WO2012072536A2

WO2012072536A2 - Production of isobutylene copolymer derivatives

Info

Publication number: WO2012072536A2
Application number: PCT/EP2011/071112
Authority: WO
Inventors: Hannah Maria KÖNIG; Klaus MÜHLBACH; Helmut Mach; Ulrich Eichenauer
Original assignee: Basf Se
Priority date: 2010-11-30
Filing date: 2011-11-28
Publication date: 2012-06-07
Also published as: AR084034A1; WO2012072536A3

Abstract

Disclosed is the production of isobutylene copolymer derivatives by radically copolymerizing (a) 10 to 90 mol-% of a monoethylenically unsaturated C₄ to C₁₂ dicarboxylic acid or the anhydride, half-ester or full ester thereof, (b) 10 to 90 mol-% of a highly reactive isobutylene polymer having a number average molecular weight of 110 to 250,000, and (c) 0 to 50 mol-% of monoethylenically unsaturated compounds that can be copolymerized with monomer components (a) and (b), and then reacting the carboxylic acid or carboxylic acid derivative functions in the obtained isobutylene copolymer with ammonia, an amine and/or an alcohol so as to form groupings having hydroxy, carboxylic acid ester, amino, quaternized amino, amido and/or imido groups. In order to produce monomer component (b), 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 at least one organic sulfonic acid and optional donors.

Description

Preparation of Derivatives of Isobutene Copolymers Description The present invention relates to an improved process for the preparation of derivatives of isobutene copolymers. Furthermore, the present invention relates to novel Isobutencopolyme- risat derivatives.

Isobutene copolymer derivatives such as are often obtained from so-called highly reactive polyisobutenes. In contrast to the so-called low-reactive polyisobutenes, highly reactive polyisobutenes are understood as meaning 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. Vinylidene groups are usually understood as meaning those double bonds whose position in the molecule is defined by the general formula

o ymer is described, i. the double bond is in the polymer chain in one

α-position. "Polymer" stands for the truncated to an isobutene polyisobutene. 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 Polyisobutenylsuccinanhydriden. 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 dispersibility. 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 having a similarly high proportion of terminal double bonds but having 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, the polymerization being carried out 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.

In the not yet disclosed European patent application with the file number

10157068.7 is a process for the preparation of highly reactive isobutene homo- or

copolymers by polymerization in the presence of an aluminum trihalide donor complex or of an aluminum alkyl halide donor complex which acts as a polymerization catalyst and which contains as donor an organic compound having at least one ether function or a carboxylic ester function and optionally an organic hydroxy compound, contains an organic halogen compound or water as an initiator. Further reactions with the highly reactive Isobutenhomo- or

Copolymers 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.

WO 95/07944 describes functional groups carrying copolymers which by free-radical copolymerization of (a) 20 to 60 mol% of at least one monoethynic unsaturated C ₄ - to Cß-dicarboxylic acid or its anhydride, (b) 10 to 70 mol% of at least one oligomer of the propene or a branched 1-olefin having 4 to 10 carbon atoms such as isobutene and an average molecular weight M _w of 300 to 5000 and (c) 1 to 50 mol% of at least one monoethylenically unsaturated compound which with the monomers (a) and (b) is copolymerizable, and subsequent functionalization of the copolymeri- sates on the anhydride or carboxyl groups with amines is available. These copolymers are suitable as fuel and lubricant additives.

However, the production methods of derivatives of copolymers based on highly reactive polyisobutenes known from the prior art 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 end- and the consistency of the derivatives, in particular the suppression of discoloration, for example caused 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, as well as the solubilities, especially in polar media, the temperature stability and the storage stability of the derivatives still in need of improvement. The derivatization methods of isobutene copolymers known from the prior art which emanate from isobutene polymers prepared by means of fluorine-containing polymerization catalysts have the disadvantage that they trigger corrosion on numerous metallic materials and types of steel due to the residual fluorine content.

The object of the present invention was to provide, starting from highly reactive polyisobutenes, an improved process for preparing derivatives of isobutene copolymers which no longer has the deficiencies of the prior art. In particular, the isobutene 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 mol -%, particularly preferably at least 90 mol%, and can be produced 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 should 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 derivatives of isobutene copolymers by free-radical copolymerization of

(a) 10 to 90 mol%, preferably 20 to 60 mol%, in particular 20 to 60 mol%,

at least one monoethylenically unsaturated C ₄ - to C 12 -dicarboxylic acid or its anhydride or its half or full ester,

(b) 10 to 90 mol%, preferably 10 to 70 mol%, in particular 10 to 70 mol%,

a highly reactive polyisobutene homo- or copolymer having a number-average molecular weight (M _n ) of from 10 to 250,000 and a content of at least 50 mol% of terminal vinylidene double bonds per polyisobutene chain end, the structural units of mono-, di- or may contain incorporated trifunctional initiators, (C) 0 to 50 mol%, preferably 0 to 50 mol%, in particular 1 to 50 mol%, of one or more monoethylenically unsaturated compounds which are copolymerizable with the monomer components (a) and (b), and subsequent reaction of part or all of the carboxylic acid or carboxylic acid derivative functions in the resulting isobutene copolymer with ammonia, a mono- or polyamine, an alcohol or a mixture of said reactants to form groups having hydroxyl and / or carboxylic ester and / or Amino- and / or quaternized amino and / or amido and / or imido groups, which is characterized in that to produce the monomer component (b) isobutene 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 as donor an organic V contains compound having at least one ether function or a carboxylic acid 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

a 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 C1 to C2o-alkyl radical, d- to C2o-haloalkyl, C5- to Ce-cycloalkyl, CQ-bis

C2o-aryl radical or a C ₇ - to C2o-arylalkyl radical, designated polymerized.

The sum of the mol% of the monomer components (a), (b) and (c) to be copolymerized with each other is 100 in all cases.

The above-mentioned polymerization method for isobutene or isobutene-containing monomer mixtures according to the invention for producing the monomer component (b) according to embodiment (A) is described in the above-cited European patent application with the file reference 10157068.7 not yet disclosed 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 copoly such polymers containing more than 2 mol% of monomers in copolymerized form, which are different 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-dimethyl-propyl, 1-ethylpropyl, n-hexyl, 1, 1-dimethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1, 1, 2-trimethylpropyl, 1, 2,2-trimethylpropyl, 1 - Ethyl 1-methylpropyl, 1-ethyl-2-methylpropyl, 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-tri-decyl, isotridecyl, n - tetradecyl, n-hexadecyl, n-octadecyl and n-eicosyl. Such C 1 - to C 20 -alkyl radicals can also to a small extent contain heteroatoms such as oxygen, nitrogen or halogen atoms, for example chlorine, and / or non-protic functional groups such as, for example

Carboxylestergruppen, 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 a small amount of heteroatoms such as oxygen, nitrogen or halogen atoms, for example chlorine, 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 chlorine 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-phenyl-butyl, optionally substituted C 1 -C 4 -alkylnaphthyl, such as naphthylmethyl, 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 can 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 C 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. Particularly suitable aluminum alkyl halide is a mono (C 1 to C ₄ alkyl) aluminum dihalide or a di (C 1 to 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 iron halide donor complex effective as a polymerization catalyst, the aluminum trihalide donor complex or aluminum alkyl halide donor complex has an organic compound having at least one ether function as donor, acetals and are also known as compounds having at least one ether function To understand hemiacetals.

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, are used 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 are C 1 - to C 20 -alkyl radicals, especially C 1 - to C 6 -alkyl radicals, C 5 - to Ce -Cycloalkyl radicals, CQ to C20- 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.

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, M ethyl 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 t-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 ethers and diphenyl ethers have donors for the iron halide donor complexes, the aluminum trihalide donor complexes or the aluminum halide 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 contains, as donor, a hydrocarbyl hydrocarbon ester of general formula R ³ -COOR ⁴ , in which the variables R ³ and R ⁴ independently of one another denote C 1 to C 20 -alkyl radicals, in particular, C 1 - to C 6 -alkyl radicals, C 5 - to C 6 -cycloalkyl radicals, CQ to C2o-aryl radicals, particularly CQ to C12 aryl radicals, or C ₇ - to C 20 arylalkyl radicals, in particular C ₇ - to Ci2 arylalkyl radicals, denote.

Examples of the abovementioned carboxylic acid hydrocarbyl esters are methyl formate, ethyl formate, formic acid n-propyl ester, 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, methyl propionate, Propionic acid ethyl ester, propionic acid n-propyl ester, propionic acid isopropyl ester, n-butyl propionate, sec.-butyl propionate, isobutyl propionate, tert-butyl propionate, methyl butyrate, ethyl butyrate, butyric acid n-butyl ester. propyl ester, butyric acid isopropyl ester, n-butyl butyrate, secbutyl butbutyrate, isobutyl butyrate, tert-butyl butyrate, cyclohexanecarboxylic acid methyl ester, cyclohexanecarboxylic acid ethyl ester, cyclohexanecarboxylic acid n-propyl ester, cyclohexanecarboxylic acid isopropyl ester, cyclohexanecarboxylic acid. sec-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 phenylacetic acid, ethylphenylacetate, n-propylphenylacetate, isopropylphenylacetic acid, n-butyl phenylacetate, phenylacetic acid sec-butyl ester, isobutyl phenylacetic acid and tert-butyl phenylacetic acid. 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 donor complexes. Complexes, proved to be particularly advantageous.

Furthermore, those dihydrocarbyl ethers and Carbonsäurehydrocarbylester as donors for the iron halide donor complexes, the aluminum trihalide donor complexes or the Aluminiumalkylhalogenid-donor complexes, in particular the iron chloride donor complexes and the aluminum trichloride donor complexes, have been particularly has been found advantageous in which the donor compound has a total carbon number of 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 particularly 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 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 may also be with a greater degree of closure of the donor compounds, often up to a 10-fold, in particular 3-fold molar excess, worked; 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 Aluminiumalkylhalogenid, in particular made of anhydrous iron chloride or aluminum trichloride, and the donor compound 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 using a monofunctional or polyfunctional, in particular mono-, di- or trifunctional tional 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 protonic acids and water. The initiator can be mono-, di- or polyfunctional, ie one, two or more hydroxyl groups or halogen atoms can 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. As monofunctional initiators suitable organic hydroxy compounds with only one

Hydroxyl group in the molecule are in particular alcohols and phenols, in particular those of the general formula R ⁵ -OH, in which R ⁵ d- to C2o-alkyl radicals, in particular, d- to Ce- alkyl radicals, C5- to Ce-cycloalkyl radicals, CQ - to 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. Furthermore, the radicals R ^{5 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 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-methoxy- phenyl) -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, tri-phenylmethanol, diphenyl (4-pyridinyl) -methanol, alpha, alpha-diphenyl-2-pyridinemethanol, 4-methoxytrityl alcohol (especially polymer bound as solid phase), alpha-tert-butyl-4-chloro-4'-methylbenzhydrol, Cylcohex yl diphenylmethanol, alpha- (p-tolyl) -benzhydrol, 1, 1, 2-triphenylethanol, alpha, alpha-diphenyl-2-pyridineethanol, alpha, alpha-4-pyridylbenzohydrol-N-oxide, 2-fluoro-triphenylmethanol, triphenylpropargyl alcohol, 4- [(Diphenyl) hydroxymethyl] benzonitrile, 1- (2,6-dimethoxyphenyl) -2-methyl-1-phenyl-1-propanol, 1, 1, 2-triphenylpropan-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, in particular from 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-dicumylalcohol), 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 radicals or C ₇ - to C 20 -aryl arylalkyl radicals, in particular C ₇ - to C 12 -arylalkyl radicals. Furthermore, the radicals R ^{6 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 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-chlorooctane, 1-bromoctane, 1-chloro 2-ethylhexane, 1-bromo-2-ethylhexane, cyclohexyl chloride, 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-bromopropane, 1-phenyl-1-chlorobutane, 1-phenyl-1-bromobutane, 1-phenyl-2-chlorobutane, 1-phenyl-2-bromobutane , 1-phenyl-3-chlorobutane, 1-phenyl-3-bromobe tan, 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 initiator is particularly preferably selected from organic hydroxy compounds in which one or more hydroxyl groups are bound to one sp ³ -hybridized carbon atom ("alcohols") or to one aromatic ring ("phenols"). genverbindungen in which one or more halogen atoms are bonded to each 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 C20 A1-I, C ₇ - to C2o-alkylaryl or phenyl, where an aromatic nucleus, one or more, preferably one or two C1 to C4 alkyl, d- to C ₄ alkoxy, C to 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 may carry up to C ₄ alkoxy, C to C ₄ hydroxyalkyl or C ₄ to C -Halogenalkylreste as substituents, one or more, preferably one or two C to C ₄ alkyl, C, respectively.

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 for the present invention to initiators which are dissolved 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, isobutanoi, 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, isobutanoi, sec-buta-nol, tert-butanol, 1-phenyl-1-chloroethane and 1, 3- or 1, 4-bis (1-hydroxy-1-methylethyl) benzene and mixtures are selected from this.

The molar ratio of said 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 individual functional point of the initiator, according to embodiment (A) is generally 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 using water 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 are incorporated in the polymer chains in embodiment (A). The proportion (Uff) 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, an aliphatic, cycloaliphatic or aromatic amine of the general formula R ⁷ -NR ⁸ R ⁹ or ammonia can be used, in which the variables R ⁷ , R ⁸ and R ^{9 are} each independently hydrogen, ci- to C 2 -C 4 -alkyl radicals, in particular, C 1 -C 6 -cycloalkyl radicals, C 5 -C 6 -cycloalkyl radicals, C 2 -C 20 -aryl radicals, in particular C 1 -C 12 -aryl radicals, or C ₇ - to C 20 -arylalkyl radicals, in particular C ₇ - to C 12 -Arylalkylreste stand. 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,

Butylamine, tert-amylamine, n-hexylamine, n-heptylamine, n-octylamine, 2-ethylhexylamine, cyclopentylamine, cyclohexylamine, aniline, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n -butylamine, di-tert-butylamine, di-sec-butylamine, di-iso-butylamine, di-tert-amylamine, di-n-hexylamine, di-n-heptylamine, di-n-octyl-amine, di - (2-ethylhexyl) amine, dicyclopentylamine, dicyclohexylamine, diphenylamine, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, tri-tert-butylamine, tri-sec. butylamine, tri-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-diphenylamine 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, such a nitrogen-containing basic compound is in particular a saturated, partially unsaturated or unsaturated nitrogen-containing five-membered or six-membered heterocycle containing one, two or three ring nitrogen atoms and one or two further ring heteroatoms from the group oxygen and sulfur and / or hydrocarbyl, in particular C 1 - 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-d- 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 also 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 to mean those polymers which contain more than 2 mol% of monomers in copolymerized form which are different 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-methylpropyl, n-heptyl, n-octyl and its constitutional isomers such as 2-ethyl-hexyl. 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-tridecyl, isotridecyl, n-tetradecyl , n-hexadecyl, n-octadecyl and n-eicosyl. Such C 1 - to C 20 -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 haloalkyl radical or a C 1 to C 12 haloalkyl radical is a radical having the basic skeletons mentioned above for C 1 - to C 20 -alkyl radicals or C 1 - to C -alkyl radicals, in which, however, to a greater extent the hydrogen atoms are represented by halogen atoms, are replaced in particular by fluorine and / or chlorine atoms. Preferably, all or nearly all hydrogen atoms are 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, eg. 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 radicals can 1 to 5 carry non-protic substituents or non-protic functional groups, 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, 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, optionally substituted d- to C4-alkylnaphthyl such as naphthylmethyl, optionally substituted ci- to C4-alkylanthracenyl such as anthracenylmethyl or optionally substituted C 1 to C ₄ alkylphenanthrenyl such as phenanthrenylmethyl. Such arylalkyl radicals can 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 C to Ce -Fluoralkyl, halogen such as chlorine or fluorine, nitro or phenyl.

As a rule, the process according to the invention for the preparation of highly reactive isobutene homo- or copolymers is carried out by a cationic reaction mechanism, owing to the use of the complex of at least one Lewis acid and optionally at least one donor and the initiators described, which is effective as a polymerization catalyst.

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, mixtures of different sulfonic acids Z-SO3H can be used. 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-halogen-alkyl radical, C5 to Ce-cycloalkyl radical, CQ to C12-aryl radical or a C ₇ - to C 12 -arylalkyl radical. Particularly preferably, Z represents a a C to C ₄ alkyl radical, a C to C ₄ haloalkyl group, an optionally substituted phenyl radical, z. A tolyl radical or a xylyl radical, or an optionally substituted C 1 to C ₄ alkylphenyl radical, e.g. 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.

Suitable Lewis acids in the polymerization catalyst or in the complex which acts as the polymerization catalyst are in principle all, by definition, Lewis acids. organic 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 in addition to the halogen substituents still one or more organic carbon radicals - especially C 1 to C ₄ alkyl radicals - carry. 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; aluminum alkyl halides as mono (Ci to C ₄ - alkyl) aluminiumdihalogenide or di (Ci to _C4 alkyl) alu-miniummonohalogenid as Methylalu- miniumdichlorid, Ethylaluminiumdichlond, Dimethylaluminiumchlond or Diethylaluminiumchlo- chloride.

In a preferred embodiment, the Lewis acid used for the polymerization catalyst or as the polymerization catalyst is at least one compound selected from the binary chlorine and fluorine compounds of the elements of FIG. to 8th subgroup 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 , TlCl ₃ , TiCl ₄ , ZrCl ₄ , HfCl ₄ , VC, VCU, NbCl ₃ , NbCl ₅ , TaCl ₅ , CrCl ₂ , CrCl ₃ , MoCl ₃ , MOCl 5, WCI _5, 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 , InCl ₃ , TIC, SiCU, GeCl ₄ , SnCl ₂ , SnCl ₃ , SnCl ₄ , PbCl ₂ , PbCl ₄ , PCI ₃ , PCI ₅ , AsCl ₃ , SbCl ₃ , SbCl ₅ and BiCl ₃ . Of these, particularly preferred are BCI ₃ , AICI ₃ , TiCU, FeCl ₂ , FeCl ₃ and ZnCl ₂ . Typical such fluorine compounds are ScF ₃ , YF ₃ , YbF ₃ , TiF ₃ , TiF ₄ , ZrF ₄ , HfF ₄ , 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, LRF _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 binary bromine compounds can be used as such Lewis acids, such bromine compounds are, for example: TiBr _3l TiBr _4l ZrBr _4, VBr _3l VBr _4, CrBr _2, CrBr _3, MoBr _3l MoBrs, WBRS, WBre, 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 1, SnBr ₂ , SnBr _3, SnBr _4, PbBr _2, PbBr.i, PBr _3l _PBr>; , AsBr ₃ , SbBr ₃ , SbBr ?, and BiBr ₃ . Very particular preference is given to 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 BCI3, AICI3, TiCk FeCb, FeCb, ZnCb, BF3, AIF3, T1F4 , FeF, FeF3 and / or ZnF? in particular, methanesulfonic acid together with AICH, BF3 or FeCb, in particular if Lewis acid complexes are used which contain the dihydrocarbyl ethers of the general formula R ¹ -O-R ² and / or carboxylic acid hydrocarbyl esters of general formula R listed below as preferred 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 organic compound with at least one ether function as donor, compounds having 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 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 C 2 - arylalkyl radicals, in particular C ₇ - to C 12 -arylalkyl radicals, denote or a carboxylic acid hydrocarbyl ester of the general formula R ³ -COOR ⁴ , in which the variables R ³ and R ⁴ independently of one another are C 1 - to C 20 -alkyl radicals, in particular to Ce-alkyl radicals, C5- to Ce-cycloalkyl radicals, CQ- to C20-aryl radicals, in particular CQ- to C 12 -aryl radicals, or C ₇ - to C 20 -aryl arylalkyl radicals, in particular C ₇ - to C 12 -aryl arylalkyl radicals.

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 acids BCI ₃ , AICI ₃ , TiCU, FeCb, FeCb and ZnCb.

Examples of the abovementioned carboxylic acid hydrocarbyl esters are methyl formate, ethyl formate, formic acid n-propyl ester, 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, methyl propionate, Propionic acid ethyl ester, propionic acid n-propyl ester, propionic acid isopropyl ester, n-butyl propionate, sec-butyl propionate, isobutyl propionate, tert-butyl propionate, methyl butyrate, ethyl butyrate, butyric acid n-propyl ester, butyric acid isopropyl ester, n-butyl butyrate, secbutyl butbutyrate, isobutyl butyrate, tert-butyl butyrate, cyclohexanecarboxylic acid methyl ester, ethyl cyclohexanecarboxylate, n-propyl cyclohexanecarboxylate, isopropyl cyclohexanecarboxylate, n-butyl cyclohexanecarboxylate, sec-butyl cyclohexanecarboxylate, isobutyl cyclohexanecarboxylate, tert-butyl cyclohexanecarboxylate, methyl benzoate, Benzoic acid ethyl ester, n-propyl benzoate, iso-propyl benzoate, n-butyl benzoate, sec-butyl benzoate, isobutyl benzoate, tert-butyl benzoate, methyl phenylacetic acid, phenylacetic acid ethyl ester, phenylacetic acid n-propyl ester, isopropyl phenylacetate, n-butyl phenylacetate, sec-butyl phenylacetate, isobutyl phenoxyacetate and tert-butyl phenylacetate. Of the carboxylic acid hydrocarbyl esters mentioned, ethyl acetate has proved to be particularly advantageous as a donor, in particular in combination with the Lewis acids BCI3, AICI3, TiCU, FeCb, FeCb and ZnCb. 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 has 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 with a total of 6 to 14, in particular 8 to 12, carbon atoms are particularly 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 said donor compounds to the Lewis acids, that is especially to said elemental halides and elemental alkyl halides, in particular to the

Lewis acids BCb, AlCb, TiCu, FeCb. FeCb and ZnCb, in the polymerization catalyst complex is usually in the range of 0.3: 1 to 1, 5: 1, in particular of 0.5: 1 to 1.2: 1, especially 0.7: 1 to 1, 1: 1; it is in most cases 1: 1. However, it may also be with a greater degree of closure of the donor compounds, often up to a 10-fold, in particular 3-fold molar excess, worked; 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 selected from organic hydroxy compounds, organic halogen compounds 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 or mixtures of one or more organic halogen compounds 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.

Alcohols and phenols, in particular those of the general formula R ⁵ -OH, in which R ^{5 is} C 1 - to C 20 -alkyl radicals, in particular, C 1 - to C 12, are particularly suitable monofunctional initiators for organic hydroxy compounds having only one hydroxyl group in the molecule - alkyl, C5-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 already mentioned, 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, cyclopropyldiphenylmethanol, 1-hydroxy-1, 1-diphenylpropan-2-one, benzilic acid, 9-phenyl-9-fluorenol, tri-phenylmethanol, diphenyl ( 4-pyyldinyl) methanol, alpha, alpha-diphenyl-2-pyn-dinmethanol, 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-fluoro-triphenylmethanol, triphenyl-propargyl alcohol, 4 - [(diphenyl) hydroxymethyl] benzonitrile, 1- (2,6-dimethoxyphenyl) -2-methyl-1-phenyl-1-propanol, 1, 1, 2-triphenylpropan-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, in particular from 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-dicumylalcohol), 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 radicals or C ₇ - to C 20 -aryl arylalkyl radicals, in particular C ₇ - to C 12 -arylalkyl radicals. Furthermore, the radicals R ^{6 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 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-chlorooctane, 1-bromoctane, 1-chloro-2-ethylhexane, 1-bromo-2-ethylhexane, cyclohexyl chloride, 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-bromopropane, 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 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). Particularly preferably, the further initiator is selected from organic hydroxy compounds in which one or more hydroxyl groups are bonded to one sp ³ -hybridized carbon atom, 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, preference is given in particular to an initiator which is selected from organic hydroxy compounds in which one or more hydroxyl groups are bound to one sp ³ -hybridized carbon atom in each case.

In the case of the organic halogen compounds, further initiators which are particularly preferred 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 C20-Al I, C7 - to C20-alkylaryl or phenyl, wherein an aromatic nucleus is one or more, preferably one or two C 1 to C 4 alkyl, C 1 to C ₄ alkoxy, d- to C4-hydroxyalkyl or C 1 to C ₄ haloalkyl radicals as substituents may 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 one or more, preferably one or two C to C ₄ alkyl, C to C ₄ alkoxy, d- to C ₄ hydroxyalkyl or d- to C ₄ -Halogenalkylreste as substituents, respectively.

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 are selected from this. Of these, particular preference is given to further initiators which are dispersed 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 individual 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 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 at Copo in particular from 0.0001: 1 to 0.1: 1, in particular from 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 0.01 to 10 mmol, in particular from 0.05 to 5.0 mmol, above all from 0.1 to 1, 0 mmol, in each case based on 1 mol of isobutene monomer used in the 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, an aliphatic, cycloaliphatic or aromatic amine of the general formula R ⁷ -NR ⁸ R ⁹ or ammonia can be used, in which the variables R ⁷ , R ⁸ and R ^{9 are} each independently hydrogen, C1- to C 2 -C 4 -alkyl radicals, in particular, C 1 -C 6 -cycloalkyl radicals, C 5 -C 6 -cycloalkyl radicals, C 2 -C 20 -aryl radicals, in particular C 1 -C 12 -aryl radicals, or C ₇ - to C 20 -arylalkyl radicals, in particular C ₇ - to C 12 -Arylalkylreste stand. 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, there 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, iso-propylamine, 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, diisopropylamine, 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-butylamine. 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-diphe nylamine or N-methyl-N-ethyl-Nn-butylamine.

Furthermore, such a nitrogen-containing basic compound can also be a compound having a plurality, in particular having two or three nitrogen atoms and having 2 to 20 carbon atoms, these nitrogen atoms each independently 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, such a nitrogen-containing basic compound is in particular a saturated, partially unsaturated or unsaturated nitrogen-containing five-membered or six-membered heterocycle containing one, two or three ring nitrogen atoms and one or two further ring heteroatoms from the group oxygen and sulfur and / or hydrocarbyl, in particular C 1 - 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-d- 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 is suitable as isobutene source in embodiment (A) and (B) both pure isobutene and isobutene-containing C4 hydrocarbon streams, such as C4 raffinates, in particular "raffinate 1 ", C ₄ cuts from isobutane dehydrogenation, C ₄ cuts from steam crackers and FCC crackers (fluid catalysed cracking), provided that they are largely freed from 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, 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. 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 an accumulation of 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, more preferably 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 to C ₄ -alkylstyrenes such as 2-, 3- and 4-methylstyrene and 4-tert-butylstyrene, halogenated styrenes 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-ethylpentene-1, 2-ethylhexene-1 and 2-propylheptene-1. Other suitable comonomers are olefins which have a silyl group, such as 1-trimethoxysilylethene, 1- (trimethoxysilyl) propene, 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 at least partially already 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. In some cases, however, block copolymers also form when all comonomers are simultaneously fed to the polymerization reaction, but one of them polymerizes significantly faster than the 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 prior art processes 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, as well as 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 slightly higher temperatures from -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 inert diluent used should be suitable for reducing the increase in the viscosity of the reaction solution which usually occurs during the polymerization reaction to such an extent that the removal of the heat of reaction formed 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 xylenes, 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. As halogenated hydrocarbons for the inert diluents mentioned above and below, chlorinated hydrocarbons, in particular pure chlorohydrocarbons, are preferred. 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 C ₄ 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: 15th 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 compounds. see hydrocarbons, especially toluene, by. 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 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 in accordance with 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 by physical and / or chemical measures before being used. 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 from the Solvent largely remove. The solvent thus treated is then preferably condensed directly into the reaction vessel. Similarly, one can also proceed with the monomers to be polymerized, in particular with isobutene or with the isobutene-containing mixtures. Drying with other conventional drying agents such as molecular sieves or predried oxides such as alumina, silica, 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 from water or traces of water with suitable drying agents, for example with calcium chloride, phosphorus pentoxide or molecular sieve. In an analogous manner, it is also possible to dry those starting materials for which a treatment with metal alkyls likewise does not come into consideration, for example vinylaromatic compounds. Even if water is used as an initiator or co-used, preferably residual moisture from solvents and monomers should be removed as far as possible prior to reaction by drying in order to use the initiator water targeted in a specified amounts, thereby obtaining a higher process control and reproducibility of the results ,

The polymerization of the isobutene or of the isobutene-containing feedstock usually takes place spontaneously when the polymerization catalyst, ie the iron halide, is brought into contact. nid donor complex, of the aluminum trihalide donor complex or of the aluminum alkyl halide donor complex, in particular of the iron chloride donor complex or of the aluminum trichloride donor complex, or of the Lewis acid containing at least one organic sulfonic acid. 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 proceed by initially introducing the monomers into the diluent, bringing them to the reaction temperature and then adding the polymerization catalyst, ie the iron halide donor complex, the aluminum trihalide donor complex or the aluminum alkyl halide donor complex, in particular the Ferric 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 donor complex. Complex, or the 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, one can proceed by initially introducing the monomers, optionally 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 halide donor complex, in particular the iron chloride donor complex or the aluminum trichloride complex. 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 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 only after a certain time, for example when at least 60%, at least 80% or at least 90% of the monomer is reacted, which adds or the other monomers. Alternatively, the polymerization catalyst, that is, 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, optionally in the dilution 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 can also be carried out in accordance with the process of the invention 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 to continuously and continuously withdraws reaction product, so that set more or less stationary polymerization in the reactor. The monomer (s) to be polymerized may 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 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, 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 solvents, liquid bed reactors, continuous fixed bed reactors and batchwise batchwise reactors.

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 the at least one 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, in particular 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 the polymerizable monomers used in copolymerization of isobutene in the range of 1:10 to 1: 5000, in particular 1:15 to 1: 1000, especially 1: 20 to 1: 250, lies.

For reaction termination, 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, e.g. an aqueous solution of 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 hydrogencarbonate such as sodium, potassium, magnesium - or calcium bicarbonate.

In the process according to the invention, the described highly reactive isobutene homopolymers or copolymers having a content of terminal vinylidene double bonds (α-double bonds) per polyisobutene chain end of at least 50 mol%, preferably of at least 60 mol%, are described as monomer component (b). , 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%, more preferably of more than 91 mol% and in particular of at least 95 mol% %, eg of nearly 100 mol% used. In particular, highly reactive isobutene copolymers are used, which are composed of isobutene and at least one vinylaromatic monomer, in particular styrene, and have a content of terminal vinylidene double bonds (α-double bonds) per polyisobutene chain end of at least 50 molar %, preferably of at least 60 mol%, preferably of at least 70 mol%, preferably of at least 80 mol%, preferably of at least 80 mol%, preferably of at least 85 mol%, particularly preferably of at least 90 mol% , more preferably more than 91 mol%, and especially at least 95 mol%, eg of nearly 100 mol%. 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 ratio by weight 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 = M _w / M _n ) of 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 special 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.

Particularly suitable monomer components (b) for the process according to the invention are those isobutene polymers which have been formed by homopolymerization of isobutene or copolymerization of isobutene with up to 20% by weight of n-butene, are monofunctional and have a number-average molecular weight (M _n ). from 500 to 5000, especially 650 to 2500 have.

In particular, suitable monomer components (b) for the process according to the invention are those isobutene polymers which are obtained by homopolymerization of isobutene or copolymerization of isobutene with up to 20% by weight of n-butene, in each case with the use of a di or trifunctional initiator (inifers), have di- or trifunctional and a number-average molecular weight (M _n ) of 500 to 10,000, especially 1000 to 5000, have.

In particular, suitable monomer components (b) for the process according to the invention are those isobutene polymers which have been formed by copolymerization of isobutene with at least one vinylaromatic comonomer, in particular styrene, if appropriate with the use of a difunctional or trifunctional initiator (inifers), mono-, di- or trifunctional and have a number average molecular weight (M _n ) of 500 to 15,000, especially 1000 to 10,000, have.

Monomer component (a) are preferably monoethylenically unsaturated dicarboxylic acids having 4 to 10, in particular 4 to 8, especially 4 to 6 carbon atoms and their anhydrides and their semiestral and full esters as their derivatives, for example maleic acid, fumaric acid, Itaconic acid, mesaconic acid, methylenemalonic acid, citraconic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, methylmalonic anhydride, monomethyl maleate, dimethyl maleate, monomethyl fumarate, fumarate, fumaric acid monoethyl ester or diethyl fumarate. Particularly suitable ester alcohols here are, in particular, C 1 - to C 20 -alkanols, especially C 1 -to-alkanols. It is also possible to use mixtures of such dicarboxylic acids or dicarboxylic anhydrides or half or full esters. In a particularly preferred embodiment, the monomer component (a) used is maleic anhydride, fumaric acid or a fumaric acid half-ester or full-ester. Suitable monomer component (c) are all those monomers which are copolymerizable with the monomer components (a) and (b).

In a preferred embodiment, the monomer component (c) used is a monethylenically unsaturated C ₃ - to C 16 -monocarboxylic acid or an ester, in particular a C ₁ - to C 40 -alkyl ester, thereof a linear 1-olefin having 2 to 40, in particular 8 to 30 carbon atoms, styrene or a styrene derivative, a vinyl ether having a total of 3 to 40, in particular 3 to 20 carbon atoms, an allyl ether having a total of 4 to 41, in particular 4 to 21 carbon atoms or a mixture of such comonomers.

Suitable monoethylenically unsaturated C ₃ - to Cio-monocarboxylic acids are, for example, acrylic acid, methacrylic acid, dimethacrylic acid, ethylacrylic acid, crotonic acid, allylacetic acid and vinylacetic acid and also their methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl , sec-butyl, tert-butyl, 2-ethylhexyl, n-decyl, n-dodecyl or n-octadecyl ester.

Suitable linear 1-olefins having 2 to 40, in particular 8 to 30, carbon atoms are, for example, 1-octene, 1 -none, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1 -Eicoses and technical mixtures such as C20-C24-I olefins or C24-C28-1 olefins.

Suitable styrene derivatives are, for example, 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.

Suitable vinyl ethers having a total of 3 to 40, in particular 3 to 20 carbon atoms are in particular vinyl alkyl ethers having 1 to 30, especially 1 to 20 carbon atoms in the alkyl radical, wherein the alkyl radical can carry further substituents such as hydroxyl groups, alkoxy radicals, amino groups or dialkylamino groups. Examples thereof are methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, n-decyl vinyl ether, n-dodecyl vinyl ether, n-octadecyl vinyl ether, 2- (dimethylamino) ethyl vinyl ether and 2- (di-n-butylamino) ethyl vinyl ether ,

Suitable allyl ethers having a total of 4 to 41, in particular 4 to 21, carbon atoms are in particular allylalkyl ethers having 1 to 30, especially 1 to 20, carbon atoms in the alkyl radical, where the alkyl radical may carry further substituents such as hydroxyl groups, alkoxy radicals, amino groups or dialkylamino groups. Examples of these are methyl allyl ether, ethyl allyl ether, n-propyl allyl ether, isobutyl allyl ether, 2-ethylhexyl allyl ether, n-decyl allyl ether, n-dodecyl allyl ether, n-octadecyl allyl ether, 2- (dimethylamino) ethyl allyl ether and 2- (di-n-butylamino) ethyl allyl ether.

In addition to the monomers mentioned but can also amides and C to C4o-alkylamides of monoethylenically unsaturated C ₃ - to Cio-monocarboxylic acids, eg. As acrylamide or methacrylamide, mono- and D1-C 1 - to C4o-alkyl esters, mono- and diamides and mono- and D1-C 1 - to C 4 -alkylamides of monoethylenically unsaturated C 4 - to Cio-monocarboxylic acids, eg. Painting monomethyl monoesters or dimethyl maleate, C ₁ to C 40 aminoalkyl esters of monoethylenically unsaturated C ₃ - to C ₁ monocarboxylic acids, eg. B. dimethylaminoethyl, vinyl and allyl esters of saturated d- to C2o-monocarboxylic acids, eg. Vinyl acetate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl laurate, vinyl stearate, vinyl pivalate, allyl acetate, allyl butyrate or allyl stearate, N-vinylcarboxamides of d- to Ce-monocarboxylic acids, e.g. B. N

Vinylformamide or N-vinylacetamide, and N-vinyl derivatives of nitrogen-containing heterocycles, eg. As N-vinylimidazole, N-vinylmethylimidazole, N-vinylpyrrolidone of N-vinylcaprolactam, as monomer components (c) find use. The copolymers of the monomer components (a), (b) and (c) can in principle be prepared by all known conventional polymerization processes, for example by bulk, emulsion, suspension, precipitation or solution polymerization. In all of the above-mentioned polymerization processes, the reaction is usually carried out in the absence of oxygen, preferably in a stream of nitrogen. Conventional apparatus can be used for all polymerization methods, for example autoclaves or stirred tanks. Particularly preferred here is the bulk polymerization; It may advantageously be carried out at temperatures of 80 to 300 ° C, in particular from 120 to 200 ° C, wherein the lowest to be selected polymerization temperature should be about 20 ° C above the glass transition temperature of the copolymer formed. The polymerization conditions in detail are suitably chosen according to the molecular weight of the copolymer to be achieved; Thus, polymerization at higher temperatures gives copolymers with lower molecular weights, while at lower polymerization temperatures copolymers with higher molecular weights result. The copolymerization of the monomer components (a), (b) and (c) is usually carried out in the presence of free-radical-forming compounds. Of these polymerization initiators usually required up to 10 wt .-%, preferably 0.2 to 5 wt .-%, based on the sum of all monomers used. Suitable polymerization initiators are, for example, peroxide compounds such as tert-butyl perpivalate, tert-butylperneodecanoate, tert-butyl perethylhexanoate, tert-butyl perisobutyrate, di-tert-butyl peroxide, di-tert-amyl peroxide, diacetyl peroxydicarbonate and dicyclohexyl peroxydicarbonate and azo compounds such as 2,2 '- Azobis (isobutyronitrile). The initiators can each be used alone or mixed with one another. In the bulk polymerization, they are preferably introduced separately or in the form of a solution into the polymerization reactor. The monomer components (a), (b) and (c) can be copolymerized at temperatures above 200 ° C in principle even in the absence of polymerization initiators.

In order to prepare lower molecular weight copolymers, it is often useful to carry out the copolymerization in the presence of regulators. For this purpose, conventional regulators such as d- to C ₄ - aldehydes, formic acid and organic compounds containing SH groups, for. Eg 2-

Mercaptoethanol, 2-mercaptopropanol, mercaptoacetic acid or tert-butyl mercaptan. be. These polymerization regulators are normally used in amounts of from 0.1 to 10% by weight, based on the total amount of all monomers.

To produce relatively high molecular weight copolymers, it is often expedient to work in the presence of chain extenders in the polymerization. Such chain extenders are compounds having di- or polyethylenically unsaturated groups, such as divinylbenzene, pentaerythritol triallyl ether, glycol diacrylate, glycerol triacrylate or polyethylene glycol diacrylates. They can be added in the polymerization in amounts of up to 5 wt .-%, based on the total amount of all monomers.

The copolymerization can be carried out continuously or batchwise.

After radical copolymerization of the monomer components (a), (b) and, if appropriate, (c), part or all of the carboxylic acid or carboxylic acid derivative functions in the resulting isobutene copolymer originating from the monomer component (a) or if one is used carboxyl-containing monomer component (c) can also be obtained from this, with ammonia, a mono- or polyamine, an alcohol or a mixture thereof converted into the corresponding derivatives, which then normally amino- and / or quaternized amino and / or amido and / or imido groups.

In a preferred embodiment, this is a part of or all carboxylic acid or carboxylic acid derivative functions in the resulting isobutene with a mono- or polyamine of the general formula HNR ¹³ R ¹⁴ , in which the radicals R ¹³ and R ^{14 may be the} same or different and for hydrogen, aliphatic or aromatic hydrocarbon radicals, primary or secondary, aromatic or aliphatic aminoalkylene radicals, polyaminoalkylene radicals, hydroxyalkylene radicals, polyoxyalkylene radicals which optionally bear amino end groups, or heteroaryl or heterocyclyl radicals which optionally carry amino end groups, or together with the nitrogen atom to which they are bonded form a ring in which even more heteroatoms may be present, or reacted a mixture of such amines, wherein a resulting Carbonsäureamid- or carboxylic acid imide derivative or by further reaction with at least one C2 to Ci2 dicarboxylic anhydride, can be modified with at least one C2 to C4 alkylene carbonate and / or with boric acid.

Resultant Carbonsäureamid- and Carbonsäureimid derivatives are often, in particular when used in the lubricant formulations, for improving the swelling behavior of elastomers, which for example in seals of engines, units or devices, with the said derivatives or with these containing lubricant formulations come in contact, are incorporated, nor modified with at least one C2 to C12 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. Suitable amine components, in particular those of the general formula HNR ¹³ R ¹⁴ , are:

• ammonia;

Aliphatic and aromatic, primary and secondary amines having 1 to 50, in particular 1 to 20 carbon atoms such as methylamine, ethylamine, n-propylamine, di-n-butylamine or cyclohexylamine; Amines in which R ¹³ and R ¹⁴ with the nitrogen atom to which they are attached form a common ring which may contain further heteroatoms, in particular nitrogen and / or oxygen and / or sulfur, such as morpholine, pyridine, piperidine , Pyrrole, pyrimidine, pyrroline, pyrrolidine, pyrazine or pyridazine; Hydroxyamylene- and polyoxyalkylene-bearing amines in which R ¹³ and / or R ^{14 is} a radical of the formula - (R ¹⁶ -O) _p -H, where R ^{16 is} a C 2 -C 10 -alkylene radical and p is an integer from 1 to 30, z. Ethanolamine, 2-aminopropanol-1 or neopentanolamine; Amino-end-bearing polyoxyalkyleneamines in which R ¹³ and / or R ^{14 is} a radical of the formula -R ¹⁷ -O- (R ¹⁶ -O) _p -R ¹⁸ -NR ¹⁹ R ² °, where R ¹⁶ , R ¹⁷ and R ^{18 is} C ₂ - to C 10 -alkylene radicals, p has the abovementioned meaning and R ¹⁹ and R ^{20 is} hydrogen, optionally hydroxy- and / or amino-substituted d- to Cio-alkyl or CQ to Cio-aryl , z. Polyoxypropylenediamines or bis (3-aminopropyl) tetrahydrofurans;

Polyamines in which R ¹³ and / or R ^{14 are} a radical of the formula - (R ¹⁶ -NR ¹⁹ ) _q -R ²⁰ in which the radicals R ¹⁶ , R ¹⁹ and R ^{20 have} the meanings given above and q is an integer from 1 to 6; such polyamines are: ethylenediamine, propylenediamine, dimethylaminopropylamine, diethylenetriamine, dipropylenetriamine, triethylenetetramine, tripropylenetetramine, tetraethylenepentamine, tetrapropylenepentamine, ethylaminoethylamine, dimethylaminoethylamine, isopropylaminopropylamine, ethylenedipropylenetetramine, 2-diisopropylaminoethylamine, aminoethylethanolamine, ethylenepropylenetriamine, Ν, Ν, Ν ', Ν'-tetra- (3-aminopropyl) -ethylenediamine, 2- (3-aminopropyl) -cyclohexylamine, 2,5-dimethylhexanediamine-2,5, N, N, N', N ", N" -penta- (3-aminopropyl) -dipropylentriamin and polyamines which contain a heterocycle as a structural component, for. B. aminoethylpiperazine.

As the amine component, it is also possible to use mixtures of different amines.

Compounds with quaternized amino groups are in particular quaternized nitrogen compounds which are obtained by addition of a compound which contains at least one anhydride-reactive oxygen- or nitrogen-containing group and additionally at least one quaternizable amino group to an anhydride moiety in the isobutene nucleus. lymerisat and subsequent quaternization, in particular with an epoxide, especially in the absence of free acid, are available, as described in EP Patent Application Az. 10 168 622.8. Polyamines having at least one primary or secondary amino group and at least one tertiary amino group such as 3- (dimethylamino) are particularly suitable as compounds having at least one anhydride-reactive oxygen- or nitrogen-containing group and additionally at least one quaternizable amino group. propylamine.

In a further preferred embodiment, the conversion into derivatives after radical copolymerization of the monomer components (a), (b) and optionally (c) a part of or all carboxylic acid or carboxylic acid derivative functions in the resulting isobutene copolymer with an alcohol of the general formula R ^15th OH, in which the radicals R ^{15 can be} an aliphatic, cycloaliphatic or aromatic hydrocarbon radical, a hydroxyalkylene radical, a polyoxyalkylene radical, or a mixture of such alcohols. In the case of the conversion with monohydric alcohols, groups with carboxylic acid ester groups are usually formed; in the case of the conversion with dihydric alcohols, groups with hydroxyl groups are formed in the end product.

Examples of such alcohols of the general formula R ¹⁵ OH are methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, n-hexanol, n-heptanol, n -Octanol, 2-ethylhexanol, n-nonanol, isononanol, n-decanol, 2-propylheptanol, n-undecanol, n-dodecanol, n-tridecanol, isotridecanol, n-tetradecanol, n-hexadecanol, n-octadecanol, cyclohexanol, phenol , Cresols, benzyl alcohol, 1-phenylethanol, 2-phenylethanol, ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol and polyethylene glycols of the formula HO- (CH 2 CH 2 O) _r H in which r is a number from 2 to 50 , in particular from 2 to 10, especially from 2 to 5, stands.

As the alcohol component it is also possible to use mixtures of different alcohols. The conversion products of the isobutene copolymers with ammonia, a mono- or polyamine, an alcohol or a mixture thereof into the corresponding derivatives are obtained in a manner known per se by reacting the isobutene copolymers with the stated reactants. The molar ratio of the isobutene to the said reactants depends on the number of acid or Anhy-dridgruppen in Isobutencopolymerisat from. This can be determined in a known manner, for example by titration with a strong base. In general, 0.1 to 3 equivalents of acid or anhydride groups or of the acid derivatives mentioned are used per mole of amine or alcohol in the isobutene copolymer. In general, the starting materials are mixed for the reaction and heated to 30 to 200 ° C. Preferably, the reaction is carried out under a protective gas atmosphere, for. B. in a stream of nitrogen. The reaction can be carried out without or in inert solvents. Suitable inert solvents suitable for this purpose are, in particular, aliphatic and aromatic hydrocarbons. Hydrocarbons such as hexane, toluene, xylene and mineral oils. The progress of the reaction can be followed, for example, by IR spectroscopy.

The present invention also relates to novel isobutene copolymer derivatives which are obtainable by free-radical copolymerization of

(a) 10 to 90 mol%, preferably 20 to 60 mol%, in particular 20 to 60 mol%,

at least one monoethylenically unsaturated C ₄ - to C 12 -dicarboxylic acid or its anhydride,

(b) 10 to 90 mol%, preferably 10 to 70 mol%, in particular 10 to 70 mol%,

of a highly reactive isobutene homopolymer having a number-average molecular weight (M _n ) of from 500 to 20,000 and a content of at least 50 mol% of terminal vinylidene double bonds per polyisobutene chain end of the general formula I

in the

R ¹⁰ , R ¹¹ and R ¹² independently of one another are hydrogen, C 1 - to C 20 -alkyl, C 5 - to

Ce-cycloalkyl, CQ- to C20-Al I, C ₇ - to C 20 -alkylaryl or phenyl, where an aromatic nucleus is also one or more C 1 to C ₄ -alkyl or C 1 to C ₄ -alkoxy radicals or groups of the general groups Formula II

as a substituent, with 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 may carry as substituents one or more C -C ₄ alkyl or C 1 to C ₄ alkoxy or one or two groups of the general formula II, respectively, and n is a number of 8 to 350, in particular 9 to 100, especially 12 to 50, where in telechelic isobutene homopolymers I the two or three variables n

may be the same or different, (C) 0 to 50 mol%, preferably 0 to 50 mol%, in particular 1 to 50 mol% of one or more monoethylenically unsaturated compounds, which with the

Monomer components (a) and (b) are copolymerizable, and subsequent reaction of a part or all of the carboxylic acid or carboxylic acid derivative functions in the resulting isobutene copolymer with ammonia, a mono- or poly- amine, an alcohol or a mixture of said reactants to form Groups with hydroxyl and / or carboxylic acid ester and / or amino and / or quaternized amino and / or amido and / or imido groups.

The derivatives of isobutene copolymers prepared according to the invention are suitable, for example, as fuel and lubricant additives. The derivatives of isobutene copolymers prepared according to the invention are prepared from polyisobutenes 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 improved. The catalyst system used for the production of the polyisobutenes in the precursor is sufficiently active, durable, easy to handle and prone to failure, 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 derivatives of isobutene copolymers by free-radical copolymerization of

(A) 10 to 90 mol% of at least one monoethylenically unsaturated C ₄ - bis

Ci2-dicarboxylic acid or its anhydride or its half or full ester,

(b) 10 to 90 mole percent of a highly reactive isobutene homo- or copolymer

having a number average molecular weight (M _n ) of from 10 to 250,000 and a content of at least 50 mol% of terminal vinylidene double bonds per polyisobutene chain end, which may contain structural units of mono-, di- or trifunctional initiators,

(c) 0 to 50 mol% of one or more monoethylenically unsaturated compounds which are copolymerizable with the monomer components (a) and (b), and subsequent reaction of part or all of the carboxylic acid or carboxylic acid derivative functions in the resulting isobutene copolymer with ammonia, a mono or the polyamine, an alcohol or a mixture of said reactants to form groups having hydroxy and / or carboxylic acid ester and / or amino and / or quaternized amino and / or amido and / or imido groups, characterized characterized in that to produce the monomer component (b) 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 Ce -cycloalkyl radical, C 2 - to C 20 -aryl radical or a C ₇ - to C 20 -arylalkyl radical, polymerized.

Process according to Claim 1, characterized in that isobutene or an isobutene-containing monomer mixture is polymerized in the presence of an iron chloride-donor complex or aluminum trichloride-donor complex which is effective as a polymerization catalyst to produce the monomer component (b) according to embodiment (A) ,

A process as claimed in claim 1 or 2, wherein an iron halide donor complex, an aluminum trihalide donor complex or an aluminum alkyl halide donor complex is used as the polymerization catalyst to produce the monomer component (b) according to embodiment (A), 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 are C 1 - to C 20 -alkyl radicals, C 5 - to C 6 -cycloalkyl radicals, C 2 - to C 20 -aryl radicals or C ₇ to C 20 arylalkyl radicals.

A process as claimed in claim 1 or 2, wherein an iron halide donor complex, an aluminum trihalide donor complex or an aluminum alkyl halide donor complex is used as the polymerization catalyst to produce the monomer component (b) according to embodiment (A), which contains, as donor, a carboxylic acid hydrocarbyl ester of the general formula R ³ -COOR ⁴ in which the variables R ³ and R ⁴ independently of one another denote C 1 - to C 20 -alkyl radicals, C 5 - to C 6 -cycloalkyl radicals, C 2 - to C 20 -aryl radicals or C ₇ - designate to C2o-arylalkyl radicals.

Process according to claims 1 to 4, characterized in that one uses for the production of the monomer component (b) according to embodiment (A) as the polymerization catalyst, an iron halide donor complex, an aluminum trihalide donor complex or an aluminum alkyl halide donor complex in which the donor compound has a total carbon number of 3 to 16.

Process according to Claims 1 to 5, characterized in that, to produce the monomer component (b) according to embodiment (A), the polymerization is carried out using an initiator selected from organic hydroxy compounds in which one or more hydroxyl groups are each bonded to an sp ³ - hybridized carbon atom or to an aromatic ring, organic halogen compounds in which one or more halogen atoms are bonded to each sp ³ -hybridized carbon atom, proton 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, 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-methylethyl) benzene and mixtures thereof. out.

8. The method according to claims 1 to 7, characterized in that for the production of the monomer component (b) according to embodiment (A), the polymerization in the presence of 0.01 to 10 mmol, each based on 1 mol of isobutene used Monomer 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 performs.

A 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 to produce the monomer component (b) according to embodiment (A), the polymerization in a halogenated halogenated halogenated 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 an 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) as 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 first 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.

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 functioning as a donor 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 C to C 20 alkyl radicals, C5 - to Ce-Cyclo alkyl radicals, CQ- to C 20 -aryl radicals or C ₇ - to C 20 -arylalkyl radicals, or a carboxylic acid hydrocarbylcarboxylic acid of the general formula R ³ -COOR ⁴ , in which the variables R ³ and R ⁴ independently of one another denote C 1 - to C 20 -alkyl radicals, C5 to Ce cycloalkyl radicals, CQ to C20 aryl radicals or C ₇ - to denote C2o arylalkyl radicals.

16. The method according to claim 15, characterized in that the functioning as a donor 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 concomitant use of at least one further initiator which mono- or polyfunctional and organic 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-methylethyl) 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.

20. The method according to claim 19, characterized in that one uses pyridine or a derivative of pyridine as the nitrogen-containing base see connection.

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 halogenated aliphatic hydrocarbons or in a mixture of at least one halogenated aliphatic hydrocarbon and at least one aliphatic, cycloaliphatic or aromatic see hydrocarbon as an inert diluent.

23. The method according to claims 1 to 22, characterized in that for the production of the monomer component (b) as a monomer source for the polymerization see a technical C4 hydrocarbon stream having an isobutene content of 1 to 100 wt .-%, 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. 24. The method according to claims 1 to 23, wherein the monomer component (b) by

Homopolymerization of isobutene or copolymerization of isobutene with up to 20% by weight of n-butene was formed, monofunctional and has a number average molecular weight (M _n ) of 500 to 5000. 25. The method according to claims 1 to 23, wherein the monomer component (b) by

Homopolymerization of isobutene or copolymerization of isobutene with up to 20% by weight of n-butene, each with the use of a di- or trifunctional initiator (Inifers), is formed, 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, wherein the monomer component (b) by copolymerization of isobutene with at least one vinyl aromatic comonomer, optionally with concomitant use of a di- or trifunctional initiator (Inifers) was formed, mono-, di- or is trifunctional and has a number average molecular weight (M _n ) of 500 to 15,000.

27. The method according to claims 1 to 26, wherein as the monomer component (a) maleic anhydride, fumaric acid or a Fumarsäurehalb- or -vollester is used. 28. The method according to claims 1 to 27, wherein the monomer component (c) is a monoethylenically unsaturated C ₃ - to Cio monocarboxylic acid or an ester thereof, a linear 1-olefin having 2 to 40 carbon atoms, styrene or a Styrene derivative, a vinyl ether having a total of 3 to 40 carbon atoms, an allyl ether having a total of 4 to 41 carbon atoms or a mixture of such comonomer is used.

29. The method according to claims 1 to 28, wherein after the radical copolymerization of the monomer components (a), (b) and optionally (c) a part of or all carboxylic acid or carboxylic acid derivative functions in the resulting isobutene with a mono- or polyamine of the general Formula HNR ¹³ R ¹⁴ , in which the radicals R ¹³ and R ^{14 may be} identical or different and are hydrogen, aliphatic or aromatic

Hydrocarbon radicals, primary or secondary, aromatic or aliphatic aminoalkyl radicals, polyaminoalkylene radicals, hydroxyalkylene radicals, polyoxyalkylene radicals which may carry amino end groups, or heteroaryl or heterocyclyl radicals which may be present Amino end groups can carry, stand or together with the nitrogen atom to which they are attached, form a ring in which further heteroatoms may be present, or a mixture of such amines are reacted, wherein a resulting Carbonsäureamid- or Carbonsäureimid derivative 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.

30. Process according to claims 1 to 28, in which after radical copolymerization of the monomer components (a), (b) and optionally (c) a part of or all carboxylic acid or carboxylic acid derivative functions in the resulting isobutene with an alcohol of the general formula R ¹⁵ OH, in which the radicals R ^{15 may be} an aliphatic, cycloaliphatic or aromatic hydrocarbon radicals, a hydroxyalkylene radical, a polyoxyalkylene radical, or a mixture of such alcohols.

31. Isobutene copolymer derivatives, obtainable by free-radical copolymerization of

(A) 10 to 90 mol% of at least one monoethylenically unsaturated C ₄ - bis

Ci2-dicarboxylic acid or its anhydride,

(B) 10 to 90 mol% of a highly reactive isobutene homopolymer with a

number average molecular weight (M _n ) of 500 to 20,000 and a content of at least 50 mol% of terminal vinylidene double bonds per polyisobutene chain end of the general formula I.

in the

R ¹⁰ , R ¹¹ and R ¹² are each independently hydrogen, C 2 -C 20 -alkyl, C 5 -C 6 -cycloalkyl, C 2 -C 20 -alkyl, C ₇ - to C 20 -alkylaryl or phenyl, where one aromatic nucleus is still one or more a plurality of C ₄ -C ₄ -alkyl or C ₄ -C ₄ -alkoxy radicals or groups of the general formula II

as a substituent, with at most one of the variables ablen 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 contain one or more d- to C ₄ - alkyl or d- to C ₄ alkoxy or one or denotes two groupings of the general formula II as substituents, and n stands for a number from 8 to 350, where in the case of telechelic isobutene homopolymers I the two or three variables n in the molecule may be identical or different,

(c) 0 to 50 mol% of one or more monoethylenically unsaturated compounds which are copolymerizable with the monomer components (a) and (b), and subsequent reaction of part or all of the carboxylic acid or carboxylic acid derivative functions in the resulting isobutene copolymer with ammonia, a mono or the polyamine, an alcohol or a mixture of said reactants to form groups having hydroxy and / or carboxylic acid ester and / or amino and / or quaternized amino and / or amido and / or imido groups.