MXPA99004112A - Polyolefins and their functionalized derivatives - Google Patents

Abstract

The present invention relates to at least simply unsaturated polyolefins with a number mean molecular weight in the range of 400 to 1,500 dalton and a dispersibility of MW/MN<1,2, obtained through catalytic dimerization from at least simply unsaturated olefin-oligomers, as well as to the method for their production. The present invention further relates to derivatives of these polyolefins which can be obtained by functionalizing at least a double link of the polyolefin. The invention also relates to the use of polyolefins and/or functionalization products as additives for fuels or lubricants.

Description

POLIOLEPHINS AND THEIR DERIVATIVES --X-NCIONA-LIZADOS The present invention relates to the onoolefinic unsaturated polyolefins and their functionalized derivatives and their use as fuel and lubricant additives or as additive concentrates. The carburetors and intake systems of gasoline engines, as well as injection systems for dosing fuel in gasoline and diesel engines are becoming increasingly contaminated by impurities. Impurities are caused by dust particles coming from the air sucked by the engine, hot exhaust gases from the combustion chamber, ventilation gases from the crankcase that pass to the carburetor and high-boiling substances and fuel stabilizers .

This waste displaces the air / fuel ratio during a cold start, during idling and in the load range in the lower part - so that the mixture is difficult to adjust and the combustion becomes more incomplete. As a result of this, the proportion of unburned or partially burned hydrocarbons in the exhaust gas and gasoline consumption increases. It is known that fuel additives to keep valves and the carburetor or clean injection systems are used to avoid these disadvantages (see, for example: M. Rossenbeck in Katalysatoren, Tenside, Mineraldladditive, editors J. Falbe, U. Hasserodt, page 223, G. Thieme verlag, Stuttgart 1978). Depending on the mode of action and the preferred place of action of these detergent additives, a difference is now made between two generations. The first generation of additives could only prevent the formation of deposits in the intake system but not eliminate the existing deposits. On the other hand, the additives of the second generation can avoid and eliminate deposits (effect keep clean and clean) .. This is allowed in particular for its excellent thermostability in areas of relatively high temperature, in particular in the intake valves. The principle of molecular structure of these second-generation additives that act as detergents is based on the bonding of polar structures with non-polar or olefinic radicals [sic], of generally higher molecular weight. However, it has been found that the polyolefins themselves are suitable for this purpose, as long as they have adequate molecular weights. Common functionalized polyolefins are polyalkylene amines (see, for example EP-A 244 616, EP-A 476 485 EP 539 821, WO 92/12221, WO 92/14806, WO 94/24231 or German Panther 3,611,230). the derivatives of these amines are suitable, for example, the ß-aminonitriles of the general formula: R Rd Ra CH2 N C C CN H | | R ° H wherein Ra is an aliphatic hydrocarbon radical having alkyl side groups and a number average molecular weight MN from 250 to 5000 and Rb, Rc and Rd independent from each other, each being hydrogen or C? -Cg alkyl or R? R is phenyl. These compounds are described, for example, in EP-A 568 873. The functionalized hydroxyl polyolefins (see, for example, EP-A 277 345 and the literature mentioned therein) and their derivatives which are obtainable by functionalization of the OH groups are also adequate. Another class of additives consists of succinic anhydrides substituted with polyalkyl and their derivatives (see, for example, DE-A 27 02 604). All mentioned derivatives are obtained by functionalization of polyolefins that also contain a reactive double bond. It has been found that polyolefins having molecular weights below 400 dalton and their functionalized derivatives have only small cleaning effects, while polyolefins with molecular weights greater than 1500 dalton and their derivatives They tend to cause the valves to stick. A narrow molecular weight distribution of polyolefins, characterized by a dispersity Mw / M? <; 1-2 (ratio of the weight average molecular weight Mw to the number average molecular weight N) is advantageous since the upper molecular weight range is not pronounced in the case of a low dispersity. The prior art discloses that monoethylenically unsaturated polyolefins having molecular weights from 400 to 1500 dalton and a reduced dispersity to a lower limit of 1.4 can be prepared by cationic polymerization. Even narrower molecular weight distributions (Mw / fTN: 1.2-1.4) can be obtained by anionic polymerization and latent cationic polymerization. Polyolefins having a narrower molecular weight distribution M "/ MN < 1.2 are, in principle, obtainable by distillation methods, but only compounds having a molecular weight of < 400 dalton (C? S) can be obtained in this way. The monoethylenically unsaturated polyolphefins having molecular weights above 400 dalton and a dispersity MM / MN < 1.2 are- to date unknown. Therefore, the same applies to the functionalized polyolefins that are obtained from these. For example, US-A 5286823 describes the monoethylenically unsaturated polyisobutenes having molecular weights from 500 to 5000 dalton in combination with a "MW / MN <2" dispersity. In the examples a polyisobutene with a number average molecular weight MW / MN of 840 dalton with MW / MN = 1.3 is described. US-A 5,068,490 describes a process for the preparation of polyisobutenes having at least 80 mol% vinylidene double bonds The obtained polyisobutenes have average molecular weights from 240 to 2800 in combination with MK / N dispersions from 1.26 to 2.29. A 490 454 discloses propylene oligomers having numerical average molecular weights from 700 to 5000 dalton and MW / MN dispersions from 1.5 to 4.0 It is an objective of the present invention to provide monoethylenically unsaturated polyolefins having molecular weights from 400 to 1500 dalton in combination with a dispersion MW / MN <1-2. We have found that this objective is achieved and that, surprisingly, the polioles fine monoethylenic unsaturated substances having Mw / M dispersity? < 1.2 can be obtained by acid-catalyzed dimerization of "monoethylenically unsaturated oligoolefins having a MW / MN <1.4 dispersibility. The present invention, therefore, relates to the polyolefins obtained by catalytic dimerization of at least mono-unsaturated olefin oligomers, the polyolefin having a number average molecular weight -MW / MN from 400 to 1500 dalton and a MW / N dispersity < 1.2 and being at least monoethylenically unsaturated. Polyolefins having a MW / MN number average molecular weight from 400 to 800 dalton are preferred according to the invention. These polyolefins are obtained by dimerization of olefin oligomers having numerical average molecular weights "MW / MN from 200 to 400 daltons. To obtain a dispersity M" / MN < 1.2 in the case of novel polyolefins, it is necessary that the oligomers of short chain have a dispersion Mu / M? <1.4, preferably MW / MN <1.2. If shorter chain olefin oligomers are used with a MW / MN <1.2 dispersity, polyolefins are obtained with an Mw / M [-j <1.1 and are preferred according to the invention.) For better control of the dimerization reaction, those short chain oligomers are preferred in which at least 50% of the double bonds are terminal double bonds, that is, vinylidene or vinylidene double bonds Oligomers having at least 60% vinyliene double bonds or at least 80% vinyl double bonds are particularly preferred.The olefin oligomers preferably have only a double bond. The short chain oligomers are obtained, as a rule in the form of volatile components in the homo- or copolymerization of olefins, preferably C2-C10 olefins, in particular C2-C6 olefins. These are, as a rule, obtained by distillation from the polymerization products. Oligomers having the desired high content of terminal vinyl or vinylidene units are obtained, for example, from the polymers prepared by cationic polymerization, preferably using catalysts containing BF3 (see, DE-2702604, US-A 5,068,490, US Pat. -A 5,286,823 or WO 85/01942), or from the polymers prepared by metallocene-catalyzed polymerization. Examples of these polymerization processes can be found, for example, in the German application open to the public DOS 4,205,932 (polymers containing vinylidene) or in EP-A 268 214 (polymers terminated in vinyl-o). The description of the publications established for the polymerization is incorporated herein by reference. Suitable catalysts for dimerization are, as a rule, Lewis acid compounds, such as boron halides, for example, BCI3, or BF3, aluminum halides such as ACI3 or alkyl aluminum halides, for example, dichlorides of aluminum alkyl, such as ethyl aluminum dichloride. The acid fluoride is also suitable as an acid catalyst. The established catalysts can can be used alone or in combination with each other or in combination with complexed agents, such as acid fluoride, acidic ion exchangers, silica gel, carboxylic acids and, if required, inorganic acids, preferably trifluoride. boron is used alone or in combination with a compound containing oxygen as an acid catalyst Examples of suitable oxygen-containing compounds are water, C1-C10 alcohols, C2-C10 diodes, C1-C20 carboxylic acids, anhydrides carboxylic acids of Cj-C12 and C2-C20 dialkyl ethers In accordance with the invention, the complexing agents before the class consisting of C1-C20 alcohols or water are preferred according to the invention, in particular C1-6 alcohols. C4, very particularly preferably monohydric, secondary alcohols of C3-C20, as described in EP-A 628 575. Very particularly preferably, boron trifluoride is used together with isopropanol and / or 2-butanol The molar ratio of BF3 to the oxygen-containing compound from -then will depend on the binding strength of the complex of the oxygen-containing compound and can be determined in a simple manner by a person skilled in the art. When alcohols are used, it is from 1: 2 to 2: 1, preferably from 1: 2 to 1: 1 and very particularly preferably from 1: 1.7 to 1: 1.1. The catalysts in which the complexes are become heterogeneous by adsorption on solids, such as silica gel or molecular sieves, are preferred. The dimerization can be carried out in the normal way by batch process or by a continuous process. If a batch process is used, as a rule the catalyst is added to the oligomer, which can be diluted with an inert solvent. Particularly suitable solvents are hydrocarbons, preferably those which can be easily removed by distillation, for example, butane, pentane, cyclopentane, hexane or issoctane. If complex catalysts are used, these can be added in the form of their complex or in free form to the complexed agent initially taken in the reaction medium. The reaction temperature will of course depend on the respective catalyst or catalyst system. However, it is generally from -100 ° C to + 40 ° C, preferably from -100 ° C to 0 ° C. If the catalyst systems containing BF3 are used, the reaction is carried out below 0 ° C, preferably below -20 ° C and, particularly preferably below -25 ° C. Depending on the catalyst used in each case, the duration of the preferred reaction is from 30 minutes to 5 hours.Dimerization is preferably carried out under isothermal conditions, since it is exothermic, the heat of the dimerization must be eliminated. This is done, for example, with the aid of a cooling apparatus that can be operated with liquid ammonia as a refrigerant.

The treatment after the reaction is advantageously carried out by deactivating the catalyst for dimerization, for example by means of water, alcohols, acetonitrile, ammonia or aqueous solutions of mineral bases such as alkali metal hydroxide and alkaline earth metal solutions, carbonates of these metals and the like. As a rule, then the washing with water is carried out. After removing the water, any volatile component is also distilled. The heterogeneous catalysts can be filtered and reused. Any catalyst residue is removed by washing (see above). The dimerization products obtained have number average molecular weights from 4001 to 1500 dalton in combination with a dispersity of from 1.0 to 1.2. When oligomers are used that have numerical average molecular weights MW / MN from 200 to 400 dalton and a dispersity Mw / Mu < 1.2 Oligomers with molecular weights of up to 800 dalton are obtained in combination with a dispersity of M? / T < 1.1-These oligomers are particularly suitable for the preparation of fuel additives. The present invention also refers to the functionalized polyolefins obtainable by functionalizing the novel polyolefins, wherein the functionalized polyolefin is of the general formula I: where R is the polyolefin radical, i is an integer from 1 to 4 and, when i is 1, X is a functional group of the general formula (II) where k and 1, independent of each other, are each 0 6 1, R 'is hydrogen, alkyl, hydroxyalkyl, aminoalkyl, cycloalkyl, aryl, aralkyl or -Y-Z, -Y- is a group Alk- - Alk' or Alk- N (R ") -Alk 'PL Jp where Alk and Alk 'are identical or different and each is C2-C4 alkylene, p is an integer from 0 to 10, and R "is hydrogen, alkyl or aryl, and it is selected from: where R 1 and R 2, independent of each other, each are hydrogen, alkyl, cycloalkyl, hydroxyalkyl, aryl or aralkyl and, if 1 is 0, it can also be R and -CH-R, where R has the meanings mentioned above or R and R, together with the nitrogen atom to which they are attached, form a substituted or unsubstituted heterocyclic structure which may contain another heteroatom selected from oxygen and nitrogen, A is C3-C5 alkylene which is unsubstituted or mono- or poly substituted by alkyl, cycloalkyl, aryl, hetaryl, aralkyl or hetaralkyl, A 'is C2-C4 alkylene or C2-C4 alkenylene, both of which are unsubstituted or mono- or poly-substituted by alkyl, cycloalkyl, aryl hetaryl , aralkyl, or hetaralkyl, or is o-arylene, m is 1 or 2, L is hydrogen, alkyl, aryl, aralkyl, hetaryl or hetaralkyl and it is selected from: where R 3 -R 12, independent of each other, each are hydrogen, alkyl, aryl, hetaryl, aralkyl, or hetaralkyl, q is from 1 to 50 and Alk "is C 2 -C 4 alkylene which is unsubstituted or substituted by hydroxyl and E is hydrogen or an equivalent ester of an aliphatic, aromatic or araliphatic mono-, di-, tri or tetracarboxylic acid, or X is a functional group of the general formula (III). where n is an integer from 0 to 50, Alk is an alkylene unit of C2-C4, and E has one of the meanings mentioned above; or X is a functional group of the formula (Illb) CH J-0 AAllkkJ-r- NH (Illb) where Alk has one of the meanings mentioned above and s is an integer from 1 to 50; or X is a functional group of the formula (IV) wherein V is alkyl, aryl, aralkyl, -O-R13 or -MR14R15 and RX3 a R1, independent of each other, each can be hydrogen, alkyl, which can also be interrupted by one or more non-adjacent oxygen atoms and / or can also have NH2- or OH-, or cycloalkyl, aryl, aralkyl, hetaryl or hetaralkyl, W can be hydrogen, alkyl, cycloalkyl, aryl, aralkyl, hetaryl or hetaralkyl, alkyl carbonyl, alkyloxycarbonyl, or alkylaminocarbonyl, or V and W, together with the carbonyl function in V, form a group: where U is oxygen or NRX6, where R1"6 can have the meanings set for R 13-R-15; or, if i is from 2 to 4, X is a group of the general formula (V) (V) where G is derived from a di-, tri- or tetravalent aliphatic radical, L has the aforementioned meanings and R is hydrogen or C1-C4 alkyl. In the following, alkyl is understood as straight or branched hydrocarbon chains, saturated with, preferably 1 to 10, carbon atoms. For example, the following radicals may be mentioned: lower alkyl, ie, Ci-Cs alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, -pentyl, sec-pentyl, isopentyl, n-hexyl, 1-, 2- or 3-methyl-pentyl; large chain alkyl radicals such as heptyl, octyl, 2-ethylhexyl, nonyl and decyl. Alkoxy is understood as alkyl that is attached by an oxygen atom. Accordingly, alkylamino and alkylcarbonyls are alkyl groups that are attached by a nitrogen atom or a carbonyl function. Amino alkyl or hydroxyalkyl is alkyl as defined above, having an amino group or hydroxyl group, preference in a terminal carbon atom. Alkyl cycle preferably means C3-C8 cycloalkyl, in particular cyclopentyl or cyclohexyl, each of which is unsubstituted or substituted by C1-C4 alkyl or C1-C4 alkoxy. "Alkylene" preferably means a 1,2-, 1,3- or 1,4-alkylene unit, for example, 1,2-ethylene, 1,2-propylene, 1,2-butylene, 1,3-propylene, 1 , 4-propylene, 1-methylpropylene, 1,2-pentylene or 1,2-hexylene. Aryl is preferably understood as phenyl or naphthyl which can carry 1, 2, 3 or 4 substituents. The hetaryl groups are preferably 5- or 6-membered aromatic ring systems containing from 1 to 4 heteroatoms selected from 0, F and N, for example, furyl, pyrrolyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, oxy diazolyl, tetraazolyl, pyridyl. , pyrimidyl, pyrazyl, piperazinyl, triazinyl, tetrazinyl and the like. Aralkyl is understood as aryl groups that are linked by an alkyl unit of Ci-Ce, for example, benzyl or phenethyl. The same applies to hetaralqui-lo. Suitable substituents are Ci-Ce alkyl, Ci-Cß alkyloxy, C2-C6 alkenyl, Ci-Cg alkanoyl, and alkycarbonyl, such as acetyl and propionyl, and hyyl which, if required, can also be ethoxylated , hyyalkyl, amino alkyl, nitro, carboxyl and a-m-mo The functionalized polyolefins of the general formula (I) wherein X is a general radical of the formula (II) with k = 1 can be obtained by hyormylation of the monoethylenically unsaturated homo- and copolymers and the subsequent reductive amination of the aldehyde function obtained by the hyormulation [sic], that is, by reaction with ammonia or a primary or secondary amine in the presence of hyen and a hyenation catalyst. This provides the compounds of the general formula (VI). -R > • CH2-N; (VI) -Rb where R and R, independent of each other, each are hyen, alkyl, which may be interrupted by one or more non-adjacent amino groups or oxygen atoms, or cycloalkyl, which may also have heteroatoms, such as N or O, in the ring, or aryl, aralkyl, hetaryl, hetaralkyl or CH? -R, where R is derived from the polyolefin. Suitable amines in addition to ammonia comprise mono- and dialkylamines of C? -C? Or, such as mono- and dimethylamine, mono and diethylamine, mono- and di-n-propylamine, mono- and di-n-butylamine, mono and di-sec-butylamine, mono- and di-n-pentylamine, mono- and di-2-pentylamine, mono- and di-n-hexylamine, and the like. Other suitable amines are diammas, such as ethylene diamine, propylene-1, 2-diamine, propylene-1, 3-diamine, butylene diamines and the mono-, di-, and trialkyl derivatives of these amines. Polyalkylene polyamines whose alkylene radicals are 2 to 6 carbon atoms, such as diethylenetriamine, triethylene tetramine and tetraethylene pentamine, can also be used. The mono- or dialkylamines in which the alkyl radical can be interrupted by one or more non-adjacent oxygen atoms and which can also have hyyl groups are also suitable. These include, for example, 4,7-dioxadecan-1, 10-diamine, ethanolamine, 3-aminopropanol, 2- (aminoethoxy) ethanol and N- (2-aminoethyl) ethanolamine. Cyclic amines, such as pyrrolidine, piperidine, piperazine or morpholine, and substituted derivatives thereof, such as N-aminoalkyl of Ci-Ce piperazines, can also be used. In addition, it is possible to use aryl, aralkyl, hetaryl, or hetaralkylamines. These preparation processes are known to those skilled in the art and are described, for example, in EP-A 244 616, DE-A 36 11 230 or WO 94/24231. If the compounds of the general formula (VI) also contain primary or secondary amino functions, they can be derived by conventional methods of organic chemistry. If these are, for example, compounds that have primary functions (lia compounds), these they can be reacted with lactones of the general formula (IX), obtaining compounds of the general formula (Ilb).

(Ha) (IX) (Hb) In the formulas (IX and (Ilb), A is alkylene of C3-Cs which can have from 1 to 5 substituents R, R ', Y and L have the meanings mentioned above. they are known and can be prepared by Bayer-Villiger oxidation, for example, starting from cyclic ketones.The use of? -, d-, or e-lactones, such as? -butyrolactone,? - or d-, is preferred. valerolactone or e-caprolactone and the mono- or poly-substituted analogues thereof The reaction is preferably carried out by a process in which the amino-functionalized polyolefin of the formula (lia) is reacted with the lactone (IX ) in the absence of a solvent or in suitable solvent, for example, tetrahydrofuran, or in another inert solvent, in a conventional manner at elevated temperatures, for example, from 200 to 320 ° C, and superatmospheric pressure, for example, from 50 to 50 ° C. 300 bar, and the formed product is obtained with elimination of water formed in the reaction and any actona not converted. If mixtures of the lactones of the general formula (IX), the novel compounds of the general formula (Ilb) can simultaneously contain different cyclic end groups. The preparation of the cyclic imides of the general formula (lie) can be carried out in a similar manner. These reactions are known in principle to a person skilled in the art and are described, for example, in J. March (Advanced Organic Chemistry 3rd edition, J. Wiley, New York, page 371 et seq.) And the literature mentioned in In this case also the primary amines of the general formula (lia) (see, in the above) are used as starting materials. These are reacted with suitable cyclic dicarboxylic anhydrides or with; the dicarboxylic acids thereof. Suitable dicarboxylic acids or dicarboxylic anhydrides are succinic anhydride, maleic anhydride and phthalic anhydride and their substituted analogues. The preparation of the compounds of the general formula (Ilb) wherein R, R ', Y, 1, L, m and Z' have the meanings mentioned above, is carried out, as a general rule, by functionalization of the primary or secondary amind functions in the compounds of the general formula (X). The compounds (X) which, where m is 2, correspond to the primary amines (lia) can, as these also be prepared by hydroformylation and the subsequent reductive amination (see above).

The compounds of the general formula (lid), where Z 'O C II R3 and R have the meanings mentioned above can be prepared by conventional methods of primary or secondary amino-acid acylation (see, J. March, Advanced Organic Chemistry 3rd edition, J. Wiley 1985, page 370 et seq. the literature mentioned in it). The compounds of the general formula (Ilb), wherein Z 'is formyl (R = H), can be prepared by reacting the primary or secondary amines of the general formula (XT with carbon monoxide or with a algal form in the presence of of alkali metal alcoholates. Sodium alcoholates or potassium alcoholates, in particular alkali metal methylates are preferably used Sodium methylate is very particularly preferred The reaction of the amine of the formula (X) with monocarbon oxide It is preferably carried out after establishing the following parameters: - Carbon monoxide is used in excess in the reaction.The ratio of carbon monoxide to amine is established by means of the partial pressure of carbon monoxide. The molar ratio of the amine (X) to the catalytically active alkali metal alcoholate - is, as a rule, from about 20,000: 1 to about 1000: 1, preferably from 12: 1 to about 5000: 1. - The reaction is These alcohols are, as a rule, primary aliphatic i-Cio alcohols, such as methanol, ethanol, isopropanol, n-butanol, n-pentanol and the like, preferably metaphors. nol or ethanol, in particular methanol.

- The reaction can be carried out in a solvent different from the aforementioned alcohols. For example, the following can be mentioned as solvents: hydrocarbons such as hexane, cyclohexane, mixtures of C5-C20 hydrocarbons, for example, mixtures of C10-C13 hydrocarbon (for example, Mihagol) and the like. The amount of solvent is, in general, from about 10 to 90% by weight, based on the total batch. - The reaction is carried out from about 10 to about 200 ° C, preferably from about 20 to about 100 ° C. The reaction pressure is from about 10 to about 200, preferably from about 20 to about 100 bar. Reaction times are, in general, from about 0.1 to 5 hours. To carry out the reactions, the reagents are mixed and then brought to the reaction temperature under CO- pressure. The treatment can be carried out in a manner known per se by separating the catalyst, distilling the solvent and, if required. purification of the reaction product by chromatography or distillation. Where the amine of formula (X) is reacted with a format, the following parameters are preferably applicable - The formats used are alkyl formats. The alkyl esters of Ci-Cß / for example, methyl formate and ethyl formate, are preferably used; the methyl format is particularly preferred. The molar ratio of the alkyl form, for example, methyl format, to the amine (X) is, as a rule, from about 10: 1 to about 1: 1. The ester of preference is used in excess, for example, in a ratio of from about 3: 1 to about 1.3: 1. The reaction can be carried out in a solvent, for example, in one of the aforementioned solvents, such as hexane, cyclohexane, C5-C20 hydrocarbon mixtures, for example mixtures of C10-C13 hydrocarbon (for example, (Mihagol), and the like The amount of solvent is, in general, from about 10 to 90% by weight, based on the total batch - The reaction is carried out from about to about 200 ° C, preferably from about 20 to about 100 ° C. The pressure of the reaction is the autogenous pressure of the reaction mixture at the chosen temperature If a pressure higher than the autogenous pressure of the mixture is desired, an inert gas, eg nitrogen, it can also be introduced The reaction times are, in general, from about 0.1 to about 5 hours.

To carry out the reaction, the reactants are mixed and then brought to the reaction temperature. The treatment can be carried out in a manner known per se by distillation of the low-boiling substances and, if required, by purification of the reaction product by chromatography or distillation. Yes, in the formula (Ilb) Z 'is a gr-upo: where In the aforementioned cases, the novel functionalized polyolefins can be obtained by reaction of the primary or secondary amines of the general formula (X) with diketenes of the formula (XI).

The preparation is carried out in the manner known per se, by reacting the amine (X) with the diketene (XI) in the absence of a solvent or in an inert solvent, with cooling at room temperature _ or at elevated temperatures, depending of the reactivity of the reagents. Examples of suitable solvents include sulfur-free and chlorine-free solvents, such as hydrocarbons high boiling point, for example, n-hexane, n-octane, n-decane or isododecane, or dipolar aprotic solvents, such as anhydrous tetrahydrofuran. The compound (X) is preferably dissolved in a suitable solvent and the diketene (XI), if necessary dissolved in the same solvent, is added dropwise with stirring. The reaction products obtained can be used without further purification, if necessary after distillation of the solvent or elimination of superfluous reagents. The novel functionalized polyolefins also include compounds of the general formula (lb), where Z 'is a group: and R 8 and R 9 have the meanings mentioned above. These compounds can be obtained by functionalizing the amino group in (X) by cyanomethylation. The cyanomethylation is carried out by the reaction of a polyalkylamine of the general formula (X) with hydrocyanic acid or with a salt thereof and at least one ketone R -C (0) -R, where R and R have the meanings before mentioned. The reaction is carried out, as a rule, in the presence of a transfer catalyst. phase. Suitable phase transfer catalysts include quaternary ammonium and phosphonium salts, but quaternary ammonium salts are preferred. Examples of suitable phase transfer catalysts are benzyltriethylammonium chloride, tetrabutylammonium bromide, methyltricapril ammonium chloride and methyltributylammonium chloride and the corresponding halogen free forms of these compounds. The reaction is carried out, as a rule, from room temperature to 100 ° C, preferably from 40 to 80 ° C. The reaction of the amine (X) is carried out in water or polar organic solvents, such as alcohols or cyclic ethers, for example tetrahydrofuran or mixtures thereof. The amine (X) is preferably initially taken together with the phase transfer catalyst in a polar organic solvent, if necessary together with water, and the hydrocyanic acid or an aqueous solution of "alkali metal or alkali metal cyanide" A suitable solution and the ketone or the aldehyde, if necessary as the solution in an organic solvent or water or mixture thereof, are added dropwise after the removal of the phase transfer catalyst by washing with water and elimination. of the solvent, the alkylated cyano product remains in a form that can be used directly.

The additives of the general formula (Ilb), where Z 'is: and R 10 to R 12 have the meanings mentioned above, can be prepared by the processes described in EP-A 568 873, which are hereby incorporated by reference in their entirety, by the cyano ethylation method, ie, the reaction of the primary or secondary amine (X) with a nitrile, β-unsaturated. The additives of the general formula (lid), where Z is a group of the general formula: and Alk '', q and E have the meanings mentioned above, can be obtained by alkoxylation of amines of the general formula X with oxides, preferably with ethylene oxide, 1,2-propylene oxide or 1,2-butylene oxide . Alcohols of the general formula (Vlla): R-CH2- NJtAlk O- ^ H] (VIIa) L2-m which are obtained by this method can then be esterified with suitable carboxylic acids or carboxylic acid derivatives to give the esters of the general formula (VII), • CH2-., X r Alk "~ O -) .- JE (VII) where R, Alk ", L, myq have the meanings mentioned above, and E is an equivalent ester of an aliphatic, aromatic or araliphatic mono-, di-, tri- or tetracarboxylic acid.The suitable esterification components are mono-, di-, tri- or tetracarboxylic acids. and dicarboxylic acids and their anhydrides or acid chlorides, and in addition, tri- and tetracarboxylic acids Suitable carboxylic acids, preferably include acetic acid, propionic acid, ethylhexanoic acid, benzoic acid, 2-phenylacetic acid, isononanoic acid, succinic acid, acid Adipic acid, maleic acid, phthalic acid, terephthalic acid, isophthalic acid, citric acid, trimellitic acid, trimesic acid, pyromellitic acid and butacarboxylic acid - The di- or polycarboxylic acids can be partially or completely esterified with the alcohols (Vlla). , these are preferably only partially esterified with alcohols (Vlla). can react with ammonia or primary or secondary amines. The ammonium, amide, imide or amino carboxylic acid salts which can be obtained by this means in the same manner have excellent dispersing properties and, therefore, are suitable as additives of fuel and lubricants. The compounds of the general formula (VII), wherein Alk "is 1,2-ethylene, 1,2- or 1,3-propylene or 1,2- or 3,4-butylene are preferred, among which is particularly preferred to the alcohols (Vlla), L is preferably hydrogen or Ci-Ce alkyl, and m is preferably 1. Particularly preferred compounds are those of the general formula (Vil) or (Vlla), wherein q is chosen so that their number-average molecular weight MN is from 1000 to 3000 dalton.These compounds can be prepared by the conventional methods of polyalkenylamine alkoxylation, as described for example in EP-A 244 616. The ammo-functionalized polyolefins of the general formula ( XII), where R, R ', Y, Z and 1 have the meanings mentioned above, which differ by a CH2 group from the amines of the general formula (VI) which are obtained by the hydroformylation / reductive amination method in the same way the subject of the present invention. Its preparation can be carried out by two different methods. For example, it is known that the double bond of Ethylenically unsaturated polyolefins can be epoxidized. The functionalized oxirane polyolefins thus obtainable can be subjected to cleavage of the ring with ammonia or primary or secondary amines to give -amino alcohols (see, for example, WO 92/12221, WO 92/14806, EP-A 476 485 and EP 539 821 ). The amino alcohols obtainable by this method can be catalytically dehydrated. The enamine formed is then hydrogenated to give the amine. The conversion of the epoxide to the amine can be carried out in separate steps. However, it is also possible to carry out the conversion of the epoxide to the amine in one step by reacting the epoxide with ammonia or a primary or secondary amine in the presence of hydrogen and a catalyst having dehydration properties and at the same time hydrogenation. The catalysts which can be used according to the invention and have dehydration and hydrogenation properties are preferably chosen from porous zeolites or oxides of Al, Si, Ti, Zr, M ", [sic] Mg and / or Zn, Acid and heteropolyacid ion angers, each of which has at least one hydrogenating metal. The hydrogenating metals used are preferably Ni, CO, Cu, Fe, Pd, Pt, Ru, Rh, or combinations thereof. The zeolite catalysts in the appropriate solid state according to the invention are described, for example, in EP-A 539 821, which is hereby incorporated by reference in its entirety. To optimize - selectivity, conversion and catalyst life, the zeolites used according to the invention can be impurified in a suitable form with other elements (see EP 539 821). The zeolites can also be contaminated with the aforementioned hydrogenating metals. Hydrogenating metals represent from 1 to 10% by weight, calculated as oxides, of the total weight of the catalytically active material. Other suitable catalysts which have hydrogenation dehydration properties are preferably acid oxides of the Al, Si, Zr, Nb, Mg or Zn elements or mixtures of thereof, which are impurified with at least one of the aforementioned hydrogenating metals. The oxide (calculated as A120, Si02, Zr02, Nb2? 5, MgO or ZnO) is present in the catalyst material in an amount from about 10 to 99, preferably from about 40 to 70% by weight. The hydrogenating metal (calculated as Nio, CoO, CuO, Fe? Os, PdO, PtO, Ru02 or RI12O3) is present in an amount from about 1 to 90, preferably from about 30 to 60% by weight based on the weight total of the catalytically active material.

In addition, the oxides used according to the invention they may contain small amounts, that is, from about 0.1 to 5% by weight (calculated for the oxides), of other elements, for example, Mo or Naj to improve the catalytic properties, such as selectivity and catalyst life. These oxides ~ their preparation are described, for example, in EP-A 696 572, which is fully incorporated herein by reference. The conversion of the epoxides to the amines can be carried out continuously and in batches. The temperatures in both process variants are from about 80 to 250 ° C, preferably from about 150 to 210 ° C. The reaction is carried out at hydrogen pressures up to about 600, preferably from about 80 to 300 bar. The amine is used in a molar ratio of from about 1: 1 to about 40: 1, preferably in an excess from about 5: 1 to about 20: 1, based on the -epoxide. The reaction may be carried out in the absence of a solvent or in the presence of a solvent (for example, of a hydrocarbon such as hexane or tetrahydrofuran). Examples of suitable amines in addition to ammonia are: ethylene-1,2-diamine, propylene-1,2-diamine, propylene-1,3-diamine, butylenedianes and monoalkyl-, dialkyl and trialkyl derivatives of these amines, example, N, N-dimethylpropylene- 1,3-diamine. Polyalkylene polyamines whose alkylene radicals are no more than 6 carbon atoms, for example polyethylene polyamines, such as diethylene triamines, triethylene tetramine and tetraethylene pentamine, and polypropylene polyamines can also be used. Mono- or dialkylamines in which the alkyl radicals are interrupted by one or more non-adjacent oxygen atoms and which may also have hydroxyl groups or other amine groups, such as 4,7-dioxandecan-1, 10-diamine, ethanolamine , 3-aminopropanol, "2- (2-a-minoethoxy) ethanol, N- (2-aminoethyl) ethanolamine, are also suitable." Other examples are N-amino-alkyl of C1-C6 piperazines The ammonia is preferably the used / The amines of the general formula (XII) obtainable by this method, in particular the primary amines (Xlla) in this case Z in the formula (XII) is NH2 and 1 is 0), which are obtained by the reaction of oxiranes with ammonia, can also be functionalized by the methods described above- NH2 (Xlla) The second route for the amino functionalized polyalkenes of the formula (XII) includes subjecting the monoethylenically unsaturated polyalkenes to a reaction of Ritter. This should be understood as the reaction of olefins with HCN or low nitriles acid catalysis. The reaction is carried out by formamide or acyl derivatives, which can then be hydrolyzed to the primary amines of the general formula (Xlla) ', where R has the meanings mentioned above. The Ritter reaction is described in Houben-Weyl E5, pages 103-1041 (1985) or Houben-Weyl, XI / 1 page 994 et seq. (1987). The preparation of the polyalkylene amines by the Ritter reaction is described, for example, in the application of German Patent Laid-Open No. 2,061,057 or EP-A 567 810, which is hereby incorporated by reference in its entirety. Another class of lubricant and fuel additives comprises compounds of the general formula (XIII) -CH2- • AlkH-O E (XIII) -Jn - Corresponding to the compounds of the general formula I, where X is: in this case, Alk, E and n have the meanings mentioned above. One embodiment of the present invention are these compounds, where n obtains the values "from 0 to 10, another modality refers to these compounds, where the average value of n is in the range from 11 to 50, preferably from 15 to 35. In the last mentioned modality E of Preference is given to hydrogen, which are prepared in the same manner for the preparation of the functionalized amino derivatives of the general formula (VI), starting from the hydroformylation product of the novel polyolefins, which is then hydrogenated under an excess of hydrogen to give the corresponding alcohol of the general formula (Villa). These processes are described, for example, in EP-A 277 345, which is incorporated herein by reference in its entirety.The alcohols obtainable in this manner and the formula general (Villa), R CH2 OH (Villa) where R has the meanings mentioned above, they can be alkoxylated by the known methods of organic chemistry to give the compounds of the general formula (XlIIa), R CH2J-0- Alk- -OH (xnia) I- -ln where R, Alk and n have the meanings mentioned above, and / or can be esterified to give the compounds of the general formula (XIV) or (VIII).

-CH2-O-E (VIII) CH2-? Lk- _0 E (XI) n The addition reaction of the alkylene oxides with alcohols in the presence of basic catalysts is well known. In particular, the ethylene oxide, propylene oxide and butylene oxide and the mixtures thereof are of industrial importance, but addition reactions of the compounds such as cyclohexene oxide are also possible. The alkoxylation reactions can also be carried out on the crude products obtained from the hydroformylation reaction because the alcohols (Villa) are formed in appreciable amounts during the hydroformylation. -Further, the aldehydes, R-CHO will be disproportionate in the sense of a cannibal reaction in the alcohol (Villa) and a carboxylate salt R-C02M, where M is the cation of the conventionally used alkoxylation catalyst. Other suitable lubricant-fuel additives are the esters of the alcohols (Villa) and their alkoxylation products (XlIIa). Suitable esterification components are mono- and dicarboxylic acids and their anhydrides or acid chlorides, and also tri- and tetracarboxylic acids. Suitable mono- or polycarboxylic acids include acetic acid, propionic acid, ethylhexanoic acid, isononanoic acid, succinic acid, adipic acid, maleic acid, phthalic acid, terephthalic acid, citric acid, trimellitic acid, trimesic acid, pyromellitic acid, and Tetracarboxylic butan The di- or polycarboxylic acids can be partially or completely esterified, but these are preferably only partially esterified with the alcohols of the general formula (Villa) or (XlIIa) .The free carboxylic acid functions can react with ammonia. or primary or secondary amines The ammonium, amide, imide or amino acid salts obtainable thereby - in the same way have excellent dispersing properties and, therefore, are also suitable as fuel and lubricant additives. compounds are the amines of the formula (XlVb) • CH2 J- < Alk- -NH2 (XlVb ) L Ja where R has one of the meanings mentioned above, s is an integer from 1 to 50, preferably from 10 to 40, and Alk has one of the meanings mentioned above and, preferably is 1,2-ethylene or 1 , 2-propylene. These amines (XlVb) are obtainable for example from alcohols (Villa) or aldehydes R-CHO by an alkoxylation reaction in the presence of basic catalysts such as sodium hydroxide or potassium hydroxide or alkaline earth metal oxides such as barium oxide by the products of alkoxylation reaction of the formula R-CH02- [O-Alk], -OH, where R, Alk and s have the meanings mentioned above, by reacting the compounds with ammonia / hydrogen in the presence of hydrogenation catalysts such as Raney Nickel or Raney Cobalt at high pressure, for example 100 'at 300 bar and high temperature for example from 100 to 300 ° C.

A third class of novel functionalized polyolefins comprises the compounds of the general formula (XIV), wherein R, V and W have the meanings mentioned above. The succinic acid derivatives of the general formula (XV), wherein U is oxygen or NR and R have the meanings mentioned above, are preferred. _U is particularly preferably NR.

These compounds are obtained by subjecting the monoethylenically unsaturated polyalkenes to an ene reaction with α, β-unsaturated carbonyl compounds of the formula general (XVI) The compounds of the general formula (XVI) are preferably maleic anhydride, which is subsequently functionalized with a primary amine of the general formula H 2 NR or an alcohol. These processes are known to those skilled in the art and are described, for example, in DE-A 2702604. A fourth class of novel functionalized polyolefins comprises the compounds of the general formula I, wherein i is from 2 to 4, and X is a group of the general formula (V).

CK.-H: (V) where G is derived from a di-, tri- or tetravalent organic radical, L and k have the meanings mentioned above and R1 is hydrogen, alkyl, aryl, aralkyl or hetaryl, but preferably it is hydrogen. L is in the same way preferably hydrogen. These compounds can be prepared by reaction of the novel amines of the general formula (X) (see above) or (XVII) (the formula (XVII) corresponds to the formula (XII) with Z '= NHmL2-m, where L and has the meanings previously-mentioned) with glycidyl ethers of the general formula (XVIII).

G-f-O CH (XVIII) R "where R, G and i have the meanings mentioned above, by known processes- The glycidyl ethers (XVIII) are formally derived from divalent, trivalent, tetravalent or higher valence aliphatic alcohols, such as glycol, 1 , 2- or 1, 3-propanediol, 1,2-, 1,3-6,4,4-butanediol, diethylene glycol, triethylene glycol, glycerol, trimethylolpropane, mannitol [sic] erythritol, pentaerythritol, arabitol, adonitol, xylitol or In the glycidyl ethers (XVIII), from 2 to 4 of the OH groups of the established polyhydroxy compounds are etherified with glycidyl groups In the preferred compounds of the general formula (I), where X is a group of the general formula (V), the general formula (V) is derived from 1,2-, 1,3- or 1,4-butanediol, trimethylol propane or pentaerythritol, in which all the OH groups have been etherified with glycidyl groups. the compounds of the general formula (I) where i is 1 and X is a radical. OH H0H2C HC CH2 N (CH2) L These compounds are obtained by the reaction of glycidol with an amine (X) or (XVII). As in the case of novel, non-functionalized polyolefins, the novel functionalized polyolefins of the general formula (I) can also be used in the normal way as fuel or lubricant additives A common fuel composition, for example a fuel for gasoline and diesel engines contains the novel polyolefins and / or the compounds of the general formula (I) in amounts from 20 to 5000, preferably from approximately 50 to 1000 mg / kg of fuel. It also needs to be introduced together with other additives, which serve, in particular, as detergents to keep the fuel intake system clean.These additive-containing fuels have highly cleansing effects, that is, a low level of deposits in the valves. The invention further relates to lubricating compositions containing at least one polyolefin functionalized, novel of the general formula (I), according to the above definition, if required in combination with other conventional lubricant additives. Examples of conventional additives are corrosion inhibitors, anti-wear additives, viscosity improvers, detergents, antioxidants, anti-foaming agents, lubricity improvers and pour point improvers. The novel compounds are usually present in the lubricant composition in amounts from 0.5 to 15, preferably from about 1 to 10% by weight, based on the total weight. Examples of the lubricants prepared according to the invention include oils and greases for motor vehicles and industrially used drive units, in particular engine oils, gear oils and turbine oils. The following examples illustrate the invention, however, not Limit- Examples -Analysis The numerical average molecular weight MN of the initial materials was determined by gas chromatography / mass spectrometry combined according to known methods. Otherwise, the molar masses of the reaction products were determined by means of gel permeation chromatography (GPC): the discrimination according to the molar masses was carried out on 5 combined B columns (1 = 300 mm, d = 7.5 mm, loaded with PL-gel) from Polymer Laboratories, which were connected in series. The mobile phase used was tetrahydrofuran. The detection was carried out by the refractive index using a Waters RI-Detector 410 apparatus. Commercial polyisobutene standards were used for calibration. Chromatography was carried out at T = 35 ° C and a flow rate of 1.2 ml / min.

The dimers were characterized with respect to their molecular weight distribution by means of the known methods of permeation chromatography in ijel (GPC) and by means of the known methods of gas chromatography (evaluation of peak integrals). The calculation was based on the following formulas: In this case, Mj. is the molecular weight of the individual species of the polymer i and cx is the part by weight of the polymeric species i in the polymer or mixture of oligomers, obtainable from the chromatograms. The proportion of vinylidene double bonds in the initial oligomers was determined by means of 13C-NMR spectroscopy (100.7 MHz), based on characteristic signals at 114.4 and 143.6 ± 0-4 ppm, (see, US 5,286,823).

Determination of functionalization yields and amine numbers The performance of hydroformylation functionalization was determined by preparative liquid chromatography. For this purpose, 20 g of the sample of the -hydroformylation batch (see, below) were freed from the solvent at 230 ° C / 2 -mbar, heavy, taken in 20 ml of heptane and applied to a column of silica gel - (1 = 1 m, d = 40 mm), whose free volume It was filled with n-heptane. The elution was carried out with 2 1 of heptane in the course of 2 to 3 hours, and the eluate was liberated from the solvent at 230 ° C / 2 mbar and reweighed. The performance of functionalization F was calculated from the R of the new weight and the weight of the sample S: F = 100 (S - R) / S. The amine numbers were determined as follows. First, the total amine number was determined by a p'otenciometric titration with tri-fluoro ethane sulfonic acid in acetic or glacial acid. The primary amine was obtained by reaction with a 25% strength by weight solution of acetylacetone in pyridine, and the Primary amine content was determined by re-titration with sodium methylate solution. To determine the tertiary amine, the primary and secondary amine was acetylated and the remaining tertiary amine was then determined by potentiometric titration with trifluoroethane sulfonic acid in glacial acetic acid. The content of the secondary amine was calculated by subtraction of the primary and secondary amine. [sic] from the total number of amines. The OH number, the ester number, the carbonyl number and the acid number were determined by known methods. The adequacy of functionalized, novel polyolefins as fuel additives was tested with the help of engine tests, which were carried out in test equipment with an Opel Kadett engine of 1.2 1 in accordance with CEC-F-04- A-87. The fuel used is European premium grade according to DIN 51607, together with reference oil L293.

Initial materials The oligobut-1-ene distillate used originated from the polymerization of but-1-ene by means of zirconocene catalysis: Triisobutylaluminoxane was prepared by the method in EP-A 575 356. 3.5 g of a solution of isobutylaluminoxane in heptane (3% by weight, based on AL, 3.89 mmol of Al), 0.27 g of trimethylaluminium and 18 g of 1-butene were initially introduced in succession into a reaction vessel with inert gas, and bis chloride was added. solid cyclopentadienylzirconium (IV) (0.32 g). The mixture was heated for 22 hours at 50 ° C, after which hydrochloric acid at 10% concentration was introduced while being cooled with ice. The organic phase was separated and subjected to fractional distillation to remove the solvent. According to "GC-MS and GPC, the oligomer had a numerical average molecular weight SN of 286 and a dispersity M" / MN <1.07 (34.2% by weight of the tetramer, 226.5% by weight of the pentamer, 17.1% by weight of the hexamer, 11.1% by weight of the heptane, 6.2% by weight of the octave, 3.5% by weight of the nonamer and 1.4% by weight of the decamer.) The distillate of the propene oligomerization used was obtained in the same manner as for -the 1-butene oligomer.The numerical average molecular weight Mu according to GC-MS and GPC was 290, and the MW / MN dispersity was 1.2 (0.2% by weight of the pentomer, 45% by weight of the hexamer, 31% by weight of the heptaraero, 14.4% by weight of the octamer, 6% by weight of the number, 2.7% by weight of the decamer and 0.17% by weight of an undecamer.) The isobutene oligomer used is the distillate of the preparation of -isobutene from of polyisobutene with catalysis of BF3 according to example 2 of US-A 5 286 823. According to GC-MS and GPC, the oligomer had a number average molecular weight MN of 202 and a MW / MN dispersity of 1.05 (47.3% by weight of trimer, 31.7% by weight of tetramer, 14.5% by weight pentamer, 5.1% by weight of hexamer and 1.4% by weight of heptamers).

Preparation of the dimer 500 g of the oligobut-1-ene distillate were diluted with 300 g of n-hexane, and the water content was reduced to 1 ppm by treatment with a 3 Á molecular sieve. -3.7 g of 2-butanol were added to the solution in a one-liter double jacket flask, and the mixture was cooled to -30 ° C. 3.4 g of boron trifluoride were passed to the solution in the course of 30 minutes at -30 ° C, and this temperature was maintained for another 30 minutes. Afterwards, the mixture was heated to 20 ° C, 250 g of de-mineralized water were added and the solution was left for another 15 minutes. The water was then separated and the organic phase was washed with a total of 500 g of demineralized water and distilled.At a lower temperature of 230 ° C and a pressure of 2 mbar, 395 g of the desired polyolefin remained in the residue of the distillation The results are summarized in Table 1.

Example 2 The distillate of the propene oligomerization (see above) was reacted - similarly as in Example 1. 380 g of the polyolefin remained in the distillation residue. The results are summarized in Table 1.

Example 3 Oligomeric isobutene (see inside ----) was reacted in the same manner as for example 1. 310 of polyisobutene remained in the distillation residue. The properties of the polyisobutene are summarized in Table 1.

Table 1 proportion of vinylidene double bonds, in accordance with C-NMR determination by means of GPC (see above) determined by means of GC (see above) Preparation of functionalized polyolefins Example 4 395 g of polybutene of Example 1, 100 g of dodecane and 5 g of octacarbonyl cobalt are heated in an autoclave at 280 bar CO / H 2 (1: 1) for 5 hours at 185 ° C. Then the mixture is cooled to room temperature, the The catalyst is removed with 400 such of a 10% aqueous solution of acetic acid and the reaction product is then washed to neutrality.The obtained oxo product is hydrogenated together with 0.1 1 ammonia and 300 g ethanol and 100 g. "Raney cobalt g in an autoclave at a hydrogen pressure of 200 bar at 180 ° C for 5 hours (reductive amination). The mixture is then cooled to room temperature, the catalyst is filtered, the excess ammonia is evaporated and the solvent is distilled off. 333 g of amino functionalized polybutene remains in 417 g of the residue. The performance of the hydrofor ilacidn functionalization was 85%, and the conversion of the oxo product to the amines was 94%. The amine number of the functionalized polybutene was 51- The amount of primary amine was 35% by weight, that of the secondary amine 52% by weight, and that of the tertiary amine 13% by weight. The results of the test engine are summarized in Table 2.

Example 5 380 g of the distillation residue of Example 3 were hydroformylated in the same manner as in Example 4 in the presence of 6 g of octacarbonyl cobalt and then subjected to reductive amination. The performance of the hydroformylation functionalization was 86% and the conversion of the oxo product to the amines was 95%. The amipase number of the functionalized polypropylene was 72. The amount of primary amine was 33% by weight, that of the secondary amine 51% by weight and that of the tertiary amine 16% by weight. The results of the motor test are summarized in Table "2.

Example 6 310 g of the distillation residue of Example 3 were dissolved in 62 g of dodecane and hydroformylated in the same manner as in Example 5. Then the reaction product was hydrogenated in the presence of Raney Nickel at a hydrogen pressure. of 190 bar and 190 ° C. The performance of hydroformylation functionalization was 82%, while the CO index was < 0.5 and the OH index was 111. The resulting solution of the hydrogenated product was reacted with 51 g of phthalic anhydride in the presence of 0.4 g of tetraisopropyl orthotitanate, first for 2 hours at 220 ° C and atmospheric pressure, and then for 2 hours at 220 ° C (batch temperature) and 2 mbar, with the excess of dodecane being distilled. After precipitation of the titanate with water and filtration, the residual dodecane was distilled at 230 ° C and 2 mbar. 371 g of the esterification product were obtained. The ester had an ester number of 96 and an acid number of < 1.

Example 7 380 g of the distillation residue of Example 3 were dissolved in 100 g of dodecane and hydroformylated in the same manner as in Example 4 in the presence of 6 g of octacarbonyl cobalt "(Co2 (CO) 8). the active compounds were approximately 65% (mixture of alcohol, aldehyde, alcohol formate and some carboxylic acid.) 3.8 g of KOH were added to the hydroformylation mixture, the mixture was then heated to 130 ° C. 50 g of a mixture of dodecane and water were distilled, then the mixture was pressurized with 1160 g of 1,2-propylene oxide, after 6 hours the pressure dropped to approximately 2 bar, the mixture was cooled to 80 ° C. and the pressure was released The volatile products were evaporated by evacuation / aereation with nitrogen 3 times. Then, 10 g of acidic ion exchange resin were added, stirred for 30 minutes and removed by filtration on a filter with a pore size of 0.2μ. The polyether obtained had an indigo d-e OH- of 32, a numerical average molecular weight MN (GPC) of 1730 and a dispersity M? / M? -j of 1.22.

Example 8 The polyether of Example 7 was reacted "with ammonia / hydrogen in the presence of Raney cobalt in the same manner as in Example 4 (reductive animation [sic]). The product of the reaction had an amine number of 28. The results of the motor test are summarized in Table 2.

Table 2: engine test

Claims (1)

1. CLAIMS A polyolefin obtained by catalytic dimerization of at least monounsaturated olefin oligomers which are homo- or co-oligomers of C3-C6 olefins, selected from propene, 1-butene, isobutene, 1-pentene, 2-methylbutene, 1-hexene, 2 -methylpentene, 3-methylpentene or 4-methylpentene, if required in combination with ethylene, the polyolefin having a number average molecular weight from 400 to 1500 dalton and a dispersity in MW / MN < 1.2 and being at least monoethylenically unsaturated. The polyolefin as claimed in claim 1, wherein the olefin oligomers have a number average molecular weight from 200 to 400 dalton.The polyolefin as mentioned in any of the preceding claims, wherein at least 50% of the olefin oligomers have a terminal double bond A process for the preparation of a polyolefin as recited in any of claims 1 to 3, wherein the monounsaturated olefin oligomers having a MW / MN dispersibility <1.4 are dimerized in presence of an acid catalyst and the catalyst is separated after the end of the reaction. 5. The process as recited in claim 4, wherein the acid catalyst is BF3 or a complex of BF3 with an oxygen-containing compound. 6. The process as recited in claim 5, wherein the oxygen-containing compound is C? -C8 alcohol. 7. The process as mentioned in any of claims 4 to 6, wherein the dimerization is carried out from 0 to -100 ° C. 8. A functionalized polyolefin that can be obtained by functionalizing a polyolefin that is obtained by catalytic dimerization of at least mono-unsaturated olefin oligomers, the polyolefin having a number average molecular weight from 400 to 1500 dalton and a dispersity Mw / M? < 1.2 and being at least monoethylenically unsaturated, wherein the functionalized polyolefin is of the following formula (I): Ri-X (I) where R is the radical, polyolefin, i is an integer from 1 to 4 and, when i is 1, X is a functional group of the general formula (II) where k and 1, independent of each other, are each 0 or 1, R 'is hydrogen, alkyl, hydroxyalkyl, aminoalkyl, cycloalkyl, aryl, aralkyl or -YZ, -Y- is a group Alk- -O Xj- Alk' -f- Alk- - N (R ") - HAlk '- IIDD where Alk and Alk 'are identical or different "each is C2-C4 alkylene, p is an integer from 0 to 10, and R" is hydrogen, alkyl or aryl, and Z is selected from: where R1 and R2 independent of each other, each are hydrogen, alkyl, cycloalkyl, hydroxyalkyl, arylated or aralkyl and, if 1 is 0, it can also be R and -CH2-R, where R has the meanings mentioned above or R Y - R, together with the nitrogen atom to which it is they are joined, form a substituted or unsubstituted heterocyclic structure which may contain another heteroatom selected from oxygen and nitrogen, is C3-C5 alkylene which is unsubstituted or mono- or poly substituted by alkyl, cycloalkyl, aryl, hetaryl, aralkyl or - hetaralkyl, is C2-C4 alkylene or C2-C4 alkenylene, both of which are unsubstituted or mono- or poly-substituted by alkyl, cycloalkyl, aryl, hetaryl, aralkyl, or hetaralkyl, or is o-arylene, m is 1 or 2, L is hydrogen, alkyl, aryl, aralkyl, hetaryl or hetaralkyl it is selected from: where, independent of each other, each is hydrogen, alkyl, aryl, hetaryl, aralkyl, or hetaralkyl, is from 1 to 50 and Alk "is C2-C- alkylene which is unsubstituted or substituted by hydroxyl and is hydrogen or an equivalent ester of an aliphatic, aromatic or araliphatic mono-, di-, tri or tetracarboxylic acid; or X is a functional group of the general formula (III). where n is an integer from 0 to 50, Alk is an alkylene unit of C2-C4, and E has one of the meanings mentioned above; or X is a functional group of the formula (Illb) -CH2 í ° -A Ail? -t-s NH2 < nib) s where Alk has one of the meanings mentioned above and s is an integer from 1 to 50; or X is a functional group of the formula (IV) wherein V is alkyl, aryl, aralkyl, -0-R13 or -MR14R15 and R13 a R, independent of each other, each can be hydrogen, alkyl, which can also be interrupted by one or more non-adjacent oxygen atoms and / or can also have NH2-6 OH-, or cycloalkyl, aryl, aralkyl, hetaryl or -hetaralkyl, W can be hydrogen, alkyl, cycloalkyl, aryl, aralkyl, hetaryl or hetaralkyl, alkyl carbonyl, alkyloxycarbonyl, or alkylaminocarbonyl, or V and W, together with the carbonyl function in V, form a group: where U is oxygen or NR1, where R can have the meanings set for R 13-R15; or, if i is from 2 to 4, X is a group of the general formula (V) where G is derived from a di-, tri- or tetravalent aliphatic radical, L has the aforementioned meanings and R17 is hydrogen or C1-C4 alkyl. 9. The functionalized polyolefin as mentioned in claim 8, of the formula (VI). -CH2- -NR R (VI) where R has the meanings set forth in claim 8, and Ra and Rb, independent of each other, may be hydrogen, alkyl, which may be interrupted by one or more non-adjacent amino groups or oxygen atoms, or cycloalkyl, which may also be have heteroatoms in ring, or aryl, aralkyl, hetaryl, hetaralkyl or CH2-R. The functionalized polyolefin as mentioned in claim 8, of the formula (VII). R CH2- NJ Alk O- ^ E (vil) L2-m where R, L, E, m and q have the meanings mentioned above and Alk "is 1,2-ethylene, 1,2- or 2,3-propylene or 1 , 2- or 3,4-butylene The functionalized polyolefin as mentioned in claim 8 of the formula (VIII). R-CH2-O E (VIII) where R and E have the meanings as mentioned in claim 8. 12. The functionalized polyolefin as recited in claim 8 of the formula (XIV) -CH2--Alk-f-0-E- (XIV) wherein R, Alk, and E have the meanings as set forth in claim 8, and n is an integer from 11 to 50. 13. The functionalized polyolefin as mentioned in claim 8 of the formula (XlVb). 10 -CH-Alk- -NH2 (XlVb) -ls where R and Alk have the meanings as set forth in claim 8, and s is an integer in the range of 10 to 40. 15 14. The use of a polyolefin as mentioned in any of claims 1 to 3 or of a functionalized polyolefin as mentioned in any of claims 8 to 13 or an additive for fuel or lubricant additive. 15. An additive mixture for fuel or lubricants, containing at least one compound as recited in claims 1 to 3 or 8 to 13, if required in combination with conventional fuel additives or lubricants. 16. A lubricant composition containing, in a conventional liquid or pasty lubricant, at least one compound as mentioned in any one of claims 1 to 3 or 8 to 13 in a total amount from 1 to 15% by weight based on the total weight of the composition, if required in combination with other lubricant additives. A fuel composition containing, a conventional fuel, at least one compound as recited in any of claims 1 to 3 or 8 to 13 in a total amount from about 20 to 5000 mg / kg of the fuel, if required in combination with other conventional fuel additives.