US3065184A

US3065184A - Acetone-formaldehyde reaction product corrosion inhibitor

Info

Publication number: US3065184A
Application number: US686591A
Authority: US
Inventors: Mortimer T Harvey
Original assignee: Harvel Research Corp
Current assignee: Harvel Research Corp
Priority date: 1957-09-27
Filing date: 1957-09-27
Publication date: 1962-11-20
Anticipated expiration: 1979-11-20

Description

United States Patent Qfitice 3,%5,l84 Patented Nov. 20, 1962 3,965,184 ACETONE-FORMAEDEHYDE REACTEQN PRODUCT CGRRGSION IYHEBITGR Mortimer T. Harvey, South Orange, N.J., assignor to illarvel Research Corporation, a corporation of New ersey No Drawing. Filed Sept. 27, 1957, Ser. No. 686,591 1 (ilaim. (Cl. 252146) The present invention relates generally to the art of cleaning metal surfaces with pickling agents and to the art of electroplating on metal surfaces, and the present invention relates more particularly to the protection of metal surfaces against the action of pickling agents during the cleaning of metal surfaces and against the action of electrolytes during the electroplating of metal surfaces.

An object of the present invention is to provide a composition of chemicals for use in the cleaning of metal surfaces and in electroplating on metal surfaces, which composition is eifective in its primary function and is also effective in protecting the metal surface against any deleterious action of the cleaning agent itself on the metal being cieanedand against any deleterious action of the electrolyte on the metal on which plating is to be done or is being done in an electroplating solution.

Another object of the present invention is to provide a composition of chemicals comprising a cleaning agent and a restraining agent or inhibitor for cleaning purposes and for electroplating uses in which the inhibitor protects metal to be cleaned, and metal on which electroplating is to be or is being done, against any deleterious action of the cleaning agent or of the electrolyte in electroplating operation.

Another object of the present invention is to provide an electroplating solution which is advantageous to the obtaining of good adherence between metal deposited and the metal surface on which the deposited metal is laid during electroplating operation, said electroplating solution comprising (1) an acidic agent and (2) an inhibitor capable of preventing deleterious action of said acidic agent with respect to the metal surface onto which electroplating is being done.

Another object of the present invention is to provide a solution for electroplating comprising (1) an acidic electrolyte and (2) an inhibitor which is continuously opera- .tive during electroplating process -to restrain deleterious action of said acidic electrolyte with respect to the surface onto which electrodeposition is being done.

Another object of the present invention is to provide a combination of an acidic material and an inhibitor for use in electroplating baths in which the inhibitor in which .the latter acts continuously and substantially uniformly over the surface onto which metal is to be deposited wherebythe deposition is made continuously uniform and thereby higher current densities can be economically used in .the electrodeposition and whereby good adherence is obtained between the metal onto which plating is done and the metal deposited thereon and further between the successive increments of the deposited metal.

It is also an object of the present invention to provide a composition of chemicals comprising (1) an acidic electrolyte and (2) an inhibitor for use in the flash electroplating of successive layers of different metals on a metal base whereby the deposited metals are protected against deleterious action of electrolytes used in the electrodeposition of succeeding metals; for example, as in the successive deposition of copper, nickel and chromium on steel.

I have discovered that certain water soluble ketonealdehyde reaction products, e.g., acetone-formaldehyde reaction product, when included in pickling baths, in electroplating baths and in primary and secondary batteries have the property of cutting down the action of hydrogen at the surface of metal without limiting the effectiveness of electrolytes in the removal of oxides, greases and other undesirable materials in pickling operation and without limiting the electrolytic actions occurring in electroplating baths and in primary and secondary batteries, and I have discovered further that the presence of said water soluble ketone-aldehyde reaction products in such said baths and batteries enhances the desired operation or action.

I have also discovered that the presence of water soluble ketone-aldehyde reaction products in electroplating baths cuts down the entrainment of metals and metal compounds by vapors which pass out of said baths when the latter are hot.

Following are examples of (A) Water soluble ketonealdehyde reaction products, (B) pickling baths, (C) electroplating baths or solutions, (D) primary battery mixtures and (E) electrolytes for use in secondary or storage batteries.

For General Examples (A) reference is made to the US. Patent No. 2,683,133 which describes water soluble ketone-aldehyde reaction products, and the methods for making them, suitable for use in the practice of the present invention.

More particular Examples A are as follows.

EXAMPLE Al (One Mole of Acetone With Four Moles of Formaldehyde) 300 lbs. acetone 1700 lbs. formaldehyde (37% concentration) 25 lbs. .NaOH in 60 lbs. Water The caustic soda-water solution was divided into four equal portions. The unit was loaded with acetone and formaldehyde with the steam on and stirring equipment in operation and the material was heated to -125" F. The first portion of caustic soda-water solution was added and the steam cut off. As the temperature rises to F. and the cold water is turned on, an exothermic reaction takes place and the temperature slowly rises to 200 F. then slowly begins to fall. At 185 F. the second portion of caustic soda-water solution is added whereupon the temperature again rises to 200 F. Upon cooling to 185 F. the procedure is repeated allowing the temperature to rise and fall between the additions of caustic sodawater solution and keeping the cold water on the jacket at all times. The mass is then allowed to cool to F. at which time the cold water is shut off. Vacuum is turned on keeping the vent open. The vent is slowly closed and the steam turned on. Dehydration may be continued to produce a resin of 75%-l00% solids.

EXAMPLE A2 (One Mole 0f Acetone With Three illoles Formaldehyde) 30 parts of acetone 126 parts formaldehyde (37% concentration) 2 parts NaOH in 4 part water The caustic soda-solution was divided into three equal portions. Using the same procedure as that set forth in Example 1, the resultant resinous product produced was amber colored and measured more than 75% of the combined weights of acetone and formaldehyde in the original charge. The resin was soluble in water.

i? EXAMPLE A3 The following additional example of water soluble ketone-aldehyde reaction product and method for making it are given.

120 parts by weight of acetone 340 parts of commercial 37 /2 solution of formaldehyde 4 parts of diethylaminopropyl amine are brought together in steps to control exothermic reaction and after the latter subsides the reaction mass is heated under a condenser and to refluxing temperature for /2 hour and then dehydrated to about 70% solids. The resulting product is an acetone-formaldehyde reaction product in solution in water.

In the General Examples A of water soluble ketonealdehyde reaction products there can be included those made by substituting a part of the acetone by other ketones and/ or a part of the formaldehyde by other aldehydes. About 50% of the acetone can be substituted by one or more of methyl ethyl ketone, methyl isopropyl ketone, mesityl oxide, diacetone alcohol or others and/or about 50% of the formaldehyde can be substituted by one or more of acetaldehyde, propinaldehyde, butyraldehyde or others to obtain water soluble ketone-aldehyde reaction products suitable for the practice of the present invention.

EXAMPLE B1 A cleaning or pickling solution is made up of the following:

100 parts by weight of water, 25 parts of hydrochloric acid and 12 parts of the material of Example A1.

EXAMPLE B2 A cleaning or pickling solution is made up of the following:

100 parts by weight of water, 10 parts of sulphuric acid and 10 parts of the material of Example A1.

Other examples can be made by following Examples B1 and B2 and substituting any of the other water soluble ketone-aldehyde reaction products given in said US. patent identified above or described herein in place of all or any part of material of Example Al.

EXAMPLE C1 An example of a chromium plating bath, according to the present invention, is as follows:

100 parts by weight of water, 25 parts of chromic acid, sulphuric acid in amount to make the ratio of chromic acid to S0,, to be 100:1, and 10 parts of the material of Example A1.

EXAMPLE C2 For a copper plating bath the following is made up: 100 parts by weight of water, 4 parts of copper metal, 5 parts of sulphuric acid and 8 parts of the material of Example A1.

Other examples can be made by following the formulas of Examples C1 and C2 and substituting any of the other water soluble ketone-aldehyde materials given in said US. patent identified above or described herein in place of all or any part of material of Example A1.

EXAMPLE D To 100 parts by weight of a sulphuric acid-water solution of specific gravity from 1.200 to 1.300, 10 parts of the material of Example A1 are added and any of the other Water-soluble ketone-aldehyde reaction products described in said US. Patent 2,683,133 or defined herein (1 can be used in place of all or any part of said material of Example A1.

EXAMPLE E In a dry cell battery comprising a containing negative electrode of zinc and a carbon rod as a positive electrode and a water solution of sal ammoniac and zinc chloride mixed into a depolarizer comprising powdered coke, graphite and manganese dioxide, the material of Example A1 is added to enhance the function of the depolarizer and the addition is made in amount by weight about /2 to 10% of the sal ammoniac and zinc chloride.

While Water has been stated as being the solvent in the baths and solutions of the present invention, variation thereof may be made by adding thereto other liquids such as alcohols (ethyl, methyl, propyl alcohol, for examples) in accordance with general practice known to those skilled in the art; also electrolytes other than those recited can be added to the materials recited in the examples hereof, such as for example as ammonia compounds and nitro compounds (ammonium sulphate, nitrobenzene) without departing from the spirit of the invention.

Although I have indicated in specific examples that the mole ratio of aldehyde to ketone in the formation is 2 to 4 moles of aldehyde to one mole of ketone, it is considered that the present invention is operative when using water soluble reaction product made from 2 to 6 moles of aldehyde to one mole of ketone by the methods given for the more specific examples, and these reaction products as used in the practice of the present invention are those which in the presence of acids are soluble in water to the amount of /2.% to 30% of the water by weight, and the acids are used in amount from /2% to 35% of the water.

Having thus described my invention, what I claim is:

The method for cleaning a surface of a metal element comprising subjecting said element to an aqueous solution of an inorganic acid capable of cleaning a surface of said element, said solution containing a water-soluble acetoneformaldehyde reaction product in an amount sufficient to protect said element from deleterious action of said inorganic acid which would otherwise occur, said reaction product produced by reacting under alkaline conditions acetone and formaldehyde in the mole ratio of 1 mole of acetone to 2-6 moles of formaldehyde.

References Cited in the file of this patent UNITED STATES PATENTS 1,470,225 Holmes Oct. 9, 1923 1,716,542 Ellis June 11, 1929 2,049,517 Saukaitis Aug. 4, 1936 2,152,406 Ducamp Mar. 28, 1939 2,259,169 Little Oct. 14, 1941 2,666,738 Kardos Ian. 19, 1954 2,683,133 Harvey et a1. July 6, 1954 2,711,971 Miller et al. June 28, 1955 2,733,198 Nobel et al Ian. 31, 1956 2,758,970 Saukaitis et al Aug. 14, 1956 2,766,218 Harvey et a1 Oct. 9, 1956 FOREIGN PATENTS 810,779 France Jan. 6, 1937 1,114,697 France Dec. 19, 1955 346,162 Great Britain Apr. 9, 1931 OTHER REFERENCES Corrosion Handbook, by Uhlig, pages 910-912, John Wiley, New York 1948).