EP1049727A1

EP1049727A1 - Catalyst system for gas phase polymerisation of conjugated dienes

Info

Publication number: EP1049727A1
Application number: EP99903606A
Authority: EP
Inventors: Michael Dauben; Jürgen Schneider; Gerd Sylvester; Norbert Steinhauser
Original assignee: Bayer AG
Current assignee: Bayer AG
Priority date: 1998-01-20
Filing date: 1999-01-07
Publication date: 2000-11-08
Also published as: DE19801857A1; WO1999037694A1; AU2420099A; US6576727B1; CA2318054A1; JP2002501092A

Abstract

A catalyst system for gas phase polymerisation of conjugated dienes, consisting of a rare earth compound, an aluminium organic compound, another Lewis acid, optionally a conjugated diene, an inert inorganic or organic support and a co-catalyst applied to an inorganic support, in order to improve the flowability of rubber thus produced.

Description

Catalyst system for gas phase polymerization of conjugated dienes

The invention relates to a catalyst system for gas phase polymerization of conjugated dienes, consisting of a rare earth compound, an organoaluminum compound, a further Lewis acid, optionally a conjugated diene, an inert, inorganic or organic carrier material and additionally one applied to an inorganic or organic carrier material Co-catalyst while improving the flowability of the rubber produced in this way.

Polybutadiene with a high proportion of cis-1,4 units has been produced on an industrial scale for a long time and used for the production of tires and other rubber products.

For environmental reasons, efforts are being made to carry out the polymerization of this and other conjugated dienes in the gas phase, since no solvents have to be used and emission and waste water pollution can be reduced.

In addition, the process can be used to create novel rubbers with special ones

Establish product properties. In particular, particularly well-dispersed fillers are obtained in the polymer if they are present during the polymerization as a carrier of the active component of the catalyst.

From EP-B-0647657 it is already known that the polymerization of conjugated dienes, in particular butadiene, can be carried out in the gas phase without the addition of solvents by using a catalyst system based on rare earth compounds, an organoaluminum compound a particulate, inert, inorganic solid with a specific surface area greater than 10 m ² / g (BET) and a pore volume of 0.3 to 15 ml / g. - 2 -

EP-B-0605001 claims the use of silica of a certain particle size as carrier material and inert particulate materials to improve the flowability of sticky polymers.

EP-A-0442452 describes the use of inert particulate materials

Particle diameters of 0.01-10 μm to improve the flowability of sticky polymers in polymerizations described above the softening temperature of said sticky polymers.

EP-A-0530709 describes the use of inert particulate materials

Particle diameters of 0.01-150 μm to improve the flowability of sticky polymers in polymerizations described above the softening temperature of said sticky polymers.

WO-88/02379 describes the use of inert powdery inorganic

Materials in amounts between 0.005-0.2% by weight based on the fluidized bed to improve the flowability of polymers.

WO-96/04323 describes the use of inert particulate materials to improve the flowability of BR and IR in polymerizations, the reactor temperature being below the dew point of one of the constituents of the cycle gas.

EP-A-704464 describes a resin particle with a sticky core and a non-sticky shell which consists of 10-90% ethylene.

EP-A-570960 describes a resin particle with a sticky core and a non-sticky shell made of inert particulate particles.

In all of the processes described above, inert materials are used, with increasing emphasis being placed on the term inert. US Pat. No. 5,162,463, on the other hand, teaches that agglomeration of the sticky particles in a fluidized bed can be avoided by metering an inert material which is coated with a polysiloxane layer into the fluidized bed.

Finally, WO-97/08211 describes the addition of stabilizers in a carrier

Shape.

It was now completely unexpected for the person skilled in the art that through the use of particulate materials coated with cocatalysts, the activity of u. a. in EP-B-0647657 protected catalyst system consisting of

A) an alcoholate of rare earths (I), a carboxylate of rare earths (II), a complex compound of rare earths with diketones (III)

and or

an addition compound of the rare earth halides with an oxygen or nitrogen donor compound (IV) of the following formulas:

(RO) ₃ M (I)

(R-CO ₂ ) ₃ M (II)

(R - C- CH- R) ₃ sts

(III)

O O

and

MX ₃ ^• y Donor (IV) - 4 -

an aluminum trialkyl, a dialkyl aluminum hydride and / or an alumoxane of the formulas (V) - (VII):

Al (H) x (R ¹ ) ₃ . _x (V)

R '

R ¹ (AO) _n Ai /

¹ R (VI)

R ¹

and

c (A O) n + 1

R

being in the formulas

M is a trivalent element of the rare earths with the

Atomic numbers 57 to 71 means

the rest

R, identical or different, is an alkyl radical with C ₁ -C ₂ n,

the rest

R ¹ , identical or different, denote a d-Cio-alkyl radical,

X represents chlorine, bromine or iodine

x represents 0 or 1, - 5 -

y is 1 to 6 and

n means 1 to 50,

C) a further Lewis acid and

D) a particulate, inorganic or organic solid with a specific surface area greater than 10 m ² / g (BET), a grain size of 10 to 1000 μm, preferably 100 to 500 μm, and a pore volume of 0.3 to 15 ml / g (if soot is used, additional DBP adsorption of more than 30 ml / 100 g),

can be increased very strongly.

All co-catalytically active constituents are suitable as co-catalysts, in particular the materials listed under B). All particulate materials are suitable as support materials for these cocatalysts, in particular the materials listed under D).

If, on the other hand, a cocatalyst (eg aluminum alkyl) described under B) is metered into the liquid phase, be it in concentrated form or in dilute solution, before and / or during the polymerization, the moving reaction mass runs, for example, in a stirred fixed bed or a fluidized bed, through spontaneous agglomeration and gluing into an unstable state of fluidization. The result is a drastically reduced reactor service life. Not so if the supported co-catalyst solids according to the invention are metered into the gas phase process and they have the desired effect through intimate contact with the above or u. can evolve occupied Nd catalyst described in EP-B-0647657. Furthermore, the distribution within the reactor or the fluidized mass is more homogeneous than is the case, for example, when a liquid co-catalyst material is injected into the reaction volume. Also completely unexpected was the effect that the effectiveness of the cocatalyst in separately supported form is significantly higher compared to the same amount of cocatalyst carried together with the catalyst. The reaction acceleration or activity increase achieved by the separate support of the cocatalyst is well over 30% compared to the common support.

In component A), M is a trivalent element of the rare earths with atomic numbers 57 to 71 identified in the periodic table. Preferred compounds are those in which M is lanthanum, cerium, praseodymium or neodymium or a mixture of rare earth elements, which has at least one the

Contains elements of lanthanum, cerium, praseodymium or neodymium in at least 10% by weight. Compounds in which M is lanthanum or neodymium or a mixture of rare earths which contain at least 30% by weight of lanthanum or neodymium are very particularly preferred.

The radicals R in the formulas (I) to (IV) are, in particular, straight-chain or branched alkyl radicals having 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms, such as methyl, ethyl, n-propyl, n-butyl, n-pentyl , Isopropyl, isobutyl, tert-butyl, 2-ethylhexyl, neo-pentyl, neo-octyl, neo-decyl, neo-dodecyl.

As alcoholates of component A) z. B. called: neodymium (III) -n-propanolate, neodymium (III) -n-butanolate, neodymium (III) -n-decanolate, neodymium (III) -isopropanolate, neodymium (III) -2-ethyl-hexanolate , Praseodymium (III) -n-propanolate, praseodymium (III) -n-butanolate, praseodymium (III) -n-decanolate, praseodymium (III) -iso-propanolate, praseodymium (III) -2-ethyl-hexanolate, Lanthanum (III) -n-propanolate, lanthanum (III) -n-butanolate, lanthanum (III) -n-decanolate, lanthanum (III) -isopropanolate, lanthanum (III) -2-ethyl-hexanolate, preferably neodymium ( III) -n-butanolate, neodymium (III) -n-decanolate, neodymium (III) -2-ethylhexanolate.

Suitable carboxylates of component A) are: lanthanum (III) ρropionate, lanthanum

(IΙI) diethyl acetate, lanthanum (III) -2-ethyl-hexanoate, lanthanum (III) stearate, lanthanum (III) benzoate, lanthanum (III) cyclohexane carboxylate, lanthanum (III) oleate, lanthanum (III) - versa- tat, lanthanum (III) naphthenate, praseodymium (III) propionate, praseodymium (III) diethyl acetate, praseodymium (III) -2-ethylhexanoate, praseodymium (III) stearate, praseodymium (III) benzoate, praseodymium (III) -cyclohexane carboxylate, praseodymium (III) oleate, praseodymium (III) versatate, praseodymium (III) naphthenate, neodymium (III) propionate, neodymium (III) diethyl acetate, neodymium (III) -2-ethylhexanoate, neodymium (III) stearate, neodymium (III) bezoate, neodymium (III) cyclohexane carboxylate, neodymium (III) oleate, neodymium (III) versatate, neodymium (III) naphthenate, preferably neodymium (III) -2 -ethylhexanoate, neodymium (III) versatate, neodymium (III) naphthenate. Neodymium versatate is particularly preferably used.

The following may be mentioned as complex compounds of component A): lanthanum (III) acetyl acetonate, praseodymium (III) acetylacetonate, neodymium (III) acetylacetonate, preferably neodymium (III) acetylacetonate.

Examples of addition compounds of component A) with donors are: lanthanum (III) chloride with tributyl phosphate, lanthanum (III) chloride with tetrahydrofuran, lanthanum (III) chloride with isopropanol, lanthanum (III) chloride with pyridine, Lanthanum (III) chloride with 2-ethylhexanol, lanthanum (III) chloride with ethanol, praseodymium (III) chloride with tributyl phosphate, praseodymium (III) chloride with tetrahydrofuran, praseodymium (III) chloride with isopropanol , Praseodymium (III) chloride with pyridine, praseodymium (III) chloride with 2-ethylhexanol, praseodymium (III) chloride with ethanol, neodymium (III) chloride with tributyl phosphate, neodymium (HI) chloride with Tetrahydrofuran, neodymium (III) chloride with isopropanol, neodymium (III) chloride with pyridine, neodymium (III) chloride with 2-ethylhexanol, neodymium (III) chloride with ethanol, lanthanum (III) bromide with tributyl phosphate, lanthanum (III) bromide with tetrahydrofuran, lanthanum (III) bromide with isopropanol, lanthanum (III) bromide with pyridine, lanthanum (III) bromide with 2-

Ethylhexanol, lanthanum (III) bromide with ethanol, praseodymium (III) bromide with tributyl phosphate, praseodymium (III) bromide with tetrahydrofuran, praseodymium (III) bromide with isopropanol, praseodymium (III) bromide with pyridine, praseodymium (III) bromide with 2-ethylhexanol, praseodymium (III) bromide with ethanol, neodymium (III) bromide with tributyl phosphate, neodymium (III) bromide with tetrahydrofuran, neodymium (III) bromide with iso-

Propanol, neodymium (III) bromide with pyridine, neodymium (III) bromide with 2-ethylhexanol, neodymium (III) bromide with ethanol, preferably lanthanum (III) chloride with tributyl phosphate, lanthanum (III) chloride with pyridine, lanthanum (III) chloride with 2-ethylhexanol, praseodymium (III) chloride with tributyl phosphate, praseodymium (III) chloride with 2-ethylhexanol, neodymium (III) chloride with tributyl phosphate, neodymium (III) chloride with tetrahydrofuran, neodymium (III) chloride with 2-ethylhexanol, neodymium (III) chloride with pyridine, neodymium (III) chloride with 2-ethylhexanol, neodymium (III) - chloride with ethanol.

The rare earth compounds can be used individually or as a mixture with one another.

Neodymium versatate, neodymium octanoate and / or are very particularly preferred

Neodymnaphthenate used as component A).

In the formula (V) to (VII) of component B), R ^{1 is} a straight-chain or branched alkyl radical having 1 to 10 C atoms, preferably 1 to 4 C atoms. Examples of suitable aluminum alkyls of the formula (V) are:

Trimethyl aluminum, triethyl aluminum, tri-n-propyl aluminum, triisopropyl aluminum, tri-n-butyl aluminum, triisobutyl aluminum, tripentyl aluminum, trihexyl aluminum, tricyclohexyl aluminum, trioctyl aluminum, diethyl aluminum hydride and aluminum hydride, di-aluminum hydride. Triethyl aluminum, triisobutyl aluminum and di-iso-butyl aluminum hydride are preferred. Di-isobutyl aluminum hydride is particularly preferred.

Examples of alumoxanes (VI) and (VII) are: methylalumoxane, ethylalumoxane and isobutylalumoxane, preferably methylalumoxane and isobutylalumoxane.

So-called Lewis acids are used as component C). Examples include the organometallic halides in which the metal atom belongs to group 3 a) or 4a), and halides of the elements in groups 3a), 4a) and 5a) des

Periodic table, as shown in the "Handbook of Chemistry and Physics" 45th Edition 1964-65. The following are mentioned in particular: Methyl aluminum dibromide, methyl aluminum dichloride, ethyl aluminum dibromide, ethyl aluminum dichloride, butyl aluminum dibromide, butyl aluminum dichloride, dimethyl aluminum bromide, dimethyl aluminum chloride, diethyl aluminum bromide, diethyl aluminum chloride, dibutyalaluminum chloride,

Methyl aluminum sesquibromide, methyl aluminum sesquichloride, ethyl aluminum sesquibromide, ethyl aluminum sesquichloride, aluminum tribromide, antimony trichloride, antimony pentachloride, phosphorus trichloride, phosphorus pentachloride, tin tetrachloride.

Diethyl aluminum chloride, ethyl aluminum sesquichloride, ethyl aluminum dichloride, diethyl aluminum bromide, ethyl aluminum sesquibromide and / or ethyl aluminum dibromide are preferably used.

As component C), the reaction products of aluminum compounds, as described as component B), with halogens or halogen compounds, for. B. triethyl aluminum with bromine or triethyl aluminum with butyl chloride can be used. In this case, the reaction can be carried out separately, or the amount of alkyl aluminum compound required for the reaction is added to the amount required as component B).

Ethyl aluminum sesquichloride, butyl chloride and butyl bromide are preferred.

As component D), particulate, inorganic or organic solids with a specific surface area greater than 10, preferably 10 to 1000 m ² / g (BET), a grain size of 10 to 1000 μm, preferably 50 to 500 μm, and a pore volume of 0.3 to 15 ml / g, preferably from 0.5 to 5 ml / g used. When using carbon blacks, DBP adsorption is used as a suitability criterion in addition to the pore volume. This should be between 10 to 300 ml / 100 g, preferably between 60 to 150 ml / 100 g, particularly preferably between 90 and 130 ml / 100 g. - 10 -

The specific surface area (BET) is determined in the usual way according to S. Brunauer, P.H. Emmet and Teller, J. Anorg. Chem.Soc. 60 (2), 309 (1938), the pore volume is determined by the centrifugation method according to M. McDaniel., J.CoUoid Interface Sei. 78, 31 (1980) and the DBP adsorption according to DIN 53 601.

Particularly suitable as inorganic solids are silica gels, precipitated silicas, clays, aluminosilicates, talc, zeolites, carbon black, inorganic oxides such as silicon dioxide, aluminum oxide, magnesium oxide, titanium dioxide, silicon carbide. Silica gels, precipitated silicas, zeolites and carbon black are preferred, particularly preferred precipitated silicas and carbon black. In this case, inert is understood to mean that the solids are composed in this way or by pretreatment, such as e.g. Calcine, pretreated so that the reactive surface does not hinder the formation of an active catalyst or reacts with the monomers.

The above-mentioned inorganic solids, which meet the above-mentioned specification and are therefore suitable for use, are described in more detail, for example, in Ullmanns, Encyclopedia of Industrial Chemistry, volume 21, p. 439 ff. (Silica gel), volume 23, p. 311 ff. (Tone), volume 14, p. 633 ff. (Soot), volume 24, S575 ff. And volume 17, p. 9 ff. (Zeolites).

The inorganic solids can be used individually or in a mixture with one another.

Also suitable as organic solids are polymeric materials, preferably in the form of free-flowing powders, which are so designed or pretreated by pretreatment, such as drying, for example, that the reactive surface does not hinder the formation of an active catalyst, or with the monomers reacted, a grain size in the range of 10 to 1000 microns and which have a pore volume in the range of 0.3 to 15 ml g. An example of such a material is powdered polypropylene. - 11 -

The molar ratio in which the catalyst components A) to D) are used can be varied within wide limits.

The molar ratio of component A) to component B) is 1: 1 to 1: 1000, preferably 1: 3 to 1: 200, particularly preferably 1: 3 to 1: 100. The molar ratio of component A) to component C) is 1: 0.4 to 1:15, preferably 1: 0.5 to 1: 8.

For 100 g of component D) 0.1 mmol to 1 mol of component A), preferably 1 to 50 mmol of component A) are used.

It is also possible to add a further component E) to the catalyst components A) to D). This component E) is a conjugated diene, which can be the same diene that is later to be polymerized with the catalyst. Butadiene and isoprene are preferably used.

If component E) is added to the catalyst, the amount of E) is preferably 1 to 1000 mol, based on 1 mol of component A), particularly preferably 1 to 100 mol, based on 1 mol of component A). 1 to 50 mol, based on 1 mol of component A), of E) are very particularly preferably used.

The supported co-catalyst according to the invention is produced by applying a solution of the co-catalyst or cocatalysts preferably described under B) to the particulate solid D).

Preferably before, during and possibly after the application of the cocatalyst solution, the solid is agitated, e.g. in a stirred tank with a conventional stirring unit, such as. B. a cross bar stirrer or a spiral stirrer, or in a further preferred form in a ploughshare mixer.

The support material can also be impregnated with a cocatalyst solution in a fluidized bed. This is done on the carrier material by an inert gas stream - 12 -

is fluidized, the drug solution is applied, e.g. by spraying with a nozzle. The inert gas can be returned to the reactor via an internal circuit after it has been freed from the solvent which is also transported. The inert solvent can be reused for the preparation of the active ingredient solution.

Since the co-catalyst system can react with air and / or moisture, it is advantageous to dry the solid powder D) before applying the co-catalyst solution, to remove the air and under an inert gas atmosphere before, during and after the application of the co- Keep catalyst solution. The application of the co-catalyst solution is preferably controlled so that the added, preferably atomized, solution is immediately taken up by the solid D). The formation of clumps and inhomogeneities is thus minimized.

The catalyst system and / or supported co-catalyst can also be prepared continuously.

Furthermore, it is possible to control the efficiency level of the catalyst system by adjusting the ratio of the metered amount of supported co-catalyst material to the Nd catalyst present. Preferably, only as much cocatalyst solution should be applied to the solid as it can absorb.

The solids ulver can thus continue to be easily stirred and moved as a free-flowing powder after the application of the active ingredient solution.

In principle, it is possible to vary the amount of inert solvent used within wide limits. As shown, however, the amount is kept as low as possible for ecological and economic reasons. The amount depends on the amount and the solubility of the co-catalyst component (s) and the pore volume / DBP adsorption of component D). An amount of 10 to 2,000 parts of the solvent, based on 100 parts of component D), is preferably used. - 13 -

The supported cocatalyst can be produced in a wide temperature range. In general, the temperature is between the melting point and boiling point of the cocatalyst component B) or the inert solvent. The usual procedure is at temperatures from -20 to 100 ° C, preferably 20 to 40 ° C.

In a preferred embodiment, following the impregnation of the carrier material with active ingredient solution, the inert solvent is removed by distillation. The distillation can be carried out both in the same container in which the impregnation was carried out and in a separate apparatus, e.g. a fluidized bed dryer. When removing the solvent, the entry of air and moisture must be avoided. Depending on the solvent used, the distillation is carried out at temperatures from 0 to 150 ° C., preferably at 10 to 80 ° C., and pressures from 0.001 mbar to 20 bar absolute, preferably 0.001 mbar to normal pressure. The distillation can also be carried out continuously.

The condensate collected under inert conditions can be reused without further processing as a solvent for the active ingredients used in the impregnation.

In a further preferred embodiment, the inert solvent is not removed.

The invention also relates to the use of the supported co-catalyst prepared according to the invention in a process for the polymerization of conjugated dienes, e.g. of 1,3-butadiene, isoprene, pentadiene or dimethylbutadiene in the gas phase.

This polymerization is carried out by bringing the gaseous conjugated diene into contact with the above-described or, inter alia, EP-B-0647657 and the supported co-catalyst prepared according to the invention. Further gases can be mixed into the gaseous monomer, which serve either for dilution or heat dissipation or for regulating the molecular weight. The poly - 14 -

merisatioη can be carried out at pressures from lmbar to 50 bar, preferably 1 to 20 bar.

In general, the polymerization is carried out at temperatures from -20 to 250 ° C., preferably at 0 to 200 ° C., particularly preferably at 20 to 160 ° C.

The polymerization can be accomplished in any apparatus suitable for gas phase polymerization. So z. B. a stirred reactor, a rotating reactor or a fluidized bed reactor or a combination of these types of reactors.

The polymers obtained have a cis-1,4 double bond content of about 60 to 99%. The molecular weight can be changed by the composition of the catalyst and by varying the polymerization conditions. Molecular weights of 10 ³ to 10 ⁶ , as measured with GPC (gel permeation chromatography as described, for example, in M. Hoffmann, H. Krömer, R. Kuhn,

"Polymeranalytik 1", Georg Thieme Verlag, Stuttgart, 1977, pp. 349 ff. With universal calibration).

The Mooney viscosity, ML (1 + 4 ', 100 ° C)) is usually in the range between 30 and 180 ME. The polymerization in the gas phase can also be used to produce very high molecular weight polymers, which are only accessible with extremely great effort because of the high viscosity and the possibility of transfer reactions through the solvent used.

The polymers obtained can be compounded and vulcanized in the usual way.

In a common embodiment, the polymerization of 1,3-butadiene is carried out as follows:

The catalyst system described above or, inter alia, in EP-B-0647657 is, after prior mixing with the co-catalyst system prepared according to the invention - 15 -

or else separately it is transferred to an apparatus which is suitable for keeping the powdery catalyst and the supported particulate cocatalyst in motion. That can e.g. B. by stirring, turning and / or a gas stream. The inert gas initially located in the gas space, e.g. B. nitrogen is replaced by the gaseous monomer. An immediate polymerization starts and the temperature rises. The monomer, optionally diluted, is fed to the reactor with an inert gas so rapidly that the desired reaction temperature is not exceeded. The reaction temperature can also be set in the usual way by heating or cooling. The polymerization is terminated by switching off the monomer feed. The polymer can be further treated in the known manner by deactivating the catalyst and treating the polymer with known anti-aging agents.

The following examples are intended to illustrate the use of the catalyst system described here for the gas-phase polymerization of conjugated dienes, consisting of a rare earth compound, an organoaluminum compound, a further Lewis acid, optionally a conjugated diene, an inert, inorganic or organic support material and additionally one on one Describe inorganic or organic support material applied co-catalyst while improving the flowability of the rubber produced here, but without restricting it to the examples, and clarify the unexpected and significant increase in activity when using the co-catalyst system according to the invention in addition to the catalyst system described above.

- 16 -

Examples

example 1

la) pretreatment of the support material for the cocatalyst:

Zeosil 1165 MP was used as the support material for the cocatalyst. Zeosil 1165 MP is an agglomerated precipitated silica from Rhönen-Poulenc with a BET surface area of 139 m ² / g. The pore volume is 1.97 ml / g. Before use, the Zeosil 1165 MP is dried at 900 ° C in a rotary kiln in a nitrogen countercurrent and then filled with the exclusion of air and moisture.

Carbon black N115, a product from Degussa, was also used as the carrier material. The carbon black has a BET surface area of 145 m ² / g and a DBP adsorption of 113 ml / 100 g. The average particle diameter is 485 μm. This material was dried under nitrogen at 450 ° C. for 32 hours and transferred and stored under nitrogen.

lb) Preparation of a supported co-catalyst

General information:

Most of the pure or solution-based cocatalyst starting materials used, as well as the fully supported cocatalyst, are sensitive to air and moisture. Weighing-in, reaction and filling must be carried out using Schlenck work technology to the exclusion of oxygen and moisture.

1000 g of pretreated Zeosil 1165 are placed in a 10 liter double jacket vessel under protective gas and mixed thoroughly with the inclined blade stirrer (100

Rpm). A solution of 71 g (0.5 mol) of DIBAH in 876 g of hexane is added within

Pumped on the carrier for 3 hours. The inside temperature should be 20 to 30 ° C. - 17 -

After the coating, the mixture is stirred at 20 ° C. for 30 minutes and then the hexane is distilled off at 0.1 mbar and 50 ° C. 1055 g of a free-flowing white powder are obtained.

Example 2

The same general instructions apply as for example 1. The carrier material is pretreated as described in example 1.

1000 g of pretreated carbon black N 115 (from Degussa) are placed in a 10-liter double-jacket vessel under protective gas and mixed thoroughly with the inclined-blade stirrer (100 rpm). A solution of 71 g (0.5 mol) of DIBAH in 600 g of hexane is pumped onto the support within 3 hours. The inside temperature should be 20 to 30 ° C. After the coating, the mixture is stirred at 20 ° C. for 30 minutes and then the hexane is distilled off at 0.1 mbar and 50 ° C. 1060 g of a free-flowing black powder are obtained.

Polymerizations:

Example 3a

The polymerization was carried out in a 2 liter Büchi glass autoclave equipped with a spiral stirrer, which was charged with a bar of nitrogen before the start of the reaction. 3 g of a Zeosil-supported catalyst, as described in EP-B-0647657, in this case with 3.7 mmol Nd, 148 mmol DIBAH, 3.7 mmol

EASC and 7.4 mmol of isoprene per 100 g of material were conveyed into the reactor by means of a lock, and the reaction temperature was regulated via the jacket circuit in such a way that a temperature of 80 ° C. could be established in the stirred bed. The polymerization was started by metering preheated gaseous butadiene into the reactor, starting with a butadiene partial pressure of 2 bar. At the start of the reaction, the bed temperature rose to about 84 ° C. despite jacket countercooling, and the reaction was able to proceed after 10 minutes run isothermally at 80 ° C over the entire course. The experiment was carried out in the semi-batch mode, ie the amount of butadiene consumed in the reaction was always replenished, but no catalyst and no supported cocatalyst, and no product was removed until the end of the experiment. The rapid increase in the agitated bed from the beginning, which is also referred to as a pseudo fluidized bed due to the vigorous mixing with the spiral stirrer, was well observed in the glass reactor, and a steady increase in the product grain size of a few 100 initially μm in diameter to more than 1 mm in the end. Slight particle agglomerations occurred in the course of the reaction, but did not significantly impede mixing.

The experiment was ended after 22 hours.

After the residual butadiene still in the reactor had reacted, the product was discharged via a ball valve in the bottom plate of the reactor and then immediately by mixing in 3 g of stearic acid and 3 g of Vulkanox BKF

Bayer AG stopped and stabilized on the roller.

The average polymerization activity of the catalyst system in this experiment was about 220 [kg BR / (mol Nd ^■ bar butadiene ^• h)].

Example 3b

The polymerization was carried out as in Example 3a), but this time, together with the Nd catalyst described, 4.5 g of the supported cocatalyst from Example Ib) according to the invention were conveyed into the reactor using the lock.

No particle agglomeration was observed in the course of this experiment. There was also a significant increase in the polymerization activity of the catalyst system, which was about 40% on average over 2'Λ hours. Initially, that is

Activity around 30% above that measured in Example 3a) and even 50% above at the end of the reaction. At the same time, this means a significantly weaker one - 19 -

relative decrease in polymerization activity with time when using the supported co-catalyst system compared to the system without supported co-catalyst.

Example 3c

The polymerization was carried out as in Example 3a), but this time, together with the Nd catalyst described, 4.5 g of a zeosil which had been pretreated according to Example la) but not covered with DIB AH according to Example Ib) were conveyed into the reactor via the lock .

No particle agglomeration was observed in the course of this experiment. Within the scope of the reproducibility accuracy, the polymerization activity corresponded to that from Example 3a) over the entire reaction period.

Example 4a

The polymerization was carried out as in Example 3a), 3 g of a carbon black-supported catalyst as described initially or, inter alia, in EP-B-0647657, with an occupancy of 3.7 mmol Nd, 148 mmol DIBAH, 3, 7 mmol EASC and 7.4 isoprene per 100 g material were used. At the start of the reaction, the bed temperature rose to about 86 ° C. despite jacket countercooling. After 15 minutes, the reaction could be carried out isothermally at 80 ° C. over the entire course. Slight particle agglomerations occurred in the course of the reaction, but did not significantly impede mixing. The experiment was ended after 2 ^× A hours.

After the residual butadiene still in the reactor had reacted, the product was discharged via a ball valve in the bottom plate of the reactor and then immediately stopped and stabilized on the roller by mixing in 3 g of stearic acid and 3 g of Vulkanox BKF from Bayer AG. - 20 -

The average polymerization activity of the catalyst system in this experiment was about 450 [kg BR / (mol Nd • bar butadiene • h)].

Example 4b

The polymerization was carried out as in Example 4a), but this time, together with the Nd catalyst described, 12 g of the supported co-catalyst according to the invention from Example 2) were conveyed into the reactor using the lock.

No particle agglomeration was observed in the course of this experiment. There was also a significant increase in the polymerization activity of the catalyst system, which is about 63% on average over 2 hours. Initially, the activity is around 50% above that measured in Example 4a), and even 80% towards the end of the reaction). Here, too, the relative drop in the polymerization activity over time when using the supported co-catalyst system is significantly less pronounced compared to the system without a supported co-catalyst.

Example 4c

The polymerization was carried out as in Example 4a), but this time, together with the Nd catalyst described, 20 g of a carbon black previously pretreated according to Example la) but not coated with DIBAH according to Example 2) were conveyed into the reactor via the lock.

No particle agglomeration was observed in the course of this experiment. Within the scope of the reproducibility accuracy, the polymerization activity corresponded to that from Example 4a) over the entire reaction period.

Claims

- 21 patent claims

1. Catalyst system essentially consisting of:

and or

(RO) ₃ M (I)

(R-CO ₂ ) ₃ M (II)

(R-CH-C-R) ₃

(III)

O O

and

MX ₃ y Donor (IV)

B) an aluminum trialkyl and / or a dialkylaluminium hydride

Formula (V) and / or an alumoxane of the formulas (VI) - (VII):

Al (H) x (R ¹ ) ₃ . _x (V) 22 -

R ¹ (AO) _n AI ^

R (VI) R ¹

and

r (AP) = Γ

(NU)

R '

being in the formulas

the radicals R, identical or different, stand for an alkyl radical with CyCi _Q ,

M denotes a trivalent element of the rare earths with the atomic numbers 57 to 71,

X represents chlorine, bromine or iodine,

x represents 0 or 1,

y is 1 to 6 and

n means 1 to 50,

the radicals R ¹ , identical or different, stand for an alkyl radical with C _j -Cio,

another Lewis acid and - 23 -

D) an inert, particulate, inorganic or organic solid with a specific surface area greater than 10 m ² / g (BET) and a pore volume of 0.3 to 15 ml / g and, if carbon black is used, a DBP adsorption of 10 -300 ml / 100 g,

and additionally a cocatalyst applied to an inorganic or organic support material.

2. Catalyst system according to claim 1, characterized in that silica, carbon black, precipitated silica, zeolites, as support material for the co-catalyst,

Clay, talc, organic solids and / or mixtures of two or three or more of these substances is used.

3. A catalyst system according to claim 1 to 2, characterized in that the supported cocatalyst is used in amounts between 0.1 and 50 percent by mass based on the amount of fixed or fluidized bed.

4. Catalyst system according to claim 1 to 3, characterized in that the carrier material is moved at least during the application of the cocatalyst.

5. A catalyst system according to one or more of claims 1 to 4, characterized in that the support material is dried before application, freed from oxygen and is kept under an inert gas atmosphere before, during and after application of the co-catalyst.

6. Catalyst system according to one or more of claims 1 to 5, characterized in that the rate of application of the co-catalyst solution is controlled so that the added solution is immediately absorbed by the support material. - 24 -

7. A catalyst system according to one or more of claims 1 to 6, characterized in that the effectiveness level of the catalyst system is set by the ratio of supported cocatalyst to the remaining catalyst system.

8. A catalyst system according to one or more of claims 1 to 7, characterized in that the carrier material is evenly coated with active ingredients.

9. A catalyst system according to one or more of claims 1 to 8, characterized in that a support material with a grain size of 10 to 1000 microns is used.

10. A catalyst system according to one or more of claims 1 to 9, characterized in that it is completely or in individual components in one

Fluidized bed reactor is produced.

11. A process for the polymerization of conjugated dienes in the gas phase, characterized in that a catalyst system according to one or more of claims 1 to 10 is used.

12. Use of support materials coated with co-catalysts in a process for the polymerization of conjugated dienes in the gas phase.

13. Use of support materials covered with parts of the catalyst system in a process for polymerization in the gas phase.

14. Use according to claim 12 or 13, characterized in that silica, carbon black, precipitated silica or organic solids are used as the carrier material for the active component. - 25 -

15. Particles with a core made of polybutadiene or polyisoprene and a shell made of support material coated with cocatalyst prepared according to one or more of claims 1 to 14.

16. Particles with a core made of polybutadiene or polyisoprene and a shell made of support material coated with cocatalyst.