DE1245526B - Lubricating oil additive - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. CL:

ClOm

C 1OM 169/00 B42

German KL: 23 c -1/01

Number: 1245 526

File number: E 21595IV c / 23 c

Filing date: August 29, 1961

Opened on: July 27, 1967

To reduce or avoid deposits in the operation of internal combustion engines It has long been customary to add metal-free additives to lubricating oils.

So is from the German patent specification 1 053 125 and the corresponding French patent specification 1137 043 already known a lubricating oil mixture, which as additives on the one hand a with phosphorus sulfide and an alkylene oxide with 2 to 6 carbon atoms reacted hydrocarbon, in particular a polyisobutylene, and on the other hand a copolymer of an unsaturated ester and a contains alkoxylated partial ester of an unsaturated dicarboxylic acid. Although these lubricating oil mixtures already lead to a significant reduction in dirt accumulation is due to the ever increasing Requirements for the quality of lubricants further improve the cleaning effect urgently desired.

It has now been found, surprisingly, that lubricating oils have an even greater reduction in dirt deposits have if they are a mixture of additives

a) a phosphorus sulphurized and reacted with an alkylene oxide with 2 to 6 carbon atoms Hydrocarbon, especially a polyisobutylene with a molecular weight between 800 and 1600, and

b) a copolymer

a vinyl ester of a monocarboxylic acid with 2 to 6 carbon atoms,

an anhydride or half-ester of an oc, jö-unsaturated dicarboxylic acid and
unsaturated esters of mono- or dicarboxylic acids, alcohols with 1 to 20 carbon atoms

contain.

The phosphorus-sulphurized and alkoxylated hydrocarbon used according to the invention can be prepared from paraffins, olefins or their polymers, diolefins, hydrocarbons with acetylene bonds, alkyl aromatic or cycloaliphatic hydrocarbons and petroleum fractions, for example mineral lubricating oils, bright stocks and waxes, preferably bright stocks and polyolefins, in particular polyisobutylene, with a molecular weight between about 800 and 1600, can be obtained by reaction with a phosphorus sulfide, for example P ₂ S ₅ , or a mixture of elemental phosphorus and sulfur and subsequent alkoxylation. 1 to 10, preferably 2 to 5, mol of hydrocarbons can be added at temperatures in the range from 87 to 316 ° C

Applicant:

Esso Research and Engineering Company,
Elizabeth, NJ (V. St. A.)

Representative:

Dr. rer. nat. J.-D. Mr. v. Uexküll, patent attorney, Hamburg-Hochkamp, Königgrätzstr. 8th

Named as inventor:

Max Cohen, Bois-Guillaume, Seine-Maritime;

Robert Tirtiaux, Rouen, Seine-Maritime;

Roger Tourret,

Bolbec, Seine-Maritime (France)

Claimed priority:

France of September 15, 1960 (838 696)

preferably 149 to 288 ^° C. with 1 mol of phosphorus sulfide. The reaction time can be between about 1 and 10 hours, depending on the degree of conversion desired. The reaction is preferably carried out in a non-oxidizing atmosphere such as nitrogen.

For the alkoxylation, the phosphorus-sulphurized hydrocarbon is present at an elevated temperature a catalyst reacted with an alkylene oxide having 2 to 6 carbon atoms. To carry out the alkoxylation can take 1 mole of the phosphorus-sulphurized hydrocarbon at temperatures between 110 and 149 ° C in the presence of a suitable catalyst, for example a boron trifluoride-ether complex or caustic soda are reacted with 1 to 10 moles of alkylene oxide for 1 to 5 hours. By stripping of the phosphorus sulphurized hydrocarbon before the reaction with the alkylene oxide the stability of the product obtained can be increased.

According to the invention in a mixture with the phosphorus-sulphurized and alkoxylated hydrocarbon The copolymer used contains unsaturated esters of mono- or dicarboxylic acids and alcohols having 1 to 20 carbon atoms and

709 618/489

Vinyl esters of monocarboxylic acids with 2 to 6 carbon atoms or anhydrides or half esters of Ä,) 5-unsaturated dicarboxylic acids. Vinyl acetate is preferably used as the vinyl ester. The unsaturated esters can be derived both from unsaturated monocarboxylic acids, for example acrylic acid, alkyl acrylic acid or itaconic acid, and from unsaturated dicarboxylic acids, in particular maleic acid or fumaric acid, and with one or more alcohols having 1 to 20, preferably 8 to 18 carbon atoms or one obtained from natural products or synthetic produced alcohol mixture, for example coconut alcohol or oxo alcohol be esterified. Maleic anhydride is preferred among the anhydrides Λ, / 3-unsaturated dicarboxylic acids and maleic acid monoesters of one or more monoalcohols having 3 to 18 carbon atoms are preferred among the half-esters ix, β-vm saturated dicarboxylic acids.

Suitable copolymers can, for example, from a mixture with a content of 1 to 60 percent by weight of fumaric or maleic acid dialkyl esters of one or more alcohols with 10 to 20 carbon atoms, 1 to 60 weight percent fumaric or maleic acid dialkyl esters of one or more several monoalcohols with 1 to 10 carbon atoms per alkyl radical, 0.1 to 20 percent by weight Maleic acid monoesters of one or more monoalcohols having 3 to 18 carbon atoms and 1 to 80 percent by weight of vinyl esters of monocarboxylic acids having 2 to 6 carbon atoms are obtained.

The mixture used in the present invention is added to the lubricant in amounts of 0.1 to 15, preferably 0.5 to 5 percent by weight admixed. The amount of phosphorus sulphurized, alkoxylated hydrocarbon and copolymer are each between 0.05 and 10 percent by weight.

The lubricating oils can be mineral oil fractions as well as oils of animal or vegetable origin, for example 'castor oil' or fish oils, or synthetic oils, for example oxidized mineral oils, mono- or diesters such as dioctyl adipate or sebacate, complex esters of mono- or dicarboxylic acids, one or dihydric alcohols and polyalkylene glycol or glycol ethers.

Further known additives such as oil-soluble oxidation inhibitors , for example oc- or / I-naphthylamine, phenothiazine, their alkyl-substituted derivatives, alkylphenols such as 2,4-dimethyl-6-tert.-octylphenol, substituted diphenylamines such as dioctyldiphenylamine and diphenols can also be added to the lubricating oils High pressure additives, for example alkyl- or aryl-substituted phosphates and phosphites, sulfurized hydrocarbons, sulfurized sperm oil or metal dialkyldithiophosphates, and viscosity index improvers such as polyisoolefins or degraded rubber-like copolymers can be added.

To carry out the comparative experiments, a phosphorus-sulphurized, ethoxylated polyisobutylene was used, which was obtained by heating a polyisobutylene with a molecular weight of 1200 with 15 percent by weight P ₂ S ₅ to 221 ° C. for eight hours, diluting the product obtained with 100 parts of mineral oil, stripping for 4 hours with steam at 121 ° C ⁰ C and subsequent 3-hour reaction with 8 parts of ethylene oxide at 171 ⁰ C in the presence of a boron trifluoride-ether complex had been obtained. This product is referred to as additive A in the following.

The copolymer Bl used in the comparative experiments was one by copolymerization Mixture of vinyl acetate, maleic acid monobutyl ester and fumaric acid alkyl esters with 4 to 10 carbon atoms per alkyl group at 80 ° C in a mineral oil diluent in the presence of azodiisobutyronitrile produced as a catalyst.

Another inventive copolymer B 2 was obtained by copolymerizing a mixture from vinyl acetate, maleic anhydride and fumaric acid alkyl esters with 8 to 18 carbon atoms per Alkyl group in a mineral oil diluent in the presence of benzoyl peroxide as a catalyst obtain.

For comparison, a product II of German Patent 1,053,125 was also used Copolymer of 18 g vinyl acetate, 37 g maleic acid dinonyl ester, 37 g maleic acid diester of oxo alcohols with an average of 17 carbon atoms and 8 g of one by conversion of equimolar amounts Maleic anhydride and nonyl alcohol and subsequent alkoxylation with 2.5 times the molar Amount of ethylene oxide obtained ethoxylated maleic acid monononyl ester used. This product is referred to as C in the following.

In the comparative tests, the effect of adding a or more of the above-mentioned additives to the lubricating oil used on keeping it clean of the engine parts examined.

In a first series of tests, the so-called Petter A.V.I. test (Journal Inst, of Petroleum, September 1953) and a lubricating oil with a viscosity at 99 ° C of 13 cSt and a viscosity index of 101 is used. The indicator for the cleanliness of the engine parts was determined without prior washing of the examined parts. The results of this investigation are compiled in the following table I:

Table 1

Content of the lubricating oil Addition B2 5 Petter A. V.l. attempt Addition A ■ Addition Bl Weight percent Total- 1 identification number 1 60 2 4: 88 3 - i 4 - 74 4th - i - 9 65 5 2 1 2 - 96 6th 4 I - 98

The above numerical values show that the inventive additive combinations A + B1 and A + B 2 lead to a synergistic increase in the cleaning effect.

In a second series of tests, engine test runs were carried out according to the CRC FL ₂ standard with a Peugot 203 engine with a paraffinic lubricating oil, SAE 30 with a viscosity at 99 ° C. of 11.8 cSt and a viscosity index of 137. The purity of the individual engine parts was assessed on the basis of a scale from 0 to 10, with the value 0 indicating a complete coating of the examined part with deposits and the value 10 indicating a complete absence of deposits

is equivalent to. The results of these test runs are summarized in Table II below:

Table II

Attempt7 try Composition of the lubricating oil Lubricating oil, weight percent 98 98 Additive A, percent by weight 1 1 Additive B1, percent by weight - 1 Additive C, percent by weight 1 - Viscosity at 99 ° C, cSt 12.5 13.2 Viscosity index 140 145 ' Pour point, ° C -33 -33 Engine testing purity Combustion chamber 8.9 9 Side walls of the pistons (Resin deposition) 9.85 9.85 Cylinder chuck (Resin deposition) 8.4 9.2 Valve lifters (Resin deposition) easy very Sludge deposition on the oil filter, g 0.2 0.2 on the crankshaft, g 1.8 1.7

The numerical values given above show that the additive combination A + B1 according to the invention the well-known additive combination A + C, especially with regard to the purity of the cylinder liner, but is also considerably superior in terms of the viscosity index.

Claims (1)

Claim:
Using a mixture of a) a phosphorus sulphurized and an alkylene oxide with 2 to 6 carbon atoms converted hydrocarbon, in particular a polyisobutylene with a molecular weight between 800 and 1600, and b) a copolymer a vinyl ester of a monocarboxylic acid with 2 to 6 carbon atoms,
an anhydride or half-ester of a «^ -unsaturated dicarboxylic acid and
unsaturated esters of mono- or dicarboxylic acids and alcohols with 1 to 20 carbon atoms as a lubricating oil additive. Considered publications:
German Patent No. 1,053,125;
British Patent Nos. 760994, 767 033;
French patents nos. 1 076 398,1088 008, 1161098.