WO2007104711A1

WO2007104711A1 - Method for the cationic polymerization of cationically polymerizable ethylenically unsaturated monomers in the presence of epoxy ethers

Info

Publication number: WO2007104711A1
Application number: PCT/EP2007/052215
Authority: WO
Inventors: Szilard Csihony; Hans Peter Rath; Heike Pfistner
Original assignee: Basf Se
Priority date: 2006-03-16
Filing date: 2007-03-09
Publication date: 2007-09-20

Abstract

The invention relates to a method for the cationic polymerization of cationically polymerizable ethylenically unsaturated monomers in the presence of one or more Lewis acids. The invention is characterized in that polymerization is carried out in the presence of one or more epoxy ethers I, formula (I), wherein R1 represents a hydrolizable hydrocarbyl group with 1 to 20 carbon atoms, R2, R3 and R4 independently represent hydrogen or a hydrocarbyl group with 1 to 20 carbon atoms, and A represents an alkylene group with 2 to 6 carbon atoms.

Description

Process for the cationic polymerization of cationically polymerizable ethylenically unsaturated monomers in the presence of epoxy ethers

description

The present invention relates to an improved 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 this process for cationic polymerization. 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 in other combinations not only in the particular concretely specified combination but also in the context of the invention.

In the preparation of isobutene polymers by cationic polymerization (also referred to as "living cationic polymerization"), initiator systems comprising a Lewis acid and an organic compound which forms a carbocation or a cationogenic complex with the Lewis acid are employed. The terms 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. Thus, EP-A 713 883 describes the preparation of telechelic isobutene polymers using an at least bifunctional initiator such as dicumyl chloride. A disadvantage of this 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. 1993, 31, pp. 2387-2391), which impairs the synthesis of defined telechelic isobutene polymers.

Substituted cycloalkanes can be used according to the application WO 05/44766 as initiators for the cationic polymerization.

WO 99/29744 discloses epoxides containing alkyl, aryl or aralkyl radicals, for example 2,4,4-trimethylpentyl-1,2-epoxide, epoxidized α-methylstyrene or hexaepoxyqualenes, as initiators for cationic polymerization. There is a continuing need for improved processes for cationic polymerization in which initiators are used which do not have the adverse side reactions described above and in particular are easy to prepare and stable in storage.

The object of the present invention was therefore to develop an improved 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 particular, initiators should be developed which do not undergo rearrangement or reactions to indanyl or diindane groups.

The object is achieved by a process for the cationic polymerization of cationically polymerizable ethylenically unsaturated monomers in the presence of one or more Lewis acids, which is characterized in that in the presence of one or more epoxy ethers of general formula I

in the

R ¹ denotes a hydrolyzable hydrocarbyl radical having 1 to 20 carbon atoms,

R ² , R ³ and R ⁴ independently of one another denote hydrogen or a hydrocarbyl radical having 1 to 20 carbon atoms and

A is an alkylene group having 2 to 6 carbon atoms,

is polymerized.

Hydrocarbyl radicals are to be understood as meaning hydrocarbon radicals which are either composed only of carbon and hydrogen or contain a small amount of heteroatoms and / or functional groups, without impairing the predominantly hydrocarbon character of the radical. In the presence of such heteroatoms or functional groups, they must be inert, i. they must not interfere with the cationic polymerization reaction of the invention and subsequent reactions of the resulting polymers.

In the case of the variable R ¹ , the hydrocarbyl radical must be hydrolyzable, ie, in a subsequent reaction, the ether function R ¹ -OA- present in the epoxyethers I must be convertible into the hydroxy function HO-A- by hydrolysis. Suitable radicals R ¹ are therefore, in particular C 1 -C 20 -alkyl radicals, preferably C 1 -C 5 -alkyl radicals, C 3 -C 20 -alkenyl radicals, preferably C 3 -C 18 -alkenyl radicals, C 5 -C 12 -cycloalkyl radicals, preferably C 6 -C 8 -cycloalkyl radicals, and C 7 -C 20 -arylalkyl radicals, preferably C 7 -C 12 -arylalkyl radicals.

Examples of C 1 -C 20 -alkyl radicals or C 1 -C 5 -alkyl radicals which may be linear or branched are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n -Pentyl, 2-methylbutyl, neopentyl, n -hexyl, 2-methylpentyl, 3-methylpentyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 2-ethylbutyl, n -heptyl, n-octyl and 2-ethylhexyl ,

Examples of C 3 -C 20 -alkenyl radicals or C 3 -C -alkenyl radicals are allyl, oleyl, linolyl and linolenyl.

Examples of C 5 -C 12 cycloalkyl radicals or C 5 -C 8 cycloalkyl radicals are cyclopentyl, methylcyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl and cycloheptyl.

Examples of C7-C20-arylalkyl radicals or C7-C12-arylalkyl radicals are benzyl, 1-phenylethyl, 2-phenylethyl, 3-phenylpropyl, 4-phenylbutyl and o-, m- or p-methylbenzyl.

In a preferred embodiment, the variable R ¹ denotes a hydrolyzable alkyl radical having 1 to 8 carbon atoms, in particular a tert-butyl radical.

In a further preferred embodiment, the variables R ² , R ³ and R ⁴ independently of one another are hydrogen or a methyl group, in particular all three variables R ² , R ³ and R ^{4 are} hydrogen.

The bridging variable A preferably represents a methylene group, a 1,1-ethylene group, a 1,2-ethylene group, a 1,3-propylene group, a 1,4-butylene group or a 2,2-propanediyl group.

With very particular preference, the epoxy ether of the general formula I is tert-butyl glycidyl ether.

Epoxy ethers of the general formula I are known in principle as substances and are therefore generally available. If they can not be purchased, they may be prepared by methods known to those skilled in the art.

The epoxy ethers I act advantageously 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. Usually, the described epoxy ethers I in their function as initiators 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 ethylenic unsaturated monomers used.

The polymers obtained with the aid of the epoxy ethers I as initiators contain at the opposite end of the polymer chain a hydroxy group derived from the epoxide function and the ether function R ¹ -OA-. By subsequent hydrolysis of this ether function, a second hydroxy group can be generated at this chain end, which can be further functionalized.

Therefore, the present invention also provides polymers obtainable by the process according to the invention described. The end groups of these polymers have in particular C = C double bonds.

The present invention also provides for the use of the described epoxy ethers of the general formula I as initiators for the cationic polymerization of cationically polymerizable ethylenically unsaturated monomorers in the presence of one or more Lewis acids.

Suitable cationically polymerizable, ethylenically unsaturated monomers are, in the context of the process according to the invention, in particular electron-rich olefin derivatives. Preference is given to using isobutene, vinylaromatic compounds such as styrene or α-methylstyrene or Cs-do-isoolefins such as 2-methylbutene-1, 2-methylpentene-1, 2-methylhexene-1,2-ethyl-pentene-1,2-ethylhexene-1 or 2-Propylhepten -1. Preferably, the process is used to produce homo-, co- or block copolymers of isobutene.

Suitable isobutene feedstocks are isobutene itself as well as isobutene-containing C4 hydrocarbon streams, for example C4 raffinates, C4 cuts from isobutene dehydrogenation, C4 cuts from steam crackers, FCC crackers (FCC: Fluid Catalyzed Cracking), insofar as 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. When using C4 cuts or C4 raffinates as the feedstock, hydrocarbons other than isobutene play the role of an inert solvent.

It is also possible to react monomer mixtures of isobutene with other ethylenically unsaturated monomers which are copolymerizable with isobutene under cationic polymerization conditions. The process according to the invention is also suitable for the block copolymerization of isobutene with ethylenically unsaturated comonomers polymerizable under cationic polymerization conditions. net. If monomer mixtures of isobutene are to be polymerized with suitable comonomers, the content of isobutene can vary within wide limits, as required. Preferably, the monomer mixture contains more than 60 wt .-%, in particular more than 80 wt .-%, and, more preferably, more than 95 wt .-% isobutene, and less than 40 wt .-%, preferably less than 20 Wt .-%, and in particular less than 5 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 4-tert-butylstyrene, n-butene and Cs-do -olefins such as 2-methylbutene-1, 2-methylpentene-1, 2-methylhexene-1, 2-ethylpentene-1, 2-ethylhexene-1 or 2-propylheptene-1. Furthermore, other electron-rich olefin derivatives can be used as comonomers. Other suitable comonomers are 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.

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 in the art, for example from JP. 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 used in an amount sufficient to form an initiator complex of one or more Lewis acids and one or more epoxy ethers I as initiators. The molar ratio of Lewis acids to initiators is generally from 10: 1 to 1: 1, especially from 2.5 to 1: 1.

It has proven useful to carry out the cationic polymerization in the inventive process additionally in the presence of an electron donor or the mixture of several electron donors. 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, α-, ß- or γ-picoline and 2,6-dimethyl-pyridine, and 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, for example 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 or triphenylphosphine; or non-polymerizable, aprotic, organosilicon compounds which have at least one oxygen-bonded organic radical.

Among the abovementioned donors, pyridine, in particular picolines, or sterically hindered pyridine derivatives, and in particular organosilicon compounds, are preferred. Examples of such preferred 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 2 to 8, preferably 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 also n-octane or its isomers, cyclic alkanes having 5 to 8 carbon atoms, such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, cycloheptane, acyclic alkenes having preferably 2 to 8 carbon atoms, such as ethene, iso or n Propene, n-butene, n-pentene, n-hexene or n-heptene, cyclic olefins such as cyclopentene, cyclohexene or cycloheptene, aromatic hydrocarbons such as toluene, xylene, ethylbenzene and halogenated hydrocarbons such as halogenated aliphatic hydrocarbons, eg chloromethane, Dichloromethane, trichloromethane, chloroethane, 1, 2-dichloroethane or 1, 1, 1-trichloroethane or 1-chlorobutane, and halogenated aromatic hydrocarbons such as chlorobenzene or Fluorobenzene. 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. In the polymerization of isobutene as an ethylenically unsaturated monomer and the use of feedstock from C4 cuts or C4 raffinates, the hydrocarbons other than isobutene play the role of an inert solvent. Particularly preferred solvents are aromatic hydrocarbons, toluene being particularly preferred. Also preferred are solvent mixtures comprising at least one halogenated hydrocarbon and at least one aliphatic or aromatic hydrocarbon. In particular, 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, in particular largely anhydrous reaction conditions. Under 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. As a rule, therefore, the feedstocks will be dried physically and / or by chemical means before being used. For example, the aliphatic or cycloaliphatic hydrocarbons used as solvent can be added after usual pre-cleaning and predrying with an organometallic compound, for example an organolithium, organomagnesium or organoaluminum compound, in an amount sufficient to remove traces of water from the solvent. The solvent thus treated is then condensed directly into the reaction vessel. In a similar manner, it is also possible to use the monomers to be polymerized, in particular the isobutene.

As a rule, the cationic polymerization is carried out by the process according to the invention at temperatures below 0 ° C., for. In the range of 0 to -140 ° C, preferably in the range of -10 to -120 ° C, and more preferably in the range of -20 to -110 ° C. The reaction pressure is generally of minor importance.

It has proven to be advantageous to activate the described epoxyether initiators before the start of polymerization by adding a partial amount or the entire amount of the Lewis acids and / or electron donors used in order to obtain polymers having better properties, for example a lower polydispersity index PDI. Thus, a typical embodiment of the cationic polymerization according to the invention comprises the co-dissolution of the epoxy ethers I used together with the Lewis acids and / or electron donors in a suitable solvent or solvent mixture before addition of the monomers. 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 evaporative cooling, the use of ethene or mixtures of ethene with the solvents mentioned above as being preferred has proven particularly useful.

For the preparation of block copolymers, 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, be implemented. For example, it is possible first to homopolymerize isobutene and then to add the comonomer. 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, for example, reacted again with isobutene to form higher block copolymers.

For termination of the reaction, 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 their mixtures with water.

In order to obtain difunctional (telechelic) polymers, for example isobutene polymers, by the process of cationic polymerization, one terminates the distal, that is to say the reactive, chain end to form an ethylenically unsaturated group, it being possible, for example, to obtain B. Reacting the reactive chain end with a terminating reagent which adds or appropriately treats an ethylenically unsaturated group at the chain end to convert the reactive chain end into such a group.

In one embodiment, the reactive chain end is prepared by adding a trialkylalylsilane compound, e.g. Trimethylallylsilane, terminated. 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.

In another embodiment, the reactive chain end is thermally converted, for example, by heating to a temperature of 70 to 200 ⁰ C, or by treatment with a base in a methylidene double bond. Suitable bases include alkali metal alkoxides such as sodium methoxide, sodium ethoxide or potassium tert-butoxide, basic alumina, 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. Preferably, potassium tert-butoxide is used. In a further embodiment, the reactive chain end is reacted with a conjugated diene, for example butadiene, as described in DE-A 40 25 961.

In a further embodiment, 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. Trialkylsilylgruppen, so that the cationic center of a reactive chain end can attach in a concerted reaction with cleavage of the leaving group and displacement of the double bond. Other coupling agents have at least one conjugated system to which the cationic center of a reactive chain end can add electrophilically to form a stabilized cation. By cleavage of a leaving group, e.g. of a proton, the formation of a stable bond to the polymer chain ensues as the conjugated system is reformed. Several of these conjugated systems can be linked by inert spacers.

Suitable coupling agents include:

(i) Compounds having at least two 5-membered heterocycles having a heteroatom selected from oxygen, sulfur and nitrogen, e.g. organic compounds having at least two furan rings, such as

Q → Q

wherein R is Ci-Cio-alkylene, preferably methylene or 2,2-propanediyl; (ii) compounds having at least two allyl-containing trialkylsilyl groups, such as

1,1-bis (trialkylsilylmethyl) ethylene, e.g. 1,1-bis (trimethylsilylmethyl) ethylene, or bis [(trialkylsilyl) propenyl] benzenes, e.g.

(where Me is methyl),

(iii) compounds having at least two vinylidene groups conjugated to each two aromatic rings, such as bis-diphenylethylenes, e.g.

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; WO 99/24480; 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. In addition, the same solvents and temperatures are suitable for carrying out the coupling reaction as are chosen for carrying out the actual polymerization reaction. Conveniently, the coupling can therefore be used as a one-pot reaction following the polymerization reaction in the perform the same solvent in the presence of the Lewis acid used for cationic polymerization. Usually, a molar amount of the coupling agent is used which corresponds approximately to the quotient of the molar amount of the initiator of the formula (I) used for cationic polymerization divided by the number of coupling sites of the coupling agent.

After termination or coupling, the solvent is usually removed in suitable units such as rotary, falling-film or thin-film evaporators or by relaxation of the reaction solution.

The polymers prepared by the process of the invention obtained by the cationic polymerization process, such as isobutene polymers, have a narrow molecular weight distribution. The polydispersity index PDI = M _w / M _n is preferably below 2.0, more preferably below 1.60, in particular below 1.40.

In principle, polymers of all molecular weight ranges can be produced by the process according to the invention. In the case of 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 obtained by the cationic polymerization process, in particular isobutene polymers, may be subjected to one of the following derivatization reactions:

Electrophilic substitution on aromatics

The polymer obtained by the cationic polymerization method such as the isobutene polymer can be reacted with an aromatic or heteroaromatic 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, Verlag John Wiley & Sons, pages 534-539, to which reference is hereby made becomes.

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. Particular preference is given to phenol, the cresol isomers, catechol, resorcinol, pyrogallol, fluoroglucinol or the xylenesol isomers. In particular, phenol, o-cresol or p-cresol are used. Examples of suitable catalysts are AICb, AIBr ₃ , BF ₃ , BF ₃ .2CoH 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 cocatalyst, 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 For example, as an ion exchange resin, 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.

For further functionalization, the polymer obtained by the process for cationic polymerization and then alkylated, in particular polyisobutenylphenol, a reaction in the Mannich reaction with at least one aldehyde, for example formaldehyde, and at least one amine containing at least one primary or secondary amine function, to give a compound alkylated with a polymer obtained by the cationic polymerization process, in particular a polyisobutylene-alkylated and additionally at least partially aminoalkylated compound. It is also possible to use reaction and / or condensation products of aldehyde and / or amine. 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.

epoxidation

The polymer obtained by the cationic polymerization method, especially polyisobutene, can be epoxidized with a peroxide compound. Suitable methods for epoxidation are described in J. March, Advanced Organic Chemistry, 4th Edition, John Wiley & Sons, S. 826-829, incorporated herein by reference. Preferably, 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. The preparation of the peracids can be carried out in situ from the corresponding acids and hydrogen peroxide (H ₂ O ₂ ) optionally in the presence of mineral acids. Further suitable epoxidation 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, conventional 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.

hydroboration

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. 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 hydrogenation reagents are, for example, diborane, which is generally generated in situ by reaction of 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-dimethyl sulfide, alkyldichloroboranes or H3B-N (C2H ₅ ) 2.

Usually, the alkyl boranes formed are not isolated, but converted by subsequent reaction directly into the desired products. A very important implementation of the alkylboranes is the reaction with alkaline hydrogen peroxide to give an alcohol which preferably corresponds formally to the anti-Markovnikov hydration of the alkene. Furthermore, the resulting alkylboranes can be subjected to a reaction with bromine in the presence of hydroxide ions to obtain the bromide.

Ene reaction

The polymer obtained by the cationic polymerization method, especially polyisobutene, can be reacted with at least one alkene having 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.) In the En reaction, an alkene designated as En having an allylic hydrogen atom is reacted with an electrophilic alkene, the so-called enophile, This reaction involves the formation of a carbon-carbon bond, a double-bond shift, and a hydrogen transfer reaction. [Vor Vor] In particular, the polymer obtained by the cationic polymerization process, in particular polyisobutene, reacts as En They are also used as dienophiles in the Diels-Alder reaction. Preferred as Enophil Maleinsäurea used nhydride. This results, at least in part, in Bern tartaric 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:

α) reaction with at least one amine to give a polymer which is at least partially functionalized with succinimide groups and / or succinamide groups and which has been obtained by the process for cationic polymerization, in particular a polyisobutene functionalized at least in part with succinimide groups and / or succinamide groups;

β) reaction with at least one alcohol to give a polymer which is at least partially functionalized with succinic ester groups and which has been obtained by the cationic polymerization process, in particular a polyisobutene functionalized at least in part with succinic ester groups; and

γ) Reaction with at least one thiol to give a polymer which is at least partially functionalized with succinothioester groups and which has been obtained by the cationic polymerization process, in particular a polyisobutene functionalized at least in part with succinothioester groups.

The inventive method for cationic polymerization is carried out in the presence of one or more epoxy ethers of the general 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. Compared to those in the

WO 99/29744 described by means of initiators based on epoxides with alkyl, aryl or aralkyl radicals polymers prepared with the present Epoxye- I offer because of the second by hydrolysis of the ether function R ¹ -OA- generated hydroxyl group at the chain end further possibilities for derivatization. Examples:

Example 1: Preparation of polyisobutene with tert-butylglycidyl ether as initiator

1.7 g (7 mmol) of phenyltriethoxysilane, 3.3 g (25 mmol) of tert-butylglycidyl ether and 8.5 g (45 mmol) of titanium tetrachloride were dissolved in a mixture of 150 ml of hexane (dried over molecular sieve) and 150 ml of dichloromethane ( dried over molecular sieve) in a 1 liter round bottomed flask with reflux condenser and gas inlet capillary at -76 ° C. Dry nitrogen was continuously passed through the solution. The polymerization was started by the addition of 200 ml (2 mol) of isobutene. The temperature of the solution rose to -70 ° C, gradually turning yellow. The solution was cooled again to -76 ° C. After 2 hours, the polymerization was stopped by adding 10 ml of ethanol. 150 ml of heptane was added and extracted three times with water. The organic phase was dried over sodium sulfate. The solvents were distilled off at 5 mbar and 50 ° C. This gave 15.1 g of polyisobutene having a molecular weight M _n of 8320 g / mol determined by gel permeation chromatography and a polydispersity index PDI of 1.62.

Example 2: Preparation of polyisobutene with tert-butyl glycidyl ether as initiator

200 ml (2 mol) of isobutene were dissolved in a mixture of 150 ml of hexane (dried over molecular sieve) and 150 ml of dichloromethane (dried over molecular sieve) in a 1 liter round bottom flask with reflux condenser and gas inlet capillary at -76 ° C. Dry nitrogen was continuously passed through the solution. 3.3 g (25 mmol) of tert-butyl glycidyl ether were added. The polymerization was started by the addition of 1.7 g (7 mmol) of phenyltriethoxysilane and 8.5 g (45 mmol) of titanium tetrachloride. The temperature of the solution rose to -60 ° C, gradually turning yellow. The solution was cooled again to -76 ° C. After 2 hours, the polymerization was stopped by adding 10 ml of ethanol. 150 ml of heptane was added and extracted three times with water. The organic phase was dried over sodium sulfate. The solvents were distilled off at 5 mbar and 50 ° C. This gave 61.6 g of polyisobutene having a molecular weight M _n of 3180 g / mol, determined by gel permeation chromatography, and a polydispersity index PDI of 2.64.

analytics:

To perform gel permeation chromatography (GPC), a combination of two styragel columns (1000 and 10,000 angstroms) was used. The calibration was done according to isobutene standard. M _n: 6001 g / mol, M _w: 7561 g / mol; D: 1, 26; M _p : 7493 g / mol.

Claims

claims

1. A process for the cationic polymerization of cationically polymerizable ethylenically unsaturated monomorer in the presence of one or more Lewis acids, characterized in that in the presence of one or more epoxy ethers of general formula I

in the

R ¹ denotes a hydrolyzable hydrocarbyl radical having 1 to 20 carbon atoms,

A is an alkylene group having 2 to 6 carbon atoms,

is polymerized.

2. The method according to claim 1, characterized in that the variable R ¹ denotes a hydrolyzable alkyl radical having 1 to 8 carbon atoms, in particular a tert-butyl radical.

3. The method according to claim 1 or 2, characterized in that the variables R ² , R ³ and R ^{4 are} independently hydrogen or a methyl group.

4. Process according to claims 1 to 3, characterized in that the variable A is a methylene group, a 1, 1-ethylene group, a 1, 2-ethylene group, a 1, 3-propylene group, a 1, 4-butylene group or a 2,2-Propanediylgruppe stands.

5. The method according to claim 1, characterized in that it is the tert-Butylglycidylether in the E- poxyether of general formula I.

6. Process according to claims 1 to 5, characterized in that the cationically polymerisable ethylenically unsaturated monomers comprise isobutene.

7. Use of the epoxy ethers of the general formula I as defined in claims 1 to 5 as initiators for the cationic polymerization of cationically polymerizable ethylenically unsaturated monomorer in the presence of one or more Lewis acids.

8. Polymers obtainable by a process according to any one of claims 1 to 6.

9. Polymers according to claim 8, characterized in that the end groups of the polymers have C = C double bonds.