AU2011340776A1

AU2011340776A1 - Polytetrahydrobenzoxazines and bistetrahydrobenzoxazines and use thereof as additive to fuel or lubricant

Info

Publication number: AU2011340776A1
Application number: AU2011340776A
Authority: AU
Inventors: Harald Bohnke; Ivette Garcia Castro; Wolfgang Grabarse; Markus Hansch; Hannah Maria Konig; Arno Lange; Ludwig Volkel
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2010-12-09
Filing date: 2011-12-05
Publication date: 2013-06-20
Also published as: CA2819770A1; EP2649054A1; JP2014502278A; EP3263563A1; MX2013006289A; CN103261175A; ES2643013T3; WO2012076428A1; BR112013013583A2; CN103261175B; KR20140001982A; EP2649054B1

Abstract

Polytetrahydrobenzoxazines and bistetrahydrobenzoxazines obtainable by (A) reaction of at least one diamine of formula H

Description

Polytetrahydrobenzoxazines and bistetrahydrobenzoxazines and use thereof as additive to fuel or lubricant Description 5 The present invention relates to novel polytetrahydrobenzoxazines which can be defined by the preparation process specified below or alternatively by the general structural formula I specified below. The polytetrahydrobenzoxazines may also be present in quaternized form. 10 The present invention further relates to novel bistetrhydrobenzoxaznes which occur as intermediates in the preparation of the polytetrahydrobenzoxazines, The present lirvention further relates to the use of the polytetrahydrobenzoxazines and 15 of the bistetrahydrobenzoxazines as a fuel additive or lubricant additive, especially as a detergent additive for diesel fuels, in particular for direct-injection diesel engines, and to additive concentrates, fue compositions and lubricant compositions which comprise the polytetrahydrobenzoxazines or bistetrahydrobenzoxazines. 20 In direct-injection diesel engines, the fuel is injected and distributed ultrafinely (nebulized) by a multihole injection nozzle which reaches directly into the combustion chamber in the engine, instead of being introduced into a prechamber or swirl chamber as in the case of the conventional (chamber) diesel engine. The advantage of the direct-injection diesel engines ies in their high performance for diesel engines and a 25 nevertheless low fuel consumption. Moreover, these engines achieve a very high torque even at low speeds. At present, essentially three methods are being used to inject the fuel directly into the combustion chamber of the diesel engine: the conventional distributor injection pump, 30 the pump-nozzle system (unit-injector system or unit-pump system) and the common rail system. in the common-rail system, the diesel fue is conveyed by a pump with pressures up to 2000 bar into a high-pressure line, the common rail Proceeding from the common rail, 35 branch lines run to the different injectors which inject the fuel directly into the combustion chamber. The full pressure is always applied to the common rail, which enables multiple injection or a specific injection form. In the other injection systems, in contrast, only lesser variation of injection is possible. The injection in the common rail !s divided essentially into three groups: (1.) pre-injection, by which essentially softer 40 combustion is achieved, such that hard combustion noises ('naling") are reduced and the engine appears to run quietly; (2.) main injection, which is responsible especially for a good torque profile: and (3.) post-injection, which especially ensures a iow nitrogen oxide value in the exhaust gas- In this post-injection, the fuel is generally not 2 combusted, but instead evaporated by 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 red ucing agent for the nitrogen oxides. 5 The variable, cylinder-individual injection in the common-ral injection system can positively influence the pollutant emission of the engine, for example the emission of nitrogen oxides (NOj, carbon monoxide (CO) and especially of particulates (soot). This makes it possible, for example, that engines equipped with common-rail injection systems can meet the Euro 4 standard theoretically even without additional particulate 10 filters, In modern common-rail diesel engines, under particular conditions, for example when biodiesei-containing fuels or fuels with metal impurities such as zinc compounds, copper compounds, lead compounds and further metal compounds are used, deposits 15 can form on the injector orifices, which adversely affect the injection performance of the fuel and hence impair the performance of the engine, Le. especially reduce the power, but in some cases also worsen the combustion. The formation of deposits is enhanced further by further developments of the injector construction, especially by the change in the geometry of the nozzles (narrower, conical orifices with rounded outlet). For lasting 20 optimal functioning of engine and injectors, such deposits in the nozzle orifices must be prevented or reduced by suitable fuel additives, WO 20091040582 describes the use of a Mannich reaction product of an aldehyde, a polyamine and a substituted phenol with a substituent which has a mean molecular 25 weight of less than 300 as a diesel additive for improving the efficiency of the diesel engine, especially reducing the power loss in the engine and reducing the level of deposits on the injectors. WO 20091040583 describes the use of the combination of a Mannich reaction product 30 of an aldehyde, a polyamine and a substituted phenol with a polyisobutylsuccinimide as a diesel additive for improving the efficiency of the diesel engine, especially reducing the power loss in the engine and reducing the level of deposits on the injectors. WO 20091040584 describes a meta-containing diesel fuel which, as an efficiency 35 improving additive, comprises a Mannich reaction product of an aldehyde, a polyamine of the structure of an optionally substituted ethylenediamine and a substituted phenol. The improvement in efficiency consists especially in the reduction in the power loss in the engine, the reduction in the level of deposits on the injectors, the reduction in the level of deposits in the fuel filter, and the reduction of fuel consumption. 40 WO 20091040585 describes the use of a Mannich reaction product of an aldehyde, a polyamine and a substituted phenol, where the molar ratio of phenol to polyamine in the reaction mixture is at least 1.5 : 1, as a diesel additive for improving the efficiency 3 of the diesel engine, especially reducing the power loss in the engine, reducing the level of deposits on the injectors, reducing the level of deposits in the fuei fiter and reducing fuei consumption. 5 GB-A 2 468 130 discloses a diesel fuel which comprises one or more efficiency enhancing additives from the group of the polymeric or nonpolymeric phenol-ammonia aldehyde Mannich adducts, the polyisobutylsuccinimides, the antioxidants, the mixtures of poIdsobutylsuccinimides with polyether carrier oils and the phenol-polyamine aldehyde Mannich adducts. These additives bdng about an improvement in the 10 efficiency of the diesel engine and a reduction in the level of deposits in the diesel engine. WO 20081027881 describes quatemary ammonium salts as reaction products of Mannich adducts which have a tertiary amino group and are obtainable from a 15 substituted phenol, an aidehyde and an amine, and a quatemtng agent. These quaternary ammonium salts are suitable inter alLa as additives in fuels. However, the additive systems described in the prior art have a series of disadvantages - especially in the case of direct-injection diesel engines, in particular in 20 those with common-rail injection systems. Excessive deposits still occur in the injection systems of the engines, and the fuel consumption and the power loss are still too high Furthermore, the diesel fueis addiftzed with the additive systems described in the prior art stili have iow-temperature properties which are in need of improvement. The compatibility of motor oils with the additive systems desonbed in the prior art is aiso still 25 not optimal It is therefore an object of the present invention to provide fuel and lubricant additives with improved efficiency. The object is achieved by the polytetrahydrobenzoxazines and bistetrahydrobenzoxazines described hereinafter. 30 The inventive polytetrahydrobenzoxazines can be defined by the process for preparing them Accordingly, the present invention provides polytetrahydrobenzoxazines wtich are obtainable by the reaction steps of 35 (A) reacting at least one diamine of the general formula H 2 N-A-NHt, in which the bridging member A is C- to C r-aikylene which may be interrupted by up to 10 oxygen atoms and/or tertiary nitrogen atoms, C- to Crakenylene, C- to Ce 0 cycloaikylene, Ce,- to Czrarylene or C- to Cwrraraikylene with at least one C- to C-aldehyde and at least one C- to Craikanol at a temperature of 20 to 80"C 40 with elimination and removal of water, where both the aidehyde and the alcohol may be used in each case in more than double the molar amount compared to the diamine; 4 (B) reacting the condensation product from reaction step (A) with at least one phenol which bears at least one long-chain substituent having 6 to 30 carbon atoms in a stoichiometric ratio to the diamine originally used in step (A) of 12: 1 to 35: 1 at a temperature of 30 to 120'Q 5 (C) heating the reaction product from reaction step (B) to a temperature of 125 to 280*C for at least 10 minutes. Cr to CQnalkyiene for the bridging member A represents linear or mono- or 10 polybranched saturated hydrocarbon bridging members having 1 to 20, especially 1 to 10 and in particular 1 to 4 carbon atoms, for example -CH-, -(CH ) 2 -, -CH(CHa)-, -(CHe)a-, -CH 2 -CH(CH), -(CH)C4-, -H2CHrCH(CHs)-, -CH-CH(CH3)-CH-, -(CH)-, -C HrC(CH3)rCH 2 -, -(CH)r, -CH(CH)-(CHz)rCH(CHs), -CH(CH 3 )-(CHrCH(CH)-,

-(CH

2

)

7 - or 15 In the case of an interruption of the Ce to Cas-alkylene bridging member by up to 10, especially by up to 4 and in particular by one or two or three oxygen atoms and/or tertiary nitrogen atoms, to following are examples of possible structures for A: -CHrO CH-, -CHCH2-C-C:H 2

CH

2 -, -CHrOO-CH2C H-O-0 H-, -OftC-C H2CHrQ-CHaCHrO 20 CH- -CHHC

H

-O-CH OHr-CH 2 C~t, -CHCHrO-CHp-OH2C~O-CH 2 CHr

CH-N(CH

3 )-C r or ~H2

-

N(-N(0H 2

)-CH

2 CH-, The side chains on interrupting tertiary nitrogen atoms are typically CI to C(alkyl radicals such as methy or ethyl; in the case of occurrence of such tertiary nitrogen atoms, the maximum carbon number of 20, espedally of 10 and in particular of 4 is not exceeded even including the alkyl side 25 chains. C2- to C-kenyiene for the bridging member A represents mono- or polyunsaturated, especially mono unsaturated, hydrocarbon bridging members having 1 to 20, especialy i to 10 and in particular 1 to 4 carbon atoms, for example -CH=CH, -CH=CCH-r, 30 -CH=CH-C&OH 2 -, -CHrCH=CH-Hr, C H-CH=CH, -CH(CHq)-CHCH- or -Ot-C(CHs)=CH-. C5- to C2-cycloalkylene, especially Cr to Cecycloalkylene, for the bridging member A is, for example, 1,1-, 1,2- or 1 3-cyclopenty]ene, 1,1- 1,2-, 1,3- or 1,4-cyclohexyiene, 35 1,1 -, 1,2-, 1,3- or 1 ,4-cycloheptyiene or 1,1-, 1,2-, 1,3-, 1,4- or 1,5-cyckoctylene, which may additionally bear one or more Cr to C-alkyl substituents such as methyl or ethyll groups, or is a dicyclohexyimethane skeleton with free valences in the 4 and 4' positions on the cyclohexyl rings. 40 C to C2-arylene, especially CC- to C-arylene, for the bridging member A is, for example, ortho-, meta- or para-phenyiene, naphthylenes., anthracylenes, phenan thrylenes or 4,4 diphenylene, which may additionally bear one or more C- to Crakyi substituents such as methyl or ethyl groups on their aromatic rings.

5 Cr to Cm-aralkylene, especially C- to Csr'arakyne, for the bridging member A represents structures with one free valence originating from an spz-hybridized carbon atom in an aromatic ring and with the other free valence originating from an sp 5 hybridized carbon atom in a size chain of the aromatic ring such as a phenyl ring, or with both free valences originating from spthybrdized carbon atoms in different side chains of an aromatic ring, for example ortho, meta- or para-Cel-tCH2-, ortho-, meta or para-CeH 4

-CH

2

CH

2 -, ortho-, meta- or para-CaH(CH2)n ortho-, meta- or para-C 6

H

(CH

2 )e or ortho-, meta- or par-CH2-CeH 4 -CHr. 10 In a preferred embodiment, the inventive polytetrahydrobenzoxazines are obtainable in reaction step (A) from at least one diamine of the general formula H 2 N-(CHx-NH 2 [iLe. A = -(CHi,) in which x is a number from 1 to 10. Particular preference Is given to diamines of the general formula H2N-(CH2)rNH 2 , in which x is a number from I to 8, 15 espedally a number from 1 to 4, in particular the number 2, When x = 2, said diam ine is 1,2-ethylenediamine. Suitable Ce to Cradehydes, especially Cr to Cr1aldehydes, are, for example, formaldehyde, acetaldehiyde, propionaldehyde, butyraldehyde, valeraldehyde or 20 benzaldehyde, In a preferred embodiment, the inventive polytetrahydrobenzoxazines are obtainable in reaction step (A) from formaIdehyde or a polymeric form of formaldehyde, such as paraformaidehyde or i,3,5-trioxane, Suitable Ce to Cralkanols, especially C,- to C4-alkanols, are, for example, methanol, 25 ethanol, r-propanol, isopropanol, n-butanol, sec-butano, isobutanol, tert-butano, n pentanol, sec-pentanol, isopentanoi, tert-pentanol, n-haxanol, rheptanol, n-octano, 2 ethylhexanol, n-nonanol, isononanol or n-decano, and also mixtures of such alkanols, In a preferred embodiment, the inventive polytetrahydrobenzoxazines are obtainable in reaction step (A) from at least one C% or C4-ealkanoL. 30 The diamine of the formula H2N-A-NH 2 is reacted with the 0- to C(> 2 aldehyde and the Cr to CralkanoI generally at room temperature to slightly elevated temperature, i.e. at 20 to 80*C, especially at 25 to 70*C and in particular at 30 to 60*C. Preference is given to working under gentle vacuum, i.e, at 20 mbar to standard pressure, especially at 30 35 to 700 mbar, in particular at 40 to 500 mbar, in order to be able to better remove the water eliminated from the reaction mixture - for example by azectropic distllation, The optimal temperature and pressure settings depend of course on the boiling point of the Ce to Cralkano(s) used. The preferred ranges specified above for temperature and pressure settings are particularly recommended in the case of use of 0 r or C4 40 alkanols. The diamine of the formula H2N-A-NH 2 is reacted with the C- to Crealdehyde and the Cr to Cralkanol advantageously in an inert organic solvent or a mixture of such 6 solvents, especially a hydrocarbon such as hexane, cyclohexane, toluene or xylene, or a halohydrocarbon such as chloroform or chlorobenzene, In many cases, it has been found to be advantageous first to in ially charge the C- to Craldehyde and the Cr to Cralkanol at room temperature or very low temperature in the inert solvent, then to 5 add the diamine and then - optionaly under reduced pressure - to heat to reaction temperature and to remove the water eliminated. The reaction time is typically I to 10 hours. in a preferred embodiment, the stoichiometic ratio of diamine to aldehyde in reaction 10 step (A) is 1 : 4, where a deviation from this ratio of up to 10% can be tolerated, and the alkanol is used in at least 3.5 times the motar amount, especialy 4 times the molar amount, compared to the diamine. The alcohol can also be used in a higher amount, L.e, in excess, for example in 4 to 8 times the molar amount compared to the diamine, The preferred stoichiometric ratio of damine to aldehyde is thus typically in the range 15 of i : (3,6 - 4.4) or of (0.9 - 1A) : 4, especially of 1 : (3.9 -4r1) or of (0.97-103) : 4. In reaction step (A), the active agent for the reaction with the phenol is obtained in reaction step (B), which is generally a mixture of the partly or fuly hydroxyaikylated diamine which is in partly or fully etherified form with the C ,- to Ca-ailkanol, and possibly 20 ring-closed conversion products such as imidazolidines. The individual components of this mixture are typically in chemical equilibrium with one another, such that normally all or almost all components of this mixture are available for further reaction in the next reaction step, (B), for the purposes of the present invention. 25 Such a mixture, which is obtainable, for example, by reacting ethylenediarnine, formaldehyde and isobutanol, is represented below by way of example with Its components: 7 0 H 0 OH HN- N H ~ H HD N N ,H 4 OH O H H O N HOHO OH 01 N H HO \ OH \AN No The phenol used in reaction step (B) bears, as the at least one long-chain substituent 5 having 6 to 3000 carbon atoms, typically a corresponding hydrocarbyl radical A hydrocarbyl radical shall be understood here to mean a hydrocarbon radical of any structure which, however, in a minor amount, may also comprise heteroatoms such as oxygen atoms and/or nitrogen atoms and/kr halogen atoms, and/or may bear functional groups such as hydroxyl groups, carboxyl groups, carboxylic ester groups, cyano 10 groups, nitro groups and/or sulfo groups. Said long-chain hydrocarbyl radical may be saturated or unsaturated in nature; it may have a linear or branched structure; it may comprise aromatic and/or heterocyclic substructures, The at least one long-chain substituent on the phenol serves principally to make the inventive polytetrahydrobenzoxazines better soluble in mineral oil products such as fuels and 15 lubricants.

a This relatively iong-chain hydrocarbyl radical on the phenol is preferably a hydrocarbyl radical having 6 to 30 carbon atoms or a polyisobutyi radical having 16 to 3000 carbon atoms. 5 Useful hydrocarbyl radicals having 6 to 30 carbon atoms on the phenol are preferably C to Cm-alkenyl radicals, especially C- to Cralkenyl radicals, in particular Cr to Cir alkenyl radicals and very especially Cr to Cr,-alkyl radicals, especially C- to Cwralkyl radicals, and in particular Cr to C-aikyl radicals. The phenol may bear one, two or three such long-chain substituents; the phenol preferably bears one such iong-chain 10 substituent. In addition to the long-chain substituents, the phenol may also bear one, two or three shorter-chain alkyl or alkenyl radicals such as methyl, ethy, n-propyl, isopropyl, n-butyi, sec-butyl, isobutyl tert-buty, vinyl or aylI radIcals, and/or one, two or three functional groups such as halogen atoms., for example chlorine or bromine, nitro groups, cyano groups, carboxyl groups, carboxylic ester groups or sulfo groups, where 15 the total number of substituents on the phenol is not more than 5, preferably not more than 4 and in particular not more than 3. Examples of said phenols having at least one long-chain substituent having 6 to 30 carbon atoms are phenols with an n-hexyl, n-heptyl, n-octyl, tert-octyl, 2-ethylhexy, n 20 nony, isononyl, n-decy, 2-propylheptylt n-undecy. n-dodecyi, n-tridecyl, isotridecyl, n tetradecyl n-hexadecyl, n-octadecyl, oleyl, linoly or linolenyl radical in the ortho or para position, and also ortho-cresol having one of the abovementioned long-chain alkyl or alkenyl radicals in the 4 or 6 position, meta-cresol having one of the abovemenioned long-chain alkyl or alkenyl radicals in the 4 or 6 position, para-cresol having one of the 25 abovementioned long-chain alkyl or alkenyt radicals in the 2 or 6 position, and phenols having two identical or different aboveneritioned long-chain alkyl or alkenyl radicals in the 2 and 4 position, In the case of polyisobutyl radicals, these comprise preferably 21 to 1000, especially 26 30 to 3000 or especially 26 to 500, in particular 30 to 3000 or in particular 30 to 250 carbon atoms, or they have number-average molecular weights Ma of 183 to 42 000., preferably 500 to 15 000, especially 700 to 7000, in particular 900 to 3000, most preferably 900 to 1100, 35 The phenol may bear one, tvo or three such polyisobuty radicals; the phenol preferably bears one such polyisobuty radical, In addition to the polyisobuty radicals, the phenol may also bear, one, two or three shorter-chain hydrocarbyl radicals such as methyl, ethy, n-propyl, isopropyl, n-butyl, sec-butyt. isobutyt fert-butyl, viny ally- n pentyl sec-penty, isopentyl tert-pentyt n-hexyl, n-heptyl noctyl, tert-octyb, 2 40 ethyihexyl, n-nony, isononyl, n-decy, 2-propylheptyl, n-undecyl. n-dodecyl, n-tridecyl, isotridecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, oleyl, linolyl or linolenyl radicals and/or one, two or three functional groups such as halogen atoms, for example chlorine or bromine, nitro groups, cyano groups, carboxy groups, carboxylic ester groups or 9 sulfo groups, where the total number of substituents on the phenol is not more than 5, preferably not more than 4 and in particular not more than 3, In a preferred embodiment, the inventive polytetrahydrobenzoxazines are obtainable in 5 reaction step (B) from at least one phenol which bears, in the para position (4 position) to the hydroxyl group, a Ca- to C 2 -alky radical or a polyisobuty1 radical having 16 to 3000 carbon atoms. The reaction of the condensation product from reaction step (A) with the at least one 10 long-chain-substituted phenol is effected in reaction step (B) at higher temperatures than in reaction step (A), i.e. at 30 to 120"C, especially at 35 to 105*C, in partoular at 40 to 90*C. Preference is given to working at standard pressure. The reaction Is effected advantageously in an inert organic solvent or a mixture of such solvent, especially an aromatic hydrocarbon such as toluene, xylene or a technical mixture of 15 relatively high-boiling aromatic hydrocarbons, for example SolvessoM 100, 150, 200, 150 ND or 200 ND. The reaction time is typically 1 to 10 hours. The stoichiometric ratio of phenol to diarmne used in reaction step (A) is preferably 1.5: 1 to 3.0: 1, especially '1.75 : 1 to 2.75 : 1, in particular 1.9 : 1 to 2.6 : 1, 20 The product obtained in reaction step (B) has, or has predominantly, the structure of a bistetrahydrobenzoxazine of the general formula 11 2 Rt RR R, A, in wich 25 x is the number 1, 2 or 3, RI denotes identical or different C- to Czaorhydrocarbyl radicals, where each benzene ring bears at least one C06 to Caohydrocarbyl radical, 30

R

2 denotes hydrogen or identical or different Cr to G-alkyl radicals, and A is a bridging member having I to 20 carbon atoms, 35 and ring-opened forms of the bistetrahydrobenzoxazines of the general formula Il resulting from hydrolysis of one or both tetrahydrooxazine rings, where R" are the substtuents of the phenol used, R 2 is the radical of the aldehyde used, and A corresponds to the bridging member A in the general formWa for the diamine H2N-A-NH.

10 In the compounds iI, it is also possible for different R1 substituents to occur when mixtures of different phenols are used in reaction step (B). 5 A typical example of a bistetrahydrobenzoxazine of the general formula I is the compound of the formula Ia reproduced below: R N C (Hla) 10 in which R, is, for example, tert-octyt n-nony, n-dodecyl or polyisobutyl having an Mn of 1000. Reaction step (C) is undertaken by heating the reaction product from reaction step (B) to temperatures distinctly above those of step (B). Preference is given here to working 15 at 150 to 250*C, especially at 175 to 230*C, in particular at 190 to 2200C, and preferably at standard pressure. The heating to the temperature range specified is effected for at least 10 minutes, preferably for at least 30 minutes, in particular for 45 to 120 minutes. The bistetrahydrobenzoxazines II polymerize essentially with opening of tetrahydrooxazne rings and form a higNy branched - but not arosslinked to the extent 20 that it is sparingly soluble or insoluble in mineral oil media - twc to threedimenslonal polymer system. The heating of the reaction product from reaction step (B) is effected in reaction step (C) advantageously in an inert organic solvent or a mixture of such solvents, especially 25 an aromatic hydrocarbon such as toluene, xylene or a technical mixture of higher boiling aromatic hydrocarbons, for example SoLvessoM 100, 150, 200, 150 ND or 200 ND. A typical example of a polytetrahydrobenzoxazine formed in reaction step (C) is 30 reproduced below as the compound of the general formula la: 11 N R N N OH OH HO Ri R1 R a The substituents R, are each as defined above; it is also possible for different substituents R 1 to occur in the molecule when mixtures of different phenols are used in reaction step (B). The serial number n typically assumes values of 2 to 10, especialLy 4 5 to 8, In the inventive polytetrahydrobenzoxazlnes, the ends of the side chains usually still consist of closed tetrahydrooxazine rings, As a result of hydrolysis of some or all tetrahydrobenzoxazine rings still present in the end product, the inventive 10 polytetrahydrobenzoxazines may, however, also have ring-opened forms. Whether such a hydrolytic ring opening occurs depends substantially on the boundary conditions of the polymerization in reaction step (0) - for example the moisture content and the presence of compounds with catalytic ring-opening action, such as protons or Lewis acids, 15 The inventive polytetrahydroberzoxazines preferably have a number-average molecular weight (Mr) of 700 to 50 000, especially of 1500 to 25 000, in particular of 2500 to 10 000, and a polydispersity index (PDM) of 1.5 to 7.5, preferably of 2.0 to 5;0. 20 To modify or improve the efficacy as fuel or lubricant additives, the polytetrahydrobenzoxazines described can be subsequently quatemized, Therefore, the present invention also provides quaternized polytetrahydrobenzoxazines which are obtainable by the reaction steps (A), (B) and (C) described, and additionally the reaction step 25 (D) quaterniz'ng some or all quaternizable amino functions of the reaction product front reaction step (C), The quatemizable amino functions in the polytetrahydrobenzoxazines described are 30 the tertiary nitrogen atoms.

12 Useful quaternizing agents are in principle all compounds suitable as such. in a preferred embodiment, the inventive quatem[zed polytetrahydrobenzoxazines are obtainable in reaction step (D) by quaternizing with at least one epoxide, 5 This epoxide is preferably a hydrocarbyl epoxide whose four substitutents are the same or different and are each hydrogen or hydrocarbyl radicals, whore the hydrocarbyl radicals each have 1 to 10 carbon atoms and at least one such hydrocarby1 radical must be present. More particularly, these are aliphatic or aromatio radicals, for example linear or branched Cr to C 1 u-aIkyl radicals, or aromatic radicals such as phenyl or C, 10 to C4alkyiphenyt. Suitable such hydrocarbyl epoxides are, for example, aliphatic and aromatic alkyiene oxides, such as especially C? to Cialkylene oxdes, e.g. ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 2-methyl-1,2-propene oxide (isobutene 15 oxide),. 1,2-pentene oxide, 2,3-pentene oxide, 2-nethyl1,2-butene oxide, 3-methyl-1,2 butene oxide, 1,2-hexene oxide, 2,3-hexene oxide, 3,4-hexene oxide, 2-methyl-1,2 pentene oxide, 2-ethyl-1,2-butene oxide, 3-methyb1,2-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 oxide, especialy 20 styrene axide or 4-methylstyrene oxide. In the case of use of epoxides as quaternizing agents, they are usually used in the presence of free acids, especially in the presence of free erotic acids, such as in particular with Cr to Co -monocarboxylic acids, e.g. formic acid, acetic acid or 2:5 propionic acid, or C2- to Cu-dicarboxylic acids, e.g, oxaic acid or adipic acid, or else in the presence of sulfonic acids, e.g. benzenesulfonic acid or toluenesufonic acid, or aqueous mineral acids, e.g. sulfuric acid or hydrochloric acid, To perform the quaternization, the polytetrahydrobenzoxazine from reaction step (C) is 30 admixed typicaly with at least one epoxide, especially in the stoichiometric amounts required to achieve the desired quatemization. Per equivalent of quatemizable tertiary nitrogen atom, it is possible to use, for example, 0.1 to 1,5 equivalents, or 0.5 to 1.25 equivalents, of quaternizing agent. More particularly, however, approximately equinolar proportions of the epoxide are used to quatemize a tertiary amine group. 35 The temperatures employed here are typically in the range from 15 to 90C, especially from 20 to 80C or from 30 to 70*C. The reaction time may be in the region of a few minutes or a few hours, for example about 10 minutes up to about 24 hours. The reaction can be effected at a pressure of about 0.1 to 20 bar, for example I to 10 or 1,5 to 3 bar, but especially at approximately standard pressure. More particuilary, an inert 40 gas atmosphere, for example nitrogen, is appropriate. If required, the reactants can be initially charged in a suitable inert organic aliphatic or aromatic solvent or a mixture of such solvents for the quaternization, or a sufficient 13 proportion of solvent from reaction step (C) is still present. Typical examples of suitable solvents are those of the abovementioned SolvessoTO series, and also toluene or xyiene. 5 The present invention also provides a process for preparing polytetrahydrobenzoxazines, which comprises successively performing the reaction steps already described above, namely (A) reacting at least one diamine of the general formula H2N-A-NH 2 , in which the 10 bridging member A is C to C0oalkylene which may be interrupted by up to 10 oxygen atoms andfor tertiary nitrogen atoms, C2- to C2s-alkenylene, Cs to C0q cycloalkylene, Cr to Cn-arylene or C7- to CO-araikylene with at least one C- to Ciraldehyde and at least one Cr to C-aikanol at a temperature of 20 to 80"C with elimination and removal of water, where both the aldehyde and the alcohol 15 may be used in each case in more than double the molar amount compared to the diamine: (B) reacting the condensation product from reaction step (A) with at least one phenol which bears at least ore long-chain substituent having 6 to 3000 carbon atoms in 20 a stoichiometric ratio to the diamine originally used in step (A) of 1.2: 1 to 3.5. 1 at a temperature of 30 to 120"C: (C) heating the reaction product from reaction step (S) to a temperature of 125 to 280'C for at least 10 minutes. 25 In a preferred embodiment, a further characterizing feature of this process for preparing quaternized polytetrahydrobenzoxazines is that reaction steps (A), (B) and (C) and additionally the reaction step also already described in detail above, namely 30 (D) quaternizing some or all quatemizable amino functions of the reaction product from reaction step (C), are performed successively, 35 The inventive polytetrahydrobenzoxazines can aternatively also be defined by their general chemical structure. Accordingly, the present invention provides polytetrahydrobenzoxazines of the general formula I 14 0 Q HO R HO RH HO< R' XA <A ' R^' R in which 5 x is the number 1, 2, 3 or 4, where the values of x may be different on the different aromatic rings, n is an integer from 2 to 10, especially from 4 to 8, 10 RI denotes identical or different Cr to C%on-hydrocarbyl radicals, where each benzene ring bears at least one C- to C~owrhydrooarby radical,

R

2 denotes hydrogen or identical or different Ci- to Cialkyl radicals, 15 A is a bridgng member having 2 to 20 carbon atoms and Q is the radical of a tetrahydrobenzoxazine unit which is attached via a nitrogen atom and which may be present in cyclic form according to the formula R KO NN 20 or in rngopened form resulting from hydrolysis of the tetrahydrooxazine ring, where the variables R1 R 2 and x are each as defined above. In this formula, R! are the substituernts of the phenol used in the above-described reaction step (3), R 2 is the 25 radical of the aldehyde used in the reaction step (A) described above, and A corresponds to the bridging member A in the general formula for the diamine H2N-A-NH 2 used in the above-described reaction step (A), Since the bistetrahydrobenzoxazines described, as intermediates and also as potential 30 fuel and lubricant additives, are new compounds, the present invention likewise provides bistetrahydrobenzoxazies of the general formula II 15 RR R N-PA R2 -< P(1) in which x is the number 1, 2, 3 or 4, where the values of x may be different on the two different 5 aromatic rings, R1 denotes identical or different C- to Csacrhydrocarbyl radicals, where each benzene ring bears at least one C- to C3-mrhydrocarbyl radical, 10 R2 denotes hydrogen or identical or different C- to C-alkyl radicals, A is a bridging member having 2 to 20 carbon atoms, and ring-opened forms of the bistetrahydrobenzoxazines of the general formula il 15 resulting from hydrolysis of one or both tetrahydrooxazine rings, where R 1 are the substitutents of the phenoa used in the above-described reaction step (B), R2 is the radical of the aldehyde used in the above-described reaction step (A), and A corresponds to the bridging member A in the general formula for the diamine H2N-A-NH 2 used in the above-described reaction step (A). 20 The inventive polytetrahydrobenzoxazines and quaternized polytetrahydrobenzoxazines and the inventive bistetrahydrobenzoxazines are outstandingly suitable as fuel additives or lubricant additives. Fuels in which the inventive poiytetrahydrobenzoxazines or quaternized polytetrahydrobenzoxazines or 25 the inventive bistetrahydrobenzoxazines can be used as a fuel additive here are especially gasoline fuels and middle distillate fuels, and here in particular diesel fuels and heating oils. To a very particular degree, the inventive polytetrahydrobenzoxazines and quaternized 30 polytetrahydrobenzoxazines and the inventive bistetrahydrobenzoxazines are suitable as a detergent additive for diese fuels. Especially in their capacity as a detergent additive for diesel fuels, the inventive polytetrahydrobenzoxazines and quaternized polytetrahydrobenzoxazines and the 35 inventive bistetrahydrobenzoxazines find use as an additive for reducing the level of or preventing deposits in injection systems of direct-injection diesel engines, especially in common-rail injection systems, for reducing fuel consumption of direct-injection diesel engines, especially of diesel engines with common-rail injection systems, and/or for 16 minimizing power loss in direct-injection diesel engines, especially in diesel engines with common-rail injection systems, The present invention also provides an additive concentrate which comprises, in 5 combination with further fuel additives, especially diesel fuel additives, at least one inventive polytetrahydrobenzoxazine or quatemized polytetrahydrobenzoxazine, or an inventive bistetrahydrobenzoxazine. The inventive polytetrahydrobenzoxazines or quaternized polytetrahydrobenzoxazine 10 or the inventive bistetrahydrobenzoxazines are present in the inventive additive concentrate preferably in an amount of 0.1 to 100% by weight, more preferably of I to 80% by weight and especially of 10 to 70% by weight, based on the total weight of the concentrate, 15 The present invention further provides a fuel composition, especially a diesel fuel composition, which comprises, in a majority of a customary base fuel, especially of a diesel fuel an effective amount of at least one inventive polytetrhydrobenzoxazine or quaternized polytetrahydrobenzoxazine or of an inventive bistetrahydrobenzoxazine. 20 The present invention further provides a lubricant composaion, which comprises, in a majority of a customary lubricant formulation, an effective amount of at least one inventive polytetrahydrobenzoxazine or quaternized polytetrahydrobenzoxazine or of an inventive bistetrah-iydrbenzoxazine. 25 Useful gasoline fuels include all commercial gasoline fuel compositions. Typical representatives which shall be mentioned here include the market standard Eurosuper base fuel to EN 228. Further possible fields of use for the Present invention are also gasoline fuel compositions of the specification according to WO 00/47698. 30 Useful middle distillate fuels include all commercial diesel fuel and heating oil compositions, Diesel fuels are typically mineral ol raffinates which generally have a boiling range of from 100 to 400*. These are usually distillates having a 95% point up to 360*C or even higher, However, they may also be so-called "Ultra low sulfur diesel" or "City diesel, characterized by a 95% point of, for example, not more than 345vC and 35 a sulfur content of not more than 0,005% by weight, or by a 95% point of, for example, 285*C and a sulfur content of not more than 0.001 % by weight. In addition to the diesel fuels obtainable by refining, whose main constituents are relatively long-chain paraffins, those obtainable by coal gasification or gas liquefaction ["gas to liquid" (GTL) fuels are suitable. Also suitable are mixtures of the aforementioned diesel fuels with renewable 40 fuels such as biodiesel or bioethanol. Of particular interest at the present time are diesel fuels with a low sulfur content, i e. with a sulfur content of less than 0.05% by weight, preferably of less than 0,02% by weight, in particular of less than 0-005% by weight and especially of less than .OI % by weight of sulfur. Diesel fuels may also 17 comprise water, for example in an amount up to 20% by weight, for example in the form of diesel-water microemulsions or as so-called "white diesel". Heating oils are, for example. low-sulfur or sulfur-rich mineral oil raffinates or 5 bituminous coal or brown coal distillates which typicaly have a boiling range of from 150 to 400*C. Heating oils may be standard heating oil according to DIN 51603-1, which has a sulfur content of from 0.005 to 02% by weight, or they are low-sulfur heating oils having a sulfur content of from 0 to 0.005% by weight. Examples of heating oi include especially heating oil for domestic oil-fired boilers or EL heating oil. 10 The inventive polytetrahydrobenzoxazines or quaternized poiytetrahydrobenzoxazines or the inventive bistetrahydrobenzoxazines can either be added to the particular base fuel, especially the gasoline or the diesel fuel, alone or in the form of fuel additive packages, for example the so-called diesel performance packages. Such packages are 15 fuel additive concentrates and generally comprise, as well as solvents, also a series of further components as coadditives. for example carrier oils, cold flow improvers, corrosion inhibitors, demulsiflers, dehazers, antifoams, further cetane number improvers, further combustion improvers, antoxidants or stabilizers, anistats, metallocenes, metal deactivators, solubilizers, markers and/or dyes. 20 In a preferred embodiment, the additized gasoline or diesel fuel comprises, in addition to the inventive polytetrahydrobenzoxazines or quatemized polytetrahydrobenzoxazines or inventive bistetrahydrobenzoxazines, as further fuel additives, especially at least one (further) detergent additive, referred to hereinafter as 25 component (D). Detergents or detergent additives (D) typically refer to deposition inhibitors for fuels, The detergents are preferably amphiphilic substances which have at least one hydrophobic hydrocarbyl radical having a number-average molecular weight (M,) of 85 30 to 20 000, especially of 300 to 5000 and in particular of 500 to 2500., and at least one polar moiety which is selected from (Da) mono- or polyamino groups having up to 6 nitrogen atoms, at least one nitrogen atom having basic properties; 35 (Db) nitro groups, optionally in combination with hydroxyl groups; (Dc) hydroxyl groups in combination wih mono- or polyamino groups, at least one nitrogen atom having basic properties; 40 (Dd) carboxyl groups or their alkali metal or alkaline earth metal salts; (De) sutfo groups or their alkali metal or alkaline earth metal salts; 18 (Df) polyoxy-G0-Caikylene moieties terminated by hydroxyl groups, mono- or polyamino groups, at least one nitrogen atom having basic properties, or by carbarmate groups; 5 (Dg) carboxylic ester groups; (Dh) moieties derived from succinic anhydride and having hydroxyl and/or amino and/or amido and/or imido groups; and/or 10 (Di) moieties obtained by Mannich reaction of substituted phenols with aldehydes and mono- or polyamines. The hydrophobic hydrocarbon radical in the above detergent additives, which ensures 15 the adequate solubility in the fuel oil composition, has a number-average molecular weight (M,) of 85 to 20 000, especially of 300 to 5000, in particular of 500 to 2500. Useful typical hydrophobic hydrocarbyl radicals, especially in conjunction with the polar moi.eties (Da), (Dc), (Dh) and (Di), are relatively long-chain alkyl and alkenyl groups, especially the polypropeny, polybutenyl and polyisobuteny radicals each having M = 20 300 to 5000, especialy 500 to 2500, in particular 700 to 2300, Exam pies of the above groups of detergent additives include the following; Additives comprising monc~ or polyamino groups (Da) are preferably polyalkenemono 25 or poiyalkenepolyamines based on polypropene or conventional (i.e. having predominantly intema double bonds) polybutene or polyisobutene having M = 300 to 5000, When the preparation of the additives proceeds from polybutene or polyisobutene having predominantly intema double bonds (usually in the p and y positions), one possible preparative route Is by chlorination and subsequent aminahon 30 or by oxidation of the double bond with air or ozone to give the carbonyl or carboxyl compound and subsequent arnination under reductive (hydrogenating) conditions. The amines used here for the amination may be, for example, ammonia, rnonoamines or polyamines such as dimethylaminopropyllamine, ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine. Corresponding additives based on 35 polypropene are described in particular in WO-A-94/24231. Further preferred additives comprising monoamino groups (Da) are the hydrogenation products of the reaction products of polyisobutenes having an average degree of polymerization P = 5 to 100 with nitrogen oxides or mixtures of nitrogen oxides arid 40 oxygen, as described in particular in WO-A-97/03946 Further preferred additives comprising monoamino groups (Da) are the compounds obtainable from polyisobutene epoxides by reaction with amines and subsequent 19 dehydration and reduction of the amino alcohols, as described in particular in DE-A 196 20262. Additives comprising nitro groups (Db), optionally in combination with hydroxyl groups, 5 are preferably reaction products of polyisobutenes having an average degree of polymerzation P = 5 to 100 or 10 to 100 with nitrogen oxides or mixtures of nitrogen oxides and oxygen, as described in particular in WO-A-96/03367 and in WO-A 96/03479, These reaction products are generally mixtures of pure nitropolyisobutenes (e.g. a, -dinitropolyisobutene) and mixed hydroxynitropolyisobutenes (ag c-nitro-s 10 hydroxypolyisobutene). Additives comprising hydroxyl groups in combination with mono- or polyamino groups (D) are in particular reaction products of polylsobutene epoxides obtainable from polyisobutene having preferably predominantly terminal double bonds and Mn = 300 to 15 5000, with ammonia or mono- or polyamines, as described in particular in EP-A 476 485, Additives comprising carboxyl groups or their aikalt metal or alkaline earth metal seats (Dd) are preferably copolymers of C2-eciefns with maleic anhydride which have a 20 total molar mass of 500 to 20 000 and some or all of whose carboxyl groups have been converted to the alkali metal or alkaline earth metal salts and any remainder of the carboxyl groups has been reacted with alcohols or amines, Such additives are disclosed in particular by EP-A-307 815, Such additives serve mainly to prevent valve seat wear and can, as described in VV-A-87/01126, advantageously be used in 25 combination with customary fuel detergents such as poly(so)buteneamires or polyetheram ines. Additives comprising sulfo groups or their alkali metal or alkaline earth metal salts (De) are pref-ably alkali metal or alkaline earth metal salts of an alkyl sulfosuccinate, as 30 described in particular in EP-A-639 632. Such additives serve mainly to prevent valve seat wear and can be used advantageously in combination with customary fuel detergents such as poly(so)buteneamines or polyetheramines. Additives comprising poiyoxy-CzCrakyiene moietes (Df) are preferably poiyethers or 35 polyetherarnines which are obtainable by reaction of C0C6kanols. CeC alkanediots, mono- or di-Cr-ralkyiamines, CrC-alkyicyclohexanois or CrCwu alkylphenols with 1 to 30 mol of ethylene oxide 2nd/or propylene oxide and/or butylene oxide per hydroxyl group or amino grup and, in the case of the polyetheramines, by subsequent reductive amination with ammonia, monoamines or polyamines. Such 40 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, isotidecanol 20 butoxylates, isononylphenoi butoxylates and polyisobutenol butoxylates and propoxylates and also the corresponding reaction products with ammonia, Additives comprising carboxylic ester groups (Dg) are preferably esters of mono-, di- or 5 tricarboxylic acids with long-chain alkanols or polyols, in particular those having a minimum viscosity of 2 mms at 100*C, as described in particular in DE-A-38 38 918. The mono-, di- or tricarboxylic acids used may be aliphatic or aromatic acids, and particularly suitable ester alcohols or ester poiyols are tong-chain representatives having, for example, 6 to 24 carbon atoms. Typical representatives of the esters are 10 adipates, phthalates, Isophthalates, terephthalates and trimellitates of isooctanoi, of isononanoi, of isodecanol and of isotridecanolt Such products also have carrier oii properties. Additives comprising moieties derived from succinic anhydride and having hydroxyl 15 and/or amino and/or amido and/or imido groups (Dh) are preferably corresponding derivatives of alkyl- or alkenyl-substituted succinic anhydride and especially the corresponding derivatives of polyisobutenysuccinic anhydride which are obtainable by reacting convention or high-reactivity polyisobutene having K = 300 to 5000 with maleic anhydride by a thermal route or via the chlorinated polyisobutene, Of particular 20 interest in this context are derivatives with aliphatic polyamines such as especially ethylenediamine, diethylenetriamirne, triethylenetetramine or tetraethylenepentamine The moieties having hydroxy and/or amino and/or amido and/or imido groups are, for example, carboxylic acid groups, acid amides of monoamines, acid amides of di- or polyamines which, in addition to the amide function, also have free amine groups, 25 succinic acid derivatives having an acid and an amide function, carboximides with monoamines, carboximides With di- or polyarnmnes whIch, in addition to the imide function, also have free amine groups, or dilmides which are formed by the reaction of di- or polyamnMes with two succinic acid derivatives, Such fuel additives are common knowledge and are described especially in US-A-4 849 572. 30 The detergent additives from group (Dh) are preferably the reaction products of alkyl or alkeny-substituted succinic anhydrides, especially of polyisobutenylsuccinic anhydrides, wfth amines and/or alcohols. These are thus derivatives which are derived from alkyi-, alkenyl- or polyisobutenylsucinic anhydride and have amino and/or amido 35 and/or imido and/or hydroxyl groups. It is self-evident that these reaction products are obtainable not only when substituted succinic anhydride is used., but also when substituted succinic acid or suitable acid derivatives, such as succinyl halides or succinic esters, are used. 40 The add itized fuei preferably comprises at least one detergent based on a polyisobutenyl-substituied succinimide. Especially of interest are the imides with aliphatic polyamines,. Particularly preferred polyamines are ethylenediamine, diethylenetriamine, triethylenetetrarnine, pentaethylenehexamine and in particular 21 tetraethylenepentamine. The polyisobutenyl radical has a number-average molecular weight Mr of preferably from 500 to 5000, more preferably from 500 to 2000 and in particular of about 1000, 5 Additives comprising moieties (Di) obtained by Mannich reaction of substituted phenols with aldehydes and mono- or polyamines are preferably reaction products of polyisobutene-substituted phenols with formaldehyde and mono- or polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or dimethylaminopropylamine The polyisobutenyi-substituted phenols may originate 10 from conventional or high-reactiity polyisobuterie having M, = 300 to 5000. Such "polyisobutene Mannich bases' are described especially in EP-A-831 141. The detergent additives (D) mentioned are preferably used together with the inventive polytetrahydrobenzoxazines or quaterized polytetrahydrobenzoxazines or the 15 inventive bistetrahydrobenzoxazines in combination wih at least one earrer oit Suitabke mineral carter oiIs are the fractions obtained in crude oil processing, such as brightstock or base oils having viscosities, for example, from the SN 500 - 2000 class; but also aromatic hydrocarbons, paraffinic hydrocarbons and alkoxyalkanols Likewise 20 useful is a fraction which is obtained in the refining of mineral oil and is known as "hydrocrack air (vacuum distillate cut having a boiling range of from about 360 to 500*C, obtainable from natural mineral oil which has been catalytically hydrogenated under high pressure and isomerized and also deparaffinized). Likewise suitable are mixtures of abovementioned mineral carrier oils 25 Examples of suitable synthetic carrier oils are selected from: polyolefins (poly-alpha olefins or poly(intemal olefin)s), (poly)esters, (poly)alkoxylates, polyethers, aliphatic polyetheramines, alkylphenobstarted polyethers, alkylphenol-started polyetheramines and carboxylic esters of long-chain aikanois. 30 Examples of suitable polyolefins are olefin polymers having M, = from 400 to 1800, in particular based on polybutene or polyisobutene (hydrogenated or unhydrogenated). Examples of suitable polyethers or polyetheramines are preferably compounds 35 comprising polyoxy-C2-Calkylene moieties which are obtainable by reacting CrGw alkanols, CrCaralkanediols, mono- or di-CrCw 3 -alkylamines, CI-3alkylcyclo hexanols or Csoralkylphenols with from 1 to 30 mol of ethylene oxide and/or propylene oxide and/or butylene oxide per hydroxyl group or amino group, and, in the case of the polyeiheramines, by subsequent reductive amination with arnmonia, 40 moncamines or polyamines. Such products are described in particular in EP-A 310 875, EP-A 356 725, EP-A 700 985 and US-AA,877,416, For example, the polyetheramines used may be poly-Q-Cralkylene oxide amines or functional derivatives thereof. Typical examples thereof are tridecanol butoxylates or isotridecanol 22 butoxylates, isononylpheno butoxylates and also polyisobutenol butoxylates and propoxylates, and also the corresponding reaction products with ammonia, Examples of carboxylic esters of long-chain alkanols are in particular esters of mono-, 5 di- or tricarboxylic acids with long-chain alkanols or polyols, as described in particular in DE-A 36 38 918. The mono-, di- or tricarboxylic acids used may be aliphatic or aromatic acids; suitable aster alcohols or polyols are in partcular long-chain representatives havi ng, for example, from , to 24 carbon atoms. Typical representatives of the esters are adipates, phthaiates, isophthalates, terephthalates 10 and trimellitates of isooctanol, isononanol, isodecanol and isotridecanol, for example di(n- or isotridecyi) phthaiate. Further suitable carrier oii systems are described, for example, in DE-A 38 26 608, DE-A 41 42 241, DE-A 43 09 074, EP-A 0 452 328 and EP-A 0 548 617. 15 Examples of particularly suitable synthetic carrier oils are alcohokstarted polyethers having from about 5 to 35, for example from about 5 to 30, CvC-alkylene oxide units, for example selected from propylene oxide, n-butylene oxide and isobutylene oxide units, or mixtures thereof, Nonlimiting examples of suitable starter alcohols are long 20 chain alkanols or phenols substituted by long-chain alkyi in which the long-chain alkyl radical is in particular a straight-chain or branched Griralkyl radical Preferred examples include tridecanol and nonylpheno. Further suitable synthetic carrier oils are alkoxylated alkyiphenols, as described in 25 DE-A 101 02 913. Preferred carrier oils are synthetic carrier oils, particular preference being given to polyethers, 30 The inventive fuel composition comprises the inventive polytetrahydrobenzoxazines or quatemnized polytetrahydrobenzoxazines or the inventive bistetrahydroberzoxazines in an amount of typically 10 to 2000 ppm by weight, more preferably of 20 to 1000 ppm by weight, even more preferably of 30 to 500 ppm by weight and especially of 40 to 200 ppm by weight, z. B. von 50 to 150 ppm by weight 35 When the inventive polyteirahydrobenzoxazines or quaternized polytetrahydrobenzoxazines or the inventive bistetrahydrobenzoxazines are added to the fuel in combination with one or more (further) detergent additives from group (D), the total amount of these two additive types is typically 10 to 3000 ppm by weight, mare 40 preferably from 20 to 1500 ppm by weight, even more preferably from 30 to 1000 ppm by weight and especially from 40 to 500 ppm by weight, for example from 50 to 300 ppm by weight, 23 When a carrier oi is used in addition, it is added to the inventive adtdiized fuel in an amount of preferably from 1 to 1000 ppm by weight, more preferably from 10 to 500 ppm by weight and in particular from 20 to 100 ppm by weight 5 Gold flow improvers suitable as further coadditives are, for example, copolymers of ethylene with at least one further unsaturated monomer, e.g. ethylene-vinyl acetate copolymers, Corrosion inhibitors suitable as further coadditives are, for example, succinic esters, in 10 particular with polyols, fatty acid derivatives, for example oleic esters, oligomerized fatty adds and substituted ethanolamines. Demulsifiers suitable as further coadditives are, for example, the alkali metal and alkaline earth metal salts of alkyl-substituted phenol- and naphthalenesulfonates and 15 the alkali metal and alkaline earth metal salts of fatty acid, and also alcohol alkoxylates, e.g. alcohol ethoxylates, phenol alkoxylates, e.g. tert-butylphenol ethoxylales or tert pentylphenol ethoxylates, fatty acid, alkylphenols, condensation products of ethylene oxide and propylene oxide, e.g. ethylene oxide-propylene oxide block copolymers, polyethyleneimines and polysiloxanes. 20 Dehazers suitable as further coadditives are, for example, alkoxyiaed phenol formaldehyde condensates. Antifoarns suitable as further coadditives are, for example, polyether-modmfied 25 polysiloxanes, Cetane number and combustion improvers suitable as further coadditives are, for example, alkyl nitrates, e.g. cyclohexyl nitrate and especially 2-ethyihexyl nitrate, and peroxides, e.g. di-tert-butyl peroxide. 30 Antioxidants suitable as further coadditives are, for example, substituted phenols, e.g. 2,6-di-ted-butyphenol and 2,6-di-tert-buty.3-.methylpheno, and also phenylenediam ines, eg. N, N'dlsec-butyip-phenyienediamine. 35 Metal deactivators suitable as further coadditives are, for example, salicylic acid derivatives, e.g. NN-disalicyiidene-2-propanediamine. Suitable solvents, especially for fuel additive packages, are, for example, nonpolar organic solvents, especially aromatic and aliphatic hydrocarbons, for example toluene, 40 xylenes, "white spirit" and the technical solvent mixtures of the designations Shellsolo (manufacturer: Royal Dutch / Shell Group), Exxol@ (manufacturer: ExxonMobil) and Solvent Naphtha. Also useful here, especially in a blend with the nonpolar organic 24 solvents mentioned, are polar organic solvents, in particular alcohols such as 2 ethyihexanol, decano[ and isotridecanol. When the coadditives and/or solvents mentioned are used in addition in gasoline or 5 diesel fuel, they are used in the amounts customary therefor. The inventive polytetrahydrobenzoxazines and quaternized poiytetrahydrobenzoxazines and the inventive bistetrahydrobenzoxazines are also particularly advantageously suitable as a lubricant additive. Lubricants or lubricant 10 compositions are intended to refer here to motor olU, lubricant ol s, transmission oils including manual and automatic oils, and related liquid compositions which serve to lubricate mecha nically moving parts - usually in metal form. The inventive polytetrahydrobenzoxazines and quaternized polytetrahydrobenzoxazines and the inventive bistetrahydrobenzoxazines act principally as dispersant additive and/or as 15 detergent additive In the lubricant compositions. The inventive lubricant composition comprises the inventive polytetrahydrobenzoxazines or quatemized polyttrahydrobenzoxazines or the inventive bistetrahydrobenzoxazines in an amount of typically 0.001 to 20% by weight, 20 preferably 0.01 to 10% by weight, especially 0.05 to 8% by weight and in particular 0.1 to 5% by weight, based on the total amount of the lubricant composition. The economically most important lubricant compositions are motor oils, and also transmission oils including manual and automatic oils. Motor oils consist typically of 25 mineral base oils which comprise predominantly paraffinic constituents and are produced in the refinery by costly inconvenient workup and purification processes, having a fraction of approx 2 to 10% by weight of additives (based on the active substance contents). For specific applications, for example high-temperature applications, the mineral base oils may be replaced partly or fully by synthetic 30 components such as organic esters, synthetic hydrocarbons such as olefin oligomers, poly-a-olefins or polyoiefins of hydrocracking oils. Motor oils also have to have sufficiently high viscosities at high temperatures in order to ensure impeccable lubrication effect and good sealing between cylinder and piston. Moreover, the flow properties of motor oils have to be such that the engine can be started without any 35 problem at low temperatures. Motor oiis have to be oxidation-stable and must generate only small amounts of decomposition products in liquid or solid form and deposits even under difficult working conditions. Motor oils disperse solids (dispersant behavior), prevent deposits (detergent behavior), neutralize acidic reaction products and form a wear protective film on the metal surfaces in the engine. Motor oils are typically 40 characterized by viscosity classes (SAE classes). With regard to their base components and additives, transmission oils including manual and automatic oiis have a similar composition to motor oils. The force is transmitted in 25 the gear system of gearboxes to a high degree through the liquid pressure in the transmission oil between the teeth. The transmission oil accordingly has to be such that it withstands high pressures for prolonged periods without decomposing. In addition to the viscosity properties, wear, pressure resistance, friction, shear stability, traction and 5 running-in performance are the crucial parameters here. In addition to the inventive polytetrahydrobenzoxazines or quaternized polytetrahyd robe nzoxazines or the inventive bistetrahydrobertzoxazines, motor oils and transmission oils including manual and automatic oiis generally also comprise at least 10 one, but usually some or al, of the additives listed below in the amounts customary therefor (which are stated in brackets in % by weight, based on the overall lubricant composition): antioxidants (0.1 to 5%): 1:5 sulfur compounds, for example reaction products of terpenes (a-pfnene), resin oils or low molecular weight polybutenes with sulfur, dialky sulfides, dialkyl trisufides, polysuifides, diaryl sulfides, modified thiols, mercaptobenzimidazoles, mercaptotriazines, thiophene derivatives, xanthates, zinc dialkyldithiocarhamates, 20 thioglycols, thioaldehydes, dibenzyl disulfide, alkylphenol sulfides, dialkylphenol sulfides or sulfur-containing carboxylic acids phosphorus compounds, for example triaryl and trialkyl phosphites, dialkyi 3,5-di tet-butyl-4-hydroxybenzylphosphonate or phosphonic acid piperazides 25 sulfur-phosphorus compounds, for example zinc dialkyldithiophosphates (metal dialkyldithiophosphates also act as corrosion inhibitors and high-pressure additives in lubricant oils) or reaction products of phosphorus pentasuffide with terpenes (c pinene, dipentene), polybutenes, olefins or unsaturated esters 30 phenol derivatives, for example sterically hindered mono-, bis- or trisphenols, sterically hindered polycyclic phenols, polyaIkylphenols, 2,6-di-tert-butyl4 methyiphenol or methylene-4,4Tbis(2,6-dtert-butiphenol) (phenol derivatives are often used in combination with sulfur-based or amine-based antioxid ants) 35 mines, for example arylamines such as diphenylamine, phenya-naphthyamine or 4,4'-tetramethyldiaminodipherylmethane metal deactivators in the narrower sense, for example N-salicylideneethylamine, 40 NN'-disa licylideneethylenediamire, NN-disalicylidenedI2-propanedamine, triethylenediamine, ethylenediaminetetraacetic acid, phosphoric acd, citric acid, glycolic acid, lecithin, thiadiazole, imidazole or pyrazole derivatives 26 viscosity index improvers (0.05 to 10%), for example: polyisobutenes having a molecular weight of typically 10 000 to 45 000, polymethacrylates having a molecular weight of typically 15 000 to 100 000, homo- and copolymers of 1, 3 dienes such as butadiene or isoprene having a molecular weight of typically 80 000 5 to 100 000, 13-diene-styrene copolymers having a molecular weight of typically 80 000 to 100 000, maleic arnhydride-styrene polymers in esterified form having a molecular weight of typically 60 000 to 120 000, star-shaped polymers with block Like structure by virtue of units composed of conjugated dienes and aromatic monomers having a molecular weight of typically 200 000 to 500 000, 10 polyalkylstyrenes having a molecular weight of typically 80 000 to 150 000, polyclefins composed of ethylene and propylene or styrene-yclopentadiene norbornene terpolymers having a molecular weight of typically 60 000 to 140 000 pour point depressants (cold flow improvers) (0,03 to 1 %), for example bicyclic 15 aromatics such as naphthalene with different long-chain aikyl radicals, polymethacrylates with 12 to 18 carbon tons in the alcohol radical, a degree of branching between 10 to 30 mol% and an average molecular weight of 5000 to 500 000, long-chain alkylphenols and dialkylaryl phthalates or copolymers of different olefins 20 * detergents (HD additives) (0.2 to 4%), for example calcium naphthenates, lead naphthenates, zinc naphthenates and manganese naphthenates, calcium dichlorostearates, calcium phenylstearates, calcium chiorophenylstearates, sulfonation products of alkylaromatics such as dodecylbenzene, petroleum 25 sulfonates, sodium sulfonates, calcium sulfonates, barium sulfonates or magnesium sulfonates, neutral, basic and overbased sulfonates, phenates and carboxylates, salicylates, metal salts of alkylphenols and alkylphenol sulfides, phosphates, thiophosphates or aikanylphosphonic acid derivatives 30 * ashless dispersants (0.5 to 10%), for example Mannich condensates of alkylphenol, formaldehyde and polyalkylenepolyarnines, reaction products of poiyisobutenylsuccinic anhydrides with polyhydroxyl compounds or polyamines, copolymers of alkyi methacrylates with diethylaminoethyl methacrylate, N vinylpyrrolidone, N-vinylpyridine or 2-hydroxyethyl methacrylate or vinyl acetate 35 fumarate copolymers * high-pressure additives (extreme pressure additives) (0,2 to 2.5%), for example chlorinated paraffins with chlorine content 40 to 70% by weight, chlorinated fatty acid (especially having trichloromethyl end groups), dialkyl hydrogenphosphites, 40 triaryl phosphates, aryl phosphates such as tricresyl phosphate, dialkyl phosphates, trialkyl phosphates such as tibutyl phosphate, trialkylphosphines, diphosphoric esters, nitroaromatics, aminophenol derivatives of naphthenic acid, carbamic esters, dithiocarbamic acid derivatives, substituted 1,2,3-triazoles, mixtures of 27 benzotriazole and alkyisuccinic anhydride or aikyimaleic anhydride, 1,2,4 thiad[azole polymers, morpholinobenzothiadiazole disulfide, chlorinated alkyl sulfides, sulfurized olefins, sulfurized chloronaphthalenes, chlorinated alkyl thiocarbonates, organic sulfides and polysulfides such as bis(4-chlorobenzyl) 5 disulfide and tetrachlorodiphenyi sulfide, trichloroacrolein mercaptals or especially zinc dialkyldithiophosphates (ZDDPs) * friction modifiers (0,05 to 1%), especially polar ol-soluble compounds which generate a thin layer on the frictional surface by adsorption, for example fatty 10 alcohols, fatty amides, fatty acid salts, fatty acid alkyl esters or fatty acid glycerides * antifoam additives (0.0001 to 02%), for example liquid silicones such as polydimethylsiloxanes or polyethylene glycol ethers and sulfides 15 a demu Isfiers (0.1 to 1%), for example di nonyinaphthalenesu fonates in the form of their alkali metal and alkaline earth metal salts 0 corrosion inhibitors (also known as metal deactivators) (0.01 to 2%), for example tertiary amines and salts thereof, imino esters, amid oximes, diarninomethanes, 20 derivatives of saturated or unsaturated fatty acids with alkanolamines, alkylamines, sarcosines, imidazolines, alkylbenzotriazoles, dimercaptothiadiazole derivatives, diaryl phosphates, thiophosphoric esters, neutral salts of primary n-Cr-% aikylamines or cycloaikylamines wit dialkyl phosphates having branched ClrCe alkyl groups, neutral or basic alkaline earth metal sulfonates, zinc naphthenates, 25 mono- and dialkyiaryisulfonates, barium dinonyinaphtalenesulfonates, lanolin (wool fat), heavy metal salts of naphthenic acid, dicarboxylic acid, unsaturated fatty acids, hydroxy fatty acids, fatty acid esters, pentaerythrityi monooleates and sorbitan monooleates, 0-stearoyialkanolarnines, polyisobutenyisuccinic acid derivatives or zinc dialkyldithiophosphates and zinc dialkyldithiocarbarates 30 em.ulsifiers (0.01 to 1%), for example long-cbain unsaturated, naturally occurring carboxylic acid, naphthenic acids, synthetic carboxylic acid, sulfonamides, N oleylsarcosine, alkanesulfamidoacetic acid, dodecylbenzenesulfonate, long-chain alkylated ammonium salts such as dimethyidodecyibenzyammonium chloride, 35 imidazoiinlum salts, alkyl-, alkylaryk, acy-, alkylamino- and acylamrinopolyglycols or long-chain acyleted mono- and diethanolamines " dyes and fluorescence additives (0.001 to 02%) 40 - preservatives (0.001 to 05%) " odor improvers (0.001 to 0.2%), 28 TypicaO ready-to-use motor oli compositions and transmission oil, including manual and automatic oil, compositions in the context of the present invention have the following composition, the data for the additives relating to the active substance contents and the sum of all components always adding up to 100% by weight. IV 80 to 99:3% by weight, in particular 90 to 98% by weight of motor oil base or transmission oil, including manual and automatic oil, base (mineral base oils and/ar synthetic components) including the fractions of solvent and diluent for the additives 10 * 0.1 to 8% by weight of inventive polytetrahydrobenzoxazines or quaterized polytetrahydrobenzoxazines or the inventive bistetrahydrobenzoxazines * 0.2 to 4% by weight, in particular 13 to 2.5% by weight of detergents of group (d) 15 * 0,5 to 10% by weight, in particular 1,3 to 6.5% by weight of dispersants of group (C) * 0,1 to 5% by weight, in particular 0.4 to 2,0% by weight of antioxidants of group 20 (a) and/or high-pressure additives of group (f) and/or friction modifiers of group (g) * 0.05 to 10% by weight, in particular 0.2 to 1.0% by weight of viscosity index improvers of group (b) 25 * 0 to 2% by weight of other additives of groups (c) and (h) to (n), The invention wil be llustrated in detail with reference to the nonrestrictive examples which follow. 30 Preparation examples Example I [reaction step (A)l 35 250 g (3s37 mol) of isobutanol and 60 g (2.0 mol) of paraformaldehyde were suspended at 20'C in 250 g of cyclohexane. This was followed by the addition of 30 g (0.50 mci) of 1,2-ethylenediamin, The reaction mixture was heated under reflux at 40"G under a reduced pressure of 83 mbar for 5 hours. Water eliminated was removed azeotropically from the reaction mixture. A conversion of 75% was determined from the 40 amount of water eliminated. After the cyclohexane solvent and the excess isobutano had been distilled off, a product mixture comprising compounds IlIla, IliIb and IIc (in a weight ratio of I : 0.7 :04) as main products was obtained: 29 rOH N 0 HOO 0 0 (I lib) 5HO ~N N O0H Also present in minor amounts in this product mixture are the corresponding tetAMs (hydroxymethyi)ethylenediamine etterified with isobutanol on only one hydroxymethyl moiety, and the corresponding tris(hydroxymethyl)ethyoenediamine etherified with 10 isobutanol on ory one hydroxymethyl moiety. This product mixture shows, in the +H NMR spectom (CDCL, i in ppm) the fbowlng significant signals: 1 5 for lia: 0.9 (m, -CH), 1 .83 (mi, -CH-(CH3)), 2.9 (s, -NCH 2 CH2-), 3.25 (d, -OCH-) and 4.18 (s, -NCH 2 0-); for 111b: 0.9 (:m, -CH), 1 3 (m, -CH-(CHX)2), 3,0 (s, -NCH&2CH2N), 3.25 (d, -OCHr) and 4.3 (s, -NCH 2 0-); 20 for 1c1: 37 (s, -NCH 2 CH2N-) and 3.8 (s, -NCH2N-). Example 2 [reaction step (B)) 25 The product mixture prepared in example I was dissolved together with 262 g (1.0 mol) of 4-ndodecylphenol in 525 g of SovessoM 150, and heated to 90'C for 2 hours. Subsequently, the solvent was distilled off under reduced pressure. The result was a 30 bistetrahydrobenzoxazine of the tbrmula Ila (RI = n-dodecyl) which had, in the 1H NMR spectrum (CDCh, 5 in ppm), the following signals: 0.5-1,6 (m, -(CH 2 )nCH), 30 (s, -NCH2CH 2 N-), 4.0 (s, -NCHr), 4.9 (s, -OCH2N-), 6.7 5 (s, aromat. CH, meta position), 6.8 and 7,0 (d. aromat. CH, ortho and meta position). Example 3 [reaction step (B)] The product mixture prepared in example I was dissolved together with 265 g 10 (1.28 mol) of 4-tert-octyiphanoll in 520 g of toluene, and heated to 4:0' for 2 hours. Subsequently, the solvent was distilled off under reduced pressure. The result was a blstetrahydrobenzoxazine of the formula lia (RI n-tert-octy) which had, in the ^H NMR spectrum (CDCb, 6 in ppm), the following signals: 15 1.3 (s, CH 3 ), 1,7 (, -CHr), 3.0 (s, -NCH 2 CH2N-), 4.0 (a, -NCHr), 4.9 (s, -OCH2N-), 6.9 (s, arornat CH, meta position), 7.1-73 (n, aromat CH, ortho and meta position). Example 4 [reaction step (B)] 20 The product mixture prepared in example I was dissolved together with 281 g (1.29 mol) of 4-rnonyiphenol in 520 g toluene, and heated to 4040 for 2 hours. Subsequently, the solvent was distilled off under reduced pressure. The result was a bistetrahydrobenzoxazine of the formula Ila (R= n-nony!) which had, in the 1 H NMAR spectrum (CDCa, 6 in ppm), the following signals: 25 0.5-1,7 (m, -(CH 2 )CH), 3.0 (s, -NCH 2

CH

2 N-), 4.0 (s, -NCH-), 4,9 (s, -OCH 2 N-), 6.7 (s, arornat. CH, meta positIon), 6.8 and 7,0 (d, aromat. OH, ortho and meta position). Example 5 [reaction step (C)) 30 The bistetrahydrobenzoxazine from example 2 was dissolved in a weight ratio of 1: 1 in SolvessTM 150, and heated to 205*C for I hour. After the solvent had been distilled off under reduced pressure, the result was a polytetrahydrobenzoxazine of the formula la (R= n-dodecy, n = approx. 6), which had a number-average molecular weight (MW) 35 of 4600 g/mol, a number-average molecular weight (M,) of 1500 g/mo and a polydispersity index (PD1) of 3.07, and exhibited the following signals in the IH NMR spectrum (CDC, 6 in ppm): 0.5-1.6 (m, -(CH 2 )iCH), 3.0 (s, -NCH 2

CH

2 N-), 4.0 (s, -NCHr), 4.9 (s -OCH 2 N-), 6.7 40 (a, aromat CH, meta position), 6.8 and 7.0 (d, aromat. CH, meta and ortho position). Use example 31 To examine the influence of the compounds described on the performance of direct injection diesel engines operated w[th The inventive fuel composition, the power loss was determined based on the official test method CEC F-98-08. The power loss is a direct measure of formation of deposits in the injectors. 5 A conventional direct-injection diesel engine with a common-ral system was used. For more economical execution of the determinations, a shortened engine run cycle was used compared to CEC F-98-08, i.e, 1 x 12 hours of run time compared to 4 x 8 hours of run time interrupted by 3 x 8 hours of soak time of the original test method. in 10 addition, inectors which had already been run in and cleaned were used, All other test details were fulfilled as in CEG F-98-08. The fuel used was a commercial diesel fuel from Haltermann (RF-06-03 Batch 12). To synthetically induce the formation of deposits on the injectors, 2 ppm by weight of zinc 15 didodecanoate were added thereto. The additive used was the compound from example 5. The table which follows shows the results of the power loss determinations: 20 Test run No. Detergent additive Dosage Power loss, 12 h {ppm by weight of [at 4000 rpm) active substance] 25 Base value none 4.34% 1 Example 5 150 0.41% 2 Example 5 150 0.71%

Claims

2. A polytetrahydrobenzoxazine according to claim 1, obtainable in reaction step (A) from at east one diamine of the general formula H2N-(CH2)rNH 2 in which z is a number from 1 to 10. 25 3, A polytetrahydrobenzoxazine according to claim I or 2, obtainable in reaction step (A) from formaldehyde or a polymeric form of formaldehyde.
4. A polytetrahydrobenzoxazine according to claims 1 to 3, obtainable in reaction step 30 (A) frorn at least one C7 Or 4 -aikanl.
5. A polytetrahydrobenzoxazine according to claims 1 to 4, wherein the stoichiometric ratio of diamine to aldehyde in reaction step (A) is 1 : 4, where a deviation from this reaction of up to 10% can be tolerated, and the alkanol is used in at least 3.5 times 35 the molar amount compared to the diam ine.
6. A polytetrahydrobenzoxazine according to claims 1 to 5, obtainable in reaction step (B) from at least one phenol which beers, in the para position to the hydroxyl group, a Ce to Calky radical or a polyisobutyl radica! having 16 to 3000 carbon atoms. 40 33
7. A polytetrahydrobenzoxazine according to claims I to 6 having a number-average molecular weight (M) of 700 to 50 000 and a polydispersity index (PDI) of -5 to 7.5 5 8. A quaternzed polytetrahydrobenzoxazine obtainable by reaction steps (A), (B) and (C) according to claims 1 to 7 and additionally the reaction step of (D) quatemizing some or all quaternizable amino functions of the reaction product from reaction step (C). 10
9. A quaternerized polytetrahydrobenzoxazine according to claim 8, obtainable in reaction step (D) by quaternizing with at least one epoxide.
10. A process for preparing polytetrahydrobenzoxazines, which comprises successively 15 performing the reaction steps of (A) reacting at least one diamine of the general formula H2NA-NH 2 , in which the bridging member A is Ce- to C2-alkylene, Ce- to Q2-cycloalkylene, CEh to Crarylene or Cr to c-aralkylene with at least one C- to Ciradehyde 20 and at least one Cr to Cralkano at a temperature of 20 to 30*C with elimination and removal of water, where both the aldehyde and the alcohol may be used in each case in more than double the molar amount compared to the diamiie; 25 (B) reacting the condensation product from reaction step (A) with at least one phenol which bears at least one long-chain substituent having 6 to 3000 carbon atoms in a stoichiometric ratio to the diamine originally used in step (A) of 1.2: 1 to 3: 1 at a temperature of 30 to 120'C; 30 (C) heating the reaction product from reaction step (B) to a temperature of 125 to 280*C for at least 10 minutes,
11. A process for preparing quaterized polytetrahydrobenzoxazines. which comprises successively performing reaction steps (A), (8) and (C) according to claim 10 and 35 additionally the reaction step of (D) quaternizing some or al quaternizable amino functions of the reaction product from reaction step (C). 40 12. A polytetrahydrobenzoxazine of the general formula I 34 QQ HO RO, R H 0 [-N N R RR R in which x is the number 1, 2, 3 or 4, where The values of x may be different on the different 5 aromatic rings, n is an integer from 2 to 10, R 1 denotes identical or different C,- to Caro-hydrocarby radicals, where each 10 benzene ring bears at least one Ce to C 0 ar-hydrocarbyl radical, R2 denotes hydrogen or identical or different Cr to C raikyi radicals, A is a bridging member having 2 to 20 carbon atoms and 15 Q is The radical of a tetrahydrobenzoxazine unit which is attached via a nitrogen atom and which may be present in cyclic form according to the formula R O R I i R 20 or in ring-opened form resulting from hydrolysis of the tetrahydrooxazine ring, where the variables R, R 2 and x are each as defined above. 13 A bistetrahydrobenzoxazine of the generaI formula i 25 262 RR N RR 2 0 R in which x is the number 1, 2, 3 or 4, where the values of x may be different on the two 30 different aromatic rings, 35 R denotes identical or different C- to Cn-hydrocarbyl radicals, where each benzene ring bears at least one C- to C-rhydrocarby radical, 5 R denotes hydrogen or identical or different C- to C-alkyl radicals, A is a bridging member having 1 to 20 carbon atoms., and ring-opened forrns of the bistetrahydrobenzoxaZnes of the general formula 11 10 resulting from hydrolysis of one or both tetrahydrooxazine rings.
14. The use of the polytetrahydrobenzoxazine or quatemLzed polytetrahydrobenzoxazines or bistetrahydrobenzoxazines according to claims I to 13 as a fuel additive or liu bricant additive. 15
15. The use according to claim 14 as a detergent additive for diesel fuels,
16. The use according to claim 15 as an additive for reducing or preventing deposits in injection systems of direct-injection diesel engines, especially in common-rail 20 injection systems, for reducing fuel consumption of direct-injection diese engines, especially of diesel engines wilt common-rail injection systems, and/or for minimizing power loss in direct-injection diesel engines, especially in diesel engines with common-rail injection systems. 25 17. An additive concentration comprising, in combination with further fuel additives, especially diesel fuel additives, at least one polytetrahydrobenzoxazine or quatemized polytebahydrobenzoxazine or bistetrahydrobenzoxazine according to claims I to 13. 30 18, A base fuel composition comprising, in a majority of a customary base fuel, an effective amount of at least one polytetrahydrobenzoxazine or quatemnized polytetrahydrobenzoxazine or bistetrahydrobenzoxazine according to claims 1 to 35 19. A base lubricant composition comprising, in a majority of a customary base lubricant, an effective amount of at least one polytetrahydrobenzoxazine or quaternized polytetrahydrobenzoxazine or bistetrahydrobenzoxazine according to claims I to 13.