CA1181196A - Isopropenyl phosphonic acid copolymers and methods of use thereof - Google Patents

Abstract

Abstract of the Disclosure A water soluble isopropenylphosphonic acid copolymer composition and method of use thereof are disclosed. The copolymer comprises repeat units (a) of the formula wherein X = OH or OM, wherein M is a cation; and repeat units (?? ??
the formula

Description

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ISOPROPENYL PHOSPHONIC ACID COPOLYMERS AND
METHODS OF USE THEREOF

Field of the Invention The present invention pertains to a composition and method of utilization of same to inhibit corrosion and control the formation - and deposition of scale imparting compounds in water systems such as cooling, boiler and gas scrubbing systems.

Background of ~he Xnvention The problems of corrosion and scale fonmation and a~tendant e~fects have troubled water systems for yearsO For instance, scale tends to accumulate on internal walls of various water systems, such as boiler and cooling systems, and thereby materially lessens the operational efficiency of the sys~em.

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 agglomeration of these scale imparting compounds along or around the metal surfaces which contact the flowing water circula-ting through the system. In this manner, heat transfer functions of the particular system are severely impeded.

3~' ~., Corrosion9 on the other hand, is a degradative electro-chemical 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 oxide is refined into steel.
When the steel corrodes, it forms iron oxide which, if unattended, may result in failure or des~ruc~ion of the metal, causing the par-ticular water system to be shut down until the necessary repairs can be made.

Typically, in cooling water systems, the formation of cal cium sulfate, calcium phosphate and calcium carbonate, among others, has proven deleterious to the overall efficacy of the cooling water system. Recently, due to the popularity of cooling treatments using high levels of orthophosphate to promote passivation of the me~al surfaces in contact with the system water, it has become critically important to control calcium phosphate crystallization so tha~ rela-tively high levels of orthophosphate may be maintained in the sys-tem, to achieve the desired passivation, without resulting in foul-ing or impeded heat transfer functions which would normally be caused by calcium phosphate crystallization.

Although steam generating systems are somewhat different from cooling water systems, they share a common problem in regard to deposit formation.

As detailed in the Betz Handbook of Industrial Water Con-ditioning, 8th Edition, 1g80, Betz Laboratori~s, Inc., Trevose, PA
Pages 85-96, the formation of scale and sludge deposits on boiler heating surfaces is a serious problem encountered in steam genera-tion. Although current industrial steam producing systems make use of sophisticated external treatments of the boiler feedwater9 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, silts and hardness-imparting ions escape the treatment, and eventually are introduced into the stream generating system.

In addition to the problems caused by mud, sludge or silts, the industry has also had to contend with boiler scale. Al-though external treatment is utilized specifically in an attempt toremove 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 the scale imparting compounds and their deposi-tion. The carbonates of magnesium and calcium are not the only problem compounds as regards scale, but also waters having high con-tents 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 with each and deposit as boiler scale. As is obvious, the deposition of scale on the structural parts of a steam generating system causes poorer cir-culation and lower heat transfer capacity, resulting accordingly in an overall loss in efficiency.

Detailed D_escription_of the Invention In accordance with the invention, it has surprisingly been discovered that a copolymer (I) having repeat unit moieties la) and (b), as hereinbelow defined, is efficacious in controlling the for-mation of mineral deposits and inhibiting corrosion in various watersystems. Repeat unit moiety (a) has the structure l .
_--CH2 ~ C - _ X - P - X
O (a~
-wherein X = OH, or OM wherein M is a cation.

Repeat unit ~b) is characterized by the formula _ _--CH2~ C _ C = O
_ R1 _ (b~

wherein R1 is chosen from the group consis~ing of hydroxy, hydroxy-lated alkoxy, and amide, and water soluble salts thereof. Prefera-bly, R1 is hydroxylated lower alkyl o-f from abou~ 2-6 carbon atoms.
R2 in the above formula may equal alkyl of From 1-3 carbon atoms, or H, moieties. Based upon experimental data, the preferred repeat unit (b) is 2-hydroxypropylacrylate.

It is to be noted that terpolymers comprising two or more different members selected from the repeat unit (b) grouping and a member from the repeat unit (a) grouping are also within the purview of the invention.

In addition to the above two noted essential repeat units, (a) and (b), an optional third repeat unit (c) may be incorporated into the polymer backbone. Preferably, this third unit (c) is a maleic acid or maleic anhydride moiety.

The phosphonic acid monomer corresponding to repeat unit (a) above, which is to be co-polymerized with a monomer or monomers corresponding to repeat unit (b), may be prepared by a reaction mechanism involving the nucleophilic addition of PC13 to the carbonyl group of acetone. For instance, the reaction may proceed in accordance with the following equations:

H3C ~ 3 (1) /C=O + PC13 ~ /C \
H3C H3C P+Cl3 H3C O~ H3C Cl \ / ~ HOAc \ /

(2) C > C
~ \ (HCl) / \
H3 P+Cl3 H3C PO(OH)2 H3C\ /Cl 10 (3) /C > CH2 = C - PO(OH)2 H3C PO(OH)z CH3 In this manner, the isopropenylphosphonic acid monomer (a) may be produced in a most cost efFective manner due to the relativity low economic cost of the precursor acetone.

It is also possible to produce the desired monomer ~a) via dehydration, by heating.2-hydroxy-2-propane phosphonic acid at a temperature of about 125-250C, as is detailed in U. S. Patent 2,365,466.

As to monomer (b), hydroxylated alkyl acrylates are pre-ferred, with the 2-hydroxypropylacrylate being most preferred.
These moieties can be readily prepared via an addition reaction be-tween acrylic acid or its derivatives or water soluble salts and the o~ide of the alkyl derivative desired. For example, to prepare 2-hydroxypropylacrylate, acrylic acid may be reacted with propylene oxide.

With respect to other monomeric possibili-ties correspond-ing to repeat unit (b), they are well known in the art. For in-stance, acrylic acid may be prepared directly from ethylene cyano-hydrin. Methacrylic acid may be prepared from acetone cyanohydrin, and acrylamide monomers may be prepared from acrylonitrile via treat-ment wi~h H2S04 or HCl.

If desired, it is possible to prepare a terpolymer utili-zing a third monomer (c) such as maleic acid or its anhydride.

After the desired monomers are obtained, copolymerizationmay proceed under step~reaction techniques in bulk, suspension, emul-sion, solution, or thermal polymerization conditions. For instance, an aqueous solution system may be used with ammonium persulfate serving as the initiator. Other standard copolymerization systems utilizing initiators such as benzoyl peroxide, azobisisobutyronitrile or ferrous sulfate may also ~e employed. The molecular weights of the copolymers may be controlled utilizing standard chain control agents such as secondary alcohols (isopropanol), mercaptans, halo-carbons, etc.

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The resulting copolymers (I) most advantageously have amolar ratio of moieties (a:b) of from about 3:1 to about 0.5:1, and most preferably from about 1:1, to 2:1.

Based upon presently available experimental data the pre-ferred copolymer (I) is isopropenylphosphonic acid/2-hydroxypropyl-acrylate (molar ratio a:b = 1:1).

The fact that polymers were formed, in accordance with inYention, was substantiated by 31PMR spectroscopy where broad absorptions between about -2G and -40 ppm (vs. o-H3P04) are known to indicate significant polymer formation.

Thé copolymers (I) should be added to the aqueous system, for which corrosion inhibiting, and/or deposit control activity is desired, in an amount effective for the purpose. This amount will vary depending upon the particular system for which treatment is desired and will be influenced by factors such as9 the area subject to co~rosion, pH, temperature, water quantity and the respective concentrations in the water of the potential scale and deposit form-ing species. For the most part, the copolymers will be effective when used at levels of about 0.1-500 parts per million parts of water, and preferably from about 10 to 20 parts per million of water contained in the aqueous system to be treated. The co-polymers may be added directly into the desired water system in a fixed quantity and in the state of an aqueous solution, either continuously or intermittently.

The copolymers of the present invention are not limited to use in any specific category of water system. 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 inventive polymers may be used include heat distribution type sea water de-salting apparatus and dust collection systems in iron and steelmanufacturing indus~ries.

The copolymers of the present invention can also be used with other components in order to enhance the corrosion inhibition and scale controlling properties thereof. For instance the co-polymers may be used in combination ~ith one or more kinds of - compounds selected from the group consisting o~ inorganic phosphoric acids, phosphonic acid salts, organic phosphoric acid esters, and polyvalent metal salts.

Examples of such inorganic phosphoric acids include con densed phosphoric acids and ~ater soluble salts thereof. The phosphoric acids include an orthophosphoric acid, a primary phos-phoric acid and a secondary phosphoric acid. 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.

As to the other phosphonic acid derivatives which are to be added in addition to the copolymers of the present invention, there may be mentioned aminopolyphosphonic acids such as aminotri-methylene phosphonic acid, ethylene diamine tetramethylene phos-phonic acid and the like, methylene diphosphonic acid, hydroxyethylidene~ diphosphonic acid, 2-phosphonobu~ane-1,2,4-tri-carboxylic acid, etc.

~3~6 Exemplary organic phosphoric acid esters which may be com-bined 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 poly-oxyalkyla~ed 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.
-Inorganic phosphoric acid, phosphonic acid, and organic phosphoric acid esters may be salts, pre~erably salts of alkali metal, ammonia, amine and so forth.

Exemplary polyvalent metal salts with may be combined withthe polymers of Formula (I) above include those capable of dissociat-ing polyvalent metal cations in water such as Zn~+, Ni++, e~c,which include zinc chloride, zinc sulfate, nickel sulfate, nickel chloride and so Forth.

'~hen the copolymer (I) is added to the aqueous system in combination with an additional component selected from the group consisting o-F inorganic phosphoric acids, phosphonic acids, organic phosphoric acids esters, or their water-soluble salts (all being re-ferred to hereinafter as phosphoric compounds), and polyvalent metal salts, a fixed quantity of said copolymer (I) may be added separately and in the state of aqueous solution into the system.
The copolymers (I) may be added either continuously or inter-mittently. Alternatively, the copolymers (I) may be blended witn the above noted phosphoric compounds or polyvalent metal salts and then added in the state oF aqueous solution into the water system either continuously or intennittently. The phosphoric compounds or polyvalent metal salts are utilized in the usual manner for corro-sion and scale preventing purposes. For instance, the phosphoric compounds or polyvalent metal salts may be added to a water sys~m continuously or intermittently to maintain their necessary concentrations.

Generally, the phosphoric compounds should be present in the aqueous system in an amount of about 1-100 ppm (as P04) or the polyvalent metal salts should be present in an amount of about I to 50 ppm (as metal cation).

As is conventional in the art, the phosphoric compounds or polyvalent me~al salts may be added, as pretreabment dosages, to the water system in an amount of about 20 to about 500 ppm, and thereafter a small quantity of chemicals may be added, as maintenance dosages.

The copolymers (I) may be used in combination with conven-tional corrosion inhibitors for iron, steel 9 copper, copper alloys or other metals, conventional scale and contamination inhibitors, metal ion seques~ering agents, and other conventional water treating agents. Exemplary corrosion inhibitors comprise chromates, bichro-mates, tungstate, molybdates, nitrites, borates, silicates, oxycar-boxylic acids, amino acids, catechols, aliphatic amino surface active agents, benzotriazole, and mercaptobenzothia~ole. Other scale and contamination inhibitors include lignin deriva~ives, tannic acids, starch, po1yacrylic soda, polyacrylic amide, etc. Metal ion seques-tering agents include ethylene diamine, diethylene triamine and thelike and polyamino carboxylic acids including nitrilo triacetic acid, ethylene diamine tetraacetic acid, and diethylene triamine pentaacetic acid.

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Examples The 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 inve~tion.

Preparation of Isopropenyl/Phosphonic Acid Monomer To a 3 liter 3 neck flask equipped with a magnetic stirrer, thermometer, and pressure compensated addition funnel, was added 300 9 (5.2 mole) of acetone. Phosphorus trichloride (730 9; ~.3 mole) was added rapidly through the addition funnel. The addition ~as only slightly exothermic. The mixture was stirred for 4 1/2 hours.
Acetic acid (1500 ml) was then added and a reflux condenser was added to the flask. The mixture became cloudy and refluxed as a copius quantity of hydrogen chloride was evolved. After the refluxing had subsided, hydrogen chloride gas was bubbled through the solution for 1/2 hour. The reaction mixture was then allowed to stir at room temperature overnigh~. The flask was equipped for distillation and volatiles were removed at atmospheric pressure until a head temperature of 118C was reached. A water aspirator was attached and the distillation continued until the pot tempera-ture reached 175C. The remainder of the Yolatiles were removed at ~ 1 mm and a pot temperature of 180-190C. The product was a viscous golden-yellow liquid and weighed 571 9 (91%). After the mixture was cooled sufficient water was added to give a 50% aqueous solution. The l3CMR spec~rum of aqueous product showed three doubiets at ~ = 140.4, 132.7 ppm (J = 172.1 Hz~; 129.9, 129.5 ppm (J= 9.8 Hz); 19.4, 18.9 ppm (J = 13.4 Hz). The 31PMR spectrum showed a single peak at ~ = -19.0 ppm. There was a trace of an inorganic pnosphorus impurity.

Example 1 Preparation of_Isopropenyl Phosphonic Acid/
Hy_roxypropylacrylate Copolymer (1:1 molar ratlo) To a 500 ml resin kettle equipped wi-th a mechanical stir-rer, thermometer, pressure compensated addition funnel, and re-Flux condenser, was added hydroxypropylacrylate (26.6 9; 0.2 mole). Iso-propenyl phosphonic acid (25.4 g; 0.2 mole) was dissolved in 154.2 9 water and added rapidly to the kettle. -The reaction mixture was then sparged with nitrogen for 1/2 hour. Ammonium persulfate (6 9) - 10 was added and the nitrogen sparge continued for an additional 1/2 hour. The mixture was heated to reflux for 2 hours. An additional 6 9 of ammonium persulfate was added. The mixture was then refluxed for an additional 2 hours. There was a definite increase in vis- -cosity after the second addition of ammonium persulfate. The yellow product had a pH of 1.00 and was tested without further purifica-tion. A 31PMR spectrum showed broad polymer absorptions centered at ~ = 32.9 and -34.7 ppm and a small amount of monomer at ~ =
-19.0 ppm. There was also a trace of inorganic phosphate.

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Example 2 Isopropenyl Phosphonic Acid/
. . .
Hydroxypropylacrylate Copolymer _1.1 molar ratio) The polymer was formed as in Example 1 except that the aqueous solution of isopropenylphosphonic acid was neutralized to pH 2.5 before addition to the reaction kettle. The amount of ammo-nium persulfate was reduced to 2 x 2.5 9. The yellowish brown solu-tion had a pH of 2.55. The 31PMR spectrum showed polymer absorp-tions centered at S = -33.1, -31.0, -27.5 and -24.7 ppm. There was no evidence of phosphorus monomer.

Exa_ple 3 Isopropenyl Phosphonic Acid/
_ _ Hydroxypropylacrylate Copolymer (1:1 molar ratio) __.

The polymer was formed as described in Example 2 except that the pH of the isopropenylphosphonic acid solution was adjusted to 4.0 before polymerization. The yellow aqueous product had a final pH of 3.67. The 31PMR spectrum showed polymer absorptions centered at -28~9 and -22.9 ppm. There were also trace quantities of inorganic phosphates.

Example_4 Isopropenyl Phosphonic Ac d/
Hydroxypropylacrylate-copolymer (3:1 molar ratio) Using the same polymerization apparatus as described in Example 1, 17.1 9 (0.13 mole) of hydroxypropylacrylate and 49.8 9 (0.41 mole3 of isopropenylphosphonic acid in 202.5 9 water (neutralized to pH 2.5) was heated to reflux with 6 9 of ammonium persulfate. After 2 hours of reflux an additional 6 9 of initiator was added followed by 2 hours of reflux. The final pH of the brown solution was 2.7. The 31PMR spectrum of the product had polymer absorptions at -30 to -33 ppm and -2~ ppm.

Example 5 Isopropenyl Phosphonic Acid/
Hydroxypropylacrylate Copolymer (2:1 molar ratio) Using the apparatus and methodology as described in Exam-ple 1, isopropenyl phosphonic acid (61.6 9, 54%, 0.27 mole), hydroxy-propylacrylate ~16.6 9, 0.13 mole) and water (121.8 9) were charged in the reactor. Ammonium persulfate (6 9) was added. After 1-1/2 hours of reflux, 6 9 additional persulfate was added followed by an equivalent reflux period. The final pH of the yellow solu~ion was 0.72.

Example 6 Isopropenylphosphonic Acid/
Hydroxypropylacrylate Copolymer (0.5:1 molar ratio) Used the method of Example 5, isopropenyl phosphonic acid (30.7 g, 54%, 0.14 mole), hydroxypropylacrylate (36.4 g, 0.28 mole) and water (144.9 g) were charged in the reactor . The bulk of the polymer crystallized during the first period of reflux and was found to be insoluble in water. -Example 7 Isopropenyl Phosphonic Acid/
Acrylamide Copo ymer (1:1 molar ratio) . . _ Aqueous isopropenyl phosphonic acid (47 9; 54%9 0.2 mole) 5 and aqueous acrylamide (28 9, 50%, 0.2 mole) were mixed in a resin kettle as previously described. Ammonium persulfate (6 9) and an additional 84 9 oF water were then added. The solution was sparged with nitrogen for 1/2 hour and heated to reflux. After 1-1/2 hours, an additional 6 9 of initiator was added followed by an additional - 10 1-1/2 hours of reflux. The aqueous product was yellow with a finalpH of 1.3. The 31PMR showed polymeric absorptions at ~ = -30.2 to -33.7 ppm and -25 to -29 ppm.

Example_8 Isopropenyl Phosphonic Acid/
. . . _ Hydroxyethylmethacrylate ~3:1 molar ratio) Aqueous isopropenyl phosphonic acid (71 9, 54%, 0.3 mole) S and hydroxyethylme~hacrylate (13 9, 0.1 mole) were mixed with 121.6 g water in a resin kettle. Ammonium persulfate (6 9) was added.
After 1-1/2 hours of reflux, an additional 6 9 of initiator was added followed by another 1-1/2 hours of reflux. The final product was a yellow solution with a pH of 0.68. The 31PMR showed polymeric absoprtions centered at ~ = -29.5 and -24.3 ppm.

Example 9 Isopropenyl Phosphonic Acid/Hydroxypropylacrylate/
Acrylic Acid Terpolymer 4:4:1 (molar ratio) Aqueous isopropenyl phosphonic acid (47 9, 54%, 0.2 mole), hydroxypropylacrylate (26 9, 0.2 mole) and maleic anhydride (5 g, 0.05 mole, neutralized to pH 5 in 50 ml water) were mixed with 82.6 g waker in a resin kettle under nitrogen. Ammonium persulfate (6 g) was added followed by 1-1/2 hours of reflux. An equivalent amount of initiator was added and the reflux period repeated. The final product was yellow with a pH of 0.99. The 31PMR showed polymer absorptions centered at ~ = -34, -32.3 and -28.8 ppm.

Example 10 Isopropenyl Phosphonic Acid/Hydroxypropylacrylate/
_ Methyl Acrylate Terpolymer (15:5:3 molar ratio) . . . ~
Aqueous isopropenyl phosphonic acid (71 9, 54%, 0.3 mole), hydroxypropylacrylate (13 9, 0.1 mole) and methyl acrylate (5 9, 0.06 mole) were mixed with 121.6 9 water containing 6 9 of ammonium pursulfate. After sparging with nitrogen for 1/2 hour, the mixture was heated to reflux for 1-1/2 hours. An additional 6 9 of initia-tor was added followed by an equivalent period of reflux. The final product had a pH of 0.65. The 31PMR showed significant polymeric absorptions at -32.4 and -24~3 ppm.

Example 11 Isopropenyl Phosphonic Acid/Hydroxyeropylacrylate/
Acrylic Ac~d Terpolymer ( 3.3:1 molar ratio) In a manner described in Example 8, aqueous isopropenyl phosphonic acid (47 9, 54%, 0.2 mole)~ hydroxypropylacrylate (26 9, 0.2 mole) and acrylic acid (5 9, 0.07 mole, neutralized to pH 5 in 50 ml wa~er) were mîxed wi~h 82.6 9 of water and polymerized. The final product had a pH of 1.08.

Example 12 In ~rder to evaluate the efficacy of isopropenylphosphonic acid/2-hydroxypropylacrylate copolymer (produced in accordance with Example 1) as a corrosion inhibitor and deposit control agent for cooling water systems, this copolymer was tested utili~ing a pro-cedure commonly referred to as the "Recirculator Test." According to this test, mild steel corrosion test coupons, and admiralty cor-rosion test coupons are cleaned, weighed and disposed on a rotating holder in a simulated cooling water bath which is contained within a 17 liter glass. The temperature of the system was maintained at about 120F and the rotational speed of the coupon holder was ad-justed so as to give a water velocity of about 1.3 feet per second past the coupons. Certain of the coupons were pretreated with zinc polyphosphate whereas the remaining coupons were not so pretreated.-The system has a constant makeup of new water and chemicals andblowdown. A heat transfer tube is also present in the system allow-ing a study of the effect of corrosion and scaling on a heat trans-fer surface. One end of the heat transfer tube is pretreated in similar fashion to coupon pretreatment.

Corrosion rate measurement was determined by weight loss measurement. At the end of one day, one mild steel coupon, one pretreated mild steel coupon, and one admiralty coupon were removed from the bath and a second weight measurement taken for each. At the termination of the test run, the remaining coupons were removed, cleaned and weighed.

Corrosion rates for the coupons were computed by differen-tial weight loss according to the following equation:

Corrosion Rate = Nth Day Weight LOSTS - lSt Day ~lght_Loss wherein N = 6 or 7.

The simulated cooling water was manufactured to give the following conditions:

~00 ppm Ca+2 as CaC03 300 ppm Mg+2 as CaC03 30 ppm total phosphates 18 ppm total inorganic phosphates 12 ppm orthophosphates pH = 7.0 A system pretreatmen~ step at a 25 ppm level (actives) of the copolymer was carried out over the first day of testing. After one day of this system pretreabment, the copolymer concentration was maintained at 10 ppm tactives) for the remainder of the test.

Results A~erage corrosion rates for the mild steel and admiralty coupons, respectively, were a highly acceptable 1.5 mpy and 0.3 mpy.
A blue black film of unknown composition formed on the mild steel coupons and on the non-pretreated end of the heat transfer tube.

At the 25 ppm level of copolymer, the system water was clear and an analytical test indicated no loss of orthophosphate in the water. The heat transfer surface was free of scale.

At a 10 ppm level of copolymer, the precipitation of ortho-phosphate was completely inhibited. This observation was supported by both physical and chemical analyses. The system water filtered easily through 0.2 um, and the chemical analyses for phosphate showed no loss of orthophosphate. At this copolymer treatment level, a black tightly adherent film formed on the heat transfer surface. It is not believed that this film would significantly re-duce heat transfer.

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Example 14 Another method of evaluating deposit control activity of a material consists of measuring its abilit~ to prevent bulk phase precipitation of a salt at conditions for which the salt would S usually precipitate. It is additionally important to recognize that the material being evaluated is tested at l'substoichiometric" con-centrations. That is, typical molar ratios of precipitating cation to the material being evaluated are on the order of 20:1 and much greater. Consequently, stoichiometric sequestration is not the route through which bulk phase precipitation is prevented. The well known phenomenon is also called "threshold" treatment and is widely practiced in water treatment technology for the prevention of scale (salt~ deposits from forming on various surfaces. In the results that follo~l calcium phosphate, commonly found in industrial water systems under various conditions, was selected as a precipitant.
The copolymers of the present invention have been evaluated for their ability to prevent precipitation (i.e., inhibit crystalli-7ation) of this salt. The results are expressed as "percent inhi-bition", positive values indicate the stated percentage of the precipitate was prevented from being formed. Except as where noted to the contrary, the following conditions, solutions, and testing procedure were utilized to perform the calcium phosphate and inhibition tests, the results of which are reported herein in the following table:

$

-2~-CALÇIUM PHOSPHATE INHIBITION PROCEDURE
~ ~ . . .
Conditions Solutions T = 70C 36.76 CaCl2 2H20/liter DIH20 pH 8.5 0.4482g NazHP04/liter DIH20 17 hour equilibration Ca+2 = 250 ppm as CaC03 P04~3 = 6 ppm Procedure 1) To about 1800 ml DIH20 in a 2 liter volumetric flask, add 20 ml of CaCl2 2H~0 solution followed by 2 drops of conc. HCl.
2) Add 40 ml of Na2HP04 solution.
3) Bring volume to 2 liters with DI water.

4~ Place 100 ml aliquots of solution in 4 oz glass bottles.

5) Add treatment.

6) Adjust pH as desired.

7) Place in 70~C water ba~h and equilibrate for 17 hours.

8) Remove samples and filter while hot through 0.2 u filters.

9) Cool to room temperature and ~ake Absorbance measurements using Leitz photometer (640 nm).
Preparation for Leitz a. 5 mls filtrate b. 10 mls Molybdate Reagent c. 1 dipper Stannous Reagent d. Swirl 1 minute, pour into Leitz cuvette;
wait 1 minute before reading.

10) Using current calibration curve (Absorbance vs ppm P04~3) find ppm Po4-3 of each sample.
Calculation:
% Inhibition = pPpPmm PPo4-3 (sttoecakt)ed) pPpm Po4-3 (Cconntrol) X 100 CL O ~ ~ N ~ Ln Cl~ O
O ~ 00 Ln ~ ; I
O O C~ 1 C~J ~
Q ~ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ ._ _ _ _ _ _ _ _ _ _ U~ O
0~E ~ ~ ~ ~ ~) O
~(~ C~ ~) N ~ C~ Lt) ~) Ln .,_ ~
~~ __ ___________________________--_ E
O~ 0~ ~ Ot) (S> 1-- ~ O q' O N
L~') N N N .--1 .--1 ~I N N ~
___ =============_==_====--====_=

V~
al ~ ~ ~D L~ 00 ~ ~ U~ O ar, ;~ ~ ~D 1-- Ot) C0 1-- d- O ~ ~D ~
~ N N N C`.l N ~') N .C~ C~J N
__ ____________________________ .

O ~ O N ~ OD cn OC) CO O
~r- ~ O Lf) ~ N ~D cn ~ O ~
a~2 --I N ~) N O ~1 0 0 0 ~ E
~
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~ a~ o, ~> a) cl: c~ 5 c~ > 2 ~ 2 aJ 2 ~ ~
O ~ I I I ~ 1~ ~? E ~ I O C I--- 0 ~ ~.
1~ r I~
Q ~L Q Q 2_ Q Q s ' ~ ~ s CL. ~ v~ Q ~ n~ ~_ O ~ S ~ E ~~-- E ~a ~ 0 ._ o `J --I ~ ~. ~. - ~ O 1--n ~ ~-- ' _ C Q
V- l l l l l l l I I ._ ~
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c~3 ~ ~t u> ~ c~ cn o ~ u. a~ cL
~ -~ ''O OQ ~
al a~ ) a a.l ~ ~ s o Q Q Q l::L Q Q Q /::~ Q C- ~ o-a E~ E E E E E E E E E E ~ ~ >~
:~ vcs ~ r S
-- X X X X X X X X X X
o E E E E E E E E~ E E '6 ~ C ~ Q Q

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While certain features of this invention have been described in detail with respect to various embodiments thereof~ it w;ll, of course, be apparent that other modifications can be made within the spirit and scope of this invention and it is not in-tended to limit the invention to the exact details shown above ex-cept insofar as they are defined in the appended claims.

Claims (40)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. Composition comprising a water soluble copolymer, said copolymer comprising repeat unit moieties (a) and (b) wherein said repeat unit moiety (a) comprises the structure, wherein X = OH or OM, wherein M is a cation, said repeat unit moiety (b) comprising the structure wherein R2 is H, or lower alkyl of from about 1-3 carbon atoms, and wherein R1 comprises a member selected from the group consisting of hydroxy, hydroxylated alkoxy, and amide, and water soluble salt forms thereof.

2. Composition as defined in Claim 1 further comprising a third repeat unit moiety (c) selected from the group consisting of maleic acid and maleic anhydride.

3. Composition as defined in Claim 1 wherein the molar ratio of said moieties a:b is from about 1:1 to 3:1.

4. Composition as defined in Claim 1 wherein said co-polymer comprises at least two different repeat unit moieties (b).

5. Composition as defined in Claim 1 wherein R2 = H and wherein R1 = hydroxylated alkoxy.

6. Composition as defined in Claim 5 wherein R1 = 2-hydroxypropyl.

7. Composition as defined in Claim 1 wherein R2 =
CH3 and wherein R1 = hydroxylated alkoxy.

8. Composition as defined in Claim 7 wherein R1 =
hydroxyethyl.

9. Composition as defined in Claim 1 wherein R2 =
H and R1 = NH2.

10. Composition as defined in Claim 4 wherein one of said moieties (b) comprises acrylic acid.

11. Composition as defined in Claim 4 wherein one of said moieties (b) comprises hydroxylated alkyl methacrylate.

12. Composition as defined in Claim 4 wherein one of said moieties (b) comprises methyl acrylate.

13. Composition as defined in Claim 1 further comprising an effective amount of a corrosion inhibitor compound (II) selected from the group consisting of inorganic phosphoric acids and water soluble salts thereof, phosphonic acids and water soluble salts thereof, organic phosphoric acid esters and water soluble salts there of, and polyvalent metal salts capable of being dissociated to poly-valent metal ions in water.

14. Composition as defined in Claim 13 wherein said inorganic phosphoric acid (II) is a member selected from the group consisting of orthophosphoric acid, primary phosphoric acid, secondary phosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, trimetaphosphoric acid, tetrametaphosphoric acid and water soluble salts thereof.

15. Composition as defined in Claim 13 wherein said phos-phonic acid (II) is a member selected from the group consisting of ethylene diamine tetramethylene phosphonic acid, methylene diphos-phonic acid, hydroxyethylidene-1,1-diphosphonic acid and 2-phos-phonobutane 1,2,4-tricarboxylic acid.

16. Composition as defined in Claim 13 wherein said poly-valent metal salt is a member selected from the group consisting of zinc chloride, nickel chloride, zinc sulfate and nickel sulfate.

17. Method of controlling the deposition of scale impart-ing precipitates on the structural parts of a system exposed to an aqueous medium comprising scale imparting precipitates under deposit forming conditions, said method comprising adding to said aqueous medium an effective amount for the purpose of a water soluble co-polymer (I) comprising repeat unit moieties (a) and (b), said repeat unit moiety (a) comprising the structure wherein X = OH or OM, wherein M is a cation, said repeat unit moiety (b) comprising the structure wherein R2 is H, or lower alkyl of from about 1-3 carbon atoms, and wherein R1 comprises a member selected from the group con-sisting of hydroxy, hydroxylated alkoxy, and amide, and water soluble salt forms thereof.

18. Method as defined in Claim 17 wherein said copolymer (I) is added to said aqueous medium in an amount of about 0.1-500 parts copolymer (I) per one million parts of said aqueous medium.

19. Method as defined in Claim 18 wherein said system is steam generating system.

20. Method as defined in Claim 18 wherein said system is a cooling water system.

21. Method as defined in Claim 18 wherein said system is a gas scrubbing system.

22. Method as defined in Claim 17 wherein R1 in said re-peat unit moiety (b) comprises hydroxylated alkoxy, and wherein R2 in said repeat unit moiety (b) is H.

23. Method as defined in Claim 22 wherein R1 in said re-peat unit moiety is 2-hydroxypropyl.

24. Method as defined in Claim 17 further comprising adding to said system, an effective amount for the purpose, of a compound (II) selected from the group consisting of inorganic phosphoric acids and water soluble salts thereof, phosphonic acids and water soluble salts thereof, organic phosphoric acid esters and water soluble salts thereof, and polyvalent metal salts capable of being dissociated to polyvalent metal ions in water.

25. Method as defined in Claim 24 wherein said inorganic phosphoric acid (II) is a member selected from the group consisting of orthophosphoric acid, primary phosphoric acid, secondary phosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, trimetaphosphoric acid, tetrametaphosphoric acid and water soluble salts thereof.

26. Method as defined in Claim 24 wherein said phosphonic acid (II) is a member selected from the group consisting of ethylene diamine tetramethylene phosphonic acid, methylene diphosphonic acid, hydroxyethylidene-1,1-diphosphonic acid and 2-phosphonobutane 1,2,4-tricarboxylic acid.

27. Method as defined in Claim 24 wherein said polyvalent metal salt is a member selected from the group consisting of zinc chloride, nickel chloride, zinc sulfate and nickel sulfate.

28. Method as defined in Claim 24 wherein said compound (II) is added to said system in an amount of 20 to about 500 parts per million parts of said system.

29. Method of inhibiting corrosion of metallic parts of an aqueous system comprising adding to said system an effective amount of a water soluble copolymer (I), said copolymer (I) having repeat unit moieties (a) and (b) wherein said repeat unit moiety (a) com-prises the structure, wherein X = OH or OM, wherein M is a cation, said repeat unit moiety (b) comprising the structure wherein R2 is H, or lower alkyl of from about 1-3 carbon atoms and wherein R1 comprises a member selected from the group consisting of hydroxy, hydroxylated alkoxy, and amide, and water soluble salt forms thereof.

30. Method as defined in Claim 29 wherein said copolymer (I) is added to said aqueous medium in an amount of about 0.1-500 parts polymer (I) per one million parts of said aqueous medium.

31. Method as defined in Claim 30 wherein said system is a steam generating system.

32. Method as defined in Claim 30 wherein said system is a cooling water system.

33. Method as defined in Claim 30 wherein said system is a gas scrubbing system.

34. Method as defined in Claim 29 wherein R1 in said re-peat unit moiety (b) comprises hydroxylated alkoxy, and wherein R2 in said repeat unit moiety (b) is H.

35. Method as defined in Claim 34 wherein R1 in said re-peat unit moiety (b) is 2-hydroxypropyl.

36. Method as defined in Claim 29 further comprising adding to said system, an effective amount for the purpose, of a compound (II) selected from the group consisting of inorganic phosphoric acids and water soluble salts thereof, phosphonic acids and water soluble salts thereof, organic phosphoric acid esters and water soluble salts thereof, and polyvalent metal salts capable of being dissociated to polyvalent metal ions in water.

37. Method as defined in Claim 36 wherein said inorganic phosphoric acid (II) is a member selected from the group consisting of orthophosphoric acid, primary phosphoric acid, secondary phos-phoric acid, pyrophosphoric acid, tripolyphosphoric acid, trimeta-phosphoric acid, tetrametaphosphoric acid and water soluble salts thereof.

38. Method as defined in Claim 36 wherein said phosphonic acid (II) is a member selected from the group consisting of ethylene diamine tetramethylene phosphonic acid, methylene diphosphonic acid, hydroxyethylidene-1,1-diphosphonic acid and 2-phosphonobutane 1,2,4-tricarboxylic acid.

39. Method as defined in Claim 36 wherein said polyvalent metal salt is a member selected from the group consisting of zinc chloride, nickel chloride, zinc sulfate and nickel sulfate.

40. Method as defined in Claim 36 wherein said compound (II) is added to said system in an amount of 20 to about 500 parts per million parts of said system.