WO2013021058A1 - Verfahren zur herstellung von hochreaktiven isobutenhomo- oder -copolymeren - Google Patents
Verfahren zur herstellung von hochreaktiven isobutenhomo- oder -copolymeren Download PDFInfo
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- WO2013021058A1 WO2013021058A1 PCT/EP2012/065751 EP2012065751W WO2013021058A1 WO 2013021058 A1 WO2013021058 A1 WO 2013021058A1 EP 2012065751 W EP2012065751 W EP 2012065751W WO 2013021058 A1 WO2013021058 A1 WO 2013021058A1
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- 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
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- C—CHEMISTRY; METALLURGY
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- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/08—Butenes
- C08F210/10—Isobutene
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
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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
- C08F4/00—Polymerisation catalysts
- C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
- C08F4/12—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen of boron, aluminium, gallium, indium, thallium or rare earths
- C08F4/14—Boron halides or aluminium halides; Complexes thereof with organic compounds containing oxygen
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
- C08F4/16—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen of silicon, germanium, tin, lead, titanium, zirconium or hafnium
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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
- C08F4/00—Polymerisation catalysts
- C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
- C08F4/26—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen of manganese, iron group metals or platinum group metals
Definitions
- the present invention relates to a novel process for the preparation of highly reactive isobutene homopolymers or copolymers having a terminal vinylidene double bond content per polyisobutene chain end of at least 50 mol%. Furthermore, the present invention relates to novel isobutene polymers.
- highly reactive isobutene homopolymers or copolymers are understood to mean those polyisobutenes which contain a high content of terminal ethylenic double bonds (a-double bonds), in practice usually at least 80 mol%, based on the individual chain ends of the polyisobutene macromolecules.
- vinylidene groups are understood as meaning those double bonds whose position in the polyisobutene macromolecule is represented by the general formula
- o ymer i. the double bond is in the polymer chain in one
- Polymer stands for the truncated to an isobutene polyisobutene.
- the vinylidene groups show the highest reactivity, for example in the case of thermal addition to sterically demanding reactants such as maleic anhydride, whereas a double bond further inside the macromolecules shows in most cases no or lower reactivity in the case of functionalization reactions.
- Highly reactive polyisobutenes are used inter alia as intermediates for the preparation of additives for lubricants and fuels, as described for example in DE-A 27 02 604.
- Such highly reactive polyisobutenes are, for example, according to the method of
- DE-A 27 02 604 obtainable by cationic polymerization of isobutene in the liquid phase in the presence of boron trifluoride as a catalyst.
- the disadvantage here is that the resulting polyisobutenes have a relatively high polydispersity.
- Polyisobutenes having a similarly high proportion of terminal double bonds but having a narrower molecular weight distribution are obtainable, for example, by the process of EP-A 145 235, US Pat. No. 5,408,018 and WO 99/64482, the polymerization being carried out in the presence of a deactivated catalyst, for example a Complex of boron trifluoride with alcohols and / or ethers, takes place.
- a deactivated catalyst for example a Complex of boron trifluoride with alcohols and / or ethers
- Highly reactive polyisobutenes are also obtainable by living cationic polymerization of isobutene and subsequent dehydrohalogenation of the resulting polymerization product, for example according to the process of US Pat. No. 5,340,881.
- a process is expensive, since the halogen end group introduced with the living cationic polymerization has to be eliminated in a separate step in order to generate the double bond.
- Lewis acid aluminum trichloride can be used as a polymerization catalyst for isobutene, for example, from High Polymers, Volume XXIV (Part 2), pp 713-733 (Editor: Edward C. Leonard), published by J. Wiley & Sons, New York, 1971.
- Double bonds can be obtained.
- a polyisobutene prepared with AlC which has a number-average molecular weight M n of 1000-2000, a polydispersity M w / M n of 2.5-3.5 and a content of Vinylidene isomer ( ⁇ -double bond) of only 5% (besides 65% “Tri", 5% " ⁇ " and 25% “Tetra”).
- the international patent application with the file reference PCT / EP201 1/051929 describes a process for the preparation of highly reactive isobutene homo- or copolymers having a content of terminal vinylidene double bonds per polyisobutene chain end of at least 50 mol%, in which Isobutene or an isobutene-containing monomer mixture in the presence of an effective as a polymerization catalyst aluminum trihalide donor complex or an aluminum alkyl halide donor complex polymerized, which contains as donor an organic compound having at least one ether function or a carboxylic acid ester function.
- iron (III) chloride is suitable as a coinitiator in the cationic isobutene polymerization for the preparation of highly reactive polyisobutenes and their copolymers.
- initiators water, phenols, protic acids such as sulfuric acid, tertiary alcohols, tertiary chlorides, tertiary carboxylic acid esters and carboxylic acids themselves are recommended.
- protic acids such as sulfuric acid, tertiary alcohols, tertiary chlorides, tertiary carboxylic acid esters and carboxylic acids themselves are recommended.
- As a complexing agent for the polymerization initiating systems in particular alkyl ethers are mentioned.
- WO 2006/01 1868 describes the polymerization of olefins using fluorohydrocarbons as solvent.
- the initiator system for the polymerization may include, among others, sulfonic acids.
- the object of the present invention was to provide a process for the preparation of highly reactive isobutene homo- or copolymers containing vinylidene terminal compounds.
- the catalyst system used should be sufficiently active, durable, easy to handle and not susceptible to failure.
- the object has been achieved by a process for the preparation of highly reactive isobutene homo- or copolymers having a content of terminal vinylidene double bonds per polyisobutene chain end of at least 50 mol% by polymerization of isobutene or a monomer mixture containing isobutene in the presence of at least one polymerisate.
- At least one initiator is an organic sulfonic acid of the general formula Z-SO3H, in which the variable Z denotes a C to C 20 -alkyl radical, C to C 20 -haloalkyl radical, C 5 to C 8 -cycloalkyl radical, C 6 to C 20 -aryl radical or a C 7 to C 20 -arylalkyl radical.
- isobutene homopolymers are understood to mean those polymers which, based on the polymer, are composed of at least 98 mol%, preferably at least 99 mol%, of isobutene.
- isobutene copolymers are understood to mean those polymers which contain more than 2 mol% of monomers in copolymerized form which are different from isobutene, for example linear butenes.
- a C to Cs alkyl radical is a linear or branched alkyl radical having 1 to 8 carbon atoms. Examples of these are methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert.
- Such C 1 to C 1 alkyl radicals can also to a small extent heteroatoms such as oxygen, nitrogen or halogen atoms, eg. As chlorine or fluorine, and / or non-protic functional groups such as carboxyl ester groups, cyano groups or nitro groups.
- heteroatoms such as oxygen, nitrogen or halogen atoms, eg. As chlorine or fluorine, and / or non-protic functional groups such as carboxyl ester groups, cyano groups or nitro groups.
- a C 1 to C 20 alkyl radical is a linear or branched alkyl radical having 1 to 20 carbon atoms. Examples of these are the abovementioned C 1 -C 5 -alkyl radicals and furthermore n-nonyl, isononyl, n-decyl, 2-propylheptyl, n-undecyl, n-dodecyl, n-tridecyl, isotridecyl, n-tetradecyl, n-hexadecyl, n-octadecyl and n-eicosyl.
- Such C 1 - to C 20 -alkyl radicals can also to a small extent heteroatoms such as oxygen, nitrogen or halogen atoms, eg. As chlorine or fluorine, and / or non-protic functional groups such as carboxyl ester groups, cyano groups or nitro groups.
- heteroatoms such as oxygen, nitrogen or halogen atoms, eg. As chlorine or fluorine, and / or non-protic functional groups such as carboxyl ester groups, cyano groups or nitro groups.
- a C 2 to C 20 haloalkyl radical or a C 1 to C 1 haloalkyl radical is a radical having the above-mentioned basic structures for C 1 to C 20 -alkyl radicals or C 1 to C 6 -alkyl radicals, in which, however, the hydrogen atoms are more widely protected by halogen atoms, are replaced in particular by fluorine and / or chlorine atoms. Preferably, all or nearly all hydrogen atoms are replaced by halogen atoms, in particular by fluorine and / or chlorine atoms.
- radicals are C 1 - to C 4 -alkyl radicals in which at least 60%, in particular at least 75%, especially at least 90% of the number of hydrogen atoms are replaced by fluorine and / or chlorine atoms, for example dichloromethyl, trichloromethyl, difluoromethyl, Trifluoromethyl, chlorodifluoromethyl, fluorodichloromethyl, pentachloroethyl or pentafluoroethyl.
- a C5 to C8 cycloalkyl group is a saturated cyclic group which may contain alkyl side chains. Examples include cyclopentyl, 2- or 3-methylcyclopentyl, 2,3-, 2,4- or 2,5-
- C5 to C7 cycloalkyl radicals can also to a small extent heteroatoms such as oxygen, nitrogen or halogen atoms, for. As chlorine or fluorine, and / or non-protic functional groups such as carboxyl ester groups, cyano groups or nitro groups.
- a C 6 to C 20 aryl radical or a C 6 to C 12 aryl radical is preferably optionally substituted phenyl, optionally substituted naphthyl, optionally substituted anthracenyl or optionally substituted phenanthrenyl.
- Such aryl groups may carry 1 to 5 non-protic substituents or non-protic functional groups, for example C 1 to C 6 alkyl, C 1 to C 5 haloalkyl such as C 1 to C 6 chloroalkyl or C 1 to C 8 fluoroalkyl, halogen such as chlorine or fluoro, nitro , Cyano or phenyl.
- aryl radicals are phenyl, naphthyl, biphenyl, anthracenyl, phenanthrenyl, tolyl, nitrophenyl, chlorophenyl, dichlorophenyl, pentafluorophenyl, pentachlorophenyl, (trifluoromethyl) phenyl, bis (trifluoromethyl) phenyl, (trichloro) methylphenyl and bis (trichloromethyl) phenyl.
- a C 7 - to C 20 -arylalkyl radical or a C 7 - to C 12 -arylalkyl radical is preferably optionally substituted C 1 -C 4 -alkylphenyl, such as benzyl, o-, m- or p-methylbenzyl, 1- or 2-phenylethyl, 1 -, 2- or 3-phenylpropyl or 1 -, 2-, 3- or 4-phenyl-butyl, optionally substituted C 4 to C -Alkylnaphthyl as naphthylmethyl, optionally substituted C 1 to C 4 -Alkylanthracenyl as anthracenylmethyl or optionally substituted Cr to C 4 alkylphenanthrenyl such as phenanthrenylmethyl.
- C 1 -C 4 -alkylphenyl such as benzyl, o-, m- or p-methylbenzyl, 1- or 2-phenylethyl, 1
- arylalkyl radicals can carry 1 to 5 non-protic or non-protic functional groups, in particular on the aryl part, for example C 1 to C 6 -alkyl, C 1 to C 5 -haloalkyl such as C 1 to C 5-chloroalkyl or C 1 to C 5 -fluoro- alkyl, halogen such as chlorine or fluorine, nitro or phenyl.
- the process according to the invention for the preparation of highly reactive isobutene homopolymers or copolymers proceeds as a result of the use of the polymerization catalyst complex of at least one Lewis acid and optionally at least one donor and the initiators described, according to a cationic reaction mechanism.
- the feature essential to the invention is the use of an organic sulfonic acid of the general formula Z-SO3H as at least one initiator in the polymerization process according to the invention.
- an organic sulfonic acid of the general formula Z-SO3H as at least one initiator in the polymerization process according to the invention.
- mixtures of different sulfonic acids Z-SO3H can also be used.
- further initiator molecules from other chemical classes can be used.
- the variable Z preferably represents a C to Cs-alkyl radical, C to Cs-haloalkyl radical, C5 to Cs-cycloalkyl radical, C6 to C12-aryl radical or a C7 to C12-arylalkyl radical.
- Z represents a a C to C 4 alkyl radical, a C to C 4 haloalkyl group, an optionally substituted phenyl radical, z.
- At least one initiator is an organic sulfonic acid selected from methanesulfonic acid, trifluoromethanesulfonic acid, trichloromethanesulfonic acid and toluenesulfonic acid or mixtures thereof.
- Lewis acid suitable as a polymerization catalyst or in the effective complex as a polymerization catalyst in principle all by definition as Lewis acids designated inorganic molecules, but especially halogen compounds of metals and semimetals of the Periodic Table of the Elements whose valences are completely saturated by halogen atoms or in addition to the halogen substituents still one or more organic carbon radicals - in particular C to C 4 alkyl radicals - wear.
- Suitable halogen substituents in these element halides and elemental alkyl halides are iodine, bromine and, in particular, fluorine and especially chlorine.
- mixtures of such Element halides or those Elementalkylhalogenide each with each other and with each other are used.
- the halides or alkyl halides of aluminum are used as such Lewis acids, typically the following species can be used: aluminum trifluoride, aluminum trichloride, aluminum tribromide; aluminum alkyl halides as mono (Ci to C 4 - alkyl) aluminiumdihalogenide or di (Ci to C4 alkyl) aluminiummonohalogenid as Methylalu- miniumdichlorid, ethylaluminum dichloride, dimethylaluminum chloride or Diethylaluminiumchlo-.
- the Lewis acid used for the polymerization catalyst or as the polymerization catalyst is at least one compound selected from the binary chlorine and fluorine compounds of the elements of FIG. to the 8th subgroup and the 3rd to 5th main group of the periodic table, wherein the binary chlorine compound fertilize over the binary fluorine compounds of these elements may be preferred.
- Typical of such binary chlorine compounds are SCCI 3, YC, YbCI 3, TiC, TiCl 4, ZrCl 4, HfCI 4 VCIs, VCU, NbCl 3, NbCl 5, TaCI 5, CrCl 2, CrCl 3, M0CI3, MoCI 5, WCI 5, WCI 6 , MnCl 2 , ReCl 3 , ReCl 5 , FeC, FeCl 3 , RuCl 3 , OsCl 3 , C0Cl 2, C0Cl 3 , RhCl 3 , IrCu, NiC, PdC, PtC, CuCl, CuC, AgCl, AuCl, ZnCl 2 , CdCl 2 , HgCI, HgCl 2 , BCI 3 , AICI 3 , GaCl 3 , InCl 3 , TICI 3 , SiCU, GeCl 4 , SnCl 2 , SnCl 3 , SnCl 4 , PbC,
- Typical such fluorine compounds are ScF 3 , YF 3 , YbF 3 , TiF 3 , TiF 4 , ZrF 4 , HfF 4 , VF 3 , VF 4 , NbF 3 , NbF 5 , TaF 5 , CrF 2 , CrF 3 , MoF 3 , MoF 5 , WF 5 , WF 6 , MnF 2 , ReF 3 , ReF 5 , FeF 2 , FeF 3 ,
- bromine compounds are, for example: TiBr 3 , TiBr 4 , ZrBr 4 , VBr 3 , VBr 4 , CrBr 2 , CrBr 3 , MoBr 3 , MoBr 5 , WBr 5 , WBr 6 , MnBr 2 , FeBr 2 , FeBr 3 , CoBr 2 , CoBr 3 , NiBr 2 , PdBr 2 , PtBr 2 , CuBr, CuBr 2 , AgBr, AuBr, ZnBr 2 , CdBr 2 , HgBr, HgBr 2 , BBr 3 , AIBr 3 , SiBr 4 , SnBr 2 , SnBr 3 , SnBr 4 , PbBr 2 , PbBr 4 , PBr 3 , PBr 5 , As
- a complex which acts as a polymerization catalyst and which contains as donor an organic compound having at least one ether function or one carboxylic ester function. It is of course also possible to use mixtures of different organic compounds having at least one ether function and / or of different organic compounds having at least one carboxylic acid ester function. If the complex acting as the polymerization catalyst has an organic compound with at least one ether function as donor, compounds having at least one ether function are also to be understood as meaning acetals and hemiacetals.
- the dihydrocarbyl ethers mentioned may be open-chain or cyclic, wherein in the case of the cyclic the two variables R 1 and R 2 form a ring, such rings also being able to contain two or three ether oxygen atoms.
- open-chain and cyclic dihydrocarbyl ethers are dimethyl ether, diethyl ether, di-n-propyl ether, diisopropyl ether, di-n-butyl ether, di-sec-butyl ether, diisobutyl ether, di-n-pentyl ether, di-n-hexyl ether , Di-heptyl ether, di-n-octyl ether, di- (2-ethylhexyl) ether, methyl n-butyl ether, methyl sec-butyl ether, methyl isobutyl ether, methyl tert-butyl ether, ethyl n buty
- dihydrocarbyl ethers di-n-butyl ether and diphenyl ether have proved to be particularly advantageous as donors, in particular in combination with the Lewis acid BCI3, AICI3, TiCU, FeC, FeC and ZnC.
- carboxylic acid hydrocarbyl esters are methyl formate, ethyl formate, n-propyl formate, formic acid isopropyl ester, n-butyl formate, sec-butyl formate, isobutyl formate, ants tert-butyl ester, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, sec-butyl acetate, isobutyl acetate, tert-butyl acetate, Propionic acid methyl ester, ethyl propionate, n-propyl propionate, isopropyl propionate, n-butyl propionate, sec-butyl propionate, isobutyl propionate, tert-butyl propionate, methyl butyrate, ethyl butyrate, Butyric acid n
- dihydrocarbyl ethers and Carbonkladocarbylester as donors have been found to be particularly advantageous in which the donor compound has a total carbon number of 3 to 16, preferably from 4 to 16, in particular from 4 to 12, especially from 4 to 8, having.
- the dihydrocarbyl ethers especially those having a total of 6 to 14, in particular 8 to 12, carbon atoms are preferred.
- the carboxylic acid hydrocarbyl esters in particular, especially those having a total of 3 to 10, in particular 4 to 6, carbon atoms are preferred.
- the molar ratio of said donor compounds to the Lewis acids, ie especially to said elemental halides and elemental alkyl halides, in particular to the Lewis acids BCI3, AICI3, TiCu, FeC, FeC and ZnC, in the complex polymerization complex is generally in the range of 0.3: 1 to 1, 5: 1, in particular from 0.5: 1 to 1, 2: 1, especially 0.7: 1 to 1, 1: 1; it is in most cases 1: 1.
- it can also be used with a greater degree of closure of the donor compounds, often up to a 10-fold, in particular 3-fold molar excess; the excess amount of donor compounds then additionally acts as a solvent or diluent.
- the polymerization catalyst complex is prepared before the polymerization separately from the one or more Lewis acids mentioned, which are usually used in anhydrous form, and the donor or the compounds and then - usually dissolved in an inert solvent such as a halogenated Hydrocarbon, for example dichloromethane - added to the polymerization medium.
- an inert solvent such as a halogenated Hydrocarbon, for example dichloromethane - added to the polymerization medium.
- the complex can also be prepared in situ prior to polymerization.
- the polymerization is carried out with concomitant use of at least one further initiator which is mono- or polyfunctional, in particular mono-, di- or trifunctional, and is selected from organic hydroxy compounds, organic halogen compounds, protic acids and water. It is also possible to use mixtures of such further initiators, for example mixtures of two or more organic hydroxy compounds, mixtures of two or more organic halogen compounds, mixtures of one or more organic hydroxy compounds and one or more organic halogen compounds, mixtures of one or more organic hydroxy compounds and water , Mixtures of one or more organic halogen compounds and water or mixtures of one or more protic acid and water.
- the initiator may be mono-, di- or polyfunctional, i.
- One, two or more hydroxyl groups or halogen atoms may be present in the initiator molecule at which the polymerization reaction starts.
- di- or polyfunctional initiators it is customary to obtain telechelic isobutene polymers having two or more, in particular two or three, polyisobutene chain ends.
- Suitable monofunctional initiators organic hydroxy compounds having only one hydroxyl group in the molecule are in particular alcohols and phenols, especially those of the general formula R 5 -OH, in the R 5 d- to C2o-alkyl radicals, in particular, d- to Cs-alkyl radicals , Cs to Cs-cycloalkyl radicals, C6 to C20-aryl radicals, in particular C6 to C12-aryl radicals, or C7 to C20-arylalkyl radicals, in particular C7 to C12-arylalkyl radicals.
- radicals R 5 may also contain mixtures of the abovementioned structures and / or have functional groups other than those already mentioned, for example a keto function, a nitroxide or a carboxyl group, and / or heterocyclic structural elements.
- organic monohydroxy compounds are methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, isobutanol, tert-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, 2 -Ethylhexanol, cyclohexanol, phenol, p-methoxyphenol, o-, m- and p-cresol, benzyl alcohol, p-methoxybenzyl alcohol, 1- and 2-phenylethanol, 1- and 2- (p-methoxyphenyl) ethanol, 1 -, 2 and 3-phenyl-1-propanol, 1-, 2- and 3- (p-methoxyphenyl) -1-propanol, 1- and 2-phenyl-2-propanol, 1- and 2- (p-methoxyphenyl) -1-propan
- Particularly suitable bifunctional initiators organic hydroxy compounds having two hydroxyl groups in the molecule are especially dihydric alcohols or diols having a total carbon number of 2 to 30, in particular from 3 to 24, especially from 4 to 20, and bisphenols having a total carbon number of 6 to 30, especially of 8 to 24, especially from 10 to 20, for example, ethylene glycol, 1, 2 and 1, 3-propylene glycol, 1, 4-butylene glycol, 1, 6-hexylene glycol, 1, 2, 1, 3 or 1,4-bis (1-hydroxy-1-methylethyl) benzene (o-, m- or p-dicumylalcohol), bisphenol A, 9,10-dihydro-9,10-dimethyl-9,10-anthracenediol, 1 , 1-diphenylbutan-1, 4-diol, 2-hydroxytriphenylcarbinol and 9- [2- (hydroxymethyl) phenyl] -9-fluorenol.
- Particularly suitable monofunctional initiators for organic halogen compounds having a halogen atom in the molecule are compounds of the general formula R 6 -Hal, in which shark is a halogen atom selected from fluorine, iodine and in particular chlorine and bromine, and R 6 is C 2 -C 20.
- Alkyl radicals in particular, d- to Cs-alkyl radicals, Cs to Cs-cycloalkyl radicals or C7- to C20-arylalkyl radicals, in particular C7- to C12-arylalkyl radicals.
- radicals R 6 may also contain mixtures of the abovementioned structures and / or have functional groups other than those mentioned above, for example a keto function, a nitroxide or a carboxyl group, and / or heterocyclic structural elements.
- organic monohalogen compounds are methyl chloride, methyl bromide, ethyl chloride, ethyl bromide, 1-chloropropane, 1-bromopropane, 2-chloropropane, 2-bromopropane, 1-chlorobutane, 1-bromobutane, sec-butyl chloride, sec-butyl bromide, isobutyl chloride, isobutyl bromide, tert-butyl chloride, tert-butyl bromide, 1-chloropentane, 1-bromopentane, 1-chlorohexane, 1-bromohexane, 1-chloroheptane, 1-bromoheptane, 1-chlorooctane, 1-bromoctane, 1 Chloro-2-ethylhexane, 1-bromo-2-ethylhexane, cyclohexyl chloride, cyclohexy
- Suitable difunctional initiators organic halogen compounds having two halogen atoms in the molecule are, for example, 1, 3-bis (1-bromo-1-methylethyl) benzene, 1, 3-bis (2-chloro-2-propyl) benzene (1, 3 Dicumyl chloride) and 1,4-bis (2-chloro-2-propyl) benzene (1,4-dicumyl chloride).
- the further initiator is particularly preferably selected from organic hydroxy compounds in which one or more hydroxyl groups are bonded to one sp 3 -hybridized carbon atom ("alcohols") or to one aromatic ring ("phenols”), organic halogen compounds in which one or more halogen atoms are bonded to one sp 3 -hybridized carbon atom, proton acids and water.
- alcohols organic hydroxy compounds in which one or more hydroxyl groups are bonded to one sp 3 -hybridized carbon atom
- phenols aromatic ring
- organic halogen compounds in which one or more halogen atoms are bonded to one sp 3 -hybridized carbon atom, proton acids and water.
- organic halogen compounds as further initiators to those in which the one or more halogen atoms are each bonded to a secondary or in particular to a tertiary sp 3 -hybridized carbon atom.
- the radicals R 5, R 6 and R 7 carry, which are independently hydrogen, Cr to C2o-alkyl, Cs to Cs cycloalkyl , C 6 - to C 20 -aryl, C 7 - to C 20 -alkylaryl or phenyl, where one aromatic nucleus contains one or more, preferably one or two C 1 to C 4 -alkyl, C 1 to C 4 -alkoxy, C 1 to C 4 - hydroxyalkyl or Cr to C 4 - may bear as substituents haloalkyl denote, wherein at most one of the variables R 5, R 6 or R 7 is hydrogen and at least one of the variables R 5, R 6 or R 7 is phenyl, which still one or more, preferably one or two C to C 4 alkyl, C to C 4 alkoxy, C to C 4 hydroxyalkyl or C to C 4
- initiators which are water, one or more protic acids, methanol, ethanol, 1-phenylethanol, 1 - (p-methoxyphenyl) ethanol, n-propanol, isopropanol, 2-phenyl-2-propanol (Cumene), n-butanol, isobutanol, sec-butanol, tert-butanol, 1-phenyl-1-chloroethane, 2-phenyl-2-chloropropane (cumyl chloride), tert-butyl chloride and 1, 3- or 1, 4-bis (1-hydroxy-1-methylethyl) benzene and mixtures thereof are selected.
- protic acids methanol, ethanol, 1-phenylethanol, 1 - (p-methoxyphenyl) ethanol, n-propanol, isopropanol, 2-phenyl-2-propanol (Cumene), n-butanol, isobutanol, sec-
- further initiators which, under water, one or more protic acids, methanol, ethanol, 1-phenylethanol, 1- (p-methoxy-phenyl) -ethanol, n-propanol, isopropanol, 2-phenyl-2-propanol ( Cumene), n-butanol, Isobutanol, sec-butanol, tert-butanol, 1-phenyl-1-chloroethane and 1, 3- or 1, 4-bis (1-hydroxy-1-methylethyl) benzene and mixtures thereof are selected.
- protic acids methanol, ethanol, 1-phenylethanol, 1- (p-methoxy-phenyl) -ethanol, n-propanol, isopropanol, 2-phenyl-2-propanol ( Cumene), n-butanol, Isobutanol, sec-butanol, tert-butanol, 1-phenyl-1-chloroethan
- the molar ratio of water alone to the isobutene monomer used in homopolymerization of isobutene or to the total amount of the polymerizable monomers used at Copo in particular from 0.0001: 1 to 0.1: 1, in particular from 0.0002: 1 to 0.05: 1.
- the proportion (Uff) of polymer chains which are started by such a built-in organic initiator molecule can be up to 100%, usually from 0 to 90% and can be from 5 to 90%.
- the remaining polymer chains are formed either by moisture-derived water as the initiator molecule or by chain transfer reactions.
- the polymerization is carried out in the presence of from 0.01 to 10 mmol, in particular from 0.05 to 5.0 mmol, especially from 0.1 to 1.0 mmol, in each case based on 1 mol used isobutene monomer in homopolymerization of isobutene or to 1 mol of the total amount of the polymerizable monomers used in copolymerization of isobutene, a nitrogen-containing basic compound.
- an aliphatic, cycloaliphatic or aromatic amine of the general formula R 7 -NR 8 R 9 or ammonia can be used, in which the variables R 7 , R 8 and R 9 are each independently hydrogen, C1- to C 2 -C 4 -alkyl radicals, in particular, C 5 -C -alkyl radicals, C 5 -C -cycloalkyl radicals, C 6 -C 20 -aryl radicals, in particular C 6 -C 12 -aryl radicals, or C 7 -C 20 -arylalkyl radicals, in particular C 7 -C 12 -arylalkyl radicals, stand.
- a tertiary amine is present. If none of these variables is hydrogen, a tertiary amine is present. If one of these variables is hydrogen, a secondary amine is present. If two of these variables are hydrogen, a primary amine is present. If all of these variables are hydrogen, ammonia is present.
- Typical examples of such amines of the general formula R 7 -NR 8 R 9 are methylamine, ethylamine, n-propylamine, iso-propylamine, n-butylamine, tert-butylamine, sec-butylamine, isobutylamine, tert.
- Methyl-N-phenylamine N, N-dimethyl-N-phenylamine, N-methyl-N, N-diphenylamine or N-methyl-N-ethyl-N-n-butylamine.
- nitrogen-containing basic compound a compound having a plurality, in particular having two or three nitrogen atoms and having 2 to 20 carbon atoms are used, these nitrogen atoms each independently of one another carry hydrogen atoms or aliphatic, cycloaliphatic or aromatic substituents.
- polyamines are 1, 2-ethylenediamine, 1, 3-propylenediamine, 1, 4-butylenediamine, diethylenetriamine, N-methyl-1, 2-ethylenediamine, N, N-dimethyl-1, 2-ethylenediamine, N , N'-dimethyl-1, 2-ethylenediamine or N, N-dimethyl-1,3-propylenediamine.
- such a nitrogen-containing basic compound is in particular a saturated, partially unsaturated or unsaturated nitrogen-containing five-membered or six-membered heterocycle containing one, two or three ring nitrogen atoms and one or two further ring heteroatoms from the group oxygen and sulfur and / or hydrocarbyl, in particular C 1 to C 4 -alkyl radicals and / or phenyl, and / or functional groups or heteroatoms as substituents, in particular fluorine, chlorine, bromine, nitro and / or cyano, for example pyrrolidine, pyrrole, imidazole, 1, 2, 3- or 1, 2,4-triazole, oxazole, thiazole, piperidine, pyrazane, pyrazole, pyridazine, pyrimidine, pyrazine, 1, 2,3-, 1, 2,4- or 1, 2,5-triazine, 1 , 2,5-oxathiazine, 2H-1, 3,5-thiadiazine
- nitrogen-containing basic compound is pyridine or a derivative of pyridine (in particular a mono-, di- or tri-d- to C 4 - alkyl-substituted pyridine) such as 2-, 3-, or 4-methylpyridine ( Picolines), 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, 3,5- or 3,6-dimethylpyridine (lutidines), 2,4,6-trimethylpyridine ( Collidine), 2-, 3, - or 4-tert.
- pyridine or a derivative of pyridine in particular a mono-, di- or tri-d- to C 4 - alkyl-substituted pyridine
- 2-, 3-, or 4-methylpyridine Picolines
- isobutene or an isobutene-containing monomer mixture as a monomer to be polymerized is suitable as an isobutene source both pure isobutene and isobutene-containing C4 hydrocarbon streams, such as C4 raffinates, especially "raffinate 1", C4 cuts from isobutane -Dehydrogenation, C4 slices from steam crackers and from fluid catalysed cracking (FCC) crackers, provided they are largely free of 1,3-butadiene contained therein.
- a C4 hydrocarbon stream from an FCC refinery unit is also known as a "b / b" stream.
- Suitable isobutene-containing C4 hydrocarbon streams are, for example, the product stream of a propylene-isobutane co-oxidation or the product stream from a metathesis unit, which are generally used after customary purification and / or upconcentration.
- Suitable C4 hydrocarbon streams typically contain less than 500 ppm, preferably less than 200 ppm, butadiene. The presence of 1-butene and of cis- and trans-2-butene is largely uncritical.
- the isobutene concentration in said C4 hydrocarbon streams is in the range of 40 to 60 weight percent.
- raffinate 1 usually consists essentially of 30 to 50 wt .-% of isobutene, 10 to 50 wt .-% 1-butene, 10 to 40 wt .-% cis- and trans-2-butene and 2 to 35 wt .-% butane;
- the unbranched butenees in raffinate 1 are generally virtually inert and only the isobutene is polymerized.
- the monomer used for the polymerization is a technical C 4 -hydrocarbon stream having an isobutene content of from 1 to 100% by weight, in particular from 1 to 99% by weight, in particular from 1 to 90% by weight. %, more preferably from 30 to 60% by weight, in particular a raffinate 1 stream, a b / b stream from an FCC refinery unit, a product stream from a propylene-isobutane co-oxidation or a product stream from a metathesis unit ,
- Said isobutene-containing monomer mixture may contain small amounts of contaminants such as water, carboxylic acids or mineral acids, without resulting in critical yield or selectivity losses. It is expedient to avoid an enrichment of these impurities by removing such pollutants from the isobutene-containing monomer mixture, for example by adsorption on solid adsorbents such as activated carbon, molecular sieves or ion exchangers.
- monomer mixtures of isobutene or of the isobutene-containing hydrocarbon mixture with olefinically unsaturated monomers which are copolymerizable with isobutene.
- the monomer mixture contains preferred at least 5 wt .-%, particularly preferably at least 10 wt .-% and in particular at least 20 wt .-% isobutene, and preferably at most 95 wt .-%, particularly preferably at most 90 wt .-% and in particular at most 80 wt. % Comonomers.
- Suitable copolymerizable monomers are: vinylaromatics such as styrene and a-
- 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.
- comopters also include isoprene, 1-butene and cis- and trans-2-butene.
- copolymers are to be prepared by the process according to the invention, the process can be designed such that preferably random polymers or preferably block copolymers are formed.
- block copolymers it is possible for example to feed the various monomers successively to the polymerization reaction, the addition of the second comonomer taking place in particular only when the first comonomer has already been at least partially polymerized. In this way, both diblock, triblock and higher block copolymers are accessible, which have a block of one or the other comonomer as a terminal block, depending on the order of monomer addition.
- block copolymers also form when all comonomers are simultaneously added to the polymerization reaction, but one of them polymerizes significantly faster than either one or the other.
- isobutene and a vinylaromatic compound, in particular styrene are copolymerized in the process according to the invention.
- block copolymers are formed with a terminal polystyrene block. This is due to the fact that the vinylaromatic compound, especially styrene, polymerizes significantly slower than isobutene.
- the polymerization can be carried out both continuously and discontinuously.
- Continuous processes can be carried out in analogy to known prior art processes for the continuous polymerization of isobutene in the presence of boron trifluoride-based catalysts in the liquid phase.
- the inventive method is suitable both for carrying out at low temperatures, for example at -90 ° C to 0 ° C, and in particular at higher temperatures, ie at least 0 ° C, for example at 0 ° C to + 50 ° C or at 0 ° C to + 30 ° C, suitable.
- the polymerization according to the inventive method is preferably carried out at a temperature of -30 ° C to + 50 ° C, in particular at 0 ° C to + 30 ° C, for example at room temperature (+20 to + 25 ° C). If the polymerization according to the process according to the invention takes place at or above the boiling point of the monomer or monomer mixture to be polymerized, it is preferably carried out in pressure vessels, for example in autoclaves or in pressure reactors.
- the polymerization is carried out according to the process of the invention in the presence of an inert diluent.
- the inert diluent used should be suitable for reducing the increase in the viscosity of the reaction solution which usually occurs during the polymerization reaction to such an extent that the removal of the heat of reaction formed can be ensured.
- Suitable diluents are those solvents or solvent mixtures which are inert to the reagents used.
- Suitable diluents are, for example, aliphatic hydrocarbons such as n-butane, n-pentane, n-hexane, n-heptane, n-octane and isooctane, cycloaliphatic hydrocarbons such as cyclopentane and cyclohexane, aromatic hydrocarbons such as benzene, toluene and the xylenes, and halogenated Hydrocarbons, in particular halogenated aliphatic hydrocarbons, such as methyl chloride, dichloromethane, trichloromethane (chloroform), 1, 1-dichloroethane, 1, 2-dichloroethane, trichloroethane and 1-chlorobutane and halogenated aromatic hydrocarbons and alkylaromatics halogenated in the alkyl side chains, such as chlorobenzene, monofluoromethylbenzene, Difluoro
- chlorinated hydrocarbons in particular pure chlorohydrocarbons
- Fluorohydrocarbons are preferably excluded from the inert diluents which can be used here in order to largely exclude residual contents of fluorine in the polymer.
- the inert constituents of isobutene-containing C 4 hydrocarbon streams are also used as diluents or as constituents of the solvent mixtures mentioned.
- the polymerization according to the invention is preferably carried out in an aliphatic, cycloaliphatic or aromatic hydrocarbon, in a halogenated hydrocarbon, in particular in a halogenated aliphatic hydrocarbon, or in a mixture of aliphatic, cycloaliphatic and / or aromatic hydrocarbons or halogenated hydrocarbons, in particular halogenated aliphatic hydrocarbons, or in a mixture of at least one halogenated hydrocarbon, in particular a halogenated aliphatic hydrocarbon, and at least one aliphatic, cycloaliphatic or aromatic hydrocarbon as an inert diluent, for example a mixture of dichloromethane and n-hexane, usually in the Vol.
- a halogenated hydrocarbon in particular in a halogenated aliphatic hydrocarbon
- a mixture of aliphatic, cycloaliphatic and / or aromatic hydrocarbons or halogenated hydrocarbons in particular halogen
- the diluents are freed before use of impurities such as water, carboxylic acids or mineral acids, for example by adsorption on solid adsorbents such as activated carbon, molecular sieves or ion exchangers.
- the polymerization according to the invention is carried out in halogen-free aliphatic or, in particular, halogen-free aromatic hydrocarbons, in particular toluene.
- water has proven to be particularly advantageous as a further initiator, optionally in combination with the said organic hydroxy compounds and / or the said organic halogen compounds.
- the polymerization is carried out according to the process of the invention under largely aprotic, in particular under substantially anhydrous reaction conditions.
- largely aprotic or largely anhydrous reaction conditions it is understood that the water content (or the content of protic impurities) in the reaction mixture is less than 50 ppm and in particular less than 5 ppm.
- the feedstocks will be dried before use by physical and / or chemical means.
- the aliphatic or cycloaliphatic hydrocarbons used as solvent after conventional pre-cleaning and predrying with an organometallic compound, such as an organolithium, organomagnesium or organoaluminum compound, in an amount sufficient to remove the traces of water from the Solvent largely remove.
- organometallic compound such as an organolithium, organomagnesium or organoaluminum compound
- the solvent thus treated is then preferably condensed directly into the reaction vessel.
- halogenated solvents which are not suitable for drying with metals such as sodium or potassium or with metal alkyls, are freed from water or traces of water 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.
- Even if water is used as an initiator residual moisture from solvents and monomers should preferably be removed as far as possible or completely before the reaction by drying in order to be able to use the further initiator of water in a specified amount in a targeted manner, thereby obtaining a higher process control and reproducibility of the results.
- the polymerization of the isobutene or the isobutene-containing starting material takes place spontaneously when the complex effective as the polymerization catalyst is contacted with the isobutene or the isobutene-containing monomer mixture at the desired reaction temperature.
- isobutene copolymers For the preparation of isobutene copolymers, it is possible to proceed by initially introducing the monomers, if appropriate in the diluent, and then adding the complex. The adjustment of the reaction temperature can be carried out before or after the addition of the complex. It is also possible to initially provide only one of the monomers, if appropriate in the diluent, then to add the complex and to react it only after a certain time, for example when at least 60%, at least 80% or at least 90% of the monomer have reacted or adding the further monomers. Alternatively, one may submit the complex, optionally in the diluent, then add the monomers simultaneously or sequentially and then adjust the desired reaction temperature. The beginning of polymerization is then that time at which the complex and at least one of the monomers are contained in the reaction vessel.
- the polymerization can also be carried out in accordance with the process of the invention as a continuous process.
- the starting materials i. the monomer (s) to be polymerized, optionally the diluent and optionally the complex polymerization complex, are continuously added to the polymerization reaction and continuously remove reaction product, so that more or less stationary polymerization conditions are established in the reactor.
- the monomer (s) to be polymerized may be supplied as such, diluted with a diluent or solvent, or as a monomer-containing hydrocarbon stream.
- the complex which is effective as a polymerization catalyst is generally dissolved, dispersed or suspended in the polymerization medium. Also, a support of the complex on conventional substrates is possible.
- Suitable reactor types for the polymerization process of the present invention are usually stirred tank reactors, loop reactors and tubular reactors, but also fluidized bed reactors, fluidized bed reactors, stirred tank reactors with and without solvent, liquid bed reactors, continuous fixed bed reactors and batchwise batchwise reactors.
- the complex polymerization catalyst is generally used in such an amount that the molar ratio of element in the preferred as Lewis acids Elementhalogeniden or Elementalkylhalogeniden to isobutene in homopolymerization of isobutene or to the total amount of polymerizable Monomers in the copolymerization of isobutene in the range of 1: 5 to 1: 5000, preferably 1: 10 to 1: 5000, in particular 1: 15 to 1: 1000, especially 1: 20 to 1: 250, is located.
- the reaction mixture is preferably deactivated, for example by adding a protic compound, in particular by adding water, alcohols, such as methanol, ethanol, n-propanol and isopropanol or mixtures thereof with water, or by adding an aqueous base, for example an aqueous solution an alkali or alkaline earth hydroxides such as sodium hydroxide, potassium hydroxide, magnesium hydroxide or calcium hydroxide, an alkali or alkaline earth metal carbonate such as sodium, potassium, magnesium or calcium carbonate, or an alkali or Erdalkalihydrogencarbonats such as sodium, potassium, magnesium or calcium bicarbonate.
- a protic compound in particular by adding water, alcohols, such as methanol, ethanol, n-propanol and isopropanol or mixtures thereof with water, or by adding an aqueous base, for example an aqueous solution an alkali or alkaline earth hydroxides such as sodium hydroxide, potassium hydroxide, magnesium hydrox
- the process according to the invention is used to prepare highly reactive isobutene homopolymers or copolymers having a content of terminal vinylidene double bonds (a double bonds) per polyisobutene chain end of at least 50 mol%, preferably of at least 60 mol%, preferably of at least 70 mol -%, preferably of at least 80 mol%, preferably of at least 85 mol%, particularly preferably of at least 90 mol%, particularly preferably more than 91 mol% and in particular of at least 95 mol%, for example of nearly 100 mol%.
- isobutene copolymers which are composed of isobutene and at least one vinylaromatic monomer, in particular styrene, and a content of terminal vinylidene double bonds (a-double bonds) per polyisobutene chain end of at least 50 mol -%, preferably of at least 60 mol%, preferably of at least 70 mol%, preferably of at least 80 mol%, preferably of at least 80 mol%, preferably of at least 85 mol%, particularly preferably of at least 90 mol% %, more preferably more than 91 mol%, and especially at least 95 mol%, eg of nearly 100 mol%.
- Typical values for PDI are 1, 2 to 1, 7 for optimum process control.
- the highly reactive isobutene homo- or copolymers prepared by the process according to the invention preferably have a number-average molecular weight M n (determined by gel permeation chromatography) of preferably 500 to 250,000, more preferably 500 to 100,000, more preferably 500 to 25,000 and in particular 500 to 5,000.
- Isobutene homopolymers even more preferably have a number average molecular weight M n of from 500 to 10,000 and in particular from 500 to 5,000, for example from about 1,000 or from about 2300.
- the isobutene polymers having terminal vinylidene double bonds which occur in the isobutene homopolymers prepared according to the invention are those which are known as Containing initiator molecules incorporated organic sulfonic acids, new compounds are Therefore, the subject of the present invention are also isobutene polymers of the general formula I.
- R 10 denotes a sulfonic acid grouping of the general formula -O-SO 2 Z in which the variable Z is a C 2 -C 20 -alkyl radical, C 2 -C 20 -haloalkyl radical, C 5 -C 5 -cycloalkyl radical, C 6 -C 20 -aryl radical or a C 7- to C2o-arylalkyl radical, and R 11 and R 12 independently of one another are hydrogen, C 1 - to C 20 -alkyl radicals, C 5 - to C 8 -cycloalkyl radicals, C 6 - to C 20 -aryl radicals or C 7 - to C 20 -alkylaryl radicals, and n is a number from 9 to 4500 stands.
- R 11 and R 12 independently of one another denote hydrogen, C 1 -C 4 -alkyl, in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl, or phenyl which may also carry one or two C 1 to C 4 -alkyl or C 1 to C 4 -alkoxy radicals as substituents, and n is a number from 9 to 4500, preferably from 9 to 180, in particular from 9 to 90, especially 15 to 45 stands.
- Example 2 Polymerization of "Raffinate 1" with FeC'B ⁇ O and with methanesulfonic acid as initiator in dichloromethane at -20 ° C 14.86 g of "raffinate 1" containing 5.94 g (106.0 mmol) of pure isobutene were dissolved in 130 ml of dichloromethane at -20 ° C. with 0.53 mmol of the catalyst complex of anhydrous iron (III).
- Example 5 Polymerization of "Raffinate 1" with AICb'Bi ⁇ O and with methanesulfonic acid as initiator in dichloromethane at + 20 ° C.
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EP12745871.9A EP2742073A1 (de) | 2011-08-11 | 2012-08-10 | Verfahren zur herstellung von hochreaktiven isobutenhomo- oder -copolymeren |
CN201280039216.8A CN103764695A (zh) | 2011-08-11 | 2012-08-10 | 生产高反应性异丁烯均聚物或共聚物的方法 |
JP2014525415A JP6099648B2 (ja) | 2011-08-11 | 2012-08-10 | 高反応性イソブテンホモポリマーまたはイソブテンコポリマーの製造法 |
KR1020147004816A KR20140049024A (ko) | 2011-08-11 | 2012-08-10 | 고반응성 이소부텐 단독- 또는 공중합체의 제조 방법 |
SG2014004303A SG2014004303A (en) | 2011-08-11 | 2012-08-10 | Process for preparing high-reactivity isobutene homo- or copolymers |
RU2014108711A RU2608510C2 (ru) | 2011-08-11 | 2012-08-10 | Способ получения высокореакционноспособных гомополимеров или сополимеров изобутилена |
BR112014002551A BR112014002551A2 (pt) | 2011-08-11 | 2012-08-10 | processo para preparar homo ou copolímeros de isobuteno de alta reatividade, e, polímeros de isobuteno |
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JP2014173091A (ja) * | 2013-03-12 | 2014-09-22 | Univ Of Massachusetts | 重合開始系および高反応性オレフィン機能性高分子の製造方法 |
EP2860206A1 (de) * | 2013-10-11 | 2015-04-15 | University of Massachusetts | System zur Polymerisierungseinleitung und Verfahren zur Herstellung hochreaktiver funktionaler Olefinpolymere |
US9771442B2 (en) | 2015-05-13 | 2017-09-26 | University Of Massachusetts | Polymerization initiating system and method to produce highly reactive olefin functional polymers |
US10047174B1 (en) | 2017-06-28 | 2018-08-14 | Infineum International Limited | Polymerization initiating system and method to produce highly reactive olefin functional polymers |
US10167352B1 (en) | 2017-06-28 | 2019-01-01 | University Of Massachusetts | Polymerization initiating system and method to produce highly reactive olefin functional polymers |
US10174138B1 (en) | 2018-01-25 | 2019-01-08 | University Of Massachusetts | Method for forming highly reactive olefin functional polymers |
US10829573B1 (en) | 2019-05-21 | 2020-11-10 | Infineum International Limited | Method for forming highly reactive olefin functional polymers |
WO2023232613A1 (en) * | 2022-06-03 | 2023-12-07 | Basf Se | Process for manufacturing of higher functional polyisobutenes |
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JP6903069B2 (ja) * | 2016-02-16 | 2021-07-14 | ビーエイエスエフ・ソシエタス・エウロパエアBasf Se | 高反応性イソブテンホモポリマーまたはコポリマーの製造方法 |
CN107586248A (zh) * | 2016-07-08 | 2018-01-16 | 上海纳克润滑技术有限公司 | 一种基于微通道反应进行α‑烯烃齐聚的方法 |
JP6839004B2 (ja) * | 2017-03-21 | 2021-03-03 | 株式会社カネカ | イソブチレン系重合体の製造方法 |
CN107033260A (zh) * | 2017-04-14 | 2017-08-11 | 上海欧勒奋生物科技有限公司 | 一种基于甲烷磺酸改性的三氯化铝催化合成pao9基础油的方法 |
EP3444283B1 (de) * | 2017-08-17 | 2020-02-26 | Basf Se | Verfahren zur herstellung von hochreaktiven isobuten-homo- oder -copolymeren |
KR102203006B1 (ko) * | 2019-04-24 | 2021-01-13 | 대림산업 주식회사 | 고반응성 폴리부텐의 제조 방법 |
CN110183560B (zh) * | 2019-06-14 | 2020-08-28 | 华东理工大学 | 一种利用铁钛复合催化剂制备中分子量聚异丁烯的方法 |
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JP2014173091A (ja) * | 2013-03-12 | 2014-09-22 | Univ Of Massachusetts | 重合開始系および高反応性オレフィン機能性高分子の製造方法 |
EP2860206A1 (de) * | 2013-10-11 | 2015-04-15 | University of Massachusetts | System zur Polymerisierungseinleitung und Verfahren zur Herstellung hochreaktiver funktionaler Olefinpolymere |
JP2015074785A (ja) * | 2013-10-11 | 2015-04-20 | ユニバーシティ オブ マサチューセッツ | 高反応性オレフィン機能性ポリマーを作製する重合開始系および方法 |
KR20150042739A (ko) * | 2013-10-11 | 2015-04-21 | 유니버시티 오브 매사추세츠 | 중합 개시 시스템 및 고도로 반응성인 올레핀 작용성 폴리머를 제조하는 방법 |
US9631038B2 (en) | 2013-10-11 | 2017-04-25 | University Of Massachusetts | Polymerization initiating system and method to produce highly reactive olefin functional polymers |
KR102065510B1 (ko) | 2013-10-11 | 2020-01-13 | 유니버시티 오브 매사추세츠 | 중합 개시 시스템 및 고도로 반응성인 올레핀 작용성 폴리머를 제조하는 방법 |
US9771442B2 (en) | 2015-05-13 | 2017-09-26 | University Of Massachusetts | Polymerization initiating system and method to produce highly reactive olefin functional polymers |
US10047174B1 (en) | 2017-06-28 | 2018-08-14 | Infineum International Limited | Polymerization initiating system and method to produce highly reactive olefin functional polymers |
US10167352B1 (en) | 2017-06-28 | 2019-01-01 | University Of Massachusetts | Polymerization initiating system and method to produce highly reactive olefin functional polymers |
US10174138B1 (en) | 2018-01-25 | 2019-01-08 | University Of Massachusetts | Method for forming highly reactive olefin functional polymers |
US10829573B1 (en) | 2019-05-21 | 2020-11-10 | Infineum International Limited | Method for forming highly reactive olefin functional polymers |
WO2023232613A1 (en) * | 2022-06-03 | 2023-12-07 | Basf Se | Process for manufacturing of higher functional polyisobutenes |
Also Published As
Publication number | Publication date |
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SG10201606556WA (en) | 2016-09-29 |
JP2014524492A (ja) | 2014-09-22 |
EP2742073A1 (de) | 2014-06-18 |
SG2014004303A (en) | 2014-03-28 |
BR112014002551A2 (pt) | 2017-03-14 |
JP6099648B2 (ja) | 2017-03-22 |
KR20140049024A (ko) | 2014-04-24 |
MY166046A (en) | 2018-05-22 |
CN103764695A (zh) | 2014-04-30 |
RU2608510C2 (ru) | 2017-01-18 |
AR087514A1 (es) | 2014-03-26 |
RU2014108711A (ru) | 2015-09-20 |
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