CA1077268A - Multipurpose and detergent fuel additive blend or mixture - Google Patents

Abstract

MULTIPURPOSE AND DETERGENT FUEL
ADDITIVE BLEND OR MIXTURE
Abstract of the Disclosure A new multipurpose carburetor detergent for addition to gasoline is disclosed and claimed. The novel multipurpose detergent material shows excellent activity as a carburetor detergent, induction system detergent (% deposit reduction), combustion chamber detergency and, in addition, provides effective rust inhibition when used in automotive gasoline fuels at low concentrations. The new composition of matter is a blend or mixture of a poly-isobutene phenol/epichlorohydrin/amine adduct and an ester of a polycarboxylic acid, preferably a mixed ester of a dicarboxylic acid. The novel amine product may also be described as the reaction product of a polyisobutene phenol with epichlorohydrin followed by amination with ethylene diamine.

Description

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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.

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- 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.
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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 . ' . . .

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(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:
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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 .
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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.

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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.

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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
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(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 , .
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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.

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The gasolin~ used in the BBCDT-KC test is an Ms-o8 gasoline having the following properties:
Gravity:

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.

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(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(~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 ~,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 .' ' ,. .

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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~

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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 ,~, 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-;, . . .
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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:
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2 moles ~ Rl + H2NCH2CH2NH

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).
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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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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
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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:
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*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.

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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

., . . 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". .
.

.
. ., .

; .
. ~

; ' ' ' .

. ~ .

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 .~ .

.

~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 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.

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.

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 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 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.

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-~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.

` ~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~

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.

';

~077Z~

~ OH
PIBH35-~0~ 0-CH2CHCH2 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 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 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

, ' ~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 ~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.) 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.

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.

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:

- 1~ 7 7'~

OH
PIP ~ OCH2CHCH2NHCH2CH2NH2 where PIP is the polyisopropyl substituent.

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

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.

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 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.
,,, -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.

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.

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.

. . , . ~. ,.

~^ 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 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.

~~~~~~ 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 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 ., .

, .~ ~ . .. ..... . .
...... . . . .
:'` ' ~ . ~ : , .
. ~ .

~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.

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.
.,: .
. ~

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.

. .

~ 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 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.

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.

Claims (43)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE PROPERTY
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. As a novel composition of matter, a multipurpose gasoline fuel additive comprising a mixture or blend of (a) an additive of the formula:

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.

2. A composition of matter according to claim 1 wherein the polycarboxylic acid ester is a mixed ester.

3. A composition according to claim 1 wherein the alkyl group is polyisobutyl or polyisopropyl.

4. A composition according to claim 1 wherein the alkyl group is polyisobutyl.

5. A composition of matter according to claim 1 wherein the polycarboxylic acid ester is a mixed ester com-prising a dicarboxylic mixed acid ester containing a C1 to C20 alkyl group and an alkyl phenoxy (alkyl of C4 to C20) polyethoxy ethanol containing 1 to 20 moles of condensed ethylene oxide.

6. A composition according to claim 5 wherein the mixed 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.

7. A composition of matter according to claim 1 wherein the (a) component has the following formula:

wherein PIBH35 is polyisobutyl of number average molecular weight of about 670, and R1 is either PIBH35 or hydrogen.

8. A composition according to claim 4 wherein the polyisobutene portion of (a) has a number average molecular weight in the range of about 500 to 2000.

9. A novel fuel composition of matter compris-ing (a) a major amount of gasoline and (b) a minor amount of the additive mixture Or claim 1 in the gasoline.

10. A novel composition or matter comprising (a) a major amount of gasoline and (b) incorporated in the gasoline a minor amount of the additive mixture of claim 2.

11. A novel composition of matter comprising (a) a major amount of gasoline and (b) incorporated or mixed therein a minor amount of the additive mixture of claim 2 wherein the amine adduct is present in an amount of about 20 to 300 ppm and the mixed ester is present in an amount or about 100 to 650 ppm.

12. A novel composition of matter comprising (a) a major amount of gasoline and (b) incorporated in the gasoline the additive mixture of claim 5 wherein the amine adduct is present in the gasoline in an amount of about 20 to 300 ppm and the mixed ester is present in the gaso-line in an amount of about 100 to 650 ppm.

13. A novel composition of matter comprising (a) a major amount or gasoline and (b) incorporated or mixed in the gasoline a minor amount of the additive mixture of claim 6 and wherein the amine adduct is present in the gasoline in an amount of about 20 to 300 ppm and the adi-pate ester is present in the gasoline in an amount or about 100 to 650 ppm.

CLAIMS SUPPORTED BY THE SUPPLEMENTARY
DISCLOSURE

14. 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 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.

15. A multipurpose additive for a hydrocarbon fuel, a lubricating oil, or a mixture or a hydrocarbon fuel and a lubricating oil, comprising a mixture or:

(1) the reaction product or (a) a glycidyl ether compound or the formula where R6 is an aliphatic hydrocarbon group having at least 8 carbon atoms and m is 1-3, and (b) an amine having at least one amino group having at least one active hydrogen atom, and (2) a polycarboxylic acid ester wherein the ester group is the residue of a C1-C20 alkanol, an alkyl phenoxy poly-ethoxy ethanol, or the mixed residue of said alkanol and said ethanol.

16. The additive of Claim 15 wherein said amine has the formula:

where R1, R2 and R3 independently are hydrogen, C1-C6 alkyl or C.-C6 alkyl substituted by -NH2 or -OH R4 is a C1-C6 divalent hydrocarbon radical, R5 is hydrogen or C1-C6 alkyl, and n is 0 to about 5; and the ester group of the ester component (2) is a mixed residue of a C1-C20 alkanol and an alkyl phenoxy polyethoxy ethanol.

17. The additive of Claim 16 wheren R1, R2 and R3 are hydrogen and R4 is ethylene or propylene.

18. The additive of Claim is wherein the mole ratio of said glycidyl ether compound to said amine is 2:1 to about 4:1, R6 is polyalkylene having a molecular weight of about 500 to 2000, and m is 1-2.

19. The additive of Claim 18 wherein said amine has the formula:

where R1, R2 and R3 independently ar hydrogen, C1-C6 alkyl or C1-C6 alkyl substituted by -NH2 or -OH, R4 is a C1-C6 divalent hydrocarbon radical, R5 is hydrogen or C1-C6 alkyl, and n is 0 to about 5.

20. The additive of Claim 19 wherein R1, R2 and R3 are hydrogen, R4 is ethylene or propylene, and the ester group of the ester component (2) is a mixed residue

21. The additive of Claim 15 wherein the mole ratio of said glycidyl ether compound to said amine is 2:1 to about 4:1, R6 is nonyl, and m is 1-2.

22. The additive of Claim 21 wherein said amine has the formula where R1, R2 and R3 independently are hydrogen, C1-C6 alkyl or C1-C6 alkyl substituted by -NH2 or -OH, R4 is a C1-C6 divalent hydrocarbon radical, R5 is hydrogen or C?-C6 alkyl, and n is 0 to about 5.

23. The additive of Claim 22 wherein R1, R2 and R3 are hydrogen and R4 is ethylene or propylene.

24. The additive of Claim 15 wherein R6 is polyisobutylene or polyisopropylene and said R6 has a molecular weight of about 500 to 2000, m is 1-2, the mole ratio of said glycidyl ether compound to said amine is 1:
to about 2:1, and said amine is selected from ethylene diamine, N-(3-aminopropyl) morpholine, 3-aminomethyl pyridine, 2-aminoethylaminoethanol, N,N-dimethylethylenediamine, aniline and hexylamine.

25. The additive of Claim 15 wherein R6 is nonyl, m is 1-2, the mole ratio of said glycidyl ether compound to said amine is 1:1 to about 4:1, and said amine is selected from ethylene diamine, N-(3-aminopropyl) morpholine, 3-aminomethyl pyridine, 2-aminoethylaminoethanol, N,N-dimethylethylenediamine, aniline and hexylamine.

26. The additive of Claim 15 wherein reaction product (1) is selected from and mixtures thereof, wherein R6 is polyisobutyl of number average molecular weight of about 670 and R7 is hydrogen or the same as R6.

27. A composition comprising a major proportion of gasoline, and a minor amount of the additive of Claim 15 in amounts of said reaction product (11 of about 20-300 ppm and said polycarboxylic acid ester (2) of about 100-650 ppm.

58 23. The additive of claim 15 wherein the alkyl group of the alkyl phenoxy polyethoxy ethanol is C4-C20 and said alkyl phenoxy polyethoxy ethanol contains 1-20 moles of condensed ethylene oxide.

29. The additive of claim 23 wherein the ester component (2) is an ester of adipic acid, isodecanol, and octyl phenoxy polyethoxy ethanol containing an average of 5 moles of condensed ethylene oxide.

30. A composition comprising a blend of (A) a major proportion of a hydrocarbon fuel and 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 where R2iis a benzene ring having attached thereto at least one aliphatic hydrocarbon substitutent, and (b) an amine having at least one amino group having at least one active hydrogen atom; and (2) a polycarboxylic acid ester.

31. A composition comprising a blend of (A) a major 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 addi-tive comprising a mixture of:
(1) the reaction product of (a) a glycidyl ether compound of the formula where R6 is an aliphatic hydrocarbon group having at least 8 carbon atoms and m is 1-3, and (b) an amine having at least one amino group having at least one active hydrogen atom, and (2) a polycarboxylic acid ester wherein the ester group is the residue of a C1-C20 alkanol, an alkyl phenoxy poly-ethoxy ethanol, or the mixed residue of said alkanol and said ethanol.

32. The composition of Claim 31 wherein said amine has the formula:

where R1, R2 and R3 independently ar hydrogen, C1-C6 alkyl or C1-C6 alkyl substituted by _ NH2 or -OH, R4 is a C1-C6 divalent hydrocarbon radical, R5 is hydrogen or C1-C6 alkyl, and n is 0 to about 5; and the ester group of the ester component (2) is a mixed residue of a C1-C20 alkanol and an alkyl phenoxy polyethoxy ethanol.

33. The composition of Claim 32 wherein R1, R2 and R3 are hydrogen and R4 is ethylene or propylene.

34. The composition of Claim 31 wherein the mole ratio of said glycidyl ether compound to said amine is 2:1 to about 4:1, R6 is polyalkylene having a molecular weight of about 500 to 2000, and m is 1-2.

35. The composition of Claim 34 wherein said amine has the formula:

where R1, R2 and R3 independently are hydrogen, C1-C6 alkyl or C1-C6 alkyl substituted by -NH2 or -OH, R4 is a C1-C6 divalent hydrocarbon radical, R5 is hydrogen or C1-C6 alkyl. and n is 0 to about 5.

36. The composition of Claim 35 wherein R1, R2 and R3 are hydrogen, R4 is ethylene or propylene, and the ester group of the ester component (2) is a mixed residue of a C1-C20 alkanol and an alkyl phenoxy polyethoxy ethanol.

37. The composition of Claim 31 wherein the mole ratio of said glycidyl ether compound to said amine is 2:1 to about 4:1, R6 is nonyl, m is 1-2, and the ester group of the ester component (2) is a mixed residue of a C1-C20 alkanol and an alkyl phenoxy polyethoxy ethanol.

38. The composition of Claim 37 wherein said amine has the formual:

where R1, R2 and R3 independently are hydrogen, C1-C6 alkyl or C1-C6 alkyl substituted by - NH2 or -OH, R4 is a C1-C6 divalent hydrocarbon radical, R5 is hydrogen or C1-C6 alkyl, and n is 0 to about 5.

39. The composition of Claim 38 wherein R1, R2 and R3 are hydrogen and R4 is ethylene or propylene.

40. The composition of Claim 31 wherein R6 is polyisobutylene or polyisopropylene and said R6 has a molecular weight of about 500 to 2000, m is 1-2, the mole ratio of said glycidyl ether compound to said amine is 1:1 to about 2:1, and said amine is selected from ethylene diamine, N-(3-aminopropyl) morpholine, 3-aminoethyl pyridine, 2-aminoethylaminoethanol, N,N-dimethylethylenediamine, aniline and hexylamine.

41. The composition of Claim 37 wherein R6 is nonyl, m is 1-2, the mole ratio of said glycidyl ether compound to said amine is 1:1 to about 4:1, and said amine is selected from ethylene diamine, N-(3-aminopropyl) morpholine, 3-amino-methyl pyridine, 2-aminoethylaminoethanol, N,N-dimethylethylene-diamine, aniline and hexylamine.

42. The composition of Claim 31 wherein the alkyl group of the alkyl phenoxy polyethoxy ethanol is C4-C20 and said alkyl phenoxy polyethoxy ethanol contains 1-20 moles of condensed ethylene oxide.

43. The composition of Claim 42 wherein the ester component (2) is an ester of adipic acid, isodecanol, and octyl phenoxy polyethoxy ethanol containing an average of 5 moles of condensed ethylene oxide.