DE2720232A1 - METHOD OF GRINDING A FIXED COMPOUND OF A TRANSITION METAL WITH ORGANIC COMPOUNDS - Google Patents

Description

Tn V

IEDTKE - BUHLING - fViNNf -

Patent attorneys: Dipl.-Ing. Tiedtke Dipl.-Chem. Bühling

Bavariaring 4, P.O. Box 20 24 03

8000 Munich 2 Tel .: (0 89) 53 96 53-56 Telex: 5 24 845tipat

cable. Germaniapatent Munich

5th time 1977 B 8127

ICI case Po 28761

IMPERIAL CHEMICAL INDUSTRIES LIMITED London / Great Britain

Process for grinding a solid compound of a transition metal with organic compounds

or. na. 709845/1099

ORIGINAL INSPECTED

? 272U232

The present invention relates to a method of treating compounds of transition metals and the use of the treated compounds as a component of a catalyst for Polymerization of olefins.

The present invention therefore provides a method for grinding a solid compound of a transition metal of groups IVA to VIA des Periodic table with a smaller proportion of at least one organic compound, which is an organophosphorus compound and / or an organosilicon compound, which is characterized in that the solid compound of the transition metal also with a smaller proportion of at least one Schwciel containing organic compound is brought into contact, which is selected from the following group of compounds has been:

Sulphones of the formula

Sulfonamides dor I'ormel

and

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Sulphides of I'oriw:]

where mean:

-X - regardless of judo in other X - a halogen atom, an alkyl, aryl, alkoxy, aryloxy, Alkyltliio-, arylthio oiler a NRH group, where two X groups together are a saturated or unsaturated Kohlenwassorstof fr i ng Y - independently of any other Y - is a halogen atom, an alkyl, aryl, alkoxy, aryloxy, alkylthio, arylthio or cine NRR group, where two groups Y together can form a saturated or unsaturated hydrocarbon ring , wherein a group X and a group Y can be replaced by a link between the two rhenyl groups connected by an SO_-Gruppo and the compound either directly or by a group -O-, -CH ₂ -, -NR-, -S- or —CO—, Z - independently of any other Z - is an ilalogen atom, an alkyl, aryl, alkoxy, aryloxy, alkylthio, arylthio or NRR group, two groups Z together being a saturated or unsaturated one Hydrocarbon]} ng can form, D - independent of n every other D - a halogen

atom, an alkyl, aryl, alkoxy, aryloxy, alkylthio, arylthio or an NRR group, T -S-, -Ο-, -NR ¹ - or -CO-,

Π a hydrogen atom or a hydrocarbon1 rent,

R a leftover Kohlonwnssoi fabric,

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R is a hydrocarbon residue or a group

n, ni, ρ and q - each independently one integer from 0 to 5 and χ is a positive integer.

The smaller portion of the organic compound and the sulfur-containing organic compound amounts to at least 0.01, jetloch not more than 1.00 mol per gram atom of transition r.meta L I, which is in the solid Connection of the Ubergancjsmeta I Is is present.

For the sake of simplicity, the following the Ai. ; print "organic compound" for organic Compounds used that are organophosphorus compounds or are organolium compounds; and the The term "sulfur compound" is used to refer to sulfur-containing organic compounds are used that have one of the defined formulas.

[! ei Ir connection of the transition. =; »! * '? Ta I Is it is preferred that the metal is one of si; inet having "maximum value lying valence [> ns Ubergangsiiie ta II can z.ti. zirconium or vanadium its However, it is particularly preferred to use a compound of titanium Preferably, the compound of the flborgangsmeti;... L l ^i; a Obergangy -

2b meta II halide or oxyhalide (ζ.Is. V (KH ₂ ), in particular a chloride, the titanium triochloride being of particular importance. The term "titanium trichloid", which is used here, does not apply

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only on pure TltantrichLorid, but also on Titanium trichloride compositions containing other materials in particular ALuin Ln LumchLor Ld or alkylaluinine iumchlor ide, e Irish L divide. Such forms of titanium trichloride are produced by the reduction of Titanium tetrachloride with aluminum in turnetal1 or one Orcjanoa Ium Ln iuniverb Inching received. materials of the type TLtantr IchlorLd / A1 to Ln Lumchlor Ld, which by means of Reduction of titanium tetrachloride with aluminum metal have been fulfilled are particularly preferred .

For the sake of simplicity, the expression "cjemahlene connection des [Jbergancjsmeta L Is" for the chosen the following facts: "Fei; te connection of a transition metal L Ls of groups IVA to VIA des Periodic table, with a smaller proportion at least one organic compound has been ground, which is a ÜrgunophosphorverbLundung and / or e ine Organos i L Ic Lumve rb induncj da rr; te LIt ".

When it comes to the organic bond e Lnt! Organophosphot vet 1> iridation, preferably has it a! ■ '(μ m · I

in which K has the voisLeading defined Uedoutunfj and y is 0 or I. The (It lips K can sciLn differently, but are mostly all the same. The groups Ii include all alkyl groups with IjLs 20 KoIi li-dung ι iM af omen or aryl groups with 6 to I ^r > Koh 1 em; t ot tatoiiien, ■ / .. H. Tr ibu Ly! Phosphine or Triplietiy 1 iilioi [) li L π, dir.

7 Ü ^C JB 4 B / I ü Π 9

ORIGINAL INSPECTED

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When the organic prebond is an organosilicon compound is- is never an organosilane either, a siloxane or a compound containing at least one Si-N bond., e.g. Octamethylcyclotetrasiloxane

Si

a polysiloxane of the form]

(CH ₃ ) ₃ si (osi (CH ₃ ) ₂

Hexamethyldisilazane

I (CH ₃ ) ₃ SiNHSi (CIl ₃ ) ₃ )

or Tetrakis (dimethylami no) si lan

The sulfur compound can be a suI hair dryer, such as diphenyl sulfone, a substituted derivative thereof, a compound such as phenoxathiin-10,10-dioxide or Tiioxanthene-10, 10-dioxi d. A.idoro sulfur compounds record N, N-Di iithy] -4-phenoxy benzo] su] f onamid, N, N-diphenyl-benzene sul f onanii d and Plienoxathi in.

The fixed pre-tie ties iJborqangsmotal Is will jO ground with at least one organic pre-binding. You will also use at least one sulfur compound brought in contact. The I nkont al: tbringon can get through Mixing the ground compound dr · :. Transition metal with a) solution of the sulfur compound or by having a meal veryi tf: ■; take place,

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in which the connection of the transition mechanism is in the presence a sulfur compound is ground.

The sulfur compound can be brought into contact with the transition metal compound after grinding the compound of the transition metal with the organic compound is. However, all components, if the solid compound of the transition metal with the organic Compound and the sulfur compound is milled, the milling device before performing the milling to be added. The bringing into contact is then carried out simultaneously. In fact, in Depending on the order in which the ingredients are introduced into the grinding device, the Sulfur compound with the solid compound of the transition metal before adding the organic compound be brought into contact.

When the ground connection of the transition metal is mixed with a solution of the sulfur compound, this can advantageously be done by heating to a temperature of at least 60 ⁰ C. The mixture of the milled compound of the transition metal and the solution of the sulfur compound is preferably heated to a temperature of 80 to 120 ⁰ C. The mixture is advantageously kept at a temperature of at least 60 ^° C. for a time of 0.5 up to 25 hours, in particular for 2 to 20 hours. The mixture is preferably stirred while it is in contact.

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If the solid compound of the transition metal with both the organic compound and the Sulfur compound is milled, the milling can be carried out in two separate process stages. During the first stage only the organic compound is present and during the second process stage the sulfur compound is also present. 'If the grinding is in two separate stages a metal halide such as aluminum chloride can be used during the second stage of milling or titanium tetrachloride, also be present. It becomes clear, however, that all the components including the optionally used metal halides, ground together in a single grinding process can be.

The amount of organic compound that is ground with the compound of the transition metal, is at least 0.01 mole and not more than 1 mole per gram atom of the transition metal present in the solid Connection exists. It is preferably from 0.01 to 0.50 mol, with the range from 0.05 to 0.20 mol per gram atom of transition metal present in the solid compound is particularly preferred.

The amount of the sulfur compound is also at least 0.01 mol and not more than 1.00 mol per every gram atom of transition metal present in the solid compound. It is preferably 0.05 to 1.00 mol, in particular the range from 0.10 to 0.50 mol per gram atom of transition metal which is in the solid connection is present, is preferred. It is particularly preferred that the amount of the sulfur compound is at least equal to the amount of the organic compound.

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When a metal halide such as titanium tetrachloride or aluminum chloride is present during milling it is preferred that the amount - in moles of the titanium tetrachloride or aluminum chloride is the The amount - in moles - of the sulfur compound does not exceed. The amount of the metal halide is preferably between 0.01 and 0.50 moles per each Gramm-'atom of transition metal present in the solid compound is present, with the range from 0.10 to 0.40 moles being particularly preferred.

The milling is conveniently carried out using a ball mill. It is preferred that at least part of the milling takes place in the dry state, ie in the absence of added solvents and suspending liquids. The materials to be milled can be placed in the mill or in another milling device, either in the absence of solvents or in the form of a solution or suspension in a suitable inert diluent, which is then removed by heating and / or applying reduced pressure. Milling can be done at any suitable temperature. Satisfactory results may be achieved by milling at room temperature (about 20 to 25 ° C), although it is also apparent that higher or lower temperatures - if desired - may be chosen, for example from -10 ⁰ C to 100 ⁰ C. The grinding may take place for any length of time. Typical meals are between one and 100 hours or more. For example, 5 to 72 hours can be selected. It can be seen that the grinding time depends on the intensity of the grinding. When using a rotary ball mill, it depends on the material, the size

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and the number of balls used and the speed of rotation depend on the ball mill. A typical time is between 24 and 72 hours. Other grinding techniques can be used, e.g. grinding in a vibratory mill. When using other techniques, different Times and temperatures for grinding may be beneficial.

The milled product can be removed from the milling device in the form of a dry solid will. But it becomes particularly easy by adding a suitable liquid medium, especially an inert organic liquid such as an aliphatic hydrocarbon, and through Washing out of the ground solid removed in the form of a suspension in a liquid medium. One convenient procedure is to use a suitable inert liquid medium of the mill and its Add content to continue the milling process for a short period of time, preferably no longer than 30 minutes and in particular between one and 20 minutes. The resulting Suspension is readily removed from the mill. Remaining amounts can be used further quantities of inert liquid medium are washed out. During the wet milling stage a rapid reduction in the particle size of the solid occurs. To an undesirable particle size reduction To avoid wet milling for only a relatively short period of time is preferred perform.

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The method according to the present invention is carried out in an inert atmosphere, i. in the absence of any amount of oxygen-containing materials, such as air and water vapor, the presence of which is sufficient to ensure the properties of the milled product as a component of a catalyst Adversely affecting polymerization of olefins.

It can be seen that the process of the present invention works in the absence of the organo-compounds is carried out by metals not counting among the transition metals, e.g. Organoaluminum compounds act as an activator component of a catalyst for polymerization of olefins can be used.

The ground product can - especially if it is produced by grinding in the presence of titanium tetrachloride - washed with, for example, an inert aliphatic or aromatic hydrocarbon before it is used as part of a catalyst for the polymerization of olefins.

The ground compound of the transition metal that is brought into contact with the sulfur compound has been used to produce a catalyst for the polymerization of ethylenically unsaturated Suitable for hydrocarbon monomers.

Accordingly, the present invention further relates to a catalyst for polymerization of olefins containing

1) a compound of a transition metal that is a product of the above

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the procedure described, and

2) at least one organometallic compound of aluminum or one not to the transition metals counting metal of group HA of the periodic table or a complex of an organometallic Compound of a metal from group IA that does not belong to the transition metals or HA of the periodic table and an organoaluminum compound.

Component 2), the organometallic compound, can be a Grignard reagent, which is essentially free of ether, or a compound of the Mg (C ₆ H ₅ ) 2 type. The constituent 2) can optionally be a complex of an organometallic compound of a metal from groups IA or HA, such as, for example, Mg (Al (C ₂ H ₁ -) ₄ ) ₂ or a lithium aluminum tetraalkyl. It is preferred that component 2) is an organoaluminum compound such as a bis (dialkylaluminum) oxyalkane, a bis (dialkylaluminum) oxide, an aluminum hydrocarbyl sulfate, an aluminum hydrocarbyloxyhydrocarbyl or especially an aluminum trihydrocarbyl or dihydrocarbyl aluminum hydride or aluminum halide, especially aluminum triethyl chloride.

A mixture of compounds can be used if desired, e.g. a mixture of one Aluminum trialkyl and an aluminum dialkyl halide. It can be beneficial to use catalysts too which provide a low level of halogen remaining in the polymerized product, wherein In this case, component 2) is preferably a halogen-free compound,

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in particular an aluminum trihydrocarbyl. As used herein, "hydrocarbyl" means a hydrocarbon radical in the broadest sense.

In addition to any organic Lewis Base compounds used in the Component 1) of the catalyst can also contain a further amount of an organic Lewis base (Part 3)) are available. The further organic Lewis base can be such a Lewis base that the Activity and / or stereospecificity of a Ziegler catalyst system effectively changed.

The use of organic Lewis bases or complexes containing organic Lewis bases in Catalysts for the polymerization of olefins are described in the following publications, among others:

GB-PSs 803 198, 809 717, 880 998, 896 509, 920 118, 921 954, 933 236, 940 125, 966 025, 969 074, 971 248, 1 013 363, 1 017 977, 1 049 723, 1 122 010, 1 150 845, 1 208 815, 1 234 657, 1 324 173, 1 359 328, 1 383 207, 1 423 658, 1 423 659 and 1 423 660 and BE-PS 693 551.

However, it is preferred that the further organic Lewis base contains at least one atom of sulfur, nitrogen and / or phosphorus. Thus: include preferred organic Lewis bases that can be used as optional ingredient 3) of the catalyst, "sulfur compounds" (as defined above) such as diphenyl sulfone, secondary or tertiary amines such as dibutylamine or tributylamine, diamines such as Ν, Ν, Ν ¹ , N'-Tetramethyläthylendiamxn, and compounds that contain both phosphorus and nitrogen atoms, such as hexamethylphosphorus

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acid triamid, N, N, N ', N'-tetramethylethylphosphorodiamidate, Ν, Ν, Ν ¹ , N ¹ , N "-pentamethyl-N" -ß-dimethylaminoethylphosphoric acid triamide, 2-dimethylamino-1,3-dimethyl-1,3, 2-dlazaphospholidine-2-oxide and octamethylpyrophosphoric acid amide.

In addition to or instead of the organic Lewis base, which is component 3), the Catalyst also include a substituted or unsubstituted polyene (component 4)), wherein it is an acyclic polyene, such as 3-methylheptatriene (1,4,6), or a cyclic polyene, such as cyclooctatriene, Cyclooctatetraen or cycloheptatriene, or derivatives of such polyenes, such as alkyl or Alkoxy-substituted polyenes, tropylium salts or complexes, tropolone or tropone can act.

The proportions or proportions of the various catalyst constituents can be varied within wide limits vary, both from the materials used and the absolute concentrations of the constituents depends. However, in general, per gram atom of the transition metal contained in component 1) of the catalyst is contained, at least 0.05, preferably at least 1.0 mol of component 2) before. However, it may be desirable to use larger amounts of ingredient 2), e.g.

50 moles or even more per gram atom of the transition metal. In general, it is preferred no more than 25, in particular not more than 10, moles of component 2) per gram atom of the transition metal to use. The amount of the organic Lewis base serving as optional ingredient 3) is in in the range from 0.01 to 10, preferably from 0.05

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to 5.0 moles per gram atom of the transition metal that is present in component 1) of the catalyst, the range from 0.2 to 2 mol being particularly preferred will. The amount - in moles - of the component 3) is not less than the amount - in moles of component 2). The number of moles of each polyene that is present in the catalyst should preferably less than the number of moles of component 2) of the catalyst · at each mole of component 2) are preferably 0.01 to 1.0, in particular 0.05 to 0.5, e.g. 0.2 mol of polyene present. If the catalyst is both the constituents

3) as well as 4) should contain the total number of moles of the organic Lewis base making up the constituent

3) and the polyene will be less than the number of moles of ingredient 2) of the catalyst. If the catalyst has the two components 3) and

4), then these can advantageously be used in equimolar proportions. However, the relative proportions of these components can be changed in order to achieve an optimal result.

The Lewis base representing component 3) of the catalyst is advantageously one of the following compounds: hexamethylphosphoric triamide, 2-dimethylamino-1, 3-dimethyl-1,3,2-diazaphospholidine-2-oxide, N, N, N ^f , N ¹ , N "-pentamethyl-N" -ß-dimethylaminoethylphosphoric acid triamide, tetramethylethylenediamine, tributylamine or diphenylsulfone.

The catalysts of the present invention are particularly useful for polymerization and copolymerization of olefinic monomers suitable, where

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at least one olefinic monomer with one
Catalyst of the type defined above in
Contact is brought. In particular, the
Invention a process for the preparation of a polymer or copolymer from olefinic monomers

created, wherein at least one olefinic monomer or a mixture of at least one olefinic Monomers and ethylene with a catalyst of the type described above for polymer

sation of olefins is brought into contact. Any olefinic monomer, especially one
Mono-α-olefin monomer obtained using a
Ziegler catalyst is polymerizable, can
polymerized according to the method of the present invention. Thus, monomers which can be polymerized by the present process include butene- (1), 4-methylpentene- (1) and especially propylene. These olefins can be copolymerized. However, it is preferred to carry out the copolymerization with ethylene, preferably one
Serial polymerisation process (sequential polymerisation process) is carried out, which is carried out in the
GB-PS 970 478, 970 479 and 1 014 944 described
will.

It has been found that the process of the present invention can be used to polymerize propylene to give a high yield of polymer based on the amount of polymer used
Catalyst - to achieve and also a relative

to form low levels of undesirable soluble polymers.

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It is well known that the Ziegler-type catalysts are degraded in effectiveness by impurities are adversely affected. In addition, the activity and the stereospecificity of such catalysts adversely affected by the presence of small amounts of contaminants especially by oxygen-containing and polar compounds such as water and alcohol in the monomers and / or diluents - if used. As a result, the polymerization of olefinic monomers using Ziegler catalysts are known to be pure monomers and diluents used. However, when catalysts according to the present invention are used, these can be used in smaller proportions than the conventional catalysts of the Ziegler type will. As a result, they are more susceptible to any contamination present in the system. Therefore, when using catalysts according to the present invention, the aim is that the Monomers and all diluents that show the commercial purity are subjected to further cleaning measures.

The cleaning treatment can be carried out in several stages or - if desired - in one stage. The particular cleaning treatment used depends on the nature of the contamination of the source material Lukewarm.

Satisfactory purity can in most cases be achieved by using the Monomers (and diluents, if used) is passed through a bed of material,

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capable of absorbing the impurities contained in the monomer or diluent as described, for example, in British Patents 1,111,493 and 1,226,659.

Using the catalysts according to the present invention, the polymerization in Presence or absence of an inert diluent such as a suitably purified paraffinic Hydrocarbon. If no diluent is used, the Polymerization can be carried out in the liquid phase, with excess liquid monomer as Suspending medium is used for the catalyst and the polymer product. When the monomer is in a When gas phase is used, the polymerization can be carried out by any suitable technique for gas / solid reactions, such as those in a fluidized bed reactor system or in a reactor type of countercurrent mixer.

The polymerization can be carried out either batchwise or continuously. The catalyst components can be placed separately in the polymerization tank. However it will preferably, in particular in the case of the polymerization carried out continuously, all catalyst constituents to mix before they are introduced into the polymerization reactor.

The polymerization can take place in the presence of a chain transfer agent such as hydrogen or Zinc dialkyl to reduce the molecular

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adjust the weight of the product formed. If hydrogen is used as a chain transfer agent, this is preferably done in an amount from 0.01 to 5.0, in particular from 0.10 to 2.0 mol%, based on the monomer. The amount of chain transfer fiängt on the polymerization conditions, particularly the temperature, which is typically in the range of 20 to 100 ⁰ C, preferably between 50 and 85 ° C.

When using catalysts according to the present invention, propylene can be polymerized are based on a polymer with high flexibility modulus (flexural modulus) in high yield on the transition metal content of the catalyst.

The present invention will hereinafter be described in various ways with reference to the following examples Explained in more detail. In the examples, all measures are under one Nitrogen atmosphere carried out, unless otherwise stated.

example 1

In a stainless steel mill with a length of 15.2 cm and a diameter of 7.9 cm, with four metal strips arranged inside, 200 stainless steel balls became one Diameter of 12.7 mm and 200 stainless steel balls with a diameter of 6.35 mm.

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brings. The mill was sealed, evacuated to a pressure of 0.2 mm Hg and flushed with nitrogen, to create a nitrogen atmosphere in the mill.

5.86 g of diphenyl sulfone (0.20 mol - based on the titanium trichloride content of a Stauffer TiCl -, - ΑΑ below placed in the mill) were placed in the mill, followed by the addition of 1.0 ml of octamethylcyclotetrasiloxane (0.096 moles re-

fetching units of the siloxane - based on the

Titanium trichloride content of the Stauffer TiCl ₃ ~ AA - subsequently introduced into the mill) followed. The mill was evacuated to 0.2 mm Hg and filled with nitrogen
flushed. 26.7 g titanium trichloride (Stauffer-TiCl ₃ ~ AA)

was then added and finally 1.47 ml

Titanium tetrachloride (0.10 moles - based on the titanium trichloride content of the Stauffer TiCl ₃ ~ AA).

The mill was set at a rotation of 120 revolutions per minute and water at a temperature of 20 ^° C. was run over the exterior of the mill
calmly. After milling for 24 hours, the mill turned off
brought to a standstill. 100 ml of an inert aliphatic hydrocarbon liquid (boiling point range about 170 to 180 ^° C.) were added. Milling was continued for an additional 5 minutes. The resulting slurry was transferred to a storage container. The mill was filled twice with 100 ml
washed aliquots of the same inert hydrocarbon diluent. The washing media

were transferred to the storage container.

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- 26 Example 2

The procedure of Example 1 was repeated except that a polysiloxane the formula

(CH ₃ ) ₃ Si (OSi (CH ₃ ) ₂ ) gOSi (CH ₃ ) ₃

was used, an amount of 0.082 mol of siloxane repeating units - based on the titanium trichloride content of the Stauffer TiCl ₃ ~ AA - was used. Milling was carried out in the presence of an inert hydrocarbon liquid for only 2 minutes.

Examples 3 and 4

The titanium trichloride products of Examples 1 and 2 were used to polymerize propylene.

The propylene used in the polymerization had been purified by passing gaseous propylene through a column (76.2 mm diameter, 0.914 m length / 3 inches, 3 feet) containing 1,587 nonnegranules of Alcoa F1 alumina at 50% to 60 ^° C. and then through a similar column which contained a BTS catalyst (copper (II) oxide which had been reduced to finely divided metallic copper on a magnesium oxide support) at 40 to 50 ^° C. was passed. The exiting gas was condensed and the liquid propylene at 25 ° C through four columns (all 76.2 mm in diameter, two 0.91 m (3 feet) long, two one length)

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6 feet), each 1.587 mm beads (1/16 inch) of Union Carbide SA molecular sieves.

This treatment reduced the water content of the monomer from 5 to 10 ppm (volume) <1 ppm (volume) and the oxygen content of 1 to 2 ppm (volume) <0.5 ppm (volume). The level of inert compounds (nitrogen, fithan, etc.) remained unchanged at 0.3%, and the level of unsaturated hydrocarbons (allene, methylacetylene, etc.) remained unchanged at <1 ppm.

A polymerization flask equipped with an effective stirrer and with a jacket designed for water was carefully dried and 1 liter of an inert hydrocarbon diluent with a boiling range of about 170 to 180 ^° C. was introduced. The diluent was flushed with nitrogen under vacuum at 70 ^° C. and kept under vacuum. This treatment effectively reduced the water and oxygen content of the diluent to less than 10 ppm by weight. The diluent was then saturated to atmospheric pressure with purified propylene containing 0.15 volume percent hydrogen. Ten millimoles of diethylaluminum chloride were added to the polymerization vessel, followed immediately by 1.0 millimoles of tri-n-butylamine. 2 millimoles of TiCl ₃ materials, obtained as described in Examples 1 and 2, were introduced. The temperature was maintained at 70 ^° C. and the pressure in the reaction vessel at 1 atmosphere by supplying propylene with a content of 0.15% by volume of hydrogen. After a period of

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4 hours - counted from the introduction of the TiCl ₃ , the operation was carried out using 10 ml of isopropanol and

Finished 5 ml of propylene oxide. A sample of the excess liquid was withdrawn to determine the concentration of the polymer dissolved in the polymerization diluent. The solid was filtered off and washed three times with petroleum ether and dried in a vacuum oven for one hour at 120 ⁰ C. The results obtained are recorded in the table below.

Tabel

example Type of TiCl Yield to % By weight of the im (a) solid poly Dilution mers (g / mM medium soluble TiCl ₃ ) chen polymers 1 (b) (C) 3 2 35.70 1.40 4th 36.80 1.27

Notes on the table:

(a) 1 and 2 are products of Examples 1 and 2, respectively

(b) Calculated as a solid polymer, based only on the TiCl ₃ content of the catalyst

(c) percentage of the total polymer formed (solid + dissolved)

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- 29 Example 5

Stauffer-AA was made using tributylphosphine, diphenylsulfone, and titanium tetrachloride the mill described in Example 1 ground. The grinding measures were as follows:

Stauffer- _{TiCl 3} -AA (20.1 g) was introduced into the mill under nitrogen, after which tributylphosphine in an amount of 0.15 mol based on the titanium trichloride content of the Stauffer AA was added while the mill was rotating. The mill was rotated at 120 revolutions per minute and water at 18 ^° C. was run over the outside of the mill.

After 16 hours of milling, the water spray was stopped and the mill stopped rotating. Diphenyl sulfone (0.05 mole based on the titanium trichloride content of the Stauffer AA) and then titanium tetrachloride (0.20 mole based on the titanium trichloride content of the Stauffer AA) were then added to the mill. The sulfon and titanium tetrachloride were added under an inert atmosphere of dry nitrogen. The titanium tetrachloride was slowly introduced via syringe while the mill was rotating and distributed as evenly as possible within the mill. The grinding was continued at 120 revolutions per minute and water was allowed to run at 18 ^° C. over the outside of the mill. After 24 hours, 100 ml of an inert aliphatic hydrocarbon liquid - as described in Example 1 - were added and

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milling continued for an additional 5 minutes. The resulting slurry was placed in a storage container convicted. The mill was rinsed three times with 100 ml aliquots of the same inert hydrocarbon diluent washed. The washings were transferred to a storage container.

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Claims (15)

272U232 claims 1. A method of grinding a solid compound of a transition metal from Groups IVA to VIA of the Periodic table with a smaller proportion of at least one organic compound, which is an organophosphorus compound and / or an organosilicon compound, characterized in that the solid compound des Transition metal also with a smaller proportion of at least one sulfur-containing organic Compound is brought into contact, which has been selected from the following group of compounds is: Sulphones of the formula Sulphonamides of the formula and Sulphides of the formula 709845/1099 where mean: X - independently of each other X - a halogen atom, an alkyl, aryl, alkoxy, aryloxy, alkyl thio, arylthio or a NRR group, where two X groups may form a saturated or unsaturated hydrocarbon ring together, Y - independently of any other Y - is a halogen atom, an alkyl, aryl, alkoxy, aryloxy, alkyl thio, arylthio or a NRR group in which two groups Y may form a saturated or unsaturated hydrocarbon ring together with an Group X and a group Y by a link between the two by a SO _? -Group connected phenyl groups can be replaced and the Vijrbondung either directly or through a group -O-, -CH ₂ -, -NR-, -S- or -CO-, Z - independently of any other Z - a halogen atom, a Alkyl, aryl, alkoxy, aryloxy, alkylthio, arylthio or an NRR group, where two groups Z together can form a saturated or unsaturated hydrocarbon ring, D - independently of any other D - a halogen atom, an alkyl , Aryl, alkoxy, aryloxy, alkylthio, arylthio or an NRR group, T -S-, -Ο-, -NR ¹ - or -CO-, R is a hydrogen atom or a hydrocarbon rest, R is a hydrocarbon residue, R is a hydrocarbon residue or a group η, m, ρ and q - each independently of one another - one 709845/1099 B 8127 integer from 0 to 5 and
χ a positive integer. 2. The method according to claim 1, characterized in that the smaller proportion of the organic The compound and the sulfur-containing organic compound are at least 0.01 and at most 1.00 mol 'per gram atom of transition metal present in the solid Compound of the transition metal is present. 3. The method according to claim 1 or 2, characterized in that the metal of the compound of the Transition metal has a valence that is below its maximum valence, and the compound represents a material containing titanium trichloride. 4. The method according to any one of claims 1 to 3, characterized in that the organophosphorus compound the formula R ¹ ₃ P (O) _y where y is 0 or 1. 5. The method according to any one of claims 1 to 3, characterized in that the organosilicon compound is an organosilane, a siloxane or a compound containing at least one Si-N bond. 6. The method according to any one of claims 1 to 5, characterized in that the sulfur-containing organic compound diphenyl sulfone, phenoxathiin-10,10-dioxide, Thioxanthene-10,10-dioxide, N, N-diethyl- 709845/1099 D 8127 4-phenoxybenzenesulfonamide, N, N-diphenylbenzenesulfonamide and / or is phenoxathiine. 7. The method according to any one of claims 1 to G, characterized in that the compound of the transition metal is ground with at least one organic compound, the milled product is mixed with a solution of the sulfur-containing organic compound and the mixture is heated ^{to a temperature of at least 60 ° C} . 8. The method according to any one of claims 1 to 6, characterized in that the compound of the transition metal is milled in the presence of the sulfur-containing organic compound. 9. The method according to claim 8, characterized in that during the grinding with the sulfur containing organic compound aluminum chloride or titanium tetrachloride are present. 10. The method according to claim 8 or 9, characterized in that all components. Together in be ground in a single grinding stage. 11. The method according to any one of claims 1 to 10, characterized in that the compound of the transition metal is milled with at least one organic compound, the sulfur-containing Puts compound in contact, and the product obtained with an inert aliphatic or aromatic Hydrocarbon is washed. 709845/1099 COPY 12. Catalyst for the polymerization of olefins with a content of 1) a compound of a transition metal and 2) at least one organometallic compound of aluminum or one that is not one of the transition metals counting metal of group IIA of the periodic table or a complex of an organometallic Compound of a metal from group IA or not belonging to the transition metals HA of the periodic table and an organoaluminum compound, characterized in that the component 1) of the Catalyst is the product obtainable by the process of claims 1 to 11. 13. Catalyst according to claim 12, characterized .j.'is, that it, in addition to any organic Lewis base contained in component 1), also 3) contains an additional amount of organic Lewis base. 14. Catalyst according to claim 12 or 13, characterized in that it is also 4) a substituted or urusubs t L tu ed polyene contains. 15. Use of a Katulysators according to one of the Claims 12 to 14 for the preparation of polymers or copolymers of olefinic monomers, wherein at least an olefinic monomer or a mixture of at least one olefinic monomer and ethylene are polymerized. 709845/1099 COPY