Method for preparing main catalyst for olefin polymerization

Abstract

The present invention relates to a method for preparing a procatalyst suitable for preparing a catalyst composition for olefin polymerization, the method comprising the steps of: step A) providing or preparing a Grignard compound; step B) contacting the Grignard compound with a silane compound to produce a solid support; step C) activating the solid support to obtain an activated solid support, which comprises two sub-steps: step C1) contacting the solid support obtained in step B) with at least one first activating compound and a second activating compound; and step C2) a second activation step of contacting the partially activated solid support obtained in step C1) with an activating electron donor; and step D) reacting the activated solid support obtained in step C) with a halogen-containing Ti compound, optionally an activator, and at least one internal electron donor in several sub-steps to obtain the procatalyst. The present invention also relates to a procatalyst, a catalytic system comprising the procatalyst, a method for preparing polyolefins using the catalyst system, and the polyolefins obtained thereby.

Description

Background Art

[0001] The present invention relates to an improved method for preparing a procatalyst suitable for use in a catalyst system for olefin polymerization. The present invention also relates to the procatalyst obtained and a catalyst system comprising the procatalyst. In addition, the present invention relates to a method for producing polyolefins by contacting at least one olefin with the catalyst system. In addition, the present invention relates to a polymer obtained by polymerization using the procatalyst, and to a shaped article of the polymer. The present invention also relates to the use of toluene as a dispersant (and / or solvent) in the method for preparing the procatalyst.

[0002] Ziegler-Natta catalyst systems and their components suitable for preparing polyolefins are well known. An overview of this type of catalyst is provided, for example, by T. Pullukat and R. Hoff in Catal. Rev.-Sci. Eng. 41, Vol. 3 and 4, pp. 389-438, 1999. The preparation of this procatalyst is disclosed, for example, in WO 96 / 32427 A1.

[0003] An object of the present invention is to provide an improved process for preparing a procatalyst for olefin polymerization, in particular with improved environmental friendliness and reduced costs, but at the same time maintaining excellent performances. Summary of the Invention

[0004] At least one of the aforementioned objects of the present invention is achieved in the following aspects.

[0005] In a first aspect, the present invention relates to a method for preparing a procatalyst suitable for preparing a catalyst composition for olefin polymerization, the method comprising the steps of: step A) providing or preparing a Grignard compound; step B) contacting the Grignard compound with a silane compound to produce a solid support; step C) activating the solid support in a single activation step or in a double activation step to obtain an activated solid support; and step D) reacting the activated solid support obtained in step C) with a halogen-containing Ti compound, optionally an activator, and at least one internal electron donor to obtain the procatalyst.

[0006] Another aspect of the present invention is a procatalyst directly obtainable by the method according to the present invention. Another aspect of the present invention is a method for preparing a polyolefin, preferably a polypropylene, comprising contacting a procatalyst with an olefin and optionally an external donor and / or optionally a cocatalyst, or contacting a catalyst system comprising a procatalyst, an external donor, and a cocatalyst with an olefin. Another aspect of the present invention is a polyolefin, preferably a polypropylene, obtainable by the method. Another aspect is a shaped article. Another aspect is the use of toluene in a method for preparing a procatalyst. These aforementioned aspects and several embodiments thereof will be described in more detail below.

[0007] definition

[0008] The following definitions are used in this specification and claims to define the subject matter described. Other terms not mentioned below are intended to have meanings commonly understood in the art.

[0009] As used herein, "Ziegler-Natta catalyst" refers to a transition metal-containing solid catalyst compound comprising a catalytic substance supported on a metal or metalloid compound (eg, a magnesium compound or a silica compound).

[0010] As used in this specification, "catalytic material" means a transition metal-containing material comprising a transition metal halide selected from the group consisting of titanium halide, chromium halide, hafnium halide, zirconium halide and vanadium halide.

[0011] As used in this specification, "internal donor" or "internal electron donor" refers to an electron donating compound that contains one or more oxygen (O) and / or nitrogen (N) atoms.

[0012] As used herein, "external donor" or "external electron donor" refers to an electron donating compound used as a reactant in olefin polymerization, which contains at least one functional group capable of donating at least one pair of electrons to a metal atom.

[0013] As used herein, "activator" refers to an electron donating compound containing one or more oxygen (O) and / or nitrogen (N) atoms, which is used in the procatalyst synthesis process and is added before or simultaneously with the addition of the internal donor.

[0014] As used in this specification, "activating compound" refers to a compound used to activate the solid support before the solid support is contacted with a catalytic substance.

[0015] As used in this specification, "procatalyst" refers to the components of a catalyst composition, generally comprising an activated solid support, a transition metal-containing catalytic material, and one or more internal donors.

[0016] As used in this specification, "halide ion" or "halogen" means: a fluoride ion (F - ), chloride ion (Cl - ), bromide ion (Br - ) and / or iodide ions (I - ) ions.

[0017] As used in this specification, "heteroatom" means an atom other than carbon or hydrogen.

[0018] As used in this specification, "hydrocarbyl" means: a substituent containing hydrogen and carbon atoms, or a linear, branched or cyclic saturated or unsaturated aliphatic group, such as alkyl, alkenyl, diene and alkynyl; an alicyclic group, such as cycloalkyl, cycloalkadienyl, cycloalkenyl; an aryl group, such as a monocyclic or polycyclic aryl group, and combinations thereof, such as alkaryl and aralkyl. The hydrocarbyl group may be substituted with one or more non-hydrocarbyl substituents. A non-limiting example of a non-hydrocarbyl substituent is a heteroatom. An example is an alkoxycarbonyl group (i.e., a carboxylate group). When "hydrocarbyl" is used in this specification, it may also be a "substituted hydrocarbyl group" unless otherwise specified.

[0019] As used herein, "alkyl" means: an alkyl group is a functional group or side chain consisting of carbon and hydrogen atoms and having only single bonds. The alkyl group may be linear or branched, and may be unsubstituted or substituted.

[0020] As used herein, "aryl" means that the aryl group is a functional group or a side chain derived from an aromatic ring. The aryl group may be unsubstituted or substituted with a linear or branched hydrocarbon group.

[0021] As used in this specification, "alkoxide" or "alkoxy" refers to a functional group or side chain derived from an alkanol. It consists of an alkyl group bonded to a negatively charged oxygen atom.

[0022] As used herein, "aryl oxide" or "aryloxy" or "phenoxide" refers to a functional group or side chain derived from an aromatic alcohol. It consists of an aromatic group bonded to a negatively charged oxygen atom.

[0023] As used in this specification, "Grignard reagent" or "Grignard compound" refers to: 4 z MgX 4 2-z The compound or mixture of compounds (R 4 , z and X 4 as defined below under "Phase I") or it may be a complex with more Mg clusters, such as R 4 Mg3Cl2.

[0024] As used herein, "bulk density" or "BD" means the weight of a material per unit volume, including the voids inherent in the material being tested. Bulk density is measured as the apparent density according to ASTM D1895-96 Reapproved 2010-e1, Test Method A.

[0025] As used in this specification, "XS" or "xylene soluble fraction" means the weight percent (wt %) of the isolated polymer that is soluble in xylene, as measured according to ASTM D5492-10.

[0026] As used in this specification, "productivity" means: the amount in kg of polymer produced (product rate) / the number of grams of procatalyst consumed in the polymerization reaction per hour.

[0027] As used in this specification, "MFR" or "melt flow rate" is measured at a temperature of 230°C and a load of 2.16 kg, measured according to ISO 1133:2005.

[0028] Unless otherwise specified, when claiming that any R group is "independently selected from", this means that when there are several identical R groups in the molecule, they may have the same meaning or they may not have the same meaning. The present invention is described in more detail below. All embodiments described in relation to one aspect of the present invention may also be used for other aspects of the present invention, unless otherwise specified. DETAILED DESCRIPTION

[0029] Surprisingly, it has been found that the performance of the procatalyst can be improved by using toluene as a dispersant (and / or solvent) in step D of the process according to the improved process of the first aspect of the present invention. One advantage of the present invention of using toluene in step D of the process is that a higher internal donor incorporation rate is achieved. Another advantage is that the MFR of the polyolefin obtained is increased.

[0030] As mentioned above, a first aspect of the present invention relates to a multi-step process comprising steps A), B), C) and D) disclosed in the claims. Each of these steps is disclosed in more detail below.

[0031] The present invention also relates to the use of toluene as a dispersant (and / or solvent) in a method for preparing a procatalyst for olefin polymerization, the method comprising contacting a magnesium-containing support with a halogen-containing titanium compound and an internal electron donor, the toluene being used as a dispersant (and / or solvent) to increase the level of internal electron donor introduced into the procatalyst.

[0032] The present invention also relates to the use of toluene as a dispersant (and / or solvent) in a method for preparing a main catalyst for olefin polymerization, the method comprising contacting a magnesium-containing support with a halogen-containing titanium compound, an activator, and an internal electron donor, the toluene being used as a dispersant (and / or solvent) to increase the content of the activator introduced into the main catalyst and optionally to increase the content of the internal electron donor introduced into the main catalyst.

[0033] In one embodiment, the procatalyst is obtained by a method similar to that described in EP2027164B1, except that toluene is used in step D). Example 1 of EP2027164B1 (including all sub-embodiments (IA to IE)) is incorporated into this specification sheet. More details about different embodiments are disclosed in paragraphs

[0016] to

[0089] of EP2027164B1. All of these embodiments relating to these methods and products are incorporated into this specification sheet by reference. In the following part of the specification sheet, the different steps and stages of the method for preparing the procatalyst according to the present invention will be discussed. All of these embodiments of the method also relate to above-mentioned purposes.

[0034] The method for preparing the procatalyst according to the present invention comprises the following stages and steps:

[0035] Stage I): Preparation of a solid support for the procatalyst (step A) and step B);

[0036] Stage II): Activation of the solid support obtained in stage I using a single-step activation or a two-step activation with at least two activation steps (both using at least two activating compounds) to obtain an activated solid support (step C));

[0037] Stage III): said activated solid support obtained in stage II is brought into contact with a catalytic substance, optionally an activator and at least one internal donor (step D)).

[0038] Optionally, there may be a modification step using a modifying agent as stage IV, which is disclosed in EP 2 027 164 B1 and is incorporated into the present description.

[0039] The procatalyst thus prepared can be used for olefin polymerization using, for example, an external electron donor and a cocatalyst.The individual steps for preparing the catalyst according to the present invention are described in more detail below.

[0040] Stage I: Preparation of solid support for catalyst

[0041] This stage I comprises a step A) of providing or preparing a Grignard reagent and a step B) of reacting the Grignard reagent with a silane compound.

[0042] Step A) may include providing a previously prepared or commercially available Grignard reagent, or may include preparing a Grignard reagent. The Grignard reagent provided or prepared in step A) is compound R 4 z MgX 4 2-z . R 4Independently selected from linear, branched or cyclic hydrocarbon groups, which are independently selected from alkyl, alkenyl, aryl, aralkyl or alkylaryl and one or more combinations thereof; wherein the hydrocarbon group may be substituted or unsubstituted, may contain one or more heteroatoms and preferably has 1 to 20 carbon atoms; preferably R 4 is phenyl or butyl, more preferably butyl. X 4 is independently selected from fluoride ion (F - ), chloride ion (Cl - ), bromide ion (Br - ) or iodide ion (I - ), preferably chloride ion. z is greater than 0 and less than 2, i.e., 0 < z < 2. For example, R 4 z MgX 4 2-z is n-butylmagnesium chloride or phenylmagnesium chloride, where R 4 are n-butyl or phenyl respectively, z = 1 and X = Cl. Step A) includes many embodiments, which are described in detail on page 15, line 14 to page 16, line 28 of WO2015091984A1 by the same applicant, the entire part of which is incorporated herein by reference.

[0043] Step B) includes contacting the compound R 4 z MgX 4 2-z (defined above in step A)) with a silane compound Si(OR 5 ) 4-n (R 6 ) n to produce a solid support Mg(OR 1 ) x X 1 2-x , where R 1 , R 5 and R 6 each independently selected from linear, branched or cyclic hydrocarbon groups, which are independently selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl and one or more combinations thereof; wherein the hydrocarbon group may be substituted or unsubstituted, may contain one or more heteroatoms, preferably having 1 to 20 carbon atoms; Х 1 is independently selected from fluoride ion (F - ), chloride ion (Cl - ), bromide ion (Br - ) or iodide ion (I - ), preferably chloride ion; n is from 0 to 4, preferably n ranges from 0 up to and including 1; x is greater than 0 and less than 2, i.e., 0 < x < 2. Preferably, tetraethoxysilane (TES; R 5= ethyl, n = 0) is used in step B) as a silane compound to provide a silane compound of the formula Mg(OR 1 ) x X 1 2-x A compound wherein R 1 is ethyl (Et) and X 1 Step B) comprises many embodiments, which are described in detail in WO2015091984A1 on page 16, line 30 to page 22, line 25, the entire portion of which is incorporated herein by reference.

[0044] Stage II: Activation of the solid support for the catalyst (step C)

[0045] This stage consists of one step (step C)) or two sub-steps (steps C1) and C2)).

[0046] Step C) and step C1) are very similar and each comprises contacting the solid support obtained in step B) with at least one activating compound to obtain a partially activated reaction product, the activating compound being of formula M 1 (OR 2 ) v-w (OR 3 ) w or M 2 (OR 2 ) v-w (R 3 ) w Metal (metalloid) alkoxide compounds; wherein: M 1 is a metal (or metalloid) selected from Ti, Zr, Hf, Al and Si; M 2 is Si (metalloid); v is M 1 or M 2 valence, and w is less than v; v is, for example, 3 or 4, and w is, for example, 0, 1 or 2; R 2 and R 3Each is a linear, branched or cyclic hydrocarbon group, which is independently selected from an alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl group and one or more combinations thereof; wherein the hydrocarbon group may be substituted or unsubstituted, may contain one or more heteroatoms, and preferably has 1 to 20 carbon atoms. A second activating compound, i.e., an activating electron donor, is used. It should be noted that in the case where this stage includes two sub-steps, step C1) may include contacting the solid support first with a first activating compound (e.g., TET) and then with a second activating compound (e.g., EtOH); it may include contacting the solid support first with a second activating compound (e.g., EtOH) and then with the first activating compound (e.g., TET). More preferably, an alcohol such as methanol or ethanol is used as the activating electron donor, more preferably ethanol. A method is described in detail on page 23, line 3 to page 28, line 14 of WO2015091984A1 by the same applicant, which discloses activation using a single activating compound as an activating electron donor or metal alkoxide, the entire portion of which is incorporated herein by reference.

[0047] Step C2) involves a second activation using an activating electron donor, preferably an alcohol, more preferably methanol, ethanol, or propanol, and most preferably ethanol. Due to the relatively high toxicity of methanol, ethanol is preferred over methanol. In one embodiment, the activating electron donor used in step C2) can be the same as the activating electron donor used in step C1).

[0048] In one embodiment, step C1) comprises a first activation step using an activating electron donor, preferably methanol or ethanol, most preferably ethanol; and 1 (OR 2 ) v-w (OR 3 ) w of a metal alkoxide compound, preferably titanium tetraethoxide (TET); and step C2) comprises a second activation step, which is carried out using an activating electron donor, preferably ethanol. In a specific embodiment, step C1) uses TET and ethanol, and step C2) uses ethanol. More information about double activation and activating compounds can be found in WO2018 / 059955A1, the sections "Activated Metal Alkoxide Compound" (page 10, lines 10 to 34), "Activating Electron Donor" (page 11, lines 1 to 17) and "Conditions in Step C) (for both C1) and C2))" (page 11, lines 19 to page 12, line 5) are incorporated into this specification by reference.

[0049] Phase III: Preparation of the primary catalyst

[0050] Step D) comprises reacting the activated solid support obtained in step C) (which may be a single-activated or double-activated support) with a halogen-containing Ti compound, optionally an activator and at least one internal electron donor, preferably in several sub-steps or stages. The present invention relates to the use of toluene in this step D). For step D), the halogen-containing Ti compound is mixed with toluene (preferably in a volume ratio of 1:2 to 2:1, for example 1:1.5 to 1.5:1, for example 1:1) before being added to the activated solid support. In addition, the internal donor and optionally the activator are preferably also added to the activated solid support as a solution in toluene.

[0051] Step D) may comprise several stages (e.g., I, II, and III and optionally IV). In each of these successive stages, the activated solid support is contacted with at least one catalytic substance in toluene. In other words, the addition or reaction of the catalytic substance may be repeated one or more times. Preferably, the same catalytic substance is used in each stage. Preferably, titanium tetrachloride (TiCl4) is used as the catalytic substance in all stages of step D). The catalytic substance may be added first, followed by addition of an activator and / or an internal electron donor in any stage.

[0052] In one embodiment, the sub-steps or stages include:

[0053] DI in the first stage) (stage I): contacting the activated solid support obtained in step C) with a halogen-containing Ti compound in toluene, optionally with an activator and optionally (a portion of) the internal donor in toluene;

[0054] D-II in the second stage) (stage II): contacting the product obtained in step DI) with a halogen-containing Ti compound in toluene, optionally with an activator and optionally (a portion of) an internal electron donor in toluene;

[0055] D-III in the third stage) (stage III): contacting the product obtained in step D-II) with a halogen-containing Ti compound in toluene, optionally with an activator and optionally (a portion of) an internal electron donor in toluene;

[0056] fourth stage (optionally D-IV) (stage IV): contacting the product obtained in step D-III) with a halogen-containing Ti compound in toluene, optionally with an activator and optionally (a portion of) an internal electron donor in toluene;

[0057] The internal electron donor is added in at least one of stages DI, D-II, D-III and D-IV to obtain the main catalyst.

[0058] This stage D) (also referred to as stage III) is described in detail in WO2015091984A1 of the same applicant, page 28, line 15 to page 31, line 13, the entire portion of which is incorporated herein by reference. In addition, the specific embodiments of the temperature and time of stage D on page 13, lines 10-25 of WO2018 / 059955A1 are incorporated herein by reference.

[0059] Without wishing to be bound by any theory, the inventors believe that the main purpose of the activator is to increase catalyst productivity (the activator can be added at any stage); whereas the main purpose of the internal donor is to control the stereospecificity of the product, i.e. xylene solubles.

[0060] Catalytic substances

[0061] Step D) comprises, in all sub-steps, reacting the activated solid support with a transition metal halide (e.g., titanium halide, chromium halide, hafnium halide, zirconium halide, vanadium halide), but preferably a titanium halide, such as TiX4, wherein X is chloride or fluoride, preferably chloride. Step D) (also referred to as step iii)) is described in detail in WO2015091984A1, page 29, line 28 to page 31, line 13, the entirety of which is incorporated herein by reference.

[0062] Activator

[0063] An activator may be added in step D). The molar ratio of activator to magnesium may vary within wide limits, for example, from 0.02 to 1.0. Preferably, the 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 in step D).

[0064] Several types of activators can be used, such as benzamides, alkyl benzoates, and monoesters. Each of these will be discussed below.

[0065] The benzamide activator has a structure disclosed on page 13, line 13 to page 14, line 37 of WO2015091983A1 of the same applicant, the entire portion of which is incorporated herein by reference.

[0066] Benzamide can be prepared according to formula X:

[0067]

[0068] where R 70 and R 71 Each is independently selected from hydrogen or alkyl, and R 72 、R 73 、R 74 、R 75 、R 76Each is independently selected from hydrogen, a heteroatom (preferably a halide ion) or a hydrocarbon group selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl and one or more combinations thereof, preferably benzamide (BA or BA-2H, R 70 -R 76 =H), N-methylbenzamide (BA-HMe, R 70 =Me, R 71 to R 76 =H) or N,N-dimethylbenzamide (BA-2Me, R 70 , R 71 =Me and R 72 to R 76 =H). Suitable non-limiting examples of "benzamide" include benzamide (BA-2H), methylbenzamide (BA-HMe) or N,N-dimethylbenzamide (BA-2Me).

[0069] A detailed description of the use of monoesters as activators is found in WO2015091984A1 of the same applicant, page 42, line 12 to page 43, line 24, which is incorporated herein by reference. A detailed description of the use of alkyl benzoates as activators is found in WO2015091984A1 of the same applicant, page 42, lines 1 to 12, which is incorporated herein by reference. The activator is, for example, ethyl benzoate (EB).

[0070] Internal electron donor

[0071] In step D), at least one internal electron donor is added. Mixtures of internal electron donors can also be used. Examples of internal electron donors are disclosed below. The molar ratio of the internal electron donor relative to magnesium can vary within wide limits, for example, from 0.01 to 0.75. Preferably, the molar ratio is from 0.02 to 0.5; more preferably, from 0.03 to 0.3. The internal donor can be added in a single portion in one of stages I, II, III or IV. It can also be added in portions, for example in two or three or even more portions. When the internal donor is added in two portions, it can be added, for example, in stages I and II or in stages II and III. When the internal donor is added in three portions, it can be added, for example, in stages I, II and III or in stages II, III and IV. More information on this can be found in the section on internal donors from page 15, line 18 to page 21, line 32 of WO2018 / 059955, which is incorporated into this specification.

[0072] In one embodiment, 4-[(ethoxycarbonyl)(methyl)amino]pentan-2-ylethylcarbamate (AB-OEt) is used as the internal donor. More information and several embodiments of this internal electron donor can be found in WO2015 / 185489, which is incorporated herein by reference. The preparation of this donor is disclosed in Example A of WO2015 / 185489, which is incorporated herein by reference. In one embodiment, the internal donor is a carbonate-carbamate compound according to Formula A:

[0073]

[0074] Where: R 81 、R 82 、R 83 、R 84 、R 85 and R 86 are the same or different and are independently selected from hydrogen or a linear, branched or cyclic hydrocarbon group selected from an alkyl group, an alkenyl group, an aryl group, an aralkyl group or an alkylaryl group and one or more combinations thereof, preferably having 1 to 20 carbon atoms; R 87 is 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 having 1 to 20 carbon atoms; each R 80 The groups are independently linear, branched or cyclic hydrocarbon groups selected from alkyl, alkenyl, aryl, aralkyl or alkylaryl groups and one or more combinations thereof, preferably having 1 to 30 carbon atoms; R 80 It is preferably selected from an alkyl group 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 is a nitrogen atom; O is an oxygen atom; and C is a carbon atom; preferably 4-[(ethoxycarbonyl)(methyl)amino]pentan-2-ylethylcarbamate (AB-OEt).

[0075] In one embodiment, an aminobenzoate compound according to formula B is used as the internal donor:

[0076]

[0077] Each R 90 The groups are independently substituted or unsubstituted aryl groups, preferably having 6 to 20 carbon atoms; R 91 、R 92 、R 93 、R 94 、R 95 、R 96Each is independently selected from hydrogen or a hydrocarbon group, preferably hydrogen or a linear, branched or cyclic hydrocarbon group, the hydrocarbon group being selected from alkyl, alkenyl, aryl, aralkyl or alkylaryl and one or more combinations thereof, preferably having 1 to 20 carbon atoms; R 97 is hydrogen or a linear, branched, or cyclic hydrocarbon group selected from an alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl, or alkylaryl group, and one or more combinations thereof, preferably having 1 to 20 carbon atoms; N is a nitrogen atom; O is an oxygen atom; and C is a carbon atom; preferably 4-[benzoyl(methyl)amino]pentan-2-ylbenzoate (AB). Further information and several embodiments of this internal electron donor can be found in WO 2014 / 001257 A1, which is incorporated herein by reference. The preparation of this donor is disclosed in WO 2014 / 001257 A1. The examples of this donor preparation disclosed in this patent are incorporated herein by reference.

[0078] In one embodiment, the activator is added in stage I, and the internal donor is added in stage III. In one embodiment, the activator is added in stage I, and the internal donor is added in stages II, III, and optionally IV. Preferably, the activator is a monoester, and the internal donor is an aminobenzoate. In a specific embodiment, the activator EB is added in stage I, and AB is added in stage III. In a specific embodiment, the activator EB is added in stage I, and AB is added in stages II and III. In a specific embodiment, the activator EB is added in stage I, and AB is added in stages II, III, and IV.

[0079] In one embodiment, a 1,3-diether is used as the internal donor, preferably 9,9-bis(methoxymethyl)fluorene (Flu). More information and several embodiments of this internal electron donor can be found in WO 2015 / 091983 A1, which is incorporated herein by reference. An example of a 1,3-diether is the 1,3-diether of formula C:

[0080]

[0081] where R 51 and R 52 Each is independently selected from hydrogen or a hydrocarbon group selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl and one or more combinations thereof, and R 53 and R 54 Each hydrocarbon group is independently selected from, for example, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkoxycarbonyl group, or an alkylaryl group, and one or more combinations thereof, preferably 9,9-bis(methoxymethyl)fluorene (Flu).

[0082] co-catalyst

[0083] The catalyst system according to the present invention includes a cocatalyst. As used herein, " cocatalyst " is a term well known in the field of Ziegler-Natta catalyst technology, and is considered to be a substance capable of converting a primary catalyst into an active polymerization catalyst. Generally, a cocatalyst is an organometallic compound, which contains the 1st, 2nd, 12th or 13th group metal of the IUPAC periodic table (Handbook of Chemistry and Physics, 70th edition, CRC Press, 1989-1990). Cocatalysts can include any compound known in the art as " cocatalyst ", as described in page 59, row 1 to page 60, row 30 in WO2015091984A1 of the same applicant, which is incorporated herein by reference.

[0084] External electron donor

[0085] The catalyst system according to the present invention preferably includes an external electron donor. One of the functions of the external donor compound is to influence the stereoselectivity of the catalyst system during the polymerization of olefins having 3 or more carbon atoms. Therefore, it can also be referred to as a selectivity control agent. Examples of external donors suitable for use in the present invention are internal donor benzoates and 1,3-diethers. Additionally, the following external donors can be used: alkylaminoalkoxysilanes, alkylalkoxysilanes, imidosilanes, and alkylimidosilanes. The Al / 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 include from about 0.1 mol% to about 99.9 mol% of a first external donor and from about 99.9 mol% to about 0.1 mol% of a second or additional alkoxysilane external donor disclosed below. When a silane external donor is used, the Si / Ti molar ratio in the catalyst system can be 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.

[0086] Documents EP1538167A1 and EP1783145A1 disclose a Ziegler-Natta catalyst type comprising a catalyst of the formula Si(OR c )3(NR d R e ) as an external donor, wherein R c is a hydrocarbon group having 1 to 6 carbon atoms, R d is a hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom, and R e is a hydrocarbon radical having 1 to 12 carbon atoms, which is used as an external electron donor. Examples of suitable external donors according to the present invention are known from WO2015091984A1 and are compounds according to formula III, alkyl-alkoxysilanes according to formula IV, formula Si(OR a ) 4-n Rb n The organosilicon compound according to formula I is an imidosilane (R a and R b As defined in WO2015091984A1), an alkylimidosilane according to formula I, as described on page 61, line 26 to page 67, line 8, which is incorporated herein by reference. Alkoxysilane halides are used to prepare imidosilanes and alkylimidosilane internal donors, and are respectively according to formula XXIVa: Z n Si(OR 11 ) 4-n Japanese style XXIVa: Z n Si(OR 11 ) 4-n-m (R 12 ) m (R 11 and R 12 As defined in WO2015091984A1). In the alkoxysilane halides represented by formulas XXIVa and XXIVb, Z is a halogen group, more preferably a chlorine group; n = 1, 2, or 3; and m = 1 or 2. Regarding external donors, examples of formula I' of WO2015091984A1 are described on page 67, lines 9-22, in WO2015091984A1 by the same applicant, which is incorporated herein by reference.

[0087] According to the outer donor of the present invention, other compounds can be one or more alkoxysilanes, as described in WO2015091984A1 of the same applicant on page 67, line 24 to line 4 of page 69, which is incorporated herein by reference. In one embodiment, the silane compound for other outer donors is dicyclopentyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, methylcyclohexyldimethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, dimethylaminotriethoxysilane and one or more combinations thereof. Preferably, outer donor is an alkyl-alkoxysilane (preferably n-propyltrimethoxysilane or n-propyltriethoxysilane) or cyclohexylmethyldimethoxysilane according to formula IV or another dialkyldialkoxysilane.

[0088] Catalyst system

[0089] The present invention also relates to a method for producing a catalyst system by contacting a Ziegler-Natta type procatalyst, a cocatalyst, and optionally one or more external electron donors. The procatalyst, cocatalyst, and external donor can be contacted in any manner known to those skilled in the art; and as also described herein, more particularly as described in the Examples. The present invention further relates to a method for producing a polyolefin by contacting at least one olefin with a polymerization catalyst system comprising a procatalyst according to the present invention. Preferably, the polyolefin produced using the catalyst system of the present invention is polypropylene. For example, the external donor in the catalyst system according to the present invention can be complexed with the cocatalyst and mixed (premixed) with the procatalyst before contacting the procatalyst with the olefin. The external donor can also be added separately to the polymerization reactor. Before being added to the polymerization reactor, the procatalyst, cocatalyst, and external donor can be mixed or otherwise combined. Contacting the olefin with the catalyst system according to the present invention can be carried out under conventional polymerization conditions known to those skilled in the art. See, for example, Pasquini, N. (ed.) "Polypropylene handbook", 2nd edition, Carl Hanser Verlag Munich, 2005, Chapter 6.2, incorporated herein by reference.

[0090] Aggregation Method

[0091] Polymerization process can be the gas phase, slurry or bulk polymerization process carried out in one or more than one reactor.One or more olefin monomers can be introduced into polymerization reactor to react with primary catalyst and form olefin-based polymer (or fluidized bed or stirred bed of polymer particles).In slurry (liquid phase), polymerization and information description about preparation / polyolefin that can be prepared are described in WO2015091984A1 of the same applicant on page 70, line 10 to page 71, line 23, and this part is introduced into this paper by reference; Information about gas phase polymerization process is described in WO2015091984A1 of the same applicant on page 71, line 25 to page 72, line 26, and it is introduced into this paper by reference.

[0092] Olefins

[0093] The olefin according to the present invention may be selected from monoolefins and diolefins containing 2 to 40 carbon atoms; reference is also made to WO2015091984A1 of the same applicant, page 72, line 28 to page 73, line 5, which is incorporated herein by reference. Preferably, the olefin is propylene or a mixture of propylene and ethylene to produce a propylene-based polymer, such as a propylene homopolymer or a propylene-olefin copolymer. The olefin may be an α-olefin having up to 10 carbon atoms, such as ethylene, 1-butene, 1-hexene, 1-heptene, 1-octene.

[0094] polyolefins

[0095] The present invention also relates to a polyolefin, preferably polypropylene, obtained or obtainable by a method comprising contacting an olefin, preferably a mixture of propylene or propylene and ethylene with a procatalyst according to the present invention. More information about the polymer formed is disclosed in WO2015091984A1 of the same applicant on page 73, lines 6-23 and 25-34 and page 74, line 26 to page 75, line 24, which are incorporated herein by reference as a whole. The present invention also relates to a polyolefin, preferably a propylene-based polymer, obtained or obtainable by a method comprising contacting propylene or a mixture of propylene and ethylene with a catalyst system according to the present invention as described above. In one embodiment, the present invention relates to producing a polypropylene homopolymer. Several polymer properties are discussed herein.

[0096] The xylene soluble fraction (XS) is preferably from 0.5 wt% to 10 wt%, or at least 0.5 wt% or at least 1.0 wt%. It is preferably at most 8 wt%, or at most 7 wt%. The productivity is preferably from 1 kg / g / hour to 100 kg / g / hour, or at least 20 kg / g / hour, or at most 90 kg / g / hour. The MFR is preferably from about 0.01 g / 10 min to about 2000 g / 10 min. It is preferably at least 0.01 g / 10 min, or at least 0.1 g / 10 min. It is preferably at most 1000 g / 10 min, or at most 500 g / 10 min, or at most 150 g / 10 min, or at most 100 g / 10 min.

[0097] Uses of polyolefins

[0098] The present invention also relates to the use of the polyolefins according to the present invention, preferably propylene-based polymers (also referred to as polypropylene), for applications such as injection molding, blow molding, extrusion molding, compression molding, casting, thin-wall injection molding, etc., for example in contact with food. In addition, the present invention relates to a shaped article comprising a polyolefin according to the present invention, preferably a propylene-based polymer. The polyolefins according to the present invention, preferably propylene-based polymers, can be converted into shaped (semi-) finished articles using a variety of processing techniques. Examples of suitable processing techniques include injection molding, injection-compression molding, thin-wall injection molding, extrusion, and extrusion-compression molding. Injection molding is widely used to produce articles such as caps and lids, battery packs, barrels, containers, automotive exterior parts such as bumpers, automotive interior parts such as dashboards, or automotive parts under the hood. Extrusion is widely used, for example, to produce articles such as rods, sheets, films and tubes. Thin-wall injection molding can, for example, be used to manufacture thin-wall packaging applications used in both the food and non-food sectors. This includes barrels and containers and butter / margarine tubs and dairy cups.

[0099] Specific implementation plan

[0100] Several specific embodiments are disclosed below. Three combinations of activators and internal electron donors are discussed below. The first combination of activators and internal electron donors is EB and AB.

[0101] Specific implementation plan 1

[0102] A method for preparing a procatalyst suitable for preparing a catalyst composition for olefin polymerization, the method comprising the steps of:

[0103] Step A): providing or preparing a butylmagnesium chloride Grignard compound;

[0104] Step B): contacting a butylmagnesium chloride Grignard compound with TES to produce a solid support;

[0105] Step C): activating the solid support, which comprises two sub-steps: step C1) a first activation step: contacting the solid support obtained in step B) with at least one first activating compound TET; and step C2) a second activation step: contacting the partially activated solid support obtained in step C1) with ethanol;

[0106] Step D): before or simultaneously with the addition of AB as an internal donor, toluene and TiCl4 as solvents and ethyl benzoate as an activator are added to the activated solid support obtained in step C) to obtain the procatalyst.

[0107] A second combination of activator and internal electron donor is EB with 4-[(ethoxycarbonyl)(methyl)amino]pentan-2-ylethylcarbamate (AB-OEt).

[0108] Specific implementation plan 2

[0109] A method for preparing a procatalyst suitable for preparing a catalyst composition for olefin polymerization, the method comprising the steps of:

[0110] Step A): providing or preparing a butylmagnesium chloride Grignard compound;

[0111] Step B): contacting a butylmagnesium chloride Grignard compound with TES to produce a solid support;

[0112] Step C): activating the solid support, which comprises two sub-steps: step C1) a first activation step: contacting the solid support obtained in step B) with at least one first activating compound TET; and step C2) a second activation step: contacting the partially activated solid support obtained in step C1) with ethanol;

[0113] Step D): before or simultaneously with the addition of AB-OEt, toluene and TiCl4 are added to the activated solid support obtained in step C), and ethyl benzoate as an activating agent to obtain the main catalyst.

[0114] The third combination of activator and internal electron donor is Ba-2Me and Flu.

[0115] Specific implementation plan 3

[0116] A method for preparing a procatalyst suitable for preparing a catalyst composition for olefin polymerization, the method comprising the steps of:

[0117] Step A): providing or preparing a butylmagnesium chloride Grignard compound;

[0118] Step B): Contacting butylmagnesium chloride Grignard compound with TES to produce a solid support

[0119] Step C): activating the solid support, which comprises two sub-steps: step C1) a first activation step: contacting the solid support obtained in step B) with ethanol as a second activating compound, and then contacting with at least one first activating compound, namely TET; and step C2) a second activation step: contacting the activated solid support obtained in step C1) with ethanol;

[0120] Step D): before or simultaneously with the addition of Flu as an internal donor, toluene and TiCl4, and BA-2Me as an activating agent are added to the activated solid support obtained in step C) to obtain the procatalyst.

[0121] The present invention will now be further illustrated by the following non-limiting examples.

[0122] Example

[0123] Example 1

[0124] Step A) Preparation of a solution of butylmagnesium chloride

[0125] This step is carried out according to the procedure proposed in Example III of EP1222214B1. 280g of magnesium powder is filled into a stainless steel reactor of 16L volume. Reactor is placed under nitrogen. Magnesium is heated at 80 ℃ for 1 hour, and thereafter a mixture of dibutyl ether (1.5L) and normal chlorobutane (80mL) is added. The mixture is warmed to 75 ℃, and iodine (0.7g) is added to the reaction mixture. After the color of iodine disappears, the other mixture of dibutyl ether (10L) and normal chlorobutane (1.1L) is slowly added within 3 hours. The temperature of the reaction mixture is maintained at 76 to 78 ℃. The reaction mixture is stirred for another 4 hours at a temperature of 76 ℃. Then stirring and heating are stopped, and solid material is settled for 48 hours. The solution on the solid material is removed by decantation, and a solution (product A) of butylmagnesium chloride in dibutyl ether is obtained by it, and its concentration is 0.86molMg / L.

[0126] Step B) Preparation of solid support

[0127] Before addition, the reagents in the carrier preparation were premixed using a mini mixer equipped with an agitator and a jacket, as proposed in Example 1 of EP1222214B1. The volume of the mini mixer was 3.0 mL, and the volume of the pipeline between the mini mixer and the reactor was 0.6 mL. The premixing time was approximately 9.3 seconds. A 16L stainless steel reactor was equipped with a blade stirrer, two baffles, and a jacket. 4L of dibutyl ether was filled into the reactor. The reactor temperature was set at 35°C and a stirring speed of 115 rpm was used. The temperature in the mini mixer was set at 3°C ​​and a stirring speed of 1000 rpm was used. The product of step A) was a solution of product A (6.8 L, 5.85 mol Mg) and a solution of 979 mL of TES in 1060 mL of dibutyl ether, both of which were cooled to 3°C and then fed to the reactor simultaneously via the mini mixer. This enabled the product A and TES solution to be premixed. The feeding time to the reactor was 340 minutes. The stirring speed in the reactor was 115 rpm at the start of the feeding and then gradually increased until it reached 160 rpm at the end of the feeding period. Once the feeding was completed, the reaction mixture was heated to a temperature of 60° C. during a 30-minute heating period and maintained at this temperature for 1 hour. The stirring was then stopped and the solid material was allowed to settle. The supernatant was removed by decantation. The solid material was pre-washed four times using 8 L of heptane. A white solid material (product B) was obtained as a solid support in the form of a suspension in 2 L of heptane. The average particle size of the support was 17.3 μm, and the SPAN value (d90-d10) / d50 was 0.62.

[0128] Step C): Support activation

[0129] Solid support (product B) uses the first activation compound TET and the second activation compound, i.e., activation electron donor ethanol (EtOH), to activate via the following two-stage procedure. First, the suspension of the product B comprising 600g of solid support obtained in step B) is added to a 16L stainless steel reactor and diluted to 10L volume with heptane. The agitator speed of the reactor is set to 150rpm and the reactor is cooled to a temperature of 10°C. Then, within 60 minutes, at a temperature of 10°C, a solution of 600mL of 28.8mL ethanol in 571.2mL heptanes is slowly fed to the reactor. The mol ratio of ethanol to magnesium (EtOH / Mg) is 0.1. After feeding is complete, the reaction mixture is kept at 10°C for 30 minutes. Then, at a temperature of 10°C, 600mL of a solution of 102ml TET in heptane is added within 1 hour, and the mol ratio of TET to magnesium (TET / Mg) is 0.1. Then, in a 30-minute heating period, the slurry was heated to a temperature of 30 ℃ and kept at this temperature for 120 minutes. Then, stop mixing, and make solid sedimentation, and decanted the supernatant thereafter. The solid reaction product obtained was cleaned once with 7L heptane. Thereafter 10L heptane was added into the reactor, and the reaction product was cooled to a temperature of 15 ℃. Subsequently, at 15 ℃ of temperature and a feeding time of 60 minutes, 800mL solution (the molar ratio of ethanol to magnesium is 0.3) of 86.5mL ethanol in 713.5mL heptane was fed. Thereafter, in a 30-minute heating period, the slurry was heated to a temperature of 30 ℃, and kept at this temperature for 120 minutes. Subsequently, stop mixing, and make solid sedimentation, and decanted the supernatant. The solid product (product C, i.e. the activated solid carrier) was cleaned once with 7L heptane.

[0130] Step D): Preparation of catalyst

[0131] Phase I: A 0.3 L glass reactor was placed under a nitrogen atmosphere, and 100 ml of titanium TiCl₄ was added to the reactor. A suspension of 5 g of the activated solid support obtained in step C) in 15 mL of heptane was added to the reactor with stirring. The reaction mixture was maintained at 20°C for 60 minutes. The reaction mixture was then heated to 105°C over a 60-minute heating period. During the first 15 minutes, as the temperature increased from 20°C to approximately 50°C, 1.58 g of EB in 3 mL of toluene (EB to magnesium molar ratio of 0.3) was added to the reactor. After the additions were complete, the reaction mixture was stirred at 105°C for 90 minutes. Stirring was then stopped, and the solids were allowed to settle. The supernatant was removed by decantation, and the solid product was then rinsed once with 120 mL of toluene at 100°C for 20 minutes. The rinse solution was then removed by decantation.

[0132] Stage II: A mixture of 60 mL of TiCl4 and 60 mL of toluene was added to the solid product obtained in Stage I. The reaction mixture was heated to 105°C, after which a solution of 0.57 g of AB in 3 mL of toluene was added, with a molar ratio of AB to magnesium of 0.05. The reaction mixture was stirred at 105°C for 60 minutes. Stirring was then stopped, and the solid material was allowed to settle. The supernatant was removed by decantation.

[0133] Stage III: A solution of 0.51 g of AB in 3 ml of toluene was added to the solid obtained in Stage II, with a molar ratio of AB to magnesium of 0.045. The reaction mixture was stirred at 105°C for 60 minutes. Stirring was then stopped, and the solid material was allowed to settle. The supernatant was removed by decantation. A mixture of 60 mL of TiCl4 and 60 mL of toluene was then added, and the reaction mixture was stirred at 105°C for 30 minutes. Stirring was then stopped, and the solid material was allowed to settle. The supernatant was removed by decantation, and the obtained solid was washed five times, using 150 mL of heptane at 60°C for each wash. The primary catalyst was obtained.

[0134] Step E): Propylene polymerization

[0135] Propylene polymerization was carried out in a 0.7 L stainless steel reactor in 300 mL of heptane at 70° C., a total pressure of 0.7 MPa, and in the presence of 55 mL of hydrogen for 60 minutes in the presence of a catalyst system comprising: i) the procatalyst obtained in step D), triethylaluminum (TEAL) as a cocatalyst, and cyclohexylmethyldimethoxysilane (C-donor) as an external electron donor. The concentration of the procatalyst component was 0.023 g / L; the TEAL concentration was 4.0 mmol / L; and the C-donor concentration was 0.2 mmol / L. Table 1 below shows the performance data of the catalyst in propylene polymerization.

[0136] Example 2

[0137] Steps A), B), C) and E) were performed as described in Example 1. Step D) was performed as disclosed below.

[0138] Step D): Preparation of catalyst

[0139] This step was carried out as described in Example 1, except that the stirring time duration after each addition of TiCl4 and toluene and after the addition of AB was 100 minutes instead of 60 or 30 minutes according to Example 1. Table 1 below gives the performance data of the catalyst in propylene polymerization.

[0140] Comparative Example 1 (CE1)

[0141] Steps A), B), C) and E) were performed as described in Example 1. Step D) was performed as disclosed below.

[0142] Step D): Preparation of catalyst

[0143] This step was carried out as described in Example 1, except that chlorobenzene was used as solvent instead of toluene in all stages of the catalyst preparation; the same amount of solvent was used. Table 1 below gives the performance data of the catalyst in propylene polymerization.

[0144] Comparative Examples 2 and 3 (CE2, CE3)

[0145] Steps A), B), C) and E) were performed as described in Example 1. Step D) was performed as disclosed below.

[0146] Step D): Preparation of catalyst

[0147] This step was carried out as described in Example 1, except that heptane was used as solvent instead of toluene in all stages of the catalyst preparation; the same amount of solvent was used. Table 1 below gives the performance data of the catalyst in propylene polymerization.

[0148] Table 1. Results

[0149]

[0150] 1 Screening data

[0151] Table 1 shows that the catalyst prepared according to the method of the present invention using toluene as the solvent has surprisingly higher MFR values ​​(1.1 to 1.3 vs. 0.7 g / 10 min), which is desirable. Table 1 further shows that the catalyst prepared according to the method of the present invention using toluene as the solvent has surprisingly higher internal donor content; the method of the present invention thus provides more efficient use of the internal donor, which is environmentally and economically desirable, while maintaining high activity, high PP bulk density, and narrow SPAN. In addition, toluene is a safer solvent for the environment than chlorobenzene.

Claims

1. A method for preparing a procatalyst suitable for preparing a catalyst composition for olefin polymerization, the method comprising the steps of: Step A): Providing or preparing compound R 4 z MgX 4 2-z ,in: *R 4 independently selected from linear, branched or cyclic hydrocarbon groups, the hydrocarbon groups being independently selected from alkyl, alkenyl, aryl, aralkyl or alkylaryl groups, and one or more combinations thereof; wherein the hydrocarbon group is substituted or unsubstituted, optionally contains one or more heteroatoms and has 1 to 20 carbon atoms; *X 4 are independently selected from fluoride, chloride, bromide, or iodide; and *z is greater than 0 and less than 2, that is, 0 <z<2; Step B): Compound R 4 z MgX 4 2-z With silane compound Si(OR 5 ) 4-n (R 6 ) n Contact to produce Mg(OR 1 ) x X 1 2-x ,in: *R 1 、R 5 and R 6 each independently selected from a linear, branched or cyclic hydrocarbon group, the hydrocarbon group being independently selected from an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkoxycarbonyl group or an alkylaryl group, and one or more combinations thereof; wherein the hydrocarbon group is substituted or unsubstituted, optionally contains one or more heteroatoms and has 1 to 20 carbon atoms; * 1 independently selected from fluoride, chloride, bromide, or iodide; *n is 0 to 4; and *x is greater than 0 and less than 2, that is, 0 <x<2; step C): activating the solid support by contacting the solid support product obtained in step B) with at least one first activating compound and a second activating compound to obtain an activated solid support, The first activating compound is of formula M 1 (OR 2 ) v-w (OR 3 ) w or M 2 (OR 2 ) v-w (R 3 ) w A metal or metalloid alkoxide compound; wherein: *M 1 is a metal or metalloid selected from Ti, Zr, Hf, Al and Si; *M 2 It is Si; *v is M 1 or M 2 valence of; *w is less than v; *R 2 and R 3 each is a linear, branched or cyclic hydrocarbon group independently selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl, and one or more combinations thereof; wherein the hydrocarbon group is substituted or unsubstituted, optionally contains one or more heteroatoms and has 1 to 20 carbon atoms; The second activating compound is an activating electron donor; Step D): adding toluene, a halogen-containing Ti compound and at least one internal electron donor to the activated solid support obtained in step C), and optionally adding an activator before or simultaneously with the addition of the internal electron donor, and reacting to obtain the procatalyst, Wherein step C) activating the solid support comprises two sub-steps: Step C1) First activation step: by contacting the solid support obtained in step B) with a second activating compound, ie, an activating electron donor, and with at least a first activating compound, ie, a compound of formula M 1 (OR 2 ) v-w (OR 3 ) w or M 2 (OR 2 ) v-w (R 3 ) w The solid support is partially activated by contacting a metal or metalloid alkoxide compound; wherein M 1 is a metal or metalloid selected from Ti, Zr, Hf, Al or Si; M 2 is Si; v is M 1 or M 2 valence; w is less than v; R 2 and R 3 each is a linear, branched or cyclic hydrocarbon group independently selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl, and one or more combinations thereof; wherein the hydrocarbon group is substituted or unsubstituted, optionally contains one or more heteroatoms and has 1 to 20 carbon atoms; and step C2) a second activation step: obtaining an activated solid support by contacting the partially activated solid support obtained in step C1) with an activating electron donor.

2. The method according to claim 1, wherein step D) comprises the following stages: DI) first stage: contacting the activated solid support obtained in step C2) with a halogen-containing Ti compound, optionally an activator and optionally at least a portion of an internal electron donor; D-II) second stage: contacting the product obtained in step DI) with a halogen-containing Ti compound and optionally at least a portion of an internal electron donor; D-III) third stage: contacting the product obtained in step D-II) with a halogen-containing Ti compound and optionally at least a portion of an internal electron donor; D-IV) optionally a fourth stage: contacting the product obtained in step D-III) with a halogen-containing Ti compound and optionally at least a portion of an internal electron donor; wherein the internal electron donor is added in at least one of stages D-1, D-II, D-III and D-IV.

3. The process according to claim 1 , wherein titanium tetraethoxide is used as the first activating compound in step C1), and wherein ethanol is used as the second activating compound in step C1), and wherein ethanol is used as the activating electron donor in step C2).

4. The process according to claim 1 , wherein as activator one of the following is used: 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 p-chlorobenzoate, ethyl p-bromobenzoate, methyl p-toluate and ethyl cyclohexane; or ii) a benzamide according to formula X: where R 70 and R 71 Each is independently selected from hydrogen or alkyl, and R 72 、R 73 、R 74 、R 75 、R 76 Each is independently selected from hydrogen, a heteroatom, or a hydrocarbon group selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl, or alkylaryl, and one or more combinations thereof.

5. The method according to any one of claims 1 to 2, wherein one of the following is used as an internal electron donor: i) a carbonate-carbamate compound according to formula A: in: R 81 、R 82 、R 83 、R 84 、R 85 and R 86 are the same or different and are independently selected from hydrogen or a linear, branched or cyclic hydrocarbon group selected from an alkyl group, an alkenyl group, an aryl group, an aralkyl group or an alkylaryl group and one or more combinations thereof, having 1 to 20 carbon atoms; R 87 is hydrogen or a linear, branched or cyclic hydrocarbon group selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl and one or more combinations thereof, having 1 to 20 carbon atoms; each R 80 The groups are independently linear, branched or cyclic hydrocarbon groups selected from alkyl, alkenyl, aryl, aralkyl or alkylaryl groups and one or more combinations thereof, having 1 to 30 carbon atoms; N is a nitrogen atom; O is an oxygen atom; and C is a carbon atom; or (ii) an aminobenzoate compound according to formula B: Each R 90 The groups are independently substituted or unsubstituted aryl; R 91 、R 92 、R 93 、R 94 、R 95 and R 96 Each is independently selected from hydrogen or a linear, branched or cyclic hydrocarbon group selected from an alkyl group, an alkenyl group, an aryl group, an aralkyl group or an alkylaryl group and one or more combinations thereof, having 1 to 20 carbon atoms; R 97 is hydrogen or a linear, branched or cyclic hydrocarbon group selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl, and one or more combinations thereof, having 1 to 20 carbon atoms; N is a nitrogen atom; O is an oxygen atom; and C is a carbon atom; or iii) 1,3-diether represented by formula C: where R 51 and R 52 Each is independently selected from hydrogen or a hydrocarbon group selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl and one or more combinations thereof, and R 53 and R 54 Each is independently a hydrocarbyl group selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups, and one or more combinations thereof.

6. The process according to claim 1 , wherein in step D), N,N-dimethylbenzamide is added as an activator and 9,9-bis(methoxymethyl)fluorene is added as an internal electron donor, or wherein in step D), ethyl benzoate is added as an activator and wherein 4-[(ethoxycarbonyl)(methyl)amino]pentan-2-ylethylcarbamate or 4-[benzoyl(methyl)amino]pentan-2-ylbenzoate is added as an internal electron donor.

7. The method according to claim 2, wherein the internal electron donor is added in two stages of step D) in multiple portions: * in two parts, wherein the amount of the internal electron donor is distributed between the two parts in a weight ratio of 80%:20% to 20%:80% based on the total amount of the internal electron donor; or * In three parts, wherein the amount of the internal electron donor is distributed among the three parts at a weight ratio of 20% to 40% per part based on the total amount of the internal electron donor, wherein the sum of the three parts is 100%.

8. A procatalyst directly obtained by the method according to any one of claims 1 to 7.

9. A catalyst system comprising the procatalyst according to claim 8, a cocatalyst and optionally an external electron donor.

10. A method for preparing polyolefins, comprising contacting the catalyst system according to claim 9 with propylene to prepare a polypropylene homopolymer, or with a mixture of propylene and an olefin to prepare a propylene-olefin copolymer.

11. Polyolefin obtainable by the process according to claim 10, or a shaped article comprising said polyolefin.

12. Use of toluene as a dispersant in a method according to any one of claims 1 to 7, said method comprising contacting the activated solid support with a halogen-containing titanium compound and an internal electron donor, and said toluene serving as a dispersant to increase the introduction of the internal electron donor into the procatalyst.

13. Use of toluene as a dispersant in the method according to any one of claims 1 to 7, wherein the method comprises contacting the activated solid support with a halogen-containing titanium compound, an activator, and an internal electron donor, and wherein the toluene is used as a dispersant to increase the introduction content of the activator into the main catalyst and optionally to increase the introduction content of the internal electron donor into the main catalyst.

Images