RU2201432C2 - Motor oil additive and motor oil containing thereof - Google Patents

Abstract

FIELD: lubricants. SUBSTANCE: additive contains, wt %: calcium sulfonate, 15-50; sulfurized C9- C12-alkylphenolate calcium salt with alkalinity 140-250 mg KOH/g, 20-50; sulfurized C9-C12-alkylphenol, 5-15; and product of consecutive treatment of mixture of isopropyl and n-butyl alcohols taken in molar ratio 1:(0.7-8.0) with phosphorus pentasulfide and zinc oxide, 10-20. Additive can also contain calcium sulfonate with alkalinity 12-31mg KOH/g and mineral oil as diluent up to 15%. Mineral- and/or synthetic-origin motor oil for internal combustion engines may contain 3-10 wt % of aforesaid additive and may further contain ashless dispersant, thickening agent, depressant, and antifoaming agent. EFFECT: improved antioxidant and anticoking properties of additive and increased service time of oil and overhaul period. 5 cl, 2 tbl, 17 ex

Description

 The invention relates to the refining and automotive industries, in particular, to the composition of the additive to motor oils and motor oil containing it, intended for use in internal combustion engines.

 Known motor oil based on petroleum oil containing polyalkylene succinimide polyamine, metal dithiophosphate, alkaline earth metal alkyl phenolate, sulphide calcium alkyl phenolate (UK patent 1360981, C 10 M 1/46, 1974).

 Famous oil has a low washing properties.

 For example, an additive to motor oils is known, which contains zinc alkyl aryl dithiophosphate, calcium alkyl aryl sulfonate, calcium alkyl salicylate with various alkalinity, bisuccinimide, polyisobutylene and antifoam (A.S. Czechoslovakia 236333, C 10 M 1/14, 1988).

 A motor oil containing this additive based on a mixture of hydrogenated fractions and selective refined raffins is also described there.

 However, the well-known additive oil does not have sufficiently high antioxidant properties.

 The closest technical solution to the claimed is an additive to motor oils, including a salt of dithiophosphoric acid esters, calcium sulfonate, sulphide alkyl- (C9-C12) calcium phenolate with an alkalinity of 140-250 mg KOH / g and sulphide alkyl (C9-C12) phenol, moreover, as a salt of dithiophosphoric acid esters, the additive contains a sequential treatment product of alkyl (C8-C12) phenol with five-sulfur phosphorus, zinc oxide and an aliphatic amine containing 3-5 nitrogen atoms (RF patent 2102441, C 10 M 141/10, 1998) .

 With the development of motor industry, requirements for motor oils are increasing and the additive of a known composition does not provide the required level of antioxidant properties and thermal stability.

 The objective of the invention is the development of additives to motor oils with higher thermal stability and better antioxidant properties, as well as the development of motor oils containing this additive.

To solve this problem, an additive to motor oils is proposed, containing in wt.%:
Calcium Sulphonate - 15-50
Sulfurized alkyl (C9-C12) -phenolate of calcium with an alkalinity of 140-150 mg KOH / g - 20-50
Sulfur alkyl (C9-C12) phenol - 5-15
The product of sequential processing of a mixture of isopropyl and n. butyl alcohols taken in a molar ratio of 1: 0.7-8.0, five-sulfur phosphorus and zinc oxide - 10-20
Moreover, the additive contains calcium sulfonate with an alkalinity of 120-310 mg KOH / g and may additionally contain a mineral oil diluent in an amount of up to 15 wt.%.

 A motor oil based on mineral and / or synthetic oil is also provided containing the above additive in an amount of 3-10 wt.%. The proposed oil may also contain ashless dispersant, thickening, depressant and antifoam additives.

 The novelty of the claimed technical solution is the use of sequential processing of a mixture of isopropyl and n as part of the product additive. butyl alcohols taken in the stated ratio, pentasulfide phosphorus and zinc oxide.

 The introduction of additives in the amount of 3-10 wt.% In mineral and / or synthetic oil allows you to get a motor oil with improved antioxidant properties and greater thermal stability. The result obtained is unexpected, since it is known that the zinc salts of dithiophosphoric acid esters obtained from a mixture of lower alcohols containing secondary alcohols are less thermostable compared to the zinc salts of dithiophosphoric acid obtained from higher molecular weight alcohols, as well as compared to zinc salts dithiophosphoric acid derived from alkyl phenol.

 The use of the proposed oil in internal combustion engines will increase the oil change period and the overhaul distance of the engine.

 The following is a description of the components used in the composition of the proposed additives.

 Calcium sulfonate is a calcium salt of petroleum sulfonic acids or alkylbenzenesulfonic acids containing a dispersion of calcium carbonate. Calcium sulfonate has an alkalinity of 120-310 mg KOH / g, contains 4.8-12 wt.% Calcium and 28-40 wt.% The active substance.

 Sulfurized calcium alkyl phenolate is the product of the interaction of alkyl (C9-C12) phenol, elemental sulfur, vicinal glycol and calcium oxide (hydroxide), followed by treatment of the reaction mixture with carbon dioxide. The interaction product has an alkalinity of 140-250 mg KOH / g, contains 5.0-9.0 wt.% Calcium and 3.0-5.0 wt.% Sulfur.

 Sulfurized alkyl phenol is the product of the interaction of alkyl (C9-C12) phenol with sulfur in the presence of glycol and calcium oxide (hydroxide). The interaction product contains 8-12 wt.% Sulfur.

 An example of the preparation of a product of sequential processing of a mixture of isopropyl and n-butyl alcohols with pentasulfide phosphorus and zinc oxide.

148 g (2 mol) of N. butanol and 30 g (0.5 mol) of isopropyl alcohol are mixed and 111 g (0.5 mol) of pentasulfur phosphorus are added to the prepared mixture at a temperature of 40-50 ^{° C.} over 30 minutes. It is stirred for 1 hour at 60 ^° C. After cooling and filtration, a mixture of dithiophosphoric esters is obtained. 25 g of mineral oil I-20A are added to this mixture, and 102 g (1.25 mol) of zinc oxide are added over 1 hour at 60-65 ^{° C.} The mixture is stirred for 30 minutes at 65 ^° C. The reaction water is distilled off in vacuo at 70 ^° C. After purification by centrifugation at 60-70 ^{° C.} , a finished product is obtained having a pH of 5.7. Found%: zinc - 9.5, phosphorus - 9.0.

Mineral oil diluent is a distillate oil fraction having a viscosity in the range of 4-10 mm / s and a flash point not lower than 160 ^o C.

The proposed additive is prepared by mixing the above components at a temperature of 40-100 ^o With constant stirring. The prepared additive is introduced into the base oil at a temperature of 20-100 ^o C.

 As the base oil can be used distillate, residual oil fractions or mixtures thereof, as well as synthetic oil, for example, alkyl aromatics, polyalphaolefins, esters of dibasic acids, etc., as well as mixtures of mineral and synthetic components.

 The proposed engine oil may contain: an ashless dispersant, for example, alkenyl succinimide polyethylene polyamine or a high molecular weight Mannich base, a thickening additive - polymethacrylate or hydrogenated styrene-butadiene or isoprene copolymer, a depressant additive - polymethacrylate or chloromethylene phenol polyethylphenol and alkynyl phenol polyethanol antifoam additives.

 Table 1 shows the compositions of the samples of the proposed additive (examples 1-5), as well as samples for comparison, in which the dithiophosphoric acid ester salt was used according to the prototype additive (example 6) and the zinc salt of dithiophosphoric acid obtained from a mixture of primary (isooctyl and isobutyl) alcohols taken in a ratio of 1: 1.7 - additive DF-11 (example 7).

 In the table. 2 shows the compositions of the samples of the proposed engine oil containing the additive according to examples 1-5 (examples 7-15), and also for comparison, the sample containing the additive according to example 6 (example 16) and the additive according to example 7 (example 17).

When preparing samples of motor oil, the following oils were used as a base oil: a distillate oil fraction having a kinematic viscosity at 100 ^° C of 7.4 mm / s, a viscosity index of 94, and pour point of minus 15 ^° C (examples 7 through 13, as well as 16 and 17), synthetic - polyalphaolefin oil having a viscosity of 8.5 mm / s at 100 ^o C (example 14), semi-synthetic, representing a mixture of the above mineral and polyalphaolefin oils (example 15).

In examples 1, 2, 4, 5, the proposed additive contains a mineral oil diluent - a distillate oil fraction having a viscosity of 4.8 mm / s at 100 ^o C and a flash point of 170 ^o C.

 Samples of motor oil were tested by the following laboratory methods to evaluate their thermal stability and antioxidant properties.

The method of assessing thermal stability is that the oil is subjected to heat treatment at 240 ^o C for 10 min, while its optical density increases due to contamination with products of thermal degradation. An indicator of thermal stability is the optical density of the oil sample after heat treatment, expressed in arbitrary units. A smaller value of this indicator corresponds to a higher thermal stability. The accuracy of the method is 0.01 srvc.

The antioxidant and antinagar properties were evaluated by laboratory methods under conditions of thermocatalytic oxidation at a temperature of 23 ^o C. The assessment was carried out by the change in optical density and the increase in viscosity as a result of 3-hour oxidation.

 The methods described above allow with a sufficient degree of reliability to predict the effectiveness of motor oils in the process of engine operation.

 From the test results presented in table. 2, it follows that the engine oil with the proposed additive has the best anoxidizing and anti-stick properties and thermal stability.

 The use of the proposed additive in the form of a package in the composition of motor oils will increase the oil change period and the overhaul mileage.

Claims (4)

1. Additive to motor oils, including a salt of dithiophosphoric acid esters, calcium sulfonate, sulphide alkyl (C9-C12) calcium phenolate with an alkalinity of 140-250 mg KOH / g and sulphide alkyl (C9-C12) phenol, characterized in that as a salt of dithiophosphoric acid esters it contains the product of sequential processing of a mixture of isopropyl and n. butyl alcohols taken in a molar ratio of 1: 0.7-8.0, five-sulfur phosphorus and zinc oxide in the following ratio of components, wt. %:
Calcium Sulphonate - 15-50
Sulfurized alkyl (C9-C12) calcium phenolate - 20-50
Sulfur alkyl (C9-C12) phenol - 5-15
The product of sequential processing of a mixture of isopropyl and n. butyl alcohols taken in a molar ratio of 1: 0.7-8.0, five-sulfur phosphorus and zinc oxide - 10-20
2. The additive according to claim 1, characterized in that it contains calcium sulfonate with an alkalinity of 120-310 mg KOH / g.  3. The additive according to paragraphs. 1 and 2, characterized in that it further comprises a mineral diluent oil in an amount of up to 15 wt. %  4. Motor oil based on mineral and / or synthetic oil and additives, characterized in that it contains 3-10 wt. % additives for PP. 1-3.  5. Motor oil according to claim 4, characterized in that it further comprises an ashless dispersant, thickening, depressant and antifoam additives.

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