DE1085995B - Emulsifiable anti-rust agent - Google Patents

Description

GERMAN

The invention relates to emulsifiable rust inhibitors which are stable when mixed with 1 to 10 parts of water Form emulsions, consisting of a certain mixture of a mineral lubricating oil, an alkali salt and a oil-soluble sulfonic acid, a neutral wool fat, a coupling agent and one from an organic amine mixture and water composite leveling agent.

In the manufacture of high precision machined metal parts, it is common to have between the individual Use a rust preventive in the various operations to prevent corrosion of the metal surfaces. the The usual type of rust inhibitor used for this purpose consists of a mixture of a corrosion inhibitor and a petroleum solvent. The rust preventive film is usually quite thin and will rarely from the metal parts between successive ones Operations removed. These common anti-rust agents are often quite good in terms of their anti-rust effect satisfactory but suffer from a number of disadvantages. So are z. B. the vapors developed by the petroleum solvents are often unpleasant for the worker. This is especially the case when working in which metal parts are washed in hot water in order to prevent the Application of the anti-rust compound to remove metal chips and traces of metalworking compounds. In such cases, when the metal parts are dipped in the rust preventive, they are usually in place at a temperature in the vicinity of 82 ° C, and the heat causes an annoying development of steam the solvent. Apart from that, the anti-rust agents are based on petroleum solvents quite easily flammable and therefore flammable.

In order to remedy these deficiencies, rust inhibitors have been developed in which the petroleum solvent is replaced by water. These water-based rust inhibitors can be applied in the same manner are like the usual compositions based on solvents, e.g. B. by painting, Dipping, wiping, or atomizing. These water-based rust inhibitors have the advantage that they are non-flammable and do not emit unpleasant fumes. They are also less expensive to use Use.

The water-based rust inhibitors are often heated to prevent the water from evaporating from the having to accelerate workpieces coated with the agent. The product therefore only meets the requirements when the emulsion is heat resistant. Emulsifiable rust inhibitors consist of hydrocarbon oils, which contain the necessary corrosion inhibitors and emulsifiers. Before their application will be emulsified them with 1 to 10 parts of water.

Although these prior art rust preventive agents are emulsifiable rust preventive agents

Applicant:

Esso Research and Engineering Company, Elizabeth, N.J. (V.St.A.)

Representative: E. Maemecke, Berlin-Lichterfelde West,

and Dr, W. Kühl, Hamburg 36, Esplanade 36 a,

Patent attorneys

Claimed priority:
V. St. v. America February 2, 1956

based on water represent a step forward compared to means based on petroleum solutions, they still have various shortcomings. The one remaining on the coated workpiece Oily film tends to run off the metal, leaving part of it unprotected. The oily film can be easily dislodged from the surface with finger pressure, and parts that are in the hand after being pulled over are therefore subject to corrosion due to fingerprints.

It has now been found that there is an emulsifiable rust inhibitor which does not contain any of the above Has defects, from a mixture of a hydrocarbon oil, a petroleum sulfonate, a wool fat, a Can produce coupling means and a compensating means.

The constituents of the emulsions according to the invention which are stable when mixed with 1 to 10 parts of water forming rust preventive agents are described in detail below.

The mineral oil component has a viscosity in the range from about 9.5 to 650 cSt at 37.8 ° C. For this purpose, Any conventionally refined mineral oil distillate can be used, regardless of whether it is naphthenic or paraffinic Is of origin. Preferred mineral oils have a viscosity in the range from 17 to 108 cSt at 37.8 ° C. The acid-refined, naphthenic distillates dewaxed by means of propane are particularly suitable Crude oils.

The sulfonates are based on sulfonic acids derived from petroleum or synthetic alkyl aromatics, usually by handling a lube oil fraction

009 568/326

i Uö 3

or an alkyl aromatic hydrocarbon with fuming sulfuric acid. One can also use synthetic sulfonic acids. So are z. B. Polypropylbenzenesulfonic acids, Didodecyltoluenesulfonic acids, octadecylnaphthalene sulfonic acids and polypropylnaphthalene sulfonic acids suitable. The acids useful herein have molecular weights in the range of about 250 to 800 and an average molecular weight in the range of about 400 to 550. For purposes of the invention sulfonic acids having an average molecular weight in the range of about 420 to 500 are preferred. The oil-soluble sulfonates are according to the invention in the form of alkali soaps, for. B. as soda soap, potash soap and lithium soap are used. The production of these soaps is known from literature and does not constitute one Part of the present invention. The rust inhibitors according to the invention are particularly suitable for production the alkali soaps of sulfonic acids derived from petroleum products and medium molecular weights from about 420 to 520. Sodium petroleum sulfonates are particularly preferred.

The wool fat itself is obtained by solvent washing wool. When distilling off the solvent a dark-colored mass remains from the washing residue. This mass, the raw wool fat, can be refined to any desired degree of purity by various processes known per se. That Wool grease to be used according to the invention is practically completely neutral and has the following typical characteristics on:

Free fatty acid (as oleic acid) 0.30%

Moisture 0.18

Ash 0.09

Melting point (ASTM D-127) 46 ° C

Mineral acid acidity none

Iodine number (Wij s) 51.0

Saponification number 98.0

Resting penetration (ASTM D-937) 141

Precipitation number (ASTM D-91) 0.10

The coupling agent is the component of the emulsifiable rust inhibitor according to the invention, which is used for Emulsification is used. According to the invention, glycol ethers or polyglycol ethers are used as coupling agents with 5 to 15 carbon atoms in the molecule. It is particularly advantageous to select a coupling agent that is used in the has essentially the same volatility as water, thus both from the finished protective film when drying the water and the coupling agent evaporate and a film remains that does not emulsify again, when water is deposited on it. The glycol ethers which can be used according to the invention include Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, propylene glycol monoethyl ether and as a particularly preferred glycol ether, ethylene glycol monobutyl ether. To the invention Usable polyglycol ethers include z. B. diethylene glycol monomethyl ether or the equivalent Monoethyl or phenyl ethers and from the series of dipropylene glycol ethers z. B. the monoethyl ether. from Diethylene glycol monobutyl ether is particularly preferred among the polyglycol ethers.

The leveling agent is the component of the emulsifiable rust inhibitor according to the invention, which is used for Stabilizes the emulsions at normal and higher temperatures and serves to prevent emulsion separation. This balancing agent consists of a mixture of an organic amine base with water in certain proportions. The organic Amine base is preferably an organic amine with

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several hydroxyl groups or one produced by reacting an alkylene oxide with fatty amines or diamines Polyoxyamine. Of the amines with several hydroxyl groups, triethanolamine is particularly preferred. The polyalkylene oxide derivatives of fatty amines are prepared by adding 1 to 10 moles of an alkylene oxide, preferably ethylene oxide, with 1 mole of a fatty amine or diamine, which has 12 to 24 carbon atoms in the Contains molecule. The manufacture of these substances is in

ίο described literature and does not form an object of Invention. Monoamines, such as tetradecylamine, hexadecylamine and octadecylamine, mixtures can be used as amines such monoamines or diamines, such as N-dodecylethylenediamine, N-octadecylethylenediamine, N-tetradecylethylenediamine, N-tetradecylpropylenediamine and N-octadecylpropylenediamine, as well as mixtures of these Diamines can be used. Although ethylene oxide is preferably used as the alkylene oxide, others can also be used Alkylene oxides, such as propylene oxide, butylene oxide or mixtures thereof, work. Particularly preferred Among the alkylene oxide derivatives of fatty amines or diamines, the polyethylene oxide derivative of N-tetradecylpropylenediamine is which contains about 5 ethylene oxide units. The ratio of the Water to the organic amine in the leveling agent. If the balancing agent is one of several Hydroxyl-containing amine, such as triethanolamine, prepared so should the ratio of water to Amine between 4: 1 and 14: 1. You work with a polyalkylene oxide derivative of an organic amine, the ratio should be between 1: 1 and 14: 1.

To provide an emulsifiable rust preventive with the particularly preferred characteristic properties obtained, the relative proportions of the components must be within narrow limits.

The base mix of mineral oil, metal sulfonate, and wool fat makes up 72 to 95 percent by weight, preferably 77 to 94 percent by weight, of the total mass. The coupling agent is 1 to 10 weight percent, preferably 2 to 8 percent by weight, and the balancing agent to 1 to 18 percent by weight, preferably to 3 to 15 percent by weight of the total mass. The table below shows the generally applicable ones and the preferred ranges indicated.

Basic mix

mineral oil

Alkali sulfonate

Wool fat

Coupling agent

Compensatory means

Amine with several
Hydroxyl groups ..

(Ratio of water
to Amin)

Polyoxyalkyleneamine derivative

(Ratio of water

to Amin)

Ranges (percent by weight)

Generally

applicable

72.0 to 95.0 10.0 to 25.0 10.0 to 25.0 20.0 to 50.0 1.0 to 10.0

1.0 to 18.0

(4: Ibis 14: 1) 1.0 to 18.0

(1: 1 to 14: 1)

Preferred

77.0 to 94.0 15.0 to 23.0 15.0 to 23.0 35.0 to 45.0 2.0 to 8.0

3.0 to 15.0

(7: 1) 2.0 to 15.0

(4: 1)

In order to explain the invention in detail, were

various mixtures falling under the claim or used for comparison are produced and according to standardized,

C7 «J

investigated test methods known in the art for emulsifiable rust inhibitors.

The test for emulsifiability is carried out as follows: 20 ecm of the mass are at room temperature (25 ± 2.8 ° C) in a 100 ccm measuring cylinder of 80 ecm with a ground glass stopper Water added. The cylinder is reversed once and returned to its original position. then it is shaken vigorously twenty times. Each shaking movement consists of a downward (or upward) movement Movement of the hand and return to the starting position, the hand each time a distance of covers no less than 30 cm and no more than 60 cm. This shaking should last 10 to 15 seconds. The content is then checked for completeness of the emulsification and, if necessary, a further 20 or Shaken 40 times in the manner described above. If not complete after 60 shaking movements Emulsion is formed, the emulsifiability is said to be poor. Complete emulsification between 20 and 40 shaking movements are considered sufficient, while the rating "good" is a complete one Means emulsification after 20 shaking movements.

In addition to the test for emulsifiability, the test for emulsion resistance was carried out. to For this purpose, a total of 100 ecm of water and test mixture is added (with different ratios from water to test mixture), as in the test described above, into a 100 ccm measuring cylinder. The mixture is shaken 60 times without interruption as described above. Then the graduated cylinder Stored for 24 hours at 25 or 71 ° C. The amount and type of phase separation that has taken place are then determined.

TabeUe I Emulsifiable anti-rust agents

Mixture No.
3 4

Composition (weight percent)

Basic mix *

Coupling agent
Diethylene glycol monobutyl ether

Ethylene glycol monobutyl ether

Compensatory means
Triethanolamine

Addition product of ethylene oxide with an amine mixture with 10 to 18 Carbon atoms

Addition product of ethylene oxide with N-aminopropyloctadecylamine ....

water

Ratio of water to amine

Test results
Emulsifiability **

Emulsion resistance
(deposited in 24 hours, ° / ₀ ) at room temperature

at 71 ° C

100.0

bad

> 30

90.0

10.0

sufficient

> 30 80.0

20.0

bad

I.
95.0 93.0 94.0 5.0 5.0 5.0 - 1.0 - I. 1.0 1.0 - 1: 1 - Well Well Well <2 <2 <2 35 <2 43

94.0

Well

<2
30th

(Continuation of Table I)

8th 9 10 Mixture No.
11 I 12 80.0
5.0 13th 14th 15th Composition (weight percent)
Basic mix * 93.0
5.0 80.0
5.0 80.0
5.0 80.0
5.0 80.0
5.0 75.0
10.0 70.0
10.0 Coupling agent
Diethylene glycol monobutyl ether
Ethylene glycol monobutyl ether

* 25.0 percent by weight sodium petroleum sulfonate (average molecular weight 460); 50.0 percent by weight neutral wool fat; 25.0 percent by weight mineral oil (2OcSt at 37.8 ° C).
** Ratio of the ingredients of the errrrulsion:

Water to concentrate = 4: 1, in the case of mixtures No. 12 to 16, however, 3: 1.

7th 8th 9 10 Gemis
11 ί ch no.
12th J 13th 14th 15th 1.0 3.0 1.9 1.3 - 1.0 1.0 1.0 Compensatory means
Triethanolamine 1.0
1: 1 12.0
4: 1 13.1
6.9: 1 13.7
10.5: 1 15.0 14.0
14: 1 14.0
14: 1 19.0
19: 1 Addition product of ethylene oxide
an amine mixture with 10 to 18
Carbon atoms Well
<2
30th Well
<2
7th Well
<2
4th Well
<2
<2 Well
<2
20th Well
<2
<2 Well
25th Well
20th Addition product of ethylene oxide
of N-aminopropyloctadecylamine
water Ratio of water to amine Test results
Emulsifiability ** Emulsion resistance
(deposited in 24 hours,%)
at room temperature at 71 ° C

(Continuation of Table I)

I 17 18th Mixture No. 20th 21 22nd 16 94.0 90.0 19th 80.0 90.0 80.0 80.0 5.0 5.0 90.0 5.0 5.0 - 5.0 - - 5.0 - - 5.0 - - - - - - 3.0 - 1.0 2.5 - 1.0 5.0 - - - 1.0 - - - 1.0 - 2.5 - 14.0 - 12.0 14.0 - 1: 1 4.0 14: 1 - 4: 1 14: 1 Well Well 4: 1 Well Well Well Well <2 <2 Well <2 <2 <2 <2 20th 4th <2 <2 20th <2 <2 <2

Composition (weight percent)

Basic mix *

Coupling agent

Diethylene glycol monobutyl ether

Ethylene glycol monobutyl ether

Compensatory means

Triethanolamine

Addition product of ethylene oxide with an amine mixture with 10 to 18 Carbon atoms

Addition product of ethylene oxide with N-aminopropyloctadecylamine.

water

Ratio of water to amine

Test results

Emulsifiability **

Emulsion resistance
(deposited in 24 hours, ° / ₀ )
at room temperature

at 71 ° C

80.0

14.0 14: 1

Well

<2 <2

* 25.0 percent by weight sodium petroleum sulfonate (average molecular weight 460); 50.0 percent by weight neutral wool fat; 25.0 percent by weight Mineral oil (20 cSt at 37.8 ° C). ** Ratio of the emulsion components:

Water to concentrate = 4: 1, in the case of mixtures No. 12 to 16, however, 3: 1.

A careful examination of the values in Table I shows the critical features of the invention.

Mixture No. 1 shows that the emulsifiability of the basic mixture is in itself insufficient. To the Mixtures Nos. 2 to 4 can be seen that varying amounts of coupling agent improve emulsifiability can, however, do not improve the resistance at high temperature (71 ° C). The mixtures No. 5 and 6 show that with 2.0 percent by weight

Leveling agent with a water-amine ratio of 1: 1 is an excellent product and that the omission of the amine leads to the separation of the emulsion at high temperature.

Mixtures No. 7 to 11 and 13 to 15 contain amines with several hydroxyl groups in the molecule. A Comparison of the values for Mixture Nos. 7-11 shows that water is a necessary component of the leveling agent and that a water-amine ratio of

at least 4: 1 for good resistance at high Temperature is required. Mixtures Nos. 13 to 15 show that the upper limit of the amount of coupling agent is about 10.0 percent by weight.

From mixture no. 12 you can see that even with S 15.0 percent by weight of water, if not organic Amine is present, an unsatisfactory product with poor emulsion resistance at high temperature receives.

Mixtures No. 17 to 21 contain the reaction product of a mixture of amines with 10 to 18 C atoms with 5 units of ethylene oxide and prove that this balancing agent with a water-amine ratio can work from 1: 1 to 14: 1. Mixture # 16 illustrates the applicability another type of polyoxyalkylene derivative of an amine.

Mixtures No. 22 and 23 contain a glycol ether as coupling agents and show that such coupling agents give excellent results receives.

Mixtures Nos. 5 and 13 of Table I were also used for their emulsion resistance investigated by water of different degrees of hardness.

The complete results of these tests are given in Table II. In addition, these rust inhibitors the standard test for service life is carried out in the humidity chamber. The results too this investigation appear in the table.

Table II
Emulsifiable anti-rust agents

Mixture. No. 5 I 13

Composition, percent by weight

Basic mixture A *

Diethylene glycol monobutyl ether

Addition product of ethylene oxide with an amine mixture with 10 to 18 carbon atoms

Triethanolamine

water

Ratio of water to amine

Composition of the emulsion, water to total mixture ...

Test results
Emulsifiability

Emulsion resistance

deposited in 24 hours, ° / ₀

at 25 ° C, tap water ... at 71 ° C, tap water ...

Hardness of the water, parts Ca per million

at 25 ° C

0

150

300

600

* See table I.

93.0 5.0

1.0

1.0 1: 1

4: 1 good

<2 <2

80.0 5.0

1.0 14.0 14: 1

3: 1 good

<2

<2

<2

Mixture No.
5 I 13 2 at 71 ° C
0 2 150 2 300 10 600 > 600 Check for service life in the
Humidity chamber, hours ** > 600

** The plates were immersed in the emulsion at 71 ° C, Hanged in the laboratory for 16 hours and placed in the humidity chamber.

Briefly summarized, the invention relates to emulsifiable rust inhibitors, which are composed of a base mixture, consist of a coupling agent and a compensating agent, these individual basic components in the proportions described above are present.

A particularly preferred emulsifiable rust inhibitor has the following composition:

Components by weight

Mineral oil (20 cSt at 37.8 ° C) 20.0

Sodium Petroleum Sulphonate (Medium

Molecular weight 460) 20.0

Neutral WoU fat 40.0

Diethylene glycol monobutyl ether 5.0

Triethanolamine 1.0

Water 14.0

(Ratio of water to amine = 14: 1)

Claims (1)

PATENT CLAIM: Emulsifiable rust inhibitor, which is stable when mixed with 1 to 10 parts of water Forms emulsions consisting of a mixture of 72 to 95, preferably 77 to 94 percent by weight a base mixture containing 10 to 25, preferably 15 to 23 percent by weight of a mineral lubricating oil a viscosity of 9.5 to 650, preferably 17 to 108 cSt at 37.8 ° C, 10 to 25 percent by weight an alkali salt of a sulfonic acid having a molecular weight in the range from 250 to 800, is expedient an average molecular weight between 400 and 550, in particular between 420 and 500, and 20 Contains up to 50, preferably 35 to 45 percent by weight of natural wool fat, with 1 to 10, preferably 2 to 8 percent by weight of a glycol ether or polyglycol ether with 5 to 15 carbon atoms in the molecule as coupling agent and 1 to 18, preferably 3 to 15 percent by weight of a balancing agent, which either from an amine containing several hydroxyl groups in the molecule and water in the ratio of water to amine of 4: 1 to 14: 1 or from a polyalkylene oxide derivative of a fatty amine and water in a ratio from 1 to 14 parts of water per part of amine, the percentages being based on the total product relate. <2 <2 <5 Considered publications:
German Patent Nos. 909 132, 891 312;
USA.-File transcript No. 2 408 971 or its report in Metalloberfläche, Edition A, 1951, p. A 26, right column, para. 3.