DE102005002772A1 - Process for the preparation of polyisobutene - Google Patents

Abstract

The present invention relates to a process for the preparation of bifunctional isobutene polymers having a narrow molecular weight distribution, in which isobutene or an isobutene-containing monomer mixture is polymerized in the presence of an initiator and a Lewis acid in a solvent, the solvent being at most 35% by weight. % halogenated hydrocarbon solvents, based on the total weight of the reaction mixture, and wherein isobutene is not fully reacted.

Description

The The present invention relates to a process for the preparation of bifunctional isobutene polymers with a narrow molecular weight distribution.

Homo- and copolymers of isobutene find use in a variety of ways, for example for the production of fuel and lubricant additives, as Elastomers, as adhesives or adhesive raw materials or as a basic component of sealants and sealants.

For further processing, For example, to sealants and sealants or adhesive (raw) materials, particularly suitable polyisobutenes are telechelic, i. they point two or more reactive end groups. These end groups are it is mainly carbon-carbon double bonds that be further functionalized, or with a scheduling agent functionalized groups.

The Preparation of telechelic polyisobutenes by living cationic Polymerization of isobutene is known. As a living cationic Polymerization is generally referred to the polymerization of iso-olefins or vinyl aromatics in the presence of metal or semimetal halides as Lewis acid catalysts and tertiary alkyl halides, Benzyl or allyl halides, esters or ethers as initiators, which with the Lewis acid form a carbocation or a cationogenic complex. A comprehensive overview can be found in Kennedy / Ivan "Carbocationic Macromolecular Engineering ", Hauser Publishers 1992. For the preparation of telechelic polyisobutenes As a rule, a bifunctional initiator, such as dicumyl chloride, is used.

Around to as possible uniform polyisobutenes, it is necessary that the cationic centers of growing in the course of the polymerization Polymer chains are stabilized. For this it considers the state of Technique as required in a solvent with a relative high dielectric constant work. So far, in particular halogenated for this purpose Hydrocarbons, optionally mixed with aliphatic or aromatic hydrocarbons, used as solvent.

Of further is the isobutene polymerization in the prior art rather low initial concentrations of isobutene, wherein usually consumed isobutene in the course of the polymerization is replaced (so-called "incremental monomer addition "). Furthermore the isobutene used is substantially completely implemented.

For example, EP-A 722 957 describes the preparation of telechelic isobutene polymers using an at least bifunctional initiator, such as dicumyl chloride, in chlorinated C ₃ -C ₈ hydrocarbons. The initial concentration of isobutene in the examples is less than 30% by volume. A disadvantage of the known processes is that under the reaction conditions present, aromatic initiators, such as 1,3- and 1,4-dicumyl chloride, can react to form indanyl or diindene groups (compare Cr Pratrap, SA Mustafa, JP Heller, J. Polym Sci., Part A, Polym. Chem., 1993, 31, pp. 2387-2391), so that only monofunctional polyisobutenes, ie those having only one reactive end group, are obtained to a considerable extent. This not only affects the targeted synthesis of defined telechelic polyisobutenes; the uniformity of the polymers also decreases (ie the polydispersity index (PDI), which corresponds to the quotient of weight-average molecular weight (M _w ) and number-average molecular weight (M _n ) (PDI = M _w / M _n ), increases).

task The present invention was to provide a process for the preparation of polyisobutene, with which predominantly telechelic, especially bifunctional polyisobutenes can be obtained. In addition, the polyisobutenes should a narrow molecular weight distribution (i.e. small PDI value). In particular, should be for this purpose when using dicumyl chloride as an initiator, the formation of Indanes and diindanes are prevented or at least reduced to obtain a high proportion of bifunctional polyisobutenes.

Surprisingly, it was found in the context of the present invention that polyisobutenes having a high molecular uniformity and a high proportion of bifunctional polymers are obtained if the isobutene used is not completely reacted in the polymerization and if the halogenated solvent is used in relation to the isobutene used and, if appropriate existing another Solvents used in a relatively small proportion. Even better results are achieved, if one also assumes a high initial isobutene concentration.

• a) das Lösungsmittel höchstens 35 Gew.-% halogenierte Kohlenwasserstoff-Lösungsmittel, bezogen auf das Gesamtgewicht des Reaktionsgemischs, enthält; und
• b) höchstens 80 Gew.-% des eingesetzten Isobutens polymerisiert werden.

The object has accordingly been achieved by a process for the preparation of isobutene polymers having a number average molecular weight of 270 to 5000, in which isobutene or an isobutene-containing monomer mixture in the presence of an initiator which is selected from 1,3-bis (2) chloro-2-propyl) benzene (1,3-dicumyl chloride; 1,3-DCC) and 1,4-bis (2-chloro-2-propyl) benzene (1,4-dicumyl chloride; 1,4-DCC), and a Lewis acid in a solvent polymerized, characterized in that

• a) the solvent contains at most 35% by weight of halogenated hydrocarbon solvents, based on the total weight of the reaction mixture; and
• b) at most 80 wt .-% of the isobutene used are polymerized.

In the context of the present invention, halogenated hydrocarbon solvents are understood as meaning aliphatic or alicyclic saturated or unsaturated as well as aromatic hydrocarbons in which at least one hydrogen atom has been replaced by a halogen atom, especially chlorine. Preference is given to halogenated aliphatic compounds, in particular halogenated alkanes, for example halogenated C ₁ -C ₈ -alkanes. Examples thereof are methyl chloride, methylene chloride, chloroform, carbon tetrachloride, chloroethane, dichloroethane, trichloroethane, tetrachloroethane, chloropropane, chlorobutane and the like. Particular preference is given to halogenated C ₁ -C ₂ -alkanes, such as methyl chloride, methylene chloride, chloroform, carbon tetrachloride, chloroethane, dichloroethane, trichloroethane and tetrachloroethane, and mixtures thereof, halogenated C ₁ -alkanes, such as methyl chloride, methylene chloride, chloroform and carbon tetrachloride, and mixtures thereof are even more preferred especially because of their favorable solution viscosity and heat transfer. Specially used methylene chloride.

Of the halogenated hydrocarbon is usually mixed with other hydrocarbon solvents (Co-solvents) used. Examples of this are aliphatic or alicyclic saturated or unsaturated as well aromatic hydrocarbons.

Under Hydrocarbons are understood in the context of the present invention organic molecules, which are composed of carbon and hydrogen atoms and in the Essentially contain no heteroatoms. Heteroatoms are all elements other than carbon and hydrogen, such as oxygen, Nitrogen, sulfur and halogen. The phrase "essentially contains no heteroatoms "means that the aliphatic or alicyclic hydrocarbons less as 1% by weight, preferably less than 0.5% by weight, more preferably less than 0.1% by weight and in particular less than 0.01% by weight Heteroatoms, based on the total weight of the hydrocarbons used, contain.

Saturated aliphatic hydrocarbons are alkanes. C ₄ -C ₁₀ -alkanes and in particular C ₄ -C ₈ -alkanes are preferred. C ₄ -C ₈ -alkanes are, for example, butane, isobutane, pentane, hexane, heptane and octane and also their constitution isomers. In addition, C ₄ -C ₁₀ -alkanes are nonane and decane and also their constitutional isomers.

Saturated alicyclic hydrocarbons are, for example, cycloalkanes. C ₅ -C ₈ -cycloalkanes and in particular C ₅ -C ₆ -cycloalkanes are preferred. Examples of C ₅ -C ₆ -cycloalkanes are cyclopentane and cyclohexane. In addition, C ₅ -C ₈ cycloalkanes further include, for example, cycloheptane and cyclooctane.

in the The scope of the present invention is understood to mean unsaturated aliphatic hydrocarbons aliphatic hydrocarbons, which have at least one olefinic double bond. Under unsaturated Alicyclic hydrocarbons are understood to be alicyclic (i.e. cyclic, non-aromatic) hydrocarbons which are at least have an olefinic double bond. With several double bonds these can conjugated or isolated in the molecule.

The unsaturated aliphatic hydrocarbons are preferably alkenes, for example C ₂ -C ₁₀ -alkenes, alkadienes, for example C ₄ -C ₁₀ -alkadienes, or alkatrienes, for example C ₆ -C ₁₀ -alkatrienes, or mixtures thereof. Particularly preferred are C ₂ -C ₆ -alkenes, C ₄ -C ₆ -alkadienes and mixtures thereof.

C ₂ -C ₁₀ alkene is a monounsaturated linear or branched hydrocarbon of 2 to 10 carbon atoms. Examples of these are ethene, propene, 1-butene, 2-butene, isobutene, 1-pentene, 2-pentene, 1-hexene, 2-hexene, 3-hexene, 1-heptene, 2-heptene, 3-heptene, 1 Octene, 2-octene, 3-octene, 4-octene, 1, 2, 3, 4-nonene, 1, 2, 3, 4 and 5-decene and constitutional isomers thereof. C ₂ -C ₆ -alkene is a monounsaturated linear or branched hydrocarbon having 2 to 6 carbon atoms. Examples are ethene, Propene, 1-butene, 2-butene, isobutene, 1-pentene, 2-pentene, 1-hexene, 2-hexene, 3-hexene and constitutional isomers thereof.

C ₄ -C ₁₀ -alkadiene is a diunsaturated linear or branched hydrocarbon having 4 to 10 carbon atoms. Examples of these are butadiene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene and decadiene and constitution isomers thereof. C ₄ -C ₆ -alkadiene is a diunsaturated linear or branched hydrocarbon having 4 to 6 carbon atoms. Examples of these are 1,3-butadiene, 1,3- and 1,4-pentadiene and 1,3-, 1,4-, 1,5- and 2,4-hexadiene, as well as constitutional isomers thereof.

C ₆ -C ₁₀ alkatriene is a triunsaturated linear or branched hydrocarbon of 6 to 10 carbon atoms. Examples of these are hexatriene, 1,3,5- and 1,4,6-heptatriene, 1,3,5-, 1,3,6-, 1,3,7-, 1,4,6-, 1, 4,7- and 2,4,6-octatriene, nonatriene and decatriene, and constitutional isomers thereof.

The unsaturated alicyclic hydrocarbons are preferably cycloalkenes, for example C ₅ -C ₆ -alkenes, such as cyclopentene or cyclohexene, or cycloalkadienes, for example C ₅ -C ₆ -alkadienes, such as cyclopentadiene or cyclohexadiene. It goes without saying that the alicyclic compounds do not have so many conjugated double bonds that an aromatic system is present.

aromatic Hydrocarbons are hydrocarbons that are an aromatic System included, like benzene. Suitable solvents are aromatic Hydrocarbons can also be substituted. Examples are toluene, nitrobenzene, Chlorobenzene, dichlorobenzene and the like.

Preferred co-solvents are selected from aliphatic hydrocarbons, in particular alkanes, for example C ₄ -C ₁₀ -alkanes, and alkenes, for example C ₂ -C ₁₀ -alkenene, each in admixture with alkadienes, for example C ₄ -C ₁₀ -alkadienes , and / or alkatrienes, for example C ₆ -C ₁₀ -alkatrienes may be present Preferred alkenes are 1-alkenes and isoalkenes. Particularly preferred cosolvents are selected from C ₄ -C ₈ -alkanes and C ₂ -C ₆ -alkenes, which may each be present in admixture with C ₄ -C ₆ -alkadienes. Examples of suitable C ₂ -C ₆ -alkenes are ethene, propene, 1- and 2-butene, isobutene, 1- and 2-pentene, 1-, 2- and 3-hexene and their constitution isomers and mixtures of these alkenes. Examples of suitable C ₄ -C ₈ -alkanes are butane, isobutane, pentane, hexane, heptane, octane and their constitution isomers and mixtures of these alkanes. Examples of suitable C ₄ -C ₆ -alkadienes are butadiene, 1,3- and 1,4-pentadiene, 1,3-, 1,4- and 2,4-hexadiene and their constitution isomers and mixtures of these alkadienes. More preferred alkenes are propene, 1-butene and isobutene, as well as mixtures of these alkenes. Even more preferred alkenes are isobutene and 1-butene, as well as mixtures thereof. If the alkanes and / or alkenes are used in a mixture with alkadienes and / or alkatrienes, the mixture contains the polyenes in an amount of preferably at most 1% by weight, more preferably at most 0.5% by weight, more preferably at most 0 , 2 wt .-%, in particular at most 0.05 wt .-%, especially at most 0.02 wt .-%, based on the total weight of the co-solvent. In particular, the co-solvent used is C ₄ -C ₈ -alkanes and especially hexane or heptane.

Alternatively, preferred co-solvents are selected from technical mixtures of aliphatic hydrocarbons. Preferred technical mixtures are C ₄ -hydrocarbon mixtures, ie mixtures containing hydrocarbons with 4 carbon atoms, such as butane, isobutane, 1-butene, 2-butene, isobutene and butadiene. Examples include C ₄ raffinates, C ₄ cuts from isobutane dehydrogenation, C ₄ cuts from steam crackers, FCC (Fluid Catalyzed Cracking) crackers, especially if it at least partially freed from 1,3-butadiene contained therein are. Suitable C ₄ -hydrocarbon mixtures preferably contain at most 1% by weight, more preferably at most 0.5% by weight, more preferably at most 0.2% by weight, in particular at most 0.05% by weight, especially at most 0, 02 wt .-%, butadiene, based on the total weight of the mixture.

There Isobutene in the process according to the invention not completely polymerized, it always acts as a co-solvent. Isobutene is not as pure substance, but in the mixture with further Components are used, so do the other components of this mixture, unless they are reacted in the polymerization reaction, as a co-solvent.

In a particularly preferred embodiment contains the solvent in addition to the co-solvents, resulting from the provision of the monomer (i.e., excess isobutene or when using isobutene-containing mixtures as a monomer source also the other components of this mixture), no further cosolvents. That is, that solvent includes in addition to excess isobutene and optionally other components of the monomer source which are not polymerized, and optionally the halogenated Solvent, especially preferred no further cosolvents.

Irrespective of the type of solvent, the isobutene to be polymerized can be present both in the form of isobutene itself and in the form of isobutene-containing C ₄ -hydrocarbon mixtures, ie mixtures containing, in addition to isobutene, further hydrocarbons having 4 carbon atoms, such as butane, isobutane, 1 Butene, 2-butene and butadiene. The above statements on suitable C ₄ -hydrocarbon mixtures apply here accordingly. Preferred hydrocarbon mixtures are, for example, raffinate I and C ₄ cuts from FCC crackers or from isobutane dehydrogenation. Raffinate I is a C ₄ hydrocarbon stream having approximately the following composition: 0-5% isobutane; 4-12% n-butane; 35-55% isobutene; 15-55% 1-butene; 10-25% 2-butene and 0-0.5% 1,3-butadiene. C ₄ cuts from FCC crackers have approximately the following composition: 5-15% n-butane, 15-25% isobutane, 14-18% isobutene, 15-25% trans-but-2-ene, 10-20 % cis-but-2-ene and 10-20 1-butene. C ₄ cuts from the isobutane dehydrogenation have approximately the following composition: 45-55% isobutene, 40-50% butane and 2-10% 1- and 2-butenes.

There the technical mixtures sometimes do not contain sufficient isobutene, one for the inventive method If necessary, they must have sufficient initial isobutene concentration enriched with isobutene before use.

Preferably However, one uses isobutene itself.

It can also monomer mixtures of isobutene or isobutene-containing Hydrocarbon mixture with olefinically unsaturated monomers, which with Isobutene copolymerizable under cationic Polymerisationsbedlngungen are to be implemented. The inventive method is also for block copolymerization of isobutene with ethylenic polymerizable under cationic polymerization conditions unsaturated Comonomers suitable. If monomer mixtures of isobutene with suitable comonomers to be copolymerized, contains the monomer mixture preferably more than 80% by weight, particularly preferably more than 90 Wt .-%, and in particular more than 95 wt .-% isobutene, and less as 20% by weight, preferably less than 10% by weight, and in particular less than 5% by weight Comonomers.

Suitable copolymerizable monomers are vinylaromatics such as styrene and α-methylstyrene, C ₁ -C ₄ -alkylstyrenes such as 2-, 3- and 4-methylstyrene and 4-tert-butylstyrene, isoolefins having 5 to 10 C atoms such as 2-methylbutene-1 , 2-methylpentene-1, 2-methylhexene-1, 2-ethylpentene-1, 2-ethylhexene-1 and 2-propylheptene-1. Comonomers also include 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.

to Preparation of block copolymers can be the living chain ends also in the presence of unreacted isobutene with suitable Comonomers are implemented. Suitable comonomers are in particular those who have a higher Have nucleophilicity as isobutene. Examples are vinyl aromatics such as α-methylstyrene. For bulk polymerization, e.g. first homopolymerize isobutene and add the comonomer in due course. The thereby emerging Comonomerstämmige reactive chain end is either deactivated or after one of Embodiments described below scheduled to form a functional end group or to Education higher Block copolymers reacted again with isobutene.

Covalent metal halides and semimetallic halides having an electron-pair gap may be considered as the Lewis acid. Such compounds are known to the person skilled in the art, for example from JP Kennedy et al. in US 4,946,889 . US 4,327,201 . US 5,169,914 EP-A-206 756, EP-A-265 053 and JP Kennedy, B. Ivan, "Designed Polymers by Carbocationic Macromolecular Engineering", Oxford University Press, New York, 1991. They are usually selected from halogen Compounds of titanium, tin, aluminum, vanadium or iron, as well as the halides of boron. The chlorides are preferred, and in the case of aluminum also the monoalkylaluminum dichlorides and the dialkylaluminum chlorides. Preferred Lewis acids are titanium tetrachloride, boron trichloride, boron trifluoride, tin tetrachloride, aluminum trichloride, vanadium pentachloride, iron trichloride, alkylaluminum dichlorides and dialkylaluminum chlorides. Particularly preferred Lewis acids are titanium tetrachloride, boron trichloride and ethylaluminum dichloride, and especially titanium tetrachloride. Alternatively, it is also possible to use a mixture of at least two Lewis acids, for example boron trichloride mixed with titanium tetrachloride.

It has proven useful to carry out the polymerization in the presence of an electron donor. Suitable electron donors are aprotic organic compounds which have a free electron pair located on a nitrogen, oxygen or sulfur atom. Preferred donor compounds are selected from pyridines such as pyridine itself, 2,6-dimethylpyridine, and sterically hindered pyridines such as 2,6-diisopropylpyridine and 2,6-di-tert-butylpyridine; Amides, in particular N, N-dialkylamides of aliphatic or aromatic carboxylic acids such as N, N-dimethylacetamide; Lactams, in particular N-alkyl lactams such as N-methylpyrrolidone; Ethers, for example dialkyl ethers, such as diethyl ether and diisopropyl ether, cyclic ethers, such as tetrahydrofuran; Amines, in particular trialkylamines such as triethylamine; Esters, in particular C ₁ -C ₄ -alkyl esters of aliphatic C ₁ -C ₆ -carboxylic acids, such as ethyl acetate; Thioethers, in particular dialkylthioethers or alkylarylthioethers, such as methylphenylsulfide; Sulfoxides, in particular dialkyl sulfoxides, such as dimethyl sulfoxide; Nitriles, in particular alkylnitriles such as acetonitrile and propionitrile; Phosphines, in particular trialkylphosphines or triarylphosphines, such as trimethylphosphine, triethylphosphine, tri-n-butylphosphine and triphenylphosphine and non-polymerizable, aprotic organosilicon compounds which have at least one oxygen-bound or ganic radical.

Especially the donor compounds are selected from non-polymerisable, aprotic organosilicon compounds containing at least one of oxygen having bound organic radical. Examples of such Radicals are alkyloxy, cycloalkyloxy, aryloxy, arylalkyloxy and acyloxy (Alkylcarbonyloxy).

Under Alkyl is a linear or branched saturated Hydrocarbon radical having usually 1 to 20 carbon atoms, and preferably 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, 2-butyl, n-pentyl, 2-methylbutyl-1, 2-methylpentyl-1,2-ethylbutyl-1, n-hexyl, 2-hexyl, 2-methylhexyl-1,2-ethylhexyl-1, n-heptyl, n-octyl, isooctyl, n-decyl, and comparable residues.

Aryl is an aromatic hydrocarbon radical having generally 6 to 20 C atoms, such as phenyl, naphthyl and comparable groups which may have one or more C ₁ -C ₁₀ -alkyl groups as substituents, for example tolyl, isopropylphenyl, xylyl or tert. butylphenyl.

Cycloalkyl as used herein means a generally 5-, 6- or 7-membered, saturated carbocycle which may optionally have one or more C ₁ -C ₁₀ -alkyl groups as substituents.

arylalkyl stands for an alkyl radical having usually 1 to 10 carbon atoms, and preferably 1 to 4 carbon atoms, which is represented by an aryl radical as defined above, substituted, e.g. For Benzyl or 2-phenylethyl.

alkyloxy stands for over one Oxygen atom bound alkyl. Accordingly, aryloxy, Cycloalkyloxy and arylalkyloxy for over Oxygen atom bonded aryl, cycloalkyl or arylalkyl.

acyloxy stands for one over Oxygen-bonded alkylcarbonyl radical, preferably 1 to Has 6 C atoms in the alkyl moiety, e.g. for acetyloxy, propionyloxy, Butyroxy etc.

The organosilicon compounds may be one or more, e.g. 2 or 3, silicon atoms having at least one oxygen-bonded organic Rest have. Preferred are those organosilicon compounds, the one, two or three, and especially 2 or 3, via oxygen having bound organic radicals per silicon atom.

Preferred such organosilicon compounds are those of the following general formula: R ^a _r Si (OR ^b ) _4-r wherein r is 1, 2 or 3,
R ^{a may be the} same or different and independently of one another C ₁ -C ₂₀ -alkyl, C ₃ -C ₇ -cycloalkyl, aryl or aryl-C ₁ -C ₄ -alkyl, where the latter three radicals also have one or more C ₁ -C ₁₀ alkyl groups may have as substituents, and
R ^{b are the} same or different and are C ₁ -C ₂₀ alkyl or in the event that r is 1 or 2, two radicals R ^b together may be alkyls.

In the above formula, r is preferably 1 or 2. R ^a is preferably a C ₁ -C ₈ alkyl group, and in particular a branched or bonded via a secondary carbon atom alkyl group, such as isopropyl, isobutyl, sec-butyl, or a 5-, 6- or 7-membered cycloalkyl group, or an aryl group, in particular phenyl. The variable R ^b is preferably a C ₁ -C ₄ alkyl group or a phenyl, tolyl or benzyl radical.

Examples for such preferred compounds are dimethoxydiisopropylsilane, dimethoxyisobutylisopropylsilane, Dimethoxydiisobutylsilane, dimethoxydicyclopentylsilane, dimethoxyisobutyl-2-butylsilane, Diethoxyisobutylisopropylsilane, triethoxytoluylsilane, triethoxybenzylsilane and triethoxyphenylsilane.

In the context of the present invention, C ₁ -C ₄ -alkyl is a branched or linear alkyl radical, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl. C ₁ -C ₈ -alkyl furthermore represents pentyl, hexyl, heptyl _; Octyl and its positional isomers. In addition, C ₁ -C ₁₀ -alkyl is nonyl and decyl and their positional isomers. C ₁ -C ₂₀ alkyl furthermore represents undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl and their positional isomers.

C ₃ -C ₇ -cycloalkyl is, for example, cyclopropyl, cyclopentyl, cyclohexyl and cycloheptyl. C ₅ -C ₇ -cycloalkyl is, for example, cyclopentyl, cyclohexyl and cycloheptyl.

aryl stands in particular for Phenyl, naphthyl or tolyl.

Aryl-C ₁ -C ₄ -alkyl is especially benzyl or 2-phenylethyl.

Alkylene is, for example, C ₂ -C ₅ -alkylene, such as 1,2-ethylene, 1,2- and 1,3-propylene, 1,4-butylene and 1,5-pentylene.

In a further preferred embodiment of the process according to the invention, the polymerization is carried out in the presence of an alkylammonium halide. Suitable alkylammonium halides are both monoalkylammonium salts and di-, tri- or tetraalkylammonium halides. Suitable alkyl radicals are C ₁ -C ₁₀ -alkyl radicals, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl, and their constituent isomers. Preferred alkyl radicals are C ₁ -C ₆ -alkyl radicals, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl and their constituent isomers. In the di-, tri- and tetraalkylammonium salts, the alkyl radicals may be the same or different. Preference is given to tetraalkylammonium halides, in particular those having four identical alkyl radicals. Suitable halide counterions are fluoride, chloride and bromide, with chloride and bromide being preferred. Examples of suitable tetraalkylammonium halides are tetramethylammonium fluoride, tetramethylammonium chloride, tetramethylammonium bromide, tetraethylammonium fluoride, tetraethylammonium chloride, tetraethylammonium bromide, Tetrapropylammoniumfluorid, tetrapropylammonium chloride, tetrapropylammonium bromide, tetrabutylammonium fluoride, tetrabutylammonium chloride, tetrabutylammonium bromide, Tetrapentylammoniumfluorid, tetrapentylammonium chloride, tetrapentylammonium bromide, Tetrahexylammoniumfluorid, tetrahexylammonium and tetrahexylammonium.

The Polymerization can be both batchwise (discontinuous) and be carried out in a continuous manner.

It has proven to be advantageous in the polymerization at relative high initial monomer concentrations perform, as this pushes Indan formation further back. The initial content of isobutene is therefore preferably at least 50% by weight, more preferably at least 60% by weight, stronger preferably at least 65% and in particular at least 70% by weight, e.g. at least 80% by weight, based on the total weight of the reaction mixture.

Becomes the polymerization is carried out in a continuous manner, so is Again, preferably the isobutene content at the feed point at least 50% by weight, more preferably at least 60% by weight, stronger preferably at least 65% and in particular at least 70% by weight, e.g. at least 80% by weight, based on the total weight of height of Feed point located reaction mixture.

According to the invention used isobutene is not completely polymerized, but to a maximum of 80 % By weight reacted. Preferably, at most 60% by weight is particularly preferred at the most 50% by weight, stronger preferably at most 40 wt .-%, in particular at the most 35% by weight and especially at most 30 Wt .-% of the isobutene used polymerized. Not by the full Conversion (partial conversion) of the isobutene used is at the beginning the polymerization the molar ratio from isobutene to initiator especially large, reducing the likelihood Indan formation of initiator and the first and / or the second annealed isobutene molecule intramolecular ring closure is reduced. In addition, the partial sales also leads that the isobutene used always acts as a solvent.

Preferably In the course of the polymerization, no further isobutene is added.

Also the reduced content of halogenated hydrocarbons in the reaction mixture contributes to Pushing back the Indan formation at. Preferably, the halogenated hydrocarbon in a crowd of at most 30% by weight, more preferably at most 25% by weight, more preferably from at most 20 wt .-%, in particular of at most 15% by weight and especially of at most 10% by weight, based on the total weight of the reaction mixture, used. In a specific embodiment, the polymerization even done in a system These are essentially no halogenated hydrocarbon solvents contains. The term "essentially contains no halogenated hydrocarbon solvents "means that the Reaction mixture less than 2 wt .-%, preferably less than 1 wt%, more preferably less than 0.5 wt%, even more preferably less than 0.1% by weight and in particular less than 0.05% by weight, e.g. less than 0.01% by weight, halogenated hydrocarbon solvents, based on the total weight of the reaction mixture. This especially applies when the polymerization in the presence of an electron donor and / or an alkylammonium halide.

In In an alternative preferred embodiment, the halogenated solvent in an amount of from 2 to 35% by weight, preferably from 2 to 30% by weight, more preferably from 2 to 25% by weight, more preferably from 2 to 20 Wt .-%, in particular from 2 to 15 wt .-%, especially from 2 to 10 % By weight, based on the total weight of the reaction mixture. In this case it is also possible to conduct the polymerization so that no electron donor or Alkyammoniumhalogenid used or in only minor amounts, e.g. in a total of at most 10 mmol / l, based on the total volume of the reaction mixture. In this case, it is also preferable to use the halogenated solvent in a molar ratio to the initiator of preferably 20: 1 to 1: 1 use.

The volume ratio from halogenated hydrocarbon solvent to used Isobutene is preferably 1: 3 to 1: 100, more preferably 1: 4 to 1: 100, more preferably 1: 4.5 to 1: 100, especially 1: 5 to 1: 100 and especially 1: 6 to 1: 100. In extreme cases, the ratio can also be 0: 1.

The Lewis acid is used in an amount sufficient to interact with the initiator to form an initiator complex. The molar ratio of Lewis acid to initiator is preferably 10: 1 to 1:10, more preferably 5: 1 to 1: 5, especially preferably 2: 1 to 1: 5 and especially 1.5: 1 to 1: 4.

The Initial concentration of Lewis acid in the reaction mixture (i.e., the amount used) is preferably in the Range of 5 to 200 mmol / l, more preferably 10 to 100 mmol / l and in particular 10 to 80 mmol / l, based on the total volume of the reaction mixture.

Becomes a mixture of at least two polymerization-active Lewis acids used, so lies one of the Lewis acids preferably in excess in front. Polymerization-active Lewis acids are those which are also individually initiate isobutene polymerization in combination with the initiator can. Specially when using a boron trichloride / titanium tetrachloride mixture the molar ratio from boron trichloride to titanium tetrachloride preferably 1.5: 1 to 100: 1, particularly preferably 2: 1 to 20: 1 and in particular 5: 1 to 10: 1.

When Initiator is in the process of the invention 1,3- or 1,4-dicumyl chloride used, with 1,4-dicumyl chloride is preferred. Preferably, the initiator is in an amount of at least 10 mmol / l, more preferably at least 50 mmol / l and in particular at least 100 mmol / l used, based on the total volume of the reaction mixture. The maximum quantity at initiator amounts preferably at most 300 mmol / l, more preferably at most 250 mmol / l and in particular not more than 200 mmol / l, based on the total volume of the reaction mixture. Especially in the case of 1,3-dicumyl chloride is the maximum amount to initiator preferably 100 mmol / l, in particular 70 mmol / l, based on the total volume of the reaction mixture.

Becomes the polymerization is carried out in the presence of an electron donor, so is the molar ratio of Lewis acid to electron donor generally 20: 1 to 1:10, preferably 10: 1 to 1: 1.

Becomes the polymerization is carried out in the presence of an alkylammonium halide, see above is the molar ratio of Lewis acid to alkyl ammonium halide generally 10: 1 to 1: 3, preferably 5: 1 to 1: 2, more preferably 3: 1 to 1: 1.

The Alkylammonium halide is used in an amount of preferably 5 to 100 mmol / l, more preferably 10 to 80 mmol / l and in particular 20 to 60 mmol / l, based on the total volume of the reaction mixture, used.

It It goes without saying that the polymerization is largely under aprotic, especially under anhydrous, reaction conditions performs. Under aprotic or anhydrous reaction conditions it is understood that the water content (or the content of protic Impurities) in the reaction mixture less than 50 ppm and in particular less than 5 ppm. As a rule, therefore, one will use the starting materials before their use dry physically and / or by chemical means. Especially has it proven the preferred as a solvent used unsaturated Aliphatic or alicyclic hydrocarbons according to customary Pre-cleaning and predrying with an organometallic compound, for example, an organolithium, organomagnesium or organoaluminum compound to put in an amount that is sufficient to remove the traces of water from the solvent to remove. The solvent thus treated is then directly condensed into the reaction vessel. In similar You can also with the monomers to be polymerized, in particular the isobutene or isobutene-containing mixtures. The halogenated solvent is suitably with suitable drying agents, for example with calcium chloride, phosphorus pentoxide or molecular sieve, from traces of water) freed.

The Pre-cleaning or predrying of the solvents and the isobutene takes place in usual Way, preferably by treatment with solid drying agents such as molecular sieves or predried oxides such as alumina, Silica, calcium oxide or barium oxide. In an analogous way to dry the feedstocks for which treatment with metal alkyls is not suitable, for example, the initiator or styrene comonomers.

The Polymerization of the isobutene or the isobutene-containing feedstock occurs spontaneously when mixing the initiator system (i.e., Lewis acid and Initiator) with the isobutene or the isobutene-containing feedstock at the desired Reaction temperature. This can be done so that isobutene or optionally the isobutene-containing feedstock in the solvent submits, brings to reaction temperature and then the Initiator system admits. You can also do that, that one Initiator system optionally present in the solvent and then the Isobutene or the isobutene-containing starting material admits. In the Addition of the initiator system will usually proceed in such a way that the components of the initiator system are added separately. Preferably becomes the Lewis acid as the last component of the reaction system added to the probability to minimize the start of polymerization by protons. at The discontinuous mode of operation described here can be so for example proceed by first using the initiator and optionally the electron donor and / or the alkylammonium halide optionally in the solvent submitted, then the isobutene or the isobutene-containing feedstock and subsequently the Lewis acid admits. The beginning of polymerization is then the time, containing all components of the initiator system in the reaction vessel are. Preferably, however, it is done so that you first isobutene or the isobutene-containing feed optionally in the solvent then the initiator and optionally the electron donor and / or the alkylammonium halide and then the Polymerization by addition of the Lewis acid starts.

Next The discontinuous procedure described here can be make the polymerization as a continuous process. This leads the starting materials, i. the monomers to be polymerized, optionally the solvent and the initiator system of the polymerization reaction continuously to and de continuously absorbs reaction product, so that in the Reactor more or less stationary polymerization to adjust. The components of the initiator system can thereby both separately and together, preferably diluted in the solvent supplied be, with the separate addition being preferred. The polymerizable Isobutene or the isobutene-containing feedstock can be used as such, diluted with a solvent or fed as an isobutene-containing hydrocarbon stream. Preferably, isobutene or the isobutene-containing feedstock first contacted with the initiator, for example, by the two components are already supplied as a mixture to the reactor or by feeding the initiator directly behind the monomer feed he follows. Become also electron donors and / or alkylammonium halides used, their contact with the monomer is preferably carried out even before the contact of the latter with the Lewis acid. For this become electron donors and / or alkylammonium halides either fed in admixture with the monomer and / or the initiator or the feed takes place directly behind the monomer feed. The Lewis acid preferably comes after mixing the monomer with the Initiator and optionally the electron donor and / or the alkylammonium halide with the rest Reactants in contact.

The reaction is preferably carried out such that the polymer concentration is in the range from 1 to 90% by weight, more preferably from 2 to 80% by weight and in particular from 5 to 50% by weight, based on the total weight of the reaction mixture , In the continuous reaction regime, the weight ratios refer to the stationary polymer concentration or to the polymer concentration in the reactor Outlet or at the Polymerisationsabbruch.

In The rule will be the process of the invention at temperatures in the range of 60 to -140 ° C, preferably in the range of 0 to -120 ° C, and especially preferably in the range of -30 to -80 ° C. Of the Reaction pressure is of subordinate importance at temperatures below -10 ° C, since isobutene is condensed at these temperatures and thus practically not compressible any further. Only at higher temperatures and / or using even lower boiling solvents like ethene or propene, when using a forced circulation with outside lying heat exchangers or a tube (bundle) reactor is preferably carried out at elevated reaction pressure, for example at a pressure of 3 to 20 bar.

The removal the heat of reaction carried out in the batch as well as in the continuous reaction in usual Way, for example by internal or external built-in heat exchangers and / or by wall cooling and / or taking advantage of a Siedekühlung.

When Reaction vessels for the implementation of the inventive method basically come all Reactors as they usually do in a cationic polymerization of isobutene, e.g. a cationic one Polymerization of isobutene with boron trifluoride-oxygen complexes, be used. In that regard, here on the relevant status directed to the technique. Come in discontinuous reaction the usual for this stirred tank in consideration, preferably with a Siedekühlung, suitable mixers, inlets, heat exchanger elements and inerting devices are equipped. The continuous reaction can in the usual for this Reaction boilers, reaction cascades, tubular reactors, tube bundle reactors, in particular circular out Tube and shell and tube reactors, carried out which are preferably in the manner described above for stirred tanks equipped are. A particularly preferred type of reactor is, for example in EP-A-1395620 Wendelrohrreaktor described.

To the Reaction termination, the living chain ends are deactivated, for example by adding a protic compound, in particular by adding of water, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol or tert-butanol, or mixtures thereof with water.

By means of the process according to the invention, telechelic (bifunctional) polyisobutenes are obtained which contain a functional group at both termini (chain ends). This functional group is preferably a group -CH ₂ -C (CH ₃ ) ₂ -halogen. This is usually formed during reaction quenching with a protic deactivator. The halogen atom in this terminal group is usually derived from the initiator used for the polymerization. Preferably, halogen is chlorine. These telechelic polyisobutenes are valuable intermediates for the preparation of other bifunctional polyisobutene derivatives. Examples of the derivatization include the alkylation of phenols and the elimination of hydrogen halide from the group -CH ₂ -C (CH ₃ ) ₂ -halogen to form an ethylenically unsaturated terminal group.

The conversion of the terminal group -CH ₂ -C (CH ₃ ) ₂ -halogen into an ethylenically unsaturated radical (methylidene double bond) can be carried out, for example, thermally, for. B. by heating to a temperature of 70 to 200 ° C, preferably under vacuum, or by treatment with a base. Suitable bases are, for example, alkali metal alkoxides, such as sodium methoxide, sodium ethoxide and potassium tert-butoxide, basic aluminum oxide, alkali metal hydroxides, such as sodium hydroxide, and tertiary amines, such as pyridine or tributylamine, cf. Kennedy et al., Polymer Bulletin 1985, 13, 435-439. Preferably, sodium ethoxide or potassium tert-butoxide is used.

However, it is also possible to obtain ethylenically terminated polyisobutenes at the end of the chain without first introducing the group -CH ₂ -C (CH ₃ ) ₂ -halogen. For this purpose, the living chain ends of the isobutene polymer are suitably reacted with a terminating reagent which adds an ethylenically unsaturated group to the end of the chain.

Suitable termination reagents are, for example, trialkylallylsilane compounds, for example trimethylallylsilane. The living chain ends are thereby terminated by adding a trialkylallylsilane compound. The use of allyl silanes leads to the termination of the polymerization with the introduction of an allyl radical at the polymer chain end, cf. EP 264 214 ,

Another example of a termination reagent is 1,1-diphenylethylene. The living chain ends are terminated by addition of 1,1-diphenylethylene and a base, whereby a diphenyl-substituted double bond is introduced at the chain end, cf. J. Feldthusen, B. Iván, AHE Müller and J. Kops, Macromol. Rep. 1995, A32, 639, J. Feldthusen, B. Iván and AHE Müller, Macromolecules 1997, 30, 6989 and Macromolecules 1998, 31, 578, DE-A 19648028 and DE-A 19610350.

Further are conjugated dienes, e.g. Butadiene, as termination reagents suitable. Here, the reactive chain end is conjugated with the Diene implemented and then deactivated as described above, cf. DE-A 40 25 961.

In addition, two or more living polymer chains can be coupled for termination by adding a coupling agent. "Coupling" means the formation of chemical bonds between the reactive chain ends such that two or more polymer chains become one molecule. The molecules obtained by coupling are symmetric telechelic or star-shaped molecules whose other living chain ends must be terminated according to one of the methods described above. By coupling of living copolymers of the AB ⁺ type, it is possible, for example, to prepare triblock copolymers of the AB-BA type in which A is a polyisobutene block and B is a polymer block other than a polyvinyl aromatic block.

suitable Coupling agents, for example, at least two allylständig to same or different double bonds arranged elektrofuge Leaving groups, e.g. Trialkylsilyl groups, on, so that the cationic center of a reactive chain end in a concerted Reaction with elimination of the leaving group and shift of the Can attach double bond. Other coupling agents have at least a conjugated system to which the cationic center a reactive chain end to form a stabilized Cations can electrophilically add. By cleavage of a leaving group, e.g. of a proton, then arises under reformation of the conjugated Systems a stable s-bond to the polymer chain. Several of these conjugated systems can be interconnected by inert spacer.

• (i) Verbindungen, die wenigstens zwei 5-gliedrige Heterocyclen mit einem unter Sauerstoff, Schwefel und Stickstoff ausgewählten Heteroatom aufweisen, z.B. organische Verbindungen, die wenigstens zwei Thiophen- oder vorzugsweise Furanringe aufweisen, wie
  
  worin R für C₁-C₁₀-Alkylen steht, vorzugsweise Methylen oder 2,2-Propandiyl;
• (ii) Verbindungen mit wenigstens zwei allylständigen Trialkylsilylgruppen, wie 1,1-Bis(trialkylsilylmethyl)ethylene, z.B. 1,1-Bis(trimethylsilylmethyl)ethylen, Bis[(trialkylsilyl)-propenyl]benzole, z.B.
  
  (worin Me für Methyl steht),
• (iii) Verbindungen mit wenigstens zwei konjugiert zu jeweils zwei aromatischen Ringen angeordneten Vinylidengruppen, wie Bis-diphenylethylene z.B.

Suitable coupling agents include:

• (I) compounds having at least two 5-membered heterocycles having a heteroatom selected from oxygen, sulfur and nitrogen, for example organic compounds having at least two thiophene or preferably furan rings, such as
  
  wherein R is C ₁ -C ₁₀ alkylene, preferably methylene or 2,2-propanediyl;
• (ii) compounds having at least two allyl-containing trialkylsilyl groups, such as 1,1-bis (trialkylsilylmethyl) ethylenes, eg 1,1-bis (trimethylsilylmethyl) ethylene, bis [(trialkylsilyl) -propenyl] benzenes, eg
  
  (where Me is methyl),
• (iii) compounds having at least two vinylidene groups conjugated to two aromatic rings each, such as bis-diphenylethylenes, for example

A description of suitable coupling agents can be found in the following references; the coupling reaction can be carried out analogously to the reactions described there: R. Faust, S. Hadjikyriacou, Macromolecules 2000, 33, 730-733; R. Faust, S. Hadjikyriacou, Macromolecules 1999, 32, 6393-6399; R. Faust, S. Hadjikyriacou, Polym. Bull. 1999, 43, 121-128; R. Faust, Y. Bae, Macromolecules 1997, 30, 198; R. Faust, Y. Bae, Macromolecules 1998, 31, 2480; R. Storey, Maggio, Polymer Preprints 1998, 39, 327-328; WO99 / 24480; US 5,690,861 and US 5,981,785 ,

The Coupling usually takes place in the presence of a Lewis acid, wherein such Lewis acids are suitable, which also to carry out the actual polymerization reaction can be used. To carry out the Coupling reactions are also also the same solvents and temperatures suitable for carrying them out actual polymerization reaction begins. Conveniently, can be the coupling therefore as a one-pot reaction following the Polymerization reaction in the same solvent in the presence of Carry out the Lewis acid used for the polymerization. Usually one uses one molar amount of the coupling agent, which is about the quotient of the Polymerization used molar amount of initiator, divided by the number of coupling sites of the coupling agent.

To the termination (deactivation and / or introduction of an ethylenically unsaturated terminal group and / or coupling) will usually be the solvent and excess isobutene in suitable aggregates such as rotary, falling film or thin film evaporators or removed by relaxation of the reaction solution.

One Another object of the present invention are isobutene polymers, those by the method according to the invention available are.

The isobutene polymers produced by the process according to the invention have a narrow molecular weight distribution. The polydispersity index (PDI = M _w / M _n ) is preferably at most 1.50, particularly preferably at most 1.40, more preferably at most 1.35 and especially at most 1.30, for example at most 1.25 or at most 1.20. In particular, it is in the range of 1.05 to 1.20.

By the inventive method receives one as well polymeric products which are predominantly, i. at least 90%, preferably at least 95%, more preferably consist of at least 98% bifunctional polyisobutenes, i.e. of polyisobutenes having two halo termini or two ethylenic unsaturated (Vinyl or vinylidene) termini or with two allyl chloride termini.

The process according to the invention is generally used for the preparation of polyisobutenes having a number average molecular weight M _{n of} from 270 to 5,000, preferably from 380 to 5,000 and in particular from 500 to 5,000.

The isobutene polymers prepared according to the invention are terminated at the chain ends by a group -CH ₂ -C (CH ₃ ) ₂ -halogen, particularly preferably -CH ₂ -C (CH ₃ ) ₂ -Cl. Alternatively, the groups at the chain ends are preferably ethylenically unsaturated groups which, as described above, are present thermally or by reacting the halogen-substituted chain ends with a suitable base or by reacting the living polyisobutene chains formed during the polymerization with a trialkylallylsilane compound, with 1, 1-diphenylethylene or a conjugated diene are available.

• i) Hydrosilylierung,
• ii) Hydrosulfurierung,
• iii) elektrophile Substitution an Aromaten,
• iv) Epoxidierung und ggf. Umsetzung mit Nucleophilen,
• v) Hydroborierung und ggf. oxidative Spaltung,
• vi) Umsetzung mit einem Enophil in einer En-Reaktion,
• vii) Addition von Halogenen oder Halogenwasserstoffen,
• viii) Hydroformylierung und gegebenenfalls Hydrierung oder reduktive Aminierung des erhaltenen Produkts,
• ix) Copolymerisation mit einer olefinisch ungesättigten Dicarbonsäure oder einem Derivat davon, oder
• x) Aminierung durch nucleophile Substitution

The polyisobutenes obtained according to the invention can furthermore be subjected to the following functionalization reactions:

• i) hydrosilylation,
• ii) hydrosulfurization,
• iii) electrophilic substitution on aromatics,
• iv) epoxidation and optionally reaction with nucleophiles,
• v) hydroboration and optionally oxidative cleavage,
• vi) reaction with an enophile in an ene reaction,
• vii) addition of halogens or hydrogen halides,
• viii) hydroformylation and optionally hydrogenation or reductive amination of the product obtained,
• ix) copolymerization with an olefinically unsaturated dicarboxylic acid or a derivative thereof, or
• x) Amination by nucleophilic substitution

i) hydrosilylation

to Functionalization can be a method according to the invention produced polyisobutene (especially with ethylenically unsaturated Groups terminated polyisobutene) of a reaction with a silane in the presence of a silylation catalyst to give at least one partially functionalized with silyl functionalized polyisobutene become.

Suitable hydrosilylation catalysts are, for example, transition metal catalysts, wherein the transition metal is preferably selected from Pt, Pd, Rh, Ru and Ir. Examples of suitable platinum catalysts include platinum in finely divided form ("platinum black"), platinum chloride and platinum complexes such as hexachloroplatinic acid or divinyldisiloxane-platinum complexes, eg tetramethyldivinyldisiloxane-platinum complexes. Suitable rhodium catalysts are, for example, (RhCl (P (C ₆ H ₅ ) ₃ ) ₃ ) and RhCl ₃ . Also suitable are RuCl ₃ and IrCl ₃ . Suitable catalysts are also Lewis acids such as AlCl ₃ or TiCl ₄ and peroxides. It may be advantageous to use combinations or mixtures of the aforementioned catalysts.

suitable Silanes are e.g. halogenated silanes, such as trichlorosilane, methyldichlorosilane, Dimethylchlorosilane and trimethylsiloxydichlorosilane; alkoxysilanes such as methyldimethoxysilane, phenyldimethoxysilane, 1,3,3,5,5,7,7-heptamethyl-1,1-dimethoxytetrasiloxane and trialkoxysilanes, e.g. For example, trimethoxysilane and triethoxysilane, and Acyloxysilanes. Trialkoxysilanes are preferably used.

The Reaction temperature in the silylation is preferably in one Range from 0 to 140 ° C, more preferably 40 to 120 ° C. The reaction usually becomes carried out under normal pressure, but can also be elevated at To press, such as. in the range of about 1.5 to 20 bar, or reduced pressures, e.g. 200 to 600 mbar.

The Reaction can be without solvent or in the presence of a suitable solvent. When solvent for example, toluene, tetrahydrofuran and chloroform are preferred.

ii) Hydrosulfurization

For functionalization, a polyisobutene (specifically polyisobutene terminated with ethylenically unsaturated groups) prepared by the process according to the invention can be reacted with hydrogen sulfide or a thiol, such as alkyl- or arylthiols, hydroxymercaptans, aminomercaptans, thiocarboxylic acids or silanethiols, to give a polyisobutene which is at least partially functionalized with thio groups be subjected. Suitable hydro-alkylthio additions are described in J. March, Advanced Organic Chemistry, 4th Edition, John Wiley & Sons, pp. 766-767, incorporated herein by reference. The reaction can usually be carried out both in the absence and in the presence of initiators and in the presence of electromagnetic radiation. Upon addition of hydrogen sulfide, functionalized polyisobutenes are obtained with thiol groups. The addition of hydrogen sulfide is preferably carried out at temperatures below 100 ° C and a pressure of 1 to 50 bar, more preferably of about 10 bar. In addition, the addition is preferably carried out in the presence of a cation exchange resin, such as Amberlyst 15. In the reaction with thiols in the absence of initiators, the Markovnikov addition products to the double bond are generally obtained. Suitable initiators of the hydro-alkylthio addition are, for example, protic and Lewis acids, such as concentrated sulfuric acid or AlCl ₃ and acidic cation exchangers, such as Amberlyst 15. Suitable initiators are furthermore those which are capable of forming free radicals, such as peroxides or azo compounds , Hydro-alkylthio addition in the presence of these initiators usually gives the anti-Markovnikov addition products. The reaction can furthermore be carried out in the presence of electromagnetic radiation having a wavelength of 400 to 10 nm, preferably 200 to 300 nm.

iii) Electrophilic substitution at aromatics

to Derivatization can be a method according to the invention produced polyisobutene with a compound which at least has an aromatic or heteroaro matic group, in the presence an alkylation catalyst are reacted. Suitable aromatic and heteroaromatic compounds, catalysts and reaction conditions These so-called Friedel-Crafts alkylation are, for example in J. March, Advanced Organic Chemistry, 4th edition, John Wiley & Sons, Pp. 534-539 described, which is hereby incorporated by reference.

Preferably For the alkylation an activated aromatic compound is used. Suitable aromatic compounds are, for example, alkylaromatics, Alkoxyaromatics, hydroxyaromatics or activated heteroaromatics, like thiophenes or furans.

worin R¹ und R² unabhängig voneinander für Wasserstoff, OH oder CH₃ stehen. Besonders bevorzugt sind Phenol, die Kresol-Isomere, Katechol, Resorcinol, Pyrogallol, Fluoroglucinol und die Xylenol-Isomere. Insbesondere werden Phenol, o-Kresol und p-Kresol eingesetzt. Gewünschtenfalls können auch Gemische der zuvor genannten Verbindungen zur Alkylierung eingesetzt werden.The aromatic hydroxy compound used for the alkylation is preferably selected from phenolic compounds having 1, 2 or 3 OH groups which may optionally have at least one further substituent. Preferred further substituents are C ₁ -C ₈ -alkyl groups and in particular methyl and ethyl. Particular preference is given to compounds of the general formula

wherein R ¹ and R ^{2 are} independently hydrogen, OH or CH ₃ . Particularly preferred are phenol, the cresol isomers, catechol, resorcinol, pyrogallol, fluoroglucinol and the xylenol isomers. In particular, phenol, o-cresol and p-cresol are used. If desired, it is also possible to use mixtures of the abovementioned compounds for the alkylation.

Suitable are also polyaromatics, such as polystyrene, polyphenylene oxide or polyphenylene sulfide, or copolymers of aromatics, for example with butadiene, isoprene, (Meth) acrylic acid derivatives, Ethylene or propylene.

The catalyst is preferably selected from Lewis acidic alkylation catalysts, which in the context of the present application is understood as meaning both individual acceptor atoms and acceptor-ligand complexes, molecules, etc., provided that these have overall (outwardly) Lewis acid (electron acceptor) properties exhibit. These include, for example, AlCl ₃ , AlBr ₃ , BF ₃ , BF ₃ .2C ₆ H ₅ OH, BF ₃ [O (C ₂ H ₅ ) ₂ ] ₂ , TiCl ₄ , SnCl ₄ , AlC ₂ H ₅ Cl ₂ , FeCl 3 ₃ , SbCl ₅ and SbF ₅ . These alkylation catalysts can be used together with a cocatalyst, for example an ether. Suitable ethers are di (C ₁ -C ₈ ) alkyl ethers, such as dimethyl ether, diethyl ether, di-n-propyl ether, and tetrahydrofuran, di (C ₅ -C ₈ ) cycloalkyl ethers, such as dicyclohexyl ether and ethers having at least one aromatic hydrocarbon radical like anisole. If a catalyst-cocatalyst complex is used for the Friedel-Crafts alkylation, the molar ratio of catalyst to cocatalyst is preferably in the range from 1:10 to 10: 1. The reaction can also be catalyzed with protic acids such as sulfuric acid, phosphoric acid, methanesulfonic acid or trifluoromethanesulfonic acid. Organic protic acids can also be present in polymer-bound form, for example as ion exchange resin. Also suitable are zeolites and inorganic polyacids.

The Alkylation can be solvent-free or in a solvent carried out become. Suitable solvents are, for example, n-alkanes and mixtures thereof and alkylaromatics, such as toluene, ethylbenzene and xylene as well as halogenated derivatives from that.

The Alkylation is preferably carried out at temperatures between -10 ° C and + 100 ° C. The Reaction becomes common at atmospheric pressure carried out, but also at higher To press (e.g., volatile solvents) or at lower pressures carried out become.

By suitable choice of molar ratios of aromatic or heteroaromatic compound to polyisobutene and the catalyst may be the proportion of alkylated products obtained and their degree of alkylation are adjusted. Substantially monoalkylated Polyisobutenylphenols are generally in excess on phenol or in the presence of a Lewis acid alkylation catalyst get if in addition an ether is used as cocatalyst.

to Further functionalization can be the resulting polyisobutenylphenol an implementation in the sense of a Mannich reaction with at least one Aldehyde, for example formaldehyde, and at least one amine, that at least one primary or secondary Has amine function, wherein one with polyisobutene alkylated and in addition at least partially aminoalkylated compound. It can too Reaction and / or condensation products of aldehyde and / or amine be used. The preparation of such compounds are in WO 01/25 293 and WO 01/25 294, to the full extent hereby Reference is made.

iv) epoxidation

For functionalization, a polyisobutene (specifically polyisobutene terminated with ethylenically unsaturated groups) prepared according to the process of the invention can be reacted with at least one peroxide compound to give an at least partially epoxidized polyisobutene. Suitable methods for epoxidation are described in J. March, Advanced Organic Chemistry, 4th Edition, John Wiley & Sons, S. 826-829, incorporated herein by reference. Preferably, the peroxide compound used is at least one peracid, such as m-chloroperbenzoic acid, performic acid, peracetic acid, trifluoroperacetic acid, perbenzoic acid and 3,5-dinitroperbenzoic acid. The preparation of the peracids can be carried out in situ from the corresponding acids and H ₂ O ₂ optionally in the presence of mineral acids. Other suitable epoxidation reagents are, for example, alkaline hydrogen peroxide, molecular oxygen and alkyl peroxides such as tertiary butyl hydroperoxide. Suitable solvents for the epoxidation are, for example, conventional, non-polar solvents. Particularly suitable solvents are hydrocarbons such as toluene, xylene, hexane or heptane. The epoxide formed is relatively stable and can then be reacted ring-opening with water, acids, alcohols, thiols or primary or secondary amines to give, inter alia, diols, glycol ethers, glycol thioethers and amines. However, this functionalization route often proceeds with relatively low yields because of steric hindrance at the tertiary carbon atom of the epoxy group. On the other hand, if the epoxide is converted to the corresponding carbonyl compound, which can be done, for example, by means of zeolites or Lewis acids, then the carbonyl compounds formed can be derivatized with significantly better yields, for example by subjecting them to the reactions A) to C) described under ix).

The epoxide can also be converted to a 2-polyisobutenyl-1,3-propanediol by reaction with a borane and subsequent oxidative cleavage of the resulting ester. Suitable boranes are, for example, diborane (B ₂ H ₆ ) and also alkyl and arylboranes RBH ₂ (R = alkyl or aryl). The reaction with the borane is suitably carried out in a borane-coordinating solvent. Examples of these are open-chain ethers, such as dialkyl, diaryl or alkylaryl ethers, and cyclic ethers, such as tetrahydrofuran or 1,4-dioxane. The oxidative cleavage to the 1,3-diol can be carried out, for example, as described in v). The conversion of the epoxide into a 2-polyisobutenyl-1,3-propanediol is described, for example, in EP-A-0737662, to which reference is hereby made in its entirety.

v) hydroboration

For functionalization, a polyisobutene (specifically polyisobutene terminated with ethylenically unsaturated groups) prepared according to the process of the invention can be subjected to a reaction with a (optionally generated in situ) borane to give an at least partially hydroxylated polyisobutene. Suitable hydroboration processes are described in J. March, Advanced Organic Chemistry, 4th Edition, John Wiley & Sons, pp. 783-789, which is hereby incorporated by reference. Examples of suitable hydroborating reagents are diborane, which is generally generated in situ by reacting sodium borohydride with BF ₃ etherate, diisamylborane (bis [3-methylbut-2-yl] borane), 1,1,2-trimethylpropylborane, 9- Borbicyclo [3.3.1] nonane, diisocamphenylborane, which are obtainable by hydroboration of the corresponding alkenes with diborane, chloroborane-dimethylsulfide, alkyldichloroboranes or H ₃ BN (C ₂ H ₅ ) ₂ .

Usually you lead hydroboration in a solvent by. Suitable solvents for hydroboration are, for example, acyclic ethers such as diethyl ether, methyl tert-butyl ether, Dimethoxyethane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, cyclic ethers such as tetrahydrofuran or dioxane and hydrocarbons such as hexane or toluene or mixtures thereof. The reaction temperature is usually from the reactivity of the hydroborating agent and is usually between the Melting and boiling point of the reaction mixture, preferably in Range of 0 ° C up to 60 ° C.

Usually, the hydroborating agent is used in excess with respect to the alkene. The boron atom preferably adds to the less substituted and thus sterically less hindered Koh lenstoffatom.

Usually The formed alkyl boranes are not isolated, but by subsequent conversion transferred directly into the value products. A very significant implementation of alkylboranes is the reaction with alkaline Hydrogen peroxide to give an alcohol, preferably formally corresponds to the anti-Markovnikov hydration of the alkene. Furthermore you can the resulting alkylboranes a reaction with bromine in the presence be subjected to hydroxide ions to obtain the bromide.

vi) ene reaction

to Functionalization can be a method according to the invention produced polyisobutene (especially with ethylenically unsaturated Groups terminated polyisobutene) with at least one alkene, the has an electrophile-substituted double bond, in one En-reaction can be implemented (see, for example, DE-A 4 319 672 or H. Mach and P. Rath in "Lubrication Science II (1999), p. 175-185, which is incorporated by reference). In the ene reaction is an alkene called En with an allyl-containing hydrogen atom with an electrophilic alkene, the so-called enophile, in one pericyclic reaction comprising a carbon-carbon bond, a Double bond shift and a hydrogen transfer implemented. In the present case, the polyisobutene reacts as ene. Suitable enophiles are compounds, as well as dienophiles in the Diels-Alder reaction be used. The preferred enophile is maleic anhydride used. This results at least partially with succinic anhydride groups (Succinanhydridgruppen) functionalized polyisobutenes. Depending on the molecular weight and the double bond type of the polyisobutene used, the maleic anhydride concentration and the temperature is usually 70 to 90% of the used Polymers functionalized. The new in the polyisobutene chain If desired, the double bond formed can then be further functionalized be, for example by reaction with maleic anhydride in a further ene reaction with attachment of another succinic anhydride group.

The En-reaction may optionally be carried out in the presence of a Lewis acid as Catalyst can be performed. Suitable examples are aluminum chloride and ethylaluminum chloride.

• a) Umsetzung mit wenigstens einem Amin unter Erhalt eines wenigstens teilweise mit Succinimidgruppen und/oder Succinamidgruppen funktionalisierten Polyisobutens,
• b) Umsetzung mit wenigstens einem Alkohol unter Erhalt eines wenigstens teilweise mit Succinestergruppen funktionalisierten Polyisobutens, und
• c) Umsetzung mit wenigstens einem Thiol unter Erhalt eines wenigstens teilweise mit Succinthioestergruppen funktionalisierten Polyisobutens.

For further functionalization, it is possible, for example, to subject a polyisobutene derivatized with succinic anhydride groups to a subsequent reaction which is selected from:

• a) reaction with at least one amine to give a polyisobutene which is at least partially functionalized with succinimide groups and / or succinamide groups,
• b) reaction with at least one alcohol to give a polyisobutene at least partially functionalized with succinic ester groups, and
• c) reaction with at least one thiol to obtain a polyisobutene functionalized at least in part with succinothioester groups.

vii) addition of halogen or hydrogen halides

to Functionalization can be a method according to the invention produced polyisobutene (especially with ethylenically unsaturated Groups terminated polyisobutene) of a reaction with hydrogen halide or a halogen to give at least partially halogen groups be subjected to functionalized polyisobutene. Suitable reaction conditions the hydrohalo addition are described in J. March, Advanced Organic Chemistry, 4th edition, publisher John Wiley & Sons, Pp. 758-759 described, which is hereby incorporated by reference. For the addition of hydrogen halide In principle, HF, HCl, HBr and HI are suitable. The addition of HI, HBr and HF can usually be done at room temperature, whereas for the addition of HCl usually elevated temperatures and / or elevated pressure be used.

The Addition of hydrogen halides can in principle be in the absence or in the presence of initiators or of electromagnetic Radiation done. In addition in the absence of initiators, especially of peroxides, are usually the Markovnikov addition products receive. With the addition of peroxides, the addition of HBr leads to usually to anti-Markovnikov products.

The halogenation of double bonds is described in J. March, Advanced Organic Chemistry, 4th Edition, John Wiley & Sons, pp. 812-814, incorporated herein by reference. For the addition of Cl, Br and I, the free halogens can be used. To obtain mixed-halogenated compounds, the use of interhalogen compounds is known. Fluorine-containing compounds such as CoF ₃ , XeF ₂ and mixtures of PbO ₂ and SF ₄ are generally used for the addition of fluorine. Bromine usually adds up Room temperature in good yields of double bonds. Chlorine-containing reagents, such as SO ₂ Cl ₂ , PCl _5, etc., can be used in addition to the free halogen to add chlorine.

The formed dihalides can if desired for example, be dehydrohalogenated by thermal treatment, to obtain allyl halide-terminated polymers.

Becomes for halogenating chlorine or bromine in the presence of electromagnetic Radiation used, so receives one essentially the products of radical substitution on the polymer chain and not or only to a minor extent addition products to the terminal Double bond.

viii) hydroformylation

to Functionalization can be the polyisobutene (especially with ethylenic unsaturated Groups terminated polyisobutene) of a reaction with carbon monoxide and hydrogen in the presence of a hydroformylation catalyst undergo an at least partially hydroformylated polyisobutene is obtained.

Suitable hydroformylation catalysts are known and preferably comprise a compound or a complex of an element of Group VIII of the Periodic Table, such as Co, Rh, Ir, Ru, Pd or Pt. For influencing the activity and / or selectivity, hydroformylation catalysts modified with N- or P-containing ligands are preferably used. Suitable salts of these metals are, for example, the hydrides, halides, nitrates, sulfates, oxides, sulfides or the salts with alkyl or arylcarboxylic acids or alkyl or arylsulfonic acids. Suitable complex compounds have ligands selected, for example, from halides, amines, carboxylates, acetylacetonate, aryl or alkylsulfonates, hydride, CO, olefins, dienes, cycloolefins, nitriles, N-containing heterocycles, aromatics and heteroaromatics, ethers, PF ₃ , Phospholes, phosphabenzenes and mono-, bi- and polydentate phosphine, phosphinite, phosphonite, phosphoramidite and phosphite ligands.

In general, catalytically active species of the general formula H _x M _y (CO) _z L _{q are} formed under hydroformylation conditions from the particular catalysts or catalyst precursors used, where M is a metal of subgroup VIII, L is a ligand and q, x, y , z are integers, depending on the valence and type of metal and the ligand L's binding.

To a preferred embodiment For example, the hydroformylation catalysts are used in situ for the hydroformylation reaction produced reactor produced.

A another preferred form is the use of a carbonyl generator, in the prefabricated carbonyl z. B. is adsorbed on activated carbon and only the desorbed carbonyl is fed to the hydroformylation, but not the salt solutions, from which the carbonyl is produced.

suitable Rhodium compounds or complexes are e.g. Rhodium (II) and rhodium (III) salts, such as rhodium (III) chloride, rhodium (III) nitrate, rhodium (III) sulfate, Potassium rhodium sulfate, Rhodium (II) or rhodium (III) carboxylate, rhodium (II) and rhodium (III) acetate, Rhodium (III) oxide, salts of rhodium (III) acid, trisammonium hexachlororhodate (III) etc. Furthermore, rhodium complexes, such as Rhodiumbiscarbonylacetylacetonat, Acetylacetonato-bis-ethyl rhodium (I), etc.

Also suitable are ruthenium salts or compounds. Suitable ruthenium salts are, for example, ruthenium (III) chloride, ruthenium (IV), ruthenium (VI) or ruthenium (VIII) oxide, alkali metal salts of ruthenium oxygen acids such as K ₂ RuO ₄ or KRuO ₄ or complex compounds, such as. B. RuHCl (CO) (PPh ₃ ) ₃ . The metal carbonyls of ruthenium such as dodecacarbonyltriruthenium or octadecacarbonylhexaruthenium, or mixed forms can, in which CO has been partly replaced by ligands of the formula PR _3, such as Ru (CO) ₃ (PPh _{3) 2} is used.

suitable Cobalt compounds are, for example, cobalt (II) chloride, cobalt (II) sulfate, Cobalt (II) carbonate, cobalt (II) nitrate, their amine or hydrate complexes, Cobalt carboxylates, such as cobalt formate, cobalt acetate, cobalt ethylhexanoate, Cobalt naphthanoate, as well as the cobalt-caprolactamate complex. Also here we can the carbonyl complexes of cobalt such as dicobaltoctacarbonyl, tetracobalt dodecacarbonyl and Hexacobalthexadecacarbonyl be used.

The above and other suitable compounds are known in principle and in the literature described enough.

Suitable activating agents which can be used for hydroformylation are, for. B. Bronsted acids, Lewis acids, such as. B. BF ₃ , AlCl ₃ , ZnCl ₂ , and Lewis bases.

The Composition of the synthesis gas used from carbon monoxide and hydrogen can vary widely. The molar ratio of Carbon monoxide and hydrogen is usually about 5:95 to 95: 5, preferably about 40:60 to 60:40. The temperature at the hydroformylation is generally in a range of about 20 to 200 ° C, preferably about 50 to 190 ° C. The reaction is usually at the partial pressure of the reaction gas at the chosen Reaction temperature performed. In general, the pressure is in a range of about 1 to 700 bar, preferably 1 to 300 bar.

The carbonyl number of the resulting hydroformylated polyisobutenes depends on the number average molecular weight M _n .

Preferably becomes the predominant one Part of the used in the medium molecular weight, reactive polyisobutene converted double bonds by the hydroformylation in aldehydes. By Use of suitable hydroformylation catalysts and / or an excess Hydrogen in the synthesis gas used can be the predominant Part of the ethylenically unsaturated double bonds contained in the starting material also be converted directly into alcohols. This can also be done in a two-stage Functionalization according to the im Reaction step B) described below.

The obtained by hydroformylation functionalized polyisobutenes are advantageous as intermediates for further processing by Functionalization of at least a part of the contained in them Aldehyde functions.

A) Oxocarboxylic acids

to Further functionalization can be obtained in step viii) hydroformylated polyisobutenes with an oxidizing agent below Obtaining an at least partially functionalized with carboxy polyisobutene implement.

For the oxidation from aldehydes to carboxylic acids can generally a big one Number of different oxidants and processes used, the z. In J. March, Advanced Organic Chemistry, John Wiley & Sons, 4th edition, P. 701ff. (1992). These include z. Oxidation with permanganate, Chromate, atmospheric oxygen, etc. The oxidation with air can both catalytically in the presence of metal salts as well as in the absence of catalysts. As metals are preferred used, which are capable of a valency change, such. B. Cu, Fe, Co, Mn, etc. The reaction usually succeeds even in the absence a catalyst. In air oxidation, sales can easily exceed the Reaction time to be controlled.

According to a further embodiment, the oxidizing agent is an aqueous hydrogen peroxide solution in combination with a carboxylic acid, such as. As acetic acid used. The acid value of the resulting polyisobutenes having carboxyl function depends on the number average molecular weight M _n .

B) Oxo alcohols

To another suitable embodiment can the hydroformylated polyisobutenes obtained in step viii) a reaction with hydrogen in the presence of a hydrogenation catalyst to obtain an at least partially functionalized with alcohol groups Polyisobutene be subjected.

suitable Hydrogenation catalysts are generally transition metals such. B. Cr, Mo, W, Fe, Rh, Co, Ni, Pd, Pt, Ru, etc., or mixtures thereof, to increase the activity and stability on carriers, like z. As activated carbon, alumina, diatomaceous earth, etc., are applied can. To increase the catalytic activity can Fe, Co, and preferably Ni also in the form of the Raney catalysts as Metal sponge can be used with a very large surface area.

The Hydrogenation of the oxo-aldehydes from stage viii) takes place in dependence from the activity the catalyst preferably at elevated temperatures and elevated pressure. Preferably, the reaction temperature is about 80 to 150 ° C and the Pressure at about 50 to 350 bar.

The alcohol number of the obtained hydroxy-containing polyisobutenes depends on the number-average molecular weight M _n .

C) amine synthesis

To another suitable embodiment become the hydroformylated polyisobutenes obtained in step viii) for the further functionalization of a reaction with hydrogen and ammonia or a primary or secondary Amin in the presence of an amination catalyst to obtain a at least partially functionalized with amine groups polyisobutene subjected.

suitable Amination catalysts are those previously described in step B) Hydrogenation catalysts, preferably copper, cobalt or nickel, in the form of Raney metals or on a carrier can be used. Also suitable are platinum catalysts.

In the amination with ammonia aminated polyisobutenes are obtained with predominantly primary amino functions. Primary and secondary amines suitable for amination are compounds of the general formulas R-NH ₂ and RR'NH, in which R and R 'are, for example, C ₁ -C ₁₀ -alkyl, C ₆ -C ₂₀ -aryl, C ₇ -C ₂₀ - Arylalkyl, C ₇ -C ₂₀ alkylaryl or cycloalkyl. Diamines such as N, N-dimethylaminopropylamine and N, N'-dimethylpropylene-1-3-diamine are also suitable.

The amine value of the resulting amino-functional polyisobutenes depends on the number-average molecular weight M _n and on the number of incorporated amino groups.

ix) copolymerization with olefinically unsaturated dicarboxylic acids

The Copolymerization of unsaturated terminated polyisobutenes with unsaturated dicarboxylic acids, such as maleic or fumaric acid, or suitable derivatives thereof, such as maleic anhydride, maleic acid esters or fumaric acid ester, is in EP-A-0644208 to which reference is hereby incorporated by reference. The resulting copolymers can subsequently further derivatized, for example by esterification or Transesterification at the carboxyl groups of the dicarboxylic acid building block used or by their reaction with mono- di- or polyamines to the corresponding ammonium salts or amides, and when using maleic or their derivatives as a comonomer also to imides, diimides or Polyimides.

x) Nucleophilic substitution by amines

Especially Allyl halide-terminated polyisobutenes obtained by reaction of the living chain ends with a conjugated diene and subsequent hydrolytic Workup available are, by reaction with ammonia, primary or secondary Amines under such reaction conditions, which for a nucleophilic substitution at an allylic center, into the corresponding amine-terminated ones Transfer polymers. suitable Reaction conditions are for example in Jerry March, Advanced Organic Chemistry, 3rd Edition, 1985, John Wiley & Sons, page 364ff.

The with the method according to the invention obtained bifunctional polyisobutenes serve as macromonomers for further Polymerizations, polycondensation, network formation or coupling. Besides, they are they as precursors for the functionalization reactions i) to x) described above are suitable.

preferred Functionalization products are polyisobutenes with hydroxy groups, in particular with 2 or 4 hydroxy groups, with amine groups, in particular with 2 amine groups, with thiol groups, in particular with 4 or 6 SH groups, with alkoxysilane groups, in particular with 2 alkoxysilane groups, with Succinic acid groups, especially with 2 succinic anhydride or with 2 succinimide groups, and with phenolic groups, especially with 2 phenolic groups.

typically, find the bifunctional polyisobutenes and their functionalization products in adhesives and sealants, in elastomers, e.g. in tire materials, or as additives in the mineral oil sector, e.g. in fuels and lubricants, application.

The The following examples are intended to illustrate the invention in more detail.

1. Production of difunctional isobutene polymers

When Apparatus were two 1 liter four-necked flask A and B were used, over a closable Connected with each other. Both pistons A (condensation piston) and B (reaction flask) were with a magnetic stirrer, a thermometer, a Septum, a dropping funnel with pressure compensation and an attached dry ice condenser equipped with drying tube and a heating and cooling bath. piston B was as well with a React-IR (IR measuring device for the reaction control) of the Fa.

Equipped Mettler Toledo. In the condensation flask A phenanthroline, methylene chloride and optionally hexane were presented. Isobutene was condensed in the dropping funnel and emptied into the flask A. The mixture was then titrated through the septum with a 1.6 M n-butyllithium solution in hexane until it turned brown for 5 minutes. The stopcock was then opened to flask B and the contents of flask A were transferred to flask B, to which had previously been added 1,3- or 1,4-dicumyl chloride, with heating, where it condensed on the dry ice condenser. The solution was added with 1.1 g of phenyltriethoxysilane and then cooled to -76 ° C. Titanium tetrachloride was then added and the isobutene conversion was monitored by React-IR. The predicted decrease in absorbance at 890 cm ^-1 terminated the polymerization by adding 10 ml of ethanol. After excess isobutene had evaporated overnight, the mixture was treated with 150 ml each of water and heptane, mixed vigorously and transferred to a separatory funnel. The aqueous phase was discarded; the organic phase was washed twice with 150 ml of water each time and then dried over sodium sulfate. Subsequently, the solvent was removed at room temperature under reduced pressure. The reaction conditions and the properties of the respective polymers obtained are shown in the following tables.

In Examples 1 to 8, 1,4-dicumyl chloride was used as the initiator, while in Examples 9 to 16 1,3-dicumyl chloride was used. In Examples 1 to 5 and 9 to 14, the polymerization was stopped so as to obtain polymers having an M _n of about 2,000, whereas in Examples 6 to 8 and 15 and 16, polymers having a M _n of about 500 were desired.

Table 1: Use of 1,4-dicumyl chloride (1,4-DCC) as initiator

Table 2: Use of 1,3-dicumyl chloride (1,3-DCC) as initiator

• IB = isobutene
• DCC = dicumyl chloride
• PDI = polydispersity index M _w / M _n
• Indane [%]: proportion of monofunctional polyisobutene (due to of indan formation) in total polymer yield
• * Polymerization with the addition of 8 g (25 mmol) of tetrabutylammonium bromide in piston B

Claims (17)

Process for the preparation of isobutene polymers with a number average molecular weight of 270 to 5000, at the isobutene or an isobutene-containing monomer mixture in the presence an initiator who selected is under 1,3-bis (2-chloro-2-propyl) benzene and 1,4-bis (2-chloro-2-propyl) benzene, and a Lewis acid in a solvent polymerized, characterized in that a) the solvent at the most 35% by weight of halogenated hydrocarbon solvents, based on the total weight of the reaction mixture; and b) at the most 80 wt .-% of the isobutene used are polymerized. The method of claim 1, wherein the initial content isobutene, based on the total weight of the reaction mixture, at least 50 wt .-% is. Method according to one of claims 1 or 2, wherein the solvent at the most 30 wt .-% of halogenated hydrocarbon solvents, based on the Total weight of the reaction mixture, contains. Method according to one of the preceding claims, wherein at the most 50 wt .-% of the isobutene used are polymerized. Method according to one of the preceding claims, wherein the Lewis acid is selected from titanium tetrachloride and boron trichloride. Method according to one of the preceding claims, wherein the Lewis acid in an amount of 5 to 200 mmol / l, based on the volume of Reaction mixture is used. Method according to one of the preceding claims, wherein the initiator in an amount of 10 to 300 mmol / l, based on the volume of the reaction mixture is used. Method according to one of the preceding claims, wherein the polymerization as well in the presence of an electron donor. The method of claim 8, wherein the electron donor selected is among non-polymerizable, aprotic organosilicon Compounds containing at least one oxygen-bonded organic Rest have. Method according to one of the preceding claims, wherein the polymerization as well in the presence of an alkylammonium halide. The method of claim 10, wherein the alkylammonium halide in an amount of 5 to 100 mmol / l, based on the total volume of the reaction mixture is used. Method according to one of the preceding claims, wherein the polymerization stopped by addition of a protic compound becomes. The method of claim 12, wherein after termination product obtained by polymerization with a protic compound subsequently is treated thermally or with a base. Method according to one of claims 1 to 11, wherein the at the polymerization of isobutene or the isobutene-containing monomer mixture formed polyisobutene with a trialkylallylsilane compound, a conjugated diene or 1,1-diphenylethene is reacted together with a base. Isobutene polymer obtainable according to the method of one the claims 1 to 14. Functionalized isobutene polymer, obtainable thereby that is an isobutene polymer according to claim 15 subjects one of the following functionalization reactions: i) hydrosilylation, ii) hydrosulforation, iii) electrophilic Substitution of aromatics, iv) epoxidation and optionally conversion with nucleophiles, v) hydroboration and optionally oxidative cleavage, vi) Reaction with an enophile in an ene reaction, vii) Addition of halogens or hydrogen halides, viii) hydroformylation and optionally hydrogenation or reductive amination of the obtained product, ix) copolymerization with an olefinically unsaturated dicarboxylic acid or a derivative thereof, or x) amination by nucleophilic Substitution. Functionalized isobutene polymer according to claim 15, wherein the isobutene polymer at least 2 hydroxy groups, at least 2 amino groups, at least 2 thiol groups, at least 2 alkoxysilane groups, at least 2 succinic anhydride groups, at least 2 succinimide groups or at least 2 phenolic groups.