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Патент USA US3083098

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3,083,088
. 1;
Patented Mar. 26, I953
2
3,083,088
in which R3 is a monovalent hydrocarbon radical, prefer
ably of 1-6 carbon atoms and either or both R1 and R2
are hydrocarbon-ring aryl radicals of up to 10 carbon
atoms in the ring structure, that is, phenyl or naphthyl.
Dennis R. Carlson, Park Forest, Everett N. Case, Hotne
wood, and Seymour I-I. Patinkin, Chicago, ilh, assign
If one of R1 or R2 is non-aryl, it is a hydrogn or mono
LEADED GASOLINE CONTAINING AROMATHC
SUBSTITUTED TESTERS
valent hydrocarbon radical, e.g. an alkyl radical of 14
ors, by mesne assignments, to Sinclair Research inc,
carbon atoms. The hydrocarbon radicals and the carbon
New York, N.Y., a corporation oi’ Deiaware
atom adjacent R1 may be substituted, for example with
No Drawing. Filed June 15, 196i}, Ser. No. 36,150
alkyl, alkoxy or hydroxy. The R3 group may be aryl or
9 Claims. (Cl. ‘tit-69)
10 lower alkyl, preferably a lower alkyl group having 1-4
carbon atoms. The selected substituents will usually pro
This invention relates to an improved gasoline composi
vide an ester of up to about 20 carbon atoms. The acid
tion which is of high octane number, which contains a lead
residue or acyl group
compound as an anti-knocking agent, and also contains
an octane rating booster.
By and large, modern gasolines for use in spark-ignited 15
internal combustion engines, e.g., automotive and airplane
(R3—O)
may be derived from, for example, acetic or benzoic acid
and generally will contain 2-10 carbon atoms, preferably
2 to 7 carbon atoms. Exemplary preparations of useable
engines have an octane number of at least 85 RON, that
is, as determined by the research method. Almost With
out exception producers of gasoline use non-hydrocarbon
agents to raise the octane number of the gasoline to sup 20 esters are as follows:
press knocking. Generally this agent is an alkyl lead
PREPARATION OF oc-PHENYL ETHYL ACETATE
compound especially a tetra-lower alkyl lead, usually a
small amount within the range from about 0.5 to 3.0‘ cc.
per gallon, or even as much as approximately 5 or 6 cc.
per gallon. Tetra-ethyl lead is the most widely used anti 25
knock agent, and is effective in raising the octane and
thereby reducing the knock caused by abnormal combus
tion of gasoline of inferior octane rating. Other lead
compounds, such as the lower-alkyl lead carboxylates dis
closed in copending application S.N. 855,006, ?led Novem 30
ber 24, 1959, are useful as anti-knock agents. However,
the quantity of lead compound which may be used in a
To a solution of 122 grams (1.0 mole) a-phenyl ethyl.
alcohol and 95 grams (1.2 mole) pyridine in 200 ml. an
percentages, and by the fact that lead compounds cause
hydrous ether was added dropwise 85' ml. (1.2 mole.)
lead-containing deposits in the cylinders as well as by 35 acetyl chloride. The reaction occurred immediately with
gasoline is limited by decreasing e?ectiveness at higher
economic, health and legal considerations.
evolution of heat and precipitation of pyridine hydrochlo
Several methods are used for determining the octane
ride. The heat of reaction maintained the temperature
at 40 to 45° C. through most of the addition. The reac
rating of a gasoline and each method usually gives a dif
ferent ?gure; for example, the motor method of deter
tion mixture was allowed to cool to room temperature
mining octane rating generally gives a lower ?gure than 40 after which an equal volume of water was added to the re
the research method. The spread between the two ?gures
action mixture to dissolve the pyridine hydrochloride and
is termed the “sensitivity” of the fuel. Gasolines are sold
hydrolyze any unreacted acetyl chloride. The ether solu
on the basis of their research octane number but the make
tion was washed with dilute NaHCOa solution, and then
of the car and the type of driving determines whether it
water, and dried over anhydrous MgSO4. The ether was
45
operates closer to the motor method or research method
stripped off and the crude product distilled under reduced
rating; however, the road octane is usually, numerically,
in the space between the two. A gasoline having motor
pressure.
method‘and research method octane numbers which are
C. at 760 mm. Hg) was collected for a 92% yield of
closer is less sensitive in its performance to variations in
a-phenyl ethyl acetate.
.
The fraction boiling at 73° C. at 3.0 mm. Hg (220°
operating conditions.
2
ANALYSIS
In accordance with this invention, certain gasoline
compatible, i.e., soluble, miscible or dispersible, aromatic
[nnNsr'rYgi-Lrozes]
esters are incorporated in a leaded gasoline as an octane
booster. The improvement in the gasoline is sometimes
greater in the motor method of determining octane rating 55
and sometimes greater when the octane is determined by
the research method. The fuel may have less spread be
tween its research method number and its motor method
number, and would accordingly be considered as less sensi
60
tive.
The ester incorporated in gasoline according to this in
Cale.
Sap. equiv __________________________________ _.
Percent C ________________ __
Percent H ___________________________________ . _
342
73. 22
7. 33
7. 34
ACETATE
one which contains the residues of a lower carboxylic acid
and a primary or secondary lower aliphatic alcohol hav 65
332.
73. 25
PREPARATION OF 1,2-DIPHENYL ETHYL
vention is a primary or secondary mono- or di-aryl substi
tuted lower alkyl ester of a lower carboxylic acid, that is,
Det.
H 311
-
t
E
/
~
CH3
ing an aryl substituent. The ester may be represented by
=0
70
Toa solution of 50 grams (0.25 mole) 1,2-diphenyl
3,083,088
3
4
ethyl alcohol and 24 grams (0.3 mole) pyridine in 100
ml. anhydrous ether was added dropwise 22 ml. (0.3
mole) acetyl chloride. The reaction occurred imme
and contained 25.1% para?ins, 3.2% naphthenes and
71.7% aromatics.
tion of:
diately evolving heat and precipitating pyridine hydro
The fraction had an ASTM distilla
chloride. The heat of reaction held the temperature at
40-45° C. through most of the addition of ace-tyl chlo
ride. After cooling the reaction mixture to room tem
IBP ________________________________ __° F__ 313
50% _______________________________ __° F__ 334
perature an equal volume of water was added to dissolve
EP _________________________________ __° F__ 442
Rec. _____________________________ "percent" 98.5
907%
the pyridine hydrochloride and hydrolyze any unreacted
_____
__
____
° F__
368
acetyl chloride. The ether solution was Washed with 10 Res. ______________ _.. _______________ __do____ 1.0
Loss _______________________________ __do____ 0.5
dilute NaHCO3 solution and then Water, and dried over
anhydrous MgSO4. After stripping oi the ether the
Gasoline blend Dv comprised 28.4% of these tower bot-~
crude product was distilled under reduced pressure.
toms, 28.4% light‘?uid catalytically cracked gasoline,
The fraction boiling at 122° C. at 0.8 mm. Hg (319°
19.0% mixed xylenes, 19.0% alkylate fuel and 5.2%
C. at 760 mm. Hg) (reported Hauser, Shivers and 15 butane. This gasoline had an API gravity of 53.0 and a
Skell, JACS 67, 409412 [1945], B.P. 312° C. at 760
bromine number of 35.0. It analyzed as 34.9% paraf
mm. Hg) was collected for a 75% yield of 1,2-diphenyl
?ns, 15.1% ole?ns, 7.1% naphthenes and 42.9% aromat
ethyl acetate.
lCS.
Its ASTM distillation was:
ANALYSIS
[DENSITY2+£=1.0794]
Cale. J Det.
20 13? _________________________________ __°
10% ________________________________ __°
50% ________________________________ __°
90% ________________________________ __°
F..- 92
F_._ 133
F__ 256
F__ 329
EP __________________________________ __° F__ 403
25
Sap. equiv __________________________________ ._
Percent C ___________________________________ _.
234
80. 00
210
80. 46
Percent H ___________________________________ _.
6. 67
6.76
The ester is included in the gasoline composition in
Percent rec ________________________________ __ 98.0
a
30'
Percent res ________________________________ __
1.0
Percent loss ________________________________ __
1.0
Gasoline blend E had a bromine number of 38.5 and
an API gravity of 50.7 and an ASTM distillation of:
the ratio of from about 1 to 50 moles of ester per mole
of lead compound and su?icient to increase the octane
number of the leaded gasline. The molar ratio of ester
to lead compound is preferably about 2 to 40. In terms
of volume, the fuel usually contains about 0.1 to 3 vol 35
IBP _________________________________ __°
5% __________________________________ __°
20% _________________________________ __°
50% _________________________________ __°
ume percent of the ester, preferably about 0.2 to 1.5%,
70% _________________________________ __° F__ 306
and in amount su?icient to increase the octane rating
of the fuel. The concentration of the additive is im
portant in that larger percentages may decrease the oc
EP ___
tane rating of the gasoline below the rating of the
base fuel. Also, the optimum range of effectiveness of
_
F__
F"
F__
F__
103
103
188
272
_____° F-.. 408
It contained the following components (i5%):
Percent
40
Full-range straight run naphtha reformate ________ __ 30
the octane booster varies with the lead content of the
gasoline. In general, with greater amounts of, for ex
Light ?uid catalytically cracked gasoline _________ __ 30
Heavy straight-run naphtha reformate ___________ __ 30
ample, tetraethyl lead, not only is the octane increased,
Butane __________ -5 _________________________ __
10
but the octane boosting ability of the ester is also in 45 and analyzed as
creased and the optimum range for this additive is
slightly raised.
7
Gasolines are usually blends of low boiling mineral
oil hydrocarbon fractions derived by distillation, crack
ing, and other re?ning and chemical conversion processes 50
practiced upon crude petroleum. The gasoline will con
tain varying proportions of parat?ns, ole?ns, naphthenes
and aromatics and generally will boil primarily in the
Vol. percent
Para?ins ___
_
__
34.3
_
27.2
Naphthenes _____________________________ __
Aromatics _______________________________ __
4.7
33.8
Ole?ns
___-
_____
Sulfur (weight percent) ___________________ __ 0.0213
Samples of these base gasolines were obtained and
range of about 100 to 425° F. The gasoline of this
mixed with varying amounts of tetraethyl lead and phenyl
invention has aromatic components which are at least 55 substituted lower alkyl esters of lower carboxylic acids.
about 30 volume percent, preferably at least about 40
The octane determinations for each sample are reported
percent of the hydrocarbon fuel. A typical premium
in Table I below. Samples 1-6 and 71-76 contained
gasoline besides a small amount of lower-alkyl lead.
2.9 cc./gal. TEL added as Motor MiX. Samples 11—16
compound as an anti-knock agent, may also contain
and 41-46 contained 3 cc./ gal. of pure tetraethyl lead.
small amounts of other non-hydrocarbon constituents 60 The rest of the samples contained 6 cc./gal. of pure
used to impart various properties to the gasoline in its
tetraethyl lead.
use in internal combustion engines, e.g. scavengers, cor
a Table I
rosion inhibitors, etc.- Such gasolines frequently have a
research method octane number of about 90 to 105 and a
motor method octane number of about 80—98.
BASE: BLEND E (2.9 00. TEL/GAL.)
The 65
most widely used tetra-lower-alkyl lead compound added
to gasolines as an anti-knock agent is tetra-ethyl lead.
“TEL Motor Mix” is used in commercial practice to
add tetraethyl lead and scavengers to the gasoline. “Mo
tor Mix” contains 59.2% tetra-ethyl lead, 13.0% ethyl 70
ene dibromide, 23.9% ethylene dichloride and 3.9% hy
drocarbon diluent, dyes, etc. Several gasoline blends
were used in the examples and tests reported below.
Base gasoline M was a naphtha reformate distillation
tower bottoms fraction which had an API gravity of 34.1
Sample
1 ____ --
Additive
V 1
0 .
per~
cent
None ___________________ __
2 ____ ._ a-ptiicenyl ethyl ace2. e.
0.25
Octane
Change from base
Motor Research Motor Research
method method method method
88.5
99.5
88.4
99.6
_______________ __
—0.1
+0.1
88. 4
88.5
88.4
99. 7
99.8
99.9
—0. 1
0
—0.1
+0. 2
+0.3
+0.4
_88. 5
99. 7
0
+0. 2
3,088,088
Table I—Continued
Table l-Continued
BASE; BLEND D (a co. TEL/GAL.)
BASE: BLEND D (0 0o. TEL/GAL.)
V 1
°-
..
sample
Addmve
Octane
Change from base
5
Sample
V01
per:
Additive
012%; Motor Research Motor Research
Octane
cent Motor Research Motor Research
method method method method
method method method method
91__
11_____
None ___________________ __
12_____ a-lt?’lenyl ethyl ace- 0.25
92.4
92.7
109.5
103.7
+0.3
__
'
+0.2
None _________________ __
_
~
:
92"“ ‘8 15.155336011511350
ate-
_
1'0
'
92-7
103-5
+°~3
i823
9217
10412
+03
Change from base
94.3
106.5
95-4
10“
_______________ ..
'H'l
+O'2
94.8
105.9
+0.5
+0 4
0
94.9
107.1
+0.0
+0 0
ig-g
95.5
107.3
+1.2
+0 8
+07
95'2
107'?’
+°"9
+0 8
BASE: BLEND D (0 0o. TEL/GAL.)
BASE: BLEND D (0 CO. TEL/GAL.)
None ___________________ __
95.0
10“
a-phenylethylace-
06.0
106.3
0.50
tate-
15
.
None ___________________ __
04.5
106.4
6111201312’; teethyl
95.1
100.0
+0.6
+ .2
95.1
106.9
+0_@
+0 5
95.0
100.7
+0.5
+0 3
95.1
100.7
+0.0
+0 3
95.0
100.9
+0.5
+0 5
.
1.0
'
0
-
g
'
M
'
+ '
O7
+
____________ "6-
BASE: FRACTION M <0 00. TEL/GAL.)
BASE: BLEND D (6 CC. TEL/GAL.)
1H
Nam,
112____. ?-rghenyltethyl
1.25
94_2
103‘0 _______________ __
94.7
103.4
+0.5
+0.4
6112037 8
31___-_
None ___________________ ._
32“--. a-gntenyletnyincea 0.
1. 75
94.5
105.9
90.0
107.4
+2.1
+1.5
95.2
103.6
1.0
0.6
9549
107"‘
+14
+15
95.0
100.7
11.4
1:07
107 1
+231
+132
107 0
+1.8
+1.1
39-;
96:6
90.3
_______________ __
‘
95.4
95.4
+1.2
+1.2
+0.0
+0.5
.
_
_
The above examples, which
are to be considered
111110
30
(3 OG_ TEL/GAL’)
103.0
105.5
trative only and not limiting, show that the addition of
the enumerated esters to a leaded gasoline boosts the
921
1024 _______________ __
92.3
102.5
+0.2
+0.1
92.8
102.7
+0.7
+0.3 35
ggig
102:7
+017
Egg
g ig-g
octane rating of gasoline fuels.
It is claimed;
i8 2
1. A leaded gasoline consisting essentially of base
hydrocarbon gasohne containing at least about 30% aro
+0'_3
matic hydrocarbons, a small amount of lower alkyl lead
anti-knock agent suf?cient to reduce knock and about
40 l to 50 moles per mole of_lead compound and su?iclent
to improve the octane rating of the leaded gasoline of
94 3
103 4
a gasoline-compatible aryl substituted lower alkyl ester
9419
10317 “15f; ""153
of a lower carboxylio acid of up to about 20 carbon atoms
1.50
1.75
95.1
94 s
103.0
103.0
+0.8
+0 5
+0.2
+0.2
2.00
2.25
95
1
955
103.5
103.8
+1.3
+0 23
+0.1
45
+0.4
2.50
95 7
103.8
+1 4
+0.4
2.75
95 0
103.7
+0 7
+0.3
3'00
95 5
103-6
+1 2
‘to-2
BASE. FRACTION M (6 CO_ TEL/GAL)
N
géjjjjj B_g§§5;,i-e-t-1;;.;;c;- ‘135*
tatc.
and having the formula:
H H
é a
R1~ — ~—O—G—R=
H i
_
H
7
0
in WhlCh R3 is a monovalent hydrocarbon radical, R1
and R2 are selected from the group consisting of hydro
BASE: BLEND D (6 00- TEL/GAL.)
50 gen and monovalent hydrocarbon radicals, with the pro
viso that at least one of R1 and R2 is a hydrocarbon-ring
01_____ None __________________ __
95.1
105. 7 _______________ __
02"--- ?-iégteélylethyl?ce- 0-50
94*’
105-5
—0-2
-0~2
95,3
105,7
+02
0
35-4
105~7
+03
0
58
90.0
105.9
1059
+0.7
+0.2
+0.2
95.0
105.7
+0.5
‘
95.9
100.0
+0.9
+0.8
aryl radical 0t up to 10 carbon atoms in the ring structure.
2. A gasoline composition according to claim 1 1n
which R3 has 1 to 6 carbon atoms.
55
0
+0.5
BASE: BLEND E (2.9 00. TEL/GAL.)
3. A gasoline composition according to claim 1 con
. .
taming
about 2 to 40 moles of ester per mole of lead
compound‘
.
. .
.
.
4. A gasoline composition according to claim 1 con
taining at least about 40% aromatic hydrocarbons.
6O
5. A gasoline composition according to claim 3, con
taining at least about 40% aromatic hydrocarbons in
which the ester is an acetate.
~1_____
None ___________________ _-
i2..-" 1,2-diphenyl ethyl 0.50
acetate’
88.6
88.4
99.4
8&6
99A
88:8
+8.1
9910 i014
99.5
_______________ -_
+0.2
+0.1
+0_2
0
None ___________________ __
82“--. mégeirli?znyl ethyl 1.50
‘
'
94.9
105.0
,
_
_
_
_
é 65 7. A gasoline composition according to claim 5 in
+012
which the ester is ?-phenyl ethyl acetate.
8. A gasoline composition according to claim 5 in
BASE: BLEND D (6 CG TEL/GAL)
s1__.__
_
6. A gasoline composition according to claim 5 in
which the ester is a-phenyl ethyl ‘acetate.
which the ester 1s 1,2-d1phenyl ethyl acetate.
_
.
9. A gasoline composition according to clam 5 in
70 which the ester is ,B-phenyl ethyl benzoate.
_______________ ._
95-8
100.0
+0.9
2.1.
95.
97.10
100.
100.2a
+1.4
+2.2
0. 7
inc
2~
98-0
1063
+3-1
+07
_
+0.4
_
References Cited in the ?le of this patent
FOREIGN PATENTS
75
42,139
Australia ______________ __ Oct, 8, 1958
571,921
Belgium _____________ __ Oct. 10, 1958
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