DE10240790B3 - A process for preparation of polymerisates using conjugated dienes and vinyl aromatic compounds useful in the production or use of damping materials and/or tires, especially winter, slush, and snow tires, preferably ire treads - Google Patents

Abstract

A process for preparation of polymerisates using conjugated dienes and optionally vinyl aromatic compounds by ionic polymerization at 40-160degreesC in an inert reaction medium in the presence of at least one organic Li compound, at least one amino compound, where the conjugated diene = 1.3-butadiene and/or isoprene, and the organic Li compound is a 1-20C monlithium compound is new. A process for preparation of polymerisates using conjugated dienes and optionally vinyl aromatic compounds by ionic polymerization at 40-160degreesC in an inert reaction medium in the presence of at least one organic Li compound, at least one amino compound of formula (R1(R2)-N-X-O-R3: R1-R3 = 1-10C alkyl,5-8C cycloalkyl, 6010C aryl, 7-15 aralkyl, R1 and R2 form a 4-7C ring with optionally 1-2 O in the form of ether bonds, X = 1-5C hydrocarbon or Y-O-Z, Y and Z = CH2CH2, CH(CH3)CH2, CH2CH(CH3) and/or CH2CH2CH2, and at least one organic alkali compound, where the organic Li compounds comprise up to 0.01-1 parts by weight on 100 parts by weight of monomer, the organic alkali compounds are in a mole ratio of 0.01:1 to 10:1 relative to the number of moles of amino compound, the organic alkali compound is an alkali metal compound of formula R4OM, inclusive of an alkali metal alcoholate of a multihydric alcohol, R5COOM, R6R7NM, R4-R7 = 1-20C hydrocarbon, M = Na or K, R6 or R7 can be H, the conjugated diene = 1.3-butadiene and/or isoprene, and the organic Li compound is a 1-20C monlithium compound. An Independent claim is included for a polymerisate obtainable as above.

Description

The invention relates to a method for the production of polymers using conjugated Serve and optionally vinyl aromatic compounds by anionic Polymerization in the presence of a catalyst, a cocatalyst and an alkali organic compound produced by this method Polymers and their use.

Vehicle tires are among the most stressed parts of a vehicle. With a footprint that only about postcard size per tire, it is their task to keep increasing engine power in motion implement, to ensure traction when cornering fast and to achieve short braking distances even on wet roads.

That vehicle tires with the ever increasing Requirements regarding Keep up with safety, environmental protection and economy, is particularly difficult because the desired Properties often contradict each other. So a reduced rolling resistance contributes while reducing gas consumption, it worsens usually but wet grip and therefore safety. The development of tires with a perfected property profile represents a complex Optimization task, in which the tire manufacturer is in the field of tension of the "magic Triangle ", from rolling resistance, Abrasion resistance and wet slip resistance moves.

The successful development of Tires with low rolling resistance with almost unchanged wet skid and abrasion resistance is currently based on optimal interaction of innovative solution SBR (SBR = styrene butadiene rubber) and the simultaneous use of silica as a filler. The The result is a significantly reduced rolling resistance at the same time improved wet grip and largely constant abrasion properties. This makes it possible reduce fuel consumption by up to five percent.

This knowledge and development Market-ready solution SBR types has already increased the market volume of solution SBR compared to the classic emulsion SBR, who is for the future will continue. An essential reason for this Development lies in the higher flexibility of the solution across from the emulsion process with regard to the variation of the microstructure of the rubber molecules.

In the case of emulsion polymerization the microstructure of the tire polymer is difficult to control. So it can especially for Tire technology only important glass temperature (Tg) of the rubber molecules the styrene content in the polymer molecule be managed.

The situation is on the other hand at the solution SBR when initiated with lithium catalysts much cheaper. The molecular weights can be varied and in a wide range also the strictly linear structure of the molecules with a narrow molecular weight distribution let yourself by adding e.g. Divinylbenzene (DVB) up to a similar to the emulsion SBR Shift characteristic. additionally you have the opportunity the glass temperature not only due to the amount of styrene installed, but also also by influencing the incorporation of the diene monomers, which change of the vinyl content in the polymer, to change.

The extensive control of the microstructure by adding polar substances, so-called microstructure regulators or cocatalysts, therefore leads to the anionic polymerization to the opening up an abundance new rubber molecules.

Conjugated by polarization There are various reaction centers for the installation of the diene in the Polymer available. Both 1,4 and 1,2 incorporation are possible with butadiene. isoprene offers about it the 3,4 alternative. The chain growth over the addition leads to the 1,4-position to linear polymer while the growth over the addition in the 1,2- or 3,4-position vinyl or isopropenyl substituents generated along the polymerization chain.

Without adding the microstructure regulator polymers are formed when the conjugated diene monomers are incorporated with mostly cis 1.4 and trans 1.4 microstructures and significantly higher Glass transition temperature. The polymerization of butadiene with butyllithium carried out in the presence of a suitable microstructure controller, the usually acts as a Lewis base, then an increase in the vinyl group content occurs over the normal value of 10%. Depending on the type and amount of Lewis base the vinyl content is between 10 and greater than 80%.

There have been a number in the past of processes for the preparation of polymers based on conjugated Dien have been developed according to which different polar substances, which are often referred to as cocatalysts, as microstructure regulators be used.

• gute Regelwirkung auch bei hohen Temperaturen und möglichst geringer Konzentration,
• Steigerung der Polymerisationsgeschwindigkeit,
• vollständiger Monomerumsatz, gute Stabilität, d.h. kein Abbruch der lebenden Kettenenden, insbesondere auch bei höheren Temperaturen,
• ausreichende Randomisierwirkung, d.h. statistischer Einbau der unterschiedlichen Monomere bzw. unterschiedlich eingebauten Monomereinheiten,
• vollständige Abtrennbarkeit des Mikrostrukturreglers vom Polymerisationslösungsmittel.

Fundamentally, extensive requirements are placed on a suitable microstructure controller, although depending on the specific conditions of the respective polymerization plant, the priorities can be weighted differently with regard to the requirements:

• good control effect even at high temperatures and as low a concentration as possible,
• Increase in the rate of polymerization,
• complete monomer conversion, good stability, ie no termination of the living chain ends, especially at higher temperatures,
• sufficient randomizing effect, ie statistical incorporation of the different monomers or differently installed monomer units,
• complete separation of the microstructure regulator from the polymerization solvent.

The use of large quantities of cocatalyst and an insufficient microstructure regulation effect has an immediate impact on the profitability of a production process. Therefore, the one you want Effect already with a molar ratio of cocatalyst / catalyst less than 10: 1 can be reached.

In order to improve the processing behavior of the solution rubbers at the tire manufacturer, it is common to use branched rubbers. A particularly preferred variant of the polymerization technique consists in converting the living polymer ends into star-shaped polymers with the aid of a coupling agent, that is to say using divinylbenzene or, for example, SiCl _4, to achieve a coupling to star-shaped block copolymers. For this purpose, the microstructure regulator must be largely inert to the “living chain end” at high temperatures and must not break off the living ends.

In the technical production of Solution SBR become common Hydrocarbons such as hexane or cyclohexane as a solvent used. So that the solvent for one economic production can be driven in a circle full The cocatalyst can be separated from the solvent.

• a.) aminische Verbindungen und
• b.) ethergruppenhaltige Verbindungen.

A large number of microstructure controllers are described in the prior art, which can essentially be divided into two groups:

• a.) aminic compounds and
• b.) Compounds containing ether groups.

common Representatives from the group of aminic compounds are: trimethylamine, Triethylamine, N, N, N ', N'-tetramethylethylenediamine, N-methylmorpholine, N-ethylmorpholine and N-phenylmorpholine.

Typical representatives of ether groups Lewis bases are: diethyl ether, di-n-propyl ether, diisopropyl ether, di-n-butyl ether, Tetrahydrofuran, dioxanes, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, Diethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether Etc.

Aliphatic dialkyl ethers, e.g. Diethyl ether, and cyclic ethers such as tetrahydrofuran (THF) unfold often insufficient microstructure control (see T.A. Antkowiak et al, J. of Polymer Science Part A-1, Vol 10, pp. 1319 to 1334 (1972). In the anionic polymerization of butadiene with butyllithium in the presence of an even 85-fold excess of THF, one obtains Polybutadiene with only 49% of a 1,2-structural unit. The stake such a big one Amount of cocatalyst is economic Viewpoint not acceptable.

Ethylene glycol dimethyl ether shows in contrast, a significantly higher control effect with a low use concentration. However, this microstructure controller has other disadvantages. On the one hand, it is not sufficiently separable from hexane other amounts the coupling yield 0%. It can be assumed that the other two in State of the art representatives of this class of compounds, namely ethylene glycol diethyl ether and ethylene glycol dibuty ether, the above requirements in total also do not do it justice.

A class of microstructure regulators, that comes closest to the previously defined requirement profile, is described in EP 0304589-B1. Subject of the European patent is a process for the production of solution SBR and solution ISBR (Isoprene styrene butadiene rubber) using asymmetrical Dialkyl ethers such as ethylene glycol tert-butyl ether as cocatalysts.

However, they are still in place Microstructure controllers described in the art need improvement, in particular what their performance in relation to the ratio of cocatalyst: initiator, building one if possible uniform chain structure at both low and high polymerization temperatures Generation of high vinyl or isopropenyl contents and randomization of monomers. Many microstructure control systems have also the disadvantage that the vinyl contents at higher polymerization temperatures drop drastically and thus a temperature-sensitive microstructure control subject. One consequence of this is also that in manufacturing high-styrene rubbers the block styrene content increases, causing larger amounts of cocatalyst in the ratio necessary to the initiator are.

The invention is based on the object a procedure is available to steep that the mentioned disadvantages of previously known microstructure control systems does not have and in particular the production of largely non-blocking Polymers with low microstructure regulator proportions allowed.

• – konjungierte Diene und gegebenenfalls vinylaromatische Verbindungen in Gegenwart von
• – zumindest einer lithiumorganischen Verbindung (Katalysator),
• – zumindest einer Aminoverbindung (Cokatalysator) der Formel (R¹)(R²)-N-X-O-R³ worin R¹, R², R³ unabhängig voneinander stehen für Alkylreste mit 1 bis 10, bevorzugt 1 bis 4 Kohlenstoffatomen, Cycloalkylreste mit 5 bis 8, bevorzugt 5 bis 6 Kohlenstoffatomen, Arylreste mit 6 bis 10, bevorzugt 6 Kohlenstoffatomen, Aralkylreste mit 7 bis 15, bevorzugt 7 bis 9 Kohlenstoffatomen, oder R¹ und R² einen – ggf. verzweigten – Ring mit 4 bis 7 Kohlenstoffatomen und ggf. 1 oder 2 Sauerstoffatomen in der Form von Etherbindungen bilden, X für C1- bis C5-Kohlenwasserstofreste steht, vorzugsweise gesättigte Kohlenwasserstoffreste, oder -Y-O-Z-, worin Y und Z unabhängig voneinander -CH₂CH₂-, -CH(CH₃)CH₂-, -CH₂CH(CH₃)- und/oder -CH₂CH₂CH₂- sind, und
• – zumindest einer alkaliorganischen Verbindung,
• – wobei die lithiumorganischen Verbindungen zu 0,01 bis 1 Gewichtsteilen pro 100 Gewichtsteile Monomer,
• – die alkaliorganische(n) Verbindungen) in einem Molverhältnis von 0,01 1 bis 10 : 1 bezogen auf die Molzahl der Aminoverbindung eingesetzt wird/werden,
• – die alkaliorganische Verbindung eine Alkalimetallverbindung der Formel R⁴OM, einschließlich der Alkalimetallalkoholate mehrwertiger Alkohole, R⁵COOM, R⁶R⁷NM ist
• – worin R⁴, R⁵, R⁶ und R⁷ unabhängig voneinander für Kohlenwassserstoffgruppen mit 1 bis 20 C-Atomen und
• – M für Natrium oder Kalium steht,
• – wobei ein R⁶ oder R⁷ auch Wasserstoff sein kann, und
• – als konjugiertes Dien 1,3-Butadien und/oder Isopren und
• – als lithiumorganische Verbindung eine Monolithiumverbindung mit 1 bis 20 Kohlenstoffatomen eingesetzt wird.

The present invention surprisingly provides a method which advantageously achieves the tasks described above. The process according to the invention consists in reacting in an inert reaction medium at temperatures from 40 to 160 ° C. by anionic polymerization:

• - Conjugated dienes and optionally vinyl aromatic compounds in the presence of
• - at least one organolithium compound (catalyst),
• - At least one amino compound (cocatalyst) of the formula (R ¹ ) (R ² ) -NXOR ³ wherein R ¹ , R ² , R ³ independently of one another represent alkyl radicals having 1 to 10, preferably 1 to 4 carbon atoms, cycloalkyl radicals having 5 to 8, preferably 5 to 6 carbon atoms, aryl radicals having 6 to 10, preferably 6 carbon atoms, aralkyl radicals having 7 to 15, preferably 7 to 9 carbon atoms, or R ¹ and R ^{2 form} an - optionally branched - ring with 4 to 7 carbon atoms and optionally 1 or 2 oxygen atoms in the form of ether bonds, X represents C1 to C5 hydrocarbon radicals , preferably saturated hydrocarbon radicals, or -YOZ-, where Y and Z independently of one another are -CH ₂ CH ₂ -, -CH (CH ₃ ) CH ₂ -, -CH ₂ CH (CH ₃ ) - and / or -CH ₂ CH ₂ CH ₂ - are, and
• - at least one organic alkali compound,
• The organolithium compounds being 0.01 to 1 part by weight per 100 parts by weight of monomer,
• The alkali organic compounds are used in a molar ratio of 0.01 1 to 10: 1, based on the mol number of the amino compound,
• - The alkali organic compound is an alkali metal compound of the formula R ⁴ OM, including the alkali metal alcoholates of polyhydric alcohols, R ⁵ COOM, R ⁶ R ⁷ NM
• - wherein R ⁴ , R ⁵ , R ⁶ and R ⁷ independently of one another for hydrocarbon groups with 1 to 20 C atoms and
• - M stands for sodium or potassium,
• - wherein an R ⁶ or R ^{7 can} also be hydrogen, and
• - As conjugated diene 1,3-butadiene and / or isoprene and
• - A monolithium compound with 1 to 20 carbon atoms is used as organolithium compound.

Essentially non-blocking, optionally coupled polymers. Preferred embodiments are the subject of the subclaims.

The catalyst system stands out characterized in that the alkali metal compounds, in combination with the lithium catalyst and the microstructure regulator (amino compound) are used.

The in the inventive method Amino compounds used stand out from others microstructure regulators known in the prior art in particular characterized in that the decrease in the microstructure control effect with rising temperature is low. This offers the opportunity work at high polymerization temperatures, reducing the space-time yield increases.

A possible disadvantage with alone The use of the amino cocatalysts according to the invention consists in that in the manufacture of copolymers / terpolymers that are vinyl aromatic Contain monomer, the proportion of block structures in the polymer increases.

Surprisingly it was found that by adding alkali organic compounds, preferably Alcoholates, on the one hand the block structure formation are suppressed can and also found that the addition of alkali organic Connection synergistically affects the reaction rate.

The combination of amino compounds according to the invention (Cocatalyst) and alkali organic compound causes the Polymerization at higher Temperatures performed can be achieved, whereby an increase in space / time yield is achieved and at the same time no downsides regarding Vinyl group regulation and randomization of the vinyl aromatic building blocks occur. This will make the polymerization process more economical significantly increased.

catalysts

Organolithium compounds are used as catalysts used, which preferably have the structure R-Li, in which R describes a hydrocarbon radical with 1 to 20 carbon atoms. Generally, monofunctional Organolithium compounds with 1 to 10 carbon atoms. As representative examples are: called this point: methyl lithium, ethyl lithium, isopropyllithium, n-butyllithium, sec-butyllithium, n-outyllithium, tert-outyllithium, n-decyllithium. The use of n-butyllithium or sec-butyllithium is preferred.

The content of the lithium catalyst varies depending on the type and the molecular weight of the manufactured Rubber. The general rule here is that the molecular weight of the polymer is inversely proportional to the amount of catalyst used behaves. In principle, 0.01 to 1 part by weight per 100 parts by weight Monomer of the lithium catalyst used.

At a desired molecular weight in Range from 50,000 to 400,000 g / mol, based on 100 parts by weight Monomers, preferably 0.128 to 0.016 parts by weight of n-butyllithium needed.

Cocatalysts (microstructure regulator)

The cocatalysts (R ¹ ) (R ² ) -NXOR ³ according to the invention have the structure defined above.

Preferred cocatalysts are compounds with R ¹ , R ² , R ³ = methyl and ethyl and X = -CH ₂ -CH ₂ - or -CH ₂ -CH ₂ -CH ₂ -. Particularly preferred cocatalysts are 1- (N, N-dimethylamine) - (2-ethoxy) ethane and 1- (N, N-dimethylamine) - (3-ethoxy) propane. The preparation of the amino compounds preferably used as cocatalyst in the process according to the invention is described in the prior art. A possible manufacturing process is known for example from EP 0 518 013-A1.

The cocatalyst is used in a ratio of 2: 1 to 30: 1, preferably 2: 1 to 15: 1, based on the Molecular number of the catalyst (based on the atoms of lithium) used.

The cocatalyst acts as a microstructure regulator can also influence the copolymerization parameters and / or have the statistical incorporation of a copolymer or terpolymer.

alkali Organic links

Typical examples of alkali organic compounds which can be used in the process according to the invention are compounds having the following structure: R ⁴ OM, R ⁵ COOM, R ⁶ R ⁷ NM with M = Na / K, where R ⁴ , R ⁵ , R ⁶ , R ^{7 represent} alkyl groups with 1 to 20 carbon atoms, cycloalkyl groups with 3 to 20 carbon atoms, alkenyl groups with 2 to 20 carbon atoms, aryl groups with 6 to 20 carbon atoms or phenyl groups. One of the radicals R ⁶ and R ⁷ can also represent hydrogen. Alkali metal alcoholates of mono- or polyhydric alcohols are preferably used as alkali organic compounds.

The use of alkali metal alcoholates is preferred with the structure M-OR, where R is a linear or branched alkyl group with 1 to 10 carbon atoms. M is preferably sodium or potassium. Sodium or potassium alcoholates are particularly preferred, which contain 3 to 8 carbon atoms. Typical examples are Sodium / potassium tert-butoxide and sodium / potassium tert-amylate.

An accelerating effect on the conversion of the monomers is achieved in particular at one molar ratio Alkali metal alcoholate: cocatalyst from 0.01: 1 to 10: 1. Preferably is the relationship Alkali metal alcoholate: cocatalyst at 0.01: 1 to 0.5: 1.

monomers

As a conjugated diene who Polymerization can be used, e.g. considered: 1,3-butadiene, Isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 2-ethylbutadiene, 2-methyl-1,3-pentadiene, 4-butyl-1,3-pentadiene and 1,3-hexadiene.

As vinyl aromatic compounds, which can be copolymerized with the conjugated dienes the following of interest: styrene, 1-vinylnaphthalene, 2-vinylnaphthalene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstryrene, 4- (phenylbutyl) styral.

Preferred monomers are Butadiene, isoprene, styrene with isoprene, styrene with butadiene or styrene used with butadiene and isoprene.

coupling agent

Before or during the polymerization reaction can corresponding coupling agents optionally used as crosslinkers become. Aromatics, in particular, are the several vinylic ones Have groups. Typical representatives of this group are e.g. Di (vinyl / isopropenyl) benzene and tri (vinyl / isopropenyl) benzene, especially 1,3,5-trivinylbenzene and 1,3- and 1,4-divinylbenzene. These monomers cause so-called long chain branching of the individual polymer chains.

A particularly preferred variant of the method according to the invention consists in that after largely complete conversion of the monomers polymerization units obtained, the so-called living polymer chains, to couple with a coupling agent to form star-shaped polymers. Suitable coupling agents are in particular tetrahalides Elements silicon, germanium, tin and lead as well as aromatics, the least Carry 2 vinyl groups, e.g. 1,3,5-trivinylbenzene and 1,3- and 1,4-divinylbenzene.

solvent

The reaction medium is an inert organic solvent centers Diluent. Primarily, hydrocarbons with 5 to 15 carbon atoms, such as. Pentane, hexane, heptane and octane and their cyclic analogues as well as their mixtures. Aromatic solvents, such as benzene, toluene etc. can be used. Saturated, aliphatic solvents, such as cyclohexane and hexane are preferred.

There are basically different ones possibilities the execution of the method according to the invention. For one, can the cocatalyst and the alkali metal alcoholate individually, in principle be added before the actual polymerization. Here recommends the addition of the alcoholate in the form of a solution. The is preferred Mixing the alcoholate with an inert solvent, e.g. Hexane as Reaction medium.

Another preferred embodiment consists in mixing the alcoholate in the process according to the invention to use cocatalysts used. Miscibility in particular the preferred alkali metal alcoholates, sodium / potassium tert-butoxide and / or sodium / potassium tert-amylate in the corresponding cocatalysts is sufficient to get the one you want Amount of alcoholate to be included in the polymerization process. Thereby the rubber manufacturer is given the opportunity to produce a finished product Compound, consisting of cocatalyst and alkali organic compound, dosed and coordinated to use, which makes it Polymerization process can be simplified.

In batch production the rubbers according to the process of the invention recommend it himself, everyone Ingredients such as cocatalyst (amino compound), solvents, Submit monomers and optionally crosslinker compound in the next step titrate with an organolithium compound and then that needed for the polymerization Add amount of catalyst. The organolithium titer is used to remove impurities (Scavenger), especially those with active hydrogen atoms.

The polymerization of the monomer units is at 0 to 160 ° C carried out. A preferred temperature range is 40 to 120 ° C. there the polymerization process can be carried out batchwise or continuously carried out become. The coupling also takes place in the preferred temperature range from 40 to 120 ° C.

The polymers according to the invention are preferred after known vulcanization steps in tires, in particular in the tire treads, used. Appropriately manufactured tires have excellent High speed, wet and snow properties and are therefore suitable as slush and snow tires (M + S tires) or winter tires.

Examples

A hydrocarbon mixture was used as the solvent used that consisted of about 50% of n-hexane and as a C6 cut referred to as. Other constituents of this mixture were in particular Pentane, heptane and octane and their isomers. The solvent was about a molecular sieve with a pore size of 0.4 nm, so that the Water content was reduced below 10 ppm, and then with N2 stripped.

The organic lithium compound was n-butyllithium (BuLi), which was in the form of a 15 percent by weight solution Hexane was used. The styrene monomer was removed from the stabilizer distilled off and with n-butyllithium in the presence of o-phenathroline titrated. The cocatalyst was treated with n-butyllithium in the presence of Titrated o-phenathroline. The Na alcoholate was in the cocatalyst solved used. The divinylbenzene (DVB) represents a mixture of the m- and p-divinylbenzene and was used in the form of a 64 percent solution in hexane.

The sales were determined by changing the solids content after evaporation of the solvent and the monomers determined. The microstructure was determined by IR spectroscopy certainly. The block styrene content was determined according to Houben-Weyl, Methods of org. Chemie Vol. 14/1 (1961), page 698. Parts mean Parts by mass, percent (%) stands for Mass%.

Examples 1 to 3 butadiene / styrene

In one with dry nitrogen flushed V4A autoclaves were 475 parts hexane, a monomer mixture of 60 Parts of 1.3 butadiene and 40 parts of styrene are introduced and passed through a molecular sieve (0.4 nm) dried. Thereafter, 0.02 parts were added DVB and the specified amount of cocatalyst or cocatalyst Na alcoholates. Under thermoelectric control with butyllithium titrated. The polymerization was carried out at 40 ° C or 50 ° C by adding 0.06 parts n-Butyllithium started. The temperatures rose briefly despite cooling up to a maximum of 79 ° C on. The conversion was determined by means of solids determination and the Approach completely polymerized.

After cooling to 40 ° C Polymerization by adding a solution of 0.5 part of 2,2'-methylene-bis (4-methyl-6-tertiary-butylphenol) stopped in 2 parts of wet toluene. The solvent was evaporated with water distilled off and the polymer 24 hours at 70 ° C in a forced air drying cabinet dried.

Claims (13)

Process for the preparation of polymers using conjugated dienes and otherwise vinyl aromatic compounds by anionic polymerization at temperatures from 40 to 160 ° C, in an inert reaction medium in the presence of - at least one organolithium compound, - at least one amino compound of the formula (R ¹ ) (R ² ) -NXOR ³ - wherein R ¹ , R ² , R ³ independently of one another are alkyl radicals with 1 to 10, cycloalkyl radicals with 5 to 8, aryl radicals with 6 to 10, and aralkyl radicals with 7 to 15 carbon atoms or R ¹ and R ^{2 are} a ring with Form 4 to 7 carbon atoms and optionally 1 or 2 oxygen atoms in the form of ether bonds, X represents a C1 to C5 hydrocarbon radical or -YOZ-, where Y and Z independently of one another -CH ₂ CH ₂ -, -CH (CH ₃ ) CH ₂ -, -CH ₂ CH (CH ₃ ) - and / or - CH ₂ CH ₂ CH ₂ -, and - at least one alkali organic compound, - wherein the organolithium compounds to 0.01 to 1 part by weight per 100 parts by weight of monomer , - The alkali organic compounds) are used in a molar ratio of 0.01: 1 to 10: 1 based on the number of moles of the amino compound, - The alkali organic compound is an alkali metal compound of the formula R ⁴ OM, including the alkali metal alcoholates of polyhydric alcohols, R ⁵ COOM, R ⁶ R ⁷ NM is - w orin R ⁴ , R ⁵ , R ⁶ and R ⁷ independently of one another for hydrocarbon groups with 1 to 20 C atoms and - M stands for sodium or potassium, - wherein an R ⁶ or R ^{7 can} also be hydrogen, - as conjugated diene 1 , 3-butadiene and / or isoprene and - a monolithium compound having 1 to 20 carbon atoms is used as organolithium compound. Method according to claim 1, characterized in that at least one of the vinyl aromatic compounds selected is from the group consisting of styrene, 1-vinylnaphthalene, 2-vinylnaphthalene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstryrene and 4- (phenylbutyl) styrene. Procedure according to a of the preceding claims, characterized in that before or during the polymerization reaction Aromatics with several vinyl groups or alkyl aromatics with several Vinyl groups can be added as crosslinking coupling agents. Method according to claim 1 or 2, characterized in that at the end of the polymerization the living chain ends are implemented with coupling agents, being selected are from the group of aromatics with several vinyl groups, alkyl aromatics with multiple vinyl groups, silicon tetrachloride and tin tetrachloride. Method according to one of the preceding claims, characterized in that R ⁴ , R ⁵ , R ⁶ and R ⁷ independently of one another are hydrocarbon groups having 1 to 10 carbon atoms. Procedure according to a of the preceding claims, characterized in that the alkali organic compound together with the organolithium compound or together with the amino compound added to the polymerization mixture in the form of a finished mixture becomes. Procedure according to a of the preceding claims, characterized in that as the inert reaction medium cyclohexane and / or hexane can be used. Procedure according to a of the preceding claims, characterized in that 1- (N, N-dimethylamine) - (2-ethoxy) -ethane as the amino compound and 1- (N, N-dimethylamine) - (3-ethoxy) propane can be used. Procedure according to a of the preceding claims, characterized in that as an organolithium compound Monolithium compound with 2 to 12 carbon atoms, in particular 4 to 6 carbon atoms is used. Procedure according to a of the preceding claims, characterized in that the organolithium compounds used to 0.01 to 0.2 parts by weight per 100 parts by weight of monomer become. Procedure according to a of the preceding claims, characterized in that the alkali organic compound in a molar ratio from 0.01: 1 to 0.5: 1, based on the number of moles of the amino compound, is used. Polymers can be prepared according to one of the preceding Expectations. Use of the according to one of claims 1 to 12 polymers produced for the production of or use in damping materials and / or tires, especially winter tires and slush and snow tires, preferably in the tire treads.