CA1047251A - Motor fuel composition - Google Patents
Motor fuel compositionInfo
- Publication number
- CA1047251A CA1047251A CA292,116A CA292116A CA1047251A CA 1047251 A CA1047251 A CA 1047251A CA 292116 A CA292116 A CA 292116A CA 1047251 A CA1047251 A CA 1047251A
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- mono
- ester
- moles
- ethylene oxide
- alkyl
- Prior art date
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Abstract
ABSTRACT OF THE DISCLOSURE
The invention described herein relates to a multi-functional additive composition suitable for addition to distillate hydrocarbon fuels the major proportion of which distils within the gasoline distillation range, which additive composition comprises a mixture of (1) about 20 to about 250 parts by weight of a tertiary alkyl primary amino having a branched backbone and a total of 6 to 24 carbon atoms; and (2) about 100 to 650 parts by weight of an adipic acid ester comprising a Cl-C20 alkyl/alkyl phenoxy (alkyl of C4 to C9) polyethoxyethanol (containing 1 to 20 moles of ethylene oxide) ester of adipic acid.
If desired, there may also be included in this composition from 5 to 100 parts by weight of a surface active alkyl ammonium carboxylate salt - ethoxylated alkyl phenol ester of trimex or dimex acid. These compositions of matter are useful in substantially reducing or even eliminating deposits which would otherwise form in the intake valves and ports and combustion chamber of an internal combustion engine, and in the carburetor.
The invention described herein relates to a multi-functional additive composition suitable for addition to distillate hydrocarbon fuels the major proportion of which distils within the gasoline distillation range, which additive composition comprises a mixture of (1) about 20 to about 250 parts by weight of a tertiary alkyl primary amino having a branched backbone and a total of 6 to 24 carbon atoms; and (2) about 100 to 650 parts by weight of an adipic acid ester comprising a Cl-C20 alkyl/alkyl phenoxy (alkyl of C4 to C9) polyethoxyethanol (containing 1 to 20 moles of ethylene oxide) ester of adipic acid.
If desired, there may also be included in this composition from 5 to 100 parts by weight of a surface active alkyl ammonium carboxylate salt - ethoxylated alkyl phenol ester of trimex or dimex acid. These compositions of matter are useful in substantially reducing or even eliminating deposits which would otherwise form in the intake valves and ports and combustion chamber of an internal combustion engine, and in the carburetor.
Description
10~725~ - _ Disclosure This lnvention relates to motor fuel compositions for spark ignition, internal combustion -engines. More particularly, this invention relates to ~-~ 5 a detergent motor fuel containing addltives which ; reduce or prevent the formation of deposits in the carburetor as well as in the induction system and combustlon chamber Or an internal combustion engine.
Thus, the formulations of the present invention are particularly effective as carburetor detergents to clean up and maintain the cleanlines~ of the carburetor ; and to prevent, reduce or minimize against deposits `! .
forming in the induction sy~tem such a~ the area around . . .
the valves and ports. This invention also relates to an additive concentrate of one or more of the additives 1~ mixture, solution or combination.
Modern internal combustion engine design is undergoing and has undergone important changes to meet str~cter standards for engine and exhaust gas emissions.
.. . .
A ma~or change ~n engine design is the feeding or recycling o~ 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 atmosphere, as in the past The blowby gases contain su~stantial .
.. ' . qF
.. . .
."' ~ . . , ' .
' ~
` 1~47:Z51 ' - ' , - `
amount~ of deposlt-~orming substances and are known to ~or,m deposits in and around the throttle body area of the carburetor. These deposlts restrict the flow of air through the carburetor at idle and at low s~eeds so that an overrich fuel mixture results. This condition ! . ~
produces rough engine idllng, stalling and also results in excessive hydrocarbon and carbon monoxide exhaust emissions being emltted to the atmosphere.
In addition to the changes that have already ; 10 been made, it is anticipated that additlonal burdens and demands will be placed on present day internal combu~tlon englnes and their fuels with the advent of new emission control devices, such as exhaust'gas recirculation ~ ~ystems and catalytlc exhaust murflers, A1SO~ the : 15 use o~ certain fuel additives such as the alkyl ammonium phosphate detergent~ may have to be restrlcted or eliminated because catalytic exhaust mufflers which .;:, .
` utiliæe metal catalyst~ will be poisoned by phosphorus-; containing compounds.
' 20 It is an object o~ the'present in-~ention to provide a detergent motor fuel which will have certain ~ . , .
carburetor detergent properties and which will clean up .. ; . , . ~
'' and maintain the cleanliness of the carburetor and also .. .
t~e remainder of the fuel induction system such as the valves and ports and reduce the octane requirement ,, .
~ - 2 -. , .
, . .
. , ' .
,,; ,. . . .
~:' ' ' . ` l -04'7Z51 ~ncrea~e Or an internal combustion engine. It 1~ another ; obJfect o~ the present invention to prov-ide a detergent uel which will maintain a low level of hydrocarbon and carbon monoxide exhaus' gas emissions and which Will avold the use Or phosphorus-containing additives.
It is still a further ob~ect of th~ present invention to provide a detergent fuel which ha~ other desirable properties such as rust and corroslon protection, ~Jater demulsibility properties, anti-icing properties, etc.
It is a ~urther ob~ect of the present invention to provide multi-functionalf gasoline additives or additive combinations effective in inhibiting the formation of lntake valve de~osits in addition to being effective as carburetor detergents, and which can be used at , 'r 15 relatively low concentrat1ons (and thus at relatively low cost) for example at a treating level Or about 1000 parts per million (ppm on a wei~ht basis in the ~" .. :,..................... . . .
gasoline), or less, and more preferably 600 ppm or less, and even more preferably 400 ppm or less.
There, areJ of course, other detergent motor fuel compositions available today, but they generally suffer from one or more deficlencies. Either they are .:,. .
used at very-high concentrations, for example, somethir.g o~ the order o~ 4000 ppm; or ir used at the use levels ~n which we are interested, the available formulations suffer from one or more defects.
., ~
; - 3 _ .: . i . .
fffff ~04q2Sl We have discovered that the combination of (1) ~elected tertiary alkyl primary amines haYing branched backbones and a total of about 6 to-24 carbon atoms, and more preferably~ a total Or 12 to 22 carbon atoms, (2) a surface active alkyl ammonium carboxylate salt-ethOxylated al~yl phenol ester of a trimer or dimer acid; and (3) a dimer or trimer acid ester comprising the essentially completely 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 mono carboxylic -acid having between 16 and 18 carvon atoms per molecule which is esterified with (or incoporates) a mixture of aliphatic and ethoxylated aromatic alcohols, are eLfective in reducing or preventing ~he formation of carDuretor .
~nd other induction system deposits.
According to one aspect of the present . .
invention, therefore, we provide a normally liquid, -mul~i-functional, additive composition for addition to a leaded, low lead, or unleaded gasoline, i.e~, to a distillate hydrocarbon fuel comprising a ma~or ~, propor~ion of a hydrocarbon base fuel distilling within the gasoliné distillation range. The three component , . ' . ' . -: . , .. ' ', ~ i' "' " ' .
f .~ ' ' ' ' ` . ' .
I--~
. .
j composition ranging from a total of about 125 to about ! 1000 parts, on a weight basisJ i3 compri~ed of about -20 to about 250 part~, and more preferably, about 50 to 100 . . .
~arts by welght Or (1) a tertiary alkyl branched ~hain primary amineJ 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 al~yl phenol ester of a trimer or dimer acid, as above described; and about 100 to about 650 parts 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 alternative embodiment of the lnvention and where induction system control, per se, i~ primarily desired, then components (1) and (2) can be omitted, and component (3) can be utilized ltself i'n the fuel, on a t'otal we'ight 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 blend providing good carburetor detergency and good induction . . .
~ sy~tem deposit control, or component (3) can be used with .
~:l oth'er carburetor detergents and/or other rust inhibitors.
~ . When us~ng a combination or mixture Or components (1) and '~ (3), they are used in the same amount as noted above, i.e., about 20 to 250 ppm of (1), more preferably, about 50 to 100 ppm of (1) and about 100 to 650 ppm, more preferably, ,.' '' " ' ' - .
. - ~ . . , - ~
. '; . ` ' - ~ ' ''- .' , '-`'"~`.. , ~ : .
I` ` - 10472Sl :j sbout 200 to 400 ppm of (3).
¦ On.a ruel treatlng level bas~s, l.e., on a level ! related to the gasoline, the three component addltive compositlon should be added to or used in the gasol~ne at a total level of about 125 t.o about 1000 ppm (weight basis) and, on~an indlvidual or component basis, in an amount of from about 20 to 250 ppm, and more preferably 50 to 100 ppm of (1);
about 5 to about 100 ppm, more preferably about 10 to about : 25 of (2); and about 100 to about 650 ppm, more preferàbly 200 to 400 ppm of (3). On a pound~ per barrel of gasoline basis, this is about 5 to 62.5, more preferably 12.5 to ~5 lbs./1000 barrels (bbl~). o~ gasoline of ~1); 1.25 to 25, more preferably 2.5 to 6.25 lbs./1000 bbls. of gasoline of
Thus, the formulations of the present invention are particularly effective as carburetor detergents to clean up and maintain the cleanlines~ of the carburetor ; and to prevent, reduce or minimize against deposits `! .
forming in the induction sy~tem such a~ the area around . . .
the valves and ports. This invention also relates to an additive concentrate of one or more of the additives 1~ mixture, solution or combination.
Modern internal combustion engine design is undergoing and has undergone important changes to meet str~cter standards for engine and exhaust gas emissions.
.. . .
A ma~or change ~n engine design is the feeding or recycling o~ 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 atmosphere, as in the past The blowby gases contain su~stantial .
.. ' . qF
.. . .
."' ~ . . , ' .
' ~
` 1~47:Z51 ' - ' , - `
amount~ of deposlt-~orming substances and are known to ~or,m deposits in and around the throttle body area of the carburetor. These deposlts restrict the flow of air through the carburetor at idle and at low s~eeds so that an overrich fuel mixture results. This condition ! . ~
produces rough engine idllng, stalling and also results in excessive hydrocarbon and carbon monoxide exhaust emissions being emltted to the atmosphere.
In addition to the changes that have already ; 10 been made, it is anticipated that additlonal burdens and demands will be placed on present day internal combu~tlon englnes and their fuels with the advent of new emission control devices, such as exhaust'gas recirculation ~ ~ystems and catalytlc exhaust murflers, A1SO~ the : 15 use o~ certain fuel additives such as the alkyl ammonium phosphate detergent~ may have to be restrlcted or eliminated because catalytic exhaust mufflers which .;:, .
` utiliæe metal catalyst~ will be poisoned by phosphorus-; containing compounds.
' 20 It is an object o~ the'present in-~ention to provide a detergent motor fuel which will have certain ~ . , .
carburetor detergent properties and which will clean up .. ; . , . ~
'' and maintain the cleanliness of the carburetor and also .. .
t~e remainder of the fuel induction system such as the valves and ports and reduce the octane requirement ,, .
~ - 2 -. , .
, . .
. , ' .
,,; ,. . . .
~:' ' ' . ` l -04'7Z51 ~ncrea~e Or an internal combustion engine. It 1~ another ; obJfect o~ the present invention to prov-ide a detergent uel which will maintain a low level of hydrocarbon and carbon monoxide exhaus' gas emissions and which Will avold the use Or phosphorus-containing additives.
It is still a further ob~ect of th~ present invention to provide a detergent fuel which ha~ other desirable properties such as rust and corroslon protection, ~Jater demulsibility properties, anti-icing properties, etc.
It is a ~urther ob~ect of the present invention to provide multi-functionalf gasoline additives or additive combinations effective in inhibiting the formation of lntake valve de~osits in addition to being effective as carburetor detergents, and which can be used at , 'r 15 relatively low concentrat1ons (and thus at relatively low cost) for example at a treating level Or about 1000 parts per million (ppm on a wei~ht basis in the ~" .. :,..................... . . .
gasoline), or less, and more preferably 600 ppm or less, and even more preferably 400 ppm or less.
There, areJ of course, other detergent motor fuel compositions available today, but they generally suffer from one or more deficlencies. Either they are .:,. .
used at very-high concentrations, for example, somethir.g o~ the order o~ 4000 ppm; or ir used at the use levels ~n which we are interested, the available formulations suffer from one or more defects.
., ~
; - 3 _ .: . i . .
fffff ~04q2Sl We have discovered that the combination of (1) ~elected tertiary alkyl primary amines haYing branched backbones and a total of about 6 to-24 carbon atoms, and more preferably~ a total Or 12 to 22 carbon atoms, (2) a surface active alkyl ammonium carboxylate salt-ethOxylated al~yl phenol ester of a trimer or dimer acid; and (3) a dimer or trimer acid ester comprising the essentially completely 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 mono carboxylic -acid having between 16 and 18 carvon atoms per molecule which is esterified with (or incoporates) a mixture of aliphatic and ethoxylated aromatic alcohols, are eLfective in reducing or preventing ~he formation of carDuretor .
~nd other induction system deposits.
According to one aspect of the present . .
invention, therefore, we provide a normally liquid, -mul~i-functional, additive composition for addition to a leaded, low lead, or unleaded gasoline, i.e~, to a distillate hydrocarbon fuel comprising a ma~or ~, propor~ion of a hydrocarbon base fuel distilling within the gasoliné distillation range. The three component , . ' . ' . -: . , .. ' ', ~ i' "' " ' .
f .~ ' ' ' ' ` . ' .
I--~
. .
j composition ranging from a total of about 125 to about ! 1000 parts, on a weight basisJ i3 compri~ed of about -20 to about 250 part~, and more preferably, about 50 to 100 . . .
~arts by welght Or (1) a tertiary alkyl branched ~hain primary amineJ 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 al~yl phenol ester of a trimer or dimer acid, as above described; and about 100 to about 650 parts 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 alternative embodiment of the lnvention and where induction system control, per se, i~ primarily desired, then components (1) and (2) can be omitted, and component (3) can be utilized ltself i'n the fuel, on a t'otal we'ight 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 blend providing good carburetor detergency and good induction . . .
~ sy~tem deposit control, or component (3) can be used with .
~:l oth'er carburetor detergents and/or other rust inhibitors.
~ . When us~ng a combination or mixture Or components (1) and '~ (3), they are used in the same amount as noted above, i.e., about 20 to 250 ppm of (1), more preferably, about 50 to 100 ppm of (1) and about 100 to 650 ppm, more preferably, ,.' '' " ' ' - .
. - ~ . . , - ~
. '; . ` ' - ~ ' ''- .' , '-`'"~`.. , ~ : .
I` ` - 10472Sl :j sbout 200 to 400 ppm of (3).
¦ On.a ruel treatlng level bas~s, l.e., on a level ! related to the gasoline, the three component addltive compositlon should be added to or used in the gasol~ne at a total level of about 125 t.o about 1000 ppm (weight basis) and, on~an indlvidual or component basis, in an amount of from about 20 to 250 ppm, and more preferably 50 to 100 ppm of (1);
about 5 to about 100 ppm, more preferably about 10 to about : 25 of (2); and about 100 to about 650 ppm, more preferàbly 200 to 400 ppm of (3). On a pound~ per barrel of gasoline basis, this is about 5 to 62.5, more preferably 12.5 to ~5 lbs./1000 barrels (bbl~). o~ gasoline of ~1); 1.25 to 25, more preferably 2.5 to 6.25 lbs./1000 bbls. of gasoline of
(2); and 25 to 162.5, more preferably 50 to 100 lbs ~1000 bbls.
of gasoline of (3).
For the concentration of the addi~ive component
of gasoline of (3).
For the concentration of the addi~ive component
(3), above, (~-hen used alone) the ppm concentration and the . pounds per barrel of gasoline treating level i9 t~e s~le as . noted ror component (3) above, i.e., about 25 to 162.5, more ~;, .
preferably about 50 to 100 lbs./1000 bbls. (barrels) of gasoline, or about lOO to 650 ppm~ more preferably about 200 to about 400 ppm of (3`).
- For the concentration of the additive mixture (1) and (3) in gasoli'ne, the treating level should be in the range Or about 20 to 250 ppm, more preferably about 50 to 100 ppln, of component (1), and about 100 to 650 ppm, more .. -. ' .
' ~ ' ` ` ' ' ' . ' . ' , , 1047~5~ ~
pre~erably about 200 to 400 ppm of component (3). On a pounds per barrel of gasoline basis, this amounts to about 5 to about 62.5 lbs,, more preferably about 12.5 to 25 lbs.
; per 1000 bbls. of gasol~ne of component (1); and about 25 .
to 162.5 lbs., more preferably ~0 to 100 lbs per 1000 bbls.
of gaso~ne of component (3).
The tertiary (tert.) or t-alkyl primary amine, having at least one branched chain, may be represented by the general formula (I).
, , '~ ' ' ' ' ' ` `
Rl - R C ~~ NH2 (I) . I , -. . ' I ' ` . ..
; R3 ' . . ' ' '~
:
. . . . , . .' . .
~' ' " , `' ', `~ ' ` '' ;. .
' , ' ., .' ,. . . .
' '' . -10472Sl .
in which Rl, R2, and R3 are alkyl groups whose total -~
carbon atom content ranges from 6 to 24. It 1s preferred that two of the R groups, for example, the Rl and R3 of the t-alkyl primary amlne 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 of two s~f: 10 or more of such amines. 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 acidic media.
. ., ~
Commercially avallable t-alkyl primary amines are often ;; 15 mixtures. t-Octylamine having a branched structure has the formula;
CH CH
, 13 13 .', .
20 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 containing C6H13C (CH3)2NH2 ,:
'.' . .
: . - 8 - .
'.' ~::., :........ ~ . .
.. .. .. -, . . - .
.. .,.~, - . . . - , . . .
. . . . . .~
. , 10472Sl and C7H15C(cH3)2 2 and has a neutral equivalent of abou~ 142. A com~;ercial . preparation Nhich can be used in the present invention is .
readily available under the trademark Primene 81-R
which i5 the trademark used for a mixture Or t-dodecyl-, t-tr~decyl- and t-tetradecylamines or principally a - .
mixture of t-C12H25NH2 to t-C14H29NH2 a neu~ral equivalent o~ about 191. Another commercial preparation which i~ useful in the present lnvention i~ available under the trademark "Primene JM-T". "Primene ~M-T" i~ principally a mlxture of t-ClgN37NH2 to --t-C22H4sNH2 amines and has a neutral equivalent of acout 315. The important consideration is that in a t-alkyl primary amine, the NH2 group is always attached to a ~ 15 carbon atom containing no hydrogen atoms and in the present invention at least one of the alkyl groups is -branched. - --., 1 .
; The alkyl ammonium carboxylate sal~-ethoxylated alk~rl phenol ester of a trimer or dimer acid (or mlxture thereof) is added or included primarily to provide rust . and/or corrosion protection although there is also some modest carburetor detergéncy activity, has the following .. , . ~ . ~
~ormula (II):
g _ . - ' .
, . . . .
... .
~047251 / [~ - 0(cH2cH2o)n R4 ~
- Z \ \ ~ (II) [C2 ~ H3R6]y - R5 x where n is an average number from about 1 to 12.5 and more pre~erably ~rom about 3 to 10; and in the case of a ~alt-ester derlved ~rom 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 ~rom ....
a dimer acid, both x and y are each l;
R4 is an alkyl group containing 4 to 12 carbon atoms;
R5 i5 H or an alkyl group containing 4 to 12 carbon atoms;
~6 is an alhyl group containlng 2 to 24 carbon atoms which may be ~traight or branched chain or an amine substituted alhyl group of 2 to 24 carbon atoms. Pre~erably, R~ contains 12 to 22 carbon atoms; and Z is a saturated or unsaturated hydro^arbon residue o~ the acid, said hydrocarbon residue having 34 to 51.carbon atomsO tZ 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).
. -- 10 --` ' -` : ' , !
.
: ~ . .' ' 047ZSl The alkyl ammonlum carboxylate salt-ester, l.e., component (2), may be u~ed as all trimer acld deri~-ative or all dimer acid derivative, or an~ mixture of the dimer and trimer acid derivatives may be used in the pr~sent invention.
Also, the presence of some monocarboxylic Clg . , .
~sl acid~ or the like in the ester or salt ~orm, or mixtures 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 es~entially all - : .
; octyl, i.e. -CgH17, 2nd-~ is H and which are usable in the present invention are g~ven in Table I below:
TABLE I
: ~lkyl Ammonium Carboxylate .
. . Salt-Ester n ~ X Y
., . .
. . A 1.5t-C12-14 1 2 ,, ; B 1.5t-C12-14 ~ 2 !2 ' 20 C 312 14 1 2 .. . .
~: D 3 t-C12-14 2 , .~ .
.j . E 5 t-C12-14 1 2 F . 7.5 t-C12-14 1 2 G 9.5 t-C12-14 1 2 ~ t-~12-14 2 ~:.
.5 t C12-1~ 1 2 :,. . . .
, ,~ . , . - .' ' , .. .. .
... . . . .
., , , ~,",. ..
- . . .
10472Sl TABLE I (Cont ' d) :. Alkyl Amm onium Carboxylate Salt-Ester n R6 X Y
. J 3 CH~CH2NH2 2 . 5 K . 3 (CH2CH2NH2 )H 2 l L 3 (CH2CH2NH)3H 2 :1 M 1. 5 t-C12-14 N 3 t-C12-14 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 C 4 2 , X 10 t-C12-14 2 Y 1 . 5 t-C18-22 2 z 5 t-C18-22 2 A I 1 t-C12-14 1 2 . B ~ 1~ t-C12-14 1 2 .~. .
. . . C ~ 1 t-C18-22 1 2 D t , 5 t-C18-22 1 2 .. ,~ . . . . .
.
` I . . ' .'~ ' ` ' :. .- : . , ,, : ,, .
., . . .. ~ . , ~
. ~ . . . ..
~ 1047251 The alkyl ammonium carbox~la~e salt ester can be made in known fashion, by ~he acid catalyzed esterification Or a suitable dimer or trlmer acid, or mixture thereo~, ~or example, ln the case of the diester-monQsalt~
With two moles o~ a suitable ethoxylated alkyl phenol followed by conversion of the remaining carboxylic acid functio~ality to an alkyl ammonium carboxylate salt with the addition of a suitable amine. The trimer acid may be the product deriued rrom ~he trimerization reaction of a Clg unsaturated fat~y acid; an example of a suitable trimer acid is that available under the trademark "Empol 1041 The preparation of such dimer and trimer acids is described in United States Patent 2,632,695. A generalized ; reaction scheme ror the preparation of an alkyl ammoni~
,, . ~ .
. carboxylate salt-~ster is sho~n below using a trimer acid for illustrative purposes:
. ~C02(CH2CH20)n ~ ~
CsltC02H)~2H0(CH2CH20)n ~ 5 2) -2H20 C02H R~2 C / C02(CH2CH20)n~R~ ~
~, i .
Where n, R4, R5 and R6 h2ve the values given previously, and C5l is the carbon atom content of the hydrocarbon residue.
. In order to provide induction system and combustion , ^ chamber deposi~ 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.
,~ :. . ..
. I ` - ` 10472Sl .
Th~ mixed polyesters as well as the dimer and trlmer acids may be prepared in kno~n fashion. For exæmple, an unsa~urated aliphatic monocarboxylic acid having between about 16 and 18 carbon atoms per molecule, for example linoleic acid can be polymerized or condensed to form essentially the dimer o~ linoleic acid, a dicarboxylic acid, and al30 the aliphatic monocarboxylic acid can be polymerized to form essentially the trimer of linoleic acid, a tricarboxylic acid. Mixtures of such dicarboxylic and tricarboxylic acids may also be rormed. Similarly, other C16 and C18 unsaturated aliphatic mono~arboxylic acids, including ricinoleic and linolenic acid can be polymerized to dimer and trimer acids or mixtures of such dimer and trimer acids. The preparation o~ such dimer and trimer acids is descrlbed in United States Patent 2,63~,695. The mixed polyesters used in the present s~ inventio~ are prepared by reacting a suitable amount of ; a mixture of an aliphatic alcohol and an ethylo~ylated aromatic alcohol with the polycarboxylic acid to esteri~y essentially all of the carboxyl groups in the acid.
Esteri~ication is conducted according ~o convencional, known methods. The aliphatic alcohols which are suitable for this purpose a~e preferably satura~ed alipha~ic alcohols, having from about 1 to 24 carbon atoms.
Representative aliphatic alcohols include meth~-l alcohol, .. . .
propyl alcohol, n-b-tyl alcohol, iso-bu~yl alcGhcl~
hexyl alcohol, 2-ethylhexyl alcohol, decyl alcohol~
clodecyl alcohol, tridecyl alcohol, isodecyl alcohol, - -lauryl alcohol, stear~l alcohol, hexadecyl alcohol, ' and nondecyl alcohol. ~referably, the aromatic or aromati~ containing alcohols which are used are alkylated phenols which'have been ethoxylated with varying ~lounts of an alkylene oxide such as ethylene oxide. (These ;`
materials are known generally as alkylphenoxypol~etho~
ethanols.) The number of moles of ethylene oxide which may bc condensed with the alkylated phenol may vary from ;~
about one to about 20 ethylene oxide units, and more preferably' from abou~ one to four moles Or ethylene oxide. ~Jhile the ;l presence o~ some unreacted alcohols and some completely esteri~ied all-aliphatic or all-ethoxylated aromatic ' esters will be present in the esterification mixture, the principal active ingredient or the principal active 'I mixed polyester has the following general formula-~, / [3-o(CH2cH2o)n---~ ]p ' 20 Zl R8 :~ , \ [ C02Rg ] q ~ wherein n is an average number Or from about 1 . . .
to 20 and, more preferably, of from about 1 to about 4, and in the case Or the mixed polyester derived from a trimer , 25 acid, p is 1 or 2 and q i5 1 or 2, the su~ of p and q'being 3; and in th~ case of the mixe~ ester derived froM a dimer ~ 15-.''~ ' ' ' ' ' ' ' ~ ' ; i , ~0472Sl acid, both p and q are each l; and where Zl is a saturated o:r unsaturated hydrocarbon residue having an average o~ 34 to 5:1 carbon atoms, said residue being the residue of a dimer or trimer acid of linoleic acid, or mixture o~ said dimers and tri~ers o~ linoleic acid;
-15a-, .1 , "
`I .
.,. . ,' . ' ,.
' . 11 . ., . j I
.
.
, . .
~ ~ .
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' ' ' ' . ~ ' '. ' ' ' ' ' ' ;' 1C~47251 - R7 is an alk~l group conta nin~ 4 to 12 c2rbon atoms, more preferably 8 or 9 carbon atoms;
R8 is H or an al~yl group containing 4 to 12 carbon ato~s, more preferably H;
Rg is an al~yl group containing 1 to ~4 carbon atoms which may be straight or branched chain.
The aromatic alkoxylated al~yl phenols are preferably based on either octyl or nonyl phenol and can contain - approximately 1 to ~0 moles of ethylene oxide, and more preferably about 1 to about 4 moles of condensed 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 containin~
i:; .
at least about 60% trimer acid, and more preferably, , 15 at least about 8G~ trimer acid.
tj ~ !
In the following examples ~hich illustrate this invention, all parts and percentages are by weight, unless otherwise stated. The ability Or the additive or additive combinations of this invention to clean up and maintain the cleanliness of the carburetor of an internal combustion engine is illustrated, and its ability to remove or protect against the formation of induction ,~ , .
i system deposits is also lllustrated below. Also illustrated ~
below is the ability of the additives to reduce octane ~5 requirement increase in an internal combustlon engine.
. . ~ . .
. - 16 -- , , f ~ . ' ' '' ~ '',' .
. -- -- ~--1047~Sl Unless othe~Yise stated, an MS-o8 gasoline ~uel i~ used for the Blowby carburetor detergency Keep-Clean engine tes~ and a Howell Unleaded Gasoline i3 used for the Induction System Deposit Test. The Xo~Jell Unleaded Gasoline has the ~ollowlng properties:
Howell Unleaded Gasollne: Fuel Specification EL-72-1 .
Aromatic Content 30.2~
Olefins 11.6%
Saturates 58.2~
Lead 0.03 g/gal Sulfur 0.009 Wgt Gravity --. 57.9 API
Reed Vapor Pressure 8.1 Research Octane 91.7 Motor Octane 83.8 Initial BP 94F
5 ~ Distilled 228F .
90% Distilled 35lcF
Distillation End Point 4~6F
Engine Test Evaluation of Multipur~ose Carburetor ~etergents A. Blowby Carburetor Detergency Keep Clean Engine Test 1. Engine Test ~rocedure The Blo~by Carburetor Detergency Keep Clean Engine Test (BBCDT-KC) measures the ability o~ a gasoline .~ .
; additive to keep clean the carburetor throttle body area, and is run in a 1970 Ford 351 CID ~T-8 engine equipped by means o~ a special ~tyl~ inta~e manifold with two one- -: barrel carburetors, which can be independently ad~usted .
and activated. With this arrangement, a separ2te test fuel can be ~valuated by each carburetor which feeds four : of the eight cylinders via the non-in~erconnected inta~e manirold. The carburetors are modified ~r1th re~,~cvable alumirum sleeves in order to ~aci~ltate we~hing o~ the , , . ~ 1 ,. ~
17 -- ~
1047~51 deposits which accumulate ln the throt~le body area. ...
I'he severity of the test is ad~usted to an appropri~te l.evel by recycling the entire amount Or blowby gase~, approximately 90-110 CFH, to the top of the air cleaner 30 ; 5 that each carburetor recelves an equal volume of these gases. Equal intake mixture flow through each carburetor is ad~usted during the first hour of operation of means of intake manifold differential pressure and C0 exhaust gas analysis. The following test cycle and operating , . . . - .
0 conditions are employed:
~ Test Cycle:
~' Phase I 650 engine rpm, 8 min.
, . . .
Phase II 3000 engine rpm, 1 min.
Test Duration~ hrs. 10 '~ 1 Intake Air, F 135 ~ 10 ,. . . .
.~ Jacket Water, F 190 10 " .
. Engine Oil-Sump, F 210 ~ 10 % C0 in Exhaust 3.0 ~ 0.2 Blowby, CFH 90 - 110 The weight (mgsO) of deposits accumul~ted on the aluminum sleeve is measured, and the average value ~ of four tests per additive or additive mixture is ,.,,~ . .
reported. - - - -The gasollne used in the BBC~T-KC test is an MS-o8 gasoline having the follo~ing properties:
, . . .
- 18 _ ,, .
, . . . ' .
~0~725~ -Gra~ity 59 7 : Sp. Gr. at 60F. -74 ~SI~ D-86 D~s~ t~on, F.
IBP -'93 10% 123 5% - .- 205 90% ~48 E. P. 405 ' 10 % Recovered 98 '; % Residue % Loss - . % Sulrur 0.11 ; ' Lead, Gm/gal .. 3.o8 FIA Composition .~ ~romatics, % ' 23.1 Olefins, % 20.0 ' Saturates, % 56.9 ` . - O. Oxidation Stability, ~inutes 600+
.. 20 ASTM Gum (Unwashed), mg/100 ml 1.0 -' Research Octane Number 95.5 % H 13.10 ' % C - 86.61 -H/C . 1.80 :
~ 25 B. ''_nduction System Deposit Engine Test .
., , ~, 1. Engine Test Procedure ....
.
. The Induction System Deposit Test (ISDT) which is used to evaluate the ability of ~asoline additives or mixtures of additives to control induction system deposits, 3 is run using a new a~r-cooled, single cylinder, 4 cycle, .:2.5 H.P. Briggs and Stratton engine for each test. The .'engine is run for 150 hours' at 3000 rp~ and 4.2 ft. lb~. -`load~ wlt~ a 1 hour'shutdo~n every 10 hours to check the , ~ 19 - .
.,; .
: -- - ' .
. ._ . t :
.- . ~ ',, - . .
o~l level. Carbon monoxlde exhau~t emission measuremen~s are made eacn houI~ to insule that a constant air to fuel (A/F) ratio is being maintained.
I Upon completion of a test,run, the en~ine is 1 5 partially disassembled, and the intake valve and port - are rated and valve and port deposits are collected and weighe d .
.. . .
C. Rusting Test Method .
A rusting test method for fuel additive rus~
, 10 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 modification of ;' the ba'sic ASTM method D665. The ob~ect of the test ~;' ig to evaluate the ability of a gasoline additive to inhibit rusting of ~errous parts such as encountered in gasoline storage and transportation systems. The ~.ethod ~ lnvolves stirring a mixture Or 300 ml. of an additive ; blend in depolarized isooctane with 30 ml. of de-ion~zed - sea-water, , - dlstilled water, medium hard water, or syn-hetic ~or ~¦ 20 5 hours at a temperatllre of 100F. (37.8C) with a cylindrical steel specimen completely il~nersed therein.
Test results a~ 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 of pitting and 0 , .. .
being the best. The type ~ medium hard water is prep~red as fGl10ws;
,~ ' .
*This~ is a published U.S. milit!ary specification available to the public from the Department o~f Defence, Washington, D,C.~U.S.A.
,. . _, . . . . ~ . . ...................................... . .
.
~047Z5~ 9 3 stock solutions using ACS reagent-grade - chemicals in dlstllled water containing, respectively, 16.4 g/liter ~aHC03, 13.2 g/literCaC12.2H20, and ~.2 ~liter ~gS04.7H20. Ten ml. of the NaHC03 sto_k solution are ; 5 pipetted into 800 ml. of distilled water in a l-liter ~
volumetric flask, and then shaken vigorously. Whiie i ~wirling the contents Or the flask,-10 ml. o~ the CaC12 ~ -stock solu~ion are pipetted into the ~lask and then 10 ml, Or the MgS04 stock solution are also pipetted into the ; 10 flask, distilled water is then added to bring the volume ; to 1 liter and mixed thoroughly. The final blend should : be clear and free of precipitate.
D. Combustion Chamber Deposit En~ine Test .: . .
1, Engine Tesf, Procedure ,,.
The Combustion Chamber Deposit ~n~ine Test (CCDET) is used to evaluate the abilityof a gasoline additive, or mixture of additives to control or reduce the , . . .
octane number requirement increase (ONRI), in an internal co~nbustion engine, the test is run using a 19l2 Chevrolet .. . ~ 20 350 CID v-8 engir.e equipped with a two barrel carburetor and a 1972 Tubo Hydromatic 350 transmission which is conne~ted to a 1014-2 WIG dynamometer equipped with a ; .
200.3 lb-ft lnertia wheel. The following test cycle ~; and operating conditions are employed and are intended ..... .
to ~imulate an urban taxi cab.
.
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--\ --10~7251 .~-Test C~cle P~ase I Start - idle, 650-750 rpm PhaLse II Accelerate - 1 to 2 shif~, 5.5 ~ec., 2900-3000 rpm Phase III Accelerate - 2 to 3 shift, 9.5 sec.
~ 2800-2900 rpm ~hase IV 3rd ~ear, 10.0 sec., 2600 rpm ;~
Phase V Decelerate to idle, 15.0 sec.
Test Duration 200 hrs.
~uel 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 requ'rement is determined at 24 hr~.
lnterval under the following engine conditions: transmission ,i'! in 3rd gear with an output shaft speed controlled at 1500 rpm and the engine throttle wide open. The octane nwnber 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 o~ known octane number until audible knock is perceived. The lowest standardized octane n~unber blend at which the en~ine does not knock is recorded as the octane nwnber requirement.
Octane num~er requirement in^rease is tnen the dif~erence bet~een the init~' octane nwn~er requirement and the final octane n~ber requirement ~or a p~rticu'ar test.
." ' ' ' ~ , .
- ~0~7251 - The novel fuel compositions may be prepared by adding the indi~idual additives directly ~o the fuel, or an additive blend or mixture of one or more of thP
components may be prepared or a concentrate o~ one or more o~ the additives in a su~table solvent such as toluene or xyiene may be prepared. Also, all o~ 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 typ~cal mixed pol~Jester employed in the fuel of the invention is as follows:
PREPARATION OF TRI~R ACID, DIISOD~CYL, MONO-OCTYLPHENOXYPOLYETHOXYEIHANOL (3 MOLE~ ETH~I.E~ OXIDE) i TRIEST~R
; 15 To a 3-1 three-necked round bottom flas'~
ritted with a mechanical stirrer, thermometer, and Dean-Stark trap with reflux condenser are c~arged 845 g.
. (1 mole~ of a trimer acid mixture (E~e~ Industries 1834-18R trimer acid,) comprising 70-80~ trimer acid and 30 to 20% dimer acid, 316 g. (2 moles) o~ isodecyl alcohol, 338 g. (1 mole) of octylphenoxypolyethoxyethanol containing about 3 moles of condensed ethylene oxide, 200 ml of toluene, and 1.0 gO Or p-toluenesulfonic acid.
The reaction mixture is heated toreflux (w~th stirring) which occurs near 135C. Refluxing is continued ~or 6 ., . ' .
.'' ' . ' .
.: c ~, ' ;
.
... . .. . . . .
~047251 hours durin~ which time the theoretical quantity of ~at;er is evolved. Toluene solvent is stripped under vacuum, 3.0 g. of Na2C03 aQded to neutralize the p-toluenesulfonic acid, and the product filtered. The material prepared in this.way generally has an acid near 1.0 The theoretical product distribution assuming that eqvilibrium has been obtalned and that there are no free energy formation differences between the various esters is the followin~:
wt % mole %
trim~r acid, triisodecyl triester 25.9 29.6 trimer ac~d, diisodecyl~mono-octylphenoxypolyethoxyethanol ; 15 (3 moles ethylene oxide) 44.5 44.5 trimer acid, isodecyl di-- octylphenoxypolyethoxyethanol (3 moles ethylene oxide) triester 25.0 22.2 ~; 20 trimer acid, ~ri-. ¦ octylphenoxypolyethoxyethanol (3 moles e'hylene oxide) 4.6 3.7 Actual analysis shows the diisodecylmono-octylphenoxypol~ethoxyethanol ester to be present in the preponderant numerical percentage amount, and actual chromatographic analysis conforms substantially :,.
. _ 2L~ -": ., ' , '' . . ' ' ~047251 ~
with the predicted amount. Changes in the ra~lo of the ester components may be obtained, by alterin~ ~he esterification condition~.
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 l dimethyl/mono-octyl- Ester of trimer phenoxy polyethoxy- of linoleic acid.
ethanol containing ~ `
average of 3 moles of -\ condensed ethylene oxide.
Example 2 dibutyl/mono-octyl- Ester of the trimer i~ 15 phenoxy polyethoxy- of linoleic acid.
ethanol with average of 3 moles Or ethylene , oxide.
,~ .
Example 3 di-2-ethylhexyl/mono- Ester of the trimer ; 20 octylphenoxy poly- of linoleic acid.
ethoxyethanol with 3 moles of ethylene ; oxide.
."
Example 4 diisodecyl/mono-oc~yl- Ester of the trimer phenoxy polyethoxy- of linoleic acid.
ethanol with avera~e of 3 moles of ethylene oxide.
.
Example 5 di Cl6_20 aliphatic Ester of the trimer alcohol/ mono- of linoleic acid.
octylphenoxy poly-ethoxyethanol with 3 moles of ethylene oxide.
35 Ex~npie 6 mo~o-isodecyl/di-octyl- Ester of the trimer - phenoxy polyethoxy- Or linoleic acid.
ethanol with 3 moles o~ ethylene oxideO
. - , .
.
,: -., .
.. . . . ~ .
1047ZSl TABLE II (Cont~d) Example 7 diisodecyl/mono-octyl- Ester of the trimer phenoxy polyethoxy- of l~noleic acld.
ethanol with average of 5 moles of ethylene o~ide.
Example 8 dimethyl/mono-oc'yl- Ester of the trimer phenoxy ethoxye~hanol of linoleic acid - with average of 1 mole of ethylene oxide.
E~ample 9 mono-isodecyl/mono-octyl- Ester of t~e dimer of phenoxy polyethoxy linoleic acid.
ethanol wlth 3 moles ethylene oxide.
The esterification reaction is usually acid catalyzed and can be carried out over a broad range o~
, - te~peratures, but usually the temperature wlll vary fro~
about 75C, to about 180C. The mixture Or aliphatic alcohol and ethoxylated aromatic alcohols can also vary fairly ~lidely depending on the products desired, but ordinarily the ratio of the aliphatic alcohol to ,;' the ethoxylated aroma~ic alcohol wlll vary from abou~
~ ,A "
(on a molar basis) one to four to about four to one, and more preferably about one to two to abo~ two to one.
. ~ .
The quantity of mixed alcohols used shoulà be suf~icient to essentially completly es~erify the polycarboxylic acid . ~ , .
(i.e. the trimer or dimer acid,o~ mi*ture thereof) and there can be used an equivalent amount or slight molar-excess of alcohols in relation to the polycarboxylic ; 3 acid during the esterif~cation reaction.
, . . . . .. .
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The base ruel employed in the following Examples (Tables III, IV, ànd V belo~r) ~s a Howell unleaded gasoline a~s described hereinabove, except for the BBCDT-KC tests wherein an MS-08 gasoline as described hereinabove is used.
s Induction System Deposit Test results (ISDT) are reported in milligrams (mg.) of deposit as are the Blowby Carburetor Deter-gency Keep Clean Engine Test results. Percent rusting is also reported. These test procedures are described above.
TABLE III .
Ex~mple Fuel Additive and ISDT, mg,BBCDT2-~C
Concentration ppmdeposit mg. deposit Gasoline (Valve and , . port Control Untre2ted Gasloline 365 .13 triisodecyl ester CxaPpale A of trimer of linoleic 170 acid, 300 ppm ` mixed dimethy poly-. 20 No. 10 ester of Example 172 (see Table II), 300 ppm mixed dibutyl poly-No. 11 ester Or Example 235 18.1 .: (Table II above) . 3 ppm -. - mixed diisodecyl No. 12 polyester of 37 14.2 Example 4 (Table II aboue) 300 ppm .; ' .
3 mixed diisodecyl polyester of Exa~ple No. 1~ 7 (Table II above) 475 3O ppm .. trl-octylpolyeth-: 35 oxyethanol ester Or . Mo, 14 trimer of linoleic 186 acid with 3 moles eth~lene oxide, 500 ppm ,.
. - ~ I
; ; - 27 -, 1047~51 .
TABLE III (Cont~d) Example Fuel Addi~ive and ISDTl mg. ~BCDT2-~C ~-Concentration ppm deposit mg. deposit Gasoline (Valve and . port) .
Comparative commercially avail-Example B able and used a].kyl435 4 0 ~ .ammonium phosphate, 50 ppm Comparative co~nercially avail-Example C able and used poly- 1247 3.3 ; butene succinimide, ~; 140 pp~
... . ..
(1) Induction System D.eposit Test, as , 15 described above.
(2) Blowby Carburetor Detergency Keep Clean Engine Test, as described above.
In Table IV, below, there are shown results .
obtained with a combination or mixture Or additives ~ .
;,! 20 according to the present invention.
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TABLE IV (Conttd) . 1 WHERE
Zl is the hydrocarbon residue of the product of trimerization . of an unsaturated C18 fatty ac~d, such as linoleic acid, 5whlch ~s~a mixture of about 70-80~ trimer acid (C54) and` .
and about 30-20,q~ of dimer aoid (C36), all parts by W-igbt.
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; TABLE V
(Octane Number Requirement Increase~
Ex2mple Fuel Additive and Octane N~.ber*
Concentration, ppm, Requirement in Gasoline Increase Control Untreated gasoline, i.e. 10 . ~ base fuel Commercially available ComparatiVe and used polybutene 8 Examp e D succininide, 140 ppm Same additive package or No. 22 blends as in Example No.
15 (Table IV) (total = 370 ppm) Same additive as Example No. 23 No. 2, Table ~I at 5 : 300 ppm * As measured b~J the Combustion Chamber Deposit Engine Test.
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.
. 104q'2Sl As is evident from the date in Table III, the mixed polyesters of this invention ~Yhile individuall~-aflording no carburetor detergency activity, per se, are very effective at controlling induction system deposits in an internal combustion engine.
~Jhen the mixed polyesters are used i~ combination with rust inhibitors and carburetor ~etergents as shown in Table IV so that a multipurpose additive package is formed, the activlty of e~amples 15, 16, and l9 is significantly better than the base fuel in all three performance categories, ; i.e., rust inhibitor, carburetor detergency, and induction sys~em detergency. hlt}lough examples 17, 18, 20, 21, and 22 sho~J higher levels of induction system deposits than the base fuel their total performance is significantly better than the base fuei treated with currently used commercial additives such as the alkyl ammonium phosphates and ~he polybutene succinimides. It is important to remember that untreated gasoline is rarely used in present day l automobiles and that gasoline treated with conventional : 20 carburetor detergents and rust inhibitors ~ill normally s~ .
give higher levels of induction system deposits than the base gasoline as is shown in Comparative Examples B and . ~ .
C of Table III.
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~0~72Sl Although the mechanlsm o~ ~ctivity is not clear, i~ is evident ~rom the data in Table V that the additive combination of our invention is effective in modifying the deposits in the combustion chamber such that the octane number requirement increase Or the engine is less than ; with either untreated gasoline or base gasoline treated with a commercially used polybutene succinimlde, ; In a specific example of an alternative embodiment o~ this invention, wherein the carburetor detergent (1) and induction system deposit control additive (3) are used (with-out any added rust inhibitor) in gasoline, at a total con-.
cen~ration of about 350 ppm, (50 ppm of 1 and 300 ppm Or 3), the follo~ring results are obtained: for the ISDT Test, 201 milligr~ns (m~,) of deposits; and for the BBCDT-KC Test, 1.3 mg. of deposits. In this test, component (1) was a t-Clg-C22 alkyl amine such as was used in Example 15, and component (3) was the mixed polyester of Example 4. As noted previously, a Howell unleaded gasoline is used ror the ISDT tests, and MS-o8 gasoline is used ~or the BBCDT-KC tests.
' In another alternative embodiment of this invention, other dicarboxylic acid esters, such as an adipa~e diester ` may be substituted in whole or part ~or component (3) o~
the detergent composition, noted above, to provide induction ` systems deposit control. Thus, an adipate diester compris ng 1 25 the mono-isodecyl, mono-octyl pheno~ polyetho~ eth~nol ~ (containin~ an average of 3 moles o~ condensc-d ethylene : - 34 - .
- - t , . . .
.
. . . .
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/al~yl phenoxy (alkyl of C4 to Cg~ polyethoxy ethanol tcontaining 1 to 20 moles, and ~o~e preferably about 1 to 5 moles condensed ethylene oxide) ester may also be used to provide induction system deposit control either alone, or in combination 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 oombination with components (l)* and (2)*, noted above.
Other results using 300 ppm of the specific monoisdecyl, mono-octyl phenoxy polyethoxy ethanol (3 moles ethylene oxide) adipic ester noted above in combination with 50 ppm of the t-C18-C22 alkyl amine (component (1~ above) are as follows:
in the ISDT te~t, 225 ~g.iof deposit, and~in the BBCDT-KC test, i 2.3 mg~ of deposit. Wh~n 10 ppm of the rust inhibitor component - ~2) of Example No. 15 is added to the mixture 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 ~e~, 327 mg. of deposit, 2.2 mg. of deposit in the s BBCDT-KC test, and 0% area rusted in the rust 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.
,: 3D
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In another example using 50 ppm of the t-Clg-C22 alkyl amine (component (1) above~, 5 ppm of the rust inhibitor component (2) of Example ~rO. 15, and 300 ppm of the mono- -i~odecyl, mono-octyl phenoxy polyethox~Jethanol (containing 5 moles o~ ethylene oxide~ adipate ester the follo~Jing results ~ere obtained: in the ISDT test, 237 mg. of deposit, in the BBCDT-KC test, 305 mg. of deposit, and 0% area rusted ~ in the rust test.
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. ~
. ~, .
.~ ' , "
.
~ 3~ -.
:. . . - -
preferably about 50 to 100 lbs./1000 bbls. (barrels) of gasoline, or about lOO to 650 ppm~ more preferably about 200 to about 400 ppm of (3`).
- For the concentration of the additive mixture (1) and (3) in gasoli'ne, the treating level should be in the range Or about 20 to 250 ppm, more preferably about 50 to 100 ppln, of component (1), and about 100 to 650 ppm, more .. -. ' .
' ~ ' ` ` ' ' ' . ' . ' , , 1047~5~ ~
pre~erably about 200 to 400 ppm of component (3). On a pounds per barrel of gasoline basis, this amounts to about 5 to about 62.5 lbs,, more preferably about 12.5 to 25 lbs.
; per 1000 bbls. of gasol~ne of component (1); and about 25 .
to 162.5 lbs., more preferably ~0 to 100 lbs per 1000 bbls.
of gaso~ne of component (3).
The tertiary (tert.) or t-alkyl primary amine, having at least one branched chain, may be represented by the general formula (I).
, , '~ ' ' ' ' ' ` `
Rl - R C ~~ NH2 (I) . I , -. . ' I ' ` . ..
; R3 ' . . ' ' '~
:
. . . . , . .' . .
~' ' " , `' ', `~ ' ` '' ;. .
' , ' ., .' ,. . . .
' '' . -10472Sl .
in which Rl, R2, and R3 are alkyl groups whose total -~
carbon atom content ranges from 6 to 24. It 1s preferred that two of the R groups, for example, the Rl and R3 of the t-alkyl primary amlne 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 of two s~f: 10 or more of such amines. 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 acidic media.
. ., ~
Commercially avallable t-alkyl primary amines are often ;; 15 mixtures. t-Octylamine having a branched structure has the formula;
CH CH
, 13 13 .', .
20 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 containing C6H13C (CH3)2NH2 ,:
'.' . .
: . - 8 - .
'.' ~::., :........ ~ . .
.. .. .. -, . . - .
.. .,.~, - . . . - , . . .
. . . . . .~
. , 10472Sl and C7H15C(cH3)2 2 and has a neutral equivalent of abou~ 142. A com~;ercial . preparation Nhich can be used in the present invention is .
readily available under the trademark Primene 81-R
which i5 the trademark used for a mixture Or t-dodecyl-, t-tr~decyl- and t-tetradecylamines or principally a - .
mixture of t-C12H25NH2 to t-C14H29NH2 a neu~ral equivalent o~ about 191. Another commercial preparation which i~ useful in the present lnvention i~ available under the trademark "Primene JM-T". "Primene ~M-T" i~ principally a mlxture of t-ClgN37NH2 to --t-C22H4sNH2 amines and has a neutral equivalent of acout 315. The important consideration is that in a t-alkyl primary amine, the NH2 group is always attached to a ~ 15 carbon atom containing no hydrogen atoms and in the present invention at least one of the alkyl groups is -branched. - --., 1 .
; The alkyl ammonium carboxylate sal~-ethoxylated alk~rl phenol ester of a trimer or dimer acid (or mlxture thereof) is added or included primarily to provide rust . and/or corrosion protection although there is also some modest carburetor detergéncy activity, has the following .. , . ~ . ~
~ormula (II):
g _ . - ' .
, . . . .
... .
~047251 / [~ - 0(cH2cH2o)n R4 ~
- Z \ \ ~ (II) [C2 ~ H3R6]y - R5 x where n is an average number from about 1 to 12.5 and more pre~erably ~rom about 3 to 10; and in the case of a ~alt-ester derlved ~rom 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 ~rom ....
a dimer acid, both x and y are each l;
R4 is an alkyl group containing 4 to 12 carbon atoms;
R5 i5 H or an alkyl group containing 4 to 12 carbon atoms;
~6 is an alhyl group containlng 2 to 24 carbon atoms which may be ~traight or branched chain or an amine substituted alhyl group of 2 to 24 carbon atoms. Pre~erably, R~ contains 12 to 22 carbon atoms; and Z is a saturated or unsaturated hydro^arbon residue o~ the acid, said hydrocarbon residue having 34 to 51.carbon atomsO tZ 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).
. -- 10 --` ' -` : ' , !
.
: ~ . .' ' 047ZSl The alkyl ammonlum carboxylate salt-ester, l.e., component (2), may be u~ed as all trimer acld deri~-ative or all dimer acid derivative, or an~ mixture of the dimer and trimer acid derivatives may be used in the pr~sent invention.
Also, the presence of some monocarboxylic Clg . , .
~sl acid~ or the like in the ester or salt ~orm, or mixtures 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 es~entially all - : .
; octyl, i.e. -CgH17, 2nd-~ is H and which are usable in the present invention are g~ven in Table I below:
TABLE I
: ~lkyl Ammonium Carboxylate .
. . Salt-Ester n ~ X Y
., . .
. . A 1.5t-C12-14 1 2 ,, ; B 1.5t-C12-14 ~ 2 !2 ' 20 C 312 14 1 2 .. . .
~: D 3 t-C12-14 2 , .~ .
.j . E 5 t-C12-14 1 2 F . 7.5 t-C12-14 1 2 G 9.5 t-C12-14 1 2 ~ t-~12-14 2 ~:.
.5 t C12-1~ 1 2 :,. . . .
, ,~ . , . - .' ' , .. .. .
... . . . .
., , , ~,",. ..
- . . .
10472Sl TABLE I (Cont ' d) :. Alkyl Amm onium Carboxylate Salt-Ester n R6 X Y
. J 3 CH~CH2NH2 2 . 5 K . 3 (CH2CH2NH2 )H 2 l L 3 (CH2CH2NH)3H 2 :1 M 1. 5 t-C12-14 N 3 t-C12-14 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 C 4 2 , X 10 t-C12-14 2 Y 1 . 5 t-C18-22 2 z 5 t-C18-22 2 A I 1 t-C12-14 1 2 . B ~ 1~ t-C12-14 1 2 .~. .
. . . C ~ 1 t-C18-22 1 2 D t , 5 t-C18-22 1 2 .. ,~ . . . . .
.
` I . . ' .'~ ' ` ' :. .- : . , ,, : ,, .
., . . .. ~ . , ~
. ~ . . . ..
~ 1047251 The alkyl ammonium carbox~la~e salt ester can be made in known fashion, by ~he acid catalyzed esterification Or a suitable dimer or trlmer acid, or mixture thereo~, ~or example, ln the case of the diester-monQsalt~
With two moles o~ a suitable ethoxylated alkyl phenol followed by conversion of the remaining carboxylic acid functio~ality to an alkyl ammonium carboxylate salt with the addition of a suitable amine. The trimer acid may be the product deriued rrom ~he trimerization reaction of a Clg unsaturated fat~y acid; an example of a suitable trimer acid is that available under the trademark "Empol 1041 The preparation of such dimer and trimer acids is described in United States Patent 2,632,695. A generalized ; reaction scheme ror the preparation of an alkyl ammoni~
,, . ~ .
. carboxylate salt-~ster is sho~n below using a trimer acid for illustrative purposes:
. ~C02(CH2CH20)n ~ ~
CsltC02H)~2H0(CH2CH20)n ~ 5 2) -2H20 C02H R~2 C / C02(CH2CH20)n~R~ ~
~, i .
Where n, R4, R5 and R6 h2ve the values given previously, and C5l is the carbon atom content of the hydrocarbon residue.
. In order to provide induction system and combustion , ^ chamber deposi~ 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.
,~ :. . ..
. I ` - ` 10472Sl .
Th~ mixed polyesters as well as the dimer and trlmer acids may be prepared in kno~n fashion. For exæmple, an unsa~urated aliphatic monocarboxylic acid having between about 16 and 18 carbon atoms per molecule, for example linoleic acid can be polymerized or condensed to form essentially the dimer o~ linoleic acid, a dicarboxylic acid, and al30 the aliphatic monocarboxylic acid can be polymerized to form essentially the trimer of linoleic acid, a tricarboxylic acid. Mixtures of such dicarboxylic and tricarboxylic acids may also be rormed. Similarly, other C16 and C18 unsaturated aliphatic mono~arboxylic acids, including ricinoleic and linolenic acid can be polymerized to dimer and trimer acids or mixtures of such dimer and trimer acids. The preparation o~ such dimer and trimer acids is descrlbed in United States Patent 2,63~,695. The mixed polyesters used in the present s~ inventio~ are prepared by reacting a suitable amount of ; a mixture of an aliphatic alcohol and an ethylo~ylated aromatic alcohol with the polycarboxylic acid to esteri~y essentially all of the carboxyl groups in the acid.
Esteri~ication is conducted according ~o convencional, known methods. The aliphatic alcohols which are suitable for this purpose a~e preferably satura~ed alipha~ic alcohols, having from about 1 to 24 carbon atoms.
Representative aliphatic alcohols include meth~-l alcohol, .. . .
propyl alcohol, n-b-tyl alcohol, iso-bu~yl alcGhcl~
hexyl alcohol, 2-ethylhexyl alcohol, decyl alcohol~
clodecyl alcohol, tridecyl alcohol, isodecyl alcohol, - -lauryl alcohol, stear~l alcohol, hexadecyl alcohol, ' and nondecyl alcohol. ~referably, the aromatic or aromati~ containing alcohols which are used are alkylated phenols which'have been ethoxylated with varying ~lounts of an alkylene oxide such as ethylene oxide. (These ;`
materials are known generally as alkylphenoxypol~etho~
ethanols.) The number of moles of ethylene oxide which may bc condensed with the alkylated phenol may vary from ;~
about one to about 20 ethylene oxide units, and more preferably' from abou~ one to four moles Or ethylene oxide. ~Jhile the ;l presence o~ some unreacted alcohols and some completely esteri~ied all-aliphatic or all-ethoxylated aromatic ' esters will be present in the esterification mixture, the principal active ingredient or the principal active 'I mixed polyester has the following general formula-~, / [3-o(CH2cH2o)n---~ ]p ' 20 Zl R8 :~ , \ [ C02Rg ] q ~ wherein n is an average number Or from about 1 . . .
to 20 and, more preferably, of from about 1 to about 4, and in the case Or the mixed polyester derived from a trimer , 25 acid, p is 1 or 2 and q i5 1 or 2, the su~ of p and q'being 3; and in th~ case of the mixe~ ester derived froM a dimer ~ 15-.''~ ' ' ' ' ' ' ' ~ ' ; i , ~0472Sl acid, both p and q are each l; and where Zl is a saturated o:r unsaturated hydrocarbon residue having an average o~ 34 to 5:1 carbon atoms, said residue being the residue of a dimer or trimer acid of linoleic acid, or mixture o~ said dimers and tri~ers o~ linoleic acid;
-15a-, .1 , "
`I .
.,. . ,' . ' ,.
' . 11 . ., . j I
.
.
, . .
~ ~ .
,; , . .
... .
.'. . .
~ " ' ' ' .
' ' ' ' . ~ ' '. ' ' ' ' ' ' ;' 1C~47251 - R7 is an alk~l group conta nin~ 4 to 12 c2rbon atoms, more preferably 8 or 9 carbon atoms;
R8 is H or an al~yl group containing 4 to 12 carbon ato~s, more preferably H;
Rg is an al~yl group containing 1 to ~4 carbon atoms which may be straight or branched chain.
The aromatic alkoxylated al~yl phenols are preferably based on either octyl or nonyl phenol and can contain - approximately 1 to ~0 moles of ethylene oxide, and more preferably about 1 to about 4 moles of condensed 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 containin~
i:; .
at least about 60% trimer acid, and more preferably, , 15 at least about 8G~ trimer acid.
tj ~ !
In the following examples ~hich illustrate this invention, all parts and percentages are by weight, unless otherwise stated. The ability Or the additive or additive combinations of this invention to clean up and maintain the cleanliness of the carburetor of an internal combustion engine is illustrated, and its ability to remove or protect against the formation of induction ,~ , .
i system deposits is also lllustrated below. Also illustrated ~
below is the ability of the additives to reduce octane ~5 requirement increase in an internal combustlon engine.
. . ~ . .
. - 16 -- , , f ~ . ' ' '' ~ '',' .
. -- -- ~--1047~Sl Unless othe~Yise stated, an MS-o8 gasoline ~uel i~ used for the Blowby carburetor detergency Keep-Clean engine tes~ and a Howell Unleaded Gasoline i3 used for the Induction System Deposit Test. The Xo~Jell Unleaded Gasoline has the ~ollowlng properties:
Howell Unleaded Gasollne: Fuel Specification EL-72-1 .
Aromatic Content 30.2~
Olefins 11.6%
Saturates 58.2~
Lead 0.03 g/gal Sulfur 0.009 Wgt Gravity --. 57.9 API
Reed Vapor Pressure 8.1 Research Octane 91.7 Motor Octane 83.8 Initial BP 94F
5 ~ Distilled 228F .
90% Distilled 35lcF
Distillation End Point 4~6F
Engine Test Evaluation of Multipur~ose Carburetor ~etergents A. Blowby Carburetor Detergency Keep Clean Engine Test 1. Engine Test ~rocedure The Blo~by Carburetor Detergency Keep Clean Engine Test (BBCDT-KC) measures the ability o~ a gasoline .~ .
; additive to keep clean the carburetor throttle body area, and is run in a 1970 Ford 351 CID ~T-8 engine equipped by means o~ a special ~tyl~ inta~e manifold with two one- -: barrel carburetors, which can be independently ad~usted .
and activated. With this arrangement, a separ2te test fuel can be ~valuated by each carburetor which feeds four : of the eight cylinders via the non-in~erconnected inta~e manirold. The carburetors are modified ~r1th re~,~cvable alumirum sleeves in order to ~aci~ltate we~hing o~ the , , . ~ 1 ,. ~
17 -- ~
1047~51 deposits which accumulate ln the throt~le body area. ...
I'he severity of the test is ad~usted to an appropri~te l.evel by recycling the entire amount Or blowby gase~, approximately 90-110 CFH, to the top of the air cleaner 30 ; 5 that each carburetor recelves an equal volume of these gases. Equal intake mixture flow through each carburetor is ad~usted during the first hour of operation of means of intake manifold differential pressure and C0 exhaust gas analysis. The following test cycle and operating , . . . - .
0 conditions are employed:
~ Test Cycle:
~' Phase I 650 engine rpm, 8 min.
, . . .
Phase II 3000 engine rpm, 1 min.
Test Duration~ hrs. 10 '~ 1 Intake Air, F 135 ~ 10 ,. . . .
.~ Jacket Water, F 190 10 " .
. Engine Oil-Sump, F 210 ~ 10 % C0 in Exhaust 3.0 ~ 0.2 Blowby, CFH 90 - 110 The weight (mgsO) of deposits accumul~ted on the aluminum sleeve is measured, and the average value ~ of four tests per additive or additive mixture is ,.,,~ . .
reported. - - - -The gasollne used in the BBC~T-KC test is an MS-o8 gasoline having the follo~ing properties:
, . . .
- 18 _ ,, .
, . . . ' .
~0~725~ -Gra~ity 59 7 : Sp. Gr. at 60F. -74 ~SI~ D-86 D~s~ t~on, F.
IBP -'93 10% 123 5% - .- 205 90% ~48 E. P. 405 ' 10 % Recovered 98 '; % Residue % Loss - . % Sulrur 0.11 ; ' Lead, Gm/gal .. 3.o8 FIA Composition .~ ~romatics, % ' 23.1 Olefins, % 20.0 ' Saturates, % 56.9 ` . - O. Oxidation Stability, ~inutes 600+
.. 20 ASTM Gum (Unwashed), mg/100 ml 1.0 -' Research Octane Number 95.5 % H 13.10 ' % C - 86.61 -H/C . 1.80 :
~ 25 B. ''_nduction System Deposit Engine Test .
., , ~, 1. Engine Test Procedure ....
.
. The Induction System Deposit Test (ISDT) which is used to evaluate the ability of ~asoline additives or mixtures of additives to control induction system deposits, 3 is run using a new a~r-cooled, single cylinder, 4 cycle, .:2.5 H.P. Briggs and Stratton engine for each test. The .'engine is run for 150 hours' at 3000 rp~ and 4.2 ft. lb~. -`load~ wlt~ a 1 hour'shutdo~n every 10 hours to check the , ~ 19 - .
.,; .
: -- - ' .
. ._ . t :
.- . ~ ',, - . .
o~l level. Carbon monoxlde exhau~t emission measuremen~s are made eacn houI~ to insule that a constant air to fuel (A/F) ratio is being maintained.
I Upon completion of a test,run, the en~ine is 1 5 partially disassembled, and the intake valve and port - are rated and valve and port deposits are collected and weighe d .
.. . .
C. Rusting Test Method .
A rusting test method for fuel additive rus~
, 10 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 modification of ;' the ba'sic ASTM method D665. The ob~ect of the test ~;' ig to evaluate the ability of a gasoline additive to inhibit rusting of ~errous parts such as encountered in gasoline storage and transportation systems. The ~.ethod ~ lnvolves stirring a mixture Or 300 ml. of an additive ; blend in depolarized isooctane with 30 ml. of de-ion~zed - sea-water, , - dlstilled water, medium hard water, or syn-hetic ~or ~¦ 20 5 hours at a temperatllre of 100F. (37.8C) with a cylindrical steel specimen completely il~nersed therein.
Test results a~ 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 of pitting and 0 , .. .
being the best. The type ~ medium hard water is prep~red as fGl10ws;
,~ ' .
*This~ is a published U.S. milit!ary specification available to the public from the Department o~f Defence, Washington, D,C.~U.S.A.
,. . _, . . . . ~ . . ...................................... . .
.
~047Z5~ 9 3 stock solutions using ACS reagent-grade - chemicals in dlstllled water containing, respectively, 16.4 g/liter ~aHC03, 13.2 g/literCaC12.2H20, and ~.2 ~liter ~gS04.7H20. Ten ml. of the NaHC03 sto_k solution are ; 5 pipetted into 800 ml. of distilled water in a l-liter ~
volumetric flask, and then shaken vigorously. Whiie i ~wirling the contents Or the flask,-10 ml. o~ the CaC12 ~ -stock solu~ion are pipetted into the ~lask and then 10 ml, Or the MgS04 stock solution are also pipetted into the ; 10 flask, distilled water is then added to bring the volume ; to 1 liter and mixed thoroughly. The final blend should : be clear and free of precipitate.
D. Combustion Chamber Deposit En~ine Test .: . .
1, Engine Tesf, Procedure ,,.
The Combustion Chamber Deposit ~n~ine Test (CCDET) is used to evaluate the abilityof a gasoline additive, or mixture of additives to control or reduce the , . . .
octane number requirement increase (ONRI), in an internal co~nbustion engine, the test is run using a 19l2 Chevrolet .. . ~ 20 350 CID v-8 engir.e equipped with a two barrel carburetor and a 1972 Tubo Hydromatic 350 transmission which is conne~ted to a 1014-2 WIG dynamometer equipped with a ; .
200.3 lb-ft lnertia wheel. The following test cycle ~; and operating conditions are employed and are intended ..... .
to ~imulate an urban taxi cab.
.
; ,!, :....... .
.~ . . .
:1: ' ' , ,, : . . .
, . . . . .
0. ~
--\ --10~7251 .~-Test C~cle P~ase I Start - idle, 650-750 rpm PhaLse II Accelerate - 1 to 2 shif~, 5.5 ~ec., 2900-3000 rpm Phase III Accelerate - 2 to 3 shift, 9.5 sec.
~ 2800-2900 rpm ~hase IV 3rd ~ear, 10.0 sec., 2600 rpm ;~
Phase V Decelerate to idle, 15.0 sec.
Test Duration 200 hrs.
~uel 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 requ'rement is determined at 24 hr~.
lnterval under the following engine conditions: transmission ,i'! in 3rd gear with an output shaft speed controlled at 1500 rpm and the engine throttle wide open. The octane nwnber 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 o~ known octane number until audible knock is perceived. The lowest standardized octane n~unber blend at which the en~ine does not knock is recorded as the octane nwnber requirement.
Octane num~er requirement in^rease is tnen the dif~erence bet~een the init~' octane nwn~er requirement and the final octane n~ber requirement ~or a p~rticu'ar test.
." ' ' ' ~ , .
- ~0~7251 - The novel fuel compositions may be prepared by adding the indi~idual additives directly ~o the fuel, or an additive blend or mixture of one or more of thP
components may be prepared or a concentrate o~ one or more o~ the additives in a su~table solvent such as toluene or xyiene may be prepared. Also, all o~ 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 typ~cal mixed pol~Jester employed in the fuel of the invention is as follows:
PREPARATION OF TRI~R ACID, DIISOD~CYL, MONO-OCTYLPHENOXYPOLYETHOXYEIHANOL (3 MOLE~ ETH~I.E~ OXIDE) i TRIEST~R
; 15 To a 3-1 three-necked round bottom flas'~
ritted with a mechanical stirrer, thermometer, and Dean-Stark trap with reflux condenser are c~arged 845 g.
. (1 mole~ of a trimer acid mixture (E~e~ Industries 1834-18R trimer acid,) comprising 70-80~ trimer acid and 30 to 20% dimer acid, 316 g. (2 moles) o~ isodecyl alcohol, 338 g. (1 mole) of octylphenoxypolyethoxyethanol containing about 3 moles of condensed ethylene oxide, 200 ml of toluene, and 1.0 gO Or p-toluenesulfonic acid.
The reaction mixture is heated toreflux (w~th stirring) which occurs near 135C. Refluxing is continued ~or 6 ., . ' .
.'' ' . ' .
.: c ~, ' ;
.
... . .. . . . .
~047251 hours durin~ which time the theoretical quantity of ~at;er is evolved. Toluene solvent is stripped under vacuum, 3.0 g. of Na2C03 aQded to neutralize the p-toluenesulfonic acid, and the product filtered. The material prepared in this.way generally has an acid near 1.0 The theoretical product distribution assuming that eqvilibrium has been obtalned and that there are no free energy formation differences between the various esters is the followin~:
wt % mole %
trim~r acid, triisodecyl triester 25.9 29.6 trimer ac~d, diisodecyl~mono-octylphenoxypolyethoxyethanol ; 15 (3 moles ethylene oxide) 44.5 44.5 trimer acid, isodecyl di-- octylphenoxypolyethoxyethanol (3 moles ethylene oxide) triester 25.0 22.2 ~; 20 trimer acid, ~ri-. ¦ octylphenoxypolyethoxyethanol (3 moles e'hylene oxide) 4.6 3.7 Actual analysis shows the diisodecylmono-octylphenoxypol~ethoxyethanol ester to be present in the preponderant numerical percentage amount, and actual chromatographic analysis conforms substantially :,.
. _ 2L~ -": ., ' , '' . . ' ' ~047251 ~
with the predicted amount. Changes in the ra~lo of the ester components may be obtained, by alterin~ ~he esterification condition~.
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 l dimethyl/mono-octyl- Ester of trimer phenoxy polyethoxy- of linoleic acid.
ethanol containing ~ `
average of 3 moles of -\ condensed ethylene oxide.
Example 2 dibutyl/mono-octyl- Ester of the trimer i~ 15 phenoxy polyethoxy- of linoleic acid.
ethanol with average of 3 moles Or ethylene , oxide.
,~ .
Example 3 di-2-ethylhexyl/mono- Ester of the trimer ; 20 octylphenoxy poly- of linoleic acid.
ethoxyethanol with 3 moles of ethylene ; oxide.
."
Example 4 diisodecyl/mono-oc~yl- Ester of the trimer phenoxy polyethoxy- of linoleic acid.
ethanol with avera~e of 3 moles of ethylene oxide.
.
Example 5 di Cl6_20 aliphatic Ester of the trimer alcohol/ mono- of linoleic acid.
octylphenoxy poly-ethoxyethanol with 3 moles of ethylene oxide.
35 Ex~npie 6 mo~o-isodecyl/di-octyl- Ester of the trimer - phenoxy polyethoxy- Or linoleic acid.
ethanol with 3 moles o~ ethylene oxideO
. - , .
.
,: -., .
.. . . . ~ .
1047ZSl TABLE II (Cont~d) Example 7 diisodecyl/mono-octyl- Ester of the trimer phenoxy polyethoxy- of l~noleic acld.
ethanol with average of 5 moles of ethylene o~ide.
Example 8 dimethyl/mono-oc'yl- Ester of the trimer phenoxy ethoxye~hanol of linoleic acid - with average of 1 mole of ethylene oxide.
E~ample 9 mono-isodecyl/mono-octyl- Ester of t~e dimer of phenoxy polyethoxy linoleic acid.
ethanol wlth 3 moles ethylene oxide.
The esterification reaction is usually acid catalyzed and can be carried out over a broad range o~
, - te~peratures, but usually the temperature wlll vary fro~
about 75C, to about 180C. The mixture Or aliphatic alcohol and ethoxylated aromatic alcohols can also vary fairly ~lidely depending on the products desired, but ordinarily the ratio of the aliphatic alcohol to ,;' the ethoxylated aroma~ic alcohol wlll vary from abou~
~ ,A "
(on a molar basis) one to four to about four to one, and more preferably about one to two to abo~ two to one.
. ~ .
The quantity of mixed alcohols used shoulà be suf~icient to essentially completly es~erify the polycarboxylic acid . ~ , .
(i.e. the trimer or dimer acid,o~ mi*ture thereof) and there can be used an equivalent amount or slight molar-excess of alcohols in relation to the polycarboxylic ; 3 acid during the esterif~cation reaction.
, . . . . .. .
, . ~
, ~
.. . . . . . .
i:.. , ~ , . .
: .
1047ZS~:
The base ruel employed in the following Examples (Tables III, IV, ànd V belo~r) ~s a Howell unleaded gasoline a~s described hereinabove, except for the BBCDT-KC tests wherein an MS-08 gasoline as described hereinabove is used.
s Induction System Deposit Test results (ISDT) are reported in milligrams (mg.) of deposit as are the Blowby Carburetor Deter-gency Keep Clean Engine Test results. Percent rusting is also reported. These test procedures are described above.
TABLE III .
Ex~mple Fuel Additive and ISDT, mg,BBCDT2-~C
Concentration ppmdeposit mg. deposit Gasoline (Valve and , . port Control Untre2ted Gasloline 365 .13 triisodecyl ester CxaPpale A of trimer of linoleic 170 acid, 300 ppm ` mixed dimethy poly-. 20 No. 10 ester of Example 172 (see Table II), 300 ppm mixed dibutyl poly-No. 11 ester Or Example 235 18.1 .: (Table II above) . 3 ppm -. - mixed diisodecyl No. 12 polyester of 37 14.2 Example 4 (Table II aboue) 300 ppm .; ' .
3 mixed diisodecyl polyester of Exa~ple No. 1~ 7 (Table II above) 475 3O ppm .. trl-octylpolyeth-: 35 oxyethanol ester Or . Mo, 14 trimer of linoleic 186 acid with 3 moles eth~lene oxide, 500 ppm ,.
. - ~ I
; ; - 27 -, 1047~51 .
TABLE III (Cont~d) Example Fuel Addi~ive and ISDTl mg. ~BCDT2-~C ~-Concentration ppm deposit mg. deposit Gasoline (Valve and . port) .
Comparative commercially avail-Example B able and used a].kyl435 4 0 ~ .ammonium phosphate, 50 ppm Comparative co~nercially avail-Example C able and used poly- 1247 3.3 ; butene succinimide, ~; 140 pp~
... . ..
(1) Induction System D.eposit Test, as , 15 described above.
(2) Blowby Carburetor Detergency Keep Clean Engine Test, as described above.
In Table IV, below, there are shown results .
obtained with a combination or mixture Or additives ~ .
;,! 20 according to the present invention.
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TABLE IV (Conttd) . 1 WHERE
Zl is the hydrocarbon residue of the product of trimerization . of an unsaturated C18 fatty ac~d, such as linoleic acid, 5whlch ~s~a mixture of about 70-80~ trimer acid (C54) and` .
and about 30-20,q~ of dimer aoid (C36), all parts by W-igbt.
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; TABLE V
(Octane Number Requirement Increase~
Ex2mple Fuel Additive and Octane N~.ber*
Concentration, ppm, Requirement in Gasoline Increase Control Untreated gasoline, i.e. 10 . ~ base fuel Commercially available ComparatiVe and used polybutene 8 Examp e D succininide, 140 ppm Same additive package or No. 22 blends as in Example No.
15 (Table IV) (total = 370 ppm) Same additive as Example No. 23 No. 2, Table ~I at 5 : 300 ppm * As measured b~J the Combustion Chamber Deposit Engine Test.
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. 104q'2Sl As is evident from the date in Table III, the mixed polyesters of this invention ~Yhile individuall~-aflording no carburetor detergency activity, per se, are very effective at controlling induction system deposits in an internal combustion engine.
~Jhen the mixed polyesters are used i~ combination with rust inhibitors and carburetor ~etergents as shown in Table IV so that a multipurpose additive package is formed, the activlty of e~amples 15, 16, and l9 is significantly better than the base fuel in all three performance categories, ; i.e., rust inhibitor, carburetor detergency, and induction sys~em detergency. hlt}lough examples 17, 18, 20, 21, and 22 sho~J higher levels of induction system deposits than the base fuel their total performance is significantly better than the base fuei treated with currently used commercial additives such as the alkyl ammonium phosphates and ~he polybutene succinimides. It is important to remember that untreated gasoline is rarely used in present day l automobiles and that gasoline treated with conventional : 20 carburetor detergents and rust inhibitors ~ill normally s~ .
give higher levels of induction system deposits than the base gasoline as is shown in Comparative Examples B and . ~ .
C of Table III.
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~0~72Sl Although the mechanlsm o~ ~ctivity is not clear, i~ is evident ~rom the data in Table V that the additive combination of our invention is effective in modifying the deposits in the combustion chamber such that the octane number requirement increase Or the engine is less than ; with either untreated gasoline or base gasoline treated with a commercially used polybutene succinimlde, ; In a specific example of an alternative embodiment o~ this invention, wherein the carburetor detergent (1) and induction system deposit control additive (3) are used (with-out any added rust inhibitor) in gasoline, at a total con-.
cen~ration of about 350 ppm, (50 ppm of 1 and 300 ppm Or 3), the follo~ring results are obtained: for the ISDT Test, 201 milligr~ns (m~,) of deposits; and for the BBCDT-KC Test, 1.3 mg. of deposits. In this test, component (1) was a t-Clg-C22 alkyl amine such as was used in Example 15, and component (3) was the mixed polyester of Example 4. As noted previously, a Howell unleaded gasoline is used ror the ISDT tests, and MS-o8 gasoline is used ~or the BBCDT-KC tests.
' In another alternative embodiment of this invention, other dicarboxylic acid esters, such as an adipa~e diester ` may be substituted in whole or part ~or component (3) o~
the detergent composition, noted above, to provide induction ` systems deposit control. Thus, an adipate diester compris ng 1 25 the mono-isodecyl, mono-octyl pheno~ polyetho~ eth~nol ~ (containin~ an average of 3 moles o~ condensc-d ethylene : - 34 - .
- - t , . . .
.
. . . .
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/al~yl phenoxy (alkyl of C4 to Cg~ polyethoxy ethanol tcontaining 1 to 20 moles, and ~o~e preferably about 1 to 5 moles condensed ethylene oxide) ester may also be used to provide induction system deposit control either alone, or in combination 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 oombination with components (l)* and (2)*, noted above.
Other results using 300 ppm of the specific monoisdecyl, mono-octyl phenoxy polyethoxy ethanol (3 moles ethylene oxide) adipic ester noted above in combination with 50 ppm of the t-C18-C22 alkyl amine (component (1~ above) are as follows:
in the ISDT te~t, 225 ~g.iof deposit, and~in the BBCDT-KC test, i 2.3 mg~ of deposit. Wh~n 10 ppm of the rust inhibitor component - ~2) of Example No. 15 is added to the mixture 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 ~e~, 327 mg. of deposit, 2.2 mg. of deposit in the s BBCDT-KC test, and 0% area rusted in the rust 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.
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In another example using 50 ppm of the t-Clg-C22 alkyl amine (component (1) above~, 5 ppm of the rust inhibitor component (2) of Example ~rO. 15, and 300 ppm of the mono- -i~odecyl, mono-octyl phenoxy polyethox~Jethanol (containing 5 moles o~ ethylene oxide~ adipate ester the follo~Jing results ~ere obtained: in the ISDT test, 237 mg. of deposit, in the BBCDT-KC test, 305 mg. of deposit, and 0% area rusted ~ in the rust test.
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Claims (9)
1. A multi-functional additive composition suitable for addition to distillate hydrocarbon fuels having a major proportion of a hydrocarbon base fuel distilling within the gasoline distillation range, the additive composition com-prising 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 650 parts by weight of an adipic acid ester comprising a Cl-C20 alkyl/alkyl phenoxy (alkyl of C4 to C9) polyethoxyethanol (containing 1 to 20 moles of ethylene oxide) ester of adipic acid.
2. A multi-functional additive composition accord-ing to claim 1, suitable for addition to gasoline, said additive composition comprising a mixture of (1) and (2), and wherein (2) is the mono-isodecyl, mono-octyl phenoxy poly-ethoxyethanol (containing 3 moles of ethylene oxide) ester of adipic acid.
3. An improved detergent motor fuel composition comprising (a) a major amount of a hydrocarbon base fuel boiling in the gasoline boiling or distillation range; and (b) about 100 to about 650 ppm of the mono-isodecyl, mono-octyl phenoxy polyethoxyethanol (containing about 3 moles of ethylene oxide) ester of adipic acid.
4. Composition according to claim 1, wherein (2) is the mono-isodecyl mono-octyl phenoxy polyethoxyethanol (containing about 5 moles of ethylene oxide) ester of adipic acid.
5. A multi-functional additive composition suitable for addition to distillate hydrocarbon fuels having a major proportion of a hydrocarbon base fuel distilling within the gasoline distillation range, the additive composition compris-ing 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 100 parts by weight of a surface active alkyl ammonium carboxylate salt-ethoxylated alkyl phenol ester of trimer or dimer acid;
(3) about 100 to 650 parts by weight of a diester prepared from the reaction of adipic acid and a mixture of an aliphatic alcohol having from about 1 to 24 carbon atoms and an alkoxylated alkyl phenol.
(2) about 5 to 100 parts by weight of a surface active alkyl ammonium carboxylate salt-ethoxylated alkyl phenol ester of trimer or dimer acid;
(3) about 100 to 650 parts by weight of a diester prepared from the reaction of adipic acid and a mixture of an aliphatic alcohol having from about 1 to 24 carbon atoms and an alkoxylated alkyl phenol.
6. A composition according to claim 5, wherein (3) is the mono-isodecyl, mono-octyl phenoxy polyethoxy ethanol (with an average of 3 moles of ethylene oxide) adipate.
7. A composition according to claim 5, wherein (3) is the mono-isodecyl, mono-octyl phenoxyethanol (with an average of 5 moles of ethylene oxide) adipate.
8. A composition according to claim 5, wherein (1) is a tertiary alkyl primary amine having a carbon atom content of about 18 to 22 carbon atoms, (2) is the mono-octyl phenoxy polyethoxy ethanol (containing about 3 moles of ethylene oxide) ester di ammonium carboxylate salt (tertiary alkyl primary amine having a carbon atom content of about 18 to 22 carbon atoms) of the trimer of linoleic acid, and wherein (3) is the mono-isodecyl, mono-octyl phenoxy poly-ethoxy ethanol (with an average of 3 moles of ethylene oxide) adipate.
9. A composition according to claim 5, wherein (1) is a tertiary alkyl primary amine having a carbon atom content of about 18 to 22 carbon atoms, (2) is the mono-octyl phenoxy polyethoxy ethanol (containing about 3 moles of ethylene oxide) ester di ammonium carboxylate salt (tertiary alkyl primary amine having a carbon atom content of about 18 to 22 carbon atoms) of the trimer of linoleic acid, and wherein (3) is the mono-isodecyl, mono-octyl phenoxyethanol (with an average of 5 moles of ethylene oxide) adipate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US00356655A US3846089A (en) | 1972-08-11 | 1973-05-02 | Motor fuel composition |
| CA196,530A CA1039302A (en) | 1973-05-02 | 1974-04-01 | Motor fuel composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1047251A true CA1047251A (en) | 1979-01-30 |
Family
ID=25667528
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA292,116A Expired CA1047251A (en) | 1973-05-02 | 1977-12-01 | Motor fuel composition |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1047251A (en) |
-
1977
- 1977-12-01 CA CA292,116A patent/CA1047251A/en not_active Expired
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