FR2494700A1 - METHOD FOR POLYMERIZING 1-OLEFINS AND CATALYTIC SYSTEM FOR CARRYING OUT SAID METHOD - Google Patents

Abstract

THE INVENTION CONCERNS A PROCESS FOR POLYMERIZING 1-OLEFINS, ISOLATION OR AT THE SAME TIME AS AT LEAST ONE COPOLYMERISABLE MONOMER. ACCORDING TO THE INVENTION, A CATALYTIC OLEFIN POLYMERIZATION SYSTEM IS USED INCLUDING A MIXTURE OF COCATALYZERS, ONE OF WHICH IS AN INTERMETAL COMPOUND ACTIVE BY A HALOGENIDE AND WHICH IS THE PRODUCT OF THE REACTION OF A POLYMERIC OXIDE-ALCOXIDE POLYMER. TRANSITION AND A REDUCING METAL HAVING A HIGHER OXIDIZATION POTENTIAL THAN TRANSITION METAL. THE INVENTION ALSO CONCERNS THE CATALYTIC SYSTEM FOR THE IMPLEMENTATION OF THIS PROCESS.

Description

- 1 - Process for the polymerization of 1-olefins and system

  Catalyst for the implementation of this method.

  The invention relates to intermetallic compounds of alkoxides (also called alkoxides) of transition metals and processes for their preparation. More particularly, the invention provides catalyst progenitors for reacting on haiide promoters to form a catalyst component.

  suitable for the polymerization of o -olefins.

  Polyethylene has been commercially manufactured for many years by low pressure or autoclave solution or dispersion processes or

  tubular reactors at higher pressures.

  Recently, there has been interest in linear low density polyethylene resins characterized by their linearity and by short branching provided by alkene-type comonomers and which exhibit a restricted molecular weight distribution, improved strength properties, improved high melt viscosity, higher softening point, better ESCR (resistance to stress cracking under the action of the medium) and better brittleness at low temperature. These properties, as well as related properties, provide benefits to the user in applications such as blown sheets, wire and cable coating, cast sheets,

  coextrusion and injection molding and spinning.

  Typically, to manufacture the linear polymers of olefins, catalysts of the general type described by Ziegler, thus including a transition metal compound, usually a titanium halide, are used.

  mixed with an organometallic compound such as an alkyl

  aluminum. The transition metal component can be activated by reacting it with a halide activator such as an alkylaluminum halide. Among the improved catalysts of this type are those which comprise a magnesium component, usually through the interaction of magnesium or a compound thereof with the transition metal component or the organometallic component, for example by grinding, reaction It is also intended to prepare intermediates leading to high density resins with modified characteristics using such coordination catalysts. In particular, resins having a broader molecular weight distribution and a higher molecular weight distribution are desired.

higher melt index.

  The subject of the invention is a catalytic system of

  olefin polymerization comprising a mixture of cocatalyst

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

the transition metal.

  The subject of the invention is also a polymerisation process

  1-olefins, alone or together with at least one copolymerizable monomer, under temperature and pressure conditions suitable for polymerization, with a catalyst system for olefin polymerization comprising a mixture of cocatalysts, one of which is a halide activated intermetallic compound which is the reaction product of a transition metal polymeric oxide-metal oxide and a reducing metal having a potential

  oxidation higher than the transition metal.

  Transmetal metal-containing intermetallic compounds are prepared by reacting a transition metal polymeric oxide-alkoxide on at least one metal

  reducing agent, that is to say a metal having a potential of oxy-

  higher than the transition metal. Thus, a titanium polymer alkoxide or oxoalkoxide is reacted with the metallic magnesium to form a reaction product which can be activated to form a constituent

  of olefin polymerization catalyst.

  The transition metal polymeric oxide-alkoxide can be prepared by controlled hydrolysis of the alkoxide, or the polymeric oxoalkoxide can be obtained by in situ reaction, for example by hydrolysis in a reaction medium comprising the reducing metal. . For example, titanium or zirconium tetrabutoxide can be reacted

  on magnesium metal in a solvent of the hydro-

  carbide and in the presence of a regulated source of water,

Z494700

  Preferably a hydrated metal salt such as a halide

of magnesium hexahydrate.

  Alkoxides of transition metals, particularly titanium, are known for their colligative properties in organic solvents and their sensitivity to hydrolysis. It has been reported that the hydrolysis reaction from the oligomeric, usually trimeric, titanium alkoxides results in titanium polymeric oxides, which is generally expressed as follows: Ti (OR) 4 H 2 O TiOn (OR) 42n + 2n RON Ti (OR) 4 + nHO20 Condensation reactions leading to structures with primary metal-oxygen bridges, such as

GOLD GOLD

I I

OR - Ti - O - Ti - OR I i

GOLD GOLD

  which may, in turn, constitute or contribute to the formation of hydrolysis reaction progenitors. These titanium polymeric alkoxides or oxoalkoxides (sometimes also referred to as u-oxoalkoxides) may be represented by the series [Ti3 (x + 1) O4x (OR) 4 (x + 3)] in which x O, 1, 2, 3 ....., the structure reflecting the tendency of the metal to extend its coordination beyond its primary valence, together with the property that has the alkoxide to bridge two or more atoms

of metal.

  Whatever the particular form that is attributed to the alkoxide, it is sufficient in practice to understand that the alkoxy oligomers form, by controlled hydrolysis, a series of polymeric oxides-oxides ranging from dimer to linear polymer up to an indefinite chain length, through cyclic forms. On the other hand, a more complete hydrolysis leads to the precipitation of insoluble products which result, by complete hydrolysis, to orthotitanic acid.

  To facilitate the description, we will call these

  polymeric oxides-alkoxides of transition metals

  respective, representing the products of partial hydrolysis.

  The hydrolysis reaction can be carried out separately, the products isolated and stored 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 is evidence that the same hydrolysis reaction

in situ.

  The hydrolysis reaction itself can be adjusted directly by the amount of water supplied to the transition metal alkoxide and the rate of addition. It is necessary to supply water gradually or in a staggered or sequenced manner. A mass addition does not lead to the desired reaction and causes excessive hydrolysis with precipitation of insoluble bodies. A dropwise addition is suitable, as well as the use of water of reaction, but it has been found more convenient to supply water in the form of water of crystallization, sometimes called

  cationic, anionic, reticular or zeolitic water.

  Thus, commonly used hydrated metal salts are usually used when the presence of the salts themselves is not detrimental to the system. It appears that the binding provided by the coordinated water sphere in a hydrated salt is able to regulate the release and / or the availability, for the system, of the water or of species related to water, as well as it is necessary to achieve, prime

or adjust the reaction.

  The overall quantity of water used, as mentioned above, has a direct impact on the polymer oxide-oxide form obtained and is therefore chosen in view of the catalytic result (it seems, without being limiting that the stereoconfiguration of the partially hydrolysed transition metal alkoxide determines the nature of the catalyst active component or the result of its catalytic action or contributes to it

in part).

  In general, it has been found sufficient to provide only? eUtooqooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooe

  AND MESSAGE TO A LITERATURE AND ANOTHER SEDULMA AURAE AUTHOR.

  ap azlulod apAxoo-le-apxo a sTsT ':: n uo aeoua, z; aald a (v - !, oT'4pUei. ap Ile. UtTanb 9AeTg snld uolepAxop telua9od mun uevA [e xneoonpal Telam an Ins uoT eTuvla ap xnelam Where aep sa.zUAtod oep.xoote-seapAxa seaT x6U9; e; uo ", ± O * snqxeooZp tecUA; np lueATos a 2ed 9.usmrtdurqs 4, uenTTP el ua SaTsap the 9T-Tdoaddu neaATu ne uoT9e.4.uaouoo us z: laod naed uo; a aBe: ioo; s ap saTeuLou suoTF1puoo sat suep aTqe: s enualqo.eT.zem VI * lUeST ;; ss ls Srse s.neq m: a selnuTm ot? OT e9ua TIslTdmoo uauemTTeanlnTqeq se Tnb edura 'a; uepued sazexTem sep Oe: .UOc aTdurps a * aZTUesseaou sedo ao sTem'eeanqieooxpAq ocAl np U.UveToS asuItTn naed uo * s aeTodcl u suopuoo ap sud T9 a: 0ssau or aa aaeznlz9dm; x ep 0 uoTsseald oo greetethe 0o :: o'i puo soBl suup talno.gp as asTlozpAq, p uoTIoeaz VI uoi:: Op sessealA sel 4seaqTlTnb9 sgt zaouenTeuT; nsd touwOTuep * uloçuoo uo-emeo; eT' -emea seum op uoT; oup i; - a; t, zl sazqTlTnb sesT.ms u'uraTe6: 9 uenT; uT9 uT9 UT ST to: 'nssaooid sep anb ea anae'onp9 , x Tla9m aT 'ns uo; Oes' el zed .Tnsua a: e; ssaou aOOaeT asn; e.zadma. el y nad enblenb XS "l, pom as ueAned asAToapqq, p; Tnpocd np on * -a auleqo ep m = nan6uoT and eauewosToeoa.s a-, o; el anb stue: dmoo uO :: * Trtnsns I sea IT, nb TsuTe 'seuo uute.zao sueup OT nea, p etaxe uTe.jao a aesTT; n, p Ti'do.zidde s TT sTvm Sluetoful! Nbg' uemtaTTaTUassOa 1TOe UO; Do9. " eul eanb elqms II: * UOeCt dToad ap aoe.x a. Use UOTTppe, TUesseOao and Tq9P el uenuuTMp ua Sd; ouTad ua zTueA.ed A; ned uo * einqleoozpAq ed.I np ueeAlos neTlTm np; uae; TdlToxd had S 1WrOZpAq, p s' rnpocl sap anb IZS; Ag; ned uo, t anb sTO; enbeuqp

  salvsTTTn; uos eatoOm o'z; ueu6Tae; '49; TIuenb sapuez6.

  : SnTd ap; a; ueuuOiuoo Olol SO'T, tnbn; uelQtR 59Tueuunb saE -uoTsTue'l ap Telmw ep aTom 2ed nea, p aTom 'OOZ6Z:,. suitably taking into account the electric potentials, so as to minimize the side reactions, in a known manner; in general, to provide preferred levels of activity for the polymerization of olegins, the system is provided with a magnesium content by suitably selecting the reducing metal and the salt.

hydrated metal.

  In the preferred embodiment (hereinafter referred to by way of example for convenience), titanium tetra-n-butoxide (TBT) is reacted with magnesium turnings and a hydrated metal salt. preferably magnesium chloride hexahydrate, at a temperature of 50 to 1500C, in a reactor, under the autogenous pressure. TBT may be the reaction medium or a solvent of the type may be used

  hydrocarbon. The molar ratios Ti / Mg can vary -

  between 1% and 11% but, for the most homogeneous reaction system, it is preferable that the vo stoichiometric ratio Ti / I g is 1: 1, the amount of metal salt hydrate to be fed during the reaction being about 1 mole of water per mole of Mg The hydrocarbon-soluble catalyst progenitor mainly comprises a Ti content associated with a Mg content, in one or more complexes

  stereoconfiguration, which appear to be mainly

  oxygen species. Some traces of mixed oxidation states of the titanium content suggest a system of interconnected whole species comprising Ti, Ti and Ti contents, perhaps in a quasi-equilibrium relationship, at least under conditions dynamic reaction. It seems, without being limiting, that the preferential progenitor contains

Ti-0-Mg bridging structures.

  The intermetallic compounds are especially useful as catalyst progenitors, in supported or unsupported systems, for isomerization,

2494700 "

  dimerization, oligomerization or polymerization of substituted alkenes, alkynes or alkenes, in the presence or absence of reducing agents or activators, for example organometallic compounds of Group IA, IA, IIIA metals or IIB. In the preferred use of these progenitors they are reacted on a halide activator such as an alkylaluminum halide and are associated with them.

  & an organometallic compound to form a system.

  Catalyst suitable particularly for the polymerization of ethylene and comonomers with the formation of polyethylene resins. *:

* É '"',!.

  The constituent & transition metal is an alkoxide,

  normally a titanium or zirconium alkoxide, comprising.

  essentially -OR substituents, in which R -

  may comprise up to 10 carbon atoms, preferably from 2 to 5, and is more preferably an alkyl-n group, for example butyl-n. The constituent chosen is normally liquid under ambient conditions i

  and reaction temperatures to facilitate handling

  and, for ease of use, it is also: i soluble in hydrocarbons. "" 'To facilitate the conduct of the hydrolysis reaction C! Accordingly, it is generally preferable to use transition metal compounds comprising only alkoxide substituents, although other substituents may be contemplated when they do not interfere with the reaction by significantly modifying the result in use. In;

  In general, n-alkoxides which are free of halide are used.

  The transition metal component is provided in the highest oxidation state of the transition metal, so as to provide the desired structure of stereoconfiguration.

  guration, among other considerations. The most advantageous-

  As we have said, the alkoxide is an alkoxide of ..

  titanium or zirconium. Suitable titanium compounds.

  These include titanium tetraethoxides and related compounds containing one or more alkoxyl radicals, including n-propoxyl, isopropoxyl, n-propoxyl, and n-propoxyl radicals. butoxyl, isobutoxyl, secondary butoxyl, tertiary butoxyl, n-pentoxyl, tertiary pentoxyl, tertiary amyloxyl, n-hexyloxyl, n-heptyloxyl, nonyloxyl etc. Some facts suggest that the rate of hydrolysis of normal derivatives decreases as chain length increases and velocity decreases with tertiary, secondary, normal # molecular complexity: these factors must be taken into account in the choice of a preferred derivative. Titanium tetrabutoxide is very suitable for the practice of the invention and the related tetraalkoxides are also preferred, It is understood that mixed alkoxides are very suitable and can be used when conveniently disposed. if using complex titanium alkoxides, sometimes including

other metallic constituents.

  The reducing metal is provided at least in part in the zero oxidation state as a necessary element of the reaction system. A convenient source is formed by the familiar turns, ribbon or powder. As commercially available, these bodies may be in the oxidized, passivated surface and it is sometimes desirable to grind them to at least some new surface, at least to control the reaction rate. The reducing metal may be provided, as appropriate, in the form of a slurry in the transition metal component and / or hydrocarbon diluent or may be added

directly into the reactor.

  Whether in the case of the insitu preparation or for the independent preparation of the transition metal polymeric alkoxide, the source of water or the water-related species is supplied in such a way that amounts of water are released or disseminated or become accessible.

  depending on the case, at a rate delayed during the reaction.

  As mentioned above, it has been found that the coordination sphere provided by a hydrated metal salt is suitable for this purpose; however, other sources of water in the same proportions are also usable. Thus, calcined silica gel free from other active constituents but containing controlled amounts of combined water can be used. In general, the preferred source of water is a naquo "complex in which water is coordinated

  to the main body in a known manner.

  Suitable bodies include metal salts

  hydrates, especially mineral salts such as halo-

  serums, nitrates, sulfates, carbonates and carboxylates of 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 with a possibility of reflux of volatile constituents at the high temperatures generated in the reactor. Autogenous pressure is used, since the reaction proceeds smoothly in the reactor. the ambient conditions, heating to prime and maintain the reaction. As in any reaction of this kind, it is preferable to stir, simply to avoid agglomeration or encrustation on the reactor surfaces, to intimately mix the constituents and to ensure a system of

homogeneous reaction.

  Usually, a hydrocarbon-type solvent such as hexane, heptane, octane, decahydronaphthalene, mineral spirits and the like is also used to facilitate the mixing of the constituents, the transfer.

  of heat and the maintenance of a homogeneous reaction system.

  Saturated hydrocarbons having a boiling point of 60 to 190 ° C. are preferred. The transition metal liquid component can also be used at least in part.

- 10 -

  reaction medium, especially when no added solvent is used. The reaction has 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 perform the reaction through intermediate stages with appropriate reaction times, to bring the volatile bodies back to the reaction zone. Thus, butanol is formed when the titanium component is titanium tetra-n-butoxide and it forms an azeotrope with the hydrocarbon solvent. 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 a certain extent a matter of choice, in a wide range, depending on

  the reaction rate that it is appropriate to use.

  It has been found that the reaction system (consisting of the transition metal liquid component, the dissolved hydrated metal salt, the reducing metal particles and the solvent if desired) has a visible gas formation between about 60 and 700C, which suggests that the initiation temperature or activation energy level is about 50 ° C, which is therefore the minimum temperature necessary for the reaction of the polymeric oxyalkoxyl on the reducing metal. The reaction is somewhat exothermic during the reduction of the reducing metal and, therefore, can be easily pushed to the next stage, which is the reflux temperature. Since the alkanol formed is consumed widely 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 a visible metal consumption and / or or in that the reflux temperature of the pure solvent is reached,

2 49470 0

  in a time that is only 30 minutes to 4 hours or more. These temperatures can reach 140 to 1900C and, of course, one could apply

  higher temperatures, but with no apparent benefit.

  S The most convenient is to operate between 50 and 1500C, preferably between 70 and 140OC. In the absence of solvent, the upper limit will simply be established by the reflux temperature of the alkanol generated during running.

of the reaction.

  The reaction of the constituents is especially clearly revealed by the marked color change, with exotherm, which accompanies the beginning of the evolution of gas. When the solution is neither opaque nor cloudy and allows observation, a gas evolution, varying from bubble formation to vigorous effervescence, is most evident on the surface of the metal and the solutions, generally light color, become immediately grayish, then quickly darker, becoming blue, sometimes purple, usually black-blue, sometimes with a greenish hue. The analysis of the gas shows no HC1 and is essentially HH. After the rapid change of color there is a certain obscuration of the color during a gradual rise in temperature, with further evolution of 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 appears to consume gradually in a flow-related manner at the same time as

the remaining reducing metal.

  The reaction product is at least partially soluble in hydrocarbons and is maintained in the form of a slurry for convenience of use

  ulterior. When the viscous product is isolated at half

  solid, it shows # the ray diffraction analysis

  X. an essentially amorphous character.

  The molar ratios of the constituents may vary

- 12 -

  in certain ranges, without significantly affecting the result given by the catalyst precursor in the end use. Thus, to avoid competing reactions that make the product inconveniently gelatinous or unmanageable, the transition metal component is ordinarily supplied in at least a molar ratio relative to the reducing metal, but the transition metal / reducing metal ratio may vary between 0, About 5X1.0 and 3.0: 1.0 or more; it is preferably between 1% and 1%. An insufficient level of reducing metal causes a lowering of the reaction temperature, so that the reflux temperature of the pure solvent is not yet reached; on the other hand, an excess of reducing metal is immediately visible by the non-consumed fraction thereof, so that the person skilled in the art will easily determine the desired quantity of this constituent. In these ranges, a variable proportion of the product of The reaction may form a hydrocarbon-insoluble component, but it can be diluted with the soluble component and is usually done for use, for example, for a further reaction on a halide activator for the formation of a hydrocarbon-insoluble component. olefin polymerization catalyst. The amount of this insoluble component can be adjusted in part 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, It has been found that equimolar amounts of the Ti / 4g / H 2 O components, for example, are most suitable for forming a

homogeneous reaction product.

  The 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. Thus, in the case of MgCl.sub.2.6H.sub.2 O, an amount of 0.17 mole provides during the reaction about 1 mole of water and this proot.p up to about 2 moles of water ensures the most effective reactions. easy with one or more moles of transition metal component. More generally, the amount of H 0 can vary from about 0.66 to about 3 moles per mole of transition metal. Of course, the amount of water present at any given stage of the reaction is likely to be much lower, up to catalytic proportions relative to the remaining components, depending on the mode and rate of participation in the reaction process. who are currently unknown. However, it is especially contemplated, without limitation, as a working hypothesis, that the water, or the related species governing the rate of reaction, is activated, released, made accessible or diffused so as to provide this species in a regular, sequenced manner. constant or variable, r related to speed. However, the same molar proportion of free water supplied at the beginning of the reaction is entirely ineffective for initiating the reaction at this temperature or at a higher temperature and results in reactions.

  complete hydrolysis that are undesirable.

  The amount of water measured is substantially in equilibri molar or molar excess relative to the reducing metal component and appears to be related to its

  consumption in the reaction, as a lack of

  The molar amount of water invariably leads to the persistence of an excess of reducing metal. In general, a moderate excess of water of 10 to 40% is appropriate to ensure complete reactioui. Larger proportions are suitable, without limitation, but must be maintained in stoichiometric equilibrium with respect to the transition metal component. The choice of "aquo" complexes or hydrated metal salts, when used, is aimed essentially at regulating the availability of the water supplied to the system. Thus #, sodium acetate trihydrate may be suitable, as well as

- 14 -

  magnesium acetate tetrahydrate, magnesium sulfate

  heptahydrate and magnesium fluorosilicate hexahydrate.

  A salt having the maximum degree of hydration compatible with the controlled release provided by the coordinated bond should be preferred. The most appropriate is to use a hydrated magnesium halide such as

  magnesium hexahydrate or magnesium bromide hexahydrate.

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

modified & this effect.

  The reaction system as defined above does not require, but tolerates, an electron donor or a Lewis base, or a solvent that partly plays 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 not clear whether a proton or electron donor transfer mechanism

  exists concurrently in the reaction system.

  No separation is necessary since at least a portion of the reaction product is soluble in the saturated hydrocarbon when it is used as a solvent or provides a solvation medium such that even when a precipitate occurs also, and even after storage, one can easily form a reactive slurry usable. According to a preferred aspect of the invention, the reaction product (catalyst progenitor) is further reacted with a halide type activator such as an alkylaluminium halide, a silicon halide, an alkyluilicon halide or a halide. titanium-15- or an alkylbore halide. It has been found that the catalyst progenitor can easily be 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 a slurry or stored for later use. Usually, to have the best control of the molecular weight and especially to manufacture a low density resin, one only uses as

  catalyst the solid product washed with a hydrocarbon.

  The halide activator is commonly provided for interaction at a molar ratio (between

  aluminum, silicon or boron and the transition metal

  between 3: 1 and 6sl, although it has been used

  successfully reports of 2sl or more.

  The catalytic product obtained can be used directly in the polymerization reaction, but typically it is diluted in a suitable manner to provide, in a suitable feed, an amount of catalyst which is equivalent to 80 to 100 mg of transition metal. , based on a nominal productivity greater than 200,000 g of polymer per gram of transition metal, in continuous polymerizations, this productivity being r

  ordinarily exceeded by the catalyst according to the invention.

  Those skilled in the art make adjustments for responsiveness and efficiency, usually by

  simple dilution and by adjusting the flow rates.

  For use in the polymerization, the transition metal catalyst is combined with an organometallic cocatalyst such as triethylaluminum or triisobutylaluminum or a nonmetallic compound such as triethylborane.

- 16 -

  polymerization comprises 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 in A1), which is introduced into a reactor maintained at 4.5 MPa relative and 71 C. In general, the amount of cocatalyst is calculated, when used, so that it is about 30 to 50 ppm, calculated

  in A1 or B, relative to isobutane.

  Examples of cocatalysts are trialkylaluminum compounds such as triethylaluminum, triisobutylaluminum, tri-n-octylaluminium, alkylaluminium halides, alkylaluminum alkoxides,

  dialkylzinc, dialkyl magnesium compounds and

  metal borates, including those of alkali metals, especially sodium, lithium and potassium, and

  those of magnesium, beryllium and aluminum. The cocata-

  Metalless lysers include alkylbore compounds such as triethylborane, triisobutylborane and trimethylborane and boron hydrides such as

  diborane, pentaborane, hexaborane and decaborane.

  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 as a granular solid.

  The low pressure polymerization reaction, for example 1.4 to 6.9 MPa, and a temperature of 38 to 93 ° C is conducted by applying hydrogen as desired to control the molecular weight distribution. Other normal alkenes, in the minority relative to ethylene, can be fed to the reactor to copolymerize therewith. Typically, butene-1 or a mixture thereof and hexene are used at a level of about 3 μmol, although other levels of comonomer-olefin can be readily used. such n-alkenes are used as comonomers, it is possible to

  give the resin densities of 0.91 & 0.96.

:: Q

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-, - 7! '3'!

  Other olefin comonomers such as 4-methylpentene-1, 3-methylbutene-1, isobutylene, heptene-1, decene-1 or dodecene-1 can also be used. from 0.2% by weight only, especially when using monomer mixtures. However, polymerization can be carried out at higher pressures, for example 138 & 276 MPa, in autoclaves or tubular reactors, if desired. "When speaking here of" compound "or" complex "intermetallic, it means any reaction product," formed by coordination or association or in the form

  one or more inclusion or occlusion compounds ,.

  of clusters etc ..., under the applicable conditions, the integrated reaction being generally revealed by a change of

  color and a gas release that probably translates -

  a reduction-oxidation, a rearrangement and an association between the non-consumed constituents of the

reaction system. -

  The following examples, taken together with

  the above description serve to illustrate

  The invention as well as its mode of execution and use, All parts are by weight, unless otherwise indicated. The melting indices are respectively measured under conditions E and F of ASTM D- 1238-57T for MI and HLMI values, on powder or resin samples, as specified The HI4I / MI or MIR ratio is the melt index ratio, which is a measure of shear sensitivity, reflecting the distribution molecular weight. The other tests are such that we:

  indicates them or as they are classically driven -

in related branches.

EXAMPLE I.

  A. Reactor is blended with 6.0 parts of

  Ti (OBu) 4 (TBT) and 4.2 parts CrC13.6H2O.

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  Chromium dissolves partially and some heat is released when shaken. The complete dissolution is carried out with moderate heating between 60 and 700C. A further 3.3 parts of chromium salt are dissolved with stirring over a period of 20 minutes. To the green solution, in total, 0.3 parts of shavings are added in portions

  magnesium, which causes a vigorous release of gas.

  The cooled, excess magnesium-free reaction product (which has completely disappeared) is a viscous green liquid soluble in hexane B. In a similar operation, anhydrous chromium chloride is used with titanium dioxide, but no reaction occurs when heating above 100 ° C for half an hour. By adding zinc powder and pushing the heating above 1500C, no reaction is observed. The replacement of magnesium clots does not give a reaction either. It is concluded that the hydrated salt was a constituent

  necessary reaction system.

EXAMPLE II

  A. In a stirred reactor equipped with an electric heating jacket, 0.121 moles of TBT, 0.015 moles of CrCl3.6H2O and 0.0075 moles of MgO were combined. The chromium salt dissolves completely at about 60 ° C. and the reaction on the magnesium clots is revealed by a gas evolution at 850 ° C., vigorous at 1000 ° C., calming at 116 ° C. while a little Mg remains. After dissolving the remaining Mg, heating is continued to a total reaction time of 1 hour 45 minutes. The reaction product at room temperature is a dark green liquid which dissolves readily in hexanea B. Similarly, a reaction product comprising 0.116 moles TBT, 0.029 moles CrCl 3 is prepared. 6H20 and 0.029 moles Mg. A dirty green reaction product formed at 118 ° C becomes bluish-blue in color and the evolution of gas continues. We stop

- 19 - ..

  reaction after the magnesium has disappeared after 1 hour 15 minutes The product is soluble in hexane C. The above operations are repeated with 0.116 mol of TBT, 0.058 mol of CrCl 3 0145 moles Mg .: "3 The reaction is complete in 115 minutes and

a product soluble in hexane.

  D. The proportions of reagents, ie 0.115 moles of TBT, 0.0287 moles of CrC 13.6H 2 O and 0.0144 moles of Mg are again modified in another operation. A dirty green matter that appears at 114oC becomes blue on the surface of the Mg. The product is soluble in hexane. E. In a similar operation, 0.176 X mole of TBT, 0.30 mole of CrC13.6H2O and 0.176 mole of Mg are reacted in octane. The light green color of the reaction at 70 ° C becomes dirty with increased gas evolution and almost black at 90 ° C. The color becomes green again at 119 ° C. and the reaction terminates at 121 ° C. with disappearance. complete magnesium. The product (6.9% Ti, 3.5% Mg,

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

  In a further operation, 0.150 moles of TBT, 0.051 moles of 13.6H.sub.2 O CrC, and 0.150 moles of Mg are reacted in an octane reaction (about 50% by volume). Again, the dirty green color changes to almost black, with vigorous effervescence, forming, at 109 ° C, a dark blue-black product (5.7% Ti, 2.9% Mg, -,

2.1% Cr by weight).

EXAMPLE III

  A. In a reactor, the reaction product was combined with isobutylaluminum chloride added dropwise in desired proportions to give an Al / Ti molar ratio of 3: 1: 1. The green color mix initially goes to violet-brown at 38 C and, upon completion of! the addition of reagents to 39 C, it became red-brown. After 30 minutes of further stirring,

"4 ',;

,% z., "|.

- 20 -

  stops the reaction, the product comprising a liquid

  dark red-brown and a dark brown precipitate.

  B. The reaction product IIF is similarly reacted with isobutylaluminum chloride (molar ratio Al / Ti 31). The maximum temperature, at the end of the addition, is 48 ° C, but no brown turn is observed. The product consists of 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 C, 10 mole% ethylene, 0.0002 part of catalyst calculated as Ti, about 45 ppm of triethylaluminum, calculated as A1, H2 as indicated), the results being shown in Table I below:

TABLE I

  H2, kPa Product, Catalyst Resin Relative Properties g Pe / q Tih MI - I H LMI / MI

IIIA 414 35160 10.1 265 26.3

827 29220 18.9 618 32.6

IIIB 414 30380 9.6 264 27

827 26880 32.8 855 26.1

  In the following example, the catalyst component of the invention is prepared starting from the reagent mixture.

in the absence of added solvent.

EXAMPLE V

  A. 0.1212 moles of Ti (OBu) 4 (TBT), 0.121 moles of magnesium turnings and 0.0012 moles of MgCl2 · 6H2O (TBT / Mg) were combined in a stirred reactor equipped with an electric heating jacket. /MgC12.6H2O = 1: 1SO4, 01 in moles). The magnesium salt dissolves entirely at room temperature, forming a homogeneous mixture. The mixture is heated gradually and, & 950C, the release of

  gas begins on the surface of magnesium turnings.

  At 140C, with reflux, the release became more

, r ..?

  - 21 - vigorous. The solution darkens and the release ceases

  at 170 C1 the reaction is stopped. The product contains -

  an excess of magnesium - only about 8.5% of the introduced magnesium reacted - and it is soluble in hexane.

  B. In another operation, increase the proportion.

  molar of HgC12.6H20 (TBT / Mg / MgC12-6H20 - l2l.0, l) Golden yellow liquid becomes greyish with evolution of

  gas at 104 C and darkens when heated to 168 C.

  After 125 minutes of reaction, the product contains

  some magnesium excess, about 63% reacted.

  C. In another operation, the molar ratio is 0.005. The dark blue product is very viscous and is not easily diluted with hexane. All magnesium "i

A15 is consumed. l.

  The following example shows the preparation performed

  in a hydrocarbon solvent.

EXAMPLE VI

  A. In a stirred reactor equipped with an electric heating jacket, 50.2 parts (0.148 mole) Ta of TBT are added to 58.6 parts of octane. 0.074 moles of magnesium turnings are added, stirring is begun and 0.0125 moles of MgCl 2 · 6H 2 O is added over a period of one minute while heating. At 75 ° C (20 minutes) the magnesium salt has completely dissolved and at 95 ° C (25 minutes), the gas evolution begins at the surface of the "turnings": magnesium, it increases while the solution becomes

  greyish then dark blue, with reflux at 117 C (35 minutes).

  The magnesium metal reacted completely in 1 hour (128 to 129 ° C.) and the reaction was stopped. It is calculated that the octane-solubilized blue product (a small amount of greenish precipitate remains) contains, by weight, 6.8% Ti and 2.0% Mg (Ti / Mg 3.4: 1). in weight,

1.7: 1 in moles). -

  B. The above operation is practically repeated except that the molar proportions are changed.

- 22 -

  reagents, with the following results

Molar ratio Modal report

  Ti / Ng / MgCl2.6H2wire Ti / Mg Rem arques

1.0 / 0.65 / 0.11 1.32

1.0 / 0.75 / 0.128

1.0 / 1.0 / 0.085

1/1 / 0.17

1/1 / 0.34

1/1/0, 51

1/2 / 0.17

1/2 / 0.34

  1.14 0.92 0.85 0.75 0.66 0.46 0.43 1.70 1.50

* 2/1 / 0.17

2/1 / 0.34

3/1 / 0.51

  1.99 Black-dark blue liquid precipitated green. 6.6% Ti, 2.6%

Mg by weight (calculated).

  Blue solution with greenish shade. 6.5% Ti, 2.8% Mg by weight (calculated) Black-blue liquid with slight green precipitate (insoluble in acetone, alkanes and methylene chloride). A

few minutes.

  Black-dark blue liquid, 6.6% Ti, 3.9% Mw by weight (calculated) Black darkblue liquid, 6.7% Ti, 4.6% Mw by weight (calculated) Milky blue liquid, 3.7% Tif 2.9 Mg by weight (calculated) Dark blue-black liquid and viscous green gel. A little unaltered MgO. Dark blue-black liquid and gel

viscous. A little unaltered Mg &.

Example IIA

Black-blue solution. 7.1% Ti,

2.3% Mg by weight (calculated).

  Black-blue liquid with slight shade 6.1% Ti, 1.6%

Mw by weight (calculated 6).

  C. Preparation 1/1 / 0.34 above is repeated except that 63.7 parts of TBT are used with 67.5 parts of hexane as reaction solvent medium. A dark blue-black liquid containing, at the

  calcination, 8.2% Ti and 1.6% Mg by weight.

  The following example shows the step preparation of the catalyst component

EXAMPLE VII

  2.61 parts of MgCl 2 · 6H 2 O - 23 and 34.2 parts of TBT are combined with stirring. In 30 minutes, the mixture of yellow liquid and crystalline salt is replaced by a milky yellow opaque viscous liquid. Prolonged agitation causes the disappearance of the haze and gives in 2 hours a transparent yellow liquid (in a second operation conducted in the 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 examples.

  above, using the light yellow liquid prepared above and 1.83 parts Mg, with a molar ratio of 1: 0.75 / 0.128 in the octane "The reaction progresses steadily, giving a dark blackblue liquid and a green precipitate in the same manner as other mentioned reactions. The product is activated by ethylaluminium dichloride at an Al / Ti ratio of 3: 1 to form a

  catalyst for the polymerization of olefins.

  The following example shows the meaning of the rate

combined water.

EXAMPLE VIII

  A series of identical operations is carried out at a molar ratio of 1/0, 75 / 0.128 (TBT / Mg / MgCl 2 · 6H 2 O), with the exception that the degree of hydration of the magnesium salt

is changed.

  When using MgCl 2 O 4 H 2 O (H 2 O / Mg. 0.68 / 1 versus 11 for MgCl 2 .6H 2 O) Only 89.1% of the magnesium metal react. The use of MgCl 2 .H 2 at the same overall molar ratio (H 2 O / Mg 0.34: 1) results in only a 62.1% reaction of Mg 9. In repeated operations, the amount of hydrated salt introduced is increased to give an H20 / Mig ratio of 1 = 1. All the magnesium metal reacts. It is also observed that the amount of insoluble product increases with the level of salt. The following example illustrates the use of other insoluble products.

- 24 -

titanium compounds.

EXAMPLE IX

  A. 45.35 parts (0.1595 moles) of Ti (OPri) 4, 0.1595 moles of Mg and 50.85 parts of octane are placed in a stirred flask equipped with an electric heating jacket. add 0.027 moles of MgCl2 · 6H2O. The milky yellow mixture turns gray with reflux, about 88 ° C, and turns blue at 90 ° C. with effervescence. Based on the remaining magnesium, it is concluded that the reaction is partially

  inhibited by the presence of the octane / isopropanol azeotrope.

  B. The reaction described in A is repeated with a molar ratio of 1: 0.75: 0.18, using decahydronaphthalene as diluent (boiling point 185 to 189 ° C.). After 6 hours, the reflux temperature reaches 140 ° C and the reaction is stopped. A dark blue-black liquid with a small amount of dark precipitate is obtained. 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 is obtained.

  dark precipitate. About 50% of the magnesium react.

  D. Titanium tetranonylate was similarly used with magnesium and MgC 12.6H 2 O at a molar ratio of 1: 0.75: 0.128. A blue liquid is formed,

  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 under similar conditions. to the examples above. About half of the magnesium is consumed in about 3 hours and a dark blue-black liquid and an olive-green precipitate (50/50 by volume) are recovered.

  The following example uses a zirconium alkoxide.

2494700, -:? /:

- 25- -,

EXAMPLE X

  A. In a reactor, 12.83 parts (0.028 moles) D of Zr (OBu) 40BuOH, 0.34 parts (0.14 moles) of Mg in the form of commercial forms and 8.8 parts of octane are added. The mixture is refluxed at 125 ° C. with stirring for minutes, without noticing a reaction. 0.97 part (0.005 mol) of MgCl 2 · 6H 2 O is added, vigorous effervescence is noted and the mixture becomes milky: B. In a second operation, 31.7 parts (0.069 mol) of the title compound are combined. zirconium, 0.069 mol of magnesium metal and 57.6 parts of mineral spirits (boiling point 170 to 195 ° C.) and 4.79 parts of MgCl 2 · 6H 2 O (0.0235 mol) are added with stirring. Heat is applied to the reactor by an electrical jacket. Within 5 minutes, the mixture became opaque and gas evolution on the surface of the magnesium metal was evident when the temperature reached eC after 8 minutes of reaction. The evolution of gas continues with vigorous effervescence, the temperature rising to 108 ° C, when a whitish solid appears.

  When heating continues at 1330C (1 hour reaction).

  all the metallic magnesium disappeared, the reactor containing a milky white liquid and a white solid. The mixture is cooled and 92 parts of a mixture containing 6.8% by weight Zr and 2.4% Mg (Zr / Mg = 2.8: 1 by weight,

  0.75 mol%) which is soluble in hydrocarbons.

  The product can be activated in a known manner, for example with an alkylaluminum halide, by reacting it preferably on a molar ratio: Al / Zr of from about 3: 1 to about 6: 1, to obtain, in combination with an organic or organometallic reducing agent, a catalyst system for the polymerization of olefins suitable for the formation of polyethylene resin. P The following example shows the replacement of magnesium i

  by calcium as a reducing metal.

- 26 -

EXAMPLE XI

  A. In a stirred reactor equipped with an electric heating jacket, 0.074 moles of Ti (OBu) 4, 0.074 moles of Ca (commercially thickened commercial turnings into smaller pieces) and 0.0125 moles of MgCl 2 are combined. 6H20 in octane. When it reaches 105 ° C, the solution darkens and at 108C, with evolution of gas, the solution takes a dark gray appearance. At 1 L, 5 C, a rapid evolution of gas followed by the formation of a dark blue liquid is observed. After 90 minutes, the reaction is stopped and a liquid product is isolated.

  black-dark blue with greenish uoenuance.

  The operation is repeated at the same molar ratio. 50% of the calcium reacts giving a dark blue liquid and a gray solid containing, by weight, 6, 2% Ti, 2.6% Ca

  and 1.1% Mg (1 / 0.5 / 0.34 molar ratio) (XI Al).

  In another operation, the same reagents are combined in a molar ratio of 0.75 / 0.128. Calcium reacts at 63% and gives a black-blue liquid and a green solid. The product (molar ratio 1 / 0.47 / 0.128) contains,

  by weight, 6.6% Ti, 2.6% Ca and 0.4% Mg (XI A2).

  B. Reaction product XI Al is then reacted with ethylaluminum chloride in an Al / Ti molar ratio of 3/1 and 6/1. The products are diluted with hexane and the activator of the type is slowly added.

  halide to control the highly exothermic reaction.

  In the 3/1 operation, the whitish slurry formed initially is transformed, upon completion of the reaction, into a pink liquid and a white precipitate. Has a report

  Al / Ti 6/1, the mixture turns gray then lime green.

  Product XI A2 is also treated with EtAlCl 2 in an Al / Ti molar ratio of 3/1 and 6/1. Reactions are regular, giving 3/1 a dark brown mush

  and at 6/1 a red-brown liquid with a brown precipitate.

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

shown in the following table.

TABLE II

  TBT / Ca / MgCl2 molar ratio. 6H20 Reaction Reaction H2 'kPa Relative Productivity (gPE / g Ti.h) Properties of Mi HLMI MIR Resin Powder

1 / 0.5 / 0.34

1 / 0.47 / 0.128

3/1 6/1 3/1 6/1 950

43,810

930

11,260

27,420

33,050

  3.84 1.03 1.73 7.0 0.35 1.75 47.7 73.7 21.0 34.1 46.3 42.6, 7, 1 66.0 Conditions in the reactor & the bench scale bench s Isobutane diluent Temperature g 88 C Hydrogen as indicated Triethylaluminum cocatalyst (TEAL) & approx. 45 ppm Al Ethylene X 10 mol% Time s 60 minutes I l N 4- o On O "4 O: 4 li Buried Ue =

- 28 -

  The operations show a slightly larger molecular weight distribution of the resin, in comparison

  the case where magnesium is used as the reducing metal.

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

EXAMPLE XII

  Ao In a stirred closed system equipped with reflux and heated externally, 0.204 mole of TBT is collected,

  0.153 moles of ZnO granules and 0.026 moles of MgCl2.6H2O.

  Within 13 minutes (85 ° C), there is a fast turn to blackblue with increasing gas release,

  leading to a vigorous effervescence and a foaming.

  The product, which is a black-blue liquid (without precipitate) comprising 7.7% Ti, 0.9% Zn and 0.5% Mg by weight, yellowed

when exposed to the air.

  B. The reaction product TiZnMg is reacted

  (molar ratio 1 / 0.86 / 0.128) on isobutyl chloride

  aluminum at an Al / Ti molar ratio of 3/1, in hexane

between 10 and 130C (XII Bl).

  C. The preparation of the product TiZnMg (XII A) is repeated using zinc powder with similar results. Another operation with zinc foam uses only 7% zinc and one observes the formation

  a green layer on the surface of zinc.

  D. The activated product XII B1 prepared as above is thoroughly washed with hexane and used in the preparation of a low density polyethylene resin. The reactor was precooled with sufficient butene-1 to provide the desired density and the reaction (by adding butene-1 in portions along with ethylene) was carried out at 77 ° C. and 241 kPa of H 2 in the presence of triethylaluminum as a catalyst. The recovered resin has the following properties: density

0.9165, MI 1.68, HLMI 52.1, MIR 31.

  The following example involves the use of potassium

as a reducing metal.

- 29 -

EXAMPLE XIII

  In a closed system equipped with reflux and heated externally, 62.7 mmol of TBT, 47 mmol of fresh metal potassium (freed of its coating of oxide / hydroxide by scraping under octane) and 8.0 mmol of MgCl 2 are combined. .6H20. In 2 minutes at 350C, the color changes to black-blue and bubbles appear. It follows a vigorous release of gas and an effervescence. When the metallic potassium has disappeared, the reaction is stopped (after 5 hours). A dark blue-black 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. 112.31 parts (0.33 moles) of Ti (OBu) 4, 8.91 parts of Al (aluminum powder) were mixed in a reactor, while stirring and applying heat through an electrical jacket. Alfa Inorganiesphericall lower & 0.35 mm) and 11.4 parts (0.056 mole) MgCl 2 · 6H 2 O (molar ratio)

llO, 17).

  When it reaches 1000C in about 10 minutes, the yellow color is darkened and at 1181C, a vigorous effervescence begins with release of gas. At 1220C,

  the reflux liquid takes on a gray shade and the temperature

  The color stabilizes while the color changes from dark gray with blue shade to dark blue to black-blue after 27 minutes of heating. The temperature is maintained, it is raised to 145 ° C. in the course of 1 hour 20 minutes, the evolution of gas is then practically

complete and stop the reaction.

  The product is at room temperature a liquid

  viscous with unaltered aluminum particles.

  The unreacted aluminum is separated, washed and weighed, and 6.7 parts of Al.sub.2 O are found to have reacted. The product contains, by weight, 7.9% Ti, 3.4% Al and 0.7% Mg

(1s0 molar ratio, 75: 0.17).

  B. In a reactor placed in a bath of

- 30 -

  After cooling, 9.10 parts of the product prepared above (0.719 parts of Ti, ie 0.015 moles) were added to 13.0 parts of hexane. 0.045 mol of ethylaluminum dichloride is gradually added while maintaining the temperature between 5 and 20 ° C. The mixture, stirred for 30 minutes, gives a dark brown-brown slurry and a non-solid.

Handy (Bi).

  A second operation (0.175 mol of Ti / 0.0525 mol of Al) is carried out without cooling, to a maximum temperature of 38 ° C. and a slurry is formed again.

  red-brown with a non-handy solid deposit (B2).

EXAMPLE XV

  The products of Example XIV are used as catalysts in the polymerization of ethylene under standardized conditions (88 ° C., 414 kPa relative to H 2), using triethylaluminium as cocatalyst, with the following results:

MI KMIR

B1 0.14 6.45 46.1

B2 0.38 17.4 45.7

EXAMPLE XVI

  A. Similar to the foregoing, 0.133 moles of TBT, 0.100 moles of A1 and 0.017 moles of AlC 13.6H 2 O are combined in octane and reacted at 3- 2 within 7 minutes. hours 15 minutes to get a liquid

  black-dark blue and a small amount of a gray solid.

  About 40% of the aluminum reacts giving a product containing, by weight 6.6% Ti and 1.6% Al

(XVI Ai).

  In the same way, the same reagents are combined in a molar ratio of 1/1 / 0.17. About 58% of the Al react, 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 A1 and XVI A2) are activated by the

  Ethylaluminum chloride at an Al / Ti ratio of 3/1.

  C. The solid fraction of the supernatant is isolated

Z 4 9? 00 -

* 7 'h: *

2494700 '

  31, activated reaction product (XVI A2) and used, with: TEA as cocatalyst, in the polymerization of: ethylene, at 77 C and 103 kPa relative H to obtain: a resin characterized by MI 0 , 02, HLMI 1, 01, MIR 50.5: S and in a second operation, MI 0.02, HIMI 0.45 and

MIR 22.5. '

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

EXAMPLE XVII

  A. In a heated reactor, 0.0335 moles, TBT and 0.0335 moles of Mg in octane are stirred and 0.0057 moles of MgBr 2 · 6H 2 O are added (1: 1 molar ratio). , 17). The 2 * 2 salt dissolves in 6 minutes with heating & 650C. It appears a gray color with effervescence and the solutio -'a becomes blue then black-blue with greenish unenuance. The reaction is stirred at 123 ° C (about 10% unmodified Mg) after a reaction time of 4 hours 10 minutes.

(XVII A).,.,

  Similarly, a product with a Ti / Mg / MgBr 2 · 6H 2 O molar ratio (1 / 0.65 / 0.11) is prepared. A black-blue liquid and a dark green precipitate are obtained. -; '

  (6.5% Ti, 2.5% Mg by weight, calculated).

  B. The decanted product (XVII A) is combined with isobutylaluminum dichloride at Al / Ti ratios of f 3/1 and 6/1 by gradually adding the halide

  alkylaluminum. In the first operation (Al / Ti 3/1) ,.

  a maximum temperature of 42 C is reached with addition - at the rate of 1 drop every 2 to 3 seconds and the green liquid becomes brown. The product comprises a red brown liquid and a brown precipitate (IVB1) .The product 6/1 (IV B2) is prepared in a similar manner with the same results. The product obtained after 30 minutes of reaction at a ratio of "Si / Ti of 3/1" comprises a light yellow liquid and a reaction mixture.

'E ,,, ::

"r '" ":

- 32 -

  brown precipitate. A similar operation gives a product

Si / Ti 6/1.

  C. Activated products XVII B1 and XVII B2 (1% by weight) are used in the polymerization of ethylene (10 mol% in isobutane) & 88 C with hydrogen as modifier and triethylaluminum as cocatalyst ( 45 ppm Al) and compared to an identical operation using hydrated magnesium chloride, with the results shown in Table III below. Ti (OBu) 4-Mg-A A catalyst MgCl 2. 6H A = MgC12.6H2O MgB 2.6H2o Al / Ti molar ratio 3/1 3/1 6/1 H2, kPa relative Properties of the resin powder Productivity (g PE / g Ti.h)

MI HLMI HLMI / MI

1.7 12.2, 3 17.8 _ o

   % - 5''t To _- ':.; .._' ';' i - ,. - = {'= ... = f ":' _..- .. '-

, 9 28.5, 9! w I 24947o00

- 34 -

EXAMPLE XVIII

  A. 42.23 parts (0.124 moles) of TBT and 3.02 parts (0.124 moles) of Mg in octane (42.23 parts (0.124 moles) of TBT and 3.02 parts (0.124 moles) of Mg in octane were 42.8 parts) in the presence of 5.7 parts (0.02 mole) of FeCl 3 H 2 O (molar ratio T / Mg / Fe - 1/1/0, 17). The heating is started and in the space of 6 minutes at 65 ° C, the evolution of gas begins. The dirty yellow color turns dark brown & 80 C (7 minutes) and the gas evolution increases. In about 30 minutes, the evolution of gas slows down and then stops with consumption of Mg and the reaction is stopped. The very dark liquid

  has no residues (XVIII A1).

  In a second operation, the same reagents are combined with a molar ratio T / Mg / Fe - 1/1 / 0.34, with similar results. Dilution with hexane

  cause neither precipitate nor deposit of residue (XVIII A2).

  B. The product XVIII A1 is activated by reaction on a 50% by weight solution of ethylaluminum chloride in hexane at an Al / Ti ratio of 3/1. A brown liquid and a solid containing 16.5 mg of Ti / g are recovered.

(XVIII B1).

  Similarly, the product (XVIII A2) is activated.

  The dark brown liquid changes to a purple and then dark gray porridge. The clear liquid and the gray precipitate

obtained contain 16 mg Ti / g.

  C. The activated product XVIII B1 was used in the polymerization of ethylene at 88 ° C and 414 kPa H 2. It is recovered 114 320 g PE / g Ti / h and the product & properties

  following s MI 5,1, HLM4I 155,3, MIR 30,3.

EXAMPLE XIX

  A. In a stirred reactor, 0.160 moles of Ti (OBu) 4, 0.160 moles of magnesium turnings and 0.027 moles of CoC12.6H0 are combined with 61.2 parts of octane. The violet crystals of cobalt salt give, on dissolving, a dark blue solution. The mixture is heated by means of a

-35 '' '

  aB 'û., has electrical shirt and it appears at 58 C on the surfaces of magnesium a release of gas which increases until vigorous effervescence & 107 C in the space of 12 minutes. :: The light blue color becomes greyish when We continue to heat and almost black between 123 and 125 C when all the magnesium has disappeared and we stop the reaction, at; 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 results practically -

  identical. B. Shake the product obtained above and combine

  this (0.0111 mol of Ti) to isobutyl chloride

  aluminum (0.0333 mole Al) fed dropwise to a reactor. The temperature reaches a maximum of 40 C with the formation of a greyish precipitate which, after a new addition of BuAlC12, becomes brown. After 30 minutes of additional stirring, the reaction is stopped and:

  gets a dark brown-red liquid and a brown precipitate.

  C. The prepared catalyst component is used:

  in Example XIX above in the polymerization of.

  ethylene (88 C, 10 mole% ethylene, 0.0002 part of catalyst calculated as Ti, about 45 ppm of triethyl-% aluminum calculated as A1, H2 as indicated) with the results shown in Table IV below. t :,

TABLE IV

  H2, kPa Product, Properties of the relative catalyst, _ PE / q Ti / h MI HLMI

XIX B 414 105 180 6.2 206 33.6!

827 75 290 33.9 950 28'1 '

EXAMPLE XX

  A. 0.169 mol of Ti (OBu) 4 (TBT), 0.169 mol of magnesium turnings and 0.029 mol of AlCl 3 * 6H 2 O are obtained in a stirred reactor equipped with an electric heating jacket. octane as diluent. Salt*-:

2 ,,,,,

- 36 -

  Hydrated aluminum dissolves partially and at 110 ° C, the solution quickly darkens to a black liquid with vigorous effervescence due to a gas release on the surface of the magnesium. The solution takes a blue color and with gentle reflux to 122eC, it forms a

  Black-dark blue liquid with some residual magnesium.

  At 125 C, all the metallic magnesium disappeared, the solution having a slight green shade. Stop the reaction and recover a dark blue-black liquid and precipitate

  green, in a volume ratio of about 95/5.

  B. The above product is combined with isobutylaluminum chloride in an Al / Ti molar ratio of 3: 1 and 6: 1 by adding the chloride dropwise into a reactor containing the titanium product. In the first reaction (31sl), the alkyl chloride is added at a rate of one drop every 2 & 3 seconds until a maximum temperature of 42 C with a turn of green-blue to brown is reached. After stirring for a further 30 minutes, the product which comprises a liquid is isolated

  red-brown and a brown precipitate (XX B).

  C. Similarly, an Al / Ti product is prepared

  6s1 with the same results (XX C).

  D. XXB and XXC products with triethylaluminum as cocatalyst (45 ppm Al) in the polymerization of ethylene (10 mol%) with isobutane

  as diluent, at 88 ° C. with hydrogen as indicated.

  The operations are stopped after 60 minutes with the

  results shown in Table V below.

TABLE V

  EH2, kPa E, Product, Catalyst Properties relative moles a PE / q Ti / h MI HEU4

XX B 414 406 84 580 17.2 517 30.1

827 542 75 280 54.9 1413 25.7

XX C 414 245 54 440 4.11 129 31.4

827 183 34 860 26.2 801 30.5

r

- 37 -

EXAMPLE XXI

  A. 0.153 mol of Ti (OBu) 4 (TBT) 0.13 mol of Mg turnings and 0.026 mol of NiCl 6 H 2 O 2 & 61.75 were combined in a stirred reactor equipped with an electric heating jacket. octane parts. When heating & 44 "C, the" yellow solution takes a darker color and one starts? to observe at approximately 570C a gas evolution on the surface of the magnesium metal. As heating continues, the evolution of gas increases until, at 102 ° C (15 minutes of reaction), the system turns a slightly dirty brown color. A vigorous effervescence

  continues with obscuration of the brown color up to -

  what, & 126eC (75 minutes), all the magnesium has; faded away! the reaction is then stopped. The product (XXI AI) comprises a dark brown liquid soluble in hydrocarbons;

  bures and a small amount of a fine precipitate.

  In a second operation, 0. 149 mol of TBT, 0.149 mol of Mg and 0.051 mol of NiC 12.6H 2 O are combined in the octane in the same manner. The metallic Mg disappears at 120 ° C. (120 minutes) to give a hydrocarbon-soluble dark black-brown liquid which, on standing, separates into a very fine dark precipitate and a liquid.

  yellow, about 50/50 by volume (XXI A2). -

  B. The reaction product IA 1 is stirred and placed

  a portion (0.0137 mole of Ti) in a reactor with -

  hexane as a diluent and iBuAlCl (0.0411 mol of A1) dropwise at a rate of one drop every 2 to 3 seconds to 28 C and one drop per second until a maximum temperature of 390C. After completion of the addition, the contents of the reactor are stirred for 1 minute and the product comprising a dark brown-red liquid and a dark gray precipitate (XXI B1) is isolated. The same product (XXI A1) is combined with ethylaluminum chloride in the same way, with a Al / Ti molar ratio of 3/1. The product includes a deep brown-red liquid and a dark gray solid (XXI B2). i

- 38 -

  In a substantially identical manner, the product XXI A2 (Ti / Mg / Ni 1/1 / 0.34 molar ratio) is combined with iBuAlCl 2 with an Al / Ti ratio of 31sl, with the same results, except that the supernatant liquid is brown-red

(XXI B3).

  In another operation, the product XXI A2 is reacted in the same way on iBuAlCl 2 with a molar ratio Al / Ti of 6: 1 to similarly form a

  dark liquid and a dark precipitate (XXI B4).

  The same product XXIA2 is similarly combined with ethylaluminium chloride and a liquid is obtained.

  dark red-brown and a dark gray solid (XXI B5).

EXAMPLE XXII

  A. Example XXI is repeated by bringing the reagents to a molar Ti.Mg / Ni ratio of 0.105: 0.11. The color changes from dark yellow-brown to dark brown with gas evolution, then to brown-gray and then to dark-blue-black, with consumption of magnesium, in a reaction that

takes place in 6 hours (XXII A).

  B. The product XXII A is combined with ethyl chloride

  aluminum in the manner of Example XXI B, with an Al / Ti molar ratio of 3: 1. We recover a red-brown liquid

  and a red-brown precipitate (XXII B).

EXAMPLE XXIII

  Example XXII is repeated by feeding the reactants with a molar ratio of 1: 0.75: 0.128. The brown product

  Dark contains 5.9% Ti, 2.2% Mg and 0.97% Ni.

  The product is then treated with isobutyl chloride

  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 as catalyst components in the polymerization of ethylene (88 C, mol% of ethylene, approximately 45 ppm of triethylaluminium calculated in A1, H2 as indicated ), with the results shown in Table VI below

- 39 -

TABLE VI

Catalyst

* XXIB-3

XXIB-4

XXIIB

XXIB-2

XXIB-5

  H2, relative kPa Productivity, PE / g Ti / h 750

104,980

111,940

112,260

59,790

62,720

57,890

64.740

238,670

271,560

  The average MI 9.55 24.6 0.29 3.1 0.25 1.0 1.66 6.13 0.65 6.7 low ln aaa HMI, 7, 9 43.6 54.9 19, 5 1 Operations with a high hydrogen content are extremely fast and result in an accumulation of

  polymer that forces & stop operations.

E2EMPLE XXV

  = 27.8 16.8 18.9 t3.6 3.6 33.1 29.8 D0.2

O8,1 2

  2.1 A. TBT, MgO and MgSiF6.6H20 were combined in octane in a heated reactor equipped with reflux, as in 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 the

  Ethylaluminum chloride in an Al / Ti ratio of 3/1.

  C. The resulting brown precipitate is separated from the supernatant brown-red liquid and used with TEA to provide about 45 ppm Al, under normal conditions, for the polymerization of ethylene (88 C, 414 kPa relative). H2) is obtained, at a rate of 107,500 g PE / g Ti / h,

  a resin characterized by MI 2.85, HLMI 84.5 and MIR 29f6.

  D. The reaction product 1/1/0034 prepared above is also activated with isobutylaluminum chloride at an Al / Ti ratio of 3/1. The solid product is repeatedly washed with hexane and used with TEA in an ethylene polymerization reactor, preloaded with butene-1, to obtain a resin having the desired density, δ 77 C and 207 kPa. of H2, starting from J 'J t

-.J $;

Y * to years - X 1W.-,

1, -

1g 1-he,% ,,,)

1, 1 -,

  1, 1, 11, 1, 1

- 40 -

  ethylene / butene-1 feed. The resin has a density

  0.9193, MI 1.91, HLMI 60.8, MIR 31.8.

  In the following example, we activate the constituents

  of catalyst by reaction on a halide component.

EXAMPLE XXVI

  A. In the following operations, TMMg reaction products are reacted on the halide component which is gradually added thereto, usually dropwise to control the exothermic reaction. The reaction is conducted under ambient conditions for a time sufficient to complete the addition with stirring of the reagent, for 10 to 30 minutes after the onset of the maximum temperature (if applicable, the solid TMMg and liquid to a slurry and used in this form). The reagents and their proportions are given below. Catalyst component, molar ratio Ti / Mg / MgCl 2 · 6H 2 O (H 2 O) promoter halide Molar ratio 1 / 0.65 / 0.11 (0.66) Bu 1 AlCl 2 / 1 Al / 'i 1 / 0.65 / 0.11 (0.66) BulAl2 3/1 1 / 0.65 / 0.11 (0.66) Bu A1C12 4/1 1 / 0.65 / 0 , 11 (0.66) Bu AlCl2 6/1 1 / O, 65 / 0.11 (0.66) EtAlCl2 3/1 1 / 0.65 / 0.11 (0.66) EtBC12 1 25/1 ( B / Ti) 1/0, 65 / 0.11 (0.66) EtBC12 3/1 (B / Ti) 1 / 0.65 / 0.11 (0.66) SiC14 3/1 (Si / U [ ) 1 / 0.65 / 0.11 (0.66) SiC14 6/1 (Si / Ti) 1 / 0.75 / 0.128 (0.768) EtAlC12 3/1 1 / 0.75 / 0.128 (0.768) Et3A12Cl3 3 / 1 1 / 0.75 / 0.128 (0.768) BulA1C12 3/1

- 41 -

  Catalyst component, Ti / Mg / MgCl 2 · 6H 2 O (H 2 O) molar ratio

1 / 0.75 / 0.128 (0.768)

1 / 0.75 / 0.128 (0.768)

1 / 0.75 / 0.128 (0.768)

1 / 0.75 / 0.128 (0.768)

1 / 0.75 / 0.128 (0.768)

1 / 0.75 / 0.128 (0.768)

1 / 0.75 / 0.128 (0.768)

1 / 0.75 / 0.128 (0.768)

1 / 0.75 / 0.128 (0.768)

1/1 / 0.17 (1.02)

1/1 / 0.17 (1.02)

1/1 / 0.34 (2.04)

1/1/0 # 34 (2.04)

1/1 / 0.51 (3.06)

1/1 / 0.51 (3.06)

2/1 / 0.17 (1.02)

2/1 / 0.17 (1.02)

2/1 / 0.34 (2.04)

2/1 / 0.34 (2.04)

3/1 / 0.51 (3.06)

3/1 / 0.51 (3.06)

  Activator of the halide type Bu AlC12 EtBC12 (CH3) 2SiCl2 (CH3) 3 SiCl (CH3) 2SiHC1 SiC14 SiC14 TiCl4 TiCl4 BulAlC12 EtA1C12 BulAlic2 BulAlC12 BulAlC12 BulAlC12 BulA1c12 Bu AlC12 Bu AlC12 i BulA1c12 BulAlC12 BuiAlC2 Bu AiC12 Bu A1c12 BiAC Bu AiClX2 Molar ratio 6/1 3/1 (B / Ti) 6/1 (Si / Ti) 6/1 (Si / Ti) 6/1 (Si / Ti) 3/1 (Si / Ti) 6/1 (Si / Ti) 1, 5/1 (Ti / ri) 3/1 (Ti / r) i 3/1 3/1 3/1 6/1 3/1 6/1 3/1 6/1 3/1 6/1 3/1 6/1

- 42 -

EXAMPLE XXVII

  A. Bu AlC12 activated catalyst samples (Al / Ti 3: 1) were used in a series of polymerization operations, with the results shown in Table VII below.

TABLE VII

  Ti / gC12.6H (molar ratio) (molar ratio) H2, kPa relative Productivity (q PE / g Ti / h) Properties of the resin powder HMI HLMI / MI

1/1 / 0.17 5.9

1/1 / 0.34 2.9

2/1 / 0.34 5.9

3/1 / 0.51 5.9

1 / 0.75 / 0.128 7.8

1 / 0.65 / 0.11 9.1

2/1 / 0.17 11.8

  Conditions in the reactor S isobutane diluent Temperature t 88 C Hydrogen as indicated Cocatalyst triethylaluminum Catalyst reaction product Ethylene s 10 mol%

Duration 60 minutes.

42,870

49,102

63.385

43,655

57,510

54,200

53,975

56,560

124,930

116,990

76,785

61,550

138,820

89,900

  1.7 12.2 3.8, 7 2.5 12.5 2.4 13.2, 3 22.8 8.1 44.5 2.25 17.4 67.3 (45 ppm Al) Ti (OBu) 4-Mg-MgCl 2 · 6H 2 0 activated by Bu AlCl 2, 9 28.5, 33.0 32, 36.2 37.1 32.6 33.8 27.6, 29.9 28.2 (Al / Ti 3s1) __ - s

- - II- - -

I w I o NO CD I i I

- 44 -

  As can be seen by comparing the molar ratio Ti / MgC12.6H20, the maximum melt index is observed at a ratio of 9z1 (Ti / H20 1.51) o B. In the following additional operations, the effect of Al / Ti ratio in TMMg catalysts

  activated (molar ratio 1 / 0.65 /, 011), in the polymerization

  ethylene. The results obtained are shown in Table VIII below.

TABLE VIII

  Molar ratio of activator compound / Ti 2/1 3/1 4,5 / 1 6/1 3/1 3/1

1.25 / 1

  H2, relative kPa Productivity (q PE / g Ti.h)

54,285

670

76,785

61,550

66,410

67,255

43,830

44,370

790

97,310

94,755

56,290

34,300

27,290

  Properties of BuaMI / M HMI resin nester 16.8 8.1 44.5 7.7, 5 2.7, 0 7.0 3.7 21.5 3.5 29.1 28.2, 2 33 , 4 31.5, 6 34.6 28.6 Conditions in the reactor s Diluent I isobutane Temperature s 88 C Hydrogen as indicated Cocatalyst s Triethylaluminium Catalyst I reaction product Ethylene s 10 mol%

Duration 60 minutes.

  (45 ppm Al) Ti (OBu) 2-Mg-MgCl 2 · 6H 2 O Activated as above Activator Compound BuiAlC12 i BuiAlC12 i Bu AlC12 Bu AlC12 EtAlC12 EtB12 EtBC12 I I -g-. -qc, - C> O

- 46 -

  C. In another series of experiments using a TMMg catalyst with a molar ratio of 1: 0.75: 0.128, the effect of the enhancer is analyzed with the results shown in Table IX below: <Ty8p wdd stI ) SSS'bZ

0S6 TC

OL9 TL

0C8 SbT

YES T9

O0T 8T

OTO Cú

OLL 8Z

OZT TE

098 tE 09 08 058 t6

066 9TT

  0C6 tET TU (ZTL b // gab) LE8 KT LEZ 91T LE8 1T) LE8 LEZ 1Tt LE8 t11 LE8 tTP LE8 1T1

B; TIQTOS

  9TAT: onpoad Ud tH um 09 z *, 9% TOU OT s auT T TAl'Z wnuTuTunTTAn-4.T: t :; sxnemBtUvzOD qnbTpuT hOuNHeS aui6opXH Do8 8 g o.xn: lvadura eue-nqosT s. uenTTa S znea. ############################################################################################################################################################################################################################################################################################ aneAT-40 T: T n t S -; D c> Il. 4. O '4- IUr 8Z C' 6E Z'LE 9'9E E'SE 6j'6V 0 'at' missed O'gE 6 a CL ZoILC I 1 '' I L6E THE T9 6EZZ 0 '6E TT9 OTE 86T TS 1TZ E COT OC9 6LT 8'8 8'T 96'L 66'0 98'8 6Z'L 96'T C'9T SZ 'LI' OT O6E E'le SEIr 8'S Mm 9'LE 8'úúC T - / 'zeH - .. ev - L% ev 71T I -.Abâtardissements -t' -L -L'T ..,

- 48 -

  D. Polymerization operations were carried out at 88 ° C. with the catalyst TMMg 1 / 0.75 / 0.128 (boiled, separated from the supernatant liquid and washed with hexane) and the cocatalyst TEA, using ethylene and butene-1 as a comonomer, by varying the butene-1 feed, the activators and the levels of activators. The results are shown in Table X below.

PAINTINGS

Brought in

thylene (%

weight of the

  Rated in the reactor) 4.41 2.39 3.02 2.43 2.32 2.34 1.75 Feeding of butene-1 (% by weight of the total monomer) 7.55 7.14 11.56 11, 59 __ 14.66, 77 17.82 17.82 Molar ratio H2 / ethylene 0.12 0.06 0.05 0.07 0.03 0.03 0, Q6 MI tablets 12.7 1.9 1.0 3.2 3.9 0.6 0.7 0.6, 8 1.1

HLMI / MI

  41.2 28.5 28.6 33.4, 2 31.3 29.7 43.9 Annealed Density 0.948 0.939 0.934 0.939 0.934 0.931 0.929 0.928 0.935 0.924 Activator 6/1 Al / Ti iBuAlC12 6/1 Al / Ti iBuAlC12 6/1 Al / Ti iBuAlC12 3/1 Al / Ti EADC 3/1 Al / Ti EADC 3/1 Al / Ti EADC 3/1 Al / Ti EADC 3/1 Al / Ti EADC 3/1 Al / Ti EADC 6/1 Al / Ti EADC J

Opera-

  n A B C D E F G H I J g I M 4- 4- C> CD 1 f

I. -1 ..-

1,, - .-

- 50 -

  The batches of resins collected as above were stabilized with 100 ppm of calcium stearate and 1000 ppm of "Irganox 1076", characterized by standard tests and converted into a blown sheet in a 38 mm Hartig extruder ( screw 60 rpm, die

  76 mm, die gap 2.08 mm, cooling air

  2.8 to 4.4 ° C) and then tested, all as shown in Tables XI and XII. s) Properties of linear low density resins Eta 10 X 10-3 Swelling in the die & Eta 1000 Resistance tensile strength, MPa & 508 mm / min Flow limit, MPa & 508 mm / min Elongation,% at 508 mm / min Tensile modulus, MPa Tensile strength, J / cm2 Vicat, C Low temperature fragility, C Hardness Shore D "1,56 le, 56 B367 3,67 C

4, 36MF

146 164 -

D 3.56 3.35

3.95> 1V

4OOMF1

# 4 00MN1

152 150

27.3 12.3 12.8 12.5 11.7 15.5 23.6

, 0 22.1 19.9

-76 -76

61 58

  19.1 27.3 -76 22.2 18.6 -76 19.5 16.6 -76 18.4 44.9 -76 17.1 56.2 -76 H

3,90MF1

2,891 2.89 4.15

- 146,165

22.8 11.4 13.2

  16.5 62.8 -76, 1, 3 -76 14.1 38.2 -76 i - at least some fragility of fusion indicating the

  need to optimize the conditions for the actual extrusion.

  o "4- LI - C> S0S *: CAPb + Xa ^ C $ erpt: t X04: s64:; X: f: eW * r [^ KffiR: X -Et; Mt WMeS: S" JII OTUUigAeu'4 . UoFc09SrP euwqom uoTFDoaZp s edY ,. UOC; oezx ua oTnpow eTUexoAsUU UOT-oS2TP euTgql uo $ Dog Tp * uni / E 'Oota S wsv eznTqqog "eTuSoxAsuxz UOTDO.zTp eUT4DUu UOTFlogTp s uw / E, zOpUemTj ean = zqOga eTveIzaAsueuz uoTOaaTp OUTqoeum UOTIOXTp S%' 8uSma6UOTTY eTeuSeABsuX UOT -OaZTP eUTqiamu UOT-4DSTp s - '4uemuTnoog.p -TuiT, I eTusz. Euuz UOT; ..XTP euTqou UOTPOeTPp sw' UOTOW.ZTX eoDUUsTSog% 'o09' IUvTTTX% 'OTqnozl #ur (' .TTTne; T ap znossTUda IIx nimifli c CD O -4 oP N4 NI / 1 ln t TITLE LT 6L00T 8LET OSS OOL 9 '9T O'ST 8' Cc 6'Lu T'L TS a L9t T8u 9'iT Z ' AND OLU6T LZ8 O88 OL9 T'9T is 0'lt 8'Tt 6'u Z'Z SZ úTS STL, 8'9T 8'9T LZ8 08L OL9 T'8T S'9T 6'ZL '8u 6't TS Ett ú '/ LT 0'0t 9út O9CE S' 9T 9'LT is ú''T '8Z g'S o' 0ú SZ T1,9 66, C 'LT T'6T 0ú9 0o8e OSL 9' 6T 8'ST S 'SI TS 9TUUP ANBs' y * ZTU9uTT UOUTSgX op.'TeNo0 SRTTTnOZ BOp 8; s9TXdOd

TABLE XII

  Arrow Fall, g (pm) Dynamic Burst & Ball, cm-kg (pm) Span, pm Melting Point, C Head Pressure, Relative MPa Cooling Air Temperature, OC (Continued) Blown Sheet Properties of linear & low density resins

B C

f

72 (56) 10.5 (25) 92 (56) 45 (33)

2.44 1.40 (25) 3.94 (56) 2.48 (30)

- 66.35 - 5.08

166,166 182,182

23.4 23.4 26.5 26.5

3.3 3.3 3.9 3.9

F

81 (51)

4.26 (51)

  , 7 3,3 - ', 0> CD g ut nw I this M ST T 086T 868C OT9 ú'TT 6'EZ 9'Et 0'9 0'0 SZ O lot' sr * C 8S5 ú '%, T 8'I, T

6 (H ,, T

OSTC OSTC 0u8 OL9

/. AND

The lt

ú ', T!

  6'6 0'9 TS Liu 96Z '0Z 800U 09ZT OT8 OZE 6'CT T'ú5 T'9 6' 8T g5 06c 6Tu O'LT t "8T 9060T OSTE ST S'CT Z'9E 1>" 6C 9 '5 IZ TS 8LEU TU 9'Tt IS 0689T L80Z 0ú8, t' 4'TS * CT S'9C 8'L / '9'5 9'Z SZ H 06c 6TE O'LT t' 8T 9060T OSTE 0S8 E'ST IS "9C '6E 9'S TS UdN guOflD0vaZ ue eTnpow wd / 6' t0OOT WT, SV aenaTolqoaI uu / 6 '92opuaOmT axnLTqoaQ%' uamaeue6uoTTY laR uemaaTnooaep aiTUrFQ UOTIODeV Vt aoul9sTsu% 'o09 * IUVTTTag%' * Tqno & L wUR, alTnae wT ap = naseTuda tD 9WTSUap asseq saTeuTT sauTae ap saeTnog saTTTnae sap s9qzTJdOxd (0WFQS> s) Iix nv3wiYL o 'c0 0% Gold TBEAU XII (cont'd) Properties of blown sheets of linear & low density resins a' Fall Arrest, g (pm) Dynamic Ball Burst, cm-kg (pm) Span, pm Melting Point, C Head Pressure, Relative MPa Cooling Air Temperature, C

109 (53)

6.50 (58)

31.0 3.3

38 (25)

311 (25)

7.62 31.0 3.3 N o -'J o o

-

J M

109 (53)

6.50 (58)

33.1 2.8

36 (25)

414 (25)

33.1 2.8 (64)

6.62 (61)

26.9 4.4

43 (30)

3.62 (30)

7.62 26.9 4.4 I

- 56 -

  E. In other large scale polymerizations conducted in a similar manner with the TMMg catalyst (slurry separated from the supernatant liquid and washed with hexane, at a molar ratio of 1: 0.75: 0.128 (Al / Ti 3/1). , EADC), hexene-1 is fed to the reactor as a comonomer with ethylene, and then replaced with butene-1 by obtaining, according to the analysis of the evolved gases, ethylene / butene-1 copolymers. / hexene-1 and terpolymers during the operation The results are shown in Table XIII below: Comonomer Hexene Hexene / Butene Density Butane

.9339

.9293

.9157

0, 9148

O. # 9148

0 9135

TABLE XIII

  mI 0.83 0.73 0.94 0.70 0.70 0.94 f, HIM: 26.9 23.9 31.4, 2, 2 29.9 tn I ul to No. 1% O 0o - C, C.

- 58 -

EXAMPLE XXVIII

  A TMMg catalyst prepared according to the examples and activated by isobutylaluminum chloride (Al / Ti 3/1) is also used to prepare other copolymers with a variable precharge of comonomer with isobutane as a diluent, a temperature of 77 ° C. in the reactor, a relative pressure of 207 to 276 kPa of H2 and TEA to provide 60 ppm Al, with the following results: Ethylene / 3-methylbutene-1 MI MIR Density

1.25 27.4 0.9488

1.25 28.9 0.9483

1.36 27.9 0., 9507

1.55 27.7 0.9497

1.56 27.5 0.9495

1.87 29.9 0.9496

1.63 28.5 0.9455

2.25 28.8 0.9437

1.46 30.0 0.9428

, 01 30.3 0.9411

1.59 31.9 0.9400

Isobutylene 0.37 32.4 0.9518

1.35 29.6 0.9564

1.79 31.1 0.9542

1.17 31.7 0.9567

4.20 30.1 0.9582

3.30 32.9 0.9557

  Polymerization or copolymerization of other olefins such as

  propylene, 4-methylpentene-1, acrylates and metha-

  alkyl crylates and alkyl esters.

  The following comparative experiments are also conducted *

* COMPARATIVE EXAMPLES

  A. In the same reactor used for other prepara-

  The anhydrous TBT, Mg and MgCl 2 were pooled in octane, mole ratio 2: 1: 0.34 and refluxed for 15 minutes without reaction. The MgC12

-59 -

  Anhydrous remains undissolved. See also example I B ci-

  above. B. In the same system, a quantity of free water equivalent to an Mg / MgCl 2 H 2 O ratio of k 1 / 0.34 is added in bulk, but no change is observed. C. TBT and Mg are combined in a molar ratio of 2/1 in octane and heated to reflux. The yellow color becomes a little more intense house does not observe any reaction. d. In system C above, a quantity of free water equivalent to a ratio Mg / MgCl e26H 0 of 1 / 0.34 is added. A small amount of light yellow precipitate is formed which indicates hydrolysis of the

  titanium but the magnesium remains unaltered.

  E. TBT and 14gCl2.6H20 are pooled in octane to

  a molar ratio of 1: 0.34 and heated to reflux.

  Once the salt is completely dissolved, the solution becomes turbid and a little viscous with continuous reflux for 3 hours but clarifies and deposits overnight giving a turbid yellow liquid and a whitish precipitate. Another operation at a molar ratio of 1: 0.128 yields a clear golden yellow liquid with refluxing heating for only 16 minutes. At a molar ratio of 1: 1.17, foaming and formation,

  a thick gel of cream color end the reaction-

  after 45 minutes. Compare Example VII above * * * * * * * * * * * * * * *

999999 "

9, 9, j 1 <99

- 60 -

Claims (17)

  Process for the polymerization of 1-olefins, alone or together with at least one copolymerizable monomer, under conditions of temperature and pressure suitable for polymerization, characterized in that a catalytic system of olefin polymerization comprising a mixture of cocatalysts, one of which is a halide-activated intermetallic compound and which is the reaction product of a transition metal polymer-metal oxide and a reducing metal having a potential   oxidation higher than the transition metal.   2. A process according to claim 1, characterized in that the polymeric oxide metal oxide of transition metal is obtained by partial hydrolysis of the transition metal alkoxide.   3. A process according to claim 2, characterized in that the hydrolysis is carried out with a complex laquo as a source of water.   4. A process according to claim 3, characterized in that the water is supplied in the form of a hydrated salt such as a hydrated salt of aluminum, cobalt, of iron, magnesium or nickel.   5. A process 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 by the fact that the molar ratio between the transition metal and the water is between 10 and 5 and about 11.5.   7.- Method according to one of claims 1 & 6,   characterized in that the reducing metal is magnesium, calcium, zinc, aluminum or a mixture of these.   80- Method according to one of claims 1 & 7,   characterized by the fact that the transition metal is - 61 - titanium or zirconium.   9.- krocédé according to claim 8, characterized in that the transition metal and the reducing metal are present in a molar ratio of between 0.5zl and 31sl approximately. 10. A process according to claim 9, characterized in that the transition metal and the reducing metal are in a molar ratio between 1: 0.1 and 11 approximately.   11. A process according to one of claims 1 to 10,   characterized by the fact that the halide type activator -   is represented by at least one of the following compounds: an alkylaluminum halide, a silicon halide, an alkylsilicon halide, a titanium halide or an alkylbore halide.   12. Process according to one of claims 1 to 11,   characterized in that the cocatalyst is an organoaluminum or organoboron compound, preferably the   triethylaluminum or triethylborane.   13. Catalytic system for the polymerization of olefinea, characterized in that it comprises a mixture of cocatalysts, one of which is a halide-activated intermetallic compound and which is the product of the reaction of a polymeric oxide-alkoxide. of transit metal / Q and a reducing metal having an oxidation potential   higher than the transition metal.   14. A system according to claim 13, characterized in that the activator of the halide type is represented by at least one of the following compounds: an alkylaluminium halide, a silicon halide, an alkylsilicon halide, a halide of titanium or an alkylbore halide.   15.- System according to one of claims 13 and 14,   characterized by the fact that the transition metal is titanium or zirconium.   16.- System according to one of claims 13 to 15, 1 - 62 -   characterized in that the reducing metal is magnesium, calcium, zinc, aluminum or a mixture of these.   17.- System according to one of claims 13 & 16,   characterized by the fact that the transition metal oxide polymer is the product of hydrolysis   partial setting of a titanium alkoxide.   18.- System according to one of claims 13 to 17,   characterized in that the transition metal and the reducing metal are present in a molar ratio between 0, # 5l and about 3sl.   19. System according to claim 18, characterized in that the ratio is between ls0,1 and lsl approx.