DE2043746A1 - Process for polymerizing butadiene and butadiene in a mixture with other conjugated diolefins - Google Patents

Description

Dipi.-ing. Walter Meissner Dipi.-ing. Herbert Tischer

1 BERLIN 33, Herbertstrasse 22 MUNICH

Telephone: 8 87 72 37 - Wired word: Invention Berlin
Postal checking account: W. Meissner, Berlin West 12282

Bank account: W. Meissner, Berliner Bank A.-Q, Depka 3β, « _Λ -. _Λ

Berlln-Halensee, KurfOrstendamm 130, account no.96 716 ₁ BERLIN 33 (GRUNEWALD), the J I. AUQ. 1970

Herbertstrasse 22

6742 GE

TUE GOODYEAR TIRE AlJD RUBBER COMPAIiY, Akron, Ohio 44316, USA ■

Process for polymerizing butadiene and butadiene in a mixture with other conjugated diolefins

The invention relates to a method for polymerizing butadiene and butadiene in a mixture with other conjugated diolefins to form polymers with a high content of cis-1,4-additives. The invention also relates to catalyst systems suitable for this purpose.

Polymers made from butadiene or butadiene mixed with other conjugated ones üiolefinen, which contain a high proportion of butadiene units in the cis-1,4-configuration, have properties that make them suitable as synthetic rubbers and impart high impact resistance to the plastics.

The object on which the invention is based is to create a process by which butadiene is increased to a high level can be polymerized on an eis 1,4 structure, i.e. an eis-1,4 content greater than 90%. Another object on which the invention is based is to create a catalyst system by means of these polymerizations can be carried out.

Line another object of the invention is copolymers of Form Isprens or other conjugated diolefins and butadiene in which repeating units of butadiene are high Content of cis-1,4-structure are derived.

The catalytically promoted polymerization of conjugated diolefins Is well known. Many of the catalysts proposed for the polymerization of 1,3-dienes are »owuhl catalysts of the Ziegler-Uatta type as well as alkali metal catalysts, such as Dutyllitüium. Usually these have known catalysts

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-T-

led to polydienes of mixed structures, ie Gamischs with cis-1,4; trans -}, 4 ;, 1,2 and 3,4 structure. However, it has been found that some of the previously known catalysts predominantly lead to the expedient cis-1,4 structure. One such system is a ternary catalyst system consisting of (1) an alkylaluminum halide, (2) a cermetallic chelate compound, and (3) a trialkylaluminum or trialkylaluminum hydride. Another such system is also a ternary catalyst system which consists of (1) at least one organometallic compound in which the metal is selected from the class of the compounds of groups I, II and III of the Periodic Table, (2) at least one organo-nickel salt or organic nickel complex compound and (3) at least one compound is selected from the class consisting of boron trifluorine and complex compounds thereof.

The catalyst system according to the invention now differs significantly of the previously known catalyst systems in such a way that the catalyst components according to the invention from Jer group, ordering from "inorganic" ".etall concerned luorboraten," etallhfcxaf luorophosphates, 1 -, 'etallhexaf luurantttir.onaten and organic derivatives the Ilexaf luorpiios [hate and Ilexaf luorantimonntr »selected are.

Erflndungsyeroäß butadiene or Futadien is used in combination with WEL w direct konjugierton Jioloflnen by InberührungbrLn <IPN polymerized under Lösuncjspolymerlsationsbe-dlngungen with a Katalysatorsyster \, the r Jr-out (Λ) v / enlgstens an organometallic compound, wherein the rirtall from the groups I, II and III the. Periodic Systerii. Is selected, (L) at least one compound selected from the group consisting of .jlckelsalts von carboxylic acids, organic KoiaplexverblindunMer des wlcktls and Lyickc ltutracarbonyl, selected Ii'.t, uiilI (C) at least one compound which. from the group, at; dividing au-; (1) Töti at luurboratfii des Lithiuws, Lerylliums, Ca IcI unuj, Mc \ vjru>Hluiiit;, iilck »? Lr. and cobalts, (2) Llthiumhexailuorph (^; phat, (J) Mthiuiuaexat 1 uurant iiuonat and (4) organic derivatives dea HexaL Luor £> hosplii.itü and llexnt luorantlinonats selected IiJt, ..) (. · ;; tf ^ ht .

BADORfGINAt " ³ " 1 0 '. ·. I: W 1 7 9 2

The monomers useful in the present invention are those such as they are commonly known as conjugated diolefins and which conform to the following formula:

^R 1 ^R 2
H ₃ -C = CC = CR ₃

where R ₁ , R 2 and R _{3 are selected} from the group consisting of hydrogen and alkyl radicals having 1 to about 10 carbon atoms, and R., R ₂ and R ₃ can be the same or different. Typical examples of conjugated diolefins are 1,3-butadiene; Isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 2-methyl-3-ethyl-1,3-butadiene; 1,3-hexadiene; 3-methy1-1,3-pentadiene and the like.

With regard to the organometallic compounds which contain metals of groups I, II and III, it is preferred according to the invention organo-aluminum compounds, organo-lithium aluminum compounds, use organomagnesium compounds and organozinc compounds.

The term "organoaluminum compound" includes organoaluminum Compounds to understand those of the formula:

Al

where R. is selected from the group consisting of hydrogen, fluorine and a monovalent hydrocarbon radical such as an alkyl, alkenyl, aryl, aralkyl, alkaryl, cycloalkyl and alkoxy radical having from about 1 to about 20 carbon atoms, and R ₂ and R _{3 are} monovalent hydrocarbon radicals selected from the group consisting of alkylene, alkenylene, arylene, aralkylene, alkarylene, and cycloalkylene having from about 1 to about 20 carbon atoms. Examples of such compounds corresponding to this formula are: diethyl aluminum fluoride, di-n-propyl aluminum fluoride, di-n-butyl aluminum fluoride, dihexyl aluminum fluoride, dioctyl aluminum fluoride and diphenyl aluminum fluoride. These also include diethy! Aluminum hydride, di-n-propy! Aluminum hydride, di-n-propy! Aluminum hydride, di-n-buty!

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Phenylethyl aluminum hydride, phenyl-n-propyl aluminum hydride, p-tolyl ethyl aluminum hydride, p-ToIy1-n-propy! aluminum hydride, p-tolylisopropy! aluminum hydride, Benzylethylaluminum hydride and other organoaluminum hydrides. Also included are: Xthoxydiäthylaluminium, Äthoxydipropylaluminium, Xthoxydiisobutylaluminium and other alkoxydialkylaluminum compounds, as well as trimethylaluminum, triethylaluminum, tri-npropylaluminiura, Triisopropyl aluminum, tri-n-butyl aluminum, triisobutyl aluminum, tripentyl aluminum, trihexyl aluminum, Tricyclohexyl aluminum, trioctyl aluminum, triphenyl aluminum, Tri-p-tolylaluminum, tribenzylaluminum, ethyldiphenylaluminum, Ethyl-di-p-tolylaluminum, ethyldibenzylaluminum, diethylphenylaluminum, Diethyl-p-tolylaluminum, diethylbenzylaluminum and further aluminum triorganic compounds.

The expression "organolithium aluminum" compound is to be understood as any organolithium aluminum compound which ^{corresponds to the formula R 1} R "JLiAl, where R * is hydrogen or an alkyl, alkaryl or aralkyl group, and R" is an alkyl, alkaryl or Aralky! Group can be. Where R ¹ and R "are alkyl, alkaryl or aralky! Groups , the same or different. Examples of such compounds are n-butyltriisobutyllithium aluminum, tetrabutyllithium aluminum, tetraethyllithium aluminum, tetraethyllithium, aluminum and the like and the like

The expression "organomagnesium compounds" is to be understood firstly as any organomagnesium complex which has the formula ^R a ** ^9X be ^nt8 P ^rlcnt # where R is a monovalent hydrocarbon radical having 1 to about 20 carbon atoms; X Wass are halogen and "a" and "b" are garbage fractions, the sum of which is equal to 2, while the ratio of a / b is greater than 2 but not infinitely. Characteristic for compounds which correspond to the above formula are ethyl magnesium chloride complex, the cyclohexyl magnesium bromide complex and the phenyl magnesium chloride complex. These compounds are usually made in the absence of ether.

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"Organomagnesium compounds" are further to be understood as meaning any organomagnesium compound or organomagnesium halide of the Grignard type, corresponding to the following formulas R ₂ Mg or RNgY, where R is an alkyl, alkenyl, aryl, aralkyl or alkaryl radical and Y is Fluoride or R ¹ R ¹¹ Hg, where R * can be an alkyl, alkenyl, aryl or alkaryl radical and R ″ can be either an alkyl, alkenyl, aryl, aralkyl or alkaryl radical. Examples of compounds which corresponding to the above formulas are diethylmagnesium, dipropylmagnesium, ethylmagnesium fluoride and phenylmagnesium fluoride.

The expression "organozinc compound" is to be understood as meaning any organozinc compound which _{corresponds to the formula R 2} Zn, where R is a monovalent hydrocarbon radical, such as an alkyl, alkenyl, aryl, aralkyl, alkaryl and cycloalkyl radical from about 1 to is about 20 carbon atoms. Examples of compounds which correspond to this formula are diethylaagnesiua, dipropylamagnesium, ethylmagnesiuafluoride and phenylmagnesiuafluoride.

By the term "organozinc compound" is meant any organozinc compound To understand compound that corresponds to the formula R ^ Sn, where R is a monovalent hydrocarbon radical, such as a Is alkyl, alkenyl, aryl, aralkyl, alkaryl and cycloalkyl radical with about 1 to about 20 carbon atoms. Characteristic for such compounds are diethyl zinc, dibutyl zinc and diphenyl zinc.

Characteristic examples of further organometallic compounds in which the metals from groups I, II and III of the periodic Systems are selected are compounds that combine at least one of the metals sodium or potassium with at least contain an organic radical which is selected from the group of alkyls, alkaryl · / aralkyls and aryls.

The (B) catalyst component is from the class consisting of Nlokel salts of carboxylic acids, organic complex compounds des nickel «and nickel tetracarbonyl. These connections Can make compounds of this metal with a mono- or bidentate organic ligands with up to 20 carbon atoms.

1 0 ': '. I Ί I 1 7 9 2 " ⁶ "

"Llgand" is defined as an ion or molecule attached to a Metal atom or ion is bonded or considered to be bonded thereto, bin-toothed means that there is a position through which covalent or coordinative bonds can be formed with the metal. Mehvsahni two-toothed means that two places are present, through which covalent or coordinative bonds can be formed with the metal.

Typical examples of such nickel salts of carboxylic acids and organic complex compounds of nickel are nickel benzoate, nickel acetate, Mlckelnaphthenat, bis (α-Fury Ddioximni disgust, Nickel octanoate, hickel palmate, nickel stearate, hick lac tylace- * clay, bis (sallcylaldehyde) äthyleridllmlnlekel, nlckelsallcylaldehyd and the like

The (C) catalyst component is from the group consisting of Tetrafluoroborates of lithium, beryllium, calcium, magnesium, nickel and cobalt} lithium hexafluorophosphate; Llthlumhexafluorantimonat and organic ammonia of hexafluorophosphate and hexafluoroantimonate is selected.

Characteristic examples of the tetrafluoroborates and organic derivatives of hexafluorophosphate and hexafluoroantimonate are lithium fluoroborate, beryllium fluoroborate, calcium fluoroborate, magnesium fluoroborate, nickel fluoroborate, cobalt fluoroborate, triphenyl- _B methylhexafluorophosphate, tri-hexylmethyl-hexafluorophosphate, tri-hexylmethyl-hexafluorophosphate, tri-hexylmethyl-hexafluorophosphate, tri-hexylmethyl-hexafluorophosphate, tri-hexylmethyl-hexafluorophosphate, tri-hexylmethyl-hexafluorophosphate, tri-hexylmethyl-hexafluorophosphate,

The compounds useful as the (C) catalyst component are usually supplied as suspensions in an inert solvent applied. The term "inert solvent" is to be understood as meaning that the solvent is the specific compound of the substances used (C) Does not attack the catalyst component. Such solvents are usually aliphatic, aromatic and cycloaliphatic Hydrocarbons such as pentane, hexane, heptane, benzene, Toluene, cyclohexane and the like.

The three-component catalyst system according to the invention has shown polymerization activity over a wide range of catalyst rates and catalyst ratios. Obviously I t- * k <m the three catalyst components to form the

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active catalyst together. As a result, the optimal concentration for each individual catalyst component depends on the concentration of the other catalyst components. Although the polymerization takes place over a wide range of catalyst concentrations and proportions occur, polymers are obtained in a narrower range which have very useful properties own. It has been found that polymerization occurs when the molar ratio of the (A) component of the catalyst system changes to the (B) catalyst component to about 0.3 / 1 to about 200/1, and the molar ratio of the (C) catalyst component to the (B) catalyst component to about 1 / L to about 300/1 and the molar ratio of the (A) catalyst component to the (C) catalyst component ranges from 0.05 / 1 to about 5/1.

The preferred (A) / (B) molar ratio is in a range from about 2/1 to about 40/1; the preferred (C) g (B) molar ratio ranges from etsaw 2/1 to about 100/1, and the preferred (A) / (C) molar ratio ranges from about 0.15 / 1 to about 2/1.

The three catalyst components can be added to the polymerization system are added as separate catalyst components either gradually or simultaneously, occasionally also as "in situ" designated. The three components can also be used outside the polymerization system "pre-formed" with all catalyst components be mixed in the absence of butadiene either with or without an inert diluent and the obtained completely homogeneous mixture is then added to the polymerization system added.

The catalyst can also be used outside the polymerization system "Are preformed" with all ketalysate components in the presence a small amount of butadiene or other conjugated diolefins are mixed. The amount of butadiene present can can be varied over a wide range, but should be one be catalytic amount. To get good results you can The molar ratio of butadiene to the (B) catalyst component is in a range from about l / l to ets »1000/1. A preferred one Molar ratio of butadiene to the (B) catalyst component from about 3/1 to about 300/1.

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The concentration of the total catalyst system used depends on the number of factors such as the purity of the system, the desired rate of polymerization, temperature and others Factors and thus no specific concentrations can be given except that catalytic amounts are applied will. Some specific concentrations and ratios that will result in polymers with the desired properties are indicated in the examples.

In general, the polymerizations according to the invention in carried out in any inert solvent and thus represent solution polymerizations. The expression "inert solvent" it is to be understood that the solvent or diluent does not and also does not enter into the structure of the polymer obtained does not adversely affect the properties of the polymer, nor any adverse effect on the activity of the applied Catalyst has. Such solvents are usually aliphatic, aromatic, cycloaliphatic hydrocarbons and ethers, and examples of these are pentane, hexane, heptane, toluene, Benzene, cyclohexane, diisopropyl ether and the like. Preferred solvents are hexane and benzene. The solvent / monomer volume ratio can vary over a wide range. It can up to 20 or more to 1 volume ratio of the solvent to it Monomer are applied. It is usually preferred or more convenient to have a solvent / monomer volume ratio of about 3/1 to about 6/1 to be used. Suspension polymerizations can be carried out using a solvent such as butane or pentane in which the polymer formed is insoluble. It should be understood, however, that bulk polymerizations are not of scope the invention should be excluded. The polymerization can be carried out continuously or batchwise.

The temperatures used according to the invention have not proven to be critical and can vary from a low temperature, such as -10 ° C. or below, to high temperatures of 100 ^° C. or above. However, a more suitable temperature range is about 20 to about 80 ° C. Normal pressures are usually used, but higher or lower pressures can also be used.

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As used in the description, the inherent viscosity (Γ [) defined as the natural logarithm of the relative viscosity at 30 ° C divided by the polymer concentration for a 0.5% (W / V) solution in toluene and is expressed in deciliters per gram (dl / g) expressed.

The cis-1,4 structure of the polymer is determined by means of infrared analysis certainly.

The invention is illustrated below with the aid of a number of exemplary embodiments explained in more detail.

example 1

Purified butadiene (BD) in benzene solution containing 100 g of butadiene per liter of solution is introduced into 100 ml bottles. Nitrogen is flushed over the surface of the premix and the catalyst is added in situ. The catalyst system used consists of a 0.25 molar solution of triethylaluminum (TEAL) in benzene, a 0.05 molar solution of nickel octanoate (NiOct) in benzene and a 0.23 molar suspension of nickel fluoroborate hydrate (Ni (BF _{4 I 2} .XH ₂ O) in benzene The nickel fluoroborate hydrate is obtained by drying crystals of nickel tetrafluoroborate hexahydrate (Ni (BF ₄ ) ₂ .6 H ₂ O) at 94 ° C. under a vacuum of 73.5 cm Hg for 16 hours The weight loss during drying is 29% of the theoretical water of hydration.

After the catalysts have been injected, the sealed bottles are placed end over end in a 50 ° C water bath turned. The polymerizations are deactivated by the addition of a suitable interruptor and an antioxidant added. The microstructure of the polymer produced according to experiment no. 5 is 96.5% vls-1.4, 1.5% tranβ-1.4 and 2.1% 1,2-polybutadiene was found. The microstructure of the nach the polymer produced in experiment no. 9 is 95.4% cis-1,4, 2.7% trans-1,4 and 1.9% 1,2-polybutadiene found. The following Table I gives further important data.

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Table I.

Trial millimoles / 100 g BD reaction yield (s) No. TEAL NiOct Ni-Fluor- time wt.%

borate h

1 0.75 0.02 0.75 example 4th 2 60 2.8 2 0.75 0.05 0.75 18th 93 3.0 3 IfO 0.05 0.35 18th 55 3.1 4th 1.0 0.05 0.45 18th 83 3.2 5 1.0 0.05 0.75 4th 76 2.8 6th 1.0 0.05 1.50 1 45 3.1 7th 1.0 0.05 1.50 4th 84 3.0 8th 0.6 0.10 0.75 17th 75 2.8 9 1.0 0.10 1.50 16 94 2.8 10 1.0 0.10 3.0 18th 93 2.5 11 1.0 0.10 6.0 18th 95 2.1 12th 1.5 0.10 1.5 16 96 2.5

A series of polymerization reactions similar to those of Example 1 are carried out with the exception that the
Polymerization bottles ^{treated at 80 0} C instead of 50 ° C
will. The catalyst components used in this series were the same as those according to Example 1. The microstructure
ψ of the produced after the experiment no. 4 Polymer w ^T de as being composed of 95.4% cis-1,4-, trans-1,4- 2.0% and 2.6% 1,2-Polybatadien found. Table II illustrates the
Polymerization conditions and results in more detail.

Table Il

Trial millimoles / 100 g BD reaction yield (n) K ^ ₄ TEAL NiOc £ Ni fluoroborate 2§4S.i - & --..._- §§! I. & S ._

4 54 2.7

4 80 2.1

2 77 2.2

2 80 1.9

4 34 1.7

0.75 0.05 0.30 0.75 0.05 0.45 0.75 o, os' 0.75 1.0 0.05 0.75 1.0 0.05 1.50

13/1? Q ■>

- ■ ii -

Example 3

A series of polymerizations is carried out similar to that of Example 1 with the exception that a 0.25 molar solution of tetraethyl II tMumalumJJtlvmi (LiAlEt ₄ ) in a mixture of 20% by volume of tetrahydrofuran (THF) and 80% by volume of benzene instead TEAL according to Example 1 is applied. The nickel fluoroborate is produced from Ni (BF ₄ ) .. 6 H ₂ O by means of azeotropic distillation of toluene in order to remove part of the water of hydration. Sufficient benzene is then added to make a 0.45 molar suspension. Analysis by Karl Fischer method (ASTM E-2O3-64) of an aliquot of the nickel fluoroborate suspension indicates that 22% of the theoretical amount of the water of hydration has been removed. The microstructure of the polymer formed according to experiment 1 was found to be 95.6% cis-1,4-polybutadiene and according to experiment no. 5 to 95.9% cis-1,4-polybutadiene. All reactions are carried out for a period of 18 hours. The amounts of the various catalyst components used, the yields and the inherent viscosities are shown in Table III below.

Table III

Attempt-
No. Millimoles / 100 g BD
LiAlBt. HiOct Ni-Fluor-
* borate 0.01 0.75 yield
Weight% (η) 1 0.75 0.01 0.75 67 2.6 2 0.01 1.50 48 3.2 3 1.0 0.02 l, 50 74 2.7 4th IrO 0.05 1.50 93 2.5 5 1, O Example 4 97 2.6

There will be a series of polymerization reactions similar to those carried out according to Example 1 with the exception that instead of a single Hlckelfluorborate five nickel fluoroborates with different amounts of hydration water can be used. The nickel fluoroborate after experiment by Mr. 1 1st not dried and contains 6 moles of water of hydration. The nickel fluoroborate in experiment t 2 was dried under heat and vacuum (84 ° C. at 73.5 cm Hg) 16 hours and experiences a weight loss equivalent

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lent 9% of the theoretical water of hydration. The nickel fluoroborate used in Experiment 3 is dried with the application of heat and vacuum (94 ° C. at 73.5 cm Hg) for 16 hours and loses the equivalent of 29% by weight of its water of hydration. The nickel fluoroborate used in experiment no. 4 is dried with the application of heat and vacuum for 60 hours (Hl ⁰ C, at 73.5 cm Hg); analysis by the Karl Fischer method (ASTM £ -203 64) shows that it has lost 33% of its water of hydration. The nickel fluoroborate used in experiment no. 5 is obtained by distillation of benzene from Ni (BP-) ,. 6 HO produced. This partially dry nickel fluoroborate contains approximately 5 moles of water of hydration. Table IV gives the characteristic numerical values.

Table IV

attempt
Mr. Millimoles / 100 g BD
TEAL NiOct Ni fluoroborate 0.05 1.5 example yield
2 h 5 Wt.% At
18 h 2.9 1 1.0 0.05 1.5 50 91 2.8 2 1.0 0.05 1.5 79 94 2.8 3 1.0 0.05 1.5 78 95 2.7 4th 1.0 0.05 1.5 48 92 2.9 5 1.0 73 95

A series of polymerizations similar to those of Example 1 is carried out, with the exception that a 0.3 molar suspension of lithium fluoroborate (LiBF ^) in benzene is used instead of nickel fluoroborate. In experiment no. 6, a 0.25 molar solution of tetraethyllithium aluminum (LiAlEt ^) is used instead of the TEAL used in the previous polymerizations. It was found that the microstructure of the polybutadiene formed according to experiment No. 4 consists of 94.6% cis-1,4, 3.2% trans-1,4 and 2.2% 1,2-polybutadiene. The microstructure of the polybutadiene formed in Experiment No. 4 consists of 96.9% cis-1,4, 1.0% tear-1,4 and 2.1% 1,2-polybutadiene. All experiments of this series are at 50 ⁰ C for 17 hours, carried out with the exception of the experiment no. 6, where it is reacted for 40 hours at 50 ° C. Table V gives the important numerical values

again.ν ,,

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2043748

- 13 Table V

attempt
gr. Millimoles
Al MiOct 0.05 (100 g BD yield
LiBF ₄ % by weight 65 Example 6 (I ₁ ) 1 0.75 0.10 4th 44 3.4 2 0.75 0.05 6th 67 3.4 3 1.0 0.10 6th 80 3.3 4th 1.0 0.10 6th 83 2.9 5 1.0 0.05 12th 35 2.3 6th 0.5 4th 2.7

It will of butadiene monomer performed two polymerization reactions employing a reversed addition of the individual Katalysatorkomponentenf Thus, a 0.3 molar suspension of lithium fluoroborate (LiBF ₄₎ in benzene were added to the reaction bottle, and, subsequently to a 0.05 molar solution of nickel octanoate (NiOct) in benzene and a 0.25 molar solution of triethylaluminium (TEAL) in benzene was added. The reactions are run for 17 hours. Table VI gives the corresponding numerical values.

Table VI

attempt
No. Millimoles / 100
LiBF ₄ NiOct 0.1 g BD
TBAL Temp.
° C 7th yield
Weight% (I ₁ ) 1 4.0 0.1 1.0 50 53 3.4 2 5.0 1.0 80 69 1.9 example

There are three butadiene polymerization reactions similar to those according to Example 1 using a preformed catalyst mixture consisting of butadiene, a 0.25 molar TIAL solution, a 0.05 molar NiOot solution and a 0.23 molar Ni (BF ₄ ) ₂ . XH ₂ O suspension carried out. The polymerizations are carried out for 18 hours at 50.degree. C. with the exception of experiment no. 3, which is carried out at 80.degree. Dl · Table VII shows the corresponding Sahlen values. The polymer produced according to experiment no. 1 has an ois-1,4-polybutadiene content of M.4%.

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- 14 Table VII

verse
No. uch millimoles / 100 g
BD TEAL NiOct 0.05 BD
Ni fluoroborate yield <1 ) 1 15.0 1.0 0.075 0.75 78 2 , 7 2 22.5 1.5 0.05 1.12 83 2 , 5 3 15.0 1.0 0.75 71 2 , 2 Example 8

A series of polymerizations similar to those according to Example 1 is carried out with the exception that the (C) catalyst component is selected from the group consisting of a 0.1 molar lithium hexafluorophosphate (LiPFg) suspension in benzene, a 0.1 clear Dl ( 2-ethylhexy1) ammonium hexa £ luorophosphate ((C ₈ H ₁₇ ) ₂ NH suspension in benzene, a 0.1 molar triphenylmethylhexafluorophosphate (Ph ₃ CPFg) suspension in benzene and a 0.36 molar triphenylmethylhexafluoroantimonate (Ph ₃ CSbFg) suspension in benzene, The corresponding numerical values are given in Tables Villa and VIHb. The tests according to Table Villa are carried out for 17 hours in benzene at 50 ° C. The tests according to Table VIIIb are carried out in hexane at 50 ° C. for 17 hours carried out.

Table villa

Ver (C) catalysis millimoles / 100 g Bd Yield (n)% cis-1,4. such torkoaponente TEAL NiOct (C) wt.% content Ψ No.

1 LiPF ₆ 0/85 0.10 5.0 66 1.6 95

2 (C ₆ Hj) ₃ CPF ₆ 0.85 0.10 1.0 25 1.4 ^(ä) 94

3 (C ₈ H ₁₇ ) 2 ^NH 2 ^PP 6 ^Of85 ° ^{'25 lf25 53} ND ^(b) ND

(a) 'polymerization is carried out at 8O ⁰ C (b) ND - not determined

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(C) Katalyea-
gate component Table VIIIb 0.05 g BD
(C) yield
Gev.% ⁽ * tcis-1,4-
salary Ver
search
No. C ₆ H ₅ ) ₃ CSbF ₆ Milllaole / 100
TEAL HiOct 0.10 0.6 63 2.7 96 J. ( C ₆ H ₅ ) ₃ CPF ₆ 0.60 0.10 0.5 51 2.6 96 2 ( (J ₆ H ₅ ) ₃ CPF ₆ 0.60 0.10 1.0 49 2.8 ND ^(a) 3 ( C ₈ H ₁₇ ) ₃ NH ₂ PF ₆ 0.60 1.25 16 3.1 94 4 ( l, 50 (a) ND «Not starry.

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Claims (7)

Dipi.-ing. Walter Meissner Dipi.-ing. Herbert Tischer 1 BERLIN 33, Herbertstrasse 22 IL MUNICH Telephone: 8 87 72 37 - Wireword: Invention Berlin ' Poetic check account: W. Meissner, Berlin West 12282
Bank account: W. Meissner, Berliner Bank A.-G., OepkB 36,
Berlln-Halensee, KurfOrstenäamm 130, Account No. 95 716, g _ERUN 33 (GRUNEWALD), den THE GOODYEAR TIRE AND H-b-t * -. 22nd RUBBER COMPANY Claims t \ Process for polymerizing butadiene and butadiene in a mixture with other conjugated diolefins to form polymers which have at least 90% of the butadiene units in the cis-1,4 configuration, characterized in that at least 1 diolefin under polymerization conditions with a catalyst system in Is brought into contact, which consists of (A) at least one organometallic compound, wherein the metal is selected from groups 1.11 and III of the Periodic Table, (B) at least one compound selected from the group consisting of nickel salts of carboxylic acids, organic Complex compounds of nickel and nickel tetracarbonyl is selected, (C) at least one compound selected from the group consisting of (1) tetrafluoroborates of lithium, beryllium, calcium, Magnesium, nickel and cobalt, (2) lithium hexafluorophosphate, (3) lithium hexafluoroantimonate; and (4) organic derivatives of hexafluorophosphate and hexafluoroantimonate is selected, consists, wherein the molar ratio of the catalyst component (A) to the catalyst component (B) to about 0.3 / 1 to about 200/1, the molar ratio of the catalyst component (C) to the Catalyst component (B) to about 1/1 to about 300/1 and the molar ratio of the catalyst component (A) to the catalyst component (C) ranges from about 0.05 / 1 to about 5/1. 2. The method according to claim 1, characterized in that 1,3-butadiene is used as the conjugated diolefin. 3. The method according to claim 1, characterized in that a trialkylaluminum compound is used as catalyst component (A) will. 4. The method according to claim 1, characterized in that the catalyst component (A) is a tetraalkyllithium aluminum compound is applied. 103813/1792 Copy 5. The method according to claim 1, characterized in that as a catalyst component (C) the Llthiuratetrafluorborat, nickel tetrafluoroborate, Lithium hexafluorophosphate, triphenylmethylhexafluoroantimonate, Triphenylmethylhexafluorophosphate and di (2-ethyl) -hexyDanunoniumhexaf luorophosphate can be applied. 6. The method according to claim 1, characterized in that the preferred molar ratio of (A) / (B) is about 2/1 to about 40/1, the preferred molar ratio of (C) / (B) to about 2/1 to about 100/1; and the preferred molar ratio of (A) / (C) to about Ranges from 0.15 / 1 to about 2/1. 7. catalyst mass, characterized in that the same (A) at least one compound selected from the group consisting of trialkylaluminum compounds and tetraalkyllithiuraaluminum compounds 7 (B) at least one compound selected from the group consisting of nickel salts of carboxylic acids and organic ones Complex compounds of nickel and (C) at least one compound selected from the group consisting of lithiurate tetrafluoroborate, Nickel tetrafluoroborate, lithium hexafluorophosphate, triphenylmethylhexaf luo ran timonat, triphenylmethylhexafluorophosphate and Di- (2-ethylhexyl) ammoniuinhexafluorophosphate contains, whereby the molar ratio of (A) / (B) to about 0.3 / 1 to about 20O / 1, the molar ratio of (C) / (B) to about 1/1 to about 300/1 and that The molar ratio of (A) / (C) is from about 0.05 / 1 to about 5/1. Dipl.-IngifcTischer. A6 No. 60/70 (§461 Pat. AO) 10 i : 1 Ί / 1 7 9 2 Copy