LU85968A1 - PROCESS FOR THE PREPARATION OF A ZIRCONIUM OR HAFNIUM CATALYST AND PROCESS FOR POLYMERIZATION OR COPOLYMERIZATION OF UNSATURATED COMPOUND USING THE SAME - Google Patents

Description

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PROCESS FOR THE PREPARATION OF A ZIRCONIUM OR HAFNIUM CATALYST AND PROCESS FOR POLYMERIZATION OR COPOLYMERIZATION OF UNSATURATED COMPOUND

_USING THIS CATALYST_ 5 'The present invention relates to a homopolymerization or copolymerization process of α-olefins in the very broad sense of ethylene, characterized by the use of a new catalytic system consisting of a catalyst based on titanium, magnesium, zirconium or haf-10 nium. The catalytic system resulting from the association of this catalyst with two other constituents, as specified below, has such a special and surprising behavior that it is effective, inter alia, in the preparation of homopolymers having a wide weight distribution mo-15 lecular; or else in the preparation of copolymer also having a high resistance to cracking under stress, in a surface-active medium (R.F.C.), property which is required for particular articles, such as for example bottles; in addition to other characteristics, such a wide distribution of molecular weight makes the products particularly suitable for the manufacture of films or tubes, as will be seen more clearly below.

The polymerization of ethylene using titanium-based catalysts is widely described in the patent literature. Far example in the application this French patent Nc 8101505 it is described ur: process of homopolymerization (or this copolymerization) of unsaturated compounds, in particular of ethvlèr.e and higher a-ole ins to obtain homopolymers (or copolymers) 30 having a wide distribution of molecular weights (8 £ Mp / Mn £ 12) able to be transformed by blow molding techniques not particularly suitable for real articles such as films or these tubes . This process uses as catalyst, in coririr.ri? R * 3c s with a cornoos 'oraarir'ré ’·?' 'i ^ u0 of aluminum' me c: · ^ - »- 2 - * * t chemical position based on titanium rrinalogénide having the following formula:

Ti X3. mM-Yn. g -M "ï'p · c Al Y" 3_sRs in which X is a halogen ion. and m, q, cf M ', M ", Y, 5 Y', Y", n, p, s, R have the meanings reported in the specification of the above-mentioned 2nd patent application.

In the French patent application No. 8212867, however, a process for the polymerization and copolymerization of α-olefins (including ethylene) is also described in the presence of conjugated diolefins, and in particular of polymerization of ethylene with 1,3-butadiene, based on the use of a multi-component catalytic system in which one of these components contains titanium and magnesium, the polymers obtained by this process having in any way a narrow distribution of molecular weights (3 _ <Mp / Mn _ <5).

The authors of the present invention have now discovered, and this is the object of the present invention, that a particularly suitable catalyst can be obtained as a catalytic component in the homopolymerization of ethylene or in the copolymerization of ethylene with α-olefins.

This catalyst which is the subject of the present invention is obtained by a process comprising the following stages: 2c vaporization of macnesium under vacuum and reaction of the vapors obtained with a quadrivalent titanium comoose in the presence of a compound donor of halogen atoms and a zirconium and / or hafnium compound: b) heat treatment of the mixture obtained by adding 1 30 to the cold solution previously prepared an alcohol of formula ROH, in which F. is a linear or branched aliphatic chain containing from 1 to 10 carbon atoms, possibly a substitute - ~ ~~~ ________.

νΓυ-ρθί aromatiguct, ci treatment th "'' -; - - ~. , - --- "-n- a revival ootenu in agonranτ 35 to the orenaré solution ^ · ~ ^ _ f * · - ~ m- ------ merv, at least one organometallic compound ec of aluminum having the formula AlR'g X ^, 'in which R' represents a hydrocarbon radical; X represents a halogen atom and Y is a number equal to or in the range 0 to 2, such that 5 1 <halogen / Al <2.

The vaporization in stage a is carried out at pressures between 1.33 x 10u and 1.33 x -4 10 mbar, or equal to these values, at a temperature ranging from 300 to 600 ° C. The reaction of these vapors thus obtained with the titanium compound in the presence of the halogen donor is carried out at low temperature, usually at temperatures between -80 and + 20 ° C or equal to these values. In order to maintain the reaction mixture in the liquid state, it is possible to add to the cooled reagents, generally in the range of -100 to + 10 ° C., an inert hydrocarbon diluent such as for example n.heptane or n .hexa-ne.

The heat treatment in stage b takes place at temperatures equal to 50-100 ° C or included in this interval for durations equal to δΟ'-ΙδΟ ', or included in this interval while stirring.

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The organometallic aluminum compound is added in stage c as it is or in the form of a solution in a hydrocarbon, the preferred compound being Al ~, Et-.Cl_.

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The heat treatment in stage c is carried out at a temperature equal to 80-100 ° C or included in this range while stirring. The following molar ratios are used: 30 0.3 <Mg / RQH <2 5 <Mg / Ti <20 2 <Mg / Zr <5 1 <Mc / Hf <10

The cor-rosé of zirconium or hafnium, yes for fear of being also introduced in the second stage, is chosen from among them. very and alconiates. and in particular - we use zirconium tetra-alcoholate, zirconium tetrachloride, hafnium tetrachloride.

The alcohol ROH can be a primary, secondary or tertiary alcohol, in which R is a branched linear aliphatic-5 chain gu containing from 1 to 10 carbon atoms, optionally substituted by aromatic groups, but preferably the alcohols are used butyl, amyl, isoamyl, benzyl.

As halogen donors, organic halides can be used, in particular those having the formula C H ~ X, in which X s Cl, Br; m represents m 2m + 2-xx '^' '- - feels a number equal to 1-18 or included in this interval, and x is a number equal to 1-4 or included in this interval, and in this case these halides can also constitute said dilute medium or else it is possible to use mineral halides of elements having a high valence state, but which can exist in at least two oxidation states, such as SnCl 4, SbCl 4, POCl 4 r VCl ^.

As for the titanium compound, it can be chosen from a wide range of products such as, for example, titanium trihalides and tetrahalides, titanium te-tra-alcoholates and titanium halo-alcoholates, titanium derivatives. tetrabenzyl and titanium-ha-logeno-benzyl, titanium-tetra-allyl and titanium-ha-25 logeno-allyl, titanium amides and amido-halides, titanium chelates, etc. Their use is particularly effective, and this represents a second object of the present invention, as constituents of catalytic systems in the homopolymerization of ethylene or in the copolymerization of ethylene with α-olefins.

The authors of the present invention have in fact discovered that these polymers or these co-mothers of ethylene can be prepared by causing the polymerization to take place. cook in the presence of the courtyard, a system consisting of a derivative of 1 aluminum of formula, because s which F: is ur.

t <_ c _ - /. * hydrocarbon residue; X is a halogen atom / and p is equal to 1-3 or included in this range, and by a catalyst based on zirconium or hafnium as just defined.

5 The α-olefins to be copolymerized with ethylene are preferably butene-1, propene, hexene-1, octene-1. Said composition can be used directly in the polymerization, as obtained from the preparation process described above, without the need for filtration or separation. The polymerization is carried out in turn in the presence of a hydrocarbon solvent which can naturally be the same as the diluent used for the preparation of the titanium derivative, at temperatures ranging from 20 to 200 ° C., and under pressures. ranging from 1.013 bar to 60.78 bar.

Alternatively, the polymerization can be carried out by passing the monomer or monomers directly in the gaseous state over the catalytic system. The polymers and copolymers of ethylene are obtained with high yields, a wide distribution of molecular weights, as can be seen from the values of Mp / Mn, obtained by gel permeation chromatography, (GPC ) in the range of 12 to 20.

These polymers are particularly suitable for extrusion and blow molding techniques, in particular for the manufacture of film.

Thanks to their high resistance to cracking under stress in a surface-active medium, the products are particularly suitable for certain applications such as detergent containers and large containers.

The present invention is illustrated by the following descriptive and nonlimiting examples.

Example 1 3t j, -ret-arstxon du consrxruanr catalvcxcue pi The first stage of preparation is carried out in -6-- * <a rotating balloon in the center of which is a filament. - of tungsten wound in a spiral which is connected to a source of electrical energy.

About 500 cm3 of anhydrous heptane, 0.60 cm3 (5.4 mmol) of TiCl 4, 6 g (25.7 mmol) of ZrCl 4 and 25 cm3 are introduced into the flask under an azo-5 te atmosphere. (237 mmol) of chlorobutane.

Around the tungsten spiral, 3 g of Mg (125 atom-mg) are wound. The flask is cooled to -70 ° C, a vacuum of 1.33 x 10 "mbar is applied, and the spiral is heated to vaporize the magnesium.

After 20 ', nitrogen is introduced into the flask and in the second stage of the cold suspension, 7.43 cm3 of iso-amyl alcohol are added while stirring. The flask is brought to room temperature, then the reaction mass is brought to the boiling temperature for 2 hours, obtaining a brown suspension.

In the third stage of preparation, 108 mmol of Al 2 Et 4 Cl 4 are added to the suspension obtained beforehand, and the whole of the reaction mass is brought to the boiling temperature for 3 hours. The color of the pendant light turns blue-green.

The catalyst thus obtained is washed with hep-tane and has the following elementary composition: 25 Ti = 1.55%

Mg = 14.65%

Zr = 14.34%

Cl = 69.4%

Example 2 30 Polymerization

2 1 of anhydrous and deaerated n.heptane and t halves of aluminum isobutylate (Al (iso) are introduced into a 5-liter autoclave, free of air and humidity, and fitted with a stirrer with a magnetic armature. .drank),).

3Ξ1 We temperature the temperature at 80 ° C and then introduced "" -in the gold lease. In the order indicated 5.6 bars of H-,? T -! - of butene-1, an amount of suspension of the prepared catalyst according to example No. 1 equivalent to 0.0212 atom-mg of titanium, and ethylene until a total pressure of 9.4 bars is obtained. The introduction of ethylene into 3 l the autoclave is continued for 2 hours i, or b- 0 holding the pressure at a constant value. At the end of this time, the reaction is stopped and the atmosphere is relaxed in the autoclave. 359 g of polymer equivalent to 355,000 are obtained. g per g of metallic titanium The characteristics 10 of the product are as follows: hot melt index under a load of 2.16 kg (MFI2 16 standard ASTM 1238 / E) = 0.35 g / 10 '.

- shear sensitivity (S.S. MFI-- c / MFIn = 101.

£ I f Ό £. j I Ό - density (djnorm ASTM D 1505) = 0.9548 kg / dm3.

15 - shear speed (yc, ASTM D 1703 standard) = 1000 s \ - crack resistance under stress in surfactant medium (RFC, ASTM D 1693 standard) = 220 hours.

- Mp / Mn = 14.5 (G.P.C.)

Example 3 Preparation of the catalytic component

The catalyst is prepared as in Example 1. 300 cm3 of anhydrous hepane are introduced into the flask, 0.6 cm3 (5.4 mmol) of TiCl4, 6 g (25.7 minores) of ZrCl ^ and 26 cm3 (790 mmol) of 1-chlorohexane 25 under a nitrogen atmosphere. Around the tungsten spiral is wound 2.45 g of magnesium (100 atoms-'mç) and the Vaporization is carried out as in Example 1.

To the cold suspension is added 7.5 cm 3 of buryl alcohol while stirring. In the third stage of preparation, 100 mmol of A ^ Lt-Cl- are added to the suspension and the suspension is heated during 3 hours. The product is washed with heptane, and after having dried it has the following elementary composition ï Ti = 1.78% 35 Mg = 13.36% jt Zr = 16.38 ï - 8 - * 'Cl = '68, 15%

Example 4 -

Polymerization

The operation is carried out with the same equipment and in the same manner as in Example 2.

At 80 ° C., 5.6 bars of, 6 g of bu-tene-1 are introduced, an amount of suspension of the catalyst prepared according to example 3 equivalent to 0.02 atom-mg of titanium and ethylene up to 'to have a total pressure of 9.4 bar. After 2 hours of polymerization, 320 g of polymer are obtained, equal to a production of 333,000 g / g of titanium. The product characteristics are as follows: MFI2 16 = 0.16 g / 10 'Ερ / Πή = 16 15 SS = 95 d = 0.9565 kg / dm3 γ = 850 s "1 1 c RFC = 500 hours Example 5 20 Polymerization

The polymerization is carried out as in Example 4 except that the comonomer ^ which is in this case propene / is used in an amount of 5 g. The product obtained, 360 g, has the following characteristics: 25 MPI, 16 = 0.32 g / 10 'SS = 105 d = 0.9572 kg / dm3 v = 1800 s-1' c RFC = 100 hours 30 Mp / Hn = 13.5 Example 6

Preparation of the catalytic component The preparation of the catalyst is carried out by entering in the flask under nitrogen atmosphere 300 cm5 of anhydrous hectare, 0.48 cm3 * 4.3 mmclesj of iCV, 3.2 crs. [2- ~ robins ;. fa chlorobutane. Art: vr of the tune spiral - ί - 9 - - 'sten 0.6 g of magnesium wire (25 mg atoms) is wound and this wire is vaporized as in Example 1. At the suspension • cold, 4.6 g (14.4 mmol) of HfCl 4 and 5.2 cm3 (57.6 mmol of n.butanol are added while stirring. In the third stage of preparation, 42.5 mmol are added of Al0Et ^ Cl_, to the suspension and the suspension is brought to the boiling temperature for 3 hours.

The product is washed with heptane and after drying it has the following elementary composition: 10 Ti = 2.7%

Mg = 7.66%

Hf = 34.2%

Cl = 55.3%.

Example 7 15 Polymerization

The same equipment and the same procedure are used as in Example 2. Six bars of H2, 6 g of butene-1 are introduced, an amount of suspension of the catalyst obtained according to Example 6 equivalent to 0.0374 atom- 20 mg of titanium, and ethvene up to a total pressure of 9.4 bar.

After two hours of polymerization, 206 g of polymer are obtained, equal to a production of 115,000 g / g of titanium.

25 The product characteristics are as follows: MFI2 = 0.21 g / 10 'S.S. = 145 d = 0.9579 kg / dm3 30 γ = 750 s-1 c RFC = 500 hours AMp / MÜ = 15.

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Claims (12)

1. Process for the preparation of a catalyst based on zirconium or hafnium, characterized in that it comprises the following stages: 5 a) vaporization of magnesium under vacuum and reaction of the vapors thus obtained with a quadrivalent titanium compound in the presence of a halogen atom donor compound and a zirconium and / or hafnium compound; b) heat treatment of the mixture obtained by adding to the fluid solution prepared above an alcohol of formula ROH, in which R is an aliphatic chain, linear or branched, containing from 1 to 10 carbon atoms, optionally substituted by aromatic groups; C) heat treatment of the mixture obtained by adding to the solution prepared above an organometallic aluminum compound having the formula AlR '^. YXy / in which R' represents a hydrocarbon radical; X is a halogen atom, and y is a number equal to 0-2 or 20 within this range, so that we have 1 <halogen / AL 2. 2. Process for the preparation of a catalyst based on zirconium or hafnium according to the preceding claim, characterized in that the vaporization of the magnesium is carried out under a pressure equal to 1.33 x 10 * ^ - -4 1.33 x 10 mbar or included in this range. 3. A process for the preparation of a zirconium or hafnium-based catalyst according to claim 1, characterized in that the vaporization of the magnesium is carried out at a temperature equal to 300-600 ° C or included in this range. 4. A method of preparing a zirconium or hafnium-based catalyst, according to claim 1, cavc2-téri-sé in that the reaction between the metal vapors- 3. li-rPJÄ ~ Π1Τ TTSr? Pûcium " 1 rm AA £ * "* - τ <* - - v. V" j Ί λτ ** 4- - ^ - w "-1 ...„ - livûj.uiu, jute ~ -1 wQîjC vdur J. v aiSÏJU ^ r - 11 - t * zirconium and / or hafnium occurs at temperatures equal to -80 - + 20 ° C or included in this range. 5. Process for the preparation of a zirconium or hafnium catalyst according to claim 1, characterized in that the heat treatment of stage b takes place at temperatures equal to 50-100 ° C or included in this interval. 6. Process for the preparation of a zirconium or hafnium catalyst according to claim 1, characterized in that the heat treatment of stage b is carried out for durations equal to 60'-180 'or inclusive in this interval. 7. A process for the preparation of a zirconium or hafnium catalyst according to claim 1, characterized in that the heat treatment for stage c is carried out at temperatures equal to 80-100 ° C or included in this interval. 8. A process for preparing a zirconium or hafnium-based catalyst according to claim 1, characterized in that the process is carried out with the following molar ratios: 0.3 <Mg / ROH <2, 0 5 <Mg / Ti <20 2 <Mg / Zr <5 25 1 <Mg / Hf <10. 9. ~ A process for the preparation of a catalyst based on zxrconium or hafnium according to claim par} characterized in that the oraanometallic aluminum compound is preferably - '' £ ': E ~ ci · * / 10. A process for preparing a catalyst based on zirconium or hafnium according to claim \ characterized in that the compound of zirconium and / or a'haf-muni ssii OüOxsx äs ^ z- tî ^ 0 c $ · Därrii j. ^ S S'ti 2 "? Alcoholates. 35 11.- Process for the preparation of a catalyst & sr: ase S * l of zirconium or c'hafnium according to claim 1:, -.: - .. - ~ P! I * "b '" - 12 - Λ - terized by the fact that the zirconium or hafnium compound is preferably chosen from zirconium tetra-alcoholate, zirconium tetrachloride, hafnium tetrachloride . 12. Process for the preparation of a catalyst based on zirconium or on hafnium according to claim Λ, characterized in that the alcohol RQH is preferably chosen from butyl alcohol, amyl alcohol, iso alcohol -amyl, benzyl alcohol. 10 13, - Process for the preparation of a catalyst based on zirconium or hafnium according to claim ^ characterized in that the halogen donor compound is chosen from organic halides, preferably from those corresponding to the general formula <- 'mIÎ2m + 2-xXx 1 15 wherein X is chlorine or bromine; m represents; "a number in the range from 1 to 18, and x is a number from 1 to 4. 14. Process for the preparation of a zirconium or hafnium base catalyst according to claim 1, characterized in that the halogen donor is chosen from mineral halides of high valency of elements capable of existing in at least two valence states, preferably among SnCl ^, SbCl ^, POCl ^ and VCl ^. 15. A process for the preparation of a zirconium or hafnium ba-25 se catalyst according to claim caractériséf, characterized in that the titanium compound is preferably chosen from titanium trihalide, titanium tetra-halide, titanium tetra-alcoholate, titanium ha-logeno-alcohol, titanium-tetrabenzyl derivative, titanium-halo benzenz derivative, titanium-tetra-allyl, titanium halo-allyl, amides titanium, titanium amido halides and titanium chelates. 16. Process for the homopolymerization of ethylene and the copolymerization of ethylene with α-olefins consisting of c? T-_ vir. * 1 and 1_gs / 4 * A * en - 13 - * - α-olefins with a catalytic system constituted by an aluminum derivative of formula Al R X0, R being a .. P 3 “P; • hydrocarbon residue; X is a halogen atom / and p is between 1 and 3 ,. and by a catalyst based on zir-5 conium or hafnium according to any one ce s-, claims 1 to 15. If ~~ '<== py- lS