SU353422A1 - METHOD OF OBTAINING DERIVATIVE TRANSITION METALS - Google Patents

Description

The invention relates to a process for the preparation of new derivatives of transition metals, as well as

some may find

and polymerization initiating catalysts or proc. The known method produced

receiving

metals, consisting in the fact that the divalent oxychloride metal is subjected to interaction with the halide, oxyhalide, oxyalkyl metal 1VB, VB, VIB groups of the periodic system, with the release of the final product with known nrnemami.

The proposed method consists in that the inert matrix material with a surface containing hydroxyl groups freed from adsorption water is subjected to interaction With a transition metal complex of the general formula RMmXp, where R is substituted by 1a or a substituted alkyl or alkeyl group containing alkyl as the substituent the general formula is CH2Y, where Y is unsubstituted or substitutedan aromatic, polyaromatic group, cycloalkenyl, halo or M (R) group, where M is cremation, germanium, tin, lead, and R is hydrogen, alkyl;

M - transition metal 1VA-VIA groups of the periodic system of elements;

X - monovalent

ligaid, for example

halogen;

p - from O to the valence of the metal minus 2, with the selection of the target product are known. mn techniques.

As the matrix material take alumina, (belt or a mixture of them. A preliminary proportion of 1A) complex

the transition metal and the inert matrix material are selected so that each reactive hydrocarbon group reacts with the hydroxyl group of the matrix material. The process is preferably Westp in the medium of a hydrocarbon solvent.

It is essential that the matrix material does not contain adsorbed water capable of reacting and destroying the comilex connection of the transition metal. The matrix material can be easily freed from such adsorbed water by, for example, simple heat treatment.

The reaction between the complex compound of the transition metal and the matrix material consists in displacing (or replacing) one or more hydrocarbon groups with hydrogen, OP groups, or groups, from the discharge. The reaction can be represented by the following equation:

Matrix- {OH) n + MRmXp Matrix (O) "MRm-nXp - | - FTiRH,

in which M, R, X, m and p have the above values for them, and ga is an integer not greater than m -1. It turned out that, with the interaction of the components of the transition metal comnotation, all but one of the hydrocarbon groups of the organometallic derivative can be replaced with the OH-primers of the matrix, so that only one hydrocarbon group remains bound or joined to the transition metal. This occurs regardless of the number of reactive hydroxyl groups on the surface of the matrix.

The term Matrix - (ОН) „under {) is an inert material of matrices containing a minimum of n reactive hydroxylic primers on its surface. The number of reactive hydroxyl groups, i.e. the number of those capable of entering into this reaction, depends on the nature and conditions of the matrix material.

Thus, for example, in some materials, due to their molecular configuration, some of the existing hydroxyl groups are not reactive under the specified conditions. It is advisable that the matrix, but at least initially, eariip () iui,; ia with an excess of complex transition metal compound, so that there is a certain number of hydroxyl groups capable of reacting.

Over the course of the reaction proceeding by the equation, you can easily monitor the release of free hydrocarbon, pH and the change in color of the reagents. The fact that the product to be obtained is a chemical compound, and not a physical mixture, i.e., that the transition metal complex is not simply adsorbed to the granular matrix material, can be proved by removing the product — a dye-insoluble compound — from the reagent medium and washing it with a solvent removed the adsorbed calplex with a matrix of 1, s. Upon completion of this operation, the complex remains on the matrix. In contrast, when mixed with complexed compounds with an inert matrix material that does not contain reactive hydroxyl primer, for example with silica calcined at 1200 ° C, despite the fact that the complex compound is adsorbed on the matrix material, it can be easily removed by washing with solvent.

The proposed method for the preparation of transition metal derivatives can be realized in two ways.

of the material in an inert liquid and titration with a solution of the transition metal complex in an inert solvent until all reactive hydroxy groups of the matrix material are reacted.

The second way is that the excess complex compound of the transition metal or Grignard reagent is added to one

portions of the matrix material, pre-gel 110 released from the adsorbed water, n determine the amount of hydrocarbon molecules released, then a sufficient amount of the corresponding transition metal comilex is added to the second norm of the same matrix material until the equivalent carbon quality of carbon is separated.

Example 1. A matrix matrix material containing hydrated precipitated silica with particles ranging in size from 15 to 20 µm is heated for 2 hours at 200 ° C under a pressure below torr to remove adsorbed water. After treatment, the hydroxyl content on the surface is determined by adding an excess of methylmagnesium iodide. The amount of methane released is 0.86 lg, "ol / g silica.

When excess tetrakis- (p-allyl) zirconium is added to the suspension by the analogous way of silica obtained in toluene, propylene is released at 0.86 mmol / g of silica. The gradual introduction of the zirconium complex

to CRE; 1beam shows that two propylene molecules are released per molecule of the zirconium complex.

The combination of the non-stock metal is obtained by adding 0.43 mmol of tetrakis - {/ g-allyl) zircoia to the suspension of dry silica (1 g prepared by the above-described method) in toluene. The dark K1) acne color of the zirconium derivative disappears and the zirconium composition appears green

colors. The composition should be stored in a dry inertia atmosphere, or iodine with toluene, or free from liquid.

So, adding only X million tetrakis (p-allyl) -zirconium, where X is less than 0 ,, to 1 g

silica gives X mmol of cosmosis along with inert silica matrix material containing Y-2X hydroxyl groups, but not reactive, and Y means the content of hydroxyl

group (pas 1 g of cremiesema).

PRI mme R 2. A sample of silica - 1 g, obtained by the method described in Nimer 1, is suspended in toluene. Reactive hydroxy groups are titrated

a solution of methyl (/ g-allyl) -zirconium in toluene. It turns out that 0.43 mmol is consumed before the occurrence of the color of the idesic liquid. The resulting zirconium composite has a brown (brown)

Another sample of the transition metal composition in accordance with the present invention is prepared by introducing a solution of tris (p-allyl) zirconium bromide into a suspension of silica in toluene in an amount of 0.43 mmol of a zirconium derivative per gram of silica.

Example s 3-5. Compositions in accordance with the present invention are prepared as described in Example 1 using the same matrix material. The components used are listed below.

Components

composition The amount of propylene released

per mole of a transition metal complex reacting with SiO2,

mol / mol

Cr (metal)

Hf ("-Allyl) 4-5U22

2g ("- allyl) 2Bg2SiO21

Example 6. High-purity-alumina is subjected to dehydration by heating for 2 hours at 600 ° C under a vacuum of at least Torr. It is then cooled in a dry nitrogen atmosphere and suspended in a dry bepzole without admixture of oxygen.

A sample of the suspension is titrated with a solution of tetrabenzyl zirconium in benzene and the quenching point is recognized by the appearance of a constant color of the solvent. With the gradual addition of the same zirconium complex to another sample of alumina suspension, it can be noted that two toluene molecules are released per molecule of the zirconium complex.

The composition of tetrabepzil zirconium is prepared by adding 0.4 mmol of tetrabenzyl zinc to 1 g of dry alumina suspended in toluene. The yellow color (caused by tetrabenzyl zirconium) of toluene disappears and a yellow composition is obtained.

Example 7. The composition of tetrakis- (pallil) -zirconium and gliozem is obtained by adding 0.4 mmol of the zirconium complex per 1 g of dry hl of the earth, as described in Example 6, in a single procedure. A composition is obtained.

2 mol of propylene are liberated in green, and for each (gram) zirconium atom.

Examples 8-9. The operation described in Example 7 was repeated using, respectively, tetraalkis - (; g-allyl) -cyrconium and tetrakis- (p-allyl) -molybdenum. In example 7, comilex blue (blue) and the composition is brown. In Example 9, the complex is blue-green, and the composition is brown.

Subject invention

A method for the derivatization of transition metal derivatives, characterized in that the inert matrix material with a surface containing hydroxyl groups freed from adsorbed water is reacted with a transition metal complex of the general formula RMmXp,

where R is an unsubstituted or substituted alkyl or alkenyl group containing, as a substituent, an alkyl of the general formula -CHoY, where Y is an unsubstituted or substituted aromatic, iro-aromatic group, cycloalkane, halo or M (R),

where M is silicon, germanium, tin, lead;

R is hydrogen, alkyl;

M - transition metal 1VA-VIA groups of the periodic system of elements;

t - from two to the highest valleptness of metal M;

X is a monovalent ligap, for example halogen;

p - from O to the valence of the metal minus 2, with the selection of the target product by known techniques.

2. Method of clause 1, characterized in that alumina, or KpeMHe3eNt, or a mixture thereof is taken as the matrix material.

3. Method but paragraphs 1 and 2, characterized in that the proportion of the transition metal complex and the inner matrix material is selected so that each of the reactive hydrocarbon groups reacts with the hpdroxyl group of the matrix material.

4. Method according to paragraphs. 1-3, characterized in that the process is conducted in a hydrocarbon solvent medium.