Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F10/04—Monomers containing three or four carbon atoms
  • C08F10/08—Butenes
  • C08F10/10—Isobutene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F110/04—Monomers containing three or four carbon atoms
  • C08F110/08—Butenes
  • C08F110/10—Isobutene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F210/04—Monomers containing three or four carbon atoms
  • C08F210/08—Butenes
  • C08F210/10—Isobutene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/52—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from boron, aluminium, gallium, indium, thallium or rare earths

Definitions

• 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.
• highly reactive polyisobutene homopolymers or copolymers are understood as meaning polyisobutenes which contain a high content of terminal ethylenic double bonds.
• highly reactive polyisobutenes are to be understood as meaning polyisobutenes which have a proportion of vinylidene double bonds ( ⁇ -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.
• vinylidene groups are understood to mean those double bonds whose position in the polyisobutene macro-molecule is represented by the general formula
• 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.
• 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.
• 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.
• EP-A 1 598 380 describes fluoro-elemental-donor complexes, for example HBF 4 • O (CH 3) 2, as polymerization catalysts for isobutene.
• 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.
• 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.
• 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
• variable Y k is a weakly coordinating k-valent anion containing at least one carbon-containing moiety
• x denotes a number> 0,
• 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.
• 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-ethylbuty
• n-decyl n-dodecyl
• n-tridecyl isotridecyl
• n-tetradecyl n-hexadecyl or n-octadecyl
• 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 .
• 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.
• silyl groups containing C 1 -C 30 -hydrocarbon groups examples include C 1 -C 30 -hydrocarbon groups, reference may be made to the specific silyl compounds listed in the preferred embodiments mentioned below.
• a boron-containing compound of the general formula II is used as the proton-acidic catalyst complex for the process according to the invention
• 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 Ci ⁇ 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
• n is the number 0 or 1
• n stands for the number 0 or 1
• x denotes a number> 0.
• 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
• 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.
• 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.
• 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.
• 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.
• 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-eth
• 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.
• heteroatoms may also be part of the underlying hydrocarbon chains or rings, for example oxygen in the form of ether functions, eg.
• the nitrogen-containing bridge member A which forms covalent bonds to the boron atoms via its nitrogen atoms
• 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.
• 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.
• a compound of the general formula III is used as the proton acid catalyst complex for the process according to the invention
• M represents a metal atom from the group boron, aluminum, gallium, indium and thallium,
• 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,
• 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.
• 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.
• 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.
• 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.
• 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 ,
• 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.
• 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-
• 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.
• heteroatoms may also be part of the underlying hydrocarbon chains or rings, for example oxygen in the form of ether functions, eg.
• 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.
• 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.
• variables R 7 in the connection I 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.
• 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.
• neutral solvation molecules L can also be present.
• 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 ] + .
• 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.
• 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.
• 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.
• 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.
• the corresponding silver salt in a protic, moderately polar solvent is treated with hydrogen halide and thereby eliminated, sparingly soluble silver halide separated.
• 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 ⁇ -methylstyrene and 4-methylstyrene, styrene and styrene derivatives-containing monomer mixtures, alkadienes such as butadiene and isoprene and mixtures thereof.
• isobutene, styrene or mixtures thereof are used as monomers in the polymerization process according to the invention.
• 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.
• 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.
• the content of isobutene is 30 to
• 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 .-%.
• the content of isobutene is 0.5 to
• 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 .-%.
• 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 .-%.
• 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 .-%.
• 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.
• 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.
• 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.
• 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 ⁇ -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.
• vinylaromatics such as styrene and ⁇ -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.
• 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.
• 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
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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
• halogenated hydrocarbon optionally in admixture with at least one of the abovementioned aliphatic or aromatic hydrocarbons.
• dichloromethane is used.
• 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.
• the feedstocks will be dried before use by physical and / or chemical means.
• 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.
• 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.
• the catalyst complex i.e., compound I, or preferably II, or preferably IM
• the catalyst complex for example as a loose bed or as a fixed bed
• 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.
• the catalyst complex 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.
• the catalyst complex 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.
• 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).
• weaker electrostatic interaction may also occur.
• 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.
• 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.
• 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.
• 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.
• 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).
• 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.
• 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.
• the polymerization can also be designed as a continuous process.
• 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 ons sued.
• the monomer or monomers to be polymerized can be supplied as such, diluted with a solvent or as a monomer-containing hydrocarbon stream.
• 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.
• 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 hydrox
• 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 ( ⁇ -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%.
• 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.
• the process of the invention is used to prepare highly reactive isobutene-styrene copolymers.
• the highly reactive isobutene-styrene copolymers have a content of terminal vinylidene double bonds ( ⁇ -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.
• 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.
• PDI M w / Mn
• 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.
• 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.
• 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).
• 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).

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