BRPI0719243B1 - ANTEINVOVO AGENTS COVERED BY SULFONATE OR SULFATE - Google Patents

Description

Patent Descriptive Report for "ANTINÉVOA AGENTS COVERED BY SULPHONATE OR SULPHATE". CROSS REFERENCE TO RELATED APPLICATION. This Application claims the benefit, under Law 35 USC § 119, of United States Copending Provisional Application Serial Number 60 / 828,389, filed October 6, 2006, the entire contents of which are incorporated herein by reference.

BACKGROUND OF THE INVENTION Field of the Art The present invention relates to controlling mist formation above electrolyte solutions during processes such as electrodeposition, electroplating and metal electroforming where a potentially hazardous mist is formed.

Background and Related Art Electroplating is the process by which metals are recovered from aqueous electrolyte solutions that result from the extraction of the metal ion from an acid or base bleach solution. It is often employed in the recovery of metals, such as copper, from their metal-containing ore, wherein the leaching, solvent extraction, depletion and electrodeposition of metals from their ores have many of the same common unit operations or steps. These steps often include: (1) the valuable metals in mined and crushed ore being converted to an acidic and soluble form, possibly by oxidizing burning or reduction; (2) the ore from step (1) being leached, as with an aqueous solution of a strong acid, usually sulfuric acid, to form an aqueous acidic bleach solution having a pH of 0.9 to 2.0, containing the desired metal ion and relatively small amounts of other metal ions (impurities to be removed prior to final recovery of desired metals); (3) the resulting metal-impregnated aqueous acid bleach solution (s) being mixed in tanks (possibly with one or more repeats to improve metal recovery and / or to separate desired metal value (s)) with an extraction reagent, such as an oxime or mixture of oximes, that is selective for the desired goal (s), and dissolved in a water-insoluble and water-immiscible organic solvent and to form a complex / chelate metal extractor which is separated from the depleted aqueous phase of metal (s), for example in a settling tank; (4) The charged organic phase of the metals is then mixed (again possibly with one or more repeats) with a highly acidic extraction solution (eg concentrated sulfuric acid), which breaks apart from the complex, dissolving the ions. metals in another aqueous solution which, after another phase separation from the now depleted organic phase of the metal, is normally directed to an electrodeposition storage tank; and (5) in the storage tank, metal values are deposited on the cathodes by electroplating and then recovered from those plates. Other processes may be employed with other metals, such as nickel, zinc, and the like, to produce an electrolyte from which their respective metal values may be electrodeposited. It is during the electrodeposition step that an acid mist is often generated above the electrolyte (depletion of the aqueous phase). This mist is a result of small bubbles of oxygen that is generated in the anode while the metal is deposited in the cathode, and when oxygen rises as bubbles to the surface of the electrolyte solution and bursts, the small electrolyte particles Acid acids are dispersed in the air, resulting in an acid mist. Electroplating is the process of applying a metal coating to an article by passing an electric current through an electrolyte in contact with that article. ASTM adds some quality constraints by defining the term galvanize to be the electrodeposition of an adherent metal coating on an electrode such that a surface having different properties or dimensions than those of the base metal is formed.

In the electroplating process, metals or metalloids (non-metals that are semiconductor, for example arsenic, germanium, and the like, 1 which can be galvanized in the same way as metals) that are being used may be present in the compositions. aqueous in metallic and / or anionic form, and may be one or more of zinc, nickel, copper, chrome, manganese, iron, cobalt, gallium, germanium, arsenic, selenium, ruthenium, radio, palladium, silver, cadmium , Indian, tin, lead, bismuth, mercury, antimony, gold, iridium and / or platinum. In addition, many alloys such as brass, bronze, many gold alloys, lead-tin, nickel-iron, nickel-cobalt, nickel-phosphorus, tin-nickel, tin-zinc, zinc-nickel, zinc-cobalt, and Iron-zinc, even lead-indium, nickel-manganese, nickel-tungsten, palladium alloys, silver alloys, and zinc-manganese are also commercially galvanized.

Another type of electrodeposition for commercial use is a composite form, in which insoluble materials are coded together with the electrodeposited metal or alloy to produce particular desirable properties. Polytetrafluoroethylene (PTFE) particles are coded with nickel to improve lubricity. Silicon carbide and other hard particles, including diamond, are co-deposited with nickel to improve wear properties or to make cutting and grinding tools. .

The essential components of an electrogalvanization process are an electrode to be galvanized (the cathode); a second electrode to complete the circuit (the anode); an electrolyte containing the metal ions to be deposited; and an electric source of direct current. The electrodes are immersed in the electrolyte such that the anode is attached to the positive pole of the electrical source and the cathode to the negative pole. As the current is increased from zero, a minimum point is reached where metallic galvanization begins to take place in the cathode. .

Galvanizing tanks are made of materials that are either totally inert to the galvanizing solution or are coated with inert materials to protect the tank. For alkaline galvanizing solutions, mild steel materials are used. For acid galvanizing solutions, other materials are used depending on the chemical composition of the galvanizing bath such as titanium and various stainless steel alloys, polytetrafluoroethylene, KARBATE® waterproof graphite, HASTALLOY® nickel alloys, zirconium alloys and the like.

Galvanization tanks are fitted to the electrical source, 5 usually with round copper shielded busbars, with filters to remove fine particulate matter. Heating or cooling units may be present through the use of heating coils or cooling water coils, and two types of anodes may be used, namely soluble or insoluble (when soluble insoD anodes are used, The pH of the galvanizing solution is reduced along with the metal ion concentration, and in some galvanizing baths, a part of the anodes is replaced by insoluble anodes to avoid either metal ion concentration or reducing metal ion concentration). See, for example, Kirk-Othmer, Encyclopedia of Chemical Technology, 4th Edition, under the title, "Electroplating".

Since electroplating occurs exactly on the molecular surface of a job, it is important that the substrate surface is absolutely clean and receptive to electroplating, so there is usually a need for substrates to be electroplated to be prepared prior to electroplating. In an effort to achieve the substrate in this condition, several separate steps may be required, such as wiping, followed by electroleaning, followed by rinsing.

Galvanizing bath formulations may be flexible in some systems and very sensitive to variations, in others many of the most recent changes have been the result of useless treatments and safety requirements. In addition to the ability to deposit a coating having acceptable appearance and physical properties, the desired properties of the galvanizing bath include: high metal solubility, good electrical conductivity, good anode and cathode current efficiencies, non-corrosivity to substrates. , non-fumigation, stable, low risk, low anode dissolution during downtime, good starting power, good coating power, wide galvanizing range of current density, easy waste treatment, and economical to use. Few formulas have all these attributes, with only a few galvanizing solutions being used commercially without special additives, although chemical prices often constitute a relatively low percentage of the total cost of electroplating. Such additives are used in these solutions to clarify, reduce dot formation, and / or otherwise modify the character of the deposit or solution performance to meet some of the above criteria, with particular additive suppliers typically specifying formulations. preferred to use. Purification, often required once a galvanizing bath is prepared, is performed periodically to keep galvanizing solutions in working condition. Zinc alkaline galvanizing solutions are sensitive to a few mg / L heavy metal contamination, which can be precipitated using sodium sulfide and then filtered. Nickel galvanizing solutions may contain excess iron, which may be removed by oxidation with peroxide, precipitated to a pH of approximately 5, and filtered. More complex, less water-soluble organic contaminants, along with some trace metals, are removed with activated carbon treatments in separate treatment tanks. A purification treatment commonly used in both new and used galvanizing solution is so-called silencing, where heavy metal impurity is removed by electrolysis, usually at low current densities, using large disposable steel cathodes, good agitation and pH. lower speed the process.

Relatively simple analysis and testing, requiring little equipment, is required whenever a new galvanizing solution is composed, and thereafter at periodic intervals. Trace metal contaminants can be analyzed using the smear tests, colorimetrically, and by atomic absorption spectrometry. Additives, chemical equilibrium, the effects of impurities, and many other variables are tested with small galvanizing cells, such as Hull cells. The exact replacement of the galvanizing bath compositions depends on the metal that is galvanized. For example, copper cyanide galvanizing baths typically contain metallic copper, copper cyanide, potassium cyanide, potassium hydroxide, Rochelle salts, and sodium carbonate, while copper galvanizing baths typically contain metal copper, sulfate. copper, sulfuric acid, and various additives, and watt nickel galvanizing baths typically contain nickel metal, nickel sulfate, nickel chloride, boric acid, and various additives, while nickel sulfamate galvanizing baths contain nickel sulphates instead of nickel sulphate. Electroforming is the production or reproduction of articles by electrodeposition on a permanent or consumable axis or mold that is subsequently separated from the electrodeposit, with the electrodeposit becoming the article produced. Of all metals, copper and nickel are the most widely used in electroforming.

A common problem with all the above mentioned electrolysis procedures is the presence of acid or alkaline mist generated above the electrolyte solutions. Such mist is a serious health hazard and causes corrosion on plant facilities and operating equipment. To reduce the amount of mist, anti-fog agents (also referred to as defoggers and mist suppressants) are commonly added to electrolyte solutions. However, currently available anti-fog agents are not completely satisfactory due to limited defogging capacity, high loss rate of such anti-fog agents, interference with the electrolysis process, and / or ecological incompatibilities. In the case of electroplating, acid mist is particularly noteworthy and cumbersome, and the use of mist suppressing agents may interfere with the related extraction process (eg due to partial solubility in the organic extraction solution, promote formation emulsion, promote slow phase separation, and interfere with depletion or extraction kinetics). In addition, foam can also be a significant problem. Tjernlund, DM, et al., In "A Studyofthe Fire and Explosion Hazards Associated with the Electrowinning of Copper in Arizona Surface Mine Plants", Section 8, US Department of Labor Safety and Health Administration, Investigative Report, March 1999, reports on the formation of acid mist in the electrodeposition as follows: "Oxygen bubbles created at the anode rise to the electrolyte surface. On the surface, these bubbles expand above the liquid and then burst, releasing trapped oxygen into the atmosphere. The liquid in the bubble wall just before it ruptures is composed of the acid electrolyte solution. Like liquid wall ruptures, this liquid disintegrates into extremely small droplets that are rapidly transported through the air. The macroscopic effect of this process is the creation of a mist. strong acid just above the cells.This mist readily migrates to all parts of the workplace and represents a potential health hazard to storage tank personnel. Such mist also creates a corrosive atmosphere that can be detrimental to equipment and the very structure of storage tanks. "In Section 8c," Strategy 4: Surfactants, "the authors continue:" In most storage tanks, a Water soluble surface tension reducer is used to disfavor the formation of mist ... by reducing the surface tension of the electrolyte, the gas bubble wall becomes thinner when it hits and emerges on the electrolyte surface. This causes the bubble to burst earlier with smaller generation of mist droplets. "

The authors also note that 3M FC-100 and FC-1100 FLOURAD® products were the most commonly used antifog agents. They reported that FC-100 trapped the rising gas in traps in soap-foam-like bubbles above the surface, even at very low concentrations (a few hundred ppm). They also noted, however, that the resulting foamed layer also created significant potential fire / explosion problems. They included that the FC-1100 surfactant was significantly less prone to blistering than FC-100, but at higher concentrations also generated an undesirable bubble layer. 3M states that FC-1100 FLOURAD® contains 45% to 55% fluorochemical solids in 45% to 55% water and provides suppression of sulfuric acid mist in the copper electrodeposition storage tank without formation of a stable foam blanket on the surface of the electrodeposition cell. The exact nature of the fluorochemical solid has not been described. -. CY Cheng et al, in Evaluation of Saponins as Acid Mist Suppressants in Zinc Electrowinning, Hydrometallurgy, Volume 73 (2004), pages 133 to 145, report two products rich in saponins (Mistop® Quillaja Saponaria Extract and QLZinc® Saponin Extract). ) and includes the use of Mistop® saponins in a commercial copper electroplating operation. The authors report that saponins (the high molecular weight glycosides of steroids, steroid alkaloids or triterpenes found in plants, consisting of a sugar moiety attached to a steroidal triterpene or aglycone, often referred to as unrefined · Quillaja extracts ) are natural surface activation compounds which. provide stable foams in aqueous solutions. United States Patent No. 6,833,479 B2 (Witschger, et al), incorporated herein by reference in its entirety, discloses antifoaming agents which are alkoxy coated amines and trialkylol compounds having the structure: R ((AO) nH) mHp (formula (a)), wherein each AO group is independently an alkylenoxy group selected from ethylenoxy, 1,2-propylenoxy, 1,2-butylenoxy, and styrylenoxy groups; n is an integer from 2 to 100; m is an integer from 1 to the total number of -OH plus the -NH hydrogens in the group R before alkoxylation; the sum of m plus p equals the number of -OH plus the hydrogens of -NH in the group R before alkoxylation; and group R is a group selected from the compounds of nine formulas, two of which are: N (CH 2 CH 20) 3 (b) and CH 3 CH 2 C (CH 20) 3 (c). On the other hand, the group R of four other formulas represents amine derivatives, as exemplified by formula (b) above; the group R of another formula represents the alkoxylated trimethylol ethane or alkoxylated trimethylol compounds as exemplified by formula (c) above; R group of still another formula represents alkoxylated pentaerythritols; and the final alternative group R represents alkoxylated phenylenediamine. During the test, however, the particularly preferred triethanolamine monoethanolamine derivative of formula (b) of that reference, when containing six propylene oxide groups and eleven ethylene oxide groups, showed unacceptable interference with the copper electrodeposition process, where, with use led to the formation of nodules on the necessarily smooth surface of the cathode. Nodule formation is particularly undesirable, as nodules may grow to the point where they physically touch the anode, resulting in a short circuit in the electrodeposition cell, and / or they tend to entrap impurity in the copper deposited on the cathode, resulting in in a poorer quality of the recovered co-15 bre.

Additionally, test work performed with another compound of U.S. Patent No. 6,833,479 showed that approximately half of those antifouling agents were extracted from the aqueous phase to the organic phase during depletion, potentially resulting in an increase in the concentration of surfactant in the organic phase, leading to eventual phase separation problems. The presence of these surfactants, in particular, also adversely affected the extraction kinetics. Given these negative impacts, these types of mist reagents are unacceptable for use in systems involving solvent extraction of copper 25 followed by electrodeposition.

Extensive research has been devoted to the ability to reduce mist during electrodeposition, electroplating, and electroforming processes, especially in electrodeposition processes in acidic aqueous metal ion electrolyte solutions are typically used in the electrodeposition step. By far the most common solution is to add an anti-fog agent to reduce fog. However, currently available anti-fog agents are not completely satisfactory, and there is still a need for improved anti-fog agents that are: ecologically compatible; are effective even at low concentrations; have a low loss rate; are compatible with other galvanizing bath chemicals and additives; and further, do not interfere with metal depletion or phase separation kinetics in the metal recovery process if the anti-fog agent is present during these steps.

Thus, there is still a need for improved anti-fog agents for electrolysis / electrodeposition, particularly in relation to copper electrodeposition.

BRIEF SUMMARY OF THE INVENTION Improved antifogging agents for acid or alkaline mist control generated above electrolyte solutions during electrodeposition, electroplating, and metal electroforming have been found to be alkoxylated compounds that are covered with sulfonate or sulphate according to the Formulas: R ((AO) nX) m ((AO) nH) p (I) or R3C (0) NH (CH2) zN + (CH3) 2CH2CHR4CH2S03 · (IX), where: each group AO is independently an alkylenoxy group selected from ethylenoxy (ΈΟ "), 1,2-propylenoxy (" PO "), 1,2-butylenoxy, and styrylenoxy groups, preferably EO or PO; n is independently a number from 0 to 40, preferably from 2 to 30, more preferably from 2 to 20, and most preferably from 2 to 10, m is a number from 1 to the total number of hydrogens -OH in the group R before alkoxylation; a number such that the sum of m plus p equals the number of hydrogen -OH in the group R before alkoxylation; SO3Y, (CH2) qSO3Y, CH2CH0HCH2SO3Y or CH2CH (CH3) OH03Y, where q is from 2 to 4; and Y is a cation, preferably a hydrogen, sodium, potassium or ammonium ion; R3 represents C1 -C6 alkyl, preferably C1 -C6 alkyl; R4 represents H or OH; z is 2 or 3; and R is a group selected from Formulas (II) to (VIII): R1C (CH20) 3 (II), where R1 is H, methyl, ethyl, or propyl; C (CH 2 O) 4 (III); 0C (CH 2 O) 2 (IR); N (CH 2 CH 2 O) 3 (V); (R2) x N (CH2 CH2 O) y (VI), where R2 is a C1 -C4 alkyl, y is 1 to 3, and x + y = 3; O (CH 2) r O (VII), where r is a number from 2 to 6; and 0 (CH (CH 3) CH 2) 0 (VIII).

In another aspect, the invention includes aqueous electrolyte solutions comprising an effective amount of anti-fog agents according to Formulas (I) and / or (IX) above, to suppress the mist generated above such electrolyte solutions (preferably of 2 to 100 ppm, often 2 to 30 ppm) during electrolysis procedures, where all variables are as defined above.

In a further aspect, the present invention includes a method for reducing mist formation in electrolyte solutions containing metal ions by adding to it an amount of the mist suppressor of at least one of the above antifouling agents of Formulas (I) and (IX). where all variables are as defined above.

DETAILED DESCRIPTION OF THE INVENTION Unlike what is otherwise indicated or understood, all numbers expressing the amounts of the components or the reaction conditions used herein should be construed as modified in all examples by the term "approximately". In addition, it is understood that the term "metals" also includes metalloids.

In Formula (I) above, compounds which are fully alkoxylated are preferred.

In Formula (II), when R1 is methyl or ethyl, and in Formula (V), m is preferably from 1.5 to 3. More preferably in these cases, m is greater than 2.

It will be appreciated by those skilled in the art that the compounds of the Formulas (II) to (VIII) of the invention may be mixtures of the compounds having different types and amounts of alkylenoxy moieties reacted on side R groups.

It will also be appreciated by the skilled artisan that the compounds of Formulas (VI) and (VIII) may be covered at one or both ends.

Styrylenoxy groups may be unsubstituted, or may contain substituents on the phenyl group, such as one or more C1 -C6 alkyl groups, C1 -C6 alkoxy groups, and / or other groups that will not interfere with electrolysis. The compound of Formula (II) wherein R 1 is methyl or ethyl, that is, alkoxylated ethane trimethylol or alkoxylated trimethylol propane compounds, covered by the sulfonate or sulfate, are the preferred compounds of the invention. Such compounds, wherein AO is EO or PO, are preferred, and those wherein AO is EO are more preferred. Most preferred are the propane derivatives of Formula (II) wherein R 1 is ethyl. Preferred compounds of the present invention are those trimethylolpropane derivatives derived from Formula (II), wherein R 1 is methyl or ethyl containing seven ethylene oxide groups.

The compounds of Formula (I), wherein the group R is represented by Formula (V), are alkoxylated sulfonate or sulfate covered pentaerythritols.

For the sulfobetaine antifouling agents of Formula (IX), R 3 is preferably methyl, ethyl, propyl, butyl, pentyl or hexyl, and z is preferably 3.

The above compounds can be readily produced by alkoxylating the corresponding alcohols and / or amines by methods well known to those skilled in the art, for example by reacting the amines of and / or alcohols with the desired amounts of alkylene oxides.

The novel antifogging agents according to the present invention are useful for reducing or minimizing misting problems that may be present in electrodeposition compositions, electroplating and / or electroforming compositions, and / or procedures which use aqueous metal ion electrolyte solutions or aqueous dispersions of metal electrolytes in metallic form as well as in residual solutions containing dissolved metals. In all these cases, it is understood that metal / metalloid components may be present in ionic and / or elemental form. And in metal electrolysis of aqueous electrolyte solutions containing the metal (s) to be captured, the utility of the compound according to the present invention is not dependent on the presence of particular metal (s) in electrolyte solutions.

The anti-fog agents of the present invention are effective in amounts as low as a few parts per million based on the electrolyte composition, for example from 2 ppm to 100 ppm, preferably from 2 ppm to 30 ppm, and most preferably from 5 ppm. at 25 ppm. In an electroplating application, they may be added to the aqueous extraction solution used in the dewatering step after the solvent extraction step, or to the metal-impregnated aqueous solution resulting from the depletion of the organic phase in the dewatering stage, or preferably to the metal containing electrolyte / aqueous depletion phase in the electrodeposition storage tank. Also, in relation to electrodeposition processes, different extraction processes can be used in relation to metal ore. For example, nickel ore is typically leached with ammonia, extracted from ammonia solutions, and depleted with acid to form an acidic aqueous electrolyte solution used in the electrodeposition step. In electrodeposition of acidic aqueous electrolyte solutions containing zinc ions, it is not necessary to perform the solvent extraction process described above for copper to pre-concentrate the metal ions for electrodeposition.

There are several methods of electroplating for which the defogging agents of the present invention may be used. Materials such as steel strips can be galvanized into galvanizing tanks where the steel coils are uncoiled in a continuous mode, fed by a series of preparation steps, and then into the galvanizing tank. The wire that is unwound from the reels or coils into which it was wound can be passed through various processing steps and then galvanized with metals such as copper, copper alloys, zinc, iron, iron alloys, nickel alloys, nickel, gold or silver in the form of individual ribbons. Stamping, molding and casting products are typically mounted on racks specially designed for electroplating. Small parts, for example, dipped into galvanizing baskets and barrels made of inert plastic materials, can be electroplated by bulk galvanizing methods. Where the parts are large areas where only the smallest parts are to be galvanized, brush galvanization is used, that is, using galvanizing tools which are anode-formed materials covered with an absorbent material saturated with the galvanizing solution.

Insoluble anodes are used exclusively in the galvanizing baths of the present invention. Chrome plating solutions use lead-tin, lead-antimony, or only lead anodes; Galvanizing processes of gold and other precious metals use stainless steel anode, keeping inventory costs low.

However, the use of insoluble anodes can unfortunately also result in side effects. In alkaline cyanide solutions, the generation and increase of carbonate concentration is accelerated as a result of the use of insoluble anodes, along with a significant reduction in alkalinity. In acidic solutions, the pH decreases, requiring frequent adjustments. In nickel sulfamate galvanizing solutions, insoluble anodes, and even slightly passive soluble anodes, partially oxidize the sulfamate ion to form the sulfur-bearing compound that alters the character and performance of the deposit. (See Kírk-Othmer, supra).

Production of Compounds of the Invention The synthesis of sulfoalkyl derivatives of the compound of Formula I (i.e. those where X = (CH2) qS03Y) can typically be performed as a two-step reaction that can be performed in the same reaction vessel. The first step of the reaction involves the addition of metallic sodium to the alkoxylated polyol product of the respective R group compounds to form the corresponding terminal sodium alkoxide. The second step of the reaction is the addition of 1,3 propane sultone to the sodium alkoxide formed in the first step. Toluene (or other inert organic solvent) is used as a solvent throughout the process.

Sulfonate-covered derivatives of the compounds of Formula (I) wherein X = CH 2 CHOHCH 2 SO 3 Y (2-hydroxypropanesulfonate) may also typically be formed by a two-step reaction (known as Williamson synthesis) which may be performed in the same reaction vessel. preferably in an inert organic solvent such as toluene. The first step of the reaction involves the addition of metallic sodium to the alkoxylated polyol product of the respective R group compounds as above to form the corresponding terminal sodium alkoxide. The second step of the reaction is the addition of 3-chloro-2-hydroxy-1-propanesulfonic acid sodium salt to the sodium alkoxide formed in the first step, and the product is recovered by adding water to the organic phase after cooling. The aqueous phase is then isolated. The production of sulfate-covered derivatives of the compound of Formula (I), that is, those where X = SO03Y, can be performed starting with the same R group of ethoxylated polyols and converting their terminal hydroxyl groups to sulfate through known reactions. in technique. Alternatively, the terminal hydroxyl may be covered by reacting with the alkyl chloride, and then adding sulfuric acid through the double bond to provide a slightly different type of sulfate coverage.

The alkoxylated compounds of Formulas (I) and (IX) above may be readily prepared by alkoxylating the corresponding alcohols and / or amines by methods well known to those skilled in the art, for example, by reacting the alcohols and / or amines to the desired amounts. of alkylene oxide. Such a synthesis is illustrated and / or exemplified in Synthetic Detergents, AS Davidsohn and B. Milwidsky, Seventh Edition, Longman Scientific and Technical, 1987, pages 178-191, and Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd Edition, Volume 9, John Wiley and Sons, New York, 1980, p. 437, among other places. ■ Compounds of Formula (IX) are classified as sulfobutaines and hydroxy sulfobetaines. Such compounds, where z = 3, are called 2 - hydroxy-3 - [(3-alkylamino propyl) sulfonate of 3 - [(3-alkylamino-propyl) -N, N-dimethylammonium] -propane or sulfonate. ) -N, N-dimethylammonium-propane (if the group R3 is C1, then substitutes "alkyl" for "methyl"; if the group R3 is C2, then replaces the word "alkyl" with "ethyl"; R3 for C3, then replaces the word "alkyl" with "propyl", and so on). The first step in synthesis in both cases is the reaction of 3- (dimethylamino) propyl amine with an ester under standard transamidification conditions to generate the corresponding amide. In the second step, the resulting amide is reacted with 1,3 propane sultone or 2-hydroxy-3-chloropropane sulfonic acid under conditions known in the art. The invention is also illustrated, but not limited to, by the following Examples, the compounds for which they were first prepared by reacting ethylene oxide with triethanolamine, then reacting the resulting product with 1.2 propylene oxide. .

Example 1 Preparation of sodium sulfopropyl etherate from ethoxylated 2-ethyl-2- (hydroxymethyl) propane-1,3-diol (Compound A) The following step is a typical three-run preparation. To a 5,000 ml round bottom flask equipped with a Dean-Stark trap / condenser / drying tube, mechanical stirrer, and pressure equalizing funnel, 199.5 g (0.45 mol) of trimethylol propane was reacted with seven mmol of ethylene oxide and 2.75 L to 3 L of toluene. The solution was refluxed for four hours to remove all water (by azeotrope using the Dean-Stark trap). The Dean-Stark trap was then removed, and the condenser was replaced with a dry condenser. The temperature of the reaction flask was kept only at the toluene reflux temperature (overheating causes the solution to darken considerably). To the reaction flask was then added 31.05 g (1.35 mol, 1 molar equivalent to the trimethylolpropane hydroxyl groups containing seven ethylenoxy groups) of sodium metal, washed with hexane prior to use, over a period of 1 hour. The addition of metallic sodium resulted in a substantial increase in temperature. The solution was then stirred for an additional four hours. Even if there is some sodium still in the reaction vessel, it will be completely consumed in the next phase of the reaction. 1,3-Propane sultone (165.0 g, 1.35 mol) was transferred to the addition funnel together with 400 mL of toluene. Addition of 1,3 propane sultone was performed over a period of 20 to 30 minutes. Addition of 1,3 propane sultone was carefully controlled because of the extreme temperature increase at the beginning of the addition, and the formation of an untreatable solid at the end of the addition. The solution was stirred while 1.3 propane sultone was added, and continued to stir until solid product formation caused the mechanical stirrer to stop, then toluene was decanted while still hot. To remove the solid, the contents of the flask had to be dried using a vacuum pump and the solid scraped apart with a steel rod. The solid was collected, triturated, and washed with hot toluene. The ground solid was dried using a 500 millitorr vacuum, and was pulverized using grit and pestle. The yields of three runs were 95.45%, 91.37%, and 97.8%, respectively.

Example 2 Anti-Fog Capability To demonstrate the anti-fog characteristics of these products, two compounds of the invention: trimethylolpropane trisodium sulfopropyl ether containing seven ethylenoxy groups (Compound A) and triethanolamine trisodium sulfopropyl ether containing six polyoxypropylene groups and eleven polyoxyethylene groups (Compound B) were tested against 500 mL samples of the copper electrolyte solution (50 g / l Cu + 2; 0.2 g / l Co + 2; 1.5 g / l Fe + 3; 170 g / l sulfuric acid) in a large jacketed container controlled at 45 ° C, with mist generated by air passing through a thin melt (4 to 8 micron) blister nozzle with sintered glass into the copper electrolyte. The mist was sampled by air suction through a 3.81 cm (1.5 inch) sampling tube above liquid level, the tube being connected to a water trap. At timed intervals, the trap water was titrated with sodium hydroxide to a blue endpoint for bromophenol to determine the amount of acid contained in it, the results in the Table being calculated in millimeters per hour of sulfuric acid captured per hour. . The results of the anti-fog tests are shown in Table 1: Table 1 - Anti-Fog These results demonstrate that Compound A and Compound B of the invention substantially reduce the mist level to commercially acceptable concentrations.

Example 3 Comparison of Copper Electroplating Three antifouling agents according to the invention (Compound A [of Example 2, where m is ~ 3], monoethanamine sodium sulfopropyl ether containing six propylene oxide groups and eleven oxide groups. ethylene, where m is ~ 3 [Compound C] and monoethanolamine containing six propylene oxide groups and eleven ethylene oxide groups, reacted with only two moons of propane sultone for each mol of monoethanolamine, where m is ~ 2 [Compound D ]) and monoethanolamine contacted with six mo of propylene oxide and eleven mo of ethylene oxide (Compound 1, preferred embodiment of U.S. Patent No. 6,843,479), and a blank run without anti-fog agents were tested. in an electrodeposition device with guar added as a softening agent. The basis of the three new molecules is either Compound 1 or trimethylolpropane containing seven ethylenoxy groups. The three anti-fog agents tested according to the invention were: The results showed that Compound A provided a clean and smooth plate. The plate of Compound B was almost as good quality as that of Compound A. However, the plate of Compound C showed a slight tendency to nodule formation. Prior to testing it was shown that Compound I plaque contained substantial nodule growth which not only resulted in poor plaque quality for copper recovery but could also produce hazardous electrical conditions in the cell.

Procedure For each 16-hour run, 35 L of electrolyte was prepared with concentrations of 38 g / l Cu, 2 g / l Fe3 +, 0.1 g / l Co, 0.01 g / l Cl, and 175 g / l H2SO4. This was accomplished by dissolving the appropriate levels of CuSO4, Fe2 (SO4) 3, CoSO4, NaCl, and H2SO4 in deionized water. Each solution was then partitioned into two 18.93 liter (5 gallon) buckets to feed the electrodeposition for two days for eight hours each day.

An electrodeposition cell housing a cathode and two year olds was made of PVC plastic and fitted with a water jacket so that the cell could be kept at a certain temperature. The cathodes were cut from stainless steel with a surface galvanizing area of approximately 7.62 cm x 7.62 cm (3 inches x 3 inches) (0.58 cm2 (0.0625 ft2) counting both sides) and a thickness slightly smaller than 0.16 centimeter (1/6 inch); the anodes were lead plates and slightly smaller in width and height than the cathodes. The electrolyte in the cell during the run measured 11 cm deep x 8 cm wide x 12.5 cm long for a volume of 1.1 L and was pumped in and out of the cell at a rate of 28 ml / min to achieve a 3 g / L drop in Cu concentration across the cell. The current density used in the experiments was 322.9 A / m2 (30A / ft2) (with a typical current density within the storage tank between 129.2 A / m2 and 409 A / m2 (12 and 38A / ft2), and based on the surface area of the whole, the current that needed to flow to the cell was calculated to be 3.75 A.

At the beginning of each test, 0.07 g (4 ppm) of the Galaetasol® 40H4CD guar gum derivative and 0.175 g (10 ppm) of the potential defogging agent of that run were added while stirring with a stirrer to one of the two buckets. containing the electrolyte. The electrodeposition cell jacket was filled with deionized water and connected to a recirculating water bath to keep the electrolyte in the cell at 45 ° C. The inlet tube to the cell was supplied by a 28 ml / min peristaltic pump assembly and placed in the bucket containing the spiked electrolyte, which had been heated in a 45 ° C heating plate, with the outlet tube being placed in a clean, empty 18 gallon (5.93 gallon) bucket. The 1,200 ml of hot electrolyte was added to the cell to fill it to the appropriate level (so that the submerged cathode area was 0.58 cm2 (0.0625 ft2)). The anode and cathode were connected to a constant current electrical source, and the pump was turned on. Once the lines were full and the electrolyte flowed through the cell, the electrical source was turned on and set to 3.75 A of direct current.

This arrangement was run for eight hours prior to the disconnection of the power supply, the water bath supplied to the jacket, the peristaltic pump, and the wire to the cathodes of the power supply were disengaged to prevent back current. After allowing the cathode to rest in the bath overnight, the cathode was dried, weighed, and photographs of it taken. The above procedure was repeated the next day with the second batch of test solutions. Again, after allowing the cathode to rest in the bath overnight, the cathode was dried, weighed, and photographs of it taken.

The electrodeposition tests of Compound A and Compound D (Compound C was not verified) were repeated in a 40 hour run to ensure no obvious negative characteristics of the copper deposit. Each 40-hour run required 70 L of electrolyte, divided into five 14 L batches, each batch receiving 0.056 g (4 ppm) of guar polymer and 0.14 g (10 ppm) of the defogging agent being evaluated. These runs confirmed that Compound A produces high quality plaques and Compound D tends to produce plaques having a limited number of small nodules.

Example 4 Effects on Copper Extraction Circuit Kinetics Extraction circuit kinetics tests were run using the standard Cognis quality control test method to determine if the antifouling agents tested were too soluble in the organic phase or produce an effect. negative in phase separation in the depletion phase. A 10 L to 10% v / v batch of LIX® 984N was mixed with the ketoxime / aldoxime extraction reagents and was composed in the Conoco® 170Exempt aliphatic diluent. One liter of Cognis QC electrolyte batches (six in total) was spiked to levels of 20 ppm and 50 ppm (three with 20; three with 50), respectively, with each of Compounds A, C and D (from Example 3). . One liter of QC Electrolyte, without any defogging agent, was run by the QC Test as a control batch. A 400 ml sample of the LIX 984N reagent solution was contacted with 400 ml of one of the electrolyte solutions for 3 minutes by vigorously shaking in a 1 L separatory funnel. The solutions were allowed to separate, a sample from the organic equilibrate ( EO) was taken, and 350 ml of the organic was placed in a large 1 L disconnected beaker. A shaker was lowered into the organic solution so that the top of the polypropylene shaker shaft was at the surface level of the organic material. The shaker was started at 1,750 rpm and 350 ml of the control feed (6.0 g / l Cu, 3.0 g / l Fe + 3, pH = 2.0) was added over five seconds. A sample of the emulsion was taken within 30 seconds to obtain a sample of the organic material (E30). Mixing continued for a total of 300 seconds when mixing time was stopped. The time required for complete phase separation was then determined (phase break time). A sample of the organic after 300 seconds of mixing (E300) was then taken. The organic and aqueous phases were transferred to a 1 L separatory funnel and allowed to separate again. A 325 ml sample of which organic was placed in a large 1 L disconnected beaker and a clean shaker was placed at the same level as in the extraction test. The shaker was started at 1,750 rpm and 325 ml of the same QC Electrolyte as the first contact was added for 5 seconds. An emulsion sample was taken within 30 seconds to obtain a sample of the organic (S30). Mixing continued for a total of 300 seconds, where the mixing time was stopped, and the interval between phases was then determined. A sample of the organic phase was then taken (S300), with the results of the seven kinetic tests shown in Table 2.

Table 2 - Kinetics Test Results The extraction circuit kinetics data above demonstrate that Compound A and Compound C have no substantial impact on solvent extraction performance. However, Compound D does indeed appear to have a slight negative impact on phase separation. Example 5 Surface Voltage Determinations Surface voltages were measured on the QC Electrolyte with Compound A, C and D, FC110Q, and Mistop at levels of 5, 10, 20, and 40 ppm. Results are shown in Table 3.

Table 3 - Determination of Surface Tension Based on tabulated data above surface tension comparisons, Compounds A, B, and C are equally as effective in reducing electrolyte surface tension as commercially accepted FC1100.

Claims (13)

An anti-fog compound having the formula: wherein: each AO group is independently an alkylenoxy group selected from ethylenoxy groups, 1,2- (1). propylenoxy, 1,2-butylenoxy and styrylenoxy; n is independently a number from 0 to 40; m is a number from 1 to the total number of hydrogen -OH in the group R before alkoxylation; p is a number such that the sum of m plus p equals the number of hydrogen -OH in the group R before alkoxylation; X is SO3Y, (CH2) qSO3Y, CH2CH0HCH2SO3Y, or CH2CH (CH3) SO03Y, where q is a number from 2 to 4, and Y is a cation; and R is a compound selected from: R 1C (CH 2 O) 3 (II), wherein R 1 is H, methyl, ethyl, or propyl; C (CH 2 O) 4 (III); 0C (CH 2 O) 2 (IR); N (CH 2 CH 2 O) 3 (V); (R 2) x N (CH 2 CH 2 O) y (VI). wherein R2 is a C1 -C4 alkyl, y is a number from 1 to 3, and x is a number such that x + y = 3; O (CH 2) r 0 (VII), where r is a number from 2 to 6; and 0 (CH (CH 3) CH 2) 0 (VIII). Anti-fog compound according to claim 1, wherein n ranges from 2 to 15. The anti-fog compound of claim 1, wherein R is the compound of formula (II), R 1 is methyl or ethyl, and m ranges from 1.5 to 3. The anti-fog compound of claim 1, wherein R is the compound of formula (V), and m ranges from 1.5 to 3. Anti-fog compound according to claim 1, wherein AO is selected from ethylenoxy, 1,2-propylenoxy, and mixtures thereof. Anti-fog compound according to claim 5, wherein n ranges from 2 to 15. Anti-fog compound according to claim 1, wherein AO is ethylenoxy. The anti-fog compound according to claim 1 wherein Y is a hydrogen, potassium, sodium or ammonium cation. An anti-fog compound having the formula: wherein R 3 represents C 1 -C 8 -alkyl, R 3 C (O) NH (CH 2) z N + (ch 3) 2ch 2 chr 4 ch 2 SO 3 ·; R4 represents H or OH; and is 2 or 3. 10. Aqueous electrolyte solution containing: A) a metal, selected from the group consisting of copper, nickel and zinc, in metallic, ionic or dispersed form; and B) an amount effective to inhibit mist formation from the electrolyte solution of an anti-fog compound as defined in claim 1. 11. Aqueous electrolyte solution containing: A) a metal or metalloid in metallic, ionic or dispersed form, wherein the metal is selected from the group consisting of copper, nickel and zinc; and B) an amount effective to inhibit the formation of mist from the electrolyte solution of a compound selected from sulfobetaine antifouling agents of the formula: R3C (0) NH (CH2) zN + (CH3) 2CH2CHR4CH2S03 · (IX), wherein R3 represents C1 -C6 alkyl, R4 represents H or OH, and z is 2 or 3. A method for reducing mist formation of electrolyte solutions containing at least one metal or metalloid in metallic, ionic or dispersed form, the method comprising adding to it an amount of mist suppressor of at least one of the antifouling compounds. sulfonate or sulfate covered mist, alkoxylated having the formula: wherein each AO group is independently an alkylenoxy group selected from ethylenoxy groups 1,2-propylenoxy, 1,2-butylenoxy and styryloxy; n is independently a number from 0 to 40; m is a number from 1 to the total number of hydrogen -OH in the group R before alkoxylation; p is a number such that the sum of m plus p equals the number of hydrogen -OH in the group R before alkoxylation; X is SO3Y, (CH2) qSO3Y, CH2CH0HCH2SO3Y, or CH2CH (CH3) SO03Y, where q is a number from 2 to 4, and Y is a cation; and R is a group selected from formulas (II) to (VIII): R1C (CH20) 3 (II), wherein R1 is H, methyl, ethyl, or propyl; C (CH 2 O) 4 (III); 0C (CH 2 O) 2 (IR); N (CH 2 CH 2 O) 3 (V); (R2) x N (CH2 CH2 O) y (VI) wherein R2 is a C1 -C4 alkyl and x + y = 3, y is 1-3; O (CH 2) r 0 (VII), where r is a number from 2 to 6; and 0 (CH (CH 3) CH 2) 0 (VIII). A method of reducing mist formation in electrolyte solutions containing at least one metal or metalloid in metallic, ionic or dispersed form, the method comprising adding to it an amount of mist suppressor of at least one of the anti-oxidant compounds. alkoxylated mist covered by sulfonate or sulfate, having the formula: