DE2257137A1 - POLYMERIZATION PROCESS - Google Patents

Description

Polymerization process

The invention relates to a process for the polymerization of butadiene and / or butadiene in a mixture with other diolefins with the formation of polymers with a high. Content of cis- »1,4-addition, ie 90 percent or more _o It also relates to catalyst systems which can be used for this purpose. It has been found that such polymers have properties which make them useful as synthetic rubbers.

The aim of the invention is a process by which butadiene can be polymerized to a high content, ie 90 to 98 percent, of cis ~ 1 _B 4-polybutadiene. Another goal is a catalyst system with which these polymerizations can be carried out. “Another goal is the formation of copolymer seeds from isoprene and butadiene in which the polybutadiene segment has a high content of cis-1,4 structure.” Other goals will be apparent from the following description.

According to the invention, butadiene or butadiene is polymerized in a mixture with other diolefins by bringing this into contact under the conditions of solution polymerization with a catalyst which (1) at least one organometallic compound in which the metal from groups I ₉ II and III

«. 2 ~ 30982 2/107 0

of the perlode system is selected »(2) at least one nickel compound selected from the class of nickel salts of carboxylic acids, organic complex compounds of nickel, nickel tetracarbonyl, and (3) at least one hydrogen fluoride complex, which is formed by complexing hydrogen fluoride with a compound from the ketone class »Ethers, esters, alcohols» nitriles and the water produced contains _p

The organometallic compounds which can be used according to the invention are organometallic compounds of such metals as lithium, sodium, Potassium, rubidium, cesium, magnesium, calcium, strontium, Beryllium, barium, zinc, cadmium, aluminum, gallium and indium, With the term "Oragnometall-" alkyl-, cycloalkyl- ,, Aryl, Arylalkyl-, Alkarylreste detected, which unttir on the metal Formation of the organic charge of the special metal are bound «,

Of the organometallic compounds which according to the invention are usable, the use of organoaluminum ver * = bonds, organomagnesium compounds, organozinc compounds and organolithium compounds are preferred.

With the term "organoaluminum compound" is one Organoaluminum compound meant which of the formula:

^R 1
Al ^R 2

^R 3

corresponds to, in which R ^ aua the group: alkyl (including cycloalkyl), aryl, alkaryl, arylalkyl ,, alkoxy, hydrogen and fluoro, R2 and R «selected from the group: alkyl (including cycloalkyl), aryl, alkaryl and arylalkyl is. Representative of compounds which correspond to the formula given above are: diethylaluminum fluoride, di ~ n ~ propylaluminum fluoride, DI η butylaluminum fluoride, diisobutylaluminum fluoride, dihex; ¹ IaIu miniumfluorld, dioctylaluminum fluoride and diphenylaluminum fluoride. These also include diethyl aluminum hydride, di ^ npropyl aluminum hydride, di n-butyl aluminum hydride, dilsobutyl

- 3 309822/1070

^ Lumiumhydrid, Diphenylaluminiumhydrid, di-p-tolylaluminiumhydrid, Dibenzylalurainiumhydrid, PhenylSthylalumlniumhydrid, phenyl n-propyl, y> ~ Tolyäthylalumlniumhydrid, ρ ο tolyl-n-'propylaluminluinhydrid, p ~ Tolylisopropylaluminiumhydrid, Benzyläthylaluminiumhydrid, benzyl «n ~ propyl" anhydride and BenzylisopropylaluMniumhydrid and other Organoaluminiumhydrideo This also includes trimethylaluminum, Triäthylaluminlum, tri ~ n = propyl, Tx ¹ Iisopropylaluminium, tri-n ~ butylaluminum, triisobutylaluminum., TripentylaluminiUBV trihexylaluminum _f Trlc ^ rclohexylaluminium, tri "octylaluminum, triphenylaluminum, tri-p-tolylaluminum, tribenzylaluminum , ÄthyldipheGtylaluminium, Äthyldi-p-tolylaluminum, Äthyldibenzylaluminium, Diethylphenylaluminum ,. Diethyl-potolylaluminiuoi ,, diethylbenzylaluminium and other triorganoaluminum compoundso These also include diethylaluminium ethoxide, diisobutylaluminum ethoxide and dipropylaluminum ethoxide * '"■ - ·

"Organomagnesium compounds" is initially used to denote any organomagnesium _{complex which corresponds to the formula R 0} StSgX ^, where R is alkyl, aryl, arylalkyl or alkaryl; X is a halogen and a and b are molar fractions, the sum of which equals 2 let, while the ratio of a / b is greater than 2 "but not infinitely". The ethylmagnesium chloride complex is representative of the compounds which correspond to the formula given above , Cyclohexyl magnesium bromide complex and phenyl magnesium chloride = complex. Such compounds are usually made in the absence of ether

ⁿ organomagnesium compound £ 9n ^{N also} means an organomagnesium compound or an organomagnesium halide of the Grignard type, which corresponds to the formulas ^ Mg or RMgY, where R is alkyl, aryl, arylalkyl or alkaryl and Y is fluorine or R = R ⁰ »Mg, where R" is alkyl , Aryl or alkaryl and R ⁰ "can be either alkyl" aryl, arylalkyl or alkaryl. Representative of the compounds which correspond to these formulas are diethyl magnesium, ethyl magnesium fluoride and phenyl magnesium fluoride.

"4 -

309822/1070

The term "organozinc compound" denotes an organozinc compound which corresponds to the formula RgZn, in which R can be alkyl, aryl, alkaryl, or arylalkyl. Representative for such compounds are diethylzinc, dibutylzinc or Diphenyl zinc.

The term "organolithium compounds ¹¹ " denotes an organolithium compound which corresponds to the formula R-L1 "in which R" is an alkyl, alkaryl, arylalkyl or aryl group. Ethyllithium is representative of the compounds which correspond to the formula given above , Propylllthium, n-, sec- or tert-butyllithium, hexyllithium, styryllithium or phenyllithium. The term ⁿ organolthium aluminum compounds ^N also denotes a compound which corresponds to the formula RR * ', LiAl, in which R * and R "are alkyl -, alkaryl or arylalkyl groups. (R ¹ and R * ^f can be the same or different.) Representative of these compounds are n-butyltriisobutyllithium aluminum, tetrabutyllithium aluminum, tetraisobutylthium aluminum, butyltriethylethylene-lithium aluminum and styrene-aluminum-lithium aluminum.

Representative of other organometallic compounds which can be used are sodium, Potassium, calcium, beryllium, camlum and mercury alkyls, -alkaryl, -arylalkylβ and aryl

The component of the catalyst according to the invention which contains nickel can be any organonickel compound. It is preferred to use a soluble compound of nickel. These soluble nickel compounds are usually Compounds of nickel with a one- or two-digit organic ligand which contains up to 20 carbon atoms. "LIgSHd" is defined as an ion or molecule that attaches to a Metal atom or ion is considered bonded or all bonded. Blinking means that there is a place about which covalent or coordinative bonds can be formed with the metal; two-digit means that there are two digits are via which covalent or coordinative bonds with the

~ 5> -309822/1076

Metal can be formed. The term "soluble" means soluble in inert solvents. Therefore, any salt or organic acid containing from about 1 to 20 carbon atoms can be used. Representative of organonickel compounds are nickel benzoate, nickel acetate, Niokelnaphthenat, nickel octanoate, Bia (oj-furyldioxime) nickel Nickelpalmitat _t, nickel stearate, nickel acetylacetonate, Nickelsalloaldehyd, bis (salicylaldehyde) ethylene diiminnickel, bis (cyclopentadiene) nickel, nickel tetracarbonyl Cyclopentadienylnickelnltrosyl and. The preferred nickel-containing component is a nickel salt of a carboxylic acid or an organic complex compound of nickel.

The component of the catalyst of the present invention which contains the complexes associated with hydrogen fluoride should be compounds which rapidly associate with hydrogen fluoride form.

The compounds which associate with the hydrogen fluoride to form this catalyst component are such that they are capable of association with the hydrogen fluoride due to their strong hydrogen bonding character. Such Assoziationaverbindungen contain an atom or a group dl · are befähig _r, the hydrogen fluoride to borrow electrons or share electrons nit hydrogen fluoride. Compounds capable of association are ethers, alcohols, ketones, esters, nitriles and water.

The subclass of ketones can be defined by the formula R ¹ GR, in which R ¹ and R represent alkyl, cycloalkyl, aryl, alkaryl and arylalkyl radicals containing from 1 to about 30 carbon atoms; where R * and R can be identical or different. These ketones represent a class of compounds which has a carbon atom bonded to oxygen via a double bond. Representative, but not exhaustive, of the ketones which can be used in the preparation of the ketone-hydrogen fluoride complexes according to the invention are dimethyl ketone, methyl ethyl ketone, dibutyl ketone, methyl aobutyl ketone, ethyl octyl ketone

303822/1070

ketone, 2,4-pentanedione, butylcycloheptanone, acetophenone, amylphenylketone, butylphenylketone, benzophenone, phenyltolylketone, Quinone and the like. The preferred ketones for forming the ketone hydrogen fluoride of this invention are the dialkyl ketones, from «fled acetone is most preferred.

The subclass of nitriles can be represented by the formula RCN, where R is alkyl, cycloalkyl, aryl, alkaryl and is arylalkyl and contains up to about 30 carbon atoms. The nitriles contain a triple bond carbon atom bonded to a nitrogen atom. Representative, However, not exhaustive for the nitrile subclass are acetonitrile, butyronitrile, acrylonitrile, benzonitrile, tolunitrile, Phenylacetonitrile and the like. The preferred hydrogen fluoride-nitrile complex, which is made from the nitriles, Is a Fluorwaseeratoff-Benzonitrll complex.

The subclass of alcohols can be defined by the formula ROH, where R is alkyl, cycloalkyl, aryl, alkaryl and Aryla & kylreste, which about 1 to about 30 carbon atoms: contain. These alcohols represent a class of compounds represents, which is a bonded to oxygen via a single bond Have carbon atom, which in turn has a single bond a vaesstoff is bound. Representative, but not exhaustive, of the alcohols that can be used in the preparation of the hydrogen fluoride complexes are methanol, ethanol, n-propanol, Isopropanol, phenol, benzyl alcohol, cyclohexanol, butanol, Hexanol and pentanol. The preferred hydrogen fluoride-alcohol complex is a hydrogen fluoride-phenolate complex

The ether subclass can be defined by the formula R'OR, in which R and R ^{1 are} alkyl- »cycloalkyl-. Represent aryl, alkaryl, and arylalkyl radicals which contain from about 1 to about 30 Koblenatoffatome, wherein R and R ^{1 can be the} same or different. The radical "R *" can also be connected to the ether oxygen via an ordinary carbon bond with the formation of a cyclic ether, which forms an integral part of the cyclic structure, such as tetrahydrofuran, furan or dioven. These

- 7th 303822Π070

A * the? represent a class of compounds, which have two carbon atoms, which have a single bond to an oxygen atom are bound. Representative but not exhaustive for them in the preparation of the hydrogen fluoride complexes of this invention useful ethers are dimethyl, DJLäthyl, dibutyl, diamyl, Diisopropyl ether or tetrahydrofuran, anisole, diphenyl ether, Ethyl ethyl ether, benzyl ether and the like. The ones made of ethers. Preferred hydrogen fluoride-ether complexes formed are Fluoi? Vaeeeretoff ~ diethyl etherate ~ and hydrogen fluoride dibutyl ether complexes »

. The subclass of esters can be represented by the formula:

-.C-O-R

are defined »where R and R * are alkyl, cycloalkyl, aryl, Represent alkaryl and arylalkyl radicals which contain 1 to about 20 carbon atoms. The esters contain a carbon atom, which is linked by a double bond to an oxygen, such as specified, is bound. Representative, but not exhaustive, of the esters are ethylbenzoate, anyluenzoate, phenyl acetate, Phenyl benzoate and other esters corresponding to the above formula. The preferred hydrogen fluoride ester complex is a hydrogen fluoride ethyl benzoate complex.

Hydrogen fluoride is a clear liquid, which is strong The air smokes, is very poisonous, forms tumor-like wounds when it comes into contact with the skin, and is very dangerous too handle or manipulate. By complex binding of the hydrogen fluoride with the complexing agents mentioned here some of the advantages of the invention are in one safe, lighter and more precise handling of the hydrogen fluoride components of the catalyst system. Hydrogen fluoride complexes usually have a lower vapor pressure and don't smoke as heavily as hydrogen fluoride. The hydrogen fluoride complex can be dissolved in a solvent and therefore lifted it up as a liquid solution and added it to the system will * - 8 -

The solvent which can be used can be Alkyl, alkaryl, arylalkyl or an aryl hydrocarbon be. For example, benzene is a convenient solvent system.

The complexes of this invention are usually prepared by simply adding appropriate amounts of the complexing agent, sum example of a ketone, an ether, an ester, an alcohol, a nitrile or water, dissolved in a suitable solvent and a suitable amount of the hydrogen fluoride in a suitable solvent and both Mixing solvent systems. This mixing should be done in the absence of water vapor. Another possible procedure would be to dissolve either the hydrogen fluoride or the complexing agent in a suitable solvent and the add another component. Yet another method of milling would be to dissolve the complexing agent in a solvent and simply pass through gaseous hydrogen fluoride pass through the system until all the complexing agent has reacted with hydrogen fluoride. The concentration can go through the weight gain or chemical titration can be determined.

The three catalyst components of this invention can be fed separately to the reactor, which contains the butadiene and / or mixtures thereof with other diolefins and the solvent system therefor, either gradually or simultaneously. It has been found that when the three catalyst components of this invention are mixed together outside of the reactor and then fed to the reactor, the catalyst system is not very active. Therefore, the catalyst should not be preformed by mixing the three catalyst component clays before they come into contact with butadiene.

However, an improved pre-formed catalyst system can be prepared by using the three catalyst components together when a small amount of a conjugated diolefin such as butadiene or isoprene is present. It seems & a3 by mixing together the three ketalysator coraponents in

. "9 -

The catalyst system is present on the small slope of the diolefin is stabilized and the formation of a «very active, pre-educated Catalyst is possible.

Dee diolefin obviously reacts with the catalyst components to form a Katalysatorkorapiexes, which is more stable and active, in particular, "if the polymerization more impurities where the individual Katalysatorkoniponenten be added to the reactor as the ⁿ in situ" -Katalyea ~ tor ", which has a very large The improved preformed catalyst can be prepared by dissolving a small amount of diolefin in a hydrocarbon solvent such as benzene or hexane and then dissolving the organometallic component, the NI component and then, the HF complex component is added to the solvent.

The special order of addition when preparing the Catalysts can be varied somewhat, but it is advantageous to (1) add the diolefin before adding both the organomotalic component as well as the HI component takes place, and (2) submit the Ni component before adding both the organometallic component as well as the HF complex catalyst component takes place «the quantity« of the diolefin, which for the purpose Formation of the improved preformed catalyst can be present / can be varied within a wide range and lot etii # as of the other catalyst concentrations, of course addicted.

The amount of diolefin used to preform the catalyst can be within the range of about 0.001 to 3.0 percent of the total amount of monomer to be polymerized. In terms of the molar ratio of conjugated diolefin to nickel complex, the amount of diolefin present during the pre-blowing step can be within the range of about 1 to about 3,000 ami of the concentration of nickel. Tins preferred molar ratio of konjugiere »» »diolefin to nickel eats nttrm 5RT to 500: 1st Most preferred is »IT

- 10 ~

BATH

"Do" 90 "1 blah to use about 10OiI.

This system of the three-component catalyst has a polymerisation activity in a wide range of catalyst concentrations and catalyst ratios. The three catalyst components react with one another to form the active catalyst. As a result, the optimal concentration for each individual catalyst is very dependent on the concentrations of each of the other two catalyst components. In addition, "although polymerization takes place over a wide range of catalyst concentrations and ratios," polymers have the most desirable properties "when they are in a" narrower range can be obtained. Polymerization can take place when the molar ratio of the organonetallic compound (He) to the organononeal compound (Ni) is in the range from about 0.3 / 1 to about 500/1 about 2/1 to about 300/1 and the molar ratio of hydrogen fluoride coaplex to organic metal compound is in the range from about O ₉ 2/1 to about 15/1. However, the preferred ""! Ratios of He / Nl are in the range of about 2/1 to about 60/1 "the preferred molar ratio of HFC / tfi Id range of about 9/1 to about 100/1 and the preferred molar ratio of HFC / Me ranges from about 0.4 / 1 to about 7/1.

The concentration of the catalyst used depends on factors such as purity, the desired speed, and temperature other factors; therefore do not know specific concentrations are given "Bit Aiii after the statement that k & talytisobe Slopes can be used. Some epezlflsöh »concentrations and VerhCLitaA8 * e, which-a Elaatofiiere with desirable properties deliver »are in the here to explain the inventus & sgeii & Sen Lehress given examples are explained.

In general, the polyurizations of this compound are made with an inaccessible measurement and ittol, and are therefore LC-aungpolynerlations. The term »toertes solvent * means that the USavn & aiiXti®! ou ^ r thickener not

. - 11 -

enters into the structure of the polymer obtained, nor has an adverse effect on the properties of the polymer obtained, or any contrary effect on the activity of the catalyst used. Such solvents are usually aliphatic, aromatic or cycloaliphatic Hydrocarbons; Examples of these are pentane, hexane, Toluene, benzene, cyclohexane and the like. Preferred solvents are hexane and benzene. The volume of solvent / MoiXHnerea can be varied over a wide range. A volume ratio of solvent to monomers * of up to 20 or more to 1 can be used "It is usually preferred or more convenient to use a solvent / monomer Vclu" ratio iron about 3/1 to about 6/1. One Suspension polymerization can be carried out using a lonan, e.g., butane or pentan, in which the polymer formed is insoluble. However, it should be understood that block polymerizations or bulk polymerizations are not excluded from the aim of this application are.

It is usually desirable to polymerize these Invention using air-free and moisture-free Performing techniques.

The temperatures used in the erfindungsgemäden polymerization are not critical and can vary from a very low temperature, such as "10 ° C or below, up to high temperatures, such as 100 ⁰ C or higher. Ea is, however, usually more favorable, ^ iSe ^ ss ^^ ksDäßJ ^ e ^ i-T ^^ pjiratur between

about 50 ⁰ C and about 90 ⁰ C asu use ». ^

The practical Durohftihrung disser invention is further based & 9T following examples, which are merely representative but not dsm Ashman should ken limita this invention. If "Eighth stated otherwise," meaning all parts and Fro £ * r ^j t £ i Q «« lchtsteile and -proasfinte The öor rerdtfcnt "" XS weighed (DSV) is sjjid ffolüol "at 30 ⁰ C

3Q9822: IC7IJ

BAO ORlGJNAt

Example I.

Purified butadiene in benzene solution, which contained 10 g of butadiene per 100 μl of solution, was placed in a series of 113 ml bottles. Nitrogen protected the premix while the catalysts were added "in situ". The catalysts added were (a) triethylaluminum (TEAL), which was added as a 0.25 molar (H) solution in benzene, (b) 0.15M nickel octanoate (Niöct) in benzene, and (c) 0.50 H hydrogen fluoride ether -Cooplex (HP.Et ₂ O) in benzene. The tubes were closed tightly, placed in a water bath maintained at 50 ° C., and then tilted lengthways for the periods of time given in Table 1. The polymerizations were terminated by mixing the polymer rubber solutions with one (1) part of both triisopropanolamine and dibutyl-p-cresol per 100 parts of monomer originally used. The polybutadiene polymer sates obtained were dried under vacuum.

The amount of TEAL and NiOct added to each bottle was 0.1 and 0.0075 mmoles; the amount of HF.Et ₂ O was varied as indicated in the table. The poly aereate yields and viscosities of the dilute solution (DSV) obtained with the polybutadienes are also shown in Table 1!

JoMöle yes 1 } Table 1 yield DSV Ver 10 g Bd * • J Polyjaerisa- Wt.-tf dl / g search IfF _-1 It ₂ O _- tion time »R. 0.08 Hours. 2 m2) 1 0.13 18th 31 «2) 2 0.16 1 56 5 _t 4 3 0.25 1 81 4.6 4th 0.30 1 62 3.0 5 0.30 1 96 * 2) 6th 0.40 18th 83 2.0 7th 0.60 18th 2o «2) β 1.00 18th 6th * 2) 9 18th

- 13 -303822/107 0

³⁶² *

Reh bsstteat,

The working method is the same as in B © lspl®l I ₉ with that

it was «

V »r— SMbIe Λβ -"

such 10 § Bd tioneseii Hr, HP-Bt ₂ O. tS * Ov-w ';

1 0.08 19 10 Z 0.13 19 "βΟ 5.5 ■

3. 0.16 1 a © 4 _B a

-4 0.29 1 SS ¹ - 5 * 0

5 0.35 1 62 2 _# 8

6 0.49 19 .86. 2.0

7 0.60 19 43 1.4 '

8 1.00 19 7 ie2)

Böispißl XXl

The incorrect way of working is the same as in B®i »pl * l X, with the assumption that the Polf @ i # rIs @ tioB @ lHsimg8isiitt3i H®pt« a was instead of the benzene vmd the Η1 ~ Όα @ 1ΐ6 _φ ^ ie given in Table 3, varied »

Ver ~ Ni-Verbin- sü-tole A & Poljasrisationa-Kuch dung 10 g Bd since (hours)

No. HF, Et «O

1 HiNaph ■ '0 «25

2. KiOct ⁵ ^ '0.25 O _e ? F

3 NlAcAo "· -" - 0, «. ^."

4 Hi (CO) ₄ ¹¹⁴ ^ 0 ₉ 25 · 1 ₀

^ _ MiAoAc 0 _ρ 19 1,

6 Hi (CO) ₄ '0.15 S _r

LL U / IJ

^m1 ^ Niokelnaphthenat ¹¹² ) Nickel octanoate "^ 'Nickel acetylacetonate ^mi * ) Nickel tetracarbonyl

Example IY

The procedure used was the same as in Example I except that different complexes of HF were compared as shown in Table 4.

Tabel

Try «aMole ever

No. 10 g Bd Polymer! Sation »- yield DSV HF complex tent (hours) weight - * dl / q

1 0.29 HF.Et ₂ O 1 80 4.7

2 0.30 HF.Et ₂ O 2 77 4.0

3 0.25 HFeBu ₂ O * ¹ ) 1 60 4.7

4 0.30 HF.Bu ₂ O " ¹ > 1 55 4.3

5 0.30 HF.THF 2 52 5.2

6 0.30 HF.BH 2 45 4.8

7 0.30 HF.Pyr «, 18 0 -

8 0.30 HF.acetone * ² * 4 76 4.1

¹¹¹ ^ 0.075 Bltole TEAL and 0.005 HiOo-t

.j BHoIe MiOct Et ₂ O - diethyl ether Bu ₂ O - dibutyl ether THF - tetrahydrofuran BS - benzonyltrile pyr »- pyridine

Example. V

The operation is the same as in Example · I "with the Ausnmhue that the Katalyaatorkonzentretionen were varied" Di Polymerisationezeit was for "lie experiments four hours _u

3 0 9 S 2 2 M ·) 7

Tabel

Trial µmoles / 10 β Bd yield DSV

Mr. TEAL HIOot HF, Et ^ O wt .- $ dl / g 1 0.0? 0 * 005 0.25 S3 2.6 2 0.10 o _t oo5 o. 3o ao 2.9 3 0.15 0.0075 0.45 86 2.8

Example VI

The working line is the same as in Example I; However is triisobutylaluoinluin (7IBAL), 0.110 saMole, instead of the tri-ethylaluminum (TEAL) is used and different Hydrogen fluoride alkcholete and lasser

attempt s & ole each 10 g Bd Polyaerlsatieas = • yield DS? HF.AUsoholat 3SU% (StA) Weight-96 1 0.4 methanol 19.0 10.8 .- 2 0.8 methanol 19.0 4.4 _; «. 3 0.4 ethanol 19.0 . 11.8 4th 0.8 xthanol : 19.0 5.3 5 0.4 propanol 19.0 49.4 8.31 6th 0.8 propanol 19.0 4.7 7th 0.4 isopropane ^ l ■ 2.5 25.6 6.56 8th 0.8 isopropanol 19.0 9.5 M. 9 0.4 cyclohexanol 2.2 32.9 6.87 10 0.8 cyclohexanol 19.0 15.4 - 11 0.4 Fh «npl 2.5. 68.4 5.23 12th 0.8 Ρ & ϊή & ί. 19 * 0 70.4 2.66 13th 0.4 water 19.0 70.0 - Example VII

The method used is Ähtlioh that in example I, oils

der Ausahfte, da0 der ^ KAtftlyeatc ;? Xn Qegimmxt one! Yours

Quantity ^ »a Hozumeran» Butadiene, is preformed. Venn the organs »-

■ '· ■ "■ - 16 -

309822/1070

BAO 0BI6INM.

Metallic Compound If the nickel compound and the HF complex are mixed together before they are added to the premix, the gray slurry obtained has almost no catalytic polymer gas activity. However, if the 1st _f preformed "catalyst itself present a small amount of butadiene or another conjugated diolefin very active. Butadiene must be present before the connection has the opportunity to react either to the connection or to the HF. . _4th

In this example, the standard order of addition was to the Mix the catalyst beaters

1, solvent

2. Butadiene

3. Organometallic compound

4, Rl compound 3- HF complex.

Table 7 Versuoh Bd ι Ni * polymer DSV Mn No. molar ratio yield # dl / g osmotlsoh

_ at 4 atd " ,

1 O 1 ■ -

2 40 56 3.3 not determined

3 100 71 3.3 137.ΟΟΟ

4,300 73 3.2 not determined

* The amount of Bd in the presented catalysts varied and was 0.3, 7, 9 and 22.9 mNole per 100 g of Bd,

Example VIII

The procedure used was the same as in Example VII, old the exception, de3 the exemplary conjugated diolefin Myrsen (7 ~ Met & yl-3 ~ methylen ~ 1,6-octadlene), an isoprene-Dlmeres, is *

- 1V

3 0 9 8 221 ? CT0

8AD ORIGINAL

Z 0.379

0.1 ©

O ₉ 10 0.0075 2

dan elude is fir

rtm (tebe & t or

- 18th

"309822/1010

Claims (1)

22571 - ie - NOV 17. Claims Process for the polymerization of butadiene and of butadiene In other diolefins mixture old purposes formation of polymers which contain a high proportion d "r butadiene units in the OIS 1.4 Konflguratlon, characterized in that a nlixdvstens Moooateree from the group t butadiene and butadiene la mixture Ddt other diolefins, under Polymerisatlanabedlngungen with a catalyst which brings (1) at least one orgenometallic pre-bond in which the metal is selected from groups I, II and III of the period (2) at least one nickel compound, outside the class of nickel salts is selected from carboxylic acids, organic complex compounds of nickel, Nlokeltetraoarbonyls, and (3) at least one hydrogen fluoride f-Koapls ?, which is produced by coaplex formation of hydrogen fluoride with a member of the class of the ketones, esters, ethers, alcohols, nitriles and water, contains. 2. The method 'according to claim 1 _e, characterized in that ButAdlen-1,3 is used alone. 3 «Method according to Claim 1, characterized in that the catalyst is preformed in the presence of a conjugated diolefin. h, The method of claim 1, gekannzeichnet characterized in that the organoaetallisohen compounds of metals from groups I, II and III of the Perlodensysteas be selected from the groups <consisting Organoaluainluaverbindungen, Organoaagnealmverblndungen, organozinc compounds and Organolithiuieverbindungen bestehest the Organonickelverblndxmg from the group dor Nickel salt from carboxylic acids and organic complex compounds of nickel is selected {and the hydrogen fluoride ~ cosq> lex from the hydrogen fluoride ~ aoeton ~ Koaple.x, hydrofluoric acid-Tetrahyaroruran-Kosrplax, Fl 322 / TO *; C. BATH ORIGINAL Hydrogen fluoride-Xthanol complex, Hydrogen fluoride propanol complex, Hydrogen fluoride Zsopropanol ~ X0aplax ₉ Hydrogen fluoride-Benzylalcohol complex, Hydrogen fluoride Diftthyl & ther ~ oaplex, Hydrogen fluoride phenolic acid, Hydrogen fluoride group, Hydrogen fluoride benzyl alcohol complex is selected 3. The method according to claim 1, characterized in that the molar ratio of the organo-metallic compound of the metals / organoniocular compound listed from groups I, II and ZZZ of the periodic table ia range from about O ₉ 3/1 to about 5QQ / Λ, the ratio of the HF -Xomplexes / organonickel compound in the range from about 2/1 to about 300/1 and the molar ratio of the HToKostplexes / organometallic compound with metals from groups Z, ZZ, and ZZZ of the periodic table in the range from about O ₉ 2/1 to about 15 / 1 lies. 6. The method according to claim 4, characterized in that the preferred molar ratio of organosotallic compounds with metals from groups I, ZZ and ZZZ of the periodic table / organonickol compound ia range from about 2/1 to about 60/1; the preferred molar ratio of the HF complex / organometallic disc Compounds with metals of groups Z, ZZ and ZZI of the periodic table is in the range from about 0.4 / 1 to about 7/1. 7. The method according to claim 4, characterized in that the organosetallic compounds with metals from group I, IZ and IZI of the periodic table are an organoaluminium compound are. Θ. Method according to claim 7, characterized in that the Organoaluminium compound & among others the group of aluminum trialkyls is selected « 9. The method according to claim 1, characterized in that the org & noaetallic compound an organoaluminum compound iat and the hydrogen fluoride complex by complex formation of Hydrogen fluoride old a zither from class r - 20 -309-97.2 / .1070 0AD Dift * B * atteer, fvtrsJvdrofttrsn and ZfttratyUther »or« Μ Ur IXaMMi Diawtt »ja * eton, or« ine «alcohol tu» the JOasses methanol * ethanol, n-propanol, ifopropeiiol _v phenol »bensyl alcohol tad cyclohexanolitrile» or an aromatic alcohol tad cyclohexanolitrile out of hate BensonltrJl, or old water is produced. 10. The catalyst is characterized by the fact that it (1) has at least one organic compound in which the metal e is selected from groups I, II and III of the periodic table « (2) Bladesten eloe Qrgsnoniokelvsr ^ liidtinf »those from the class of the Hlokel salts of carboxylic acids »organic complexes of the Hlok "ls" Niokeltetraoarbonyls is au & gt "ttlt, and (3) at least a fluorohydrogen complex, possibly by Koapl" c ^ Formation of hydrogen fluoride with a member from the class of Ketone Xther »Alcohols» Nitriles and Water Manufactured 1st »Contains. 11. Katalyssibrstoff naoh claim 10 _r characterized in that the KatAlyaator is preformed in the presence of a conjugated diolefin. 12. M & see naoh Claim 10, characterized by the fact that the molar ratio of the organometallic connection with metal from groups I, II and IZI / Berlod “n £ ysteas / Org & noniokel ▼ arbinding la range from about 0.3 / 1 to about 300/1 »the MoI-vflrbÄltrds d« e HF complex / '* ganonickely connection In the range from about 2/1 to about 3OC /} and the molar ratio of the HF · Kamplexei / organo-metallic compound with metals from the αηφρικλ l _t II and IXI des Perloderitrsteiie la Bereloh Jtrsn et 0 _t 2/1 to «rtm12i / 1. Dipl.-In Z ./ '.' · Ti " ^f 0 BATH ORIGINAL