DE1521762A1 - Metal protectants and deactivators - Google Patents

Description

The present invention relates to the use of certain bis-benzotriazoles as corrosion inhibitors for metals and as Metal deactivators, as well as compositions of substances that contain Come into contact with metal surfaces and contain bis-benzotriazoles.

It has been found that the bis-benzotriazole of the formula I

CD

X is a straight-chain alkylene group with 1 to 6 carbon atoms, which are unsubstituted or substituted by alkyl groups with 1 to 5 carbon

_ω material atoms, cycloalkyl groups, preferably the cyclohexyl

to group, or polymethylene groups, preferably the Penta-00

w methylene group, is substituted, a carbonyl group, a

to. · ~

22 sulfonyl group, an oxygen from or a sulfur atom

co- means and
00

η is O or 1,

have a very good corrosion-inhibiting and metal-deactivating effect.

If the bridge member X is an alkylene group, it preferably contains a total of at most 6 carbon atoms. X contains one or more alkyl or cycloalkyl, it can

Documents (Art. 7 J ί Section 2 No. I Satt J d ·· Andwungag «. V. 4 9. TM?}

■ - 2 -

for example, the methyl, ethyl n-propyl, isopropyl, act n-amyl or cyclohexyl group. Examples of allylene groups as bridge member X are: methylene, 1,1-dimethyl-methylene, Cyclohexylidene, ethylene, n-propylene, n-butylene, n-amylene, n-hexylene, 1-methyl-ethylene, 1,2-dimethyl-ethylene, 1-methyl-n-propylene, 2-methyl-n-propylene, 1,2-dimethyl-n-propylene, 1,3-dimethyl-n-propylene, 1,2,3-trimethyl-n-propylene, 1-methylene-n-amylene, 1-ethylethylene, 1-ethyl-n-propylene, 1-ethyl-n-butylene, l-methyl-2-ethyl-ethylene, l-methyl-2-ethyl-n-propylene, 1-cyclohexyl-ethylene, l-cyclohexyl-n-propylene, 1-cyclohexyl-n-butylene, l-cyclohexyl-2-ethyl-ethylene, 2-cyclohexyl-n-propylene, 1,1-dimethyl-ethylene, 1,1-dimethyl-n-propylene, 2,2-dimethyl-n-propylene, 1-methyl-ethyl-ethylene, 1-methyl-l-cyclohexyl-ethylene, 1-methyl-l-ethyln-propylene, 1-methyl-1-cyclohexyl-n-propylene, 2-methyl-2-ethyln-propylene or 2-methyl-2-cyclohexyl-n-propylene.

Examples of usable in the invention Bisbenztriazolverbindungen are: bis (benzotriazolyl-5), mp 320 ⁰ C, bis (benzotriazolyl-5) -methane mp 24O ⁰ C, l, 2-bis (benzotriazolyl-5) -ethane,..! , l-bis-Cbenztriazolyl-Si-cyclohexane propane, 2,2-bis (benzotriazolyl-5), bis (benzotriazolyl-5) ketone mp. 285 ⁰ C, bis (benzotriazolyl-5) ether m.p. 243 ⁰ C., bis (benzotriazolyl-5) sulfone, mp. 300 ⁰ C.

The bisbenzotriazoles used according to the invention have valuable corrosion and corrosion properties when used on metal surfaces tarnish-resistant and other protective properties. You can as corrosion and tarnishing inhibiting compounds in a large number of substances used, be it that the metal surface to which they are applied, by these substances of corrosion exposed, or that the functional properties

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of the substances suffer from contact with the metal surface. The bisbenzotriazoles can therefore be used in combinations of substances Metal protectants or serve as metal deactivators.

Metal surfaces can be treated with the bisbenzotriazole compounds to protect them against corrosion and tarnishing the compounds are brought together with you in the vapor phase or in the form of solutions. The connections can after a Usual methods are applied, for example by spraying them in a solution onto the metal surface, the metal in dipping such a solution or by putting the metal in paper ^ or other packaging material containing the bis-benzotriazole.

The metal is treated in a solution of the Bisbenztriazoiverbindungen, the solution preferably contains 0.01 to 5 wt.% Of the compound and in particular 0.1 to 1 wt.%. The bisbenzotriazole compounds of the formula I are sparingly soluble in water or aqueous media. However, organic solvents, especially oxygen-containing hydrocarbons, for example dialkyl ketones such as acetone, alkanols such as isopropanol, alkoxyalkanols such as 2-methoxyethanol, alkylene glycols or dialkyl glycols such as ethylene glycol, can be used.

Also as components of substance compositions such as antifreeze, Cooling mixtures or machine fluids, for example synthetic lubricants or hydraulic fluids, The compounds of the formula I are normally in contact with metal or metal alloy surfaces Use.

A preferred method of protecting metals is to wet the surface of the metal or metal alloy with it the solution of one or more bisbenzotriazole compounds of the formula I,

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preferably 0.01 to 1.0 wt. ^, but in particular from 0.1 to 1.0 weight ^., in a suitable solvent, at elevated temperature, for example from 60 ° to 100 ⁰ C, and then drying the surface in air or removing the remaining solvents by heating.

Another method of protecting metals is to wrap the surface of the metal in a material, such as tissue paper, that has been impregnated with a bisbenzotriazole compound of formula I. The impregnation of the packaging material may be at Bisbenztriazolverbindung by immersion in a solution of 0.1 to 5 wt.%.

Another method of protecting metals is by placing or suspending the metal in an atmosphere saturated with the compound of formula I vapor. The steam is kept at a constant temperature of 85 ⁰ G in the process. The metal can be cooled beforehand in order to accelerate the condensation of the steam.

Another method of protecting metals is to treat the surface of the metal with a non-abrasive wax or polishing agent containing bisbenzotriazole compounds of Formula I. The wax or polishing agent preferably contains 0.1 to 10 wt.% Bisbenztriazolderivate. If solid wax is used, the bisbenzotriazole derivative can be stirred into the melted wax. If liquid wax is used, the bisbenzotriazole derivative

oo in a solution compatible with the liquid base of the wax

to be attached.

^ J You can also use the surface of a metal with a

O ₀ . Treat suspension of an abrasive that is suspended in a liquid or semi-liquid medium and containing the Bisbenztriazolverbindungen of formula I in an amount of 0.01 to 5 wt.%.

The bisbenzotriazole compounds of formula I impart Metal or metal alloy surfaces, in particular surfaces of copper, cadmium or their alloys have corrosion-inhibiting properties. For example, you can use the Corrosion and tarnishing of metal or metal alloy surfaces that are exposed to the effects of sulfur dioxide, hydrogen sulfide, Ammonia or other corrosive gases. For example, brass or another copper alloy with a Compound of formula I are treated, which also causes corrosion when deformed by the action of sulfur dioxide on the metal is prevented.

The compounds of the formula I are advantageously used as starting and corrosion inhibitors or as additives to such agents used in media that are in contact with copper or other metal surfaces. They can also be components of metal protectants in polishes or other compositions of materials that protect or improve the appearance of metal surfaces be used. The compounds of formula I are also valuable metal deactivators in materials their functionality is adversely affected by contact with a metal, especially copper. Such materials can for example Be working media. The compounds of the formula I are particularly advantageous metal deactivators for machine fluids that are exposed to high temperatures, e.g. for synthetic High temperature lubricant ±; t, tel,

The Bisbenztriazoles of the formula I are by reaction of 3,3 ', 4,4'-tetra aminodipheny compounds of the formula

in which X and η have the same meaning as in formula I, prepared with nitrous acid in the stoichiometric amount required for the diazotization of only two of the four amino groups. The 3,3 ', 4, 4'- _: tetra-aminodiphenyl compound can, for example, be treated with a mixture of an alkali metal nitrite and an inorganic or organic acid. If necessary, the reaction can be carried out under similar conditions as in a conventional diazotization. The desired bisbenzotriazole of the formula I is then obtained by the simultaneous splitting off of two molecules of water under the diazotization conditions.

The invention is explained in more detail below with the aid of the examples. In this, parts by weight relate to parts by volume as Kilograms to liters. Unless otherwise stated, percentages are based on weight.

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example 1

Samples of shiny copper foil treated in an acid bath are immersed in the following solutions: 0.01 $ aqueous solution of benzotriazole; 0.01 $ aqueous Solution of bis (benztriazolyl-5) -Eiethanj 0.01 $ solution of Benzotriazole in technical alcohol; 0.01 $ solution of bis (benztriazolyl-5) methane in technical alcohol; 0, liquid solution of benzotriazole in technical alcohol; 0. Solution of Bis (benzotriazolyl-5) methane in technical alcohol. The six immersed samples are held at 65 ° for 5 minutes, then in washed with distilled water and dried with hot air.

The resistance of the copper foils to tarnishing is compared with that of a seventh, also immersed in the acid bath, but compared otherwise untreated copper foil by exposing all samples to an atmosphere containing 10 ppm hydrogen sulfide. The time elapsed until a visible coating is formed assumed as a measure of the resistance to tarnishing.

The results are shown in Table I below.

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Table I.

Copper sample
treated with: time in
Minutes untreated comparison sample 2 0.01 # aqueous benzotriazole 10 0.01 $ aqueous bis (benzotriazolyl-5) -
methane 20th 0.01 $ solution of benzotriazole in techn.
alcohol 10 OjOljSlser solution of bis (benztriazolyl-5) -
in techn. alcohol 20th 0, liquid solution of benzotriazole in techn.
alcohol 10 0.1% solution of bis (benztriazolyl-5) -
in techn. alcohol > 30

These results show that compounds used according to the invention protect copper against tarnishing and that their protective properties are superior to those of benzotriazole.

Example 2

Samples of the same cadmium foil are immersed in the following solutions: 0.01 # solution of bis (benzotriazolyl-5) methane in technical alcohol, 0.01 $ solution of bis (benztriazolyl-5) methane in water. The two Immersed samples are kept at 65 ° for five minutes, then washed with distilled water and dried in hot air . 90 9 8 39/139 8

The resistance of the cadmium samples to tarnishing is compared with that of an untreated sample of the same cadmium foil as a control by comparing the three samples with a 10 ppm Exposed to an atmosphere containing hydrogen sulphide. The time span until the appearance of a visible deposit is taken as a measure for corrosion resistance.

The results are shown in Table II below.

Table "II

These results prove the effectiveness of the invention used compound as protection against tarnishing of cadmium. .

Cadmium sample
treated with: time in
hours untreated comparison sample
0.01 # aqueous bis- (benz-
triazolyl-5) methane
OjOl ^ iger solution of bis- (benz-
triazolyl-5) methane
in techn. alcohol 3
> 24
> 24

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Example 3

Samples of shiny copper treated in an acid bath are each treated with an aqueous isopropanol suspension of an abrasive, one of which also contains 0.3 $ bis (benzotriazolyl-5) methane. A sample of the same copper is also treated with the same abrasive material containing 1% benzotriazole.

The polished copper samples are then tested for tarnishing resistance by applying a 10 ppm Exposed to an atmosphere containing hydrogen sulphide. The time until the appearance of a visible deposit is taken as a measure of the corrosion resistance caused by the abrasive on the copper surface.

The results are shown in Table III below.

Table III

Copper sample
treated with: time in
Minutes a polish without
Corrosion inhibitor
a $ 0.3 bis (benztriazolyl-5)
methane-containing polishing agents
one containing 1% benzotriazole
Polishes. 5
13th
17th

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These results clearly show the anti-corrosion effect obtained by treatment with an inventive of the formula I containing polishing agents on a copper surface is achieved.

Example 4

Samples of a shiny copper foil treated in an acid bath are immersed in the following solutions: O1, 0.1, 0.5, aqueous solution of benzotriazole; M 0.01 $ solution of bis (benzotriazolyl-5) ketone in a mixture of 90 parts of water and 10 parts of technical alcohol; 0.01 $ solution of bisbenzotriazole in a mixture of 90 parts of water and 10 parts of technical alcohol; 0.01 $ aqueous solution of bis (benztriazolyl-5) methane; 0.01 $ aqueous solution of bis (benzotriazolyl-5) ether.

The seven immersed samples are held at 65 ° - 70 ° for 2 minutes and then at 145 ° in dried in an oven. The resulting coating has a uniform golden brown color. Persistence becomes a control of the copper samples against tarnishing were compared with that of an eighth copper foil also immersed in the acid bath but otherwise untreated. The period of time until the appearance of a visible deposit is recorded in Table IV below.

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Table IV

Solution in which the copper sample is immersed

control

¹ time

0.01 # aqueous solution of benzotriazole 5 0, aqueous solution of benzotriazole 5 0.5 # aqueous solution of benzotriazole 5 0.01 # aqueous alcoholic solution of
Bis (benzotriazolyl-5) ketone 15th Q, Ql $ aqueous alcoholic solution of
Bis-benztrlazole 15th G, 01 # aqueous solution of bis- (benz-
triazolyl-5) methane 20th 0.01 # aqueous solution of bis-
(benztriazolyl-5) ether 20th

The results shown in Table IV show. . achieved with the compound used according to the invention _? ic .arg! Significantly increased tarnishing resistance to untreated copper or copper treated with benzotriazole.

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1 & 2T762

Example 5

Samples of shiny acid-immersed Copper are made up of an abrasive emulsified in water from ordinary sand soap and $ 0.2 bis-benzotriazole., Bis (benztriazolyl-5) methane or bis (benztriazolyl-5) ketone or bis (benzotriazclyl) ether. A sample of the same Copper is also treated with this water-emulsified abrasive which, however, does not contain a bis-benzotriazole compound.

The polished samples are then tested for tarnish resistance by exposing them to an atmosphere containing 10 ppm hydrogen sulfide. The time until a visible deposit appears is a measure of the tarnishing resistance brought about by the abrasive on the copper surface.
The results are summarized in Table V below.

Table V

Additive to abrasives Time in minutes control
0.2% bis-benzotriazole
0.2 $ bis (benzotriazolyl-5) methane
0.2 $ bis (benzotriazolyl-5) ketone
0.2 $ bis (benzotriazolyl-5) ether 2
3
3
3
3

ORIGINAL INSPECTED

These results prove the increased resistance to: Sulphide formation on copper with abrasives containing according to the invention usable compound was treated.

Example 6

Samples of shiny, acid-immersed copper are treated with an abrasive consisting of an aqueous isopropanol slurry of an abrasive material, plus 0.2 $ bis (benzotriazolyl-5) methane or 0.2 ^ bis (benztriazolyl- 5) contains ~ ether. A sample of the copper was treated with the same abrasive, except that it did not contain a bis-benzotriazole compound. The copper samples are tested in the same way as described in Example 5 for their resistance to tarnishing.
The results are summarized in Table VI below.

Table VI

Additive to abrasives

Time in minutes

control

Bis (benzotriazolyl-5) ether Bis (benztriazolyl-5) methane

2 6th

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ORIGINAL INSPECTED

These results demonstrate the increased resistance to sulfide formation on copper with abrasives containing it Compounds which can be used according to the invention have been treated.

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Claims (2)

Claims 1. Bis-benzotriazoles of the formula I (D X is a straight-chain alkylene group with 1 to 6 carbon atoms, which are unsubstituted or by alkyl groups with 1 to 5 carbon atoms, cycloalkyl groups or polymethylene groups is substituted, a carbonyl group, a sulfonyl group, an oxygen atom or a Sulfur atom means and η is 0 or 1. 2. Use of bis-bentriazoles of the formula I. 909839/1398 ., .... .. - ^ ₁ ;, ts.2 U. ■ '..; * .: 3 des An ^ erunasses. v. 4.9.196 / j X is a straight-chain alkylene group with 1 to 6 carbon atoms, which are unsubstituted or by alkyl groups with 1 to 5 carbon atoms, cycloalkyl groups or polymethylene groups is substituted, a carbonyl group, a sulfonyl group, an oxygen atom or a Sulfur atom means and η is 0 or 1, as a corrosion-inhibiting and metal-deactivating agent. 909839/1398 ORIGINAL INSPECTED