N-SUBSITUTED CARBAMATES AND THEIR USE AS FUEL ADDITIVES

Abstract: The invention provides N-substituted carbamates of formula R - A - - OR¹ (I) in which R is a poly(olefin) polymer chain having an average molecular weight in the range 500 to 9,900; R¹ is a hydrocarbyl or substituted hydrocarbyl group containing up to 20 carbon atoms; and A is derived from an N-substituted amino group in which the substituent is a hydrocarbyl or substituted hydrocarbyl group containing up to 20 carbon atoms, their preparation and their use as fuel additives, particularly in gasolines.

Description: This invention relates to N-substituted carbamates, to their preparation, to concentrates containing them for incorporation in liquid fuels, and to motor fuel compositions containing them. It is known that during the initial operation of a new or clean internal combustion engine, a gradual increase in octane requirement (OR), i.e., the fuel octane number required for knock-free operation, increases with the buildup of combustion chamber deposits until a stable level is reached which generally corresponds to a time when deposits remain relatively constant. The actual stable level can vary with engine design and even with individual engines of the same design. Many additives are known which can be added to hydrocarbon fuels to attempt to prevent or reduce deposit formation or remove or modify formed deposits in the combustion chamber and adjacent surfaces, such as valves, ports, and spark plugs, in order to reduce octane requirement. Continued improvement in design of internal combustion engines, e.g., fuel injection and the like, brings changes to the atmosphere of the combustion chamber so there is a continuing need for new additives to control the problem of deposits and improve drivability which is usually related to deposits. According to the present invention there are provided N-substituted carbamates (polyolefin-N-substituted-carbamates) of general formula in which R is a polyolefin radical having an average molecular weight in the range 500 to 9,900; R¹ is a hydrocarbyl group optionally substituted by ring-O, ring-N or a keto, hydroxy, nitro, cyano, alkoxy or acyl group, containing up to 20 carbon atoms; and R² is an alkyl group containing from 1 to 10 carbon atoms, an alkenyl group containing from 2 to 7 carbon atoms, a cycloalkyl group containing from 3 to 7 ring carbon atoms and a total of 3 to 10 carbon atoms, an aryl, aralkyl or alkaryl group containing from 6 to 10 total carbon atoms, or a group of formula wherein each R' is independently an alkylene group containing from 1 to 8 carbon atoms, each R'' is independently a hydrogen atom or an alkyl group containing from 1 to 7 carbon atoms and x is 0 to 5. The polyolefin-N-substituted-carbamates of the invention are a new class of additives, useful for fuels, e.g., in the gasoline boiling range, for preventing deposits in engines while also readily breaking down cleanly producing very little residue and are miscible with carriers, such as polymeric olefins and the like. Spark plugs from some engines run on some of the fuels containing the polyolefin-N-substituted-carbamates of the invention have been found to be exceptionally clean. Non-limiting illustrative embodiments of the invention include those of formula I wherein: R R¹ N(R²) hydrogenated polyisoprene ethyl phenyl-N ethylene-propylene copolymer phenyl ethyl-N polybutadiene cyclobutyl methyl-N polypropylene benzyl benzylethyl-N polybutylene vinyl isopropyl-N polyisobutylene methyl 3-(N,N-dimethyl)aminopropyl-N polyisobutylene ethyl 3-(N,N-diethyl)aminopropyl-N polyisobutylene isobutyl 2-(N,N-propyl)aminopropyl-N The polyolefin-carbamate compounds of formula I of the invention are conveniently prepared by treating a polyolefin-secondary-amine intermediate of formula R-N(R²)-H with a carboxylate compound of the formula IV in which Z is a halogen, alkoxy or alkylthio group and R¹ is as defined above. The hydrocarbyl and substituted hydrocarbyl groups of R¹ in formula IV include aliphatic, alicyclic, aromatic or heterocyclic groups. The substituted hydrocarbyl groups include those hydrocarbyl groups substituted by non-interfering atoms or substituents including ring-O, ring-N, and keto, hydroxy, nitro, cyano, alkoxy and acyl groups. The compounds of formula IV are generally available in the art. Suitable such halides or esters of formula IV include carbonates and thiocarbonates. Preferably, the compounds of formula IV include those compounds wherein R¹ is an alkyl group containing from 1 to 10 carbon atoms, an alkenyl group containing from 2 to 7 carbon atoms, a cycloalkyl group containing from 3 to 7 ring carbon atoms and a total of 3 to 10 carbon atoms or an aryl, aralkyl or alkaryl group containing from 6 to 10 total carbon atoms. Preferably, R¹ is an alkyl group containing 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl. Preferably, R¹ is methyl, ethyl, n-butyl or isobutyl. Z is preferably a halogen, such as chlorine. The reaction to produce the compounds of formula I is usually conducted in a solvent which is non-reactive with chloroformates and in which the two reactants are soluble. Hydrocarbon solvents such as toluene, xylene or the like are suitable. The reaction is conveniently conducted under relatively moderate conditions. The pressure is readily atmospheric pressure and temperatures of about 0 to about 40°C, e.g., ambient temperature, are convenient. Other moderate temperatures and pressures can be used which will not decompose the desired product. The polyolefin-carbamate product of formula I is recovered by conventional techniques, such as drying by stripping water or by using anhydrous sodium sulfate or the like. The solvent is usually removed, e.g., by stripping, for neat analysis. However, for practical applications some or all of the solvent can be retained as a diluent. Small amounts of polyolefin-secondary-unreacted amine intermediate need not be removed from the product as the presence thereof does not interfere with the usefulness of the product of formula I. Unreacted amine can aid in the effects of the polyolefin-N-substituted-carbamates of the invention by acting as a carrier, assisting in enhancing the preventing, removing or retarding of engine deposits (particularly when the carbamate is of methyl or a non-beta hydrogen group) or by providing their known fuel detergents properties. Other known materials for use in fuels can also serve one or more of these purposes, including the polymer additives described later. Preferred poly(olefin)-N-substituted-carbamates of the invention comprise N-substituted carbamates of formula I in which R and R² are as defined above, and R¹ is a hydrocarbyl group containing up to 20 carbon atoms. Preferred compounds of formula I of the invention include those compounds wherein R is a polyolefin radical having an average molecular weight in the range 550 to 4,900, preferably 600 to 1300. Preferably R is a polyisobutylene radical. R¹ is preferably an alkyl group containing from 1 to 10 carbon atoms, an alkenyl group containing from 2 to 7 carbon atoms, a cycloalkyl group containing from 3 to 7 ring carbon atoms and a total of 3 to 10 carbon atoms or an aryl, aralkyl or alkaryl group containing from 6 to 10 total carbon atoms. R¹ is preferably an alkyl group containing 1 to 4 carbon atoms. R² is an alkyl group containing from 1 to 10 carbon atoms, an alkenyl group containing from 2 to 7 carbon atoms, an cycloalkyl group containing from 3 to 7 ring carbon atoms and a total of 3 to 10 carbon atoms, an aryl, aralkyl or alkaryl group containing from 6 to 10 total carbon atoms, or, more preferably, a group of formula III wherein each R' is independently an alkylene group containing from 1 to 8 carbon atoms and each R'' is independently a hydrogen atom or an alkyl group containing from 1 to 7 carbon atoms and x is 0 to 5. Preferably, when R² is a group of formula III, each R' is independently an alkylene group containing from 1 to 4 carbon atoms; each R'' is independently an alkyl group containing from 1 to 4 carbon atoms and x is 0 to 2, e.g., 0 or 1. Especially preferred is for R' to be propylene, each R'' to be a methyl group and x to be 0. The polyolefin-secondary-amine intermediates (including polyamines) of formula R-N(R²)-H can be prepared by reacting olefinic polymers with amines employing conventional procedures as hereinafter described. These oil soluble polyolefin-secondary amine intermediates contain a polymer chain having a molecular weight in the range from 500 to 9,900 preferably from 550 to 4,900, and more preferably from 600 to 1,300, which can be saturated or unsaturated and straight or branched chain and which is attached to a nitrogen atom of the amine. Preferred poly(olefin)-N-substituted-secondary-amine intermediates are polyalkylene polyamines having the structural formula V wherein R is as defined above, each R' is an alkylene radical having from 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, each R'' is hydrogen or lower alkyl containing 1 to 7 carbon atoms and x is 0 to 5. Preferred is a polyalkylene polyamine wherein R is a branch-chain polyolefin radical in the molecular weight range of 550 to 4,900, with a molecular weight range of 600 to 1300 being particularly preferred. The polyolefins which give rise to R in formulas I and V are reacted with amines to form the polyolefin-N-substituted-secondary-amine intermediates of the present invention, and are known in the art, such as U.S. Patent No. 4,357,148, and include polyolefins derived from alkanes or alkenes with straight or branched chains, which may or may not have aromatic or cycloaliphatic substituents, for instance, groups derived from polymers or copolymers of olefins which may or may not have a double bond. Examples of non-substituted alkenyl and alkyl groups are polyethylene groups, polypropylene groups, polybutylene groups, polyisobutylene groups, polyethylene-polypropylene groups, polyethylene-polyalpha-methyl styrene groups and the corresponding groups without double bonds. Particularly preferred are polypropylene and polyisobutylene groups. The R'' group can be hydrogen but is preferably lower alkyl, i.e., containing up to 7 carbon atoms, and more preferably is an alkyl group containing from 1 to 4 carbon atoms, e.g., methyl, ethyl, propyl and butyl. Suitable amine reactants are broadly referred to as (poly)amines to include both polyamines and monoamines as hereinafter more fully described. The (poly) amines used to react with the polyolefins to form the polyolefin-N-substituted-secondary-amine intermediates include aliphatic, alicyclic, aromatic or heterocyclic monoamines or polyamines. A variety of such amines is well documented in the art including U.S. Patent No. 4,191,537. The amines can contain other non-reactive substituents. Suitable substituents for such amines include alkyls such as methyl, ethyl, propyl, butyl, isobutyl, pentyl, hexyl and octyl; and alkenyls such as propenyl, isobutenyl, hexenyl and octenyl. Preferred substituents are C₁-C₆ alkyl groups. The amine reactants include mixtures of compounds, such as mono and polysubstituted polyamines or isomers. The polyamines used to form the preferred polyolefin polyamine intermediate compounds of this invention include low molecular weight aliphatic polyamines such as ethylene diamine, diethylene triamine, triethylene tetramine, propylene diamine, butylene diamine, trimethyl trimethylene diamine, tetramethylene diamine, diaminopentane or pentamethylene diamine, hexamethylene diamine, heptamethylene diamine, diaminooctane, decamethylene diamine, and higher homologues up to 18 carbon atoms. Compounds possessing triamine as well as tetramine and pentamine groups are applicable for use because these can be prepared from technical mixtures of polyethylene polyamines, which offer economic advantages. The polyamine starting materials from which the polyamine groups can be derived can also be a cyclic polyamine, for instance, the cyclic polyamines formed when aliphatic polyamines with nitrogen atoms separated by ethylene groups are heated in the presence of hydrogen chloride. Monoamines which can be used to prepare the polyolefin-secondary-amines include monoamines in which the hydrocarbyl groups contain from 1 to 14 carbon atoms. For example, each hydrocarbyl group is independently selected from an alkyl group containing from 1 to 10 carbon atoms, an alkenyl group containing from 2 to 7 carbon atoms, a cycloalkyl group containing from 3 to 7 ring carbon atoms and a total of 3 to 10 carbon atoms or an aryl, aralkyl, or alkaryl group containing from 6 to 10 total carbon atoms. Preferably, the hydrocarbyl groups are independently selected from an alkyl group containing from 1 to 4 carbon atoms, e.g., ethyl or propyl. An example of a suitable process for the preparation of the polyolefin-amine compounds employed according to the invention is the reaction of a halogenated hydrocarbon having at least one halogen atom as a substituent and a hydrocarbon chain as defined hereinbefore with a (poly)amine. The halogen atoms are replaced by a (poly)amine group, while hydrogen halide is formed. The hydrogen halide can then be removed in any suitable way, for instance, as a salt with excess (poly)amine. The reaction between halogenated hydrocarbon and (poly)amine is preferably effected at elevated temperature in the presence of a solvent; particularly a solvent having a boiling point of at least 160°C. The reaction between halogenated hydrocarbon and a (poly)amine having more than one nitrogen atom available for this reaction is preferably effected in such a way that cross-linking is reduced to a minimum, for instance, by applying an excess of (poly)amine. The (poly)amine reactants can be prepared, for example, by alkylation of low molecular weight aliphatic (poly)amines. For instance, a (poly)amine is reacted with an alkyl or alkenyl halide. The formation of the alkylated (poly)amine is accompanied by the formation of hydrogen halide, which is removed, for instance, as a salt of starting (poly)amine present in excess. With this reaction between alkyl or alkenyl halide and the strongly basic (poly)amines, dehalogenation of the alkyl or akenyl halide may occur as a side reaction, so that hydrocarbons are formed as by-products, which need not be removed. The invention also provides a motor fuel composition comprising a mixture of hydrocarbons of the gasoline boiling range, containing an N-substituted carbamate of formula I as defined above. Suitable liquid hydrocarbon fuels of the gasoline boiling range are mixtures of hydrocarbons having a boiling range of from 25°C (77°F) to 232°C (450°F), and comprise mixtures of saturated hydrocarbons, olefinic hydrocarbons and aromatic hydrocarbons. Preferred are gasoline blends having a saturated hydrocarbon content ranging from about 40 to about 80 percent volume, an olefinic hydrocarbon content from about 0 to about 30 percent volume and an aromatic hydrocarbon content ranging from about 10 to about 60 percent volume. The base fuel can be derived from straight run gasoline, polymer gasoline, natural gasoline, dimer and trimerized olefins, synthetically produced aromatic hydrocarbon mixtures, from thermally or catalytically reformed hydrocarbons, or from catalytically cracked or thermally cracked petroleum stocks, and mixtures of these. The hydrocarbon composition and octane level of the base fuel are not critical. Any conventional motor fuel base can be employed in the practice of this invention. The hydrocarbon fuel mixtures to which the invention is applied may be substantially lead-free, but may contain minor amounts of blending agents such as methanol, ethanol, ethyl tertiary butyl ether and the like. The fuels may, however, also contain antiknock compounds such as tetraethyl lead, methyl cyclopentadienylmanganese tricarbonyl or orthoazidophenol. An effective amount polyolefin-N-substituted carbamates of the present invention can be introduced into the combustion zone of the engine in a variety of ways to prevent build-up of deposits, or to accomplish reduction or modification of deposits. Thus, the polyolefin-carbamates can be injected into the intake manifold intermittently or substantially continuously, as described, preferably in a hydrocarbon carrier having a final boiling point (by ASTM D86) lower than about 232°C (450°F). A preferred method is to add the agent to the fuel. For example, the agent can be added separately to the fuel or blended with other fuel additives. The effective amount of polyolefin-N-substituted carbamates of the invention used will of course depend on the particular compound(s) used, the engine and the fuel and carrier types. For example, the polyolefin-N-substituted carbamates may be used in an amount of from about 20 to about 750 ppm weight based on the total weight of the fuel composition and preferably from about 40 to about 500 ppm by weight. For use in the fuel compositions of the invention, mixtures of different polyolefin-N-substituted carbamates can be used. For example, a mixture where R¹ in formula I is methyl and is isobutyl. Alternatively, N(R²) and/or R could be mixtures of different groups in formula I. The polyolefin-N-substituted carbamate of the invention can also be used in combination with certain polymeric components which are polymers of monoolefins having up to 6 carbon atoms; poly (oxyalkylene) alcohols, glycols or polyols; or polyolefin amines. Such materials are well known in the art. For example, polymers of monoolefins are disclosed in U.S. Patents Nos. 2,692,257, 2,692,258, 2,692,259, 2,918,508 and 2,970,179. Preferred motor fuel compositions of the invention further comprise (b) at least one polymeric component which is selected from (i) a polymer of a C₂ to C₆ monoolefin, (ii) a copolymer of a C₂ to C₆ monoolefin, (iii) a hydrogenated polymer or copolymer of C₂ to C₆ monoolefin, (iv) a poly (oxy-C₂ to C₆ alkylene) alcohol, glycol or polyol, and (v) a poly(olefin)amine of a C₂ to C₆ monoolefin. The polymeric component (b) may conveniently have an average molecular weight by osmometry in the range of from 500 to 3500, preferably 500 to 1500. Particularly preferred are those having average molecular weight in the range from 600 to 950. Mixtures of polymers wherein a substantial portion of the mixture has a molecular weight above 1500 are considerably less effective. The polyolefins may be prepared from unsaturated hydrocarbons having from 2 to 6 carbon atoms including, e.g., ethylene, propylene, butylene, isobutylene, butadiene, amylene, isoprene, and hexene. Preferred as components (b) for their efficiency and commercial availability are polymers of propylene and butylene; particularly preferred are polymers of polyisobutylene. Also suitable are derivatives resulting after hydrogenation of these polymers. Poly(-C₂ to C₆-oxyalkylene) alcohols, glycols and polyol carriers can be used singly or in mixtures, such as the "Pluronics" (trade mark) marketed by BASF Wyandotte Corp., U.S.A., and the "UCON" LB-series (trade mark) fluids marketed by Union Carbide Corp., U.S.A. Preferably, these carriers include poly(oxypropylene) alcohol, glycol or polyol of molecular weight in the range 300 to 4000, which may or may not be capped by an alkyl group, e.g., a (C₁₋₁₀ hydrocarbyl)poly(oxypropylene) alcohol and polyethylene glycols of molecular weight of from 300 to 4000. The poly(olefin) amines of a C₂ to C₆ monoolefin, described hereinbefore for use as the starting materials used to make the compounds of formula I are also useful as the poly(olefin) amine fuel additives. The invention further provides a concentrate for use in liquid (hydrocarbon) fuel in the gasoline boiling range comprising (a) from 25 to 500 ppm by weight (preferably from 50 to 200 ppm) of at least one N-substituted carbamate of formula I; (b) from 10 to 1000 ppm (preferably 50 to 400 ppm) by weight of at least one polymeric component which is selected from (i) a polymer of a C₂ to C₆ monoolefin, (ii) a copolymer of a C₂ to C₆ monoolefin, (iii) a hydrogenated polymer or copolymer of C₂ to C₆ monoolefin, (iv) a poly(oxy-C₂ to C₆-alkylene) alcohol, glycol or polyol, and (v) a poly(olefin)amine of a C₂ to C₆ monoolefin, (c) optionally from about 0 to about 20 ppm by weight of a dehazer and (d) balance a diluent, boiling in the range from 50°C (122°F) to 232°C (450°F). Very suitable diluents include oxygen-containing hydrocarbons and non-oxygen-containing hydrocarbons. Suitable oxygen-containing hydrocarbon solvents include, e.g., methanol, ethanol, propanol, methyl tert-butyl ether and ethylene glycol monobutyl ether. The solvent can be an alkane such as heptane, but preferably is an aromatic hydrocarbon solvent such as toluene, xylene alone or in admixture with said oxygen-containing hydrocarbon solvents. Optionally, the concentrate can contain from about 0 to about 20 ppm by weight of a dehazer, particularly a polyester-type ethoxylated alkylphenol-formaldehyde resin, or other conventional dehazer. The invention further provides a method for operating a spark ignition internal combustion engine (ICE) which comprises introducing with the combustion intake fuel charge to said engine a deposit preventing or reducing effective amount of at least one polyolefin-N-substituted carbamate of formula I as defined above. The preferences expressed earlier with regard to (a) the polyolefin-N-substituted carbamates of formula I and/or (b) the polymeric component or other additives also apply to the concentrate, motor fuel composition and method of operating the ICE. The invention will be further understood from the following illustrative examples. Example 1 - Preparation of a Compound of Formula I with R¹=n-butyl; R = polyisobutylene of 900 average molecular weight; and N(R²) = N-CH₂CH₂CH₂NMe₂ Five Hundred grams of polyisobutylene-NH-(CH₂)₃NMe₂ (80.5% non-volatile, 19.5% xylenes, and containing 1.50% basic nitrogen) were charged to a 1000 ml, round-bottomed flask equipped with an air-driven stirrer, reflux condenser, thermometer, and addition funnel. To the addition funnel were added 45.5 grams of n-butyl chloroformate and 21 ml of toluene. The toluene solution was added dropwise at room temperature to the round-bottomed flask with stirring. The addition took about 10 minutes with an increase of 36°C in reaction temperature. The reaction flask was heated to 160°C after the addition was completed and maintained at that temperature for 1 hour. The addition funnel was removed and replaced with a powder funnel. Through this latter funnel was added a solution of 44.3 grams of sodium carbonate in 177 grams of water. Upon completion of the addition, the flask was heated to 100°C for one hour. The contents of the reaction flask were transferred to a 2000 ml separatory funnel where the layers were seaparated and the lower water layer was removed. The remaining layer was treated three times with 150 ml of water. The water was removed and the contents of the funnel were transferred to a 2000 ml Erlenmeyer flask. Five hundred ml of toluene was added to the flask together with anhydrous sodium sulfate. After one hour of stirring, the contents of the Erlenmeyer flask were filtered and solvent removed by rotary evaporation. Evaluation of the neat material revealed a basic nitrogen content of 0.82%w and a total nitrogen of 1.71%w confirming that one of the two nitrogens had reacted and was now rendered non-basic. Examination by IR (Infra-Red Spectrometry) showed a typical carbamate absorption at 1700 cm⁻¹ (uncorrected). Example 2 A series of compounds of formula I wherein R and A are as in Example I were made by similar procedures to that described in Example I and these compounds are set forth in Table 1 below: R¹ N t ) , %w N b ) , %w IR, cm⁻¹ Methyl 1.87 1.09 1720 Ethyl 1.80 0.93 1715 n-Butyl 1.71 0.82 1700 i-Butyl 1.73 0.76 1715 n-Octyl 1.68 0.83 1710 Example 3 - Engine Tests Fuels shown in Table 2 were tested in a 1983 Chevrolet 2.0 litre and a 1987 Ford 3.0 litre V-6 engine with Port Fuel Injection (PFI) to determine the effectiveness of the polyolefin-N-substituted-carbamates of the invention on induction system cleanliness, fuel economy and deposit de-adhesion. The base fuel comprised premium unleaded gasoline. The polyolefin-N-substituted-carbamates were according to Example 2 above. Polyolefin carrier fluid was added in some tests. Each engine was in clean condition at the start of the test, i.e., oil and filters were changed and all deposits had been removed from the intake manifolds, intake ports and combustion areas of the engine. In order to test for the accumulation of deposits in the engine during each test, the engines were operated on a cycle consisting of idle mode and cruising modes of 48.3, 56.3, 72.4, 88.5 and 104.6 kilometres an hour (30, 35, 45, 55 and 65 miles an hour) with accelerations and decelerations. The tests were conducted for 100 hours and then the valves and port deposits were visually rated on a scale of 1 to 10, in which "10" is essentially free of deposit by comparison to representative photographs of values having ratings of 10, 9, 8, etc. The weight of the value deposits was also measured. Results of these tests are set forth in Table 2 below: Results of these tests demonstrate that the polyolefin-N-substituted-carbamates of the invention are very useful in very significantly preventing the accumulation of deposits in the engines tested as compared to the effects of the base fuel as shown by the much lower average valve deposits and the higher average visual rating of valve and port deposits. The use of polyisobutylene as a carrier fluid for the N-substituted carbamates also results in preventing the accumulation of deposits.

Claims: Claims for the following Contracting States : BE, DE, FR, GB, IT, NL An N-substituted carbamate of formula in which R is a polyolefin radical having an average molecular weight in the range 500 to 9,900; R¹ is a hydrocarbyl group optionally substituted by ring-O, ring-N or a keto, hydroxy, nitro, cyano, alkoxy or acyl group, containing up to 20 carbon atoms; and R² is an alkyl group containing from 1 to 10 carbon atoms, an alkenyl group containing from 2 to 7 carbon atoms, a cycloalkyl group containing from 3 to 7 ring carbon atoms and a total of 3 to 10 carbon atoms, an aryl, aralkyl or alkaryl group containing from 6 to 10 total carbon atoms, or a group of formula wherein each R' is independently an alkylene group containing from 1 to 8 carbon atoms, each R'' is independently a hydrogen atom or an alkyl group containing from 1 to 7 carbon atoms and x is 0 to 5. A carbamate according to claim 1, wherein R¹ is a hydrocarbyl group containing up to 20 carbon atoms. A carbamate according to claim 1 or claim 2, wherein each R' is independently an alkylene group containing from 1 to 4 carbon atoms, each R'' is independently an alkyl group containing from 1 to 4 carbon atoms and x is 0 to 2. A carbamate according to claim 3, wherein R' is propylene, each R'' is a methyl group and x is 0. A carbamate according to any one of claims 1 to 4, wherein R is a polyolefin radical having an average molecular weight in the range 550 to 4,900. A carbamate according to any one of claims 1 to 5, wherein R is a polyolefin radical having an average molecular weight in the range 600 to 1,300. A carbamate according to any one of claims 1 to 6, wherein R is a polyisobutylene radical. A carbamate according to any one of claims 1 to 7, wherein R¹ is an alkyl group containing from 1 to 10 carbon atoms, an alkenyl group containing from 2 to 7 carbon atoms, a cycloalkyl group containing from 3 to 7 ring carbon atoms and a total of 3 to 10 carbon atoms or an aryl, aralkyl or alkaryl group containing from 6 to 10 total carbon atoms. A carbamate according to any one of claims 1 to 8, wherein R¹ is an alkyl group containing 1 to 4 carbon atoms. A concentrate suitable for incorporation in liquid fuels of the gasoline boiling range comprising (a) from 25 to 500 ppm by weight of at least one N-substituted-carbamate according to any one of claims 1 to 9; (b) from 10 to 1000 ppm by weight of at least one polymeric component which is selected from (i) a polymer of a C₂ to C₆ monoolefin, (ii) a copolymer of a C₂ to C₆ monoolefin, (iii) a hydrogenated polymer or copolymer of C₂ to C₆ monoolefin, (iv) a poly(oxy-C₂ to C₆-alkylene) alcohol, glycol or polyol, and (v) a poly(olefin)amine of a C₂ to C₆ monoolefin; (c) optionally from 0 to 20 ppm by weight of a dehazer; and (d) balance a diluent, boiling in the range from 50°C to 232°C. A motor fuel composition comprising a mixture of hydrocarbons of the gasoline boiling range, containing an N-substituted carbamate according to any one of claims 1 to 9 or a concentrate according to claim 10. A process for the preparation of an N-substituted carbamate of formula I as defined in any one of claims 1 to 9 which comprises reacting an amine of formula R-N(R²)-H, where R and R² are as defined in claim 1, with a carboxylate compound of formula where R¹ is as defined in claim 1 and Z is a halogen atom, an alkoxy or a alkylthio group. Claims for the following Contracting State : ES A process for the preparation of an N-substituted carbamate of formula in which R is a polyolefin radical having an average molecular weight in the range 500 to 9,900; R¹ is a hydrocarbyl group optionally substituted by ring-O, ring-N or a keto, hydroxy, nitro, cyano, alkoxy or acyl group, containing up to 20 carbon atoms; and R² is an alkyl group containing from 1 to 10 carbon atoms, an alkenyl group containing from 2 to 7 carbon atoms, a cycloalkyl group containing from 3 to 7 ring carbon atoms and a total of 3 to 10 carbon atoms, an aryl, aralkyl or alkaryl group containing from 6 to 10 total carbon atoms, or a group of formula wherein each R' is independently an alkylene group containing from 1 to 8 carbon atoms, each R'' is independently a hydrogen atom or an alkyl group containing from 1 to 7 carbon atoms and x is 0 to 5, which comprises reacting an amine of formula R-N(R²)-H, where R and R² are as in formula I, with a carboxylate compound of formula where R¹ is as in formula I and Z is a halogen atom, an alkoxy or alkylthio group. A process according to claim 1, wherein R¹ is a hydrocarbyl group containing up to 20 carbon atoms. A process according to claim 1 or claim 2, wherein each R' is independently an alkylene group containing from 1 to 4 carbon atoms, each R'' is independently an alkyl group containing from 1 to 4 carbon atoms and x is 0 to 2. A process according to claim 3, wherein R' is propylene, each R'' is a methyl group and x is 0. A process according to any one of claims 1 to 4, wherein R is a polyolefin radical having an average molecular weight in the range 550 to 4,900. A process according to any one of claims 1 to 5, wherein R is a polyolefin radical having an average molecular weight in the range 600 to 1,300. A process according to any one of claims 1 to 6, wherein R is a polyisobutylene radical. A process according to any one of claims 1 to 7, wherein R¹ is an alkyl group containing from 1 to 10 carbon atoms, an alkenyl group containing from 2 to 7 carbon atoms, a cycloalkyl group containing from 3 to 7 ring carbon atoms and a total of 3 to 10 carbon atoms or an aryl, aralkyl or alkaryl group containing from 6 to 10 total carbon atoms. A process according to any one of claims 1 to 8, wherein R¹ is an alkyl group containing 1 to 4 carbon atoms. A process for the preparation of a concentrate suitable for incorporation in liquid fuels of the gasoline boiling range which comprises mixing (a) from 25 to 500 ppm by weight of at least one N-substituted-carbamate of formula I as defined in any one of claims 1 to 9; (b) from 10 to 1000 ppm by weight of at least one polymeric component which is selected from (i) a polymer of a C₂ to C₆ monoolefin, (ii) a copolymer of a C₂ to C₆ monoolefin, (iii) a hydrogenated polymer or copolymer of C₂ to C₆ monoolefin, (iv) a poly(oxy-C₂ to C₆-alkylene) alcohol, glycol or polyol, and (v) a poly(olefin)amine of a C₂ to C₆ monoolefin; (c) optionally from 0 to 20 ppm by weight of a dehazer; and (d) balance a diluent, boiling in the range from 50°C to 232°C. A process for the preparation of a motor fuel composition which comprises mixing a mixture of hydrocarbons of the gasoline boiling range, with an N-substituted carbamate of formula I as defined in any one of claims 1 to 9 or a concentrate prepared according to claim 10.

Inventors: JOHNSON, THOMAS HOWARD
Applicants: SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V.
Application year: 1989
Main classification: C08F8
IPC codes: C10L1, C08F8