DD219189B1 - PROCESS FOR THE PREPARATION OF ALKYLPHENOLSULFIDES - Google Patents

Description

Field of application of the invention

The invention relates to a process for the preparation of alkylphenol sulfides which can be used as additives in high-performance lubricating oils and functional fluids, as an intermediate in the preparation of phenolate-type additives and as promoters in the production of ash-containing sulfonate additives.

Characteristic of the known state of the art

It is known to produce as a lubricant additives and used for the production of lubricant additives Alkylphenolsulfide in such a way that alkylphenols are reacted with sulfur chlorides or that alkylphenols are reacted in the presence of an alkaline catalyst with elemental sulfur at temperatures of 120 to 160 ⁰ C.

The catalysts used are usually alkali metal compounds in concentrations of 0.1 to 1 mole per mole of alkylphenol or alkaline earth metal compounds in equimolar amounts, but at least in an amount of 0.5 mole per mole of alkylphenol.

InDE-OS 1543 535 the usability of oxides, alkoxides, hydroxides or sulfides of the elements of the groups IA or II A of the Periodic Table is called; in the examples given alkali metal hydroxides are used in amounts of 0.167 to 0.170 mole per mole of alkylphenol.

According to DE-PS 10 55 006 0.5 to 0.8MoI alkaline earth metal base per mole of phenol are required in the I.Stufe as a catalyst for the reaction with elemental sulfur.

Before further use of alkylphenol sulfides prepared in this way, removal of the alkali by reaction with an equivalent amount of an inorganic compound, for example phosphoric acid, and removal of the resulting inorganic salt is necessary. In addition, even in the reaction with sulfur, small amounts of resinous by-products occur, which also have to be separated off.

When using alkyl metal compounds as a catalyst in the sulfurization of alkylphenol and waiving a treatment with phosphoric acid and filtration according to DE-OS 1543535 precipitation phenomena occur after only a few days of storage. From the point of view of practical use and intermediate storage, therefore, a purification of the alkylphenol sulfides produced is absolutely necessary.

Object of the invention

The aim of the invention is the development of a simple, inexpensive process for the preparation of Alkylphenolsulfiden, without causing solid waste products and the process step of the purification is required.

Explanation of the essence of the invention

The invention has for its object to produce alkylphenol sulfides based on oil-soluble alkylphenols and elemental sulfur under certain conditions and using a catalyst such that they are used as lubricant additives with oxidation, corrosion and wear-inhibiting properties and as intermediates in the preparation of additives from Phenolattyp and as promoters in the production of ash-containing Sulfonatadditives are suitable.

According to the invention, the process for the preparation of alkylphenol sulfides of the general formula

Place Oh

in which R is an alkyl radical of chain length C ₈ to C ₃₀ , preferably C ₉ and / or Ci ₂ , and η 0.5 to 1, by reacting corresponding alkylphenols with elemental sulfur at temperatures of 150 to 200 ⁰ C using barium hydroxide as Catalyst essentially characterized in that the catalyst is used in an amount of 0.01 to 0.1 moles per mole of alkylphenol.

The catalyst used is preferably barium hydroxide in the form of octahydrate, which is added to the alkylphenol at a temperature of from 40 to 90 ^° C. before metering in the sulfur.

The amount ratio of sulfur to alkylphenol is 0.5 to 1.0 mol of sulfur per mole of alkylphenol.

The sulfur is added at a temperature of at least 150 ^° C.

After completion of the reaction, no further process steps are required, and there are no solid by-products. The remaining catalyst in the form of the alkaline earth metal salts of the alkylphenols and sulfurized alkylphenols are oil-soluble and show no negative effects in the further use.

In the prior art, it did not seem possible to carry out the reaction of alkylphenols with elemental sulfur in the presence of less than 0.1 mole of alkaline earth metal hydroxide per mole of alkylphenol. In such a case, it would have been expected that due to the lower reactivity of alkaline earth metal compounds to alkali metal compounds, there would not be sufficient catalytic activity, that is, the reaction of alkylphenols with sulfur would be incomplete using standard temperatures or forming resinous products when used higher temperatures would expire.

Contrary to expectations, however, the inventively made use of only 0.01 to 0.1 mol barium hydroxide per mole of alkylphenol proved sufficient to achieve a complete reaction of the alkylphenols with sulfur at ordinary temperatures.

embodiments

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

example 1

In a stirred vessel 440 g (2MoI) of nonylphenol is heated to 65 ° C and treated while stirring with 6.3 g (0,02MoI) Bariumhydroxidoktahydrat. After heating to 160 ° C 32 g (1 mol) of elemental sulfur is added within 2 hunter slight nitrogen fuming and stirred for a further 4h at 18O ⁰ C. Obtained without the use of cleaning operations, a clear, reddish-brown, completely soluble in mineral oil product.

Example 2

440 g (2 mol) of nonylphenol are reacted with 15.8 g (0.05 mol) of barium hydroxide octahydrate and 48 g (1.5 mol) of sulfur analogously to Example 1.

Example 3

In a stirred vessel, 440 g (2MoI) of nonylphenol is heated to 7O ⁰ C and mixed with stirring with 31.5 g (0.1 mol) of barium hydroxide octahydrate. After heating to 170 ⁰ C elemental sulfur is added over 3 h under a slight nitrogen purge 56g (1,75MoI) and stirred for 5 h at 185 ⁰ C. Obtained without the use of cleaning operations, a clear, reddish-brown, completely soluble in mineral oil product.

Example 4

440 g (2 mol) of nonylphenol are reacted with 63 g (0.2 mol) of barium hydroxide octahydrate and 64 g (2 mol) of sulfur analogously to Example 3.

Example 5

1 mol of an alkylphenol having an average molecular weight of 350, which was prepared by alkylation of phenol with a mixture of oligomeric propene of chain length C ₁₆ and C, ₈ , with 3.2 g (0.01 mol) of barium hydroxide octahydrate and 16g (0, 5MoI) sulfur reacted analogously to Example 1.

Example 6

350 g (1 mol) of an alkylphenol as in Example 5 is reacted with 7.9 g (0.025 mol) of barium hydroxide octahydrate and 24 g (0.75 mol) of sulfur analogously to Example 1.

Example 7

350 g (1 mol) of an alkylphenol as in Example 5 is reacted with 9.5 g (0.05 mol) of barium hydroxide monohydrate and 27.2 g (0.8 mol) of sulfur analogously to Example 3.

Example 8

350 g (1 mol) of an alkylphenol as in Example 5 is reacted with 18.9 g (0.1 mol) of barium hydroxide monohydrate and 32 g (1 mol) of sulfur analogously to Example 3.

Example 9

1 mole of an alkylphenol with an average molecular weight of 460, which was obtained by alkylation of phenol with a technical mixture of chlorine paraffins of chain length C ₂ 2 to C ₃₀ , is mixed with 3.2 g (0.01 mol) of barium hydroxide octahydrate and 16 g (0, 5MoI) sulfur reacted analogously to Example 1.

Example 10

460 g (1 mol) of an alkylphenol as in Example 9 wiFd with 7.9 g (0.025 mol) Bariumhydroxidoktahydrat and 16g (0.5 mol) of sulfur analogously to Example 3 implemented.

Example 11

460 g (1 mol) of an alkylphenol as in Example 9 is reacted with 15.8 g (0.05 mol) of barium hydroxide octahydrate and 27.2 g (0.8 mol) of sulfur analogously to Example 3.

Example 12

460 g (1 mol) of an alkylphenol as in Example 9 is mixed with 31.5 g (0.1 mol) of barium hydroxide octahydrate and 32 g (1 mol) of sulfur

implemented analogously to Example 3.

A summary of analytical characteristics of the samples from the examples is given in Table 1.

Table 1

Appearance

Solubility in mineral oil

Content of sulfur

sulfated ash

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12

maroon / clear Completed 3.5 maroon / clear Completed 5.6 maroon / clear Completed 6.0 maroon / clear Completed 6.5 maroon / clear Completed 2.5 maroon / clear Completed 3.8 maroon / clear Completed 4.2 maroon / clear Completed 4.6 dark brown / clear Completed dark brown / clear Completed 2.9 dark brown / clear Completed 3.1 dark brown / clear Completed 3.4

1.0 2.4 4.7 8.7 0.7 1.6 3.1 5.9

1,2 2,4 4,6

The alkylphenol sulfides prepared according to the invention are particularly suitable as promoters in the preparation of solutions of highly basic calcium sulfonates in mineral oil and in combination with other additives for use in motor oils. Two typical use cases should clarify the possible use.

Use case A

A solution of highly basic calcium sulfonates in mineral oil is obtained as follows:

12 parts by mass in% of an alkylphenol sulfide according to the invention prepared according to Example 1,

52 parts by weight in% of a solution of a technical synthetic alkylbenzenesulfonic acid in spindle oil with a neutralization number of 25 mg KOH / g,

13 parts by mass in% methanol, 1 part by mass in% water, 7 parts by mass in% monoethanolamine and 15 parts by mass in% of a technical calcium hydroxide

are mixed intensively at 50 ° C. in a stirred vessel for 15 minutes. Thereafter, 60 l / h of carbon dioxide are introduced over a period of 55 minutes. The temperature rises to 64 ⁰ C. Then the reaction mixture is heated to 170 ⁰ C while distilling off methanol, water and partially monoethanolamine and then separated by centrifugation of oil-insoluble constituents. The obtained calcium sulfonate has a TBN of 270 mg KOH / g and a sulfate ash of 31.7 mass parts in%.

A solution of 5 wt.% Of this calcium sulfonate in a mineral oil raffinate is compared with calcium sulfonates obtained using nonylphenol and dinonylphenol as promoter.

Table 2 compares the results of the test on the Wolf strip test with and without the presence of catalytic amounts of active iron compounds. The test conditions are 12 h, 24O ⁰ C and optionally 20 ppm iron.

Table 2

Sheet metal strip test without iron points

Increase of the resin content

Sheet metal strip test with 20 ppm iron points Increasing the resin content

Calcium sulfonate using the

Alkylphenolsulfides according to the invention as a promoter 9.5 to calcium sulfonate according to DD-PS 117 247 Example 5 using nonyl and

Dinonylphenol as promoter 9.0 to 9.5

9.5 0.75

2.5 10.2

The results demonstrate the superiority of the use of calcium sulfonates using the alkylphenol sulfides promoted according to the present invention, especially when tested in the presence of catalytic amounts of active

Iron compounds.

Use case B

A commercial multigrade petrol engine oil of viscosity grade SAE 20W30 and the performance level 2 based on medium barium sulfonates, zinc dithiophosphates and VI improvers of the type of polymethacrylates and a suitable mineral base oil is by the additional use of 0.5 wt .-% in accordance with the invention according to Example 4 produced Alkylphenolsulfides significantly improved in the thermal-oxidative stability. The positive influence by adding the Alkylphenolsulfides is achieved without prior separation of the catalyst, that is without additional

Cleaning operation.

Table 3 compares the test results on the Wolf strip test.

The test conditions are 12h, 250 ⁰ C and 20ppm iron.

Table 3

Sheet metal strip test with 20 ppm iron

Points increase the resin content

Commercial multigrade engine oil Performance level 2 commercial multigrade engine oil Performance level 2 + 0.5 mass parts in% Alkylphenol sulfide according to Example 4

14.9

10.6

Claims (1)

Claim: Process for the preparation of alkylphenol sulfides of general formula _# in which R is an alkyl radical of chain length C ₈ to C ₃₀ and η 0.5 to 1, by reacting corresponding alkylphenols with elemental sulfur at temperatures of 150 to 200 ⁰ C using barium hydroxide as catalyst, characterized in that the catalyst in an amount of 0.01 to 0.1 mole per mole of alkylphenol is used.