JP6099648B2 - Method for producing highly reactive isobutene homopolymer or isobutene copolymer - Google Patents

Description

  The present invention relates to a novel process for producing highly reactive isobutene homopolymers or isobutene copolymers having a content of at least 50 mol% of terminal vinylidene double bonds per polyisobutene chain end. Furthermore, the present invention relates to a novel isobutene polymer.

によって記載される二重結合であると解釈され、すなわちこの二重結合は、ポリマー鎖においてα位に存在する。「ポリマー」は、１つのイソブテン単位だけに省略したポリイソブテン基を表わす。ビニリデン基は、例えば立体的要求度が大きい反応成分、例えば無水マレイン酸への熱的な付加の際に最も高い反応性を示し、それに反して、高分子の内部に存在する二重結合は、多くの場合に官能化反応の際に反応性を示さないかまたは僅かな反応性を示す。高反応性ポリイソブテンは、とりわけ、例えばドイツ連邦共和国特許出願公開第２７０２６０４号明細書の記載と同様に、潤滑剤用添加剤および燃料用添加剤を製造するための中間生成物として使用される。 High-reactivity isobutene homopolymers or isobutene copolymers, unlike so-called low-reactivity polymers, contain a high content of terminally disposed ethylenic double bonds (α-double bonds) and, in practice, are polyisobutenes. It is taken to be a polyisobutene which usually contains at least 80 mol% of that content relative to the individual chain ends of the polymer. The vinylidene group is within the scope of the present invention, and the position of the group in the polyisobutene polymer is a general formula.

The double bond is in the α position in the polymer chain. “Polymer” refers to polyisobutene groups omitted for only one isobutene unit. Vinylidene groups exhibit the highest reactivity upon thermal addition to, for example, sterically demanding reaction components such as maleic anhydride, whereas the double bonds present inside the polymer are In many cases, there is little or no reactivity during the functionalization reaction. Highly reactive polyisobutenes are used, inter alia, as intermediate products for the production of lubricant additives and fuel additives, as described, for example, in German Offenlegungsschrift 2,702,604.

This type of highly reactive polyisobutene is obtained, for example, by cationic polymerization of isobutene in the liquid phase in the presence of boron trifluoride as a catalyst, according to the method of DE-A-2702604. In this case, it is disadvantageous that the polyisobutene obtained at that time exhibits a relatively high polydispersity index. The polydispersity index is a standard for the molecular weight distribution of the obtained polymer chain and corresponds to the quotient from the mass average molecular weight M _w and the number average molecular weight M _n (PDI = M _w / M _n ).

  Polyisobutenes with a similar high proportion of terminal double bonds but with a narrower molecular weight distribution are described, for example, in EP-A-145235, US Pat. No. 5,408,018 and WO 99/64482. The polymerization is carried out in the presence of a deactivated catalyst, for example a complex of boron trifluoride with an alcohol and / or ether.

  Further, the highly reactive polyisobutene can be obtained, for example, by subjecting isobutene to living cationic polymerization and dehydrohalogenating the obtained polymerization product by the method from US Pat. No. 5,340,881. However, this method is expensive. This is because the halogen end groups introduced by living cationic polymerization must be removed in a separate step in order to generate double bonds.

  Furthermore, aluminum trichloride, a Lewis acid, can be used as a catalyst for the polymerization of isobutene. For example, High Polymers, Volume XXIV (Part 2), pp. 713-733 (editor: Edward C. Leonard), Verlag J. et al. Wiley & Sons, New York, 1971.

Topics in Catalysis Vol. 23, pp. 175-181 (2003), in the article “Cationic polymerisation using heteropolyacid salt catalysts”, James D. Burrington et al. Uses aluminum trichloride as a catalyst for the polymerization of isobutene. And that only low-reactivity polyisobutenes with a low content of terminal vinylidene double bonds (α-double bonds) can be obtained. Table 1 of this article on page 178 lists examples of polyisobutenes made with AlCl ₃ , which have a number average molecular weight M _{n of} 1000-2000, 2.5-3. The polydispersity index M _w / M _n of 5 and the content of vinylidene isomers (α-double bonds) of only 5% (in addition to “tri” 65%, “β” 5% and “tetra” 25%) Have.

Polymer Bulletin Vol. 52, pp. 227-234 (2004), in the article “Novel initiating system based on AlCl ₃ etherate for quasi-polymerizing of style,” Sergey V. For this purpose, a catalyst system consisting of 2-phenyl-2-propanol and aluminum trichloride-Dn-butyl ether complex is described. The polydispersity index M _w / M _n of the styrene polymer thus produced is “about 2.5” (see summary) or “about 3” (see page 230).

  In an international patent application having the serial number PCT / EP2011 / 051929, a process for producing a highly reactive isobutene homopolymer or isobutene copolymer having a content of terminal vinylidene double bonds of at least 50 mol% per polyisobutene chain end is provided. In this case, isobutene or a monomer mixture containing isobutene is polymerized in the presence of an aluminum trihalide-donor complex or an aluminum alkyl halide-donor complex which acts as a polymerization catalyst, said complex Contains as donors organic compounds having at least one ether function or carboxylic acid ester function.

  From Chinese Patent Application No. 10195558 it is known that iron (III) chloride is suitable for the production of highly reactive polyisobutenes and copolymers thereof as coinitiators in the polymerization of cationic isobutene. As initiators, water, phenol, protic acids such as sulfuric acid, tertiary alcohols, tertiary chlorides, tertiary carboxylic esters and carboxylic acids themselves are recommended. As complexing agents for the system initiating the polymerization, mention may in particular be made of alkyl ethers.

  WO 2006/011868 describes the polymerization of olefins using fluorohydrocarbons as solvent. As far as isobutene polymers are mentioned, in particular isobutene-isoprene copolymers (“butyl rubber”) are emphasized and do not mention the possible high content of terminal vinylidene double bonds. The initiator system for the polymerization can include sulfonic acid, among others.

  The object of the present invention is to provide a highly reactive isobutene homopolymer having a content of terminal vinylidene double bonds of at least 80 mol% per polyisobutene chain end and simultaneously having a narrow molecular weight distribution (ie low polydispersity index). Or it was to provide a process for producing an isobutene copolymer in an acceptable yield. In so doing, the catalyst system used should be sufficiently active, durable, free of problems in handling and resistant to interference.

The task is to use at least one initiator as a general formula Z—SO ₃ H, wherein the variable Z is a C ₁ -C ₂₀ alkyl group, a C ₁ -C ₂₀ halogenated alkyl group, a C ₅ -C ₈ cycloalkyl. At least 50 mol% of terminal vinylidene per polyisobutene chain end, characterized in that an organic sulfonic acid of the group, C ₆ -C ₂₀ aryl group or C ₇ -C ₂₀ arylalkyl group is used] Highly reactive isobutene homopolymer or isobutene copolymer having a double bond content in the presence of at least one Lewis acid suitable as a polymerization catalyst or at least one donation acting as a polymerization catalyst Of the monomer mixture containing isobutene or isobutene in the presence of a complex comprising It was solved by a method of manufacturing the.

  An isobutene homopolymer is understood within the scope of the present invention to be a polymer in which at least 98 mol%, in particular at least 99 mol%, are formed from isobutene with respect to said polymer. Correspondingly, an isobutene copolymer is taken to be a polymer containing a polymer different from isobutene, for example more than 2 mol% of linear butene.

Within the scope of the present invention, the following definitions apply to groups that are generally defined:
C ₁ -C ₈ alkyl groups are straight-chain or branched alkyl group having 1 to 8 carbon atoms. Examples for this are methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, t-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-dimethyl Butyl, 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 Pills, n- heptyl, n- octyl, and structural isomers thereof, such as 2-ethylhexyl. C ₁ -C ₈ alkyl groups of this kind are only slightly heteroatoms such as oxygen, nitrogen or halogen atoms, such as chlorine or fluorine, and / or aprotic functional groups such as carboxyl ester groups, cyano groups or nitro groups. May be included.

C ₁ -C ₂₀ alkyl groups are straight-chain or branched alkyl group having 1 to 20 carbon atoms. Examples for this are the above C ₁ -C ₈ alkyl groups and also n-nonyl, isononyl, n-decyl, 2-propylheptyl, n-undecyl, n-dodecyl, n-tridecyl, isotridecyl, n-tetradecyl, n-hexadecyl, n-octadecyl and n-eicosyl. C ₁ -C ₂₀ alkyl groups of this kind are only slightly heteroatoms such as oxygen, nitrogen or halogen atoms such as chlorine or fluorine, and / or aprotic functional groups such as carboxyl ester groups, cyano groups or nitro groups. May be included.

C ₁ -C ₂₀ halogenated alkyl group or a C ₁ -C ₈ halogenated alkyl group is a group having the elementary backbone relative C ₁ -C ₂₀ alkyl or C ₁ -C ₈ alkyl group However, in this group, for the most part, hydrogen atoms are replaced by halogen atoms, in particular fluorine atoms and / or chlorine atoms. In particular, all or almost all hydrogen atoms are replaced by halogen atoms, in particular fluorine atoms and / or chlorine atoms. Typical examples of such groups are C ₁ -C ₄ alkyl groups, such as dichloro, in which at least 60%, in particular at least 75%, in particular at least 90% of the number of hydrogen atoms are replaced by fluorine and / or chlorine atoms. Methyl, trichloromethyl, difluoromethyl, trifluoromethyl, chlorodifluoromethyl, fluorodichloromethyl, pentachloroethyl or pentafluoroethyl.

C ₅ -C ₈ cycloalkyl group, a saturated cyclic group which may contain an alkyl side chain. Examples for this are cyclopentyl, 2-methylcyclopentyl or 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, 2,4-dimethylcyclopentyl or 2,5-dimethylcyclopentyl, cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl Or 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 2,4-dimethylcyclohexyl, 2,5-dimethylcyclohexyl, 2,6-dimethylcyclohexyl, 3,4-dimethylcyclohexyl, 3,5-dimethylcyclohexyl, or 3, 6-dimethylcyclohexyl, cycloheptyl, 2-methylcycloheptyl, 3-methylcycloheptyl or 4-methylcycloheptyl, cyclooctyl, 2-methylcyclooctyl, 3 Methyl cyclooctyl, 4-methyl cyclooctyl or 5-methyl-cyclooctyl.

C ₅ -C ₈ cycloalkyl groups of this kind are only slightly heteroatoms such as oxygen, nitrogen or halogen atoms such as chlorine or fluorine and / or aprotic functional groups such as carboxyl ester groups, cyano groups or nitro groups. It may contain a group.

A C ₆ -C ₂₀ aryl group or a C ₆ -C ₁₂ aryl group represents inter alia an optionally substituted phenyl, an optionally substituted naphthyl, an optionally substituted anthracenyl or an optionally substituted phenanthrenyl. This kind of aryl groups are 1-5 aprotic substituents or aprotic functional groups, for example C ₁ -C ₈ alkyl, C ₁ -C ₈ alkyl halides, for example C ₁ -C ₈ chloroalkyl or C ₁ -C ₈ fluoroalkyl, it may have halogen, such as chlorine or fluorine, nitro, cyano or phenyl. Examples of such aryl groups are phenyl, naphthyl, biphenyl, anthracenyl, phenanthrenyl, tolyl, nitrophenyl, chlorophenyl, dichlorophenyl, pentafluorophenyl, pentachlorophenyl, (trifluoromethyl) phenyl, bis (trifluoromethyl) phenyl, (trichloro ) Methylphenyl and bis (trichloromethyl) phenyl.

C ₇ -C ₂₀ arylalkyl group or C ₇ -C ₁₂ arylalkyl group, especially, C ₁ -C ₄ alkyl optionally substituted phenyl, such as benzyl, o- methylbenzyl, m- methylbenzyl or p- methyl Benzyl, 1-phenylethyl or 2-phenylethyl, 1-phenylpropyl, 2-phenylpropyl or 3-phenylpropyl or 1-phenylbutyl, 2-phenylbutyl, 3-phenylbutyl or 4-phenylbutyl, optionally substituted It has been C ₁ -C ₄ alkylnaphthyl, e.g. naphthylmethyl, optionally substituted C ₁ -C ₄ alkyl anthracenyl, for example C ₁ -C ₄ alkyl phenanthrenyl substituted with anthracenylmethyl or any For example phenanthrenylmethyl.

Arylalkyl groups of this type, 1-5 aprotic substituents or aprotic functional groups, for example C ₁ -C ₈ alkyl, C ₁ -C ₈ alkyl halides, for example C ₁ -C ₈ chloroalkyl Alternatively, C ₁ -C ₈ fluoroalkyl, halogen such as chlorine or fluorine, nitro or phenyl can be present, in particular on the aryl moiety.

  The process according to the invention for producing highly reactive isobutene homopolymers or isobutene copolymers usually consists of a complex consisting of at least one Lewis acid and optionally at least one donor and the initiator described which acts as a polymerization catalyst Proceeds according to the cation reaction mechanism.

An essential feature of the present invention is the use of an organic sulfonic acid of the general formula Z—SO ₃ H as at least one initiator in the polymerization process according to the invention. Of course, it may be a mixture of different acid Z-SO ₃ H is used. In addition to the sulfonic acid initiator, further initiator molecules consisting of other chemical species may be shared.

Variable Z is, inter alia, C ₁ -C ₈ alkyl group, C ₁ -C ₈ halogenated alkyl group, C ₅ -C ₈ cycloalkyl group, a C ₆ -C ₁₂ aryl group or C ₇ -C ₁₂ arylalkyl group Represent. Particularly preferably, Z is, C ₁ -C ₄ alkyl group, C ₁ -C ₄ halogenated alkyl group, optionally substituted phenyl group, for example a tolyl group or xylyl group, or an optionally substituted C ₁ -C, ₄ represents an alkylphenyl group, for example a benzyl group.

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

As the Lewis acid, all inorganic molecules that are suitable as polymerization catalysts or that have proved to be Lewis acids in principle in accordance with the provisions in complexes that act as polymerization catalysts are suitable, however, In particular, the periodic table of the elements whose valence is entirely saturated with halogen atoms or in addition to the halogen substituents further one or more organic carbon groups, in particular C ₁ -C ₄ alkyl groups. The metal and metalloid halides are suitable. In this case, iodine, bromine and in particular fluorine, in particular chlorine, correspond to this as halogen substituents in the element halides and the element alkyl halides. Of course, mixtures of the elemental halides or elemental alkyl halides, respectively, as well as mixtures of each other, may be used.

For example, when an aluminum halide or alkyl halide is used as the Lewis acid, typically the following types can be used: aluminum trifluoride, aluminum trichloride, aluminum tribromide; Aluminum alkyl halides include mono (C ₁ -C ₄ alkyl) aluminum dihalides or di (C ₁ -C ₄ alkyl) aluminum monohalides such as methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum chloride or diethylaluminum chloride. Can be used.

  In a preferred embodiment, elements from the first subgroup to the eighth subgroup and the third main group to the fifth main group of the periodic table as a Lewis acid for the polymerization catalyst or as a complex acting as a polymerization catalyst. At least one compound selected from the two-component chlorine compounds and the two-component fluorine compounds is used, and the two-component chlorine compounds are advantageous in comparison with the two-component fluorine compounds of the above elements. Can do.

Typical two component chlorine compounds of this _{type, ScCl 3, YCl 3, YbCl} 3, TiCl 3, TiCl 4, ZrCl 4, HfCl 4, VCl 3, VCl 4, NbCl 3, NbCl 5, TaCl 5, CrCl ₂ , CrCl ₃ , MoCl ₃ , MoCl ₅ , WCl ₅ , WCl ₆ , MnCl ₂ , ReCl ₃ , ReCl ₅ , FeCl ₂ , FeCl ₃ , RuCl ₃ , OsCl ₃ , CoCl ₂ , CoCl ₃ , RhCl ₃ , IrCl ₃ , NiCl ₂ , PdCl ₂ , PtCl ₂ , CuCl, CuCl ₂ , AgCl, AuCl, ZnCl ₂ , CdCl ₂ , HgCl, HgCl ₂ , BCl ₃ , AlCl ₃ , GaCl ₃ , InCl ₃ , TlCl ₃ , SiCl ₄ , GeCl ₄ , _{SnCl 2, SnCl 3, SnCl 4} , PbCl 2, PbCl 4, PCl 3, PCl 5, As l _3, is SbCl _3, SbCl ₅ and BiCl _3. Of these, BCl ₃ , AlCl ₃ , TiCl ₄ , FeCl ₂ , FeCl ₃ and ZnCl ₂ are particularly preferred.

Typical two-component fluorine compounds of this _{type, 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, InF 3, TlF 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 , AlF ₃ , TiF ₄ , FeF ₂ , FeF ₃ and ZnF ₂ are particularly preferred. A mixture of a binary chlorine compound and a binary fluorine compound may be used.

Often, two-component bromine compounds may be used as this kind of a Lewis acid, the bromine compound, for example, are as _{follows: 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, AlBr 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 .

The preferred sulfonic acid initiators methanesulfonic acid, trifluoromethanesulfonic acid, trichloromethanesulfonic acid and toluenesulfonic acid are particularly preferred Lewis acids or BCl ₃ , AlCl ₃ , TiCl ₄ , FeCl ₂ , FeCl ₃ , ZnCl. ₂ , used in conjunction with Lewis acid complexes having BF ₃ , AlF ₃ , TiF ₄ , FeF ₂ , FeF ₃ and / or ZnF ₂ , in particular the general formulas described below as being preferred as donors When a Lewis acid complex containing a dihydrocarbyl ether of R ¹ —O—R ² and / or a carboxylic acid hydrocarbyl ester of the general formula R ³ —COOR ⁴ is used, the methanesulfonic acid is AlCl ₃ , BF ₃ or Used with FeCl ₃ .

  In particular, in the case of the process according to the invention, a complex is used as donor which acts as a polymerization catalyst and contains an organic compound having at least one ether function or carboxylic ester function. Of course, mixtures of various organic compounds having at least one ether function and / or various organic compounds having at least one carboxylic ester function may be used. If the complex acting as a polymerization catalyst has an organic compound having at least one ether functional group as a donor, the compound having at least one ether functional group is also interpreted as an acetal and a hemiacetal. sell.

In a preferred embodiment of the invention, a complex consisting of at least one Lewis acid and at least one donor is used which acts as a polymerization catalyst, the organic compound functioning as a donor being represented by the general formula R ¹ —O—R ^{2 wherein} the variables R ¹ and R ² are independently of each other a C _{1 to} C ₂₀ alkyl group, in particular a C _{1 to} C ₈ alkyl group, a C _{5 to} C ₈ cycloalkyl group, C ₆ -C ₂₀ aryl group, in particular C ₆ -C ₁₂ aryl group or C ₇ -C ₃₀ arylalkyl group, in particular whether the dihydroxy ribs ether of representing a C ₇ -C ₁₂ arylalkyl group] or general, wherein R ³ -COOR ⁴ [wherein the variables R ³ and R ⁴ are, independently of one another, C ₁ -C ₂₀ alkyl radical, especially C ₁ -C ₈ alkyl group, C ₅ -C ₈ cycloalkyl group, C ₆ -C ₂₀ aryl groups, especially C ₆ -C ₁₂ Aryl group or a C ₇ -C ₂₀ arylalkyl group, a carboxylic acid hydrocarbyl ester of particular represent C ₇ -C ₁₂ arylalkyl group].

The described dihydrocarbyl ethers can be open-chain or cyclic, in which case the two variables R ¹ and R ² are closed into one ring, In some cases, the ring may contain 2 or 3 ether oxygen atoms. Examples of this type of open-chain dihydrocarbyl ether and cyclic dihydrocarbyl ether are dimethyl ether, diethyl ether, di-n-propyl ether, diisopropyl ether, di-n-butyl ether, di-s-butyl ether, diisobutyl ether, di-n. -Pentyl ether, di-n-hexyl ether, di-n-heptyl ether, di-n-octyl ether, di- (2-ethylhexyl) ether, methyl-n-butyl ether, methyl-s-butyl ether, methyl-isobutyl ether Methyl-t-butyl ether, ethyl-n-butyl ether, ethyl-s-butyl ether, ethyl-isobutyl ether, n-propyl-n-butyl ether, n-propyl-s-butyl ether, n-propyl-isobutyl ether Tellurium, n-propyl-t-butyl ether, isopropyl-n-butyl ether, isopropyl-s-butyl ether, isopropyl-isobutyl ether, isopropyl-t-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-dioxane, 1,3-dioxane and 1,4-dioxane, dicyclohexyl ether, diphenyl ether, ditolyl ether, dixylyl ether and dibenzyl ether A. Among the dihydrocarbyl ethers mentioned, di-n-butyl ether and diphenyl ether are used as donors, in particular the Lewis acids BCl ₃ , AlCl ₃ , TiCl ₄ , FeCl ₂ , FeCl ₃ and ZnCl ₂ . It was found that this combination was particularly preferable.

Examples of the carboxylic acid hydrocarbyl esters described are: formic acid-methyl ester, formic acid-ethyl ester, formic acid-n-propyl ester, formic acid-isopropyl ester, formic acid-n-butyl ester, formic acid-s-butyl ester, formic acid-isobutyl Ester, formic acid-t-butyl ester, acetic acid-methyl ester, acetic acid-ethyl ester, acetic acid-n-propyl ester, acetic acid-isopropyl ester, acetic acid-n-butyl ester, acetic acid-s-butyl ester, acetic acid-isobutyl ester, Acetic acid-t-butyl ester, propionic acid-methyl ester, propionic acid-ethyl ester, propionic acid-n-propyl ester, propionic acid-isopropyl ester, propionic acid-n-butyl ester, propionic acid-s-butyl ester, propio Acid-isobutyl ester, propionic acid-t-butyl ester, butyric acid-methyl ester, butyric acid-ethyl ester, butyric acid-n-propyl ester, butyric acid-isopropyl ester, butyric acid-n-butyl ester, butyric acid-s-butyl ester, butyric acid -Isobutyl ester, butyric acid-t-butyl ester, cyclohexanecarboxylic acid-methyl ester, cyclohexanecarboxylic acid-ethyl ester, cyclohexanecarboxylic acid-n-propyl ester, cyclohexanecarboxylic acid-isopropyl ester, cyclohexanecarboxylic acid-n-butyl ester, Cyclohexanecarboxylic acid-s-butyl ester, cyclohexanecarboxylic acid-isobutyl ester, cyclohexanecarboxylic acid-t-butyl ester, benzoic acid-methyl ester, benzoic acid-d Ester, benzoic acid-n-propyl ester, benzoic acid-isopropyl ester, benzoic acid-n-butyl ester, benzoic acid-s-butyl ester, benzoic acid-isobutyl ester, benzoic acid-t-butyl ester, phenylacetic acid-methyl Esters, phenylacetic acid-ethyl ester, phenylacetic acid-n-propyl ester, phenylacetic acid-isopropyl ester, phenylacetic acid-n-butyl ester, phenylacetic acid-s-butyl ester, phenylacetic acid-isobutyl ester and phenylacetic acid-t-butyl Ester. Among the carboxylic acid hydrocarbyl esters described, ethyl acetate is used as a donor, in particular in combination with Lewis acids BCl ₃ , AlCl ₃ , TiCl ₄ , FeCl ₂ , FeCl ₃ and ZnCl _2. Was found to be particularly preferable.

Furthermore, the dihydrocarbyl ethers and carboxylic acid hydrocarbyl esters prove to be particularly preferred as donors, in particular in combination with Lewis acids BCl ₃ , AlCl ₃ , TiCl ₄ , FeCl ₂ , FeCl ₃ and ZnCl _2. The donor compounds here have a total carbon number of 3 to 16, in particular 4 to 16, in particular 4 to 12, in particular 4 to 8. In the case of dihydrocarbyl ethers, in particular dihydrocarbyl ethers having a total of 6 to 14 and in particular 8 to 12 carbon atoms are particularly preferred. In the case of carboxylic acid-hydrocarbyl esters, carboxylic acid-hydrocarbyl esters having a total of 3 to 10, in particular 4 to 6, carbon atoms are preferred.

In the complexes acting as polymerization catalysts, the described donor compounds: Lewis acids, ie the element halides mentioned in particular and the element alkyl halides, in particular the Lewis acids BCl ₃ , AlCl ₃ , TiCl ₄ , The molar ratio of FeCl ₂ , FeCl ₃ and ZnCl ₂ is usually 0.3: 1 to 1.5: 1, in particular 0.5: 1 to 1.2: 1, in particular 0.7: 1 to 1. It fluctuates within the range of 1: 1 and is usually 1: 1. However, it may be worked up with a more significant excess of the donor compound, often up to a 10-fold, in particular a 3-fold molar excess, and the excess of the donor compound may further be used as a solvent or diluent. Works.

  Usually, the complex that acts as a polymerization catalyst is prepared from the described Lewis acid and the donor compound or compounds, which are used separately, usually in anhydrous form, before polymerization, They are usually dissolved in an inert solvent, such as a halogenated hydrocarbon, such as dichloromethane, and added to the polymerization medium. However, the complex may be prepared in-situ before polymerization.

  In a preferred embodiment of the invention, the polymerization is monofunctional or polyfunctional, in particular monofunctional, difunctional or trifunctional and is selected from among organic hydroxy compounds, organic halogen compounds, protonic acids and water. Performed while sharing at least one additional initiator that has been selected. Mixtures of such further initiators, for example mixtures consisting of two or more organic hydroxy compounds, mixtures consisting of two or more organic halogen compounds, mixtures consisting of one or more organic hydroxy compounds and one or more organic halogen compounds A mixture of one or more organic hydroxy compounds and water, a mixture of one or more organic halogen compounds and water, or a mixture of one or more protonic acids and water may be used. The initiator can be monofunctional, difunctional or polyfunctional, ie, within the initiator molecule, one, two or more hydroxyl groups, respectively, that initiate the polymerization reaction, or A halogen atom may be present. In the case of difunctional or polyfunctional initiators, telechelic difunctional isobutene polymers having usually more than 2, in particular 2 or 3, polyisobutene chain ends are obtained.

Organic hydroxy compounds which have only one hydroxyl group in the molecule and are suitable as monofunctional initiators are in particular alcohols and phenols, in particular the general formula R ⁵ —OH, wherein R ⁵ is C ₁ -C ₂₀ alkyl groups, especially C ₁ -C ₈ alkyl groups, C ₅ -C ₈ cycloalkyl groups, C ₆ -C ₂₀ aryl groups, especially C ₆ -C ₁₂ aryl groups, or C ₇ -C ₂₀ aryl alkyl groups may particularly include the alcohols and phenols represent C ₇ -C ₁₂ arylalkyl group]. Furthermore, the group R ⁵ can comprise a mixture of the above structures and / or have further functional groups as already described groups, for example keto functional groups, nitroxides or carboxyl groups and / or hetero It can have cyclic structural elements.

  Typical examples of this type of organic monohydroxy compound are methanol, ethanol, n-propanol, isopropanol, n-butanol, s-butanol, isobutanol, t-butanol, n-pentanol, n-hexanol, n- Heptanol, n-octanol, 2-ethylhexanol, cyclohexanol, phenol, p-methoxyphenol, o-cresol, m-cresol and p-cresol, benzyl alcohol, p-methoxybenzyl alcohol, 1-phenylethanol and 2-phenyl Ethanol, 1- (p-methoxyphenyl) ethanol and 2- (p-methoxyphenyl) ethanol, 1-phenyl-1-propanol, 2-phenyl-1-propanol and 3-phenyl-1-propanol, 1 (P-methoxyphenyl) -1-propanol, 2- (p-methoxyphenyl) -1-propanol and 3- (p-methoxyphenyl) -1-propanol, 1-phenyl-2-propanol and 2-phenyl-2 -Propanol, 1- (p-methoxyphenyl) -2-propanol and 2- (p-methoxyphenyl) -2-propanol, 1-phenyl-1-butanol, 2-phenyl-1-butanol, 3-phenyl-1 -Butanol and 4-phenyl-1-butanol, 1- (p-methoxyphenyl) -1-butanol, 2- (p-methoxyphenyl) -1-butanol, 3- (p-methoxyphenyl) -1-butanol and 4- (p-methoxyphenyl) -1-butanol, 1-phenyl-2-butanol, 2-phenyl 2-butanol, 3-phenyl-2-butanol and 4-phenyl-2-butanol, 1- (p-methoxyphenyl) -2-butanol, 2- (p-methoxyphenyl) -2-butanol, 3- ( p-methoxyphenyl) -2-butanol and 4- (p-methoxyphenyl) -2-butanol, 9-methyl-9H-fluoren-9-ol, 1,1-diphenylethanol, 1,1-diphenyl-2- Propin-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, α, α-diphenyl-2-pyridinemethanol, 4-methoxytrityl alcohol (especially polymer-bound as stationary phase), α-t-butyl-4-chloro-4′-methylbenzhydrol, cyclohexyldiphenyl Methanol, α- (p-tolyl) -benzhydrol, 1,1,2-triphenylethanol, α, α-diphenyl-2-pyridineethanol, α, α-4-pyridylbenzohydrol-N-oxide, 2-fluorotriphenylmethanol, triphenylpropargyl alcohol, 4-[(diphenyl) hydroxymethyl] benzonitrile, 1- (2,6-dimethoxyphenyl) -2-methyl-1-phenyl-1-propanol, 1,1 , 2-Triphenylpropan-1-ol and p-anisaldehyde carbi Is Lumpur.

  Organic hydroxy compounds having two hydroxyl groups in the molecule which are suitable as bifunctional initiators are, in particular, dihydric alcohols having a total carbon number of 2-30, in particular 3-24, in particular 4-20. Or diols and bisphenols having a total carbon number of 6-30, in particular 8-24, in particular 10-20, such as ethylene glycol, 1,2-propylene glycol and 1,3-propylene glycol, 1,4-butylene glycol, 1,6-hexylene glycol, 1,2-bis (1-hydroxy-1-methylethyl) benzene, 1,3-bis (1-hydroxy-1-methylethyl) benzene or 1,4-bis (1- Hydroxy-1-methylethyl) benzene (o-dicumyl alcohol, m-dicumyl alcohol or p-dicumyl alcohol), Sphenol 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.

Organohalogen compounds having one halogen atom in the molecule and suitable as monofunctional initiators are, inter alia, of the general formula R ⁶ -Hal, where Hal is selected from fluorine, iodine and especially chlorine and bromine R ⁶ represents a C ₁ -C ₂₀ alkyl group, in particular a C ₁ -C ₈ alkyl group, a C ₅ -C ₈ cycloalkyl group or a C ₇ -C ₂₀ arylalkyl group, in particular it can include a compound of representing a C ₇ -C ₁₂ arylalkyl group]. Furthermore, the group R ⁶ can comprise a mixture of the above structures and / or have further functional groups as already described groups, for example keto functional groups, nitroxides or carboxyl groups, and / or hetero It can have cyclic structural elements.

  Typical examples of this type of organic monohalogen compound are methyl chloride, methyl bromide, ethyl chloride, ethyl bromide, 1-chloropropane, 1-bromopropane, 2-chloropropane, 2-bromopropane, 1-chlorobutane, 1-bromobutane, s-butyl chloride, s-butyl bromide, isobutyl chloride, isobutyl bromide, t-butyl chloride, t-butyl bromide, 1-chloropentane, 1-bromopentane, 1-chlorohexane, 1-bromohexane, 1-chloroheptane, 1-bromoheptane, 1-chlorooctane, 1-bromooctane, 1-chloro-2-ethylhexane, 1-bromo-2-ethylhexane, cyclohexyl chloride, 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- -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 It is.

  Organohalogen compounds having two halogen atoms in the molecule suitable as a bifunctional initiator are, for example, 1,3-bis- (1-bromo-1-methylethyl) benzene, 1,3-bis- ( 2-chloro-2-propyl) benzene (1,3-dichloromilk chloride) and 1,4-bis- (2-chloro-2-propyl) -benzene (1,4-dichloromilk chloride) may be included. .

Particularly preferred are organic hydroxy compounds, one or more halogens, each having one or more hydroxyl groups bound to sp ³ hybridized carbon atoms (“alcohols”) or to an aromatic ring (“phenol”). Further initiators selected from organohalogen compounds, protonic acids and water, each atom bonded to an sp ³ hybrid carbon atom. Of these, particularly preferred are initiators selected from organic hydroxy compounds in which one or more hydroxyl groups are each bonded to an sp ³ hybridized carbon atom.

In the case of organohalogen compounds as further initiators, furthermore, organohalogen compounds in which one or more halogen atoms are each bonded to a secondary sp ³ hybrid carbon atom or in particular to a tertiary sp ³ hybrid carbon atom. Is particularly preferred.

In particular, further initiators having groups R ⁵ , R ⁶ and R ⁷ in addition to the hydroxyl group at the sp ³ hybrid carbon atom are preferred, provided that the groups R ⁵ , R ⁶ and R ⁷ are independent of one another. Te, hydrogen, C ₁ -C ₂₀ represents alkyl, C ₅ -C ₈ cycloalkyl, C ₆ -C ₂₀ aryl, C ₇ -C ₂₀ alkylaryl or phenyl, the aromatic nucleus in its further one or more, in particular it is possible to have one or two C ₁ -C ₄ alkyl group, C ₁ -C ₄ alkoxy group, a C ₁ -C ₄ hydroxyalkyl group or a C ₁ -C ₄ halogenated alkyl group as a substituent, the variables R ⁵ when, up to one R ⁶ or R ⁷ represents hydrogen, and variables R ^5, R ⁶ or at least one R ⁷ is, furthermore one or more, especially 1 or 2 C ₁ -C ₄ alkyl group, C ₁ -C ₄ alkoxy, C ₁ Phenyl which may have a C ₄ hydroxyalkyl group or a C ₁ -C ₄ halogenated alkyl group as a substituent.

  Examples of the protic acid include hydrochloric acid, hydrobromic acid, hydrofluoric acid, sulfuric acid, hydrocyanic acid, and mixtures thereof. However, protonated ethers may be used as the protonic acid.

  For the present invention, water, one or more protonic acids, methanol, ethanol, 1-phenylethanol, 1- (p-methoxyphenyl) ethanol, n-propanol, isopropanol, 2-phenyl-2-propyl (cumene) , N-butanol, isobutanol, s-butanol, t-butanol, 1-phenyl-1-chloroethane, 2-phenyl-2-chloropropane (cumyl chloride), t-butyl chloride and 1,3-bis (1-hydroxy) Particularly preferred are further initiators selected from -1-methylethyl) -benzene or 1,4-bis (1-hydroxy-1-methylethyl) -benzene and mixtures thereof. Among these, in particular, water, one or more protonic acids, methanol, ethanol, 1-phenylethanol, 1- (p-methoxy-phenyl) -ethanol, n-propanol, isopropanol, 2-phenyl-2-propanol ( Cumene), n-butanol, isobutanol, s-butanol, t-butanol, 1-phenyl-1-chloroethane and 1,3-bis (1-hydroxy-1-methylethyl) -benzene or 1,4-bis ( Further initiators selected from 1-hydroxy-1-methylethyl) -benzene as well as mixtures consisting of these are preferred.

The sum of the further initiators mentioned, which should be shared in common with the organic sulfones of the general formula Z—SO ₃ H according to the invention: the molar ratio of the isobutene monomers used when homopolymerizing isobutene, or Sum of the further initiators described, which should be optionally shared with the organic sulfones used according to the invention of the general formula Z—SO ₃ H: the total amount of monomers having a polymerization capacity used when copolymerizing isobutene The molar ratio of the amounts is usually from 0.001: 1 to 0.5 for all individual functional group sites of the initiator (in which case the organic sulfonic acid can be regarded as monofunctional). : 1, especially 0.01: 1 to 0.4: 1, especially 0.1: 1 to 0.3: 1. Water only: used when homopolymerizing isobutene when water is shared as the only further initiator or when water is shared as a further initiator in combination with an organic hydroxy compound and / or an organic halogen compound. The molar ratio of isobutene monomer, or water only: when isobutene is copolymerized, is preferably from 0.0001: 1 to 0.1: 1, especially 0. .0002: 1 to 0.05: 1.

A portion of the initiator molecule added as an organic sulfonic acid, and optionally as an organic hydroxy compound or halogen compound, may be incorporated into the polymer chain. The proportion of polymer chains initiated by the incorporated organic initiator molecule (l _eff ) can be up to 100%, usually the proportion is 0-90% and is 5-90% Can be. The remaining polymer chains are generated by water derived from a small amount of moisture as initiator molecules or by chain transfer reactions.

  In a further preferred embodiment of the invention, the polymerization is carried out in each case from 0.01 to 10 mmol, in particular from 0.05 to 5 nitrogen-containing basic compounds, relative to 1 mol of isobutene monomer used in each case when isobutene is homopolymerized. Nitrogen-containing basic compound with respect to 1 mol of the total amount of monomers having a polymerization ability which is carried out in the presence of 0.0 mmol, in particular 0.1-1.0 mmol, or is used when copolymerizing isobutene The polymerization is carried out in the presence of 0.01 to 10 mmol, in particular 0.05 to 5.0 mmol, in particular 0.1 to 1.0 mmol.

As this type of nitrogen-containing basic compound, aliphatic amines, alicyclic amines or aromatic amines of the general formula R ⁷ —NR ⁸ R ⁹ can be used or ammonia can be used, wherein the variables R ⁷ , R ⁸ and R ⁹ are each independently hydrogen, C ₁ -C ₂₀ alkyl group, in particular C ₁ -C ₈ alkyl group, C ₅ -C ₈ cycloalkyl group, C ₆ -C ₂₀ aryl groups, in particular C ₆ -C ₁₂ aryl group or C ₇ -C ₂₀ arylalkyl group, in particular represents a C ₇ -C ₁₂ arylalkyl group. Where the variable does not represent hydrogen, a tertiary amine is present. If one of the variables represents hydrogen, a secondary amine is present. When two of the variables represent hydrogen, a primary amine is present. If all of the variables represent hydrogen, ammonia is present.

Typical examples of such amines of the general formula R ⁷ —NR ⁸ R ⁹ are methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, t-butylamine, s-butylamine, isobutylamine, t-amylamine. , N-hexylamine, n-heptylamine, n-octylamine, 2-ethylhexylamine, cyclopentylamine, cyclohexylamine, aniline, dimethylamine, diethylamine, di-n-propylamine, di-isopropylamine, di-n- Butylamine, di-t-butylamine, di-s-butylamine, di-isobutylamine, di-t-amylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di- (2 -Ethylhexyl) amine, dicyclopentylamine Dicyclohexylamine, diphenylamine, trimethylamine, triethylamine, tri-n-propylamine, tri-isopropylamine, tri-n-butylamine, tri-t-butylamine, tri-s-butylamine, tri-isobutylamine, tri-t-amylamine, Tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri- (2-ethylhexyl) amine, tricyclopentylamine, tricyclohexylamine, triphenylamine, dimethylethylamine, methyl-n-butylamine N-methyl-N-phenylamine, N, N-dimethyl-N-phenylamine, N-methyl-N, N-diphenylamine or N-methyl-N-ethyl-Nn-butylamine.

  Furthermore, as this type of nitrogen-containing basic compound, a compound having a plurality of, in particular, 2 or 3 nitrogen atoms and having 2 to 20 carbon atoms may be used. The atoms each independently have a hydrogen atom or an aliphatic, alicyclic or aromatic substitution. Examples of the polyamine include 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, in this case, as such nitrogen-containing basic compounds, one or two further ring heteroatoms and / or hydrocarbyls containing 1, 2 or 3 ring nitrogen atoms and from the group of oxygen and sulfur Can have groups, in particular C ₁ -C ₄ alkyl groups and / or phenyl, and / or functional groups or heteroatoms as substituents, in particular fluorine, chlorine, bromine, nitro and / or cyano, in particular Saturated, partially unsaturated or unsaturated nitrogen-containing five-membered heterocyclic compounds or nitrogen-containing six-membered heterocyclic compounds such as pyrrolidine, pyrrole, imidazole, 1,2,3-triazole or 1,2,4- Triazole, oxazole, thiazole, piperidine, pyrazane, pyrazole, pyridazine, pyrimidine, pyrazine, 1,2,3- Triazine, 1,2,4-triazine or 1,2,5-triazine, 1,2,5-oxathiazine, the 2H-1,3,5-thiadiazine or morpholine are suitable.

However, in particular, as nitrogen-containing basic compounds of this kind, pyridine or pyridine derivatives (especially mono C ₁ -C ₄ alkyl substituted pyridine, di C ₁ -C ₄ alkyl substituted pyridine or tri C ₁ -C ₄ alkyl substituted) Pyridine), for example 2-methylpyridine, 3-methylpyridine or 4-methylpyridine (picoline), 2,3-dimethylpyridine, 2,4-dimethylpyridine, 2,5-dimethylpyridine, 2,6-dimethylpyridine, 3,4-dimethylpyridine, 3,5-dimethylpyridine or 3,6-dimethylpyridine (lutidine), 2,4,6-trimethylpyridine (collidine), 2-t-butylpyridine, 3-t-butylpyridine or 4-t-butylpyridine, 2-t-butyl-6-methylpyridine, 2,4-di-t-butylpidine 2,5-di -t- Buchirupijin, 2,6-di -t- Buchirupijin or 3,5-di -t- Buchirupijin or 2-phenylpyridine, 3-phenylpyridine or 4-phenylpyridine are suitable.

  Individual nitrogen-containing basic compounds or mixtures of such nitrogen-containing basic compounds can be used.

In order to use isobutene or a monomer mixture containing isobutene as the monomer to be polymerized, as isobutene source, pure isobutene and isobutene-containing C ₄ hydrocarbon streams such as C ₄ raffinate, in particular “Raffinate 1”, isobutene C ₄ cut from the dehydrogenation, C ₄ cut and FCC cracking from steam cracking: C ₄ cut from (fluid catalysed cracking fluid catalytic cracking) is included in these 1,3-butadiene is sufficiently Suitable as long as it has been removed. The C ₄ hydrocarbon stream from the FCC refinery unit is also known as the “b / b” stream. Further suitable isobutene-containing C ₄ hydrocarbon streams are, for example, product streams from propylene-isobutane-cooxidation products or metathesis units, which are usually used after conventional purification and / or concentration. Suitable C ₄ hydrocarbon stream, usually less than 500ppm of butadiene, containing in particular less than 200 ppm. The presence of 1-butene and the presence of cis-2-butene and trans-2-butene are less important. Typically, isobutene concentration of C ₄ hydrocarbon stream which is described, is in the range of 40 to 60 wt%. That is, raffinate 1 is usually essentially 30-50% by weight of isobutene, 10-50% by weight of 1-butene, 10-40% by weight of cis-2-butene and trans-2-butene and 2 to 35% by weight of butane. In the case of the polymerization process according to the invention, the unbranched butenes in raffinate 1 are usually practically inert and only isobutene is polymerized.

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

  In particular, when using a raffinate stream as the isobutene source, it is possible to share water as the only additional initiator or to share water with additional initiators selected from organic hydroxy compounds and organic halogen compounds. In particular, it has been demonstrated to be effective during polymerization at temperatures of -30 ° C to + 50 ° C, especially 0 ° C to + 30 ° C.

  The described isobutene-containing monomer mixture can contain trace amounts of contaminants, such as water, carboxylic acids or mineral acids, without causing a critical yield or loss of selectivity. It is suitable for the purpose to avoid enrichment of the pollutants by removing the harmful substances from the isobutene-containing monomer mixture, for example by adsorption with solid adsorbents such as activated carbon, molecular sieves or ion exchangers. ing.

  A monomer mixture of isobutene or a monomer mixture of an isobutene-containing hydrocarbon mixture may be reacted with an olefinically unsaturated monomer that is copolymerizable with isobutene. If the monomer mixture of isobutene is to be copolymerized with a suitable comonomer, the monomer mixture contains, in particular, at least 5% by weight, particularly preferably at least 10% by weight, in particular at least 20% by weight, and the comonomer. In particular at most 95% by weight, particularly preferably at most 90% by weight, in particular at most 80% by weight.

Examples of copolymerizable monomers include the following: vinyl aromatic compounds such as styrene and α-methyl styrene, C ₁ -C ₄ alkyl styrene such as 2-methyl styrene, 3-methyl styrene and 4- Methylstyrene and 4-t-butylstyrene, halogenated styrene such as 2-chlorostyrene, 3-chlorostyrene or 4-chlorostyrene and isoolefins having 5 to 10 carbon atoms such as 2-methylbutene-1, 2-methylpentene-1, 2-methylhexene-1, 2-ethylpentene-1, 2-ethylhexene-1 and 2-propylheptene-1. Further, as comonomer, olefin having a silyl group such as 1-trimethoxysilylethene, 1- (trimethoxysilyl) propene, 1- (trimethoxysilyl) -2-methylpropene-2, 1- [tri (methoxyethoxy) These include) silyl] -ethene, 1- [tri (methoxyethoxy) silyl] -propene, and 1- [tri (methoxyethoxy) silyl] -2-methylpropene-2. Furthermore, depending on the polymerization conditions, isoprene, 1-butene, and cis-2-butene and trans-2-butene also fall under this category.

  If a copolymer is to be produced by the process according to the invention, the process can advantageously be configured to the extent that a random polymer or preferably a block copolymer is produced. In order to produce a block copolymer, for example, various monomers can be fed to the polymerization reaction sequentially, in which case the addition of a second comonomer is notably the first comonomer already at least partially polymerized. This is the first time it has been done. Thus, diblock copolymers, triblock copolymers and more block copolymers are available that have one comonomer or another comonomer block as a terminal block, depending on the order of monomer addition. However, block copolymers also occur in some cases when all comonomers are actually fed into the polymerization reaction simultaneously, but one comonomer therein is significantly faster than one or more other comonomers. Polymerize. This is especially true when isobutene and vinyl aromatic compounds, especially styrene, are copolymerized in the process according to the invention. In this case, block copolymers with terminal polystyrene blocks in particular are produced. This is attributed to the fact that vinyl aromatic compounds, especially styrene, polymerize significantly more slowly than isobutene.

  The polymerization can be carried out continuously as well as discontinuously. The continuous process can be carried out in the same manner as known in the state of the art in which isobutene is continuously polymerized in the liquid phase in the presence of a boron trifluoride based catalyst.

  The process according to the invention is suitable for operation at low temperatures, for example -90 ° C to 0 ° C, as well as at particularly higher temperatures, ie at least 0 ° C, for example 0 ° C to + 50 ° C or 0 ° C to + 30 ° C. It is also suitable for implementation. However, the polymerization according to the process according to the invention is carried out in particular at temperatures between -30 ° C. and + 50 ° C., in particular at 0 ° C. to + 30 ° C., for example at room temperature (+20 to + 25 ° C.).

  When the polymerization according to the process according to the invention is carried out at or above the boiling temperature of the monomer or monomer mixture to be polymerized, this polymerization is carried out in particular in a pressure vessel, for example in an autoclave or in a pressure reactor. .

In particular, the polymerization according to the process according to the invention is carried out in the presence of an inert diluent. As long as the derivation of the resulting heat of reaction can be ensured, the inert diluent used is suitable for reducing the increase in viscosity of the reaction solution that usually occurs during the polymerization reaction. Suitable diluents are 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, alicyclic hydrocarbons such as cyclopentane and cyclohexane, aromatic carbon Hydrogen such as benzene, toluene and xylene, and halogenated hydrocarbons, especially 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 alkyl aromatics halogenated in the alkyl side chain, such as chlorobenzene, monofluoromethylbenzene, difluoromethylbenzene and trifluoromethylbenzene, and Serial mixtures of diluents. As halogenated hydrocarbons for the aforementioned inert diluents and the inert diluents described below, chlorinated hydrocarbons, in particular pure chlorohydrocarbons, are preferred. In particular, from the inert diluents that can be used here, fluorohydrocarbons are excluded in order to sufficiently eliminate the residual content of fluorine in the polymer. The proportion of inert components of the isobutene-containing C ₄ hydrocarbon stream is also used as diluent or as a component of the solvent mixture described.

  In particular, the polymerization according to the invention can be carried out in aliphatic hydrocarbons, alicyclic hydrocarbons or aromatic hydrocarbons, in halogenated hydrocarbons, in particular in halogenated aliphatic hydrocarbons, or in the form of inert diluents. In mixtures of aromatic hydrocarbons, alicyclic hydrocarbons and / or aromatic hydrocarbons, or in mixtures of halogenated hydrocarbons, in particular halogenated aliphatic hydrocarbons, or at least one halogenated hydrocarbon, in particular In a mixture of one halogenated aliphatic hydrocarbon and at least one aliphatic hydrocarbon, alicyclic hydrocarbon or aromatic hydrocarbon, for example in a mixture of dichloromethane and n-hexane, usually 10: It is carried out in a volume ratio of 90 to 90:10, in particular 50:50 to 85:15. In particular, the diluent is freed of contaminants such as water, crotonic acid or mineral acid prior to use of the diluent, for example by adsorption with a solid adsorbent 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 hydrocarbons or in particular halogen-free aromatic hydrocarbons, in particular toluene. For this embodiment, water proved to be particularly preferred as an additional initiator, optionally in combination with the described organic hydroxy compounds and / or the described organic halogen compounds.

  In particular, the polymerization according to the process according to the invention is carried out under largely aprotic reaction conditions, in particular mostly under anhydrous reaction conditions. A roughly aprotic reaction condition or a roughly anhydrous reaction condition is taken to mean that the water content (or the content of protic contaminants) in the reaction mixture is less than 50 ppm, in particular less than 5 ppm. Therefore, the raw material is usually dried by physical and / or chemical means before use of the raw material. In particular, aliphatic hydrocarbons or alicyclic hydrocarbons used as solvents contain metal organic compounds such as organolithium compounds, organomagnesium compounds or organoaluminum compounds from the above-mentioned solvents after normal prepurification and predrying. It has proven effective to be added in an amount sufficient for removal, mostly in small amounts of water. The solvent thus treated is more particularly introduced directly into the reaction vessel. Likewise, the process can be carried out with the monomers to be polymerized, in particular with isobutene or with isobutene-containing mixtures. Also suitable are drying with other conventional desiccants such as molecular sieves or pre-dried oxides such as aluminum oxide, silicon dioxide, calcium oxide or barium oxide. Halogenated solvents not suitable for drying with metals, such as sodium or potassium or with metal alkyls, are removed with a suitable desiccant, for example calcium chloride, phosphorus pentoxide or molecular sieves. . Similarly, raw materials that are similarly not treated with metal alkyls, such as vinyl aromatic compounds, may be dried. Even when water is shared as an initiator, the residual moisture is most extensively dried by drying prior to the reaction from the solvent or monomer, especially because the additional initiator water can be used in a deliberately defined amount. It should be removed extensively or removed completely, thereby achieving a higher degree of process control and reproducibility of the results.

  The isobutene or isobutene-containing feedstock is usually spontaneously polymerized at the desired reaction temperature upon contact of the complex acting as a polymerization catalyst with the isobutene or isobutene-containing monomer mixture. In this case, it can be carried out to the extent that the monomer in the diluent is initially charged, brought to the reaction temperature, and subsequently the complex is added. Moreover, it can carry out to such an extent that the complex in a diluent is arbitrarily charged previously and a monomer is subsequently added. Furthermore, the point at which all reactants are contained in the reaction vessel is considered to be the start of polymerization.

  In order to produce the isobutene copolymer, it can optionally be carried out to the extent that the monomer in the diluent is previously charged and the complex is subsequently added. The reaction temperature can be adjusted before or after the addition of the complex. Also, initially, optionally, only one of the monomers in the diluent is pre-charged, followed by addition of the complex, and after some time, for example at least 60% of the monomer, at least 80% or at least 90% of the monomer To the extent that one or more additional monomers are added only when is reacted. Alternatively, the complex in the diluent can optionally be pre-charged and subsequently the monomers added simultaneously or sequentially and then adjusted to the desired reaction temperature. Furthermore, the point of time when at least one of the complex and the monomer is contained in the reaction vessel is regarded as the start of polymerization.

  In addition to the discontinuous processes described here, the polymerization according to the process according to the invention may be configured as a continuous process. In this case, the raw material, i.e. the monomer (s) to be polymerized, optionally the diluent and optionally the complex acting as a polymerization catalyst is continuously fed into the polymerization reaction and the reaction product is continuously removed. As a result, more or less steady polymerization conditions occur in the reactor. The monomer or monomers to be polymerized can themselves be diluted with a diluent or solvent or supplied as a monomer-containing hydrocarbon stream.

  The complex which acts as a polymerization catalyst is usually present in the polymerization medium either dissolved, dispersed or suspended. Further, the complex can be supported on a normal carrier material. Suitable reactor types for the polymerization process of the present invention are typically stirred tank reactors, loop reactors and tubular reactors, but fluidized bed reactors, fluidized bed reactors, with or with solvents A stirred tank reactor, a fluidized bed reactor, a continuous fixed bed reactor and a discontinuous fixed bed reactor (batch mode of operation).

  In the process according to the invention, the complex which acts as a polymerization catalyst is usually the molar ratio of isobutene when homopolymerizing the element: isobutene in the element halide or the element alkyl halide advantageously used as a Lewis acid. Or the molar ratio of the total amount of monomers having polymerization ability used when copolymerizing the element: isobutene in the element halide or the element alkyl halide advantageously used as a Lewis acid is 1: 5. It is used in an amount in the range 1: 5000, in particular 1:10 to 1: 5000, in particular 1:15 to 1: 1000, in particular 1:20 to 1: 250.

  Due to the interruption of the reaction, the reaction mixture is inter alia added, for example, by adding protic compounds, in particular water, alcohols such as methanol, ethanol, n-propanol and isopropanol or mixtures thereof with water. Or aqueous bases such as alkali metal hydroxides or alkaline earth metal hydroxides such as aqueous solutions of sodium hydroxide, potassium hydroxide, magnesium hydroxide or calcium hydroxide, alkali metal carbonates or alkaline earth metals Carbonates such as aqueous solutions of sodium carbonate, potassium carbonate, magnesium carbonate or calcium carbonate, or alkali metal bicarbonates or alkaline earth metal bicarbonates such as sodium bicarbonate, potassium bicarbonate, magnesium bicarbonate or charcoal It is inactivated by adding an aqueous solution of calcium hydrogen.

  The process according to the invention is at least 50 mol%, in particular at least 60 mol%, in particular at least 70 mol%, in particular at least 80 mol%, in particular at least 85 mol%, particularly preferably at least 90 mol%, per polyisobutene chain end. Producing highly reactive isobutene homopolymers or copolymers having a content of terminal vinylidene double bonds (α-double bonds) of more than 91 mol%, particularly preferably at least 95 mol%, for example approximately 100 mol%, Used in the way. In particular, the process according to the invention is composed of isobutene and at least one vinyl aromatic monomer, in particular styrene, and at least 50 mol%, in particular at least 60 mol%, per polyisobutene chain end. At least 70 mol%, in particular at least 80 mol%, in particular at least 80 mol%, in particular at least 85 mol%, particularly preferably at least 90 mol%, particularly preferably more than 91 mol%, in particular at least 95 mol%, for example It is also used in a process for producing highly reactive isobutene copolymers having a content of terminal vinylidene double bonds (α-double bonds) of approximately 100 mol%. In order to produce a copolymer consisting of isobutene and at least one vinyl aromatic monomer, in particular styrene, isobutene or isobutene-containing hydrocarbon cuts are made from at least one vinyl aromatic monomer and from 5 to 95 to 95 to 5, in particular. Are copolymerized in a mass ratio of 30-70 to 70-30 isobutene to vinyl aromatic compound.

In particular, highly reactive isobutene homopolymers or isobutene copolymers, in particular isobutene homopolymers produced by the process according to the invention, are less than 1.05 to 3.5, in particular less than 1.05 to 3.0, in particular 1.05. It has a polydispersity index (PDI = M _w / M _n ) of less than 2.5, in particular 1.05 to 2.3, particularly preferably 1.05 to 2.0, in particular 1.1 to 1.85. Typical values for PDI are 1.2 to 1.7 in the implementation of the optimal method.

In particular, highly reactive isobutene homopolymers or isobutene copolymers produced by the process according to the invention are in particular number average molecular weights of 500 to 250,000, particularly preferably 500 to 100,000, particularly preferably 500 to 25000, in particular 500 to 5000. M _n (determined by gel permeation chromatography). Isobutene homopolymers more particularly preferably have a number average molecular weight M _n of 500 to 10,000, in particular 500 to 5000, for example about 1000 or about 2300.

〔式中、
Ｒ¹⁰は、一般式−Ｏ−ＳＯ₂Ｚのスルホン酸基を表わし、上記式中、変数Ｚは、Ｃ₁〜Ｃ₂₀アルキル基、Ｃ₁〜Ｃ₂₀ハロゲン化アルキル基、Ｃ₅〜Ｃ₈シクロアルキル基、Ｃ₆〜Ｃ₂₀アリール基またはＣ₇〜Ｃ₂₀アリールアルキルを表わし、Ｒ¹¹およびＲ¹²は、互いに独立して、水素、Ｃ₁〜Ｃ₂₀アルキル基、Ｃ₅〜Ｃ₈シクロアルキル基、Ｃ₆〜Ｃ₂₀アリール基またはＣ₇〜Ｃ₂₀アルキルアリール基を表わし、および
ｎは、９〜４５００の数を表わす〕のイソブテンポリマーでもある。 The isobutene polymer produced as a major proportion in the isobutene homopolymer prepared according to the present invention having a terminal vinylidene double bond, incorporating the organic sulfonic acid used as the initiator molecule, is a novel compound. Accordingly, the subject of the present invention is the general formula I

[Where,
R ¹⁰ represents a sulfonic acid group of the general formula —O—SO ₂ Z, in which the variable Z is a C _{1 to} C ₂₀ alkyl group, a C _{1 to} C ₂₀ halogenated alkyl group, or a C _{5 to} C _8. Represents a cycloalkyl group, a C ₆ -C ₂₀ aryl group or a C ₇ -C ₂₀ arylalkyl, and R ¹¹ and R ¹² , independently of one another, represent hydrogen, a C ₁ -C ₂₀ alkyl group, a C ₅ -C ₈ cyclo Represents an alkyl group, a C ₆ -C ₂₀ aryl group or a C ₇ -C ₂₀ alkylaryl group, and n represents a number of 9 to 4500].

In a preferred embodiment, R ¹¹ and R ¹² are, independently of one another, hydrogen, C ₁ -C ₄ alkyl, in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl or t- Butyl, or phenyl which may have further 1 or 2 C ₁ -C ₄ alkyl groups or C ₁ -C ₄ alkoxy groups as substituents, and n is 9-4500, in particular 9-180, in particular 9 to 90, especially 15 to 45.

  By the process according to the invention, isobutene or a mixture of monomers containing isobutene are obtained under cationic conditions with a satisfactory or high conversion of usually 20 to 100%, in particular 35 to 90%, usually 5 to 120 minutes, in particular With a short reaction time of 5 to 60 minutes, a polyisobutene chain end with a content of terminal vinylidene double bonds of at least 90 mol% and a narrow molecular weight distribution, most often at least 90 mol%. Polymerized to reactive isobutene homopolymer or isobutene copolymer.

  The following examples illustrate the invention but do not limit the invention.

Example 1: Preparation of a catalyst-initiator mixture causing a polymerization reaction An initiator capable of causing a polymerization reaction according to the invention of a monomer mixture containing a Lewis acid and isobutene or isobutene as polymerization catalyst optionally containing a donor The following mixture consisting of or a precursor thereof was prepared as a typical representative of this type of system:
(A) 1.4 g (0.015 mol) of methanesulfonic acid was dissolved in 75 ml of dichloromethane, and then 0.77 g (5.9 mmol) of di-n-butyl ether was added.

  (B) 1.4 g (0.015 mol) of methanesulfonic acid was dispersed in 125 ml of toluene, and then 0.77 g (5.9 mmol) of di-n-butyl ether was added.

  (C) 2.0 g (0.015 mol) of aluminum trichloride is suspended in 75 ml of dichloromethane, followed by 0.77 g (5.9 mmol) of di-n-butyl ether and 1.4 g (0.015 mol) of methanesulfonic acid. Added.

  (D) 2.0 g (0.015 mol) of aluminum trichloride is suspended in 125 ml of toluene, followed by 0.77 g (5.9 mmol) of di-n-butyl ether and 1.4 g (0.015 mol) of methanesulfonic acid. Added.

  (E) 2.4 g (0.015 mol) of iron (III) chloride was suspended in 75 ml of dichloromethane, and then 0.77 g (5.9 mmol) of di-n-butyl ether was added.

  (F) 2.4 g (0.015 mol) of iron (III) chloride was suspended in 125 ml of toluene, and then 0.77 g (5.9 mmol) of di-n-butyl ether was added.

  (G) 2.4 g (0.015 mol) of iron (III) chloride was suspended in 75 ml of dichloromethane, and subsequently 0.77 g (7.5 mmol) of diisopropyl ether and 1.4 g (0.015 mol) of methanesulfonic acid were added. did.

  (H) 2.0 g (0.015 mol) of zinc chloride was suspended in 75 ml of dichloromethane, and then 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 is 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 did.

  (J) 2.0 g (0.015 mol) of zinc chloride was suspended in 75 ml of dichloromethane, and then 1.4 g (0.015 mol) of methanesulfonic acid was added.

  (K) 2.4 g (0.015 mol) of iron (III) chloride was suspended in 75 ml of dichloromethane, and then 1.4 g (0.015 mol) of methanesulfonic acid was added.

  (L) 2.0 g (0.015 mol) of aluminum trichloride was suspended in 75 ml of dichloromethane, and then 1.4 g (0.015 mol) of methanesulfonic acid was added.

  (M) 1.4 g (0.015 mol) of methanesulfonic acid was dispersed in 75 ml of dichloromethane, and then 1.0 g (0.015 mol) of boron trifluoride was introduced.

  (N) 1.4 g (0.015 mol) of methanesulfonic acid was dispersed in 125 ml of toluene, and then 1.0 g (0.015 mol) of boron trifluoride was introduced.

  (O) 2.6 g (0.015 mol) of p-toluenesulfonic acid was dissolved in 75 ml of dichloromethane, and then 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, and then 1.0 g (0.015 mol) of boron trifluoride was introduced.

Example 2: Polymerization of “Raffinate 1” with FeCl ₃ .Bu ₂ O and methanesulfonic acid as initiator in dichloromethane at −20 ° C. “Raffinate containing 5.94 g (106.0 mmol) of pure isobutene 14.86 g of 1 ”0.53 mmol of a catalyst complex consisting of anhydrous iron (III) chloride and di-n-butyl ether in a molar ratio of 1: 1 at −20 ° C. in 130 ml of dichloromethane (1 mol solution in dichloromethane) In the presence of 0.015 mol of methanesulfonic acid as an initiator, with a 68% conversion, a number average molecular weight M _{n of} 2285, a polydispersity index of 2.34 and Polyisobutene having a terminal double bond content of 91.7 mol% was obtained.

Example 3: Polymerization of “Raffinate 1” with FeCl ₃ .Bu ₂ O and methanesulfonic acid as initiator in dichloromethane at + 20 ° C. “Raffinate 1 containing 2.97 g (53.0 mmol) of pure isobutene 7.43 g of 0.53 mmol of a catalyst complex consisting of anhydrous iron (III) chloride and di-n-butyl ether in a molar ratio of 1: 1 at + 20 ° C. in 65.0 ml of dichloromethane (1 mol solution in dichloromethane) In the presence of 0.015 mol of methanesulfonic acid as an initiator, with a 92% conversion, a number average molecular weight M _{n of} 822, a polydispersity index of 1.81 and Polyisobutene having a content of 93.1 mol% terminal double bonds was obtained.

Example 4: Polymerization of “Raffinate 1” with FeCl ₃ · Bu ₂ O and methanesulfonic acid as initiator in toluene at + 20 ° C. “Raffinate 1 containing 2.97 g (53.0 mmol) of pure isobutene 7.43 g of catalyst complex consisting of anhydrous iron (III) chloride and di-n-butyl ether in a molar ratio of 1: 1 at + 20 ° C. in 65.0 ml of toluene (1 mol solution in dichloromethane) In the presence of 0.015 mol of methanesulfonic acid as an initiator, with a 20% conversion, a number average molecular weight M _{n of} 1000, a polydispersity index of 2.20 and Polyisobutene having a content of 85.0 mol% terminal double bonds was obtained.

Example 5: Polymerization of “Raffinate 1” with AlCl ₃ .Bu ₂ O and methanesulfonic acid as initiator in dichloromethane at + 20 ° C. “Raffinate 1 containing 5.79 g (103.4 mmol) of pure isobutene 14.49 g of a catalyst complex consisting of anhydrous aluminum chloride and di-n-butyl ether in a molar ratio of 1: 1 in 125 ml of dichloromethane at + 20 ° C. (in the form of a 1 molar solution in dichloromethane) Polymerized within 5 minutes in the presence of 0.03 mol of methanesulfonic acid as initiator, with a conversion of 73%, a number average molecular weight _{Mn of} 2491, a polydispersity index of 2.97 and 90.0 mol% Polyisobutene having a content of 2 terminal double bonds.

Claims (15)

Highly reactive isobutene homopolymers or isobutene copolymers having a content of terminal vinylidene double bonds of at least 50 mol% per polyisobutene chain end in the presence of at least one Lewis acid suitable for polymerization or for polymerization A process prepared by polymerization of isobutene or a mixture of monomers containing isobutene in the presence of a complex of at least one Lewis acid and at least one donor and acting as a catalyst in the presence of at least one initiator. Te, as at least one initiator of the general formula Z-SO ₃ H [wherein, the variable Z is, C ₁ -C ₂₀ alkyl group, C ₁ -C ₂₀ halogenated alkyl group, C ₅ -C ₈ cycloalkyl group , C ₆ -C ₂₀ aryl group or C ₇ -C organic sulfonic acid is used in ₂₀ an arylalkyl group] Characterized in Rukoto, said method.   2. The organic sulfonic acid selected from methane sulfonic acid, trifluoromethane sulfonic acid, trichloromethane sulfonic acid and toluene sulfonic acid or a mixture thereof, as at least one initiator. the method of.   As a Lewis acid for a complex that acts as a polymerization catalyst, binary chlorine compounds and binary fluorine of elements of the first subgroup to the eighth subgroup and the third main group to the fifth main group of the periodic table The method according to claim 1 or 2, wherein at least one compound selected from compounds or a mixture thereof is used. As a Lewis acid, a binary chlorine compound selected from BCl ₃ , AlCl ₃ , TiCl ₄ , FeCl ₂ , FeCl ₃ , ZnCl ₂ , BF ₃ , AlF ₃ , TiF ₄ , FeF ₂ , FeF ₃ and ZnF ₂ or two 4. A process according to claim 3, wherein component fluorine compounds are used.   5. The complex according to claim 1, wherein the donor is a complex that acts as a polymerization catalyst and contains an organic compound having at least one ether functional group or carboxylic ester functional group. the method of. The organic compound that functions as a donor has the general formula R ¹ —O—R ² , wherein the variables R ¹ and R ² are independently of each other a C _{1 to} C ₂₀ alkyl group, a C _{5 to} C ₈ cycloalkyl. A dihydrocarbyl ether of the group, representing a C ₆ -C ₂₀ aryl group or a C ₇ -C ₂₀ arylalkyl group], or a compound of the general formula R ³ —COOR ^{4 wherein} the variables R ³ and R ⁴ are independently, is a C ₁ -C ₂₀ alkyl group, carboxylic acid hydrocarbyl ester of a C ₅ -C ₈ cycloalkyl group, a C ₆ -C ₂₀ aryl group or C ₇ -C ₂₀ arylalkyl group], claim 5. The method according to 5.   7. The method of claim 6, wherein the organic compound that functions as a donor has a total carbon number of 3 to 16.   The polymerization is carried out while sharing at least one further initiator that is monofunctional or polyfunctional and is selected from among organic hydroxy compounds, organic halogen compounds, protonic acids and water. 8. The method according to any one of items 7 to 7.   At least one further initiator is water, one or more protonic acids, methanol, ethanol, 1-phenylethanol, 1- (p-methoxy-phenyl) -ethanol, n-propanol, isopropanol, 2-phenyl-2- Propanol, n-butanol, isobutanol, s-butanol, t-butanol, 1-phenyl-1-chloroethane, 2-phenyl-2-chloropropane, t-butyl chloride and 1,3-bis (1-hydroxy-1- 9. A process according to claim 8, which is selected from methylethyl) -benzene or 1,4-bis (1-hydroxy-1-methylethyl) -benzene and mixtures thereof.   The polymerization is carried out in the presence of 0.01 to 10 mmol of a nitrogen-containing basic compound with respect to 1 mol of isobutene monomer used for homopolymerization of isobutene each time, or used for copolymerization of isobutene. The method according to any one of claims 1 to 9, which is carried out in the presence of 0.01 to 10 mmol of a nitrogen-containing basic compound with respect to 1 mol of the total amount of monomers having a polymerization ability.   The method according to claim 10, characterized in that pyridine or a pyridine derivative is used as the nitrogen-containing basic compound. Producing highly reactive isobutene homopolymers or isobutene copolymers having a number average molecular weight M _n of from 500 to 250,000, a method according to any one of claims 1 to 11.   13. A process according to any one of the preceding claims, wherein a highly reactive isobutene homopolymer or isobutene copolymer having a polydispersity index of less than 1.05 to 3.5 is produced.   The process according to any one of claims 1 to 13, characterized in that the polymerization is carried out at a temperature of -30 ° C to + 50 ° C.   The polymerization can be an aliphatic hydrocarbon, alicyclic hydrocarbon or aromatic hydrocarbon, halogenated aliphatic hydrocarbon, or aliphatic hydrocarbon, alicyclic hydrocarbon and / or aromatic as an inert diluent. In a mixture of aromatic hydrocarbons, or in a mixture of halogenated aliphatic hydrocarbons, or at least one halogenated aliphatic hydrocarbon and at least one aliphatic hydrocarbon, alicyclic hydrocarbon or aromatic hydrocarbon The process according to claim 1, wherein the process is carried out in a mixture consisting of