DD219792A5 - ASH-FREE DETERGENZ DISPERSANT ADDITIVES AND THEIR PREPARATION - Google Patents

Abstract

An ashless additive for motor oil contains 50% by weight of polybuthenylmonosuccinimide and 50% by weight of polybutenyl bis-succinimide in paraffin olefins. The free NH 2 groups of the monosuccinimide are blocked by a reaction with maleic acid. The preparation process is characterized in that maleic anhydride is treated with a chlorinated polyisobutene having a chlorine content of 4 to 6% by weight and a molecular weight of 750 to 2,000 at a molar ratio between maleic anhydride and the equivalent in grams of chlorine of 1.1: 1.2 The mixture of polybutenylsuccinic anhydride and unreacted maleic acid is condensed with a polyalkylenepolyamine at a molar ratio between polybutenylsuccinic anhydride, polyamine and maleic acid of 1: 0.7: 0.1 at 70 to 90 for 10 hours at 200 ° C in paraffins or an aromatic solvent C condenses and finally the reaction product Entwaessert. The result is an additive that gives the oil good dispersing properties at low temperatures.

Description

Ashless detergent and dispersant-containing additive and method of making the same Field of application of the invention

The invention relates to an ashless detergenz- and dispersant-containing additive for improving the quality of engine oil and a process for the production thereof.

Characteristic of the known technical solutions

The ashless additives of the above kind are widely used as an additive for engine oils for the purpose of improving their dispersing properties. >

Low temperature dispersant additives are known which contain as components succinimides obtained by condensation of melamine acids with low molecular weight polyolefins and subsequent condensation of the polyalkylene succinic anhydrides thus obtained with polyalkylene polyamines. In some ramparts, it has been found that such succinimide-type additives also have some negative effects, namely, increased corrosion of copper lead layers or deterioration of detergency at higher temperatures. To overcome these errors, various methods have been developed, which have generally focused on blocking the free HN ₂ groups of the additives by various reactions, for example reactions with aldehydes, monocarboxylic acids, phosphorothioic acids, etc. These reactions are carried out with polyamines either before imidization or after the imidization reaction performed. However, these processes mean an additional reaction phase, and in some cases also additional purification phases, which considerably complicate the production process and lower the efficiency. , ·

Object of the invention.

With the invention, the disadvantages described are to be eliminated.

Explanation of the essence of the invention

According to the invention, the additive consists of a mixture of about 50 wt .-% polybutenyl monosuccinimide with about 50 wt .-% polybutenyl bis-succinimide in paraffin oil having a viscosity of 3 to 5 ° E / 50 ° C, wherein about 20% of the free ions of Polybuthenylmonosuccinimides were blocked by a maleic acid reaction.

The process for the preparation of the additive is characterized by reacting maleic anhydride with a chlorinated polyisobutene having a chlorine content of 4 to 6% by weight and a molecular weight of 750 to 2000 at a molar ratio between maleic anhydride and equivalent in grams of chlorine of 1.1: 1 , 2 brings for 10 hours at 200 ⁰ C in paraffin oil for condensation, then the mixture of polybutenylsuccinic anhydride and unreacted maleic acid with a Poiyalkylenpolyamin at a molar ratio between polybutenyl succinic anhydride, polyamine and maleic acid in paraffin oil brings to condensation and finally the resulting reaction product at 130 to 150 ⁹ C drained. Instead of paraffin oil, a suitable other aromatic solvent may also be used.

embodiment

Based on two examples, the invention will be explained in more detail below.

Example 1 .

In a reactor with a mechanical stirrer, a thermometer, a heating mantle and a reflux condenser 1000 g polyisobutene with a molecular weight of 950 are introduced, this is chlorinated at a temperature of 100 ° C by passing gaseous chlorine (time 4 to 5 hours). The chlorine flow is 0.02 kg of chlorine / polyisobuthen and hour. After completion of the reaction phase, a treatment with nitrogen to remove traces of chloric acid is carried out to give a chlorinated polyisobuthene containing 4.7% by weight of chlorine.

The product obtained is condensed with maleic anhydride at a molar ratio of 1.1 moles of maleic acid per equivalent of grams of chlorine, this means for the amount used 150 g of anhydride. The condensation reaction takes place at a temperature of 200 ° C within a period of 10 hours, it is monitored by the escape of hydrochloric acid. The crude product thus obtained has an acid index of about 120 mg KOH / g, an organically bound chlorine content of 0.4 wt .-% and a content of unreacted maleic anhydride of 2Gew .-%.

The product is subjected by heating under vacuum at a temperature of 200 ⁰ C a Strippreaktion until the content of unreacted maleic anhydride to a content of 1 wt .-% and the acid value decreased to 110 mg / KOH / g. The product obtained after the stripping reaction is diluted with 1160 g of paraffinic mineral oil having a viscosity of 3-5 ° E / 50 ° C and cooled to a temperature of 60 ⁰ C. At this temperature, 136 g of tetramethylenepentamine are metered into the reactor. When dosing the polyamine, do not exceed the temperature of 80 ° C, possibly with water. After the metering of the polyamine, the temperature is gradually increased to 15O ⁰ C, initially at atmospheric pressure and later in vacuo to remove the water from the

Imidization. After completion of the imidization reaction, the product is diluted in a weight ratio of 1: 1 with an extraction gasoline of fraction 80-110 ⁰ C and then filtered or centrifuged. As a result, mechanical impurities are removed. Thereafter, it is distilled for the purpose of recovering the gasoline. The product is a mixture of about 50% mono- and 50% bis-polybutenyl succinimide in which about 20% of the free. _NH ₂ groups of the polybutenyl monosuccinimide were partially blocked by the reaction with maleic anhydride. The product has a nitrogen content of 1.9% by weight and a basicity index (TBN) of about 30 mg KOH / g.

Example 2 ^/

In a reactor similar to the reactor used in Example 1, 1000 g of polybutenylsuccinic anhydride prepared by the method described above are introduced. This has a content of 1 wt .-% unreacted maleic anhydride. The product is diluted with 500 g of xylene and heated to 60 ⁰ C. Thereafter, 63 g of diethylenetriamine are introduced into the reactor. The temperature must not exceed 80 ° C. After the introduction of the polyamine, the reaction mixture is heated to reflux and the water (azeotrope of water-xylene) is eliminated.

After completion of the imidization process, the product is diluted with 1050 g of paraffin oil having a viscosity of 3-5 ° E / 50 ° C, and the xylene recovered by distillation, initially at atmospheric pressure and in the

Final phase under vacuum. -.

The product obtained has a nitrogen content of 1.1% by weight and a basicity index (TBN) of 15 mg KOH / g.

The products obtained in Examples 1 and 2 were blended on SAE 30 paraffinic oil containing 1% by weight of dialkyldithiophosphate antioxidant additive with 3Gew% of alkylaryl calcium sulfonate surfactant additive superbasic with an iBN of 250 mg KOH / g and 2% by weight. % Dispersant additive of the above examples

tested. , ,

The results in engines are given in the following table:. ;

Formulation · Note by Peter ₍ - Detergent Approaches

withAddition MotorWi. note Peter on Fiat

Viscosity ^v Corrosion AV-i Filters »

increase in stock "' _t _ 600D,

mg / 63 cycles

1% AO ^X + 3% D ^XX 35 18 97 95 1% AO ^X + 3% D ^XX + 2% S ₁ * 34 ^ 17 98 12 ' 1% AO ^X + 3% D ^XX + 2% S ₂ 37 20 97 25

It means:

AO ^X : Antioxidant additives, ^J '

D ": superbasic detergent additive,

S ₁ X: dispersant additive according to Example 1,

S ₂ × x: Dispersant additive according to Example 2.

From the data given above, it can be seen that the additives obtained according to Examples 1 and 2 can be used with good results to achieve the dispersing properties of oils without adversely affecting the detergent properties or stability upon oxidation. .. ·· The new additive and its manufacturing process have the following advantages:

The additive makes it possible to improve the dispersing properties of motor oil without adversely affecting the stability during oxidation and detergency. /

The process allows easy preparation of the succinimide dispersant with a small number of reaction phases, thereby ensuring high yields.

Claims (3)

Invention claims: An ashless detergent and dispersant-containing additive, in particular for improving the quality of motor oil, characterized in that it consists of a mixture of about 50 wt .-% polybutenyl monosuccinimide with about 50 wt .-% polybutenyl bis-succinimide in paraffin oil with a viscosity of 3 to 5 ° E / 50 ° C, wherein about 20% of the free NH ₂ groups of the polybuthenyl monosuccinimide were blocked by a reaction with maleic acid. 2. A process for the preparation of the additive according to item 1, characterized by reacting maleic anhydride with a chlorinated polyisobutene having a chlorine content of 4 to 6Gew .-% and a molecular weight of 750 to 2000 at a molar ratio between maleic anhydride and equivalent in grams of chlorine , 1: 1.2 TO hours in paraffin oil at 200 ⁰ C for condensation, then the mixture of polybuthenylsuccinic anhydride and unreacted maleic acid with a polyalkylenepolyamine at a molar ratio between * polybutenylsuccinic anhydride, polyamine and maleic acid of 1: 0.7: 0, 1 at 70 to 90 ° C in paraffin oil brings to condensation and finally the resulting reaction product is dehydrated at 130 to 150 ⁰ C. 3. The method according to item 2, characterized by using an aromatic solvent instead of paraffin oil.