DE1268761B - Process for the production of corrosion-inhibiting coating agents - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. α .:

German class:

Number:
File number:
Registration date:
Display day:

C09d

C07c; C08h;

C23f

22 g-7/02

120-11; 120-23 / 01;

39 b-23; 48 dl -15/00 "

July 22, 1964

May 22, 1968

The corrosion of metal objects is of great economic importance. The corrosion of the Ferrous metals show up as rust formation, i.e. H. in an oxidation of iron to iron (II), III) oxyhydrate.

This oxidation can be prevented or at least inhibited by coatings that are as impermeable as possible, which exclude the access of moisture and / or oxygen to the metal surface. These Coatings are often exposed to high humidity, corrosive atmospheres, etc. Once these coatings are damaged, they no longer have a corrosion-inhibiting effect. It is also important that these coatings adhere firmly to the metal surface, do not peel off and do not form hairline cracks or blisters. A satisfactory corrosion-inhibiting coating must therefore withstand weathering and high humidity and withstand corrosive atmospheres such as salt spray or industrial air.

The invention relates to a process for the production of corrosion-inhibiting coating agents using carbonized (carbon dioxide-reacted) basic alkaline earth metal salts of a carboxylic or sulfonic acid in solution in a mineral oil, these salts having a metal equivalent ratio of at least about 4.5, which is characterized by is that at a temperature between about 25 and about 200 ⁰ C, the flowable mineral oil solution with a content of about 10 to about 70% of the carbonized basic alkaline earth metal salt of carboxylic and / or sulfonic acid, which contains at least about twelve aliphatic carbon atoms, with about 1 to about 80%, based on the metal salt, of a lower aliphatic carboxylic acid, water or one or more aqueous alcohols with an alcohol content of up to about 80 percent by weight as compounds containing active hydrogen atoms.

The coating agents produced according to the invention are suitable for the corrosion protection of metal objects, especially made of ferrous metals. The coatings are resistant to water, if desired, can however, easily remove.

The coating compositions prepared according to the invention can be applied to metal surfaces by customary methods be applied, e.g. B. by brushing, spraying or dipping. The viscosity of the coating agent can by adding volatile diluents such as benzene, xylene, white spirit, mineral oil or turpentine any desired value can be set. The coated metal surfaces are either on the Air dried or by heating. If the coating agent has a suitable viscosity so that it applied directly to the metal surface wer-method for the production

of corrosion-inhibiting coating agents

Applicant:

The Lubrizol Corporation,
Cleveland, Ohio (V. St. A.)

Representative:

Dr. E. Jung and Dr. V. Vossius, patent attorneys,

8000 Munich, Siegesstr. 26th

Named as inventor:
Richard Leo McMillen,
Painesville, Ohio (V. St. A.)

Claimed priority:

V. St. v. America July 25, 1963 (297 701) - -

can, for example a fat consistency, no solvent is used, and it is also no drying

required. The thickness of the coating is not critical. A coating of 50 to 2000 mg per 9.3 dm ^{2 of} surface is usually sufficient to provide adequate protection against corrosion.

In practice, the process according to the invention can be carried out in such a way that the constituents in the appropriate proportions, for example, homogenized by violent movement or mixing, until the reaction mixture has a greasy consistency. In most cases, at least one must 1 hour are homogenized. The volatile components can be removed from the product by evaporation or distilling. The process is preferably carried out at the reflux temperature or something carried below.

The presence of the compound containing active hydrogen atoms is essential for the formation of the coating agent necessary.

Suitable alcohols are aliphatic, cycloaliphatic and aromatic substituted aliphatic Alcohols. Alcohols having less than about 12 carbon atoms are particularly useful. The lower ones

809 550/503

3 4

Alcohols with less than about 8 carbon atoms are paraffin wax sulfonic acid, cetyl cyclopentanesulfone preferred. acid, lauryl-cyclohexanesulfonic acid and polyethylene-Specific examples of suitable alcohols are sulfonic acid with a molecular weight of 750. Methanol, ethanol, isopropanol, n-propanol, iso- As carboxylic acids, aliphatic or arobutanol, sec-butanol, cyclopentanone, cyclohexanol, 5 matic carboxylic acids can be used. Specific 4-methyl-cyclohexanol, isooctanol, dodecanol, examples are palmitic acid, stearic acid, myristic benzyl alcohol, Cinnamon alcohol, 2-cyclopentylpropanol, acid, oleic acid, linoleic acid, behenic acid, hexatriacon-chlorhexanol, Bromactanol, ethylene glycol mono tanoic acid, tetrapropylene substituted glutaric acid, methyl ether, diethylene glycol, ethylene glycol, tri- with polyisobutene with a molecular weight of 5000 substimethylene glycol, Hexamethylene glycol, triethylene-io tuted succinic acid, with polypropylene from moleglycol, 1,4-Butanediol, 1,4-Cyclohexanediol, Glycerin kulargewicht 10,000 substituted succinic acid, with and pentaerythritol. the octadecyl radical substituted adipic acid, chlorine-die Use of a mixture of water and stearic acid, 9-methylstearic acid, dichlorostearic acid or more of the alcohols mentioned is acid, stearylbenzoic acid, with wax (Eikosan) polybesonders requesting response. This often reduces the substituted naphthoic acid, dilauryl decahydronaph reaction time shortened. Aqueous alcohols with a thaline carboxylic acid, didodecyl tetraline carboxylic acid, di-alcohol content up to 80 percent by weight are plano-octyl-cyclohexanecarboxylic acid and its anhydrides if appropriate. A very effective combination is acids.

an aqueous mixture of alcohol (or alcohols), the carbonized basic alkaline earth metal salts of the

the 25 to 75 percent by weight alcohol (alcohols) 20 mentioned oil-soluble acids must be a

contains. Metal equivalent ratio of at least about 4.5

The lower aliphatic carboxylic acids contain. The expression "metal equivalent ratio"

less than about 8 carbon atoms in the molecule. denotes the ratio of the total chemical

Specific examples are formic acid, acetic acid, equivalents of the metal in the metal salt to the chemical

Propionic acid, butyric acid, valeric acid, isovalerian- 25 mix equivalents of the metal, which in the form

acid, isobutyric acid, caproic acid, heptanoic acid, a normal salt is present, d. H. as neutral

Caprylic acid, chloroacetic acid, dichloroacetic acid and organic acid salt. As an illustration

Trichloroacetic acid. let it be said that a metal salt, which is 5 equi

Of these, formic acid, acetic acid and metal pro-valents are each equivalent of the organic acid

pionic acid preferred. The anhydrides of these acids contain 3 ° residues, a metal equivalent ratio of 5

are just as useful, and in the present possession; a neutral metal salt has a metal equi

writing and the claims includes the valent ratio of 1. The requirement of this

The expression "acid" both the acid and the high metal equivalent ratio results from

Anhydride of acid. noting that the use of a salt with

The concentration of active hydrogen atoms corresponds to a metal equivalent ratio of less than 4.5

holding compound is about 1 to about 80%, in the process according to the invention no product results,

based on the weight of the carbonized basic which has a fat consistency. Such a product

Alkaline earth salt, preferably at least about 10%, does not give a satisfactory coating agent. Another-

and usually less than 60% · concentrations on the other hand have been found to be the use of salts

above 80% have no additional effects. 40 with a metal equivalent ratio between about

The carbonized 8 and 20 used according to the process are particularly advantageous, albeit salts

basic alkaline earth salts are the salts of the magnet - with even higher metal equivalent ratios -

siums, calcium, strontium and barium with one case are effective.

long chain sulfonic acid or carboxylic acid. Mixtures The production of the carbonized basic Erdsolcher Salts are also useful. The acid is said to be best carried out by alkali salts in a known manner at least about twelve aliphatic carbon atoms converting a substantially anhydrous gel Molecule included. The sulfonic acids include the mixture of carboxylic and / or sulfonic acids with minaliphatic and the aromatic sulfonic acids, at least about 4.5 equivalents of an alkaline earth metal namely the petroleum sulfonic acids and the sulfonic acids, each equivalent of the acid with carbon dioxide in the base which are obtained by treating the alkylated 50 in the presence of an accelerator. The metal base can aromatic hydrocarbons with a SuUo- an oxide, hydroxide, bicarbonate, sulfide, mercaptide, nating agents, such as chlorosulfonic acid, sulfur trioxide, hydride, alcoholate or phenolate of an alkaline earth oleum, Sulfuric acid or sulfur dioxide and chlorine. being metal. It is preferably an oxide, alcoholate The sulphonic acids obtained by sulphonating the alky- or hydroxide of barium or calcium. the Lated benzene, naphthalene, phenol, phenol sulfide or 55 carbonization is made in a solvent, preferably diphenyl oxide are obtained, mineral oil is particularly useful. The solvent bar. can also η-hexane, naphtha, n-decane, dodecane, specific examples of sulfonic acids are mahogany benzene, toluene, xylene or any other liquid acid, naph hydrocarbon monosubstituted with wax (eikosan).

thalinesulfonic acid, dodecylbenzenesulfonic acid, Dido- ^6o The accelerator is preferably an alcohol decylbenzenesulfonic acid, dinonylbenzenesulfonic acid, or phenol. It is also possible to use a mercaptan, amine, an octadecyl diphenyl ether sulfonic acid, octadecyl diaci nitro compound or an enol compound, phenylamine sulfonic acid, cetyl chlorobenzenesulfonic acid. Specific examples of alcohols and bis - cetylphenyl disulfide - sulfonic acid, cetoxycapryl phenols as accelerators are methanol, ethanol, benzenesulfonic acid, dilauryl - /? - naphthalenesulfonic acid, isopropanol, cyclohexanol, decanol, dodecanol, the sulfonic acid used in the treatment of polyiso-behenyl , Ethylene glycol, diethylene glycol, tributene with a molecular weight of 1500 with ethylene glycol, ethylene glycol monomethyl ether, tri-chlorosulphonic acid, nitronaphthalenesulphonic acid, methylene glycol, hexamethylene glycol, glycerine,

5 6

Pentaerythritol, benzyl alcohol, phenylethyl alcohol, A. To a mixture of 3245 g (12.5 equivalents)

Phenol, naphthol, cresol, pyrocatechol, p-tert-barium petroleum sulfonate, 1460 g (7.5 equivalents) hep-butylphenol, with polyisobutene of molecular weight tylphenol and 2100 g water in 8045 g mineral oil 350 phenol substituted in the m-position, ο , ρ-Dido- are given at 82 ⁰ C 7400 g (96.5 equivalents) of barium decylphenol, α-hexyl-β-naphthol, m-cyclohexyl-5 oxide. The temperature rises to 145 ° C. phenol, 4,4'-methyl-bis-phenol and 2,2'-methylene. This temperature is maintained until the 4,4'-dioctyl-bis-phenol. Examples of other- all water is distilled off. In the mixture is more accelerated are z. B. Acetoacetate, Acetylacetone, Acet- then carbon dioxide is introduced until it is neutral. The amide, ethanolamine, diethanolamine, triethanolamine, product is diluted with 5695 g of mineral oil and filtered nitromethane, nitropropane, nitrodecane, nitrobenzene, io it. The filtrate has a barium sulfate ash content of nitrotoluene, methylamine, dimethylamine, aniline, Phe-30.5% ^and a metal equivalent ratio of 8.1.
nylenediaminejNjN'-dimethylphenylenediamine.Toluidine, B. A mixture of 1145 g of a mineral solution

Cyclohexylamine, N-methyl-decylamine, naphthylamine, of a 40% solution of barium Mahoganysulfonat o-chlorophenol, m-nitrophenol, o-methoxyphenol, (1 equivalent) and 100 g of methanol at 55 ⁰ C with thiophenol, methyl mercaptan, dodecyl mercaptan , 15 220 g of barium oxide are added, while in the mixture isooctyl mercaptan and benzyl mercaptan etc. carbon dioxide at a rate of 56.5 to

When mixed with the alkaline earth metal base forms 851 / hr. is initiated. Become this mixture the sulfonic acid or carboxylic acid is a metal salt that contains 78 g of methanol and then 460 g of barium oxide before carbonization, a large excess of which is added while carbon dioxide is added to the mixture Contains metal base. Such a mixture is heterogeneous, 20 introduces. The carbonized product is on for 1 hour primarily due to the presence of the large 150 ° C heated and filtered. The filtrate has one Excess of the insoluble metal base. With the barium sulfate ash content of 53.8% and a metal progression the carbonization becomes the metal base equivalent ratio of 8.9.

dissolved in the organic phase, and the carboni- C. A carbonized basic alkaline earth salt becomes

If necessary, a homogeneous product like B is produced, but a total of 15 equi-masses containing an unusually large amount of metal valent barium oxide per equivalent of that used. The mechanism of formation of the homogeneous barium mahogany sulfonate is used. The product product is unknown. However, a metal equivalent ratio of 13.4 is suggested.
assume that the carbonization of the metal base D. A mixture of 520 parts (by weight

Converts excess into a carbonate or bicarbonate, based on 30) mineral oil, 480 parts of a sodium earth which forms a homogeneous complex with the metal salt oil sulfonate (molecular weight 480) and 84 parts of the oil-soluble acid. The complex is in water and ^{heated to 100 °} C. for 4 hours. The Ge hydrocarbon solvents such as benzene and xylene mix then become readily soluble with 86 parts of a 76% aqueous and mineral oil. Lent to form a releasable solution of calcium chloride and 72 parts of lime, homogeneous product but it is not ER-35 (90% purity) was added and conducive for 2 hours at 100 ⁰ C, that the entire heated in the process mixture, a by heating to water content of present metal base so converted by carbonizing less than 0.5% dehydrated, cooled to 50 ⁰ C, is converted with. In many cases already obtained a 130 parts of methanol and then at 5O ⁰ C and the homogeneous product, when only 75% of the metal base treated carbon dioxide until it is substantially neutral carbonated surplus. The expression "carbo-40 is. The mixture is then heated to 150 ⁰ C to nisiertes basic alkaline earth metal salt, "the homo- methanol and water referred to distill off. The oil solution of the carbonized product without specific reference to the basic calcium sulfonate is filtered. That would take on the degree of conversion of the metal base filtrate has a calcium sulfate ash content of 16% excess due to carbonization. and a metal equivalent ratio of 2.5. A business

The carbonization temperature depends largely on the accelerator used, a mixture of 1305 g of the carbonized calcium sulfonate. When 930 grams of mineral oil, 220 grams of methanol, 72 g of isobutanol, a phenol is used as an accelerator, is the 38 g of amyl alcohol is heated to 35 ° C and four temperature usually subjected in the range of about 80 to the following operating cycle: mixing and 300 ⁰ C. , preferably between 100 and 200 ^° C. with 143 g of 90% calcium hydroxide and treating. Overall the reflux temperature of the reaction mixture, the resulting product is then heated for 9 hours at 155 ⁰ C to residential not, and preferably does not exceed the alcohols to be removed. Then it is at this 100 ⁰ C. temperature through a silicic acid-containing filter aid

After carbonization, the accelerator can be filtered, 55 medium. The filtrate has a calcium sulfate if it is a volatile compound, from the pro-ash content of 39.5% and a metal equivalent can be removed by distillation. If the ratio is 12.2.

Accelerator is a non-volatile compound, E. Will be a carbonized basic alkaline earth salt

it is usually left in the product. Process for prepared as D, but the weakly basic preparation of the carbonized basic alkaline earth metal ^6o calcium sulfonate with a metal equivalent ratio salts are described for example in the USA of 2.5 replaced by a mixture of the calcium sulfonate patents 2,616,905, 2,616,924, 2 695,910, (280 parts by weight) and tall oil acids (970 parts by weight 2,971,014 and 3,027,325 parts with an equivalent weight of 340). the

The production of such carboni- total amount of the calcium hydroxide used based basic alkaline earth metal salts or their solutions 65 is 930 parts by weight. The resulting highly basic described, which in the subsequent execution metal salt has a calcium sulfate ash content of examples in the inventive production of the 48%> ^em metal equivalent ratio of 7.7 and a coating agent can be used. Oil content of 31%.

7 8

F. A highly basic alkaline earth metal salt carbonized 99 ⁰ C. It is particularly useful in a mineral oil is prepared as D, however, the output as quality of SAE 5 to SAE120.

material used weakly basic calcium sulfonate The following examples explain the invention

with a metal equivalent ratio of 2.5 replaces conventional procedures. The penetration values were

measured by tall oil acids (1250 parts by weight with a 5 according to ASTM test standard D-217 at 25 ° C.

Equivalent weight of 340). The total amount of the

Calcium hydroxide used is 772 wt

share. The highly basic metal salt obtained has an amount of 733 g of the carbonized basic metal salt B.

Metal equivalent ratio of 5.2, a calcium within 90 minutes 179 g of acetic acid and

sulfate ash content of 41% ^and an oil content of 10 275 g of a mineral oil with a viscosity of 2000

33%. SUS given at 38 ⁰ C with stormy movement.

G. A highly basic alkaline earth metal salt carbonized The mixture is prepared then for 2 hours at 150 ⁰ C homo as D but is genisiert as output. The resulting coating agent is a materially used weakly basic calcium sulfonate fat.

replaced by a mixture of Example 2 used for E

basic calcium sulfonate (555 parts by weight) and

Tall oil acids (694 parts by weight with one equivalent- A mixture of 960 g of the carbonized basic

weight of 340). The amount of CaI metal salt C, 256 g of acetic acid and 300 g of a calcium hydroxide used is 772 parts by weight. The mineral oil with a viscosity of 2000 SUS with the metal salt maintained has a metal equivalent ratio of 20 38 ⁰ C is homogenized by 2 hours of stormy stirring at 7.9, a calcium sulfate ash content of 45% 150 ⁰ C. The coating agent obtained and an oil content of 32% is a fat.

H. A carbonized basic alkaline earth salt is Example 3

manufactured as D, but the amount of

applied weakly basic calcium sulfonate 1672 25 to 150 parts of the carbonized basic metal parts and the amount of calcium salt E used becomes 75 parts of a mineral oil with a hydroxids 704 parts. The resulting highly basic viscosity of 2000 SUS at 38 ° C and 50 parts of vinegar metal salt has given a metal equivalent ratio of acid. The mixture is by east 12.2 and a calcium sulfate ash content of 40 %stormous agitation homogenized at 100 ° C, inside

I. In the manufacture of a product such as D, the mixture is heated to 150 ° C. for 30 half 3 hours, with 75 parts of the the sodium petroleum sulfonate is diluted by an equivalent mineral oil and then diluted to 130 to 4 hours Amount of sodium polydodecylbenzenesulfonate replaced. 145 ° C heated, with the volatile components The highly basic metal salt obtained has to be removed. The residue is a fat. Calcium sulfate ash content of 41.5% and a metal. .

equivalent ratio of 13.1. 35 B e 1 s ρ 1 e 1 4

The mineral oil solution of the carbonized basic A mixture of 150 parts of the carbonized

Alkaline earth salt can be obtained by dissolving the metal-basic metal salt F, 45 parts of acetic acid and salt in a mineral oil. If the 100 parts of a mineral oil with a viscosity of metal salt in the presence of another solvent, 2000 SUS at 38 ° C is made for 5 hours at 100 ° C and like mineral oil, then the solvent 40 is then 9V for ₂ hours at 145 to 115 ° C homogenized, removed by distillation after the metal salt The product is a fat with a penetration value in a mineral oil. For the invention of 229.

According to procedures it is important that the mineral oil Example 5

solution of the metal salt free of insoluble impurities

cleaning is. Therefore, if any impurities are present in the mineral oil solution, a mixture of 45 parts acetic acid and 50 parts, for example a mineral oil with a viscosity of 2000 SUS as a result of insufficient carbonization at 38 ° C, will increase at 100 ° C in 5 hours 150 parts of alkaline earth metal base which, overbased basic alkaline earth metal salt was used optionally for the production of the carbonized of the carbonized basic metal salt G, the mixture is 2 ¹ I ₂ hours at this temperature, the oil solution is preferably filtered 5o homogenized, within 2% hours at 150 ⁰ C or centrifuged before it is heated in the erfindnugsgemäße, diluted with 50 parts of the mineral oil and he method is used. The reason for removing Neut 4 hours at 140-197 ⁰ C is homogenized. That of the insoluble impurities results from the product is a fat with a penetration value finding that the obtained greasy coating agent of 260.

does not have the same degree of homogeneity, 55 Example6

if the impurities are not removed.

The concentration of the carbonized basic - Example 5 is repeated, but the homo-alkaline earth metal salt in the mineral oil solution is minimized at 138 and 145 ⁰ C carried out. That earth at least 10 percent by weight. If the concentration of fat has a penetration value of 343. tration is below about 10%, then 60% can usually be used.

a fatty coating agent cannot be produced. Example 7

A mixture of 150 parts of the carbonized oil should also contain a sufficient amount of mineral oil

Solution present so that the initial mixture of fluent metal salt G, 15 parts of methanol, 10.5 is capable. Usually the solution will contain at least about parts n-pentyl alcohol and 15 parts water will contain percent by weight mineral oil. The mineral oil that can be used here for 5 hours at the reflux temperature (74 ° C.) is preferably one of the mineral oils. Thereafter, the mixture 8 _^3/4 hour at a viscosity value in the range of from 50 SUS (Say- homogenized 148 ⁰ C, wherein the volatile Kompobolt Universal Seconds) at 38 ⁰ C to 500 SUS be removed when components. The product is a fat with

9 10

a drop point above 260 ⁰ C and a pene- Verdeichsbeisoiel 14

tration value of 333. ^{6 l}

". -ίο ^ in a mixture of 2000 parts of a weakly ba-

P ^le sic calcium sulfonate with a metal equivalent

A mixture of 150 parts of the carbonized 5 ratio of 2.5 (prepared as D), 160 parts of mebasic metal salt D, 15 parts of methanol, 10.5 ethanol, 80 parts of n-pentyl alcohol and 80 parts of n-pentyl alcohol and 45 parts of water is water is heated for 96 hours at 57-66 ⁰ C and then 13 hours under reflux at 71 to 74 ⁰ C. Homogenized for 2 hours at 15O ⁰ C. A fat becomes The mixture solidifies. It is not received on this within. This shows how critical the metal is ^{heated to 144 °} C. for 6 hours and with 126 parts of an 10 equivalent ratio of the mineral oil used in the process with a viscosity of 2000 SUS in the case of carbonized basic metal salt.
38 ⁰ C diluted. The mixture is 4V ₂ hours "....... . ,,

144 ° C heated. The product is a fat with a comparative example 15

Penetration value of 257. A mixture of 167 parts of the weakly basic

15 calcium sulfonate with a metal equivalent ratio

Example ^{9 ms of} 2.5 (manufactured as D), 80 parts of mineral oil,

70 parts of calcium hydroxide, 29 parts of methanol,

A mixture of 200 parts of carbonized 94 parts of isobutanol, 50 parts of amyl alcohol and basic metal salt D, 16 parts of methanol, 8 parts of 18 parts of water is treated with carbon dioxide, n-pentyl alcohol and 8 parts of water is homogenized according to Example 9 for 5 hours. The mixture heated under reflux at 70 to 72 ⁰ C, showing no tendency to form a fat within.
3 hours in an open vessel ^{heated to 133 0} C The fat-

and then homogenized ^{at 133 °} C. for 1 hour. Since such coating agents are characterized by homo-cooling, a fat is obtained with a penetration strength and stability against air, heat and moisture value of 255. 25. You can ^s in the consistency and hardness of Example 10 ^ ^{he s} g ° t ^enann quality no. 0 (penetration value of

355 to 385) up to quality no.6 (penetration value

A mixture of 500 parts of the carbonized vary from 85 to 115).

basic metal salt H and 60 parts of water

heated to 100 ⁰ C and held for 30 hours at this temperature-30 coating agents against deterioration by Feuchtigratur. The mixture is heated within 4 hours or water is exemplified by heated to 150 ° C and 3 hours at this temperature equal penetration values, which are held before and after while blowing it with nitrogen. the processing of the coating agent can be measured. The residue is a fat. The processing consists essentially in that

τ, · · 1 11 35 one brings the coating agent into a cylinder and

ΰ e 1 s ρ 1 e 1 11 lets a piston perform 100,000 strokes at 25 ° C.

A mixture of 300 parts of the carbonized fat produced according to Example 9 shows 1.24 parts of methanol before and basic metal salt, 12 parts after processing, penetration values of 322 or n-pentyl alcohol and 9 parts of water is 337 for 5 hours. A penetration value of 338 for this fat after ^{heated to 70 to 72 0} C under reflux, then in 40 its mixing with 10% of its weight in an open vessel within 4 hours to 150 ⁰ C water and after processing the mixture with heated and homogenized. After cooling, 100,000 strokes are obtained at 25 ^° C., which is an indication that you have a fat with a penetration value of 271. excellent water stability.

Various fat-like over-

B e i s ρ i e 1 12 +5 traction means applied to metal surfaces. These

Coating agents would have to be added with certain

A mixture of 200 parts of water and 1000 parts of rust preventive agents are reinforced to prevent a technical carbonized highly basic Ma- Contact of water and moisture with the gnesiumsulfonats with a metal equivalent ratio metal surface and the resulting rust formation of 8.3, a magnesium content of 7, 2% and a 50 lower. These additives often had the post-magnesium sulfate ash content of 31.4% is partially inside to make the fat water absorbable what half of 2 ¹ I ₂ hours 98 ⁰ C and then within about a change in the grease structure and often the formation of 2 Heated to 150 ⁰ C hours. The residue is caused by emulsions, whereby the effectiveness of the desired fat, which has a coating agent penetration value as a rust inhibitor, is 225. 55 The corrosion inhibitors produced according to the invention

. . Biting coating agents allow the water to do so

Example 13 does not, between the metal surface and the coating

A mixture of 50 parts of water, 125 parts of the medium to creep. The following tests show the product D and 125 parts of a technical carbo-effectiveness of the super-basic magnesium sulfonate produced according to the invention with a 60 tensile agent in reducing the corrosion of metal equivalent ratio of 8.3, a magnetic metal objects and the ability of the Aufgesium content of 7, 2% and a magnesium sulphate applied coatings, then to remain effective themselves, ash content of 31.4% is heated to 100 ⁰ C and when ausdieser over long periods of moisture temperature boiled for 1 hour under reflux. be set.

The reflux condenser is removed and the mixture is heated to 150 ° C. for 2 hours. The residue is converted to reduce the corrosion of metal objects an open beaker and 15 minutes at is determined by a salt spray corrosion test, mixed 150 ⁰ C. The residue is a fat. as stated in MIL regulation G-16908, amendment 1,

October 23, 1952. Three clean polished steel plates are coated with the the grease to be tested. The fat is applied in such an amount that the total weight is 0.21 g when the fat is applied to a panel approximately 2.5 x 7.6 x 0.32 cm. A cover Uniform strength is applied by putting the fat directly on the plate with a metal spatula distributed. The panels are left to stand in a dust-free atmosphere at room temperature for 24 hours, then they are sprayed with a 5% aqueous sodium chloride solution for at least 100 hours at 35 ° C, where they are held at an angle of 45 °. In order to receive the rating “passed”, at least no corrosion will be visible on two out of three panels. Corrosion on the edges of the panels and on the Surfaces within 3.2 mm of the edges are not taken into account. The results of this test are in Table I shown.

Table I.
MIL salt spray corrosion test (100 hours)

Steel plate

Untreated

Treated with the coating agent from Example 9

Treated with the coating agent from Example 4

Treated with the coating agent from Example 13

Treated with commercially available carboxylate fat (calcium complex)

valuation

failure exists exists exists failure

35

The superiority of the fat-like coating compositions of the invention over the carbonized basic ones Alkaline earth salts, which do not have a fatty consistency, result from the same test (MIL regulation G-16908) on steel panels. Those listed in Table I-A Results show that these coating agents are unsatisfactory.

Excellent results are obtained when using the corrosion-inhibiting coating agents Invention applies to metal objects, which by means of a novel aqueous phosphating solution which is described in U.S. Patent 3,090,709.

The effectiveness of such a treatment is illustrated by the following salt spray corrosion test. Eight 10 , 6 parts of zinc oxide, 36.8 parts of 85% phosphoric acid, 11.5 parts of calcium nitrate hexahydrate and 11.1 parts of a 50% aqueous solution of sodium hydroxide. A phosphate coating weight of 200 mg per 9.3 dm ^{2 is} applied by spray-coating the cleaned steel panels with the phosphate solution at 75 to 80 ° C. for 2 minutes. After spray rinsing with water at room temperature, the panels are spray rinsed for 1 minute at room temperature with dilute aqueous zinc dichromate solution (1 g of CrO ₃ per liter as zinc dichromate) and dried.

All eight panels are then sprayed with 50% ligroin solution of the fat from Example 9. A 0.076 to 0.127 mm thick coating is applied. The coated panels are then subjected to the salt spray corrosion test described in ASTM test standard B 117-57T. In this test, the panels are exposed to a mist of a 5% aqueous sodium chloride solution for a certain time (in this case 264 and 528 hours) at 35 ± I ⁰ C. The panels are removed from the salt spray chamber, washed with water to remove salt deposits, and examined to determine the extent of rust formation. The results of these experiments are given in Table II.

Table II
Salt spray corrosion test

Steel type covered with
Fat from example 9

Table I-A MIL Salt Spray Corrosion Test (100 Hours)

Results

45 264 hours

Steel panels treated with
52.6 ° / ₀ strength oil solution of valuation Mass A fails
fails
consists Mass D Mass of example 9

50

As mentioned, the corrosion-inhibiting coating compositions of the invention can be applied to metal objects be applied in solution. The effectiveness of this method of reducing corrosion metal objects are subjected to a different salt spray corrosion test (ASTM test standard B117-51T) shown. After this test, an uncoated steel panel corrodes over the entire surface End of 24 hours, whereas a steel plate, which with a 60% solution of the mass of example 9 coated in ligroin using a brush shows only slight corrosion at the end of 96 hours. Likewise, a table shows which one with 54% solution of Example 9 was treated in mineral oil, no corrosion at the end of 96 hours.

Simple

Phosphated *

Simple

Phosphated ..

no rust
no rust

528 hours

60% heavy rust no rust

* Steel panels that have been phosphated (as described above), but not with the coating agents according to the invention were coated to 50% after 16 hours in the salt spray chamber and complete after 30 hours covered with rust.

Two 10 x 20 cm sheets of 0.5 mm thick cold rolled steel SAE 1020 are coated with a 60% Solution of the product from Example 9 in mineral oil sprayed to a coating thickness of 0.076 to 0.127 mm.

Two similar steel panels are made with a 40% solution of the product from Example 9 in a light No. 2 fuel oil sprayed to a thickness of 0.076-0.127mm. One of each set of panels is then included a sharp steel instrument scratched so that

a deep scratch through the coating and into the metal which starts 2.5 cm from the top of the panel and 2.5 cm from its lower part ends. The test results are given in Table III.

Table III
Salt spray corrosion test (96.5 hours)

7o uer
% Λ f \ rt rt ^ * solution Heating oil Results Degree of rust, Dimensions mineral 7o the which at 60 oil 7o blackboard Scoring 40 ° / o _ Free of is visible 40 60 rust zero Example 9 - 100 NuU Example 9 100

10

It should be noted that the effectiveness of the method according to the invention is independent of the manner in which in which the fat mass is deposited on the metal object ao. This test illustrates also the ability of the fat coatings of the invention to correct any damage, whichever the coating grows from a blister or scratch.

Claims (5)

Patent claims: 1. Process for the production of corrosion-inhibiting coating compositions using of carbonized (reacted with carbon dioxide) basic alkaline earth salts of a carbon or Sulphonic acid in solution in a mineral oil, these salts having a metal equivalent ratio of have at least about 4.5, characterized in that that at a temperature between about 25 and about 200 ° C, the flowable mineral oil solution with a content of about 10 to about 70% of the carbonized basic alkaline earth metal salt of carboxylic and / or sulfonic acid, which contains at least about twelve aliphatic carbon atoms, with about 1 to about 80% » based on the metal salt, a lower aliphatic carboxylic acid, water or an or several aqueous alcohols with an alcohol content of up to about 80 percent by weight as active Reacts compounds containing hydrogen atoms. 2. The method according to claim 1, characterized in that that a calcium salt is reacted as a carbonized basic alkaline earth salt. 3. The method according to claim 1 and 2, characterized in that the metal salts with Acetic acid converts as a lower aliphatic carboxylic acid. 4. The method according to claim 1 and 2, characterized in that the metal salts with an aqueous lower alcohol having less than about 8 carbon atoms. 5. The method according to claim 1 and 4, characterized in that the metal salts with a Reacts mixture of 2 parts of methyl alcohol, 1 part of pentyl alcohol and 1 part of water. 809 550/503 5.68 © Bundesdruckerei Berlin