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2,410,829
Patented Nov. 12, 1946
UNITED STATES .tPATENT OFFICE
2,410,829
STABILIZATION OF GASOLINE AND OF
ADDITION AGENTS THEREFOR
Daniel B. Luten, Jr., Berkeley, Calif., assigno'r to
Shell Development Company, San Francisco,
Calif., a corporation of Delaware
No Drawing. Application January 17, 1944,
Serial No. 518,667
11 ‘Claims. (Cl. 44-69)
.
This invention is based on the ?nding of the
unique and unusual properties of certain ortho,
para or di-alkyl phenols in stabilizing certain
substances commonly employed as motor fuel or
gasoline additives. In particular, it pertains to
the stabilization of aromatic amines and to the
stabilization of hydrocarbon compositions such as
gasoline which contain these amines alone or
in combination with metal antiknock additives
such as tetra alkyl lead, metallic carbonyls, etc.
It is an object of the invention to produce
stabilized aromatic hydrocarbon amines. These
stabilized or inhibited aromatic amines may be
2
,
.
, how difficult it may be to ?nd a substance which
will stabilize such aromatic amines themselves,
both before and after their addition to'gasoline.
For this problem, the broad class of known
gasoline inhibitors has been found ineffective.
Indeed many of them act as pro-oxidants or.
oxidation accelerators for the amino compounds.
Commonly used gasoline stabilizers which were
found to be pro-oxidants‘for aromatic amines in
19 clude: para benzyl amino phenol, alpha-naphthol,
4-tertiary butyl catechol, hydroquinone, pyro
gallol, beta-naphthol, para phenylene diamine
and diphenyl phenylene diamine. Other pro;
oxidant substances include thiophenol, thiodi
dissolved in gasoline or other motor fuel; hence,
it is an object of the invention to provide motor 15 glycollic acid, FeS, sulfanilic acid, salicyclic acid,
fuels containing aromatic amino compounds
brom benzene, dianisidine,-iodine, iron or gal
which fuels are stabilized against oxidation or
vanizeda iron surfaces, sodium nitrite, benzoyl
decomposition. Another purpose is to provide
peroxide, lead peroxide, copper phenyl pro
motor fuels containing tetra alkyl lead and/or
pionate, manganese oleate and stannous chloride.
metallic carbonyl compounds which compounds 20 Gasoline inhibitors which were found to be with
are stabilized by the additives of the present in
out inhibiting e?fect on aromatic amines include:
vention. ,An additional object is to provide im
phenyl - alpha - naphthylamine,
mixtures, ‘of
proved motor fuels such as aviation' gasoline
cresylic acids boiling between about 220° C. and
having high antiknock ratings and improved
240° C., 2,3,5,6-tetra methyl phenol, penta-methyl
oxidation or storage stability. Further objects 25 phenol, 2,3,5-trimethyl " phenol, para, para’
will be apparent from the following description.
dihydroxy diphenyl, guaiacol, durohydroquinone,
Aromatic amino compounds, upon exposure to
thymol, resorcinol, anthraquinone, etc.
air, often exhibit a tendency to change color as
It has now been found, however, that‘ a
their period of contact with oxygen lengthens.
particular ‘group of di-alkyl phenols in which the
This color change is the ?rst noticeable symptom 30 alkyl groups are attached at the 2 and 4 or ortbo
of oxidative decomposition which, since it is ' and para positions, as hereafter more fully de
catalytic in nature, proceeds, if unchecked, at
an accelerated rate until the amino compounds
are entirely altered in composition and useful
ness.
-
scribed, have unique stabilizing properties for
aromatic amino compounds, either when the
amines are alone or when they are dissolved in
35 gasoline. The stabilizing agents of, the present
A particular employment for aromatic amino
invention are dialkyl phenols in which the 4 or
compounds, especially those of low molecular‘
para position and one ortho position (2 or 6) are
weight, is in motor fuels such as gasoline in which
occupiedbya primary, secondary or tertiary alkyl
they exert a bene?cial anti-knock effect. It will
radical. Only one of the alkyl radicals may be
be appreciated, therefore, that if such aromatic 40 tertiary, however, so one may have a di-primary
amines are produced for incorporation in gaso
alkyl, di-secondary alkyl, mono-primary mono
line, it is especially desirable that they be
secondary alkyl, mono-tertiary mono-primary
stabilizedlagainst oxidation, since if such de
alkyl, or mono-tertiary ‘mono-secondary alkyl'
composition sets in either before or after their
phenol.
addition to the base fuel, it will not only decrease 45 The ortho and para alkyl radicals (only one of
their own value as a fuel component but may
which, as just stated, being a tertiary alkyl)
also promote the decomposition of the base fuel,
may conveniently be methyl, ethyl, n-propyl, iso
resulting in gum ‘formation, increased knock '
propyl, n-, iso-,' secondary and tertiary butyl,'
rating, volatility changes etc.
and the various primary, secondary or tertiary
Aromatic amines have also been added to 50 amyl, hexyl, heptyl, octyl, and homologous radi
cracked gasolines in small quantities in order to
cals. In general, radicals containing not more
decrease the gum forming tendencies of the
than about 16 or 20 carbonatoms are preferred,
gasoline. Since such inhibition of the oxidation
those 2,4 di-alkyl phenols containing a total of
of the gasoline is achieved by the preferential
not more than about 12 carbon atoms in all alkyl
' oxidation of the amino inhibitor, it will be realized 55 groups being particularly desirable (i. e. those
2,410,829
4
tion of colored products and oxidation of the
xylidine occur simultaneously on aging, the de
crease of light transmitted through the solution
having a maximum of about 18 carbon atoms
counting the nuclear'carbon atoms). The alkyl
radicals should generally be such as to render the
is an indication of the extent of oxidation. The
are added. Too high a number of carbon atoms b1 following determinations were made at 70° 0.,
one atmosphere of air and employing inhibitor
causes the compounds to be waxy and di?icultly
phenols soluble in the composition to which they
concentrations of 0.2% by weight.
soluble. However, particularly in gasolines of
appreciable aromatic contents, phenols with rela
tively large wax radicals containing up to say 35
lncremc in 10%
or 40 or even more carbon atoms may be suitable, 10
especially if those radicals contain branched
chains.
Time to reach
10% transmission
inhibitor
The ortho or para radicals may also
transmission due
to inhibition,
as percent of
blank
comprise one or more aromatic groups such as
phenyl, tolyl, benzyl, etc., although strictly ali
'
None __________________________ ..
Hours
35
0
butyl-‘i-methyl phenol.
78
120
phatic radicals are generally superior.
15 2~tertiary
2-tertiary butyl-i-cthyl phenol. .
66
89
The above limitations regarding the nature and
2,4-dimetl1yl phenol ___________ _ _
54
54
2-metliyl-4-lertiary butyl phenol.
44
26
placement of the several hydrocarbon radicals on
the phenol are very important. In this connec
tion, it is of interest that 2,4,6-tri tertiary alkyl
It has also been found that combinations of
phenols, for example 2,4,6-tri tertiary butyl 20 the present poly alkyl phenols and aromatic
phenol, have little anti-oxidant value for aro
amines, such as the earlier ‘enumerated monocycle
matic amines-some phenols are worse than no
monocyclic aromatic amines having less than a
inhibitor at all. Thus, some tri alkyl phenols
total of about 7 carbon atoms in all alkyl groups, '
found to be pro-oxidants for aromatic amines are
exhibit an inhibiting or stabilizing e?ect on gaso
2,6-ditertiary butyl-4-methyl or -ethyl phenols, 25 line, which e?ect is greater than the calculated
2,6-dimethyl-4-tertiary butyl pheno, 2,5-dimeth
total of the inhibition produced by each additive
yl-4-tertiary butyl phenol and 2,4-ditertiary
alone. This effect is particularly noticeable in
butyl-5-methyl phenol.
saturate or initially stable gasoline such as avia
The aromatic amines generally added to gaso
line for their antiknock value are usually mono
tion gasoline composed of straight run, cyclopen
30
tane,- aromatics, alkylate, hydroformed fractions
and the like, which initially stable gasoline has
' nuclear monoamines having not more than a.
total of 6 carbon atoms in all alkyl radicals. Par
been rendered unstable by the incorporation of
ticular mention may be made of the following:
tetra alkyl lead.
aniline, N-, mono- and di- methyl or higher
Another tri alkyl phenol, 2,4-dimethyl-6-ter
alkyl anilines (which may alsobe substituted in 35 tiary butyl‘ phenol is a singularly successful in
the nucleus); -mono-, di-, and tri methyl and
higher'nuclearly alkylated anilines (which may.
hibitor of tetra alkyl lead ?uid or of initially
stable gasoline composed of saturate fraction
(such as enumerated above) which gasoline has
been rendered unstable by tetra alkyl lead. This
cumidine, etc., as well as suitable substituted de 40 phenol will also inhibit the oxidation of the pres
rivatives. Mixtures of aromatic amines, as well
ent aromatic amines. Hence when stabilizing
as the individual amines, may be employed and ‘ amine-containing leaded gasoline or aromatic
also be substituted on the N'atom), such as
toluidines, xylidines, cymidine, cumidine, pseudo
poly-amines may also be used. Likewise, aro- '
amines which are later to be incorporated into
matic-rich petroleum fractions may be nitrated
leaded gasoline (in particular into saturated type
and reduced to give mixtures such as described 45 gasoline such as aviation gasoline) it may be ad
vantageous to employ 2,4-dimethyl-6-tertiary
in U. S. Patents 1,844,362 and 2,252,099, which
butyl phenol together with a dialkyl phenol of
the present invention. Thus, for example, the
mixtures may be blended in a motor fuel ac
cording to the present invention.
However, the di-alkyl phenolic inhibitors will
tetra ethyl lead will be stabilized by the 2,4-di
also stabilize mcnonuclear amines having a 50 methyI-G-tertiary butyl phenol while the aromatic
greater number of carbon atoms than indicated
amines will be stabilized by one or more of the
present dialkyl phenols such as 2-tertiary butyl
above, i. e. greater than 6, as well as poly-cyclic
4-methyl phenol, Z-tertiary butyl-4-ethyl phenol,
aromatic hydrocarbon amines, e. g. various naph
2,4-dimethyl phenol, 2-inethyl-4-tertiary butyl
thylamines, alkyl naphthylamines, aryl naph
thylamines, anthracylamines and the like.
55 phenol, etc.
_
It is understood that the inhibitor must be well
Effective total amounts of the poly alkyi phe
distributed throughout the substance to be pro
nolic inhibitors in a gasoline are generally be
tected. Thus, it the amine is a liquid under nor
tween about 0.001% to 0.1% (by weight), a pre
ferred range being from about 0.001% to about
mal conditions, the inhibitor should be in- true
or colloidal solution. If it is a solid, the inhibitor 60 0.01% or 0.1%. The aromatic amines may be em
may be incorporated by ?rst melting the amine,
ployed in about 0.25% to 3% (by volume) in a
gasoline although higher or lower quantities can
distributing the necessary amount of inhibitor as
by dissolving it, and then allowing the mixture to
also be used. The upper limit is usually prescribed
solidify; or else by merely spraying the inhibitor
by maximum boiling range speci?cations of the
or a solution thereof onto the solid amine. In 65 gasolines. Since the amines are relatively high
boiling, they may raise the upper boiling range of
undiluted aromatic amines, the content of the
poly alkyl phenol may range from about 0.01%
the gasoline above permissible limits it used in
to 1% (by weight), preferably about 0.1% to
- 0.5%.
excessive amounts. On the other hand, amounts .
of the amines below the lower limit indicated give,
Quantitative determinations of the effective 70 as a rule, insuilicient improvement in knock rat
ness of inhibitors of the present invention in sta
ing to warrant their use.
bilizing xylidine were made by determining the
light transmission through various xylidine sam
ples for a speci?c wave length 0:550 mu) using
a Coleman spectrophotometer. Since the forma 76
found to be particularly advantaageous. The
combination of aromatic amines and the speci?c
poly alkyl phenols has a synergistic stabilizing
About 1% has been
e?'ect when applied particularly to saturated,
2,410,829
initially stable gasolines rendered unstable by the
quate to stabilize the metallic carbonyl in a gas
addition of metal antiknock compounds, as well
oline.v Particularly when tetra alkyl lead is also
present, a part of'the phenolic inhibitor content
as to unsaturated, initially unstable gasolines
(such as cracked gasolines). with or without metal
anti-knock compounds. Up to about 6 cc. per
gallon of tetra ethyl lead or an‘equivalent amount
of another tetra alkyl lead may normally be added
to gasoline.
, \ .
may be 2,4-dimethyl-6-tertiary butyl phenol.
The invention claimed is:
containing a knock-reducing amount of a mono
'
nuclear aromatic amine in which the total num
ber of carbon atoms in all alkyl radicals is less
Solubilizers for the aromatic amines may also
be present, particularly in gasolines which con
tain but a small amount of aromatic constituents.
v
1. _A composition comprising hydrocarbons
10 than 7 and a stabilizing amount of a 2,4-dialkyl
phenol in which one alkyl substituent is selected
from the group consisting of primary, secondary
weight'alcohols, ethers, ketones (in particular ?ve
81nd tertiary alkyl radicals and the other alkyl
or six carbon atom unsymmetrical ketones) ,_ varo
substituent‘is selected from the group consisting
matics such as benzene, toluene, etc. i
_
15 of primary and secondary alkyl radicals.
Such mutual solvents may be low molecular
1 ‘A further advantage in the use of the combi
nation of aromatic amine and poly alkyl phenol
'
2. A composition _ comprising hydrocarbons
containing a knock-reducing amount of a mono
nuolear aromatic amine in which the total num
ber of carbon atoms in all alkyl radicals is less
is that when the inhibitor e?ectiveness of the
compounds begins to wear off, a sharp break in
the induction period does not occur, but rather 20 than 7 and a stabilizing amount of a 2,4-dialkyl
the formation of deterioration products proceeds
phenol having a maximum of about 18 carbon
slowly and a visible precipitate forms only after
atoms and in which one alkyl. substituent is se
extended aging. This is in marked contrast to
lected from the group consisting of primary, sec
the action of most oxidation inhibitors whose
ondary and tertiary alkyl radicals and the other
e?ectiveness is usually terminated quite sudden
alkyl substituent is selected from the group con-.
ly at the end of their period of stabilization with
sisting of primary and secondary alkyl radicals.
the rapid formation of degradation products in
3. A composititon comprising hydrocarbons
the gasoline and the consequent prompt termina
containing about 0.25% to 3% (by volume) of a
tion of the usefulness of the motor fuel.
'
mononuclear aromatic amine in which'the total
It has also been found that the combination of 30 number of carbon atoms in all alkyl radicals is
the present poly alkyl phenols withv aromatic ‘ less than 7_ and about 0.001% to 0.1% (by weight)
amines shows extraordinary stabilizing power for
of a 2,4-dialkyl phenol in which one alkyl sub
metallic carbonyl compounds contained in gaso
' stituent is selected from the group consisting of
line or other motor fuel.
‘primary, secondary and tertiary alkyl radicals
It is known that numerous metallic carbonyl 35 and the other alkyl substituent is selected from
compounds possess desirable antiknock proper
the group consisting of primary and secondary
ties when incorporated in a hydrocarbon fuel.
alkyl radicals.
However, various di?iculties have beset their par
4. A composititon comprising gasoline hy
ticular utilization, notable among which has been
drocarbons containinga tetra alkyl lead com
their chemical instability and ease of decompo 40 pound, a knock-reducing amount of a mononu
sition on standing, as well as their tendency to
clear aromatic amine in which the total number
catalyze the breakdown of the hydrocarbon fuel,
of carbon atoms in all alkyl radicals is less than
producing such e?ects as gum formation and the
7 and a stabilizing amount of a 2,4-dialkyl phenol V ‘
like.
Although the anti-knock function of me
having a maximum of about 18 carbon atoms and
tallic carbonyls in gasoline may often be per- 45 in which one alkyl substituentis selected from
formed in part by other compounds such as tetra
the group consisting of primary, secondary and
ethyl lead, there are particular applications in
tertiary alkyl radicals and the other alkyl sub
which such other substances are not applicable
stituent is selected from the group consisting, of
as in a “break in” fuel or in a heavily leaded fuel
to which the addition of more tetra alkyl lead 50
would have little effect.
'
5. A composition of matter comprising a mix
ture of gasoline hydrocarbons which has been
rendered potentially unstable by the addition of
tetra alkyl lead, about 0.25% to 3% (by volume)
Metallic carbonylic compounds contemplated
by the present application are, for example, the
various carbonylic compoundsof iron, nickel, co
of a mononuclear aromatic amine in which the
total number of-carbon atoms in all alkyl radicals
is less than 7 and a total of about 0.001% to 0.1%
balt, molybdenum, mercury, etc., as well as their
various applicable‘ derivatives.v Among these may
be mentioned Fe(CO)4, Fe(CO)5, FE4(CO)15NO,
FeNi(CO)9, Ni(CO)4, Co(CO)3NO, M0(CO)s,
Hg(Co(CO)4)2. Compounds which decompose
primary and secondary alkyl radicals.
(by weight) of two phenols, one of which is 2,4
dimethyl-G-tertiary butyl phenol and the other
.
being a 2,4-dialkyl phenol having a maximum of
under engine conditions’ to produce metallic car 60 about 18 carbon atoms and in which one alkyl
bonyls may also be employed, such as complexes
substituent is selected from the group consisting
‘of primary, secondary and tertiary alkyl radicals, of carbonyls with ammonia, amines, alkanol
amines, etc.
and the other alkyl substituent is selected from
In general, an amount of metallic carbonylic
the group consisting of primary and secondary
compound in the range of about 0.25 to _3 'cc./gal 65 alkyl radicals.
'
lon is adequate for a break-in fuel,'although up
6. A composition comprising gasoline hydro
to about 10 cc./gallon may be used. In addition,
carbons containing up to about 6 cc. tetra ethyl
there may be present up to-about 6 cc. of commer
cial tetra alkyl lead per gallon as well as various
lead per gallon of-said composition, about 0.25%
to 3% (by volume) of xylidine and about 0.001%
solutizers such as alcohols, ketones, esters, pyri 70 to 0.1% (by‘weight) of a mixture of 2,4-dimethyl
dine, aromatic constituents such as benzene and
(i-tertiary butyl phenol and 2-tertiary butyl-4
the like.
.
'. methyl phenol.
About 0.001% to 0.1% by weight of the alkyl
7. A composition suitable for addition to'a mix
ated phenol in association with about 0.25% to
ture of gasoline hydrocarbons containing a tetra
3% by volume aromatic amine is generally ade 75 alkyl lead compound, which comprises a xylidine
2,410,829
and a total of about 0.01% to 1% (based on the
xylidine weight) of 2,4-dimethyl-6-tertiary butyl
phenol and a 2,4-dialkyl phenol having a maxi
mum of about 18 carbon atoms and in which one
alkyl substituent is selected from the group con
sisting of primary, secondary and tertiary alkyl ,
radicals and the other allwl substituent is selected
10. A composition consisting essentially of a
mixture of normally stable saturated hydrocar
bon fuels containing a knock-reducing amount of
a mononuclear aromatic amine in which the total
number of carbon atoms in all alkyl radicals is
less than 7 and a stabilizing amount of a 2,4-di
alkyl phenol in which one alkyl substituent is
selected from the group consisting of primary,
secondary and tertiary alkyl radicals and the
8. A composition comprising gasoline hydro 10 other alkyl substituent is selected from the group
from the group consisting of primary and second
ary alkyl radicals.
carbons containing a metal carbonyl, stabilized
by an aromatic amine and by a 2,4-dialkyl phenol
in which one alkyl substituent is selected from
gzoanliisting of primary and secondary alkyl rad
C
.
.
’
11. A composition consisting essentially of a
mixture of normally stable saturated hydrocar
the group consisting of primary, secondary and
bon
fuels containing an amount ‘of tetra alkyl
15
tertiary alkyl radicals and the other alkyl sub
stituent is selected from the group consisting of
primary and secondary alkyl radicals.
9. A composition comprising gasoline hydro
carbons containing iron carbonyl and tetra alkyl
lead su?icient to render it relatively unstable on
storage, about 0.25% to 3% (by volume) of a
mononuclear aromatic amine in which the total
number of carbon atoms in all alkyl radicals is
lead which composition is stabilized by a mono 20 less than 7 and a total of about 0.001% to 0.1%
(by weight) of two phenols, one of which is 2,4
nuclear aromatic amine in which the total num
dimethyl-G-tertiary
butyl phenol and the other
'ber of carbon atoms in all alkyl radicals is less
‘ being a 2,4-dialkyl phenol having a maximum of
than 7, by 2,4-dimethyl-6-tertiary butyl phenol
and by a 2,4-dialkyl phenol having a maximum
of about 12 carbon atoms in all alkyi radicals and
in which one alkyl substituent is selected from
the group consisting of primary, secondary-and
tertiary alkyl radicals and the other alkyl sub
stituent is selected from the group consisting of
primary and secondary alkyl radicals.
.30
about 18 carbon atoms and in which one alkyl
substituent is selected from the group consisting
‘of primary, secondary and tertiary alkyi radicals,
and the other alkyl substituent is selected from
the group consisting of primary and secondary
alkyl radicals.
DANIEL B. LU'I'EN, J a.
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