[go: up one dir, main page]
More Web Proxy on the site http://driver.im/

WO2006077117A1 - Procede pour produire un polyisobutene - Google Patents

Procede pour produire un polyisobutene Download PDF

Info

Publication number
WO2006077117A1
WO2006077117A1 PCT/EP2006/000452 EP2006000452W WO2006077117A1 WO 2006077117 A1 WO2006077117 A1 WO 2006077117A1 EP 2006000452 W EP2006000452 W EP 2006000452W WO 2006077117 A1 WO2006077117 A1 WO 2006077117A1
Authority
WO
WIPO (PCT)
Prior art keywords
isobutene
reaction
group
polymerization
initiator
Prior art date
Application number
PCT/EP2006/000452
Other languages
German (de)
English (en)
Inventor
Hans Peter Rath
Arno Lange
Original Assignee
Basf Aktiengesellschaft
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Publication of WO2006077117A1 publication Critical patent/WO2006077117A1/fr

Links

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

Definitions

  • the present invention relates to a process for the preparation of isobutene polymers in which isobutene or an isobutene-containing monomer mixture is polymerized in the presence of an initiator and a Lewis acid in a hydrocarbon solvent containing at least one unsaturated aliphatic hydrocarbon and / or unsaturated alicyclic Hydrocarbon and contains substantially no halogenated or aromatic hydrocarbons.
  • Homopolymers and copolymers of isobutene find use in a variety of ways, for example for the preparation of fuel and lubricant additives, as elastomers, as adhesives or cement raw materials or as a basic constituent of sealing and sealing compounds.
  • suitable polyisobutenes are telechelic, i. they have two or more reactive end groups. These end groups are mainly carbon-carbon double bonds that can be further functionalized or groups functionalized with a terminating agent.
  • Living cationic polymerization is generally understood to mean the polymerization of iso-olefins or vinylaromatics in the presence of metalloid or semimetal halides as Lewis acid catalysts and tertiary alkyl halides, benzyl or allyl halides, esters or ethers as initiators, which are reacted with the Lewis acid catalyst. Acid form a carbocation or a cationogenic complex.
  • a bifunctional initiator such as dicumyl chloride
  • EP-A 722 957 describes the preparation of telechelic isobutene polymers using an at least bifunctional initiator, such as dicumyl chloride, in chlorinated C 3 -C 8 hydrocarbons.
  • aromatic initiators such as 1, 3 and 1, 4-dicumyl chloride, can react to indanyl or Diindan weakness (See Cr Pratrap, SA Mustafa, JP Heller, J. Polym., Part A, Polym. Chem., 1993, 31, pp. 2387-2391), so that to a considerable extent only monofunctional polyisobutenes, ie with only one reactive end group.
  • EP-A-0713883 describes a process for the preparation of polyisobutene in which solvents having a specific dielectric constant are used.
  • Halogen-free solvent systems used are mixtures of aromatic hydrocarbons with alkanes. By contrast, when using alkanes as the sole solvent, no satisfactory polyisobutenes are obtained.
  • the object of the present invention was to provide a process for the preparation of polyisobutene, which manages without halogenated solvents and nevertheless leads to polymers with good product properties.
  • the object is achieved by polymerizing isobutene or an isobutene-containing monomer mixture in the presence of initiator and Lewis acid in a solvent containing at least one unsaturated aliphatic and / or alicyclic solvent contains substantially no halogenated and aromatic hydrocarbon solvents.
  • a solvent containing at least one unsaturated aliphatic and / or alicyclic solvent contains substantially no halogenated and aromatic hydrocarbon solvents.
  • dicumyl chloride is used as the initiator, the process results in polyisobutenes having high molecular uniformity and a high content of bifunctional polymers.
  • the object was accordingly achieved by a process for the preparation of isobutene polymers having a number average molecular weight of from 200 to 5000, in which isobutylene isobutene or an isobutene-containing monomer mixture in the presence of an initiator and a Lewis acid in a hydrocarbon solvent containing at least one solvent selected from unsaturated aliphatic and unsaturated alicyclic hydrocarbons and less than 2% by weight, based on the total weight of the hydrocarbon solvent, of halogenated and aromatic hydrocarbon solvents.
  • aliphatic hydrocarbons which have at least one olefinic double bond are understood to mean unsaturated aliphatic hydrocarbons.
  • Unsaturated alicyclic hydrocarbons are understood as meaning alicyclic (ie, cyclic, non-aromatic) hydrocarbons having at least one olefinic double bond. For multiple double bonds, these may be conjugated or isolated in the molecule.
  • hydrocarbons is meant organic molecules that are composed of carbon and hydrogen atoms and contain essentially no heteroatoms. Heteroatoms are all elements other than carbon and hydrogen, such as oxygen, nitrogen, sulfur, and especially halogen.
  • the term "contains substantially no heteroatoms” means that the aliphatic or alicyclic hydrocarbons less than 1 wt .-%, preferably less than 0.5 wt .-%, more preferably less than 0.1 wt .-% and in particular less as 0.01 wt .-% heteroatoms, in particular halogen atoms, based on the total weight of the hydrocarbons used, contain.
  • the hydrocarbon solvent used in the isobutene polymerization contains a total of less than 2 wt .-%, preferably less than 1 wt .-%, more preferably less than 0.5 wt .-%, even more preferably less than 0.1 wt .-% and in particular less than 0.05 wt .-%, eg less than 0.01 wt .-%, halogenated and aromatic hydrocarbons, based on the total weight of the hydrocarbon solvent.
  • Halogen in the context of the present invention is fluorine, chlorine or bromine, in particular fluorine or chlorine and especially chlorine.
  • Halogenated hydrocarbons are in the context of the present invention aliphatic or alicyclic, saturated or unsaturated hydrocarbons in which at least one hydrogen atom is replaced by a halogen atom, especially chlorine.
  • these are halogenated alkanes, preferably halogenated C 1 -C 8 -alkanes. Examples thereof are methyl chloride, methylene chloride, chloroform, carbon tetrachloride, chloroethane, dichloroethane, trichloroethane, tetrachloroethane, chloropropane, chlorobutane and the like.
  • Aromatic hydrocarbons are hydrocarbons containing an optionally substituted aromatic system. Examples of these are benzene, toluene, nitrobenzene, chlorobenzene, dichlorobenzene and the like.
  • the unsaturated aliphatic hydrocarbons are preferably alkenes, for example C 2 -C 10 -alkenes, alkadienes, for example C 4 -C 10 -alkadienes, or alkatrienes, for example C 6 -C 10 -alkatrienes, or mixtures thereof. Particularly preferred are C 2 -C 6 -alkenes, C 4 -C 6 -alkadienes and mixtures thereof.
  • C 2 -C O alkene is a mono-unsaturated linear or branched hydrocarbon having 2 to 10 carbon atoms.
  • examples of these are ethene, propene, 1-butene, 2-butene, Isobutene, 1-pentene, 2-pentene, 1-hexene, 2-hexene, 3-hexene, 1-heptene, 2-heptene, 3-heptene, 1-octene, 2-octene, 3-octene, 4-octene, 1-, 2-, 3-, 4-nonene, 1-, 2-, 3-, 4- and 5-decene and constitutional isomers thereof.
  • C 2 -C 6 -alkene is a monounsaturated linear or branched hydrocarbon having 2 to 6 carbon atoms. Examples thereof are ethene, propene, 1-butene, 2-butene, isobutene, 1-pentene, 2-pentene, 1-hexene, 2-hexene, 3-hexene, and constitutional isomers thereof.
  • C 4 -C 10 -alkadiene is a diunsaturated linear or branched hydrocarbon having 4 to 10 carbon atoms. Examples of these are butadiene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene and decadiene, as well as constitution isomers thereof.
  • C 4 -C 6 -alkadiene is a diunsaturated linear or branched hydrocarbon having 4 to 6 carbon atoms. Examples of these are 1, 3-butadiene, 1, 3 and 1, 4-pentadiene and 1, 3, 1, 4, 1, 5 and 2,4-hexadiene and constitution isomers thereof.
  • C 6 -C 10 alkatriene is a triunsaturated linear or branched hydrocarbon of 6 to 10 carbon atoms. Examples of these are hexatriene, 1,3,5- and 1,6,6-heptatriene, 1,3,5-, 1,3,6-, 1, 3,7-, 1, 4,6-, 1, 4,7- and 2,4,6-octatriene, nonatriene and decatriene and constitutional isomers thereof.
  • C 4 -C 6 -alkanes are, for example, butane, isobutane, pentane and hexane and also their constitutional isomers.
  • C 4 -C 0 are alkanes beyond heptane, octane, nonane, and decane and their constitutional isomers.
  • the unsaturated alicyclic hydrocarbons are preferably cycloalkenes, for example C 5 -C 6 -alkenes, such as cyclopentene or cyclohexene, or cycloalkadienes, for example C 5 -C 6 -alkadienes, such as cyclopentadiene or cyclohexadiene. It goes without saying that the alicyclic compounds do not have so many conjugated double bonds that an aromatic system is present.
  • Preferred solvents are selected from unsaturated aliphatic hydrocarbons, preferably among alkenes, for example C 2 -C 10 -alkenes, optionally in admixture with alkanes, for example C 4 -C 10 -alkanes, alkadienes, for example C 4 -C 10 -alkadienes, and or alkatrienes, for example C 6 -Cio-alkatrienes, are used.
  • alkenes are 1-alkenes and isoalkenes.
  • Particularly preferred solvents are selected from C 2 -C 6 -alkenes, which are optionally present in admixture with C 4 -C 6 -alkanes and / or C 4 - C ⁇ -alkadienes.
  • suitable C 2 -C 6 -alkenes are ethene, propene, 1- and 2-butene, isobutene, 1- and 2-pentene, 1, -2- and 3-hexene and their constitution isomers and mixtures of these alkenes.
  • suitable C 4 -C 6 -alkanes are butane, isobutane, pentane, hexane and their constitution isomers and mixtures of these alkanes.
  • C 4 -C 6 -alkadienes examples include butadiene, 1, 3 and 1, 4-pentadiene, 1, 3, 1, 4 and 2,4-hexadiene and their constitution isomers and mixtures of these alkadienes. More preferred alkenes are propene, 1-butene and isobutene and mixtures of these alkenes. Even more preferred alkenes are isobutene and 1-butene, as well as mixtures thereof.
  • the mixture contains the polyenes in an amount of preferably at most 1 wt .-%, particularly preferably at most 0.5 wt .-%, more preferably at most 0.2 wt .-%, in particular at most 0.05 wt .-%, especially at most 0.02 wt .-%, based on the total weight of the mixture.
  • the mixture contains the alkanes in an amount of preferably at most 50% by weight, particularly preferably at most 40% by weight, more preferably at most 30% by weight and in particular at most 25% by weight. -%, for example at most 20 wt .-%, based on the total weight of the mixture.
  • isobutene is used as the solvent.
  • preferred solvents are selected from technical mixtures of aliphatic hydrocarbons.
  • Preferred technical mixtures are C 4 - hydrocarbon mixtures, ie mixtures containing hydrocarbons having 4 carbon atoms, such as butane, isobutane, 1-butene, 2-butene, isobutene and butadiene. Examples of this are C 4 raffinates, C 4 cuts from isobutane dehydrogenation, C 4 -
  • Suitable C 4 -hydrocarbon mixtures preferably contain at most 1% by weight, more preferably at most 0.5% by weight, more preferably at most 0.2% by weight, in particular at most 0.05% by weight, especially at most 0, 02 wt .-%, butadiene, based on the total weight of the mixture.
  • Preferred C 4 - hydrocarbon mixtures are isobutene-containing mixtures. Preferred hydrocarbon mixtures are therefore, for example, raffinate I and C 4 cuts from FCC crackers or from isobutane dehydrogenation.
  • Raffinate I is a C 4 hydrocarbon stream having approximately the following composition: 0-5% isobutane; 4-12% n-butane; 35-55% isobutene; 15-55% 1-butene; 10-25% 2-butene and 0-0.5% 1,3-butadiene.
  • C 4 cuts from FCC crackers have approximately the following composition: 5-15% n-butane, 15-25% isobutane, 14-18% isobutene, 15-25% trans-but-2-ene, 10-20 % cis-but-2-ene and 10-20% 1-butene.
  • C 4 cuts from the isobutane dehydrogenation have approximately the following composition: 45-55% isobutene, 40-50% butane and 2-10% 1- and 2-butenes.
  • isobutene or an isobutene-containing hydrocarbon mixture is used as the solvent, this means that the monomer to be polymerized or monomer-containing mixture simultaneously also acts as a solvent.
  • the isobutene to be polymerized can be in the form of isobutene itself or in the form of isobutene-containing C 4 -hydrocarbon mixtures, ie mixtures containing, in addition to isobutene, further hydrocarbons having 4 carbon atoms, such as butane, isobutane , 1-butene, 2-butene and butadiene.
  • C 4 -hydrocarbon mixtures ie mixtures containing, in addition to isobutene, further hydrocarbons having 4 carbon atoms, such as butane, isobutane , 1-butene, 2-butene and butadiene.
  • the monomer mixture preferably contains more than 80% by weight, more preferably more than 90% by weight, and in particular more than 95% by weight of isobutene, and less than 20% by weight. %, preferably less than 10% by weight, and in particular less than 5% 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 4-tert-butylstyrene, isoolefins having 5 to 10 C atoms such as 2-methylbutene-1, 2 Methylpentene-1, 2-methylhexene-1, 2-ethyl-pentene-1, 2-ethylhexene-1 and 2-propylheptene-1.
  • 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.
  • 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.
  • the living chain ends can also be reacted in the presence of unreacted isobutene with suitable comonomers.
  • suitable comonomers are, in particular, those which have a higher degree of nucleophilicity than isobutene. Examples of these are vinylaromatics such as ⁇ -methylstyrene.
  • For bulk polymerization e.g. first homopolymerize isobutene and add the comonomer in due course.
  • the newly formed comonomer-containing reactive chain end is either deactivated or terminated according to one of the embodiments described below to form a functional end group or reacted again with isobutene to form higher block copolymers.
  • the initiator is an organic compound having at least one functional group FG which can form a carbocation or a cationogenic complex under polymerization conditions with the Lewis acid.
  • the terms "carbocation” and “cationogenic complex” are not strictly separated, but include all intermediates of solvent separated ions, solvent separated ion pairs, contact ion pairs, and highly polarized positive charge charged complexes on a C atom of the initiator molecule.
  • all organic compounds which have at least one nucleophilically displaceable leaving group X and which can stabilize a positive charge or partial charge on the carbon atom which carries the leaving group X are suitable as initiators.
  • These include, as is known, compounds which have at least one leaving group X attached to a secondary or tertiary aliphatic carbon atom or to an allylic or benzylic carbon atom.
  • leaving groups according to the invention halogen, alkoxy, preferably C 1 -C 6 -alkoxy, and acyloxy (alkylcarbonyloxy), preferably CrCe-alkylcarbonyloxy, into consideration.
  • Halogen is here in particular chlorine, bromine or iodine and especially chlorine.
  • C 1 -C 6 -alkoxy may be both linear and branched, and is, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, n-pentoxy and n-hexoxy, in particular methoxy.
  • C 1 -C 6 -alkylcarbonyloxy is, for example, acetoxy, propionyloxy, n-butyroxy and isobutyroxy, in particular acetoxy.
  • X is selected from halogen, C 1 -C 6 -alkoxy and C r C 6 -acyloxy,
  • R 1 is hydrogen or methyl
  • R 2 is methyl, or with R 1 or the moiety to which the FG functional group is attached forms a C 5 -C 6 cycloalkyl ring, R 2 may also be hydrogen when the FG functional group is an aromatic or olefinically unsaturated C atom is bound.
  • the initiators preferably have one, two, three or four, in particular one or two, and particularly preferably two functional groups FG.
  • X in formula (FG) preferably represents a halogen atom, in particular chlorine.
  • Preferred initiators obey the general formulas I-A to I-F:
  • n and k are independently 0, 1, 2, 3, 4 or 5;
  • n 1, 2 or 3;
  • R 3 , R 4 and R 10 are independently hydrogen or methyl
  • R 5 , R 6 and R 7 independently of one another are hydrogen, C 1 -C 4 -alkyl or a group CR 3 R 4 -X, where R 3 , R 4 and X have the meanings given above;
  • R 8 is hydrogen, methyl or a group X
  • R 9 and R 11 are hydrogen or a group X
  • A is an ethylenically unsaturated hydrocarbon radical having a vinyl group or a cycloalkenyl group.
  • R 3 and R 4 are preferably both methyl.
  • R 6 is , for example, a group CR 3 R 4 -X which is arranged in para or meta position to the CR 3 R 4 X group, in particular when R 5 is hydrogen. It may also be in the meta position if the group R 5 is Cr C 4 alkyl or a group CR 3 R 4 -X.
  • Preferred compounds IA are z. For example: 2-chloro-2-phenylpropane and 1,4-bis (2-chloro-2-propyl) benzene (1,4-dicumyl chloride, 1,4-bis (2-chloro-2-propyl) benzene). DCC) or 1, 3-bis (2-chloro-2-propyl) benzene (1, 3-dicumyl chloride, 1, 3-DCC).
  • Examples of compounds of the formula I-B are allyl chloride, methallyl chloride, 2-chloro-2-methylbutene-2 and 2,5-dichloro-2,5-dimethylhexene-3.
  • R 3 is preferably methyl.
  • R 9 preferably represents a group X, and in particular halogen, especially when R 10 is methyl.
  • Examples of compounds of the general formula IC are 1, 8-dichloro-4-p-menthane (limonene dihydrochloride), 1, 8-dibromo-4-p-menthane (limonene dihydrobromide), 1 - (1-chloroethyl-S-chlorocyclohexane, 1 - (1-chloroethyl-4-chloro-cyclohexane, 1- (1-bromoethyl) -3-bromocyclohexane and 1- (1-bromoethyl) -4-bromocyclohexane.
  • R 8 is a methyl group.
  • R 8 is a group X, and in particular a halogen atom, when n> 0.
  • A is a radical of the formulas A.1, A.2 or A.3
  • n is a number from 0 to 3, in particular 0, 1 or 2, and p is 0 or 1.
  • m is preferably 1.
  • X is preferably chlorine
  • m is preferably 1 or 2 and particularly preferably 1.
  • a preferred compound of the formula I-F is 3-chlorocyclopentene.
  • initiators compounds of the formula IA and in particular 1,4-bis (2-chloro-2-propyl) benzene (1,4-dicumyl chloride, 1,4-DCC) or 1,3-bis (2-chloro 2-propyl) benzene (1, 3-dicumyl chloride, 1, 3-DCC), with 1, 4-dicumyl chloride being particularly preferred.
  • Covalent metal halides and semimetallic halides having an electron-pair gap may be considered as the Lewis acid.
  • Such compounds are known to the person skilled in the art, for example from J.P. Kennedy et al. in US 4,946,889; US 4,327,201; US 5,169,914; EP-A-206,756; EP-A-265 053; and J.P. Kennedy, B. Ivan, "Designed Polymers by Carbocationic Macromolecular Engineering,” Oxford University Press, New York, 1991. They are typically selected from halogen compounds of titanium, tin, aluminum, vanadium, or iron, as well the halides of the boron.
  • the chlorides are preferred, and in the case of aluminum also the monoalkylaluminum dichlorides and the dialkylaluminum chlorides.
  • Preferred Lewis acids are titanium tetrachloride, boron trichloride, boron trifluoride, tin tetrachloride, aluminum trichloride, vanadium pentachloride, iron trichloride, alkylaluminum dichlorides and dialkylaluminum chlorides.
  • Particularly preferred Lewis acids are titanium tetrachloride, boron trichloride and ethylaluminum dichloride, and especially titanium tetrachloride.
  • Suitable electron donors are aprotic organic compounds which have a free electron pair located on a nitrogen, oxygen or sulfur atom.
  • Preferred donor compounds are selected from pyrrides such as pyridine itself, 2,6-dimethylpyridine, as well as sterically hindered pyridines such as 2,6-diisopropylpyridine and 2,6-di-tert-butylpyridine; Amides, in particular N 1 N- dialkylamides of aliphatic or aromatic carboxylic acids such as N, N-dimethylacetamide; Lactams, in particular N-alkyl lactams such as N-methylpyrrolidone; Ethers, for example dialkyl ethers, such as diethyl ether and diisopropyl ether, cyclic ethers, such as tetrahydrofuran; Amines, in particular trialkylamines such as triethylamine; Esters,
  • Particularly preferred electron donor compounds are selected from pyridines and nonpolymerizable, aprotic, organosilicon compounds which have at least one oxygen-bonded organic radical.
  • the donor compounds are selected from non-polymerizable, aprotic, organosilicon compounds which have at least one oxygen-bonded organic radical.
  • organosilicon compounds which have at least one oxygen-bonded organic radical.
  • examples of such radicals are alkyloxy, cycloalkyloxy, aryloxy, arylalkyloxy and acyloxy (alkylcarbonyloxy).
  • alkyl is meant a linear or branched saturated hydrocarbon radical having generally 1 to 20 C atoms, and preferably 1 to 10 C atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert Butyl, 2-butyl, n-pentyl, 2-methylbutyl-1, 2-methylpentyl-1,2-ethylbutyl-1, n-hexyl, 2-hexyl, 2-methylhexyl-1,2-ethylhexyl-1, n-heptyl, n-octyl, isooctyl, n-decyl, and comparable radicals.
  • Aryl is an aromatic hydrocarbon radical having generally 6 to 20 C atoms, such as phenyl, naphthyl and comparable groups which may have one or more C 1 -C 10 -alkyl groups as substituents, for example ToIyI, isopropylphenyl, Xy-IyI or tert-butylphenyl.
  • Cycloalkyl means a generally 5-, 6- or 7-membered saturated carbocycle cycius, optionally containing a plurality CRCI or O may have alkyl groups as substituents here.
  • Arylalkyl is an alkyl radical having usually 1 to 10 C atoms, and preferably 1 to 4 C atoms, which is substituted by an aryl radical as defined above, e.g. for benzyl or 2-phenylethyl.
  • Alkyloxy is alkyl bound via an oxygen atom. Accordingly, aryloxy, cycloalkyloxy and arylalkyloxy are aryl, cycloalkyl and arylalkyl bonded via an oxygen atom.
  • Acyloxy is an oxygen-bonded alkylcarbonyl radical which preferably has 1 to 6 C atoms in the alkyl moiety, for example for acetyloxy, propionyloxy, butyroxy etc.
  • the organosilicon compounds may have one or more, eg 2 or 3, silicon atoms with at least one oxygen-bonded organic radical. Preference is given to those organosilicon compounds which have one, two or three, and in particular 2 or 3, oxygen-bonded organic radicals per silicon atom.
  • organosilicon compounds are those of the following general formula:
  • r 1, 2 or 3
  • R a may be identical or different and independently of one another are C 1 -C 20 -alkyl, C 3 -C 7 -cycloalkyl, aryl or ArVl-C 1 -C 4 -alkyl, where the last three radicals mentioned are also C 1 -C 20 -alkyl radicals; C 1o- alkyl groups may have as substituents, and
  • R b are the same or different and are C 1 -C 20 -alkyl or, in the case where r is 1 or 2, two radicals R b together may be alkylene.
  • R a is preferably a Gi-C ⁇ -alkyl group, and in particular a branched or bonded via a secondary carbon atom alkyl group, such as isopropyl, isobutyl, sec-butyl, or a 5- , 6- or 7-membered cycloalkyl group, or an aryl group, in particular phenyl.
  • the variable R b is preferably a C 1 -C 4 alkyl group or a phenyl, ToIyI or benzyl radical.
  • Examples of such preferred compounds are dimethoxydiisopropylsilane, dimethoxyisobutylisopropylsilane, dimethoxydi-isobutylsilane, dimethoxydicyclopentylsilane, dimethoxyisobutyl-2-butylsilane, diethoxyisobutylisopropylsilane, triethoxytoluylsilane, triethoxybenzylsilane and triethoxyphenylsilane.
  • C 1 -C 4 -alkyl is a branched or linear alkyl radical, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl.
  • C 1 -C 6 -alkyl is pentyl, hexyl, heptyl, octyl and their positional isomers.
  • C 1 -C 10 -alkyl represents nonyl and decyl and their positional isomers.
  • -C 2 -alkyl also stands for undecyl, dodecyl, tridecanol cyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl and their positional isomers.
  • C 3 -C 7 -cycloalkyl is, for example, cyclopropyl, cyclopentyl, cyclohexyl and cycloheptyl.
  • C 5 -C 7 -cycloalkyl is, for example, cyclopentyl, cyclohexyl and cycloheptyl.
  • Aryl is in particular phenyl, naphthyl or ToIyI.
  • Aryl-C 1 -C 4 -alkyl is especially benzyl or 2-phenylethyl.
  • Alkylene is, for example, C 2 -C 5 -alkylene, such as 1, 2-ethylene, 1, 2 and 1, 3-propylene, 1, 4-butylene and 1, 5-pentylene.
  • the polymerization is carried out in the presence of an alkylammonium halide.
  • Suitable alkylammonium halides are both monoalkylammonium salts and di-, tri- or tetraalkylammonium halides.
  • Suitable alkyl groups are C r Ci 0 - alkyl radicals such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl and their Konstituionsisomere.
  • Preferred alkyl radicals are C 1 -C 6 -alkyl radicals, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl and their constitutional isomers.
  • the alkyl radicals may be the same or different. Preference is given to tetraalkylammonium halides, in particular those having four identical alkyl radicals. Suitable halide counterions are fluoride, chloride and bromide, with chloride and bromide being preferred.
  • tetraalkylammonium moniumhalogenide examples include tetramethylammonium fluoride, tetramethylammonium chloride, tetramethylammonium bromide, tetraethylammonium fluoride, Tetraethylammoniumchlo- chloride, tetraethylammonium bromide, Tetrapropylammoniumfluorid, Tetrapropylammoni- monium chloride, ammonium chloride tetrapropylammonium bromide, tetrabutylammonium fluoride, tetrabutylammonium chloride, tetrabutylammonium bromide, Tetrapentylammoniumfluorid, Tetrapenty- lammoniumchlorid, tetrapentylammonium bromide, Tetrahexylammoniumfluorid, tetra- hexylammoniumchlorid
  • the polymerization can be carried out both batchwise (batchwise) and in a continuous mode.
  • the initial content of isobutene is preferably at least 10% by weight, more preferably at least 20% by weight and in particular at least 30% by weight, based on the total weight of the reaction mixture.
  • the isobutene content at the feed point is preferably at least 10% by weight, more preferably at least 20% by weight and in particular at least 30% by weight, based on the total weight of the at Feed point located reaction mixture.
  • 1,3- or 1,4-dicumyl chloride is used as the initiator, it is preferred to carry out the polymerization with even higher isobutene initial concentrations, for example with at least 50% by weight, preferably at least 60% by weight, in particular at least 70 wt .-%, for example at least 80 wt .-%, based on the total weight of the reaction mixture or in the case of continuous reaction control to the total weight of the reaction mixture located at the level of the feed point.
  • the Lewis acid is used in an amount sufficient to form an initiator complex with the initiator.
  • the molar ratio of Lewis acid to initiator is preferably 10: 1 to 1:10, more preferably 1: 1 to 1: 6, more preferably 1: 2 to 1: 5 and especially 1: 3 to 1: 4.
  • the initial concentration of the Lewis acid in the reaction mixture (ie the amount used) is preferably in the range of 5 to 200 mmol / l, more preferably 10 to 100 mmol / l and especially 10 to 60 mmol / l, based on the total volume of the reaction mixture ,
  • polymerization-active Lewis acids are those which can also initiate isobutene polymerization individually in combination with the initiator.
  • the molar ratio of boron trichloride to titanium tetrachloride is preferably from 1.5: 1 to 100: 1, more preferably from 2: 1 to 20: 1, and especially from 5: 1 to 10: 1.
  • the initiator is preferably used in such an amount that per 1 l reaction mixture preferably at least 20 mmol, more preferably at least 100 mmol and in particular at least 200 mmol leaving groups X, which are contained in the functional groups FG of the initiator molecule, are used.
  • the maximum amount of initiator is preferably not more than 600 mmol, more preferably not more than 500 mmol and in particular not more than 400 mmol leaving groups X, based on 1 l of the reaction mixture.
  • monofunctional initiators ie those having a group FG and corresponding to a group X
  • monofunctional initiators are used in an amount of preferably at least 20 mmol / l, more preferably at least 100 mmol / l and especially at least 200 mmol / l, based on the total volume of the reaction mixture
  • the maximum amount of monofunctional initiator is preferably not more than 600 mmol / l, particularly preferably not more than 500 mmol / l and in particular not more than 400 mmol / l, based on the total volume of the reaction mixture.
  • bifunctional initiators are used in an amount of preferably at least 10 mmol / l, particularly preferably at least 50 mmol / l and in particular at least 100 mmol / l, based on the total volume of the reaction mixture .
  • the maximum amount of bifunctional initiator is preferably at most 300 mmol / l, particularly preferably at most 250 mmol / l and in particular at most 200 mmol / l, based on the total volume of the reaction mixture.
  • the molar ratio of Lewis acid to electron donor is generally 10: 1 to 1:10, preferably 10: 1 to 1: 1, more preferably 5: 1 to 1: 1.
  • the molar ratio of Lewis acid to alkylammonium halide is generally 10: 1 to 1: 3, preferably 5: 1 to 1: 2, more preferably 3: 1 to 1: 1.
  • the alkylammonium halide is used in an amount of preferably 5 to 100 mmol / l, particularly preferably 10 to 80 mmol / l and in particular 20 to 50 mmol / l, based on the total volume of the reaction mixture.
  • the polymerization is carried out under largely aprotic, 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 physically and / or by chemical means before being used.
  • an organometallic compound for example an organolithium, organomagnesium or organoaluminium compound, in an amount which is sufficient to remove the traces of water from the solvent.
  • the solvent thus treated is then condensed directly into the reaction vessel.
  • the pre-cleaning or predrying of the solvents and of the isobutene is carried out in a customary manner, preferably by treatment with solid drying agents, such as molecular sieves or predried oxides, such as aluminum oxide, silicon dioxide, calcium oxide or barium oxide.
  • solid drying agents such as molecular sieves or predried oxides, such as aluminum oxide, silicon dioxide, calcium oxide or barium oxide.
  • the polymerization of the isobutene or the isobutene-containing feed takes place spontaneously on mixing the initiator system (ie Lewis acid and initiator) with the isobutene or the isobutene-containing feedstock at the desired reaction temperature.
  • the initiator system ie Lewis acid and initiator
  • adding the initiator system one will usually proceed by separately adding the components of the initiator system.
  • the Lewis acid is added as the last component of the reaction system in order to minimize the probability of initiation of polymerization by protons.
  • continuous operation can be carried out by first initially introducing the initiator and optionally the electron donor and / or the alkylammonium halide in a solvent other than isobutene or isobutene-containing hydrocarbon mixtures, then the isobutene or the isobutene-containing starting material and then the Lewis acid admits. The beginning of polymerization is then the time at which all components of the initiator system are contained in the reaction vessel.
  • the polymerization can also be designed as a continuous process.
  • the components of the initiator system can be supplied both separately and together, preferably diluted in the solvent, wherein the separate addition is preferred.
  • the isobutene to be polymerized or the isobutene-containing feedstock can be supplied as such, diluted with a solvent or as an isobutene-containing hydrocarbon stream.
  • isobutene or the isobutene-containing feedstock is first brought into contact with the initiator, for example, by feeding the two components already as a mixture to the reactor or by the initiator feed takes place directly behind the monomer feed.
  • electron donors and / or alkylammonium halides are also used, their contact with the monomer is preferably also before the contact of the latter with the Lewis acid.
  • electron donors and / or alkylammonium halides are fed either in the mixture with the monomer and / or the initiator or the feed takes place directly behind the monomer feed.
  • the Lewis acid preferably comes into contact with the other reactants only after the monomer has been mixed with the initiator and optionally the electron donor and / or the alkylammonium halide.
  • the reaction is preferably carried out such that the polymer concentration is in the range from 1 to 90% by weight, more preferably from 2 to 80% by weight and in particular from 5 to 50% by weight, based on the total weight of the reaction mixture ,
  • the weight ratios refer to the polymer concentration at the end, ie shortly before the termination of the reaction.
  • the weight ratios refer to the stationary polymer concentration or, in particular in the tubular reactor, to the polymer concentration in the discharge or the termination.
  • Isobutene consumed during the reaction can be partially or completely replaced or even overcompensated by the addition of fresh isobutene (so-called “incremental monomer addition” technique.)
  • Both the isobutene originally used and the isobutene optionally added in the course of the polymerization can be complete or else only However, it is preferred, especially when using 1,3-dicumyl chloride or 1,4-dicumyl chloride as initiator, if the isobutene used is not completely polymerized, in which case the isobutene used is preferably not more than 80% by weight.
  • the method according to the invention at temperatures ranging from 60 to -140 0 C, preferably in the range from 0 to -120 0 C, and particularly forthcoming Trains t in the range of -30 to -8O 0 C perform.
  • the reaction pressure is of subordinate importance at temperatures below -10 0 C, since isobutene is present condensed at these temperatures and thus is practically not further compressible.
  • Only at higher temperatures and / or when using still lower boiling solvents such as ethene or propene, when using a forced circulation with external heat exchanger or a tube (bundle) reactor is preferably carried out at elevated reaction pressure, for example at a pressure of 3 to 20 bar.
  • the dissipation of the heat of reaction in the discontinuous as well as in the continuous reaction is carried out in a conventional manner, for example by internally installed heat exchangers and / or by wall cooling and / or taking advantage of a Siedekühlung.
  • the continuous reaction can be carried out in the customary reaction vessels, reaction cascades, tubular reactors, tube bundle reactors, in particular circularly guided tube and tube bundle reactors, which are preferably equipped in the manner described above for stirred tank.
  • a particularly preferred reactor type is the helical tube reactor described, for example, in EP-A-1395620.
  • the living chain ends are deactivated, for example by adding a protic compound, in particular by adding water, Alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol or tert-butanol, or mixtures thereof with water.
  • a protic compound in particular by adding water, Alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol or tert-butanol, or mixtures thereof with water.
  • the process according to the invention gives polyisobutenes which contain a functional group at at least one terminus (chain end).
  • This functional group is preferably a group -CH 2 -C (CH 3 ) 2 -halogen. This is usually formed during reaction quenching with a protic deactivator.
  • the halogen atom in this terminal group is usually derived from the initiator used for the polymerization. Preferably, halogen is chlorine.
  • Telechelic (bifunctional) polyisobutenes are also obtained when initiators are used which themselves contain a functionality, for example initiators of the formulas IB, IE and IF.
  • the telechelic polyisobutenes are valuable intermediates for the preparation of other bifunctional polyisobutene derivatives.
  • Examples of the derivatization include the alkylation of phenols and the elimination of hydrogen halide from the group -CH 2 -C (CH 3 ) 2 -halogen to form an ethylenically unsaturated terminal group.
  • a ethylenically unsaturated radical for example, thermally, for. B. by heating to a temperature of 70 to 200 0 C, preferably under vacuum, or by treatment with a base.
  • bases are, for example, alkali metal alkoxides, such as sodium methoxide, sodium ethoxide and potassium tert-butoxide, basic aluminum oxide, alkali metal hydroxides, such as sodium hydroxide, and tertiary amines, such as pyridine or tributylamine, cf. Kennedy et al., Polymer Bulletin 1985, 13, 435-439.
  • sodium ethoxide or potassium tert-butoxide is used.
  • Suitable termination reagents are, for example, trialkylallylsilane compounds, e.g. Trimethyallylsilane.
  • the living chain ends are thereby terminated by adding a trialkylallylsilane compound.
  • allyl silanes leads to the termination of the polymerization with the introduction of an allyl radical at the polymer chain end, cf. EP 264 214.
  • a termination reagent is 1,1-diphenylethylene.
  • the living chain ends are terminated by addition of 1, 1-diphenylethylene and a base, whereby a diphenyl-substituted double bond is introduced at the chain end, see. J. Feldthusen, B. Ivan, AHE Mueller and J. Kops, Macromol. Rep. 1995, A32, 639, J. Feldthusen, B. Ivän and AHE Müller, Macromolecules 1997, 30, 6989 and Macromolecules 1998, 31, 578, DE-A 19648028 and DE-A 19610350.
  • conjugated dienes e.g. Butadiene
  • termination reagents e.g. butadiene
  • the reactive chain end is reacted with the conjugated diene and then deactivated as described above, cf. DE-A 40 25 961.
  • two or more living polymer chains can be coupled for termination by adding a coupling agent.
  • “Coupling” means the formation of chemical bonds between the reactive chain ends, so that two or more polymer chains are combined into one molecule.
  • the molecules obtained by coupling are symmetric telechelic or star-shaped molecules whose other living chain ends must be terminated according to one of the methods described above.
  • Coupling of living copolymers of the AB + type makes it possible, for example, to prepare triblock copolymers of the AB-BA type in which A is a polybutylene block and B is a different polymer block, for example a polyvinylaromatic block.
  • Suitable coupling agents include, for example, at least two electrolytic leaving groups, all of which are allylated to the same or different double bonds, e.g. Trialkylsilyl phenomenon, so that the cationic center of a reactive chain end can attach in a concerted reaction with cleavage of the leaving group and displacement of the double bond.
  • Other coupling agents have at least one conjugated system to which the cationic center of a reactive chain end can add electrophilically to form a stabilized cation. By cleavage of a leaving group, e.g. of a proton, then forming a stable s-bond to the polymer chain with reformation of the conjugated system.
  • Several of these conjugated systems can be linked together by inert spacers.
  • Suitable coupling agents include:
  • R is d-Cio-alkylene, preferably methylene or 2,2-propanediyl
  • the coupling is usually carried out in the presence of a Lewis acid, with those Lewis acids are suitable, which are also useful for carrying out the actual polymerization reaction.
  • a Lewis acid for carrying out the coupling reaction, the same solvents and temperatures are also suitable as are used for carrying out the actual polymerization reaction.
  • the coupling can therefore be carried out as a one-pot reaction following the polymerization reaction in the same solvent in the presence of the Lewis acid used for the polymerization.
  • a molar amount of the coupling agent is used which corresponds approximately to the quotient of the molar amount of initiator used for the polymerization, divided by the number of coupling sites of the coupling agent.
  • the solvent and excess isobutene are generally removed in suitable aggregates such as rotary, falling film or thin film evaporators or by relaxation of the reaction solution.
  • Another object of the present invention are isobutene polymers obtainable by the process according to the invention.
  • the isobutene polymers produced by the process according to the invention have a narrow molecular weight distribution.
  • the process according to the invention is generally used for the preparation of polyisobutenes having a number average molecular weight M n of from 200 to 5,000, preferably from 300 to 5,000 and in particular from 500 to 5,000.
  • the isobutene polymers prepared according to the invention are terminated at least at one chain end by a group -CH 2 -C (CH 3 ) 2 -halogen, particularly preferably -CH 2 -C (CH 3 ) 2 -CI.
  • the groups at the ends of the chain are preferably ethylenically unsaturated groups which, as described above, are present thermally or by reacting the halogen-substituted chain ends with a suitable base or by reacting the living and polymer components formed during the polymerization.
  • the polyisobutene chains are obtainable with a trialkylallylsilane compound, with 1, 1-diphenylethylene or a conjugated diene.
  • polyisobutenes obtained according to the invention can furthermore be subjected to the following functionalization reactions:
  • the functionalization reactions described can be carried out not only on the chain terminus terminated as described above but also on the opposite unsaturated end group (derived from the initiator derived). Due to the different reactivity of the terminated chain end and the opposite unsaturated group, these can also be functionalized differently.
  • a polyisobutene (specifically polyisobutene terminated with ethylenically unsaturated groups) prepared according to the process according to the invention can be subjected to a reaction with a silane in the presence of a silylation catalyst to give a polyisobutene which is at least partially functionalized with silyl groups.
  • Suitable hydrosilylation catalysts are, for example, transition metal catalysts, wherein the transition metal is preferably selected from Pt, Pd, Rh, Ru and Ir.
  • suitable platinum catalysts include platinum in finely divided form (“platinum black"), platinum chloride and platinum complexes such as hexachloroplatinic acid or divinyldisiloxane-platinum complexes, eg tetramethyldivinyldisiloxane-platinum complexes.
  • Suitable rhodium catalysts are, for example, (RhCl (P (C 6 H s ) 3 ) 3 ) and RhCl 3 . Also suitable are RuCl 3 and IrCl 3 .
  • Suitable catalysts are also Lewis acids such as AICI 3 or TiCl 4 and peroxides. It may be advantageous to use combinations or mixtures of the aforementioned catalysts.
  • Suitable silanes include halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane and trimethylsiloxydichlorosilane; Alkoxysilanes, such as methyldimethoxysilane, phenyldimethoxysilane, ISS ⁇ . ⁇ JJ-heptamethyl-i .i-dimethoxytetrasiloxane and trialkoxysilanes, z. B. trimethoxysilane and triethoxysilane, and acyloxysilanes. Preference is given to using trialkoxysilanes.
  • the reaction temperature in the silylation is preferably in a range from 0 to 140 0 C, particularly preferably 40 to 12O 0 C.
  • the reaction is usually carried out under normal pressure, but can also at elevated pressures, such as in the range of about 1, 5 to 20 bar, or reduced pressures, such as 200 to 600 mbar done.
  • the reaction can be carried out without solvent or in the presence of a suitable solvent.
  • Preferred solvents are, for example, toluene, tetrahydrofuran and chloroform.
  • a polyisobutene (specifically polyisobutene terminated with ethylenically unsaturated groups) prepared by the process according to the invention of a reaction with hydrogen sulfide or a thiol, such as alkyl- or arylthiols, hydroxymercaptans, aminomercaptans, thiocarboxylic acids or silanethiols, can be obtained at least partially be subjected to polyisobutene functionalized with thio groups.
  • Suitable hydro-alkylthio-additions are described in J. March, Advanced Organic Chemistry, 4th Edition, John Wiley & Sons, pp. 766-767, which is hereby incorporated by reference in its entirety.
  • the reaction can usually be carried out both in the absence and in the presence of initiators and in the presence of electromagnetic radiation.
  • Upon addition of hydrogen sulfide functionalized polyisobutenes are obtained with thiol groups.
  • the addition of hydrogen sulfide is preferably carried out at temperatures below 100 0 C and a pressure of 1 to 50 bar, more preferably of about 10 bar.
  • the addition is preferably carried out in the presence of a cation exchange resin, such as Amberlyst 15.
  • a cation exchange resin such as Amberlyst 15.
  • Suitable initiators of the hydro-alkylthio addition are, for example, protic and Lewis acids, such as concentrated sulfuric acid or AICI 3 , and acidic cation exchangers, such as Amberlyst 15. Suitable initiators are furthermore those which are capable of forming free radicals, such as peroxides or Azo compounds. Hydro-alkylthio addition in the presence of these initiators usually gives the anti-Markovnikov addition products.
  • the reaction can furthermore be carried out in the presence of electromagnetic radiation having a wavelength of 400 to 10 nm, preferably 200 to 300 nm.
  • a polyisobutene prepared according to the process of the invention may be reacted with a compound having at least one aromatic or heteroaromatic group in the presence of an alkylation catalyst.
  • an alkylation catalyst Suitable aromatic and heteroaromatic compounds, catalysts and reaction conditions of this so-called Friedel-Crafts alkylation are described, for example, in J. March, Advanced Organic Chemistry, 4th Edition, published by John Wiley & Sons, pages 534-539, which is incorporated herein by reference.
  • an activated aromatic compound is used for the alkylation.
  • Suitable aromatic compounds are, for example, alkylaromatics, alkoxyaromatics, hydroxyaromatics or activated heteroaromatics, such as thiophenes or furans.
  • the aromatic hydroxy compound used for the alkylation is preferably selected from phenolic compounds having 1, 2 or 3 OH groups, which may optionally have at least one further substituent.
  • Preferred further substituents are C r C 8 -alkyl groups and in particular methyl and ethyl. Particular preference is given to compounds of the general formula
  • R 1 and R 2 are independently hydrogen, OH or CH 3 .
  • Particularly preferred are phenol, the cresol isomers, catechol, resorcinol, pyrogallol, fluoroglucinol and the xylenol isomers.
  • phenol, o-cresol and p-cresol are used. If desired, it is also possible to use mixtures of the abovementioned compounds for the alkylation.
  • polyaromatics such as polystyrene, polyphenylene oxide or polyphenylene sulfide, or copolymers of aromatics, for example with butadiene, isoprene, (meth) acrylic acid derivatives, ethylene or propylene.
  • the catalyst is preferably selected from Lewis acidic alkylation catalysts, which in the context of the present application are understood as meaning both individual acceptor atoms and acceptor-ligand complexes, molecules, etc., provided that they contain (outwardly) Lewis acid (electron acceptor). ) Have properties. These include, for example, AICI 3 , AIBr 3 , BF 3 , BF 3 2 C 6 H 5 OH, BF 3 [O (C 2 H 5 ) 2 ] 2 , TiCl 4 , SnCl 4 , AIC 2 H 5 Cl 2 , FeCl 3 , SbCI 5 and SbF 5 . These alkylation catalysts can be used together with a cocatalyst, for example an ether.
  • Suitable ethers are di (C 1 -C 8 ) alkyl ethers, such as dimethyl ether, diethyl ether, di-n-propyl ether, and tetrahydrofuran, di (C 5 -C 8 ) cycloalkyl ethers, such as dicyclohexyl ether and ethers having at least one aromatic hydrocarbon radical like anisole.
  • di (C 1 -C 8 ) alkyl ethers such as dimethyl ether, diethyl ether, di-n-propyl ether, and tetrahydrofuran
  • di (C 5 -C 8 ) cycloalkyl ethers such as dicyclohexyl ether and ethers having at least one aromatic hydrocarbon radical like anisole.
  • the molar ratio of catalyst to cocatalyst is preferably in the range of 1:10 to 10: 1.
  • the reaction can also be catalyzed with protic acids such as sulfuric acid, phosphoric acid, methanesulfonic acid or trifluoromethanesulfonic acid.
  • protic acids such as sulfuric acid, phosphoric acid, methanesulfonic acid or trifluoromethanesulfonic acid.
  • Organic protic acids may also be present in polymer bound form, for example as ion exchange resin. Also suitable are zeolites and inorganic polyacids.
  • the alkylation can be carried out solvent-free or in a solvent.
  • suitable solvents are n-alkanes and mixtures thereof and alkylaromatics such as toluene, ethylbenzene and xylene and halogenated derivatives thereof.
  • the alkylation is preferably carried out at temperatures between -10 0 C and + 10O 0 C.
  • the reaction is usually carried out at atmospheric pressure, but can also be carried out at higher pressures (for example in the case of volatile solvents) or at lower pressures.
  • the proportion of alkylated products obtained and their degree of alkylation can be adjusted.
  • Substantially monoalkylated polyisobutenylphenols are generally obtained with an excess of phenol or in the presence of a Lewis acidic alkylation catalyst if an additional ether is used as cocatalyst.
  • the polyisobutenylphenol obtained can be subjected to a reaction in the Mannich reaction with at least one aldehyde, for example formaldehyde, and at least one amine having at least one primary or secondary amine function, one alkylated with polyisobutylene and additionally at least partly aminoalkylated compound. It is also possible to use reaction and / or condensation products of aldehyde and / or amine. The preparation of such compounds are described in WO 01/25293 and WO 01/25294, to which reference is hereby fully made.
  • a polyisobutene (specifically polyisobutene terminated with ethylenically unsaturated groups) prepared according to the process of the invention can be reacted with at least one peroxide compound to give an at least partially epoxidized polyisobutene.
  • the peroxide compound used is at least one peracid, such as m-chloroperbenzoic acid, performic acid, peracetic acid, trifluoroperacetic acid, perbenzoic acid and 3,5-dinitroperbenzoic acid.
  • the preparation of the peracids can be carried out in situ from the corresponding acids and H 2 O 2 optionally in the presence of mineral acids respectively.
  • suitable epoxidizing reagents are, for example, alkaline hydrogen peroxide, molecular oxygen and alkyl peroxides, such as tert-butyl hydroperoxide.
  • suitable solvents for the epoxidation are, for example, conventional, non-polar solvents. Particularly suitable solvents are hydrocarbons such as toluene, xylene, hexane or heptane.
  • the epoxide formed is relatively stable and can then be reacted ring-opening with water, acids, alcohols, thiols or primary or secondary amines to give, inter alia, diols, glycol ether, glycol thioethers and amines.
  • this functionalization route often proceeds with relatively low yields because of steric hindrance at the tertiary carbon atom of the epoxy group.
  • the epoxide is converted to the corresponding carbonyl compound, which can be done, for example, by means of zeolites or Lewis acids, then the carbonyl compounds formed can be derivatized with significantly better yields, for example by subjecting them to reactions (i) to (C) described under (i).
  • the epoxide can be further reacted by reaction with a borane and subsequent oxidative cleavage of the ester formed to give a 2-polyisobutenyl-1,3-propanediol.
  • the reaction with the borane is suitably carried out in a borane-coordinating solvent. Examples include open-chain ethers, such as dialkyl, diaryl or alkylaryl ethers, and cyclic ethers, such as tetrahydrofuran or 1, 4-dioxane.
  • the oxidative cleavage to the 1, 3-diol can be carried out, for example, as described in v).
  • the conversion of the epoxide into a 2-polyisobutenyl-1, 3-propanediol is described for example in EP-A-0737662, which is hereby incorporated by reference.
  • a polyisobutene (specifically polyisobutene terminated with ethylenically unsaturated groups) prepared according to the process of the invention can be subjected to a reaction with a (optionally generated in situ) borane to give an at least partially hydroxylated polyisobutene.
  • Suitable hydroboration processes are described in J. March, Advanced Organic Chemistry, 4th Edition, John Wiley & Sons, pp. 783-789, which is hereby incorporated by reference.
  • Suitable hydroboration reagents are, for example, diborane, which is generally generated in situ by reacting sodium borohydride with BF 3 etherate, diisamylborane (bis [3-methylbut-2-yl] borane), 1,1,2-trimethylpropylborane, 9- Borbicyclo [3.3.1] nonane, diisocamphenylborane, which are obtainable by hydroboration of the corresponding alkenes with diborane, chloroborane-dimethyl sulfide, alkyldichloroboranes or H 3 BN (C 2 Hs) 2 .
  • the hydroboration is carried out in a solvent.
  • suitable solvents for the hydroboration are, for example, acyclic ethers, such as diethyl ether, methyl tert-butyl ether, dimethoxyethane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, cyclic ethers, such as tetrahydrofuran or dioxane, and hydrocarbons. hydrocarbons such as hexane or toluene or mixtures thereof.
  • the reaction temperature is generally determined by the reactivity of the hydroboration and is typically between the melting and boiling point of the reaction mixture, preferably in the range of from 0 ° C to 6O 0 C.
  • the hydroborating agent is used in excess with respect to the alkene.
  • the boron atom preferably adds to the less substituted and thus less sterically hindered carbon atom.
  • the alkyl boranes formed are not isolated, but converted by subsequent reaction directly into the desired products.
  • a very important reaction of the alkyl boranes is the reaction with alkaline hydrogen peroxide to give an alcohol, which preferably corresponds formally to the anti-Markovnikov hydration of the alkene.
  • the resulting alkyl boranes may be subjected to reaction with bromine in the presence of hydroxide ions to give the bromide.
  • a polyisobutene (specifically polyisobutene terminated with ethylenically unsaturated groups) prepared according to the process of the invention can be reacted with at least one alkene which has an electrophile-substituted double bond in an ene reaction (see, for example, DE-A 4 319,672 or H. Mach and P. Rath in "Lubrication Science Il (1999), pp.
  • an alkene having an allyl-containing hydrogen atom designated as En is used an electrophilic alkene, the so-called enophile, in a pericyclic reaction comprising a carbon-carbon bond, a double bond shift, and a hydrogen transfer reaction
  • the polyisobutene reacts as ene.
  • Suitable enophiles are compounds such as dienophiles in the Diels-Alder
  • the enophile used is preferably maleic anhydride at least partially functionalized with succinic anhydride groups (Succinanhydrid tendency) polyisobutenes.
  • the maleic anhydride concentration and the temperature, 70 to 90% of the polymer used is generally functionalized.
  • the double bond newly formed in the polyisobutene chain can then be further functionalized, for example by reaction with maleic anhydride in a renewed ene reaction with attachment of a further succinic anhydride group.
  • the ene reaction may optionally be carried out in the presence of a Lewis acid catalyst.
  • a Lewis acid catalyst Suitable examples are aluminum chloride and ethylaluminum chloride.
  • a polyisobutene derivatized with succinic anhydride groups may be subjected to a subsequent reaction which comprises is chosen under:
  • a polyisobutene (specifically polyisobutene terminated with ethylenically unsaturated groups) prepared by the process according to the invention can be subjected to a reaction with hydrogen halide or a halogen to give a polyisobutene which is at least partially functionalized with halogen groups.
  • Suitable reaction conditions of hydrohalo-addition are described in J. Maren, Advanced Organic Chemistry, 4th Edition, John Wiley & Sons, pp. 758-759, which is incorporated herein by reference.
  • HF, HCl, HBr and Hl are suitable for the addition of hydrogen halide.
  • the addition of HI, HBr and HF can generally be carried out at room temperature, whereas elevated temperatures and / or increased pressure are generally used for the addition of HCl.
  • the addition of hydrogen halides can be carried out in principle in the absence or in the presence of initiators or of electromagnetic radiation.
  • initiators especially peroxides
  • the Markovnikov addition products are generally obtained.
  • peroxides the addition of HBr usually leads to anti-Markovnikov products.
  • halogenation of double bonds is described in J. March, Advanced Organic Chemistry, 4th Edition, John Wiley & Sons, pp. 812-814, incorporated herein by reference.
  • Cl, Br and I the free halogens can be used.
  • interhalogen compounds Fluorine-containing compounds such as CoF 3 , XeF 2 and mixtures of PbO 2 and SF 4 are generally used for the addition of fluorine.
  • Bromine usually adds at room temperature in good yields of double bonds.
  • Chlorine-containing reagents such as SO 2 Cl 2 , PCI 5, etc., can be used in addition to the free halogen.
  • the dihalides formed can be dehydrohalogenated, for example by thermal treatment, to give allyl halide-terminated polymers. If chlorine or bromine is used for the halogenation in the presence of electromagnetic radiation, essentially the products of the radical substitution on the polymer chain are obtained, and not or only to a minor extent addition products to the terminal double bond.
  • the polyisobutene (especially polyisobutene terminated with ethylenically unsaturated groups) can be subjected to a reaction with carbon monoxide and hydrogen in the presence of a hydroformylation catalyst to give an at least partially hydroformylated polyisobutene.
  • Suitable hydroformylation catalysts are known and preferably comprise a compound or a complex of an element of Group VIII of the Periodic Table, such as Co, Rh, Ir, Ru, Pd or Pt.
  • hydroformylation catalysts modified with N- or P-containing ligands are preferably used.
  • Suitable salts of these metals are, for example, the hydrides, halides, nitrates, sulfates, oxides, sulfides or the salts with alkyl or arylcarboxylic acids or alkyl or arylsulfonic acids.
  • Suitable complex compounds have ligands which are selected, for example, from halides, amines, carboxylates, acetylacetonate, aryl or alkylsulfonates, hydride, CO, olefins, dienes, cycloolefins, nitrites, N-containing heterocycles, aromatics and heteroaromatics , Ethers, PF 3 , phospholes, phosphabenzenes and mono-, bi- and multidentate phosphine, phosphinite, phosphonite, phosphoramidite and phosphite ligands.
  • ligands which are selected, for example, from halides, amines, carboxylates, acetylacetonate, aryl or alkylsulfonates, hydride, CO, olefins, dienes, cycloolefins, nitrites, N-containing heterocycles, aromatics and
  • catalytically active species of the general formula H x M y (CO) z L q are formed under hydroformylation conditions from the particular catalysts or catalyst precursors used, where M is a metal of subgroup VIII, L is a ligand and q, x, y , z are integers, depending on the valence and type of metal and the ligand L's binding.
  • the hydroformylation catalysts are prepared in situ in the reactor used for the hydroformylation reaction.
  • Another preferred form is the use of a carbonyl generator in which prefabricated carbonyl z. B. adsorbed on activated carbon and only the desorbed carbonyl hydroformylation is supplied, but not the salt solutions from which the carbonyl is produced.
  • Suitable rhodium compounds or complexes are, for. Rhodium (II) and rhodium (III) salts, such as rhodium (III) chloride, rhodium (III) nitrate, rhodium (III) sulfate, potassium rhodium sulfate, rhodium (II) or Rhodium (II) - carboxylate, rhodium (II) - and rhodium (III) acetate, rhodium (III) oxide, salts of rhodium (III) acid, Trisammoniumhexa- chlororhodat (III), etc.
  • Rhodium complexes such as rhodiumbiscarbo- nylacetylacetonate, acetylacetonato-bis-ethyl rhodium (I), etc.
  • ruthenium salts or compounds are, for example, ruthenium (III) chloride, ruthenium (IV), ruthenium (VI) or ruthenium (VIII) oxide, alkali metal salts of ruthenium oxygen acids such as K 2 RuO 4 or KRuO 4 or complex compounds, such as. B. RuHCl (CO) (PPh 3 ) 3 .
  • metal carbonyls of ruthenium such as trisruthenium dodecacarbonyl or hexaruthenium octadecacarbonyl, or mixed forms in which CO has been partly replaced by ligands of the formula PR 3 , such as Ru (CO) 3 (PPh 3 ) 2 l .
  • Suitable cobalt compounds are, for example, cobalt (II) chloride, cobalt (II) sulfate, cobalt (II) carbonate, cobalt (II) nitrate, their amine or hydrate complexes, cobalt carboxylates, such as cobalt formate, cobalt acetate, cobalt ethylhexanoate, cobalt naphthanoate, and cobalt -Caprolactamat complex.
  • the carbonyl complexes of the cobalt such as dicobalt octacarbonyl, tetracobalt dodecacarbonyl and hexacobalt hexadecarbonyl, can be used.
  • Suitable activating agents which can be used for hydroformylation are, for. B. Bronsted acids, Lewis acids, such as. B. BF 3 , AICI 3 , ZnCl 2 , and Lewis bases.
  • composition of the synthesis gas used from carbon monoxide The composition of the synthesis gas used from carbon monoxide and
  • Hydrogen can vary widely.
  • the molar ratio of carbon monoxide and hydrogen is usually about 5:95 to 95: 5, preferably about 40:60 to 60:40.
  • the temperature in the hydroformylation is generally in a range of about 20 to 200 0 C, preferably about 50 to 190 0 C.
  • the reaction is usually carried out at the partial pressure of the reaction gas at the selected reaction temperature. In general, the pressure is in a range of about 1 to 700 bar, preferably 1 to 300 bar.
  • the carbonyl number of the resulting hydroformylated polyisobutenes depends on the number average molecular weight M n .
  • the majority of the double bonds contained in the medium molecular weight, reactive polyisobutene is converted by the hydroformylation in aldehydes.
  • suitable hydroformylation catalysts and / or an excess of hydrogen in the synthesis gas used the majority of the ethylenically unsaturated double bonds present in the educt can also be converted directly into alcohols. This can also be done in a two-stage functionalization according to the reaction step B) described below.
  • the functionalized polyisobutenes obtained by hydroformylation are advantageously suitable as intermediates for further processing by functionalizing at least part of the aldehyde functions contained in them.
  • the hydroformylated polyisobutenes obtained in step viii) can be reacted with an oxidizing agent to give a polyisobutene which is at least partially functionalized with carboxy groups.
  • oxidizing agents and processes can generally be used, e.g. In J. March, Advanced Organic Chemistry, John Wiley & Sons, 4th edition, p. 701 et seq. (1992). These include z.
  • the oxidation with air can be carried out both catalytically in the presence of metal salts and in the absence of catalysts.
  • metals are preferably used those which are capable of a valency change, such as. As Cu, Fe, Co, Mn, etc.
  • the reaction usually succeeds even in the absence of a catalyst. In the case of air oxidation, the conversion can easily be controlled over the duration of the reaction.
  • the oxidizing agent is an aqueous hydrogen peroxide solution in combination with a carboxylic acid, such as. As acetic acid used.
  • a carboxylic acid such as. As acetic acid used.
  • the acid value of the resulting polyisobutenes having carboxyl function depends on the number average molecular weight M n .
  • the hydroformylated polyisobutenes obtained in step viii) can be subjected to a reaction with hydrogen in the presence of a hydrogenation catalyst to give a polyisobutene which is at least partially functionalized with alcohol groups.
  • Suitable hydrogenation catalysts are generally transition metals such. As Cr, Mo, W, Fe, Rh, Co, Ni, Pd, Pt, Ru, etc., or mixtures thereof, to increase the activity and stability on carriers such. As activated carbon, alumina, diatomaceous earth, etc., can be applied. To increase the catalytic activity Fe, Co, and preferably Ni can also be used in the form of Raney catalysts as metal sponge with a very large surface area.
  • the hydrogenation of the oxo-aldehydes from stage viii) takes place, depending on the activity of the catalyst, preferably at elevated temperatures and elevated pressure.
  • the reaction temperature is about 80 to 150 0 C and the pressure at about 50 to 350 bar.
  • the alcohol number of the obtained hydroxy-containing polyisobutenes depends on the number-average molecular weight M n .
  • the hydroformylated polyisobutenes obtained in step viii) are subjected to further functionalization of a reaction with hydrogen and ammonia or a primary or secondary amine in the presence of an amination catalyst to give a polyisobutene which is at least partially unfunctionalized with amine groups.
  • Suitable amination catalysts are the hydrogenation catalysts described above in step B), preferably copper, cobalt or nickel, which can be used in the form of the Raney metals or on a support. Also suitable are platinum catalysts.
  • Primary and secondary amines suitable for amination are compounds of the general formulas R-NH 2 and RR'NH, where R and R 'are, for example, C 1 -C 10 -alkyl, C 6 -C 2 0-aryl, C 7 -C 2 0-arylalkyl , C 7 -C 2 o-alkylaryl or cycloalkyl.
  • Diamines such as N, N-dimethylaminopropylamine and N 1 N'-dimethylpropylene-i-3-diamine, are also suitable.
  • the amine value of the polyisobutenes with amino function obtained depends on the number average molecular weight M n and on the number of incorporated amino groups.
  • allyl halide-terminated polyisobutenes obtainable by reaction of the living chain ends with a conjugated diene and subsequent hydrolytic work-up can be prepared by reaction with ammonia, primary or secondary amines under such reaction conditions as are suitable for a nucleus. ophile substitution at an allylic center, into the corresponding amine-terminated polymers. Suitable reaction conditions are described, for example, in Jerry March, Advanced Organic Chemistry, 3rd Edition, 1985, John Wiley & Sons, page 364ff.
  • polyisobutenes obtained by the process according to the invention and in particular the bifunctional polyisobutenes serve as macromonomers for further polymerizations, polycondensations, network formation or coupling.
  • they are suitable as precursors for the functionalization reactions i) to x) described above.
  • Preferred functionalization products are polyisobutenes having at least one hydroxyl group, in particular having 2 or 4 hydroxyl groups, with at least one amine group, in particular with 2 amine groups, with at least one thiol group, in particular with 4 or 6 SH groups, with at least one alkoxysilane group, in particular with 2 alkoxysilane groups, with at least one succinic acid group, in particular with 2 succinic anhydride or with 2 succinimide groups, and with at least one phenol group, in particular with 2 phenol groups.
  • the polyisobutenes and especially the difunctional polyisobutenes and their functionalization products are found in adhesives and sealants, in elastomers, e.g. in tire materials, or as mineral oil additives, e.g. in fuels and lubricants, application.
  • Flask A reaction flask
  • Flask B condensation flask
  • Flask A reaction flask
  • Flask B condensation flask
  • the pressure equalization tube of the dropping funnel was provided with a lateral connection with three-way cock. To condense the monomer mixture of the dropping funnel was closed and the three-way valve was set so that only the way to dry ice was released. From a liquefied gas cylinder, 417 ml of raffinate I were passed via a riser pipe via the three-way cock of the pressure equalizing tube of the dropping funnel to the dry ice cooler where it was condensed and collected in the dropping funnel. Then phenanthroline was added as an indicator, the three-way cock of the dropping funnel pressure equalization tube placed on pressure equalization and the contents of the dropping funnel in the condensation piston B, the connection to the piston A was closed, so emptied that a moderate reflux was formed.
  • the monomer mixture was titrated via the septum with a 1, 6 M n-butyl lithium solution in hexane to brown color (10 ml n-BuLi). After 5 minutes, the stopcock was opened to flask A and the monomer mixture of flask B was transferred under heating to flask A, previously dried overnight under a light, dry nitrogen stream, where it condensed on the dry ice condenser.
  • Example 1.1 The polymerization was carried out as in Example 1.1, but the solvent was removed on a rotary evaporator at 10 ° C under reduced pressure. The residue containing the dichloro-terminated polyisobutene was then dissolved in 112 g of tetrahydrofuran and mixed at room temperature with 26 g of potassium tert-butoxide, left for 16 h and then heated to reflux for 1 h. After cooling to room temperature, the mixture was treated with 200 ml of hexane and washed twice with 200 ml of water. Removal of the solvent on a rotary evaporator at 150 ° C. and degassing for 30 minutes at 2 mbar gave an isobutene polymer having the same M n , PDI and viscosity values as in Example 1.1, but with a vinylidene double bond content of 96%.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne un procédé pour produire des polymères d'isobutène, selon lequel un isobutène ou un mélange de monomères contenant un isobutène est polymérisé en présence d'un amorceur et d'un acide de Lewis dans un solvant d'hydrocarbures, lequel contient au moins un hydrocarbure aliphatique insaturé et/ou un hydrocarbure alicyclique insaturé, mais pratiquement pas d'hydrocarbures halogénés ou aromatiques.
PCT/EP2006/000452 2005-01-20 2006-01-19 Procede pour produire un polyisobutene WO2006077117A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005002722.9 2005-01-20
DE200510002722 DE102005002722A1 (de) 2005-01-20 2005-01-20 Verfahren zur Herstellung von Polyisobuten

Publications (1)

Publication Number Publication Date
WO2006077117A1 true WO2006077117A1 (fr) 2006-07-27

Family

ID=35976529

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2006/000452 WO2006077117A1 (fr) 2005-01-20 2006-01-19 Procede pour produire un polyisobutene

Country Status (2)

Country Link
DE (1) DE102005002722A1 (fr)
WO (1) WO2006077117A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008058448A1 (de) 2007-11-23 2009-06-25 Basf Se Polyisobutylderivate als Polymerisationskatalysatoren
DE102009037787A1 (de) 2008-08-19 2010-03-11 Basf Se Hydroborierung von Isobutenpolymeren

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0264214A2 (fr) * 1986-10-16 1988-04-20 Dow Corning Corporation Procédé de préparation de polyisobutène à groupes terminaux allyliques
EP0713883A1 (fr) * 1994-06-09 1996-05-29 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Procede de production d'un polymere d'isobutene
EP0722957A1 (fr) * 1995-01-17 1996-07-24 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Polymère d'isobutylène et procédé de sa préparation
DE19610350A1 (de) * 1996-03-15 1997-09-18 Basf Ag Initiatoren für die anionisch initiierte Polymerisation von wenigstens eine ethylenisch ungesättigte Gruppe aufweisenden Monomeren
WO2001025293A1 (fr) * 1999-10-06 2001-04-12 Basf Aktiengesellschaft Procede de preparation de produits d'addition de mannich contenant du poly-isobutenphenol
WO2002048215A2 (fr) * 2000-12-12 2002-06-20 Basf Aktiengesellschaft Procede de production de polyisobutenes
WO2002079283A1 (fr) * 2001-03-28 2002-10-10 Texas Petrochemicals Lp Polyisobutylene a teneur moyenne de vinylidene et preparation associee
WO2002096964A2 (fr) * 2001-05-25 2002-12-05 Basf Aktiengesellschaft Procede pour realiser des copolymeres et des homopolymeres d'isobutene
WO2003074577A1 (fr) * 2002-03-04 2003-09-12 Basf Aktiengesellschaft Procede de fabrication de polymeres isobutene
DE10209404A1 (de) * 2002-03-04 2003-09-18 Basf Ag Verfahren zur Herstellung von Isobutenpolymeren
DE10232157A1 (de) * 2002-07-16 2004-02-05 Basf Ag Verfahren zur Herstellung von Isobutenpolymeren

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0264214A2 (fr) * 1986-10-16 1988-04-20 Dow Corning Corporation Procédé de préparation de polyisobutène à groupes terminaux allyliques
EP0713883A1 (fr) * 1994-06-09 1996-05-29 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Procede de production d'un polymere d'isobutene
EP0722957A1 (fr) * 1995-01-17 1996-07-24 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Polymère d'isobutylène et procédé de sa préparation
DE19610350A1 (de) * 1996-03-15 1997-09-18 Basf Ag Initiatoren für die anionisch initiierte Polymerisation von wenigstens eine ethylenisch ungesättigte Gruppe aufweisenden Monomeren
WO2001025293A1 (fr) * 1999-10-06 2001-04-12 Basf Aktiengesellschaft Procede de preparation de produits d'addition de mannich contenant du poly-isobutenphenol
WO2002048215A2 (fr) * 2000-12-12 2002-06-20 Basf Aktiengesellschaft Procede de production de polyisobutenes
WO2002079283A1 (fr) * 2001-03-28 2002-10-10 Texas Petrochemicals Lp Polyisobutylene a teneur moyenne de vinylidene et preparation associee
WO2002096964A2 (fr) * 2001-05-25 2002-12-05 Basf Aktiengesellschaft Procede pour realiser des copolymeres et des homopolymeres d'isobutene
WO2003074577A1 (fr) * 2002-03-04 2003-09-12 Basf Aktiengesellschaft Procede de fabrication de polymeres isobutene
DE10209404A1 (de) * 2002-03-04 2003-09-18 Basf Ag Verfahren zur Herstellung von Isobutenpolymeren
DE10232157A1 (de) * 2002-07-16 2004-02-05 Basf Ag Verfahren zur Herstellung von Isobutenpolymeren

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008058448A1 (de) 2007-11-23 2009-06-25 Basf Se Polyisobutylderivate als Polymerisationskatalysatoren
DE102009037787A1 (de) 2008-08-19 2010-03-11 Basf Se Hydroborierung von Isobutenpolymeren

Also Published As

Publication number Publication date
DE102005002722A1 (de) 2006-08-03

Similar Documents

Publication Publication Date Title
EP1483303B1 (fr) Procede de fabrication de polymeres isobutene
EP1641844B1 (fr) Procede de production de polyisobutenes
EP1343829B1 (fr) Procede de production de polyisobutenes
EP2536768B1 (fr) Procédé de production d'homo- ou de copolymères d'isobutène hautement réactifs
EP1347995B1 (fr) Procede de production d'homopolymeres et de copolymeres d'isobutene
EP1590379B1 (fr) Fonctionnalisation de polymeres d'isobutene insatures, par hydroboration
WO2015007553A1 (fr) Polyisobutylène à réactivité élevée et à haute teneur en doubles liaisons vinylidène dans les chaînes latérales
EP1224230A1 (fr) Procede pour la production de polyisobutenes hautement reactifs
EP1495058A1 (fr) Polyisobutene-amines
EP2646478A2 (fr) Préparation de dérivés d'homopolymères ou de copolymères d'isobutène
WO2006077116A1 (fr) Procédé pour produire un polyisobutène
WO2006077117A1 (fr) Procede pour produire un polyisobutene
DE102005038282A1 (de) Verfahren zur Herstellung von Copolymeren aus Isobuten und wenigstens einer vinylaromatischen Verbindung
DE10232157A1 (de) Verfahren zur Herstellung von Isobutenpolymeren
EP2906604A1 (fr) Procédé de production de polyisobutenes
DE102007044933A9 (de) Verfahren zur Herstellung von Polyisobuten
EP1682471B1 (fr) Cycloalcanes substitues et leur utilisation comme initiateurs pour la polymerisation cationique
EP1626997B1 (fr) Procede de production de polyisobutenes termines par un groupe carboxyle
DE10209404A1 (de) Verfahren zur Herstellung von Isobutenpolymeren
WO2007104711A1 (fr) Procédé pour la polymérisation cationique de monomères éthyléniquement insaturés cationiquement polymérisables en présence d'époxy-éthers
WO2007104728A1 (fr) Procédé pour la polymérisation cationique de monomères éthyléniquement insaturés cationiquement polymérisables en présence de produits de dimérisation bisfonctionnalisés du cyclopentadiène ou de ses dérivés
WO2007104727A1 (fr) Alcene substitue en tant qu'amorceur de polymerisation cationique

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application
DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 06706307

Country of ref document: EP

Kind code of ref document: A1

WWW Wipo information: withdrawn in national office

Ref document number: 6706307

Country of ref document: EP