CA1096381A - N-substituted [(alkylphenoxy)-2- hydroxypropyl]alkylene polyamine as multipurpose fuel and lubricating oil additives - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
The present invention as disclosed provides a multi-purpose additive for a hydrocarbon fuel, a lubricating oil, or a mixture of a hydrocarbon fuel and a lubricating oil, comprising the reaction product of (a) a glycidyl ether compound of the formula

Description

109638~

THE DISCLOSURE
This invention relates to a novei multipur?ose detergent for addition to gasoline. The novel multipur-pose 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, in the range of about 20 to 600 ppm (parts per million) and, - 10 more preferably, in the range of about 60 to ~00 p?m.
The new product is a polyisobutene phenol/epichlorohydrin/
amine adduct. The novel product may also be described as, for example, the reaction proauct of a polyisobutene or polyisopropene phenol wlth epichlorohydrin follcwed by amination with ethylene diamlne.
It is an object of the present invention to provide a detergent motor fuel which will have certain carburetor detergent ?roperties 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 pr~sent invention to ?rovide a detergent fuel which will m~intain a low level of hydrocarbon and carbon ~onoxide e~;haust gas emissions and which will avoid the use of phos?horus-containing additi-~es. It ls st il a further obiect of the ?resent invention to ?rovide a detergent fuel whicr has other desirable propertl2s, auch -as rust and corrosion pro~ection, water de~ulsibllity ` ~.

1~9~i38 1 properties, anti-icing properties, etc. It is a further object of the present invention to provide a multi-functional gasoline additive or additive combination effective in inhibiting the formation of intake valve deposits in addition to being effect-ive as carburetor detergents and which can be used at relativelylow concentrations (and thus at relatively low cost), for example, at a treating level of about 20 to 600 parts per million (ppm on a weight basis in the gasoline) and, more preferably, 60 to 400 ppm.
There are, of course, other detergent motor fuel compos-itions available today, but they generally suffer from one or more deficiencies. Either they are used at very high concentra-tions, for example, something of the order of 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, epichlorohydrin and amines show excellent carburetor, induction system and combustion chamber detergency and, in addition, provide effective rust inhibition when used in automotive gasoline fuels at low con-centrations, i.e., between about 20 to 600 ppm and, more pre-ferably, between about 60 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. Our preferred product is the N,N Bis r3-(p-H35-polyiso-b~tylphenoxy)-2-hydroxypropyl~ ethylene diamine. The PIB is our abbreviation for a polyisobutene generically of any molecular weight. The H35 is the commercial designation for Amoco's poly-1~363t31 isobutene of Mn -~-670. The structural formula for the prefer-red product is as follows~
OIH OH

t 2 2 2 2 CH2CHCH2 ~ ,Rl ~ 0~ Rl :.
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 preferably, 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.2., a polyisobutene radical of number average molecular weight of about 500 to 2000 and, more preferably, about 600 to 1500;
or Rl may alternatively simply be hydrogen, i.e., H.
According to one aspect of the present invention, there-fore, we provide a normally liquid, multifunctional additive composition for addition to a leaded, low lead, or unleaded gas-oline, i.e., to a distillate hydrocarbon fuel comprising a majorproportion of a hydrocarbon base fuel distilling within the gas-oline distillation range. This additive provides carburetor, induction system and combustion chamber detergency, rust inhib-ition and good handling properties to a higher degree than nor-mally found with typical current first generation multipurposecarburetor detergents of the alkyl ammonium phosphate or polyol-efin succinimide type. The increased performance we are seeking is necessitated in part by the ~; - 4 -1~9~:3~31 . .
advent of emissions control hardware which must remain 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 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. ~herefore, we feel there is currently no additive available which is completely acceptable in terms of economics, treating level and performance.
The preferred chemical gasoline additive com-pound of this invention is prepared by the following reac-tion sequence:
a) Phenol is alkylated with polyisobutene, i.e., polyisobutylene, of Mn ~670 (Amoco H35) using an acid catalyst.
bj 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.

~.~9~31~1 I

OH 1) NaOH .0 PI~H35 + ~ ~s~ PI ~3 ~ -0~ _ 3 PIB 5_ ~--OCH2cH-bH2 + 1/2 NH2CH2CH2 2 OH OH
--~ PIBH35 ~ 2CHCH2NHCH2CH2NHCH2bHCH2 0 ~--PI~35 \Rl Rl~
(Preferred Product of this invention and application, : . where Rl is PI ~35 or H.) 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 be~-ieved 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.

.~ -963~31 o a) a~
~a ~
a ~P~
O o~
r~
~ bD O
o r~-r~
c ~ ~ L~
rd :~
H
, :~ O ` .
1~ ~ ~ x E~ ~ O
U~
:~~¢ ~ . ,~
h`--~a) ~ ,~
E~ ~ ~ ~a 1~ ~ ~; O \L: ~ h h ~ ~ O~
~q O ~-~
~;~,n ~n o .
C0 3 0 rl ~h o ~:: ~ rd ~;~ ~ ~ ~ ~
H¦ Hh ~ .,~

~:1 t:~ t~S O
. b.O ' E~ ~ ~
. - ~ ~ ~ ~ ~ O
~ ~E~p; 8 o ~ ~ ~
~+~ ~ ~ o ~ o ~q~ a) ~,n ~C¢ ~ ¢ , O ~ r1 ~3 u7 a~
~;* r~
~i.~* , ~ u~ u~
.4~ u) 1_1 ~;rd C) ~-I ~ ~ .n o~D ~ O O ~
j:4 rd 0.~ ,~ _, ~ s:: ~ o . c~
P~bOO O ~
~ s~ o I o r~ ~a o ,~
O ~rl r-~ O O h ~1 C) +~ ~ ~_~ . h O
. P~ a) - u~
h ,Q ~ ~ e,o Et r~l . ~ h ~
~ h-rl O
. .
a) c.~ a) ~D ~ ra ~ ~2 S~ ~ h O
~r~ O r-l O <~ c~ ~ ,c~ h h rlh O ~ u~ h ~ ~ (D O~ r-l a) ~i5 rd ~ u~ u~a) ~ ~ ~ u~ ~1 ~ o ~ ~d ,~ S *
~ v m c~ 4 *

1~91~38~

Table I~ presents data showing the ability of the pre-ferred product of the present invention to control the increase in the octane number requirement of an engine. Although the mechanism of activity is not firmly established, the additive presumably works by preventing the buildup of deposits in the combustion chamber.
TABLE II
OCTANE NUMBER REQUIREMENT INCREASE

Treating Level,*Octane Number (C) lbs.~1000 bbls in Requirement AdditiveGasoline (Nonleaded)Increase -Untreated - 10 Base Gasoline Preferred 75 5 Product (PP) (Amine Adduct 15 where Rl is H or PIBH35) *As measured by the Combustion Chamber Deposit Engine Test The Blowby Carburetor Detergency Test above, showing %
deposit reduction, is described below. MS-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 Engine Test.

ENGINE TEST EVALUATION OF MULTIPURPOSE
CARBURETOR DETERGENTS 5 (A) BLOWBY CARBURETOR DETERGENCY KEEP CLEAN ENGINE TEST
Engine Test Procedure The Blowby Carburetor Detergency Keep Clean Engine Test (BBCDT-KC) measures the ability of a gasoline additive to keep clean the carburetor throttle body area, and is run in a 1970 Ford 351 CID V-8 engine equipped ~i ~ o96381 by means of a special "Y" intake manifold with two 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. lrhe 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 0 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 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, 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_ ~9~381 The gasoline used in the BBCDT-KC test is an MS-o8 gasoline having the following properties:
Gravity:
API 59.7 Sp. gr. at 600 F. 0.74 ASTM D-86 distillation, F.:
I.B.P. 93 10% 123 5% 205 90% 348 E.P. 405 Percent recovered 98 Percent residue Percent loss Percent sulfur O.11 Lead, gm./gal. 3.08 FIA composition:
Aromatics~ percent 23.1 Olefins~ percent 20.0 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~ is described below.

~9~3t31 (B) INDUCTION SYSTEM DEPOSIT ENGINE TEST
En~ine Tes-t 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, 4 cycle,

2.5 H.P. Briggs and Stratton engine 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 monoxide 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 tèst 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.
; 20 (C) COMBUSTION CHAMBER DEPOSIT ENGINE TEST
En~ine Test Procedure The Combustion Chamber Deposit Engine Test (CCDET) is used to evaluate the ability of a gasoline additive or mixture of additives to control or reduce the octane number requirement increase (ONRI) in an internal combustion engine. The test is run using a 1972 Chevrolet

3~0 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. inertia wheel. The following test cycle and ~963~1 operating conditions are employed and are intended to simulate an urban taxi cab.
Test C~Tcle:
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) - In+ake air, F. Ambient Jacket water, F. 180 Engine oil-sump, F. 220 + 10 Octane number requirement is determined at 24 15 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., 20 the engine is run on a series of blends of isooctane and n-heptane of known octane number until audible knock is perceived. The lowest standardized octane number blend at which the engille 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 tile final octane number requirement for a particular test.
The ~A) test procedure, i.e., the description 1~9~;i3131 of the Blowby Carburetor Detergency Keep Clean Engine Test, beginning at line 22 of page 8 of the specification, 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 Deposit Engine Test, beginning at the top of 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 Chamber Deposit Engine Test~ beginning at line 20 of page 11 of the speci-fication, refers to the results shown in Table II, column 3, on page 8 of the specification.
One of the unique features of 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 ashless 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 fuel additives. The general structure of the novel compounds of this invention may be expressed as follows:
OH OH
CH2CHCH2(NHCH~CH2~NHCH2CHCH2 wherein n is an integer of from 1 to 5, and 1~9~3~1 . .
wherein R2 is an alkyl substituted benzene ring, and wherein the alkyl substituent (or substituents) is poly-isobutyl 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 H~ Phenol Reaction:
OH OH

P 1 i obutene H3s Amberlyst 15 b PI ~ ~-_, M W. 94 -660 ~754 .W.=Molecular Weight) (Theoretical M.W.) ~he product is actually a mixture of alkylated phenols with an average molecular weight of 548 based upor.
oxygen analysis (2.92%) and 556 calculated from W spectra:
parameters.
The experimental procedure is described below.
To a 5-1. 3-ne~cked flask equipped with a ther-mometer, mechanical stirrer and reflux condenser with Dean-Stark trap was charged 1920 g. (2.9 moles) of Poly-isobutene 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 100-107 C.) under a nitrogen atmosphere for 24 hours, during which time 5.4 ml. of water had separated. After cooling to 60-800 C., the mixture was filtered to remove the res n *Registered trademark of Rohm and Haas Company for a macro-- reticular sulfonic cation exchange resin catalyst.

1~963~31.

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-5 retical: 2.12%).
(Part B) 1,2-Epoxy-3-[p-(H35-polyisobutyl)phenoxy]
~ro~ane . . _ _ Reaction:
OH

+ ClCH2C~1--CH2 + NaOH

M.W. ~754 92.540 2 \0/ 2 l + NaCl + H20 ~810 To a 5-1. 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 97.4% assay) of sodium hydroxide pellets ? 45 ml. of 2-propanol and 450 ml. of toluene. The stirred mixture was heated under a ni-trogen 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 CO The reaction mixture was then cooled~ filtered, 20 and the salt (107 g. dry) washed with toluene. The fil-1~96381 trate was stripped (100 C./15 mmO) to give 1075.3 g. of product residue.
(Part C) N,Nl-Bis[3-(p-H35-polyisobutylphenoxy)-2-hydroxypropyll ethylene diamine Reaction:

1 H2CH_ CH2 2 moles ~ Ri + H2NCH2CH2NH2 X~le~

PIB
M.W. ~810 60.1 OH OH
O CH2 cHcH2 NHcH2 cH2NHcH2 cHcH2 o ,R

PIBH35 PI~H35 ~1680 A mixture of 1018.4 g. of the above epoxide, 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.), there was obtained 105304 g. of turbid residue which was filtered through a bed of "Celite 545'i* in a steam-heated Buchner funnel to give clear, yellow viscous product.
The product prepared in this way had 1.26% basic N (1.67% theory) and 5.26~ 0 (3.81% theory).

*Trademark of Johns-Manville Company for a brand of diatomaceous earth filter aid.

1~96381 The gasoline additive or additives or gasoline fuel addi-tive or additives of the present invention act to control spar~
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 e~ample, the reaction product of a polyisobutene or polyisopropane phenol with epichlorohydrin follcwed ; 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 pro-ducts. The term "Preferred Product", 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. ~or the sake of illustration and brevity, only one of the possible reaction products has been depicted in this disclosure; however, the preferred product in the case where n=l can be a mixture of (a) and (b), or (a) or (b) tal;en singly. In other-words, on a parts per 100 parts basis, (a) can vary from 1 to 99 parts ~c 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, more complex mixtures can form where alkylation can occur at any of the available nitrogen sites; such cases are ta~en to be covered by the pres-ent disclosure. The overall amount for use in gasoline of the new product or amine adduct (s) remains the same no matter what the internal proporticn or ratio or amount of (a) or (b) is.

3~ 0~ 0~
~CH2CHCH2(N~CH2c~2)~NHcH2cHcH2 (a) R2 R~
- , L7~
.

1~9~i381.

OH

N(CH2CH2NH)nH (b) OH
where n=l to 5 and R2 is a polyisobutyl or a polyisopropyl sub-stituted benzene ring as hereinbefore disclosed.
This application is related to copending, concurrently filed, Canadian Patent Application 242,178 of Warren H.
Machleder and Joseph M. Bollinger, said application being entitled "Multipurpose Fuel Additive and Mixture or Blend".
This application is also related to copending, concur-rently 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".

- 17a -las63sl SUPpLEMENTARY DISCLOSURE
The present invention, in one aspect, as described in the Principal Disclosure of this application, resides in a multi-purpose gasoline fuel additive which comprises the product of reaction of a polyisobutene or polyisopropene phenol with epich-lorohydrin followed by amination with a polyamine.
In another aspect, the invention as described in the Principal Disclosure, resides in a composition of matter as de-fined in the immediately preceding paragraph which comprises a compound of the following formula:
OIH OIH
/ CH2cHcH2(NHcH2cH2)nNHcH2cHcH2 (a) O O

wherein n is an integer of from 1 to 5, and wherein R2 is an alkyl substituted benzene ring wherein the alkyl group is polyisobutyl or polyisopropyl of a number average molecular weight in the range of about 500 to 2000, or a compound of the formula ` 20 OH

N (CH2CH2NH)nH (b) : R20CH2CHCH2 OH
wherein n and R2 are as defined above; or mixtures of (a) and (b).

1~96381 A further, preferred, aspect of the present invention as set forth in the Principal Disclosure, is a composition of matter as above which has the following formula OH OH
-cH2cHcH2NHcH2cH2NHcH2cHcH2-o wherein PIBH35 is polyisobutyl of number average molecular weight of about 670, and Rl is either PIBH35 or hydrogen.
me invention as set forth in the Principal Disclosure hereof, in another aspect, resides in a motor fuel composition comprising (1) a major propcrtion by weight of gasoline, and (2) a minor proportion by weight, i.e. about 20 to 600 ppm, of the above-defined polyisobutene phenol/epichloro-hydrin/amine adduct.
Now, according to a further broad aspect of the present invention, as described more fully hereinafter in this :

- 18a -. :. ..;
.... . .

1~963~1 Supplementary Disclosure, there is provided a multipurpose add-itive for a hydrocarbon fuel, a lubricating oil, or a mixture of a hydrocarbon fuel and a lubricating oil, comprising the reaction product of (a) a glycidyl ether compound of the formula /. /o\
6~0CH2CH - 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.
Also provided by the invention as described in this Sup-plementary Disclosure is a composition comprising a mixture of (l) a major proportion of a hydrocarbon fuel, a lubricating oil, or a mixture of a hydrocarbon fuel and a lubricating oil, and (2) a minor detergent amount of a multipurpose additive comp-rising the reaction product of (a) a glycidyl ether compound of the formula /0\
6 ~ ~ ~ OCH2CH - CH2 where R6 is an aliphatie hydrocarbon group having at least 8 earbon atoms and m is 1-3, and (b) an amine having at least one amino group having at least one aetive hydrogen atom.
Aeeording to a preferred aspeet of the invention as set forth in this Supplementary Diselosure, the amine moiety of the additive has the formula ~ - 19 -~63~1 R N7~ R4 - N~R4 _ NH
R2 ~ R5 n R3 where Rl, R2 and R3 independently are hydrogen, Cl-C6 alkyl or Cl-C6 alkyl substituted by -NH2 or -OH, R4 iS a Cl-C6 divalent hydrocarbon radical, R5 iS hydrogen or Cl-C6 alkyl, and n is O
to about 5.
According to still another aspect of the present inven-tion, there is provided a compound represented by the formula O~H
6 ~ O - CH2 - CH - CH2 - NH~ X - Y ~ H
R' in which Rl is a hydrocarbon radical having from 1 to 4 carbon atoms, R6 is a hydrocarbon radieal having a molecular weight ranging from about 200 to 1500, X is a divalent hydrocarbon radical having from 2 to 6 carbon atoms, Y is NH or O, and z has a value from 1 to 10.
Thus, it has been found that the additives as originally diselosed herein need not be restrieted only to what is set forth in the Prineipal Diselosure, in the following respeets:
(a) the amine reaetants whieh may be used;
(b) the ehain length of the alkyl group on the phenol;

(e) the extent of substitution of the glyeidyl ether alkyl phenol on the amine; and (d) the number of alkyl substituents on the phenol.

1~9G381 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 cleanliness of the carburetor and other elements of the fuel induction system, such 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 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.

.i ~^
'.~

' 5 ` ~ ~
. . _ . ,G' , , 1~963~

It has been conceived and demonstrated that the reaction products of certain substituted phenols, epi- .
chlorohydrin and amines show excellent carburetor, induc-tion system and combustion chamber detergency and, in addition, provide effective rust inhibition when used in hydrocarbon fuels at low concentrations, i.e., between about 20 to 600 ppm and, more preferably, between about 60 to 400 ppm. In addition to their activity as fuel addi-tives, these compounds are also ashless rust inhibitors and dispersants for use in lubricating oils at concen-trations of about 0.1 to 10% by weight, preferably about 0.5 to ~ by weight. The products may also be described as, for example, the reaction products of an alkyl phenol with epichlorohydrin followed by amination with an amine such as ethylene diamine or other primary or secondary mono or polyamine. As hydrocarbon motor fuel (such as gasoline or diesel fuel) additives, the adducts of the invention act to control spark plug fouling and thus help to keep the spark plugs relatively clean and free of deposits.
According to a preferred aspect of the present invention, there is provided a normally liquid, multi-purpose composition for addition to a leaded, low lead, manganese or unleaded gasoline, l.e., to a distillate - ~ !

`` 1~9G381 hydrocarbon fuel comprising a ma~or proportion of a hydro-. carbon base ~uel distllling within the gasoline distilla-tlon range. The addltlve provides carburetor, inductlon system and combustlon chamber deter~ency, rust lnhibitlon and good handling properties to a hl~her degree than normally found with current ~irst generatlon multlpurpose carburetor detergents of the al'~yl ammonlum phosphate or polyolefin 3uccinimide type. The increased performance 30ught ls necessitated in part by the advent o~ emissions ; J~ control hardware which must remain deposit-free if the new automobiles are to remain within the United State9 EPA
emissions speciflcation3 for 50,000 mile3 a3 requlred ~or vehicle certi~lcation.
. ~
In its broadest aspect th.e present invention resides in a multipurpose additive for a hydrocarbon fueI, a lubricating oil, or a mixture of a hydrocarbon fuel and a lubricating oil, comprising the reaction product of ~a) a glycidyl ether compound of the formula ~0\

~ ~I R2-0--CH2CH-CH2 where R2 is a benzene ring having attached theret~ at least one aliphatic hydrocæbon motor fuel or lubricating oil solubilizing group having at least 8 carbon atoms, and ~b) an amine having at least one amino group having at least one active hydrogen atom.
The multipurpose additives of the present invention in a further broad aspect are the reaction products of ~.
~.. .. .

1~9G3~1 (a) a glycidyl ether compound (I) of the formula:

~O\
/ ~ OCH2CH ~ CH2 where R6 is an aliphatic hydrocarbon group containing at least 8 carbon atoms and m is 1-3, and (b) a primary or second-ary 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 - 23a -! "~

63~31 amino hydrogen atoms and theoxetically therefore can be tetra-substituted with the glycidyl ether reactant, the degree of sub-stitution 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 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 substitu-tion on different nitrogen atoms may occur.
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 sub-stituents are chosen to provide the required degree of solubility of the final glycidyl ether compound/amine adduct in hydrocarbon . 20 fuels or lubricating 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, ~96381 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, pre-dominating in ortho and para substituted products. Preferred products are those containing at least 60% of the alkyl sub-stituent para to the phenolic hydroxyl group. The monoalkylated phenol is the preferred product but di- or tri-alkylated prod-ucts 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, bu'ylene, pentene and decene, and then alkylating the phenol with the polyolefin. Preferably, the resulting poly-alkylene 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 preferred R6 substituent is made by the polymerization of propylene or butene, or a mixture thereof, to produce a polyisopropylene or polyiso-butene 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 ` 1~3~3l~1 one active hyd~ogen atom may be reacted with the glycidyl ether compounds (I) to foxm the adducts of the invention. Accord-ingly, 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 con-tain 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 cc~pound nor the pr~perties 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-polymerizable 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, tri-acontyl 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, dipentacontyl amine, and the 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 1~9G3~31 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 like-wise useful including morpholine, thiomorpholine, N-(3-amino-propyl)morpholine, pyrrole, pyrroline, pyrrolidine, 3-amino-methyl pyridine, tetrahydrofurfuryl amine, indole, pyrazole, pyrazoline, pyrazolidine, imidazole, imidazoline, imidazolidine, piperidine, phenoxazine, phenothiazine, 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:

R R4l5n R4 RH3 II

where Rl, R2 and R3 independently are hydrogen, Cl-C6 alkyl sub-stituted by -NH2 or -OH, R4 is a Cl-C6 divalent hydrocarbon radical (alkylene or phenylene), R5 is hydrogen or Cl-C6 alkyl, and n is O 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.
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-butanediamine, and N,N-dialkyl-2,3-(4-methylpentane)diamine.

1~39G3~31 Some examples of diamine reactants in which the amine groups are bonded to carbon atoms on the alkylene radical rep-resented 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(a-minoalkyl)-1,4-butane-diamine, 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, secbutyl, 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-propanediamine; 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-prop-anediamine; N,N-di(2-hydroxybutyl)-1,3-propanediamine; N,N-di-(6-hydroxyhexyl)-1,1-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.

-~ - 28 -~i 1~9638~
;
Other useful polyamines are ethylene- and propylenepoly-amines and include ethylenediamine, diethylenetriamine, trie-thylenetetramine~ tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, propylenediamine, dipropylenetriamine, tripropylenetetramine, tetrapropylenepentamine, pentapropylene-hexamine, and hexapropyleneheptamine. 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 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 ; 20 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 inven-tion include mixed products as well as single products.

!~

- - .
1~963~1 As pointed out in the Principal Disclosure, a pre-ferred product of the present invention is N,N'-bis[3-(p-H35-; -polyisobutylphenoxy)-2-hydroxypropyl]ethylene diamine, shown by the structural formula III where R6 is hydrogen or PIBH35:
OIH fH

.. , ~H2CHCH2NHcH2cH2NHcH2cHcH~R6 where PIB is an abbrevlatlon for a polyisobutene;
generically of any molecular welght. H35 is the commerclal deslgnatlon for Amoco Chemical Company~s polylsobutene havlng a number average molecular welght (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 polylsobutene may be in the ortho position (R6). R6 may, therefore, simply be the same as PIB or R6 may be hydrogen.
As indicated in the general descriptlon above, the preferred product can be a mlxture of structure III
and structure (IV ) set forth below or it can be II or IV
taken singly. In other words, on a parts per 100 parts basis, rI-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 basls.

_30-!

l~9G3t~1 R
r< OI H
PIB -- O ;_O-CH2CHCH2 PIB --~ O ~ O-CH2CHCH2 \R6 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.
As previously disclosed in the Principal Disclosure, a preferred chemical gasoline additive compound of this invention is prepared by the following reaction sequence where R6 is 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.

,~

1~9G3~1 Od 2) CH ClCH-CH
PIBH35 ~ OJ ~cid Cat~l~st>PIB ~ ~ Od 2 ~ PIBH ~ OCH2cH-cH2 d2 2CH2Nd2 ----~PIBH3 ~ CH2C CH2NHcH2cH2NHcH CBCH -- ~--PIBH35 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. If 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 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. Tables I and II as set forth in pages 7 and 8 and the Principal Disclosure report such properties.

~, - 32 --~i9G3l31 The test procedures (A, B, C) are described after the Tables (see pages 8-12 of the Principal Disclosure), One of the unique features of the products of this inven-tion 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 ashless rust inhibitor is a key component in formulating an ashless engine oil. Therefore, the products 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 hydrocarbon 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 additives 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 1~9~;3~
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.
The fuel or lubricating oils containing an amine adduct of the invention may also be formulated with any of the conven-tional additives, including antiknock agents, ignition acceler-ators, 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, stabil-izers 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 suppres-sors.
In the following examples and throughout the specifica-tion 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. (Example 1, Parts A-C, appears in pages 14-16 of the Principal Disclosure).

~63~1.

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 nitrogen, 1150 g (2.0 moles) Ampol C20 polypropylene. The reaction 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 95 C and held there 5 hours. The reaction mixture was then cooled to 70 C, 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 80 C and the layers were allowed to separate. After discard-ing 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-bottomed 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 mix-ture heated with stirring to reflux (118 C) 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 o ~

63~1.

then cooled to 65C and 792 g (8.55 mole~)-epichlorohydri`n ' ~
, 'was added and the reaction heated to reflux-(r~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 J 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 poly-lsobutene phenol/epichlorohydrin adduct of Part B of Example 1. The product may also contain N,N-diadduct and I
N or N~ monoadduct. l , The additive of Example 2 was tested in the Carburetor DetergencyJ Induction System Deposits and ASTM
D-665 Rust,tests described in Table I and thereafter aboveJ
with the following improved results , TABLE III

(A) (B) Conc. ASTM-D665 Carburetor Induction Addi- lbs.7 Rust TestJ% DetergencyJSystem tive 1000 bbls. Area Rusted mg.deposit Deposits,mg.

Base gasoline -- 100 20 2200 Chevron F-310 1050 5-15 0.2 100 Ex. 2 adduct 75 o_o <1 11 5 0-5 0.8-1.9 219 5-10 1.4 761 ' 1~963~
, 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 ~ OcH2cHcH2NHcH2cH2NH2 where PIP is the polyisopropyl substituent.
The Carburetor Detergency, Induction System Deposits and ASTM D-665 Rust tests described in Table I
and thereafter above were performed,using the product of this example,with the following improved results:

TABLE IV

- Base Unleaded Ex. 3 Additive Fuel Additive Conc.Jppm (A) Carb. Deterg., mg. deposit 100 11 60 (B) Induction System Deposits, mg. 2280 1190 60 __ 93 3 Rust Test, %
area rusted 100 0 300 Octylphenol/Epichlorohydrin/Ethylene Diamine Adduct To a 3-literJ ~-necked round-bottomed flask fitted with a condenser, addition funnel, stirrer, and thermometer is charged 418 g. (2.0 moles) octylphenol. A
50% aqueous NaOH solution (160 g., 2.0 moles) is then 1~9~;3~1 added and the mixture heated with stirring to reflux and held there 0.5 hours. The ~ixture is then vacuum-stripped at 100 C
(0.5 mm) to remove water! charged with 50 g. toluene, and re-stripped (105! 0.5 mm) to azeotropically remove the last traces of water. The reaction is then cooled to 65~C and 925 g. (10 moles) epichlorohydrin is added and the reaction heated to re-flux (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 invention and has the following structure:

r==~ OH H H OH /===~
H17C8--<\~OCH2CHCH2NCH2CH2~CH2CHCH20 ~ C8H17 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.

~9~

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, ~ri or tetra adducts identified by the following structural :. formula:

j ~ IOH ~ (Hl)p (~)q / OH
19 9 ~ ~ OCH2CHCH2~ NCH2CH2N ~CH2 2 ~ 9 1 Additive x y p q Mono adduct 1 0 1 2 Di adduct 2(1) 0(1) 0 2 Tri adduct 2 1 0 Tetra adduct 2 2 0 0 The four reaction produc~s, when tested as in Examples 2 and 3 at a concentration of 300 ppm, gave the following improved results, wherein it will be noted that the tetra adduct gave the best results:
TABLE V

Base Nonleaded Additive Fuel Mono Di Tri Tetra (A) Carb. Deterg., mg. deposit 100 1.3 0.6 0.6 2.1 : 25 (B) Induction System Deposits, mg. 2280 1290 283 304 36 Rust Test, ~
.~ Area Rusted 100 0 0 0 0-5 :`

: - 39 -~ l~9G31~1 EXA~RLE 6 N-(3-Aminopropyl)-Moxpholine Adduct With Polypropylphenyl Glycidyl Ether A one-liter, 4-necked ~lask 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)morpho-line and 350 cc xylene. The flask was fitted with a stirrer, condenser, and thermometer. The reaction was heated at 150 C
for 5 hours, then vacuum stripped at 150 C (0.1 mm). The res-idue 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 multipurpose additive when used as described in Examples 1-5.

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-aminomethylpyridine, and 250 cc xylene. The flask was fitted with a stirrer, con-denser, and a thermometer. The reaction was refluxed 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 ~il G3~

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 Examples 1-5.

2-Aminoethylaminoethanol 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 g. (0.56 moles) 2-aminoethylaminoethanol, and 250 cc xylene. The flask was fitted with a stirrer, conden-ser, and a thermometer. The reaction was heated 5 hours at 150 C, 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 pro-duct solution was rewashed with hot water, vacuum stripped at 120', and filtered hot to afford 318 g. product having multi-purpose additive utility when used as described in Examples 1-5.

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.

1~96381 The flask was fitted with a stirrer, condenser, and a thermo-meter. The reaction was heated 5 hours at 150, then vacuum stripped at 150 (0.15 mm). The product was dissolved in 300 cc toluene and washed with a mixture of 300 cc saturated salt sol-ution and 200 cc n-butanol. The product was further washed with 300 water, vacuum stripped at 120 , and filtered hot to afford 328 g. product having utility as a multipurpose additive when used as described in Examples 1-5.

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. dimethylethylene-diamine, 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 t0.2 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 frac tion was rewashed with 400 cc water (four times), then vacuum stripped at 120 (0.25 mm) and filtered hot to afford 313 g.
product (2.30% basic nitrogen). The product is a multipurpose additive when used as described in Examples 1-5.

: 30 ~i ~ > ~

1~9~i3t31 , ' ! ~ . . . j: . _ 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) hexylamine, and 225 cc xylene. The flask was f`itted 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, satu-rated 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.
product (1.25% basic nitrogen).having utility as a multi-purpose addltive when used as descrlbed in Examples 1-5.

. I .

-43~

~ i 63til1 In genexal, as indicated in the foregoing specification, the additives of the invention provide detergency, rust inhibi-tion and other benefits in liquid hydrocarbon blends, wherein the liquid hydrocarbons boil in the range of about 80 to 1000 F.
Such hydrocarbons include gasoline or motor fuels boiling from about 85 to 450F, distillate fuels (such as kerosene) boiling from about 350 to 650F, and mineral lubricating oils boiling from about 650 to 1000 F.
The gasoline motor fuel which is benefited by the addi-tive of the invention may be leaded or unleaded and may consist of straight-chain or branched-chain paraffins, cycloparaffins, olefins and aromatic hydrocarbons and mixtures of these. The base fuel can be derived from straight run naphtha, polymer gasoline, natural gasoline or from catalytically cracked or thermally cracked hydrocarbons and catalytically reformed stocks.
The hydrocarbon composition and the octane level of the base fuel are not generally critical. Any conventional motor fuel base may be employed in the practice of this invention.
In general, the additive of the invention is added to a mineral oil composition in a minor amount, i.e., an amount effective to provide detergency to the oil composition. The additive is effective in a mineral oil in an amount ranging from about 0.001 to 5.0 weight percent based on the total composition.
In a fuel composition, an amount ranging from about 0.001 to 0.2 weight percent is preferred with the most preferred concentration ranging j ~)96381 from about 0.002 to 0.10 weight percent. It ls understood, of course, that the additi~e can be employed in an oil concentrate for ease of handling containing from about 5.0 to about 50 weight percent of the additive.
,;' OTHER MONOADDUCTS
Certain of the addi'ives of the invention alter-natively may be defined by the following formula (V):

R6~ 0 - CH2 - Cl~ - CH2 - NH(X Y~Z
R' in whic~l R6 is a hydrocarbon radical having a molecular weight ranging from about 200 to 1500, R' is a hydrocarbon radical having from 1 to 4 carbon atoms, x is a divalent hydrocarbon radlcal havlng from 2 to 6 carbon atoms, Y is .~H or O (oxy), and z has a value from 1 to lO, preferably l to 6.

It will be apparent from formula V that such com-pounds are the monoadducts resulting from the condensation reaction between a glycidyl ether of formula I and an amine or aminoalcohol in such proportions as to avoid sub-stitution 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 polyamines and hydroxy-substituted amines such as ethylene dlamlne, dlethylene-triamine, triethylene tetramine, tetraethylene pentamine, 1~963~1 tri~ethylenediamine, tetramethylenediamine, pentaethylene hexamine, N-hydroxyethyl ethylene diamine monoëthanol-amine, and the like.
Accordingly, the monoadducts of formula V resu~t 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 l:l, 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 gasollne, or 300 to lO00 when the adduct is used in a mineral oil composition comprising a mi~ture of hydro-carbons boiling in the range from about 80 to 1000F.
The rollowing examples illustrate the foregoing monoadducts. These adducts are useful multipurpose fuel and lubricating oil additives when used as previously 1¦
described. The Mn below the structure refers to the R6 substituent 963~

OH

~ O ~ocH2cHcH2NHcH2cH2NH

where R is polyisopropy (~n ~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 (325 g, 3.8 moles) was then added and the reaction heated to reflux (~-120 C) 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 (118-120 C) 3 hours. The reaction mixture was vacuum stripped at 120 C 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 80 C. The layers were then separated and the aqueous layer dis-carded. The solution was then washed three more times at 80 C
- with 750 cc saturated NaC1 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.

.~1 1~9~i3~81 EXA~PLE 13 OH
R6 OcH2lHcH2NHcH2cH2oH

where R6 is polyisopropyl (Mnf-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 of 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 thermometer were charged 950 g (0.76 moles) of the polyisopropylphenol prepared above. A 50% NaOH solution (61.0 g, 0.76 moles) was then added and the mixture heated with stirring to reflux (118 C) and held there for 0.5 hours. The mixture was then vacuum stripped at 100 C to remove water and cooled to 60 C. 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. Ethanol amine (46 g, 0.76 moles) was then added and the reaction was refluxed (118-120 C) 3 hours. The reaction mixture was vacuum stripped at 120~C 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 80~C. The layers were then separated and the aqueous layer discarded. The solution was then washed three more times at 8G wlth 750 cc saturated NaCl soiu-tlon, vacuum stripped, and fil,,ered hot. The yield was 910 g. (87~), % basic nitrogen = 0.5,of the monoadduct , whose structure ls set forth above. ' OH
R ~ OcH2cHcH2NHcH2cH2l~H2 ¦~
where R6 ls polyisopropyl (.~ln~860) The procedures Or Example 12 were repeated in all essential respects except for substitutlon of' Ampol C60 polypropylene (1720 g, 2.0 moles) for Ampol C20. The yleld of pol,-yisopropylphenol was 1810 g. (95~), r~n about 1232. The yield of monoadduct of the above structure was 916 g. (88~), % baslc nitrogen = o.8.

EXAMPLE 15 , .
OH

R ~ cH2cllcH2NHcH2cH2oH

where R6 is polyisopropyl (A~;n~-575) ;
The procedures of Example 12 were repeated in all essential respects except for substitution of N-methyl-ethanol amine (57 g, 0.76 moles) for ethylene diamine.
The yield of monoadduct of the above structure was 48~ g.

(79~ basic nltrogen = 0.9.

~ , `.

-1i~96381 EXAIi~PLE 16 OH
R ~ Oc~2cHcH2~HcH2c~2~(cH3)2 where R is polyisobutyl (~ln ~ 660) To a 300-ml. 3-nec~ed flask equipped wlth a thermometer, mechanical stirrer and reflux condenser with Dean-Stark trap was charged 99.0 g (0.15 mole) of poly-isobutylene ("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 9~-99C) under a nitrogen atmosphere for 12 hou-s. Gravity filtratlon through a glass wool plug at 70C followed by a 10 ml. hexane bead rinse gave a clear, essentially colorless filtrate. Vacuum concentration 'o a pot temperature of 150C at 1 mm. ~ afforded 101.8 g.
(90% yield) of product polybutenephenol as a viscous, golden brown oil havin~ an i~n of 700 a3 determined b~-oxygen analysis and W spectral parameters. Vola~iles collected amounted to 13.2 g while 10.3 g of "Amberlyst 15"
were recovered.
The procedures of Example 12 were then repeated in all essential respects except for substi~ution of the ~oregoing polybutenephenol (530 g., 0.76 moles) for the polyisopropylphenol of Example 12, and the substitution of N,N-dimeth~1-1,3-propane diamine (388 g, 3.8 moles) for the eth~Jlene diamine of E;ample 12. The product was a mono-adduct of the above structure.

*Trademark 50 .
.~. 1, . ~ , .

1~96381 ~H
R _ /\ ~ O-cH2cHcH2(NHcH2cH2)2N 2 where R6 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.

.

~i

Claims (33)

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 gas-oline fuel additive which comprises the product of reaction of a polyisobutene or polyisopropene phenol with epichlorohydrin followed by amination with a polyamine.

2. A composition of matter according to claim 1 which comprises a compound of the following formula (a) wherein n is an integer of from 1 to 5, and wherein R2 is an alkyl substituted benzene ring wherein the alkyl group is polyisobutyl or polyisopropyl of a number average molecular weight in the range of about 500 to 2000, or a compound of the formula (b) wherein n and R2 are as defined above; or mixtures of (a) and (b).

3. A composition of matter according to claim 1 having the following formula:

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

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

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

6. A novel composition of matter comprising (a) a major amount of gasoline and (b) incorporated or mixed therein a minor amount in the range of about 20 to 600 ppm of the additive of claim 2.

7. A novel composition of matter comprising (a) a major amount of gasoline and (b) incorporated in the gasoline a minor amount of the gasoline additive of claim 3 in the range of about 20 to 600 ppm.

CLAIMS SUPPORTED BY THE SUPPLEMENTARY DISCLOSURE

8. A multipurpose additive for a hydrocarbon fuel, a lubricating oil, or a mixture of a hydrocarbon fuel and a lub-ricating oil, comprising 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 motor fuel or lubricating oil solubilizing group having at least 8 carbon atoms, and (b) an amine having at least one amino group having at least one active hydrogen atom.

9. A multipurpose additive for hydrocarbon fuel, a lubricating oil, or a mixture of a hydrocarbon fuel and a lub-ricating oil, comprising the reaction product of (a) a glycidyl ether compound of the formula where R6 is an aliphatic hydrocarbon motor fuel or lubricating oil solubilizing 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.

10. The additive of Claim 9 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.

11. The additive of Claim 10 wherein R1, R2 and R3 are hydrogen and R4 is ethylene or propylene.

12. The additive of Claim 9 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.

13. The additive of Claim 12 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 O
to about 5.

14. The additive of Claim 13 wherein R1, R2 and R3 are hydrogen and R4 is ethylene or propylene.

15. The additive of Claim 9 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.

16. The additive of Claim 15 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.

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

18. The additive of Claim 9 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-aminomethyl pyridine, 2-aminoethylaminoethanol, N,N-dimethyl-ethylenediamine, aniline and hexylamine.

19. The additive of Claim 18 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-amino-propyl) morpholine, 3-aminomethyl pyridine, 2-aminoethyl-aminoethanol, N,N-dimethylethylenediamine, aniline and hexylamine.

20. A composition comprising a mixture of (1) a major proportion of a hydrocarbon fuel, a lubricating oil, or a mixture of a hydrocarbon fuel and a lubricating oil, and (2) a minor amount of the multipurpose additive of claim 8.

21. A composition comprising a mixture of (1) a major proportion of a hydrocarbon fuel, a lubricating oil, or a mix-ture of a hydrocarbon fuel and a lubricating oil, and (2) a minor detergent amount of a multipurpose additive comprising the reaction product of (a) a glycidyl ether compound of the formula where R6 is an aliphatic hydrocarbon motor fuel or lubricating oil solubilizing 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.

22. The composition 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 C1-C6 alkyl, and n is 0 to about 5.

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

24. The composition of Claim 21 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.

25. The composition of Claim 24 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.

26. The composition of Claim 25 wherein R1, R2 and R3 are hydrogen and R4 is ethylene or propylene.

27. The composition of Claim 21 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.

28. The composition 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 C1-C6 alkyl, and n is 0 to about 5.

29. The composition of Claim 28 wherein R1, R2 and R3 are hydrogen and R4 is ethylene or propylene.

30. The composition of Claim 21 wherein R6 is polyiso-butylene 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-dimethyl-ethylene-diamine, aniline and hexylamine.

31. The composition of Claim 21 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.

32. A motor fuel composition according to claim 24 containing from about 0.001 to 0.2 weight percent of said multipurpose additive.

33. A reaction product according to claim 8 having the formula in which R' is an aliphatic hydrocarbon radical having from 1 to 4 carbon atoms, R6 is an aliphatic hydrocarbon radical having a molecular weight ranging from about 200 to 1500, X is a divalent hydrocarbon radical having from 2 to 6 carbon atoms, Y is NH
or O, and z has a value from 1 to 10.