FI69864B - SMOERJMEDELSKOMPOSITIONER INNEHAOLLANDE EN ANTIOXIDATIV MAENGDAV EN BLANDNING AV EN BENZOTRIAZOLADDUKT OCH EN ALKYLDIAM ERAPTOTIADIAZOLE - Google Patents

Description

kfcÄF ^ l ΓΒ1 m ^ ANNOUNCEMENT 69864

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(45) Patent rc-P’clat PG.5.8G

(51) Kv.lk.7int.CI. * C 10 M IA 1/08 FINLAND —FINLAND (21) Patent application- Patenunsökning 802527 (22) Application date - Ansökningsdag 1 2.08 .8 0 (23) Starting date - Giltighetsdag 1 2.08.80 (41) Made public - Blivit offentlig ^ 02 82

National Board of Patents and Registration Date of publication and publication. - '

Patent- och registerstyrelsen '' Ansökan utlagd och utl.skriften publicerad> '· (32) (33) (31) Privilege claimed - Begärd priority (71) Mobil Oil Corporation, 150 East A2nd Street, New York, New York, USA ( US) (72) Joosup Shim, Gloucester, New Jersey, USA (US) (7A) Berggren Oy Ab (5A) Lubricant containing a mixture of a benzotriazole adduct and an idiomaptaptothiazole. The present invention relates to lubricant preparations which are normally sensitive to oxidation by disintegration in the form of an antioxidant game and an antioxidant game and a mixture of benzotriazole adducts and a 1 ky Idimerk-aptot iad iazol.

Triazoles have been used in lubricant preparations as metal deactivators. For example, U.S. Patent No. 3,597,353 discloses the use of tetrahydrobenzotriazole as a metal deactivating additive for natural and synthetic lubricants. Similarly, U.S. Patent No. 3,413,227 describes the use of a C 2 -C 4 alkyl substituted benzotriazole as corrosion or fading inhibitors. U.S. Patent No. 4,060,497 discloses the use of 5-alkylbenzotriazole to reduce wear between moving surfaces against steel.

The reaction products of benzotriazoles are also known. For example, U.S. Patent No. 3,788,993 describes the reaction of benzotriazoles with alkyl or alkenyl succinic anhydrides to form products that impart corrosion inhibiting properties to lubricating oils.

U.S. Patent No. 2,698,064 discloses the use of esters of benzotriazoles and adducts of unsaturated dicarboxylic acids or anhydrides to impart anti-corrosion properties to organic preparations.

It has now been found that combinations of benzotriazole adducts and certain thiadiazoles have very valuable properties. In particular, they give lubricating oils good antioxidant and corrosion resistance properties.

The present invention therefore relates to a lubricant preparation characterized in that it contains as a main ingredient a mixture of a lubricant and an antioxidant comprising (1) a benzotriazole compound of the formula

; Ό f N

OF

i

B

wherein R is a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and an ether of the formula R'CH = CHOR "or a vinyl ester of the formula

O

«R1CH = CHOCR '' 'wherein R' is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms in any isomeric form, R'1 is an alkyl group having 1 to 18 carbon atoms in any isomeric form and R '' 'means the same as R' ' or it is an aryl group having 1 to 18 carbon atoms, an alkaryl group or an aralkyl group, an adduct and (2) an alkyl dimercaptothiadiazole having the formula:

N -N

4 «H 5

R - (S) -S-C C-S- (S) -R

X \ / X

S

3 69864 4 5 wherein R and R, which may be the same or different, are hydrocarbon groups having 1 to 30 carbon atoms and X is 0 to 8.

The benzotriazole adducts used in the compositions of this invention are formed by reacting a benzotriazole compound with a vinyl ether or vinyl ester of a carboxylic acid.

They are described in European Patent Application No. 79301128 (Publication No. 6710).

Preferred are those benzotriazole compounds in which R is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Benzotriazole and tolutriazole are particularly preferred.

Preferred are those vinyl ethers and vinyl esters in which R 'is a hydrogen atom or an alkyl group having 1 to 11 carbon atoms, R' 'is an alkyl group having 1 to 8 carbon atoms, and R''1 is an alkyl, aralkyl group having about 1 to 14 carbon atoms. or an alkaryl group.

Particularly preferred are those vinyl ethers and vinyl esters in which R 'is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, R'1 is an alkyl group having 1 to 4 carbon atoms, and R' * * is an alkyl or aryl group having 1 to 6 carbon atoms.

Benzotriazole adducts are formed by reacting a benzotriazole compound with a vinyl ether or vinyl ester of a carboxylic acid in a ratio of 1: 1 to 1:10, preferably 1: 1: 1, and preferably 1: 1 to 1: 1 in a molar ratio of benzotriazole compound to vinyl ether or vinyl carboxylate.

Temperatures between 25-150 ° C and preferably between 80-120 ° C are used. Generally, the reagents are kept in contact for 1-8 hours, preferably 2-4 hours. The reaction time used in each case depends on the temperature and reagents used, and at higher temperatures the reaction time may be shorter than the time at lower temperatures for a given pair of reagents.

The reaction often proceeds in the absence of a catalyst. However, catalysts of an acidic nature, such as acetic acid, propionic acid 4,69864, toluenesulfonic acid, phosphonic, or polyphosphonic and methanesulfonic acids can be used. Alkaline catalysts can also be used. Typical examples are sodium or potassium alkoxides, sodium or potassium metal and their hydroxides.

The benzotriazole products of this invention may contain multiple isomers, i.e., vinyl ethers and vinyl esters may be attached to the benzotriazole at either the 1-H or 2-H position. Both Markownikow and anti-Markownikow additions can also occur. It has been found that each isomer is individually effective in imparting improved antioxidant and anti-corrosion properties to lubricant formulations. Thus, as used herein, the phrase "adducts" or "benzotriazole products" may refer to any of the isomers or mixtures of isomers produced.

4 5

Examples of R and R in the formula of alkyl dimercaptothiadiazole include alkyl, aryl, alkaryl and aralkyl groups and are preferably alkyl groups and typical examples are methyl, butyl, octyl, decyl, dodecyl, octadecyl, phenyl. , tolyl and benzyl groups.

They can be prepared according to the method described in U.S. Patent No. 2,719,125 and are commercially available.

The present invention provides improved durability of oxidation of lubricating media such as lubricating viscosity liquid oils or fats. Both mineral (paraffinic or naphthenic) and synthetic oils as well as mixtures thereof can be used as a lubricant or grease. A wide variety of materials can be used as thickeners or gelling agents for fats. These may include conventional metal salts or soaps and other thickeners, such as non-soap thickeners, for example, surface-modified clays and silicic acids, aryl ureas, and calcium complexes.

Typical synthetic carriers include polyolefins, poly-glycols and esters such as polybutenes, hydrogenated poly-decenes, polypropylene glycol, polyethylene glycol, tri-69864 methylolpropane esters, neopentyl and pentaerythritol esters and di (2-ethyl) ethyl (2-ethyl) ) adipate.

The antioxidant compositions of this invention are unexpectedly effective in mineral oils having a high sulfur content.

Lubricants may also contain other materials, such as corrosion inhibitors, extreme pressure improvers, viscosity index improvers, co-antioxidants, and anti-wear agents.

The compositions of this invention may be used in any amount effective to provide the desired degree of improvement in oxidation. It is effective to use the mixture in amounts ranging from 0.001 to 0.2% by weight and preferably from 0.01 to 0.1% of the total weight of the preparation. When preparing a mixture of the two compounds, 20-80% and preferably 50-70% of a benzotriazole adduct and 80-20% and preferably 30-50% of thiadiazole are used. All percentages are calculated on the weight of the whole mixture.

The following examples form specific descriptions of the above invention.

Example 1

Additives of benzotriazole and n-butyl vinyl ether A mixture of 59.5 g of benzotriazole, 100 g of n-butyl vinyl ether and 100 ml of benzene was heated at 90 ° C (refluxing) for 6 hours. An additional 50 g of n-butyl vinyl ether was added and refluxing at 90 ° C was continued for about 5 hours, after which the unreacted n-butyl vinyl ether and benzene solvent were removed by distillation. Petroleum ether (b.p. 30-60 ° C) was added to the residue, and the precipitated unreacted benzotriazole (9.1 g) was removed by filtration. Distillation of the solvent from the filtrate left 90 g (97%) of the mixed isomer addition product.

Gas chromatography showed that the reaction product consisted of two main components (isomers) which could not be separated by distillation. A narrow verse by kp. was 100-103 ° C below 69864 at 0.1 mm Hg, was judged to be a 30:70 mixture of isomeric monoaddition products by gas chromatography.

Elemental analysis corresponded to the monoadduct reaction product of the empirical formula C12H17N3O:

Analysis (% by weight) C H N

calculated from C12H17N3O: 65-73 7.81 19.16

Experimental: 66.34 7.63 19.9

The second isomer (designated isomer A) was separated by elution from a column packed with Alcoa F-20 alumina (Alcoa is the trade name) using petroleum ether (b.p. 30-60 ° C) as the solvent. Satisfactory Elemental Analysis was obtained for the monoadduct:

Analysis for isomer A (% by weight) C H N

Calculated for c 12 H 17 N 3 O: 65.73 7.81 19.16 Experimentally: 66.31 8.08 19.0

The ultraviolet spectrum of isomer A showed maxima at 284.2, 277.6, 272.5 and a shoulder at 266.0 nm. The ultraviolet spectrum for the starting benzotriazole was significantly different, with maxima at 276, 259, and 254 nm. The NMR proton spectrum showed a quartet, indicating proton cleavage by an adjacent methyl group, indicating that the isomer is an adduct of Markownikow1. Based on these data, it is concluded that isomer A has the following structure: / c “3

N —CH

X o C4H9

The second isomer (designated isomer B) was isolated by benzene ingestion from a neutral alumina column. A satisfactory Elemental analysis for the monoadduct was also obtained:

Analysis for isomer B (% by weight) C H N

Calculated for C12H12N3O: 65.73 7.81 19.16

Experimental: 65.60 7.78 19.4

The ultraviolet spectrum of isomer B showed maxima at 7 69864 282, 261 and 254.5 nm. This is similar to the ultraviolet spectrum of the starting benzotriazole, which showed maxima at 276, 259, and 254 nm. The infrared spectrum of isomer B showed significant differences from the spectrum of isomer A. The NMR proton spectrum of isomer B also contained a quartet, indicating that the methyl group cleaves one adjacent proton and this isomer is also a Markownikow adduct. Based on these results, it is concluded that isomer B has the following structure:

© J

CH3-C-OC4H9

B

Example 2

Addition product of toluathiazole and n-butyl vinyl ether A mixture of 190 g of tolutriazole (5-methylbenzotriazole), 300 g of n-butyl vinyl ether and 200 ml of benzene was heated at reflux at 88-92 ° C for a total of 14 hours. The unreacted n-butyl vinyl ether and benzene solvent were removed by distillation under reduced pressure, and the residue was cooled and filtered through a pad of Super Cel (trade name) filter medium. 306 g of adduct were obtained, a pure dark amber liquid representing 92% of the yield.

Example 3

Addition product of benzotriazole and vinyl acetate - base catalyzed

To benzotriazole (59.5 g) and potassium tert-butoxide in toluene (100 mL) heated to 103-105 ° C was added vinyl acetate (86 g) over about 2.25 hours. The reaction mixture was then heated at 98 ° C with stirring for an additional 5 hours. The reaction mixture was washed with water, dried and the solvent was stripped off by rotary evaporation. Addition product (50.5 g), m.p. 63-64 ° C was obtained from the residue by extraction with cyclohexane. Recrystallization from benzene gave a white crystalline solid, m.p. 64-65 ° C. The infrared spectrum was consistent with the structure of the adduct. Elemental analysis was satisfactory: 69864

C H N

Analysis calculated by the formula C] _oH] _] _ ° 2N3: 88.53 5.40 20.48

Experimentally 58.81 5.46 20.4

Example 4 Product Review

The alkyl dimercaptothiadiazole used in the mixtures below was purchased under the tradename Amoco 150. It is the product of Example VI of U.S. Patent No. 3,719,125.

Three different mixtures prepared as follows were evaluated in different experiments: 1. Soluble paraffinic neutral mineral oil (viscosity 35 cSt at 38 ° C) with 0.55% standard additive system and (1) 60% reaction product; formed by 1 mole of butyl vinyl ether and 1 mole of tolyl litriazole, and (2) 40% alkyl dimercaptothiadiazole.

2. A mixture containing a highly purified basic raw material (viscosity 35 cSt at 38 ° C; viscosity index 111) mixed with a standard additive system.

3. A mixture containing 25% product 1 and 75% product 2.

These tests included neutralization number (NN) determination, foaming tendency, rust, copper corrosion, and rotational bomb oxidation (RBOT).

Copper Corrosion Test - ASTM D-130

The polished copper strip is immersed in the sample and kept at the temperature and time characteristic of the material to be tested. At the end of this period, the copper strip is removed, washed and compared to ASTM copper strip corrosion standards. A temperature of 49 ° C and a time of 3 hours was used.

Rotary Bomb Oxidation Test (RBOT) - ASTM D-2272 'propellant oil, water, and a copper co-catalyst coil inside a covered glass container are placed in a bomb equipped with a pressure gauge. The bomb is charged with oxygen at a pressure of 620 kPa, placed in a constant temperature oil bath set at 150 ° C and rotated axially at 100 rpm at an angle of 30 ° from the horizontal. The time taken for the test oil to react with a given volume of oxygen is measured, with a typical pressure drop indicating the end of the time, in this case a pressure drop of 172 kPa.

Rust Test - ASTM D-665

The method involves stirring a mixture of 300 ml of test oil and 30 ml of distilled or synthetic seawater, as appropriate, at 60 ° C with the cylindrical steel test piece completely immersed in it. It is customary to continue the experiment for 24 hours; however, the trial period may be shorter or longer at the discretion of the Parties. The experiment was continued for 24 hours using seawater at 60 ° C.

Foam Test - ASTM D-892 A sample maintained at 24 ° C is blown with air at a constant rate for 5 minutes, then allowed to settle for 10 minutes. The volume of foam is measured at the end of both cycles. The experiment is repeated with another sample at 93 ° C and then after compression of the foam at 24 ° C.

The results are summarized in Table 1.

table 1

Mixture 1 2 3 NN 0.07 0.20 0.32

Foam test 180/0 225/0 190/0

Rust test passes passes passes

Copper corrosion test IB IA Ia RBOT, min 390/425 260 110

Other blends were prepared as follows: 1. Base fluid containing 99.45% 35 cSt (38 ° C) turbine base oil and a standard additive kit.

2. A mixture of 1 plus 0.05% by weight of a mixture containing (1) 60% by weight of a reaction product consisting of 1 mole of butyl 10 6 9 8 6 4 vinyl ether and 1 mole of tolyltriazole, and (2) 40 % by weight of alkyl dimercaptothiadiazole.

3. Mixture 1 plus 0.05% by weight of the reaction product of mixture 2 (1).

4. Mixture 1 plus 0.05% by weight of alkyl dimeraptothiadiazole of mixture 2.

These were evaluated in the dried tests below.

Total Oxidation Products Test (CIGRE) -IP 280 Oxygen is passed for 164 hours through an oil sample to which a soluble metal catalyst, iron and copper has been added and is maintained at 120 ° C. The volatile acid products, the acidity of the oil and the sludge formed are determined. If a measurement of the length of time required to achieve a clear change in the rate of volatile acid evolution is required, the acidity / time curve can be obtained by determining the daily volatile acids. The catalyst is a soluble copper salt.

Rotary Bomb Oxidation Test (RBOT) - ASTM D-2272 Described above.

Turbine Oil Stability Test (TOST) - An ASTM P-943 oil sample is brought to 90 ° C in the presence of water, oxygen and iron-copper catalyst. The experiment was performed for 2500 hours.

The results were as follows:

Table 2

Mixture 1 2 3 4 CIGRE, total oxidation products 5.53 0.29 1.15 5.22 RBOT, min 315 440 400 395 TOST, sludge,% by weight 0.76 0.16 0.28 0.36

Claims (7)

1. Lubricate the solvent composition, characterized in that it contains as a major component a lubricant and an antioxidant amount of a mixture of (1) an adduct of a benzotriazole compound of formula: ISO 3 H where R is a hydrogen atom or a hydrocarbon group containing 1-12 carbon atoms, and a vinyl ether of formula R1CH = CHOR "or a vinyl ester of formula 0 II R1CH = CHOCR" 'in which formulas R' is a hydrogen atom or an alkyl group containing 1-8 carbon atoms in which isomer isomeric form, R "is an alkyl group containing from 1 to 18 carbon atoms in which isomer isomeric form and R" is as defined as R "or is an aryl group, an alkaryl group or an aralkyl group containing 1 to 18 carbon atoms and (2) the formula: N - N 4. II 5 R_ (S) - SC CS- (S) -------- R x, xs / 4 where R and R, which are the same or different, represent hydrocarbon groups containing 1- carbon atoms and x are 0-8.