PREPARATION OF DERIVATIVES OF ISOBUTENE HOMOPOLYMERS OR COPOLYMERS.

Abstract

Preparation of isobutene homo- or copolymer derivatives with a residue of a hydrophobic polyisobutene polymer having a number-averaged molecular weight of 110 to 250,000 and low molecular weight polar groups, each containing amino groups, nitro groups, hydroxyl groups, mercaptan groups, carboxylic acid or carboxylic acid derivative groups, sulfonic acid or sulfonic acid derivative groups, aldehyde groups and / or silyl groups, wherein isobutene or an isobutene-containing monomer mixture 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 as a donor an organic compound with an ether function or a carboxylic ester function, or a Lewis acid complex containing organic sulfonic acids with or without donors.the resulting highly reactive isobutene polymer reacts with a compound introducing the low molecular weight polar group or a substructure thereof, and in the case of reaction with a substructure, the formation of the low molecular weight polar group is completed by subsequent reactions.

Description

[0001] The present invention relates to an improved process for the production of isobutene homopolymer or copolymer derivatives. Furthermore, the present invention relates to novel isobutene homopolymer derivatives.

[0002] Isobutene homopolymers or copolymers such as polyisobutenamines or polyisobutenyl succinic anhydrides are frequently obtained from so-called highly reactive isobutene homopolymers or copolymers. Highly reactive isobutene homopolymers or copolymers, in contrast to so-called low-reactive polymers, are defined as polyisobutenes containing a high content of terminally arranged 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 to be those double bonds whose position in the polyisobutene macromolecule is described by the general formula As described, the double bond is located in the polymer chain in an α-position. "Polymer" refers to the polyisobutene residue shortened by one isobutene unit. Vinylidene groups exhibit the highest reactivity, for example, in thermal addition to sterically demanding reactants such as maleic anhydride, whereas a double bond located further inside the macromolecule usually shows no or lower reactivity in functionalization reactions.

[0003] Such highly reactive polyisobutenes are used, among other things, as intermediates in the production of additives for lubricants and fuels. For example, according to the patent DE-A 27 02 604, they are reacted with maleic anhydride to form polyisobutenylsuccinic anhydrides. However, the highly reactive polyisobutenes obtained by the process of DE-A 27 02 604 through cationic polymerization of isobutene in the liquid phase in the presence of boron trifluoride as a catalyst have some disadvantages, such as a relatively high polydispersity. Polydispersity is a measure of the molecular weight distribution of the resulting polymer chains and corresponds to the quotient of weight-mean molecular weight Mw and number-mean molecular weight Mn (PDI = Mw / Mn).

[0004] Polyisobutenes with a similarly high proportion of terminal double bonds, but with a narrower molecular weight distribution, are available, for example, according to the process of EP-A 145 235, US 5 408 018 and WO 99 / 64482, whereby the polymerization takes place in the presence of a deactivated catalyst, for example a complex of boron trifluoride with alcohols and / or ethers.

[0005] Highly reactive polyisobutenes can also be obtained by living cationic polymerization of isobutene and subsequent dehydrohalogenation of the resulting polymerization product, for example according to the process from US 5,340,881. However, such a process is complex because the halogen end group introduced by the living cationic polymerization must be cleaved in a separate step to generate the double bond.

[0006] It has also long been known that the Lewis acid aluminium 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), J. Wiley & Sons, New York, 1971.

[0007] The unpublished European patent application with file number 10157068.7 discloses a process for the production of highly reactive isobutene homo- or copolymers by polymerization in the presence of an aluminum trihalide donor complex acting as a polymerization catalyst or an aluminum alkylhalide donor complex, which contains as the donor an organic compound with at least one ether function or a carboxylic ester function and optionally an organic hydroxy compound, an organic halogen compound, or water as the initiator. Further reactions with the highly reactive isobutene homo- or copolymers thus produced are not described therein.

[0008] From CN 101955558 A, it is known that iron(III) chloride is suitable as a co-initiator in the cationic isobutene polymerization for the production of highly reactive polyisobutenes and their copolymers. Water, phenols, protic acids such as sulfuric acid, tertiary alcohols, tertiary chlorides, tertiary carboxylic acid esters, and carboxylic acids themselves are recommended as initiators. Alkyl ethers are specifically mentioned as complexing agents for the systems initiating the polymerization.

[0009] However, the derivatization methods known from the prior art for highly reactive isobutene homo- or copolymers, for example for the synthesis of polyisobutenyl succinic anhydrides according to DE-A 27 02 604, exhibit a number of shortcomings. For instance, the content of terminal vinylidene double bonds in the precursor is still too low. The yields in the conversion to the derivatives require improvement. The appearance and consistency of the derivatives, in particular the suppression of discoloration, for example caused by undesired coking reactions under thermal stress during derivatization, are not yet optimal.Furthermore, the physical properties of the derivatives, in particular their viscosity behavior at low temperatures, such as those encountered in practical applications in lubricating oils, as well as their solubilities, especially in polar media, their temperature stability, and their storage stability, still require improvement. The derivatization processes for isobutene polymers known from the prior art, which start with isobutene polymers produced using fluorine-containing polymerization catalysts, have the disadvantage that, due to the residual fluorine content, they cause corrosion on numerous metallic materials and steel grades.

[0010] The object of the present invention was to provide an improved process for the preparation of isobutene homo- or copolymer derivatives, starting from highly reactive isobutene homo- or copolymers, which no longer exhibits the shortcomings of the prior art. In particular, the isobutene homo- or copolymer derivatives should be able to be prepared from isobutene polymers with 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%, and particularly preferably at least 90 mol%, in acceptable yields. Furthermore, the appearance and consistency of the derivatives, for example their color, should be improved.Furthermore, the physical properties of the derivatives, in particular their viscosity behavior at low temperatures, as well as their solubilities, especially in polar media, their temperature stability, and their storage stability, are to be improved. A catalyst system used for the production of the isobutene polymers in the precursor stage should be sufficiently active, long-lasting, easy to handle, and reliable; in particular, it should be fluorine-free to avoid undesirable corrosion on metallic materials and steel grades caused by residual fluorine content.

[0011] The problem was solved by a process for the preparation of isobutene homo- or copolymer derivatives of the general formula I POL(-A) n (I) in which POL denotes the n-functional residue of a hydrophobic polyisobutene homo- or copolymer with a number-averaged molecular weight (M n ) of 110 to 250,000, which may contain structural units of mono-, di- or trifunctional initiators incorporated,

[0012] A means a low molecular weight polar group, which contains one or more amino functions and / or nitro groups and / or hydroxyl groups and / or mercaptan groups and / or carboxylic acid or carboxylic acid derivative functions, in particular succinic anhydride or succinic acid derivative functions, and / or sulfonic acid or sulfonic acid derivative functions and / or aldehyde functions and / or silyl groups, and where the variable n represents the number 1, 2, or 3, and where n = 2 and n = 3 the variables A can be the same or different, which is characterized in that isobutene or a monomer mixture containing isobutene is reacted in the presence of (A) an iron halide donor complex, an aluminum trihalide donor complex, or an aluminum alkyl halide donor complex acting as a polymerization catalyst, the donor being an organic compound with at least one ether function or a carboxylic ester function, or (B) at least one Lewis acid suitable as a polymerization catalyst or a complex acting as a polymerization catalyst consisting 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 C₁ to C₂₀ alkyl group, C₁ to C₂₀ -Halogenalkyl group,A C5 to C8 cycloalkyl group, a C6 to C20 aryl group, or a C7 to C20 arylalkyl group is polymerized, and the resulting highly reactive isobutene homo- or copolymer, which has a content of at least 50 mol% of terminal vinylidene double bonds per polyisobutene chain end, is reacted with at least n equivalents of a compound introducing the low molecular weight polar group A or a substructure of the low molecular weight polar group A, and in the case of reaction with a substructure, the formation of the low molecular weight polar group A is completed by subsequent reactions.

[0013] The polymerization method essential to the invention for isobutene or isobutene-containing monomer mixtures according to embodiment (A) is essentially described in the above-cited unpublished European patent application with file number 10157068.7 and is reproduced below.

[0014] Within the scope of the present invention, isobutene homopolymers are understood to be polymers that consist of at least 98 mol%, preferably at least 99 mol%, of isobutene. Accordingly, isobutene copolymers are understood to be polymers that contain more than 2 mol% of monomers other than isobutene, for example, linear butenes.

[0015] Within the scope of the present invention, the following definitions apply to generically defined residues: A C 1 to C 8 alkyl residue is a linear or branched alkyl residue with 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-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-methyl-propyl, n-Heptyl, n-Octyl and its constitutional isomers such as 2-Ethylhexyl.Such C1 to C8 alkyl groups may also contain small amounts 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.

[0016] A C1 to C20 alkyl group is a linear or branched alkyl group with 1 to 20 carbon atoms. Examples include the C1 to C8 alkyl groups mentioned above, as well as n-nonyl, iso-nonyl, n-decyl, 2-propylheptyl, n-undecyl, n-dodecyl, n-tridecyl, iso-tridecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, and n-eicosyl. Such C1 to C20 alkyl groups may also contain small amounts of heteroatoms such as oxygen, nitrogen, or halogen atoms (e.g., chlorine), and / or non-protic functional groups such as carboxyl ester groups, cyano groups, or nitro groups.

[0017] A C5 to C8 cycloalkyl group is a saturated cyclic residue that may contain alkyl side chains. Examples include 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, and cyclooctyl, 2-, 3-, 4- or 5-methylcyclooctyl. Such C5 to C8 cycloalkyl residues may also contain small amounts 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.

[0018] A C6 to C20 aryl group or a C6 to C12 aryl group preferably represents optionally substituted phenyl, optionally substituted naphthyl, optionally substituted anthracene, or optionally substituted phenanthrene. Such aryl groups can bear 1 to 5 non-protic substituents or non-protic functional groups, for example, C1 to C8 alkyl, C1 to C8 haloalkyl such as C1 to C8 chloroalkyl or C1 to C8 fluoroalkyl, halogen such as chlorine or fluorine, nitro, cyano, or phenyl. Examples of such aryl groups are phenyl, naphthyl, biphenyl, anthracenyl, phenanthrenyl, tolyl, nitrophenyl, chlorophenyl, dichlorophenyl, pentafluorophenyl, pentachlorophenyl, (trifluoromethyl)phenyl, bis(tri-fluoromethyl)phenyl, (trichloro)methylphenyl and bis(trichloromethyl)phenyl.

[0019] A C7 to C20 arylalkyl group or a C7 to C12 arylalkyl group preferably represents optionally substituted C1 to C4 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 C1 to C4 alkylnaphthyl such as naphthylmethyl, optionally substituted C1 to C4 alkylanthracenyl such as anthracenylmethyl or optionally substituted C1 to C4 alkylphenanthrenyl such as phenanthrenylmethyl. Such arylalkyl residues can bear 1 to 5 non-protic substituents or non-protic functional groups, especially on the aryl part, for example C 1 to C 8 alkyl, C 1 to C 8 haloalkyl such as C 1 to C 8 chloroalkyl or C 1 to C 8 fluoroalkyl, halogen such as chlorine or fluorine, nitro or phenyl.

[0020] Suitable iron halides in the corresponding complexes with donors include, for example, iron(II) fluoride, iron(III) fluoride, iron(II) chloride, iron(III) chloride, iron(II) bromide, and iron(III) bromide, as well as mixtures thereof. Iron chlorides, i.e., iron(II) chloride and iron(III) chloride, as well as mixtures of iron(II) chloride and iron(III) chloride, are preferred, but iron(III) chloride alone is particularly preferred. Iron halides, especially iron chlorides, produced from iron-containing metal alloys can also be used; these alloys contain other metal halides in addition to iron halides, especially iron chlorides, with the iron halides, especially iron chlorides, preferably constituting the main components of such mixtures.

[0021] Suitable aluminum trihalides include, in particular, aluminum trifluoride, aluminum trichloride, or aluminum tribromide. Suitable aluminum alkyl halides include, in particular, a mono(C1- to C4-alkyl)aluminum dihalide or a di(C1- to C4-alkyl)aluminum monohalide, for example, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum chloride, or dithylaluminum chloride. In a preferred embodiment, isobutene or an isobutene-containing monomer mixture is polymerized in the presence of an aluminum trichloride donor complex acting as a polymerization catalyst.

[0022] If the iron halide donor complex, aluminum trihalide donor complex or aluminum alkyl halide donor complex, acting as a polymerization catalyst, has an organic compound with at least one ether function as the donor, then compounds with at least one ether function also include acetals and hemiacetals.

[0023] 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 an iron chloride donor complex or an aluminum trichloride donor complex, is used, which contains as a donor a dihydrocarbyl ether of the general formula R 1< -OR 2<, in which the variables R 1< and R 2< independently denote C 1 to C 20 alkyl groups, in particular C 1 to C 8 alkyl groups, C 5 to C 8 cycloalkyl groups, C 6 to C 20 aryl groups, in particular C 6 to C 12 aryl groups, or C 7 to C 20 arylalkyl groups, in particular C 7 to C 12 arylalkyl groups.

[0024] The dihydrocarbyl ethers mentioned can be open-chain or cyclic, with the two variables R 1< and R 2< closing to form a ring in the cyclic ones, and such rings can also contain two or three ether oxygen atoms. Examples of such open-chain and cyclic dihydrocarbyl ethers are dimethyl ether, diethyl ether, dipropyl ether, diisopropyl ether, di-n-butyl ether, di-sec-butyl ether, diisobutyl ether, dipentyl ether, di-n-hexyl ether, di-n-heptyl ether, di-n-octyl ether, di-(2-ethylhexyl) ether, methyl n-butyl ether, methyl sec-butyl ether, methyl isobutyl ether, methyl tert-butyl ether, ethyl n-butyl ether, ethyl sec-butyl ether, ethyl isobutyl ether, n-propyl n-butyl ether, n-propyl sec-butyl ether, n-propyl isobutyl ether, n-propyl tert-butyl ether, isopropyl n-butyl ether, isopropyl sec-butyl ether, isopropyl isobutyl ether, isopropyl tert-butyl ether-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, dicylcohexyl ether, diphenyl ether, ditolyl ether, dixylyl ether and dibenzyl ether. Of the aforementioned dihydrocarbyl ethers, di-n-butyl ethers and diphenyl ethers have proven to be particularly advantageous as donors for the iron halide donor complexes, the aluminum trihalide donor complexes or the aluminum alkyl halide donor complexes, in particular the iron chloride donor complexes or the aluminum trichloride donor complexes.

[0025] 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 an iron chloride donor complex or an aluminum trichloride donor complex, is used as a donor, which contains as a carboxylic acid hydrocarbyl ester of the general formula R 3< -COOR 4<, in which the variables R 3< and R 4< independently denote C 1 to C 20 alkyl groups, in particular C 1 to C 8 alkyl groups, C 5 to C 8 cycloalkyl groups, C 6 to C 20 aryl groups, in particular C 6 to C 12 aryl groups, or C 7 to C 20 arylalkyl groups, in particular C 7 to C 12 arylalkyl groups.

[0026] Examples of the aforementioned carboxylic acid hydrocarbyl esters are methyl formate, ethyl formate, n-propyl formate, isopropyl formate, n-butyl formate, sec-butyl formate, isobutyl formate, tert-butyl formate, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, sec-butyl acetate, isobutyl acetate, tert-butyl acetate, methyl propionate, ethyl propionate, n-propyl propionate, isopropyl propionate, n-butyl propionate, sec-butyl propionate, isobutyl propionate, tert-butyl propionate, methyl butyrate, ethyl butyrate, n-propyl butyrate, and isopropyl butyrate. Butyric acid n-butyl ester, butyric acid sec-butyl ester, butyric acid isobutyl ester, butyric acid tert.-butyl ester, cyclohexane carboxylic acid methyl ester, cyclohexane carboxylic acid ethyl ester, cyclohexane carboxylic acid n-propyl ester, cyclohexane carboxylic acid isopropyl ester, cyclohexane carboxylic acid n-butyl ester, cyclohexane carboxylic acid sec-butyl ester, cyclohexane carboxylic acid isobutyl ester, cyclohexane carboxylic acid tert-butyl ester, benzoic acid methyl ester, benzoic acid ethyl ester, benzoic acid n-propyl ester, benzoic acid isopropyl ester, benzoic acid n-butyl ester, benzoic acid sec-butyl ester, benzoic acid isobutyl ester, benzoic acid tert-butyl ester, phenylacetic acid methyl ester, phenylacetic acid ethyl ester, phenylacetic acid n-propyl ester, phenylacetic acid isopropyl ester, phenylacetic acid n-butyl ester, phenylacetic acid sec-butyl ester Isobutyl phenylacetic acid esters and tert-butyl phenylacetic acid esters. Of the aforementioned carboxylic acid hydrocarbyl esters, ethyl acetate has proven to be a suitable donor for the iron halide donor complexes, the aluminum trihalide donor complexes, and so on.The aluminum alkyl halide donor complexes, in particular the iron chloride donor complexes or the aluminum trichloride donor complexes, were highlighted as being particularly advantageous.

[0027] Furthermore, those dihydrocarbyl ethers and carboxylic acid hydrocarbyl esters have proven particularly advantageous as donors for the iron halide-donor complexes, the aluminum trihalide-donor complexes, and the aluminum alkyl halide-donor complexes, especially the iron chloride-donor complexes and the aluminum trichloride-donor complexes, in which the donor compound has a total number of carbon atoms of 3 to 16, preferably 4 to 16, particularly 4 to 12, and especially 4 to 8. For the dihydrocarbyl ethers in particular, those with a total of 6 to 14, and especially 8 to 12, carbon atoms are preferred. For the carboxylic acid hydrocarbyl esters in particular, those with a total of 3 to 10, and especially 4 to 6, carbon atoms are preferred.

[0028] The molar ratio of the aforementioned donor compounds to the iron halide, aluminum trihalide, or aluminum alkyl halide, especially to iron chloride or aluminum trichloride, in the donor complex is generally in the range of 0.3:1 to 1.5:1, particularly from 0.5:1 to 1.2:1, and especially from 0.7:1 to 1.1:1; in most cases, it is 1:1. However, it is also possible to work with a greater excess of donor compounds, often up to a tenfold, and especially a threefold, molar excess; the excess amount of donor compounds then also acts as a solvent or diluent.

[0029] Typically, the iron halide donor complex, the aluminum trihalide donor complex, or the aluminum alkyl halide donor complex, especially the iron chloride donor complex or the aluminum trichloride donor complex, is prepared separately from the iron halide, the aluminum trihalide, or the aluminum alkyl halide (especially from anhydrous iron chloride or aluminum trichloride) and the donor compound before polymerization. It is then added to the polymerization medium, usually dissolved in an inert solvent such as a halogenated hydrocarbon, for example, dichloromethane. However, the complex can also on site They are produced before polymerization.

[0030] In a preferred embodiment of the present invention, the polymerization is carried out using a mono- or polyfunctional, in particular a mono-, di-, or trifunctional initiator, which is selected from organic hydroxy compounds, organic halogen compounds, protic acids, and water. Mixtures of the aforementioned initiators can also be used, for example, mixtures of two or more organic hydroxy compounds, mixtures of two or more organic halogen compounds, mixtures of one or more organic hydroxy compounds and one or more organic halogen compounds, mixtures of one or more organic hydroxy compounds and water, mixtures of one or more organic halogen compounds and water, or mixtures of one or more protic acids and water. The initiator can be mono-, di-, or polyfunctional, i.e.,The initiator molecule can contain one, two, or more hydroxyl groups or halogen atoms, at which the polymerization reaction starts. In the case of di- or polyfunctional initiators, telechelic isobutene polymers with two or more, in particular two or three, polyisobutene chain ends are typically obtained.

[0031] Suitable monofunctional initiators include organic hydroxy compounds with only one hydroxyl group in the molecule, particularly alcohols and phenols, especially those of the general formula R5-OH, where R5 denotes C1 to C20 alkyl groups, in particular C1 to C8 alkyl groups, C5 to C8 cycloalkyl groups, C6 to C20 aryl groups, in particular C6 to C12 aryl groups, or C7 to C20 arylalkyl groups, in particular C7 to C12 arylalkyl groups. Furthermore, the R5 groups can also contain mixtures of the structures mentioned above and / or possess additional functional groups beyond those already mentioned, for example, a keto group, a nitroxide, or a carboxyl group, and / or heterocyclic structural elements.

[0032] 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- und p-Kresol, Benzylalkohol, p-Methoxybenzylalkohol, 1- und 2-Phenylethanol, 1- und 2-(p-Methoxyphenyl)ethanol, 1-, 2- und 3-Phenyl-1-propanol, 1-, 2- und 3-(p-Methoxyphenyl)-1-propanol, 1- und 2-Phenyl-2-propanol, 1- und 2-(p-Methoxyphenyl)-2-propanol, 1-, 2-, 3- und 4-Phenyl-1-butanol, 1-, 2-, 3- und 4-(p-Methoxyphenyl)-1-butanol, 1-, 2-, 3- und 4-Phenyl-2-butanol, 1-, 2-, 3- und 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)benzonitril, Cyclopropyldiphenylmethanol, 1-Hydroxy-1,1-diphenylpropan-2-on, Benzilsäure, 9-Phenyl-9-fluorenol, Triphenylmethanol, Diphenyl(4-pyridinyl)methanol, alpha,alpha-Diphenyl-2-pyridinmetha-nol, 4-Methoxytritylalkohol (insbesondere polymergebunden als Festphase), alpha-tert.-Butyl-4-chlor-4'-methylbenzhydrol, Cylcohexyldiphenylmethanol, alpha-(p-Tolyl)-benzhydrol, 1,1,2-Triphenylethanol, alpha,alpha-Diphenyl-2-pyridinethanol, alpha,alpha-4-Pyridylbenzohydrol-N-oxid, 2-Fluortriphenylmethanol, Triphenylpropargylalkohol, 4-[(Diphenyl)hydroxymethyl]benzonitril, 1-(2,6-Dimethoxyphenyl)-2-methyl-1-phenyl-1-propanol, 1,1,2-Triphenylpropan-1-ol und p-Anisaldehydcarbinol.

[0033] Suitable bifunctional initiators include, in particular, dihydric alcohols or diols with a total carbon number of 2 to 30, especially 3 to 24, and especially 4 to 20, and bisphenols with a total carbon number of 6 to 30, especially 8 to 24, and especially 10 to 20, for example ethylene glycol, 1,2- and 1,3-propylene glycol, 1,4-butylene glycol, 1,6-hexylene glycol, 1,2-, 1,3- or 1,4-bis(1-hydroxy-1-methylethyl)benzene (o-, m- or p-dicumyl alcohol), bisphenol A, and 9,10-dihydro-9,10-dimethyl-9,10-anthracenediol. 1,1-Diphenylbutane-1,4-diol, 2-hydroxytriphenylcarbinol and 9-[2-(Hydroxymethyl)phenyl]-9-fluorenol.

[0034] Suitable monofunctional initiators for organic halogen compounds with one halogen atom in the molecule include, in particular, compounds of the general formula R< 6< -Hal, where Hal represents a halogen atom selected from fluorine, iodine, and especially chlorine and bromine, and R< 6< denotes C1 to C20 alkyl groups, especially C1 to C8 alkyl groups, C5 to C8 cycloalkyl groups, or C7 to C20 arylalkyl groups, especially C7 to C12 arylalkyl groups. Furthermore, the R< 6< groups can also contain mixtures of the structures mentioned above and / or possess additional functional groups beyond those already mentioned, such as a keto group, a nitroxide, or a carboxyl group, and / or heterocyclic structural elements.

[0035] 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 chloride, tert-butyl bromide.-Butylbromid, 1-Chlorpentan, 1-Brompentan, 1-Chlorhexan, 1-Bromhexan, 1-Chlorheptan, 1-Bromheptan, 1-Chloroctan, 1-Bromoctan, 1-Chlor-2-ethylhexan, 1-Brom-2-ethylhexan, Cyclohexylchlorid, Cyclohexylbromid, Benzylchlorid, Benzylbromid, 1-Phenyl-1-chlorethan, 1-Phenyl-1-bromethan, 1-Phenyl-2-chlorethan, 1-Phenyl-2-bromethan, 1-Phenyl-1-chlorpropan, 1-Phenyl-1-brompropan, 1-Phenyl-2-chlorpropan, 1-Phenyl-2-brompropan, 2-Phenyl-2-chlorpropan, 2-Phenyl-2-brompropan, 1-Phenyl-3-chlorpropan, 1-Phenyl-3-brompropan, 1-Phenyl-1-chlorbutan, 1-Phenyl-1-brombutan, 1-Phenyl-2-chlorbutan, 1-Phenyl-2-brombutan, 1-Phenyl-3-chlorbutan, 1-Phenyl-3-brombutan, 1-Phenyl-4-chlorbutan, 1-Phenyl-4-brombutan, 2-Phenyl-1-chlorbutan, 2-Phenyl-1-brombutan, 2-Phenyl-2-chlorbutan, 2-Phenyl-2-brombutan, 2-Phenyl-3-chlorbutan, 2-Phenyl-3-brombutan, 2-Phenyl-4-chlorbutan und 2-Phenyl-4-brombutan.

[0036] Examples of difunctional initiators of organic halogen compounds with two halogen atoms in the molecule include 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).

[0037] The initiator is particularly preferably selected from organic hydroxy compounds in which one or more hydroxyl groups are bonded to an sp³-hybridized carbon atom ("alcohols") or to an aromatic ring ("phenols"), organic halogen compounds in which one or more halogen atoms are bonded to an sp³-hybridized carbon atom, protic acids, and water. Of these, an initiator selected from organic hydroxy compounds in which one or more hydroxyl groups are bonded to an sp³-hybridized carbon atom is particularly preferred.

[0038] Particularly preferred as initiators for organic halogen compounds are those in which one or more halogen atoms are bonded to a secondary or, in particular, to a tertiary sp 3< -hybridized carbon atom.

[0039] Preferably, initiators are designated which, in addition to the hydroxyl group, bear the substituents R10<, R11< and R12< on such an sp3< hydrogenated carbon atom, which independently represent hydrogen, C1 to C20 alkyl, C5 to C8 cycloalkyl, C6 to C20 aryl, C7 to C20 alkylaryl or phenyl, wherein an aromatic core may further bear one or more, preferably one or two, C1 to C4 alkyl, C1 to C4 alkoxy, C1 to C4 hydroxyalkyl or C1 to C4 haloalkyl substituents, wherein at most one of the variables R10<, R11< or R12< represents hydrogen and at least one of the variables R10<, R11< or R12< represents phenyl. which may bear one or more, preferably one or two, C 1 to C 4 alkyl, C 1 to C 4 alkoxy, C 1 to C 4 hydroxyalkyl or C 1 to C 4 haloalkyl groups as substituents.

[0040] Examples of protic acids include hydrochloric acid, hydrobromic acid, hydrofluoric acid, sulfuric acid, hydrocyanic acid, and mixtures thereof. Protonated ethers can also be used as protic acids.

[0041] Particularly preferred for the present invention are initiators selected under water, one or more protic acids, methanol, ethanol, 1-phenylethanol, 1-(p-methoxyphenyl)ethanol, n-propanol, isopropanol, 2-phenyl-2-propanol (cumene), n-butanol, isobutanol, sec-butanol, tert-butanol, 1-phenyl-1-chloroethane, 2-phenyl-2-chloropropane (cumyl chloride), tert-butyl chloride and 1,3- or 1,4-bis-(1-hydroxy-1-methylethyl)benzene, as well as mixtures thereof. Of these, initiators are particularly preferred which are selected under water, one or more protic acids, methanol, ethanol, 1-phenylethanol, 1-(p-methoxyphenyl)ethanol, n-propanol, isopropanol, 2-phenyl-2-propanol (cumene), n-butanol, isobutanol, sec-butanol, tert-butanol, 1-phenyl-1-chloroethane and 1,3- or 1,4-bis-(1-hydroxy-1-methyl-ethyl)benzene, as well as mixtures thereof.

[0042] The molar ratio of the aforementioned initiators to the isobutene monomer used in the homopolymerization of isobutene, or to the total amount of polymerizable monomers used in the copolymerization of isobutene, is, according to embodiment (A), generally 0.0005 : 1 to 0.1 : 1, in particular 0.001 : 1 to 0.075 : 1, and especially 0.0025 : 1 to 0.05 : 1, based on each individual functional site of the initiator. When water is used as the sole initiator, or in combination with organic hydroxy compounds and / or organic halogen compounds as further initiators, the molar ratio of water to the isobutene monomer used in the homopolymerization of isobutene, or to the total amount of polymerizable monomers used in the copolymerization of isobutene, is in particular 0.0001 : 1 to 0.1 : 1, especially 0.0002 : 1 to 0.05 : 1.

[0043] In embodiment (A), some of the initiator molecules added as organic hydroxy or halogen compounds are incorporated into the polymer chains. The proportion (leff) of polymer chains initiated by such an incorporated organic initiator molecule can be up to 100%, but is typically between 5% and 90%. The remaining polymer chains are formed either by water originating from trace amounts of moisture as an initiator molecule or by chain transfer reactions.

[0044] 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 0.05 to 5.0 mmol, especially 0.1 to 1.0 mmol, in each case based on 1 mol of isobutene monomer used in homopolymerization of isobutene or on 1 mol of the total amount of polymerizable monomers used in copolymerization of isobutene, a nitrogen-containing basic compound.

[0045] Such a nitrogen-containing basic compound can be an aliphatic, cycloaliphatic, or aromatic amine of the general formula R7 - R8 R9 or even ammonia, in which the variables R7, R8, and R9 each independently represent hydrogen, C1 to C20 alkyl groups, in particular C1 to C8 alkyl groups, C5 to C8 cycloalkyl groups, C6 to C20 aryl groups, in particular C6 to C12 aryl groups, or C7 to C20 arylalkyl groups, in particular C7 to C12 arylalkyl groups. If none of these variables represents hydrogen, the compound is a tertiary amine. If one of these variables represents hydrogen, the compound is a secondary amine. If two of these variables represent hydrogen, the compound is a primary amine. If all of these variables represent hydrogen, then ammonia is present.

[0046] Typical examples of such amines of the general formula R 7< -NR 8< R 9< are methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, tert-butylamine, sec-butylamine, isobutylamine, tert-amylamine, n-hexylamine, n-heptylamine, n-octylamine, 2-ethylhexylamine, cyclopentylamine, cyclohexylamine, aniline, dimethylamine, diethylamine, di-n-propylamine, di-isopropylamine, di-n-butylamine, di-tert-butylamine, di-sec-butylamine, di-isobutylamine, di-tert-amylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-(2-ethylhexyl)amine, dicyclopentylamine. Dicyclohexylamine, diphenylamine, trimethylamine, triethylamine, tri-n-propylamine, tri-iso-propylamine, 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.

[0047] Furthermore, a compound with several, in particular with two or three, nitrogen atoms and with 2 to 20 carbon atoms can also be used as such a nitrogen-containing basic compound, wherein these nitrogen atoms each independently bear 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.

[0048] However, a saturated, semi-saturated, or unsaturated nitrogenous five- or six-membered ring heterocycle is particularly suitable as such a nitrogen-containing basic compound. This heterocycle may contain one, two, or three ring nitrogen atoms and may have one or two further ring heteroatoms from the oxygen and sulfur group and / or hydrocarbyl residues, in particular C1 to C4 alkyl residues and / or phenyl, and / or functional groups or heteroatoms as substituents, in particular fluorine, chlorine, bromine, nitro, and / or cyano. Examples include pyrrolidine, pyrrole, imidazole, 1,2,3- or 1,2,4-triazole, oxazole, thiazole, piperidine, pyrazine, pyrazine, pyrazole, pyridazine, pyrimidine, pyrazine, 1,2,3-, 1,2,4- or 1,2,5-triazine, and 1,2,5-oxathiazine. 2H-1,3,5-thiadiazine or morpholine.

[0049] However, pyridine or a derivative of pyridine (especially a mono-, di- or tri-C 1 - to C 4 -alkyl-substituted pyridine) such as 2-, 3-, or 4-methylpyridine (picolins), 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, 3,5- or 3,6-dimethylpyridine (lutidines), 2,4,6-trimethylpyridine (collidin), 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 is particularly suitable as such a nitrogen-containing basic compound.

[0050] One can use a single nitrogen-containing basic compound or mixtures of such nitrogen-containing basic compounds.

[0051] The polymerization method essential to the present invention for isobutene or isobutene-containing monomer mixtures according to embodiment (B) is described below.

[0052] Within the scope of the present invention, isobutene homopolymers are understood to be polymers that consist of at least 98 mol%, preferably at least 99 mol%, of isobutene. Accordingly, isobutene copolymers are understood to be polymers that contain more than 2 mol% of monomers other than isobutene, for example, linear butenes.

[0053] Within the scope of the present invention, the following definitions apply to generically defined residues: A C 1 to C 8 alkyl residue is a linear or branched alkyl residue with 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-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 C1 to C8 alkyl groups can also contain small amounts of heteroatoms such as oxygen, nitrogen or halogen atoms, e.g.containing chlorine or fluorine, and / or non-protic functional groups such as carboxyl ester groups, cyano groups or nitro groups.

[0054] A C1 to C20 alkyl group is a linear or branched alkyl group with 1 to 20 carbon atoms. Examples include the C1 to C8 alkyl groups mentioned above, as well as n-nonyl, iso-nonyl, n-decyl, 2-propylheptyl, n-undecyl, n-dodecyl, n-tridecyl, iso-tridecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, and n-eicosyl. Such C1 to C20 alkyl groups may also contain small amounts of heteroatoms such as oxygen, nitrogen, or halogen atoms (e.g., chlorine or fluorine), and / or non-protic functional groups such as carboxyl ester groups, cyano groups, or nitro groups.

[0055] A C1 to C20 haloalkyl group or a C1 to C8 haloalkyl group is a group with the basic frameworks described above for C1 to C20 alkyl groups or C1 to C8 alkyl groups, respectively, in which, however, a greater number of hydrogen atoms are replaced by halogen atoms, 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 groups are C1 to C4 alkyl groups in which at least 60%, in particular at least 75%, and 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.

[0056] A C5 to C8 cycloalkyl group is a saturated cyclic residue that may contain alkyl side chains. Examples include 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, and cyclooctyl, 2-, 3-, 4- or 5-methylcyclooctyl. Such C5 to C8 cycloalkyl groups may also contain small amounts of heteroatoms such as oxygen, nitrogen, or halogen atoms, e.g., hydrogen, nitrate, or nitrate. B. chlorine or fluorine, and / or non-protic functional groups such as carboxyl ester groups, cyano groups or nitro groups.

[0057] A C6 to C20 aryl group or a C6 to C12 aryl group preferably represents optionally substituted phenyl, optionally substituted naphthyl, optionally substituted anthracene, or optionally substituted phenanthrenyl. Such aryl groups can bear 1 to 5 non-protic substituents or non-protic functional groups, for example, C1 to C8 alkyl, C1 to C8 haloalkyl such as C1 to C8 chloroalkyl or C1 to C8 fluoroalkyl, halogen such as chlorine or fluorine, nitro, cyano, or phenyl. Examples of such aryl groups are phenyl, naphthyl, biphenyl, anthracenyl, phenanthrenyl, tolyl, nitrophenyl, chlorophenyl, dichlorophenyl, pentafluorophenyl, pentachlorophenyl, (trifluoromethyl)phenyl, bis(tri-fluoromethyl)phenyl, (trichloro)methylphenyl and bis(trichloromethyl)phenyl.

[0058] A C7 to C20 arylalkyl group or a C7 to C12 arylalkyl group preferably represents optionally substituted C1 to C4 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 C1 to C4 alkylnaphthyl such as naphthylmethyl, optionally substituted C1 to C4 alkylanthracenyl such as anthracenylmethyl or optionally substituted C1 to C4 alkylphenanthrenyl such as phenanthrenylmethyl. Such arylalkyl residues can bear 1 to 5 non-protic substituents or non-protic functional groups, especially on the aryl part, for example C 1 to C 8 alkyl, C 1 to C 8 haloalkyl such as C 1 to C 8 chloroalkyl or C 1 to C 8 fluoroalkyl, halogen such as chlorine or fluorine, nitro or phenyl.

[0059] The inventive process for the production of highly reactive isobutene homo- or copolymers generally proceeds according to a cationic reaction mechanism - due to the use of the complex consisting of at least one Lewis acid and optionally at least one donor and the initiators described, which acts as a polymerization catalyst.

[0060] The essential feature of 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 Z-SO₃H sulfonic acids can also be used. In addition to these sulfonic acid initiators, other initiator molecules from other chemical classes can also be used.

[0061] The variable Z preferably represents a C1 to C8 alkyl group, a C1 to C8 halogenated alkyl group, a C5 to C8 cycloalkyl group, a C6 to C12 aryl group, or a C7 to C12 arylalkyl group. Particularly preferably, Z represents a C1 to C4 alkyl group, a C1 to C4 halogenated alkyl group, an optionally substituted phenyl group, e.g., a tolyl group or a xylyl group, or an optionally substituted C1 to C4 alkylphenyl group, e.g., a benzyl group.

[0062] 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.

[0063] In principle, all inorganic molecules classified as Lewis acids by definition are suitable as polymerization catalysts or as polymerization catalysts within complexes. However, halogen compounds of metals and metalloids from the periodic table are particularly suitable, provided their valences are completely saturated by halogen atoms or they contain one or more organic carbon groups—especially C1 to C4 alkyl groups—in addition to the halogen substituents. Suitable halogen substituents in these elemental halides and elemental alkyl halides include iodine, bromine, and especially fluorine and, above all, chlorine. Mixtures of such elemental halides or elemental alkyl halides can, of course, also be used, both individually and in combination.

[0064] For example, if the halides or alkyl halides of aluminum are used as Lewis acids, the following species can typically be used: aluminum trifluoride, aluminum trichloride, aluminum tribromide; as aluminum alkyl halides, mono(C 1 - to C 4 -alkyl)aluminium dihalides or di(C 1 - to C 4 -alkyl)aluminium monohalide such as methylaluminium dichloride, ethylaluminium dichloride, dimethylaluminium chloride or diethylaluminium chloride.

[0065] In a preferred embodiment, at least one compound selected from the binary chlorine and fluorine compounds of the elements of groups 1 to 8 and 3 to 5 of the periodic table is used as the Lewis acid for the polymerization catalyst or complex acting as a polymerization catalyst, wherein the binary chlorine compounds may be preferred over the binary fluorine compounds of these elements.

[0066] Typical such binary chlorine compounds are ScCl 3 , YCl 3 , YbCl 3 , TiCl 3 , TiCl 4 , ZrCl 4 , HfCl 4 , VCl 3 , VCl 4 , NbCl 3 , NbCl 5 , TaCl 2 , ClCl CrCl 3 , MoCl 3 , MoCl 5 , WCl 5 , WCl 6 , MnCl 2 , ReCl 3 , ReCl 5 , FeCl 2 , FeCl 3 , RuCl 3 , OsCl 3 , CoCl 2 , CoCl 3 , RCl 3 , ICl NiCl 2 , PdCl 2 , PtCl 2 , CuCI, CuCl 2 , AgCl, AuCI, ZnCl 2 , CdCl 2 , HgCl, HgCl 2 , BCl 3 , AlCl 3 , GaCl 3 , InCl 3 , TLC 34 , SiCl , SnCl 2 , SnCl 3 , SnCl 4 , PbCl 2 , PbCl 4 , PCl 3 , PCl 5 , AsCl 3 , SbCl 3 , SbCl 5 and BiCl 3 . Particularly affected are BCl 3 , AlCl 3 , TiCl 4 , FeCl 2 , FeCl 3 and ZnCl 2 .

[0067] Typical examples of such binary fluorine compounds are ScF₃, YF₃, YbF₃, TiF₃, TiF₄, ZrF₄, HfF₄, VF₃, VF₄, NbF₃, NbF₅, TaF₅, CrF₂, CrF₃, MoF₃, MoF₅, WF₅, WF₆, MnF₂, ReF₃, ReF₅, FeF₂, FeF₃, RuF₃, OsF₃, CoF₂, CoF₃, RhF₃, IrF₃, NiF₂, PdF₂, PtF₂, CuF, CuF₂, AgF, AuF, ZnF₂, CdF₂, HgF₆ HgF₂, BF₃, AlF₃, GaF₃, InF₃, TIF₃, SiF₄, GeF₄, SnF₂, SnF₃, SnF₄, PbF₂, PbF₄, PF₃, PF₅, AsF₃, SbF₃, SbF₅, and BiF₃. Of these, BF₃, AlF₃, TiF₄, FeF₂, FeF₃, and ZnF₂ are particularly preferred. Mixtures of binary chlorine and fluorine compounds can also be used.

[0068] Binary bromine compounds can often also be used as such Lewis acids; examples of such bromine compounds are: TiBr₃, TiBr₄, ZrBr₄, VBr₃, VBr₄, CrBr₂, CrBr₃, MoBr₃, MoBr₅, WBr₅, WBr₆, MnBr₂, FeBr₂, FeBr₃, CoBr₂, CoBr₃, NiBr₂, PdBr₂, PtBr₂, CuBr, CuBr₂, AgBr, AuBr, ZnBr₂, CdBr₂, HgBr, HgBr₂, BBr₃, AlBr₃, SiBr₄, SnBr₂, SnBr 3 , SnBr 4 , PbBr 2 , PbBr 4 , PBr 3 , PBr 5 , AsBr 3 , SbBr 3 , SbBr 5 and BiBr 3 .

[0069] Particularly preferred are the use of 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 BCl 3 , AlCl 3 , TiCl 4 , FeCl 2 , FeCl 3 , ZnCl 2 , BF 3 , AlF 3 , TiF 4 , FeF 2 , FeF 3 and / or ZnF 2 , especially methanesulfonic acid together with AlCl 3 , BF 3 or FeCl 3 , particularly when Lewis acid complexes are used which contain the dihydrocarbyl ethers of the general formula R 1< -OR 2< and / or carboxylic acid hydrocarbyl esters of the general formula R 3< -COOR 4< listed below as preferred donors.

[0070] Preferably, the process according to the invention employs a complex acting as a polymerization catalyst, which contains as a donor an organic compound with at least one ether group or a carboxylic ester group. Of course, mixtures of different organic compounds with at least one ether group and / or of different organic compounds with at least one carboxylic ester group can also be used. If the complex acting as a polymerization catalyst has as a donor an organic compound with at least one ether group, compounds with at least one ether group also include acetals and hemiacetals.

[0071] In a preferred embodiment of the present invention, a complex acting as a polymerization catalyst is used, comprising at least one Lewis acid and at least one donor, wherein the organic compound acting as donor is a dihydrocarbyl ether of the general formula R1< -OR2< , in which the variables R1< and R2< independently denote C1 to C20 alkyl groups, in particular C1 to C8 alkyl groups, C5 to C8 cycloalkyl groups, C6 to C20 aryl groups, in particular C6 to C12 aryl groups, or C7 to C20 arylalkyl groups, in particular C7 to C12 arylalkyl groups, or a carboxylic acid hydrocarbyl ester of the general formula R3< -COOR4< , in which the variables R3< and R4< independently denote C1 to C20 -Alkyl groups, in particular, C1 to C8 alkyl groups, C5 to C8 cycloalkyl groups, C6 to C20 aryl groups, in particular C6 to C12 aryl groups, or C7 to C20 arylalkyl groups,especially C7 to C12 arylalkyl groups.

[0072] The dihydrocarbyl ethers mentioned can be open-chain or cyclic, with the two variables R 1< and R 2< closing to form a ring in the cyclic ones, and such rings can also contain two or three ether oxygen atoms. Examples of such open-chain and cyclic dihydrocarbyl ethers are dimethyl ether, diethyl ether, dipropyl ether, diisopropyl ether, di-n-butyl ether, di-sec-butyl ether, diisobutyl ether, dipentyl ether, di-n-hexyl ether, di-n-heptyl ether, di-n-octyl ether, di-(2-ethylhexyl) ether, methyl n-butyl ether, methyl sec-butyl ether, methyl isobutyl ether, methyl tert-butyl ether, ethyl n-butyl ether, ethyl sec-butyl ether, ethyl isobutyl ether, n-propyl n-butyl ether, n-propyl sec-butyl ether, n-propyl isobutyl ether, n-propyl tert-butyl ether, isopropyl n-butyl ether, isopropyl sec-butyl ether, isopropyl isobutyl ether, isopropyl tert-butyl ether-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, dicylcohexyl ether, diphenyl ether, diitolyl ether, dixylyl ether and dibenzyl ether. Of the aforementioned dihydrocarbyl ethers, di-n-butyl ether and diphenyl ether have proven particularly advantageous as donors, especially in combination with the Lewis acids BCl₃, AlCl₃, TiCl₄, FeCl₂, FeCl₃ and ZnCl₂.

[0073] Examples of the aforementioned carboxylic acid hydrocarbyl esters are methyl formate, ethyl formate, n-propyl formate, isopropyl formate, n-butyl formate, sec-butyl formate, isobutyl formate, tert-butyl formate, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, sec-butyl acetate, isobutyl acetate, tert-butyl acetate, methyl propionate, ethyl propionate, n-propyl propionate, isopropyl propionate, n-butyl propionate, sec-butyl propionate, isobutyl propionate, tert-butyl propionate, methyl butyrate, ethyl butyrate, n-propyl butyrate, and isopropyl butyrate. Butyric acid n-butyl ester, butyric acid sec-butyl ester, butyric acid isobutyl ester, butyric acid tert.-butyl ester, cyclohexane carboxylic acid methyl ester, cyclohexane carboxylic acid ethyl ester, cyclohexane carboxylic acid n-propyl ester, cyclohexane carboxylic acid isopropyl ester, cyclohexane carboxylic acid n-butyl ester, cyclohexane carboxylic acid sec-butyl ester, cyclohexane carboxylic acid isobutyl ester, cyclohexane carboxylic acid tert-butyl ester, benzoic acid methyl ester, benzoic acid ethyl ester, benzoic acid n-propyl ester, benzoic acid isopropyl ester, benzoic acid n-butyl ester, benzoic acid sec-butyl ester, benzoic acid isobutyl ester, benzoic acid tert-butyl ester, phenylacetic acid methyl ester, phenylacetic acid ethyl ester, phenylacetic acid n-propyl ester, phenylacetic acid isopropyl ester, phenylacetic acid n-butyl ester, phenylacetic acid sec-butyl ester Phenyleacetic acid isobutyl ester and phenyleacetic acid tert-butyl ester.Of the aforementioned carboxylic acid hydrocarbyl esters, ethyl acetate has proven to be particularly advantageous as a donor, especially in combination with the Lewis acids BCl 3 , AlCl 3 , TiCl 4 , FeCl 2 , FeCl 3 and ZnCl 2 .

[0074] Furthermore, such dihydrocarbyl ethers and carboxylic acid hydrocarbyl esters have proven particularly advantageous as donors, especially in combination with the Lewis acids BCl₃, AlCl₃, TiCl₄, FeCl₂, FeCl₃, and ZnCl₂, where the donor compound has a total carbon number of 3 to 16, preferably 4 to 16, particularly 4 to 12, and especially 4 to 8. For dihydrocarbyl ethers in particular, those with a total of 6 to 14, and especially 8 to 12, carbon atoms are preferred. For carboxylic acid hydrocarbyl esters in particular, those with a total of 3 to 10, and especially 4 to 6, carbon atoms are preferred.

[0075] The molar ratio of the aforementioned donor compounds to the Lewis acids, specifically the elemental halides and elemental alkyl halides mentioned, particularly the Lewis acids BCl₃, AlCl₃, TiCl₄, FeCl₂, FeCl₃, and ZnCl₂, in the complex acting as a polymerization catalyst, is generally in the range of 0.3:1 to 1.5:1, especially 0.5:1 to 1.2:1, and most often 0.7:1 to 1.1:1; in most cases, it is 1:1. However, a greater excess of donor compounds, often up to a tenfold, and especially a threefold, molar excess, can also be used; the excess amount of donor compounds then additionally acts as a solvent or diluent.

[0076] The complex acting as a polymerization catalyst is usually prepared separately before polymerization from the Lewis acid(s) mentioned, which are generally used in anhydrous form, and the donor compound(s), and then added to the polymerization medium – usually dissolved in an inert solvent such as a halogenated hydrocarbon, for example, dichloromethane. However, the complex can also on site They are produced before polymerization.

[0077] In a preferred embodiment of the present invention, the polymerization is carried out using 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, protic acids and water. Mixtures of such further initiators can also be used, for example, mixtures of two or more organic hydroxy compounds, mixtures of two or more organic halogen compounds, mixtures of one or more organic hydroxy compounds and one or more organic halogen compounds, mixtures of one or more organic hydroxy compounds and water, mixtures of one or more organic halogen compounds and water, or mixtures of one or more protic acids and water. The initiator can be mono-, di- or polyfunctional, i.e.,The initiator molecule can contain one, two, or more hydroxyl groups or halogen atoms, at which the polymerization reaction starts. In the case of di- or polyfunctional initiators, telechelic isobutene polymers with two or more, in particular two or three, polyisobutene chain ends are typically obtained.

[0078] Suitable monofunctional initiators include organic hydroxy compounds with only one hydroxyl group in the molecule, particularly alcohols and phenols, especially those of the general formula R5-OH, where R5 denotes C1 to C20 alkyl groups, in particular C1 to C8 alkyl groups, C5 to C8 cycloalkyl groups, C6 to C20 aryl groups, in particular C6 to C12 aryl groups, or C7 to C20 arylalkyl groups, in particular C7 to C12 arylalkyl groups. Furthermore, the R5 groups can also contain mixtures of the structures mentioned above and / or possess additional functional groups beyond those already mentioned, for example, a keto group, a nitroxide, or a carboxyl group, and / or heterocyclic structural elements.

[0079] 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- und p-Kresol, Benzylalkohol, p-Methoxybenzylalkohol, 1- und 2-Phenylethanol, 1- und 2-(p-Methoxyphenyl)ethanol, 1-, 2- und 3-Phenyl-1-propanol, 1-, 2- und 3-(p-Methoxyphenyl)-1-propanol, 1- und 2-Phenyl-2-propanol, 1- und 2-(p-Methoxyphenyl)-2-propanol, 1-, 2-, 3- und 4-Phenyl-1-butanol, 1-, 2-, 3- und 4-(p-Methoxyphenyl)-1-butanol, 1-, 2-, 3- und 4-Phenyl-2-butanol, 1-, 2-, 3- und 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)benzonitril, Cyclopropyldiphenylmethanol, 1-Hydroxy-1,1-diphenylpropan-2-on, Benzilsäure, 9-Phenyl-9-fluorenol, Triphenylmethanol, Diphenyl(4-pyridinyl)methanol, alpha,alpha-Diphenyl-2-pyridinmethanol, 4-Methoxytritylalkohol (insbesondere polymergebunden als Festphase), alphatert.-Butyl-4-chlor-4'-methylbenzhydrol, Cylcohexyldiphenylmethanol, alpha-(p-Tolyl)-benzhydrol, 1,1,2-Triphenylethanol, alpha,alpha-Diphenyl-2-pyridinethanol, alpha,alpha-4-Pyridylbenzohydrol-N-oxid, 2-Fluortriphenylmethanol, Triphenylpropargylalkohol, 4-[(Diphenyl)hydroxymethyl]benzonitril, 1-(2,6-Dimethoxyphenyl)-2-methyl-1-phenyl-1-propanol, 1,1,2-Triphenylpropan-1-ol und p-Anisaldehydcarbinol.

[0080] Suitable bifunctional initiators include, in particular, dihydric alcohols or diols with a total carbon number of 2 to 30, especially 3 to 24, and especially 4 to 20, and bisphenols with a total carbon number of 6 to 30, especially 8 to 24, and especially 10 to 20, for example ethylene glycol, 1,2- and 1,3-propylene glycol, 1,4-butylene glycol, 1,6-hexylene glycol, 1,2-, 1,3- or 1,4-bis(1-hydroxy-1-methylethyl)benzene (o-, m- or p-dicumyl alcohol), bisphenol A, and 9,10-dihydro-9,10-dimethyl-9,10-anthracenediol. 1,1-Diphenylbutane-1,4-diol, 2-hydroxytriphenylcarbinol and 9-[2-(Hydroxymethyl)phenyl]-9-fluorenol.

[0081] Suitable monofunctional initiators for organic halogen compounds with one halogen atom in the molecule include, in particular, compounds of the general formula R< 6< -Hal, where Hal represents a halogen atom selected from fluorine, iodine, and especially chlorine and bromine, and R< 6< denotes C1 to C20 alkyl groups, especially C1 to C8 alkyl groups, C5 to C8 cycloalkyl groups, or C7 to C20 arylalkyl groups, especially C7 to C12 arylalkyl groups. Furthermore, the R< 6< groups can also contain mixtures of the structures mentioned above and / or possess additional functional groups beyond those already mentioned, such as a keto group, a nitroxide, or a carboxyl group, and / or heterocyclic structural elements.

[0082] 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 chloride, tert-butyl bromide.-Butylbromid, 1-Chlorpentan, 1-Brompentan, 1-Chlorhexan, 1-Bromhexan, 1-Chlorheptan, 1-Bromheptan, 1-Chloroctan, 1-Bromoctan, 1-Chlor-2-ethylhexan, 1-Brom-2-ethylhexan, Cyclohexylchlorid, Cyclohexylbromid, Benzylchlorid, Benzylbromid, 1-Phenyl-1-chlorethan, 1-Phenyl-1-bromethan, 1-Phenyl-2-chlorethan, 1-Phenyl-2-bromethan, 1-Phenyl-1-chlorpropan, 1-Phenyl-1-brompropan, 1-Phenyl-2-chlorpropan, 1-Phenyl-2-brompropan, 2-Phenyl-2-chlorpropan, 2-Phenyl-2-brompropan, 1-Phenyl-3-chlorpropan, 1-Phenyl-3-brompropan, 1-Phenyl-1-chlorbutan, 1-Phenyl-1-brombutan, 1-Phenyl-2-chlorbutan, 1-Phenyl-2-brombutan, 1-Phenyl-3-chlorbutan, 1-Phenyl-3-brombutan, 1-Phenyl-4-chlorbutan, 1-Phenyl-4-brombutan, 2-Phenyl-1-chlorbutan, 2-Phenyl-1-brombutan, 2-Phenyl-2-chlorbutan, 2-Phenyl-2-brombutan, 2-Phenyl-3-chlorbutan, 2-Phenyl-3-brombutan, 2-Phenyl-4-chlorbutan und 2-Phenyl-4-brombutan.

[0083] Examples of difunctional initiators of organic halogen compounds with two halogen atoms in the molecule include 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).

[0084] Particularly preferred is the further initiator selected from organic hydroxy compounds in which one or more hydroxyl groups are bonded to an sp³-hybridized carbon atom, organic halogen compounds in which one or more halogen atoms are bonded to an sp³-hybridized carbon atom, protic acids, and water. Of these, an initiator selected from organic hydroxy compounds in which one or more hydroxyl groups are bonded to an sp³-hybridized carbon atom is particularly preferred.

[0085] Particularly preferred as further initiators for organic halogen compounds are those in which one or more halogen atoms are bonded to a secondary or, in particular, to a tertiary sp 3< -hybridized carbon atom.

[0086] Preferred are, in particular, further initiators which, on such an sp³-hydrogenated carbon atom, bear the residues R₅, R₆, and R₇, in addition to the hydroxyl group, which independently represent hydrogen, C₁ to C₂₀ alkyl, C₅ to C₈ cycloalkyl, C₆ to C₂₀ aryl, C₇ to C₂₀ alkylaryl, or phenyl, wherein an aromatic core may further bear one or more, preferably one or two, C₁ to C₄ alkyl, C₁ to C₄ alkoxy, C₁ to C₄ hydroxyalkyl, or C₁ to C₄ haloalkyl residues as substituents, wherein at most one of the variables R₅, R₆, or R₇ represents hydrogen and at least one of the variables R₅, R₆, or R₇ represents phenyl, which may further represent one or more, preferably one or can bear two C 1 to C 4 alkyl, C 1 to C 4 alkoxy, C 1 to C 4 hydroxyalkyl or C 1 to C 4 haloalkyl groups as substituents.

[0087] Examples of protic acids include hydrochloric acid, hydrobromic acid, hydrofluoric acid, sulfuric acid, hydrocyanic acid, and mixtures thereof. Protonated ethers can also be used as protic acids.

[0088] Particularly preferred for the present invention are further initiators selected under water, one or more protic acids, methanol, ethanol, 1-phenylethanol, 1-(p-methoxyphenyl)ethanol, n-propanol, isopropanol, 2-phenyl-2-propanol (cumene), n-butanol, isobutanol, sec-butanol, tert-butanol, 1-phenyl-1-chloroethane, 2-phenyl-2-chloropropane (cumyl chloride), tert-butyl chloride and 1,3- or 1,4-bis(1-hydroxy-1-methylethyl)benzene, as well as mixtures thereof. Of these, further initiators are particularly preferred, which are selected 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, as well as mixtures thereof.

[0089] The molar ratio of the sum of the organic sulfonic acids of the general formula Z-SO₃H used according to the invention and the optionally used further initiators mentioned above to the isobutene monomer used in the homopolymerization of isobutene or to the total amount of polymerizable monomers used in the copolymerization of isobutene, based on each individual functional site of the initiator (where the organic sulfonic acids are to be considered monofunctional), is generally 0.001 : 1 to 0.5 : 1, in particular 0.01 : 1 to 0.4 : 1, especially 0.1 : 1 to 0.3 : 1. When water is used as the sole further initiator or in combination with organic hydroxy compounds and / or organic halogen compounds as further initiators, the molar ratio of water alone to the isobutene monomer used in the homopolymerization of isobutene or...The total amount of polymerizable monomers used in the copolymerization of isobutene is in particular 0.0001 : 1 to 0.1 : 1, especially 0.0002 : 1 to 0.05 : 1.

[0090] Some of the initiator molecules added as organic sulfonic acids and, if applicable, as organic hydroxy or halogen compounds, can be incorporated into the polymer chains. The proportion (Ieff) of polymer chains initiated by such an incorporated organic initiator molecule can be up to 100%, but is typically between 0 and 90%, and can range from 5 to 90%. The remaining polymer chains are formed either by water originating from trace amounts of moisture as an initiator molecule or by chain transfer reactions.

[0091] 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 0.05 to 5.0 mmol, especially 0.1 to 1.0 mmol, in each case based on 1 mol of isobutene monomer used in homopolymerization of isobutene or on 1 mol of the total amount of polymerizable monomers used in copolymerization of isobutene, a nitrogen-containing basic compound.

[0092] Such a nitrogen-containing basic compound can be an aliphatic, cycloaliphatic, or aromatic amine of the general formula R7 - R8 R9 or even ammonia, in which the variables R7, R8, and R9 each independently represent hydrogen, C1 to C20 alkyl groups, in particular C1 to C8 alkyl groups, C5 to C8 cycloalkyl groups, C6 to C20 aryl groups, in particular C6 to C12 aryl groups, or C7 to C20 arylalkyl groups, in particular C7 to C12 arylalkyl groups. If none of these variables represents hydrogen, the compound is a tertiary amine. If one of these variables represents hydrogen, the compound is a secondary amine. If two of these variables represent hydrogen, the compound is a primary amine. If all of these variables represent hydrogen, then ammonia is present.

[0093] Typical examples of such amines of the general formula R 7< -NR 8< R 9< are methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, tert-butylamine, sec-butylamine, isobutylamine, tert-amylamine, n-hexylamine, n-heptylamine, n-octylamine, 2-ethylhexylamine, cyclopentylamine, cyclohexylamine, aniline, dimethylamine, diethylamine, di-n-propylamine, di-isopropylamine, di-n-butylamine, di-tert-butylamine, di-sec-butylamine, di-isobutylamine, di-tert-amylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-(2-ethylhexyl)amine, dicyclopentylamine. Dicyclohexylamine, diphenylamine, trimethylamine, triethylamine, tri-n-propylamine, tri-iso-propylamine, 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.

[0094] Furthermore, a compound with several, in particular with two or three, nitrogen atoms and with 2 to 20 carbon atoms can also be used as such a nitrogen-containing basic compound, wherein these nitrogen atoms each independently bear 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.

[0095] However, a saturated, semi-saturated, or unsaturated nitrogenous five- or six-membered ring heterocycle is particularly suitable as such a nitrogen-containing basic compound. This heterocycle may contain one, two, or three ring nitrogen atoms and may have one or two further ring heteroatoms from the oxygen and sulfur group and / or hydrocarbyl residues, in particular C1 to C4 alkyl residues and / or phenyl, and / or functional groups or heteroatoms as substituents, in particular fluorine, chlorine, bromine, nitro, and / or cyano. Examples include pyrrolidine, pyrrole, imidazole, 1,2,3- or 1,2,4-triazole, oxazole, thiazole, piperidine, pyrazine, pyrazine, pyrazole, pyridazine, pyrimidine, pyrazine, 1,2,3-, 1,2,4- or 1,2,5-triazine, and 1,2,5-oxathiazine. 2H-1,3,5-thiadiazine or morpholine.

[0096] However, pyridine or a derivative of pyridine (especially a mono-, di- or tri-C 1 - to C 4 -alkyl-substituted pyridine) such as 2-, 3-, or 4-methylpyridine (picolins), 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, 3,5- or 3,6-dimethylpyridine (lutidines), 2,4,6-trimethylpyridine (collidin), 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 is particularly suitable as such a nitrogen-containing basic compound.

[0097] One can use a single nitrogen-containing basic compound or mixtures of such nitrogen-containing basic compounds.

[0098] For the use of isobutene or an isobutene-containing monomer mixture as the monomer to be polymerized, both pure isobutene and isobutene-containing C4 hydrocarbon streams are suitable as isobutene sources in embodiments (A) and (B). Examples include C4 raffinates, in particular "Raffinate 1", C4 sections from isobutane dehydrogenation, C4 sections from steam crackers, and from FCC crackers (fluid-catalyzed cracking), provided they are largely free of the 1,3-butadiene they contain. A C4 hydrocarbon stream from an FCC refinery unit is also known as a "b / b" stream. Other suitable isobutene-containing C4 hydrocarbon streams include, for example, the product stream from a propylene-isobutane co-oxidation or the product stream from a metathesis unit, which are generally used after conventional purification and / or concentration.Suitable C4 hydrocarbon streams typically contain less than 500 ppm, preferably less than 200 ppm, of butadiene. The presence of 1-butene, as well as cis- and trans-2-butene, is largely uncritical. Typically, the isobutene concentration in the aforementioned C4 hydrocarbon streams is in the range of 30 to 60 wt.%. Thus, raffinate 1 generally consists essentially of 30 to 50 wt.% 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 unbranched butenes in raffinate 1 generally behave practically inertly, and only the isobutene is polymerized.

[0099] In a preferred embodiment, a technical C4 hydrocarbon stream with an isobutene content of 1 to 100 wt.%, in particular 1 to 99 wt.%, especially 1 to 90 wt.%, and particularly preferably 30 to 60 wt.%, is used as the monomer source for the polymerization. This includes, in particular, a raffinate 1 stream, a b / b stream from an FCC refinery unit, a product stream from a propylene-isobutane co-oxidation, or a product stream from a metathesis unit.

[0100] The aforementioned isobutene-containing monomer mixture can contain small amounts of contaminants such as water, carboxylic acids, or mineral acids without causing critical losses in yield or selectivity. It is advantageous to prevent the accumulation of these impurities by removing them from the isobutene-containing monomer mixture, for example, by adsorption onto solid adsorbents such as activated carbon, molecular sieves, or ion exchangers.

[0101] Monomer mixtures of isobutene or the isobutene-containing hydrocarbon mixture can also be reacted with olefinically unsaturated monomers that are copolymerizable with isobutene. If monomer mixtures of isobutene are to be copolymerized with suitable comonomers, the monomer mixture preferably contains at least 5 wt.%, more preferably at least 10 wt.%, and particularly at least 20 wt.% isobutene, and preferably at most 95 wt.%, more preferably at most 90 wt.%, and particularly at most 80 wt.% comonomers.

[0102] Potential copolymerizable monomers include: vinyl aromatics such as styrene and α-methylstyrene, C1 to C4 alkylstyrenes such as 2-, 3- and 4-methylstyrene and 4-tert-butylstyrene, halogenated styrenes such as 2-, 3- or 4-chlorostyrene, and isoolefins with 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 comonomers that can be used include olefins containing 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. Depending on the polymerization conditions, isoprene, 1-butene, and cis- and trans-2-butene can also be used as comonomers.

[0103] If copolymers are to be produced using the process according to the invention, the process can be designed to preferably yield statistical polymers or, more preferably, block copolymers. For example, to produce block copolymers, the various monomers can be added to the polymerization reaction one after the other, with the addition of the second comonomer occurring, in particular, only when the first comonomer has already been at least partially polymerized. In this way, diblock, triblock, and higher block copolymers are accessible, which, depending on the order of monomer addition, have a block of one or another comonomer as a terminal block. In some cases, however, block copolymers are also formed when all comonomers are added to the polymerization reaction simultaneously, but one of them polymerizes significantly faster than the other(s).This is particularly the case when isobutene and a vinylaromatic compound, especially styrene, are copolymerized in the process according to the invention. Block copolymers with a terminal polystyrene block are preferably formed. This is due to the fact that the vinylaromatic compound, especially styrene, polymerizes significantly more slowly than isobutene.

[0104] The polymerization can be carried out both continuously and batchwise. Continuous processes can be performed analogously to known prior art methods for the continuous polymerization of isobutene in the presence of boron trifluoride-based catalysts in the liquid phase.

[0105] The process according to the invention is suitable for carrying out the polymerization at both low temperatures, e.g., from -90°C to 0°C, and higher temperatures, i.e., at least 0°C, e.g., from 0°C to +30°C or from 0°C to +50°C. However, in embodiment (A), polymerization according to the process is preferably carried out at lower temperatures, generally from -70°C to -10°C, particularly from -60°C to -15°C, and in embodiment (B) at somewhat higher temperatures from -30°C to +50°C, particularly from 0°C to +30°C, for example, at room temperature (+20°C to +25°C).

[0106] If the polymerization according to the inventive process takes place at or above the boiling temperature 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.

[0107] Preferably, the polymerization according to the inventive process is carried out in the presence of an inert diluent. The inert diluent used should be suitable for reducing the increase in viscosity of the reaction solution that typically occurs during the polymerization reaction to such an extent that the dissipation of the heat generated by the reaction can be ensured. Suitable diluents are solvents or solvent mixtures that are inert with respect to the reagents used.Suitable diluents include, 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, as well as halogenated aromatic hydrocarbons and alkyl aromatics halogenated in the alkyl side chains such as chlorobenzene, monofluoromethylbenzene, difluoromethylbenzene and trifluoromethylbenzene, and mixtures of the aforementioned diluents. Chlorinated hydrocarbons, in particular pure chlorinated hydrocarbons, are preferred as halogenated hydrocarbons for the inert diluents mentioned above and below.Preferably, fluorocarbons are excluded from the inert diluents used here in order to largely eliminate residual fluorine content in the polymer. The inert portions of isobutene-containing C4 hydrocarbon streams also serve as diluents or as components of the aforementioned solvent mixtures.

[0108] 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 in halogenated aliphatic hydrocarbons, or in a mixture of at least one halogenated hydrocarbon, in particular a halogenated aliphatic hydrocarbon, and at least one aliphatic, cycloaliphatic or aromatic hydrocarbon as an inert diluent, for example a mixture of dichloromethane and n-hexane, typically in a volume ratio of 10:90 to 90:10, in particular from 50:50 to 85:15. Preferably, the diluents are freed from impurities such as water, carboxylic acids or mineral acids before their use, for example by adsorption onto solid adsorbents such as activated carbon, molecular sieves or ion exchangers.

[0109] In a further preferred embodiment (A), the polymerization according to the invention is carried out in halogen-free aliphatic or, in particular, halogen-free aromatic hydrocarbons, especially toluene. For this embodiment, water in combination with the aforementioned organic hydroxy compounds and / or the aforementioned organic halogen compounds, or especially as the sole initiator, has proven to be particularly advantageous.

[0110] 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 of halogenated aliphatic hydrocarbons or in a mixture of at least one halogenated aliphatic hydrocarbon and at least one aliphatic, cycloaliphatic or aromatic hydrocarbon as an inert diluent.

[0111] Preferably, the polymerization according to the inventive process is carried out under largely aprotic, and in particular under largely anhydrous, reaction conditions. Largely aprotic or largely anhydrous reaction conditions are understood to mean 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, the starting materials are therefore dried before use by physical and / or chemical means. In particular, it has proven advantageous to add a metal-organic compound, for example, an organolithium, organomagnesium, or organoaluminum compound, to the aliphatic or cycloaliphatic hydrocarbons used as solvents after conventional pre-purification and pre-drying, in an amount sufficient to largely remove the traces of water from the solvent.The solvent treated in this way is then preferably condensed directly into the reaction vessel. A similar procedure can be used with the monomers to be polymerized, particularly with isobutene or with isobutene-containing mixtures. Drying with other common drying agents such as molecular sieves or pre-dried oxides like aluminum oxide, silicon dioxide, calcium oxide, or barium oxide is also suitable. Halogenated solvents, for which drying with metals such as sodium or potassium or with metal alkyls is not feasible, are dried to remove water or traces of water using suitable drying agents, for example, calcium chloride, phosphorus pentoxide, or molecular sieves. Similarly, those starting materials for which treatment with metal alkyls is also unsuitable, such as vinylaromatic compounds, can be dried in the same manner.Even when water is used or co-used as an initiator, residual moisture from solvents and monomers should preferably be largely or completely removed by drying before reaction in order to be able to use the initiator water in a specified quantity, thereby achieving higher process control and reproducibility of the results.

[0112] The polymerization of isobutene or isobutene-containing feed material generally occurs spontaneously upon contact with 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 Lewis acid complex containing at least one organic sulfonic acid, with or without donors—with the isobutene or the isobutene-containing monomer mixture at the desired reaction temperature. This can be achieved by first preparing the monomers, if necessary in a diluent, bringing them to reaction temperature, and then adding 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.The aluminum trichloride donor complex, or the Lewis acid complex containing at least one organic sulfonic acid with or without donors, is added. 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 Lewis acid complex containing at least one organic sulfonic acid with or without donors—can be added, optionally in a diluent, followed by the addition of the monomers. The polymerization is then considered to have begun when all reactants are present in the reaction vessel.

[0113] Isobutene copolymers can be prepared by first adding the monomers, optionally in a diluent, and then adding the polymerization catalyst, i.e., 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 Lewis acid complex containing at least one organic sulfonic acid, with or without donors. The reaction temperature can be adjusted before or after the addition of the polymerization catalyst, i.e., 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 Lewis acid complex containing at least one organic sulfonic acid, with or without donors.One can also proceed by initially adding only one of the monomers, possibly in the diluent, then adding the polymerization catalyst, i.e., 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 Lewis acid complex containing at least one organic sulfonic acid 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 has reacted, adding the remaining monomer(s). Alternatively, one can add the polymerization catalyst, i.e., 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.Place the aluminum trichloride donor complex, or the Lewis acid complex containing at least one organic sulfonic acid with or without donors, optionally in the diluent, in the reaction vessel. Then add the monomers simultaneously or sequentially and adjust the desired reaction temperature. Polymerization begins when the polymerization catalyst, i.e., 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 Lewis acid complex containing at least one organic sulfonic acid with or without donors, and at least one of the monomers are present in the reaction vessel.

[0114] In addition to the discontinuous procedure described here, the polymerization according to the inventive process can also be carried out as a continuous process. In this case, the starting materials, i.e., the monomer(s) to be polymerized, optionally the diluent, and optionally the polymerization catalyst, i.e., 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 Lewis acid complex containing at least one organic sulfonic acid with or without donors, are continuously fed to the polymerization reaction, and reaction product is continuously removed, so that more or less steady-state polymerization conditions are established in the reactor.The monomer(s) to be polymerized can be supplied as such, diluted with a diluent or solvent, or as a monomer-containing hydrocarbon stream.

[0115] 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 Lewis acid complex containing at least one organic sulfonic acid with or without donors, which acts as a polymerization catalyst, is generally present in the polymerization medium in dissolved, dispersed, or suspended form. It is also possible to support 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 Lewis acid complex containing at least one organic sulfonic acid with or without donors on conventional support materials.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 batch fixed bed reactors (batch operation).

[0116] In the process according to the invention, 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 Lewis acid complex containing at least one organic sulfonic acid with or without donors, acting as a polymerization catalyst, is generally used in such an amount that the molar ratio of the element from groups 1 to 8 or from groups 3 to 5 of the periodic table, especially 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 Lewis acid complex containing at least one organic sulfonic acid with or without donors, is converted to isobutene by homopolymerization of isobutene or aluminum alkyl halide donor complex.The ratio of the total amount of polymerizable monomers used in the copolymerization of isobutene is in the range of 1:10 to 1:5000, in particular 1:15 to 1:1000, especially 1:20 to 1:250.

[0117] To terminate the reaction, the reaction mixture is preferably deactivated, for example by adding a protic compound, in particular by adding water, alcohols such as methanol, ethanol, n-propanol and isopropanol or their mixtures with water, or by adding an aqueous base, e.g. an aqueous solution of an alkali or alkaline earth hydroxide such as sodium hydroxide, potassium hydroxide, magnesium hydroxide or calcium hydroxide, an alkali or alkaline earth carbonate such as sodium, potassium, magnesium or calcium carbonate, or an alkali or alkaline earth hydrogen carbonate such as sodium, potassium, magnesium or calcium hydrogen carbonate.

[0118] In the process according to the invention, the described highly reactive isobutene homo- or copolymers with a content of terminal vinylidene double bonds (α-double bonds) per polyisobutene chain end of 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%, particularly preferably more than 91 mol% and in particular at least 95 mol%, e.g. nearly 100 mol%, are used for derivatization by introducing the low molecular weight polar groups A.In particular, highly reactive isobutene copolymers are also used, which are composed of isobutene and at least one vinylaromatic monomer, especially styrene, and which have a terminal vinylidene double bond (α-double bond) content per polyisobutene chain end of 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%, particularly preferably more than 91 mol%, and especially at least 95 mol%, e.g., nearly 100 mol%. To produce such copolymers from isobutene and at least one vinylaromatic monomer, especially styrene, isobutene or an isobutene-containing hydrocarbon fraction is combined with the at least one vinylaromatic monomer in a weight of...-Ratio of isobutene to vinyl aromatic of 5 to 95 to 95 to 5, especially of 30 to 70 to 70 to 30, copolymerized.

[0119] Preferably, the highly reactive isobutene homo- or copolymers used according to the invention, and especially the isobutene homopolymers, have a polydispersity (PDI = Mw / Mn) of 1.05 to less than 3.5, preferably of 1.05 to less than 3.0, preferably of 1.05 to less than 2.5, preferably of 1.05 to 2.3, particularly preferably of 1.05 to 2.0, and especially of 1.1 to 1.85. Typical values ​​for PDI under optimal process conditions are 1.2 to 1.7.

[0120] Preferably, the highly reactive isobutene homo- or copolymers used according to the invention have a number-average molecular weight Mn (determined by gel permeation chromatography) of preferably 500 to 250,000, particularly preferably 500 to 100,000, more preferably 500 to 25,000, and especially 500 to 5,000. Isobutene homopolymers even more preferably have a number-average molecular weight Mn of 500 to 10,000, and especially 500 to 5,000, e.g., of about 1,000 or about 2,300.

[0121] In particular, the process according to the invention is suitable for the production of isobutene homo- or copolymer derivatives of general formula I, in which the POL underlying hydrophobic n-functional residue was formed by homopolymerization of isobutene or copolymerization of isobutene with up to 20 wt% n-butene, is monofunctional and has a number-mean molecular weight (M n ) of 500 to 5000, especially 650 to 2500.

[0122] In particular, the process according to the invention is also suitable for the production of isobutene homo- or copolymer derivatives of general formula I, in which the POL underlying hydrophobic n-functional residue was formed by homopolymerization of isobutene or copolymerization of isobutene with up to 20 wt% n-butene, each using a di- or trifunctional initiator (inifer), is di- or trifunctional and has a number-average molecular weight (M n ) of 500 to 10,000, especially 1000 to 5000.

[0123] In particular, the process according to the invention is also suitable for the production of isobutene copolymer derivatives of general formula I, in which the POL underlying hydrophobic n-functional residue was formed by copolymerization of isobutene with at least one vinylaromatic comonomer, optionally using a di- or trifunctional initiator (inifers), is mono-, di- or trifunctional and has a number-mean molecular weight (M n ) of 500 to 15,000, especially 1000 to 10,000.

[0124] In a preferred embodiment of the inventive process for the preparation of isobutene homo- or copolymer derivatives of general formula I, the low molecular weight polar group A is selected from among (a) Mono- or polyamino groups with up to 6 nitrogen atoms, wherein at least one nitrogen atom has basic properties; (b) Nitro groups, optionally in combination with hydroxyl groups; (c) Hydroxyl groups, optionally in combination with mono- or polyamino groups, wherein at least one nitrogen atom has basic properties; (d) Carboxyl groups or their alkali metal or alkaline earth metal salts; (e) Sulfonic acid groups or their alkali metal or alkaline earth metal salts; (f) Polyoxy-C₂-C₄ alkyl groups terminated by hydroxyl groups, mono- or polyamino groups, wherein at least one nitrogen atom has basic properties, or by carbamate groups; (g) Carboxylic acid ester groups;(h) Succinic anhydride or groups derived from succinic anhydride with hydroxy and / or amino and / or quaternized amino and / or amido and / or imido groups, which were prepared by thermal or halogen-catalyzed maleation of the inner double bond(s) and the terminal vinylidene double bond(s) of the polyisobutene homo- or copolymers underlying the POL with maleic anhydride and, in the case of groups derived from succinic anhydride with hydroxy and / or amino and / or quaternized amino and / or amido and / or imido groups, by appropriate subsequent reactions, wherein a resulting carboxylic amide or carboxylic imide derivative may be further modified by further reaction with at least one C2 to C12 dicarboxylic anhydride, with at least one C2 to C4 alkylene carbonate and / or with boric acid;(j) groups produced by Mannich reaction of POL-substituted phenols with aldehydes and mono- or polyamines; (k) phenol, alkylphenol or (hydroxyalkyl)phenol groups; (i) hydroxymethyl groups;(m) Groups formed by epoxidation of the terminal vinylidene double bond(s) of the underlying polyisobutene homo- or copolymers and subsequent (i) hydrolysis to the 1,2-diol, (ii) reaction with a thiol or a polythiol, (iii) reaction with ammonia, a monoamine, or a polyamine, (iv) reaction with a borane to form a borate ester and oxidative cleavage of the borate ester to the 1,3-diol, (v) conversion to an aldehyde, (vi) conversion to an aldehyde and conversion of the aldehyde to an oxime and reduction of the oxime to the amine, (vii) conversion to an aldehyde and conversion of the aldehyde to an azo element cation and hydrolysis to the amine, (viii) conversion to an aldehyde and conversion of the aldehyde to an alcohol, or (ix) conversion to an aldehyde and conversion of the aldehyde to a Schiff compound. A base or an enamine and reduction of Schiff's base or the enamine to the amine were produced;(n) Groups generated by hydroboration of the terminal vinylidene double bond(s) of the polyisobutene homo- or copolymers underlying the POL and subsequent oxidation of the primary hydroboration product; and (o) Groups generated by hydrosilylation of the terminal vinylidene double bond(s) of the polyisobutene homo- or copolymers underlying the POL.

[0125] Examples of the above low molecular weight polar groups A include the following: Isobutene homo- or copolymer derivatives of general formula I containing mono- or polyamino groups (a) are generally based on highly reactive polyisobutene with predominantly terminal vinylidene double bonds, especially those with a number-mean molecular weight Mn of 300 to 5000. They may also contain some internal double bonds. Polyisobutenamines based on highly reactive polyisobutene, which may contain up to 20 wt% n-butene units, are available, for example, according to EP-A 244 616, by hydroformylation and reductive amination with ammonia, monoamines, or polyamines such as dimethylaminopropylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, or tetraethylenepentamine.If the synthesis of isobutene homo- or copolymer derivatives I starts with polyisobutene containing a proportion of internal double bonds (mostly in the β- and γ-positions), the synthesis route via chlorination followed by amination or by oxidation of the double bond with air or ozone to the carbonyl or carboxyl compound and subsequent amination under reductive (hydrogenating) conditions is also possible. Amines such as ammonia, monoamines, or polyamines such as dimethylaminopropylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, or tetraethylenepentamine can be used for amination.

[0126] Other preferred isobutene homo- or copolymer derivatives I containing (a) monoamino groups are the hydrogenation products of the reaction products of polyisobutenes with a mean degree of polymerization P = 5 to 100 with nitrogen oxides or mixtures of nitrogen oxides and oxygen, as described in particular in WO-A-97 / 03946.

[0127] Other preferred isobutene homo- or copolymer derivatives I containing (a) monoamino groups are the compounds obtainable from polyisobutene epoxides by reaction with amines and subsequent dehydration and reduction of the amino alcohols, as described in particular in DE-A-196 20 262.

[0128] Other preferred isobutene homo- or copolymer derivatives I containing (a) monoamino groups are the compounds obtainable from the reaction of highly reactive polyisobutene with one or more aromatic or heteroaromatic amines. For this purpose, the highly reactive polyisobutene can be reacted, for example, with aniline, N-methylaniline, N,N-dimethylaniline, o-, m- or p-toluidine, or o-, m- or p-aminopyridine to give the corresponding compound polyisobutyl-substituted at the aromatic or heteroaromatic ring. The aromatic amines used can also be multiply, in particular doubly, substituted at the ring, especially by alkyl groups such as C1 to C4 alkyl groups; typical substitution patterns for such substituents at the aromatic ring are the 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, or 3,5-positions.Typical compounds formed in this process include, for example, 4-polyisobutylaniline, 4-polyisobutyl-N-methylaniline, 4-polyisobutyl-N,N-dimethylaniline, 4-polyisobutyl-3-methylaniline, and 5-polyisobutyl-2-aminopyridine. The synthesis of such compounds, polyisobutyl-substituted at the aromatic or heteroaromatic ring, is generally carried out using standard methods of electrophilic aromatic substitution (Friedel-Crafts alkylation) at the aromatic or heteroaromatic ring, for example, using Lewis acids such as AlCl₃, ZnCl₂, or BF₃ as catalysts and at elevated temperatures, particularly 25 to 80°C or 25 to 250°C, if necessary in an inert solvent.

[0129] Isobutene homo- or copolymer derivatives I containing nitro groups (b), optionally in combination with hydroxyl groups, are preferably reaction products of polyisobutenes of medium degree of polymerization P = 5 to 100 or 10 to 100 with nitrogen oxides or mixtures of nitrogen oxides and oxygen, as described in particular in WO-A-96 / 03367 and WO-A-96 / 03479. These reaction products generally represent mixtures of pure nitropolyisobutenes (e.g., α,β-dinitropolyisobutene) and mixed hydroxynitropolyisobutenes (e.g., α-nitro-β-hydroxypolyisobutene).

[0130] Isobutene homo- or copolymer derivatives I containing hydroxyl groups in combination with mono- or polyamino groups (c) are, in particular, reaction products of polyisobutene epoxides obtainable from polyisobutene, preferably having predominantly terminal double bonds and with Mn = 300 to 5000, with ammonia, mono- or polyamines, as described in particular in EP-A-476 485. Isobutene homo- or copolymer derivatives I containing hydroxyl groups (c) that do not have mono- or polyamino groups are, for example, reaction products of polyisobutene epoxides obtainable from polyisobutene, preferably having predominantly terminal double bonds and with Mn = 300 to 5000, with water (hydrolysis) or with alcohols such as methanol or ethanol, or the products of a reduction of the epoxide function, for example by means of lithium aluminum hydride.Isobutene homo- or copolymer derivatives I containing carboxyl groups or their alkali metal or alkaline earth metal salts (d) are generally polyisobutenes into which one or more carboxyl groups have been introduced, for example by reaction with maleic anhydride, after which the carboxyl groups are wholly or partly reacted to the alkali metal or alkaline earth metal salts and a remaining residue of the carboxyl groups is reacted with alcohols or amines.

[0131] Isobutene homo- or copolymer derivatives I containing sulfonic acid groups or their alkali metal or alkaline earth metal salts (e) are generally polyisobutenes into which one or more sulfonic acid groups have been introduced, after which the sulfonic acid groups are wholly or partially converted to the alkali metal or alkaline earth metal salts, and any remaining carboxyl group is reacted with alcohols or amines. Analogous alkali metal or alkaline earth metal salts of alkyl sulfosuccinic acid esters are described in EP-A-639 632. Such compounds are mainly used to prevent valve seat wear and can be advantageously used in combination with common fuel detergents such as poly(iso)butenamines or polyetheramines.

[0132] Isobutene homo- or copolymer derivatives I containing polyoxy-C 2 -C 4 -alkyl groups (f) are preferably polyethers or polyetheramines which are obtainable by reacting hydroxyl- or amino-containing polyisobutenes with 1 to 30 mol of ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl group or amino group and - in the case of polyetheramines - by subsequent reductive amination with ammonia, monoamines or polyamines. Analogous reaction products of C 2-C 60 alkanols, C 6-C 30 alkanediols, mono- or di-C 2-C 30 alkylamines, C 1-C 30 alkylcyclohexanols or C 1-C 30 alkylphenols with 1 to 30 mol of ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl group or amino group are described in EP-A-310 875, EP-A-356 725, EP-A-700 985 and US-A-4 877 416.

[0133] Isobutene homo- or copolymer derivatives I containing carboxylic acid ester groups (g) are preferably esters of mono-, di-, or tricarboxylic acids with hydroxyl-containing polyisobutenes. Analogous reaction products of long-chain alkanols or polyols with mono-, di-, or tricarboxylic acids are described in DE-A-38 38 918. Aliphatic or aromatic acids can be used as mono-, di-, or tricarboxylic acids. Typical examples of such esters are corresponding adipates, phthalates, iso-phthalates, terephthalates, and trimellitates.

[0134] Isobutene homo- or copolymer derivatives containing succinic anhydride (h) are, in particular, polyisobutenyl succinic anhydrides, which can be obtained by reacting highly reactive polyisobutene with Mn = 500 to 5000 with maleic anhydride via a thermal process or via the chlorinated polyisobutene. The polyisobutene used can be reacted with 1 equivalent ("monomaleination"), with 2 equivalents of maleic anhydride ("bismaleination"), or with 1 < n < 2 equivalents of maleic anhydride, e.g., with 1.05 to 1.3 equivalents of maleic anhydride.

[0135] Isobutene homo- or copolymer derivatives I derived from succinic anhydride containing groups containing hydroxy and / or amino and / or quaternized amino and / or amido and / or imido groups (h) are preferably corresponding derivatives of polyisobutyl- or polyisobutenyl-substituted succinic anhydride and in particular the corresponding derivatives of polyisobutenyl succinic anhydride, which are obtainable by reacting highly reactive polyisobutene with M n = 300 to 5000, which may still contain portions of internal double bonds, with maleic anhydride by thermal means or via the chlorinated polyisobutene. Of particular interest are derivatives with alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol or polyethers, which have been produced by oxalkylation of the aforementioned low molecular weight alkanols with C 2 to C 4 alkylene oxides.Isobutene-containing C4 hydrocarbon streams and especially aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, or tetraethylenepentamine. The groups with hydroxy, and optionally quaternized, amino, amido, and / or imido groups include, for example, carboxylic acid groups, amides of monoamines, amides of di- or polyamines that, in addition to the amide function, also have free amine groups, succinic acid derivatives with one acid and one amide function, carboxylic acid imides with monoamines, carboxylic acid imides with di- or polyamines that, in addition to the imide function, also have free amine groups, or diimides formed by the reaction of di- or polyamines with two succinic acid derivatives. Such compounds are described as fuel additives in US-A-4,849,572.

[0136] Groups derived from succinic anhydride with isobutene homo- or copolymer derivatives containing quaternized amino groups are to be understood in particular as quaternized nitrogen compounds obtainable by the addition of a compound containing at least one oxygen- or nitrogen-containing group reactive with an anhydride and additionally at least one quaternizable amino group to polyisobutenyl succinic anhydride and subsequent quaternization, in particular with an epoxide, especially in the absence of free acid, as described in EP patent application no. 10 168 622.8. Polyamines with at least one primary or secondary amino group and at least one tertiary amino group are particularly suitable as compounds with at least one oxygen- or nitrogen-containing group reactive with an anhydride and additionally at least one quaternizable amino group.One such quaternized nitrogen compound is, for example, the reaction product obtained at 40°C of polyisobutenyl succinic anhydride, in which the polyisobutenyl residue typically has an M n of 1000, with 3-(dimethylamino)propylamine, which is a polyisobutenyl succinic hemiamide, and which is subsequently quaternized with styrene oxide in the absence of free acid at 70°C.

[0137] Carboxylic acid amide and carboxylic acid imide derivatives resulting in group (h) can, particularly when used in lubricant formulations, be further modified with at least one C 2 - to C 12 −dicarboxylic acid anhydride such as maleic anhydride or phthalic anhydride, with at least one C 2 - to C 4 −alkylene carbonate such as ethylene carbonate or propylene carbonate and / or with boric acid to improve the swelling behavior of elastomers which are installed, for example, in seals of engines, assemblies or devices that come into contact with the aforementioned derivatives or with lubricant formulations containing them.

[0138] Isobutene homo- or copolymer derivatives I, produced by Mannich reaction of substituted phenols with aldehydes and mono- or polyamines, containing groups (j), are preferably reaction products of polyisobutyl-substituted phenols with aldehydes such as formaldehyde, which can also be used, for example, in oligomeric or polymeric form, e.g., as paraformaldehyde, and with monoamines, e.g., dimethylamine, diethylamine, propylamine, butylamine, or morpholine, or with polyamines, e.g., ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, or dimethylaminopropylamine. The polyisobutyl-substituted phenols may contain not only terminal vinylidene double bonds but also portions of internal double bonds. Such "polyisobutene Mannich bases" based on highly reactive polyisobutene with M n = 300 to 5000 are described in EP-A-831 141.

[0139] Isobutene homopolymer or copolymer derivatives I containing phenol, alkylphenol, or (hydroxyalkyl)phenol groups (k) are, in particular, the precursors to the polyisobutene Mannich bases in group (j), which are formed by reacting highly reactive polyisobutene with one or more corresponding phenols, optionally with subsequent reaction with an aldehyde. For this purpose, the highly reactive polyisobutene can be reacted, for example, with unsubstituted phenol, o-, m-, or p-cresol, xylenol, hydroquinone, catechol, or resorcinol. Polyisobutyl-substituted phenol formed in this way can, for example, be further converted with an aldehyde such as formaldehyde or paraformaldehyde to a polyisobutyl-substituted hydroxyalkylphenol, in particular a polyisobutyl-substituted hydroxymethylphenol, e.g., to 1-hydroxymethyl-4-polyisobutylphenol.

[0140] Isobutene homo- or copolymer derivatives containing hydroxymethyl groups (I) are, in particular, intermediates in the hydroformylation of highly reactive polyisobutene according to EP-A 244 616 in the presence of carbon monoxide and hydrogen using a suitable hydroformylation catalyst such as a rhodium or cobalt catalyst at temperatures of 80 to 200°C and CO / H₂ pressures of up to 600 bar. A hydroxymethyl polyisobutene produced in this way can be obtained as a product mixture together with a polyisobutene containing an aldehyde group.

[0141] The groups listed in group (m) under (i) to (ix), which may be contained in the isobutene homo- or copolymer derivatives I, and their production are described in more detail in the context of subsequent reactions of isobutene polymer epoxides, for example in WO 2007 / 025700, and are reproduced below: The epoxide can be hydrolyzed with water to 1,2-diols, for example, or reacted with thiols or primary or secondary amines, yielding, among other things, glycol thioethers and amines.

[0142] By reacting an isobutene polymer, which has on average at least 0.7, preferably at least 0.9, epoxy groups per molecule, with polyols or in particular polythiols such as trimethylolpropane tris-(3-mercaptopropionate) or pentaerythritol tetrakis-(3-mercaptopropionate), or polyamines such as diethylenetriamine, networks are obtained which are advantageous due to their elastic and damping properties.

[0143] In a preferred subsequent reaction, the epoxide is rearranged to the aldehyde, which can be achieved, for example, under the catalysis of aluminosilicates (e.g., zeolites), acidic aluminum oxide, Lewis acids (such as aluminum or zinc salts, e.g., zinc bromide), or protic acids (e.g., sulfuric acid). The aldehyde, in turn, is a versatile starting material for valuable products. The conversion of polyisobutenyl epoxides to aldehydes is described, for example, in WO 90 / 10022 and US 6,303,703, or Organikum, 20th ed. 1999, Wiley-VCH, p. 615.

[0144] The aldehyde can be converted to an imine using ammonia or a primary amine, and the imine can be reduced to an amine, especially by catalytic hydrogenation. Suitable primary amines are, for example, diethylenetriamine, di(methylethylene)triamine, triethylenetetramine, tri(methylethylene)tetramine, tri(ethylethylene)tetramine, tetraethylenepentamine, pentaethylenehexamine, ethylenediamine, hexamethylenediamine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, alkyl-substituted o-, m- and p-phenylenediamine, dimethylaminomethylamine, dimethylaminoethylamine, dimethylaminopropylamine, dimethylaminobutylamine, dimethylaminoheptylamine, diethylaminomethylamine, diethylaminopropylamine, diethylaminoamylamine, dipropylaminopropylamine, methylpropylaminoamylamine, propylbutylaminoethylamine, dimethylentrianiline, methylenedianiline, polymethyleneaniline and polyalkylmethyleneaniline. The reaction of the aldehyde with the primary amine and the hydrogenation of the resulting imine to a polyisobutenylamine is described in WO 90 / 10022.

[0145] The aldehyde can also be converted to an oxime, and the oxime reduced to an amine. Conveniently, hydroxylamine, obtained by neutralizing a hydroxylamine salt, is used. The hydroxylamine reacts with the aldehyde to form the oxime. The oxime is then reduced to the amine by catalytic hydrogenation. The hydrogenation takes place at a suitable temperature and pressure in the presence of a hydrogenation catalyst. Suitable catalysts include, for example, Raney nickel, nickel on diatomaceous earth, copper chromite, platinum on carbon, palladium on carbon, and the like. The reaction is described, for example, in US 6,303,703.

[0146] In another preferred embodiment, the aldehyde is converted to an azomesis cation via a Leuckart reaction. Various reagents are suitable for carrying out the Leuckart reaction; ammonium formate is preferred. The azomesis cation can then be converted to an amine by hydrolysis. The hydrolysis can suitably be carried out with dilute hydrochloric acid at a moderately elevated temperature. Preferably, a phase-transfer catalyst such as tricaprylyl methylammonium nitrate is used. The reaction is described, for example, in US 6,303,703.

[0147] The epoxide can be further reacted with a borane and subsequently oxidatively cleaved the resulting borate ester to form a 1,3-diol, for example, 2-polyisobutenyl-1,3-propanediol. Suitable boranes include, for example, diborane (B₂H₆) as well as alkyl and arylboranes. It is known to those skilled in the art that such boranes can also be prepared in situ from a borohydride and an acid, usually BF₃ etherate. The reaction with the borane is carried out in a suitable manner in a borane-coordinating solvent. Examples include open-chain ethers such as dialkyl, diaryl, or alkyl aryl ethers, as well as cyclic ethers such as tetrahydrofuran or 1,4-dioxane, but solvents such as toluene, cyclohexane, and methylene chloride are also suitable. The oxidative cleavage to a 1,3-diol can be carried out, for example, using hydrogen peroxide in the presence of a base and heating to, for example, 15°C. B. 50 to 75°C.Suitable solvents for this are ethers or mixtures of ethers and hydrocarbons.

[0148] Groups (n) resulting from hydroboration reactions, which may be contained in the isobutene homo- or copolymer derivatives I, and their generation are described in more detail, for example, in WO 2004 / 067583. General principles of hydroboration are described in J. March, Advanced Organic Chemistry, 4th edition, J. Wiley & Sons, pp. 783-789.

[0149] Suitable sources of borane include, above all, borane (BH3) itself, which usually occurs in the form of its dimer (B2H6). Advantageously, the borane is generated in situ by reacting suitable precursors, especially alkali metal or alkaline earth metal salts of the BH4 anion, with boron trihalides. Sodium borohydride and boron trifluoride etherate are typically used for this purpose.

[0150] A preferred hydroboration agent for the terminal vinylidene double bonds of polyisobutene is the reaction product of a borane source, e.g., borane generated in situ from alkali metal or alkaline earth metal salts of the BH4 anion with boron trihalides, with 0.5 to 1.8 equivalents per mole of borane of an alkene with a molecular weight of less than 250, e.g., 2-methyl-2-butene or 1-methylcyclohexene.

[0151] The subsequent oxidation of the primary hydroboration product is typically carried out with alkaline hydrogen peroxide to obtain an alcohol that preferably corresponds formally to the anti-Markovnikov hydration product of the unsaturated isobutene polymer. Alternatively, the polyisobutylboranes obtained as the primary hydroboration product can also be subjected to an oxidative reaction with bromine in the presence of hydroxide ions to obtain the bromide.

[0152] Groups (o) resulting from hydrosilylation reactions, which may be contained in the isobutene homo- or copolymer derivatives I, and their production are described in more detail, for example, in WO 2003 / 074577. For this purpose, a highly reactive polyisobutene can be subjected to a reaction with a silane in the presence of a silylation catalyst to obtain a polyisobutene at least partially functionalized with silyl groups. Silylated isobutene polymers, in turn, represent valuable starting materials for subsequent reactions to new products, for example, for moisture-curing sealants and for formulations where glass adhesion plays a role.

[0153] Suitable hydrosilylation catalysts are, in particular, transition metal catalysts, where the transition metal is selected from Pt, Pd, Rh, Ru, and Ir, e.g., finely divided platinum, platinum chloride, hexachloroplatinic acid, tetramethyldivinyldisiloxane-platinum complexes, RhCl[P(C6H5)3]3, RhCl3, RuCl3, or IrCl3. Further suitable hydrosilylation catalysts include Lewis acids such as aluminum trichloride or titanium tetrachloride, as well as peroxides.

[0154] Suitable silanes include, for example, halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane and trimethylsiloxydichlorosilane, alkoxysilanes such as trimethoxysilane, triethoxysilane, methyldimethoxysilane, phenyldimethoxysilane, 1,3,3,5,5,7,7-heptamethyl-1,1-dimethoxytetrasiloxane and acyloxysilanes.

[0155] The reaction temperature for hydrosilylation is preferably in the range of 0 to 140°C, particularly 40 to 120°C. The reaction is usually carried out at atmospheric pressure, but can also be performed at elevated pressures, e.g., 1.5 to 20 bar, or reduced pressures, e.g., 200 to 600 mbar. The reaction can be carried out without solvent or in the presence of a suitable inert solvent such as toluene, tetrahydrofuran, or chloroform.

[0156] In a preferred embodiment, the inventive process for the preparation of isobutene homo- or copolymer derivatives of general formula I, in which A represents a low molecular weight polar group containing an amino function, is carried out by combining isobutene or an isobutene-containing monomer mixture in the presence of (A) an iron halide donor complex, an aluminum trihalide donor complex, or an aluminum alkyl halide donor complex acting as a polymerization catalyst, the donor of which is an organic compound with at least one ether function or a carboxylic ester function, in particular with the use of an initiator, or (B) at least one Lewis acid suitable as a polymerization catalyst or a complex acting as a polymerization catalyst consisting of at least one Lewis acid and at least one donor and in the presence of at least one initiator, wherein at least one initiator is an organic sulfonic acid of the general formula Z-SO₃H, in which the variable Z denotes a C₁ to C₂₀ alkyl group, a C₁ to C₂₀ haloalkyl group, a C₅ to C₈ cycloalkyl group, a C₆ to C₂₀ aryl group, or a C₇ to C₂₀ arylalkyl group. polymerized, the resulting highly reactive isobutene homo- or copolymer is hydroformylated with a suitable catalyst in the presence of carbon monoxide and hydrogen, and subsequently reductively aminated in the presence of at least n equivalents of ammonia or a mono- or polyamine.

[0157] The hydroformylation and reductive amination of highly reactive polyisobutenes are described, for example, in EP-A 244 616. The hydroformylation is typically carried out in the presence of carbon monoxide and hydrogen using a suitable hydroformylation catalyst, such as a rhodium or cobalt catalyst, at temperatures of 80 to 200°C and CO / H₂ pressures of up to 600 bar. The subsequent reductive amination of the resulting oxo product (hydroxymethylpolyisobutene or a product mixture of hydroxymethylpolyisobutene and polyisobutene aldehyde of the same carbon number) is generally performed at temperatures of 80 to 200°C and hydrogen pressures of up to 600 bar, particularly 80 to 300 bar.

[0158] In a further preferred embodiment, the inventive process for the preparation of isobutene homo- or copolymer derivatives of general formula I, in which A represents a low molecular weight polar group containing an amino function, is carried out by combining isobutene or an isobutene-containing monomer mixture in the presence of (A) an iron halide donor complex, an aluminum trihalide donor complex, or an aluminum alkyl halide donor complex acting as a polymerization catalyst, the donor being an organic compound with at least one ether function or a carboxylic ester function, in particular with the addition of an initiator, or (B) at least one Lewis acid suitable as a polymerization catalyst or a complex acting as a polymerization catalyst consisting 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 C₁ to C₂₀ alkyl group, a C₁ to C₂₀ haloalkyl group, a C₅ to C₈ cycloalkyl group, a C₆ to C₂₀ aryl group, or a C₇ to C₂₀ -arylalkyl group polymerized, the resulting highly reactive isobutene homo- or -co-polymer is treated with a suitable activating agent, in particular with chlorine, and then reacted with n equivalents of ammonia or a mono- or polyamine.

[0159] In a further preferred embodiment, the inventive process for the preparation of isobutene homo- or copolymer derivatives of general formula I, in which A represents a low molecular weight polar group containing a carboxylic acid derivative function, in particular a carboxylic acid imide function, is carried out by combining isobutene or an isobutene-containing monomer mixture in the presence of (A) an iron halide donor complex, an aluminum trihalide donor complex, or an aluminum alkyl halide donor complex acting as a polymerization catalyst, the donor of which is an organic compound with at least one ether function or a carboxylic ester function, in particular with the use of an initiator; or (B) at least one Lewis acid suitable as a polymerization catalyst or a complex acting as a polymerization catalyst consisting 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 C₁ to C₂₀ alkyl group, a C₁ to C₂₀ haloalkyl group, a C₅ to C₈ cycloalkyl group, a C₆ to C₂₀ aryl group, or a C₇ to C₂₀ arylalkyl group. designated, polymerized, the resulting highly reactive isobutene homo- or copolymer with an ethylene-unsaturated C 4 - to C 12 -Dicarboxylic acid or a reactive derivative thereof, in particular with maleic anhydride, reacts thermally or halogen-catalyzed and optionally subsequently with a mono- or polyamine to form the corresponding carboxylic acid amide or carboxylic acid imide derivative, wherein the resulting carboxylic acid amide or carboxylic acid imide derivative is further converted by further reaction with at least one C 2 - to C 12 -Dicarboxylic anhydride, with at least one C 2 - to C 4 -Alkylene carbonate and / or can be modified with boric acid.

[0160] In a further preferred embodiment, the inventive process for the preparation of isobutene homo- or copolymer derivatives of general formula I, in which A represents a low molecular weight polar group containing an amino function, is carried out by combining isobutene or an isobutene-containing monomer mixture in the presence of (A) an iron halide donor complex, an aluminum trihalide donor complex, or an aluminum alkyl halide donor complex acting as a polymerization catalyst, the donor of which is an organic compound with at least one ether function or a carboxylic ester function, in particular with the use of an initiator, or (B) at least one Lewis acid suitable as a polymerization catalyst or a complex acting as a polymerization catalyst consisting of at least one Lewis acid and at least one donor and in the presence of at least one initiator, wherein at least one initiator is an organic sulfonic acid of the general formula Z-SO₃H, in which the variable Z denotes a C₁ to C₂₀ alkyl group, a C₁ to C₂₀ haloalkyl group, a C₅ to C₈ cycloalkyl group, a C₆ to C₂₀ aryl group, or a C₇ to C₂₀ arylalkyl group. polymerized, the resulting highly reactive isobutene homo- or -co-polymer is converted with a phenol into the corresponding alkylphenol and subsequently converted into the corresponding Mannich adduct by reaction with an aldehyde and a primary or secondary amine.

[0161] The present invention also relates to new isobutene homopolymer derivatives of general formula II in the R10<, R11< and R12< independently hydrogen, C1- to C20-alkyl, C5- to C8-cycloalkyl, C6- to C20-aryl, C7- to C20-alkylaryl or phenyl, wherein an aromatic ring further comprises one or more C1- to C4-alkyl or C1- to C4-alkoxy residues or groups of general formula III may be designated as substituents, wherein at most one of the variables R 10< , R 11< or R 12< denotes hydrogen and at least one of the variables R 10< , R 11< or R 12< denotes phenyl, which may also bear one or more C 1 to C 4 alkyl or C 1 to C 4 alkoxy groups or one or two groups of general formula III as substituents, Y denotes an isobutylene or an isobutenylene bridging unit, A denotes a low molecular weight polar group which contains one or more amino functions and / or nitro groups and / or a hydroxyl group and / or a carboxylic acid or carboxylic acid derivative functions, in particular succinic anhydride or succinic acid derivative functions, and / or sulfonic acid or sulfonic acid derivative functions and / or aldehyde functions and / or silyl groups, y for a number from 1 to 350, in particular from 9 to 100, especially those aged 12 to 50, stands,where, in telechelic isobutene homopolymer derivatives II, the two or three variables y in the molecule can be the same or different, and z represents the number 0 or preferably the number 1.

[0162] The isobutene homo- and copolymer derivatives produced according to the invention are suitable, for example, as fuel and lubricant additives.

[0163] The isobutene homo- or copolymer derivatives produced according to the invention are manufactured from isobutene polymers with 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 consistency of these derivatives, for example their color, are improved. The physical properties of these derivatives, in particular their viscosity behavior at low temperatures, as well as their solubilities, especially in polar media, their temperature stability, and their storage stability, are also improved. The catalyst system used for the production of the isobutene polymers in the precursor stage is sufficiently active, long-lasting, easy to handle, and resistant to malfunctions; in particular, it is fluorine-free, thus preventing undesirable corrosion on metallic materials and steel grades caused by residual fluorine content.

Claims

1. Process for the preparation of isobutene homo- or copolymer derivatives of the general formula I POL(-A) n (I) in the POL, the n-functional residue of a hydrophobic polyisobutene homo- or copolymer having a number-average molecular weight (M n) from 110 to 250,000, which can contain structural units from mono-, di- or trifunctional initiators, A is a low molecular weight polar group, each of which contains one or more amino functions and / or nitro groups and / or hydroxyl groups and / or mercaptan groups and / or carboxylic acid or carboxylic acid derivative functions, in particular succinic anhydride or succinic acid derivative functions, and / or sulfonic acid or sulfonic acid derivative functions and / or aldehyde functions and / or silyl groups, and the variable n stands for the number 1, 2 or 3, where n = 2 and n = 3 the variables A can be the same or different, where the low molecular weight polar group A is selected from the group consisting of (a) mono- or polyamino groups with up to 6 nitrogen atoms, where at least one nitrogen atom has basic properties; (b) nitro groups, optionally in combination with hydroxyl groups;(c) hydroxyl groups, optionally in combination with mono- or polyamino groups, wherein at least one nitrogen atom has basic properties; (d) carboxyl groups or their alkali metal or alkaline earth metal salts; (e) sulfonic acid groups or their alkali metal or alkaline earth metal salts; (f) polyoxy-C2-C4-alkylene groups substituted by hydroxyl groups, mono- or polyamino groups, wherein at least one nitrogen atom has basic properties; (g) carboxylic acid ester groups;(h) succinic anhydride or groups derived from succinic anhydride with hydroxyl and / or amino and / or quaternized amino and / or amido and / or imido groups, which were prepared by thermal or halogen-catalyzed maleation of the internal double bond(s) and the terminal vinylidene double bond(s) of the polyisobutene homo- or copolymers underlying POL with maleic anhydride and, in the case of groups derived from succinic anhydride with hydroxyl and / or amino and / or quaternized amino and / or amido and / or imido groups, by corresponding subsequent reactions, wherein a resulting carboxamide or carboximide derivative is further reacted with at least one C2 to C; 12-dicarboxylic acid anhydride, with at least one C2- to C4-alkylene carbonate and / or with boric acid; (j) moieties produced by Mannich reaction of POL-substituted phenols with aldehydes and mono- or polyamines; (k) phenol, alkylphenol or (hydroxyalkyl)phenol moieties; (I) hydroxymethyl groups;(m) Groupings formed by epoxidation of the terminal vinylidene double bond(s) of the polyisobutene homo- or copolymers underlying POL and subsequent (i) hydrolysis to the 1,2-diol, (ii) reaction with a thiol or a polythiol, (iii) reaction with ammonia, a monoamine or a polyamine, (iv) reaction with a borane to a borate ester and oxidative cleavage of the borate ester to the 1,3-diol, (v) conversion to an aldehyde, (vi) conversion to an aldehyde and conversion of the aldehyde to an oxime and reduction of the oxime to the amine, (vii) conversion to an aldehyde and conversion of the aldehyde to an azomethine cation and hydrolysis to the amine, (viii) conversion to an aldehyde and conversion of the aldehyde to an alcohol or (ix) conversion to an aldehyde and conversion of the aldehyde to a Schiff base or an enamine and reduction of the Schiff base or the enamine to the amine;(n) moieties produced by hydroboration of the terminal vinylidene double bond(s) of the polyisobutene homo- or copolymers underlying POL and subsequent oxidation of the primary hydroboration product; and (o) moieties produced by hydrosilylation of the terminal vinylidene double bond(s) of the polyisobutene homo- or copolymers underlying POL; characterized in thatisobutene or a monomer mixture containing isobutene is polymerized in the presence of (A) an aluminum trihalide donor complex which acts as a polymerization catalyst or an aluminum alkyl halide donor complex which contains an organic compound having at least one ether function or one carboxylic acid ester function as donor, the resulting highly reactive isobutene homo- or copolymer which has a content of at least 50 mol% of terminal vinylidene double bonds per polyisobutene chain end is reacted with at least n equivalents of a compound which introduces the low molecular weight polar group A or a partial structure of the low molecular weight polar group A, and in the case of the reaction with a partial structure, the formation of the low molecular weight polar group A is completed by subsequent reactions.

2. Method according to claim 1, characterized in thataccording to embodiment (A), the polymerization catalyst used is an aluminum trihalide donor complex or an aluminum alkyl halide donor complex which has as donor a dihydrocarbyl ether of the general formula R 1 -OR 2 in which the variables R 1 and R 2 independently of each other C1 to C 20 -alkyl radicals, C5- to C8-cycloalkyl radicals, C6- to C 20 -aryl residues or C7-to C 20 -arylalkyl radicals.

3. Method according to claim 1, characterized in that according to embodiment (A), the polymerization catalyst used is an aluminum trihalide donor complex or an aluminum alkyl halide donor complex which contains as donor a carboxylic acid hydrocarbyl ester of the general formula R 3 -COOR 4 in which the variables R 3 and R 4 independently of each other C1 to C 20 -alkyl radicals, C5 to Cs cycloalkyl radicals, C6 to C 20-aryl residues or C7- to C 20 -arylalkyl radicals.

4. Method according to one of the preceding claims, characterized in that according to embodiment (A), an aluminum trihalide donor complex or an aluminum alkyl halide donor complex is used as the polymerization catalyst, in which the donor compound has a total carbon number of 3 to 16.

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

6. Method according to claim 5, 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.

7. Process according to claims 1 to 6, characterized in that according to embodiment (A), the polymerization is carried out in the presence of 0.01 to 10 mmol, in each case based on 1 mol of isobutene monomer used in the case of homopolymerization of isobutene or on 1 mol of the total amount of polymerizable monomers used in the case of copolymerization of isobutene, of a nitrogen-containing basic compound.

8. Method according to claim 7, characterized in that pyridine or a derivative of pyridine is used as the nitrogen-containing basic compound.

9. Process according to claims 1 to 8, characterized in that according to embodiment (A), the polymerization is carried out in a halogenated aliphatic hydrocarbon or in a mixture of halogenated aliphatic hydrocarbons or in a mixture of at least one halogenated aliphatic hydrocarbon and at least one aliphatic, cycloaliphatic or aromatic hydrocarbon or in a halogen-free aliphatic or halogen-free aromatic hydrocarbon as inert diluent.

10. Process according to claims 1 to 9, characterized in that 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 from a propylene-isobutane co-oxidation or a product stream from a metathesis unit, is used as the monomer source for the polymerization.

11. Process according to claims 1 to 10 for the preparation of isobutene homopolymer or copolymer derivatives of the general formula I, in which the hydrophobic n-functional radical on which the POL is based was formed by homopolymerization of isobutene or copolymerization of isobutene with up to 20 wt.% n-butene, is monofunctional and has a number-average molecular weight (M n ) from 500 to 5000.

12. Process according to claims 1 to 11 for the preparation of isobutene homopolymers or copolymers of the general formula I, in which the hydrophobic n-functional radical on which the POL is based was formed by homopolymerization of isobutene or copolymerization of isobutene with up to 20% by weight of n-butene, in each case using a di- or trifunctional initiator (inifer), is di- or trifunctional and has a number-average molecular weight (M n ) from 500 to 10,000.

13. Process according to claims 1 to 12 for the preparation of isobutene copolymer derivatives of the general formula I, in which the hydrophobic n-functional radical on which POL is based was formed by copolymerization of isobutene with at least one vinylaromatic comonomer, optionally with the use of a di- or trifunctional initiator (inifer), is mono-, di- or trifunctional and has a number-average molecular weight (M n ) from 500 to 15,000.

14. A process for the preparation of isobutene homo- or copolymer derivatives of the general formula I, in which A is a low molecular weight polar group containing an amino function, according to claims 1 to 13, characterized in thatisobutene or a monomer mixture containing isobutene is polymerized in the presence of (A) an aluminum trihalide donor complex which acts as a polymerization catalyst or an aluminum alkyl halide donor complex which contains an organic compound having at least one ether function or one carboxylic acid ester function as donor, in particular with the use of an initiator, the resulting highly reactive isobutene homo- or copolymer is hydroformylated with a suitable catalyst in the presence of carbon monoxide and hydrogen and then reductively aminated in the presence of at least n equivalents of ammonia or a mono- or polyamine.

15. A process for the preparation of isobutene homo- or copolymer derivatives of the general formula I, in which A is a low molecular weight polar group containing an amino function, according to claims 1 to 13, characterized in thatisobutene or a monomer mixture containing isobutene is polymerized in the presence of (A) an aluminum trihalide donor complex acting as a polymerization catalyst or an aluminum alkyl halide donor complex which contains an organic compound having at least one ether function or one carboxylic acid ester function as donor, in particular with the use of an initiator, the resulting highly reactive isobutene homo- or copolymer is treated with a suitable activating agent, in particular with chlorine, and then reacted with n equivalents of ammonia or a mono- or polyamine.

16. A process for the preparation of isobutene homo- or copolymer derivatives of the general formula I, in which A is a low molecular weight polar group containing a carboxylic acid derivative function, in particular a carboximide function, according to claims 1 to 13, characterized in thatisobutene or a monomer mixture containing isobutene is polymerized in the presence of (A) an aluminum trihalide donor complex acting as a polymerization catalyst or an aluminum alkyl halide donor complex containing an organic compound having at least one ether function or one carboxylic acid ester function as donor, in particular with the use of an initiator, the resulting highly reactive isobutene homo- or copolymer having an ethylenically unsaturated C4 to C 12 -dicarboxylic acid or a reactive derivative thereof, in particular with maleic anhydride, thermally or halogen-catalyzed and optionally subsequently converted with a mono- or polyamine into the corresponding carboxamide or carboximide derivative, wherein the resulting carboxamide or carboximide derivative is further reacted with at least one C2 to C 12-dicarboxylic anhydride, can be modified with at least one C2 to C4 alkylene carbonate and / or with boric acid.

17. A process for the preparation of isobutene homo- or copolymer derivatives of the general formula I, in which A is a low molecular weight polar group containing an amino function, according to claims 1 to 13, characterized in thatisobutene or a monomer mixture containing isobutene is polymerized in the presence of (A) an aluminum trihalide donor complex acting as a polymerization catalyst or an aluminum alkyl halide donor complex which contains an organic compound having at least one ether function or one carboxylic acid ester function as donor, in particular with the use of an initiator, the resulting highly reactive isobutene homo- or copolymer is converted into the corresponding alkylphenol with a phenol and this is then converted into the corresponding Mannich adduct by reaction with an aldehyde and a primary or secondary amine.