BE891234A - POLYMERIZATION PROCESS FOR 1-OLEFINS AND CATALYSTS FOR THIS PROCESS - Google Patents

Description

       

  "Process for the polymerization of 1-olefins and catalysts

  
for this process "The invention relates to intermetallic compounds of alkoxides (also called alcoholates) of transition metals and processes for their preparation. More particularly, the invention provides catalyst progenitors intended to react on activators of the halide type to form a catalyst component

  
  <EMI ID = 1.1>

  
Polyethylene has been commercially produced since

  
  <EMI ID = 2.1>

  
dispersion at low pressure or in an autoclave or in tubular reactors at higher pressures.

  
Recently, there has been interest in low density linear polyethylene resins characterized

  
by their linearity and by a short ramification ensured by comonomers of the alkene type and which exhibit a restricted distribution of molecular weight, of properties; improved resistance, greater viscosity in the molten state, a higher softening point, better ESCR (resistance to cracking by stresses under the action of the medium) and better brittleness at low temperature. These properties, as well as related properties, provide benefits to the user within; applications such as blown sheets, coating of metal wires and cables, cast sheets, coextrusion and injection and rotational molding.

  
Typically, to manufacture linear polymers of olefins, catalysts of the general type described by Ziegler are used, therefore comprising a metal compound

  
transition, usually a titanium halide, mixed with an organometallic compound such as an aluminum alkyl. The transition metal component can be activated by reacting it with an activator of the halide type such as an alkyl aluminum halide. Among

  
improved catalysts of this type include those which include a magnesium component, usually

  
by the interaction of magnesium or a compound thereof with the transition metal component or the organometallic component, for example by grinding, chemical reaction or association.

  
  <EMI ID = 3.1>

  
leading to high density resins with @ characteristic modified using coordination catalysts

  
of this type. In particular, resins are sought with a wider molecular weight distribution and a higher melt index.

  
The subject of the invention is a catalytic system for

  
  <EMI ID = 4.1>

  
lysers one of which is an intermetallic compound activated by a halide and which is the product of the reaction of an oxide-alkoxide polymer of transition metal and a reducing metal having a higher oxidation potential than

  
the transition metal *

  
The invention also relates to a process for the polymerization of 1-olefins, individually or at the same time as at least

  
  <EMI ID = 5.1>

  
temperature and pressure suitable for polymerization, with an olefin polymerization catalytic system comprising a mixture of cocatalysts, one of which is an intermetallic compound activated by a halide and which is

  
  <EMI ID = 6.1>

  
transition metal and a reducing metal having a higher oxidation potential than the transition metal.

  
  <EMI ID = 7.1>

  
transition metal by reacting an oxide-alkoxide polymer of transition metal with at least one reducing metal, that is to say a metal having a higher oxidation potential than the transition metal. Thus, a polymeric titanium alkoxide or oxoalkoxide is reacted with metallic magnesium to form a reaction product which can be activated to form a component of olefin polymerization catalyst.

  
Polymer oxide-alkoxide can be prepared separately

  
  <EMI ID = 8.1>

  
or the polymeric oxoalkoxide can be obtained by an in situ reaction, for example by hydrolysis in a reaction medium comprising the reducing metal. For example, we

  
  <EMI ID = 9.1>

  
on metallic magnesium in a hydrocarbon solvent and in the presence of a regulated source of water "preferably a hydrated metallic salt such as a magnesium halide hexahydrate.

  
The transition metal alkoxides, in particular; of titanium, are known for their colligative properties in organic solvents and their sensitivity to hydrolysis. It has been reported that the hydrolysis reaction starting from oligomeric titanium alkoxides, usually trimeric, results in polymeric oxide-alkoxides of

  
  <EMI ID = 10.1>

  

  <EMI ID = 11.1>


  
It may also take place, especially at high temperatures, condensation reactions leading to structures that have ponta

  
  <EMI ID = 12.1>

  

  <EMI ID = 13.1>


  
which can, in turn, constitute or contribute to constituting hydrolysis reaction progenitors.

  
These titanium polymer alkoxides or oxoalkoxides
(sometimes also called u-oxoalkoxides) can be

  
  <EMI ID = 14.1>

  
the tendency of the metal to extend its coordination beyond

  
of its primary valence, along with the property

  
that the alkoxide has to bridge two or more metal atoms.

  
Whatever the particular form which one attributes to the alkoxide, it is sufficient in practice to understand that the oligomers of alkoxides form, by controlled hydrolysis, a series of polymeric oxides-alkoxides varying from dimer to a linear polymer up to an indefinite chain length, by the way

  
by cyclic forms. On the other hand, a more complete hydrolysis leads to the precipitation of insoluble products which result, by complete hydrolysis, in orthotitanic acid.

  
To facilitate the description, these polymer-oxide alkoxides of the respective transition metals will be called, representing the partial hydrolysis products. The hydrolysis reaction can be carried out separately * isolate the products and store them for later use, but this is inconvenient, especially given the possibility of further hydrolysis, so

  
that the preferred practice is to generate these bodies in the reaction medium. There are facts indicating that the same hydrolysis reaction occurs

  
in situ.

  
The hydrolysis reaction itself can be directly regulated by the amount of water supplied to the alkoxide

  
of transition metal and the addition rate. Water must be supplied gradually or in stages

  
or sequenced a mass addition does not lead to the desired reaction and causes excessive hydrolysis with precipitation of insoluble bodies. Addition drop

  
drip is suitable, as well as the use of reaction water, but it has been found more convenient to provide water in the form of water of crystallization, sometimes called

  
cationic, anionic, reticular or zeolitic water. So we usually use metallic salts

  
  <EMI ID = 15.1>

  
is not harmful to the system. It appears that the connection provided by the coordinated water sphere in a hydrated salt is capable of regulating the release and / or the availability, for the system, of water or of water-related species, as well as it is necessary to carry out, initiate or regulate the reaction.

  
The overall amount of water used, as said above, has a direct impact on the form of polymer oxide-alkoxide obtained and it is therefore chosen taking into account the catalytic result (it seems, without

  
that it is limiting, that the stereoconfiguration of the partially hydrolyzed transition metal alkoxide determines the nature of the activated catalyst component or the result of non-catalytic action or contributes in part).

  
  <EMI ID = 16.1>

  
0.5 mole of water per mole of transition metal. Amounts up to 1.5 moles are suitable and larger amounts, up to 2.0 moles, can be used whenever it is possible to prevent hydrolysis products from precipitating from solvent medium of the hydrocarbon type.

  
In principle, this can be achieved by reducing the flow and

  
by ceasing the addition to the first trace of precipitation.

  
It seems that the reaction is essentially equimolar, but it is appropriate to use a certain excess of water in certain cases, as is usual.

  
We understand that the stereoisomeric form, the length

  
chain etc ... of the hydrolysis product can change somewhat at the high temperature required then

  
by the reaction on the reducing metal and that in situ processes also influence the equilibria by the effect

  
  <EMI ID = 17.1>

  
can influence balances, reaction rates etc ...

  
The hydrolysis reaction takes place under ambient conditions of pressure and temperature and does not require special conditions. A hydrocarbon solvent can be used, but it is not necessary. A simple contact of the materials for a time which is usually between 10 to 30 minutes and 2 hours is sufficient. The material obtained is stable under normal storage conditions and its concentration can be brought to the appropriate and desired level by simply diluting it with a solvent of the hydrocarbon type.

  
The polymeric oxides-alkoxides of transition metals are reacted on a reducing metal having a higher oxidation potential than the transition metal. * Preferably, a polymeric titanium oxide-alkoxide is used at the same time as magnesium, calcium, potassium, aluminum or zinc, as reducing metal The systems of transition metal alkoxide, reducing metal and hydrated metal salt are suitably chosen taking into account the electrical potentials, so as to minimize the side reactions, in known ways in general, to ensure levels

  
  <EMI ID = 18.1>

  
the system is supplied with a magnesium content by suitably choosing the reducing metal and the hydrated metal salt

  
In the preferred embodiment (which

  
  <EMI ID = 19.1>

  
convenience) "we react the titanium tetra-n-butoxide
(TBT) on turnings of magnesium and a metal salt

  
  <EMI ID = 20.1>

  
autogenous pressure. TBT can constitute the reaction medium or a solvent of the type can be used

  
  <EMI ID = 21.1>

  
hydrated metal salt to be brought up during the reaction being approximately 1 mole of water per mole of Mg [deg.].

  
The hydrocarbon soluble catalyst progenitor mainly comprises a Ti content

  
  <EMI ID = 22.1>

  
stereoconfiguration, which seem to constitute mainly oxygenated species. Certain traces of mixed oxidation states of the titanium content suggest a system of whole species linked together comprising

  
  <EMI ID = 23.1>

  
quasi-equilibrium relationship, at least under conditions of dynamic reaction. It seems, without being limiting, that the preferential progenitor comprises Ti-O-Mg bridging structures.

  
Intermetallic compounds are especially useful as catalyst progenitors "in supported or unsupported systems, for isomerization.

  
  <EMI ID = 24.1>

  
alkenes, alkynes or substituted alkenes, in the presence or absence of reducing agents or activators, for example

  
  <EMI ID = 25.1>

  
to an organometallic compound to form a catalytic system particularly suitable for the polymerization of ethylene and comonomers with formation of resins

  
polyethylene.

  
The transition metal component is an alkoxide, normally a titanium or zirconium alkoxide, essentially comprising substituents -OR, in which R

  
may contain up to 10 carbon atoms, preferably from 2 to 5, and more preferably represents an alkyl-n group, for example butyl-ne The constituent chosen

  
is normally liquid under ambient conditions

  
and at reaction temperatures to facilitate handling and, to facilitate use, it is also soluble in hydrocarbons.

  
To facilitate the conduct of the corresponding hydrolysis reaction, it is generally preferable to use transition metal compounds comprising only alkoxide substituents, although other substituents can be envisaged when they do not interfere with the reaction by significantly modifying the result in service. In general, the halide-free n-alkoxides are used,

  
The transition metal component is supplied in the highest oxidation state of the transition metal,

  
so as to provide the desired stereoconfiguration structure, among other considerations. Most advantageously, as has been said, the alkoxide is a titanium or zirconium alkoxide. Suitable titanium compounds include titanium tetraethoxide as well as related compounds containing one or more radicals

  
  <EMI ID = 26.1>

  
n-butoxyl, isobutoxyl &#65533;, secondary butoxyl, tertiary butoxyl, n-pentoxyl, tertiary pentoxyl, tertiary amyloxyl, n-hexyloxyl, n-heptyloxyl, nonyloxyl etc ...

  
Certain facts suggest that the rate of hydrolysis of normal derivatives decreases as the chain length increases and that the rate decreases with molecular complexity, in the tertiary, secondary order,

  
  <EMI ID = 27.1>

  
the choice of a preferential derivative. In general, it has been found that titanium tetrabutoxide is very suitable for the practice of the invention and related tetraalkoxides are also preferred. It is understood that mixed alkoxides are perfectly suitable and can be used when conveniently available. It is also possible to use complex titanium alkoxides, sometimes comprising other metallic constituents.

  
The reducing metal is supplied at least in part in the zero oxidation state as a necessary element of the reaction system. A convenient source is the familiar turnings, ribbon or powder. As commercially supplied, these bodies may be in the oxidized state with a passivated surface and

  
it is sometimes desirable to grind them to obtain at least some new surface, at least to settle

  
reaction speed. The reducing metal may be supplied, as appropriate, in the form of a slurry in the transition metal component and / or the hydrocarbon type diluent, or it may be added directly to the reactor.

  
  <EMI ID = 28.1>

  
or for the independent preparation of the polymeric transition metal alkoxide, the source of water or water-related species is provided so that amounts of water are released or diffused or become accessible.

  
  <EMI ID = 29.1>

  
As we said above, we found that the sphere

  
coordination provided by a hydrated metal salt was suitable for this purpose, however. other sources of water in the same proportions are also usable., Thus, it is possible to use a calcined silica gel free of other active constituents, but containing controlled quantities of combined water. In general, the preferred source of water is an "aquo" complex in which the water is coordinated

  
to the main body in a known manner.

  
Suitable bodies include hydrated metal salts, especially mineral salts such as halides, nitrates, sulfates, carbonates and carboxylates

  
sodium, potassium, calcium, aluminum,

  
nickel, cobalt, chromium, iron, magnesium and the like.

  
Advantageously, the interaction of these constituents is carried out in a closed reactor, preferably comprising a possibility of reflux of volatile constituents at the high temperatures generated in the reactor. Autogenic pressure is used, since the reaction is

  
proceeds smoothly under ambient conditions, heating to initiate and maintain the reaction. As

  
in any such reaction, it is best

  
to agitate, simply to avoid agglomeration or encrustation on the surfaces of the reactor, to intimately mix the constituents and to ensure a homogeneous reaction system.

  
Usually, a hydrocarbon type solvent such as hexane, heptane, octane,

  
  <EMI ID = 30.1>

  
to facilitate the mixing of the constituents, the transfer

  
of heat and maintaining a homogeneous reaction system.

  
Saturated hydrocarbons with a boiling point of 60 to 190 [deg.] C are preferred. The liquid constituent to

  
transition metal can also be used at least in part <EMI ID = 31.1>

  
no solvent added. The reaction involves a stage where additional volatile constituents form azeotropes with the solvent or, if the constituents are used pure, constitute the source of reflux, but in either case it is preferable, at least to effect the reaction passing through intermediate stages with appropriate reaction times, to bring the volatiles back to the reaction zone. So. butanol is formed when the titanium component is

  
titanium tetra-n-butoxide and it forms an azeotrope with the solvent of the hydrocarbon type. It is therefore necessary to think, in a manner known to those skilled in the art, in choosing the solvent and / or the alkoxide so as to possibly limit the reaction temperature.

  
The reaction temperature is to some extent a matter of choice, over a wide range, depending on the reaction rate which is appropriate to use.

  
We have found that the reaction system (consisting of

  
the liquid transition metal component, the dissolved hydrated metal salt, the reducing metal particles and the solvent if desired)

  
  <EMI ID = 32.1>

  
which suggests that the initiation temperature or activation energy level is around 50 [deg.] C, which therefore constitutes the minimum temperature necessary for the reaction

  
polymeric oxyalkoxyl on the reducing metal. The

  
  <EMI ID = 33.1>

  
reducing metal and, therefore, it can easily be pushed to the next stage, which is the temperature

  
reflux. Since the alkanol formed is largely consumed during the course of the reaction (as an independent species), the effective temperature of the system varies and the completion of the reaction is revealed by consumption of visible metal and / or that the reflux temperature of the pure solvent is reached * in a time which is only 30 minutes to 4 hours or more. These temperatures can reach 140 to
1900C and, of course, higher temperatures could be applied, but with no apparent benefit.

  
  <EMI ID = 34.1>

  
preferably between 70 and 140 [deg.] C. In the absence of solvent * the upper limit will simply be established by the reflux temperature of the alkanol generated during the reaction.

  
The reaction of the constituents is above all revealed clearly by the marked change in color, with

  
  <EMI ID = 35.1>

  
gas. When the solution is neither opaque nor cloudy and allows observation, a release of gas, varying from the formation of bubbles to vigorous effervescence, is especially evident on the surface of the metal and the solutions, generally light in color, immediately become greyish, then quickly darker, turning blue, sometimes purple, usually black-blue, sometimes with a greenish tinge. Gas analysis does

  
  <EMI ID = 36.1>

  
After the rapid color change, some darkening of the color occurs during elevation

  
  <EMI ID = 37.1>

  
gas. At this stage, the alkanol corresponding to the alkoxide is generated in an amount sufficient to lower the boiling point of the solvent and it seems to be consumed gradually in a manner linked to the flow rate, at the same time as the remaining reducing metal.

  
The reaction product is partially soluble in hydrocarbons to the monk and is kept as a slurry for convenience of later use. When the semi-viscous product is isolated

  
  <EMI ID = 38.1>

  
X, an essentially amorphous character.

  
The molar ratios of the constituents can vary within certain ranges, without significantly influencing the result given by the catalyst progenitor in the end use. Thus, to avoid competing reactions which make the product inconveniently gelatinous or unmanageable, the transition metal component is usually supplied in at least molar proportion relative to the reducing metal, but the metal ratio

  
  <EMI ID = 39.1>

  
reducing agent results in a lowering of the reaction temperature, so that the reflux temperature of the pure solvent is not yet reached, however, an excess of reducing metal is immediately seen by the fraction

  
not consumed thereof, so that a person skilled in the art will easily determine the desired amount of this constituent.

  
In these ranges, a variable proportion of the reaction product can form a component insoluble in hydrocarbons, but it can be diluted with the soluble component and it is usually done for use, for example for a new reaction

  
on a halide activator for training

  
an olefin polymerization catalyst. The amount of this insoluble constituent can be partly regulated by the use of a solvent having an appropriate partition coefficient, but, when it is preferable for practical reasons to use as a solvent a common hydrocarbon such as octane, we found that

  
  <EMI ID = 40.1>

  
  <EMI ID = 41.1>

  
homogeneous reaction product.

  
Water or related species is also preferably provided in a molar ratio relative to the transition metal component, for similar reasons of homogeneity and ease of reaction. So in

  
  <EMI ID = 42.1> during the reaction about 1 mole of water and this proportion * up to about 2 moles of water, ensures the easiest reactions with one or more moles of constituent

  
with transition metal. More generally, the quantity

  
of H20 can vary from about 0.66 to 3 moles per mole

  
of transition metal. Of course, the quantity of water present at any given stage of the reaction is likely to be much lower, going up to catalytic proportions relative to the remaining constituents, depending on the mode and the speed of participation in the reaction process, who are currently unknown. However,

  
it is specially envisaged, without limitation, as a working hypothesis, that water, or the related species governing

  
reaction speed, is activated, released, made accessible or diffuse in order to provide this species

  
regularly, sequenced, constant or variable,

  
related to speed. However, the same molar proportion of free water supplied at the start of the reaction is entirely ineffective in initiating the reaction at this temperature.

  
or at a higher temperature and results in undesirable complete hydrolysis reactions.

  
The quantity of water measured is practically in molar equilibrium or in molar excess relative to the reducing metallic constituent and it seems that it is linked to its consumption in the reaction, since a molar insufficiency of water invariably leads to the persistence of '' an excess of reducing metal. In general, a moderate excess of 10 to 40% water is suitable for ensuring a complete reaction. Larger proportions are suitable, without limitation, but must be kept in balance

  
  <EMI ID = 43.1>

  
hydrates, when used, are primarily intended to regulate the availability of water supplied to the system * So * sodium acetate trihydrate may be suitable, as well as magnesium acetate tetrahydrate, magnesium sulfate heptahydrate and fluorosilicate magnesium hexahydrate.

  
It is necessary to prefer a salt having the maximum degree of hydration compatible with the regulated release ensured by the

  
coordinated liaison. The most suitable is to use a hydrated magnesium halide such as chloride

  
  <EMI ID = 44.1>

  
These salts, like other hygroscopic bodies, even when supplied in anhydrous commercial form, contain a certain amount of sorbed water, for example 17 mg / kg (see patent GB 1,401,708), although it is much lower than the molar quantities envisaged according to the invention. Therefore, anhydrous quality salts are not suitable here, unless specially modified for this purpose.

  
The reaction system as defined below does not require, but tolerates, an electron donor or a Lewis base, or a solvent partially playing these roles. As indicated in the examples, in the preferred embodiment, the reaction is carried out with water of crystallization and an alcohol component in

  
the system. It is therefore unclear whether a proton transfer or electron donor mechanism exists concurrently in the reaction system.

  
No separation is necessary, given

  
that at least part of the reaction product is soluble in the saturated hydrocarbon when it is used as a solvent or provides a solvating medium such that, even when a precipitate also occurs, and even after storage, it is possible to easily form a usable reactive porridge.

  
According to a preferred aspect of the invention, the reaction product is further reacted (catalyst progenitor) on an activator of the halide type such as an alkylaluminum halide, a silicon halide,

  
an alkylsilicon halide, a titanium halide or an alkyl boron halide. It has been found that the catalyst progenitor can be easily activated by simply joining the product to the halide activator. The reaction is vigorously exothermic

  
and that is why, typically, the halide activator is gradually added to the reaction system. Normally, upon completion of the addition, the reaction

  
is also complete and can be stopped. The reaction product can then be used immediately, as a solid or as a slurry, or stored for later use. Usually, to have the best control of molecular weight and particularly to make a low density resin, only the solid product washed with a hydrocarbon is used as catalyst.

  
The halide activator is commonly provided for interaction at a molar ratio (between aluminum, silicon or boron and the transition metal

  
  <EMI ID = 45.1>

  
successfully ratios of 2: 1 or more.

  
The catalyst product obtained can be used directly in the polymerization reaction, but, typically, it is diluted in the desired manner to ensure, in a suitable supply, a quantity of catalyst which is equivalent to 80 to 100 mg of transition metal, over the basis of a nominal productivity greater than 200,000 g of polymer per gram of transition metal, in continuous polymerizations, this productivity being ordinarily exceeded by the catalyst according to the invention. The shame of art makes adjustments to take into account

  
reactivity and efficiency, usually by simple dilution and by adjusting the flow rates.

  
To use it in polymerization, we bring together

  
the transition metal catalyst to an organometallic cocatalyst such as triethylaluminum or triisobutylaluminum or to a non-metallic compound such

  
than triethylborane. Thus, a typical polymerization feed includes 42 parts of isobutane as solvent, 25 parts of ethylene, 0.0002 part of catalyst
(calculated as Ti) and 0.009 part of cocatalyst (TEA, calculated as Al), which is introduced into a reactor

  
  <EMI ID = 46.1>

  
calculates the amount of cocatalyst, when useful so that it is from 30 to 50 ppm approximately, calculated as Al or B, relative to isobutane.

  
Examples of cocatalysts are trialkylaluminium compounds such as triethylaluminium, triisobutylaluminium, tri-n-octylaluminium,

  
  <EMI ID = 47.1>

  
dialkylzinc, dialkylmagnesium and metal hydrideborate compounds, including those of alkali metals, especially sodium, lithium and potassium and

  
those of magnesium, beryllium and aluminum. Metal-free cocatalysts include alkyl boron compounds such as triethylborane, triisobutylborane and trimethylborane and boron hydrides such as

  
  <EMI ID = 48.1>

  
The polymerization reactor is preferably a loop reactor suitable for operation with a slurry and a solvent such as isobutane is therefore used, from which the polymer separates in the form of a granular solid. The polymerization reaction is carried out at low pressure, for example from 1.4 to 6.9 MPa, and at a temperature of 38

  
  <EMI ID = 49.1>

  
to adjust the molecular weight distribution. It is possible to bring to the reactor other normal alkenes, in the minority relative to ethylene, in order to copolymerize them. Typically, butene-1 or a mixture thereof and hexene-1 is used, in a proportion of 3 to

  
10 mol%, although other proportions of et-olefin serving as comonomers can be easily used. When we

  
  <EMI ID = 50.1>

  
  <EMI ID = 51.1>

  
from amounts of 0.2% by weight only, especially when using mixtures of monomers.

  
However, the polymerization can be carried out at

  
  <EMI ID = 52.1>

  
autoclaves or tubular reactors, if desired.

  
When we speak here of "compound" or "complex"

  
intermetallic, this means any reaction product, formed by coordination or association or in the form of one or more inclusion or occlusion compounds, clusters, etc., under the applicable conditions, the integrated reaction generally being revealed by a change in color and a release of gas which probably reflects a reduction-oxidation, a rearrangement and an association between the unconsumed constituents of the reaction system.

  
The following examples, considered in conjunction with the description above, serve to illustrate the invention further, as well as its mode of execution and use.

  
All parts are by weight, unless otherwise indicated.

  
The melt indices are measured respectively under conditions E and F of standard ASTM D-1238-57T for the values MI and HLMI, on samples of powder or of resin, as specified. The HLMI / MI or MIR ratio is

  
the melt index ratio, which is a measure of the shear sensitivity, reflecting the distribution

  
molecular weight. The other tests are as indicated or as they are conventionally carried out in related branches.

  
  <EMI ID = 53.1>

  
A. 6.0 parts of

  
  <EMI ID = 54.1> <EMI ID = 55.1>

  
with stirring, within 20 minutes, an additional 3.3 parts of chromium salt. To the green solution,

  
0.3 parts of magnesium clippings are added in portions, in total, which causes vigorous gas evolution. The cooled reaction product, free of excess magnesium (which has completely disappeared) is a viscous green liquid soluble in hexane.

  
B. In a similar operation, anhydrous chromium chloride is used with the titanium alkoxide, but no reaction occurs when heated

  
  <EMI ID = 56.1>

  
zinc powder and pushing the heater over
150 [deg.] C, no reaction is yet observed. Replacing the magnesium trimmings does not give a reaction either. It is concluded that the hydrated salt was a necessary component of the reaction system.

EXAMPLE II

  
A. In a stirred reactor equipped with a jacket

  
  <EMI ID = 57.1>

  
1 hour 45 minute total reaction. The reaction product at room temperature is a dark green liquid which dissolves easily in hexane.

  
B. In the same way, a reaction product is prepared

  
  <EMI ID = 58.1>

  
120 [deg.] C and the evolution of gas continues. The reaction is stopped when the magnesium has disappeared, after

  
1 hour 15 minutes. The product is soluble in hexane.

  
C. The above operations are repeated with 0.116 mole

  
  <EMI ID = 59.1>

  
The reaction is completed in 115 minutes and a product soluble in hexane is obtained.

  
D. The proportions of reagents are modified again, in another operation, ie 0.115 mole of TBT, 0.0287 mole of CrC13.6H20 and 0.0144 mole of Mg. Dirty green material that appears at 114 [deg.] C turns blue on the surface of the Mg. The product is soluble in hexane.

  
E. In a similar operation, reacting 0.176 mole of TBT, 0.30 mole of CrC13.6H20 and 0.176 mole of

  
  <EMI ID = 60.1>

  
gas and almost black at 90 [deg.] C. The color turns green again

  
at 119 [deg.] C and the reaction ends at 121 [deg.] C with complete disappearance of the magnesium. The product (6.9% Ti, 3.5% Mg,

  
1.3% Cr by weight) is a dark olive-green liquid and a

  
  <EMI ID = 61.1>

  
which is deposited.

  
? In another operation, we react in

  
  <EMI ID = 62.1>

  
0.150 mole of Mg. Again, the dirty green color almost turns black, with vigorous effervescence, forming, at 109 [deg.] C, a black-dark blue product (5.7% Ti, 2.9% Mg,

  
  <EMI ID = 63.1>

EXAMPLE III

  
A. In a reactor, the reaction product IIE is combined with isobutylaluminum chloride added dropwise in desired proportions to give an Al / Ti molar ratio of 3 μl. The mixture of green color passes

  
  <EMI ID = 64.1>

  
the addition of reagents at 39 [deg.] C, it became reddish brown. After 30 minutes of additional stirring, the reaction is stopped, the product comprising a dark red-brown liquid and a dark brown precipitate.

  
B. The reaction product IIF is reacted in a similar manner with isobutylaluminum chloride (molar ratio Al / Ti 3tl). Maximum temperature at the end

  
of the addition, is 48 [deg.] C, but no browning is observed. The product includes a colorless liquid and a dark gray precipitate.

EXAMPLE IV

  
The catalyst components prepared in Example III are used for the polymerization of ethylene.
(88 [deg.] C, 10 mol% of ethylene, 0.0002 part of catalyst calculated as Ti, approximately 45 ppm of triethylaluminum, calculated

  
  <EMI ID = 65.1>

  
  <EMI ID = 66.1>

  
  <EMI ID = 67.1>

  

  <EMI ID = 68.1>


  
In the following example, the catalyst component of the invention is prepared starting from the mixture of reactants in the absence of added solvent.

EXAMPLE V

  
A. In a stirred reactor equipped with a jacket

  
  <EMI ID = 69.1>

  
magnesium salt completely dissolves at room temperature, forming a homogeneous mixture. We heat

  
  <EMI ID = 70.1>

  
gas begins on the surface of magnesium turns. At 140 [deg.] C, with reflux, the release became more vigorous. The solution darkens and the release ceases

  
  <EMI ID = 71.1>

  
The magnesium introduced reacted - and it is soluble in hexane.

  
B. In another operation, the proportion is increased

  
  <EMI ID = 72.1>

  
After 125 minutes of reaction, the product contains a certain excess of magnesium, approximately 63% have reacted.

  
C. In another operation, the molar ratio is

  
  <EMI ID = 73.1>

  
is not easily diluted with hexane. All the magnesium is consumed.

  
The following example indicates the preparation carried out in a solvent of the hydrocarbon type.

EXAMPLE VI

  
A. In a stirred reactor equipped with an electrical heating jacket, 50.2 parts (0.148 mole) of TBT are added to 58.6 parts of octane. 0.074 mole of magnesium turnings are added, stirring begins and then added in the course of one minute, while heating, 0.0125

  
  <EMI ID = 74.1>

  
has completely dissolved and at 95 [deg.] C (25 minutes), the evolution of gas begins on the surface of the magnesium turns, it increases while the solution becomes greyish then dark blue, with reflux at 117 [deg. ] C (35 minutes *). Metallic magnesium fully reacted within 1 hour
(128 to 129 [deg.] C) and the reaction is stopped. We calculate that

  
the blue product, dissolved in octane (a small amount of greenish precipitate remains) contains, by weight,

  
  <EMI ID = 75.1>

  
B. The above operation is practically repeated, except that the molar proportions of the reactants are modified, with the following results

  
  <EMI ID = 76.1>

  

  <EMI ID = 77.1>


  
C. Repeat the preparation 1/1 / 0.34 above, if this

  
  <EMI ID = 78.1>

  
parts of hexane as reaction solvent medium. We

  
obtains a dark blue-dark liquid containing. on calcination, 8.2% of Ti and 1.6% of Mg in weight.

  
The following example shows staggered preparation

  
of the catalyst component.

EXAMPLE VII

  
  <EMI ID = 79.1> <EMI ID = 80.1>

  
yellow liquid and crystalline salt is replaced by a milky yellow opaque viscous liquid. Prolonged agitation causes the disorder to disappear and gives a transparent yellow liquid in 2 hours (in a second operation carried out in octane in 30 minutes, the salt dissolves completely, giving a yellow liquid without precipitate or opacity).

  
A TM Mg product is prepared in the manner of the previous examples, using the light yellow liquid prepared above and 1.83 parts of Mg, with a molar ratio of 1 / 0.75 / 0.128 in octane. The reaction progresses steadily, giving a dark blue-black liquid and a green precipitate in the same way as other reactions mentioned.

  
  <EMI ID = 81.1>

  
at an Al / Ti ratio of 3: 1, to form a catalyst component for the polymerization of olefins.

  
The following example shows the meaning of the combined water rate.

EXAMPLE VIII

  
We carry out a series of operations identical to a

  
  <EMI ID = 82.1>

  
only the degree of hydration of the magnesium salt is changed.

  
  <EMI ID = 83.1>

  
1: 1. All the metallic magnesium reacts. It is also observed that the amount of insoluble product increases with the salt level.

  
The following example illustrates the use of other titanium compounds.

EXAMPLE IX

  
A. In a stirred flask fitted with an electric heating jacket, 45.35 parts (0.1595 mole) of

  
  <EMI ID = 84.1>

  
blue at 90 [deg.] C with effervescence. From the remaining magnesium, it is concluded that the reaction is partially inhibited by the presence of the aetane / isopropanol azeotrope.

  
B. The reaction described in A is repeated with a molar ratio of 1 / 0.75 / 0.128 using the decahydronaphthalene as diluent (boiling point 185 to 189 [deg.] C). After 6 hours, the reflux temperature reaches 140 [deg.] C

  
and we stop the reaction. A dark black-blue liquid is obtained with a small amount of dark precipitate. Only 8.8% of the magnesium reacted.

  
C. Similarly, the reaction is carried out on

  
tetraisobutyl titanate at a molar ratio of 1 / 0.75 / 0.128 and a black-blue liquid and a dark precipitate are obtained. About 50% of the magnesium reacts.

  
D. Tetranonylate is similarly used

  
  <EMI ID = 85.1>

  
1 / 0.75 / 0.128 molar. A blue liquid forms,
45% of the magnesium being consumed.

  
E. The reaction product of titanium tetrachloride and butanol (which appears to be dibutoxytitanium dichloride) is reacted with magnesium and magnesium chloride hexahydrate at a molar ratio of 1 / 0.75 / 0.128 to the examples above. About half of the magnesium is consumed in about 3 hours and a black-dark blue liquid and an olive-green precipitate (50/50 by volume) are recovered.

  
The following example uses a zirconium alkoxide.

EXAMPLE

  
  <EMI ID = 86.1>

  
form of commercial turnings and 8.8 parts of octane and the mixture is refluxed at 125 [deg.] C while stirring for

  
15 minutes, without seeing any reaction. We add 0.97

  
  <EMI ID = 87.1>

  
vigorous effervescence and the mixture becomes milky.

  
B. In a second operation, 31.7 parts are brought together
(0.069 mole) of the zirconium compound, 0.069 mole of

  
metallic magnesium and 57.6 parts of mineral spirits
(boiling point 170 to 195 [deg.] C) and we add, with

  
  <EMI ID = 88.1>

  
applies heat to the reactor with an electrical jacket. In 5 minutes, the mixture took an opaque appearance and the evolution of gas on the surface of the metallic magnesium is evident when the temperature reaches

  
85 [deg.] C, after 8 minutes of reaction. The release

  
gas continues with vigorous effervescence, the temperature

  
  <EMI ID = 89.1>

  
When one continues to heat at 133 [deg.] C (1 hour of reaction), all the metallic magnesium has disappeared, the reactor containing a milky white liquid and a white solid. We cool

  
the mixture and 92 parts of a mixture containing * by weight, 6.8% Zr and 2.4% Mg (Zr / Mg = 2.8: 1 by weight, 0.75 if in moles) which is soluble are collected in hydrocarbons.

  
You can activate the product in a known way, by

  
example with an alkylaluminum halide, preferably reacting thereon at a molar ratio

  
Al / Zr between 3: 1 and 6: 1 approximately, to obtain,

  
in combination with an organic or organometallic reducing agent, a catalytic system for the polymerization of olefins suitable for the formation of polyethylene resin.

  
The following example shows the replacement of magnesium by calcium as a reducing metal.

  
  <EMI ID = 90.1>

  
A. In a stirred reactor equipped with a jacket

  
  <EMI ID = 91.1>

  
a rapid release of gas is observed followed by the formatting of a dark blue liquid. After 90 minutes, the reaction is stopped and a product constituting a dark blue-black liquid with a greenish shade is isolated.

  
The operation is repeated at the same molar ratio. 50%

  
calcium react by giving a dark blue liquid

  
and a gray solid containing, by weight, 6.2% Ti, 2.6% Ca

  
  <EMI ID = 92.1>

  
In another operation, the same reagents are combined in a molar ratio of 0.75 / 0.128. Calcium reacts

  
at 63% and a black-blue liquid and a green solid are obtained. The product (molar ratio 1 / 0.47 / 0.128) contains,

  
  <EMI ID = 93.1>

  
B. The reaction product is then reacted

  
XI Al on ethyl aluminum chloride in an Al / Ti molar ratio of 3/1 and 6/1. We dilute the products with

  
hexane and the halide activator is added slowly to control the strongly exothermic reaction.

  
  <EMI ID = 94.1>

  
initially, upon completion of the reaction, turns into a pink liquid and a white precipitate. At an Al / Ti ratio of 6/1, the porridge turns gray then lime green.

  
  <EMI ID = 95.1>

  
in an Al / Ti molar ratio of 3/1 and 6/1. The reactions are regular, giving 3/1 a dark brown slurry and 6/1 a reddish-brown liquid with a brown precipitate.

  
C. The reaction products prepared in B are used in the polymerization of ethylene with the results indicated in the following table.

  

  <EMI ID = 96.1>


  

  <EMI ID = 97.1>
 

  
The operations show a slightly wider molecular weight distribution of the resin, compared to the case where magnesium is used as the reducing metal *

  
The following example shows the use of zinc as a reducing metal.

EXAMPLE XI I

  
A. In an agitated closed system equipped with a reflux

  
and heated externally, 0.204 mole of TBT is combined,

  
  <EMI ID = 98.1>

  
In the space of 13 minutes (85 [deg.] C), a rapid black-blue turn takes place with increasing gas evolution, leading to vigorous effervescence and foaming.

  
The product, which is a black-blue liquid (without precipitate) comprising 7.7% Ti, 0.9% Zn and 0.5% Mg by weight, turns yellow when exposed to air.

  
B. The reaction product TiZnMg is reacted
(molar ratio 1 / 0.86 / 0.128) on isobutyl chloride

  
  <EMI ID = 99.1>

  
between 10 and 13 [deg.] C (XII Bl).

  
C. The preparation of the TiZnMg product (XII A) is repeated using zinc powder with similar results. Another operation with zinc foam uses only 7% of the zinc and a green layer is observed on the surface of the zinc.

  
D. The activated product XII B1 prepared as above is washed carefully in hexane and used in the preparation of a low density polyethylene resin. The reactor is precharged with enough butene-1 to ensure the desired density and the reaction is carried out (adding butene-1 in portions at the same time

  
  <EMI ID = 100.1>

  
in the presence of triethylaluminum as a catalyst. The

  
  <EMI ID = 101.1>

  
0.9165, MI 1.68, HLMI 52.1, MIR 31.

  
The following example involves the use of potassium as the reducing metal.

EXAMPLE XIII

  
In a closed system equipped with reflux and heated

  
  <EMI ID = 102.1>

  
fresh metallic potassium (stripped of its oxide / hydroxide coating by scraping under octane) and 8.0 mmol of

  
  <EMI ID = 103.1>

  
black-blue and bubbles appear. It follows a vigorous evolution of gas and an effervescence. When the metallic potassium has disappeared, the reaction is stopped
(after 5 hours). A dark black-blue liquid and a small amount of dark blue precipitate are recovered.

  
Examples XIV and XV describe the use of aluminum as a reducing metal.

EXAMPLE XIV

  
A. In a reactor, by stirring and applying heat by an electrical jacket, 112.31 is mixed

  
  <EMI ID = 104.1>

  
When we reach 100 [deg.] C in about 10 minutes, the yellow color darkens and at 118 [deg.] C, a vigorous effervescence begins with the evolution of gas. At 122 [deg.] C,

  
the refluxing liquid takes on a gray shade and the temperature stabilizes while the color changes from dark gray with bluish shade to dark blue then to black-blue after 27 minutes of heating. We maintain the

  
  <EMI ID = 105.1>

  
minutes, the evolution of gas is then practically complete and the reaction is stopped.

  
The product is at room temperature a viscous liquid having unaltered aluminum particles. The unaltered aluminum is separated, washed and weighed

  
  <EMI ID = 106.1> cooling, 9.10 parts of the product prepared above (0.719 part of Ti or 0.015 mole) are added to 13.0 parts of hexane. 0.045 mole of ethyl aluminum dichloride is gradually added while maintaining the temperature

  
  <EMI ID = 107.1>

  
A second operation is carried out (0.175 mole of Ti / 0.0525 mole of Al) without cooling down to a temperature

  
  <EMI ID = 108.1>

  
brown-red with an unmanageable solid deposit (B2).

EXAMPLE XV

  
The products of Example XIV are used as catalysts in the polymerization of ethylene in

  
  <EMI ID = 109.1>

  
using triethylaluminum as a cocatalyst, with

  
  <EMI ID = 110.1>

  

  <EMI ID = 111.1>

EXAMPLE XVI

  
A. Similarly to the above, 0.133 mole of TBT, 0.100 mole of Alo and 0.017 mole are combined.

  
  <EMI ID = 112.1>

  
7 hours 15 minutes to obtain a dark blue-black liquid and a small amount of a gray solid. About 40% of the aluminum reacts to give a product containing, by weight 6.6% of Ti and 1.6% of Al
(XVI Al).

  
In the same way, we bring together the same reagents up

  
  <EMI ID = 113.1>

  
giving a reaction product which contains 6.5% by weight of Ti and 2.7% by weight of Al (XVI A2).

  
B. The products (XVI Al and XVI A2) are activated with ethyl aluminum chloride at an Al / Ti ratio of 3 /

  
C. The solid fraction of the activated reaction product (XVI A2) is isolated from the supernatant and used, with TEA as cocatalyst, in the polymerization of

  
  <EMI ID = 114.1>

  
The following examples relate to catalyst components prepared with other "aquo" complexes.

EXAMPLE XVII

  
A. In a heated reactor, 0.0335 mole is stirred

  
of TBT and 0.0335 mole of Mg [deg.] in octane and added

  
  <EMI ID = 115.1>

  
appears a gray color with effervescence and the solution becomes blue then black-blue with a greenish shade. The reaction is stopped at 123 [deg.] C (about 10% of unaltered Mg)

  
after a reaction time of 4 hours 10 minutes

(XVII A).

  
Similarly, a product is prepared with a

  
  <EMI ID = 116.1>

  
obtains a black-blue liquid and a dark green precipitate
(6.5% Ti, 2.5% Mg by weight, calculated).

  
B. The product (XVII A) decanted is combined with

  
  <EMI ID = 117.1>

  
3/1 and 6/1 by gradually adding the aluminum alkyl halide. In the first operation (Al / Ti 3/1), a maximum temperature of 42 [deg.] C is reached with addition. at the rate of 1 drop every 2 to 3 seconds and the green liquid then becomes brown. The product includes a. red-brown liquid and a brown precipitate (IV Bl). Product 6/1 (IV B2) is prepared in a similar manner with the same results.

  
In a separate operation, the reaction product (XVII A) is combined with SiCl4 in the same way. The product obtained after 30 minutes of reaction at a Si / Ti ratio of 3/1 comprises a light yellow liquid and a brown precipitate. A similar operation gives an Si / Ti 6/1 product.

  
  <EMI ID = 118.1>

  
(1% Ti by weight) in the polymerization of ethylene

  
  <EMI ID = 119.1>

  
(45 ppm Al) and it is compared to an identical operation using hydrated magnesium chloride, with the results indicated in Table III below.

  

  <EMI ID = 120.1>


  

  <EMI ID = 121.1>
 

EXAMPLE XVIII

  
A. In a closed stirred reactor equipped with a reflux and an electric heating jacket,
42.23 parts (0.124 mol) of TBT and 3.02 parts (0.124 mol) of Mg in octane (42.8 parts) in the presence

  
  <EMI ID = 122.1>

  
dirty yellow color turns to dark brown at 80 [deg.] C (7 minutes)

  
  <EMI ID = 123.1>

  
gas evolution slows down then stops with consumption

  
  <EMI ID = 124.1>

  
has no residue (XVIII Al).

  
In a second operation, we bring together the same

  
  <EMI ID = 125.1>

  
similar results. Dilution with hexane causes neither precipitate nor deposit of residue (XVIII A2).

  
B. The product XVIII Al is activated by reaction on

  
  <EMI ID = 126.1>

  
(XVIII Bl).

  
Similarly, we activate the product (XVIII A2).

  
The dark brown liquid changes to a purple and then dark gray porridge. The clear liquid and the gray precipitate obtained contain 16 mg of Ti / g.

  
C. The product XVIII Bl activated in the

  
  <EMI ID = 127.1>

EXAMPLE XIX

  
A. In a stirred reactor, 0.160 mole of Ti (OBu) is combined., 0.160 mole of magnesium turnings and 0.027

  
  <EMI ID = 128.1>

  
cobalt salt violets give a dark blue solution on dissolving. The mixture is heated by means of a <EMI ID = 129.1>

  
of magnesium a release of gas which increases until vigorous effervescence at 107 [deg.] C in the space of 12 minutes.

  
The light blue color becomes greyish when we continue

  
  <EMI ID = 130.1>

  
the magnesium has disappeared and the reaction is stopped after 90 minutes. The milky blue product is soluble in hydrocarbons and at rest it separates into a dark blue liquid and a dark precipitate.

  
The operation is repeated with practically identical results.

  
B. The product obtained above is stirred and combined (0.0111 mole of Ti) with isobutylaluminum chloride (0.0333 mole Al) brought dropwise to a reactor. The temperature reaches a maximum of 40 ° C. with the formation of a greyish precipitate which, after a further addition of BuAlCl-, becomes brown. After 30 minutes of additional stirring, the reaction is stopped and a dark red-brown liquid and a brown precipitate are obtained.

  
C. The catalyst component prepared in Example XIX above is used in the polymerization of ethylene (88 [deg.] C, 10 mol% of ethylene, 0.0002 part of catalyst calculated as Ti, approximately 45 ppm triethyl-

  
  <EMI ID = 131.1>

  
  <EMI ID = 132.1>

TABLE IV

  

  <EMI ID = 133.1>

EXAMPLE XX

  
A. In a stirred reactor equipped with a jacket

  
  <EMI ID = 134.1> <EMI ID = 135.1>

  
the solution quickly darkens into a black liquid with vigorous effervescence due to the release of gas on the surface of the magnesium. The solution takes on a blue coloring and with gentle reflux up to 122 [deg.] C, it forms a dark blue-black liquid with a little residual magnesium.

  
  <EMI ID = 136.1>

  
with a slight green undertone. The reaction is stopped and a dark blue-black liquid and a green precipitate are recovered, in a volume ratio of approximately 95/5.

  
B. The above product is combined with chloride

  
  <EMI ID = 137.1>

  
and 6: 1 by adding the chloride dropwise to a reactor containing the titanium product. In the first reaction (3 μl), the alkyl chloride is added at the rate of one drop every 2 to 3 seconds until a maximum temperature of 42 [deg.] C is reached with bending

  
from blue-green to brown. After another 30 minutes of stirring, the product is isolated, which comprises a brown-red liquid and a brown precipitate (XX B).

  
C. Similarly, an Al / Ti 6tl product is prepared with the same results (XX C).

  
D. The products XXB and XXC are used with triethylaluminum as cocatalyst (45 ppm Al) in

  
  <EMI ID = 138.1>

  
The operations are stopped after 60 minutes with the results indicated in Table V below.

TABLE V

  

  <EMI ID = 139.1>
 

EXAMPLE XXI

  
A. In a stirred reactor equipped with a jacket

  
  <EMI ID = 140.1>

  
metallic magnesium. As you continue to heat, the gas evolution increases until, at 102 [deg.] C

  
(15 minutes of reaction), the system takes on a slightly dirty brown color. A vigorous effervescence continues with darkening of the brown color until, at 126 [deg.] C (75 minutes), all the magnesium has disappeared, the reaction is then stopped. The product (XXI Al) comprises a dark brown liquid soluble in hydrocarbons and a small amount of a fine precipitate.

  
In a second operation, 0.149 mole of TBT, 0.149 mole of Mg and 0 # 051 mole of NiCl2.6H20 are combined in octane in the same way. The metallic Mg disappears at
115 [deg.] C (120 minutes) and a dark black-brown liquid soluble in hydrocarbons is obtained which, at rest,

  
separates into a very fine dark precipitate and a yellow liquid, about 50/50 by volume (XXI A2).

  
B. The reaction product IA 1 is stirred and a portion (0.0137 mole of Ti) is placed in a reactor with hexane as diluent and iBuAlCl is added. (0.0411 mole

  
  <EMI ID = 141.1>

  
2 to 3 seconds up to 28 [deg.] C and one drop per second up to a maximum temperature of 39 [deg.] C. After the addition is complete, the contents of the reactor are stirred for

  
30 minutes and the product comprising a liquid is isolated

  
  <EMI ID = 142.1>

  
The same product (XXI Al) is combined with ethyl aluminum chloride in the same way, with an Al / Ti molar ratio of 3/1. The product includes a red-brown liquid

  
  <EMI ID = 143.1> In a practically identical way, the product is brought together

  
  <EMI ID = 144.1>

  
In another operation, react the product XXI A2 in the same way on iBuAlCl2 with a report

  
  <EMI ID = 145.1>

  
dark liquid and a dark precipitate (XXI B4).

  
The same product is assembled in the same way XXIA2

  
with ethyl aluminum chloride and a liquid is obtained

  
  <EMI ID = 146.1>

EXAMPLE XXII

  
A. Example XXI A is repeated while bringing the reagents

  
  <EMI ID = 147.1>

  
changes from dark yellow-brown to dark brown with gas evolution, then to gray-brown and then to dark blue-black,

  
  <EMI ID = 148.1>

  
takes place in 6 hours (XXII A).

  
B. The product XXII A is combined with ethyl aluminum chloride in the manner of example XXI B, with a ratio

  
  <EMI ID = 149.1>

  
and a brown-red precipitate (XXII B).

EXAMPLE XXIII

  
Example XXII A is repeated, bringing the reactants with a molar ratio of 1 / 0.75 / 0.128. The brown product

  
  <EMI ID = 150.1>

  
aluminum at an Al / Ti molar ratio of 3/1.

EXAMPLE XXIV

  
A series of TiMgNi catalysts prepared as indicated in Examples XXI B and XXII B are used as constituents

  
  <EMI ID = 151.1>

  
  <EMI ID = 152.1>

TABLE VI

  

  <EMI ID = 153.1>


  
1 Operations with high proportions of hydrogen are extremely rapid and lead to an accumulation of polymer which means that operations must be stopped.

EXAMPLE XXV

  
  <EMI ID = 154.1>

  
octane in a heated reactor equipped with reflux, in the manner of the preceding examples, to obtain reaction products at respective molar ratios of 1/1 / 0.34 and 1 / 0.75 / 0.128.

  
B. The latter product is activated by reaction on ethyl aluminum chloride in an Al / Ti ratio of 3/1.

  
C. The brown precipitate obtained is separated from the supernatant red-brown liquid and used with TEA to provide

  
  <EMI ID = 155.1>

  
D. The reaction product 1/1 / 0.34 prepared above is also activated with isobutylaluminum chloride in an Al / Ti ratio of 3/1. The solid product is washed several times with hexane and used with TEA in an ethylene polymerization reactor, preloaded with butene-1, to obtain a resin having the

  
  <EMI ID = 156.1> <EMI ID = 157.1>

  
In the following example, the catalyst components are activated by reaction with a halide component.

EXAMPLE XXVI

  
A. In the following operations,

  
  <EMI ID = 158.1>

  
that are added gradually, usually drop by drop to control the exothermic reaction. The reaction is carried out under ambient conditions for a time sufficient to complete the addition with stirring of the reagent, for 10 to 30 minutes after the appearance of

  
the maximum temperature (if necessary, the solid and liquid TMMg constituents are mixed in a slurry and

  
we use them in this form). Reagents and their

  
  <EMI ID = 159.1>

  
Constituent of catalyst,
  <EMI ID = 160.1>
 Constituent of catalysts

  

  <EMI ID = 161.1>
 

EXAMPLE XXVII

  
A. samples of activated catalyst are used

  
  <EMI ID = 162.1>

  
polymerization, with the results indicated in Table VII below
  <EMI ID = 163.1>
  <EMI ID = 164.1>
  <EMI ID = 165.1>
 As can be seen by comparing the molar ratio

  
  <EMI ID = 166.1>

  
B. In the following additional operations, the effect of the Al / Ti ratio in the activated THUG catalysts (molar ratio 1 / 0.65 / 0.11) is studied in the polymerization of ethylene. The results obtained are indicated

  
  <EMI ID = 167.1>

  

  <EMI ID = 168.1>


  

  <EMI ID = 169.1>


  

  <EMI ID = 170.1>
 

  
C. In another series of experiments, using a

  
  <EMI ID = 171.1>

  
  <EMI ID = 172.1>

  

  <EMI ID = 173.1>


  

  <EMI ID = 174.1>


  

  <EMI ID = 175.1>
 

  
D. Polymerization operations are carried out at

  
  <EMI ID = 176.1>

  
and the TEA cocatalyst, using ethylene and butene-1 as a comonomer, by varying the supply of butene-1, the activators and the levels of activators. The

  
  <EMI ID = 177.1>

  

  <EMI ID = 178.1>


  

  <EMI ID = 179.1>
 

  
The lots of resin collected are stabilized.

  
  <EMI ID = 180.1>
  <EMI ID = 181.1>
  <EMI ID = 182.1>
  <EMI ID = 183.1>
 
  <EMI ID = 184.1>
  <EMI ID = 185.1>
 
  <EMI ID = 186.1>
  <EMI ID = 187.1>
 
  <EMI ID = 188.1>
  <EMI ID = 189.1>
 
  <EMI ID = 190.1>
  <EMI ID = 191.1>
   <EMI ID = 192.1>

  
3/1, EADC), hexene-1 is brought to the reactor as a comonomer with ethylene, then it is replaced by

  
butene-1 by obtaining, from the analysis of the gases released

  
  <EMI ID = 193.1>

  
  <EMI ID = 194.1>

  

  <EMI ID = 195.1>


  

  <EMI ID = 196.1>
 

EXAMPLE XXVIII

  
We also use a TMMg catalyst prepared according to

  
  <EMI ID = 197.1>

  
  <EMI ID = 198.1>

  

  <EMI ID = 199.1>


  
The polymerization can be carried out in a similar manner

  
  <EMI ID = 200.1>

  
alkyl crylates and alkyl esters.

  
We also conduct the following comparative experiments *

COMPARATIVE EXAMPLES

  
A. In the same reactor used for other preparations

  
  <EMI ID = 201.1> anhydrous remains undissolved. See also example 1 B above.

  
B. To the same system, a quantity is added in mass

  
  <EMI ID = 202.1>

  
in octane and heated to reflux. The yellow color becomes a little more intense but does not observe any reaction.

  
D. To system C above, add a quantity

  
  <EMI ID = 203.1>

  
1 / 0.34. A small amount of light yellow precipitate is formed which indicates hydrolysis of the titanium compound but the magnesium remains unaltered.

  
  <EMI ID = 204.1>

  
a molar ratio of 1 / 0.34 and heated to reflux. Once the salt is completely dissolved * the solution becomes cloudy and a little viscous with continuous reflux for 3 hours but clarifies and deposits overnight, giving a cloudy yellow liquid and a whitish precipitate. Another operation at a molar ratio

  
1/1228 gives a clear golden yellow liquid with reflux heating for only 16 minutes. AT

  
a molar ratio of 1 / 1.17, foaming and the formation of a thick cream-colored gel terminate the reaction after 45 minutes. Compare example VII above.

CLAIMS

  
1.- Process for the polymerization of 1-olefins, alone or at the same time as at least one copolymerizable monomer, under temperature and pressure conditions suitable for polymerization, characterized in that a catalytic system is used. polymerization of olefins comprising a mixture of cocatalysts, one of which is an intermetallic compound activated by a halide and which is the product of the reaction of an oxide-alkoxide polymer of transition metal and of a reducing metal having a potential oxidation higher than the transition metal.

  
  <EMI ID = 205.1>


    

Claims (1)

 <EMI ID = 206.1> by the fact that the transition metal polymer oxide-alkoxide is obtained by partial hydrolysis of the transition metal alkoxide.  <EMI ID = 207.1> by the fact that the hydrolysis is carried out with an "aquo" complex as a source of water.  <EMI ID = 208.1> by the fact that water is supplied in the form of a hydrated salt such as a hydrated aluminum salt. cobalt, iron, magnesium or nickel. 5.- Method according to claim 3, characterized in that the water is supplied in the form of a hydrated oxide, preferably silica gel. 6.- Method according to one of claims 3 to 5, characterized in that the molar ratio between the  <EMI ID = 209.1> 7.- Method according to one of claims 1 to 6, characterized in that the reducing metal is magnesium, calcium, zinc, aluminum or a mixture of these.  <EMI ID = 210.1> characterized in that the transition metal is titanium or zirconium. 9.- method according to claim 8, characterized in that the transition metal and the reducing metal are present in a molar ratio included  <EMI ID = 211.1> 10.- Method according to claim 9, characterized in that the transition metal and the reducing metal are in a molar ratio between  <EMI ID = 212.1> characterized by the fact that the halide type activator  <EMI ID = 213.1>  <EMI ID = 214.1> an alkylsilicon halide, a titanium halide or an alkyl boron halide.  <EMI ID = 215.1> characterized by the fact that the cocatalyst is an organoaluminum or organobore compound, preferably triethylaluminum or triethylborane.  <EMI ID = 216.1> characterized in that it comprises a mixture of cocatalysts, one of which is an intermetallic compound activated by a halide and which is the product of the reaction of an oxide-alkoxide polymer of transition metal and of a reducing metal having an oxidation potential higher than the transition metal.  <EMI ID = 217.1> by the fact that the halide activator is represented by at least one of the following compounds: an alkylaluminum halide, a silicon halide,  <EMI ID = 218.1> an alkyl boron halide.  <EMI ID = 219.1> characterized in that the transition metal is titanium or zirconium.  <EMI ID = 220.1> characterized in that the reducing metal is magnesium, calcium, zinc, aluminum or a mixture) of these.  <EMI ID = 221.1> characterized in that the transition metal polymer oxide-alkoxide is the product of controlled partial hydrolysis of a titanium alkoxide.  <EMI ID = 222.1> characterized in that the transition metal and the reducing metal are present in a molar ratio  <EMI ID = 223.1> 20.- Intermetallic compounds of transition metal oxides-alkoxides. their preparation and their use, as described above, in particular in the examples given.