BR112020001415B1 - PROCESS FOR THE PREPARATION OF HIGH REACTIVITY HOMO OR COPOLYMERS OF ISOBUTENE - Google Patents

Abstract

The present invention relates to a new process for the preparation of highly reactive isobutene homo- or copolymers with a content of terminal vinylidene double bonds per end of the polyisobutene chain of at least 70 mol%. The present invention also relates to new isobutene polymers.

Description

[001] The present invention relates to a new process for the preparation of highly reactive isobutene homo- or copolymers with a content of terminal vinylidene double bonds per end of the polyisobutene chain of at least 70 mol%. The present invention also relates to new isobutene polymers.

[002] Unlike the so-called low-reactivity polymers, high-reactivity isobutene homo- or copolymers are understood as polyisobutenes that comprise a high content of terminal ethylenic double bonds (α-double bonds)) and other susceptible reactive double bonds. to subsequent reactions, such as the Alder-Ene reaction with maleic acid anhydride, specifically in practice generally at least 70%, preferably at least 75% and most preferably at least 80 mol%, based on the ends of the chains individual polyisobutene macromolecules. In the context of the present application, vinylidene groups are understood to mean those terminal ethylenic double bonds whose position in the polyisobutene macromolecule is described by the general formula that is, the double bond is present at an α position in the polymer chain. "Polymer" represents the polyisobutene radical shortened by an isobutene unit. Vinylidene groups exhibit the greatest reactivity, for example, in the thermal addition of sterically demanding reagents such as maleic anhydride, while a double bond further into the macromolecules in most cases exhibits less reactivity, if any, in functionalization reactions. . Uses of highly reactive polyisobutenes include use as intermediates in the preparation of additives for lubricants and fuels, as described, for example, in DE-A 27 02 604.

[003] Such highly reactive polyisobutenes are obtainable, for example, by the process of DE-A 27 02 604 by cationic polymerization of isobutene in the liquid phase in the presence of boron trifluoride as a catalyst. A disadvantage here is that the polyisobutenes obtained have a relatively high polydispersity. Polydispersity is a measure of the distribution of the molecular weight of the resulting polymer chains and corresponds to the quotient of the weight-average molecular weight Mw and the numerical average molecular weight Mn (PDI = Mw/Mn).

[004] Polyisobutenes with an equally high proportion of terminal double bonds, but with a molecular weight distribution are, for example, obtained by the process of EP-A 145 235, US 5 408 018 and WO 99/64482, the polymerization being carried out in the presence of a deactivated catalyst, for example, a complex of boron trifluoride with alcohols and/or ethers.

[005] It has been known for some time that Lewis acid aluminum trichloride can also be used as a polymerization catalyst for isobutene, for example, from High Polymers, volume XXIV (part 2), p. 713-733 (editor: Edward C. Leonard), publishers of J. Wiley & Sons, New York, in the literature article "Cationic Polymerization Using Heteropolyacid Salt Catalysts" in Topics in Catalysis Vol. 23, p. 175-181 (2003), James D. Burrington et al. indicate that, with aluminum trichloride as an isobutene polymerization catalyst, only low-reactivity polyisobutenes with a low content of terminal vinylidene double bonds (α double bonds) can be obtained. For example, table 1 on page 178 of this literature article cites an example of polyisobutene prepared with AlCl3, which has a number average molecular weight Mn of 1000-2000, a polydispersity Mw/Mn of 2.5-3.5, and a vinylidene isomer content (double-α bond) of just 5% (in addition to 65% "tri", 5% "β" and 25% "tetra").

[006] In the literature article "New AlCl3 etherate-based initiation system for quasi-live cationic polymerization of styrene" in Polymer Bulletin vol. 52, p. 227-234 (2004), Sergei V. Kostjuk et al. describe a catalyst system composed of 2-phenyl-2-propanol and an aluminum trichloride/di-n-butyl ether complex for styrene polymerization. 2-Phenyl-2-propanol acts as a polymerization initiator, but does not significantly form alkoxyaluminum compounds. The Mw/Mn polydispersities of the styrene polymers thus prepared are "~2.5" (see summary) or "~3" (see page 230).

[007] Document WO 11/101281 discloses the preparation of highly reactive polyisobutene polymers by polymerizing a mixture of isobutene-containing monomers in the presence of an aluminum trihalide donor complex acting as a polymerization catalyst. The donor complex comprises an organic compound having at least one ether function or one carboxylic acid function as the donor.

[008] However, a disadvantage of AlCl3 is its low solubility in organic aprotic solvents, which requires the use of halogenated solvents such as methylene chloride or chloroform as a solvent. Therefore, a catalyst is needed with improved solubility in organic solvents, mainly halide-free solvents such as toluene or alkanes such as pentane, hexane or heptane isomers.

[009] Dmitriy I. Shiman, Irina V. Vasilenko, Sergei V. Kostjuk, Journal of Polymer Science, Part A: Polymer Chemistry 2014, 52, 23862393 disclose the preparation of polyisobutene polymers by polymerization of isobutene in the presence of a halide alkylaluminum and an ether complex as polymerization catalyst.

[0010] Unpublished International Application PCT/EP2017/053098, filed on February 13, 2017, discloses the preparation of highly reactive polyisobutene polymers with narrow polydispersity by polymerization of a mixture of isobutene-containing monomers in the presence of a donor complex alkylaluminum halide, said complex comprising, as the donor, a mixture of at least two organic compounds with at least one ether function each.

[0011] It was an object of the present invention to provide a process for the preparation of highly reactive isobutene homo- or copolymers with an increased content of terminal vinylidene double bonds per end of the polyisobutene chain of at least 70 mol% and simultaneously with a narrow molecular weight distribution (i.e. low polydispersities) in acceptable yields without the need to use mixing of different donors. The catalyst system must have both sufficient activity and useful life, its handling must be unproblematic and it must not be prone to failure.

[0012] The objective was achieved through a process of preparing highly reactive isobutene homo- or copolymers, with a content of terminal vinylidene double bonds per end of the polyisobutene chain of at least 70%, preferably at least 75%. and more preferably at least 80 mol%, which comprises polymerizing isobutene or a mixture of monomers comprising isobutene in the presence of a hydrocarbyloxy aluminum compound Al(ORa)p(Rb)qXr, or mixtures thereof, wherein Ra and Rb, independently of another, represent an organic residue of up to 20 carbon atoms, preferably C1 to C20 alkyl radical, C5 to C8 cycloalkyl radical, C6 to C20 aryl radical or C7 to C20 arylalkyl radical, , independently of another, represents a rational number greater than 0 (zero) and less than 3, q, independently of another, represents a rational number of at least 0 (zero) and less than 3, and r, independently of another, represents a rational number of at least 0 (zero) and less than 3, with the proviso that the sum of (p + q + r) is always 3, effective as a polymerization catalyst, optionally in the presence of at least one donor compound.

[0013] Isobutene homopolymers are understood in the context of the present invention to mean those polymers which, based on the polymer, are formed from isobutene to an extent of at least 98 mol%, preferably to an extent of at least 99%. in moles. Thus, isobutene copolymers are understood to mean those polymers comprising less than 2 mol%, preferably less than 1 mol%, more preferably less than 0.7 mol% and especially less than 0.5 mol% of copolymerized monomers. other than isobutene, for example isoprene or linear butenes, preferably 1-butene, cis-2-butene and trans-2-butene.

[0014] In the context of the present invention, the following definitions apply to generally defined radicals:

[0015] A C1 to C8 alkyl radical is a linear or branched alkyl radical with 1 to 8 carbon atoms. Its examples are methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethyl-propyl, 1 -ethylpropyl, n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3 - dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1 - methylpropyl, 1-ethyl-2-methylpropyl, n-heptyl, n-octyl and institutional isomers thereof, such as 2-ethylhexyls. These C1 to C8 alkyl radicals may to a small extent also comprise heteroatoms such as oxygen, nitrogen or halogen atoms, for example chlorine, and/or aprotic functional groups, for example carboxylic ester groups, cyano groups or nitro groups. However, radicals consisting merely of carbon and hydrogen are preferred.

[0016] A C1 to C4 alkyl radical is methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl or tert-butyl.

[0017] A C1 to C20 alkyl radical is a linear or branched alkyl radical with 1 to 20 carbon atoms. Examples thereof are the aforementioned C1 to C8 alkyl radicals and, additionally, n-nonyl, isononyl, n-decyl, 2-propylheptyl, n-undecyl, n-dodecyl, n-tridecyl, isotridecyl, n-tetradecyl, n-hexadecyl, n-octadecyl and n-eicosyl. These C1 to C20 alkyl radicals may, to a small extent, also comprise heteroatoms such as oxygen, nitrogen or halogen atoms, for example chlorine, and/or aprotic functional groups, for example carboxylic ester groups, cyano groups or nitro groups. However, radicals consisting merely of carbon and hydrogen are preferred.

[0018] A C5 to C8 cycloalkyl radical is a saturated cyclic radical that can comprise alkyl side chains. Examples thereof are cyclopentyl, 2- or 3-methylcyclopentyl, 2,3-, 2,4- or 2,5-dimethylcyclopentyl, cyclohexyl, 2-, 3- or 4-methylcyclohexyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, 3,5- or 3,6-dimethylcyclohexyl, cycloheptyl, 2-, 3- or 4-methylcyclohexyl, cyclo - octyl, 2-, 3-, 4- or 5-methylcyclooctyl. These C5 to C8 cycloalkyl radicals may also, to a small extent, also include heteroatoms, such as oxygen, nitrogen or halogen atoms, for example, chlorine, and/or functional groups, for example, carboxylic ester groups, cyano groups or nitro groups. However, radicals consisting merely of carbon and hydrogen are preferred.

[0019] A C6 to C20 arylalkyl radical or a C6 to C12 arylalkyl radical is preferably optionally substituted, optionally substituted naphthyl, optionally substituted anthracenyl or optionally substituted phenanthrenyl. Such aryl radicals may be 1 to 5 aprotic substituents or aprotic 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 radicals are phenyl, naphthyl, biphenyl, anthracenyl, phenanthrenyl, tolyl, nitrophenyl, chlorophenyl, dichlorophenyl, pentafluorophenyl, pentachlorophenyl, (trifluoromethyl)phenyl, bis(trifluoromethyl)phenyl, (trichloro)methylphenyl and bis(trichloromethyl)phenyl. However, radicals that purely consist of carbon and hydrogen are preferred.

[0020] A C7 to C20 arylalkyl radical or a C7 to C12 arylalkyl radical is preferably 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 alkylphenanthracenyl such as phenanthrenylmethyl. Such arylalkyl radicals may bear 1 to 5 aprotic substituents or aprotic functional groups, especially in the moiety, 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 or phenyl. However, radicals merely consisting of carbon and hydrogen are preferred.

[0021] The halide is fluoride, chloride, bromide or iodide, preferably fluoride, chloride or bromide, more preferably chloride or bromide and especially chloride.

[0022] In a preferred embodiment, hydrocarbyloxy aluminum compounds are used as mixtures of at least two of the aforementioned compounds.

[0023] Among the hydrocarbyloxy residues, the C1 to C20 alkyloxy and C6 to C20 aryloxy radicals are preferred, and the C1 to C8 alkyloxy and C6 to C12 aryloxy radicals are more preferred, with the C1 to C4 alkyloxy groups being the most preferred. Alkyl groups are preferred over aryl groups.

[0024] Among the alkyl groups, C1 to C8 alkyl groups are more preferred and C1 to C4 alkyl groups are more preferred.

[0025] Among the halides X fluoride, chloride and bromide are preferred, chloride and bromide are more preferred and chloride is the most preferred.

[0026] The preferred organic residues Ra are methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl and phenyl, very preferred are isopropyl, n-butyl and tert-butyl.

[0027] The preferred organic residues Rb are methyl, ethyl, n-propyl, isopropyl, n-butyl and isobutyl, very preferred are ethyl and isobutyl.

[0028] Useful hydrocarbyloxy aluminum compounds are bis (hydrocarbyloxy) aluminum monohalides, mono (hydrocarbyloxy) aluminum dihalides, mono hydrocarbyloxy monoalkyl aluminum halides, bis (hydrocarbyloxy) monoalkyl aluminum compounds, mono (hydrocarbyloxy) compounds ) bis alkyl aluminum, and mixtures thereof.

[0029] In the case of mixtures of the compounds Al(ORa)p(Rb)qXr, the values of p, q and r can represent rational numbers for the mixtures, for each individual compound the values of p, q and r are integers.

[0030] Preferably, p is from 0.5 to 1.5, more preferably from 0.7 to 1.3 and especially from 0.8 to 1.2.

[0031] Preferably q is not greater than 2, more preferably is not greater than 1 and r is always 3 - p - q.

[0032] In a preferred embodiment, q is 0 (zero). In this case, the most preferred aluminum hydrocarbyloxy compounds are Al(ORa)0.7 - 1.2X1.8 - 2.3.

[0033] According to the invention, the hydrocarbyloxy aluminum compound or mixtures thereof effective as a polymerization catalyst preferably comprises at least one donor compound.

[0034] Donor compounds are organic compounds comprising at least one oxygen or nitrogen atom with at least one pair of non-bonding electrons, preferably at least one oxygen atom, more preferably exactly one oxygen atom.

[0035] The donor is preferably selected from the group consisting of ethers, hydrocarbyl carboxylates, ethers, alcohols, aldehydes, ketones and phenols.

[0036] Alcohols or phenols as donors or initiators, especially 2-phenyl-2-propanol, described in Sergei V. Kostjuk et al., Polymer Bulletin Vol. 52, p. 227-234 (2004), together with aluminum halides, especially AlCl3, do not form the hydrocarbyloxy aluminum compounds effective as catalysts according to the present invention, but, in contrast, produce ion pairs according to the following formula: CumOH + AlCl3 → Cum+ AlCl3(OH)-

[0037] With CumOH = 2-phenyl-2-propanol.

[0038] For the sake of clarity, the catalysts according to the present invention are preferably free of any additional Bronsted acids, more preferably free of any hydrogen halide acids of the halide used as aluminum halide in the reaction, and especially free of hydrogen chloride.

[0039] Ethers as donors preferably mean dihydrocarbyl ethers of the general formula R1-O-R2, in which the variables R1 and R2 are each independently C1 to C20 alkyl radicals, preferably C1 to C8 alkyl radicals, especially C1 to C4 alkyl radicals, C5 to C8 cycloalkyl radicals, preferably C5 to C6 cycloalkyl radicals, C6 to C20 aryl radicals, especially C1 to C12 aryl radicals, or C7 to C20 arylalkyl radicals, especially C7 to C12 arylalkyl radicals. Furthermore, C1 to C8 haloalkyl radicals, preferably C1 to C8 chloroalkyl radicals are possible. Preference is given to C1 to C4 alkyl radicals, C6 to C12 aryl radicals and C7 to C12 arylalkyl radicals.

[0040] The mentioned dihydrocarbylic ethers can be open-chain or cyclic, where the two variables R1 and R2, in the case of cyclic ethers, can come together to form a ring, where these rings can also contain two or three atoms of ether oxygen. Examples of such open-chain and cyclic dihydrocarbyl ethers are dimethyl ether, diethyl ether, di-n-propyl ether, diisopropyl ether, di-n-butyl ether, di-sec-butyl ether, di-isobutyl ether, di- n-pentyl, di-n-hexyl ether, di-n-heptyl ether, di-n-octyl ether, di-(2-ethylhexyl ether), methyl-n-butyl ether, methyl sec-butyl ether, ether methyl isobutyl, methyl tert-butyl ether, ethyl n-butyl ether, ethyl sec-butyl ether, ethyl isobutyl ether, ethyl tert-butyl ether, n-propyl-n-butyl ether, n-propyl-sec-butyl ether, ether n-propyl isobutyl, n-propyl tert-butyl ether, isopropyl n-butyl ether, isopropyl n-butyl ether, isopropyl sec-butyl ether, isopropyl isobutyl ether, isopropyl tert-butyl ether, methyl n-hexyl ether, methyl ether n-octyl, methyl 2-ethylhexyl ether, ethyl n-hexyl ether, ethyl n-octyl ether, ethyl 2-ethylhexyl ether, n-butyl n-octyl ether, n-butyl 2-ethylhexyl ether, tetrahydrofuran, tetrahydropyran, 1,2-, 1,3- and 1,4-dioxane, dicyclohexyl ether, diphenyl ether, alkyl aryl ethers such as anisole and phenethol, Ditolyl ether, dixylyl ether and dibenzyl ether . In addition, bis(2-chloroethyl ether), 2-chloroethyl ethyl ether, 2-chloroethylmethyl ether, chloromethylmethyl and chloromethyl ethyl ether.

[0041] Furthermore, difunctional ethers, such as dialkoxybenzenes, preferably dimethoxybenzenes, more preferably veratrol, and ethylene glycol dialkyl ethers, preferably ethylene glycol dimethyl ether and ethylene glycol diethyl ether, are preferred.

[0042] Among the dihydrocarbyl ethers mentioned, diethyl ether, diisopropyl ether, di-n-butyl ether and diphenyl ether proved to be particularly advantageous as a donor for hydrocarbyloxy aluminum compound donor complexes or mixtures of hydrocarbyloxy aluminum compound donor complexes.

[0043] In a further embodiment, a mixture of dihydrocarbyl ethers comprises at least one ether with primary dihydrocarbyl groups and at least one ether with at least one secondary or tertiary dihydrocarbyl group. Ethers with primary dihydrocarbyl groups are those in which both dihydrocarbyl groups are linked to the ether functional group with a primary carbon atom, while ethers with at least one secondary or tertiary dihydrocarbyl group are those in which at least one dihydrocarbyl group is attached to the ether functional group with a secondary or tertiary carbon atom.

[0044] For the sake of clarity, for example, diisobutyl ether is considered to be an ether with primary dihydrocarbyl groups, since the secondary carbon atom of the isobutyl group is not bonded to the oxygen of the functional ether group, but the hydrocarbyl group is attached through a primary carbon atom.

[0045] Preferred examples for ethers with primary dihydrocarbyl groups are diethyl ether, di-n-butyl ether and di-n-propyl ether.

[0046] Preferred examples for ethers with at least one secondary or tertiary dihydrocarbyl group are diisopropyl ether, methyl tert-butyl ether, ethyl tert-butyl ether and anisole.

[0047] The preferred mixtures of ethers according to the invention are diethyl ether/diisopropyl ether, diethyl ether/methyl tert-butyl ether, diethyl ether/ethyl tert-butyl ether, di-n-butyl ether/diisopropyl ether, di- -n-butyl/methyl tert-butyl ether and di-n-butyl ether/ethyl tert-butyl ether. Most preferred mixtures are diethyl ether/diisopropyl ether, di-n-butyl ether/diisopropyl ether, diethyl ether/methyl tert-butyl ether and di-n-butyl ether/ethyl tert-butyl ether, the diethyl ether/tert-butyl ether mixture. diisopropyl being especially preferred.

[0048] In an additional embodiment of the present invention, as an alternative, a hydrocarbyloxy aluminum compound donor complex is used, which comprises, as a donor, a hydrocarbyl carboxylate of general formula R3-COOR4, in which the variables R3 and R4 are , each independently C1 to C20 alkyl radicals, preferably C1 to C8 alkyl radicals, especially C1 to C4 alkyl radicals, C5 to C8 cycloalkyl radicals, C6 to C20 aryl radicals, especially C6 to C12 aryl radicals, or C7 to C7 arylalkyl radicals C20, especially C7 to C12 arylalkyl radicals.

[0049] Examples of the hydrocarbyl carboxylates mentioned 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, propionate n-propyl, isopropyl propionate, n-butyl propionate, sec-butyl propionate, isobutyl propionate, tert-butyl propionate, methyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, butyrate n-butyl, sec-butyl butyrate, isobutyl butyrate, tert-butyl butyrate, methyl cyclohexanecarboxylate, ethyl cyclohexanecarboxylate, n-propyl cyclohexanecarboxylate, isopropyl cyclohexanecarboxylate, cyclohexanecarboxylate n-butyl, sec-butyl cyclohexanecarboxylate, isobutyl cyclohexanecarboxylate, tert-butyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, n-propyl benzoate, isopropyl benzoate, n-butyl benzoate, benzoate sec-butyl, isobutyl benzoate, tert-butyl benzoate, methyl phenylacetate, ethyl phenylacetate, n-propyl phenylacetate, isopropyl phenylacetate, n-butyl phenylacetate, sec-butyl phenylacetate, isobutyl phenylacetate and phenylacetate tert-butyl.

[0050] It is also possible to use polyfunctional hydrocarbylcarboxylates, for example, hydrocarbylic esters of di- or polycarboxylic acids or di- or polyfunctional alcohols esterified with monofunctional carboxylic acids.

[0051] Examples of the former are C1 to C20 alkyl esters, especially C1 to C8 alkyl esters of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, heptanedioic acid, nonanedioic acid, decanedioic acid, maleic acid, fumaric acid, phthalic acid, terephthalic acid and iso-phthalic acid.

[0052] Examples of the latter are formats, acetates, propionates, butyrates and benzoates of 1,2-ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1,4 -butylene glycol, 1,5-pentylene glycol, 1,6-hexylene glycol, 1,8-octylene glycol, 1,10-decylene glycol, glycerol, trimethylolpropane, trimethylolethane and pentaerythritol.

[0053] Among the hydrocarbylcarboxylates mentioned, ethyl acetate was found to be particularly advantageous as a donor for the donor complexes of hydrocarbyloxy aluminum compounds.

[0054] Furthermore, dihydrocarbyl ethers and hydrocarbyl carboxylates particularly advantageous as donors for hydrocarbyloxy aluminum compound donor complexes or mixtures of hydrocarbyloxy aluminum compound donor complexes have been found to be those in which the donor compound has a number total carbon from 3 to 16, preferably from 4 to 16, especially from 4 to 12, in particular from 4 to 8. In the specific case of dihydrocarbylic ethers, preference is given, in particular, to those with a total of 6 to 14 and especially 8 to 12 carbon atoms. In the specific case of hydrocarbyl carboxylates, preference is given, in particular, to those with a total of 3 to 10 and especially 4 to 6 carbon atoms.

[0055] Alcohols as donors are preferably C1-C12 hydrocarbyl alcohols and preferably have only one hydroxyl group per molecule. Particularly suitable C1-C12 hydrocarbylic alcohols are linear or branched C1-C12 alkanols, preferably linear or branched C1-C8 alkanols, more preferably linear or branched C1-C6 alkanols, especially linear or branched C1-C4 alkanols, C5-C12 cycloalkanols and arylalkanols C7-C12. Typical examples of these compounds are methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, secbutanol, tert-butanol, n-pentanol, sec-pentanol, tert-pentanol, n-hexanol, n-heptanol, n-octanol , 2-ethylhexanol, n-nonanol, n-decanol, 2-propylheptanol, n-undecanol, n-dodecanol, cyclopentanol, cyclohexanol, 2-, 3- or 4-methylcyclohexanol, cycloheptanol , benzyl alcohol, 1- or 2-phenylethanol, 1-, 2- or 3-phenylpropanol, 1-, 2-, 3- or 4-phenylbutanol, (o-, m- or p-methylphenyl)methanol, 1.2 -ethylene glycol, 1,3-propylene glycol, 1,2,3-propanetriol (glycerol), 1,2-ethylene glycol monomethyl ether, 1,2-ethylene glycol monoethyl ether, 1,3-propylene monomethyl ether glycol and 1,3-propylene glycol monoethyl ether. It is also possible to use mixtures of several C1-C12 hydrocarbyl alcohols of this type.

[0056] Particular preference is given to the use of branched and linear C1-C12 alkanols, preferably linear or branched C1-C8 alkanols, most preferably linear or branched C1-C6 alkanols, especially linear or branched C1-C4 alkanols.

[0057] Aldehydes and ketones as donors with 1 to 12 carbon atoms can be aliphatic, cycloaliphatic or aromatic in nature. They generally comprise, in addition to the aldehyde or ketone function, a pure hydrocarbon structure and are therefore predominantly hydrocarbon in character. However, they may also comprise, to a small extent, heteroatoms such as nitrogen or oxygen or other functional groups that are inert to the hydroxyl groups.

[0058] Typical examples of these aldehydes and ketones are: formaldehyde, acetaldehyde, propinaldehyde, butyraldehyde, n-pentanal, n-hexanal, n-octanal, n-decanal, n-dodecanal, cyclopentyl-carbaldehyde, cyclohexyl-carbaldehyde, benzaldehyde , phenylacetaldehyde, 2- or 3-pentanone, cyclopentanone, cyclohexanone and acetophenone. It is also possible to use mixtures of several aldehydes of this type or several ketones of this type.

[0059] As aldehydes and ketones with 1 to 12 carbon atoms, particular preference is given to the use of aldehydes and ketones with 1 to 4 carbon atoms, especially aldehydes with 1 to 4 carbon atoms.

[0060] Hemoacetals as donors can be obtained by reacting equimolar amounts of hydrocarbyl alcohol and aldehyde or ketone, preferably the alcohols and aldehydes or ketones mentioned above. The complete acetals used can be obtained by reacting two equivalents of hydrocarbyl alcohol with one equivalent of aldehyde or ketone, preferably the alcohols and aldehydes or ketones mentioned above. It is also possible to use mixtures of hemiacetals and complete acetals. The corresponding full hemiacetals and acetals are generally in chemical equilibrium with each other.

[0061] To form hemiacetals and complete acetals from hydrocarbyl alcohols and aldehydes or ketones, the presence of protic acids that make the addition of the oxygen of the alcohol in the carbonyl function to form the hemiacetal and, in the second step, the addition of the second molecule of alcohol and the elimination of water to form the complete acetal possible. Catalytic amounts of protic acids are generally sufficient. Typical protic auxiliaries here are inorganic acids such as hydrochloric acid or dilute sulfuric acid or organic acids such as carboxylic acids, e.g. acetic acid, trichloroacetic acid or trifluoroacetic acid, or sulfonic acids, e.g. methanesulfonic acid or toluenesulfonic acid .

[0062] A very particular preference is given to formaldehyde, which can be used in monomeric form, for example, in the form of its concentrated aqueous solution, or also as trioxane or as paraformaldehyde for the reaction catalyzed by protic acid with at least one alcohol C1-C12 hydrocarbyl to form hemiacetals or complete acetals.

[0063] The structure of these hemiacetals and complete acetals is shown by the following general formula (I): where the variables R15 and R16 are, independently of each other, hydrogen, C1-C12 alkyl radicals, preferably C1-C8 alkyl radicals, C5-C12 cycloalkyl radicals or C71-C12 arylalkyl radicals, wherein the two variables R15 and R16 can also form a ring and the sum of the carbon atoms in the two variables R15 and R16 must be from 1 to 12, the variable R17 is hydrogen (in the case of hemiacetals) or, in the case of acetals, a C1-C12 alkyl, a C5- cycloalkyl radical C12 or a C7-C12 arylalkyl radical and the variable R18 is a C1-C12 alkyl radical, a C5-C12 cycloalkyl radical or a C7-C12 arylalkyl radical.

[0064] Typical individual examples of these hemiacetals and complete acetals are the methanol and formaldehyde hemiacetal, the complete methanol and formaldehyde acetal, the ethanol and formaldehyde hemiacetal, the complete ethanol and formaldehyde acetal, the n-propanol and formaldehyde hemiacetal , complete acetal of n-propanol and formaldehyde, the hemiacetal of n-butanol and formaldehyde, the complete acetal of n-butanol and formaldehyde, the hemiacetal of methanol and acetaldehyde, the complete acetal of methanol and acetaldehyde, the hemiacetal of ethanol and acetaldehyde , the complete acetal of ethanol and acetaldehyde, the hemiacetal of n-propanol and acetaldehyde, the complete acetal of n-propanol and acetaldehyde, the hemiacetal of n-butanol and acetaldehyde and the complete acetal of n-butanol and acetaldehyde.

[0065] Examples of phenols as donors are substituted or unsubstituted phenols and naphthols, preferably phenols.

[0066] Very preferred examples of phenols are those with the formula wherein R19, R20 and R21 independently of each other are hydrogen or C1 to C20 alkyl, preferably C1 to C8 alkyl, more preferably C1 to C4 alkyl.

[0067] Preferably R19, R20 and R21 independently of each other are hydrogen, methyl, ethyl, isopropyl, sec-butyl and tert-butyl, more preferably hydrogen, methyl and tert-butyl.

[0068] Preferred phenols are phenol, 2-methylphenol, 2-tert-butylphenol, 2-methyl-4-tert-butylphenol and 4-methyl-2,6-di-tert-butylphenol.

[0069] The preferred donor compounds are ethers, alcohols, ketones and phenols, the most preferred are ethers, ketones and phenols, and the most preferred are ethers.

[0070] The molar ratio of the mentioned donor compounds to the hydrocarbyloxy aluminum compound in the donor complex generally varies in the range of 0.2:1 to 1.5:1, especially from 0.3:1 to 1.2:1, in particular 0.4:1 to 1.1:1; in most cases it is 0.4:1 to 1:1. However, it is also possible to work with a greater excess of donor compounds, often up to 10-fold and especially 3-fold molar excess; the excessive amount of donor compounds additionally acts as a solvent or diluent.

[0071] The molar ratio of ether compounds in a binary mixture generally ranges from 0.1:1 to 1:0.1, preferably from 0.2:1 to 1:0.2, more preferably from 0.3:1 to 1:0.3, more preferably from 0.5:1 to 1:0.5, especially from 0.66:1 to 1:0.66 and even from 0.9:1 to 1:0.9. In a preferred embodiment, the ether compounds are present in an equimolar molar ratio.

[0072] The molar ratio of the hydrocarbyloxy aluminum compound or mixtures thereof or hydrocarbyloxy aluminum compound donor complex to the isobutene monomer used in the case of isobutene homopolymerization or the total amount of polymerizable monomers used in the case of isobutene copolymerization, based at each individual functional site of the aluminum carbyloxy compound or the aluminum hydrocarbyloxy compounds or hydrocarbyloxy aluminum compound donor complex, is generally 0.001:1 to 0.2:1, preferably 0.002:1 to 0.1:1, more preferably 0.003:1 to 0.08:1, especially 0.005:1 to 0.05:1 and in particular 0.007:1 to 0.03:1.

[0073] Typically, the hydrocarbyloxy aluminum compounds or the donor complex of the hydrocarbyloxy aluminum compound are prepared separately before polymerization from aluminum trihalide or alkylaluminum dihalide or dialkylaluminum halide, especially anhydrous aluminum trichloride , alkyl aluminum dichloride or a dialkyl aluminum chloride and the aluminum trishydrocarbyloxy compound Al(ORa)3 in stoichiometric amounts representing p, q and r, and is then - normally dissolved in an inert solvent, such as a halogenated hydrocarbon, for example dichloromethane, or more preferably non-halogenated hydrocarbons - added to the polymerization medium. However, the complex can also be prepared in situ before polymerization.

[0074] Preferably, the hydrocarbyloxy aluminum compound thus obtained or mixtures thereof are then mixed with the respective donor compound or compounds and added to the polymerization medium. However, the complex can also be prepared in situ before polymerization.

[0075] It is an advantage of the hydrocarbyloxy aluminum compound or mixtures thereof or donor complexes that they exhibit better solubility in hydrocarbon solvents, especially in toluene than AlCl3. Therefore, it is possible to avoid or significantly reduce the use of halogenated solvents to dissolve the catalyst.

[0076] In a preferred embodiment of the present invention, polymerization is carried out with additional use of a mono- or polyfunctional initiator, especially mono-, di- or trifunctional, which is selected from organic hydroxyl compounds, organic halogen compounds and water. It is also possible to use mixtures of the mentioned initiators, for example, mixtures of two or more organic hydroxyl compounds, mixtures of two or more organic halogen compounds, mixtures of one or more organic hydroxyl compounds and one or more organic halogen compounds, mixtures of one or more organic hydroxyl compounds and water, or mixtures of one or more organic halogen compounds and water. The initiator can be mono-, di- or polyfunctional, that is, one, two or more hydroxyl groups or halogen atoms, which initiate the polymerization reaction, can be present in the initiator molecule. In the case of di- or polyfunctional initiators, telecelic isobutene polymers with two or more, especially two or three, polyisobutene chain termini are generally obtained.

[0077] Organic hydroxyl compounds that have only one hydroxyl group in the molecule and are suitable as monofunctional initiators include especially alcohols and phenols, in particular those of the general formula R5-OH, where R5 denotes C1 to C20 alkyl radicals, especially alkyl radicals C1 to C8, C5 to C8 cycloalkyl radicals, C6 to C20 aryl radicals, especially C6 to C12 aryl radicals or C7 to C20 arylalkyl radicals, especially C7 to C12 arylalkyl radicals. Furthermore, R5 radicals may also comprise mixtures of the above-mentioned structures and/or have other functional groups than those already mentioned, for example, a keto function, a nitroxide group or a carboxyl and/or heterocyclic structural elements.

[0078] Typical examples of these organic monohydroxyl compounds are methanol, ethanol, n-propanol, isopropanol, n-butanol, secbutanol, isobutanol, tert-butanol, n-pentanol, n-hexanol, n-heptanol, noctanol, 2- ethylhexanol, cyclohexanol, phenol, p-methoxyphenol, o-, m- and p-cresol, benzyl alcohol, p-methoxybenzyl alcohol, 1- and 2-phenylethanol, 1- and 2-(p-methoxyphenyl)ethanol , 1-, 2- and 3-phenyl-1-propanol, 1-, 2- and 3-(p-methoxyphenyl)-1-propanol, 1- and 2-phenyl-2-propanol, 1- and 2-( p-methoxyphenyl)-2-propanol, 1-, 2-, 3- and 4-phenyl-1-butanol, 1-, 2-, 3- and 4-(p-methoxyphenyl)-1-butanol, 1-, 2-, 3- and 4-phenyl-2-butanol, 1-, 2-, 3- and 4-(p-methoxyphenyl)-2-butanol, 9-methyl-9H-fluoren-9-ol, 1,1 -diphenylethanol, 1,1-diphenyl-2-propyn-1-ol, 1,1-diphenylpropanol, 4-(1-hydroxy-1-phenylethyl) benzonitrile, cyclopropyldiphenylmethanol, 1-hydroxy-1,1-diphenylpropan-2- one, benzylic acid, 9-phenyl-9-fluorenol, triphenylmethanol, diphenyl(4-pyridinyl)methanol, alpha,alpha-diphenyl-2-pyridinemethanol, 4-methoxytrityl alcohol (especially bound to the polymer as a solid phase), alpha- tert-butyl-4-chloro-4'-methylbenzhydrol, cyclohexyldiphenylmethanol, alpha-(p-tolyl)-benzhydrol, 1,1,2-triphenylethanol, alpha,alpha-diphenyl-2-pyridineethanol, alpha N-oxide ,alpha-4-pyridylbenzhydrol, 2-fluorotriphenylmethanol, triphenylpropargyl alcohol, 4-[(diphenyl)hydroxy-methyl]benzonitrile, 1-(2,6-dimethoxyphenyl)-2-methyl-1-phenyl-1-propanol, 1, 1,2-triphenylpropan-1-ol and p-anisaldehyde carbinol.

[0079] Organic hydroxyl compounds that have two hydroxyl groups in the molecule and are suitable as bifunctional initiators are especially dihydric alcohols or diols with a total carbon number of 2 to 30, especially 3 to 24, in particular 4 to 20, and bisphenols with a total carbon number of 6 to 30, especially 8 to 24, in particular 10 to 20, for example ethylene glycol, 1,2- and 1,3-propylene glycol, 1,4-butylene glycol, 1,6-hexylene glycol, 1,2-, 1,3- or 1,4-bis(1-hydroxy-1-methylethyl) benzene (o-, m- or p-dicumyl alcohol), bisphenol A, 9.10 -dihydro-9,10-dimethyl-9,10-anthracenediol, 1,1-diphenylbutane-1,4-diol, 2-hydroxytriphenylcarbinol and 9-[2-(hydroxymethyl)phenyl]-9-fluorenol.

[0080] Organic halogen compounds that have a halogen atom in the molecule and are suitable as monofunctional initiators are in particular compounds of the general formula R6-Hal in which Hal is a halogen atom selected from fluorine, iodine and especially chlorine and bromine, and R6 denotes C1 to C20 alkyl radicals, especially C1 to C8 alkyl radicals, C5 to C8 cycloalkyl radicals or C7 to C20 arylalkyl radicals, especially C7 to C12 arylalkyl radicals. Furthermore, R6 radicals may also include mixtures of the above-mentioned structures and/or have groups other than those already mentioned, for example, a keto function, a nitroxide or carboxyl group and/or heterocyclic structural elements.

[0081] Typical examples of these monohalogen compounds are methyl chloride, methyl bromide, ethyl chloride, ethyl bromide, 1-chloropropane, 1-bromopropane, 2-chloropropane, 2-bromopropane, 1-chlorobutane, 1-bromobutane , sec-butyl chloride, sec-butyl bromide, isobutyl chloride, isobutyl bromide, tert-butyl chloride, tert-butyl bromide, 1-chloropentane, 1-bromopentane, 1-chlorohexane, 1-bromine - hexane, 1-chloroheptane, 1-bromoheptane, 1-chlorooctane, 1-bromooctane, 1-chloro-2-ethylhexane, 1-bromo-2-ethylhexane, cyclohexyl chloride, bromide cyclohexyl, cyclohexyl bromide, benzyl chloride, benzyl bromide, 1-phenyl-1-chloroethane, 1-phenyl-1-bromoethane, 1-phenyl-2-chloroethane, 1-phenyl-2-bromoethane , 1-phenyl-1-chloropropane, 1-phenyl-1-bromopropane, 1-phenyl-2-chloropropane, 1-phenyl-2-bromopropane, 2-phenyl-2-chloropropane, 2-phenyl-2-bromopropane, 1 -phenyl-3-chloropropane, 1-phenyl-3-bromopropane, 1-phenyl-1-chlorobutane, 1-phenyl-1-bromobutane, 1-phenyl-2-chlorobutane, 1-phenyl-2-bromobutane, 1-phenyl -3-chlorobutane, 1-phenyl-3-bromobutane, 1-phenyl-4-chlorobutane, 1-phenyl-4-bromobutane, 2-phenyl-1-chlorobutane, 2-phenyl-1-bromobutane, 2-phenyl-2 -chlorobutane, 2-phenyl-2-bromobutane, 2-phenyl-3-chlorobutane, 2-phenyl-3-bromobutane, 2-phenyl-4-chlorobutane and 2-phenyl-4-bromobutane.

[0082] Organic halogen compounds that have two halogen atoms in the molecule and are suitable as difunctional initiators are, for example, 1,3-bis(1-bromo-1-methylethyl)benzene, 1,3-bis(2- chloro-2-propyl) benzene (1,3-dicumyl chloride) and 1,4-bis(2-chloro-2-propyl)benzene (1,4-dicumyl chloride).

[0083] The initiator is most preferably selected from organic hydroxyl compounds in which one or more hydroxyl groups are each bonded to an sp3-hybridized carbon atom, organic halogen compounds, in which one or more halogen atoms are each bonded to a carbon atom hybridized with sp3- and water. Among these, preference is given, in particular, to an initiator selected from organic hydroxyl compounds in which one or more hydroxyl groups are attached to an sp3-hybridized carbon atom.

[0084] In the case of organic halogen compounds as initiators, particular preference is given to those in which one or more halogen atoms are bonded to a secondary carbon atom or especially to a tertiary sp3-hybridized carbon atom.

[0085] Preference is given, in particular, to initiators that can bear, on an sp3-hybridized carbon atom, in addition to the hydroxyl group, the radicals R5, R6 and R7, which are each, independently, hydrogen, C1 alkyl to C20, C5 to C8 cycloalkyl, C6 to C20 aryl, C7 to C20 alkylaryl or phenyl, wherein any aromatic ring may also contain one or more, preferably one or two C1 to C4 alkyl, C1 to C4 alkoxy, C1 to C4 hydroxyalkyl radicals or C1 to C4 haloalkyl as substituents, when not more than one of the variables R5, R6 and R7 is hydrogen and at least one of the variables R5, R6 and R7 is phenyl which may also contain one or more, preferably one or two, alkyl radicals C1 to C4, C1 to C4 alkoxy, C1 to C4 hydroxyalkyl or C1 to C4 haloalkyl as substituents.

[0086] For the present invention, very particular preference is given to initiators selected from water, 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. Among these, preference is given, in particular, to initiators selected from water, 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.

[0087] The molar ratio of the aforementioned initiators to the isobutene monomer used in the case of isobutene homopolymerization or to the total amount of polymerizable monomers used in the case of isobutene copolymerization, based on each individual functional site of the initiator, is generally 0.0005:1 to 0.1:1, especially 0.001:1 to 0.075:1, in particular 0.0025:1 to 0.05:1. When water is used as the sole initiator or in combination with organic hydroxyl compounds and/or organic halogen compounds as additional initiators, the molar ratio of water to isobutene monomer used in the case of isobutene homopolymerization or to the total amount of polymerizable monomers used in the case of isobutene copolymerization is especially 0.0001:1 to 0.1:1, in particular 0.0002:1 to 0.05:1, preferably 0.0008:1 to 0.04:1 and much more. preferably, in particular, from 0.001:1 to 0.03:1.

[0088] A proportion of the initiator molecules added as organic hydroxyl or halogen compounds are incorporated into the polymer chains. The proportion (Ieff) of polymer chains that are initiated by an incorporated organic starter molecule can be up to 100% and is generally 5% to 90%. The remaining polymer chains arise from water originating from trace amounts of moisture as an initiator molecule or from chain transfer reactions.

[0089] In another preferred embodiment of the present invention, polymerization is carried out in the presence of 0.01 to 10 mmol, especially 0.05 to 5.0 mmol, in particular 0.1 to 1.0 mmol, with based in each case on 1 mol of isobutene monomer used in the case of isobutene homopolymerization, or on 1 mol of the total quantity of the polymerizable monomers used in the case of isobutene copolymerization, of a nitrogen-containing basic compound.

[0090] A less preferred nitrogen-containing basic compound used may be an aliphatic, cycloaliphatic or aromatic amine of the general formula R7-NR8R9, or else ammonia, in which the variables R7, R8 and R9 are each independently hydrogen, C1 alkyl radicals and C20, especially C1 to C8 alkyl radicals, C5 to C8 cycloalkyl radicals, C6 to C20 aryl radicals, especially C6 to C12 aryl radicals, or C7 to C20 arylalkyl radicals, especially C7 to C12 arylalkyl radicals. When none of these variables is hydrogen, the amine is a tertiary amine. When one of these variables is hydrogen, the amine is a secondary amine. When two of these variables are hydrogen, the amine is a primary amine. When all of these variables are hydrogen, the amine is ammonia.

[0091] Typical examples of such amines of the general formula R7-NR8R9 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, diisopropylamine, di-n-butylamine, di-tert-butylamine, di-sec-butylamine, diisobutylamine , di-tert-amylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-(2-ethylhexyl)amine, dicyclopentylamine, dicyclohexylamine, diphenylamine, trimethylamine, triethylamine, tri- n-propylamine, triisopropylamine, tri-n-butylamine, tri-tert-butylamine, tri-sec-butylamine, triisobutylamine, 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-N-n-butylamine.

[0092] Furthermore, this basic nitrogen-containing compound used can also be a compound having a plurality of, especially having two or three, nitrogen atoms and having 2 to 20 carbon atoms, wherein these nitrogens can each independently carry atoms of hydrogen 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.

[0093] However, a suitable nitrogen-containing basic compound of this type is especially a five- or six-membered heterocyclic ring containing saturated, partially unsaturated or unsaturated nitrogen, which comprises one, two or three nitrogen atoms in the ring and may have one or two other ring heteroatoms of the oxygen and sulfur radical group and/or hydrocarbyl, especially C1 to C4 alkyl and/or phenyl radicals, and/or functional groups or heteroatoms as substituents, especially fluorine, chlorine, bromine, nitro and/or cyano , for example, pyrrolidine, pyrrole, imidazole, 1,2,3- or 1,2,4-triazole, oxazole, thiazole, piperidine, pyrazane, pyrazole, pyridazine, pyrimidine, pyrazine, 1,2,3-, 1, 2,4- or 1,2,5-triazine, 1,2,5- oxathiazine, 2H-1,3,5-thidiazine or morpholine.

[0094] However, a very particularly suitable nitrogen-containing basic compound of this type is pyridine or a pyridine derivative (especially a pyridine substituted by C1 to C4 mono-, di- or tri-alkyl), such as 2-, 3 -, or 4-methylpyridine (picolines), 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, 3,5- or 3,6-dimethylpyridine (lutidines), 2 ,4,6-trimethylpyridine (colidine), 2-, 3, - or 4-tert-butylpyridine, 2-tert-butyl-6-methylpyridine, 2,4-, 2,5-, 2,6- or 3, 5-di-tert-butylpyridine or 2-, 3- or 4-phenylpyridine.

[0095] It is possible to use a single nitrogen-containing basic compound or mixtures of these nitrogen-containing basic compounds.

[0096] For the use of isobutene or a mixture of monomers comprising isobutene as the monomer to be polymerized, suitable isobutene sources are pure C4 isobutene and isobutene hydrocarbon streams, for example, refined C4, especially "refined 1", cuts C4 from isobutane dehydrogenation, C4 cuts from steam crackers and FCC (fluid catalyzed cracking) crackers, provided that they have been substantially free of 1,3-butadiene present therein. A C4 hydrocarbon stream from an FCC refinery unit is also known as a "b/b" stream. Additional suitable C4 isobutene hydrocarbon streams are, for example, the product stream of a propylene-isobutane co-oxidation or the product stream of a metathesis unit, which are generally used after the usual purification and/or concentration. Suitable C4 hydrocarbon streams generally comprise less than 500 ppm, preferably less than 200 ppm, of butadiene. The presence of 1-butene and cis- and trans-2-butene is substantially uncritical. Typically, the concentration of isobutene in the mentioned C4 hydrocarbon streams is in the range of 40% to 60% by weight. For example, raffinate 1 generally consists essentially of 30% to 50% by weight isobutene, 10% to 50% by weight 1-butene, 10% to 40% by weight cis- and trans-2-butene, and 2 % to 35% by weight of butanes; In the polymerization process according to the invention, the unbranched butenes in raffinate 1 generally behave practically inertly, and only isobutene is polymerized.

[0097] In a preferred embodiment, the monomer source used for the polymerization is a technical C4 hydrocarbon stream with an isobutene content of 1% to 100% by weight, especially from 1% to 99% by weight, in particular of 1% to 90% by weight, more preferably from 30% to 60% by weight, especially a raffinate stream 1, 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.

[0098] Especially when a raffinate stream 1 is used as a source of isobutene, the use of water as a sole initiator or as an additional initiator is useful, especially when polymerization is carried out at temperatures from -20°C to +30°C, especially from 0°C to +20°C. At temperatures from -20°C to +30°C, especially from 0°C to +20°C, when a raffinate stream 1 is used as a source of isobutene, it is also possible to dispense with the use of an initiator.

[0099] The mixture of isobutene monomers mentioned can comprise small amounts of contaminants, such as water, carboxylic acids or mineral acids, without yield or loss of critical selectivity. It is appropriate to prevent the enrichment of these impurities by removing these harmful substances from the mixture of isobutene monomers, for example, by adsorption on solid adsorbents such as activated carbon, molecular sieves or ion exchangers.

[00100] It is also possible to convert mixtures of isobutene monomers or isobutene hydrocarbon mixtures with olefinically unsaturated monomers copolymerizable with isobutene. When mixtures of isobutene monomers are to be copolymerized with suitable comonomers, the monomer mixture preferably comprises at least 5% by weight, more preferably at least 10% by weight and especially at least 20% by weight of isobutene and preferably at most 95 % by weight, more preferably at most 90% by weight and especially at most 80% by weight of comonomers.

[00101] Useful copolymerizable monomers include: vinylaromatics, such as styrene and α-methylstyrene, C1 to C4 alkylstyrenes such as 2-, 3- and 4-methylstyrene and 4-tert-butylstyrene, halostyrenes 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. The most useful comonomers include olefins that have a silyl group, such as 1-trimethoxysilylethene, 1-(trimethoxysilyl)propene, 1-(trimethoxysilyl)-2-methylpropene-2, 1-[tri(methoxyethoxy)silyl]ethene, 1 -[tri(methoxyethoxy)silyl]propene and 1-[tri(methoxyethoxy)silyl]-2-methylpropene-2. Furthermore - depending on the polymerization conditions - useful comonomers also include isoprene, 1-butene and cis- and trans-2-butene.

[00102] When the process according to the invention is to be used to prepare copolymers, the process can be configured to preferably form random polymers or to preferably form block copolymers. To prepare block copolymers, for example, the different monomers can be supplied successively to the polymerization reaction, in which case the second comonomer is not specially added until the first comonomer is already at least partially polymerized. In this way, diblock, triblock and higher block copolymers are able to be obtained, which, according to the monomer addition sequence, have a block of one or another comonomer as the terminal block. In some cases, however, block copolymers also form when all comonomers are supplied to the polymerization reaction simultaneously, but one of them polymerizes significantly more quickly than the other(s). This is especially the case when isobutene and a vinylaromatic compound, especially styrene, are copolymerized in the process according to the invention. This preferably forms block copolymers with a polystyrene end block. This is attributed to the fact that the vinylaromatic compound, especially styrene, polymerizes significantly more slowly than isobutene.

[00103] Polymerization can be carried out continuously or in batches. Continuous processes can be carried out in analogy to known prior art processes for continuous polymerization of isobutene in the presence of boron trifluoride-based catalysts in the liquid phase.

[00104] The process according to the invention is suitable for performance at low temperatures, e.g. at -90°C to 0°C, or at higher temperatures, i.e. at least 0°C, e.g. from 0°C to +30°C or from 0°C to +50°C. The polymerization in the process according to the invention is, however, preferably carried out at relatively low temperatures, generally from -70°C to -10°C, especially from -60°C to -15°C.

[00105] When polymerization in the process according to the invention is carried out at or above the boiling temperature of the monomer or mixture of monomers to be polymerized, it is preferably carried out in pressure vessels, for example, in autoclaves or in pressure reactors .

[00106] Polymerization in the process according to the invention is preferably carried out in the presence of an inert diluent. The inert diluent used must be suitable to reduce the increase in viscosity of the reaction solution that generally occurs during the polymerization reaction to such an extent that removal of heat from the evolving reaction can be ensured. Suitable diluents are those solvents or solvent mixtures that are inert with respect to the reagents used. Suitable diluents are, for example, aliphatic hydrocarbons such as n-butane, n-pentane, n-hexane, n-heptane, n-octane and isooctane, cycloaliphatic hydrocarbons such as cyclopentane and cyclohexane, aromatic hydrocarbons such as benzene , toluene and xylenes, and halogenated hydrocarbons, especially halogenated aliphatic hydrocarbons, such as methyl chloride, dichloromethane and trichloromethane (chloroform), 1,1-dichloroethane, 1,2-dichloroethane, trichloroethane and 1-chlorobutane, and also aromatic hydrocarbons halogenated and halogenated alkylaromatics in alkyl side chains, such as chlorobenzene, monofluoromethylbenzene, difluoromethylbenzene and trifluoromethylbenzene and mixtures of the diluents mentioned above. The diluents used or the constituents used in the mentioned solvent mixtures are also the inert components of the C4 isobutene hydrocarbon streams. A non-halogenated solvent is preferred over the list of halogenated solvents.

[00107] The polymerization of the invention can be carried out in a halogenated hydrocarbon, especially in a halogenated aliphatic hydrocarbon, or in a mixture of halogenated hydrocarbons, especially of halogenated aliphatic hydrocarbons or in a mixture of at least one halogenated hydrocarbon, especially an aliphatic hydrocarbon halogenated hydrocarbon and at least one aliphatic, cycloaliphatic or aromatic hydrocarbon as an inert diluent, for example a mixture of dichloromethane and n-hexane, normally in a volume ratio of 10:90 to 90:10, especially 50:50 to 85 :15. Before use, the diluents are preferably free of impurities such as water, carboxylic acids or mineral acids, for example by adsorption on solid adsorbents such as activated carbon, molecular sieves or ion exchangers.

[00108] In a preferred embodiment, the polymerization of the invention is carried out in halogen-free or especially halogen-free aliphatic aromatic hydrocarbons, especially toluene. For this embodiment, water in combination with the mentioned organic hydroxyl compounds and/or the mentioned halogenated organic compounds, or especially as the sole initiator, has been found to be particularly advantageous.

[00109] The polymerization in the process according to the invention is preferably carried out under substantially aprotic and substantially anhydrous reaction conditions. It is understood that substantially aprotic and substantially anhydrous reaction conditions mean that, respectively, the content of protic impurities and the water content in the reaction mixture are less than 50 ppm and especially less than 5 ppm. In general, raw materials will therefore be dried before use by physical and/or chemical measures. More particularly, it has been found useful to mix the aliphatic or cycloaliphatic hydrocarbons used as solvents, after customary pre-purification and pre-drying, with an organometallic compound, for example an organolithium, organomagnesium or organoaluminum compound, in an amount which is sufficient to substantially remove traces of water from the solvent. The solvent thus treated is then preferably condensed directly in the reaction vessel. It is also possible to proceed in a similar way with the monomers to be polymerized, especially with isobutene or isobutene mixtures. Drying with other customary desiccants such as molecular sieves or pre-dried oxides such as aluminum oxides, 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 an option are freed from traces of water or water with desiccants suitable for this purpose, for example with calcium chloride, phosphorus pentoxide or molecular sieves. It is also possible in a similar way to dry raw materials for which treatment with metal alkyls is also not an option, for example vinylaromatic compounds. Even if part or all of the initiator used is water, residual moisture should preferably be substantially or completely removed from the solvents and monomers by drying prior to reaction in order to be able to use the water initiator in a specified and controlled amount, as a result of which which provides greater process control and reproducibility of results.

[00110] The polymerization of isobutene or isobutene starting material generally occurs spontaneously when the hydrocarbyloxy aluminum compound or mixtures of hydrocarbyloxy aluminum compounds or hydrocarbyloxy aluminum compound donor complex, is contacted with the mixture of isobutene or isobutene monomer at the temperature of desired reaction. The procedure here may be to initially load the monomers, optionally into the diluent, to bring it to the reaction temperature and then add the hydrocarbyloxy aluminum compound or mixtures of hydrocarbyloxy aluminum compounds or donor complex of hydrocarbyloxy aluminum compounds. The procedure may also be to initially load the aluminum hydrocarbyloxy compound or mixtures of aluminum hydrocarbyloxy compounds or the aluminum hydrocarbyloxy compound donor complex, optionally into the diluent and then add the monomers. In this case, the beginning of polymerization is considered the moment when all reactants are present in the reaction vessel.

[00111] To prepare isobutene copolymers, the procedure may be to initially load the monomers, optionally in the diluent, and then add the hydrocarbyloxy aluminum compound or mixtures of hydrocarbyloxy aluminum compounds or hydrocarbyloxy aluminum compound donor complex. The reaction temperature can be established before or after the addition of the hydrocarbyloxy aluminum compound or mixtures thereof or donor complexes of hydrocarbyloxy aluminum compounds. The procedure may also be to first initially load only one of the monomers, optionally in the diluent, to add the aluminum hydrocarbyloxy compound or mixtures thereof or hydrocarbyloxy aluminum compound donor complex and add the additional monomer(s) only after a certain time, for example, when at least 60%, at least 80% or at least 90% of the monomer has been converted. Alternatively, the hydrocarbyloxy aluminum compound or mixtures thereof or the hydrocarbyloxy aluminum compound donor complex may optionally be loaded into the diluent; then the monomers can initially be added simultaneously or successively and then the desired reaction temperature can be established. In this case, the beginning of polymerization is considered the moment when the hydrocarbyloxy aluminum compound or mixtures thereof or hydrocarbyloxy aluminum compound donor complex and at least one of the monomers are present in the reaction vessel.

[00112] In addition to the batch procedure described here, polymerization in the process according to the invention can also be configured as a continuous process. In this case, the raw material, that is, the monomers to be polymerized, optionally the diluent and, optionally, the hydrocarbyloxy aluminum compound or mixtures thereof or the donor complex of hydrocarbyloxy aluminum compounds, are continuously supplied to the polymerization reaction, and the Reaction product is continuously removed, so that polymerization conditions are established in a more or less stable state in the reactor. The monomer(s) to be polymerized may be supplied in this form, diluted with a diluent or solvent or as a monomer-containing hydrocarbon stream.

[00113] The hydrocarbyloxy aluminum compound or mixtures thereof or the hydrocarbyloxy aluminum compound donor complex effective as a polymerization catalyst is generally present in dissolved, dispersed or suspended forms in the polymerization medium. Support of the aluminum hydrocarbyloxy compound or mixtures thereof or aluminum hydrocarbyloxy compound donor compound on customary support materials is also possible. Types of reactors suitable for the polymerization process of the present invention are typically stirred tank reactors, closed loop reactors and tubular reactors, but also fluidized bed reactors, stirred tank reactors with or without solvent, fluidized bed reactors, continuous fixed bed and batch fixed bed reactors (batch mode).

[00114] In the process according to the invention, the hydrocarbyloxy aluminum compound or mixtures thereof or the hydrocarbyloxy aluminum compound donor complex, is generally used in an amount such that the molar ratio of aluminum in the hydrocarbyloxy aluminum compound or mixtures thereof same or donor complex of hydrocarbyloxy aluminum compounds, to isobutene in the case of isobutene homopolymerization, or the total amount of polymerizable monomers used in the case of isobutene copolymerization, is in the range of 1:5 to 1:5000, preferably 1: 10 to 1:5000, especially 1:15 to 1:1000, in particular 1:20 to 1:250.

[00115] To stop the reaction, the reaction mixture is preferably deactivated, for example, by adding a protic compound, especially by adding water, alcohols such as methanol, ethanol, n-propanol and isopropanol or mixtures thereof with water or by adding a base aqueous, for example, an aqueous solution of an alkali metal or alkaline earth metal hydroxide, such as sodium hydroxide, potassium hydroxide, magnesium hydroxide or calcium hydroxide, alkali metal or alkaline earth metal carbonate, such as sodium, potassium, magnesium or calcium carbonate, or an alkali or alkaline earth metal hydrogen carbonate, such as sodium, potassium, magnesium or calcium hydrogen carbonate.

[00116] The process according to the invention serves to prepare highly reactive isobutene homo- or copolymers with a content of terminal vinylidene double bonds (double-α bonds)) per end of the polyisobutene chain of at least 70%, preferably at least 75% and more preferably at least 80 mol%, at least 85 mol%, more preferably at least 90 mol%, more preferably above 91 mol% and especially at least 95 mol% , for example, practically 100% by mol. More particularly, it also serves to prepare highly reactive isobutene copolymers, formed from isobutene and at least one vinylaromatic monomer, especially styrene, and having a content of terminal vinylidene double bonds (α-double bonds) per chain end. polyisobutene of at least 70, preferably at least 75 mol%, preferably at least 80 mol%, preferably at least 85 mol%, more preferably at least 90 mol%, more preferably more than 91 mol% and especially by at least 95 mol%, for example, practically 100 mol%. Prepare such copolymers of isobutene and at least one vinylaromatic monomer, especially styrene, isobutene or an isobutene hydrocarbon cut is copolymerized with the at least one vinylaromatic monomer in the weight ratio of isobutene to vinylaromatic of 5:95 to 95:5, especially from 30:70 to 70:30.

[00117] The highly reactive isobutene homo- or copolymers prepared by the process according to the invention and specifically the isobutene homopolymers preferably have a polydispersity (PDI = Mw/Mn) of 1.05 to less than 3.5, preferably from 1.05 to less than 3.0, preferably from 1.05 to less than 2.5, preferably from 1.05 to 2.3, more preferably from 1.05 to 2.0 and especially from 1.1 to 1.85. Typical PDI values in the case of an ideal process regime are 1.2 to 1.7.

[00118] The highly reactive isobutene homo- or copolymers prepared by the process according to the invention preferably have an average numerical molecular weight Mn (determined by gel permeation chromatography) preferably of 500 to 250,000, more preferably of 500 to 100,000 , even more preferably from 500 to 25,000 and especially from 500 to 5,000. Isobutene homopolymers even more preferably have a number average molecular weight Mn of 500 to 10,000 and especially of 500 to 5,000, for example, of about 1,000 or about 2,300.

[00119] Some of the isobutene polymers that have terminal vinylidene double bonds and also comprise incorporated initiator molecules and occur as the predominant proportion in the isobutene homopolymers prepared according to the invention are new compounds. The present invention, therefore, also provides isobutene polymers of general form I in which R10, R11 and R12 are each independently hydrogen, C1 to C20 alkyl, C5 to C8 cycloalkyl, C6 to C20 aryl, C7 to C20 alkylaryl or phenyl, wherein any aromatic ring may also contain one or more C1 to C20 alkyl radicals C4 or C1 to C4 alkoxy or fractions of general formula II as substituents, wherein not more than one of the variables R10, R11 and R12 is hydrogen and in at least one of the variables R10, R11 and R12 is phenyl which may also contain one or more C1 to C4 alkoxy or C1 to C4 alkyl radicals or fractions of general formula II as substituents, and n is a number from 9 to 4,500, preferably 9 to 180, especially 9 to 100, in particular 12 to 50.

[00120] In a preferred embodiment, R10, R11 and R12 are each independently hydrogen, C1 to C4 alkyl, especially methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl or phenyl which may also contain one or two C1 to C4 alkyl radicals C1 to C4 alkoxy or portions of general formula II as substituents, wherein not more than one of the variables R10, R11 and R12 is hydrogen and at least one of the variables R10, R11 and R12 is phenyl, which may also have one or two radicals or C1 to C4 alkyl or C1 to C4 alkoxy moieties of general formula II as substituents, and n is a number from 9 to 4,500, preferably 9 to 180, especially 9 to 90, in particular 15 to 45.

[00121] The process according to the invention successfully polymerizes isobutene or mixtures of monomers comprising isobutene under cationic conditions with satisfactory high conversions of generally 20% to 100%, especially 35% to 90%, in short reaction times of generally 5 to 120 minutes, especially 30 to 120 minutes, to give highly reactive isobutene homo- or copolymers with a content of terminal vinylidene double bonds per polyisobutene chain end of at least 70%, preferably at least 75v and more preferably at least less than 80 mol% and with a narrow molecular weight distribution.

[00122] The following examples are intended to illustrate the present invention in detail, without restricting it.

Examples

[00123] The polymerization reactions were carried out in glass tubes equipped with a cold finger condenser or, in some cases, in a stainless steel reactor with a PTFE coating under an argon atmosphere at 10°C. As an example of a typical procedure, polymerization was initiated by adding isobutylene (3.25 g, 5.8x10-2 mol) to a mixture of a total volume of 5.16 ml, consisting of solutions of diisopropyl ether (0. 38 ml, 0.1M) in n-hexane and BuOAlCl2 (0.38 ml, 1M) in toluene and n-hexane (4.4 ml). After 10 minutes of reaction time, about 2 ml of ethanol was poured into the reactor to complete the polymerization. The quenched reaction mixtures were diluted with n-hexane, washed with 0.5 M nitric acid and deionized water to remove aluminum-containing residues, evaporated to dryness under reduced pressure, and dried in vacuum (<60°C) to give the polymeric products

[00124] Product yields were determined gravimetrically. The number-average molecular weight Mn and the weight-average molecular weight Mw were determined by Size Exclusion Chromatography (SEC, MnSEC) with polystyrene standards or by 1H NMR (MnRMN). The polydispersity PDI = Mw/Mn was calculated using the values thus obtained.

[00125] The composition of the reaction products was determined by the 1H-NMR method and assigned to structures as described in Shiman, D.I.; Vasilenko, I.V.; Kostjuk, S.V. "Cationic polymerization of isobutylene by AlCl3 complexes/ether complexes in non-polar solvents: effect of ether structure on selectivity of β-H elimination", Polymer 2013, 54, 2235-2242, Figure 4.

[00126] The 1H-NMR deviations are attributed to the structural elements as follows:

[00127] In the context of the present invention, the term "exo" refers to terminal ethylenic double bonds, vinylidene groups or α-double bonds, as shown in the formula on page 1 of this document. These terms are used synonymously throughout the text.

[00128] The term "total vinylidene" means the terminal ethylenic double bonds referred to as exo above and additionally double bonds located internally in the main backbone of the polymer, as shown in the following formula:

[00129] The terms "endo" and "trisubstituted" refer to double-β bonds, as shown in the formulas above in the second line. These terms are used synonymously throughout the text.

[00130] Additionally, "tetrasubstituted" structural elements can be found as shown in the formula in the upper right corner. Additionally, a chlorinated polyisobutene (PIBCl) was found.

Example 1 (comparative)

[00131] A polymerization reaction was carried out as described above using (BuO)1AlCl2 as a catalyst in the presence of 0.1 equivalent of diisopropyl ether towards (BuO)1AlCl2. A polyisobutylene polymer with Mn(SEC) = 2100 g/mol (Mn(NMR) = 1610 g/mol) was obtained in 95% yield. Polydispersity and double bond distribution are presented in Table 1.

Example 2

[00132] A polymerization reaction was carried out as described above, but (iPrO)1AlCl2 was used instead of (BuO)1AlCl2. A polyisobutylene polymer with Mn(SEC) = 1960 g/mol (Mn(NMR) = 1470 g/mol) was obtained in 97% yield. Polydispersity and double bond distribution are presented in Table 2.

Example 3

[00133] A polymerization reaction was carried out as described in Example 1, but without an addition of ether. A polyisobutylene polymer with Mn(SEC) = 2700 g/mol (Mn(NMR) = 2100 g/mol) was obtained in 100% yield. Polydispersity and double bond distribution are presented in Table 3.

Example 4

[00134] A polymerization reaction was carried out as described in Example 1, but 0.8 equivalent of iPr2O to (BuO)1AlCl2 was introduced into the system instead of 0.1 equivalent. A polyisobutylene polymer with Mn(SEC) = 600 g/mol (Mn(NMR) = 500 g/mol) was obtained in 27% yield. The polydispersity and distribution of double bonds are presented in Table 4.

Example 5

[00135] A polymerization reaction was carried out as described in Example 1, but 0.1 equivalent of Et2O to (BuO)1AlCl2 was introduced into the system instead of 0.1 equivalent of iPr2O. A polyisobutylene polymer with Mn(SEC) = 6530 g/mol (Mn(NMR) = 5850 g/mol) was obtained in a yield of 55%. The polydispersity and distribution of double bonds are presented in Table 5.

Example 6

[00136] A polymerization reaction was carried out as described in Example 4, but (iPrO)0.8AlCl2.2 was used as a catalyst instead of (BuO)1AlCl2 in the presence of 0.8 equivalents of iPr2O. A polyisobutylene polymer with Mn(SEC) = 1140 g/mol (Mn(NMR) = 1240 g/mol) was obtained in 74% yield. Polydispersity and double bond distribution are shown in Table 6.

Example 7

[00137] A polymerization reaction was carried out as described in Example 6, but (Bu)0.8AlCl2.2 was used as a catalyst instead of (iPrO)0.8AlCl2.2 in the presence of 0.8 equivalents of iPr2O. A polyisobutylene polymer with Mn(SEC) = 680 g/mol (Mn(NMR) = 660 g/mol) was obtained in 44% yield. Polydispersity and double bond distribution are shown in Table 7.

Example 8

[00138] A polymerization reaction was carried out as described in Example 6, but (PhO)0.8AlCl2.2 was used as a catalyst instead of (iPrO)0.8AlCl2.2 in the presence of 0.8 equivalents of iPr2O. A polyisobutylene polymer with Mn(SEC) = 1760 g/mol (Mn(NMR) = 1750 g/mol) was obtained in 22% yield. The polydispersity and double bond distribution are presented in Table 8.

Example 9

[00139] A polymerization reaction was carried out as described in Example 6, but (iPrO)0.8AlBr2.2 was used as a catalyst instead of (iPrO)0.8AlCl2.2 in the presence of 0.8 equivalents of iPr2O. A polyisobutylene was obtained with a Mn(SEC) = 1050 g/mol (Mn(NMR) = 920 g/mol) in a yield of 71%. The polydispersity and double bond distribution is presented in Table 9.

Example 10

[00140] A polymerization reaction was carried out as described in Example 9, but 1.0 equivalents of iPr2O was added to the system instead of 0.8 equivalents. A polyisobutylene polymer was obtained with Mn(SEC) = 940 g/mol (Mn(NMR) = 840 g/mol) in a yield of 61%. Polydispersity and double bond distribution are presented in Table 10.

Example 11

[00141] A polymerization reaction was carried out as described in Example 9, but 0.8 equivalents of different ethers were added to the system instead of iPr2O. The yield, molecular weight, polydispersity and double bond distribution are presented in Table 11.

Example 12

[00142] A polymerization reaction was carried out as described in Example 9, but (iPO)0.6AlBr2.4 was used instead of (iPO)0.8AlBr2.2. A polyisobutylene polymer was obtained with Mn(SEC) = 780 g/mol (Mn(NMR) = 680 g/mol) in 92% yield. Polydispersity and double bond distribution are shown in Table 12.

Example 13

[00143] A polymerization reaction was carried out as described in Example 9, but 51 mM (iPO)0.8AlBr2.2 was used instead of 38 mM. A polyisobutylene polymer was obtained with Mn(SEC) = 1180 g/mol (Mn(NMR) = 1230 g/mol) in 76% yield. Polydispersity and double bond distribution are shown in Table 13.

Example 14

[00144] A polymerization reaction was carried out as described in Example 9, but 26 mM (iPO)0.8AlBr2.2 was used instead of 38 mM. A polyisobutylene polymer was obtained with Mn(SEC) = 1490 g/mol (Mn(NMR) = 1690 g/mol) in 65% yield. Polydispersity and double bond distribution are shown in Table 14.

Claims (14)

1. Process for the preparation of highly reactive isobutene homo- or copolymers with a content of terminal vinylidene double bonds per end of the polyisobutene chain of at least 70 mol%, characterized by the fact that it comprises polymerizing isobutene or a mixture of monomers comprising isobutene in the presence of a hydrocarbyloxy aluminum compound Al(ORa)p(Rb)qXr, or mixture thereof, wherein Ra and Rb, independently of each other, represent a C1 to C20 alkyl radical, C5 to C8 cycloalkyl radical, C6 to C20 aryl radical or C7 to C20 arylalkyl radical, rational number of at least 0 (zero) and less than 3, and r, independently of another, represents a rational number of at least 0 (zero) and less than 3, with the condition that the sum of (p + q + r ) is always 3, effective as a polymerization catalyst in the presence of at least one donor compound. 2. Process according to claim 1, characterized by the fact that the content of terminal vinylidene double bonds per end of the polyisobutene chain is at least at least 75%, preferably at least 80 mol%. 3. Process according to claim 1, characterized by the fact that Ra is a C1 to C4 alkyl radical. 4. Process according to any of the preceding claims, characterized by the fact that Rb is a Ci to C4 alkyl radical. 5. Process according to any one of the preceding claims, characterized in that X is selected from the group consisting of chloride and bromide. 6. Process according to any one of the preceding claims, characterized in that at least one donor compound is present, which is selected from the group consisting of ethers, hydrocarbyl carboxylates, ethers, alcohols, aldehydes, ketones and phenols . 7. Process according to claim 6, characterized by the fact that the donor is at least one ether of the general formula R1-O-R2, wherein the variables R1 and R2 are each, independently, alkyl radicals C1 to C20, preferably C1 to C8 alkyl radicals especially C1 to C4 alkyl radicals, C1 to C8 haloalkyl radicals, C5 to C8 cycloalkyl radicals, preferably C5 to C6 cycloalkyl radicals, C6 to C20 aryl radicals, especially C6 to C12 aryl radicals or C7 to C20 arylalkyl radicals , especially C7 to C12 arylalkyl radicals. 8. Process according to claim 7, characterized in that the donor is at least one hydrocarbyl carboxylate of the general formula R3-COOR4, in which the variables R3 and R4 are each independently C1 to C20 alkyl radicals, especially radicals C1 to C8 alkyl, C5 to C8 cycloalkyl radicals, C6 to C20 aryl radicals, especially C6 to C12 aryl radicals or C7 to C20 arylalkyl radicals, especially C7 to C12 arylalkyl radicals. 9. Process according to any one of the preceding claims, characterized in that the polymerization is carried out with the additional use of a mono- or polyfunctional initiator that is selected from organic hydroxyl compounds in which one or more hydroxyl groups are, each, bonded to an sp3 hybridized carbon atom, organic halogen compounds in which one or more halogen atoms are each bonded to an sp3 hybridized carbon atom, and water. 10. Process according to claim 9, characterized in that the initiator is selected from water, 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. 11. Process according to claim 9 or 10, characterized by the fact that the molar ratio of the aforementioned initiators to the isobutene monomer used in the case of isobutene homopolymerization or to the total amount of polymerizable monomers used in the case of isobutene copolymerization , based on each individual functional site of the initiator, is 0.0005:1 to 0.1:1 or when water is used as the sole initiator or in combination with organic hydroxyl compounds and/or organic halogen compounds as initiators Additionally, the molar ratio of water to isobutene monomer used in the case of isobutene homopolymerization or to the total amount of polymerizable monomers used in the case of isobutene copolymerization is 0.0001:1 to 0.1:1 12. Process according to any one of the previous claims, characterized by the fact that the polymerization is carried out at a temperature of -90°C to + 30°C. 13. Process according to any of the preceding claims, characterized in that the polymerization is carried out in a halogen-free solvent. 14. Process according to any one of the preceding claims, characterized in that the hydrocarbyloxy aluminum compound is free of any additional Bronsted acids, preferably free of any hydrogen halide acids.