CA1075000A - Motor fuel composition - Google Patents

Abstract

IMPROVED MOTOR FUEL COMPOSITION

Abstract of the Disclosure Motor fuel composition having detergent properties are disclosed and claimed which are particularly useful in spark-ignition, internal combustion engines. The fuel compositions of the present invention contain certain additives which either substantially eliminate, mitigate against, or maintain at a low level, deposits which would otherwise form in the carburetor, in the intake valves and ports, and in the combustion chamber, including the spark plugs. Such carburetor and intake system (induction system) deposits are to be avoided since they tend to restrict the flow of air through the carburetor especially at idle and at low speeds and/or cause improper valve closing and sluggish valve action. These conditions produce rough engine idling, stalling, and can also result in excessive hydrocarbon and carbon monoxide exhaust emissions. Combustion chamber deposits are to be avoided since they cause an increase in octane requirement, emissions and cause preignition.
The fuel additives of the present invention include for induction system deposit control an ester selected from a dimer or timer acid ester or from other polycarboxylic acid esters, especially dicarboxylic acid ester.

Description

1075()00 This inventioll relates to motor fuel compositions for spark i~r~tion, intcrnal combustion engines. 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 a~d combustion chamber lnciuding the spark plugs of an internal combustion engine. Thus, the formulations of the present invention are particularly effective as carburetor detergents to clean up and maintain the cleanliness of the carburetor, the combustion chamber and the spark plugs, and to prevent, reduce or minimize against deposits forming in the induction system such as the area around the valves and ports. The gasoline additive or additives or gasoline fuel additive - -or additives of the present invention act to control spark plug fouiing and thus help to keep the spark plugs relatively clean and relatively free of any deposits. This invention also relates to an additive concentrate of one or more of the additives in mi~ture, solution or combination.
Modern internal combustion engine design is undergoing and has undergone important changes to meet stricter standards for engine and exhaust gas emissions. A major change in engine design is the feeding or recycling of blowby gases from the crankcase of the engine into the intake air supply to the carburetor rather than the venting of these gases to the atmosphereJ as in the past. The blowby gases contain substantial amounts of deposit-forming substances and are known to form deposits in and around the throttle body area of the carburetor. These deposits restrict the flow of air through the carburetor at idle and at low speeds so that an overrich fuel mixture results. This condition produces rough engine idling, stalling and also results in excessive hydrocarbon and caroon monoxide exhaust emissions being emitted to the atmosphere.

-2-`` 1075000 In addition to the cha"ges that have already been made, it i8 antic~pated that additional burdens and demands will be placed on present day internal combustion engines and their fue1s with the advent of new emission control devices, such as exhaust gas recirculation systems and catalytic exhaust mufflers. Also, the use of certain fuel additives such as the alkyl ammonium phosphate detergents may have to ~e restricted or eliminated because catalytic exhaust mufflers wnich utilize metal catalysts will be poisoned by phosphorus-containing compounds.
It is an object of the present invention to provide a detergent motor fuel which will have certain carburetor deterger.t properties and which will clean up and maintain the cleanliness of the carburetor and also the remainder of the fuel induction system such as the valves and ports and reduce the octane requirement increase of an internal combustion engine. In the present invention the motor fuel used may be an unleaded fuel, a leaded fuel, a low leaded fuel, or a fuel containing manganese.
It is another object of the present invention to provide a detergent fuel which will maintain a low level of hydrocarbon and carbon monoxide exh~ust gas emissions and which will avoid the use of phosphorus containing additives. It is still a further object of the present invention to provide a detergent fuel which has other desirable properties such as rust and corrosion protection, water demulsibility properties, anti-icing properties, etc. It is a further object of the present invention to provide multi-functional gasolineadditives or additive combinations effective in inhibiting the formation of intake valve deposits in addition to being effective as carburetor detergents, and which can be used at relatively low concentrations (and thus at relatively low cost) for example at the treating level of about 100~ parts per million (p.p~m.
on a weight basis in the gasoline), or less, and more preferably 600 p.p.m. or less, and even more preferably 400 p.p.m. or less.

.

There are, of course, other detPrgent motor fuel compositions available today, but they gener~lly suPPer from one or more defici~ncies.
Either they are used at very high concantrations, for example, something of the order of 4000 p.?.m.; or if used at the use levels in which we are interested, the available formulations suffer from one or more defects.
We have discovered that the combination of (1) selected tertiary alkyl primary amines having branched backbones and a total of about 6 to 24 carbon atoms; (2) a surface active alkyl ammonium carboxylate salt-ethoxylated alkyl phanol ester of a trimer or dimar acid; and completely

(3) a dimar or trimer acid ester comprising the essentially/esterified polyester of a dimer or trimer acid, or mixture of dimer and trimer acids, produced by the polymerization or condensation of an unsaturated aliphatic monocarboxylic acid having between 16 and lg carbon atoms per molecule which is esterified with (or incorporates) a mixture of aliphatic and ethoxylated aromatic alcohols, are effective in reducing or preventing the formation of carburetor and other induction system deposits.
According to one aspect of the present inventlon, therefore?
we provide a normally liquid, multi-functional, additive composition for addition to a leaded, low lead, or llnleaded gasoline, or gasoline . .' ` ` .' .' : . .

~075000 cor.taining mqllgullese, i.e., to a distillate hydrocarbon fuel ccmpr~sin~
a major proportion of a hydrocarbon base fuel distilling wit~in the gasoline distillation range. The three component composition rarlging from n total of about 125 to about 1000 parts, on a weight basis, is comprised of about 20 to about 250 parts, and more preferably, about 50 to 100 parts by weight of ~1) a tertiary alkyl branched chain primary amlne, as above described; about 5 to about 100 parts and, more pre-ferably, about 10 to 25 parts by weight of (2) a surface active alkyl ammonium carboxylate salt-ethoxylated alXyl phenol ester of a trimer or dimer ~cid, as above described; and about 100 to about 650 parts by weight and, mora preferably, about 200 to 400 parts by weight of (3j a trimer acid or dimer acid mixed ester as above described. In an alternative embodiment of the invention and where induction system control, per se, is primarily desired, then components (1) and (2) can be omitted, and component (3) can be utili~ed itself in the fuel, on a total weight basis of about 100 to about 650 p.p.m., more preferably about 200 to 400 p.p.m., or component (3) can be used .

in con~unct1on with component (1) to provide a two-component package or blend providing good carburetor detergency and good induction system depos~t control, or component (3) can be used with other carburetor detargents and/or other rust inhibitors. When using a combination or mixture of components (1) and (3), th~y are used in the same amount as noted above, i.e., about 20 to 250 p.p.m.
of (1) and ~ore prefarably, about 50 to 100 p.p.m. of (1) and about 100 to 650 p.p.m., more preferabl~, about 200 to 400 p.p.m. of (3).
On a fuel traating lev91 basis, i e., on a level related to c 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 lCOO p.p.m. (weight basis) and on an individual or compoDent - basis, in ar. amount of from about 20 to 250 p.p.m., and more ~referably - 50 to 100 p.p.m. of (1); about 5 to about 100 p.p.m., more preferably ~about :; 10 to about 25p.p.m. of (2); and about 100 to about 650 p.p.m., more preferably 200 to 400 p.p.m. 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). of gasoline of (l);
1.25 to 25, more preferably 2.5 to 6.25 lbs./1000 bbls. of gasoline of (2); and 25 to 152.5, more preferably 50 to 100 lbs./lOQO bbls. of ~ga301ine of (3~.
~or the concentration of the additive component (3~, above (~hen ussd Alone) the p.p.m. concentration and the pounds per barrel of g~soline treating level is the same as noted for component (3) ab~ve .e.S about 25 to 16205, m~re preferably about 50 to 100 lbs./1000 bbls. (barrels) of gasolins, or about 100 to 650 p.p.m., and more prefarably abcut 200 to about 400 p.p.m. of (3).
~or the concentration of tne additive mix~ure (1) and (3) in gasoline~ the trsatiDg level should be in tho rPnge of about 20 3~ to 250 p.p.m., more preferably about 50 to 100 p.p.m., of componont ~3 .

(1), and about 100 to 650 p.p.m., more preferably about 200 to 400 p.p.m. o~ component (1). On a pounds per barrel of gasoline bssis, this amounts to about 5 to sbout 62,5 lbs., more preferably about 12.5 to 25 lbs. per 1000 bbls, of gasoline of component (1); and about 25 to 162.5 lbs., and more preferab~y 50 to 100 lbs. per 1000 bbls. of gasoline of component (3), The tertiary (tert.) or t-aIkyl primary ~m 'ne, haviDg at least one branched chain, may be represented by the general formula (I).

in which Rl, R2 and R3 are alkyl groups whose total carbon atom content ranges from 6 to 24. It is preferred that two of the R
groups, for example, and Rl and R3 of the t-alkyl primary ~;ne be methyl g.oups.
The t-alkyl primary amines with branched chains and which may bs used in the compositions of the present invention include, for example, t-octylamine,t-nonylaminej t-dodecylamine, t-tetradecyl~;ne, t-octa-decylamine, t-docosyla~ine, t-tetracosylamine and mixtures of tw~
or more of such amines. These amines are commonly prepared by reactions known to those skilled in the art such as tha reaction of nitriles with alk~nes or-secondary or tertiary alcohols in strongly acidic media. Commercially available t-aIkyl primary amines are often mixtures. t-Octylamine having a branched structure has the formula:

CH3 f CH2 C ~H2 and the alX~l group of this amine will hereinafter be referred to 2S
t-octyl. One form of t-nonylamine is prepared as a mix~ure containir.g ' ' :' -: ,, :- ' -` '` ~07,5UOO
.

. C6H~3C(CH3)2NH2 and C7H15C(CH3~2NH2 and has a neutral equivalent of about 142. A commercial preparation which can be used in the present invention is readily available under the trademark Primene ~l-R which is the trademark used for a mixture of t-dodecyl, t-tridecyl- and t-tetradecylamines or prin-cipally a mixture of t-C12H25NH2 to t-C14H29NH2 amine9 havi~g a neutral equivalent of about 191. An~ her commercial preparation ~ -.
which i9 useful in the present invention is available under the trademark Primene JM~T. Primene JN-T is principally a mixture of t-Cl~H37NH2 to t-C22H45NH2 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 co~taining no hydrogen atoms and in the present invention at least one of the alkyl groups is branched.
The alkyl a~monium carboxylate salt-ethoxylated alkyl phen~l ester of a trimer or dimer acid (or mixture thereof) is added or .
~ included primarily to provide rust and/or corrosion protection although ; there is also some modest carburetor detergency activity, has the i i-~ following formula (II):

~3~ [c--O(CN~C~O)n ~ ~ (II) [C2 NH3R6]y x where n is an average number from about 1 to 12.5 and more preferably from about 3 to 10; and in the casa 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 æalt-ester derive~ from a dimeracid, both x and y are each l;

;~
' ~ . ' ' - ' - ' . - -: - - ' , ,- ~ ' .

iO7S000 R4 is an alkyl group containing 4 to 12 carbon atoms;
R5 is H or an alkyl group containing 4 to 12 carbon ato~s;
R6 is an alkyl group containing 2 to 24 carbon atoms which may be straight or branched chain or an amlne substituted alkyl group of 2 to 24 carbon atoms. Preferably~ R6 contains 12 to 22 carbon atoms; nd Z is a saturated or unsatur&ted 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 ordin rily 34 carbon atoms in the case oI a dimer acid).
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 of the dimer and trimer acid derivatives may be used , j ' in the present invention.
:
Also, the presence of some monocsrboxylic Clg acids or the like in the ester or salt form, or mixtures of both ester and salt form, . may be tolerated in minor amounts, about 5% or less.

` Specific embodiments of the alkyl ammonium carboxylate salt-ester of the general formula II, above, and wherein, R4 is substantially or . essentially all octyl, i.e. - CgH17, and R5 is H and which are usable `~ in the present invention are given in Table I below:

TABLE I -~, n R6 X Y

Alkyl ammonium car-boxylate salt-ester A.............................. 1.5 12-14 1 2 B.............................. 1.5 t C12~14 2 C................................ 3 C12_14 1 2 D................................ 3 C12-14 2 E................................ 5 C12-1~, 1 F.............................. 7.5 t C12-14 1 2 _9_ . .

- : ' . . - . .

10751)00 n R6 X y . . _ _ _ . _ . . . _ . _ _ _ cont'd.
G......................... 9.5 C12 14 1 2 H......................... 9.5 t C12-14 2 I........................ 12.5 t C12-14 1 2 J........................... 3 CH2CH2NH2 2 K........................... 3 (CH2CH2NH)2H 2 L........................... 3 (CH2CH2NH)3H 2 M......................... 1.5 C12-14 N........................... 3 12-14 O......................... 9.5 t-CH12 14 P........................... 3 t-Glg 22 Q........................... 3 t-Clg 22 2 R........................... 3 t C18-22 1 2 S........................... 5 C12_14 T....................... ~ 1.5 t C18-22 U........................... 5 lg-22 V........................... 5 t C12-14 2 :
W......................... 7.5 C12_14 2 X.......................... 10 C12_14 2 Y......................... 1.5 C18_22 2 2................. 5 t C1~-22 2 A~................ 1 ; C12-14 1 2 .............. 10 t C12-14 1 2 C'................ 1 t C18-22 1 2 - D~................ 5 Clg_22 1 2 The alkyl ammoniu~ carboxylate salt ester can be made in known fashion, by the acid catalyzed e~terification of a suitable dimer or trimer acid, or mixture thereof, for ex&~ple, in the case of th~ diester-monosalt, with two moles of a suitab1.e ethoxylated alhyl - ~
.

"` iO75~00 phenol followed by con~ersion of the remaining csrboxylic acld func-tionslity to sn ~lkyl ammonium csrboxylate sslt with the sddition of a suitable amine. The trimer acid may be the product deri~ed from the trimerization reaction of 8 C18 unsaturated fatty scid;
sn exsmple of a suitable trimer acidis that available under the trade-msrk Empol 1041. The preparation of such dimer and trimer acids is described in U.S. Patent 2,632,695. A generalized reaction scheme for the preparation of an alkyl ammonium carboxylate salt-~ster is sho~.~ below using a trimer ~cid for illustrative purposes:

. .

C51(C02~)3 + 2~(CH2CH2)n ~ d54 (1) Acid C

[ C2~C~2C~2C)n--~ ~4s] 2 C5~

LC2(~a2~2C)n~ ]~

CO2e ~NH3R6 whera n, R4, R5 and R6 have the v lues given previously, and C51 is the carbon atom content of the hyLrocarson residue.
In order to provide induction system and combustio~ chamber dzposit control,including control against spark plug fouling, there is ncluded in the additive or additive combination, a ~ixed poly_ster of a dimer acid or a tri~er acid, or a -i075~00 mixture of such dimer and trimer acids. The mixed polyester~ as well ns tha dimar and trimer ncids may be prepared in known fashion. ~or ex~nple~ an unsatur&ted al~phatic monocarbo~:ylic acid having between about 16 and 1~ carbon atoms per molecule, for example linoleic acid can be polymerized or condensed to form essentially the ~imer of linoleic acid, a dicarboxylic acid, and also the aliphatic mono-ca boxylic acid can be polymerized to form essentially the trirner of linoleic acid, a tricarboxylic acid. Mixtures of such dicarboxylic and tricarboxylic acids may also be formed. Similarly, other C16 and C18 unsaturated aliphatic monocarboxylic acids~ ir~cl~ding ricinoleic and linolenic acid can be polymerized to dimer and trimer acids or mixtures of such dimer ar.d trimer acids. The preparation of sucb dimer and triiner acids is described in U.S. Patent 2,632,695. The mixed polyesters used in the present invention are prepared by re--acting a suitable a~ount of a mix.ture of an aliphatic alcohol and an etho~ylated aromatic alcohol with the polycarboxylic acid to esteriy essentially all of the carboxyl groups in the acid.
Esteriication is conducted according to conventional, know~ methods.

The aliphatic alcohols which are suitable for this purpose are preferably saturated aliphatic alcohols, having frGm abou~ 1 to 24 carbon atoms. Representative aliphat c alcohols include methyl alcohol, propyl alcohol, n-butyl alcohol, isobutyl ~lcohol, hexyl alcohol, 2-ethylhexyl alcohol, decyl alcohol, do~ecyl alcohol, tridecyl alcohol, isodecyl alcohol, lauryl alcohol, ste2ryl alcohol~
hex~decyl alcohol, ar.d nondecvl alcohol. Prsferably, the aromatic or aromatic containing alcohols which are used are alkylated ~henols which ha~e been ethoxylated with v~ ying amounts of an alkyiene oxide such as e'hylene oxide. (These materi&ls are kno-~ gener~lly as alkylpheno~ypolyethoxy sth&nois.) The n~mber of moles of ethy;ens oxide which may be condensed wi~h tns alkyl~+.ed phenol may vary fro~

about one to hbout 2~ ethyl~n3 oxid~ units, and more ~preferably from " 107S000 .
abcut ono to four moles of ethylene oxide. ~ ile the presence of some unreacted alcohols and some completely e~terified all-aliphatic or all-ethoxylated aromatic esters will be present in the ester;fication mixture, the principal active ingredient or the principal active mixed polyester has the following general for~ula:

~ ( 2 2 )D~

~C0 ~9]q P

wherein n is an average number of from about 1 to 20 and, more preferably, o~
from about 1 to about 4; 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 l; and where ~ is a saturated or unsaturated hydrocarbon residue having an average of 34 to 51 carbon ,: -atoms, said residue being the residua of a dimer or trimer acid of --~ linoleic acid, or mixture of said dimers and trimers of linoleic . .
~ acid; R7 is an ~lkyl group containing 4 to 12 carbon atoms, more - preferably 8 to 9 carbon atoms; Rg is H or an alkyl grcup conta ning

4 to 12 carbon atoms,more preferably H; R9 is an alkyl group contain-ing 1 to 24 carbon atoms which may be straight or branched chain.
. . .:
-~ The aromatic alkoxylated alkyl pheno;s are pre~erably based on . .
either octyl or nonyl phenol and can contain approximately 1 to 20 moles of ethylene oxide, and more preferably about 1 to about 4 - moles of condensed ethylene oxide. Also, the mixed polyester w'len base~ on a mixture of dimer and tr;mer acids, as hereinabove des-cribed, are prefera~ly based on a mixture contain~ng at least about .... .
60k trimar ac-d, and more preferably, at least about gO~ trimer acid.
- ~
'~ . -, . . .

' ' ' : '` ' ' ' ' 1075()00 In the followi~lg examr)les, arJd thro~ghout the specifi-cation, disclo3ure, and claims, all ~arts and percclltages are by weight, unless otherwise stated. The ability of the additive or additive com~inations of this invention to clean up and ~aintain the cleanliness of the carburetor of an internal combustion engine is illustrated, and its ab-lity to remove or protect against the formation of induction system deposits is also illustrated bslow. Also illustrated below is the ability of the additives to reduce octane requirement inorease in an internal combustion engine. Unless otherwise stated, an MS-08 gasoline fuel is used for the Plowby carburetor detergency Keep Clean engine test and a Howell Unleaded Gasoline is used for the Induction 5ystem Deposit Test. The Howell Urleaded Gasoline has the following propertias:
HOhELL UNLEADED GASOLINE: FUEL SPECIFICATION

Aromatic content _ _ _ _ _ percent 30.2 . . .
~ Olefins_ _ _ _ _ _ _ _ ~ _ _ _ _dc _ 11.6 c ~ Saturates do 58.2 :. _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ `:~ Lead g-/gal- 0.03 .. , _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Sulfur _ _ _ _ _ wgt.percent _ 0.009 - Gravity _ _ _ _API_ _ _ _ _ 57.9 Reed vapor pressure 8.1_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Research octane _ 91.7 Motor octane _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ g3-8 Initial B.P. _ _ ~ 94 50% distilled ~ 228 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 90% distilled _ _ _ __ _ _ _ _ _ _ _ _ F_ _ _ _ _ 351 Distillation end poiint _ F - _ _ 426 .'" ~
. .-~
~ -14-,~ .

:-. .

`` ` 1075()00 EN~INE
DETE~GENTS
(A) Blowby Carburetor netergency Keep Clean Engine Test (1) Engine test procedure -The Blowby Carburetor Detergency Keep Clean Engine Test (BBCDT-KC) measures the ability of a gasoline additive to keep clean the carburetor throttle body area, and is run irl a 1~70 Ford 351 CID V-g engine equipped by means of a special ty~ intake manifold wich two one-barrel carburetors, which can be ind0pendently adjusted and activated. With this arrange-ment, a separate test fuel can be evaluated by each carDuretor which feeds four of the eight cylinders via the non-interconnected intake manifold. The carburetors are modified with removable aluminum sleeves in order to facilitate weighing of the deposits which accumu-late in the throttle bod~r area. The severity of the test is adjusted to an appropriate level by recycling the entire amount of blowby gases, approximately 90-110 c.f.h., to the top of the air cleaner - i .. . .
90 that each carburetor receives an equal volume of these gasss.

Equ~1 intake mixture flow through each carburetor is adjusted during the first hour of operation of means of intake manifold differential pressure and C0 exhaust gas analysis. The following test cycle and operating conditions are employed:

Test cycle:

Phase I _ _ 650 engine r.p.m., ~ min.

Phase II 3000 engine r.p.m., 1 min.

Test duration, hrs. 10.

Intake air, F. _ _ _ _ _ _ _ _ 135 ~ 10.

Jacket water, F. _ _ _ _ _ 190 ~ 10.

Engine oil su p, ~ . _ 210 + 10.
.,. ' .

~ -15-.~ .

~ . - , . -: . . -: ' ' ': ~ - ', " ' " . ' '' ` ~ 075UOO

~`~ Percent CO in exha~st 3.0 + 0.2.
Blowby, c,f.h. ~ _ _ _ _ _ _ 90-110.
i~ The weight (mgs.) of deposits accum~ated on the aluminum sleeve is measured, and the average value of four tests per additive or additive mixture is reported.
The gasoline used in the BBCDT-KC test is an MS-08 gasoline having the following properties:
, . .
i Gravity:
~-................ API_______________-------------- 59-7 ~ Sp. gr. at 60 F. 0.74 ~ o ~- hSTM D-g6 distillation, F.:
I.B.P. 93 ~, ~i 10~ 123

5% 205 ~-~ 9C% _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 348 E~P. _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 405 ., ` _ _ j~ Percent reco~ered_ _ _ _ _ _ _ _ _ _ _ 98 ;
: Precent residue :. -Percent loss _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 1 Percant sulfur _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 0.11 -- ~ . :- -i~l` Lead~ gm./gal. 3.08 ,.. . . .
g FIA composition:
~,,, Aromatics, percent_ 23.1 Olefins, percent _ _ _ _ _ _ _ _ _ _ 20.0 ;;
Saturates, percent _ _ _ _ _ _ _ _ _ _ _ _ _ _ 56.9 ; Oxidation stability, minutes _ 600t :: .
ASTM gum (unwashad), mg./lCO ml. 1.0 Research octane n~nber 95,5 Percent H _ 13.10 ,-~;c ''~ , , ~' ~075000 Percent C 86.61 ... _ ._ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ H/C_ _ _ _ _ _ _ _ _ _ _ _ _ ~ _ _ _ _ _ _ _ _ _ _ _ _ l.gO
(~) Induction .Syste~ Deposit Engine Test (1) Engine test procedura. -The Induction System Deposit Test (ISDT) which is used to evaluate the abili-ty of gasoline additives or mixtures of additives to control induction system deposits, is run using a new air-cooled, single cylinder, 4 cycle, 2.5 H.P. Briggs and Stratton engine for each test. The engine is run for 150 ~i-hours at 3000 r.p.m. and 4.2 ft lbs.load, with a 1 hour shutdown every 10 hou s to check the oil level. Carbon monoxide exhaust emission measurements are made each hour to insure that a constant air to fuel (A~ ~ ratio is being maintained.
Upon completion of a test r~m, the engine is partially disassembled, and the intake valve and port are ra-ted and v~lve and port deposits are collected and weighed.
(C) Rusting Test Method A rusting test method for fuel additive rust inhibition is used which follows military specification MIL-I-25017C (Section 4.6.3~. This procedure whlch utilizes a type B medium hard watGr is a modification of the basic ASTM method D665. The object of the test is to evaluate the ability of a gasoline additive to inhibit rust-ing of ferrous parts such as encountered in gasoline storage and transportation systems. The method involves stirring amixture of 300 ml. of an additive blend in depolarized isooctane with 30 ml.
OL de-ionized-distilled water, medium hard water, or synthetic sea-water~ for 5 hours at a te~perature of 100 F. (37.g C.) with a cylindrical steel specimen completely immersed therein.
Test results are reported as percent area rustsd and a pitting rating is also optionally reported on a sc~le of 1 to 3~ with 3 being tne worst degree of pitting and 0 beir.g the best. The type B medium hard water is prepared as foll~ws:

3 stock solutions using ~CS reag~nt-2rade chemicals in dis-tilled wnter containing, respectively, 16.4 g/liter NaHC03, 13.2 g/liter CaC12'2H20, and 8.2 g./liter MgS0~'7H20. Ten ml.
of the NaHC03stock solution are pipetted into ~00 ml. of distilled water in a l-liter ~olumetric flask, and then shaken iigorously.
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 MgS04 stock solution are also pipetted into the flask, distilled water is then added to ~ring the volume to 1 liter and mixed thoroughly.
The final blend should be clear and free of precipitate.
(D) Combustion Ch&~er 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 mixture of additives to control or reduce the octane number requirement inorease (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 Turbo Hydromatic 350 transmission which is connected to ~ 1014-2 WIG dynamometer equipped with a 200.3 lb. ft. 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 r.p.m.

Phase II _ _Accelerate-l to 2 shifts, 5.5 sec., 2900-3000 r.p.m.
Phase III _ _ _ AccQlerate -2 to 3 shift, 9.5 sec., 2gO0-2900 r.p.m.
Phase IV _ 3rd gear, 10.0 sec., 260~ r.p.m.
Phase V Decslerate to idle, 15.0 sec.

r ~ 0~75(300 ~ r~

l`est duration ~ 200 hours Fuel consumption 1000 gallons (Howell u~leaded gasolir plus additive treat~ent).
Intake air F. Ambient.
Jacket water, F._ 1~0.
Engine oil-sump~ F. 220 -~ iO.
Octane number requirement is determined at 2/~ hours interval under the following engine conditions: transmission in 3rd gear with an output shaft spsed controlled at lSOO r.p.m. and the engine throttle wide open. The octane number requirement of the engine is dete~mined 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 1~-is recorded as the octane number requirement. Octane number requiremerlt increase is then the difference between the initial octane number requirement and the final octane number requirement for a - -particular test.
The novel fuel compositions may be prepared by adding the in-dividual additives 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 more of the additives in a suitable sol~ent such as toluene or xylene may be prepared. Also,all of the additive components are normally liquid materials at room temperature and are soluble or miscible with each other and may be distributed without any solvent.
The preparation of a typical mixed polyester employed in the -fuel of the invention is as follows:

PR~PARATION OF TRIMER ACID, DIISODEGYL, MONO-OCTYLPH~OXYPOLY-ETHO~Y~THANOL (3 M~LES ETHYLENE OXIDE)TRIESTER

--1~--- : ' . .
' ': ~ ~ . . , : .
.

To a 3-1~ three-necked round bottom flask ritted with a me~hanical stirrer, thermometer, and Dean-Stark trap with reflux condenser are charged 845 g. (1 mole) of a tri~er acid mixture(Emery 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 containir.
about 3 moles of condensed ethylene oxide, 200 ml. of toluene, and 1.0 g. of p~toluenesulfonio acid. The reaction mixture is heated to reflux (with stirring which occurs near 135 C. Refluxing is continued for 6 hours during which time the theoretical quantity of water is evolved. Toluene solvent is stripped under vacuum, 3.0 g. of ~la2C03 added to neutralize the p-toluenesulfonic acid~ and ~ -the product filtered. The material prepared in this way generally has an acid nu~ber near 1Ø
The theoretical product distribution assw~ing that equilibrium has been obtained and that here are no free energy formation differences between the various esters is the following:

Wt. Mole percer;t percent Trimer acid, triisodecyl triester 25.9 29.6 Trimer acid, diisodecyl/monooctylphenoxylpoly ethanol (~ moles ethylene oxide)44.5 ~4.5 Trimer acid, isodecyl dioctylphenoxypolyethoxy-ethanol (3 moles ethylene oxide) triester25.0 22.2 Trimer acid, trioctylphenoxypolyethoxyethanol (3 moles ethylene oxide) 4.6 3.7 -Actual analysis shows the di-.sod0cylmonooctylphenoxypolyethoxy-ethanol ester to be present in the preponderant numerical parcentage amount, and actual chromatographlc an~lysis conforms subst&ntially with the predicted amolmt. Changes in the ratio of the ester components l~y be obtaincd~ by aiter.llg the esteriication condit ons.
~20-oo~

The following T&'~e II li9t8 typical mixed polyesters prepared for use with the present invention and in hccordance wlth the above general method:

Example:
l.,... Dimethyl/mono-octylphenoxy poly- Ester of trimer of linoleic acid.
ethoxyethanol containing average of 3 mole~s of condensed ethylene oxide.
2..... Dibutyl~mono-octylphenoxy poly- Do ethoxyethanol with average of 3 moles of ethylene oxide.
3,~... di-2-ethylhexyl/mono-octylphenoxy Do polyethoxyethanol with 3 molas of ethylene oxide.
4..... Diisodecyl/moro-octylphsnoxy poly- Do ~ -ethoxyethanol with average of 3 moles of ethylane oxide.
5..... Di~C16 20 aliphatic alcohol/mono- Do o^tylphenoxy polyethoxyethanol with 3 molss of ethylene oxide.

6..... Mono-isodecyl/di-octylphenoxy poly Do ethoxyethanol with 3 moles of ethylene oxide.

7..... Diisodecyl/mono-octylphenoxy poly- Do ethox~ethanol with average of 5 moles of ethylsne oxide.
g..... Dimsthyl/mono-octylphenoxy eth- Do oxyethanol with average of 1 mole of ethylene oxide.

~21-.

~075000 9..... Mono-~sodecyl/mono~octylphenoxy Ester of dimer of linoleic acid.
polyethoxy ethanol w~th 3 molcs of ethylene oxide.

The esterification reaction is usually acid cataly~ed and can b~ carried out o~er a broad range of temperatures~ but usually the temperatule will vary from about 75 C., to bout 18C C.
The mixture of aliphatic alcohol and ethoxylated aromatic alcohols can 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 alcoho~s used should be sufficient to essentially completely esterify the polycarboxylic acid (i.e.

the trimer or dimer acid, or mixturs 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, r~, and V below) is a Howell unleaded gasoline as described herein-above, except for the BBCDT-KC tests wherein an MS-O~ gasoline as described hereinabove is used. Induction System Deposit Test results (I3DT) are reported in milligrams (mg.) of deposit as are the Blowby Carburetor Detergency Keep Clean Engine Test resul~s. Percent rusting is also reported. These test procedure3 are described above.

~075000 _ _TABLE III _ 1 ISDT, mg.
Fuel additive and con-Valve & port ~ample ~entration p.p.m, ~asoline m~. deposit Control...... Untreated gasoline i e.
base fuel.............................. 365 13 Comparative Triisodecyl ester of trimer Example A of linoleic acid, 300 p.p.m....... 170........... ,............ 1 -10........... Mixed dimethyl polvester of Example I (see Table II), 300 p.p.m............ 72 ........... ,., .,,. I
11. , .. Mixed dibutyl polyester of Example 2 ~Table II above) 300 p.p.m............. 3S lg.l 12,... ... .. Mixed diisodecyl polyester of Example L (Table II above) 300 p.p.m....... ~............... 37 14.2 13....... ....Nixed diiscdecyl polyester of Ex~mple 7 ~Table II above) 300 p.p.m............................. 5475 14....... ,,,. Tri-octylpolyethoxyethanol ester of trimer of linoleic acid with 3 moles ethylene oxide, ~00 p.p.m............................. 186... --Comparative Commercially available and used Example B alkyl ammonium phosphate, 500 p.p m. 435 4.0 Comparative Commercially available and used Example C polybutene succinimide~ lL0 p.p.m.
1~247 3.3 .:
Induction System Deposit Test as described above.
2Blowby Carburetor Detergency Keep Clsan Engine Test, as described above.
In Table IV, below, there are shown results obtained with a combination or mixt~e of additives according to the present invention.

~07s()00 rUI ~ C' O O O G C~ O O O
bD ~
P~
o o o ~ o ~ ~Y ~ 8 ~P~

. o ~ ~ . . ~
, . ~ (Y ~ ~ ..
~ ~o ~
oo m ~ ~ t~i . .
: : :
. .~ ~ ~ ~ ~ ~ O C~l ~ 'oO U~
~,D~ ~ ~ C~ ~O ~t) r--~\1 ~1~1 ~ ~9 ~ C~ ~C~' ~
~ ~d H P ~i h ~ +' h h p~

~ ~ ~ p~
R O ~ O ~ $, o ~1 U P. ~ ,C~ IP, ~
O :~ ~~) OC~ O~rl O ~ ~
'25 0 ::~ I O ~ I G O ~ ~-~1 X Q,,~ ~"~ Q,~ ~ Q)~ R~
~F PoX' ::2,~ Po~ Po~s Po ~ p~ ~ ~ ~ Q~
,~ X ~ X ~.X ~,X o X o X
HH H I ~~9F H~ H~ H ~F (~ ~rl ~ ri o ~
H H ~H) I o H ~ H Q) H
~ ~ a) H ~H Q) H OH Q) H ~ bD_ O r-l H O H HH s--lH HH O H O H Q) Q~
~} ~ O H PH ,~3H PS.--: ~ H ~0 H O Ul Q~ 0 ~ C~ P
S~ ~~a. H ~ ~ O H fi H E3 H
o O H Q. Q~ Q~Q~ H H H O

O C~l ~ ~ P ~ ~ C ~ ai O ~ ~I) S:H rXl E~H ~H ~H l~sH ~~ H `~ I _. r, C, ~ H H H H H H H H
a) ~ o ^ ~ o ~ o ~ o ~ ~ ~ u~
P~ Q~ h~s s~s'fi h.~. hE~ h ~ H E;
~:) Q) ~ Q~ sV ~ p r. nQ' ~ Q~ ~ ~ ~R~ ~ Q~ ~dQ S~ '~
OI s ~Qs Sl)p~s Q)Q, sYs Q~ XQ~ ~s .~ O ~ O ~ O ~ O .~ o ~' o '~ o ~ a~
rl I O ~ C~l ~ O :1~ O U~ O ~ ~ ~ C~ U~ ~S h ~ Sl ~ I O I QSI SS ~ 0 1 0 1 0 1~H H H H H H H H
O r~
.
~s~ ~ l~ ~:) O~ O s-sC~ O
. . r~ 'C\~ C~l ~

-`` 107SOOO

Component I (used in the additive package or blend of componcnts I, II~ and III abc~e) is a t-C18-C22 alkyl amirle with a highl~-branched backbone, a neutral equivalent of 315, and a molecular weight principally in ~e 269-325 range 2Additive component II is essentially an allcyl ammonium carboxylate di-salt ester of the formula [ C2 (Cl~2cH2 ~ 3~ c --1 \ [C2 NH3t-Cl~-2~ 37-4~ 2 where Zl is the hydrocarbon residue of the product of -crimerization o~ an unsaturated Glg fatty acid, such as linoleic acid, which is a mixture of about 70 - 80% trimer acid (C54) and about 30-20 of dimer acid (C36), all parts by weight.

TAB~E V
(Octane number requirement increase)*

Octane n-~mber --Fuel additive and concentration, requirement Example p.p.m., in ~asoline increase Control...... Untreated gasoline, i.e. base fuel............... 10 Comparative Commercially available and used poly- g ~xample D butsne succinide, 140 p.p~m.

23........... Same additive pacxage or blends as in 4 Example No. 15 (Table IV) (total = 370 p-p-m-) 24........... Same additive as Example No. 2, Table II 5 at 300 p.p.m.

~As measured by the Combustion Chamber Deposit Engine Test As is evident from the data in Table III~ the mixed polyesters of th s invention ~hile ir.dividually affording no carburetor detergency, activity, per se, are ve~r effecti~re at controlling induction system deposits in an internal combustion engine. -2~-~ len th~ ~ixed poly~sters ~ e usa(l in com~infltiorl with rust inhibitors and cPrburetor detergentfi as sh~ln ir, lable rv so that a multipurpose ~dditive package is formed, th~ activity of Examples 15, 1~ and ]9 is significantly ~etter thPn the base fuel in all thres performance categories, i~eO, rust i.~hibitor, carburetor detergency~ and induction system detergency. Altnough Examples 17, 18, 20, 21 nnd 22 show higher levels of induction sy3tem deoosits than the bas~ fuel their total performance is significantly better than the base fuel treated with currently used commercial additiFes such as the alkyl ammonium pnosFhates ~nd the polybutene su^ciDil~des.
It is impor~ant to remember that untreated gasoline is rarely used in pressnt day automobiles and that gasoline tre2ted with convsntional carburetor detergents and rust inhibitors will normally give higher levels of induction system deposits than the base gasoline as is shown in Compara-tive Examples B and G of Table III.
Although the mechanism of activity is not clear, it is evident from the data in Table V that the additive combination of our invention is effective in moàifying the d~po3its n the combustion chamber such that the octane number requirement increase of the engine is less +han 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 (1) and induction system deposit control additive (3) are used (without any added rust inhibitor) in gasoline, at a total concentration of about 350 pOp.m. (50 p.p.m. of 1 and 300 p.p.m. of 3), the following rcs~ts are obtaired; for the ISD~ l&st, 201 milligr~s (mg.) -2~-107SI)00 of àeposi-ts; and -)~ the B~CD~ C test, 1.3 ~g. of deposits. In this test, component (1) was a t-C1~-C22 alkyl amine such as ~as used in Ex~mple 15~ and component (3~ was the mi;ed polyester of Example 4. As noted previously~ ~ Howell unleaded gasol-r.e is used for the I5DT tests. and MS-08 gasoline is used for the BBC~T-KC tests.
In arlother ~lteInative embodiment of this invention, other dicar-bo.Yyli~ acid esters, such as an adipate diester may be substituted in ~hole or part for component (3) of the de+e~gent composition, noted abovs, to provide induction systems deposit control. Thus, an adipate diester comprising the mono-isodecyl, mono-octyl phenoxy polyethoxg ethanol (containing an average of 3 moles of condensed ethylene oxide) mixed ester of adipic acid and made by a con~entional acid esterification process, gave the following result: in the ISDT test, 160 mg. of deposit. Other adipic acid esters, a.g., the mixed adipic acid esters comprising a mixed Cl-C20 alkyl/alkyl phenoxy (alkyl of C4 to C9) polyethoxy ethanol (containing 1 to 20 moles, and mora preferably about 1 to 5 moles conden-sed ethylene oxide) ester may also be used to provide induction system depoæit control either alone, or in combination with components (1~ -and (2) above. The adip~c acid ester may be used in the same or greater amount as component (3) noted above, either alone in gasoline or in combination with components (l)* and (2)*, noted above. ~ -Other results using 300 p.p.m. of the specific mono-isodecyl~
mGno-octyl phenoxy polyethoxy ethanol ~3 moles ethylsne oxide) adipic ester noted above in combination with 50 p.p.m. of the t-Cl~-C22 alkyl amine (component (1) above) are as follows: in the ISDT test, 225 mg. Or deposit, and in the BBCDT-KC test, 203 mg. of deposit. ~n3n 10 p.p.m. of the rust inhibit~r compo- --'"

1075~)00 nent (2) of ~xample 15 is added to the mixture Or the t--CIg-C22 alkyl amine alld the adipic acid ester. noted abo~e, to give a three component systam, the following results are obtained:
in the ISDT test, 327 mg. of deposit. 2.2 mg. of depos-t in the BBCDT-~C test, and 0~ area rusted in the rust teEt described above~
In another example using 50 p.~.m. of the t-Clg-C22 P-kyl amine (component (1) abo~e)~ 5 p.p.m. of the rust inhibitor compo-nent (2) of E;amp]e No. lj, and 3CO p.p.m of tne mono-isodscyl, moIlo-octyl phano~ polyetho3yethanol (containing 5 moles of ethylene oxide) adipate ester the following results were obtained:
in the I~7DT test, 237 mg. of deposit, in the BBCDT-~C test, 3.5 mg. of deposit, and 0~ arsa rusted in the rust test.

* 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 es-ter rust inhibitor component, hereinbefore describsd.

--2g--lQ7S()OO

In another alternativc embodiment of thiY invention, other carboxylic acid ~st~rs may be us~d and substitut~d in whole or p~ t for compollent (3) of the detergent composition, noted above, to provide induction systems deposit control and a lower level Gf octane n~mber require~ent increase; that is to say, these estars may, over a period of time, decrease the le~el of octane n~unber requirem~nt increase usual-ly experierced by an automobile after it has been driven for several thousand miles. Esters which are preferred are mixed esters of di- or tr -carboxylic acids. By mixed acid esters we mean, in the case of dicar~ -boxylic acids, products comprising a mixed C]-C23 alkyl/PlXyl phenox7 (alkyl of C4 to Cg) polyethoxy ethanol (containing 1 to 20 moles or, ~ore preferably, about 1 to 5 moles of condensed ethylene oxide). The m xed ester may be used ~o provide induction system deposit contro' nd a lower level of octane number requirement increase (ONRI). By usi~g the ester either alone or in combination with component (1~, the carburetor detergent, and/or component (2), the rust inhibitor, noted above, the inductlon systsm deposit control may be provided or result nd/or a lower ONRI ~ay be provided or result. The mixed acid ester may be used in the sam~ or greater amount as component (3), noted herein~bove, e,ther alons in gasoline or in combination ~ith componsnts (1)* and/or (2)'~, noted above.
These esters are prepared in conventional manner by using aliphatic ~ alcohols and ~kyl phenoxy polyethoxy sthanols containing 1 to 20 moles of condenssd ethylene oxide. Usually, ~he aliphatic and aromatic alcohols ~re used in equal amounts.

*Component 1 refers to the t-alkyl amine (of 6 to 24 carbon ato~s) carburetor detergent comyonent, and component (2) refers to the surface active a kyl an~onium carbo~lata sait-ethox~lated alkyl phenol ester rust inhibitor compollent~ hereinbefore described.

~07s000 Th~ terms l'mi~d acid ester", ~mixed ~-olycarboxylic acid ester~, OI' more sim~,ly nmixed ester" can also be taken to mean any polyc~rbo~ylic acid (the term "poly" means two or more) containing two, three, or more carboxylic groups, wherein at laast one of the groups has been substituted wlth (or contains) a Clto C20 alkyl group ~nd at least one Or the carboxylic groups has been substituted with (or contains) an alkyl phenoxy(alkyl of G4 to C5) polyethoxy ethanol (containing 1 to 20 moles or, more preferably, about 1 to 5 moles of condensed ethylene oxide). Preferably, the polycarboxylic acid is completely esterified and substantially no free carboxylic acid groups ar~

present.

The alkyl phenols may contain condensed ethylene o~ de units or condensed propylene oxide units.
Some of the acids that may be used in this inv~ntion, for example, are listed below:
Oxalic Acid H02CC02H
Malonic Acid H02CCH2C02H
Succinic Acid H02C(CH2)2C02H
Glutaric Acid Ho2C(CH2j C02H
Adipic Acid 2 (CH2)4C02X
Pimelic Acid H 2C(c~2)5c2H
Suberic Acid Ho2C(CH23 C02H
Azelaic Acid H02C(CH2) C02H
Sebacic Acid H02C(CH2) C02H
Maleic Acid cis-H02CC~ -- CHC02H
Polybasic acids lormed by dimer or t~imerization of polyunsat-urated fatty ac~ds. Two examples in this category are ths C54 trimer and C36 dimer acids sold commercial~ly by E~ery Industries.

~3n-.
-' 1075(~
Ph~h~lic Acid ' 6 4( ~ )2 Isophthalic Acid ~3 6 4( ~ )2 Terephthalic Acid 1 4 C H (CO H) Hemimelitic hcid ' '3 6 3( 2 )3 Trimellitic Acid ' ' 6 3( 2 )3`
Trimesic Acid 1,3,5-c6H3(c02H) Sbme of the alcohols that can be used to esterify vhe above noted acids include, for example, those shown in the table below:
hcid Alcohol(s) Malonic Triton X-451~/isodecyl Succinic Triton X-45/isodecyl Sebacic Triton ~-45/isodecyl Phth~lic Triton X-45/isodecyl Oleic Triton X-45/isodecyl Other polybasic acids which may be used to provide the mixed esters include:
(a) Saturated dibasic acids fro~ oxalic to sebacic (C2-C10) (b) ~leic Acid (c) Phthalic~ isophth~ic and terephthalic acids (d) Fatty acid dimers and trimers.
~Triton X-45 C~17 ~ 0(C~2CH20) H

ExamPle 25 Triton X-~ Isodecyl Succinate To a 300-ml., three-necked, round-bottom flask equipped with a mechanical stirrer, thermometer to monitor the temperature of the reaction solution and reflu~ condenser with Dean-Stark trap is charged 24.02 g. (0.24 molej of succinic anhydride, lC2.~8 g. (0.24 mole) of Triton X-4~*, 39.89 g. (0.252 mole) of iscdec~l alcohol, 250 mg. of *Trademark -31-..

.

p-toluenesulfonic acid monohydrate and 20 ml. of toluene. The mixture is heated with stirring under a nitrogen atmosphere to reflux (pot tempera~ure 167 C.) and maintained for 3 hr. during which time approx.
5 ml. of water separates (4.3 ml. theory).
The reaction mixture is concentrated under vacuum up to a temperature of 160 C. at 0.7 mm. After cooling to 50 C., 5 g. of dried Amberlite IRA-93"1** beads are added and the mixture is stirred for 1/2 hour at tnat temperature un~er vacuum (approx. 20 mm). Vacuum filtration affords ~1 /, 153.7 g. of Triton X-45 Isodecyl Succinate as a golden oil. Yield is 96% of thaoretical; acid number is 1.5.

Anal. Calc'd. for C3~ 6609: C, 6g.43;H, 9-97; O, 21-59-Found: 68.57 10.30 20.87 Example 26 Triton X-,5 Isodoc~l AdiPate A mi.xture of 5~4 g. (4 moles) of adipic acid, 758 g. (4.8 molesj of isodecyl alcohol, 1704 g. (4 moles~ of Triton X-45, 5.8 g. of p-toluene-sulfoDic acid monohydrate and 400 ml. of toluene is haated u der a nitrogen atmosphere to reflux.in an apparatus equippsd for water separOtion. During the course of ~ hr. 1/~ ml. of water evolve ~c (144 ml. theory) and the pot temperature rises to 175 C. Vacuum concentration to 165 C. (35 mm.) is .ollowed by treatment of the residue at 50 C. with 120 g. of dried Amberlits IRA-93 for 1/2 hour.
Vacuum filtration gives 2640 g. of Triton X-45 Isodecyl Adipate (95% yield). Acid number is 0.4.
,. ..
~Triton Z-45 = Octylphenoxypolyethoxyethanol containing about 5 moles of condensed ethylene oxide. (nTriton X-45" is a trademark).
,. ., **~mberlite IP~-93 = A we~kly basic polysty e~e-pQly-m ne &nion exch&nce resin.

1. Trademark , ' ' .: ' ', : '~ -- .- :
. .

1075~00 xflmpl~ 27 Trlton X-~5 Isodecyl Seb~cats To a three-necked, round-bottom flask fitted with a mechanical stirrer~ thermometer, and reflux condellser with Dean-Stark trap is charged 32.4 g. (0~16 mole) of sebacic acid, 6g.25 g. (0.16 mola) of Trito~ ~-45, 27.g6 g. (0.176 mole) of isodecyl alcchol, 250 ~g. of p-toluenesulfonic acid monohydrate and 20 ml. of toluene. The m~xture is heated at reflux with stirring under nitrogen for 3 hr.
during which time the temperatuL~e rises 'o 158 C. and 5.4 ml. of water evolv~ (5.g ml. theory).

Concentr~tion to 175 C./~ =. is followed by treatment at 50 C.
for 1/2 hour with 4 g. of dried Amberlite IRA-93. Vacuum filtration gi~es 114.g g. (95.5% yield) of Triton X-45 Isodecyl Sebacate. Acid number is 1.1.

~nal. Calc'd. for C44H7809: C, 70.3~; ~, 10-46; 0, 19-17 Found: 71.12 10.~4 19.08 Example 28 Triton X-4~ Isodecyl Isopnthalats Isophthalic acid (36.55 g.., 0.22 mole), 93.g5 g. (0.22 mole) of Triton X-45, 37.0 g. (0.234 mole) of isodecyl alcohol, 250 mg. of p-toluenesulfonic acid monohydrate and 20 ml. of toluene are charged to a 300 ml., three-necked round-bottom flasX equipped with a mechanic~l stirrer, thermometer and refluY condenser with Dean-Stark trap. The mixture is heated at reflux witn stirring under nitrogen for 61 hr. during which time 7.4 ml. of water e~ol~e (7.9 ml. theory) and the temFerature of the solution rises to 183 C. The cooled reaction mixture is tacuu~
filtered and concentrated to 175 C./0.5 mm. Treatment of the residue for 1/2 hr. at 50 C. with 5 g. of dried Amberlite IRA-93 followed by 07s')oo /l //
Yacuum fi]tration afrord~ 1~,3.48 g. (91g yield) of Triton X-~i5 IsoAecyl IsophthPlate. Acid number is 7.2.

Anal. Calc'd. for C ~ 6609: C, 70.56; H, 9.30; Oj 20.14.
Found: 70.13 9.40 19.32.
Since the esteri~icatiol~sdescribed above (Ex&m~lg3 25-28) in~olve tile azeotropic removal of water to drive the reactions to completion, the ~emperature of the reaction mixture is determined by the reflux temperature of the pPrticular system under consideration.
Tkis of course ca~ be varied by modifying the solvent (toluene) charge.
,o ~ .or~ctical te~perature range for r_pid ~roduct form2tion would be 120-180 C.
Examples of suitable cat lysts would be p-toluenesuifonic acid, s~lfuric acid and Lawis acids (e.g.~ boron trifluoride). At lower temperatures acidic, cationic ion exchange resins such as Amberlyst 15 could be_employed.
In Canadian Patent No. 1?039,302, granted September 26, 1978 said patent bein~ entitled "MOTOR FUEL COMPOSITION", we claim the use of mixed Cl-C20 alkyl/alkyl phenoxy polyethoxy ethanol (containi~g 1 to 20 moles of ethylene o~ide~ esters of polybasic scids for octane number rsquirement incre2se cortrol (O~.~I).
Additional results showing the effecti-~er.ess of mixed esters o~ dibasic scids for controlling ~NRI are presented in Table 'VI. It is evident from tne data that the listed mixed esters provide Gr~RI control sUperiQr to that of base nonle2ded gasolina-and base gasol ne treated with twc currently used co~erc_~l gasoline additives.
Table ~I
Oc~ane Number Requirement Increase Control: Per~ormance of Dibacic ~cid 3sters in Non-leadod Fuel (P~-llips "J~

Ccncentration ONRI
Additive o~m 100 Hr. ~est ContrGl - 3-9 Colmmer^ial Bdditive ~ 80~ 4;g Concer~tration O~RI
_Add tive ~pm 100 llr. 'l'est Commercinl Additive Y 400~ 6.1 Triton X-45/Isodecyl Succinate 250 1.6 Triton X-45/Isodecyl Adipate250 0.8 Triton X-45/Isodecyl Sebacate 250 0.5 1,3 Triton X-45/Isodecyl Phthalate 250 0.5 - i~Recolwnended concentrations E~oerimen'~l Data The O~RI control data shown in Table VI were generated in a single-cylinder laboratory engine test. Test details and operating p~ocedures are as follows:
Engine Te~t: Single Cylinder CLR Engine Specifications: Compression ratio g.O:l Four-Cycle Air: Fuel 14.5:1 Temp.: Oil 190-F * 5 - Inlet Air 90 F5, 80 gr. H20/lb. d.a.
Water out 190 F ~ 5 Ignition Timing 14 BTC
Operation: Test Cycle: 1800 rym - 2 hrs. wide open throttle 1000 rpm - ~+5 min. no load Test Duration - 10O hrs.
Spark plug change - every 50 hrs.
Oil - SAE lOW-40 ~'uel - nonleaded (Phillips "J") - consumption gO gal./100 hrs. - -1075~00 The additive or additives of the present invention are nlso useful in `two cycle or ~our cycle engines. In a two cycle engine the additire or additives are first added to an oil ~or use in a two cycle engine and the oil containing the additive or additives is then added orblended ~ith the gasoline. The manner of adding or blendin~ the oil t~ or with the gasoline is im~aterial as far as this invention is concerned;
however, for example, the oil containing the additive or additives may be blended with the gasoline in a single tank as in many lawn mowers or ths oil may be added into the intake port just after the carburetcr and blended with the gasoline in the cylinder as in many motorcyclPs.
This requires two tanks - one for the two cycle oil and one for the gssoline. The ester additive, per se, note, for example, Additive "B" in Tdble VII below which is very effe^tive when added to a two cycle oil for control or prevention of deposits in the combustion chamber, e.g., E~laust Port Plugging ~d spark plug foulir.g are prevented or controlled.
Similarly, as shown in Table VTI, the multicomponent Additive "A" is also effective in preventing or controlling Exhaust Port Plugging and spark plug fouling and combustion chamber deposits. Moreover, muiticompo-nent additive "Al' is effective in preventing or controlling deposits when used with a manganese containing gasoline either in atwocycl_ engine or

8 rour cycle engine. l~len the multicom~onent additive ~A~, cr i~s analogues ~r variants is added to a gasoline containing manganese for use in a four -- -cycie engine, the overall amounts of the Additive "A" is essentially the ssme as used with other gasolines,i.e., leaded, lou-lead, or non-lead containing gasolines. The internal ratios of the three active co~ponents are given on pages 4 through 7 of tne specification. Additive ~A"
and Additive "B" as shown in Tæble VII are merely illustrative of the pres_nt in~ention, as other related addi'ives may a so be used in the present inven-tion. In Table VII, multico~pcnent additive "A" comprises about 12-1/2~ cf a t-alkyl ~mine ,':', ' - '-- - ' :' .

``` 1075()00 co~tainin~ abou' 18 -22 carbon atoms; about 1-1/4% of the di-salt mono-ester, i.e., the di-alkyl ammonium carboxylate salt-sthoxylated alkyl phenol ester of a trimer acid having a hydrocarbon residue of about 51 carbon ~toms as hereinbsfore disclosed and wherein the alkyl ammo~ium carbo~Ylate sPlt molety contains sbout 18 -22 carbon --at s and the mono ester moiety is the octylpheno~ypolyethoxyethanol, conta nin~ about 3 moles of condensed ethylene oxide; about 62-1/2%
of the monooctylphenoxypolyethoxyethanol containing about 5 moles of condensed ethylene oxide/monoisodecyl ester of adipic acid, and wherein ~0 the balance is xylene which acts as & carrier or diluent. Additive "BD

is the ester, per se, i.e., the mono-isodecyl/mono-oct~lphenoxy-polyethox~
ethanol contai~ing about 5 moles of condensed ethylene oxide, mixed ester of adipic acid.
The above description is noted in more detail in Table VII, presented hereinafter.

Table VII
- Exhaust Port Plugging "Lawn-Boy"~wo CYcle Eneine Test %Exhaust Add-tiveConcentration (ppm) Test ~ours Pcrt P1UEeine ~o Control _ 70 , 56 95*, 93*
~1) Additive "A" 400 70 , 56 47* , 56st Contrcl _ 7~ , 57, 57 96~t, 9~, 95**

(2) Additive "B" - 250 79 33~
400 57, 57 8*, 15~t ~-~MS08 leaded research fuel ~ on-leaded ressarch fuel Test Proce~ure Two "Lawn-Boy"* (two-cyele) power mowers were run, one on a test fuel and one sn a base fuel s-de-by-s de. Ths test was torminated when the en~ no ~o ru~ning on base ruel would no longer operate. At this point both ~Trademark _37 , _-` iO75000 engines were dia~rl~lntled and rated for exhau~t port plugging. The blockagc of the exhaust port was the reason the control engine would no longer operate.
The spark plugs in the additive treated engine were cleaner than those in the control enginas.

~ en the ester, per se, is added to a leaded, low-lead, non-lead or manganese containin~ gasoline for a follr cycle engine and in order to prevent or control combustion chamber deposits including spark plug deposits, it may be added in an amount of about 100 to 1000 p.p.m. or in percentage terms about 0.01% to 0.1~. Whsn the ester, per se, for example Ester ~- -Additive "B" (T~ble ~II) is added to an oil for use in a two cycle engine, the ester may be first added to an appropriate oil in a concentration of about 100 p.p.m. to 50,000 p.p.m. or 0.01% to 5%; the oil is then added ~o or blended with the gasoline in a ratio of about 1 part of the additive-containing oil to about 15 to 100 parts of gasoline, all parts being on a weight basis. The multi-component additive (such as &dditive "A" in Table VII) similarly may be added to the two-cycle oil and then to the gasoline in the same`amounts as the ester, for example Ester Additive "B" (Table VII) -per se. The relative proportion of the amine carburetor detergent, rust inhibitor, and the ester internally in additive "A" for example, may vary, ratiowise, as disclosed hereinbefore with reference to a four-cycle engine, see pages 4 through 7 of the specification ror the relative proportion~s of the three active ingredients. A small amount of xylene, as noted -~ith respect to additive l'h'1, Table VII, may be included as a carrier or diluent. Ths xylene may be included as a c~rrier or diluent.
with other additives if desired.
-.

- : .
.. - - - . ... : . . .
- , -.. . . ..

Claims (17)

CLAIMS:

1. As a new composition of matter, a mixed polycarboxylic acid ester suitable for use as a gasoline additive, said ester comprising a mixed polycarboxylic acid ester comprising a C1-C20 alkyl/alkyl phenoxy (alkyl of C4 to C9) polyethoxy ethanol (containing 1 to 20 moles of ethylene oxide) ester of said polycarboxylic acid.

2. As a new composition of matter, a mixed polycarboxylic acid ester suitable for use as a gasoline additive, said mixed carboxylic acid ester comprising an ester derived from a tricarboxylic acid and wherein at least one of the carboxylic groups has been substituted with a C1 to C20 alkyl group and at least one of the carboxylic groups has been substituted with an alkyl phenoxy (alkyl of C4 to C9) polyethoxy ethanol containing 1 to 20 moles of ethylene oxide and containing substantially no free carboxylic acid groups.

3. As a new composition of matter suitable for use as a gasoline additive, a mixed polycarboxylic acid ester wherein at least one of the carboxylic groups has been substituted with a C1 to C20 alkyl group and at least one of the carboxylic groups has been substituted with an alkyl phenoxy (alkyl of C4 to C9) polyethoxy ethanol containing 1 to 20 moles of condensed ethylene oxide and wherein the ester contains substantially no free carboxylic acid groups.

4. Composition according to claim 3, wherein the acid is selected from the group consisting of oxalic acid, malonic acid, adipic acid, succinic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, phthalic acid, isophthalic acid, terephthalic acid, hemimelitic acid, trimellitic acid and trimesic acid.

5. Method of preventing or controlling the buildup of deposits in the combustion chamber including the spark plugs and/or exhaust ports, or valves if present, of an internal combustion engine which comprises adding to gasoline from about 100 to about 650 p.p.m. of a mixed ester additive of claim 4.

6. Method according to claim S wherein the additive is the mono-isodecyl/mono octylphenoxypolyethoxy ethanol containing about 5 moles of condensed ethylene oxide mixed-ester of adipic acid.

7. Method according to claim 5 wherein the engine is a two-cycle engine and wherein the mixed ester is first added to an oil and the oil is thereafter blended with gasoline.

8. Method according to claim 7 wherein the two-cycle oil contains about 0.01% to 5% of the mixed ester additive and the two-cycle oil is thereafter blended with gasoline in a ratio of about 1 part of additive containing oil to about 15 to 100 parts of gasoline.

9. Method of preventing or controlling the buildup of deposits in the combustion chamber and spark plugs of a four-cycle internal combustion engine which comprises adding to gasoline from about 100 to about 650 p.p.m. of a mixed ester according to claim 4.

10. Method according to claim 6 wherein the gasoline is a leaded gasoline, a low-leaded gasoline, a non-leaded gasoline or a gasoline containing manganese.

11. Method according to claim 5 wherein the gasoline is a leaded gasoline, a low-leaded gasoline, a non-leaded gasoline or a gasoline containing manganese.

12. Method of preventing or controlling the buildup of deposits in the combustion chanber, including the spark plugs and/or valves if present, and/or ports if present, which comprises adding to a gasoline from about 125 to about 1000 p.p.m. of a multi-component additive comprising (a) tertiary alkyl primary amine having a branched backbone and a total of about 6 to 24 carbon atoms; (b) a surface active alkyl ammonium carboxylate salt-ethoxylated alkyl phenol ester of a trimer or dimer acid; and (c) a mono-octylphenoxypolyethoxy ethanol containing about 5 moles of condensed ethylene oxide/C1 to C20 alkyl ester of a polycarboxylic acid, the relative amounts of individual components of said additive being as follows: component (a): from about 20 to about 250 p.p.m.; component (b):
from about 5 to about 100 p.p.m.; and component (c) from about 100 to about 650 p.p.m.

13. Method according to claim 12 wherein the acid in (c) is adipic acid and the alkyl moiety of the ester is isodecyl.

14. Method according to claim 13 wherein the engine is P
four-cycle engine.

15. Method according to claim 12 wherein the additive is first added to an oil for use in a two-cycle engine.

16. Method according to claim 13 wherein the additive is first added to an oil for use in a two cycle engine and a small amount of xylene is included as a carrier or diluent.

17. Method according to claim 12 wherein the gasoline is a leaded gasoline, a low-lead gasoline, a non-leaded gasoline or a gasoline containing manganese.