EP2742073A1

EP2742073A1 - Process for preparing high-reactivity isobutene homo- or copolymers

Info

Publication number: EP2742073A1
Application number: EP12745871.9A
Authority: EP
Inventors: Hannah Maria KÖNIG; Klaus MÜHLBACH; Thomas Wettling; Ulrich Eichenauer; Herbert Mayr
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2011-08-11
Filing date: 2012-08-10
Publication date: 2014-06-18
Also published as: KR20140049024A; RU2014108711A; SG10201606556WA; RU2608510C2; JP6099648B2; CN103764695A; BR112014002551A2; SG2014004303A; MY166046A; JP2014524492A; WO2013021058A1; AR087514A1

Abstract

Preparation of high-reactivity isobutene homo- or copolymers with a content of terminal vinylidene double bonds per polyisobutene chain end of at least 50 mol% by polymerization of isobutene or isobutene-comprising monomer mixtures in the presence of Lewis acids suitable as polymerization catalysts or of complexes which are effective as polymerization catalysts and are formed from Lewis acids and donors, and in the presence of initiators, wherein the initiators used are organic sulfonic acids Z‑SO₃H in which the variable Z denotes an alkyl radical, haloalkyl radical, cycloalkyl radical, aryl radical or arylalkyl radical.

Description

Description: The present invention relates to a novel process for the preparation of highly reactive isobutene homopolymers or copolymers having a terminal vinylidene double bond content per polyisobutene chain end of at least 50 mol%. Furthermore, the present invention relates to novel isobutene polymers. In contrast to the so-called low-reactive polymers, highly reactive isobutene homopolymers or copolymers are understood to mean those polyisobutenes which contain a high content of terminal ethylenic double bonds (a-double bonds), in practice usually at least 80 mol%, based on the individual chain ends of the polyisobutene macromolecules. For the purposes of the present application, vinylidene groups are understood as meaning those double bonds whose position in the polyisobutene macromolecule is represented by the general formula

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

α-position. "Polymer" stands for the truncated to an isobutene polyisobutene. The vinylidene groups show the highest reactivity, for example in the case of thermal addition to sterically demanding reactants such as maleic anhydride, whereas a double bond further inside the macromolecules shows in most cases no or lower reactivity in the case of functionalization reactions. Highly reactive polyisobutenes are used inter alia as intermediates for the preparation of additives for lubricants and fuels, as described for example in DE-A 27 02 604.

Such highly reactive polyisobutenes are, for example, according to the method of

DE-A 27 02 604 obtainable by cationic polymerization of isobutene in the liquid phase in the presence of boron trifluoride as a catalyst. The disadvantage here is that the resulting polyisobutenes have a relatively high polydispersity. The polydispersity is a measure of the molecular weight distribution of the polymer chains obtained and corresponds to the quotient of weight-average molecular weight M _w and number-average molecular weight M _n (PDI =

Polyisobutenes having a similarly high proportion of terminal double bonds but having a narrower molecular weight distribution are obtainable, for example, by the process of EP-A 145 235, US Pat. No. 5,408,018 and WO 99/64482, the polymerization being carried out in the presence of a deactivated catalyst, for example a Complex of boron trifluoride with alcohols and / or ethers, takes place. Highly reactive polyisobutenes are also obtainable by living cationic polymerization of isobutene and subsequent dehydrohalogenation of the resulting polymerization product, for example according to the process of US Pat. No. 5,340,881. However, such a process is expensive, since the halogen end group introduced with the living cationic polymerization has to be eliminated in a separate step in order to generate the double bond.

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

In the literature article "Cationic polymerization using heteropolyacid salt catalysts" in Topics in Catalysis Vol. 23, pp. 175-181 (2003), James D. Burrington et al. point out that with aluminum trichloride as the polymerization catalyst for isobutene, only low-reactivity polyisobutenes having a low content of terminal vinylidene double bonds (cf.

Double bonds) can be obtained. Thus, on page 178 in Table 1 of this article, an example of a polyisobutene prepared with AlC is given, which has a number-average molecular weight M _n of 1000-2000, a polydispersity M _w / M _n of 2.5-3.5 and a content of Vinylidene isomer (α-double bond) of only 5% (besides 65% "Tri", 5% "β" and 25% "Tetra").

The literature article "Novel initiating system based on AlC etherates for quasi-silicating cationic polymerization of styrene" in Polymer Bulletin Vol. 52, pp. 227-234 (2004) describes Sergei V. Kostjuk et al. a catalyst system of 2-phenyl-2-propanol and an aluminum trichloride-di-n-butyl ether complex for the polymerization of styrene. The polydispersities M _w / M _{n of} the styrenic polymers produced in this way are "~ 2.5" (see summary) and "~ 3", respectively (see page 230).

The international patent application with the file reference PCT / EP201 1/051929 describes a process for the preparation of highly reactive isobutene homo- or copolymers having a content of terminal vinylidene double bonds per polyisobutene chain end of at least 50 mol%, in which Isobutene or an isobutene-containing monomer mixture in the presence of an effective as a polymerization catalyst aluminum trihalide donor complex or an aluminum alkyl halide donor complex polymerized, which contains as donor an organic compound having at least one ether function or a carboxylic acid ester function.

From CN 101955558 A it is known that iron (III) chloride is suitable as a coinitiator in the cationic isobutene polymerization for the preparation of highly reactive polyisobutenes and their copolymers. As initiators, water, phenols, protic acids such as sulfuric acid, tertiary alcohols, tertiary chlorides, tertiary carboxylic acid esters and carboxylic acids themselves are recommended. As a complexing agent for the polymerization initiating systems in particular alkyl ethers are mentioned. WO 2006/01 1868 describes the polymerization of olefins using fluorohydrocarbons as solvent. Insofar as isobutene polymers are addressed - in particular isobutene-isoprene copolymers ("butyl rubber") are put into the foreground - there is no indication of a possible high content of terminal vinylidene double bonds. The initiator system for the polymerization may include, among others, sulfonic acids.

The object of the present invention was to provide a process for the preparation of highly reactive isobutene homo- or copolymers containing vinylidene terminal compounds.

To provide double bonds per polyisobutene chain end of at least 80 mole% and at the same time with a narrow molecular weight distribution (i.e., low polydispersities) in acceptable levels. The catalyst system used should be sufficiently active, durable, easy to handle and not susceptible to failure.

The object has been achieved by a process for the preparation of highly reactive isobutene homo- or copolymers having a content of terminal vinylidene double bonds per polyisobutene chain end of at least 50 mol% by polymerization of isobutene or a monomer mixture containing isobutene in the presence of at least one polymerisate. oncatalyst suitable Lewis acid or a complex effective as a polymerization catalyst of at least one Lewis acid and at least one donor and in the presence of at least one initiator, which is characterized in that at least one initiator is an organic sulfonic acid of the general formula Z-SO3H, in which the variable Z denotes a C to C 20 -alkyl radical, C to C 20 -haloalkyl radical, C 5 to C 8 -cycloalkyl radical, C 6 to C 20 -aryl radical or a C 7 to C 20 -arylalkyl radical.

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

In the context of the present invention, the following definitions apply to generically defined radicals:

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

A C 1 to C 20 alkyl radical is a linear or branched alkyl radical having 1 to 20 carbon atoms. Examples of these are the abovementioned C 1 -C 5 -alkyl radicals and furthermore n-nonyl, isononyl, n-decyl, 2-propylheptyl, n-undecyl, n-dodecyl, n-tridecyl, isotridecyl, n-tetradecyl, n-hexadecyl, n-octadecyl and n-eicosyl. Such C 1 - to C 20 -alkyl radicals can also to a small extent heteroatoms such as oxygen, nitrogen or halogen atoms, eg. As chlorine or fluorine, and / or non-protic functional groups such as carboxyl ester groups, cyano groups or nitro groups.

A C 2 to C 20 haloalkyl radical or a C 1 to C 1 haloalkyl radical is a radical having the above-mentioned basic structures for C 1 to C 20 -alkyl radicals or C 1 to C 6 -alkyl radicals, in which, however, the hydrogen atoms are more widely protected by halogen atoms, are replaced in particular by fluorine and / or chlorine atoms. Preferably, all or nearly all hydrogen atoms are replaced by halogen atoms, in particular by fluorine and / or chlorine atoms. Typical examples of such radicals are C 1 - to C 4 -alkyl radicals in which at least 60%, in particular at least 75%, especially at least 90% of the number of hydrogen atoms are replaced by fluorine and / or chlorine atoms, for example dichloromethyl, trichloromethyl, difluoromethyl, Trifluoromethyl, chlorodifluoromethyl, fluorodichloromethyl, pentachloroethyl or pentafluoroethyl.

A C5 to C8 cycloalkyl group is a saturated cyclic group which 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, Cylcoheptyl, 2-, 3- or 4-methylcycloheptyl, cyclooctyl, 2-, 3-, 4- or 5-methylcyclooctyl. Such C5 to C7 cycloalkyl radicals can also to a small extent heteroatoms such as oxygen, nitrogen or halogen atoms, for. As chlorine or fluorine, and / or non-protic functional groups such as carboxyl ester groups, cyano groups or nitro groups.

A C 6 to C 20 aryl radical or a C 6 to C 12 aryl radical is preferably optionally substituted phenyl, optionally substituted naphthyl, optionally substituted anthracenyl or optionally substituted phenanthrenyl. Such aryl groups may carry 1 to 5 non-protic substituents or non-protic functional groups, for example C 1 to C 6 alkyl, C 1 to C 5 haloalkyl such as C 1 to C 6 chloroalkyl or C 1 to C 8 fluoroalkyl, halogen such as chlorine or fluoro, nitro , Cyano or phenyl. Examples of such aryl radicals are phenyl, naphthyl, biphenyl, anthracenyl, phenanthrenyl, tolyl, nitrophenyl, chlorophenyl, dichlorophenyl, pentafluorophenyl, pentachlorophenyl, (trifluoromethyl) phenyl, bis (trifluoromethyl) phenyl, (trichloro) methylphenyl and bis (trichloromethyl) phenyl. A C 7 - to C 20 -arylalkyl radical or a C 7 - to C 12 -arylalkyl radical is preferably optionally substituted C 1 -C ₄ -alkylphenyl, such as benzyl, o-, m- or p-methylbenzyl, 1- or 2-phenylethyl, 1 -, 2- or 3-phenylpropyl or 1 -, 2-, 3- or 4-phenyl-butyl, optionally substituted C ₄ to C -Alkylnaphthyl as naphthylmethyl, optionally substituted C 1 to C ₄ -Alkylanthracenyl as anthracenylmethyl or optionally substituted Cr to C ₄ alkylphenanthrenyl such as phenanthrenylmethyl. Such arylalkyl radicals can carry 1 to 5 non-protic or non-protic functional groups, in particular on the aryl part, for example C 1 to C 6 -alkyl, C 1 to C 5 -haloalkyl such as C 1 to C 5-chloroalkyl or C 1 to C 5 -fluoro- alkyl, halogen such as chlorine or fluorine, nitro or phenyl.

As a rule, the process according to the invention for the preparation of highly reactive isobutene homopolymers or copolymers proceeds as a result of the use of the polymerization catalyst complex of at least one Lewis acid and optionally at least one donor and the initiators described, according to a cationic reaction mechanism.

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

The variable Z preferably represents a C to Cs-alkyl radical, C to Cs-haloalkyl radical, C5 to Cs-cycloalkyl radical, C6 to C12-aryl radical or a C7 to C12-arylalkyl radical. Particularly preferably, Z represents a a C to C ₄ alkyl radical, a C to C ₄ haloalkyl group, an optionally substituted phenyl radical, z. A tolyl radical or a xylyl radical, or an optionally substituted C ₄ to C ₄ alkylphenyl radical, e.g. B. a benzyl radical.

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

As a Lewis acid suitable as a polymerization catalyst or in the effective complex as a polymerization catalyst in principle all by definition as Lewis acids designated inorganic molecules, but especially halogen compounds of metals and semimetals of the Periodic Table of the Elements whose valences are completely saturated by halogen atoms or in addition to the halogen substituents still one or more organic carbon radicals - in particular C to C ₄ alkyl radicals - wear. Suitable halogen substituents in these element halides and elemental alkyl halides are iodine, bromine and, in particular, fluorine and especially chlorine. Of course, mixtures of such Element halides or those Elementalkylhalogenide each with each other and with each other are used.

If, for example, the halides or alkyl halides of aluminum are used as such Lewis acids, typically the following species can be used: aluminum trifluoride, aluminum trichloride, aluminum tribromide; aluminum alkyl halides as mono (Ci to C ₄ - alkyl) aluminiumdihalogenide or di (Ci to _C4 alkyl) aluminiummonohalogenid as Methylalu- miniumdichlorid, ethylaluminum dichloride, dimethylaluminum chloride or Diethylaluminiumchlo-.

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

Typical of such binary chlorine compounds are SCCI _3, YC, YbCI _3, TiC, TiCl _4, ZrCl _4, HfCI ₄ VCIs, VCU, NbCl _3, NbCl _5, TaCI _5, CrCl _2, CrCl _3, M0CI3, MoCI _5, WCI _5, WCI ₆ , MnCl ₂ , ReCl ₃ , ReCl ₅ , FeC, FeCl ₃ , RuCl ₃ , OsCl ₃ , C0Cl 2, C0Cl ₃ , RhCl ₃ , IrCu, NiC, PdC, PtC, CuCl, CuC, AgCl, AuCl, ZnCl ₂ , CdCl ₂ , HgCI, HgCl ₂ , BCI ₃ , AICI ₃ , GaCl ₃ , InCl ₃ , TICI ₃ , SiCU, GeCl ₄ , SnCl ₂ , SnCl ₃ , SnCl ₄ , PbC, PbCl ₄ , PCI ₃ , PCI ₅ , AsCl ₃ , SbCl ₃ , SbCI ₅ and BiCI ₃ . Of these, particularly preferred are BCI ₃ , AICI ₃ , TiCU, FeC, FeCl ₃ and ZnCl ₂ .

Typical such fluorine compounds are ScF ₃ , YF ₃ , YbF ₃ , TiF ₃ , TiF ₄ , ZrF ₄ , HfF ₄ , VF ₃ , VF ₄ , NbF ₃ , NbF ₅ , TaF ₅ , CrF ₂ , CrF ₃ , MoF ₃ , MoF ₅ , WF ₅ , WF ₆ , MnF ₂ , ReF ₃ , ReF ₅ , FeF ₂ , FeF ₃ ,

RuF ₃ , OsF ₃ , CoF ₂ , CoF ₃ , RhF ₃ , IrF ₃ , NiF ₂ , PdF ₂ , PtF ₂ , CuF, CuF ₂ , AgF, AuF, ZnF ₂ , CdF ₂ , HgF, HgF ₂ , BF ₃ , AlF 3, GaF _3, LnF _3, TIF _3, SiF _4, GeF _4, SnF _2, SnF _3, SnF _4, PbF _2, PbF _4, PF _3, PF _5, AsF _3, SbF _3, SbF ₅ and BiF. ₃ Of these, BF ₃ , AIF ₃ , TiF ₄ , FeF ₂ , FeF ₃ and ZnF ₂ are particularly preferred. Mixtures of binary chlorine and fluorine compounds can also be used.

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

Very particular preference is given to using the preferred sulfonic acid initiators methanesulfonic acid, trifluoromethanesulfonic acid, trichloromethanesulfonic acid and toluenesulfonic acid together with the preferred Lewis acids or Lewis acid complexes with BCI ₃ , AlCl ₃ , TiCu, FeCl ₂ , FeCl ₃ , ZnCl ₂ , BF ₃ , AIF ₃ , TiF ₄ , FeF ₂ , FeF ₃ and / or ZnF ₂ , especially methanesulfonic acid together with AICI3, BF ₃ or FeCl ₃ , especially when Lewis acid complexes are used, those listed below as preferred Dihydrocarbyl ethers of the general formula R ¹ -0- R ² and / or Carbonsäurehydrocarbylester of the general formula R ³ -COOR ⁴ as donors included.

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

In a preferred embodiment of the present invention, a complex which is effective as a polymerization catalyst and comprises at least one Lewis acid and at least one donor in which the organic compound acting as donor is a dihydrocarbyl ether of the general formula R ¹ -O-R ² in which the variables R ¹ and R ² independently of one another C to C 20 -alkyl radicals, in particular, C ^{1 to} C 8 -alkyl radicals, C 8 to C 8 -cycloalkyl radicals, C 6 to C 20 -aryl radicals, in particular C 6 to C 12 -aryl radicals, or C7-C2o-arylalkyl radicals, in particular C7 to Ci2 arylalkyl radicals, denote, or represents a Carbonsäurehydrocarbylester of the general formula R ³ COOR ^4, in which the variables R ³ and R ⁴ are independently C to C2o-alkyl radicals, in particular , C to Cs-alkyl radicals, C5 to Cs-cycloalkyl radicals, C6 to C20-aryl radicals, in particular C6 to C12-aryl radicals, or C7 to C20-arylalkyl radicals, in particular C7 to C12-arylalkyl radicals.

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

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

The molar ratio of said donor compounds to the Lewis acids, ie especially to said elemental halides and elemental alkyl halides, in particular to the Lewis acids BCI3, AICI3, TiCu, FeC, FeC and ZnC, in the complex polymerization complex is generally in the range of 0.3: 1 to 1, 5: 1, in particular from 0.5: 1 to 1, 2: 1, especially 0.7: 1 to 1, 1: 1; it is in most cases 1: 1. However, it can also be used with a greater degree of closure of the donor compounds, often up to a 10-fold, in particular 3-fold molar excess; the excess amount of donor compounds then additionally acts as a solvent or diluent. Usually, the polymerization catalyst complex is prepared before the polymerization separately from the one or more Lewis acids mentioned, which are usually used in anhydrous form, and the donor or the compounds and then - usually dissolved in an inert solvent such as a halogenated Hydrocarbon, for example dichloromethane - added to the polymerization medium. However, the complex can also be prepared in situ prior to polymerization.

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

Suitable monofunctional initiators organic hydroxy compounds having only one hydroxyl group in the molecule are in particular alcohols and phenols, especially those of the general formula R ⁵ -OH, in the R ⁵ d- to C2o-alkyl radicals, in particular, d- to Cs-alkyl radicals , Cs to Cs-cycloalkyl radicals, C6 to C20-aryl radicals, in particular C6 to C12-aryl radicals, or C7 to C20-arylalkyl radicals, in particular C7 to C12-arylalkyl radicals. Furthermore, the radicals R ^{5 may} also contain mixtures of the abovementioned structures and / or have functional groups other than those already mentioned, for example a keto function, a nitroxide or a carboxyl group, and / or heterocyclic structural elements.

Typical examples of such organic monohydroxy compounds are methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, isobutanol, tert-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, 2 -Ethylhexanol, cyclohexanol, phenol, p-methoxyphenol, o-, m- and p-cresol, benzyl alcohol, p-methoxybenzyl alcohol, 1- and 2-phenylethanol, 1- and 2- (p-methoxyphenyl) ethanol, 1 -, 2 and 3-phenyl-1-propanol, 1-, 2- and 3- (p-methoxyphenyl) -1-propanol, 1- and 2-phenyl-2-propanol, 1- and 2- (p-methoxyphenyl) - 2-propanol, 1-, 2-, 3- and 4-phenyl-1-butanol, 1-, 2-, 3- and 4- (p-methoxyphenyl) -1-butanol, 1-, 2-, 3- and 4-phenyl-2-butanol, 1-, 2-, 3- and 4- (p -methoxyphenyl) -2-butanol, 9-methyl-9H-fluoren-9-ol, 1,1-diphenylethanol, 1, 1-diphenyl-2-propyn-1-ol, 1, 1-diphenylpropanol, 4- (1-hydroxy-1-phenylethyl) benzonitrile, cyclopropyldiphenyl-methanol, 1-hydroxy-1, 1-diphenylpropan-2-one . Benzilic acid, 9-phenyl-9-fluorenol, tri-phenylmethanol, diphenyl (4-pyridinyl) methanol, alpha, alpha-diphenyl-2-pyridinemethanol, 4-methoxytrityl alcohol (in particular polymer bound as solid phase), alpha-tert-butyl-4 -chloro-4'-methylbenzhydrol, cyclohexyldiphenylmethanol, alpha- (p-tolyl) -benzhydrol, 1, 1, 2-triphenylethanol, alpha, alpha-diphenyl-2-pyridineethanol, alpha, alpha-4-pyridylbenzohydrolone N-oxide, 2-fluorotriphenylmethanol, triphenylpropargyl alcohol, 4 - [(diphenyl) hydroxymethyl] benzonitrile, 1- (2,6-dimethoxyphenyl) -2-methyl-1-phenyl-1-propanol, 1, 1, 2-triphenylpropane 1 - ol and p-anisaldehyde carbinol.

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

Particularly suitable monofunctional initiators for organic halogen compounds having a halogen atom in the molecule are compounds of the general formula R ⁶ -Hal, in which shark is a halogen atom selected from fluorine, iodine and in particular chlorine and bromine, and R ^{6 is} C 2 -C 20. Alkyl radicals, in particular, d- to Cs-alkyl radicals, Cs to Cs-cycloalkyl radicals or C7- to C20-arylalkyl radicals, in particular C7- to C12-arylalkyl radicals. Furthermore, the radicals R ^{6 may} also contain mixtures of the abovementioned structures and / or have functional groups other than those mentioned above, for example a keto function, a nitroxide or a carboxyl group, and / or heterocyclic structural elements.

Typical examples of such organic monohalogen compounds are methyl chloride, methyl bromide, ethyl chloride, ethyl bromide, 1-chloropropane, 1-bromopropane, 2-chloropropane, 2-bromopropane, 1-chlorobutane, 1-bromobutane, sec-butyl chloride, sec-butyl bromide, isobutyl chloride, isobutyl bromide, tert-butyl chloride, tert-butyl bromide, 1-chloropentane, 1-bromopentane, 1-chlorohexane, 1-bromohexane, 1-chloroheptane, 1-bromoheptane, 1-chlorooctane, 1-bromoctane, 1 Chloro-2-ethylhexane, 1-bromo-2-ethylhexane, cyclohexyl chloride, cyclohexylbromide, benzylchloride, benzylbromide, 1-phenyl-1-chloroethane, 1-phenyl-1-bromoethane, 1-phenyl-2-chloroethane, 1 -Phenyl-2-bromoethane, 1-phenyl-1-chloropropane, 1-phenyl-1-bromopropane, 1-phenyl-2-chloropropane, 1-phenyl-2-bromopropane, 2-phenyl-2-chloropropane, 2-phenyl 2-bromopropane, 1-phenyl-3-chloropropane, 1-phenyl-3-bromopropane, 1-phenyl-1-chlorobutane, 1-phenyl-1-bromobutane, 1-phenyl-2-chlorobutane, 1-phenyl-2 bromobutane, 1-phenyl-3-chlorobutane, 1-phenyl-3-bromo utane, 1-phenyl-4-chlorobutane, 1-phenyl-4-bromobutane, 2-phenyl-1-chlorobutane, 2-phenyl-1-bromobutane, 2-phenyl-2-chlorobutane, 2-phenyl-2-bromobutane, 2-phenyl-3-chlorobutane, 2-phenyl-3-bromobutane, 2-phenyl-4-chlorobutane and 2-phenyl-4-bromobutane. Suitable difunctional initiators organic halogen compounds having two halogen atoms in the molecule are, for example, 1, 3-bis (1-bromo-1-methylethyl) benzene, 1, 3-bis (2-chloro-2-propyl) benzene (1, 3 Dicumyl chloride) and 1,4-bis (2-chloro-2-propyl) benzene (1,4-dicumyl chloride).

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

Especially more initiators, the atom in such an sp ³ carbon -hydrisiertem are preferred in addition to the hydroxyl group, the radicals R ^5, R ⁶ and R ⁷ carry, which are independently hydrogen, Cr to C2o-alkyl, Cs to Cs cycloalkyl , C ₆ - to C 20 -aryl, C 7 - to C 20 -alkylaryl or phenyl, where one aromatic nucleus contains 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 Cr to C ₄ - may bear as substituents haloalkyl denote, wherein at most one of the variables R ^5, R ⁶ or R ⁷ is hydrogen and at least one of the variables R ^5, R ⁶ or R ⁷ is phenyl, which still one or more, preferably one or two C to C ₄ alkyl, C to C ₄ alkoxy, C to C ₄ hydroxyalkyl or C to C ₄ haloalkyl radicals may carry as substituents. Suitable protic acids are, for example, hydrochloric acid, hydrobromic acid, hydrofluoric acid, sulfuric acid, hydrocyanic acid and mixtures thereof. As proton acids but also protonated ethers can be used.

Very particular preference is given to the present invention further initiators which are water, one or more protic acids, methanol, ethanol, 1-phenylethanol, 1 - (p-methoxyphenyl) ethanol, n-propanol, isopropanol, 2-phenyl-2-propanol (Cumene), n-butanol, isobutanol, sec-butanol, tert-butanol, 1-phenyl-1-chloroethane, 2-phenyl-2-chloropropane (cumyl chloride), tert-butyl chloride and 1, 3- or 1, 4-bis (1-hydroxy-1-methylethyl) benzene and mixtures thereof are selected. Of these, particular preference is given to further initiators which, under water, one or more protic acids, methanol, ethanol, 1-phenylethanol, 1- (p-methoxy-phenyl) -ethanol, n-propanol, isopropanol, 2-phenyl-2-propanol ( Cumene), n-butanol, Isobutanol, sec-butanol, tert-butanol, 1-phenyl-1-chloroethane and 1, 3- or 1, 4-bis (1-hydroxy-1-methylethyl) benzene and mixtures thereof are selected.

The molar ratio of the sum of the inventively used organic sulfonic acids of the general formula Z-SO3H and the optionally used further initiators to the isobutene monomer used in the homopolymerization of isobutene or to the total amount of the polymerizable monomers used in the copolymerization of isobutene, based on each individual functional Site of the initiator (wherein the organic sulfonic acids are to be regarded as monofunctional), usually 0.001: 1 to 0.5: 1, in particular 0.01: 1 to 0.4: 1, especially 0.1: 1 to 0 , 3: 1. When water is used as sole further initiator or in combination with organic hydroxy compounds and / or organic halogen compounds as further initiators, the molar ratio of water alone to the isobutene monomer used in homopolymerization of isobutene or to the total amount of the polymerizable monomers used at Copo in particular from 0.0001: 1 to 0.1: 1, in particular from 0.0002: 1 to 0.05: 1.

Some of the initiator molecules added as organic sulfonic acids and optionally as organic hydroxy or halogen compounds can be incorporated into the polymer chains. The proportion (Uff) of polymer chains which are started by such a built-in organic initiator molecule can be up to 100%, usually from 0 to 90% and can be from 5 to 90%. The remaining polymer chains are formed either by moisture-derived water as the initiator molecule or by chain transfer reactions. In a further preferred embodiment of the present invention, the polymerization is carried out in the presence of from 0.01 to 10 mmol, in particular from 0.05 to 5.0 mmol, especially from 0.1 to 1.0 mmol, in each case based on 1 mol used isobutene monomer in homopolymerization of isobutene or to 1 mol of the total amount of the polymerizable monomers used in copolymerization of isobutene, a nitrogen-containing basic compound.

As such nitrogen-containing basic compound, an aliphatic, cycloaliphatic or aromatic amine of the general formula R ⁷ -NR ⁸ R ⁹ or ammonia can be used, in which the variables R ⁷ , R ⁸ and R ^{9 are} each independently hydrogen, C1- to C 2 -C 4 -alkyl radicals, in particular, C 5 -C -alkyl radicals, C 5 -C -cycloalkyl radicals, C 6 -C 20 -aryl radicals, in particular C 6 -C 12 -aryl radicals, or C 7 -C 20 -arylalkyl radicals, in particular C 7 -C 12 -arylalkyl radicals, stand. If none of these variables is hydrogen, a tertiary amine is present. If one of these variables is hydrogen, a secondary amine is present. If two of these variables are hydrogen, a primary amine is present. If all of these variables are hydrogen, ammonia is present. Typical examples of such amines of the general formula R ⁷ -NR ⁸ R ⁹ are methylamine, ethylamine, n-propylamine, iso-propylamine, n-butylamine, tert-butylamine, sec-butylamine, isobutylamine, tert. -Amylamine, n-hexylamine, n-heptylamine, n-octylamine, 2-ethylhexylamine, cyclopentylamine, cyclohexylamine, aniline, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di tert-butylamine, di-sec-butyl-amine, di-iso-butylamine, di-tert-amylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di (2-) ethylhexyl) amine, dicyclopentylamine, dicyclohexylamine, diphenylamine, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, tri-tert-butylamine, tri-sec-butyl-amine, Tri-iso-butylamine, tri-tert-amylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-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.

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

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

However, very particularly suitable as such nitrogen-containing basic compound is pyridine or a derivative of pyridine (in particular a mono-, di- or tri-d- to C ₄ - alkyl-substituted pyridine) such as 2-, 3-, or 4-methylpyridine ( Picolines), 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, 3,5- or 3,6-dimethylpyridine (lutidines), 2,4,6-trimethylpyridine ( Collidine), 2-, 3, - or 4-tert.

Butylpyridine, 2-tert-butyl-6-methylpyridine, 2,4-, 2,5-, 2,6- or 3,5-di-tert-butylpyridine or 2-, 3, - or 4-phenylpyridine ,

It is possible to use a single nitrogen-containing basic compound or mixtures of such nitrogen-containing basic compounds. For the use of isobutene or an isobutene-containing monomer mixture as a monomer to be polymerized is suitable as an isobutene source both pure isobutene and isobutene-containing C4 hydrocarbon streams, such as C4 raffinates, especially "raffinate 1", C4 cuts from isobutane -Dehydrogenation, C4 slices from steam crackers and from fluid catalysed cracking (FCC) crackers, provided they are largely free of 1,3-butadiene contained therein. A C4 hydrocarbon stream from an FCC refinery unit is also known as a "b / b" stream. Further suitable isobutene-containing C4 hydrocarbon streams are, for example, the product stream of a propylene-isobutane co-oxidation or the product stream from a metathesis unit, which are generally used after customary purification and / or upconcentration. Suitable C4 hydrocarbon streams typically contain less than 500 ppm, preferably less than 200 ppm, butadiene. The presence of 1-butene and of cis- and trans-2-butene is largely uncritical. Typically, the isobutene concentration in said C4 hydrocarbon streams is in the range of 40 to 60 weight percent. Thus, raffinate 1 usually consists essentially of 30 to 50 wt .-% of isobutene, 10 to 50 wt .-% 1-butene, 10 to 40 wt .-% cis- and trans-2-butene and 2 to 35 wt .-% butane; In the polymerization process according to the invention, the unbranched butenees in raffinate 1 are generally virtually inert and only the isobutene is polymerized.

In a preferred embodiment, the monomer used for the polymerization is a technical C 4 -hydrocarbon stream having an isobutene content of from 1 to 100% by weight, in particular from 1 to 99% by weight, in particular from 1 to 90% by weight. %, more preferably from 30 to 60% by weight, in particular a raffinate 1 stream, a b / b stream from an FCC refinery unit, a product stream from a propylene-isobutane co-oxidation or a product stream from a metathesis unit ,

In particular, when using a raffinate 1 stream as isobutene source, the concomitant use of water as sole further or together with further initiator selected from organic hydroxy compounds and organic halogen compounds has proven itself, especially if at temperatures from -30 ° C to + 50 ° C, in particular from 0 ° C to + 30 ° C, polymerized.

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

It is also possible to react monomer mixtures of isobutene or of the isobutene-containing hydrocarbon mixture with olefinically unsaturated monomers which are copolymerizable with isobutene. If monomer mixtures of isobutene are to be copolymerized with suitable comonomers, the monomer mixture contains preferred at least 5 wt .-%, particularly preferably at least 10 wt .-% and in particular at least 20 wt .-% isobutene, and preferably at most 95 wt .-%, particularly preferably at most 90 wt .-% and in particular at most 80 wt. % Comonomers. Suitable copolymerizable monomers are: vinylaromatics such as styrene and a-

Methylstyrene, C 1 - to C 4 -alkylstyrenes such as 2-, 3- and 4-methylstyrene and 4-tert-butylstyrene, halobenzenes such as 2-, 3- or 4-chlorostyrene and isoolefins having 5 to 10 carbon atoms such as 2-methylbutene -1, 2-methylpentene-1, 2-methylhexene-1, 2-ethyl-1-pentene-1, 2-ethylhexene-1 and 2-propylheptene-1. Other suitable comonomers are olefins which have a silyl group, such as 1-trimethoxysilylethene, 1 - (trimethoxysilyl) propene, 1 - (trimethoxysilyl) -2-methylpropene-2, 1 - [tri (methoxyethoxy) silyl] -ethene , 1 - [tri (methoxyethoxy) silyl] propene, and 1 - [tri (methoxyethoxy) silyl] -2-methylpropene-2. Furthermore, depending on the polymerization conditions, comopters also include isoprene, 1-butene and cis- and trans-2-butene.

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

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

The inventive method is suitable both for carrying out at low temperatures, for example at -90 ° C to 0 ° C, and in particular at higher temperatures, ie at least 0 ° C, for example at 0 ° C to + 50 ° C or at 0 ° C to + 30 ° C, suitable. However, the polymerization according to the inventive method is preferably carried out at a temperature of -30 ° C to + 50 ° C, in particular at 0 ° C to + 30 ° C, for example at room temperature (+20 to + 25 ° C). If the polymerization according to the process according to the invention takes place at or above the boiling point of the monomer or monomer mixture to be polymerized, it is preferably carried out in pressure vessels, for example in autoclaves or in pressure reactors.

Preferably, the polymerization is carried out according to the process of the invention in the presence of an inert diluent. The inert diluent used should be suitable for reducing the increase in the viscosity of the reaction solution which usually occurs during the polymerization reaction to such an extent that the removal of the heat of reaction formed can be ensured. Suitable diluents are those solvents or solvent mixtures which are inert to the reagents used. Suitable diluents are, for example, aliphatic hydrocarbons such as n-butane, n-pentane, n-hexane, n-heptane, n-octane and isooctane, cycloaliphatic hydrocarbons such as cyclopentane and cyclohexane, aromatic hydrocarbons such as benzene, toluene and the xylenes, and halogenated Hydrocarbons, in particular halogenated aliphatic hydrocarbons, such as methyl chloride, dichloromethane, trichloromethane (chloroform), 1, 1-dichloroethane, 1, 2-dichloroethane, trichloroethane and 1-chlorobutane and halogenated aromatic hydrocarbons and alkylaromatics halogenated in the alkyl side chains, such as chlorobenzene, monofluoromethylbenzene, Difluoromethylbenzene and trifluoromethylbenzene, and mixtures of the aforementioned diluents. As halogenated hydrocarbons for the inert diluents mentioned above and below, chlorinated hydrocarbons, in particular pure chlorohydrocarbons, are preferred. Fluorohydrocarbons are preferably excluded from the inert diluents which can be used here in order to largely exclude residual contents of fluorine in the polymer. The inert constituents of isobutene-containing C ₄ hydrocarbon streams are also used as diluents or as constituents of the solvent mixtures mentioned.

The polymerization according to the invention is preferably carried out in an aliphatic, cycloaliphatic or aromatic hydrocarbon, in a halogenated hydrocarbon, in particular in a halogenated aliphatic hydrocarbon, or in a mixture of aliphatic, cycloaliphatic and / or aromatic hydrocarbons or halogenated hydrocarbons, in particular 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, usually in the Vol. Ratio from 10:90 to 90:10, especially from 50:50 to 85:15. Preferably, the diluents are freed before use of impurities such as water, carboxylic acids or mineral acids, for example by adsorption on solid adsorbents such as activated carbon, molecular sieves or ion exchangers. In a further preferred embodiment, the polymerization according to the invention is carried out in halogen-free aliphatic or, in particular, halogen-free aromatic hydrocarbons, in particular toluene. For this embodiment, water has proven to be particularly advantageous as a further initiator, optionally in combination with the said organic hydroxy compounds and / or the said organic halogen compounds.

Preferably, the polymerization is carried out according to the process of the invention under largely aprotic, in particular under substantially anhydrous reaction conditions. Under largely aprotic or largely anhydrous reaction conditions, it is understood that the water content (or the content of protic impurities) in the reaction mixture is less than 50 ppm and in particular less than 5 ppm. As a rule, therefore, the feedstocks will be dried before use by physical and / or chemical means. In particular, it has proven useful to use the aliphatic or cycloaliphatic hydrocarbons used as solvent after conventional pre-cleaning and predrying with an organometallic compound, such as an organolithium, organomagnesium or organoaluminum compound, in an amount sufficient to remove the traces of water from the Solvent largely remove. The solvent thus treated is then preferably condensed directly into the reaction vessel. Similarly, one can also proceed with the monomers to be polymerized, in particular with isobutene or with the isobutene-containing mixtures. Drying with other conventional drying agents such as molecular sieves or predried oxides such as alumina, silica, calcium oxide or barium oxide is also suitable. The halogenated solvents, which are not suitable for drying with metals such as sodium or potassium or with metal alkyls, are freed from water or traces of water with suitable drying agents, for example with calcium chloride, phosphorus pentoxide or molecular sieve. In an analogous manner, it is also possible to dry those starting materials for which a treatment with metal alkyls likewise does not come into consideration, for example vinylaromatic compounds. Even if water is used as an initiator, residual moisture from solvents and monomers should preferably be removed as far as possible or completely before the reaction by drying in order to be able to use the further initiator of water in a specified amount in a targeted manner, thereby obtaining a higher process control and reproducibility of the results. As a rule, the polymerization of the isobutene or the isobutene-containing starting material takes place spontaneously when the complex effective as the polymerization catalyst is contacted with the isobutene or the isobutene-containing monomer mixture at the desired reaction temperature. In this case, it is possible to proceed by initially introducing the monomers in the diluent, bringing them to the reaction temperature and then adding the complex. It is also possible to introduce the complex, if appropriate in the diluent, and then to add the monomers. The beginning of polymerization is then the time at which all the reactants are contained in the reaction vessel. For the preparation of isobutene copolymers, it is possible to proceed by initially introducing the monomers, if appropriate in the diluent, and then adding the complex. The adjustment of the reaction temperature can be carried out before or after the addition of the complex. It is also possible to initially provide only one of the monomers, if appropriate in the diluent, then to add the complex and to react it only after a certain time, for example when at least 60%, at least 80% or at least 90% of the monomer have reacted or adding the further monomers. Alternatively, one may submit the complex, optionally in the diluent, then add the monomers simultaneously or sequentially and then adjust the desired reaction temperature. The beginning of polymerization is then that time at which the complex and at least one of the monomers are contained in the reaction vessel.

In addition to the discontinuous procedure described here, the polymerization can also be carried out in accordance with the process of the invention as a continuous process. This leads to the starting materials, i. the monomer (s) to be polymerized, optionally the diluent and optionally the complex polymerization complex, are continuously added to the polymerization reaction and continuously remove reaction product, so that more or less stationary polymerization conditions are established in the reactor. The monomer (s) to be polymerized may be supplied as such, diluted with a diluent or solvent, or as a monomer-containing hydrocarbon stream.

The complex which is effective as a polymerization catalyst is generally dissolved, dispersed or suspended in the polymerization medium. Also, a support of the complex on conventional substrates is possible. Suitable reactor types for the polymerization process of the present invention are usually stirred tank reactors, loop reactors and tubular reactors, but also fluidized bed reactors, fluidized bed reactors, stirred tank reactors with and without solvent, liquid bed reactors, continuous fixed bed reactors and batchwise batchwise reactors.

In the process according to the invention, the complex polymerization catalyst is generally used in such an amount that the molar ratio of element in the preferred as Lewis acids Elementhalogeniden or Elementalkylhalogeniden to isobutene in homopolymerization of isobutene or to the total amount of polymerizable Monomers in the copolymerization of isobutene in the range of 1: 5 to 1: 5000, preferably 1: 10 to 1: 5000, in particular 1: 15 to 1: 1000, especially 1: 20 to 1: 250, is located.

To terminate the reaction, the reaction mixture is preferably deactivated, for example by adding a protic compound, in particular by adding water, alcohols, such as methanol, ethanol, n-propanol and isopropanol or mixtures thereof with water, or by adding an aqueous base, for example an aqueous solution an alkali or alkaline earth hydroxides such as sodium hydroxide, potassium hydroxide, magnesium hydroxide or calcium hydroxide, an alkali or alkaline earth metal carbonate such as sodium, potassium, magnesium or calcium carbonate, or an alkali or Erdalkalihydrogencarbonats such as sodium, potassium, magnesium or calcium bicarbonate.

The process according to the invention is used to prepare highly reactive isobutene homopolymers or copolymers having a content of terminal vinylidene double bonds (a double bonds) per polyisobutene chain end of at least 50 mol%, preferably of at least 60 mol%, preferably of at least 70 mol -%, preferably of at least 80 mol%, preferably of at least 85 mol%, particularly preferably of at least 90 mol%, particularly preferably more than 91 mol% and in particular of at least 95 mol%, for example of nearly 100 mol%. In particular, it also serves for the preparation of highly reactive isobutene copolymers which are composed of isobutene and at least one vinylaromatic monomer, in particular styrene, and a content of terminal vinylidene double bonds (a-double bonds) per polyisobutene chain end of at least 50 mol -%, preferably of at least 60 mol%, preferably of at least 70 mol%, preferably of at least 80 mol%, preferably of at least 80 mol%, preferably of at least 85 mol%, particularly preferably of at least 90 mol% %, more preferably more than 91 mol%, and especially at least 95 mol%, eg of nearly 100 mol%. For the preparation of such copolymers of isobutene and at least one vinylaromatic monomer, in particular styrene, isobutene or an isobutene-containing hydrocarbon cut with the at least one vinylaromatic monomer in a weight ratio of isobutene to vinyl aromatic from 5 to 95: 95 to 5 , in particular from 30 to 70 to 70 to 30, copolymerized. Preferably, the highly reactive isobutene homo- or copolymers prepared by the process according to the invention and especially the isobutene homopolymers have a polydispersity (PDI = Mw / Mn) from 1.05 to less than 3.5, preferably from 1.05 to less than 3.0, preferably from 1.05 to less than 2.5, preferably from 1.05 to 2.3, more preferably from 1.05 to 2.0 and in particular from 1.1 to 1.85. Typical values for PDI are 1, 2 to 1, 7 for optimum process control.

The highly reactive isobutene homo- or copolymers prepared by the process according to the invention preferably have a number-average molecular weight M _n (determined by gel permeation chromatography) of preferably 500 to 250,000, more preferably 500 to 100,000, more preferably 500 to 25,000 and in particular 500 to 5,000. Isobutene homopolymers even more preferably have a number average molecular weight M _{n of} from 500 to 10,000 and in particular from 500 to 5,000, for example from about 1,000 or from about 2300. The isobutene polymers having terminal vinylidene double bonds which occur in the isobutene homopolymers prepared according to the invention are those which are known as Containing initiator molecules incorporated organic sulfonic acids, new compounds are Therefore, the subject of the present invention are also isobutene polymers of the general formula I.

in the

R ¹⁰ denotes a sulfonic acid grouping of the general formula -O-SO 2 Z in which the variable Z is a C 2 -C 20 -alkyl radical, C 2 -C 20 -haloalkyl radical, C 5 -C 5 -cycloalkyl radical, C 6 -C 20 -aryl radical or a C 7- to C2o-arylalkyl radical, and R ¹¹ and R ¹² independently of one another are hydrogen, C 1 - to C 20 -alkyl radicals, C 5 - to C 8 -cycloalkyl radicals, C 6 - to C 20 -aryl radicals or C 7 - to C 20 -alkylaryl radicals, and n is a number from 9 to 4500 stands.

In a preferred embodiment, R ¹¹ and R ¹² independently of one another denote hydrogen, C 1 -C ₄ -alkyl, in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl, or phenyl which may also carry one or two C 1 to C ₄ -alkyl or C 1 to C ₄ -alkoxy radicals as substituents, and n is a number from 9 to 4500, preferably from 9 to 180, in particular from 9 to 90, especially 15 to 45 stands.

By the process according to the invention, monomer mixtures containing isobutene or isobutene under cationic conditions with satisfactory to high conversions of usually 20 to 100%, in particular 35 to 90%, in short reaction times of usually 5 to 120 minutes, in particular 5 to 60 minutes, successfully polymerized to highly reactive isobutene homo- butene copolymers having a terminal vinylidene double bond content per polyisobutene chain end of in most cases at least 90 mol% and having a narrow molecular weight distribution. The following examples are intended to illustrate the present invention without limiting it.

Example 1: Preparation of the polymerization reaction initiating catalyst-initiator mixtures

The following mixtures of optionally donor-containing Lewis acids as polymerization catalysts and initiators which can initiate the polymerization reaction according to the invention of isobutene or of isobutene-containing monomer mixtures, or precursors thereof, have been prepared as typical representatives of such systems: (a) 1.4 g (0.015 mol) of methanesulfonic acid was dissolved in 75 ml of dichloromethane, followed by the addition of 0.77 g (5.9 mmol) of di-n-butyl ether;

(b) 1.4 g (0.015 mol) of methanesulfonic acid were dispersed in 125 ml of toluene, followed by the addition of 0.77 g (5.9 mmol) of di-n-butyl ether;

(c) 2.0 g (0.015 mol) of aluminum trichloride were suspended in 75 ml of dichloromethane, followed by addition of 0.77 g (5.9 mmol) of di-n-butyl ether and 1.4 g (0.015 mol) of methanesulfonic acid;

(d) 2.0 g (0.015 mol) of aluminum trichloride were suspended in 125 ml of toluene; Subsequently, 0.77 g (5.9 mmol) of di-n-butyl ether and 1.4 g (0.015 mol) of methanesulfonic acid were added;

(e) 2.4 g (0.015 mol) of iron (III) chloride was suspended in 75 ml of dichloromethane; followed by the addition of 0.77 g (5.9 mmol) of di-n-butyl ether;

(f) 2.4 g (0.015 mol) of iron (III) chloride was suspended in 125 ml of toluene; followed by the addition of 0.77 g (5.9 mmol) of di-n-butyl ether;

(g) 2.4 g (0.015 mol) of iron (III) chloride was suspended in 75 ml of dichloromethane; followed by the addition of 0.77 g (7.5 mmol) of diisopropyl ether and 1.4 g (0.015 mol) of methanesulfonic acid;

(h) 2.0 g (0.015 mol) of zinc chloride were suspended in 75 ml of dichloromethane; Subsequently, 0.77 g (7.5 mmol) of diisopropyl ether and 1.4 g (0.015 mol) of methanesulfonic acid were added;

(i) 2.0 g (0.015 mol) of zinc chloride were suspended in 75 ml of dichloromethane; followed by the addition of 0.77 g (5.9 mmol) of di-n-butyl ether and 1.4 g (0.015 mol) of methanesulfonic acid;

(j) 2.0 g (0.015 mol) of zinc chloride were suspended in 75 ml of dichloromethane; Subsequently, the addition of 1, 4 g (0.015 mol) of methanesulfonic acid;

(k) 2.4 g (0.015 mol) of iron (III) chloride was suspended in 75 ml of dichloromethane; Subsequently, the addition of 1, 4 g (0.015 mol) of methanesulfonic acid;

(I) 2.0 g (0.015 mol) of aluminum trichloride was suspended in 75 ml of dichloromethane; Subsequently, the addition of 1, 4 g (0.015 mol) of methanesulfonic acid;

(m) 1, 4 g (0.015 mol) of methanesulfonic acid were dispersed in 75 ml of dichloromethane; then, 1.0 g (0.015 mol) of boron trifluoride was introduced;

(n) 1, 4 g (0.015 mol) of methanesulfonic acid were dispersed in 125 ml of toluene; then, 1.0 g (0.015 mol) of boron trifluoride was introduced;

(o) 2.6 g (0.015 mol) of p-toluenesulfonic acid were dissolved in 75 ml of dichloromethane; Thereafter, 1.0 g (0.015 mol) of boron trifluoride was introduced;

(p) 2.6 g (0.015 mol) of p-toluenesulfonic acid was dissolved in 125 ml of toluene; Subsequently, 1.0 g (0.015 mol) of boron trifluoride was introduced.

Example 2: Polymerization of "Raffinate 1" with FeC'B ^ O and with methanesulfonic acid as initiator in dichloromethane at -20 ° C 14.86 g of "raffinate 1" containing 5.94 g (106.0 mmol) of pure isobutene were dissolved in 130 ml of dichloromethane at -20 ° C. with 0.53 mmol of the catalyst complex of anhydrous iron (III). chloride and di-n-butyl ether in a molar ratio of 1: 1 (in the form of a 1-molar solution in dichloromethane) in the presence of 0.015 mol of methanesulfonic acid as an initiator within 30 minutes at a conversion of 68% to a polyisobutene with a number average Molecular weight M _n of 2285, a polydispersity of 2.34 and a content of terminal double bonds of 91, 7 mol% polymerized.

Example 3 Polymerization of "Raffinate 1" with FeCb'Bi ^ O and with methanesulfonic acid as initiator in dichloromethane at + 20 ° C.

7.43 g of "raffinate 1" containing 2.97 g (53.0 mmol) of pure isobutene were dissolved in 65.0 ml of dichloromethane at + 20 ° C. with 0.53 mmol of the catalyst complex of anhydrous iron (III). chloride and di-n-butyl ether in a molar ratio of 1: 1 (in the form of a 1-molar solution in dichloromethane) in the presence of 0.015 mol of methanesulfonic acid as an initiator within 30 minutes at a conversion of 92% to a polyisobutene with a number average Molecular weight M _n of 822, a polydispersity of 1, 81 and a content of terminal double bonds of 93.1 mol% polymerized. Example 4: Polymerization of "Raffinate 1" with FeCb'Bi ^ O and with methanesulfonic acid as initiator in toluene at + 20 ° C.

7.43 g of "raffinate 1" containing 2.97 g (53.0 mmol) of pure isobutene were dissolved in 65.0 ml of toluene at + 20 ° C with 0.053 mmol of the catalyst complex of anhydrous iron (III) chloride and Di-n-butyl ether in a molar ratio of 1: 1 (in the form of a 1-molar solution in dichloromethane) in the presence of 0.015 mol of methanesulfonic acid as an initiator within 30 minutes at a conversion of 20% to a polyisobutene having a number average molecular weight M _n of 1000, a polydispersity of 2.20 and a content of terminal double bonds of 85.0 mol% polymerized.

Example 5: Polymerization of "Raffinate 1" with AICb'Bi ^ O and with methanesulfonic acid as initiator in dichloromethane at + 20 ° C.

14.49 g of "raffinate 1", containing 5.79 g (103.4 mmol) of pure isobutene, were dissolved in 125 ml of dichloromethane at + 20 ° C. with 1, 0 mmol of the catalyst complex of anhydrous aluminum chloride and di-n butyl ether in a molar ratio of 1: 1 (in the form of a 1 -mola-ren solution in dichloromethane) in the presence of 0.03 mol of methanesulfonic acid as an initiator within 5 minutes at a conversion of 73% to a polyisobutene having a number average molecular weight M _n polymerized from 2491, a polydispersity of 2.97 and a content of terminal double bonds of 90.0 mol%.

Claims

claims

A process for the preparation of highly reactive Isobutenhomo- or copolymers having a content of terminal vinylidene double bonds per polyisobutene chain end of at least 50 mol% by polymerization of isobutene or an isobutene-containing monomer mixture in the presence of at least one suitable as a polymerization Lewis acid or a as Polymerization catalyst effective complex of at least one Lewis acid and at least one donor and in the presence of at least one initiator, characterized in that is used as at least one initiator an organic sulfonic acid of the general formula Z-SO3H, in which the variable Z is a C to C2O Alkyl radical, C to C 20 haloalkyl radical, C5 to C & cyclocycloalkyl radical, C 6 to C 20 aryl radical or a C 7 to C 20 arylalkyl radical.

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

Process according to Claim 1 or 2, in which at least one compound selected from the binary chlorine and fluorine compounds of the elements of the 1st to 8th transition groups and the 3rd to 5th main groups of the Periodic Table is used as the Lewis acid for the complex which acts as the polymerization catalyst or mixtures thereof.

Process according to Claim 3, in which the Lewis acid used is a binary chlorine or fluorine compound selected from BCl 3, AlCl 3, TiCU, FeC, FeC, ZnC, BF 3, AIF 3, TiF ₄ , FeF 2, FeF 3 and ZnF 2.

Process according to Claims 1 to 4, in which a complex which acts as a polymerization catalyst and contains as donor an organic compound having at least one ether function or one carboxylic ester function is used.

A process as claimed in claim 5, wherein the donor organic compound is a dihydrocarbyl ether of the general formula R ¹ -O-R ² in which the variables R ¹ and R ² independently of one another are C ¹ - to C 20 -alkyl radicals, C 5 - to C 8 -cycloalkyl radicals, C 6 to C 20 aryl radicals or C 7 to C 20 arylalkyl radicals, or a carboxylic acid hydrocarbyl ester of the general formula R ³ -COOR ⁴ , in which the variables R ³ and R ⁴ independently of one another are C to C 20 -alkyl radicals, C 5 to Cs -Cycloalkyl radicals, C6 to C20-aryl radicals or C7 to C20-arylalkyl radicals.

The method of claim 6, wherein the donor organic compound has a total carbon number of 3 to 16.

Process according to claims 1 to 7, wherein the polymerization is carried out using at least one further initiator which is mono- or polyfunctional and selected from organic hydroxy compounds, organic halogen compounds, protic acids and water.

The process of claim 8, wherein said at least one additional initiator is selected from water, one or more protonic 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.

10. The method according to claims 1 to 9, wherein the polymerization in the presence of 0.01 to 10 mmol, each based on 1 mol of isobutene monomer used in homopolymerization of isobutene or to 1 mol of the total amount of the polymerizable monomers used Copolymerization of isobutene, a nitrogen-containing basic compound performs.

1 1. A method according to claim 10, characterized in that is used as the nitrogen-containing basic compound pyridine or a derivative of pyridine.

12. The method according to claims 1 to 1 1 for the preparation of highly reactive isobutene homo- or copolymers having a number average molecular weight M _n of 500 to 250,000.

13. The method according to claims 1 to 12 for the preparation of highly reactive isobutene homo- or copolymers having a polydispersity of 1, 05 to less than 3.5.

14. The method according to claims 1 to 13, characterized in that one carries out the polymerization at a temperature of -30 ° C to + 50 ° C.

15. The method according to claims 1 to 14, characterized in that the polymerization in an aliphatic, cycloaliphatic or aromatic hydrocarbon, in a halogenated aliphatic hydrocarbon or in a mixture of aliphatic, cycloaliphatic and / or aromatic hydrocarbons or halogenated aliphatic hydrocarbons or in a mixture of at least one halogenated aliphatic hydrocarbon and at least one aliphatic, cycloaliphatic or aromatic hydrocarbon as an inert diluent.

16. isobutene polymers of the general formula I.

in the

R ¹⁰ denotes a sulfonic acid grouping of the general formula -O-SO 2 Z in which the variable Z is a C 2 -C 20 -alkyl radical, C 2 -C 20 -haloalkyl radical, C 5 -C 4 -cycloalkyl radical, C 6 -C 20 -aryl radical or a C 7- to C2o-arylalkyl radical, and

R ^{1 1} and R ¹² are independently hydrogen, Cr is up to 4500 to C2o-alkyl groups, C5 to Cs cycloalkyl, C6-C2o-aryl radicals stand up or C7-C2o-alkylaryl radicals, and n is a number from. 9