US3807976A

US3807976A - Multi-functional gasoline additives and gasolines containing them

Info

Publication number: US3807976A
Application number: US00199775A
Authority: US
Inventors: P Polss
Original assignee: EI Du Pont de Nemours and Co
Current assignee: EIDP Inc
Priority date: 1969-08-13
Filing date: 1971-11-17
Publication date: 1974-04-30
Anticipated expiration: 1991-04-30

Abstract

Hydrocarbon-soluble combinations of: (A) aliphatic C4 to C10 monoamine salts of branched chain primary C8 to C16 alkyl acid esters of orthophosphoric acid; (B) polybutenes having molecular weights in the range 400 to 3000 and viscosities in the range 500 to 900,000 SUS at 100*F. and 60 to 20,000 SUS at 210*F.; and, optionally, (C) hydrocarbon solvents. These mixtures are useful in gasolines for spark ignition engines to inhibit the formation of intake valve deposits and to clean the engine''s carburetor.

Description

United States Patent I [191 Polss [451 Apr. 30, 1974 MULTI-FUNCTIONAL GASOLINE ADDITIVES AND GASOLINES CONTAINING THEM [75] Inventor: Pei-ry' Polss, Wilmington, Del.

[73] Assignee: E. I. du Pont de Nemours and Company, Wilmington, Del.

[22] Filed: Nov. 17, 1971 [21] Appl. No.: 199,775

Related Application Data [63] Continuation-impart of Ser. No. 849,925, Aug. 13,

1969, abandoned.

[52] US. Cl 44/62, 44/72, 44/DIG. 4 ['51] Int. Cl Cl0l l/22 [58] Field of Search .Q 44/72, 80 v [56] References Cited UNITED STATES PATENTS 3,502,451 3/1970 Moore et al. 44/80 Popkin 44/72 Kautsky 44/72 Primary ExaminerDaniel E. Wyman Assistant Examiner-Mrs. Y. H. Smith 57] ABSTRACT 23 Claims, No Drawings MULTI-FUNCTIONAL GASOLINE ADDITIVES AND GASOLINES CONTAINING THEM This application is a continuation-in-part of Ser. No.

849,925 filed Aug. 13, 1969, now abandoned.

BACKGROUND OF THE INVENTION 1. Field of the Invention Liquid hydrocarbon fuels for spark ignition engines such as present day automotive gasolines are complex mixtures and normally contain relatively unstable, highmolecular weight components which tend to deposit on the surfaces of the air-fuel intake system. Naturally occurring sulfur compounds, nitrogen compounds, and polycyclic hydrocarbons, together with additives normally employed in preparing the fuels for commerce, such as antiknock compounds and other agents, contribute to the sludge and deposits that gradually form throughoutthc induction system of the engine. The increased engine use, these deposits tend to build up causing improper fuel carburetion, improper valve closing, sluggish intake valve action, loss of power and valve burning. Another source of intake system deposits, particularly those found on the intake valve tulips,

- is the oil which reaches the intake valve tulip by passing between the intake valve stem and the intake valve guide. This oil contains oxidized material and sometimes additives which accumulate onthe valve tulip as the result of oxidation and deterioration of the oil and- /or evaporation of the oil. This invention relates to multi-functional additives which are effective in inhibiting the formation of such deposits and are also effective as carburetor detergents. More particularly, it relates to novel combinations of selected polybutenes and amine salts of branched chain primary alkyl esters of' orthophosphoric acid and to automotive gasolines containing them.

2. Description of the Prior Art Polybutenes and the amine salts of aliphatic esters of orthophosphoric acid have been individually added to gasoline in the past, but for purposes other than carburetor detergency US. Pat. No. 2,049,062 discloses the incorporation of polybutene into .gasoline to increase viscosity. U.S. Pat. No. 3,228,758 discloses the use of amine salts of alkyl acid phosphates in distillateifuels, such as gasoline andfuel oils, to inhibit color and haze formation, corrosion of metal by the fuel and the formation of ice in carburetors. The two additives have not been heretofore used together, and they are not particularly noted as materials which, inhibit the formation of intake valve deposits. As previously mentioned, polybutenes were considered to be thickeners for gasoline. i

SUMMARY OF THE INVENTION This invention is directedto (I) normally liquidmulti-component multi-functional compositions for addition to distillate hydrocarbon fuels and to (2) gasolines containing such compositions, said compositions consisting essentially of A. a hydrocarbon fuel-soluble salt'of i. a C to C aliphatic monoamine wherein each aliphatic radical attached to the amine nitrogen is attached through a saturated carbon'atom and ii. a C to C branched chain primary alkyl ester of orthophosphoric acid,

B. from 1 to 50 parts by weight per part of (A) of a normally liquid polybutene having a number average molecular weight in the range 400 to 3,000 and a viscosity in the range 500 to 900,000 SUS at F. and in the range 60 to 20,000 SUS at 210F., and, optionally,

C. a hydrocarbon solvent for (A) and (B) in an amount sufficient to improve the handling characteristics of the composition, said amount corresponding normally to from 10 to 40 percent by weight, preferably about 15 to 30 percent by weight, based on the total composition.

DESCRIPTION OF THE INVENTION As previously mentioned, the amine salts of alkylacid phosphates have been added to gasoline to obtain such beneficial effects as anti-icing, corrosion inhibition and stability against haze formation. This invention is based on the discovery that the overall performance of these amine salt additives can be advantageously ex-.

tended and improved by combination with polybutenes. When the additive combinations of this invention are used in gasoline, they exert a resistance to intake valve deposit formation and a remarkable degree of effectiveness in cleaning up dirty carburetors i.e.', carburetors that have accumulated deposits over long periods of use. Thus the compositions of this invention are referred to as multi-functional additives since they provide a wide range of highly advantageous properties to present day motor gasolines.

The polybutene additives of this invention consist essentially of polyisobutenes (i.e., polybutenes wherein each monomer unit in the polymer chain is C(CH CH derived from isobutene), or polybutenes wherein the butylene units are derived from 1- butene or 2-butene, or co-polymers of the various. butenes, provided the polybutene is liquid at ordinary temperatures and has a molecular weight and viscosity as defined. For reason of availability and overall characteristics the polyisobutenes are preferred. The term polyisobutenc as used herein is meant to include polymers which may have incorporated in the polymer chain minor amounts of l-butene and Z-butene units. The polyisobutenes are conveniently obtained by polymerizing isobutene or mixtures of isobutene with small amounts of l-butene and/or 2-butene, according to known methods. Polybutenes which may be used in this invention are commercially available.

The molecular weights referred to herein are number average molecular weights determined by vapor pressure osmometry according to ASTM D-2503. Thus the polybutene additives of this invention having molecular weights in the range of 400 to 3,000 are mixtures of polybutene molecules averaging from about 7 to about 54 C H units in the polymer chain, with each molecule containing an olefinic double bond, analyzable by titration with bromine according to standard methods, such as ASTM D-l l59.

The molecular weight and molecular weight distribution among the polybutene molecules in these mixtures are such that the viscosities of these normally liquid materials range from about 500 SUS at 100F. and from about 60 SUS at 210F. for the low (400) molecular weight polymers to about 900,000 SUS at l00F. and about 20,000 SUS at 210F. for the high (3000) molecular weight polymers, the viscosities being determined according to ASTM D-445 and 446.

Preferred polybutenes have molecular weights in the range 950 to 2,700 and viscosities in the range 1,000 to 19,500 at 210F. and in the range40,000 to 890,000 SUS at 100F. Most preferably the molecular weights are in the range 1,200 to 1,400, with viscosities in the range 2000 to 3,000 SUS at 210F. and in the range 100,000 to 125,000 at 100F. In general, the polymers with molecular weights in the lower end and in the upper end of the overall 400 to 3,000 molecular weight range tend to be less effective in reducing intake system deposits. Mixtures of two or more of the various polybutenes may be used if desired.

The amine salts, useful in this invention, are hydrocarbon soluble materials and preferably for ease of handling are liquid compositions. Such salts may be prepared according to any of a number of methods which are well known in the art. Usually they are prepared by reacting primary alkyl acid phosphates, wherein the primary alkyl groups have from eight to 16 carbon atoms in branched chain configuration, with aliphatic monoamines containing a total of from four to 10 carbon atoms. Normally, a molecule of amine is used for each molecule of monoalkyl dihydrogen phosphate and for each molecule of dialkyl hydrogen phosphate. The resulting salts are generally regarded as substantially neutral, ie they exert a pH of between 6 and 7 in water.

The branched chain primary alkyl acid esters of orthophosphoric acid (acid phosphates) will be understood to be those esters in which only 1 or 2 of the three acidic hydrogen atoms of orthophosphoric acid have been replaced by alkyl groups; i.e., they are the monoalkyl dihydrogen phosphates and the dialkyl hydrogen phosphates. Such esters may be obtained according to the general methods of the art which involve reacting an alcohol with phosphorus pentoxide (P From about 2 to about 4 moles of the alcohol may be used per mole of P 0 Preferably, about 3 moles of the alcohol per mole of P 0 is used. When this 3:1 mole ratio of alcohol to P 0 is employed, the mixtures are considered to be approximately equimolar mixtures of the monoand dialkyl esters of orthophosphoric acid. On analysis however, it may be found that the range varies from about 40 to about 60 mole percent of the monoalkyl esters to about 60 to about 40 mole percent of the dialkyl esters. These mixtures of monoand dialkyl esters are preferred for reasons of economy but other mixtures, as well as the monoalkyl esters alone or the dialkyl esters alone, may also be used.

For the preparation of the branched chain primary alkyl acid phosphates, the alcohol will be a branched chain primary alcohol having eight to 16 carbon atoms, preferably eight to 13 carbons, or a mixture of two or more of such alkanols. These alcohols preferably will be the branched chain primary alkanols made by the well-known Oxo process from C0, H and a branched chain olefin such as the G y-C monoolefmic polymers and interpolymers of propylene and butylene. Such alcohols are disclosed by Smith et al. in US. Pat. No. 2,824,836 and by Rudel et al. in U.S. Pat. No. 2,884,379. Examples of preferred Oxo-alcohols that may be used are branched octyl primary alcohols from propylenebutylene interpolymers, branched tridecyl primary alcohols from triisobutylene and from tetrapropylene, and the branched hexadecyl primary alcohols from pentapropylene.

The amines that are used to produce the amine salt component are the aliphatic monoamines containing a total of four to 10 carbon atoms and wherein each aliphatic radical is attached to the nitrogen through a saturated carbon atom. The term aliphatic monoamine" will be understood to mean a compound which contains only one amino nitrogen to which is attached 1 to 3 aliphatic radicals and is sufficiently basic to form neutral salts with the defined alkyl acid phosphates. The amines may be primary, secondary, or tertiary amines, with the primary amines being preferred. Also, it is preferable to use amines which are water insoluble. The aliphatic radicals attached to the nitrogen may be acyclic (open chain) or alicyclic (cycloaliphatic) radicals. Also, the aliphatic radical may be saturated or unsaturated, provided that the carbon atom attached to the nitrogen atom is a saturated carbon atom, that is, a carbon atom that is not attached to another carbon or to the-nitrogen by a multiple bond. The aliphatic amines are generally unsubstituted hydrocarbon amines.

Preferably, the amine will be an alkyl (acyclic, saturated) monoamine of four to eight carbon atoms and most preferably eight carbon atoms. 1f the amine is a secondary amine, or a tertiary amine, it is preferable that it contain a total of at least eight carbon atoms.

Examples of suitable primary amines are: nbutylamine, isobutylamine, isoamylamine; nhexylamine; cyclohexylamine; octylamine; 2- ethylhexylamine; and l,l,3,3-tetramethylbutylamine (t-octylamine). Further examples are t-nonylamine, available commercially and consisting mainly of the C amine with small amounts of the C and C amines. Examples of useful secondary amines are di-n-butylamine, disec.-butylamine, di-isobutylamine, and diamylamine. Examples of suitable tertiary amines are N,N-dimethylcyclohexylamine and N,N-diethylcyclohexylamine.

Any of the above amines can be employed in salt formation with any of the above branched chain alkyl acid phosphates. Preferred, however, are 2- ethylhexylamine, and isobutylamine.

A preferred class of amine salt comprises substantially neutral salts wherein the alkyl acid phosphate component is a mixture of about 40 to 60 mole percent of mono- C to C -Oxo-alkyl dihydrogen orthophosphate and 60 to 40 mole percent of di- C to C -Oxo-alkyl monohydrogen orthophosphate. Particulary preferred amine salts are the isobutylamine salt and the 2-ethylhexylamine salt of the above mixture of mono- Oxo-tridecyl dihydrogen orthophosphate and di-Oxotridecyl monohydrogen orthophosphate. These are particularly preferred because of their low cost and exceptional detergency effect. Representative and preferred combinations of polybutenes and amine salts are described in the examples below.

An important advantage of this invention is that only small amounts of the low molecular weight polybutenes and of the amine salt components are necessary to exert significant action in cleaning dirty carburetors and inhibiting formation of intake valve deposits in spark ignition engines. The actual quantities required depend on the particular polybutene and amine salt employed, on the fuel and its tendency to form deposits, the extent of deposit accumulation on the engines carburetor and on the effect desired. Normally there is used sufficient quantities of these two critical components to supply to the gasoline from about 0.01 to about 0.3 percent by weight of the polybutene based on the gasoline and from about 0.0005 to about 0.008 weight percent of the amine salt component based on the gasoline. Often not more than 0.1 percent of the polybutene and not more than 0.005 percent of the amine salt need be used; and usually highly satisfactory results are obtained with from about 0.02 to 0.06 percent of the polybutene and 0.002 to 0.005 percent of the amine salt. I

Normally, the proportions of the two critical components are such that there is present fromabout 1 to 50 parts by weight of the polybutene for every part of the amine salt, preferably between 5 to 30 parts and, most preferably from about to parts. The two components may be added separately to the fuel or they may be added together, for example as a concentrate in a suitable carrier such as a liquid hydrocarbon sufficient to improvethe handling characteristics of the composition. Many of the additive combinations of this invention are viscous, and the presence of a solvent makes it easier to pour and mix the materials. For convenience in this respect, the solutions should be concencompounds. The organolead antiknock agent can be any of those known to the art for such purpose, but usually will be a lower (C -C tetraalkyl lead, such as tetramethyl lead, tetraethyl lead, methyl triethyl lead, dimethyl diethyl lead, trimethyl ethyl lead, tetraisopropyl lead, and the like. Mixtures of two or more of such organolead antiknock agents are also useful. The quantity of antiknock agent employed will depend upon the octane number of the base stock and the octane number desired in the finished product. Generally, an amount of antiknock agent is used which will provide about 0.1 to 6 grams ofleadfor each gallon of the motor fuel and preferably about 2 to 4 grams of lead per gallon. Preferably, the antiknock agent will be one or more tetraalkyl lead compounds in which the alkyl groups contain 1-2 carbon atoms. The compositions of this invention can also contain varying amounts of conventional fuel additives such as scavenging agents, dyes, antioxidants, anti-icing agents, rust inhibitors, corrosion inhibitors, inhibitors of haze formation, inhibitors of gum formation, anti-preignition agents, and the like. Any of such agents which are chemically and physically compatible with the additive compositions of this invention may be incorporated into these additives.

EXAMPLES The following Examples illustrate this invention. For convenience, the polybutenes referred to in these Examples are characterized below. Such polymers are commercially available Oronite polybutenes. These materials are liquid polymers consisting essentially of polyisobutenes and are characterized by the following properties:

(a) Number Average, by MechroLab vapor pressure osmometry, ASTM D-2503 (b) SUS, by ASTM D445 and D-446 (c) Grams Bio/100 grams'polymcr. by ASTM D-l159 of the polybutene component; and from 10 to 40 (preferably 15 to 30) percent of hydrocarbon solvent, based on the total composition. Preferred additive compositions of this invention contain: to percent of a polybutene having a 1,260 molecular weight, a IQQ E viscosity of 104,000 SUS and a 210F. viscosity of 2,460 SUS; 5 to 6 percent of 2-ethylhexylamine salt of a mixture of mono-Oxotridecyl dihydrogen orthophosphate and di-Oxo-tridecyl monohydrogen orthophosphate; and 18 to 24 percent of a hydrocarbon solvent consisting essentially of mixed xylenes. When added to gasoline in amounts of from about '50 to 250 lbs./ 1000 barrels, which corresponds to from 0.015 to 0.08 percent by weight, this preferred composition supplies from about 0.01 to 0.06 percent of the polybutene and from 0.001 to 0.005 percent of the amine salt. The preferred 75 to lbs/1000 barrels dosage provides from about 0.015 to 0.04 percent of the polybutene and about 0.0015 to 0.003 percent of the salt.

The gasolines useful in this invention can be free of additives other than the polybutene or they can contain antiknock compounds such as organolead antiknock EXAMPLES l to 7 The ability of the additive combinations of this invention to clean up a dirty engine is illustrated by the carburetor detergency test described below (involving a deposit accumulation step and a deposit clean-up step) in a fuel having the following inspection data:

includes 0.5 theory ethylenedibromide and 1.0 theory ethylenedichloride For the test, Polybutenes 1V and V described above were blended into samples of the above fuel in a concentration of 0.031 weight percent of the fuel. An amine salt of an alkyl acid phosphate was also blended into the fuel, and in this instance, it was the 2- ethylhexylamine salt of a 1:1 molar mixture of mono- Oxo-tridecyl dihydrogen orthophosphate and di-Oxotridecyl monohydrogen orthophosphate prepared according to the procedure of Example 1 of U.S. Pat. No. 3,228,758. The concentration of the amine salt, which is referred to below as 2-ethy1hexylammonium tridecyl orthophosphate, was varied as noted in Table 1.

DETERGENCY TEST PROCEDURE A Chevrolet 6 cylinder, 230 cu. in. engine was used having a Carter No. 3511- carburetor and an ice tower with heater. The ring gap of the top piston ring was increased by one-eighth inch to a gap of 0. 1 38 inch and installed in place of the second compression ring leaving the top ring groove empty thus increasing the blowby. The total engine blowby was directed to the carburetor air cleaner from the dome cover. The air cleaner filter element was eliminated. The exhaust line was modified to supply engine exhaust to the carburetor air cleaner. The distributor vacuum advance was eliminated to maintain spark advance of 4 before top center.

The operating conditions were as follows: engine speed at 700 i rpm; water outlet temperature 175 2.5F.; air/fuel mixture set for maximum vacuum; carburetor air was cooled by passage through an ice tower and then reheated to 9095F.; engine exhaust supply to the carburetor air inlet was controlled as indicated below.

A. Deposit Accumulation (Control Fuel)- New spark plugs were installed, motor oil was changed to an SAE 30 low detergent oil, carburetor, air cleaner housing and exhaust system were cleaned. The engine was started with the exhaust feed valve to engine inlet air closed. The speed was adjusted to 700 rpm at maximum vacuum. The exhaust feed valve was opened and engine speed maintained at 700 rpm. The exhaust feed valve setting is critical. This setting was such as to feed the maximum amount of exhaust that the engine would accept and still operate smoothly without stalling. By this method there is produced in the shortest time sufficient throttle body deposit for the clean-up phase of the test.

The engine was operated for 10 hours or until it could no longer be kept running under these conditions. The carburetor was removed and rated using a visual rating chart. A rating of 100 is clean. If a rating cleaner than "30 was obtained, additional deposit accumulation operation was required.

B. DEPOSIT CLEANUP The engine conditions are the same as those for (A), except that blowby and exhaust are not fed into the air inlet. The cleanup procedure was followed for 50 hours in five 10-hour segments. Ratings were made at appropriate intervals to determine the amount and speed of cleanup. Percent cleanup was determined as follows:

5 1. 100 minus rating of deposit accumulation amount available for cleanup 2. rating after cleanup minus rating of accumulation amount of cleanup 3. cleanup amount of cleanup divided by amount 10 available for cleanup multiplied by 100 Table 1 Detergency Test Results Z-Ethylhexylammonium Example Polybutene Tridecyl Phosphate No. mol. wt. wt. wt. clean Control 1 0 0 18 Control 2 0 0.0048 17 Control 3 IV 1260 0.031 0 30 20 1 do. do. 0.031 0.0010 35 2 do. do. 0.031 0.0024 46 3 do. do. 0.031 0.0048 65 4 do. do. 0.031 0.0080 44 Control 4 v 1400 0.031 0 20 5 do. do. 0.031 0.0024 24 6 do. do. 0.031 000421 311 25 7 do. do. 0.031 0.00110 411 The results show the additive combinations are remarkably effective to clean deposits from dirty carburetors. The cleanup effect is greater than additive;

ie greater than that expected from the performance of either the polybutene or the amine salt alone. The clean-up effect is particularly pronounced with the 1,260 molecular weight polybutene which, at the concentrations employed, shows peak performance at a polybutene/amine salt ratio in the range of about 5/1 to EXAMPLES 8 TO 11 Other additive combinations were tested by the procedures outlined above for examples 1 to 7 using a fuel having the following inspection data:

A.P.l. gravity 59.4 Initial b. pt., F. 96 Recovered, by volume 5% 114 20% 13s" 201 259 341 End point 410 50 Residue, by vol. 1.0

Aromatics, by vol. 25 Olefins, by vol. 12 Saturates, by vol. 63 Sulfur, by wt. 0.068 Tetraethyl lead, g./gal 2.53 includes 05 theory ethylene dibromide and 1.0 theory ethylcncdichloridc.

55 For the test the samples and fuel were blended as described above for examples 1 7 and the results are shown below in Table 11.

Y Table 11 Detergencv Test Results Example Polvbutene Amine Salts Clean up No. mol. wt. wt. No. wt.

Control 1 0 0 17 Control 2 V 1400 0.031 0 13 Control 3 0 A 0.0048 17 s v 1400 0.031 A. 0.0048 56 Control 4 0 B 0.0048 29 9 v 1400 0.031 B 0.0048 36 Control 5 0 C 00041; 14 10 v 1400 0.031 C 0.0048 26 Control 6 0 D 0.0048 28 11 v 1400 0.031 D 0.0048 24 TEST A The engine used was a 1968, 250 cubic inch, 6 cylinder Chevrolet engine equipped with Power-Glide Designation transmission and inertia flywheel. The engine was on a A isobutylammoriium o ti-tridecylphosphate B hthylhexylammonium owmdecylphosphme test stand equipped with a dynamometer to absorb the C 2-ethylhexylammoniu n oxo-octylphosphate power output. The heads were completely recondi- D l y um ammomum ow-octylphospha'etioned, deposits removed from piston tops and the car- I buretor overhauled. New PCV valve, spark plugs, oints and asoline filter were installed. The oil filter The results show that the additive combinations of l 8 9 d 1 b t was changed and l0W-30 oil put n. d efamp as l p ay F S The test was performed by operating the engine for e agency i fii g 9 t e 100 one hour cycles. Each cycle consisted of the folg g A e an mmon lowing conditions designed to similatc stop-and-go ont e scopep mventlm." exlmpe dctua y the-road conditions including moderate and high speed s ows imdgomsm m the combmed result driving alternating with stopped periods with the en- EXAMPLES 12 o gine running such as at a traffic light.

To illustrate the effectiveness of the additive combinations of this invention in preventing intake valve deposits, polymers lllthrough Vl above were blended, in 20 "m concentrations ranging from 0.012 to 24 weight per Interval Engine ed, Dyno Speed, cent, as more fully exemplified below, into samples of (mins.) rpm rpm Throttle a motor gasoline having a tendency to form intake 06 OM50 memo valve deposits under both ordinary and severe driving 600 Idle conditions. Also blended into the fuel samples was 25 660 1700 50 {Ste-W0? 2-ethylhexylammonium tridecyl phosphate (described 1: 2056: w0 above in concentrations of 0.0024 and 0.0048 weight 18-21 600 percent based on the fuel. The gasolines inspection 3:38 6 f-0 {gii data was as follows: 29-34 2:100:75 lclle 30 34-60 600 ldle-WOT* A.P.|. gravi 58.9 5 sec. idle. 5 sec. wide open throttle Initial b. pt., F. 92 Recovered, by volume 1 i Z2 8: The engine coolant fluid inlet and outlet temperatures, 8. the engine oil temperature and pressure, the transmis- 266: sion oil temperature and the engine and dynamometcr End point 3%., speeds were continuously recorded. The oil and spark Residue by vol. 1.0 plugs were changed at 50 hours. Ammalcsby 24 At the end of the cycles, the intake valves were Olefins, by vol. l5 Sa[ur tg %by VOL 61 40 removed, washed with pentane, dried and weighed. %ullfur.tl l llt.l d I These valves were then cleaned by scraping off the erae yea,g.ga l includes 0.5 theory ethylene dibi'omide and 1.0 theory ethylene dichloride per tuhp dePQSIt and welghed agaln Table reports remole of tetracthyl lead. ults obtamed Table lll Chevrolet lntake Valve Deposit Test TEST- A Amine Phos- Polymer ohate Salt* Valve Deposit Ex. No. mol. wt. wt. wt.% wt. g. (avg) Control 0 0 1.28 12 111 950 0.062 0.0024 0.22 13 IV 1260 0.031 0.0024 0.32 14 IV l260 0.031 0.0048 0.51 15 v 1400 0.031 0.0024 0.19 16 v 1400 0.012 0.0024 1.10 17 Vl 2700 0.031 0.0024 0.31

' 2-ethylhexylamine salt of mixed monoand di-(Cxo)tridecyl acid phosphate described in Examples l-7.

Buick Intake Valve Deposit Test EST B The engine used was a 401 CID Buick with export pistons and an extra head gasket (i.e., a low compression package) so that the engine was capable of operating on lower octane fuels such as are more commonly used in Europe. The carburetor was a Carter AFB carburetor with the interconnecting passageways between the barrels sealed so that two fuels could be introduced and tested simultaneously. This engine, which was without transmission and inertia flywheel, was mounted on a test stand and a dynamometer was used to provide the load. The heads were completely reconditioned, deposits removed from the piston tops and carburetor overhauled. New PCV valve, spark plugs, points and gasoline filter were installed. The oil filter was changed and lW-30 oil put in.

The test was performed by operating the engine for l hours, repeating the following idle-load cycle.

Operation (repeated ldlc Load for l 10 hours) Time-Interval in seconds 60 196 Speed, rpm 2000 i 25 2800 i 25 Torque, ft. lbs. 0 75 Air-Fuel Ratio I] 1. 1.0 l4.0:l :0.5

Table IV parts of commercial mixed xylene. This is a mobile liquid suitable for addition to gasoline. Also the aforementioned 2-ethylhexylamine salt of mixed monoand di-Oxo-tridecyl hydrogen phosphate can be used with the polybutenes designated as l and ll at the beginning of the Examples. Another preferred combination of polybutene V and the 2-ethylhexylamine salt described above is 67.5 parts polybutene, 14 parts amine salt concentrate (containing 2.8 parts kerosene) and 18.5 parts xylene. It should also be pointed out that amine salts other than those previously disclosed can be used. Among these are amine salts of approximately 1:1 molar mixtures of monoalkyl dihydrogen phosphates and dialkyl monohydrogen phosphates, prepared as concentrates in kerosene, according to the procedure described in Example 1 of US. Pat. No. 3,228,758.

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A multi-component multi-functional composition for addition to distillate hydrocarbon fuels, said composition consisting essentially of A. a hydrocarbon fuel-soluble salt of i. a C, to C aliphatic monoamine wherein each aliphatic radical attached to the amine nitrogen is attached through a saturated carbon atom and ii. a C8 to C branched chain primary alkyl acid ester of orthophosphoric acid, and

B. from 1 to parts by weight per part of said salt of a normally liquid hydrocarbon-soluble polybutene having a number average molecular weight in the range 400 to 3000 and a viscosity in the range 500 to 900,000 SUS at 100F. and in the range 60 to 20,000 SUS at 210F.

Buick Intake Valve Deposit Test TEST B 2-cthylhcxylaminc salt of mixed monoand di(0xo)tridccyl acid phosphate as described in Examples l-7 The results of Tests A and B in conjunction with the detergent test show that the additive combination is effective not only as a carburetor detergent but also as an agent to inhibit formation of intake valve tulip deposits.

2. The composition of claim 1 which contains:

C. a hydrocarbon solvent in a minor proportion sufficient to improve the handling characteristics of the composition.

3. The composition of claim 1 wherein the amine salt is a substantially neutral salt of a C, to C alkyl primary amine and a C to C Oxo-alkyl acid ester of orthophosphoric acid.

4. The composition of claim 3 wherein the alkyl groups of said orthophosphoric acid ester have eight to l3 carbon atoms each.

5. The composition of claim 4 wherein the amine salt is the 2-ethylhexylamine salt of a mixture of about 40 to 60 mole percent of tridecyl dihydrogen orthophosphate and about 60 to 40 mole percent of ditridecyl monohydrogen orthophosphate and the polybutene/amine salt weight ratio is between about 1/ 1 and about 50/1.

6. The composition of claim 4 wherein the amine salt is the isobutylammonium salt of a mixture of about 40 to 60 mole percent of tridecyl dihydrogen orthophosphate and about 60 to 40 mole percent of ditridecyl monohydrogen orthophosphate and the polybutene/amine salt weight ratio is between about 1/1 and 50/1.

7. The composition of claim 3 wherein the polybutene/amine salt weight ratio is between about /1 and 30/1.

8. The composition of claim 5 wherein thepolybutene is a polyisobutene having a molecular weight in r the range 950 to 2700 and a viscosity in the range 100,000 to 125,000 SUS at 100F. and in the range 2,000 to 3,000 at 210F.

10. A composition according to claim 2 wherein the amine salt amounts to from about 1.5 to 30 percent by weight of the composition, the polybutene amountsto from about 30 to 80 percent by weightof the composition, and the hydrocarbon solvent amounts to from 10 to 40 percent by weight of the composition. I

ll. A-composition according to claim 10 wherein A. the amine salt amounts to from 3 to percent by weight of the composition,

B. the polybutene amounts to from 60 to 80 percent by weight of the composition, and

C. the hydrocarbon solvent amounts to from 15 to 30 percent by weight of the composition.

12. A composition according to claim- 11 wherein A. the amine salt amounts to from 5 to 6 percent by weight of the composition,

B. the polybutene amounts to from 70 to 75 percent by weight of the composition, and

C. the hydrocarbon solvent consists essentially of xylene amounting to from 18 to 24 percent by weight of the composition.

13. A composition according to claim 11 wherein A. the amine salt amounts to from 10 to 12 percent by weight of the composition,

B. the polybutene amounts to from 65 to 70 percent by weight of the composition, and C. the hydrocarbon solventconsists essentiallyof xylene amounting to from 15 to percent by weight of the composition. I

14.'A gasoline comprising an 1. automotive gasoline that normally tends to form induction system deposits in use in spark ignition engines,

2. from about 0.0005 to about 0.008 weight percent based on the gasoline of a gasoline-soluble salt of i. a C to C aliphatic monoamine wherein each aliphatic radical attached to the amine nitrogen is attached through a saturated carbon atom, and

ii. a C to C branched chain primary alkyl acid ester of orthophosphoric acid, and

3. from about 0.01 to about 0.3 percent by weight based on the gasoline of a normally liquid, gasoline-soluble polybutene having a number average molecular weight in the range 400 to 3000 and a viscosity in the range 500 to 900,000 SUS at F.

and in the range 60 to 20,000 SUS at 210F.,

the polybutene/amine salt weight ratio being between about l/l to about 50/1.

15. The gasoline composition of claim 14 containing additionallyan antiknock quantity of an organolead antiknock agent.

16. The gasoline composition of claim 15 wherein the amine salt amount is between about 0.002 and 0.005 percent, the polybutene between about 0.01 and 0.1 percent, by weight of the composition.

17. The gasoline composition of claim 16 wherein the amine salt is a substantially neutral salt of a C to C}; alkyl primary amine and a C to C Oxo-alkyl acid ester of orthophosphoric acid.

18. The gasoline composition of claim 17 wherein the alkyl groups of said orthophosphoric acid ester have 8 to 13 carbon atoms each.

19. The composition of claim 17 wherein the amine salt is the isobutylammonium salt of a mixture of about 40 to '60 mole percent of tridecyl dihydrogen orthophosphate and about 60 to 40 mole percent of ditridecyl monohydrogen orthophosphate and the polybutene/amine salt weight ratio is between about 1/1 and 50/1.

20. The gasoline composition of claim 17 wherein the amine salt is the 2-ethylhexylamine salt of a mixture of about 40 to 60 mole percent of tridecyl dihydrogen orthophosphate and about 60 to 40 mole percent of ditridecyl mono-hydrogen orthophosphate, and the polybutene/amine salt weight ratio is between about 5/1 and about 30/1.

21. The gasoline composition of claim 20 wherein the polybutene/amine salt weight ratio is between about 5/1 and about 8/1.

22. The gasoline composition of claim 20 wherein the polybutene/amine salt weight ratio is'between about 10/1 and about 14/1.

23. The gasoline composition of claim 20 wherein the polybutene consists essentially of a polyisobutene having a molecular weight in the range 950 to 2700 and a viscosity in the range 40,000 to 890,000 SUS at 100F. and in the range 1,000 and 19,500 SUS at 210F.

Claims

2. from about 0.0005 to about 0.008 weight percent based on the gasoline of a gasoline-soluble salt of i. a C4 to C10 aliphatic monoamine wherein each aliphatic radical attached to the amine nitrogen is attached through a saturated carbon atom, and ii. a C8 to C16 branched chain primary alkyl acid ester of orthophosphoric acid, and
2. The composition of claim 1 which contains: C. a hydrocarbon solvent in a minor proportion sufficient to improve the handling characteristics of the composition.
3. The composition of claim 1 wherein the amine salt is a substantially neutral salt of a C4 to C8 alkyl primary amine and a C8 to C16 Oxo-alkyl acid ester of orthophosphoric acid.
3. from about 0.01 to about 0.3 percent by weight based on the gasoline of a normally liquid, gasoline-soluble polybutene having a number average molecular weight in the range 400 to 3000 and a viscosity in the range 500 to 900,000 SUS at 100*F. and in the range 60 to 20,000 SUS at 210*F., the polybutene/amine salt weight ratio being between about 1/1 to about 50/1.
4. The composition of claim 3 wherein the alkyl groups of said orthophosphoric acid ester have eight to 13 carbon atoms each.
5. The composition of claim 4 wherein the amine salt is the 2-ethylhexylamine salt of a mixture of about 40 to 60 mole percent of tridecyl dihydrogen orthophosphate and about 60 to 40 mole percent of ditridecyl monohydrogen orthophosphate and the polybutene/amine salt weight ratio is between about 1/1 and about 50/1.
6. The composition of claim 4 wherein the amine salt is the isobutylammonium salt of a mixture of about 40 to 60 mole percent of tridecyl dihydrogen orthophosphate and about 60 to 40 mole percent of ditridecyl monohydrogen orthophosphate and the polybutene/amine salt weight ratio is between about 1/1 and 50/1.
7. The composition of claim 3 wherein the polybutene/amine salt weight ratio is between about 5/1 and 30/1.
8. The composition of claim 5 wherein the polybutene is a polyisobutene having a molecular weight in the range 950 to 2700 and a viscosity in the range 40,000 to 890,000 SUS at 100*F. and in the range 1,000 and 19,500 SUS at 210*F.
9. The composition of claim 5 wherein the polybutene is a polyisobutene having a molecular weight in the range 1,200 to 1, 400 and a viscosity in the range 100,000 to 125,000 SUS at 100*F. and in the range 2,000 to 3,000 at 210*F.
10. A composition according to claim 2 wherein the amine salt amounts to from about 1.5 to 30 percent by weight of the composition, the polybutene amounts to From about 30 to 80 percent by weight of the composition, and the hydrocarbon solvent amounts to from 10 to 40 percent by weight of the composition.
11. A composition according to claim 10 wherein A. the amine salt amounts to from 3 to 15 percent by weight of the composition, B. the polybutene amounts to from 60 to 80 percent by weight of the composition, and C. the hydrocarbon solvent amounts to from 15 to 30 percent by weight of the composition.
12. A composition according to claim 11 wherein A. the amine salt amounts to from 5 to 6 percent by weight of the composition, B. the polybutene amounts to from 70 to 75 percent by weight of the composition, and C. the hydrocarbon solvent consists essentially of xylene amounting to from 18 to 24 percent by weight of the composition.
13. A composition according to claim 11 wherein A. the amine salt amounts to from 10 to 12 percent by weight of the composition, B. the polybutene amounts to from 65 to 70 percent by weight of the composition, and C. the hydrocarbon solvent consists essentially of xylene amounting to from 15 to 20 percent by weight of the composition.
14. A gasoline comprising an
15. The gasoline composition of claim 14 containing additionally an antiknock quantity of an organolead antiknock agent.
16. The gasoline composition of claim 15 wherein the amine salt amount is between about 0.002 and 0.005 percent, the polybutene between about 0.01 and 0.1 percent, by weight of the composition.
17. The gasoline composition of claim 16 wherein the amine salt is a substantially neutral salt of a C4 to C8 alkyl primary amine and a C8 to C16 Oxo-alkyl acid ester of orthophosphoric acid.
18. The gasoline composition of claim 17 wherein the alkyl groups of said orthophosphoric acid ester have 8 to 13 carbon atoms each.
19. The composition of claim 17 wherein the amine salt is the isobutylammonium salt of a mixture of about 40 to 60 mole percent of tridecyl dihydrogen orthophosphate and about 60 to 40 mole percent of ditridecyl monohydrogen orthophosphate and the polybutene/amine salt weight ratio is between about 1/1 and 50/1.
20. The gasoline composition of claim 17 wherein the amine salt is the 2-ethylhexylamine salt of a mixture of about 40 to 60 mole percent of tridecyl dihydrogen orthophosphate and about 60 to 40 mole percent of di-tridecyl mono-hydrogen orthophosphate, and the polybutene/amine salt weight ratio is between about 5/1 and about 30/1.
21. The gasoline composition of claim 20 wherein the polybutene/amine salt weight ratio is between about 5/1 and about 8/1.
22. The gasoline composition of claim 20 wherein the polybutene/amine salt weight ratio is between about 10/1 AND about 14/1.
23. The gasoline composition of claim 20 wherein the polybutene consists essentially of a polyisobutene having a molecular weight in the range 950 to 2700 and a viscosity in the range 40,000 to 890,000 SUS at 100*F. and in the range 1,000 and 19,500 SUS at 210*F.