EP1954728A1

EP1954728A1 - Method for producing highly reactive isobutylene homo- or copolymers from technical flows of c4-hydrocarbon using bronsted acid catalyst complexes

Info

Publication number: EP1954728A1
Application number: EP06819482A
Authority: EP
Inventors: Phillip Hanefeld; Volker BÖHM; Marcus Sigl; Nina Challand; Michael Röper; Hans-Michael Walter
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2005-11-21
Filing date: 2006-11-15
Publication date: 2008-08-13
Also published as: US20080249264A1; CN101331160A; DE102005055819A1; WO2007057406A1; KR20080070057A

Abstract

The invention relates to the production of highly reactive isobutylene homo- or copolymers with Mn = 500 to 1,000,000 by polymerizing isobutylene from technical flows of C4-hydrocarbon having a isobutylene content ranging from 1 to 90 % by weight in liquid phase in the presence of a dissolved, dispersed or supported catalyst complex by using, as a catalyst complex, a Bronsted acid compound (I) [H+]k Yk- Lx (I) Yk- weakly coordinating k-valent anion, which contains at least one carbon-containing grouping; L represents neutral solvent molecules, and; x = 0.

Description

Process for the preparation of highly reactive Isobutenhomo- or copolymers from technical C4 hydrocarbon streams by means of proton acid catalyst complexes

description

The present invention relates to a process for the preparation of highly reactive isobutene homopolymers or copolymers having a number average molecular weight M _{n of} from 500 to 1,000,000 by polymerization of isobutene from a technical C 4 hydrocarbon stream having an isobutene content of from 1 to 90% by weight. in the liquid phase in the presence of a dissolved, dispersed or supported catalyst complex.

In contrast to the so-called low-reactive polymers, highly reactive polyisobutene homopolymers or copolymers are understood as meaning polyisobutenes which contain a high content of terminal ethylenic double bonds. In the context of the present invention, highly reactive polyisobutenes are to be understood as meaning polyisobutenes which have a proportion of vinylidene double bonds (α-double bonds) of at least 60 mol%, preferably at least 70 mol% and in particular at least 80 mol% , based on the polyisobutene macromolecules have. For the purposes of the present application, vinylidene groups are understood to mean those double bonds whose position in the polyisobutene macro-molecule is represented by the general formula

polymer

is described, i. the double bond is in the α-position in the polymer chain. "Polymer" stands for the truncated to an isobutene polyisobutene. The vinylidene groups show the highest reactivity, whereas a double bond further inside the macromolecules shows no or definitely lower reactivity in functionalization reactions. Highly reactive polyisobutenes are used inter alia as intermediates for the preparation of additives for lubricants and fuels, as described for example in DE-A 27 02 604.

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

DE-A 27 02 604 obtainable by cationic polymerization of isobutene in the liquid phase in the presence of boron trifluoride as a catalyst. The disadvantage here is that the resulting polyisobutenes have a relatively high polydispersity. The polydispersity PDI is a measure of the molecular weight distribution of the polymer chains obtained and corresponds to the quotient of weight-average molecular weight Mw and number-average molecular weight M _n (PDI = M _w / M _n ). Polyisobutenes having a similarly high proportion of terminal double bonds but having a narrower molecular weight distribution are obtainable, for example, by the process of EP-A 145 235, US Pat. No. 5,408,018 and WO 99/64482, the polymerization being carried out in the presence of a deactivated catalyst, for example a Complex of boron trifluoride, alcohols and / or ethers, takes place. The disadvantage here is that at very low temperatures, often well below 0 ⁰ C, which causes a lot of energy, must be worked to actually get to highly reactive polyisobutenes.

EP-A 1 344 785 describes a process for the preparation of highly reactive polyisobutenes using a solvent-stabilized transition metal complex with weakly coordinating anions as the polymerization catalyst. Suitable metals are those of the 3rd to 12th group of the periodic table; Manganese complexes are used in the examples. Although it is possible with re- action above temperature range of 0 ⁰ C to be polymerized in this process, however, is disadvantageous in that the polymerization times are unacceptably long, so that an economic utilization of this process unattractive is.

EP-A 1 598 380 describes fluoro-elemental-donor complexes, for example HBF ₄ • O (CH 3) 2, as polymerization catalysts for isobutene. When

Feedstock is called isobutene-containing technical C4 hydrocarbon streams such as raffinate 1.

WO 95/26814 discloses supported polymerization catalysts for isobutene polymerization which are formed by reacting organometallic compounds of, inter alia, aluminum or boron, for example triisobutylaluminum, with strong mineral acids or organic acids such as trifluoromethanesulfonic acid and are covalently bonded to the support material. With these polymerization catalysts to achieve a content of vinylidene double bonds in the polymer of up to 40 mol%. As feedstock, isobutene-containing technical C4 hydrocarbon streams are mentioned.

It is known that catalyst systems, as used for example in EP-A 1 598 380, lead to a certain residual fluorine content in the product in the form of organic fluorine compounds. In order to reduce or avoid such by-products, fluorine atoms bound directly to a metal center should be dispensed with in such a catalyst complex.

The object of the present invention was therefore to provide a process for the preparation of low, medium and high molecular weight highly reactive polyisobutene homo- or copolymers, in particular for the preparation of polyisobutene polymers having a number average molecular weight M _n of 500 to 1,000,000 and with a overall at terminal vinylidene double bonds of at least 80 mol%, which on the one hand allows polymerization of isobutene or isobutene-containing monomer sources at not too low temperature, but at the same time allows significantly shorter polymerization times. The catalyst used in this case should not contain easily separable fluorine functions.

The object has been achieved by a process for the preparation of highly reactive isobutene homopolymers or copolymers having a number average molecular weight M _n of 500 to 1,000,000 by polymerization of isobutene from a technical C 4 hydrocarbon stream having an isobutene content of 1 to 90% by weight. % in the liquid phase in the presence of a dissolved, dispersed or supported catalyst complex, characterized in that the catalyst complex is a proton acid compound of the general formula I

[H ⁺ ] _k Y ^k -. | _ _x (I)

in the

the variable Y ^{k "is} a weakly coordinating k-valent anion containing at least one carbon-containing moiety,

L denotes neutral solvent molecules and

x denotes a number> 0,

starts.

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

In a preferred embodiment, as carbon-containing groups in the anion Y ^k - one or more aliphatic, heterocyclic or aromatic hydrocarbon radicals each having 1 to 30 carbon atoms, which may contain fluorine atoms, and / or d- to C3o hydrocarbon radicals containing silyl groups.

Suitable aliphatic hydrocarbon radicals in the anion Y ^k - for example, linear or branched alkyl radicals having 1 to 8 carbon atoms into consideration. Examples of these are methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1 Ethylpropyl, n-hexyl, 1, 1-dimethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2, 2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1, 1, 2-trimethylpropyl, 1, 2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1 Ethyl 2-methyl-propyl, n-heptyl, n-octyl and 2-ethylhexyl. However, longer-chain alkyl radicals such as n-decyl, n-dodecyl, n-tridecyl, isotridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl are also usable in principle.

Pyridines, imidazoles, imidazolines, piperidines or morpholines are suitable, for example, as heterocyclic aromatic or partially saturated or fully saturated radicals which may be present in the anion Y ^k .

Examples of suitable aromatic hydrocarbon radicals in the anion Y.sub.k ^" are C.sub.1- to C.sub.18-aryl radicals, for example unsubstituted or substituted phenyl or toidene, optionally substituted naphthyl, optionally substituted biphenyl, optionally substituted anthracenyl or optionally substituted phenothrenyl Nitro, cyano, hydroxy, chloro and trichloromethyl, for example, are mentioned here. The stated number of carbon atoms for these aryl radicals include all the carbon atoms contained in these radicals, including the carbon atoms of substituents on the aryl radicals.

All of said aliphatic, heterocyclic or aromatic hydrocarbon radicals may be substituted by one or more fluorine atoms; as examples, reference may be made to the specific fluorine compounds listed in the preferred embodiments below.

As examples of silyl groups containing C 1 -C 30 -hydrocarbon groups, reference may be made to the specific silyl compounds listed in the preferred embodiments mentioned below.

In a particularly preferred embodiment, a boron-containing compound of the general formula II is used as the proton-acidic catalyst complex for the process according to the invention

[H ⁺ ] _{m +} i [R ¹ R ² R ³ B - (- A ^{m +} -BR ⁵ R ⁶ -) n R ⁴ ] ^{(m + 1)} - • L _x (II)

in the

the variables R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ independently of one another for aliphatic, heterocyclic or aromatic fluorine-containing hydrocarbon radicals each having 1 to 18 carbon atoms or d- to Ciβ hydrocarbon radicals containing silyl groups stand,

A denotes a nitrogen-containing bridge member which forms covalent bonds to the boron atoms via its nitrogen atoms,

L denotes neutral solvent molecules,

n is the number 0 or 1,

m stands for the number 0 or 1 and

x denotes a number> 0.

In the case of the absence of a bridge element A (n = 0), its charge number m is also 0.

The variables R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ^{6 of} the weakly coordinating anion [R ¹ R ² R ³ B - (- A ^{m +} -BR ⁵ R ⁶ -) _n -R ⁴ ] < ^{m In} the case of fluorohydrocarbon radicals, independently of one another, ^+1- > are aliphatic, heterocyclic or aromatic fluorine-containing hydrocarbon radicals having in each case 1 to 18, preferably 3 to 18, carbon atoms. In the case of aliphatic radicals, those having 1 to 10, in particular 2 to 6, carbon atoms are preferred. These aliphatic radicals may be linear, branched or cyclic. They each contain 1 to 12, in particular 3 to 9 fluorine atoms. Typical examples of such aliphatic radicals are difluoromethyl, trifluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1, 2,2,2-tetrafluoroethyl, pentafluoroethyl, 1,1,1-trifluoro-2-propyl , 1, 1, 1-trifluoro-2-butyl, 1, 1, 1-trifluoro-tert-butyl and tris (trifluoromethyl) - methyl.

In a preferred embodiment, the variables R ^1, R ^2, R ^3, R ^4, R ⁵ and R ⁶ independently of one another, Ce to C-aryl radicals, in particular Ce to C-aryl radicals, having in each case 3 to 12 Fluorine atoms, in particular 3 to 6 fluorine atoms; Pentafluorophenyl radicals, 3- or 4-trifluoromethylphenyl radicals and 3,5-bis (trifluoromethyl) phenyl radicals are very particularly preferred here.

Ce- to cis-aryl or Ce- to Cg-aryl is in the context of the present invention optionally further substituted polyfluorophenyl or polyfluorotolyl, optionally further substituted Polyfluornaphthyl, optionally further substituted polyfluorobiphenyl, optionally further substituted polyfluoroanthracenyl or optionally further substituted polyfluorophenanthrenyl. Examples of further substituents which may be present mono- or polysubstituted are, for example, nitro, cyano, hydroxy, chloro and trichloromethyl. The stated number of carbon atoms for these aryl radicals include all carbon atoms contained in these radicals, including the carbon atoms of substituents on the aryl radicals.

In the case of d- to C hydrocarbon radicals containing silyl groups the variables R ^1, R ^2, R ^3, R ^4, R ⁵ and R ⁶ independently of one another, preferably silyl group for trialkyl, where the three alkyl groups may be different or preferably identical. Suitable alkyl radicals are, in particular, linear or branched alkyl radicals having 1 to 8 carbon atoms. Examples of these are methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2.2- Dimethylpropyl, 1-ethylpropyl, n-hexyl, 1, 1-dimethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1, 1, 2-trimethylpropyl, 1, 2,2- Trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, n-heptyl, n-octyl and 2-ethylhexyl. However, longer-chain alkyl radicals such as n-decyl, n-dodecyl, n-tridecyl, isotridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl are also usable in principle. Especially suitable are trimethylsilyl and triethylsilyl radicals.

The variables R ^1, R ^2, R ^3, R ^4, R ⁵ and R ⁶ can contain a minor extent also func- tional groups or heteroatoms, provided this does not impair the dominating fluorocarbon character or the dominating silylhydrocarbyl character of the radicals , Such functional groups or heteroatoms are, for example, further halogen atoms, such as chlorine or bromine, nitro groups, cyano groups, hydroxyl groups and C 1 to C 4 alkoxy groups, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy and tert-butoxy. However, heteroatoms may also be part of the underlying hydrocarbon chains or rings, for example oxygen in the form of ether functions, eg. In polyoxyalkylene chains, or nitrogen and / or oxygen as a constituent of heterocyclic aromatic or partially or fully saturated ring systems, e.g. As in pyridines, imidazoles, imidazolines, piperidines or morpholines. In any case, however, the variables R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are covalently bonded via a carbon atom to the boron atoms.

The variables R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may all be different. However, several or all of these variables can be the same. In particularly preferred embodiments (in the case of n = 1) all six variables R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ or (in the case of n = 0) all four variables R ¹ , R ² , R ³ and R ^{4 are the} same and are each pentafluorophenyl, 3,5-bis (trifluoromethyl) phenyl, trimethylsilyl or Triethylsi- IyI.

Typical unbridged proton acid compounds II (n = 0) contain as a singly negatively charged anion tetrakis (pentafluorophenyl) borane, tetrakis [3- (trifluoromethyl) - phenyl] borane, tetrakis [4- (trifluoromethyl) phenyl] borane or tetrakis [3,5-bis (trifluoromethyl) phenyl] borane.

As the nitrogen-containing bridge member A, which forms covalent bonds to the boron atoms via its nitrogen atoms, in the simplest case a unit of the formula -NH- which is formally derived from ammonia can serve. Further examples of A are aliphatic and aromatic diamines such as 1,2-diaminomethane, 1,2-ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, 1,2,4,1,3 or 1,4 Phenylenediamine-derived units.

In a preferred embodiment, the bridging member A denotes an optionally simply positively charged five- or six-membered heterocyclic unit having at least 2 nitrogen atoms, which may be saturated or unsaturated, for example pyrazolium, imidazolidine, imidazolinium, imidazolium, 1,2,3-triazolidine, 1 , 2,3-triazolium, 1, 2,4-triazolium, tetrazolium or pyrazane. Particularly preferred is imidazolium for A.

A typical bridged protic acid compound II (n = 1) as a singly negatively charged anion, the structure [(F ₅ C 6) 3B-imidazolium-B (C6F ₅₎ 3] ^", wherein the imidazolidinone to bridge over each of its two nitrogen atoms each forms a covalent bond to one of the two boron atoms.

In a further particularly preferred embodiment, a compound of the general formula III is used as the proton acid catalyst complex for the process according to the invention

H ⁺ [MXa (OR ⁷ ) _b ] - • L _x (IM)

in the

M represents a metal atom from the group boron, aluminum, gallium, indium and thallium,

the variables R ⁷ independently of one another represent aliphatic, heterocyclic or aromatic hydrocarbon radicals each having 1 to 18 carbon atoms, which may contain fluorine atoms, or silyl groups containing C 1 to C 6 hydrocarbon radicals,

the variable X represents a halogen atom,

L denotes neutral solvent molecules, a is an integer from 0 to 3 and b is an integer from 1 to 4, where the sum of a + b must be 4, and

x denotes a number> 0.

If the variables R ^{7 are} aliphatic, heterocyclic or aromatic hydrocarbon radicals having in each case 1 to 18 carbon atoms, they preferably contain one or more fluorine atoms.

The variables R ^{7 of} the weakly coordinating anion [MX _a (OR ⁷ ) b] ^" in the case of fluorohydrocarbon radicals independently of one another represent aliphatic, heterocyclic or aromatic fluorine-containing hydrocarbon radicals having in each case 1 to 18, preferably 1 to 13, carbon atoms those aliphatic radicals may be linear, branched or cyclic and contain in each case 1 to 12, in particular 3 to 9 fluorine atoms typical examples of such aliphatic radicals are difluoromethyl, trifluoromethyl, 2,2-Difluoroethyl, 2,2,2-trifluoroethyl, 1, 2,2,2-tetrafluoroethyl, pentafluoroethyl, 1,1,1-trifluoro-2-propyl, 1,1,1-trifluoro-2-butyl , 1, 1, 1-trifluoro-tert-butyl and especially tris (trifluoromethyl) methyl.

In the case of aromatic radicals which the variables R ⁷ independently of one another are preferably Ce to C-aryl radicals, in particular Ce to C-aryl radicals, having in each case 3 to 12 fluorine atoms, especially 3 to 6 fluorine atoms; Pen- tafluorophenyl radicals, 3- or 4- (trifluoromethyl) phenyl radicals and 3,5-bis (trifluoromethyl) phenyl radicals are preferred here.

In the context of the present invention, such Ce to Cis-aryl or Ce to Cg-aryl is optionally further substituted polyfluorophenyl or polyfluorotolyl, optionally further substituted polyfluoronaphthyl, optionally further substituted polyfluorobiphenyl, optionally further substituted polyfluoranthracenyl or optionally further substituted polyfluorophenanthrenyl , Examples of further substituents which may be present one or more times are, for example, nitro, cyano, hydroxy, chlorine and trichloromethyl. The stated number of carbon atoms for these aryl radicals include all carbon atoms contained in these radicals, including the carbon atoms of substituents on the aryl radicals.

In the case of silyl groups containing d- to cis-hydrocarbon radicals, the variables R ⁷ independently of one another preferably represent trialkylsilyl, it being possible for the three alkyl radicals to be different or preferably identical. Suitable alkyl radicals are, in particular, linear or branched alkyl radicals having 1 to 8 carbon atoms. Examples of these are methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1, 1-dimethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1, 1, 2-trimethylpropyl, 1, 2, 2-trimethylpropyl, 1-ethyl-1-methylpropyl, i-ethyl-2-methylpropyl, n-heptyl, n-octyl and 2-ethylhexyl. However, even longer-chain alkyl radicals such as n-decyl, n-dodecyl, n-tridecyl, isotridecyl, n-tetra-decyl, n-hexadecyl or n-octadecyl are in principle usable. Particularly suitable are trimethylsilyl and Triethylsilylreste.

The variables R ⁷ may to a lesser extent contain additional functional groups or heteroatoms, as far as this does not affect the dominant fluorohydrocarbon character or the dominant silylhydrocarbon character of the radicals. Such functional groups or heteroatoms are, for example, further halogen atoms such as chlorine or bromine, nitro groups, cyano groups, hydroxy groups and C 1 to C 4 alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy and tert-butoxy. However, heteroatoms may also be part of the underlying hydrocarbon chains or rings, for example oxygen in the form of ether functions, eg. In polyoxyalkylene chains, or nitrogen and / or oxygen as a constituent of heterocyclic aromatic or partially or fully saturated ring systems, e.g. As in pyridines, imidazoles, imidazolines, piperidines or morpholines.

In a preferred embodiment, the variables R ⁷ independently of one another are C 1 - to C 18 -alkyl radicals having 1 to 12 fluorine atoms, in particular tris (trifluoromethyl) methyl radicals, or C 6 - to cis-aryl radicals having 3 to 6 fluorine atoms, in particular pentafluorophenyl radicals , 3- or 4- (trifluoromethyl) phenyl radicals or 3,5-bis (trifluoromethyl) phenyl radicals.

If there are several variables R ⁷ in the connection I, these can all be different. However, several or all of these variables can be the same. In a particularly preferred embodiment, all variables R ^{7 are} identical and are each tris (trifluoromethyl) methyl radicals, pentafluorophenyl radicals, 3- or 4- (trifluoromethyl) phenyl radicals or 3,5-bis (trifluoromethyl) phenyl radicals.

The variables R ⁷ are part of corresponding alkoxylate units -OR ⁷ , which are located together with possible halogen atoms X as substituents on the metal atom M and are usually linked to this by covalent bonding. The number b of these alkoxylate units -OR ⁷ is preferably 2 to 4, in particular 4, and the number a of the possible halogen atoms X is preferably 0 to 2, in particular 0, wherein the sum of a + b must be 4. The metal atoms M are the metals of the group IMA (corresponding to group 13 in the new designation) of the Periodic Table of the Elements. Of these, boron and aluminum, in particular aluminum, are preferred.

The halogen atoms X are the non-metals of group VIIA (corresponding to group 17 in the new designation) of the Periodic Table of the Elements, ie fluorine, chlorine, bromine, iodine and astatine. Of these, fluorine and especially chlorine are preferred.

In the compounds of the general formula I, II and III, it is also possible for neutral solvation molecules L to be present. These solvent molecules L can also be referred to as ligands or donors. Up to x = 12 of such solvent molecules L, in particular x = 2 to 8, can usually be present per formula unit I or II or IM. They are preferably selected from open-chain and cyclic ethers, in particular from di-C 1 to C 3 -alkyl ethers, ketones, thiols, organic sulfides, sulfones, sulfoxides, sulfonic esters, organic sulfates, phosphines, phosphanoxides, organic phosphites , organic phosphates, phosphoric acid amides, carboxylic acid esters, carboxylic acid amides and alkylnitriles and aryl nitriles.

The solvent molecules L represent solvent molecules that can form coordinative bonds with the central metal atoms. These are molecules that are commonly used as solvents, but at the same time via at least one dative grouping, e.g. have a lone pair of electrons that can form a coordinative bond to a central metal. Preferred solvation molecules L are those which on the one hand bind coordinatively to the central metal but on the other hand do not represent strong Lewis bases, so that they can easily be displaced from the coordination sphere of the central metal in the course of the polymerization.

The solvent molecules L have, inter alia, the function of stabilizing the protons possibly contained in the compounds I, for example in the case of ethers as diethyl etherates [H (OEt ₂ ) ₂ ] ⁺ .

Examples of open-chain and cyclic ethers for solvent molecules L are diethyl ether, dipropyl ether, diisopropyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, tetrahydrofuran and dioxane. In the case of open-chain ethers, preference is given to di-Cr to C3-alkyl ethers, in particular symmetrical di-C 1 to C 3 -alkyl ethers.

Suitable ketones for solvent molecules L are, for example, acetone, ethyl methyl ketone, acetoacetone or acetophenone. Suitable thiols, organic sulfides (thioethers), sulfones, sulfoxides, sulfonic acid esters and organic sulfates for sulfur-containing solvent molecules L are, for example, long-chain mercaptans such as dodecyl mercaptan, dialkyl sulfides, dialkyl disulfides, dimethyl sulfone, dimethyl sulfoxide, methyl sulfonic acid methyl ester or dialkyl sulfates such as dimethyl sulfate.

Suitable phosphines, phosphine oxides, organic phosphites, organic phosphates and phosphoric acid amides for phosphorus-containing solvent molecules L are, for example, triphenylphosphine, triphenylphosphine oxide, trialkyl, triaryl or mixed aryl / alkyl phosphites, trialkyl, triaryl or mixed aryl / alkyl phosphates or hexamethylphosphoric triamide.

Suitable carboxylic acid esters for solvent molecules L are, for example, methyl or ethyl acetate, methyl or ethyl propionate, methyl or ethyl butyrate, methyl or ethyl caproate or methyl or ethyl benzoate.

Suitable carboxamides for solvent molecules L are, for example formamide, dimethylformamide, acetamide, dimethylacetamide, propionamide, benzamide or N ₁ N-dimethylbenzamide.

Suitable alkylnitriles and aryl nitriles for solvent molecules L are, in particular, C 1 - to C 5 -alkylnitriles, especially C 1 - to C 4 -alkylnitriles, for example acetonitrile, propionitrile, butyronitrile or pentylnitrile, and also benzonitrile.

Preferably, in the protic acid compounds of the general formula I, all L are the same solvent molecule.

The compounds of the general formula I, II and III can be generated in situ and used in this form as catalysts for the isobutene polymerization according to the invention. However, they can also be prepared from their preparatively readily available salts as pure substances and used according to the invention. They are usually stable in storage over a longer period in this form.

Thus, the protic acid compounds of the general formula II can be prepared from their synthetically readily accessible and therefore partially commercially available salts, for example the silver salt, as pure substances and used according to the invention. For the preparation of the protic acid compounds I, for example, the corresponding silver salt in a protic, moderately polar solvent is treated with hydrogen halide and thereby eliminated, sparingly soluble silver halide separated. Thus, for example, a four-fold excess of an alcohol of the formula R ⁷ OH with lithium aluminum hydride in an aprotic solvent can be converted into the corresponding lithium salt to prepare the compounds III. The lithium salt obtained can be treated with hydrogen halide in a subsequent step to give the compound IM with the elimination of lithium halide.

The polymerization process according to the invention is suitable for the preparation of low, medium and high molecular weight highly reactive isobutene homo- or copolymers. Preferred comonomers here are styrene, styrene derivatives such as in particular α-methylstyrene and 4-methylstyrene, styrene and styrene derivatives-containing monomer mixtures, alkadienes such as butadiene and isoprene and mixtures thereof. In particular, isobutene, styrene or mixtures thereof are used as monomers in the polymerization process according to the invention.

For the use of isobutene or an isobutene-containing monomer mixture as the monomer to be polymerized, a technical C4 hydrocarbon stream having an isobutene content of from 1 to 80% by weight is used here as the isobutene source. Particularly suitable for this purpose are C4 raffinates (raffinate 1, raffinate 1 P and raffinate 2), C4 cuts from isobutane dehydrogenation, C4 cuts from steam crackers (after butadiene extraction or partially hydrogenated) and from fluid catalysed cracking (FCC) crackers. as far as they are largely exempt from 1, 3-butadiene contained therein. Suitable C4 hydrocarbon streams generally contain less than 500 ppm, preferably less than 200 ppm, butadiene. The presence of 1-butene and of cis- and trans-2-butene is largely uncritical. Typically, the isobutene concentration in the C4 hydrocarbon streams is in the range of 30 to 70 weight percent, more preferably 40 to 60 weight percent, with raffinate 2 and FCC streams having lower isobutene concentrations, but is nevertheless suitable for the process of this invention are. The isobutene-containing monomer mixture may contain small amounts of contaminants, such as water, carboxylic acids or mineral acids, without any loss of yield or selectivity being sacrificed. It is expedient to avoid an accumulation of these impurities by removing such pollutants from the isobutene-containing monomer mixture, for example by adsorption on solid adsorbents such as activated carbon, molecular sieves or ion exchangers.

Typically, in a raffinate 1 stream, the content of isobutene is 30 to

50% by weight, 10 to 50% by weight of 1-butene, 10 to 40% by weight of cis- and trans-2-butene and 2 to 35% by weight of butanes.

Typically, in a raffinate 1 P-stream, the content of isobutene is 35 to 60% by weight, 1 to 15% by weight of 1-butene, 15 to 50% by weight of cis- and trans-2-butene of butanes 2 to 40 wt .-%. Typically, in a raffinate 2 stream, the content of isobutene is 0.5 to

10% by weight, 15 to 60% by weight of 1-butene, 5 to 50% by weight of cis- and trans-2-butene and 5 to 45% by weight of butanes.

Typically, in a C4 cut from the isobutane dehydrogenation, the isobutene content is from 20 to 70% by weight, at 1-butene <1% by weight, at cis- and trans-butene <1% by weight and at Butanes 30 to 80 wt .-%.

Typically, in a C4 cut from steam crackers after the butadiene next fraction, the content of isobutene is 30 to 50% by weight, for 1-butene 10 to 30% by weight, for cis- and trans-2-butene 10 to 30 Wt .-% and butanes 5 to 20 wt .-%.

Typically, in a partially hydrogenated C4 cut from the steam cracker (HC4 stream), the content of isobutene is 10 to 45% by weight, on 1-butene 15 to 60% by weight, of cis- and trans-2-butene 5 to 50 wt .-% and butanes 5 to 45 wt .-%.

Typically, in a FCC stream, the content of isobes is 10 to 30% by weight, 1 to 5% to 25% by weight, cis and trans 2-butene 10 to 40% by weight, and butanes From 30 to 70% by weight.

In a preferred embodiment, the technical C 4 hydrocarbon stream used in the process according to the invention contains from 30 to 70% by weight of isobutene, from 1 to 50% by weight of 1-butene, from 1 to 50% by weight of cis- and trans-2-butene, 2 to 40 wt .-% butane and up to 1000 ppm by weight of butadiene.

In a particularly preferred embodiment, the process according to the invention for the preparation of highly reactive isobutene homopolymers or copolymers is carried out by polymerization of isobutene from raffinate 1 or raffinate 1 P as a technical C 4 hydrocarbon stream. Raffinate 1 and raffinate 1 P usually have the abovementioned compositions and content of butadiene of not more than 1000 ppm by weight.

Monomer mixtures of isobutene or of the isobutene-containing hydrocarbon mixture with olefinically unsaturated monomers which are copolymerizable with isobutene can be reacted by the process according to the invention. If monomer mixtures of isobutene are to be copolymerized with suitable comonomers, the monomer mixture preferably contains at least 5% by weight, particularly preferably at least 10% by weight and in particular at least 20% by weight of isobutene, and preferably at most 95% by weight preferably at most 90% by weight and in particular at most 80% by weight of 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 also 4-tert-butylstyrene, alkadienes such as butadiene and isoprene and isoolefins having from 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. 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, as well as vinyl ethers such as tert-butyl vinyl ether.

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

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

The process according to the invention is suitable both for carrying out at low temperatures, for example at -78 to 0 ° C., and at higher temperatures, ie at at least 0 ° C., for example at 0 to 100 ° C. The polymerization is mainly for economic reasons, preferably at least 0 ° C eg at 0 to 100 ⁰ C, particularly preferably at 20 to 60 ⁰ C carried out to the energy and material consumption, which is necessary for cooling, as low as possible to hold. However, it can just as well at lower temperatures, for example at -78 to <0 ° C, preferably at -40 to -10 ° C, performed. If the polymerization takes place at or above the boiling point of the monomer or monomer mixture to be polymerized, it is preferably carried out in pressure vessels, for example in autoclaves or in pressure reactors.

Preferably, the polymerization is carried out in the presence of an inert diluent. The inert diluent used should be suitable for reducing the increase in the viscosity of the reaction solution which usually occurs during the polymerization reaction to such an extent that the removal of the heat of reaction formed can be ensured. Suitable diluents are those solvents or solvent mixtures which are inert to the reagents used. Suitable diluents are, for example, aliphatic hydrocarbons such as butane, pentane, hexane, heptane, octane and isooctane, cycloaliphatic hydrocarbons such as cyclopentane and cyclohexane, aromatic hydrocarbons such as benzene, toluene and the xylene, and halogenated hydrocarbons such as methyl chloride, dichloromethane and trichloromethane, and mixtures of the aforementioned diluents. Preference is given to using at least one halogenated hydrocarbon, optionally in admixture with at least one of the abovementioned aliphatic or aromatic hydrocarbons. In particular, dichloromethane is used. Preferably, the diluents are freed before use of impurities such as water, carboxylic acids or mineral acids, for example by adsorption on solid adsorbents such as activated carbon, molecular sieves or ion exchangers.

The polymerization is preferably carried out under largely aprotic conditions, in particular under anhydrous reaction conditions. Aprotic or anhydrous reaction conditions are understood to mean that the water content (or the content of protic impurities) in the reaction mixture is less than 50 ppm and in particular less than 5 ppm. As a rule, therefore, the feedstocks will be dried before use by physical and / or chemical means. In particular, it has proven useful to use the aliphatic or alicyclic hydrocarbons used as a solvent after conventional pre-cleaning and predrying with an organometallic compound, such as an organolithium, organomagnesium or organoaluminum compound, in an amount sufficient to remove the traces of water from the Solvent to remove. The solvent thus treated is then preferably condensed directly into the reaction vessel. In a similar manner, it is also possible to proceed with the monomers to be polymerized, in particular with isobutene or with the isobutene-containing mixtures. Drying with other customary desiccants, such as molecular sieves or predried oxides, such as aluminum oxide, silicon dioxide, calcium oxide or barium oxide, is also suitable. The halogenated solvents, which are not suitable for drying with metals such as sodium or potassium or with metal alkyls, are treated with suitable drying agents, for example with calcium chloride. cium chloride, phosphorus pentoxide or molecular sieve, freed from water (traces). In an analogous manner, it is also possible to dry those starting materials for which a treatment with metal alkyls likewise does not come into consideration, for example vinylaromatic compounds.

The polymerization of the isobutene or isobutene-containing feedstock is usually spontaneous upon contacting the catalyst complex (i.e., compound I, or preferably II, or preferably IM) with the monomer at the desired reaction temperature. In this case, it is possible to proceed by initially introducing the monomer in the solvent, bringing it to the reaction temperature and then adding the catalyst complex, for example as a loose bed. It is also possible to provide the catalyst complex (for example as a loose bed or as a fixed bed) optionally in a solvent and then to add the monomer. The beginning of polymerization is then the time at which all the reactants are contained in the reaction vessel. The catalyst complex may partially or completely dissolve in the reaction medium or be present as a dispersion. Alternatively, the catalyst complex can also be used in supported form.

If the catalyst complex is to be used in supported form, it is brought into contact with a suitable carrier material and thus converted into a heterogenized form. The contacting takes place, for example, by impregnation, impregnation, spraying, brushing or related techniques. The contacting also includes physisorption techniques. The contacting can be carried out at normal temperature and atmospheric pressure or at higher temperatures and / or pressures.

By contacting, the catalyst complex enters into a physical and / or chemical interaction with the carrier material. Such interaction mechanisms are firstly the exchange of one or more neutral solvation molecules L and / or one or more charged structural units of the catalyst complex with neutral or correspondingly charged groups, molecules or ions, which are incorporated in or attached to the support material. Furthermore, the weakly coordinating anion Y ^k - can be exchanged for a correspondingly negatively charged group or an anion from the support material or the positively charged proton from the catalyst complex for a correspondingly positively charged cation from the support material (for example an alkali metal ion). In addition to or instead of these genuine ion exchange processes, weaker electrostatic interaction may also occur. Finally, the catalyst complex can also be fixed to the support material by means of covalent bonds, for example by reaction with hydroxyl groups or silanol groups which are located inside the support material or preferably on the surface. Essential for the suitability as a carrier material in the context of the present invention are also its specific surface area and its porosity properties. In this case, mesoporous carrier materials have proven to be particularly advantageous. Mesoporous carrier materials generally have an internal surface area of from 100 to 3000 m ² / g, in particular from 200 to 2500 m ² / g, and pore diameters of from 0.5 to 50 nm, in particular from 1 to 20 nm.

Suitable carrier materials are in principle all solid inert substances with a high surface area, which can usually serve as a support or scaffold for active substance, in particular for catalysts. Typical inorganic classes of substances for such support materials are activated carbon, alumina, silica gel, kieselguhr, talc, kaolin, clays and silicates. Typical organic classes of such support materials are crosslinked polymer matrices such as crosslinked polystyrenes and crosslinked polymethacrylates, phenol-formaldehyde resins or polyalkylamine resins.

Preferably, the carrier material is selected from molecular sieves and ion exchangers.

Both cation, anion and amphoteric ion exchangers can be used as ion exchangers. Preferred organic or inorganic types of matrices for such ion exchangers are polystyrenes (crosslinked divinylbenzene-styrene copolymers) wetted with divinylbenzene, polymethacrylates crosslinked with divinylbenzene, phenol-formaldehyde resins, polyalkylamine resins, hydrophilized cellulose, crosslinked dextran, crosslinked agarose , Zeolites, montmorillonites, attapulgites, bentonites, aluminum silicates and acid salts of polyvalent metal ions such as zirconium phosphate, titanium tungstate or nickel hexacyanoferrate (II). Acid ion exchangers usually carry carboxylic acid, phosphonic acid, sulfonic acid, carboxymethyl or sulfoethyl groups. Basic ion exchangers usually contain primary, secondary or tertiary amino groups, quaternary ammonium groups, aminoethyl or diethylaminoethyl groups.

Molecular sieves have a strong adsorption capacity for gases, vapors and solutes and are generally also applicable to ion exchange processes. Molecular sieves typically have uniform pore diameters, on the order of the diameter of molecules, and large internal surfaces, typically 600 to 700 m ² / g. In particular, silicates, aluminum silicates, zeolites, silicoaluminophosphates and / or carbon molecular sieves can be used as molecular sieves in the context of the present invention.

Ion exchangers and molecular sieves with an inner surface area of 100 to 3000 m ² / g, in particular 200 to 2500 m ² / g, and pore diameters of 0.5 to 50 nm, in particular from 1 to 20 nm, are particularly advantageous. Preferably, the support material is selected from molecular sieves of the types H-AIMCM-41, H-AIMCM-48, NaAIMCM-41 and NaAIMCM-48. These molecular sieve types are silicates or aluminum silicates, on whose inner surface silanol groups adhere, which may be of importance for the interaction with the catalyst complex. However, the interaction is believed to be mainly due to the partial exchange of protons and / or sodium ions.

Both when used as a solution, as a dispersion or in supported form, the catalyst complex is used in such an amount that, based on the amounts of monomers used, in a molar ratio of preferably 1:10 to 1: 1000 .0000, especially from 1: 10,000 to 1: 500,000, and in particular from 1: 5000 to 1: 100,000, is present in the polymerization medium.

The concentration ("loading") of the catalyst complex in the carrier material is in the range of preferably 0.005 to 20 wt .-%, especially 0.01 to 10 wt .-% and in particular 0.1 to 5 wt .-%.

The catalyst complex which acts as a polymerization catalyst is present in the polymerization medium, for example as a loose bed, as a fluidized bed, as a fluidized bed or as a fixed bed. Suitable reactor types for the polymerization process according to the invention are accordingly usually stirred tank reactors, loop reactors, tubular reactors, fluidized bed reactors, fluidized bed reactors, stirred tank reactors with and without solvent, liquid bed reactors, continuous fixed bed reactors and dis-continuous fixed bed reactors (batch mode).

For the preparation of copolymers, it is possible to proceed by initially introducing the monomers, if appropriate in the solvent, and then adding the catalyst complex, for example as a loose bed. The adjustment of the reaction temperature can be carried out before or after the addition of the catalyst complex. It is also possible to initially introduce only one of the monomers, if appropriate in the solvent, then to add the catalyst complex and to react it only after a certain time, for example when at least 60%, at least 80% or at least 90% of the monomer have reacted. the one or more monomers added. Alternatively, the catalyst complex, for example, as a loose bed, optionally in solvent, submit, then add the monomers simultaneously or sequentially and then set the desired reaction temperature. The start of polymerization is then that time at which the catalyst complex and at least one of the monomers are contained in the reaction vessel.

In addition to the discontinuous procedure described here, the polymerization can also be designed as a continuous process. Here you lead the Starting materials, ie, the one or more monomers to be polymerized, optionally the solvent and optionally the catalyst complex (for example, as a loose bed) of the polymerization reaction to continuously and removes reaction product continuously, so that set in the reactor more or less stationary polymerization onsbedingungen. The monomer or monomers to be polymerized can be supplied as such, diluted with a solvent or as a monomer-containing hydrocarbon stream.

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

In a preferred embodiment of the invention, the process according to the invention is used for the preparation of highly reactive isobutene homopolymers or copolymers having a content of terminal vinylidene double bonds (α-double bonds) of at least 80 mol%, preferably of at least 85 mol% preferably at least 90 mole% and especially at least 95 mole%, eg of about 100 mol%. In particular, it is used for the preparation of highly reactive copolymers which are composed of monomers comprising isobutene and at least one vinylaromatic compound and a content of terminal vinylidene double bonds (α-double bonds) of at least 80 mol%, preferably of at least 85 mol% , more preferably at least 90 mole% and especially at least 95 mole%, eg of about 100 mol%.

In the copolymerization of isobutene or isobutene-containing hydrocarbon cuts with at least one vinylaromatic compound, block copolymers are preferably also formed with the simultaneous addition of the comonomers, the isobutene block generally being able to form the terminal, i. represents the last block formed.

Accordingly, in a preferred embodiment, the process of the invention is used to prepare highly reactive isobutene-styrene copolymers. Preferably, the highly reactive isobutene-styrene copolymers have a content of terminal vinylidene double bonds (α-double bonds) of at least 80 mol%, more preferably at least 85 mol%, more preferably at least 90 mol%, and most preferably at least 95 Mol%, for example of about 100 mol%, on. To prepare such copolymers, isobutene or an isobutene-containing hydrocarbon cut is copolymerized with at least one vinylaromatic compound, in particular styrene. Such a monomer mixture particularly preferably contains from 5 to 95% by weight, particularly preferably from 30 to 70% by weight, of styrene.

Preferably, the highly reactive isobutene homo- or copolymers prepared by the process according to the invention, especially the isobutene homopolymers, have a polydispersity (PDI = M _w / Mn) of 1.0 to 3.0, in particular of at most 2.0, preferably of 1, 0 to 2.0, more preferably from 1, 0 to 1, 8 and in particular from 1, 0 to 1, 5 on.

Preferably, the highly reactive isobutene homo- or copolymers prepared by the process of the invention have a number average molecular weight M _{n of} from 500 to 1,000,000, more preferably from 500 to 50,000, more preferably from 500 to 5,000 and especially from 800 to 2,500. Isobutene homopolymers especially still possess this More preferably, a number average molecular weight M _{n of} from 500 to 50,000 and in particular from 500 to 5,000, for example from about 1,000 or from about 2300.

By means of the process according to the invention, isobutene and isobutene-containing monomer mixtures which are polymerizable under cationic conditions and are based on technical C 4 hydrocarbon streams as feedstock are successfully polymerized with high conversions in short reaction times even at relatively high polymerization temperatures. Highly reactive isobutene homopolymers or copolymers having a high content of terminal vinylidene double bonds and having a rather narrow molecular weight distribution are obtained. The use of less volatile fluorine compounds in smaller amounts compared to boron trifluoride and boron trifluoride adducts as polymerization catalysts less pollutes wastewater and the environment. Furthermore, virtually no residual fluorine content occurs in the product in the form of organic fluorine compounds.

The present invention is further illustrated by the following examples.

example 1

Polymerization of Raffinate 1 with the Proton Acid Compound from the Simply Negatively Charged Tetrakis [3,5-bis (trifluoromethyl) phenyl] borane Anion (Catalyst A)

40 ml of a technical C4 hydrocarbon stream (raffinate 1) containing 40% by weight of isobutene were condensed into 120 ml of a mixture of equal volumes of n-hexane and dichloromethane. After cooling to -40 ° C, 200 mg of catalyst A was added under a protective atmosphere. Within 10 minutes the temperature rose to -30 ° C. After a total of 45 minutes of polymerization was quenched by the addition of 10 ml of methanol, the reaction product was taken up in more methanol and washed. After distilling off the solvents in vacuo, 6.4 g of polyisobutene having a number average molecular weight M _n of 1 160, a polydispersity of 2.0 and a content of terminal vinylidene double bonds of 91 mol%.

Example 2

40 ml of a technical C4 hydrocarbon stream (raffinate 1) containing

40 wt .-% of isobutene, were condensed in 120 ml of a mixture of equal volumes of n-hexane and dichloromethane. After cooling to -30 ° C, 200 mg of the catalyst A was added under a protective atmosphere. Within 10 minutes the temperature rose to -20 ° C. After a total of 30 minutes of polymerization was quenched by the addition of 10 ml of methanol, the reaction product was taken up in more methanol and washed. After distilling off the solvents in vacuo, polyisobutene having a number average molecular weight M _n of 1200, a polydispersity of 1, 9 and a content of terminal vinylidene double bonds of greater than 90 mol% was obtained at a conversion of 25% (based on isobutene).

Example 3

Continuous polymerization of a technical isobutene / 1-butene mixture with the protic acid compound from the singly negatively charged tetrakis [3,5-bis (trifluoromethyl) phenyl] borane anion (Catalyst A)

1.78 mol / l (based on isobutene) of a technical mixture of isobutene and 1-butene in a molar ratio of 87.5: 12.5 and 0.05 mmol / l (based on the catalyst) of a solution of the catalyst A. in dichloromethane were polymerized at -30 ° C in a conventional continuous laboratory polymerizer. The polymerization time was 30 minutes. It was quenched by the addition of 10 ml of methanol, the reaction product was taken up in additional methanol and washed. After distilling off the solvents in vacuo, polyisobutene having a number average molecular weight M _n of 1100, a polydispersity of 2.8 and a content of terminal vinylidene double bonds of 87 mol% was obtained at a conversion of 87% (based on isobutene). Example 4

1, 78 mol / l (based on isobutene) of a technical mixture of isobutene and

1-Butene in a molar ratio of 50:50 and 0.05 mmol / l (based on the catalyst) of a solution of the catalyst A in dichloromethane were polymerized in a conventional continuous laboratory Lehnungspolymerisationsapparator at -30 ° C. The polymerization time was 30 minutes. It was quenched by the addition of 10 ml of methanol, the reaction product was taken up in additional methanol and washed. After the solvents had been distilled off in vacuo, 90% (based on isobutene) of polyisobutene having a number average molecular weight M _n of 1000, a polydispersity of 2.7 and a content of terminal vinylidene double bonds of 90 mol -%.

Example 5

Polymerization of Raffinate 1 with the Diethyl Etherate Proton Acid Compound of the Formula [H (OEt ₂ ) 2] ⁺ {Al [OC (CF ₃ ) 3] 4} - (Catalyst B)

40 ml of a technical C4 hydrocarbon stream (raffinate 1) containing

40 wt .-% of isobutene, were condensed in 120 ml of a mixture of equal volumes of n-hexane and dichloromethane. After cooling to -40 ° C, 100 mg of catalyst A was added under a protective atmosphere. Within 10 minutes, the temperature rose to -30 ° C. After a total of 45 minutes of polymerization was quenched by the addition of 10 ml of methanol, the reaction product was taken up in more methanol and washed. After distilling off the solvents in vacuo, 1.7 g of polyisobutene having a number average molecular weight M _n of 2500, a polydispersity of 2.7 and a content of terminal vinylidene double bonds of 90 mol% were obtained.

Example 6

Polymerization of Raffinate 1 with the Protic Acid Compound of the Formula [H] ⁺ (Al [OC (CFa) ₃ M- (Catalyst C)]

40 ml of a technical C4 hydrocarbon stream (raffinate 1) containing 40% by weight of isobutene were condensed into 120 ml of a mixture of equal volumes of n-hexane and dichloromethane. After cooling to -30 ° C, 200 mg of Catalyst C was added under a protective atmosphere. Within 10 minutes the temperature rose to -20 ° C. After a total of 30 minutes of polymerization was quenched by the addition of 10 ml of methanol, the reaction product was taken up in more methanol and washed. After distilling off the solvents in vacuo, polyisobutene having a number average molecular weight M _n of 2500, a polydispersity of 2.7 and a content of terminal vinylidene double bonds of 90 mol% was obtained at a conversion of 20% (based on isobutene). ,

Claims

claims

1. A process for the preparation of highly reactive Isobutenhomo- or copolymers having a number average molecular weight M _n of 500 to 1,000,000 by polymerization of isobutene from a technical C4 hydrocarbon stream with an isobutene content of 1 to 90 wt. % in the liquid phase in the presence of a dissolved, dispersed or supported catalyst complex, characterized in that the catalyst complex is a proton acid compound of the general formula I

[H ⁺ ] _k Y ^k - • L _x (I)

in the

L denotes neutral solvent molecules and

x denotes a number> 0,

starts.

2. The method according to claim 1, characterized in that as carbon-containing groups in the anion Y ^k "one or more aliphatic, heterocyclic or aromatic hydrocarbon radicals each having 1 to 30 carbon atoms, which may contain fluorine atoms, and / or d- to C3o-hydrocarbon radicals Substance residues containing silyl groups occur.

3. The method according to claim 1 or 2, characterized in that the proton acid catalyst complex is a boron-containing compound of the general formula II

in the

the variables R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ independently of one another represent aliphatic, heterocyclic or aromatic fluorine-containing hydrocarbon radicals having in each case 1 to 18 carbon atoms or silyl groups containing C 1 to C ⁶ hydrocarbon radicals,

A is a nitrogen-containing bridge member which contains covalent bonds to the boron atoms. fertilizing via its nitrogen atoms,

L denotes neutral solvent molecules,

n is the number 0 or 1,

m stands for the number 0 or 1 and

x denotes a number> 0,

represents.

4. The method according to claim 1 or 2, characterized in that the proton acid catalyst complex is a compound of the general formula IM

H ⁺ [MXa (OR ⁷ ) _b ] - • L _x (IM)

in the

the variables R ⁷ independently of one another represent aliphatic, heterocyclic or aromatic hydrocarbon radicals having in each case 1 to 18 carbon atoms which may contain fluorine atoms, or silyl groups containing C 1 to C 18 hydrocarbon radicals,

the variable X represents a halogen atom,

L denotes neutral solvent molecules,

a is an integer from 0 to 3 and b is an integer from 1 to 4, where the sum of a + b must be 4, and

x denotes a number> 0,

represents.

5. The method according to claims 1 to 4, characterized in that the neutral solvent molecules are selected from open-chain and cyclic ethers, in particular from di-Ci- to C3-alkyl ethers, ketones, thiols, organic sulfides, sulfones, sulfoxides, sulfonic acid esters , organic sulphates, phosphates NEN, phosphine oxides, organic phosphites, organic phosphates, phosphoric acid amides, carboxylic acid esters, carboxylic acid amides and Alkylnitri len and Arylnitrilen.

6. Process according to claims 1 to 5 for the preparation of highly reactive Isobutenhomo- or copolymers having a content of terminal vinylidene double bonds of at least 80 mol%.

7. Process according to claims 1 to 6 for the preparation of highly reactive isobutene homo- or copolymers having a polydispersity of at most 2.0.

8. The method according to claims 1 to 7 for the preparation of highly reactive Isobutenhomo- or copolymers by polymerization of isobutene from a technical C4 hydrocarbon stream having an isobutene content of 30 to 70 wt .-%, to 1-butene of 1 to 50 Wt .-%, of cis- and trans-2-butene from 1 to

50 wt .-%, of butanes from 2 to 40 wt .-% and up to 1000 ppm by weight of butadiene.

9. The method of claim 9 for the preparation of highly reactive isobutene homo- or copolymers by polymerization of isobutene from raffinate 1 or raffinate 1 P as a technical C4 hydrocarbon stream.