US3318812A - Emission control additives - Google Patents

Description

United States Patent 3,313,212 EMISSION CONTRGL ADDITIVES Thomas H. Coiiield, Farmington, Mich, assignor to Ethyl Corporation, New York, N.Y., a corporation of Virginia No Drawing. Filed Aug. 9, 1965, Ser. No. 478,461 21 Claims. (Cl. 252-52) This application is a continuation-in-part of application Ser. No. 473,517, filed July 20, 1965 and now abandoned.

This invention relates to improved gasoline and antiknock fluid compositions. In particular, this invention relates to gasoline, :antiknock fluid, and engine lubricating oil containing an orthoester, resulting in reduced exhaust emissions when such engine lubricating oil, gasoline, or a gasoline containing such fluid, is used in an internal combustion engine.

In recent years, extensive research has been devoted to the alleviation of air pollution in many metropolitan areas. Part of this eifort has been directed to methods of reducing the unburned hydrocarbons emitted with the exhaust gas of internal combustion engines. Such unburned hydrocarbons tend to react with other atmospheric substituents to substantially contribute to air pollution and to cause smog in certain communities.

The quality and quantity of unburned and partially oxidized hydrocarbons vary widely, depending on vehicle operating conditions and upon the conditions of maintenance of the engine. For example, under idle conditions the concentration of unburned hydrocarbons in the exhaust gas stream may be as low as 300 parts per million, whereas under decelerating conditions the concentration may be over 5000 parts per million. Moreover, depending on operating conditions, a variety of partial oxidation products are present in the exhaust stream. It has also been found that the amount of unburned hydrocarbons emitted by a new engine increases with engine running time until an equilibrium is reached and that this increase is due to the build-up of deposits in the combustion chamber of the engine.

An examination of the published literature reveals that up to now the only means suggested to alleviate this problem have been to (a) modify the carburetion so as to more efliciently use the fuel, thereby lowering the emission of unused or partially used hydrocarbons and (b) trap or further oxidize the exhaust emissions in the muffler or muffler area; e.g., by the use of such devices as catalytic converters, after-burners, absorbers (liquid washing devices), porous solid absorbers, condensers, etc. These proposed solutions are only partially effective and do not reduce the amount of emitted hydrocarbons to the point where pollution and smog problems are effectively eliminated.

Accordingly, it is an object of this invention to provide a new approach to the problem of reducing exhaust emissions and combustion chamber deposits; More particularly, it is an object of this invention to provide engine lubricating oil, gasoline, and fluids for use in gasoline, containing an additive that has the effect of reducing exhaust emissions and combustion chamber deposits when such gasoline is used in an internal combustion engine. It is another object of this invention to provide for the operation of a spark-ignited internal combustion engine by using such engine oil as a lubricant or such gasoline as fuel for such engines. It is a further object of this invention to provide such engine lubricating oils, gasolines and fluids in which said additive is an orthoester. Other objects of this invention will become apparent from the following detailed description and appended claims.

The above and other objects of this invention are accomplished by providing a composition comprising (a) a antiknock fluid, and (b) an orthoester having the general formula:

wherein X is oxygen or sulfur, and R R and R are organic groups independently selected. from hydrocarbon groups such as alkyl, cycloalkyl, allrenyl, aryl, aralkyl, and alk-aryl groups, and substituted hydrocarbon groups wherein the above recited groups may contain substituents such as halogen, hydroxyl, carboxyl, alkoxycarbonyl, amino, or amide radicals.

Generally, any orthoester may be employed as an emission control additive in this invention. However, it is desirable that these additives possess certain properties. The most useful orthoesters employed in this invention are relatively stable under atmospheric conditions and thereby permit easy handling and simple and inexpensive formulation procedures. Furthermore, the preferred additives are stable in the gasoline, lubricating oil, or antiknock fluid and should not react with any of the additives already contained in said materials to destroy the activity of the additives or of the onthoformate.

The orthoester emission control additives should not yield, under combustion conditions, decomposition products which may be damaging to the engine parts or pro duce exhaust gases that are poisonous or otherwise harmful to human life.

The preparation of orthoesters is well known in the art. Ample description of the various methods of preparation may be found in Wagner et al., Synthetic Organic Chemistry, John Wiley and Sons, New York, N.Y. (1953), Chapter 16, pages 542-545, and Post, The Chemistry of the Aliphatic Orthoesters, Reinhold Publishing Corp, New York, NY. (1943), Chapter 2, pages 11-43. The various examples of orthoformates and orthothioformates' contained in Table 60, Wagner et al., supra, and Tables 1-5, Post, supra, are incorporated herein as if fully set forth.

Below are listed non-limiting examples of groups which may be present in the above general formula as R groups. These groups may be present irrespective of whether the orthoesters are orthoformates or orthothioforrnates.

Examples of alkyl groups represented by the R groups in the above general formula are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert.-butyl, n-amyl, and the various positional isomers thereof, and likewise the corresponding straight and branched chain isomers of hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, and the like.

When said R groups are cycloalkyl groups, they may be cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, and the like. They may also be such cycloaliphatic groups as a cyclopropyl-ethyl, a-cyclobutyh propyl, B-cyclob-utyl-propyl, and similar alkyl derivatives of the higher cycloalkyls.

The R groups in the above general formula may also be alkenyl groups such as ethenyl, l-propenyl, 2-propenyl, isopropenyl, l-butenyl, 2-butenyl, 3-butenyl, and the corresponding branched-chain isomers thereof as, for example, l-isobutenyl, 2-isobutenyl, 2sec-butenyl, including l-methylene-Z-propenyl, and the various isomers of pentenyl, hexenyl, heptenyl, oetenyl, nonenyl, decenyl, undecenyl, and dodecenyl, including 3,3-dimethyl-1-butenyl, 2,3-dimethyl-l butenyl, 2,3 dimethyl-Z-butenyl, 2,3-diinethyl-3-butenyl, l-methyl-I-ethyl-Z-propenyl, and the like.

When said R groups are alkaryl groups, they may be .decyl, 12-hydr0xydodecyl, and the like.

2,3-xylyl, 2,4-xylyl, 2,5-x'ylyl, 2,6-xylyl, 3,4-xylyl, 3,5- xylyl; o, m, and p-cumenyl, mesityl, o, in, and p-ethylphenyl, Z-methyl 1- naphthyl, 3 methyl-l-naphthyl, 4- methyl 1 naphthyl, 5 methyl-Z-naphthyl, 6 methyl-3- naphthyl, 7-methyl-1-naphthyl, 8 methyl-4-naphthyl, 1- ethyl-2-naphthyl, and its various positional isomers, and the like.

Examples of aryl groups which may be present in the above general formula are phenyl, naphthyl, and the like.

When said R groups are aralkyl groups, they may be benzyl, phenylethyl, l-phenylpropyl, Z-phenylpropyl, 3- phenylpropyl, 1 and 2 isomers of phenylisopropyl, 1, 2 and 3 isomers of phenylbutyl, and the like.

Furthermore, the R groups as defined above may be substituted by a halogen, hydroxyl, carboxyl, alkoxycarbonyl, amino, and amido (carbamyl) radicals. Thus, the three R groups may contain the same or different substituents or any one R group may contain one or more of said radicals substituted thereon.

As mentioned above, the R groups may be halogen substituted. Thus, chlorine, bromine, iodine, and fluorine may be substituted on the alkyl, cycloalkyl, alkenyl, alkaryl, aryl, and aralkyl groups which are present in the orthoformate molecule. Non-limiting examples of such substituted groups are chloromethyl, bromoethyl, 2- fiuoro-1,2-dibromoethyl, l-iodopropyl, Z-fluoropropyl, 1-

chlorobutyl, 2-bromobutyl, 2-iodo-2-methylpropyl, 1- chloropentyl, 3 -fluoro-2-methylbutyl, 3 -iodo-2-methylbutyl, 1-chlor0-2,2-dimethy1propyl, 2-chloroheptyl, 3-

fiuorononyl, l-chlorododecyl, and the like. Examples of halogenated cycloalkyl groups are chlorocyclopropyl, chlorocyclohexyl, 1,2-dichlorocyclohexyl, bromocyclobutyl, iodocycloheptyl, and the like.

Examples of halogen-substituted alkenyl groups are bromoethenyl (bromovinyl radical), chloroethenyl, iodoethenyl, l-brornopropenyl, l-chloropropenyl, l-chloroheptenyl, l-bromododecenyl, and the like.

Examples of halogenated alkaryl groups are chloro-otolyl, chloro-p-tolyl, chloro-m-tolyl, ar-(l-bromoethyl) benzyl, ar-(2-bromoethyl)benzyl, ar-2-bromo-ar-4-ethylbenzyl, and all positional isomers thereof, 2-bromo-3,4- xylyl, 4-bromo-2,3-xylyl, 5-bromo-2,4-xylyl, 2-bromo-4,5- xylyl, o, m and p-tolyl, 3-bromomesityl, chloro(methyl) l-naphthyl, iodo(ethyl) l-naphthyl, all positional isomers of the above, and the like. Examples of halogensubstituted aryl groups are bromobenzyl, 2-bromo-l-naphthyl, 3-bromo-1-naphthyl and all positional isomers thereof, 2,4-dibromobenzyl, 2,3-dibromobenzyl, 2,5-dibromobenzyl, 2,3,4-tribromobenzyl, 2,4,5-tribromobenzyl, 2,3,5- tribromobenzyl, 2,3,4,5 -tetrabromobenzyl, 2,3,5,6-tetrabromobenzyl, pentabromobenzyl, all isomers of chlorobenzyl, and all isomers of multichlorobenzyl; 2-chloro-lnaphthyl and the remaining isomers thereof; 2,3-dichlorol-naphthyl, 2,4-dichloro-1-naphthyl and the remaining positional isomers of dichloronaphthyl; 2,3,4,5-tetrachloro-l-naphthyl, iodobenzyl, all isomers of multiiodobenzyl; 2-iodo-l-naphthyl, and all isomers of multiiodonaphthyl; fluorobenzyl and all isomers of multifluorobenzyl; Z-fluoro-l-naphthyl, and all isomers of multifiuoronaphthyl.

The R groups in the general orthoester formula may also contain hydroxy substituents yielding different types of alcohol groups, a few non-limiting examples of which are 2 hydroxyethyl, 2 hydroxyisopropyl, 5 hydroxypentyl, 3-hydroxyheptyl, 2,3-dihydroxybutyl, IO-hydroxy- Other examples of hydroxy-containing groups are hydroxycyclopentyl, hydroxycyclohexyl, Z-hydroxyethenyl (2-hydroxyvinyl radical), 5-hydroxy-2-penten-1-yl, hydroxy-o-tolyl, hydroxym-tolyl, hydroxy -p phenyl, 2 hydroxy-l-naphthyl, 2- methyl-S-hydroxy-l naphthyl, 3-isopropyl-7-hydroxy-lnaphthyl, phenol, 2-hydroxyethylphenyl, 3-(2-hydroxyethyl)-o-tolyl and various positional isomers, 2-butyl-4- (2-hydroxyethyl)phenyl, xylenyl, and the like.

The R groups in said general formula may also be ester E (al-koxycarbonyl) groups such as Z-(methoxycarbonyl) ethyl, 5 (ethoxycarbonyl)pentyl, 8 (butoxycarbonyl) octyl, 2,4-bis(ethoxycarbonyl) cyclohexyl, 2-(phenoxycarbonyl)ethyl, 3 (phenoxycarbonyl)propyl, 2-(ethoxycarbonyl) phenyl, and the like.

When said R group contains carboxylic groups, the following may be listed as illustrative examples: Z-carboxyethyl, 4-carboxybutyl, 8-carboxyoctyl, ll-carboxyundecyl, carboxycyclopropyl, carboxycyclopentyl, carboxycyclohexenyl, 1,3-dicarboxycyclobutyl, l,4dicarboxybutenyl, 3-carboxy-2-propen-l-yl, 2-carboxyethenyl, carboxybenzyl, Z-carboxy-o-tolyl, 3-carboxy-o-tolyl, 4-carboxy-m-tolyl, 4-carboxy 2,3-dimethylbenzyl, 3-carboxy- 2,4-dimethylbenzyl, and the remaining positional isomers of dimethylbenzyl, 2-carboxy-1-naphthyl, 2-methyl-3-carboxy-l-naphthyl, 2-butyl-6-carboxy-l-naphthyl, and the like.

Amine groups may also be substituted on the R groups. Some illustrative examples of R groups containing amine substituents are aminomethyl, Z-aminoethyl, 2,2-diaminoethyl, Z-aminoisopropyl, S-aminopentyl, l'2-arninododecyl, 1,2-diaminoethyl, 'l,5-diaminopentyl, aminocyclobutyl, aminocyclohexyl, 3-amino-l-propen-l-yl, 5-amino-2-penten-l-yl, aminophenyl, (methylamino )phenyl, 2-amino-otolyl, 4-amino-m-tolyl, 3-amino-p-tolyl, and other positional isomers, various isomers of diaminophenyl, amino- 2,5-xylyl, and various positional isomers thereof, 2-aminol-naphthyl, 3-amino l-naphthyl, Z-arnino 3-methyl 1- naphthyl, 2,3-diamino-5-et-hyl-l-naphthyl, and the like.

The R groups may contain amide groups which may be illustrated by such examples as: carbamoylmethyl, 2-car- .bamoylethyl, 4-carbamoylbutyl, 8-carbamoyl-Z-ethyloctyl, 1,4-dicarbamoylbuty1, carbamoylcyclopentyl, carbamoylcyclohexyl, Z-carbamoyl-o-tolyl, Z-carbamoyl-rn-tolyl, 3- carbamoyl-p-tolyl, (carbamoylmethyl)phenyl, (Z-carbamoylet-hyl)benzyl; o, m, and p-(Z-carbamoylethyl)phenyl, and the like.

From among the different R groups illustrated above, orthoesters wherein the R groups are alkyl groups are preferred, especially those containing up to about 6 carbon atoms. Particularly, triethylformate is most highly preferred.

Tests were run to illustrate the unusual and beneficial effects of the products of this invention on reducing engine combustion chamber deposits and exhaust emissions. In such tests, an Oldsmobile type single cylinder engine with a 10.0121 compression ratio is used, using a Standard, 10W-30 commercial lubricating oil and a 26% aromatic Indolene fuel containing 3.0 ml. commercial TEL per gallon (containing 0.5 theory bromine as ethylene dibromide and 1.0 theory chlorine as ethylene dichloride).

Engine preparation.Before each test, the combustion chamber, valves and valve parts are cleaned of deposits and the valves are reseated. The old oil is drained, the oil pan is flushed with new oil and then filled with new oil. A new spark plug is installed and the fuel lines are flushed with new test fuel.

Start of test procedure.-The engine is started on isooctane, from a fuel burette, at 50 percent wide open throttle air flow, at a speed of 1370 rpm, an air/fuel ratio of about 88 percent stoichiometric, with an ignition timing of 15 B.T.C. These conditions are maintained until the water and oil sump are at :5" F. and the carburetor air is at ll0- -5 F. At this condition exhaust measurements are made for hydrocarbon and carbon monoxide so as to detect any engine changes compared to other tests in the same engine. Hydrocarbon measurements are made with a Beckman 109 Flame Ionization Hydrocarbon Detector. Carbon monoxide is measured with a Beckmann 15A Non-Dispersive Infrared Analyzer.

The engine is then switched to the test fuel and the air/ fuel ratio is adjusted to 88% of the stoichiometric airfuel ratio required by the test fuel. Using fuel burette,

the fuel flow is adjusted to the rate of 25 ml. of fuel per Time seconds 135.

Speed, r.p.m 1,

Load 50% W.O.1. Air Flow. Air/fuel rat1o A/Fi0.2.*

Ignition t1m1ng BTG.

Oil sump, 165i5.

Water, 165i5.

Carburetor air, F 110:1;5.

88% of stoiehiornetric air/fuel ratio required by test fuel.

The test is run for about 145 hours with emission measurements made every 24 hours.

Periodic emission raiings.-After about each 24 hours of test time, the engine is shut down and a new spark plug is installed. The engine is restarted with test fuel at the steady state conditions described above for Start of Test Procedure. The air/fuel ratio is adjusted by measuring fuel flow time from a burette. Hydrocarbon emission measurements are taken and the engine is again shut down to zero oil level, after which it is returned to the cycling schedule.

End of test pr0cedure.--At the end of 140145 hours of test, hydrocarbon emission measurements are taken, the engine is returned to a cycling schedule for a 1-2 hour period and then shut down. The engine head is removed and deposits are scraped, removed and weighed from the intake valve stem, the exhaust valve top, the combustion chamber-valve area and the piston area.

The following results were obtained in the above tests when a 26 percent aromatic Indone fuel, containing 3.0 m1. of oommerical TEL, with and without the indicated amount of triethyl orthoformate, was used in the test fuel.

1 End of test minus start of test results.

As demonstrated by the data in Table I, when orthoesters of the type described above are blended with gasoline, preferably in the amount of from about 0.001 to about 10 weight percent of the gasoline, spectacular results are obtained in the reduction of exhaust emissions and combustion chamber deposits. A more preferred amount is from about 0.05 to about 2.0 weight percent of the gasoline. These effects are obtained both in the presence and absence of organolead antiknock agents, in the presence or absence, together with organolead-antiknock agents, or alone, of a non-lead organometallic antiknock compound and in the presence or absence of a halohydrocarbon scavenger for the antiknock compound.

Among the organolead antiknock agents which can be present in the gasoline are lead alkyls and alkenyls and mixed lead alkenyl alkyls wherein each alkyl or alkenyl group contains up to about six carbon atoms and includes compounds such as tetramethyllead, tetraethyllead, tetravinyllead, tetraisopropyllead, tetrapropyllead, diethyldiphenyl-alkyl compounds such as tetraphenyl, trimethylphenyl, diphenyldiethyl, triphenylpropyl, etc., and mixtures thereof, may also be present. The mixtures of lead antiknocks may be redistributed mixtures such as those prepared by redistributing two or more tetraalkyl or tetraalkenyl lead compounds. These mixtures contain all the lead compounds formed by a random redistribution of the radicals bonded to lead. Generally from about 0.5 to about 6.5 grams of lead are present per gallon of gasoline.

Among the non-lead organometallic antiknock compounds that may be present are organic compounds of a metal having an atomic number of from 25-28 (i.e., manganese, iron, cobalt and nickel) as well as calcium, tin, and copper. Said organic compounds generally are hydrocarbon-soluble, covalent, and possess, in addition to said metal, only elements selected from the group consisting of carbon, oxygen, hydrogen, and nitrogen. Such compounds generally contain at least one group selected from the class consisting of cyclopentadienyl groups and the carbonyl group, and contain from. about 5 to about 20 carbon atoms in the molecule. Generally, from about 0.005 to about 6.5 grams of such organometallie compound are present per gallon of gasoline.

Among the manganese compounds are the cyclopentadienyl manganese tricarbonyls as described, for example, in U.S. Patents 2,818,416 and 2,818,417, including cyclopentadienyl manganese tricarbonyl, methylcyclopentadienyl manganese tricarbonyl, indenyl manganese tricarbonyl, manganese pentacarbonyl, and the like.

Among the nickel compounds are those described in US. Patent 2,818,416, including cyclopentadienyl nickel nitrosyl, methylcyclopentadienyl nickel nitrosyl, indenyl nickel nitrosyl, and the like.

Among the iron compounds are the dicyclopentadienyl iron compounds such as dicyclopentadienyl iron, bis- (methylcyclopentadienyl) iron, bis(butylcyclopentadienyl) iron, and the like. Other iron compounds include iron pentacarbonyl, butadiene iron tricarbonyl, and the like.

Among the cobalt compounds are the cobalt carbonyls such as cobalt tetracarbonyl, cyclopentadienyl cobalt dicarbonyl, l-pentyne-cobalt tetracarbonyl, cobalt pentacarbonyl mixed complexes, and the like.

Examples of copper and calcium antiknocks which may be present in the gasoline are the coordination compounds of these metals such as the cupric derivative of 4-ethylirnino-Z-buten-Z-ol, 4-octylimino 2 buten-2-ol, and the like, and the calcium chelate of n-octyl acetoacetonate, n-butyl acetoacetonate, and the like.

Additionally, scavengers may be present, which scavengers are organic halide compounds which react with a metal, e.g., lead, during combustion in the engine to form volatile metal halides. The halogen of these scavengers has an atomic weight between 35 and that is, the active scavenging ingredient is chlorine and/or bro mine. Such scavengers include ethylenedibromide, ethylenedichloride, carbon tetrachloride, propylene dibromide, 2-chloro 2,3 dibromobutane, 1,2,3-tribromopropane, hexachloropropylene, mixed bromoxylenes, l,4-dibromobutane, 1,4 dichloropentane, the dibromodiisopropyl ether, p,fi-dichlorodiethyl ether, trichlorobenzene, dibromotoluenes, and in general those disclosed in U.S. Patents 1,592,954; 1,668,022; 2,365,921; 2,479,900; 2,- 479,901; 2,479,902; and 2,496,983. The amount of scavenger generally employed is from about 0.5 to about 2.5 theories. Mixtures of bromine and chlorine-containing scavengers can be used and in the proportions described in US. Patent 2,398,281.

Gasoline containing an organolead antiknock, particularly tetraethyl and/or tetramethyllead, and more particularly which also contain a halohydrocarbon scavenger are generally more greatly benefitted by inclusion of a product of this invention than other gasolines.

The following examples illustrate the gasoline compositions of this invention. The types of gasolines used are characterized as follows:

8 1.0 theory of dibromobutane as scavenger are added 0.062 pounds of triethyl orthoforrnate.

Gasoline Paratlins, Olefins, Aromatics, Naphthenes, End Point, Gravity, Vapor Pres- Percent Percent Percent Percent F. API sure. p.s.1.

A .c 45. 2 29. 4 25. 4 390 59. 8. 9 B 70.1 15.6 14. 3 385 64. 4 C .2 39.1 21.1 17.1 2 8 420 61. 4 l1. 7 D 64. 8 15.1 20.1 403 56. 2 9. E 44. 0 17.9 38.1 366 54.6 I 7.8

Example 1 Example 7 To 1000 gallons of gasoline A containing 3.24 grams per gallon of tetraethyllead, 0.5 theory of ethylene dibromide and 1.0 theory of ethylene dichloride are added 18.6 pounds of triethyl orthoformate to yield a gasoline composition causing less exhaust emissions and less combustion chamber deposits than a similar gasoline without triethyl orthoformate.

Example 2 To 1000 gallon of gasoline B containing 3.5 grams per gallon of a commercial antiknock fluid, which fluid contains 57.52 weight percent tetramethyllead, 6.97 weight percent methyl cyclopentadienyl manganese tricarbonyl, 16.71 Weight percent ethylene dibromide, and 17.60 Weight percent ethylene dichloride, are added 9.3 pounds of triethyl orthoformate to yield a gasoline composition of this invention.

Example 3 To 1000 gallons of gasoline C containing 2.16 grams per gallon of a commercial TEL fluid, which fluid contains 61.41 Weight percent of tetraethyllead, and 35.68 weight percent of ethylene dibromide are added 12.4 pounds of triethyl orthoformate to yield a gasoline composition of this invention.

Example 4 To 1000 gallons of gasoline D containing 0.028 Weight percent sulfur, 2.69 grams per gallon of a commercial TEL antiknock fluid, which fluid contains 61.48 weight percent tetraethyllead, 17.86 weight percent ethylene dibromide, and 18.81 weight percent ethylene dichloride, and which gasoline has a Research Octane number of 99.4 and a Motor Octane number of 91.2 are added 3.1 pounds of triethyl orthoformate to yield a gasoline composition causing less exhaust emissions and less combustion chamber deposits than a similar gasoline without triethyl orthoformate.

Example 5 To 1000 gallons of gasoline E containing 0.65 weight percent sulfur and 2.0 grams per gallon of a commercial TML antiknock fluid, which fluid contains 50.82 Weight percent of tetramethyllead, 17.86 weight percent of ethylene dibromide, 18.81 weight percent of ethylene dichloride and 12.51 weight percent of hydrocarbons and other inerts, are added 6.2 pounds of dimethylpropyl orthoformate.

Example 6 To 1000 gallons of gasoline A containing 0.03 weight percent sulfur and 2.24 grams per gallon of tetramethyllead, 0.2 weight percent of dicyclopentadienyl iron and To 1000 gallons of gasoline B containing 0.03 weight percent of sulfur, 6 grams per gallon of lead as tetraethyllead and 1.0 theory of ethylene dibromide as scavenger are added 310 pounds of triethyl orthothioformate.

Example 8 To 1000 gallons of gasoline C containing 1 gram per gallon lead as tetrarnethyllead, 0.08 weight percent of cyclopentadienyl nickel nitrosyl and 1.0 theory of ethylene dibromide as scavenger is added 0.62 pounds of tricyclopropyl orthoformate.

Example 9 To 1000 gallons of gasoline D containing 2.5 grams per gallon of a commercial antiknock fluid, which fluid contains 56.15 Weight percent of a mixture of tetramethyllead, ethyltrimethyllead, diethyldimethyllead, triethylmethyllead, and tetramethyllead, 17.86 weight percent of ethylene dibromide and 18.81 percent of ethylene dichloride, are added 49.6 pounds of tridodecyl orthoforrnate.

Example 10 To 1000 gallons of gasoline E containing 5.0 grams per gallon of tetraethyllead, 0.23 weight percent of cobalt tetracarbonyl and 1.0 theory of propylene dibromide are added 186 pounds of triethenyl orthoformate.

Example 11 To 1000 gallons of gasoline A containing 4.2 grams per gallon of tetrapropyl lead and 2.5 theory of chlorine as carbon tetrachloride are added 124 pounds of tricyclopentadienyl orthoformate.

Example 12 To 1000 gallons of gasoline B containing 3.1 grams per gallon of tetraphenyl lead are added 31 pounds of tri-o-tolyl orthoformate.

The procedure of Example 12 is repeated except that tri-3,4-xylyl orthoformate, tris(2 methyl 1 naphthyl) orthoformate, triphenyl orthoformate, and tris(3-ethylphenyl) orthoformate are used in place of tri-o-tolyl orthoformate.

Example 13 9 Example 14 To 1000 gallons of gasoline C containing 1.0 gram per gallon of lead as tetramethyllead, 0.08 weight percent of cyclopent-adienyl nickel nitrosyl, and 1.0 theory of ethylene dibromide as scavenger, is added pounds of tri- (Z-hydroxyethyl) orthoformate.

The procedure of Example 14 is repeated employing tri(2,4 dihydroxyl 1 phenyl) orthoformate, tri(12-hydroxydodecyl) orthoformate, and -tri(3-hydroxy-o-tolyl) orthof-ormate in place of tri(2-hydroxyethyl) orthoformate.

Example 15 To 1000 gallons of gasoline B containing 0.03 weight percent of sulfur, 3.5 grams per gallon of lead as tetravinyllead, and 1.0 theory of ethylene dibromide as scavenger, are added 75 pounds of tri[2-(methoxycarbonyl ethyl ]ortl1othioformate.

In another example, tri[3-(phenoxycarbonyl)propyl]- orthoformate is used in place of tri[2-(methoxycarbonyl) ethyl] orthoformate.

Example 16 To 1000 gallons of gasoline A containing 0.03 weight percent sulfur, 2.24 grams per gallon of tetramethyllead, 0.2 weight percent of dicyclopentadienyl iron and 1.0 theory of dibroniobutane as scavenger, are added pounds of tri(2-carboxyethyl) orthoformate.

In another example, tri(6-carboxyhexyl) orthoformate and tri(2-carboxy-p-tolyl) orthoformate were used in place of tri(2-carboxyethyl) orthoformate.

Example 17 To 1000 gallons of gasoline D containing 0.028 weight percent sulfur, 2.69 grams per gallon of a commercial tetraethyllead antiknock fluid, which fluid contains 61.48 weight percent tetraethyllead, 17.86 weight percent ethylene dibromide, and 18.81 weight percent ethylene dichloride, and which gasoline has a Research Octane number of 99.4 and a Motor Octane number of 91.2 are added 3.1 lbs. of tri(2-aniinoethyl) orthoformate.

Repeating the procedure of Example 17, tri(4-amino-1- phenyl) orthoformate is used in place of tri(2-aminoethyl) orthoformate.

The orthoformates can be conveniently added to antiknock fluids and added to gasoline during blending of the gasoline with the fluid. The product can be added to concentrations of any of the above-mentioned organolead and/or non-lead organometallic antiknock compounds which concentrations can optionally contain any of the above halohydrocarbon scavengers. Thus, another embodiment of this invention is an antiknock fluid comprising an organometallic additive selected from the group consisting of organolead antiknock compounds and organic compounds of a metal having an atomic number of from 25-28 as described above, said fluid optionally containing a halohydrocarbon scavenger as described above and containing an orthoester.

The amount of exhaust emission reducing orthoester present in the fiuid can conveniently be from about 0.004 to about 280 parts of said ester per part of metal (i.e., if organolead is used, per part of lead; if another organometallic antiknock is used, per part of the metal of such antiknock) depending on the amount of antiknock and such product desired in the final formulated gasoline. A

preferred amount is from about 0.1 to about 5 parts of orthoester per part of metal.

Representative antiknock compositions of this invention are presented in Table 11 following. The parenthetic figures following the representative ingredients are parts by Weight.

TABLE II.-AN'IIKNOOK FLUID COMPOSITIONS Antiknock Agent Scavenger Product of Examples Tetramethyllead (2.67) None 1(3.4).

Do Ethylene dibrornide (226)... 2 (5.7). Do Ethylene dibromide (04) 3 (0.267).

ethylene dichloride Tetraethyllead (3.23) None: 4 (16.15).

Do Ethylene dibromide (188)- 5 (62.4). Do Ethylene dibromide (94) 6 (0.013).

21.519? ethylene dichloride Tetraphenyllead (3.00) Mixes dibromotolnenes 7 (0.5).

20 Tetraethyllead (2.70) and Mixed dibromotolnones 8 (25.0).

mcthylcyclopentadienyl (125) and ethylene di' 1(111a53iganese tricarbonyl chloride (99). Tetramethyllcad .99 and Mixed dibromotoluene 9 (28.0).

iron pentacarbonyl (0.01). (150) and 1,2,4-trichloro' benzene (175). Tetraethyllead (320) and Ethylene dibromide (94) 10 (10.8).

cobalt tetracarbouyl and mixed trichlorobendimer (2). zene (146). 'letrapropyllead (379) and Acetylene tetrabrornide 11 (30.6).

dicyclop entadienyl (346) nickel (5). Methyltriethyllead (309)-.. 1,4-dibron1obutane (216)-.. 12 (40.1).

The antiknock fluid compositions shown in the above table are presented for illustrative purposes only. Other such compositions will now be apparent to one skilled in the art. In all instances, the presence of orthoester enables the fluid to be used in gasoline with a resultant decrease in exhaust emissions.

An orthoester can also be effectively added to the engine lubricating oil. Thus, another embodiment of this invention comprises engine lubricating oil containing an exhaust emission reducing amount of an orthoester as defined above.

To prepare lubricating oils of this invention, an appropriate quantity, from about 0.01 to about 10 weight percent, and preferably from about 0.1 to about 5 weight percent, of an orthoester is blended with a lubricant base oil. Suitable base oils include mineral oils and synthetic diester oils such as sebacates, adipates, etc. The finished lubricants may also contain other additives such as antioxidants, viscosity index improvers, detergent-dispersants, corrosion inhibitors, antiwear agents, etc. The lubricants of this invention aid in the reduction of exhaust emissions and deposit weight by its consumption in the engine during operation.

The following examples illustrate lubricating oil Compositions of this invention.

Example 18 To 1000 parts of a solvent refined neutral oil V1. and 200 SUS at F. containing 6 percent of a commercial methacrylate Type VI approver which gives the finished formulation of a VI. of and a viscosity of 300 SUS at 100 F. is added 10 weight percent of triethyl orthoformate.

Example 19 To an additive-free solvent refined crankcase lubricating oil having a viscosity index of 95 and an SAE viscosity of 10 is added 0.01 weight percent of triphenyl orthoformate.

Example 20 To 100,000 parts of a petroleum hydrocarbon oil having a gravity of 30.3 APl at 60 F., a viscosity of 178.8 SUS at 100 F., a viscosity index of 154.2 and which contains 0.2 percent sulfur, is added 0.1 weight percent of tri(2- chloroethyl) orthoformate. The resulting oil allows the reduction of exhaust emissions and combustion chamber deposits.

Example 2] To 100,000 parts of a commercially available pentaerythritol ester having a viscosity at 100 F. of 22.4 centiill. stokes, and known in the trade as Thermoflex 600 is added 5.0 weight percent of tri(2-hydroxyethyl) orthoformate.

' Example 22 To 100,000 parts of dioctyl sebacate having a viscosity of 210 F. of 36.7 SUS, a viscosity index of 159, and a molecular weight of 426.7 is added 0.25 weight percent of tri(2-carboxyethyl) orthoformate.

The procedure of Example 22 is repeated employing triethyl orthothioformate and triphenyl orthothioformate in place of tri(2-carboxyethyl) orthoformate.

It was previously mentioned that the R groups in the above general formula may be alkenyl groups. In fact, trialkenyl orthoformate is another preferred embodiment of this invention. Numerous examples of alkenyl groups which may be present in the general formula are listed above, but additionally the following groups may also be present: crotonyl having the formula CH CH=CH (CH l-methyl-2-propenyl, 1,1-dimethyl-2-propenyl, 2-methyl-2-propenyl, 1,2-dimethyl-2-propenyl, 3-methyl-2-propenyl, 1,3-dimethyl-2-propenyl, 2,3-dimethyl-2-propenyl, 1,1,2-trimethyl-2-propenyl, 1,1,3-trimethyl-2apropenyl, 1,1,2,3-tetramethyl-Zpropenyl,

various halogen and nitro substituted propenyls, such as 1-chloro-2-propenyl, 1,2-dichloro-2-propenyl, 1-nitro-2-propenyl,

2-nitro-2-propenyl,

1-chloro-2-nitro-2-propenyl,

and the like. Specific examples of alkenyl orthoformates are triallyl orthoformate, tricrotonyl orthoformate, tripropenyl orthoformate and trioleyl orthoformate. Similarly, R groups in the above general formula may be benzyl groups or alkyl, alkenyl, halogen, nitro and amino substituted benzyl groups, such as 2,4-dimethyl-benzyl, 2-chl0ro- 4-methylbenzyl, Z-nitrobenzyl, 2-chloro-4-nitrobenzyl, and the like. A specific example of this type of orthoformates is tribenzyl orthoformate. Specific examples of halogenated orthoesters not mentioned above are tris(l-chloroethyl) orthoformate and tris(2-chloroethyl) orthoformate.

A highly preferred trialkenyl orthoformate is triallyl orthoformate. In Table III the test results show the high effectiveness of triallyl orthoformate in reducing the hydrocarbon content in exhaust emission gases, as Well as engine deposits. Triallyl orthoformate was employed in the indicated concentration in an Indolene fuel, which is a commercial type premium grade automotive fuel composed of 26 percent by volume of aromatics, 67 percent by volume of saturates and 7 percent by volume of olefins and containing 3.0 ml. of commercial TEL.

1 End of test minus start or test results.

Having fully described the novel uses of the compounds of this invention and their mode of preparation, it is desired that this invention be limited only within the lawful scope of the appended claims.

I claim:

1. Gasoline containing, as an emission control additive,

from 0.001 to about 10 weight percent of an orthoester having the general formula:

wherein X is oxygen or sulfur and R R and R are bydrocarbon groups having up to 12 carbon atoms and selected from the class consisting of alkyl, cycloalkyl, alkenyl, aryl, alkaryl, and aralkyl groups.

2. The composition of claim 1 wherein said R R and R are alkyl groups.

3. The composition of claim 2 wherein said alkyl groups are ethyl.

4. Gasoline containing from about 0.1 to about 2.0 weight percent of triethyl orthoformate as an emission control additive.

5. Gasoline containing from about 0.1 to about 2.0 weight percent of triethyl orthothioformate as an emission-control additive.

6. Gasoline containing an organometallic antiknock agent and from 0.001 to about 10 weight percent of an orthoester having the formula:

wherein X is oxygen or sulfur, and R R and R are hydrocarbon groups having up to 12 carbon atoms and independently selected from the class consisting of alkyl, cycloalkyl, alkenyl, aryl, alkaryl, and aralkyl groups.

7. The composition of claim 6 wherein R R and R are alkyl groups.

8. The composition of claim 7 wherein said alkyl groups are ethyl.

9. Gasoline containing a tetraalkyllead antiknock agent, a halohydrocarbon scavenger therefor, and from about 0.1 to about 2.0 weight percent of triethyl orthoformate as an emission control additive.

10. Gasoline containing an antiknock quantity of tetraethyllead, a halohydrocarbon scavenger therefor, and from about 0.1 to about 2.0 weight percent of triethyl orthothioformate as an emission control additive.

11. An antiknock fluid composition, for addition to gasoline, containing an exhaust emission reducing amount of an orthoester having the general formula:

wherein X is oxygen or sulfur, and R R and R are hydrocarbon groups having up to 12 carbon atoms and selected from the class consisting of alkyl, cycloalkyl, alkenyl, aryl, alkaryl, and aralkyl groups.

12. An antiknock fluid of claim 11 wherein said orthoester is a trialkyl orthoester.

13. An antiknock fluid of claim 12 wherein said trialkyl orthoester is triethyl orthoformate.

14. An antiknock fluid of claim 12 wherein said triallcyl orthoester is triethyl orthothioformate.

15. An antiknock fluid composition, for addition to gasoline, comprising a tetraalkyllead compound and a halohydrocarbon scavenger therefor, and containing from 0.004 to about 280 parts by weight per part by weight of lead, of a trialkyl orthoformate.

16. Engine lubricating oil containing from about 0.01 to about 10 weight percent of triethyl orthoformate as an emission control additive.

17. Gasoline containing from about 0.1 to about 2.0 weight percent of triallyl orthoformate as an emissioncontrol additive.

18. Gasoline containing an antiknock quantity of tetraethyllead, a halohydrocarbon scavenger therefor, and

13 from about 0.1 to about 2.0 Weight percent of triallyl orthoforrnate as an emission control additive.

19. An antiknock fluid composition, for addition to gasoline, comprising of tetraalkyllead compound and a halohydrocarbon scavenger therefor, and containing from 0.004 to about 280 parts by Weight per part by weight of lead, of a triallyl orthoforrnate.

20. Engine lubricating oil containing from about 0.01 to about 10 Weight percent of triallyl orthoformate as an emission control additive.

21. Engine lubricating oil containing an exhaust emission reducing amount of a trialkyl orthoformate.

References Cited by the Examiner UNITED STATES PATENTS Moran et a1 252-48.2 Brooks 260-424 Derrner et al 260-615 Webb 25245 Hinkarnp 252-52 10 DANIEL E. WYMAN, Primary Examiner. L. G. XLARHOS, Assistant Examiner.

Claims (1)

1. 21. ENGINE LUBRICATING OIL CONTAINING AN EXHAUST EMISSION REDUCING AMOUNT OF A TRIALKYL ORTHOFORMATE.