DE102008046106A1 - Mannich detergents for hydrocarbon fuels - Google Patents

Abstract

New, high potency, substantially pure Mannich detergents for use in hydrocarbon fuels reduce engine deposits in spark-ignited and auto-ignition internal combustion engines. The Mannich condensation reaction products can be obtained by reacting: (i) a polyamine having primary amino groups, (ii) a hydrocarbyl-substituted hydroxyaromatic compound, and (iii) an aldehyde, the reaction being conducted at a molar ratio of (i): (ii): (iii ) of about 1: 2: 3 or 1: 1: 2. The Mannich detergent compounds may be dispersed in a liquid carrier to provide a fuel additive concentrate for hydrocarbon engine fuels which effectively regulates engine deposit formation in intake valves, fuel injector ports, and combustion chambers.

Description

Field of the invention

These This invention relates to novel Mannich base condensation products and fuel compositions, comprising the Mannich products, which are effective engine deposits in internal combustion engines to regulate.

Background of the invention

deposits tend to build up in an engine when gasoline is not effective Contains deposition control additives. Because most Benzing bases based on similar regulated specifications may be formulated, the performance of the deposit control additives in distinguishing different gasoline brands after performance be very important. Over the years has been considerable Work in the development of additives for regulation (prevention or reduction) of deposit formation, especially in the fuel induction systems from spark-ignited internal combustion engines, plugged.

additives which could effectively regulate engine deposits in the focus of considerable research activities in the field, however, further improvements are desired.

Summary of the invention

The Invention provides Mannich reaction products with robust detergent properties in hydrocarbon fuels that are effective, improved Deposit regulation in spark-ignited and self-igniting to provide internal combustion engines. These detergent compounds are provided as Mannich condensation reaction products of: (i) a polyamine having primary amino groups, (ii) a hydroxy-substituted hydroxyaromatic compound, and (iii) an aldehyde, wherein the Mannich reaction is at a total mole ratio of (i) :( ii) :( iii) is carried out so that the For example, the polyamine (i) with the hydrocarbyl-substituted hydroxyaromatic Compound (ii) can implement, so the substantially pure intermediate to obtain this intermediate with the aldehyde (iii) with the Mannich reaction product as a substantially pure product is obtained.

One important feature of this invention is the implementation the Mannich condensation reaction, allowing the reaction product is substantially pure, especially in a process which can be easily scaled up and as a so-called "one-pot" method can be. These Mannich reaction products are not just improved Regulation of inlet valve deposits, but also improved Deposition control in "cooler" engine regions in internal spark-ignited or self-igniting internal combustion engines ready. For example, in addition to intake valve regulation discovered that they are involved in regulation (i.e., prevention and / or Reduction) of plugging of the fuel injector opening or direct injector deposits, combustion chamber deposits and inlet port patches are effective. Mannich reaction products not only meet and pass industry deposit regulation performance tests, which concern intake valves, but also industrial tests, which Fuel injector openings concern (see ASTM D-6421, PFI test bench tests), which compares well is with Mannich comparison detergents that fail the PFI test bench passed.

In One aspect of the invention may be the Mannich reaction products at least the same or improved IVD performance compared with other Mannich reaction products which at different molar ratios (1: 1: 1, 1: 2: 1, etc.) can be obtained when using the 2.3 liter Ford engine test or, for example, the Dodge Intrepid engine Is tested. This IVD performance can be obtained while also improved PFI test bench performance is obtained.

In In one aspect of the invention, the Mannich reaction products are essential pure and no complex multi-component mixtures with many by-products as they can be obtained when the Mannich reaction using molar ratios, which essentially depends on the present ratio deviate, is performed.

In one aspect of the invention, the Mannich reaction products may be in a reaction vessel which is sometimes referred to as a one-pot reaction process.

In In one embodiment, a polyamine may be primary Amino group, which is used in the Mannich reaction selected are made from (A) aliphatic cyclic polyamines with primary Amino groups, and (B) acyclic aliphatic polyamines with primary Amino groups, or combinations thereof. Preferred are the primary Amines on adjacent carbon atoms or on carbon atoms, which are separated by a methylene group, with the proviso that the selected polyamine to form a 5-membered or 6-membered heterocyclic ring having two nitrogen atoms in the ring in the reaction scheme as described herein in the Location is.

In In another embodiment, a Mannich reaction product by reacting (i) 1,2-diaminocyclohexane, 1,3-diaminopropane or 1,2-diaminoethane, (ii) polyisobutylene-substituted cresol and / or Phenol, and (iii) formaldehyde obtained using the Mannich reaction at a total molar ratio of (i) :( ii) :( iii) of about 1: 2: 3 is performed.

In In another embodiment, a Mannich reaction product by reacting (i) 1,2-diaminocyclohexane, 1,3-diaminopropane or 1,2-diaminoethane, (ii) polyisobutylene-substituted cresol and / or Phenol, and (iii) formaldehyde obtained using the Mannich reaction at a total molar ratio of (i) :( ii) :( iii) of about 1: 1: 2 is performed.

The Mannich reaction product may be in a liquid carrier be dispersed, wherein a fuel additive concentrate for Hydrocarbon motor fuels is provided. In one Aspect of this embodiment includes an exemplary Fuel additive composition (a) a Mannich reaction product, which is prepared by reacting (i) a polyamine with primary Amino groups resulting in the formation of a substantially pure intermediate in the Mannich condensation reaction capable of being the intermediate a 5-membered or 6-membered nitrogen-containing heterocyclic Unit, (ii) a hydrocarbyl-substituted hydroxyaromatic Compound, and (iii) an aldehyde is obtained, wherein the reaction using a molar ratio (i) :( ii) :( iii) is carried out so that the polyamine (i) with the React hydrocarbyl-substituted hydroxyaromatic compound (ii) can be so as to obtain the substantially pure intermediate, wherein react this intermediate with the aldehyde (iii) can, wherein the Mannich reaction product as a substantially pure product is obtained; and (b) a liquid carrier.

Yet another embodiment includes fuels for spark-ignited and self-igniting Engines into which the various Mannich reaction products described herein and / or additive concentrates of this invention have been mixed, and Method of regulation (i.e., prevention or reduction) of Engine valve deposits on a number of engine locations, which one or more of the intake valves, the fuel injector ports, Direct fuel injectors, combustion chambers, opening fuel stain and so on in an internal combustion engine, by refueling and / or operating the engine with a fuel composition of this invention. Other embodiments and features of this invention will become even more apparent from the following description and the appended claims become.

Detailed description of the preferred embodiments

Mannich reaction product. Detergent compounds are here as deposit control additives useful in motor fuels and include the Mannich reaction product of: (i) a polyamine having primary amino groups, (ii) a hydrocarbyl-substituted hydroxyaromatic compound, and (iii) an aldehyde at a total molar ratio (reactants), so that, for example, the polyamine (i) with the hydrocarbylsubstituierten hydroxyaromatic compound (ii) can be implemented so as in the to obtain substantial pure intermediate, this being Intermediate with an aldehyde (iii) can implement, with a Mannich reaction product as a substantially pure product is obtained. Preferably, a total mole ratio (i) :( ii) :( iii) be about 1: 2: 3.

One Mannich reaction product of the present invention is substantially purely. For example, a Mannich reaction product which is at least about 80% pure, preferably at least about 85% pure, can be obtained become. Basically, the Mannich reaction products of the present invention at least about 90 to at least about Be 95% pure.

Reactions of aliphatic diamines with formaldehyde are described in Krassig, macromol. Chem. 17: 119 (1956) in which a formation of 5-membered rings and 6-membered rings in T. Araki et al., Macromolecules, 21: 1995 (1988). is described.

Polyamine amine groups: The polyamine reactant used in the Mannich reaction is a polyamine which is a suitably reactive amino group (s) in the same molecule to the Mannich reaction too support. The reactive amino group may be primary or secondary amino group in the molecule although (a) primary amino group (s) may be preferred. The polyamines should be used to form a substantially pure 5-membered or 6-membered cyclic nitrogen intermediate (the intermediate has a 5-membered or 6-membered heterocyclic Unit with at least two nitrogen atoms in the ring) Reaction with the hydrocarbyl-substituted hydroxyaromatic Be able to compound, with this intermediate itself can react with the selected aldehyde, with an im essential pure Mannich reaction product is obtained. consequently the selected polyamines preferably include diamines, so as to reduce side reactions and by-products, if not to avoid. Further preferred are in a selected Diamine the amine groups primary amine groups respectively bound to adjacent carbon atoms or to respective carbon atoms, which are separated from each other by an intervening methylene group are spaced, bound.

basically, Subject of the stipulations and favors here, a representative acyclic aliphatic polyamine reactant include an alkylene polyamine having a primary amino group, which is physically sterically protected to avoid or at least essentially limit its assets, participate in the Mannich condensation reaction, with the proviso that the reactant is chosen so that substantially the desired intermediate product is produced, namely the substantially pure intermediate (the intermediate has a 5-membered or 6-membered heterocyclic moiety having at least two nitrogen atoms in the ring). Such a polyamine can selected from those described in U.S. Application No. 11 / 336,037, filed January 20, 2006, the complete disclosure of which is incorporated herein by reference becomes. The amino group is generally either a secondary one or tertiary carbon atom in the polyamine compound bound and is in support of the Mannich reaction in a position. The reactive amino group may be a primary, or secondary amino group in the molecule. Prefers the amino groups are primary, and more preferably the selected polyamine has no other substituents, which is the formation of by-products in a Mannich reaction promote or are capable of doing what the purpose of the Formation of a substantially pure intermediate with a 5-membered or 6-membered heterocyclic moiety which having at least two nitrogen atoms in the ring, in unison stands.

One suitable polyamine, which for a Mannich reaction here is useful, does not require an amino group, such as a primary Amino group which is physically sterically protected to avoid or at least substantially his fortune to participate in the Mannich reaction.

suitable Polyamines include aliphatic cyclic polyamines, in particular Polyaminocycloalkanes, such as polyaminocyclohexanes, and certain lower alkyl diamines one. The polyamine is chosen so that a desired Substantially pure 5-membered or 6-membered cyclic Intermediate can be obtained (a 5-membered or 6-membered heterocyclic unit containing at least two nitrogen atoms in the ring), which can be implemented itself, wherein a substantially pure Mannich reaction product is obtained.

The Polyaminocyclohexanes can be 1,2-diaminocyclohexanes ("DAC") as an example. 1,2-Diaminocyclohexanes are for example as a mixture of isomers, such as cis and trans isomers. Isolated or pure isomeric forms thereof can also be used as This working area can be used.

acyclic aliphatic polyamines with primary amino group (s) include ethylene diamine and 1,3-diaminopropane. These Polyamines can be used to form the desired im essentially pure 5-membered or 6-membered cyclic Intermediate can be used.

Hydrocarbyl-substituted hydroxyaromatic compound. Representative hydrocarbyl-substituted hydroxyaromatic compounds that can be used in the formation of the Mannich detergent products of the present invention are represented by the following formula:

wherein each RH, C _1-4 alkyl or a hydrocarbyl substituent having an average molecular weight (M _w ) is in the range of about 300 to about 2,000, more preferably about 500 to about 1,500 as measured by gel permeation chromatography (GPC) provided that at least is an RH and an R is a hydrocarbyl substituent as defined above.

Representative Hydrocarbyl substituents include polyolefin polymers, such as polypropylene, polybutene, polyisobutylene, and ethylene-alpha-olefin copolymers one. Other similar long-chain hydrocarbyl substituents can also be used. Close examples Copolymers of butylene and / or isobutylene and / or propylene, and one or more of the mono-olefinic copolymerizable therewith Comonomers (e.g., ethylene, 1-pentene, 1-hexene, 1-octene, 1-decene, etc.), wherein the copolymer molecule is at least 50% by weight Butylene and / or isobutylene and / or propylene units. The comonomers polymerized with propylene or such butenes may be aliphatic and may also be non-aliphatic Leftovers, z. Styrene, o-methylstyrene, p-methylstyrene, divinylbenzene and the like. So are the resulting polymers and copolymers which result in the formation of the alkyl-substituted hydroxyaromatic Compound to be used in any case in essential aliphatic Hydrocarbon polymers. Polyolefinpolymerhydrocarbylsubstituenten can be at least 20%, especially at least 50% and more particularly at least 70% of their olefin double bonds at a terminal position on the carbon chain as the highly reactive Vinylidene isomer.

polybutylene is especially useful. Unless otherwise specified here, the term "polybutylene" is used in a common sense Sinn uses polymers made of "pure" or "im essentially pure "1-butene or isobutene, or Polymers consisting of mixtures of two or all three of 1-butene, 2-butene and isobutene are made to include. Commercial qualities of such polymers can also contain insignificant amounts of other olefins.

Polyisobutylene is also particularly useful. So-called high reactivity polyisobutenes having relatively high levels of polymer molecules having a terminal vinylidene group, ie at least 20% of the total terminal olefinic double bonds in the polyisobutene, comprise an alkylvinylidene isomer, preferably at least 50% and more preferably at least 70%, formed by methods such as, for example in U.S. Pat. No. 4,152,499 and the German Offenlegungsschrift 29 04 314 are preferred polyalkenes for use in the formation of the hydrocarbyl-substituted hydroxyaromatic reactant. Also suitable for use in the formation of the long chain substituted hydroxyaromatic reactants of the present invention are ethylene-alpha olefin copolymers having a number average molecular weight of 500 to 3,000, wherein at least about 30% of the chains of the polymer contain terminal ethylidene unsaturation.

In one embodiment, the hydrocarbyl-substituted hydroxyaromatic compound has an R which is H, an R is C _1-4 alkyl and an R is a hydrocarbyl substituent having an average molecular weight in the range of about 300 to about 2,000. By using a substituted hydroxyaromatic compound having only one site at which the Mannich reaction can take place, ie, only one ortho or para position is unsubstituted (ie, where R = H), in combination with an amine group but not all primary amine groups on a polyamine as defined herein, Mannich detergent products are obtained which are very effective in preventing or even reducing engine deposits in different regions of an internal combustion engine.

In a particular embodiment, the hydrocarbyl-substituted hydroxyaromatic compound can be obtained by alkylating o-cresol with a high molecular weight hydrocarbyl polymer, such as a hydrocarbyl polymer moiety having an average molecular weight between about 300 to about 2,000, to provide an alkyl-substituted cresol. In a more specific embodiment, o-Cre sol is alkylated with polyisobutylene having an average molecular weight between about 300 to about 2,000 to provide a polyisobutylene-substituted cresol. In a most emphasized embodiment, o-cresol is alkylated with polyisobutylene (PIB) having an average molecular weight of between about 500 to about 1,500 to provide a polyisobutylene-substituted cresol (PIB-cresol).

In In another particular embodiment, the hydrocarbyl-substituted hydroxyaromatic compound by alkylation of o-phenol with a high molecular weight hydrocarbyl polymer such as a hydrocarbyl polymer residue with an average molecular weight between about 300 to about 2,000, to provide an alkyl-substituted phenol becomes. In a particular embodiment, o-cresol with polybutylene having an average molecular weight between about Alkylated from 500 to about 1,500, wherein a polybutylene-substituted Cresol is provided.

however may be any hydrocarbyl-substituted hydroxyaromatic compound, which is slightly reactive in the Mannich condensation reaction, be used. The hydrocarbyl substituents may be slightly residual Contain unsatisfaction, but are generally in the essentially saturated.

The alkylation of the hydroxyaromatic compound is typically conducted in the presence of an alkylation catalyst such as a Lewis acid catalyst (e.g., BF ₃ or AlCl ₃ ) at a temperature in the range of about 30 to about 200 ° C. For a polyolefin used as the hydrocarbyl substituent, it is preferred to have a polydispersity in the range of from about 1 to about 4, preferably from about 1 to about 2, as determined by GPC. Suitable methods for alkylating the hydroxyaromatic compounds of the present invention are generally known in the art, for example as in GB 1,159,368 and U.S. Pat. No. 4,238,628 ; 5,300,701 and 5,876,468 taught.

Aldehyde. Representative aldehydes for use in the preparation of the Mannich base products include aliphatic aldehydes and aromatic aldehydes. The aliphatic aldehydes include C ₁ to C ₆ aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde and hexanalaldehyde. Aromatic aldehydes which may be used include, for example, As benzaldehyde and salicylaldehyde. Illustrative heterocyclic aldehydes for use herein are furfural and thiophenealdehyde, etc. Also useful are formaldehyde-producing reagents such as paraformaldehyde or aqueous formaldehyde solutions such as formalin. Most preferred are formaldehyde and formalin.

synthesis from Mannich reaction product. For the production of Mannich products The invention may include a Mannich reaction of the polyamine, the hydrocarbyl-substituted hydroxyaromatic compound and aldehyde at one temperature in a range consistent with that disclosed in U.S. Application 11 / 336,037 is comparable. One suitable temperature range may be from about 40 ° C to about 200 ° C be. However, it goes without saying that the implementation at a lower temperature, such as. B. 30 ° C, begin can. The reaction can be carried out in bulk (no diluent or solvent) or in a solvent or diluents.

water Evolves and may be due to azeotropic distillation in the course the implementation will be removed. For example, the temperature is typically increased, such. B. to 150 ° C, if the water is removed, which develops in the implementation. Typical reaction times are in the range of about 3 to about 4 hours, although longer or shorter times can be used where necessary or desired, as well as from co-pending U.S. Application 11 / 336,037 will be apparent.

An exemplary process may begin by adding a hydrocarbyl-substituted hydroxyaromatic component (ii) to the reaction vessel along with a suitable aromatic solvent to obtain a mixture. (Suitable solvents also include non-aromatic solvents such as heptane, in which case the temperature may differ somewhat, as one skilled in the art will understand.) The mixture is mixed, e.g. By stirring, under an inert atmosphere, such as under an N ₂ layer, adjusting a suitable SCFH. A suitable SCFH range is nominally 0.1 to 0.2 SCFH. It is preferred to add the polyamine (i) when the mixture is homogeneous and at a moderate temperature, such as 40 to about 45 ° C. Preferably, the molar ratio of hydrocarbyl-substituted hydroxyaromatic component (ii) to polyamine (i) is about 2: 1. The resulting intermediate is substantially pure and can be used as such without the need for laborious or expensive workup or isolation. The selected aldehyde, such as. As formaldehyde is added. In the present case, the added amount of aldehyde (iii) is preferably such that the molar ratio (i) :( ii) :( iii) is about 1: 2: 3. The temperature rises, z. B. to about 45 to about 50 ° C. The temperature is reduced to less than 100 ° C, such as. B. about 80 ° C, increases, and the vessel and its contents can at such a temperature to be held for about 30 minutes to 60 minutes. Distillation may then be carried out using a water separator or equivalent, and the temperature is adjusted to an elevated temperature in the range of 130 to about 150 ° C, such as 145 ° C, and it should be appreciated that the distillation is after a period of time to allow the reaction mixture to reach about 95 to 105 ° C. After the distillation has begun, the inert gas gas flow (such as a layer below N ₂ ) may be increased to about 0.1 SCFH to about 1.0 SCFH, such as 0.5 SCFH. The temperature is maintained at the selected elevated temperature for a sufficient time, which may be about an additional 2 hours to about 2.5 hours. After distillation, to the reaction product, if desired, may be added such additional solvent that an additive concentrate (sometimes referred to as an additive package) containing the Mannich reaction product is obtained. For example, an additive concentrate may be prepared by adding selected solvent (s) such that the concentrate contains about 25% solvent. Such a concentrate is suitably subjected to quality control and is also suitable for engine testing.

One important feature of this invention is the relative molar fraction the essential reactants in the Mannich reaction. In general is the total molar ratio of the polyamine (i): hydrocarbyl-substituted hydroxyaromatic compound (ii): aldehyde (iii) such that for example, the polyamine (i) with the hydrocarbyl-substituted hydroxyaromatic compound (ii) can be implemented so as in the to obtain substantial pure intermediate, this being Intermediate with the aldehyde (iii), the Mannich reaction product is obtained as a substantially pure product. Prefers is the total mole ratio (i) :( ii) :( iii) about 1: 2: 3 as an example. In the present context means a molar ratio of about 1: 2: 3 each ± 5%, such. B. a ratio of 1 mole (± 5%) to 2 moles (± 5%) to 3 moles (± 5%). The molar ratio 1: 2: 3 is preferred, whereas the use of approximately equimolar proportions of the three Mannich reaction reactants is not preferred. When less than 1 mole of polyamine and / or less used as 1 mole of aldehyde per mole of hydroxyaromatic compound be some reactants, such as the hydroxyaromatic compound, remain unreacted, and the Mannich product becomes less Being active will be essentially less pure and may be lower IVD performance and lower performance in the PFI bench test exhibit. It was previously thought that if higher conditions above about 1: 1: 1, d. H. much more than 1 mole of polyamine and / or much more than 1 mole of aldehyde, per mole of hydroxyaromatic Compound used to be unwanted by-products or substantial amounts of unreacted Polyamine or aldehydes may be present in the finished product or have to be deducted from the reaction mixture, resulting in a waste of starting materials. The usage of the present total reactant molar ratio specified of about 1: 2: 3 together with the use of the polyamines, as selected based on the criteria described here, results in a substantially pure Mannich reaction product with excellent performance and excellent, physical properties.

If the implementations are done, it is relatively easy to maintain the present molar ratio and It can help control errors by operators to avoid commercial production. When the implementation in plant reactors on a large scale, losses are the more volatile reactants (polyamine and formaldehyde) possible, as evidenced by evaporation into the reactor headspace, Entrainment in purge streams when water is rinsed out of the reaction mixture, etc. typically can occur. Compensation of any such losses, so that the liquid reaction mixture contains the reactants the molar ratio corresponding to this invention, contains, is feasible and attractive, as one essentially pure Mannich reaction product is obtained. There the relative molar ratio is controllable and the reaction product not a complex mixture, but rather a substantial one pure reaction product is when the reaction in the present Molar ratio is carried out, the reaction can on a large scale with reduced reactant losses be performed while inappropriately expensive Post-reaction processing is avoided. The synthesis should therefore be reasonably practicable.

additive concentrates and fuel compositions. The Mannich products of this invention are preferred in connection with a liquid carrier, Induction aid or fluidizing agent used. Such Carriers can be of different types, such as for example, liquid poly-α-olefin oligomers, liquid Polyalkene hydrocarbons (eg polypropene, polybutene, polyisobutene or the like), liquid hydrogenated polyalkene hydrocarbons (eg, hydrogenated polypropene, hydrogenated polybutene, hydrogenated polyisobutene or the like), mineral oils, liquid poly (oxyalkylene) compounds, liquid Alcohols or polyols, liquid esters and the like liquid carriers or solvents. mixtures of two or more such carriers or solvents can be used.

Carrier. The Mannich products of this invention are preferably compounded with a liquid carrier, induction aid or fluidizing agent used. Such carriers can be of different types, such as liquid Poly-α-olefin oligomers, liquid polyalkene hydrocarbons, liquid hydrogenated polyalkene hydrocarbons, Mineral oils, liquid poly (oxyalkylene) compounds, liquid alcohols or polyols, liquid esters and similar liquid carriers or solvents. Mixtures of two or more such carriers or solvents can be used.

Special liquid carriers for those described here Mannich detergents include: 1) a mineral oil or a mixture of mineral oils, especially those with a viscosity index of less than about 120, 2) or a mixture of poly-α-olefin oligomers, in particular those having an average molecular weight of about 500 to 1500, 3) polyethers, especially poly (oxyalkylene) compounds having a middle Molecular weight in the range of about 500 to about 1500, 4) one or more liquid polyalkylenes, or 5) mixtures of any from 1), 2), 3) and / or 4). Although not limited to These carriers have particularly desirable performance on.

The Mineral oil carriers, which can be used include paraffin, naphthenic and asphalt oils and can be derived from various crude oils and processed in any suitable manner. For example The mineral oils can be solvent-extracted or hydrotreated oils. Regeneratmineralöle can also be used. Hydrogenated oils are the most preferred. This preferably has mineral oil used has a viscosity at 40 ° C lower than about 1600 SUS, and more preferred between about 300 and 1500 SUS at 40 ° C. paraffin mineral oils most preferably have viscosities 40 ° C ranging from about 475 SUS to about 700 SUS. For best results, it is highly desirable that the mineral oil has a viscosity index of lower than about 100, more preferably lower than about 70, and most preferably in the range of about 30 to about 60.

The poly-α-olefins (PAO) carriers which may be used include hydrogenated and non-hydrogenated poly-α-olefin oligomers, ie, hydrotreated or non-hydrogenated products, primarily trimers, tetramers and pentamers of α-olefin Monomers, wherein these monomers contain 6 to 12, generally 8 to 12 and most preferably about 10 carbon atoms. Their synthesis is in Hydrocarbon Processing, February 1982, pages 75 et seq and in US Pat. No. 3,763,244 ; 3,780,128 ; 4,172,855 ; 4,218,330 and 4,950,822 explained. The normal process essentially involves catalytic oligomerization of short chain linear alpha olefins (suitably obtained by catalytic treatment of ethylene). The poly-α-olefins used as carriers will normally have a viscosity (measured at 100 ° C) in the range of 2 to 20 centistokes (cSt). Preferably, the poly-α-olefin has a viscosity of at least 8 cSt and most preferably about 10 cSt at 100 ° C. Particularly desirable poly-α-olefin (PAO) include polybutene having an average molecular weight of from about 500 to about 1500, and more particularly polyisobutene and / or hydrogenated polyisobutene having an average molecular weight of from about 500 to about 1500.

Polyethers which may be used as the carrier are poly (oxyalkylene) compounds having an average molecular weight of between about 500 and about 1500, and may particularly include poly (oxyalkylene) compounds which are fuel soluble compounds represented by the following formula can: R ₁ - (R ₂ -O) _n -R ₃

wherein R _{1 is} typically a hydrogen, alkoxy, cycloalkoxy, hydroxy, amino, hydrocarbyl (e.g., alkyl, cycloalkyl, aryl, alkylaryl, aralkyl, etc.), amino-substituted hydrocarbyl or hydroxy-substituted hydrocarbyl radical, R _{2 is} an alkylene radical having 2 to 10 carbon atoms (preferably 2 to 4 carbon atoms), R _{3 is} typically a hydrogen, alkoxy, cycloalkoxy, hydroxy, amino, hydrocarbyl (e.g. , cycloalkyl, aryl, alkylaryl, aralkyl, etc.), amino-substituted hydrocarbyl or hydroxy-substituted hydrocarbyl radical, and n is an integer of 1 to 500, and preferably in the range of 3 to 120, which is the number (usually a number average) of alkyleneoxy repeating groups. In compounds having multiple groups -R ₂ -O-, R ₂ may be the same or different alkylene radical, and where different, may be random or in blocks. Preferred poly (oxyalkylene) compounds are monools comprising repeating units formed by reacting an alcohol with one or more alkylene oxides, preferably an alkylene oxide.

The average molecular weight of the poly (oxyalkylene) compounds used as carrier fluids is preferably in the range of about 500 to about 3000, more preferably about 750 to about 2500 and most preferably over about 1000 to about 2000.

A useful subset of poly (oxyalkylene) compounds include the hydrocarbyl terminated poly (oxyalkylene) monools, as indicated at the bottom of column 6, line 20 through column 7, line 14 of U.S. Pat. No. 4,877,416 and references cited in this paragraph, the paragraph and the references here being incorporated by reference as if fully set forth.

A preferred subgroup of poly (oxyalkylene) compounds one or a mixture of alkyl poly (oxyalkylene) monools, which in their undiluted condition a gasoline soluble Liquid with a viscosity of at least about 70 centistokes (cSt) at 40 ° C and at least about 13 cSt at 100 ° C. Of these compounds are monools, which by propoxylation of one or a mixture of alkanols with at least about 8 carbon atoms and more preferred be formed in the range of about 10 to about 18 carbon atoms, particularly preferred.

The Poly (oxyalkylene) supports which are useful in the practice of this invention preferably have viscosities in their undiluted condition of at least about 60 cSt at 40 ° C (more preferably at least about 70 cSt at 40 ° C) and at least about 11 cSt at 100 ° C (stronger preferably at least about 13 cSt at 100 ° C). moreover have the poly (oxyalkylene) compounds which in the practice of this Be used invention, preferably viscosities in their undiluted condition of not higher than about 400 cSt at 40 ° C and not higher than about 50 cSt at 100 ° C. Most preferred are theirs Viscosities should not exceed about 300 cSt at 40 ° C and will not exceed about 40 cSt at 100 ° C. The most preferred poly (oxyalkylene) compounds have viscosities of not higher than about 200 cSt at 40 ° C and not higher than about 30 cSt 100 ° C have.

Preferred poly (oxyalkylene) compounds are poly (oxyalkylene) glycol compounds and monoether derivatives thereof which satisfy the above viscosity requirements and comprise repeating units obtained by reacting an alcohol or polyhydric alcohol with an alkylene oxide such as propylene oxide and / or butylene oxide, with or without Use of ethylene oxide, and in particular products in which at least 80 mol% of the oxyalkylene in the molecule of 1,2-propylene oxide are derived. Details concerning the preparation of such poly (oxyalkylene) compounds are given, for example, in U.S. Pat Kirk-Othmer, Encyclopedia of Chemical Technology, Third Edition, Vol. 18, pp. 633-645 (copyright 1982 by John Wiley & Sons) and in references cited therein, the above excerpt from the Kirk-Othmer Encyclopaedia and the references cited therein are incorporated herein by reference in their entirety. US Pat. No. 2,425,755 ; 2,425,845 ; 2,448,664 and 2,457,139 also describe such methods and are also incorporated herein by reference as if fully set forth herein.

A particularly preferred subgroup of poly (oxyalkylene) compounds comprises one or a mixture of alkylpoly (oxyalkylene) monools, which in its undiluted state a benzinlösliche Liquid with a viscosity of at least about 70 centistokes (cSt) at 40 ° C and at least about 13 cSt at 100 ° C. Typically, the maximum Viscosities at these temperatures are not higher as about 400 cSt at 40 ° C and higher than about 50 cSt at 100 ° C. More preferred are their viscosities do not exceed about 300 cSt at 40 ° C and not exceed about 40 cSt at 100 ° C. The strongest preferred poly (oxyalkylene) compounds become viscosities of not higher than about 200 cSt at 40 ° C and not higher than about 30 cSt at 100 ° C. Of these compounds are monools produced by propoxylation of one or a mixture of alkanols having at least about 8 carbon atoms and more preferably in the range of about 10 to about 18 Carbon atoms are formed, particularly preferred.

The Poly (oxyalkylene) compounds, which according to this invention used contain a sufficient number of branched Oxyalkylene units (e.g., methyldimethyleneoxy units and / or Ethyldimethyleneoxy units) to the poly (oxyalkylene) compound to make gasoline soluble.

Another group of carrier fluids are the liquid polyalkylenes such as polypropenes, polybutenes, polyisobutenes, polyamylenes, copolymers of propene and butene, copolymers of butene and isobutene, copolymers of propene and isobutene and copolymers of propene, butene and isobutene, or mixtures thereof. Other useful polyalkylenes include hydrogenated polypropene, hydrogenated polybutene, hydrogenated polyisobutene, or the like. Preferred polyalkylene carrier fluids include polybutenes having a molecular weight distribution lower than 1.4, as in US Pat. No. 6,048,373 taught, one. Use of materials of this general type along with other carrier fluids is disclosed, for example, in U.S. Pat US Pat. No. 5,089,028 and 5,114,435 whose disclosures are incorporated herein by reference the, described.

In In some cases, the Mannich base detergent / dispersant be synthesized in the carrier fluid. In other cases is the preformed detergent / dispersant with a suitable Amount of the carrier fluid mixed. If desired, For example, the detergent / dispersant may be in a suitable solvent or carrier fluid are formed and then with an additional Amount of the same or a different carrier fluid be mixed.

Of the Proportion of the liquid carrier relative to Mannich base in the preferred additive packages and fuel compositions used in this invention is such that the fuel composition, when consumed in an engine, improved intake valve cleanliness leads compared to the inlet valve purity of the same Motors operated with the same composition, except that the liquid carrier is missing. So in general the weight ratio of the carrier fluid to the Mannich base detergent / dispersant; based on an active ingredient, d. H. including Solvent (s), if any, which are in production the Mannichbase either during or after their formation, but before the addition of the carrier fluid, normally in the range of about 0.3: 1 to about 2.0: 1 and preferably in the Range from about 0.5: 1 to about 1.5: 1.

typically, For example, the additive concentrates of this invention contain from about 12 to about 69% by weight and preferably about 22 to about 50% by weight of the Mannich base detergent / dispersant, based on an active ingredient. These additive concentrates may also contain carrier fluid, the amount of which by the desired ratio of carrier to Mannich base detergent / dispersant.

If the fuel compositions of this invention are formulated The Mannich product and carrier fluid (with or without other additives) used in quantities that reduce or Inhibition of deposit formation in an internal combustion engine are sufficient. So the fuels are Nebenbestandteilmengen the Mannich base detergent / dispersant and liquid carrier fluid in proportions as above containing the formation of engine deposits, especially intake system deposits and strongest especially intake valve deposits in spark-ignited regulate or reduce internal combustion engines. Generally In summary, the fuels of this invention are obtained to an active ingredient as defined above, an amount of the Mannich base detergent / dispersant in the range of about 5 to about 300 ptb (pound of additive, by weight, per a thousand barrels of fuel, by volume) and preferred ranging from about 10 to about 200 ptb. In the preferred Fuel compositions in which a liquid carrier fluid is used, the total amount of the carrier fluid is preferred in an amount of about 0.3 to about 2.0 parts by weight per part by weight Mannich detergent / dispersant (based on an active ingredient) be present, more preferably the carrier fluid in an amount of about 0.4 to 1.0 parts by weight per one part Mannich detergent / dispersant will be present.

Other Additives. Other optional additives, such as one or more fuel-soluble Antioxidants, demulsifiers, rust or corrosion inhibitors, Metal deactivators, combustion modifiers, alcohol co-solvents, Octane improving agent, reducing agent Emissions, friction modifiers, lubricant additives, supplemental detergent / dispersant additives, biocides, antistatic Additives, resistance-reducing agents, antifriction agents, Anti-knock additives, anti-icing agents, valve seat recess additives, Combustion improvers, marking agents, dyes and multifunctional additives (e.g., methylcyclopentadienyl manganese tricarbonyl and / or other cyclopentadienyl manganese tricarbonyl compounds), can also in the fuels and additive concentrates of this Be included invention. Which components also for use be selected in the compositions of this invention, Each component should be present in an amount which is at least for it is sufficient for its intended function or functions exercise in the finished fuel composition.

In In a preferred embodiment, the additive concentrates contain additionally at least one inert hydrocarbon solvent with a boiling point below about 200 ° C.

Fuel bases. The fuel principles used in formulating the fuels of this invention are any and all fuel principles suitable for use in the operation of spark-ignited internal combustion engines, such as those described in US Pat. As lead-free motor and aviation gasolines and so-called reformulated gasolines, which typically both hydrocarbons of gasoline boiling range as well as fuel-soluble oxygen-containing mixture components such as alcohols, ethers and other ge suitable oxygenated organic compounds. Preferred mixing agents include fuel-soluble alkanols such as methanol, ethanol and their higher homologs, and fuel-soluble ethers such as methyl tertiary butyl ether, ethyl tertiary butyl ether, methyl tertiary amyl ether and analogous compounds, and mixtures of such materials. Oxygenated compounds, when used, will normally be present in the fuel base in an amount of less than about 25% by volume, and preferably in an amount that provides an oxygen content in the total fuel in the range of about 0.5 to about 5% by volume , to be available. However, in the practice of this invention, deviations from these ranges of proportions are permitted whenever deemed necessary, suitable, or desirable.

The Additives which in formulating the preferred fuels of these Can be used in the fuel base be mixed individually or in different sub-combinations. However, it is preferred to use all components simultaneously an additive concentrate of this invention, since this is the Benefits of mutual compatibility that benefits the combination of ingredients is provided when in the Form of an additive concentrate. Also reduces use of one Concentrate the mixing time and lowers the possibility of mixed mistakes.

Deposit formation control in internal combustion engines. The fuel additives of the present Invention are for regulation (i.e., prevention and / or removal) of deposits in internal spark-ignited and auto-igniting (eg diesel) internal combustion engines useful. regulation generally concerns the formation of less deposits, but It will additionally be appreciated that the present fuel additives Prevent and remove deposits. Although research in the field, in the first place, the emphasis was on Inlet valve deposition problems, and also in a certain Extent on combustion chamber deposits, was found that the fuel additives of the present invention are more versatile are. Not only can you prevent / remove be used by deposits in intake valves, but it was also discovered to be useful in regulating deposits in so-called "cooler" engine regions, in particular the fuel injector opening, are effective. Another use is the prevention of constipation Gasoline direct injection device.

deposits, which can form on inlet valves and openings can reduce engine output as they restrict airflow and can change the air flow pattern in the cylinder. Cold-start and warm-up behavior can also be adversely affected and exhaust emissions can increase. Close other valve deposit problems with intake valves Stick the valve and burn in the valve. The fuel additives of the present invention are in the regulation of these types of Deposits effective.

combustion chambers are another engine problem region for deposit formation. Combustion chamber deposits may have the octane requirement (ONR) as it increases the combustion temperatures and the compression ratio. When the ONR of the engine too strong because of the combustion chamber deposit formation it may be that then the recommended gasoline AKI is not knocking or a loss of power prevents the knock suppression in vehicles equipped with a knock sensor, can accompany. Combustion chamber deposition disorder (CCDI) and combustion chamber deposition separation (CCDF) are additional Engine deposition problems that can occur with some engines. CCDI can call itself a booming noise of a cold engine, which is made of a physical Contact between engine deposits on the piston cover and the Cylinder head results in some engine designs. CCDF occurs when combustion chamber deposits replace and between the valve surface and the valve seat get stuck, which is low compression pressures due to poor valve closing caused. The fuel additives of the present invention are also effective in regulating these types of deposits.

Fuel injectors and carburetors are also problem regions where deposit formation takes place can. Deposits in the small fuel passages of fuel injectors, such as injector stud deposits, can reduce the fuel flow and the spray pattern change what the performance, fuel economy and can affect the driving behavior adversely. deposits may have similar problems with engines with carburettors because carburetors also have small channels and openings to dose fuel. The fuel additives of In addition, the present invention is in the regulation These types of deposits are effective.

As indicated, the fuel additives of the present invention are also effective in controlling deposits in cooler engine areas. For example, set fuel injector open (PFI) deposits another engine area where deposits can adversely affect engine performance. For example, PFI deposits can form in the time that the engine is hot after it is turned off. A residual gasoline remaining in the injector tip is exposed to an elevated temperature for longer than gasoline flowing through the injector normally experiences, which can lead to gasoline decomposition, which in turn initiates deposit formation. These deposits may restrict fuel flow and destroy the spray pattern by partially blocking or clogging meter holes of the fuel injector tip. The fuel additives of the present invention are effective, for example, in preventing the formation of deposits or in forming considerably less deposits, and in some cases can reduce the amount of deposits. Therefore, the present fuel additives are effective in controlling these types of deposits that may otherwise occur in cooler engine regions.

The The following examples are intended to illustrate and not for limiting embodiments according to the Serve invention. All percentages, ratios, parts and amounts used and described herein are on the weight, unless stated otherwise.

Example (s)

The The following examples are illustrative and not restrictive presented.

model reactions are carried out to analyze the reaction products, which are obtained according to the present invention to be able to. 2,4-dimethylphenol (2,4-DMPh) is a hydrocarbyl-substituted hydroxyaromatic Compound useful as an analysis of the reaction product easier and analytical techniques such as NMR and mass spectrometry, be carried out more easily to confirm the purities, which are obtained according to the present invention can be. Model reactions are shown in the examples 1, 2 and 3 described.

 Example 1:

A model Mannich reaction product is prepared by reacting ethylenediamine ("EDA"), a 2,4-dimethylphenol (2,4-DMPh), and formaldehyde ("FA"). The molar ratio of EDA: 2,4-DMPh: FA used in the Mannich reaction is about 1.0: 2.0: 3.0. The EDA, 2,4-DMPh and FA are reacted in the following manner in a round bottomed flask ("RBF") equipped with mechanical stirring, nitrogen feed, a water separator and a heating mantle, solvent (such as toluene) and the 2, 4-DMPh are introduced into the RBF and the mixture is stirred under low heat while under an inert atmosphere (nitrogen layer, about 0.1 SCFH) The mixture of materials is stirred to mix the components while at about 80 ° C While it is under a nitrogen gas (N ₂ ) layer, the EDA is added to the RBF A slight exotherm occurs as the temperature rises to about 55 ° C. The FA is then added slowly and the RBF and its contents are heated until it reaches a temperature of about 80 ° C. This temperature is maintained for about one hour and the temperature is raised to 145 ° C. for distillation using a water separator After about 30 minutes at a temperature of about 95 to 105 ° C. After the distillation has started, the nitrogen gas flow is adjusted to 0.5 SCFH. The temperature is maintained at 145 ° C for about 2 to 2.5 hours. Vacuum stripping can be performed.

instrument analysis (like NMR and mass spectrometry) shows that the product is purer than 80% and that to obtain a purity of at least about 85% can be.

Out the total weight of the product which is in the reaction flask after distillation (and vacuum stripping if done) remains, an amount of additional solvent, which is needed to pack the final composition to bring to 25% solvent, calculated and added.

Example 2

One Model Mannich reaction product becomes similar in a way to Example 1, except that 1,3-diaminopropane as the polyamine is used. Instrument analysis (such as NMR and mass spectrometry) shows that the reaction product is about 95% pure.

Example 3

One Model Mannich reaction product becomes similar in a way to Example 1, except that 1,2-diaminocyclohexane as the Polyamine is used.

The Model Mannich reaction products of Examples 1 to 3 are substantially more pure than the products, which, for example, at molar ratios of polyamine: 2,4-DMPh: FA of 1: 1: 1 or 1: 1: 2.

Based on the model data can the Mannich reaction products of the present invention as examples at least about 80% pure, Generally more than at least about 85% pure, although basically a Mannich reaction product of the present invention which may have a purity of at least about 90 to at least about 95%.

Example 4

in einer Weise ähnlich zu Beispiel 1 und der allgemeinen Synthese, welche in [0032]–[0033] beschrieben wird, wobei das Molverhältnis von Ethylendiamin zu PIB-Cresol zu Formaldehyd ungefähr 1:2:3 beträgt, wenn die Umsetzung durchgeführt wird. Das PIB-Cresol wird durch Alkylierung von ortho-Cresol mit einem Polyisobutylen mit einem zahlenmittelern Molekulargewicht von ungefähr 900 gebildet. Ein Mannich-Reaktionsprodukt kann mit einer Reinheit von höher als 80% erhalten werden.A Mannich reaction product is obtained as shown by the following reaction scheme:

in a manner similar to Example 1 and the general synthesis described in [0032] - [0033] wherein the molar ratio of ethylenediamine to PIB-cresol to formaldehyde is about 1: 2: 3 when the reaction is carried out. The PIB-cresol is formed by alkylating ortho-cresol with a polyisobutylene having a number average molecular weight of about 900. A Mannich reaction product can be obtained with a purity greater than 80%.

Example 5

in einer Weise ähnlich zu Beispiel 1 und der allgemeinen Synthese, wie in [0032]–[0033] beschrieben, wobei das Molverhältnis von 1,2-Diaminocyclohexan zu PIB-Cresol zu Formaldehyd ungefähr 1:2:3 beträgt, wenn die Umsetzung durchgeführt wird. Das PIB-Cresol wird durch Alkylierung von ortho-Cresol mit einem Polyisobutylen mit einem zahlenmittleren Molekulargewicht von ungefähr 900 gebildet. Ein Mannich-Reaktionsprodukt kann mit einer Reinheit von höher als 80% erhalten werden.A Mannich reaction product is obtained as shown by the following reaction scheme:

in a manner similar to Example 1 and general synthesis as described in [0032] - [0033] wherein the molar ratio of 1,2-diaminocyclohexane to PIB-cresol to formaldehyde is about 1: 2: 3 when the reaction is carried out becomes. The PIB cresol is formed by alkylating ortho-cresol with a polyisobutylene having a number average molecular weight of about 900. A Mannich reaction product can be obtained with a purity greater than 80%.

Example 6

in einer Weise ähnlich zu Beispiel 1 und der allgemeinen Synthese, welche in [0032]–[0033] beschrieben wird, wobei das Molverhältnis von 1,3-Diaminopropan zu PIB-Cresol zu Formaldehyd ungefähr 1:2:3 beträgt, wenn die Umsetzung durchgeführt wird. Das PIB-Cresol wird durch Alkylierung von ortho-Cresol mit einem Polyisobutylen mit einem zahlenmittleren Molekulargewicht von ungefähr 900 gebildet. Ein Mannich-Reaktionsprodukt kann mit einer Reinheit von höher als 80% erhalten werden.A Mannich reaction product is obtained as shown by the following reaction scheme:

in a manner similar to Example 1 and the general synthesis described in [0032] - [0033] wherein the molar ratio of 1,3-diaminopropane to PIB-cresol to formaldehyde is about 1: 2: 3 when the reaction is carried out. The PIB cresol is formed by alkylating ortho-cresol with a polyisobutylene having a number average molecular weight of about 900. A Mannich reaction product can be obtained with a purity greater than 80%.

Example 7

One Mannich reaction product becomes similar in a way too Example 4, except that the hydroxy-substituted aromatic Hydrocarbyl compound is a PIB phenol. The PIB phenol is substantially para-substituted, i. H. a phenol comes with substituted a reactive PIB unit at the para position. The Mannich reaction product may be in a purity of at least about 80% will be received.

Example 8

One Mannich reaction product becomes similar in a way too Example 5, except that the hydroxy-substituted aromatic Hydrocarbyl a PIB phenol (the same PIB phenol as in Example 7). The Mannich reaction product can in a purity of at least about 80%.

Example 9

One Mannich reaction product becomes similar in a way too Example 6, except that the hydroxy-substituted aromatic Hydrocarbyl compound is a PIB phenol, wherein the PIB unit is in the para position and a less reactive unit than is the PIB unit in the PIB phenol of Example 7. The Mannich reaction product can be obtained in a purity of at least about 80%.

Example 10

One Distilled reaction product of each of Examples 4, 5, 6, 7, 8 and 9 will be used to prepare exemplary additive concentrates used. After distillation add to the total weight of the product remains in the reaction vessel, an amount added additional solvent necessary to bring the final packing composition to 25% solvent to bring, as appropriate, for each of the reaction products Examples 4 to 9 calculated and adjusted. additional suitable ingredients may be in the additive concentrate be included if desired.

Example 11

In in a manner similar to Example 1, products are added Use of a molar ratio of polyamine: hydrocarbyl substituted hydroxyaromatic compound: aldehyde of 1: 1: 1, 1: 1: 2, 1.17: 1: 1.29 and 10: 1: 1.2, with EDA being the polyamine. Similar in a way to Example 1 are comparative products of polyamine: hydrocarbylsubstituierter hydroxyaromatic compound: aldehyde using a molar ratio of about 1: 1: 1 and about 1: 1: 2, with 1,3-diaminopropane the polyamine is. In a manner similar to Example 1 a comparison is made at a molar ratio of polyamine: hydrocarbyl substituted hydroxyaromatic compound: aldehyde of about 1: 1: 1 in a similar manner to Example 1, wherein 1,2-diaminocyclohexane is the polyamine is. Regardless of whether a different solvent may or may not be used, is not expected to be one different solvent the resulting complex Mixture (reaction product) influenced, with a comparison to a Mannich reaction product according to the present invention Invention is appropriate.

The Comparative products are complex mixtures containing the Mannich reaction product contained in the mixture. The complex mixture is not easy to purify a substantially pure Mannich reaction product to obtain. The Mannich reaction product (compound) is therefore a component in a complex mixture. The Mannich reaction product (Compound in a mixture) is therefore quite impure and his Purity is basically very low, and a purity (Mixture, reaction product) of less than about 50%, for example is a reasonable expectation.

In contrast, in one aspect of the present invention, a Mannich reaction product is substantially free of by-products and unreacted starting materials, and may be considered substantially pure, providing a more reliable, more consistent formulation of an additive package (concentrate) with a more predictable concentration of the actual Mannich reaction product (compound ), characteri be siert. This also means that a fuel can be formulated more reliably containing a desired amount of the present Mannich reaction product (compound). It should also be appreciated that the present Mannich reaction products are readily scalable on a large scale with less possible loss of materials and with less opportunity for variation (reactivity) in reactant concentration during synthesis as compared to conventional approaches to production of Mannich condensation reaction products.

• I: Intrepid IVD-Fahrzeugtest: Einlassventilablagerung (IVD). Dieser Motorreinheitsbewertungs-IVD-Test ist ähnlich zum Standard-BMW-IVD-Test (ASTM D 5500), wobei Unterschiede die Verwendung eines Dodge Intrepid-Motors anstelle eines BMW-Motors und die Verwendung eines Fahrzeugprüfstandes anstelle einer Fahrstrecke für die Gesamtlaufleistung sind.
• II: ASTM D-6421, PFI-Prüfstandtest: Kraftstofföffnungs-Labortischtest, wobei die „Bestehens"-Quote weniger als 10% Verstopfungsquote ist.
• III: ASTM D-5598, Chrysler Turbolader-PFI-Test: Kraftstoffeinspritzvorrichtungsöffnungs-(PFI)-Motortest.
• IV: CRC Ford 2,3 L IVD-Test.
• V: Mercedes M102E 2,3 L IVD-Test zur Repräsentation der europäischen IVD-Testverfahren.

Performance tests. The Mannich reaction products of the present invention and comparative Mannich reaction products can be subjected to various performance tests, such as:

• I: Intrepid IVD Vehicle Test: Intake Valve Deposition (IVD). This engine cleanliness evaluation IVD test is similar to the standard BMW IVD test (ASTM D 5500), with differences being the use of a Dodge Intrepid engine instead of a BMW engine and the use of a vehicle test bench instead of a total mileage mileage.
• II: ASTM D-6421, PFI Test Bench Test: Fuel Open Lab Test, where the pass rate is less than 10% blockage rate.
• III: ASTM D-5598, Chrysler Turbocharger PFI Test: Fuel Injector Opening (PFI) Engine Test.
• IV: CRC Ford 2.3 L IVD test.
• V: Mercedes M102E 2.3 L IVD test to represent the European IVD test procedures.

The Fuel injector opening - ( "PFI") - Tests can be modified so that the results are reproducible are.

These Tests provide a direct measure of the magnitude of the observed Deposition formation ready, which in the presence of a special Mannich detergent takes place.

The treatment rates and results for a representative IVD test (2.3 L Ford test) for two representative Mannich reaction products of the present invention are presented in Table 1 below. Test 3 is a baseline fuel (Citgo RUL fuel) without a Mannich reaction product of the present invention. The test is performed for 100 hours. Table 1 FORD 2.3 L IVD @RICHMOND 100 h Results CRC Test Method TEST DEPOSITS, mg NO. additive PTB IVD CCD 1 Nothing 537.9 1,487.7 2 Example 5 60.0 34.3 1,543.8 3 Example 6 56.4 39.2 1,356.4

The Product of Example 5 in Test No. 2 is an additive (30.4% solids content). The additive combination used is generally 1 part of the Detergents (Mannich) and 0.8 parts of a carrier (in this Case a polypropylene oxide polymer obtained by adding propylene oxide to an alkylphenol).

The Product of Example 6 in Test No. 3 is an additive concentrate (30.4% Solid content). It's in the same way as the additive in Test No. 2 formulated.

New Fuel injectors are used at the beginning of the test.

The oil consumption can be checked to make sure the engine is working correctly, but otherwise it is not a requirement this test procedure.

CCD (mg) relates to the combustion chamber deposits, and it is the Total amount of CHD (cylinder head deposits) and PTD (piston head deposits).

Of the Expression PTB refers to pounds of additive per 1000 barrels of fuel.

Treatment rates and results for a modified PFI test bench test for the two representative Mannich reaction products against one fuel (performed twice, Tests 5 and 7) are shown in Table 2 below. (The ATSM D-6421 PFI test is modified by replacement with a different injector.) Table 2 PFI Test Bench Test (Modified) treatment % Flow loss at Test no. additive rate (PTB) 44 cycles (midw.). 4 Example 5 80 7.7 5 Nothing Nothing 19.7 6 Example 6 80 8.1 7 Nothing Nothing 12.8

Of the same fuel is used in tests 4-7.

One lower flow loss means better performance and consequently less deposit formation.

The Additives in Tests Nos. 4 and 6 are in the same concentration and in the same carrier. The additive of Example 5 is using the same carrier fluid as in the test 2 formulated. The additives are in a ratio of Mannich reaction product to carrier at a ratio formulated from 1 to 0.8. The additive of Example 6 is using of the same carrier fluid as formulated in Test 3.

One representative Mannich reaction product of the present Invention shows superior and better detergent properties in the IVD and PFI test bench tests compared to baseline fuel and also to a commercial Mannich product. This can be done by the relatively lower level of deposit formation is shown obtained when a Mannich product is used, which obtained according to the present invention can be.

The efficacy of a Mannich reaction product embodying the present invention can also be assessed in the "Mercedes" test, M102E (CEC-05-A-93) Engine Cleanliness Assessment Test The untreated fuel base is also separated using the same standard engine test (Test The treatment rates for additives containing a Mannich reaction product representative of the present invention and the results for the M102E (CEC-05-A-93) tests are shown in Table 3 below M102E 2.3 L IVD T 60 h results European IVD test procedure TEST DEPOSITS, mg NO. ADDITIVE IVD CCD 8th Example 5 20.6 864.9 9 Example 6 27.1 662.4 10 Nothing 160.6 315.8

The Additives in Tests Nos. 8 and 9 are at the same concentration. The additive of Test No. 8 has a solids content of 76.9 and is using the carrier fluid as in test 2 formulated. The additive of Example 6 has a solids content of 76.9 and is using the carrier fluid as formulated in Test 3. The solids content is the mixture of detergent (Mannich reaction product) and carrier.

The IVD data for test # 10 show that IVD is significantly, adversely higher when the fuel is not An additive containing an exemplary effective amount of a Mannich reaction product of the present invention.

Of the same hydrocarbon fuel is used in tests 8 to 10 used.

Of the Fuel consumption is measured and is about 229 Liters in tests 8 and 9.

The test can use Motorcraft ^® lubricating oil (15W-40).

The oil consumption can be measured to make sure the engine is correct works, but otherwise is not a requirement of this test procedure.

A Head opening rating lower than 10 is desired. In general, in connection with the tests described here a middle classification of the inlet openings made become. A head opening rating of 10 or lower can be considered clean and can be obtained if an effective amount of a Mannich reaction product of the present invention Invention is given to a fuel. The reaction product is typically in a carrier fluid, i. H. as a Additive. In principle, a classification of about 5 or lower using an additive which is an effective Detergent amount of a Mannich reaction product of the present invention Invention contains.

One Mannich reaction product, which represents the present invention, can be a superior and improved performance in one Provide an engine test, due to the reduced levels of PFI deposits, which are obtained by using it. The results are compared with a commercial Mannich product or the untreated fuel base significantly improved.

One Fuel, to which an effective amount of detergent of a Mannich reaction product of this invention may have improved IVD performance.

Mannich reaction products, which may represent the present invention Provide a better patch rate when using a conventional patch commercial Mannich additive product is compared.

It It goes without saying that the reactants and components, on what about the chemical name somewhere in the description or the claims thereof, whether in the singular or plural form Are identified as they are before contacting with another substance, to which by the chemical name or chemical type (eg fuel base, solvent, etc.). It does not matter which chemical changes, transformations and / or transformations, if any, in the resulting mixture or Solution or the reaction medium take place, there such Changes, transformations and / or transformations the natural Result of combining the specified reactants and / or Components under the conditions corresponding to this disclosure are required. So are the reactants and components as Identify ingredients to be brought together either in carrying out a desired chemical reaction (such as a Mannich condensation reaction) or at the formation of a desired composition (such as a Additive concentrate or an offset fuel mixture). you will also recognize that the additive components in the fuel basics individually per se and / or as components involved in education of preformed additive combinations and / or subcombinations used, can be given or mixed with it can be. Likewise, preformed additive concentrates, in which higher proportions of the additive components normally with one or more diluents or solvents be mixed together, formed, so that afterwards the concentrate with a fuel base in the course of formation the finished fuel composition can be mixed. Even though the claims hereinbelow to substances, components and / or ingredients in the present refer ("comprise", "is", etc.), Accordingly, the reference to the substance, the component or ingredient as it is or has been present may have at the time just before the first time with one or more other substances, components and / or ingredients or mixed according to the present disclosure were mixed. The fact that the substance, the component or the component of their original identity through a chemical transformation or transformation during the course of such mixing or mixing operations can have lost, is so completely irrelevant for accurate understanding and judgment of this Revelation and its claims.

As used here, the term "fuel-soluble" means that the substance of interest is sufficient at 20 ° C in the fuel base should be soluble, which to Use was selected to be at least the minimum To achieve the concentration required to enable that the substance serves its intended function. Prefers the substance becomes a substantially higher solubility in have the fuel base as this. However, the must Do not dissolve substance in all proportions in the fuel base.

Any and all Patent or any other publication to which in any part of this description here in total in this disclosure by reference for all purposes included, as if they were complete here explained.

These Invention is considerable in practice Variation susceptible. Consequently, with the above Description is not intended to limit the invention to a particular to limit the examples disclosed hereinabove and should not be construed as limiting. Much more is what is intended to be encompassed in the claims and their legally permitted equivalents.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

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Claims (41)

A fuel additive composition comprising (A) a Mannich reaction product obtained by reacting (i) one Polyamine with primary amino groups, selected from the group consisting of ethylenediamine, 1,3-diaminopropane and a 1,2-diaminocycloaliphat, (ii) a hydrocarbyl-substituted one hydroxyaromatic compound, and (iii) an aldehyde, wherein the Reaction using a molar ratio (i) :( ii) :( iii), selected from the group consisting of approximately 1: 2: 3 and 1: 1: 2; and (b) one liquid carrier. A fuel additive composition according to claim 1, wherein the polyamine comprises 1,2-diaminocyclohexane. A fuel additive composition according to claim 1 or 2 wherein the polyamine comprises ethylenediamine. Fuel additive composition according to one of claims 1 to 3, wherein the polyamine is 1,3-diaminopropane includes. Fuel additive composition according to one of claims 1 to 4, wherein the hydrocarbyl-substituted hydroxyaromatic compound ortho-cresol or phenol or a Mixture of o-cresol and phenol with an aliphatic hydrocarbyl substituent, that of a polyolefin having an average molecular weight in the Range is derived from about 300 to about 2000 includes. A fuel additive composition according to claim 5, wherein the aliphatic hydrocarbyl substituent is polyisobutylene includes. Fuel additive composition according to one of claims 1 to 5, wherein the aldehyde is an aliphatic Aldehyde, a heterocyclic aldehyde, an aromatic aldehyde or a mixture thereof. A fuel additive composition according to claim 7, wherein the aldehyde comprises an aliphatic C ₁ to C ₆ aldehyde. A fuel additive composition according to claim 7 or 8, wherein the aldehyde comprises a heterocyclic aldehyde. Fuel additive composition according to one of claims 7 to 9, wherein the aldehyde is an aromatic Aldehyde includes. Fuel additive composition according to one of claims 1 to 7, wherein the aldehyde is at least one, selected from the group consisting of formaldehyde, acetaldehyde, Propionaldehyde, butyraldehyde, valeraldehyde, and hexanalaldehyde, Benzaldehyde and salicylaldehyde, is. Fuel additive composition according to one of claims 1 to 7, wherein the aldehyde is a formaldehyde comprising producing reagent. Fuel additive composition according to one of claims 1 to 7, wherein the aldehyde is selected from the group consisting of consisting of furfural, thiophenealdehyde, paraformaldehyde and formalin, is selected. Fuel additive composition according to one of claims 1 to 13, wherein the carrier is selected from the group consisting of consisting of liquid poly-a-olefin oligomers, liquid Polyalkene hydrocarbons, liquid hydrotreated Polyalkene hydrocarbons, mineral oils, liquid Poly (oxyalkylene) compounds and any mixture thereof is. A fuel additive composition comprising (a) a Mannich reaction product obtained by reacting (i) a polyamine having primary amino groups which is capable of forming a substantially pure intermediate in the Mannich condensation reaction, the intermediate being a 5-membered or Having a 6-membered nitrogen-containing heterocyclic moiety, (ii) a hydrocarbyl-substituted hydroxyaromatic compound, and (iii) an aldehyde, the reaction using a Molar ratio (i) :( ii) :( iii) is carried out so that the polyamine (i) can react with the hydrocarbyl-substituted hydroxyaromatic compound (ii), thus obtaining a substantially pure intermediate, whereby the intermediate with the Aldehyde (iii), the Mannich reaction product being obtained as a substantially pure product; (c) a liquid carrier. Mannich detergent comprising the reaction product of (i) at least one of 1,2-diaminocyclohexane, ethylenediamine or 1,3-diaminopropane, (ii) polyisobutylene-substituted cresol and / or phenol, wherein the polyisobutylene has an average molecular weight from about 300 to about 2,000, and (iii) formaldehyde, wherein the reaction using a molar ratio (i) :( ii) :( iii) of about 1: 2: 3. Essentially pure Mannich reaction product, obtained by reacting (i) a polyamine with primary Amino groups, which results in the formation of a substantially pure intermediate in the Mannich condensation reaction is capable of, wherein the Intermediate a 5-membered or 6-membered nitrogenous heterocyclic unit, (ii) a hydrocarbyl-substituted hydroxyaromatic compound, and (iii) an aldehyde, wherein the Reaction carried out using a molar ratio of (i) :( ii) :( iii) so that the polyamine (i) with the hydrocarbylsubstituierten hydroxyaromatic compound (ii) can react, with such a is obtained substantially pure intermediate, wherein the Substantially pure intermediate with the aldehyde (iii) implement can, to obtain the substantially pure Mannich reaction product becomes. Essentially pure Mannich reaction product according to claim 17, wherein the hydrocarbyl-substituted hydroxyaromatic compound ortho-cresol or phenol or a Mixture of o-cresol and phenol with an aliphatic hydrocarbyl substituent, that of a polyolefin having an average molecular weight in the Range is derived from about 300 to about 2000 includes. Essentially pure Mannich reaction product according to claim 17 or 18, wherein the aldehyde is a aliphatic aldehyde, a heterocyclic aldehyde, an aromatic Aldehyde or a mixture thereof. The substantially pure Mannich reaction product of claim 19, wherein the aldehyde comprises an aliphatic C ₁ to C ₆ aldehyde. Essentially pure Mannich reaction product according to claim 19 or 20, wherein the aldehyde is a heterocyclic aldehyde. Essentially pure Mannich reaction product according to claim 19 or 21, wherein the aldehyde is a aromatic aldehyde. Essentially pure Mannich reaction product according to any one of claims 17 to 22, wherein the aldehyde is at least one selected from the Group consisting of formaldehyde, acetaldehyde, propionaldehyde, Butyraldehyde, valeraldehyde, and hexanalaldehyde, benzaldehyde and Salicylaldehyde, is. Essentially pure Mannich reaction product according to one of claims 17 to 23, wherein the aldehyde is formaldehyde or a formaldehyde-producing Reagent includes. Essentially pure Mannich reaction product according to claim 17, wherein the aldehyde is selected from the group consisting of consisting of furfural, thiophenealdehyde, paraformaldehyde and formalin, is selected. Fuel composition for an internal An internal combustion engine comprising (a) in a major amount a spark ignitable combustible hydrocarbon fuel; and a minor amount a fuel additive comprising a Mannich reaction product according to a of claims 17 to 25 in a carrier fluid. A fuel internal combustion engine composition comprising (a) a majority of a spark ignitable combustible hydrocarbon fuel; and (b) in a minor amount, a fuel additive composition comprising a Mannich reaction product obtained by reacting (i) a polyamine selected from the group consisting of ethylenediamine, 1,3-diaminopropane and 1,2-diaminocyclohexane, (ii) a hydrocarbyl-substituted hydroxyaromatic compound, and (iii) an aldehyde; the reaction using a molar ratio (i) :( ii) :( iii), selected from the group consisting of approximately 1: 2: 3 and 1: 1: 2, wherein the Mannich reaction product is present in an amount sufficient to reduce the amount by weight of engine deposits in an internal combustion engine associated with the fuel composition is operated to reduce. A fuel composition according to claim 27, comprising the fuel additive composition in an amount in a range from about 100 to about 1,000 ppm. A fuel composition according to claim 27 or 28, wherein the Mannich reaction product is obtained by reacting of (1) 1,2-diaminocyclohexane, (2) polyisobutylene-substituted Cresol and / or polyisobutylene-substituted phenol or their mixture, wherein the polyisobutylene has an average molecular weight of about From 300 to about 2,000, and (3) formaldehyde. A fuel composition according to claim 27 or 28, wherein the Mannich reaction product is obtained by reacting of (1) ethylenediamine, (2) polyisobutylene-substituted cresol and / or polyisobutylene-substituted phenol or their mixture, wherein the Polyisobutylene has an average molecular weight of about 300 to about 2,000, and (3) formaldehyde. A fuel composition according to claim 27 or 28, wherein the Mannich reaction product is obtained by reacting of (1) 1,3-diaminopropane, (2) polyisobutylene-substituted cresol and / or polyisobutylene-substituted phenol or a mixture thereof, wherein the polyisobutylene has an average molecular weight of about From 300 to about 2,000, and (3) formaldehyde. A fuel composition according to any one of the claims 27 to 31, further comprising at least one additive selected from the group consisting of antioxidants, carrier fluid, Demulsifiers, rust or corrosion inhibitors, metal deactivators, Combustion Modifiers, Alcohol Cosolvents, Octane improving agents, reducing agents emissions, friction modifiers, lubricant additives, supplemental detergent / dispersant additives, biocides, antistatic additives, resistance-reducing agents, Anti-reflective agents, anti-knock additives, anti-icing agents, Additives against valve seat recess, combustion improvers, Marking agents and dyes. Method of regulating engine deposits in an internal combustion engine, comprising operating the engine An engine with the fuel composition of claim 26. The method of claim 33, wherein the regulated ones Engine deposits include intake valve deposits. The method of claim 33 or 34, wherein the regulated Engine deposits Fuel injection deposits include. Process according to claims 33 to 35, wherein the regulated engine deposits are combustion chamber deposits include. Process according to claims 33 to 36, wherein the regulated engine deposits are intake port patches include. Process according to claims 33 to 37, the regulated engine deposits obstructing the direct injectors include. Fuel additive composition according to one of claims 1 or 15, wherein the reaction using a molar ratio (i) :( ii) :( iii) of about 1: 2: 3 is performed. Fuel additive composition according to one of claims 1 to 15, wherein the reaction using a molar ratio (i) :( ii) :( iii) of about 1: 1: 2 is performed. A fuel additive composition according to claim 15, wherein the polyamine comprises ethylenediamine.