CORROSION INHIBITOR FOR THE PROTECTION OF SHEET METAL

Abstract: Corrosion inhibitor for preventive oils and greases is based on alcalic metal soaps of fatty acids and according to the invention contains vegetable and or animal fatty acids with the carbon chain length C₁₆-C₂₂, contains barium hydroxidate, contains reaction product of vegetable and/or animal fatty acids with the chain length C₁₆-C₂₂ with barium hydroxidate; the reaction is led so first barium hydroxicate is introduced into fatty acids preheated to the temperature of about 120°C, and this temperature of reactants is maintained during the determinant period of time, next the temperature of reactants is raised to about 180°C and the reaction is led during the determinant period of time, and the molar ratios of fatty acids to barium hydroxidate amount from 1:0,1 to 1:2. The corrosion inhibitor contains also amines of fraction C₁₂-C₂₂ and/or amines of fraction C₁₂-C₂₂ and/or fatty alco­ hols esters of fraction C₁₂-C₂₂ with fatty acids of fraction C₆-C₂₂ and/or the salts of fatty amines of fraction C₁₂-C₂₂ and of fatty acids of fraction C₆-C₂₂ and/or ethoxylic esters of fatty alcohols and of ethoxylic fatty amines, advantegous in a quantity from 0,01 to 10% of gravimetrics.

Description: Corrosion inhibitor for preventive oils and greases The subject of invention is corrosion inhibitor for preventive oils and greases. The inhibitor is used in preventive oils utilized to conservation of metal products surfaces after the plastic or mechanical working,e.g, to conservation of motor-car body sheets stored in packs. The inhibitor is also used to preventive greases and preservative -gear greases. It is noted fron the british patent specification nr 1455250 the corrosion inhibitor used to fuel tanks. This known inhibitor ccntains sodium nitrite,sodium benzoate and a small quantity of carboxyethylcellulose. The inhibitor is introduced into the fuel tarmacs in form; of tablets. This known inhibitor is usuless as inhibitor for preventive oils. It is known from the patent specification of FRG nr-1444904 the application of benzotriazole additives along with maleinic acid anhydride as corrosion inhibitors added to oils. Benzotriazole adducts are effectively working protectives for copper and its alloys,while they are less effective as concerned iron. There are also known corrosion inhibitors added to preventive and engine oils or to oils used as hydraulic fluids,which are benzotriazole adducts and oxazolines adducts containing alkyl radical,alkene radical or cycloalkyl radical with the number of carbons from 6 to 20. Oils containing small quantities of this known inhibitor:. show good anticorrosive properties as engine oils and other working oils.They have not sufficient protective properties as preservative oils for iron. There are known barium derivative of lanoline and barium sulphonate used as corrosion inhibitors for working greases. These known inhibitors show relative small anticorrosive efficiency and they are usuless for preventive oils,because after a short time of remaining on metal sheet surfaces or other metal surfaces they are polvlmerized and they become hard to remove. This defect reveals mainly by conservation of sheets in packs. After the conservation with oil containing barium derevative of lanoline and barium sulphonate as inhibitors, sheet in packs become cogliitinated and are very hard to separate. There are known from the polish patent specification nr 52975 and 48772 corrosion inhibitors being derivatives of fatty acid, especially oleic acid amines. It is known from the american patent specification nr 4166151 the corrosion inhibitor for oils and greases being carboxylic acid esters with the carbon number C10-C25 and alkohol esters. It is known from the american patent specification nr 4168292 the corrosion inhibitor for preventive oils being derivatives of fatty acids in form of acylic hydro Sylaminealcylamides. It is known from the polish patent application nr P. 212732 the composition for engine oil enriching, containing 1-50 parts by weight barium or calcium detergent with alcalic reserve 60 mg KOHlg along with polymethylosilicon compound. The composition, among others, protects the metal parts of engine from various types of corrosion. The fault of known inhibitors is a relative small inhibiting efficiency regarding atmospheric corrosion, These means do not protect effectively from appearance of black corrosion spots, mainly during storing sheets in packs. The known inhibitors are relatively expensive. There are known from the american patent specification nr 4212751 and from the british patent specification nr 852365 oils and bearings' greases containing additives of such the compounds as esters of dithiophosphoric acid, the salts of these esters and secondary alcohols in beta position having two quaternary carbons. These compounds are known from the improvement the lubricity of oils that enables to increase the bearing loading and protects from pitting corrosion. It is known from the application to The Polish Patent Office nr P 218353 the grease oil containing 2-15S gravimetrics of animal or vegetable sulphonated fats at presence of catalyst, 0,1-5% gravimetrics of reaction product of fatty acid and/or naphtenic acids with polyalcylenopolamine, 0,01-1% gravimetrics of fatty amines or diamines and a composition of kerosenic hydrocarbons in a number completed to 100 gravimetrics. It is known from the american patent specification nr 4201681 the corrosion inhibitor for cooling fluids and for gear greases,being a mixture of barium derivative of lanoline and barium sulphonate. The relevant defect of lubricant oils and greases containing the known inhibitors mentioned above is 2 poor ability of permanent and homogenous mixing and problems with reaching the stability of composition. The defect of the known corrosion inhibitioning agents is only momentary protection against corrosion. The known inhibitors are hard to remove after the long period of storing and their anticorrosive efficiency is relatively low. The objective of invention is working out the corrosion inhibitor for protective oils and greases free from the defects of known inhibitors,and the compositions based on this inhibitor will be free from the defects of compositions based on the known inhibitors. The corrosion inhibitor for preventive oils and -greases based on alcalic metal soaps according to the heart of invention is characterized by this that contains vegetable and/or animal fatty acids with carbon chain lenght Cn6-C22, contains barium hydroxide, contains the product of vegetable and/or animal fatty acids with chain lenght C16-C22 with barium hydroxidate, reactin led so that first barium hydroxidate is introduced into the fatty acids preheated to the temperature of about 12000 and this temperature is mantained during the definitive period of time,and next the temperature of reactants is raised to about 18000 and the reaction is kept during the determinant time, and the molar proportions of fatty acids to barium hydroxide amount from 1:0,1 to 1:2. It is advisable that the corrosion inhibitor according to the invention to contain also fraction amines C12-C22 and/or fraction amides C12-C22 and/cr fatty alcohols esters of fraction C12-C22,with fatty acids of fraction C6-022 and/or the salts of fatty amines of fraction C12-C22 and fatty acids of fraction C6-C22 and#/or ethoxylic esters of fatty alcohols and ethoxylic fatty amines,advisable in quantity from 0,01 to 10, gravimetrics. It is desirable the corrosion inhibitor according to the invention for preventive oils and greases to contain the fatty acid reaction product with barium hydroxide; the reaction is led so that the temperature of reactants preheated to about 12000 is mantained during about 2h and the temperature of reactants about 18000 duringlh. It is advisable the corrosion inhibitor according to the ivention to contain the fatty acid reaction product with barium hydroxide; the reactio is led so that the temperature of reactants preheated to about 1200c is mantained during about 1h and the temperature of reactants about 1800C during about 2h. It is advantegous the corrosion inhibitor according -to the invention used for greases to contain also zincum hydrohide and vegetable and/or animal fatty acid with carbon chain length C16-C22,reaction product with zincum hydroxide, and proportion of zincum hydroxide quantity to barium hydroxide gravimetrics amounts from 0,01:10 to 10:0,01,and proportion of quantity of fatty acid to the sum of hydroxide quantity amounts in molar form from 1:0,1 to 1:1. It is advisable if the corrosion inhibitor according to the invention used for greases contains also mineralic oil in quantit? from 1 to 5C,# gravimetrics introduced into reactive composition in temperature of about 12000, at least a few minutes before the temperature is raised to about 18000. It is desirable if the corrosion inhibitor according to the invention used for preventive oils contains also orthophosphoric acid and/or 1- and/or 2- and/or tri-substituted organic derivatives of phosphoric acid in a quantity from 0,01 to 5# of gravimetrics. The inhibitors according to the ivention used as additives even in very small quantities with known anticorrosive agents such as alifatic amides,polyamines,polyalkanoloamines,hetero# cyclic amines, the salts of amines and fatty acids,amides, esters of ethoxylic amines and fatty acids improve functioning of the inhibitor much more than it could be expected from the quantity of inhibitor added, taking under consideration suming of inhibiting properties. This important improvement of inhibitor properties could result from cooperation of knom compounds ith the inhibitor according to the invention, which could be consider as the result of synergism causing improvement of inhibiting properties. The surfaces formed with inhibitor according to the invention are resistant to emulgation and durable i.e their preventive properties do not deteriorate in time. The corrosion inhibitor according to the invention is shom on the manufacturing example. Example1 To the reactor are introduced 5C gravimetrics of fatty acids with chain lenght C16 6-C22 and heated to 12000 slowly adding by constant mixing #0 gravimetrics of barium hydroxide,next the mixture is heating in the same temperature and wit constant mixing. The temperature is then raised to 16coy and by constant mixing it is mantained during 30 minutes. After cooling down the contents of the reactor to the ambiental temperature, the inhibitor may be introduced into preventive oils. Example Corrosion inhibitors worked out by mixing in a temperature 12000 2,5 gravimetrics of inhibitor manufactured according to the example I and witn 0,5 gravimetrics of triethanol amine oleate. After cooling down the inhibitor made in such a way it may be introduced into preventive oils. Example 111To the corrosion inhibitor worked out as in example I are added in temperature 8000 0,7 gravimetrics of orthophosphoric acid and the mixture is cooled down to the ambiental temperature. The inhibitor made in such a way may be introduced into preventive oil. Comparative researches of preventive properties of inhibitors are worked out in accordance with the polish standard PN-72/H-04637. For examination were used plates of dimention 100x75x1 cut down from. metal sheets colled rolled and deep drawed. Before testing the plates were degreased in extraction naphta. The plates preserved with the examined agents and the unpreserved plates were plates in"Stevensor.'s House during 4 months. passing on determination of amount decrement caused by corrosion it was stated that comparing with the unpreserved samples the power of slowing down of atmospheric corrosion is as follows: : - for samples preserved with machine oil M8-30, - for samples preserved with machine oil M8 +5,J of commercial inhibitor,oleinic acid amine -50% - for samples preserved with machine oil M8 +5% according to e.g.I -80- - for samples preserved with machine oil e +5Sö of inhibitor according to e.g. II -95 > - for samples preserved with machine oil N8 +5coo of inhibitor according to e.g.III Example 50g of fatty acid of fraction C6-C22 with acid number 15G and iodine number 15 is introduced into reactor, the mixture of gases is heated to 1200C and then 16kg of zinc hydroxidate is introduced. It is heated and the temperature of the mixture is mantained on a level of 1200C during 1h. The mixture is next heated to1800C and this temperature is mantaines during 115 minutes. The mixture obtained in such a way is cooled down to the ambiental temperature. The extracted product is an effective inhibitor of atmospheric corrosion, very useful. in greases production, especially to bearings' lu brificants. Example V Into the inhibitor worked out according to e.g,I after 30 minutes of keeping the composition under temperature 12000 is added 25kg of mineralic low-viscid fluid under the commercial name Selektol 10-3G and the temperature is raised to 1800C. This temperature is mantained during 130 minutes. The content of the reactor is cooled down to the ambiental temperature. The inhibitor worked out in such a way:is useful in production of semifluid polyfunctional greases with the increased anticorrosive properties,useful mainly for conservation of precision mechanisms. Example Into the inhibitor worked out according to e.g.I after 45 min. of mantaining the composition temperature 1 it is added 1 gravimetrics of ethoxylic fatty alcohols esters with carbon chain lenght C18-C22and containing ethoxylic group 14. The temperature is raised to 1800C and mantained during 15 minutes Then it is cooled down to the ambiental temperature. The inhibitor worked out in such a way is useful for anticcorosive greases, especially for preservation of goods stored in the conditions of increased humidity.

Claims: Patent claims 1. The corrosion inhibitor for preventive oils and greases based on alcalic metal soaps of fatty acids, characte ristic of this, that it contains vegetable and/or ani mal fatty acids with the carbon chain length C16-C22, contains barium hydroxidate, contains reaction product of vegetable and/or animal fatty acids with carbon chain length C16-C22 with barium hydro#idate, the re action leading in this wayso that first barium nydro- xidate is introduced into fatty acids preheated to the temperature of about 1200 C, this temperature of re actants is maintained during the determinant time and next the tennerature of reactants is rise to about 1800C and the reaction is being kept during the determi nant time and molar ratios of fatty acids to barium hydroxidate amount from 1:0,1 to 1:2. 2. The corrosion inhibitor according to claim 1, characte ristic of this,that it contains also amines of fraction C12-C22 and/or amides of fraction C12-C22 and/or fatty alcohol esters of fraction C12-C22 with fatty acids of fraction C6-C22 and/or the salts of fatty amines of fraction C12-C22 and of fatty acids of fraction 06-C22 and/or ethoxylic esters of fatty alcohols and ethoxylic fatty amines, advisable in quantity from 0,01 to 10, of gravimetrics. 3. The corrosion inhibitor for preventive oils, according to claim 1 characteristic of this,that it contains reaction product of fatty acids with barium hydroxidate; the reaction is led so that the temperature of reactants preheated to about 120 C is tiantained during about 2h and the temperature of reac tants of about 18000 during 1h. 4. The corrosion inhibitor for greases according to claim 1, characteristic of this that it contains reaction product of fatty acids with barium hydroxidate; the reaction is led so that the temperature of reactants preheated to about 12000 is mantained during about 1h, and the temperature of reactants of about 18COC during about 2h. 5. The corrosion inhibitor for greases according to claim 1, characteristic of this that it contains also zinc hydroxidate and reaction product of vegetable znd/cr animal fatty acids with the chain lenght C16-C22 wit zinc hydroxidate and the ratio of quantity of zinc hydroxidate to barium hydroxidate amounts from 0,1 to 10 ,to 10:0,01,and the ratio of fatty acids quantities to the sum of hydroxidate quantity amounts in molar form from 1:0,1 to 1:1. 6. The corrosion inhibitor for greases according to claim 1 characteristic of this that it contains also mineralic oil in a quantity from 1 to 50 % of gravimetrics introduced into te reactive mixture in the temperature of about 1200C at least a few minutes before raising the temperature to about 1800C. 7. The corrosion inhibitor for preventive oils according to the claim 1 characteristic of this that it contains also orthophosphoric acid and/or 1- and/or 2- and/or 3-subs'Wituted organic derivatives of phosphoric acid in a quantity from 0,01 to 5 % of gravimetrics.

Inventors: BRANDT, ANDRZEJ, DAROWICKI, KAZIMIERZ, IWANOW, JERZY, KOZLOWSKI, ANDRZEJ, SZAUER, TADEUSZ, WLODARCZYK, SYLWIA
Applicants: INSTYTUT MECHANIKI PRECYZYJNEJ, POLITECHNIKA GDANSKA
Application year: 1983
Main classification: C23F15
IPC codes: C10M129, C07C51, C07C53