NO742708L - - Google Patents

Description

S lubricant additives

The present invention relates to lubricants for joints and

more particularly, certain new compounds which are useful as lubricant additives, or which in certain cases may be useful in the manufacture of lubricant additives.

Among the numerous types of additives used in

mixture of lubricants, especially, but not exclusively, car lubricants

agents, are different surface-active materials. For example, dispersants are incorporated, especially ash-free dispersants

agents, in lubricants to disperse carbon particles and other insoluble materials such as decomposition products and oxydasjcnsp.ro-

ducts of fuel, in the oil reediet which is the main component of the sraarremedien. The insoluble materials are thus suspended in

the oil medium and is prevented from forming deposits that could have an adverse effect on the operation of the machine.

According to the present invention, an amide of an alkylphenoxy-substituted aliphatic carboxylic acid is obtained where the alkyl group substituted on the phenoxy unit contains at least 30 carbon atoms.

The present invention also includes a fuel or lubricant preparation comprising a larger amount of a liquid hydrocarbon fuel or lubricating oil, and a small amount of an amide of an alkylphenoxy-substituted aliphatic carboxylic acid, where the alkyl group substituted on the phenoxy group contains at least 30 carbon atoms.

According to Norwegian patent application 740669, a compound has been provided which is a condensation product of an alkyl-substituted phenol, preferably a p-alkyl-substituted phenol, in which the alkyl substituent contains at least 8 carbon atoms, and at least one. halogen-substituted, preferably α-halogen-substituted, aliphatic carboxylic acid or ester thereof. The carboxylic acid may be substituted with two or more halogen atoms, but preferably has a single halogen substituent. With regard to the condensation reaction by which the compounds are prepared, bromine is better suited than chlorine as the halogen substituent, as the former is more reactive. For economic reasons, however, it is preferred to use a chlorine-substituted carboxylic acid or ester thereof.

According to another feature of the invention in application 74o669, a compound with the general formula has been provided:

wherein: (a) R , which are the same or different, are hydrogen; alkyl of 1-16, preferably 1-4, carbon atoms; halogen, preferably chlorine, or a group R in the ortho position in relation to the oxygen atom bound to the aromatic nucleus, is a group with the formula:

where

(i) n, being the same or different, is an integer, preferably from 1 to 6; (ii) Z, which are the same or different, is a sulfur chain with

the formula f-S> where m is from 1 to 4, preferably 1 or 2;

v 'm

a methylene group; or a residue of a carbonyl-substituted carboxylic acid or derivative thereof, which residue has the formula:

where R 7 , which are the same or different, is hydrogen, methyl or the group which is the same or different, is an integer, preferably 0, 1 or 2, and most preferably 0; Y, which are the same or different, is hydroxy, alkoxy, amino or the group -0 M where M is an ammonium, amino or monovalent metal cation; (iii) R 4 , which are the same or different, are hydrogen; alkyl of 1-16, preferably 1-4, carbon atoms; halogen, preferably chlorine; hydroxy; a group with the formula 4 or R^ form together with a residue of a carbonyl-substituted carboxylic acid constituting a group Z, a lactone ring; (iv) R 1 , which are the same or different, are hydrogen; an alkyl group of 1-16, preferably 1-4, carbon atoms; halogen, preferably chlorine; or hydroxy provided that no more than one of the groups R is hydroxy; and (v) R , which are the same or different, are hydrogen; an alkyl group of 1-7, preferably 1-4, carbon atoms; halogen, preferably chlorine; or is as R 2 ; (vi) provided that one group R 3 in the ortho position in relation to the oxygen atom bound to the aromatic ring is hydrogen, halogen, methyl or ethyl; (b) R, which may be the same or different, is straight or branched alkylene of 1-20, preferably 1-12, and most preferably 1-4, carbon atoms; (c) R"<*>", which are the same or different, is hydrogen or the residue of one hydroxy compound, preferably the residue of an alkanol of 1-4 carbon atoms; and (d) R 2 , which are the same or different, is alkyl of at least 8 carbon atoms.

The groups R 2 in the above compounds, or in the case of the condensation products defined above from application 74o669 the alkyl groups derived from the alkyl substituted phenols, contain at least 8 carbon atoms and may contain at least 30, preferably at least 50 carbon atoms.

In the case of the condensation products defined above, the alkyl substituted phenol starting material may have one or more additional substituents on it. aromatic ring, and these correspond to the groups RJ in the compounds of the above general formula. When no substituent, apart from the alkyl substituent corresponding to R 2 , is present, this corresponds to all the substituents RJ o being hydrogen, and such compounds are strongly favored.

Norwegian patent application 74o669 also includes methods for the production of new compounds. It thus includes a method in which at least one alkyl-substituted phenol, where the alkyl substituent contains at least 8 carbon atoms, is condensed with at least one halogen-substituted aliphatic carboxylic acid or ester thereof. In its preferred embodiment, the method comprises the condensation of at least one p-alkyl substituted phenol with the formula:

with at least one halogen-substituted aliphatic carboxylic acid or ester thereof of the formula: while forming a compound of the formula: where R, R 1 , R ? and RJ ^ is as indicated above, and A is chlorine or bromine. The halogen-substituted carboxylic acid or ester thereof is preferably an α-chloro- or α-bromocarboxylic acid or ester thereof, and in this case R may be a methylene group ( derived from an α-haloacetic acid or ester thereof) or may be the group where each B is hydrogen or a pendant alkyl group (e.g.

v

when derived from an α-halopropionic acid or ester thereof).

The groups R and R"'' in the product from the process can thus be determined by choosing the appropriate halogen-substituted carboxylic acid or ester thereof as starting material. The precise nature of R<1> is not critical, but can be chosen from a wide range of groups. R" *" is thus hydrogen when derived from a halogen-substituted carboxylic acid. When derived from an ester of a halogen-substituted carboxylic acid, the esterifying group constituting R"<1>", i.e. the residue of a hydroxy compound, may be any any well-known esterification group such as an alkyl group derived from an alkanol, or a glycol monoether or polyoxyalkylene glycol monoether group.

Alternatively, the hydroxy compound from which R"<*>" is derived may be a di- or poly-hydroxy compound and the remainder will have unused hydroxy groups; or the hydroxy compound may be a di- or poly-hydroxy compound in which one or more, but not all, of the hydroxy groups are replaced by groups of the formula:

in addition to that shown in the preceding formula (A).

2 3

Likewise, the precise nature of the groups R and R can be determined by the choice of the appropriate alkyl-substituted phenol starting material, and furthermore, in a special case described below, by the reaction conditions. Thus, when each RJ is hydrogen or halogen or alkyl, this is provided by choosing the appropriate substituted phenolic starting material. Similarly, compounds wherein RJ is a group of the formula: can be prepared from phenol sulfides or derivatives thereof, which have the appropriate substituents to provide the required groups R^", R^ and R^. In this case Z will be a sulfur chain. Compounds where Z is methylene can likewise be prepared from the appropriate o-methylene-phenyl derivatives. A particularly useful source of o-methylene-phenyl derivatives are phenol/formaldehyde condensation products. Finally, products where Z is a residue of a carbonyl-substituted carboxylic acid or derivative thereof, is prepared by using as starting materials the compounds that form the subject of Norwegian patent applications 4217/73 and 741399- These compounds can be prepared by condensing an alkyl-substituted phenol with a carbonyl compound, for example with the formula:

where R<7>, p and Y are as indicated above, as described in more detail in the aforementioned applications.

In all of the foregoing variations, the alkylphenol starting materials have the appropriate substituents which, with one exception, constitute the groups R₂", R₂ and R₂. The exception occurs when R₂" is a hydroxyl group. In this case, the starting material will contain two or more phenolic hydroxyl groups, and the halogen-substituted carboxylic acid may be used in an amount sufficient to react with a single phenolic hydroxyl group or with all such groups.

It is highly desirable to use an acid acceptor to neutralize the hydrogen halide released by the condensation of the alkylphenol with the halogen-substituted carboxylic acid or ester. such acid acceptors are well known, and any suitable material can be used for this purpose, e.g. a tertiary base such as pyridine. However, the preferred acid acceptor is a metal base such as an alcoholic solution of an alkali metal hydroxide, particularly sodium or potassium hydroxide, or an alkali metal or alkaline earth metal alkoxide. The latter can be easily made by dissolving the metal in an alcohol, such as methanol or ethanol, in a known manner. The acid acceptor is preferably used in the stoichiometric amount required to neutralize the hydrogen halide. When a halogen-substituted carboxylic acid is used, as opposed to its ester, the base will preferentially neutralize the carboxyl group of the acid, and additional amounts of base will be necessary to first neutralize the acid. In this case, all the base necessary to neutralize both the carboxylic acid and the hydrogen halide can be added to the reaction mixture initially. Alternatively, sufficient base to neutralize the carboxylic acid may be added initially and the remainder added dropwise during the reaction at a rate sufficient to keep the reaction mixture alkaline. similarly, when an ester of the halogen-substituted carboxylic acid is used, all the base required to neutralize the hydrogen halide may be added initially or the base may be added in portions during the course of the reaction. The portionwise addition of the acid acceptor is the preferred method.

Condensation reactions proceed easily in the presence of the acid acceptor and can be carried out at room temperature. on the other hand, relatively high reaction temperatures can also be used up to the decomposition temperature of the reaction mixture. However, in order to obtain a more easily controllable reaction at a rate that is faster than at room temperature, an intermediate reaction temperature of from 6o°C to 150°C is preferred, with a temperature of from 70°C to 100°C being the optimum reaction ion temperature. Under these conditions, the reaction is usually complete within an hour, as indicated by the fact that no additional base is consumed. Dropwise addition of the acid acceptor facilitates the determination that the reaction is complete in this way. Alternatively, a pH indicator or a pH meter can be used.

If desired, the condensation reaction may be carried out in an inert solvent-reaction medium, such as a hydrocarbon solvent or alkanol solvent. Examples of such inert solvents are benzene, toluene, xylene, n-butanol, 2-ethylhexanol and mineral oil, in particular a mineral oil with lubricating viscosity.

After completion of the reaction, the product can, if desired, be washed with water to remove the halide salt of the acid acceptor formed during the reaction. Alternatively, the reaction product can be acidified and washed with aqueous alcohol, e.g. aqueous methanol.

The present invention is thus directed in one aspect to amides of certain of the new compounds from application 740669. That is amides containing at least one alkyl substituent with at least 30 carbon atoms, and in which the group -O-R<1> in the preceding formula (A) is replaced by the residue of an amine, or in the case of the condensation products from application 74o669, amides of carboxylic acid groups obtained from the halogen-substituted aliphatic carboxylic acid or amides where an amine residue replaces the esterifying group in carboxylic acid ester groups derived from halogen-substituted carboxylic acid esters.

The present invention therefore includes compounds with the general formula:

where:

(a) R or as above,

(b) R is the residue of an amine,

(c) R 1 is alkyl of at least 30 carbon atoms, and

(d) each R<10>, which are the same or different, is hydrogen; alkyl of 1-16, preferably 1-4 carbon atoms; halogen, preferably chlorine; or an R<10-> group in the ortho position to the oxygen atom bound to the aromatic ring is a group with the formula:

where

(i) w is an integer from 1-6,

(ii) each X, whether the same or different, is a sulfur chain of the formula {S)- where m is 1 - 4) preferably 1 or 2; or a methylene group, 19 (iii) each R", which is the same or different, is hydrogen; alkyl of 1-16, preferably 1-4, carbon atoms; halogen, preferably chlorine; hydroxy; or a group of the formula -O-R-C -O-R1}0 (iv) each R 20, which are the same or different, is hydrogen; alkyl of 1-16, preferably 1-4 carbon atoms; halogen, preferably chlorine; or hydroxy,

v) provided that one, but not more than one, of the groups R1^ and R^ is hydroxy; and

1R

(vi) each R , which are the same or different, is hydrogen; alkyl of 1-29, preferably 1-4 carbon atoms; halogen, preferably

Q

chlorine; or is like R .

In a preferred embodiment of the invention, R Q is one

•alkyl group, especially a branched alkyl group, with 50 - 200 carbon atoms. Such alkyl groups can be derived from long-chain olefins such as

poly-a-olefins which may have molecular weights j. the range 700 to 3,000, more preferably 900 to 1,500, and especially approx. 1,000. Examples of suitable poly-α-olefins are polyisobutylenes (PIB) and polypropylenes such as those commercially available under the trade names "Hyvis" and "Indopol". The preferred groups R o are residues of aliphatic di- or polyamines, the preferred group R is methylene, and the preferred substituents R<1>^ are hydrogen.

Am id products according to the present invention can be prepared from the products of application 740669 by amidation, using an amine which can be selected from a wide range of amines such as those of the formula: where R<11>, which are the same or different, are a hydrogen atom or a hydrocarbon, amino-substituted hydrocarbon, hydroxy-substituted hydrocarbon, alkoxy-substituted hydrocarbon, amino, carbamoyl, thiocarbamoyl or guanyl group. Preferred amines are di- or poly-amino compounds, i.e. where at least one group R<11> is an amino-substituted hydrocarbon, and particularly preferred amines are alkylene polyamines with the general formula:

12

where s is an integer, and R is a divalent alkylene group. Pre-12

usually R is an ethylene group, and s is from 1 to 6, and more preferably from 3 to 5. Examples of such amines are ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and mixed higher polyethylene polyamines. Other alkylene polyamines such as di-(1,2-propylene)-triamine or N-(2-amino-ethyl)-trimethylene-diamine can be used if desired. Such alkylene polyamines can first be reacted with a Y-lactone > preferably Y_butyro-lactone as described in British patent document 1,054'. 370, or with dicyandiamide as described in British patent document 1,068-235.

Useful higher polyamines have molecular weights from 300 to 1000 or 5000, preferably 400 to 600, especially those prepared by polymerization of ethyleneimine. The process of polymerization of ethylenimine gives mixtures of polyethylene polyamines with a wide range of molecular weights. These can be divided into mixtures with narrower ranges of molecular weights, the ones indicated being the most useful for the present invention.

Other polyamines useful in the present invention are commercially available mixtures such as that consisting essentially of a mixture of isomeric pentaethylene hexamines of the formula ClnH„0N/ and related hexamines containing piperazine rings and

IO 2o o

12 carbon atoms. The average molecular weight of the mixture is approx. that for pentaethylene-hexamine, i.e. 233?and the mixture contains a preponderance of amines with 2-4 primary amino groups and at least two secondary amino groups.

Other suitable diamino compounds that can be used are N-dialkylamino-alkylamines of the general formula:

where R1^ is a divalent alkylene group, and R<1>^ and R<1>^ are alkyl. Examples of such N-dialkylaminoalkylamines include dimethylaminomethylamine, dimethylaminoethylamine, dimethylaminopropylamine, dimethylaminobutylamine, dimethylaminoheptylamine, diethylaminomethylamine, diethylaminopropylamine, diethylaminoamylamine, dipropylaminopropylamine, methylpropylaminoamylamine and propylbutylaminoethylamine.

Other suitable diamino compounds are bis -(N-aminoalkyl)- and N-((3-aminoalkyl)-piperazines of the formula:

where R<1>^ is the alkylene with 1-3 carbon atoms, and R<1>^ is hydrogen or a hydrocarbon or aminoalkyl group with 1-3 carbon atoms.

Various other di- or polyamine compounds which can be used in the present invention are N-(2-aminoethyl)-ethanol", amine and hydroxyethyl-triethylene-tetramine.

The amine can be reacted with the new compounds from application 740669 in approximately equimolar amounts. In this embodiment, when the preferred alkylene-polyamine coreactants or other amines which initially contain two or more primary amino groups are used, the reaction product formed will contain one or more remaining primary amino groups. Alternatively, with the preferred alkylene polyamines, the amine can be reacted with up to twice the molar amount of the new compounds from application no. 740669 or even more. It is not necessary to use exact molar amounts of the two reactants. Useful additions can be obtained by using e.g. two moles of the new compounds from application 740669 and 1.5 moles of the alkylene polyamine, giving a mixture of products.

Alternatively, the starting materials are reacted in equimolar amounts and one or more remaining amino groups are reacted with a carboxylic acid to form an amine salt, amide thereof or imidazoline or condensed with aldehydes, ketones or mixtures thereof or with mixtures of aldehydes and phenols to form Mannich bases, in a manner known in and of itself. Alternatively, the amine can first be reacted with suitable amounts of the carboxylic acids, aldehydes, ketones or mixtures of aldehydes and phenols to obtain an amine with a remaining primary or secondary amino group, and the amine formed is reacted with the new compounds from application 74o66Q. In another embodiment of the present invention, the amine is an α-alkylene polyamine in which a primary amino group has been reacted, either before or after the amine has been reacted in equimolar proportions with the new compounds from application 740669, with an alkenyl-substituted succinic acid or anhydride thereof containing from 8 to 200 carbon atoms in the alkyl substituent. Such substitutes are preferably residues of relatively low molecular weight polymers or olefins, such as isobutylene or propylene, or oligomers of such olefins. In light of the foregoing, it will be understood that the ratio between the co-actants can be varied depending on the desired end product.

The preceding method according to the invention can be easily carried out by heating the coreactants together, and a preferred reaction temperature is from 50 to 250°C, more advantageously 130 to 220°C, and preferably from 180 to 220°C. An inert solvent such as; xylene, toluene or mineral oil can be used.

The reaction can be carried out most conveniently in a vessel open to the atmosphere. If desired, however, the reaction can be carried out under vacuum or low pressure conditions or under a nitrogen blanket. The reaction is usually complete within 1-6 hours, with 2-4 hours being most common.

As mentioned, the preferred amine starting materials are di- or poly-amino compounds, from which new products according to the present invention can be prepared, which contain two or more nitrogen atoms. Such products are preferred, for example, as lubricants.

However, the present invention also includes products derived from ammonia or monoamines, in particular primary or secondary monoamines. Such products can be prepared in the same way as the new compounds according to application no. 740669 by reacting an alkyl-substituted phenol with the appropriate amide of a halogen-substituted carboxylic acid. That is to say, the reaction can be carried out in the same way as in application no. 740669, except that an amide of a halogen-substituted carboxylic acid is used instead of the acid itself or its ester. Preferred amides in this case are those derived from ammonia or monoamines with 1-8, preferably 1-4 carbon atoms. The monoamides formed can be used as starting materials in clays for the removal of lubricant additives. These can be reacted with the preferred di- or poly-amines in a "trans-amidation" reaction analogous to a trans-esterification reaction. This can be carried out by heating the amides derived from ammonia or monoamines with the preferred di- or poly-amines, e.g. at a temperature of 100 - 250°C, preferably 180 - 220°C, while the more volatile raonoarain or ammonia is driven off.

Another method by which the preferred lubricant additives according to the invention can be prepared is in the same way as the new compounds in application 740669, except that an amide derived from a di- or poly-amine and a halogen-substituted carboxylic acid is used instead of the acid and the ester itself hence.

As mentioned, the present invention comprises lubricant preparations containing the new amides according to the invention, which are preferably used in an amount from 0.3 to 15% by weight, preferably 1-6% by weight, calculated on the total weight of the lubricant.

Particularly preferred additives according to the present invention are the polybutyl-phenoxyacetamides derived from polybutenes with a molecular weight of 900-2,800, and polyethylene-polyamines with an average of 4-6 amino groups, produced by reacting polybutyl-phenoxyacetic acid or an ester thereof with polyethylene-polyamine in a raol ratio of from 2:1 to 2:1.5.

The invention also encompasses additive concentrates comprising a smaller quantity of lubricating oil and a larger quantity of one or more of the additives according to the present invention, and lubricant packages comprising a smaller quantity of lubricating oil and a larger quantity of a combination of one or more of the additives according to the present invention and at least one other lubricant additive.

The lubricating oil used in the lubricant preparations according to the invention can be any known synthetic ester oil, such as dioctyl sebacate. The preferred oils, however, are mineral oils with lubricating viscosity of a well-known type.

The present invention will now be illustrated by the following examples.

Example 1

(a) Preparation of n-butyl polyisobutylphenoxyacetate

To a solution of 107509 (0.1 mol) of PIB-phenol prepared by the alkylation of phenol with polyisobutylene of molecular weight 1,000, using etBF^/phenol complex as catalyst, and 22.6 g (0.15 mol) of n-butyl- chloracetate in 100 ml of xylene, a solution of 8.19 (0.15 mol) sodium methoxyd in 40 ml of anhydrous methanol was added slowly over the course of 1 hour. The addition was carried out at 100°C, and after the addition was complete the solution was heated at 100°C for a further 1 hour. The solution was washed with 50 ml of 10% hydrochloric acid followed by 3 x 80 ml of aqueous methanol (1:4). After drying over magnesium sulfate, the solvent was removed from the solution. The yield was 102 g.

A sample of this product was saponified with an excess of aqueous potassium hydroxide, acidified with hydrochloric acid and then washed with portions of aqueous methanol (1:4) until acid-free. The acid value of the thus formed PIB-phenoxyacetic acid (3°>5mg KOH/g) indicates a transfer of 73%.

(b) Reaction of n-butyl polyisobutylphenoxyacetate with tetraethylenepentamine to form an amide

A mixture of 50 g of PIB-phenoxybutyl acetate and 39 tetraethylene-pentamine was heated at 200°C for 4 hours under nitrogen. After dilution with mineral oil, the mixture was filtered to obtain a clear product.

Example 2 to 17

Production of n-butyl-polyisobutylphenoxyacetate

A solution of sodium methoxide prepared by dissolving 43.0 g (1.87 mol) of sodium in 600 ml of dry methanol was added to a stirred solution of 1.943 g (1.7 mol) of polyisobutylphenol (prepared by boron trifluoride-catalyzed alkylation of phenol with 1,000 M.V. polyisobutylene) and 281.4 g (1.87 mol) of n-butyl chloroacetate in 850 ml of xylene at 100°C. The addition took 1.75 hours, and the solution was then stirred at 69°C for 2 hours.

The solution was stirred with 225 ml hydrochloric acid/water (1:4) and allowed to separate. The organic layer was then washed with 3 x 500 ml water/methanol (1:4), white spirit (b.p. 62-68°C) being added to aid the separation. The solution was dried over magnesium sulfate, filtered and subjected to stripping to 170°C under vacuum. One thus obtained 1-7349 (79%) intermediate product.

Saponification figure: 40.4 mg KOH/g.

A number of intermediate esters (Examples 3 - 17) were prepared by the same general procedure, details of which are given in Table 1. In certain cases, namely in Examples 3, 4, 5, 6 and 12, the acid treatment was omitted, and the number of aqueous methanol washes was reduced to 1 or 2. In some cases the reaction solvent was mineral oil, as shown: in Table 1.

Example 18

Preparation of tetraethylene-pentamine-amide from polyisobutyl-■phenoxyacetic acid

1-500 g (1.03 mol) of the product from example 2 was stirred with 119 g (0.63 mol) tetraethylenepentamine at 200°C in a nitrogen atmosphere for 4 hours. Evolved n-butanol was allowed to escape during the reaction. The product was cooled, diluted with 276 g of mineral oil and filtered in petroleum ether solution. Removal of the solvent gave 1,650 g of the amide (91% yield).

%N 2.2 (calculated 2.2%)

Anhydrous TBN 51.5 mg KOH/g

Examples 19 to 39

One. series of amides were prepared by the same general procedure as in Example 18, full details being given in Table 2. The products were prepared as approx. 85% concentrates in mineral oil, except in example 23 and also where the intermediate products were produced in oil, in which cases the final products were approx. 60% oil concentrates. A product (Example 37) was prepared without oil addition.

For some preparations, especially where volatile amines were used, it was necessary to modify the preparation methods. With dipropylenetriamine (Example 27), the reactants were heated under reflux at 170°C for 1/2 hour, and at 200°C for 3 hours, and finally at 200°C for 1.5 hours without a cooler. With ethylenediamine (Example 28), the reactants were heated under reflux in toluene solution for 1/2 hour, the toluene was distilled off, and the heating was continued at 200°C for 3 hours without a cooler. With dimethylaraino-<p>rop<y>lamine (Example 29) an excess of the amine was used, and the mixture was heated under reflux at 160°C for 4 hours. The excess amine was distilled off, and the mixture was heated at 200°C for 3 hours.

Example 4o

A solution of sodium methoxide prepared by dissolving

12.7 g (0.55 mol) sodium in 150 ml dry methanol was added slowly to a stirred solution of 571.5 g (0.5 mol) polyisobuty1-phenol (from 1,000 M.V. PIB) and 83 g.(0 .55 mol) of n-butyl chloroacetate in 438 g of mineral oil at 7o°C. The reaction was continued for 2 hours, and the mixture was then subjected to vacuum stripping at 190°C and filtered in petroleum ether solution. The ester obtained had a saponification value of 21.7 mg KOH/g.

600 g (0.23 mol) of the ester was reacted for 4 hours at 200°C with 26.9 g (0.14 mol) of TEPA, and the product was filtered.

Example 4l

Another sample of n-butyl-PIB-phenoxyacetate was prepared in oil as described in Example 40, except that the ester was subjected to vacuum stripping in the presence of a filter aid and was filtered undiluted.

1-976 g (0.74 mol) of this ester was reacted for 4 hours at 200°C with 70.0 g (0.37 mol) TEPA, and the product was filtered.

Example 42

Preparation of N,N-dimethyl-polyisobutyl-phenoxyacetamide

A solution of 5.7 g (0.105 mol) of sodium methoxide in 28 ml of dry methanol was added over 1 hour to a stirred solution of 72.7 g (0.07 mol) of polybutylphenol (from 1,000 M.V. PTB) and 12, 89 (0.105 mol) N,N-dimethyl-chloroacetamide in xylene at 100°C. The reaction was continued for a further 1 hour, and the solution was washed with 3 x 50 ml of 20% hydrochloric acid and with 3 x 80 ml of 80% aqueous methanol.

Drying and removal of the solvent gave the product.

Example 43 to 45

Free amino groups in the amide from Example 38 were further reacted with an aldehyde to form a Schiff's base, and aldehyde and a phenol to form a Mannich base, and with a carboxylic acid to form an amide. Details for these preparations are given in Table 3-Example 46

900 g (0.609 mol) of an intermediate ester, similar to that of Example 11, was reacted with 72.0 g (0.381 mol) TEPA at 200°C for 4 hours under nitrogen. 163 Q (0.153 mol) of polyisobutenyl-succinic anhydride (prepared from 650M.V. PIK) was added and the reaction continued at 200°C for a further 4 hours. The mixture was cooled, 192 g of diluent oil was added, and the product was filtered into petroleum ether solution.

The suitability of the products according to the invention for use as ashless dispersants in lubricants was determined by "MS VC and Petter AV-B Engine tests" by "Panel Coker Tests" and by spot tests. The VC tests were carried out using standard methods on two preparations containing experimental additives.

Formulation A was a 10W/30 blend, formulated to meet US Specification MIL-L46152, containing commercially available metal sulfonate detergents, viscosity index improver and anti-oxidant/anti-wear additive, and in which the ashless dispersant typically present (4.5% ), was replaced with the experimental additive, i.e. in an amount of 4.5% or an equivalent active dose. The mixture had a sulphated ash content of 1%.

■Preparation B was similar to preparation A, but had a sulphated ash content of 0.5% and contained ashless corrosion inhibitors.

After the tests, grades were given according to the state of the test machine in the usual way, and these grades were as follows:

"Additive X" is a commercially available ashless dispersant consisting of a borated Mannich base of a polyisobutylphenol.

The "Petter AV-B" tests were also carried out according to the standard method and grades (maximum 10) were given in the usual way on the basis of the condition after testing the various parts of the test machine.

Carbon deposition in the grooves of the test machine was also measured. Rillecarbon and the total grade (maximum 100) obtained from the individual grades were as follows:

The test mixture used in the AV-B tests was an SAE 30 mixture, formulated to meet the requirements of US Specification MIL-L-2104-C, containing commercially available metal sulfonate detergents, corrosion inhibitor and antioxidant/antiwear additive, and in which the ashless dispersant which is usually present (3>5%), was replaced with the experimental addition, also at 3.5%, except where stated.

The Panel Coker tests were carried out using the same trial mixture as for the AV-B test, and were carried out for 3>5 hours in a slightly modified form of the usual apparatus. Instead of continuous oil spraying, the oil was sprayed against the aluminum plate which was held at 316°C using a cyclic method consisting of a spraying method for 15 seconds and then a 45 second period during which the paddle was stationary. The apparatus was further modified to allow a flow of moist air through the sump above the oil surface at a rate of 2.3 l per hour.

The area of the sump not normally submerged in oil was graded for percent cleanliness in much the same way that a machine piston is graded after a test, such as the "Caterpillar 1-G" test, to obtain a percent accuracy. (100 = completely clean).- It is believed that the above test agrees well with the "Caterpillar 1-G Engine Test".

In the spot samples, the experimental additives were dissolved in mineral oil

(<V>210<=><3j>5cS) in an amount of 4%, except where the additives were prepared as 60% concentrates in oil', in which cases 5.8%

addition was used. Carbon black ("Spheron 9" from Cabot Carbon 'X Co, average particle size 27 nm) (1%) was added and the mixtures (10 g) were stirred for 1 hour using an "Ultrasonic Generator" in 127 mm x 25 mm test tube. The tubes were then stored at 50°C for 16 hours and allowed to cool. Drops of oil, taken from the top 13 mm, were placed on chromatography paper using a fine glass rod. The spots were then allowed to develop for 24 hours and were scored as follows:

A = Carbon well dispersed

B = Carbon moderately well dispersed

C = Carbon poorly dispersed

D = Carbon not dispersed

The grades obtained in the "Panel Coker" and stain tests are indicated in Tables 2 and 3• The "Panel Coker" tests were carried out at a trial additive concentration of 3.5%, except where the products were prepared as 6o% concentrates in oil where 5.1% of the products were used. In the same "Panel Coker" test, a grade of 61.2 was achieved with "Additive X". In the spot test, a sample of the mineral oil without addition received a grade of D.

Claims (22)

1. Compound, characterized in that it is an amide of an alkylphenoxy-substituted aliphatic carboxylic acid where the alkyl group on the phenoxy unit contains at least 30 carbon atoms. 2. Connection according to claim 1, characterized in that the alkylphenoxy-substituted aliphatic carboxylic acid is a condensation product of an alkyl-substituted phenol in which the alkyl substituent contains at least 30 carbon atoms, and at least one halogen-substituted aliphatic acid or ester thereof. 3. Connection according to claim 2, characterized in that the alkyl-substituted phenol is a p-alkyl-substituted phenol. "4" Compound according to claim 2 or 3, characterized in that the half-substituted carboxylic acid or ester thereof is a bromine- or chlorine-substituted carboxylic acid or ester thereof. 5. Compound according to claims 2-4, characterized in that the alkyl substituent of the alkyl-substituted phenol contains at least 50 carbon atoms. 6. Connection according to claim 3, characterized in that the p-alkyl substituted phenol has the general formula: and the halogen-substituted carboxylic acid or ester thereof has the general formula: where: (a) each R 1 , which are the same or different, is hydrogen; alkyl 10 with 1-16 carbon atoms; halogen; or a group R in the ortho position to the oxygen atom bound to the aromatic ring is a group. with the formula: where: (i) w is an integer from 1-6, (ii) each X, which' are the same or different, is a sulfur chain of the formula f v S )' ■ m where m is from 1 - 4; or a methylene group; (iii) each R<1>^, which are the same or different, is hydrogen; alkyl of 1 to 16 carbon atoms; halogen; hydroxy; or a group with the formula (iv) each R 20 , which are the same or different, is hydrogen; alkyl of 1 to 16 carbon atoms; halogen; or hydroxy; (v) provided that one, but not more than one, of the groups R1^ and R^ is hydroxy; and (vi) each R 18°, which are the same or different, is hydrogen; alkyl of 1-29 carbon atoms; halogen; or is as R g; (vii) provided that a group R <10> in the ortho position to the oxygen atom attached to the aromatic ring is hydrogen, halogen, methyl or ethyl; (b) each R, which is the same or different, is straight or branched chain alkylene of 1-20 carbon atoms; (c) each R<1> , which are the same or different, is hydrogen or the residue of a hydroxy compound; (d) each R 1 , which is the same or different, is alkyl of at least 30 carbon atoms; and (e) A is chlorine or bromine. 7. Compound according to claim 6, characterized in that at least one R group is alkylene with 1-4 carbon atoms. 8- Connection according to claim 6 or 7, characterized in that at least one R^ group is the residue of an alkanol with 1-4 carbon atoms. 9. Connection according to claim 6-85 characterized in that at least one R<9>' group is derived from a poly-a-olefin with a molecular weight of from 700 to 3,000. 10. Connection according to claim 9, characterized in that the poly-a-olefin has a molecular weight of from 900 to 1,500. 11. Compound according to claim 9 or 10, characterized in that the poly-α-olefin is a poly-isobutylene or a polypropylene. 12. Compound according to claims 6-11, characterized in that all R^ groups are hydrogen. 13. Compound according to claims 1-12, characterized in that it is prepared by amidation of the alkylphenoxy-substituted aliphatic carboxylic acid using an amine of the general formula: H0 N f R <12> NH V H 2 v ' s 12 where s is an integer, and R is a divalent alkylene group. 14- Connection according to claim 13, characterized in that the amine is ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or pentaethylenehexamine. 15. Compound, characterized by the general formula: where R, R ^ and R<10> are as stated above in claims 6-12, and where R^ is the remainder of. a. amine. 16 <.>" Method according to claim 15, characterized in that R° Q is the residue of an amine with the general formula: H2 N f R <12> NH )■ H 12 where s is an integer, and R is a divalent alkylene group. 17. Connection according to claim 16, characterized in that the amine is ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or pentaethylenehexamine. 18- Procedure, characterized in that (a) an amine is reacted with the condensation product of an alkyl-substituted phenol in which the alkyl substituent has at least 30 carbon atoms, and a halogen-substituted aliphatic carboxylic acid, or (b) an alkyl-substituted phenol where the alkyl substituent has at least 30 carbon atoms is condensed with the reaction product of an amine and a halogen-substituted aliphatic carboxylic acid. 19. Method according to claim 18, characterized in that a polyethylene polyamine with 4-6 amino groups is reacted with the condensation product of a polyisobutyl-substituted phenol and monochloroacetic acid. 20. Lubricant preparation, characterized in that it comprises a larger quantity of a lubricating oil and a smaller quantity of a compound according to claims 1 - 17- 21. An additive concentrate, characterized in that it comprises a smaller amount of a lubricating oil and a larger amount of one or more of the compounds according to claims 1 - 17. 22. Additive package, characterized in that it comprises a smaller amount of lubricating oil and a larger amount of a combination of one or more compounds according to claims 1 - 17, and at least one other lubricant addition.