CA1076802A - Multipurpose fuel additive and mixture or blend - Google Patents

Abstract

D.N. 74-46A
MULTIPURPOSE FUEL ADDITIVE MIXTURE OR BLEND

Abstract of the Disclosure A new multipurpose carburetor detergent mixture or blend for addition to gasoline is disclosed and claimed.
The novel multipurpose detergent composition of matter shows excellent activity as a carburetor detergent, induc-tion 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 mixture or blend of a polyisobutene phenol/epichlorohydrin/
amine adduct and a polyisobutene phenol. 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

- ~0768~
.
THE DISCLOSURE
This invention relates to a novel multipurpose detergent mixture or blend for addition to gasoline. The novel amine and polyisobutene phenol multipurpose detergent composition of matter shows excellent activity as a car-buretor detergent~ induction system detergent (~ deposit reduction),-combustion chamber detergency and~ in addi-tion~ provides effective rust inhibition when used in automotive gasoline fuels at low concentrations.
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 polyisobutene phenol, as an additive for gasoline, and, more preferably~ about 50 to 100 ppm of the amina adduct blended or mixed with 200 to 300 ppm of the polyisobutene phenol, as an additive for gasoline. The ppm figures are based on their use in gasoline, the gasoline being a dis-tillate hydrocarbon fuel having a major proportion of a hydrocarbon base fuel distilling within the gasoline dis-tillation range. Stated otherwise, the novel composition of matter (of this application), for addition to gasoline, `~
comprise~ 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 a polyiso-butene phenol and~ more preferably, about l5 lbs. to 25 lbs. of the amine adduct b]ended or mixed with 50 lbs. to 75 lbs. of the polyisobutene phenol.
The novel composition of matter of this applica- ;
tion is a mixture or blend of a polyisobutene phenol/

~ .

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, , ~ ; ~ . : , " :. , , , . - .

1~768~2 .. .. . . i . , ; epichlorohydrin/amine adduct and a polyisobutene phen~
The amine adduct may also be described as the reaction product of a polyisobutene phenol with epichlorohydrin 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 buildup of combustion chamber deposits. It is another object of the present invention to provide a detergent fuel which will maintain a low level of hydrocarbon and 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 ;~ ;
detergent fuel which has other desirable properties~ such `~ ~
: . ~.
as rust and corrosion protection, water demulsibility `
properties, anti-icing prop~rties, etc. It is a further ob-ject of the present invention ~o 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--isobutene phenol, of about 120 to 950 parts per million (ppm on a weight basis in the gasoline) and, more prefer-ably~ 260 to 400 ppm.
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ll~7680;~

There are, Or 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 of 4000 ppm; or if used at the use leYels 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 together with the polyisobutenephenol 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 250 to ~00 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 pre-ferred products are the N,~ Bis[3-(p-H35-polyîsobutyl-20 phenoxy)-2-hydroxypropyl] ethylene diamine blended ~ith ~
a polyisobutene phenol. The PIB is our abbreviation for ~ i a polyisobutene generically of any molecular weight. The H35 is the commercial designation for Amoco's polyisobutene of Min ~'670. The structural formula for the preferred product is as follows:

' -3a- ~
~.

OH OH
O-CH2cHcH2NHcH2~I2NHc~2cHcH2-l P~BH35 PIBH35 The PI ~ 35 component (which can also be written simply as R) may have a number average molecular weight (~) of about 500 to 2000 and~ more preferably, about 6CO
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 polyisobutene -radical of number a~erage molecular weight of about 500 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- `~
I functional additive composition for addition to a leaded~
¦ - low leadj or unleaded gasoline, i.e., to a distillate ! 15- hydrocarbcn fuel comprising a major proportion of a hydro-carbon base fuel distilling within the gasoline distilla-ti~n range. This additive provides carburetor, induction system and combustion chamber detergency, rust inhibition and good handling properties to a higher degree than nor-mally found with typical current first generation multi-purpose carburetor detergents of the alkyl ammonium phosphate or polyolefin succinimide type. The increased performance we are seeking is necessitated in part by the 10768~Z .~

advent of emissions control hardware which must,re~ain ,.
deposit-free if the new automobiles are to remain within the EPA emissions specifications for 50,000 miles as re-quired for vehicle certification.
Although there are many carburetor detergents~
on the market~ to our knowledge~ only one, Chevron F-310 9 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 ~OOO ppm 9 and that may exceed the indus-try's handling or economic capabilities. Therefore9 we feel there is currently no additive available which is completely acceptable in terms of economics, treating level and performance.
The pre~erred chemical amine adduct gasoline additive c ~ ound disclosed in C~dian Application 242,180 is pre-pared 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 et~ylene diamine to form the desired product.

`I . :`
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~ 07 6 OH 1) NaOH

P B H35 + ~ Acid C~talvs~ PI ~3 ~ OH 2) CH ClCH- ~n~

~O\ ~ :
H35-- ~CH2CH CH2 ~ 1/2 NH2CH2CH~NH ~ :

OH OH

PIBH3 ~ H2CHCH2NHCH2CH2NHC~2CHCH2 0 ~--?I

~1 R~
(Preferred amine adduct product disc'osed in Application ~ ;
242,180, where Rl is PIBH35 or H.) Our experience with a large number of pr~duct 5 compounds of this type, as shown in the reaction sch~e i;
above, indicatès that a polyisobutene in the moiecular weight range of 500-2000 and a polyamine of t~.e et~yle~e diamine~ diethylene triamine type pr~duces the best bal-ance of properties in terms of detergency, rust innibi'ion and handling.
Table I present~ data comparing the preferred pro-duct 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 whioh indi-cate the percent reduction in deposits versus untreated gasolineshows that the preferred product greatly improves the perfor-mance of untreated gasoline and provides performance comparable ~.

to F-310 at a much reduced treating level.

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Table II presents data ~howing the ability of the preferred product of the present invention to control the increase in the octane nu~ber requirement of an engine. Although the mechanism`of activity is not firmly established, the additive presumably works by preventing the buildup of dèposits in the combustion chamber.
- TABLE II
OCTANE NU.~R RE~TJIRE`-~NT IN~RE~SE
Treating Level, *Octane Number (C) lbs.~1000 bbls in Requirement AdditiveGasoline (Nonleaded) _ I ncrease 10 - Untreated - 10 Base Gasoline Preferred 75 Product (PP) (Amine Adduct where Rl is ~ Dr P~H35 ~As measured by the Combustion Chamber Deposit Engine Test ~he Blowby Carburetor Detergency Test above~
- showin~ % deposit reductionj is described below ~-08 gasoline is used in the Blowby Carburetor Detergency Keep Clean Engine Test (% deposit 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 E~ine Test.

2~ ENGINE TEST E~TALUATION OF k~LTIPURPOSE l~;
CAR3URETOR DETE~G~TS
(A! BLO~BY C4~BT~ETOR DETERr-ENCY KEE~ C~EAN ENGI~TE EST
- En~ine Test Procedure The Blowby Carburetor Detergency Keep Clean Engine Test (BBCDT-KC) measures the ability of a gasoline àdditive to keep clèan the carburetor throttle bo~y area, and is run in a 1970 Ford 351 CID V-8 engine equi?ped ' ' , ' :~.
. ' 6 8~ Z

by means of a special "Y" intake manifold with t~o one-barrel- carburetors, which can be independently adjusted and activated. With this arrangement, a separate test fuel can be evaluated by each carburetor which feeds four of the eight cylinders via the non-interconnected intake manifold. -The carburetors are modified with removable aluminum sleeves in order to facilitate weighing of the deposits which accumulate in the throttle body area. The severity of the test is adjusted to an appropriate level by recycling the entire amount of blowby gases, approxi-mately 90-110 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 adjusted during the first hour of operation of means of intake mani~old differential pressure and C0 exhaust gas analysis. The fo110wing test cycle and operating con-ditions are employed:
Test Cycle: .
Phase I 650 engine rpm~ 8 min.
Phase II 3000 engine rpm, 1 min.
Test duration, hrs. 10 Intake air, F. 135 + 10 Jacket water, F. 190 + 10 Engine oil-sump~ F. 210 + 10 Percent C0 in exhaust 3.0 + 0.2 Blowby~ c.f.h. 90 - 110 `~
The weight (mgs.) of deposits accumulated on the aluminum sleeve is measured, and the average value of four tests per additive or additive mixture is reported.

_9_ ., j . ...

~ 68~Z

The gasoline used in the BBCDT-KC test is an MS-o8 gasoline having the following properties:
Gravity:
API 59.7 Sp. gr. at 6Qo F. 0.74 ASTM D-86 distillation, F.:
~ .
I.B.P. 9 10~ 123 5% 205 0 90% 348 ~.P. 405 Percent recovered 98 Percent residue Percent loss 15 - Percent sùl~ur 0.11 Lead, gm./gal. 3.08 FIA composition:
Aromatics~ percent 23.1 Olefins~ percent 20.0 ~0 Saturates~ percent 56.9 Oxidation stability, minutes 600+
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, lS described below.
.
.

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1~7680Z

(B) IND~ICTION SYST~M DEPOSIT ENGINE TEST
En~ine Test Procedure The Induction System Deposit Test (ISDT) which is used to evaluate the ability of gasoline addit ves or mixtures of additives to control induction system deposits, is run using a new air-cooled~ single cylinder, ~ cycle~
2.5 ~.P. Briggs and Stratton engine for each test. The engine is run for 150 hours at 3000 rpm and ~.2 ft. lbs.
load? with a 1 hour shutdown every 10 hours to check the oil level. Carbon monoxide exhaust emission measurements - are made each hour to insure that a constant air to fuei (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 nu~lber requirement increase, the Co~ustion Chamber Deposit Englne Test~ is described below.
(C) COMBUSTION CHA`3~ DEPOSIT ENGINE TEST
En~ine Test Procedure The Combustion Chamber Deposit Engine Test ~-tCCDET) is used to evaluate the ability of a gasoline additive or mixture of additives to control or reduce the ~:
octane number require~ent increase (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 ~ydr~matic 350 transmission which is cor-nected to a 101~-2 WIG dynamometer equipped with a 200.3 lb.-ft.2 inertia wheel. The following test cycle and - ~ ~7 6 8~ Z

operating conditions are employed and are intended to simulate an urban taxi cab.
~st C~cle:
Phase I Start - idle~ 6~0-750 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 I~ 3rd gear, 10.0 sec.~ 2600 rpm Phase ~ 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 Jack~t water, F. 180 - Engine oil-sump~ F. 220 + 10 Octane number requirement is determined at 2 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 determined at trace knock in terms of primary reference fuels; i.e.
the engine is run on a series of blends of isooctane and n-heptane of known octane number until audible knock is - pçrceived. ~he lowest standardized octane number blend at which the engine does not knock is recorded as the - octane number requirement. Octane number requirement .. ..
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 description ,. . . . ; .
. : - . . . .

~ 68()2 of the Blowby Carburet~r Detergency Keep Clean Engine ~est, beginning a~ line ~2 Or page 8 of the specirication, refers to the results shown in Table I, column ~ on page 7~of the specification. The (B) test procedure, i.e., the description of the Induction System Dkposit Engine Test~ beginning at the top o~ page 11 of the specifica-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 Cha~ber Deposit Engine Test~ beginning at line 20 of page 11 o~ the speci-fication, refers to the results shown in Table II, column

3, on page 8 Or the specification.
One Or the unique features Or the products of this invention is that they are one of the few non-ionic compounds that provide a high degree of rust inhibition.
This is an important~feature in a gasoline additive since ionic rust inhibitors, i.e.~ carboxylic and phosphoric acid salts, tend to aggravate the problem of induction system deposits. In addition, a non-ionic or ashiess ~
20 rust inhibitor is a key-component in formulating an ash- ~ ;
less engine oil. Therefore, the products of this inven-tion may find utility as lubricant additives as well as gasoline ~uel additives. The general structure of the-novel com~ound$ Or the invention in Applica-tion No. 242,180 may be expressed as follows:
OH OH
CH2cHcH2~NHcH2c~ NHcH2cHc~2 R2 ~ 2 wherein n is an int~ger ol ~ro~ 1 to ~, and ., , ., ~ , . . . .

~L~'768~Z
wherein R2 is an alkyl substituted benzene ring, and whereinthe alkyl substituent (or substituents) is polyisobutyl or polyisopropyl of 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 H35 Phenol Reaction:

OH OH

+ Polyisobutene H3s Amberlyst 15 M.W. 94 ~ 660 ~ 754 -~
~M.W.=Molecular Weight) (Theoretical M.W.) ~ ~

The product is actually a mixture of alkylated -phenols with an average~molecular weight of 548 based upon -oxygen analysis (2.92%) and 556 calculated from UV spectral parameters.
The experimental procedure is described below.
To a 5-1. 3-necked flask equipped with a thermometer, mechanical stirrer and reflux condenser with Dean-Stark trap was charged 1920 g. (2.9 moles) of Polyisobutene H35 (Amoco), 564 g. (6 moles) of phenol, 200 g. of Amberlyst ~ 15 acid catalyst, and 550 ml. of hexane. The stirred mixture was heated at reflux (pot temperature 100-107C.) under a nitrogen atmosphere for 24 hours, during wh:ich time 5.4 ml. of water had separated. After cooling to 60-80C., the mixture was filtered to remove the resin 107t~8f~;~

beads~ 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~g).
(Part B) 1~2-Epoxy-3-[p-(H3 5-polyisobutyl)phenoxy]
propane - ~ ~
Reaction:
H

~3 + ClCH2CH--CH2 + NaOH Toluene 3 M W. ~75Lt 92.5 ~o OCH CH--CH
2 \0/ 2 > ~`Rl ~ NaCl ~ H20 ~ 810 To a ~-1. 3-necked flask fitted with a ther-10 mometer, mechanical stirrer, addition funnel and reflux condenser was charged 973 g. (1.75 moles based upon 2.92%
oxygen) of Polyisobutene H35 Phenol, 72 g. (1.75 moles - based upon 97.L~% assay) of sodium hydroxide pellets, 450 ml. of 2-propanol and 450 ml. OI toluene. The stirred 15 m~xture was heated under a nitrogen atmosphere at 8L~-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 70 C The reaction mixture was then cooled, filtered, 20 and the salt (107 g. dry) washed with toluene. The fil-, ~ - : . - . .
.-. ., .

107~8~2 trate was stripped (100 C./15 mm.) to give 10?5.3 g. of product residue.
(Part C) N~Nl-Bis[3-(p-H35-polyisobutylphenoxy)-2- ~
hydroxy~ro~yl~ eth~lene diamine ;
Reaction:

() !
2 moles ~ Rl ~ H2NCH2CH2NH2 Xylen~

M.W. ~810 60.1 . ' OH OH

CH2cHcH2NEcH2cH2NHcH2cHcH2 ~3,R~ 3,R

-PIBH3 5 P l BH3 5 ~-1680 A mixture of 1018.4 g. of the above epoxide, 122.6 g. (2rO4 mo es)- 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 ( 8 mm., pot temperature of 120 C.), there w~s obtained 1053~4 g. of turbid residue which was filtered through a bed of Celite 545 in a steam-heated Buchner .. .. . .
funnel to give clear~ yellow ViSCO'.lS product.
The product prepared in this way had 1.26% basic N (1.67% theory) and 5.26% 0 (3~81% theory).

-16~

1076~3~Z

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.
The polyisobutene phenol may have a number average molec-ular weight of about 500 to 3000 and~ more preferably, about 500 to 1500. The polyisobutene phenol is prepared in accordance with Example 1, Part A, described herein-above. Blends or mixtures of the amine adduct and the polyisobutene phenol, and proportions thereof, have been mentioned hereinbefore. (~ee, for example~ page 2 of the specification.) In Table III~ performance data of the blends or mixtures are shown.

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1~768~2 As can be seen from Table III~ the mixture of the amine adduct and the polyisobutene phenol compares very favorably with the amine adduct product~ per se, and with the Chevron-F-310, It should also be noted from Table III that the Chevron ~--310 is used at a much higher level (1000 lbs. per thousancl barrels of gasoline) than is the-amine adduct or the blend of the amine adduct and the polyisobutene phenolO .
The gasoline additive or àdditives or gasoline . fuel additive or additives of the present invention act to control spark plug fouling and thùs 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 polysisobutene 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 Pro-duct", 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;
however, the preferred produqt 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 , ., " ~, .
~ -19- -076~3Q~

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-tha case -where n is gr~ater than 1, more co~plex mixtures can form where alkylation can occur at any of the available nitrogen sites; such cases are taken to be covered by the present disclosure, The overall amount for use in gasoline of the new product or amine adduct (s) remains ¦;
the same no matter what the internal proportion or ratio J

or amount of (a) or (b) is. -I OH OH
~CH2CHCH2(NHCH2CH2)nNHCH2CHC\2 (a) - _ R~ Rz OH
R2 OC~2CHCH2~ , ¦ ., N(F~2GH2~I)nH (b~
R;~OCH2CHCH~

where n=l to 5 and R2 is a polyisobutyl or a polyisopropyl ~ I
substituted benzene ring as hereinbefore disclosed.
The polyisobutene phenol is used primarily for cost considerations and lowers the treating costs of the gasoline.
The polyisobutene phenol's principal function is for percent deposit reduction in the Induction System Test and in the vehicle where it ultimately will be used.
This application is related to copending, concurrent-ly filed, Canadian Patent Application 242,179 of Warren H.
Machleder and Joseph M. Bollinger, said application being entitled "Multipurpose and Detergent Fuel Additive Blend or Mixture".
This application is also related to copending, con-currently filed, Canadian Patent Application 242,180 of Warren j H. Machleder and Joseph M. Bollinger, said application being entitled "Multipurpose Fuel Additiven.
-19a~

.
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107~i~02 ~

SUPPLEMENTARY DISCLOSURE
The present invention, in one aspect, as described .-in the Principal Disclosure of this application, resides in .
a multipurpose gasoline fuel additive comprising a mixture or blend of -(a) an additive of the formula OH OH

CH2cHcH2(N~Ic~2cH2)nN~cH2cHc\2 : -R2 ~ 2 ~ ~
wherein n is an integer of from 1 to 5, and wherein R2 is an .-alkyl-substituted benzene ring, and ~b) a polyisobutene phenol. ~
A further, prefèrredj aspect of the invention as ~ ~;
described in the Principal Disclosure hereof, is a composition .
of matter as above, wherein the (a) component has the follow- -ing formula - ..
OH OH ;

-cH2cHcH2NHcH2cH2NHcH2cHcH2- 1 :
,- ~,Rl ~ Rl , ,~

wherein PIBH35 is polyisobutyl of number average molecular weight of about 670~ and Rl is either PIBH35 or hydrogen.
The :invention as set forth in the Principal Dis- :
closure hereof, in another aspect, resides in a motor fuel :
composition comprising ~ .~ ~ ~:

; (~) 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) ad~ix~d or f~ ...... .. .

~ 6~0;2 blended with about 100 to 650 ppm of the polyisobutene phenol.
I Now,-according ~o a further broad aspéct of the --prè~ent invention~ as set forth more fully hereinafter in this Supplementary Disclosure, there is provided a mult~urpose, additive for a hydrocarbon fuel, a lubricating oil, or a mix-ture 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 (R6~ OCH2CH - CH2 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 polyalkylene phenol. .
Also provided by the invention as described in this Supplementary Disclosure is a composition comprising a blend o~
(A) a major proportion by weight 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 multi~urpose ~:
additive comprising a mixture of (1) the reaction product of (a) a glycidyl ether compound of the formula ,. , f\.

( R6 ~ 0cH2cH - CH2 ~ ... ~`

where R6 is an aliphatic hydrocarbon group having at least 8 r 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 polyalkylene phenol.

:~, ' . ': ' .

~076~2 Thus, it has been found that the additives as orig-inally disclosed herein need not be restricted only to what is set forth in the Principal Disclosure, in the following respects:
(a) the amine reactants wh;ch may be used;
(b) the chain length of the alkyl group on the phenol;
(c) the extent of substitution of the glycidyl ether alkyl phenol on the amine; and ~ d) the number of alkyl substituents on the phenol.
Detergent motor fuel and lubricating oil addi-tives available today generally suffer from one or more deficiencies. ~ither they are used at very high concen_ trations, 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 cleanliness of the carburetor and other elements of the fuel induction system, ~uch as the intake valves and ports, and to reduce the octane requirement increase of an internal combustion engine by reducing the buildup of combustion chamber deposits . Another property is the ability of the additive to maintain a low level of hydro- ~-carbon and carbon monoxide exhaust gas emissions so that phosphorus-containing additives are not required. Still other desirable properties include rust and corrosion ~'"',, -22- ;

.~

1~768()2 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 substi-tuted phenols, epichlorohydrin and amines, and (2) a polyalkylene phenol show excellent carburetor, induction system and combustion cham~er 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 o the poly-alkylene phenol (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, com- `
prises on a 1000 barrels of gasoline basis, in the broad range, about 5 lbs. to 75 lbs. of the amine adduct (1) blended or mixed with 25 lbs. to 162.5 lbs. of a polyiso-butene phenol and, more preferably, about 15 lbs. to 25 lbs. of the amine adduct blended or mixed with 50 lbs. to `~
7~ lbs. of the polyisobutene phenol. 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 ',: ` .

~4)'76802 dispersants 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 (1) 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 carbu-retor, 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 example, at a total treating level, i.e., the mixture of the amine adduct and the polyisobutene phenol, of about 120 to 950 parts per million (ppm on a weight basis in the gasoline) 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 automobilies are to remain within the United States EPA
emissions specifications for 50,000 miles as required for -vehicle certification.
Component (1) of the multipurpose additive of the present invention in its broadest aspect is the reaction `
product of (a) a glycidyl ether compound (I) of the formula: j .
,::: .
.:
:.:
.: .
;~, - :, - 24 - ;j ~07680~

(R )m ~ C~2cH C~ I

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 ethèr 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 substitu- ~ ;
tion is influenced by the number, position and bulk of the R groups. When R , 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 R is long chain ~;~
alkyl and/or bulkier in configuration, such as polyalkylene of 500 or higher molecular weight, it may be difficult to achieve more than di substitution by the glycidyl ether compound and then primarily only mono substitution on different nitrogen atoms may occur. -~
,~ .
- 25 - `~

1~76~302 The glycidyl ether compound (I) is conveniently prepared 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 lubri-cating oils.
In this specification unless otherwise stated, molecular weights are number average molecular weights and "alkyl" includes any aliphatic hydrocarbon radical, whether 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, predomi- ;
nating in ortho and para substituted products. Preferred i" :
products are thosecontaining 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 poly-alkylene 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 '"'' :. :~';;'i' :, .

~076802 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 polyalkylene is the polymerization product of propylene or butene, whether straight or branched chain or mixtures thereof. A pre-ferred R substituent is made by the polymerization of propylene or butene, or mixture thereof, to produce a polyisopropylene or polyisobutene 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. Accordingly, suitable amines include primary and secondary mono and polyamines such as aliphatic amines, aromatic amines, cyclic amines, and heterocyclic 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 substan-tially 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 - 27 - -~

.: . ,, ~, ,, . , ,:

~768()2 hydroxyl, halo, nitro, sulfide, cyano, carbonyl in various forms such as ester, amide and ketone groups, non-polymeri-zable 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-ethyl-hexyl 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 as dimethyl amine, diethyl amine, methylethyl amine, methylbutyl amine, di-n-hexyl amine, methyl dodecyl amine, dieicosyl amine, methyl triacontyl amine, dipenta-contyl amine, and the like, including mixtures thereof.
Another useful class is the N-substituted com-pounds 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, piperi-dine, phenoxazine, phenathiazine, and mixtures thereof, `
including their substituted homologs in which the substi-tuent groups include alkyl, aryl, alkaryl, aralkyl, cyclo-alkyl and the like. '`
' -' - 28 ~
.~ .

10768~2 ~

A preferred class of amines is given by the formula II:

R I (R l)n - R - NH II

where Rl, R2 and R3 independently are hydrogen, Cl-C6 alkyl substituted by -NH2 or -OH, R4 is a Cl-C divalent hydro-carbon 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-dialkyl-methylen~diamine, N,N-dialkanol-l,l-ethanediamine, and N,N-di(aminoalkyl)-2,2-propanediamine.
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 rom 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-(aminoalkyl)-1,4-butanediamine, and N,N-dialkyl-1,3-hexane-diamine. i , 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.

- ~ . . . , ,, : ~ , .. , .. - - .: . : . ..

1~768~Z

Some examples of amine substituted R , R 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 R , 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(2-hydroxyethyl)-1,3-propanediamlne; 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-3,3-di-methyl-n-butyl)-4-methyl-1,3-pentanediamine; N-(2-hydroxyethyl)-N-(2-aminoethyl)-1,3-propanediamine;
N,N-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 R , R , R3, and R
are hydrogen, R5 is ethylene, and n is 1-5. These poly-amines can be prepared by well-known methods of the art such as by the reaction of ethylene or propylenedichloride - 30 - ~ .

~07680Z

with ammonia. Most of the above polyamines are co~mercially 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 react-ants, 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. - As pointed out in the Principal Disclosure, a preferred component (l) of the additive mixtures of the invention is N,N'-bis[3-(p-H35-polyisobutylphenoxy)-2-hydroxy-propyl]ethylene diamine, shown by the structural formula III
where R is hydrogen or PIBH35:

fH fH
O-cH2cHcH2NHcH2cH2NHcH2cHcH2-o ', ~
_R6 ~ ~ R

H35 H35 `

- 31 - ~ ;

~7680Z

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 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 IU, all parts being on a weight basis. ;-~ OH
H3F ~ f ~ O-CH2CHCH2 H~- O-CH2CHCH2 -: . ~:
where R 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.

~ 7680Z

As previously disclosed in the Principal Disclosure, the preferred chemical gasoline adclitive component (1) is prepared by the following reactian-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 is 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.

`,' ~
OH 1) NaOH

H35 ~ Acid Catalyst> PIBH ~ OH 2) ~ ~ C~

R6 3) ~ NaCl `
', ~' ,.
O

> PIBH3 ~ 0CH2CH--CH2 NH2CH2cH2NH2) OH OH , -~
>IPIBH ~ OcH2cHcH2NHcH2cH2NHcH2cHcH2 ~ > ~

R6 R6 '' ,`` ".' '`,': '', . .

'~ I

~7~80Z

The reaction product may be separated from the hydrocarbon 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 hydro-carbon fuel. If the product 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 dilu-ted, if desired, to contain about 10-60~ by weight of amine adduct.
Experience with a large number of product com- ~-pounds 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 inhi-bition and handling, when used in admixture with component (2).
The polyalkylene phenol component (2) is used primarily for cost considerations and lowers treating costs. However, component (2) also promotes deposit ;
reduction as shown in the Induction System Test described. `
~omponent (2) is any of the polyalkylene phenols described above as reactants for the preparation of the glycidyl ether compounds (I), such as polyisopropylene phenol or polyisobutylene phenol having a number average ,, !

',` ' :

107~80~

molecular weight of about 500-3000, preferably about 600-1500. The polyalkylene phenols may also be mixtures of two or more of the mono, di and tri-alkylated phenols and any straight or branched chain products resulting from the alkylation of phenol. Component (2) may be present in the additive mixture as material remaining unreacted from the preparation of component ~1), or component (2) may be added separately.
Table IV presents data on the use of an additive mixture of the invention containing an adduct of formula ' III or IV and the polyisobutylene phenol prepared in Example 1, Part A (see pages 14-15 of the Principal Dis-closure). 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 III, the mixture of the amine adduct component (1) and the polyisobutene phenol component (2) compares very favorably with com- `
ponent (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 (2). A description of test procedures (A) and (B) is given in pages 8-11 of the Principal Disclosure hereof, to which the reader is re~erred.

~f D
. .
.~ . , ' ~ , .
- -- . , , ~ ~
` 1~7680Z

. - - .
~ 3~ m ~ . ~ l c, ' ~:
- ~ o ~ ~ . . -. ~.
o ~1 ~ ~ ~ ' 1.
; ~
0~ t, ~ P: o . a;~ ~ - ~ . , a)a~
~" ~,, .,, ~ ~q ~ ~
o s: ~= ~ ! ~
~ ~1 ~, ~q . . .
U~` ~ V~ ~ ~; ~ .
~ o o~ , ~ ~ . :':
X H .5::
'1-"
o . ,,, 11, a _ ~ ~ ~ ! ~ ~
- m ~ u, li~
O h ~
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~1 ~1 ~ o~ . ~
~ P ~ . I' E~ a ~ J~ O O ~ . C~
P; o ~ cr~
~: - a~ ~ o ~ ~ ~m ~ o ~ ~ ~ . , Z; ~ ~ ~ . I ',' :', . . . .
* , 'i '~
. . 1,~
O O o ~ 1n ~0 0 ~n I O ~ ~ .
O ~d O Ir~ ~
i ~ ~ ~
h ,D a) O

O ~ ~ ^ n~
Q) r 1 ~1 X '~ C~l ~
~o ~ ~ ~ ,~ ~ O : :
:
~I~ Q~ "~ :~
O H O ~1 ~1 ~ G
q:~ ~ O _ q:) O ~ ,1: 0 ~ O V _~ :"
Cc V ~ CC V *

. ... .... , . . .~. ,.. .... ~ . ; . ...

1C~768~Z
MS-08 gasoline is used in the slowby Carburetor Detergency Keep Clean Engine Test (Al. Phillips "J" Reference Fuel, an unleaded fuel, is used in the Induction System Test (B).
As stated in page 13 of the Principal Disclosure, one of the unique features of the additive mixtures o~ 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 inhibitorsr 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 component 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 like.
Accordingly, the multipurpose additive mixtures of the invention have valuable utility in two- and four-cycle combustion ignition engines for controlling or reducing car-buretor, 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 in common is multifunctional utility at relatively low use levels.
,, i~76802 The fuel or lubricating oils containing an additive mixture of the invention may also be formulated with any of the conventional additives, including antiknock agents, igni-tion accelerators, combustion improvers, power improvers, cold 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 depressants, and flammability suppressors.
In the following examples and throughout the specification and claims, all parts and percentages are by weight unless otherwise noted, and R6 is hydrogen or the same as the other hydrocarbon substituent on phenol. These examples illustrate component (1) of the additive mixtures of the in-vention. While not described separately, the polyalkylene phenols reactants used in preparing the amine adduct component " ;~;
(1) may also be used in excess or added separately to component (1) to form additive mixtures of the invention. (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 reaction was heated to 70C and 236 g (2.5 moles) of phenol were added , .

.. , , -. : ~ . ;. . . .

1~7680~

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. 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% NaOH solution (137.3 g, 1.71 moles) was then added and the mixture heated with stirring to reflux (118C) and held there for 0.5 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 product may also contain N,N-diadduct and N or Nl monoadduct.

107~80Z
. . . .

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:

OH

PIP ~ OCH2CHCH2NHCH2C~2NH2 ~ ~

`~.
,:
where PIP is the polyisopropyl substituent. ; -Octylphenol/Epichlorohydrin/Ethylene Diamine Adduct To a 3-liter, 4-necked round-bottom flask fitted :::
with a condenser, addition funnel, stirrer, and thermometer - `
is charged 418 g. (2.0 moles) octylphenol. A 50% aqueous i .
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 epichloro-hydrin 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 mixt:ure 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 fil~ered and stripped (150C, 0.1 mm).

... .
- 40 - ~

~t:976802 The reaction product is a useful multipurpose additive for hydrocarbon fuels and lubricating oils in accordance with the invention and has the following structure:

OH H H OH

H17C8 ~0CH2CHcH2NcH2cH2NcH2cHcH20 ~ C8H17 where R is H or -C~H17.
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.
EXP~LE 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 pre-dominating in mono, di, tri or tetra adducts identified by the following structural formula: ~
i OH ~ (H)p (H)q fH

~19 ~ 2 HCH~ NCH2CH2N ~ 2CHCH20 ~ ~ ;

Additive x y p q ,, : , i'~ono adduct 1 0 1 2 Di adduct 2(1) 0(1) 0 2 Tri adduct 2 1 0 1 ` .
Tetra adduct 2 2 0 0 :.

.
N- (3-Aminopropyl)-Morpholine Adduct With Polypropylphenyl ::
Glycidyl Ether A one-liter, 4-necked flask was charged with 370 g.

''. ' ~L~768~Z

(0.46 moles) of a polyisopropylphenol glycidyl ether (prepared as in Example 2, Part B), 81.2 g. (0.56 moles) N-(3-amino-propyl) 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 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 multi-purpose additive when used in a hydrocarbon fuel or lubricating oil either alone or in admixture with a polyalkylene phenol.
EXAMPLE 7 ``
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 multi-purpose additive when used as described in Example 6 and this specification. ~ ;

2-Aminoethylaminoethanol Adduct with Polypropylphenyl Glycidyl ;~
Ether A one-liter, 4 necked flask was charged with 370 g.
~:

' :~7f~80Z

(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 stirrer, condenser, and a thermometer. The reaction was heated 5 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. 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 further washed with 300 water, vacuum stripped at 120~, and filtered hot to afford 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 thermometer. 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 1~37680Z

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).

Hexylamine Adduct with Polypropylphenyl Glycidyl Ether A two-liter, 4 necked flask was charged with 320 g.
(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 (1.25% basic nitrogen). ``
OTHER MONOADDUCTS
Certain of the additives of the invention alter- ~

natively may be defined by the following formula (V): ~ -OH
R ~ O - CH2 - CH - CH2 - NH(X - Y)zH (V) R' 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 com- ~;
pounds are the monoadducts resulting from the condensation .
- 44 - ~ ~

.

; , ,,,:: , ~ .,: , , ., ;.; : : . :~; , ~9761 302 reaction between a glycidyl ether of formula I and an amine or aminoalcohol in such proportions as to avoid substitution on more than one active nitrogen atom of the amine or amino-alcohol (if the amine or aminoalcohol contains more than one active nitrogen atom). Suitable amines and aminoalcohols in-clude the alkylene polyamines and hydroxy-substituted amines such as ethylene diamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, trimethylenediamine, tetramethylenediamine, pentaethylene hexamine, N-hydroxyethyl ethylene diamine monoethanolamine, 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 -CH CH2, Y is -NH-, R has a molecular weight ranging ~-2 ~ -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 comprising 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

R ~ CH2CHCH2NHCH2CH2NH2 ::: ., .,.. .. . , . : . :
- .. . : . - ..... .. . . :: ; ,, , .. :

1~7~8V2 where R6 is polyisopropyl (Mnr-575) To a 3-liter, four~necked round-bottomed flask fitted with a condenser, addition funnel, stirrer and thermometer was charged 560 g. (0.76 moles) of the polyisopropylphenol prepared 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 ` !
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 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 discard~d. The solution was then washed ;three more times at 80C with 750 cc saturated NaCl solution, vacuum stripped, and filtered hot. The yield was 618 g. (95.3%), % basic nitrogen = 2.51, of the monoadduct whose structure is given above.

:
OH ~

R6 ~ 0CH21~HCH2NHCH2CH20H

where R6 is polyisopropyl (Mn ~ 860) The procedure of Example 2, Part A, was repeated in allessential respects except for substitution of 1720 g.
(2.0 moles) of Ampol C60 polypropylene for the Ampol C20 of lB~680Z
-Example 2. The yield was 1810 g. (95%) polyisopropylphenol (Mn about 1232).
To a 3-liter, four-necked round-bottomed flask fitted with a condenser, addition funnel, stirrer and thermo-meter were charged 950 g (0.76 moles) of the polyisopropyl-phenol prepared above. A 50% NaOH solution (61.0 g, 0.76 moles) was then added and the mixture heated with stirring to reflux (118C) and held there for 0.5 hours. The mixture was then vacuum stripped at 100C to remove water and cooled to 60C.
Epichlorohydrin (352 g, 3.8 moles) was then added and the reaction heated to reflux (~ 120C) for 3 hoursO 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 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~.0CH21HCH2NHCH2CH2NH2 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 ~ ;

. , :.

~7f~30Z

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.

R6~ocH2cHcH2NHcH2cH2oH ~ ~

where R is polyisopropyl (Mn~ 575 The procedures of 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.

, R6_ ~ CH2cHcH2NHcH2cH2N(cH3~2 ~here 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 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 deter-mined by oxygen analysis and W spectral parameters. Volatiles ~ ;
collected amounted to 13.2 g while 10.3 g of Amberlyst 15 ;

':
- 48 - ~, ' ' ! ' ` t . . , "

10768~Z

were recovered.
The procedures of Example 12 were then repeated in all essential respects except for substitution of the foregoing polybutenephenol (530 g., 0.76 moles) for the polyisopropyl-phenol of Example 12, and the substitution of N,N-dimethyl~
3-propane diamine (388 g, 3.8 moles) for the ethylene diamine of Example 12. The product was a monoadduct of the above structure.
EXAMæLE 17 1 0 "
~ ~ OH
R6_ ~ _o_cH2CHCH2(NHCH2CH2)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 magneticaliy 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 (33)

CLAIMS:

1. As a novel composition of matter, a multi-purpose 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 polyisobutene phenol.

2. A composition of matter according to claim 1 wherein the polyisobutene phenol has a number average molecular weight of about 500 to 3000.

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

4. 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.

5. A composition according to claim 1 wherein the polyisobutene portion of (b) has a number average molecular weight in the range of about 500 to 2000.

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

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

8. 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 polyisobutene phenol is present in an amount of about 100 to 650 ppm.

9. A novel composition of matter comprising (a) a major amount of gasoline and (b) incorporated in the gasoline the additive mixture of claim 4.

10. 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 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 polyalkylene phenol.

11. The additive of Claim 10 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; and said polyalkylene phenol is poly-isobutene phenol or polyisopropene phenol.

12. The additive of Claim 11 wherein R1, R2 and R3 are hydrogen and R4 is ethylene or propylene.

13. The additive of Claim 10 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, m is 1-2, and the polyalkylene phenol is polyiso-butene phenol or polyisopropene phenol of about 500-2000 number average molecular weight.

14. The additive of Claim 13 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.

15. The additive of Claim 14 wherein R1, R2 and R3 are hydrogen and R4 is ethylene or propylene.

16. The additive of Claim 10 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 polyalkylene phenol is polyisobutene phenol or polyisopropene phenol of about 500-2000 number average molecular weight.

17. The additive of Claim 16 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.

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

19. The additive of Claim 10 wherein R6 is poly-isobutylene or polyisopropylene and said R6 has a molecular weight of about 500 to 2000, m is 102, 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-aminomethyl pyridine, 2-amino-ethylaminoethanol, N,N-dimethylethylenediamine, aniline and hexylamine.

20. The additive of Claim 19 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-dimethyl-ethylenediamine, aniline and hexylamine.

21. The additive of Claim 10 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.

22. 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 additive 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 polyalkylene phenol.

23. The composition of Claim 22 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; and said polyalkylene phenol is poly-isobutene phenol or polyisopropene phenol.

24. The composition of Claim 23 wherein R1, R2 and R3 are hydrogen and R4 is ethylene or propylene, and said polyalkylene phenol has a number average molecular weight of about 500 to 3000.

25. The composition of Claim 22 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, m is 1-2, and the polyalkylene phenol is polyisobutene phenol or polyisopropene phenol of about 500-2000 number average molecular weight.

26. The composition of Claim 25 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.

27. The composition of Claim 26 wherein R1, R2 and R3 are hydrogen and R4 is ethylene or propylene.

28. The composition of Claim 22 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 polyalkylene phenol is polyisobutene phenol or polyisopropene phenol or about 500-2000 number average molecular weight.

29. The composition of Claim 28 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.

30. The composition of Claim 29 wherein R1, R2 and R3 are hydrogen and R4 is ethylene or propylene.

31. The composition of Claim 22 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.

32. The composition of Claim 22 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.

33. A composition comprising a major proportion of gasoline, and a minor amount of the additive of Claim 10 in amounts of said reaction product (1) of about 20-300 ppm and said polyalkylene phenol (2) of about 100-650 ppm.