EA041560B1 - METHOD FOR PRODUCING PROCATALYST FOR PRODUCING CATALYTIC COMPOSITION FOR OLEFIN POLYMERIZATION - Google Patents

Description

Prerequisites for the creation of the invention

The invention relates to a process for the preparation of a solid support for a procatalyst suitable for the polymerization of olefins. The present invention also relates to said solid support for the obtained procatalyst. In addition, the present invention relates to a process for producing a procatalyst and a procatalyst obtained therewith. Moreover, the present invention relates to a catalyst system for the polymerization of olefins containing the specified procatalyst, optional co-catalyst and optional external electron donor. Furthermore, the present invention relates to a process for producing polyolefins by contacting at least one olefin with said catalyst system. Moreover, the present invention relates to polymers obtained by polymerization using said procatalyst, and to molded articles from said polymers.

Catalyst systems and their components that are suitable for the production of polyolefin are well known. One type of such catalysts is commonly referred to as Ziegler-Natta catalysts. The term Ziegler-Natta is known in the art and generally refers to catalyst systems containing an organometallic compound (also commonly referred to as a co-catalyst) and optionally one or more compounds that are electron donors (e.g. external electron donors) , and a compound which is a solid catalyst containing a transition metal (also commonly referred to as a procatalyst) comprising a transition metal halide (e.g., titanium halide, chromium halide, hafnium halide, zirconium halide, vanadium halide) on a support representing the compound metal or metalloid (for example, a magnesium compound or a silicon compound). An overview of such types of catalysts is provided, for example, by T. Pullukat and R. Hoff in Catal. Rev. - Sci. Eng. 41, vol. 3 and 4, 389438, 1999. The preparation of such a procatalyst is disclosed, for example, in WO 96/32427 A1. Thus, there is currently a need in the industry for a phthalate-free polymer catalyst.

It is an object of the present invention to provide an improved process for the production of a phthalate-free olefin polymerization procatalyst.

A further object of the present invention is to provide a procatalyst that exhibits appropriate performance, in particular, exhibits improved productivity and bulk density.

Brief description of the invention

At least one of the above objects of the present invention is achieved through several aspects discussed below.

The present invention relates to a process for preparing a solid support for a procatalyst suitable for preparing a catalyst composition for the polymerization of olefins, said process for preparing said solid support comprising reacting an R ⁴ zMgX ⁴ _{2_z} compound with a silane compound Si(OR ⁵ )4.n( R ⁶ )n in a solvent and mixing the resulting mixture with a mixing device and at a certain mixing speed to obtain a solid substrate Mg(OR1) _x X1 ₂ . _x , wherein said solid substrate obtained has an average particle size of at most 17 µm, preferably at most 16 or at most 14 µm, more preferably at most 12 µm.

In the above, each of R ¹ and R ⁴ independently represents a linear, branched or cyclic hydrocarbon group independently selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups and one or more combinations thereof; where the specified hydrocarbon group may be substituted or unsubstituted, may contain one or more heteroatoms and preferably contains from 1 to 20 carbon atoms;

each X ⁴ is independently selected from the group consisting of fluoride (F-), chloride (Cl-), bromide (Br-) or iodide (I-), preferably chloride; z is in the range from more than 0 to less than 2, i.e. 0<z<2;

each R ⁵ is independently a linear, branched or cyclic hydrocarbon group independently selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups and one or more combinations thereof; where the specified hydrocarbon group may be substituted or unsubstituted, may contain one or more heteroatoms and preferably contains from 1 to 20 carbon atoms;

each R ⁶ is independently a linear, branched or cyclic hydrocarbon group independently selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups and one or more combinations thereof; where the specified hydrocarbon group may be substituted or unsubstituted, may contain one or more heteroatoms and preferably contains from 1 to 20 carbon atoms;

n is in the range from 0 to 4, preferably n is from 0 to 1 inclusive;

each X ¹ is independently selected from the group consisting of fluoride (F-), chloride (Cl-), bromide

- 1 041560 (Br-) or iodide (I-), preferably chloride;

x is in the range from more than 0 to less than 2, i.e. 0<x<2.

In one embodiment, a mixing device with propeller blades is used. In one embodiment, a reactor with at least two baffles is used. In one embodiment, mixing starts at an initial mixing speed, and where the speed is increased to a final mixing speed, where the initial mixing speed is lower than the final mixing speed, where preferably the initial mixing speed is from 30 to 450 rpm, preferably from 100 to 400 rpm and/or where the final mixing speed is from 150 to 750 rpm, preferably from 450 to 600 rpm.

The present invention also relates to a solid procatalyst support obtainable by the method of the present invention. The present invention also relates to a process for the production of a procatalyst for the production of a catalyst composition for the polymerization of olefins, said process comprising the steps of:

step 1) obtaining a solid support in accordance with the method of the present invention discussed above;

step 2) optionally contacting the solid support obtained in step 1) with at least one activating compound selected from the group formed by activating electron donors and metal alkoxide compounds of the formula M1(OR ² )v_w(OR ³ ) w or M ² (OR ² )v_w(R ³ )w to form a reaction intermediate; where M ¹ represents a metal selected from the group consisting of Ti, Zr, Hf, Al or Si; M ² is a metal which is Si; v represents the valency of M ¹ or M ² , and w<v; each of R ² and R ³ is a linear, branched or cyclic hydrocarbon group independently selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups and one or more combinations thereof; where the specified hydrocarbon group may be substituted or unsubstituted, may contain one or more heteroatoms and preferably contains from 1 to 20 carbon atoms;

step 3) reacting the solid support or reaction intermediate obtained in step 1) or 2), respectively, with a halogenated Ti compound, optionally an activator, and at least one internal electron donor to form a pronatalist.

In one embodiment, in step 3) ethyl benzoate is used as an activator and 4-[benzoyl(methyl)amino]pentan-2-ylbenzoate (AB) is used as an internal electron donor. In one embodiment, in step 3), ethyl benzoate is used as the activator and 4-[(ethoxycarbonyl)(methyl)amino]pentan-2ylethylcarbamate (AB-OEt) is used as the internal electron donor. In one embodiment, in step 3), dimethylbenzamide (BA-2Me) is used as an activator and 9,9bis(methoxymethyl)fluorene (Flu) is used as an internal electron donor. In one embodiment, in step 3), di-n-butyl phthalate (DnBP) or diisobutyl phthalate (DIBP) is used as the internal electron donor.

The present invention also relates to a procatalyst obtained or obtained using the method in accordance with the present invention. The present invention also relates to a catalyst system comprising a procatalyst according to the present invention, a co-catalyst and optionally an external electron donor. The present invention also relates to a process for the production of polyolefins comprising contacting the catalyst system according to the present invention with at least one olefin, preferably propylene, to form a polypropylene homopolymer, or a mixture of propylene and an olefin such as ethylene, butene or hexene, to obtain a copolymer of propylene and olefin. The present invention also relates to a polyolefin, preferably a polypropylene or a propylene-olefin copolymer obtainable by the process of the present invention. The present invention also relates to a molded article containing the polyolefin of the present invention.

Definitions

The following definitions are used in the present specification and claims to define the claimed subject matter. Other terms not listed below are intended to have the meanings generally accepted in the art.

The term Ziegler-Natta catalyst as used herein means a compound that is a solid transition metal catalyst that provides a catalytically active compound supported on a metal or metalloid compound support (for example, a magnesium compound or a silicon compound) .

The term catalytically active compound as used herein means a transition metal-containing compound which includes a transition metal halide selected from titanium halide, chromium halide, hafnium halide, zirconium halide and vanadium halide.

The terms internal donor or internal electron donor or ID as used herein means an electron donor compound containing one or more oxygen (O) and/or nitrogen (N) atoms.

The terms external donor or external electron donor or ED as used herein means an electron donor compound used as a reactant in the polymerization of olefins. It contains at least one functional group capable of donating at least one pair of electrons to a metal atom.

The term activator as used herein means an electron donor compound containing one or more oxygen (O) and/or nitrogen (N) atoms, which is used during the synthesis of a pronatalist before or simultaneously with the addition of an internal donor.

The term activating compound as used herein means a compound that is used to activate a solid support prior to bringing it into contact with a catalytically active compound.

The terms modifier or Group 13 metal or transition metal modifier as used herein means a metal modifier that includes a metal selected from Group 13 metals of the IUPAC Periodic Table of Elements and transition metals. When the expressions used in the description are metal modifier or metal based modifier, the Group 13 metal modifier or transition metal modifier is meant.

The term procatalyst as used herein has the same meaning: a component of a catalyst composition, typically containing a solid support, a catalytically active transition metal compound, and optionally one or more internal donors.

The terms halide or halogen as used herein means an ion selected from the group: fluoride (F-), chloride (Cl-), bromide (Br-) or iodide (I-).

The term heteroatom as used herein means an atom other than carbon or hydrogen. However, when used herein, unless otherwise indicated, such as below, when the expression one or more heteroatoms is used, then one or more of the following is meant: F, Cl, Br, I, N, O, P, B, S or Si. Thus, the heteroatom also includes halides.

The term hydrocarbon radical as used herein means a substituent containing hydrogen and carbon atoms, or a linear, branched or cyclic saturated or unsaturated aliphatic radical such as alkyl, alkenyl, alkadienyl and alkynyl; an alicyclic radical such as cycloalkyl, cycloalkadienyl, cycloalkenyl; an aromatic radical such as a monocyclic or polycyclic aromatic radical; and combinations thereof, for example alkaryl and aralkyl. The hydrocarbon group may be substituted with one or more non-hydrocarbon substituent groups. A non-limiting example of a non-hydrocarbon substituent is a heteroatom. Examples are alkoxycarbonyl (ie carboxylate) groups. If the term hydrocarbon radical is used in the present description, then it can also be a substituted hydrocarbon radical, unless otherwise indicated.

The term alkyl as used herein means an alkyl group that is a functional group or a side chain composed of carbon and hydrogen atoms that contains only single bonds. The alkyl group may be straight or branched and may be unsubstituted or substituted. The alkyl group also embraces aralkyl groups wherein one or more hydrogen atoms of the alkyl group are replaced by aryl groups.

The term aryl as used herein means an aryl group that is a functional group or a side chain derived from an aromatic ring. The aryl group may be unsubstituted or substituted, with straight or branched hydrocarbon groups. An aryl group also encompasses alkaryl groups where one or more hydrogen atoms on the aromatic ring have been replaced by alkyl groups.

The terms alkoxide or alkoxy as used herein means a functional group or side chain derived from an alkyl alcohol. It consists of an alkyl bonded to a negatively charged oxygen atom.

The terms aryloxide or aryloxy or phenoxide as used herein means a functional group or side chain derived from an aryl alcohol. It consists of an aryl bonded to a negatively charged oxygen atom.

The terms Grignard reagent or Grignard compound as used herein means: a compound or mixture of compounds of the formula R ⁴ zMgX ⁴ 2_z (R ⁴ , z and X ⁴ are defined below), or a complex containing more Mg clusters, e.g. R4Mg _3Cl2 .

The term polymer as used herein means a chemical compound containing repeating structural units, where the structural units are monomers.

The term olefin as used herein means an alkene.

The terms olefin-based polymer or polyolefin as used herein are

- 3 041560 means a polymer of one or more alkenes.

The term propylene-based polymer as used herein means a polymer of propylene and optionally a comonomer.

The term polypropylene as used herein means a polymer of propylene.

The term copolymer as used herein means a polymer made from two or more different monomers.

The term monomer used in the present description means a chemical compound that can be subjected to polymerization.

The terms MWD or molecular weight distribution used in the present description mean the same as PDI or polydispersity index. This is the ratio of the weight average molecular weight (M _w ) to the number average molecular weight (M _n ), i.e. M _w /M _n , is used as an indicator of the width of the molecular weight distribution of the polymer. M _w and M _n are determined by GPC using a Waters 150° C. gel permeation chromatograph in combination with a Viscotek 100 differential viscometer; chromatograms were obtained at 140°C using 1,2,4-trichlorobenzene as a solvent; a refractive index detector was used to generate a signal with respect to molecular weights.

The terms XS or xylene soluble fraction or CXS or xylene cold soluble fraction as used herein means the weight percent (wt%) of xylene soluble isolated polymer measured according to ASTM D 5492-10.

The term spread as used herein means: (d90-d10)/(d50) where d10, d50 and d90 are the cut-offs for 10%, 50% and 90% cumulative mass.

The term bulk density as used herein means the weight per unit volume of a material, including voids inherent in the material being tested. Bulk density is measured as apparent density according to ASTM D1895-96 Reapproved 2010-e1 Test Method A.

The term polymerization conditions as used herein means the temperature and pressure conditions in the polymerization reactor that are suitable to allow polymerization of the catalyst composition and olefin to form the desired polymer. Such conditions depend on the type of polymerization used.

The terms productivity or yield as used herein means the amount of polymer produced, expressed in kilograms, per gram of procatalyst consumed in the polymerization reactor per hour, unless otherwise indicated.

The terms MFR or melt flow rate as used herein means measurement at a temperature of 230° C. under a load of 2.16 kg and measurement in accordance with ISO 1133:2005.

Unless otherwise stated, if it is noted that any R group is independently selected from, then this means that if several identical R groups are present in the molecule, they may have the same value or they may not have the same value. The present invention is described in more detail below with reference to the accompanying schematic drawings. All embodiments described with respect to one aspect of the present invention are also applicable to other aspects of the present invention, unless otherwise indicated.

Graphic materials

In FIG. 1 shows a 3D view of an embodiment of a propeller agitator according to the present invention;

in fig. 2 shows the propeller mixer of FIG. 1 in plan view;

in fig. 3 is a side view of a prior art paddle agitator embodiment;

in fig. 4 is a side view of an embodiment of a baffle according to the present invention, and FIG. 5 is a side view of an embodiment of a reactor according to the present invention, where the reactor is shown as being transparent.

Detailed description of embodiments

Surprisingly, it has been found that the properties of the procatalyst can be improved by an improved method for producing a solid support. An advantage of the present invention is that support particles are obtained having a smaller particle size, resulting in smaller procatalyst particles, which in turn results in higher production or yield and bulk density of the polymer product.

An aspect of the present invention relates to a multi-stage process for the preparation of a procatalyst comprising steps 1), 2) and 3), namely, a process for the preparation of a procatalyst suitable for the preparation of a catalyst composition for the polymerization of olefins, said process comprising the steps: 1a) providing or obtaining a Grignard compound; step 1b) contacting the Grignard compound with an alkoxy or aryloxysilane

- 4 041560 connection to obtain a solid support; step 2) optionally bringing the resulting solid support into contact with at least one activating compound; and step 3) reacting the (activated) support with a halogenated Ti compound as catalytic compound, optionally an activator, and at least one internal electron donor.

Preferably, the Ziegler-Natta type procatalyst in the catalyst system according to the present invention is prepared by a process similar to that described in EP 2027164 B1. Example I, including all sub-examples (IA-IE), is included in the present description. More details about the various embodiments are disclosed in paragraphs [0016] to [0089]. All data embodiments that relate to the method and products are incorporated by reference into the present description. In the following part of the description, the various steps and phases of the process for producing a pronatalistic in accordance with the present invention will be discussed.

The process for producing a procatalyst according to the present invention includes the following phases or steps:

phase I) obtaining a solid support for pronatalistic (stage 1a and stage 1b); this phase is the key phase in accordance with the present invention;

phase II) optionally activating said solid support obtained in phase I using one or more activating compounds to form an activated solid support (step 2);

phase III) contacting said solid support obtained in phase I or said activated solid support obtained in phase II with a catalytically active compound, optionally an activator and at least one internal donor (step 3);

and optionally phase IV) modification of said intermediate obtained in phase III, wherein phase IV may include one of the following: modification of said intermediate obtained in phase III with a Group 13 metal or transition metal modifier, if if an internal donor was used during phase III to obtain a pronatalistic; modifying said phase III intermediate with a group 13 metal or transition metal modifier and an internal donor, if an activator was used during phase III, to obtain a procatalyst.

The procatalyst thus obtained can be used in the polymerization of olefins using, for example, an external electron donor and a co-catalyst. The various steps used to prepare the catalyst according to the present invention are described in more detail below.

Phase I. Obtaining a solid support for the catalyst.

The method for producing a solid support for a procatalyst according to the present invention comprises the steps of step 1a) providing or preparing a Grignard reagent and step 1b) reacting a Grignard compound with a silane compound.

Step 1a) may involve providing a previously obtained or commercially obtained Grignard reagent, or may involve obtaining a Grignard reagent. Said Grignard reagent provided or prepared in step A is R ⁴ zMgX ⁴ 2_ _z . R ⁴ is independently selected from a linear, branched or cyclic hydrocarbon group independently selected from alkyl, alkenyl, aryl, aralkyl or alkylaryl groups and one or more combinations thereof; where the specified hydrocarbon group may be substituted or unsubstituted, may contain one or more heteroatoms and preferably contains from 1 to 20 carbon atoms; preferably R ⁴ is phenyl or butyl, more preferably butyl. X ⁴ is independently selected from the group consisting of fluoride (F-), chloride (Cl-), bromide (Br-) or iodide (I-), preferably chloride, z is greater than 0 to less than 2, i.e. . 0<z<2. For example, R ⁴ zMgX ⁴ 2- _z is n-butyl magnesium chloride or phenyl magnesium chloride, where R ₄ is n-butyl and phenyl, respectively, z=1, and X=Cl. Step A), including many embodiments, is described in detail in WO 2015091984 A1 of the same applicant, page 15, line 14 - page 16, line 28, the entire section of which is incorporated herein by reference.

Step 1b) involves reacting an R ⁴ zMgX ⁴ _{2_z} compound, where each R ⁴ is independently a linear, branched or cyclic hydrocarbon group independently selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl, or alkylaryl groups and one or more of them. combinations; where the specified hydrocarbon group may be substituted or unsubstituted, may contain one or more heteroatoms and preferably contains from 1 to 20 carbon atoms; each X ⁴ is independently selected from the group consisting of fluoride (F-), chloride (Cl-), bromide (Br-) or iodide (I-), preferably chloride; z is in the range from more than 0 to less than 2, i.e. 0<z<2, with a silane compound Si(OR ⁵ )4_n(R ⁶ )n, where each R ⁵ is independently a linear, branched or cyclic hydrocarbon group independently selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl, or alkylaryl groups and one or more combinations thereof; where said hydrocarbon group may be substituted or unsubstituted, may contain one or more heteroatoms, and preferably contains from 1 to 20 carbon atoms; each R ⁶ is independently a linear, branched or cyclic hydrocarbon group independently selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups and one or more combinations thereof; where the specified hydrocarbon group may be substituted or unsubstituted, may contain one or more heteroatoms and preferably contains from 1 to 20 carbon atoms; n is in the range from 0 to 4, preferably n is from 0 to 1 inclusive; in a solvent and mixing the resulting mixture using a mixing device and at a certain mixing speed to obtain a solid substrate Mg(OR1) _x X1 ₂ . _x where R ¹ is the same as R ⁵ ; each X ¹ is independently selected from the group consisting of fluoride (F-), chloride (Cl-), bromide (Br) or iodide (I-), preferably chloride; and x is in the range from greater than 0 to less than 2, i. e. 0<x<2. In the present invention, in step 1b), the reaction between R ⁴ zMgX ⁴ 2- _z and Si(OR ⁵ ) ₄ _ _n (R ⁶ ) _n is carried out in a solvent and the mixture is mixed with a mixer and at a certain mixing speed. The specified mixing device is inside the specified reactor to obtain the specified solid substrate.

In one embodiment, the solvent used for the present invention may be selected from the group consisting of an aliphatic, alicyclic or aromatic solvent containing from 4 to 10 carbon atoms. In one embodiment, the solvent used is an ether, such as diethyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether, diisoamyl ether, diallyl ether, tetrahydrofuran (THF), anisole, and ethylphenyl ether. In one embodiment, dibutyl ether (DBE) is used as the solvent.

In one embodiment, the solvent is added to the reactor in such an amount that the solvent fills the volume of the reactor to a level of at least 25% or more. In other words, the fraction of the solvent volume in the reactor volume is at least 25%, which means that at least 25% or more of the reactor volume is filled with solvent; this may also be referred to as the fill factor or the reactor fill level. In one embodiment, this fill factor is the initial fill factor since the solvent is initially added to the reactor in the amounts described. If the filling volume is less than this, then there may be increased settling of solids on the sides of the reactor in the upper region, or there may be an increased risk of splashing with increasing agitation speed. The present inventors have found that a given amount of solvent provides better particle size control.

In one embodiment, the solvent is added to the reactor in such an amount that the solvent fills the volume of the reactor to a level of at least 30% or more. In other words, the fraction of the solvent volume in the reactor volume is at least 30%, which means that at least 30% or more of the reactor volume is filled with solvent. The present inventors have found that a given amount of solvent provides better particle size control. In one embodiment, the solvent is added to the reactor in such an amount that the solvent fills the volume of the reactor to a level of at least 35% or more. In other words, the fraction of the solvent volume in the reactor volume is at least 35%, which means that at least 35% or more of the reactor volume is filled with solvent. The present inventors have found that a given amount of solvent provides better particle size control. In one embodiment, the solvent is added to the reactor in such an amount that the solvent fills the volume of the reactor to a level of no more than 80% or less. In other words, the proportion of solvent volume in the reactor volume is not more than 80%, which means that not more than 80% or less of the reactor volume is filled with solvent. If the filling volume is greater than this, then there is not enough space for other materials. In one embodiment, the solvent is added to the reactor in such an amount that the solvent fills the volume of the reactor to a level of no more than 70% or less. In other words, the proportion of solvent volume in the reactor volume is no more than 70%, which means that no more than 70% or less of the reactor volume is filled with solvent. In one embodiment, said mixing device is a propeller mixer 1 according to FIG. 1 and 2. As a rule, paddle mixers are used in the prior art, such as paddle mixer 100 according to FIG. 3. The inventors of the present invention have found that when using a different type of stirrer, the particle size of the solid support decreases.

A propeller agitator 1 that can be used in the present method comprises a propeller 2 having two propeller blades 3 extending in opposite directions from a central portion of the propeller 4, the central portion of which is connected to a drive shaft 5 of the propeller agitator 1. Looking in the axial direction 6, which means parallel to the central axis of rotation 7 of the propeller agitator 1, then the blades of the propeller 3 expand from the smaller end in the central part 4 towards the wider free end 9. The blades of the propeller 3 can be considered as having a sector-shaped shape, having a curved free end 9, also visible in the radial direction. Also, the blades of the propeller 3 are bent around a radial axis 8 perpendicular to the central axis 7 to form a helical propeller. As a result, the propeller blades 3, when used, create a force component parallel to the central axis 7 on the mixture, that is, transverse to the direction of rotation.

In other embodiments, the implementation of the propeller 2 may have one blade or may have more than two blades, for example, three or four blades. For example, each of the four blades may be provided at an angle of 90° relative to adjacent blades. The propeller agitator 1 may further comprise more than one propeller 2, for example two propellers 2, 2' spaced apart along a drive shaft 5, as is the case with the paddle agitator 1' shown in the example of FIG. 5. Agitator 1' is identical to agitator 1 except for the additional propeller 2'. In the case of more than one propeller 2, the propeller blades of the first propeller of the agitator may be oriented at an angle relative to the propeller blades of the second propeller of the agitator, as viewed in the axial direction 6 of the propeller agitator 1. The upper propeller blades 2' of the agitator blade 1' of FIG. 5 are located at an angle of 90° relative to the blades of the lower propeller 2. In the example of FIG. 5 stirrer 1 can be used instead of stirrer 1'.

This is in contrast to the paddle agitator 100 used in the prior art, which is shown in FIG. 3. Such prior art paddle agitator 100 comprises a flat blade 102 extending in a vertical plane with opposite parts of the paddle 103 on both opposite sides of the vertical central axis of rotation 107 of the agitator 100. The paddle agitator has a drive shaft 105. The agitator flat blade 102 100 used in Examples 5 and 8 has the shape of an arc of a circle and has a lower central part 104 and higher free opposite ends 109.

In FIG. 5 shows a cylindrical reactor 60 containing a reactor vessel 61. FIG. 5 shows only the lower part of the reactor vessel 61; the lid for closing the tank on the top side is not shown. In one embodiment, the reactor 60 has not only a stirrer 1', but also one or more baffles 50 (eg, two baffles 50). Such baffles 50 are located on the inner wall 62 of the reactor vessel 61. The inventors of the present invention have found that by using these baffles the particle size of the solid support is reduced.

Baffles 50, also shown in FIG. 4, which can be used in accordance with the present invention, are plate-shaped and project radially inward from the inner wall 62 of the reactor vessel 61. The baffles also extend in the vertical direction 6 of the reactor. In the case of a cylindrical reactor, as shown in FIG. 5, the baffles are formed by rectangular plates 52 extending in the radial and longitudinal directions, i. e. in the vertical direction of the cylindrical reactor. The baffles 50 are designed to leave a gap between the baffles 50 and the agitator, such as the agitator 1', for example at least 2 mm or 4 mm. Two baffles 50 are inside the reactor 60 at an angle of 180° relative to each other. In another embodiment, no baffles may be present within the reactor, or more than two baffles may be present, for example, n baffles may be present at 360/n degrees relative to each other. Each of the baffles 50 has a rod 51 for installation in the reactor tank 61. In other embodiments, the baffles may be attached to the inner wall of the reactor tank without the use of such rods.

The mixing rate depends, for example, on the size of the reactor. The mixing rates refer to the reactor when dosing the Grignard reagent and the silane compound. Preferably, the pre-mixing of the Grignard reagent and the silane compound is carried out, for example, in a mini-mixer. In one embodiment, this is done at a low temperature (e.g. below 15 or even below 10° C., e.g. 5° C.) and in a very short residence time in the mini-stirrer, e.g. less than 1 minute or even less than 30 seconds, such as , 18-20 s. Due to the low temperature and short mixing time, there is very limited reaction of these two components before they are added to the reactor. For a laboratory (0.5 to 2.0 liter, eg 1.5 liter) reactor, preferred initial mixing rates are 380 to 500 rpm, preferably 400 to 480 rpm. For a laboratory reactor, the preferred final mixing speeds are from 500 to 700 rpm, preferably from 530 to 630 rpm. Examples 1-4 below were carried out on a laboratory scale (1.5 L reactor) and the initial mixing speed was 400 rpm (examples 1 and 2), 420 rpm (example 3) and 470 rpm (example 4) , and the final mixing speed in the dosing step was 550 rpm (examples 1, 2 and 3) and 570 rpm (example 4). Example 5 had an initial mixing speed of 350 rpm and a final mixing speed of 460 rpm. For a pilot scale reactor (10 to 30 L, eg 16 L), the initial mixing speed is preferably 200 to 400 rpm, preferably 250 to 380 rpm. For a pilot scale reactor, preferred final mixing rates are 400 to 600 rpm, preferably 430 to 580 rpm. Examples 6 and 7 are carried out on a semi-industrial scale with initial mixing speeds of 280 rpm (example 6) and 360 rpm (example 7) and final mixing speeds of 460 rpm (example 6) and 560 rpm (example 7). Example 8

- 7 041560 had an initial mixing speed of 130 rpm and a final mixing speed of 180 rpm. For a full scale reactor (100 to 6000 L, preferably 1000 to 6000 L, eg 2500 L), the initial mixing speed is preferably 30 to 150 rpm, preferably 40 to 140 rpm. For a full scale reactor, preferred final mixing rates are 150 to 250 rpm, preferably 160 to 230 rpm. In a preferred embodiment, the initial mixing speed is 30 to 450 rpm, preferably 100 to 400 rpm. In a preferred embodiment, the final mixing speed is 150 to 750 rpm, preferably 450 to 600 rpm.

In one embodiment, a substrate having a spread value of 0.2 to 0.9, preferably 0.3 to 0.6, is obtained using the present invention. The inventors of the present invention have found that by using this type of mixing with mixing speed differentiation, the particle size of the solid support is reduced. By increasing the mixing speed (initial mixing speed and/or final mixing speed), the particle size is reduced. If only the initial mixing speed is increased, the particle size decreases. In the event that both the initial and final mixing speeds are reduced, the particle size is further reduced.

Several other embodiments of step 1b) are described in detail in WO 2015091984 A1, page 16, line 30 - page 22, line 25, the entire section of which is incorporated herein by reference. Preferably, butyl Grignard is used during step 1b).

Phase II Activation of said solid catalyst support (step 2).

This step of activating said solid catalyst support is an optional step that is not necessary but is preferred in the present invention. This phase may include one or more stages.

Step 2) refers to the activation of a solid magnesium compound, and this step, including many embodiments, is described in detail in WO 2015091984 A1 of the same applicant, page 23, line 3 - page 28, line 14, the entire section of which is incorporated herein through a link. In accordance with the present invention, the solid support and the procatalyst preferably have an average particle size (or APS) of 8-17 microns. Particle size is measured using an analytical method based on ASTM standard analytical method according to D4464-201.

Step 2) optionally involves contacting the solid support obtained in step 1) with at least one activating compound selected from the group formed by activating electron donors and metal alkoxide compounds of the formula M ¹ (OR ² )vw(OR ³ )w or M ² (OR ² )v_w(R ³ )w to give a second reaction intermediate; where: M ¹ is a metal selected from the group consisting of Ti, Zr, Hf, Al or Si; M ² is a metal which is Si; v represents the valency of M ¹ or M ² , and w<v, such as 0, 1 or 2; each of R ² and R ³ is a linear, branched or cyclic hydrocarbon group independently selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups and one or more combinations thereof; where the specified hydrocarbon group may be substituted or unsubstituted, may contain one or more heteroatoms and preferably contains from 1 to 20 carbon atoms. Preferably, an alcohol such as methanol or ethanol is used as the activating electron donor, with ethanol being more preferred. Preferably, a compound is used as the metal alkoxide, where M ¹ = Ti, w = 0; R ² = ethyl, i.e. titanium tetraethoxide (TET). In a preferred embodiment, a combination of both an activating electron donor and a metal alkoxide compound is used, i. TET and ethanol. In one embodiment, step 2) involves two activation steps, wherein the first activation step uses an activating electron donor and a metal alkoxide compound of the formula M1(OR ² )v_w(OR ³ )w, preferably methanol or ethanol, most preferably ethanol as an activating electron donor; and titanium tetraethoxide (TET) as a metal alkoxide compound. Ethanol is preferred over methanol due to the toxicity of methanol.

Phase III. Obtaining a pro-catalyst.

Step 3) comprises reacting the first or second reaction intermediate obtained in step 1) or 2), respectively, with a halogenated Ti compound, an activator, and at least one internal electron donor. This phase can be carried out in one or more sub-steps.

An example of an embodiment involving multiple sub-steps includes:

3-I) in the first step: contacting the first or second reaction intermediate obtained in step 1) or 2, respectively, with a halogenated Ti compound, an activator and optionally a portion of an internal electron donor;

3-II) in the second step: contacting the product obtained in step 3-I) with a halogenated Ti compound and optionally a portion of an internal electron donor;

3-III) in the third step: contacting the product obtained in step 3-II) with a halogenated Ti compound and optionally a portion of an internal electron donor;

3-IV) optionally in a fourth step: contacting the product obtained in step 3III) with a halogenated Ti compound and optionally a portion of an internal electron donor;

wherein preferably said internal electron donor is added in at least two portions during at least two of steps 3-I, 3-II, 3-III and 3-IV to form said procatalyst.

This phase III, also referred to as phase D, is described in detail in WO 2015091984 A1 of the same applicant, page 28, line 15 - page 31, line 13, the entire section of which is incorporated herein by reference.

Phase III may include several stages (eg, I, II and III, and optionally IV). During each of these successive steps, the solid support is brought into contact with the catalytically active compound. In other words, the addition or reaction with said catalytic compound can be repeated one or more times. Preferably, the same catalytic compound is used in each step. Preferably, TiCl ₄ is used as catalytic compound in all steps of step 3). The catalyst particles can be added first, followed by the addition of the activator and/or donor at any of the steps.

A compound with catalytic activity.

Step 3) involves in all sub-steps reacting the solid (activated) support with a transition metal halide (eg titanium halide, chromium halide, hafnium halide, zirconium halide, vanadium halide), but preferably with a titanium halide, eg TiX ₄ , where X is chloride or fluoride, preferably chloride. Step 3 (also referred to as step iii) or step D) is described in detail in WO 2015091984 A1, page 29, line 28 page 31, line 13, the entire section of which is incorporated herein by reference.

Activator.

The activator is added during step 3). The molar ratio of activator to magnesium can vary within wide limits, for example from 0.02 to 1.0. Preferably, this molar ratio is from 0.05 to 0.8, more preferably from 0.1 to 0.6 and most preferably from 0.1 to 0.5. In one embodiment, the activator is present during this step 3). Several types of activators can be used, such as benzamide, alkyl benzoates, and monoesters. Each of them will be discussed below.

The benzamide activator is characterized by the structure disclosed in WO 2015091983 A1 of the same applicant, page 13, line 13 - page 14, line 37, the entire section of which is incorporated herein by reference. The benzamide activator is characterized by a structure according to formula X.

*75

Each of R ⁷⁰ and R ⁷¹ is independently selected from hydrogen or alkyl. Preferably said alkyl contains from 1 to 6 carbon atoms, more preferably from 1 to 3 carbon atoms. More preferably, R ⁷⁰ and R ⁷¹ are each independently selected from hydrogen or methyl. Each of R ⁷² , R ⁷³ , R ⁷⁴ , R ⁷⁵ , R ⁷⁶ is independently selected from hydrogen, a heteroatom (preferably a halide), or a hydrocarbon group selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl, or alkylaryl groups, and one or more combinations thereof . Said hydrocarbon group may be linear, branched or cyclic. Said hydrocarbon group may be substituted or unsubstituted. Said hydrocarbon group may contain one or more heteroatoms. Preferably said hydrocarbon group contains 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, even more preferably 1 to 6 carbon atoms.

Suitable non-limiting examples of benzamides include benzamide (both R ⁷⁰ and R ⁷¹ are hydrogen and each of R ⁷² , R ⁷³ , R ⁷⁴ , R ⁷⁵ , R ⁷⁶ is hydrogen), also designated BA-2H, or methyl benzamide (R ⁷⁰ is hydrogen; R ⁷¹ is methyl and each of R ⁷² , R ⁷³ , R ⁷⁴ , R ⁷⁵ , R ⁷⁶ is hydrogen), also denoted as BA-HMe, or dimethylbenzamide (R ⁷⁰ and R ⁷¹ are methyl and each of R ⁷² , R ⁷³ , R ⁷⁴ , R ⁷⁵ , R ⁷⁶ is hydrogen), also referred to as BA-2Me. Other examples include monoethylbenzamide, diethylbenzamide, methylethylbenzamide, 2-(trifluoromethyl)benzamide, N,N-dimethyl-2-(trifluoromethyl)benzamide, 3-(trifluoromethyl)benzamide, N,N-dimethyl-3-(trifluoromethyl)benzamide, 2 ,4-dihydroxy-N-(2-9041560 hydroxyethyl)benzamide, N-(III-benzotriazol-1-ylmethyl)benzamide, 1-(4-ethylbenzoyl)piperazine, 1benzoylpiperidine.

Without being limited to a particular theory, the inventors of the present invention believe that the fact that the most active activation is achieved if the benzamide activator is added during step I has the following explanation. It is believed that the benzamide activator will bind the catalytically active compound and then be replaced by the internal donor when the internal donor is added.

A detailed description regarding the use of monoesters as activators can be found in WO 2015091984 A1 of the same applicant, page 42, line 12 - page 43, line 24, a section of which is incorporated herein by reference. A detailed description regarding the use of alkyl benzoates as activators can be found in WO 2015091984 A1 of the same applicant, page 42, lines 1-12, a section of which is incorporated herein by reference. The activating agent is, for example, selected from the group consisting of butyl formate, ethyl acetate, amyl acetate, butyl acetate, ethyl acrylate, methyl methacrylate, isobutyl methacrylate, alkyl benzoate such as ethyl pmethoxybenzoate, methyl p-ethoxybenzoate, ethyl p-ethoxybenzoate, ethyl benzoate, methyl benzoate, propyl benzoate, ethyl p-chlorobenzoate, ethyl p-bromobenzoate, methyl p-toluate and ethyl naphtate; preferably ethyl acetate, ethyl benzoate, benzoyl chloride, ethyl p-bromobenzoate, n-propyl benzoate and benzoic anhydride, more preferably ethyl benzoate.

internal donors.

During step 3), an internal electron donor is also present. Mixtures of internal electron donors can also be used. Examples of internal electron donors are disclosed below. The molar ratio of internal electron donor to magnesium can vary within wide limits, for example from 0.01 to 0.75. Preferably, this molar ratio is from 0.02 to 0.5; more preferably 0.03 to 0.3. The internal donor may be added in one portion during one of steps I, II, III, or IV. The internal donor can also be added in separate portions, such as two portions, or three portions, or more. If the internal donor is added in two portions, then it can be added, for example, in steps I and II or in steps II and III. If the internal donor is added in three portions, then it can be added, for example, in steps I, II and III or in steps II, III and IV.

In one embodiment, a carbonate-carbamate compound according to formula A is used as an internal donor.

where R ⁸¹ , R ⁸² , R ⁸³ , R ⁸⁴ , R ⁸⁵ and R ⁸⁶ are the same or different and independently selected from the group consisting of hydrogen or a linear, branched or cyclic hydrocarbon group selected from alkyl, alkenyl, aryl, aralkyl or alkylaryl groups and one or more combinations thereof, preferably containing from 1 to 20 carbon atoms; R ⁸⁷ represents hydrogen or a linear, branched or cyclic hydrocarbon group selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups and one or more combinations thereof, preferably containing from 1 to 20 carbon atoms; each group R ⁸⁰ independently represents a linear, branched or cyclic hydrocarbon group selected from alkyl, alkenyl, aryl, aralkyl or alkylaryl groups and one or more combinations thereof, preferably containing from 1 to 30 carbon atoms; R ⁸⁰ is preferably selected from the group consisting of alkyl having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably methyl, ethyl, n-propyl, isopropyl , n-butyl, 2-butyl, tert-butyl, pentyl or hexyl, most preferably ethyl. N represents a nitrogen atom; O represents an oxygen atom; and C represents a carbon atom; preferably 4[(ethoxycarbonyl)(methyl)amino]pentan-2-ylethylcarbamate (AB-OEt). More information about this internal electron donor and several embodiments can be found in WO 2015/185489, which is incorporated herein by reference. The preparation of this donor is disclosed in WO 2015/185489, Example A, which is incorporated herein by reference. More information about this internal electron donor and several embodiments can be found in WO 2015/185489, which is incorporated herein by reference. The preparation of this donor is disclosed in WO 2015/185489, Example A, which is incorporated herein by reference.

In one embodiment, an aminobenzoate compound according to formula B is used as an internal donor.

where each group R ⁹⁰ independently represents a substituted or unsubstituted aromatic group; each R ⁹¹ , R ⁹² , R ⁹³ , R ⁹⁴ , R ⁹⁵ , R ⁹⁶ and R ⁹⁷ are independently the same or different and are independently selected from the group consisting of hydrogen or a linear, branched or cyclic hydrocarbon group selected from alkyl, alkenyl, aryl, aralkyl or alkylaryl groups and one or more combinations thereof, preferably containing from 1 to 20 carbon atoms; wherein N is a nitrogen atom; O represents an oxygen atom; and C represents a carbon atom; preferably 4-[benzoyl(methyl)amino]pentan-2-ylbenzoate (AB). More information about this internal electron donor and several embodiments can be found in WO 2014/001257, which is incorporated herein by reference. The preparation of this donor is disclosed in WO 2014/001257, examples, which is incorporated herein by reference.

In one embodiment, the internal donor is a 1,3-diester represented by formula C

R ⁵¹

R53Q--CH ₂ ---with--- _CH2 --QR54

R52 where each of R ⁵¹ and R ⁵² is independently selected from hydrogen or a hydrocarbon group selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups and one or more combinations thereof, and where each of R ⁵³ and R ⁵⁴ independently represents a hydrocarbon group selected from, for example, alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl, or alkylaryl groups, and one or more combinations thereof. The specified hydrocarbon group R ⁵³ -R ⁵⁴ may be linear, branched or cyclic; it may be substituted or unsubstituted; it may contain one or more heteroatoms; it may contain 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, preferably 9,9-bis(methoxymethyl)fluorene (Flu). More information about this internal electron donor and several embodiments can be found in WO 2015/091983, which is incorporated herein by reference.

Socialization.

The catalyst system in accordance with the present invention provides co-catalyst. As used herein, the term cocatalyst is well known in the art of Ziegler-Natta catalysts and means a substance capable of converting a procatalyst into an active polymerization catalyst. Typically, the cocatalyst is an organometallic compound containing a metal from groups 1, 2, 12, or 13 of the Periodic Table of the Elements (Handbook of Chemistry and Physics, 70th Edition, CRC Press, 1989-1990). The cocatalyst may include any compounds known in the art as being useful as cocatalysts as described in WO 2015091984 A1 of the same applicant, page 59, line 1 - page 60, line 30, which is incorporated herein by reference.

External electron donor.

The catalyst system according to the present invention preferably contains an external electron donor. One of the functions of the compound, which is an external donor, is to influence the stereoselectivity of the catalyst system in the polymerization of olefins having three or more carbon atoms. Therefore, it can also be called a selectivity control. Examples of external donors suitable for use in the present invention are internal donors such as benzoic acid esters and 1,3-diesters. In addition, the following external donors can be used: alkylaminoalkoxysilanes, alkylalkoxysilanes, imidosilanes and alkylimidosilanes. The aluminum/external donor molar ratio in the polymerization catalyst system is preferably 0.1 to 200; more preferably 1 to 100. Mixtures of external donors may be present and may contain from about 0.1 mole % to about 99.9 mole % of the first external donor and from about 99.9 mole % to about 0.1 mol.% either the second or additional external donor based on alkoxysilane, disclosed below. If an external silane-based donor is used, then the molar ratio

- 11 041560

The Si/Ti in the catalyst system may range from 0.1 to 80, preferably from 0.1 to 60, even more preferably from 1 to 50, and most preferably from 2 to 30.

Documents EP 1538167 and EP 1783145 disclose a type of Ziegler-Natta catalyst containing an organosilicon compound as an external donor represented by the formula Si(OR ^c )3(NR ^d R ^e ), where R ^c is a hydrocarbon group containing from 1 to 6 carbon atoms, R ^d is a hydrocarbon group containing 1 to 12 carbon atoms, or is a hydrogen atom, and R ^e is a hydrocarbon group containing 1 to 12 carbon atoms, which is used as an external electron donor. Examples of suitable external donors in accordance with the present invention are known from WO 2015091984 A1 and are compounds according to formula III, alkylalkoxysilanes according to formula IV, organosilicon compounds characterized by the formula Si(OR ^a )4.nR ^b n, imidosilanes according to formula with formula I, alkylimidosilanes in accordance with formula I', described on page 61, line 26 - page 67, line 8, while the specified document is incorporated herein by reference. Alkoxysilane halides are used to prepare imidosilane and alkylimidosilane internal donors and they correspond to formula XXIVa, ZnSi(OR ¹¹ )4_n, and formula XXIVa, Z _n Si(OR ¹¹ ) ₄ . _n .m(R ¹² )m, respectively. In the alkoxysilane halide represented by formulas XXIVa and XXIVb, Z represents a halo group and more preferably a chloro group; n=1, 2 or 3; and m=1 or 2. Specific examples in relation to an external donor, taking into account formula I' in WO 2015091984 A1, are described in WO 2015091984 A1 of the same applicant, page 67, lines 9-22, which is incorporated herein by reference.

Additional compound(s) as an external donor according to the present invention may be one or more alkoxysilanes described in WO 2015091984 A1 of the same applicant, page 67, line 24 - page 69, line 4 , a section of which is incorporated herein by reference. In one embodiment, the silane compound as an additional external donor is dicyclopentyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, methylcyclohexyldimethoxysilane, n-propyltrimethoxysilane, npropyltriethoxysilane, dimethylaminotriethoxysilane, and one or more combinations thereof. Preferably the external donor is an alkylalkoxysilane according to formula IV (preferably n-propyltrimethoxysilane or n-propyltriethoxysilane), or cyclohexylmethyldimethoxysilane, or another dialkyldialkoxysilane.

catalytic system.

The present invention also relates to a process for preparing a catalyst system by bringing into contact a Ziegler-Natta type procatalyst, a cocatalyst, and optionally one or more external electron donors. The procatalyst, cocatalyst, and external donor(s) may be brought into contact in any manner known to the person skilled in the art; and as described herein, more specifically in the examples. The present invention further relates to a process for producing a polyolefin by contacting at least one olefin with a polymerization catalyst system containing a procatalyst according to the present invention. Preferably, the polyolefin obtained by using the catalyst system of the present invention is polypropylene. For example, the external donor in the catalyst system of the present invention may be complexed with the co-catalyst and mixed with the procatalyst (premix) prior to contacting the procatalyst and the olefin. An external donor can also be independently added to the polymerization reactor. The procatalyst, cocatalyst, and external donor may be mixed or otherwise combined prior to addition to the polymerization reactor. The contacting of the olefin with the catalyst system in accordance with the present invention can be carried out under standard polymerization conditions known to the person skilled in the art. See, for example, Pasquini, N. (ed.) Polypropylene handbook 2 ^nd edition, Carl Hanser Verlag Munich, 2005, chapter 6.2, and references cited therein.

polymerization method.

The polymerization process may be a gas phase polymerization process, a slurry polymerization process, or a bulk polymerization process that is carried out in one or more reactors. One or more olefin monomers can be introduced into the polymerization reactor to react with a procatalyst to form an olefin-based polymer (or a fluidized bed or an agitated bed of polymer particles). Polymerization in suspension (liquid phase), as well as information about the polyolefins that are / can be obtained, are described in WO 2015091984 A1 of the same applicant, page 70, line 15, 10 - page 71, line 23, the section of which is incorporated herein by links; information on gas-phase polymerization methods is described in WO 2015091984 A1 of the same applicant, page 71, line 25 - page 72, line 26, which is incorporated herein by reference.

Olefin.

The olefin according to the present invention may be selected from mono- and diolefins containing from 2 to 40 carbon atoms; see also WO 2015091984 A1 of the same applicant, page 72, line 28 - page 73, line 5, a section of which is incorporated herein by reference. Preferably, the olefin is propylene or a mixture of propylene and ethylene, which provides a propylene-based polymer, such as a propylene homopolymer or a propylene-olefin copolymer. The olefin may be an alpha-olefin containing no more than 10 carbon atoms, such as ethylene, butene, hexene, heptene, octene.

Polyolefin.

The present invention also relates to a polyolefin, preferably polypropylene, obtained or obtained by a process comprising contacting an olefin, preferably propylene or a mixture of propylene and ethylene, with a procatalyst in accordance with the present invention. More information about the polymers obtained is disclosed in WO 2015091984 A1 of the same applicant, page 73, lines 6-23 and 25-34 and page 74, line 26 - page 75, line 24, the section of which is incorporated herein by reference in its entirety. The present invention also relates to a polyolefin, preferably a propylene-based polymer, obtained or obtained using the process described herein above, involving the contacting of propylene or a mixture of propylene and ethylene with a catalyst system in accordance with the present invention. In one embodiment, the present invention relates to the production of a polypropylene homopolymer. Several polymer properties are discussed in this document. The xylene soluble fraction (XS) is preferably from about 0.5 wt.% to about 10 wt.%, or from about 0.5 wt.% to about 8 wt.%, or from 1.0 to 6 wt.% . The productivity is preferably from about 1 kg/g/h to about 100 kg/g/h, or from about 20 kg/g/h to about 90 kg/g/h. The MFR is preferably from about 0.01 g/10 min to about 2000 g/10 min, or from about 0.01 g/10 min to about 1000 g/10 min; or from about 0.1 g/10 min to about 500 g/10 min, or from about 0.5 g/10 min to about 150 g/10 min, or from about 1 g/10 min to about 100 g/10 min.

The use of polyolefin.

The present invention also relates to the use of polyolefins, preferably propylene-based polymers (also referred to as polypropylenes) according to the present invention, in injection molding, blow molding, extrusion molding, injection molding, injection molding, thin wall injection molding etc., for example in food contact applications. In addition, the present invention relates to a molded article containing a polyolefin, preferably a propylene-based polymer, in accordance with the present invention. The polyolefin, preferably a propylene based polymer, according to the present invention can be formed into molded (semi)finished articles using a variety of processing techniques. Examples of suitable processing techniques include injection molding, injection molding, thin wall injection molding, extrusion, and extrusion injection molding. Injection molding is widely used to make products such as lids and closures, batteries, buckets, containers, car exteriors such as bumpers, car interiors such as dashboards, or car underhood parts. . Extrusion, for example, is widely used to produce products such as rods, sheets, films and pipes. Thin-wall injection molding, for example, can be used to implement thin-wall packaging applications for both food contact and non-food contact segments. They include buckets, and containers, and containers for oil and fat products / margarine, and glasses for dairy products.

The present invention is further described in detail using the following non-limiting examples.

Example 1

Stage A). Obtaining butyl Grignard.

A stirred flask equipped with a reflux condenser and funnel was filled with powdered magnesium (24.3 g). The flask was placed under a nitrogen atmosphere. Magnesium was heated at 80°C for 1 h, after which dibutyl ether (150 ml), iodine (0.03 g) and n-chlorobutane (4 ml) were added successively. After the disappearance of the color due to iodine, the temperature was raised to 80°C and a mixture of n-chlorobutane (105 ml) and dibutyl ether (830 ml) was added slowly over 2.5 hours. The reaction mixture was stirred for another 3 hours at 80°C . Stirring and heating were then stopped and a small amount of solid material was allowed to precipitate over 24 hours. By decanting the colorless solution above the precipitate, a butylmagnesium chloride solution was obtained at a concentration of 0.9 mol Mg/l.

Stage B). Preparation of the first reaction intermediate 350 ml of dibutyl ether were placed in a 1.5 l reactor. The reactor was equipped with a propeller stirrer. thermostatic reactor

- 13 041560 roll at 35°C. A solution of the reaction product from step A (480 ml, 0.432 mol Mg) and 240 ml of a solution of tetraethoxysilane (TES) in dibutyl ether (DBE) (48.2 ml of TES and 192 ml of DBE) were cooled to 5°C, and then simultaneously introduced in portions into a mixing device with a volume of 0.45 ml, equipped with a stirrer and a shirt. The duration of administration was 360 minutes. Thereafter, the premixed reaction product A and the TES solution were introduced into the reactor via a 0.25 ml connecting tube. The mixing device (mini-mixer) was cooled to 5° C. with cold water circulating in the mini-mixer jacket. The stirring speed in the minimixer was 1000 rpm. The stirring speed in the reactor was 400 rpm at the beginning of the introduction, and it was gradually increased to a value of 550 rpm at the end of the introduction stage. Upon completion of the introduction, the reaction mixture was heated to a temperature of 60°C and maintained at this temperature for 1 hour Then the stirring was stopped and the precipitation of a solid was ensured. The supernatant was removed by decanting. The solid was washed three times with 500 ml of heptane. This gave a pale yellow solid, reaction product B (first solid reaction intermediate; support), suspended in 200 ml of heptane. The average particle size of the substrate was 17.0 μm, and the spread value was (d ₉₀ -d ₁₀ )/d ₅₀ =0.5. Stage C). Preparation of the Second Reaction Intermediate A 250 ml glass flask equipped with a mechanical stirrer was filled under an inert nitrogen atmosphere at 20° C. with a slurry of 5 g of the reaction product from step B' dispersed in 60 ml of heptane. A solution of 0.88 ml of ethanol (EtOH/Mg=0.4) in 20 ml of heptane was added successively with stirring for 1 h. After keeping the reaction mixture at 20°C for 30 min, a solution of 0.79 ml of titanium tetraethoxide /Mg=0.1) in 20 ml of heptane for 1 h. The suspension was slowly heated to a temperature of no more than 30°C in 90 min and kept at this temperature for another 2 h. Finally, the supernatant was decanted from the solid reaction product (second reaction intermediate; activated support), which was washed once with 90 ml of heptane at 30°C.

Stage D). Obtaining a catalytic component.

The reactor was placed under a nitrogen atmosphere and 125 ml of titanium tetrachloride was added to it. A suspension containing approximately 5.8 g of activated support (step C) in 15 ml of heptane was added to the reactor with stirring. Then the temperature of the reaction mixture was raised to 110° C. over 60 minutes, and 2.0 ml of DnBP in 3 ml of heptane was added to the reactor, and the reaction mixture was kept at 115° C. for 90 minutes. The stirring was then stopped and the solids were allowed to settle. The supernatant was removed by decantation, after which the solid product was washed with chlorobenzene (125 ml) at 100°C for 20 min. The wash solution was then removed by decantation, after which a mixture of titanium tetrachloride (62.5 ml) and chlorobenzene (62.5 ml) was added. The reaction mixture was kept at 115°C for 30 min, after which the precipitation of a solid was ensured. The supernatant was removed by decanting and the last treatment was repeated once more. The obtained solid was washed five times with 150 ml of heptane while lowering the temperature from 60 to 25°C, after which a catalyst component suspended in heptane was obtained.

Stage E). polymerization of propylene.

Polymerization of propylene was carried out in a stainless steel reactor (with a volume of 0.7 l) in heptane (300 ml) at a temperature of 70°C, a total pressure of 0.7 MPa, and in the presence of hydrogen (55 ml) for 1 h in the presence of a catalytic system containing a catalytic component in accordance with stage D, triethylaluminum as a co-catalyst and cyclohexylmethyldimethoxysilane (CHMDMS) as an external donor. The concentration of the catalyst component was 0.033 g/l; the concentration of triethylaluminum was 4.0 mmol/l; the CHMDMS concentration was 0.2 mmol/L. The results are presented in the table.

Example 2

Example 1 was repeated except that in stage B the reactor was equipped with a propeller stirrer and an additional two baffles. This resulted in a substrate with an average particle size of 13.5 µm and a spread value of (d ₉₀ -d ₁₀ )/d ₅₀ = 0.66.

Example 3

Example 2 was repeated except that in step B, 420 ml dibutyl ether was added to the 1.5 liter reactor and the stirring speed in the reactor was 420 rpm at the start of the addition and was gradually increased to 550 rpm. At the end of the introduction phase. This resulted in a substrate with an average particle size of 12.9 µm and a spread value of (d ₉₀ -d ₁₀ )/d ₅₀ = 0.60.

Example 4

Example 3 was repeated, except that in step B, the stirring speed in the reactor was 470 rpm at the start of the injection, and it was gradually increased to 570 rpm at the end of the injection step. As a result, a substrate was obtained with an average particle size of 10.5 μm and a spread value of (d ₉₀ -d ₁₀ )/d ₅₀ =0.50.

Example 5

Example 5 was carried out similarly to example 1, except that in step B the reactor was equipped with a paddle agitator and the agitation speed in the reactor was 350 rpm at the beginning of the introduction, and it was gradually increased to a value of 500 rpm at the end. introduction stage. As a result, a support was obtained with an average particle size of 21 μm and a spread value of (d ₉₀ -d ₁₀ )/d ₅₀ = 0.30, and the activity of the catalyst obtained using this support was lower compared to the activities of catalysts with lower particle size (examples 1-4).

Example 6

Example 6 was carried out on a pilot scale in a 16 L reactor.

Stage A) obtaining butyl-Grignard was carried out using a procedure similar to the procedure of example 1, however, the total amount of reagents were: magnesium (260 g); n-chlorobutane (1070 ml); dibutyl ether (10.5 L); iodine (0.5 g). As a result, a solution of butylmagnesium chloride was obtained with a concentration of 0.86 mol Mg/l.

Stage B). Obtaining the first intermediate product of the reaction.

6.5 liters of dibutyl ether were placed in a 16 liter reactor. The reactor was equipped with a propeller stirrer and two baffles. The reactor thermostatically at 35°C. A solution of the reaction product from step A (5.44 L, 4.678 mol Mg) and 1700 ml of a solution of tetraethoxysilane (TES) in dibutyl ether (DBE) (522 ml of TES and 1178 ml of DBE) were cooled to 5°C, and then simultaneously introduced in portions into a mixing device with a volume of 5.6 ml, equipped with a stirrer and a jacket. The duration of administration was 340 min. Thereafter, the premixed reaction product A and the TES solution were introduced into the reactor via a 0.7 ml connecting tube. The mixing device (mini-mixer) was cooled to 5° C. with cold water circulating in the mini-mixer jacket. The stirring speed in the minimixer was 800 rpm. The stirring speed in the reactor was 280 rpm at the beginning of the introduction, and it was gradually increased to a value of 460 rpm at the end of the introduction stage. Upon completion of the introduction, the reaction mixture was heated to a temperature of 60°C and maintained at this temperature for 1 hour Then the stirring was stopped and the precipitation of a solid was ensured. The supernatant was removed by decantation. The solid was washed three times with 7.5 L of heptane. This gave a pale yellow solid, reaction product B (first solid reaction intermediate; support), suspended in 2 L of heptane. This resulted in a substrate with an average particle size of 13.5 μm and a spread value of (d ₉₀ -d ₁₀ )/d ₅₀ = 0.30. Steps C-E were carried out similarly to example 1.

Example 7

Example 7 was carried out similarly to example 6 in a 16 L reactor, however, in step B, 5 L of dibutyl ether was added to the reactor, and the stirring speed was 360 rpm at the start of the injection, and it was gradually increased to 560 rpm at the end of the injection step. As a result, a substrate was obtained with an average particle size of 9.0 μm and a spread value of (d ₉₀ -d ₁₀ )/d ₅₀ = 0.42.

Example 8

Example 8 was carried out similarly to example 7 in a 16 L reactor, except that in step B, the reactor was equipped with a paddle stirrer, 4 L of dibutyl ether was added to the reactor, and the stirring speed in the reactor was 130 rpm at the beginning of the introduction, and it was gradually increased to a value of 180 rpm at the end of the introduction stage. As a result, a substrate with an average particle size of 25.7 μm and a spread value of (d ₉₀ -d ₁₀ )/d ₅₀ = 0.70 was obtained, and the activity of the catalyst obtained using this substrate was lower compared to the activity values catalysts with a lower particle size value (examples 6-7). The results are shown in the table below.

Table. results

Example No. Obtaining a substrate Ti, cat., wt. % Yield PP, kg/g cat. XS, wt. % BD for PP, kg/m ³ MJMn Agitator type Partitions Mixing speed, rpm Reactor volume, l Substrate, µm scatter Volume fraction of solvent in volume PRLTIP 1 propeller - 400-550 1.5 17.0 0.50 23% 1.9 13.7 2.5 450 5.1 2 propeller + 400-550 1.5 13.5 0.66 23% 1.8 14.8 2.7 445 4.8 3 propeller + 420-550 1.5 12.9 0.60 28% 1.6 16.0 2.2 450 5.0 4 propeller + 470-570 1.5 10.5 0.50 28% 2.3 18.0 2.0 460 4.6 5 bladed 350-500 1.5 21.0 0.30 23% 1.9 12.5 2.4 450 5.2 6 propeller 4- 280-460 16 13.5 0.30 41% 2.3 18.2 2.0 480 4.3 7 propeller + 360-560 16 9.0 0.42 31% 2.4 17.4 2.0 470 4.5 8 bladed - 130-180 16 25.7 0.70 25% 1.8 12.7 1.8 450 5.1

The inventors of the present invention have unexpectedly found that support particles having a small particle size are obtained in accordance with the method of the present invention involving the synthesis of a support, which results in fine pronatalistic particles, which in turn leads to higher productivity values. or yield and bulk density of the polymer product. An additional unexpected feature of the present invention is that a product with a narrow molecular weight distribution (M _w /M _n ) is obtained using the support particles having a small size obtained in the present invention.

List of items

1. A method for obtaining a solid support for a procatalyst suitable for obtaining a catalyst

- 15 041560 tic composition for the polymerization of olefins, while the specified method of obtaining said solid support involves the reaction of the connection R ⁴ zMgX ⁴ 2-z, where each of R ⁴ independently represents a linear, branched or cyclic hydrocarbon group, independently selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups, and one or more combinations thereof; where the specified hydrocarbon group may be substituted or unsubstituted, may contain one or more heteroatoms and preferably contains from 1 to 20 carbon atoms; preferably R ⁴ is butyl;

each X ⁴ is independently selected from the group consisting of fluoride (F-), chloride (Cl-), bromide (Br-) or iodide (I-), preferably chloride;

z is in the range from more than 0 to less than 2, i.e. 0<z<2;

with a silane compound Si(OR ⁵ )4-n(R ⁶ )n, where each R ⁵ is independently a linear, branched or cyclic hydrocarbon group independently selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups and one or several combinations thereof; where the specified hydrocarbon group may be substituted or unsubstituted, may contain one or more heteroatoms and preferably contains from 1 to 20 carbon atoms;

each R ⁶ is independently a linear, branched or cyclic hydrocarbon group independently selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups and one or more combinations thereof; where the specified hydrocarbon group may be substituted or unsubstituted, may contain one or more heteroatoms and preferably contains from 1 to 20 carbon atoms;

n is in the range from 0 to 4, preferably n is from 0 to 1 inclusive;

in a solvent and mixing the resulting mixture using a mixing device and at a certain mixing speed to obtain a solid substrate Mg(OR1) _x X1 ₂ . _x where R ¹ is the same as R ⁵ ; each X ¹ is independently selected from the group consisting of fluoride (F-), chloride (Cl-), bromide (Br-) or iodide (I-), preferably chloride; and x is in the range from greater than 0 to less than 2, i. e. 0<x<2;

where the mixing starts from the initial mixing speed, and where the speed is increased to the final mixing speed, where the initial mixing speed is lower than the final mixing speed, preferably if the reaction is carried out in a laboratory reactor with a volume of from 0.5 l to 2.0 l, where the initial mixing speed is from 380 to 500 rpm, preferably from 400 to 480 rpm, and/or where the final mixing speed is from 500 to 700 rpm, preferably from 530 to 630 rpm.

2. A process for producing a solid support for a procatalyst suitable for producing a catalyst composition for the polymerization of olefins, said method for producing said solid support comprising reacting an R ⁴ zMgX ⁴ 2-z compound wherein each R ⁴ is independently linear, branched, or a cyclic hydrocarbon group independently selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups and one or more combinations thereof; where the specified hydrocarbon group may be substituted or unsubstituted, may contain one or more heteroatoms and preferably contains from 1 to 20 carbon atoms; preferably R ⁴ is butyl;

each X ⁴ is independently selected from the group consisting of fluoride (F-), chloride (Cl-), bromide (Br-) or iodide (I-), preferably chloride;

z is in the range from more than 0 to less than 2, i.e. 0<z<2;

with a silane compound Si(OR ⁵ )4-n(R ⁶ )n, where each R ⁵ is independently a linear, branched or cyclic hydrocarbon group independently selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups and one or several combinations thereof; where the specified hydrocarbon group may be substituted or unsubstituted, may contain one or more heteroatoms and preferably contains from 1 to 20 carbon atoms;

each R ⁶ is independently a linear, branched or cyclic hydrocarbon group independently selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups and one or more combinations thereof; where the specified hydrocarbon group may be substituted or unsubstituted, may contain one or more heteroatoms and preferably contains from 1 to 20 carbon atoms;

n is in the range from 0 to 4, preferably n is from 0 to 1 inclusive;

in a solvent, and mixing the resulting mixture with a mixing device and at a certain mixing speed to obtain a solid support Mg(OR1) _x X1 ₂ . _x where R ¹ is the same as R ⁵ ; each X ¹ is independently selected from the group consisting of fluoride (F-), chloride (Cl-), bromide (Br-) or iodide (I-), preferably chloride; and x is in the range from greater than 0 to less than 2,

-

Claims (3)

those. 0 < x < 2; where the mixing is started at an initial mixing speed, and where the speed is increased to a final mixing speed, where the initial mixing speed is lower than the final mixing speed, preferably if the reaction is carried out in a pilot scale reactor with a volume of 10 l to 30 l, where mixing is started with an initial mixing speed and where the speed is increased to a final mixing speed, where the initial mixing speed is lower than the final mixing speed, where preferably the initial mixing speed is from 200 to 400 rpm, preferably from 250 to 380 rpm, and/or where the final mixing speed is from 400 to 600 rpm, preferably from 430 to 580 rpm. 3. Method according to claim 1 or 2, where a mixing device with propeller blades is used. 4. Method according to claim 1 or 2 or 3, wherein a reactor with at least two baffles is used. CLAIM 1. A method for producing a procatalyst for producing a catalyst composition for the polymerization of olefins, said method comprising the steps of: step 1) - obtaining a solid support by reaction of the compound R ⁴ zMgX ⁴ 2_ _z , where each R ⁴ independently represents a linear, branched or cyclic hydrocarbon group independently selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups and one or several combinations thereof; where the specified hydrocarbon group contains from 1 to 20 carbon atoms, may be substituted or unsubstituted and optionally contains one or more heteroatoms; each X ⁴ is independently fluoride (F-), chloride (Cl-), bromide (Br-) or iodide (I-); z is in the range from more than 0 to less than 2, i.e. 0<z<2; with a silane compound Si(OR ⁵ )4_n(R ⁶ )n, where each R ⁵ is independently a linear, branched or cyclic hydrocarbon group independently selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl, or alkylaryl groups and one or more their combinations; where the specified hydrocarbon group contains from 1 to 20 carbon atoms, may be substituted or unsubstituted, and optionally contains one or more heteroatoms; each R ⁶ is independently a linear, branched or cyclic hydrocarbon group independently selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups and one or more combinations thereof; where the specified hydrocarbon group contains from 1 to 20 carbon atoms, may be substituted or unsubstituted and optionally contains one or more heteroatoms; n ranges from 0 to 4; in a solvent, and mixing the resulting mixture with a mixing device and at a certain mixing speed to obtain a solid support Mg(OR1) _x X1 ₂ _ _x , where R ¹ is the same as R ⁵ ; each X ¹ is independently fluoride (F-), chloride (Cl-), bromide (Br-) or iodide (I-); and x is in the range from greater than 0 to less than 2, i. e. 0<x<2; where the reaction is carried out in a full-scale reactor with a volume of 100 to 6000 liters, mixing starts at the initial mixing speed and the speed increases to the final mixing speed, while the initial mixing speed is lower than the final mixing speed, where the initial mixing speed is from 30 to 150 rpm, and the final mixing speed is from 160 to 230 rpm, where a mixing device with propeller blades is used and/or where a reactor with at least two baffles is used; and where the obtained specified solid substrate is characterized by an average particle size of not more than 17 microns; step 2) - contacting the solid support obtained in step 1) with at least one activating compound selected from the group formed by activating electron donors and metal alkoxide compounds of the formula M1(OR ² )v_w(OR ³ )w or M ² (OR ² )v_w(R ³ )w to give an intermediate reaction product; where M ¹ represents a metal selected from the group consisting of Ti, Zr, Hf, A1 or Si; M ² is a metal which is Si; v represents the valency of M ¹ or M ² , and w<v; each of R ² and R ³ is a linear, branched or cyclic hydrocarbon group independently selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups and one or more combinations thereof; where the specified hydrocarbon group contains from 1 to 20 carbon atoms, may be substituted or unsubstituted and optionally contains one or more heteroatoms; and step 3) - reaction of the solid support or reaction intermediate obtained in step 1) or 2), respectively, with a halogenated Ti compound, an activator and at least -