DD270317A1 - METHOD FOR PRODUCING SULFUR LUBRICANT ADDITIVES - Google Patents

Abstract

The invention relates to a method for producing sulfur-rich lubricant additives which are particularly suitable for use in Getriebeoelen high performance classes. The process according to the invention is based on the reaction of dicyclopentadiene with sulfur in the presence of a sulphidic catalyst and is characterized essentially by the mineral oil distillates having a viscosity of from 20 to 120 mm 2 / s 1 at 40 ° C. containing not more than 25 parts by weight of aromatic hydrocarbons as solvent % are used and the reaction product is subjected to adsorptive workup. The resulting additive stock solutions have a good long-term stability and show an excellent EP-effect and an excellent corrosion behavior.

Description

Field of application of the invention

The invention relates to a process for the preparation of sulfur-rich additives which are particularly suitable for use in gear oils of high performance classes.

Characteristic of the known state of the art

Wilson and Wells describe the direct reaction of dicyciopentadiene with sulfur without solvent addition in Chem.

Rev. 34,43 (1944). Depending on the reaction temperature and the molar sulfur-diene ratio used Polysulfidgemische be obtained with different sulfur content and different consistency. However, the products are almost insoluble in mineral oils. Partially oil-soluble products are formed when the sulfurization of dicyciopentadiene, as described in DE-OS 2417864, GB-PS 1470650 and US-PS 4033982, in the presence of catalysts at reaction temperatures of 60 to 160 ⁰ C performs. The catalysts used are ammonia, amines, phenolates and thiadiazole derivatives. The sulfur content of these products is between 15 and 40%. Dia products show some very good EP effect. The disadvantage, however, is that these sulfurization products contain a large part (30 to 70%) of oil-insoluble substances.

A significant proportion of oil-insoluble products in sulfurized dicyclopentadienes, which are formed by known technical solutions in the reaction of elemental sulfur with dicyciopentadiene, is due to the presence of higher molecular weight polysulfides in the reaction products.

Also the long-term responsibility of oily solutions is insufficient. Solutions of completely oil-soluble products show clear turbidity and an undue increase in copper corrosion after a few days.

In DE-OS 2533327 and 2742359 it is therefore proposed to further react the sulfurized dicyciopentadiene with mercaptans or olefins. However, this additional process step lowers the sulfur content and leads to a greater production cost.

In WPC10M / 303 537-4 and WPC10M / 305 538-2, the sulfurization of a technical dicyclopentadiene concentrate using a sulfidic catalyst and a sulfur to diene ratio of 2: 1 to 3: 1 in solvents such as gasoline, hexane, pyridine and the like. proposed. Under these conditions, a nearly completely oil-soluble sulfurization product is obtained.

The disadvantage of this technology is the separation of the resulting in the reaction finely divided polysulfides, which can be separated only by a complex filtration. Another disadvantage is the use and separation of considerable amounts of solvents with a flash point below 100 ⁰ C and the insufficient long-term stability.

Object of the invention

The aim of the invention is the cost-effective production of oil-soluble and stable high-sulfur lubricant additives from available technical dicyclopentadiene-containing concentrates and sulfur in high yields.

Explanation of the essence of the invention

Dc: It is the object of the invention to find workup processes for the reaction of dicyclopentadiene concentrates with sulfur, which ensure a high yield of low molecular weight oil-soluble sulfurization products and complete separation of undesired reaction components and polysulfides. According to the invention, the process for producing sulfur-rich lubricant additive by reacting pure

Dicyclopentadiene and / or technical Dicyclopentadienhattigen concentrates of petroleum or Carbochernie with Dicyclopentadiene contents of f 0 to 90 parts by weight in% with sulfur in the presence of a sulfidic catalyst and

if necessary, a solvent at temperatures of 60 to 160 ⁰ C essentially characterized in that as

Solvent mineral oil distillates of viscosity from 20 to 120mmVs " ¹ at 40 ° C with an aromatic content Hydrocarbons of not more than 26% by mass in an amount of not less than 2% by weight, relative to 1 part of the substance Dicyclopentadiene, be used and the Rgaktionsptodukt an adsorptive workup is subjected. For advantageous embodiment of the method according to the invention is a Dicyclopentadienkonzentrat. that 55 to 85% Dicyclopentadiene, 5 to 15% methyldicyclopentadiene, 7 to 8% propenylnorbornene, 1 to 5% tetrahydridoinden and 0.3 b! S 3% Stabilizer contains, in one obtained by hydrorefining of mineral oils and subsequent redistillation and a Solvent refining and a dewaxing neutralized dissolved and added to the catalyst. As a catalyst for high yields are particularly suitable Alkaiisuifido. For better effectiveness of the catalyst ports solubilizers such as DMF and dioxane u. a. in an amount of 1 to 20%

be added.

Subsequently, elemental sulfur is added in portions with stirring and slowly heated to 90 to 12O ⁰ C. The sulfur / diene molar ratio is in the range from 2: 1 to 3: 1. The reaction is completed after 6 hours. After that will be

distilled unreacted Dicyclopentadienkonzontrat and the solubilizers used in vacuo at 2 to 5kPa and the residue was cooled. This is mixed with 10 to 30% adsorbent such as alumina, bleaching earth or Bauxid, stirred for 0.5 to 2 h and filtered. A clear red-brown additive stock solution is obtained.

Surprisingly, only the polysulfidic be used by the adsorbent used in the invention Impurities and not the sulfur-rich target products from the oil solution absorbed. Just as surprising is the good Long-term stability of the ÖMösungen prepared by the described method. Compared to the previously known methods, the workup simplifies considerably, since only the solubilizers

and the unreacted Dicyclopentadienkonzentrat must be removed by distillation and the filtration without special

Filter aid can be performed. The sulfurized dicyclopentadiene concentrates prepared by the process of the present invention show excellent results EP-effect in the corresponding base oils in the VKA test according to TGL 38346. Surprisingly, the evaluation of the Copper corrosion in the TGL18622 copper strip test with grade 1 a extremely low for such highly sulfurized products. embodiments The invention will be explained in more detail below on some embodiments. example 1

24g sulfur bloom (0.75mol), 50ml dicyclopentadiene concentrate (0.29mol diene, consisting of 65% dicyclopentadiene, 10% methyldicyclopentadiene, 3% propenylnorbornene, 2% methyltetrahydridoins, 3000ppm stabilizer and various aromatic hydrocarbons), 1.5g technical grade sodium sulfide (60%) ig), 17 ml of DMF, 35 ml of dioxane and 200 ml of a obtained by Hydrorafination of mineral oils and subsequent redistillation and a solvent refining and dewaxing neutral oils having a viscosity of 2Pmm ~ ² / s ~ 'at 4O ⁰ C in a three-necked flask with reflux condenser and stirrer heated to 105 ⁰ C and stirred 6h bai this temperature. Thereafter, unreacted dicyclopentadiene concentrate, DMF and dioxane are distilled off in vacuo at about 5 kPa; the residue is cooled and mixed with 60 kg of alumina. After stirring for 2 hours, it is filtered. 2l3g of a reddish-brown, clear oil solution are obtained (S = 9.12%).

Example 2

24g sulfur bloom (0.75mol), 50ml dicyclopentadiene concentrate (0.29mol diene, consisting of 65% dicyclopentadiene, 10%

Methyldicyclopentadiene, 3% Propenylnorbornene, 2% Methyltetrahydridoinden, 3000ppm stabilizer and various

aromatic hydrocarbons), 1.5g of technical sodium sulfide (60%), 17ml of DMF, 35ml of dioxane and 200ml of one

Neutral oils according to Example 1 are heated in a three-necked flask with reflux condenser and stirrer at 105 ⁰ C and 6h in this Temperature stirred. Subsequently, unreacted dicyclopentadiene concentrate, DMF and dioxane are removed in vacuo at about 4 kPa; the The residue is cooled and treated with 60 g of bleaching earth Stassfurt "A." After stirring for 2 hours, the mixture is filtered

reddish-brown, clear oil solution is obtained (S = 9.03%).

Example 3

24g sorrel flower (0.75mol), 50ml dicyclopentadiene concentrate (0.29mol diene, consisting of 65% dicyclopentadiene, 10%

Methyldicyclopentadiene, 3% propenylnorbornene, 2% methyltetrahydridoindane, 3000ppm otabilizer and various

aromatic hydrocarbons), 1.5g of technical sodium sulfide (60%), 17ml of DMF, 35ml of dioxane and 200ml of one

Neutral oils according to Example 1 are heated in a three-necked flask with reflux condenser and stirrer at 105 ⁰ C and 6h in this Temperature stirred. Subsequently, unreacted Dicyclopentadienkonzentrat, DMF and dioxane in vacuo at about

5kPa distilled off, the residue is cooled and with 60g of bleaching earth. Stassfurt "B" offset.

Stirring for two hours is filtered. A reddish-brown, clear oil solution is obtained (S = 9.04%).

Example 4

36g sulfur bloom (1.125mol), 75ml dicyclopentadiene concentrate (0.44mol diene, consisting of 65% dicyclopentadiene, 10% methyldicyclopene: adiene, 3% propenylnorbornene, 2% methyltetrahydridoindene, 3000ppm stabilizer and various aromatic hydrocarbons), 1.5g technical grade sodium sulfide ( 60%), 17 ml of DMF, 35 ml of pyridine and 200 ml of a obtained according to Example 1 treated neutral oil having a viscosity of 89mmVs ~ ¹ are in a three-necked with

Reflux and Rühier heated to 105 ⁰ C and stirred for 6 h at this temperature. Subsequently, unurngesetztes Dicyciopentadienkonzentrat, DMF and pyridine distilled off in vacuo at about 5 kPa, the residue is cooled and with 60 g Bleicherde Stassfurt "Λ" After stirring for two hours, it is filtered and 193 g of a reddish-brown, clear oilseed

received (S = 18.16%).

The gaseous solutions containing geochwefeites Dicyclopontadien prepared according to Examples 1 to 4 were to Ermiflung

their EP effect on the four-ball apparatus according to TGL 38 346 tested. Solutions with a sulfur content of 0.5% were used.

Table 1: EP effect

Test solution Welding force in N Grtindöl 1260 Product of Example 1 3760 Product of Example 2 3650 Product of Example 3 3550 Product of Example 4 3550

For a commercial brand product of specification TM 5, a welding force of 2 660 N could be determined. The corrosion behavior of the products according to Example 1 to 4 wurda tested by the copper strip test (TGL 18622). Solutions with a sulfur content of 0.5% were used.

Table 2: Corrosion behavior

Test solution rating base oil 1a Product of Example 1 1a Product of Example 2 1a Product of Example 3 1a Product of Example 4 1a

Claims (3)

1. A process for preparing sulfur-rich lubricant additives by reacting dicyciopentadiene and / or technical, dicyclopentadiene-containing concentrates of petroleum or carbochemistry with Dicyclopentadiengehalten of 60 to 90 parts by mass with sulfur in the molar ratio diene / sulfur of 1: 1 to 1: 4 in the presence of a sulfidic Catalyst and, if necessary, a Lösungsvermitücrs at temperatures of 60 to 16O ⁰ C, characterized in da ', 5 as a solvent mineral oil distillates viscosity of 20 to 120mm ² / s ~ ¹ at 40 ⁰ C with an aromatic hydrocarbon content of at most 25 parts by mass in % in an amount of at least 2 parts by weight, based on one part by mass of dicyciopentadiene, and the reaction product is subjected to adsorptive work-up. 2. The method according to claim 1, characterized in that as a solvent obtained by hydrorefining of mineral oils and subsequent redistillation and subjected to a solvent refining and a dewaxing neutral oils are used. 3. The method according to claim 1, characterized in that the Re tion product is subjected to adsorptive workup using bleaching earths, alumina or bauxite as adsorbents.