DE2447550A1 - AMINE SALT AND ITS USE AS AN ADDITIVE TO LUBRICANTS - Google Patents

Description

The invention relates to lubricant additives having corrosion and oxidation inhibiting properties. It also relates to improved lubricant compositions containing these additives. Such lubricant compositions can be made from lubricating oils, greases or lubricants on aqueous Basis exist.

Certain types of lubricants including water-based lubricating oils, greases and cutting oils tend to deteriorate due to oxidation or

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Cause corrosion when working with various metal surfaces come into contact. In addition, such lubricants can also be subject to deterioration intended functions, e.g. the load-bearing properties, Experienced. This results in the need to incorporate effective antioxidants and corrosion inhibitors Additives in such lubricants.

When processing metals, e.g. by cutting or, machining, grinding, turning and milling, it is common to both the tool and the workpiece flush with a coolant to dissipate the heat generated during machining. It is also common these coolants in combination with various lubricating and high-pressure properties exhibiting agents for Reduction of the friction between the tool and the workpiece, especially during work such as tapping or rooms to use. In this regard, it has heretofore been customary to use aqueous compositions which contain such lubricating agents as emulsified petroleum or non-petroleum additives. or cutting fluids perform satisfactorily, it is necessary that residue deposits on the tool and the workpiece after machining. These liquids are also said to be a Have compatibility with hard water solutions, so that a separation of lubricant components does not occur and sticky residues, which interfere with the operation of the machine, as well as excessive foaming are avoided.

It has been found that the corrosion and oxidation inhibition properties can be improved by using an amine salt of the reaction product in smaller amounts

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an alkyl or alkenyl succinic anhydride and a benzotriazole or one

substituted benzotriazoles incorporated. Most of them These amine salts are used in an amount of ο, οοΐ to 40% by weight and preferably in an amount of 0.5 to 10 wt. Tb based on the total lubricant composition used.

Except for the granting of corrosion-inhibiting properties in lubricant compositions, these amine salts are also important in terms of providing anti-wear, Effective anti-rust and bactericidal properties. The salts are particularly useful in lubricants which contain a predominant part (at least 50% by weight) of water.

The additive consists of an amine salt of a benzotriazole succinic anhydride reaction product. The commonly used benzotriazole is 1,2,3-benzotriazole, however, other isomers can also be used. Substituted benzotriazoles, especially alkyl-substituted benzotriazoles such as tolyltriazole, can also be used.

The benzotriazole is made with an alkyl or alkenyl succinic anhydride enriched. The alkyl or alkenyl group in these anhydrides preferably contains at least 6 carbon atoms, usually 6 to 50 carbon atoms, a content of 12 to 30 carbon atoms being preferred will. These compounds can be prepared as usual by reacting an olefin or olefin polymer with maleic anhydride produced v / earth. The reaction takes place by addition, with a shift of the double bond in the unsaturated starting material takes place. The alkenyl unsaturated substituent can be hydrogenated to give tone, if desired to generate an alkyl substituent.

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BATH ORIGINAL

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_ 4-

Examples of various anhydrides are described in U.S. Patent 3,256,187.

Typical of such alkyl and alkenyl succinic anhydrides are octenyl succinic anhydride, dodecenyl succinic anhydride, Polybutenyl succinic anhydride, Polyisobutenyl succinic anhydride, hexadecenyl succinic anhydride, Eicosenyl succinic anhydride, triacontenyl succinic anhydride and isooctadecy / succinic anhydride.

The benzotriazole is in general with the anhydride in a molar ratio of 1: 1 to 2: 1 (benzotriazole: anhydride), preferably in an equimolecular ratio implemented.

The reaction between the benzotriazole and the anhydride can be at a temperature of loo to 15o ° C, are preferably carried out by loo to 125 ⁰ C.

The reaction product of the benzotriazole and the anhydride is then enriched with an amine or a mixture of amines. If the final amine salt is to be used in an oleophric composition, the amine is preferably a long chain (Cq-C,, preferably C-. PC _?. ) Amine, such as n-octylamine, tert-octylamine, nonylamine, decylamine, dodecylamine , Hexadecylamine, octadecylamine, octadecenylamine or octadecadienylamine. Amines of this type are commercially available ("army" amines). Particularly preferred amines are the tert-alkyl primary monoamines in which a primary amino group (-NH ₂ ) is attached to a tertiary carbon atom

C ^ -C, -, preferably C-jp-C-z - alkyl group is bonded. Examples of such amines are tert-dodecyl primary amine, tert-tetradecyl primary amine, tert-pentadecyl pri-

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BATH ORIGINAL

tertiary amine, tertiary hexadecyl primary amine, tertiary octadecyl primary amine, tertiary eicosyl primary amine, tertiary tetracoayl primary amine, tertiary triacontyl primary amine and mixtures of such amines . Amines of this type are commercially available ("Primene 81R" and "Primene JMT"). "Primene 81R" is a mixture of primary amines in which one carbon atom of a tertiary alkyl group is attached to the amino (-NH ₂ ) group and the 12 to 15 carbon atoms each. Molecule amine enthalten.Diese- i / Iischungen contain about 85 Gevr.fo tertiary-dodecyl primary amine, such as Io wt. ° / o tertiary pentadecyl-primary-amine and and relatively small amounts, for example less than 5 wt. ^, Amines with fewer than 12 and more than 15 carbon atoms. "Primene JMT" is a mixture of tertiary alkyl primary amines having 18 to 24 carbon atoms, which have a tertiary carbon atom bonded to the -NHp group and about 40 wt. ^ Tertiary octadecyl primary amine, about 3o Gev / .fo eicosyl tertiary primary amine, about 15% by weight docosyl tertiary amine, about 10% by weight tertiary tetracosyl primary amine, and a minor amount less than 5% by weight of other amines as high as tertiary triacontyl - contain primary amine.

The amine reactants can be prepared in a number of ways as is well known in the art. Specific processes for the preparation of primary tert-alkyl amines are described in The Journal of Organic Chemistry, Vol. 2o, page 295 ff (1955). Mixtures of such amines can be prepared by first ater hydrated with sulfuric acid, and V / to the corresponding alcohol, reacting the alcohol in ₄ * umwändeIt alkyl chloride with ammonia under pressure, tert to the primary of a polyolefin fraction (for example, polypropylene and Polybutylenschnitten) .-Alkylamine mixture to be obtained.

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The amines themselves can be either oil soluble or water soluble. Y / hen the finished amine salt in an aqueous If the lubricant composition is to be used, the amine is preferably an alkanolamine or a mixture of Alkanolamines Examples of such amines include mono-, di- and triethanolamines, the isopropanolamines (mono-, Di- and tri-), dimethylethanolamine, diethylethanolamine, aminoethylethanolamine, N-acetylethanolamine, phenylethanolamine, Phenyl diethanolamine and mixtures of these materials. Triethanolamine is particularly preferred.

Salt formation occurs effortlessly through reaction between the amine and the benzotriazole / anhydride reaction product Room temperature instead.

When the lubricant comprises an oil of lubricating viscosity, the lubricant can contain various mineral oils or synthetic oils of lubricating viscosity. In cases in which a high temperature stability is not a primary requirement, a mineral oil having a viscosity of at least 4o SSU at 37.8 ⁰ C (loo ° F) is preferably (4.2 centistokes at 38 ⁰ G) and in particular those fall in the range of 60 to 6000 SSU SSU at 37.8 ⁰ G (loo ° F) (Io to 13oo Gentistokes at 38 ⁰ C) was used. In some cases, the lubricant can contain a synthetic hydrocarbon oil either alone or in combination with a mineral oil. Examples of synthetic carriers include polypropylene glycol, trimethylolpropane ester, neopentyl and pentaerythritol esters, di- (2-ethylhexyl) sebacate, di- (2-ethylhexyl) adipate, dibutyl phthalate, silicate esters, esters of phosphorus-containing acids, chain-type polyphenyls. Siloxanes or alkyl substituted diphenyl esters.

The liquid lubricants can also be used in combination with a grease-forming amount of a thickening agent

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tels used to do lubricating greases to form »This Thickening or gelling agents include salts or Soaps, non-soap thickeners such as surface modified clays and silicas, aryl ureas and Calcium salt complexes.

The amine salts according to the invention are particularly useful in aqueous metalworking lubricants. Oils of this type can contain an emulsified mineral oil ("soluble oils") or they can be water-based or water-based Mixtures with a water base, e.g. polyglycol / 7 / water mixtures, be constructed.

The soluble oils usually contain a mineral oil, water, one or more emulsifying agents and additives, such as agents to improve lubricity, corrosion inhibitors, extreme pressure agents or the like. Fatty acids are often used as a means of improvement used for lubricity and petroleum sulfonates as emulsifiers and phosphoric esters, e.g. tricresyl phosphate, as extreme pressure agents (E.P. Agents).

These compositions are often manufactured industrially in the form of concentrates, which when used with Water can be diluted. "Soluble" oils are of this type for example, U.S. Patents 3-723,313, 3,723,314, 3,432,434 and 3 365 397.

Another type of metalworking lubricant to which the amine salt additives according to the invention are added is a polyoxyalkylene glycol based lubricant. Lubricants of this type contain a polyoxyalkylene glycol or glycol esters. Polyoxyethylene and polyoxypropylene glycols and their esters are the most common materials. That

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Erlycol or its ester can comprise all of the base medium of the lubricant, or it can be present with water in a predominant or minor amount. The lubricants based on polyoxyalkylene glycol (or glycol ester) mixtures with water normally contain 1 to 50% by weight, in particular 2 to 20% by weight, of glycol or glycol ester, with water forming the remainder of the base medium. Other additives, such as agents to improve lubricity (e.g. fatty acids), emulsifiers (e.g. petroleum sulfonates, ethanolamides), stabilizers, corrosion inhibitors (e.g. sodium nitrite) and extreme pressure agents (e.g. tricresyl phosphate) can also be present. Examples of glycol or glycol ester based metalworking lubricants are described in U.S. Patent 3,652,411. V / ater / glycol lubricants are described for example in DT-OS 1444 9o5 and US Patent No. 3,374,171 "

Another type of metalworking lubricant is based solely on water as a liquid medium. In addition to water / water, these lubricants can also contain agents to improve lubricity, corrosion inhibitors, Bactericides, sequestrants (e.g. the sodium salt of ethylenediaminetetraacetic acid) and other additives contain. Lubricants of this type are described, for example, in U.S. Patents 3, 256 187, 3 769 214 and 3 31o 489.

The corrosion-inhibiting properties of the amine salts of the present invention are shown in Examples 1 to 4 below, and typical compositions containing the salts are illustrated in the examples below.

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example 1

A number of add-on systems, as in the one below Table shown was according to the well-known galvanic corrosion test (North American Rockwell test) rated using a bimetallic magnesium / steel pair separated by a strip of glass cloth and shorted with a 3 inch wire. This pair is put into a trial solution of lubricant-coolant of 4o / l immersed. After 24 hours, the short-circuit wire is replaced with micro-ammeter wires, and the current was measured, values above 12o microamps indicate severe corrosion and are for denoting a rejection of the lubricant.

From the "comparative values in the table it can be seen that typical approaches used for non-ferrous metalworking considered unsatisfactory are illustrated in Examples 1, 2 and 3. In example 1 were 43 wt. $ Of an aqueous triethanolamine solution used, and it was found to stain magnesium and a current reading of 295 microamps obtain. When the amine either with the tetrapropenyl succinic anhydride reacted or combined with benzotriazole, as in each case in Examples 2 and is specified, the current values still exceed 12o microamps. However, if the triethanolamine with a tetrapropenylsuccinic acid / benzotriazole reaction product is combined, the results of the terminal corrosion test decreased (Joint corrosion) down to 62 microamps as shown in Example 4. This shows that this Additional system considered satisfactory for the machining of a non-ferrous metal, e.g. magnesium, without corrosion problems, with steel contact on the machine tool connected can be viewed.

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TABEL Aqueous coolant with inhibitors against galvanic corrosion

Tetrapropenyl natula

Bei-triethanol acid analysis amine hydride

cn 1 43, oo O CO CO 2 3o, oo - » OD 3 3o, oo - » ro CO 4th 3o, oo CO

13, oo

Tetrapropenyl water succinic acid 57, oo anhydride/ 57, oo Benzotriazole 57, oo reactive 57, oo Benzo- product triazole - - 13, oo - 13, oo

galvanic corrosion test, microampere for magnesium / steel pair (test solution 40 parts distilled water, 1 part additional concentrate

295

125

82o

62

- li -

Example 5

26 g (0.1 mol) of tetrapropeny / succinic anhydride is with 12 g (0.1 mol) of benzotriazole in ethylene glycol monobutyl ether solvent implemented at a temperature of 100 to 12o ° C. The reaction product is then with 12 g (0.1 mol) enriched triethanolamine, whereupon the amine salt is precipitated after cooling and filtered off. at In an optional method, the reaction intermediate is removed by cooling and filtering and thereafter dissolved in the liquid triethanolamine.

Example 6

The procedure of Example 5 was repeated with the exception that 35 g (0.1 mol) of isooctadecysuccinic anhydride were used.

Example 7

The procedure of Example 5 was repeated, except that the amount of benzotriazole was increased 24 g (0.2 moles) is doubled.

Examples

52 g (o, 2 moles) of tetrapropenyl succinic anhydride were dissolved at 12o ° C in ithylenglykolmonobutyläther _t and 25 g (o, 21 mole) benzotriazole was during 5o minutes ί added portionwise. After cooling, 60 g (approximately 0.2 mol) of Primene JMT were added and the Primene JMT salt was deposited after cooling.

*) (Butyl cellosolve)

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Example 9

The procedure of Example 8 was repeated except that 35 grams (approximately 0.2 moles) of Primene 81R was added to form the Primene 81R salt, which was deposited after cooling.

Example Io

t h

It became a soluble cutting oil from the following

Components manufactured:

Weight ° / o

Mineral oil A ^ ¹ ^ 8,6o

Mineral oil B ^ 5.4o

Lauroyl diethanolamide 2, oo

C, AC, Q fatty acids, mixed 9 »oo

Brdölsulfonat, sodium salt 2, oo

Amine salt according to Example 8 2, oo

Tricresyl phosphate 2, oo

Water rest

annotation

(1) Naphthenic oil with a viscosity of 20 centistokes

at 38 ⁰ C

(2) solvent refined faraffinöl having a viscosity of 2o centistokes at 38 ⁰ C.

All ingredients are combined with about one third of the water and mixed for one hour, after which they are used during another hour through a Manton-Gaulin homogenizer. After cooling, the rest of the water can be admitted.

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Example 11

A soluble cutting oil was made as follows:

Weight jo

Mineral oil A 9 »oo

Mineral oil B '6.00

Lauroyl diethanolamide 2.00

Fatty acids, mixed, ^ - \ a ~ ^ - \ q 9 »oo

petroleum sulfonate, sodium salt 2.00

Amine salt according to Example 9 2.00

Tricresyl phosphate 2.5o

Water rest

The lubricant can be according to that described in Example Io Working method are produced.

Example 12

A polyglycol based lubricant was made as follows:

Polyglycol ^
Phenyl-1-naphthylamine
Tricresyl phosphate
Amine salt according to Example 5

annotation

(.3) reaction product of propylene oxide and trimethylolpropane; Molecular weight approximately 3,000.

Example 13

A water and glycol based metalworking abrasive was prepared as follows :

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93 , 00 3 , 00 2 , 00 2 , 00

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Polyglycol ^{vt |} "' 8th

Amine salt according to Example 5 6

Water 86

annotation

(4) propylene oxide / ethylene oxide copolymer, hydroxyl number 22-38,

Example 14

A metari working lubricant on water and water Glycol base was made as follows:

Polyglycol .12

Amine salt according to Example 5'5

Parachlor-meta-cresol (bioeiid) 1

Water 82

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Claims (7)

Claims Amine salt of a reaction product of an alkyl or alkenyl succinic anhydride and a benzotriazole or substituted benzotriazole. 2. Salt according to claim 1, characterized in that the anhydride and the benzotriazole in a molar ratio from 1: 1 to 1: 2, preferably approximately 1: 1, are converted. 3. Salt according to claim 1 or 2, characterized in that the anhydride and the benzotriazole are at one temperature from ii sets are. temperature from 100 to 150 ° C, preferably from 100 to 125 ° C, 4. Salt according to one of claims 1 to 3, characterized in that the anhydride consists of a tetrapropenyl, Polybutenyl, isooctadecyl or triacontenyl succinic anhydride consists.· 5. Salt according to one of claims 1 to 4, characterized in that that the amine from a primary tert-alkyl ronoamine. consists in which the amino group is bonded to the tertiary carbon atom and preferably 12 to 24 Contains carbon atoms. 6. Salt according to one of claims 1 to 4 »characterized in that the amine is preferably an alkanolamine Triethanolamine, is. 7. Use of an amine salt according to one of claims' before 1 to 6 as an additive to a lubricant, in particular 509816/1233 a metalworking lubricant. 8. Use according to claim 7, characterized in that the lubricant contains water. 509816/1233