DE1443812C - Process for the manufacture of lubricating oil additives - Google Patents

Description

The present invention relates to the production of additives for lubricating oils, which are used as dispersants, Inhibitors and antioxidants work and have a high degree of alkalinity. These additives give the lubricating oils some very beneficial properties, especially at high Temperatures lead to the formation of varnish and, at low temperatures, the formation of sludge deposits impede.

It is known to produce lubricating oil additives with a high degree of alkalinity by having a basic alkali or alkaline earth compound in a solution of an alkali or alkaline earth metal sulfonate in one oil dispersed as a diluent and carbon dioxide at an elevated temperature in the presence of an accelerator passes through the solution, thereby reducing the amount of alkali or alkaline earth metal absorbed by the solution and thereby the alkalinity of the additive is increased. One such method is, for example described in French patent specification 1267 818.

The aforementioned results can now be significantly improved by the method according to the invention will.

The invention relates to a process for the production of lubricating oil additives, which is characterized is that an oil solution of an alkaline or alkaline earth metal sulfonate with a molecular weight from 450 to 500 or an alkylaryl alkali or alkaline earth metal sulfonate of molecular weight from 400 to 500 (each expressed as sodium sulfonate) and an aminoalkylphenols (5 to 85 percent by weight based on metal sulfonate) of the general formula

R - Ar (OH) - CH (R ¹ ) - NH - R ²

in which R is an alkyl radical with 2 to 24 carbon atoms, ίο Ar an aromatic radical, R ^{1 is} a hydrogen atom or an alkyl radical and R ^{2 is} an alkyl radical, or an aminoalkylphenol of the same formula, but in which R ^{2 is} a radical of the formula

_ (R3_NH) ₇₁ CH (R ¹ ) - Ar - (OH) - R

is, in which R ^{3 is} an alkylene radical and η is a number of at least 1, while passing through carbon dioxide with an oxide, hydroxide or hydrated hydro-

ao xyd of an alkali or alkaline earth metal is added with vigorous stirring, a temperature above 100 ° C. being maintained, and the reaction mixture is then filtered.
The preferred aminoalkylphenols are by

as condensation of an alkylphenol with formaldehyde and a di- or polyamine in the ratio of 2 moles of alkylphenol to 2 moles of formaldehyde and 1 mole of amine prepared, wherein an aminoalkylphenol of the formula

R - Ar (OH) - CH ₂ - NH - (R ³ - NH) _n - CH ₂ - Ar (OH) - R

is obtained. The condensation reaction which occurs in the presence or absence of an organic solvent can be carried out, is done only by having some of the reactants Heated for hours with stirring.

The metal of the metal sulfonate may be the same or different from that of the basic metal compound.

The amount of aminoalkylphenol used can preferably be 10 to 40 percent by weight based on the metal sulfonate in the starting solution.

According to an advantageous embodiment of the method according to the invention, a solution of the Metal sulfonate (neutral or slightly basic) and the aminoalkylphenols in oil while passing through Carbon dioxide mixed with the basic metal compound continuously, with one in the solution Temperature of over 100 ° C and preferably between 110 and 140 ° C is maintained. By the Introduced carbon dioxide is formed in situ a colloidal carbonate, which a complex with the Forms sulfonate. The addition takes place with vigorous stirring of the. Solution, for example by means of a Turbo stirrer can happen. The reaction product is then filtered through a filter aid.

In this way, additives are obtained whose alkalinity is above 200 and whose molar ratio is between Metal and sulfonate can range from 2-15.

The product according to the invention is used in lubricants, preferably in amounts from 0.001 to 30 percent by weight and in particular from 0.5 to 10 percent by weight, based on the lubricant, used.

example

A lubricating oil additive B according to the invention
was made as follows:

a) Production of the aminoalkylphenols

2 mol of nonylphenol (440 g), 2 mol of formaldehyde, 30% formaldehyde solution (200 g) and 1 mol of ethylenediamine with a purity of 69.5 ° / ₀ (87 g) were placed in a reaction vessel. This mixture was mixed with 20 percent by weight isopropyl alcohol, based on the total amount of the three above-mentioned ingredients. The reaction mixture was heated signings (83-84 ⁰ C) with stirring for Alkoholrückfluß. The hot product was then washed twice with 100 g of water in a decanting flask and then heated ^{to 110 ° C. in a stream of nitrogen to remove the last traces of alcohol and water.} In this case, a yield of 95 ° / ₀ Aminonpnylphenol as having the formula

C ₉ H ₁₉ - C ₆ H ₃ (OH) - CH ₂ - NH (CHj) ₈ NH - CH ₂ - C ₆ H ₃ (OH) - C ₉ H ₁₉

receive.

b) Production of the lubricating oil additive according to the invention

1 kg of a 26% solution of a synthetic calcium alkylarylsulfonate (with a Ca to sulfonate ratio of 1.4, an alkalinity of 11 and a molecular weight of 890, corresponding to 448, based on sodium sulfonate) in a mineral oil (viscosity index 103, viscosity 21, 1 cSt at 50 ⁰ C) was charged with 100 g Aminononylphenol (for additive B) and 100 g of nonylphenol (Bl additive according to the prior

technology for comparison) and then, while maintaining a temperature of 125 ° C., 550 g of barium oxide octahydrate were gradually added, with _{carbon dioxide being introduced at the same time for 2} hours at a rate of 22 ¹ I ₂ hours. The reaction mixture was filtered while hot and under vacuum through a filter aid to give products with the following properties:

B or Bl

Ba 14.2 percent by weight

Approx. 1.1 percent by weight

CO ₂ 4.62 percent by weight »5

Precipitation traces

Alkalinity 150.

10 Average specific consumption ... 200 g / PS / hour.

Power 4.87PS

Test duration 120 hours

The fuel used is gas oil

with a

Sulfur content

froml · /.

Paraffin coolant

Coolant temperature:
Inlet

Outlet

oil temperature in the oil pan

78 ³ C
85 ° C
55 ° C

After each test, the engine was disassembled and the degree of contamination after ; ao new »AnglamoU method according to the following

The products B and Bl were assessed in this way on the rating scale:
Form of solutions in oil containing
40 weight percent active product obtained.

c) Production of the ashless dispersants A 1 and A 3

For preparing a compound A1 100 parts of a polybutene having a molecular weight of 1200 for 8 hours were treated ₂ S ₅ at 22O ⁰ C with 15 parts of P. The product obtained was dissolved in 100 parts of oil.

Following a steam treatment at 160 ° C were irn C ^ course of 5 hours in the presence of 1 ° / o BF ₃ -ether complex 5 moles of ethylene oxide added per mole phosphorsulfuriertem hydrocarbon at 16O ^0th

To prepare a compound A3, 1 mole of a polybutene having a molecular weight of 900 was reacted with about 1 mole of maleic anhydride. The resulting product was dissolved in a solution of 50 ° / ₀ xylene and then added with maintaining a temperature of 150 ⁰ C gradually 1 mole of tetraethylene pentamine. The water of reaction was removed azeotropically by stripping off the xylene solvent. .

d) Application progress of the invention Lubricating oil additives.

The particularly interesting properties of lubricants with the additives according to the invention for lubricating diesel engines emerge from the results obtained in "Petter Anglamol AV-I" engine tests. These tests were carried out according to a procedure described in the Journal of the Institute of Petroleum, September 1953, as follows: Overall assessment with a positive rating of
0 to 100, consisting of the following individual ratings:

Purity level of the piston rings 0 to 35

Condition of the piston skirts after

Wash 0 to 30

Deposits on the entire parts .'... 0 to 10

Sludge deposits on the
Wiper rings 0 to 10

Scratches on the piston crown surface 0 to 5

Average condition of the piston ring surfaces 0 to 10

0 to 100

Assessment of the deposits with positive

Rating from 0 to 60, consisting of the

the following individual ratings:

Condition of the piston skirt after
Washing .. 0 to 30

Deposits on the entire parts ..... 0 to 10 deposits on the scraper rings 0 to 10

Average condition of the piston ring surfaces 0 to 10

0 to 60

Engine key figures

Drilling. 80 mm

Stroke HO mm

Displacement 550 cm ³

Nominal speed 1500 rpm

A rating of 0 means the highest degree of pollution that is to be assessed This point can occur, and the maximum rating means that a surface is free of all deposits and pollution is. In these tests, the lubricants in values given in the following table were obtained.

The importance of the lubricants with the addition of the lubricant according to the invention emerges from these results Product, especially when mixed with compounds of types A 1 and A 3.

5 Viscosity
index Used
Own »
viscosity
incSt
at 98.8 ° C lubricant
:be liable
viscosity
incSt
at 37.8 ° G density
at 15 ° C 6th Assessment of the
Deposits
(Maximum value 60) Composition < 71
72
72
71
74
74
74
73 11.1
11.2
11.2
11
11.6
10.3
10.3
11.4 130.5
131.5
131.5
128.6
137
113.6
113.6
133.3 0.87
0.92
0.92
0.89
0.92
0.91
0.91
0.94 total
evaluation
(Maximum value 100) 40
45
47.7
42
51
52
55
51 oil base (= mineral oil) alone ..
oil base + 3% Bl
oil base + 3% B
oil base + 3% Al ...
Oil base + 3 · /, A 3
oil base + 1.8% BI and 1.2%
Al 60 -
85
87
70
87
90
93.4
91 oil base + 1.8 / _β Β and 1.2%
Al oil base + 2 · /, B and 1% A 3

Note: The quantities of additives used are given in% active substance.

Claims (2)

Claims: “5 1. A process for the production of lubricating oil additives, characterized in that an ÖHösung an alkaline or alkaline earth metal sulfonate with a molecular weight of 450 to SOO or an alkylarylalkali or alkaline earth metal sulfonate with a molecular weight of 400 to 500 (each expressed as sodium sulfonate) and one Aminoalkyiphenols (S to 85 percent by weight based on metal sulfonate) of the general formula 33 R - Ar (OH) - CH (R ¹ ) - NH - R * in which R is an alkyl radical having 2 to 24 carbon atoms, Ar is an aromatic radical, R ^{1 is} a hydrogen atom or an alkyl radical and R * is an alkyl radical, or an aminoalkyl phenol of the same formula, but in which R * is a radical of the formula - (R ¹ - NH) _n CH (R ¹ ) - Ar - (OH) - R in which R * is an alkylene radical and π is a number of at least 1, an oxide, hydroxide or hydrated hydroxide of an alkali or alkaline earth metal is added with vigorous stirring while carbon dioxide is passed through, while a temperature above 100 ^° C. is maintained, and then the reaction mixture is filtered. 2. The method according to claim 1, characterized in that that 10 to 40 percent by weight, based on metal sulfonate, of the aforementioned aminoalkylphenols used.