Process for the preparation of a solid support for a procatalyst for the polymerization of olefins

Abstract

A method for preparing a solid support for a main catalyst, the main catalyst being suitable for preparing a catalyst composition for olefin polymerization, the method comprising: A. providing or preparing a compound R 4 z MgX 4 2‑z , wherein: R 4 is independently 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; X 4 is independently selected from fluoride ion, chloride ion, bromide ion or iodide ion; and 0 < z < 2; and B. contacting the compound R 4 z MgX 4 2‑z with a silane compound Si(OR 5 ) 4‑n (R 6 ) n to produce Mg(OR 1 ) x X 1 2‑x , wherein: R 1 , R 5 and R 6 each is 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; Х 1 is independently selected from fluoride ion, chloride ion, bromide ion or iodide ion; n is 0 - 4; 0

Description

Background Art

[0001] The present invention relates to an improved method for preparing a solid support for a main catalyst, which is suitable for a catalyst system for polymerizing olefins, and an initiator compound is used in the preparation process. The present invention also relates to the obtained solid support, the main catalyst and the catalyst system comprising the solid support. In addition, the present invention relates to a method for producing polyolefins by contacting at least one olefin with the catalyst system. Furthermore, the present invention relates to polymers obtained by polymerization using the main catalyst and shaped articles of the polymers.

[0002] Ziegler-Natta catalyst systems suitable for preparing polyolefins and their components are well known. An overview of such catalyst types is given, for example, by T. Pullukat and R. Hoff in Catal. Rev.–Sci. Eng. 41, Volumes 3 and 4, 389-438, 1999. The preparation of such main catalysts is disclosed, for example, in WO 96 / 32427 A1. An object of the present invention is to provide an improved method for preparing a solid support for a main catalyst for polymerizing olefins, especially with improved yield and xylene solubles. Summary of the Invention

[0003] At least one of the foregoing objects of the present invention is achieved by the following aspects.

[0004] In a first aspect, the present invention relates to a method for preparing a solid support for a main catalyst, which is suitable for preparing a catalyst composition for olefin polymerization, the method comprising:

[0005] Step A) providing or preparing a compound R 4 z [[ID=2,0]]MgX 4 2-z , wherein: R 4 is independently 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, preferably has 1-20 carbon atoms, preferably R 4 is butyl; X 4 is independently selected from fluoride ion (F-), chloride ion (Cl-), bromide ion (Br-) or iodide ion (I-), preferably chloride ion; and z is greater than 0 and less than 2, i.e., 0 < z < 2; and

[0006] Step B) reacting the compound R 4 z MgX 4 2-z with a silane compound Si(OR 5 )4-n (R 6 ) n Contact is made to produce Mg(OR 1 ) x X 1 U 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; where the hydrocarbon group may be substituted or unsubstituted, may contain one or more heteroatoms, preferably having 1-20 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 0-4, preferably n ranges from 0 up to and including 1; z is greater than 0 and less than 2, i.e., 0 < z < 2; and x is greater than 0 and less than 2, i.e., 0 < x < 2;

[0007] wherein an initiator compound selected from ketones, diketones, esters, diesters and benzamides is added during step B to obtain the solid support;

[0008] where the initiator compound does not contain any heteroatoms and is not a phthalate or ester.

[0009] According to another aspect, the present invention relates to a solid support or an activated solid support directly obtained or obtainable by the method according to the present invention.

[0010] According to yet another aspect, the present invention relates to a method for preparing a main catalyst suitable for preparing a catalyst composition for olefin polymerization, the method comprising: I) providing a solid support or an activated solid support according to the present invention; and II) reacting the solid support or the activated solid support with a halogen-containing Ti-compound, optionally an activator before or simultaneously with the addition of an internal donor, and at least one internal electron donor to obtain the main catalyst.

[0011] According to yet another aspect, the present invention relates to a main catalyst directly obtained or obtainable by the method according to the foregoing aspect.

[0012] According to yet another aspect, the present invention relates to a solid support or an activated solid support having an average particle size (or APS) of 8–35 μm, preferably 11-32, more preferably 18-30.

[0013] According to yet another aspect, the present invention relates to a catalyst system comprising the main catalyst of the present invention, a cocatalyst, and optionally an external electron donor.

[0014] the present invention relates to a catalyst system comprising the main catalyst of the present invention, a cocatalyst, and optionally an external electron donor.According to another aspect, the present invention relates to a method for preparing polyolefins, comprising contacting the catalyst system of the present invention with at least one olefin, preferably propylene, to prepare a polypropylene homopolymer, or contacting it with a mixture of propylene and an olefin such as ethylene, butene or hexene to prepare a propylene-olefin copolymer.

[0015] According to another aspect, the present invention relates to a polyolefin, preferably polypropylene, that can be obtained by the method according to the foregoing aspects.

[0016] According to another aspect, the present invention relates to a molded article comprising a polyolefin, preferably polypropylene, according to the invention.

[0017] definition

[0018] The following definitions are used to define the subject matter in this specification and claims. Other terms not referenced below have the meanings commonly accepted in the art.

[0019] As used in this specification, “Ziegler-Natta catalyst” means: a solid catalyst compound containing a transition metal comprises a catalyst supported on a metal or non-metal compound (e.g., a magnesium compound or a silica compound).

[0020] As used in this specification, "catalytic substance" means: a substance containing a transition metal includes a transition metal halide selected from titanium halide, chromium halide, hafnium halide, zirconium halide and vanadium halide.

[0021] As used in this specification, "internal donor" or "internal electron donor" means an electron-donating compound containing one or more oxygen (O) and / or nitrogen (N) atoms.

[0022] As used in this specification, "external donor" or "external electron donor" means: an electron-donating compound used as a reactant in olefin polymerization. It contains at least one functional group capable of donating at least one pair of electrons to a metal atom.

[0023] As used in this specification, "initiator compound" means a compound added during the synthesis of the solid support used as the main catalyst.

[0024] As used in this specification, "activator" means: an electron-donating compound containing one or more oxygen (O) and / or nitrogen (N) atoms, which is used in the synthesis of the main catalyst (i.e., in the process of adding the catalyst to the solid support) and is added before or simultaneously with the addition of the internal donor.

[0025] As used in this specification, "activating compound" means a compound used to activate the solid support before it comes into contact with the catalyst. This differs from the initiator compound because this activating compound is used after the solid support has been prepared and before the catalyst is added.

[0026] As used in this specification, "primary catalyst" has the same meaning: a component of a catalyst composition, typically comprising a (activated) solid support, a transition metal-containing catalyst, and one or more internal donors.

[0027] As used in this specification, "halogen" or "halogen" means an ion selected from fluoride (F-), chloride (Cl-), bromide (Br-) or iodide (I-).

[0028] As used herein, “heteroatom” means an atom other than carbon or hydrogen. However, as used herein—unless otherwise specified, such as below—when “one or more heteroatoms” is used, it means one or more of the following: F, Cl, Br, I, N, O, P, B, S, or Si. Therefore, heteroatoms also include halide ions.

[0029] As used in this specification, "hydrocarbon group" means: a substituent containing hydrogen and a carbon atom, or a linear, branched, or cyclic saturated or unsaturated aliphatic group, such as alkyl, alkenyl, and alkynyl; an alicyclic group, such as cycloalkyl and cycloalkenyl; an aromatic group, such as monocyclic or polycyclic aryl, and combinations thereof, such as alkylaryl and aralkyl. A hydrocarbon group may be substituted with one or more non-hydrocarbon substituents. A non-limiting example of a non-hydrocarbon substituent is a heteroatom. An example is an alkoxycarbonyl (i.e., a carboxylic ester) group. When "hydrocarbon group" is used in this specification, it can also mean "substituted hydrocarbon group" unless otherwise specified.

[0030] As used in this specification, "alkyl" means: an alkyl group or side chain consisting of carbon and hydrogen atoms with a single bond. Alkyl groups can be straight or branched, and can be unsubstituted or substituted.

[0031] As used in this specification, "aryl" means that an aryl group is a functional group or side chain derived from an aromatic ring. Aryl groups can be unsubstituted or substituted with straight-chain or branched hydrocarbon groups.

[0032] As used in this specification, "alkoxide" or "alkoxy group" refers to a functional group or side chain derived from an alkyl alcohol. It consists of an alkyl group bonded to a negatively charged oxygen atom.

[0033] As used in this specification, "aryl oxide," "aryloxy group," or "phenoxy group" refers to a functional group or side chain derived from an aryl alcohol. It consists of an aryl group bonded to a negatively charged oxygen atom.

[0034] As used in this specification, "Grignard reagent" or "Grignard compound" means: Formula R 4 z MgX 4 2-z Compounds or mixtures of compounds (R) 4 z and X 4 (as defined below), or it can be a complex with more Mg clusters, such as R4Mg3Cl2.

[0035] As used in this specification, “bulk density” or “BD” means: the weight of material per unit volume, including the inherent voids in the material being tested. Bulk density is measured as apparent density according to ASTM D1895-96 Reapproved 2010-e1, Test Method A.

[0036] As used in this specification, “XS” or “xylene-soluble portion” means the weight percentage (wt%) of soluble xylene in the isolated polymer, as measured according to ASTM D5492-10.

[0037] As used in this specification, “yield” means: the amount of polymer produced in kg (productivity) / the amount of primary catalyst consumed per hour in the polymerization reactor in g.

[0038] As used in this specification, “yield / Ti” means the yield of PP (kg) divided by the amount of titanium in 1g of the main catalyst. For example, 12.2kg PP / g catalyst and Ti = 1.8wt% corresponds to a yield of 12.2kg PP / 0.018 = 678kg PP / g Ti.

[0039] As used in this specification, “particle size” refers to the average particle size (APS) of the solid support or main catalyst. It is measured using a test method based on ASTM standard test method D4464-201.

[0040] As used in this specification, “SPAN” refers to the particle size distribution (PSD) of the solid support or polymer for the main catalyst. It is calculated according to the following formula: SPAN = (D90 – D10) / D50. The particle size distribution and average size of the support, main catalyst, and PP powder were determined on a Mastersizer 2000 instrument by laser scattering. Detailed Implementation

[0041] It has been surprisingly found that the performance of the main catalyst can be improved by an improved method for preparing a solid support for the main catalyst according to a first aspect of the invention. The use of an added initiator compound during support synthesis has shown increased yield and reduced xylene-soluble value of the resulting final polymer. Furthermore, a decrease in D50 and an increase in the pore volume of the solid support have been observed.

[0042] In addition, several classes of initiator compounds under consideration (ketones, esters, and benzamides) have been found to offer additional advantages, such as reduced bulk density of ester and benzamide compounds and increased pore volume of the main catalyst of ester compounds.

[0043] Therefore, the initiator compound is selected from ketones, diketones, esters, diesters and benzamides, wherein the initiator compound does not contain any heteroatoms and is not a phthalate.

[0044] In one embodiment, a ketone compound of Formula I or a diketone of Formula II is used as the initiator compound.

[0045]

[0046] R1, R2, R3, and R4 are each independently a linear, branched, or cyclic hydrocarbon group, independently selected from alkyl, alkenyl, aryl, aralkyl, and one or more combinations thereof, preferably using a ketone selected from: methyl isobutyl ketone, acetophenone, methyl propyl ketone, diisopropyl ketone, acetone, and acetylacetone. Methyl isobutyl ketone, acetophenone, methyl propyl ketone, diisopropyl ketone, and acetone are according to Formula I, and acetylacetone is according to Formula II.

[0047] Preferably, each of the R1, R2, R3, and R4 groups is C1-C. 12 More preferably, it consists of C1-C6 groups. Preferably, R1 is an alkyl group (preferably C1-C6) and R2 is an alkyl group (preferably C1-C6) or an aryl group (preferably C6).

[0048] In one embodiment, a monoester of formula III or a diester of formulas IV, V, and VI is used as the initiator compound.

[0049]

[0050] R5, R6, R7, R8, R9, and R10 are each independently a linear, branched, or cyclic hydrocarbon group, independently selected from alkyl, alkenyl, aryl, aralkyl, and one or more combinations thereof. Preferably, the initiator is selected from butyl acetate, ethyl acetate, ethyl benzoate, diethyl malonate, and diethyl succinate. Butyl acetate, ethyl acetate, and ethyl benzoate are according to Formula III, diethyl malonate according to Formula IV, and diethyl succinate according to Formula V. Preferably, each R5, R6, R7, R8, R9, and R10 group is C1-C1. 12 More preferably, it is a C1-C6 group. Preferably, R5 is a methyl (C1) group.

[0051] In one embodiment, an amide of formula VII is used as the initiator compound:

[0052]

[0053] R13, R14 and R15 are each independently selected from linear, branched or cyclic hydrocarbon groups, which are independently selected from alkyl, alkenyl, aryl, aralkyl and one or more combinations thereof, preferably using benzamide as the initiator compound, which is selected from N,N-dimethylbenzamide.

[0054] In one embodiment, the obtained solid support is activated using an activating electron donor and / or an activating compound. Alkyl alcohols are preferably used as the activating electron donor, more preferably methanol or ethanol. Metal alkoxides are preferred as the activating compound, more preferably titanium tetraethoxide. Ethanol and / or titanium tetraethoxide, more preferably ethanol, are used to obtain the activated solid support.

[0055] In one implementation, the initiator may be:

[0056] • Methyl isobutyl ketone (MIBK), where R1 is isobutyl (C4) and R2 is methyl (C1).

[0057] Acetophenone (AcPh), where R1 is phenyl (C6) and R2 is methyl (C1),

[0058] • Methyl propyl ketone (MPK), where R1 is n-propyl (C3) and R2 is methyl (C1).

[0059] • Diisopropyl ketone (DIPK), where R1 is isopropyl (C3) and R2 is isopropyl (C3).

[0060] • Acetone (Ac), where R1 is methyl (C1) and R2 is methyl (C1).

[0061] • Acetylacetone (AcAc), where R3 is a methyl group (C1) and R4 is a methyl group (C1).

[0062] Butyl acetate (BuAc), where R5 is methyl (C1) and R6 is n-butyl (C4).

[0063] Ethyl acetate (EA), where R5 is methyl (C1) and R6 is ethyl (C2).

[0064] Ethyl benzoate (EB), where R5 is phenyl (C6) and R6 is ethyl (C2).

[0065] • Diethyl malonate (DEM), where R7 is ethyl (C2) and R8 is ethyl (C2).

[0066] • Diethyl succinate (DES), where R9 is ethyl (C2) and R10 is ethyl (C2).

[0067] ·N,N-Dimethylbenzamide, wherein R13 is phenyl (C6) and R14 and R15 are both methyl (C1).

[0068] • Dimethyl malonate (DMM), where R7 is a methyl group (C2) and R8 is a methyl group (C2).

[0069] • Dimethyl succinate (DMS), where R9 is methyl (C2) and R10 is methyl (C2).

[0070] A method for activating a conventional solid carrier is described in detail in the applicant's WO2015091984A1, page 23, line 3 to page 28, line 14, the entire section of which is incorporated herein by reference.

[0071] In another aspect, the present invention relates to a solid carrier or an activated solid carrier that is directly obtained or can be obtained by the method according to the first aspect.

[0072] In another aspect, the present invention relates to a method for preparing a main catalyst suitable for preparing a catalyst composition for olefin polymerization, the method comprising:

[0073] I) Provide a solid support or an activated solid support according to the invention; and

[0074] II) The main catalyst is obtained by reacting the solid support or activated solid support with a halogen-containing Ti-compound, optionally with an activator and at least one internal electron donor, before or simultaneously with the addition of an internal donor.

[0075] Therefore, a suitable internal electron donor is an electron-donating compound containing one or more oxygen (O) and / or nitrogen (N) atoms. For example, the internal electron donor could be:

[0076] ·9,9-bis(methoxymethyl)fluorene (Flu).

[0077] ·4-[(ethoxycarbonyl)-(methyl)amino]pent-2-ylcarbamate (AB-OEt)

[0078] ·4-[benzoyl(methyl)-amino]pentane-2-ylbenzoate (AB)

[0079] Isopropylisopentyldimethoxypropane (IPIPEN)

[0080] Dibutyl phthalate (DBP)

[0081] In one embodiment of the method for preparing the main catalyst, it is added in II) as an activator and internal electron donor:

[0082] *N,N-Dimethylbenzamide (BA-2Me) as an activator and 9,9-bis(methoxymethyl)fluorene (Flu) as an internal donor; or

[0083] *Ethyl benzoate (EB) as an activator and 4-[(ethoxycarbonyl)-(methyl)amino]pent-2-ylcarbamate (AB-OEt) or 4-[benzoyl(methyl)amino]pent-2-ylbenzoate (AB) as an internal donor; or

[0084] *N,N-Dimethylbenzamide (BA-2Me) was used as an activator and isopropylisopentyldimethoxypropane (IPIPEN) was used as an internal donor.

[0085] In the claims, the expression "comprising / including" does not exclude other elements or steps, and the indefinite article "a" or "an" does not exclude multiple / agents. The foregoing description provides embodiments of the invention by way of example only. The scope of the invention is defined by the appended claims. One or more objectives of the invention are achieved by the appended claims.

[0086] Example

[0087] The present invention will be further illustrated by the following embodiments, which are merely illustrative and not intended to limit the invention.

[0088] I) IC dosing regime: Premix the Grignard compound and the silane compound, dosing temperature 0°C, dosing time 2 hours.

[0089] Example 1 (E1)

[0090] Overview

[0091] This embodiment uses a butyl Grignard compound on a solid support. This support is not activated. An ester compound (diester, dibutyl phthalate, or DBP) is used as the initiator compound, and the same ester, dibutyl phthalate, is used as the internal donor. Step B is performed with a DBP / Mg molar ratio of 0.1, a DBP addition temperature of 0°C, and a DBP addition time of 2 hours.

[0092] Step A) Preparation of Grignard compounds

[0093] This step follows the procedure described in Example III of EP 1222214 B1, but on a large scale. A 16L stainless steel reactor was filled with 280g of magnesium powder. The reactor was placed under a nitrogen atmosphere. The magnesium was heated at 80°C for 1 hour, after which a mixture of dibutyl ether (DBE, 1.5L) and n-chlorobutane (80ml) was added. The temperature was raised to 75°C and iodine (0.7g) was added to the reaction mixture. After the color of the iodine disappeared, a mixture of dibutyl ether (10L) and n-chlorobutane (1.1L) was slowly added over 3 hours. The reaction mixture was kept at 76-78°C. The reaction mixture was stirred at 76°C for another 4 hours. Then stirring and heating were stopped, and the solid material was allowed to settle for 48 hours. By decantation of the solution on the precipitate, a solution of butyl magnesium chloride in dibutyl ether (product A) with a concentration of 0.86 mol Mg / L was obtained in this step.

[0094] Step B) Preparation of carrier + addition of IC

[0095] This step is performed according to the procedure described in Example I of EP 1222214 B1, except that a dibutyl phthalate solution is separately added to the reactor during the component dosing process. 250 ml of dibutyl ether is introduced into a 1.5 L reactor. The reactor is equipped with a paddle stirrer. The reactor is kept at a constant temperature of 0 °C.

[0096] The product A solution (240 ml, 0.206 mol Mg) obtained in step A and the tetraethoxysilane DBE solution (30.4 ml TES + 88.6 ml DBE; Si / Mg = 0.66) were cooled to 5°C and then simultaneously added to a 0.45 ml reactor equipped with a mixing device and enclosed in a sleeve. The addition time was 120 minutes. The mixing device (mini-mixer) was cooled to 5°C by circulating cold water in the sleeve. The contact time of the reagents (product A and TES) in the mini-mixer and the connecting tube between the mini-mixer and the reactor was 14 seconds. A dibutyl phthalate (DBP) DBE solution (5.5 ml DBE and 34.5 ml DBE; molar ratio DBP / Mg = 0.1) was simultaneously added to the reactor over 120 minutes via a separate tube. The stirring speed in the reactor is 350 rpm at the beginning of the dosing phase and gradually increases to a maximum of 425 rpm at the end of the dosing phase.

[0097] After addition, the reaction mixture was heated to 60°C over 120 minutes and maintained at this temperature for 1 hour. Stirring was then stopped, and the solid product was allowed to settle. The supernatant was removed by decantation. The solid was washed three times with 900 ml of heptane. Approximately 30 g of solid product B was obtained, suspended in heptane.

[0098] Step C) Activation of the carrier

[0099] The carrier is not activated.

[0100] Step D) Preparation of the main catalyst

[0101] A 0.3 L glass reactor was placed under a nitrogen atmosphere, and 125 mL of titanium tetrachloride was added to the reactor. A suspension containing approximately 6 g of solid product B in 15 mL of heptane was added to the reactor with stirring. The reaction mixture was then heated to 100 °C over 1 hour, after which 1.6 mL of dibutyl phthalate (DBP / Mg = 0.15) was added to the reactor. The reaction mixture was then heated to 115 °C and maintained at 115 °C for 105 minutes. Stirring was then stopped, and the solid product was allowed to settle. The supernatant was decanted, and the solid product was then washed with chlorobenzene (125 mL) at 100 °C for 20 minutes. The washing solution was then decanted, and a mixture of titanium tetrachloride (62.5 mL) and chlorobenzene (62.5 mL) was added. The reaction mixture was maintained at 115 °C for 30 minutes, after which the solid product was allowed to settle, and the final treatment was repeated once. The obtained solid product was washed five times with 150 mL of heptane at 60 °C to obtain a solid main catalyst suspended in heptane.

[0102] Step E) Polymerization of propylene

[0103] The polymerization of propylene was carried out in a stainless steel reactor (volume 0.7 L) at 70 °C in heptane (300 mL), under a total pressure of 0.7 MPa and in the presence of hydrogen (55 mL), in a main catalyst system containing the main catalyst components according to step C, triethylaluminum, and cyclohexylmethyldimethoxysilane (c-donor) for 1 hour. The concentration of the main catalyst component was 0.033 g / L; the concentration of triethylaluminum was 4.0 mmol / L, and the concentration of the c-donor was 0.2 mmol / L. Table 1 shows the performance data of the main catalyst in the polymerization of propylene.

[0104] Example 2 (E2)

[0105] Overview

[0106] This example uses a butyl Grignard compound on a solid support. This support is activated. An ester compound (diester, dibutyl phthalate, or DBP) is used as the initiator compound, and the same ester, dibutyl phthalate, is used as the internal donor. This is similar to Example 1, except that step C) is performed, and an activated support is used in step D). Step B is performed with a DBP / Mg molar ratio of 0.1, a DBP addition temperature of 0°C, and a DBP addition time of 2 hours.

[0107] Step C) Activation of the carrier

[0108] The additional support activation stage was then performed by treating product B with ethanol according to the procedure proposed in EP 1661917A1. Under an inert nitrogen atmosphere at 0°C, 6 g of product B slurry dispersed in 100 mL of heptane was added to a 0.3 L glass flask equipped with a mechanical stirrer. Subsequently, a solution of 0.96 mL of ethanol in 20 mL of heptane was added over 1 hour at 0°C, resulting in an ethanol / Mg ratio of 0.4. The slurry was then slowly heated to 30°C for 90 minutes and held at that temperature for another 2 hours. Finally, the supernatant layer was decanted from the solid reaction product and washed once with 150 mL of heptane at 30°C. This yielded product C (the activated support), suspended in 15 mL of heptane.

[0109] Example 3 (E3)

[0110] Overview

[0111] This example uses a butyl Grignard compound on a solid support. This support is not activated. An ester compound (monoester, ethyl benzoate, or EB) is used as the initiator compound, and dibutyl phthalate is used as the internal donor. Steps A), D), and E) are performed as described in Example 1. Step C) is not performed. Step B is discussed below. Step B is performed with a molar ratio of EB / Mg of 0.1, an EB addition temperature of 0°C, and an EB addition time of 2 hours.

[0112] Step B) Preparation of carrier + addition of IC

[0113] Product B (carrier) was prepared as described in Example 1, except that during component dosing, an ethyl benzoate solution (2.96 ml of ethyl benzoate (0.1 EB / Mg) and 37 ml of DBE) was added to the reactor instead of the dibutyl phthalate solution.

[0114] Example 4 (E4)

[0115] Overview

[0116] This example uses a butyl Grignard compound on a solid support. The support is activated. An ester compound (monoester, ethyl benzoate, or EB) is used as the initiator compound, and dibutyl phthalate is used as the internal donor. Steps A), D), and E) are performed as described in Example 1. Step C) is performed as described in Example 2. Step B is performed as described in Example 3. Step B is performed with a molar ratio of EB / Mg of 0.1, an EB addition temperature of 0°C, and an EB addition time of 2 hours.

[0117] Example 5 (E5)

[0118] Overview

[0119] This embodiment uses a butyl Grignard compound on a solid support. The support is not activated. A ketone compound (monoketone, methyl isobutyl ketone, or MIBK) is used as the initiator compound, and dibutyl phthalate is used as the internal donor. Steps A), D), and E) are performed as described in Example 1. Step C) is not performed. Step B is performed as disclosed below. Step B is performed with a MIBK / Mg molar ratio of 0.1, a MIBK addition temperature of 0°C, and a MIBK addition time of 2 hours.

[0120] Step B) Preparation of carrier + addition of IC

[0121] Product B (carrier) was prepared as described in Example 1, except that methyl isobutyl ketone was used instead of dibutyl phthalate (2.58 ml methyl isobutyl ketone (MIBK) and 47 ml DBE; molar ratio MIBK / Mg = 0.1).

[0122] Example 6 (E6)

[0123] Overview

[0124] This embodiment uses a butyl Grignard compound on a solid support. The support is not activated. A ketone compound (diketone, acetylacetone, or AcAc) is used as the initiator compound, and dibutyl phthalate is used as the internal donor. Steps A), D), and E) are performed as described in Example 1. Step C) is not performed. Step B is performed as disclosed below. Step B is performed with a molar ratio of AcAc / Mg of 0.1, an AcAc addition temperature of 0°C, and an AcAc addition time of 2 hours.

[0125] Step B) Preparation of carrier + addition of IC

[0126] Product B (carrier) was prepared as described in Example 1, except that acetylacetone was used instead of dibutyl phthalate (2.1 ml acetylacetone (AcAc) and 47 ml DBE; molar ratio AcAc / Mg = 0.1).

[0127] Example 7 (E7)

[0128] Overview

[0129] This example uses a butyl Grignard compound on a solid support. The support is activated. A ketone compound (diketone, acetylacetone, or AcAc) is used as the initiator compound, and dibutyl phthalate is used as the internal donor. Steps A), D), and E) are performed as described in Example 1. Step C) is performed as described in Example 2. Step B is performed as described in Example 23. Step B is performed with a molar ratio of AcAc / Mg of 0.1, an Ac addition temperature of 0°C, and an Ac addition time of 2 hours.

[0130] Example 8 (E8)

[0131] Overview

[0132] This embodiment uses a butyl Grignard compound on a solid support. The support is not activated. A ketone compound (monoketone, methyl propyl ketone, or MPK) is used as the initiator compound, and dibutyl phthalate is used as the internal donor. Steps A), D), and E) are performed as described in Example 1. Step C) is not performed. Step B is performed as disclosed below. Step B is performed with a molar ratio of MPK / Mg of 0.1, an IC dosing temperature of 0°C, and an MPK dosing time of 2 hours.

[0133] Step B) Preparation of carrier + addition of IC

[0134] Product B (carrier) was prepared as described in Example 1, except that methyl propyl ketone was used instead of dibutyl phthalate (2.2 ml methyl propyl ketone (MPK) and 48 ml DBE; molar ratio MPK / Mg = 0.1).

[0135] Example 9 (E9)

[0136] Overview

[0137] This example uses a butyl Grignard compound on a solid support. The support is activated. A ketone compound (monoketone, methyl propyl ketone, or MPK) is used as the initiator compound, and dibutyl phthalate is used as the internal donor. Steps A), D), and E) are performed as described in Example 1. Step C) is performed as described in Example 2. Step B is performed as described in Example 8. Step B is performed with a molar ratio of MPK / Mg of 0.1, an MPK addition temperature of 0°C, and an MPK addition time of 2 hours.

[0138] Example 10 (E10)

[0139] Overview

[0140] This embodiment uses a butyl Grignard compound on a solid support. The support is not activated. A ketone compound (monoketone, diisopropyl ketone DIPK) is used as the initiator compound, and dibutyl phthalate is used as the internal donor. Steps A), D), and E) are performed as described in Example 1. Step C) is not performed. Step B is performed as disclosed below. Step B is performed with a DIPK / Mg molar ratio of 0.1, a DIPK dosing temperature of 0°C, and a DIPK dosing time of 2 hours.

[0141] Step B) Preparation of carrier + addition of IC

[0142] Product B (carrier) was prepared as described in Example 1, except that diisopropyl ketone was used instead of dibutyl phthalate (2.35 g diisopropyl ketone (DIPK) and 48 ml DBE; molar ratio DIPK / Mg = 0.1).

[0143] Example 11 (E11)

[0144] Overview

[0145] This example uses a butyl Grignard compound on a solid support. The support is activated. A ketone compound (monoketone, diisopropyl ketone DIPK) is used as the initiator compound, and dibutyl phthalate is used as the internal donor. Steps A), D), and E) are performed as described in Example 1. Step C) is performed as described in Example 2. Step B is performed as described in Example 10. Step B is performed with a DIPK / Mg molar ratio of 0.1, a DIPK dosing temperature of 0°C, and a DIPK dosing time of 2 hours.

[0146] Example 12 (E12)

[0147] Overview

[0148] This example uses a butyl Grignard compound on a solid support. This support is not activated. An ester compound (monoester, ethyl benzoate, or EB) is used as the initiator compound, and dibutyl phthalate is used as the internal donor. Steps A), D), and E) are performed as described in Example 1. Step C) is omitted. Step B is performed as described in Example 3, except that during component dosing, 5.92 ml of ethyl benzoate is used instead of 2.96 ml (5.92 ml of EB and 34 ml of DBE, molar ratio EB / Mg = 0.2). Step B is performed with a molar ratio EB / Mg of 0.2, an EB dosing temperature of 0°C, and an EB dosing time of 2 hours.

[0149] Example 13 (E13)

[0150] Overview

[0151] This example uses a butyl Grignard compound on a solid support. The support is not activated. An ester compound (monoester, ethyl benzoate, or EB) is used as the initiator compound, and dibutyl phthalate is used as the internal donor. Steps A), D), and E) are performed as described in Example 1. Step C) is omitted. Step B is performed as described in Example 12, except that during component dosing, 1.48 ml of ethyl benzoate (1.48 ml of EB and 38.5 ml of DBE, molar ratio EB / Mg = 0.05) is used. Step B is performed with a molar ratio EB / Mg of 0.05, an EB dosing temperature of 0°C, and an EB dosing time of 2 hours.

[0152] Example 14 (E14)

[0153] Overview

[0154] This example uses a butyl Grignard compound on a solid support. The support is not activated. An ester compound (monoester, ethyl benzoate, or EB) is used as the initiator compound, and dibutyl phthalate is used as the internal donor. Steps A), D), and E) are performed as described in Example 1. Step C) is omitted. Step B is performed as described in Example 12, except that during component dosing, 0.74 ml of ethyl benzoate (0.74 ml of EB and 39 ml of DBE, molar ratio EB / Mg = 0.025) is used. Step B is performed with a molar ratio EB / Mg of 0.025, an EB dosing temperature of 0°C, and an EB dosing time of 2 hours.

[0155] Example 15 (E15)

[0156] Overview

[0157] This example uses a butyl Grignard compound on a solid support. The support is not activated. An ester compound (diester, dibutyl phthalate, or DBP) is used as the initiator compound, and dibutyl phthalate is used as the internal donor. Steps A), D), and E) are performed as described in Example 1. Step C) is omitted. Step B is performed as described in Example 1, except that during component dosing, 22 ml of dibutyl phthalate is used instead of 5.5 ml (22 ml dibutyl phthalate and 18 ml DBE; molar ratio DBP / Mg = 0.4). Step B is performed with a molar ratio of DBP / Mg of 0.4, a DBP dosing temperature of 0°C, and a DBP dosing time of 2 hours.

[0158] Comparative Example 1 (CE1)

[0159] Overview

[0160] This embodiment uses a butyl Grignard compound on a solid support. The support is not activated. No initiator compound is used. An ester compound (diester, dibutyl phthalate, or DBP) is used as the internal donor, with a DBP / Mg ratio of 0.15. Steps A), D), and E) are performed as described in Example 1, but step C is omitted. Step B) is described below.

[0161] Step B) Preparation of the carrier

[0162] The preparation of solid product B (support) was carried out as described in Example 1, except that dibutyl phthalate solution was not used for preparation, i.e., the support synthesis procedure was close to Example 1 of EP 1222214 B1.

[0163] Comparative Example 2 (CE2)

[0164] Overview

[0165] This embodiment uses a butyl Grignard compound on a solid support. The support is not activated. No initiator compound is used. An ester compound (diester, dibutyl phthalate, or DBP) is used as the internal donor, with a DBP / Mg ratio of 0.2. Steps A), D), and E) are performed as described in Example 1, but step C is omitted. Step B) is described below.

[0166] Step B) Preparation of the carrier

[0167] The preparation of solid product B (support) was carried out as described in Example 1, except that dibutyl phthalate solution was not used for preparation, i.e., the support synthesis procedure was close to Example 1 of EP 1222214 B1.

[0168] Comparative Example 3 (CE3)

[0169] Overview

[0170] This embodiment uses a butyl Grignard compound on a solid support. The support is not activated. No initiator compound is used. An ester compound (diester, dibutyl phthalate, or DBP) is used as the internal donor, with a DBP / Mg ratio of 0.25. Steps A), D), and E) are performed as described in Example 1, but step C is omitted. Step B) is described below.

[0171] Step B) Preparation of the carrier

[0172] The preparation of solid product B (support) was carried out as described in Example 1, except that dibutyl phthalate solution was not used for preparation, i.e., the support synthesis procedure was close to Example 1 of EP 1222214 B1.

[0173] Comparative Example 4 (CE4)

[0174] Overview

[0175] This embodiment uses a butyl Grignard compound on a solid support. The support is not activated. No initiator compound is used. An ester compound (diester, dibutyl phthalate, or DBP) is used as the internal donor. Steps A), D), and E) are performed as described in Example 1, and step C is performed according to Example 2. Step B) is performed as described in Comparative Example 1.

[0176] Table 1. Examples of using DBP as an internal donor in step B with a dosing temperature of 0°C and a dosing time of 2 hours. *

[0177]

[0178] SPAN = (D90 - D10) / D50

[0179] Ti = Titanium content of the main catalyst (wt%), based on the total weight of the main catalyst; Yield = Activity used in the polymerization process (PP yield kg / main catalyst g / 1 hour); Yield / Ti = PP yield / number of grams of Ti in the main catalyst

[0180] XS = xylene soluble content (wt%), based on the total weight of the obtained polymer; BD = bulk density (g / l)

[0181]

[0182] *PVss = Pore volume of the solid carrier (VΣ), unit: cm 3 per gram of carrier

[0183] PVp = pore volume of the main catalyst (VΣ), in cm 3 per gram of carrier

[0184] SAss = Surface area of ​​solid carrier (S) BET), unit m 2 per gram of carrier

[0185] SAp = Surface area of ​​the main catalyst (S) BET ), unit m 2 per gram of carrier

[0186] The table above clearly shows that both the non-activated support and the activated support (with IC added during the support synthesis) of the present invention achieve at least one of the following: i) increased yield; ii) increased yield / wt% titanium; iii) increased pore volume and surface area of ​​the solid support; iv) increased pore volume and surface area of ​​the formed main catalyst.

[0187] By adding an initiator compound in Example 1, the DBP / Mg ratio was increased from 0.15 to 0.25 (0.1 as the initiator compound in step B and 0.15 as the internal electron donor in step D). To examine whether the lack of positive effects was solely due to the increased DBP amount or actually due to the pre-dosing of DBP in the form of the initiator compound, Comparative Examples 2 and 3 (CE2 and CE3) were conducted with DBP / Mg ratios of 0.2 and 0.25, where the full dose of DBP acted as the internal electron donor in step D. Compared to the optimal DBP / Mg = 0.15, the increased DBP amount resulted in a 20-30% decrease in activity and a deterioration in stereospecificity. Not wishing to be limited by specific theories, the inventors believe that because DBP (and other ICs) contain carboxyl groups, these carboxyl groups will interact with BuMgCl and be converted into derivatives of secondary and tertiary alcohols. In the final master catalyst obtained, such an initiator compound is no longer present; instead, it is converted during initiation activity.

[0188] Several tests were conducted to investigate the optimal IC / Mg ratio used in step B. When comparing Example 15 with Example 1 (and both with CE1), it was clear that as the IC / Mg ratio increased from 0.1 to 0.4, the overall yield decreased, and XS increased to the same level as when IC was absent. Therefore, an IC / Mg ratio of 0.1 is superior to 0.4. When comparing Example 12 with Example 3 (and both with CE1), it was clear that as the IC / Mg ratio increased from 0.1 to 0.2, the overall yield decreased, and XS increased to almost the same level as when IC was absent. Therefore, an IC / Mg ratio of 0.1 is superior to 0.2. When comparing Examples 13 and 14 with Example 3 (and both with CE1), it was clear that as the IC / Mg ratio decreased from 0.1 to 0.05 or even 0.025, the overall yield decreased, and XS increased to almost the same level as when IC was absent. Therefore, an IC / Mg ratio of 0.1 is superior to 0.05 and 0.025.

[0189] Another advantage of this invention is the increase in pore volume and specific surface area of ​​the support and catalyst obtained in the presence of an electron donor compound. This advantage will be useful for using the catalyst obtained according to this invention in copolymerization processes of propylene with other olefins. The increase in pore volume and specific surface area, as well as the increase in catalyst activity, is achieved by introducing the donor compound as an initiator compound into the support during the support synthesis process.

[0190] II) IC dosing scheme: Grignard compound and silane compound premixed, dosing temperature 35°C, dosing time 5 hours.

[0191] Example 16 (E16)

[0192] Overview

[0193] This embodiment uses a butyl Grignard compound on a solid support. This support is not activated. An ester compound (diester, dibutyl phthalate, or DBP) is used as the initiator compound, and dibutyl phthalate is used as the internal donor. Steps A), D), and E) are performed as described in Example 1. Step C) is omitted. Step B is performed as follows. Step B is performed with a DBP / Mg molar ratio of 0.1, a DBP addition temperature of 35°C, and a DBP addition time of 5 hours.

[0194] Step B) Preparation of carrier + addition of IC

[0195] Product B (carrier) was prepared as described in Example 1, except that the temperature was 35°C and the dosing time was 5 hours during the dosing stage. 300 ml of dibutyl ether was introduced into a 1.5 L reactor. The reactor was equipped with a paddle stirrer and maintained at a constant temperature of 35°C.

[0196] The solution of product A obtained in step A (450 ml, 0.387 mol Mg) and the DBE solution of tetraethoxysilane (57 ml TES + 168 ml DBE; Si / Mg = 0.66) were cooled to 5°C and then simultaneously added to a 0.45 ml reactor equipped with a mixing device and a casing. The addition time was 300 minutes. The mixing device (small mixer) was cooled to 5°C by circulating cold water in the casing. The contact time of the reagents (product A and TES) in the small mixer and the connecting tube between the small mixer and the reactor was 18.7 seconds. A DBE solution of dibutyl phthalate (DBP) (10.3 ml DBE and 39.7 ml DBE; molar ratio DBP / Mg = 0.1) was simultaneously added to the reactor over 300 minutes via a separate tube. The stirring speed in the reactor is 350 rpm at the beginning of the dosing phase and is gradually increased to a maximum of 500 rpm at the end of the dosing phase.

[0197] After addition, the reaction mixture was heated to 60°C over 30 minutes and maintained at this temperature for 1 hour. Stirring was then stopped, and the solid product was allowed to settle. The supernatant was removed by decantation. The solid was washed three times with 500 ml of heptane. Solid product B was obtained, suspended in heptane.

[0198] Example 17 (E17)

[0199] Overview

[0200] This example uses a butyl Grignard compound on a solid support. The support is activated. An ester compound (diester, dibutyl phthalate, or DBP) is used as the initiator compound, and dibutyl phthalate is used as the internal donor. Steps A), D), and E) are performed as described in Example 1. Step C) is performed according to Example 2. Step B is performed according to Example 16. Step B is performed with a molar ratio of IC / Mg of 0.1, an IC addition temperature of 35°C, and an IC addition time of 5 hours.

[0201] Example 18 (E18)

[0202] Overview

[0203] This example uses a butyl Grignard compound on a solid support. The support is activated. An ester compound (diester, dibutyl phthalate, or DBP) is used as the initiator compound, and dibutyl phthalate is used as the internal donor. Steps A), D), and E) are performed as described in Example 1. Step C) is performed as described below. Step B is performed according to Example 17. Step B is performed with a molar ratio of IC / Mg of 0.1, an IC dispensing temperature of 35°C, and an IC dispensing time of 5 hours. This differs from Example 6 in the different support activation.

[0204] Step C) Activation of the carrier

[0205] The activation of the support for product B was carried out using ethanol and titanium tetraethoxide according to a procedure similar to that described in Example 4 of EP 1661917A1. A slurry of 6 g of product B dispersed in 100 ml of heptane was filled into a 0.3 L glass flask equipped with a mechanical stirrer at 0 °C under an inert nitrogen atmosphere. Subsequently, a solution of 0.96 ml of ethanol in 20 ml of heptane was added over 1 hour at 0 °C, resulting in an ethanol / Mg ratio of 0.4. The reaction mixture was maintained at 0 °C for 30 minutes. The temperature was then raised to 20 °C, and a solution of 0.944 g of titanium tetraethoxide (TET / Mg = 0.1) in 20 ml of heptane was added over 1 hour. The slurry was then heated to 30 °C over 30 minutes and maintained at that temperature for another 3 hours. Finally, the supernatant layer was removed by decantation from the solid reaction product and washed once with 150 ml of heptane at 30 °C. The result was product C (the activated support), suspended in 15 ml of heptane.

[0206] Example 19 (E19)

[0207] Overview

[0208] This embodiment uses a butyl Grignard compound on a solid support. This support is not activated. An ester compound (monoester, ethyl benzoate, or EB) is used as the initiator compound, and dibutyl phthalate is used as the internal donor. Steps A), D), and E) are performed as described in Example 1. Step C) is omitted. Step B is performed as disclosed below. Step B is performed with a molar ratio of EB / Mg of 0.1, an EB inoculation temperature of 35°C, and an EB inoculation time of 5 hours.

[0209] Step B) Preparation of carrier + addition of IC

[0210] Product B (carrier) was prepared as described in Example 16, except that ethyl benzoate was used instead of dibutyl phthalate (5.3 ml of ethyl benzoate (EB) and 44.7 ml of DBE; molar ratio EB / Mg = 0.1).

[0211] Example 20 (E20)

[0212] Overview

[0213] This example uses a butyl Grignard compound on a solid support. The support is not activated. An ester compound (monoester, ethyl benzoate, or EB) is used as the initiator compound, and dibutyl phthalate is used as the internal donor. Steps A), D), and E) are performed as described in Example 1. Step C) is performed according to Example 2. Step B) is performed as described in Example 18. Step B is performed with a molar ratio of EB / Mg of 0.1, an EB addition temperature of 35°C, and an EB addition time of 5 hours.

[0214] Example 21 (E21)

[0215] Overview

[0216] This example uses a butyl Grignard compound on a solid support. This support is not activated. A ketone compound (monoketone acetone or Ac) is used as the initiator compound, and dibutyl phthalate is used as the internal donor. Steps A), D), and E) are performed as described in Example 1. Step C) is omitted. Step B) is performed as follows. Step B is performed with a molar ratio of Ac / Mg of 0.1, an Ac addition temperature of 35°C, and an Ac addition time of 5 hours.

[0217] Step B) Preparation of carrier + addition of IC

[0218] Product B (carrier) was prepared as described in Example 16, except that acetone was used instead of dibutyl phthalate (2.81 ml Ac and 47.2 ml DBE; molar ratio Ac / Mg = 0.1).

[0219] Example 22 (E22)

[0220] Overview

[0221] This embodiment uses a butyl Grignard compound on a solid support. This support is not activated. A ketone compound (acetophenone or AcPh) is used as the initiator compound, and dibutyl phthalate is used as the internal donor. Steps A), D), and E) are performed as described in Example 1. Step C) is omitted. Step B) is performed as follows. Step B is performed with a molar ratio of AcPh / Mg of 0.1, an AcPh inoculation temperature of 35°C, and an AcPh inoculation time of 5 hours.

[0222] Step B) Preparation of carrier + addition of IC

[0223] Product B (carrier) was prepared as described in Example 16, except that acetophenone was used instead of dibutyl phthalate (4.52 ml of acetophenone (AcPh) and 45.5 ml of DBE; molar ratio AcPh / Mg = 0.1).

[0224] Example 23 (E23)

[0225] Overview

[0226] This example uses a butyl Grignard compound on a solid support. The support is activated. A ketone compound (acetophenone or AcPh) is used as the initiator compound, and dibutyl phthalate is used as the internal donor. Steps A), D), and E) are performed as described in Example 1. Step C) is performed according to Example 2. Step B) is performed according to Example 22. Step B is performed with a molar ratio of AcPh / Mg of 0.1, an AcPh addition temperature of 35°C, and an AcPh addition time of 5 hours.

[0227] Example 24 (E24)

[0228] Overview

[0229] This embodiment uses a butyl Grignard compound on a solid support. The support is not activated. An ester compound (diester, diethyl malonate, or DEM) is used as the initiator compound, and dibutyl phthalate is used as the internal donor. Steps A), D), and E) are performed as described in Example 1. Step C) is omitted. Step B) is performed as follows. Step B is performed with a DEM / Mg molar ratio of 0.1, a DEM addition temperature of 35°C, and a DEM addition time of 5 hours.

[0230] Step B) Preparation of carrier + addition of IC

[0231] Product B (carrier) was prepared as described in Example 16, except that diethyl malonate was used instead of dibutyl phthalate (6.2 g of diethyl malonate (DEM) and 44 ml of DBE; molar ratio DEM / Mg = 0.1).

[0232] Example 25 (E25)

[0233] Overview

[0234] This embodiment uses a butyl Grignard compound on a solid support. This support is not activated. An ester compound (diester, diethyl succinate, or DES) is used as the initiator compound, and dibutyl phthalate is used as the internal donor. Steps A), D), and E) are performed as described in Example 1. Step C) is omitted. Step B) is performed as follows. Step B is performed with a DES / Mg molar ratio of 0.1, a DES addition temperature of 35°C, and a DES addition time of 5 hours.

[0235] Step B) Preparation of carrier + addition of IC

[0236] Product B (carrier) was prepared as described in Example 16, except that diethyl succinate was used instead of dibutyl phthalate (6.74 g of diethyl succinate (DES) and 44 ml of DBE; molar ratio DES / Mg = 0.1).

[0237] Example 26 (E26)

[0238] Overview

[0239] This example uses a butyl Grignard compound on a solid support. This support is not activated. A benzamide compound (N,N-dimethylbenzamide or BA) is used as the initiator compound, and dibutyl phthalate is used as the internal donor. Steps A), D), and E) are performed as described in Example 1. Step C) is omitted. Step B) is performed as follows. Step B is performed with a BA / Mg molar ratio of 0.1, a BA inoculation temperature of 35°C, and a BA inoculation time of 5 hours.

[0240] Step B) Preparation of carrier + addition of IC

[0241] Product B (carrier) was prepared as described in Example 16, except that N,N-dimethylbenzamide was used instead of dibutyl phthalate (5.77 g of N,N-dimethylbenzamide (BA) and 45 ml of DBE; molar ratio BA / Mg = 0.1).

[0242] Example 27 (E27)

[0243] Overview

[0244] This example uses a butyl Grignard compound on a solid support. The support is activated. A benzamide compound (N,N-dimethylbenzamide or BA) is used as the initiator compound, and dibutyl phthalate is used as the internal donor. Steps A), D), and E) are performed as described in Example 1. Step C) is performed according to Example 2. Step B) is performed according to Example 26. Step B is performed with a BA / Mg molar ratio of 0.1, a BA addition temperature of 35°C, and a BA addition time of 5 hours.

[0245] Example 28 (E28)

[0246] Overview

[0247] This example uses a butyl Grignard compound on a solid support. This support is not activated. An ester compound (butyl acetate monoester or BuAc) is used as the initiator compound, and dibutyl phthalate is used as the internal donor. Steps A), D), and E) are performed as described in Example 1. Step C) is omitted. Step B) is performed as follows. Step B is performed with a BuAc / Mg molar ratio of 0.1, a BuAc inoculation temperature of 35°C, and a BuAc inoculation time of 5 hours.

[0248] Step B) Preparation of carrier + addition of IC

[0249] Product B (carrier) was prepared as in Example 19, except that butyl acetate was used instead of ethyl benzoate (5.1 ml of butyl acetate (BuAc) and 45 ml of DBE; molar ratio BuAc / Mg = 0.1).

[0250] Example 29 (E29)

[0251] Overview

[0252] This example uses a butyl Grignard compound on a solid support. The support is activated. An ester compound (butyl acetate monoester or BuAc) is used as the initiator compound, and dibutyl phthalate is used as the internal donor. Steps A), D), and E) are performed as described in Example 1. Step C) is performed according to Example 2. Step B) is performed according to Example 28. Step B is performed with a BuAc / Mg molar ratio of 0.1, a BuAc inoculation temperature of 35°C, and a BuAc inoculation time of 5 hours.

[0253] Comparative Example 5 (CE5)

[0254] Overview

[0255] This embodiment uses a butyl Grignard compound on a solid support. The support is not activated. No initiator compound is used. An ester compound (diester, dibutyl phthalate, or DBP) is used as the internal donor. Steps A), D), and E) are performed as described in Example 16, but step C is omitted. Step B) is described below.

[0256] Step B) Preparation of the carrier

[0257] The preparation of solid product B (carrier) was carried out as described in Example 16, except that dibutyl phthalate solution was not used for preparation, i.e., the carrier synthesis procedure was close to Example I of EP 1222214 B1.

[0258] Comparative Example 6 (CE6)

[0259] Overview

[0260] This embodiment uses a butyl Grignard compound on a solid support. The support is activated. No initiator compound is used. An ester compound (diester, dibutyl phthalate, or DBP) is used as the internal donor. Steps A), D), and E) are performed as described in Example 16, and step C is performed according to Example 2. Step B) is performed as described in Comparative Example 5.

[0261] Table 2. Examples of using DBP as an internal donor in step B with a dosing temperature of 35°C and a dosing time of 5 hours.

[0262]

[0263] # Dual activation with TET and ETOH

[0264]

[0265] The table above clearly shows that both the non-activated support and the activated support (with IC added during support synthesis) of the present invention achieve at least one of the following: i) increased yield; ii) increased yield / wt% titanium; iii) increased pore volume and surface area of ​​the solid support; and iv) increased pore volume and surface area of ​​the formed main catalyst.

[0266] Other methods to increase yield are also known, for example, from EP 1661917, in which the support is activated by ethanol and titanium tetraoxide. When comparing Example 18 with Example 17, it can be seen that this master catalyst according to the invention, even using a single-activated support (E17), yields similar or even better results in terms of yield and XS as the dual-activated support (E18). Therefore, similar / better results were obtained using a simpler approach.

[0267] III) Examples of using different internal donors in step B, with a dosing temperature of 0°C and a dosing time of 2 hours.

[0268] Example 30 (E30)

[0269] Overview

[0270] This embodiment uses a butyl Grignard compound on a solid support. The support is activated. An ester compound (monoester, ethyl benzoate, or EB) is used as the initiator compound; ethyl benzoate is used as the activator of the internal donor; and 4-[benzoyl(methyl)-amino]pentan-2-ylbenzoate (AB) is used as the internal donor.

[0271] Steps A) and E) are performed as described in Example 1.

[0272] Step B was performed as described in Example 3, except that 1.48 ml of ethyl benzoate (1.48 ml of EB and 38.5 ml of DBE, molar ratio EB / Mg = 0.05) was used during the component dosing process.

[0273] Step C) is performed according to Example 2.

[0274] Step D) Preparation of catalyst + activator + ID

[0275] The main catalyst was prepared using two donors: ethyl benzoate (as a donor activator) and amino benzoate (AB), as described below. A 0.3 L glass reactor was placed under a nitrogen atmosphere, and 100 mL of titanium tetrachloride was added to the reactor. A suspension (containing 6 g of activated solid product B in 15 mL of heptane) was added to the reactor with stirring. The reaction mixture was maintained at room temperature for 60 min. The temperature of the reaction mixture was then gradually increased to 105 °C over 60 min, and a solution of ethyl benzoate (1.68 g in 3 mL of toluene, EB / Mg = 0.3) was added to the reactor over 15 min at a temperature of 20–50 °C. The reaction mixture was maintained at T = 105 °C for 90 min. Stirring was then stopped, and the solids were allowed to settle. The supernatant was removed by decantation, and the solid product was then washed with chlorobenzene (120 mL) at 100 °C for 20 min. The washing solution was then decanted off, followed by the addition of a mixture of titanium tetrachloride (60 ml) and chlorobenzene (60 ml). The reaction mixture was heated to 105 °C and an amino benzoate solution (0.64 g, in 3 ml toluene, AB / Mg = 0.05) was added. The reaction mixture was maintained at T = 105 °C for 60 minutes. The solid was then allowed to settle, the supernatant was decanted off, and the final treatment was repeated once, except using 0.57 g of AB (AB / Mg = 0.045). The mixture of titanium tetrachloride (60 ml) and chlorobenzene (60 ml) was then added, and the reaction mixture was maintained at T = 105 °C for 30 minutes. The solid was allowed to settle, the supernatant was decanted off, and the obtained solid catalyst was washed five times with 150 ml of heptane at 60 °C.

[0276] Example 31 (E31)

[0277] Overview

[0278] This embodiment uses a butyl Grignard compound on a solid support. The support is activated. An ester compound (monoester, ethyl benzoate, or EB) is used as the initiator compound; ethyl benzoate is used as the activator of the internal donor; and 4-[benzoyl(methyl)-amino]pentan-2-ylbenzoate (AB) is used as the internal donor.

[0279] Steps A) and E) are performed as described in Example 1.

[0280] Step B) is performed as described in Example 3, except that 0.74 ml of ethyl benzoate (0.74 ml of EB and 39 ml of DBE, molar ratio EB / Mg = 0.025) is used during the component dosing process.

[0281] Step C) is performed according to Example 2.

[0282] Step D is performed according to Example 30.

[0283] Example 32 (E32)

[0284] Overview

[0285] This embodiment uses a butyl Grignard compound on a solid support. The support is activated. An ester compound (monoester, ethyl acetate, or EA) is used as the initiator compound; N,N-dimethylbenzamide (BA-2Me) is used as the activator of the internal donor; and 9,9-bis(methoxymethyl)fluorene (Flu) is used as the internal donor.

[0286] Steps A) and E) are performed as described in Example 1.

[0287] Step B) is performed according to Example 4.

[0288] Step C) is performed according to Example 2.

[0289] Step D) is performed as follows.

[0290] Step D) Preparation of main catalyst + activator + ID

[0291] The preparation of the main catalyst was carried out using two additional donors: benzamide (BA-2Me) (as a donor activator) and fluorene (Flu), as described below. A 0.3 L glass reactor was placed under a nitrogen atmosphere, and 120 mL of titanium tetrachloride was added to the reactor. A suspension (containing 6 g of activated solid product B in 15 mL of heptane) was added to the reactor with stirring. The reaction mixture was kept at room temperature for 60 minutes. The reactor was heated to 100 °C, and 0.87 g of N,N-dimethylbenzamide (BA-2Me / Mg = 0.15 molar ratio) in 2 mL of chlorobenzene was added to the reactor. The reaction mixture was kept at 105 °C for 10 minutes, and 1.31 g of 9,9-dimethoxymethyl-9H-fluorene (flu / Mg = 0.132 molar ratio) in 3 mL of chlorobenzene was added to the reactor. The reaction mixture was kept at 105 °C for 90 minutes. Then stirring was stopped, and the solids were allowed to settle. The supernatant was removed by decantation, and the solid product was then washed with chlorobenzene (120 ml) at 100 °C for 20 min. The washing solution was then decanted, and a mixture of titanium tetrachloride (60 ml) and chlorobenzene (60 ml) was added. The reaction mixture was maintained at 105 °C for 60 min, after which the solid was allowed to settle. The supernatant was decanted, and the final treatment was repeated twice. The obtained solid was washed five times with 150 ml of heptane at 60 °C, yielding the main catalyst component, which was suspended in heptane.

[0292] Example 33 (E33)

[0293] Overview

[0294] This embodiment uses a butyl Grignard compound on a solid support. The support is activated. An ester compound (monoester, ethyl benzoate, or EB) is used as the initiator compound; N,N-dimethylbenzamide (BA-2Me) is used as the activator of the internal donor, and 9,9-bis(methoxymethyl)fluorene (Flu) is used as the internal donor. Steps A) and E) are performed as described in Example 1.

[0295] Step B) is performed according to Example 3.

[0296] Step C) is performed according to Example 2.

[0297] Step D) is performed according to Example 32.

[0298] Example 34 (E34)

[0299] Overview

[0300] This embodiment uses a butyl Grignard compound on a solid support. The support is activated. An ester compound (monoester, ethyl benzoate, or EB) is used as the initiator compound; N,N-dimethylbenzamide (BA-2Me) is used as the activator of the internal donor; and isopropylisopentyldimethoxypropane (IPIPEN) is used as the internal donor. Steps A) and E) are performed as described in Example 1.

[0301] Step B) is performed according to Example 3.

[0302] Step C) is performed according to Example 18.

[0303] Step D) is performed as follows.

[0304] Step D) Preparation of main catalyst + activator + ID

[0305] The main catalyst was prepared using two additional donors: benzamide (BA-2Me) as a donor activator and isopropylisopentyldimethoxypropane (IPIPEN) as described below. A 0.3 L glass reactor was placed under a nitrogen atmosphere, and 138 mL of titanium tetrachloride was added to the reactor. The suspension (containing 5.5 g of activated solid product B in 10 mL of heptane) was added to the reactor with stirring. The reaction mixture was maintained at room temperature for 60 minutes. The reactor was then heated to 100 °C, and 0.96 g of N,N-dimethylbenzamide (BA-2Me / Mg = 0.16 molar ratio) in 3 mL of chlorobenzene was added to the reactor. The reaction mixture was maintained at 100 °C for 10 minutes, and 0.61 g of isopropylisopentyldimethoxypropane (IPIPEN / Mg = 0.074 molar ratio) in 3 mL of chlorobenzene was added to the reactor. The reaction mixture was maintained at 100 °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 washed with chlorobenzene (138 ml) at 100 °C for 20 min. This washing solution was then decanted, and a mixture of titanium tetrachloride (69 ml) and chlorobenzene (69 ml) was added. Then, 0.55 g of isopropylisopentyldimethoxypropane (IPIPEN / Mg = 0.061 molar ratio) in 3 ml of chlorobenzene was added to the reactor. The reaction mixture was maintained at 105 °C for 60 min, after which the solids were allowed to settle. The supernatant was decanted, and the mixture of titanium tetrachloride (69 ml) and chlorobenzene (69 ml) was added, and the reaction mixture was maintained at 105 °C for 60 min. The solids were then allowed to settle, the supernatant was decanted, and the final treatment was repeated. The obtained solids were washed five times with 150 ml of heptane at 60 °C, yielding the main catalyst component suspended in heptane.

[0306] Comparative Example 7 (CE7)

[0307] Overview

[0308] This embodiment uses a butyl Grignard compound on a solid support. The support is activated. No initiator compound is used; ethyl benzoate is used as the activator of the internal donor, and 4-[benzoyl(methyl)-amino]pent-2-ylbenzoate (AB) is used as the internal donor.

[0309] Steps A) and E) are performed as described in Example 1.

[0310] Step B) is carried out according to Comparative Example 1.

[0311] Step C) is performed according to Example 2.

[0312] Step D) is performed according to Example 30.

[0313] Comparative Example 8 (CE8)

[0314] Overview

[0315] This embodiment uses a butyl Grignard compound on a solid support. The support is activated. No initiator compound is used; N,N-dimethylbenzamide (BA-2Me) is used as the activator of the internal donor, and 9,9-bis(methoxymethyl)fluorene (Flu) is used as the internal donor.

[0316] Steps A) and E) are performed as described in Example 1.

[0317] Step B) is carried out according to Comparative Example 1.

[0318] Step C) is performed according to Example 2.

[0319] Step D) is performed according to Example 32.

[0320] Comparative Example 9 (CE9)

[0321] Overview

[0322] This embodiment uses a butyl Grignard compound on a solid support. The support is activated. No initiator compound is used; N,N-dimethylbenzamide (BA-2Me) is used as the activator of the internal donor, and isopropylisopentyldimethoxypropane (IPIPEN) is used as the internal donor.

[0323] Steps A) and E) are performed as described in Example 1.

[0324] Step B) is carried out according to Comparative Example 1.

[0325] Step C) is performed according to Example 18.

[0326] Step D) is performed according to Example 34.

[0327] Table 3. Examples of different internal donors used in step B with a dosing temperature of 0°C and a dosing time of 2 hours.

[0328]

[0329]

[0330] The table above clearly shows the increase in pore volume and surface area of ​​the formed master catalysts, which makes those master catalysts very suitable for both homopolymers and heteropolymers, as more pores are needed to reach different monomers.

[0331] Therefore, those main catalysts are very suitable for obtaining copolymers or terpolymers of polypropylene with, for example, higher ethylene / rubber content.

Claims

1. A method for preparing a solid support for a main catalyst, said main catalyst being suitable for preparing a catalyst composition for olefin polymerization, said method comprising: A) Provide or prepare compound R 4 z MgX 4 2-z , wherein: R 4 is independently selected from alkyl, alkenyl, aryl, aralkyl or alkylaryl; X 4 is independently selected from fluoride ion, chloride ion, bromide ion or iodide ion; and 0 < z < 2; and B) React the compound R 4 z MgX 4 2-z with a silane compound Si(OR 5 ) 4-n (R 6 ) n to produce Mg(OR 1 ) x X 1 2-x , where: R 1 , R 5 and R 6 are each independently selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl; Х 1 is independently selected from fluoride ion, chloride ion, bromide ion or iodide ion; n is 0 - 4; 0 < z < 2; and 0 < x < 2; In step B, an initiator compound is added to obtain a solid support. N,N-dimethylbenzamide was used as the initiator compound.

2. The method according to claim 1, further comprising: C) Activate the obtained solid support by contacting it with an alkyl alcohol and / or a metal alkoxide to obtain an activated solid support, wherein the alkyl alcohol is methanol or ethanol; and wherein the metal alkoxide is titanium tetraethoxide.

3. The method of claim 2, wherein the obtained solid support is contacted with ethanol and titanium tetraoxide.

4. A solid support obtained directly by the method according to claim 1, or an activated solid support obtained by the method according to any one of claims 2-3.

5. A method for preparing a main catalyst, said main catalyst being suitable for preparing a catalyst composition for olefin polymerization, said method comprising: I) Provide the solid carrier or activated solid carrier according to claim 4; and II) The main catalyst is obtained by reacting the solid support or activated solid support with a halogen-containing Ti-compound, an activator optionally added before or simultaneously with the addition of an internal electron donor, and at least one internal electron donor. In section II), the following are added as activators and internal electron donors: • N,N-dimethylbenzamide as an activator and 9,9-bis(methoxymethyl)fluorene as an internal electron donor; or • Ethyl benzoate as an activator and 4-[benzoyl(methyl)-amino]pent-2-ylbenzoate as an internal electron donor, or • N,N-Dimethylbenzamide as an activator and isopropylisopentyldimethoxypropane as an internal electron donor.

6. The main catalyst obtained directly by the method according to claim 5.

7. The solid support or activated solid support according to claim 4, or the main catalyst according to claim 6, has an average particle size of 8-35 micrometers.

8. The solid support or activated solid support or main catalyst according to claim 7 has an average particle size of 11-32 micrometers.

9. The solid support or activated solid support or main catalyst according to claim 7 has an average particle size of 18-30 micrometers.

10. A catalyst system comprising the main catalyst, co-catalyst, and optionally at least one external electron donor as described in claim 7.

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

12. The method of claim 11, wherein the at least one olefin comprises ethylene, butene, or hexene.

13. Polypropylene obtained by the method according to claim 11 or 12.

14. A molded article comprising the polypropylene according to claim 13.

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