HU202909B - Processs for producing promoted metallic salt mixtures of oxidized ceresine and oxidized microcrystalline paraffin - Google Patents

Abstract

Oxidised resin and microcrystalline waxes in soln. react with divalent metal or alkaline-earth-metal oxides over 115 deg.C in presence of a promoter, namely 10-20C atoms contg. carboxylic, sulphonic or naphthenic acids. The wt. ratio of oxidised resin, microcrystalline wax and promoter is (0.5-1.5):(1-3):(0.01-0.1). - The concn. of metal oxides, pref. zinc or alkaline earth oxides is 1.1-1.2 g equiv. based on the acid value of the starting materials and promoter. 0.1-1% water (later removed) is also present during reaction. The removal of the solvent used is optional.

Description

The present invention relates to a process for the preparation of promoted metal salt mixtures of oxidized ceresine and oxidized microcrystalline paraffin in the presence of promoters.

Modern paraffin-based transient preservatives today generally consist of macro- and microcrystalline paraffin, their oxidized derivatives and / or mixtures, or individual metal soaps. The advantage of oxidized products is that they are more polar than the parent compounds and therefore have better adhesion to the metal surface. This advantage is exploited by H. Koehn's solution (Galvanotechnik, 60: 689-692 (1969)). Mixtures of alkali-saponified alkali saponified mixtures of macrocrystalline and microcrystalline paraffins formed during the refining of crude oil are used as polar materials to form an anti-corrosion coating. Corrosion inhibitors are added to the base material thus obtained to increase the protective effect. Our investigations have shown that these protective agents have a tendency to slip off during use and hence their corrosion inhibiting effect is not satisfactory.

No. 158, No. 310. Hungarian Patent Specification No. 4,198,125 describes the preparation of a coating material for the protection of non-ferrous metals. According to the present invention, four different substances are used in the protective agent, including organic acid esters of trivalent or polyhydric alcohols, amines or their salts with organic acids, alkali or alkaline earth metal salts of long chain organic acids and medium molecular weight polymers of 5 to 85 units each. by weight. The protective compositions produced in this way are well adhered to the metal surface due to their polarity, but in hot weather the protective layer flows on the metal surface and the formed protective film becomes sticky. Therefore, these protective materials can only be used for temporary protection of machines or components stored indoors, and the coated items need to be packaged during transport.

No. 714,808. Hungarian Patent Application for the Corrosion Protection of Metals in a mixture of metal soaps, i.e., oxidized ceresin and oxidized petrolatum, is a periodic table Π. discloses compositions containing from 0.1: 1 to 10: 1 by weight metal salts of metals of Group II, compositions containing a solvent, a metal salt of a sulfonic acid, an organic acid salt of an amine, a polymeric additive, a surfactant and a water displacement agent. The corrosion protection and slip properties of metal soap mixtures are lower than the metal salts produced in one step from oxidized cerein, oxidized microcrystalline paraffin in the presence of a promoter.

No. 3,986,995. According to a US patent, a thermoplastic polymer, a paraffin hydrocarbon wax, calcium hydroxide and a fatty acid mixture are heated at 150 ° C. The resulting adhesion-resistant protective composition is recommended for temporary corrosion protection of metal surfaces. The protective compositions produced in this way, due to their low polarity, do not adhere sufficiently to the metal surface, crack in the cold, collapse at a higher temperature of 30-40 ° C, or partially slip off the metal surface.

No. 4,180,408. According to a US patent, it oxidizes an alpha olefin fraction or microcrystalline paraffin and then forms an amine salt, which is suitably neutralized with calcium hydroxide. The compositions produced in this way are brittle, cracked and detached from the metal surface, especially in cold weather. They do not have sufficient adhesion when warm, have a low tendency to slip off, and have poor corrosion protection.

No. 4,532,060. According to a US patent, C20-50 oxidized hydrocarbon wax (acid number 35120 mgKOH / g) is mixed with polyol compounds during heating and then salted with divalent metals. The compositions produced in this way, although of high polarity, slide off the metal surfaces. The thin protective layer remaining after draining does not provide sufficient protection against corrosion. The protective film is sticky in hot weather.

Our aim was to produce a product which, when applied, has no tendency to slip off and thus has a corrosion-inhibiting effect on the entire surface.

In our work, it has been discovered that the use of metal soaps of a defined mixture of oxidized cerezine and oxidized microcrystalline paraffin in the presence of promoters instead of a mixture of the same metal soaps produced separately, results in a much better corrosion inhibiting effect and product mixes.

In the process, the starting materials used are oxidized ceresine, oxidized microcrystalline paraffin, and aliphatic carboxylic, naphthenic and / or sulfonic acids (0.5-1.5) :( 1: 3) :( 0.01-0.1) by weight. The soaps were prepared using oxides of alkaline earth metal or other divalent metals in the presence of 0.41.0% by weight of water in a solvent medium.

The oxidized ceresin used has an acid number of 20-60 mgKOH / g, a saponification number of 60-80 mgKOH / g, a drop point of 66-76 ° C, and a molecular weight of 500-700. The oxidized microcrystalline paraffin has an acid number of 1540 mgKOH / g, a saponification number of 55-85 mg KOH / g, a drop point of 60-70 ° C and a molecular weight of 400-700. The carboxylic acid used as the promoter is a C 1020 saturated and / or unsaturated fatty acid, aliphatic, aromatic, aliphatic-aromatic sulfonic acid, naphthenic acid and / or a mixture thereof. For the production of soap, oxides of divalent metals, alkaline earth metals, preferably zinc, calcium and / or magnesium are used in an amount of 1.1-1.2 grams equivalents based on the acid number of oxidized ceresin, oxidized microcrystalline paraffin and promoter. 0% by weight in the presence of water. The solvent is an aliphatic, aromatic, aliphatic-aromatic hydrocarbon, preferably white spirit, aromatic-rich gasoline and / or a mixture thereof.

The process results in ternary compositions in which the metal salt promoter is unexpectedly significantly enhanced by the inhibitory action of the metal salt mixture of oxidized cerein and oxidized microcrystalline paraffin. The inhibitor mixture thus prepared

The anticorrosive effect of EN 202 909 Β far exceeds that of the individual derivatives.

The metal salt mixtures of the present invention are prepared by weighing the required solvent, oxidized ceresin, oxidized microcrystalline paraffin, and carboxylic, naphthenic, and / or sulfonic acid as promoters into a heated, stirred apparatus.

The apparatus is heated to a temperature of 110-120 ° C and when the base material has softened, the mixer is started. The temperature of the material is gradually raised to 140-145 ° C and, after complete dissolution, the metal oxide and water are gradually added. After each addition, a sample is taken. If the sample taken is transparent and lump-free when examined on a glass slide, the addition is continued. After addition of the last metal oxide and water portion, the material is post-reacted with stirring at 140-145 ° C for 1.5-2 hours until the water introduced and the reaction formed are removed and, after repeated sampling, are clear, lump-free. material. The resulting brine was cooled to 6070 ° C and poured into barrels.

The invention is illustrated by the following non-limiting Examples.

Example 1

A 1500 liter heated, cooled, mixed duplicator was charged with 400 kg of gasoline containing 90% aromatic hydrocarbons, 200 kg of oxidized ceresin (acid number 35 mgKOH / g, saponification number 72 mgKOH / g, drop point 70 ° C), 400 kg of oxidized microcrystalline paraffin (acid number 28 mgK0H) g, saponification number 80 mgKOH / g, drop point 65 ° C), 6 kg of stearic acid. After the apparatus was heated to 120 ° C, after complete dissolution (which took 4 hours), the stirrer was started and 7.6 kg of magnesium oxide and 4 liters of tap water were added, the latter in half liter portions. After half an hour a sample was taken and it was determined that the total amount of magnesium oxide had reacted, so the addition was continued. Once all the magnesium oxide had reacted, which took 6-7 hours, the materials were reacted at 140-145 ° C for 1.5-2 hours. (During this time, the diluent and the resulting water were completely removed.) If the repeated sample was clear and lump-free, 206 kg of white spirit was added at 120 ° C and after stirring for half an hour, the mixture was stirred at 60-70 ° C. chilled the finished product into barrels.

Weight of product: 1210 kg

Dry matter content: 50.2%

The solid has a drop point of 76'C

Fraas breaking point: -16 'C

It had a sliding tendency of 0.13% by weight at 80 ° C for one minute.

Example 2

By the procedure described in Example 1, a neutral salt mixture was prepared from the following materials:

150 kg oxidized ceresin acid number: 45 mgKOH / g saponification number: 76 mgKOH / g drop point: 72 'C

450 kg oxidized microcrystalline paraffin acid number: 40 mgKOH / g saponification number: 78 mgKOH / g drop point: 68 'C kg naphthenic acid, acid number: 172 mgKOH / g kg calcium oxide 6 liter tap water

350 kg of aromatically enriched gasoline (90% aroma content) kg of white spirit

Weight of product obtained: 1020 kg

Dry matter content: 61.4%

The solid has a drop point of 130 'C and a Frass break point of -10' C

Slip tendency at 80 ° C for minutes: 0%

Example 3

By the procedure described in Example 1, a neutral salt mixture was prepared from the following materials.

200 kg oxidized ceresin acid number: 75 mgKOH / g saponification number: 80 mgKOH / g drop point: 73 'C

600 kg oxidized microcrystalline paraffin acid number: 66 mgKOH / g saponification number: 80 mgKOH / g drop point: 70 'C kg dodecylbenzenesulfonic acid, acid number 290 mgKOH / g 33 kg zinc oxide

300 kg of aromatised gasoline (90% aroma content)

100 kg of white spirit.

Weight: 1202 kg

Dry matter content: 67%

The solids have a drop point of 96 'C

Slip tendency at 80 ° C for minutes: 0%

The product may also be prepared in the form of a melt by distilling off the solvent used at atmospheric pressure and / or vacuum.

Example 4

As described in Example 1, a composition was prepared from the following materials:

200 kg oxidized ceresin (acid number 35 mgKOH / g, saponification number 72 mgKOH / g, drop point 70 'C)

400 kg oxidized microcrystalline paraffin (acid number 28 mg KOH / g, saponification number 80 mgKOH / g, drop point 65 'C)

7.6 kg of magnesium oxide per liter of tap water

206 kg of white spirit

Thus, no promoter was used to prepare the composition.

HU 202 909 Β

Example 5 This composition thus comprises a mixture of two soaps prepared by mixing the metal with the following materials.

Positioning: Metal produced by the promoted process of the examples200 kg of oxidized cerein magnesium salt mixtures from the same basic materials

With a mixture of 400 kg of oxidized microcrystalline paraffin magnesium and the same ratio of individual metal salts, the salt gave the following results:

206 kg of white spirit

Table I

Materials Physical constants Cseppe- néspont 'C Fraas-mass RESPOND 'C come-down susceptibility m% Anti-corrosion effect, month 33% oxidized cerzine and its magnesium salt 67% oxidized microcrystalline 68 -12 5.16 24 a mixture of the magnesium salt of paraffin Example 1 76 -16 0.13 36 25% by weight of oxidized ceresin calcium salt and 75% w / w oxidized microcrystalline 105 -7 2 22 a mixture of the calcium salt of paraffin Example 2 130 -12 0 28 25% by weight of zinc salt of oxidised ceresin and 75% oxidized microcrystalline 88 -13 7 24 zinc salt mixture of paraffin Example 3 96 -19 0 32

It can be seen from Table I that the products produced by the promoted process were superior to the same ratio of individual metal salts in terms of drop point, Fraas break point, slip and anti-corrosion effect.

To further demonstrate the advanced nature of the process of the present invention, comparative studies were conducted with the product of Example 1 and the product of Example 4 of similar composition but without promoter, and otherwise of identical composition of Example 5, da involvement. The results are shown in Π. are summarized in Table.

Table U.

Cseppe- néspont, 'C Fraas-mass RESPOND, 'C come-down disposition, m% Anti-corrosion effect, month Example 1 76 - 16 0.13 36 Example 4 70 - 12 4.56 27 Example 5 68 - 12 5.16 24

The Π. It can be seen from Table 1, that the products produced by the promoted process proved to be better in terms of drop point, Frass break point, slip and anti-corrosion effect than products made from the same basic material, the same composition without the promoter, or by mixing the individual metal salts.

Claims (3)

A process for preparing promoted metal salt mixtures of oxidized microcrystalline paraffin and oxidized ceresin having an acid number of 20-80 mgKOH / g, an acidification number of 6080 mgKOH / g and a drop point of 60-76 ° C, an acid number of 20-70 mgKOH / g. , A 55-85 mgKOH / g saponification, oxidized microcrystalline raffin with a drop point of 60-70 ° C, and a C10-20 aliphatic carboxylic acid, naphthenic acid and / or C8-18 alkylbenzenesulfonic acid promoter (0.5-1, 5): (1-3) :( 0.01-0.1), by weight, at a temperature above 115 ° C, of 1.11.2 grams equivalents of the alkaline earth metal oxide or 60 zinc oxide in a hydrocarbon solvent and In the presence of water, after completion of the reaction, the water is separated in a known manner and the solvent is optionally distilled off. Process according to claim 1, characterized in that the solvent is aromatic-rich gasoline and / or white spirit containing at least 90% by weight of aromatic compounds. Process according to claim 1 or 2, characterized in that the solvent is distilled off first at atmospheric pressure and then under vacuum.