WO2006077116A1 - Procédé pour produire un polyisobutène - Google Patents

Procédé pour produire un polyisobutène Download PDF

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WO2006077116A1
WO2006077116A1 PCT/EP2006/000451 EP2006000451W WO2006077116A1 WO 2006077116 A1 WO2006077116 A1 WO 2006077116A1 EP 2006000451 W EP2006000451 W EP 2006000451W WO 2006077116 A1 WO2006077116 A1 WO 2006077116A1
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isobutene
reaction
polymerization
groups
reaction mixture
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Hans Peter Rath
Heike Pfistner
Arno Lange
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BASF SE
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BASF SE
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    • 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 bifunctional isobutene polymers having a narrow molecular weight distribution.
  • 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 adhesive raw materials or as a basic constituent of sealing and sealing compounds.
  • sealants and sealants or adhesive (raw) materials particularly suitable polyisobutenes are telechel, d. H. 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.
  • telechelic polyisobutenes by living cationic polymerization of isobutene
  • living cationic polymerization is generally referred to the polymerization of iso-olefins or vinyl aromatics in the presence of metal or semi-metal halides as Lewis acid catalysts and tert-alkyl halides, benzyl or allyl halides, esters or ethers as initiators, which with the Lewis Acid form a carbocation or a cationogenic complex.
  • metal or semi-metal halides as Lewis acid catalysts and tert-alkyl halides, benzyl or allyl halides, esters or ethers as initiators, which with the Lewis Acid form a carbocation or a cationogenic complex.
  • a bifunctional initiator such as dicumyl chloride
  • isobutene polymerization in the prior art is carried out at rather low initial concentrations of isobutene, generally replacing used isobutene in the course of the polymerization (so-called incremental monomer addition) .
  • isobutene used is substantially completely reacted.
  • EP-A 722 957 describes the preparation of telechelic isobutene polymers using an at least bifunctional initiator, such as dicumyl chloride, in chlorinated C 3 -C 8 hydrocarbons.
  • the initial concentration of iso- Butene is in the examples below 30 vol .-%.
  • aromatic initiators such as 1,3- and 1,4-dicumyl chloride, can react to form indanyl or diindene groups (cf Cr. Pratrap, SA Mustafa, JP Heller, J. Polym. See Part A, Polym. Chem. 1993, 31, pp.
  • the object of the present invention was to provide a process for the preparation of polyisocyanates, with which predominantly telechelic, especially bifunctional, polyisobutenes are obtained.
  • the polyisobutenes should have a narrow molecular weight distribution (that is, the smallest possible PDI value).
  • the formation of indanes and diindanes should be prevented or at least reduced to obtain a high proportion of bifunctional polyisobutenes.
  • polyisobutenes having a high molecular uniformity and a high proportion of bifunctional polymers are obtained if the isobutene used is not completely reacted in the polymerization and if the halogenated solvent is used in relation to the isobutene used and, if appropriate existing additional solvents used in a relatively small proportion. Even better results are achieved, if one also assumes a high initial isobutene concentration.
  • the object was accordingly achieved by a process for the preparation of isobutene polymers having a number average molecular weight of 270 to 5000, in which isobutene or an isobutene-containing monomer mixture in the presence of an initiator which is selected from 1, 3-bis (2) chloro-2-propyl) benzene (1,3-dicumyl chloride; 1, 3-DCC) and 1,4-bis (2-chloro-2-propyl) benzene (1,4-dicumyl chloride; 1,4-DCC), and a Lewis acid in a solvent polymerized, characterized in that
  • the solvent contains halogenated hydrocarbon solvent in such an amount that the reaction mixture at the beginning of polymerization has a relative dielectric constant of not more than 6.5 at -76 0 C;
  • the beginning of polymerization in the context of the present invention in a discontinuous reaction regime is that time at which all components essential for the polymerization reaction, ie the monomers to be polymerized (isobutene or the isobutene-containing monomer mixture), the initiator and the Lewis acid, at least partially contained in the reaction vessel and the Isobutenumsatz is imminent.
  • this is understood to mean that point in time at which the component streams, which are essential for the polymerization, meet in the reaction zone.
  • the dielectric constant of the reaction mixture is understood to be at or shortly after the feed of those component which is last fed (generally the Lewis acid).
  • halogenated hydrocarbon solvents are understood as meaning aliphatic or alicyclic saturated or unsaturated as well as aromatic hydrocarbons in which at least one hydrogen atom has been replaced by a halogen atom, preferably chlorine and / or fluorine and especially chlorine.
  • a halogen atom preferably chlorine and / or fluorine and especially chlorine.
  • Halogenated CrC ⁇ alkanes more preferably chloroated alkanes, e.g. For example, chlorinated C ⁇ Ca alkanes, and in particular chlorinated C r C 4 alkanes.
  • methyl chloride methyl chloride, methylene chloride, chloroform, chloroethane, 1, 1 and 1, 2-dichloroethane, 1,1,1- and 1, 1, 2-trichloroethane, 1, 1,1, 2- and 1, 1, 2,2-tetrachloroethane, 1- and 2-chloropropane, 1,1-, 1, 2-, 1, 3- and 2,2-dichloropropane, 1, 1, 1, 1, 1, 1,2-, 1, 2,2- and 1,2,3-trichloropropane, 1- and 2-chlorobutane, 1,1,2-, 1,2-, 1,3- and 2,2-dichlorobutane, 1,1,1-trichlorobutane and the like , Particular preference is given to halogenated C 1 -C 2 -alkanes, such as methyl chloride, methylene chloride, chloroform, chloroethane, dichloroethane, trichloroethane and tetrachloroethane, and mixtures thereof.
  • chlorinated Q 1 -alkanes having 1 or 2 chlorine atoms such as methyl chloride, methylene chloride, chloroethane, 1,1- or 1, 2-dichloroethane and mixtures thereof.
  • Halogenated C r alkanes such as methyl chloride, methylene chloride or chloroform, and in particular chlorinated C r alkanes having 1 or 2 chlorine atoms, such as methyl chloride and methylene chloride, and mixtures thereof are even more preferred, especially because of their favorable solution viscosity and heat transfer.
  • halogenated, especially chlorinated C 3 -C 6 alkanes having 1 to 4 chlorine atoms such as 1- and 2-chloropropane, 1, 1, 1,2, 1,3 and 2,2-dichloropropane, 1, 1,1-, 1,1,2-, 1,2,2- and 1,2,3-trichloropropane, 1,1,1, 2- and 1,1,2,2-tetrachloropropane, 1- and 2 Chlorobutane, 1,1-, 1,2-, 1,3- and 2,2-dichlorobutane and 1,1,1-trichlorobutane, and mixtures thereof are particularly preferred.
  • chlorinated C 3 -C 6 -alkanes having one chlorine atom and in particular chlorinated C 3 -C 4 -alkanes having one chlorine atom, such as 1- and
  • the halogenated hydrocarbon is usually used in admixture with other hydrocarbon solvents (co-solvents).
  • hydrocarbon solvents co-solvents
  • examples include aliphatic or alicyclic saturated or unsaturated and aromatic hydrocarbons.
  • hydrocarbons are understood as meaning organic molecules which 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 halogen.
  • 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 which contain less than 0.01% by weight of heteroatoms, based on the total weight of the hydrocarbons used.
  • Saturated aliphatic hydrocarbons are alkanes. Preference is given here to C 4 -C 10 -alkanes and in particular C 4 -C 8 -alkanes.
  • C 4 -C 8 -alkanes are, for example, butane, isobutane, pentane, hexane, heptane and octane and also their constitutional isomers.
  • C 4 -C 0 are alkanes beyond nonane, and decane and their constitutional isomers.
  • Saturated alicyclic hydrocarbons are e.g. B. cycloalkanes. Preference is given to C 5 -C 8 -cycloalkanes and in particular C 5 -C 6 -cycloalkanes. examples for
  • C 5 -C 6 -cycloalkanes are cyclopentane and cyclohexane.
  • C 5 -C 8 cycloalkanes further include, for example, cycloheptane and cyclooctane.
  • 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 (i.e., cyclic, non-aromatic) hydrocarbons having at least one olefinic double bond. For multiple double bonds, these may be conjugated or isolated in the molecule.
  • the unsaturated aliphatic hydrocarbons are preferably alkenes, for. B. C 2 -C 10 alkenes, alkadienes, z. C 4 -C 10 alkadienes, or alkatrienes, e.g. C 6 -C 10 alkatrienes, or mixtures thereof. Particularly preferred are C 2 -C ⁇ - alkenes, C 4 -C 6 -alkadienes and mixtures thereof.
  • C 2 -C 10 alkene is a monounsaturated linear or branched hydrocarbon of 2 to 10 carbon atoms.
  • examples of these are ethene, propene, 1-butene, 2-butene, isobutene, 1-pentene, 2-pentene, 1-hexene, 2-hexene, 3-hexene, 1-heptene, 2-heptene, 3-heptene, 1 Octene, 2-octene, 3-octene, 4-octene, 1, 2, 3, 4-nonene, 1, 2, 3, 4 and 5-decene and constitutional isomers thereof.
  • C 2 -C 6 -alkene is a monounsaturated linear or branched hydrocarbon having 2 to 6 carbon atoms. Examples 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
  • 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.
  • the unsaturated alicyclic hydrocarbons are preferably cycloalkenes, e.g. B. C 5 -C 6 alkenes, such as cyclopentene or cyclohexene, or cycloalkadienes, z.
  • Cs-C ⁇ -alkadienes such as cyclopentadiene or cyclohexadiene. It goes without saying that the alicyclic compounds do not have so many conjugated double bonds that an aromatic system is present.
  • Aromatic hydrocarbons are hydrocarbons containing an aromatic system, such as benzene. Suitable aromatic hydrocarbons as solvents may also be substituted. Examples of these are toluene, nitrobenzene, chlorobenzene, dichlorobenzene and the like.
  • Preferred cosolvents are selected from aliphatic hydrocarbons, in particular alkanes, eg. B. C 4 -C 0 alkanes, and alkenes, z. B.
  • alkenes are 1-alkenes and isoalkenes.
  • Particularly preferred cosolvents are selected from C 4 -C 8 -alkanes and C 2 -C 6 -alkenes, which may each be present in admixture with C 4 -C 6 -alkadienes.
  • Examples of suitable C 2 -C 6 -alkenes are ethene, propene, 1- and 2-butene, isobutene, 1- and 2-pentene, 1, -2- and 3-hexene and their constitution isomers and mixtures of these alkenes.
  • Examples of suitable C 4 -C 8 -alkanes are butane, isobutane, pentane, hexane, heptane, octane and their constitution isomers and mixtures of these alkanes.
  • C 4 -C 6 -alkadienes examples include butadiene, 1,3- and 1, 4-pentadiene, 1, 3, 1, 4 and 2, 4-hexadiene and their constitutional isomers, and also 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 .-%, more preferably at most 0.5 wt .-%, more preferably at most 0.2 wt %, in particular not more than 0.05% by weight, especially not more than 0.02% by weight, relative to the total weight of the co-solvent.
  • the co-solvent used is C 4 -C 8 -alkanes and especially hexane or heptane.
  • preferred co-solvents are selected from technical mixtures of aliphatic hydrocarbons.
  • Preferred technical mixtures are C 4 -hydrocarbon mixtures, ie mixtures containing hydrocarbons with 4 carbon atoms, such as butane, isobutane, 1-butene, 2-butene, isobutene and butadiene.
  • Examples include C 4 raffinates, C 4 cuts from isobutane dehydrogenation, C 4 cuts from steam crackers, FCC (Fluid Catalyzed Cracking) crackers, especially if it at least partially freed from 1, 3-butadiene contained therein are.
  • Suitable C 4 -hydrocarbon mixtures preferably contain at most 1% by weight, more preferably at most 0.5% by weight, more preferably at most 0.2% by weight, in particular at most 0.05% by weight, especially at most 0, 02 wt .-%, butadiene, based on the total weight of the mixture.
  • isobutene Since isobutene is not completely polymerized in the process according to the invention, it always acts as a cosolvent. Isobutene is not used as a pure substance, but in admixture with other components, as well as the other components of this mixture, unless they are reacted in the polymerization reaction, act as cosolvent.
  • the solvent contains, in addition to the cosolvents resulting from the provision of the monomer (ie, excess isobutene or, if mixtures containing isobutene are used as the monomer source, also the other components of this mixture), further cosolvents - tel in an amount of at most 10 wt .-%, preferably of at most 5 wt .-% and in particular of at most 1 wt .-%, based on the total weight of the reaction mixture.
  • the cosolvents resulting from the provision of the monomer ie, excess isobutene or, if mixtures containing isobutene are used as the monomer source, also the other components of this mixture
  • further cosolvents - tel in an amount of at most 10 wt .-%, preferably of at most 5 wt .-% and in particular of at most 1 wt .-%, based on the total weight of the reaction mixture.
  • the solvent contains no further cosolvents besides the cosolvents resulting from the provision of the monomer; that is, the solvent comprises, in addition to surplus isobutene and optionally other components of the monomer source, which are not polymerized, and optionally the halogenated solvent, no further co-solvent.
  • the relative dielectric constant ⁇ r which is temperature- and pressure-dependent, indicates how many times the capacitance C of a (theoretically) vacuum condenser increases, if a dielectric (substance with dielectric properties) is placed between its plates:
  • ⁇ r C (with dielectric) / C (vacuum)
  • the relative dielectric constant is a measure of the polarizability or polarity of a substance.
  • the values of the relative dielectric constant at certain temperatures are determined, or they may be made known from the literature values (generally higher) at other temperatures were determined to be extrapolated.
  • Information on relative dielectric constants and their determination and for extrapolation to a specific temperature and for calculating the dielectric constants of mixtures can be found, for example, in Handbook of Chemistry and Physics (CRC Press, 76th Edition, 1995- 1996, Section 6-159 et seq ) and in Properties of Matter in their Physical States, Part 6, Electrical Properties I 1 Published by: KH Hellwege and AM Hellwege, Springer-Verlag 1959, pages 614 ff, to which reference is hereby fully made.
  • the values for dielectric constants always refer to the lowest numerical value in the case of a plurality of divergent values.
  • the desired relative dielectric constants of the reaction mixtures can either be determined and set experimentally, or they can be calculated according to the volume mixing rule from the relative dielectric constants of the individual components of the mixture. Conversely, a desired relative dielectric constant of the reaction mixture can be achieved by determining, by means of the volume mixing rule, in which ratio the individual components of the reaction mixture have to be used.
  • the temperature -76 0 C was chosen because on the one hand isobutene polymerizations to suppress side reactions are often carried out at low temperatures and on the other hand, this temperature can be set technically easy to start polymerization (dry ice cooling).
  • the value of the relative dielectric constant can be readily related to other temperatures, e.g. By extrapolation or experimentally.
  • the solvent contains halogenated hydrocarbon solvents in such an amount that the relative dielectric constant of the reaction mixture at -76 0 C at most 6, z. B. 3 to 6, preferably 4 to 6 or 4.5 to 6, more preferably at most 5.5, z. B. 3 to 5.5, preferably 4 to 5.5 or 4.5 to 5.5, and in particular at most 5, z. B. 3 to 5, preferably 4 to 5 or 4.5 to 5, is.
  • the isobutene to be polymerized can be present both in the form of isobutene itself and in the form of isobutene-containing C 4 -hydrocarbon mixtures, ie mixtures containing, in addition to isobutene, further hydrocarbons having 4 carbon atoms, such as butane, isobutane , 1-butene, 2-butene and butadiene.
  • C 4 -hydrocarbon mixtures are, for example, raffinate I and C 4 cuts from FCC crackers or from isobutane dehydrogenation.
  • Raffinate I is a C 4 hydrocarbon stream having approximately the following composition: 0-5% isobutane; 4-12% n-butane; 35-55% isobutene; 15-55% 1-butene; 10-25% 2-butene and 0-0.5% 1,3-butadiene.
  • C 4 cuts from FCC crackers have approximately the following composition: 5-15% n-butane, 15-25% isobutane, 14-18% isobutene, 15-25% trans-but-2-ene, 10-20 % cis-but-2-ene and 10- 20% 1-butene.
  • C 4 cuts from the isobutane dehydrogenation have approximately the following composition: 45-55% isobutene, 40-50% butane and 2-10% 1- and 2-butenes.
  • the process according to the invention is also suitable for the block copolymerization of isobutene with ethylenically unsaturated comonomers polymerizable under cationic polymerization conditions.
  • 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 wt .-%, and in particular less than 5 wt .-% 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-ethylpentene-1,2-ethylhexene-1 and 2-propylheptene-1.
  • Suitable comonomers are 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.
  • 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 block polymerization can be z.
  • B. first homopolymerize isobutene and enforce the comonomer in due course. The thereby emerging 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.
  • Covalent metal halides and semimetallic halides having an electron-pair gap may be considered as the Lewis acid.
  • Such compounds are known in the art, for example from JP. Kennedy et al. in US 4,946,889,
  • 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.
  • a mixture of at least two Lewis acids can be used, for example boron trichloride mixed with 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 pyranines such as pyridine itself, 2,6-dimethylpyridine, and sterically hindered pyridines such as 2,6-diisopropylpyridine and 2,6-di-tert-butylpyridine; Amides, in particular N, N-dialkylamides of aliphatic or aromatic carboxylic acids such as N, N-dimethylacetamide; Lactams, in particular N-alkyl lactams such as N-methylpyrrolidone; Ethern, z.
  • Dialkyl ethers such as diethyl ether and diisopropyl ether, cyclic ethers such as tetrahydrofuran; Amines, in particular trialkylamines such as triethylamine; Esters, in particular C r C 4 alkyl esters aliphatic
  • C r C 6 carboxylic acids such as ethyl acetate; Thioethers, in particular dialkylthioethers or alkylarylthioethems, such as methylphenylsulfide; Sulfoxides, in particular dialkyl sulfoxides, such as dimethyl sulfoxide; Nitriles, in particular alkylnitriles such as acetonitrile and propionitrile; Phosphines, in particular trialkylphosphines or triarylphosphines, such as tri- methylphosphine, triethylphosphine, tri-n-butylphosphine and triphenylphosphine and non-polymerizable aprotic organosilicon compounds which have at least one oxygen-bonded organic radical.
  • Thioethers in particular dialkylthioethers or alkylarylthioethems, such as methylphenylsulfide
  • Sulfoxides in particular dialky
  • 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 understood as meaning 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.
  • Aryl is an aromatic hydrocarbon radical having usually 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. ToIyI, isopropylphenyl, xylene or tert-butylphenyl.
  • Cycloalkyl here means a generally 5-, 6- or 7-membered, saturated carbocycle which may optionally have one or more C 1 -C 4 -alkyl groups as substituents.
  • 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, for. B. for benzyl or 2-phenylethyl.
  • Alkyloxy is alkyl bound via an oxygen atom. Accordingly, aryloxy, cycloalkyloxy and arylalkyloxy are aryl, cycloalkyl or arylalkyl bonded via an oxygen atom.
  • Acyloxy is an oxygen-bonded alkylcarbonyl radical which preferably has 1 to 6 carbon atoms in the alkyl moiety, eg. B. for acetyloxy, propionyloxy, butyroxy etc.
  • the organosilicon compounds may be one or more, for. B. 2 or 3, silicon atoms having 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 a r Si (ORV
  • r 1, 2 or 3
  • R a may be the same or different and are independently C 1 -C 2 O-AIKyI, C 3 -C 7 cycloalkyl, aryl or AlyI-C 1 -C 4 -alky I, where the latter three radicals also one or more CrC ⁇ alkyl groups may have as substituents, and
  • R b are identical or different and denote or C 1 -C 2O -alkyl that r is the case for 1 or 2, two radicals R b may represent alkylene together.
  • R a is preferably a C 1 -C 6 -alkyl group, and in particular a branched or secondary C-bonded alkyl group, such as isopropyl, isobutyl, sec-butyl, or a 5-, 6-alkyl group or 7-membered cycloalkyl group, or an aryl group, in particular phenyl.
  • the variable R b is preferably a C r C 4 alkyl group or a phenyl, To lIy- or benzyl radical.
  • Examples of such preferred compounds are dimethoxydiisopropylsilane, dimethoxyisobutylisopropylsilane, dimethoxydiisobutylsilane, 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 8 -alkyl represents pentyl, hexyl, heptyl, octyl and their positional isomers.
  • C 1 -C 10 -alkyl represents nonyl and decyl and their positional isomers.
  • C 1 -C 2O -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 6 -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 C 10 alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl and their constitutional isomers.
  • Preferred alkyl radicals are d-Ce-alkyl radicals, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl and their constitution 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 halides examples include tetramethylammonium fluoride, tetramethylammonium chloride, tetramethylammonium bromide, tetraethylammonium fluoride, tetraethylammonium chloride, tetraethylammonium bromide, tetrapropylammonium fluoride,
  • the polymerization can be carried out both batchwise (batchwise) and in a continuous mode.
  • the initial content of isobutene is therefore preferably at least 50% by weight, more preferably at least 60% by weight, more preferably at least 65% and especially at least 70% by weight, e.g. B. at least 80 wt .-%, based on the total weight of the reaction mixture.
  • the isobutene content at the feed point here is preferably at least 50% by weight, more preferably at least 60% by weight, more preferably at least 65% and in particular at least 70% by weight, eg. B. at least 80 wt .-%, based on the total weight of the located at the level of the feed point reaction mixture.
  • the isobutene used is not completely polymerized, but converted to at most 80 wt .-%.
  • at most 60% by weight, particularly preferably at most 50% by weight, more preferably at most 40% by weight, in particular at most 35% by weight and especially at most 30% by weight of the isobutene used is polymerized. Due to the incomplete conversion (partial conversion) of the isobutene used, the molar ratio of isobutene to initiator is particularly large at the beginning of the polymerization, which increases the likelihood of indan formation from initiator and the first and / or second added isobutene. butenmolekül is reduced by intramolecular ring closure. In addition, the partial sales also means that the isobutene used always acts as a solvent.
  • the reduced content of halogenated hydrocarbons in the reaction mixture also contributes to the reduction of indan formation.
  • the amount of halogenated hydrocarbon solvent to be used depends on the one hand on its relative dielectric constant and on the other components of the reaction mixture and especially on their contribution to the dielectric constant of the entire reaction mixture and can be determined experimentally or by calculation by a person skilled in the art.
  • the halogenated hydrocarbon solvent has a relative dielectric constant at 293.5K of greater than or equal to 8, e.g. B. from 8 to 11, such as methyl chloride, methylene chloride, dichloroethane, tetrachloroethane, 1-chloropropane, 1, 2, 1,3- and 2,2-dichloropropane, 2-chlorobutane and 1, 4-dichlorobutane, then the halogenated hydrocarbon in an amount of preferably at most 35% by weight, more preferably at most 30% by weight, more preferably at most 25% by weight, even more preferably at most 20% by weight, especially at most 15% by weight .-% and especially of at most 10 wt .-%, based on the total weight of the reaction mixture used.
  • 8 to 11 such as methyl chloride, methylene chloride, dichloroethane, tetrachloroethane, 1-chloropropane, 1, 2, 1,3- and 2,2-dichloropropane
  • 8 to 11 such as methyl chloride, methylene chloride, dichloroethane, tetrachloroethane, 1-chloropropane, 1, 2-, 1, 3- and 2,2-dichloropropane, 2-chlorobutane and 1, 4-dich
  • the polymerization it is also possible to carry out the polymerization so that no electron donor or alkyl ammonium halide is used or these are used in only small amounts, eg. B. in a total amount of at most 10 mmol / l, based on the total volume of the reaction mixture.
  • the halogenated solvent in a molar ratio to the initiator of preferably 20: 1 to 1: 1.
  • the halogenated hydrocarbon solvent has a relative dielectric constant at 293.5 K of less than 8, e.g. From about 5 to 7.9, such as chloroform, trichloroethane, 1,2,3-trichloropropane, 1-chlorobutane, 1,2-dichlorobutane, 1-chloropentane and 1-chlorohexane, the halogenated hydrocarbon is used in an amount of preferably at most 60 wt .-%, more preferably of at most 55 wt, based on the total weight of the reaction mixture.
  • the halogenated solvent having a relative dielectric constant at 293.5 K of less than 8 e.g. From about 5 to 7.9, such as chloroform, trichloroethane, 1,2,3-trichloropropane, 1-chlorobutane, 1, 2-dichlorobutane, 1-chloropentane and 1-chlorohexane, in an amount of 20 to 60 wt .-%, preferably from 40 to 60 wt .-%, particularly preferably from 45 to 60 wt .-%, in particular from 45 to 55 wt .-%, based on the total weight of the reaction mixture used.
  • chloroform such as chloroform, trichloroethane, 1,2,3-trichloropropane, 1-chlorobutane, 1, 2-dichlorobutane, 1-chloropentane and 1-chlorohexane
  • the polymerization it is also possible to carry out the polymerization so that no electron donor or alkylammonium halide is used or these are used in only small amounts, for. B. in a total amount of at most 10 mmol / l, based on the total volume of the reaction onsgemischs.
  • the halogenated solvent in a molar ratio to the initiator of preferably 20: 1 to 1: 1.
  • the polymerization may even be carried out in a system which contains substantially no halogenated hydrocarbon solvents.
  • the term "contains substantially no halogenated hydrocarbon solvents" means that the reaction mixture is less than 2 wt%, preferably less than 1 wt%, more preferably less than 0.5 wt%, even more preferably less as 0.1% by weight and in particular less than 0.05% by weight, for example less than 0.01% by weight, of halogenated hydrocarbon solvents, based on the total weight of the reaction mixture in particular, when the polymerization is carried out in the presence of an electron donor and / or an alkylammonium halide.
  • 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 5: 1 to 1: 5, more preferably 2: 1 to 1: 5, and especially 1: 5: 1 to 1: 4.
  • the initial concentration of the Lewis acid in the reaction mixture (ie the amount used) is preferably in the range from 5 to 200 mmol / l, particularly preferably 10 to 100 mmol / l and in particular 10 to 80 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. Specifically, when using a boron trichloride / titanium tetrachloride mixture, the molar ratio of boron trichloride to titanium tetrachloride Rachlorid preferably 1, 5: 1 to 100: 1, more preferably 2: 1 to 20: 1 and in particular 5: 1 to 10: 1.
  • the initiator used in the process according to the invention is 1,3- or 1,4-dicumyl chloride, preference being given to 1,4-dicumyl chloride.
  • the initiator is preferably used in an amount of 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 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 maximum amount of initiator is preferably 100 mmol / l, in particular 70 mmol / l, based on the total volume of the reaction mixture.
  • the molar ratio of Lewis acid to electron donor is generally 20: 1 to 1:10, preferably 10: 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 60 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 organoaluminum compound
  • the solvent thus treated is then condensed directly into the reaction vessel.
  • the monomers to be polymerized in particular the isobutene or isobutene-containing mixtures.
  • the halogenated solvent is correspondingly freed from water (traces) with suitable drying agents, for example with calcium chloride, phosphorus pentoxide or molecular sieve.
  • suitable drying agents for example with calcium chloride, phosphorus pentoxide or molecular sieve.
  • 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 isobutene-containing feed occurs spontaneously upon mixing of the initiator system (i.e., Lewis acid and initiator) with the isobutene or isobutene-containing feed at the desired reaction temperature.
  • the initiator system i.e., 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 a start of polymerization by protons.
  • the discontinuous procedure described here can be carried out, for example, by first initially introducing the initiator and optionally the electron donor and / or the alkylammonium halide in the solvent, then the isobutene or the isobutene-containing starting material and then the Lewis acid admits. The beginning of polymerization is then the point in time at which all components of the initiator system are at least partially contained in the reaction vessel.
  • the polymerization can also be designed as a continuous process.
  • the feedstocks ie the monomers to be polymerized
  • the solvent and the initiator system of the polymerization reaction are added continuously and the reaction product is withdrawn continuously, so that more or less stationary polymerization conditions are established in the reactor.
  • 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 used ren and / or alkylammonium halides 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 admixture 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 relate to the stationary polymer concentration or to the polymer concentration in the reactor discharge or in the case of polymerization termination.
  • the inventive method at temperatures in the range of 60 to -140 0 C, preferably in the range of 0 to -120 0 C, more preferably in the range of -30 to -80 ° C and especially in the range of -40 perform to -70 0 C.
  • 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 even 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 batchwise as well as in the continuous reaction is carried out in a conventional manner, for example by internally or externally installed heat exchangers and / or by wall cooling and / or taking advantage of a Siedekühlung.
  • reaction vessels for carrying out the process according to the invention are in principle all reactors into consideration, as they usually in a cationic see polymerization of isobutene, z.
  • a cationic polymerization of isobutene with boron trifluoride-oxygen complexes are used.
  • the stirred tanks customary for this purpose come into consideration, which are preferably equipped with evaporative cooling, suitable mixers, feeds, heat exchanger elements and inerting devices.
  • the continuous reaction can be carried out in customary reaction vessels, reaction cascades, tubular reactors, tube bundle reactors, in particular circularly guided tube and tube bundle reactors, which are preferably described in the above for stirred tank Are equipped.
  • a particularly preferred reactor type is the helical tube reactor described, for example, in EP-A-1 395 620.
  • 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.
  • telechelic (bifunctional) polyisobutenes which contain a functional group at both termini (chain ends).
  • This functional group is preferably a group -CH 2 -C (CH 3 ) 2 -halogen.
  • the halogen atom in this terminal group is usually derived from the initiator used for the polymerization.
  • halogen is chlorine.
  • the derivatization include the alkylation of phenols and the elimination of hydrogen halide from the group -CH 2 -C (CH 3 ) 2 -halogen to form an ethylenically unsaturated terminal group.
  • the conversion of the terminal group -CH 2 -C (CH 3 ) 2 -halogen into an ethylenically unsaturated radical (methylidene double bond) can be carried out, for example, thermally, for. B. by heating to a temperature of 70 to 200 0 C, preferably under vacuum, or by treatment with a base.
  • Suitable bases are, for.
  • sodium ethoxide or potassium tert-butoxide is used.
  • Suitable termination reagents are, for example, trialkylallylsilane compounds, e.g. B. trimethylallylsilane.
  • 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 at the end of the chain is inserted.
  • leads cf. J. Feldthusen, B. Ivan, AHE Mueller and J. Kops, Macromol. Rep. 1995, A32, 639, J. Feldthusen, B. Ivan and AHE Müller, Macromolecules 1997, 30, 6989 and Macromolecules 1998, 31, 578, DE-A 19648028 and DE-A 19610350.
  • conjugated dienes e.g. As butadiene, suitable as termination reagents.
  • 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 such that two or more polymer chains become one molecule.
  • the molecules obtained by coupling are symmetrical telechelic or star-shaped molecules whose further living chain ends must be terminated according to one of the methods described above.
  • By coupling of living copolymers of the type AB + can be z.
  • B. produce triblock copolymers of the type AB-BA, wherein A is a isobutenblock for poly and B for a different polymer block, for.
  • Suitable coupling agents include, for example, at least two electrolytic leaving groups arranged allyl to the same or different double bonds, e.g. As trialkylsilyl groups, so that the cationic center of a reactive chain end can accumulate 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, z. As a proton, then forming the formation of a stable ⁇ 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 C r C 10 alkylene, preferably methylene or 2,2-propanediyl
  • 1,1-bis (trialkylsilylmethyl) ethylene e.g. 1,1-bis (trimethylsilylmethyl) ethylene
  • bis [(trialkylsilyl) propenyl] benzenes e.g. B.
  • 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.
  • polymeric products which predominantly, d. H. at least 90%, preferably at least 95%, more preferably at least 98% of bifunctional polyisobutenes, d. H. from polyisobutenes having two halo termini or having two ethylenically unsaturated (vinyl or vinylidene) termini or having two allyl chloride termini.
  • the process according to the invention is generally used for the preparation of polyisobutenes having a number average molecular weight M n of from 270 to 5,000, preferably from 380 to 5,000 and in particular from 500 to 5,000.
  • the isobutene polymers prepared according to the invention are terminated at the chain ends by a group -CH 2 -C (CH 3 ) 2 -halogen, particularly preferably by -CH 2 -C (CH 3 ) 2 -CI.
  • the groups at the chain ends are preferably ethylenically unsaturated groups which, as described above, are thermal or by reaction of the halogen-substituted chain ends with a suitable base or by reacting the living polyisobutene chains formed in the polymerization with a trialkylallylsilane compound having 1,1-diphenylethylene or a conjugated diene.
  • polyisobutenes obtained according to the invention can furthermore be subjected to the following functionalization reactions:
  • 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. B. 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. B. Tetramethyldivinyldisiloxan-platinum complexes.
  • Suitable rhodium catalysts are, for example, (RhCl (P (C 6 H 5 ) 3 ) 3 ) and RhCl 3 . Also suitable are RuCl 3 and IrCl 3 .
  • Suitable catalysts are also Lewis acids such as AICI 3 or TiCl 4 and peroxides. It may be advantageous to use combinations or mixtures of the aforementioned catalysts.
  • Suitable silanes are, for. Halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane and trimethylsiloxydichlorosilane; Alkoxysilanes such as methyldimethoxysilane, phenyldimethoxysilane, 1,3,3,5,5,7,7-heptamethyl-1,1-dimethoxytetrasiloxane and trialkoxysilanes, e.g. B. trimethoxysilane and triethoxysilane, and acyloxysilanes. Trialkoxysilanes are preferably used.
  • the reaction temperature in the silylation is preferably in a range of 0 to 140 0 C, more preferably 40 to 120 0 C.
  • the reaction is usually carried out under atmospheric pressure, but can also at elevated pressures, such as. B. in the range of about 1, 5 to 20 bar, or reduced pressures such. B. 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 according to the process of the invention can be reacted with hydrogen sulfide or a thiol, such as alkyl- or arylthiols, hydroxymercaptans, aminomercaptans, thiocarboxylic acids or silanethiols to give at least in part thio groups be subjected to functionalized polyisobutene.
  • 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.
  • 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, protonic 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 take place 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 included. for example, in J. Maren, Advanced Organic Chemistry, 4th edition, John Wiley & Sons, pp. 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, phloroglucinol 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 is 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 VAIC 2 HsCl 21 FeCl 3 , SbCl 5 UfTd SbF 5 . These alkylation catalysts can be used together with a cocatalyst, for example an ether.
  • Suitable ethers are di (C r 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, such as anisole. If a catalyst-cocatalyst complex is used for Friedel-Crafts alkylation, the molar ratio of catalyst to cocatalyst is preferably in the range from 1:10 to 10: 1.
  • the reaction can also be catalyzed with protic acids such as sulfuric acid, phosphoric acid, methanesulfonic acid or trifluoromethanesulfonic acid.
  • protic acids such as sulfuric acid, phosphoric acid, methanesulfonic acid or trifluoromethanesulfonic acid.
  • Organic protic acids can also be bound in polymer Form present, for example, as an 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 + 100 0 C.
  • the reaction is usually carried out at atmospheric pressure, but may also be carried out at higher pressures (eg, for 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 (polyisobutene terminated in particular with ethylenically unsaturated groups) prepared according to the process according to the invention can be reacted with at least one peroxide compound to give an at least partially epoxidized polyisobutene.
  • Suitable methods for epoxidation are described in J. March, Advanced Organic Chemistry, 4th Edition, John Wiley & Sons, S. 826-829, incorporated herein by reference.
  • At least one peracid such as m-chloroperbenzoic acid, performic acid, peracetic acid, trifluoroperacetic acid, perbenzoic acid and 3,5-dinitroperbenzoic acid, is preferably used as the peroxide compound.
  • 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.
  • suitable epoxidation reagents are, for example, alkaline hydrogen peroxide, molecular oxygen and alkyl peroxides such as tert-butyl hydroperoxide.
  • suitable solvents for epoxidation are, for example, Wise conventional, non-polar solvent. Particularly suitable solvents are hydrocarbons such as toluene, xylene 1 hexane or heptane.
  • the epoxide formed is relatively stable and can then be reacted ring-opening with water, acids, alcohols, thiols or primary or secondary amines to give, inter alia, diols, glycol ethers, glycol thioethers and amines.
  • this functionalization route often proceeds with relatively low yields due to 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 the reactions A) to C) described under ix).
  • the epoxide can be further reacted by reaction with a borane and subsequent oxidative cleavage of the ester formed to a 2-polyisobutenyl-1, 3-propanediol.
  • Suitable boranes are z.
  • diborane (B 2 H 6 ) and alkyl and aryl boranes RBH 2 (R alkyl or aryl).
  • 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 z.
  • EP-A-0737662 which is hereby incorporated by reference in its entirety.
  • 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 -Ethera 1: _Djis_amyjboran (bis- [3-methylbut-2-yl] borane),. _ ._ - 1,1,2-Trimethylpropylborane, 9-Borbicyclo [3.3.1] nonane, diisocamphenylborane obtainable by hydroboration of the corresponding alkenes with diborane, chloroborane-dimethylsulfide, 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, such as hexane or toluene, or mixtures thereof.
  • the reaction temperature is usually determined by the reactivity of the hydroborating agent and is normally between the melting and boiling point of the reaction mixture, preferably in the range of 0 0 C to 60 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 by the process according to 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 US Pat
  • an alkene designated as En having an allyl-containing hydrogen atom with an electrophilic alkene the so-called enophile, reacted in a pericyclic reaction comprising a carbon-carbon bond, a double bond shift and a hydrogen transfer
  • the polyisobutene reacts as En.
  • Suitable enophiles are compounds such as those used as dienophiles in the Diels-Alder reaction Depending on the molecular weight and the double bond type of the polyisobutene used, the maleic anhydride concentration and the temperature, as a rule from 70 to 90% of the polymer used is obtained func nilized. If desired, the double bond newly formed in the polyisobutene chain can then be further functionalized, for example by reaction. with maleic anhydride in a further ene reaction with attachment of another 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 to a subsequent reaction which is selected from: a) reaction with at least one amine to give a polyisobutene which is at least partially functionalized with succinimide groups and / or succinamide groups,
  • 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.
  • Zurring of mixed halogenated compounds is known to be the use of "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 selected, for example, from halides, amines, carboxylates, acetylacetonate, aryl or alkylsulfonates, hydride, CO, olefins, dienes, cycloolefins, nitriles, N-containing heterocycles, aromatics and heteroaromatics , Ethers, PF 3 , phospholes, phosphabenzenes and mono-, bi- and multidentate phosphine, phosphinite, phosphonite, phosphoramidite and phosphite ligands.
  • ligands selected, for example, from halides, amines, carboxylates, acetylacetonate, aryl or alkylsulfonates, hydride, CO, olefins, dienes, cycloolefins, nitriles, N-containing heterocycles, aromatics and heteroaromatic
  • 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 (III) carboxylate, rhodium ( ll) and rhodium (III) acetate, rhodium (III) oxide, salts of rhodium (III) acid, trisammonium hexachlororhodate (III) etc.
  • rhodium complexes such as rhodium bis-carbonyl acetylacetonate, 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 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 are partly replaced by ligands of the formula PR 3 , such as Ru (CO) 3 (PPh 3 ) 2 .
  • 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.
  • the composition of the synthesis gas used from carbon monoxide and hydrogen can vary within wide ranges.
  • 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.
  • 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 functionalized at least in part 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, in which R and R 'are, for example, C 1 -C 10 -alkyl, C 6 -C 2 0 -alkyl, C 7 -C 20 -arylalkyl, C 7 -C 2 o-alkylaryl or cycloalkyl.
  • Diamines such as N, N-dimethylaminopropylamine and N, N'-dimethylpropylene-1-3-diamine are also suitable.
  • the amine value of the amino-functional polyisobutenes obtained depends on the number-average molecular weight M n and on the number of incorporated amino groups.
  • the resulting copolymers can then be further derivatized, for example by esterification or transesterification on the carboxyl groups of the dicarboxylic acid building block used or by reacting them with monodiiodo or polyamines to give the corresponding ammonium salts or amides, and using maleic acid or its derivatives as a comonomer also to imides, diimides or polyimides.
  • 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 nucleophilic 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.
  • the bifunctional polyisobutenes obtained by the process according to the invention serve as macromonomers for further polymerizations, polycondensations, network formation or coupling. In addition, they are suitable as precursors for the above-described functionalization reactions i) to x).
  • Preferred functionalization products are polyisobutenes having hydroxyl groups, in particular having 2 or 4 hydroxyl groups, with amine groups, in particular with 2 amine groups, with thiol groups, in particular with 4 or 6 SH groups, with alkoxysilane groups, in particular with 2 alkoxysilane groups, with succinic groups, in particular with 2 succinic anhydride or with 2 succinimide groups, and with phenolic groups, especially with 2 phenolic groups.
  • the bifunctional polyisobutenes and their functionalization products are found in adhesives and sealants, in elastomers, eg. As in tire materials, or as additives in the mineral oil sector, for. As in fuels and lubricants, application.
  • flasks A and B were connected to each other via a closable connection. Both flasks A (condensation flask) and B (reaction flask) were equipped with a magnetic stirrer, a thermometer, a septum, a pressure equalizing dropping funnel and an attached dry ice condenser with a drying tube and a heating and cooling bath. Flask B was also equipped with a React-IR (IR reaction control gauge) from Mettler Toledo. In the condensation flask A phenanthroline, methylene chloride and optionally hexane were presented. Isobutene was added to the dropping funnel condensed and emptied into the flask A.
  • React-IR IR reaction control gauge
  • the mixture was then titrated through the septum with a 1.6 M n-butyllithium solution in hexane until it turned brown for 5 minutes.
  • the stopcock was then opened to flask B, and the contents of flask A were transferred with heating to flask B into which had previously been added 1, 3 or 1, 4-dicumyl chloride, where it condensed on the dry ice condenser.
  • the solution was treated with 1.1 g of phenyltriethoxysilane, and then - 76 0 C cooled. Titanium tetrachloride was then added and the isobutene conversion was monitored by React-IR.
  • the polymerization was stopped by addition of 10 ml of ethanol at the pre-calculated drop in absorbance at 890 cm -1 After excess isobutene had been evaporated overnight, the mixture was mixed with 150 ml each of water and heptane, mixed vigorously and transferred to a separatory funnel The organic phase was washed twice with 150 ml of water each time and then dried over sodium sulfate, and then the solvent was removed under reduced pressure at room temperature, and the reaction conditions and the properties of the respective polymers obtained are shown in the following tables.
  • Examples 1 to 8 1, 4-dicumyl chloride was used as an initiator, while in Examples 9 to 16 1, 3-dicumyl chloride was used.
  • Examples 1 to 5 and 9 to 14 the polymerization was stopped so as to obtain polymers having an M n of about 2,000, whereas in Examples 6 to 8 and 15 and 16, polymers having a M n of about 500 were desired.
  • Example 17 The procedure was analogous to Example 1.1, but using instead of methylene chloride 1-chlorobutane.
  • phenyltriethoxysilane was used in an amount of 0.7 g, in Example 18 in an amount of 1.4 g.
  • the initiator used was 1,3-dicumyl chloride.
  • PDI polydispersity index M w / M n

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Abstract

L'invention concerne un procédé pour produire des polymères d'isobutène bifonctionnels à distribution de la masse moléculaire fine. Selon ce procédé, 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, lequel contient des solvants d'hydrocarbures halogénés en quantité telle que le mélange réactionnel, en début de polymérisation, a une constante diélectrique relative de 6,5 à -76 °C, l'isobutène n'étant pas complètement transformé.
PCT/EP2006/000451 2005-01-20 2006-01-19 Procédé pour produire un polyisobutène Ceased WO2006077116A1 (fr)

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DE102009037787A1 (de) 2008-08-19 2010-03-11 Basf Se Hydroborierung von Isobutenpolymeren

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DE102009001700A1 (de) 2008-03-25 2009-12-03 Basf Se Verfahren zur mikrowellen-unterstützten Polymerisation von ethylenisch ungesättigten Monomeren
KR20120112383A (ko) 2009-10-16 2012-10-11 바스프 에스이 폴리이소부텐 블록 및 올리고아미드 블록으로 제조된 열가소성 엘라스토머로서의 블록 공중합체

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EP0206756A2 (fr) * 1985-06-20 1986-12-30 The University of Akron Catalyseurs vivants, complexes et polymères
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

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Publication number Priority date Publication date Assignee Title
EP0206756A2 (fr) * 1985-06-20 1986-12-30 The University of Akron Catalyseurs vivants, complexes et polymères
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

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102009037787A1 (de) 2008-08-19 2010-03-11 Basf Se Hydroborierung von Isobutenpolymeren

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