EP2646478A2

EP2646478A2 - Production of isobutylene homopolymer or copolymer derivatives

Info

Publication number: EP2646478A2
Application number: EP11788494.0A
Authority: EP
Inventors: Hannah Maria KÖNIG; Klaus MÜHLBACH; Helmut Mach; Ulrich Eichenauer
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2010-11-30
Filing date: 2011-11-29
Publication date: 2013-10-09
Also published as: EP4406982A3; AR084033A1; WO2012072643A2; EP4406982A2; WO2012072643A3

Abstract

Disclosed is the production of isobutylene homopolymer or copolymer derivatives comprising a hydrophobic polyisobutylene polymer residue that has a number average molecular weight of 110 to 250,000 and low-molecular polar groups containing amino functions, nitro groups, hydroxyl groups, mercaptan groups, carboxylic acid or carboxylic acid derivative functions, sulfonic acid or sulfonic acid derivative functions, aldehyde functions and/or silyl groups. According to the invention, isobutylene or a monomer mixture containing isobutylene is polymerized in the presence of an iron halide donor complex acting as a polymerization catalyst, an aluminum trihalide donor complex or an aluminum alkyl halide donor complex containing an organic compound having an ether function or a carboxylic acid ester function as a donor, or a Lewis acid complex containing organic sulfonic acids and optional donors, the resulting highly reactive isobutylene polymer is reacted with a compound introducing the low-molecular polar group or a substructure thereof, and in case the reaction is performed using a substructure, the formation of the low-molecular polar group is completed by performing successive reactions.

Description

Preparation of isobutene homo- or copolymer derivatives Description The present invention relates to an improved process for the preparation of isobutene homo- or copolymer derivatives. Furthermore, the present invention relates to novel isobutene homopolymer derivatives.

Isobutene homo- or copolymer derivatives such as polyisobutene amines or polyisobutenyl succinic anhydrides are frequently obtained from so-called highly reactive isobutene homo- or copolymers. In contrast to the so-called low-reactive polymers, highly reactive isobutene homopolymers or copolymers are understood to mean those polyisobutenes which contain a high content of terminal ethylenic double bonds (α-double bonds), in practice 80 mol% or more, based on the individual chain ends of the polyisobutene macromolecules. By vinylidene groups are usually understood such double bonds, their position in the polyisobutene macromolec ine formula

o ymer is described, i. the double bond is in an α-position in the polymer chain. "Polymer" stands for the polyisobutene radical shortened by one isobutene unit. The vinylidene groups show the highest reactivity, for example in the case of thermal addition to sterically demanding reactants such as maleic anhydride, whereas a double bond further inside the macromolecules shows in most cases no or lower reactivity in the case of functionalization reactions.

Such highly reactive polyisobutenes are used inter alia as intermediates for the preparation of additives for lubricants and fuels, for example, they are reacted according to the teaching of DE-A 27 02 604 with maleic anhydride to polyisobutenyl succinanhydriden. However, the highly reactive polyisobutenes obtainable by the process of DE-A 27 02 604 by cationic polymerization of isobutene in the liquid phase in the presence of boron trifluoride as catalyst have some disadvantages, for example they have a relatively high polydispersity. The polydispersity is a measure of the molecular weight distribution of the polymer chains obtained and corresponds to the quotient of weight-average molecular weight M _w and number-average molecular weight M _n (PDI = M _w / M _n ).

Polyisobutenes with a similarly high proportion of terminal double bonds, but with a narrower molecular weight distribution, are obtainable, for example, by the process of EP-A 145 235, US Pat. No. 5,408,018 and WO 99/64482, where Polymerization in the presence of a deactivated catalyst, for example a complex of boron trifluoride with alcohols and / or ethers, takes place.

Highly reactive polyisobutenes are also obtainable by living cationic polymerization of isobutene and subsequent dehydrohalogenation of the resulting polymerization product, for example according to the process of US Pat. No. 5,340,881. However, such a process is expensive, since the halogen end group introduced with the living cationic polymerization has to be eliminated in a separate step in order to generate the double bond.

It has also long been known that the Lewis acid aluminum trichloride can be used as a polymerization catalyst for isobutene, for example, from High Polymers, Volume XXIV (Part 2), pp. 713-733 (Editor: Edward C. Leonard), Verlag J Wiley & Sons, New York, 1971.

European Patent Application No. 10157068.7, not yet disclosed, discloses a process for preparing highly reactive isobutene homo- or copolymers by polymerization in the presence of an aluminum trihalide-donor complex effective as a polymerization catalyst or an aluminum alkyl halide donor complex which is a donor organic compound having at least one ether function or a carboxylic ester function and optionally containing an organic hydroxy compound, an organic halogen compound or water as an initiator disclosed. Further reactions with the highly reactive isobutene homo- or copolymers prepared in this way are not described there.

From CN 101955558 A it is known that iron (III) chloride is suitable as a coinitiator in the cationic isobutene polymerization for the preparation of highly reactive polyisobutenes and their copolymers. As initiators, water, phenols, protic acids such as sulfuric acid, tertiary alcohols, tertiary chlorides, tertiary carboxylic acid esters and carboxylic acids themselves are recommended. As a complexing agent for the polymerization initiating systems in particular alkyl ethers are mentioned.

However, the derivatization methods of highly reactive isobutene homo- or copolymers known from the prior art, for example for the preparation of polyisobutylsuccinic anhydrides according to the teaching of DE-A 27 02 604, have a number of shortcomings. Thus, the content of terminal vinylidene double bonds in the precursor is still too low. The yields in the conversion to the derivatives are in need of improvement. The appearance and the consistency of the derivatives, in particular the suppression of discoloration caused, for example, by undesired coking reactions under thermal stress during derivatization, are still not optimal. Furthermore, the physical properties of the derivatives, in particular the viscosity behavior at low temperatures, as may occur, for example, in practical use in lubricating oils, and the solvents Possibilities, in particular in polar media, the temperature stability and storage stability of derivatives still in need of improvement. The known from the prior art derivatization of isobutene polymers which emanate from isobutene polymers prepared by means of fluorine-containing polymerization catalysts have the disadvantage that they cause corrosion on numerous metallic materials and steel grades due to the residual fluorine content.

The object of the present invention was, starting from highly reactive Isobutenhomo- or copolymers, to provide an improved process for the preparation of isobutene homo- or copolymer derivatives, which no longer has the deficiencies of the prior art. In particular, the isobutene homo- or copolymer derivatives of isobutene polymers having a high content of terminal vinylidene double bonds, in particular at least 50 mol%, preferably at least 60 mol%, preferably at least 70 mol%, preferably at least 80 mol%, preferably at least 85 mole%, more preferably at least 90 mole%, and can be prepared in acceptable yields. Furthermore, the appearance and the consistency of the derivatives, for example their color, should be improved. Furthermore, the physical properties of the derivatives, in particular the viscosity behavior at low temperatures, and the solubilities, in particular in polar media, the temperature stability and the storage stability of the derivatives are to be improved. A catalyst system used for the production of isobutene polymers in the precursor should be sufficiently active, durable, easy to handle and not susceptible to interference, in particular, it should be free of fluorine to avoid unwanted due to residual fluorine content related corrosion on metallic materials and steel grades.

The object has been achieved by a process for the preparation of isobutene homo- or copolymer derivatives of the general formula I POL (-A) _n (I) in the

POL denotes the n-functional radical of a hydrophobic polyisobutene homo- or copolymer having a number-average molecular weight (M _n ) of 1 10 to 250 000, which may contain structural units of mono-, di- or trifunctional initiators,

A is a low molecular weight polar group, which in each case has one or more amino functions and / or nitro groups and / or hydroxyl groups and / or mercaptan groups and / or carboxylic acid or carboxylic acid derivative functions, in particular succinic anhydride or succinic acid derivative functions, and / or sulfonic acid or sulfonic acid derivative functions and / or contains aldehyde functions and / or silyl groups, means and the variable n is the number 1, 2 or 3, where at n = 2 and n = 3, the variables A may be the same or different, which is characterized in that isobutene or a isobutene-containing monomer mixture in the presence of a Polymerization catalyst of effective iron halide donor complex, an aluminum trihalide donor complex or an aluminum alkyl halide donor complex which contains as donor an organic compound having at least one ether function or a carboxylic acid ester function, or (B) at least a Lewis acid which is suitable as a polymerization catalyst or a complex of at least one Lewis acid and at least one donor which acts as a polymerization catalyst and in the presence of at least one initiator, where at least one initiator is an organic sulfonic acid of the general formula Z-SO3H the variable Z is a C1 to C2o-alkyl, d- to C2o-haloalkyl rest, C5- to Ce-cycloalkyl, CQ-bis

C2o-aryl radical or a C ₇ - to C2o-arylalkyl radical, designated polymerized, the resulting highly reactive isobutene homo- or copolymer having a content of at least 50 mol% of terminal vinylidene double bonds per polyisobutene chain end, with at least n equivalents of a the low molecular weight polar group A or a partial structure of the low molecular weight polar group A implementing compound and in the case of implementation with a partial structure completes the formation of the low molecular weight polar group A by subsequent reactions.

The above-mentioned polymerization method for inventive isobutene or isobutene-containing monomer mixtures according to embodiment (A) is essentially described in the above-cited European patent application, not yet disclosed, with the file reference 10157068.7 and is reproduced below.

In the context of the present invention, isobutene homopolymers are understood to mean those polymers which, based on the polymer, are composed of at least 98 mol%, preferably at least 99 mol%, of isobutene. Accordingly, isobutene copolymers are understood as meaning those polymers which contain more than 2 mol% of monomers copolymerized in a different form from isobutene, for example linear butenes.

In the context of the present invention, the following definitions apply to generically defined radicals: A C to Ce alkyl radical is a linear or branched alkyl radical having 1 to 8 carbon atoms. Examples of these are methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1, 1-dimethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methyl-pentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl,

1, 3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1, 1, 2-trimethylpropyl, 1, 2,2-trimethylpropyl, 1 - Ethyl 1-methylpropyl, 1-ethyl-2-methyl-propyl, n-heptyl, n-octyl and its constitutional isomers such as 2-ethylhexyl. Such C 1 - to C 6 -alkyl radicals can also contain, to a small extent, heteroatoms such as oxygen, nitrogen or halogen atoms, for example chlorine, and / or non-protic functional groups such as, for example, carboxyl ester groups, cyano groups or nitro groups. A C 2 to C 20 alkyl radical is a linear or branched alkyl radical having 1 to 20 carbon atoms. Examples of these are the abovementioned C 1 - to C 6 -alkyl radicals and furthermore n-nonyl, isononyl, n-decyl, 2-propylheptyl, n-undecyl, n-dodecyl, n-tricycde, isotridecyl, n Tetradecyl, n-hexadecyl, n-octadecyl and n-eicosyl. Such C 2 to C 20 alkyl radicals can also contain, to a small extent, heteroatoms such as oxygen, nitrogen or halogen atoms, for example chlorine, and / or non-protic functional groups such as, for example, carboxyl ester groups, cyano groups or nitro groups.

A C5 to Ce cycloalkyl group is a saturated cyclic group which may contain alkyl side chains. Examples of these are cyclopentyl, 2- or 3-methylcyclopentyl, 2,3-,

2,4- or 2,5-dimethylcyclopentyl, cyclohexyl, 2-, 3- or 4-methylcyclohexyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, 3,5- or 3,6-dimethylcyclohexyl, cycloheptyl, 2-, 3- or 4-methylcycloheptyl, cyclooctyl, 2-, 3-, 4- or 5-methylcyclooctyl. Such C5 to Ce cycloalkyl radicals may also contain, to a small extent, heteroatoms such as oxygen, nitrogen or halogen atoms, for example chlorine, and / or non-protic functional groups such as, for example, carboxyl ester groups, cyano groups or nitro groups.

A CQ to C 20 -aryl radical or a C 10 to C 12 aryl radical is preferably optionally substituted phenyl, optionally substituted naphthyl, optionally substituted anthracenyl or optionally substituted phenanthrenyl. Such aryl groups may carry from 1 to 5 non-protic substituents or non-protic functional groups, for example, C 1 to C 6 alkyl, C 1 to C 6 haloalkyl such as C 1 to C 6 chloroalkyl or C 1 to C 6 fluoroalkyl, halogen such as chloro or Fluorine, nitro, cyano or phenyl. Examples of such aryl radicals are phenyl, naphthyl, biphenyl, anthracenyl, phenanthrenyl, tolyl, nitrophenyl, chlorophenyl, dichlorophenyl, pentafluorophenyl, pentachlorophenyl, (trifluoromethyl) phenyl, bis (trifluoromethyl) phenyl, (trichloro) methylphenyl and bis (trichloromethyl ) phenyl. A C ₇ - to C 20 -arylalkyl radical or a C ₇ - to C 12 -arylalkyl radical is preferably optionally substituted C 1 -C 4 -alkylphenyl, such as benzyl, o-, m- or p-methylbenzyl, 1- or 2-phenylethyl , 1-, 2- or 3-phenylpropyl or 1-, 2-, 3- or 4-phenylbutyl, for optionally substituted C 1 -C 4 -alkylnaphthyl, such as naphthylmethyl, for optionally substituted C 1 -C 4 -alkylanthracenyl, such as anthracenylmethyl or optionally substituted C 1 to C 4 alkylphenanthrenyl, such as phenanthrenylmethyl. Such arylalkyl radicals may carry 1 to 5 non-protic or non-protic functional groups, in particular on the aryl part, for example d- to Ce-alkyl, d- to Ce-haloalkyl such as d- to Ce-chloroalkyl or d- to Ce-fluoroalkyl, halogen such as chlorine or fluorine, nitro or phenyl.

Suitable iron halides in the corresponding complexes with donors are, for example, iron (II) fluoride, iron (III) fluoride, iron (II) chloride, iron (III) chloride, iron (II) bromide and iron ( III) bromide and mixtures thereof. Preference is given to iron chlorides, ie iron (II) chloride and iron (III) chloride, and mixtures of iron (II) chloride and iron (III) chloride, but especially iron (III) chloride alone. It is also possible to use iron halides, in particular iron chlorides, which have been produced from iron-containing metal alloys, ie in addition to iron halides, in particular iron chlorides, also contain other metal halides, the iron halides, in particular iron chlorides, preferably being the main constituents of such mixtures.

As aluminum trihalide is particularly suitable aluminum trifluoride, aluminum trichloride or aluminum tribromide. Suitable aluminum alkyl halide is, in particular, a mono (C 1 -C 4 -alkyl) aluminum dihalide or a di (C 1 -C 4 -alkyl) aluminum monohalide, for example methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum chloride or diethylaluminum chloride. In a preferred embodiment, isobutene or an isobutene-containing monomer mixture is polymerized in the presence of an aluminum trichloride-donor complex which acts as a polymerization catalyst.

If the polymerization catalyst has an effective iron halide donor complex, aluminum trihalide donor complex or aluminum alkyl halide donor complex donor as an organic compound having at least one ether function, among compounds having at least one ether function also acetals and Halbaceta- le to understand.

In a preferred embodiment of the present invention, an iron halide donor complex, an aluminum trihalide donor complex or an aluminum alkyl halide donor complex, in particular a ferric chloride donor complex or an aluminum trichloride donor complex, is used which acts as a donor a dihydrocarbyl ether of the general formula R ¹ -O-R ² in which the variables R ¹ and R ² independently of one another are C 1 - to C 20 -alkyl radicals, in particular, C 1 - to C 6 -alkyl radicals, C 5 - to C 6 -cycloalkyl radicals, C 2 - to C 20 -aryl radicals, in particular C 1 - to C 12 -aryl radicals, or C ₇ - to C2o-arylalkyl radicals, in particular C ₇ - to Ci2 arylalkyl radicals, denote.

The dihydrocarbyl ethers mentioned may be open-chain or cyclic, wherein in the case of the cyclic the two variables R ¹ and R ² form a ring, such rings also being able to contain two or three ether oxygen atoms. Examples of such open-chain and cyclic dihydrocarbyl ethers are dimethyl ether, diethyl ether, di-n-propyl ether, diisopropyl ether, di-n-butyl ether, di-sec-butyl ether, diisobutyl ether, di-n-pentyl ether, di-n-hexyl ether, di -n-heptyl ether, di-n-octyl ether, di- (2-ethylhexyl) ether, methyl n-butyl ether, methyl sec-butyl ether, methyl isobutyl ether, methyl tert-butyl ether, ethyl n- butyl ether, ethyl sec-butyl ether, ethyl isobutyl ether, n-propyl n-butyl ether, n-propyl sec-butyl ether, n-propyl isobutyl ether, n-propyl tert-butyl ether, isopropyl n-butyl ether, isopropyl sec-butyl ether, isopropyl isobutyl ether, isopropyl tert-butyl ether, methyl n-hexyl ether, methyl n-octyl ether, methyl (2-ethylhexyl) ether, ethyl n-hexyl ether, ethyl n-octyl ether, ethyl (2-ethylhexyl) ether, n-butyl n-octyl ether, n-butyl (2-ethylhexyl) ether, tetrahydrofuran, tetrahydropyran, 1, 2, 1, 3 and 1, 4 Dioxane, dicyclohexyl ether, diphenyl ether, ditolyl ether, dixylyl ether and dibenzyl ether. Of the dihydrocarbyl ethers mentioned, di-n-butyl ethers and diphenyl ethers have donors for the iron halide donor complexes, the aluminum trihalide donor complexes or the aluminum alkyl halide donor complexes, in particular the iron chloride donor complexes or the Aluminum trichloride donor complexes, found to be particularly advantageous.

In a further preferred embodiment of the present invention, an iron halide donor complex, an aluminum trihalide donor complex or an aluminum alkyl halide donor complex, in particular a ferric chloride donor complex or an aluminum trichloride donor complex, is used as an alternative - Rather than donor a Carbonsäurehydrocarbylester of the general formula R ³ -COOR ⁴ contains, in which the variables R ³ and R ⁴ independently of one another C to C 20 -alkyl radicals, in particular, d- to Ce-alkyl radicals, C5 to Ce cycloalkyl radicals, CQ - Denote C2o-aryl radicals, in particular CQ- to Ci2-aryl radicals, or C ₇ - to C 2o-arylalkyl radicals, in particular C ₇ - to C 12 -arylalkyl radicals.

Examples of the said carboxylic acid hydrocarbyl esters are methyl formate, ethyl formate, n-propyl formate, formic acid isopropyl ester, n-butyl formate, sec-butyl formate, formic acid isobutyl ester, formic acid tert -butyl ester, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, sec-butyl acetate, isobutyl acetate, tert-butyl acetate, propionic acid. acid methyl ester, ethyl propionate, n-propyl propionate, propionic acid isopropyl ester, n-butyl propionate, sec-butyl propionate, propionic acid acid isobutyl ester, tert-butyl propionate, methyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, secbutyl butyrate, isobutyl butyric acid, butyric acid tert -butyl ester, methyl cyclohexanecarboxylate, n-propyl cyclohexanecarboxylate, n-propyl cyclohexanecarboxylate, n-butyl cyclohexanecarboxylate, sec-butyl cyclohexanecarboxylate, isobutyl cyclohexanecarboxylate, tert-butyl cyclohexanecarboxylate, Methyl benzoate, ethyl benzoate, n-propyl benzoate, iso-propyl benzoate, n-butyl benzoate, sec-butyl benzoate, isobutyl benzoate, tert-butyl benzoate, methyl phenylacetate, phenyl- ethyl acetate, n-propyl phenylacetate, isopropyl isopropylacetoacetate, n-butyl phenylacetate, phenylacetic acid sec . butyl ester, isobutyl phenylacetate and tert-butyl phenylacetate. Of the carboxylic acid hydrocarbyl esters mentioned, ethyl acetate has been used as donor for the iron halide donor complexes, the aluminum trihalide donor complexes or the aluminum alkyl halide donor complexes, in particular the iron chloride donor complexes or the aluminum trichloride complexes. Donor complexes, proved to be particularly advantageous.

Furthermore, those dihydrocarbyl ethers and carboxylic acid hydrocarbyl esters have been found to be particularly useful as donors for the iron halide donor complexes, the aluminum trihalide donor complexes and the aluminum alkyl halide donor complexes, in particular the iron chloride donor complexes and the aluminum trichloride donor complexes, respectively has been found advantageous in which the donor compound has a total carbon number of from 3 to 16, preferably from 4 to 16, in particular from 4 to 12, especially from 4 to 8. In the case of the dihydrocarbyl ethers, especially those having a total of 6 to 14, in particular 8 to 12, carbon atoms are preferred. In particular, those having a total of 3 to 10, in particular 4 to 6, carbon atoms are preferred for the carboxylic acid hydrocarbyl esters in particular. The molar ratio of said donor compounds to the iron halide, to the aluminum trihalide or to the aluminum alkyl halide, in particular to the iron chloride or to the aluminum trichloride, in the donor complex generally ranges from 0.3: 1 to 1.5: 1 , in particular from 0.5: 1 to 1, 2: 1, especially 0.7: 1 to 1, 1: 1; it is in most cases 1: 1. However, it is also possible to work with a greater degree of overshoot of the donor compounds, often up to a 10-fold, in particular 3-fold, molar excess; the excess amount of donor compounds then additionally acts as a solvent or diluent.

Usually, the iron halide donor complex, the aluminum trihalide donor complex or the aluminum alkyl halide donor complex, in particular the iron chloride donor complex or the aluminum trichloride donor complex, before the polymerization separately from the iron halide, the aluminum trihalide or the aluminum alkyl halide, in particular from anhydrous iron chloride or aluminum halide. umtrichlorid, and the donor compound prepared and then - usually dissolved in an inert solvent such as a halogenated hydrocarbon, such as dichloromethane - added to the polymerization medium. However, the complex can also be prepared in situ prior to polymerization.

In a preferred embodiment of the present invention, the polymerization is carried out with the use of a mono- or polyfunctional, in particular mono-, di- or trifunctional initiator, which is selected from organic hydroxy compounds, organic halogen compounds, protic acids and water. It is also possible to use mixtures of the initiators mentioned, for example mixtures of two or more organic hydroxy compounds, mixtures of two or more organic halogen compounds, mixtures of one or more organic hydroxy compounds and one or more organic halogen compounds, mixtures of one or more organic hydroxy compounds and water , Mixtures of one or more organic halogen compounds and water or mixtures of one or more protic acids and water. The initiator may be mono-, di- or polyfunctional, i. One, two or more hydroxyl groups or halogen atoms may be present in the initiator molecule at which the polymerization reaction starts. In the case of di- or polyfunctional initiators, it is customary to obtain telechelic isobutene polymers having two or more, in particular two or three, polyisobutene chain ends.

Suitable monofunctional initiators organic hydroxy compounds having only one hydroxyl group in the molecule are especially alcohols and phenols, especially those of the general formula R ⁵ -OH, in the R ⁵ d to C2o-alkyl radicals, in particular, d- to Ce-alkyl radicals , C5- to Ce-cycloalkyl, CQ to C2o-aryl radicals, particularly CQ to Ci2-aryl, or C ₇ - to C2o-arylalkyl radicals, in particular C ₇ - to Ci2 arylalkyl radicals, respectively. Furthermore, the radicals R ^{5 may} also contain mixtures of the abovementioned structures and / or have functional groups other than those mentioned above, for example a keto function, a nitroxide or a carboxyl group, and / or heterocyclic structural elements.

Typical examples of such organic monohydroxy compounds are methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, isobutanol, tert-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, 2 Ethylhexanol, cyclohexanol, phenol, p-methoxyphenol, o-, m- and p-cresol, benzyl alcohol, p-methoxybenzyl alcohol, 1- and 2-phenylethanol, 1- and 2- (p-methoxyphenyl) ethanol, 1 -, 2 and 3-phenyl-1-propanol, 1-, 2- and 3- (p-methoxyphenyl) -1-propanol, 1- and 2-phenyl-2-propanol, 1- and 2- (p-methoxyphenyl ) -2-propanol, 1-, 2-, 3- and 4-phenyl-1-butanol, 1-, 2-, 3- and 4- (p-methoxyphenyl) -1-butanol, 1 -, 2 , 3- and 4-phenyl-2-butanol, 1-, 2-, 3- and 4- (p-methoxyphenyl) -2-butanol, 9-methyl-9H-fluoren-9-ol, 1, 1-diphenylethanol, 1,1-diphenyl-2-propyn-1-ol, 1,1-diphenylpropanol, 4- (1-hydroxy-1-phenylethyl) benzonitrile, cyclopropyldiphenyl methanol, 1-hydroxy-1, 1-diphenylpropan-2-one, benzilic acid, 9-phenyl-9-fluorenol, triphenylmethanol, diphenyl (4-pyridinyl) methanol, alpha, alpha-diphenyl-2-pyridinemethanol, 4-methoxytrityl alcohol (in particular polymer-bound as solid phase), alpha- tert -butyl-4-chloro-4'-methylbenzhydrol, cyclohexyldiphenylmethanol, alpha- (p-tolyl) -benzhydrol, 1, 1, 2-triphenylethanol, alpha, alpha- Diphenyl-2-pyridineethanol, alpha, alpha-4-pyridylbenzohydrol-N-oxide, 2-fluorotriphenylmethanol, triphenylpropargyl alcohol, 4 - [(diphenyl) hydroxymethyl] benzonitrile, 1- (2,6-dimethoxyphenyl) -2- methyl 1-phenyl-1-propanol, 1, 1, 2-triphenylpropane-1-ol and p-anisaldehyde carbinol. Particularly suitable bifunctional initiators organic hydroxy compounds having two hydroxyl groups in the molecule are especially dihydric alcohols or diols having a total carbon number of 2 to 30, in particular from 3 to 24, especially from 4 to 20, and bisphenols having a total carbon number of 6 to 30, especially of 8 to 24, especially from 10 to 20, for example, ethylene glycol, 1, 2 and 1, 3-propylene glycol, 1, 4-butylene glycol, 1, 6-hexylene glycol, 1, 2, 1, 3 or 1,4-bis (1-hydroxy-1-methylethyl) benzene (o-, m- or p-dicumyl alcohol), bisphenol A, 9,10-dihydro-9,10-dimethyl-9,10-anthracenediol , 1, 1-diphenylbutane-1, 4-diol, 2-hydroxytri- phenylcarbinol and 9- [2- (hydroxymethyl) phenyl] -9-fluorenol. Suitable monofunctional initiators organic halogen compounds having a halogen atom in the molecule are especially compounds of general formula R ⁶ -hal call, in the shark a halogen atom selected from fluorine, iodine and in particular chlorine and bromine, and R ⁶ d- to C2o Alkyl radicals, in particular, d- to Ce-alkyl radicals, C5- to Ce-cycloalkyl or C ₇ - to C 2o-arylalkyl radicals, in particular C ₇ - to Ci2-Arylalkylreste designated. Furthermore, the radicals R ^{6 may} also contain mixtures of the abovementioned structures and / or have functional groups other than those already mentioned, for example a keto function, a nitroxide or a carboxyl group, and / or heterocyclic structural elements. Typical examples of such organic monohalogen compounds are methyl chloride, methyl bromide, ethyl chloride, ethyl bromide, 1-chloropropane, 1-bromopropane, 2-chloropropane, 2-bromopropane, 1-chlorobutane, 1-bromobutane, sec-butyl chloride, sec-butyl bromide , Isobutyl chloride, isobutyl bromide, tert-butyl chloride, tert-butyl bromide, 1-chloropentane, 1-bromopentane, 1-chlorohexane, 1-bromohexane, 1-chloroheptane, 1-bromoheptane, 1-chloroctane, 1-bromoctane, 1 Chloro-2-ethylhexane, 1-bromo-2-ethylhexane, cyclohexylchloride, cyclohexylbromide, benzylchloride, benzylbromide, 1-phenyl-1-chloroethane, 1-phenyl-1-bromoethane, 1-phenyl-2-chloroethane, 1 Phenyl 2-bromoethane, 1-phenyl-1-chloropropane,

1 - phenyl-1-bromopropane, 1-phenyl-2-chloropropane, 1-phenyl-2-bromopropane, 2-phenyl-2-chloropropane, 2-phenyl-2-bromopropane, 1-phenyl-3-chloropropane, 1 - Phenyl-3-bromopro- pan, 1-phenyl-1-chlorobutane, 1-phenyl-1-bromobutane, 1-phenyl-2-chlorobutane, 1-phenyl-

2-bromobutane, 1-phenyl-3-chlorobutane, 1-phenyl-3-bromobutane, 1-phenyl-4-chlorobutane, 1-phenyl-4-bromobutane, 2-phenyl-1-chlorobutane, 2-phenyl-1 - bromobutane, 2-phenyl-2-chloro butane, 2-phenyl-2-bromobutane, 2-phenyl-3-chlorobutane, 2-phenyl-3-bromobutane, 2-phenyl-4-chlorobutane and 2-phenyl-4-bromobutane.

Suitable difunctional initiators for organic halogen compounds having two halogen atoms in the molecule are, for example, 1,3-bis (1-bromo-1-methylethyl) benzene, 1,3-bis (2-chloro-2-propyl) benzene (1 , 3-dicumyl chloride) and 1, 4-bis (2-chloro-2-propyl) benzene (1, 4-dicumyl chloride).

The initiator is particularly preferably selected from organic hydroxy compounds in which one or more hydroxyl groups are bonded to one sp ³ -hybridized carbon atom ("alcohols") or to one aromatic ring ("phenols"), organic halogen compounds in which one or more halogen atoms are bonded to one sp ³ -hybridized carbon atom, proton acids and water. Of these, particular preference is given to an initiator which is selected from organic hydroxy compounds in which one or more hydroxyl groups are bonded to one sp ³ -hybridized carbon atom in each case.

Particular preference is given in the case of the organic halogen compounds as initiators to those in which the one or more halogen atoms are each bonded to a secondary or in particular to a tertiary sp ³ -hybridized carbon atom.

Primary preference is given to initiators which, in addition to the hydroxyl group, carry the radicals R ¹⁰ , R ¹¹ and R ¹² on such an sp ³ -hydrified carbon atom, which independently of one another are hydrogen, C 1 - to C 20 -alkyl, C 5 - to C 6 -cycloalkyl , CQ to C 20 aryl, C ₇ - to C2o-alkylaryl or phenyl, where an aromatic nucleus, one or more, preferably one or two C-C4 alkyl, C-C4 alkoxy, C -C ₄ - hydroxy-alkyl or C can carry as substituents up to C ₄ -Halogenalkylreste denote, wherein at most one of the variables R ^10, R ¹¹ or R ¹² is hydrogen and at least one of the variables R ^10, R ¹¹ or R ¹² is phenyl, which still one or more, preferably one or two C to C ₄ alkyl, C to C ₄ alkoxy, C to C ₄ - hydroxyalkyl or C to C ₄ haloalkyl radicals may carry as substituents. Suitable protonic acids are, for example, hydrochloric acid, hydrobromic acid, hydrofluoric acid, sulfuric acid, hydrocyanic acid and mixtures thereof. As proton acids but also protonated ethers can be used. Very particular preference is given to initiators which are present under water, one or more protic acids, methanol, ethanol, 1-phenylethanol, 1 - (p-methoxyphenyl) ethanol, n-propanol, isopropanol, 2-phenyl-2- propanol (cumene), n-butanol, isobutanol, sec-butanol, tert-butanol, 1-phenyl-1-chloroethane, 2- Phenyl-2-chloropropane (cumyl chloride), tert-butyl chloride and 1, 3- or 1, 4-bis (1 - hydroxy-1-methylethyl) benzene and mixtures thereof are selected. Of these, particular preference is given to initiators which, under water, one or more protic acids, methanol, ethanol, 1-phenylethanol, 1- (p-methoxyphenyl) ethanol, n-propanol, isopropanol, 2-phenyl-2-propanol (cumene), n-butanol, isobutanol, sec-butanol, tert-butanol, 1-phenyl-1-chloroethane and 1, 3- or 1, 4-bis (1-hydroxy-1-methyl-ethyl) benzene and mixtures thereof are selected.

The molar ratio of said initiators to the isobutene monomer used in homopolymerization of isobutene or to the total amount of polymerizable monomers used in the copolymerization of isobutene, based on each individual functional point of the initiator according to embodiment (A) is usually 0.0005: 1 to 0.1: 1, in particular 0.001: 1 to 0.075: 1, especially 0.0025: 1 to 0.05: 1. When water is used as the sole initiator or in combination with organic hydroxy compounds and / or organic halogen compounds as further initiators, the molar ratio of water to isobutene monomer used in homopolymerization of isobutene or to the total amount of the polymerizable monomers used in copolymerization of isobutene in particular 0, 0001: 1 to 0.1: 1, especially 0.0002: 1 to 0.05: 1.

Part of the initiator molecules added as organic hydroxy or halogen compounds is incorporated into the polymer chains in embodiment (A). The proportion (ff) of polymer chains which are started by such a built-in organic initiator molecule can be up to 100%, usually from 5 to 90%. The remaining polymer chains are formed either by moisture-derived water as the initiator molecule or by chain transfer reactions.

In a further preferred embodiment of the present invention, the polymerization is carried out in the presence of from 0.01 to 10 mmol, in particular from 0.05 to 5.0 mmol, especially from 0.1 to 1.0 mmol, in each case based on 1 mol used isobutene monomer in homopolymerization of isobutene or to 1 mol of the total amount of the polymerizable monomers used in copolymerization of isobutene, a nitrogen-containing basic compound. As such nitrogen-containing basic compound it is possible to use an aliphatic, cycloaliphatic or aromatic amine of the general formula R ⁷ -NR ⁸ R ⁹ or else ammonia, in which the variables R ⁷ , R ⁸ and R ^{9 are} each independently of one another hydrogen, d C 2 - to C 20 -alkyl radicals, in particular, C 1 - to C ₆ -alkyl radicals, C 5 - to C ₆ -cycloalkyl radicals, C 2 - to C 20 -aryl radicals, in particular C 2 - to C 12 -aryl radicals, or C ₇ - to C 20 -arylalkyl radicals, in particular C ₇ - to Ci2-arylalkyl radicals. If none of these variables is hydrogen, a tertiary amine is present. If one of these variables is hydrogen, a secondary amine is present. Stand two of these variables for Hydrogen, is a primary amine. If all of these variables are hydrogen, ammonia is present.

Typical examples of such amines of the general formula R ⁷ -NR ⁸ R ⁹ are methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, tert-butylamine, sec-butylamine, isobutylamine, tert. Amylamine, n-hexylamine, n-heptylamine, n-octylamine, 2-ethylhexylamine, cyclopentylamine, cyclohexylamine, aniline, dimethylamine, diethylamine, di-n-propylamine, di-iso-propylamine, di-n-butylamine, di-tert. -butylamine, di-sec-butylamine, di-iso-butylamine, di-tert-amylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di (2-) ethylhexyl) amine, dicyclopentylamine, dicyclohexylamine, diphenylamine, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, tri-tert-butylamine, tri-sec-butyl-amine, Tri-iso-butylamine, tri-tert-amylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octyl-amine, tri (2-ethylhexyl) amine, tricyclopentylamine, tricyclohexylamine, triphenylamine, Dimethylethylamine, methyl-n-butylamine, N-methyl-N-phenylamine, N, N-dimethyl-N-phenylamine, N-methyl-N, N-di phenylamine or N-methyl-N-ethyl-Nn-butylamine.

Furthermore, as such nitrogen-containing basic compound, a compound having a plurality, in particular having two or three nitrogen atoms and having 2 to 20 carbon atoms are used, these nitrogen atoms each independently of one another carry hydrogen atoms or aliphatic, cycloaliphatic or aromatic substituents. Examples of such polyamines are 1, 2-ethylenediamine, 1, 3-propylenediamine, 1, 4-butylenediamine, diethylenetriamine, N-methyl-1, 2-ethylenediamine, N, N-dimethyl-1, 2-ethylenediamine, N , N'-dimethyl-1, 2-ethylenediamine or N, N-dimethyl-1,3-propylenediamine.

However, a saturated, partially unsaturated or unsaturated nitrogen-containing five-membered or six-membered heterocycle which contains one, two or three ring nitrogen atoms and one or two further ring heteroatoms selected from the group consisting of oxygen and sulfur and / or hydrocarbyl radicals, in particular d-butyl, is particularly suitable as such nitrogen-containing basic compound. to C ₄ -alkyl radicals and / or phenyl, and / or functional groups or heteroatoms as substituents, in particular fluorine, chlorine, bromine, nitro and / or cyano, may have, for example pyrrolidine, pyrrole, imidazole, 1, 2,3 - or 1, 2,4-triazole, oxazole, thiazole, piperidine, pyrazane, pyrazole, pyridazine, pyrimidine, pyrazine, 1, 2,3-, 1, 2,4- or 1, 2,5-triazine, 1, 2,5-oxathiazine, 2H-1, 3,5-thiadiazine or morpholine.

However, very particularly suitable as such nitrogen-containing basic compound is pyridine or a derivative of pyridine (in particular a mono-, di- or tri- to C ₄ -alkyl-substituted pyridine) such as 2-, 3-, or 4-methylpyridine ( Picolines), 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, 3,5- or 3,6-dimethylpyridine (lutidines), 2,4,6-trimethylpyridine ( Collidine), 2-, 3, - or 4-tert-butylpyridine, 2-tert-butyl-6-methylpyridine, 2,4-, 2,5-, 2,6- or 3,5-di-tert .-Butylpyridine or 2-, 3, - or 4-phenylpyridine. One can use a single nitrogen-containing basic compound or mixtures of such nitrogen-containing basic compounds. The invention for the present invention mentioned polymerization method for isobutene or isobutene-containing monomer mixtures according to embodiment (B) is reproduced below.

In the context of the present invention, isobutene homopolymers are understood to mean those polymers which, based on the polymer, are composed of at least 98 mol%, preferably at least 99 mol%, of isobutene. Accordingly, isobutene copolymers are understood as meaning those polymers which contain more than 2 mol% of monomers copolymerized in a different form from isobutene, for example linear butenes. In the context of the present invention, the following definitions apply to generically defined radicals:

A C to Ce alkyl radical is a linear or branched alkyl radical having 1 to 8 carbon atoms. Examples of these are methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1, 1-dimethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methyl-pentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1, 1, 2-trimethylpropyl, 1, 2,2-trimethylpropyl, 1 - Ethyl 1-methylpropyl, 1-ethyl-2-methyl-propyl, n-heptyl, n-octyl and its constitutional isomers such as 2-ethylhexyl. Such d- to Ce-alkyl radicals can also to a small extent heteroatoms such as oxygen, nitrogen or halogen atoms, eg. As chlorine or fluorine, and / or non-protic functional groups such as carboxyl ester groups, cyano groups or nitro groups.

A C 2 to C 20 alkyl radical is a linear or branched alkyl radical having 1 to 20 carbon atoms. Examples of these are the abovementioned C 1 - to C 6 -alkyl radicals and furthermore n-nonyl, isononyl, n-decyl, 2-propylheptyl, n-undecyl, n-dodecyl, n-tricycde, isotridecyl, n Tetradecyl, n-hexadecyl, n-octadecyl and n-eicosyl. Such C to C 20 -alkyl radicals can also to a small extent heteroatoms such as oxygen, nitrogen or halogen atoms, for. As chlorine or fluorine, and / or non-protic functional groups such as carboxyl ester groups, cyano groups or nitro groups. A C 2 to C 20 haloalkyl radical or a C 1 to C 10 haloalkyl radical is a radical having the abovementioned skeletons for C 1 - to C 20 -alkyl radicals or C 1 - to C 6 -alkyl radicals, in which, however, the hydrogen atoms are replaced by halogen atoms, are replaced in particular by fluorine and / or chlorine atoms. Preferably, all or almost all hydrogen atoms replaced by halogen atoms, in particular by fluorine and / or chlorine atoms. Typical examples of such radicals are C ₁ - to C ₄ -alkyl radicals in which at least 60%, in particular at least 75%, especially at least 90% of the number of hydrogen atoms are replaced by fluorine and / or chlorine atoms, for example dichloromethyl, trichloromethyl , Difluoromethyl, trifluoromethyl, chlorodifluoromethyl, fluorodichloromethyl, pentachloroethyl or pentafluoroethyl.

A C5 to Ce cycloalkyl group is a saturated cyclic group which may contain alkyl side chains. Examples of these are cyclopentyl, 2- or 3-methylcyclopentyl, 2,3-, 2,4- or 2,5-dimethylcyclopentyl, cyclohexyl, 2-, 3- or 4-methylcyclohexyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, 3,5- or 3,6-dimethylcyclohexyl, cycloheptyl, 2-, 3- or 4-methylcycloheptyl, cyclooctyl, 2-, 3-, 4- or 5 -Methylcyclooctyl. Such C5 to Ce- cycloalkyl radicals may also to a small extent heteroatoms such as oxygen, nitrogen or halogen atoms, for. As chlorine or fluorine, and / or non-protic functional groups such as carboxyl ester groups, cyano groups or nitro groups.

A CQ to C 20 -aryl radical or a C 12 to C 12 -aryl radical is preferably optionally substituted phenyl, optionally substituted naphthyl, optionally substituted anthracenyl or optionally substituted phenanthrenyl. Such aryl groups may carry from 1 to 5 non-protic substituents or non-protic functional groups, for example, C 1 to C 6 alkyl, C 1 to C 6 haloalkyl such as C 1 to C 6 chloroalkyl or C 1 to C 6 fluoroalkyl, halogen such as chloro or Fluorine, nitro, cyano or phenyl. Examples of such aryl radicals are phenyl, naphthyl, biphenyl, anthracenyl, phenanthrenyl, tolyl, nitrophenyl, chlorophenyl, dichlorophenyl, pentafluorophenyl, pentachlorophenyl, (trifluoromethyl) phenyl, bis (trifluoromethyl) phenyl, (trichloro) methylphenyl and bis (trichloromethyl) phenyl.

A C ₇ - to C 20 -arylalkyl radical or a C ₇ - to C 12 -arylalkyl radical is preferably unsubstituted or substituted C 1 -C ₄ -alkylphenyl, such as benzyl, o-, m- or p-methylbenzyl, 1- or 2- Phenylethyl, 1-, 2- or 3-phenylpropyl or 1-, 2-, 3- or 4-phenylbutyl, for optionally substituted C 1 to C ₄ -alkylnaphthyl, such as naphthylmethyl, for optionally substituted C 1 to C ₄ -alkylanthracenyl, such as Anthracenylmethyl or optionally substituted Cr to C ₄ alkylphenanthrenyl such as phenanthrenyl methyl. Such arylalkyl radicals may carry 1 to 5 non-protic or non-protic functional groups, in particular on the aryl part, for example d- to Ce-alkyl, d- to Ce-haloalkyl such as d- to Ce-chloroalkyl or d- to Ce-fluoroalkyl, halogen such as chlorine or fluorine, nitro or phenyl. The process according to the invention for the preparation of highly reactive isobutene homo- or co-polymers is generally carried out-owing to the use of the complex, which is effective as a polymerization catalyst, of at least one Lewis acid and optionally at least one donor and the initiators described - after a cationic reaction mechanism.

The feature essential to the invention is the use of an organic sulfonic acid of the general formula Z-SO3H as at least one initiator in the polymerization process according to the invention. Of course, it is also possible to use mixtures of different sulfonic acids Z-SO3H. In addition to these sulfonic acid initiators further initiator molecules from other chemical classes can be used.

The variable Z preferably represents a C to Ce-alkyl radical, C to Ce-haloalkyl radical, C5 to Ce-cycloalkyl radical, CQ to C 12 -aryl radical or a C ₇ to C 12 -arylalkyl radical. Z is particularly preferably a C 1 to C ₄ -alkyl radical, a C ₄ to C ₄ -haloalkyl radical, an optionally substituted phenyl radical, eg. B. rest a tolyl radical or a xylyl radical, or an optionally substituted C -C ₄ alkylphenyl, z. B. a benzyl radical.

In a particularly preferred embodiment of the present invention, at least one initiator is an organic sulfonic acid selected from methanesulfonic acid, trifluoromethanesulfonic acid, trichloromethanesulfonic acid and toluenesulfonic acid or mixtures thereof.

As a Lewis acid suitable as a polymerization catalyst or in the polymerization complex acting in principle all by definition as Lewis acids designated inorganic molecules, but in particular halogen compounds of metals and semimetals of the Periodic Table of the Elements whose valences are completely saturated by halogen atoms or the next the halogen substituents still one or more organic carbon radicals - in particular Cr to C ₄ - alkyl radicals - wear. Suitable halogen substituents in these element halides and elemental alkyl halides are iodine, bromine and, in particular, fluorine and especially chlorine. It is of course also possible to use mixtures of such elemental halides or those elemental alkyl halides with one another and with one another. If, for example, the halides or alkyl halides of aluminum are used as such Lewis acids, typically the following species can be used: aluminum trifluoride, aluminum trichloride, aluminum tribromide; as aluminum alkyl halides, mono- (C 1 -C ₄ -alkyl) aluminum dihalides or di (C 1 -C ₄ -alkyl) aluminum monohalides, such as methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum chloride or diethylaluminum chloride.

In a preferred embodiment, the Lewis acid used for the polymerization catalyst or polymerization complex as active at least a compound selected from the binary chlorine and fluorine compounds of the elements of the 1st to 8th transition group and the 3rd to 5th main group of the periodic table, wherein the binary chlorine compounds may be preferred over the binary fluorine compounds of these elements.

Typical such binary chlorine compounds are ScCl ₃ , YCl ₃ , YbCl ₃ , TiCl ₃ , TiCl ₄ , ZrCl ₄ , HfCl ₄ , VCI 3, VCU, NbCl ₃ , NbCl ₅ , TaCl ₅ , CrCl ₂ , CrCl ₃ , MoCl ₃ , MOCl 5, WCI5, WCI _6, MnCl _2, ReCl _3, ReCl _5, FeCl _2, FeCl _3, RuCl _3, OSCI _3, C0CI2, CoCI _3, RhCl _3, LRCI _3, NiCl _2, PdCl _2, PtCl _2, CuCl, CuCl ₂ , AgCl, AuCl, ZnCl ₂ , CdCl ₂ , HgCl, HgCl ₂ , BCI ₃ , AICI ₃ , GaCl ₃ , Inda, TIC, SiCl ₄ , GeCl ₄ , SnCl ₂ , SnCl ₃ , SnCl ₄ , PbCl ₂ , PbCl ₄ , PCI ₃ , PCI5, AsCI ₃ , SbCI ₃ , SbC and BiCI ₃ . Of these, particularly preferred are BCI ₃ , AICI ₃ , TiCl ₄ , FeCl ₂ , FeCl ₃ and ZnCl ₂ .

Typical of such binary fluorine compounds are ScF _3, YF _3, YbF _3, TiF _3, TiF _4, ZrF _4, HfF, VF _3, VF _4, NbF _3, NbF _5, TaF _5, CrF _2, CrF _3, MoF _3, M0F5 , WF ₅ , WF ₆ , MnF ₂ , ReF ₃ , ReF ₅ , FeF ₂ , FeF ₃ , RuF ₃ , OsF ₃ , CoF ₂ , CoF ₃ , RhF ₃ , IrF ₃ , NiF ₂ , PdF ₂ , PtF ₂ , CuF , CuF ₂ , AgF, AuF, ZnF ₂ , CdF ₂ , HgF, HgF ₂ , BF ₃ , AIF ₃ , GaF ₃ , InF ₃ , TIF ₃ , SiF ₄ , GeF ₄ , SnF ₂ , SnF ₃ , SnF ₄ , PbF ₂ , PbF ₄ , PF ₃ , PF ₅ , AsF ₃ , SbF ₃ , SbF ₅ and BiF ₃ . Of these, BF ₃ , AIF ₃ , TiF ₄ , FeF ₂ , FeF ₃ and ZnF ₂ are particularly preferred. Mixtures of binary chlorine and fluorine compounds can also be used.

Often, it is also possible to use binary bromine compounds as such Lewis acids; such bromine compounds are, for example: TiBr ₃ , TiBr ₄ , ZrBr ₄ , VBr ₃ , VBr ₄ , CrBr ₂ , CrBr ₃ , MoBr ₃ , MoBr ₅ , WBr ₅ , WBr ₆ , MnBr ₂ , FeBr ₂ , FeBr ₃ , CoBr ₂ , CoBr ₃ , NiBr ₂ , PdBr ₂ , PtBr ₂ , CuBr, CuBr ₂ , AgBr, AuBr, ZnBr ₂ , CdBr ₂ , HgBr, HgBr ₂ , BBr ₃ , AIBr ₃ , SiBr ₄ , SnBr ₂ , SnBr ₃ , SnBr ₄ , PbBr ₂ , PbBr ₄ , PBr ₃ , PBr ₅ , AsBr ₃ , SbBr ₃ , SbBr ₅ and BiBr ₃ .

Very particular preference is given to using the preferred sulfonic acid initiators methanesulfonic acid, trifluoromethanesulfonic acid, trichloromethanesulfonic acid and toluenesulfonic acid together with the preferred Lewis acids or Lewis acid complexes with BCI ₃ , AlCl ₃ , TiCl ₄ , FeCl ₂ , FeCl ₃ , ZnCl ₂ , BF ₃ , AIF ₃ , TiF ₄ , FeF ₂ , FeF ₃ and / or ZnF ₂ , especially methanesulfonic acid together with AICI3, BF ₃ or FeCl ₃ , especially when Lewis acid complexes are used, those below as preferred listed dihydrocarbyl ethers of the general formula R ¹ -O-R ² and / or Carbonsäurehydrocarby- ester of the general formula R ³ -COOR ⁴ as donors included.

The process according to the invention preferably uses a complex which acts as a polymerization catalyst and contains as donor an organic compound having at least one ether function or one carboxylic ester function. It is of course also possible to use mixtures of different organic compounds having at least one ether function and / or of different organic compounds having at least one carboxylic acid ester function. If the complex acting as the polymerization catalyst has an orga- nische connection with at least one ether function on, compounds with at least one ether function are also to be understood as meaning acetals and hemiacetals.

In a preferred embodiment of the present invention, a polymerization catalyst complex of at least one Lewis acid and at least one donor is used in which the donor organic compound is a dihydrocarbyl ether of the general formula R ¹ -O-R ² , in which Variables R ¹ and R ^{2 are} independently C ¹ - to C 20 -alkyl radicals, in particular, C 1 - to C 6 -alkyl radicals, C 5 - to C 6 -cycloalkyl radicals, C 2 - to C 20 -aryl radicals, in particular C 1 - to C 12 -aryl radicals, or C ₇ - to C2o-arylalkyl radicals, in particular C ₇ - to Ci2 arylalkyl radicals, denote, or R ^{3 is} a Carbonsäurehydrocarbylester the general formula - COOR ⁴ group, in which the variables R ³ and R ⁴ are independently C to C 20 alkyl radicals, especially d- to Ce-alkyl, C5- to Ce-cycloalkyl, CQ to C20 aryl groups, particularly CQ to Ci2-aryl, or C ₇ - to C2o-arylalkyl radicals, in particular C ₇ - to Ci2 arylalkyl radicals, denote.

The dihydrocarbyl ethers mentioned may be open-chain or cyclic, wherein in the case of the cyclic the two variables R ¹ and R ² form a ring, such rings also being able to contain two or three ether oxygen atoms. Examples of such open-chain and cyclic dihydrocarbyl ethers are dimethyl ether, diethyl ether, di-n-propyl ether, diisopropyl ether, di-n-butyl ether, di-sec-butyl ether, diisobutyl ether, di-n-pentyl ether, di-n-hexyl ether , Di-n-heptyl ether, di-n-octyl ether, di- (2-ethylhexyl) ether, methyl n-butyl ether, methyl sec-butyl ether, methyl isobutyl ether, methyl tert-butyl ether, ethyl n-butyl ether, ethyl sec-butyl ether, ethyl isobutyl ether, n-propyl n-butyl ether, n-propyl sec-butyl ether, n-propyl isobutyl ether, n-propyl tert-butyl ether, iso propyl n-butyl ether, isopropyl sec-butyl ether, isopropyl isobutyl ether, isopropyl tert-butyl ether, methyl n-hexyl ether, methyl n-octyl ether, methyl (2-ethylhexyl) ether, ethyl n-hexyl ether , Ethyl n-octyl ether, ethyl (2-ethylhexyl) ether, n-butyl n-octyl ether, n-butyl (2-ethylhexyl) ether, tetrahydrofuran, tetrahydropyran, 1, 2, 1, 3 and 1,4-dioxane, dicyclohexyl ether, diphenyl ether, ditolyl ether, dixylyl ether and dibenzyl ether. Of the dihydrocarbyl ethers mentioned, di-n-butyl ether and diphenyl ether have proven to be particularly advantageous as donors, in particular in combination with the Lewis acid BCI3, AICI3, TiCu, FeC, FeC and ZnC. Examples of the abovementioned carboxylic acid hydrocarbyl esters are methyl formate, ethyl formate, n-propyl formate, formic acid isopropyl ester, n-butyl formate, sec-butyl formate, formic acid isobutyl ester, formic acid tert -butyl ester, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, sec-butyl acetate, isobutyl acetate, tert-butyl acetate, propionic acid. acid methyl ester, ethyl propionate, n-propyl propionate, propionic acid isopropyl ester, n-butyl propionate, sec-butyl propionate, isobutyl propionate, tert-butyl propionate, methyl butyrate, Buttersäu- N-ethyl ester, n-propyl butyrate, n-butyl butyrate, n-butyl butyrate, secbutyl butbutyrate, isobutyl butyrate, tert-butyl butyrate, methyl cyclohexanecarboxylate, ethyl cyclohexanecarboxylate, n-propyl cyclohexanecarboxylate Isopropyl cyclohexanecarboxylate, n-butyl cyclohexanecarboxylate, sec.butyl cyclohexanecarboxylate, isobutyl cyclohexanecarboxylate, tert.-butyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, n-propyl benzoate, benzoic acid iso - propyl ester, n-butyl benzoate, sec-butyl benzoate, isobutyl benzoate, tert-butyl benzoate, methyl phenylacetate, ethyl phenylacetate, n-propyl phenylacetic acid, isopropyl phenylacetate, phenylacetic acid n butyl ester, phenylacetic acid sec-butyl ester, phenylacetic acid isobutyl ester and phenylacetic acid tert-butyl ester. Of the carboxylic acid hydrocarbyl esters mentioned, ethyl acetate as donor, in particular in combination with the Lewis acids BCI ₃ , AICI ₃ , TiCU, FeCb, FeCb and ZnCb, has proven to be particularly advantageous.

Furthermore, such dihydrocarbyl ethers and Carbonsäurehydrocarbylester as donors, especially in combination with the Lewis acids BCI3, AICI3, TiCU, FeCb, FeCb and ZnCb, have been found to be particularly advantageous in which the donor compound a total carbon number of 3 to 16, preferably from 4 to 16, in particular from 4 to 12, especially from 4 to 8, having. In the case of the dihydrocarbyl ethers, especially those having a total of 6 to 14, in particular 8 to 12, carbon atoms are preferred. In the case of the carboxylic acid hydrocarbyl esters in particular, especially those having a total of 3 to 10, in particular 4 to 6, carbon atoms are preferred.

The molar ratio of the said donor compounds to the Lewis acids, ie in particular to the said elemental halides and elemental alkyl halides, in particular to the Lewis acids BCI3, AICI3, TiCu, FeCb, FeCb and ZnCb, in the polymerization catalyst complex moves in the Rule in the range of 0.3: 1 to 1, 5: 1, in particular from 0.5: 1 to 1, 2: 1, especially 0.7: 1 to 1, 1: 1; it is in most cases 1: 1. However, it is also possible to work with a greater degree of closure of the donor compounds, often up to a 10-fold, in particular 3-fold, molar excess; the excess amount of donor compounds then additionally acts as a solvent or diluent.

Usually, the polymerization catalyst complex is prepared before the polymerization separately from the one or more Lewis acids mentioned, which are usually used in anhydrous form, and the donor or the compounds and then - usually dissolved in an inert solvent such as a halogenated Hydrocarbon, for example dichloromethane - added to the polymerization medium. However, the complex can also be prepared in situ prior to polymerization. In a preferred embodiment of the present invention, the polymerization is carried out with concomitant use of at least one further initiator which is mono- or polyfunctional, in particular mono-, di- or trifunctional, and is chosen from organic hydroxy compounds, organic halogen compounds, protic acids and water. It is also possible to use mixtures of such further initiators, for example mixtures of two or more organic hydroxy compounds, mixtures of two or more organic halogen compounds, mixtures of one or more organic hydroxy compounds and one or more organic halogen compounds, mixtures of one or more organic hydroxy compounds and water , Mixtures of one or more organic halogen compounds and water or mixtures of one or more protic acids and water. The initiator may be mono-, di- or polyfunctional, ie in each case one, two or more hydroxyl groups or halogen atoms may be present in the initiator molecule, at which the polymerization reaction starts. In the case of di- or polyfunctional initiators, it is customary to obtain telechelic isobutene polymers having two or more, in particular two or three, polyisobutene chain ends.

Typical examples of such organic monohydroxy compounds are methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, isobutanol, tert-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, 2 Ethylhexanol, cyclohexanol, phenol, p-methoxyphenol, o-, m- and p-cresol, benzyl alcohol, p-methoxybenzyl alcohol, 1- and 2-phenylethanol, 1- and 2- (p-methoxyphenyl) ethanol, 1 -, 2 and 3-phenyl-1-propanol, 1-, 2- and 3- (p-methoxyphenyl) -1-propanol, 1- and 2-phenyl-2-propanol, 1- and 2- (p-methoxyphenyl ) -2-propanol, 1-, 2-, 3- and 4-phenyl-1-butanol, 1-, 2-, 3- and 4- (p-methoxyphenyl) -1-butanol, 1 -, 2 , 3- and 4-phenyl-2-butanol, 1-, 2-, 3- and 4- (p-methoxyphenyl) -2-butanol, 9-methyl-9H-fluoren-9-ol, 1, 1-diphenylethanol, 1,1-diphenyl-2-propyn-1-ol, 1,1-diphenylpropanol, 4- (1-hydroxy-1-phenylethyl) benzonitrile, cyclopropyldiphenylmethanol, 1-hydroxy-1,1-diphenylpropane -2-one, benzilic acid, 9-phenyl-9-fluorenol, triphenylmethanol, diphenyl (4 -pyridinyl) methanol, alpha, alpha-diphenyl-2-pyridinemethanol, 4-methoxytrityl alcohol (in particular polymer-bound as solid phase), alpha- tert -butyl-4-chloro-4'-methylbenzhydrol, cyclohexyldiphenylmethanol, alpha- (p-) Tolyl) benzhydrol, 1, 1, 2-triphenylethanol, alpha, alpha-diphenyl-2-pyridinethanol, alpha, allyl pha-4-pyridylbenzohydrol-N-oxide, 2-fluorotriphenylmethanol, triphenylpropargyl alcohol, 4 - [(diphenyl) hydroxymethyl] benzonitrile, 1- (2,6-dimethoxyphenyl) -2-methyl-1-phenyl-1 - propanol, 1, 1, 2-triphenylpropane-1-ol and p-anisaldehyde carbinol. Particularly suitable bifunctional initiators organic hydroxy compounds having two hydroxyl groups in the molecule are especially dihydric alcohols or diols having a total carbon number of 2 to 30, in particular from 3 to 24, especially from 4 to 20, and bisphenols having a total carbon number of 6 to 30, especially of 8 to 24, especially from 10 to 20, for example, ethylene glycol, 1, 2 and 1, 3-propylene glycol, 1, 4-butylene glycol, 1, 6-hexylene glycol, 1, 2, 1, 3 or 1,4-bis (1-hydroxy-1-methylethyl) benzene (o-, m- or p-dicumyl alcohol), bisphenol A, 9,10-dihydro-9,10-dimethyl-9,10-anthracenediol , 1, 1-diphenylbutane-1, 4-diol, 2-hydroxytri- phenylcarbinol and 9- [2- (hydroxymethyl) phenyl] -9-fluorenol. Suitable monofunctional initiators organic halogen compounds having a halogen atom in the molecule are especially compounds of general formula R ⁶ -hal call, in the shark a halogen atom selected from fluorine, iodine and in particular chlorine and bromine, and R ⁶ d- to C2o Alkyl radicals, in particular, d- to Ce-alkyl radicals, C5- to Ce-cycloalkyl or C ₇ - to C 2o-arylalkyl radicals, in particular C ₇ - to Ci2-Arylalkylreste designated. Furthermore, the radicals R ^{6 may} also contain mixtures of the abovementioned structures and / or have functional groups other than those already mentioned, for example a keto function, a nitroxide or a carboxyl group, and / or heterocyclic structural elements. Typical examples of such organic monohalogen compounds are methyl chloride, methyl bromide, ethyl chloride, ethyl bromide, 1-chloropropane, 1-bromopropane, 2-chloropropane, 2-bromopropane, 1-chlorobutane, 1-bromobutane, sec-butyl chloride, sec-butyl bromide , Isobutyl chloride, isobutyl bromide, tert-butyl chloride, tert-butyl bromide, 1-chloropentane, 1-bromopentane, 1-chlorohexane, 1-bromohexane, 1-chloroheptane, 1-bromoheptane, 1-chloroctane, 1-bromoctane, 1 Chloro-2-ethylhexane, 1-bromo-2-ethylhexane, cyclohexylchloride, cyclohexylbromide, benzylchloride, benzylbromide, 1-phenyl-1-chloroethane, 1-phenyl-1-bromoethane, 1-phenyl-2-chloroethane, 1 Phenyl 2-bromoethane, 1-phenyl-1-chloropropane,

2-bromobutane, 1-phenyl-3-chlorobutane, 1-phenyl-3-bromobutane, 1-phenyl-4-chlorobutane, 1-phenyl-4-bromobutane, 2-phenyl-1-chlorobutane, 2-phenyl-1 - bromobutane, 2-phenyl-2-chlorobutane, 2-phenyl-2-bromobutane, 2-phenyl-3-chlorobutane, 2-phenyl-3-bromobutane, 2-phenyl-4-chlorobutane and 2-phenyl- 4-bromobutane.

Suitable difunctional initiators organic halogen compounds having two halogen atoms in the molecule are, for example, 1, 3-bis (1-bromo-1-methylethyl) benzene, 1, 3-bis (2-chloro-2-propyl) benzene (1, 3-dicumyl chloride) and 1, 4-bis (2-chloro-2-propyl) benzene (1, 4-dicumyl chloride) ,

The further initiator is particularly preferably selected from organic hydroxy compounds in which one or more hydroxyl groups are bonded to one sp ³ -hybri-disiert carbon atom, organic halogen compounds in which one or more halogen atoms bonded to each sp ³ -hybridized carbon atom are, protic acids and water. Of these, an initiator is particularly preferable which is selected from organic hydroxy compounds in which one or more hydroxyl groups are each bonded to an sp ³ -hybridized carbon atom selected.

Further preferred initiators in the organic halogen compounds are those in which the one or more halogen atoms are each bonded to a secondary or in particular to a tertiary sp ³ -hybridized carbon atom.

Above all, preference is given to further initiators which, in addition to the hydroxyl group, carry the radicals R ⁵ , R ⁶ and R ⁷ on such an sp ³ -hydrified carbon atom, which independently of one another are hydrogen, C 1 - to C 20 -alkyl, C 5 - to C 6 -cycloalkyl, CQ- to C2 ₀ -A1 I, C ₇ - to C 20 -alkylaryl or phenyl, where one aromatic nucleus is one or more, preferably one or two C 1 to C ₄ alkyl, C 1 to C ₄ alkoxy, C to C ₄ - Hydroxyl-alkyl or C to C ₄ haloalkyl radicals as substituents, denote, wherein at most one of the variables R ⁵ , R ⁶ or R ^{7 is} hydrogen and at least one of the variables R ⁵ , R ⁶ or R ⁷ phenyl, which or one or more, preferably one or two C to C ₄ alkyl, C to C ₄ alkoxy, C to C ₄ - hydroxyalkyl or C to C ₄ haloalkyl radicals may carry as substituents. Suitable protonic acids are, for example, hydrochloric acid, hydrobromic acid, hydrofluoric acid, sulfuric acid, hydrocyanic acid and mixtures thereof. As proton acids but also protonated ethers can be used. Very particular preference is given to the present invention further initiators which are water, one or more protic acids, methanol, ethanol, 1 - phenylethanol, 1 - (p-methoxyphenyl) ethanol, n-propanol, isopropanol, 2-phenyl-2-propanol (Cumene), n-butanol, isobutanol, sec-butanol, tert-butanol, 1-phenyl-1-chloroethane, 2-phenyl-2-chloropropane (cumyl chloride), tert-butyl chloride and 1, 3 or 1 4-bis (1-hydroxy-1-methylethyl) benzene and mixtures thereof are selected. Of these, particular preference is given to further initiators which, under water, one or more protic acids, methanol, ethanol, 1-phenylethanol, 1- (p-methoxyphenyl) ethanol, n-propanol, isopropanol, 2-phenyl-2-propanol ( Cumene), n-butanol, Isobutanol, sec-butanol, tert-butanol, 1-phenyl-1-chloroethane and 1, 3- or 1, 4-bis (1 - hydroxy-1-methylethyl) benzene and mixtures thereof are selected.

The molar ratio of the sum of the inventively used organic sulfonic acids of the general formula Z-SO3H and the optionally used further initiators to the isobutene monomer used in the homopolymerization of isobutene or to the total amount of the polymerizable monomers used in the copolymerization of isobutene, based on each single functional site of the initiator (wherein the organic sulfonic acids are to be regarded as monofunctional), usually 0.001: 1 to 0.5: 1, in particular 0.01: 1 to 0.4: 1, especially 0.1: 1 to 0.3: 1. When water is used as the sole further initiator or in combination with organic hydroxy compounds and / or organic halogen compounds as further initiators, the molar ratio of water alone to the isobutene monomer used in homopolymerization of isobutene or to the total amount of the polymerizable monomers used in copolymerization of In particular, isobutene is 0.0001: 1 to 0.1: 1, especially 0.0002: 1 to 0.05: 1.

Some of the initiator molecules added as organic sulfonic acids and optionally as organic hydroxy or halogen compounds can be incorporated into the polymer chains. The proportion (Uff) of polymer chains which are started by such a built-in organic initiator molecule can be up to 100%, usually from 0 to 90% and can be from 5 to 90%. The remaining polymer chains are formed either by moisture-derived water as the initiator molecule or by chain transfer reactions.

In a further preferred embodiment of the present invention, the polymerization is carried out in the presence of from 0.01 to 10 mmol, in particular from 0.05 to 5.0 mmol, especially from 0.1 to 1.0 mmol, in each case based on 1 mol Isobutene monomer used in homopolymerization of isobutene or to 1 mole of the total amount of the polymerizable monomers used in copolymerization of isobutene, a nitrogen-containing basic compound.

As such nitrogen-containing basic compound it is possible to use an aliphatic, cycloaliphatic or aromatic amine of the general formula R ⁷ -NR ⁸ R ⁹ or else ammonia, in which the variables R ⁷ , R ⁸ and R ^{9 are} each independently of one another hydrogen, d C 2 - to C 20 -alkyl radicals, in particular, C 1 - to C ₆ -alkyl radicals, C 5 - to C ₆ -cycloalkyl radicals, C 2 - to C 20 -aryl radicals, in particular C 2 - to C 12 -aryl radicals, or C ₇ - to C 20 -arylalkyl radicals, in particular C ₇ - to Ci2-arylalkyl radicals. If none of these variables is hydrogen, a tertiary amine is present. If one of these variables is hydrogen, a secondary amine is present. If two of these variables are hydrogen, a primary amine is present. If all of these variables are hydrogen, ammonia is present. Typical examples of such amines of the general formula R ⁷ -NR ⁸ R ⁹ are methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, tert-butylamine, sec-butylamine, isobutylamine, tert-amylamine, n-hexylamine, n-heptylamine, n-octylamine, 2-ethylhexylamine, cyclopentylamine, cyclohexylamine, aniline, dimethylamine, diethylamine, di-n-propylamine, di-iso-propylamine, di-n-butylamine, di-tert-butylamine , Di-sec-butylamine, di-iso-butylamine, di-tert-amylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di- (2-ethylhexyl) amine, dicyclopentylamine, dicyclohexylamine, diphenylamine, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, tri-tert-butylamine, tri-sec-butyl-amine, tri-n-propylamine. iso-butylamine, tri-tert-amylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri (2-ethylhexyl) amine, tricyclopentylamine, tricyclohexylamine, triphenylamine, dimethylethylamine, Methyl-n-butylamine, N-methyl-N-phenylamine, N, N-dimethyl-N-phenylamine, N-methyl-N, N-diph enylamine or N-methyl-N-ethyl-Nn-butylamine.

Furthermore, as such nitrogen-containing basic compound, a compound having a plurality, in particular having two or three nitrogen atoms and having 2 to 20 carbon atoms are used, these nitrogen atoms each independently of one another carry hydrogen atoms or aliphatic, cycloaliphatic or aromatic substituents. Examples of such polyamines are 1, 2-ethylenediamine, 1, 3-propylenediamine, 1, 4-butylenediamine, diethylenetriamine, N-methyl-1, 2-ethylenediamine, N, N-dimethyl-1, 2-ethylenediamine, N , N'-dimethyl-1, 2-ethylenediamine or N, N-dimethyl-1,3-propylenediamine. However, a saturated, partially unsaturated or unsaturated nitrogen-containing five-membered or six-membered heterocycle which contains one, two or three ring nitrogen atoms and one or two further ring heteroatoms selected from the group consisting of oxygen and sulfur and / or hydrocarbyl radicals, in particular d-butyl, is particularly suitable as such nitrogen-containing basic compound. to C ₄ -alkyl radicals and / or phenyl, and / or functional groups or heteroatoms as substituents, in particular fluorine, chlorine, bromine, nitro and / or cyano, may have, for example pyrrolidine, pyrrole, imidazole, 1, 2,3 - or 1, 2,4-triazole, oxazole, thiazole, piperidine, pyrazane, pyrazole, pyridazine, pyrimidine, pyrazine, 1, 2,3-, 1, 2,4- or 1, 2,5-triazine, 1, 2,5-oxathiazine, 2H-1, 3,5-thiadiazine or morpholine.

However, very particularly suitable as such nitrogen-containing basic compound is pyridine or a derivative of pyridine (in particular a mono-, di- or tri-Ci- to C ₄ -alkyl-substituted pyridine) such as 2-, 3-, or 4-methylpyridine ( Picolines), 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, 3,5- or 3,6-dimethylpyridine (lutidines), 2,4,6-trimethylpyridine ( Collidine), 2-, 3, - or 4-tert-butylpyridine, 2-tert-butyl-6-methylpyridine, 2,4-, 2,5-, 2,6- or 3,5-di-tert .-Butylpyridine or 2-, 3, - or 4-phenylpyridine. One can use a single nitrogen-containing basic compound or mixtures of such nitrogen-containing basic compounds.

For the use of isobutene or an isobutene-containing monomer mixture as the monomer to be polymerized, the isobutene source in embodiment (A) and (B) is both pure isobutene and isobutene-containing C ₄ hydrocarbon streams, for example C ₄ raffinates. in particular "raffinate 1", C ₄ cuts from isobutane dehydrogenation, C ₄ cuts from steam crackers and FCC (fluid catalysed cracking) crackers, provided that they are largely freed of 1,3-butadiene contained therein. A C ₄ hydrocarbon stream from an FCC refinery unit is also known as a "b / b" stream. Further suitable isobutene-containing C ₄ -hydrocarbon streams are, for example, the product stream of a propylene-isobutane co-oxidation or the product stream from a metathesis unit, which are generally used after customary purification and / or concentration. Suitable C ₄ -hydrocarbon streams generally contain less than 500 ppm, preferably less than 200 ppm, of butadiene. The presence of 1-butene and of cis- and trans-2-butene is largely uncritical. Typically, the isobutene concentration in said C ₄ hydrocarbon streams is in the range of 30 to 60 weight percent. Thus, raffinate 1 usually consists essentially of 30 to 50 wt .-% of isobutene, 10 to 50 wt .-% 1-butene, 10 to 40 wt .-% cis- and trans-2-butene and 2 to 35 wt .-% butanes; In the polymerization process according to the invention, the unsubstituted butenes in the raffinate 1 are generally virtually inert and only the isobutene is polymerized. In a preferred embodiment, the monomer used for the polymerization is a technical C ₄ -hydrocarbon stream having an isobutene content of from 1 to 100% by weight, in particular from 1 to 99% by weight, in particular from 1 to 90% by weight. %, more preferably from 30 to 60% by weight, in particular a raffinate 1 stream, a b / b stream from an FCC refinery unit, a product stream of a propylene-isobutane co-oxidation or a product stream from a metathesis unit.

The said isobutene-containing monomer mixture may contain small amounts of contaminants, such as water, carboxylic acids or mineral acids, without resulting in critical yield or selectivity losses. It is expedient to avoid enriching these impurities by removing such pollutants from the isobutene-containing monomer mixture, for example by adsorption on solid adsorbents such as activated carbon, molecular sieves or ion exchangers.

It is also possible to react monomer mixtures of isobutene or of the isobutene-containing hydrocarbon mixture with olefinically unsaturated monomers which are copolymerizable with isobutene. If monomer mixtures of isobutene are to be copolymerized with suitable comonomers, the monomer mixture preferably contains at least 5% by weight, particularly preferably less than 5% by weight. at least 10% by weight and in particular at least 20% by weight of isobutene, and preferably at most 95% by weight, particularly preferably at most 90% by weight and in particular at most 80% by weight of comonomers. Suitable copolymerizable monomers are: vinylaromatics such as styrene and α-methylstyrene, C 1 -C 4 -alkylstyrenes such as 2-, 3- and 4-methylstyrene and 4-tert-butylstyrene, halostyrenes such as 2, 3 or 4 Chlorostyrene and isoolefins having 5 to 10 carbon atoms such as 2-methylbutene-1, 2-methylpentene-1, 2-methylhexene-1, 2-ethyl-1-pentene, 2-ethylhexene-1 and 2-propylhepten-1. Other suitable comonomers are olefins which have a silyl group, such as 1-trimethoxysilylethene, 1- (trimethoxysilyl) propene, and 1- (trimethoxysilyl) -2-methylpropene-2,1- [tri (methoxyethoxy) silyl]. - ethene, 1 - [tri (methoxyethoxy) silyl] propene, and 1 - [tri (methoxyethoxy) silyl] -2-methylpropene-2. Furthermore, depending on the polymerization conditions, comopters also include isoprene, 1-butene and cis- and trans-2-butene.

If copolymers are to be prepared by the process according to the invention, the process can be designed such that preferably random polymers or preferably block copolymers are formed. For the preparation of block copolymers, it is possible for example to feed the various monomers successively to the polymerization reaction, the addition of the second comonomer taking place in particular only when the first comonomer is already at least partially polymerized. In this way, both diblock, triblock and higher block copolymers are accessible, which have a block of one or the other comonomer as a terminal block, depending on the order of monomer addition. However, in some cases block copolymers are also formed when all comonomers are simultaneously fed to the polymerization reaction, but one of them polymerizes significantly faster than either one or the other. This is the case in particular when isobutene and a vinylaromatic compound, in particular styrene, are copolymerized in the process according to the invention. Preferably, block copolymers are formed with a terminal polystyrene block. This is because the vinyl aromatic compound, especially styrene, polymerizes significantly slower than isobutene.

The polymerization can be carried out both continuously and discontinuously. Continuous processes can be carried out in analogy to known processes of the prior art for the continuous polymerization of isobutene in the presence of boron trifluoride-based catalysts in the liquid phase.

The inventive method is suitable both for carrying out at low temperatures, for example at -90 ° C to 0 ° C, and at higher temperatures, ie at least 0 ° C, for example at 0 ° C to +30 ° C or at 0 ° C to + 50 ° C, suitable. However, the polymerization according to the process of the present invention is preferably carried out at lower temperatures in embodiment (A), usually at -70 ° C to -10 ° C, especially at -60 ° C to -15 ° C, and in embodiment (B). at a slightly higher temperature temperatures of -30 ° C to + 50 ° C, in particular at 0 ° C to + 30 ° C, for example at room temperature (+20 to + 25 ° C) carried out.

If the polymerization according to the process according to the invention takes place at or above the boiling point of the monomer or monomer mixture to be polymerized, it is preferably carried out in pressure vessels, for example in autoclaves or in pressure reactors.

Preferably, the polymerization is carried out according to the process of the invention in the presence of an inert diluent. The used inert

Diluent should be suitable to reduce the increase in the viscosity of the reaction solution which usually occurs during the polymerization reaction to such an extent that the dissipation of the resulting heat of reaction can be ensured. Suitable diluents are those solvents or solvent mixtures which are inert to the reagents used. Suitable diluents are, for example, aliphatic hydrocarbons such as n-butane, n-pentane, n-hexane, n-heptane, n-octane and isooctane, cycloaliphatic hydrocarbons such as cyclopentane and cyclohexane, aromatic hydrocarbons such as benzene, toluene and the xylene, and halogenated hydrocarbons, in particular halogenated aliphatic hydrocarbons, such as methyl chloride, dichloromethane, trichloromethane (chloroform), 1, 1-dichloroethane, 1, 2-dichloroethane, trichloroethane and 1-chlorobutane, and halogenated aromatic hydrocarbons and alkylaromatics halogenated in the alkyl side chains, such as Chlorobenzene, monofluoromethylbenzene, difluoromethylbenzene and trifluoromethylbenzene, and mixtures of the aforementioned diluents. Preferred halogenated hydrocarbons for the inert diluents mentioned above and below are chlorinated hydrocarbons, in particular pure chlorohydrocarbons. Fluorohydrocarbons are preferably excluded from the inert diluents which can be used here in order to largely exclude residual contents of fluorine in the polymer. The inert constituents of isobutene-containing C4 hydrocarbon streams are also used as diluents or as constituents of the solvent mixtures mentioned.

Preferably, according to embodiment (A), the polymerization according to the invention is carried out in a halogenated hydrocarbon, in particular in a halogenated aliphatic hydrocarbon, or in a mixture of halogenated hydrocarbons, in particular halogenated aliphatic hydrocarbons, or in a mixture of at least one halogenated hydrocarbon, in particular a halogenated one aliphatic hydrocarbon, and at least one aliphatic, cycloaliphatic or aromatic hydrocarbon as an inert diluent, for example a mixture of dichloromethane and n-hexane, usually in the Vol. ratio of 10:90 to 90:10, in particular from 50:50 to 85:15. Preferably, the diluents are freed before use of impurities such as water, carboxylic acids or mineral acids, for example by adsorption on solid adsorbents such as activated carbon, molecular sieves or ion exchangers.

In a further preferred variant of embodiment (A), the polymerization according to the invention is carried out in halogen-free aliphatic or, in particular, halogen-free aromatic hydrocarbons, in particular toluene. For this embodiment, water has proven to be particularly advantageous in combination with said organic hydroxy compounds and / or the said organic halogen compounds or in particular as the sole initiator.

Preferably, according to embodiment (B), the polymerization according to the invention is carried out in an aliphatic, cycloaliphatic or aromatic hydrocarbon, in a halogenated aliphatic hydrocarbon or in a mixture of aliphatic, cycloaliphatic and / or aromatic hydrocarbons or halogenated aliphatic hydrocarbons or in a mixture of at least one halogenated aliphatic hydrocarbon and at least one aliphatic, cycloaliphatic or aromatic hydrocarbon as an inert diluent. Preferably, the polymerization is carried out according to the process of the invention under largely aprotic, in particular under substantially anhydrous reaction conditions. Under largely aprotic or largely anhydrous reaction conditions, it is understood that the water content (or the content of protic impurities) in the reaction mixture is less than 50 ppm and in particular less than 5 ppm. As a rule, therefore, the feedstocks will be dried before use by physical and / or chemical means. In particular, it has proven useful to use the aliphatic or cycloaliphatic hydrocarbons used as solvent after conventional pre-cleaning and predrying with an organometallic compound, such as an organolithium, organomagnesium or organoaluminum compound, in an amount sufficient to remove the traces of water largely removed from the solvent. The solvent thus treated is then preferably condensed directly into the reaction vessel. In a similar manner, it is also possible to use the monomers to be polymerized, in particular isobutene or mixtures containing isobutene. Drying with other conventional drying agents such as molecular sieves or predried oxides such as aluminum oxide, silicon dioxide, calcium oxide or barium oxide is also suitable. The halogenated solvents, which are not suitable for drying with metals such as sodium or potassium or with metal alkyls, are freed of water or traces of water with suitable drying agents, for example calcium chloride, phosphorus pentoxide or molecular sieve. In an analogous manner, it is also possible to dry those starting materials for which treatment with metal alkyls is likewise not suitable, for example vinylaromatic compounds. Even if water is used as initiator or if is used, residual moisture from solvents and monomers should preferably be removed as far as possible or completely before the reaction by drying in order to use the initiator water targeted in a specified amounts, whereby one receives a higher process control and reproducibility of the results se.

The polymerization of the isobutene or of the isobutene-containing feedstock usually takes place spontaneously upon contacting the polymerization catalyst, ie the iron halide donor complex, the aluminum trihalide donor complex or the aluminum alkyl halide donor complex, in particular the iron chloride donor complex. nor complex or of the aluminum trichloride donor complex, or of the at least one organic sulfonic acid-containing Lewis acid complex with or without donors, with the isobutene or the isobutene-containing monomer mixture at the desired reaction temperature. In this case, it is possible to initially charge the monomers in the diluent, to bring them to the reaction temperature and then to add the polymerization catalyst, ie the iron halide donor complex, the aluminum trihalide donor complex or the aluminum alkyl halide donor complex, in particular the iron chloride donor complex or the aluminum trichloride donor complex, or the at least one organic sulfonic acid-containing Lewis acid complex with or without donors, admits. It is also possible to use the polymerization catalyst, ie the iron halide donor complex, the aluminum trihalide donor complex or the aluminum alkyl halide donor complex, in particular the iron chloride donor complex or the aluminum trichloride complex. Donor complex, or the containing at least one organic sulfonic acid containing Lewis acid complex with or without donors, optionally in the diluent, and then adding the monomers. The beginning of polymerization is then the time at which all the reactants are contained in the reaction vessel. For the preparation of isobutene copolymers, it is possible to initially charge the monomers, if appropriate in the diluent, followed by the polymerization catalyst, ie the iron halide donor complex, the aluminum trihalide donor complex or the aluminum alkyl halide donor complex , in particular the iron chloride donor complex or the aluminum trichloride donor complex, or the at least one organic sulfonic acid-containing Lewis acid complex with or without donors, admits. The adjustment of the reaction temperature can be carried out before or after the addition of the polymerization catalyst, ie the iron halide donor complex, the aluminum trihalide donor complex or the aluminum alkyl halide donor complex, in particular the iron chloride donor complex or the Aluminum trichloride donor complex, or the at least one organic sulfonic acid-containing Lewis acid complex with or without donors carried out. It is also possible to initially introduce only one of the monomers, if appropriate in the diluent, followed by the polymerization catalyst, ie the Iron halide donor complex, the aluminum trihalide donor complex or the Aluminiumalkylhalogenid-donor complex, in particular the iron chloride donor complex or the aluminum trichloride donor complex, or the at least one organic sulfonic acid-containing Lewis acid complex with or without donors, and only after a certain time, for example when at least 60%, at least 80%, or at least 90% of the monomer are reacted, the one or more monomers are added. Alternatively, the polymerization catalyst, ie the iron halide donor complex, the aluminum trihalide donor complex or the Aluminiumalkylhalogenid-donor complex, in particular the iron chloride donor complex or the aluminum trichloride donor complex, or the at least one organic Sulfonic acid-containing Lewis acid complex with or without donors, optionally in the diluent, submit, then add the monomers simultaneously or sequentially and then set the desired reaction temperature. The beginning of polymerization is then the point in time at which the polymerization catalyst, ie the iron halide donor complex, the aluminum trihalide donor complex or the aluminum alkyl halide donor complex, in particular the iron chloride donor complex or the aluminum trichloride Donor complex, or the at least one organic sulfonic acid-containing Lewis acid complex with or without donors, and at least one of the monomers are contained in the reaction vessel.

In addition to the discontinuous procedure described here, the polymerization according to the process of the invention can also be designed as a continuous process. This leads to the starting materials, i. the monomer or monomers to be polymerized, if appropriate the diluent and optionally the polymerization catalyst, ie the iron halide donor complex, the aluminum trihalide donor complex or the aluminum alkyl halide donor complex, in particular the iron chloride donor complex or The aluminum trichloride-donor complex, or the at least one organic sulfonic acid-containing Lewis acid complex with or without donors, the polymerization continuously added to and continuously withdrawing reaction product, so that set more or less stationary polymerization in the reactor. The monomer or monomers to be polymerized can be supplied as such, diluted with a diluent or solvent, or as a monomer-containing hydrocarbon stream.

The iron halide donor complex effective as the polymerization catalyst, the aluminum trihalide donor complex or the aluminum alkyl halide donor complex, in particular the iron chloride donor complex or the aluminum trichloride donor complex, or the at least one organic sulfonic acid-containing Lewis acid complex with or without donors is usually dissolved, dispersed or suspended in the polymerization medium. Also, a support of the iron halide donor complex, the aluminum trihalide donor complex or the Aluminiumalkylha- lelide donor complex, in particular the iron chloride donor complex or the Aluminum trichloride donor complex, or the at least one organic sulfonic acid-containing Lewis acid complex with or without donors on conventional support materials is possible. Suitable reactor types for the polymerization process of the present invention are usually stirred tank reactors, loop reactors and tubular reactors, but also fluidized bed reactors, fluidized bed reactors, stirred tank reactors with and without solvent, liquid bed reactors, continuous fixed bed reactors and discontinuous fixed bed reactors (batchwise).

In the process according to the invention, the iron halide donor complex effective as the polymerization catalyst, the aluminum trihalide donor complex or the aluminum alkyl halide donor complex, in particular the iron chloride donor complex or the aluminum trichloride donor complex, or at least an organic sulfonic acid-containing Lewis acid complex with or without donors, usually used in such an amount that the molar ratio of element of the 1st to 8th subgroup or the 3rd to 5th main group of the periodic table, especially of Iron and aluminum in the iron halide donor complex, aluminum trihalide donor complex or aluminum alkyl halide donor complex, in particular in the iron chloride donor complex or aluminum trichloride donor complex, or in the corresponding at least one organic sulfonic acid-containing Lewis acid complex with or without donors, to isobutene in homopolymerization of isobutene or to the total amount of polym isomerizable monomers in the copolymerization of isobutene in the range from 1:10 to 1: 5000, in particular from 1:15 to 1: 1000, especially from 1:20 to 1: 250. To terminate the reaction, the reaction mixture is preferably deactivated, for example by adding a protic compound, in particular by adding water, alcohols, such as methanol, ethanol, n-propanol and isopropanol or mixtures thereof with water, or by adding an aqueous base, for example an aqueous solution an alkali metal or alkaline earth metal hydroxide such as sodium hydroxide, potassium hydroxide, magnesium hydroxide or calcium hydroxide, an alkali metal or alkaline earth metal carbonate such as sodium, potassium, magnesium or calcium carbonate, or an alkali metal or alkaline earth metal bicarbonate such as sodium, potassium, magnesium or calcium bicarbonate - nat. In the process according to the invention, the described highly reactive isobutene homo- or copolymers having a content of terminal vinylidene double bonds (a-double bonds) per polyisobutene chain end of at least 50 mol%, preferably of at least 60, are described for derivatization by introduction of the low molecular weight polar groups A. Mol%, preferably of at least 70 mol%, preferably of at least 80 mol%, preferably of at least 85 mol%, more preferably of at least 90 mol%, particularly preferably of more than 91 mol% and in particular of at least 95 mole%, eg, of nearly 100 mole%. In particular, one also uses highly reactive isobutene copolymers consisting of isobutene and at least one vinylaromatic monomer, in particular styrene, and a content of terminal vinylidene double bonds (a-double bonds) per polyisobutene chain end of at least 50 mol%, preferably of at least 60 mol%, preferably of at least 70 Mole%, preferably of at least 80 mole%, preferably of at least 80 mole%, preferably of at least 85 mole%, more preferably of at least 90 mole%, more preferably of more than 91 mole% and especially of at least 95 mole%, eg, of nearly 100 mole%. To prepare such copolymers from isobutene and at least one vinylaromatic monomer, in particular styrene, isobutene or an isobutene-containing hydrocarbon cut with the at least one vinylaromatic monomer in a weight ratio of isobutene to vinylaromatic from 5 to 95: 95 to 5, in particular 30 from 70 to 70 to 30, copolymerized.

The highly reactive isobutene homo- or copolymers and especially the isobutene homopolymers used according to the invention preferably have a polydispersity

(PDI = Mw / Mn) from 1.05 to less than 3.5, preferably from 1.05 to less than 3.0, preferably from 1.05 to less than 2.5, preferably from 1.05 to 2, 3, more preferably from 1, 05 to 2.0 and in particular from 1, 1 to 1, 85 on. Typical values for PDI are 1, 2 to 1, 7 for optimal process control.

The highly reactive isobutene homo- or copolymers used according to the invention preferably have a number-average molecular weight M _n (determined by gel permeation chromatography) of preferably 500 to 250,000, particularly preferably 500 to 100,000, more preferably 500 to 25,000 and in particular 500 to 5000 isobutene homopolymers even more preferably, have a number average molecular weight M _{n of} from 500 to 10,000, and more preferably from 500 to 5,000, eg from about 1,000 or from about 2,300.

In particular, the process according to the invention is suitable for the preparation of isobutene homo- or copolymer derivatives of the general formula I in which the POL-based hydrophobic n-functional radical is obtained by homopolymerization of isobutene or copolymerization of isobutene with up to 20% by weight n Has a monofunctional and a number average molecular weight (M _n ) of 500 to 5000, especially 650 to 2500, has.

In particular, the process according to the invention is furthermore also suitable for the preparation of isobutene homo- or copolymer derivatives of the general formula I in which the POL underlying hydrophobic n-functional radical by homopolymerization of isobutene or copolymerization of isobutene with up to 20 wt .-% n Each with the concomitant use of a di- or trifunctional initiator (Inifers), is di- or trifunctional and has a number average molecular weight (M _n ) of 500 to 10,000, especially 1000 to 5000, having. In particular, the process according to the invention is furthermore also suitable for the preparation of isobutene copolymer derivatives of the general formula I in which the POL is based hydrophobic n-functional radical by copolymerization of isobutene with at least one vinylaromatic comonomer, optionally with Mit- using a di- or trifunctional initiator (Inifers), is mono-, di- or trifunctional and has a number average molecular weight (M _n ) of 500 to 15,000, especially 1000 to 10,000.

In a preferred embodiment of the process according to the invention for the preparation of isobutene homo- or copolymer derivatives of the general formula I, the low molecular weight polar group A is selected from

(a) mono- or polyamino groups having up to 6 nitrogen atoms, at least one nitrogen atom having basic properties;

(b) nitro groups, optionally in combination with hydroxyl groups;

(C) hydroxyl groups, optionally in combination with mono- or polyamino groups, wherein at least one nitrogen atom has basic properties;

(d) carboxyl groups or their alkali metal or alkaline earth metal salts;

Sulfonic acid groups or their alkali metal or alkaline earth metal salts; (f) polyoxy-C 2 -C 4 -alkylene groups represented by hydroxyl groups, mono- or

Polyamino groups, wherein at least one nitrogen atom has basic properties, or terminated by carbamate groups;

Carbonsäureestergruppen;

Succinic anhydride or succinic anhydride-derived moieties having hydroxy and / or amino and / or quaternized amino and / or amido and / or imido groups obtained by thermal or halogen catalyzed malination of the internal double bond (s) and the terminal vinylidene double bond (EN) the POL underlying Polyisobutenhomo- or copolymers were prepared with maleic anhydride and in the case of derived from succinic anhydride groups having hydroxy and / or amino and / or quaternized amino and / or amido and / or imido groups by appropriate subsequent reactions, wherein a resultant carboxylic acid amide or carboxylic acid imide derivative even by further reaction with at least one C2 to Ci2-dicarboxylic acid anhydride, with at least one C 2 to C ₄ - alkylene carbonate may be modified and / or with boric acid; (j) Mannich reaction of polyphenol-substituted phenols with aldehydes and mono- or polyamines;

Phenol, alkylphenol or (hydroxyalkyl) phenol moieties;

(I) hydroxymethyl groups;

Groupings formed by epoxidation of the terminal vinylidene double bond (s) of the POL underlying polyisobutene homo- or copolymers and subsequent

(i) hydrolysis to the 1, 2-diol,

(ii) reaction with a thiol or a polythiol,

(iii) reaction with ammonia, a monoamine or a polyamine,

(iv) reaction with a borane to give a borate ester and oxidative cleavage of the borate ester to the 1,3-diol,

(v) conversion to an aldehyde,

(vi) conversion to an aldehyde and conversion of the aldehyde to an oxime and reduction of the oxime to the amine,

(vii) conversion to an aldehyde and conversion of the aldehyde into an azo-methine cation and hydrolysis to the amine,

Conversion into an aldehyde and conversion of the aldehyde into an alcohol or alcohol

Conversion into an aldehyde and conversion of the aldehyde into a vessel see base or an enamine and reduction of the ship's base or enamine to the amine were generated;

(n) moieties formed by hydroboration of the terminal vinylidene double bond (s) of the polyisobutene homo- or poly- copolymers underlying POL and subsequent oxidation of the primary hydroboration product; and

(o) groupings formed by hydrosilylation of the terminal vinylidene double bond tion (s) of POL underlying polyisobutene homo- or copolymers were produced.

As examples of the above low molecular weight polar groups A, the following are mentioned:

Mono- or polyamino-containing isobutene homo- or copolymer derivatives of the general formula I are generally based on highly reactive polyisobutene having predominantly terminal vinylidene double bonds, in particular those having a number average molecular weight M _{n of} from 300 to 5,000 may also contain proportions of internal double bonds. Polyisobuteneamines based on highly reactive polyisobutene, which may contain up to 20% by weight of n-butene units, are, for example, according to EP-A 244 616 by hydroformylation and reductive amination with ammonia, monoamines or polyamines, such as dimethylaminopropylamine, ethylenediamine, Diethylenetriamine, triethylenetetramine or tetraethylenepentamine available. If polyisobutene with a proportion of internal double bonds (usually in the β and γ position) is used in the preparation of the isobutene homo- or copolymer derivatives I, the preparation route is also possible by chlorination and subsequent amination or by oxidation the double bond with air or ozone to the carbonyl or carboxyl compound and subsequent amination under reductive (hydrogenating) conditions. For amination here amines, such as. For example, ammonia, monoamines or polyamines, such as dimethylaminopropylamine, ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine, are used.

Further preferred monoamine groups (a) containing isobutene homo- or -copolymer derivatives I 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 and oxygen, as described in particular in WO A-97/03946 are described.

Further preferred monoamine groups (a) containing isobutene homo- or -copolymer derivatives I are the compounds obtainable from polyisobutene epoxides by reaction with amines and subsequent dehydration and reduction of the amino alcohols, as described in particular in DE-A-196 20 262 ,

Further preferred monoamino groups (a) containing isobutene homo- or -copolymer derivatives I are the compounds obtainable from the reaction of highly reactive polyisobutene with one or more aromatic or heteroaromatic amines. The highly reactive polyisobutene can be used, for example, with aniline, N-

Methylaniline, Ν, Ν-dimethylaniline, o-, m- or p-toluidine or o-, m- or p-aminopyridine are converted to the corresponding at the aromatic or heteroaromatic nucleus polyisobutyl-substituted compound. The aromatic amines used may also be substituted several times, in particular twice, at the nucleus, in particular by alkyl groups such as, for example, C 1 - to C ₄ -alkyl groups; Typical substitution patterns for such substituents on the aromatic nucleus are the 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-position. Typical compounds formed here are, for example, 4-polyisobutylaniline, 4-polyisobutyl-N-methylaniline, 4-polyisobutyl-N, N-dimethylaniline, 4-polyisobutyl-3-methylaniline or 5-polyisobutyl-2-aminopyridine. The synthesis of such on the aromatic or heteroaromatic core polyisobutyl-substituted compounds is carried out usually by the usual methods of electrophilic aromatic substitution (Friedel-Crafts alkylation) on aromati- see or heteroaromatic core, for example using Lewis acids such as AlC , ZnC, or BF3 as catalysts and at elevated temperatures, in particular 25 to 80 ° C or 25 to 250 ° C, if necessary in an inert solvent. Nitro groups (b), optionally in combination with hydroxyl groups, containing Isobutenhomo- or copolymer derivatives I are preferably reaction products of polyisobutenes of average degree of polymerization P = 5 to 100 or 10 to 100 with nitrogen oxides or mixtures of nitrogen oxides and oxygen, as described in particular WO-A-96/03367 and WO-A-96/03479. As a rule, these reaction products are mixtures of pure nitropolyisobutenes (eg, α, β-dinitropolyisobutene) and mixed hydroxynitropolyisobutenes (eg, α-nitro-β-hydroxy polyisobutene).

Hydroxyl groups in combination with isobutene homo- or copolymer derivatives I containing mono- or polyamino groups (c) are in particular reaction products of polyisobutene epoxides obtainable from polyisobutene preferably having predominantly terminal double bonds with M _n = 300 to 5000, with ammonia, mono- or polyamines, as described in particular in EP-A-476 485. Isobutene homo- or copolymer derivatives I containing hydroxyl groups (c) which have no mono- or polyamino groups are, for example, reaction products of polyisobutene epoxides obtainable from polyisobutene preferably having predominantly terminal double bonds with M _n = 300 to 5000, with water (hydrolysis) or with alcohols such as methanol or ethanol or the products of a reduction of the epoxide function, for example by means of lithium aluminum hydride.

Isobutene homo- or copolymer derivatives I containing carboxyl groups or their alkali metal or alkaline earth metal salts (d) are generally polyisobutenes into which one or more carboxyl groups have been introduced, for example by reaction with maleic anhydride, after which the carboxyl groups are wholly or partly to the alkali metal or alkaline earth metal salts and a remaining radical of the carboxyl groups are reacted with alcohols or amines.

Isobutene homo- or copolymer derivatives I containing sulfonic acid groups or their alkali metal or alkaline earth metal salts (e) are generally polyisobutenes in which a or several sulfonic acid groups have been introduced, after which the sulfonic acid groups are completely or partially converted to the alkali metal or alkaline earth metal salts and a remaining group of the carboxyl groups with alcohols or amines. Analogous alkali metal or alkaline earth metal salts of sulfosuccinic acid alkyl esters are described in EP-A-639 632. Such compounds serve primarily to prevent valve seat wear and may advantageously be used in combination with conventional fuel detergents such as poly (iso) butenamines or polyetheramines. Isobutene homo- or copolymer derivatives I containing polyoxy-C 2 -C 4 -alkylene groups (f) are preferably polyethers or polyetheramines obtained by reacting hydroxyl- or amino-containing polyisobutenes with 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 polyetheramines - by subsequent reductive amination with ammonia, monoamines or polyamines are available. Analogous reaction products of C 2 -C 6 -alkanols, C 6 -C 30 -alkanediols, mono- or di-C 2 -C 30 -alkylamines, C 1 -C 30 -alkylcyclohexanols or C 1 -C 30 -alkylphenols with 1 to 30 mol of ethylene oxide and / or propylene oxide and / or Butylene oxide per hydroxyl group or amino group are described in EP-A-310 875, EP-A-356 725, EP-A-700 985 and US-A-4 877 416.

Carboxylic acid ester groups (g) containing isobutene homo- or copolymer derivatives I are preferably esters of mono-, di- or tricarboxylic acids with hydroxylgruppenhal- term polyisobutenes. Analogous reaction products of long-chain alkanols or polyols with mono-, di- or tricarboxylic acids are described in DE-A-38 38 918. As mono-, di- or tricarboxylic acids it is possible to use aliphatic or aromatic acids. Typical representatives of such esters are corresponding adipates, phthalates, isophthalates, terephthalates and trimellitates. In particular, isobutene homo- or copolymer derivatives I containing succinic anhydride (h) are polyisobutenyl succinic anhydrides obtainable by reaction of highly reactive polyisobutene with M _n = 500 to 5000 with maleic anhydride by thermal means or via the chlorinated polyisobutene. The polyisobutene used can be reacted with 1 equivalent ("monomaleination"), with 2 equivalents of maleic anhydride ("bismaleination") or with 1 <n <2 equivalents of maleic anhydride, eg. B. with 1, 05 to 1, 3 equivalents of maleic anhydride are reacted.

Derived from succinic anhydride moieties with hydroxy and / or amino and / or quaternized amino and / or amido and / or imido (h) containing Isobutenhomo- or copolymer derivatives I are preferably corresponding derivatives of polyisobutyl or polyisobutenyl-substituted succinic anhydride and especially the corresponding derivatives of polyisobutenylsuccinic anhydride hydride, which can be obtained by reaction of highly reactive polyisobutene with M _n = 300 to 5000, which may still contain proportions of internal double bonds, with maleic anhydride by thermal means or via the chlorinated polyisobutene. Of particular interest here are derivatives with alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol or polyethers which are obtained by alkoxylation of the mentioned low-molecular alkanols with C 2 to C 4 ₄ -alkylene oxides have been prepared. Isobutene-containing C ₄ - hydrocarbon streams and especially aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine. The groups having hydroxyl, optionally quaternized amino, 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, are still free Amine groups, succinic acid derivatives having an acid and an amide function, carboximides with monoamines, carboxylic imides with di- or polyamines which in addition to the imide function still have free amine groups, or diimides formed by the reaction of di- or polyamines with two succinic acid derivatives. Such compounds are described as fuel additives in US-A-4,849,572.

By succinic anhydride derived groups having quaternized amino groups containing isobutene homo- or copolymer derivatives I are in particular quaternized nitrogen compounds to be understood by addition of a compound containing at least one reactive with an anhydride oxygen or nitrogen-containing group and additionally at least one quaternizable amino group containing polyisobutenyl succinic anhydride and subsequent quaternization, in particular with an epoxide, in particular in the absence of free acid, are obtainable, as described in EP patent application Az. 10 168 622.8. Suitable compounds having at least one anhydride-reactive oxygen or nitrogen-containing group and additionally at least one quaternizable amino group are in particular polyamines having at least one primary or secondary amino group and at least one tertiary amino group. Such a quaternized nitrogen compound is, for example, the reaction product of polyisobutenylsuccinic anhydride obtained at 40 ° C., in which the polyisobutenyl radical typically has an M _n of 1000, with 3- (dimethylamino) propylamine, which is a polyisobutenylsuccinic acid hemiamide and which is subsequently reacted with styrene oxide in the absence of free acid is quaternized at 70 ° C.

In the group (h) resulting Carbonsäureamid- and Carbonsäureimid derivatives, especially when used in lubricant formulations, for improving the swelling behavior of elastomers, for example, in seals of engines, units or devices containing or containing said derivatives Lubricant formulations come into contact, are incorporated, nor with at least one C2 to Ci2 dicarboxylic anhydride such as maleic anhydride or phthalic anhydride, with at least one C2- to C4-alkylene carbonate such as ethylene carbonate or propylene carbonate and / or with boric acid.

By Mannich reaction of substituted phenols with aldehydes and mono- or polyamines generated groupings (j) containing isobutene homo- or -co polymer derivatives I are preferably reaction products of polyisobutyl-substituted phenols with phenolated aldehydes such as formaldehyde, which, for example, in oligomeric or polymeric form, e.g. B. as paraformaldehyde, used, and with monoamines, z. For example, dimethylamine, diethylamine, propylamine, butylamine or morpholine, or with polyamines, eg. As ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or dimethylaminopropylamine. The polyisobutyl-substituted phenols may also contain portions of internal double bonds in addition to the terminal vinylidene double bonds. Such "polyisobutene Mannich bases" based on highly reactive polyisobutene with M _n = 300 to 5000 are described in EP-A-831 141.

Isobutene homo- or copolymer derivatives I containing phenol, alkylphenol or (hydroxyalkyl) phenol groupings (k) are, in particular, the precursors of the polyisobutene Mannich bases in group (j) which are obtained by reacting highly reactive polyisobutene with one or more corresponding phenols, optionally with subsequent reaction with an aldehyde, are formed. For this purpose, the highly reactive polyisobutene can be reacted, for example, with unsubstituted phenol, o-, m- or p-cresol, xylenol, hydroquinone, pyrocatechol or resorcinol. Thus formed polyisobutyl-substituted phenol may, for example, further with an aldehyde such as formaldehyde or paraformaldehyde to a polyisobutyl-substituted hydroxyalkyl kylphenol, in particular a polyisobutyl-substituted hydroxymethylphenol, z. B. to 1-hydroxymethyl-4-polyisobutylphenol be converted.

Hydroxymethyl groups (I) containing Isobutenhomo- or copolymer derivatives I are in particular the intermediates in the hydroformylation of highly reactive polyisobutene according to EP-A 244 616 in the presence of carbon monoxide and hydrogen by means of a suitable hydroformylation catalyst such as a rhodium or cobalt catalyst at temperatures of 80 to 200 ° C and CO / h pressures of up to 600 bar. A hydroxymethylpolyisobutene produced in this way can be obtained as a product mixture together with a polyisobutene containing an aldehyde group.

The groupings listed under (i) to (ix) in the group (m), which may be present in the isobutene homo- or copolymer derivatives I, and their production are within the scope of subsequent reactions of isobutene polymer epoxides, for example in WO 2007 / 025700 and are reproduced below: The epoxide can z. B. be hydrolyzed with water to 1, 2-diols or reacted with thiols or primary or secondary amines to give, inter alia, glycol thioethers and amines. By reacting an isobutene polymer having on average at least 0.7, preferably at least 0.9, epoxy groups per molecule, with polyols or in particular polythiols such as trimethylolpropane tris (3-mercaptopropionate) or pentaerythritol tetrakis- (3-mercaptopropionate) , or polyamines such as diethylenetriamine, one obtains networks which are advantageous due to their elastic and damping properties.

In a preferred subsequent reaction, the epoxide is converted to the aldehyde, which is carried out, for example, by catalysis using aluminosilicates, eg. As zeolites, acidic alumina, Lewis acids such as aluminum or zinc salts, for. As zinc bromide, or protic acids such as sulfuric acid, can take place. The aldehyde is itself a versatile starting material for valuable products. Conversion of polyisobutenyl epoxides to aldehydes is known e.g. in WO 90/10022 and US 6,303,703 or Organikum, 20th ed. 1999, Wiley-VCH, p. 615. It is possible to convert the aldehyde with ammonia or a primary amine into an imine and reduce the imine to the amine, in particular catalytically hydrogenating. Suitable primary amines are e.g. Diethylenetriamine, di (methylethylene) triamine, triethylenetetamine, tri (methylene) tetramine, tri (ethylenethrene) tetramine, tetraethylenepentamine, pentaethylenehexamine, ethylenediamine, hexamethylenediamine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, alkyl- substituted o-, m- and p-phenylenediamine, dimethylaminomethylamine, dimethylaminoethylamine, dimethylaminopropylamine, dimethylaminobutylamine, dimethylaminoheptylamine, diethylaminomethylamine, diethylaminopropylamine, diethylaminoamylamine, dipropylaminopropylamine, methylpropylaminoamine, propylbutylaminoethylamine, dimethyltrianiline, methylenedianiline, polymethyleneananiline and polyalkylmethyleneaniline , The reaction of the aldehyde with the primary amine and the hydrogenation of the obtained imine to a polyisobutenylamine is described in WO 90/10022.

It is also possible to convert the aldehyde into an oxime and reduce the oxime to the amine. Conveniently, hydroxylamine is used which is obtained by neutralizing a hydroxylammonium salt. The hydroxylamine reacts with the aldehyde to oxime. The oxime is then reduced to the amine by catalytic hydrogenation. The hydrogenation takes place at a suitable temperature and pressure in the presence of a hydrogenation catalyst. Suitable catalysts are, for. Raney nickel, nickel on kieselguhr, copper chromite, platinum on carbon, palladium on carbon and the like. The implementation is z. As described in US 6,303,703. In a further preferred embodiment, the aldehyde is converted into an azomethine cation in a Leuckart reaction. Various reagents are suitable for carrying out the Leuckart reaction; ammonium formate is preferred. The azomethine cation can then be converted to an amine by hydrolysis. The hydrolysis may suitably be carried out with dilute hydrochloric acid at a moderately elevated temperature. Preference is given to using a phase transfer catalyst such as tricaprylylmethylammonium nitrate. The reaction is described, for example, in US Pat. No. 6,303,703. The epoxide can be further reacted by reaction with a borane and subsequent oxidative cleavage of the borate ester formed to a 1, 3-diol, for example, to 2-polyisobutenyl-1, 3-propanediol. Suitable boranes are z. B. diborane (B2H6) and alkyl and arylboranes. The skilled worker is aware that such boranes can also be prepared in situ from a borohydride and an acid, usually BF ₃ etherate. The reaction with the borane is suitably carried out in a borane-coordinating solvent. Examples include open-chain ethers such as dialkyl, diaryl or alkylaryl ethers, and cyclic ethers such as tetrahydrofuran or 1, 4-dioxane, but also solvents such as toluene, cyclohexane and methylene chloride are suitable. The oxidative cleavage to a 1, 3-diol can, for example, by means of hydrogen peroxide in the presence of a base with heating to z. B. 50 to 75 ° C take place. Suitable solvents for this are ethers or mixtures of ethers and hydrocarbons.

Groupings resulting from hydroboration reactions, which may be present in the isobutene homo- or copolymer derivatives I, and their production are described in more detail, for example, in WO 2004/067583. General principles of hydroboration are described in J. March, Advanced Organic Chemistry, 4th edition, published by J. Wiley & Sons, pp. 783-789. Among the suitable borane sources is especially borane (BH ₃ ) itself, which usually occurs in the form of its dimer (B2H6). Suitably, the borane is generated in situ by reacting suitable precursors, especially alkali metal or alkaline earth metal salts of the BHU anion with boron trihalides. Typically, sodium borohydride and boron trifluoride etherate are used.

A preferred hydroborating agent for the terminal vinylidene double bonds of the polyisobutene is the reaction product of a borane source, e.g. B. in situ from alkali metal or alkaline earth metal salts of the BHU anion with boron trihalides borane, with 0.5 to 1, 8 equivalents per mole of borane of an alkene of a molecular weight of less than 250, z. For example, 2-methyl-2-butene or 1-methylcyclohexene.

The subsequent oxidation of the primary hydroboration product is typically carried out with alkaline hydrogen peroxide to give an alcohol which is preferably formally corresponds to the anti-Markovnikov hydration product of the unsaturated isobutene polymer. Alternatively, the polyisobutylboranes obtained as the primary hydroboration product may also be subjected to oxidative reaction with bromine in the presence of hydroxide ions to give the bromide.

Groups resulting from hydrosilylation reactions (o), which may be contained in the isobutene homo- or copolymer derivatives I, and their production are described in more detail, for example, in WO 2003/074577. For this purpose, a highly reactive polyisobutene can be subjected to a reaction with a silane in the presence of a silylation catalyst to give a polyisobutene which is at least partially functionalized with silyl groups. Silylated isobutene polymers in turn represent valuable starting materials for subsequent reactions to new products, for example for moisture-curing sealants and for formulations in which glass adhesion plays a role.

Suitable hydrosilylation catalysts are in particular transition metal catalysts wherein the transition metal is selected from Pt, Pd, Rh, Ru and Ir, e.g. Finely divided platinum, platinum chloride, hexachloroplatinic acid, tetramethyldivinyldisiloxane-platinum complexes, RhCl [P (C ₆ H ₅ ) 3] 3, RhCl ₃ , RuCl ₃ or IrCl ₃ . Suitable hydrosilylation catalysts are furthermore Lewis acids, such as aluminum trichloride or titanium tetrachloride, and also peroxides.

Suitable silanes are z. As halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane and trimethylsiloxydichlorosilane, alkoxysilanes such as trimethoxysilane, triethoxysilane, methyldimethoxysilane, phenyldimethoxysilane, 1, 3,3,5,5,7,7-heptamethyl-1, 1-dimethoxytetrasiloxane and acyloxysilanes.

The reaction temperature in the hydrosilylation is preferably in the range of 0 to 140 ° C, especially at 40 to 120 ° C. The reaction is usually carried out at atmospheric pressure, but can also be carried out at elevated pressures, eg. B. at 1, 5 to 20 bar, or reduced pressures, for. B. b egg 200 to 600 mbar done. The reaction can be carried out without solvent or in the presence of a suitable inert solvent such as toluene, tetrahydrofuran or chloroform. In a preferred embodiment, the process according to the invention for preparing isobutene homo- or copolymer derivatives of the general formula I in which A is a low molecular weight polar group which contains an amino function is carried out by reacting isobutene or a monomer containing isobutene. mixed in the presence

(A) an effective as a polymerization catalyst iron halide donor complex, an aluminum trihalide donor complex or a Aluminiumalkylhalogenid-donor complex which donor as an organic compound containing at least one ether function or a carboxylic acid ester function, in particular with concomitant use of an initiator, or

(B) at least one Lewis acid which is suitable as a polymerization catalyst or a complex of at least one Lewis acid and at least one donor which acts as a polymerization catalyst and in the presence of at least one initiator, where at least one initiator is an organic sulfonic acid of the general formula Z- SO3H in which the variable Z denotes a C 1 - to C 20 -alkyl radical, C 1 - to C 20 -haloalkyl radical, C 5 - to C ₆ -cycloalkyl radical, C 2 - to C 20 -aryl radical or a C ₇ - to C 20 -arylalkyl radical, polymerizes resulting highly reactive Isobutenhomo- or copolymer with a suitable catalyst in the presence of carbon monoxide and hydrogen hydroformylated and then aminiert in the presence of at least n equivalents of ammonia or a mono- or polyamine reductively.

The hydroformylation and the reductive amination of highly reactive polyisobutene are described, for example, in EP-A 244 616. The hydroformylation in the presence of carbon monoxide and hydrogen is usually carried out by means of a suitable hydroformylation catalyst such as a rhodium or cobalt catalyst at temperatures of 80 to 200 ° C and CO / H2 pressures of up to 600 bar. The subsequent reductive amination of the oxo product obtained (hydroxymethylpolyisobutene or product mixture of hydroxymethylpolyisobutene and polyisobutene-aldehyde of the same carbon number) is generally carried out at temperatures of 80 to 200 ° C. and hydrogen pressures of up to 600 bar, in particular 80 to 300 bar.

In a further preferred embodiment, the process according to the invention for preparing isobutene homo- or copolymer derivatives of the general formula I in which A is a low molecular weight polar group which contains an amino function is carried out in such a way that isobutene or an isobutene-containing mono - Merengemisch in the presence

(A) an effective as a polymerization catalyst iron halide donor complex, an aluminum trihalide donor complex or a Aluminiumalkylhalogenid-donor complex, which donor as an organic compound having at least one ether function or a carboxylic acid ester function contains, in particular with concomitant use of an initiator, or (B) at least one suitable as a polymerization catalyst Lewis acid or effective as a polymerization catalyst complex of at least one Lewis acid and at least one donor and in the presence of at least one initiator, wherein as at least one initiator organic sulfone acid of the general formula Z-SO3H: in which the variable Z is a C1 to C2o alkyl, d- to C2o-haloalkyl, C5-Ce cycloalkyl, CQ to C2o-aryl radical or a C ₇ - to C2o- Arylalkyl radical, polymerized, the resulting highly reactive Isobutenhomo- or co-polymer with a suitable activating agent, in particular with chlorine, treated and then reacted with n equivalents of ammonia or a mono- or polyamine.

In a further preferred embodiment, the process according to the invention for preparing isobutene homo- or copolymer derivatives of the general formula I in which A is a low molecular weight polar group which contains a carboxylic acid derivative function, in particular a carboxylic imide function, is carried out in such a way that isobutene is used or an isobutene-containing monomer mixture in the presence of (A) as a polymerization catalyst effective iron halide donor complex, an aluminum trihalide donor complex or a Aluminiumalkylhalogenid-donor complex which donor as an organic compound having at least one ether function or a carboxylic acid ester function, in particular with concomitant use of an initiator, or

(B) at least one Lewis acid which is suitable as a polymerization catalyst or a complex of at least one Lewis acid and at least one donor which acts as a polymerization catalyst and in the presence of at least one initiator, where at least one initiator is an organic sulfonic acid of the general formula Z- SO3H: in which the variable Z is a C1 to C2o alkyl, d- to C2o-haloalkyl, C5-Ce cycloalkyl, CQ to C2o-aryl radical or a C ₇ - to C2o-arylalkyl radical referred polymerized, the resulting highly reactive Isobutenhomo- or copolymer with an ethylenically unsaturated C ₄ - to C ₂ -dicarboxylic acid or a reactive derivative thereof, in particular with maleic anhydride, thermally or halogenated catalyzed and optionally subsequently with a mono- or polyamine in the entspechende carboxylic acid amide or Carbonsäureimid derivative wherein the resulting carboxylic acid amide or carboxylic acid im id derivative can be modified by further reaction with at least one C2 to Ci2 dicarboxylic anhydride, with at least one C2 to C ₄ alkylene carbonate and / or with boric acid.

In a further preferred embodiment, the process according to the invention for preparing isobutene homo- or copolymer derivatives of the general formula I in which A is a low molecular weight polar group which contains an amino function is carried out in such a way that isobutene or a monomer mixture comprising isobutene in present (A) an iron halide donor complex which acts as a polymerization catalyst, an aluminum trihalide donor complex or an aluminum alkyl halide donor complex which contains as donor an organic compound having at least one ether function or one carboxylic ester function holds, in particular with concomitant use of an initiator, or at least one suitable as a polymerization catalyst Lewis acid or effective as a polymerization catalyst complex of at least one Lewis acid and at least one donor and in the presence of at least one initiator, wherein at least one initiator is an organic sulfone acid of the general formula Z-SO3H, in which the variable Z is a C 1 - to C 20 -alkyl radical, C 1 - to C 20 -haloalkyl radical, C 5 - to C ₆ -cycloalkyl radical, C 2 - to C 20 -aryl radical or a C ₇ - to C 2 - Arylalkyl radical, polymerized, the resulting highly reactive isobutene homo- or co-polymer with a phenol in there s converts corresponding alkylphenol and this then converted by reaction with an aldehyde and a primary or secondary amine in the corresponding Mannich adduct. The present invention also relates to novel isobutene homopolymer derivatives of the general formula II

in the

R ¹⁰ , R ¹¹ and R ¹² independently of one another are hydrogen, C ₂ -C 20 -alkyl, C 5 -C 6 -cycloalkyl, CQ-C _{2 0} -Al-1, C ₇ - to C 20 -alkylaryl or phenyl, where an aromatic nucleus is still one or more C 1 to C ₄ alkyl or C ₄ to C ₄ alkoxy radicals or groupings of the general formula III

as at least one of the variables R ¹⁰ , R ¹¹ or R ^{12 is} hydrogen and at least one of the variables R ¹⁰ , R ¹¹ or R ¹² phenyl, which is one or more C ₄ to C ₄ alkyl or C to C ₄ alkoxy or carry one or two moieties of the general formula III as a substituent can,

Y is an isobutylene or an isobutenylene bridge unit, A is a low molecular weight polar group which has one or more amino functions and / or nitro groups and / or a hydroxyl groups and / or a carboxylic acid or carboxylic acid derivative functions, in particular succinic anhydride or succinic acid derivative functions, and / or sulfonic acid or sulfonic acid derivative functions and / or aldehyde functions and / or silyl groups, y is a number from 1 to 350, in particular from 9 to 100, especially from 12 to 50, wherein in telechelic isobutene homopolymer derivatives II the two or three variables y in the molecule may be the same or different, and z is the number 0 or preferably the number 1.

The isobutene homo- and copolymer derivatives prepared according to the invention are suitable, for example, as fuel and lubricant additives. The isobutene homo- or copolymer derivatives prepared according to the invention are prepared from isobutene polymers having a high content of terminal vinylidene double bonds, which is usually significantly higher than 90 mol%, and can thus be produced in high yields. Furthermore, the appearance and the consistency of these derivatives, for example their color, are improved. Furthermore, the physical properties of these derivatives, in particular the viscosity behavior at low temperatures, and the solubilities, in particular in polar media, the temperature stability and the storage stability of the derivatives are also improved. The catalyst system used for the production of the isobutene polymers in the precursor is sufficiently active, durable, easy to handle and not susceptible to interference, in particular it is free of fluorine, thus undesirable due to residual fluorine content-related corrosion on metallic materials and steel grades is avoided.

Claims

claims

1 . Process for the preparation of isobutene homo- or copolymer derivatives of general formula I.

POL (-A) _n (I) in the

POL denotes the n-functional radical of a hydrophobic polyisobutene homo- or copolymer having a number-average molecular weight (M _n ) of 110 to 250,000, which may contain structural units of mono-, di- or trifunctional initiators,

A is a low molecular weight polar group which in each case has one or more amino functions and / or nitro groups and / or hydroxyl groups and / or mercaptan groups and / or carboxylic acid or carboxylic acid derivative functions, in particular succinic anhydride or succinic acid derivative functions, and / or sulfonic acid or sulfonic acid derivative functions and / or aldehyde functions and / or silyl groups, means and the variable n is the number 1, 2 or 3, wherein when n = 2 and n = 3, the variables A may be the same or different, characterized in that isobutene or an isobutene containing monomer mixture in the presence

(A) an iron halide donor complex effective as a polymerization catalyst, an aluminum trihalide donor complex or an aluminum alkyl halide donor complex containing as donor an organic compound having at least one ether function or carboxylic ester function, or

(B) at least one suitable as a polymerization catalyst Lewis acid

or a complex effective as a polymerization catalyst of at least one Lewis acid and at least one donor and in the presence of at least one initiator, wherein at least one initiator is an organic sulfonic acid of the general formula Z-SO3H in which the variable Z is a d- to C2o Alkyl radical, C 1 - to C 20 haloalkyl radical, C 5 - to C ₆ -cycloalkyl radical, C 2 - to C 20 -aryl radical or a C ₇ - to C 2 -aryl arylalkyl radical, polymerizes, the resulting highly reactive isobutene homo- or copolymer, which has a content of at least 50 mol% of terminal vinylidene double bonds per polyisocyanate Sobutene chain end having at least n equivalents of the low molecular weight polar group A or a partial structure of the low molecular weight polar group A introducing compound and in the case of reaction with a partial structure completes the formation of the low molecular weight polar group A by subsequent reactions.

Process according to Claim 1, characterized in that isobutene or a mixture of isobutene-containing monomers is polymerized in the presence of a ferric chloride donor complex or aluminum trichloride donor complex which is effective as a polymerization catalyst in accordance with embodiment (A).

Process according to claim 1 or 2, characterized in that, according to embodiment (A), the polymerization catalyst used is an iron halide donor complex, an aluminum trihalide donor complex or an aluminum alkyl halide donor complex which contains as donor a dihydrocarbyl ether of the general formula R ¹ -O-R ² , in which the variables R ¹ and R ² independently of one another denote d- to C ² -alkyl radicals, C 5 - to C ₆ -cycloalkyl radicals, C 2 - to C 20 -aryl radicals or C ₇ - to C 20 -arylalkyl radicals.

Process according to claim 1 or 2, characterized in that, according to embodiment (A), the polymerization catalyst used is an iron halide donor complex, an aluminum trihalide donor complex or an aluminum alkyl halide donor complex which contains as donor a carboxylic acid hydrocarbyl ester of the general formula R ³ - COOR ⁴ contains, in which the variables R ³ and R ⁴ independently of one another C to C 20 alkyl radicals, C5 to Ce cycloalkyl radicals, CQ to C 2o aryl radicals or C ₇ - to C 2o arylalkyl radicals.

Process according to Claims 1 to 4, characterized in that, according to embodiment (A), the polymerization catalyst used is an iron halide donor complex, an aluminum trihalide donor complex or an aluminum alkyl halide donor complex in which the donor compound is a total Having carbon number from 3 to 16.

Process according to claims 1 to 5, characterized in that, according to embodiment (A), the polymerization is carried out using an initiator which is selected from organic hydroxy compounds in which one or more hydroxyl groups are attached to one sp ³ -hybridised carbon atom or to one are bound to aromatic ring, organic halogen compounds in which one or more halogen atoms are bonded to each sp ³ -hybridized carbon atom, protic acids and water.

A method according to claim 6, characterized in that the initiator is selected from water, one or more protic acids, methanol, ethanol, 1-phenylethanol, 1- (p-methoxyphenyl) ethanol, n-propanol, isopropanol, 2-phenyl-2- propanol, n-butanol, isobutane nol, sec-butanol, tert-butanol, 1-phenyl-1-chloroethane, 2-phenyl-2-chloropropane, tert-butyl chloride and 1, 3 or 1, 4-bis (1-hydroxy-1 - methylethyl) benzene and mixtures thereof. 8. The method according to claims 1 to 7, characterized in that according to embodiment (A) the polymerization in the presence of 0.01 to 10 mmol, each based on 1 mol of isobutene monomer used in homopolymerization of isobutene or 1 mol the total amount of the polymerizable monomers used in copolymerization of isobutene, performs a nitrogen-containing basic compound.

9. The method according to claim 8, characterized in that is used as the nitrogen-containing basic compound pyridine or a derivative of pyridine.

10. The method according to claims 1 to 9, characterized in that according to embodiment (A) the polymerization in a halogenated aliphatic hydrocarbon or in a mixture of halogenated aliphatic hydrocarbons or in a mixture of at least one halogenated aliphatic hydrocarbon and at least one aliphatic, cycloaliphatic or aromatic hydrocarbon or in a halogen-free aliphatic or halogen-free aromatic hydrocarbon as inert diluent.

1 1. A method according to claim 1, characterized in that according to embodiment (B) is used as at least one initiator, an organic sulfonic acid selected from methanesulfonic acid, trifluoromethanesulfonic acid, trichloromethanesulfonic acid and toluenesulfonic acid or mixtures thereof.

12. The method according to claim 1 or 1 1, characterized in that according to embodiment (B) selected as the Lewis acid for the complex effective as the polymerization catalyst at least one compound selected from the binary chlorine and fluorine compounds of the elements of the 1st to the 8th subgroup and the 3rd to 5th main group of the periodic table or mixtures thereof.

13. The method according to claim 12, characterized in that as Lewis acid, a binary chlorine or fluorine compound selected from BCI ₃ , AICI3, TiCu, FeC, FeC, ZnC, BF3, AIF3, TiF ₄ , FeF ₂ , FeF 3 and ZnF ₂ uses this.

14. The method according to claims 1, 1 1, 12 and 13, characterized in that one uses according to embodiment (B) a complex effective as a polymerization catalyst containing as donor an organic compound having at least one ether function or a carboxylic acid ester function ,

15. The method according to claim 14, characterized in that the donor acting organic compound is a dihydrocarbyl ether of the general formula R ¹ -0-R ² , in which the variables R ¹ and R ^{2 are} independently d- to C2o-alkyl radicals, C5- to Ce-cyclo- alkyl, CQ to C2o-aryl radicals or C ₇ - to C2o-arylalkyl radicals denote a carbonyl or bonsäurehydrocarbylester of the general formula R ³ COOR ^4, in which the variables R d ³ and R ^{4 are} independently to C2o-alkyl, C5- to Ce-cycloalkyl, CQ to C 20 aryl or C ₇ - to denote C2o-arylalkyl radicals, represents.

16. The method according to claim 15, characterized in that the donor acting organic compound has a total carbon number of 3 to 16.

17. The method according to claims 1, 1 1, 12, 13, 14, 15 and 16, characterized in that according to embodiment (B) the polymerization is carried out with the concomitant use of at least one further initiator which mono- or polyfunctional and under organic see hydroxy compounds, organic halogen compounds, proton acids and water is selected.

18. The method according to claim 17, characterized in that the at least one additional initiator is selected from water, one or more protic acids, methanol, ethanol, 1-phenylethanol, 1- (p-methoxyphenyl) ethanol, n-propanol, Isopropanol, 2-phenyl-2-propanol, n-butanol, isobutanol, sec-butanol, tert-butanol, 1-phenyl-1-chloroethane, 2-phenyl-2-chloropropane, tert-butyl chloride and 1, 3 - or 1, 4-bis (1-hydroxy-1-methyl-ethyl) benzene and mixtures thereof. 19. The method according to claims 1, 1 1, 12, 13, 14, 15, 16, 17 and 18, characterized in that according to embodiment (B), the polymerization in the presence of 0.01 to 10 mmol, in each case based on 1 mol of isobutene monomer used in homopolymerization of isobutene or to 1 mol of the total amount of the polymerizable monomers used in copolymerization of isobutene, a nitrogen-containing basic compound performs.

20. The method according to claim 19, characterized in that is used as the nitrogen-containing basic compound pyridine or a derivative of pyridine. 21. Process according to claims 1, 1, 1, 12, 13, 14, 15, 16, 17, 18, 19 and 20, characterized in that, according to embodiment (B), the polymerization is carried out at a temperature of -30 ° C to +50 ° C performed.

22. The method according to claims 1, 1 1, 12, 13, 14, 15, 16, 17, 18, 19, 20 and 21, characterized in that according to embodiment (B) the polymerization in an aliphatic, cycloaliphatic or aromatic Hydrocarbon, in a halogenated aliphatic hydrocarbon or in a mixture of aliphatic, cycloaliphatic and / or aromatic hydrocarbons or from halogenated aliphatic hydrocarbons or in a mixture of at least one halogenated aliphatic hydrocarbon and at least one aliphatic, cycloaliphatic or aromatic hydrocarbon as an inert diluent.

23. Process according to claims 1 to 22, characterized in that a technical C 4 hydrocarbon stream having an isobutene content of 1 to 100% by weight, in particular a raffinate 1 stream, is used as the monomer source for the polymerization. a b / b stream from an FCC refinery unit, a propylene-isobutane co-oxidation product stream, or a metathesis unit product stream.

24. The method according to claims 1 to 23 for the preparation of isobutene homo- or - copolymer derivatives of general formula I, in which the POL underlying hydrophobic n-functional radical by homopolymerization of isobutene or copolymerization of isobutene with up to 20 wt .-% n-butene, is monofunctional and has a number average molecular weight (M _n ) of 500 to 5,000.

25. The method according to claims 1 to 23 for the preparation of isobutene homo- or copolymer derivatives of the general formula I, in which the POL underlying hydrophobic n-functional radical by homopolymerization of isobutene or copolymerization of isobutene with up to 20 wt. % n-butene, each with the concomitant use of a di- or trifunctional initiator (inifers), is di- or trifunctional and has a number average molecular weight (M _n ) of 500 to 10,000. 26. The method according to claims 1 to 23 for the preparation of isobutene copolymers of the general formula I, in which the POL underlying hydrophobic n-functional radical by copolymerization of isobutene with at least one vinyl aromatic comonomer, optionally with the concomitant use of a di- or trifunctional Initiator (Inifers), is mono-, di- or trifunctional and has a number average molecular weight (M _n ) of 500 to 15,000.

27. The method according to claims 1 to 26 for the preparation of isobutene homo- or copolymer derivatives of general formula I, wherein the low molecular weight polar group A is selected from

(b) nitro groups, optionally in combination with hydroxyl groups;

Hydroxyl groups, optionally in combination with mono- or polyamino groups, wherein at least one nitrogen atom basic properties Has;

(d) carboxyl groups or their alkali metal or alkaline earth metal salts; (e) sulfonic acid groups or their alkali metal or alkaline earth metal salts;

(f) polyoxy-C 2 -C 4 alkylene moieties terminated by hydroxyl groups, mono- or polyamino groups, wherein at least one nitrogen atom has basic properties, or terminated by carbamate groups;

(g) carboxylic acid ester groups;

(h) succinic anhydride or succinic anhydride-derived moieties having hydroxy and / or amino and / or quaternized amino and / or amido and / or imido groups obtained by thermal or halogen catalyzed maleination of the internal double bonds) and the terminal vinylidene double bond ( en) the POL underlying polyisobutene homo- or copolymers with maleic anhydride and in the case of derived from succinic anhydride groups having hydroxy and / or amino and / or quaternized amino and / or amido and / or imido groups were prepared by appropriate subsequent reactions, wherein a resulting carboxylic acid amide or Carbonsäureimid derivative can be modified by further reaction with at least one C2 to Ci2 dicarboxylic anhydride, with at least one C2 to C4 alkylene carbonate and / or boric acid;

(j) Mannich reaction of polyphenol-substituted phenols with aldehydes and mono- or polyamines; (k) phenol, alkylphenol or (hydroxyalkyl) phenol moieties;

(I) hydroxymethyl groups;

(m) Groupings formed by epoxidation of the terminal vinylidene double bond (s) of the POL underlying polyisobutene homo- or copolymers and subsequent

(i) hydrolysis to the 1, 2-diol, (ii) reaction with a thiol or a polythiol,

Reaction with ammonia, a monoamine or a polyamine, (iv) reaction with a borane to give a borate ester and oxidative cleavage of the borate ester to the 1,3-diol,

(v) conversion to an aldehyde,

(vii) conversion to an aldehyde and conversion of the aldehyde to an azomethine cation and hydrolysis to the amine,

(viii) conversion to an aldehyde and conversion of the aldehyde to an alcohol or

(ix) conversion to an aldehyde and conversion of the aldehyde to a Schiff base or enamine and reduction of Schiff's

Base or the enamine were generated to the amine;

(n) moieties formed by hydroboration of the terminal vinylidene double bond (s) of the polyisobutene homo- or polyols underlying POL and subsequent oxidation of the primary hydroboration product; and

(o) Groupings generated by hydrosilylation of the terminal vinylidene double bond (s) of the underlying polyisobutene homo- or co-polymers.

28. A process for the preparation of isobutene homo- or copolymer derivatives of general formula I, in which A is a low molecular weight polar group which contains an amino function, according to claims 1 to 27, characterized in that isobutene or an isobutene-containing Monomer mixture in the presence

(A) an effective as a polymerization catalyst iron halide donor complex, an aluminum trihalide donor complex or an aluminum alkyl halide donor complex containing as donor an organic compound having at least one ether function or a carboxylic ester function, in particular with concomitant use of a Initiator, or (B) at least one suitable as a polymerization catalyst Lewis acid or effective as a polymerization catalyst complex of at least one Lewis acid and at least one donor and in the presence of at least one initiator, wherein at least one initiator is an organic sulfonic acid of the general formula Z-SO3H in which the

Variable Z denotes a C 1 - to C 20 -alkyl radical, C 1 - to C 20 -alkyl radical, C 5 - to C ₆ -cycloalkyl radical, C 2 - to C 20 -aryl radical or denotes a C ₇ - to C 20 -arylalkyl radical, polymerizes the resulting highly reactive isobutene homo- or copolymer hydroformylated with a suitable catalyst in the presence of carbon monoxide and hydrogen and then reductively aminated in the presence of at least n equivalents of ammonia or a mono- or polyamine. 29. A process for the preparation of isobutene homo- or copolymer derivatives of general formula I in which A is a low molecular weight polar group which contains an amino function, according to claims 1 to 27, characterized in that isobutene or an isobutene-containing A monomer mixture in the presence of an effective as a polymerization catalyst iron halide donor complex, an aluminum trihalide donor complex or an aluminum alkyl halide donor complex containing as donor an organic compound having at least one ether function or a carboxylic ester function, in particular with concomitant use of a Initiator, or

(B) at least one suitable as a polymerization catalyst Lewis acid

or a complex effective as a polymerization catalyst of at least one Lewis acid and at least one donor and in the presence of at least one initiator, wherein at least one initiator is an organic sulfonic acid of the general formula Z-SO3H, in which

Variable Z denotes a C 1 - to C 20 -alkyl radical, C 1 - to C 20 -alkyl radical, C 5 - to C ₆ -cycloalkyl radical, C 2 - to C 20 -aryl radical or denotes a C ₇ - to C 20 -arylalkyl radical, polymerizes the resulting highly reactive isobutene homo- or copolymer with a suitable activating agent, in particular with chlorine, and then reacted with n equivalents of ammonia or a mono- or polyamine.

30. A process for the preparation of isobutene homo- or copolymer derivatives of general formula I in which A is a low molecular weight polar group which contains a carboxylic acid derivative function, in particular a carboxylic imide function, means, according to the claims Chen 1 to 27, characterized in that isobutene or a isobutene-containing monomer mixture in the presence

(A) an effective as a polymerization catalyst iron halide donor complex, an aluminum trihalide donor complex or a

Aluminumalkylhalogenid-donor complex which contains as donor an organic compound having at least one ether function or a carboxylic acid ester function, in particular with concomitant use of an initiator, or

(B) at least one suitable as a polymerization catalyst Lewis acid

Variable Z is a C 1 - to C 20 -alkyl radical, C 1 - to C 20 -haloalkyl, C 5 - to

Ce-cycloalkyl radical, CQ- to C 20 -aryl radical or a C ₇ - to C 20 -arylalkyl radical, polymerized, the resulting highly reactive isobutene homo- or copolymer with an ethylenically unsaturated C ₄ - to C 12 -dicarboxylic acid or a reactive derivative thereof, especially with maleic anhydride, thermally or halogen-catalyzed and, where appropriate, subsequently converted with a mono- or polyamine into the corresponding carboxylic acid amide or carboxylic acid imide derivative, the resulting carboxylic acid amide or carboxylic acid imide derivative remaining by further reaction with at least one C2- can be modified to Ci2-Dicarbonsäureanhy-anhydride, with at least one C 2 to C ₄ -Alkylencarbonat and / or with boric acid. A process for the preparation of isobutene homo- or copolymer derivatives of general formula I in which A is a low molecular weight polar group which contains an amino function, according to claims 1 to 27, characterized in that isobutene or an isobutene-containing monomer mixture in present

(B) at least one suitable as a polymerization catalyst Lewis acid

or a complex of min. at least one Lewis acid and at least one donor and in the presence of at least one initiator, wherein at least one initiator is an organic sulfonic acid of the general formula Z-SO3H, in which the variable Z is a C 1 - to C 20 -alkyl radical, C 1 - to C 20 haloalkyl, C5-Ce cycloalkyl, CQ to C2o-aryl radical or a C ₇ - to C2o-arylalkyl radical, designated polymerized, the resulting highly reactive isobutene homo- or copolymer with a phenol converted into the corresponding alkyl phenol and then by reacting this with an aldehyde and a primary or secondary amine into the corresponding Mannich adduct.

32. Isobutene homopolymer derivatives of the general formula II

in the

as at least one of the variables R ¹⁰ , R ¹¹ or R ^{12 is} hydrogen and at least one of the variables R ¹⁰ , R ¹¹ or R ¹² phenyl, which is one or more C ₄ to C ₄ alkyl or C 1 to C ₄ alkoxy radicals or one or two groupings of the general formula III as substituents,

Y represents an isobutylene or an isobutenylene bridge unit,

A is a low molecular weight polar group which contains one or more amino functions and / or nitro groups and / or hydroxyl groups and / or carboxylic acid or carboxylic acid derivative functions, in particular succinic anhydride or succinic acid derivative functions, and / or sulfonic acid or sulfonic acid derivative functions and / or aldehyde functions and / or silyl groups . y is a number from 1 to 350, wherein in the case of telechelic isobutene homopolymer derivatives II, the two or three variables y in the molecule may be identical or different, and z is the number 0 or 1.