DE1545177C - Process for the preparation of catalysts for the polymerization of unsaturated organic compounds - Google Patents

Description

3 4

vinylcycloaliphatic compounds are used and mixtures or addition compounds of these

the. Examples include ethylene, propylene, groups of substances such as Al (OR) ₄ AI ₂ CI ₅ (R = aliphatic

Butene-1, hexene-1, heptene-1, octene-1, dodecene-1 and the rest, e.g. methyl or ethyl), are suitable. Also tri-

Isobutylene; Vinyl chloride, vinyl acetate, acrylic acid alkylsiloxyaluminum dihalides, such as R _s SiOAlCl ₂

derivatives; Styrene and its derivatives, vinylcyclohexane. 5 (R = aliphatic radical, ζ. Β. Methyl) can also

With the catalysts obtained according to the invention, such as AlBr ₃ , Al isopropylate, gallium trichloride or boron gates, the halides can be used with a simultaneous reduction in the number of halides. All these substances can beute the required amount of catalyst, the space-time-Aus also in the form of their addition compounds with AlkyU, z. B. in the polymerization of ethylene, on _% halides, such as CH ₃ Br or C ₂ H ₅ Cl, are used over twenty times as much as compared to the above. Finally, the commercially available written polymerization processes are also suitable, _{increased AlCl 3} -TiCl _{3 -KOmPIeXe,}
the. In addition, reproducible molar AlCl ₃ reacts with the polymeric silicon compounds used according to the invention and molecular weight distributions when the temperature is maintained. ... temperatures between 10 and ₇ 20O ^? C with resolution of the

The process according to the invention is preferably used as a solid, as long as no substantial molar concentration in the presence of inert auxiliary shots known per se is used; only given liquids, such as saturated aliphatic carbon, if any impurities in the AlCl ₃ are present, remain undissolved. Hydrocarbons, such as n-pentane, η-hexane, n-heptane, iso- When using very pure AlCl ₃ , ie with only octane, ligroin or cycloaliphatic or small aromatic residues, the hydrocarbons obtained, such as benzene or xylene, can be 20 solution immediately led to reaction with the metal compound. The IV. To VIII. Subgroups continue to be used,

Halogenated aliphatic and aromatic carbons and you can do the first stage in the polymerization vessel

Carry out hydrogens such as trichlorethylene or chlorobenzene yourself; otherwise filtered or decanted

can also be used as auxiliary liquids. one before. -

However, if possible, only a minimum of 25, based on a mol of polysiloxane unit, is possible

Auxiliary liquid, namely that amount which is required for 0.001 to 10, preferably 0.01 to 1 mol of compound

division of the reaction participants and for the removal of elements of the III. Main group are used,

the heat of reaction necessary is used. Leave the products made in the first stage

In the organs used for the production of catalysts, with the exclusion of moisture, for any length of time

ganopolysiloxanes of the formula given above is 30 preserve.

R preferably CH ₃ . - When moving these products with one or more

As further examples of R there may be mentioned alkyl radicals of the compounds mentioned in claim 1

such as ethyl, propyl and octadecyl, cycloalkyl radicals such as metals from IV. to VIII. B. TiCl ₄

Cyclopentyl and cyclooctyl, aryl radicals such as phenyl and or VOCl ₃ are formed after a short period of time when heated

Anthracyl, alkoxy radicals, cycloalkoxy radicals, aryloxy- 35 time, expediently in a somewhat inert auxiliary liquid.

residues or substitution products of any of the colored precipitates in very finely divided form, the

called organic radicals such as chlorophenyl or with aliphatic alcohols or ketones in solution

Tolyl residues. ■ go. These catalyst suspensions are air and

These organopolysiloxanes can be cyclic or sensitive to moisture, but not in air

be linear. You can make homopolymers out of themselves again - 40 spontaneously.

Bringing similar units, such as methyl water- Suitable compounds of the metals of IV. to siloxane polymers, or copolymers, for example, VIII. 3 mol percent meth tetrachloride, vanadium tetrachloride, chromium trichloride, oxyhydrogen siloxane, 1.5 mol percent cyclopentyl 45 molybdenum pentachloride, hafnium tetrachloride, hydrogen siloxane and 0.5 mol percent dimethyl rampantachloride, iron halide, cobalt halide units. Furthermore, the oxyhalides and oxyhaloalkoxides, such as the following units, may be present: 3,3,3-tri- z. B. isopropoxytitanium, zirconium oxychloride, Vafluorpropylwasserstoff-, Methylphenylwasserstoff-, octyl nadinoxytrichlorid, Vanadinoxychloridalkoxyde as tadecylwasserstoff-, Cyclooctylwasserstoff-, ethoxy _a 50 V OCI ₃ (OCH _{3) 3,} Molybdänalkoxychloride.wieMoCI ₃ -methylwasserstoff-, Chlorphenylwasserstoff-, Jodme - (0C _a H _B ) _a , and chromium oxychloride (CrO ₈ CI ₂ ), furthermore the hydrogen ethyl and dibromophenyl hydrogen siloxane alcoholates, such as titanium tetrabutylate, tetra- (2-ethylhexyl units. Mixtures of homolate) and tetraoctylate are also effective , Zirconium tetrabutylate, zirconium tetracyclopolymers, from mixed polymers or from both types hexylate, -tetra- (3-methylcyclohexylate), -tetra- (2-phenyl of polymers. All these polymers can contain up to 55 ethylate), thorium tetra-t-butylate and acetates and 90 mol percent, but preferably not more than acetylacetonates, such as titanium dichlorodiacetate, zirconium-10 mol percent of Si-bonded hydrogen tetraacetate and zirconium, thorium, cobalt and chromium mfreien siloxane units, such as dimethylsiloxane, acetylacetonate tri-, further halogen-containing metallmethylsiloxan-, phenylmethylsiloxane or SiO _4/2 -on- organic cyclopentadienyl compounds such as Diheiten contain. It is advantageous to use polysiloxanes end-blocked with triorgano-60 and monochloro-bis-icyclopentadienyl) compounds. of titanium, zirconium, vanadium and chromium or The degree of polymerisation of the polymeric silicon compounds cyclopentadienyltitanium trihalides.
bonds is between 3 and 120. Of course, you can also use mixtures of the

When carrying out the inventive method, use compounds and achieve the same

In the first stage, the amount of _{catalyst remaining in the first stage is preferably AlCl 3} 65 in most cases

used. In addition, however, other halides are also a further increase in the activity of the catalyst. The

or alkoxides, haloalkoxides, aroxides or metal contained in the metal compounds can be the

logenaroxyde of elements of III. Main group highest or a lower level of importance

own. It can - especially to achieve higher molecular weights - be expedient to use mixtures of compounds of the metals in two different valency levels, e.g. B. TiCl ₄ and TiCl ₃ or VOCl ₃ and VCl ₄ to use. S.

Higher molecular weights are also obtained if mixtures of compounds of different metals of subgroups IV. To VIII. B. TiCl ₄ and VOCl ₃ , used at the same time. The replacement of AlCl ₃ by aluminum isopropylate, ie a variation of the anion, is e.g. B. associated with an increase in molecular weight in the polymerization of ethylene. .

The metal compounds of subgroups IV to VIII can be used in amounts of 0.02 to 2, preferably 0.05 to 0.5 mol per mol of polysiloxane unit used be used. It has been found that in the formation of the catalysts of the invention from three Components the molar amount of compound of the IV. To VIII. Subgroup both significantly lower as well as much larger than the amount of compound of III. Main group can be.

The level of the molecular weight of the polymers obtained with the aid of the catalysts prepared according to the invention also depends on the proportions of these components described above. The chain length of the hydrogen polysiloxanes used and the reaction conditions, such as reaction time and temperature, also play a role in the preparation of the catalyst. ,

The presence of hydrogen halide accelerates the preparation of the catalyst, especially at low levels Concentrations, catalyst formation.

Before the polymerization, the catalyst can be removed from adhering in the preparation or in the polymerization vessel Free the hydrogen halide by evacuating it several times.

The inventive method can in the presence of - preferably finely divided - solid Carriers such as organic synthetic resins, e.g. B. polyethylene, polypropylene, polystyrene, or inorganic inert substances, e.g. B. NaCl or known under the name "Aerosil", obtained pyrogenically in the gas phase Silica.

The choice and amount of the solid support will of course depend on the intended use of the According to the invention catalyst to be prepared polymers set up. In terms of quantity, there are only limits to this extent set when the suspension carrier / auxiliary liquid should remain easily stirrable.

The addition of the carrier can be carried out all at once or in at any point during the procedure Shares are made. However, it is advantageous to use the solid carrier materials in finely powdered form for some time generally not longer than 1 hour, to be suspended in the reaction mixture from stage I with stirring.

The activity of the catalysts produced according to the invention from three components can additionally be increased by subjecting them to time and / or temperature aging. You can also go to or a kind of dilution aging follows during stage II, with the original catalyst concentration can be diluted in the auxiliary liquid to a concentration at which one wishes to begin the polymerization. Or you can do without the catalyst preparation at all on the presence of auxiliary liquids and dilutes only at the beginning or during the aging of the catalyst.

Because of the fine distribution of the catalysts obtained according to the invention, this differs from hitherto known catalyst systems, metering is very easily possible, which means that the polymerization is carried out continuously is of great benefit.

The particularly high effectiveness of the catalysts prepared according to the invention results from that even at normal pressure in the single gas process, unsaturated organic compounds, such as ethylene, can polymerize to high molecular weight, solid substances with good space-time yields.

As is readily apparent from the tables in the examples for the normal pressure polymerization of ethylene, by changing the molar ratios of the three components, eg. B. AlCl ₃ , TiCl ₄ and polysiloxane, achieve an optimum space-time yield of solid polyethylene with the same catalyst preparation and polymerization procedure and with the same amount of catalyst.

If _{the amount of TiCl 4 and polysiloxane is kept constant and the A1Q 3} concentration is increased step-by-step, an almost linear increase in the yield is surprisingly observed; after a maximum, the activity of the catalyst drops off steeply. The position and width of this maximum depends on the ratio of the compound of subgroups IV to VIII / polysiloxane. It was also found that the dependence of the space-time yield with increasing amount of compound of IV. To VIII. Subgroup and keeping a given concentration of compound of III. Group and polysiloxane, again based on the constant amount of catalyst, can be expressed by curves which, after initially having a linear increase, pass through a broad maximum and then gradually decrease.

The recovery of the catalyst described can be carried out with advantage even in the presence of the unsaturated monomers are carried out; if the latter are gaseous or become gaseous under the reaction conditions, they replace this here Usually inert protective gases such as nitrogen are used. ■ "

Polymerization is carried out either at normal pressure or at elevated pressures in a stirred vessel. In general you will get by with 10 atm. However, the catalysts prepared according to the invention can can also be used at significantly higher pressures, up to 100 atmospheres and more.

The polymerization temperature depends largely on the composition and activity of the catalyst, on the particular monomer and on the desired molecular weight. Temperatures between 20 and 200 ° C., generally between 50 and 130 °, are expedient ^. C.

The polymerization can be carried out at maximum dilution and / or with the maximum amount of catalyst begin, but can also meter in auxiliary liquid and / or catalyst suspension during the polymerization.

A continuous polymerization, e.g. B. in a pipe system with a circulation pump appears to dissipate the heat of polymerization particularly advantageous and can be with the inventively prepared Carry out catalytic converters particularly easily. It turned out that z. B. in the polymerization of ethylene neither in the stirred kettles nor in one

7 8

Tube system polymer deposits or film-forming polymers used very well

genes can be observed, even if there are still free minorities.

group element connection, e.g. B. TiCl _{4 is} present. For example, shows that made in accordance with the invention

With the inventively produced Kataly- polyethylene powder when applied to metal surfaces

Sators can also be used in discontinuous operation using the fluidized-bed sintering or immersion process

constant polymerization speed does not produce any bubbles and is completely pore-free

will. - - coatings.

The polymer products fall in a very finely divided chemical reaction, such as chlorination, sulfochlo-

Shape. This results in significant advantages of ration, introduction of hydroperoxide groups, etc.,

for the processing and isolation of the with the help of the io are easy and with the achievement of homogeneous products

obtain catalysts prepared according to the invention,

ten polymer products. ■ * '. ·' ■. The polymer powders can be particularly advantageous

While one z. B. with the previously known Kata as carrier materials for catalysts, such as those produced for lysers low-pressure polyethylene after ethylene polymerization, are used,
the decomposition of the catalyst with for example, methanol is used in the following examples The Methylerst after heating at 5 ° / oig ^he HNO ₃ completely color- wasserstoffpolysilpxan is linear and received by Trimethyllos, can be blocked with the present invention the manufacturing siloxy groups,
Provided catalysts obtained polymers · .-, '. "
even in the cold by simple washing, preferably with aliphatic alcohols, during the FiI ao examples 1 to 48
Tration or on the centrifuge practically completely free of adhering catalyst and pure white. In 50 ml of cleaned, well-vented paraffin contents. ·,. · .. hydrocarbons with a boiling point of 200 to 235 ^° C. are each

It turns out that then obviously an opti-methyl hydrogen polysiloxane (viscosity 32 cSt / 25 ° C)

painter decomposition and wash-out effect can be obtained as below with AlCl ₃ in the ratio indicated at 90 ⁰ C

can, if the aliphatic alcohols, in particular nitrogen, are heated to react. Included

Isopropanol or n-butanol, up to 15 percent by weight, the amounts are measured so that the total

percent, based on the alcohol, aliphatic ketones amount including the third component (TiCl ₄ )

are mixed in. Acetone is particularly suitable and always amounts to 5.0 g. After about 20 minutes comes in handy

Methyl ethyl ketone. 3 »everything went into solution. The solution is

The washing process can also be carried out in such a way that small residues enter the polymer

that you use the same auxiliary liquid as in the sationsgefäß, consisting of a 1-1 four-necked flask

Polymerization itself is used, which, however, is carried out with a stirrer, reflux condenser, gas inlet tube and

aliphatic alcohols and ketones in the thermometer above, pressed over, with another 50 ml

given ratio in small amount, e.g. B. up to 35 paraffin hydrocarbons with the specified boiling point

10 volume percent, based on the washing liquid, diluted range and heated to 9O ⁰ C. Now will

added. quickly add the specified amount of TiCl _{4 with a pipette}

This method has the advantage that it is added at the same time. Keeping the temperature constant

any low molecular weight polymer and stirring will after a short time become a colloidal,

products, e.g. B. waxes, observed during the washing process 40 dark-colored precipitate, which is in

removed. its number increased rapidly.

It is thus possible without great effort to use the method described above

Ash contents reach below 0.01 ° / o ^z u and the product catalyst made as follows. After 20 minutes

cent content of the grooves from the polymer product with acetone, the inert gas is replaced by dried ethylene

extractable low molecular weight fractions below 0.1 to 45 replaced the catalyst suspension with a further 100 ml

to reduce. . Paraffinic hydrocarbon diluted and 3 hours at

The polymers obtained are distinguished by a constant stirring speed and 85 ^° C. as much

a linear structure from which initiated by the high er- ethylene that just left some gas out

softening or Melting points is expressed. the apparatus emerges. The ethylene uptake remains

The higher molecular types in particular show almost 50% of the

a remarkable stant without the addition of stabilizers, provided that one

Thermal stability and when pre-pressing under increased thinning with fresh auxiliary liquid for the upright

Pressure and temperature conditions do not cause discolouration of uniform stirrability

exercises. ,wearing. ,

Further advantages of the very fine polymer grain are 55 After the specified polymerization time

are suitable for a wide variety of applications: the catalyst during cooling by adding

Easily mixed with additives, such as filler isopropyl alcohol, which is about 15% (vol.) Methyl

substances, dyes, lubricants, stabilizers, ethyl ketone, decomposes. The mixture is stirred for a further ₂ hours

networks. at normal temperature.

This results in better processability. The work-up is carried out by suctioning off the pure

from Z. B. filled polyethylene on the extruder, so white polymer product on the nutsche

that the addition of lubricants, such as organopoly and subsequent washing with the auxiliary liquid,

siloxanes, not necessary, but of course not from the 1% (vol.) of the above decomposition liquid, added

is closed. would. After drying at 8O ⁰ C., a very

For the production of z. B. Polyolefin dispersions 65 fine-grained polyethylene with grain sizes from 2 to

or polyolefin coatings on metals, glass or 3 μ. The powder melts (polarization microscope)

Paper, from insulation to metal wires, can be sown /, between'127 and 134 "C within I bis

those produced with the help of the Kafaly- 2 (irudcn.

Table I.

Dependence of the catalyst activity, expressed in gram polyethylene yield, on the molar ratio AlCl / TiCyPolysiloxane

Molar ratio 0.033 0.133 ' Molar ratio of TiCl ₁ to polysiloxane 0.232 0.332 0.57 AICl ₃ to polysiloxane 0 0 0.199 0 0 0 ' 0; ■ .... - '· ·. 27.8. .--: 0 , ■ ·, '·. _ ^ - \>: · .-- · ■■>'43.2. ·· - ■ - ^: 0.045 6.3 33.6 - - ■■■ .- · ^: 67.7 - 82.5. 73.1 0.09 - 54.0 54.2 93.9 101.8 91.5 0.135 10.2 62.5 91.8 84.0 ■ 85.9 83.9 0.18 ..-- ■ 14.4 69.1 81.5 86.5 86.0 64.2 0.225. - 51.8 - 85.6 69.6 ■ - ■ - 51.9 32.0 0.27 0.9 2.4 62.7 2.3 2.0 = ■■ '- ■■ 1.5 0.315 0 ■ 0 3.6 0 0 0 0.36 Ibis 6. 7 to 15 0 24 to 31 32 to 40 41 to 48. example 16 to 23

The stated yields of polymer product can be used in most of the examples given Increase further if you use a higher stirring speed and / or a longer one if possible Polymerization time selects.

B e i s ρ i e 1 49

According to the invention, a catalyst is prepared from methyl hydrogen polysiloxane, AlCl ₃ and TiCl ₄ , the amounts used and the molar ratios corresponding to Example 35. However, there are the filtered solution from the reaction polysiloxane / AlCl _3, being used instead of 50 ml of diluent 30 ml, 5 g feinstgepulvertes, dry and deaerated polyethylene added and the suspension at 50 ⁰ C for 10 minutes, stirred well. The mixture is then diluted with a further 70 ml of paraffinic hydrocarbon and the same procedure as in Example 35.

If this catalyst is used, 114.5 g of white polyethylene powder with a melting point of 131 ° to 132 ° C. are obtained. _; .

Example 50

Catalyst preparation and polymerization as described in Example 49, instead of nitrogen however, dried and purified ethylene is used as a protective gas.

When using the catalyst thus prepared according to the invention, there is a further increase in yield Recorded: 133.0 g of polyethylene, the properties of which are similar to those of the previous ones The products mentioned in the examples.

Example 51 /

The procedure described in Example 35 is followed, but under-works in the preparation of the catalyst Ethylene gas protection. -

In the application of the catalyst according to the invention thus produced 120.7 g of white polyethylene are obtained with a melting point of 130.5 to 131 ⁰ C.

B e i s ρ i e 1 52

The molar ratio of the three components is selected as given in Example 18, but the catalyst suspension (100 ml of ligroin) is stirred for an hour at 85 ^° C. and after dilution with a further 100 ml of ligroin for 1 hour at the same temperature. After adding 100 ml of solvent again, evacuation takes place briefly three times (150 mm Hg), each

ao Weil brought back to normal pressure with ethylene will.

The use of the catalyst so prepared according to the invention in ethylene polymerization and working up is carried out as described in Example 18. There are 125.5 g of fine-grained white polyethylene powder receive; Particle size between 1 and 3 μ, melting point 132 ° C, molecular weight 90,000 (the molecular weight was determined viscometrically in decalin at 135 ° C and according to H. W e s s 1 a u, Kunststoffe, 49, p. 330, 1959, calculated). ■

That with the catalyst according to Example 18 without dilution aging The polyethylene produced had a molecular weight of 61,000.

For example 53

10 ml of methyl hydrogen polysiloxane and 3 g of _AlCl3 are placed in 100 ml ligroin (bp. 70 to 85 ⁰ C) with stirring and Erwärmeir at 90 ⁰ C for reaction. After 22 minutes, almost everything has dissolved, with the exception of a small amount of residue. The mixture is filtered with the exclusion of moisture and the solvent is evaporated off in vacuo (10 mm Hg). A mobile, almost colorless oil remains, the viscosity of which hardly differs from the hydrogen polysiloxane used.

The Al / Si ratio in the oil is determined analytically and then enough is removed that after dilution with 100 ml of paraffinic hydrocarbon boiling from 90 to 140 ° C and after addition of TiCl ₄ 'in a molar ratio of TiCl ₄ / polysiloxane of 0, 33 together with 5 g of the three components are available for catalyst preparation. '' Even when heated under nitrogen, a dark, black-brown catalyst suspension is formed which - after a reaction time of three hours at 90 ° C, hardly increases any more. After dilution with a further 200 ml of hydrocarbon and brief stirring, the resulting very finely divided suspension can be stored for any length of time under lock and key or air and moisture exclusion.

Before use, you can easily settle the slowly settling catalyst, for. B. by a stream of inert gas, put back into suspension. This catalyst suspension can also be used without Press further through openings with clear widths of less than 1 mm.

Half the amount of the catalyst suspension prepared according to the invention as described above is used after 3 months of storage and after a short period of

blow pressed with purified nitrogen in an autoclave of 0,711, still 250 ml hydrocarbon added and after pressing atm with ethylene gas to 10 at this pressure and polymerized at 65 ⁰ C. The polymerization begins immediately, moderately exothermic. Appropriate valve position ensures that fresh ethylene gas flows in continuously. It is noticeable that the uptake of ethylene is particularly uniform. Only if stirring is difficult does the polymerization end after 5 hours.

After blowing off the catalyst in the autoclave, it is decomposed with 150 ml of gasoline which contains 5% by volume of a mixture of 90 parts by volume of isobutyl alcohol and 12 parts by volume of acetone, and the mixture is briefly stirred. After removal of the polymer material with a further 200 ml of solvent mixture is filtered on a suction filter, washed with a solvent mixture and dried at 8O ⁰ C. Pure white, fine powder, 125 g, melting point 131.5 ° C; low molecular weight fractions extractable with acetone: 0.08%.

B e i s ρ i e 1 54

According to the invention 5 ml of methylhydrogenpolysiloxane with 2 g of distilled Al isopropylate by brief heating at 85 ⁰ C are reacted. A colorless, fairly viscous oil results. This oil "is taken up with 50 ml ligroin (bp. 80 ° -90 ° C) mixed with 1.2 ml of TiCl _4. Upon heating a finely divided, dark brown catalyst precipitated at 50 ⁰ C, the amount thereof is increased rapidly Appropriately diluted. If the work is too concentrated, gelatinous precipitates can form.Both the gelatinous as well as the suspended catalysts dissolve clearly in, for example, butyl alcohol with a deep blue-violet color.

The finely dispersed catalyst obtained according to the above information is in one Polymerization vessel used for normal pressure polymerization of ethylene.

At 4 hours of polymerization and workup as in the previous examples, 39.8 g of white polyethylene powder are obtained of melting point 133.2 ⁰ C.

An analogous test procedure with non-pretreated polysiloxane reveals no catalyst formation; this only sets in for much longer periods of time, at higher temperatures and at a much lower rate Amount a.

Example 55

500 mg sublimed AlCl ₃ are reacted with 2 ml of methyl hydrogen polysiloxane in 40 ml paraffin hydrocarbon having a boiling range from 90 to 14O ⁰ C at 100 ° C under stirring. Without filtration is treated with 150 mg of sublimed FeCl ₃ and 0.5 ml of TiCl ₄ and heated to 110 ⁰ C. A catalyst with a dark, brown-violet color is produced in large quantities. Further auxiliary liquid is expediently added during the last phase of the catalyst preparation. The catalyst is clearly soluble in deaerated butanol with a dark purple color. ·

If you use the information given above according to the invention obtained catalyst for ethylene polymerization under normal pressure and under conditions As described in Examples 1 to 48, 78 g of white polyethylene powder are obtained.

_{If no FeCl 3 is} used in the preparation of the catalyst according to the invention, but only 1.05 g of TiCl ₄ , 69.5 g of polyethylene are obtained when this catalyst is used. . ./...'...,L

Be i s pie I 56 "

A reaction solution which is obtained from 5 ml of methyl hydrogen polysiloxane and 2.0 g of AlCl ₃ and 100 ml of gasoline (boiling point 110 to 150 ° C.) is used to prepare

ίο with 1.2 ml of vanadium oxychloride at 90 ° C according to the invention a catalyst, which in finely divided form and_ dark green color is omitted and active is enough to turn ethylene into a high-molecular, solid substance with a melting point of 133, - ° C in the single-gas process

to polymerize. .-. '■ _.

- If, instead of AlCl _3, distilled Al isopropylate is used, almost the same test results are obtained, but the catalyst has a somewhat lower activity for the polymerization of ethylene.

activity. _v

Comparative tests with non-activated methyl hydrogen polysiloxane show that both the catalyst formation (light green, little) and the Polymerization of ethylene is much slower.

Examples 57 and 58

2 ml of methyl hydrogen polysiloxane and 0.23 g of AlCl _{3 are left} in 30 ml of paraffinic hydrocarbon (bp.

200 react to 232 ° C) at 9O ⁰ C, filtered and, with 0.6 ml of TiCl ₄ at 87 ⁰ C for 20 minutes under Äthylengasschutz according to the invention a catalyst. To the. Using the same, it is diluted with a further 200 ml of paraffinic hydrocarbon, heated briefly to 75 ° C. and the catalyst suspension is pressed into a 1-1 stirred autoclave. Polymerization is carried out with purified and dry ethylene at 10 ° and 80 to 85 ° C. Another 150 ml of paraffinic hydrocarbon

■ are metered in during the polymerization. After catalyst decomposition and work-up, as in the described in the previous examples, with a space-time yield of 53 g / h / l 161.4 g are white Polymer powder obtained; Molecular weight 60,000, ash content 0.01% -

An analogous experiment using dilution aging during or after the inventive method Catalyst preparation, after the first preparation phase (30 ml, 20 minutes) with 50 ml Solvent diluted and stirred for a further 30 minutes, then diluted as indicated above and heated and aged overnight at normal temperature shows a substantial increase in molecular weight to 120,000 with a yield of 157.8 g and a space-time yield of 66.7 g / h / l; Ash content 0.009%.

Comparison tests'

Is prepared by a reaction of 10 ml of methylhydrogenpolysiloxane and 3g AlCl, at 90 ⁰ C in 100 ml of petroleum ether and subsequent filtration, a solution diluted with a further 200 ml of benzene, the solution was suppressed in a stirred autoclave, heated to 85 ° C and pressed with ethylene on 10 atü. No decrease in pressure is observed; an increase in pressure to 50 atmospheres and / or temperature variation between 50 and 150 ⁰ C can also be no Äthylenaufnahme recognize. No solid polymer product after cooling down and opening the autoclave.

13 14

The same batch, with a 1-1 stirred autoclave being pressed in instead of the polysiloxane. One polymerizes

3 ml of TiCl ₄ are used, shows that the AlCl ₃ ethylene at 9 atmospheres and 70 to 75 ⁰ C. With this method

only a very small portion (about 5%) i ^m 'gasoline examined observes a very uniform exothermic

solves. Without filtration, the AlCl ₃ suspension, like the reaction, is evidently due to the great dilution.

described above, used for the polymerization. No 5 things. With a space-time yield of

solid polymer product. , 30 g / h / l obtained 132.5 g of white powder. Melting point

η ■ ■ _M o 132.3 "C, molecular weight 80,000; with acetone ex-

- ^P tractable wax 0.08%.

In general, the procedure is as in Example 57. The polymerization batch is reproducible, ie, it is written, but at the same time as the TiCl ₄ , the yields and properties of the polymer-0.5 g of finely powdered, violet TiCl ₃ are added. The catalyst products remain essentially unchanged,
Sator formation takes place very quickly and extensively, whereby, on the other hand, it is only noticeable for comparison that the TiCl ₃ apparently undergoes a reaction with the three components without a separate reaction and changes into the dark brown catalyst color. management for 15 minutes at 88 ⁰ C in the polymer catalyst preparation at 89 ° C for 15 minutes. 15 sation vessel a catalyst, so under otherwise

When using this catalyst, 145 g of the same conditions only 102 g of polyethylene with a '

Obtained polyethylene, the polymer product having a molecular weight of 46,000 and wax proportions of

this example apparently obtained through the influence of the 0.42%. ~

turned TiCl ₃ in flakes and fibers. A further significant worsening of the work-up is therefore expediently mechanical prey if, for the sake of comparison, the catalyst niche comminution in gasoline suspension, for example in preparation in a single-stage reaction in 550 ml of a star mix, is switched on. Melting point 132.5 to. Paraffinic carbon is made; it is 134 ° C, molecular weight 85,000. Only 11.3 g of polyethylene with a high ash content

'. . isolated.

Example 1 60 ₂ .

According to the invention, one prepares in the first reaction

from 4 ml of methyl hydrogen polysiloxane and 0.43 g of inventive catalyst preparation in two

technical AlCl ₃ in 50 ml of ligroin (bp 70 to 8O ⁰ C) reaction phases from 1.3 ml of methyl hydrogen poly-

at 8O ⁰ C and subsequent filtration a solution, siloxane, 0.385 g AlCl ₃ and 0.76 ml TiCl ₄ in 25 ml Pa-

this added rapidly with 1.2 ml of TiCl ₄ and prepares below 30 refine hydrocarbon (bp. 200 to 230 ⁰ C) at 87 ⁰ C.

Ethylene gas protection at 88 ° C for 15 minutes one for 16 minutes under ethylene protection; that included

Catalyst, which is used as a catalyst support for the polymerization of the polyethylene formed.

Ethylene in a 1-1 stirred autoclave with 200 ml Li- To use the inventively prepared

thinned groin. After dilution with a further 225 ml

It is polymerized at 7O ⁰ C and 10 atm, after 35 paraffin hydrocarbon is heated to 75 ° C, in a

30 minutes and after a further 16 minutes each 200 ml of 1-1 stirred autoclave are pressed in and pressed on

Ligroin are added. The polymerization of ethylene at 10 atm polymerized at 83 ⁰ C. Encore

uniformly exothermic, and it is also evident after 2 · 200 ml of solvent during the polymer

Failure of the stirrer still strong ethylene uptake, sation. 146.7 g polyethylene in a space-time configuration

so that polymerized for a long time without stirring 40 bags of 40 g / h / l; Molecular weight 37,000.

can be. After relaxing and cooling down, that's the. . _{Λ / 1} ■

Autoclave completely filled with polymer product, which Example 64

in a star mix with a gasoline-alcohol-ketone mixture. According to the invention, 225 ml of methyl water

is cleaned. 297.5 g of pure white powder in a material polysiloxane with 64.5 g of technical grade AlCl ₃ in 4 1

Space-time yield of 43.2 g / h / l, melting point 45 paraffinic hydrocarbon (boiling range 90 to 14O ⁰ C)

130.5 ⁰ C. The autoclave is no skinning fixed under stirring. Of little unsolved

placed. Residues are filtered off with quartz wool and

Example 61 ^m '* ^ »~' solvent rinsed. Then will

110 ml of TiCl ₄ added under ethylene protection and

In the first reaction stage, the mixture is heated from 841 mg of 50, with the catalyst already exhausting at 65 ^° C.

AlCl ₃ and 2.81 ml of methyl hydrogen polysiloxane begins to fall in. During 35 minutes between

100 ml of gasoline (boiling range 110 to 150 ⁰ C) held by he 85 and 100 ⁰ C, then 40 minutes at 75 to

warming a solution and then added with 1.68 ml of 8O ⁰ C. After addition of another solvent 51

TiCl ₄ and 0.54 ml VOCl ₃ - after 20 minutes at 87 bis, the catalyst suspension gradually increases from 75 to

89 ⁰ C has cooled down ^{55 60 0} C under dry nitrogen,

formed according to a black catalyst suspension. From the catalyst prepared according to the invention

This catalyst polymerizes ethylene under normal 1.61 for other experimental purposes

painting pressure or pressures up to 10 atü too high molecular weight and the main amount in a 150-1 stirred autoclave

larene polyethylenes (molecular weight over 400,000). pressed, in which 1001 presented dispersant

_R. . Turn 60. Ethylene is polymeric at 10 atmospheres and 75 ^{° C}

Example _s j _ert ^ ^^ something else during the polymerization

From 2 ml methyl hydrogen polysiloxane, 0.2 g AlCl ₃ paraffin hydrocarbon is added.

and 1.2 ml of TiCl ₄ in 50 ml of paraffin hydrocarbons - the stirrability of the resulting 40 minutes is ensured

material (Kp. 90 to 140 ⁰ C) as in Example 61 of invention already impaired polymer suspension. After

according to a catalyst prepares. 65 Cooling and blowing off become dilution

After adding 500 ml of solvent and 15 liters of gasoline, the polymer slurry

warming to 75 ° C is briefly evacuated three times (150mm continuously through a tube system on a centrifuge

Hg) and then abandoned the catalyst suspension in one. It is also continuously about

15 16

the same. Volume amount of decomposition or with the polymer product immediately as a white, fine washing liquid, consisting of paraffin hydro- granular PVC accrues. Yield after filtration and fabric with 3.5 percent by volume isopropyl alcohol, the 15% washing on the filter 140 g, K value 57, ash content Contains acetone, added. Also, on the 0.01%.

Centrifuge with the above washing liquid continuously 5 Example 68

washed. ,

The polymer product, upon drying, precipitates as pure. 5 ml of one having trimethylsiloxy groups is left

white powder with an ash content below 0. Ql% wkI end-blocked polysiloxane, which 54 mole percent below 0.1% of the proportion that can be extracted with acetone. OSi (CH ₃ H) units and 45 mol percent dimethyl-29.4 kg polyethylene in a space-time yield of iosiloxane units, with 0.8 g AlCl ₃ in 50 ml Ben-30 g / h / l, melting point 132 , 2 ° C, molecular weight react zin (boiling range 100 to 150 ° C) and dropwise 119 000, heat resistance after V icat (5 kg loading then at 20 ⁰ C with good stirring 0.5 g CrO ₈ Cl ₂ in ■ utilization) 75 ° C. The 10 ml of gasoline pressed for the Vicat determination. In an exothermic reaction, a sample shows no discoloration, while a poly- dark brown colloidal solution. At 45 ° C ethylene commercial grade additionally with a comparable molecular added 15 ml of TiCl ₄ and 0.4 at 85 ⁰ C, a weight was discolored yellow brownish. dark purple-brown catalyst prepares, the opposite

If you work the same approach under analogous over ethylene and propylene extraordinarily polymeric conditions with a decomposition .bzw. Is washing active.
liquid that does not contain ketones, Example 69

an ash content of 0.08% and extracting ao with acetone

^ bare shares of 0.25% found. According to the invention, a solution of 5 ml

s J. Methyl hydrogen polysiloxane in 95 ml of purified,

Example 65 nitrogen-saturated gasoline from boiling point 100 to

140 ⁰ C given 0.168 g of aluminum chloride. To

Is prepared from 5 ml of methylhydrogenpolysiloxane 25 2 hours of heating at 80 to 90 ⁰ C with stirring

and 0.5 g of technical AlCl ₃ in ligroin (bp. 70 to 25 ml of the clear solution with 0.60 ml of titanium-8O ⁰ C) and filtration, a solution, of these added tetrachloride and 20 minutes at 90 ⁰ C for 3 ml of distilled titanium o-butyl ester and warmed further reaction. After the formation of the under nitrogen protection. The result is a red-brown, red-brown catalyst suspension is can be used with 75 ml fine precipitate, which was diluted as a catalyst for poly-30 fuel and the colloidal temporarily polymerization of 1-olefins and aged solution a further 2 hours at 85 ⁰ C.

clear in n-butanol with a deep blue-violet color - At a molar ratio of 3.62: 0.05: 1.0 (Si / Al /

j solves. 'Ti) is the catalyst used for the polymerization

For example 66. Sator amount 2.33 g.

35 After transferring into the rinsed with ethylene

5 ml of methyl hydrogen polysiloxane are reacted with 0.1 g of ll-glass pressure reaction vessel may according to 4V ₂ AlCl _StUn-8 in 50 ml of ligroin (bp. 70 ° -80 ° C) ended the reaction of polymerization at 70 to 8O ⁰ C and 8 to. After filtration, 105 g of purified polyethylene from the Mosion of 1 g of TiCl ₃ and 0.5 g of TiCl ₈ in ligroin, which are obtained in a molecular weight of 74,000, the Geeiner ball mill is manufactured, are added to 100 ml of a suspension 10 atmospheric pressure after 40 samtlösungsmittelmenge 0.551 gasoline at the time the addition of 0.2 ml of TiCl ₄ at 100 ⁰ C according to the invention is the interruption with isopropanol. :

a catalyst prepares. ■

} With the black catalyst suspension in 'Example 70

a pressure autoclave liquid propylene at 115 bis

12O ⁰ C polymerized. A tough, sticky composition is obtained, according to the invention, of the catalyst and rubber-like mass, which takes place after the catalyst suspension as in Example 69, the decomposition and thorough washing with alcohol-ketone solvent amounts as well as the Tempe mixture being white , asbestos-like and fibrous proportions and times are kept the same. The impression remains. 15.6% of the amount of aluminum chloride extracted with ether can be added to 1.0 g; the residue is highly crystalline, high melting point. At a molar ratio of 3.62: 0.32: 1.00 155 point to 165 ⁰ C. (Si / Al / Ti), the total used Kataly

Sator amount 2.54 g.

Example 67 The polymerization is carried out at

the same conditions as in Example 69. After

10 ml of methyl hydrogen polysiloxane are in 200ml 55 llstündiger reaction time hog purified petroleum (bp. 90 to 14O ⁰ C) are mixed with 0.5 g of AlCl ₃ at 9O ⁰ C polyethylene of molecular weight 27 000 placed with one to the reaction. The filtered solution will now receive an amount of gasoline of 0.501. 90% of the polymer _{mixed with 1 ml of TiCl 4} and at 105 ° C. for 2 hours are formed during the first hour. _;
which a catalyst according to the invention prepares. . . "

The cooled catalyst suspension becomes an Example 71

Night with exclusion of air and moisture. Carrying out the catalyst preparation as

stored, then with a further 100 ml of paraffin carbons, the polymerization also takes place diluted under the hydrogen and put into an autoclave settings of Example 69. The amount of aluminum chloride is filled. 250 g of distilled and purified vinyl chloride is increased to 3.0 g. The amount of catalyst is to be pressed with nitrogen and the polymerisation 65 g of 3.04 at a ratio of 3.02: 1.08: 1.0 sation at 7O ⁰ C and 10 atm for 20 hours throughput (Si / Al / Ti ).

guided. After cooling and blowing off, the When using the obtained according to the invention

Catalyst decomposed with n-butanol-acetone mixture, the catalyst can be by 2 ¹ / »hours polymerisation

17 18

sation time 45 g of purified polyethylene from the molecular brown catalyst precipitate is 20 minutes

Large weight 32,400 with a gasoline merge of 0.3 l, stirred at 87 ° C and after diluting to 100 ml

keep. After a reaction time of one and a half hours, no gasoline can be kept at 85 ° C for a further 2 hours,

further ethylene uptake can be determined. The amount of ca-

5 talysators is 3.0 g at a molar ratio of

: B e i s ρ i e I 72 3.15: 0.41: 1.0 (Si / Al / Ti). After 1.5 hours of polymerization under the conditions of Example 70 in

When using 0.5 g of aluminum chloride, the 0.51 of petrol will be 175 g of purified polyethylene

Amount of hydrogen polysiloxane increased to 10 ml, average molecular weight 68,000 obtained,
and diluted with 90 ml of gasoline. The further through- io

The procedure is analogous to Example 69. In a Molyer example 78

ratio of 7.0: 0.15: 1.0 (Si / Al / Ti) is the Ka- *:

amount of catalyst 3.66 g. ^J 1.437 g of AlCl ₃ are mixed with "4.82 ml of methyl hydrogen

When using the polysiloxane obtained according to the invention in 107 ml of gasoline for 40 minutes at 82 ° C

Catalyst brought 15 reaction after 4 ^x / _{2 hour polymerization.} To 50 ml of this solution become

at an amount of 0.551 gasoline as an auxiliary liquid, 1.27 ml of TiCl _{4 were} added and the ^{mixture was heated at 82 °} C. for 20 minutes

Stir 120 g of purified polyethylene of molecular weight. The brown catalyst suspension that

84,000 won. forms slowly, becomes with after further dilution

n / A; cn, · a1 71 50 ml of gasoline ^{held at 85 °} C. for a further 2 hours.

ao With the same molar ratio as in Example 77

The amount of aluminum chloride used is loaded with 3.0 g of this catalyst after 1.5 hours

carries 6.0 g, whereby, under otherwise identical conditions, the polymerization time under the conditions of the

The amounts of polysiloxane mentioned in Example 72, for example 69 in 0.501 gasoline, 80 g of purified polyethylene

be turned. Obtained at a molar ratio of 44,000 molecular weight.

7n.iM.1n «ϊ / δι / τλ ^a 5 I ⁿ Examples 69 to 78 is linear methyl

hydrogen polysiloxane with a chain length of

5.04 g of catalyst are used. 30 silicon atoms used.

After 10 hours of polymerization, 0.51

Gasoline HOg purified polyethylene from molecular example 79

weight 53 300 received. 30th . ■,

'η · · 1 74 1.40 g of aluminum chloride with 23.0 ml

Hei game / 4 methyl hydrogen polysiloxane - containing 6 Si atoms

Under the conditions of Example 69, 20 minutes at 85 ° C. in 10 ml of gasoline are used per chain

1.6 g of AlCl ₃ reacted with 15 ml of methyl hydrogen polysiloxane and with 3.81 ml of titanium tetrachloride

diluted with 85 ml of gasoline to react. 35 offset. Otherwise, as in Example 76,

At a molar ratio of 10.0: 0.30: 1.0 (Si / Al / worked ..

Ti) and an amount of catalyst of 5.04 g. With 3.0 g of this catalyst at a molar ratio

the yield after 8 hours of polymerization is 9.85: 0.30: 1.0 (Si / Al / Ti)

and with 0.61 gasoline 170 g of purified polyethylene from _a polymerization time of 47 hours in 0.251 gasoline

Molecular weight 156,000. 40 50 g of purified polyethylene with an average

_n . . , _. Obtained molecular weight of HO 000.

Example 75 ^e

The amount of aluminum chloride is increased to 10.0 g. . Example 80
Otherwise, the same conditions apply as in Example 74. 1.22 g of aluminum chloride with 18.0 ml

The amount of catalyst is 7.20 g for one mole of methyl hydrogen polysiloxane - 100 Si atoms per

ratio of 10.0: 2.45: 1.0 (Si / Al / Ti), whereby according to the chain - in 10 ml of gasoline for 20 minutes at 85 ⁰ C for

2.8 hour polymerization time brought 150 g of polyethylene reaction and 3.32 ml of titanium tetrachloride

can be obtained with a molecular weight of 42,000 in 0.51 gasoline. offset; then continue as in Example 77.

50 3.0 g of this catalyst at a molar ratio

. '· Example 76 of 9.85: 0.30: 1.0 (Si / Al / Ti) gives after one

Polymerization time in 0.201 gasoline for 2 ^{3/4 hours}

There are 0.766 g of aluminum isopropylate among the 32 g of purified polyethylene of the medium molecular

Conditions of Example 74 reacted, weight 93,000. "

50 ml of this solution are mixed with 1.2 ml of titanium tetra 55 Example 81

chloride added and treated further as in Example 69. *

The amount of catalyst is 4.98 g with a mol- a) A mixture of 5 ml of methyl hydrogen poly ratio of 10.0: 13.0: 1.0 (Si / Al / Ti). siloxane with 5OcSt / 25 ° C and 2 g freshly distilled

After 2.15 hours of polymerization in 0.651 tem aluminum isopropylate, under nitrogen

Gasoline, 200 g of polyethylene of molecular heated 9 minutes 60 to 85 ⁰ C. The thus obtained

weight 147,000 received. colorless oil is first mixed with 100 ml paraffin

_R. . . __ hydrocarbon, bp. 80 to 9O ⁰ C and then

Example // mixed with 1.2 ml TiCl ₁ and under nitrogen

3.354 g AlCl ₃ are heated with 11.5 ml Methylwasserstoff- 10 minutes 85 ⁰ C,
polysiloxane placed in 10 ml gasoline for 20 minutes at 88 ⁰ C for 65 according to the invention thus obtained catalyst reaction, hydrochloric acid and chlorosilanes was suspension are mixed with 200 ml Paraffinkohlenentbunden. 6.7 ml of titanium hydrogen of the type described above, tetrachloride, are added to this solution. After the immediate formation of the diluted ethylene and introduced instead of nitrogen,

the temperature being held at 75 ° C. for 4 hours. 35.8 g of polyethylene were obtained.

b) For comparison, the procedure described above under a) was repeated with the modification that to prepare the catalyst suspension, a mixture of 5 g of methyl hydrogen polysiloxane with 50cSt / 25 ° C, 2 g of freshly distilled aluminum isopropoxide and 1.2 ml of TiCl ₄ in 100 ml of the paraffinic hydrocarbon was heated to 85 ° C. under nitrogen for 20 minutes.
Only 4.5 g of polyethylene were obtained.

Example 82

a) A mixture of 5 ml of methyl hydrogen polysiloxane with 50 cSt / 25 ° C and 2 g of AlCl ₃ in 100 ml of paraffinic hydrocarbon with a boiling point of 110 to 150 ° C was heated to 90 ° C under nitrogen for 20 minutes. The resulting solution was filtered,

mixed with 1.2 ml VOCl ₃ and 0.2 ml TiCl ₄ and heated to 90 ° C for 10 minutes under nitrogen.
The catalyst suspension thus obtained according to the invention was diluted with 200 ml of paraffinic hydrocarbon of the type described above and ethylene was passed in instead of nitrogen, the temperature being kept at 80 ° C. for 3 hours. 35.0 g of practically colorless polyethylene were obtained.

b) For comparison, the procedure described above under a) was repeated with the modification that a mixture of 5 ml methyl hydrogen polysiloxane with 50cSt / 25 ° C, 2.0 g AlCl ₃ , 1.2 ml VOCl ₃ and 0 , 2 ml of TiCl ₄ in 100 ml of the paraffinic hydrocarbon of the type described above was heated to 90 ° C. under nitrogen for 30 minutes. Only 21.0 g of slightly greenish-colored polyethylene were obtained.

Claims (6)

1 2 of the periodic table and polymeric silicon compounds: fertilizers containing Si-bonded hydrogen, unsaturated organic compounds, especially olefins, 1. Process for the preparation of catalysts at low pressures and temperatures, expedient for the polymerization of unsaturated organic 5 in the presence of inert auxiliary liquids, too high compounds from organopolysiloxanes of the all-molecular solid and slightly branched products common formula can polymerize or copolymerize. It is also known that when using the above catalysts by adding compounds that «.» _{Generally known as} Friedel-Crafts catalysts can achieve an increase in the rate of polymerization. These additional catalysts (R = optionally halogenated alkyl, cyclo previously relied during · catalyst preparation alkyl, alkoxy, cycloalkoxy, aryl or aroxy in the polymerization vessel or at the beginning or during rest; m = 1, 2 or 3; " = 0, 1 or 2; m - \ - η 15. However, it was found that then = 1, 2 or 3) and halides, oxyhalides, the molecular weights with regard to their distribution alcoholates, halogen alcoholates, aroxides or and size different polymerization approaches haloaroxides of elements of III. Mainly not or only with difficulty were reproducible. In addition, group of the periodic table and halides, the rate of polymerization and the Aus-Oxyhalogeniden, Oxyhalogenalkoxden, Alcohol left a lot to be desired. Occasionally latates, halogen alcoholates, aroxides and halogen-discolored products were also obtained. aroxides, acetates, acetylacetonates or cyclo- ■ In the process according to the invention, dapentadienyl compounds of metals of the IV. to against catalysts for the polymerization are unge-VIII. Subgroup of the periodic table, optionally saturated compounds are obtained which do not have the disadvantages described above, if in the presence of auxiliary liquids, d a- 95. In contrast, characterized in that in addition to the best known catalysts for the two separate reaction stages, the catalysts according to the invention contain no aluminum niche compounds, the organopolysiloxanes, if necessary in the presence of the unsaturated organopolysiloxanes. alkyls and are therefore not self-igniting in the air - 10 to 200 ⁰ C initially with the compounds of 30 Hch. · . Elements of III. Main group can react, the subject of the invention is a method for producing where for 1 mole of siloxane 0.001 to 10 moles of connection of catalysts for the polymerization of elements of III. Main group of unsaturated organic compounds are used from organo and the product obtained is an- polysiloxanes with structural units of the general, followed by the compounds of metals of the formula
IV. To VIII. Subgroup converts, with on 1 mol of siloxane 0.02 to 2 mol of the metal compound _D t come into use. ■ ^ 2. The method according to claim 1, characterized in that 0.01 40 per mole of organopolysiloxane
to 1 mole of compounds of elements of the III. Main group and 0.05 to 0.5 mol of the compounds (R = optionally halogenated alkyl, cycloalkyl, compounds of metals from IV. To VIII. Minor alkoxy, cycloalkoxy, aryl or aroxy radicals; m = 1, 2 group used. Or 3; η - 0,. 1 or 2; m + η = 1,2 or 3, and 3. The method according to claim 1 and % characterized 45 halides, oxyhalides, alcoholates, halogens that one is used as a compound of the alcoholates, aroxides or haloaroxides of III. Main group halides and / or alcoholates elements of III. Main group of the periodic table of aluminum used. and halides, oxyhalides, oxyhaloalk- 4. The method according to claim 1 to 3, characterized by oxides, alcoholates, halogen alcoholates, aroxides, characterized in that in the first process 50 haloaroxides, acetates, acetylacetonates or rensstufe obtained reaction product before the cyclopentadienyl compounds of metals of the IV. further implementation of insoluble and / or up to VIII. subgroup of the periodic table, possibly volatile Separates components. if in the presence of auxiliary liquids, thereby 5. The method according to claim 1 to 4, characterized in that it is separated into two, that the catalysts are used in opposite reaction stages - optionally in the presence manufactured from solid carriers. . of unsaturated organic compounds - the or- 6. The method according to claim 1 to 4, characterized ge ganopolysiloxane at 10 to 200 ⁰ C initially with the indicates that the preparation of the catalyst compounds of elements of III. Main group sators can react in the presence of dry halogen, taking 0.001 to hydrogen per mole of siloxane. 60 10 mol compound of elements of III. Main group are applied, and the product obtained then with the compounds of metals of the IV. To VIII. Subgroup converts, with 1 mol Siloxane 0.02 to 2 mol of the metal compound are used. The catalysts obtained by the process It is known that one can use catalysts from Ver for the polymerization of olefins, aliphatic bonds of metals from IV. to VI. Subgroup vinyl compounds and vinyl aromatic and