DE2164515A1 - Process for the production of polybutadiene with predominantly cis-1,4-structure and controllable molecular weight - Google Patents

Description

SUMITOMO CHEMICAL COMPANY, LIMITED
Osaka, Japan

Process for the production of polybutadiene with predominantly cis-1,4 structure and controllable molecular weight

Priorities: Dec 28, 1970, Japan, No. 129 959/70

Dec. 28, 1970, Japan, No. 129 960/70.

Dec. 29, 1970, Japan, No. 124 346/70. Dec. 29, 1970, Japan, No. 124 349/70

The present invention relates to a process for the preparation of polybutadiene with a predominantly cis-l / 4 structure and einregel- \ Barem molecular weight by polymerization of 1,3-butadiene in the presence of a novel catalyst system.

For the production of polybutadiene with a cis-1,4 structure are already a large number of catalyst systems have been recommended. Typical examples of such known catalyst systems are: (1) A combination of a halogenated titanium compound and a trialkylaluminum compound; (2) a combination of one halogenated cobalt compound and an alkylaluminum halogen oxide

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and (3) a combination of a nickel or cobalt compound, a trialkylaluminum compound and a Lewis acid, such as an inorganic halogenated compound or its derivative.

Of these known catalyst systems, the ternary system (3) containing a nickel or cobalt compound has owing to high catalytic activity and the most diverse advantages in practical use have received the greatest attention.

The inventors found earlier in the present case (cf. BeIg. Patent 750 514 and Dutch patent application 70/07183) that the polymerization of 1,3-butadiene is advantageous carried out in the presence of a catalyst system of the following composition;

(A) At least one nickel and cobalt compound; (3) a trialkyl aluminum compound; (C) a benzotrifluoride of Formula I below

in which R,> R ₀ , R-, R. and R _c , .... , _TT . __ 12 3 4 5 independently of each other hydrogen,

represents a halogen atom, an alkyl group or a fluoroalkyl group, and
(D) a hydroquinone of the general formula II below

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in which R, ' _t R- ¹ , R-, ¹ and R-' each independently of one another denote hydrogen or a halogen atom, or R, 'and R ₃ ¹ or R' and R ¹ each together form an aromatic fused ring, while any remaining substituents still present are hydrogen or a halogen atom.

When using these known catalyst systems the polymerization reactions carried out, the molecular weight of the polybutadiene can be adjusted in a manner known per se for example by appropriate control of the composition of the polymerization batch, by controlling the process conditions and the concentration of the catalyst system, by appropriate Adjustment of the monomer concentration and the polymerization temperature. For the implementation of such control and control measures, however, is a special technical experience and care required.

The invention is based on the task of these in practice but to overcome quite significant disadvantage and to provide a polymerization process that is easy and can be carried out easily and in particular enables the regulation of the molecular weight in a particularly simple manner.

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Surprisingly, it has now been found that it diireh _r corresponding adjustment of the Wassergehaltes- Reaktionsmisehungen is possible in accordance with the _{f-MoiefcuJLargew} icfct of Solybutadulens; cease ^ and that the presence wan Was-seor in äer leaktioas-Eiisctong contrary to expectation ^ amen nlcM: dSie Fo..l.yHteri.sat.ionsges; c'h'wln he increased the "PolymerisationsgeschsiiEEdiigfceit in \ Fergieieh. zsia leads anhydrous work.

The process according to the invention for the production of polybutadiene with predominantly cis-1,4 structure and adjustable. Molecular weight is characterized in that l _r 3-butadiene either 1) in the presence of water and at least one alcohol,. a carboxylic acid and / or a phenol and in the presence of a catalyst system of the following composition

A) at least one nickel or cobalt compound;

B) a trialkyl aluminum compound;

C) a benzotrifluoride of the formula below

in which R ^, R ₂ , R ^, R ^ and E, - independently of one another, each denote hydrogen, a halogen atom, a C 1, 4 -alkyl group or a C, g-fluoroalkyl group;
D) a hydroquinone of the formula below

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- iC -.

In the ^ t% ^ 2 "*" ^ 3 * ^ ¹³² ^ ^R 4 * 3 ^SSiie; * mean -l ^s ^ naMiängig one another are hydrogen or a Halogenafcam or R * and R * respectively _..: R, 'and R ₄ * each zusaBEßen form an aromatic fused ring, while the remaining substituents may still be present is hydrogen or a Are halogen atom, or

2) J.n presence of a catalyst system of the following composition

A) at least one nickel or cobalt compound; D) a hydroquinone of the formula II given above and F) a dialkyl aluminum monofluoride;

and optionally in the presence of water and optionally at least one alcohol, a carboxylic acid and / or a phenol
is polymerized.

Unless otherwise stated, the term "alkyl" in the context of the invention means an alkyl group having 1 to 6 carbon atoms and the term "halogen" means chlorine, bromine, iodine and fluorine.

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The various salts and organic complex compounds of nickel and cobalt can be used as nickel and cobalt compounds, such as Ni halides, for example Ni chloride, Ni sulfate / the salts of organic acids, such as Ni acetate, Ni naphthenate, Ni octanoate ; the nickel salts of organic sulfonic acids / complex compounds of nickel salts such as the pyridine complex of Ni chloride, tris (d ± - pyridyl) Ni chloride ,. Bis- {ethylenediamine} -Ni-sulfate, organic coordination compounds of nickel or Ni chelates _/ v / ie bis-dimethylglyoxymato-Ni ^ 'j-bisethylacetacetate-Ni or bis-acetylacetonate-Ni and the corresponding cobalt compounds. Nickel compounds are generally preferably used.

Examples of the trialkylaluminum compound are trimethylaluminum, Triethyl aluminum, tri-n-butyl aluminum, triisobutyl aluminum and tri-n-hexylaluminum.

Examples of the benz trifluoride compound (T) are benz trifluoride,. 2-chlorobenz trifluoride, 3-chlorobenz trifluoride, 4-chlorobenz trifluoride, 2-bromobenz trifluoride, 3-bromobenz trifluoride, 4-bromobenz trifluoride, 2,5-dichlorobenz trifluoride, 3,4-dichlorobenz trifluoride, 2,3-dichlorobenz trifluoride, 2,3-dichlorobenz trifluoride, 2,3-dichlorobenz trifluoride , 3,5-difluorobenztrifluoride, 2-methylbenztrifluoride, 3-methylbenztrifluoride, 4-methylbenztrifluoride, 2-hexylbenztrifluoride, 4-hexylbenztrifluoride, 2-dodecylbenztrifluoride, 3-dodecylbenztrifluoride, 3-dodecylbenzotrifluoride, 3-dodecylbenztrifluoride, 3-dodecylbenzotrifluoride, 3-dodecylbenzotrifluoride, 3-dodecylbenzotrifluoride, 3-dodecylbenzotrifluoride, 3-dodecylbenzotrifluoride, 3-dodecylbenzotrifluoride, 3-dodecylbenzotrifluoride, 3-dodecylbenzotrifluoride, trifluoromethyl) benzene, 3- (3'-fluoropropyl) -benztrifluoride, 4- (2 *, .3 ¹ -difluoropropyl) benzene trifluoride, 1,3,5-tris (trifluoromethyl) benzene,

209831/0929.

2-methyl-4-chlorbenztrifluorid, 3-bromo-4-Äthylbenztrifluorid _r 2-methyl-4-trifluormethylbenztrifluorid.und 3-Pluor-4-trifluoro-_ methylbenztrifluorid.

Examples of the hydroquinone compound (II) are tetrachlorohydroquinone, 2,3,5-trichlorohydroquinone, 2,5-dichlorohydroquinone, 2-chlorohydroquinone, tetrabromohydroquinone, 2,3,5-tribromohydroquinone, 2,5-dibromohydroquinone, 2-bromohydroquinone, tefcrajodhydroquinone, 2,3,5-triiodohydroquinone, 2,5-diiodohydroquinone, 2-iodohydroquinone. Hydroquinone, 1,4-dihydronaphthalene, 1,4-dihydroxy-2,3-dichloronaphthalene, 9,10-dihydroxyanthracin, 1,4-dihydroxyanthrac in, and 1,4-dihydroxy phenanthri η.

Examples of the dialkylaluminium monofluoride are dimethylaluminum monofluoride, Diethyl aluminum monofluoride, diisopropyl aluminum monofluoride, Di-n-butylaluminum monofluoride, diisobutylaluminum monofluoride and di-n-hexyl aluminum raonofluoride.

As the alcohol, it is possible to use saturated and unsaturated aliphatic alcohols, aromatic alcohols, alicyclic alcohols or halogenated alcohols. Specifically there may be used methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, amyl alcohol, isoamyl, neopentyl, Hexy! Alcohol, Isohexylalkohol, heptyl, isoheptyl, octyl alcohol, isooctyl alcohol / Nony! Alcohol, Isonony! Alcohol, decyl alcohol, Isodecylalkohoi, Dodecy! Alcohol, Myristy! Alcohol ,, cetyl alcohol, stearyl alcohol, sea-butyl alcohol, tert-butyl alcohol, -see -aemj -! Alcohol, tert.-amyl alcohol, sec-hexyl alcoholj

2 0 9831/0929

tert.-hexylalkah.ol _f Äfehyleneglycol ^ .Progylen-gl.ycol · ,; glycol, tetramethylene glycol, glycerin, allyl alcohol _F Crotyla! crude oil, oley! alcohol ,. Butene-2-diol, propargyl alcohol ,. Benzyl alcohol * Cyclohexyl alcohol _f 2-chloroethyalkohol 2-bromoethyl alcoholitol and glycerine-2-monochlorohyorine.

Saturated and unsaturated aliphatic carboxylic acids, aromatic carboxylic acids, alicyclic carboxylic acids or halogenated carboxylic acids can be used as the carboxylic acid. Specifically there may be used acetic acid, propionic acid, valeric acid, isovaleric _f butyric acid, isobutyric acid, caproic acid, heptanoic acid, caprylic acid, pelargonic acid, capric acid, ündecansäure, lauric acid, myristic acid, palmitic acid, stearic acid, Rhodininsäure, Naphtheninsäure, disproportionated Rhödininsäure, 2-Äthylcapronsäure, benzoic acid, hexahydrobenzoic , ß-chloropropionic acid, 2,4-dichlorobenzoic acid and 2,5-dichlorobenzoic acid.

Phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 3,5-xylenol, 3,4-xylenol, p-tert ♦ -butylphenol, 2,6-dimethyl-4-tert.-butylphenol, 3-methyl-6-tert.-butylphenol, 2-methyl-4,6-di-tert-butylphenol, 2,4-tert-butylphenol, 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, -Naphthol, ß-naphthol, anthranol, o-chlorophenol, m-chlorophenol, p-chlorophenol, p-bromophenol, o-bromophenol, m-bromophenol, 2,3-dichlorophenol, 2,4,6-trichlorophenol. And 2,4,5-trichlorophenol.

The dialkylaluminium monofluoride compound can be obtained by that Trialky! aluminum with a perfluoroalkylsubsti-

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tüierte aromatic Wrlaiaaäung.feei temperatures of about -2Θ to iSO ^Q G in the presence or in the absence of an inert organic solvent * such as an aromatic hydrocarbon, z. Bi benzene * toluene or xylene, an aliphatic hydrocarbon ί such as hexane., Heptane barren gasoline, an all cyclic hydrocarbon "as Cyclöhexan or decalin, and a hydrogenated hydrocarbon, such as! Jeträlin, and its fluorinated derivative under substantially water-free conditions, along with other Brings inhibitors, such as oxygen, carbon monoxide or carbon dioxide, to the implementation.

As perfluoroalkyl-substituted. aromatic compound, an aromatic hydrocarbon, such as benzene or naphthalene, can be used, the at least one. Perf luoiraikylgruppe of the general formula -CF _{2 +} . in which η is an integer from 1 to 4, and which does not contain any further non-reactive substituents in the aromatic ring. Particularly preferred are aromatic hydrocarbons with 1 to 3 trifluoromethyl groups, such as benz trifluoride, 2-chlorobenz trifluoride, 3-chlorobenz trifluoride, 4-chlorobenz trifluoride, 2-bromobenz trifluoride, 3-bromobenz trifluoride, 4-bromobenz trifluoride, 4-bromobenz trifluoride, 3,4-dichlorobenz trifluoride, 2,4-dichlorobenzene trifluoride , 2,3-Dibromobenztrifluorid, 2,5-Dibromobenztrifluorid, 2,5-Dif luorbenztrifluorid, 3,5-Dif luorbenztrifluorid, 2 ^ -Methyl 1-Benztrifluorid, 3-Methylbenztrifluorid, 4-Methylbenztrifluorid, 2-Hexylbenz, 2-Hexylbenz, 2-hexylbenz, 2-hexylbenz -Dodecylbenztrifluoride, 4-dodecylbenztrifluoride, 2-monofluoromethylbenztrifluoride, 3-difluoromethylbenztrifluoride, 1,3-bis- {trifluoromethyl) -benzene, 3- (3'-fluoropropyl) -benztrifluoride 3, 4- (2 ', benz trifluoride, 1,3,5-

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- ^l0 "2164111

Tris- (met luormethy 1} -benzene * 2-methyl-4-GhIOrJS often ζ fcrii JLuörid -,

naphthalene, i-Tirlflüörinöthyin ^ phthäiih / 5 -, 8-Öiöhlör- i-trifiüoriflethyinäphtftälin and 1-TrifluarinethyX-S- (3 '-iiukörperiröpyl) -naphthalin. These connections can be ended alone or in Köiribinäfeiön.

109831/032!

It is not absolutely necessary to use the dialkylaluminium ionofluoride to isolate from the reaction mixture, plural marriage at the Implementation of the trialkylaluminum compound with the perfuoroalkyl-substituted aromatic compound is obtained. Rather, such a reaction mixture can also be used as such of the catalyst components are used. The catalytic Activity of the catalyst systems used according to the invention depends on the mixing ratio of the components, of the Order in which these components are mixed together, on the concentration of each catalyst component, on the temperature used in the preparation of the catalyst system as well as other factors of this kind. In particular, the mixing ratio of the individual catalyst components has one great influence on the catalyst activity. The inventive polymerization should with molar ratios of the nickel or Cobalt compound to the trialkylaluminum compound or the dialkylaluminum monofluoride (i.e. the ratio of the components A / B or A / F) from 0.001: 1 to 2: 1 and preferably from 0.01: 1 to 1: 1. Preferred molar ratios the. Trialkylaluminum compounds to the benzotrifluoride (B / C) are in the range from 0.1: 1 to 5.0: 1 and in particular from 0.2:. 1 to 4.0: 1. The molar ratio of the nickel or cobalt compound to the hydroquinone should be kept in the range from 0.01: 1 to 100: 1 and preferably from 0.1: 1 to 10: 1. Furthermore, the polymerization reaction in particular with molar ratios of water or the alcohol, the carboxylic acid / or the phenol to the trialkylaluminum compound in the range from 0.1 oil: 1 to 2: 1, preferably from 0.1: 1 to 1.2: 1 or in the range

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-12- 21S4515

rich, from O _r Ol r 1 to O, 5: 1 dtirciigefli & rfc-

With the erfindungsgerttäSen. PolYmerisatioitsverfatsren d nickel CKler cobalt compound in amounts of O _r OOl to 2 rn £ iol _r preferably from O _f Ol to 1 heMdI * 1 Koi employed monomeric 1 _f 3-Butadierij durchgeführt- If the amount of the above-mentioned catalyst components to If the catalytic activity of the catalyst system is large or too small, the catalytic activity of the catalyst system is reduced to an extraordinarily high degree and can almost drop to 0.

The mixing of the individual catalyst components can take place in any order and is usually done in presence a diluent. For the production of catalyst systems with very high activity, it is appropriate to use the Nickel or cobalt compound and the trialkylaluminum compound or the dialkylaluminum monofluoride in the presence of a small one Amount of an aliphatic conjugated diene, e.g. of 1,3-butadiene, Isoprene or dimethylbutadiene> to be mixed with one another. In this way, it is possible for the formation of insoluble material during the preparation of the catalyst system to prevent the damaging influence on one as much as possible to keep the low value caused by a pollution of the PoIymerisatiorisansatzes with a small amount, an impurity can be exerted.

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la -. ■ 218451

The setting © aj & es € &% i® & 3mg®qmM§ <m Katalfsstorsysteias

feel eiaaer iPesnperator in visited by -SO up

wad vwmigsweisie in the Ber ^ JLeli ν @ ΐί -20 to SO ⁰ CU To a catalyst sy stern snii; to obtain increased catalytic activity, 1st. It is necessary that the mixture in question, after all the catalyst components have been homogeneously mixed with one another, is finally fermented at a temperature in the range from 0 to 100 ° C.

The catalyst system No. 2 of the present invention can be prepared, for example, as follows; Mixing the dialkylaluminum monofluoride with a diluent, is initially a small amount of 1, 3-butadiene and then the nickel or cobalt compound and, finally, the hydroquinone added / the addition of the last-mentioned components may also take place in umgekeherter order. Finally, the mixture obtained in this way is aged at a temperature suitable for this. According to another embodiment, the nickel or cobalt compound and the hydroquinone are dissolved or in a suitable diluent. suspended. Then a small amount is added while cooling with ice. 1,3-butadiene is added, the dialkylaluminum monofluoride is then mixed in and finally ages at a suitable temperature.

To in the process according to the invention, the molecular weight of the To be able to adjust the polybutadiene to the desired value, a predetermined amount of water or a mixture of water is used and at least one alcohol, a carboxylic acid or one

, either to that. Catalyst system .. r? R _? % od © .r to the poly

The molar ratio of water to dialkylalifflinium mprigfluoride

should be in the lereigh yon Q.05 i 1 big l _f ß ι 1 and wisely in the range from 0.1? 1 to l _f 2; ■ 1. If an alcohol, a carboxylic acid and / or a phenol are used together with the water, their molar ratio to the dialkyl aluminum monofluoride is in the range from 0.01: 1 to P ₁ S? 1.

Mixing in the water, alcohol, carboxylic acid and / or the phenol in the polymerization batch can be carried out in the most varied of ways. According to one embodiment, v / ground these ingredients were added directly to the # 1 catalyst system during its manufacture. These components can be used in their Total amount or part of the nickel or cobalt compound, the trialkylaluminum compound, the benzotri-

Hydro
fluoride of the formula I and / or the / quinone of the formula II.

For example, one can proceed as follows: The trialkylaluminum compound is added to the benzotrifluoride of the formula I in a diluent. This mixture is heated to a corresponding temperature, then cooled with ice to about ⁰ ° C., then the alcohol, the carboxylic acid and / or the phenol and a small amount of -1,3-butadiene are added, and the mixture is finally mixed Nickel or cobalt compound and a mixture of the hydroquinone of the formula II and water are added in the order given and the mixture thus obtained ages. This way of working can also be modified in such a way that

that you first add the hydroquinone of the formula II and then a mixture of the nickel or cobalt compound with water. According to Another embodiment works as follows: The Nickel or cobalt compound and the hydroquinone of the formula II. are dissolved or suspended in a diluent. then a small amount of 1,3-butadiene is added while cooling with an ice bath, then a previously prepared solution is mixed Trialkylaluminum compound, the benzotrifluoride of the formula I and an alcohol »a carboxylic acid and / or the phenol are added, finally add Wa-e ^ r 'and finally age this mixture at an appropriate temperature. One can also use the following procedure in the preparation of the catalyst system procedure: Dissolve the alcohol, the carboxylic acid and / or the phenol, a small amount of 1,3-butadiene and the nickel or. Cobalt compound in a diluent, then mixed this "solution with a previously prepared solution, which the Contains trialkylaluminum compound and the benzotrifluoride, finally adds water and the hydroquinone and finally ages this mixture at an appropriate temperature.

According to another embodiment, the aforementioned Components can also be absorbed in 1,3-butadiene, or they can be admixed with a diluent that .by doing. Reaction s ans at ζ is used for the polymerization, or you can use the finished mixture of the catalyst system, 1,3-butadiene and a diluent before or during the Implementation of the polymerization are incorporated.

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The Eimarbeifceimgr ^ foee water »Alkaitoi, a Carlaomsctaare rand / or a phenol in the catalyst system: eM Ifr »2 lianam in any way before the production of this catalyst system take place, i.e. one for sale or the total amount of the Connections could be in part or all of the set nickel or cobalt compound, dialkyl almai nofluoridverbindungen and / or the hydroquinone be included. According to another embodiment, the compounds in question can also be added directly to the polymerization batch, by absorbing them ept ^ e-ier in '1,3-butadiene or the' A diluent is added which is used in the reaction s an sat ζ or by adding them to a premix from the catalyst system ", 1,3-butadiene and a diluent added before or during the polymerization reaction.

If you put the alcohol, the carboxylic acid and / or the phenol together added with water, the formation of insoluble substances during the aging of the catalyst can be completely avoided, while otherwise under certain conditions; For example, if the water content is too high, such insoluble substances precipitate. The catalyst system can therefore be made completely soluble in the polymerization mixture, whereby the continuous Production of the polybutadiene becomes possible.

The polymerization reaction is carried out under conditions in which there are practically no inhibiting substances, as is usually the case with catalysts from Ziegler ^ Natta Type are present. If a common catalyst is dated

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ι? - 2184515

g - is used, the © ine

contains bond, the polymerisation reaction is carried out under practically anhydrous conditions, because the presence of water reduces the polymerisation rate, which practically prevents polymerisation. in the

what about this in the process according to the invention? Application of the new catalog struc- tures

h the presence of water. "despite the gieieh presence an organizing Aium initiation connection " "Bärüberhinäüs lets you look at the inventive method * ren the Mölektilargeweh of the oil paeren with the adjustment of the oil Divide what amount to a predetermined value *

As a solvent and diluent for the catalyst system and / or the Polymeriöationsanöätg are among other things, aromatic Hydrocarbons such as Benzolι toluene or xylene, also ali ^ Jphatic hydrocarbons such as hexane, heptane and gasoline, furthermore alicyclic hydrocarbons, such as cyclohexane and decalin / and also hydrogenated aromatic hydrocarbons such as tetralin.

The polymerization is carried out by the · 1,3-butadiene in a liquid medium at a temperature ranging from -30 to 150 ⁰ C and preferably from O to 100 ° C with the particular catalyst system brings into contact. The order in which the catalyst system and monomeric 1,3-butadiene are fed into the reactor is not mandatory and is also not mandatory

the feeding in the presence or absence of the dilution «- by means of *

The polybutadiene formed can be obtained from the reaction mixture in a manner known per se *, for example, the leaction mixture is poured into a large amount of an aqueous or alcoholic medium such as methanol, isopropanoJU © in a mixture of methanol and acetone or hot water. If desired, an antioxidant can be added beforehand to this medium, for example phenol-β-naphthylamine or 2,6- di-tert-butyl-p-cresol. The precipitate is then filtered off and washed out with methanol. In this way, a practically colorless rubber-like polymer is obtained.

The polybutadiene produced according to the present invention is rubbery Solid or a high viscosity material. An analysis of the microstructure of these types of polybutadiene using infrared absorption confirms the presence of a predominantly cis-1,4 structure in most of the butadiene building units.

The following examples illustrate the invention, the viscosity number of the polymer given for characterization has been measured in a toluene solution at 30 ° C. The microstructure of the polymer in question is determined by inclusion of the infrared absorption spectrum determined according to the method of Morero, 'cf. Morero and colleagues: "Chira. E Ind.", 41, 758 (1959). .

B e i s ρ i e 1 1

The working method described below is carried out until it is completed the polymerization carried out in an argon atmosphere. All starting materials as well as the solvent will be carefully dehydrated and deoxygenated beforehand.

A solution of 4.0 mol of triethylaluminum in 3.54 ml of toluene as well 0.37 ml (3.0 mmol) of benzotrifluoride becomes 13.3 ml of anhydrous Toluene is added and this mixture is heated to 100 ° C for one hour. After cooling to room temperature 6.7 ml (4.5 g) of liquefied butadiene and a solution of 0.4 mmol of nickel naphthenate in 1.58 ml of toluene are added. the The mixture is stirred for 30 minutes at room temperature and then it is made up to a total volume of 100 ml with toluene. In this way, the catalyst solution to be used below is obtained.

A glass reaction tube is filled with a solution of 0.08 mmol of alcohol in 4 ml of toluene, with 7.5 ml of toluene with a water content of O, O445% (exactly determined according to the method of Karl Fischer) and charged with a solution of 0.04 mmol of tetrachlorohydroquinone in 8 ml of toluene. Then 10 ml of the above Catalyst solution added. This mixture is heated to 40 ° C. for 15 minutes and, after cooling, 70 ml anhydrous toluene added. The mixture is cooled further to −10 ° C. and then 3O ml (22 g) of liquefied butadiene are added. The reaction tube is then melted and polymerized three

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S-tune long at from. Phenyl- w., XB becomes a

C. ¹ Zm cEer Keakfcioms ^ sctarog will eimse-

sbLa in toluene zagesefezfe: vmu. this -wan Pheayl-g-Bapfafcfaylasiito in. Mefciiamo / l eiiige-

H _

pour. Bas is atisscheiöende kamtscaEufcarfcige Poljpioearisat is dried under vacuum at a temperature iumterhalb 5O ^Q C :.

The yield and physical properties of the so obtained Polybutadiene are given in Table I below.

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TABLE I.

ψ. alcohol Molar ratio -.-
nis to Mi-.,
naphtheaat Polymerization product 79.5 3.00 97.4 trans-1 ^ 4 Citt 1 link 2.0 I.
yield 75.5 3.63 9T.S. 1 * 5 HMiTiitu. .til .2 Isopropy alcohol 2.0 /63.2 ' 3.55 I ms : '1 * 3 1 »5 3 n-ootyl alcohol ^ / 2.0, 17.5 72.5 \ , 5.41 97.4, 1.5. · ; ! .a, 4th Lauryl alcohol 2.0 16.6 59.1 5.54 97.4 : 13 ; l »ft. 5 Stearyl alcohol .2.0. 68.6 3.00 \ 97.5 i '1.2 ! l »5 6th Allyl alcohol 2.0 15.9 ; 75.9 * 2.94 \ 97.3 ■ ' r 1.5, 11.4 7th Stylish chlorohydrin - .. 2.0 15.0 87.7 \ 2.54 ['97 .3 • i * 5 ^: ; i * 4. 8th Benzyl alcohol - 115.1 I 1.3 1 * 4 No addition .. ■ 16.7 1 * 4 19.5

*): During the production of the catalyst system: bi.ldeii "" s £ ch ' insoluble substances.

2164518

B ■ eis ρ ί e. 1 %

4.0 ntMol TriMthylaiumiiiium and 3.0 MMa1 benzotrifluoride heated in toluene according to the procedure of Example 1 and the total volume of this mixture is adjusted to 50 ml with anhydrous toluene *,

A reaction tube is filled with 5 ml of the catalyst solution described above, which contains 0.4 ml of triethylaluminum * and with a solution of 0.04 to 58. mmol of stearyl alcohol in 2 to 5 ml of toluene and also with a solution of 0.23 g of 1,3-butadiene in 3 ml of toluene and also a solution of 0.04 mmol of nickel naphthenate in 4 ml of toluene * This mixture is charged for 15 minutes warmed to 25 ° C for a long time. Subsequently, sets 3 to 6 ml of water-containing toluene and a solution of O, O4 ittMol tetrachlorohydroquinone in 8 ml of toluene are added and this mixture is aging for 15 minutes at 40 ⁰ C to give a clear very uniformly obtained catalyst solution * Then, with anhydrous toluene to made up to a total of 100 ml. This mixture is cooled to -10 ° C. Then 22 × f (30 ml) of liquefied butadiene are added and the reaction tube is melted. The polymerization is carried out at a temperature of 40 ° C. for 3 hours. The reaction mixture is worked up in accordance with the procedure of Example. The results obtained are summarized in Table II below.

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TABLE II

■ No. Molar ratio.
by StearyIaI-:
alcohol to Ni Molar ratio
nis' of, · What
ser "to 'Ni-', ¹ . Polymerization product yield 50.9 ■ Μ) χ
(dl / g) ι micro structure% trans-1.4 1.2 naphthenate naphthenate (δ) 82.3 2.45 cis-1.4 1.4. 1.3 1 '1.5 2.0 11.2 75.5 2.63 97.3 1.4 1.4. 2 2.0 2.0 18.1 83.2 3.10 97.2 1.4 1.3 3 2.5 ■ 2.0 16.6 79 * 5 2.84 97.3 1.4 1.4 4th 1.0 3.0 18.3 77.3 3.08 97.2 1.4 1.3 5 1.5 3.0 17.5 75.0 3.17 · 97.3 1.4 1.2 6th 2.0 3.0 17.0 79.5 2.92 '97 .4 1.4 · 1.3 7th 1.0 4.0 16.5 79.1 3.19 ■ "'97.3 1.5 ' 1.2 8th 1.5 4.0 17.5 3.38 97.3 1.4 1.2 9 2.0 4.0. 17.4 97.4

Example

A catalyst solution is prepared according to the procedure of Example 1 and then according to this procedure under Use of such a catalyst solution polymerizes 1,3-butadiene. In contrast to the procedure of Example 1, however, phenol is used instead of the alcohol. The one with it Results obtained are summarized in Table III below.

209831/0929

. TABLE III

phenol Molyer holder
nis to Ni- '- ■
naphthenate ' ., Polymerization product 76.4 (dl / g) • Microstructure.% 1.4 1.2 '- ■ · * "■■ .Link - 2.0 .Yield 83.2 2.85 cis-1.4itrans-1.4 1.4 1.2 1 phenol 2.0 (s) 79.1 1.73 97.4 1.4 1.3 2 o-chlorophenol - "2.O ₁ 16.8 83.2 2.16 97.3 1.4 1.4 3 p-chlorophenol 2.0 18.3 84.1 1.46 97.2 1.4 1.4 4th 2,4-dichlorophenol 2.0 17.4 85.0
80.4 1.50 97.2 1.4
Ί.4 1.4 VJl 2,4,5-trichlorophenol " 2.0
2.0 18.3 84.1 2.19
2.62 97.2 1.4 1.4
1.3 6th
7th 2,6-di-tert-butyl-4-
methylphenol
β-naphthol - 18.5 2.40 97.2
97.3 1.3 8th No, addition 18.7 '
16.4 97.3 ' 18.5

Example 4

Following the procedure of Example 1, a catalyst solution is prepared and 1,3-butadiene is prepared using this Polymerized catalyst solution. Instead of alcohol will be however, a carboxylic acid is used. The results obtained in this example are shown in Table IV below summarized.

209831/0929

TABLE IV

No. Carboxylic acid Molar ratio
.nis to Ni
nanhthenat Polymerization product 62.3
29.5
67.3
78.6 Ά .MicroStructure% trans-1,4 1.2 1
2
3
4th link O O O
CVI CM Ol yield 3.10
3.66
2.78
2.34 cis-1.4 1.5 '
1.5
1.5
1.4 1.3
1.2
1.3
1.3 Acetic acid.
2-ethylhexanoic acid. _ _<L
Benzoic acid ■
No. Addition KS) j \ / °) 97.2
97.3
97.2
97.3 13.7
6.5
14.8
17.3

Example 5

A reactor with a capacity of 170 ml and equipped with a stirrer is charged at a temperature of 30 ° C. with a toluene solution which contains 7.16 mmoles of nickel naphthenate and 237 mmoles of 1,3-butadiene per liter. In addition, a toluene solution is fed in which contains 30.1 mmol of triethylaluminum, 22.58 mmol of benzotrifluoride, 7.53 mmol of stearyl alcohol and 100 mmol of 1,3-butadiene per liter. This last-mentioned solution has been prepared by heating triethylaluminum and benzotrifluoride in toluene to 100 ° C. and then adding stearyl alcohol at a rate of 1.4-3 ml / h and 1,3-butadiene at a rate of 340 ml / h. This entire reaction mixture is transferred to a flask equipped with a stirrer reactor of 64 ml capacity ^ and then at a temperature of 30 ⁰ C wet toluene is fed with a water content of 0.0495 percent by weight at a rate of 189 ml / h. This reaction mixture is in turn transferred to a reactor of 75 ml capacity equipped with a stirrer, and then a toluene solution containing 5.0 mmol / l tetrachlorohydroquinone and 165 mmol / l 1,3-butadiene is added at a temperature of 40 ° C admixed at a rate of 205 ml / h. In this way a transparent solution with a theoretical nickel content of 1.167 mmol / 1 is obtained. Even 6 hours after preparation of this solution, no gel formation can be observed.

If, on the other hand, in the procedure described above, no Stearyl alcohol is used, so in the third reaction

209831/0929

tor a large amount of gel, which on the inner wall of the reactor sticks. Therefore, continuous production cannot be ensured for a long period of time.

110 g of 1,3-butadiene and 480 ml of toluene are fed into a 1 liter capacity reactor equipped with a stirrer. In addition, 170 ml of the catalyst solution, which has been prepared in the manner described above, is added with cooling. The reactor is then well sealed and polymerized for 3 hours at 40 ° C. After adding a toluene solution which contains 2,6-di-t-butyl-p-cresol and isopropanol, the reaction mixture is poured into a large amount of methanol. The precipitate is filtered off and dried in vacuo. This gives 79.5 g (72% yield) of polybutadiene with a viscosity number of 2.97 and a Mooney viscosity (100 ° C., ML _1. ) Of 47. Examination of the microstructure shows that this polybutadiene is 97.3% the cis-1,4 structure, 1.4% of the trans-1,4 structure and 1.3% of the vinyl structure.

. Example 6

A solution of 4 mmol of diethyl is placed in a glass reaction tube aluminum monofluoride fed into 20 ml of toluene, and then continues a solution of 2.4 g of 1,3-butadiene in 74 ml of toluene and a solution of 0.4 mmol of nickel naphthenate in 6 ml of toluene are added. These The mixture is heated to 25 ° C. for 30 minutes while stirring. 10 ml are then withdrawn and this portion of the catalyst solution is transferred in a glass reactor with a capacity of 2OO ml

209831/0929

, suitable for a Druckpölymerisat'ion. Subsequently, moist toluene with a water content of 0.0417 percent by weight and a solution of 0.04 mmol of tetrachlorohydroquinone in 8 ml of toluene are added and the mixture is heated to 40 ° C. for 15 minutes while stirring. It is then made up to a total volume of 130 ml with toluene. After the mixture has cooled to a temperature below -20 ° C., 22 g of 1,3-butadiene are added and the reaction tube is melted. All of the operations described above are carried out in a stream of argon. The reaction tube is placed in a rotating bath which is kept at a constant temperature of 40 ^° C., and then the polymerization is carried out for 180 minutes. The reaction mixture is then poured into methanol which contains a small amount of 2,6-di-tbutyl-p-cresol, whereby the polymerization is terminated. The precipitated polymer is separated off and dried in vacuo at room temperature. The yield obtained and the physical properties of the polybutadiene thus obtained are shown in Table V below.

209831/0929

TABLE V-

No. Molar ratio of
Water too, diethvl
alumini um-rMonö-
fluoride Polymeri
station
apit. '
VMin./. ., Polymerization product 2.87
2.26 Microstructure% ' trans-1.4 1.2 ■ ι
2 0.7
0.2 180
180 yield
{%) cis-i, 4 1.7
1.7 2.2
2.3 81.3
58.1 96.1
96.2

cn cn cn

Example 7

According to the procedure of Example 6, a catalyst system is prepared, but 0.02 mmol of nickel naphthenate and 0.2 mmol Diethylaluminum monofluoride are applied and the total amount of the catalyst solution is adjusted to 20 ml. The polymerization is then according to the procedure of Example 6 using 44 g of 1,3-butadiene for 2 hours at 25 ° C carried out. The results thereby obtained are as follows summarized in Table VI.

209831/0929

TABLE VI

1
2 Moly ratio * of
Tetrachiorhydro- • Molar ratio .; ._. ".
of water 'to ,. , ■■ 77.
44. 3 Polymerization product. (dl / g) .MicroStructure trans-1,4 _% " 2 chinön zu_Ni.7_ ■;,
naphthenate ' D.iath.ylaluminium-
Wo.no.fluorid 5
6th 3.04
3.82 cis-1.4 1.6
1.6 I ₁ 1
0 5
1 0
0.6 Uti 96.3
96.4 2.
2. κ> 39831 ■ / 0929

Example 8

A catalyst system is prepared according to the procedure of Example 6, except that 0.05 mmoles of nickel naphthenate and 0.5 mmoles of diethylaluminum monofluoride are used are used and the total volume of the catalyst solution is adjusted to 50 ml. The subsequent Polymerization is also carried out according to the procedure of Example 6 using 10.2 g of 1,3-butadiene in carried out a polymerization tube of 100 ml capacity,

The results obtained are summarized in Table VII below.

209831/0929

■ TABLE VII

•No. < Component (D), 10
5 Molar ratio . P.polymeri-
sations-.
go,
(Min.) .. , Polymerization product.,. LH]
(dl / g) Mikroat.rvikfcur% ... trans-1,4 1.2 1
2 from water to di ^
ethylaluininiuni " 300
180 Au sb.,.
(*) 1.03
2.43 cis-1.4 1.7
2.3 2.6
3.4 verc inciuncj 0
0.8 83.6
82.7 95.7
94.3 Tetrachlorohydroquinone _
Tetrabromhy'droquinone

Example 9

All of the hatreds described below are rolled into one Argon flow carried out. The starting materials as well as the solvents are carefully dehydrated and de-oxygenated beforehand. ".

A solution of 4 mmol of diethyl is placed in a glass reaction tube. aluminum monofluoride in 20 ml of toluene, and then a solution of 2.4 3 g of 1,3-butadiene in 10 ml of toluene and a, Solution of 0.4 mmol of nickel naphthenate in 4 ml of toluene was added. This mixture is stirred for 30 minutes at room temperature and then made up with toluene to a total volume of 100 ml.

A suitable for a pressure polymerization reactor tube made of glass with a capacity of 200 ml is with a solution of 0.08 mmol of alcohol in 4 ml of toluene and with 7.5 ml of hydrous toluene (water content! 0.0445 percent by weight, determined by the method von Karl Fischer) and also charged with a solution of 0.04 mmol of tetrachlorohydroquinone in 8 ml of toluene. Also be 10 ml of the catalyst solution described above were added. This mixture is heated to 40 ° C. for 15 minutes and then cooled. Then 70 ml of anhydrous toluene are added. After further cooling to a temperature of -10 C, 30 ml (22 g) liquefied butadiene added. The reactor tube is then melted and polymerized at 40 ° C. for 3 hours. The reaction mixture is mixed with a solution of phenyl-ß-naphthyl-

209831/0929

amine is mixed in toluene, and this mixture is made into one large Poured amount of methanol, which phenyl-ß-napthylarain dissolved contains. The rubber-like polymer which is deposited is dried in vacuo at a temperature below 50 ° C.

The yield obtained and the physical properties of the polybutadiene are summarized in Table VIII below. · "

209831/0929

TABLE VIII

mV Alcohol. Molar ratio ■
nis to ni-.
naphthenate Polymerization product [11
(dl / g) Microstructure tr ans-1,4 % 1.2 y A * Ju link 2.0 Education. '
' W 3.48
I. cis-1.4 1.5 1.7 1 Isopropyl alcohol , 2.0 60.5 3.69- 96.8 1.5 ' 1.2 2 n-octyl alcohol ..;. ·, 2.0 57.3 4.08 97.3 1.5 1.6 3 Allyl alcohol; 2.0 48.5 3.70 96.9 1.3 1.3 4th Ethylene chlorohydrin_ ' 2.0 53.5 3.41 97.4 1.4 1.4 5 Benzyl alcohol. - 62.1 2.93 97.2 1.3 1.4 6th No addition 63.5 97.3

*): During the manufacture of the catalytic converter system insoluble substances.

Example 10

A pressure-resistant glass polymerization tube is charged with a solution of 0.4 mmol of diethylaluminum monofluoride in 5 ml of toluene / and a solution of 0.04 to 0.08 mmol of stearyl alcohol in 2 to 5 ml of toluene and a solution of 0, 23 g of 1,3-butadiene in 3 ml of toluene and a solution of 0.04 mmol of nickel naphthenate in 4 ml of toluene were added. The mixture obtained in this way is heated to 25 ° C. for 15 minutes. Then 3 to 6 ml of moist toluene and a solution of 0.04 mmol of tetrachlorohydroquinone in 8 ml of toluene are added. This mixture is aged for 15 minutes at 40 ^° C., whereby a transparent, uniform catalyst solution is obtained. With anhydrous toluene filled up to a total volume of 100 ml and then cooled to -10 ⁰ C. Is then reacted 22 g (30 ml) added liquified butadiene, and melts from the polymerization tube. The polymerization is carried out at 40 ° C. for 3 hours. The further work-up is carried out as in Example 9. The results obtained are summarized in Table IX below.

209831/0929

TABLE IX

No.

Molar ratio tlol ratio ι

from stearyl alcohol to water to '-,

go to Ni-diethylaluminum-misbeüte Polymerization products

naphthenate '.

um monofluoride "

1 1.5 2 2.0 09831 3
4th 2.5
1.0 / 092 5
6th 1.5
2.0 "O '7 1.0 8th 1.5 9 2.0

0.2
0.2
0.2
0.3
0.3
0.3
0.4
0.4
0.4

65.9 64.8 57.5 73.2 70.8 70.1 68.5 .62.8 55.1 3.41
3.52
3.78

3.43 '

3.67

3.82

3.62

5.85

4.13

Microstructures

cis-1,4 trans-I, 4

97.1 97.3 97.5 97.1 97.0 97.3 97.2 97.4 97.3

1.5 1.3 1.1

1.3 lP 1.4 1.4 1.3. 1.4

2154515

Il

It is produced -a Iiatalpsatorlaspag- -according to the method of operation ¹ VOJi at 9j, ■ säöbei jeclDeli instead of φθιϊ Älfeohcsl phenol VTlarä- .13ie white Boljraerisafcioa - »on 1,3-eutadiene li - use of this 3i ^ talysatoxig also takes place The results obtained from the oils are shown below in
/! Table X summarized »

209831/0329

• TABLE X

No. ,Phenol t4Ql ratio
nis to ni-
naphthenate . Yield i " olvmeri cis-i _r 4 ~ | 'X3' .1,2 1 link 2.0 ' 55.5 m
(dl / g) 97 .x : X3 a.4; 2 phenol 2 * 0, _t 65.2 3.53 ■ 91 ^ i ■ X3 X ^. 5 p-chlorophenol 2.0 63.8 2.92 97.2 V ■ 1.5: 4th
5 2,4,5-trichlorophenoi ' 2.0
I.
2.0 70 .1
61st, 0 2.25 ^: -97.4 '
97..0; ..: '1 * 4: 6th 2, S-di-tert-butyl-4-
methylO-henol
ß-naphthol , _ 60.2 2.82
3 * 01 m.z \ no addition 3.QS

-43- 2184515

Example 12

A catalyst solution is prepared according to the procedure of Example 9, but using a carboxylic acid instead of the alcohol begins. The polymerization of 1,3-butadiene using this catalyst solution is also carried out according to the procedure of Example 9.

The results obtained are summarized in Table XI below.

209831/0929

TABLE XI

O CO CSO

No. Carboxylic acid Molar ratio
nis to ni-
naphthenöt'i Polymerization product Yield ...
W- (dl / g) Micro link no% trans-1,4 1.2 1
2
3
4th ■ ··. link 2.0
2.0
3.0 45.8
38.3
51.5
58.2. 3.41
3.84
3.23
2.92 CXS-I, 4 1.5
1.6
1.3
1.2 1.7
1.2
1.5
1.5 _v acetic acid
2-ethylcaproic acid '
Benzoic acid.
No addition 96.8
97.2
■ 97.2
97.3.

(J) CJI

Example 13

A three-necked flask with a capacity of 300 ml is charged under a stream of nitrogen with a solution of triethylaluminum purified by vacuum distillation (boiling point 75-78 ° C./5.0 mmHg; 100 mmol) in 91.5 ml of toluene. This solution has a concentration of triethylaluminum of 1.095 mmol per ml. In addition, 12.3 ml (100 mmol) of a benzotrifluoride (boiling point 10 3.5 ° C./760 mmHg) purified by distillation are added. The mixture thus obtained is heated to 80 ° C. for one hour with stirring. After cooling to room temperature, the reaction mixture is fractionally distilled. The first fraction obtained is a distillate with a boiling point of 110 ° C./760 mmHg, which consists of 85 ml of toluene containing 67 mmol of unreacted benzotrifluoride. The second fraction with a boiling point of 45 to 70 ° C./2 mmHg is a colorless, transparent liquid (5.4 ml) which contains 11.0 mmol of unreacted triethylaluminum and 4.0 mmol of diethylaluminum monofluoride. The third fraction with a bp of 95 to 120 ° C / 2 mmHg is a colorless, transparent liquid (6.0 ml) of high viscosity _} which consists practically of pure diethylaluminum monofluoride. The distillation residue (0.7 g) is a colorless, transparent solid which is probably a mixture of diethylaluminum monafluoride and monoethylaluminum difluoride. The total yield of diethyl aluminum monofluoride in the second and third fractions is 77.6%, based on the triethyl aluminum used as the starting material.

209831/0929

Examples 14-17

The reaction is carried out according to the procedure of Example 13, except that one of the substituted benzotrifluorides indicated in the table below is used instead of benzotrifluoride. The distillation of the reaction mixture obtained in this way is also carried out according to the procedure of Example 13. The results obtained are shown below in
Table XII summarized.

20983170329

TABLE XII

at
game
Jr. Substituted
Benz trifluoride Molar ratio
to triethyl
aluminum - j Third parliamentary group Destil-
lational
berap.
( ⁰ C) Al
At om) P.
(mg-
^ tom) Education /
<% ·) * H Chemical Be
drawing 1.0 )shock
fTorr) 95-
123 70.3 70.0 70.2 15th 2-chlorobenzene
trifluoride 1.0 2.0 95-
120 68.2 67.5 68.0 16 2-BrorabenzT
trifluoride 1.0 2.0 92-
118 70.5 70.3 70.3 17th 2,4-dichloro
benztrifluo
rid 1.0 2.0 95-
120 76.3 75.2 75.5 3-trifluoro
methylbenzene
trifluoride 2.0

*) <Calculated for the third only Amount of diethylalminium monofluoride contained in the fraction

209831/0929

Claims (8)

-48- 2184515 P a, tei t ai sp r le tie "X / method zrair manufactiacr ^ on. PcÄ-ffoBtadieOi rait, fifoerwxegea ice — 1 *. 4-Straktor tiimd egg-yellow Kolefctilargewlclifcr thereby. gekenEizexcIinet: «. öaS l ^ S-BmfcadüeH. either in the presence of, water soi ^ ie at least one alcohol, a carboxylic acid and / or a Piiemols tirtd in the presence of a catalyst system of the following composition:
A) at least one nickel or cobalt compound; B) a trialkyl aluminum compound; C) a benzotrifluoride of the formula below (D ,, R ₂ / R ₃ 1 R ₄ and R, in which R - independently jev; Eils hydrogen, a halogen atom, a C, ggruppe or a C ₆ _ fluoroalkyl group; D) a hydroquinone of the formula below (II) 209831/0929 - m ^ ' - -2194118 in ^ elefaer- R ₁ , ü ₂ % B hydrogen © the ap afikeinöeiisierti Sing form _f while nctph existing re ^ tlipjieri Hydrogen © de ^ r a H ^ 3.ogenati? M sip4 ^ or 2) in Änv / eseiiheil: a catalatarsystein öer j | aehst: eliend, §n Addition? A) at least one NipkeX- pder ^ Q ^ aitvepbendungj P) a hydroquinone of the formula II given above and F) a Dialkylalyminiummonofltiorid,. and optionally in the presence of water and optionally at least one alcohol , a carboxylic acid and / or a phenol
is polymerized. 2. The method according to claim 1, characterized in that the polymerization is carried out with a catalyst system, in which the molar ratio of the nickel or cobalt compound increases the trialkylaluminum compound or the dialkylaluminum mono * - fluoride in the range from 0.001: 1 to 2: 1, the molar ratio of the trialkylaluminum compound to the benzotrifluoride in the range from 0.1: 1 to 5: 1 and the molar ratio of the nickel or cobalt compound to the hydroquinone in the range from 0.01: 1 to 100: 1. 2A 2114111 3. Method according to claim 1 and 2 _f gekenjizeichnet that the polymerization at MQl ¥ eriiältni§gep γ, ο, η $ & §§ ££ lazw? Alcohol, carboxylic acid uiid / qder phenol gu der- TrialJtylalv} iRi! Iii4in ¥ connection vpn 0 _# 0l: 1 to 2: 1 bsw ·? 0ϊΐ Q ^ 01- \% |> is Q _? p «1 is carried out. 4. The method neieh claims 1 and 2 _f characterized in that the polymerization at Mplverhä ^ ltnisseR νο, η water to the dialkyl aluminum monofluoride vpn O _? Q5: 1 to 1.5? 1 is carried out. 5. The method according to claim 1 and 2, characterized in that polymerization in the presence of water with molar ratios of alcohol, a carboxylic acid and / or a phenol to dialkylaluminum monofluoride from O, OI: 1 to 0.5: 1. 6. The method according to claim 1 to 5, characterized in that the polymerization with O, OÖ1 to 2 mmol of the nickel or cobalt compound per mole of 1,3-butadiene used as starting material. 7. The method according to claim 1 to 6, characterized in that the polymerization is carried out in the liquid reaction medium at temperatures in the range from -30 ° C to 150 ° C, 8. The method according to claim 1 to 7, characterized in that the polymerization is carried out by means of a dialkylaluminum monofluoride obtained by reacting a TrLalkylaluminum compound with a perfluoroalkyl-substituted aromatic 209831 / ÖSai Compound at a temperature of −20 ° C. to + 150 ° C. , if necessary in the presence of an inert organic solvent _f . 2 09831/0929