 7, wherein the ratio c:d:e ranges from 20:10:1 to 1:1:20. 10. The composition as claimed in claim 7, wherein the molecular weight Mw ranges from 1,000 to 50,000. 11. The composition as claimed in claim 7, wherein the molecular weight Mw ranges from 1,000 to 25,000. 12, The composition as claimed in claim 7, wherein n ranges from 1 to 20. 13. A method of inhibiting the formation and deposition of scale imparting species on surfaces exposed to an aqueous system comprising adding to said aqueous system an effective amount for the purpose of a water-soluble or water- dispersible polymer of the formula: wherein E is the repeat unit remaining after polymerization of an ethylenically unsaturated compound; R1 is H or lower (C1-C4)alkyl; G is - CH2 - or -CHCH3-; R2 is - (CH2 - CH2-0)n or -(CH2-CHCH3-0-)n; wherein n ranges from 1 to 20 ; X is SO3, PO3 or COO; Z is H, hydrogens, or a water-soluble cationic moiety; F is a repeat unit of the formula: wherein R4 is H or lower (C1-C4) alkyl, R5 is hydroxy substituted alkyl or alkylene having from 1 to 6 carbon atoms; c and d are positive integers; and e is a non-negative integer. 14. The method as claimed in claim 13, wherein said ethylenically unsaturated compound is one or more of: carboxylic acid, sulfonic acid, phosphonic acid, or amide form thereof or mixtures thereof. 15". The method as claimed in claim 14, wherein said ethylenically unsaturated compound is one or more of: acrylic acid, methacrylic acid, acrylamide, methacrylamide, N-methyl acrylamide, N,N-dimethyl acrylamide, N-isopropyl acrylamide, maleic acid or anhydride, fumaric acid, itaconic acid, styrene sulfonic acid, vinyl sulfonic acid, isopropenyl phosphonic acid, vinyl phosphonic acid, vinylidene diphosphonic acid, 2-acrylamido-2-methylpropane sulfonic acid or mixtures thereof. 16. The method as claimed in claim 13, wherein said water-soluble cationic moiety is selected from the group Na+, K+, Ca+2 or NH4+. 17. The method as claimed in claim 13, wherein the molecular weight Mw ranges from 1,000 to 50,000. 1%. The method as claimed in claim 13, wherein the molecular weight Mw ranges from 1,500 to 25,000. 19. The method as claimed in claim 13, wherein the ratio c:d:e ranges from 20:10:1 to 1:1:20. 20. The method as claimed in claim 13, wherein e is zero and the ratio c:d ranges from 30:1 to 1:20. 21. The method as claimed in claim 13, wherein said polymer is added to said aqueous system in an amount from 0.1 to ppm to 500 ppm. 2Z. The method as claimed in claim 13, wherein said polymer is added to said aqueous system in an amount of from 1 ppm to 100 ppm. 23. The method as claimed in claim 13, wherein said aqueous system is a steam generating system. 24. The method as claimed in claim 13, wherein said aqueous system is a cooling water system. 25". The method as claimed in claim 13, wherein said aqueous system is a gas scrubber system. 26. The method as claimed in claim 13, wherein said water-soluble or water- dispersible polymer is added in combination with at least one or more topping agents. 2?. A method of inhibiting the formation and deposition of scale imparting species on surfaces exposed to an aqueous system comprising adding to said aqueous system an effective amount for the purpose of a water-soluble or water- dispersible polymer of the formula: wherein n ranges from 1-20, Z is hydrogen or a water-soluble cation and wherein the ratio c:d ranges from 30:1 to 1:20. 28. The method as claimed in claim 27, wherein said water soluble cation is selected from the group consisting of Na+, K+, Ca+2 or NH4+ or mixtures thereof. 2.1 The method as claimed in claim 2 7, wherein the molecular weight Mw ranges from 1,000 to 50,000. 30. The method as claimed in claim 27, wherein the molecular weight Mw ranges from 1,000 to 25,000. 3\.. The method as claimed in claim 27, wherein said polymer is added to said aqueous system in an amount from 0.1 ppm to 500 ppm. 32- The method as claimed in claim 2.7, wherein said polymer is added to said aqueous system in an amount of from 1 ppm to 100 ppm. 33. The method as claimed in claim 27, wherein said aqueous system is a steam generating system. 34. The method as claimed in claim 27, wherein said aqueous system is a cooling water system. 35. The method as claimed in claim 27, wherein said aqueous system is a gas scrubber system. 36. The method as claimed in claim 27, wherein said water-soluble or water- dispersible polymer is added in combination with at least one or more topping agents. 37. A method of inhibiting the formation and deposition of scale imparting species on surfaces exposed to an aqueous system comprising adding to said aqueous system an effective amount for the purpose of a water-soluble or water- dispersible polymer of the formula: wherein n ranges from 1-20, and Z is hydrogen or a water-soluble cation and wherein the ratio c:d:e ranges from 20:10:1 to 1:1:20. 39. The method as claimed in claim 37, wherein said water soluble cation is selected from the group consisting of Na+, K+, Ca+2 or NH4+ or mixtures thereof. 39. The method as claimed in claim 37, wherein said polymer is added to said aqueous system in an amount from 0.1 ppm to 500 ppm. 40. The method as claimed in claim 37, wherein said polymer is added to said aqueous system in an amount of from 1 ppm to 100 ppm. 4\|. The method as claimed in claim 37, wherein said aqueous system is a steam generating system. 42. The method as claimed in claim 37, wherein said aqueous system is a cooling water system. 43. The method as claimed in claim 37, wherein said aqueous system is a gas scrubber system. 44. The method as claimed in claim 37, wherein the molecular weight Mw ranges from 1,000 to 50,000. 4b". The method as claimed in claim 37, wherein the molecular weight Mw ranges from 1,000 to 25,000. 46. The method as claimed in claim 37, wherein said water-soluble or water- dispersible polymer is added in combination with at least one or more topping agents. A composition suitable for inhibiting the formation and deposition of scale imparting species, comprising a water-soluble or water dispersible polymer of the formula: wherein E is the repeat unit remaining after polymerization of an ethylenically unsaturated compound said ethylenically unsaturated compound is one or more of: carboxylic acid, sulfonic acid, phosphonic acid or amide form thereof or mixtures thereof; R1 is H or lower (C1-C4) alkyl; G is - CH2- or CHCH3-; R2 is - (CH2-CH2-0-)n; wherein n ranges from 1 to 20; X is S03, P03 or COO; Z is H or a water soluble cationic moiety; F is a repeat u nit of the formula: wherein R4 is H or lower (C1-C4) alkyl, R5 is hydroxy substituted alkyl or alkylene having from 1 to 6 carbon atoms; and c, d and e are positive integers.

Full Text

FIELD OF THE INVENTION
The present invention relates to novel polymeric compositions and their
use in methods of inhibiting corrosion and controlling the formation and
deposition of scale imparting compounds in aqueous systems such as cooling,
boiler and gas scrubbing systems; pulp and paper manufacturing processes; in the
pretreatment of metals; as rheology modifiers for concrete and cement additives;
as cleaning agents for membranes; and as hydrophilic modifier components in
personal care,cosmotic and pharmaceutical formulations. The novel polymeric
compositions which are useful in accordance with the present invention comprise
water-soluble or water-dispersible copolymers of ethylenically unsaturated
monomers with sulfate, phosphate, phosphite or carboxylic terminated
polyalkylene oxide allyl ethers.
BACKGROUND OF THE INVENTION
The problems of corrosion and scale formation and the attendant effects
have troubled water systems for years. For instance, scale tends to accumulate on
internal walls of various water systems, such as boiler and cooling systems, and
thereby materially lessen the operational efficiency of the system.
Deposits in lines, heat exchange equipment, etc., may originate from
several causes. For example, precipitation of calcium carbonate, calcium sulfate
and calcium phosphate in the water system leads to an accumulation of these
scale-imparting compounds along or around the metals' surfaces which contact
the flowing water circulating through the system. In this manner, heat transfer
functions of the particular system are severely impeded.
Corrosion, on the other hand, is a degradative electrochemical reaction of
a metal with its environment. Simply stated, it is the reversion of refined metals
to their natural state. For example, iron ore is iron oxide. Iron ore is refined into

steel. When steel corrodes, it forms iron oxide which, if unattended, may result
in failure or destruction of the metal, causing the particular water system to shut
down until the necessary repairs can be made.
Typically, in cooling water systems, the formation of calcium sulfate,
calcium phosphate and calcium carbonate, among others, has proven deleterious
to the overall efficiency of the cooling water system. Recently, due to the
popularity of cooling treatments using high levels of orthophosphate to promote
passivation of the metal surfaces in contact with the system water, it has become
critically important to control calcium phosphate crystallization so that relatively
high levels of orthophosphate may be maintained in the system to achieve the
desired passivation without resulting in fouling or impeded heat transfer
functions which would normally be caused by calcium phosphate deposition.
Silica (SiO2) is present in most natural waters. When these waters are cycled
in a cooling tower, the silica level increases and often a level is reached where
precipitation of a silica species occurs. Sometimes the precipitation proceeds by
the polymerization of silica itself, resulting in a silica gel. For this to occur, a
relatively high SiO2 concentration is required, usually greater than approximately
200 ppm. However, when certain cations are present, silica species can
precipitate at much lower concentrations. Cations that promote silica
precipitation include, but are not limited to, Al3+, Mg2+, Zn2+ and Fe3+.
Aluminum is very insoluble in water and readily precipitates under cooling water
conditions. When aluminum gets into a cooling system (such as by carryover) it
can cause serious precipitation problems. One such problem is the precipitation
of phosphate species which may be present as a corrosion inhibitor. Such
precipitates can be problematic due to both deposition and corrosion effects.
Although steam generating systems are somewhat different from cooling
systems, they share a common problem in regard to deposit formation.
As detailed in the Betz Handbook of Industrial Water Conditioning, 9th
Edition, 1991, Betz Laboratories Inc., Trevose, Pa, Pages 96-104, the formation

of scale and sludge deposits on boiler heating surfaces is a serious problem
encountered in steam generation. Although current industrial steam producing
systems make use of sophisticated external treatments of the boiler feedwater,
e.g., coagulation, filtration, softening of water prior to its feed into the boiler
system, these operations are only moderately effective. In all cases, external
treatment does not in itself provide adequate treatment since muds, sludge and
hardness-imparting ions escape the treatment, and eventually are introduced into
the steam generating system.
In addition to the problems caused by mud, sludge or silt, the industry has
also had to contend with boiler scale. Although external treatment is utilized
specifically in an attempt to remove calcium and magnesium from the feedwater,
scale formation due to residual hardness, i.e., calcium and magnesium salts, is
always experienced. Accordingly, internal treatment, i.e., treatment of the water
fed to the system, is necessary to prevent, reduce and/or retard formation of scale
imparting compounds and their resultant deposition. In addition to carbonates of
magnesium and calcium being a problem as regards scale, having high
concentrations of phosphate, sulfate and silicate ions either occurring naturally or
added for other purposes cause problems since calcium and magnesium, and any
iron or copper present, react and deposit as boiler scale. As is obvious, the
deposition of scale on the structural parts of a steam generating system causes
poorer circulation and lower heat transfer capacity, resulting in an overall loss in
efficiency.
RELATED ART
U. S. Patent No. 4,471,100 to Tsubakimoto et al. discloses a copolymer
consisting of maleic acid and polyalkyleneglycol monoallyl ether repeat units
useful as a dispersant for cement and paint and as a scale inhibitor for calcium
carbonate.
U. S. Patents Nos. 5,180,498; 5,292,379; and 5,391,238 to Chen et al.,

disclose copolymers of acrylic acid and polyethyleneglycol allyl ether for boiler
water treatment and metal pretreating applications.
U. S. Patent No. 5, 362,324 describes terpolymers of (meth) acrylic acid
and polyethyleneglycol-monomethylether-(meth) acrylate and
polypropyleneglycol di(meth)acrylate for superplasticizer applications. U. S.
Patent No. 5,661,206 and EP448717 disclose similar technology but using
diepoxy based compounds as crosslinking agents. Japanese Patents 93660,
226757 and 212152 disclose acrylic acid terpolymers with sodium
methallylsulfonate and methoxy polyethylene glycol-monomethacrylate for
superplasticizer applications.
U. S. Patent No. 5,575,920 to Freese et al. discloses terpolymers of
acrylic acid, allyloxy-2-hydroxypropylsulfonic ester (AHPS) and
polyethyleneglycol allyl ether for cooling water treatment as calcium phosphate
inhibitors.
U. S. Patent No. 3,875,202 to Steckler discloses polymerizable
ammonium and alkali metal salts of sulfated monoethylenically unsaturated
alcohols of from 3 to 12 carbon atoms and of the alkenoxylated adducts of such
alcohols. The polymerizable monomers are useful as co-polymerizable
surfactants for self-stabilizing latexes and as comonomers in the
copolymerization with otter monomers in the preparation of co- or ter-polymeric
films and fibers, especially as receptors for basic dyes and to build in anti-static
properties. Monomers such as vinyl chloride, ethyl acrylate, 2-ethylhexyl
acrylate, vinyl acetate and N-methyl acrylamide are disclosed in the patent to be
copolymerizable with the ammonium salt of sulfated monoethylenically
unsaturated alcohols. The copolymers disclosed are not water-soluble.
U. S. Patent No. 5,705,665 to Ichinohe et al. relates to organic silicon
compounds having as one of the components ethoxylated allyl alcohol with alkali
metal salt of sulfonate group in the molecule. The resulting compound is useful

as a surface treating agent and modifier for inorganic material. The copolymers
disclosed are not water-soluble or dispersible.
DETAILED DESCRIPTION OF THE INVENTION
The present invention pertains to novel water-soluble or water dispersible
polymers, which contain pendant functional groups and their use in controlling
the formation and deposition of mineral deposits and in inhibiting corrosion in
various aqueous systems. The novel polymers useful in the present invention are
copolymers or terpolymers having the structure of Formula I.

Wherein E is the repeat unit remaining after polymerization of an
ethylenically unsaturated compound; preferably, a carboxylic acid, sulfonic acid,
phosphonic acid, or amide form thereof or mixtures thereof. R1 is H or lower
(C1-C4) alkyl. G is -CH2- or -CHCH3-; R2 is (CH2-CH2-O)n or ( CH2-
CHCH3-O)m where n and m range from about 1 to 100, preferably n is greater
than 10 and m ranges from about 1 to 20. X is an anionic radical selected from
the group consisting of SO3, P03, or COO; Z is H or hydrogens or any water
soluble cationic moiety which counterbalances the valence of the anionic radical

X, including but not limited to Na, K, Ca, or NH4. F, when present, is a repeat
unit having the structure of Formula II.

In Formula II, X and Z are the same as in Formula I. R4 is H or lower
(C1-C4) alkyl. R5 is hydroxy substituted alkyl or alkylene having from about 1 to
6 carbon atoms.
With respect to E of Formula I, it may comprise the repeat unit obtained
after polymerization of acarboxylic acid, sulfonic acid, phosphonic acid, or
amide form thereof or mixtures thereof. Exemplary compounds include but are
not limited to the repeat unit remaining after polymerization of acrylic acid,
methacrylic acid, acrylamide, methacrylamide, N-methyl acrylamide, N, N-
dimethyl acrylamide, N-isopropylacrylamide, maleic acid or anhydride, fumaric
acid, itaconic acid, styrene sulfonic acid, vinyl sulfonic acid, isopropenyl
phosphonic acid, vinyl phosphonic acid, vinylidene di-phosphonic acid, 2-
acrylamido-2-methyIpropane sulfonic acid and the like and mixtures thereof.
Water—soluble salt forms of these acids are also within the purview of the present
invention. More man one type of monomer unit E may be present in the polymer
of the present invention.

Subscripts c, d, and e in Formula I are the molar ratio of the monomer
repeating unit. The ratio is not critical to the present invention providing that the
resulting copolymer is water-soluble or water-dispersible. Subscripts c and d are
positive integers while subscript e is a non-negative integer. That is, c and d are
integers of 1 or more while e can be 0, 1,2.. .etc.
A preferred copolymer of the present invention, that is where e = 0, is
acrylic acid/polyethyleneglycol monoallyl ether sulfate of the structure:

Wherein n is greater than 10. Z is hydrogen or a water-soluble cation
such as Na, K, Ca or NH4.
Molar ratio c:d ranges from 30:1 to 1:20. Preferably, the molar ratio of
c:d ranges from about 15:1 to 1:10. The ratio of c to d is not critical to the
present invention providing that the resulting polymer is water-soluble or water-
dispersible.
A preferred terpolymer of the present invention, that is where e is a
positive integer, is acrylic acid/polyethyleneglycol monoallyl ether sulfate/1-
allyloxy-2-hydroxypropylsulfonic acid of the structure.

Wherein n ranges from about 1-100, preferably n is greater than 10. Z is
hydrogen or a water-soluble cation such as, Na, K, Ca or NH4. Z may be the
same or different in c, d and e. The mole ratio of c:d:e is not critical so long as
the terpolymer is water-soluble or water-dispersible. Preferably the mole ratio
c:d:e ranges from about 20:10:1 to 1:1:20.
The polymerization of the copolymer and/or terpolymer of the present
invention may proceed in accordance with solution, emulsion, micelle or
dispersion polymerization techniques. Conventional polymerization initiators
such as persulfates, peroxides, and azo type initiators may be used.
Polymerization may also be initiated by radiation or ultraviolet mechanisms.
Chain transfer agents such as alcohols, preferably isopropanol or allyl alcohol,
amines or mercapto compounds may be used to regulate the molecular weight of
the polymer. Branching agents such as methylene bisacrylamide, or polyethylene
glycol diacrylate and other multifunctional crosslinking agents may be added.

The resulting polymer may be isolated by precipitation or other well-known
techniques. If polymerization is in an aqueous solution, the polymer may simply
be used in the aqueous solution form.
The molecular weight of the water-soluble copolymer of Formula I is not
critical but preferably falls within the range Mw of about 1,000 to 1,000,000.
More preferably from about 1,000 to 50,000 and most preferably from about
1,500 to 25,000. The essential criteria is that the polymer be water-soluble or
water-dispersible.
USE OF THE POLYMERS
The polymers of the invention are effective for water treatment in cooling
water, boiler and steam generating systems as deposit control and/or corrosion
inhibition agents. The appropriate treatment concentration will vary depending
upon the particular system for which treatment is desired and will be influenced
by factors such as the area subjected to corrosion, pH, temperature, water
quantity and the respective concentrations in the water of the potential scale and
deposit forming species. For the most part, the polymers of the present invention
will be effective when used at levels of from about 0.1-500 parts permillion parts
of water, and preferably from 1 about to 100 parts per million of water contained
in the aqueous system to be treated. The polymers may be added directly into the
desired water system in an aqueous solution, continuously or intermittently.
The polymers of the present invention are not limited to use in any
specific category
of aqueous system. They would be expected to inhibit the formation and
deposition of scale forming salts in any aqueous system prone to that problem.
For instance, in addition to boiler and cooling water systems, the polymers may
also be effectively utilized in scrubber systems and the like wherein corrosion
and/or the formation and deposition of scale forming salts is a problem. Other
possible environments in which the polymers of the present invention may be

used include heat distribution type seawater desalting apparatus, dust collection
systems in iron and steel manufacturing industries, mining operations and
geothermal systems. The polymers of the present invention are also efficacious
as deposit and pitch control agents in the paper and pulp manufacturing processes
for preventing deposit of pitch, calcium oxalate and barium sulfate. They can
also be used as viscosity modifiers in mining and mineral processing applications
to reduce the viscosity of slurries.
The water-soluble or dispersible polymers of the present invention may be
used in combination with topping agents in order to enhance the corrosion
inhibition and scale controlling properties thereof. For instance, the polymers of
the present invention may be used in combination with one or more compounds
selected from the group consisting of inorganic phosphoric acids or salts thereof,
phosphonic acid salts, organic phosphoric acid esters, and polyvalent metal salts
or mixtures thereof. Such topping agents may be added to the system being
treated in an amount of from about 1 to 500 ppm.
Examples of inorganic phosphoric acids include condensed phosphoric
acids and water-soluble salts thereof. Examples of phosphoric acids include
orthophosphoric acids, primary phosphoric acids and secondary phosphoric acids
and salts thereof. Examples of inorganic condensed phosphoric acids include
polyphosphoric acids such as pyrophosphoric acid, tripolyphosphoric acid and
the like, metaphosphoric acids such as trimetaphosphoric acid and
tetrametaphosphoric acid and salts thereof.
Examples of other phosphoric acid derivatives, which can be combined
with the polymers of the present invention include aminopolyphosphonic acids
such as aminotrimethylene phosphonic acid, ethylene diaminotetramethylene
phosphonic acid and the like, methylene diphosphonic acid, hydroxyethylidene
diphosphonic acid, 2-phosphonobutane 1,2,4, tricarboxylic acid, etc and salts
thereof.

Exemplary organic phosphoric acid esters which may be combined with
the polymers of the present invention include phosphoric acid esters of alkyl
alcohols such as methyl phosphoric acid ester, ethyl phosphoric acid ester, etc.,
phosphoric acid esters of methyl cellosolve and ethyl cellosolve, and phosphoric
acid esters of polyoxyalkylated
polyhydroxy compounds obtained by adding ethylene oxide to polyhydroxy
compounds such as glycerol, mannitol, sorbitol, etc. Other suitable organic
phosphoric esters are the
phosphoric acid esters of amino alcohols such as mono, di, and tri-ethanol
amines. The
water-soluble polymers may also be used in conjunction with molybdates such
as, sodium molybdate, potassium molybdate, lithium molybdate, ammonium
molybdate, etc.
The polymers of the present invention may be used in combination with
yet other topping agents including corrosion inhibitors for iron, steel, copper, and
copper alloys or other metals, conventional scale and contamination inhibitors,
metal ion sequestering agents, and other conventional water treating agents.
Examples of other corrosion inhibitors include tungstate, nitrites, borates,
silicates, oxycarboxylic acids, amino acids, catechols, aliphatic amino surface
active agents, benzotriazole, halogenated triazoles and mercaptobenzothiazole.
Other scale and contamination inhibitors include lignin derivatives, tannic acids,
starches, polyacrylic acids and their copolymers including but not limited to
acrylic acid/2-acrylamido-2-methylpropanesulfonic acid copolymers and acrylic
acid/allyloxy-2-hydroxypropane-3-sulfonic acid copolymers, maleic acids and
their copolymers, polyepoxysuccinic acids and polyacrylamides, etc. Examples
of metal ion sequestering agents include polyamines, such as ethylene diamine,
diethylene triamine and the like and polyamino carboxylic acids, such as nitrilo
triacetic acid, ethylene diamine tetraacetic acid, and diethylenetriamine
pentaacetic acid.

U.S Patents Nos. 4,659,481; 4,717,499; 4,759,851; 4,913,822; and
4,872,995 disclose the use of specific copolymers in treating cooling, boiler,
steam generating and other aqueous heat transfer systems to inhibit deposition of
scales such as calcium phosphate, calcium phosphonate, calcium oxalate, iron
oxide, zinc oxide and silica. Based upon the deposit control efficacy exhibited by
the polymers of the present invention, it is believed that they could be substituted
for the polymers disclosed in the above and other similar patents to provide
improved performance in a wide variety of water based treatment applications.
The copolymers of the present invention can be used alone or in
combination with conventional cleaning agents such as surfactants, chelating
agents, citric acid, phosphoric acid and other common reagents to remove deposit
and prevent fouling on membranes used in the micro filtration, ultra filtration and
reverse osmosis applications.
The copolymers of the present invention can also be used as
superplasticizers or retarders with cementitious materials in the construction
industry applications. In addition, the polymers of the present invention are
useful as viscosity modifiers to slurry viscosity in the mining and mineral
processing and oil field operations.
The present invention will now be further described with reference to a
number of specific examples which are to be regarded solely as illustrative and
not as restricting the scope of the present invention.
EXAMPLES
Example 1.
Preparation of Acrylic Acid/ Ammonium Allylpolyethoxy (10) Sulfate
Copolymer
A suitable reaction flask was equipped with a mechanical agitator, a
thermometer, a reflux condenser, a nitrogen inlet and two addition inlets for the

initiator and monomer solutions. The flask was charged with 73.5 g of deionized
water and 58.5 g (0.1 mol) of ammonium allyl polyethoxy(10) sulfate. While
sparging with nitrogen, the solution was heated to 85 °C. An initiator solution
containing 2.2 g of 2,2'-azobis(2-amidinopropane) hydrochloride (Wako V-50,
from Wako Chemical Company) was sparged with nitrogen for ten minutes. The
initiator solution and 21.6 g. (0.3 mol) of acrylic acid were added gradually to the
reaction flask over a two-hour period. Following the addition, the solution was
heated to 95 °C and held for 90 minutes. The reaction was then cooled to lower
than 40 °C and 50% caustic solution was added until the pH measured 8-9. The
structure of the resulting copolymer was verified by Carbon 13 NMR. The
polymer solution was diluted to 30% solids and had a Brookfield viscosity of
48.6 cps at 25 °C.
Example 2
Preparation of Acrylic Acid/ Ammonium Allylpolyethoxy (10) Sulfate
Copolymer
Utilizing the procedure and apparatus similar to the prior example, 147 g
of deionized water and 61.9 g (0.11 mol) of ammonium allyl polyethoxy(l0)
sulfate (DVP-010, from Bimax Inc.) were charged to the reaction flask. The
solution was heated to 85 °C. An initiator solution containing sodium persulfate
1.9 g in water was sparged with nitrogen for ten minutes. The initiator .solution
and 22.9 g (0.32 mol) of acrylic acid were gradually added to the reaction flask
over a two-hour period. Following the addition, the solution was heated to 95 °C
and held for 90 minutes. The reaction was cooled to lower than 40 °C and 50%
caustic solution was added until the pH measured 4-5. The structure of the
resulting copolymer was verified by Carbon 13 NMR. The polymer solution was
diluted to 30% solids and had a Brookfield viscosity of 13.0 cps at 25 °C.
Example 3

Preparation of Acrylic Acid/ Ammonium Allylpolyethoxy (10)
Sulfate/Allyloxy-2-hydroxypropane-3-sulfonic Acid Terpolymer
Utilizing the procedure and apparatus similar to Example 1,84.7 g of
deionized water, 21.8 g (0.1 mol) of allyloxy-2-hydroxypropane-3-sulfonic acid
and 58.5 g (0.1 mol) of the ammonium allyl polyethoxy-(10)-sulfate monomer
were charged to the reaction flask. While sparging with nitrogen, the solution
was heated to 85 °C. An initiator solution of 2,2'-azobis(2-
amidinopropane)hydrochloride and 21.6 g (0.3 mol) of acrylic acid were added to
the reaction flask over a 3.5 hour period. Following the addition, the solution
was heated to 95 °C and held for two hours. The reaction was cooled and a 50%
caustic solution was added for pH adjustment. The structure of the resulting
copolymer was verified by Carbon 13 NMR. The polymer solution was diluted
to 30% solids and had a Brookfield viscosity of 27.2 cps at 25 °C.
Example 4
Preparation of Acrylic Acid/Methacrylic Acid/Ammonium Allylpolyerhoxy
(10) Sulfate Terpolymer
Utilizing the procedure and apparatus similar to Example 1, 109.7 g of
deionized water, 20.6g of isopropyl alcohol and 58.5 g (0.1 mol) of ammonium
allyl polyethoxy-(10)-sulfate monomer mixture were charged to the reaction
flask. While sparging with nitrogen, the solution was heated to 85 °C. A
solution of sodium persulfate and 21.6 g (0.3 mol) of acrylic acid and 8.6 g (0.1
mol) of methacrylic acid were added separately to the reaction flask over a two-
hour period. Following the addition, the solution was heated to 95 °C and held
for two hours. After the reaction, isopropyl alcohol was removed from the

solution before cooling down and pH adjustment. The structure of the resulting
copolymer was verified by Carbon 13 NMR. The polymer solution was diluted
to 25% solids and had a Brookfield viscosity of 21.0 cps at 25 °C.
Example 5
Preparation of Acrylic Acid/2-Acrylamido-2-methylpropanesulfonic acid
/Ammonium Allylpolyethoxy (10) Sulfate Terpolymer
Utilizing the procedure and apparatus similar to Example 4,127.9 g of
deionized water, 20.5 g of isopropyl alcohol and 58.5 g (0.1 mol) of ammonium
allyl polyethoxy-(10)-sulfate monomer were charged to the reaction flask. While
sparging with nitrogen, the solution was heated to 85 °C. Sodium persulfate
solution and a solution containing 21.6 g (0.3 mol) of acrylic acid and 20.7 g (0.1
mol) of 2-acrylamido-2-methylpropane sulfonic acid (AMPS ®, from Lubrizol
Inc.) were added separately to the reaction flask over a two-hour period.
Following the addition, the solution was heated to 95 °C and held for two hours
before cooling down and pH adjustment. The structure of the resulting
copolymer was verified by Carbon 13 NMR. The polymer solution was diluted
to 25% solids and had a Brookfield viscosity of 17.0 cps at 25 °C.
Example 6
Preparation of Allylpolyethoxy (10) Phosphate
A suitable reaction flask was equipped with a mechanical agitator, a
thermometer, and a reflux condenser. 20 g of hydroxypolyethoxy-(10)-allyl ether
(0.04 mol., AAE-10, from Bimax Inc.) were charged to the reactor. 6.16 g of
phosphorous oxychloride (0.04 mol) was added drop-wise to the reactor. The
mixture was stirred vigorously for one hour followed by heating to 50 °C and
holding for 4.5 hours. After cooling to ambient temperature, the reaction was

quenched by slow addition to water. The pH was adjusted to 4 with caustic
solution. Carbon 13 NMR analysis indicated the presence of phosphate ester.
Example 7
Preparation of Acrylic Acid/ Allylpolyethoxy (10) Phosphate Copolymer
Utilizing the procedure and apparatus similar to Example 1, 41.3 g of
deionized water and 60.3 g (0.05 mol) of 49.8% allylpolyethoxy (10) phosphate
from Example 6 were charged to the reaction flask. While sparging with
nitrogen, the solution was heated to 85 °C. A solution of 2,2,-azobis(2-
amidinopropane)hydrochloride (1.07 g) and 10.7 g (0.147 mol) of acrylic acid
were added gradually to the reaction flask over a two-hour period. Following the
addition, the solution was heated to 95 °C and held for 90 minutes before cooling
down and pH adjustment. The structure of the resulting copolymer was verified
by Carbon 13 NMR. The polymer solution was diluted to 25% solids and had a
Brookfield viscosity of 221.0 cps at 25 °C.
Example 8
Preparation of Acrylic Acid/ Allylpolyethoxy (10) Sulfate Copolymer
Utilizing the procedure and apparatus similar to Example 1,58.6 g of
deionized water, 58.6 g (0.1 mol) of allylpolyethoxy (10) sulfate and 0.8 g of
allyl alcohol were charged to the reaction flask. While sparging with nitrogen,
the solution was heated to 85 °C. A solution of sodium persulfate (1.92 g) in 6.0
g of water and 21.6 g (0.147 mol) of acrylic acid were added gradually to the
reaction flask over a two-hour period. Following the addition, the solution was
heated to 95 °C and held for 90 minutes before cooling down and pH adjustment.
The structure of the resulting copolymer was verified by Carbon 13 NMR. The
polymer solution was diluted to 25% solids and had a Brookfield viscosity of
65.0 cps at 25 °C.

Table 1 summarizes the composition and physical properties of the
copolymers prepared in accordance to the procedure described above. In Table 1,
Examples 1-8 were prepared in accordance with the above correspondingly
numbered descriptions. Example 9 was prepared in accordance with the
description above for Examples 3-5 with a modified comonomer molar ratio.
Examples 10-20 were prepared in accordance with the descriptions of Examples
1 and 2 with modified comonomer molar ratios and molecular weights. The
molecular weights were obtained by Size Exclusion Chromatography analysis
using polyacrylic acid as standards.

MAA = methacrylic acid
APES = ammonium allylpolyethoxy(l0) sulfate, containing 10 moles of ethylene
oxide, DVP-0I0, from Bimax Inc.
AHPS = l-allyloxy-2-hydroxypropyl-3 -sulfonic ether, from BetzDearborn Inc.
AAE-10 Phosphate = polyethyleneglycol (10 moles of ethylene oxide) allyl ether
phosphate
AMPS ®= 2-acrylamido-2-methylpropanesulfonic acid, from Lubrizol Inc.
Example 9
Phosphate Scale Inhibition - Bottle Test Protocol
The testing of phosphate scale inhibition was undertaken in a static beaker
test at varying treatment levels. The test protocol involved adding the treatment
to a 100 ml solution containing calcium and phosphate ions and having a pH of
8.2 at 70° C. After 18 hours, a portion was filtered hot and the pH adjusted to
determination of phosphate concentrations in the treated, stock and control
solutions. The solution appearance was evaluated by visual inspection and
compared to stock solutions. The conditions of the tests were: 400 ppm Ca, 100
ppm Mg and 35 ppm M-alkalinity all as CaCC3. Table 2 summarizes the percent
inhibition of a known polymeric inhibitor/dispersant and polymers in accordance
with the present invention over a broad range of treatment dosages. Table 3
summarizes the percent inhibition of a known polymeric inhibitor/dispersant and
polymers in accordance with the present invention over a broad range of treatment
dosages in the presence of 3 ppm FeCl2 .The data in tables 2 and 3 show the
efficacy of the polymeric treatments of the present invention compared to a
known treatment.

Example 10
Phosphate Scale Inhibition - Dynamic Heat Transfer Simulations
Developmental testing was also initiated with the AA/APES (3:1), Mw
about 18,000, chemistry under dynamic heat transfer conditions in a laboratory
scale cooling test rig. The water matrix contained 600 ppm Ca, 300 ppm Mg, 50
ppm M-alkalinity (all asCaCC3), 15 ppm orthophosphate, 3 ppm pyrophosphate,
1.2 ppm halogen substituted azole corrosion inhibitor, and either the AA/APES
(Mw about 18,000), AA/AHPS (Mw about 15,000) or AA/AHPS/APES (Mw
about 13,000) polymer. Operating parameters included a bulk temperature of 120°
heat transfer rate of 8,00Q(BTU/(ft2hr)across a mild steel heat transfer tube, a
water velocity of 2.8 ft/se, a retention time of 1.4 days (to 75% depletion) and a
test duration of 7 days. Both mild steel and admiralty brass coupons were also
inserted into the test rig. A summary of the polymer comparison is shown below.

In this simulation, three parameters are monitored which are indicative of
polymer performance. They are 1) the bulk turbidity values which develop in the
cooling water, 2) the average delta phosphate values (the difference between
filtered and unfiltered phosphate concentrations), and 3) the amount of deposition
which is observed on the heat transfer tube. Under this recirculating rig
condition, 5 ppm AA/AHPS is necessary to maintain acceptable heat transfer
deposit control. A lower dosage of 4 ppm AA/AHPS results in a failure as
indicated by slight deposition having been observed on the tube surface. In
contrast, 2 ppm of the AA/APES chemistry not only keeps bulk turbidity and
delta phosphate values low but also keeps the heat transfer surface free of
deposition. This is a significant reduction (60%) in the amount of polymer
necessary to control deposition in this cooling water.
Additional testing was conducted under two upset conditions, i.e. elevated
temperature/heat flux and 3 ppm iron contamination. These results are shown below

The high temperature/flux evaluations were conducted using a bulk

temperature of l40o F and a heat flux of 16,00 across the mild steel
heat transfer tube. Again, the AA/AHPS simulation, at a dosage of 5 ppm,
resulted in a test failure with significant heat transfer deposition having been
observed. During the 2 ppm AA/APES evaluation, only a very slight amount of
deposit was observed under this stressed condition.
The iron contamination studies were conducted by adding 0.5 ppm iron
(Fe+2) to the cooling water after the initial 24 hours of the evaluation. At this
point, continuous feed of an iron solution was initiated into the test rig targeting a
3 ppm iron level, i.e. a 100 ppm Fe+2 solution was now fed to the rig at a rate of
0.24 Under this condition, AA/AHPS was shown to be ineffective at
both a 9 ppm and a 12 ppm dosage. Elevated turbidity (7-13 NTU) and delta
phosphate values (1-3.7 ppm) were observed, in addition to unacceptable
deposition having formed on the heat transfer surface. The AA/APES chemistry,
at a lower dosage of 6 ppm, maintained a lower bulk turbidity (5.3 ntu), a lower
delta phosphate value (0.6 ppm) and, most importantly, prevented deposition on
the heat transfer tube surface.
Example 11
Silica Polymerization Inhibition
Testing of silica polymerization inhibition was undertaken. The testing
involved preparing 100 ml of a 500 ppm silica solution adjusted to pH 7.4, and
adding 30 ppm of a treatment This solution was placed in a 30° C water bath and
monomeric silica determinations were initiated and repeated every 30 minutes.
The Hach Molybdate Reactive Silica test was utilized to determine the
polymerization of silica. As polymerization occurs, the monomeric silica levels
decrease. If the treatment is effective, elevated monomeric concentrations are
realized relative to the untreated control. Tables 4 and 5 summarize the results of

testing of several conventional treatments as well as a polymer in accordance with
the present invention. At each time interval, the AA/APES chemistry maintains
higher monomeric silica levels i.e. inhibits polymerization, than the other
treatments.

Acumer 1100 is polyacrylic acid available from Rohm & Haas.
Belclene 400 is available from FMC Corp.
PESA is polyepoxysuccininc acid
Example 12
Silica Deposition Inhibition
Bottle tests were conducted to evaluate the effects of treatments of the present
invention on the solubility of silica and phosphate in the presence of aluminum.
The test waters contained 700 ppm calcium, 185 ppm magnesium and 35 ppm M
Alkalinity (all as CaCO3), 90 ppm S1O2, 14 ppm orthophosphate, 2 ppm
pyrophosphate + a specific treatment. Treatments included a copolymer of
AA/AHPS (Mw about 15,000), a second copolymer of AA/AHPS with a higher
molecular weight (Mw about 55,000), and HEDP (hydroxyethylidene
diphosphonic acid). The test waters were placed in 100 ml aliquots. A dosage of
5.0 ppm Al3+ was added to each aliquot, the pH adjusted to 8.0 and the aliquots
held at 130 °F overnight. Filtered/unfiltered (FAJF) analyses of the water
constituents were then conducted. The following table shows the results.

As the table shows, AA/AHPS 1 (Mw about 15,000), AA/AHPS-2 (Mw
about 55,000), and AA/AHPS-2 + HEDP, were ineffective in maintaining
solubility, even at very high dosages. In striking contrast, the AA/APES (Mw
about 13,000) polymer kept all the species soluble, even when fed at lower
dosages.
While this invention has been described with respect to particular
embodiments thereof, it is apparent that numerous other forms and modifications
of this invention will be obvious to those skilled in the art. The appended claims
and this invention generally should be construed to cover all such obvious forms
and modifications which are within the true
spirit and scope of the present invention.

WE CLAIM:
1. A composition suitable for inhibiting the formation and deposition of
scale imparting species, comprising a water-soluble or water dispersible
polymer of the formula:

wherein E is the repeat unit remaining after polymerization of an
ethylenically unsaturated compound said ethylenically unsaturated
compound is one or more of: carboxylic acid, sulfonic acid, phosphonic
acid or amide form thereof or mixtures thereof; R1 is H or lower (C1-C4)
alkyl; G is - CH2- or CHCH3-; R2 is -(CH2-CH2-0-)n; wherein n ranges from
1 to 20; X is SO3, PO3 or COO ; Z is H or a water soluble cationic moiety;
F is a repeat u nit of the formula:

wherein R4 is H or lower (C1-C4) alkyl, R5 is hydroxy substituted alkyl or
alkylene having from 1 to 6 carbon atoms; and c, d and e are positive
integers.
2. The polymer as claimed in claim 1, wherein said ethylenically unsaturated
compound is one or more of : acrylic acid , methacrylic acid, acrylamide,
methacrylamide, N-methylacrylamide, N,N-dimethyl acrylamide, N-isopropyl
acrylamide, maleic acid or anhydride , fumaric acid, itaconic acid, styrene sulfonic
acid, vinyl sulfonic acid, isopropenyl phosphonic acid, vinyl phosphonic acid,
vinylidene diphosphonic acid, 2-acrylamido-2-methylpropane sulfonic acid or
mixtures thereof.
3. The composition as claimed in claim 1 wherein said water soluble cationic
moiety is selected from the group consisting of Na+, K+, Ca+2 and NH4+.
4. The composition as claimed in claim 1, wherein the molecular weight Mw
ranges from 1,000 to 50,000.
5. The composition as claimed in claim 1, wherein the molecular weight Mw
ranges from 1,500 to 25,000.
6. The composition as claimed in claim 1, wherein the ratio c:d:e ranges from
20:10:1 to 1:1:20.

7. A composition comprising a water-soluble or water dispersible polymer of the
formula

wherein n ranges from 1-20; Z is hydrogen or a water soluble cation; and c, d
and e are positive integers.
S. The composition as claimed in claim 7, wherein said water soluble cation is
selected from the group consisting of Na+, K+, Ca+2, NH4+ and mixtures thereof.
9 . The composition as claimed in claim 7, wherein the ratio c:d:e ranges from
20:10:1 to 1:1:20.
10. The composition as claimed in claim 7, wherein the molecular weight Mw
ranges from 1,000 to 50,000.
11. The composition as claimed in claim 7, wherein the molecular weight Mw
ranges from 1,000 to 25,000.

12, The composition as claimed in claim 7, wherein n ranges from 1 to 20.
13. A method of inhibiting the formation and deposition of scale imparting
species on surfaces exposed to an aqueous system comprising adding to said
aqueous system an effective amount for the purpose of a water-soluble or water-
dispersible polymer of the formula:

wherein E is the repeat unit remaining after polymerization of an ethylenically
unsaturated compound; R1 is H or lower (C1-C4)alkyl; G is - CH2 - or -CHCH3-;
R2 is - (CH2 - CH2-0)n or -(CH2-CHCH3-0-)n;
wherein n ranges from 1 to 20 ; X is SO3, PO3 or COO; Z is H, hydrogens, or a
water-soluble cationic moiety; F is a repeat unit of the formula:

wherein R4 is H or lower (C1-C4) alkyl, R5 is hydroxy substituted alkyl or
alkylene having from 1 to 6 carbon atoms; c and d are positive integers; and e is
a non-negative integer.
14. The method as claimed in claim 13, wherein said ethylenically unsaturated
compound is one or more of: carboxylic acid, sulfonic acid, phosphonic acid, or
amide form thereof or mixtures thereof.
15". The method as claimed in claim 14, wherein said ethylenically unsaturated
compound is one or more of: acrylic acid, methacrylic acid, acrylamide,
methacrylamide, N-methyl acrylamide, N,N-dimethyl acrylamide, N-isopropyl
acrylamide, maleic acid or anhydride, fumaric acid, itaconic acid, styrene sulfonic
acid, vinyl sulfonic acid, isopropenyl phosphonic acid, vinyl phosphonic acid,
vinylidene diphosphonic acid, 2-acrylamido-2-methylpropane sulfonic acid or
mixtures thereof.
16. The method as claimed in claim 13, wherein said water-soluble cationic
moiety is selected from the group Na+, K+, Ca+2 or NH4+.
17. The method as claimed in claim 13, wherein the molecular weight Mw
ranges from 1,000 to 50,000.
1%. The method as claimed in claim 13, wherein the molecular weight Mw
ranges from 1,500 to 25,000.
19. The method as claimed in claim 13, wherein the ratio c:d:e ranges from
20:10:1 to 1:1:20.

20. The method as claimed in claim 13, wherein e is zero and the ratio c:d
ranges from 30:1 to 1:20.
21. The method as claimed in claim 13, wherein said polymer is added to said
aqueous system in an amount from 0.1 to ppm to 500 ppm.
2Z. The method as claimed in claim 13, wherein said polymer is added to said
aqueous system in an amount of from 1 ppm to 100 ppm.
23. The method as claimed in claim 13, wherein said aqueous system is a
steam generating system.
24. The method as claimed in claim 13, wherein said aqueous system is a
cooling water system.
25". The method as claimed in claim 13, wherein said aqueous system is a gas
scrubber system.
26. The method as claimed in claim 13, wherein said water-soluble or water-
dispersible polymer is added in combination with at least one or more topping
agents.
2?. A method of inhibiting the formation and deposition of scale imparting
species on surfaces exposed to an aqueous system comprising adding to said
aqueous system an effective amount for the purpose of a water-soluble or water-
dispersible polymer of the formula:

wherein n ranges from 1-20, Z is hydrogen or a water-soluble cation and
wherein the ratio c:d ranges from 30:1 to 1:20.
28. The method as claimed in claim 27, wherein said water soluble cation is
selected from the group consisting of Na+, K+, Ca+2 or NH4+ or mixtures thereof.
2.1 The method as claimed in claim 2 7, wherein the molecular weight Mw
ranges from 1,000 to 50,000.
30. The method as claimed in claim 27, wherein the molecular weight Mw
ranges from 1,000 to 25,000.
3\.. The method as claimed in claim 27, wherein said polymer is added to said
aqueous system in an amount from 0.1 ppm to 500 ppm.
32- The method as claimed in claim 2.7, wherein said polymer is added to said
aqueous system in an amount of from 1 ppm to 100 ppm.
33. The method as claimed in claim 27, wherein said aqueous system is a
steam generating system.
34. The method as claimed in claim 27, wherein said aqueous system is a
cooling water system.

35. The method as claimed in claim 27, wherein said aqueous system is a gas
scrubber system.
36. The method as claimed in claim 27, wherein said water-soluble or water-
dispersible polymer is added in combination with at least one or more topping
agents.
37. A method of inhibiting the formation and deposition of scale imparting
species on surfaces exposed to an aqueous system comprising adding to said
aqueous system an effective amount for the purpose of a water-soluble or water-
dispersible polymer of the formula:

wherein n ranges from 1-20, and Z is hydrogen or a water-soluble cation
and wherein the ratio c:d:e ranges from 20:10:1 to 1:1:20.
39. The method as claimed in claim 37, wherein said water soluble cation is
selected from the group consisting of Na+, K+, Ca+2 or NH4+ or mixtures thereof.

39. The method as claimed in claim 37, wherein said polymer is added to said
aqueous system in an amount from 0.1 ppm to 500 ppm.
40. The method as claimed in claim 37, wherein said polymer is added to said
aqueous system in an amount of from 1 ppm to 100 ppm.
4|. The method as claimed in claim 37, wherein said aqueous system is a
steam generating system.
42. The method as claimed in claim 37, wherein said aqueous system is a
cooling water system.
43. The method as claimed in claim 37, wherein said aqueous system is a gas
scrubber system.
44. The method as claimed in claim 37, wherein the molecular weight Mw
ranges from 1,000 to 50,000.
4b". The method as claimed in claim 37, wherein the molecular weight Mw
ranges from 1,000 to 25,000.
46. The method as claimed in claim 37, wherein said water-soluble or water-
dispersible polymer is added in combination with at least one or more topping
agents.

A composition suitable for inhibiting the formation and deposition of scale
imparting species, comprising a water-soluble or water dispersible polymer of the
formula:
wherein E is the repeat unit remaining after polymerization of an ethylenically
unsaturated compound said ethylenically unsaturated compound is one or more
of: carboxylic acid, sulfonic acid, phosphonic acid or amide form thereof or
mixtures thereof; R1 is H or lower (C1-C4) alkyl; G is - CH2- or CHCH3-; R2 is -
(CH2-CH2-0-)n; wherein n ranges from 1 to 20; X is S03, P03 or COO; Z is H or
a water soluble cationic moiety; F is a repeat u nit of the formula:
wherein R4 is H or lower (C1-C4) alkyl, R5 is hydroxy substituted alkyl or alkylene
having from 1 to 6 carbon atoms; and c, d and e are positive integers.

Documents:

910-KOLNP-2003-FORM-27.pdf

910-kolnp-2003-granted-abstract.pdf

910-kolnp-2003-granted-assignment.pdf

910-kolnp-2003-granted-claims.pdf

910-kolnp-2003-granted-correspondence.pdf

910-kolnp-2003-granted-description (complete).pdf

910-kolnp-2003-granted-examination report.pdf

910-kolnp-2003-granted-form 1.pdf

910-kolnp-2003-granted-form 18.pdf

910-kolnp-2003-granted-form 2.pdf

910-kolnp-2003-granted-form 26.pdf

910-kolnp-2003-granted-form 3.pdf

910-kolnp-2003-granted-form 5.pdf

910-kolnp-2003-granted-reply to examination report.pdf

910-kolnp-2003-granted-specification.pdf

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Patent Number

231342

Indian Patent Application Number

910/KOLNP/2003

PG Journal Number

10/2009

Publication Date

06-Mar-2009

Grant Date

04-Mar-2009

Date of Filing

15-Jul-2003

Name of Patentee

BETZDEARBORN INC.

Applicant Address

4636 SOMERTON ROAD, TREVOSE, PA

Inventors:

#	Inventor's Name	Inventor's Address
1	CHEN FU	1057 BALLINTREE LANE, WEST CHESTER, PA 19389
2	BUENTELLO KRISTIN E,	8 ROSENFIELD DRIVE NEWTOWN, PA 18940
3	KAECHELIN JULIE A	315 STEEL ROAD, APT. A9, FEASTERVILLE, PA 19053
4	KESSLER STEPHEN M	201 DONNA DRIVE, PLYMOUTH TOWNSHIP, PA 19462
5	MAY ROGER C.	279 ANN LANE, WARMINSTER, PA 18974
6	KOLSON NATALIE A	411 NORTH WALNUT STREET, WEST CHESTER, PA 19380

PCT International Classification Number

C02F 5/10

PCT International Application Number

PCT/US2002/06370

PCT International Filing date

2002-03-01

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	09/808,679	2001-03-15	U.S.A.