DD263788A1 - METHOD FOR PRODUCING SULFUR AND NITROGEN-CONTAINING LUBRICANT COMPOSITIONS - Google Patents

Abstract

The invention relates to a process for the preparation of sulfur-rich and nitrogen-containing lubricant additives, which are particularly suitable for use in Getriebeoelen high performance classes. The oeleal products of high long-term stability are produced directly from technical dicyclopentadiene concentrates and pyridine base slices of the boiling point 125 to 250C by sulfide-catalyzed reaction with sulfur at reaction temperatures of 60 to 160 ° C.

Description

Field of application of the invention

The invention relates to a process for the preparation of low-ash sulfur-rich and nitrogen-containing lubricant additives, which are particularly suitable for use in transmission oils of high performance classes.

Characteristic of the known state of the art

Sulfur-rich and nitrogen-containing lubricant additives form an important class of modern low-ash lubricant additives. DE-OS 2417864, GB-PS 1,470,650 and US-PS 4,033,982 describe processes for the preparation of sulfurized dicyclopentadiene under various reaction conditions. At temperatures of 60 to 160 ⁰ C and catalysts such as ammonia, amines, phenates or thiadiazole derivatives products are obtained with 15 to 40% sulfur.

The products show z.T. very good EP effect. However, it is disadvantageous that these sulfur-containing products contain a large proportion (30 to 70% / of oil-insoluble substances which are attributable to the formation of polymeric polysulfides.) This leads to unusable by-products, the separation of which makes the process more expensive.

In addition, the solutions have insufficient long-term stability, which results in a noticeable reduction in the quality of the alloyed oils, for example by an increase in copper corrosion.

In DE-OS 2533327 and 2742359 it is therefore proposed to further convert the sulfurized üicyclopentadiene with mercaptans or olefins. However, this additional process step lowers the sulfur content and leads to higher production costs.

Starting material of all previously known processes for the preparation of sulfurized dicyclopentadiene is pure dicyclopentadiene.

The technical-economic effort for tanning of dicyclopentadiene as a starting material for a technical synthesis is anyhow unacceptably high. In the petrol and Cai bochemie fall to technical Dicyciopentadienkonzentrate, which are therefore not previously considered as a starting point for the production hochgeschwefelter Schmierstoffzus.Mze into consideration.

Object of the invention

The aim of the invention is the cost-effective production of oil-soluble, nitrogen-containing and stable sulfur-rich Schmierzuszusäizen available technical dicyclopentadienhaltigen concentrates.

Explanation of the essence of invention

The invention is based on the object. To find catalysts and reaction conditions that ensure high conversion to low molecular weight oil-soluble products for the reaction of technical Dicyclopentadienkonzentrat with elemental sulfur.

According to the invention, the object is achieved by producing sulfurized dicyclopentadiene concentrate according to the method described below:

The dicyclopentadiene concentrate containing 55 to 85% dicyclopentadiene, 5 to 15% methyl dicyclopentadiene, 2 to 8% propenylnorbornene, 1 to 5% tetrahydridoindene and 0.3 to 3% stabilizer is used in a technical pyridine based millbase carbocation Dissolved 125 to 23O ⁰ C and treated with the catalyst. When using the low-boiling ι Pyridinbasenschnitte (bp. 125 to 145 ⁰ C) are especially suitable as a catalyst for high yields of alkali metal and / or Alkyiammoniumsulfide the chain length C ₁ to C ₁₅ . Since in the higher boiling Pyridinbasenst cut in small

Amines are present in their use, the catalyst is generated by introducing hydrogen sulfide during the reaction.

Subsequently, elemental sulfur is added in portions with stirring and the solution is heated to 60 to 16O ⁰ C, preferably 30 to 140 ° C. The molar sulfur to diene ratio should be in the range from 1: 1 to 1: 5, preferably 1: 2 to 1: 4. The reaction is completed after 1 to 8 hours, depending on the reaction temperature used.

It is then filtered, and the unreacted Dicyclopentadienkonzentrat and the pyridine bases are distilled off in a water-jet vacuum. A red-brown oily substance is obtained which contains both sulfurized dicyclopentadiene concentrate and sulfurized pyridine bases and is completely oil-soluble.

The products prepared by the process according to the invention show an excellent EP activity (VKA test according to TGL 38346). Surprisingly, the evaluation of copper corrosion (copper strip test according to TGL 18622) with grades of 1 to 2 for such hochgeschwefelte products is very low.

embodiments

The invention will be explained in more detail below on some embodiments.

example 1

40g sulfur blossom (1.25mol), 115ml techn. Dicyclopentadiene concentrate (0.60 moles of diene consisting of 65% dicyclopentadiene, 10% methyldicyclopentadiene, 3% propenylnorbornene, 2% methyltetrahydridoindene, 3000ppm stabilizer and various aromatic hydrocarbons), 2g sodium sulfide, 30ml DMF, and 550ml picoling mixture are placed in a three necked flask. slowly heated to 11O ⁰ C and 6 h stirring at this oeratur Ten. Then unumgesotztes dicyclopentadiene concentrate and picolines are removed in a water jet vacuum. Brückstand is taken up with petrol (bp 100 to 14O ⁰ C), shaken in a separating funnel with distilled water and the organic phase dried with CaCl ₂ . After back-distillation of the gasoline, 145 g (106% of theory based on the diene content of the dicyclopentadiene concentrate and trithiane formation) of a red-brown oil are obtained (S: 33.4%, N: 0.5%).

example

40g sulfur blossom (1.25mol), 115ml techn. Dicyclopentadiene concentrate (0.60 moles of diene consisting of 65% of cyclopentadiene, 10% of methyldicyclopentadiene, 3% of propenyinorbornene, 2% of methyltetrahydriodoindine, 3000 ppm of stabilizato and various aromatic hydrocarbons), 2 g of sodium sulfide, 3 mM of DMF and 550 ml of picolene mixture are dissolved in cooked in a three-necked flask for 6h at reflux. The work-up is carried out analogously to Example 1.

169.5 g (123% of theory based on the diene content of the concentrate and trithiane formation) of a red-brown oil can be isolated (S: 31.9%, N: 0.6%).

Example 3

40 g of sulfur bloom (1.25 mol), 100 ml technical Üicyclopentadierikonzentrat (0.5 mol diene /, 200ml pyridine base cut (bp 145 to 180 ⁰ C) are slowly heated in a three-necked flask at 107 to 110 "C, and at the same time hydrogen sulfide in a weak stream .. After 2.5 hours, the reaction solution passed v / ith the Reakticnsma ^r se cooled and filtered Working up is carried out analogously to example 1. There are a 144,6g rotbraunon uid viscous oil-soluble product obtained (S: 27.8%; N: 1 , 2%).

Example 4

40g sulfur bloom (1.25mol), 100ml technical Dicyclopentadienkonzentrat ₍ 0,5mol Diene), 200ml Pyridinbasenschnitt (bp 190 to 23O ⁰ C) are slowly in a three-necked flask to 115 to 12O ⁰ C e: heated and at the same time hydrogen sulfide in a weak stream passed the reaction solution. After 2 hours, the reaction mass is cooled and filtered. The work-up is carried out analogously to Example 1. 183.6 g of a red-viscous viscous and oil-soluble product are obtained (S: 27.4%, N: 1.6%).

The sulfurized Dicyclrpentadienkonkonate prepared according to aen Examples 1 to 4 were used to determine their EP effect on the Vierkugelappara ·. tested according to TGL 38346. Ef, 5% solutions were used.

Test solution VerschweiP.Kraft (in N) base oil 1260 Product according to Example 1 5000 Product according to Example 2 447c Product according to Example 3 4 ^ / 0 Product according to Example 4 .470

For a commercial brand product of the specification TM 5, which was dissolved to 6% in the base oil, a welding force of 3350N could be determined. The corrosive behavior of the products according to Examples 1 to 4 was tested according to the dom copper strip test (TGL 18622). 3% oily solutions of the products in the base oil were used at a test temperature of 120 ° C.

Additive rating

Product according to Example 1 1 c

Product according to Example 2 2 a

Product according to Example 3 2 b

Product according to Example 4 2 b

Claims (5)

1. A process for the preparation of sulfur-rich and nitrogen-containing lubricant additives by conversion of dicyclopentadiene with sulfur in the presence of a sulfidic catalyst in organic solvents at temperatures of 60 to 16O ⁰ C, characterized in that technical dicyclopentadiene-containing concentrates of petroleum or carbochemistry with a diene content of 70 to 80% with elemental sulfur in the molar ratio diene / sulfur of 1: 1 to 1: 5 using alkali metal and / or alkylammonium sulfides as catalyst and technical pyridine base distillates of the boiling point of 125 to 23O ⁰ C, both as a solvent and as Reaction component act, be implemented. 2. The method according to claim 1, characterized in that technical Dicyclopentadienkonzenirate be used which contain 55 to 85% dicyclopentadiene, 5 to 15% methyldicyclopentadienes, 2 to 8% Propenylnorbornen, 1 to 5% Methyltetrahydridoinden and 0.3 to 3% stabilizer. 3. The method according to claim 1 and 2, characterized in that the molar ratio diene / sulfur 1: 2 to 1: 4. 4. The method according to claim 1, characterized gekehnzeichnet that the sulfide catalyst can be added both in substance and can be generated by introducing hydrogen sulfide in the reaction solution. 5. The method according to claim 1, characterized in that the technical Pyridinbasendestillate of carbochemistry for the most part contain alkyl-substituted pyridines.