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~l~~r~~t~
Case EP-6800-A
- 2 -
Also, a specified type of lubricating oil fraction may be
included in the additive mixture. The polyoxyalkylene
glycol derivatives referred to in the text of the patent
include the ethers, esters and ether aminoacid esters of the
polyoxyalkylene glycol.
Canadian patent application 2,089,833 bearing a publi-
aation date of August 21 , 1993 describes a similar additive
system. In particular, the gasoline is to contain (a) from
75 to 450 ppmw of ,a specified group of Mannich base deter-
gents in combination with (b) from 75 to 175 ppmw of an oil-
soluble'poly(oxyalkylene) alcohol, glycol or polyol or mono
or di ether thereof, wherein the weight ratio of (a) to (b)
in the mixture is at least 0.43.
THE INVENTION
It has now been discovered that oil-soluble poly(oxy-
a~kyl,ene) alcohols, glycols or polyols or mono or di ethers
thereof do not yield equivalent results on intake valve
cleanliness when used in conjunction with a Mannich base
detergent; and that-for reasons not presently understood,
the viscosity properties of the poly(oxyalkylene) component
appear to have a profound effect on the intake valve clean-
liness performance of the overall.composition.
Accordingly, in one of'its embodiments; this invention
provides, a fuel-soluble additive composition which com
prises
a) a'Mannich reaction'product of (i) a high molecular
weight alkyl-substituted phenol, (ii) amine; and (iii)
aldehyde: and
~b) ~a-po7.y(o~yalkylene} compound shaving 'in its undiluted
state a viscosity of at least about 70 centistokes
(cSt) at 40°C and at least about 13 cSt at 100°C.
preferably, he.composition-will contain one or more liquid
hydrocarbons which, whether a single hydrocarbon or a mix-
ture of different hydrocarbons, has a viscosity that is not
substantially in excess of the viscosity of the paly(oxyal-
kylene) compaund.
Case EP-6800-A
- 3 -
In another of its embodiments, this invention provides
a fuel composition which comprises gasoline containing a
minor intake valve deposit controlling amount of
a) a Mannich reaction product of (i} a high molecular
weight alkyl-substituted phenol, (ii) amine, and (iii)
aldehyde: and
b} a poly(~xyalkylene) compound having in its undiluted
state a viscosity of at least about ?0 centistokes
(cSt} at 40°C and at least about 13 cSt at 100°C.
1~ Typically the :proportions of a} to b} in the composi-
tions of this invmtion are such that there are from about
0.2 to about 5' parts by weight of a) peg part by weight of
b),~preferably from about 0.5 to about 3 parts by weight of
a) per part by'weight of b), and mare preferably from about
0.8 to about 2 parts by Freight of a} per part by weight of
b}, with the weight of a) being on an °'active ingredient
basis~~. ' By this is meant that component a} will usually be
supplied in admixture on'a weight basis with a minor amount
of a hydrocarbon diluent and a minor amount of unreacted
polyolefin used in making the alkylated phenol from which
the Mannish detergent is produced. Thus the foregoing
proportions of,a) to b),are based on the content of Mannish
base detergent iri component a) excluding the weight of any,
diluent or-solvent and any unreac~~d polyolefin which may be
associated therewith in 'the form in rahich it is supplied.
Component b} wily: normally be supplied in undiluted form,
and. iW such.case .its. weight can be used directly in calcu-
lating tho ratio of a) to b}. But if the poly(oxyalkyIene)
vocampound is,boing' blended with a} when the' poly(oityal,kylenej
30. compound is in admixture with a solvent or diluent, the
weight of b} should be. based on the weight of the poly(oxy-
alkylene) compound 'itself and should likewise exclude the
weight of any such solvent or diluent associated therewith.
It will be understcaod that any such ancillary solvent
or diluent, whether hydrocarbon or otherwise; must not
adversely affect the intake valve deposit control porfor
Case EP-6800-A
- 4 -
manes of the above additive composition in any material way.
Thus as long as they do not exert such: adverse effect,
ethers, esters or other inert solvents o~ diluents may be
present in the additive composition. Preferably, however,
the only ancillary diluents or solvents in the additive
composition are hydrocarbons which collectively have visco-
shies at 40°C and 100°C that are not substantially in
excess of the viscosity of the poly(oxyalkylene} compound.
For example, these collective hydrocarbon viscosities are
preferably not more than approximately 25 percent higher
than the corresponding 40°C and 100°C viscosities of the
poly(oxyaTkylene) compound being used. Not only does th~.s
ensure: that the intake valve deposit control effectiveness
of.the composition will not'be adversely affected in any
material way, but it keeps the cost of the additive composi-
Lion to a minimum.
In another embodiment, this invention provides a method
:for reducing intake valve deposits in gasoline engines. The
method comprises fueling said engines with a fuel composi-
tion comprising (a) a major amount of hydrocarbonaceous fuel
in the gasoline boiling range and-(b) a minor intake valve
deposit controlling amount of
.a) a Manniah reaction product of (i) a high molecular
weight alkyl-substituted phenol, (ii} amine, and (iii)
aldehyde; and
b} a poly(oxyalkylene) compound having in its undiluted
state a viscosity of at least about 70 centistokes
(cSt) at 40°C and at least about 13 cSt at'100°C.
,, ~ i , ; ,
As noted'above, the Mannish reaction product component
of this invention typically contains a significant portion
of hydrocarbonaceous ingredients which are inactive in the
sense that they do not possess polarity or surface'activity
and therefore do not serve as detergents. For example, sub-
sequent to the manufacture of the Mannish reaction product;
hydrocarbon solvent is typically added to dilute the product
to facilitate handling and blending. Thus, the ,Mannish
'"1 Case EP-6800-A
- 5 -
product as received typically contains about 40 to about 55
wt.~ of the active Mannich base ingredient, the balance
being solvent or diluent, and unreacted materials from the
synthesis steps, such as polyolefin polymer. A generally
used dilution solvent is a mixture of aromatic hydrocarbons
such as o-, p-, and m-xylene, mesitylene, and higher boiling
aromatics such as Aromatic 150 (commercially available from
~h~mtech).
The Mannich reaction products of this invention are
~,0 obtained by condensing an alkyl-substituted hydroxyaromatic
compound whose alkyl-substituent has a number average mol~
cula~ weight'of from about 600 to about 14,000, preferably
alkylphenol whose alkyl substituent is derived from 1-~mono
olefin polymer'having a number average molecular weight~'of
'from about 600'to about 3000, preferably about'750 to. about
1200, more preferably about 800 to about 1200, and most pre-
ferabZy about 800 to about 950; an amine having-at least one
r>NH group, preferably an alkylene polyamine of the formula
HzN - (A - NIi -)xH
where A is a divalent alkylene radical having 2 to 10 carbon
atoms and x is an integer from 1. to 10; and an aldehyde,
preferably formaldehyde or a formaldehyde precursor, in the
presence of a solvent.
commercial grades of alkylene polyamines often contain
mixtures of linear, branched and cyclic species:
High molecular weight Mannieh reaction products useful
as additives in the fuel additive compositions of this in
., ,v~ntion are preferably ;prepared according' to conventional
methods employed for the preparation of Mannish condensation
products, using the'abo~e-named reactants in the respective
'molar ratios of (i) high'molecular weight alkyl-substituted
hydroxyaromatic compound, (ii') amine, and (iii) aldehyde of
ap~aroximately l.0 0.1-10 i-10. Usually the reactants
are charged in proportions such that there are an excess of
the aldehyde and an excess o~ a polyamine relative to he
hydroxyaromatic compound such as an alkylphenol which
f"°:: Case EP-6800-A ~s c r ,. ..
~~.~3 l ~~i
thereby becomes the limiting reactant: For example it is
common to charge about l to 3 moles of polyamine and about
1:2 to 4 moles of aldehyde per mole of (i). A suitable
condensation procedure involves adding at a temperature of
from room temperature to about 95°C, the formaldehyde rea-
gent (e. g:, Formalin) to a mixture of amine and alkyl-sub-
stituted hydroxyaromatic compounds alone or in an easily
remoued organic salvent, such as benzene, xylene, or toluene
or in solvent-refined neutral oil and then heating'the re-
action mixture at an elevated temperature (120°-175'°C) while
preferably blowing with an inert stripping gas, such as ni-
trogen, carbon dioxide, etc., until dehydration is complete.
The reaction product so obtained is finished by filtration
and dilution with solvent as desired:
Preferred Mannich reaction product additives employed
in his -invention are derived from high molecular weight
Manni.ch condensation products, formed by reacting an alkyl- ~ .
phenol, an ethylene polyamine, and a formaldehyde affording
reactants in the respective molar ratio of 1.0': 0:5-2:0
'1.0-3.0, wherein the alkyl group of the alkylphenol has a
number average molecular weight (Mn) of from about 600 to a-
bout':3,000, and more preferably .from' about 750 to about
1,208.
Representative of the high molecular weight alkyl
substituted hydroxyaromatic compounds are- polypropylphenol
(formed by alkylating,phenol with;polypropylene); polybutyl
phenol (formed by alkyLating phenol with polybutenes or
poly isobut~rlefie) , mind other similar.long-chain al~kylpheriols.
polypropylphenol is the most; preferred reactant. Polyalkyl
phenols may be obtained by the a~kylation, in the presence
of an alkylating oatalyst such as BF3,: of phenol with high
molecular weight polypropylene, polybutyl.ene and other poly-
alkylene compounds o give alkyl substituents on the benzene
ring of phenol'having.a number average'molecular weight '(Mn)
'of from about 600 to about 14,000.
Case EP-6800-A
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The alkyl substituents on the hydroxyaromatic compounds
may be derived from high molecular weight polypropylenes,
polybutenes, and other polymers of mono-olefins, principally
1-mono-olefins. Also useful are copolymers of mono-olefins
with monomers copolymerizable therewith wherein the copoly-
mer molecule contains at least 90% by weight, of ~ano-olefin
units. Specific examples are copolymers of butanes (butene-
1, butane-2, and isobutylene) with monomers copolymerizable
therewith wherein the copolymer molecule contains at least
90% by weight of propylene and butane units, respectively.
The'monomers copolymerizable with propylene or butanes in-
clude mon~mers containing a small proportion of unreactive
polar groups such as chloro, bromo, keto, ether, aldehyde,
which do appreciably lower the oil-solubility of the.poly-
mar: The comonomers polymerized with propylene or such bu-
tenes may be aliphatic and can also contain non-aliphatic
groups, e:g:, styrene, methylstyrene, p-dimethylstyrene,
divinyl benzene and the like: from the foregoing limitation
placid on the monomer copolymerized with propylene or the
butanes, it is clear that the resulting polymers and copoly-
mers are substantially aliphatic hydrocarbon polymers:
Thus; the resu7aing alkylated phenols, contain substantially
alkyl hydrocarbon substituents having a number average
molecular weight (Mn) of from about 600 to about 14,000.
Tn addition to the foregoing high molecular weight hy-
droxyaromatic compounds, other phenolic compounds which may
be used include, high molecular weight alkyl-substituted
derivatives of resorcinol; hydroquinone, cresol, catechol,
xylenol, hydroxydi-phenyl, benzylphenol,~ phenethylphenol,
naphthol, to3ylnaphthal, among others. Preferred for the
preparation of such preferred Mannich condensation products
aye the polyaTkylphenol reactants, e.g., polypropylphenol
and polybutylphenol whose alkyl, group has a number average
molecular weight of 600-3000, the more preferred alkyl
groups having a number average molecular weight of 740-1200,
while the most preferred type of alkyl groups is a poly-
Case EP°6800-A
8
propyl group having a number average molecular weight of
about 900950.
The preferred configuration of the alkyl-substituted
hydroxyaromatic compound is that of a para-substituted mono-
alkylphenol. However, any alkylphenol readily reactive in
the Mannich condensation reaction may be employed: Thus,
Mannich products made from alkylphenols having only one ring
alkyl substituent, or two ring alkyl substituents are suit-
able for use in this invention:
1Q ' Representative amine reactants are alkylene polyamines,
principally polyethylene polyamines. Other representative
organic compounds containing at least one FiN< group, suitable
for use in the~preparation of the Mannish reaction'products
are well known and include he mono and 'di-amino alkaries and
theix substituted analogs, e.g., ethylamine, dimethylamine,
dimethylaminopropyl amine, and diethanol amine; aromatic di
amines, e:g., phenylene diamine, diamino naphthalenes; het
erocyclic amines, e.g., morgholine, pyrrole, pyrrolidine,
imidazole; imidazolidine, and piperidine; melamine and their
substituted analogs.
The'alkylene polyamine reactants which are useful with
this.:invention include polyamines whicli~are linear, branched
or cyclic; or a.mixture of ;linear, branched and~or cyclic
polyamines wherein each alkylene group contains from about
1 to.about 10 carbon atoms: A-preferred polyamine is a
polyamine containing from 2 to 10 nitrogen atoms per mole-
,c~lfe, or a ~ mixture off." polyamines containing' an; average -; ~of
from about 2 to about 10 nitrogen atoms per molecule such as
ethylenediamine, diethylene triamine, triethylene tetramine,
tetraethylene pentamine, pentaethylene hexaminehexaethyl-
ene heptamine, heptaethylene octamine, octaethylene nona-
mine, nonaethylene; decamine, and' mixtures of such amines.
Corresponding propylene: polyamines such as propylene di-
amine, and dipropylene triamine; tripxopylen,e tetramine,
tetrapropylene pentamine, pentapropylene hex~mine are also
Case EP-6800-A
_ g -
suitable reactants. A particularly preferred polyamine is
a polyamine or mixture of polyamines having from about 3 to
7 nitrogen atoms with diethylene triamine or a combination
or mixture of ethylene polyamines whose physical and chemi-
cal properties approximate that of diethylene triamine being
the most preferred. In selecting an appropriate polyamine,
consideration should be given to the compatibility of the
resulting detergent/dispersant with the gasoline fuel mix-
ture with which it is mixed:
Ordinarily the most highly preferred polyamine, dieth-
ylene triamine, will comprise a commercially available mix-
ture having the general overall physical and/or chemical
composition approximating 'that of pure diethylene triamine
but which can .contain minor amounts of branched-chain and
cyclic species as well as some other linear polyethylene
polyamines such as triethylene tetramine and tetraethylene
pentamine. For best, results, such mixtures should contain
at least 50~ and preferably at least 70% by weight of the
:linear polyethylene polyamines of which at Least-50 mole o
'is diethylene triamine.
The alkylene polyamines, are usually obtained bg the
reaatioz~ of ammonia and di:haloalkanes, such as dichloro-
alkanes. Thus, the alkylene polyamines are obtained from-
the reaction of 2 to lL moles., of ammonia with 1 to 10 moles
of dichloroaTkanes having 2 to 6 carbon atoms and chlorine
atoms on different'carbon atoms:
Representative aldehydes for use in the,preparat~ion-of
i
high molecular weight Mannich products include the aliphatic
aldehydes uch as formaldehyde, acetaldehyde, propionalde-
hyde, butyraldehyde, valeraldehyde, caproaldehyde, heptal-
dehyde, stearaldehyde. Aromatic aldehydes which may be used
include benzaldehyde and salicylaldehyde: illustrative het-
erocyclic aldehydes for use -herein are furfural and thio-
phene aldehyde; etc': AIso useful are formaldehyde-producing
reagents such as paraformaldehyde, or aqueous formaldehyde
CdSe EP-6800-A
- 10
solutions such as formalin. Most preferred is formaldehyde
or formalin.
hnportant considerations insofar as the present inven
tion is concerned, are to insure that the alkylphenol having
an alkyl substituent with the desired number average molecu
lar weight be reacted with the preferred polyethylene poly-
amine and aldehyde comgounds and that the reactants be em-
ployed in.proportiorrs such that the resultant Mannich reac-
tion product contains the requisite proportions of the chem-
'ically combined reactants, all as specified herein. When
utilizing'this combination of features, he resultant compo
itions of this invention not only possess exceptional
effectiveness in control~.ing;or reducing the amount of in
duction system,deposits formed during engine operation but
which permit adequate demulsification performance.
A key feature. of this invention is that the Mannich
reaction products are used in coiabination with one or more
poly(oxyalkylene) compounds having the requisite viscosity
parameters referred to hereinabove.
The poly(oxyalkylene) compounds suitable for use in the
practice of this invention comprise one or more gasoline-
soluble poly(oxyalkylene) alcohol , glycols or polyols or
mono or diethers thereof, with the proviso that such com-
pounds have in theirvundi:luted state a viscosity of at least
about 70 centistokes,(cSt) at 40°C and'at Least about 13 cSt
at-104°C. Such compounds can be represented by the follow-
i~a formula , i. , y ~,
~~
Rt- ( -R20-) n-.R3 ( I
wherein R~;is a hydrogen atom,-or hydroxy, alkyl,'cycloalkyl,
aryl, alkaryl, aralkyl, alkoxy, cycloalkoxy; or amino group
having in. the range of 1-200 carbon atoms, RZ is an alkylene
group having '2-10 carbon atoms (-preferably 2-5 carbon
atoms}, R3: is a hydrogen atom or alkyl, cycloalkyl, aryl,
alkaryl, aralkyl, or hydrocarbylamino group having 1-200
carbon atoms, and n is an integer in the range from 1 to 500
CA 02133796 2004-09-15
- 1 1 -
(and preferably in the range of from 3 to 120) representing
the number of repeating alkyleneoxy groups, all with the
proviso that the product in its undiluted state is a gaso-
line-soluble liquid having a viscosity of at least about 70
centistokes (cSt)- at 40°C and at least about 13 cSt at
100°C.
Generally speaking, the poly(oxyalkylene) compounds
used in the practice of this invention will have viscosities
of no more than about 400 cSt at 40°C and no more than about
50 cSt at 100°C. Preferably, the viscosities of the poly
(oxyalkylene) compounds used will not exceed about 300 cSt
at 40 ° C and about 40 cst at 100 ° C. The most preferred poly
(oxyalkylene) compounds will have viscosities of no more
than about 200 cSt at 40°C, and no more than about 30 cSt at
100°C.
Preferred poly(oxyalkylene) compounds are poly(oxyal-
kylene) glycol compounds and monoether derivatives thereof
that satisfy the above viscosity requirements and that are
comprised of repeating units formed by reacting an alcohol
or polyalcohol with an alkylene oxide, such as propylene
oxide and/or butylene oxide with or without use of ethylene
oxide, and especially products in which at least 80 mole %
of the oxyalkylene groups in the molecule are derived from
1,2-propylene oxide. Details concerning preparation of such
poly(oxyalkylene) compounds are referred to, for example, in
Kirk-Othmer, Encyclopedia of Chemical Technology, Third
Edition, Volume 18, pages 633-645 (Copyright 1982 by John
Wiley & Sons), and in references cited therein. U.S. Patent
Nos. 2,425,755; 2,425,845; 2,448,664; and 2,457,139 also
describe such procedures.
Case EP-6800-A
- 12 -
Preferred poly(oxyalkylene) compounds can be represent-
ed by the formula
R40 (RSC!) p R6 (II)
wherein R4 is a hydrogen atom, or a hydrocarbyl group having
up to l8 carbon atoms, and more preferably an alkyl group
having up to 10-l2 carbon atoms; RS is an alkylene group of
2-5 carbon atoms which thus can be an ethylene group (i.a.,
dimethylene) group, but which preferably is a propylene
(i:e., methyldimethylene) group, or a butylene (i:e., ethyl-
dimethylene), group; R~'is a hydrogen atom, or a hydrocarbyl
group having up to-18 carbon atoms; and more preferably an
alkyl group havr~g up to 10-12 carbon atoms; 'and p is a
integer that yields a product having the viscosity parame-
ters given above.'Commercially available products are.often
15- composed of mixtures in which°the individual species'iof the
mixture,have different numerical values for p, and'thus in
the case of such mixtures the value of p for the' overall
product represents an average value. The alkylene groups R~
can all be the same or they can be different and if differ-
ent, can be arranged either randomly' ar in prearranged
blocks or sequences. Particularly preferred are the poly-
(oxyalkylene) alcohols and glycols in which from 70 to 100%
and especially 80 to 100% of the .alkylene' groups are pro-
pylene groups (methyldimethylene groups) derived from use
'1,2-propylene oxide in the alkoxylation reaction usually
employed in the production. of such ;products. In these
particularly preferred poly(oxyalkylene) alcohols, glycols
and diethers, if less than 100% of the-alkylene groups are
propylene groups, the: remainder are either ethylene or
~ b~ty~.ene~ groins,, ~ or bath, proport~.oned ,to yie~,d a nliqu,id
gasoline-soluble product having the requisite viscosity
properties specified above. Monools derived by, propoxy-
lation of alkanols (R4 in Formula (II) is alkyl;, RS is
methyldimethylene groups, Rb is~a'hydrogen atom, and p 'is a~
defined above) are'most preferred'. Such compoua~ds can also
be thought of as monoethers of poly(oxyalkylene) glycols-.
CA 02133796 2004-09-15
- 13 -
Other poly(oxyalkylene) glycols and ethers which may be
employed can be represented by the formula
RIO- ( -R80- ) q-Rq- ( -ORS o- ) ~-OR> > ( I I I )
wherein R~ and R» can be the same or different and each is
independently a hydrogen atom or a hydrocarbyl group, pre-
ferably an alkyl group of up to 18 carbon atoms, and more
preferably of up to 10-12 carbon atoms; R$ and Rio can be the
same or different and are alkylene groups of 2-5 carbon
atoms each, which thus can be ethylene groups (i.e., dimeth-
ylene groups), but which preferably comprise or consist of
propylene (i.e., methyldimethylene) groups, and/or butylene
(i.e., ethyldimethylene) groups; R9 is an divalent hydrocar-
bylene group derived from the initiator, and thus can be a
group such as a phenylene group or an alkylene group which
is preferably an ethylene (i.e., dimethylene) group, a
propylene (i.e., methyldimethylene) group, or a butylene
(i.e., ethyldimethylene) group, and q and r are independent-
ly integers that yield a product having the viscosity para-
meters given above. Commercially available products are
often composed of mixtures in which the individual species
of the mixture have different numerical values for q and
different numerical values for r, and thus in the case of
such mixtures the values of q and r for the overall product
represent average values. As noted, the alkylene groups can
all be the same or they can be different and if different,
can be arranged either randomly or in blocks or sequences.
The poly(oxyalkylene) compounds used pursuant to this
invention will contain a sufficient number of branched
oxyalkylene units (e. g., methyldimethyleneoxy units and/or
ethyldimethyleneoxy units) to render the poly(oxyalkylene)
compound gasoline soluble.
The most preferred poly(oxyalkylene) glycol derivative
compound useful in the compositions and methods of this
invention is known commercially as EMKAROX AF22 available
from ICI Chemicals & Polymers Ltd. This compound has a pour
point of about -42°C, a density of about 0.980 g/ml at 20°C,
*Trade-mark
Case EP-6800-A
14 -
an open cup flash point of about 230°C, a viscosity of about
90 cSt (typically in the range of about 87 to about 98 cSt)
CA 02133796 2004-09-15
- 15 -
preferably about 10 centistokes at 100°C. The volatility of
the poly-a-olefin is also of significance and may be deter-
mined by the Volatility Determination Method described
below.
To determine the volatility of a substance the follow-
ing Volatility Determination Method is used. The substance,
e.g., a poly-a-olefin (110-135 grams) is placed in a three-
neck, 250 mL round-bottomed flask having a threaded port for
a thermometer. Such a flask is available from Ace Glass
(Catalog No. 6954-72 with 20/40 fittings). Through the
center nozzle of the flask is inserted a stirrer rod having
a Teflon blade, 19 mm wide x 60 mm long (Ace Glass catalog
No.. 8085-07). The substance (e. g., poly-a-olefin) is heated
in an oil bath to 300°C for 1 hour while stirring the sub-
stance in the flask at a rate of 150 rpm. During the heat-
ing and stirring, the free space above the substance in the
flask is swept with 7.5 L/hr of inert gas (e. g., nitrogen,
argon, etc.). The volatility of the substance poly-a-olefin
thus determined is expressed in terms of the weight percent
of material lost based on the total initial weight of mate
rial tested. Utilizing the foregoing procedure, it is
particularly preferred to select poly-a-olefins for use in
the additive formulations of this invention that have a
volatility of less than about 50~, more preferably less than
about 25%.
While not required for the purposes of this invention,
it is preferred that the fuel compositions of this invention
include other conventional additives such as antioxidants,
demulsifiers, corrosion inhibitors, aromatic solvents, etc.
Accordingly, components for use in the formulations of this
invention will now be described.
Antioxidant. Various compounds known for use as oxi-
dation inhibitors can be utilized in the practice of this
invention. These include phenolic antioxidants, amine anti-
oxidants, sulfurized phenolic compounds, and organic phos-
*Trade-mark
<IMG>
/.-.~ Case EP-6800-A ~ r ~ r; s H
~~~~ ~~Jv
- 17
trademark by Emery Chemicals. Another useful type of
corrosion inhibitor for use in the practice of this invert-
tion are the alkenyl succinic acid and alkenyl succinic
anhydride corrosion inhibitors such as, for example, tetra-
;propenylsuccinic acid, tetrapropenylsuccinic anhydride,
tetradecenylsuccinic acid, tetradecenylsuccinic anhydride,
hexadecenylsuccinic acid, hexadecenylsucci:nic anhydride, and
the life. Also useful are the half esters of alkenyl suc- -
citzic acids having 8 to 24 carbon'atoms in the alkenyl group
with alcohols such as the polyglycols. Also useful are the
aminosuccinic acids or derivatives thereof represented by
the formula:
R5 0
R6 C C OR4
R3 C C 0Rt
R2 ~~
wherein each of R2,, R3, RS and R6' is, independently; a hydro
gen atom or a hydrocarbyl group containing 1 to 30 carbon
atoms, and wherein each of Rt and R4 is, independently, a
'hydrogen atom; a hydrocarbyl group containing 1 to 30 carbon
atoms, pr an aryl group containing- from 1 0 30 carbon
'atoms.
,i . ~ , ,;
The groups R~. R2~ R3, R4, R5> and R6 when in the form of
' hydrocarbyl groups; can be, for example, alkyl; cycloalkyl
or aromatic containing groups. Preferably R'; R2, R3, R4 and
RS are hydrogen or the samQ or different straight-chain or
branched-chain hydrocarbon radicals containing 1-20 carbon
atoms. Most preferably, R', RZ, R3, R4, and R5 are hydrogen
<IMG>
'na'. .
Case EP-6800-A
- 19 -
weight) of antioxidant; from 0 to 10 parts by weight (pre-
ferably, from 0.1 to 3 parts by weight) of demulsifier; from
25 to 80 parts by weight (preferably 30 to 75 parts by
weight) of aromatic hydrocarbon solvent (including any dilu-
ant or solvent present in the Mannish .detergent as re-
ceived); and from 0 to 5 parts by weight (preferably, from
0.025 to 1.0 parts by raeight) -of corrosion inhibitor per
each one hundred parts by weight of fuel additive composi-
tion.
7,0, The above additive compositions of this invention are
preferably employed in hydrocarbon mixtures in he gasoline
boiling range or hydrocarbon/oxygenate mixtures, or oxygen-
ates, but are also suitable far use in middle distillate
fuels, notably, diesel fuels and fuels for gas turbine en-
gives. The nature of such fuels is so well known to those
skirled in the art as +_o require no further comment. By
oxygenates is meant alkanols and ethers such 'as methanol,
ethanol, propanal,~nethyl-tart-butyl ether, ethyl=tart-butyl
ether, tart-amyl-methyl; ether and the'like, or combinations
'thereof. It will of'course be understood that the base
fuels may contain other commonly used ingredients such as
'; ,
cold startling aids, dyes, metal deactivators, lubricity
additives, octane improvers, cetane improvers, emission con-
trol additives, antioxidants; metallic combustion imprbvers,
and the-like: Cyclopentadienyl manganese tricarbonyl aom-
pounds such as methylcyclopentadienyl manganese tricarbonyl
are preferred because of their outstanding ability to reduoe
ta~;lpipe emissions such as NOX and smog'forming precursors
<IMG>
Case EP-6800-A
- 21 -
be blended into the fuel individually or in various sub-
combinations. However, it is definitely preferable to blend
all of the components concurrently using an additive con-
centrate of this invention as this takes advantage of the
mutual compatibility afforded by the combination of ingredi-
eats when in the form of an additive-concentrate, and re-
duces the possibility of blending errors.
In order to illustrate the 'advantages of this inven
ion, the following examples are given. In these examples,
7,0 the concentrations of additives are. typically referred to. in
terms of pounds per thousand barrels (ptb). One pound per
'thousand barrels of additive in a gasoline of typical spec-
ifid gravity is generally equivalent to about 3.8 to about
4.0 parts; per million (ppm) on a weight basis. In addition,
'the amount of the Mannich dispersant is given on an "as
received basis~~. Since the Mannich dispersant contained
approximately 40% by weight of; active Mannish Reaction
Product (the balance being hydrocarbon diluent and unreacted
polyolefin), the actualquantityof active Mannish detergent
is approximately 4U% of the values reported in the examples.
' I i ~ ' ' ~ ~ i,~
Examtol a . 1
The'vital importance of the viscosity properties of
component b) in providing the exhaust valve deposit'control
perfarmance achievable by the practice of this invention was
~5 demonstrated bx a series of series of 'engine tests: For
each: run, a 1991 Oldsmabile Cutlass equipped with a General
Case EP-6800-A
Motors 2.3L QUAD 4 engine was operated on an chassis dyna-
mometer far the equivalent of 5,000 miles and the amount of
CA 02133796 2004-09-15
- 23 -
hydrocarbon diluent was 70:35:100. The additive concen-
trates were then blended into separate quantities of the
same base fuel and the resultant fuel compositions were then
evaluated in the above engine test. A control run was also
carried out in which the clear (i.e., unadditized) base fuel
was used in the test.
Six different poly(oxyalkylene) products from different
commercial manufacturers were used in these tests. Two met
the viscosity requirements of this invention, the other four
did not.
The two poly(oxyalkylene) products meeting the viscosi-
ty parameters of this invention were:
A - EMKAROX AF22 (ICI Chemicals & Polymers Ltd.), apparent-
ly a poly(oxypropylene) monool with a molecular weight
of about 1700 with a viscosity typically in the range
of about 87 to about 98 cSt at 40°C and about typically
in the range of about 15 cSt at 100°C. The sample used
had a viscosity of 96 cSt at 40°C and 17 cSt at 100°C.
B - DFA36 (ICI Chemicals & Polymers Ltd.), a proprietary
experimental poly(oxyalkylene) product obtained under
a non-analysis agreement, for which the manufacturer
specified a viscosity of 73 cSt at 40°C and 13.5 cSt at
100°C. other properties given were Appearance, Clear
by Method C&P Appendix 2-1; Water Content, 0.055% by
Method C&P/CO/pm/584; Color (Hazen), 10 by Method
C&P/CO/pm/579; Density, 0.9725 g/mL by Method
C&P/CO/pm/561; Pour Point, -34_°C by Method NFT60105;
and Flash Point, 228°C by Method C&P/CO/pm/578.
*Trade-mark
Case EP-6800-A
24 -
The four poly(oxyalkylene) products not meeting the
viscosity parameters of this invention were:
C - An experimental proprietary poly(oxyalkylene) monool
having a viscosity of 63 cSt at 40°C and 8 cst at
100°C. Properties specified by the manufacturer were
Approximate Molecular Weight, 1000; Mw/Mn, 1.79: OH
Number (meq KOH/g), 86: and Viscosity, 120 cP at 25°C.
D - A commercially available polyoxypropylene glycol butyl
ether'having a viscosity of 57 cSt at 40°C and 11 cSt
~0 at 100°C. Typical properties specified by the manufac
turer were Average Molecular Weight, 1150; Average
Freezing Point,, -40°C; Flash Point (PMCC), >400°F
(>204.r~°C); Refractive Index, 1°446 at 25°C; Specific
Gravity, 0.9888 at 25°C; and Viscosity Index, 177:
E - A proprietary experimental poly(oxyalkylene) product
obtained under a non~analysis agreement, but identified
by the manufacturer to be::an alkylphenol propoxylate.''
Iic has a viscosity of 67 to 70 cSt at 40°C and 10 cSt
at 100°C.
F - A proprietary experimental pol,y(axya2kylene)'product
obtained under a non'-analysis agreement having a vis-
cosity of 44 to 45 cSt at 40°C and 8.4 to 8.6 cSt at
1'p0 ° ~ ~ Other properties' given were Appearance; Clear
by Method C&P Appendix 2-1; Water Content; 0.07% 'by
M~thod C&P/~CO/pm/584Color (Hazen), 15 by Method
G&P/CO/pm/579; Density, 0.9586 g/mL by Method
C&PjCO/pm/561; Paur Point, -39°C by Method NFT60105;
and Flash Point,, 220°C by Method C&P/CO/pm/578:
''~ Case EP-6800-A
- 25 -
The intake valve deposit performance of this series of
tests is summarized in Table 1. The fuels designated A
through F contained the poly(oxyalkylene)'compounds identi-
Pied above as A through F, respectively. Thus fuels A and
B were fuels of this invention whereas Fuels C, D, E and E
were fuels not of this inventi4n: Fuels A through F each
contained component a) at a concentration of 70 pounds per
th.ou~and barrels (equivalent to approximately 0.027 wt~),
the respective,poly(oxyalkylene) compound at a concentration
of 35 pounds per thousand -barrels (ec;uivalent ' to approxi-
mately 0.013 wto), and the aromatic hydrocarbon solvent .
(which in effect became part of: the gasoline) at a concen-
tration of 100 pounds per thousand barrels (equivalent to
aPProximately 0.04 wt%).
I i .' a ' , i ,!,
Case EP-6800-A
- 26 -
Table 1
Fuel 40C Viscosity, 100C Viscosity, Intake
csb cgt Valve De-
posits, mg
A 96 2~ 36.3*
B 73 13.5 ?4.2
C 63 8 221.5
D 5? 11 143.4
E 67- l0 142.6
7 0
F 44-45 8:4-86 105:3
Control -- 128.0
* Average'of
two runs.
In addition,
the total
combustion
chamber
deposits
formed
when
using
fuels
A and
B was
almost
3% less
than
the
total
combustion
chamber
deposits'formed
in the
runs,
using
:fuels
C, p,
E and
F:
Example
2-
Another
group
of tests
was conducted
in a
191,
General
Motors
2:3L
QUAD
4 engine
operated
as described
in Example
2. Once
again
the base
fuel:was
an unadditized
regular
un-
leaded
gasoline,iand
the fuel
detergent
used
was the
reac-
;; ,
:
,
tion product
of (i)
a 900
number
average
mole~ulax
weight
polypropyl-substituted
phenol,
(ii)
formalin,
and (iii)
di--
ethylene
triamine.
In this
group
of tests
some
of the
test
fuels.contained,
in addition-to
the combination
of the
de-
tergent
and a
poly(oxyalkylehe)
compound,
a poly-a-olefin
oligomer
(a lO.cSt
unhydrotreated
poly-a-olefin
of 1-decene,
CA 02133796 2004-09-15
- 27 -
hereinafter referred to as PAO) or an antioxidant (HiTEC°
4733 additive (commercially available from Ethyl Petroleum
Additives, Inc.). HiTEC~ 4733 additive is a mixture of tert-
butyl phenols containing about 10 wt.% 2-tert-butyl phenol,
about 75 wt.% 2,6-di-tert-butyl phenol, about 2 wt.% 2,4-di-
tert-butyl phenol, and about 13 wt.% 2,4,6-tri-tert-butyl
phenol.
The poly(oxyalkylene) compounds used both satisfied the
requirements of this invention, one of them being the poly-
(oxyalkylene) product identified as A in Example 1. The
other product, G, is P1200 (Dow Chemical Company), a com-
mercially available polyoxypropylene glycol having a typical
viscosity of about 90 cSt at 40°C and about 13.5 cSt at
100°C. Typical properties as given by the manufacturer were
Average Molecular Weight, 1200; Average Pour Point, -40°C;
Flash Point (PMCC) , 345°F (174°C) ; Refractive Index,
1.448
at 25°C; Specific Gravity, 1.007 at 25°C; and Viscosity
Index, 161.
Table 2 gives the compositions of additives in the fuel
for each run (where ptb is pounds per thousand barrels) as
well as the average of the intake valve (IVD) and combustion
chamber deposits (CCD) for each cylinder. The combustion
chamber deposits are a combination of the piston top depo-
sits and the cylinder head deposits. Runs 1 and 2 give base
line results for the unadditized fuel, and fuel containing
Mannich detergent and PAO only. Runs 3-8 are of the inven-
tion and illustrate the reduction in deposits that can be
*Trade-mark
Case EP-6800-A
_ 2g _
achieved by additive formulations containing Mannich deter-
gentjdispersant and a poly(oxyalkylene) compound having the
viscosity properties required pursuant to this invention.
Table 2
Run HiTEC~HiTEC~ Prod. Prod. PAO, Avg.
No: X997, 4733,, A, G, ptb dep.,
ptb ptb ptb ptb, mg
;
1 _- 905
2 $~ 4 40 g77
3- g0 __ 4p _ 962
4 80 4 40, _. T36
5 80 20 20 864
6 80 4 40 _ 846
80 20 20 805
8 80 40 -- 746
' Example
3
In 1985,
another Ford
series
of
runs,
a
stationary
2.3~, cylinder,
4 single
spark
plug
engine
was
run
for
200
hours l and
under con-
various
loads
utilizing
Union'oil
fue
taini.ng the transient
additives
indicated
ih
Table
3.
The
, dle
.t,est; consiisted
cy of
2
minutes
at
1,4f0
rpmiand
under'
a
load l8 minutes
of inches at
of
Hg
intake
manifold
vacuum,
5
2,000
rgm
and
a
load
of
22
inches
'of
Hg
intake
manifold
vacuum, 'and Hg intake
3'minutes
at
2,500
rpm
at
10
inches
manifold was
vacuum: main-
The
engine
coolant
temperature
tamed at controlled
about
74C
and
the
combustion
air
was
at grains
a of
temperature
of
32C
and
a
humidity
of
80
Case EP-6800-A
- 29 -
moisture per pound of dry air. The test is primarily an
intake valve deposit test; but measurements of combustion
chamber deposits and octane requirement increase can be
made: In Table 3 octane requirement increase is the dif-
ferenae in pctane requirement of the'engine as measured at
0 and 200 hours. The crankcase oil used in the test runs
was an SAE 5W-30 SG APL-quality oil. New intake valves and
valve stem seals were installed after each test run, and new
exhaust valves were installed every fourth test run. Prior
to and subsequent to each test run, the intake valves,
ports, manifolds, and throttle blade were weighed and/or
rated. Runs 10, 11, and 12, are given for comparative pur-
poses and represent the baseline case of fuel without addi-
tive. Runs 10, 11, 12, and 13 were run with a different lot
of the same fuel;as runs ,14, 15-, 16, and 17. Results of the
tests indicate a sign.ficant reduction in intake valve depo-
sibs (IVDj with surprisingly little change in 0RI or combus-
tion chamber deposits. The poly(o~cyalkylene) compound used
pursuant to the: invention was the same as product A of
Example 1. The fuelin Run 26 contained 4 ptb of sulfurized
2,6-di-tart-butylphenol as antioxidant and the fuel in run
17 had 4 ptb of nonyl phenol sulfide as antioxidant: No
antioxidant, was added to ' the athe~ ~fttels . of ! ~his~ series . ~'
Case EP-6800-A
- 30 -
Table 3
Run HiTEC~ Product PAO IVD CCD ORI
No. 4997 A (ptb) (mg) (mg)
(ptb) (ptb)
1~ __ _o _- 721.0 1587 10
1~; __ 519.8 1668 8
12 _ ~_ 577 1855 8-10
13 90 g5 _ 28.3 2210 11
14 90 4~ - 43.1 1481 10
90 22:5 22:5 41.6 1655 11
10 ~.6 90 45 -- 37.8 1745 .11
1'7 ,90 45 28.0 1740 9
Example 4
This series of runs is similar to the runs of Example
2. Tn this series of runs, a 1985, 2:3L,- 4 cylinder Ford
15 engine containing a single spark plug was run for 112 hours,
operating between a 3-minute "power" cycle (37 HP) at 2,800
rpm and a 1-minute "idle" cycle (0-4 HP) at 2,000 rpm. The
engine coolant temperature was maintained at about 74°C and-
the combustion air was not temperature and humidity can-
trolled: The octane requirement increase is the difference
inn octane requirement as measured ~~at 0 and 112''hours. ' the
crankcase oil used in the test runs was an SAE loW-40 SG
APT-quality oil. New intake valves and valve stem seals
were installed after each test run, and new exhaust valves
were installed every fourth-test run: Prior to grad subse-
quent to each test run; the intake valves; ports; manifolds,
and throttle blade were weighed andjor rated. Table 4
Case EP-6800-A ~ ~, ~ ~ ~ ~1
- 31
illustrates the advantages of fuel additives of this
invention. The poly(oxyalkylene) compound,'used pursuant to
the invention was the same as product A of Example 1. The
fuel in Run 16 contained 4 ptb of sulfurized 2, 6-di-tert-
butylphenol as antioxidant and the fuel in run 17 had 4 ptb
of nonyl phenol sulfide as antioxidant. No antioxidant was
added to the other fuels of this series.
Table 4
Run HiTEC~ Product PAO IVD CCD DRI
A'
No. 499T (ptb). (ptb) (mg) (mgt
(ptb)
18 90 45 19.8 1348 7
19 90 45 - 14.1 1469 8
90 22.5 22.5 22.5 1282 10
2a g0 ,~5 - 29.6 1273 8
15 22 90 45 -- 24.9 11g3 10
Example
5
This to the runs
series of
of runs Example
is similar
4. >In rk plug,4 cylinder
this 2:3
series,
a 1993,
dua3.
spa
L Fdrd 'opera~ting
engine between
was a 3-
run
for
100
hours,
20 minute and 1-minute
"power" a "idle"
cycle
at 2800 ' ,
rpm . ~
I j
, :
.. i
, w
,
. .. .
L,. air .
s ~ was controlled
~ , .. at
~cycl~ a
at 2,000
rpm:
The
combustion
temperature f 80,grains
of 32C of
and moisture
a humidity
o
per pound were
of dry run
air. at
Runs an
23-27 engine
coolant 29
temperature were
of 91C run
and at
Runs
28 and
an engine C. the octane
coolant require-
emperature
of 74
meat octane requirement
increase' as
is the
difference
in
Case EP-6800-A ~ ~ ~ ~ ~ ~ D
- 32 -
measured at 0 and 100 hours. The crankcase oil used in the
test runs was an SAE 5W-30 SG API-quality oil. Prior to and
subseguent to each test run, the intake valves, ports, mani-
folds, and throttle blade were weighed and/or rated. New
spark plugs, intake valves and valve guide seals were in-
stalled every test run. New exhaust valves were installed
every fourth test run. ' Table 5 illustrates the advantages
of fu~l additives of this invention: The fuels in Runs 26
and 27 contained 4 ptb of sulfurized 2,6-di-tert-butylphenol
as antioxidant. No antioxidant was added to the other fuels
of 'this series.
Run HiTEC~ Product A PAO IV~ CCD ORI
No. 4997 (p~b~ (ptb~ (mg} (mq)
tptby
23 ._ 261.0 647 6
24 ~0 45 -- 41.6 961 5
,
g0 22'~ 22.5 29.5 1283 5
26 90 45 - 31.2 1183 6
-
2? 90 22.5 22.5 3T:3 2258 6
20 28 _- 338.0 719 8
29, 90 45 - 29.5 1283 5
Example 6
A group of road tests conducted in a 1991 Pontiac Grand
Prix equipped with a General Motors 2.3L QUAD 4 engine de-
25 monstrated the excellent intake valve cleanliness perfor
mance achievable by, practice of this invention. Tn these
Table 5
Case EP-6800-A ~ ~ ~ ~ ~
- 33 -
tests comparisons were made of the performance of unleaded
regular gasoline fuels of this invention, versus the same
base fuel containing a commercially available proprietary
detergent composition regarded as one of the most effective
detergent additives in use in current gasolines. This
7: b . /" J
Case EP-6800-A
34 -
about 840 miles per day. Before each test was begun, the
intake manifold and cylinder head were cleaned and inspect-
ed, the fuel injectors were checked for proper flow and
spray pattern. Following each cleaning and inspection, tha
Run Mannich Product ProductIVD CCD
A
No. Detergent (pt~} X (mg) (mg)
(ptb} (ptb)
1 80 40 4.7 1622
2 80 40 2p.2 1653
3 80 40 6:2 1498
4* --~ 125 28.4 1770
*
Average
of two
runs.
Example
7
Similar performance
excellent was
exhibited
in
a pair
of standard tests
BMW conducted
engine in
the
same
vehicle
using l, an
the unleaded
same regular
base gasoline.
fue In
,, ~
one : ~.
run ,,
the fuel
fuel of
was this
a invention
wherein
the
'base ptb
fuel of
contained HiTEC~
80 4997
additive
as
coin-
ponent Product
a} and'40 A of
ptb Example
of l as
componen~c
b}. The composition
fuel in
additive the
comparative
fuel
was product
X-at
tYie
125
ptb
concentration
level.
Table
?
'summarizes-
the
results.
5 engine was rebuilt with new intake valves and the crankcase
oil was changed. The results of these tests are summarized
in Tsble 6.
Table 6
Case EP-6800-A
35 -
Table 7
Composition tested IVD, mg, CCD, mg
Fuel of this Invention 1.8 1423.5
Fuel
not
of
this
Invention
230.5
1389.2
As
used
herein
he
term
"fuel
soluble"
means
that
the
additive
under
discussion
has
sufficient-solubility
in
the
particular:
gasoline
fuel
composition
in
which
it
is
being
used
to
dissolve
at
20C
to
the
extent
of
at
least
the
minimum
concentration
required
to
achieve'control
of
intake
valve
deposits,in.an
internal
combustion
engine
operated.
on
the
resulting
fuel..
Preferably,
and
in
almost
all
cases,.
the
additive
should
(and
will)
have
a
substantially
greater
gasoline
solubility
than
this.
However,;the
term
does
not
require
hat
the
additive
be
soluble
in
all
proportions
in
the;
gasoline:
fuel:
composition.
~
~
~~
I
!
a
~
~
?',.
