CA1039302A

CA1039302A - Motor fuel composition

Info

Publication number: CA1039302A
Application number: CA196,530A
Authority: CA
Inventors: Robert R. Kuhn; Warren H. Machleder
Original assignee: Rohm and Haas Co
Current assignee: Rohm and Haas Co
Priority date: 1973-05-02
Filing date: 1974-04-01
Publication date: 1978-09-26
Also published as: NL177017B; SE7705732L; FR2228103A1; DE2420305A1; GB1476381A; SE412250B; SE412251B; NL7405930A; SE7705733L; GB1476384A; ZA742604B; IL44736A; JPS5014705A; JPS585230B2; IL51754A0; IL51753A0; BE813498A; NL177017C; IL44736A0; GB1476382A

Abstract

(1) ABSTRACT OF THE DISCLOSURE
Disclosed herein is a novel composition of matter comprising a mixed polyester of the formula:

wherein n is an average number of from about 1 to 20; and in the case of the mixed polyester derived from a trimer acid p is 1 or 2 and q is 1 or 2, the sum of p and q being 3; and in the case of the mixed ester derived from a dimer acid, both p and q are each 1;
R7 is an alkyl group containing 4 to 12 carbon atoms;
R8 is H or an alkyl group containing 4 to 12 carbon atoms;
R9 is a straight or branched chain alkyl group containing 1 to 24 carbon atoms; and Z1 is a saturated or unsaturated hydrocarbon residue having about 34 to about 51 carbon atoms, said residue being the residue of a dimer or trimer acid or mixture thereof.
Also described are detergent additive compositions suitable for addition to gasoline comprising a mixture of (1) about 20 to about 250 parts by weight of a tertiary alkyl primary amine having a branched backbone and a total of 6 to 24 carbon atoms;
and (2) about 100 to about 650 parts by weight of a mixed polyester as defined above. The specification also describes a (2) multifunctional additive composition suitable for addition to gasoline comprising a mixture of (1) and (2) as defined above, together with (3) about 5 to 100 parts by weight of a surface active alkyl ammonium carboxylate salt-ethoxylated alkyl phenol ester of a trimer or dimer acid of the formula where n is an average number from 1 to 12.5; and wherein in the case of the salt-ester derived from a trimer acid x is 1 or 2, and y is 1 or 2, the sum of x and y being 3;
and in the case of the salt-ester derived from a dimer acid, both x and y are each 1;
R4 is an alkyl group containing 4 to 12 carbon atoms;
R5 is H or an alkyl group containing 4 to 12 carbon atoms;
R6 is an alkyl group containing 2 to 24 carbon atoms which may be straight or branched chain or an amine substituted alkyl group of 2 to 24 carbon atoms; and Z is a saturated or unsaturated hydrocarbon residue of the acid, said hydrocarbon residue having 34 to 51 carbon atoms. These compositions of matter are useful in substantially eliminating, or at least substantially reducing, deposits which would otherwise form in the intake valves and ports, and in the combustion chamber, of an internal combustion engine, and in the carburetor.

Description

~` 1039302 Disclo3ure This lnvention relates to motor fuel compos~t ons for spark ignition, internal combustion ~-englnes. More particularly, this invention relates to a detergent motor fuel containing additives which ¦~
reduce or prevent the formation of deposits in the carburetor as well as in the induction system and combu~tion chamber of an internal combustion engine.
Thus, the formulation~ of the present lnvention are ~-particularly effective as carburetor detergents to clean up and maintain the cleanllness of the carburetor and to prevent, reduce or minimize against depo~its rorming ln the induction system such as the area around the valves and ports. This invention also relates to an additive concentrate of one or more of the additives in mixture, solutlon or combination.
Modern internal combustlon engine design is undergoing and has undergone important changes to meet stricter standards for engine and exhaust ga~ emissions.
A ma~or change in engine design is the feeding or recycling of blo~Jby gases from the crankcase of the engine into the intake air supply to the carburetor ~ather ~han the venting of these gases to the atmosphere, - `
a~ in the past. The blowby gases contain substantial ;,' :
.''. ~ .
,, .

~ . ~

amount~ o~ deposit-~orming substances and are known to ~orm deposits in and arou~d the throttle body area of the carburetor. 'rhese deposits restrict the ~10W of air through the carburetor at ldle and at low speeds so that an overrich ~uel m$xture results. This condition ,~ , ~ . , produces rough engine idling, stalling and also results in excessive hydrocarbon and carbon monoxide exhaust emissions belng emltted to the atmosphere.
In addition to the changes that have already been made, it ls anticlpated that additional burdens and demands will be placed on present day lnternal combustlon engines and thelr ~uels wlth the advent o~ new emisslon control devices, such as exhaust gas recirculation ~ystems and catalytlc exhaust mu~lers. Also, the use o~- certain ~uel additives such as the alkyl ammonium phosphate detergents may have to be restrlcted or - eliminated because catalytic exhaust mufflers which ; utilize metal catalysts w1ll be polsoned by phosphorus-containing compounds.
It is an ob~ect of the present, lnventlon to proviae a detergent motor fuel which will have certain carburetor detergent properties and which will clean up and malntain the cleanliness o~ the carburetor and also the remainder o~ the ~uel induction system such as t,he valves and ports and reduce tha octane requirement i,. . .

lncrease Or an internal combustion engine. It i~ another - ob~ect o~ the present invention to provide a detergent ~uel which will maintain a low level o~ hydrocarbon and carbon monoxide exhaust gas emlssions and which will avoid the use Or phosphorus-containing additives.
It is still a further ob~ect of the present inventlon to provide a detergent fuel which has other desirable properties such as rust and corrosion protection, water demulsibility properties, anti-icing properties, etc.
It ls a further ob~ect Or the present invention to provide multi-functional gasoline additives or additive combinations effective in inhibiting the formation of intake valve ~eposlts in addition to being e~ective-a~ carburetor detergents, and which can be used at relatively low concentratlon~ (and thus at relatively low cost) for example at a treating level Or about lO00 parts per million (ppm on a weight basis in the gasollne), or less, and more preferably 600 ppm or less, and even more preferably 400 ppm or less.
There, are, Or course, ot~er detergent motor fuel compositions available today, but they generally suffer from one or more deficlencles. Either they are used at very high concentrations, for example, something Or the order of 4000 ppm; or if used at the use levels ln whlch we are interested, the available rormulations ~u~er rrom one or more derect3.

.

~' . .

We have discovered that the combinatlon o~
(1) selected tertiary al~yl primary amines havlng branched backbones and a total o~ about 6 to 24 carbon atoms, and more preferably, a total Or 12 to 22 carhon atoms, (2) a surrace active alkyl am~onium carboxylate salt-ethoxylated alkyl phenol ester Or a trimer or dlmer acid; and (3) a dimer or trimer acid ` ester comprising the essentially completely esterified polyester o~ a dlmer or trimer acid, or mixture Or dimer and trimer acids, produced by the polymerization or condensation Or an unsaturated aliphatic mono carboxylic acid having between 16 and 18 carbon atoms per molecule . which is esterl~ied with (or incoFporates) a mixture of aliphatlc and ethoxylated aromatic alcohols, are e~rective in reducing or preventlng the rormation o~ carburetor and other induction system deposits.
~ According to one aspect Or the present inventlon, thererore, we provlde a normally liquid, multi-functional, additive composition ~or addltion 20 to a leaded, low lead, or unleaded gasoline, l.e., to a dlstlllate hydrocarbon ruel comprislng a maJor proporbion Or a hydrocarbon b~e ~uel dlstllllng within the gasoline distillatlon range. The three component . ~ .

: ` 10393 . composi~ion ran~ng from a total of about 125 tG about 1000 parts, on a weight basis) is conprised of about 20 to a.bout 250 parts, and more preferably~ about 50.to 100 parts b~ weight of (1) a tertiary alkyl branched . .
chain primary amine, as above described, about 5 to about 100 parts-and, more preferably, about 10 to about 25 .
parts by weight of (2) a surface active alkyl ammonium .
.: carboxylate salt-ethoxylated alkyl phenol ester of a trimer or dimer acld, as above described; and about 100 to about 650 pa ts by weight and, more preferably, about . 200 to 400 parts by weight of (3) a trimer acid or dimer acid mixed ester as above described. In an alternati~e embodiment of the inventlon and where induction syste~
control, per se, is prlmarily desired, then components : .
(1) and (2) can be omltted, and component (3) can be --utilized itself in the fuel, on a total weight basis of about 100 to about 650 ppm, more preferably about 200 to 400 ppm, or component (3) can be used in con~unction with component (1) to provide a two-component package or -20 blend providing good carburetor detergency and good lnduction system deposit control, or component (3) can be used ~Jith other carburetor detergent~ and/or other rust inhibitors.
When usin~ a comblnation or mixture o~ components (1) a~d ~3), they are used in the same amount as noted above, i.e., about 20 to 250 ppm Or (1), more preferably, about 50 to 100 ppm of (1) and about 100 to 650 ppm, more preferably, , - about 200 to 400 ppm of (3).
On a fuel treating level basi~, i.e., on a ~evel - related to the gasoline, the three component additive composition should be added to or used in the gasoline at a total level of about 125 to about 1000 ppm (welght basis) and, on~an individual or component basis, in an amount of from S
about 20 to 250 ppm, and more prefer~bly 50 to 100 ppm Or (l);
about 5 to about lOO ppm, more preferably about 10 to about ` 25 o~ (2), and about 100 to about 650 ppm, more preferably 200 to 400 ppm of (3). On a pounds per barrel of gasoline basis, this is about 5 to 62.5, more preferably 12.5 to 25 lbs./1000 barrels (bbls). o~ gasoline Or ~1); 1.25 to 25, ~ 4~
more preferably 2.5 to 6.25 lb~./1000 bbls. of gasoline Or

(2); and 25 to 162.5, more preferably 50 to 100 lbs.~lCOO bbls.
Or ~asoline of (3).
For the concentration of the additive c~mponent

(3), above, (~-hen used alone) the ppm concentration and the .
pounds per barrel of gasoline treating level is the same as noted for component (3) above, i.e., about 25 to 16205, more preferably about 50 to 100 lbs./1000 bbls. (barrels) of gasGline, or about lOO to 650 ppm, more preferably about 200 to about 400 ppm of (3).
For the concentration Or the additi~e mixture (1) and (3) in gasoli'ne, the treating level should be in the range of about 20 to 250 ppm, more prererably about 50 to 100 ppm, of component (1), and about 100 to 650 ppm, more "

preferably about 2CO to 400 ppm o~ component (3~. On a pounds per barrel o~ gasoline basis, thi3 ~nounts to about : 5 to about 62.5 lbs., more preferably abou~ 1205 to 25 lbs.
.: per 1000 bbls. of gasoline of component tl); and about 25 to 162.5 lbso~ more pre~erably 50 to 100 lbs. per 1000 bbls.
of gaso~ine of component (3).
The tertiary (tert.) or t-alkyl primary amlne, having at least one branched chain, may be represented by the general formula (I).

.: . ...
Rl ' '~.'.

R2 -- C NH2 (I) - ,-in whlch Rl, R2, and R3 are alkyl groups whos~ total carbon atom content ranges from 6 to 24. It is preferred that two of the R groups, for example, the Rl and R3 Of the t-alkyl primary amine be methyl groups.
The t-alkyl primary amines with branched chains and which may be used in the compositions of the present invention include, for example, t-octylamine, t-nonylamine, ` t-dodecylamine, t-tetradecylamine, t-octadecylamine, t-docosylamine, t-tetracosylamine and mixtures Or two or more of such amine 5 . These amines are commonly prepared by reactions known to those skilled in the art such as the reaction of nitriles with alkenes or secondary or tertiary alcohols in strongly acldic media.
Commercially available t-alkyl primary amines are often mixtures. t-Octylamine having a branched structure has the formula: ¦

CH3 C CH2 ~ ---N~2 I

and the alkyl group of this amine will hereinafter be referred to as t-octyl. One form of t-nonylamine is prepared as a mi~ture contalning C6H13C(cH3)2N~2 ` - 103930Z

and C7}I15C (CH3)2NH , .
and has a neutral equivaient of about 142. A co~.ercial preparation which can be used in the present inv~ntion i 3 A readily available under the trademark'Primene 81-F.l ,~
which is the trademark used for a mixture of ~-dodecyl-, ,-t-tridecyl- and t-tetradecylamines or principally a ixture of t-C12H25NH2 to t-C14H29NH2 amines having a neutral equivalent of about 191. Another commercial preparation which is useful in the present invention is avallable under the trademark Primene JM-T. ~Primene JM-T4is principally a mixture of t-ClgN37NH2 to t-C22H4sNH2 amines and has a neutral equivalent of about 315. The important consideration is that in a t-alkyl --primary amine, the NH2 group is always attached to a carbon atom containing no hydrogen atoms and in the -present invention at least one Or the alkyl groups is branched. - -- -The alkyl ammonium carboxylate salt-ethoxylated ; alk~l phenol ester of a trlmer or dimer acid (or mixture thereof) ~s added or included primarily to provide rust and/or corrosion protection although there is also some modest carburetor detergency activity, has the following formula (II):

_ g _ - f l03g302 / [C - O(CH2CH2)n ~ R4 -Z < ~ (II) \ [C2 ~ H ~`6]Y R~ x - where n is an average number from about 1 to 12.5 and more preferably from about 3 to 10; and in the case of a salt-ester - derived from a trimer acid x is 1 or 2, and y is 1 or 2, the sum of x and y being 3;
and in the case of the salt-ester derived from a dimer acid, both x and y are each l;
- R4 is an alkyl group containing 4 to 13 carbon atoms;
R5 is H or an alkyl group containing 4 to 12 carbon atoms;
R6 is an alkyl group containing 2 to 24 carbon atoms ; which may be straight or branched chain or an amine- substituted alkyl group of 2 to 24 carbon atoms.Preferably, R6 contains 12 to 22 carbon atoms; and Z is a saturated or unsaturated hydrocarbon residue of the acid, said hydrocarbon residue having 34 to 51 carbon atoms.
(Z will ordinarily have 51 carbon atoms in the case of a trimer acid, and ordinarily 34 carbon atoms in the case of a dimer acid).
The above-described alkyl ammonium carboxylate salt-ethoxylated alkyl phenol ester of a dimer or trimer acid is also ~20 disclosed in U. S. Patent 3,782,912, issued January 1, 1974 to Rol~ert R. Kuhn ard Warren 11. Machleder.

,' ' .
,' ;
'' - ' '' C -10-.

,', ,' ' : , .'', ' , ' ,". , ~ "
, , ; .. . .

~` 103930Z
The alkyl ammonium carboxylate salt-ester, i.e., . component (2), may be used as all trimer acid derivative or all dimer acid derivative, or any mixture o~ the dimer and trimer acid derivatives may be used in the present invention.
Also, the presence o~ some monocarboxylic Clg -:-acids or the like in the ester or salt form, or mixtures o~ both ester and salt ~orm, may be tolerated in minor amounts, about 5~ or l~ss.
Speclfic embodiments Or the alkyl ammonium .` carboxylate salt-ester of the general formula II, above, and wherein, R4 is substantially or essentially all octyl~ l-e -C8H17i and Rs is H and which are usable in the present invention are glven in Table I below:
TABLE I

: Alkyl Ammonium Carboxylate Salt-Ester n ~ X Y
: A i.5 t-C12-14 1 2 : B 1.5 t-C12-14 ~ 2 C 3 t-C12-14 1 2 : D 3 t C12-14 2 . E 5 t-C12-14 1 2 F 7.5 t-C12-14 1 2 G 9.5 t C12-14 1 2 H 9.5 t-C12-14 2 I l?.5 t-C12-14 1 2 ., .

~039302 TABLE I (Cont'd) .
Al~l Ammon~.um Carboxylate : Salt-Ester ~ ~6 X Y

K . 3 (C~I2CH2NH2)H 2 L 3 (cH2cH2NH)3H 2 . ' M 1.5 t-C12-14 N 3 t-C12-14 0 9.5 t-C12-14 p 3 t-C18-22 Q 3 t-C18-22 2 R 3 t C18-22 1 2 . S . 5 t-C12-14 ;~ T 1.5 t-C18-22 U 5 t-C18-22 ; V 5 t-C12-14 2 . W 7.5 t-C12-14 2 : X 10 t-C12-14 2 y 1.5 t-C18-22 2 Z 5 t-C18-22 2 At 1 t-C12-14 1 2 B' 10 t-C12-14 1 2 - C~ 1 t-C18-22 1 2 Dt , 5 t-C18-22 1 2 ,, - .
~ - 12 -, , . ; :
. . . . .
.. . .

The alkyl ammonium carboxylate salt ester can be made in known fashion, by the acid catalyzed esterification of a suitable dimer or trimer acid, or mixture thereof, for example, in the case of the diester-monosalt, with two moles of a suitable ethoxylated alkyl phenol followed by conversion of the remaining carboxylic acid functionality to an alkyl ammonium carboxylate salt with the addition of a suitable amine. The trimer acid may be the product derived from the trimerization reaction of a Cl8 unsaturated fatty acid; an example of a suitable trimer acid is that available under the trademarkY~pol 1041". The preparation ; of such dimer and trimer acids is described in United States Patent 2,632,695. A generalized reaction scheme for the pre-paration of an alkyl ammonium carboxylate salt-ester is shown below using a trimer acid for illustrative purposes:

C (CO2H)3+2HO(CH2CH2O) ~ 4 l) Acid C ~ 2 2 2 n ~ ~ 2 LCO2(CH2CH2O) ~ 4 ~ R ~
\ C2 NH3R6 ;
Where n, R4, R5 and R6 have the values given pre-viously, and C5l is the carbon atom content of the hydrocarbon residue. -~
In order to provide induction system and combustion chamber deposit control, there is included in the additive or !' additive combination, a mixed polyester of a dimer or trimer -acid, or mixture of such dimer and trimer acids.

:.

~039302 -- s The mixed polye~t~rs as well as th~ di~er and trimer acids may be prepared in known ~ashion. ~or example, an unsaturated aliphatic monocarboxylic acid havlng bet~een about 1~ and 18 carbon atoms per molecule, ~or example 5linoleic acid can be pol~Jmerized or condensed to form essentially the dimer o~ linoleic a^ld, a dicarboxylic t acid, and also the aliphatic mGnocarboxylic acid can be polymerized to form essentially the trimer of linoleic acid, a tricarboxylic acid~ Mixtures of such dicarboxylic 10and tricarboxylic acids may also be formed. Similarly, other C16 and C18 unsaturated aliphatic monocarboxylic acids, including ricinoleic and linolenic acid can be polymeriæed to dimer and trimer acids or mixtures of such dimer and trimer acids. The preparation of such dimer 15and trimer acids i3 described in United States Patent 2,632,695. The mlxed polyesters used in the present invention are prepared by reacting a suitable amount of a mixture o~ an aliphatic alcohol and an ethylo~Jlated ,~
aromatic alcohol with the polycarboxylic acid to esterify 20essentially all of the carboxyl groups in the acid.
- E5teri~1cation is conducted according to conven'cional, --known methods. The aliphatic alcohols which are suitable for this purpose are preferably saturated aliphatic alcohols, having from about l to 24 carbon atoms.
~epresentative aliphatic alcohols include methyl alcohol, ;- propyl alcohols n-butyl alcohol, iso-butyl alcohol, ', .... . . .
. .
.
, hexyl alcohol, 2-ethylhexyl alcohol, decyl alcohol, dodecyl alcohol, tridecyl alcohol, lsodecyl alcohol, lauryl alcohol, stear~l alcohol, hexadecyl alcohol, and nondecyl alcohol. ~referably, the aromatic or aromat1c containing alcohols which are used are alkylated -~ phenols which have been ethox~lated with varying amounts of an alkylene oxide such as ethylene oxide. (These materials are known generally as alkylphenoxypolyetho~
ethanols.) The number o~ moles Or ethylene oxide which may bc condensed with the aikylated phenol may vary from about one to about 20 ethylene oxide units, and more preferably rrom about one to rour moles o~ ethylene oxide. ~ile the presence of some unreacted alcohols and some completely esterified all-aliphatic or all-ethoxylated aromatic esters will be present in the esterirication mixture, the princlpal active ingredient or the principal active mixed polyester ~as the rollowing general rormula.

/ tC~(CH2CN2)n ~ \ p Zl R8 ~C02Rg]q ' '~
wherein n i~ an average number of from about 1 to 20 and, more pre~erably, o~ from about 1 to about ~3 and in the case of the mixed polyester derived ~rom a trimer acid, p is 1 or 2 and q is 1 or 2, the swm of p and q being 33 and in the case of the ~lixed ester derived from a dimer ~ 15-,'~ .

.. .
acid, both p and q are each 1; and where Zl is a saturated or unsaturated hydrocarbon residue having an avera~e of 34 to 51 carbon atoms, said residue being the residue of a dimer or trimer ac~d of linoleic acid, or mixture of 8aid dimers and trimers of linoleic acid, -15a-:.... . ,-:
.' - . , ..
,. -:,' . ,~ .
.. . . ...

.

~ 1039302 R7 is an alk~l ~roup conta ning 4 to 12 czrbon atoms~ more pre~erably 8 or 9 carbon atoms;
':
R8 is H or an al~yl group contalning 4 to 12 ; carbon atoms, more preferably H; and Rg is an alk~l group containing 1 to 24 carbon atoms which may be straight or branched chain.
The aromatic alkoxylated alkyl phenols are prefer2bly based on either octyl or nonyl phenol and can contain i,......... . .
approximately 1 to ~0 moles o~ ethylene oxide, and more ~ 10 preferably about 1 to about 4 moles of condensed i ethylene oxide, Also, the mixed polyester ~hen based on a mixture of dimer and trimer acids, as hereinabove described, are preferably based on a mixture containing --at least about 6 ~ trimer acid, and more preferably, at least about 8G% trimer acid.
In the rollowin~ examples which lllustrate this invention, all parts and percentages are by weight, - unless otherwlse stated. The abillty Or the add~tlve or addltlve combinations Or thls lnvention to clean up and maintaln the cleanliness Or the carburetor o~ an lnternal ---combustlon englne ls lllustrated, and 1ts abllity to remove or protect agalnst the formatlon Or lnductlon -~ -.. .. .
syætem deposlts is also lllustrated below. Also illustrated ; below is the ability Or the additives to reduce octane requirement lncrease ln an lnternal com~ustlon engine.

,. -."" P~

., , . .; .

- - -- ~

. -Unless other-Sse stated, an MS-o8 ~asoline ~uel i~ used for the ~1OWbY carburetor detergency Keep Clean engine te~t and a Howell Unleaded Gasoline is used for the Induction System -Deposit Test. The Xo~ell U~leaded Gasollne has the ~'ollowing properties~

Howell Unleaded Gasoline: Fuel Speclfication EL-72-1 Aromatic Content 30.2~
Ole~ins 11.6%
Saturates 58.2%
Lead .3 g/gal Sulfur 0.009 Wgt Gravity - 57.9 API
Reed Vapor Pre~sure 8.1 Research Octane 91.7 Motor Octane 83.8 Initial BP 94F
50% Distilled 228F
- 90% ~ist~lled 351F
; Distillation End Point 426F

Engir,e Test Evaluation Or Multipur~ose Carburetor Deterger,ts A. Blowby Carburetor Detergency Keep Clean Engine -~ Test 1. Engine Test Procedure The Blowby Carburetor Detergency Keep Clean Engine Test (BBCDT-KC) measure~ the ability o~ a gasoline .
additlve to ~eep clean the carburetor throttle body area, and is run ln a 1970 Ford 351 CID V-8 engine equipped by means o~ a special "Y" intake manifold with two one-barrel carburetors, ~hich can be independently ad~usted and activated. With this arrangement, a separate test ~uel can b~ evaluated by each carburetor ~hich feeds four o~ the eight cylirders vla the non-lnterconnected intake ma~ifola, The carburetorY are modified ~Jlth rerllovable al~lnum ~.le~ves ln order to ~cllltate wel~hing of thc ,, `, ,, ~, , ,,, ` , .

deposlts which accwnulate in the throttle bod~J area.
- The severity o~ the test is ad~usted to an appropriate level by recycling the entire ~nount oI blowby ga~ea, approxim~tely 90~110 CFH, to the top of the air clearJer 30 .
that e~ch carDuretor receives an equal volume of these ~, gases. Equal intake mixture ~lo-~ through each carburetor : i9 ad~usted during the first hour of operation of means of intake manifold di~ferential pressure and CO exhaust `~ gas analysis. The rOllOwing test cycle and operating conditions are employed:
Test C~cle:
Phase I 650 engine rpm, 8 min.
Phase II 3000 engine rpm, 1 min.
Test Duration, hrs. 10 Intake Air, F 135 ~ 10 Jacket ~Jater, F 190 ~ 10 Engine Oil-Sump, F 210 -~ 10 ~ CO in Exhaust 3.0 ~ 0.2 ~ -Blowby, CFH 90 - 110 The weight (mgs~) of deposits accumulated on the aluminum sleeve is measured, and the average value Or four tests per additive or additive mixture is reported.
The gasoline used in the BBCDT-KC test is an MS-o8 gasoline having the following properties:

~ 18 -, .

' 10393Z

ravity 59,7 API
Sp. Gr. at 60F, -74 ~ ~S~ D-85 ~sti~lation, F.
:. 5 IBP -93 10% 123 5o~ 205 9% 348 - 10 % ~ecovered 98 : % Residue % Loss ` % Sul~ur Ooll Lead, Gm/gal . 3.08 FIA Composition Aromatics, ~ 23.1 Ole~ins, % 20.0 Saturates, ~ 56.9 ;. Oxidation Stability, Minutes600+
.. 20 ASTM Gum (Unwashed), mg/100 rnl 1.0 Research Octane l~-~mber 95.5 % H 13.10 . % C 86.61 -.-. H/C 1,80 ;
B. Induction System Deposit Engine Test -. 1. Engine Test Procedure . . .
The Induction System Deposit Test (ISDT) ~hich -.
.: is used to evaluate the abillty of gasoline additives or -~
mixtures o~ additives to control induction system deposits, 3 is run using a new air-coo~ed, ~ingle cylinder, 4 cycle, ..
.5 H.P. Briggs and Stratton engine ~or each test. The . engine is run fo. 150 hour3 at 3000 rpm and 4.2 fto lb~. : lo~d, uith a 1 hour shutdown every 10 hours to check the ,,, - lg -, , ,, . : . ,, :

.: . , ' , i 103930Z
; -oil level. Carbon monoxide exhaust emission measuremerJt~
are made each houl- to insure that a constant air to ~uel (A/F) ratlo is being malntained.
Upon completion o~ a test,run, the engine is partially disassembled, and the intake valve and port . . .
are rated and valve and port deposits are collected and weighed.
C. Rusting Test Method .
A rusting test method ~or ~uel additive rust inhibition is used which follows military specification MIL-I-25017C, (Section 4.6.3). This procedure which utilizes a type B medium hard water is a modlrication o~
the basic ASTM method D665. The ob~ect of the test is to evaluate the ability o~ a gasoline additive to ~`
inhibit rustirJg o~ ferrous parts such as encountered in ; gasoline storage and transportation systems. The method involves stirring a mixture Or 300 ml. Or an additive blend in depolarized lsooctane with 30 ml. o~ de-ionized - - distilled water, medium hard water, or synthetic/ for 5 hours at a temperature of 100F. (37.8C) with a cylindrical steel specimen completely lmmersed therein.
Test results are reported as percent area rusted and a pitting rating is also optionally reported on a scale of 1 to 3, with 3 being,the worst degree o~ pitting and 0 being the best. The type B medium hard water is prepared as ~cllows:

*Thi~ i8 a publi~hed U.S. mili~ary specification available to the publ$c rom the Department of Defence, Washington, D.C. U.S.A.
~ .

. . , -~ 3 stock solutions using ACS reagent-grade chemicals in distilled water containing, respectively, 16.4g/liter NaHCO3, 13.2 g/liter CaC12 2H2O, and 8.2 g/liter MgSO4 7H2O. Ten ml.
of the NaHCO3 stock solution are pipetted into 800 ml. of distilled water in a l-liter volumetric flask, and then shaken vigorously. While swirling the contents of the flask, 10 ml.
of the CaC12 stock solution are pipetted into the flask and then 10 ml. of the MgSO4 stock solution are also pipetted into the flask, distilled water is then added to bring the volume 10 to 1 liter and mixed thoroughly. The final blend should be clear and free of precipitate. -D. Combustion Chamber Deposit Engine Test ~-1. Engine Test Procedure The Combustion Chamber Deposit Engine Test (CCDET) is used to evaluate the ability of a gasoline additive, or mix-ture of additives to control or reduce the octane number require-ment increase (ONRI), in an internal combustion engine, the test is run using a 1972 Chevrolet 350 CID V-8 engine equipped with a two barrel carburetor and a 1972 Tubo Hydromatic 350 20 transmission which is connected to a 1014-2 WIG dynamometer : equipped with a 200.3 lb-ft2 inertia wheel. The following -~ test cycle and operating conditions are employed and are - --- intended to simulate an urban taxi cab.

.~ ' , - : .
, .

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

, .. . . . . . . .
.
,. . . . ..
,: :

; Test Cycle Phase I Start - idle, 650-750 rpm Phase II Accelerate - 1 to 2 shift, 5.5 sec., 29D0-3000 rpm Phase III Accelerate - 2 to 3 shift, 9.5 sec.
- 2800-2900 rpm Phase IV 3rd gear, 10.0 sec., 2600 rpm Phase V Decelerate to idle, 15.0 sec.
Test Duration 200 hrs.
Fuel Consumption 1000 gallons (Howell unleaded gasoline plus additive treatment) Intake Air F Ambient Jacket Water, F 180 Engine Oil-Sump, F 220 + 10 Octane number requirement is determined at 24 hrs.
interval under the following engine conditions: transmission ; in 3rd gear with an output shaft speed controlled at 1500 rpm and the engine throttle wide open. The octane number requirement of the engine is determined at trace knock in .
terms of primary reference fuels, i.e., the engine is run on a series of blends of isooctane and n-heptane of known octane number until audible knock is perceived. The lowest standardized ... .
octane number blend at which the engine does not knock is recorded as the octane number requirement. Octane number requirement increase is then the difference between the initial - octane number requirement and the final octane number require-ment for a particular test.

:. 10393 Z
The novel ~uel compositions may be prepared by adding the ~ndividual add'tives directly to the fuel, or an additive blend or mixture of one or more of the components may be prepared or a concentrate of one or : 5 more of the additives in a suitable solvent such as toluene or xylene may be prepared. Also, all of the additlve components are normally liquid materials at room temperature and are soluble or miscible with each other and may be distributed without any solvent, - 10 The preparation of a typical mixed polyester employed in the fuel o~ the invention is as follows:
PREPARATIO~ OF TRI~R ACID, DIISODECYL, :.
: MONO-OCTYLPHENOXYPOLYET~OXYETHANOL (3 MOLES RTi~I,EI~ OXIDE) - TRIESTER
To a 3-1 three-necked round bottom flask fltted with a mechanical stirrer, thermGmeter, and Dean-Stark trap with reflux condenser are charged 845 g. -(1 mole) Or a trimer acid mixture (~mery Industries -~
1834-18R trimer acid,) comprising 70-80% trimer acid and - -:,. ...
30 to 20% dimer acid, 316 g. (2 moles) of isodecyl alcohol, 338 g. (1 mole) of octylphenoxypolyethoxyethanol contalning about 3 moles of condensed ethylene oxide, .~-200 ml of toluene, and 1.0 gO Or p-toluenesulronic acid.
- The reaction mixture is heated toreflux (with stirring) which occur~ near 135C. Refluxing is contin-led ~or 6 , hours during which time the theoretical quantlty of water ls evolved. Toluene ~olvent is stripped under vacuum, 3.0 g. of Na2C03 added to neutralize the p-toluene~ulfonic acid, and the product filtered. The material prepared in this.way generally has an acid near 1Ø
The theoretical product distribution assuming that equilibrium has been obtained and that there are no rree energy formatlon difrerences between the various ester~ is the ~ollowing:
` wt ~ mole . . .
trimer acid, triisodecyl triester25.929.6 trimer acid, diisodecyl~mono-,', octylphenoxypolyethoxyethanol (3 moles ethylene oxide) 44.5 44.5 trimer acid, isodecyl di-octylphenoxypolyethoxyethanol -~ (3 moles ethylene oxlde) trlester 25.0 22.2 - 20 trimer acld, tri-ockylphenoxypolyethoxyethanol (3 moles elhylene ox~de) 4.6 ~.7 Actual analysis showa the diisodecylmono-octylphenoxypol~ethoxyethanol ester to be present in the preponderant numerical percentage amount, and - actual chromatographic analysis conforms substantially --.

~" , .

with the predicted amount. Changes in the ratio of the ester components may be obtained, by altering the esterification conditions.
The following Table II lists typical mixed polyesters ; prepared for use with the present invention and in accordance with the above general method:
TABLE II

Example 1 dimethyl/mono-octylphenoxy poly- Ester of ethoxyethanol containing average trimer of of 3 moles of condensed ethylene oxide. lioleic acid.
Example 2 dibutyl/mono-octylphenoxy poly- Ester of ethoxyethanol with average of 3 the trimer moles of ethylene oxide. of linoleic -Example 3 di-2-ethylhexyl/mono-octylphenoxy Ester of ;~ polyethoxyethanol with 3 moles of the trimer -ethylene oxide. of linoleic acid.

,' Example 4 diisodecyl/mono-octylphenoxy poly- Ester of ethoxyethanol with average of 3 moles the trimer -of ethylene oxide. of linoleic -acid. -Example 5 di C16_20 aliphatic alcohol/mono- Ester of ~, octylphenoxy polyethoxyethanol the trimer with 3 moles of ethylene oxide. of linoleic acid.
Example 6 mono-isodecyl/di-octylphenoxy Ester of polyethoxyethanol with 3 moles the trimer -of ethylene oxide. of linoleic - :
acid.
.. . .
::

,' , ~ ', , ' , ,", - ' ' ' . :., 103930Z ~
TABLE II (Cont'd) -Example 7 diisodecyl/mono-octylphenoxy poly- Ester of the ethoxyethanol with average of 5 trimer of moles of ethylene oxide. linoleic acid.
Example 8 dimethyl/mono-octylphenoxy ethoxy- Ester of the ethanol with average of 1 mole of trimer of ethylene oxide. linoleic acid.
Example 9 mono-isodecyl/mono-octylphenoxy poly- Ester of the - ethoxy ethanol with 3 moles of dimer of ethylene oxide. linoleic acid.
i ~
The esterification reaction is usually acid catalyzed and can be carried out over a broad range of temperatures, but usually the temperature will vary from about 75C. to about 180C. The mixture of aliphatic alcohol and ethoxylated aromatic alcohols can also vary fairly widely depending on the products desired, but ordinarily the ratio of the aliphatic alcohol to the ethoxylated aromatic alcohol will vary from about (on a molar basis) one to four to about four to one, and more preferably about one to two to about two to one. The quantity of mixed alcohols used should be sufficient to essentially completely esterify the polycarboxylic acid (i.e. the trimer - or dimer acid, or mixture thereof) and there can be used an equivalent amount or slight molar excess of alcohols in relation to the polycarboxylic acid during the esterification reaction.

', ., .
The base fuel employed in the following Examples (Tables III, IV, and V below) is a Howell unleaded gasoline as described hereinabove, except for the BBCDT-KC tests wherein .. . .
an MS-08 gasoline as described hereinabove is used. Induction System Deposit Test results (ISDT) are reported in milligrams - (mg.) of deposit as are the Blowby Carburetor Detergency ; Keep Clean Engine Test results. Percent rusting is also -, reported. These test procedures are described above.
TABLE III
: 10 Example Fuel Additive and ISDTl mg BBCDT -KC
`~ Concentration ppm deposit mq. deposit -: Gasoline (Valve and --por`t) .. , ', :
Control Untreated Gasoline : i.e. base fuel 365 13 ,~
Comparative triisodecyl ester of Example A trimer of linoleic acid, 300 ppm 170 No. 10 mixed dimethyl poly-ester of Example 1 ~ -(see Table II), 300 ppm 72 .. . ..
No. 11 mixed dibutyl poly-ester of Example 2 (Table II above) 300 ppm 35 18.1 . .. ~, .
,; No. 12 mixed diisodecyl -polyester of Example 4 (Table II above) 300 ppm 37 14.2 No. 13 mixed diisodecyl poly-ester of Example 7 (Table II above) 300 ppm 475 --No. 14 tri-octylpolyethoxy-ethanol ester of trimer of -~
linoleic acid with 3 moles : -ethylene oxide, 500 ppm 186 . ' .

,; :

.

; 103930Z
TABLE III (Cont'd) `:
'' Example Fuel Additive and ISDT , mg. BBCDT -KC
Concentration ppm deposit mg. depo-s t Gasoline (Valve and ~ort) -,:
'' Comparative commercially available Example B and used alkyl ammonium phosphate, 50 ppm 435 4.0 , :
-~- Comparative commercially available '' Example C and used polybutene succinimide, 140 ppm 1247 3.3 (1) Induction System Deposit Test, as described above.

' 10 (2) Blowby Carburetor Detergency Deep Clean Engine Test, as described above.
' In Table IV, below, there are shown results obtained with a combination or mixture of additives according to the present invention.

'-' 20 '- 30 /
.. .: . ; -,, , ,, . ., : .

o 1039302 ~ U~ o o o o o : .............. ~ ~

. ~ _ .... ~ ~
..
o o o ~:r o ':.' ..

,, . .
.,: U~
K
. I~a ~ .

.',. ~
~tn o H ~ ~ N ~ ~ O ..

E ~1~
H¦ O o R 30 . ~ ~ ~ O ~ Id `Q, O : .

:~ ~ x~ cnC ~ nc U

, 1 . 0 I E E ~ ~ E E ~ ~, ~ E E ~ C ~14 ~ E '~
U~ '~ ~ '~ ~ ~q o o . ~ , , 1 ~ , 1 1 1 1 1 ~4' 1 1 l a)~ I 1 1 1~ H HH _~ H H ~H H HH Ht) ~ HH ~H H
O
u~

, w æ z z z z ", j . , .

.: ~

c)~
103930Z ',, o o o o ~ ~ ~1 .,. ~.
~Q ~ o ,, ,, 4~
-- ~ ,c .4:, '~ ~ ~ o O
O
H_I O

t~ o ¦ E
C ) H ` ~1 al ~
: H ~
x~

~'' _ O ~ '~

Q. ~
_ a~ ~ R~ R:S
.- H Id H11) H tl) H ~ X

~¦ s ~ SF~

~1) ~ _~ s ~ ~ UO~ 0 .- ~ O r~ X ~~rl X ~ ~1 X
~ ~ ~ ~ ~ O ~ R rl " g~ ~ X ~ X _ ~ ~ X E~ H
1 O U~ 1 00 U~ O 0 I I I ~ II I I ~ R I I I ~ $ ~

14 H H ~HH HH tHJ~ H H ~H a a a o ~
,~ O _I ~ O ~ ~ ~

~I z z z c~ s o s ~ .

~' :
,, )~ 30- :"

, ". , ~ , , . " . , - . " , . : ., .

:` ~03930Z

,. ,.
o~
.. ,, C,~ ~., -: I m~

ô

C~ zm '- .:

.,' ~ /
\
:' \,~/ - '-.''', ~
, ' .
.
. '' .,.
.
- 30a -~:
,' :

,, " , , , , .,; , .
, . ; , ' '' , ,' ,;" :' . ':
",. . .. . . .

1039302 ' - t TABLF. ~J_(Cont~d) WHERE
Zl is the hydrocarbon residue of the product o~ trimerization . of an unsaturated C18 fa~ty acid, such as linoleic acid, which i~.. a mixture of about 70-80~ trimer acid (C54) and and about 30-20% of dimer acid (C36), all parts by weight.

:

; ' ' ' ' .. . .
", ~ ` ~
~.03930Z
TABLE V
~(Octane Number Requirement Increase) Example Fuel Additive and Octane Number * ;- -Concentration, ppm, Requirement in Gasoline Increase Control Untreated gasoline, i.e.
~: base fuel 10 ` Comparative Commercially available Example D and used polybutene succinimide, 140 ppm 8 ; No. 22 Same additive package or blends as in Example No. 15 (Table IV) (total = 370 ppm) 4 .: 10 No. 23 Same additive as Example No. 2 ~
Table II at 300 ppm 5 -- .-* As measured by the Combustion Chamber Deposit Engine Test.

. - ...

:- .
. .
,:
-''.
. . , , 20 ~,,'' .
.
.,4.
",-," -.
' . .
, ,, - , ~ 103930Z
As is evident rrom the date in Table IXI, the mixed polyesters o~ this invention while individually a~lording no carburetor detergency activity, per se, :- are very e~ective at contro71ing induction system deposits in an internal combustion engine.
~hen the mixed polyesters are used in combination . with rust inhibitors and carburetor detergents as shown in Table IV so that a multipurpose additive package is ~ormed, the activlty o~ examples 15, 16, and l9 is significantly better than the base fuel ln all three per~ormance categories, i.e., rust inhibitor, carburetor detergency, and induction system detergency. Although examples 17, 18, 20, 21, and 22 show higher levels o~ induction system deposits than the base ruel their total perrormance is signiricantly better than ` 15 the base fuel treated with currently used commercial additives such as the alkyl ammonium phosphates and the polybutene suc~inlmides. It is important to remember . that untreated gasoline is rarely used in present day automobiles and that gasoline treated with conventional . 20 carburetor detergents and rust lnhibitors will normally give higher levels of induction system deposits than the base gasoline as is shown in Comparative Examples B and C Or Table III. ~

:'.

_3~_ ,, ~ , .

,' . ",, ~'~

Although the mechanism of activity is no~ clear, it - is evident from the data in Table V that the additive combina-- tion of our invention is effective in modifying the deposits in the combustian chamber such that the octane num~er require-ment increase of the engine is less than with either untreated gasoline or base gasoline treated with a commercially used polybutene succinimide.
In a specific example of an alternative embodiment of -this invention, wherein the carburetor detergent tl) and 10 induction system deposit control additive (3) are used (without any added rust inhibitor) in gasoline, at a total concentration of about 350 ppm, (50 ppm of 1 and 300 ppm of 3), the following : results are obtained: for the ISDT Test, 201 milligrams (mg.) - of deposits; and for the BBCDT-KC Test, 1.3 mg. of deposits. In this test, component (1) was a t-C18-C22 alkyl amine such as was used in Example 15, and component (3) was the mixed poly-ester of Example 4. As noted previously, a Howell unleaded -. gasoline is used for the ISDT tests, and MS-08 gasoline is used for the BBCDT-KC tests.
In another alternative embodiment of this invention, other dicarboxylic acid esters, such as an adipate diester :. may be substituted in whole or part for component (3) of the detergent composition, noted above, to provide induction systems deposit control. Thus, an adipate diester comprising -- the mono-isodecyl, mono-octyl phenoxy polyethoxy ethanol (containing an average of 3 moles of condensed ethylene ,:

~, " .
f oxide) mixed ester of adipic acid and made by a conventional acid esterification process, gave the following result: in the ISDT test, 160 mg. of deposit. Other adipic acid esters, e.g., the mixed adipic acid esters comprising a mixed Cl-C20 alkyl/alkyl phenoxy (alkyl of C4 to Cg) polyethoxy ethanol (containing 1 to 20 moles, and more preferably about 1 to 5 moles condensed ethylene oxide) ester may also be used to pro-vide induction system deposit control either alone, or in com-bination with component (1) and (2) above. The adipic acid ester is used in the same amount as component (3) noted above, either alone in gasoline or in combination with components (l)*
and (2)*, noted above.
Other results using 300 ppm of the specific mono-isodecyl, mono-octyl phenoxy polyethoxy ethanol (3 moles ethylene oxide) adipic ester noted above in combination with ppm of the t-C18-C22 alkyl amine (component (1) above) are as follows: in the ISDT test, 225 mg. of deposit, and in the BBCDT-KC test, 2.3 mg. of deposit. When 10 ppm of the rust ,-inhibitor component (2) of Example No. 15 is added to the mix-~ .......... .
ture of the t-C18-C22 alkyl amine and the adipic acid ester, noted above, to give a three component system, the following -results are obtained: in the ISDT test, 327 mg. of deposit, 2.2 mg. of deposit in the BBCDT-KC test, and 0~ area rusted in the r-ust test described above.

*Component (1) refers to the t-alkyl amine (of 6 to 24 carbon atoms) carburetor detergent component and component (2) refers to the surface active alkyl ammonium carboxylate salt-ethoxylated alkyl phenol ester rust inhibitor component, hereinbefore described.
,;' . .

,, ., ~039~302 ~ Ir~ anot~ler e~ample using 50 ppm Or the ~-Clg-C2~
alkyl .~mine (component (1) a~o~e), ~ ppm of the rust inhibitor component (2) of Example ~o. 15J and 300 ppm Or the mono-isodecyl, mono-octyl phenoxy polye~hoxyethanol (contairing 5 moles of ethylene oxide~ adipate ester the fol].otJing results ~ere obtalned: in the ISDT test, 237 mg. of deposit, ; in the ~BCDT-K5 test, 305 mg. of deposit, and 0% area rusted in the rust tes~.

-~
.

. ' , ' --.
:

:

,~ . .
. .

Claims

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A multi-functional additive composition suitable for addition to distillate hydrocarbon fuels having a major proportion of a hydrocarbon base fuel distilling with the gasoline distillation range, the additve composition comprising a mixture of (1) about 20 to about 250 parts by weight of a tertiary alkyl primary amine having a branched backbone and a total of 6 to 24 carbon atoms;
(2) about 5 to about 100 parts by weight of a surface active alkyl ammonium carboxylate salt-ethoxylated alkyl phenol ester of a trimer or dimer acid of the formula ]x where n is an average number from 1 to 12.5; and wherein in the case of the salt-ester derived from a trimer acid x is 1 or 2, and y is 1 or 2, the sum of x and y being 3;
and in the case of the salt-ester derived from a dimer acid, both x and y are each 1;
R4 is an alkyl group containing 4 to 12 carbon atoms;
R5 is H or an alkyl group containing 4 to 12 carbon atoms;
R6 is an alkyl group containing 2 to 24 carbon atoms which may be straight or branched chain or an amine substituted alkyl group of 2 to 24 carbon atoms; and Z is a saturated or unsaturated hydrocarbon residue of the acid, said hydrocarbon residue having 34 to 51 carbon atoms;
(3) about 100 to 650 parts by weight of a polyester prepared from the reaction of a dimer or trimer acid and a mixture of an aliphatic alcohol having from about 1 to 24 carbon atoms and an alkoxylated alkyl phenol, said dimer and trimer acid having been produced by the polymerization of an unsaturated aliphatic monocarboxylic acid having between 16 and 18 carbon atoms, said polyester having the general formula where Z1 is a saturated or unsaturated hydrocarbon residue having 34 to 51 carbon atoms and is the residue of a dimer or trimer acid, or mixture thereof; and n is an average number of from about 1 to 20; in the case of the mixed polyester derived from a trimer acid, p is 1 or 2 and q is 1 or 2, the sum of p and q being 3; and in the case of the mixed ester derived from a dimer acid, both p and q are each l;
R7 is an alkyl group containing 4 to 12 carbon atoms;
R8 is H or an alkyl group containing 4 to 12 carbon atoms; and R9 is a straight or branched chain alkyl group containing 1 to 24 carbon atoms.

2. A composition according to claim 1 wherein the tertiary alkyl primary amine has a carbon atom content of 12 to 22 carbon atoms.

3. A composition according to claim 2 wherein the tertiary alkyl primary amine is present in an amount of from about 50 to 100 parts by weight.

4. A composition according to claim 1 wherein the polyester is a mono-(ethoxylated alkyl phenol), di-isodecyl ester of the trimer of linoleic acid, the ethoxylated alkyl phenol having an alkyl group of 8 or 9 carbon atoms and an average of about 3 ethylene oxide units.

5. A composition according to claim 1 wherein in the formula of component (2), n is 3 to 10, x is 1, y is 2 and Z
is a hydrocarbon acid residue having about or an average number of 51 carbon atoms.

6. A composition according to claim 5 wherein n is 3.

7. A composition according to claim 1 wherein com-ponent (1) is present in an amount of about 50 to about 100 parts by weight, component (2) is present in an amount of about 10 to about 50 parts by weight, and component (3) is present in an amount of about 200 to about 400 parts by weight.

8. A composition according to claim 1, wherein in the formula of component (3), n is a number ranging from about 1 to about 4.

9. A composition according to claim 1 wherein, in the formula of component (3), R7 is an alkyl group containing 8 or 9 carbon atoms.

10. A composition according to claim 1 wherein, in the formula of component (3), R8 is hydrogen.

11. An improved detergent motor fuel composition comprising (a) a major proportion of a hydrocarbon base fuel boiling in the gasoline boiling or distillation range and (b) about 125 to about 1000 ppm of the additive composition of claim 1.

12. An improved detergent motor fuel composition comprising (A) a major proportion of a hydrocarbon base fuel boiling in the gasoline boiling or distillation range and (B) about 150 to about 750 ppm of the multi-functional additive composition of claim 1.

13. A detergent additive composition suitable for addition to gasoline comprising a mixture of (1) about 20 to about 250 parts by weight of a tertiary alkyl primary amine having a branched backbone and a total of 6 to 24 carbon atoms; and (2) about 100 to about 650 parts by weight of a mixed polyester of the formula wherein n is an average number of from about 1 to 20; and in the case of the mixed polyester derived from a trimer acid p is 1 or 2 and q is 1 or 2, the sum of p and q being 3; and in the case of the mixed ester derived from a dimer acid, both p and q are each 1;
R7 is an alkyl group containing 4 to 12 carbon atoms, R8 is H or an alkyl group containing 4 to 12 carbon atoms;
R9 is a straight or branched chain alkyl group containing 1 to 24 carbon atoms;
Z1 is a saturated or unsaturated hydrocarbon residue having about 34 to about 51 carbon atoms, said residue being the residue of a dimer or trimer acid, or mixture thereof.

14. A composition according to Claim 13 wherein, in the formula of component (2), n is a number ranging from about 1 to about 4.

15. A composition according to Claim 13 wherein, in the formula of component (2), R7 is an alkyl group containing 8 or 9 carbon atoms.

16. A composition according to Claim 13 wherein, in the formula of component (2), R8 is hydrogen.

17. A composition according to Claim 13 wherein (1) is present in an amount of about 50 to about 100 parts by weight and (2) is present in an amount of about 200 to about 400 parts by weight.

18. A composition according to claim 13 wherein (1) is a tertiary alkyl primary amine having a carbon atom content of 18 to 22 carbon atoms, and wherein (2) is the diisodecyl mono-octylphenoxypolyethoxyethanol (containing 3 moles of ethylene oxide) ester of the trimer of linoleic acid.

19. An improved detergent motor fuel composition comprising (A) a major proportion of a hydrocarbon base fuel boiling in the gasoline or distillation range and (B) about 120 to 900 ppm of the additive composition of Claim 13.

20. As a novel composition of matter a mixed polyester of the formula wherein n is an average number of from about 1 to 20; and in the case of the mixed polyester derived from a trimer acid p is 1 or 2 and q is 1 or 2, the sum of p and q being 3; and in the case of the mixed ester derived from a dimer acid, both p and q are each 1;
R7 is an alkyl group containing 4 to 12 carbon atoms;
R8 is H or an alkyl group containing 4 to 12 carbon atoms;
R9 is a straight or branched chain alkyl group containing 1 to 24 carbon atoms; and Z1 is a saturated or unsaturated hydrocarbon residue having about 34 to about 51 carbon atoms, said residue being the residue of a dimer or trimer acid or mixture thereof.

21. The mixed polyester of claim 20 wherein n is a number ranging from about 1 to about 4.

22. The mixed polyester of Claim 20 wherein R7 is an alkyl group containing 8 or 9 carbon atoms.

23. The mixed polyester of Claim 20 wherein R8 is hydrogen.

24. A composition comprising (A) a major amount of a hydrocarbon base fuel boiling in the gasoline range and (B) a minor amount of about 100 to about 650 ppm of the mixed polyester of Claim 20.

25. A composition according to Claim 24 wherein the mixed polyester is the diisodecyl mono-octylphenoxypoly-ethoxyethanol (containing an average of 3 moles of ethylene oxide) ester of the trimer of linoleic acid.