DE2119448C3 - Stabilizing additive for lubricating oils and greases - Google Patents

Description

It is known (Journal of the American Society of Lubrication Engineers, October 1969, pp. 401 to 411), that the reaction products of polyhalopolyhydropolycyclodicarboxylic acids or derivatives thereof with certain amino compounds have desirable properties as additives for lubricating oils and greases own and also phosphorus salts such · :. ' Reaction products very effective as additives for Lubricating oils and greases are.

The invention is based on the object of further improved stabilizing additives for lubricating oils and To create lubricating greases on the basis of such reaction products.

Surprisingly, it has been found that mixtures of certain such reaction products and certain phosphate salts have improved properties as stabilizing additives for lubricating oils and own greases.

Accordingly, the invention relates to a stabilization additive for lubricating oils and greases, which is identified by this. that it consists of one Mixture of (1) one by reacting one to two molar proportions of amino compound and one Molar percentage of polyruilopolyhydiopolycyelodicarboxylic acid or anhydride at a temperature of H) to C formed reaction product and (2) a Salt of a phosphorus compound and an amino compound. wherein the amino compound of the reaction product (1) and the salt (2) independently of one another from the group of long-chain alkyl monoamines and the N-alkyldiaminoalkanes having 8 to 26 carbon atoms in the alkyl group and to 6 carbon atoms are selected in the alkane group.

The mixture prescribed according to the invention shows a synergistic effect. This is not the case Comparative and useful examples listed later, in which a direct comparison between the application of predetermined amounts of each of the components alone and an application of the made the same total amount of an additive consisting of a mixture of the two components became. According to the results of these examples, significantly higher operating loads were found a cress achieved when applying the mixture. This increase in load is surprising and could not have been foreseen according to the state of the art.

The stabilizing additive preferably contains a reaction product according to (1). which has been obtained by reacting one to two molar portions of amino compound and a molar portion of 5,6.7.8.9.9-HeXaChIOrO-U ₁ -IA 4a.5.8.8a - octahydro - 5.X - methano - 2.3 - naphlhylenedicarboxylic acid or its anhydride.

The above-mentioned 5.6,7.8.9,9-hexachloro-1.2.3.4.4a.5.8.8a - octahydro - 5.K - methano - 2,3 - naphthylenedicarboxylic acid or their anhydride. where the latter is also used here as an "A" -Anhy-

drid is called, as well as others for making of the reaction product usable acids can be represented by the general formula

(XCX) ₁ ,,

X \

y-c-y "

-C - OH

10

C-OH

25th

40

be reproduced; Here, X tin denotes a halose atom, in particular chlorine and / or; Bromine, a hydrogen atom or an alkyl radical with 1 to 10 and preferably 1 to 4 carbon atoms, where at least two of the groups X consist of halogen atoms, Y denotes a halogen atom, a hydrogen atom or an alkyl radical with 1 to 10 and preferably 1 to 4 carbon atoms , m is an integer from 1 to 4, / 1 is in the range 0 to 4 ^ and ρ is in the range 0 to 4.

The above formula illustrates the dicarboxylic acids. For the sake of simplicity, this is the appropriate one Anhydride is not shown; it is particularly evident from the above formula As stated, the preferred acid is 5,6,7,8,9,9-hexachloro-1,2,3,4,4a, 5,8,8a-octahydro-5,8-methano-2,3-naphthalenedicarboxylic acid. Other preferred acidic compounds include 5,6,7,8,9.9-Hcxachloro-l ^^^ a ^ S ^ a-octahydro-lAS.S-dimethano- 2,3 - naphthalenedicarboxylic acid-1,4,5,6,7,7 - hexachlorodicyclo- (2.2, l) -5-heptene-2,3-dicarboxylic acid and the corresponding anhydrides.

While the acid or anhydride is preferred, an ester of the acid can also be used. This is produced by reacting the acid with an alcohol, releasing water. The alcohol can contain 1 to 18 carbon atoms, preferably it contains 1 to 4 carbon atoms. Examples of suitable alcohols are _4S methanol, ethanol, propanol, butanol, pentanol and hexanol.

The said amino compound is used in the preparation of both components of the mixture Application, the amino compounds used for the two components being the same or different could be. The amino compounds are selected from the following groups:

I. Monoamines with 8 to 26 carbon atoms, here referred to as long-chain alkyl monoamines for the sake of simplicity. The monoamine can be a primary, secondary or tertiary alkylamine, preferably a primary or secondary alkylamine. So come into consideration: Octylamine. Nonylamine, decylamine. l'ndecylamine. Dodecylamine, tridecylamine, fetradecylamine. Pentadccylamine. Hexadecylamine, hepladecylamine. Octadccylamine. Nonadecylamine. Eicosylamine. Neicosylamine. Docosylamine. Tricosylamine. Tctracosylamine. Penlacosylamine and hexacosylamine. The amines can expediently be prepared from fatty acid derivatives, these include / .. B. tallow amine. hydrogenated sebum amine. Laurylamine. Slearylamine. Olcylamine.

55

f> o linoleylamine, soyamine, and coconutamine. Also suitable are the / i-alkylamines, also referred to as / i-amines in which the nitrogen atom to which (I or second carbon atom of the uppe ^r Alkylg is bound.

2. N-alkyldiaminoalkanes having 8 to 26 carbon atoms in the alkyl group and 2 to 6 carbon atoms in the alkane group. This includes in particular the N-alkyl-l, 3-diaminopropanes, in which the alkyl group contains 8 to 26 carbon atoms. Examples of such N-alkyl-1,3-diaminopropanes are:

N-Ociyl-1,3-diaminopropane,
N-nonyl-1,3-diaminopropane,
N-decyl-1,3-diaminopropane,
N-undecyl-1,3-diaminopropane.
N-dodecyl-1 3-diaminopropane.
N-tridecyl-1,3-diaminopropane.
N-tetradecyl-1,3-diaminopropane,
N-pentadecyl-1,3-diaminopropane,
N-hexadecyl-1,3-diaminopropane,
N-heptadecyl-1,3-diaminopropane,
N-octadecyl-1,3-diaminopropane,
N-nonadecyl-1,3-diaminopropane,
N-eicosyl-1,3-diaminopropane.
N-neicosyl-1,3-diaminopropane,
N-Ducosyl-1,3-diaminopropane,
N-tricosyl-1,3-diaminopropane.
N-tetracosyl-1,3-diaminopropane,
N - pentacosyl-1,3-diaminopropane and
N-hexacosyl-1,3-diaminopropane.

These include, in particular, the N-alkyl-1,3-diaminopropanes. in which the alkyl group is derived from sebum. The diamines on the market are mixtures in which amines with alkyl groups of 16 to 18 carbon atoms predominate. The corresponding substituted diaminoethanes, diaminopropanes, diaminobutanes, Diaminopentanes and diaminohexanes.

Other suitable diaminoalkanes are the / i-alkyldiamines. in which at least one alkyl group is bonded to a nitrogen atom. that on // - or second carbon atom of the alkyl group sits, z. B. an N- / i-alkyl-propylenediamine, in which the alkyl group Contains 17 carbon atoms. This compound can also be called N-1-methyl-heptadccylpropylenediamine are designated. Other, i'-alkyldiamines can also be used, including these N-l-methyl-alkyl-alkylenediamines, in which the alkyl component, excluding the methyl group, contains 7 to 25 carbon atoms; this means that the total number the carbon atoms in the alkyl group is 8 to 26 carbon atoms.

The mixture further comprises the salt of a phosphorus compound and the amino compound. Preferably the phosphorus compound is an acidic alkyl orthophosphate. including the Monoalkyl esters. Dialkyl esters and mixtures thereof: preferably at least one alkyl group is from Contain at least 6 carbon atoms, in particular from 6 to 20 or more carbon atoms than Examples of acidic orthophosphorus are: Acid monohexyl orthophosphate. acidic Dihcxylorthophosphat, a mixture of acidic mono- and Dihexyl orthophosphate. acid monoheptyl orthophosphate. acid diheptyl orthophosphate. a business

Mixture of acid mono- and diheptyl orthophosphate, acid monooctyl orthophosphate, acid dioctyl orthophosphate, a mixture of acid mono- and dioctyl orthophosphate, acid monononyl orthophosphate, acidic dinonyl orthophosphate. a mixture of acidic mono- and dinonyl orthophosphate, acidic Monodecyl orthophosphate, acid didecyl orthophosphate, a mixture of acid mono- and didecyl orthophosphate, acid monoundecyl orthophosphate, acid diundecyl orthophosphate, a mixture of acid mono- and diundecyl orthophosphate, acid monododecyl orthophosphate, acid didodecyl orthophosphate, a mixture of acid mono- and didodecyl orthophosphate, acid monotridecyl orthophosphate, acid ditridecyl orthophosphate Mixture of acidic mono- and ditridecyl orthophosphate, acidic monotetradecyl orthophosphate, acidic Ditetradecyl orthophosphate, a mixture of acidic mono- and ditetradecyl orthophorphate, acidic Monopentadecyl orthophosphate, acidic dipentadecyl orthophosphate, a mixture of acidic mono- and Dipentadecyl orthophosphate, acid monohexadecyl orthophosphate, acid dihexadecyl orthophosphate Mixture of acid mono- and dihexadecyl orthophosphate, acid monoheptadecyl orthophosphate. sour Diheptadecyl orthophosphate, a mixture of acidic mono- and diheptadecyl orthophosphate, acidic Monooctadecyl orthophosphate, acidic dioctadecyl orthophosphate, a mixture of acidic mono- and dioctadecyl orthophosphate, acid monomadecyl orthophosphate, acidic dinonadecyl orthophosphate, a mixture of acidic mono- and dinonadecyl orthophosphate, acid monoeicosyl orthophosphate, acid dieicosyl orthophosphate and a mixture of acid mono- and dieicosyl orthophosphate. Mixtures of the phosphates with alkyl groups can also be used different chain lengths can be used.

The phosphorus compound used to prepare the salt can also be obtained by reacting a aliphatic or aromatic alcohol with an alkylene oxide, d. H. Oxyalkylenation of alcohol, and then forming the phosphate therefrom. Aliphatic alcohols for oxyalkylenation may be saturated or unsaturated, and they preferably contain at least 4 and suitably 6 to 20 or more carbon atoms. Examples include: butyl alcohol, pentyl alcohol, Hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, dodecyl alcohol, Tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, hexadecyl alcohol, heptadecyl alcohol, Octadecyl alcohol, nonadecyl alcohol and eicosyl alcohol. These alcohols can be useful originate from fatty acids and accordingly also include z. B. lauryl alcohol, myristyl alcohol, palmityl alcohol, Stearyl alcohol, decylenyl alcohol, dodecylenyl alcohol, palmitoleyl alcohol, oleyl alcohol, linoleyl alcohol, Linolenyl alcohol and gadoleyl alcohol.

Suitable aromatic alcohols are phenol and, in particular, alkylphenols. The alkylphenols contain preferably at least 4 and especially 6 to 20 carbon atoms in the alkyl group. as Examples are: hexylphenol, heptylphenol, octylphenol, nonylphenol, dccylphenol, undecylphenol, Dodecylphenol, tridecylphenol, tetradccylphenol, pentadecylphenol, hexadecylphenol, heptadecylphenol, Octadccylphenol, Nonadecylphenol and Eicosylphenol as well as dialkyl- and trialkylphenols, in which the alkyl groups correspond to the above information. Furthermore, the polyalkylphenols one or more alkyl groups having 1 to 6 carbon atoms and one or more alkyl groups containing 6 to 20 carbon atoms.

Ethylene oxide is preferred for the oxyalkylenation of the aliphatic or aromatic alcohol, but propylene oxide, butylene oxide, pentylene oxide or hexylene oxide can also be used. The oxyalkylenated alcohol or the oxyalkylenated phenol expediently contains 2 to 12 and in particular 2 to 6 oxyalkylene groups. The oxyalkylenation is generally conducted at a temperature from ambient temperature to 175 ° C to 150 ⁰ C, preferably in the presence of a catalyst such as sodium hydroxide, potassium hydroxide, a tertiary amine or a quaternary hydroxide, in particular from 9G. If the oxyalkylenation is to be restricted to the introduction of an oxy group, the catalyst is used in the case of the alkanols, while it can be omitted in the case of the alkylphenols. Superatmospheric pressures can be used, e.g. B. in the range of 1.7 to 69 atm.

The oxyalkylenated aliphatic or aromatic alcohol is then _{reacted with P 2} O ₅ to form the desired phosphate. A molar proportion of P ₂ O ₅ or another suitable phosphorus oxide is reacted with one or two molar proportions of the oxyalkylenated compound. Generally an excess of P ₂ O _{5 is} used to ensure complete reaction. The reaction takes place at a temperature in the range from ambient temperature to about 110 ^° C. under essentially anhydrous conditions. The resulting free acid form of the phosphate is usually recovered as a viscous liquid.

The method of preparation of the reaction product from the polycyclic acid or the corresponding anhydride with the amino compound depends on whether the reaction product is prepared with a salt, prepared without releasing water, or an imide, amide, imide-amine, amide-amine or ester Release of water, should be. Mild conditions are used to manufacture the salt to avoid the release of water. The salt can be the mono- or half-salt or the double salt. If the mono- or half-salt is desired, the reactants are reacted in equal molar proportions of acid and amine. If the double salt is desired, the reactants are reacted in a proportion of 1 mole of acid and 2 moles of amine. The salt is suitably prepared by intimately mixing the reactants at ambient temperature (about 10 to about 32 ⁰ C), but it can also elevated temperatures, in general not 70 ° C exceeding applied, in particular if the reaction, for under pressure. B. 1.3 to 35 atm. is carried out. The mixing time should be sufficient to bring about an essentially complete reaction; B. 0.25 to 12 hours or more. Preferably a solvent is used, suitably an aromatic hydrocarbon, e.g. B. benzene. Toluene. Xylene. Ethyl benzene, cumene, or mixtures thereof.

Other suitable solvents are paraffinic hydrocarbons and ethers.

If the reaction is to take place with the release of water, the reactants become in a ratio of 1 molar proportion of the acid or its derivative and 1 to 2 molar proportions of the amino compound implemented under stricter conditions. If an I mid is to be formed, is preferred the anhydride used. If an amide is to be formed, the acid is preferably used. If an ester is to be formed, the acid or the anhydride can be used. Appropriate first solutions of one or both reactants in suitable solvents prepared, the reactants then mixed together and the mixture finally under reflux conditions heated, generally at 80 to 280 C and 1.3 to 35 Alm for a period of 0.5 to 12 hours. The water formed in the reaction is preferably continuously removed from the Reaction zone removed. When an N-alkyldiaminoalkane and an anhydride can be used as a reactant and the reaction mixture in the is refluxed in the manner indicated above, the reaction product is likely to pass from an imide-amine.

The salt of the phosphorus compound and the amino compound is expediently made by mixing of the two components at ambient or elevated temperature, in general Not exceeding 70 C and a pressure of atmospheric pressure to 7.8 atm or more. The mixing time is a few minutes to 24 hours or more, generally 0.25 to 4 hours. If desired, the phosphorus halligc Compound are mixed in a solvent with the amino compound.

In general, the basic salts of the phosphorus compound are used and the amino compound are preferred. The neutral salt becomes more sloichiometric by using it Equivalents made in terms of amino groups and acid groups. The individually applied Amounts of the reactants depend accordingly on whether the orthophosphate salt or a pyrophosphate salt is to be produced and whether a monoamine compound or a polyamine compound is used. The proportions of the reactants used in the preparation of the salt can be in the range from about 0.1 to 1 base equivalent per 1 acid equivalent or from about 0.1 to 1 acid equivalent per 1 base equivalent are, preferably 0.25 to 1 equivalent of one component per 1 equivalent of the other component.

The reaction product and the salt can each be obtained together with a solvent and can be used in this way to form the additive, but the solvent can also be used if desired be separated from one or both components. If the product is without solvent is obtained, a solvent can be added to the mixture to increase the solubility of the To improve additives in the substrate. Particularly suitable solvents are, for. B. alkylphenols and Polyalkylphenols in which the alkyl group or groups each contain 6 to 20 carbon atoms. The phenol can be used in a concentration of 5 and preferably 20 to 200%. based on weight of the active components of the additive.

The reaction product and the salt can be mixed in wide proportions, wherein an indication in the form of the ratio of halogen, especially chlorine, to phosphorus in the final Mixture is appropriate. The acids given above contain 6 chlorine atoms per molecule. When specifying in the manner mentioned, the reaction product and the salt in a halogen / phosphorus ratio, in particular chlorine / phosphorus ratio, from about 0.1 to 300 and preferably about 12 to 100 to be mixed.

The additive is intended for use in lubricating oil and especially in lubricating oil, which has stringent requirements must suffice. The lubricating oil can be of natural or synthetic origin. as Examples of mineral oils are oils derived from petroleum, such as engine lubricating oils, railway lubricating oils, Marine oils, transformer oils, turbine oils, differential oils, diesel lubricating oils, gear oils, cylinder oils and called specialty oils. Other natural oils include oils of animal, oceanic or of vegetable origin.

Many types of synthetic lubricating oils can also be stabilized. These include z. B. aliphatic esters, polyalkylene oxides, silicones, esters of phosphoric and silicic acids and high fluorinated hydrocarbons. Of the aliphatic esters, di- (2-ethylhexyl) sebacate is technically in used on a relatively large scale. Other suitable aliphatic esters are e.g. B. dialkyl azelates, Dialkyl suberates. Dialkyl pimelates, dialkyl adipates and dialkyl glutarals. As specific examples of such Esters are mentioned:

Dihexyl azelate.

Di- (2-ethylhexyl) -a7clate,

Di-3,5,5-methylhexyl-glutarai.

Di-3.5.5-trimethylpentyl glutarate,

Di (2-ethylhexyl) pimelate.

Di- (2-ethylhexyl) adipate,

Triamyl tricarballylate.

Pentacrythritol tetracaproate.

Dipropylene Glycol Dipelargonate and

1,5-pentanediol-di- (2-ethylhexanonate).

The polyalkylene oxides include, in particular, polyisopropylene oxide. Polyisopropylcnoxide - diethcr and polyisopropylene oxide diesters. Examples of silicones are methyl silicone and methyl phenyl silicone. and tetraisooclylsilicate is mentioned as an example of silicates. To the highly fluorinated hydrocarbons belong e.g. B. fluorinated oil and perfluorocarbons.

Other suitable synthetic lubricating oils are (1) neopentyl glycol esters, in which the ester group Contains 3 to over 12 carbon atoms, in particular Neopcntylglykolpropionate. Neopentyl glycol butyrate Ncopentylglykolcaproate, Neopentylglykolcaprylatc and Ncopentylglykolpclargonate; (2) trimethylol alkanes, e.g. B. trimethylolethane, trimethylolpropane, trimethylolbulane, trimethylpentane, trimethylol hexane, trimethylolhptane, trimethylol octane, tri methylol decane. Trimethylolundecane and trimethylol dodecane, as well as their esters and especially tri esters, in which the Estcrantcilc each 3 to 12 Koh Containing lcnstoffatomc and can be selected from the groups which are detailed above ii

509 622/17

Connection with the explanation of the neopentyl glycol esters were called; (3) tricresyl phosphate, trioclyl phosphate. Trinonyl phosphate. Tridecyl phosphate and mixed aryl and alkyl phosphates.

The additive can also be used for the stabilization of lubricating greases by association produced by one or more thickeners with an Ul of natural or synthetic origin will. It can be synthetic metal-based greases such as LilhiumfeUe. Sodium-free. Calcium fats. Barium fats. Strontium fats and aluminum fats, act. The grease can be one or contain several thickeners, e.g. B. silica. Soot. Talc or organically modified bentonite. Polyacrylates. Amides. Polyamides. Aryl ureas or methyl-N-n-octadecyl-tcrephthalomal. It can also be lubricating greases made from oxidized petroleum wax. Other types of grease, in which the additive can be used with advantage are, for. B. petroleum greases, whale greases. Wool fats and Greases made from inedible fats, tallow and butchery waste.

Oils of lubricant viscosity are also used as transmission media and hydraulic media Od. Like. Used and the additive can also be used to improve the properties of such oils will. The same goes for cutting oils. Rolling oils, soluble oils and dressing agents as well as or anti-rust oils.

The additive is added to the lubricating oil depending on the im Individual intended use in a concentration of about 0.01 to 25% and preferably about 0.05 to 10% based on the weight of the oil is added. This concentration information refer to the active ingredients without that optionally used solvents or solubilizing phenol. When used in usual Lubricating oils, the additive is generally in a concentration of 0.01 to 2 percent by weight of the Oil used. When used in lubricating oils for more severe operating conditions. e.g. hypoid gear oils. the additive is used in concentrations of about 1 to 20 percent by weight of the oil. Using of the oil to form a grease, the additive usually comes in one concentration from about 0.5 to 5 percent by weight, based on the oil, for use. When used in cutting oils, The additive can be used for rolling oils, soluble oils or drawing molds in concentrations of about 0.1 to 10 percent by weight and in the case of preservative or rust protection oils in concentrations of about 0.1 to ] 5% by weight or more based on the oil. Find application.

The additive according to the invention can be used together with other additives such as those incorporated in oils for specific purposes. In most cases it is advisable to add an additional antioxidant to the oil. Preferred antioxidants are those of the phenol type, including 7. B. tcrt.-butylpyxcalcchine. 2.6 - di - tert. - butyl - 4 - methylphenol. 2.4 - Dimethyl-6-tert-butylphenol. 2-tcrt.-Butyl-4-meihoxyphcnol. 2-lert-butyl-4-ethoxyphonic and the like. B. Metal deactivators. Dyes, viscosity index improvers. Flow point nicdriger. Antifoams and detergents. In some cases, in particular when used with the additional antioxidants specified above, a further synergistic effect and thus an even more pronounced improvement in the properties of the substrate is achieved.

The additive and the technical advantages that can be achieved are further illustrated below by means of examples.

Example I.

A number of different mixtures with different proportions of the components were produced manufactured. The reaction product and the phosphorus salt were each prepared separately and then used for Formation of the mixtures mixed together in different amounts.

The reaction product was prepared by First 4000 g of toluene were introduced into a reactor and then slowly, with stirring, 1700 g (4MoI) 5,6,7,8,9,9 - hexachloro - 1,2,3,4.4a.5.8,8a - oetahydro-5,8 - methano - 2,3 - naphthylenedicarboxylic anhydride were admitted; then 1070g (4MoI) Oleylamine added with stirring. The mixture was then held at reflux, with a total of 79 ml of water were collected. The reaction mixture was allowed to cool and then with Treated potassium carbonate. The resulting imide was obtained as a viscous amber-colored oil and analyzed; it had a bromine number of 23.5, corresponding to a theoretical bromine number of 23.8. a total nitrogen content of!, 97%. corresponding to a theoretical value of 2.08%, a total chlorine content of 32.1%. corresponding to a theoretical value of 31.75% and a molecular weight of 630. corresponding to a theoretical value of 671.

The phosphorus salt was made by mixing, at room temperature, of 268 g (1 equivalent) oleylamine and 37Og (1 equivalent) of a mixture of acid mono- and ditridyl cylon phosphate. The mixture then became heated on a steam bath and further mixed, the salt fell in the form of a clear, amber-colored, viscous liquid.

As already mentioned, the reaction product and the salt were produced in different ways mixed to form different mixtures. It separate mixtures were prepared with the following chlorine-phosphorus ratios: 6: 1. 1-: 1 and 24: 1. All of these mixtures are dark amber viscous liquids

Example 2

The mixture of this example was prepared from (1) the reaction product which is approximately the same way as in Example 1 by converting of the anhydride was made with oleylamine and (2) a salt of mixed acidic mono and Diiridccylorthophosphat and N-TaIg-U-di aminopropane. That used in this example) N-Talg-1,3-diaminopropane is available as a hand-made product and contains mainly 16 to 18 coals stoffalomc in the sebum group.

The reaction product was prepared in much the same manner as in Example 1, except that a larger batch was made. Hicrzi were 4250 g (10 moles) of the anhydride with 6 l of toluo mixed and then 2860 g (10 moles) of olicyclic amine was added with mixing. wonu: f the Gcmiscl

, / ■ ■

held at reflux while recovering 181 g of water became. The reaction mixture was treated with potassium carbonate, filtered and stored at 3 to Evaporated 4 mm Hg; there were 6627 g of a flowable product with a molecular weight of 638th compared to a theoretical molecular weight of 671st and a total chlorine content of 30.93%. corresponding to a theoretical chlorine content of 31.75%.

The salt was prepared by placing at room temperature 166 g (1 equivalent) of the N-TaIg-1,3-diaminopropane and 370 g (! Equivalent) of the mixed acidic mono- and dilridecyl orthophosphates were mixed, with subsequent heating of the Mixture on a steam bath with wciterer mixing. The salt fell as a clear amber color viscous liquid. The above components became different mixtures with chlorine phosphorus ratios of 12: 1. 24: 1, 48: 1 and 60: 1 mixed.

Example 3

A mixture was prepared by first dissolving the reaction product using the im Example 1 described anhydride with an N-alkyl-l, 3-diaminopropane, in which the Alkylgruppc Containing 18 carbon atoms was formed. This amine is commercially available, it is a / i-alkyl diamine. The reaction product was made by 1700 g (4MoI) of the »aft anhydride, 1500 g (4 moles plus 10% excess) of the above amine and 3000 g of toluene at one temperature refluxed up to 120 "C became. About 92 ml of water was removed during the reflux treatment, the latter was continued, until no more water was released. The reaction mixture was made with anhydrous potassium carbonate treated and filtered. A 100 g sample of the reaction mixture was used for removal of the solvent is distilled. The solvent-free product was a light amber oil with a basic nitrogen equivalent of 1.50 meg. corresponding the theoretical basic nitrogen equivalent of 1,515.

The salt used in this example was prepared by adding 830 g (5 weight equivalents) at room temperature. N-TaIg-1,3-diaminopropane and 1300 g (5 equivalent weights) mixed acidic mono- and dioctyl orthophosphate were blended. The components were mixed at room temperature and then heated on a steam bath and further mixed.

The reaction product and salt were then added in appropriate amounts to form mixtures with a chlorine / phosphorus ratio of 6: 1. 12: 1, 18: 1. 24: 1. 30: 1, 36: 1, 42: 1. 48: 1 and 54: 1 mixed.

Example 4

The mixture of this example comprised as one component a reaction product which is as in the example 1, except that stcarylamine was used in place of olcylamine was, and as the other component a salt, which is produced by the reaction of mixed acidic monofts and dioclyl orthophosphate and stearylamine was formed; the chlorine / phosphorus ratio was 24: 1.

Example 5

The mixture of this example comprised, as one component, a reaction product obtained by reaction of a molar proportion of 5,6,7.8.9,9-hexabromo-1.2.3.4.4a, 5,8.8a - octahydro - 1,4.5.8 - dimethano-2,3-naphthalenediearboxylic acid anhydride with a molar proportion of the amine mentioned in Example 3 and comprising N-1-methyl-heptadccylpropylenediamine / -'-diamines had been produced. The other component of the mixture consisted of a salt, that by reacting N-1-methyl-heptadecylpropylcndiamine was made with mixed acidic mono- and didecyl orthophosphorus. That The reaction product and the salt were used to form a mixture having a bromine / phosphorus ratio mixed by 36: 1.

Example 6

As stated above, the additive of the invention is of particular advantage when used in Materials that are subject to high temperatures during use. An example of such materials are lubricating oils for hypoid gears that meet stringent requirements in terms of conditions low speed high moment, high speed low moment and high moment Moment - high speed must suffice. The requirements are made even more stringent by that such oils must retain their lubricating properties over very long periods of time, for example with regard to the requirement not to have an oil change for a whole year or even longer or up to a mileage of 30,000 to 160,000 km or even during the entire service life of the Vehicle to have to make.

The Falex machine is a method for examining extreme pressure boiling oils. This test method is described in detail in "Lubricant Testing". EG Ellis. Scientific Publications (Great Britain) Limited, 1953, pp. 150 to 154. In short, the Falex machine consists of a rotating pin that runs between two V-shaped bearings that are spring-loaded against the pin and with means for changing the Load are equipped. The oil to be tested is poured into a metal trough, the pin and bearings are partially submerged. The machine was operated at 114, 227, 341 and 454 kg loads for 5 minutes each and at 568 kg load for 45 minutes. In particular, the temperature of the oil at each load and the torque at each load as well as the wear were determined as measured values; the latter was determined with a ratchet arrangement in which the teeth are advanced to maintain the desired load. Each tooth corresponds to about 5.5 · 10 * ⁵ cm. Preferable additives are those that give the oil a low temperature, low torque and low wear. The lubricating oil used in this example was a commercially available one; Lubricating oil of an SAE quality of 90, the oil was free of additives.

According to another test method, the machine was run for 5 minutes at each load, before 114 kg starting with an increase in load of 114 kg each until eating. The maximum load and di < The time, in minutes, at this load until the seizure is given, as well as the temperature of the oil

In this case a higher temperature is more favorable, since this means that the oil will work satisfactorily at a higher temperature.

Experiment 1 in Table 1 below was carried out using the lubricating oil containing no additive, thus constituting the An empty or comparative test.

Experiment 2 was using the mixture prepared according to Example 1 with a Chlorine / phosphorus ratio of 12: 1 carried out. The mixture was in a total additive concentration of 5 percent by weight, namely 3.38 percent by weight of the reaction product and 1.62 percent by weight of the salt.

Experiment 3 was using the mixture prepared according to Example 1 with a Stirred chlorine / phosphorus ratio of 24: 1. Again, the mixture was in a total

additive concentration of 5 percent by weight applied, consisting of 4.04 percent by weight of the reaction product and 0.96 percent by weight of the Salt.

Experiment 4 was using the mixture prepared according to Example 1 with a Chlorine / phosphorus ratio of 24: 1 carried out. The mixture was in a total additive concentration of 10 percent by weight, consisting of 8.07 percent by weight of the reaction product and 1.93 percent by weight of the salt.

It can be seen from the values in Table 1 that with the lubricating oil without an additive, i.e. H. while trying 1, seizure occurred under a load of 228 kg.

In contrast to this, all tests ran with those containing the additives according to the invention Lubricating oils flawlessly at 568 kg for the full duration of the 45-minute test.

Tabel

Attempt 1
Attempt 2
Attempt 3
Attempt 4

Moment, cm - kg load, kg

114 228 7-8 S. 6-7 12-20 7-8 17-19 7-8 10-15

341

19-21 19-23 16-19

454

23-25 22-24 19 22

56N

27-35 25-127 22 36

Trial 1 ..
Attempt 2 ..
Trial 3 ..
Trial 4 ..

S = eat.

Wear (number of teeth advanced on the ratchet wheel) Load, kg

114

0
0
0
0

228

o-s

5
2

341

3
1

454 568

34
46

32

Minutes at 568 kg load

45 45 45

oil temperature

at

568 kg load. C "

255 325 287

Example 7

The mixtures prepared according to Example 2 were also prepared in the same manner as in Example 6 examined. In this case, however, a lubricating oil made from a mixture of commercially available of additive-free lubricating oils blended to a 90 S.A.E.

The pins and bearings used in the machine have been replaced. It was found that exams at 500 kg were equivalent to those tests with the pins and bearings used first 568 kg have been carried, i.e. H. the values given in example 6.

The test series of this example were carried out with the mixtures prepared according to example 2. In all cases the total additive

concentration 10%. however, the chlorine phosphorus ratios from 12: 1 to 60: 1.

The experiment in Table II below was made carried out with the additive-free lubricating oil and thus represents the empty or comparison test.

Table II

Attempt 5
Trial 6
Trial 7
Trial 8
Attempt 9

121

107

Temperature. C. Load, kg 454 5 (K) 1 14th 9 228 Moment, cm - Load, kg kp 454 -23 - 7th -8th 16 341 -23 228 202 209 7th 8th Μ 24 -74 144 199 213 7th 9 Ι 4- 19-21 22- 23 146 193 195 7th 7th 14th 17th 19-20 141 186 182 6th 13th 17th 19-20 21 140 17th 17--19 132 341 16 - 175 173 170 173

5 (X)

21 25

20 24

20 23

17 22

...—- ■ »■ -

continuation

16

114 Wear I number of on Ratchet wheel advanced teeth) SlK) Minutes at 0 Lasl. ki! ... '(K) ky Lasl 0 21 0 ! 228 341 16 _ Trial 5 .. 0 12th 45 Experiment 6 .. 0 3 14th 45 Verruch 7 .. 3 45 Experiment 8 .. 4th 45 Experiment 9 .. 3 S = eat. 0-S 454 2 1 4th 2 2 4th 5

Experiment 6 was carried out using a mixture with a chlorine-phosphorus ratio of 12: 1, consisting of 7.05 percent by weight of the reaction product and 2.95 percent by weight of the salt.

Experiment 7 was carried out using the mixture with a chlorine / phosphorus ratio of 24: 1 carried out, consisting of 8.27 percent by weight of the reaction product and 1.73 percent by weight of the salt.

Experiment 8 was carried out using the mixture with a chlorine-to-phosphorus ratio of 48: 1 carried out, consisting of 9.05 percent by weight of the reaction product and 0.95 percent by weight of the salt.

Experiment 9 was carried out using the mixture with a chlorine / phosphorus ratio of 60: 1 carried out, consisting of 9.22 percent by weight of the reaction product and 0.78 percent by weight of the salt.

Again it can be seen that the .Additive according to of the invention were effective at 500 kg for the full duration of the 45 minute study. in the In contrast, with the oil without additive, seizure occurred at 228 kg.

Example 8

Another advantage of the additive of the invention is its high thermal and hydrolytic properties Stability. This is proven by the investigations given in the present example, in which the mixture prepared according to Example 1 with a chlorine / phosphorus ratio of 24: 1 in a commercially available Gear oil was tested to determine the limiting coefficient of friction. The investigation was done in a modified Bowden life machine with a pin and washer. The Bowden Life Method is described by Bowden and Ta bor in “The Friction and Lubrication of Solids ", 1954, p. 74. This method is also discussed in a publication by E. Rabinowicz, "The Boundery Friction of Very Well Lubricated Surfaces," A.S.L.E. 9th Annual Meeting Cincinnati, April 5, 1954, published in "Lubricating Engineering", July-August 1954 issue The modification used in the experiments given here rotates a highly polished steel disc in contact with an upwardly protruding rounded steel pin. The pen and the washer will be then immersed in a bowl containing the (<κ contains oil. The arrangement is inserted into a housing, which can be heated to change the target temperature; with those carried out here Ollcmperalur

at

5 (Xi leu Lasl. C.

209
213
195
182

Tests have done this in the range from 38 to 177 C. The test arrangement further comprises a speed control device for changing the number of revolutions of the disc and means for changing the load. With every attempt the wear or Break-in period from a gradual increase in the rotational speed to 196 rpm at 2000 g Load and decrease the speed of rotation to rpm, whereupon the speed of rotation increases 196 rpm is increased. The load changes in the range from 500 g to 2000 g, and the coefficient of friction was determined at speeds decreasing to 0.1. A voltage measuring circuit is used as a sensing device to convert the Frictional effects are used in equivalent electrical measurands, the latter being on a continuous basis running strip chart recorder.

Experiment 10 of Table III below was carried out with the gear oil containing 10 percent by weight of the mixture prepared according to Example 1 with a chlorine / phosphorus ratio of 24: 1, carried out.

The stated values are those at the stated various temperatures and rotational speeds determined coefficient of friction.

Table III

177 C experiment H)

0.070 0.074 0.072 0.070 0.068 0.062 0.057 0.055 0.053 0.950 0.034 0.024 0.020 0.015 ' 0.009 0.007 509 622Ί7Ι

Speed 38 C
Attempt H) 94 C "
Attempt H) 135 C
Attempt St. age
(U mini 0.073 0.082 0.082 196 0.075 0.088 0.085 175 0.077 0.092 0.085 155 0.080 0.095 0.085 137 0.082 0.098 0.085 110 0.085 0.104 0.087 88 0.087 0.104 0.093 65 0.090 0.102 0.097 47 0.092 0.100 0.098 35 0.097 0.098 0.102 23 0.102 0.105 0.115 12th 0.109 0.112 0.114 6th 0.109 0.121 0.110 3 0.104 0.134 0.117 I. 0.100 0.127 0.110 0.25 (1.098 0.127 0.104 0.1

iSiiiii

It can be seen from the data in Table III that the additive according to the invention has high stability and the oil has a low coefficient of friction. These properties show that the additive for applications in differentials with limited slip is effective.

Example 9

To determine whether the addition of water is harmful, another investigation was made into the same Manner as carried out in Example 8, with the exception that 1 weight percent water to the The oil used was added according to the investigation described in Example 8 and then a further test was carried out with the used oil. The results are in Table IV below listed.

The test series listed in Table IV (test 11) was carried out with the oil that the synergistic mixture prepared according to Example J. contained, it corresponds to the test series according to Example 8.

The values given are those given at different temperatures and rotational speeds Coefficient of friction.

It can be seen that the additive of the invention worked well in the presence of water. it is accordingly, very advantageous in those cases where water can get into the lubricating oil.

Table IV

speed
(U, min I

196

175

155

137

110

88

65

47

35

23

38 C 94 C Attempt 11 Attempt 11 0.079 0.060 0.082 0.062 0.084 0.060 0.085 0.062 0.085 0.063 0.088 0.065 0.090 0.067 0.092 0.070 0.093 0.072 0.095 0.079

135 C experiment 11

0.066 0.072 0.075 0.080 0.082 0.084 0.084 0.080 0.074 0.070

177 C attempt 11

0.062 0.060 0.060 0.058 0.055 0.053 0.05 ') 0.047 0.043 0.038

Speed
age
(U mini 38 C
Attempt 11 12th 0.091 6th 0.090 3 0.090 1 0.102 0.25 0.110 0.1 0.112

94 C
Attempt 11

0.077
0.098
0.109
0.100
0.075
0.058

135 C
Attempt 11

0.053
0.044
0.040
0.036
0.028
0.028

0.035
0.026
0.021
0.014
0.008
0.008

Example 10

As already stated, it will be a synergistic one Effect achieved when using the mixture of components compared to using it separately each component alone. This is going through

the data of this example prove! in which a comparison is made for the application (11 of the reaction product prepared according to Example 1 and (2) of the salt from the mixed acidic mono- and diisooclyl orthophosphates and N-TaIg-1,3-diaminopropane.

Next, two different mixtures of the reaction product and the salt with chlorine were phosphorus ratios of 36: 1 or 48: 1.

The values given in Table V below were in the Falex machine as in the above

Example 6 described, determined.

Experiment! 2 of the table was carried out using 10 percent by weight of the reaction product carried out.

Run 13 of the table was carried out using 10 percent by weight of the phosphate salt carried out.

Experiment 14 of the table was carried out using a mixture of 9.1 percent by weight of the Reaction product and 0.9 percent by weight of the phosphate salt with a chlorine / phosphorus ratio carried out by 36: 1. The total additive concentration was also 10 percent by weight in this case.

Run 15 was performed using a mixture of 9.3 percent by weight of the reaction product and 0.7 percent by weight of the phosphate salt carried out, the mixture had a chlorine / phosphorus ratio of 48: 1. Again fraud the total additive concentration 10 weight percent.

Table V

Attempt 12
Trial 13
Attempt 14
Attempt 15

Composition. Weight percent

Reaction product

10.0

9.1
9.3

Phosphate dep

10.0
0.9

0.7

Ratio Cl / P

only Cl

only P

36

48

Free.! conditions load
kg Line
min Tcmp.
t 114 Wear (number of on the ratchet wheel
advanced teeth) read
341 ..kg
454 568 6.X. 454 5 283 0 228 T 28 568 1.4 252 0 1 5 7th 4-S 682 0.1 235 0 0 τ -) IO 0-S 682 0.6 244 0 2 7th VS 0

12th 114 attempt 13th 99 attempt 14th 88 attempt 15th 85 attempt 92

Temperature, C
Load ki;

228 341 454 127 177 283 137 164 184 137 166 188 134 170 188

lortset / unii

568 682 250 219 235 212 244

22X moment , LlH - kj! ,1 454 568 Last, kü .14 14-17 19-32 42-69 - 15-19 20-23 23-25 29-S 8-10 13-15 19-21 22 24 25-29 7 - 9 14-16 21-23 23-25 25-28 7-8 8-9

682

35-S
32-S

S = eat.

From the values in Table V it can be seen that test 12, ie with 10 percent by weight of the reaction product alone, showed a certain effectiveness, but that here a rapid increase in temperature, a high torque and high tooth wear occurred under a load of 454 kg , which indicates a decrease in lubricating properties. In test 13, ie with 10 percent by weight of the phosphate salt alone, seizure occurred under a load of 568 kg. In contrast to this, in tests 14 and 15, ie when using synergistic mixtures according to the invention, there was no seizure up to a load of 682 kg. This proves a very desirable improvement in the lubricating properties of the mixtures compared to the use of one of the components alone. This improvement was unforeseeable and surprising.

Example Il

35

A comparison similar to that in Example 10 was used as further evidence of the synergistic effect carried out in which the phosphate = salt of mixed acidic mono- and ditridecyl orthophosphates and oleylamine was formed. So the amine used was a long chain alkyl monoamine. while in Example 10 an N-alkyldiaminoalkane was used as the amine for the preparation of the phosphate salt.

The values in Table VI below were determined in the same way as in Example 10.

Experiment 12 is identical to experiment 12 of Example 10.

Experiment 16 was carried out using 10 percent by weight of the salt from the acidic mono- and ditridecyl orthophosphates and oleylamine.

Run 17 was carried out using a mixture of 6.84 weight percent of the same Reaction product as used in experiment 12 and 3.16 percent by weight of the phosphate salt, as used in Experiment 16, with the mixture having a chlorine / phosphorus ratio of 12: 1. The total additive concentration was again 10 percent by weight.

Run 18 was carried out using a mixture of 8.13 weight percent of the same Reaction product and 1.87 percent by weight of the aforementioned phosphate salt stirred the mixture had a chlorine / phosphorus ratio of 24: 1. Again the total additive concentration was 10 weight percent.

Run 19 was carried out using a mixture of 9.05 weight percent of the same Reaction product and 0.95 percent by weight of the aforementioned phosphate salt stirred the mixture had a chlorine / phosphorus ratio of 48: 1. Here, too, the Gcsami additive concentration was 10 percent by weight.

The results of the tests are summarized in Table VI.

Table Vl

Attempt 12
Attempt 16
Attempt 17
Attempt 18
Attempt 19

Add
Gc
Reactionary
product immense /
weight pro?
Phosphai-
s; il / ιιημ.
cm
relationship
Cl P rrc
load .! means
Time
min en
Temp.
C. 114 Vcrschlci
prev
228 ß (number ι
! esc high
read
341 ler at the K
ncn tough
.kü
454 left wheel
ic)
568 682 10.0 All Cl 454 5 283 0 2 2 28 10.0 All P 568 1.7 210 0 0 6th 7th 7-S 6.84 3.16 12th 682 0.4 269 0 1 T 4th 8th 2-S 8.13 1.87 24 682 1.8 260 0 I. 1 3 4th 4-S 9.05 0.95 48 682 0.9 247 <> 1 4th 4th 0-S

continuation

it

114 228 Temperature, C t. kg 568 99 136 read -. '54 79 142 341 283 210 Attempt 12 90 137 177 193 213 Attempt 16 85 132 169 195 204 Attempt 17 97 133 169 133 210 Attempt 18 165 ! 84 Attempt 19 162

114 228 341 8-10 14-17 19-21 7-10 17-21 22-25 7-9 15-17 20-22 8-9 14-17 20-21 8-9 14-16 19-20

Moment, cm - kg
Load, kμ

454

42—

25-29

23-2Y

22-24

21-23

56 «

30-S
28-31

25-27
24-27

37-28
34-

S = eat.

From the values in Table VI it can be seen that in test 12 a certain effectiveness but it was observed that a rapid increase in temperature, a high moment and a high Tooth wear occurred at a load of 4M kg. This shows a reduction in the lubricating properties of the oil. In experiment 16 ~ d. H. with 10% of the phosphate salt alone, seizure occurred under a load of 568 kg. This contrasted with the experiments using the synergistic mixtures according to the invention no seizure up to one Load of 682 kg. This in turn proves the synergistic effect that occurs when the mixture is used of the components is achieved, a result that was unforeseeable and surprising.

Example 12

The mixture prepared according to Example 1 with a chlorine / phosphorus ratio of 6: 1 was used in a concentration of 1 percent by weight as an additive in a lubricating grease. The additive was incorporated into a commercial mid-continent lubricating oil with an SAE viscosity of 20. 92% of the lubricating oil was then mixed with 8 weight percent lithium stearate. The mixture was on 232 ° C heated with constant stirring. Thereafter, the grease became on with continued stirring 121 ° C and then slowly cooled further to room temperature.

The stability of the grease was tested according to ASTM method D-942. With this method a sample of the grease is placed in a bomb and at a temperature of 12PC held. Oxygen is introduced into the bomb and the time it takes for a pressure drop of 0.35 atm required is taken as the induction period. A sample of the grease with no additive reached the induction period in about 8 hours. In contrast, the sample of the grease, containing 1% by weight of the additive, the induction period did not exceed 100 hours.

The following examples serve to further illustrate the invention and that therewith achieved technical advantages when using a salt of a phosphate of an oxyalkylenated Alcohol and an amino compound as a salt component of the synergistic mixture.

Example 13

The reaction product was prepared by first charging about 4000 grams of toluene into a reactor were and then slowly with stirring 1700 g (4MoI) 5,6,7,8.9.9 - Hexachloro - 1,2,3.4,4a, 5,8,8a - octahydro - 5.8 - methano - 2,3 - naphthyl dicarboxylic acid anhydride were admitted; Then 1070 g (4 mol) of oleylamine were added with stirring The mixture was then set to reflux held, with a total of 79 ml of water were caught. The reaction mixture was cooled

ίο left and then treated with potassium carbonate The imide formed was obtained as a viscous amber-colored oil and analyzed. It had one Bromine number of 23.5, corresponding to a theoretical bromine number of 23.8. a chlorine content of 32.1%. ent corresponding to the theoretical value of 31.75%. unc has a molecular weight of 630, corresponding to a r theoretical value of 671.

The mixture of this example was prepared by mixing them in the above manner provided the reaction product with a phosphate salt obtained by reacting oleylamine with polyoxy Ethylenated nonylphenol phosphate with about 5 oxyethylene groups in the middle had been produced The oxyethylene nonylphenol phosphate is one

Liquid at room temperature and has a phosphorous reverberation of 4.9% and a specific weight at 25 ° C of 1.07. The salt was prepared using 108 g (0.5 equivalents) of oleyl at room temperature amine and 236 g (0.4 equivalents) of the polyoxyethy

lenited nonylphenol phosphate were mixed with subsequent heating on a water steam bath and further mixing. The SaI; became a clear amber viscous liquid obtain.

The reaction product and the salt prepared in the above-mentioned manner were combined into one Mixture mixed with a chlorine / phosphorus ratio before 24: 1. This mixture was in various which concentrations are used as an additive in lubricating oil, as in a following example will be explained in more detail.

Example 14

The mixture of this example contained the react prepared according to Example 13 as the single component

tion product and as the other component eir

Salt made from polyoxyethylene nonylphenol phosphate with an average of 1.5 oxyethylene groups unc

N-TaIg-1,3-diaminopropane was prepared. There:

Oxyethylene nonylphenol phosphate was a liquid

fluid at room temperature and had a Phos

phosphorus content of 5.8% and a specific weight at 25'C of 1.08. The used N-tallow-1,3-di Aminopropane is commercially available and contains primarily 16 to 18 carbon atoms in the tallow group. The salt was prepared by mixing at room temperature, 51.7 g (0.1 equivalents of polyoxyethylene nonylphenol phosphate:

and 0.1 equivalents of the N-tallow-1,3-diaminopropane. After mixing at room temperature, the mixture became homogeneous to form Lösunu heated.

Example 17

B e i s ρ i

15th

To form the synergistic mixture, the reaction product was first prepared using the anhydride described in Example 13 and an N-alkyl-i ^ -diaminopropane in which the alkyl group contained 18 carbon atoms. This amine is commercially available; it is a / 7-alkyldiamine. The reaction product was prepared by refluxing 1700 g (4 moles) of the "A" anhydride, 1500 g (4 moles plus 10% excess) of the amine and 3000 g of toluene at a temperature of up to 120 ^° C. About 92 ml of water were added removed during the reflux treatment, the latter continued until no more water was released. The reaction mixture was treated with anhydrous potassium carbonate and filtered. A 100 g sample of the reaction mixture was distilled to remove the solvent. The solvent-free product was a light amber-colored oil with a basic nitrogen equivalent of 1.50 mg / g, which corresponds to the theoretical basic nitrogen equivalent of 1.515.

The salt of this example was prepared by adding 5 equivalent weight of stearylamine at room temperature and 5 equivalent weights of oxypropylenated tridecyl alcohol phosphate with an average of 2 oxypropylen groups were mixed. The components were mixed at room temperature and on a The steam bath is heated and mixed further.

The Rcaktionsprodukl and the SaI / were then in amounts to form mixtures with chlorine phosphorus ratios of 6: 1, 12: 1. 18: 1, 24: 1, 30: 1. 36: 1, 42: 1, 48: 1 and 54: 1 mixed up.

Example 16

To prepare the mixture of this example, the reaction product of 1.4.5, 6,7,7 - hexachlorodicyclo - (2,2,1) - 5 - heptene - 2,3 - dicarboxylic acid anhydride and N-olcyl-U-diaminopropane educated. The other component of the mixture was a salt obtained by reacting N-oleyl-1,3-diaminopropane with polyoxyethylated nonylphenol phosphate, which contained an average of 1.5 ethylene groups. The reaction product and the salt were used to form a Mixture with a chlorine / phosphorus ratio of 48: 1 mixed.

The mixture of this example contained, as a component, a reaction product obtained by reaction of a molar fraction of 5.6.7,8.9.9-hexabromole, 2.3,4.4a.5.8.8a - octahydro - 1.4.5.8 - dimethano-2,3-naphthalenedicarboxylic acid anhydride with a mole fraction of the commercially available / i-diamine that N-1-methyl-heptadccyl-propylenediamine became. The other component of the mixture consisted of a salt that by reaction of N-1-methyl-heptadccyl-propylenediamine was made with oxyäthylcniertcm octylphenol phosphate. The reaction product and the salt were then blended to form a mixture having a chlorine-to-phosphorus ratio of 36: 1.

The Falex machine was again examined the effect of the additives according to the invention, in which the phosphorus compound of a oxyalkylenated alcohol phosphate is used. In these test series, the ones used hold Mixtures with a chlorine / phosphorus ratio of 24: 1, the influence was used as a variable in this example different concentrations of this mixture tested.

Run 1 of Table VIl below was carried out using the lubricating oil that did not contain any Contained additive, it is therefore an empty or comparative test.

Experiment 2 was carried out with the lubricating oil, which here had an additive concentration of 6 percent by weight in total contained, consisting of 4.55 percent by weight of the reaction product and 1.45 percent by weight of the salt.

Experiment 3 was carried out with the lubricating oil, which here contained a total of 7 percent by weight of the additive, consisting of 5.31 percent by weight of the reaction product and 1.69 percent by weight of the salt, carried out.

Experiment 4 was carried out with the lubricating oil, which here had a total additive concentration of 8 percent by weight contained, consisting of 6.06 percent by weight of the reaction product and 1.94 percent by weight of the salt.

Experiment 5 was carried out with the lubricating oil, which here had a total additive concentration of 9 percent by weight contained, consisting of 6.82 percent by weight of the reaction product and 2.18 percent by weight of the salt.

Run 6 was performed using the lubricating oil that had a total additive concentration here of 10 percent by weight, consisting of 7.58 percent by weight of the reaction product and 2.42 percent by weight of the salt.

Table VI

Attempt I.
Attempt 2
Attempt 3
Attempt 4
Attempt 5
Trial 6

22K Temperature. C. 454 233 7th 114 22nd 14th Moment.
load .M 18th cm -
kg 1 kg 454 114 110 226 8th -8th S. 14- 20th 81 130 192 219 7th 9 15th 20th 20th 23-24 87 107 152 209 8th 9 14th 17th 19th 21 23-24 77 127 197 222 8th 9 14th 17th 20th 22nd 24-27 94 130 195 7th 9 17th 21 24 25 83 133 195 8th 17th 21 24 25 84 17th MI 159 128 167 162 164

568

24 31

25 29
25 31
25 29
24 29

509 622/170

26th

"orisct / ung

Trial 1 .. 0 Attempt 2 .. 0 Trial 3 .. 0 Trial 4 .. 0 Trial 5 .. 0 Experiment 6 .. 0 S = hressen.

Wear and tear (number of. In the Klinkr; id advanced / similar

Load, kg 114 I 228 I 341 I.

o-s

0
0
0
1
0

3
0

3 3 1 0 568

12th
15th
18th
16
18th

Minutes at
kg load

45

45
45
45
45

From the values in Table VI it can be seen that the oils with the different concentrations of the additive of the invention in which the phosphorus component is comprised of an oxyalkylenated alcohol-phosphate exists, all effective in the investigations over the full 45 minutes with a load of 568 kg was. Also of importance is the fact that the oil did not darken after the tests had occurred; this again demonstrates the high thermal and hydrolytic stability of the mixture.

Example 18

The technical advantage of the additive of the invention in terms of high thermal and hydrolytic Stability is also proven by the studies cited in this example, in which the Mixture prepared according to Example 13 with a chlorine / phosphorus ratio of 24: 1 in a commercially available Gear oil was investigated to determine the limiting coefficient of friction. The investigation was done in the modified Bowden life machine with pin and disc, like the one above has been described.

Run 7 of Table VIII was used of the gear oil with a content of 10 percent by weight of that prepared according to Example 13 Mixture that had a chlorine / phosphorus ratio of 24: 1 was carried out.

The stated values are those at the stated various temperatures and rotational speeds determined coefficient of friction.

From the values in Table VIII it can be seen that the mixture according to the invention has a high Has stability and the oil has a low coefficient of friction granted. These properties show that the additive has door applications in differentials is effective with limited slip.

Table VIII

20th

Speed 38 C age attempt (U min) 0.087 65 0.090 47 0.093 35 0.105 23 0.105 12th 0.106 6th 0.103 3 0.100 1 0.092 0.25 0.095 0.1

C.
Trial 7

0.097
0.097
0.098
0.100
0.100
0.099
0.100
0.097
0.094
0.093

C.
Trial 7

!!!temperature

at

5fi8 kg load. V

233
226
219
209

177 C Experiment 7

0.095
0.097
0.095
0.098
0.196
0.092
0.086
0.072
0.056
0.050

0.079 0.075 0.074 0.067 0.043 0.027 0.022 0.012 0.008 0.005

35 Example 19

Speed 38 C
Trial 7 94 C
Trial 7 age
lrpm) 0.072 0.084 196 0.075 0.085 175 0.077 0.088 155 0.079 0.090 137 0.082 0.092 110 0.085 0.093 88

135 C

Trial 7

0.086
0.088
0.090
0.090
0.090
0.093

177 C
Trial 7

0.085
0.085
0.085
0.085
0.084
0.080 To determine whether the addition of water is harmful. Another study was carried out in the same manner as in Example 18, with dei

Except that 1 percent by weight of water is added to the The oil used was added according to the investigation described in Example 18 and then another Hrulung was carried out with the used oil. The results are in Table IX below

45 listed.

The series of tests listed in Table IX was carried out with the oil that contained that according to Example 13 produced mixture contained, it corresponds to the test series according to Example 19.

The values given are those for various Determined Icmpcratures and rotational speeds Coefficient of friction.

It can be seen that the synergetic mixture works well when mixed in the presence of water.

was sam, the mixture is accordingly very advantageous In cases where water can get into the lubricating oil.

Table IX

6o

Speed 38 C age Try S (U mini 0.072 196 0.077 175 0.079 155 0.079 137

¹ MC
Trial 8

0.080
0.082
0.080
0.080

C.

Trial 8

0.066
0.074
0.074
0.068

177 C attempt 8

0.051 0.050 0.050 0.048

continuation

Speed 38 C ') 4 C 135 C 177 C age
(U mini Trial 8 Trial 8 Trial 8 Trial 8 110 0.080 0.082 0.067 0.047 88 0.080 0.084 0.063 0.044 65 0.082 0.087 0.060 0.040 47 0.084 0.087 0.058 0.037 35 0.084 0.088 0.055 0.033 23 0.085 0.097 0.052 0.030 12th 0.081 0.087 0.047 0.026 6th 0.084 0.079 0.040 0.024 3 0.083 0.070 0.042 0.021 1 0.086 0.087 0.0 « 0.017 0.25 0.092 0.101 0.045 0.012 0.1 0.093 0.100 0.035 0.012

Example 20

The synergistic effect achieved according to the invention when using the mixture of components compared to the separate application of each component alkine is further enhanced by the Data of this example. Here is a comparison

drawn for the sole use of (1) the reaction product according to Example 13 and (2) the phosphate salt, the reaction of oleylamine and polyoxyethylene nonylphenol phosphate with im Means about five oxyethylene groups was produced. The synergistic mixture of reaction product and salt was prepared to establish a chlorine / phosphorus ratio of 24: 1.

Run 9 of Table X was carried out using 10 percent by weight of the reaction product.

Run 10 of the table was carried out using 10 percent by weight of the phosphate salt carried out.

Experiment 11 of the table was carried out using a mixture of 6.82 percent by weight of the Reaction product and 2.18 percent by weight of the phosphate salt carried out. The mixture became that is, used in a total additive concentration of 9 percent by weight.

From the values in Table X it can be seen that when using the synergistic mixture of Components seizure did not occur until a load of 954 kg, while each of the components was applied eating alone occurred at loads of 454 and 682 kg. This again proves the pronounced synergistic effect Effect achieved by using the mixture compared to using it separately each component alone.

Table X

Attempt 9.
Attempt 10
Attempt 11

Composition. Weight percent

Reaction product

10.0
6.82

Phosphalsal /

10.0

Temperature. C.
Load, kg

114

99 80 83

228

127 125 134

454,

283
190
199

568

209
219

682 795 226 - 234 248

909

272

Attempt 9
Attempt 10
Attempt 11

load

454
682
954

Experiment 9 ...
Attempt 10 ..
Trial 11 ..

S = eat.

ediniii
/ hurry.
min nong
Temp ..
C " 114 10 228 341 32 moment
read
454 cm - kg
t. kg
568 682 16 5 283 8 ~ - 8th 14-17 19th 22nd 42 69 34 1.0 226 7— 8th 14-16 21 22nd 25 27 29 30 32-1 0 298 7— 15-17 21- 24-27 27-30 29—

114

0
0
0

909

35 -37

Wear (number of teeth advanced on the ratchet wheel)
Load, kg

228

2 1 0

341

568 682 795 9 <W 2 0-S --- - 5 3 6th 23

example

The mixture prepared according to Example 13 was introduced with 65 oil with an SAE viscosity of 20. 92

in a concentration of 1 percent by weight as the lubricating oil were then 8 percent by weight

Used as an additive in a lubricating grease. The additive lithium clearate is mixed. The mixture was;

was heated in a commercially available Mid-> C '") ntincnt lubricant-232" C, with constant stirring. Dana

29 30

the grease was increased with continued stirring and the time required for a pressure drop of 0.34 A

121 C cooled and then slowly further down to room is required, is called the induction period gene

temperature cooled. men. A sample of the grease without A.dd

The stability of the grease was found to have an induction period of about 8 hours

ASTM method D-942 tested. In this test 5, on the other hand, there was a sample of the lubricating grease

a sample of the grease is placed in a bomb containing 1 percent by weight of the additive,

introduced and at a temperature of 121 "C induction period in more than 100 hours n <

held. Oxygen is introduced into the bomb. not reached.

Claims (10)

Patent claims: 1. Stabilizing additive door lubricating oils and greases, characterized in that that it consists of a mixture of (Ij one by reacting one to two molar proportions of amino compound and one molar proportion of polyhalopolyhydropolycyclodicarboxylic acid or anhydride at a temperature of 10 to 280 ° C formed reaction product and (2) a salt of a Phosphorus compound and an amino compound, the amino compound being the reaction product (1) and the salt (2) independently of one another from the group of long-chain alkyl monoamines and the N-alkyldiaminoalkanes having 8 to 26 carbon atoms in the alkyl group and 2 to 6 carbon atoms are selected in the alkane group. 2. StabiJisierungsadditiv according to claim 1, characterized characterized in that it contains a reaction product according to (1), which by reaction from one to two molar proportions of amino compound and one molar proportion of 5,6,7,8,9,9-hexachloro-1,2,3, 4,4a, 5,8,8a - octahydro - 5,8 - methano - 2,3 - naphthylenedicarboxylic acid or the anhydride of which has been obtained. 3. Stabilizing additive according to claim I or 2, characterized in that it consists of a mixture whose long-chain alkyl monoamine component contains 8 to 26 carbon atoms. 4. Stabilizing additive according to claim 3, characterized in that it consists of a mixture whose long-chain alkyl monoamine component is a fatty acid amine. 5. Stabilizing additive according to claim 4, characterized in that it consists of a mixture exists, whose long-chain alkyl monoamine component is an oleylamine or stearylamine. 6. Stabilizing additive according to one of claims 1 to 5, characterized in that it consists of a mixture whose N-alkyldiaminoalkane component an N-alkyl-aminopropane is. 7. Stabilizing additive according to one of claims 1 to 6, characterized in that it consists of a mixture whose phosphorus component is an oxyalkylenated alcohol phosphate is. 8. Stabilizing additive according to claim 7, characterized in that it contains a reaction product according to (2) , the phosphate component of which consists of an oxyalkylenated alkylphenol phosphate with 1 to 12 oxyalkylene groups of 2 to 6 carbon atoms and 4 to 20 carbon atoms in the alkyl group. 9. Stabilizing additive according to one of claims 1 to 6, characterized in that it contains a reaction product according to (2), the phosphorus component of which consists of an acidic alkyl orthophosphate consists. 10. Stabilizing additive according to one of claims 1 to 6, characterized in that it contains a reaction product according to (2), the phosphorus components of which are composed of mixed acidic Mono- and dialkyl orthophosphates, in which at least one alkyl group has 6 to 20 carbon atoms contains.