EA040104B1 - METHOD FOR PRODUCING PROCATALYST FOR OLEFIN POLYMERIZATION - Google Patents

Description

Prerequisites for the creation of the invention

The present invention relates to a process for the preparation of an olefin polymerization procatalyst containing an activator and an internal donor. The present invention also relates to said procatalyst obtained. In addition, 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. In addition, the present invention relates to a method for producing polyolefins by bringing at least one olefin into contact with the specified 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 good performance, in particular, improved productivity, bulk density and Mn (low oligomer content) and narrow MWD.

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 the preparation of a procatalyst suitable for the preparation of a catalyst composition for the polymerization of olefins, said process comprising the following steps:

step A) providing or obtaining a Grignard compound;

step B) bringing the Grignard compound into contact with an alkoxy or aryloxysilane compound to form a solid support;

step C) optionally bringing the resulting solid support into contact with at least one activating compound; and step D) reacting the (activated) support with a halogenated Ti compound as a catalytic compound, an activator, and at least one internal electron donor in several sub-steps, where the internal donor is added in portions during at least two of these steps to obtain procatalyst.

The first aspect of the present invention is 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 disclosed in claim 1 or 2 of the claims. This method involves the separate addition of an internal donor.

The second aspect of the present invention is presented in paragraph 13 or 14 of the claims. This method provides for a lower temperature during the addition of the activator and optionally an internal donor and/or provides for an increased mixing time during stages I and/or II of the titanation of stage D) of obtaining a procatalyst.

These aspects and embodiments will be described in more detail below.

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) .

- 1 040104

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 comprising 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, it may 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, for example R ₄ Mg _{3 Cl2} .

- 2 040104

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 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 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 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 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 are measured at a temperature of 230° C. under a load of 2.16 kg and are measured in accordance with ISO 1133:2005.

Unless otherwise indicated, when it is noted that any R group is independently selected from, 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. 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.

Detailed description of embodiments

Surprisingly, it has been found that the properties of the procatalyst can be improved by an improved method in accordance with the first or second aspects of the present invention.

The advantage of the present invention is to obtain a catalyst with high productivity. Another advantage is to provide an increased bulk density of the polyolefin. Another advantage is the narrower molecular weight distribution of the resulting polyolefin. Another advantage is the increased Mn (low oligomer content) and low xylene solubles content of the resulting polyolefin. Therefore, improved physical and mechanical product properties such as fibers, injection molded products and films are expected to be provided if such products are produced using the present invention.

As stated above, the first aspect of the present invention relates to a multi-stage process comprising steps A), B), C) and D), i.e. to 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 of: step A) providing or obtaining a Grignard compound; step B) bringing the Grignard compound into contact with an alkoxy or aryloxysilane compound to form a solid support; step C) optionally bringing the resulting solid support into contact with at least one activating compound; and also step D) carrying out the reaction of the (activated) support with the halogenated Ti compound as the catalytic compound, the activator and at least one internal electron donor

- 3 040104 thrones for several substages, where the internal donor is added in portions during at least two of these stages to obtain procatalyst. Each of these steps is described in more detail below. These steps are shown in claims 1 and 10 of the claims for the first and second aspects of the present invention.

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 202716 B1l. 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 A and stage B);

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

phase III): bringing said solid support obtained in phase I or said activated solid support obtained in phase II into contact with a catalytically active compound, an activator and at least one internal donor (step D);

and optionally phase IV): modification of said phase III intermediate, wherein phase IV may comprise one of the following: modification of said phase III intermediate with a Group 13 or transition metal modifier if an internal donor was used during phase III in order to obtain a pronatalistic; modifying said phase III intermediate with a Group 13 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 process for preparing a solid support for a procatalyst according to the present invention includes the following steps: step A) providing or obtaining a Grignard reagent; and step B) reacting the Grignard compound with the silane compound.

Step A) may include providing a previously prepared or commercially obtained Grignard reagent, or may include 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 in the range from more 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 from the same applicant, page 15, line 14 - page 16, line 28, the entire section of which is incorporated herein by reference.

Step B) involves bringing the compound R ⁴ zMgX ⁴ 2-z (where R ⁴ and X ⁴ are the same as above) into contact with the silane compound, Si(OR ⁵ )4_n(R ⁶ )n, to obtain the first intermediate product reaction, which is a solid Mg(OR ¹ )xX ¹ 2_ _x , where each of R ¹ , R ⁵ and R ⁶ is independently selected from 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; X ¹ 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. Preferably, tetraethoxysilane (TES; R ⁵ is ethyl and n = 0) is used during step B) as the silane compound to give Mg(OR ¹ )xX ¹ 2_x, where R ¹ is Et, and X ¹ is Cl. Step B), including many embodiments, is described in detail in WO 2015091984 A1, page 16, line 30 - page 22, line 25, the entire section of which is included in

- 4 040104 this document by reference. Preferably, butyl Grignard is used during step A).

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

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 C) refers to the activation of a solid magnesium compound, and this step, including many embodiments, is described in detail in WO 2015091984 A1 from the same applicant, page 23, line 3 - page 28, line 14, the entire section of which is included to this document by reference. In accordance with the present invention, the solid support and the procatalyst preferably have an average particle size (or APS) of 18-30 microns. Particle size is measured using an analytical method based on ASTM standard analytical method according to D4464-201.

Step C) optionally includes bringing the solid support obtained in step B) into contact 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 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 that is Si; v is the valency of M ¹ or M ² , and w < v, eg 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 C) comprises an activation step with 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 the activating electron donor and tetraethoxide titanium (TET) as a metal alkoxide compound. Ethanol is preferred over methanol due to the toxicity of methanol.

Phase III. Obtaining a pro-catalyst.

Step D) comprises reacting the first or second reaction intermediate obtained in step B) or C), respectively, with a halogenated Ti compound, with an activator and at least one internal electron donor, in several substeps:

D-I) in a first step bringing the first or second reaction intermediate obtained in step B) or C) respectively into contact with a halogenated Ti compound, with an activator and optionally with a portion of an internal electron donor;

D-II) in a second step, bringing the product obtained in step D-I) into contact with a halogenated Ti compound and optionally a portion of an internal electron donor;

D-III) in a third step, bringing the product obtained in step D-II) into contact with a halogenated Ti compound and optionally a portion of an internal electron donor;

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

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

This phase III, also referred to as phase D, is described in detail in WO 2015091984 A1 from 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 of 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 D). 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.

Stage D) includes in all substages the implementation of the reaction of a solid (activated) substrate

with a transition metal halide (eg titanium halide, chromium halide, hafnium halide, zirconium halide, vanadium halide), but preferably with a titanium halide, for example TiX ₄ where X is chloride or fluoride, preferably chloride. Stage D (also called stage III)) 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 D). 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 D). 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 from 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 the structure according to the formula X

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 of them. combinations. 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 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-(2hydroxyethyl)benzamide, N-(1H-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 from 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 from 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, an alkyl benzoate such as ethyl p-methoxybenzoate, methyl p-ethoxybenzoate, ethyl p-ethoxybenzoate, ethyl benzoate, methyl benzoate, propyl benzoate, ethyl pchlorobenzoate, ethyl p-bromobenzoate, methyl p-toluate and ethyl naphtate; preferably ethyl acetate, ethylben

- 6 040104 zoate, benzoyl chloride, ethyl p-bromobenzoate, n-propyl benzoate and benzoic anhydride, more preferably ethyl benzoate.

internal donors.

During step D), 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, 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, it can be added, for example, in steps I, II and III or steps II, III and IV.

In one embodiment, the internal electron donor is added in two portions, with the amount of internal donor divided between the two portions in a weight ratio of 80% : 20% to 20% : 80%, more preferably 60% : 40% to 40% : 60 %, most preferably about 50%:50%.

In one embodiment, the internal electron donor is added in three portions, with the amount of internal donor divided between the three given portions with a weight fraction of 20% to 40% for each portion, where the three portions add up to 100%, most preferably each portion is from 30 up to 35% of the total amount of the internal donor.

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

Formula A where R ⁸¹ , R ⁸² , R ⁸³ , R ⁸⁴ , R ⁸⁵ and R ⁸⁶ are 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; 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 by reference into this application. The preparation of this donor is disclosed in WO 2015/185489, example A, which is incorporated by reference into the present application.

In one embodiment, the activator is added during step I and the internal donor is added during steps II and III and optionally IV, preferably said activator is a monoester and the internal donor is a carbonate carbamate. In a specific embodiment, the EB activator is added during step I and AB-OEt is added during step II and step III. In a specific embodiment, the EB activator is added during step I and AB-OEt is added during steps II, III and IV.

In one embodiment, during step I of step D, EB is added as an activator, while during steps II, III, and IV, AB-OEt is added as an internal donor in three portions, each portion having a weight fraction of 30 to 35%, while three servings add up to 100%.

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In one embodiment, during step I of step D, EB is added as an activator, and during steps II and III, AB-OEt is added as an internal donor in two portions, with each portion represented in a weight ratio of 60%:40% up to 40%:60%, with two servings adding up to 100%.

More information about this internal electron donor and several embodiments can be found in WO 2015/185489, which is incorporated by reference into this application. The preparation of this donor is disclosed in WO 2015/185489, example A, which is incorporated by reference into the present application.

In a particular embodiment, butylmagnesium Grignard is used in step A), TES is used in step B), TET and ethanol are used in step C), TiCl ₄ is used as catalytic compound in all steps of step D); EB is used as an activator in step DI), AB-OEt is used as an internal donor in steps II and III. In a particular embodiment, butylmagnesium Grignard is used in step A), TES is used in step B), first in step C) TET and ethanol are used, and then ethanol is used in step C), TiCl4 is used as catalytic compound in all steps of step D); EB is used as an activator in step DI), AB-OEt is used as an internal donor in steps II and III. In a particular embodiment, butylmagnesium Grignard is used in step A), TES is used in step B), TET and ethanol are used in step C), TiCl ₄ is used as catalytic compound in all steps of step D); EB is used as an activator in step DI), AB-OEt is used as an internal donor in steps II, III and IV.

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

Formula B wherein each R ⁹⁰ group is independently 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 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 by reference into this application. The preparation of this donor is disclosed in WO 2014/001257, examples, which is incorporated by reference into the present application.

In one embodiment, the activator is added during step I and the internal donor is added during step III. In one embodiment, the activator is added during step I and the internal donor is added during steps II and III, and optionally IV. Preferably, said activator is a monoester and the internal donor is an aminobenzoate. In a specific embodiment, the EB activator is added during step I and AB is added during step III. In a specific embodiment, EB activator is added during step I and AB is added during steps II and III. In a specific embodiment, the EB activator is added during step I and AB is added during steps II, and III, and IV.

In one embodiment, during step I of step D), EB is added as an activator, and during steps II and III, AB is added as an internal donor in two portions, with each portion represented in a weight ratio from 60%:40% to 40%:60%, with two servings adding up to 100%.

In one embodiment, during step I of step D), EB is added as an activator, and during steps II, III, and IV, AB is added as an internal donor in three portions, each portion having a weight fraction of 30 to 35%, where the three servings add up to 100%.

In a particular embodiment, butylmagnesium Grignard is used in step A), TES is used in step B), TET and ethanol are used in step C), TiCl ₄ is used as catalytic compound in all steps of step D); EB is used as an activator for one hundred

- 8 040104 di DI), AB is used as an internal donor in stages II and III. In a particular embodiment, Grignard butylmagnesium is used in step A), TES is used in step B), TET and ethanol are first used in step C), TiCl ₄ is used as the catalytic compound in all steps of step D); EB is used as an activator in step DI), AB is used as an internal donor in step III. In a particular embodiment, butylmagnesium Grignard is used in step A), TES is used in step B), TET and ethanol are used in step C), TiCl4 is used as catalytic compound in all steps of step D); EB is used as an activator in step DI), AB is used as an internal donor in steps II and III. In a particular embodiment, butylmagnesium Grignard is used in step A), TES is used in step B), first in step C) TET and ethanol are used, and then ethanol is used in step C), TiCl4 is used as catalytic compound in all steps of step D); EB is used as an activator in step DI), AB is used as an internal donor in steps II, III and IV.

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

R ⁵¹

R ⁵³ O--CH ₂ ---s---CH ₂ --OR ⁵⁴

^R52

Formula C wherein R ⁵¹ and R ⁵² are each 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 wherein R ⁵³ and R ⁵⁴ are each independently is a hydrocarbon group selected, for example, from 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 by reference into this application.

In one embodiment, the activator is added during step I and the internal donor is added during step I, preferably said activator is a benzamide and the internal donor is a 1,3-diester. In a specific embodiment, the BA-2Me activator is added during step I and Flu is added during step I.

In one embodiment, the activator is added during step I and the internal donor is added during steps I and II, preferably said activator is a benzamide and the internal donor is a 1,3-diester. In a specific embodiment, the activator BA-2Me is added during step I and Flu is added during step I and step II.

In one embodiment, during step I of step D) BA-2Me is added as an activator, and during steps I and II, Flu is added as an internal donor in two portions, with each portion present in a weight ratio of 60%:40 % to 40%:60%, where two servings add up to 100%.

In a particular embodiment, butylmagnesium Grignard is used in step A), TES is used in step B), TET and ethanol are used in step C), TiCl4 is used as catalytic compound in all steps of step D); BA-2Me is used as an activator in steps D-I), Flu is used as an internal donor in steps I and II. In a particular embodiment, butylmagnesium Grignard is used in step A), TES is used in step B), TET and ethanol are first used in step C), TiCl4 is used as catalytic compound in all steps of step D); BA-2Me is used as an activator in steps D-I), Flu is used as an internal donor in steps I and II.

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 from the same applicant, page 59, line 1 - page 60, line 30, co

- 9 040104 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 to about 99.9 mole % of the first external donor and from about 99.9 to about 0.1 mole % of either the second or additional external donor based on alkoxysilane, disclosed below. If a silane-based external donor is used, the Si/Ti molar ratio 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 according to the 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_n} R ^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 halogen group and more preferably a chlorine group; n = 1, 2 or 3; 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 from the same applicant, page 67, line 922, which is incorporated herein by reference.

Additional compound(s) as an external donor in accordance with the present invention may be one or more alkoxysilanes described in WO 2015091984 A1 from 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, n-propyltriethoxysilane, 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.

In one embodiment of this aspect in step D-I) the temperature at which the contacting is carried out is -30°C to 120°C, or 0 to 100°C, or 10 to 60°C; and the contacting time is 10 to 150 minutes or 40 to 100 minutes. The resulting reaction mixture is then stirred at a temperature of 60 to 140°C or 90 to 120°C for a period of 10 to 150 minutes or 40 to 100 minutes; and the addition temperature during this first step is 0 to 40°C, or 20 to 30°C, or 25°C; in step D-II) the resulting reaction mixture is stirred at a temperature of 60 to 140°C or 90 to 120°C for a period of 10 to 150 minutes or 40 to 100 minutes; in step D-III) the resulting reaction mixture is stirred at a temperature of 60 to 140° C. or 90 to 120° C. for a period of 10 to 150 minutes, or 20 to 80 minutes; in step D-IV) the resulting reaction mixture is stirred at a temperature of 60 to 140°C or 90 to 120°C for a period of 10 to 150 minutes or 20 to 80 minutes.

A process for preparing a pronatalistic agent involving a low addition temperature and a longer mixing time in step D).

In another aspect, the present invention relates to 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

- 10 040104 stage A) providing connection R ⁴ zMgX ⁴ 2-z, where R ⁴ , X ⁴ and z are described above;

step B) bringing the compound R ⁴ zMgX ⁴ 2-z into contact with the silane compound, Si(OR ⁵ )4-n(R ⁶ )n, to obtain a first reaction intermediate which is solid Mg(OR ¹ )xX ¹ 2-x, where R ¹ , R ⁵ , R ⁶ , X ¹ , n, x and z are described above;

step C) optionally bringing the solid support obtained in step B) into contact with at least one activating compound selected from the group formed by activating electron donors and metal alkoxide compounds of formula M ¹ (OR2)vw(OR ³ ) w or M2(OR2) _vw (R ³ ) _w to form a second reaction intermediate; where M ¹ , M ² ; R ² , R ³ , and v and w are described above;

step D) carrying out the reaction of the first or second reaction intermediate obtained respectively in step B) or C), with a halogenated Ti compound, with an activator and at least one internal electron donor in several sub-steps:

D-I) in a first step, bringing the first or second reaction intermediate obtained respectively in step B) or C) into contact with a halogenated Ti compound, with an activator and optionally with an internal electron donor at a temperature of from -30°C to 120° C, preferably from 0 to 100°C, more preferably from 10 to 60°C, for a period of time from 10 to 150 minutes, preferably from 40 to 100 minutes, and then stirring the resulting reaction mixture at a temperature of 60 to 140 °C, preferably from 90 to 120°C, for a period of time from 10 to 150 minutes, preferably from 40 to 100 minutes; while preferably the temperature of addition during this first stage is from 0 to 40°C, more preferably from 20 to 30°C, for example 25°C;

D-II) in the second step, bringing the product obtained in step D-I) into contact with a halogenated Ti compound and optionally an internal electron donor, and stirring the resulting reaction mixture at a temperature of 60 to 140°C, preferably 90 to 120°C , over a period of time from 10 to 150 minutes, preferably from 40 to 100 minutes;

D-III) in the third step, bringing the product obtained in step D-II) into contact with a halogenated Ti compound and optionally an internal electron donor, and stirring the resulting reaction mixture at a temperature of 60 to 140° C., preferably 90 to 120 °C, over a period of time from 10 to 150 minutes, preferably from 20 to 80 minutes;

D-IV) optionally in a fourth step, bringing the product obtained in step D-III) into contact with a halogenated Ti compound and optionally an internal electron donor, and stirring the resulting reaction mixture at a temperature of 60 to 140° C., preferably 90 to 120°C, for a period of time from 10 to 150 minutes, preferably from 20 to 80 minutes;

to obtain the specified procatalyst.

In one embodiment, the temperature for adding the components during step I of step D) is 0 to 40°C, eg 20 to 30°C, eg 25°C.

In one embodiment, the mixture from step I of step D) is stirred at the addition temperature for a period of 10 to 150 minutes, preferably 20 to 100 minutes, such as 40 to 90 minutes, such as 60 minutes, after which the temperature is raised.

In a special embodiment of step D) during step I, the addition is carried out at a temperature of 20 to 30°C and then the resultant is stirred for a period of time from 40 to 90 minutes, then the temperature is raised to a value of 90 to 120°C and the resultant is then stirred for a period of 40 to 90 minutes; during step II, the components are added at a temperature of 90 to 120° C. and then stirred for a period of 40 to 80 minutes; during step III, the components are added at a temperature of 90 to 120° C. and then stirred for a period of 20 to 60 minutes; during step IV, the components are added at 90 to 120° C. and then mixed for a period of 20 to 60 minutes.

In a specific embodiment, when using a combination of BA-2Me and Flu, step I is carried out with the addition of BA-2Me at a temperature of 25°C, heating to a reaction temperature of 115°C, and stirring for a period of 60 minutes ; stage II is carried out at 115°C for 60 minutes, stage III at 115°C for 60 minutes and stage IV at 115°C for 30 minutes. In a particular embodiment, step I is carried out with the addition of BA-2Me at a temperature of 25°C, heating to a reaction temperature of 115°C, and stirring for a period of 60 minutes; stage II is carried out at 105°C for 60 minutes, stage III at 105°C for 30 minutes and stage IV at 105°C for 60 minutes.

In a specific embodiment, when using a combination of EB and AB-OEt, step I is carried out with the addition of EB at a temperature of 25°C, heating to a reaction temperature of 115°C, and stirring for a period of time of 90 minutes; stage II is carried out at 115°C for 60 minutes, stage III at 115°C for 30 minutes and stage IV at 115°C for 30 minutes.

In a specific embodiment, in the case of using a combination of EB and AB, step I is carried out with the addition of EB at a temperature of 25°C, heating is carried out to the temperature of the reaction

- 11 040104 ion, component 115°C, and stirred for a period of time constituting 90 min; stage II is carried out at 115°C for 60 minutes, stage III at 115°C for 30 minutes and stage IV at 115°C for 30 minutes.

In one embodiment of this aspect, step II) is carried out using ethanol as an activating electron donor. In one embodiment of this aspect, step II) is carried out using an activating electron donor and a metal alkoxide compound of the formula M1(OR ² )v_w(OR ³ )w in step II), preferably ethanol as the activating electron donor and tetraethoxide titanium (TET) as a metal alkoxide compound. In one embodiment of this aspect, the internal donor is added in at least two steps of step D) or three steps of step D).

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 independently also be added to the polymerization reactor. The procatalyst, cocatalyst, and external donor may be mixed or otherwise combined prior to addition to the polymerization reactor. Bringing the olefin into contact with the catalyst system in accordance with the present invention can be performed under standard polymerization conditions known to the person skilled in the art. See, for example, Pasquini, N. (ed.) Polypropylene handbook ^2nd edition, Carl Hanser Verlag Munich, 2005, ch. 6.2, as well as the links provided in this document.

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). Suspension polymerization (liquid phase), as well as information about the polyolefins that are / can be obtained, are described in WO 2015091984 A1 from the same applicant, page 70, line 15 10 - page 71, line 23, the section of which is included in this document by reference; information on gas phase polymerization methods is described in WO 2015091984 A1 from 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 from 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 α-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 bringing an olefin, preferably propylene or a mixture of propylene and ethylene, into contact with a procatalyst in accordance with the present invention. More information about the resulting polymers is disclosed in WO 2015091984 A1 from the same applicant, p. 73, lines 6-23 and 25-34 and p. 74, line 26 - p. links. The present invention also relates to a polyolefin, preferably a propylene-based polymer, obtained or obtained using the process described herein above, involving contacting 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 to about 10 wt.%, or from about 0.5 to about 8 wt.%, or from 1.0 to 6 wt.%. Pro

- 12 040104 productivity is preferably from about 1 to about 100 kg/g/h or from about 20 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 and so on, for example, in applications involving food contact. 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 tubes. 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.

Examples

Example 1 [not in accordance with the first aspect of the present invention; according to the second aspect of the present invention].

Stage A). Preparation of the Grignard reagent.

A 1.7 L flask equipped with a reflux condenser and funnel was filled with powdered magnesium (40.0 g, 1.65 mol). The flask was placed under a nitrogen atmosphere. Magnesium was dried at 80° C. for 2 hours under a nitrogen purge, after which dibutyl ether (200 ml), iodine (0.05 g) and n-chlorobutane (10 ml) were added successively and stirred at 120 rpm. The temperature was maintained at 80°C and a mixture of n-chlorobutane (146 ml) and dibutyl ether (1180 ml) was added slowly over 3 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 0.90 mol Mg/l.

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

Get the substrate.

A solution of the reaction product from step A (500 ml, 0.45 mol Mg) and 260 ml of a solution of tetraethoxysilane (TES) in dibutyl ether (DBE) (47 ml of TES and 213 ml of DBE) were cooled to 5°C and then fed simultaneously into the mixing device (mini-mixer) with a volume of 0.45 ml, equipped with a stirrer and a shirt. The mini mixer was cooled down to 5° C. with cold water circulating in the jacket of the mini mixer. The stirring speed in the mini mixer was 1000 rpm.

From the mixer, the mixed components were directly introduced into a 1.3 L reactor equipped with a paddle and containing 350 ml of dibutyl ether. The temperature of the introduction into the reactor was 35° C. and the duration of the introduction was 360 minutes. Upon completion of the introduction, the reaction mixture was heated to a temperature of not more than 60°C for 30 min and kept at this temperature for 1 h. 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 700 ml of heptane at a reactor temperature of 50° C. three times. A pale yellow solid, reaction product B (first solid reaction intermediate; support) was obtained after drying under a nitrogen purge. The average particle size of the substrate was 20 μm.

Stage C). Obtaining the second intermediate product of the reaction.

Underlay activation.

A 1000 ml glass flask equipped with a mechanical stirrer was filled under an inert nitrogen atmosphere at 20° C. with 50 g of reaction product B dispersed in 500 ml of heptane and stirred at 250 rpm. A solution of 2.7 ml of ethanol (EtOH/Mg=0.1) in 20 ml of

- 13 040104 heptane with stirring for 1 hour. After keeping the reaction mixture at 20°C for 30 minutes, a solution of 9.5 ml of titanium tetraethoxide (TET/Mg=0.1) in 20 ml of heptane was added over 1 hour.

The slurry was allowed to slowly warm to 30°C over a period of 30 minutes and kept at this temperature for another 2 hours. Finally, the supernatant was decanted from the solid reaction product (second reaction intermediate C; activated support), which washed once with 500 ml of heptane at 30°C and dried by purging with nitrogen.

Stage D). Obtaining pronatalistic A.

Stage I of obtaining pronatalistic.

The reactor with a volume of 300 ml, which is a flask for filtering, was introduced into a nitrogen atmosphere and 125 ml of titanium tetrachloride was added, then 5.5 g of the first activated substrate in 15 ml of heptane at 25°C was added to the reactor. Then, 0.89 g of K,K-dimethylbenzamide (molar ratio BA-2Me/Mg=0.15) in 4 ml of chlorobenzene was added to the reactor after 10 min, and 1.0 g of 9,9-bismethoxymethyl-9H-fluorene was added to the reactor (molar ratio Flu/Mg=0.1) in 3 ml chlorobenzene after 10 min. The temperature of the reaction mixture was raised to 100°C, and then the reaction mixture was stirred at 100°C for 60 minutes. The contents of the flask were filtered, after which the solid product was washed with chlorobenzene (125 ml) at a temperature of from 100 to 105°C for 20 min. The contents of the flask were then filtered.

Stage II obtaining pronatalistic.

A mixture of titanium tetrachloride (62.5 ml) and chlorobenzene (62.5 ml) was added to the reactor. The reaction mixture was stirred at 115°C for 60 min. The contents of the flask were then filtered.

Stage III obtaining pronatalistic.

A mixture of titanium tetrachloride (62.5 ml) and chlorobenzene (62.5 ml) was added to the reactor. The reaction mixture was stirred at 115°C for 60 min. The contents of the flask were then filtered.

Stage IV of obtaining pronatalistic.

A mixture of titanium tetrachloride (62.5 ml) and chlorobenzene (62.5 ml) was added to the reactor. The reaction mixture was stirred at 115°C for 30 min. The contents of the flask were then filtered.

Pronatalistic processing.

The resulting solid was washed five times with 125 ml of heptane, starting at 60° C., with stirring for 5 minutes per wash, after which it was filtered. During washings, the temperature was gradually lowered from 60 to 25°C. Finally, the obtained solid product was dried by blowing with nitrogen at a temperature of 25°C for 2 hours. The composition of the obtained solid procatalyst A is given in table. 1.

Example 2 [not in accordance with the first aspect of the present invention; according to the second aspect of the present invention].

Obtaining pronatalistic B.

Example 2 was carried out in the same way as example 1, except that steps II, III and IV of the preparation of the procatalyst were carried out at 105°C instead of 115°C. The composition of the obtained solid procatalyst B is given in table. 1.

Example 3 [in accordance with the first aspect of the present invention; according to the second aspect of the present invention].

Obtaining pronatalistic C.

Steps A)-C) are carried out in the same way as in example 1. Step D) was carried out as follows.

Stage I of obtaining pronatalistic.

The reactor with a volume of 300 ml, which is a flask for filtering, was introduced into a nitrogen atmosphere and 125 ml of titanium tetrachloride was added, then 5.5 g of the first activated substrate in 15 ml of heptane was added to the reactor. The contents of the reactor were stirred for 60 minutes at room temperature of 25°C. Then, 0.89 g of K,K-dimethylbenzamide (molar ratio BA-2Me/Mg = 0.15) in 4 ml of chlorobenzene was added to the reactor after 10 min, and 0.5 g of 9,9-bismethoxymethyl-9H-fluorene was added to the reactor (molar ratio Flu/Mg = 0.05) in 3 ml chlorobenzene after 10 min. The temperature of the reaction mixture was raised to 100°C, and then the reaction mixture was stirred at 100°C for 60 minutes. The contents of the flask were filtered, after which the solid product was washed with chlorobenzene (125 ml) at a temperature of from 100 to 105°C for 20 min. The contents of the flask were then filtered.

Stage II obtaining pronatalistic.

A mixture of titanium tetrachloride (62.5 ml) and chlorobenzene (62.5 ml) was added to the reactor. Then 0.5 g of 9,9-bis-methoxymethyl-9H-fluorene (molar ratio Flu/Mg = 0.05) in 3 ml of chlorobenzene was added to the reactor after 10 minutes. The reaction mixture was stirred at 115°C for 60 min. The contents of the flask were then filtered.

Stage III obtaining pronatalistic.

A mixture of titanium tetrachloride (62.5 ml) and chlorobenzene (62.5 ml) was added to the reactor. The reaction mixture was stirred at 115°C for 60 min. The contents of the flask were then filtered.

Stage IV of obtaining pronatalistic.

A mixture of titanium tetrachloride (62.5 ml) and chlorobenzene (62.5 ml) was added to the reactor. reactionary

- 14 040104 the mixture was stirred at 115°C for 30 minutes. The contents of the flask were then filtered.

Pronatalistic processing.

The resulting solid was washed five times with 125 ml of heptane, starting at 60° C., with stirring for 5 minutes per wash, after which it was filtered. During washings, the temperature was gradually lowered from 60 to 25°C. Finally, the obtained solid product was dried by blowing with nitrogen at a temperature of 25° C. for 2 hours. The composition of the obtained solid procatalyst C is shown in Table 1.

Example 4 [in accordance with the first aspect of the present invention; according to the second aspect of the present invention].

Obtaining pronatalistic D.

Example 4 was carried out in the same way as example 3, except that 0.7 g instead of 0.5 g of 9,9-bis-methoxymethyl-9H-fluorene was used in stage I of the procatalyst preparation and 0 .7 g instead of 0.5 g of 9,9-bis-methoxymethyl-9H-fluorene. The composition of the obtained solid procatalyst D is given in table. 1.

Example 5 [in accordance with the first aspect of the present invention; according to the second aspect of the present invention]

Obtaining pronatalistic E.

Stage A)-C) is carried out as in example 1. Stage D) was carried out as follows.

Stage I of obtaining pronatalistic.

The reactor with a volume of 300 ml, which is a filter flask, was introduced into a nitrogen atmosphere and 125 ml of titanium tetrachloride was added, then 5.5 g of the second activated substrate in 15 ml of heptane at 25°C was added to the reactor. Then 1.78 ml of ethyl benzoate, EB (EB/Mg = 0.30) in 4 ml of chlorobenzene was added to the reactor after 10 minutes. The temperature of the reaction mixture was raised to 115°C and then the reaction mixture was stirred at 115°C for 90 minutes. The contents of the flask were filtered, after which the solid product was washed with chlorobenzene (125 ml) at a temperature of from 100 to 105°C for 20 min. The contents of the flask were then filtered.

Stage II obtaining pronatalistic.

A mixture of titanium tetrachloride (62.5 ml) and chlorobenzene (62.5 ml) was added to the reactor. Then 0.60 g of 4-[(ethoxycarbonyl)(methyl)amino]pentan-2-yl-ethylcarbamate (AB-OEt/Mg = 0.06) in 4 ml of chlorobenzene was added to the reactor after 10 min. The reaction mixture was stirred at 115°C for 60 min. The contents of the flask were then filtered.

Stage III obtaining pronatalistic.

A mixture of titanium tetrachloride (62.5 ml) and chlorobenzene (62.5 ml) was added to the reactor. Then 0.48 g of 4-[(ethoxycarbonyl)(methyl)amino]pentan-2-yl-ethylcarbamate (AB-OEt/Mg = 0.05) in 4 ml of chlorobenzene was added to the reactor after 10 min. The reaction mixture was stirred at 115°C for 30 min. The contents of the flask were then filtered.

Stage IV of obtaining pronatalistic.

A mixture of titanium tetrachloride (62.5 ml) and chlorobenzene (62.5 ml) was added to the reactor. The reaction mixture was stirred at 115°C for 30 min. The contents of the flask were then filtered.

Pronatalistic processing.

The resulting solid was washed five times with 125 ml of heptane, starting at 60° C., with stirring for 5 minutes per wash, after which it was filtered. During washings, the temperature was gradually lowered from 60 to 25°C. Finally, the obtained solid product was dried by blowing with nitrogen at a temperature of 25° C. for 2 hours. 1.

Example 6 [in accordance with the first aspect of the present invention; according to the second aspect of the present invention].

Obtaining pronatalistic F.

Stage A)-C) is carried out as in example 1. Stage D) was carried out as follows.

Stage I of obtaining pronatalistic.

The reactor with a volume of 300 ml, which is a filter flask, was introduced into a nitrogen atmosphere and 125 ml of titanium tetrachloride was added, then 5.5 g of the activated once substrate in 15 ml of heptane at 25°C was added to the reactor. Then 1.78 ml of ethyl benzoate, EB (EB/Mg = 0.30) in 4 ml of chlorobenzene was added to the reactor after 10 minutes. The temperature of the reaction mixture was raised to 115°C and then the reaction mixture was stirred at 115°C for 90 minutes. The contents of the flask were filtered, after which the solid product was washed with chlorobenzene (125 ml) at a temperature of from 100 to 105°C for 20 min. The contents of the flask were then filtered.

Stage II obtaining pronatalistic.

A mixture of titanium tetrachloride (62.5 ml) and chlorobenzene (62.5 ml) was added to the reactor. Then 0.36 g of 4-[(ethoxycarbonyl)(methyl)amino]pentan-2-yl-ethylcarbamate (AB-OEt/Mg = 0.03) in 4 ml of chlorobenzene was added to the reactor after 10 min. The reaction mixture was stirred at 115°C for 60 min. The contents of the flask were then filtered.

- 15 040104

Stage III obtaining pronatalistic.

A mixture of titanium tetrachloride (62.5 ml) and chlorobenzene (62.5 ml) was added to the reactor. Then 0.36 g of 4-[(ethoxycarbonyl)(methyl)amino]pentan-2-yl-ethylcarbamate (AB-OEt/Mg = 0.03) in 4 ml of chlorobenzene was added to the reactor after 10 min. The reaction mixture was stirred at 115°C for 30 min. The contents of the flask were then filtered.

Stage IV of obtaining pronatalistic.

A mixture of titanium tetrachloride (62.5 ml) and chlorobenzene (62.5 ml) was added to the reactor. Then 0.36 g of 4-[(ethoxycarbonyl)(methyl)amino]pentan-2-yl-ethylcarbamate (AB-OEt/Mg = 0.03) in 4 ml of chlorobenzene was added to the reactor after 10 min. The reaction mixture was stirred at 115°C for 30 min. The contents of the flask were then filtered.

Pronatalistic processing.

The resulting solid was washed five times with 125 ml of heptane, starting at 60° C., with stirring for 5 minutes per wash, after which it was filtered. During washings, the temperature was gradually lowered from 60 to 25°C. Finally, the obtained solid product was dried by blowing with nitrogen at a temperature of 25° C. for 2 hours. 1.

Example 7 [not in accordance with the first aspect of the present invention; without correspondence with the second aspect of the present invention].

Obtaining pronatalistic G.

Step A'). The stage of formation of the Grignard reagent.

Preparation of the Grignard reagent.

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 (110 ml) and dibutyl ether (750 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 1.0 mol Mg/L butylmagnesium chloride solution was obtained.

Step B'). Obtaining the first intermediate product of the reaction.

Get the substrate.

This step was carried out as described in Example XX of EP 1222214 B1, except that the temperature of the introduction into the reactor was 35°C, the duration of the introduction was 360 minutes, and a stirrer was used. 250 ml of dibutyl ether were placed in a 1 liter reactor. Provided temperature control of the reactor at 35°C.

A solution of the reaction product from step A' (360 ml, 0.468 mol Mg) and 180 ml of tetraethoxysilane (TES) in dibutyl ether (DBE) solution (55 ml of TES and 125 ml of DBE) were cooled to 10°C and then simultaneously introduced into the mixing 0.45 ml device equipped with stirrer and jacket. From the mixing device, the mixed components were directly introduced into the reactor. The mixing device (mini-mixer) was cooled to 10° C. with cold water circulating in the jacket of the mini-mixer. The duration of administration was 360 minutes. The stirring speed in the mini-mixer was 1000 rpm.

Upon completion of the introduction, the reaction mixture was heated to a temperature of not more than 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 22 μm, and the range of values was (d90d10)/d50=0.5.

Step C'). Obtaining the second intermediate product of the reaction.

Underlay activation.

Support activation was carried out as described in Example IV of WO 2007134851 to give a 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 0.22 ml of ethanol (EtOH/Mg=0.1) in 20 ml of heptane was added successively with stirring for 1 h. After keeping the reaction mixture at 200°C for 30 min, a solution of 0.79 ml of titanium tetraethoxide (TET /Mg=0.1) in 20 ml of heptane for 1 hour.

The suspension was allowed to slowly heat up to a temperature of no more than 300°C over 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

- 16 040104 were washed once with 90 ml of heptane at 300°C.

Step D'). Obtaining a pro-catalyst.

Stage I of obtaining pronatalistic.

The reactor with a volume of 250 ml contribute to a nitrogen atmosphere and add 125 ml of titanium tetrachloride. The reactor is heated to 90° C. with stirring and a suspension containing approximately 5.5 g of activated support in 15 ml of heptane is added to it with stirring. Then K,K-dimethylbenzamide (molar ratio BA-2Me/Mg = 0.15) in 2 ml of chlorobenzene is added to the reactor. Then add 9,9-bis-methoxymethyl-9H-fluorene (molar ratio Flu/Mg = 0.1) in 2 ml of chlorobenzene. The reaction mixture was kept at 90°C for 60 min. A solid was allowed to precipitate and washed with 125 ml of chlorobenzene at 90° C. for 15-20 minutes. The solid was allowed to settle and was decanted.

Stage II obtaining pronatalistic.

Then a mixture of 62.5 ml of titanium tetrachloride and 62.5 ml of chlorobenzene was added to the reactor. The reaction mixture was kept at 90°C for 30 min with stirring. The solid was allowed to settle and was decanted.

Stage III obtaining pronatalistic.

Then a mixture of 62.5 ml of titanium tetrachloride and 62.5 ml of chlorobenzene was added to the reactor, the temperature of the reactor was set at 115°C. The temperature of the reaction mixture was maintained at 115°C and the reaction mixture was kept at 115°C for 30 minutes. The stirring was then stopped and the solids were allowed to settle. The supernatant was removed by decanting.

Stage IV of obtaining pronatalistic.

Then a mixture of 62.5 ml of titanium tetrachloride and 62.5 ml of chlorobenzene was added to the reactor, the temperature of the reactor was set at 115°C. The temperature of the reaction mixture was maintained at 115°C and the reaction mixture was kept at 115°C for 30 minutes. The stirring was then stopped and the solids were allowed to settle. The supernatant was removed by decantation.

Pronatalistic processing.

The obtained solid was washed five times with 100-150 ml of heptane at 60°C, after which the procatalyst suspended in heptane was obtained. The composition of the obtained solid procatalyst G is given in table. 1.

Example 8 [in accordance with the first aspect of the present invention; without correspondence with the second aspect of the present invention].

Obtaining pronatalistic H.

Steps A'), B') and C') were carried out as in example 7. Step D') was carried out as follows.

Step D'). Obtaining a pro-catalyst.

Stage I of obtaining pronatalistic.

The reactor was brought under a nitrogen atmosphere and 125 ml of titanium tetrachloride was added to it. The reactor was heated to 100° C. and a suspension containing approximately 5.5 g of activated support (step C')) in 15 ml of heptane was added to it while stirring. The temperature of the reaction mixture was then raised to 110°C over 10 min, and 1.76 g of ethyl benzoate (molar ratio EB/Mg = 0.3) in 2 ml of chlorobenzene was added to the reactor, and the reaction mixture was kept at 110°C for 60 min. 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 decanting.

Stage II obtaining pronatalistic.

Then a mixture of titanium tetrachloride (62.5 ml) and chlorobenzene (62.5 ml) was added. The reaction mixture was kept at 115°C. Then, 0.55 g of the internal donor, 4[(ethoxycarbonyl)(methyl)amino]pentan-2-ylethylcarbamate (molar ratio AB-OEt/Mg = 0.50), in 2 ml of chlorobenzene was added and stirred at 115°C for 60 min, after which the precipitation of the solid was ensured. The supernatant was removed by decantation.

Stage III obtaining pronatalistic.

Then a mixture of titanium tetrachloride (62.5 ml) and chlorobenzene (62.5 ml) was added. The reaction mixture was kept at 115°C. Then, 0.44 g of the resulting internal donor, 4[(ethoxycarbonyl)(methyl)amino]pentan-2-ylethylcarbamate (molar ratio AB-OEt/Mg = 0.40), in 2 ml of chlorobenzene was added and stirred at 115°C for for 30 min, after which the precipitation of the solid was ensured. The supernatant was removed by decantation.

Stage IV of obtaining pronatalistic.

Then 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 decantation.

Pronatalistic processing.

- 17 040104

The obtained solid was washed five times with 150 ml of heptane at 60°C, after which the procatalyst suspended in heptane was obtained.

The composition of the obtained solid procatalyst H is given in table. 1.

Polymerization of propylene using procatalysts A-H.

Polymerization in the liquid layer of propylene was carried out in a laboratory reactor with a volume of one gallon. The polymerization process involves heat treating the polymerization reactor at 110°C for 60 minutes, performing three nitrogen purges at high pressure (15 bar) at 110°C, then lowering the reactor temperature to 30°C while purging the reactor with nitrogen. The reactor was then purged three times with 50 g of propylene during each purge. Then, 1.375 kg of liquid propylene was introduced into the reactor, followed by the addition of hydrogen to the reactor at a pressure of 200 psig. from a 75 ml stainless steel cylinder. The reactor temperature was then raised to 62° C. and the stirring speed was set to 500 rpm. Then, 0.25 mmol of a pure external electron donor, which is cyclohexylmethyldimethoxysilane, was introduced into the reactor. Then, 2.0 mmol of triethyl aluminum cocatalyst was introduced into the reactor. Then, a procatalyst corresponding to 0.01 mmol Ti was introduced into the reactor. The reactor temperature was raised to 67° C., the stirring speed was increased to 1500 rpm, and the polymerization was carried out for 1 hour. After this period of time, propylene was vented from the reactor and a product was obtained which was polypropylene. Yield was determined after allowing the product to dry. The results of the analysis of polymerization and product are given in table. 2.

_________________________________________________________________________________Table 1

Cat. Etc. d50 [µm] Mg [%] Ti [%] ID ID [%] Activator Activator [%] EtO [%] A 1 19.17 16.78 2.17 Flu 15.45 BA-2Me 1.28 1.92 G 7 18.33 18.20 1.95 Flu 16.00 BA-2Me 1.24 2.90 IN 2 17.70 18.20 2.10 Flu 14.60 BA-2Me 0.87 2.50 WITH 3 17.78 18.10 1.79 Flu 17.70 BA-2Me 1.10 2.90 D 4 16.81 17.40 2.11 Flu 19.11 BA-2Me 0.86 2.33 E 5 20.55 19.00 1.82 AB-OEt 3.09 EB 0.92 2.70 H 8 17.48 14.77 2.09 AB-OEt 9.86 EB 0.70 2.40 F 6 21.95 21.73 2.29 AB-OEt 2.83 EB 1.02 2.75

table 2

Cat. Etc. Prod. [kg/g cat.] BD [kg/ ^m3 ] APS [mm] Dispersed substances [%] Mw [g/mol] Mp [g/mol] MWD MI [2.16 kg] XS [%] A 1 24.6 371 243607 55057 4.40 10.9 3.11 G 7 12.4 326 - - 193422 29176 6.63 - 2.50 IN 2 24.5 369 0.494 0.05 291000 54000 5.40 13.9 2.85 C 3 27.0 395 0.483 0.19 275401 65878 4.20 13.3 2.07 D 4 25.0 383 0.512 0.10 255456 57222 4.46 13.7 1.92 E 5 21.2 400 0.523 0.09 411556 82082 5.00 2.09 2.87 H 8 17.3 399 - - 405694 61216 6.63 - 3.34 F 6 22.5 401 0.502 0.24 385528 81882 4.65 2.92 3.14

The effect of lower temperature during the addition of donors during step I is noticeable when comparing examples 1-4 with example 7 (which is a comparative example). The performance of the catalyst more than doubled from 12.4 to 24.5 to 27.0. Bulk density increases from 326 to 369 to 395. MWD decreases from 6.63 to 4.20 to 5.40. Mn doubles from 29176 to 54000 to 65878, hence less oligomers are present. Thus, one or more of the objectives of the present invention is achieved: high catalyst productivity, high bulk density, narrow molecular weight distribution, high Mn (low oligomers) and low xylene solubles. Improved physical and mechanical properties of the product are expected, such as the properties of fibers, injection molded products, and films made with such products.

When comparing example 1 with example 7 (comparative), it can be seen that the low temperature of adding reagents in stage I of stage D (25°C in example 1 compared to 90°C in example 7), as well as the longer mixing time in stage II stages D (60 min in example 1 compared to 30 min in example 7) provide a doubling of productivity (from 12.4 to 24.6), an increase in bulk density (from 326 to 371), an increase in Mw and Mn and a decrease in MWD (from 6.63 to 4.40).

When comparing example 5 with example 8, it can be seen that the low temperature of addition of reagents in stage I of stage D) (25°C in example 5 compared to 100°C in example 8), as well as the longer mixing time in stage I of stage D) ) (90 min in example 5 compared to 60 min in example 8)

- 18040104 provide performance increase (from 17.3 to 21.2), more Mn (fewer oligomers) and narrower MWD (from 6.63 to 5.00) and lower XS (from 3.34 to 2 .87).

Moreover, it can be deduced from the present invention that, unexpectedly, temperature during the course of the process can be used to control product parameters such as MI, MWD and XS. It should be noted that the temperature in steps II, III and IV was lowered from 115°C in example 1 to 105°C in example 2. This provides the following. MWD is higher (5.4 compared to 4.4); MI is higher (13.9 compared to 10.6); and XS is lower (2.85 compared to 3.11).

Separate (eg, two or three times) addition of the internal donor improves incorporation of the internal donor into the catalyst form, which means significant savings associated with the use of the donor. This provides an increase in productivity, bulk density, MI and a decrease in XS. Also surprisingly, Mn is higher (fewer oligomers) when the internal donor is added separately.

Comparing example 3 (half Flu in step I and half Flu in step II) with example 1 (all Flu in step I, same total), the following effects can be seen. Productivity is higher (27.0 compared to 24.6); bulk density is higher (395 compared to 371); MI is higher (13.3 compared to 10.9); and XS is lower (2.07 compared to 3.11). Separate addition provides an increase in the inclusion of Flu in the catalyst from 15.45 to 17.7%.

When comparing example 6 (three times adding AB-OEt) with example 5 (two times adding AB-OEt), the following effects can be seen. Performance is slightly better (22.5 compared to 21.2); MI is higher (2.92 compared to 2.09); MWD is lower (4.65 compared to 5.00).

Surprisingly, the procatalyst of the present invention has been found to exhibit high procatalyst productivity, high bulk density, narrow molecular weight distribution, high Mn (low oligomers) and low xylene solubles. Improved physical and mechanical properties of the product are expected, such as the properties of fibers, injection molded products, and films made with such products. Therefore, one or more objects of the present invention have been achieved.

Claims (16)

CLAIM 1. A process for preparing a procatalyst suitable for preparing a catalyst composition for the polymerization of olefins, said process comprising the steps of: step A) providing or obtaining a compound having the formula R ⁴ zMgX ⁴ 2_ _z , where R ⁴ independently represents a linear, branched or cyclic hydrocarbon group selected from alkyl, alkenyl, aryl, aralkyl or alkylaryl groups and one or more combinations thereof; where the specified hydrocarbon group is substituted or unsubstituted and may contain one or more heteroatoms, and contains from 1 to 20 carbon atoms; 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; step B) bringing the compound R ⁴ zMgX ⁴ _{2_z} obtained in step A) into contact with the silane compound Si(OR ⁵ )4_n(R ⁶ )n to obtain a first reaction intermediate which is solid Mg(OR ¹ ) xX ¹ 2_ _x , where each of R ¹ , R ⁵ and R ⁶ independently represents a linear, branched or cyclic hydrocarbon group selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups and one or more combinations thereof; where the specified hydrocarbon group is substituted or unsubstituted and may contain one or more heteroatoms, and contains from 1 to 20 carbon atoms; X ¹ is independently fluoride (F ^- ), chloride (Cl ^- ), bromide (Br ^- ) or iodide (I ^- ); n ranges from 0 to 4; z is in the range from more than 0 to less than 2, i.e. 0 < z < 2; x is in the range from more than 0 to less than 2, i.e. 0<x<2; step D) carrying out the reaction of the first reaction intermediate obtained in step B), with a halogenated compound Ti, with an activator and at least one internal electron donor in several sub-steps: D-I) in a first step, bringing the first reaction intermediate obtained in step B) into contact with a halogenated Ti compound and with an activator; D-II) in a second step, bringing the product obtained in step D-I) into contact with a halogenated Ti compound; D-III) in the third step, bringing the product obtained in step D-II) into contact with halo - 19 040104 holding connection Ti; where each of said at least one internal electron donor is added in at least two portions during at least two of steps D-I), D-II) and D-III), to obtain said procatalyst. 2. A process for preparing a procatalyst suitable for preparing a catalyst composition for the polymerization of olefins, said process comprising the steps of: step A) providing or obtaining a compound having the formula R ⁴ zMgX ⁴ 2-z, where R ⁴ independently represents a linear, branched or cyclic hydrocarbon group selected from alkyl, alkenyl, aryl, aralkyl or alkylaryl groups and one or more combinations thereof; where the specified hydrocarbon group is substituted or unsubstituted and may contain one or more heteroatoms, and contains from 1 to 20 carbon atoms; 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; step B) bringing the compound R ⁴ zMgX ⁴ 2-z obtained in step A) into contact with the silane compound Si(OR ⁵ )4-n(R ⁶ )n to obtain a first reaction intermediate which is solid Mg( OR ¹ )xX ¹ 2-x, where each of R ¹ , R ⁵ and R ⁶ independently represents a linear, branched or cyclic hydrocarbon group selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups and one or more of them combinations; where the specified hydrocarbon group is substituted or unsubstituted and may contain one or more heteroatoms, and contains from 1 to 20 carbon atoms; X ¹ is independently fluoride (F ^- ), chloride (Cl ^- ), bromide (Br ^- ) or iodide (I ^- ); n ranges from 0 to 4; z is in the range from more than 0 to less than 2, i.e. 0 < z < 2; x is in the range from more than 0 to less than 2, i.e. 0<x<2; step C) bringing the first reaction intermediate obtained in step B) into contact with at least one activating compound formed by an activating electron donor and a metal alkoxide compound of the formula M ¹ (OR ² )vw(OR ³ )w or M ² (OR ² )vw(R ³ )w to give a second reaction intermediate; where M ¹ represents a metal Ti, Zr, Hf, Al or Si; M ² is a metal that is Si; v is a valence 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 is substituted or unsubstituted and may contain one or more heteroatoms, and contains from 1 to 20 carbon atoms; step D) carrying out the reaction of the second reaction intermediate obtained in step C), with a halogenated compound Ti, with an activator and at least one internal electron donor in several sub-steps: D-I) in a first step, bringing the second reaction intermediate obtained in step C) into contact with a halogenated Ti compound and with an activator; D-II) in a second step, bringing the product obtained in step D-I) into contact with a halogenated Ti compound; D-III) in the third step, bringing the product obtained in step D-II) into contact with a halogenated Ti compound; where each of the specified at least one internal electron donor is added in at least two portions during at least two of the steps D-I), D-II) and D-III) to obtain the specified procatalyst. 3. The method according to claim 1 or 2, in which X ⁴ is chloride; X ¹ is chloride; and/or n is from 0 to 1 inclusive. 4. The method according to any one of claims 1 to 3, further comprising in step D) a fourth step D-IV) bringing the product obtained in step D-III) into contact with a halogenated Ti compound and optionally a portion of an internal electron donor. 5. The method according to any one of the preceding claims, wherein the internal electron donor is added in two portions, wherein the amount of internal electron donor is divided between the two portions in a weight ratio of 80%:20% to 20%:80%, more preferably from 60%: 40% to 40%:60%, most preferably about 50%:50%. 6. The method according to any one of the preceding claims, wherein the internal electron donor is added in three portions, wherein the amount of internal electron donor is divided among the three given portions with a weight fraction of 20 to 40% for each portion, with the three portions totaling 100%, - 20 040104 most preferably each portion is from 30 to 35% of the total amount of internal to the hole. 7. The process according to any one of the preceding claims, wherein the activator is one of the following: i) a monoester selected from the group consisting of butyl formate, ethyl acetate, amyl acetate, butyl acetate, ethyl acrylate, methyl methacrylate, isobutyl methacrylate, ethyl p-methoxybenzoate, methyl- p-ethoxybenzoate, ethyl p-ethoxybenzoate, ethyl benzoate, methyl benzoate, propyl benzoate, ethyl pchlorobenzoate, ethyl p-bromobenzoate, methyl p-toluate and ethyl naphtate, or benzoyl chloride, or benzoic anhydride, preferably ethyl acetate, ethyl benzoate, benzoyl chloride, ethyl p-bromobenzoate, npropyl benzoate or benzoic anhydride, more preferably ethyl benzoate; or ii) benzamide according to formula X R ⁷⁵ where each of R ⁷⁰ and R ⁷¹ independently represents hydrogen or alkyl, and each of R ⁷² , R ⁷³ , R ⁷⁴ , R ⁷⁵ and R ⁷⁶ independently represents 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, preferably benzamide (BA or BA-2H) when R ⁷⁰ -R ⁷⁶ = H, N-methylbenzamide (BA-HMe) when R ⁷⁰ = Me, R ⁷¹ -R ⁷⁶ = H, or N,Ndimethylbenzamide (BA-2Me) when R ⁷⁰ , R ⁷¹ = Me, and R ⁷² -R ⁷⁶ = H. 8. A method according to any one of the preceding claims, wherein the internal electron donor is one of the following: i) carbonate-carbamate compound according to formula A where R ⁸¹ , R ⁸² , R ⁸³ , R ⁸⁴ , R ⁸⁵ and R ⁸⁶ are the same or different and independently represent hydrogen or a linear, branched or cyclic hydrocarbon group selected from alkyl, alkenyl, aryl, aralkyl or alkylaryl groups and one or several 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 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-2ylethylcarbamate (AB-OEt); or ii) an aminobenzoate compound according to formula B - 21 040104 where each group R ⁹⁰ independently represents a substituted or unsubstituted aromatic group; R ⁹¹ , R ⁹² , R ⁹³ , R ⁹⁴ , R ⁹⁵ , R ⁹⁶ and R ⁹⁷ are the same or different and independently represent 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); or iii) a 1,3-diester represented by formula C R ⁵¹ R ⁵³ O—sn ₂ ---s—sn ₂ OR ⁵⁴ R ⁵² where each of R ⁵¹ and R ⁵² independently represents 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 is a hydrocarbon group selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups and one or more combinations thereof; while 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 said 1,3-diester according to formula C is 9,9bis(methoxymethyl)fluorene (Flu). 9. The method according to any one of claims 1 to 8, wherein N,N-dimethylbenzamide is added as an activator during step I of step D) and 9,9-bis(methoxymethyl) is added as an internal electron donor during steps I and II )fluorene in two portions, with each portion present in a weight ratio of 60%:40% to 40%:60%, while the two portions add up to 100%. 10. The method according to any one of claims 1 to 8, wherein ethyl benzoate is added as an activator during step I of step D) and 4[(ethoxycarbonyl)(methyl)amino] is added as an internal electron donor during steps II and III pentan-2-ylethylcarbamate in two portions, each portion being present in a weight ratio of 60%:40% to 40%:60%, the two portions adding up to 100%, or where during step I of step D) as an activator ethyl benzoate is added, and moreover, during steps II, III and IV, 4-[(ethoxycarbonyl)(methyl)amino]pentan-2-ylethylcarbamate is added as an internal electron donor in three portions, each portion having a weight fraction from 20 to 40% , preferably from 30 to 35%, where the three servings add up to 100%. 11. The method according to any one of claims 1 to 8, wherein ethyl benzoate is added as an activator during step I of step D) and 4[benzoyl(methyl)amino]pentan- 2-ylbenzoate in two portions, with each portion present in a weight ratio of 60%:40% to 40%:60%, with the two portions adding up to 100%. 12. The process according to any one of the preceding claims, wherein step C) is carried out using an activating electron donor and a metal alkoxide compound of the formula M ¹ (OR ² )vw(OR ³ )w, preferably using ethanol as the activating electron donor and titanium tetraethoxide (TET) as a metal alkoxide compound. 13. A process for producing a pronatalistic for a catalyst composition intended for the polymerization of olefins, said process comprising the steps of: stage A) providing or obtaining the connection R ⁴ zMgX ⁴ 2-z, where R ⁴ independently represents a linear, branched or cyclic hydrocarbon group 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 and may contain one or more heteroatoms, and contains from 1 to 20 carbon atoms; X ⁴ is independently fluoride (F ^- ), chloride (Cl ^- ), bromide (Br ^- ) or iodide (I ^- ); - 22 040104 z is in the range from more than 0 to less than 2, i.e. 0 < z < 2; step B) bringing the compound R ⁴ zMgX ⁴ 2-z into contact with the silane compound Si(OR ⁵ )4-n(R ⁶ )n to obtain a first reaction intermediate which is a solid Mg(OR ¹ )xX ¹ 2- x, where each of R ¹ , R ⁵ and R ⁶ 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 and may contain one or more heteroatoms, and contains from 1 to 20 carbon atoms; X ¹ is independently fluoride (F ^- ), chloride (Cl ^- ), bromide (Br ^- ) or iodide (I ^- ); n ranges from 0 to 4; x is in the range from more than 0 to less than 2, i.e. 0<x<2; z is in the range from more than 0 to less than 2, i.e. 0 < z < 2; step D) carrying out the reaction of the first reaction intermediate obtained in step B), with a halogenated compound Ti, with an activator and at least one internal electron donor in several sub-steps: D-I) in the first step, bringing the first reaction intermediate obtained in step B) into contact with the halogenated Ti compound and the activator at a temperature of 0 to 40° C. for a period of 10 to 150 minutes, and then stirring the resulting reaction mixture at a temperature of 60 to 140° C. for a period of 10 to 150 minutes; D-II) in a second step, contacting the product obtained in step D-I) with a halogenated Ti compound and stirring the resulting reaction mixture at a temperature of 60 to 140° C. for a period of 10 to 150 minutes; D-III) in the third step, contacting the product obtained in step D-II) with a halogenated Ti compound and stirring the resulting reaction mixture at a temperature of 60 to 140° C. for a period of 10 to 150 minutes; where each of the specified at least one internal electron donor is added in at least two portions during at least two of the steps D-I), D-II) and D-III), to obtain the specified procatalyst. 14. A process for producing a pronatalistic for a catalyst composition intended for the polymerization of olefins, said process comprising the steps of: stage A) providing or obtaining the connection R ⁴ zMgX ⁴ 2-z, where R ⁴ independently represents a linear, branched or cyclic hydrocarbon group 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 and may contain one or more heteroatoms, and contains from 1 to 20 carbon atoms; 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; step B) bringing the compound R ⁴ zMgX ⁴ 2-z into contact with the silane compound Si(OR ⁵ )4-n(R ⁶ )n to obtain a first reaction intermediate which is a solid Mg(OR ¹ )xX ¹ 2- x, where each of R ¹ , R ⁵ and R ⁶ 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 and may contain one or more heteroatoms, and contains from 1 to 20 carbon atoms; X ¹ is independently fluoride (F ^- ), chloride (Cl ^- ), bromide (Br ^- ) or iodide (I ^- ); n ranges from 0 to 4; x is in the range from more than 0 to less than 2, i.e. 0<x<2; z is in the range from more than 0 to less than 2, i.e. 0 < z < 2; step C) bringing the first reaction intermediate obtained in step B) into contact with at least one activating compound formed by an activating electron donor and a metal alkoxide compound of the formula M ¹ (OR ² )vw(OR ³ )w or M ² (OR ² )vw(R ³ )w to give a second reaction intermediate; where M ¹ represents a metal Ti, Zr, Hf, Al or Si; M ² is a metal that is Si; v is a valence 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 is substituted or unsubstituted and may contain one or more heteroatoms, and contains from 1 to 20 carbon atoms; - 23 040104 stage D) carrying out the reaction of the second intermediate reaction product obtained in stage C), with a halogenated Ti compound, with an activator and at least one internal electron donor in several substages: D-Ι) in a first step, bringing the second reaction intermediate obtained in step C) into contact with a halogenated Ti compound and an activator at a temperature of 0 to 40° C. for a period of 10 to 150 minutes, and then stirring the resulting reaction mixture at a temperature of 60 to 140° C. for a period of 10 to 150 minutes; D-II) in the second step, bringing the product obtained in step D-I) into contact with a Ti halogen compound and stirring the resulting reaction mixture at a temperature of 60 to 140° C. for a period of 10 to 150 minutes; D-III) in the third step, contacting the product obtained in step D-II) with a halogenated Ti compound and stirring the resulting reaction mixture at a temperature of 60 to 140° C. for a period of 10 to 150 minutes; where each of the specified at least one internal electron donor is added in at least two portions during at least two of the steps D-I), D-II) and D-III), to obtain the specified procatalyst. 15. The method according to claim 13 or 14, in which X ⁴ is chloride; X ¹ is chloride; η is from 0 to 1 inclusive; the contact temperature in step D-I) is 0 to 40°C, preferably 20 to 30°C, for example 25°C; the contact period in step D-Ι) is 40 to 100 minutes; the stirring temperature in step D-I) is 90 to 120° C.; the mixing period in step D-I) is 40 to 100 minutes; the stirring temperature in step D-II) is 90 to 120° C.; the mixing period in step D-II) is 40 to 100 minutes; the stirring temperature in step D-III) is 90 to 120° C.; and/or the mixing period in step D-III) is 20 to 80 minutes. 16. The method according to any one of paragraphs. 13-15, further comprising in step D) fourth step D-IV) bringing the product obtained in step D-III) into contact with a halogenated Ti compound and optionally an internal electron donor, and stirring the resulting reaction mixture at a temperature of 60 to 140°C, preferably from 90 to 120°C, for a period of time from 10 to 150 minutes, preferably from 20 to 80 minutes.