WO2007104727A1 - Alcene substitue en tant qu'amorceur de polymerisation cationique - Google Patents

Alcene substitue en tant qu'amorceur de polymerisation cationique Download PDF

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WO2007104727A1
WO2007104727A1 PCT/EP2007/052263 EP2007052263W WO2007104727A1 WO 2007104727 A1 WO2007104727 A1 WO 2007104727A1 EP 2007052263 W EP2007052263 W EP 2007052263W WO 2007104727 A1 WO2007104727 A1 WO 2007104727A1
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formula
cationic polymerization
reaction
polymers
alkyl
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PCT/EP2007/052263
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German (de)
English (en)
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Heike Pfistner
Szilard Csihony
Hans Peter Rath
Herbert Mayr
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Basf Aktiengesellschaft
Ludwig-Maximilians-Universität
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
    • C07C17/08—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated hydrocarbons
    • 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 cationic polymerization of cationically polymerizable ethylenically unsaturated monomers in the presence of one or more Lewis acids. Furthermore, the invention relates to polymers which are obtainable by the process for cationic polymerization. Furthermore, the invention comprises processes for the preparation of substituted alkenes which have leaving groups in an allylic position to the double bond. Further embodiments of the present invention can be taken from the claims, the description and the examples. It is understood that the features mentioned above and those still to be explained below of the article according to the invention can be used not only in the specific concretely specified combination but also in the context of the invention in other combinations.
  • initiator systems comprising a Lewis acid and an organic compound which forms a carbocation or a cationogenic complex with the Lewis acid are employed.
  • initiator systems comprising a Lewis acid and an organic compound which forms a carbocation or a cationogenic complex with the Lewis acid are employed.
  • isobutene polymer and polyisobutene are used equivalently in the context of this invention.
  • Isobutene polymers which are particularly suitable for further processing, for example, into sealing and sealing compounds or to adhesive raw materials are telechelic, i. they have two or more reactive end groups. These end groups preferably contain carbon-carbon double bonds which can be further functionalized or the end groups are groups functionalized with a terminating agent.
  • EP-A 713 883 describes the preparation of telechelic isobutene polymers using an at least bifunctional initiator, such as dicumyl chloride.
  • a disadvantage of the known process is that the aromatic initiators described can react to indanyl or diindane groups (as described, for example, in: G. Pratrap, SA Mustafa, JP Heller, J. Polym., Part A, Polym. Chem. 31, pp. 2387-2391), which impairs the synthesis of defined telechelic isobutene polymers.
  • Substituted cycloalkanes can be used according to the application WO 05/044766 as initiators for the cationic polymerization.
  • WO 04/1 13402 discloses initiators (initiators) for cationic polymerization which simultaneously contain ethylenically unsaturated hydrocarbon radicals which comprise vinyl groups or cycloalkenyl groups and functional group selected from halogen, C 1 -C 6 -alkoxy and C 1 -C 4 -cycloalkyl. C6 acyloxy.
  • a typical example of such a starter is 2-chloro-2-methylbut-3-ene.
  • the object of the present invention was therefore to develop a process for cationic polymerization, in particular for the cationic polymerization of isobutene. Furthermore, compounds should be found that can be used as novel initiators. The initiators should be easy to prepare and stable in storage. Another object of the invention was to develop initiators which show no reaction to indanyl or diindane groups.
  • the object is achieved by a process for the cationic polymerization of cationically polymerizable ethylenically unsaturated monomers, in which polymerization is carried out in the presence of one or more Lewis acids and in the presence of one or more substituted alkenes of the formula (I).
  • the substituted alkenes of formula (I) have a leaving group X in allylic position to the double bond,
  • R 1 is H or C 1 -C 5 -alkyl
  • R 2 is d-C ⁇ -alkyl
  • X is halogen, OR 3 or OCOR 3 , wherein R 3 is C 1 -C 6 -alkyl.
  • C 3 -Cb designates in the context of this invention chemical compounds or substituents having a certain number of carbon atoms.
  • the number of carbon atoms can be selected from the entire range from a to b, including a and b, a is at least 1 and b is always greater than a.
  • Further specification of the chemical compounds or substituents is made by terms of the form C 3 -Cb-V.
  • V stands for a chemical compound class or substituent class, for example for alkyl compounds or alkyl substituents.
  • d-Cs-alkyl or Ci-C ⁇ -alkyl are linear or branched alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, 2 Methylbutyl, neopentyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl or 2-ethylbutyl.
  • Halogen is fluorine, chlorine, bromine or iodine, preferably chlorine, bromine or iodine, particularly preferably chlorine or bromine and especially chlorine.
  • R 1 is H or C 1 -C 3 -alkyl, preferably H or methyl, in particular H.
  • R 2 is preferably C 1 -C 4 -alkyl, preferably methyl or ethyl, in particular methyl.
  • X is preferably halogen; Acetyloxy or propionyloxy; Methoxy, ethoxy, propoxy or butoxy, particularly preferably halogen and in particular chlorine.
  • alkenes of the formula (I) are those in which R 1 is H and R 2 is methyl and in which X has the meaning given in formula (I), in particular X is chlorine.
  • the preferred alkene is 2-chloro-pent-3-ene.
  • the double bond in formula (I) can have both ice and trans configuration.
  • the alkenes of the formula (I) can act as initiators in the cationic polymerization of cationically polymerizable ethylenically unsaturated monomers. Polymers are obtained which contain at one end of the polymer chain in the end group a double bond introduced by the initiator. The side reactions known from dicumyl chloride are not possible.
  • the described alkenes of the formula (I) in amounts of 0.001 to 10 mol%, in particular 0.01 to 7 mol%, especially 0.05 to 5 mol%, based on the total amount of cationically polymerizable ethylenically unsaturated Monomers, used.
  • Suitable cationically polymerizable, ethylenically unsaturated monomers are, in the context of the process according to the invention, in particular electron-rich olefin derivatives.
  • isobutene vinylaromatic compounds such as styrene or ⁇ -methylstyrene or Cs-Cio-isoolefins such as 2-methylbutene-1, 2-methylpentene-1, 2-methylhexene-1,2-ethyl-pentene-1,2-ethylhexene-1 or 2-Propylhepten -1.
  • the process is used to produce homo-, co- or block copolymers of isobutene.
  • C 4 raffinates When isobutene feedstocks are both isobutene itself and isobutene-C4 hydrocarbon streams, for example C 4 raffinates, C 4 cuts from isobutene dehydrogenation, C 4 cuts from steam crackers and FCC crackers (FCC: Fluid Catalysis zed cracking), provided that they are largely exempt from 1, 3-butadiene contained therein.
  • C4 hydrocarbon streams suitable according to the invention generally contain less than 500 ppm, preferably less than 200 ppm of butadiene.
  • the hydrocarbons that are different from isobutene play the role of an inert solvent.
  • the monomer mixture contains more than 50 wt .-%, in particular more than 70 wt .-%, and, more preferably, more than 90 wt .-% isobutene, and less than 50 wt .-%, preferably less than 30 Wt .-%, and in particular less than 10 wt .-%, comonomers.
  • Comonomers in monomer mixtures with isobutene are other ethylenically unsaturated monomers, such as vinylaromatics, for example styrene or C 1 -C 4 -alkyl styrenes, such as 2-, 3- or 4-methylstyrene, and also 4-tert-butylstyrene, n-butene, Cs -Cio-iso-olefins such as 2-methylbutene-1, 2-methylpentene-1, 2-methylhexene-1, 2-ethylpentene-1, 2-ethylhexene-1 or 2-propylheptene-1 into consideration.
  • vinylaromatics for example styrene or C 1 -C 4 -alkyl styrenes, such as 2-, 3- or 4-methylstyrene, and also 4-tert-butylstyrene, n-butene, Cs -Cio-iso
  • olefins which have a silyl group, such as 1-trimethoxysilyl ethene, 1- (trimethoxysilyl) propene, 1- (trimethoxysilyl) -2-methylpropene-2, 1- [tri (methoxyethoxy) -silyl ] ethene, 1- [tri (methoxyethoxy) silyl] propene, or 1- [tri (methoxyethoxy) silyl] -2-methylpropene-2.
  • silyl group such as 1-trimethoxysilyl ethene, 1- (trimethoxysilyl) propene, 1- (trimethoxysilyl) -2-methylpropene-2, 1- [tri (methoxyethoxy) -silyl ] ethene, 1- [tri (methoxyethoxy) silyl] propene, or 1- [tri (methoxyethoxy) silyl] -2-methylpropene-2
  • Suitable Lewis acids in the process according to the invention are essentially covalent metal halides or semimetallic halides which have an electron pair gap. Mixtures of several Lewis acids can also be used. Such compounds are known to the person skilled in the art, for example from J.P. Kennedy et al. in US 4,946,889, US 4,327,201, US 5,169,914, EP-A-206 756, EP-A-265 053 and JP Kennedy, B. Ivan, "Designed Polymers by Carboc- tic Macromolecular Engineering", Oxford University Press, New York 1991.
  • Particularly preferred Lewis acids for isobutene polymerization are titanium tetrachloride, boron trichloride or boron trifluoride, in particular titanium tetrachloride.
  • the Lewis acid or mixture of Lewis acids is employed in an amount sufficient to form an initiator complex of one or more Lewis acids and one or more alkenes of Formula (I).
  • the molar ratio of Lewis Acids to initiators are generally from 10: 1 to 1: 1, especially from 2.5 to 1: 1.
  • 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 pyridines such as pyridine itself, 2,6-dimethylpyridine, as well as sterically hindered pyridines such as 2,6-diisopropylpyridine or 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; Ethers, e.g.
  • Dialkyl ethers such as diethyl ether or diisopropyl ether, cyclic ethers such as tetrahydrofuran; Amines, in particular trialkylamines such as triethylamine; Esters, in particular C 1 -C 4 -alkyl esters of aliphatic C 1 -C 6 -carboxylic acids, such as ethyl acetate; Thioethers, in particular dialkylthioethers or alkylarylthioethers, such as methylphenylsulfide; Sulfoxides, in particular dialkyl sulfoxides, such as dimethyl sulfoxide; Nitriles, in particular alkylnitriles such as acetonitrile or propionitrile; Phosphines, in particular trialkylphosphines or triarylphosphines, such as trimethylphosphine, triethylphosphine, tri-n-butylphosphine
  • pyridine or sterically hindered pyridine derivatives and in particular organosilicon compounds preference is given to pyridine or sterically hindered pyridine derivatives and in particular organosilicon compounds.
  • organosilicon compounds are dimethoxydiisopropylsilane, dimethoxyisobutylisopropylsilane, dimethoxydiisobutylsilane, dimethoxydicyclopentylsilane, dimethoxyisobutyl-2-butylsilane, diethoxyisobutylisopropylsilane, triethoxytoluylsilane, triethoxybenzylsilane or triethoxyphenylsilane.
  • the cationic polymerization is usually carried out as a solution polymerization.
  • Suitable solvents are all low molecular weight, organic compounds or mixtures thereof which have a suitable low dielectric constant and no abstractable protons and which are liquid under the cationic polymerization conditions.
  • Preferred solvents are hydrocarbons, for example acyclic hydrocarbons having from 2 to 8 and preferably from 3 to 8 carbon atoms, such as ethane, iso- or n-propane, n-butane or its isomers, n-pentane or its isomers, n-hexane or its isomers , and n-heptane or its isomers, and n-octane or its isomers, cyclic alkanes having from 5 to 8 carbon atoms such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, cycloheptane, acyclic alkenes having preferably from 2 to 8 carbon atoms such as Ethene, iso- or n-propene, n-butene, n-pentene, n-hexene or n-heptene, cyclic olefins
  • halogenated hydrocarbons When halogenated hydrocarbons are used as the solvent, the possible halogenated hydrocarbons do not include compounds in which halogen atoms are attached to secondary or tertiary carbon atoms.
  • the hydrocarbons other than isobutene play the role of an inert solvent.
  • solvents are aromatic hydrocarbons, of which toluene is particularly preferred.
  • solvent mixtures comprising at least one halogenated hydrocarbon and at least one aliphatic or aromatic hydrocarbon.
  • the solvent mixture comprises hexane and chloromethane or dichloromethane, as well as mixtures of hexane and chloromethane and dichloromethane.
  • the volume ratio of hydrocarbon to halogenated hydrocarbon is preferably in the range of 1:10 to 10: 1, more preferably in the range of 4: 1 to 1: 4 and in particular in the range of 2: 1 to 1: 2.
  • the cationic polymerization is usually carried out under largely aprotic, especially 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.
  • the aliphatic or cycloaliphatic hydrocarbons used as solvent can be added after conventional prepurification and predrying with an organometallic compound, for example an organolithium, organomagnesium or organoaluminium compound, in an amount sufficient to remove traces of water from the solvent.
  • an organometallic compound for example an organolithium, organomagnesium or organoaluminium compound
  • the cationic polymerization is carried out by the process according to the invention, at temperatures below 0 ° C, z. In the range of 0 to -140 ° C, preferably in the range of -30 to -120 ° C, and more preferably in the range of -40 to -110 ° C by.
  • the reaction pressure is generally of minor importance.
  • the removal of the heat of reaction can be carried out in the usual way, for example by wall cooling or by utilizing a boiling cooling, or by a combination of these measures. In the case of boiling cooling, in particular the use of ethene or mixtures of ethene with the solvents mentioned above as preferred has proved suitable.
  • the distal chain end i. the end of the polymer removed from the initiator and obtained by the cationic polymerization process, for example the distal chain end of the isobutene polymer, with comonomers such as those listed above, e.g. Vinyl aromatics are implemented. So you can, for example first homopolymerize isobutene and then add the comonomer. The thereby emerging comonomer-derived reactive chain end is either deactivated or terminated according to one of the embodiments described below to form a functional end group or reacted again with isobutene to form higher block copolymers.
  • the 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 the like Mixtures 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 the like Mixtures with water.
  • difunctional (telechelic) polymers prepared by the cationic polymerization method such as isobutene polymers
  • the reactive chain end is prepared by adding a trialkylalylsilane compound, e.g. Trimethylallylsilane, terminated.
  • a trialkylalylsilane compound e.g. Trimethylallylsilane
  • the use of the allyl silanes leads to the termination of the cationic polymerization with the introduction of an allyl radical at the polymer chain end, as described, for example, in EP 264 214.
  • the reactive chain end is thermally converted, for example, by heating to a temperature of 70 to 200 0 C under vacuum, or by treatment with a base in a methylidene double bond.
  • Suitable bases are, for example, alkali metal alkoxides, such as sodium methoxide, sodium ethoxide or potassium tert-butoxide, basic aluminum oxide, alkali metal hydroxides, such as sodium hydroxide, or tertiary amines, such as pyridine or tributylamine.
  • Suitable bases are described in the specification: Kennedy et al., Polymer Bulletin 1985, 13, 435-439.
  • potassium tert-butylate is used.
  • the reactive chain end is reacted with a conjugated diene, such as butadiene, as described in DE-A 40 25 961.
  • two or more living polymer chains are coupled by the addition of a coupling agent.
  • “Coupling” means the formation of chemical bonds between the reactive chain ends and the coupling agent such that two or more polymer chains are joined to form a molecule.
  • Suitable coupling agents include, for example, at least two electrolytic leaving groups, all of which are allylated to the same or different double bonds, e.g. Trialkylsilyl phenomenon, so that the cationic center of a reactive chain end can attach in a concerted reaction with cleavage of the leaving group and displacement of the double bond.
  • Other coupling agents have at least one conjugated system to which the cationic center of a reactive chain end can add electrophilically to form a stabilized cation.
  • cleavage of a leaving group e.g. of a proton
  • the formation of a stable bond to the polymer chain ensues as the conjugated system is reformed.
  • conjugated systems can be linked together by inert spacers.
  • Suitable coupling agents include:
  • R is Ci-Cio-alkylene, preferably methylene or 2,2-propanediyl
  • Coupling agents suitable for the process according to the invention are known to the person skilled in the art and the coupling reaction can be carried out analogously to the reactions described in the following references: R. Faust, S. Hadjikyria cou, Macromolecules 2000, 33, 730-733; R. Faust, S. Hadjikyriacou, Macromolecules 1999, 32, 6393-6399; R. Faust, S. Hadjikyriacou, Polym. Bull. 1999, 43, 121-128; R. Faust, Y. Bae, Macromolecules 1997, 30, 198; R. Faust, Y. Bae, Macromolecules 1998, 31, 2480; R. Storey, Maggio, Polymer Preprints 1998, 39, 327-328; WO99 / 24480; US 5,690,861 and US 5,981,785.
  • the coupling is usually carried out in the presence of a Lewis acid, with such Lewis acids are suitable, which are also useful for carrying out the actual polymerization reaction.
  • the same solvents and temperatures are suitable for carrying out the coupling reaction as are chosen 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 cationic polymerization.
  • a molar amount of the coupling agent is used which is approximately equal to the quotient of the cationic polymerization.
  • molar amount of the initiator of formula (I) divided by the number of coupling sites of the coupling agent corresponds.
  • the solvent is generally removed in suitable aggregates such as rotary, falling film or thin-film evaporators or by relaxation of the reaction solution.
  • the polymers prepared by the process of the present invention and obtained by the cationic polymerization process have a narrow molecular weight distribution.
  • the polydispersity index PDI M w / M n is generally dependent on the molecular weight and is preferably below 1.40, more preferably below 1.35.
  • the PDI in polymers prepared by the process according to the invention such as, for example, isobutene polymers having a molecular weight M w greater than 10,000 g / mol is in the range from 1.1 to 1.2.
  • polymers of all molecular weight ranges can be produced by the process according to the invention.
  • isobutene these usually have a specific by gel permeation chromatography number average molecular weight M n of 500 to 1,000,000, in particular from 800 to 200,000, especially 1,000 to 50,000, on.
  • the telechelic polymers produced by the process according to the invention are used in further processing, for example to sealants and sealants or to adhesive (raw) substances. Further uses arise in the further processing into adhesive and sealant formulations, paints, fuel additives or polyurethane compounds.
  • the telechelic polymers obtained by the cationic polymerization process in particular isobutene polymers, can be subjected to one of the following derivatization reactions:
  • the polymer obtained by the cationic polymerization method such as the isobutene polymer can be reacted with a (hetero) aromatic compound in the presence of an alkylation catalyst.
  • a (hetero) aromatic compound in the presence of an alkylation catalyst.
  • Suitable aromatic and heteroaromatic compounds, catalysts and reaction conditions of this so-called Friedel-Crafts alkylation are described, for example, in J. March, Advanced Organic Chemistry, 4th Edition, published by John Wiley & Sons, pages 534-539, which is incorporated herein by reference.
  • Particularly suitable are aromatic compounds having 1 or 2 or 3 OH groups, which may optionally have at least one further substituent.
  • Preferred further substituents are methyl or ethyl.
  • phenol the cresol isomers, catechol, resorcinol, pyrogallol, fluoroglucinol or the xylenesol isomers.
  • phenol, o-cresol or p-cresol are used.
  • Suitable catalysts are AICb, AIBr 3 , BF 3 , BF 3 .2 CeH 5 OH, BF 3 [O (C 2 H 5 -b, TiCl 4 , SnCl 4 , AIEtCl 2 , FeCl 3 , SbCl 5 or SbF 5 .
  • the catalysts can be used together with a co-catalyst, for example an ether, such as dimethyl ether, diethyl ether, di-n-propyl ether or tetrahydrofuran
  • a co-catalyst for example an ether, such as dimethyl ether, diethyl ether, di-n-propyl ether or tetrahydrofuran
  • the reaction can also be catalyzed with protic acids, such as sulfuric acid, phosphoric acid or trifluoromethanesulfonic acid
  • Organic proton acids can also be used in polymer-bound form
  • zeolites and inorganic polyacids are also suitable.
  • the alkylation can be carried out solvent-free or in a solvent.
  • Suitable solvents are, for example, n-alkanes or mixtures thereof or alkylaromatics, such as toluene, ethylbenzene or xylene and halogenated derivatives thereof.
  • the preparation can be carried out analogously to the preparation of such compounds as described in WO 01/25 293 and WO 01/25 294, to which reference is hereby made in their entirety.
  • the polymer obtained by the cationic polymerization process can be epoxidized with a peroxide bond. Suitable methods for epoxidation are described in J. March, Advanced Organic Chemistry, 4th Edition, John Wiley & Sons, pp. 826-829, which is incorporated herein by reference.
  • the peroxide compound used is at least one peracid, such as m-chloroperbenzoic acid, performic acid, peracetic acid, trifluoropropylacetic acid, perbenzoic acid or 3,5-dinitroperbenzoic acid.
  • peracid such as m-chloroperbenzoic acid, performic acid, peracetic acid, trifluoropropylacetic acid, perbenzoic acid or 3,5-dinitroperbenzoic acid.
  • the manufacturer Development of peracids can be carried out in situ from the corresponding acids and H2O2 optionally in the presence of mineral acids.
  • epoxidizing reagents are, for example, alkaline hydrogen peroxide, molecular oxygen or alkyl peroxides, such as tert-butyl hydroperoxide.
  • Suitable solvents for the epoxidation are, for example, customary, non-polar solvents. Particularly suitable solvents are hydrocarbons such as toluene, xylene, hexane or heptane.
  • the epoxide formed can then be reacted ring-opening with protic compounds or electron donors, such as water, acids, alcohols, thiols or primary or secondary amines to give, inter alia, diols, glycol ethers, glycol thioethers or amines.
  • the polymer obtained by the cationic polymerization process in particular polyisobutene, can be reacted with a borane (optionally generated in situ), wherein an at least partially hydroxylated polymer obtained by the cationic polymerization process, in particular partially hydroxylated polyisobutene , is obtained.
  • a borane optionally generated in situ
  • Hydroborating reagents are, for example, diborane, which is generally generated in situ by reacting sodium borohydride with BF 3 etherate, disiamylborane (bis [3-methylbut-2-yl] borane), 1, 1, 2-trimethylpropylborane, 9-borbicyclo [ 3.3.1] nonane, diisocamphenylborane, which are obtainable by hydroboration of the corresponding alkenes with diborane, chloroborane-dimethylsulfide, alkyldichloroboranes or H3B-N (C2Hs) 2.
  • diborane which is generally generated in situ by reacting sodium borohydride with BF 3 etherate, disiamylborane (bis [3-methylbut-2-yl] borane), 1, 1, 2-trimethylpropylborane, 9-borbicyclo [ 3.3.1] nonane, diisocamphenylborane, which are obtainable by hydro
  • 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.
  • the polymer obtained by the cationic polymerization process in particular polyisobutene, can be reacted with at least one alkene which has an electrophile-substituted double bond in an ene reaction (see, for example, DE-A 4 319 672 or H Mach and P. Rath in "Lubrication Science Il (1999), pp. 175-185, which is incorporated herein by reference.)
  • an alkene designated as En having an allylic hydrogen atom with an electrophilic alkene the so-called Enophilic, converted in a pericyclic reaction puts. This includes a carbon-carbon bond, a double bond shift, and a hydrogen transfer.
  • the polymer obtained by the cationic polymerization process reacts as En.
  • Suitable enophiles are compounds such as those used as dienophiles in the Diels-Alder reaction.
  • Preference is given to using maleic anhydride as the enophile. This results, at least in part, in succinic anhydride groups (succinic anhydride groups) functionalized polymers obtained by the cationic polymerization process, especially partially succinic anhydride functionalized polyisobutenes.
  • the succinic anhydride derivatized polymer obtained by the cationic polymerization process in particular the polyisobutene derivatized with succinic anhydride groups, may be subjected to a sequential reaction selected from:
  • substituted alkenes of the formula (I) used in the process according to the invention can be obtained in many different ways, for example by addition of a compound HX to conjugated alkadienes.
  • the primary addition products may be further derivatized, if appropriate.
  • a further subject of the present invention is a process for the preparation of a substituted alkene of the formula (I) in which a conjugated alkadiene of the formula (II):
  • Each of the double bonds in formula (II) can have both ice and trans configuration.
  • Preferred conjugated alkadiene is the 1,3-pentadiene.
  • the compound HX is expediently a hydrogen halide or an organic carboxylic acid R 3 COOH.
  • suitable hydrogen halides are hydrogen chloride, hydrogen bromide or hydrogen iodide.
  • suitable organic carboxylic acids R 3 COOH are formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid or caproic acid.
  • a hydrogen halide in particular hydrogen chloride.
  • the hydrogen halide is preferably used in gaseous form or in the form of a solution in an organic solvent, for.
  • ethers such as diethyl ether, methyl tert-butyl ether, propyl ether, isopropyl ether, tetrahydrofuran or dioxane.
  • gaseous hydrogen halides in particular gaseous hydrogen chloride.
  • the compound HX is used in at least a stoichiometric amount relative to the conjugated alkadiene, preferably in a molar excess of from 1 to 1 to 10 times.
  • the reaction is carried out in the process according to the invention in general at a temperature of less than 40 ° C, preferably from - 25 to + 25 ° C, particularly preferably from -10 to +10 ° C.
  • the reaction can be carried out both at atmospheric pressure and at overpressure. Preferably, the pressure is from 1 to 10 bar.
  • the reaction can be carried out in the presence of a solvent. All solvents or mixtures thereof are suitable which have a suitable low dielectric constant and which are liquid under the reaction conditions.
  • alkanes having from 4 to 8, preferably from 5 to 8, carbon atoms such as butane, pentane, hexane, heptane, octane or their isomers
  • haloalkanes such as methyl chloride, methyl bromide, methylene chloride, methylene bromide, trichloromethane, Carbon tetrachloride, chloroethane, dichloroethane or trichloroethane
  • the reaction takes place in the absence of a solvent.
  • reaction of the conjugated alkadiene of the formula (II) with the compound HX can also be carried out in the presence of a catalyst, such as Lewis and / or Bronsted acids.
  • a catalyst such as Lewis and / or Bronsted acids.
  • Suitable Lewis acids are aluminum chloride, boron trifluoride, boron trifluoride alcoholate or boron trifluoride etherate, boron trichloride, titanium tetrachloride or tin tetrachloride.
  • Suitable Brönsted acids are those with greater acid strength than the compound HX.
  • the Brönsted acid may be either an inorganic acid such as sulfuric acid, phosphoric acid or hydrogen iodide (if X does not correspond to iodine) or a strong organic acid such as trifluoroacetic acid or trifluoromethanesulfonic acid.
  • the strong organic acid may also be in bound form, e.g. B. as an ion exchange resin.
  • reaction of the conjugated alkadiene of the formula (II) with the compound HX can also be carried out in the presence of an ammonium salt, such as tetraethylammonium chloride.
  • an ammonium salt such as tetraethylammonium chloride.
  • the reaction of the conjugated alkadiene of the formula (II) and the compound HX can be carried out by customary processes.
  • the conjugated alkadiene optionally present in a solvent and optionally together with a catalyst, at the reaction temperature and the compound HX admit.
  • the addition of compound HX is according to the nature of this compound.
  • hydrogen halides used in gaseous form can be passed through the initial educt or through its solution.
  • the hydrogen halide also gradually, for example, according to the consumption, in the pressure vessel be initiated.
  • the workup is carried out by conventional methods.
  • excess hydrogen halide can be removed, for example, by stripping with an inert gas, such as nitrogen, or by distillation, e.g. B. under reduced pressure, are removed.
  • an inert gas such as nitrogen
  • distillation e.g. B. under reduced pressure
  • the solvent is usually removed after removal of the hydrogen halide, which can be done for example by distillation.
  • acids R 3 COOH as compound HX or in the reaction of alkadienes of the formula (II) in the presence of Lewis or Brönsted acids these are usually extractive, z. B. by extraction of the reaction mixture with water or an aqueous base removed.
  • the product can then be purified by conventional methods, for example by distillation, in particular under reduced pressure.
  • the reaction product is often also available without purification in a degree of purity which is sufficient for further applications.
  • the cationic polymerization process according to the invention is carried out in the presence of one or more substituted alkenes of the formula (I).
  • Replacement of dicumyl chloride, which is often used in this context, which can unintentionally react to indanyl or diindanyl groups, has the advantage of avoiding the side reactions known from dicumyl chloride.
  • GPC To perform gel permeation chromatography, a combination of two styragel columns (1000 and 10000A) was used. The calibration was carried out according to isobutene standard. M n: 6001 g / mol, M w: 7561 g / mol; PDI: 1, 26; M p : 7493 g / mol.

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Abstract

L'invention concerne un procédé de polymérisation cationique de monomères à insaturations éthyléniques polymérisables cationiquement en présence d'un ou de plusieurs acides de Lewis, caractérisé en ce que la polymérisation a lieu en présence d'un ou de plusieurs alcènes substitués de formule (I), dans laquelle R<SUP>1</SUP> représente H ou un alkyle en C<SUB>1</SUB>-C<SUB>5</SUB>, R<SUP>2</SUP> représente un alkyle en C<SUB>1</SUB>-C<SUB>6</SUB>, X représente un halogène, OR<SUP>3</SUP> ou OCOR<SUP>3</SUP>, R<SUP>3</SUP> représentant un alkyle en C<SUB>1</SUB>-C<SUB>6</SUB>.
PCT/EP2007/052263 2006-03-16 2007-03-12 Alcene substitue en tant qu'amorceur de polymerisation cationique WO2007104727A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3931306A (en) * 1973-10-23 1976-01-06 International Flavors & Fragrances Inc. Process for producing isomer mixtures containing high proportions of cis-2-methyl-3-pentenoic acid
GB1524695A (en) * 1974-07-22 1978-09-13 Int Flavors & Fragrances Inc Flavouring and fragrance compositions
EP0489508A2 (fr) * 1990-11-28 1992-06-10 BP Chemicals Limited Polymérisation cationique de 1-oléfines
US20040015029A1 (en) * 2000-12-12 2004-01-22 Arno Lange Method for producing polyisobutenes

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3931306A (en) * 1973-10-23 1976-01-06 International Flavors & Fragrances Inc. Process for producing isomer mixtures containing high proportions of cis-2-methyl-3-pentenoic acid
GB1524695A (en) * 1974-07-22 1978-09-13 Int Flavors & Fragrances Inc Flavouring and fragrance compositions
EP0489508A2 (fr) * 1990-11-28 1992-06-10 BP Chemicals Limited Polymérisation cationique de 1-oléfines
US20040015029A1 (en) * 2000-12-12 2004-01-22 Arno Lange Method for producing polyisobutenes

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
MAYR, HERBERT ET AL: "Lewis acid catalyzed additions of 1,3-alkyl substituted allyl chlorides to alkenes", CHEMISCHE BERICHTE , 117(8), 2555-79 CODEN: CHBEAM; ISSN: 0009-2940, 1984, XP009085607 *
MUKS, ELVI ET AL: "Carbocationic additions of allylic chlorides to isoalkenes. Steric effects of substituents", EESTI TEADUSTE AKADEEMIA TOIMETISED, KEEMIA , 41(1), 26-9 CODEN: ETAKE9, 1992, XP009085602 *
MUKS, ELVI: "Pathways to the higher products in Lewis acid-catalyzed additions of allylic chlorides to isoalkenes and isoprene", JOURNAL OF CHEMICAL RESEARCH, SYNOPSES , (12), 496-7 CODEN: JRPSDC; ISSN: 0308-2342, 1995, XP009085593 *
NORDLANDER, J. ERIC ET AL: "Regiochemistry of the addition of hydrochloric acid-d to trans-1,3- pentadiene", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY , 101(5), 1288-9 CODEN: JACSAT; ISSN: 0002-7863, 1979, XP002438987 *

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