JPS5821029B2 - Rust inhibitors and compositions - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel compounds having rust-inhibiting and/or corrosion-protecting properties and to hydrocarbon mixtures or compositions containing one or more such compounds.

The new substances are generally alkyl ammonium carboxylate salts of polycarboxylic acids having at least two carboxyl groups - ethoxylated alkylphenol esters, where the polycarboxylic acids are as described in detail below. , preferably a trimmer or a timer (or a mixture thereof).

Polycarboxylic acids are typically polymerization products of C16-0□8 unsaturated or hydroxy-substituted aliphatic C16 to C18 monocarboxylic acids, and polycarboxylic acid products contain up to 5 or more individual carboxylic acid groups. of polycarboxylic acids, but the polycarboxylic acid product itself has an average number of acid groups or acid functionality ranging from about 1.9 to 3.5, more preferably from about 2 to 3. (For pure trimer acids, the acid functionality is 3; for pure dimer acids, the acid functionality is 2).

The novel salt-ester materials of the present invention have a ratio of amine salt (or alkylammonium) functionality to ester functionality of about 1 to 4.
The ratio should range from about 4:1 to about 4:1, more preferably from about 1:2 to about 2:1.

In the case of alkylammonium carboxylate salts of trimer or dimer acids (or mixtures thereof) - ethoxylated alkylphenol esters, the product may be represented by the following general formula (1): where n is about 1 to 12 stones. , more preferably an average number from about 1 to 5; and in the case of salt-esters derived from trimer acids, X is an average number from 1 to 2, and y is an average number from 1 to 2. , the sum of X and y is 3, and in the case of a salt-ester derived from a dimer acid, both X and y each average 1 (or an average number of 1), and R4 contains from 4 to 12 carbon atoms. R5 is H or an alkyl group containing from 4 to 12 carbon atoms; R6 is an alkyl group containing from 1 to 24 carbon atoms, which may be linear or branched, or an amine-substituted alkyl group; or 24
is an alkyl group of carbon atoms.

Desirably R6 contains 12 to 22 carbon atoms; R7 is defined as the same as R6 or can be H and R8
6 or can be H; 2 is an acidic saturated or unsaturated hydrocarbon residue having about 34 to 51 carbon atoms.

Z typically has 51 carbon atoms in the case of trimer acids;
Dimer acids usually have 34 carbon atoms; the ratio of y to X ranges from about 1:2 to 2:1.

The alkylammonium carboxylate salt-ester rust inhibitor or corrosion protectant can be used as an all-trimer acid derivative or an all-dimer acid derivative, or any mixture of dimer and trimer or higher acid derivatives can be used in the present invention.

Also, the presence of some 018 monocarboxylic acids or analogs in the form of esters or salts, or mixtures of both esters and salts, may be tolerated in small amounts of about 10% or less.

In the present invention (general formula (■) above), R4 is virtually or substantially all octyl, that is, -C3H1□, R5 is H, R7 is H, and 8 is H. Certain representative examples of alkylammonium carboxylate salt-esters (which form part of this invention) are shown in Table I.

Alkylammonium carboxylate salt-esters can be produced by known methods.

Thus, a suitable dimer or trimer acid, or a mixture thereof, is acid-catalyzed esterified, for example with 2 moles of a suitable ethoxylated alkylphenol in the case of a diester-mono salt, and then the residual carboxylic acid functionality is removed with a suitable amine. by adding and converting it to an alkyl ammonium carboxylate salt.

The esterification reaction is generally carried out at a temperature in the range of about 100°C to 200°C, more preferably in the range of about 130°C to 170°C.

Concentrated H2SO4 is a typical catalyst.

Salt formation readily occurs at room temperature or higher temperatures if desired.

Trimer acids can be products derived from the trimerization of C18 unsaturated fatty acids; an example of a suitable trimer acid is Empo
It can be used under the trademark 1041.

The production of such dimer and trimer acids is described in U.S. Pat.
No. 632,695.

The general reaction scheme for the preparation of alkylammonium carboxylate salt-esters is shown below using trimer acids as an example.

Here.

, R4, R5, and R6 have the aforementioned values, and C5□ is the carbon atom content of the hydrocarbon residue.

The amines used in the preparation of the alkylammonium salt-esters may contain primary, secondary or tertiary nitrogen, the alkyl group may have a straight or branched chain, and R6 is usually about 1 to 2
4, preferably 8 to 24 carbon atoms, R
7 and R8 can be H or contain 1 to 24 carbon atoms, but are preferably H or contain 1 to 4 carbon atoms.

These amines may be represented by the general formula (■): Special embodiments include tertiary or t-alkyl primary amines with at least one branch, which facilitate the formation of salt-esters. and can be expressed by the general formula (to).

Here R1, R2 and R3 are alkyl groups whose total carbon atom content ranges from 6 to 24.

Preferably, the two R groups, eg R1 and R3 of the t-alkyl primary amine, are methyl groups.

Tert-alkyl primary amines having a branched chain and which can be used in the compositions of the invention include, for example, t-octylamine, t-nonylamine, t-dodecylamine, t-tetradecylamine, t-octadecylamine. , t-tocodylamine,
Included are t-tetradecylamine and mixtures of two or more such amines.

Such amines are commonly prepared by reactions known to those skilled in the art, such as the reaction of nitriles with alkenes or secondary or tertiary alcohols in strongly acidic media.

Commercially available t-alkyl primary amines are often mixtures.

A branched t-octylamine has the formula: and the alkyl group of this amine is hereinafter referred to as t-octyl.

One form of t-nonylamine is prepared as a mixture containing C6H13C(CHs)2NH2 and C7H15C(CH3)2NH2 and has a neutral equivalent of about 142.

General formula products useful in the present invention are trademarked Primene 8
1-R, which is t-dodecyl-1
t-t-lysosyl- and t-tetradecylamine or t-C1□H25NH2 with primarily neutral equivalent weights of about 191
to tC14H2QNH2amine.

Other common products useful in the present invention are under the trademark Primene
JM T can be used, which is mainly t-C□8
It is a mixture of H3□NH2 to t-C22H45NH2 and has a neutral equivalent weight of about 315.

An important consideration is that when t-alkyl primary amines are used, the NH2 group is always attached to a carbon atom that does not have a hydrogen atom, and that at least one of the alkyl groups is branched. It is something that should be done.

Some linear amines that can be used are butylamine, decylamine, dodecylamine, tridecylamine, tetradecylamine, hexadecylamine, octadecylamine.

Dimer and trimer acids are known substances and can be produced by known methods.

For example, unsaturated aliphatic monocarboxylic acids having from about 16 to about 18 carbon atoms per molecule, such as linoleic acid, can be polymerized or condensed to form substantially dimers of linoleic acid, dicarboxylic acids, and also aliphatic monocarboxylic acids. The acid can be polymerized to form substantially a trimer of linoleic acid, a tricarboxylic acid.

Mixtures of such dicarboxylic and tricarboxylic acids may also be formed.

Similarly, other C16s including ricinoleic acid and linoleic acid
and unsaturated aliphatic monocarboxylic acids can be polymerized to dimer and trimer acids or mixtures of such dimer and trimer acids.

The production of such dimer and trimer acids is described in U.S. Pat.
No. 632,695.

As an example of manufacturing a mono-salt, mono-tertiary C1□-C
A 14-alkylammonium salt-diester, a di(octylethoxylated phenol, containing about 3 moles of ethylene oxide) ester of trimer acid, is prepared as follows.

Example I To a 200 m2 round bottom flask equipped with a Dean -5 tark water trap, magnetic cooler and thermometer, toluene, octyl ethoxylated phenol,
Contains about 3 moles of condensed ethylene oxide, molecular weight -3
38 g, trimer acid, approximately 90% of formula C5□(CO2H)3,
A molecular weight of about 845.50.0 g and concentrated sulfuric acid 0.02 g were added.

The reaction solution was heated to reflux with a pot temperature in the range of 150-160°C.

After 3 hours 1.8 ml of water was collected (theory 2.17)
.

The reaction solution is then cooled to below 70°C at which point the t-alkylamine NH2C1214H2 with a molecular weight of about 200 is added.
5-29, 11,89 were added in 5 minutes.

When the addition is complete, the reaction solution is diluted with 1 ml to ensure homogeneity.
Stirred for an hour.

Stripped samples of seven salts and di-esters have an acid value of -
16.5; coefficient NB=0.77.

As an example of the production of G salt, namely G (tertiary C12
C14 Alkylammonium Carboxylate Salt) Mono-ester, a heptanooctyl ethoxylated phenol of trimer acid, an ester containing about 3 moles of ethylene oxide is prepared as follows.

Example 2 Toluene 50% was added to eleven 30 round bottom flasks equipped with a Dean-5tark water trap, mechanical stirring and a thermometer.
m1, trimer acid (same as described in Example 1)2
50.0 g, ethoxylated octylphenol (as described in Example 1) 100. C1 and.

0.1 g of concentrated sulfuric acid was added.

After refluxing for 2 hours at 133 °C, 5.5 g of water was collected (theory = 5.4 m).

The reaction solution is cooled to below 70°C, at which point the t-alkylamine 118. ! i' (same as described in Example 1) 11
8, O,! i' was added in 30 minutes.

When the addition was complete, the reaction solution was maintained at 70° C. for 1 hour with stirring to ensure homogeneity.

Ester/disalt was stripped by flash evaporation, acid number = 55.7, 54.5; %NB = 1.78
, 1.77 was obtained.

To demonstrate the utility of alkylammonium carboxylate salts-ethoxylated alkylphenol esters, various compounds were tested for rust and/or corrosion protection in various hydrocarbon mixtures by the following method.

The results are shown in Tables ■ and ■. It will be done.

A. Rust test method (please refer to Table ■) Rust suppression additive for suppression use in hydrocarbon fuel 1] Evaluation method is military standard MIL-I-25017C (chapters 4, 6, 3)
It is.

Using type B intermediate hard water, this method is based on ASTM method D6.
The test control, a modification of No. 65, is to evaluate the ability of gasoline additives to inhibit rust on ferrous parts such as those encountered in gasoline storage or transportation systems.

The method consists of a depolarized additive blend of 30.0 - in isooctane and deionized distilled water;
Mixture with medium hard water or artificial seawater 30-100% below (3
7,8° C.) for 5 hours with a cylindrical steel sample completely immersed therein.

Test results are reported as a percentage of rusted area and a pitting rating (p
Itting ratings) are also reported from 1 to 3 from time to time.

3 is the worst degree of pitting, and 0 is the best.

Type B medium hard water is adjusted as follows: 16.4, respectively! i' / 1NaHCO3,1
3,2g/1CaCI2・2H20 and 8.29/I
AC in distilled water containing t Mg SO4.7H20
3 stock solutions using 8 reagent grade chemicals.

10 ml of Na HCOs stock solution is pipetted into 800 ml of distilled water in 11 volumetric flasks and shaken vigorously.

While the flask contents are swirling, add CaCl2 stock solution 1
0 ml was pipetted into the flask and then added again with MgS.
10rrIl of O4 stock solution is pipetted into the flask, then distilled water is added to 11 volumes and mixed well.

The final blend should be clear and free of sediment.

The preparation of artificial seawater follows the procedures described in ASTM D665 Procedure B.

Please refer to the literature for this. B Rust Test Method (See Table ■) The method used to evaluate rust inhibiting additives for use in industrial hydrocarbon oils and hydrocarbon lubricating oils is ASTM D665.
．． 135/64.

ASTM standard annual book 17mm (11mm)
), 1972, 235-242.

Table 11. As seen in H., the new salt-esters are highly effective rust inhibitors even in very small amounts, as evidenced by the small area of rust on the samples.

Examples of hydrocarbon products in which these rust inhibitors may be used include: 1) Crude oil, 2) A4, 5, or 6 fuels, including gasoline, kerosene, K2 distillate, residual oil, and Bunker C. heating oils, 3) lubricating oils such as crankcase oils, automatic transmission fluids, thrashing compounds, turbine oils, mineral oil-based or oil-in-water and water-in-oil emulsions, cutting oils, gear oils and greases.

The rust inhibitor or corrosion protectant should be used in an effective amount to inhibit rust formation.

Usually this is a small amount and varies significantly depending on the fuel or oil in which the rust inhibitor is used.

This amount is also somewhat influenced by certain factors such as temperature conditions, humidity conditions, etc.

This is common in the surrounding environment or climate in which the fuel or oil is used, transported or stored.

Typically, the amount will be from about 0.0001% to about 5% or about 1
pI)I[l to about 50.0001)P.

More desirably this amount is about 0.0005% to 2-3
%, i.e. 5pIMIl to about 20,000 to 30,0
Changes to OOp door.

Still more desirably, the amount of rust inhibitor used in the fuel or oil will vary from a minimum of about 0.0015 to 0.0035 parts to a maximum of about 2 or 3 parts.

In the case of fuel, for example, in the case of gasoline, about 1 to 1
0001) The amount of INII is usually sufficient.

More preferably, in the case of gasoline, about 5 to ioop
pm would be sufficient.

For hydraulic and industrial fluids and general lubricating oils, this amount will normally range up to higher amounts depending on the conditions mentioned above.

Particularly in the case of cutting oil, a relatively large amount of rust inhibitor can be used. As mentioned above, the amount is about 0.0
05% to about 5%, more preferably about o, oo25%
It will vary from up to about 2 or 3%.

In the Examples, Detailed Description, and Claims, all parts and percentages are by weight unless otherwise indicated.

Claims (1)

[Claims] 1 Formula: [In the formula, n is an average number of 1 to 12.5; in the case of a salt-ester derived from a trimer acid, X is an average number of 1 to 2, and y is 1 an average number of ~2, the sum of X and y is 3, and in the case of salt-esters derived from dimer acids, X and y each have an average of 1, and the sum of X and y is 2; is an alkyl group containing from 4 to 12 carbon atoms, R6 is hydrogen or an alkyl group containing from 4 to 12 carbon atoms, and the lump is a straight-chain or branched alkyl group containing from 1 to 24 carbon atoms. or an amine-substituted alkyl group of 2-1-24 carbon atoms, R7 and A8 are both H or an alkyl group similar to R6, and 2 is an acid saturated or unsubstituted alkyl group of 34 to 51 carbon atoms; Rust inhibitor based on alkylammonium carboxylate salt of polycaribonic acid (which is a saturated hydrocarbon residue) - ethoxylated alkylphenol ester 2 Polycarboxylic acid is esterified with ethoxylated alkylphenol in the presence of an acid catalyst, and then Converted with an amine to an alkyl ammonium carboxylate salt of the formula: where n is an average number from 1 to 12.5 and in the case of a salt-ester derived from a nitrimeric acid, X is an average number from 1 to 2. , y is an average number from 1 to 2, the sum of X and y is 3, and in the case of salt-esters derived from dimer acids, X and y are each an average of 1, and the sum of X and y is 2; R4 is an alkyl group containing 4 to 12 carbon atoms; R5 is hydrogen or an alkyl group containing 4 to 12 carbon atoms; R6 is a straight alkyl group containing 1 to 24 carbon atoms; a chain or branched alkyl group, such as an amine-substituted alkyl group of 2 to 24 carbon atoms; R7 and R8 are both H or an alkyl group similar to R6; 2 is an acid of 34 to 51 carbon atoms; a saturated or unsaturated hydrocarbon residue having a saturated or unsaturated hydrocarbon residue.