PROCESS TO PREPARE QUATERNIZED NITROGEN COMPOUNDS, QUATERNIZED NITROGEN COMPOUND, USE OF A QUATERNIZ

专利摘要:
process to prepare quaternized nitrogen compounds, quaternized nitrogen compound, use of a quaternized nitrogen compound, additive concentrate, and, composition. the invention relates to new acid-free quaternized nitrogen compounds and to production and their use as fuel and lubricant additives, such as in particular as detergent additives, as anti-sedimentation wax (wasa) additives or as additives to reduce internal diesel injector deposits (idid). the invention also relates to additive packages that contain said compounds and to fuels and lubricants that contain said additives. the invention further relates to the use of said acid-free quaternized nitrogen compounds as fuel additives to reduce or prevent deposits in injection systems for direct injection diesel engines, in particular in common rail injection systems, to reduce fuel consumption. fuel from directed injection diesel engines, in particular from diesel engines having common ramp injection systems, and to minimize power loss in direct injection diesel engines, in particular from diesel engines having common ramp injection systems.
公开号:BR112013000297B1
申请号:R112013000297-2
申请日:2011-07-06
公开日:2020-10-06
发明作者:Wolfgang Grabarse；Harald Böhnke；Christian Tock；Cornelia Röger-Göpfert；Ludwig Völkel
申请人:Basf Se；
IPC主号:

专利说明:

The present invention relates to new acid-free quatemized nitrogen compounds, their preparation and their use as a fuel and lubricant additive, more particularly as a detergent additive, as a wax anti-sedimentation additive (WASA) or as an additive to reduce internal diesel injector deposits (IDID); the additive packages they comprise, these compounds; and fuels and lubricants so added. The present invention also relates to the use of these acid-free quatemized nitrogen compounds as a fuel additive to reduce or prevent deposits in injection systems for direct injection diesel engines, especially in common boom injection systems, to reduce consumption fuel for direct injection diesel engines, especially diesel engines with common rail injection systems, and to minimize power loss in direct injection diesel engines, especially diesel engines with common rail injection systems. State of the art:
In direct injection diesel engines, fuel is injected and distributed in an ultra-fine (nebulized) way through a multiple-port injection nozzle that reaches directly into the combustion chamber in the engine, instead of being introduced into a pre-chamber or fuel chamber. swirling as in the case of the conventional diesel engine (chamber). The advantage of direct injection diesel engines relies on their high performance for diesel engines and despite low fuel consumption. In addition, these engines achieve very high torque even at low speeds.
At present, essentially three methods are being used to inject fuel directly into the combustion chamber of the diesel engine: the conventional dispensing injection pump, the nozzle pump system (unitary injection system or unitary pump system) and the common boom system .
In the common ramp system, diesel fuel is transported by a pump with pressures up to 2000 bar on a high pressure line, the common ramp. Proceeding from the common ramp, branching lines go to the different injectors that inject the fuel directly into the combustion chamber. Full pressure is always applied to the common ramp, which allows for multiple injection or a specific injection form. In other injection systems, on the contrary, only minor variation in injection is possible. The injection in the common ramp is essentially divided into three groups; (1.) pre-injection, by which essentially smoother combustion is obtained, such that more severe combustion noises (“nailing”) are reduced and the engine appears to be running quietly; (2.) main injection, which is responsible especially for a good torque profile; and (3.) post-injection, which especially guarantees a low NOx value. In this post-injection, the fuel in general is not combusted, but instead evaporated by the residual heat in the cylinder. The exhaust gas / fuel mixture formed is transported to the exhaust gas system, where the fuel, in the presence of suitable catalysts, acts as a reducing agent for NOX nitrogen oxides.
The injection of individual cylinder, variable in the common ramp injection system can positively influence the pollutant emission from the engine, for example the emission of nitrogen oxides (NOx), carbon monoxide (CO) and especially of particulates (soot). This makes it possible, for example, that engines equipped with common boom injection systems can theoretically reach the Euro 4 standard even without additional particulate filters.
In modern common rail diesel engines, under particular conditions, for example when fuels containing biodiesel or fuels with metallic impurities such as zinc compounds, copper compounds, lead compounds and other metallic compounds are used, deposits can form in the injector orifices , which adversely affect the fuel injection performance and consequently communicate the performance of the engine, that is, especially reduce power, but in some cases also worsen combustion. The formation of deposits is further enhanced by further developments in the construction of the injector, especially by the change in the geometry of the nozzles (tapered holes, narrower with rounded outlet). For optimal long-term operation of the engine and injectors, such deposits in the nozzle orifices must be avoided or reduced by the appropriate fuel additives.
WO 2006/135881 describes quaternized ammonium salts prepared by condensing a hydrocarbyl-substituted acylating agent and a compound containing oxygen or nitrogen with a tertiary amino group, and subsequent quaternization by means of hydrocarbon epoxy in the presence of stoichiometric amounts of an acid, especially acetic acid. Stoichiometric amounts of the acid are required to ensure the complete ring opening of the epoxide quaternizing agent and consequently very substantially quantitative quaternization. The reaction of a dicarboxylic-based acylating agent, such as the PIBSA used in the examples in this one, with an amine, such as dimethylaminopropylamine (DMAPA), under condensation conditions, ie water elimination, forms a succinimide DMAPA which is then quatemized with epoxide and acid in equimolar amounts in each case.
Following the technical disclosure of WO 2006/135881, the presence of the stoichiometric amounts of acid, which are additionally absolutely necessary to balance the charge for the imide detergent quatemized therein, is found to be particularly disadvantageous. In order to reduce the acid content of the imide at this point, or in order to completely remove the acid, additional process measures would be required, which would make the product preparation more complex and consequently make it much more expensive. The epoxide quaternized imide prepared according to WO 2006/135881 is therefore - without further purification - used in the form of the carboxylate salt as a fuel additive in the tests described in the application.
On the other hand, however, it is known that acids can cause corrosion problems in fuel additives (as, for example, Sugiyama et al; SAE International, Technical Paper, Product Code: 2007-01-2027; Publication Date: 23-07-2007). The epoxide-based additive supplied in accordance with WO 2006/135881 is therefore afflicted with significant application risks due to the considerable corrosion risks that exist. In addition, the product has distinct disadvantages with respect to engine oil compatibility and low temperature properties.
In modern diesel engine injection systems, deposits cause significant performance problems. It is common knowledge that such deposits in the spray channels can lead to a decrease in the flow of fuel and consequently to a loss of power. The deposits at the tip of the injector, in contrast, impair the ideal formation of mist from the fuel spray and, as a result, cause worsened combustion and associated higher emissions and increased fuel consumption. In contrast to these conventional “external” deposition phenomena, internal deposits (collectively referred to as internal diesel injector deposits (IDID)) in particular on parts of the injectors, such as the nozzle needle, control piston, piston valve, on the valve seat, on the control unit and on the guides of these components, also increasingly causes performance problems. Conventional additives exhibit inadequate action against these IDIDs.
It is therefore an object of the present invention to provide improved quaternized fuel additives, especially based on hydrocarbyl-substituted polycarboxylic anhydrides, which no longer have the mentioned drawbacks of the prior art. Brief description of the invention:
It has now been discovered that, surprisingly, the above objective is achieved by providing an addition process, achievable under acid-free conditions, to prepare additives containing epoxide-quaternized nitrogen based on hydrocarbyl-substituted polycarboxylic anhydrides and compounds that have amino groups and are reactive with them, and for the acid-free reaction products thus obtained.
The inventive reaction regime surprisingly allows the addition of free acid to be dispensed completely, especially free protic acid which, according to the prior art, necessarily has to be added to the alkylene oxide quaternizing reagent. This is because the inventive process regime, due to the addition of the nitrogen-containing quaternizable compound over the hydrocarbyl-substituted polycarboxylic anhydride and the opening of the anhydride ring, generates an intramolecularly linked acid function and it is assumed that, without being bound to this model consideration, that this intramolecularly generated carboxyl group activates the alkylene oxide in the quaternization reaction and, through the protonation of the intermediate alcohol that forms after the addition of the alkylene oxide, forms the reaction product in the form of a betaine structure.
Surprisingly, the inventive additives thus prepared are superior in several respects to the prior art additives prepared in a conventional manner by epoxide / acid quaternization. Description of figures:
Figure 1 shows the power loss of different diesel fuels in a DW10 engine test. In particular, this is shown for non-additive fuel (squares) and an additive fuel according to the invention (diamonds), compared to a comparative fuel mixed with the prior art additive at the same dosage (triangles). Detailed description of the invention: Al) Specific embodiments
The present invention relates in particular to the specific embodiments which follow: 1. A process for preparing quaternized nitrogen compounds, wherein a. a compound comprising at least one group containing oxygen or nitrogen reactive with the anhydride, for example an -OH and / or a primary or secondary amino group, and additionally comprising at least one quaternizable amino group is added to an anhydride compound polycarboxylic anhydride, especially a polycarboxylic anhydride or a hydrocarbyl substituted polycarboxylic anhydride, especially a polyalkylene substituted polycarboxylic anhydride, and b. the product from stage a) is quaternized with a quaternizing agent especially free of H + donor and in particular acid free. 2. The process according to embodiment 1, wherein the polycarboxylic anhydride compound is a di-, tri- or tetracarboxylic anhydride. 3. The process according to each of the preceding embodiments, wherein the polycarboxylic anhydride compound is the anhydride of a C4-C10 dicarboxylic acid. 4. The process according to any of the preceding embodiments, wherein the polycarboxylic anhydride compound comprises at least one high molecular weight hydrocarbyl substituent, especially polyalkylene substituent, having a numerical average molecular weight (Mn) in the range from about 200 to 10,000, for example from 300 to 8000, especially from 350 to 5000. 5. The process according to any of the preceding embodiments, wherein the anhydride-reactive compound is selected from a. mono- or polyamines that are replaced by low molecular weight hydroxyhydrocarbyl, especially low molecular weight hydroxyalkyl, and have at least one primary, secondary or tertiary amino group; B. straight or branched, cyclic, heterocyclic, aromatic or non-aromatic polyamines having at least one primary or secondary amino group (reactive to anhydride) and having at least one qualifying primary, secondary or tertiary amino group; ç. piperazines. 6. Process according to embodiment 5, in which the compound reactive with the anhydride is selected from a. primary, secondary or tertiary monoamines replaced by low molecular weight hydroxyhydrocarbyl, especially low molecular weight hydroxyalkyl, and primary, secondary or tertiary diamines replaced by hydroxyalkyl, b. straight or branched aliphatic diamines having two primary amino groups; di- or polyamines having at least one primary and at least one secondary amino group; di- or polyamines having at least one primary and at least one tertiary amino group; aromatic carbocyclic diamines having two primary amino groups; aromatic heterocyclic polyamines having two primary amino groups; aromatic or non-aromatic heterocycles having a primary and a tertiary amino group. 7. The process according to any of the preceding embodiments, wherein the quaternizing agent is selected from epoxides; especially epoxides replaced with hydrocarbyl. 8. The process according to embodiment 7, characterized by the fact that the quaternization is carried out without the addition of an H + donor, especially without the addition of acid. 9. The process according to any of the preceding embodiments, in which stage a), i.e. the addition reaction, is carried out at a temperature of less than about 80 ° C and especially at a temperature in the range from about 30 to 70 ° C, in particular from 40 to 60 ° C. 10. The process according to any of the preceding embodiments, in which stage a) is carried out in a period of 1 minute to 10 hours or 10 minutes to 5 hours or 16 minutes to 4 hours or 2 to 3 hours. 11. The process according to any of the preceding embodiments, in which stage b), that is to say, the quaternization, is carried out at a temperature in the range of 40 to 80 ° C. 12. The process according to any one of the preceding embodiments, in which stage b) is performed over a period of 1 to 10 hours. 13. The process according to any of the preceding embodiments, wherein stage b) is carried out with an epoxide, especially low molecular weight hydrocarbyl epoxide, as the quaternizing agent in the absence of (stoichiometric amounts of) free acid (other than the polycarboxylic acid compound). 14. The process according to any of the preceding embodiments, wherein the reaction according to stage a) and / or b) is carried out in the absence of a solvent, in particular in the absence of a protic organic solvent. 15. A quaternized nitrogen compound or reaction product obtainable by a process according to any of the preceding embodiments. 16. A quaternized nitrogen compound or reaction product according to embodiment 15, which comprises at least one compound of the general formulas:
especially Ia-1, optionally in combination with Ia-2 and / or Ia-3, or
especially Ib-1, optionally in combination with Ib-2 and / or Ib-3, where Ri is H or a straight or branched hydrocarbyl radical that can be optionally mono- or polysubstituted by hydroxyl, carboxyl radicals, hydrocarbiloxy and / or acyl, or has one or more ether groups on the hydrocarbyl chain, and is especially H or short-chain hydrocarbyl, especially alkyl; R2 is H or alkyl; R3 is hydrocarbyl, especially long-chain hydrocarbyl, for example a polyalkylene radical; at least one of the radicals R4, R5 and R4 is a radical introduced by the quaternization, especially a low molecular weight hydrocarbyl radical or low molecular weight hydrocarbyl radical, and the remaining radicals are selected from 15 weight hydrocarbyl radicals straight or branched low molecular, cyclic hydrocarbyl radicals, which are optionally mono- or polysubstituted and / or have one or more heteroatoms; R-7 is H or a straight or branched chain low molecular weight hydrocarbyl radical that can optionally be mono- or polysubstituted, for example di-, tri- or tetra-substituted, by hydroxyl, carboxyl, hydrocarbyloxy radicals low and / or acyl identical or different, or has one or more ether groups in the hydrocarbyl chain, or R7 together with one of the radicals R4, R5 and R $ forms a bridging group, for example an alkylene or alkenylene group; L! is a chemical bond or a straight or branched alkylene group and L2 is a straight or branched alkylene group that optionally carries one or more hetero atoms, especially selected from -O- and / or substituents. 17. A quaternized nitrogen compound or reaction product according to embodiment 15 or 16 which is essentially donor-free, especially essentially acid-free, and especially does not comprise any of the short-chain inorganic or organic acid additions. 18. The use of a quaternized nitrogen compound or reaction product according to any of embodiments 15 to 17 as a fuel additive or lubricant additive. 19. The use according to embodiment 18 as a detergent additive for diesel fuels. 20. The use according to embodiment 18 as an anti-sedimentation wax additive (WASA) for intermediate distillate fuels, especially diesel fuels. 21. The use according to embodiment 19 as an additive to reduce or prevent deposits in direct injection diesel engine injection systems, especially in common rail injection systems, to reduce the fuel consumption of diesel engines direct injection, especially of diesel engines with common rail injection systems and / or to minimize the loss of power in direct injection diesel engines, especially in diesel engines with common rail injection systems. 22. Use according to embodiment 21 as an additive to control (prevent or reduce, especially partially, essentially complete node or completely reduce) deposits of internal diesel engine (IDID), ie deposits in the injector interior; especially wax or deposits like soap and / or polymeric deposits like carbon. 23. Additive concentrate comprising, in combination with other fuel additives, especially diesel fuel additives, at least one nitrogenized nitrogen compound or a reaction product according to each of embodiments 15 and 16. 24. Composition of fuel comprising, in a majority of a standard base fuel, an effective amount (in detergency) of at least one nitrogenized nitrogen compound or a reaction product according to each of embodiments 15 and 16. 25. Lubricating composition comprising, in a majority of a usual lubricant, an effective amount (in detergency) of at least one nitrogen compound or a reaction product according to each of the embodiments 15 and 16. A2) General definitions
An "H + donor" or "proton donor" refers to any chemical compound that is capable of releasing a proton to a proton acceptor. Examples are especially protic acids, but also "acid-free" in the context of the present invention means the absence of low molecular weight inorganic or organic acid and / or its corresponding anion, and includes both the lack of acid addition during the preparation process according to the invention regarding, more particularly, the absence of acid and / or its anion in the quaternized reaction product used as the additive. The acid exemption includes especially the absence of stoichiometric amounts of such acids and their anions (stoichiometry based on the quaternizing agent used, such as especially the epoxide), and exists especially when, the quaternizing agent based on the used epoxide, the acid free or its anion are present only in substoichiometric amounts, for example in molar ratios of less than 1: 0.1, or less than 1: 0.01 or 1: 0.001, or 1: 0.0001, of quaternizing agent for acid. The acid exemption especially also includes the complete absence of an inorganic or organic protic acid and / or its anion (this is when protic acid and / or its anion is no longer analytically detectable). An "acid" in this context is especially a free protic acid.
Examples of free "protic acids" include inorganic acids or mineral acids, such as HCl, H2SO4, HNO3, H2CO3 and organic carboxylic acid, especially RCOOH type monocarboxylic acids where R is a short-chain hydrocarbyl radical.
"Free" or "unbound" acid means that the acid function is not itself part of a quaternized compound, that is, in principle it is removable from the compound, for example by ion exchange.
Typical protic acid "anions" are, for example, carboxylate anions, for example acetate and propionate.
Nitrogen groups or "quaternizable" amino groups especially include primary, secondary and tertiary amino groups.
A "condensation" or "condensation reaction" in the context of the present invention describes the reaction of two molecules with the elimination of one molecule, especially a molecule of water. When such an elimination is not detectable, more particularly not detectable in stoichiometric quantities, and the two molecules react nonetheless, for example with the addition, the reaction in question of the two molecules is "without condensation".
A "betaine" refers to a specific saline form of a chemical compound that has both a negative charge and a positive charge on one and the same molecule, where the charge, however, cannot be eliminated by intramolecular ion transfer.
“IDID” means “internal diesel injector deposits”, as seen in modern diesel engines. Although conventional (external) deposits are deposits such as coke in the region of the needle tips and in the spray nozzles of the injection nozzles, meanwhile there is an accumulation of deposits inside the injection nozzles, which leads to significant performance problems, for example blockage of the internal moving parts of the valve and the associated worsening or lack of control of fuel injection, loss of power and others. IDIDs occur in the form of wax deposits or as a soap (fatty acid residues and / or analytically detectable Ci2 or Ci6 succinic acid residues) or in the form of polymeric carbon deposits. The latter in particular takes particular demands regarding its removal / avoidance.
In the absence of instructions to the contrary, the following general conditions apply:
"Hydrocarbyl" can be interpreted widely and comprises straight and branched straight and branched hydrocarbon radicals, both of which can optionally additionally comprise heteroatoms; for example O, N, NH, S, in your chain.
"Cyclic hydrocarbyl radicals" can comprise aromatic or non-aromatic rings and optionally have one or more ring hetero atoms selected from O, S, N, NH.
The "long chain" or "high molecular weight" hydrocarbyl radicals have a numerical average molecular weight (Mn) of 85 to 20,000, for example 113 to 10,000, or 200 to 10,000 or 350 to 5000, for example from 350 to 3000, from 500 to 2500, from 700 to 2500, or from 800 to 1500. More particularly, they are formed essentially of C2.6 monomer units, especially C2.4, such as ethylene, propylene, n- or isobutylene or their mixtures, where different monomers can be copolymerized in random distribution or as blocks. Such long-chain hydrocarbyl radicals are also referred to as polyalkylene radicals or poly-C2.6 or poly-C2.4 alkylene radicals. Suitable long-chain hydrocarbyl radicals and their preparation are also described, for example, in WO 2006/135881 and in the literature cited therein.
Examples of particularly useful polyalkylene radicals are polyisobutenyl radicals derived from “high reactivity” polyisobutenes which are notable for a high content of terminal double bonds. Terminal double bonds are alpha-olefinic double bonds of the type
which are also referred to collectively as vinylidene double bonds. Suitable high reactivity polyisobutenes are, for example, polyisobutenes that have a vinylidene double bond ratio of more than 70 mol%, especially greater than 80 mol% or greater than 85 mol%. Preference is given especially to polyisobutenes that have homogeneous polymeric structures. The homogeneous polymeric structures are possessed especially by those polyisobutenes formed from isobutene units to a degree of at least 85% by weight, preferably to a degree of at least 90% by weight and more preferably to a degree of at least 95% in weight. Such highly reactive polyisobutenes preferably have a numerical average molecular weight within the range mentioned above. In addition, high reactivity polyisobutenes can have a polydispersity in the range of 1.05 to 7, especially from about 1.1 to 2.5, for example less than 1.9 or less than 1.5. Polydispersity is understood to mean the weighted average molecular weight quotient Mw divided by the numerical average molecular weight Mn.
Particularly suitable high reactivity polyisobutenes are, for example, BASF SE's Glissopal brands, especially Glissopal 1000 (Mn = 1000), Glissopal V 33 (Mn = 550) and Glissopal 2300 (Mn = 2300) and mixtures thereof. Other numerical average molecular weights can be established in a manner known in principle by mixing polyisobutenes of different numerical average molecular weights or by extracting polyisobutenes from particular molecular weight ranges.
The "short chain hydrocarbyl" or "low molecular weight hydrocarbyl" is especially straight or branched alkyl or alkenyl, optionally interrupted by one or more, for example 2, 3 or 4; heteroatom groups such as -O- or -NH-, or optionally mono- or polysubstituted, for example di-, tri- or tetra-substituted.
The "short chain hydrocarbiloxy" or "low molecular weight hydrocarbiloxy" is especially straight or branched chain alkyloxy or alkenyloxy, optionally interrupted by one or more, for example 2, 3 or 4, heteroatom groups such as -O- or -NH-, or optionally mono- or polysubstituted, for example di-, tri- or tetra-substituted.
The "hydroxyl substituted hydrocarbyl" or "hydroxyhydrocarbyl" especially represents the hydroxyl substituted analogs of the alkyl or alkenyl radicals defined herein.
"Alkyl" or "lower alkyl" represent specially saturated, straight or branched chain hydrocarbon radicals having 1 to 4, 1 to 6, 1 to 8, or 1 to 10 or 1 to 20, carbon atoms , for example methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2 , 2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl , 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1 -ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl; and also n-heptyl, n-octyl, n-nonyl and undecyl, and their analogues single or multiply branched.
"Hydroxyalkyl" represents especially the mono- or polyhydroxylated analogs, especially monohydroxylated, of the above alkyl radicals, for example the monohydroxy analogues of the straight or branched alkyl radicals above, for example linear hydroxyalkyl groups with such a primary hydroxyl group. such as hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl.
"Alkenyl" represents mono- or polyunsaturated, especially monounsaturated, straight or branched hydrocarbon radicals having 2 to 4, 2 to 6, 2 to 8, 2 to 10 or 2 to 20 carbon atoms and one double bond at any position, for example C2-C6 alkenyl such as ethylene, 1-propenyl, 2-propenyl, 1-methylethyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2- methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl- 1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl- 3- butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, l- ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-l-pentenyl, 3-methyl-l-pentenyl, 4-methyl-l-pentenyl, l-methyl-2-pentenyl, 2-methyl-2-penten ila, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3- butenyl, 1,2-dimethyl-1-butyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butyl, 1,3-dimethyl-1 - butenyl, 1,3-dimethyl-2- butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3- butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl- l-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, l-ethyl-l-methyl-2-propenyl, l-ethyl-2- methyl-1-propenyl and 1-ethyl-2-methyl-2-propenyl.
"Hydroxyalkenyl" especially represents the mono- or polyhydroxy analogues, especially monohydroxylates, of the alkenyl radicals above.
"Alkyloxy" and "alkenyloxy" represent especially the oxygen-linked analogues of the radicals "alkyl" and "alkenyl" above.
"Alkylene" represents straight or mono- or poly-branched hydrocarbon bridge groups having from 1 to 10 carbon atoms, for example C1-C7 alkylene groups selected from -CH2-, - (CH2) 2-, - ( CH2) 3-, - (CH2) 4-, - (CH2) 2-CH (CH3) -, -CH2-CH (CH3) -CH2-, (CH2) 4-, - (CH2) 5-, - ( CH2) 6, - (CH2) 7-, -CH (CH3) -CH2-CH2-CH (CH3) - OR -CH (CH3) -CH2-CH2-CH2-CH (CH3) - OR C1- alkylene groups C4 selected from -CH2-, - (CH2) 2-, - (CH2) 3-, - (CH2) 4-, - (CH2) 2-CH (CH3) -, -CH2-CH (CH3) -CH2- ; or represents C2-Cg alkylene groups, for example CH2-CH (CH3) -, -CH (CH3) -CH2-, CH (CH3) -CH (CH3) -, -C (CH3) 2-CH2-, -CH2 - C (CH3) 2-, -C (CH3) 2-CH (CH3) -, -CH (CH3) -C (CH3) 2-, -CH2-CH (Et) -, - CH (CH2CH3) -CH2 -, -CH (CH2CH3) -CH (CH2CH3) -, C (CH2CH3) 2-CH2-, -CH2- C (CH2CH3) 2-, -CH2-CH (n-propyl) -, -CH (n-propyl) ) -CH2-, -CH (n-propyl) - CH (CH3) -, -CH2-CH (n-butyl) -, -CH (n-butyl) -CH2-, -CH (CH3) - CH (CH2CH3 ) -, -CH (CH3) -CH (n-propyl) -, -CH (CH2CH3) -CH (CH3) -, - CH (CH3) -CH (CH2CH3) -> or represents C2-C4 alkylene groups, for example example selected from - (CH2) 2-, -CH2-CH (CH3) -, -CH (CH3) -CH2-, -CH (CH3) - CH (CH3) -, -C (CH3) 2-CH2-, -CH2-C (CH3) 2-, -CH2-CH (CH2CH3) -, - CH (CH2CH3) -CH2-,
"Alkenylene" represents the mono- or polyunsaturated analogs, especially monounsaturated, of the above alkylene groups having 2 to 10 carbon atoms, especially. C2-C7 alkenylenes or C2-C4 alkenylenes, such as -CH = CH-, -CH = CH-CH2-, -CH2-CH = CH-, - CH = CH-CH2-CH2-, -CH2-CH = CH -CH2- -CH2-CH2-CH = CH-, -CH (CH3) - CH = CH-, -CH2-C (CH3) = CH-.
"Acyl" represents straight or branched chain radicals, optionally mono- or polyunsaturated, optionally substituted C1-C24 monocarboxylic acids, especially C1-C12 or Ci-Cg. For example, useful acyl radicals are derived from the following carboxylic acids: saturated acids such as formic acid, acetic acid, propionic acid and n- and i-butyric acid, n- and i-valeric acid, capronic acid, enantic acid , caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, marginal acid, stearic acid, nonadecanoic acid, arachic acid, beenic acid, lignocic acid, cerotic acid melissic; monounsaturated acids such as acrylic acid, crotonic acid, palmitoleic acid, oleic acid and erucic acid; and di-unsaturated acids such as sorbic acid and linoleic acid. When double bonds are present in fatty acids, they can be in cis or trans form.
"Cyclic hydrocarbyl radicals" especially comprise: - cycloalkyl: carbocyclic radicals having 3 to 20 carbon atoms, for example C3-C12 cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cycloneyl, cyclodecyl, cycloundecyl and cyclodecyl and cyclodecyl ; preference is given to cyclopentyl, cyclohexyl, cycloeptyl, and also cyclopropylmethyl, cyclopropylethyl, cyclobutylmethyl, cyclobutylethyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl, or cycloalkyl, cyclopentyl, cyclopentyl, cyclopentyl, cyclopentyl, cyclopentyl, cyclohexyl, cyclohexyl, cyclohexyl cyclopentylethyl, cyclohexylmethyl, where the bond, to the rest of the molecule can be via any suitable carbon atom. - cycloalkenyl: monocyclic, mono-unsaturated hydrocarbon groups having 5 to 8; preferably up to 6, ring carbon members, such as cyclopenten-1-yl, cyclopenten-3-yl, cyclohexen-1-yl, cyclohexen-3-yl and cyclohexen-4-yl; - aryl: mono- or polycyclic aromatic radicals, preferably mono- or bicyclic, optionally substituted having from 6 to 20, for example from 6 to 10, ring carbon atoms, for example phenyl, biphenyl, naphthyl such as 1- or 2 -naftila, tetrahydronaftila, fluorenila, indenila and fenantrenila. These aryl radicals can optionally be 1, 2, 3, 4, 5 or 6 identical or different substituents. - arylalkyl: aryl substituted analogs of the above alkyl radicals, where aryl is in the same way as defined above, for example phenyl-alkyl CrC4 radicals selected from phenylmethyl and phenylethyl. - heterocyclyl: radicals of heterocycles or five to seven membered partially unsaturated or aromatic heterocyclyl (= heteroaryl or hetaryl) comprising one, two, three or four heteroatoms in the O, N and S group. For example, the following subgroups may be mentioned: - saturated or monounsaturated 5- or 6-membered heterocyclic comprising one or two nitrogen atoms and / or an oxygen or sulfur atom or one or two oxygen and / or sulfur atoms as ring members, for example 2- tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 1-pyrrolidinyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 3-isothiazolidinyl, 4-isothiazolidinyl, 4- pyrazolidinyl, 4-pyrazolidinyl, 5-pyrazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl, 5-thiazolidinyl, 2-amidazolidinyl, 4-imidazolidinyl, 2-pyrrolin-2-yl 2-pyrrolin-3-yl, 3-pyrrole in-2-yl, 3-pyrrolin-3-yl, 1-piperidinyl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 1,3-dioxan-5-yl, 2-tetrahydropyranyl, 4-tetrahydropyranyl, 2-tetrahydrothienyl, 3-hexahydro-pyridazinyl, 4-hexahydropyridazinyl, 2-hexahydropyrimidinyl, 4-hexahydro-pyrimidinyl, 5-hexahydropyrimidinyl and 2-piperazinyl; - 5-membered aromatic heterocyclyl comprising, as well as carbon atoms, one, two or three nitrogen atoms or one or two nitrogen atoms and a sulfur or oxygen atom as ring members, for example 2-furyl, 3- furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, el, 3,4-triazol-2-yl; - aromatic 5-membered heterocyclyl having 1, 2, 3 or 4 nitrogen atoms as ring members, such as 1-, 2- or 3-pyrrolyl, 1-, 3- or 4-pyrazolyl, 1-, 2- or 4-imidazolyl, 1,2,3- [1H] -triazol-4-yl, 1,2,4- [1H] -triazol-1-yl, 1,2,4- [1H] -triazole-5 -yl, 1,2,4- [4H] -triazol-4-yl, 1,2,4- [4H] -triazol-3-yl, [lH] -tetrazol-l-yl, [lH] -tetrazole -5-yl, [2H] -tetrazol-2-yl and [2H] -tetrazol-5-yl; - aromatic 5-membered heterocyclyl having 1 heteroatom selected from oxygen and sulfur and optionally 1, 2 or 3 nitrogen atoms as ring members, for example 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 3- or 4-isoxazolyl, 3- or 4-isothiazolyl, 2-, 4- or 5-oxazolyl, 2-, 4- or 5-thiazolyl, 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazole -5-yl, 1,3,4-thiadiazol-2-yl, 1,2,4-oxadiazol-5-yl, 3,4-oxadiazol-2-yl; - 6-membered heterocyclyl comprising, as well as carbon atoms, one or two, or one, two or three, nitrogen atoms as ring members, for example 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl , 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1,2,4-triazin-3-yl; 1,2,4-triazin-5-yl, 1,2,4-triazin-6-yl and 1,3,5-triazin-2-yl.
"Substituents" for the radicals specified herein are specially selected from keto groups, -COON, -COO-alkyl, -OH, -SH, -CN, amino, -NO2, alkyl, or alkenyl groups. A3) Polycarboxylic anhydride compounds, such as especially polycarboxylic anhydrides and hydrocarbyl substituted polycarboxylic anhydrides;
The anhydride used is derived from any di- or polybasic aliphatic (eg tri- or tetrabasic), especially di-, tri- or tetracarboxylic acids, and is optionally substituted by one or more (eg 2 or 3), especially one long-chain alkyl radical and / or a high molecular weight hydrocarbyl radical, especially a polyalkylene radical. Examples are anhydrides of C3-C10 polycarboxylic acids, such as malonic dicarboxylic acids, succinic acid, glutaric acid, adipic acid, pyelic acid, submeric acid, azelaic acid and sebacic acid and their branched analogs; and citric tricarboxylic acid. Anhydrides can also be obtained by adding at the end the corresponding monounsaturated acids of at least one long chain alkyl radical and / or high molecular weight hydrocarbyl radical. Examples of suitable monounsaturated acids are fumaric acid, maleic acid, itaconic acid.
The hydrophobic “long chain” or “high molecular weight” hydrocarbyl radical that ensures sufficient solubility of the quaternized product in the fuel has a numerical average molecular weight (Mn) of 85 to 20,000, for example 113 to 10,000, or 200 to 10,000 or 350 to 5000, for example from 350 to 3000, from 500 to 2500, from 700 to 2500, or from 800 to 1500. Typical hydrophobic hydrocarbyl radicals include polypropenyl, polybutenyl and polyisobutenyl radicals, for example with a weight molecular numerical average Mn from 3500 to 5000, from 350 to 3000, from 500 to 2500, from 700 to 2500 and from 800 to 1500.
Suitable hydrocarbyl substituted anhydrides are described, for example, in DE 43 19 672 and WO 2008/138836.
Suitable hydrocarbyl substituted polycarboxylic anhydrides also comprise the polymeric, especially dimeric, forms of such hydrocarbyl substituted polycarboxylic anhydrides. The dimeric forms comprise, in particular, two groups of acid anhydride which can be reacted independently with the quantifiable nitrogen compound in the preparation process according to the invention. A4) Quaternizing Agents:
The useful quaternizing agents are in principle all compounds suitable as such. In a particular embodiment, however, at least one quaternizable tertiary nitrogen atom is quaternized with at least one quaternizing agent selected from epoxides, especially hydrocarbyl epoxides:
wherein the radicals Ra present there are the same or different and are each H or a hydrocarbyl radical, where the hydrocarbyl radical has at least 1 to 10 carbon atoms. In particular, these are aliphatic or aromatic radicals, for example straight or branched CMO aquyl radicals, or aromatic radicals, such as phenyl or C4.4 alkylphenyl.
Suitable hydrocarbyl epoxides are, for example, aliphatic and aromatic alkylene oxides, such as especially 62-12 alkylene oxides, such as ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-oxide -butylene, 2-methyl-1,2-propene oxide (isobutene oxide), 1,2-pentene oxide, 2,3-pentene oxide, 2-methyl-1, 2-butene oxide, 3-oxide -methyl-1,2-butene, 1,2-hexene oxide, 2,3-hexene oxide, 3,4-hexene oxide, 2-methyl-1,2-pentene oxide, 2-ethyl oxide - 1,2-butene, 3-methyl-1,2-pentene oxide, 1,2-decene oxide, 1,2-dodecene oxide or 4-methyl-1,2-pentene oxide; and also aromatic substituted ethylene oxides, such as optionally substituted styrene, especially styrene oxide or 4-methylstyrene oxide.
In the case of the use of epoxides as quaternizing agents, they are used especially in the absence of free acids, especially in the absence of free protic acids, such as in particular CM2 monocarboxylic acids such as formic acid, acetic acid or propionic acid, or dicarboxylic acids C2-12, such as oxalic acid or adipic acid; or even in the absence of sulfonic acids such as benzenesulfonic acid or toluenesulfonic acid or aqueous mineral acids such as sulfuric acid or hydrochloric acid. The quaternization product thus prepared is thus "acid-free" in the context of the present invention. A5) Quaternized or quaternizable nitrogen compounds:
The reactive nitrogen compound that is quantifiable with the anhydride is selected from a. hydroxyalkyl-substituted mono- or polyamines having at least one quaternized amino group (e.g. choline) or primary, secondary or tertiary quaternizable; B. straight or branched, cyclic, heterocyclic, aromatic or non-aromatic polyamines having at least one primary or secondary amino group (reactive to anhydride) and having at least one quaternized or primary, secondary or tertiary amino group; ç. piperazines,
The quantifiable nitrogen compound is specially selected from a. primary, secondary, tertiary or quaternary monoamines substituted with hydroxyalkyl and primary, secondary, tertiary or quaternary diamines replaced with hydroxyalkyl; B. straight or branched aliphatic diamines having two primary amino groups; di- or polyamines having at least one primary and at least one secondary amino group; di- or polyamines having at least one primary and at least one tertiary amino group; di- or polyamines having at least one primary amino group and at least one quaternary; aromatic carbocyclic diamines, having two primary amino groups; aromatic heterocyclic polyamines having two primary amino groups; aromatic or non-aromatic heterocycles having a primary and a tertiary amino group.
Examples of suitable "hydroxyalkyl substituted mono- or polyamines" are those provided with at least one hydroxyalkyl substituent, for example 1, 2, 3, 4, 5 or 6 hydroxyalkyl substituents.
Examples of "hydroxyalkyl substituted monoamines" include: N-hydroxyalkyl monoamines, N, N-dihydroxyalkyl monoamines and N, N, N-trihydroxyalkyl monoamines. Where the hydroxyalkyl groups are the same or different and are also as defined above. Hydroxyalkyl is especially 2-hydroxyethyl, 3-hydroxypropyl or 4-hydroxybutyl.
For example, the following “hydroxyalkyl substituted polyamines” and especially the “hydroxyalkyl substituted diamines” can be mentioned: (N-hydroxyalkyl) alkylenediamines, N, N-dihydroxyalkylalkylenediamines, where the hydroxyalkyl groups are the same or different and are also different as defined above. Hydroxyalkyl is especially 2-hydroxyethyl, 3-hydroxypropyl or 4-hydroxybutyl; alkylene is especially ethylene, propylene or butylene.
Suitable "diamines" are alkylenediamines, and their analogues substituted with N-alkyl, such as N-monoalkylated alkylene diamines and N, N- or N, N'-dialkylated alkylenediamines. Alkylene is especially straight or branched C1.7 or CM alkylene as defined above. Alkyl is especially CM alkyl as defined above. Examples are, in particular, ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, 1,4-butylenediamine and its isomers, pentanediamine and its isomers, hexanediamine and its isomers, heptanediamine and its isomers, and also mono- or di-alkylates, such as for example, mono- or di-alkylated C1-C4, such as methylated, for example, derivatives of the aforementioned diamine compounds, such as, for example, 3-dimethylamino-1-propylamine (DMAPA) , N, N-diethylaminopropylamine, and N, N-dimethyl-aminoethylamine.
Suitable straight chain "polyamines" are, for example, dialkylenetriamine, trialkylenetetramine, tetraalkylenepentamine, pentaalkyleneexamine, and their substituted N-alkyl analogues, such as N-monoalkylated alkylenopolyamines and N, N- or N, N-dialkylated. Alkylene is especially straight or branched C1.7 or CM alkylene as defined above. Alkyl is especially CM alkyl as defined above.
Examples are especially diethylenetriamine, triethylene-tetramine, tetraethylene-pentamine, pentaethyleneexamine, dipropylene-triamine, tripropylene-tetramine, tetrapropylene-pentamine, penta-propyleneexamine, dibutylenetriamine, tributylenetetramine, tetra-butylene-pentaminamine; and its N, N-dialkyl derivatives, especially its N, N-dialkyl derivatives CM-OS Examples include: N, N-N, N-diethyl-dimethyl-enotriamine, N, N-N, N-dimethyl -diethylene-1,2-triamine, N, N- N, N-dipropylethylene-1,2-triamine, N, N-dimethyldipropylene-1,3-triamine (i.e. DMAPAPA), N, N-diethyldipropylene-1, 3-triamine, N, N-dipropyl-dipropylene-1,3-triamine, N, N-dimethyldibutylene-1,4-triamine, N, N-diethyldibutylene-1,4-triamine, N, N-dipropyldibutylene-1, 4- triamine, N, N-dimethyldipentylene-1,5-triamine, N, N-diethyldipentylene-1,5-triamine, N, N-dipropyldipentylene-1,5-triamine, N, N-dimethyldiexylene-1,6- triamine, N, N-diethyliexylene-1,6,6-triamine and N, N-dipropyldylene-1,6-triamine.
The "aromatic carbocyclic diamines" having two primary amino groups are those substituted by benzene diamino, biphenyl, naphthalene, tetrahydronaphthalene, fluorene, indene and phenanthrene.
The "aromatic or non-aromatic heterocyclic polyamines" having two primary amino groups are the derivatives, substituted by two amino groups, of the following heterocycles: 5- or 6-membered, saturated or monounsaturated heterocycles comprising one to two nitrogen atoms and / or an oxygen or sulfur atom or one or two oxygen and / or sulfur atoms as ring members, for example tetrahydrofuran, pyrrolidine, isoxazolidine, isothiazolidine, pyrazolidine, oxazolidine, thiazolidine, imidazolidine, pyrroline, piperidine, piperidinyl, 1,3 -dioxane, tetrahydropyran, hexahydropyridazine, hexahydropyrimidine, piperazine; - 5-membered aromatic heterocycles comprising, in addition to the carbon atoms, two or three nitrogen atoms or one or two nitrogen atoms and a sulfur or oxygen atom as members of the ring, for example furan, tiano, pyrrole, pyrazole, oxazole, thiazole, imidazole and 1,3,4-triazole; isoxazole, isothiazole, thiadiazole, oxadiazole; - 6-membered heterocycles comprising, in addition to the carbon atoms, one or two, or one, two or three, nitrogen atoms as ring members, for example pyridinyl, pyridazine, pyrimidine, pyrazinyl, 1,2,4-triazine , 1, 3,5-triazin-2-yl.
The "heterocycles having a primary and tertiary amino group are, for example, the N-heterocycles mentioned above which are aminoalkylated on at least one nitrogen atom of the ring, and especially carry a C1.4 alkyl-alkyl group.
The "aromatic or non-aromatic heterocycles having a tertiary amino group and a hydroxyalkyl group" are, for example, the N-heterocycles mentioned above which are hydroxyalkylated on at least one nitrogen atom of the ring, and especially carry a hydroxyalkyl group Ci.4.
Mention should be made especially of the groups that follow from individual classes of eligible nitrogen compounds: Group 1:

Group 2:

Group 3:

A6) Preparation of inventive additives:
a) Addition of amine and addition of alcohol
The hydrocarbyl substituted polycarboxylic anhydride compound is reacted with the quaternizable nitrogen compound under 5 thermally controlled conditions, such that it is essentially present in the condensation reaction. More particularly, according to the invention, no reaction water formation is observed. More particularly, the reaction is carried out at a temperature in the range of 10 to 80 ° C, especially from 20 to 60 ° C or from 30 to 50 ° C. The reaction time can be in the range of a few 10 minutes or a few hours, for example from about 1 minute to about 10 hours. The reaction can be carried out at a pressure of about 0.1 to 2 atm, but especially at approximately standard pressure; In particular, an atmosphere of inert gas, for example nitrogen, is appropriate.
The reagents are initially loaded especially in about equimolar amounts; optionally, a small molar excess of the anhydride, for example a 0.05 to 0.5 fold excess, for example a 0.1 to 0.3 fold excess, is desirable. If required, the reagents can be initially loaded in a suitable organic aliphatic or aromatic inert solvent or a mixture of these. Typical examples are, for example, solvents from the Solvesso series, toluene or xylene. However, in another particular embodiment, the reaction is carried out in the absence of organic solvents, especially protic solvents.
In the case of inventive performance of the reaction, the anhydride ring is opened with the addition of the quaternizable nitrogen compound via its oxygen or reactive nitrogen group (for example hydroxyl group or primary or secondary amine group), and without the elimination of water condensation. The reaction product obtained comprises a polycarboxylic intermediate with at least one newly formed acid amide group or ester group and at least one intramolecular bond, newly formed carboxylic acid or carboxylate group, in a stoichiometric ratio to the intramolecularly bonded amino group. by the addition reaction.
The reaction product thus formed theoretically can be further purified, or the solvent can be removed. Usually, however, this is not absolutely necessary, such that the reaction step can be carried forward without further purification in the synthesis step following the quaternization. b) Quaternization
The epoxide-based quaternization in reaction step (b) is then carried out without the addition of acid in a complete departure from the prior art methods described so far. The carboxyl radical formed by the addition of amine promotes the opening of the epoxide ring and consequently the quaternization of the amino group. The reaction product obtained therefore does not have a free acid anion. However, the product is not loaded due to its betaine structure.
To perform the quaternization, the reaction product of the reaction mixture from stage a) is mixed with at least one epoxide compound of the formula (II) above, especially in the stoichiometric amounts required to obtain the desired quaternization. It is possible to use, for example, from 0.1 to 1.5 equivalent, or from 0.5 to 1.26 equivalent, of quaternizing agent per equivalent of quaternizable tertiary nitrogen atom. More particularly, however, approximately equimolar proportions of the epoxide are used to quaternize a tertiary amine group. Correspondingly higher amounts of use are required to categorize a secondary or primary amine group.
Typical working temperatures here are in the range 15 to 90 ° C, especially 20 to 80 ° C or 30 to 70 ° C. The reaction time can be in the range of a few minutes or a few hours, for example from about 10 minutes to about 24 hours. The reaction can be carried out at a pressure of about 0.1 to 20 bar, for example 1 to 10 or 1.5 to 3 bar, but especially around the standard pressure. More particularly, an atmosphere of inert gas, for example nitrogen, is appropriate.
If required, the reagents can be initially charged for epoxidation in a suitable inert aromatic or aliphatic organic solvent or a mixture thereof, or a sufficient proportion of solvent from reaction step a) is still present. Typical examples are, for example, solvents from the Solvesso series, toluene or xylene. In another particular embodiment, the reaction, however, is carried out in the absence of organic solvents, especially protic (organic) solvents.
The "protic solvents", which are not especially used according to the invention, are especially those with a dielectric constant of more than 9. Such protic solvents usually comprise at least one HO group and can additionally contain water. Typical examples are, for example, glycols and glycolic ethers and alcohols such as aliphatic, cyclic-aliphatic, aromatic or heterocyclic alcohols. c) Work of the reaction mixture The final reaction product thus formed theoretically can be further purified, or the solvent can be removed. Usually, however, this is not absolutely necessary, and so the reaction product can be used without further purification as an additive, optionally after mixing with other additive components (see below), especially since naturally there are also no free protic auxiliaries. corrosive substances present in the reaction product. d) General example
As a non-limiting example of the reaction of a polyalkylene substituted dicarboxylic anhydride compound by the addition of amine or addition of alcohol and subsequent quaternization, reference is made to the illustrative reaction schemes that follow where Rj to R7, Li and L2 are each as defined above: Stage 1 Preparation of substituted dicarboxylic anhydride
Stage 2a: Amination and quaternization
Stage 2b: Ester training and quaternization
B) Other additive components
Fuels additive with the inventive quaternized additive is a gasoline fuel or especially an intermediate distillate fuel, in particular a diesel fuel.
The fuel can also comprise customary additives to improve efficiency and / or suppress wear.
In the case of diesel fuels, there are primarily usual detergent additives, carrier oils, cold flow improvers, lubricity improvers, corrosion inhibitors, demulsifiers, turbidity inhibitors, defoamers, cetane number improvers, combustion enhancers, antioxidants or stabilizers. , antistatic, metallocene, metal deactivators, dyes and / or solvents.
In the case of gasoline fuels, these are in particular lubricity enhancers (friction modifiers), corrosion inhibitors, demulsifiers, turbidity inhibitors, defoamers, combustion enhancers, antioxidants or stabilizers, antistatic, metallocene, metal deactivators, dyes and / or solvents.
Typical examples of suitable coadditives are listed in the following section: 81) Detergent additives
The usual detergent additives are preferably amphiphilic substances that have at least one hydrophobic hydrocarbon radical with a numerical average molecular weight (Mn) of 85 to 20,000 and at least one polar portion selected from (Da) groups of mono- or polyamine having up to 6 nitrogen atoms, at least one nitrogen atom having basic properties; (Db) nitro groups, optionally in combination with hydroxyl groups; (Dc) hydroxyl groups in combination with mono- or polyamino groups, at least one nitrogen atom having basic properties; (Dd) carboxyl groups or their alkali metal or alkaline earth metal salts; (De) groups of sulfonic acid or its alkali metal or alkaline earth metal salts; (Df) C2 to C4 polyoxyalkylene moieties terminated by hydroxyl groups, mono- or polyamine groups, at least one nitrogen atom having basic properties, or by carbamate groups; (Dg) carboxylic ester groups; (Dh) portions derived from succinic anhydride and having hydroxyl and / or amino and / or starch and / or imido groups; and / or (Di) portions obtained by the Mannich reaction of phenols substituted with aldehydes and mono- or polyamines.
The hydrophobic hydrocarbon radical in the above detergent additives, which ensures adequate solubility in the fuel, has a numerical average molecular weight (Mn) of 85 to 20,000, preferably from 113 to 10,000, more preferably from 300 to 5000, even more preferably from 300 to 3000, especially more preferably from 500 to 2500 and especially from 700 to 2500, in particular from 800 to 1500. As typical hydrophobic hydrocarbon radicals, especially in conjunction with the polar portions, especially polypropenyl, polybutenyl and polyisobutenyl with a numerical average molecular weight Mn, in each case preferably from 300 to 5000, more preferably from 300 to 3000, even more preferably from 500 to 2500, especially even more preferably from 700 to 2500 and especially from 800 to 1500 are taken into account.
Examples of the above groups of detergent additives include the following:
Additives comprising the mono- or polyamino (Da) groups are preferably mono- or polyalkylene polyamines based on polypropene or polybutene or polyisobutene with high reactivity (i.e. having predominantly double bonds at the end) or conventional (i.e. having predominantly internal double bonds) ) having Mn from 300 to 5000, more preferably from 500 to 2500 and especially from 700 to 2500. Such additives based on high reactivity polyisobutene, which can be prepared from polyisobutene which can comprise up to 20% by weight of units of n-butene by hydroformylation and reductive amination with ammonia, monoamines or polyamines such as dimethylaminopropylamine, ethylene diamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine, are especially known from EP-A 244 616. When polybutene or polyisobutene has double internal bonds positions β and y) are used as starting materials in the prep aration of the additives, a possible preparation route is by subsequent chlorination and amination or by oxidation of the double bond with air or ozone to give the carbonyl or carboxyl compound and the subsequent amination under reducing conditions (hydrogenation). The amines used here for the amination can be, for example, ammonia, monoamines or the polyamines mentioned above. The corresponding polypropene-based additives are described in particular in WO-A 94/24231.
Other particular additives that comprise the monoamino (Da) groups are the hydrogenation products of the polyisobutene reaction products having an average degree of polymerization P = 5 to 100 with nitrogen oxides or mixtures of nitrogen and oxygen oxides, as described in particularly in WO-A 97103946.
Other particular additives comprising monoamino (Da) groups are compounds obtainable from polyisobutene epoxides by reaction with amines and the dehydration and subsequent reduction of amino alcohols, as described in particular in DE-A 196 20 262.
Additives comprising nitro groups (Db), optionally in combination with hydroxyl groups, are preferably reaction products of polyisobutenes having an average degree of polymerization P = 5a 100 or 10a 100 with nitrogen oxides or mixtures of nitrogen and oxygen oxides, such as described in particular in WO-A 96/03367 and WO-A 96/03479. These reaction products are generally mixtures of pure nitropolyisobutenes (for example, α, β-dinitropolyisobutene) and mixed hydroxynitropolyisobutenes (for example, a-nitro-β-hydroxypolyisobutene).
Additives comprising hydroxyl groups in combination with mono- or polyamino (Dc) groups are in particular reaction products of polyisobutene epoxides obtainable from polyisobutene preferably having predominantly terminal double bonds and Mn - 300 to 5000, with ammonia or mono- or polyamines, as described in particular in EP-A 476 485.
Additives comprising carboxyl groups or their alkali metal or alkaline earth metal (Dd) salts are preferably C2 to C40 olefin copolymers with maleic anhydride that have a total molar mass of 500 to 20,000 and some or all of this carboxyl group has been converted to the alkali metal or alkaline earth metal salts and any remaining carboxyl groups were reacted with alcohols or amines. Such additives are disclosed in particular by EP-A 307 815. Such additives mainly serve to prevent wear of the valve seat and as described in WO-A 87/01126, they can advantageously be used in combination with common fuel detergents such as poly (iso) butenoamines or polyetheramines.
Additives comprising groups of sulfonic acid or its alkali metal or alkaline earth metal (De) salts are preferably alkali metal or alkaline earth metal salts of an alkyl sulfosuccinate, as described in particular in EP-A 639 632. Such additives they mainly serve to prevent wear of the valve seat and can be used advantageously in combination with common fuel detergents such as poly (iso) butene-amines or polyetheramines.
Additives comprising portions of C2-C4 polyoxyalkylene (Df) are preferably polyethers or polyetheramines which are obtainable by the reaction of C2 to Ceo alkanols, C6 to C30 alkanediols, C2 to C30 mono- or di-alkyl amines, C1 to C1 alkylcyclohexanes C30 or Ci to C30 alkylphenols with 1 to 30 moles of ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl group or amino group and, in the case of polyetheramines, by the subsequent reductive amination with ammonia, monoamines or polyamines . Such products are described in particular in EP-A 310 875, EP-A 356 725, EP-A 700 985 and US-A 4,877,416. In the case of polyethers, such products also have carrier oil properties. Typical examples of these are tridecanol butoxylates, isotridecanol butoxylates, isononylphenol butoxylates and polyisobutenol butoxylates and propoxylates and also the corresponding reaction products with ammonia.
Additives comprising carboxylic ester (Dg) groups are preferably esters of mono-, di- or tri-carboxylic acids with long-chain alkanols or polyols, in particular those having a minimum viscosity of 2 mm / s at 100 ° C, as described in particular in DE-A 38 38 918. The mono-, di- or tri-carboxylic acids used can be aliphatic or aromatic acids, and particularly suitable ester alcohols or polyol esters are representative of long chain having, for example , from 6 to 24 carbon atoms. Typical representatives of the esters are adipates, phthalates, isophthalates, terephthalates and trimellites of isooctanol, isononanol, isodecanol and isotridecanol. Such products also have carrier oil properties.
Additives comprising portions derived from succinic anhydride and having hydroxyl and / or amino and / or starch and / or especially imido (Dh) groups are preferably the corresponding derivatives of succinic anhydride substituted with alkyl or alkenyl and especially the corresponding derivatives of polyisobutenylsuccinic anhydride which are obtainable by the reaction of conventional or high reactivity polyisobutene having Mn preferably from 300 to 5000, more preferably from 300 to 3000, even more preferably from 500 to 2500, even more especially preferably from 700 to 2500 and especially from 800 to 1500, with malic anhydride via a thermal route in an ene reaction or via the chlorinated polyisobutene. The portions having hydroxyl and / or amino and / or starch and / or imido groups are, for example, carboxylic acid groups, monoamine acid amides, di- or polyamine acid amides which, in addition to the amide function, also have free amine groups, derivatives of succinic acid having an acid function and an amide, carboximides with monoamines, carboximides with di- or polyamines which, in addition to the imide function, also have free amine groups, or diimides that are formed by the reaction of di- or polyamines with two succinic acid derivatives. In the presence of portions of imido D (h), the additional detergent additive in the context of the present invention is, however, used only up to a maximum of 100% by weight of the compounds with betaine structure. Such fuel additives are common knowledge and are described, for example, in documents (1) and (2). They are preferably the reaction products of succinic acids substituted with alkyl or alkenyl or their derivatives with amines and more preferably the reaction products of succinic acids substituted with polyisobutenyl or their derivatives with amines. Of particular interest in this context are reaction products with aliphatic polyamines (polyalkyleneimines) such as especially ethylenediamine, diethylene triamine, triethylene tetramine, tetraethylene pentaamine, pentaethyleneexamine and hexaethylene eptamine, which have an imide structure.
Additives comprising portions (Di) obtained by the Mannich reaction of phenols substituted with aldehydes and mono- or polyamines are preferably reaction products of phenols substituted with polyisobutene with formaldehyde and mono- or polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylene- pentamine or dimethylaminopropylamine. Polyisobutenyl-substituted phenols can originate from conventional or highly reactive polyisobutene having Mn = 300 to 5000. Such "Mannich-based polyisobutene" are described in particular in EP-A 831 141.
One or more of the detergent additives mentioned can be added to the fuel in such an amount that the dosage of these detergent additives is preferably from 25 to 2500 ppm by weight, especially from 75 to 1500 ppm by weight, in particular from 150 to 1000 ppm in weight. B2) Carrier oils
Carrier oils additionally used can be mineral or synthetic in nature. Suitable mineral carrier oils are the fractions obtained in the processing of crude oil, such as shiny stocks or base oils having viscosities, for example, of the SN class from 500 to 2000; but also aromatic hydrocarbons, paraffinic hydrocarbons and alkoxyalkanes. Also useful is a fraction that is obtained in the refining of mineral oil and is known as "hydrocracking oil" (vacuum distillate cut having a boiling range of about 360 to 500 ° C, obtainable from natural mineral oil that was catalytically hydrogenated and isomerized under high pressure and also dewaxed). Also suitable are mixtures of the mineral carrier oils mentioned above.
Examples of suitable synthetic carrier oils are polyolefins (polyalphaolefins or internal polyolefins), (poly) esters, (poly) alkoxylates, polyethers, aliphatic polyetheramines; alkylphenol-initiated polyethers, alkylphenol-initiated polyetheramines and long chain alkanols carboxylic esters.
Examples of suitable polyolefins are olefin polymers having Mn = 400 to 1800, in particular based on polybutene or polyisobutene (hydrogenated or non-hydrogenated).
Examples of suitable polyethers or polyetheramines are preferably compounds comprising portions of C2a C4 polyoxyalkylene which are obtainable by the reaction of C2 to C60 alkanols, Cóa C30 alkanediols, C2a C30 mono- or dialkyl amines, C1 to C30 alkylcyclohexanes or C 1 to C 30 alkylphenols with 1 to 30 moles of ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl group or amino group, and, in the case of polyetheramines, by the subsequent reductive amination with ammonia, monoamines or polyamines . Such products are described in particular in EP-A 310 875, EP-A 356 725, EP-A 700 985 and US-A 4,877,416. For example, the polyetheramines used can be alkylene polyoxide amines or their functional derivatives. Typical examples are tridecanol butoxylates or isotridecanol butoxylates, isononylphenol butoxylates and also polyisobutenol butoxylates and propoxylates, as well as the corresponding reaction products with ammonia.
Examples of carboxylic esters of long chain alkanols are in particular esters of mono-, di- or tri-carboxylic acids with long chain alkanols or polyols, as described in particular in DE-A 38 38 918. Mono-, di- or tri-carboxylic acids used can be aliphatic or aromatic acids; suitable alcohol esters or polyols are in particular representative of long chain having, for example from 6 to 24 carbon atoms. Typical representatives of the esters are adipates, phthalates, isophthalates, terephthalates and trimellites of isooctanol, isononanol, isodecanol and isotridecanol, for example di (n- or isotridecyl) phthalate.
Other suitable carrier oil systems are described, for example, in DE-A 38 26 608, DE-A 41 42 241, DE-A 43 09 074, EP-A 452 328 and EP-A 548 617.
Examples of particularly suitable synthetic carrier oils are alcohol-initiated polyethers having from about 5 to 35, preferably from about 5 to 30, more preferably from 10 to 30, and especially from 15 to 30 units of C3 to C6 alkylene oxide , for example selected from units of propylene oxide, n-butylene oxide and isobutylene oxide, or mixtures thereof, per alcohol molecule. Non-limiting examples of suitable starting alcohols are alkanols or long chain phenols substituted by long chain alkyl wherein the long chain alkyl radical is in particular a straight or branched C 6 to C 6 alkyl radical. Particular examples include tridecanol and nonylphenol. Particularly preferred alcohol-initiated polyethers are the reaction products (polyetherification products) of C (, to C1 aliphatic monohydric alcohols with C3 to C $ alkylene oxides. Examples of aliphatic C6-CIS monohydric alcohols are hexanol, heptanol, octanol , 2-ethylexanol, nonyl alcohol, decanol, 3-propylptanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, octadecanol and their constitutional and positional isomers.The alcohols can be used in the form of pure isomers or in the form of mixtures A particularly preferred alcohol is tridecanol. Examples of C3 to C6 alkylene oxides are propylene oxide, such as 1,2-propylene oxide, butylene oxide, such as 1,2-butylene oxide, 2,3-butylene, isobutyiene oxide or tetrahydrofuran, pentylene oxide and hexylene oxide Particular preference among these is given to Cato C4-alkylene oxide, ie propylene oxide such as 1,2-propylene oxide and butylene oxide such as 1,2-butylene oxide, 2,3-butylene oxide and isobutylene oxide. Especially butylene oxide is used.
Other suitable synthetic carrier oils are alkoxylated alkylphenols, as described in DE-A 10 102 913.
The particular carrier oils are synthetic carrier oils, with particular preference being given to the alcohol-initiated polyethers described above.
The carrier oil or the mixture of different carrier oils is added to the fuel in an amount preferably from 1 to 1000 ppm by weight, more preferably from 10 to 500 ppm by weight and especially from 20 to 100 ppm by weight. B3) Cold flow improvers
Suitable cold flow improvers are in principle all organic compounds that are capable of improving the flow performance of medium distillate fuels or diesel fuels under cold conditions. For the intended purpose, they must have sufficient oil solubility. In particular, cold flow improvers useful for this purpose are cold flow improvers (intermediate distillate flow improvers, MDFIs) typically used in the case of intermediate distillates of fossil origin, i.e. in the case of usual mineral diesel fuels. However, it is also possible to use organic compounds that partially or predominantly have the properties of an anti-sedimentation wax additive (WASA) when used in regular diesel fuels. They can also act partially or predominantly as nucleators. However, it is also possible to use mixtures of organic compounds effective as MDFIs and / or effective as WAS As and / or effective as nucleators.
The cold flow improver is typically selected from (Kl) copolymers of a C2 to C40 olefin with at least one other ethylenically unsaturated monomer; (K2) comb polymers; (K3) polyoxyalkylenes; (K4) polar nitrogen compounds; (K5) sulfocarboxylic acids or sulfonic acids or their derivatives; and (K6) poly (meth) acrylic esters.
It is possible to use mixtures of different representatives of one of the particular classes from (Kl) to (K6) or mixtures of representatives of the different classes (Kl) to (K6).
The C2 to C40 olefin monomers suitable for class (Kl) copolymers are, for example, those having from 2 to 20 and especially from 2 to 10 carbon atoms, and from 1 to 3 and preferably from 1 or 2 double bonds of carbon-carbon, especially having a carbon-carbon double bond.
In the latter case, the carbon-carbon double bond can be terminally arranged (α-olefins) or internally. However, preference is given to α-olefins, more preferably α-olefins having from 2 to 6 carbon atoms, for example propene, 1-butene, 1-pentene, 1-hexene and in particular ethylene.
In class (Kl) copolymers, the at least one other ethylenically unsaturated monomer is preferably selected from alkenyl carboxylates, (meth) acrylic esters and other olefins.
When other olefins are also copolymerized, they are preferably higher in molecular weight than the olefin-based monomer C2 to C40 mentioned above. When, for example, the olefin-based monomer used is ethylene or propene, other suitable olefins are in particular C10 to C40 α-olefins. Other olefins are in most cases only additionally copolymerized when monomers with carboxylic ester functions are also used.
Suitable (meth) acrylic esters are, for example, esters of (meth) acrylic acid with C 1 to C 2 alkanols, especially C 1 to C 10 alkanols, in particular with methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol, isobutanol, tert-butanol, pentanol, hexanol, heptanol, octanol, 2-ethylexanol, nonanol and decanol, and their structural isomers.
Suitable alkenyl carboxylates are, for example, C2a C14 alkenyl esters, for example the vinyl and propenyl esters of carboxylic acids having from 2 to 21 carbon atoms, the hydrocarbon radical of which may be linear or branched. Among these, preference is given to vinyl esters. Among the carboxylic acids with a branched hydrocarbon radical, preference is given to those whose branch is in the α position in relation to the carboxyl group, the α carbon atom most preferably being tertiary, i.e. the carboxylic acid being a so-called neocarboxylic acid. However, the hydrocarbon radical of the carboxylic acid is preferably linear.
Examples of suitable alkenyl carboxylates are vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylexanoate, vinyl neopentanoate, vinyl hexanoate, vinyl neononanoate, vinyl neodecanoate and the corresponding propylene esters. given to vinyl esters. A particularly preferred alkenyl carboxylate is vinyl acetate; the typical copolymers of the group (Kl) resulting from these are ethylene-vinyl acetate copolymers (“EVAs”), which are some of the most frequently used ethylene-vinyl acetate copolymers in a particularly advantageous way and their preparation is described in WO 99/29748.
Suitable copolymers of the (Kl) class are also those that comprise two or more different alkenyl carboxylates in copolymerized form, which differ in alkenyl function and / or in the carboxylic acid group. Also suitable are copolymers which, like alkenyl carboxylate (s), comprise at least one olefin and / or at least one (meth) acrylic ester in copolymerized form.
Terpolymers of a C2 to C4o a-olefin, a Q to C2o alkyl ester of an ethylenically unsaturated monocarboxylic acid having 3 to 15 carbon atoms and a C2 to Cu alkenyl ester of a saturated monocarboxylic acid having 2 to 21 atoms of carbon are also suitable as copolymers of the (Kl) class. Terpolymers of this type are described in WO 2005/054314. A typical terpolymer of this type is formed from ethylene, 2-ethylhexyl acrylate and vinyl acetate.
The at least one or the other ethylenically unsaturated monomer (s) are copolymerized in the class (KI) copolymers in an amount preferably from 1 to 50% by weight, especially from 10 to 45% by weight. weight and in particular from 20 to 40% by weight, based on the overall copolymer. The main proportion in terms of the weight of the monomer units in the class (Kl) copolymers therefore originates in general from the C2 to C40 base olefins.
Copolymers of the class (Kl) preferably have a numerical average molecular weight Mn of 1000 to 20,000, more preferably of 1000 to 10,000 and in particular from 1000 to 8000.
The comb polymers typical of component (Q) are, for example, obtainable by copolymerizing malic anhydride or fumaric acid with another ethylenically unsaturated monomer, for example with an a-olefin or an unsaturated ester, such as vinyl acetate, and subsequent esterification of the anhydride or acid function with an alcohol having at least 10 carbon atoms. Other suitable comb polymers are copolymers of esterified α-olefins and comonomers, for example esterified copolymers of styrene and malic anhydride or esterified copolymers of styrene and fumaric acid. Suitable comb polymers can also be polyfumarates or polyimaleates. Homo- and copolymers of vinyl ethers are also suitable comb polymers. Comb polymers suitable as components of class (K2) are, for example, also those described in WO 2004/035715 and in "Comb-Like Polymers, Structure and Properties", N. A. Plate and V. P. Shibaev, J. Poly. Sci. Macromolecular Revs. 8, pages 117 to 253 (1974) ”. Mixtures of comb polymers are also suitable.
Polyoxyalkylenes suitable as components of class (K3) are, for example, polyoxyalkylene esters, polyoxyalkylene ethers, polyoxyalkylene ester / ethers and mixtures thereof. These polyoxyalkylene compounds preferably comprise at least one linear alkyl group, preferably at least two linear alkyl groups, each having 10 to 30 carbon atoms and a polyoxyalkylene group having a numerical average molecular weight of up to 5000. Such polyoxyalkylene compounds are described, for example, in EP-A 061 895 and also in US 4,491,455. Particular polyoxyalkylene compounds are based on polyethylene glycols and polypropylene glycols having a numerical average molecular weight of 100 to 5000. Additionally suitable are polyoxyalkylene fatty acid mono- and diesters having 10 to 30 carbon atoms, such as stearic acid or behenic acid.
Polar nitrogen compounds suitable as components of class (K4) can be ionic or non-ionic and preferably have at least one substituent, in particular at least two substituents, in the form of a tertiary nitrogen atom of the general formula> NR where, R is a hydrocarbon radical Cg to C40. Nitrogen substituents can also be categorized, that is, be in cationic form. An example of such nitrogen compounds is that of the ammonium salts and / or amides that are obtainable by reacting at least one amine substituted by at least one hydrocarbon radical with a carboxylic acid having 1 to 4 carboxyl groups or with a derivative of this suitable. The amines preferably comprise at least one Cg to C40 alkyl radical. The primary amines suitable for preparing the mentioned polar nitrogen compounds are, for example, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tetradecylamine and the upper linear homologs. Secondary amines suitable for this purpose are, for example, dioctadecylamine and methylbeenylamine. Also suitable for this purpose are amine mixtures, in particular amine mixtures obtainable on an industrial scale, such as fatty amines or hydrogenated amines, as described, for example, in the Ullmanris Encyclopedia of Industrial Chemistry, 6th Edition, chapter “Aliphatic Amines, ”. Suitable acids for the reaction are, for example, cyclohexane-1,2-dicarboxylic acid, cyclohexene-1,2-dicarboxylic acid, cyclopentane-1,2-dicarboxylic acid, naphthalene-dicarboxylic acid, italic acid, isophthalic acid, terephthalic acid and succinic acids replaced by long chain hydrocarbon radicals.
In particular, the class (K4) component is a reaction product soluble in poly oil (C2 to C20 carboxylic acids) having at least one tertiary amino group with primary or secondary amines. The poly (carboxylic acids C2 to C20) which have at least one tertiary amino group and form the basis of this reaction product preferably comprise at least 3 carboxyl groups, especially from 3 to 12 and in particular from 3 to 5 carboxyl groups. The carboxylic acid units in the polycarboxylic acids preferably have 2 to 10 carbon atoms, and are especially acetic acid units. Carboxylic acid units are suitably linked to polycarboxylic acids, usually via one or more carbon and / or nitrogen atoms. These are preferably linked to tertiary nitrogen atoms which, in the case of a plurality of nitrogen atoms, are linked via hydrocarbon chains.
The class (K4) component is preferably a water-soluble reaction product based on poly (C2 to C20 carboxylic acids) which have at least one tertiary amino group and are of the general formulas lia or Ilb
wherein variable A is a straight or branched C2 to C6 alkylene group or the portion of formula III.
and variable B is a C1 to C19 alkylene group. The compounds of the general formulas Ila and lib especially have the properties of a WASA.
In addition, the preferred oil-soluble reaction product of the component (K4), especially that of the general formulas IIa or IIb, is an amide, an amide-ammonium salt or an ammonium salt in which none, one or more groups of carboxylic acid were converted to the amide groups.
The straight or branched C2 to Cg alkylene groups of variable A are, for example, 1,1-ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,3-butylene, 1 , 4-butylene, 2-methyl-1,3-propylene, 1,5-pentylene, 2-methyl-1,4-butylene, 2,2-dimethyl-1,3-propylene, 1,6-hexylene (hexamethylene ) and in particular 1,2-ethylene. The variable A preferably comprises from 2 to 4 and especially 2 or 3 carbon atoms.
The C to C19 alkylene groups of variable B are, for example, 1,2-ethylene, 1,3-propylene, 1,4-butylene, hexamethylene, octamethylene, decamethylene, dodecamethylene, tetradecamethylene, hexadecamethylene, octadecamethylene, nonadecamethylene and especially methylene . The variable B preferably comprises from 1 to 10 and especially from 1 to 4 carbon atoms.
Primary and secondary amines as a reaction partner for polycarboxylic acids to form the (K4) component are typically monoamines, especially aliphatic monoamines. These primary and secondary amines can be selected from a multitude of amines that carry hydrocarbon radicals that can optionally be linked together.
These precursor amines of the oil-soluble reaction products of the components (K4) are usually secondary amines and have the general formula HN (R) 2 in which the two variables R are each independently straight or branched C 1 to C 30 alkyl radicals , especially Cu to C24 alkyl radicals. These relatively long chain alkyl radicals are preferably straight or only slightly branched. In general, the secondary amines mentioned, with respect to their relatively long chain alkyl radicals, are derived from naturally occurring fatty acids and their derivatives. The two radicals R are preferably identical.
The secondary amines mentioned can be linked to polycarboxylic acids by means of amide structures or in the form of ammonium salts, it is also possible for only one portion to be present as amide structures and another portion as ammonium salts. Preferably only a few, if any, free acid groups are present. The oil-soluble reaction products of the component (K4) are preferably present completely in the form of the amide structures.
Typical examples of such components (K4) are reaction products of nitrilotriacetic acid of ethylenediaminetetraacetic acid or propylene-1,2-diaminetetraacetic acid with in each case from 0.5 to 1.5 mol per carboxyl group, especially from 0, 8 to 1.2 mol per dioleylamine carboxyl group, dipalmitinamine; grease amine dicoco, distearylamine, dibeenylamine or especially di-sebum grease amine. A particularly preferred component (K4) is the reaction product of 1 mol of ethylenediaminetetraacetic acid and 4 moles of hydrogenated di-sebum amine grease.
Other typical examples of component (K4) include the 2-N 'N, N-dialkylammonium salts, N'-dialkylamidobenzoates, for example the reaction product of 1 mol of phthalic anhydride and 2 mol of di-tallow amine, the latter being hydrogenated or non-hydrogenated, and the reaction product of 1 mol of an alkenylspirobislactone with 2 moles of a dialkylamine, for example di sebum amine grease and / or tallow amine grease, the last two being hydrogenated or not hydrogenated.
Other types of structures typical for the class (K4) component are cyclic compounds with tertiary or condensed amino groups of primary or secondary long-chain amines with polyethers containing carboxylic acid, as described in WO 9308115.
Sulfocarboxylic acids, sulfonic acids or their derivatives that are suitable as cold flow improvers of the (K5) class are, for example, the oil-soluble carboxamides and ortho-sulfobenzoic acid carboxylic esters in which the function of sulfonic acid is present as a sulfonate with ammonium cations substituted with alkyl, as described in EP-A 261,957.
Poly (meth) acrylic esters suitable as cold flow improvers of class (K6) are homo- or copolymers of acrylic and methacrylic esters. Preference is given to copolymers of at least two different (meth) acrylic esters that differ with respect to esterified alcohol.
The copolymer optionally comprises a different olefinically unsaturated monomer in copolymerized form. The weighted average molecular weight of the polymer is preferably 50,000 to 500,000. A particularly preferred polymer is a copolymer of methacrylic acid and methacrylic esters of saturated C1-4 and C1-5 alcohols, the acid groups were neutralized with hydrogenated amine. Suitable poly (meth) acrylic esters are described, for example, in WO 00/44857.
The cold flow improver or the mixture of different cold flow improver is added to the intermediate distillate fuel or diesel fuel in a total amount preferably of 10 to 5000 ppm by weight, more preferably of 20 to 2000 ppm by weight, even more preferably of 50 to 1000 ppm by weight and especially from 100 to 700 ppm by weight, for example 200 to 500 ppm by weight. B4) Lubricity Enhancers
Suitable lubricity improvers or friction modifiers are typically based on fatty acids or fatty acid esters. Typical examples are tall oil fatty acid, as described, for example, in WO 98/004656, and glyceryl monooleate. The reaction products, described in US 6 743 266 B2, of natural or synthetic oils, for example triglycerides, and alkanolamines are also suitable as such lubricity enhancers. B5) Corrosion inhibitors
Suitable corrosion inhibitors are, for example, succinic esters, in particular with polyols, fatty acid derivatives, for example oleic esters, oligomerized fatty acids, substituted ethanolamines, and products sold under the trade name RC 4801 (Rhein Chemie Mannheim, Germany) or HiTEC 536 (Etyl Corporation). B6) Demulsifiers
Suitable demulsifiers are, for example, alkali metal or alkaline earth metal salts of phenol- and naphthalene sulfonates substituted with alkyl and alkali metal or alkaline earth metal salts of fatty acids, and also neutral compounds such as alcohol alkoxylates, eg alcohol ethoxylates, phenol alkoxylates, eg tert-butylphenol ethoxylate or tert-pentylphenol ethoxylate, fatty acids, alkylphenols, ethylene oxide (EO) and propylene oxide (PO) condensation products, for example example including EO / PO block copolymers, polyethyleneimines or polysiloxanes. B7) Turbidity inhibitors
Suitable turbidity inhibitors are, for example, alkoxylated phenol-formaldehyde condensates, for example products available under the trade names NALCO 7D07 (Nalco) and TOLAD 2683 (Petrolite). B8) Defoamers
Suitable defoamers are, for example, polyether modified polysiloxanes, for example products available under the trade names TEGOPREN 5851 (Goldschmidt), Q 25907 (Dow Corning) and RHODOSIL (Rhone Poulenc). B9) Cetane number enhancers
Suitable cetane number improvers are, for example, aliphatic nitrates such as 2-ethylhexyl nitrate and cyclohexyl nitrate and peroxides such as di-tert-butyl peroxide. B10) Antioxidants
Suitable antioxidants are, for example, substituted phenols, such as 2,6-di-tert-butylphenol and 6-di-tert-butyl-3-methylphenol, and also phenylenediamines such as N, N'-di-sec-butyl- p-phenylenediamine. B11) Metal deactivators
Suitable metal deactivators are, for example, derivatives of salicylic acid such as N, N'-disalicylidene-1,2-propanediamine. B12) Solvents
Suitable solvents are, for example, non-polar organic solvents such as aromatic and aliphatic hydrocarbons, for example toluene, xylenes, turpentine and products sold under the trade names SHELLSOL (Royal Dutch / Shell Group) and EXXSOL (ExxonMobil), as well as solvents polar organics, for example, alcohols such as 2-ethylexanol, decanol and isotridecanol. Such solvents are usually added to diesel fuel together with the aforementioned additives and coadditives, which are intended to dissolve or dilute for better handling, C) Fuels
The inventive additive is exceptionally suitable as a fuel additive and can be used in principle in any of the fuels. It promotes a full range of beneficial effects in the operation of internal combustion engines with fuels. Preference is given to the use of the inventive quatemized additive in intermediate distillate fuels, especially in diesel fuels.
The present invention therefore also provides fuels, especially intermediate distillate fuels, with a content of the inventive quaternized additive that is effective as an additive to obtain advantageous effects in the operation of internal combustion engines, for example diesel engines, especially diesel engines injection molding, in particular diesel engines with common rail injection systems. This effective content (dosage) is in general from 10 to 5000 ppm by weight, preferably from 20 to 1500 ppm by weight, especially from 25 to 1000 ppm by weight, in particular from 36 to 750 ppm by weight, based on each case in the total amount of fuel.
Intermediate distillate fuels such as diesel fuels or heating oils are preferably mineral oil raffinates which typically have a boiling range of 100 to 400 ° C. These are usually distilled having a 95% point up to 360 ° C or even more high. These can also be called "diesel with ultra low sulfur" or "city diesel", characterized by a 95% spot, for example, of not more than 345 ° C and a sulfur content of not more than 0.005 % by weight or by a 95% point, for example, 285 ° C and a sulfur content of not more than 0.001% by weight. In addition to mineral distillate fuels or diesel fuels obtainable by refining, those obtainable by coal gasification or gas liquefaction [“gas to liquid” (GTL) fuels) or by biomass liquefaction [“biomass to liquid” fuels ( BTL)] are also suitable. Also suitable are mixtures of intermediate distillate fuels or diesel fuels mentioned above with renewable fuels, such as biodiesel or bioethanol.
The qualities of heating oils and diesel fuels are detailed, for example, in DIN 51603 and EN 590 (as also Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, Volume A12, p. 617 ff).
In addition to its use of the above mentioned intermediate distillate fuels of fossil, vegetable or animal origin, which are essentially hydrocarbon mixtures, the inventive quaternized additive can also be used in mixtures of such intermediate distillates with biofuel oils (biodiesel). Such mixtures are also covered by the term "intermediate distillate fuel" in the context of the present invention. They are commercially available and usually comprise biofuel oils in smaller quantities, typically in quantities from 1 to 30% by weight, especially from 3 to 10% by weight, based on the total amount of intermediate distillate of fossil, vegetable or animal origin and biofuel oil.
Biofuel oils are generally based on fatty acid esters, preferably essential on alkyl fatty acid esters derived from vegetable and / or animal oils and / or fats. Alkyl esters are typically understood to mean lower alkyl esters, especially C1-C4 alkyl esters, which are obtainable by the transesterification of glycerides that occurs in vegetable and / or animal oils and / or fats, especially triglycerides, by means of lower alcohols, for example example ethanol or in particular methanol (“FAME”). The lower alkyl esters based on typical vegetable and / or animal oils and / or fats, which find use as a biofuel oil or its components, are, for example, sunflower methyl ester, palm oil methyl ester (“SME”) ), soybean oil methyl ester (“SME”) and especially rapeseed oil methyl ester (“RME”).
Intermediate distillate or diesel fuels are more preferably those having a low sulfur content, i.e. having a sulfur content of less than 0.05% by weight, preferably less than 0.02% by weight, more particularly less than 0.005% by weight and especially less than 0.001% by weight of sulfur.
Useful gasoline fuels include all commercial gasoline fuel compositions. A typical representative that should be mentioned here is the Eurosuper base fuel for the EN 228, which is common in the market. In addition, gasoline fuel compositions of the specification according to WO 00/47698 are also possible fields of use for the present invention.
The inventive quaternized additive is especially suitable as a fuel additive in fuel compositions, especially in diesel fuels, to overcome the problems outlined at the beginning in direct injection diesel engines, particularly in those with common boom injection systems.
The invention is now illustrated in detail by the following working examples: Experimental Section: A. General test methods
a) Determination of the amide or imide content by IR spectroscopy The presence of amide or imide in a sample is examined by IR spectroscopy. The characteristic IR range for amide is 1667 ± 5 cm’1, while the characteristic IR range for imide is 1705 ± 5 cm’1. For this purpose, the samples were diluted 50% (w / w) in Solvesso and analyzed in a 29 pm CaF2 cuvette.
b) Engine test bl) XUD9 test - determination of flow restriction
The procedure was in accordance with CEO F-23-1-01 standard stipulations. b2) DW10 test - determination of power loss as a result of injector deposits on the common rail diesel engine
To examine the influence of additives on the performance of targeted injection diesel engines, the power loss was determined based on the official CEC test method F-098-08. The loss of power is a direct measure of the formation of deposits in the injectors.
A direct injection diesel engine with a common ramp system according to the CEO F-098-08 test method was used. The fuel used was commercial diesel fuel from Haltermann (RF-06-03). To synthetically include the formation of deposits in the injectors, 1 ppm of zinc was added to it in the form of a solution of zinc didodecanoate. The results illustrate the power loss relative to 4000 rpm, measured during 12 hours of constant operation. The “t0” values indicate the loss of normalized power (100%) to the value after 10 minutes; the “tl” value indicates the power loss normalized to the value after one hour
c) Short sedimentation test (BS test) - determination of the action as a cold flow enhancer
In the course of storing diesel fuels in a storage tank or vehicle at temperatures below the cloud point (CP), precipitated paraffins can settle. The paraffin-rich bottom phase that forms has relatively poor cold performance, and can block vehicle filters, thus leading to the collapse of release rates.
The BS test simulates and visually assesses possible sedimentation in vehicle tanks. The CP and CFPP values of the paraffin-enriched diesel fuel phase obtained in the test are determined by comparing these values with those for the non-sedimented fuel and allows conclusions about the cold performance of the fuel. For this purpose, the delta CP or delta CFPP values are determined.
In the test, the diesel fuel (DF) optionally added to be tested is processed at -13 ° C for a total of 16 h. It is evaluated visually. Subsequently, 80% by volume of the upper fuel phase is carefully sucked from the top. After heating and homogenizing the remaining 20% of the lower phase, your cloud point (CPCC) and your Geld filter plugging point (CFPPCC) are determined with devices known to you.
The procedure is to filter the required sample quantities through a fluted filter, (for DIN EN 116) to remove dirt, coke constituents, water or other undissolved impurities. The sample vessel (graduated measuring cylinder) is filled with 550 ml of sample liquid. If required, the sample is mixed with an additive. It is heated to 50 ° C in a water bath. The sample vessel is removed from the water bath and dried. The sample is homogenized by inversion and agitation. The starting (“original”) CP and CFPP values for the portions are determined. The sample temperature is adjusted to close to 25 ° C by standing under air.
The sample vessel containing 500 ml of sample is suspended in a liquid bath by means of a containment device. Heat treatment starts at 25 ° C. The sample is cooled to -13 ° C within 2 h and 40 min. The sample is stored at -13 ° C for 13 h and 20 min.
Using a suction device, the sample is sucked from the top to a residual amount of 100 ml (20%). The movement and turbulence of the sample should be kept as low as possible. The sample vessel with the lower 20% phase remaining in it is heated to 50 °
C. The lower phase is homogenized and used to determine the final CP and CFPP values (ie CPCC and CFPPCC).
d) Detection of the betaine structure
The betaine structure in the inventive additives and their synthesis precursors are detected by mass determination using Matrix-Assisted Laser Desorption / Flight Time Mass Spectrometry Ionization Time (MALDI-TOF-MS). The analysis is carried out under the following conditions:
Bruker's BIFLEX 3 instrument and a 337 nm wavelength UV laser are used. The laser power is increased until the ion ionization threshold is reached. The matrix consists of 20 g / 1 of dithranol in THF (ionically exchanged), using a polymer concentration of approx. 2 g / 1 in THF. The procedure is as follows: the matrix is mixed with the particular polymer in a 1: 1 ratio, and 1 p.1 of it is dried on the target (“dry droplet technique”). The dried fractions are then dissolved in 20 µl of the matrix solution and finally analyzed. A total of 100 individual spectra are added together per measurement.
In addition, the analysis is also carried out using ESI-LC / MS (electrospray ion chromatography - mass spectrometry) in the THF solvent. For this purpose, the LTQIFT (Thermo) MS system and the LC system consisted of HP 1100 bin pump, HP 1100 ALS and HP 1100 DAD are used. Approx. 10 mg of test substance is dissolved in 1 ml of THF and analyzed at room temperature. The resolution is 100,000.
e) Determination of compatibility with diesel fuel engine oil (OF)
The determination was made by the methods in the criteria catalog compiled by Deutsche Wissenschaftliche Gesellschaft kw Erdol, Erdgas and Kohle e.V. (DGMK) for the testing of lubricity additives in diesel fuels (DGMK Report 531)
In the fuel system of diesel vehicles, it is possible for small amounts of engine oil to be admitted to the diesel fuel circuit. In some cases, it has been observed that reactions have occurred between the constituents of engine oil and the additives present in diesel fuels, and have led to fuel filter blockages and consequently to vehicle failure. Therefore, a test method was developed, with the help of which the reactions between the engine oil and diesel fuel additives that would lead to the filter blocks are recognized and evaluated.
The additive to be tested is mixed with the same quantity of the stipulated motor oil and conditioned at 90 ° C in three days. After this conditioning, the mixture is diluted with diesel fuel and mixed, and evaluated, with the help of the SEDAB test (DGMK Report 531, appendix II-A). The results of both tests allow an opinion about the “engine oil compatibility” of the diesel fuel additive to be tested. Equipment and test medium:
- 500 ml Erlenmeyer flask with ground glass stopper NS19 - alpha-methylnaphthalene - diesel fuel that passes the SEDAB test flawlessly - engine oil (CEC Reference Lube RL-189, S AE 15 W-40)
The DF provided for test performance and the engine oil must be evaluated with the help of the SEDAB test before its first use. For this purpose, 10 g of motor oil are dissolved in 500 ml of DF. To improve solubility, it may be necessary to add 10 ml of alpha-methylnaphthalene and repeat homogenization. This mixture is evaluated immediately in the SEDAB test. When the mixture is impeccably filterable, the DF can be used for the performance of the test. 10 g of motor oil and 10 g of the additive to be tested are weighed each in a 500 ml Erlenmeyer flask, and then homogenized by tilting the flask. In case of insufficient miscibility, 10 ml of alpha-methylnaphthalene are additionally added and the mixture is again homogenized. This mixture is closed with a glass lid and conditioned at a temperature of 90 ° C in a drying cabin for three days.
After conditioning, the mixture is allowed to cool to room temperature for one hour and evaluated visually for any deposits, turbidity, gel formation, etc. The mixture is made up to 500 ml with diesel fuel and mixed carefully. It is evaluated visually. If deposits have formed, they must be placed in suspension by vigorous stirring before the performance of the SEDAB test. After standing for two hours, the mixture is evaluated visually again and then filtered through a 0.8 pm filter at a differential pressure of 800 mbar (see the SEDAB test method). The total quantity must be filterable within the set time.
In the event of deposits, turbidity, gel formation and / or insufficient filterability in the SEDAB test, the additive cannot be classified as compatible with motor oil. In the case of good filterability and impeccable visual appearance, the additive can be classified as compatible with motor oil. Specifications for the SEDAB test:
500 ml of a pretreated DP is sucked through a membrane filter. The time in seconds required to filter this volume at 20 ± 2 ° C and 200 hPa (ie pressure differential of approx. 800 hPa) is determined. When this takes more than two minutes, the amount of filtrate present after two minutes is noted. Instruments / materials required • Membrane filter: from Sartorius, made of cellulose nitrate, white, smooth, 50 mm in diameter, pore size 0.8 pm. • Filtration device: Filtration unit with 500 ml funnel: Sartorius SM 16 201 • Suction bottle: 1000 ml capacity • Vacuum system: for example, constant vacuum TOM-VAC 1 Automatic Zerosystem with a minimum pressure of 200 hPa. • Drying booth for heat treatment at 90 ± 3 ° C, without air circulation • Tweezers • Glass Petri dish, diameter approx. 125 mm, with acceptable lid • Sample vessel: measuring cylinder (500 ml capacity) with gasket and glass lid. To prepare the sample, the sample vessel of the original fuel sample is shaken with 20 vertical movements. The sample is left to stand at room temperature for 16 hours. Immediately before measurement, the fuel is homogenized once more by stirring (10 movements) and introduced into the 500 ml funnel of the tester.
The membrane filters are conditioned at 90 +/- 3 o C for half an hour in a drying cabin and then stored in a desiccator until use. The correspondingly prepared membrane filter is placed inside the filtration device. The 500 ml funnel is filled with the entire sample (500 ml) and then a pressure of 200 hPa, (absolute, corresponds to the pressure differential of approx. 800 hPa) is applied immediately. It must be ensured that no fuel samples are poured in after that. The filtration time is reported rounded up to the complete seconds. If a filtration time of two minutes is exceeded without the entire sample being filtered, the test is terminated and the volume of fuel that has passed through to this point is measured. In this case, the result is reported as "> 2 minutes" and the amount of sample (ml) filtered at the time the test was stopped. When the sample's filtration time is longer than two minutes, a corresponding specimen must be heated to 50 ° C for 30 minutes and then filtered. If the test result is again above two minutes, the total dirt content of the fuel must be determined in accordance with DIN 51 419.
After filtration, the funnel and filter are rinsed with n-heptane and then with petroleum ether (40/80) to release them from the DF. The membrane filter is carefully removed from the filter plate with tweezers, placed in a clean Petri dish and dried in a drying cabinet at 90 ± 3 ° C with the lid half open for 30 minutes. After that, the Petri dish is placed inside the desiccator to cool for at least 15 minutes.
Samples that are filterable within two minutes by the process described above are classified as "non-critical" with respect to the present test method. Diesel fuels that are not filterable within this time must be classified as "critical" and can lead to filter blockages in vehicles and filling stations. In the case of samples with critical behavior, the membrane filter must be studied optically (microscopically) or by means of infrared spectroscopy as to the cause of the blockage.
B. Examples of preparation and analysis: Reagents used: PIBSA: Mw = 1100; hydrolysis number = 85 mg KOH / g DMAPA: Mw = 102.18 Styrene oxide: Mw = 120A5 Acetic acid: Mw - 60.05
Preparation example 1: Synthesis of an inventive acid-free quaternized succinamide (PIBSA / DMAPA / styrene oxide * amidation at 40 ° C)
386.8 g (0.35 mol) of polyisobutenosuccinic anhydride 5 (PIBSA 1000) are dissolved in 176 g of Solvesso 150 in a 2-liter four-mouthed flask at room temperature under a gentle N2 stream. After adding 29.9 g (0.29 mol) of 3-dimethylamino-1-propylamine (DMAPA), the reaction temperature rises to 40 ° C. The solution is stirred at 40 ° C for 10 minutes. Subsequently, 34.2 g (0.29 10 mol) of (1,2-epoxyethyl) benzene are added, which is followed by an additional reaction time of 7 hours at 70 ° C under N2. The solution is finally adjusted to a 50% active ingredient content with 274.9 g of Solvesso 150.
Through the IR analysis, it was possible to detect the formation of the inventive amide addition product (A).
Using ESI-LC / MS and MALDI-TOF-MS, the betaine structure of (A) was determined experimentally.

The global experiment is carried out under a smooth N2 current. The initial load of PIBSA 1000 (481.61 g) and Pilot 900 oil (84.99 g) is stirred at 110 ° C. Then DMAPA (3728 g) is introduced at 110 to 115 ° C within 42 minutes. A slightly exothermic reaction is observed. Subsequently, the mixture is heated to 150 ° C and stirred at 150 ° C for 3 h to remove the reaction water. The mixture is then cooled to room temperature, and successively mixed with MeOH (152 g), acetic acid (21.91 g) and styrene oxide (43.84 g). The mixture is then stirred until reflux (67 to 69 ° C) for 5 h. After standing at 30 to 35 ° C overnight, the mixture is concentrated by distillation (1 h / 6 mbar / oil bath at 36 ° C). The final weight of 661.1 g is adjusted to an active ingredient content of 50% with Pilot 900 oil (493.07 g).
Through the IR analysis, it was possible to detect the formation of imide (B).
By means of ESI-LC / MS and MALDI-TOE-MS, the absence of a betaine structure in (B) was experimentally demonstrated.
C. Examples of use:
In the usage examples that follow, additives are used as a pure substance (as synthesized in the preparation examples above) or in the form of an additive package. The following packages have been used: M2450: inventive additive package
M2452: Comparative additive package

Usage example 1: determination of the additive action in the formation of deposits in diesel engine injection nozzles a) XUD9 tests Used fuel RF-06-03 (reference diesel, Haltermann Products, Hamburg)
The results are compiled in the table below:
b) DW10 test
The test results are shown in figure 1. The tO 10 values are plotted there.
It is found that, at the same dosage (100 mg / kg of active ingredient, that is 200 ppm of preparation example 1), the inventive amide additive (diamonds) and the comparative imide additive (triangles) significantly reduces the loss of potency observed for non-additive fuel (squares), although the inventive additive stabilizes the remaining power loss in the region of about 0.5% over the entire test duration, ie 99.5% of the original maximum engine power is maintained.
With the corresponding comparative additive, however, only 98.5% of the original maximum engine power is maintained.
Usage example 2: Determination of low temperature properties - short sedimentation test
Commercially available winter DF was added in the manner specified in the table below with additive according to preparation example 1 (# 3) and additive according to preparation example 2 (# 2), and also with additive package M2450 ( # 5) or M2452 (# 4), and subjected to a BS test. The comparison (# 1) used was DF with cold-flow additive without amide and imide.
The test fuel used was diesel fuel from Bayemoil, (CP -6.5 ° C).
All fuel samples (# 1 to # 5) were additionally added with commercial intermediate distillate cold flow enhancer (MDFI) and anti-wax sedimentation additive (WASA).
It can be deduced from the test data compiled in the table below that the delta CP and CFPPCC values of the DFs additive according to the invention are significantly improved compared to the DFs containing imide. The addition of amide can thus significantly improve the cold performance of DFs.
CFPP: CFPP of the global fuel CFPPCC: CFPP of the lower phase CPCC: CP of the lower phase Delta CP: Difference of the CP of fuels added only with cold flow enhancer without the addition of preparation examples 1 or 2 Example of use 3: Determination of engine oil compatibility
The determination was made according to the specifications of DGMK Report 531.
Used motor oil: Wintershall 14W40 Multi Record Top
Diesel fuel (DF) used: RF-06-03 (reference diesel, Haltermann Products, Hamburg)
The additive to be tested is mixed with the same amount of mineral oil (10 g at a time), conditioned at 90 ° C for 3 days and evaluated visually in its course. Subsequently, the mixture is made up to 500 ml with diesel fuel, mixed and evaluated with the help of the SEDAB filtration test (also defined in DGMK Report 531).
The results are compiled in the table below:
a) since both products comprised different types of solvent (Solvesso 150 or Pilot 900) as a result of the synthesis, they were mixed with the same amount of the other solvent in each case before the test performance, in order to give test conditions identical.
Usage example 4: Determining the effects of IDIDs
The determination was made in a passenger vehicle operation test. Commercial diesel fuel (DF) EN590 was added (with the usual DF additives). The additive to be tested (inventive additive according to preparation example 1) was added to DF EN590. For comparison, commercial EN590 fuel that was not mixed with an inventive additive was used. After the engine test ended, the injectors were checked for deposits. A surprisingly evident positive effect on IDIDs is seen. Test Procedure:
A passenger vehicle with common ramp injectors (magnetic type), in which injector deposits were found, was used for the evaluation of the additive for the removal of these internal injector deposits.
The occurrence of brown internal deposits in the injectors was detected by visual inspection of the face of the solenoid coil, the valve plate in front of the face and the face of the valve seat, and was also noticeable through the rough and noisy operation of the engine. It was also possible to deduce from the reading data that the amount of fuel injected into the cylinder deviated distinctly from the normal value.
The engine was first operated on the road with a tank filled with conventionally additive diesel without the inventive additive, EN590 base fuel (50 liters, 750 km in mixed operation on motorways, other main roads and in the city center). No improvement in internal deposits was observed when the vehicle was operated with a tank filled with non-additive fuel (as shown in the table below).
In the next stage, the tank was filled with the same EN590 base fuel, but it was mixed with the inventive additive in a dosage of 120 mg / kg of active material. The car was driven again for 750 km in mixed operation. The deposits after 750 km were distinctly reduced after this test operation with added fuel, as was already detectable by the smoother, quieter engine operation. The reading data from the engine control unit also showed that the injected fuel quantities declined to the target value.
After two tank fillings and operation in 1500 km with fuel additive according to the invention, the injector deposits 5 stored disappeared completely from the face of the solenoid coil, the valve plate in front of the face and the face of the valve seat, as it was visually discernible after the injector was opened.
These results clearly illustrate that the inventive additive completely removed internal injector deposits (IDIDs) in low dosage. It can be similarly concluded from the test results that the additive is also able to prevent the formation of IDIDs even at low dosage rates. In addition, it has been discovered that the inventive additive is able to eliminate not only IDIDs such as wax and soap but also solid polymeric deposits, such as carbon. Table

Reference is made explicitly to the publication of the publications cited here.

权利要求:
Claims (26)
[0001]
1. Process for preparing quaternized nitrogen compounds, the process characterized by the fact that a) a compound comprising at least one group containing oxygen or nitrogen reactive with the anhydride and additionally comprising at least one quaternizable amino group is added to a compound polycarboxylic anhydride, in which the reaction is carried out at a temperature below 80 ° C; and b) the product of stage a) is quatemized, in which quaternization is carried out without the addition of an H + donor for a period of 1 to 10 hours at a temperature of 40 to 80 ° C.
[0002]
Process according to claim 1, characterized in that the polycarboxylic anhydride compound is a di-, tri- or tetracarboxylic anhydride.
[0003]
Process according to claim 1 or 2, characterized in that the polycarboxylic anhydride compound is the anhydride of a C4-C10 dicarboxylic acid.
[0004]
Process according to any one of the preceding claims, characterized in that the polycarboxylic anhydride compound comprises at least one hydrocarbyl substituent having a numerical average molecular weight (Mn) in the range of 200 to 10,000, especially 350 to 5000 .
[0005]
Process according to any one of the preceding claims, characterized by the fact that the reactive compound with the anhydride is selected from a) hydroxyalkyl-substituted mono- or polyamines having at least one quaternizable primary, secondary or tertiary amino group; b) polyamines, cyclic, heterocyclic, aromatic or non-aromatic, straight or branched having at least one primary or secondary amino group and having at least one qualifying primary, secondary or tertiary amino group; c) piperazines.
[0006]
6. Process according to claim 5, characterized by the fact that the reactive compound with the anhydride is selected from a) hydroxyalkyl substituted primary, secondary or tertiary monoamines and hydroxyalkyl substituted primary, secondary or tertiary diamines, b) aliphatic diamines straight or branched chain having two primary amino groups; di- or polyamines having at least one primary and at least one secondary amino group; di- or polyamines having at least one primary and at least one tertiary amino group; aromatic carbocyclic diamines having two primary amino groups; aromatic heterocyclic polyamines having two primary amino groups; aromatic or non-aromatic heterocycles having a primary and a tertiary amino group.
[0007]
Process according to any one of the preceding claims, characterized by the fact that the quaternizing agent is selected from epoxides, especially hydrocarbyl epoxides.
[0008]
8. Process according to claim 7, characterized by the fact that the quaternization is carried out without the addition of acid.
[0009]
Process according to any one of the preceding claims, characterized by the fact that stage a) is carried out at a temperature in the range of 30 to 70 ° C, in particular from 40 to 60 ° C.
[0010]
10. Process according to any one of the preceding claims, characterized by the fact that stage a) is carried out in a period of 1 to 120 minutes, especially 10 to 30 minutes.
[0011]
Process according to any one of the preceding claims, characterized by the fact that stage b) is carried out with a hydrocarbyl epoxide as the quaternizing agent in the absence of free acid.
[0012]
Process according to any one of claims 4, characterized in that the hydrocarbyl substituent of the polycarboxylic anhydride compound is a polyisobutenyl radical derived from highly reactive polyisobutene.
[0013]
Process according to claim 12, characterized in that the highly reactive polyisobutene is a fraction of vinylidene double bonds of more than 80 mol%.
[0014]
Process according to claim 12 or 13, characterized in that the highly reactive polyisobutene is composed to an extent of at least 85% by weight, preferably at least 90% by weight and more preferably at least 95% by weight of isobutene units.
[0015]
Process according to any one of claims 12 to 14, characterized in that the highly reactive polyisobutene has a polydispersity in the range of 1.1 to 2.5, in particular less than 1.9.
[0016]
16. Quaternized nitrogen compound, characterized by the fact that it is obtainable by a process as defined in any of the preceding claims.
[0017]
17. Quaternized nitrogen compound according to claim 16, characterized by the fact that it comprises at least one compound of the general formulas:
[0018]
A nitrogenized nitrogen compound according to claim 16 or 17, characterized by the fact that it is essentially free from H + donor, especially free from acid and in particular does not comprise any of the inorganic acids or short chain organic acids.
[0019]
19. Use of a quaternized nitrogen compound as defined in any of claims 16 to 18, characterized by the fact that it is as a fuel additive or lubricant additive.
[0020]
20. Use according to claim 19, characterized by the fact that it is as a detergent additive for diesel fuels.
[0021]
21. Use according to claim 19, characterized by the fact that it is as an anti-sedimentation wax additive (WASA) for intermediate distillate fuels, especially diesel fuels.
[0022]
22. Use according to claim 20, characterized by the fact that it is as an additive to reduce or prevent deposits in injection systems for direct injection diesel engines, especially in common rail injection systems, to reduce fuel consumption of direct injection diesel engines, especially diesel engines with common rail injection systems, and / or to minimize power loss in direct injection diesel engines, especially diesel engines with common rail injection systems.
[0023]
23. Use according to claim 22, characterized in that it is as an additive to control (prevent or reduce) power loss due to deposits in the injector as determined by the DW10 test method.
[0024]
24. Additive concentrate, characterized by the fact that it comprises, in combination with other fuel additives, especially diesel fuel additives, at least one qualified nitrogen compound as defined in claim 16 or 17.
[0025]
25. Fuel composition, characterized by the fact that it comprises, in a majority of a common base fuel, an effective amount of at least one quantized nitrogen compound as defined in claim 16 or 17.
[0026]
26. Lubricant composition, characterized by the fact that it comprises, in a majority of a usual lubricant, an effective amount of at least one quantized nitrogen compound as defined in claim 16 or 17.

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公开号 | 公开日

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EP3327044B1|2020-10-28|

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MX2013000054A|2013-03-18|

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AU2011275778A1|2013-01-24|

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BR112013000297A2|2016-05-24|

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AU2011275778B2|2016-03-03|

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EP2591016B1|2015-01-21|

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ES2655470T3|2018-02-20|

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WO2012004300A1|2012-01-12|

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EP2591016A1|2013-05-15|

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AU2017228610A1|2017-10-05|

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EP3747915A1|2020-12-09|

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ES2844403T3|2021-07-22|

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JP2013532163A|2013-08-15|

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AU2019210580A1|2019-08-22|

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AU2016200898A1|2016-03-03|

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PL3327044T3|2021-07-19|

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CA2804322C|2020-02-11|

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CN103080145B|2014-12-10|

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KR20130041926A|2013-04-25|

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EP2808350B1|2017-10-25|

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AU2016200898B2|2017-06-15|

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PL2808350T3|2018-04-30|

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ES2535192T3|2015-05-06|

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AU2017228610B2|2019-05-16|

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HUE052753T2|2021-05-28|

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EP3327044A1|2018-05-30|

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CN103080145A|2013-05-01|

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EP2808350A1|2014-12-03|

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PL2591016T3|2015-07-31|

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法律状态:
2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-10-15| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-08-04| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-10-06| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 06/07/2011, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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EP10168622|2010-07-06|

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EP10168622.8|2010-07-06|

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EP11165920|2011-05-12|

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EP11165920.7|2011-05-12|

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PCT/EP2011/061398|WO2012004300A1|2010-07-06|2011-07-06|Acid-free quaternised nitrogen compounds and use thereof as additives in fuels and lubricants|

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