EP0000007B1 - Process for the polymerisation of alpha-olefins and method for preparing solid catalytic complexes for use in this polymerisation process - Google Patents

Process for the polymerisation of alpha-olefins and method for preparing solid catalytic complexes for use in this polymerisation process Download PDF

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Publication number
EP0000007B1
EP0000007B1 EP78200026A EP78200026A EP0000007B1 EP 0000007 B1 EP0000007 B1 EP 0000007B1 EP 78200026 A EP78200026 A EP 78200026A EP 78200026 A EP78200026 A EP 78200026A EP 0000007 B1 EP0000007 B1 EP 0000007B1
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compounds
compound
chosen
amongst
magnesium
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EP0000007A1 (en
EP0000007B2 (en
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Charles Bienfait
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Solvay SA
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Solvay SA
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/06—Catalyst characterized by its size
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/908—Containing catalyst of specified particle size

Definitions

  • the present invention relates to an improved process for the polymerization of alpha-olefins. It also relates to a process for the preparation of solid catalytic complexes which can be used for this polymerization.
  • the morphology of the particles of these polymers therefore poses problems during their drying, their storage, their transport, their handling and their use by known molding techniques.
  • the attempts made so far to increase the average particle size of the polymers obtained directly by polymerization using the catalyst systems described above have not been completely satisfactory. It has thus been found that a certain increase in the average diameter of the particles can be obtained by raising the temperature at which the aluminum halide is used. This increase in the mean diameter is however unfortunately accompanied by a decrease in the apparent specific weight and a significant widening of the particle size distribution.
  • the main object of the present invention is therefore to obtain, without the above-mentioned harmful side effects, polyolefins in which the percentage of fine particles is reduced and in which the average particle size is higher.
  • polyolefins are increasingly used in the form of powders, that is to say in the form of dense and regular particles, a large percentage of which have an average diameter greater than 250 microns, preferably greater than 500 microns.
  • Polyolefin powders are particularly appreciated for processing by injection.
  • Other interesting outlets for polyolefin powders are the production of coatings by various techniques (electrostatic coating, spray coating, etc.) and the use as additives, release agents, waxes, compositions for paints, binders for nonwoven textiles. , etc.
  • Another object of the present invention is the manufacture of polyolefin powders by means of polymerization processes which directly give polymers in the form of particles which have the morphological characteristics of the powders used in the processes mentioned above.
  • the invention is based on the surprising discovery that a quite particular class of catalytic systems described above makes it possible to obtain without affecting the advantages inherent in these systems, polvolefins in the form of dense and hard particles, of large average diameter. , of tight particle size distribution and high apparent specific gravity. These properties make them particularly suitable for being used in the form of powders when they are transformed into finished objects.
  • organic oxygenated compounds of magnesium and titanium is meant to designate all compounds in which any organic radical is linked to the metal via oxygen, that is to say all the compounds comprising at least one sequence of metal-organic radical oxygen bonds per metal atom.
  • the organic radicals linked to the metal via oxygen are arbitrary. They are preferably chosen from the radicals comprising from 1 to 20 carbon atoms and, more particularly, from those comprising from 1 to 10 carbon atoms. The best results are obtained when these radicals contain from 2 to 6 carbon atoms.
  • These radicals can be saturated or unsaturated, branched chain, straight chain or cyclic; they can also be substituted or contain heteroatoms, such as silicon, sulfur, nitrogen or phosphorus, in their chain.
  • alkyl radicals linear or branched
  • alkenyl aryl, cycloalkyl, arylalkyl, alkylaryl, acyl and their substituted derivatives.
  • halogenated compounds of magnesium and titanium is intended to denote all the compounds comprising at least one metal-halogen bond.
  • the metal bound halogen can be fluorine, chlorine, bromine or iodine.
  • the halogen is chlorine.
  • organic and halogenated oxygenated compounds which are suitable, use is preferably made of those which contain only metal-oxygen-organic radical bonds and / or metal-halogen bonds to the exclusion of any other bond.
  • the solid catalytic complexes used in the present invention are prepared from reactants (1) which are magnesium compounds (M).
  • the organic oxygenated compounds (M) can comprise, in addition to the organic radicals linked to magnesium via oxygen, other radicals.
  • These other radicals are preferably oxygen and the inorganic radicals linked to the metal via oxygen, such as the radicals -OH, - (S4) "2, -N0 3 , - (PO 4 ) 1/3 , - (CO 3 ) 1 ⁇ 2 and -CI0 4.
  • They can also be organic radicals directly linked to magnesium by carbon.
  • magnesium compounds containing both a magnesium-halogen bond and an organic radical as defined above linked to magnesium via oxygen is also part of the invention.
  • the compounds of this type giving the best results are of course, chloralkoxides and chlorphenoxides such as Mg (OCH 3 ) CI, Mg (OC 2 H 5 ) Cl and Mg (OC e H s ) CI for example.
  • the reagents (2) used to prepare the catalytic complexes according to the invention are titanium compounds (T).
  • the tetravalent titanium compounds are preferably used because they are more often liquid and in any case more often and better soluble than those where this metal is at a valence of less than 4.
  • the organic oxygenated compounds (T) of the titanium which can be used as reactants (2) can also be compounds comprising metal-oxygen bonds and condensed compounds comprising sequences of metal-oxygen-metal bonds, provided that they also comprise at least one sequence of metal-oxygen-organic radical bonds by molecule.
  • the organic oxygenated compounds (T) can be represented by the general formula (TiO x (OR) 4-2x ] m where R represents an organic radical as defined above, where x is a number such that 0 ⁇ x ⁇ 1, 5 and where m is an integer We prefer to use organic oxygenated compounds where x is such that 0 ⁇ x ⁇ 1 and m such that 1 ⁇ m ⁇ 6.
  • organic oxygenated compounds (T) comprising several different organic radicals also falls within the scope of the present invention.
  • alpha-olefin polymers of wide molecular weight distribution it may be advantageous, for the manufacture of alpha-olefin polymers of wide molecular weight distribution, to additionally use at least one additional transition metal compound (reagent (4)) to prepare the solid catalytic complexes of l 'invention.
  • This additional compound is then a compound (Z) chosen from organic oxygenated compounds and halogenated zirconium compounds.
  • the solid catalytic complexes which can be used according to the present invention are finally prepared from reagents (3) which must be organoaluminum chlorides of general formula AIR n CI 3-. in which R is an alkyl radical, linear or branched, comprising from 4 to 18 carbon atoms and in which n is from 1 to 1.5.
  • the side chain is preferably single and short, and is in particular a methyl group.
  • the branched radical is a single “iso” radical, that is to say a radical in which the substituent group is in position ⁇ with respect to the terminal carbon of the radical.
  • organoaluminum chlorides correspond to the above formula, in which n is 1.
  • Organic chlorides meeting this definition are, for example, n-butyl- and isobutylaluminum dichlorides, n-octyl- and isooctylaluminium, n-hexadécylaluminium, n-octadécylaluminium.
  • a particularly preferred and easily accessible organoaluminum chloride is isobutylaluminum dichloride AI (iC Q H 9 ) CI 2 .
  • reagent (3) is an essential characteristic of the invention. It is indeed the nature of this reagent which, surprisingly, is at the basis of the substantial improvement in the morphology of the polyolefins obtained according to the process of the invention.
  • organoaluminum chlorides are not excluded from the scope of the invention, provided that the alkyl radicals contained in each of them contain at least 4 carbon atoms.
  • organoaluminum chlorides can be prepared, optionally "in situ” and preferably prior to their use, in particular by mixing the corresponding trialkylaluminums with aluminum chlorides containing more chlorine than the chloride which it is desired to obtain.
  • the scope of the invention is not limited to the use of organoaluminum chlorides consisting exclusively of compounds corresponding to the general formula above mentioned but that it extends to technical products containing, in addition to a substantial proportion of these compounds, by-products such as the reagents used for their preparation. However, it is preferred that these products contain at least 80% by weight of organoaluminum chlorides corresponding to the general formula.
  • the solid catalytic complexes of the invention can be prepared from the reactants (1), (2), (3) and optionally (4) above according to all the methods inducing a chemical reaction between them.
  • a diluent in particular when the reagents are not themselves liquid under the operating conditions or when there are not enough liquid reagents.
  • a diluent is generally chosen from those which are capable of dissolving at least one of the reactants and in particular from alkanes, cycloalkanes and aromatic hydrocarbons comprising from 4 to 20 carbon atoms such as for example the isobutane, hexane, heptane, cyclohexane, benzene, toluene, etc.
  • polar solvents such as ethers and alcohols comprising from 1 to 12 carbon atoms (ethanol and diethyl ether, for example), tetrahydrofuran, pyridine, methylene chloride, etc.
  • a diluent dissolving at least one of the reagents it is preferred that the total concentration of the dissolved reagent (s) is greater than 5% by weight and preferably 20% by weight relative to the diluent.
  • the reaction medium is preferably in the form of a relatively viscous liquid in which materials may be present. solid in dispersed state.
  • the order of addition of the reagents is arbitrary.
  • the reagents (3) can, in particular, be introduced into the reaction medium at any time during the preparation of the solid catalytic complex.
  • reagent (3) takes place at the end of the preparation of the catalytic complexes, that is to say as soon as possible while the reagents (1) and ( 2) are brought together.
  • the best results are obtained when the reagent (3) is used after the reagents (1) and (2) have been brought together in their entirety.
  • the methods for preparing the solid catalytic complexes according to the invention also extend to the use, in place of the reactants (1) and (2) preformed, of magnesium, of a hydroxylated organic compound such as alcohol and reagent (2).
  • the pressure under which the preparation of the catalytic complexes is carried out, the rate of addition of the reactants and the duration of their contact are not critical factors. For reasons of convenience, one generally works under atmospheric pressure; the speed is generally chosen so as not to cause a sudden heating of the reaction medium due to a possible self-acceleration of the reaction; the duration can generally vary between 5 minutes and 12 hours.
  • the reaction medium is generally stirred so as to promote its homogenization during the duration of the reaction.
  • the reaction can be carried out continuously or batchwise.
  • the temperature at which the reagent (1) and the reagent (2) are brought into contact is not critical. For reasons of convenience, it is generally chosen between 200 and -50 ° C, preferably between 150 ° C and room temperature (25 ° C).
  • the temperature at which this reaction is carried out has an influence on the morphology of the polyolefin powder finally obtained.
  • the temperature at which this reagent (3) is added or produced resulting from the prior mixing of the reagents (1) and (2) is preferably between 30 and 65 ° C. The best results are obtained between around 45 and 60 ° C.
  • the preparation of the catalytic complexes in accordance with the invention can advantageously be completed by a treatment of the ripening carried out at a temperature generally equivalent to or higher than that at which the reaction with the reagent (3) takes place for a non-critical period ranging from 5 minutes. at 12 o'clock in general, preferably for at least 1 hour.
  • the amount of compound (M), compound (T) and organoaluminum chloride (A) to be used preferably are specified below.
  • the quantity of the compound (s) (T) to be used is defined relative to the total quantity of the compound (s) (M) used. It can vary to a large extent. In general, it is between 0.01 and 10 at.-g (gram atom) of metal present in the compound (T) per at.-g of magnesium present in the compound (M). It has been observed that the performance of the catalytic complexes of the invention is optimal when a ratio of between 0.025 and 5 at.-g of titanium per at-g of magnesium is used.
  • the amount of organoaluminum chloride to be used is also defined relative to the total amount of the compound (s) used. It can also vary widely. In general, it is between 1 and 100 moles of organoaluminum chloride per mole of compound (M). Preferably, this amount is between 1 and 20 moles per mole. The best compromise (as defined above) is obtained when this ratio is between 2 and 10 moles per mole.
  • the catalytic complexes according to the invention are solid. They are insoluble in alkanes and cycloalkanes which can be used as diluents. They can be used in polymerization as they are obtained, without being separated from the reaction reaction medium. They can however be separated from this reaction medium, in particular when they are prepared in the presence of a polar solvent, by any known means.
  • the reaction medium is liquid, it is possible to use, for example, filtration, decantation or centrifugation.
  • the catalytic complexes can be washed so as to remove the excess reactants with which they could still be impregnated. Any inert diluent can be used for this washing, for example those which can be used as constituents of the reaction medium, such as alkanes and cycloalkanes. After washing, the catalytic complexes can be dried, for example, by sweeping with a stream of dry nitrogen or under vacuum.
  • the catalytic systems according to the invention also comprise an organometallic compound which serves as an activator.
  • organometallic compounds of the metals of groups la, Ila, llb, Illb and IVb of the Periodic Table are used such as the organometallic compounds of lithium, magnesium, zinc, aluminum or tin. The best results are obtained with organoaluminum compounds.
  • Fully alkylated compounds can be used, the alkyl chains of which contain from 1 to 20 carbon atoms and are straight or branched, such as, for example, n-butyllithium, diethylmagnesium, diethylzinc, tetraethyltin, tetrabutyltin and trialkylaluminums.
  • alkyl metal hydrides in which the alkyl radicals also comprise from 1 to 20 carbon atoms such as diisobutyl aluminum hydride and trimethyl tin hydride.
  • metal alkyl halides in which the alkyl radicals also comprise from 1 to 20 carbon atoms such as ethyl aluminum sesquichloride, diethyl aluminum chloride and diisobutyl aluminum chloride.
  • organoaluminum compounds obtained by reacting trialkylaluminiums or dialkylaluminium hydrides whose radicals contain from 1 to 20 carbon atoms with diolefins comprising from 4 to 20 carbon atoms, and more particularly the compounds called isoprenylaluminiums.
  • trialkylaluminiums whose alkyl chains are straight and contain from 1 to 18 carbon atoms. It is in fact found, quite surprisingly, that when these compounds serve as activators for the catalytic complexes prepared in accordance with the invention, that is to say by involving a reagent (3) which is an organoaluminum chloride as defined above, the molecular weight distributions of the polyolefins obtained are wider, all other conditions equal, than those of the polyolefins obtained in the presence of catalytic complexes prepared by making use of the usual reagents (3) (ethyl aluminum dichloride).
  • reagents (3) ethyl aluminum dichloride
  • the process of the invention applies to the polymerization of olefins with terminal unsaturation, the molecule of which contains from 2 to 20 atoms, and preferably from 2 to 6 carbon atoms, such as ethylene, propylene, butene. 1, 4-methylpentene-1 and hexene-1. It also applies to the copolymerization of these olefins together as well as with diolefins comprising preferably from 4 to 20 carbon atoms.
  • diolefins can be unconjugated aliphatic diolefins such as 1,4-hexadiene, monocyclic diolefins such as 4-vinylcyclohexene, 1,3-divinylcyclohexane, cyclopentadiene or 1,5-cyclooctadiene, diolefins alicyclics having an endocyclic bridge such as dicyclopentadiene or norbornadiene and conjugated aliphatic diolefins such as butadiene and isoprene.
  • unconjugated aliphatic diolefins such as 1,4-hexadiene, monocyclic diolefins such as 4-vinylcyclohexene, 1,3-divinylcyclohexane, cyclopentadiene or 1,5-cyclooctadiene, diolefins alicyclics having an endocyclic bridge such as dicyclopen
  • the process of the invention is particularly applicable to the manufacture of homopolymers of ethylene and of copolymers containing at least 90 mol% and preferably 95 mol% of ethylene.
  • the polymerization can be carried out according to any process designed: in solution or in suspension in a hydrocarbon solvent or diluent or even in the gas phase.
  • solvents or diluents similar to those used for the preparation are used.
  • preparation of the catalytic complex these are preferably alkanes or cycloalkanes such as isobutane, pentane, hexane, heptane, cyclohexane, methylcyclohexane or their mixtures. It is also possible to carry out the polymerization in the monomer or one of the monomers maintained in the liquid state. It is particularly advantageous to carry out polymerization processes in which the polymers are generated directly in the form of particles.
  • the polymerization processes in suspension in a liquid hydrocarbon diluent under the polymerization conditions are preferred, which, after separation of the unreacted monomer and the diluent, provide, in the presence of catalytic systems of the invention, polymer particles which have the morphological characteristics of the powders used in the transformation processes mentioned above.
  • the polymerization pressure is generally between atmospheric pressure and 100 kg / cm 2 , preferably 50 kg / cm 2 .
  • the temperature is generally chosen between 20 and 200 ° C. It is preferably between 60 and 120 ° C so as to directly obtain the polymer in solid form. No degradation in the morphology of the polyolefin particles obtained in the presence of the catalytic systems of the invention is observed when the polymerization temperature is lowered in this preferred zone. On the contrary, when solid catalytic complexes are prepared from the usual reagents (3) of the prior art, it is found that the lowering of the polymerization temperature exerts a detrimental effect on the morphology of the polyolefin obtained (the particles are thinner and less harsh).
  • the polymerization can be carried out continuously or batchwise.
  • the organometallic compound and the catalytic complex can be added separately to the polymerization medium. They can also be brought into contact, at a temperature between -40 and 80 ° C, for a period of up to 2 hours, before introducing them into the polymerization reactor. We can also put them in contact in several stages or add a part organometallic compound before the reactor or add several different organometallic compounds.
  • the total amount of organometallic compound used can vary to a large extent. It is generally between 0.02 and 50 mmol per dm 3 of solvent, diluent or reactor volume and preferably between 0.5 and 2.5 mmol per dm 3 .
  • the ratio of the amounts of organometallic compound and catalytic complex is also not critical. It is generally chosen so that the organometallic compound / titanium ratio expressed in mole / at.-g is greater than 1 and preferably greater than 10.
  • the average molecular weight, and hence the melt index of the polymers produced according to the process of the invention can be adjusted by the addition to the polymerization medium of one or more molecular weight modifiers such as hydrogen, zinc or cadmium diethyl, alcohols or carbon dioxide.
  • molecular weight modifiers such as hydrogen, zinc or cadmium diethyl, alcohols or carbon dioxide.
  • the specific gravity of the homopolymers produced according to the process of the invention can also be adjusted by the addition to the polymerization medium of an alkoxide of a metal from groups IVa and Va of the Periodic Table.
  • polymerization medium of an alkoxide of a metal from groups IVa and Va of the Periodic Table.
  • alkoxides suitable for this adjustment those of titanium and vanadium whose radicals contain from 1 to 20 carbon atoms each are particularly effective. These include Ti (OCH 3 ) 4 , Ti (OC 2 H 5 ) 4 , Ti [OCH 2 CH (CH 3 ) 2 ] 4 , Ti (OC 8 H 17 ) 4 and TI (OC 16 H 33 ) 4 .
  • the process of the invention makes it possible to manufacture polyolefins with very high productivities.
  • productivity expressed in grams of polyethylene per gram of catalytic complex used regularly exceeds 10,000 and in some cases 20,000.
  • the activity related to the amount of transition metals present in the catalytic complex is also very high.
  • homopolymerization of ethylene also expressed in grams of polyethylene per at.-g of titanium used, it regularly exceeds 200,000. In the most favorable cases, it is greater than 500,000.
  • the content of catalytic residues in the polymers produced according to the process of the invention is extremely low. More particularly, the content of residual transition metal is excessively low.
  • the content of the troublesome polymers in residues is so low that it is possible to economize on the purification treatment (for example an alcohol treatment), which is compulsory when the content of catalytic residue is high and is a costly operation in terms of raw materials and energy and requires considerable downtime.
  • the purification treatment for example an alcohol treatment
  • the polyolefin powders produced in accordance with the invention are therefore characterized by a remarkable morphology and can be used in this form. This is particularly the case for powders of ethylene polymers.
  • the polyolefins obtained according to the invention can however be granulated and be used in the form of granules according to conventional molding techniques: by injection, by extrusion, by extrusion blow molding, by calendering, etc.
  • a stock solution (S) is prepared by heating together, at 150 ° C, with stirring and for 2 hours, 9 moles of the reagent (2) and 4.5 moles of the reagent (1). ).
  • the Ti / Mg atomic ratio is therefore approximately 2 at.-g / at.-g.
  • 500 ml of the stock solution (S) in which there has been almost complete dissolution of the reagent (1) and which has been previously cooled, are added 1000 ml of hexane, so as to obtain a solution at about 500 g / bed.
  • organoaluminum chlorides used according to Examples 2, 3, 4 were prepared, from sales sold by Schering.
  • organoaluminum chlorides used according to Examples 2, 3, 4 were also prepared in known manner by reaction of the corresponding trialkylaluminum with aluminum trichloride.
  • organoaluminum chlorides are used in the form of solutions in hexane at 400 g / bed. They are added gradually to fractions of stock solutions (S), diluted as indicated above, at a temperature of approximately 50 ° C and with stirring, for approximately 90 minutes. At the end of this addition, the reaction mixture is subjected to curing for 1 hour at 60 ° C.
  • the amount of organoaluminum chloride used in each of the examples is such that the molar ratio of organoaluminum chloride / magnesium ethylate is approximately 10.
  • the catalytic complexes thus formed are used as such, without being separated from their reaction medium, in polymerization tests the general conditions of which are defined below.
  • the polymerization is continued for 1 h with stirring while keeping the total pressure constant by continuous addition of ethylene. After 1 h, the autoclave is degassed and the polyethylene thus produced is collected.
  • Table 1 lists the conditions specific to each test, the results obtained and the morphological characteristics of the polyethylenes produced.
  • Table 1 shows that the use of organoaluminum chlorides meeting the definition of the invention as reagents (3) (examples 1 to 4) leads, with improved catalytic activities, to polyethylenes which contain a proportion of large particles clearly greater than that present in the polyethylenes obtained with the usual reagent (3) of the prior art (example 5 R).
  • Example 7 R is given for comparison.
  • Catalytic complexes are prepared according to the preceding examples except that the reactants (2) and (1) are mixed so that the atomic ratio Ti / Mg is approximately 1.2 at-g / at.-g, that the amount of chloride organoaluminic implementation is such that the molar ratio organoaluminic chloride / magnesium ethylate is approximately 3.5 and that the organoaluminum chloride is added at a temperature of approximately 30 ° C.
  • Example 6 the catalytic complex is prepared by using isobutylaluminum dichloride as the organoaluminum chloride.
  • Example 7 R the catalytic complex is prepared using ethylaluminum dichloride as the organoaluminous chloride.
  • the catalytic complexes obtained are used in the form of a suspension in the medium which served to prepare them for carrying out ethylene polymerization tests under general conditions absolutely identical to those described in the previous examples.
  • organoaluminum chloride (reagents (3)) meeting the definition of the invention remain acquired despite significant changes in the molar ratios between reagents.
  • Catalytic complexes are prepared in accordance with Examples 1 to 5 R using them isobutylaluminum dichloride as organoaluminum chloride.
  • Catalytic complexes are prepared in accordance with Examples 1 to 5 R using isobutylaluminum dichloride used at 50 ° C, as the organoaluminum compound in Examples 13 to 15, and ethylaluminum dichloride, used at 30 ° C, in examples 16 R to 18 R.

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Description

La présente invention concerne un procédé perfectionné pour la polymérisation des alpha-oléfines. Elle concerne également un procédé de préparation de complexes catalytiques solides utilisables pour cette polymérisation.The present invention relates to an improved process for the polymerization of alpha-olefins. It also relates to a process for the preparation of solid catalytic complexes which can be used for this polymerization.

Il est connu d'utiliser, pour la polymérisation à basse pression des oléfines, des systèmes catalytiques comprenant un composé de métal de transition et un composé organométallique.It is known to use, for the low pressure polymerization of olefins, catalytic systems comprising a transition metal compound and an organometallic compound.

On connaît aussi, par les brevets belges 791 676 du 21.11.1972 et 799 977 du 24.5.1973 au nom de la Demanderesse, des systèmes catalytiques dont un constituant est obtenu en faisant réagir entre eux:

  • (1) un composé oxygéné organique ou un halogénure d'un métal, tels que l'éthylate de magnésium ou le dichlorure de magnésium,
  • (2) un composé oxygéné organique d'un métal de transition, tel que le tétrabutylate de titane, et
  • (3) un halogénure d'aluminium, tel que le dichlorure d'éthylaluminium.
Also known, by the Belgian patents 791,676 of November 21, 1972 and 799,977 of July 24, 1973 in the name of the Applicant, catalytic systems, a component of which is obtained by reacting with each other:
  • (1) an organic oxygenated compound or a metal halide, such as magnesium ethylate or magnesium dichloride,
  • (2) an organic oxygenated compound of a transition metal, such as titanium tetrabutylate, and
  • (3) an aluminum halide, such as ethyl aluminum dichloride.

Ces systèmes catalytiques sont uniques par les avantages extrêmement importants qu'ils présentent. Ainsi, leur activité et leur productivité sont très élevées. Leur préparation est extrêmement simple et ne conduit à aucun sous-produit polluant. Enfin, la morphologie du polymère obtenu permet de polymériser en suspension en continu avec une teneur relative en polymère très élevée et donc une quantité relative de diluant à traiter avant recyclage très faible.These catalytic systems are unique in that they have extremely important advantages. Thus, their activity and their productivity are very high. Their preparation is extremely simple and does not lead to any polluting by-product. Finally, the morphology of the polymer obtained makes it possible to polymerize in suspension continuously with a very high relative content of polymer and therefore a very small amount of diluent to be treated before recycling.

Cependant, l'utilisation de systèmes catalytiques tels que celui décrit ci-dessus présente encore un inconvénient sérieux lorsqu'ils sont utilisés dans un procédé où le polymère est obtenu directement sous forme de particules. On a constaté en effet que les polymères obtenus en particules directement à leur intervention, quoique de granulométrie régulière, contiennent un pourcentage relativement élevé de particules fines et ont une grosseur moyenne des particules relativement faible.However, the use of catalytic systems such as that described above still presents a serious drawback when they are used in a process where the polymer is obtained directly in the form of particles. It has in fact been found that the polymers obtained in particles directly upon their intervention, although of regular particle size, contain a relatively high percentage of fine particles and have a relatively small average particle size.

La morphologie des particules de ces polymères pose dès lors des problèmes au cours de leur séchage, de leur stockage, de leur transport, de leur manipulation et de leur mise en oeuvre par les techniques connues de moulage. Les tentatives réalisées jusqu'à présent pour augmenter la grosseur moyenne des particules des polymères obtanues directement par polymérisation au moyen des systèmes catalytiquès décrits ci-dessus n'ont pas été complètement satisfaisantes. C'est ainsi qu'on a constaté qu'une certaine augmentation du diamètre moyen des particules pouvait être obtenue en élevant la température à laquelle on met l'halogénure d'aluminium en oeuvre. Cette augmentation du diamètre moyen s'accompagne toutefois malencontreusement d'une diminution du poids spécifique apparent et d'un élargissement important de la distribution granulométrique des particules.The morphology of the particles of these polymers therefore poses problems during their drying, their storage, their transport, their handling and their use by known molding techniques. The attempts made so far to increase the average particle size of the polymers obtained directly by polymerization using the catalyst systems described above have not been completely satisfactory. It has thus been found that a certain increase in the average diameter of the particles can be obtained by raising the temperature at which the aluminum halide is used. This increase in the mean diameter is however unfortunately accompanied by a decrease in the apparent specific weight and a significant widening of the particle size distribution.

Le but principal de la présente invention est donc l'obtention, sans les effets secondaires néfastes susmentionnés, de polyoléfines dont le pourcentage de fines particules est réduit et dont la grosseur moyenne des particules est plus élevée.The main object of the present invention is therefore to obtain, without the above-mentioned harmful side effects, polyolefins in which the percentage of fine particles is reduced and in which the average particle size is higher.

Par ailleurs, les polyoléfines sont de plus en plus fréquemment mises en oeuvre sous forme de poudres, c'est-à-dire sous forme de particules denses et régulières dont un pourcentage important présente un diamètre moyen supérieur à 250 microns, de préférence supérieur à 500 microns.Furthermore, polyolefins are increasingly used in the form of powders, that is to say in the form of dense and regular particles, a large percentage of which have an average diameter greater than 250 microns, preferably greater than 500 microns.

Les poudres de polyoléfines sont appréciées particulièrement pour la mise en oeuvre par injection. D'autres débouchés intéressants des poudres de polyoléfines sont la réalisation d'enduits par diverses techniques (enduction électrostatique, enduction par pulvérisation, etc) et l'utilisation comme additifs, agents de démoulage, cires, compositions pour peintures, liants pour textiles non tissés, etc.Polyolefin powders are particularly appreciated for processing by injection. Other interesting outlets for polyolefin powders are the production of coatings by various techniques (electrostatic coating, spray coating, etc.) and the use as additives, release agents, waxes, compositions for paints, binders for nonwoven textiles. , etc.

Un autre but de la présente invention est la fabrication de poudres de polyoléfines au moyen de procédés de polymérisation qui donnent directement des polymères sous forme de particules qui ont les caractéristiques morphologiques des poudres utilisées dans les procédés mentionnés plus haut.Another object of the present invention is the manufacture of polyolefin powders by means of polymerization processes which directly give polymers in the form of particles which have the morphological characteristics of the powders used in the processes mentioned above.

L'invention est basée sur la découverte surprenante qu'une classe tout à fait particulière de systèmes catalytiques décrits plus haut permet d'obtenir sans affecter les avantages inhérents à ces systèmes, des polvoléfines sous forme de particules denses et dures, de diamètre moyen élevé, de distribution granulométrique serrée et de poids spécifique apparent élevé. Ces propriétés les rendent particulièrement aptes à être mises en oeuvre sous forme de poudres lors de leur transformation en objets finis.The invention is based on the surprising discovery that a quite particular class of catalytic systems described above makes it possible to obtain without affecting the advantages inherent in these systems, polvolefins in the form of dense and hard particles, of large average diameter. , of tight particle size distribution and high apparent specific gravity. These properties make them particularly suitable for being used in the form of powders when they are transformed into finished objects.

La présente invention concerne donc un procédé pour la polymérisation des alpha-oléfines dans lequel on opère en présence d'un système catalytique comprenant un composé organométallique d'un métal des groupes la, lla, Ilb, Illb et IVb du Tableau Périodique et un complexe catalytique solide préparé en faisant réagir entre eux:

  • (1) au moins un composé (M) choisi parmi les composés oxygénés organiques et les composés halogénés du magnésium
  • (2) au moins un composé (T) choisi parmi les composés oxygénés organiques et les composés halogénés du titane
  • (3) au moins un halogénure d'aluminium (A), ce dernier étant choisi parmi les chlorures organoaluminiques de formule générale AIR"CI3_" dans laquelle R est un radical alkyle comprenant de 4 à 18 atomes de carbone et n est un nombre tel que 1 < n < 1,5.
The present invention therefore relates to a process for the polymerization of alpha-olefins in which one operates in the presence of a catalytic system comprising an organometallic compound of a metal from groups la, lla, Ilb, Illb and IVb of the Periodic Table and a complex solid catalytic prepared by reacting with each other:
  • (1) at least one compound (M) chosen from organic oxygenated compounds and halogenated magnesium compounds
  • (2) at least one compound (T) chosen from organic oxygenated compounds and halogenated titanium compounds
  • (3) at least one aluminum halide (A), the latter being chosen from organoaluminum chlorides of general formula AIR "CI3_" in which R is an alkyl radical comprising from 4 to 18 carbon atoms and n is such a number that 1 <n <1.5.

Par composés oxygénés organiques du magnésium et du titane, on entend désigner tous les composés où un radical organique quelconque est lié au métal par l'intermédiaire de l'oxygène, c'est-à-dire tous les composes comprenant au moins une séquence de liaisons métal-oxygène radical organique par atome de métal. Les radicaux organiques liés au métal par l'intermédiaire de l'oxygène sont quelconques. Ils sont choisis de préférence parmi les radicaux comprenant de 1 à 20 atomes de carbone et, plus particulièrement, parmi ceux comprenant de 1 à 10 atomes de carbohe. Les meilleurs résultats sont obtenus lorsque ces radicaux comprennent de 2 à 6 atomes de carbone. Ces radicaux peuvent être saturés ou insaturés, à chaîne ramifiée, à chaîne droite ou cycliques; ils peuvent également être substitués ou comporter des hétéroatomes, tels que le silicium, le soufre, l'azote ou le phosphore, dans leur chaîne. Ils sont choisis de préférence parmi les radicaux hydrocarbonés et en particulier parmi les radicaux alkyle (linéaires ou branchés), alkényle, aryle, cycloalkyle, arylalkyle, alkylaryle, acyle et leurs dérivés substitués.By organic oxygenated compounds of magnesium and titanium is meant to designate all compounds in which any organic radical is linked to the metal via oxygen, that is to say all the compounds comprising at least one sequence of metal-organic radical oxygen bonds per metal atom. The organic radicals linked to the metal via oxygen are arbitrary. They are preferably chosen from the radicals comprising from 1 to 20 carbon atoms and, more particularly, from those comprising from 1 to 10 carbon atoms. The best results are obtained when these radicals contain from 2 to 6 carbon atoms. These radicals can be saturated or unsaturated, branched chain, straight chain or cyclic; they can also be substituted or contain heteroatoms, such as silicon, sulfur, nitrogen or phosphorus, in their chain. They are preferably chosen from hydrocarbon radicals and in particular from alkyl radicals (linear or branched), alkenyl, aryl, cycloalkyl, arylalkyl, alkylaryl, acyl and their substituted derivatives.

Par composés halogénés du magnésium et du titane, on entend désigner tous les composés comprenant au moins une liaison métal-halogène. L'halogène lié au métal peut être le fluor, le chlore, le brome ou l'iode. De préférence, l'halogène est le chlore.The term “halogenated compounds of magnesium and titanium” is intended to denote all the compounds comprising at least one metal-halogen bond. The metal bound halogen can be fluorine, chlorine, bromine or iodine. Preferably, the halogen is chlorine.

Parmi tous les composés oxygénés organiques et halogénés qui conviennent, on utilise de préférence ceux qui ne contiennent que des liaisons métal-oxygène-radical organique et/ou des liaisons métal-halogène à l'exclusion de toute autre liaison.Among all the organic and halogenated oxygenated compounds which are suitable, use is preferably made of those which contain only metal-oxygen-organic radical bonds and / or metal-halogen bonds to the exclusion of any other bond.

Les complexes catalytiques solides utilisés dans la présente invention sont préparés à partir de réactifs (1) qui sont des composés (M) du magnésium.The solid catalytic complexes used in the present invention are prepared from reactants (1) which are magnesium compounds (M).

Les composés oxygénés organiques (M) peuvent comporter, en plus des radicaux organiques liés au magnésium par l'intermédiaire de l'oxygène, d'autres radicaux. Ces autres radicaux sont de préférence l'oxygène et les radicaux inorganiques liés au métal par l'intermédiaire de l'oxygène tels que les radicaux -OH, ―(S4)"2, -N03, -(PO4)1/3, ―(CO3)½ et -CI04. Il peut s'agir également de radicaux organiques liés directement au magnésium par le carbone.The organic oxygenated compounds (M) can comprise, in addition to the organic radicals linked to magnesium via oxygen, other radicals. These other radicals are preferably oxygen and the inorganic radicals linked to the metal via oxygen, such as the radicals -OH, - (S4) "2, -N0 3 , - (PO 4 ) 1/3 , - (CO 3 ) ½ and -CI0 4. They can also be organic radicals directly linked to magnesium by carbon.

Parmi les composés (M) entrant dans la famille des composés oxygénés organiques du magnésium, on peut citer:

  • -les alkoxydes, tels que le méthylate, l'éthylate, l'isopropylate, Îe décanolate et le cyclohexanolate,
  • -les alkylalkoxydes, tels que l'éthyléthylate,
  • ―les hydroxyalkoxydes, tels que l'hydroxyméthylate,
  • -les phénoxydes, tels que le phénate, le naphténate, l'anthracénate, le phénantrénate et le crésolate,
  • -les carboxylates éventuellement hydratés, tels que l'acétate, le stéarate, le benzoate, le phénylacétate, l'adipate, le sébacate, le phtalate, l'acrylate et l'oléate,
  • -les composés oxygénés azotés organiques, c'est-à-dire des composés comprenant des séquences de liaisons magnésium-oxygène-azote-radical organique, tels que les oximates, en particulier, le butyloximate, le diméthylglyoximate et le cyclohexyloximate, les sels d'acides hydroxylamines en particulier le dérivé de la N - nitroso - N - phényl - hydroxylâmine,
  • -les chélates, c'est-à-dire les composés oxygénés organiques dans lesquels le magnésium possède au moins une séquence de liaisons normales du type magnésium oxygène-radical organique et au moins une liaison de coordination de manière à former un hétérocycle dans lequel le magnésium est inclus, tels que les énolates et en particulier l'acétylacétonate, ainsi que les complexes obtenus à partir de dérivés phénoliques possédant un groupe électrodonneur par exemple en position ortho ou méta par rapport au groupe hydroxyle et en particulier le 8-hydroxyquinoléinate,
  • -les silanolates, c'est-à-dire des composés comprenant des séquences de liaisons magnésium-oxygène-silicium-radical hydrocarbone, tels que le triphénylsilanolate.
Among the compounds (M) belonging to the family of organic oxygenated magnesium compounds, there may be mentioned:
  • alkoxides, such as methylate, ethylate, isopropylate, decanolate and cyclohexanolate,
  • -alkylalkoxides, such as ethylethylate,
  • Hydroxy hydroxyalkoxides, such as hydroxymethylate,
  • -phenoxides, such as phenate, naphthenate, anthracenate, phenanthrenate and cresolate,
  • optionally hydrated carboxylates, such as acetate, stearate, benzoate, phenylacetate, adipate, sebacate, phthalate, acrylate and oleate,
  • -organic nitrogenous oxygenated compounds, that is to say compounds comprising sequences of magnesium-oxygen-nitrogen-organic radical linkages, such as oximates, in particular, bu tyloximate, dimethylglyoximate and cyclohexyloximate, the salts hydroxylamine acids, in particular the N - nitroso - N - phenyl - hydroxylamine derivative,
  • chelates, that is to say organic oxygenated compounds in which magnesium has at least one normal bond sequence of the magnesium oxygen-organic radical type and at least one coordination bond so as to form a heterocycle in which the magnesium is included, such as the enolates and in particular acetylacetonate, as well as the complexes obtained from phenolic derivatives having an electron donor group for example in ortho or meta position with respect to the hydroxyl group and in particular 8-hydroxyquinoline,
  • silanolates, that is to say compounds comprising sequences of magnesium-oxygen-silicon-hydrocarbon radical linkages, such as triphenylsilanolate.

Il est bien entendu qu'entrent également dans le cadre de l'invention les composés oxygénés organiques du magnésium suivants:

  • -les composés comprenant plusieurs radicaux organiques différents, tels que le méthoxyéthylate de magnésium,
  • -les alkoxydes et phénoxydes complexes du magnésium et d'un autre métal, tels que Mg(Al(OR)4]2 et Mg[Al(OR)6]2, et
  • -les mélanges de deux ou de plusieurs des composés oxygénés organiques du magnésium définis ci-dessus.
It is understood that the following organic oxygenated magnesium compounds also fall within the scope of the invention:
  • -compounds comprising several different organic radicals, such as magnesium methoxyethylate,
  • the complex alkoxides and phenoxides of magnesium and of another metal, such as Mg (Al (OR) 4 ] 2 and Mg [Al (OR) 6 ] 2 , and
  • -mixtures of two or more of the organic oxygenated magnesium compounds defined above.

Parmi les composés halogénés du magnésium (M), on peut citer:

  • -les dihalogénures du type commercial qui sont appelés conventionnellement "anhydres" et qui sont en fait des dihalogénures hydratés contenant une molécule et moins d'eau par molécule de dihalogénure; les dichlorures de magnésium "anhydres du commerce" sont un exemple typique de ces composés;
  • -les dihalogénures complexés au moyen de divers donneurs d'électrons, comme par exemple les complexes avec l'ammoniac, tels que MgCl2.6NH3, MgCI2.2NH3, et les complexes avec les alcools, tels que MgCl2.6CH3OH, MgCl2.6C2.H50H et MgCl2.6C3HOH,
  • -les dihalogénures hydratés contenant plus d'une molécule d'eau par molécule de dihalogénure, tels que MgCl2.6H2O, MgCl2.2H2O,
  • -les composés comprenant, outre la liaison magnésium-halogène, un radical inorganique, lié au magnésium par l'intermédiaire de l'oxygène, tel qu'un radical hydroxyle, comme dans Mg(OH)Cl et Mg(OH)Br,
  • -les composés comprenant, outre la liaison magnésium-halogène (de préférence la liaison magnésium-chlore) une liaison magnésium-radical organique, de préférence une liaison magnésium-radical hydrocarboné (tel que défini plus haut), comme dans Mg(C2H5)Cl et Mg(C6H5)Cl,
  • -les produits de l'hydrolyse des halogénures (de préférence des chlorures) hydratés du magnésium, pour autant que ces produits contiennent encore des liaisons magnésium-halogène,
  • -les compositions mixtes comprenant des composés halogènes et oxygénés du magnésium. Des exemples typiques de ces compositions sont les halogénures (de préférence les chlorures) basiques de magnésium tels que MgCI2.MgO.H20, MgCl2.3MgO.7H2O et MgBr2.3MgO.6H20,
  • -les mélanges de deux ou plusieurs des composés halogénés du magnésium définis ci-dessus. Enfin, il est bien entendu que l'utilisation de deux ou plusieurs composés tels que définis ci-dessus entre également dans le cadre de la présente invention.
Among the halogenated magnesium compounds (M), there may be mentioned:
  • -the commercial type dihalides which are conventionally called "anhydrous" and which are in fact hydrated dihalides containing one molecule and less water per molecule of dihalide; "commercial anhydrous" magnesium dichlorides are a typical example of these compounds;
  • dihalides complexed by means of various electron donors, such as for example complexes with ammonia, such as MgCl 2 .6NH 3 , MgCl 2 .2NH 3 , and complexes with alcohols, such as MgCl 2 .6CH 3 OH, MgCl 2 .6C 2 .H 5 0H and MgCl2 . 6C 3 HOH,
  • hydrated dihalides containing more than one molecule of water per molecule of dihalide, such as MgCl 2 .6H 2 O, MgCl 2 .2H 2 O,
  • the compounds comprising, in addition to the magnesium-halogen bond, an inorganic radical, linked to magnesium via oxygen, such as a hydroxyl radical, as in Mg (OH) Cl and Mg (OH) Br,
  • the compounds comprising, in addition to the magnesium-halogen bond (preferably the magnesium-chlorine bond) a magnesium-organic radical bond, preferably a magnesium-hydrocarbon radical bond (as defined above), as in Mg (C 2 H5 ) Cl and Mg (C 6 H 5 ) Cl,
  • -the products of the hydrolysis of halides (preferably chlorides) hydrated with magnesium, provided that these products still contain magnesium-halogen bonds,
  • - mixed compositions comprising halogenated and oxygenated magnesium compounds. Typical examples of these compositions are the halides (preferably chlorides) of basic magnesium such as MgCl 2 .MgO.H 0 2, MgCl 2 and MgBr 2 O .3MgO.7H 2 .3MgO.6H 2 0,
  • - mixtures of two or more of the halogenated magnesium compounds defined above. Finally, it is understood that the use of two or more compounds as defined above also falls within the scope of the present invention.

De même, l'utilisation de composés du magnésium contenant à la fois une liaison magnésium-halogène et un radical organique tel que défini ci-dessus lié au magnésium par l'intermédiaire de t'oxygène fait également partie de l'invention. Les composés de ce type donnant les meilleurs résultats sont bien entendu, les chloralkoxydes et les chlorphénoxydes tels que Mg(OCH3)CI, Mg(OC2H5)Cl et Mg(OCeHs)CI par exemple.Likewise, the use of magnesium compounds containing both a magnesium-halogen bond and an organic radical as defined above linked to magnesium via oxygen is also part of the invention. The compounds of this type giving the best results are of course, chloralkoxides and chlorphenoxides such as Mg (OCH 3 ) CI, Mg (OC 2 H 5 ) Cl and Mg (OC e H s ) CI for example.

Les meilleurs résultats sont obtenus lorsque le composé (M) du magnésium est un dialkoxyde.The best results are obtained when the compound (M) of magnesium is a dialkoxide.

Les réactifs (2) utilisés pour préparer les complexes catalytiques selon l'invention sont des composés (T) du titane. On utilise de préférence les composés du titane tétravalent parce qu'ils sont plus souvent liquides et en tout cas plus souvent et mieux solubles que ceux où ce métal se trouve à une valence inférieure à 4. Les composés oxygénés organiques (T) du titane utilisables comme réactifs (2) peuvent également être des composés comprenant des liaisons métal-oxygène et les composés condensés comprenant des séquences de liaisons métal-oxygène-métal, pourvu qu'ils comportent aussi au moins une séquence de liaisons métal-oxygène-radical organique par molécule.The reagents (2) used to prepare the catalytic complexes according to the invention are titanium compounds (T). The tetravalent titanium compounds are preferably used because they are more often liquid and in any case more often and better soluble than those where this metal is at a valence of less than 4. The organic oxygenated compounds (T) of the titanium which can be used as reactants (2) can also be compounds comprising metal-oxygen bonds and condensed compounds comprising sequences of metal-oxygen-metal bonds, provided that they also comprise at least one sequence of metal-oxygen-organic radical bonds by molecule.

On peut représenter les composés oxygénés organiques (T) par la formule générale (TiOx(OR)4-2x]m où R représente un radical organique tel que défini plus haut, où x est un nombre tel que 0 ≤ x < 1,5 et où m est un nombre entier. On préfère utiliser les composés oxygénés organiques où x est tel que 0 < x < 1 et m tel que 1 < m < 6.The organic oxygenated compounds (T) can be represented by the general formula (TiO x (OR) 4-2x ] m where R represents an organic radical as defined above, where x is a number such that 0 ≤ x <1, 5 and where m is an integer We prefer to use organic oxygenated compounds where x is such that 0 <x <1 and m such that 1 <m <6.

L'utilisation de composés oxygénés organiques (T) comprenant plusieurs radicaux organiques différents entre également dans le cadre de la présente invention.The use of organic oxygenated compounds (T) comprising several different organic radicals also falls within the scope of the present invention.

Parmi les composés oxygénés organiques (T) du titane, on peut citer:

  • ―les alkoxydes, tels que Ti(OC2H5)4, Ti(OnC3H7)4, TI(OnC4H9)4, TI(OC4H9)4, et Ti(O-tertC4H9)4,
  • -les phénoxydes, tels que Ti(OC6H5)4.
  • -les oxyalkoxydes, tels que TiO(OC2H5)2,
  • -les alkoxydes condensés, tels que Ti2O(OiC3H7)6,
  • -les carboxylates, tels que Ti(OOCCH314,
  • -les énolates, tels que l'acétylacétonate de titane.
Among the organic oxygenated compounds (T) of titanium, there may be mentioned:
  • Alkalkoxides, such as Ti (OC 2 H 5 ) 4 , Ti (OnC 3 H 7 ) 4 , TI (OnC 4 H 9 ) 4 , TI (OC 4 H 9 ) 4 , and Ti (O-tertC 4 H 9 ) 4 ,
  • -phenoxides, such as Ti (OC 6 H 5 ) 4 .
  • - oxyalkoxide, such as TiO (OC 2 H 5 ) 2 ,
  • - condensed alkoxides, such as Ti 2 O (OiC 3 H 7 ) 6 ,
  • -carboxylates, such as Ti (OOCCH 3 1 4 ,
  • -enolates, such as titanium acetylacetonate.

Parmi les composés halogénés (T) du titane, on peut citer:

  • -les tétrahalogénures, tels que TiCl4, TiBr4,
  • ―les halogénures complexés au moyen de divers donneurs d'électrons, tels que TiCI4.6NH3, TiCl4.2C5H5N, TiCl4.C4H8O2,
  • -les halogénures complexes de titane et d'un métal alcalin, tels que K2TiCl6 et Na2TiCl6,
  • -les oxyhalogénures, tels que TiOCl2,
  • -les halogénoalkoxydes, tels que Ti(OC2H5)2Cl2, Ti(OC2H5)3Cl, Ti(OiC3H7)3Cl, Ti(OiC4H9)2Cl2.
Among the halogenated compounds (T) of titanium, there may be mentioned:
  • -tetrahalides, such as TiCl 4 , TiBr 4 ,
  • Complex halides complexed using various electron donors, such as TiCI 4 .6NH 3 , TiCl 4 .2C 5 H 5 N, TiCl 4 .C 4 H 8 O 2 ,
  • complex halides of titanium and an alkali metal, such as K 2 TiCl 6 and Na 2 TiCl 6 ,
  • oxyhalides, such as TiOCl 2 ,
  • - haloalkoxide, such as Ti (OC 2 H 5 ) 2 Cl 2 , Ti (OC 2 H 5 ) 3 Cl, Ti (OiC 3 H 7 ) 3 Cl, Ti (OiC 4 H 9 ) 2 Cl 2 .

Les meilleurs résultats sont obtenus avec les tétraalkoxydes du titane.The best results are obtained with titanium tetraalkoxides.

Il va de soi que l'utilisation de plusieurs composés (T) différents du titane entre également dans le cadre de l'invention.It goes without saying that the use of several compounds (T) different from titanium also falls within the scope of the invention.

Il peut être avantageux, pour la fabrication de polymères d'alpha-oléfines de distribution large des poids moléculaires, d'utiliser en outre au moins un composé de métal de transition supplémentaire (réactif (4)) pour préparer les complexes catalytiques solides de l'invention. Ce composé supplémentaire est alors un composé (Z) choisi parmi les composés oxygénés organiques et les composés halogénés du zirconium.It may be advantageous, for the manufacture of alpha-olefin polymers of wide molecular weight distribution, to additionally use at least one additional transition metal compound (reagent (4)) to prepare the solid catalytic complexes of l 'invention. This additional compound is then a compound (Z) chosen from organic oxygenated compounds and halogenated zirconium compounds.

Ces composés (Z) répondent en tous points aux définitions et limitations énoncées ci-avant en rapport avec les composés (T).These compounds (Z) meet in all respects the definitions and limitations set out above in relation to the compounds (T).

A titre d'exemples de composés du zirconium (Z) utilisables, on peut citer:

  • -les alkoxydes, tels que Zr(OC4H9)4,
  • -les phénoxydes, tels que Zr(OC6H5)4,
  • -les oxyalkoxydes, tels que Zr[OZr(OC2H5)3]4,
  • -les carboxylates, tels que Zr(OOCCH3)4, Zr(C2O4)2·
  • -les énolates, tels que l'acétylacétonate de zirconium,
  • -les tétrahalogénures, tels que ZrCl4 et ZrF4,
  • -les halogénures complexés au moyen de divers donneurs d'électrons, tels que ZrC14.8NH3, ZrC14.4NH3 et ZrCL4.4C5H5N,
  • -les oxyhalogénures, tels que ZrOF2 et ZrOCl2.8H2O,
  • -les halogénoalkoxydes, tels que Zr(OC4H9)Cl3.
As examples of zirconium (Z) compounds which can be used, mention may be made of:
  • -alkoxides, such as Zr (OC 4 H 9 ) 4 ,
  • -phenoxides, such as Zr (OC 6 H 5 ) 4 ,
  • - oxyalkoxide, such as Zr [OZr (OC 2 H 5 ) 3 ] 4 ,
  • -carboxylates, such as Zr (OOCCH 3 ) 4 , Zr (C 2 O 4 ) 2 ·
  • -enolates, such as zirconium acetylacetonate,
  • -tetrahalides, such as ZrCl 4 and ZrF 4 ,
  • the halides complexed using various electron donors, such as ZrC1 4 .8NH 3 , ZrC1 4 .4NH 3 and ZrCL 4 .4C 5 H 5 N,
  • oxyhalides, such as ZrOF 2 and ZrOCl 2 .8H 2 O,
  • - haloalkoxide, such as Zr (OC 4 H 9 ) Cl 3 .

Les meilleurs résultats sont obtenus avec les tétralkoxydes et le tétrachlorure de zirconium.The best results are obtained with tetralkoxides and zirconium tetrachloride.

Dans ce mode de réalisation particulier de l'invention, on préfère mettre ces différents composés (T) et (Z) en oeuvre comme décrit dans le brevet belge 840 378 déposé le 5.4.1976 au nom de la Demanderesse, dont le contenu est applicable en tout point au présent mode particulier de réalisation de l'invention.In this particular embodiment of the invention, it is preferred to use these different compounds (T) and (Z) as described in Belgian patent 840,378 filed on 5.4.1976 in the name of the Applicant, the content of which is applicable at any point in this particular embodiment of the invention.

Les complexes catalytiques solides utilisables selon la présente invention sont préparés enfin à partir de réactifs (3) qui doivent être des chlorures organoaluminiques de formule générale AIRnCI3-. dans laquelle R est un radical alkyle, linéaire ou branché, comprenant de 4 à 18 atomes de carbone et dans laquelle n vaut de 1 à 1,5.The solid catalytic complexes which can be used according to the present invention are finally prepared from reagents (3) which must be organoaluminum chlorides of general formula AIR n CI 3-. in which R is an alkyl radical, linear or branched, comprising from 4 to 18 carbon atoms and in which n is from 1 to 1.5.

Lorsque le radical alkyle est branché, la chaîne latérale est de préférence unique et courte, et est en particulier un groupe méthyle. De préférence, le radical branché est un radical "iso" unique, c'est-à-dire un radical dans lequel le groupe substituant est en position α par rapport au carbone terminal du radical.When the alkyl radical is connected, the side chain is preferably single and short, and is in particular a methyl group. Preferably, the branched radical is a single “iso” radical, that is to say a radical in which the substituent group is in position α with respect to the terminal carbon of the radical.

Les meilleurs résultats sont obtenus lorsque les chlorures organoaluminiques répondent à la formule ci-dessus, dans laquelle n vaut 1. Des chlorures organiques répondant à cette définition sont par exemple les dichlorures de n-butyl- et d'isobutylaluminium, de n-octyl- et d'isooctylaluminium, de n-hexadécylaluminium, de n-octadécylaluminium. Un chlorure organoaluminique tout particulièrement préféré et facilement accessible est le dichlorure d'isobutylaluminium AI(i-CQH9)CI2.The best results are obtained when the organoaluminum chlorides correspond to the above formula, in which n is 1. Organic chlorides meeting this definition are, for example, n-butyl- and isobutylaluminum dichlorides, n-octyl- and isooctylaluminium, n-hexadécylaluminium, n-octadécylaluminium. A particularly preferred and easily accessible organoaluminum chloride is isobutylaluminum dichloride AI (iC Q H 9 ) CI 2 .

Le choix du réactif (3) est une caractéristique essentielle de l'invention. C'est en effet la nature de ce réactif qui, de manière surprenante, est à la base de l'amélioration sensible de la morphologie des polyoléfines obtenues selon le procédé de l'invention.The choice of reagent (3) is an essential characteristic of the invention. It is indeed the nature of this reagent which, surprisingly, is at the basis of the substantial improvement in the morphology of the polyolefins obtained according to the process of the invention.

L'utilisation de plusieurs chlorures organoaluminiques différents n'est pas exclue du cadre de l'invention, pour autant que les radicaux alkyles contenus dans chacun d'eux contiennent au moins 4 atomes de carbone.The use of several different organoaluminum chlorides is not excluded from the scope of the invention, provided that the alkyl radicals contained in each of them contain at least 4 carbon atoms.

Ces chlorures organoaluminiques peuvent être préparés, éventuellement "in situ" et de préférence préalablement à leur mise en oeuvre, notamment en mélangeant les trialkylaluminiums correspondants avec des chlorures d'aluminium contenant plus de chlore que le chlorure que l'on souhaite obtenir. Il va de soi que la portée de l'invention n'est pas limitée à l'utilisation de chlorures organoaluminiques constitués exclusivement de composés répondant à la formule générale susmentionnée mais qu'elle s'étend aux produits techniques contenant, outre une proportion substantielle de ces composés, des sous-produits tels que les réactifs ayant servi à leur préparation. On préfère toutefois que ces produits contiennent au moins 80% en poids de chlorures organoaluminiques répondant à la formule générale.These organoaluminum chlorides can be prepared, optionally "in situ" and preferably prior to their use, in particular by mixing the corresponding trialkylaluminums with aluminum chlorides containing more chlorine than the chloride which it is desired to obtain. It goes without saying that the scope of the invention is not limited to the use of organoaluminum chlorides consisting exclusively of compounds corresponding to the general formula above mentioned but that it extends to technical products containing, in addition to a substantial proportion of these compounds, by-products such as the reagents used for their preparation. However, it is preferred that these products contain at least 80% by weight of organoaluminum chlorides corresponding to the general formula.

On peut préparer les complexes catalytiques solides de l'invention au départ des réactifs (1), (2), (3) et éventuellement (4) ci-dessus selon toutes les méthodes induisant une réaction chimique entre eux.The solid catalytic complexes of the invention can be prepared from the reactants (1), (2), (3) and optionally (4) above according to all the methods inducing a chemical reaction between them.

On préfère réaliser la réaction de formation des complexes en milieu liquide. Pour ce faire, on peut opérer en présence d'un diluant, notamment lorsque les réactifs ne sont pas liquides eux-mêmes dans les conditions opératoires ou lorsqu'il n'y a pas assez de réactifs liquides. Lorsqu'on fait usage d'un diluant, on le choisit généralement parmi ceux qui sont capables de dissoudre au moins un des réactifs et en particulier parmi les alkanes, cycloalkanes et hydrocarbures aromatiques comprenant de 4 à 20 atomes de carbone comme par exemple l'isobutane, l'hexane, l'heptane, le cyclohexane, le benzène, le toluène, etc. On peut aussi utiliser des solvants polaires comme les éthers et les alcools comprenant de 1 à 12 atomes de carbone (éthanol et éther diéthylique, par exemple), le tétrahydrofuranne, la pyridine, le chlorure de méthylène, etc. Lorsqu'on utilise un diluant dissolvant au moins un des réactifs, on préfère que la concentration totale du ou des réactifs dissous soit supérieure à 5% en poids et de préférence à 20% en poids par rapport au diluant.It is preferred to carry out the reaction for forming the complexes in a liquid medium. To do this, it is possible to operate in the presence of a diluent, in particular when the reagents are not themselves liquid under the operating conditions or when there are not enough liquid reagents. When a diluent is used, it is generally chosen from those which are capable of dissolving at least one of the reactants and in particular from alkanes, cycloalkanes and aromatic hydrocarbons comprising from 4 to 20 carbon atoms such as for example the isobutane, hexane, heptane, cyclohexane, benzene, toluene, etc. It is also possible to use polar solvents such as ethers and alcohols comprising from 1 to 12 carbon atoms (ethanol and diethyl ether, for example), tetrahydrofuran, pyridine, methylene chloride, etc. When using a diluent dissolving at least one of the reagents, it is preferred that the total concentration of the dissolved reagent (s) is greater than 5% by weight and preferably 20% by weight relative to the diluent.

Dans tous les cas, que l'on utilise un diluant ou qu'il y ait suffisamment de réactifs liquides dans les conditions opératoires, le milieu réactionnel se présente de préférence sous la forme d'un liquide relativement visqueux dans lequel peuvent se trouver des matières solides à l'état dispersé.In all cases, whether a diluent is used or there are sufficient liquid reagents under the operating conditions, the reaction medium is preferably in the form of a relatively viscous liquid in which materials may be present. solid in dispersed state.

L'ordre d'addition des réactifs est quelconque. Les réactifs (3) peuvent, en particulier, être introduits dans le milieu réactionnel à n'importe quel moment de la préparation du complexe catalytique solide.The order of addition of the reagents is arbitrary. The reagents (3) can, in particular, be introduced into the reaction medium at any time during the preparation of the solid catalytic complex.

Pour des raisons de commodité, on préfère cependant préparer ces complexes catalytiques solides selon l'une des méthodes ci-après:

  • 1) on met en présence le réactif (1) et le réactif (2) en les mélangeant progressivement ou en les ajoutant l'un à l'autre; on ajoute ensuite progressivement le réactif (3);
  • 2) on mélange, de préférence rapidement, le réactif (2) et le réactif (3), puis on ajoute le réactif (1);
  • 3) on mélange simultanément et progressivement les trois réactifs.
For reasons of convenience, however, it is preferable to prepare these solid catalytic complexes according to one of the methods below:
  • 1) the reagent (1) and the reagent (2) are brought together by gradually mixing them or by adding them to each other; the reagent (3) is then gradually added;
  • 2) the reagent (2) and the reagent (3) are mixed, preferably rapidly, then the reagent (1) is added;
  • 3) the three reagents are mixed simultaneously and gradually.

Quelle que soit la méthode choisie, on préfère donc que l'addition du réactif (3) se fasse à la fin de la préparation des complexes catalytiques, c'est-à-dire au plus tôt pendant que les réactifs (1) et (2) sont mis en présence. Les meilleurs résultats sont obtenus lorsque le réactif (3) est mis en oeuvre après que les réactifs (1) et (2) ont été mis en présence dans leur totalité.Whichever method is chosen, it is therefore preferred that the addition of reagent (3) takes place at the end of the preparation of the catalytic complexes, that is to say as soon as possible while the reagents (1) and ( 2) are brought together. The best results are obtained when the reagent (3) is used after the reagents (1) and (2) have been brought together in their entirety.

Les méthodes de préparation des complexes catalytiques solides selon, l'invention s'étendent également à la mise en oeuvre, à la place des réactifs (1) et (2) préformés, de magnésium, d'un composé organique hydroxylé tel qu'un alcool et du réactif (2).The methods for preparing the solid catalytic complexes according to the invention also extend to the use, in place of the reactants (1) and (2) preformed, of magnesium, of a hydroxylated organic compound such as alcohol and reagent (2).

La préparation de pareils complexes catalytiques est décrite dans le brevet belge 819 609 du 6.9.1974 au nom de la Demanderesse dont le contenu est applicable en tout point au présent mode particulier de réalisation de l'invention.The preparation of such catalytic complexes is described in Belgian patent 819,609 of September 6, 1974 in the name of the Applicant, the content of which is applicable in all respects to this particular embodiment of the invention.

La pression sous laquelle on effectue la préparation des complexes catalytiques, la vitesse d'addition des réactifs et la durée de leur contact ne sont pas des facteurs critiques. Pour des raisons de commodité, on travaille généralement sous pression atmosphérique; la vitesse est choisie en général de manière à ne pas provoquer un échauffement brusque du milieu réactionnel dû à une auto-accélération éventuelle de la réaction; la durée peut varier généralement entre 5 minutes et 12 heures. On agite généralement le milieu réactionnel de manière à favoriser son homogénéisation pendant la durée de la réaction. La réaction peut être réalisée en continu ou en discontinu.The pressure under which the preparation of the catalytic complexes is carried out, the rate of addition of the reactants and the duration of their contact are not critical factors. For reasons of convenience, one generally works under atmospheric pressure; the speed is generally chosen so as not to cause a sudden heating of the reaction medium due to a possible self-acceleration of the reaction; the duration can generally vary between 5 minutes and 12 hours. The reaction medium is generally stirred so as to promote its homogenization during the duration of the reaction. The reaction can be carried out continuously or batchwise.

La température à laquelle on met en présence le réactif (1) et le réactif (2) n'est pas critique. Pour des raisons de commodité, elle est généralement choisie entre 200 et -50°C, de préférence entre 150°C et la température ambiante (25°C). Par contre, lorsqu'on procède à la préparation des complexes catalytiques en faisant réagir le réactif (3) avec le mélange résultant de la mise en présence du réactif (1) et réactif (2), on constate, de manière surprenante, que la température à laquelle cette réaction est réalisée exerce une influence sur la morphologie de la poudre de polyoléfine obtenue finalement. Toutes autres choses étant égales, il est possible de renforcer l'action favorable du chlorure organoaluminique conforme à l'invention sur la grosseur, la dureté et la granulométrie des particules de la polyoléfine et sur son poids spécifique apparent, en choisissant convenablement la température à laquelle ce réactif (3) est ajouté ou produit résultant du mélange préalable des réactifs (1) et (2). Cette température, qui est généralement supérieure à 0°C et inférieure à la température d'ébullition sous pression ordinaire du chlorure organoaluminique, est de préférence comprise entre 30 et 65°C. Les meilleurs résultats sont obtenus entre 45 et 60°C environ. La préparation des complexes catalytiques conformes à l'invention peut être avantageusement terminée par un traitement du mûrissage effectué à une température généralement équivalente ou supérieure à celle à laquelle a lieu la réaction avec le réactif (3) pendant une durée non critique allant de 5 minutes à 12 heures en général, de préférence pendant au moins 1 heure.The temperature at which the reagent (1) and the reagent (2) are brought into contact is not critical. For reasons of convenience, it is generally chosen between 200 and -50 ° C, preferably between 150 ° C and room temperature (25 ° C). On the other hand, when the catalytic complexes are prepared by reacting the reagent (3) with the mixture resulting from the bringing together of the reagent (1) and reagent (2), it is surprisingly found that the temperature at which this reaction is carried out has an influence on the morphology of the polyolefin powder finally obtained. All other things being equal, it is possible to reinforce the favorable action of the organoaluminum chloride according to the invention on the size, hardness and particle size of the particles of the polyolefin and on its apparent specific weight, by suitably choosing the temperature at which this reagent (3) is added or produced resulting from the prior mixing of the reagents (1) and (2). This temperature, which is generally above 0 ° C and below the boiling temperature under ordinary pressure of organoaluminum chloride, is preferably between 30 and 65 ° C. The best results are obtained between around 45 and 60 ° C. The preparation of the catalytic complexes in accordance with the invention can advantageously be completed by a treatment of the ripening carried out at a temperature generally equivalent to or higher than that at which the reaction with the reagent (3) takes place for a non-critical period ranging from 5 minutes. at 12 o'clock in general, preferably for at least 1 hour.

La quantité de composé (M), de composé (T) et de chlorure organoaluminique (A) à mettre en oeuvre de préférence sont précisées ci-après.The amount of compound (M), compound (T) and organoaluminum chloride (A) to be used preferably are specified below.

La quantité du ou des composés (T) à utiliser est définie par rapport à la quantité totale du ou des composés (M) utilisée. Elle peut varier dans une large mesure. En général, elle est comprise entre 0,01 et 10 at.-g (atome-gramme) de métal présent dans le composé (T) par at.-g de magnésium présent dans le composé (M). On a observé que les performances des complexes catalytiques de l'invention sont optimales lorsqu'on utilise un rapport compris entre 0,025 et 5 at.-g de titane par at.-g de magnésium. Le meilleur compromis entre la productivité (c'est-à-dire la quantité de polymère produite rapportée à la quantité de complexe catalytique utilisée), et l'activité spécifique (c'est-à-dire la quantité de polymère produite rapportée à la quantité de titane et/ou de zirconium mise en oeuvre) des complexes catalytiques, d'une part, et la morphologie de la polyoléfine obtenue, d'autre part, est obtenu lorsque ce rapport varie entre 0,10 et 2 at.-g par at.-g environ.The quantity of the compound (s) (T) to be used is defined relative to the total quantity of the compound (s) (M) used. It can vary to a large extent. In general, it is between 0.01 and 10 at.-g (gram atom) of metal present in the compound (T) per at.-g of magnesium present in the compound (M). It has been observed that the performance of the catalytic complexes of the invention is optimal when a ratio of between 0.025 and 5 at.-g of titanium per at-g of magnesium is used. The best compromise between productivity (that is to say the quantity of polymer produced compared to the quantity of catalytic complex used), and specific activity (that is to say the quantity of polymer produced compared to the amount of titanium and / or zirconium used) of the catalytic complexes, on the one hand, and the morphology of the polyolefin obtained, on the other hand, is obtained when this ratio varies between 0.10 and 2 at.-g by at.-g approx.

La quantité de chlorure organoaluminique à mettre en oeuvre est définie également par rapport à la quantité totale du ou des composés (M) utilisée. Elle peut également varier dans une large mesure. En général, elle est comprise entre 1 et 100 moles de chlorure organoaluminique par mole de composé (M). De préférence, cette quantité est comprise entre 1 et 20 moles par mole. Le meilleur compromis (tel que défini plus haut) est obtenu lorsque ce rapport est compris entre 2 et 10 moles par mole.The amount of organoaluminum chloride to be used is also defined relative to the total amount of the compound (s) used. It can also vary widely. In general, it is between 1 and 100 moles of organoaluminum chloride per mole of compound (M). Preferably, this amount is between 1 and 20 moles per mole. The best compromise (as defined above) is obtained when this ratio is between 2 and 10 moles per mole.

Les complexes catalytiques selon l'invention sont solides. Ils sont insolubles dans les alkanes et les cycloalkanes utilisables comme diluants. Ils peuvent être utilisés en polymérisation tels qu'ils sont obtenus, sans être séparés du milieu réactionnel de préparation. On peut toutefois les séparer de ce milieu réactionnel, notamment lorsqu'ils sont préparés en présence d'un solvant polaire, selon n'importe quel moyen connu. Lorsque le milieu réactionnel est liquide, on peut utiliser par exemple la filtration, la décantation ou la centrifugation.The catalytic complexes according to the invention are solid. They are insoluble in alkanes and cycloalkanes which can be used as diluents. They can be used in polymerization as they are obtained, without being separated from the reaction reaction medium. They can however be separated from this reaction medium, in particular when they are prepared in the presence of a polar solvent, by any known means. When the reaction medium is liquid, it is possible to use, for example, filtration, decantation or centrifugation.

Après séparation, les complexes catalytiques peuvent être lavés de manière à éliminer les réactifs en excès dont ils pourraient être encore imprégnés. Pour ce lavage, on peut utiliser n'importe quel diluant inerte et par exemple ceux qui sont utilisables comme constituants du milieu réactionnel tels que les alkanes et les cycloalkanes. Après lavage, les complexes catalytiques peuvent être séchés, par exemple, par balayage au moyen d'un courant d'azote sec ou sous vide.After separation, the catalytic complexes can be washed so as to remove the excess reactants with which they could still be impregnated. Any inert diluent can be used for this washing, for example those which can be used as constituents of the reaction medium, such as alkanes and cycloalkanes. After washing, the catalytic complexes can be dried, for example, by sweeping with a stream of dry nitrogen or under vacuum.

Le mécanisme de la réaction de formation des complexes catalytiques de l'invention n'est pas connu. L'analyse élémentaire des complexes catalytiques, après séparation et lavage, montre qu'il s'agit bien de complexes chimiquement liés, produits de réactions chimiques, et non pas du résultat de mélanges ou de phénomènes d'adsorption. En effet, il est impossible de dissocier l'un ou l'autre des constituants de ces complexes en utilisant des méthodes de séparation purement physiques.The mechanism of the reaction for the formation of the catalytic complexes of the invention is not known. Elementary analysis of the catalytic complexes, after separation and washing, shows that these are indeed chemically linked complexes, products of chemical reactions, and not the result of mixtures or adsorption phenomena. Indeed, it is impossible to dissociate one or the other of the constituents of these complexes using purely physical separation methods.

Les systèmes catalytiques conformes à l'invention comprennent également un composé organométallique qui sert d'activateur. On utilise les composés organométalliques des métaux des groupes la, Ila, llb, Illb et IVb du Tableau Périodique tels que les composés organométalliques du lithium, du magnésium, du zinc, de l'aluminium ou de l'etain. Les meilleurs résultats sont obtenus avec les composés organoaluminiques.The catalytic systems according to the invention also comprise an organometallic compound which serves as an activator. The organometallic compounds of the metals of groups la, Ila, llb, Illb and IVb of the Periodic Table are used such as the organometallic compounds of lithium, magnesium, zinc, aluminum or tin. The best results are obtained with organoaluminum compounds.

On peut utiliser des composés totalement alkylés dont les chaînes alkyles comprennent de 1 à 20 atomes de carbone et sont droites ou ramifiées tels que par exemple le n-butyllithium, le diéthylmagnésium, le diéthylzinc, le tétraéthylétain, le tétrabutylétain et les trialkylàluminiums.Fully alkylated compounds can be used, the alkyl chains of which contain from 1 to 20 carbon atoms and are straight or branched, such as, for example, n-butyllithium, diethylmagnesium, diethylzinc, tetraethyltin, tetrabutyltin and trialkylaluminums.

On peut également utiliser les hydrures d'alkylmétaux dans lesquels les radicaux alkyles comprennent également de 1 à 20 atomes de carbone tels que l'hydrure de diisobutylaluminium et l'hydrure de triméthylétain. Conviennent également les alkylhalogénures de métaux dans lesquels les radicaux alkyles comprennent aussi de 1 à 20 atomes de carbone tels que le sesquichlorure d'éthylaluminium, le chlorure de diéthylaluminium et le chlorure de diisobutylaluminium.It is also possible to use alkyl metal hydrides in which the alkyl radicals also comprise from 1 to 20 carbon atoms such as diisobutyl aluminum hydride and trimethyl tin hydride. Also suitable are metal alkyl halides in which the alkyl radicals also comprise from 1 to 20 carbon atoms such as ethyl aluminum sesquichloride, diethyl aluminum chloride and diisobutyl aluminum chloride.

On peut encore utiliser des composés organoaluminiques obtenus en faisant réagir des trialkylaluminiums ou des hydrures de dialkylaluminium dont les radicaux comprennent de 1 à 20 atomes de carbone avec des dioléfines comprenant de 4 à 20 atomes de carbone, et plus particulièrement les composés dénommés isoprénylaluminiums.It is also possible to use organoaluminum compounds obtained by reacting trialkylaluminiums or dialkylaluminium hydrides whose radicals contain from 1 to 20 carbon atoms with diolefins comprising from 4 to 20 carbon atoms, and more particularly the compounds called isoprenylaluminiums.

Pour la fabrication de certaines qualités de polyoléfines, on préfère utiliser les trialkylaluminiums dont les chaînes alkyles sont droites et comprennent de 1 à 18 atomes de carbone. On constate en effet, de manière tout à fait surprenante, que lorsque ces composés servent d'activateurs aux complexes catalytiques préparés conformément à l'invention, c'est-à-dire en faisant intervenir un réactif (3) qui est un chlorure organoaluminique tel que défini plus haut, les distributions des poids moléculaires des polyoléfines obtenus sont plus larges, toutes autres conditions égales, que celles des polyoléfines obtenues en présence de complexes catalytiques préparés en faisant usage des réactifs (3) habituels (dichlorure d'éthylaluminium).For the manufacture of certain qualities of polyolefins, it is preferred to use trialkylaluminiums whose alkyl chains are straight and contain from 1 to 18 carbon atoms. It is in fact found, quite surprisingly, that when these compounds serve as activators for the catalytic complexes prepared in accordance with the invention, that is to say by involving a reagent (3) which is an organoaluminum chloride as defined above, the molecular weight distributions of the polyolefins obtained are wider, all other conditions equal, than those of the polyolefins obtained in the presence of catalytic complexes prepared by making use of the usual reagents (3) (ethyl aluminum dichloride).

Ce résultat inattendu (distribution élargie des poids moléculaires) est particulièrement avantageux lorsque la polyoléfine est destinée à la fabrication d'objets de grande dimension tels que les fûts et grands récipients par des techniques d'extrusion-soufflage.This unexpected result (wider distribution of molecular weights) is particularly advantageous when the polyolefin is intended for the manufacture of large objects such as drums and large containers by extrusion-blowing techniques.

Le procédé de l'invention s'applique à la polymérisaiton des oléfines à insaturation terminale dont la molécule contient de 2 à 20 atomes, et de préférence de 2 à 6 atomes de carbone, telles que l'éthylène, le propylène, le butène-1, le 4-méthylpentène-1 et l'hexène-1. Il s'applique également à la copolymérisation de ces oléfines entre elles ainsi qu'avec des dioléfines comprenant de 4 à 20 atomes de carbone de préférence. Ces dioléfines peuvent être des dioléfines aliphatiques non conjugées telles que l'hexadiène-1,4, des dioléfines monocycliques telles que le 4-vinylcyclohexène, le 1,3-divinylcyclo- hexane, le cyclopentadiène ou le cyclooctadiène-1,5, des dioléfines alicycliques ayant un pont endocyclique telles que le dicyclopentadiène ou le norbornadiène et les dioléfines aliphatiques conjugées telles que le butadiène et l'isoprène.The process of the invention applies to the polymerization of olefins with terminal unsaturation, the molecule of which contains from 2 to 20 atoms, and preferably from 2 to 6 carbon atoms, such as ethylene, propylene, butene. 1, 4-methylpentene-1 and hexene-1. It also applies to the copolymerization of these olefins together as well as with diolefins comprising preferably from 4 to 20 carbon atoms. These diolefins can be unconjugated aliphatic diolefins such as 1,4-hexadiene, monocyclic diolefins such as 4-vinylcyclohexene, 1,3-divinylcyclohexane, cyclopentadiene or 1,5-cyclooctadiene, diolefins alicyclics having an endocyclic bridge such as dicyclopentadiene or norbornadiene and conjugated aliphatic diolefins such as butadiene and isoprene.

Le procédé de l'invention s'applique particulièrement bien à la fabrication d'homopolymères de l'éthylène et de copolymères contenant au moins 90% molaires et de préférence 95% molaires d'éthylène.The process of the invention is particularly applicable to the manufacture of homopolymers of ethylene and of copolymers containing at least 90 mol% and preferably 95 mol% of ethylene.

La polymérisation peut être effectuée selon n'importe quel procédé conu: en solution ou en suspension dans un solvant ou un diluant hydrocarboné ou encore en phase gazeuse. Pour les procédés en solution ou en suspension, on utilise des solvants ou diluants analogues à ceux employés pour la. préparation du complexe catalytique: ce sont de préférence des alkanes ou des cycloalkanes tels que l'isobutane, le pentane, l'hexane, l'heptane, le cyclohexane, le méthylcyclohexane ou leurs mélanges. On peut également opérer la polymérisation dans le monomère ou un des monomères maintenu à l'état liquide. Il est particulièrement avantageux de mettre en oeuvre des procédés de polymérisation dans lesquels les polymères sont générés directement sous forme de particules. Parmi ces procédés, on préfère les procédés de polymérisation en suspension dans un diluant hydrocarboné liquide dans les conditions de polymérisation qui, après séparation du monomère qui n'a pas réagi et du diluant, fournissent, en présence de systèmes catalytiques de l'invention des particules de polymère qui ont les caractéristiques morphologiques des poudres utilisées dans les procédés de transformation mentionnés plus haut.The polymerization can be carried out according to any process designed: in solution or in suspension in a hydrocarbon solvent or diluent or even in the gas phase. For the processes in solution or in suspension, solvents or diluents similar to those used for the preparation are used. preparation of the catalytic complex: these are preferably alkanes or cycloalkanes such as isobutane, pentane, hexane, heptane, cyclohexane, methylcyclohexane or their mixtures. It is also possible to carry out the polymerization in the monomer or one of the monomers maintained in the liquid state. It is particularly advantageous to carry out polymerization processes in which the polymers are generated directly in the form of particles. Among these methods, the polymerization processes in suspension in a liquid hydrocarbon diluent under the polymerization conditions are preferred, which, after separation of the unreacted monomer and the diluent, provide, in the presence of catalytic systems of the invention, polymer particles which have the morphological characteristics of the powders used in the transformation processes mentioned above.

La pression de polymérisation est comprise en général entre la pression atmosphérique et 100 kg/cm2, de préférence 50 kg/cm2. La température est choisie généralement entre 20 et 200°C. Elle est de préférence entre 60 et 120°C de manière à obtenir directement le polymère sous forme solide. On n'observe aucune dégradation de la morphologie des particules de polyoléfine obtenues en présence des systèmes catalytiques de l'invention lorsqu'on abaisse la température de polymérisation dans cette zone préférée. Au contraire, lorsque des complexes catalytiques solides sont préparés à partir des réactifs (3) habituels de l'art antérieur, on constate que l'abaissement de la température de polymérisation exerce un effet néfaste sur la morphologie de la polyoléfine obtenu (les particules sont plus fines et moins dures).The polymerization pressure is generally between atmospheric pressure and 100 kg / cm 2 , preferably 50 kg / cm 2 . The temperature is generally chosen between 20 and 200 ° C. It is preferably between 60 and 120 ° C so as to directly obtain the polymer in solid form. No degradation in the morphology of the polyolefin particles obtained in the presence of the catalytic systems of the invention is observed when the polymerization temperature is lowered in this preferred zone. On the contrary, when solid catalytic complexes are prepared from the usual reagents (3) of the prior art, it is found that the lowering of the polymerization temperature exerts a detrimental effect on the morphology of the polyolefin obtained (the particles are thinner and less harsh).

La polymérisation peut être effectuée en continu ou en discontinu.The polymerization can be carried out continuously or batchwise.

Le composé organométallique et le complexe catalytique peuvent être ajoutés séparément au milieu de polymérisation. On peut également les mettre en contact, à une température comprise entre -40 et 80°C, pendant une durée pouvant aller jusqu'à 2 heures, avant de les introduire dans le réacteur de polymérisation. On peut aussi les mettre en contact en plusieurs étapes ou encore ajouter une partie du composé organométallique avant le réacteur ou encore ajouter plusieurs composés organométalliques différents.The organometallic compound and the catalytic complex can be added separately to the polymerization medium. They can also be brought into contact, at a temperature between -40 and 80 ° C, for a period of up to 2 hours, before introducing them into the polymerization reactor. We can also put them in contact in several stages or add a part organometallic compound before the reactor or add several different organometallic compounds.

La quantité totale de composé organométallique mise en oeuvre peut varier dans une large mesure. Elle est comprise en général entre 0,02 et 50 mmoles par dm3 de solvent, de diluant ou de volume de réacteur et de préférence entre 0,5 et 2,5 mmoles par dm3.The total amount of organometallic compound used can vary to a large extent. It is generally between 0.02 and 50 mmol per dm 3 of solvent, diluent or reactor volume and preferably between 0.5 and 2.5 mmol per dm 3 .

La quantité de complexe catalytique mise en oeuvre est déterminée en fonction de la teneur en titane du complexe catalytique. Elle est choisie-en général de manière que la concentration soit comprise entre 0,001 et 2,5 et de préférence entre 0,01 et 0,25 mat.-g de titane ou de zirconium par dm3 de solvant, de diluant ou de volume de réacteur (mat.-g = milliatome-gramme).The amount of catalytic complex used is determined as a function of the titanium content of the catalytic complex. It is generally chosen so that the concentration is between 0.001 and 2.5 and preferably between 0.01 and 0.25 mat.-g of titanium or zirconium per dm 3 of solvent, diluent or volume of reactor (mat.-g = milliatome-gram).

Le rapport des quantités de composé organométallique et de complexe catalytique n'est pas critique non plus. On le choisit en général de manière que le rapport composé organométallique/titane exprimé en mole/at.-g soit supérieur à 1 et de préférence supérieur à 10.The ratio of the amounts of organometallic compound and catalytic complex is also not critical. It is generally chosen so that the organometallic compound / titanium ratio expressed in mole / at.-g is greater than 1 and preferably greater than 10.

Le poids moléculaire moyen, et partant l'indice de fluidité (melt index) des polymères fabriqués selon le procédé de l'invention peut être réglé par l'addition au milieu de polymérisation d'un ou de plusieurs agents de modification du poids moléculaire comme l'hydrogène, le zinc ou le cadmium diéthyle, les alcools ou l'anhydride carbonique.The average molecular weight, and hence the melt index of the polymers produced according to the process of the invention can be adjusted by the addition to the polymerization medium of one or more molecular weight modifiers such as hydrogen, zinc or cadmium diethyl, alcohols or carbon dioxide.

Le poids spécifique des homopolymères fabriqués suivant le procédé de l'invention peut etre egalement réglé par l'addition au milieu de polymérisation d'un alkoxyde d'un métal des groupes IVa et Va du Tableau Périodique. C'est ainsi qu'on peut fabriquer des polyéthylènes de poids spécifique intermediaire entre celui des polyéthylènes à haute densité classiques et celui des polyéthylènes prépares selon un procédé à haute pression.The specific gravity of the homopolymers produced according to the process of the invention can also be adjusted by the addition to the polymerization medium of an alkoxide of a metal from groups IVa and Va of the Periodic Table. Thus it is possible to manufacture polyethylenes of specific weight intermediate between that of conventional high density polyethylenes and that of polyethylenes prepared according to a high pressure process.

Parmi les alkoxydes convenant pour ce réglage, ceux du titane et du vanadium dont les radicaux contiennent de 1 à 20 atomes de carbone chacun sont particulièrement efficaces. On peut citer parmi eux Ti(OCH3)4, Ti(OC2H5)4, Ti[OCH2CH(CH3)2]4, Ti(OC8H17)4 et TI(OC16H33)4 . Among the alkoxides suitable for this adjustment, those of titanium and vanadium whose radicals contain from 1 to 20 carbon atoms each are particularly effective. These include Ti (OCH 3 ) 4 , Ti (OC 2 H 5 ) 4 , Ti [OCH 2 CH (CH 3 ) 2 ] 4 , Ti (OC 8 H 17 ) 4 and TI (OC 16 H 33 ) 4 .

Le procédé de l'invention permet de fabriquer des polyoléfines avec des productivités très élevées. Ainsi, dans l'homopolymérisation de l'éthylène, la productivité exprimée en grammes de polyéthylène par gramme de complexe catalytique mis en oeuvre dépasse régulièrement 10 000 et dans certains cas 20000. L'activité rapportée à la quantité de métaux de transition présente dans le complexe catalytique est également très élevée. Dans l'homopolymérisation de l'éthylène, également exprimée en grammes de polyéthylène par at.-g de titane mis en oeuvre, elle dépasse régulièrement 200 000. Dans les cas les plus favorables, elle est supérieure à 500 000. Elle est dans tous les cas au moins au niveau des activités conférées aux systèmes catalytiques préférés de l'art antérieur, comprenant les complexes catalytiques solides préparés à partir de dichlorure d'éthylaluminium comme réactif (3), et elle est même souvent supérieure à ces activités.The process of the invention makes it possible to manufacture polyolefins with very high productivities. Thus, in the homopolymerization of ethylene, the productivity expressed in grams of polyethylene per gram of catalytic complex used regularly exceeds 10,000 and in some cases 20,000. The activity related to the amount of transition metals present in the catalytic complex is also very high. In the homopolymerization of ethylene, also expressed in grams of polyethylene per at.-g of titanium used, it regularly exceeds 200,000. In the most favorable cases, it is greater than 500,000. It is in all cases the cases at least at the level of the activities conferred on the preferred catalytic systems of the prior art, comprising the solid catalytic complexes prepared from ethylaluminum dichloride as reagent (3), and it is even often superior to these activities.

De ce fait, la teneur en résidus catalytiques des polymères fabriqués selon le procédé de l'invention est extrêmement basse. Plus particulièrement, la teneur en métal de transition résiduel est excessivement faible. Or ce sont les dérivés des métaux de transition qui sont surtout gênants dans les résidus catalytiques en raison des complexes colorés qu'ils forment avec les antioxydants phénoliques habituellement utilisés dans les polyoléfines et du caractère toxique desdits métaux.As a result, the content of catalytic residues in the polymers produced according to the process of the invention is extremely low. More particularly, the content of residual transition metal is excessively low. However, these are the derivatives of the transition metals which are especially troublesome in the catalytic residues because of the colored complexes which they form with the phenolic antioxidants usually used in polyolefins and the toxic nature of said metals.

Dans le procédé de l'invention, la teneur des polymères en résidus gênants est tellement faible que l'on peut faire l'économie du traitement d'épuration (par exemple un traitement à l'alcool), qui est obligatoire lorsque la teneur en résidus catalytiques est élevée et qui est une opération coûteuse en matières premières et en énergie et nécessitant des immobilisations considérables.In the process of the invention, the content of the troublesome polymers in residues is so low that it is possible to economize on the purification treatment (for example an alcohol treatment), which is compulsory when the content of catalytic residue is high and is a costly operation in terms of raw materials and energy and requires considerable downtime.

Les poudres de polyoléfine fabriquées conformément à l'invention se caractérisent donc par une morphologie remarquable et peuvent être mises en oeuvre sous cette forme. C'est le cas en particulier des poudres des polymères d'ethylène. Les polyoléfines obtenus selon l'invention peuvent cependant être granulées et être mises en oeuvre sous forme de granules selon les techniques de moulage conventionnelles: par injection, par extrusion, par extrusion-soufflage, par calandrage, etc.The polyolefin powders produced in accordance with the invention are therefore characterized by a remarkable morphology and can be used in this form. This is particularly the case for powders of ethylene polymers. The polyolefins obtained according to the invention can however be granulated and be used in the form of granules according to conventional molding techniques: by injection, by extrusion, by extrusion blow molding, by calendering, etc.

Les exemples qui suivent sont destinés à illustrer l'invention et n'en limitent pas la portée.The examples which follow are intended to illustrate the invention and do not limit its scope.

Exemples 1 à 4 et exemple comparatif 5RExamples 1 to 4 and comparative example 5R

On utilise les réactifs suivants:

  • (1) de l'éthylate de magnésium Mg(OCZHS)2 vendu par Dynamit Nobel
  • (2) du tétrabutylate de titane Ti(OnC4H9)4 vendu par Dynamit Nobel
  • (3) différents chlorures organoaluminiques définis ci-après.
The following reagents are used:
  • (1) magnesium ethylate Mg (OCZHS) 2 sold by Dynamit Nobel
  • (2) titanium tetrabutylate Ti (OnC 4 H 9 ) 4 sold by Dynamit Nobel
  • (3) various organoaluminum chlorides defined below.

On prépare une solution-mère (S) en chauffant ensemble, à 150°C, sous agitation et pendant 2 heures, 9 moles du réactif (2) et 4,5 moles du réactif (1). ). Dans ce mélange, le rapport atomique Ti/Mg vaut donc environ 2 at.-g/at.-g.500 ml de la solution-mère (S), dans laquelle il y a eu dissolution quasi- complète du réactif (1 ) et qui a été préalablement refroidie, sont additionnés de 1000 ml d'hexane, de manière à obtenir une solution à environ 500 g/lit.A stock solution (S) is prepared by heating together, at 150 ° C, with stirring and for 2 hours, 9 moles of the reagent (2) and 4.5 moles of the reagent (1). ). In this mixture, the Ti / Mg atomic ratio is therefore approximately 2 at.-g / at.-g. 500 ml of the stock solution (S), in which there has been almost complete dissolution of the reagent (1) and which has been previously cooled, are added 1000 ml of hexane, so as to obtain a solution at about 500 g / bed.

Les différents chlorures organoaluminiques mis en oeuvre sont:

  • -dans l'exemple 1, du dichlorure d'isobutylaluminium Al(iC4H9)Cl2;
  • -dans l'exemple 2, du dichlorure de n-butylaluminium Al(nC4H9)Cl2;
  • -dans l'exemple 3, du dichlorure de n-octylaluminium Al(nC8H17)Cl2;
  • -dans l'exemple 4, du dichlorure de n-octadécylaluminium Al(nC18H37)Cl2;
  • -dans l'exemple comparatif 5R, du dichlorure d'éthylaluminium Al(C2H5)Cl2.
The different organoaluminum chlorides used are:
  • in Example 1, isobutylaluminum dichloride Al (iC 4 H 9 ) Cl 2 ;
  • in Example 2, n-butylaluminum dichloride Al (nC 4 H 9 ) Cl 2 ;
  • in Example 3, n-octylaluminum dichloride Al (nC 8 H 17 ) Cl 2 ;
  • in Example 4, n-octadecylaluminum dichloride Al (nC 18 H 37 ) Cl 2 ;
  • in comparative example 5R, ethyl aluminum dichloride Al (C 2 H 5 ) Cl 2 .

Les chlorures organoaluminiques mis en oeuvre selon les exemples 2, 3, 4 ont été préparés, de commerciaux vendus par Schering.The organoaluminum chlorides used according to Examples 2, 3, 4 were prepared, from sales sold by Schering.

Les chlorures organoaluminiques mis en oeuvre selon les exemples 2, 3, 4 ont é53 préparés, de manière connue, par réaction du trialkylaluminium correspondant avec du trichlorure d'aluminium.The organoaluminum chlorides used according to Examples 2, 3, 4 were also prepared in known manner by reaction of the corresponding trialkylaluminum with aluminum trichloride.

Ces chlorures organoaluminiques sont mis en oeuvre sous forme de solutions dans l'hexane à 400 g/lit. Ils sont ajoutés progressivement à des fractions de solutions-mères (S), diluées comme indiqué plus haut, à une température d'environ 50°C et sous agitation, pendant environ 90 minutes. A la fin de cette addition, le mélange réactionnel est soumis à un murissage pendant 1 heure à 60°C. La quantité de chlorure organoaluminique mise en oeuvre dans chacun des exemples est telle que le rapport molaire chlorure organoaluminique/éthylate de magnésium vaut environ 10.These organoaluminum chlorides are used in the form of solutions in hexane at 400 g / bed. They are added gradually to fractions of stock solutions (S), diluted as indicated above, at a temperature of approximately 50 ° C and with stirring, for approximately 90 minutes. At the end of this addition, the reaction mixture is subjected to curing for 1 hour at 60 ° C. The amount of organoaluminum chloride used in each of the examples is such that the molar ratio of organoaluminum chloride / magnesium ethylate is approximately 10.

Les complexes catalytiques ainsi formés sont utilisés tels quels, sans être séparés de leur milieu réactionnel, dans des essais de polymérisation dont les conditions générales sont définies ci-dessous.The catalytic complexes thus formed are used as such, without being separated from their reaction medium, in polymerization tests the general conditions of which are defined below.

On introduit des quantités déterminées de complexe catalytique et 0,5 mmole de triéthylaluminium dans un autoclave de 1,5 1 contenant 0,5 1 d'hexane. La température de l'autoclave est portée ensuite à 85°C environ. On introduit de l'éthylène sous une pression partielle de 10 kg/cm2 et de l'hydrogène sous une pression partielle de 4 kg/cm2.Determined quantities of catalytic complex and 0.5 mmol of triethylaluminum are introduced into a 1.5 l autoclave containing 0.5 l of hexane. The temperature of the autoclave is then brought to approximately 85 ° C. Ethylene is introduced under a partial pressure of 10 kg / cm 2 and hydrogen under a partial pressure of 4 kg / cm 2 .

On poursuit la polymérisation pendant 1 h sous agitation en maintenant la pression totale constante par addition continue d'éthylène. Après 1 h, on dégaze l'autoclave et on recueille le polyéthylène ainsi fabriqué.The polymerization is continued for 1 h with stirring while keeping the total pressure constant by continuous addition of ethylene. After 1 h, the autoclave is degassed and the polyethylene thus produced is collected.

Le Tableau 1 mentionne les conditions particulières à chaque essai, les résultats obtenus et les caractéristiques morphologiques des polyéthylènes fabriqués.Table 1 lists the conditions specific to each test, the results obtained and the morphological characteristics of the polyethylenes produced.

Dans ce Tableau, et dans les exemples qui suivent:

  • -PSA signifie "poids spécifique apparent" du polymère et est exprimé en kg/dm3;
  • -D signifie "dureté" du polymère et est exprimée en pour cent. Cette dureté est appréciée en mesurant le PSA du polymère, de manière connue, par écoulement, avant et après un broyage d'une durée de 6 secondes dans un broyeur à lamelles tournant à plus de 20 000 trs1min. La dureté est donnée par la formule empirique
    Figure imgb0001
In this Table, and in the following examples:
  • -PSA means "apparent specific weight" of the polymer and is expressed in kg / dm 3 ;
  • -D means "hardness" of the polymer and is expressed in percent. This hardness is assessed by measuring the PSA of the polymer, in a known manner, by flow, before and after grinding for a duration of 6 seconds in a lamellar mill rotating at more than 20,000 rpm. Hardness is given by the empirical formula
    Figure imgb0001

Plus la valeur obtenue est élevée, plus les particules de polymère sont dures;

  • -la distribution granulométrique G du polymère est aussi exprimée en pour cent et est mesurée après broyage dans les conditions définies ci-dessus.
  • -MI représente l'indice de fluidité du polyéthylène, exprimé en g/10 min. et mesuré selon la norme ASTM-D 1238-70.
  • -la quantité de suspension en complexe catalytique mise en oeuvre est exprimée indirectement par le poids, en mg, de titane qu'elle contient.
  • -HLMI représente l'indice de fluidité du polyéthylène sous forte charge, exprimé en g/10 min, mesuré selon la norme ASTM-D 1238-70.
  • -le rapport HLMI/MI est représentatif de l'étalement de la distribution des poids moléculaires. Il est d'autant plus élevé que la distribution est large.
    Figure imgb0002
The higher the value obtained, the harder the polymer particles;
  • the particle size distribution G of the polymer is also expressed in percent and is measured after grinding under the conditions defined above.
  • -MI represents the melt index of the polyethylene, expressed in g / 10 min. and measured according to ASTM-D 1238-70.
  • the quantity of suspension in catalytic complex used is expressed indirectly by the weight, in mg, of titanium which it contains.
  • -HLMI represents the melt index of polyethylene under high load, expressed in g / 10 min, measured according to standard ASTM-D 1238-70.
  • the HLMI / MI ratio is representative of the spread of the molecular weight distribution. The higher the distribution, the higher the distribution.
    Figure imgb0002

Le Tableau 1 montre que l'utilisation des chlorures organoaluminiques répondant à la définition de l'invention comme réactifs (3), (exemples 1 à 4) conduit, avec des activités catalytiques amélioréçs, à des polyéthylènes qui contiennent une proportion de grosses particules nettement supérieure à celle présente dans les polyéthylènes obtenus avec le réactif (3) habituel de l'art antérieur (exemple 5 R).Table 1 shows that the use of organoaluminum chlorides meeting the definition of the invention as reagents (3) (examples 1 to 4) leads, with improved catalytic activities, to polyethylenes which contain a proportion of large particles clearly greater than that present in the polyethylenes obtained with the usual reagent (3) of the prior art (example 5 R).

Examples 6 et 7 RExamples 6 and 7 R

L'exemple 7 R est donné à titre comparitif.Example 7 R is given for comparison.

Des complexes catalytiques sont préparés conformément aux exemples précédents sauf que les réactifs (2) et (1) sont mélangés de manière que le rapport atomique Ti/Mg soit d'environ 1.2 at-g/at.-g, que la quantité de chlorure organoaluminique mise en oeuvre est telle que le rapport molaire chlorure organoaluminique/éthylate de magnésium vaut environ 3,5 et que le chlorure organoaluminique est ajouté à une température d'environ 30°C.Catalytic complexes are prepared according to the preceding examples except that the reactants (2) and (1) are mixed so that the atomic ratio Ti / Mg is approximately 1.2 at-g / at.-g, that the amount of chloride organoaluminic implementation is such that the molar ratio organoaluminic chloride / magnesium ethylate is approximately 3.5 and that the organoaluminum chloride is added at a temperature of approximately 30 ° C.

Dans l'exemple 6, le complexe catalytique est préparé en faisant usage de dichlorure d'isobutylaluminium comme chlorure organoaluminique.In Example 6, the catalytic complex is prepared by using isobutylaluminum dichloride as the organoaluminum chloride.

Dans l'exemple 7 R, le complexe catalytique est préparé en faisant usage de dichlorure d'éthylaluminium comme chlorure organanoaluminigue.In Example 7 R, the catalytic complex is prepared using ethylaluminum dichloride as the organoaluminous chloride.

Les complexes catalytiques obtenus sont utilisés sous forme de suspension dans le milieu qui a servi à les préparer pour effectuer des essais de polymérisation de l'éthylène dans des conditions générales absolument identiques à celles décrites dans les exemples précédents.The catalytic complexes obtained are used in the form of a suspension in the medium which served to prepare them for carrying out ethylene polymerization tests under general conditions absolutely identical to those described in the previous examples.

Les caractéristiques morphologiques des polyéthylènes obtenus sont rassamblés dans le Tableau II.

Figure imgb0003
The morphological characteristics of the polyethylenes obtained are collated in Table II.
Figure imgb0003

On constate donc que les résultats avantageux de l'utilisation de chlorure organoaluminiques (réactifs (3)) répondant à la définition de l'invention restent acquis malgré des modifications importantes des rapports molaires entre réactifs.It is therefore found that the advantageous results of the use of organoaluminum chloride (reagents (3)) meeting the definition of the invention remain acquired despite significant changes in the molar ratios between reagents.

Exemples 8 à 12Examples 8 to 12

Des complexes catalytiques sont préparés conformément aux exemples 1 à 5 R-en faisant usage de dichlorure d'isobutylaluminium comme chlorure organoaluminique.Catalytic complexes are prepared in accordance with Examples 1 to 5 R using them isobutylaluminum dichloride as organoaluminum chloride.

Toutefois, la solution dans l'hexane de ce réactif est ajoutée à la solution-mère (S) à des températures variables.However, the hexane solution of this reagent is added to the stock solution (S) at varying temperatures.

Des essais de polymérisation de léthylène sont effectués avec les complexes catalytiques ainsi préparés dans les conditions générales décrites aux exemples 1 à 5 R.Polymerization tests of ethylene are carried out with the catalytic complexes thus prepared under the general conditions described in Examples 1 to 5 R.

Les conditions particulières à chaque essai, les résultats obtenus et les caractéristiques morphologiques des polyéthylènes fabriqués sont rassamblés dans le Tableau III.

Figure imgb0004
The conditions specific to each test, the results obtained and the morphological characteristics of the polyethylenes produced are collated in Table III.
Figure imgb0004

On constate donc, que dans le cas particulier de l'utilisation de dichlorure d'isobutylaluminium comme réactif (3), les résultats relatifs à la morphologie du polymère et les performances catalytiques sont supérieures lorsque la température à laquelle ce composé est mis en oeuvre est supérieure à 30°C. En outre, l'augmentation de la température à laquelle ce composé est ajouté n'entraîne pas de diminution du PSA ni d'élargissement de la distribution granulométrique.It can therefore be seen that, in the particular case of the use of isobutylaluminum dichloride as reagent (3), the results relating to the morphology of the polymer and the catalytic performances are higher when the temperature at which this compound is used is higher than 30 ° C. In addition, increasing the temperature at which this compound is added does not decrease the PSA or widen the particle size distribution.

Exemptes 13 à 15 et exemples comparatifs 16 R à 18 RFree 13 to 15 and comparative examples 16 R to 18 R

Des complexes catalytiques sont préparés conformément aux exemples 1 à 5 R en faisant usage de dichlorure d'isobutylaluminium mis en oeuvre à 50°C, comme composé organoaluminique dans les exemples 13 à 15, et de dichlorure d'éthylaluminium, mis en oeuvre à 30°C, dans les exemples 16 R à 18 R.Catalytic complexes are prepared in accordance with Examples 1 to 5 R using isobutylaluminum dichloride used at 50 ° C, as the organoaluminum compound in Examples 13 to 15, and ethylaluminum dichloride, used at 30 ° C, in examples 16 R to 18 R.

Des essais de polymérisation de l'éthylène sont effectués avec les complexes catalytiques ainsi préparés dans les conditions générales décrites aux exemples 1 à 5 R mais en faisant usage des composés organoaluminiques suivants comme activateurs des systèmes catalytiques:

  • -du triéthylaluminium Al(C2H5)3 dans les exemples 13 et 16 R;
  • -du trioctylaluminium Al(C8H17)3 dans les exemples 14 et 17 R;
  • -du trioctadecylaluminium Al(C18H37)3 dans les exemples 15 et 18 R.
Tests for the polymerization of ethylene are carried out with the catalytic complexes thus prepared under the general conditions described in Examples 1 to 5 R but using the following organoaluminum compounds as activators of the catalytic systems:
  • - triethylaluminium Al (C 2 H 5 ) 3 in Examples 13 and 16 R;
  • - trioctylaluminium Al (C 8 H 17 ) 3 in Examples 14 and 17 R;
  • - trioctadecylaluminium Al (C 18 H 37 ) 3 in Examples 15 and 18 R.

Les conditions particulières à chaque essai, les résultats obtenus et les caractéristiques des polyéthylènes fabriqués sont rassemblés au Tableau IV.

Figure imgb0005
Figure imgb0006
 The conditions specific to each test, the results obtained and the characteristics of the polyethylenes produced are collated in Table IV.
Figure imgb0005
Figure imgb0006

L'examen de ce Tableau permet de conclure que lorsqu'on fait usage de chlorures organoaluininiques (réactifs (3)) conformes à l'invention, on obtient dans des conditions de polymérisation strictement indentiques, des polyéthylènes, qui, outre leur morphologie plus avantageuse, présentent des distributions des poids moléculaires plus larges que lorsque les complexes catalytiques sont préparés avec le réactif (3) préféré de l'art antérieur.Examination of this table can be concluded that when use is made of gold chlorides g anoaluinini q ues (reagents (3)) according to the invention are obtained under strictly indentic polymerization conditions, polyethylenes, which, in addition their more advantageous morphology has wider molecular weight distributions than when the catalytic complexes are prepared with the preferred reagent (3) of the prior art.

Claims (10)

1. Process for the polymerisation of alpha-olefines, which process is carried out in the process of an organometallic compound of a metal from groups la, Ila, lib, lllb and lVb of the Periodic Table and a solid catalytic complex prepared by reacting the following with one another:
(1) at least one compound (M) chosen from amongst organic oxygen-containing compounds and halogen-containing magnesium compounds;
(2) at least one compound (T) chosen from amongst organic oxygen-containing compounds and halogen-containing titanium compounds; and
(3) at least one aluminium halide (A),

characterised in that the latter is chosen from amongst organo-aluminium chlorides of the general formula AIRnCl3-n, in which R is a linear or branched alkyl radical containing from 4 to 18 carbon atoms and n is a number such that 1 < n < 1.5.
2. Process according to Claim 1, characterised in that R is an alkyl radical containing from 4 to 8 carbon atoms and n has the value 1.
3. Process according to Claim 2, characterised in that the organo-aluminium chloride is isobutylaluminium dichloride.
4. Process according to any one of Claims 1 to 3, characterised in that the compound (M) is chosen from amongst magnesium dialkoxides and the compound (T) is chosen from amongst titanium compounds only containing sequences of metal/oxygen/organic radical linkages.
5. Process according to any one of Claims 1 to 4, characterised in that the solid catalytic complex is prepared by reacting with one another, in addition to the compound (M), the compound (T) and the aluminium halide (A), a compound (Z) chosen from amongst organic oxygen-containing compounds and halogen-containing zirconium compounds.
6. Process according to any one of Claims 1 to 5, characterised in that the solid catalytic complex is prepared by introducing the aluminium halide (A) at the end of the preparation.
7. Process according to any one of Claims 1 to 6, characterised in that the temperature of the reaction medium while the organo-aluminium chloride introduced is between 30 and 65°C.
8. Process according to any one of Claims 1 to 7, characterised in that the amounts of compounds (T), (M) and (A) used to prepare the catalytic complex are such that the ratio of the amount of titanium to the amount of magnesium is between 0.025 and 5 g.atams/g.atom and the ratio of the amount of compound (A) to the amount of compound (M) is between 1 and 20 mols/mol.
9. Process according to any one of Claims 1 to 8, characterised in that the polymerisation process is a process for polymerisation in suspension in a hydrocarbon diluent which is liquid under the polymerisation conditions.
10. Process for the preparation of solid catalytic complexes, in which process the following are reacted with one another:
(1) at least one compound (M) chosen from amongst organic oxygen-containing compounds and halogen-containing magnesium compounds;
(2) at least one compound (T) chosen from amongst organic oxygen-containing compounds and halogen-containing titanium compounds; and
(3) at least one aluminium halide (A),

characterised in that the latter is chosen from amongst organo-aluminium chlorides of the general formula AIRnCl3-n, in which R is a linear or branched alkyl radical containing from 4 to 18 carbon atoms and n is a number such that 1 < n < 1.5.
EP78200026A 1977-06-06 1978-06-01 Process for the polymerisation of alpha-olefins and method for preparing solid catalytic complexes for use in this polymerisation process Expired EP0000007B2 (en)

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FR2529211A1 (en) * 1982-06-24 1983-12-30 Bp Chimie Sa Alpha olefin! polymerisation using titanium cpd. catalyst - on magnesium chloride support and organo-aluminium co-catalyst, for fluidised bed polymerisation
US4426316A (en) 1982-09-10 1984-01-17 The Dow Chemical Company Catalyst prepared from organomagnesium compound, organic hydroxyl-containing compound, reducing halide source and transition metal compound
EP0099774A1 (en) * 1982-06-24 1984-02-01 BP Chimie Société Anonyme Process for the polymerization and copolymerization of alpha-olefins in a fluidized bed
EP0099772A1 (en) * 1982-06-24 1984-02-01 BP Chimie Société Anonyme Catalysts for the polymerization and copolymerization of ethylene, and polymerization processes using such catalysts
EP0101978A1 (en) * 1982-08-05 1984-03-07 Phillips Petroleum Company Olefin polymerization
US4456547A (en) * 1982-10-21 1984-06-26 Fuentes Jr Ricardo Catalyst prepared from organomagnesium compound, organic hydroxyl-containing compound, reducing halide source and complex formed from admixture of a transition metal compound and an organozinc compound
US4526943A (en) * 1982-07-29 1985-07-02 The Dow Chemical Company Process for polymerizing olefins in the presence of a catalyst prepared from organomagnesium compound, organic hydroxyl-containing compound, reducing halide source and transition metal compound
US4529715A (en) * 1983-10-17 1985-07-16 The Dow Chemical Company Catalyst prepared from organomagnesium compound, carbon dioxide, reducing aluminum source, transition metal compound and zinc compound
US4544647A (en) * 1982-07-29 1985-10-01 The Dow Chemical Company Catalyst prepared from organomagnesium compound, organic hydroxyl-containing compound, reducing halide source and transition metal compound
US4569975A (en) * 1984-03-19 1986-02-11 The Dow Chemical Company Polymerization of olefins in presence of a catalyst prepared from organomagnesium compound, carbon dioxide compound, reducing halide source and transition metal compound
US4604374A (en) * 1982-09-20 1986-08-05 The Dow Chemical Company Catalyst prepared from organomagnesium compound, epihalohydrin reducing halide source and transition metal compound
US4605715A (en) * 1982-09-20 1986-08-12 The Dow Chemical Company Process for polymerizing olefins in the presence of a catalyst prepared from organomagnesium compound, epihalohydrin reducing halide source and transition metal compound
US4661465A (en) * 1985-10-31 1987-04-28 The Dow Chemical Company Method for preparing transition metal component of Ziegler-Natta catalysts
US4783512A (en) * 1985-05-20 1988-11-08 The Dow Chemical Company Process for polymerizing olefins in the presence of a catalyst prepared from organomagnesium compound, organic hydroxyl-containing compound, reducing halide source and transition metal compound
US5045612A (en) * 1990-04-18 1991-09-03 The Dow Chemical Company Catalyst and process for polymerizing olefins
US5114897A (en) * 1990-04-18 1992-05-19 The Dow Chemical Company Catalyst and process for polymerizing olefins

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FR2529211A1 (en) * 1982-06-24 1983-12-30 Bp Chimie Sa Alpha olefin! polymerisation using titanium cpd. catalyst - on magnesium chloride support and organo-aluminium co-catalyst, for fluidised bed polymerisation
EP0099774A1 (en) * 1982-06-24 1984-02-01 BP Chimie Société Anonyme Process for the polymerization and copolymerization of alpha-olefins in a fluidized bed
EP0099772A1 (en) * 1982-06-24 1984-02-01 BP Chimie Société Anonyme Catalysts for the polymerization and copolymerization of ethylene, and polymerization processes using such catalysts
FR2529208A1 (en) * 1982-06-24 1983-12-30 Bp Chimie Sa Ethylene (co)polymerisation catalyst - using magnesium chloride based support of specified properties, suitable for suspension or fluidised bed polymerisation
US4544647A (en) * 1982-07-29 1985-10-01 The Dow Chemical Company Catalyst prepared from organomagnesium compound, organic hydroxyl-containing compound, reducing halide source and transition metal compound
US4526943A (en) * 1982-07-29 1985-07-02 The Dow Chemical Company Process for polymerizing olefins in the presence of a catalyst prepared from organomagnesium compound, organic hydroxyl-containing compound, reducing halide source and transition metal compound
EP0101978A1 (en) * 1982-08-05 1984-03-07 Phillips Petroleum Company Olefin polymerization
US4426316A (en) 1982-09-10 1984-01-17 The Dow Chemical Company Catalyst prepared from organomagnesium compound, organic hydroxyl-containing compound, reducing halide source and transition metal compound
US4605715A (en) * 1982-09-20 1986-08-12 The Dow Chemical Company Process for polymerizing olefins in the presence of a catalyst prepared from organomagnesium compound, epihalohydrin reducing halide source and transition metal compound
US4604374A (en) * 1982-09-20 1986-08-05 The Dow Chemical Company Catalyst prepared from organomagnesium compound, epihalohydrin reducing halide source and transition metal compound
US4456547A (en) * 1982-10-21 1984-06-26 Fuentes Jr Ricardo Catalyst prepared from organomagnesium compound, organic hydroxyl-containing compound, reducing halide source and complex formed from admixture of a transition metal compound and an organozinc compound
US4529715A (en) * 1983-10-17 1985-07-16 The Dow Chemical Company Catalyst prepared from organomagnesium compound, carbon dioxide, reducing aluminum source, transition metal compound and zinc compound
US4569975A (en) * 1984-03-19 1986-02-11 The Dow Chemical Company Polymerization of olefins in presence of a catalyst prepared from organomagnesium compound, carbon dioxide compound, reducing halide source and transition metal compound
US4783512A (en) * 1985-05-20 1988-11-08 The Dow Chemical Company Process for polymerizing olefins in the presence of a catalyst prepared from organomagnesium compound, organic hydroxyl-containing compound, reducing halide source and transition metal compound
US4661465A (en) * 1985-10-31 1987-04-28 The Dow Chemical Company Method for preparing transition metal component of Ziegler-Natta catalysts
US5045612A (en) * 1990-04-18 1991-09-03 The Dow Chemical Company Catalyst and process for polymerizing olefins
US5114897A (en) * 1990-04-18 1992-05-19 The Dow Chemical Company Catalyst and process for polymerizing olefins

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