JPH05239484A - Lubricant composition containing alkaline earth metal salt - Google Patents

Abstract

PURPOSE: To provide a lubricant composition preventing formation of carbonaceous material, etc., within an engine by adding specific calcium and magnesium hydroxyalkylsulfonates.

CONSTITUTION: This lubricant composition comprises a lubricating oil, a main composition, and a small amount of an alkaline earth metal salt selected from a calcium or a magnesium salt of hydroxyalkylsulfonic acid shown by the formula. In the formula, each R¹, R², R³, and R⁴ independently represents a hydrogen, or a linear or branched alkyl with a condition that the total of these carbon atoms is within a range of 8-30. As the salt of the acid to be used and shown by the formula, calcium is preferable. And, it is preferable that at least one of R¹ or R², and at least one of R³ or R⁴ represents alkyl group. As a lubricating base oil to be applied, a mineral or a synthetic hydrocarbon lubricating oil is preferable, but an ester lubricating base oil or a vegetable oil is also applicable.

COPYRIGHT: (C)1993,JPO

Description

Detailed Description of the Invention

[0001]

This invention relates to lubricating oil compositions and concentrates containing alkaline earth metal salts selected from calcium and magnesium hydroxyalkyl sulfonates.
It relates to a method of making said composition and to the use of said sulfonate as a detergent additive in a lubricating oil composition.

[0002]

The use of alkaline earth metal salts of organic sulfonic acids as additives for lubricating oil compositions is well known. These salts have detergent properties and, when applied to such lubricating oil compositions, keep the inside of the engine cylinder clean and prevent the deposition of carbonaceous products on the piston and in the piston groove, thus It is possible to prevent the ring from adhering.

The basicity (or overbased (ove) of such acids is
It is also well known to produce rbased)) alkaline earth metal salts. Overbased stores alkalinity,
When incorporated into a lubricating oil composition, it reacts with and neutralizes the acidic compounds that are formed during the operation of the engine using the composition. That is, the sludge that is produced remains dispersed due to the detergent properties of the salt, and the acids that enhance sludge and rust formation are neutralized.

US Pat. No. 3,704,105 describes about 1
A sulfonated olefin derivative obtained by sulfonation of a mixture of acyclic monoolefins having 4 to about 30 carbon atoms is mixed with a C ₁ -C ₅ alkanol and a small amount of water to give a sulfonated olefin derivative. A stoichiometric excess of inorganic barium compound, such as barium oxide, barium hydroxide, and barium hydroxide hydrate (eg, barium hydroxide monohydrate) in a hydrocarbon medium, is reacted to form a mixture. To a temperature of about 35 ° C. to about 150 ° C. and introducing a stream of sulfur dioxide or carbon dioxide into the heated mixture until the mixture is acidic.
A method of making an overbased barium olefin-derived sulfonate is disclosed. The product obtained by this method is
It is useful as a smoke reducing fraction fuel additive.

European Patent Application Publication No. 351 928
The internal olefin having 8 to 26 carbon atoms in the liquid film reactor has a molar ratio of 1.1 to
Reacting with a sulfonating agent of 1.25: 1 while cooling the reactor by cooling means which keeps the temperature not exceeding 35 ° C.,
A process for the preparation of internal olefin sulfonates is disclosed which then comprises neutralizing and hydrolyzing the reaction products of the sulfonation step. The hydrolysis can be carried out using an alkali (earth) metal hydroxide, carbonate or bicarbonate. However, there is no mention in EP-A-351 928 of the use of the product obtained by the process.

US Pat. No. 3,896,057 discloses water soluble salts or acids of alkene sulfonates and hydroxyalkyl sulfonates containing from about 10 to about 24 carbon atoms per molecule. Sulfonates have properties that make them useful as cleaning and laundry active compositions.

US Pat. No. 3,883,583 has substantially 32 to 40 carbon atoms and has the general formula:

[0008]

[Chemical 2]

[Wherein R ′, R ″ and R ′ ″ are not all hydrogen, and the total number of carbon atoms of R, R ′, R ″ and R ″ ′ is 30 to 38. R is within the range of
It is a saturated alkyl group having either a straight chain structure or a branched chain structure, and R ′, R ″ and R ′ ″ each have hydrogen or either a straight chain structure or a branched chain structure. A saturated alkyl group], a high molecular weight oil-soluble anionic surfactant comprising one or more compounds selected from the group consisting of sulfonic acids, sulfonates (salts) of aliphatic monoolefins represented by Is disclosed. The disclosed surfactants have excellent lubricating properties,
It is said to have corrosion resistance, emulsifying action, and hydrating action required for dry cleaning detergents.

Surprisingly, certain calcium and magnesium hydroxyalkyl sulfonates have been found to be extremely effective as detergent additives in lubricating oils.

The present invention comprises a main component lubricating oil and a small amount of the general formula (I):

[0012]

[Chemical 3]

[In the formula, each of R ¹ , R ² , R ³ and R ⁴ independently has the total number of carbon atoms of 8 to 30, preferably 12 to 22, and particularly 13 to 17] Which represents hydrogen or a linear or branched alkyl group] and an alkaline earth metal salt selected from the calcium and magnesium salts of hydroxyalkyl sulfonic acids.

The preferred salt is the calcium salt.

It is preferable that at least one of R ¹ and R ² represents an alkyl group, and at least one of R ³ and R ⁴ represents an alkyl group.

The calcium and magnesium salts used in the present invention may be neutral salts, that is, those containing stoichiometrically equivalent amounts of the metal moiety and the sulfonate moiety, or may be overbased salts as described below. You can also Overbased salts are preferred.

The lubricant base oil present in the composition of the present invention is preferably a mineral or synthetic hydrocarbon base oil, but ester base oils and vegetable oils may also be used. The composition can also include a mixture of lubricating base oils. An example of such a mixture is a mixture of mineral lubricating oils, such as a mixture of lubricating oil fractions and lubricating oil bottoms. Other examples of such mixtures include mixtures of mineral lubricating oils and synthetic hydrocarbon lubricating oils. Examples of suitable synthetic hydrocarbon lubricating oils include polyolefins such as polyisobutylene. Preferably, the lubricating base oil component of the composition of the present invention is a mineral lubricating oil or a mixture of mineral lubricating oils. The viscosity of the lubricating base oil present in the lubricating oil composition can vary over a wide range, but is generally 3 to 35 mm at 100 ° C.
² / s.

In the preparation of the calcium and magnesium hydroxyalkyl sulfonates used in the present invention, C ₁₀ -C ₃₂ , preferably C ₁₄ -C ₂₄ , especially C ₁₅ -C.
For example, ₁₉ olefins may be prepared according to European Patent Application No. 351 92
Sulfonate using a sulfonating agent as described in No. 8. The sulfonation is preferably carried out with sulfur trioxide in a liquid membrane reactor. Preferred is a falling film reactor.

The β-sultone thus produced is converted to its neutral salt by reacting with magnesium or preferably a calcium compound in water according to any known method. For example, if the sulfonation is carried out in a liquid membrane reactor, the reaction mixture containing β-sultone is led from the liquid membrane reactor to a hydrolysis / neutralization unit where calcium or magnesium hydroxide and / or Alternatively, it can be mixed with an aqueous suspension of an oxide to obtain the neutral calcium or magnesium salt of the hydroxyalkyl sulfonic acid of formula I above. The neutral salt is then purified according to the usual known methods and, if desired, mixed with further calcium or magnesium hydroxide and / or oxide, an accelerator and a small amount of water in an organic solvent, to obtain the It is converted to the overbased salt by passing carbon dioxide through the mixture. In the present invention, an overbased salt means a calcium or magnesium salt (AS) of a hydroxyalkyl sulfonic acid of the above formula I.
The basicity (ba) defined as the equivalent ratio of total calcium or magnesium (as determined by ASTM D874-82) to (as determined by TMD2896).
(sicity index, BI) refers to a salt greater than 1. A detailed description of the overbasing process is given in numerous patent specifications, for example in British Patent No. 786167.

The organic solvent is conveniently a hydrocarbon, for example an aromatic hydrocarbon or an aromatic-rich hydrocarbon fraction (eg gasoline), with compounds such as benzene, toluene or especially xylene being preferred.

The promoter can be, for example, a C ₁ -C ₃ alcohol, preferably methanol. The amount of water used is conveniently 1 mole per equivalent of calcium or magnesium hydroxyalkyl sulfonate.

In the lubricating oil composition of the present invention, the total amount of calcium and / or magnesium hydroxyalkyl sulfonate is, for example, 0.1 based on the total composition.
It can vary in the range from -20% by weight, preferably 0.1-10% by weight, in particular 0.2-5% by weight.

The invention further provides an alkaline earth metal salt selected from the calcium and magnesium salts of the hydroxyalkyl sulfonic acids of formula I above in amounts of 10 to 80% by weight, based on the lubricating oil and the concentrate as a whole. Lubricating oil concentrates including and are also provided. Such concentrates generally include the lubricating oil as a solvent / diluent and one or more concentrate form additives.

The present invention further comprises a lubricating base oil, which has the formula I above.
There is also provided a method of preparing a lubricating oil composition comprising admixing with an alkaline earth metal salt selected from the calcium and magnesium salts of hydroxyalkyl sulfonic acids of or the lubricating oil concentrate of the present invention.

As will be appreciated by those skilled in the art, the lubricating oil composition of the present invention comprises antioxidants, antiwear agents, friction modifiers, foam suppressants, anticorrosive agents, viscosity index improvers, pour point depressants. Numerous other additives can be included.

If desired, the lubricating oil composition further comprises an alkaline earth metal alkyl salicylate and / or an alkylphenate, and / or a C _15-40 alkyl orthoxylene sulfonate, and / or a C _15-40 alkylbenzene. It may also include a sulfonate.

The invention further provides a lubricating oil composition containing a high proportion of lubricating oil, in an amount of at least 0.1% by weight, based on the total composition, of a calcium salt of a hydroxyalkyl sulfonic acid of the above formula I and Also provided is the use of an alkaline earth metal salt selected from magnesium salts as a detergent additive.

[0028]

EXAMPLES The invention will be further understood by the following examples.

Example (A) Neutral calcium β-hydroxyalkylsulfone
It was derived from the over door of production "SHELL" higher olefins process,
The sulfonation of a mixture of C ₁₅ -C ₁₉ internal olefins with an average molecular weight of 230 was carried out in a continuous falling film reactor with a diameter of 2.54 cm and a length of 6 m.

Sulfur trioxide was prepared by reacting sulfur dioxide with oxygen (dry air) at about 450 ° C. under vanadium pentoxide catalyst.

The C ₁₅ -C ₁₉ internal olefin was allowed to flow downwards as a film-like stream along the inner portion of the reactor wall to react with sulfur trioxide (sulfur trioxide / olefin molar ratio 1.06). And). The reactor was cooled by flowing cold water along the outside of the reaction tube so that the temperature of the reaction mixture did not exceed 35 ° C. The reaction mixture is then combined with a calcium hydroxide-water slurry (1.45 equivalents of calcium hydroxide with respect to sulfur trioxide), continuous hydrolysis / equation with a pump / high speed shear mixer combination and two heat exchangers. Feed to the neutralization loop. The resulting mixture was thoroughly mixed by a pump / high speed shear mixer at 35-40 ° C, then introduced into an open container equipped with stirring means and filled with a mixture of water and calcium hydroxide. Temperature 35-40 ℃
After being placed in an open vessel for about 40 minutes, the mixture is introduced into a layered tubular hydrolysis reactor where it is heated to 170-170 for about 30 minutes.
Heated to 190 ° C.

Once cooled to room temperature (20 ° C.), the mixture was analyzed and then purified using conventional, known methods. Analysis of the mixture showed that it contained 24% by weight of neutral calcium β-hydroxyalkyl sulfonate (measured according to ISO 2271).

(B) Preparation of overbased sulfonate 420 g of the neutral calcium β-hydroxyalkyl sulfonate (CaHAS) prepared in (A) and 1900 g of xylene were placed in a 3 liter glass reactor and Ca
Heat at 50 ° C. with stirring until all the HAS is dissolved. Then 129 g of calcium hydroxide was added to the reaction mixture, another 21 g of water and 390.7 g of methanol (9
7%) was added. 23.31 g carbon dioxide was slowly added to the stirred reaction mixture over 20 minutes while maintaining the reaction temperature at 50 ° C. The reaction mixture is kept stirring for another 5 minutes and then 2 times to remove excess calcium hydroxide.
It was centrifuged at 300 rpm for 2 hours. Two liquid layers were obtained by centrifugation, the thin upper layer containing mainly methanol and the main lower layer containing xylene and overbased CaHAS. The lower layer is isolated and 1796 g of "HVI 60"
Base oil (viscosity of 4.4 to 4.9 mm ² / s at 100 ° C. (A
STM D445) and minimum flash point 200 ° C (ASTM
D92) with a clear, transparent high viscosity base oil). Xylene and residual methanol were removed from the oil mixture by rotary evaporation at 130 ° C. and 10 Pa pressure, and 56.6 m as measured by ASTM D2896.
Total alkalinity of g KOH / g (Tatal Basi
(City Number, TBN) and a basicity (BI) of 3.0, overbased C in "HVI 60" base oil.
A clear solution containing aHAS was obtained.

(C) Highly over base
23.0 g of neutral calcium β-hydroxyalkyl sulfonate (CaHAS) prepared in (A) and xylene 1
05.7g was put into a 500ml glass reactor and Ca
Heat at 50 ° C. with stirring until all the HAS is dissolved. Then 22.16 g of calcium hydroxide was added to the reaction mixture, followed by 1.16 g of water and 21.9 g of methanol (97%). Carbon dioxide was slowly added to the stirred reaction mixture at a rate of 0.064 liters / minute over 84 minutes while maintaining the reaction temperature at 50 ° C. 2300 reaction mixture to remove excess calcium hydroxide
It was centrifuged at rpm for 2 hours. Two liquid layers were obtained by centrifugation, the thin upper layer containing mainly methanol and the main lower layer containing xylene and overbased CaHAS.
The lower layer was isolated and mixed with 66.3 g of "HVI 60" base oil. Xylene and residual methanol were removed from the oil mixture by rotary evaporation at 130 ° C. and 10 Pa pressure, overbased CaHAS in “HVI 60” base oil with a TBN of 252.9 mg KOH / g and a BI of 9.2. A clear solution containing was obtained.

(D) Caterpillar with engine test performance of 252 hours
In a 1K piston clean test, the effect of overbased calcium β-hydroxyalkyl sulfonates on the formation of carbonaceous and lacquer deposits in diesel engines was evaluated. Caterpillar 1K is a diesel engine test that measures the effect of oil on oil consumption and piston deposits, American Petroleu.
m Institute (API) CF-4 lubricating oil specifications. In this test, a single cylinder supercharged engine was tested according to ASTM Research Report RR: D.
Operate for 252 hours according to 02-1273.

Piston cleanliness was evaluated for all grooves and lands and overall weighted demerits based on carbon and lacquer deposits below crown and pin cavity areas,% heavy carbon on crown lands and% carbon in top grooves. did.

To demonstrate the diesel detergency of this component, the overbased sulfonate product according to (B) above in "HVI 60" base oil (9.4 wt% sulfonate detergent).
A general-purpose engine oil formulation (SAE) containing a VI (viscosity index) improver, a zinc-based antiwear additive and a dispersant.
15W40 grade) was mixed in an amount to give 2.26% by weight of sulfonate detergent as active substance, and the performance of the resulting oil was evaluated. The results obtained are shown in Table I below.

Products according to Table I (B) Total Weighted Disadvantages 219 Topland Heavy Carbon (%) 0 Top Groove Clogging (%) 3 Net Oil Consumption (g / kWh) 0.251.

(E) Engine Test Performance The overbased sulfonate product according to (B) above was treated with VI
It was mixed in a base oil containing an additive package consisting of a (viscosity index) improver, a zinc-based antiwear additive and a polymethacrylate pour point depressant in an amount to give 1.34% by weight as active substance. The performance of the obtained oil is shown in Sequence 5.
EAST M ("Sequence 5 Etest P
", 7th Draft, May 19, 1988; ASTM Monitoring Center,
4400 5th Avenue, Pittsburg
h, described in USA). Sequence 5E test is a gasoline engine test required for API SG lubricant specifications,
p-go) 2.3 liter Ford 4 operated in a cyclic operating process designed to simulate operating conditions
It tests the ability of oil to control sludge and varnish deposits and valve mechanism wear in cylinder gasoline engines. The results obtained are shown in Table II below.

Table II Engine Test Products AES RCS AEV PSV B 9.34 9.32 7.42 7.10 AES = Average Engine Sludge RCS = Rocker Cover Sludge AEV = Average Engine Varnish PSV = Piston Skirt Varnish Scale 0- Represented by 10, 10 indicates no sludge or varnish.

Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI Technical indication location C10N 10:04 30:04 40:25 (72) Inventor Cristinus Cornelis Juan de Kamp Dutch country, 1031・ S.M.Amsterdam, Badhaisueich 3 (72) Inventor Rudolf Ricardo Juan Well, Netherlands, 1031.S.A.M.Amsterdam, Badhaisueich 3 (72) Invention Inventor Minne Boerens Netherlands, 1031 Sem Amsterdam, Badhaisueich 3 (72) Inventor Johann Stapelsma Netherlands, 1031 Sem Amsterdam, Badhaisueich 3

Claims (10)

[Claims] 1. A main component lubricating oil and a small amount of general formula (I): [Wherein each of R ¹ , R ² , R ³ and R ⁴ is independently hydrogen or a linear or branched alkyl group, provided that the total number of carbon atoms thereof is in the range of 8 to 30. A group] and an alkaline earth metal salt selected from calcium and magnesium salts of hydroxyalkyl sulfonic acid. 2. The composition according to claim 1, wherein the salt is a calcium salt. 3. The composition according to claim 1, wherein the salt is an overbased salt. 4. The composition according to claim ¹ , wherein the total number of carbon atoms in R ¹ , R ² , R ³ and R ^{4 is} in the range of 12 to 22. 5. The composition according to claim ^4, wherein the total number of carbon atoms in R ¹ , R ² , R ³ and R ^{4 is} in the range of 13 to 17. 6. The composition according to claim 1, wherein at least one of R ¹ and R ² represents an alkyl group, and at least one of R ³ and R ⁴ represents an alkyl group. 7. An alkaline earth metal alkylsalicyate and / or alkylphenate, and / or a C _15-40 alkyl orthoxylene sulfonate, and / or
_{Alternatively,} the composition according to any one of claims 1 to 6, which comprises C _15-40 alkylbenzene sulfonate. 8. An alkaline earth metal salt selected from the calcium and magnesium salts of hydroxyalkyl sulfonic acids of formula I according to any one of claims 1 to 7, based on the total concentrate. A lubricating oil concentrate comprising in an amount of 10 to 80% by weight. 9. A lubricating base oil comprising an alkaline earth metal salt selected from the calcium and magnesium salts of hydroxyalkyl sulfonic acids of formula I according to claim 1 or claim 8. A method of making a lubricating oil composition comprising mixing with the concentrate of claim 1. 10. In a lubricating oil composition based on lubricating oil, the formula I according to claim 1, in an amount of at least 0.1% by weight, based on the total composition. Use of an alkaline earth metal salt selected from the calcium and magnesium salts of hydroxyalkyl sulfonic acids as a detergent additive.