CS262451B1 - Catalyst for the polymerization of 1-alkenes - Google Patents

Abstract

The present invention relates to a carrier catalyst for the polymerization of 1-alkenes. Catalyst formed by sequential application to inert inorganic silicon oxide or aluminum oxide at least one organic aluminum compound and optionally magnesium, at least one compound transition metal 4a or 5a group periodic system and, where appropriate, at least one organic magnesium compound is phlegmatized 0.5 to 50% by weight paraffinic hydrocarbon, m.p. 150 ° C, which is applied either together with the active ones catalyst components or separately or a prepolymerization is formed on the catalyst 1-alkenes.

Description

The invention relates to single-phase supported catalysts for the polymerization and copolymerization of 1-alkenes in which oxides are used as the support and saturated hydrocarbons are used as the protective layer.

Polymers and copolymers of 1-alkenes are usually prepared using transition metal catalyst systems that can be supported and are typically activated by reaction with a cocatalyst - an alkyl compound - just prior to entering the reactor or up to the polymerization apparatus. These catalysts exhibit high transition metal activity and readily copolymerize higher 3-alkenes. The type of transition metal and ligands bound to the transition metal can influence the polymerization activity, molecular weight distribution, rheological and mechanical-physical properties of the polymers.

Addition of electron donor substances can polymerize propene and raise 1-alkenes to stereoregular polymers.

The source of serious technological complications is the activation of the catalyst with an organometallic compound immediately prior to or into the reactor. The design of these catalysts is based on a precursor of a suitable composition, which is not polymerically active. Interaction with the organometallic compound results in a polymerization active system which rapidly loses activity in the absence of monomer and / or the presence of monomer is required to form the active center. Therefore, this step is carried out only in the polymerization reactor. This means that two components - a catalytic precursor - usually in powder form - and an organometallic solution are fed into the reactor. The free organometallic initiates olefin oligomerization, which causes undesirable deposits on the inner walls of the polymerization apparatus. The reaction with oxygen and system impurities, whose access (diffusion) is practically unavoidable, decomposes the organometallic to aluminum oxide, which contributes to further formation of deposits. Aluminum oxide oligomer settlements are very difficult to remove and often have to be eliminated by narrow profiles and replaced with new ones (eg recycle coolers in gas phase polymerization).

The presence of free organometallic also adversely affects the kinetics of the polymerization, since sustained contact of the organometallic compound with the active centers results in both adolescence and thus a reduction in the number of free centers capable of polymerization and undesirable mechanical center changes (reduction of transition metal). activity and inappropriate particle size distribution of the polymer - high content of dust and particles with a diameter below 0.1 mm.

Another factor that significantly affects the properties of polymers is the quality of anchoring the active component on the support. In most of the prior art catalyst systems, perfect immobilization of the reaction products on the support surface is not ensured, which allows the individual components to migrate with one another and thus further undesirable reactions leading to the disappearance of the active centers. Post-activation transition metal catalyst systems are described, for example, in U.S. Pat. Nos. 4,302,566, 3,787,384, 4,148,754, 4,063,009, 4,173,547.

US 4,490,514 A, GB 1,484-254, GB 2,099,834.

In recent years, single-phase transition systems based on transition metals 4a and 5a of the periodic system have been developed. In the polymerization of 1-alkenes on single-phase catalysts based on titanium, vanadium and zirconium, there are no complications with dosing of cocatalysts, no deposits on the walls of the polymerization apparatus, and the obtained polymer has the desired particle morphology. Titanium-based single-phase catalyst systems are described, for example, in BE 884 513, BE 886 420, JA 5 200 880.

Single-phase catalyst systems are highly active in the polymerization of 1-alkenes and, due to the small amount of organometallic compound, are easily deactivated by reaction with impurities. The reactivity of these substances can be greatly reduced by covering the surface with an inert solid layer and thereby creating an effective diffusion barrier. This surface phlegmatization is very effective and allows the protection of highly active substances for any length of time (depending on the thickness of the protective layer). In the actual polymerization, the catalyst must be in its active form, the rate of diffusion of the monomer to the active centers must not be reduced. Therefore, it is possible to provide a protective layer of a substance with a melting point between ambient temperature and polymerization temperature. Practically, saturated hydrocarbons and mixtures thereof can be used.

U.S. Pat. No. 4,200,715 discloses a solid phase dispersion of a supported catalyst formed by mixing a paraffin wax with a liquid low molecular weight hydrocarbon. The catalyst thus treated is resistant to the diffusion of impurities and can be fed practically without inert gas into the reactor. The dispersion is carried out only with the finished catalyst, it is not possible to change the chemical parameters of the catalyst by anchoring the paraffinic phase at the deposition stage of the catalytic components. EP 159 736 describes the treatment of a one-component non-carrier catalyst by coating with a layer of viscous mineral oil. The resulting free-flowing powder is characterized by long-term shelf life and stability of polymerization activity.

The protective hydrocarbon layer can also be formed on the catalyst surface by prepolymerization of 1-alkene. This method also has other advantages. Active transition metal-polymer bonds are formed which are more stable than transition metal-alkyl bonds. Further, a different polymer can be formed by the composition and modify the properties of the final polymer.

Prepolymerization in order to improve the activity of the supported catalyst MgClj and abrasion resistance is the subject of patent FR 2 529 211. Elimination of stickiness of polymer particles and formation of a seal using the prepolymerization reactor is the subject of EP 102 895 (support based on MgCl ₂ and AlCl ^) and HO 8 505 111 A (non-carrier catalyst). GB 2,154,242 A discloses a reduction of the fine polymer particles after prepolymerization of a small amount of ethylene, optionally with admixture of 1-alkenes. According to JA 59 215 301, 1-butene or 4-methyl-1-pentene is prepolymerized on a highly active non-carrier titanium catalyst, whereupon either a portion of the polymer formed is dissolved and another monomer is prepolymerized. In the actual polymerization of ethylene and copolymerization with 1-alkenes, higher bulk density polymers are formed at a higher rate.

A process for producing transition metal catalysts and oxide supports is described in U.S. Pat. No. 256,961 and £. This invention relates to a process for phlegmatizing this type of catalyst to improve polymerization parameters.

SUMMARY OF THE INVENTION The present invention provides a catalyst for the polymerization and copolymerization of 1-alkenes formed by sequential anchoring to the porous oxide of Group 3b and / or Group 4b of at least one organic aluminum and optionally magnesium compound, at least one titanium and / or vanadium compound and optionally at least one organic compound % of magnesium containing from 0.5 to 50% by weight of a paraffinic hydrocarbon, m.p. 25-150 ° C.

In particular, the present invention provides such paraffinic hydrocarbon catalysts formed by the deposition of a paraffinic hydrocarbon in admixture with a catalyst component or on an active catalyst, and catalysts in which the paraffinic hydrocarbon is formed on the active catalyst by prepolymerization of 1-alkene.

For catalysts useful in the production of the polymers and copolymers of the present invention, a suitable support is silica and / or alumina having a specific surface area of 50-500 m ² / g, a pore volume of 0.5-3 ml / g having hydroxyl groups bound to the surface. the number can be changed by the dehydration temperature.

This is done by blowing the support layer through a stream of dry nitrogen or air. This is done by first increasing the temperature gradually and slowly up to 200 ° C, so that the water vapor is sufficient to leave without disturbing the carrier structure or condensing in the colder parts of the device. The dehydration of the carrier is generally carried out for 4 hours at a selected temperature in the range of 200 to 850 ° C. The carrier is cooled by a stream of nitrogen having a water and oxygen content of less than 1 ppm,

In the hydrocarbon solvent medium or in the gas phase, the support is then treated with at least one organometallic compound, e.g., trialkyls, dialkyl hydrides, dialkyl halides.

I alkyldihalides or. aluminum dialkylalkoxides or magnesium dialkyls, whereby the organometallic compound is firmly anchored. For uniform application, the carrier suspension or the carrier layer must be vigorously stirred, preferably the interaction is performed in a fluidized bed. The temperature during the interaction may vary within wide limits depending on the vapor pressure of the organometallic compound, preferably at a temperature of 10 to 70 ° C, preferably at ambient temperature.

Next, at least one transition metal compound of the group 4a or 5a, e.g. a halide, oxyhalide, haloalkoxide or cyclopentadienyl derivative of this metal, is deposited on the support with the anchored organometallic compound. The reaction of the product formed by the interaction of the organometallic with the hydroxyl groups of the carrier with the transition metal compound can be carried out preferably in a hydrocarbon medium or by direct contact of the transition metal compound vapors with the solid phase intermediate, preferably at room temperature.

The chemical bonding of the organometallic to the free hydroxyl groups of the bearer results in a modification of its reducing and alkalizing properties and at the same time immobilization on the surface. By fixing the organometallic on the support surface, selecting the ratio of the organometallic compound to the hydroxyl groups and the ratio of the transition metal compound to the organometallic compound, optimum active centers on the support surface are obtained which have the ability to polymerize 1-alkenes. Perfect anchoring of the components in and on the pores of the support is a prerequisite for a high and stable catalyst activity, good handling of the catalyst powder and its long shelf life.

According to AO No. 259 736, the properties of a single-phase catalyst can be significantly improved by applying an additional component - an organomagnesium compound - a dialkyl magnesium. This layer has only minor alkylating and reducing effects and serves primarily to protect the active centers in the pores of the carrier from penetrating impurities during the final phase of catalyst production, storage, transport and dosing. The conditions and method of deposition of the organomagnesium compound are the same as those of the previous components.

An important step in preparing the catalyst of the present invention is to deposit a paraffinic hydrocarbon on the surface of the catalyst particles. It is important that the melting point of the paraffinic hydrocarbon lies between the polymerization temperature and the maximum normal temperature of the environment in which the catalyst is produced, stored and transported. Preferably, paraffin having a melting point of from 50 ° C to 70 ° C, atactic polypropylene or other saturated hydrocarbons of suitable melting point may be used. The presence of double bonds and heteroatoms in the paraffinic hydrocarbon chains is undesirable as it reduces the activity of the catalyst. Low molecular weight impurities of the electron donor type have the same negative effect. The paraffinic hydrocarbon may be applied to the finished catalyst suspended in the hydrocarbon solvent or concurrently with the last catalyst component; ie, either in admixture with a transition metal compound or an organomagnesium compound, if used. The paraffinic hydrocarbon is applied to a content of from 0.5 to 50% by weight of catalyst, preferably from 1 to 10% by weight. The principle of action of a paraffinic hydrocarbon is to encapsulate the catalyst particles and prevent the diffusion of impurities during the isolation, storage, transport and dosing of the catalyst to the active centers. The formation of a diffusion barrier on the surface of the catalyst further stabilizes the catalyst system in the absence of monomer, reactivity of the catalyst components and the particulate grain, and a large proportion of the active centers are formed only after the paraffinic hydrocarbon has melted in the reactor.

The final stage in the preparation of the single-phase catalyst of the present invention is the desiccation of the hydrocarbon solvent with an inert gas stream, evacuation, or raising the temperature above the boiling point of the solvent.

The polymerization of the 1-alkenes according to the invention on a single-phase catalyst can be carried out in a mechanically or pneumatically stirred fluidized bed. It is polymerized at 50 to 120 ° C; lower temperatures are preferred in the polymerization of higher 1-alkenes of lower softening point, higher temperatures can be used in the homopolymerization of ethylene and copolymerization of ethylene with 1-alkenes. The polymerization temperature must be kept 5-10 ° C below the melting point of the polymer to avoid sticking

of particles. The polymerization pressure is 0.5 to 4.0 MPa. The optimum is 1.8 to 2.2 MPa, since at lower monomer pressures the catalyst productivity is lower (directly proportional to the monomer pressure), at higher pressures above 2.2 MPa, the costs for the acquisition and operation of pressure vessels and the compression of working media increase. . The polymerization is preferably carried out at a constant pressure, temperature and concentration of the individual components with continuous feed of catalyst, monomer mixture, hydrogen as chain transfer agent and continuous product withdrawal. The discontinuous process can also be implemented, but it is not economically advantageous.

The molecular weight can be controlled by the addition of hydrogen. Without hydrogen, ultra-high molecular weight polymers (UHMW) are formed, and as the hydrogen content increases, the polymer melt flow index decreases sharply.

Typically, the hydrogen content of the monomer mixture for injection and blow molding is 2 to 5% by volume. With hydrogen contents of 10 to 20% by volume, strongly liquid polymer types (fiber types) are obtained.

The catalyst dosage can be controlled by the instant polymerization rate (polymerization heat produced). The catalyst is powdered, well flowable, retains the properties of the original support even at relatively high levels of catalyst active ingredients (including solvent and paraffinic hydrocarbon) - up to 50% by weight.

During the polymerization, spherical polymer particles are formed which are similar in shape to the parent catalyst particles and hence the carrier. The magnification factor is 20 to 50 times, the polymerization produces compact particles of 0.5 to 5 mm in size, depending on the polymerization time (for the batch process) or residence time (for the continuous process). The usual polymerization time or residence time is 1 to 8 hours, most often 2 to 6 hours. At shorter polymerization times the ash and catalytic residue content of the polymer is higher, the reactor productivity is high, while at longer polymerization times the purity of the polymer improves and the reactor productivity is reduced.

At the outlet of the reactor, the catalyst is deactivated by air, steam or carbon monoxide, the catalytic residues need not be washed. The polymer is stabilized by conventional stabilizers against UV radiation and oxidation at higher temperatures; due to the high activity of the catalyst and hence the low content of catalyst residues, a small amount of stabilizers is sufficient. Due to the high bulk density of the powder and the large particles, granulation is not necessary, thus eliminating one thermal stress.

An advantage of producing polyolefins with the catalyst of the present invention is that an active catalyst system is used, requiring no further activation in the polymerization apparatus. The fixation of the components to the support and the additional deposition of the paraffinic hydrocarbon prevent the catalyst components from migrating with each other and thereby undesirable side reactions leading to the disappearance of the active centers. Coating the catalyst particles with a solid paraffinic hydrocarbon prevents the impurities from diffusing to the active centers between the catalyst production and the actual polymerization in the reactor. The fixed active centers in the pores of the carrier allow the polymer to be polymerized at high speed without the formation of unwanted melted polymer slices. This is achieved

- removal of the initial phase of a rapid rise in polymerization rate and its subsequent decrease,

- constant polymerization rates for 6 to 8 hours, that is to say, for a residence time in continuous reactors,

- prevention of deposits on the internal walls of the polymerisation equipment,

- high polymer bed weights ensuring high polymerisation productivity,

- absence of particulate matter in the polymer and particles below 0,1 mm in diameter,

- high bulk density of polymer powder (450 to 480 kg / m ¹ ),

- the ability to control polymer properties by the type of catalyst system used and the polymerization conditions,

- stability of the catalyst activity over many months to years and its resistance to electron donor impurities.

- improving the theological properties of the polymer over polymers containing no paraffinic hydrocarbon.

The following Examples illustrate the preparation of catalysts. % in the examples are by weight unless otherwise indicated.

Examples 1 and 2

To the cleaned reactor containing 50 ml of stripped n-heptane, 2 g of silica containing 0.5 mmol of hydroxyl groups per g were added upstream of pure nitrogen, a measured amount of organoaluminum and organomagnesium compound I was added - ratios see Table 1. After ca 30 minutes of reaction at normal temperature, the determined amount of the transition metal compound II (TiCl 2 - Example 1 and VCl 2 - Example 2) was measured and stirred for an additional 30 minutes. Then a quantity of paraffin with a melting point of 48-50 ° C according to Table 1 was added. After dissolution with stirring, the solvent was removed by evacuation. The product was an off-white powder with similar mechanical properties to the starting oil.

Example 3

In a 100 mL glass reaction vessel, 50 mL of n-heptane was purified by bubbling about 15% of the original amount of n-heptane by bubbling ultrapure nitrogen at 80-90 ° C. 2.0 g of Davison 952 silica, activated by the passage of ultrapure nitrogen for 4 hours at 600 ° C, were added. At room temperature, 1.2 mmol of triethylaluminum as a hydrocarbon solution was added. After stirring for about 30 minutes, 0.24 mmol of TiCl4 was added and the suspension was again stirred for 30 minutes. Finally, the organomagnesium compound -0.24 mmol of butylethylmagnesium was added as a solution in the hydrocarbon. After an additional 30 minutes of stirring, a mixture of ethylene with 60% by volume hydrogen was introduced into the slurry to polymerize 50 mmol of ethylene to oligomers at normal solid temperature. Upon completion of this prepolymerization, most of the solvent was removed by evacuation to form a free-flowing, well-moving powder. About 3.6 g of a supported single-phase catalyst capable of polymerizing 1-alkenes at a high rate were formed without the need for additional activation just prior to or in the polymerization reactor. The catalyst is non-sticky at ambient temperature, resistant to the diffusion of impurities and practically indefinitely stored prior to polymerization.

Example 4

In a 100 ml glass reactor, n-heptane was stripped so that at least 15% of the volume was left to evaporate 50 ml. Upon nitrogen flow, 2 g of silica containing 0.75 mmol of hydroxyl groups per g was added to n-heptane, a measured amount of organoaluminum compound or mixture I according to Table 1 was added. After stirring at room temperature for about 30 minutes the titanium compound II was added. . The suspension was again stirred for 30 minutes, after which the organomagnesium compound in the form of a heptane solution with paraffin of melting point 53-55 ° C was metered in. After stirring again for about 30 minutes, the n-heptane was removed by purging with pure nitrogen until an off-white free-flowing catalyst was obtained.

ExampleS

The procedure is the same as in Example 3 except that instead of triethylaluminum a mixture of ethylaluminum dichloride and dlethylaluminum chloride according to Table 1 was used, instead of TiCl4 Ti was used (OEt) and instead of butylethyl magnesium 40 mmol of 1-butene with 10 mmol of hydrogen were added and stirring was continued at normal temperature until the polymerization of 1-butene was complete. Upon completion of prepolymerization, most of the heptane was purged with nitrogen purge to give 4.2 g of a 1-alkene polymer active single-phase supported catalyst without the need for additional activation with any additional component.

Ί

Example 6

The procedure is the same as in Example 3 except that the ingredients of Table 1 were used for the preparation and, after the deposition of dibutyl magnesium and about 30 min of stirring, 20 mmol of 1-hexene with 5 mmol of hydrogen were added. and stirring was continued for 2 h. A vigorous stream of nitrogen led to the bottom of the canister while maintaining the temperature at 50 ° C evaporated the excess solvent to give 4.0 g of a supported single-phase catalyst capable of polymerizing ethylene without requiring additional activation with an organometallic compound.

Example7a8

The procedure is the same as in Example · í ·. by using 2.0 g of alumina containing 0.75 mmol of hydroxyl groups per gram, and after deposition of the ingredients of Table 1, 10 mmol of 1-octene (Example 7) or 5 mmol of 1-octene were injected into the reaction vessel instead of ethylene; decene (Example 8) together with 2 mmol hydrogen. The mixture was heated to 80 ° C and stirring was continued for 4 hours. The excess solvent was then evaporated with ultrapure nitrogen. About 3.5 g of a supported single-phase catalyst capable of polymerizing 1-alkenes was obtained.

Example. 9

To a 100 mL glass reaction vessel was charged 60 mL of n-heptane, 2 g of paraffin melting at 55-57 ° C and 2.0 g of Davison 952 silica activated with ultra-pure nitrogen for 4 h at 800 ° C, the suspension was heated to 80-90 ° C and 10 ml of n-heptane was evaporated by bubbling ultrapure nitrogen. 1.43 mmol < 1 &gt; was added to the suspension. 1minium dichloride as a solution in n-heptane and stirring for 30 min. After stirring for 30 min, butylethyl magnesium was added. After stirring briefly, the n-heptane was evaporated to a white powdered state.

The poodle-coated catalysts of Examples 1 to 9 can be obtained in the form of dry and free-flowing powders containing a small amount of low molecular weight solvent up to a maximum of about 50%. The catalysts can be stored indefinitely in commonly used tanks using conventional valves or taps. If electron donor-type impurities penetrate the catalysts, the catalyst bed must be thoroughly purged with ultra-pure nitrogen prior to polymerization to prevent impurities from entering the polymerization apparatus.

The polymerizations were performed according to the following example:

Example 10

The powdered catalyst is placed sealed in a glass vial in a 1.5 L laboratory reactor crushing plant to allow the preparation of 300 g of polymer. The reactor was purged with ultra-pure nitrogen flow overnight (16 hours), then alternately pressurized nitrogen to 2 MPa 5 times at a future polymerization temperature and evacuated, then pressurized twice with 2 MPa ethylene and re-evacuated. Finally, the reactor was pressurized with a mixture of monomers with hydrogen - ratios, see Table 2. The polymerization was started by crushing a glass flask containing 50 to 100 mg of catalyst. The fluidized bed was kept buoyant by mechanical agitation, the rate of polymerization was measured from the consumption of the monomer mixture supplied. 'After some time (typically 4 hours), the reactor was depressurized, opened and the polymer isolated.

After deactivation of the catalyst with air, water vapor or carbon monoxide, the polymers need to be stabilized against UV radiation and oxidation at higher temperatures by conventional stabilizers.

For example, a mixture of a sterically hindered phenolic antioxidant and tris (nonylphenyl) phosphite in a weight ratio of 1: 0.5 to 1.5 in an amount of 0.01 to 0.03% per polymer can be used. Due to the high activity of the catalysts, the amount of stabilizers required is low. The polymer consists of large particles (usually 0.5 mm and larger), so it is not necessary to granulate it by processing.

> 1

Λ

U 44 • rl Ή

C Ό • rl w iw!> <* (0 h h r-j <0 Λ & 3 xr co

CN and xr 1 O «Η 1 i-1 1 r-1 1 r4 1 Xř 1 3 3 3 3 3 Λ AND CN CN A AND AND 44 44 3 3 44 44 P H W AND AND M W « θ ' θ ' θ ' θ ' θ ' θ ' θ ' with £ £ £ £ £ £

cn m in m r- »-i o m m in t I I I I I I

CN in <<? xr pq r4 xr xr i — I ^ * r4r-IOUMr4r4 u η υ υ - οαυυ • H U * H · Ή Ή · Η · Η «Η ·> ^> Η ^ ΒηΗΕμΕ-ΙΕ-Ι

BJ

O

ro 44 « O CN r4 at 0 44 +4 44 w W W H H »-L C

0 3 3 N 3, £ g

in what σ \ O O WHAT m 03 σ » p o CN r4 O o o CN CN CN CN r4 r4 r4 rH <O U at at what CO U <P 44 44 44 44 44 44 «« H « AT «« r4 r4 r-l r4 r4 H r4

Catalyst composition x

r-l

0 «0

Em

Φ> O

G * H • H »

CbO θ '3 C ^' X H § '* 8

O g O

I <0 G

Note: Davison 952 having a specific surface area of 250-300 m / g pore volume of 1.6 ml / g was used as carrier with a maximum pore radius of 11 nm, dried at 800 ° C (Examples 1 and 2) and 600 ° C (Examples). 3 to 6 and 9) and alumina having a specific surface area of 150 m ^ / g pore volume of 2.5 ml / g with a maximum pore radius of 25 mm, dried at 800 ° C (Examples 7 and 8).

Et = ethyl, Bu = butyl (*

<*>

β

Φ> N »H O MO

- o *

B o x> iTO tP β H X -H X X) P P P>))))) .. ... xo + J (i CP fi Φ * ss * * i o β

Osfl XX p g to to o, «o <n 3 Kc WWHN>, β

• H tP fiX

Hall

3oT

5 ”fn« KU • a χ α © Re »Φ Φ ο β xowo e CP β X

X p O * * β TOX (ΏΜ Nrltí

I o

X fi

X

X β

M a

MHNNNNONOHNNHHHHNNMN ooooooooooooooooooooooo u> (M © mcic4rxtnor »<soix (n <M © c40Qi ** ©« ΐχρ * «νοιηϊχ (θοιιπιη (θβ'θβ ^, β · οο n nι ©)

X

CMinoroTOxoHcoo (Mxococ4 ^ rx © oooo

OOOOOOOOOOOOOOOOOOOOOO

©ίΛΟίηοΟΟΙΛίΛίΛΟΙΛΝΟίΛΟΟίΛΛΟ βΜβΡΙβΙΟβΗ ^ ΗΜΗΓ'ΚηΠΜΙΛΊ'ΡΙΜ TO © © WHAT WHAT WHAT

ΛΟΟίΠίΛ ^ βΟΦίΛΗβΟΟΟΟΙΠΟΟΦ r »THIS« no <*) rH «HC4 (M (ηβ ^ ωιηοΗΝ Ν © Ν * ΙΛ« *) <M TO β · β · β · β · β * β · f

fi

β.

w **> N> 1> 1 β *.

X IH 3 «» 3

I ^M 32

II 41 KU b ^c 'n £ Q β 04 04 fe tPX

N X

Ji with δ ^&

Λ «

Ji δ s * β N> 1 3 3 β X

Ž 3 β

x

3.

o δ

s, β

N> 1 ^ CM ^ CM CM »» CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM <Ό

ΙΠ © ©

ΟΟΟΟΟΐΛΗ «ΝΟΝΟΟΟΟΟΟΟΟβ © 04 © Cx © <Μ« Η (β © © © © Μ 00 00 ©

CM © CM ί *> β © © Γ- β · β · © © β ·

I I I I I I I © © I »I © Ο © I

0 »Ρ β β * 0 Φ β > Φ β ο δ > Μ © β 0 Ρ 5 X Η Ρ β «0 X μ Φ * β Μ Χ < 5 fl Ν Φ β © 0 < > ι> ιΛ) χ <β Φ © © Μ

β

X ž

X β

X €

3S & 3323

32 ^ 32 ^ 3

S ^& M «3333 ni feM>» 5 0 * 9 O OM0 fiX 0 Λ OH & N © Ml M M1 MX> Ρ | | Χ & X on 3 on on H H H Ufl U U t ΛΜΟ ΛΜΟ 38> X HM

II

Ϊ3 oť§

H what U

I <<<ί © <<<<<© © © © © © οοο ι ι | © I I 1 I 00 I Ο I I I © © © 00 © β · ©

I 00 Ρ © ΙΟΙ ΙΟΙ 00 00 00 00 00 00 00 00 00 00 00 Γ 00 00 00 00 | | | © | © © © © © © ©

ΟΟΟΟ © Ο Ο © Ο ©Iοοοοοοοοοοοο

00000000000000000000

© TOlAmOTOTOTOTOtATOH (fíTOOTOChATOTO ©© ΜΠβ> β · β · β> β · β ^| β ^{| β, β>>} ΑΦνθ (ΧβΟΟ) <Ρ

X β 14 β 14 υκ £ fe fe CM © CM <*) β * (Λ <*) <

AND

262451 10

Claims (2)

subject to finding CLAIMS 1. Catalyst for the polymerization of 1-alkenes, obtainable by sequential deposition on an inert inorganic silicon and / or aluminum oxide of at least one organic aluminum compound and optionally magnesium, at least one transition metal compound 4a and 5a of the periodic group and optionally at least one organic magnesium compound; characterized in that it contains 0.5 to 50% by weight of a paraffinic hydrocarbon having a melting point of 25 to 150 ° C. 2. Catalyst for the polymerization of 1-alkenes according to claim 1, characterized in that the paraffinic hydrocarbon is a product of prepolymerization of 1-alkene on an active catalyst.