Note: Descriptions are shown in the official language in which they were submitted.
~7 7 Z ~ ~
THE DISCLOSURE
This invention relates to a novel multipurpose
detergent blend or mixture for addition to gasoline. The
novel amine adduct and polycarboxylic acid ester multi-
purpose detergent composition of matter shows excellentactivity as a carburetor detergent, induction system
detergent (% deposit reduction)~ combustion chamber deter-
gency and~ in addition, provides effective rust inhibition
when used in automotive gasoline fuels at low concentra-
tions.
The novel composition of matter of this appli-
cation comprises, in the broad range, about 20 to 300 ppm
(parts per million on a weight basis in gasoline) of the
amine adduct blended or mixed with 100 to 650 ppm of the
polycarboxylic acid ester~ as an additive for gasoline,
and~ more preferably, about 60 to 100 ppm of the amine
adduct blended or mixed with 200 to 300 ppm of the poly-
carboxylic acid ester, as an additive for gasoline. The
ppm figures are based on their use in gasoline, the gaso-
line being a distillate hydrocarbon fuel having a majorproportion of a hydrocarbon base fuel distilling within
the gasoline distillation range. Stated otherwise, the
novel composition of matter (of this application), for
addition to gasoline, comprises on a 1000 barrels of gaso-
line basis, in the broad range, about 5 lbs. to 75 lbs.of the amine adduct blended or mixed with 25 lbs. to 162.5
lbs~ of the polycarboxylic acid ester and, more preferably,
.,
-~ about 15 lbs. to 25 lbso of the amine adduct blended or
mixed with 50 lbs. to 75 lbs. of the polycarboxyllc acid
ester.
-2-
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~.1)77Z~
- The novel composition of ~atter-of this appli-
cation is a blend or mixture of a polyisobutene phenol/
epichlorohydrin/amine addu~t and a polycarboxylic acid
ester. The amine adduct may also be described as the
; 5 reaction product of a polyisobutene phenol with epichloro-
' hydrin followed by amination with ethylene diamine.
.~. . . . ................................................... .
It is an object of the present invention 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
the remainder of the fuel induction system~ such as the
valves and ports, and reduce the octane requirement in-
crease of an internal combustion engine by reducing the
I buildup of combustion chamber deposits. It is another
¦ 15 object of the present invention to provide a detergent
f~el which will maintain a low level of hydrocarbon and
A; I
carbon monoxide exhaust gas emissions and which will avoid '
the use of phosphorus-containing additives. It is still
a further object of the present invention to provide a
l 20 detergent fuel which has other desirable properties, such
- as rust and corrosion protection, water demulsibility
properties, anti-icing properties, etc. It is a further ob-
ject of the present invention to provide a multi-functional
gasoline additive or additive combination effective in
inhibiting the formation of intake valve deposits in addi-
tion to being effective as carburetor detergents and which
.. . .
can be used at relatively low concentrations (and thus at
` relatively low cost)~ for example, at a total treating ~~
^~ level~ i.e., the mixture of the amine adduct and the poly-
30 carbox~lic acid ester of about 120 to 950 parts per million
', -3
. '
. . .
~7 7 ~ ~
(ppm on a weight basis in the gasoline) and~ more prefer-
ably~ 260 to 400 ppm.
There are, of course, other detergent motor
fuel compositions available today, but they generally
suffer from one or more deficiencies. Either they are
used at very high concentrations, for example~ something
of the order o~ 4000 ppm; or if used at the use levels in
which we are interested~ the available formulations suffer
from one or more defects.
It has been conceived and demonstrated that
the reaction products of certain alkylphenols, epichloro-
hydrin and amines blended or mixed together with the
polycarboxylic acid ester show excellent carburetor,
induction system and combustion chamber detergency and,
in addition, provide effective rust inhibition when used
in automotive gasoline fuels at low concentrations, i.e.,
between about 120 to 950 ppm and, more preferably, between
about 260 to 400 ppm. In addition to their activity as
fuel additives, these compounds are also potential ashless
rust inhibitors and dispersants for use in lubricating
oils. The preferred products are the N,Nl Bis[3-(p-H35-
polyisobutylphenoxy)-2-hydroxypropyl] ethylene diamlne
blended or mixed with a polycarboxylic acid ester. The
PIB is our abbreviation for a polyisobutene generically
of any molecular weight. The H35 is the commercial desig-
nation for Amoco's polyisobutene of Mn ~'670. The struc-
tural formula for the preferred product is as follows:
-3a-
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"
.~, , . ,
~ OH OH
I I . '
O-CH2cHcH2NHcH2cH2NHcH2cHcH2 1
~ ~ PIBH3 5 BH3 5
.: :
The PIBH35 component (which can also be written
simply as R) may have a number average molecular weight
(Mn) of about 500 to 2000 and, more pre~erably, about 600
,; . ,
to 1500. Optionally~ some of the polyisobutene may be in
the ortho position where it is denominated Rl. Rl may,
. therefore, simply be the same as R, i.e., a polyisobutcne
~l radlcal of number average molecular weight of about ~00
to 2000 and~ more preferably~ about 600 to 1500; or R
may alternatively simply be hydrogen~ i.e.~ H.
According to one aspect of the present inven-
~ tion~ therefore, we provide a normally liquid, multi-
,: .
functional additive composition for addition to a leaded,
,, ~
low lead, or unleaded gasoline, i.e., to a distillate -
i
- ~ 15 ~ hydrocarbon fuel comprising a ma~or proportion of a hydro-
,. ;~ ~
carbon base fuel distilling within the gasoline distilla-
tion range. This additive provides carburetor, induction
system and combustion chamber detergency~ rust inhibition
~1 ~ ` and~good har.dling properties to a higher degree than nor-
~`J' ~, 20 mally found with typical current first generation multi-
purpose carburetor detergents of the alkyl ammonium
: ~ ~ . - -p~osphate or polyolefin succinimide type. The increased
~ performance we are seeking is necessitated in part by the
0 4-
.
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advent of emissions control hardware which must remain deposit-
free ifthe new automobiles are to remain within the EPA
emissions specifications for 50,000 miles as required for
vehicle certification.
Although there are many carburetor detergents on
the market, to our knowledge, only one, "Chevron F-310"*,
can be classified as a true second generation additive
possessing the broad based activity we are seeking and
have achieved. However, F-310 is recommended at a high
treating level of 4000 ppm, and that may exceed the indus-
try's handling or economic capabilities. Therefore, we
feel there is currently no additive available which is
completely acceptable in terms of economics, treating
level and performance.
The preferred chemical amine adduct gasoline additive
compound disclosed in our copending Canadian Patent Application
No. 242,180, filed concurrently herewith, is prepared by the
following reaction sequence:
a~ Phenol is alkylated with polyisobutene,
i.e., polyisobutylene, of Mn ~670
"(Amoco H35)"** using an acid catalyst.
b) The polyisobutylphenol is converted to
the sodium phenoxide using sodium hydroxide
and then reacted with epichlorohydrin.
c) Two moles of the epichlorohydrin adduct
are reacted with ethylene diamine to
form the desired product.
* Trademark of Chevron Research Company for a polybutene amine
gasoline additive.
**Trademark.
~077~
qH 1) NaOH
PIBH35 ~ Acid Catal~s~ PIBH35 ~ OH 2) CH2ClCE~ - CH2
Rl 3) - NaCl
35 ~ / \CH + 1/2 NH2CH2 2 2
, 1
OH OH
PIBH35 ~ OCH2CHCH2NHCH2CH2NHCH2CHCH2 O ~ E~35
R Rl
Our experience with a large number of product
compounds of this type, as shown in the reaction scheme
above, indicates that a polyisobutene in the molecular
weight range of 500-2000 and a polyamine of the ethylene
diamine, diethylene triamine type produces the best bal-
ance of properties in terms of detergency, rust inhibition
and handling.
Table I presents data comparing the preferred
product of the present case with "Chevron F-310"*. (The
essential component in "Chevron F-310" is believed to be a
polybutene amine, as described in U.S. Patent 3,438,757.)
The data which indicate the percent reduction in deposits
versus untreated gasoline shows that the preferred product
greatly improves the performance of untreated gasoline and
~.
provides performance comparable to F-310 at a much reduced
treating level.
* Trademark
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. Table II presents data showing the ability of
the preferred product of the present invention to control
the increase in the octane number requirement of an
, . .
~ngine. Although the mechanism of activity is not firmly
established~ the additive presumably works by preventin~
the buildup of deposits in the combustion chamber.
~ . . . TABLE II
:. . OCTANE ~J.~ER REGUIRE`~ INCRE~S~
.
. ~reating Level, *Octane Number (C)
~ lbs./1000 bbls in ~equire~lent
-~ - AdditiveGasoline (Nonleaded) Increase
10 Untreated - 10
Base
Gas.oline ..
.. ~ Preferred 75 5
;. Product (PP)
: .(Amine Adduct
where Rl is ~ or PI~H35)
*As measured by the Combustion Chamber Deposit Engine Test
: 1 ^ .
~The Blowby Carburetor Detergency Test above,
`~. showing % deposit reduction, is described below. MS-o8
.15 gasoline is used in the Blowby Carburetor Detergency Keep
^.~ Clean Engine Tèst (~ dep.osit reduction). Phillips "J"
Reference Fuel, an unleaded fuel, is used in the Induction
.. System Test, single cylinder, % deposit reduction, and -
;also in the Combustion Chamber Deposit Engine Test.
: 20ENGINE TEST EVALUATION OF ~TLTIPURPGSE
j CARB-~RETOR DETERGENTS
. , .
(A! BLO~rBY C.~RBURETOR DET~R5ENC~ KEEP CLEAN EN5INE ~ST
:` . En~ine_Test Procedure
~ .
`~ The Blowby Carburetor Detergency Keep Clean
.. . . .
Engine Test (BBCDT-KC) measures the ability of a gasolir.e
. additive to keep. clean the carburetor throttle body area,
~i and is run in a.1970 Ford 351 CID V-8 engine equipped
, .
., .
., ~ .
. ` . .. .
.
,
~077Z~
by means Or a special "Y" intake manifold with two one-
barrel carburetors, which can be indep~ndently adjusted
and activated. With this arrangement, a separate test
fuel can be evaluated by eac~ carburetor which feeds four
of the eight cylinders via the non-interconnected intake
manifold. The carburetors are modified with removable
aiuminum sleeves in order to facilitate weighing of the
deposits which accumulate ln the throttle body area. The
severity of the test is ad~usted to an appropriate level
by recycling the entire amount of blowby gases, approxi-
mately 90-llO c.f.h., to the top of the air cleaner so
that each carburetor receives 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 con-
ditions are employed:
Test Cycle:
Phase I 650 engine rpm, 8 min.
Phase II - 3000 engine rpm~ l min.
Test duration, hrs. lO
Intake air, F. 135 + lO
Jacket water, F. 190 + lO
Engine oil-sump~ F. 210 + lO
Percent C0 in exhaust 3.0 + 0.2
Blowby, c.f.h. 90 - llO
The weight (mgs.) of deposits accumulated on the
aluminum sleeve is measured~ and the average value of Lour
tests per additive or additive mixture is reported.
_g _ .
,.
1077Z~;~
The gasolin~ used in the BBCDT-KC test is an
Ms-o8 gasoline having the following properties:
Gravity:
API 59-7
Sp. gr. at 600 F. 0.74
ASTM D-86 distillation~ F.:
I.B.P.
10% 123
50% 205
90% 348
E.P. 45
Percent recovered 98
Percent residue
Percent loss
Percent sulfur 0.11
Lead~ gm./gal. 3.08
FIA composition:
Aromatics~ percent 23.1
Olefins, percent 20.0
Saturates, percent 56.9
Oxidation stability~ minutes600+
ASTM gum (unwashed)~ mg./100 ml. 1.0
Research octane number 95.5
Percent H 13.10
Percent C 86.61
H/C 1.80
The Induction System Deposit Test, showing %
deposit reduction, is described below.
--10--
- ~
1077Z~
(B) INDUCTION SYSTE.~ DEPOSIT ENGINE TEST
~ine Test Procedure
The Induction System Deposit Test (ISDT) which
is used to evaluate the ability of gasoline additives or
mixtures of additives to control induction system deposits,
is run using a new air-cooled~ single cylinder, ~ cycle~
2.5 H.P. Briggs and Stratton englne for each test. The
engine is run for 150 hours at 3000 rpm and 4.2 ft. lbs.
load~ with a 1 hour shutdown every 10 hours to check the
oil level. Carbon ~onoxide exhaust emission measurements
are made each hour to insure that a constant air to fuel
(A~F) ratio is being maintained.
Upon completion of a test run~ the engine is
partially disassembled~ and the intake valve and port are
rated and valve and port deposits are collected and
weighed.
The test procedure used to measure octane number
requirement increase, the Combustion Chamber Deposit Engine
Test~ is described below.
(C) COMBUSTION CHA~ER DEPOSIT ENGI~E TEST
En~ine Test Procedure
The Combustion Chamber Deposit Engine Test
(CCDET) is used to evaluate the ability of a gasoline
additlve or mixture of additives to control or reduce the
;25 octane number requirement i~crease (ONRI) in an internal
combustion engine. The test is run using a 1972 Chevrolet
350 CID V-8 engine equipped with a two-barrel carburetor
and a 1972 Turbo Hydromatic 350 transmission which is con-
- nected to a 1014-2 WIG dynamometer equipped with a 200.3
lb.-ft.2 inertia wheel. The following test cycle and
--1 1--
1(~772ti~
operating conditions are employed and are intended to
simulate an urban taxi cab.
Test C~cle-
.
Phase I Start - idle, 650-750 rpm
Phase II Accelerate - 1 to 2 shift~
- 5.5 sec., 2900-3000 rpm
- Phase III Accelerate - 2 to 3 shift,
9.5 sec., 2800-2900 rpm
Phase IV 3rd gear, 10.0 sec., 2600 rpm
- Phase V Decelerate to idle~ 15.0 sec.
- Test duration 200 hrs.
Fuel consumption 1000 gal. (Phillips "J" Refer-
ence Fuel~ an unleaded fuel)
Intake air, F. Ambient
Jacket water~ F. 180
Engine oil-sump~ F. 220 + 10
~ Octane number requirement is determined at 24
hrs. interval under the following engine conditions:
transmission in 3rd gear with an output shaft speed con-
trolled at 1500 rpm and the engine throttle wide open.
The octane number requirement of the engine is deter~ined
at trace knock in terms of primary reference fuels; i.e.,
the engine is run on a series of blends o~ isooctane and
n-heptane of known octane number until audible knock is
perceived. The lowest standardized octane number blend
at which the engine does not knock is recorded as the
octane number requirement. Octane number requirement
25 increase is then the difference between the initial octane
number requirement and the final octane number requirement
for a particular test.
The (A) test procedure, i~e.~ the descr~ption
12-
~,077Z~
of the Blol~by Carburetor Det~rgency ~ep Clean En~;ine
Test~ beginning at line 22 Or page 8 o~ the specification~
refers to the results shown in Table I~ column 4~ on page
7~of the specification. The (B) test procedure, i.e.,
the description Or the Induction System Deposit Engine
Test~ beginning at the top o~ page 11 of the specific3-
tion~ refers to the results shown in Table I~ column 5~
on page 7 of the specification. The (C) test procedure,
i.e.~ the description of the Combustion Chamber Deposit
Engine Test~ beginning at line 20 of page 11 of the speci-
fication, refers to the r~sults shown in Table II~ column
3, on page 8 Or the specificat~on.
One Or the unique features of the products of
this invention is that they are one Or the few non-ionic
compounds that provide-a high degree Or rust inllibition.
This is an important feature in a gasoline additive since
ionic rust inhibitors~ l.e.~ carboxylic and phosphoric
acid salts~ tend to aggravate the problem Or induction
system deposits. In addition~ a non-ionic or ashless
rust inhibitor is a key component in formulating an ash-
less engine oil. Therefore~ the products of this inven-
tion may rind utility as lubricant additives as well as
gasoline fuel additives. me general structure of the
;novel compounds of the invention d ~ ribed in C~ ~ n Patent
pplicat~ S.N. 242,180, may be exp ~ ~ æ ~llows:
OH OH
~CH2CHCH2(NHCH2CH ~ NH~H2CHCH2
R~ ~ 2
wherein n is an integer of from 1 to 5, and
.--13-- r
.' ' ,. .
~ ~r,~ ' , .. , I ~
1077Z6
wherein R2 is an alkyl substituted benzene ring, and
wherein the alkyl substituent (or substituents) is poly-
isobutyl or polyisopropyl Or about 500 to 2000 molecular
(number average) weight.
In Example 1 and throughout the specification
and claims, all parts and percentages are by weight unless
. .
otherwise noted. -
, ExamPle 1 .
(Part A) PolYisobutene H~5 Phenol
., . .
Reaction:
OH OH
+ P0lYi50butene E35 A~berly5t 15~
PI ~ 35
M.W. 94 ~-660 ~ 754
(M.W.=Molecular Weight) (Theoretical N.W.)
The product is actually a mixture of alkylated
phenols with an average molecular weight of 548 based upon
oxygen analysls (2.92%) and 556 caiculated from W spectra'
~ parameters.
; The experimental procedure is described below.., ! .
To a 5-1. 3-necked flask equipped with a ther-
` 20 mometer, mechanical stirrer and reflux condenser with
` Dean-Stark trap was charged 1920 g. (2.9 moles) Or Poly-
iso~utene H35 '(~mX~) *~564 g. (6 moles) of phenol, 20C g.
of"Anberlyst 15"~* gcid catalyst, and 550 ml. of hexane. The
- stirred mixture was heated at reflux (pot temperature 100-
s~ 25 107 C-) under a nitrogen atmosphere for 2~ hours, durin~
~' which time 5.4 ml. Or water had separated. After cooling
to 60-ôO C.~ the mixture was filtered to remove the resi~
* Trademark ~
** Trademark of Rohm and Haas Company for a macroreticular, .
-: f~ strongly acidic c~tion exchange resin. -
i
... . . . .
1~77Z~8
beadsj the latter being washed with hexane~ and the fil-
trate subjected to vacuum concentration with a pot tem-
perature of 160 C. There was obtained 1971.4 g. of
product residue having an oxygen content of 2.92% (theo-
retical: 2.12%).
tPart B) 1,2-Epoxy-3-[p-(H35~polyisobutyl)phenoxy~
~ro~ane
Reaction:
OH
ClCH2CH- CH2 + NaOH 2~0
PI ~35
M.W. ~754 92.5 40
OCH2CH--CH2
,~, O
1 + NaCl + H20
PI ~35
~ 810
To a 5-1. 3-necked flask fitted with a ther-
mometer, mechanical stirrer, addition funnel and reflux
condenser was charged 973 g. (1.75 moles based upon 2.92%
oxygen) o~ Polyisobutene H35 Phenol, 72 g. (1.75 moles
based upon 97.4% assay) of sodium hydroxide pellets, 450
ml. of 2-propanol and 450 ml. of toluene. The stirred
mixture was heated under a nitrogen atmosphere at 84-900 C.
for one hour to effect the dissolution of the base. Epi-
chlorohydrin (161.9 g., 1.75 moles) was then added dropwise
at 600 C. during 2.5 hours, followed by a hold period at
700 C. The reaction mixture was then cooled, filtered~
and the salt (107 g. dry) washed with toluene. The fil-
;,
. . .
- ' ~ . . .
( t (
1077'~
trate was stripped (100 C./15 mm.) to give 1075.3 g. Or
product residue.
(Part C) N,Nl-Bis~3-(p-H35-polyiso~utylphenoxy)-2-
hYdroxYpro~yll ethylene diamine
Reaction:
1 2 ~O~ .
2 moles ~ Rl + H2NCH2CH2NH
PIBH35
M.W. ~810 60.1
OH OH
OCH2CHCH2NHCH2C~2NHCH2CHCH2 0
" ~R
~ 35 PIBH
~1680
A mixture of 1018.4 g. of the above epoxide7
;-~ 122.6 g. (2.04 moles) of ethylene diamine and xylene
(700 ml.) was heated at reflux (131-6 C.) with stirring
under a nitrogen atmosphere for 18 hours. After vacuum
stripping (18 mm.~ pot temperature of 120 C.3~ there was
obtained 1053.4 g. of turbid residue which was filtored !
through a bed of "Celite 545"*in a steam-heated Buchner
~unnel to give clear~ yellow viscous product. ,
The produc~ prepar~d in this way had 1.26% ~asic ;
N (1.67% theory) and 5.26% 0 (3.81% theory).
:' . ' . .
* Tra~Erkof the Johns-~nville Company for a diatomaceous
~earth filt~ation aid.
, ~
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As stated hereinbefore, the polyisobutene compo-
nent may have a number average molecular weight (Mn) of
about 500 to 2000 and, more preferably, about 600 to 1500.
Blends or mixtures of the amine adduct and the polycar-
boxylic acid esters, and proportions thereof~ have beenmentioned hereinbefore. (See, for example, page 2 of the
specification.)
The preferred polycarboxylic acid esters are
mixed esters of di- or tri-carboxylic acids. An espe-
cially preferred polycarboxylic acid ester is the mixed
adipate diester comprising the mono-isodecyl, mono-octyl
phenoxy polyethoxy ethanol (containing an average of 5
; moles of condensed ethylene oxide) mixed ester of adipic
acid made by a conventional acid esterification process.
In Table III~ performance data of the blends or mixtures
are shown.
The relative proportions of the amine adduct
and the mixed polycarboxylic acid esters are given on
page 2 of the specification.
The proportions or amounts of the polycarboxylic
acid esters useful in this invention are given on page 2
of the specification; and these proportions or amounts
apply whether the polycarboxylic acid ester is completely
esterified with the same alcohol or whether the polycar-
boxylic acid ester is esterified with different alcohols,
in which case it is referred to as a mixed acid ester or
a mixed polycarboxylic acid ester, e.g., the mixed dicar-
i boxylic acid ester in column 1 of Table ~II, wherein is
shown the mixed ester of adipic acid esterified with a
mono-isodecyl alcohol and a mono-octyl phenoxy polyethoxy
ethanol containing 5 moles of ethylene oxide.
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IY ~ ~ ~ ~ X
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a) ~
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.~, E~ ~1 C) a
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O h H
O h
rl o !> a~
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O ~r~ * . tq
~ h c
t~ ~ *~ a) ~1 ~1 ~ ~
O * ~ h c) OD G~ u7
a) ,~ ~ c ~ ~ h a~ S~ X ~1
O
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a~ ~ * x
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~rl O O h~ ~ tn O ~ ~:1 h
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As can be seen from Table IIT, the mixture of
~ the amine adduct and the mixed acid ester of adipic acid
: compares very favorably with the amine adduct product~
C per se~ and with the Chevron F-310. It should also be
noted from Table III that the Chevron F-310 i.s used at a
much higher level (1000 lbs. per thousand barrels of
gasoline) than is the amine adduct or the blend of the
. amine adduct and the mixed acid ester of adipic acid.
. . . Other adipic acid esters may also be used~ e.g.,
lO the.mixed adipic acid esters compris~ng a mixed Cl to C20
. alkyl/alkyl phenoxy (alkyl of C4 to C20 polyethoxy ethanol
; ~containing l to 20 moles of condensed ethylena oxide and~
more preferably~ about 1 to 5 moles of condensed ethylene
oxide) ester. These mixed esters may then be blended or
mixed with the amine adduct~ as indicated in Takle ITI.
. (See last entry in column l of Table III.)
Some of the.other acids, besides adipic, that
may be used in the present invention (used in the ester
,.
or mixed ester form) with a Cl to C20 alcohol and an aro.-
matic alkyl phenoxy alcohol (alkyl of C4 to C20 and con~
-taining 1 to 20 moles of and~ more preferably, l to 5
moles of ethylene oxide~ include~ for example:
, . Oxalic Acid H02CC02H
. ! .. Malonic Acid H02CCH2C02H
Succinic Acid H02C(CH2)2C02H
. Glutaric Acid H2C(CH2)3C2H
. . Adipic Acid X2C(CH2)4C2H
~,~! , , Pimelic Acid H 2C(cH2)5c2H
. ~ .
SuberlF Acid H02C(.CH2)6 2
_l9_
: ,, . ' - , ' .,
. . r , ~
r
1(~772~8
Azelaic Acid. H02C(CH2) CO~H _
Sebaclc Acid H02C(~H2)8C02~ .
Maleic Acid cis-H02CCH = CHC02H
Polybasic acids formed by dimer or trimeriza-
tion of polyunsaturated fatty acids. Two examples in
this category are the C54 trimer and C36 dimer acids sold
commercially by Emery Industries..
Phthalic Acid 1,2 C6H4(C02H)2
.. Isophthalic Acid 1~3 C6H4(C02H~2
. Terephthalic Acid 1,4-C6H4(C02H)
Hemimellitic Acid 1 ~2'3-C6H3(C02H)
Trimellitic Acid 1~2~4-C6H3(C02H)
Trimesic Acid 1,3,5-~6H3(C2H)3
Some of the alcohols that may be used to esteri-
fy the above noted acids include~ for example~ those show~
in the table below:
Acid Alcohol(s)
Malonic "Triton X-45" */isodecyl
Succinic "Triton X 45"/isodecyl
Sebacic "Triton X-45"/isodecyl
Phthalic. "Triton X-45n/isodecyl
Oleic "Triton X-45n/isodecyl
Other polybasic acids which may be used to pro-
vide the mixed esters include:
.' ~ '' ~ .
*nTrlto~ X-45n C8H17 ~ ~CH2CH20)5H
"Triton X-45W is the registered trademark of Rohm and Haas
Company for ethoxylated aIkyl phenoxy.alcohols and .
surfactants.
-20-
- ~.,
' '~''" .
.~
.; .
1077Z~;8
(a) Saturated dibasic acids from oxalic to
sebacic (C2-C10)
(b) Maleic acid
(c) Phthalic~ isophthalic and terephthalic
acids
(d) Fatty acid dimers and trimers,
The gasoline additive or additives or gasoline fuel
additive or additives of the present invention act to control
spark plug fouling and thus help to keep the spark plugs
relatively clean and relatively free of any deposits.
The novel amine product or adduct or adducts used in
this invention may be described as, for example, the reaction
product of a p~lyisobutene phenol with epichlorohydrin followed
by amination with ethylene diamine, or some other polyamine.
It is recognized that the alkylation of a polyamine
is a reaction which in general leads to complex mixtures of
products.The term " Preferred PrGduct", as used throughout
the specification, should be recognized by one skilled in the
art as encompassing all of the amine adduct product (s) derived
from the reaction sequence as described hereinabove. For the
sake of illustration and brevity, only one of the possible
reaction products has been depicted in this disclosure; how-
ever,the preferred product in the case where n=l can be a
mixture of (a) and (b), or (a) or (b) taken singly. In other
words, on a parts per 100 parts basis, (a) can vary from 1
to 99 parts and (b) can vary from 99 to 1 part; or there can
be 100 parts of (a) or 100 parts of (b), all parts being on
a weight basis. In the case where n is greater than 1, mGre
complex mixtures can form where alkylati~n can occur at any
of the available nitrogen sites; such cases are taken to
_~_
77Z~
- be covered by the present disclosure. The overall amount or
use in gasoline of th~ new product or amine adduct (s) remains
the same no matter what the internal proportion or ratio
or amount of ~a) or (b) is.
OH ~
CH2~HCH2(N~CH2CH2) NHCH2CHCH2 - (a)
R
R2
., . . I
~ IH
: . . R2OCH2C~C~2
` ~ (CH2CH2NH)nH (b)
20C~I2~CEIC~12
OH
where n=l *o 5 and R2 is a polyisobutyl or a polyisopropyl
substituted benzene ring as hereinbefore disclosed.
.?
The polycarboxylic acid ester is used primarily for
cost considerations and lowers the treating costs of the gasoline.
The polycarboxylic acid ester's principal function is for
per cent deppsit reduction in the Induction System Test
and in the vehicle where it ultimately will be used.
;: I
'
.
.
.
;
-21a-
~77Z68
. .
Thls application is related to copending, con-
currently filed,;Canadian Patent App'lication 242,178 of -
Warren H. Machleder and Joseph M. ~ollinger, said application
being entitled "Multipurpose Fuel Additive and Mixture or ,
Blend" .
This application is also related to copending, ~
concurrently filed, Canadian Patent Application 242,180 of
Warren H. Machleder and Joseph M. Bollinger, said application
being entitled "Multipurpose Fuel Additive". .
.
.
. .,
.
; .
. ~
; ' ' ' .
-22-
. ~ .
1077Z~
. I
SUPPLEMENTARY DISCLOSURE --
The present invention, in one-aspect,ja~ described
in the Principal Disclosure of thi application, resides in a
multipurpose gasoline fuel addtive comprising a mixture or
blend of
(a) an additive of the formula
OH OH
2CHCH2 (NHCH2CH2 ) nNI~C~2CHCH2
R2 \R2
wherein n is an integer of from 1 to 5, and wherein R2 is an
alkyl-substituted benzene ring, and
(b) a polycarboxylic acid ester.
The invention as set forth in the Principal Dis-
closure hereof, in another aspect, resides in a motor fuel
composition which comprises
(1) a major proportion by weight of gasoline, and
(2) a minor proportion by weight, i.e. about 20 to
300 ppm of the above-defined amine adduct (a) admixed with
about 100 to 650 ppm of the polycarboxylic acid ester.
Now, according to a further broad aspect of the
present invention, as described more fully hereinafter in this
Supplementary Disclosure, there is provided a multipurpose
addttive for a hydrocarbon fuel, a lubricating oil, or a
mixture of a hydrocarbon fuel and a lubricating oil, comprising
a mixture of
(1) the reaction product of (a) a glycidyl
ether compound of the formula
(R ~ OCH2CR !CR2
-23-
.~ .
.
~0~7Z68
where R6 is an aliphatic hy~ocarbon group
having at least 8 carbon atoms and m is
1~3, and tb) an amine having at least
one amino group having a~ least one ;
active hydrogen atom, and
(2) a polycarboxylic acid ester wherein
the ester group is the residue of a :
Cl-C20 alkanol, an alkyl phenoxy poly- .
ethoxy ethanol, or the mixed residue of
said alkanol and said ethanol.
In its broadest aspect, the present invention
resides in a multipurpose additive for a hydrocarbon fuel,
a lubricating oil, or a mixture of a hydrocarbon fuel
~ and a lubricating oil, comprising a mixture of:
; (1) the reaction product of (a) a glycidyl ether
compound of the formula
:'
:'~ /0~ .,
R2 0-CH2 . CH2
where R2 is a benzene ring having attached thereto at least
one aliphatic hydrocarbon substituent, and (b) an amine
having at least one amino group having at least one active
hydrogen atom; and
(2) a polycarboxylic acid ester. ,
Also provided by the invention as described in
" this Supplementary Disclosure is a composition comprising a
blend of (A) a ~ajor proportion of a hydrocarbon fuel, a
lubricating oil or a mixture of a hydrocarbon fuel and a
lubricating oil, and ~B) a minor detergent amount of a
multipurpose additive comprising a mixture of
(1) the reaction product of (a) a glycidyl
,- ether compound of the formula
''
~ - 24 _
1(~77'~
o
( R 6 3;~
where R6 is an aliphati~ hydrocarbon
~roup having at least 8 carbon atoms
and m is 1-3, and (b) an amlne having
at least one amino group having at least
one actlve hydrogen atom, and
(2) a polycarboxylic acid ester wherein
the ester group is the residue 0~ a
Cl-C20 alkanol, an alkyl phenoxy poly-
ethoxy ethanol, or the mlxed re~idue o~
said alkanol and ~aid ethanol.
. 20
- 24a -
~ _i
-- .
~.077Z~
Detergent motor fuel and lubricating oil additives
available today generally suffer from one or more deficiencies.
Either they are used at very high concentrations, for example,
- of the order of 4000 ppm, or if used at lower, more economical
levels, their detergency and other desirable properties are
substantially diminished or lost.
The motor fuel detergency properties relate to
ability of the additive to clean up and maintain the clean-
liness of the carburetor and other elements of the fuel in-
duction system, such as the intake valves and ports, and to
reduce the octane requirement increase of an internal com-
bustion engine by reducing the buildup of combustion chamber
deposits. Another property is the ability of the additive
to maintain a low level of hydrocarbon and carbon monoxide
exhaust gas emissions so that phosphorus-containing
additives are not required. Still other desirable properties
include rust and corrosion protection, water demulsibility
properties, anti-icing properties, and the like.
, ~
It has been conceived and demonstrated that mixtures
of (1) the reaction products of certain substituted phenols,
epichlorohydrin and amines, and (2) a polycarboxylic acid
ester show excellent carburetor, induction system and combus-
tion chamber detergency and, in addition, provide effective rust
inhibition when used in hydrocarbon fuels at low concentrations,
i.e., about 20 to 300 ppm of reaction product (1) and about
100 to 650 of the polycarboxylic acid ester (2) and, more
preferably, about 60 to 100 ppm of (1) and about 200 to 300 ppm
of (2). Stated on another basis, the novel composition of
matter (of this application), for addition to gasoline for
example, comprises on a 1000 barrels of gasoline basis, in the
broad range, about 5 lbs. to 75 lbs. of the amine adduct
blended or mixed with 25 lbs. to 162.5 lbs. of the polycarboxylic
- 25 -
10'~7Z~
acid ester and, more preferably, about 15 lbs. to 25 lbs. of
the amine adduct blended or mixed with 50 lbs. to 75 lbs. of
the ester. As hydrocarbon motor fuel (such as gasoline or
diesel fuel) additives, the mixtures of the invention act to
control spark plug fouling and thus help to keep the spark
plugs relatively clean and free of deposits.
In addition to their activity as fuel additives,
these mixtures are also ashless rust inhibitors and disper-
sants for use in lubricating oils at concentrations of about
0.1 to 10% by weight, preferably about 0.5 to 8% by weight,
wherein the ratios of (l) to (2) are about equivalent to
those set forth above.
According to a preferred aspect of the present
invention, there is provided a normally liquid, multi-purpose
additive mixture for addition to a leaded, low lead, manganese
or unleaded gasoline, i.e., to a distillate hydrocarbon fuel
comprising a major proportion of a hydrocarbon base fuel
distilling within the gasoline distillation range. The
additive mixture provides carburetor, induction system and
combustion chamber detergency, rust inhibition and good
handling properties to a high degree and at relatively low
concentrations (and thus at relatively low cost), for ex-
ample, at a total treating level, i.e., the mixture of the
amine adduct and the polycarboxylic acid ester, of about 120
to 950 parts per million (ppm on a weight basis in the gaso-
line) and, more preferably, 260 to 400 ppm. The increased
performance sought is necessitated in part by the advent of
emissions control hardware which must remain deposit-free if
the new automobiles are to remain within the Unites States EPA
emissions specifications for 50,000 miles as required for
vehicle certification.
- 26 -
107726~
Component (1) of the multipurpose additive of the
present invention in its broadest aspect is the reaction pro-
duct of (a) a glycidyl ether compound (I) of the formula:
; ~ /0\
~ -OCH2CH - CH2
where R6 is an aliphatic hydrocarbon group containing at least
8 carbon atoms, m is 1-3, and (b) a primary or secondary
monoamine or polyamine, that is, an amine having at least
one amino group having at least one active hydrogen atom.
The mole ratio of glycidyl ether to amine can be 1:1, less
than 1:1 or at least 1:1, depending on the number of active
hydrogen atoms available for reaction, the extent of glycidyl
ether substitution desired, and the economics of the reaction
; considering the ease or difficulty with which the substitution
can take place. Thus, while ethylene diamine has four active
amino hydrogen atoms and theoretically therefore can be
tetra-substituted with the glycidyl ether reactant, the
degree of substitution is influenced by the number, position
and bulk of the R6 groups. When R6, for example, is C8 or
Cg and m is 1 or 2, tetra substitution on ethylene diamine
occurs with ease. A glycidyl ether compound to amine mole
ratio of at least 4:1 is therefore appropriate, although a
lower degree of substitution can be achieved by a lower mole
ratio, if desired. However, when R6 is long chain alkyl and/or
bulkier in configuration, such as polyalkylene of 500 or higher
molecular weight, it may be difficult to achievemore than di
substitution by the glycidyl ether compound and then primarily
only mono substitution on different nitrogen atoms may occur.
- 27 -
1077268
The glycidyl ether compound (I) is conveniently pre-
pared by condensing a metal alkoxide of a phenol having 1-3
aliphatic hydrocarbon substituents ~R6) with an excess of
epichlorohydrin. The carbon content and number of aliphatic
hydrocarbon substituents are chosen to provide the required
degree of solubility of the final glycidyl ether compound/amine
adduct in hydrocarbon fuels or lubricating oils.
- In this specification unless otherwise stated, molec-
ular weights are number average molecular weights and "alkyl"
includes any aliphatic hydrocarbon radical, wherther straight or
branched chain, derived from an alkane.
A variety of alkyl phenols are commercially available
for preparing the glycidyl ether compounds, including octyl
phenol, nonyl phenol, dodecyl phenol, octadecyl and pentadecyl
phenol, in their various mono, di and tri-substituted forms
and isomeric mixtures thereof. As is well-known, the alkylation
of phenol produces a mixture of mono-, di- and tri-alkylated
phenols, predominating in ortho and para substituted products.
Preferred products are those containing at least 60~ of the
alkyl substituent para to the phenolic hydroxyl group. The
mono-alkylated phenol is the preferred product but di- or tri-
alkylated products need not be removed from the admixture.
The substituted phenols wherein the substituent is polyalkylene
are prepared by methods well-known in the art, for example, by
the acid-catalyzed alkylation of phenol with an olefin. They
are also readily prepared by polymerizing a low molecular weight
mono-olefin containing from about 2 to 10 carbon atoms, such
as ethylene, propylene, butylene, pentene and decene, and then
alkylating the phenol with the polyolefin. Preferably, the
resulting polyalkylene substituent will have a molecular weight
of about 500-2000, more preferably about 600-1500, wherein the
- 28 -
iO772~;~
polyalkylene is the polymerization product of propylene or
butene, whether straight or branched chain or mixtures
thereof. A preferred R6 substituent is made by the poly-
merization of propylene or butene, or mixture thereof, to
produce a polyisopropylene or polyisobu-tene mixture. While
the major product of the alkylation is the para substituted,
mono polyalkylene phenol, some di- and tri- substitution will
also occur. Accordingly, the invention includes the use of
such substituted mixed products. Any amine having at least
one amino group having at least one active hydrogen atom may
be reacted with the glycidyl ether compounds (I) to form the
adducts of the invention. ~ccordingly, suitable amines in-
clude primary and secondary mono and polyamines such as
aliphatic amines, aromatic amines, cyclic amines, and heter-
ocyclic amines. A single amine may also contain both primary
and secondary amino groups. The amines may also carry one or
more inert substituents, that is, substituents which do not
substantially affect the reactivity of an amine group toward
the glycidyl ether compound nor the properties of the final
adducts as multipurpose additives for fuels and lube oils.
Among such relatively inert substituents may be mentioned
hydroxyl, halo, nitro, sulfide, cyano, carbonyl in various
forms such as ester, amide and ketone groups, non-polymeriz-
able unsaturated groups, and tertiary amino groups.
Examples of the amines include the primary alkyl
amines such as methyl amine, ethyl amine, n-propyl amine,
isopropyl amine, n-butyl amine, isobutyl amine, 2-ethylhexyl
amine, dodecyl amine, stearyl amine, hexyl amine, eicosyl
amine, triacontyl amine, pentacontyl amine, and the like,
including those in which the alkyl group contains from 1 to
about 50 carbon atoms. Also, dialkyl amines may be used such
- 29 -
1077Z~
as dimethyl amine, diethyl amine, methylethyl amine, methyl-
butyl amine, di-n-hexyl amine, methyl dodecyl amine, dieicosyl
amine, methyl triacontyl amine, dipentacontyl amine, and the
I like, including mixtures thereof.
Another useful class is the N-substituted compounds
such as the N-alkyl imidazolidines and pyrimidines. Also,
aromatic amines having a reactive hydrogen atom attached to
nitrogen can be used. These include aniline, N-methyl aniline,
ortho, meta and para phenylene diamines, ~-naphthyl amine,
N-isopropyl phenylene diamine, and the like. Heterocyclic
amines are likewise useful including morpholine, thiomorpholine,
N-(3-aminopropyl)morpholine, pyrrole, pyrroline, pyrrolidine,
3-aminomethyl pyridine, tetrahydrofurfuryl amine, indole,
pyrazole, pyrazoline, pyrazolidine, imidazole, imidazoline,
imidazolidine, piperidine, phenoxazine, phenathiazine, and
mixtures thereof, including their substituted homologs in
which the substituent groups include alkyl, aryl, alkaryl,
aralkyl, cycloalkyl and the like.
A preferred class of amines is given by the formula
II:
RlN (R4N) R4 NH
~ R5n 13 II
where Rl, R2 and R3 independently are hydrogen, Cl-C6 alkyl
substituted by -NH2 or -OH, R4 is a Cl-C6 divalant hydrocarbon
radical (alkylene or phenylene), R5 is hydrogen or Cl-C6 alkyl,
and n is 0 to about 5. These amines include amines wherein
the amino groups are bonded to the same or different carbon
atoms. Some examples of diamine reactants where the amine
groups are attached to the same carbon atoms of the alkylene
radical R4 are N,N-dialkylmethylenediamine, N,N-dialkanol-l,
l-ethanediamine, and N,N-di(aminoalkyl)-2,2-propanediamine.
- 30 -
107726~
- Some examples of diamine reactants in which the
amine groups are bonded to adjacent carbon atoms of the R4
alkylene radical are N,N-dialkyl-1~2-ethanediamine, N,N-
dialkanol-1,2-propanediamine, N,N-di(aminoalkyl)-2,3-butane-
diamine, and N,N-dialkyl-2,3-(4-methylpentane)diamine.
,,
. Some examples of diamine reactants in which the
amine groups are bonded to carbon atoms on the alkylene
radical represented by R4 which are removed from each other
by one or more intervening carbon atoms are N,N-dialkyl-1,3-
propanediamine, N,N-dialkanol-1,3-butanediamine, N,N-di(amino-
alkyl)-1,4-butanediamine, and N,N-dialkyl-1,3-hexanediamine.
Some examples of hydroxyl substituted radicals
are 2-hydroxy-n-propyl, 2-hydroxyethyl, 2-hydroxy-n-hexyl,
3-hydroxy-n-propyl, 4-hydroxy-3-ethyl-n-butyl, and the like.
~' Some examples of amine substituted Rl, R2 and R3 radicals
' are 2-aminoethyl, 2-amino-n-propyl, 4-amino-n-butyl, 4-
amino-3,3-dimethyl-n-butyl, 6-amino-n-hexyl, and the like.
Preferred Rl, R2 and R3 radicals are unsubstituted alkyl ;~
radicals such as methyl, ethyl, n-propyl, isopropyl, sec-
butyl, n-amyl, n-hexyl, 2-methyl-n-pentyl, and the like.
"
Some specific examples of diamine reactants are:
N,N-dimethyl-1,3-propanediamine; N,N-dibutyl-1,3-propane-
diamine; N,N-dihexyl-1,3-propanediamine; N,N dimethyl-1,2-
propanediamine; N,N-dimethyl-l,l-propanediamine; N,N-
dimethyl-1,3-hexanediamine; N,N-dimethyl-1,3-butanediamine;
; N,N-di(Z-hydroxyethyl)-1,3-propanediamine; N,N-di(2-
hydroxybutyl)-1,3-propanediamine; N,N-di(6-hydroxyhexyl)-1,
l-hexanediamine; N,N-di(2-aminoethyl)-1,3-propanediamine;
N,N-di(2-amino-n-hexyl)-1,2-butanediamine; N,N-di(4-amino-
- 30 3,3-di-methyl-n-butyl)-4-methyl-1,3-pentanediamine; N-(2-
hydroxyethyl)-N-(2-aminoethyl)-1,3-propanediamine; N,N-
- 31 -
~077'~
dimethylethylenediamine; 2-aminoethylaminoethanol; and
1,4-cyclohexyldiamine.
Other useful polyamines are ethylene- and propyl-
enepolyamines and include ethylenediamine, diethylenetri-
amine, triethylenetetramine, tetraethylenepentamine,
pentaethylenehexamine, hexaethyleneheptamine, propylene-
diamine, dipropylenetriamine, tripropylenetetramine, tetra-
propylenepentamine, pentapropylenehexamine, and hexapro-
pyleneheptamine. The ethylenepolyamines are preferred,
that is, amines of formula II wherein Rl, R2, R and R are
hydrogen, R5 is ethylene, and n is 1-5. These polyamines
can be prepared by well-known methods of the art such as by
the reaction of ethylene or propylene dichloride with ammonia.
Most of the above polyamines are commercially available.
As indicated, when the amine contains two or more
active hydrogen atoms and when more than two moles of the
glycidyl ether compound (I) are used in preparing the additives
of the invention, poly-substitution can occur. Accordingly,
depending upon the selection of polyamine and glycidyl ether
compound and the mole ratios of the reactants, the reaction
product can have none, some, or all of the terminal or internal
amino groups of the polyamine substituted. Those skilled in
the art will appreciate the fact that in a condensation
reaction of the type of this invention, involving a reactant
(polyamine) having multiple reaction sites, the reaction
product will usually be a mixture of the possible reaction
products, although one or more of the products may predominate
over the others. Accordingly, it will be understood that the
reaction products of the invention include mixed products
as well as single products.
- 32 -
` ~077Zf~
As pointed out in pages 3a and 4 of the Principal
Disclosure, a preferred component (1) of the additive mix-
tures of the invention is N,N'-bis~3-(p-H35-polyisobutyl-
phenoxy)-2-hydroxypropyl]ethylene diamine, shown by the
structural formula III where R6 is hydrogen or PIBH35:
OH OH
.' I I
~CH 2N~CH 2 CN 2N}ICH 2 CH CH~
PIBH35 H35
where PIB is an abbreviation for a polyisobutene generically
¦ of any molecular weight. H35 is the commercial designation
for Amoco Chemical Company's polyisobutene having a number
¦ average molecular weight (Mn) of about 670.
¦ More generally, the PIB component may have a number
, average molecular weight of about 500 to 2000, preferably about
;~20 600 to 1500. Optionally, some of the polyisobutene may be in
the ortho position. R6 may, therefore, simply be the same as
PIB or R6 may be hydrogen.
As indicated in the general description above, the
preferred component (1) can be a mixture of structure III and
structure (IV) set forth below or it can be III or IV taken
singly. In other words, on a parts per 100 parts basis, III
can vary from 1 to 99 parts and IV can vary from 99 to 1 part;
~; or there can be 100 parts of III or 100 parts of IV, all parts
being on a weight basis.
- 33 -
';
~077Z~
R6
~ OH
PIBH35-~0~ 0-CH2CHCH2
/N CH2CH2NH2 IV
H35 ~ ~ ~J ~ o-cH2cHcH2
~ OH
~R6
where R6 is as defined in structure III.
The overall amount for use of the amine adduct(s)
remains the same no matter what may be the proportions of
isomers in the product.
As previously disclosed in pages 5 and 6 of the
Principal Disclosure, the preferred chemical gasoline
additive component (1) is prepared by the following reac-
tion sequence where R is PIBH35:
a) Phenol is alkylated with polyisobutene,
i.e., polyisobutylene, of molecular weight
of about 670 ("Amoco H35")* using an acid
catalyst.
b) The polyisobutylphenol i5 converted to the
sodium phenoxide using sodium hydroxide and
then reacted with epichlorohydrin.
c) Two moles of the epichlorohydrin adduct are
reacted with one mole of ethylene diamine
to form the desired product.
:~.
* Trademark
- 34 -
10772~
OM 1 ) NaOH
H35 ~ Acid Catalys~ PIBH3 ~OH 2) CH2ClCH CH2
~ PIBH3~ 2 CH2 NH2CH2CH2NH2
PIHH ~ OCHzCHCH2NHCH2CH2NHCH2CHCH2 O ~ PIHH35
The reaction product may be separated from the hydro-
carbon solvent usually employed as the reaction medium or the
- product may be left in the solvent and the mixture used as a
concentrate for blending with a hydrocarbon fuel. It the pro-
duct is to be used in a heating oil or a lubricating oil, or
even if it is to be used in a motor fuel, a concentrate in
neutral oil (about one-third neutral oil and two-thirds amine
adduct) is a convenient blending composition. The concentrate
may be further diluted, if desired, to contain about 10-60%
by weight of amine adduct.
Experience with a large number of product compounds
of the type shown in the reaction scheme above, indicates that
a polyisobutene substituent in the molecular weight range of
500-2000 and a polyamine of the ethylene diamine, diethylene
triamine type produces the best balance of properties in terms
of detergency, rust inhibition and handling, when used in
admixture with component (2).
1~77Z6~
The polycarboxylic acid ester component (2) is
used primarily for cost considerations and lowers treating
costs. However, component (2) also promotes deposit reduc-
tion as shown in the Induction System Test described below.
Component (2) preferably is a mixed ester of a di-
or tri-carboxylic acid, although polycarboxylic acid esters,
wherein the ester groups are the same, are also useful. An
- especially preferred polycarboxylic acid ester is the mixed
adipate diester comprising the mono-isodecyl, mono-octyl phenoxy
polyethoxy ethanol (containing an average of 5 moles of con-
densed ethylene oxide) mixed ester of adipic acid made by a
conventional acid esterification process.
- The proportions or amounts of the polycarboxylic
acid esters useful in the invention apply whether the poly-
carboxylic acid is completely esterified with the same
alcohol or whether the polycarboxylic acid is esterified
with different alcohols, in which case it is referred to
as a mixed acid ester or a mixed polycarboxylic acid ester,
e.g., the mixed dicarboxylic acid ester for which test
results are reported in Table IV below.
In Table IV the comparison primarily is with
"Chevron F-310"*. The essential component in "Chevron F-310"
is believed to be a polybutene amine as described in U.S.
Patent 3,438,757. As can be seen from Table I, the mixture
of the amine adduct component (1) and the polycarboxylic
acid ester component (2) compares very favorably with component
(1) and with the "Chevron F-310", when the latter two additives
are used alone. It should also be noted from Table IV that
the "Chevron F-310" is used at a much higher level (1000 lbs.
per thousand barrels of gasoline) than is either the amine
adduct component or the mixture of component (1) and component
* Trademark
- 36 -
10772~
(2). Descriptions of test procedures (A) and (B) follow Tables
I and II in pages 8-11 of the Principal Disclosure, to which
the reader is referred.
'. 10
. ~ . .. .
10772~
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m ~
~ a)
QU ~ 3 H ~
U o
~: 0 h
o a ~-'' o ~ 00 .~
.,,.,, ~ I U~ ~
,~ ~ Z _~ o
H
:~ ~
~1 oa~ I ~
O
,. ~ ~ O
~ ~ ~ . ~ o
~ o a
-- H O
~ ~) H O S J
;~ ~ O 1 ~ ~
o * * O O o ~ '
X X U O ~ ~
.~ m ~ ~ ~ ~ ~ ~ ~ ~
O ~ 5--1 X O O O U
~ ~ ~: * C,) ¦ O
,
'
-- 38 --
~0~72~;~
AS stated in page 13 of the Principal Disclosure,
one of the unique features of the additive mixtures of the
invention is that they are one of the few non-ionic additives
that provide a high degree of rust inhibition. This is an
important feature in a gasoline additive since ionic rust in-
hibitors, i.e., carboxylic and phosphoric acid salts, tend to
aggravate the problem of induction system deposits. In
addition, a non-ionic or ashless rust inhibitor is a key com-
ponent in formulating an ashless engine oil. Therefore, the
mixtures of this invention have utility as natural or synthetic
lubricating oil additives as well as motor fuel additives.
In addition to use in all types of gasoline fuels,
the products have multipurpose utility in other liquid hydro-
carbon motor fuels, particularly of the diesel and jet engine
types, and in heating fuel oils such as furnace oils, burner
oils, and the llke.
Accordingly, the multipurpose additive mixtures of
the invention have valuable utility in two- and four-cycle
combustion ignition engines for controlling or reducing
carburetor, induction system and combustion chamber deposits,
and for control or reduction of octane number requirement
increase, spark plug fouling and power loss; and in compression
ignition (diesel) engines for controlling piston and fuel
injector deposits, and for reducing smoke emissions and power
loss. While optimum use levels in various systems may differ,
an advantage provided ïn common is multifunctional utility at
relatively low use levels.
The fuel or lubricating oils containing an additive
mixture of the invention may also be formulated with any of the
conventional additives, including anti-knock agents, ignition
accelerators, combustion improvers, power improvers, cold
- 39 -
~77Z~
starting aids, autoignition inhibitors, antioxidants, gum
inhibitors, corrosion inhibitors, sludge inhibitors, detergents,
metal deactivators, stabilizers, dispersants, tetra-ethyl
lead stabilizers, stabilizers for metal carbonyls, varnish
inhibitors, upper cylinder lubricants, scavengers, octane-
requirement-increase depressants, surface ignition inhibitors,
spark plug fouling inhibitors, dyes, foam inhibitors, odor
inhibitors, odor masking agents, anti-icing agents, decolorizing
agents, odorants, identification markers, freezing point de-
pressants, and flammability suppressors.
In the following examples and throughout the speci-
fication and claims, all parts and percentages are by weight
unless otherwise noted, and R6 is hydrogen or the same as the
ôther hydrocarbon substituent on phenol. These examples il-
lustrate component (1) of the additive mixtures of the invention.
The polycarboxylic acid ester components (2) may be readily
blended with the adduct component (1) to form the additive
mixtures of the invention as previously described. (Example 1,
Parts A-C, appears in pages 14-16 of the Principal Disclosure.)
EXAMPLE 2
Part A: Polyisopropylphenol
~;
To a 5-liter, 4-necked round-bottomed flask fitted
with a stopcock on the bottom, a condenser, a stirrer, a
thermometer, and an addition funnel, were charged, under nitro-
gen, 1150 g(2.0 moles) "Ampol"* C20 polypropylene. The re-
action was heated to 70C and 236 g (2.5 moles) of phenol were
added followed by the dropwise addition (10 minutes) of 102.4 g
(0.4 mole) BF3 Phenol complex. The reaction mixture was heated
to 95C and held there 5 hours. The reaction mixture was then
cooled to 70C, diluted with 600 cc toluene, and a solution of
131.4 g (1.24 moles) Na2CO3 in 1050 cc water was slowly added.
* Trademark of Ampol Petroleum Ltd.
- 40 -
1(~77Z~
The mixture was heated to 80C and the layers were allowed to
separate. After discarding the aqueous layer, the organic
layer was washed with 100 cc water. The organic layer was
then vacuum stripped (180, 0.25 mm~ to afford 1260 g ~94%)
polyisopropylphenol (Mn ~737).
Part B: Polyisopropylphenyl Glycidyl Ether
To a 5-liter, 4-necked round-bottom flask fitted with
a condenser, addition funnel, stirrer, and thermometer were
charged 1260 g (1.71 moles) above polyisopropylphenol. A 50%
NaO~ solution (137.3 g, 1.71 moles) was then added and the
mixture heated with stirring to reflux (118C) and held there
! for ~.S hours. The mixture was vacuum stripped at 100 (0.5 mm)
to remove water, recharged with 50 g toluene, and restripped
(105, 0.2 mm) to azeotropically remove the last traces of
water. The reaction was then cooled to 65C and 792 g (8.55
moles) epichlorohydrin was added and the reaction heated to
reflux (~ 120C) for three hours. The excess epichlorohydrin
was then vacuum stripped at 120 (0.05 mm) to yield ~1450 g
of the crude glycidyl ether.
Part C: N,N'-Bis[3-(p-polyisopropylphenoxy)-2-hydroxypropyl]
ethylene diamine
Part C of Example 1 was repeated in all essential
respects except for substitution of the polyisopropyl (PIP)
glycidyl ether adduct of Part B above for the polyisobutene
phenol/epichlorohydrin adduct of Part B of Example 1. The pro-
duct may also contain N,N-diadduct and N or N' monoadduct.
EXAMPLE 3
The procedures of Example 2 were repeated in all
essential respects except that only one equivalent of ethylene
diamine was reacted with the polyisopropylphenyl glycidyl ether
adduct. The product was primarily the N-monoadduct of the
formula:
- 41 -
- 1~ 7 7'~
OH
PIP ~ OCH2CHCH2NHCH2CH2NH2
where PIP is the polyisopropyl substituent.
EXAMPLE 4
Octylphenol/Epichlorohydrin/Ethylene Diamine Adduct
To a 3-liter, 4-nec~ed round-bottomed flask fitted
with a condenser, addition funnel, stirrex, and thermometer
is charged 418 g. (2.0 moles) octylphenol. A 50% aqueous NaOH
solution (160 g., 2.0 moles) is then added and the mixture
heated with stirring to reflux and held there 0.5 hours. The
mixture is then vacuum-stripped at 100C (0.5 mm) to remove
water, charged with 50 g. toluene, and restripped (105, 0.5
mm) to azeotropically remove the last traces of water. The
reaction is then cooled to 65C and 925 g. (10 moles)
epichlorohydrin is added and the reaction heated to reflux
(about 120C~ for three hours. The excess epichlorohydrin is
then vacuum stripped at 120C (0.1 mm) to afford the crude
glycidyl ether intermediate.
To the crude glycidyl ether is added 300 cc xylene.
The reaction mixture is then heated to 150C. Ethylene diamine ;~
(60.1 g, 1.0 mole) is added over a two hour period, and the
reaction is held at 150C for an additional two hours. The
reaction mixture is filtered and stripped (150C, 0.1 mm). The
reaction product is a useful multipurpose additive for hydro-
carbon fuels and lubricating oils in accordance with the inven-
tion and has the following structure:
~ OH H .~ OH
~I H17C8 ~ 0CH2CHCH2~1CH2CH2NCH2CHCH20 ~ C8H17
R R6
4~ _
~077Z~;8
where R is H or -C8H17.
Although the N,N' structure is shown above, it will
be understood that the product may also be the N,N structure
or a mixture of the N,N' and N,N structures.
EXAMPLE 5
The procedure of Example 4 is repeated in all essential
respects except for substitution of nonylphenol for octylphenol
and mole ratio of nonylphenol/epichlorohydrin intermediate to
ethylene diamine, to afford products predominating in mono, di,
tri or tetra adducts identified by the following structural
formula:
~ OH (H) (H) OH
/~\ I ~ I P I q~ I /='\ \
\~19 9~ H2CHCH,~) NCH2CH2N ~12CHCH20~ ,~y
Additive x y p q
, . .
Mono adduct1 0 1 2
Di adduct2(1) 0(1) 0 2
l Tri adduct 2 1 0
¦ 20 Tetra adduct 2 2 0 0
EXAMPLE 6
N-(3-Aminopropyl)-Morpholine Adduct With Polypropylphenyl Glycidyl
I Ether
¦ A one-liter, 4-necked flask was charged with 370 g.
(0.46 moles) of a polyisopropylphenol glycidyl ether (prepared
;¦ as in Example 2, Part B), 81.2 g. (0.56 moles) N-(3-aminopropyl)
morpholine and 350 cc xylene. The flask was fitted with a
stirrer, condenser, and thermometer. The reaction was heated
. at 150C for 5 hours, then vacuum stripped at 150C (0.1 mm).
The residue was diluted with 400 cc toluene and washed with a
solution of 300 cc water, 100 cc saturated NaCl solution, and
~Ij .
~ - 43 -
`:
~ 10772f~8
300 Cc n-butanol. The washed organic fraction was vacuum stripped
at 120, and then filtered hot to afford 360 g product (2.28%
~ basic nitrogen). The product is a multipurpose additive when
t used in a hydrocarbon fuel or lubricating oil either alone or in admixture with a polyalkylene phenol.
A ~ EXAMPLE ?
3-Aminomethyl Pyridine Adduct With Polypropylphenyl Glycidyl
Ether
A one-liter, 4 necked flask was charged with 370 g.
(0.46 moles) of a polyisopropylphenyl glycidyl ether (prepared
as in Example 2, Part B), 60.8 g. (0.56 moles) 3-aminomethyl-
pyridine, and 250 cc xylene. The flask was fitted with a
stirrer, condenser, and a thermometer. The reaction was re-
fluxed at 135-40 for 5 hours. The reaction product was then
vacuum stripped at 120, dissolved in 400 cc toluene, and ;
washed with a mixture of 300 cc saturated salt solution and
300 cc n-butanol. The product was further washed with 300 cc
water, vacuum stripped at 110C (0.2 mm), and filtered hot to
afford 327 g. product (2.56% basic nitrogen). The product is
a multipurpose additive when used as described in Example 6
and this specification.
,,,
EXAMPLE 8
-j 2-Aminoethylaminoethanol Adduct with Polypropylphenyl Glycidyl
Ether
' 'I
A one-liter, 4-necked flask was charged with 370 g
l (0~46 moles) of a polyisopropylphenyl glycidyl ether (prepared
- as in Example 2, Part B), 60 g. (0.56 moles) 2-aminoethyl-
~ aminoethanol, and 250 cc xylene. The flask was fitted with a
;~I stirrer, condenser, and a thermometer. The reaction was heated
S hours at 150C, then vacuum stripped at 150 (0.1 mm). The
product was then diluted with 250 cc toluene, and washed with
'!' a mixture of 300 cc saturated salt solution and 300 cc n-butanol.
.
, ~
~ 44
: ~ ... .
.. . .
. ~.
1~ 7 7Z ~ ~
The product solution was rewashed with hot water, vacuum
stripped at 120, and filtered hot to afford 318 g. of product.
EXAMPLE 9
Aniline Adduct with Polypropylphenyl Glycidyl Ether
A one-liter, 4 necked flask was charged with 362 g.
(0.45 moles) of a polyisopropylphenyl glycidyl ether (prepared
as in Example 2, Part B), 52 g. (0.56 moles) aniline, and 250
cc xylene. The flask was fitted with a stirrer, condenser,
and a thermometer. The reaction was heated 5 hours at 150
then vacuum stripped at 150 (0.15 mm). The product was dis-
solved in 300 cc toluene and washed with a mixture of 300 cc
saturated salt solution and 200 cc n-butanol. The product
was fur~her washed with 300 water, vacuum stripped at 120,
and filtered hot to af~ord 328 g. of product.
EXAMPLE 10
Dimethylethylenediamine Adduct with Polypropylphenyl Glycidyl
Ether
A two-liter, 4 necked flask was charged with 326 g
(0.4 moles) of a polyisopropylphenyl glycidyl ether (prepared
as in Example 2, Part B), 70.5 g (0.8 moles) unsym. dimethyl-
ethylenediamine, and 225 cc xylene. The flask was fitted with
a stirrer, condenser, and a thermome'cer. The reaction was
heated 5 hours at 120, then vacuum stripped at 120 (0.2 mm).
The product was dissolved in 400 cc toluene and washed with a
mixture of 400 cc hot water, 80 cc n-butanol, and 6 g 50% NaOH.
The organic fraction was rewashed with 400 cc water (four times),
then vacuum stripped at 120 (0.25 mm) and filtered hot to
, afford 313 g. of product (2.30% basic nitrogen).
EXA~IPLE 11
Hexylamine Adduct with Polypropylphenyl Glycidyl Ether
A two-liter, 4 necked flas~ was charged with 320 g.
- 45 -
. . , . ~. ,.
~^ 1077Z68
(0.4 moles) of a polyisopropylphenyl glycidyl ether (prepared
as described in Example 2, Part B), 147 g. (1.4 moles) hexyl-
amine, and 225 cc xylene. The flask was fitted with a stirrer,
condenser, and thermometer. The reaction was heated 5 hours
at 120, then vacuum stripped at 120 (0.15 mm). The product
was dissolved in 400 cc toluene and washed with a mixture of
400 cc warm, saturated salt solution, and 6 g 50% NaOH. The
organic fraction was rewashed with water, then vacuum stripped
at 120C (0~15 mm) and filtered hot to afford 315 g. of product
0 (1.25% basic nitrogen).
OTHER MONOADDUCTS
.. . .
Certain of the additives of the invention alternatively
may be defined by the following formula (V): -
OH
R ~ O - CH2 - 1H - CH2 ~ NH (X - Y) zH (~)
R~ :
i in which R is a hydrocarbon radical having a molecular weight
ranging from about 200 to 1500, R' is hydrogen or an alkyl
radical having from 1 to 4 carbon atoms, X is a divalent hydro-
carbon radical having from 2 to 6 carbon atoms, Y is NH or O
(oxy), and z has a value from 1 to 10, preferably 1 to 6.
. It will be apparent from formula V that such compounds
are the monoadducts resulting from the condensation reaction
between a glycidyl ether of formula I and an amine or amino-
,.
~ alcohol in such proportions as to avoid substitution on more
., .
,, than one active nitrogen atom of the amine or aminoalcohol (if
the:amine or aminoalcohol contains more- than one active nitrogen
atom). Suitable amines and aminoalcohols include the alkylene
30 polyamines and hydroxy-substituted amines such as ethylene di-
amine, diethylenetriamine, triethylene tetramine, tetraethylene
- 46 -
107726~
pentamine, trimethylenediamine, tetramethylenediamine, penta-
ethylene hexamine, N-hydroxyethyl ethylene diamine monoethanol-
amine, and the like.
Accordingly, the monoadducts of formula V result
from the reaction of such amines or aminoalcohols in a mole
ratio of amine or aminoalcohol to glycidyl ether of formula I
of at least 1:1, preferably in molar excess, of the order
of 2:1 or more.
Preferred compounds of formula V are those wherein
X is -CH2CH2, Y is -NH-, R has a molecular weight ranging
from 200 to 1500, z has a value from 2 to 5. More preferably,
R has a molecular weight ranging from 250 to 1200 when the
adduct is used in a motor fuel such as gasoline, or 300 to
1000 when the adduct is used in a mineral oil composition com-
prising a mixture of hydrocarbons boiling in the range from
about 80 to 1000F.
The following examples illustrate the foregoing
monoadducts. These adducts are useful multipurpose fuel and
lubricating oil additives when used as previously described.
The Mn below the structure refers to the R6 substituent.
EXAMPLE 12
~~~~~~ OH
R6 ~ 0CH21HCH2NHCH2CH2NH2
where R is polyisopropyl (Mn ~ 575)
To a 3-liter, four-necked round-bottom flask fitted
with a condenaer, addition funnel, stirrer and thermometer was
charged 560 g. (0.76 moles) of the polyisopropylphenol pre-
pared in Part A of Example 2. A 50% NaOH solution (61.0 g.,
0.76 moles) was then added and the mixture heated with stirring
- 47 -
10~7Z~i8
to reflux (118C~) and held there for 0.5 hours. The mixture
was then vacuum stripped at 100 to remove water and cooled
to 60. Epichlorohydrin (352 g, 3.8 moles) was then added and -
the reaction heated to reflux (~ 120C) for 3 hours. The
reaction was vacuum stripped at 120C and diluted with 250 cc
~'~ xylene. Ethylene diamine (230 g, 3.8 moles) was then added
and the reaction was refluxed (118-120C) 3 hours. The reaction
~ mixture was vacuum stripped at 120C and diluted with 750 cc
:~ toluene and 750 cc saturated aqueous NaCl solution. Enough
` 10 NaOH solution t3.4 g. of 50% solution) was then added to make
the aqueous phase just alkaline and the mixture was heated with
stirring to 80C. The layers were then separated and the aqueous
layer discarded. The solution was then washed three more times
; at 80C with 750 cc saturated NaCl solution, vacuum stripped,
;l and filtered hot. The yield was 618 g. (95.3%), % basic
~j nitrogen = 2.51, of the monoadduct whose struct~re is given
above. EXAMPLE 13
R6 ~ OCH2CNC~2~CH2c~
where R is polyisopropyl (Mn ~860)
.:
The procedure of Example 2, Part A, was repeated in
all essential respects except for substitution of 1720 g.
(2.0 moles) of "Ampol" C60 polypropylene for the "Ampol" C20
ii of Example 2. The yield was 1810 g. (95%) polyisopropylphenol
(Mn about 1232).
To a 3-liter, four-necked round-bottom flask fitted
;l with a condenser, addition funnel, stirrer and thermometer
were charged 950 g (0.76 moles)-of the polyisopropylphenol
prepared above. A 50% NaOH solution (61.0 g, 0.76 moles) was
., .
- 48 -
,
.~ ~ . .. ..... . .
...... . . . .
:'` ' ~ . ~ : , .
. ~ .
~077Z~
then added and the mixture heated with stirring to reflux (118C)
and held there for 0.S hours. The mixture was then vacuum
stripped at 100C to remove water and cooled to 60C. Epi-
chlorohydrin (352 g, 3.8 moles~ was then added and the reaction
heated to reflux (^-120C) for 3 hours. The reaction was
vacuum stripped at 120C and diluted with 250 cc xylene. Ethanol
amine (46 g, 0.76 moles) was then added and the reaction was
refluxed (118-120C) 3 hours. The reaction mixture was vacuum
stripped at 120C and diluted with 750 cc toluene and 750 cc
; 10 saturated aqueous NaCl solution. Enough NaOH solution (3.4 g.
of 50% solution) was then added to make the aqueous phase just
` alkaline and the mixture was heated with stirring to 80C. The
layers were then separated and the aqueous layer discarded.
The solution was then washed three more times at 80 with 750 cc
saturated NaCl solution, vacuum stripped, and filtered hot.
The yield was 910 g. (87%), % basic nitrogen = 0.5, of the
; monoadduct whose structure is set forth above.
EXAMPLE 14
OH
R6 ~ CH2CHCH2NHCH2CH2NH2
where R is polyisopropyl (Mn ~860)
The procedures of Example 12 were repeated in all
essential respects except for substitution of "Ampol" C60
polypropylene (1720 g, 2.0 moles) for "Ampol" C20. The yield
of polyisopropylphenol was 1810 g. (95%), Mn about 1232. The
yield of monoadduct of the above structure was 916 g. (88%),
; % basic nitrogen = 0.8.
.,: .
. ~
- 49 -
10~7Zf~
~ EXAMPLE 15
:,
OH
R ~ OcH2cHc~2N~cH2cH2oH
where R is polyisopropyl (Mn-v575)
The proceduresof Example 12 were repeated in all
essential respects except for substitution of N-methylethanol
amine (57 g, 0.76 moles) for ethylene diamine. The yield of
monoadduct of the above structure was 485 g. (79%), % basic
nitrogen = 0.9.
EXAMPLE 16
. .
~ R ~ oCH2C~C~2N~C~2C82N(CH3)2
:, .
where R is polyisobutyl (Mn ~660)
To a 300-ml. 3-necked flask equipped with a thermo-
meter, mechanical stirrer and reflux condenser with Dean-Stark
'20 trap was charged 99.0 g (0. 15 mole) of polyisobutylene ("Indopol
H-35,"* Amoco), 14.1 g (0.15 mole) of phenol, 28 ml. of hexane
and 10.3 g. of "Amberlyst 15" acid catalyst. The stirred
mixture was heated at reflux (pot temperature 96-99C) under
a nitrogen atmosphere for 12 hours. Gravity filtration through
; a glass wool plug at 70C followed by a 10 ml. hexane bead
rinse gave a clear, essentially colorless filtrate. Vacuum
concentration to a pot temperature of 150C at 1 mm. Hg afforded
101.8 g. (90~ yield) of product polybutenephenol as a viscous,
golden brown oil having an Mn of 700 as determined by oxygen
analysis and W spectral parameters. Volatiles collected
.
* Trademaxk of Amoco Chemical Company
** Trademark
- 50 -
1~'7~72~
amounted to 13.2 g while 10.3 g of "Amberlyst 15" were re-
covered.
The procedures of Example 12 were then repeated
in all essential respects except for substitution of the fore-
going polybutenephenol (530 g., 0.76 moles) for the polyiso-
propylphenol of Example 12 ~ and the substitution of N,N-dimethyl-
1,3-propane diamine (388 g., 3.8 moles) for the ethylene diamine
of Example 12A The product was a monoadduct of the above
structure.
EXAMPLE 17
R6 <~o-cH2cHcH2 (NHCH2 CH2 ) 2NH2
where R is polyisobutyl (Mn ~ 660)
To a 500 ml round-bottomed flask were charged 150 g.
(about 0.25 mole) of polyisobutyl phenylglycidyl ether (4.58%
oxygen by difference of C and H analysis, 5.19% direct), 104.5
g (1.01 moles) of diethylenetriamine, and 100 ml toluene. The
reaction mixture was stirred magnetically and, when the solution
was homogeneous, heating to just below reflux was begun. This
temperature was held for 16 hours. Toluene was then removed on
the rotary evaporator and the excess amine with the vacuum
pump. The yield of monoadduct of the above structure was 155 g.,
% basic nitrogen = 2~ 43.
- 51 -
