DE1264209B - Anti-corrosive agents - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

Number:
File number:
Registration date:
Display day:

C23f

German KL: 48 dl - 11/10

P13491VIb / 48dl
3rd February 1955
March 21, 1968

The present invention is concerned with corrosion protection, including that caused by oxidation Corrosion, especially with the corrosion of ferrous metals. The corrosion is caused by this prevents the use of any of the polyamine salts or salt complexes described.

The present invention relates to the use of salt-like or complex reaction products of 1 mole of one containing at least two basic nitrogen atoms, optionally heterocyclic polyamino compound which can also contain oxygen and at least one having a hydrophobic group of at least eight contiguous carbon atoms, with at least 1 mole of a polycarboxylic acid containing no more than four, preferably three or four, carboxyl groups and at least one hydrocarbon radical having not less than 8 carbon atoms exclusively which contains carboxyl carbon atoms, optionally mixed with 8 to 32 carbon atoms containing monocarboxylic acids, as an inhibitor in corrosive action on metals Liquids or gases, especially in liquid hydrocarbons, those with ferrous metals among come into contact with aerobic or anaerobic conditions.

The anti-corrosion agents used can be used in the presence or absence of oxygen will.

The salt-like or complex reaction products used according to the invention are simple or multiple salts or single or multiple salt complexes.

Is in the neutralization of the polyamino compound, i. H. a partial neutralization, a total neutralization or a neutralization in which a salt complex is formed, both a polycarboxylic acid as well as a cleaning agent-forming monocarboxylic acid are used, this creates extraordinary effective corrosion chipping agent.

A particularly effective group of anti-corrosion agents used according to the invention are Salt complexes of cyclic amidines, which are derived from triamines, the salt complexes from 1 mol of a dibasic cyclic amidine, which preferably contains a five-membered ring (ζ. B. imidazoline), about 1 mole of a monounsaturated fatty acid with 8 to 22 carbon atoms, such as oleic acid, and about 1 mole of a dimeric or trimeric acid obtained by condensation of unsaturated, aliphatic Monocarboxylic acids or oxymonocarboxylic acids with about 16 to 18 carbon atoms in the Anti-corrosive agents

Applicant:

Petrolite Corporation,

Webster Groves, Mo. (V. St. A.)

Representative:

Dr. W. Schalk and DipL-Ing. P. Wirth,

Patent attorneys,

6000 Frankfurt, Große Eschenheimer Str. 39

Named as inventor:

William John Ries, St. Louis, Mo. (V. St. A.)

Claimed priority:
V. St. v. America 5 February 1954
(408 617, 408 627)

Molecule, such as linseed oil fatty acid, are obtained.

The products used according to the invention are mostly surface-active, i. that is, the polyamino compounds are surface-active as free or hydrated bases or in the form of a salt. This Salt can be mixed with a low molecular acid, such as acetic acid or glycolic acid, etc., with gluconic acid or with other higher molecular weight monocarboxylic acids, as will be described below, z. B. higher fatty acids are formed.

For the sake of clarity, the following explanations are divided into 5 parts, with part 1 is again divided into six sections.

Part 1 relates in its entirety to the high molecular weight polyamino compounds that are used to implement to be used with the acidic products.

Part 1, Section A, relates to the polyamino compounds known as polyamines.

Part 1, Section B, concerns the polyamino compounds known as cyclic amidines will.

Part 1, Section C, concerns the polyamino compounds known as amides.

Part 1, Section D, relates to the polyamino compounds known as esters.

809 519/635

Part 1, Section E, concerns the polyamino compounds known as oxazolines.

Part 1, Section F, relates to other polyamino compounds, the at least two basic amino nitrogen atoms and at least one hydrophobic, at least eight uninterrupted Having carbon atoms. Contain group and have anti-rust properties.

Part 2 concerns suitable polycarboxylic acids which contain no more than 4 carboxyl groups and of which the dimerized fatty acids represent a subgroup.

Part 3 concerns high molecular weight, detergent-forming monocarboxylic acids with 8 to 32 carbon atoms, including monoethylenic monocarboxylic acids having 8 to 22 carbon atoms (such as oleic acid), naphthenic acids, resin acids, which together with the polycarboxylic acids can be used.

Part 4 concerns the preparation of the salts or salt complexes from those described in Part 1 Polyamines and the polycarboxylic acids described in Part 2, where appropriate the Monocarboxylic acids described in Part 3 can also be used.

Part 5 relates to the use of the salts or salt complexes described in Part 4 in Compound, with gasoline, lubricating oil or flushing oil for the production of corrosion and Rust preventives and also relates to a method for corrosion or rust protection by using the compounds mentioned.

cycloaliphatic, aromatic or aralkyl radical or for the same as R. R and R ″ can also Contain ether oxygen atoms and / or hydroxyl groups.

The amino nitrogen atoms should so by a substituted or unsubstituted di-, tri- or Tetramethylene group be separated.

Suitable polyamines are e.g. B. those of the formula

R - NH - (CH ₂ ) ₃ - NH ₂

where R stands for the residues of lauric acid, coconut oleic acid ' or abietic acid, or ethylenediamines, triethylenetetramines which are more highly alkylated on the nitrogen and butylenediamines.

Part 1

Section B Suitable cyclic amidines are, for. B.

,A.D'

R - C (

I.
—CH-R '

R "

where R = alkyl, preferably higher alkyl, alkenyl, abietyl, cycloalkyl, R '= H or lower Alkyl, R "= H or

R '"- N

R ₅ R ₅

Part 1
Section A.

R "'= alkylene, R ₁ = H, alkyl, R ₅ = H, alkyl, oxyalkyl, acyl, acylated oxyalkyl, χ * = 0, 1, 2 ... The polyamines in question contain 40 means, and compounds of formula

at least one high molecular weight group and can

can be represented by the following formula: ™, pu ^ r ^ pu n.

H
R —N

χ = 0 to 8.

• R '- In - R'I— n:

/ R "

45 R '- CH - N /
R "

^ N-CH-R '

In this formula, R stands for a radical formed by a high molecular weight cleaning agent Derives monocarboxylic acid, e.g. B. a saturated or unsaturated aliphatic acid with 8 to Carbon atoms, a naphthenic acid, a resin acid, one by oxidation of waxes obtained acid, etc .; R 'is a divalent residue here, such as

- CH ₂ - CH ₂ - CH ₂ - - CH ₂ - CH ₂ - CH ₂ - CH- CH ₂ - CH-CH ₂ -Re radical of a dibasic acid, R, R ', R "as defined above.

All suitable polyamines can be used to prepare the imidazolines, which are described in Section A.

The corresponding tetrahydropyrimidines of the formula can also be used

A.D'

^ / CHR '

^X N -CHR '

60

CH ₃

CH ₃ R "

- CH - CH -
Il
CH ₃ CH ₃ ■

and R "represents hydrogen or an aliphatic, where R, R ', R" are as defined above, are used.

The present invention is limited to cyclic amidines that are no more than two and preferably only one ring included.

Cyclic amidines containing more than one ring are illustrated by the following formula :

R - i

; N - CH ₂

Ί
-N - CH ₂

C ₂ H ₄

CH ₂ -N
CH ₂ - N ^x

NC ₂ H ₄

IC -

R = hydrocarbon radical with 8 to 32 carbon atoms.

Cyclic amidine that contains a basic tertiary amino group is listed as follows:

■ c:

* N - CH ₂

^ N - CH ₂ CH ₃

C ₂ H ₄ -NH-C ₂ H ₄ -NH-C ₂ H ₄ -N-CH ₃ saturated aliphatic acids with 8 to 32 carbon atoms, naphthenic acids, resin acids, acids obtained by the oxidation of waxes, etc., and polyamines, in all of which nitrogen atoms are substituted with an alkyl or oxyalkyl group so that ester formation occurs instead of amide formation.

Suitable oxyalkyl polyamines are polymers of N-methyldiethanolamine, triethanolamine and N-methyl - diisopropanolamine, triisopropanolamine, N - ethyl - dibutanolamine, tributanolamine and Monomers and polymers of N, N'-tetraoxyethylethylenediamine, N, N'-tetraoxypropylpropylenediamine, Pentaoxyethyl - diethylenetriamine and other amines.

Suitable basic esters are e.g. B. those of the formulas

20th

RCOO R '

R '"

Part 1

Section C.

The amides in question are derived from high molecular weight, detergent-forming monocarboxylic acids from, e.g. B. saturated or unsaturated aliphatic acids with 8 to 32 carbon atoms, Naphthenic acids, resin acids, acids obtained by oxidation of waxes, etc., and polyamines, as described above in Part 1, Section A.

Examples of suitable acid amides are expressed by the following formulas:

R '"

R "'

RCO - NH - f - R'N -4 - R'N

CO - NH 4 - R'N -f = - R'N

R ₄

CO - NH 4 - R'N -V- R'N

In these formulas, R = higher alkyl, alkenyl, R '= alkylene, R "= H, alkyl, R'" = H, alkyl, acyl, Rj = residue of a divalent acid, χ = O, 1, 2 ...

The amido nitrogen atoms can optionally also be alkylated.

Part 1
Section D.

The esters in question are derived from high molecular weight, detergent-forming monocarboxylic acids from, e.g. B. of saturated or un-R = higher alkyl, R '= alkylene radical, optionally interrupted by ether oxygen atoms, R "= H, alkyl, oxyalkyl, R" '= R "or RCOO, Ri = remainder

/ R '"of a divalent acid, * = O, 1, 2 ...

Although it is stated that the

^S R '"radicals derived from high molecular weight acids are hydrocarbon radicals and this is usually the case, these radicals can under certain circumstances contain one or more oxygen atoms without affecting their hydrocarbon nature.

/ R '" . For example, the acid residue from the

Ricinoleic acid or oxystearic acid can be obtained

^ R "'and so have a hydrophilic group without

thereby the hydrophobic character of the rest in

/ R '" 50 is decreased in some way.

The rest can also contain ether bonds,

^ R '"if you use a glycidyl ether as an oxyalkylation

medium used, whereby not only an ether bond, but also an oxy group is introduced be e.g. B. if you have a glycidyl ether of the formula

R - O - CH ₂ - CH - CH,

60

65

in which R is a radical derived from castor oleic acid or oxystearic acid, is used.

Part 1
Section E.

The following are very generally suitable for the preparation of suitable oxazolines, 1,2- and 1,3-alkylolamines

Formulas:

JHLO C * JHL C -Jtio Ct) L

NH,

H ₂ N - CH ₂ - CH ₂ - CHOH - CH ₂ - CH ₃

H ₂ N - CH ₂ - CH ₂ - CHOH - CH ₂ - CH ₂ - NHCH ₃ H ₂ N - CH ₂ - CH ₂ - CHOH - CH ₂ - CH ₂ - CHOH - CH ₂ - CH ₂ - NH ₂

respectively.

HO - CH ₂ - CH ₂ - NH ₂

H ₂ N - CH ₂ - CHOH - CH ₂ - CH ₃

H ₂ N - CH ₂ - CHOH - CH ₂ - CH ₂ - NHCH ₃

H ₂ N - CH ₂ - CHOH - CH ₂ - CH ₂ - CHOH - CH ₂ - CH ₂ - NH ₂

From the above formulas it can be seen that the only essential groups in 1,2- or 1,3-position oxy and primary amino groups are. In addition to these essential groups, the alkylolamines can have further substituents or groups included. These additional substituents or groups can, for. B. one or be several alkylene chains containing oxy groups or secondary or tertiary amino groups.

Monoethanolamine is preferred because of its cheapness and ready availability Alkylolamine. Can be used e.g. B. also mono-isopropanolamine, mono-n-propanolamine, 2-amino-1-butanol, 2-amino-2-methylpropanol, 2-amino-1 - hexanol, 2 - amino - 2 - methyl -1,3 - propanediol, 2-amino-1-butanol, 2-amino-4-pentanol, 2-amino-4-hexanol, 2-amino-3-heptanol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol and tris (oxymethyl) aminomethane.

To prepare the oxazolines, mono-, di- or tricarboxylic acids can be used, e.g. B, those as described in Part 2.

Are z. B. 2-Amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol and tris (oxymethyl) aminomethane used, oxazolines are formed which contain oxy groups as substituents. Such oxazolines are known and of these for example, the following are listed:

2-ethyl-4-oxymethyl-4-methyloxazoline,

2-isopropyl-4-oxymethyl-4-methyloxazoline,

2-heptyl-4-oxymethyl-4-ethyloxazoline,

2-tridecyl-4-oxymethyl-4-methyloxazoline,
2-octyl-4-oxymethyl-4-ethyloxazoline,
2-Hendecyl-4-oxymethyl-4-methyloxazoline,
2-Hendecyl-4-oxymethyl-4-ethyloxazoline,
2-heptyl-4-oxymethyl-oxazoline,
2-heptyl-4,4-bis (oxymethyl) oxazoline,
2-Hendecyl-4,4-bis (oxymethyl) oxazoline etc.

Such oxazolines with reactive oxy group can with 1 to 3 moles of an alkylenimine, such as. B. Ethylenimine or propylenimine, are reacted and so polyaminooxazolines are obtained, which for the present purposes are useful.

Polyamino compounds containing a tertiary nitrogen atom / can be obtained by instead of ethyleneimine or propyleneimine, a compound is used which is obtained by reacting a secondary amine such as diethylamine, dipropylamine, dibutylamine, diamylamine, etc., with epichlorohydrin is obtained, and then the ring closure occurs. These known compounds have the following Structure:

R.
R.

N -CH, -CH-CH ₇

R = alkyl.

45 If such an aminoalkylene oxide is used instead of an alkyleneimine, a basic one is obtained tertiary amino group.

Suitable oxazolines are e.g. B. obtained by the following reactions:

CH,

a) CH ₂ -C-CH ₂ + RCOOH

OH

OH

H, N

R = higher alkyl, alkenyl.

b) I + R ₂ - CH CH ₂
NH

HIGH ₂ - C 2H ₂ O -CH ₂ N
Y I.
0 R. CH ₃ ^ H ₃ R ₂ NH) _x C ₂ H ₃ R ₂ / ~ * -CH ₂ + N O OCH ₂ -

R ₂ = alkyl; χ = O, 1.2 ...

9 10

CH ₃

c) I + ³ ^ N-CH ₂ -CH CH ₂ > ³ ^ n-CH ₂ -CHOH-CH ₂ -O-CH ₂ -C CH ₂

R ₃ ⁷ \ _o / R ₃ ⁷ II

^ü NO

R ₃ = alkyl.

R ₆ \ / Re

) C Ns / N- C (

d) HOOCR ₅ COOH + 2R ₆ R ₇ C CHOH > R ₇ ^/ | ) C -R ₅ -Cf | ^X R ₇

IIR ₈ -CH-O / ^X O-CH

NH ₂ R ₈ I.

R ₈

R ₆ to R ₈ = H, alkyl; R ₅ = divalent radical of a dicarboxylic acid

e) Suitable 6-membered ring systems are ζ. Β. obtained by the following reactions:

ι CH η f,

H ₂ N-CH ₂ -CH ₂ -CR ₉ + RCOOH > N ^ ² / CHR ₉

I ^ c o /

OH I

R ₉ = alkyl, H; R = alkyl, cycloalkyl, alkenyl. I.

/ Rio / Rio H ₂ CC -CH ₂ -CH ₂ -N (

f) NH ₂ -CH ₂ -CH-CH ₂ -CH ₂ -N \ + RCOOH> | | \ r _u

I ^X R _U NO

OH \ _c /

R = as above; R ₁₀ , R ₁₁ = H, alkyl, oxyalkyl, acyl, acylated oxyalkyl.

Corresponding pentoxazolines can also be produced.

Part 1
Section F.

In addition to the various classes of polyamino compounds already described, others are presented here known compounds listed, e.g. B. Connections, such as

CH ₂ H ₂ C CH ₂ H ₂ C

X N - CH - N X

CH ₂ H ₂ CR ₁ CrI ₂ H ₂ C

in which R _{1 is} an alkyl-substituted phenyl radical in which the alkyl radical is propyl, butyl and X stands for an oxygen or CH ₂ bridge.

Another class is derived from piperazine derivatives of the following structure:

CH ₂ - H ₂ C

X f- OC ₂ H ₄ ) ,,, - N N- (C ₂ H ₄ O) ₁₁ -C ₂ H ₄ OR '

CH ₂ - H ₂ C

In this formula, X stands for R or RCO, where R 65 is a lower acyl radical, m and /; mean whole

is a long-chain aliphatic radical, so that the numbers from 1 to 20.

The carbon content of X is between 8 and 24. Other suitable polyamino compounds can

and R 'is hydrogen, lower alkyl, or by suitable acylation, e.g. B.

by one of the described monocarboxylic acids containing at least 8 carbon atoms and a Polyamine of the following formula is used:

HO

CH ₂ - NH - CH ₂ - CH ₂ - N (CH ₂ CH ₂ OH) ₂

QH ₁₀

CH, - H, C

CH, - H, C

HIGH

CH - NH - CH ₂ - CH ₂ - NH - CH CH - OOCR

CH, - H ₇ C

R is a radical with at least 7 carbon atoms.

NC ₈ H ₁₇

CH-C «H

17th

HCOOCR

R is a radical with at least 7 carbon atoms.

C ₄ H ₉

• N '

CH,

CH ₂ -N- C ₁ H

17th

Compounds of the type described above or analogs or derivatives can be mixed with alkylenimines, such as ethyleneimine, propyleneimine, are reacted in order to introduce one or more amino groups. Such derivatives are easily accessible to acylation, whereby z. B. a high molecular weight group a higher fatty acid can be introduced.

Other suitable polyamino compounds are obtained using compounds such as dimethylhydantoin with 1 or more moles of an imine such as ethyleneimine or propyleneimine.

These products can also be acylated in the manner described above.

Reference is also made to the nitrogen-containing products described in US Pat. No. 2,618,606 referenced, which should essentially prevent fogging or tarnishing. These products can evidently often reacted with 1 or more moles of one of the alkylenimines described and then acylated with a higher fatty acid or reacted with a substituted phenylglycidyl ether, making a useful polyamino compound. the at least one high molecular weight group with 8O or contains more carbon atoms.

Another useful group of compounds already mentioned are the non-cyclic amidines the general formula

R, \ * ^ NH

^N NH,
in which Ri and Ro are hydrogen or an alkyl-CH ₂ - H ₂ C

group and π is an integer from 7 to 13 (see British Patent 518 575).

Other suitable polyamino compounds which form the salts or salt complexes described, can acyl radicals or an acyl radical of a low molecular weight monocarboxylic acid, such as. B. acetic acid, Propionic acid, butyric acid, glycolic acid, lactic acid, etc. This is not only true of the cyclic ones Amidines, but also of other compounds such as high molecular weight polyamines or esters hydroxylated polyamines.

Of course, comparable compounds can also be derived from other types of cyclic amidines, z. B. tetrahydropyrimidines can be obtained.

Other suitable compounds for the present purpose are obtained by high molecular weight Diamines of the formula

R - NH - CHo - CHo - CHo - NHo

where R stands for a hydrocarbon radical with 8

to 18, in particular with 12 to 18 carbon atoms, are reacted with a single mole of a low molecular weight monocarboxylic acid, such as acetic acid, propionic acid, butyric acid.
It should be noted that the described

Polyamino compounds are characterized in that they are built up exclusively from the elements carbon, hydrogen, oxygen and nitrogen.
Such polyamino compounds are preferably

fertilize used, which is different from polyalkyleneamines. such as polyethylene amines, or polypropylene amines derive comparable connections. The reason is obviously that these compounds the cheapest source of basic nitrogen

containing materials represent that they are relatively inexpensive in combination with others Raw materials, such as higher fatty acids, can be easily processed into anti-corrosion agents and also the manufacturing process usually

can be carried out quickly and is relatively cheap. The main amount of the polyamino compounds mentioned consists of monomeric, non-resinous compounds. However, some are already made that are polymeric, mostly linear poly-

mers, since crosslinked polymers are often insoluble in mineral oil fractions. Such polymeric polyamino compounds are linear polymers, e.g. B. those produced by the reaction of triethylenetetramine or tetraethylenepentamine with a high molecular weight di-

carboxylic acid, e.g. B. one of said dimerized fatty acids can be obtained.

Of course, you can also do this before neutralization a mixture instead of a single

create a bond, d. That is, a mixture of the various high molecular weight compounds described in Part 1 can be used Use amino compounds before making the salts or salt complexes. Such Mixtures can be prepared by adding the separately prepared high molecular weight Amino compounds are mixed or usually more simply by a process in which these are the same as Mixture incurred.

Furthermore, it is sometimes desirable for economic reasons to use a mixture of polyamino compounds to use, e.g. B. one mole: mole mixture of methyl ethylenediamine and tetraethylene pentamine. In this case, whatever later method is used, more becomes received as a connection. A mixture of diethylenetriamine and pentaethylene hexamine can also be used be used in molar proportions.

Another possibility is the combination of a hydroxylated and a non-hydroxylated one Polyamine, the former being made by the use of an alkylene oxide. Such a mixture enables the introduction of ester groups under the appropriate conditions.

Part 2

As already stated, a large number of polycarboxylic acids can be used for the present invention be used. These polycarboxylic acids have two to four carboxyl groups and are therefore characterized in that, in addition to the carboxylic acid groups, they also contain at least one hydrocarbon radical with not fewer than 8 carbon atoms contain.

Suitable polycarboxylic acids are in the following USA. - Patent specifications described: 2,329,432, 2 625 555, 2 450 627, 2 320 217, 2 339 218.

Some particularly useful tricarboxylic acids are obtained by maleic anhydride and a suitable unsaturated acid, e.g. B. the linolenic acid, converts. A distinction is made depending on Kind of unsaturated fatty acid used two types. One of these is usually the clocker adduct compounds designated (see U.S. Patents 2,188,883 to 2,188,890). A Example of such a reaction is

warmth

CH ₃ CH ₂ CH = CHCH ₂ CH = CHCH ₂ CH = CH (CH ₂ ) ₇ COOH

Linolenic acid + HC = CH

Maleic anhydride CH ₃ CH ₂ CH CHCH ₂ CH = CHCH ₂ CH = CH (CH ₂ ) ₇ COOH

HC
C.

CH
C.

O'

Similar compounds are described in U.S. Patents 2,124,628, 2,264,354, 2,517,563, 2,390,024, 2,359,980 and 2,039,243.

Many dicarboxylic acids suitable for the present purposes are also known. This special Dicarboxylic acids should - apart from the carboxyl groups - at least one hydrocarbon group contain at least 8 carbon atoms.

The dicarboxylic acids can contain up to 32 and more carbon atoms, especially if they are made by the oxidation of wax or by the processes described below have been. Generally known dicarboxylic acids which, apart from the carboxylic acid groups, 8 or contain more carbon atoms, are the sebacic acid, the methylenedisalicylic acid. Similar disalicylic acids, in which both phenolic nuclei have alkyl substituents up to 10 carbon atoms have been introduced are known.

Other known dibasic acids are the so-called Adduct acids derived from maleic anhydride. Examples are the adduct acids called, which are obtained by reaction of maleic anhydride with terpenes and which have the hydrophobic properties described above. Likewise, adducts can be made from Maleic anhydride and monoolefinic hydrocarbon can be used (see U.S. Patents 2 055 456, 2 124 628, 2 133 734 and 2 230 005). In a similar way, monocarboxylic acids, like sorbic acid, reacted with an unsaturated fatty acid like linolenic acid and thus useful compounds are obtained. Other acids can be obtained from the Clocker adducts Similar products can be obtained, with an addition next to an unsaturated one Binding, but without using this binding itself, occurs, e.g. B. if oleic acid as one of the Starting products is used. Sometimes this occurs during the production of the adduct acids Anhydride as an intermediate product, which, however, is easily converted into the corresponding acid with water can be.

Numerous dimeric fatty acids have been made or described (see, e.g., U.S. Patents 2,417,739 and 2,632,695).
Further, the various dicarboxylic acids obtained from abietic acid, etc. can be generally referred to as dimerized resin acids. Find application. There have also been dimerized acids from fish oil fatty acids in which the

Total number of carbon atoms is between 20 and 24 is obtained; the dimerized acids can therefore contain up to about 44 and more carbon atoms. The same is true for certain dimerized ones Acids obtained from the oxidation of wax. Furthermore, esters were dimerized Acids with aromatic compounds such as alkylated or polyalkylated naphthalene in The presence of aluminum chloride reacted and so usable dicarboxylic acids with up to 50 carbon atoms manufactured.

Another class of analogous compounds are the substituted malonic acids, such as cetylmalonic acid, Stearylmalonic acid, oleylmalonic acid, octylcetylmalonic acid.

Other useful polycarboxylic acids are described in U.S. Patents 2,497,673, 2,369,640, 2,459,717, 2 394 044, 2 182 178, 1 702 022, 1 721 560, 1 944 730,

1 993 025, 2 230 005, 2 232 435, 2 368 602, 2 402 825,

2,490,744, 2,514,533, and 2,518,495. In U.S. Patent 2,360,426, the

Preparation of higher alkylene-substituted dicarboxylic acids of the general formula

R.

Alkylene-C-COOH

H-C-COOH

described. In this formula, R stands for hydrogen and alkyl radicals, alkylene for an alkylene group having 5 to 16 carbon atoms.

part 3

In connection with the polycarboxylic acids it can form a high molecular weight detergent Monocarboxylic acid, e.g. B. a saturated or unsaturated aliphatic acid with 8 to 32 carbon atoms, a naphthenic acid, resin acid or an acid obtained by oxidation of wax is used will. Suitable acids are the caprylic, capric, stearic, oil, castor oil, lauric, palmitic, Oxystearic, abietic, oxyabietic acid and fatty acids from animal or vegetative raw materials, such as coconut oil, rapeseed oil, palm oil, olive oil, cottonseed oil, fish oil. These acids result with soluble bases such as sodium or potassium hydroxide, soap or detergent-like products.

Of the unsaturated acids that are used to produce salt complexes together with cyclic ones Amidines derived from triamines are particularly found to have 8 to 22 carbon atoms containing higher fatty acids with only one ethylenic bond application. Some of these connections are the usual unsaturated fatty acids and can be obtained from fat raw materials; others can be obtained by synthesis. These acids include 2-octenoic acid, 2-nonenoic acid, 2-decenoic acid, 10-undecenoic acid and especially undecylenic acid (1-undccen-11-carboxylic acid), a commercial product obtained by destructive distillation of castor oil.

The preferred unsaturated acid used is because of its price and particular utility the oleic acid. Other acids with only one double bond can be obtained from fats that contain hydrolysis to provide fatty acids with a carbon content of up to 22 carbon atoms. Such acids can selectively hydrogenated and thus acids containing up to 22 carbon atoms with only one unsaturated Bond are preserved.

Either oleic acid or undecylenic acid is used in the following examples.

Part 4

The production of a salt or salt complex is relatively simple, since it is only one Neutralization or a neutralization with subsequent Requires complex formation. The implementation of the procedure depends primarily on whether the reactants or the resulting product are solids or liquids. Man may optionally be a solvent, especially a non-aqueous solvent, especially one Use a hydrocarbon such as xylene.

The corresponding polyamino compound, e.g. B. a cyclic amidine, is heated to a temperature at which it is liquid and so can be easily handled, e.g. B. to 50 to 60 ' ³ C. Then the appropriate amount of monocarboxylic acid, z. B. oleic acid added. The mixture is stirred for about 10 to 60 minutes, then an appropriate second reaction agent, e.g. B. a dimerized fatty acid, added and stirring continued. The temperature mentioned is maintained during the entire reaction and, if necessary, increased somewhat to achieve a completely homogeneous mass. In most cases, an increase in temperature due to the heat of reaction can be observed. When the reaction has ended and the product is homogeneous, this can optionally be treated with any conventional solvent, e.g. B. xylene, are diluted. The practical implementation is illustrated by the following examples.

The preferred polyamino compounds used are cyclic amidines, since these or their Derivatives such as the amino or amidoamidines are readily available. Another reason is that the cyclic amidine is a tertiary ammo radical contains and therefore, as already mentioned, a complex formation is possible, a property that also other compounds having a basic tertiary amino group which, however, do not form part of this group of a cyclic amidine ring contain.

In the following, the polyamino compounds are referred to as "compound A".

With "Compound B" are high molecular weight detergents forming monocarboxylic acids, such as abietic acid, naphthenic acid, and especially higher ones Called fatty acids. "Compound C" becomes dimerized fatty acids, especially dimerized ones Linseed oleic acid, which was used because of its easy accessibility, is called. With »connection D «denotes the other dicarboxylic acids which do not correspond to the dimerized fatty acids. As a rule, these dicarboxylic acids are obtained by reacting maleic acid and olefins. "Compound E" is the name for tricarboxylic acids and "Compound F" for tetracarboxylic acids.

example 1

The amine used was aminopropyl soy amine, which is derived from soy fatty acid. the corresponding formula is

R - NH - CH ₂ - CH ₂ - CH ₂ - NH ₂

R = hydrocarbon residue from soybean oil fatty acid. The molecular weight is 321.321 g (1 mol) of the polyamine were mixed with 284 g (1 mole) of stearic acid and 600 g (1 mole) of dileinoleic acid. the Mixture was heated to 60 ° C. and stirred until homogeneous. For easier execution the mixture can optionally be diluted with the same amount of xylene.

Connection A:

a) Cyclic compounds such as imidazolines, tetrahydropyrimidines, oxazolines, pent-oxazolines, or

b) non-cyclic compounds, such as polyamines, basic esters (see the corresponding above in Part 1 given general formulas).

Connection B:

Stearic, oleic, lauric, ricinoleic acid.

Connection C:
Dileinoleic acid.

Connection D:

Octadecenyl, hexadenyl, dodecenyl, nonenyl succinic acid.

Connection E:

l, l, 3-tri- (ß-carboxyethyl) indene, tri (/ i-carboxyethyl) acetophenone.

Connection F:

2,6-tetra- (w-carboxyethyl) -cyclohexanone.

The above-mentioned compounds were mixed in such proportions that

a) the total acidity of the carboxyl groups in excess of the usual basicity of the polyamino compounds is,

b) the total acidity is not in excess, d. H. the neutralization just now is complete or even incomplete.

The anti-corrosion agents according to the invention can be di-, tri- or tetracarboxylic acids alone or contain a mixture of di- and / or tri- and / or tetracarboxylic acids. If necessary, can each mixture still contains monocarboxylic acid.

With regard to the preparation of the derivatives of the polyamine compounds, reference must be made to two facts will. One is that in certain cases a salt is referred to as a complex salt the second in the appearance of special properties.

Namely, it has been found that an apparently dibasic polyamino derivative, e.g. B. a cyclic amidine derived from a triamine can combine with three carboxyl groups, although only a combination with two carboxyl groups is to be expected. This was called salt complexation designated. Furthermore, it has been found that when two of the three carboxyl groups of one of the Dimer acids described below originate, the product obtained as a corrosion protection agent - including corrosion by oxidation - is unusually effective and also for other uses is useful, e.g. B. as an "antistripping agent" for asphalt. It so prevents that the asphalt separates from the mineral aggregates. It is enough if it is in proportion to the asphalt from 1 to 25: 1000 is added and this is then added to the mineral aggregates.

On the other hand, it has been found that e.g. B. a yourself

cyclic amidine derived from a triamine, when neutralized with two different acids, one of which is an unsaturated higher fatty acid such as oleic acid and the other of which is one of the dimerized fatty acids described, the resulting mixed salt in association with a normally liquid mineral oil fraction as Corrosion inhibitor and rust preventive is particularly effective. This is the case when the mixed salt or what is at first sight regarded as a mixed salt is obtained by approximately the following mixing ratios: 1 mol of an apparently dibasic, cyclic amidine derivative, 1 mol of a monocarboxylic acid with an ethylenic double bond and 1 mole of a dimer acid.
The only explanation of the processes seems to be described in the publication by JL Riebsomer, "The synthesis of imidazolines from 1,2-diamines and carboxylic acids," Journal of the American Chemical Society, 70, 1629 (1948).

Reference is made to the publication by Samuel Kaufman and C. R. Singleterry, “The Reaction between tertiary amines and organic acids in non-polar solvents «in Journal of Physical Chemistry, 56, No. 5, p. 604 (1952).

If the imidazolines are replaced by tetrahydropyrimidines, the same structures are obtained. Apparently the 5- and 6-membered cyclic amidines have a special structure. It should be pointed out that the use of dimeric acids or the use of triamines derived cyclic amidines is not described in the cited publication by Riebsomer. In the examples below, the preparation of the salt complex is from some of triamines derived cyclic amidines.

Example la

700 g of 1-aminoethyl-2-heptadecylimidazoline were heated to 52 "C., 570 g of oleic acid were added and the mixture was heated to about 58" C. while stirring. After _{stirring for 1/2} hour, 600 g of dimeric acid (dileinoleic acid) were added and the temperature V was _{kept at about 60 ° C. for 2} hours with uniform stirring. The end product was completely homogeneous. The following table illustrates some other examples according to the invention.

809 519/635

example
No. R. At the in +
R2 Amine
G oleic acid
G Undecylenic acid
ε Dimer acid
G 1 a Ci ₇ H ₃₅ C ₂ H ₁ H -7- 700 570 600 or 1200 2a CsiHiH CoHi H 480 570 - 600 or 1200 3a Ci ₇ H ₃₃ CoHi H 700 520 - 625 or 1250 4a Cn H ₂ , C ₂ Hi H 530 560 - 625 or 1250 5a Cf ₁ H _n CH ₂ C ₂ H, H 450 - 285 625 or 1250 6a Ci ₇ H ₃₅ C ₃ H ₀ CH ₃ CHo 758 - 285 600 or 1200 7a C ₁₇ H ₅₅ C ₂ Hi H CH ₂ 730 550 - 600 or 1200 8a C _n H ₂₃ C _:! H _(i H 590 570 - 610 or 1220

N - CHR ₂ R - C ^ ^ v

N-CH ₂

R '- NH,

As can be seen, the molar ratios are only approximate. The reason lies in the use of Commercial products with only technical purity. For example, it is in the case of the cyclic amidine practically impossible to obtain a technical product of 100% purity. This also applies to the dimer acids mentioned, and to a somewhat lesser extent also for oleic acid and undecylenic acid.

In the process described, the monocarboxylic acid tfhd was added first, then the dimeric acid. However, it is also possible to use the acids in reverse order or in a mixture. It is very likely that there will be an equilibrium when mixed with the petroleum product a, no matter how the salt was made, and also presumably an equilibrium arises in the actual production of the salt complex, regardless of the order in which they are used Components were added. It is therefore immaterial how the salt complex is produced.

Part 5

The salts or salt complexes described in the table above, for example listed, provide Products that are soluble in various hydrocarbons. These can be corrosion and oxidation inhibiting Properties are imparted when the appropriate salt is added in a relatively small amount.

Generally, the amount added to the hydrocarbon is from 5 to about 50, usually about 10 parts per million. This value applies to gasoline, which is not so much the mixture as such should be anti-corrosive and anti-rust, but rather the formation of rust on the with the gasoline during the Transport, the storage of ferrous metals coming into contact should be prevented. With others Products, such as kerosene, fuel oils, lubricating oils, the amount used is also around 5 to 50 parts per million, depending on the risk of rust in the system.

To prevent oxidation, it is often sufficient to inject the appropriate antioxidant into a pipe, through which the products are passed to a distribution tank, a pipeline and in which may contain some air or oxygen due to normal working conditions. In this Trap should not so much have corrosion and rust preventive properties as such, but rather the formation of impurities and rusting of the device in which the Passage or storage taking place should be avoided.

It has already been indicated that polyamines are used as such or certain salts prevent corrosion in an oxygen-free system. The ones described above Monocarboxylic acids have a comparatively low rust protection effect. Dimers Acids of the type described, the use of which is described in U.S. Patent 2,632,695, are well-known rust inhibitors. The invention However, salts are more effective than the dimer acids or the polyamines alone.

The salts or salt complexes described are intended to prevent corrosion, including rust protection, more effective than the individual components alone, or the individual components formed by each acid alone Salts are not as effective as the salts or formed jointly by the two acids Salt complexes. This has been proven by the usual tests and there is no doubt as to the unforeseen interaction of the individual components or the special properties the salts themselves.

The products described herein prevent corrosion particularly when oxygen is present alone or in admixture with other corrosive components. The products mentioned are therefore particularly suitable for rust protection; however, they are also effective in preventing corrosion, only part of which is caused by oxidation. The products are therefore also effective for corrosion protection in the absence of air or oxygen, that is, under anaerobic conditions, that is, under conditions in which no oxidation or rusting occurs.
The products according to the invention are particularly effective for preventing corrosion in oil and gas pipeline installations, especially if the products according to the invention are used in those flowing through

Materials are injected; also for the prevention of corrosion in refineries or oil pipeline facilities, where special anaerobic conditions prevail.

The compounds described for corrosion prevention can be used in the usual way (see e.g. USA.-Reissue-Patent

23 227, especially column 9, line 62, to column 11, line 52). The only difference is that that instead of the compound described there, a compound according to the present invention is used.

The effectiveness of some salts of polybasic polyamines or amine derivatives as rust inhibitors in various hydrocarbons, such as gasoline, '5 kerosene, fuel oil, lubricating oil, was modified after the ASTM test D 665-50 T. carried out. This test works under twice as severe conditions, how they actually occur in the pipelines; the test conditions are e.g. B. thereby It is clearer that a much larger relative amount of water is present and the test materials always are saturated with oxygen. This ASTM. Test was performed by lowering the temperature from 60 to 27 to 30 C and reducing the duration of

24 modified to 2 hours. The amount of rust on

The end of the 2-hour test period is generally a measure of the rust protection obtained.

In order to be able to compare the effectiveness of the rust protection, the following classes were set up:

Great Appearance of the specimen 1 rust free 2 Traces of rust, few stains 3 less than 5% of the surface ver rusts 4th 5 to 50% of the surface is rusted 5 50 to 99 ⁽⁾ / (i of the surface rusted 6th easier to be the whole surface covering grate 7th stronger, the whole surface be covering grate

The following table summarizes the test results obtained during the implementation of the modified ASTM.-D 665-50 T-test with distilled water. All information with regard to the classes are proven by at least five results.

additive

Concentration of
Additional 1:10 "

No addition

Dileinoleic acid

Dileinoleic acid

Cyclic amidine

Cyclic amidine

Monocarboxylic acid salt of cyclic amidine
Monocarboxylic acid salt of cyclic amidine

Salt complex of the cyclic amidine

Salt complex of the cyclic amidine

Salt complex of the cyclic amidine

Salt complex of the cyclic amidine

No addition

It is particularly pointed out that for the preparation of all described in this invention Compounds, salts, multiple salts, salt complexes and multiple salt complexes in the Patent protection is not claimed within the scope of the present invention.

55

Claims (7)

Patent claims: 1. Use of salt-like or complex reaction products of 1 mol of a polyamino compound containing at least two basic nitrogen atoms, optionally heterocyclic, which may also contain oxygen and has at least one hydrophobic group of at least eight contiguous carbon atoms, with at least 1 mol of a polycarboxylic acid which is not more than four, preferably three or four, carboxyl groups and at least one non-zero hydrocarbon radical
10
20th
10
20th
10
20th
10
20th
10
20th 0 · Hydrocarbon petrol petrol petrol petrol petrol petrol petrol petrol petrol Kerosene Kerosene Kerosene Great 3- 1 1 1 1 1 7 contains less than 8 carbon atoms excluding the carboxyl carbon atoms, optionally in a mixture with 8 to 32 carbon atoms containing monocarboxylic acids, as an inhibitor in Liquids or gases that corrode metal, especially in liquid hydrocarbons, that come into contact with ferrous metals under aerobic or anaerobic conditions. 2. Use of a reaction product of 1 mol of a polyamino compound with at least 1 mole of a polycarboxylic acid and at least 1 mole of a monocarboxylic acid as a corrosion inhibitor according to claim 1. 3. Use of a reaction product that is derived from a non-resinous polyamino compound is derived, as a corrosion inhibitor according to claims 1 and 2. 4. Use of a reaction product of a polyalkyleneamine, preferably one Polyethylene amine, is derived, as a corrosion inhibitor according to claims 1 to 3. 5. Use of a reaction product which is derived from a surface-active polyamino compound is derived, as a corrosion inhibitor according to claims 1 to 4. 6. Use of a reaction product derived from a tricarboxylic acid, the tricarboxylic acid being obtained from an unsaturated higher fatty acid, e.g. B. linseed oil fatty acid, and an a, ß-un saturated dicarboxylic acid derivative, e.g. B. maleic anhydride, as a corrosion inhibitor according to claim 1 to 5. 7. Use of a reaction product that from 1 mole of a dibasic cyclic amidine, which is preferably a five-membered ring (e.g. imidazoline) and contains about 1 mole of a monounsaturated fatty acid with 8 to 22 carbon atoms (e.g. oleic acid) and about 1 mol of a dimeric or trimeric condensate of a monounsaturated aliphatic monocarboxylic acid or oxymonocarboxylic acid having 16 to 18 carbon atoms (e.g. linseed oil fatty acid) is produced as a corrosion inhibitor according to claims 1 to 6. Considered publications:
U.S. Patent Nos. 2,599,384, 2,599,385, 622,018, 2,640,029, 2,668,100. Legacy Patents Considered: German Patent No. 958 234. 809 519/635 3. 68 © Bundesdruckerei Berlin