DE102009019470A1 - Polymerizing cationically polymerizable monomers e.g. isobutene, comprises providing two liquid streams comprising the monomer, boron trifluoride complex and/or solvent, mixing liquids in microstructured mixer and polymerizing - Google Patents

Abstract

Method for continuous polymerization of cationically polymerizable monomers, comprises: (a) providing at least two liquid streams comprising at least one of the monomer, at least one boron trifluoride complex and/or optionally at least one solvent, provided that the stream comprising the boron trifluoride complex does not contain the monomer; (b) mixing the two liquid streams to obtain a reaction mixture, where the mixing is successive or simultaneous and is carried out in a mixer having microstructures; and (c) polymerizing the reaction mixture in at least one reaction zone. Method for continuous polymerization of cationically polymerizable monomers, comprises: (a) providing at least two liquid streams comprising at least one cationically polymerizable monomer, at least one boron trifluoride complex having at least one cocatalyst and/or optionally at least one solvent, provided that the stream comprising the boron trifluoride complex does not contain the monomer; (b) mixing the two liquid streams to obtain a reaction mixture, where the mixing is successive or simultaneous and is carried out in a mixer having microstructures; and (c) polymerizing the reaction mixture in at least one reaction zone. Independent claims are included for a device, for carrying out the above process, comprising at least two or three storage containers (1,4) for liquid starting materials; two feeders, each one for feeding the liquid stream from at least two storage containers; one or more sequentially-connected mixers (3) to which the liquid streams are fed and in which the obtained reaction mixture is mixed, where at least the last mixer in the direction of flow is equipped with microstructures before entering into the reaction zone(s); at least one reaction zone, which is microstructured; and a discharge container (11) that is optionally provided with one or more devices for adding and/or mixing.

Description

The The present invention relates to a method and a device for the continuous polymerization of cationically polymerizable Monomers using Bortrifluoridkomplexkatalysatoren, at the at least two starting materials in one or more mixers mixed with microstructures and then in at least a reaction zone are polymerized.

beschrieben wird, d. h. die Doppelbindung befindet sich in der Polymerkette in α-Position. ”Polymer” steht für den um eine Isobuteneinheit verkürzten Polyisobutenrest.The preparation of polymers and in particular polyisobutenes having a high proportion of terminal olefinic double bonds is known. Polyisobutenes having a high content of terminal double bonds are also referred to as highly reactive. In contrast to low-reactive polyisobutenes, highly reactive polyisobutenes are understood to mean those polymers which have a content of terminal vinylidene double bonds (α-double bonds) of at least 60 mol%, preferably at least 70 mol% and in particular of at least 80 mol%, based on the entirety of all macromolecules possess. Vinylidene double bonds are those whose position in the macromolecule is represented by the following general formula

is described, ie the double bond is located in the polymer chain in α-position. "Polymer" stands for the truncated to an isobutene polyisobutene.

terminal Vinylidene groups have the highest reactivity while lying further inside the molecule Double bonds no or definitely a much lower Show reactivity. A high reactivity is however, requirement or at least a substantial advantage for the functionalization of the polyisobutenes. Functionalized polyisobutenes are used for example as fuel and lubricant additives.

Known methods of the prior art for the preparation of highly reactive polyisobutenes, for example, those in the EP-A-0628575 described methods, use a boron trifluoride complex catalyst, which is fed in continuous processes directly into the reactor to prevent premature polymerization. A disadvantage of these methods is that they usually have to be carried out at low temperatures, since the molecular weight of the polymer chains formed decreases greatly with increasing reaction temperatures. Another disadvantage is that relatively large amounts of catalyst are required.

The WO 99/54362 describes a process for continuous radical solution polymerization, in which at least two reactants are passed through a micromixer and brought together, mixed together and then polymerized in a tubular reactor.

task The present invention was a more economical process for the production of polymers with a high content available at terminal olefinic double bonds to deliver. In particular, the process should be continuously feasible be, a high conversion with relatively short residence times in the reactor allow and require smaller amounts of catalyst than the methods of the prior art.

Surprisingly, has been found that cationically polymerizable monomers at high Sales in short reaction times to products with a sufficient high molecular weight with less amount of catalyst than in the state The technique can be polymerized when the starting materials prior to introduction into the reaction zone in at least one Mixer with microstructures mixed and then preferably in a heat exchange-intensive reaction zone for the reaction to be brought. By the use according to the invention of micromixers, it is also surprisingly possible to carry out the polymerization in heterogeneous phase, without blockages in the reaction system (eg mixers, lines, Reactor (parts)) comes.

• (a) Bereitstellen von wenigstens zwei flüssigen Strömen, wobei die wenigstens zwei Ströme jeweils eine oder mehrere der folgenden Komponenten umfassen: wenigstens ein kationisch polymerisierbares Monomer, wenigstens einen Bortrifluoridkomplex mit wenigstens einem Cokatalysator und gegebenenfalls wenigstens ein Lösungsmittel, mit der Maßgabe, das derjenige Strom, der den wenigstens einen Bortrifluoridkomplex enthält, kein Monomer enthält;
• (b) Mischen der wenigstens zwei flüssigen Ströme unter Erhalt eines Reaktionsgemischs, wobei im Fall, dass mehr als zwei flüssige Ströme in Schritt (a) bereitgestellt werden, das Mischen der Ströme sukzessive oder gleichzeitig erfolgen kann und wobei wenigstens ein Mischvorgang in einem Mischer mit Mikrostrukturen durchgeführt wird; und
• (c) Polymerisieren des Reaktionsgemischs in wenigstens einer Reaktionszone.

The invention thus provides a process for the continuous polymerization of cationically polymerizable monomers, comprising the following steps:

• (A) providing at least two liquid streams, wherein the at least two streams each comprise one or more of the following components: at least one cationically polymerizable monomer, at least one boron trifluoride complex with at least one cocatalyst and optionally at least one solvent, with the proviso that the stream containing at least one boron trifluoride contains complex, contains no monomer;
• (b) mixing the at least two liquid streams to obtain a reaction mixture, wherein in case more than two liquid streams are provided in step (a), the mixing of the streams may be successive or simultaneous and wherein at least one mixing operation is in a mixer Microstructures is performed; and
• (c) polymerizing the reaction mixture in at least one reaction zone.

In the context of the present invention, the following generic terms have the following meanings, unless expressly deviating definitions are given:
By alkyl is meant a linear or branched saturated hydrocarbon radical having generally 1 to 20 C atoms (= C ₁ -C ₂₀ -alkyl), and preferably 1 to 10 C-atoms (= C ₁ -C ₁₀ -alkyl),
C ₁ -C ₄ -alkyl represents a linear or branched alkyl group having 1 to 4 carbon atoms. Examples of these are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl.

C ₁ -C ₆ -alkyl represents a linear or branched alkyl group having 1 to 6 carbon atoms. Examples of these are, in addition to the radicals mentioned above for C ₁ -C ₄ -alkyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, 1,1-dimethylpropyl, 1,2 Dimethyl propyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3 Dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl and others Positional isomers thereof.

C ₁ -C ₈ -alkyl represents a linear or branched alkyl group having 1 to 8 carbon atoms. Examples of these are the abovementioned C ₁ -C ₆ -alkyl radicals and furthermore heptyl, octyl and their constitutional isomers such as 2-ethylhexyl.

C ₁ -C ₁₀ alkyl represents a linear or branched alkyl group having 1 to 10 carbon atoms. Examples thereof are the above-mentioned C ₁ -C ₈ -alkyl radicals and additionally nonyl, decyl and their constitutional isomers.

C ₁ -C ₁₉ -alkyl represents a linear or branched alkyl group having 1 to 19 carbon atoms. Examples thereof are the abovementioned C ₁ -C ₁₀ -alkyl radicals and furthermore undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and their constitutional isomers.

C ₁ -C ₂₀ -alkyl represents a linear or branched alkyl group having 1 to 20 carbon atoms. Examples thereof are the abovementioned C ₁ -C ₁₉ -alkyl radicals and furthermore eicosyl and constitutional isomers thereof.

Aliphatic C ₁ -C ₃₀ monoalcohols are linear or branched aliphatic hydrocarbons, preferably saturated linear or branched aliphatic hydrocarbons (alkanes) having 1 to 30 carbon atoms in which a hydrogen atom is replaced by a hydroxy group. Examples of saturated aliphatic C ₁ -C ₃₀ monoalcohols are methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, isobutanol, tert-butanol, 1-, 2- or 3-pentanol, neopentanol (2, 2-dimethylpropanol), 1-, 2- or 3-hexanol, heptanol, octanol, 2-ethylhexanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol, henicosanol, docisanol , Tricosanol, tetracosanol, pentacosanol, hexacosanol, heptacosanol octacosanol, nonacosanol, squanol and the conformational isomers thereof.

Aliphatic C ₁ -C ₁₀ monoalcohols are linear or branched aliphatic hydrocarbons, preferably saturated linear or branched aliphatic hydrocarbons (alkanes) having from 1 to 10 carbon atoms in which a hydrogen atom is replaced by a hydroxy group. Examples of saturated aliphatic C ₁ -C ₁₀ -monoalcohols are methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, isobutanol, tert-butanol, 1-, 2- or 3-pentanol, neopentanol (2, 2-dimethylpropanol), 1-, 2- or 3-hexanol, heptanol, octanol, 2-ethylhexanol, nonanol, decanol and the conformational isomers thereof.

Saturated C ₁ -C ₄ aliphatic monoalcohols are linear or branched alkanes of 1 to 4 carbon atoms in which a hydrogen atom is replaced by a hydroxy group. Examples are methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, isobutanol and tert-butanol.

Saturated C ₁ -C ₃ aliphatic monoalcohols are linear or branched alkanes of 1 to 3 carbon atoms in which a hydrogen atom is replaced by a hydroxy group. Examples are methanol, Ethanol, n-propanol and isopropanol.

Aliphatic C ₂ -C ₃₀ diols are linear or branched aliphatic hydrocarbons, preferably saturated linear or branched aliphatic hydrocarbons (alkanes) having 2 to 30 carbon atoms, in which two hydrogen atoms are replaced by two hydroxy groups, which are preferably not attached to the same carbon atom , Examples of saturated aliphatic C ₂ -C ₃₀ diols are ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, the higher isomers and the conformational isomers thereof.

Cycloaliphatic C ₃ -C ₃₀ monoalcohols are cycloaliphatic hydrocarbons, preferably saturated cycloaliphatic hydrocarbons (cycloalkanes) having from 3 to 30 carbon atoms in which a hydrogen atom is replaced by a hydroxy group. Examples of saturated cycloaliphatic C ₃ -C ₃₀ monoalcohols are cyclopropanol, cyclobutanol, cyclopentanol, cyclohexanol, cycloheptanol, cyclooctanol and the like.

Cyclaliphatic C ₃ -C ₃₀ diols are cycloaliphatic hydrocarbons, preferably saturated cycloaliphatic hydrocarbons (cycloalkanes) having from 3 to 30 carbon atoms, in which two hydrogen atoms are replaced by two hydroxy groups, which are preferably not attached to the same carbon atom. Examples of saturated cycloaliphatic C ₂ -C ₃₀ diols are cyclopropanediol, cyclobutanediol, cyclopentanediol, cyclohexanediol, cycloheptanediol, cyclooctanediol and the like.

C ₁ -C ₂₀ carboxylic acids are compounds having one, two or three carboxyl groups (COOH) and 1 to 20 carbon atoms (including the carbon atoms of the carboxyl groups). The carbon skeleton may be aliphatic or cycloaliphatic, saturated or mono- or polyunsaturated, or it may be aromatic. Examples are saturated, linear or branched fatty acids, such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, pentanoic acid, valeric acid, isovaleric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, Stearic acid, nonadecanoic acid, tuberculostearic acid and arachic acid; monounsaturated fatty acids such as crotonic acid, palmitoleic acid, oleic acid and eicosenoic acid; diunsaturated fatty acids such as sorbic acid and linoleic acid; triunsaturated fatty acids such as linolenic acid and elaeostearic acid; quadruply unsaturated fatty acids, such as arachidonic acid; saturated aliphatic dicarboxylic acids such as oxalic acid, malic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid and sebacic acid; monounsaturated aliphatic dicarboxylic acids such as maleic acid and fumaric acid; diunsaturated aliphatic dicarboxylic acids such as 2,4-hexadienedioic acid; and aromatic mono- and dicarboxylic acids such as benzoic acid, phthalic acid, isophthalic acid and terephthalic acid.

C ₄ -C ₂₀ carboxylic anhydrides are the internal anhydrides of dicarboxylic acids having 4 to 20 carbon atoms (including the carbon atoms of the carboxyl groups). Examples of these are the anhydrides of aliphatic saturated dicarboxylic acids such as succinic anhydride, glutaric anhydride, adipic anhydride, pimelic anhydride, azelaic anhydride and sebacic anhydride; the anhydrides of aliphatic monounsaturated dicarboxylic acids, such as maleic anhydride; and the anhydrides of aromatic dicarboxylic acids, such as phthalic anhydride.

Aliphatic C ₂ -C ₂₀ ethers are compounds of the formula RO-R ', wherein R and R' independently of one another represent a linear or branched aliphatic radical, preferably a linear or branched alkyl radical having 1 to 19 carbon atoms, with the proviso in that the sum of the carbon atoms of the radicals R and R 'is from 2 to 20. Examples are dimethyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, propyl tert-butyl ether, isopropyl tert-butyl ether and the like.

Cyclic C ₄ -C ₁₀ ethers are formally internal ethers of diols, preferably of alkyl diols, more preferably of α, ω-alkyl diols having from 4 to 10 carbon atoms. Examples include terahydrofuran and 1,3- and 1,4-dioxane.

The below given details of individual preferred features the inventive method and the invention Devices are considered as taken alone also in every possible combination with each other.

The term "liquid streams" refers to the state of matter as present under the conditions of step (b). For example, a component that can be stored at room temperature (25 ° C) and at atmospheric gas pressure is provided as a liquid stream when presented under the temperature and / or pressure conditions of step (b) (eg, low temperature and / or elevated pressure).

Under a reaction zone is used in the context of the present invention Section of a reactor in the flow direction of the liquid Understood material flows in which the polymerization proceeds. A reaction zone may be within a part of a reactor, within a single reactor or within two or more reactors be ordered to. Located in a preferred embodiment each reaction zone in a separate reactor.

When monomers to be polymerized all come ethylenically unsaturated Monomers under cationic polymerization conditions are polymerizable. Examples of these are linear alkenes, such as Ethene, propene, the n-butenes, such as 1- and 2-n-butene, the n-pentenes, such as 1- and 2-n-pentene, and the n-hexenes, such as 1-, 2- and 3-n-hexene, Alkadienes such as butadiene and isoprene, isoalkenes such as isobutene, 2-methylbutene-1,2-methylpentene-1,2-methylhexene-1,2-ethylpentene-1,2-ethylhexene-1 and 2-propylheps-1, cycloalkenes, such as cyclopentene and cyclohexene, vinylaromatic compounds, such as styrene, α-methylstyrene, 2-, 3- and 4-methylstyrene, 4-tert-butylstyrene and q2, 3- and 4-chlorostyrene, and olefins having 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, as well as mixtures of these monomers.

preferred Monomers are isobutene, isobutene-containing monomer mixtures, vinylaromatic Compounds, such as styrene, styrene-containing monomer mixtures, styrene derivatives, in particular α-methylstyrene and 4-methylstyrene, the above mentioned cycloalkenes, the abovementioned alkadienes and mixtures from that.

Especially preferred monomers are isobutene, isobutene-containing monomer mixtures, vinyl aromatic compounds, in particular styrene and styrene-containing Monomer mixtures, and mixtures of the aforementioned monomers. Especially if the polymerization process according to the invention is used Isobutene, styrene or mixtures thereof as monomers. specially the process according to the invention serves for the polymerization of isobutene or isobutene-containing monomer mixtures and still more specific of isobutene.

If isobutene or an isobutene-containing monomer mixture is used as the monomer to be polymerized, the isobutene source is both isobutene itself and also isobutene-containing C ₄ hydrocarbon streams, for example C ₄ raffinates, C ₄ cuts from isobutane dehydrogenation, C ₄ slices from steam crackers and fluid catalysed cracking (FCC) crackers, provided that they are largely free of 1,3-butadiene contained therein. Suitable C ₄ hydrocarbon streams generally 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. Typically, the isobutene concentration in the _C4 hydrocarbon streams is in the range of 40 to 60 wt .-%. The 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 accumulation 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.

When Polymerization catalyst according to the invention a Bortrifluoridkomplex used with at least one cocatalyst.

One Boron trifluoride cocatalyst is within the scope of the present invention a compound capable of reacting with the boron trifluoride molecule to form a donor-acceptor complex. Accordingly contains the cocatalyst has a lone pair with the hole in the electron of the boron trifluoride may interact. The strength of coordination can vary over a relatively wide range, they However, it must be sufficiently large to control the Lewis acid activity of the boron trifluoride. Suitable cocatalysts are Compounds containing atoms with a lone pair of electrons such as O, S or N, which has sufficient Lewis basic properties. Suitable cocatalysts are, for example, water, alcohols, Carboxylic acids, anhydrides, aldehydes, ketones, nitriles, phenols and dialkyl ethers. The boron trifluoride-forming Lewis donor-acceptor complex possesses the use of protic donors, such as alcohols or Carboxylic acids, (also) Bronsted acid properties.

Cocatalysts which are preferably used are oxygen-containing compounds which contain at least one divalent oxygen atom. Preferably, the oxygen compounds are selected from water, C ₁ -C ₃₀ aliphatic monoalcohols, C ₂ -C ₃₀ aliphatic diols, C ₃ -C ₃₀ cycloaliphatic monoalcohols, cycloaliphatic C ₃ -C ₃₀ -diols, C ₁ -C ₂₀ -carboxylic acids, C ₄ -C ₁₂ -carboxylic anhydrides, open-chain C ₂ -C ₂₀ ethers and cyclic C ₄ -C ₁₀ ethers. Particularly preferred are the oxygen compounds selected from water, saturated aliphatic C ₁ -C ₁₀ monoalcohols, saturated aliphatic C ₂ -C ₁₀ diols, saturated cycloaliphatic C ₅ -C ₈ monoalcohols, saturated cycloaliphatic C ₅ -C ₈ diols , C ₁ -C ₁₀ -carboxylic acids, C ₄ -C ₆ -carboxylic anhydrides, open-chain C ₂ -C ₁₀ ethers and cyclic C ₄ -C ₆ ethers. More preferably, the oxygen compounds are selected from water, C ₁ -C ₁₀ saturated aliphatic monoalcohols, and C ₂ -C ₁₀ dialkyl ethers. Particularly suitable boron trifluoride complexes have both Lewis and Brönsted acid properties. Accordingly, even more preferred oxygen compounds are selected from water and saturated aliphatic C ₁ -C ₄ monoalcohols, such as methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol, isobutanol and tert-butanol, and especially under water and saturated aliphatic C ₁ -C ₃ monoalcohols, such as methanol, ethanol, propanol and isopropanol. In particular, methanol is used as cocatalyst.

in the Boron trifluoride complex is the molar ratio from boron trifluoride to cocatalyst preferably 1: 1 to 1:10, especially preferably 1: 1 to 1: 5 and in particular 1: 1 to 1: 3. The term "complex" in the Related to the indicated molar ratios of boron trifluoride to cocatalyst should not be construed restrictive and above all, is not intended to be a limiting statement hit the coordination sphere of the boron atom. The term "complex" in the Related to the indicated molar ratios relates that the boron trifluoride complex is converted by the reaction of Boron trifluoride with the cocatalyst in the above molar ratios is available.

The Boron trifluoride complexes are generally prepared by introducing gaseous boron trifluoride in or the relevant Cocatalyst (s) or preferably in a solution of the / cocatalyst / cocatalysts in a solvent produced. The representation of these complexes is usually at Temperatures from -60 to + 40 ° C, preferably at -20 to + 40 ° C. The application of lower temperatures is also possible, but requires an increased technical Effort to produce such low temperatures. The complex formation of boron trifluoride with the cocatalyst (s) usually exothermic, which is why the reaction mixture advantageously Is cooled to the desired temperature to keep. Many complexes of boron trifluoride with cocatalysts are highly viscous liquids at low temperatures or, such as the boron trifluoride complexes with polyvalent ones secondary alcohols, even solids. In such cases it is advantageous to the Bortrifluoridkomplexe in a solvent to create. Suitable solvents are, for example Hydrocarbons, such as pentane, hexane and isooctane, or halogenated Hydrocarbons, such as methylene chloride or chloroform. It can of course also solvent mixtures be used. As a rule, the more polar the used Solvent is, the better the formed boron trifluoride complexes are soluble in it. The Bortrifluoridkomplexe are preferably in preformed for separate reactors prior to their provision in step (a), stored after their formation and as needed liquid Electricity provided. For temporary storage, the solutions the preformed boron trifluoride complexes, optionally after dilution with further solvent, conveniently filled in coolable containers and at Temperatures of generally below 0 ° C to their Use stored.

In Step (a) of the method according to the invention at least two liquid streams, e.g. B. two, three or four streams which are for polymerization required educts (at least one monomer, at least one boron trifluoride complex, Solvent). To be favoured two or three streams and in particular two streams provided.

The Streams must be liquid, d. H. if one of the components under given conditions of steps (a), (b) and (c) and in particular (b) and (c) are not liquid is, it must be dissolved in a solvent.

Suitable solvents are all low molecular weight, organic compounds or mixtures thereof, which have a suitable dielectric constant and no abstractable protons and which are liquid under the mixing and polymerization conditions. Preferred solvents are hydrocarbons, e.g. B. acyclic hydrocarbons having 2 to 8 and preferably 3 to 8 carbon atoms, in particular alkanes, such as ethane, iso and n-propane, n-butane and its isomers, n-pentane and its isomers, n-hexane and its isomers, n -Heptane and its isomers, and also n-octane and its isomers, cyclic alkanes having 5 to 8 carbon atoms, such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, cycloheptane, acyclic alkenes preferably having 2 to 8 carbon atoms, such as ethene, iso- and n-propene, n-butene, n-pentene, n-hexene and n-heptene, cyclic olefins such as cyclopentene, cyclohexene and cycloheptene, aromatic hydrocarbons such as toluene, xylene, ethylbenzene, and halogenated hydrocarbons such as halo nierte aliphatic hydrocarbons, eg. As such as chloromethane, dichloromethane, trichloromethane, chloroethane, 1,2-dichloroethane and 1,1,1-trichloroethane and 1-chlorobutane, and halogenated aromatic hydrocarbons such as chlorobenzene, 1,2-dichlorobenzene and fluorobenzene. The halogenated hydrocarbons used as solvents do not include compounds in which halogen atoms are attached to secondary or tertiary carbon atoms.

Especially preferred solvents are the abovementioned alkanes, especially hexane and heptane, and the halogenated alkanes, in particular Methylene chloride and chlorobutane, and mixtures thereof. Especially but are also preferred solvent mixtures, at least a halogenated hydrocarbon, in particular at least one Chloroalkane, and at least one aliphatic hydrocarbon, in particular at least one alkane. The volume ratio From carbon hydrogen to halogenated hydrocarbon is thereby preferably in the range from 1:10 to 10: 1, more preferably in the Range of 4: 1 to 1: 4 and in particular in the range of 3: 1 to 1: 3. If solvent mixtures are used, then the mixtures also formed only during the mixing process (b) be, for example by mixing two or more streams, containing different solvents. This approach offers the advantage of having different components, such as monomer and Boron trifluoride complex in different solvents have sufficiently good solubility, first in the for each optimum solvent solved and only when mixing in step (b) with a less optimal Solvent come into contact. That way Dosage and constipation problems during transfer the streams provided in the mixing step (b) avoided. On the other hand, the invention allows Process the use of solvents that are in it component to be dissolved is not or not completely solve, without causing constipation problems because the micromixer for the training of a sufficient fine distribution Dispersion ensures. For example, the boron trifluoride complex dispersed in one of the abovementioned alkanes or cycloalkanes, preferably in one of the above-mentioned alkanes and in particular in hexane or heptane, in step (a), without that there are blockages in the reaction system. Specially used however, as a solvent for the boron trifluoride complex halogenated alkanes, in particular methylene chloride, chlorobutane or Mixtures thereof. If the at least one monomer is also in a solvent is to be provided, it is preferable to use a solvent, in which this is well soluble, preferably one of above-mentioned alkanes, in particular hexane, heptane or mixtures from that.

The streams provided in step (a) only individual components (eg a monomer, a boron trifluoride complex, each optionally in a solvent (mixture)) or but contain mixtures of the individual components. However, it is true the proviso that the boron trifluoride complex (s) is not may be provided in admixture with the monomer (s), since they are already before reaching the mixer (s) or anyway react before reaching the reaction zone, which would affect the polymerization reaction.

• (i-1) wenigstens ein flüssiger Strom, der wenigstens ein kationisch polymerisierbares Monomer und gegebenenfalls wenigstens ein Lösungsmittel enthält; und
• (ii-1) wenigstens ein flüssiger Strom, der wenigstens einen Bortrifluoridkomplex mit wenigstens einem Cokatalysator und gegebenenfalls wenigstens ein Lösungsmittel enthält;

bereitgestellt.In a preferred embodiment, in step (a)

• (i-1) at least one liquid stream containing at least one cationically polymerizable monomer and optionally at least one solvent; and
• (ii-1) at least one liquid stream containing at least one boron trifluoride complex with at least one cocatalyst and optionally at least one solvent;

provided.

• (i-1) ein flüssiger Strom, der wenigstens ein kationisch polymerisierbares Monomer und gegebenenfalls wenigstens ein Lösungsmittel enthält; und
• (ii-1) ein flüssiger Strom, der wenigstens einen Bortrifluoridkomplex mit wenigstens einem Cokatalysator und gegebenenfalls wenigstens ein Lösungsmittel enthält; bereitgestellt wird.

It is particularly preferred if

• (i-1) a liquid stream containing at least one cationically polymerizable monomer and optionally at least one solvent; and
• (ii-1) a liquid stream containing at least one boron trifluoride complex with at least one cocatalyst and optionally at least one solvent; provided.

• (i-1) ein flüssiger Strom, der ein kationisch polymerisierbares Monomer und gegebenenfalls wenigstens ein Lösungsmittel enthält; und
• (ii-1) ein flüssiger Strom, der einen Bortrifluoridkomplex mit einem Cokatalysator und wenigstens ein Lösungsmittel enthält;

bereitgestellt wird.It is more preferable if

• (i-1) a liquid stream containing a cationically polymerizable monomer and optionally at least one solvent; and
• (ii-1) a liquid stream containing a boron trifluoride complex with a cocatalyst and at least one solvent;

provided.

• (i-2) wenigstens ein flüssiger Strom, der wenigstens ein kationisch polymerisierbares Monomer und gegebenenfalls wenigstens ein Lösungsmittel enthält;
• (ii-2) wenigstens ein flüssiger Strom, der wenigstens einen Bortrifluoridkomplex mit wenigstens einem Cokatalysator und gegebenenfalls wenigstens ein Lösungsmittel enthält; und
• (iii-2) wenigstens ein flüssiger Strom, der wenigstens ein Lösungsmittel enthält;

bereitgestellt.In an alternative preferred embodiment, in step (a)

• (i-2) at least one liquid stream containing at least one cationically polymerizable monomer and optionally at least one solvent;
• (ii-2) at least one liquid stream containing at least one boron trifluoride complex with at least one cocatalyst and optionally at least one solvent; and
• (iii-2) at least one liquid stream containing at least one solvent;

provided.

• (i-2) ein flüssiger Strom, der wenigstens ein kationisch polymerisierbares Monomer und gegebenenfalls wenigstens ein Lösungsmittel enthält;
• (ii-2) ein flüssiger Strom, der wenigstens einen Bortrifluoridkomplex mit wenigstens einem Cokatalysator und gegebenenfalls wenigstens ein Lösungsmittel enthält; und
• (iii-2) ein flüssiger Strom, der wenigstens ein Lösungsmittel enthält;

bereitgestellt wird.It is particularly preferred if

• (i-2) a liquid stream containing at least one cationically polymerizable monomer and optionally at least one solvent;
• (ii-2) a liquid stream containing at least one boron trifluoride complex with at least one cocatalyst and optionally at least one solvent; and
• (iii-2) a liquid stream containing at least one solvent;

provided.

• (i-1) ein flüssiger Strom, der wenigstens ein kationisch polymerisierbares Monomer und gegebenenfalls wenigstens ein Lösungsmittel enthält; und
• (ii-1) ein flüssiger Strom, der wenigstens einen Bortrifluoridkomplex mit wenigstens einem Cokatalysator und gegebenenfalls wenigstens ein Lösungsmittel enthält;

bereitgestellt.In particular, however, in step (a)

• (i-1) a liquid stream containing at least one cationically polymerizable monomer and optionally at least one solvent; and
• (ii-1) a liquid stream containing at least one boron trifluoride complex with at least one cocatalyst and optionally at least one solvent;

provided.

Prefers is the at least one boron trifluoride complex in at least one Solvent provided.

• (i-1) ein flüssiger Strom, der wenigstens ein kationisch polymerisierbares Monomer und gegebenenfalls wenigstens ein Lösungsmittel enthält; und
• (ii-1) ein flüssiger Strom, der einen Bortrifluoridkomplex mit einem Cokatalysator und wenigstens ein Lösungsmittel enthält;

bereitgestellt.Specifically, in step (a), accordingly

• (i-1) a liquid stream containing at least one cationically polymerizable monomer and optionally at least one solvent; and
• (ii-1) a liquid stream containing a boron trifluoride complex with a cocatalyst and at least one solvent;

provided.

Some cationically polymerizable monomers are present in the appropriate mixing and reaction temperatures (see below) are liquid and can therefore also be provided without solvent. is but this is not the case, so are the monomers in one Solvent dissolved provided.

In terms of suitable and preferred monomers, Bortrifluoridkomplexe and solvent Reference is made to the above statements.

The for the respective component (monomer, boron trifluoride complex) suitable solvents are determined by the physical Properties of the compound to be dissolved, such as dielectric constant, Stability in the respective solvent etc. conditioned and are generally known or can be known to the person skilled in the art be determined by simple preliminary tests.

The in step (a) provided liquid streams are then subjected to the mixing step (b).

In In a preferred embodiment, the mixing takes place the liquid streams at or below the reaction temperature the subsequent polymerization. The reaction temperature is thereby as the temperature at which the polymerization in the Reaction zone is performed. If it is a temperature interval, this is the lowest temperature set in the reaction zone meant. This can initiate the reaction mixture during the mixing process avoided and a defined reaction start and defined residence times in the subsequent polymerization become.

Preferably, the mixing is carried out at -100 to 10 ° C, more preferably -80 to 0 ° C, stronger be preferably -50 to 0 ° C and especially -30 to 0 ° C.

The Mixing temperature is usually determined by the temperature in step (a) provided streams (i.e., cooling the Currents to the desired mixing temperature). In addition, however, the mixers themselves can be cooled, which is especially useful if the mixing process is exothermic.

In In a first preferred embodiment, the mixing takes place the liquid streams in one stage in a mixer with microstructures (= micromixer). For this all will in step (a) provided liquid streams fed into a micromixer and mixed.

In an alternatively preferred embodiment, the Mixing the liquid streams in several stages, wherein at least the last mixer in the flow direction before entry in the reaction zone (s) is a mixer with microstructures.

The Of course, multilevel mixing is only possible when at least three liquid streams are mixed should be.

At the multistage mixing, it is preferred to use the stream or streams, containing the at least one boron trifluoride complex, as the last Add component to avoid the polymerization too early, d. H. before the occurrence of the step (b) generated Reaction mixture in the reaction zone, is used. Preferably at least that mixer in which the one or more streams, which contain the at least one boron trifluoride complex mixed will / become a micromixer.

Prefers is the one-step mixing.

To the Mixing can be mixed at x in each mixer Components x streams containing the individual components be prepared and fed into the mixer. Prefers however, premixes are used. So first of all for example, a premix of various monomers and optionally, solvent and prepared as a first be provided with liquid electricity and then with the further current (s) according to step (b) are mixed. In the preparation of the premix can Both conventional mixers and micro mixers are used become. Conventional mixers are for manufacturing the premix described here in most cases completely adequate.

The Residence time in the individual mixers and especially in that one Mixer in which the at least one boron trifluoride complex is mixed and which is preferably a micromixer, must be so short that no spontaneous polymerization begins, otherwise the mixer and especially a micromixer clog up and completely could fail. Preferably, the residence time in the mixer in which the at least one boron trifluoride complex is mixed, less than a second. In the if necessary used remaining mixers to the mixer, in the the at least one boron trifluoride complex is mixed in, upstream are, the residence time can be slightly longer.

In terms of suitable and preferred mixer and in particular micromixer is based on the comments on the invention Directed devices.

The in step (b) obtained reaction mixture is then passed into a reaction zone and subjected to polymerization (Step (c)).

The Polymerization may be one-step or two or more than two, d. H. in 2, 3, 4, 5 or more stages. Preferably takes place they single-stage.

in the Case of multi-stage polymerization can be between at least two of the polymerization stages at least one additional Current (for example, one, two, three, four, or five streams) be mixed. This may be a monomer-containing stream, Boron trifluoride complex-containing stream, a mixture thereof and / or to act any other material flow.

In In a preferred embodiment, the person is / are additional power (s) over one Mixer with microstructures mixed. Particularly preferred for mixing this additional stream or this additional Streams and for the others. Reaction at least a reactor with mixing function used.

The Polymerization is preferably at a temperature in the range from -100 to 10 ° C, more preferably -80 to 5 ° C, more preferably -50 to 0 ° C, even more preferably -40 to 0 ° C, especially -35 to 0 ° C and especially -30 to 0 ° C performed.

The Of course, polymerization can be equally successful at lower temperatures, however purely for energy and economic reasons is not preferred.

The Polymerization temperature is determined on the one hand by the temperature of the adjusted in step (b) obtained reaction mixture. This one will again by the temperature provided in step (a) Currents and optionally by the cooling specified at the mixers. As the polymerization is usually exothermic on the other hand, it is often necessary to that also the reaction zone in which the polymerization takes place, is cooled. Accordingly, the reaction zone or the reactor in which it is arranged, preferably tempered and preferably has a good heat exchange ability. With regard to suitable reaction zones or containing them Reactors will be referred to the following to the invention Device directed.

The Polymerization is usually carried out under atmospheric pressure Pressure, but it may also be diminished or increased Pressure to expire. A suitable pressure range is between 1 and 25 bar.

specially for isobutene as the monomer to be polymerized is the reaction pressure at reaction temperatures below -10 ° C of Of minor importance, since isobutene is condensed at these temperatures and thus is practically not compressible. Only at higher Temperatures and / or when using even lower boiling Solvents such as ethene or propene are preferably added increased reaction pressure, for example at a pressure from 3 to 20 bar.

The Residence time in the reaction zone for the polymerization is preferably in the range of 5 seconds to 30 minutes, more preferably in the range of 10 seconds to 15 minutes and in particular in the range of 2 min to 10 min.

It It goes without saying that the polymerization is largely under aprotic, especially under anhydrous, reaction conditions performs. Under aprotic or anhydrous Reaction conditions are understood to mean that the water content (or the Content of protic impurities) in the reaction mixture less than 50 ppm and in particular less than 5 ppm. As a rule, therefore, one will use the starting materials before their use dry physically and / or by chemical means. Especially it has been proven, preferably as a solvent used unsaturated aliphatic or alicyclic Hydrocarbons after conventional pre-cleaning and predrying with an organometallic compound, for example an organolithium, Organomagnesium or organoaluminum compound, in an amount sufficient to remove the traces of water from the solvent to remove. In a similar way one can also with the to be polymerized monomers, in particular the isobutene or isobutene-containing Mixtures proceed. Depending on the degree of purity and type of solvent and monomers may also be sufficient for distillation to be in the Essentially anhydrous starting materials available too put.

The Pre-cleaning or predrying of the solvents and the Monomers in the usual manner, preferably by Treatment with solid drying agents such as molecular sieves or pre-dried oxides such as alumina, silica, calcium oxide or barium oxide. In an analogous manner, the starting materials can be dried, for the treatment with metal alkyls not considered comes, for example, vinyl aromatic monomers. Also a distillative Pre-cleaning or predrying of the starting materials is possible.

The components (monomer, boron trifluoride complex) are provided in such amounts in the streams in step (a) and fed into the mixing process (b) at such flow rates that they react in the polymerization reaction in the following proportions:
The total weight ratio of monomer to boron trifluoride complex is preferably 2: 1 to 10,000: 1, more preferably 2: 1 to 5000: 1 and especially 5: 1 to 1000: 1.

In a preferred embodiment of the process according to the invention in the at least one reaction zone, the heat transfer coefficient on the side of the reaction medium at least 50 W / m ² K, more preferably at least 100 W / m ² K, more preferably at least 200 W / m ² K and especially at least 400 W / m ² K. The ratio of heat exchange surface to reaction volume is preferably greater than 250 m ² / m ³ , more preferably greater than 500 m ² / m ³ , more preferably greater than 1000 m ² / m ³ and in particular greater than 2000 m ² / m ³ .

In a preferred embodiment of the invention Process becomes at least one for the polymerization in step (c) microstructured reaction zone used. In terms of The definition of microstructured reaction zones is based on Versions of the invention Directed devices.

Preferably the polymerization in step (c) takes place in a single reaction zone, which is preferably microstructured.

The Polymerization occurs when the reaction mixture in the at least one reaction zone and is deactivated by deactivation the boron trifluoride complex terminated.

For this the product from the (last) reaction zone is in a preferably guided and led discharge container subjected to a reaction stop.

To the Reaction termination of the boron trifluoride complex is deactivated, for example by adding a protic compound or by introducing into a protic compound, in particular by adding or initiating in water, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol or tert-butanol, or their Mixtures with water, acetonitrile, ammonia or aqueous Solutions of mineral bases, such as alkali or alkaline earth metal hydroxides or carbonates.

alternative the reaction termination can also take place continuously. For this purpose is after the (last) reaction zone in the flow direction over a feed a liquid stream containing a termination reagent, z. B. one or more of the o. G. Compounds contains, supplied and the mixture then flows through a dwell time zone, so that the catalyst deactivates before the discharge vessel becomes.

In usually the deactivated reaction mixture will be further worked up then extractively to remove catalyst residues cleaned, z. B. by washing one or more times with water or Methanol, and then by distillation into unreacted monomer, solvent, Oligomers and polymers separated. Distillatively recovered monomers, If desired, solvents and oligomers may be used in step (a) of the method according to the invention to be led back.

By receives the inventive method man polymers characterized by a high content of terminal olefinic Double bonds and a relatively high number average molecular weight distinguished.

When isobutene is used as a monomer, the resulting isobutene homopolymers have a number average molecular weight (M _n ) of preferably 500 to 10,000 daltons, more preferably 500 to 5000 daltons, more preferably 700 to 4000 and especially 800 to 3500 daltons. The polydispersity (ratio of the weight-average molecular weight (M _w ) to the number-average molecular weight, PD = M _w / M _n ) is preferably at most 10, e.g. From 1.1 to 10, or preferably from 1.3 to 10; more preferably at most 8, e.g. From 1.1 to 8, or preferably from 1.3 to 8; more preferably at most 5, e.g. From 1.1 to 5, or preferably from 1.3 to 5; even more preferably at most 4, e.g. B. 1.1 to 4 or preferably 1.3 to 4; and in particular at most 3.5, z. B. 1.1 to 3.5 or preferably 1.3 to 3.5. The content of terminal vinylidene double bonds (α-double bonds) is preferably at least 70 mol%, particularly preferably at least 80 mol% and in particular at least 85 mol%.

The information to be paid in the context of the present invention. and weight average molecular weights refer to values as determined by gel permeation chromatography (GPC) (Polyisobutene standards).

The statements made in the context of the present invention on terminal olefinic double bonds in general and on the vinylidene contents of polyisobutenes in particular refer to values obtainable by ¹³ C-NMR spectroscopy (integration of the signals in ¹³ C-NMR).

The inventive method allows the polymerization of cationically polymerizable compounds in a continuous procedure. In particular, the process according to the invention allows the preparation of polymers having a high content of terminal olefinic double bonds and at the same time sufficiently high number average molecular weights, using significantly smaller amounts of catalyst than the Method of the prior art. At the same time, a high conversion can be achieved with short reaction times. The use of micromixers according to the invention also makes it possible to carry out the polymerization in a heterogeneous phase without causing blockages in the reaction system (eg mixers, lines, reactor (parts)).

• – wenigstens zwei Vorlagebehälter für flüssige Ströme,
• – je eine Zuführung für die flüssigen Ströme aus den wenigstens zwei Vorlagebehältern,
• – einen oder mehrere hintereinander geschalte Mischer, dem/denen die flüssigen Ströme zugeführt und in denen sie unter Erhalt eines Reaktionsgemisches vermischt werden, wobei zumindest der in Stromrichtung letzte Mischer vor Eintritt in die Reaktionszone(n) mit Mikrostrukturen ausgestattet ist,
• – wenigstens eine Reaktionszone, wovon wenigstens eine mikrostrukturiert ist, und
• – einen Austragsbehälter, der gegebenenfalls mit einer oder mehreren Zugabe- und/oder Mischvorrichtungen versehen ist.

Another object of the invention relates to a device A for the continuous production of polymers, comprising:

• At least two supply containers for liquid streams,
• - One supply for the liquid streams from the at least two storage containers,
• One or more mixers connected in series to which the liquid streams are fed and in which they are mixed to obtain a reaction mixture, at least the last mixer in the flow direction being provided with microstructures before entry into the reaction zone (s),
• At least one reaction zone, at least one of which is microstructured, and
• - A discharge, which is optionally provided with one or more addition and / or mixing devices.

• – wenigstens drei Vorlagebehälter für flüssige Ströme,
• – je eine Zuführung für die flüssigen Ströme aus den wenigstens drei Vorlagebehältern,
• – einen oder mehrere hintereinander geschalte Mischer, dem/denen die flüssigen Ströme zugeführt und in denen sie unter Erhalt eines Reaktionsgemisches vermischt werden, wobei zumindest der in Stromrichtung letzte Mischer vor Eintritt in die Reaktionszone(n) mit Mikrostrukturen ausgestattet ist,
• – wenigstens eine Reaktionszone, und
• – einen Austragsbehälter, der gegebenenfalls mit einer oder mehreren Zugabe- und/oder Mischvorrichtungen versehen ist.

Another object of the invention relates to a device B for the continuous production of polymers, comprising:

• At least three supply containers for liquid streams,
• - One supply for the liquid streams from the at least three storage containers,
• One or more mixers connected in series to which the liquid streams are fed and in which they are mixed to obtain a reaction mixture, at least the last mixer in the flow direction being provided with microstructures before entry into the reaction zone (s),
• At least one reaction zone, and
• - A discharge, which is optionally provided with one or more addition and / or mixing devices.

devices A and B are for carrying out the invention Suitable method.

The The following statements refer to both Device A and the device B, if not explicitly only one of the devices is referred to.

In terms of suitable and preferred monomers, boron trifluoride complexes and solvents, which are contained in the liquid streams is Referring to the above statements.

When Mixers may be mixers known in the art be used. It can in principle be mixer with or act without microstructures, if defined at the outset Conditions are met. Suitable mixers without microstructures, in the context of the present application as "conventional" or "conventional" mixer are all for continuous mixing of Liquids suitable and sufficiently known to those skilled Mixer. They are according to the process requirements selected.

conventional Mixers differ from mixers with microstructures (= micromixer) by their characteristic dimension in the for mixing relevant zone. Under the characteristic dimension of a flowed through Device, z. B. a mixer, is understood in the context of the present Invention the smallest, perpendicular to the flow direction Expansion. The characteristic dimension of a micromixer is significantly smaller than that of a conventional mixer (For example, often at least by a factor of 10 or at least by a factor of 100 or at least by a factor of 1000 lower) and is usually in the micrometer to millimeter range. The zone relevant for mixing (relevant mixer area) depends on the type of mixer and is the expert known.

in the The scope of the present invention is intended to be under a micromixer to be understood one whose characteristic dimension is at most 10,000 microns. Corresponding in the context of the present invention, the term "conventional Mixer "a mixer whose characteristic dimension is> 10 mm.

The characteristic dimension of the mixer according to the invention with microstructures is at most 10,000 microns, z. B. 1 micron to 10,000 microns or preferably 10 to 10,000 microns or more preferably 25 to 10,000 microns; preferably at most 8000 microns, z. B. 1 to 8000 or preferably 10 to 8000 microns or more preferably 25 to 8000 microns; more preferably at most 5000 microns, z. B. 1 to 5000 or preferably 10 to 5000 microns or more preferably 25 to 5000 microns; more preferably at most 4000 microns, z. B. 1 to 4000 or preferably 10 to 4000 microns or more preferably 25 to 4000 microns; even more preferably at most 3000 microns, z. B. 1 to 3000 or preferably 10 to 3000 microns or more preferably 25 to 3000 microns; and in particular at most 1000 microns, z. B. 1 to 1000 or preferably 10 to 1000 microns or more preferably 25 to 1000 microns. The optimum characteristic dimension results from the requirements of the mixing quality and the clogging susceptibility of the mixing device. Microstructure mixers are also referred to as micromixers.

Examples suitable mixers without microstructures are both conventional dynamic mixers, such as mixing pumps and continuous flow stirred tank, as well as in Piping built-in mixing devices such as baffles, Apertures, jet mixers, T and Y pieces as well as static ones Mixer.

• I. statische Mischer
• I.1. laminare Diffusionsmischer
• I.1.a) ”chaotisch-laminare” Mischer, wie beispielsweise T-Mischer, Y-Mischer, oder Zyklonmischer
• I.1.b) Multilaminationsmischer bzw. Interdigitalmischer
• I.2. laminare Diffusionsmischer mit konvektiver Quervermischung, wie beispielsweise geformte Mischkanäle oder Kanäle mit Sekundärstrukturen
• I.3. Split-Recombine-Mischer, wie beispielsweise Raupenmischer
• II. dynamische Mischer, wie beispielsweise Mischpumpen
• III. Kombinatinen davon;

wobei diese selbstverständlich den o. g. Bedingungen für die charakteristische Dimension genügen.Examples of suitable micromixer mixers are:

• I. static mixer
• I.1. laminar diffusion mixers
• I.1.a) "chaotic-laminar" mixers, such as T-mixers, Y-mixers, or cyclone mixers
• I.1.b) Multilamination mixer or interdigital mixer
• I.2. laminar diffusion mixers with convective cross-mixing, such as shaped mixing channels or channels with secondary structures
• I.3. Split recombine mixers, such as crawler mixers
• II. Dynamic mixers, such as mixing pumps
• III. Combinations thereof;

these, of course, satisfy the above-mentioned conditions for the characteristic dimension.

Suitable are mixers with microstructures that have at least one mixing channel exhibit. Mixing in the micromixers can be laminar, laminar-chaotic or turbulent.

in the The following are preferred micromixers according to the invention explained in more detail.

worin

s

halbe Strömungslamellendicke [m]

D

Diffusionskoeffizient [m²/sec]

bedeutet.In the case of laminar diffusion mixers, the mixing of partial flows of the fluid, which has been fanned on a microstructure into a multitude of microscopically small flow lamellae with a thickness in the range from 10 to 2000 μm, especially 20 to 1000 μm and in particular 40 to 500 μm, takes place exclusively by molecular diffusion perpendicular to the main flow direction. A design of the mixer can be done via the Fourier number Fo = τ / τ _D , which represents the ratio of residence time in the mixer to the diffusion time between the individual flow lamellae. For the diffusion time T _D applies

wherein

s

half flow lamella thickness [m]

D

Diffusion coefficient [m ² / sec]

means.

This Ratio is greater than 1, preferably greater than 2, more preferably larger chosen as 3 and especially greater than 4, for the best possible molecular mixing of the material flows to ensure at the outlet of the mixer.

Laminar diffusion mixers can be designed as simple T or Y mixers or as so-called multilamination mixers. In the T or Y mixer, the two (or more than two) to be mixed streams are fed to a single channel through a T or Y-shaped arrangement. Decisive for the transverse diffusion path S _diff here is the channel width δ _K. For typical channel widths between 100 .mu.m and 1 mm, typical mixing times in the range of seconds to minutes result for liquids. If, as in the present process, liquids are mixed, it is advantageous to additionally support the mixing process, for example by flow-induced cross-mixing.

In multi-lamination mixers or interdigital mixers to be mixed streams are in ei Distributed nem manifold in a large number of microcurrent fibers and then fed alternately in lamellae at the outlet of the manifold the mixing section. For liquids, mixing times in the range of seconds are achieved with the classic multilamination mixers. Since this is not sufficient for some applications (eg in the case of rapid reactions), the basic principle has been further developed so that the flow lamellae are additionally focused additionally geometrically or hydrodynamically. The geometric focusing is achieved by a narrowing in the mixing section. The hydrodynamic focusing is achieved by two side streams, which flow perpendicular to the main stream and thus further compress the flow fins. The focussing described makes it possible to realize lateral dimensions of the flow lamellae of a few micrometers, so that even liquids can be mixed within a few 10 ms.

When laminar diffusion mixers with convective cross-mixing can Micro mixers are used with textured walls. Micromixers with textured walls are secondary Structures (grooves or webs) arranged on the channel walls. Preferably, they are at a certain angle to the main flow direction arranged, for example at an angle of about 30 ° to to 90 °. In the case of inertia-dominated flow conditions As a result, secondary vortices form, which cause the mixing process support.

In Another suitable design is as a mixer with Microstructure used a split recombine mixer. Split-recombine mixers characterized by stages of recurrent separation and merge from streams. Two areas of unmixed fluid flow (in most cases one starts from two equal slats) are each led away from each other in one stage, divided into two new areas, and merged again. All four areas are arranged alternately next to each other, that the original geometry is restored. In each of these Stages, the number of fins is thus doubled in stages and thereby Slat thickness and diffusion path halved. examples for suitable split-recombine mixers are the caterpillar mixers of the Company IMM and the Caterpillar mixer from the company BTS-Ehrfeld.

Examples for example, suitable dynamic micromixers Micro-mixing pumps.

Prefers you use static micromixers.

• – ”chaotisch-laminare” Mischer, wie beispielsweise T- oder Y-Stücke mit einem sehr kleinen Kapillardurchmesser im Bereich von 100 μm bis 1500 μm und bevorzugt 100 μm bis 800 μm am Mischpunkt und Zyklonmischer;
• – Multilaminationsmischer, wie beispielsweise die Schlitzplattenmischer LH2 und LH 25 oder größere Typen von der Firma Ehrfeld sowie die Interdigitalmischer SIMM und Starlam^® von der Firma IMM;
• – Mikromischer nach dem Multilaminationsprinzip mit überlagerter Dehnströmung, wie beispielsweise der SuperFocus Interdigital Mikrostrukturmischer SFIMM von der Firma IMM.

Examples of preferred static micromixers are in particular the following laminar diffusion mixers:

• "Chaotic-laminar" mixers, such as T or Y pieces with a very small capillary diameter in the range of 100 μm to 1500 μm and preferably 100 μm to 800 μm at the mixing point and cyclone mixer;
• - Multilaminationsmischer, such as the slotted plate LH2 and LH 25 or larger types from Ehrfeld and the interdigital mixer SIMM and Starlam ^® from IMM;
• - Multi-laminating micromixer with superimposed expansion flow, such as the SuperFocus Interdigital microstructure mixer SFIMM from IMM.

The Devices A and B according to the invention comprise according to a preferred embodiment a or two and especially one reaction zone.

Under a reaction zone, as already stated, in the sense the present invention, a section of a reactor in the flow direction understood the liquid streams in which the Polymerization takes place. A reaction zone can be within a part of a reactor, within an entire reactor or be arranged within two or more reactors. In a preferred embodiment is each reaction zone in a separate reactor.

In a special embodiment, the inventive Devices at least one further feeder for a liquid stream, which in the course of a reaction zone or is arranged following a reaction zone.

In a more specific embodiment, the inventive Devices at least one further feeder for a liquid stream containing a termination reagent, which is located after the (last) reaction zone.

In the device A according to the invention, at least one reaction zone is microstructured. The reactor in which this reaction zone is arranged is therefore a micro-reactor structured reaction zone. With regard to the definition of microstructured reaction zones, reference is made to the following statements.

In Device B can be used as reactors in which the reaction zone (s) is / are, generally all for the continuous Polymerization conventional reactors are used. Preferably are temperature-controlled tube reactors, tube bundle heat exchangers, Plate heat exchangers or temperature-controlled tubular reactors with Internals.

Especially However, in device B, at least one reactor is preferred with at least one microstructured reaction zone for used the polymerization.

Of the Reactor with a microstructured reaction zone is here and hereinafter also referred to as reactor with microstructures, microstructured Reactor or microreactor. Microstructured reactors are suitable, the thermal homogeneity transverse to the flow direction to ensure and allow such a polymerization under possible isothermal conditions. It points in principle each differential volume element is substantially the same Temperature over the respective flow cross section on. The maximum permissible temperature differences in one Flow cross-section depend on the desired Product properties. Preferably, the maximum Temperature difference in a flow cross-section less than 40 ° C, more preferably less than 20 ° C, more preferably less than 10 ° C and especially less than 5 ° C.

conventional Reactors and microreactors differ by their characteristic Dimension and in particular by the characteristic dimension their reaction zones. Under the characteristic dimension of a Device, z. B. a reactor, is understood in the context of the present Invention the smallest, perpendicular to the flow direction Expansion. The characteristic dimension of the reaction zone of a Microreactor is significantly smaller than that of a conventional one Reactor (eg at least a factor of 10 or at least around the Factor of 100 or even at least a factor of 1000) and is usually in the range of a hundred nanometers to a few tens of millimeters. in the Compared to conventional reactors therefore show microreactors in relation to the running heat and mass transfer processes a significantly different behavior. By the bigger one Ratio of surface to reactor volume is For example, allows a very good heat supply and removal, which is why strongly endo- or exothermic reactions are almost isothermal let carry out.

in the The scope of the present invention is intended to be under a microreactor to be understood one whose characteristic dimension maximum 30 mm. Designated accordingly in the context of the present invention the term "conventional Reactor "a reactor whose characteristic dimension is> 30 mm.

The characteristic dimension of the reaction zone of a reactor with Microstructures is within the scope of the present invention at most 30 mm, z. B. 0.1 to 30 mm or preferably 0.2 to 30 mm, or more preferably 0.4 to 30 mm; preferably at most 20 mm, z. B. 0.1 to 20 mm or preferably 0.2 to 20 mm or more preferably 0.4 to 20 mm; especially preferably at most 15 mm, z. B. 0.1 to 15 mm or preferably 0.2 to 15 mm or more preferably 0.4 to 15 mm; stronger preferably at most 10 mm, z. B. 0.1 to 10 mm or preferably 0.2 to 10 mm or more preferably 0.4 to 10 mm; even stronger preferably at most 8 mm, z. B. 0.1 to 8 mm or preferably 0.2 to 8 mm or more preferably 0.4 to 8 mm; especially at most 6 mm, z. B. 0.1 to 6 mm or preferably 0.2 to 6 mm or more preferably 0.4 to 6 mm; specifically at most 4 mm, z. 0.1 to 4 mm, or preferably 0.2 to 4 mm, or especially preferably 0.4 to 4 mm, more preferably at most 3 mm, z. 0.1 to 3 mm or preferably 0.2 to 3 mm or especially preferably 0.4 to 3 mm.

The microreactors are preferably selected from temperature-controlled tubular reactors, shell-and-tube heat exchangers and plate heat exchangers. Preferably, they have characteristic dimensions of tube or capillary diameter in the range of 0.1 mm to 25 mm, more preferably in the range of 0.5 mm to 6 mm, more preferably in the range of 0.7 to 4 mm and in particular in the range from 0.8 mm to 3 mm, and layer heights or channel widths in the range of preferably 0.2 mm to 10 mm, particularly preferably in the range of 0.2 mm to 6 mm and in particular in the range of 0.2 mm to 4 mm on. Pipe reactors with internals to be used according to the invention have pipe diameters in the range from 5 mm to 500 mm, preferably in the range from 8 mm to 200 mm and particularly preferably in the range from 10 mm to 100 mm. Alternatively, also comparable plate channels with inserted mixing structures can be used according to the invention. They have heights in the range of 0.5 mm to 20 mm, preferably 1 to 10 mm, and widths in the range of 10 mm to 1000 mm and in particular in the range of 10 mm to 500 mm. Optionally, the tubular reactors may contain mixing elements which are traversed by cooling channels (such. As the type CSE-XR ^® from Fluitec, Switzerland).

The optimal characteristic dimension results from the Requirements for the permissible anisothermic behavior of the reaction, the maximum allowable pressure loss and the susceptibility to blockage of the Reactor.

• – Rohrreaktoren aus Kapillaren, Kapillarbündeln mit Rohrquerschnitten von 0,1 bis 25 mm, bevorzugt von 0,5 bis 6 mm, besonders bevorzugt von 0,7 bis 4 mm, mit oder ohne zusätzliche mischende Einbauten, wobei die Rohre bzw. Kapillaren von einem Temperiermedium umspült werden können;
• – Rohrreaktoren, bei dem der Wärmeträger in den Kapillaren/Rohren geführt wird, und das zu temperierende Produkt um die Rohre geführt und durch Einbauten (Mischelemente) homogenisiert wird, wie beispielsweise der Typ CSE-SX^® von der Firma Fluitec, Schweiz;
• – Plattenreaktoren, die wie Plattenwärmetauscher mit isolierten parallelen Kanälen, Netzwerken von Kanälen oder Flächen, welche mit oder ohne strömungsbrechenden Einbauten (Pfosten) ausgerüstet sind, aufgebaut sind, wobei die Platten Produkt und Wärmeträger parallel oder in einer Schichtstruktur, welche abwechselnd Wärmeträger- und Produkt-Lagen aufweist, führen, so dass während der Reaktion die chemische und thermische Homogenität sichergestellt werden kann; sowie
• – Reaktoren mit ”flachen” Kanalstrukturen, welche nur in der Höhe eine ”Mikrodimension” aufweisen und nahezu beliebig breit sein können, deren typische kammförmige Einbauten die Ausbildung eines Strömungsprofils verhindern und zu einer für die definierte Reaktionsführung und Verweilzeit wichtigen, engen Verweilzeitverteilung führen.

Particularly preferred microreactors are:

• - Tubular reactors of capillaries, capillary bundles with tube cross sections of 0.1 to 25 mm, preferably from 0.5 to 6 mm, more preferably from 0.7 to 4 mm, with or without additional mixing internals, wherein the tubes or capillaries of a Temperiermedium can be washed around;
• - Tubular reactors, in which the heat transfer medium is guided in the capillaries / tubes, and the temperature-controlled product is guided around the tubes and homogenized by internals (mixing elements), such as the type CSE-SX ^® from the company Fluitec, Switzerland;
• - Plate reactors, such as plate heat exchangers with insulated parallel channels, networks of channels or surfaces, which are equipped with or without flow-breaking internals (posts) are constructed, wherein the plates product and heat carrier in parallel or in a layer structure, which alternately heat transfer and product -Lagen, so that during the reaction, the chemical and thermal homogeneity can be ensured; such as
• - Reactors with "flat" channel structures, which have a "micro dimension" only in height and can be almost arbitrarily wide whose typical comb-shaped internals prevent the formation of an airfoil and lead to an important for the defined reaction and residence time, narrow residence time.

In a preferred embodiment of the invention is at least a reactor with plug flow characteristics is used, the residence time characteristic of a plug flow having. Is in a tubular reactor, a plug flow ("Plug-flow") before, so can the state of the reaction mixture (eg temperature, composition, etc.) in the flow direction vary, perpendicular to each individual cross section Flow direction, however, is the state of the reaction mixture equal. As with all have entering the tube volume elements the same residence time in the reactor. Visually flows through the liquid the tube as if it were a sequencer easily slipping through the pipe. In addition, can the cross-mixing through the intensified mass transport vertically to the flow direction the concentration gradient perpendicular compensate for the flow direction. Despite the mostly laminar Flow through devices with microstructures So avoid backmixing and a close residence time distribution similar as with an ideal flow tube.

mit

u

Strömungsgeschwindigkeit [ms^–1]

L

Länge des Reaktors [m]

D_ax

axialer Dispersionskoeffizient [m²h^–1]

The Bodenstein number is a dimensionless index and describes the ratio of the convection current to the dispersion current (eg. M. Baerns, H. Hofmann, A. Renken, Chemical Reaction Engineering, Textbook of Technical Chemistry, Volume 1, 2nd Edition, p. 332 et seq ). It thus characterizes the backmixing within a system.

With

u

Flow velocity [ms ^-1 ]

L

Length of the reactor [m]

D _ax

axial dispersion coefficient [m ² h ^-1 ]

A Soil count of zero corresponds to complete backmixing in an ideal continuous stirred tank. An infinite large number of stones, however, means absolutely no backmixing, as with the continuous flow of an ideal Flow tube.

In capillary reactors, the desired backmixing behavior can be adjusted by adjusting the ratio of length to diameter as a function of the material parameters and the flow state. The underlying calculation rules are known to the person skilled in the art (eg M. Baerns, H. Hofmann, A. Renken: Chemical Reaction Engineering, Textbook of Technical Chemistry, Volume 1, 2nd Edition, p. 339 ff ). If a backmixing behavior is to be achieved as far as possible, then the above-defined number of bottom stones is preferably chosen to be greater than 10, particularly preferably greater than 20 and in particular greater than 50. For a Bodenstein number of greater than 100, the capillary reactor then has a largely Propfenströmungscharakter.

As materials for the present invention to be used mixers and reactors, low temperature range have corrosion resistant Hastelloy ^® grades, glass or ceramic as materials and / or corresponding coatings, such as TiN _3, Ni-PTFE, Ni-PFA or the like, has proven to be advantageous , Also suitable is PEEK (polyetheretherketones: high temperature resistant thermoplastics). However, it is also possible to use austenitic stainless steels, such as 1.4541 or 1.4571, generally known as V4A or as V2A, and stainless steels of the US types SS316 and SS317Ti, for the mixers and reactors to be used according to the invention.

Due to the high heat transfer coefficients and due to a high ratio of surface area to reaction volume, the heat transfer is chosen such that temperature deviations from the temperature of the temperature control medium of less than 40 ° C., preferably less than 20 ° C., more preferably less than 8 ° C and in particular less than 5 ° C occur. Thus, the reaction can proceed under largely isothermal and thus defined and controlled conditions. To realize this, depending on the exothermicity and characteristic reaction time of the polymerization reaction, a ratio of heat exchange surface to reaction volume of greater than 250 m ² / m ³ , preferably greater than 500 m ² / m ³ , particularly preferably greater than 1000 m ² / m ³ and in particular greater than 2000 m ² / m ^{3 are} selected.

In the at least one reaction zone, the product of heat transfer coefficient and volume-specific heat transfer area is preferably greater than 12500 W / m ³ K, more preferably greater than 50,000 W / m ³ K, more preferably greater than 200,000 W / m ³ K and in particular greater than 800,000 W. / m ³ K.

worin

α

Wärmeübergangskoeffizient [W/m²K],

A/V

volumenspezifische Wärmeübergangsfläche [m²/m³],

ΔH

Reaktionsenthalpie [J/kg],

ΔT

zulässige maximale Temperaturabweichung im Reaktionsmedium [K],

ρ

Partialdichte der Monomers im Reaktionsgemisch [kg/m³] und

Δt_R

charakteristische Reaktionszeit [s]

bedeuten.The following relation can be used to determine the product of volume-specific heat transfer surface and heat transfer coefficient:

wherein

α

Heat transfer coefficient [W / m ² K],

A / V

Volume-specific heat transfer area [m ² / m ³ ],

AH

Reaction enthalpy [J / kg],

.DELTA.T

permissible maximum temperature deviation in the reaction medium [K],

ρ

Partial density of the monomers in the reaction mixture [kg / m ³ ] and

Δt _R

characteristic reaction time [s]

mean.

This results in the reaction zone, a product of heat transfer coefficient and volume-specific heat transfer surface of preferably greater than 12500 W / m ³ K, more preferably greater than 50,000 W / m ³ K, more preferably greater than 200,000 W / m ³ K and in particular greater than 800,000 W / m ³ K.

The inventive device is based on the 1 explained in more detail below.

A monomer-solvent mixture or a condensed monomer becomes from a master tank 1 with conventional dosing and regulating devices via a filter 2 in a mixer 3 guided. The mixer 3 is designed as a mixer with microstructure. A boron trifluoride complex solvent mixture is removed from a receiver tank 4 via usual dosing and regulating devices (eg pumps) and a filter 5 also in the mixer 3 fed. In the mixer 3 the two liquid streams are mixed at reaction temperature or lower temperature.

That from the mixer 3 resulting mixture is placed in a reactor 9 led, which is tempered and at almost constant temperature, ie is largely operated isothermally. This reactor 9 may optionally be designed as a microstructured reactor.

The reactor 9 Optionally, a third temperature-controlled mixer 10 be followed, for example, to add additives. The mixer 10 may optionally be designed as a mixer with microstructure.

Subsequently, the product is in a temperature-controlled discharge container 11 with optional stirring device. Here, the catalyst is deactivated.

One Another object of the present invention is the use the devices A or B according to the invention for continuous production of a polymer by cationic polymerization.

In terms of suitable and preferred features of the invention Devices and cationic polymerization are referred to the above Referred to.

The The invention will be apparent from the following non-limiting Examples explained in more detail.

Examples

• ¹ bezogen auf Monomer
• ² Verweilzeit in der Reaktionskapillare

Liquid isobutene was continuously mixed with a pre-cooled in a tempering to reaction temperature solution of a boron trifluoride-methanol complex (molar ratio BF ₃ : MeOH = 0.7: 1) in chlorobutane (50 wt .-%) in a micromixer at reaction temperature. The resulting reaction solution was then pumped through a tempered reaction capillary at a defined constant flow rate. The experiment was carried out at different temperatures, residence times and flows according to Table 1. The diameter or the length of the capillary was 0.8 mm and 30 m in the first part and 2 mm and 16 m in the second part. Table 1 Ex. Flow [ml / h] BF ₃ -methanol complex [% by weight] ¹ Residence time [min] ² T [° C] 1 170 4 8th -30 2 170 4 8th -10 3 60 4 23 -30 4 60 4 23 -10 5 100 8th 14 -30 6 100 4 14 -10 7 170 4 8th -20 8th 170 4 8th 0 9 60 2 23 -20 10 60 4 23 0 11 100 8th 14 -20 12 100 4 14 0

• ¹ based on monomer
• ² residence time in the reaction capillary

The polyisobutenes obtained in Examples 1 to 12 had the properties listed in Table 2. Table 2 example Sales [%] M _n [g / mol] PD Vinylidene content [mol%] 1 28 3003 2.27 2 67 1112 1.81 3 71 2601 2.50 4 84 1020 1.87 5 79 2736 2.13 6 77 963 1.95 7 62 1894 1.90 8th 66 790 1.49 9 34 1570 3.09 10 69 911 1.48 11 92 1076 3.20 12 69 908 1.43

1

storage container

2

filter

3

mixer with microstructure

4

storage container

5

filter

9

Reactor, temperature controlled, optionally with microstructure

10

optional Mixer, optionally with microstructure, tempered

11

discharge tank, heatable

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• - EP 0628575 A [0004]
• WO 99/54362 [0005]

Cited non-patent literature

• - M. Baerns, H. Hofmann, A. Renken, Chemical Reaction Engineering, Textbook of Technical Chemistry, Volume 1, 2nd Edition, p. 332 ff. [0129]
• - M. Baerns, H. Hofmann, A. Renken: Chemical Reaction Engineering, Textbook of Technical Chemistry, Volume 1, 2nd Edition, p. 339 ff [0131]

Claims (21)

Process for continuous polymerization of cationically polymerizable monomers, comprising the following steps: (A) Providing at least two liquid streams, wherein the at least two streams are each one or more of the following components include: at least one cationically polymerizable Monomer, at least one boron trifluoride complex having at least one Cocatalyst and optionally at least one solvent, with the proviso that the current that the least contains a boron trifluoride complex, contains no monomer; (B) Mixing the at least two liquid streams under Obtaining a reaction mixture, wherein in case more than two liquid streams are provided in step (a) be, mixing the streams successively or simultaneously and at least one mixing process in a mixer is performed with microstructures; and (c) polymerizing the reaction mixture in at least one reaction zone. The method of claim 1, wherein in step (a) (I-1) at least one liquid stream, at least one cationic polymerizable monomer and optionally at least one solvent contains; and (ii-1) at least one liquid Stream containing at least one boron trifluoride complex with at least a cocatalyst and optionally at least one solvent contains; to be provided. The method of claim 1, wherein in step (a) (I-2) at least one liquid stream, at least one cationic polymerizable monomer and optionally at least one solvent contains; (ii-2) at least one liquid Stream containing at least one boron trifluoride complex with at least a cocatalyst and optionally at least one solvent contains; and (iii-2) at least one liquid Stream containing at least one solvent; to be provided. Method according to one of the preceding claims, wherein the at least one cationically polymerizable monomer is selected is among linear alkenes, isoalkenes, alkadienes, cycloalkenes, vinyl aromatic compounds, silyl-containing alkenes and mixtures from that. The method of claim 4, wherein the at least one cationically polymerizable monomer is selected from Isobutene, vinyl aromatic compounds and mixtures thereof. The method of claim 5, wherein the at least one cationic polymerizable monomer is isobutene. Method according to one of the preceding claims, wherein the at least one cocatalyst is selected from water, aliphatic C ₁ -C ₃₀ monoalcohols, C ₂ -C ₃₀ aliphatic diols, cycloaliphatic C ₃ -C ₃₀ monoalcohols, cycloaliphatic C ₃ -C ₃₀ Diols, C ₁ -C ₂₀ carboxylic acids, C ₄ -C ₁₂ carboxylic acid anhydrides, open-chain C ₂ -C ₂₀ ethers and cyclic C ₄ -C ₁₀ ethers. The process of claim 7, wherein said at least one cocatalyst is selected from water, C _{1 to} C ₁₀ saturated aliphatic alcohols, and C _{2 to} C ₁₀ dialkyl ethers. The method of claim 8, wherein the at least one Cocatalyst is selected from water, methanol, ethanol, Propanol and isopropanol. Method according to one of the preceding claims, wherein the molar ratio of boron trifluoride to cocatalyst in the boron trifluoride complex is 1: 1 to 1: 3. Method according to one of the preceding claims, wherein the mixing of the liquid streams in step (b) at or below the reaction temperature of the following Polymerization in step (c) takes place. Method according to one of the preceding claims, wherein the mixing of the liquid streams in one step done in a mixer with microstructures. A method according to any one of claims 1 and 3 to 11, wherein the mixing of the liquid streams is more stepped, wherein at least the last in the flow direction mixer before entering the reaction zone is a mixer with microstructures. The method of claim 13, wherein the stream or the streams containing the at least one boron trifluoride complex containing at least one cocatalyst, as the last component be mixed. Method according to one of the preceding claims, wherein for the polymerization in step (c) at least one microstructured Reaction zone is used. A process according to any one of the preceding claims wherein in the at least one reaction zone the product of heat transfer coefficient and volume specific heat transfer area is greater than 12500 W / m ³ K. Apparatus for continuous polymerization of cationically polymerizable monomers comprising - at least two storage tanks for liquid starting materials, - ever a feed for the liquid streams from the at least two storage containers, - one or several successively switched mixer, the / those the liquid Supplied streams and in which they receive a reaction mixture are mixed, wherein at least the in Current direction of the last mixer before entering the reaction zone (s) equipped with microstructures, - at least a reaction zone, at least one of which is microstructured, and - A discharge container, if necessary provided with one or more addition and / or mixing devices is. Apparatus for continuous polymerization of cationically polymerizable monomers comprising - at least three storage tanks for liquid starting materials, - ever a feed for the liquid streams from the at least three storage containers, - one or several mixers connected in series, to which the liquid ones Supplied streams and in which they receive a reaction mixture are mixed, wherein at least the in Current direction of the last mixer before entering the reaction zone (s) equipped with microstructures, - at least a reaction zone, and A discharge container, optionally provided with one or more addition and / or mixing devices is. The device of claim 18, wherein at least one the reaction zones is microstructured. Device according to one of claims 17 to 19, the at least one more feeder for has a liquid stream, which in the course of a reaction zone or is arranged following a reaction zone. Use of the device, as in one of Claims 17 to 20 is defined, for continuous polymerization of cationically polymerizable monomers.