HU199551B - Process for production of derivatives of multifunctional anticorrosion amin and amid - Google Patents

Abstract

Multi-functional corrosion inhibiting amine or amide derivs. are prepd. by dissolving in water at 100 deg.C max. 1-2 pts.wt. of alkali-sulphonates (300-700 average mol.wt.) 0.5-1 pt.wt. ceresine and 1-2 pt.wt. micro-crystalline wax (400-700 mol.wt.). Stoichiometric quantities of amines or alcohol-amines are added, based on acid values. This mixt. is converted at 80-100 deg.C to a complex salt by adding tannic or phosphoric acids and/or converted at 140-160 deg.C to acid amides. Two phases formed by the foregoing prepn. are sepd. Excess water is distilled off and the remainder is opt. diluted by a hydrocarbon solvent.

Description

FIELD OF THE INVENTION This invention relates to a process for the preparation of complex salts and acid amides of sulfonic acid mixtures with amines and amino alcohols having anticorrosive and anticorrosive properties. 5

Related literature discloses the preparation of basic alkali and alkaline earth metal salts of protective compositions, such as metal soaps of oxidized macro- and microcrystalline paraffins, as well as ammonium salts of sulfonic acids including petroleum sulfonic acids. According to H. Kochn (Galvanotechnik 60, 689-692 (1969)), mixtures of partially macerated and partially oxidized macro- and microcrystalline paraffins formed during the refining of crude oil and polished with alkali are used as polarizing agents. Corrosion inhibitors are added to the base material thus produced to increase the protective effect. Nos. 2,966,458 and 3,048,607. U.S. Pat. Sehter Jn. N. and Tyetyerina L.N. (Nefthererabotka Neftehimija 9, 17-20, 1971) disclose a process for reacting alkylarylsulfonic acids with urea or succinimide and examining the polarity and corrosion inhibitory effect of the sulfonic acid amides formed.

The additives thus obtained, or mixtures thereof, do not provide a perfect protective effect when mixed with the base material and therefore additional corrosion inhibitors are added to the composition.

Our aim was to provide an anticorrosive additive which had an effect far superior to that of the additives or additive mixtures disclosed in the literature, and furthermore had anticorrosive properties.

In our work, it was found that when the alkali metal salts of sulfonic acids formed by sulfuric, oleic or sulfur trioxide ⁴⁵ refining of the alkali metal salts of petroleum sulfonic acids or petroleum oils, pre-melted oxidized ceresin and oxidized microcrystalline paraffin were added to the hot aqueous solution. and from the resulting mixture to form a sample salt or an acid amide with tannic acid or phosphoric acid above a stoichiometric amount, a better and more durable corrosion inhibiting effect than the protective agents known and used hitherto. In addition to its anticorrosive properties, the product thus obtained has anti-corrosive properties.

It relates to a process for inhibiting corrosion and rust converters ⁶⁰ complex salts or acid amide derivatives of the invention. The process according to the invention is carried out as follows: Sulfuric, oleum or sulfuric trioxide refining of alkali metal salts of petroleum sulfonic acids and / or petroleum oils with an average molecular weight of 300-700, 40-60 mg KOH / g acid. not more than

50-100 parts by weight of a solution having an molecular weight of 400-700 with an acid number of 20-60 mg KOH / g,

60-80 mg KOH / g with a saponification number and oxidized ceresin having a drop point of 65-80 ° C (and 100-200 parts by weight with a 400-700 molecular weight, 15-40 mg KOH / g acid number, 55-1 mg KOH / g saponification number) , 60-1

Oxidized microcrystalline paraffin with a drop point of 70 ° C, followed by a

a chiometric amount of an amine compound, namely a C 5 -C 16 aliphatic amine, dicyclohexylamine, mono-, di- or triethanolamine, or amino-aniline optionally substituted on the nitrogen atom by a C 1 -C 4 alkyl moiety, is added to the —Combined with 15 parts by weight of tannic acid and / or phosphoric acid at 80-100 ° C to form a complex salt.

or at 140-160 ° C to convert it to the acid amide, the two phases formed during the reaction are separated, the remaining water is distilled off and the product is optionally diluted with an aliphatic or aliphatic-aromatic hydrocarbon solvent or a mixture thereof. .

In the reaction, the tannin and gallic acid used to form the complex salt or acid amide are characterized by a high solubility in 1 part by weight of water or 2 parts by weight of alcohol and a solution of ferric chloride. forming a bluish-black bitch. The required phosphoric acid} i

65-85% by weight in aqueous solution. |

Products of the invention?

multifunctional additives admixed with base material and protective corners;

in addition to their anticorrosive properties, they also have a rust converter {(property. Rustproof- <!

their curing effect is that IJ converts the rust on the metal surface to ferric phosphate or ferric tannate, thereby passivating the metal surface. The protective layer formed;

They also inhibit the aggressiveness of Ί bacteria that cause corrosion. - j *

Ü

Preferably, the process according to the invention is carried out as follows:

alkaline metal salt, with stirring, in an amount of 1,5 to 6 times I (preferably 3 times) hot | dissolved in water. In another dish, | Melting the required amount of oxidized ceresin 1 and oxidized microcrystalline paraffin, adding the melt to a hot aqueous solution of the sulfonic acid alkali metal salt, and adding to the resulting hot suspension 1 an equivalent amount of the amino acid S of the components. The required amount of tannic acid and / or phosphoric acid is then added and the reaction mixture is maintained at 80-100 ° C to form comp-2HU 199551 51 lex salt and the reaction mixture is maintained at 140-160 ° C to form the acid amide. The two phases were separated and the water in the organic phase was evaporated under reduced pressure. If desired, the product thus obtained is diluted with aliphatic and / or aliphatic-aromatic hydrocarbon solvents.

The invention is further illustrated by the following non-limiting examples.

Example 1

200 g of sodium sulphosapear obtained from a 500 molar sulfonic acid mixture of 50 mg KOH / g acid by means of oleic refining of petroleum jelly were dissolved in 400 ml of boiling water and mixed with 100 g of oxidized ceresin melted in another vessel: 28 mg KOH / g, saponification number 60 mg KOH / g, drop point 76 ° C) and 200 g oxidized microcrystalline paraffin (average molecular weight 400, acid number 35 mg KOH / g, saponification number 72 mg KOH / g, drop point 61 ° C) ). Subsequently, 13.6 g of dicyclohexylamine were added to the suspension. The material was heated to 90-100 ° C and then 11 g of 75% w / w aqueous phosphoric acid was added slowly. The material was then post-reacted with stirring at the above temperature for 2 hours. When the material reacted perfectly, the aqueous portion was drained and the remaining water was removed by vacuum distillation. The product, which was cooled to 40-50 ° C, was then diluted with a mixture of 70 g of aromatic gasoline and 30 g of white spirit.

Example 2

As described in Example 1, an anticorrosive anticorrosive composition was prepared from the following components, except that after removal of water, the acid amide formation reaction was conducted at 150-160 ° C for 2 hours:

Potassium salt of a petroleum sulphonic acid mixture of sulfur trioxide with an average molecular weight of 200 g400, 53 mg KOH / g

300 g water

Oxidized cerezine having an average molecular weight of 100 g450, an acid number of 32 mg KOH / g, a saponification of 68 mg KOH / g and a drop point of 72 ° C

Oxidized microcrystalline paraffin with an average molecular weight of 200 g, an acid number of 17 mg KOH / g, an acidification number of 55 mg KOH / g and a drop point of 70 ° C

11.2 g of normal octylamine 16.0 g of tannic acid

Example 3

As described in Example 1, an anticorrosive corrosion inhibitor composition was prepared from the following components:

200 g300 average molecular weight, 57 mg

Sodium salt of petroleum sulphonic acids of acidic acid KOH / g

400 g water

100 g oxidized cerezine having an average molecular weight of 700, an acid number of 21 mg KOH / g, an acidification number of 62 mg KOH / g and a drop point of 76 ° C.

200 g500 average molecular weight 32 mg

Oxidized microcrystalline paraffin with KOH / g acid number, 78 mg KOH / g saponification, drop point 66 ° C

14.5 g of triethanolamine 9.0 g of phosphoric acid (75% by weight) g of aromatic gasoline 30 g of white spirit

Example 4

As described in Example 1, an anticorrosive corrosion inhibitor composition was prepared from the following components:

200 g of sodium salt of sulfonic acid obtained by sulfuric acid refining of petroleum jelly with an average molecular weight of 680 and having an acid number of 40 mg KOH / g

400 g water

Oxidized cerezine, 100 g, average molecular weight 550, 50 mg KOH / g acid number, 72 mg KOH / g saponification, 73 ° C drop point

200 g of oxidized microcrystalline paraffin having an average molecular weight of 500, 37 mg KOH / g acid number, 82 mg KOH / g saponification with a drop point of 63 ° C.

12.1 g of p-amino-N ', N'-diethylaniline 6.0 g of phosphoric acid (75% by weight)

5.0 g tannic acid g Aromatic gasoline 30 g White spirit

Example 5

As described in Example 1, a rust conversion composition was prepared from the following components:

200 g300 average molecular weight, 57 mg

Sodium salt of petroleum sulphonic acids of acidic acid KOH / g

400 g water

100 g oxidized cerezine of average molecular weight 700, 21 mg KOH / g acid, 62 mg KOH / g saponification, drop point 76 ° C

200 g500 average molecular weight 32 mg

Oxidized microcrystalline paraffin with KOH / g acid number, 78 mg KOH / g saponification, drop point 66 ° C

5.9 g of monoethanolamine

9.0 g of phosphoric acid (75% by weight) g of aromatic gasoline g of white spirit

-3HU 199551 Β

Example 6

As described in Example 1, an anticorrosive corrosion inhibitor composition was prepared from the following components:

200 g of sodium salt of petroleum sulphonic acids of average molecular weight 300, 57 mg of KOH / g, obtained from the oleum process

400 g water

Oxidized cerezine having an average molecular weight of 100 g700, an acid number of 21 mg KOH / g, an acidification number of 62 mg KOH / g and a drop point of 76 ° C

Oxidized microcrystalline paraffin with 200 g of average molecular weight 500, 32 mg KOH / g acid number, 78 mg KOH / g saponification, 66 ° C drop point

10.2 g of diethanolamine 9.0 g of phosphoric acid (75% by weight) g of aromatic gasoline 30 g of white spirit

Example 7

As described in Example 1, a rust conversion composition was prepared from the following components:

Sodium salt of sulphonic acid, obtained by sulfuric acid refining of petroleum jelly, with an average molecular weight of 100 g680, 40 mg KOH / g

Sodium salt of petroleum sulphonic acids, obtained by the oleum process, having an average molecular weight of 100 g300 and an acid number of 57 mg KOH / g

400 g water

Oxidized cerezine, 100 g, average molecular weight 550, 50 mg KOH / g acid number, 72 mg KOH / g saponification, 73 ° C drop point

Oxidized microcrystalline paraffin with 200 g of average molecular weight 500, 37 mg KOH / g acid number, 82 mg KOH / g saponification, 63 ° C drop point

7.8 g of p-phenylene diamine

6.0 g of phosphoric acid (75% by weight)

5.0 g tannic acid 70 g aromatised gasoline 30 g white spirit

Example 8

As described in Example 1, an anticorrosive corrosion inhibitor composition was prepared from the following components:

200 g of sodium salt of sulphonic acid obtained by oleic refining of petroleum jelly, with a molecular weight of 500, of a molecular weight of 50 mg KOH / g

400 g water

Having a mean molecular weight of 100 g600, 28 mg

Oxidized Ceresin with KOH / g acid number, 60 mg KOH / g, saponification, drop point 76 ° C

Oxidized microcrystalline paraffin with an average molecular weight of 200 g400, 35 mg KOH / g acid, 72 mg KOH / g saponification with a drop point of 61 ° C

13.6 g of dodecylamine g of phosphoric acid (75% by weight) g of aromatic gasoline 30 g of white spirit

Example 9

The activity of the anticorrosive and rust converting agents of the present invention was compared with that of two commercially available formulations (Tectyl 400 D, manufactured by Valvoline, and Olvikor 350 NL, manufactured by the Tisza Petroleum Company). Both known formulations contained sulfonic acid derivatives (sulfonic acid metal salts and sulfonic acid amides) as anticorrosive components. The results of the tests are reported in Table I below.

Based on the results shown in Table I, the anticorrosive properties of the compounds of the present invention are superior to those of Tectyl 400 D and they have the advantage of having a rust-modifying property compared to Olvikor 350 NL.

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Claims (1)

A process for the preparation of anticorrosive and rust-converting complex amine salts or acid amide derivatives comprising alkali metal or sulfuric acid derivatives of alkali metal salts of sulfuric acid, oleum or sulfur of alkali metal salts of petroleum sulfonic acids with an average molecular weight of 300 to 700 mg KOH / g With an aqueous solution of alkali metal salts of sulfonic acids having an average molecular weight of 300-700, KOH / g of 40-60 mg at a temperature not exceeding 100 ° C, with stirring, a petroleum-containing product containing microcrystalline paraffin, followed by stoichiometric amine and Aliphatic amines having 5 to 16 carbon atoms, dicyclohexylamine or mono, di- or triethanolamine or aminoanilines optionally substituted on one or more C 1 -C 4 alkyl groups are added to the mixture at a concentration of 4 to 15 parts by weight based on the sulphonic acid alkali metal salt. acidic reacting with a substance which may be phosphoric acid, separating the two phases formed by the reaction and distilling off the remaining water, characterized in that the petroleum product is 50-100 parts by weight of 20-60 mg KOH / g of acid having a molecular weight of 400-700, 60-80 mg KOH / g with a saponification number and oxidized ceresin having a drop point of 65-80 ° C and 100-200 parts by weight of a 400-700 molecular weight, 15-40 mg KOH / g acid number, 55-85 mg KOH / g with a saponification number, 60-70 ° C, oxidized microcrystalline paraffin with a drop point, tannic acid and / or phosphoric acid as the acidic material, reaction at 81-100 ° C to produce a complex salt or 140-160 ° C to produce an acid amide, and optionally the product is aliphatic or aliphatic. diluted with an aromatic hydrocarbon solvent or mixture thereof.