CA1062696A - Lubricating oil dispersant containing a polyisobutyl phenoxy substituted acetic amide - Google Patents

Abstract

C A N A D A

"LUBRICANT ADDITIVES"

ABSTRACT OF THE DISCLOSURE

Novel compounds, useful as lubricant additives, are amides of alkylphenoxy substituted aliphatic carboxylic acids wherein the alkyl group substituted on the phenoxy moiety contains at least 30 carbon atoms.
Lubricant compositions containing the novel compounds are also disclosed.

Description

~06Z696 ~ s invention relates to lubricant additives, more particu~arly to lubricant oil dispersants.
Amongstthe numerous types of additives used in blend-ing lubricants, particularly but not exclusively auto-motive lubricants, are;various surface active materials.For example dispersants, particularly ashless dispersants, are incorporated in lubricants in order to disperse carbon particles and other insoluble materials such as decom-position products and fuel oxidation products in the oil medium which is the major constituent of the lubricants.
The insoluble materials are thus suspended in the oil medium and prevented from forming deposits which can de-leteriously affect engine operation.
According to the present invention there is pro-vided a lubricating oil dispersant containing a polyisobutyl phenoxy substituted acetic amide, said dispersant being pre-pared by the process comprising ti) reacting a polyisobutyl substituted phenol wherein said polyisobutyl substituent contains from 50 to 200 carbon atoms with a Cl_4 alkyl chloroacetic ester to form an intermediate mlxture con-- taining polyisobutylphenoxy-substituted acetic ester, and (ii) reacting said intermediate mixture with an ethylene polyamine without removing unreacted C50_200 polyisobutyl-phenol to convert said acetic ester to carboxylic amide, said dispersant having a high amide and low polyisobutyl-phenol content.
The present invention also includes a lubricating oil containing a dispersing amount of such a dispersant.
In our copending Patent Application No 193507 there is provided a compound which is a condensation product of an alkyl-substituted phenol, preferably a p-alkyl-substituted phenol, in which the alkyl substltuent contains at least 8 carbon at~ms and at least one halogen substituted, preferably ~-halogen substituted, aliphatic carboxylic acid or ester thereof.
Application No 193507 also includes processes for preparing the novel substances of that application. Thus, ~pplicatioll No i9350, inci~d~s a process w~herein at ieast one alkyl-substituted phenol, in which the alkyl f~ ' ~

.. . .
, subs~ituent contains at least 8 carbon atoms, is condensed with at least one halogen suhstituted ali-phatic carboxylic acid or ester thereof.
It is highly desirable to employ an acid acceptor to neutralise the hydrogen halide liberated in the condensation of the alkylphenol with the chloroacetic acid ester. Such acid acceptors are well known and any suitable material can be used for this purpose, e.g. a tertiary base such as a pyridine. However, the preferred acid acceptsr is a metal base such as an alcoholic solution of an alkali metal hydroxide, part-icularly sodium or potassium hydroxide or an alkali metal or alkaline earth metal alkoxide. The latter can ~ ;
be readily prepared by dissolving the metal in an alcohol, such as methanol or ethanol, in well known manner. The acid acceptor is preferably used in the stoichiometric ~ quantity required to neutralise the hydrogen halide.
; All the base required to-neutralise the hydrogen halide may be added initially or the base may be added in portions throughout the reaction. The portion-wise addition of the acid acceptor is the pre~erred technique.
The condensation reaction proceeds very readily in the presence of the acid acceptor and may be carried out at ambient temperature. Conversely, comparatively high reaction temperatures can also be used up to the decomposition temperature of the reaction mixture.
However, to provide a more easily controllable reaction .
~- at a rate more rapid than at ambient temperature, a compromise reaction temperature of from 60C to 150C
is preferable, a temperature of from 70C to 100C being C ! 3-~062696 the optinum reaction temperature. Under these conditions the reaction is usually complete within one hour, completion being denoted when no further base is ~ ~-consumed. Dropwise addition of the acid acceptor facilitates the indication of the completion of the reaction in this way. Alternatively, a pH indicator or a pH meter may 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, especially a mineral oil of lubricating viscosity.
After completlon of the reaction the product may, if desired, be washed with water to remove the halide ,~ :
salt of the acid acceptor formed during the reaction.
~; Alternatively the reaction product may be acidified and washed with aqueous alcohol e.g. aqueous methanol.
Preferred amines are ethylene polyamines having ~ ~ 20 the general formula:-; ~ H2 N ~ R NH t s H

wherein Rl2 is an ethylene radical and s is an integer ~,r, "~
from l to 6, more preferably from 3 to 5. Examples of such amines are ethylene diamine, diethylene triamine, .
~ triethylene tetramine, tetraethylene pentamine, penta-:
ethylene hexamine and mixed higher polyethylene polyamines.
Useful higher ethylene polyamines have molecular weights from 300 to l,000 or 5,000, preferably 400 to 600, i 4-especially those prepared by polymerising ethylene imine. The process of polymerising ethylene imine gives rise to mixtures of polyethylene polyamines having a wide range of molecular weiyhts. These may be divided into mixtures havincJ narrow ranges of molecular weights, those indicated being the most useful in this invention .
Other polyamines which are useful in this invention.
are commercially available mixtures such as that pre-dominantly consisting of a mixture of isomeric penta-ethylene hexamines of formula C10 H28 N6 and related hexamines containing piperazine rings and 12 C atoms.
The average molecular weight of the mixture is approx-imately that of pentaethylene hexamine, i.e. 233, and lS the mixture contains a predominance of amines having

2 - 4 primary amino groups and at least two secondary amino groups.
Further suitable diamino compounds are bis (N-amino-ethyl) and N-(~ -amino-ethyl) piperazines of formula:
_,,CH2 - CH
2 2C 2 N \ / (CH2 CH2)aH

wherein a is O or 1.
The amine may be reacted with the intermediate mixture in approximately equimolar proportions. The resultiny reaction product will contain one or more residual primary amino groups. Alternatively, with the preferred linear alkylene polyamines the amine may be reacted with up to twice the molar quantity of the intermediate mixture or even more. It is not necessary f~ ~ 5.

~06Z696 to use exactly molar quantities of the two reactants.
Useful additives can be obtained by employing, for example, two moles of the intermediate mixture and 1.5 moles of the alkylene polyamine, giving a mixture of products.
Alternatively, the starting materials are reacted in equimolar proportions and one or more residual 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 manner known per se. Alternatively, the amine may be first reacted with appropriate quantities of the ' , carboxylic acids, aldehydes, ketones or mixtures of aldehydes and phenols to provide an amine having a residual primary or secondary amino group, and the resulting amine reacted with the intermediate mixture.
In another embodiment of the present invention the amine is an ethylene polyamine in which one primary amino group is reacted, either before or after the amine ' ;
has been reacted in equimolar proportions with the intermediate mixture, with an alkenyl substituted succinic acid or anhydride thereof containing from 8 to ~00 carbon atoms in the alkyl substituent. Such substituents are preferably residues of comparatively low molecular weight polymers or olefins, such as isobutylene or propylene, or oligomers of such olefins.
In view of the foregoing it will be understood that the proportions of the co-reactants may be varied according to the final product required.

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The foregoing process of the present invention may be readily carried out by heating the co-reactants together and a preferred reaction temperature is from 50 to 250C, more preferably 130 to 220 C, most pre-ferabl~ from 180 to 220C. An inert solvent, such as xylene, toluene or mineral oil may be used.
The reaction may be most conveniently carried out ! in a vessel which is open to the atmosphere. However, if desired the reaction can be carried out under vacuum or low pressure conditions or under a nitrogen blanket.
The reaction is usually completed within 1 to 6 hours, 2 to 4 hours being most common.
As hereinbefore indicated the present invention includes lubricant compositions containing dispersing amounts of the dispersant of the present invention, which are preferably used in an amount of from 0.3% to 15% by : weight, more preferably 1~ to 6% by weight, based on the total weight of the lubricant com.position.
Particularly preferred additives in accordance with the present invention are the polybutyl phenoxyacetamides .
derived from polybutenes of molecular weight 900 - 2800 and polyethylene polyamines having an average of from 4 to 6 amino groups, prepared by reactin~ a polybutyl ~:~ phenoxyacetic with the polyethylene polyamine in a molar ~ .
; 25 ratio of 2 : 1 - 1.5. :
:~ Also included within the scope of the present invention are additive concentrates comprising a minor amount of a lubricating oil and a major amount of one or more additives in accordance.with the present invention, ~:
including additive concentrates comprising a minor amount of a lubricating oil and a major amount of a combination of one or more additives in accordance with the present invention and at least one other lubricant additive.
The lubricating oil used in the lubricating com-S positions of the present invention may be any of the well known synthetic ester oils, such as dioctyl sebacate.
The preferred oils, however, are mineral oils o lubrica-ting viscosity of well known type.
The present invention will now be illustrated with reference to the following examples.
Example l (a) Preparation of n-Butyl polyisobutylnhenoxyacetate To a solution of PIB phenol (107.0g., O.lm.), pre-2ared by alkylation of phenol with lOOO molecular weight polyisobutylene using a BF3/nhenol complex as catalyst, and n-butyl chloroacetate (2~.6g., O.lSm.) in xylene ~ -(lOOml.) was slowly added, over about one hour, a solution of sodium methoxide (8.lg., O.lSm.) in anhydrous methanol (40ml.). The addition was carried out at 100C. and on ~completion the solution was heated at this temperature ;~ for a further one hour. The solution was washed with 10% hydrochloric acid (50ml.) followed by 3 x 80ml.
portions of a~ueous methanol (1:4). After being dried over magnesium sulphate the solution was stripPed of solvent.
Yield = 102g.
A sample of this product was saponi.ied with excess . ~ .
aqueous potassium hydroxide, acidified with hydrochloric acid and then washed with portions of aqueous methanol (l:4) untiI acid free. The acid value of the thus .

formed PIB phenoxy acetic acid (36.Smg. KOH/a. ) indica-ted that a conversion of 73~ had been obtained.
(b) Reaction of n-Butyl PolyisobutylPhenoxvacetate tetra ethvlene ~entamine to form an amide A mixture of PIB phenoxy butyl acetate (50g.) and tetra ethylene nentamine (3g.) was heated at 200C. for four hours under an atmosphere of nitrogen. After dilu-tion with mineral oil the mixture was filtered to give a clear product.
% nitrogen = 1.8 (calc. = 1.8) acidity = 5mg. KOH/g.

TBN = 37mg. KOH/g.
Exam~les 2 to 13 Prenaration of n-ButYl polyisobutylp-henoxyacetate lS A solution of sodium methoxide, nre?ared by dissol-ving sodium (43.0g., 1.87 mole) in dried methanol (60 c.c.) was added to a stirred solution of nolyisobutyl phenol (1943g., 1.7 ~ole) (prepared by boron trifluoride catalysed alkylation of phenol with 1000 M.~. polyiso~
butylene) and n-butyl chloroacetate (2~1.4q., 1.87 mole) in xylene (850 c.c.) at 100C. The addition took 1~
hours and the solution was then stirred at 69C for 2 hours.
The solution was stirred with hydrochloric acid/
water (1-4) (225 c.c.) and allowed to separate. The organic layer was then washed with water/methanol (1:4) (3 x 500 c.c.), petroleum spirit (b.p. 62-68C) being added to assist seoaration. The solution was dried over magnesium sulphate, filtered and stripped to 170 C. -~
under vacuum.

9.
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~06Z6g6 1734g. (7q~) of the intermediate was thus obtained.
Saponification value:- 40.4mg. KOTI/g.
A number of intermediate esters (~xamples 3 to 17) ~ere ~repared by the same general method, details being given in Table 1. In certain cases, namely ~xamples 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.
Exam*le 14 Pre~aration of Tetraethylene ~entamine amide of Polyisobutyl~henoxyacetic acid.
The product of Example 2 (1500g., 1.03 moles) was stirred with tetraethylenepentamine (119g., 0.63 mole) at 200C., in an atmos~here of nitrogen for 4 hours.
"
Evolved n-butanol was permitted to escape during the reaction. The product was cooled, diluted with mineral oil (276g.) and~filtered in petroleum ether solution.
Removal of the solvent gave the amide (1650~., ~1~). ;
20 ~ %~ 2.2; (calc. 2.2.~) Anhydrous TBN 51.5mg. KOH/g.
;~ Examples 15 to 26 ~ : , , A number of amides were nrepared by the same general method as for Example 1~, full details heing aiven in ~; 25 Table 2. Products were prepared as approxi~ately 85~
concentrates in mineral oil, except for Examle No. 23 ~h ~ and~also where the intermediates were ~renared in oil, in which case the final products were approximately 60%
oil concentrates. One product (Example 37) was prepared wlthout oil addition.
, 10 .

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~06Z6g6 For some pre~arations, particularl~ whcre volatile amines were used, it was necessary to modi y the prepara-tive procedure. Ilith ethylenediamine (Example 28) the reactants were heated under reflux in toluene solution for ~ hour, the toluene was distilled out, and heating was continued at 200C. for 3 hours, without a condenser.
Example 27 A solution of sodium methoxide, ~reParec~ by dissol-ving sodium (12.7g., 0.55 mole) in dry methanol (150 c.c.) was added slowly to a stirred solution of ?olyiso-butyl phenol (from 1000 M.'l. PIB) (571.5~., 0.5 mole) and n-butyl chloroacetate (83g., 0.~55 mole) in minera] oil (438g.) at 70C. ~eaction was continued for 2 hours and the mixture was then vacuum-strip?ed at 1~0C. and fil-tered in the petroleum ether solution. mhe resultant ester had a saponification value of 21.7mg. KOH/g.
600g. (0.23 mole) of the ester were reacted for 4 hours at 200C. with TEPA (26.9g., 0.14 mole), and the product was filtered.
Yield:- 550g., 90%
%N:- 1.5 (Calc. 1.55%) TBN:- 39.mg. KOH/g Spot test rating:- B
Example 28 A further sample of n-butyl PIB phenoxyacetate was prepared in oil, as described in ~xample 27, except that the ester was vacuum-stripped in the Presence of a filter-aid and was filtered neat.
1976g. (0.74 mole) of this ester were reacted for 4 hours at 200 C. with TEPA (70.0g., 0.37 mole), and Cl ::.

1~6Z696 the product was filtered.
Yield:- 1920~., 96~ ~-~N:- 1.2 (calc. 1.2~) TBN:- 30mg. KO~/g.
Spot testing rating:- B
Examples ~a to 31 Free amino groups in the amide of Example 25 were .. t~
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 of these ~reparations are given in Table 3.
Example 32 An intermediate ester, similar to that of Example 9 (9OOg., 0.60~m) was reacted with TEPA (7.~0g., 0.3~1m) at 200C. for 4 hours under nitrogen. Polysiobutyl succinic anhydride (prepared from 650 M.~. PTB) (163g., 0.153m) was added and reaction was continued at 200C.
for a further ~ hours. The mixture was cooled, diluent oil (192g.) was added, and the product was filtered in petroleum ether solution.
%N: 1.9 (Calc., 1.9%) ;~ TBN:- 30mg. KOH/g.
Panel coker rating:- 69.5 Spot test rating:- A
Suitability of the products of the present invention ; for use as ashless dispersants in lubricants were de-termined by MS VC and Petter AV-B Engine tests, by Panel Coker Tests and by Spot Tests.
The VC tests were carried out by the standard method on two formulations containing test additives.

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Formulation A was a lOI~/30 blend, formulated to meet U.S. S~ecification MIL-L-46152, containing commer-cially available metal sulphonate detergents, viscosity index improver and antioxidant/antiwear additi~e and in which the ashless dispersant normally present (4.5~) was replaced by the test additive, also at 4.5~.or at equiva-lent active dosage. The blend had a sul.phated ash con-tent of 1%. Formulation B was similar to formulation A, but having a sulphated ash content of 0.5% and con-taining ashless corrosion inhibitors.
After the tests, merit ratings were assigned accor-ding to the condition of the test engine in the usual.
way and these ratings were as follows:-FORMl1LATION A
.15 Test Average Sludge Average Varnish Piston Additive(Max lO) (Max lO) Skirt :, Varnish (Max lO) Product of Example 24 (5.3%) 9.0 8.3 8.5 .
~; Additive X(4.5%) 4.9 7.5 7.2 FORMULATIO'~
Test Average Sludge Average Varnish Piston Additive(Max lO) (Max lO) . Skirt Varnish :: ?
(Max lO) Product of Example ~ 14 (475%) 9.0 8.3 8.5 : l3. .~:

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.. , ... . ................... ... . , . ~ . :

~06Z696 FORMULATIO~ B Cont'd _ Test Average Sludge Average Varnish Piston Additive (Max 10) (Max lo) Skirt _._____ _ .. __................. . !.~
Varnish ' (~lax 10) Product of Example 22 (6.4~) 9.2 8.2 8.3 Additive X is a commercially available ashless dispersant consisting of a borated Mannich base of a poly-isobutyl phenol.
The Petter AV-B tests were also carried out according to the standard procedure and merit ratings (maximum 10) assigned in the usual way according to the condition, after test of various parts of the test engine.
Carbon deposition in the grooves of the test en~ine were also measured. Groove carhon and the overall merit rating (maximum 100) derived from the individual ratings were as follows:-Test Additive Groove Carbon (~) Overall Rating 1st 2nd 3rd Product of Example 24 (4.06%) 76.8 1.0 Nil 74.8 Product of Example 23 10 Nil Trace 91.4 Product of repeat of Example 38 Nil Nil 83.3 ~; 25 Product of Example 27 (4.95~) 66 3 Nil 70.3 Product of Example 28 (4.95~) 26.1 Nil Nil 87.0 Additive X 93.0 30.1 0.8 50.7 14.
~`1 .
.. ,, ........ .... . - , -106;~696 .,~, The test blend used in the AV-B tests was an S~E
30 blend, formulated to meet the requirements of U, S .
S~ecification MIL-L-2104-C, containing commercially available sulphonate detergents, corrosion inhibitor and antioxidant/antiwear additive, ancl in which the ashless dispersant normally present (3.5%) was replaced by the test additive, also at 3.5% except where stated.
The Panel Coker tests were carried out usiny the same test blend as for the AV-B test and were carried out for 3~ hours in a slightly modified form of the normal apparatus. Instead of continuous oil splashing, the oil was splashed against the aluminium panel maintained at 600F. with a cycling procedure consisting of a splashing period of 15 seconds and a 45 second period when the paddle was stationary. The apparatus was further modified to allow a flow of moist air through the sump a~ove the oil surface at the rate of 2.3 litres per hour. ?
The area of the sump not normally immersed in oil Z0 was rated according to the percentage cleanliness in much the same manner as an engine piston is rated after a test such as the Caterpillar l-G test, to give a ~
Merit Rating (100 = Perfectly clean). It is believed -that the above-mentioned test correlates well with the ;
Caterpillar 1-G Engine Test.
In the spot tests the test additives were dissolved in mineral oil (V21o=3.5cS) at 4~, except where the additives had been prepared as 60~ concentrates in oil in which cases 5.8~ additive was used. Carbon black (Spheron 9- ex Cabot Carbon Coy - average particle '`.

C ~ 15.

~062696 size = 27m) (1~) was added and the mixtures (lOg) were agitated for 1 hour, using an Ultrasonic Generator in 5" x 1" test-tubes. The tubes were then stored at 50C. for 16 hours and allowed to cool. Drops of oil, taken from the top ~", were spotted on to chromatography paper, using a fine glass rod. The spots were then allowed to develop for 24 hours, and rated as follows:-A = Carbon well dispersed B = Carbon moderately well dispersed C = Carbon poorl~r dispersed D = Carbon not dispersed The ratings obtained in the Panel Coker and spottests are recorded in the following Tables 2 and 3.
15 The Panel Coker tests were carried out at a test additive concentration of 3.5% except where the products had been prepared as 60% concentrates in oil when 5.1% of the products was used. In the same Panel Coker test a rating of 61.2 was obtained with additive X. In the spot test a sample of the mineral oil without additlve gave a D rating.

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'76.

Claims (6)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A lubricating oil dispersant containing a polyisobutyl phenoxy sub-stituted acetic amide, said dispersant being prepared by the process compris-ing (i) reacting a polyisobutyl substituted phenol wherein said polyisobutyl substituent contains from 50 to 200 carbon atoms with a C1-4 alkyl chloro-acetic ester to form an intermediate mixture containing polyisobutylphenoxy-substituted acetic ester, and (ii) reacting said intermediate mixture with an ethylene polyamine without removing unreacted C50-200 polyisobutylphenol to convert said acetic ester to carboxylic amide, said dispersant having a high amide and low polyisobutylphenol content.

2. A dispersant of claim 1 wherein said reacting of a polyisobutyl sub-stituted phenol with an alkyl chloroacetic ester is carried out in the presence of a base which functions as a HCl acceptor.

3. A dispersant of claim 1 wherein said polyethylene polyamine is tetra-ethylene pentamine.

4. Lubricating oil containing a dispersing amount of a dispersant of claim 1.

5. An additive concentrate containing a minor amount of lubricating oil and a major amount of a dispersant of claim 1.

6. A dispersant of Claim 1 wherein said alkyl chloro-acetic ester is butyl-.alpha.-chloroacetate.