Catalyst system for olefin polymerization

Abstract

The present invention relates to a process for preparing a procatalyst for preparing a catalyst composition for olefin polymerization from a solution of R4zMgX42-z, wherein the solution of R4zMgX42-z is prepared by a process comprising the steps of: (i) reacting magnesium powder with an organic halide in the presence of an organic solvent at a temperature of T1; (ii) stirring the reaction mixture obtained in step (i) at T1 for at least one hour; (iii) raising the temperature of the reaction mixture obtained in step (ii) to a temperature T2; (iv) stirring the reaction mixture obtained in step (iii) at T2 for at least one hour; (v) decanting or filtering the reaction mixture obtained in step (iv) to obtain a transparent solution of R < 4 > z MgX < 4-z > in an organic solvent; wherein T1 is in the range of 70 DEG C to 90 DEG C and T2 is in the range of T1 + 30 DEG C to T1 + 40 DEG C.

Description

Technical Field

[0001] The present invention relates to a process for preparing a procatalyst for preparing a catalyst composition for olefin polymerization. In addition, the present invention relates to a process for preparing a magnesium-based support. The present invention also relates to a procatalyst obtained or obtainable by the process. The present invention further relates to a process for preparing polyolefins. The present invention also relates to polyolefins and polypropylene homopolymers. Background Art

[0002] Catalyst systems and components suitable for preparing polyolefins are generally known. One type of such catalyst is generally referred to as a Ziegler-Natta catalyst. The term "Ziegler-Natta" is known in the art and generally refers to a catalyst system comprising a solid catalyst compound containing a transition metal (also generally referred to as a procatalyst), an organometallic compound (also generally referred to as a cocatalyst), and optionally one or more electron donor compounds (e.g., an external electron donor).

[0003] The solid catalyst compound containing transition metal comprises transition metal halide (for example titanium halide, chromium halide, hafnium halide, zirconium halide, vanadium halide), and the transition metal halide is supported on metal or metalloid compound (for example magnesium compound or silicon dioxide compound). Such catalyst type is reviewed for example in Catal.Rev.-Sci.Eng.41 of T.Pullukat and R.Hoff, vol.3 and 4, 389-438,1999.

[0004] Other methods for preparing Ziegler-Natta catalyst components suitable for olefin polymerization are also disclosed in the art. Document WO96 / 32426A discloses a three-step method for preparing a catalyst for olefin polymerization, wherein in the first two steps, a compound Mg(OAIk) having a certain morphology is prepared. x Cl y , and then the solid Mg compound is contacted with titanium tetrachloride and an electron donating compound.

[0005] EP398698A1 also discloses a method for polymerizing olefins in the presence of a solid catalyst component, wherein the solid catalyst component is obtained by firstly reacting Mg(OR 1 ) n (OR 2 ) 2-n 、Ti(OR 3 )4, Ti(OAIk)4 and Si(OR 4 )4 reacts in solution to form an intermediate product, which further reacts with TiX m (OR5) 4-m and an electron donating compound, wherein R 1 , R 2 , R3 , R 4 and R 5 A description is provided in the same patent application. The preparation of such a procatalyst is disclosed, for example, in WO 96 / 32427 A1.

[0006] WO2015091983A1 discloses a method for preparing a procatalyst suitable for preparing a catalyst composition for olefin polymerization, the method comprising the following steps: providing a magnesium-based support, contacting the magnesium-based support with a Ziegler-Natta type catalyst, an internal donor and an activator to generate a procatalyst, wherein the activator is benzamide.

[0007] RU2674440C1 discloses a method for preparing a catalyst for olefin polymerization and a method for olefin polymerization. The method for preparing a catalyst for olefin polymerization is carried out by contacting metal magnesium with an organic halide RX, wherein R is an organic group containing 5 to 20 carbon atoms and X is a halogen atom, thereby forming a soluble product (I), then adding a silicon compound containing an alkoxy group or an aryloxy group to the product (I), thereby forming a solid product (II), then treating the product (II) with titanium tetrachloride and an electron donor compound, and contacting the metal magnesium with the organic halide RX in the presence of an aromatic hydrocarbon containing 6 to 10 hydrocarbon atoms.

[0008] A disadvantage of the above-mentioned prior art is that the activity of the procatalyst is not high enough for certain applications where a narrow molecular weight distribution is required.

[0009] Therefore, an object of the present invention is to provide a highly stable R 4 z MgX 4 2-z The solution thus obtains a procatalyst showing better performance in olefin polymerization, in particular with respect to polypropylene yield.

[0010] One or more of the above-mentioned objects of the present invention are achieved by various aspects of the present invention. Summary of the invention

[0011] The present invention relates to a process for preparing a procatalyst for preparing a catalyst composition for olefin polymerization. In addition, the present invention relates to a process for preparing a magnesium-based support.

[0012] The inventors have surprisingly found that the magnesium-based support obtained by using the process of the present invention shows a better magnesium-based support yield and correspondingly a better catalyst yield.

[0013] In a first aspect, the present invention relates to a method for preparing a procatalyst for preparing a catalyst composition for olefin polymerization, the method comprising the steps of:

[0014] a. Provided by R 4 z MgX 4 2-z A magnesium-based support prepared from a solution of

[0015] Where R 4 is independently selected from a linear, branched or cyclic hydrocarbon group, which is independently selected from an alkyl, alkenyl, aryl, aralkyl or alkaryl 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, preferably R 4 is butyl;

[0016] 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 in the range of greater than 0 and less than 2, and is 0 <z<2;

[0017] b. optionally activating the magnesium-based support using an activator;

[0018] c. contacting a magnesium-based support with a Ziegler-Natta type catalytic species and one or more internal donors;

[0019] wherein R is prepared by a method comprising the following steps 4 z MgX 4 2-z Solution:

[0020] (i) reacting magnesium powder with an organic halide in the presence of an organic solvent at a temperature of T1;

[0021] (ii) stirring the reaction mixture obtained in step (i) at T1 for at least 1 hour;

[0022] (iii) raising the temperature of the reaction mixture obtained in step (ii) to temperature T2;

[0023] (iv) stirring the reaction mixture obtained in step (iii) at T2 for at least 1 hour;

[0024] (v) decanting or filtering the reaction mixture obtained in step (iv) to obtain R 4 z MgX 4 2-z Clear solutions in organic solvents;

[0025] Among them, T1 is in the range of 70℃-90℃, and T2 is in the range of T1+20℃ to T1+60℃.

[0026] In one embodiment of the first aspect, T1 is in the range of 70°C-90°C, preferably 75°C-85°C; T2 is in the range of T1+20°C to T1+60°C, preferably T1+30°C to T1+40°C.

[0027] In one embodiment of the first aspect, the internal donor is selected from aminobenzoates, succinates, silyl esters, silyl glycol esters, diethers, phthalates, or any combination thereof.

[0028] In another embodiment of the first aspect, the organic solvent is selected from diethyl ether, isopropyl ether, butyl ether, isobutyl ether, isoamyl ether, allyl ether, tetrahydrofuran, anisole and octyl ether. Preferably, the organic solvent is butyl ether.

[0029] In another embodiment of the first aspect, the organic halide is R 4 X 4 , where R 4 is independently selected from a linear, branched or cyclic hydrocarbon group, which is independently selected from an alkyl, alkenyl, aryl, aralkyl or alkaryl 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, preferably R 4 is butyl;

[0030] X 4 Independently selected from fluoride ion (F-), chloride ion (Cl-), bromide ion (Br-) or iodide ion (I-), preferably chloride ion.

[0031] In another embodiment of the first aspect, the preferred organic halide is selected from butyl chloride, butyl bromide and 1,2-dibromoethane or a combination thereof.

[0032] In another embodiment of the first aspect, the activator is selected from benzamide, alkyl benzoate, monoester or any combination thereof. Preferably, the activator is benzamide, alkyl benzoate or a combination thereof.

[0033] In one embodiment of the first aspect, the obtained R 4 z MgX 4 2-z The concentration of the clear solution in the organic solvent is at most 3 mol / l, or from 1 to 2.5 mol / l, or from 1 to 2 mol / l.

[0034] In another embodiment of the first aspect, the method is substantially free of phthalates.

[0035] In another embodiment of the first aspect, a method for preparing a procatalyst for preparing a catalyst composition for olefin polymerization comprises the following steps:

[0036] A) providing a procatalyst by a method comprising the steps of:

[0037] i) Make R 4 z MgX 4 2-z Contacting with an alkoxy- or aryloxy-containing silane compound to produce a first intermediate reaction product, which is solid Mg(OR 5 ) x X 1 2-x , where: R 5 is a linear, branched or cyclic hydrocarbon group independently selected from an alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkaryl 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; wherein R 4 is a linear, branched or cyclic hydrocarbon group independently selected from an alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkaryl 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, preferably R 4 is butyl; wherein X 2 and X 1 Each is independently selected from fluoride ion (F-), chloride ion (Cl-), bromide ion (Br-) or iodide ion (I-), preferably chloride ion; z is in the range of greater than 0 and less than 2, and is 0 <z<2;

[0038] ii) optionally subjecting the solid Mg(OR) obtained in step i) to 5 ) x X 1 2-x contacting with at least one activating compound to obtain a second intermediate product, wherein the activating compound is selected from the group consisting of an activating electron donor and a 1 (OR 6 ) v-w (OR 7 ) w or M 2 (OR 6 ) v-w (R 7 ) w A group formed by metal alkoxide compounds; wherein: M 1is a metal selected from Ti, Zr, Hf, Al or Si; v is M 1 The valence of 2 is metal Si; v is M 2 The valence of 6 and R 7 Each is a linear, branched or cyclic hydrocarbon group, which is independently selected from an alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkaryl 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; wherein w is less than v, preferably v is 3 or 4;

[0039] iii) contacting the first intermediate reaction product or the second intermediate reaction product obtained in step i) or ii) respectively with a halogen-containing Ti compound and an internal donor.

[0040] In another embodiment of the aspect, contacting the first intermediate reaction product or the second intermediate reaction product obtained in step i) or ii) respectively with a halogen-containing Ti compound comprises the following steps: contacting the intermediate reaction product with a halogen-containing Ti compound to produce a first intermediate as a first step, and a second step of contacting the intermediate reaction product with a halogen-containing Ti compound to produce a second intermediate reaction product, and a third step of contacting the intermediate reaction product with a halogen-containing Ti compound to produce a procatalyst, and preferably wherein an activator according to formula (I) is added in the first and / or second step, more preferably wherein an activator according to formula (I) is added in the first step.

[0041] In another embodiment of the first aspect, magnesium and R 4 X 4 The concentration relative to the organic solvent is 1 to 4 mol / l, preferably 1 to 3.5 mol / l, more preferably 1 to 3 mol / l.

[0042] In another embodiment of the first aspect, magnesium and R 4 X 4 The concentration relative to the organic solvent is 1 to 5 mol / l, preferably 1 to 4 mol / l, preferably 1 to 3.5 mol / l, more preferably 1 to 3 mol / l.

[0043] In another embodiment of the first aspect, the internal donor is selected from aminobenzoates represented by formula (I):

[0044]

[0045] in:

[0046] R 80are independently selected from substituted or unsubstituted aryl, aralkyl or alkaryl groups and one or more combinations thereof, and

[0047] R 81 , R 82 , R 83 , R 84 , R 85 and R 86 each independently selected from hydrogen or a linear, branched or cyclic hydrocarbyl group selected from an alkyl, alkenyl, aryl, aralkyl or alkaryl group and one or more combinations thereof, preferably having 1 to 20 carbon atoms;

[0048] Where R 87 is selected from hydrogen, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, phenyl, benzyl, substituted benzyl and halophenyl groups; and

[0049] Where R 88 is selected from hydrogen or a linear, branched or cyclic hydrocarbon group, the hydrocarbon group being selected from an alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkaryl group and one or more combinations thereof, preferably having 1 to 20 carbon atoms, and more preferably R 88 It is phenyl.

[0050] or wherein the internal donor is selected from diethers according to formula (II),

[0051]

[0052] Where R 51 and R 52 Each is independently selected from hydrogen or a hydrocarbyl group selected from an alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkaryl group and one or more combinations thereof.

[0053] R 53 and R 54 Each is independently selected from hydrogen, halogen or a hydrocarbon group selected from an alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkaryl group and one or more combinations thereof.

[0054] or wherein the internal donor is selected from succinates according to formula (III)

[0055]

[0056] R 60 and R 61Each independently is a hydrocarbyl group selected from an alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkaryl group and one or more combinations thereof. The hydrocarbyl group may be linear, branched or cyclic. The hydrocarbyl group may be substituted or unsubstituted. The hydrocarbyl group may contain one or more heteroatoms. Preferably, the hydrocarbyl group has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, even more preferably 1 to 6 carbon atoms.

[0057] R 62 , R 63 , R 64 and R 65 Each independently selected from hydrogen or a hydrocarbyl group, the hydrocarbyl group is selected from an alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkaryl group and one or more combinations thereof. The hydrocarbyl group may be linear, branched or cyclic. The hydrocarbyl group may be substituted or unsubstituted. The hydrocarbyl group may contain one or more heteroatoms. Preferably, the hydrocarbyl group has 1 to 20 carbon atoms.

[0058] or wherein the internal donor is selected from phthalates according to formula (IV)

[0059]

[0060] R 40 and R 41 Each independently is a hydrocarbyl group, which is selected from an alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkaryl group and one or more combinations thereof. The hydrocarbyl group can be linear, branched or cyclic. The hydrocarbyl group can be substituted or unsubstituted. The hydrocarbyl group can contain one or more heteroatoms. Preferably, the hydrocarbyl group has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, even more preferably 1 to 6 carbon atoms. Suitable examples of hydrocarbyl groups include alkyl, cycloalkyl, alkenyl, diene, cycloalkenyl, cycloalkadienyl, aryl, aralkyl, alkaryl and alkynyl groups.

[0061] R 42 , R 43 , R 44 , R 45 Each independently selected from hydrogen, halogen or hydrocarbyl group, the hydrocarbyl group is selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkaryl group and one or more combinations thereof. The hydrocarbyl group can be linear, branched or cyclic. The hydrocarbyl group can be substituted or unsubstituted. The hydrocarbyl group can contain one or more heteroatoms. Preferably, the hydrocarbyl group has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, even more preferably 1 to 6 carbon atoms.

[0062] Suitable non-limiting examples of phthalates include dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-tert-butyl phthalate, diisoamyl phthalate, di-tert-amyl phthalate, dineopentyl phthalate, di(2-ethylhexyl)phthalate, di(2-ethyldecyl)phthalate, bis(2,2,2-trifluoroethyl)phthalate, diisobutyl-4-tert-butylphthalate, and diisobutyl-4-chlorophthalate. The phthalate is preferably di-n-butyl phthalate or diisobutyl phthalate,

[0063] Or wherein the internal donor is selected from one or more compounds of formula (I), formula (II), formula (III), formula (IV) or a combination thereof.

[0064] In another embodiment of the first aspect, the preferred internal donor is an aminobenzoate as represented by formula (I) or a diether as represented by formula (II) or a combination thereof.

[0065] In a second aspect, the present invention relates to a procatalyst obtained or obtainable by the process described herein.

[0066] In yet another aspect, the present invention relates to a process for preparing polyolefins, preferably polypropylene and copolymers of propylene and alpha-olefins, comprising contacting a catalyst composition comprising a procatalyst as described herein with an olefin, optionally with an alpha-olefin, and optionally an external donor and / or optionally a cocatalyst and / or an activity limiting agent. The alpha-olefin is preferably ethylene, 1-butene and / or 1-hexene.

[0067] In another aspect, the present invention relates to polyolefins, preferably polypropylene and copolymers of propylene and α-olefins, obtained or obtainable by the process described herein, wherein the α-olefin is preferably ethylene, 1-butene and / or 1-hexene.

[0068] In yet another aspect, the present invention relates to a shaped article comprising a polyolefin as described herein.

[0069] These aspects and embodiments are described in more detail below.

[0070] The procatalyst according to the present invention is advantageous in that it exhibits excellent productivity when used in a catalyst system. Furthermore, the polyolefins obtained using the catalyst according to the present invention exhibit broad or medium MWD.

[0071] The following definitions are used in this specification and claims to define the stated subject matter.Other terms not cited below are intended to have the meanings generally accepted in the art.

[0072] The "Ziegler-Natta catalyst" used in this specification means: a solid catalyst compound containing a transition metal, wherein the compound comprises a transition metal halide selected from titanium halide, chromium halide, hafnium halide, zirconium halide or vanadium halide, and the transition metal halide is supported on a metal or metalloid compound (such as a magnesium compound or a silica compound).

[0073] As used herein, "Ziegler-Natta type catalyst species" or "catalytic species" means a transition metal-containing species comprising a transition metal halide selected from titanium halide, chromium halide, hafnium halide, zirconium halide or vanadium halide.

[0074] "Internal donor" or "internal electron donor" or "ID" as used in this specification means: an electron donating compound containing one or more oxygen atoms (O) and / or nitrogen atoms (N). The ID is used as a reactant to prepare a solid procatalyst. Internal donors are generally described in the prior art as being used to prepare solid supported Ziegler-Natta catalyst systems for olefin polymerization; i.e., by contacting a magnesium-containing support with a halogen-containing Ti compound and an internal donor.

[0075] "External donor" or "external electron donor" or "ED" as used in this specification means: an electron donating compound used as a reactant in the polymerization of olefins. ED is a compound added independently of the procatalyst. It is not added during the formation of the procatalyst. It contains at least one functional group capable of donating at least one pair of electrons to a metal atom. ED can affect catalyst properties, non-limiting examples of which are stereoselectivity, hydrogen sensitivity, ethylene sensitivity, randomness of comonomer incorporation, and catalyst productivity of the catalyst system in the polymerization of olefins having 3 or more carbon atoms.

[0076] As used in this specification, "activator" means an electron donating compound containing one or more oxygen atoms (O) and / or nitrogen atoms (N), which is used during the synthesis of the procatalyst prior to or simultaneously with the addition of the internal donor.

[0077] As used in this specification, "activating compound" means a compound used to activate a solid support before the solid support is contacted with a catalytic species.

[0078] "Activity limiting agent" (ALA) as used in this specification means a material that reduces the activity of the catalyst at elevated temperatures, ie reduces thermal runaway of the catalyst.

[0079] "Modifier" or "Group 13 or transition metal modifier" as used in this specification means: a metal modifier comprising a metal selected from Group 13 metals and transition metals of the IUPAC Periodic Table of Elements. When the term metal modifier or metal-based modifier is used in the specification, it means a Group 13 or transition metal modifier.

[0080] As used in this specification, "procatalyst" and "catalyst component" have the same meaning: a component of a catalyst composition that generally comprises a solid support, a transition metal-containing catalytic species and one or more internal donors.

[0081] A "metering phase" is a phase in a process in which the components of the reaction mixture of this particular phase are added or charged at a specific time and temperature.

[0082] A "hold phase" is a phase in a process wherein the reaction mixture is held and stirred at a specific temperature for a specific amount of time.

[0083] The "halide ion" or "halide ion" or "halogen" or "halogen atom" used in the present specification means an ion selected from the group consisting of fluoride ion (F-), chloride ion (Cl-), bromide ion (Br-) or iodide ion (I-).

[0084] As used in this specification, "heteroatom" means: an atom other than carbon or hydrogen. However, as used herein - unless otherwise stated, for example as follows - when "one or more heteroatoms" is used it means one or more of the following atoms: F, Cl, Br, I, N, O, P, B, S or Si. Thus, heteroatoms also include halogens.

[0085] As used in the present specification, "heteroatoms selected from Group 13, 14, 15, 16 or 17 of the IUPAC Periodic Table" means: heteroatoms selected from B, Al, Ga, In, Tl [Group 13], Si, Ge, Sn, Pb [Group 14], N, P, As, Sb, Bi [Group 15], O, S, Se, Te, Po [Group 16], F, Cl, Br, I, At [Group 17]. More preferably, "heteroatoms selected from Group 13, 14, 15, 16 or 17 of the IUPAC Periodic Table" includes N, O, P, B, S or Si.

[0086] The "hydrocarbon group" used in this specification means: a substituent containing hydrogen atoms 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 aromatic group, such as a monocyclic or polycyclic aromatic group, and combinations thereof, such as alkaryl and aralkyl.

[0087] As used in this specification, "substituted hydrocarbyl" means a hydrocarbyl group substituted by one or more non-hydrocarbyl substituent groups. Non-limiting examples of non-hydrocarbyl substituents are heteroatoms. Examples are alkoxycarbonyl (i.e., carboxylate) groups. Unless otherwise stated, when "hydrocarbyl" is used in this specification, it may also be a "substituted hydrocarbyl".

[0088] "Alkyl" as used in this specification means: an alkyl group consisting of carbon atoms and hydrogen atoms having only single bonds as a functional group or side chain. The alkyl group may be linear or branched and may be unsubstituted or substituted. It may or may not contain heteroatoms such as oxygen (O), nitrogen (N), phosphorus (P), silicon (Si) or sulfur (S).

[0089] "Aryl" as used in this specification means: an aryl group derived from an aromatic ring as a functional group or side chain. The aryl group may be unsubstituted or substituted by a straight or branched hydrocarbon group. It may or may not contain heteroatoms such as oxygen (O), nitrogen (N), phosphorus (P), silicon (Si) or sulfur (S). Aryl groups also include alkaryl groups in which one or more hydrogen atoms on the aromatic ring have been replaced by an alkyl group.

[0090] "Aralkyl" as used in the present specification means: an arylalkyl group, which is an alkyl group in which one or more hydrogen atoms have been replaced by an aryl group.

[0091] "Alkoxy" or "alkoxy" as used in this specification means: a functional group or side chain derived from an alkyl alcohol. It consists of an alkyl group bonded to a negatively charged oxygen atom.

[0092] "Aryloxide" or "aryloxy" or "phenoxy" used in the present specification means: a functional group or side chain derived from an aryl alcohol, which consists of an aryl group bonded to a negatively charged oxygen atom.

[0093] The term "Grenier reagent" or "Grenier compound" used in this specification refers to: 4 z MgX 4 2-z (R 4 , z and X 4 As defined below), or it may be a complex having multiple Mg clusters, such as R 4 Mg3Cl2.

[0094] As used herein, "polymer" means a chemical compound comprising repeating structural units, wherein the structural units are monomers.

[0095] The "olefin" used in this specification means: a chain alkene.

[0096] "Olefin-based polymer" or "polyolefin" as used in this specification means: a polymer of one or more alkenes.

[0097] "Propylene-based polymer" as used in this specification means: a polymer of propylene and optional comonomers.

[0098] "Polypropylene" (PP) used in this specification means: a polymer of propylene.

[0099] "Copolymer" as used in this specification means: a polymer prepared from two or more different monomers.

[0100] "Monomer" as used in this specification means: a chemical compound that can undergo polymerization.

[0101] "Thermoplastic" as used in this specification means: capable of softening or melting when heated and capable of hardening again when cooled.

[0102] The "polymer composition" used in this specification means: a mixture of two or more polymers or a mixture of one or more polymers and one or more additives.

[0103] The "polymerization conditions" used in this specification refer to the temperature and pressure parameters in the polymerization reactor suitable for promoting the polymerization between the procatalyst and the olefin to form the desired polymer. These conditions depend on the type of polymerization used.

[0104] "Production rate" or "productivity" as used in this specification means the amount of kilograms of polymer produced per gram of procatalyst consumed in the polymerization reactor per hour, unless otherwise stated.

[0105] "APP weight %" or "weight percentage of atactic polypropylene" as used in this specification means: the proportion of polypropylene obtained in the slurry polymerization that remains in the solvent. APP can be determined by taking 100 ml of the filtrate ("y", in milliliters) obtained during separation from the polypropylene powder ("x", in grams) after the slurry polymerization. The solvent is dried on a steam bath and then dried at 60°C under vacuum. This produces APP ("z", in grams). The total amount of APP ("q", in grams) is (y / 100)*z. The weight percentage of APP is (q / q+x))*100%.

[0106] "MFR" or "melt flow rate" as used in this specification is measured at a temperature of 230°C with a load of 2.16 kg and is measured according to ISO 1133:2005.

[0107] "Bulk density" as used in this specification means: the mass of particles of a polymer divided by the total volume occupied by these particles. It is measured according to ASTM D 1895.

[0108] In the context of the present invention, "span value" means an indication of the breadth of the particle size distribution measured according to ISO 13320:2009.

[0109] Unless otherwise stated, when it is stated that any R group is "independently selected from", this means that when several identical R groups are present in a molecule, they may have the same meaning or they may not have the same meaning. For example, for the compound RM, where R is independently selected from ethyl or methyl, both R groups may be ethyl, both R groups may be methyl, or one R group may be ethyl and the other R group may be methyl. DETAILED DESCRIPTION

[0110] The invention is described in more detail below. Unless otherwise stated, all embodiments described in relation to one aspect of the invention also apply to the other aspects of the invention.

[0111] As described above, when R prepared according to the present invention 4 z MgX 4 2-z When a solution of MgO was used in the catalyst system, the magnesium-based support showed better yield.

[0112] The R according to the present invention is obtained by a method comprising the following steps 4 z MgX 4 2-z Solution:

[0113] (i) reacting magnesium powder with an organic halide in the presence of an organic solvent at a temperature of T1;

[0114] (ii) stirring the reaction mixture obtained in step (i) at T1 for at least 1 hour;

[0115] (iii) raising the temperature of the reaction mixture obtained in step (ii) to temperature T2;

[0116] (iv) stirring the reaction mixture obtained in step (iii) at T2 for at least 1 hour;

[0117] (v) decanting or filtering the reaction mixture obtained in step (iv) to obtain R 4 z MgX 4 2-z Clear solutions in organic solvents;

[0118] Among them, T1 is in the range of 70℃-90℃, and T2 is in the range of T1+20℃ to T1+60℃.

[0119] In one embodiment of the first aspect, T1 is in the range of 70°C-90°C, preferably 75°C-85°C; T2 is in the range of T1+20°C to T1+60°C, preferably T1+30°C to T1+40°C.

[0120] In another embodiment of the first aspect, stirring of the reaction mixture obtained in step (i) is carried out for 1 to 5 hours, preferably 3 to 4 hours, preferably 2 hours, more preferably 1 hour, and stirring of the reaction mixture obtained in step (iii) is carried out for 1 to 5 hours, preferably 3 to 4 hours, preferably 2 hours, more preferably 1 hour.

[0121] In another embodiment, R is prepared by a process comprising the steps of 4 z MgX 4 2-z Solution:

[0122] (i) reacting magnesium powder with an organic solvent and an organic halide at a temperature of T1 to obtain a reaction mixture;

[0123] (ii) raising the temperature of the reaction mixture obtained in step (i) to temperature T1′ and adding an organic solvent and an organic halide to the reaction mixture;

[0124] (iii) stirring the reaction mixture obtained in step (ii) at T1' for at least 1 hour;

[0125] (iv) raising the temperature of the reaction mixture obtained in step (iii) to temperature T2;

[0126] (v) stirring the reaction mixture obtained in step (iv) at T2 for at least 1 hour;

[0127] (vi) decanting the reaction mixture obtained in step (v) to obtain R 4 z MgX 4 2-z Clear solutions in organic solvents;

[0128] Wherein T1 is in the range of 70°C-80°C, T1' is in the range of T1+5°C to T1+15°C, and T2 is in the range of T1+20°C to T1+60°C.

[0129] The stirring of the reaction mixture obtained in step (ii) is carried out for 1 to 5 hours, preferably 3 to 4 hours, preferably 2 hours, more preferably 1 hour, and the stirring of the reaction mixture obtained in step (iv) is carried out for 1 to 5 hours, preferably 3 to 4 hours, preferably 2 hours, more preferably 1 hour.

[0130] The organic solvent is selected from ethyl ether, isopropyl ether, butyl ether, isobutyl ether, isoamyl ether, allyl ether, tetrahydrofuran, anisole and octyl ether or a combination thereof, and preferably the organic solvent is butyl ether.

[0131] Organic halides are composed of R 4 X 4 Indicates that R 4 is independently selected from a linear, branched or cyclic hydrocarbon group, which is independently selected from an alkyl, alkenyl, aryl, aralkyl or alkaryl 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, preferably R 4 is butyl;

[0132] 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 in the range of greater than 0 and less than 2, and is 0 <z<2。

[0133] Preferred organic halides are selected from butyl chloride, butyl bromide and 1,2-dibromoethane or combinations thereof.

[0134] The present invention furthermore includes internal donors in the procatalyst.

[0135] Without being bound to any particular theory, it is believed that the internal electron donor helps regulate the formation of active sites, thereby enhancing the catalyst stereoselectivity.

[0136] Because of increasingly stringent governmental regulations on the maximum phthalate content of polymers, preference is given to using so-called phthalate-free internal donors. This leads to an increased demand for phthalate-free procatalysts.

[0137] The internal donor used in the present invention is selected from aminobenzoic acid esters, succinic acid esters, silyl esters, silyl glycol esters, diethers, phthalates or any combination thereof.

[0138] The inventors have surprisingly found that the combination of a magnesium based support obtained according to the present invention with a diether based internal donor or an aminobenzoate based internal donor or a combination thereof shows a better combined yield.

[0139] The internal donors represented by formula (I) or formula (II) or a combination thereof are suitable internal donors according to the present invention:

[0140]

[0141] in:

[0142] R 80 are independently selected from substituted or unsubstituted aromatic groups, or R 81 , R 82 , R 83 , R 84 , R 85 and R 86each independently selected from hydrogen or a linear, branched or cyclic hydrocarbyl group selected from an alkyl, alkenyl, aryl, aralkyl or alkaryl group and one or more combinations thereof, preferably having 1 to 20 carbon atoms;

[0143] Where R 81 and R 82 are each a hydrogen atom, and R 83 , R 84 , R 85 and R 86 independently selected from C1-C10 straight and branched alkyl; C3-C10 cycloalkyl; C6-C10 aryl; and C7-C10 alkaryl and aralkyl groups, preferably selected from C1-C10 straight and branched alkyl, and more preferably selected from methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, phenyl groups;

[0144] When R 83 and R 84 One of the 85 and R 86 has at least one carbon atom, then R 83 and R 84 The other and R 85 and R 86 The other of each is a hydrogen atom;

[0145] Where R 87 is selected from hydrogen, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, phenyl, benzyl, substituted benzyl and halophenyl groups; and

[0146] Where R 88 is selected from hydrogen or a linear, branched or cyclic hydrocarbon group, the hydrocarbon group being selected from an alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkaryl group and one or more combinations thereof, preferably having 1 to 20 carbon atoms, and more preferably R 88is phenyl, preferably, wherein the internal electron donor is selected from 4-[benzoyl(methyl)amino]pentan-2-yl benzoate; 2,2,6,6-tetramethyl-5-(methylamino)heptan-3-ol dibenzoate; 4-[benzoyl(ethyl)amino]pentan-2-yl benzoate, 4-(methylamino)pentan-2-yl bis(4-methoxy)benzoate), 3-[benzoyl(cyclohexyl)amino]-1-phenylbutylbenzoate, 3-[ dibenzoate, 3-(methyl)amino-2,2-dimethylpropane-1-ol dibenzoate, and 4-(methylamino)pentan-2-yl bis(4-methoxy)benzoate).

[0147] or

[0148]

[0149] Wherein R shown in formula (VI) 51 and R 52 Each independently selected from hydrogen or a hydrocarbyl group, the hydrocarbyl group is selected from an alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkaryl group and one or more combinations thereof. The hydrocarbyl group can be linear, branched or cyclic. The hydrocarbyl group can be substituted or unsubstituted. The hydrocarbyl group can contain one or more heteroatoms. Preferably, the hydrocarbyl group has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, even more preferably 1 to 6 carbon atoms. Suitable examples of hydrocarbyl groups include alkyl, cycloalkyl, alkenyl, diene, cycloalkenyl, cycloalkadienyl, aryl, aralkyl, alkaryl and alkynyl groups.

[0150] R shown in formula (II) 53 and R 54 Each independently selected from hydrogen, halogen or hydrocarbyl group, the hydrocarbyl group is selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkaryl group and one or more combinations thereof. The hydrocarbyl group can be linear, branched or cyclic. The hydrocarbyl group can be substituted or unsubstituted. The hydrocarbyl group can contain one or more heteroatoms. Preferably, the hydrocarbyl group has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, even more preferably 1 to 6 carbon atoms.

[0151] Suitable examples of the dialkyl diether compound include 1,3-dimethoxypropane, 1,3-diethoxypropane, 1,3-dibutoxypropane, 1-methoxy-3-ethoxypropane, 1-methoxy-3-butoxypropane, 1-methoxy-3-cyclohexyloxypropane, 2,2-dimethyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane, 2,2-di-n-butyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2-ethyl-2-n-butyl-1,3-dimethoxypropane, 2-n-propyl-2-cyclopentyl-1,3-dimethoxypropane, 2,2-dimethyl-1,3-diethoxypropane, 2-n-propyl-2-cyclohexyl-1,3-dimethoxypropane, and 2,2-dimethyl-1,3-diethoxypropane. 3-diethoxypropane, 2-(2-ethylhexyl)-1,3-dimethoxypropane, 2-isopropyl-l,3-dimethoxypropane, 2-n-butyl-1,3-dimethoxypropane, 2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-1,3-dimethoxypropane, 2-phenyl-1,3-diethoxypropane, 2-cumyl-1,3-diethoxypropane, 2-(2-phenylethyl)-1,3-dimethoxypropane, 2-(2-cyclohexylethyl)-1,3-dimethoxypropane, 2-(p-chlorophenyl)-1,3-dimethoxypropane, 2-(diphenylmethyl)-1,3-dimethoxypropane, 2-(1-naphthyl)-1,3-dimethoxypropane, 2-(fluorophenyl)-1,3 -dimethoxypropane, 2-(1-decahydronaphthyl)-1,3-dimethoxypropane, 2-(p-tert-butylphenyl)-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-di-n-propyl-1,3-dimethoxypropane, 2-methyl-2-n-propyl-1,3-dimethoxypropane, 2-methyl-2-benzyl-1,3-dimethoxypropane, 2-methyl-2-ethyl-1,3-dimethoxypropane, 2-methyl-2-phenyl-1,3-dimethoxypropane, 2-methyl-2-cyclohexyl-1,3-dimethoxypropane, 2,2-bis(p-chlorophenyl)-1,3-dimethoxypropane, 2,2-bis(2-cyclohexylethyl)-1,3-dimethoxypropane, 2-methyl-2-isobutyl-1,3-dimethoxypropane, 2-methyl-2-(2-ethylhexyl)-1,3-dimethoxypropane, 2-methyl-2-isopropyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2,2-dibenzyl-1,3-dimethoxypropane, 2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-diethoxypropane, 2,2-diisobutyl-1,3-di-n-butoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2,2-di-sec-butyl-1,3-dimethoxypropane, 2,2-di-tert-butyl-1,3-dimethoxypropane, 2,2-dineopentyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2-phenyl-2-benzyl-1,3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane, 2-isopropyl-2-(3,7-dimethyloctyl)1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclohexylmethyl-1,3-dimethoxypropane, 2,2-diisopentyl-1,3-dimethoxypropane Oxypropane, 2-isopropyl-2-cyclohexyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclopentyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2-n-heptyl-2-n-pentyl-1,3-dimethoxypropane, 9,9-bis(methoxymethyl)fluorene (flu), 1,3-dicyclohexyl-2,2-bis(methoxymethyl)propane, 3,3-bis(methoxymethyl)-2,5-dimethylhexane, or any combination of the foregoing. In one embodiment, the internal electron donor is 1,3-dicyclohexyl-2,2-bis(methoxymethyl)propane, 3,3-bis(methoxymethyl)-2,5-dimethylhexane, 2,2-dicyclopentyl-1,3-dimethoxypropane, and combinations thereof. ,

[0152] Examples of preferred diethers are ethyl ether, butyl ether, isoamyl ether, anisole and ethylphenyl ether, 2,3-dimethoxypropane, 2,3-dimethoxypropane, 2-ethyl-2-butyl-1,3-dimethoxypropane, 2-isopropyl-2-isoamyl-1,3-dimethoxypropane and 9,9-bis(methoxymethyl)fluorene (flu) of formula (V):

[0153]

[0154] In a more preferred embodiment, the internal donor is 9,9-bis(methoxymethyl)fluorene and 2-isopropyl-2-isopentyl-1,3-dimethoxypropane or a combination thereof.

[0155] The present invention relates to Ziegler Natta type catalysts. Ziegler Natta type procatalysts generally comprise a solid support, a transition metal-containing catalytic species and one or more internal donors and one or more activators. The present invention further relates to a catalyst system comprising a Ziegler Natta type procatalyst, a cocatalyst and an optional external electron donor. The term "Ziegler Natta" is known in the art.

[0156] The transition metal-containing solid catalyst compound comprises a transition metal halide (eg, titanium halide, chromium halide, hafnium halide, zirconium halide, vanadium halide) supported on a metal or metalloid compound (eg, a magnesium compound or a silica compound).

[0157] Specific examples of several types of Ziegler Natta catalysts are disclosed below.

[0158] Preferably, the present invention relates to so-called TiNo catalysts, which are supported titanium halide catalysts based on magnesium optionally comprising one or more internal donors.

[0159] EP 1 273 595 of Borealis Technology discloses a method for producing an olefin polymerization procatalyst in the form of particles having a predetermined size range, the method comprising: preparing a solution of a complex of a Group IIa metal and an electron donor or a precursor thereof by reacting a Group IIa metal compound with an electron donor or a precursor thereof in an organic liquid reaction medium; reacting the complex with at least one transition metal compound in the solution to produce an emulsion, the dispersed phase of the emulsion containing more than 50 mol % of the Group IIa metal in the complex; maintaining the particles of the dispersed phase in an average size range of 10 to 200 μm by stirring in the presence of an emulsion stabilizer and solidifying the particles; and recovering, washing and drying the particles to obtain the procatalyst.

[0160] EP 0 019 330 of Shell discloses a Ziegler-Natta type catalyst composition. The olefin polymerization catalyst composition comprises: a) the reaction product of an organoaluminum compound and an electron donor, and b) a catalyst having the formula MgR 1 R 2 and contacting the halogenated product with a tetravalent titanium compound to obtain a solid component, wherein R 1 is an alkyl, aryl, alkoxy or aryloxy group, R 2 is an alkyl, aryl, alkoxy or aryloxy group or a halogen.

[0161] The examples of US 5,093,415 to Dow disclose an improved method for preparing a catalyst. The method comprises a reaction between titanium tetrachloride, diisobutyl phthalate and diethoxymagnesium to obtain a solid material. The solid material is then slurried in a solvent and phthaloyl chloride is added. The reaction mixture is heated to obtain a solid material, which is re-slurried with titanium tetrachloride in a solvent. This is heated again and the solid is collected. The solid is once again re-slurried in a solution of titanium tetrachloride to obtain a catalyst.

[0162] Example 2 of US 6,825,146,2 of Dow discloses another improved method for preparing a catalyst. The method comprises the reaction of titanium tetrachloride in solution with a precursor composition (prepared by reacting diethoxymagnesium, tetraethoxytitanium and titanium tetrachloride in a mixture of o-cresol, ethanol and chlorobenzene) and ethyl benzoate as an electron donor. The mixture is heated and the solid is recovered. A solvent and benzoyl chloride are added to the solid titanium tetrachloride. The mixture is heated to obtain a solid product. The last step is repeated. The resulting solid procatalyst is treated to provide a catalyst.

[0163] US 4,771,024 discloses the preparation of a catalyst from column 10, line 61 to column 11, line 9. The "catalyst manufacture on silica" section is incorporated herein by reference. The method comprises combining dried silica with a carbonated magnesium solution (bubbling diethoxymagnesium in ethanol with CO2). The solvent is evaporated at 85°C. The resulting solid is washed and a 50:50 mixture of titanium tetrachloride and chlorobenzene is added to the solvent along with ethyl benzoate. The mixture is heated to 100°C and the liquid is filtered. TiCl4 and chlorobenzene are added again, then heated and filtered. Finally, TiCl4, chlorobenzene and benzoyl chloride are added, then heated and filtered. The catalyst is obtained after washing.

[0164] WO03 / 068828 discloses a method for preparing catalyst components at "preparation of solid catalyst components" on page 91, and the said part is incorporated into the present application by reference. Magnesium chloride, toluene, epichlorohydrin and tributyl phosphate are added to a reactor under nitrogen and then heated. Phthalic anhydride is then added. The solution is cooled to -25°C and TiCl4 is added dropwise, and then heated. An internal donor (1,3-diphenyl-1,3-propanediol dibenzoate, 2-methyl-1,3-diphenyl-1,3-propanediol dibenzoate, 1,3-diphenyl-1,3-propanediol dipropionate, or 1,3-diphenyl-2-methyl-1,3-propanediol dipropionate) is added, and a solid is obtained after stirring and washed. The solid is treated twice with TiCl4 in toluene and then washed to obtain the catalyst component.

[0165] US 4,866,022 discloses a catalyst component comprising a product formed by: A. forming a solution containing magnesium species from magnesium carbonate or magnesium carboxylate; B. reacting a transition metal halide with a catalyst having the formula R n SiR' 4-nThe invention relates to a method for preparing a catalyst, wherein the solid particles are precipitated from the magnesium-containing solution by treating the solid particles with an organosilane of 1, wherein n=0 to 4 and wherein R is hydrogen or an alkyl, haloalkyl or aryl group containing 1 to about 10 carbon atoms or a halosilyl group or haloalkylsilyl group containing 1 to about 8 carbon atoms, and R is halogen; C. reprecipitating the solid particles from a mixture containing a cyclic ether; and D. treating the reprecipitated particles with a transition metal compound and an electron donor. The method for preparing the catalyst is incorporated herein by reference.

[0166] The procatalyst may be produced by any method known in the art.

[0167] The procatalyst can also be produced as disclosed in WO96 / 32426A; this document discloses a process for polymerizing propylene using a catalyst comprising a catalyst component obtained by the following process: wherein a catalyst having the formula Mg(OAlk) is reacted with a catalyst having the formula Mg(OAlk) in the presence of an inert dispersant. x Cl y (wherein x is greater than 0 and less than 2, y is equal to 2-x, and each Alk independently represents an alkyl group) is contacted with a tetraalkoxytitanium and / or an alcohol to form an intermediate reaction product, and wherein the intermediate reaction product is contacted with titanium tetrachloride in the presence of an internal donor, the internal donor being di-n-butyl phthalate.

[0168] Preferably, the Ziegler Natta type procatalyst in the catalyst system according to the present invention is obtained by the method described in WO 2007 / 134851 A1. The method is disclosed in more detail in Example 1. Example 1 including all sub-examples (IA-IE) ​​is incorporated into this specification. From page 3, line 29 to page 14, line 29, more details about different embodiments are disclosed. These embodiments are incorporated into this specification by reference.

[0169] In the following part of the description the different steps and phases of the method for preparing the procatalyst according to the invention will be discussed.

[0170] The method for preparing the procatalyst according to the invention comprises the following steps:

[0171] - Step A): Preparation of a solution of butylmagnesium chloride (BuMgCl);

[0172] - Step B): Preparation of a solid support for the procatalyst;

[0173] - step C): optionally, activating the solid support obtained in step B) using one or more activating compounds to obtain an activated solid support;

[0174] - step D): contacting the solid support obtained in step B) or the activated solid support in step C) with a catalytic species, wherein step D) comprises one of the following:

[0175] * contacting said solid support obtained in step B) or said activated solid support in step C) with a catalytic species and one or more internal donors to obtain said procatalyst; or

[0176] * contacting the solid support obtained in step B) or the activated solid support in step C) with a catalytic species and one or more internal donors to obtain an intermediate product; or

[0177] * contacting the solid support obtained in step B) or the activated solid support in step C) with a catalytic species and an activator to obtain an intermediate product;

[0178] - Optional step D1): modifying the intermediate product obtained in step D), wherein step D1) comprises one of the following:

[0179] * in case an internal donor is used during step D), modifying said intermediate product obtained in step D) with a Group 13 or transition metal modifier, thereby obtaining a procatalyst;

[0180] * In case an activator is used during step D), said intermediate product obtained in step D) is modified with a Group 13 or transition metal modifier and one or more internal donors, thereby obtaining a procatalyst.

[0181] The procatalyst thus prepared can be used for olefin polymerization using an external donor and a cocatalyst.

[0182] The individual steps for preparing the catalyst according to the invention (and the prior art) are described in more detail below.

[0183] Step A): Preparation of a solution of Grignard reagent:

[0184] It can be achieved by reacting metallic magnesium with an organic halide R 4 X 4 Contacting the Grignard reagent R used in step B) 4 ZGar 4 2-z , as described in WO 96 / 32427 A1 and WO 01 / 23441 A1. All forms of metallic magnesium can be used, but finely divided metallic magnesium, such as magnesium powder, is preferred. In order to obtain a rapid reaction, the magnesium is preferably heated under nitrogen before use.

[0185] Where R 4is a hydrocarbon group independently selected from an alkyl, alkenyl, aryl, aralkyl, alkaryl or alkoxycarbonyl group, wherein the hydrocarbon group may be linear, branched or cyclic, and may be substituted or unsubstituted; the hydrocarbon group preferably has 1 to 20 carbon atoms or a combination thereof. 4 The group may contain one or more heteroatoms.

[0186] X 4 is selected from fluoride ion (F-), chloride ion (Cl-), bromide ion (Br-) or iodide ion (I-). The value of z is in the range of greater than 0 and less than 2: 0 <z<2

[0187] It is also possible to use two or more organic halides R 4 X 4 combination.

[0188] Magnesium and organic halides R 4 X 4 can react with each other without using a separate dispersant; organic halide R 4 X 4 Excessive use.

[0189] It is also possible to make organic halides R 4 X 4 and magnesium are in contact with each other and with an inert dispersant. Examples of these dispersants are: aliphatic, alicyclic or aromatic dispersants containing from 4 to 20 carbon atoms.

[0190] Preferably, in the preparation of R 4 z MgX 4 2-z In this step, ether is also added to the reaction mixture. Examples of ethers are: ethyl ether, isopropyl ether, butyl ether, isobutyl ether, isoamyl ether, allyl ether, tetrahydrofuran and anisole. Preferably, butyl ether and / or isoamyl ether are used. Preferably, an excess of chlorobenzene is used as the organic halide R 4 X 4 Therefore, chlorobenzene acts as a dispersant as well as the organic halide R 4 X 4 .

[0191] A small amount of iodine and / or alkyl halide can be added to result in the formation of a reaction mixture of magnesium metal and an organic halide R 4 X 4 The reaction between the organic halide and the organic halide proceeds at a higher rate. Examples of alkyl halides are butyl chloride, butyl bromide, and 1,2-dibromoethane. 4 X 4 In the case of an alkyl halide, iodine and 1,2-dibromoethane are preferably used.

[0192] Preparation of R 4z MgX 4 2-z The reaction temperature of step A) is generally 50°C to 150°C; the reaction time is generally 0.5 to 20 hours during the metered addition phase. In addition, the temperature of the reaction mixture is increased by 10°C to 60°C from the temperature of the reaction mixture during the metered addition phase. The reaction mixture is maintained for at least 1 hour during the holding phase. Further stopping stirring and heating can separate the dissolved reaction product from the solid residual product. The reaction can be mixed. The stirring speed can be determined by a person skilled in the art and should be sufficient to agitate the reactants.

[0193] Step B): Preparation of solid support of catalyst:

[0194] In the process of the present invention, preferably a magnesium-containing support is used. Such magnesium-containing supports are known in the prior art as typical components of Ziegler-Natta procatalysts. This step of preparing a solid support for the catalyst is the same as in the prior art process. The following description explains the method for preparing a magnesium-based support. Other supports may also be used.

[0195] The synthesis of magnesium-containing supports such as magnesium halides, alkyl magnesiums and aryl magnesiums, and alkoxy magnesium and aryloxy magnesium compounds for polyolefin production, especially polypropylene production, is described, for example, in US4978648, WO96 / 32427A1, WO01 / 23441A1, EP1283222A1, EP1222214B1; US5077357; US5556820; US4414132; US5106806 and US5077357, but the present method is not limited to the disclosure in these documents.

[0196] Preferably, the method for preparing a solid support for a procatalyst according to the present invention comprises the following steps:

[0197] Step i): Compound R 4 z MgX 4 2-z (where R 4 , X 4 and z as discussed above) are contacted with an alkoxy- or aryloxy-containing silane compound to produce a first intermediate reaction product. The first intermediate reaction product is a solid magnesium-containing support.

[0198] Thus, in step i), the first intermediate reaction product is prepared by contacting the following reactants: * Grignard reagent (which is a compound of formula R 4 z MgX 4 2-zThe present invention relates to a compound or a mixture of compounds) and a silane compound containing an alkoxy group or an aryloxy group. Examples of these reactants are disclosed in WO 96 / 32427A1 and WO 01 / 23441A1.

[0199] Compound R used as starting product 4 z MgX 4 2-z Also known as Grignard compound. 4 z MgX 4 2-z In, X 4 Preferred is chlorine or bromine, more preferred is chlorine.

[0200] R 4 It can be an alkyl group, an aryl group, an aralkyl group, an alkoxy group, a phenoxy group, or a mixture thereof. 4 Suitable examples of are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, hexyl, cyclohexyl, octyl, phenyl, tolyl, xylyl, mesityl, benzyl, phenyl, naphthyl, thienyl, indolyl. In a preferred embodiment of the present invention, R 4 represents an aromatic group, for example a phenyl group.

[0201] In formula R 4 z MgX 4 2-z In the Grignard compound of , z is preferably about 0.5 to 1.5.

[0202] Compound R 4 z MgX 4 2-z It may be prepared in step A discussed above, prior to step i) or may be obtained from a different process.

[0203] It is explicitly noted that the Grignard compound used in step i) may alternatively have a different structure, for example a complex. Such complexes are known to those skilled in the art; a specific example of such a complex is phenyl 4Mg3Cl2.

[0204] The alkoxy- or aryloxy-containing silane used in step i) is preferably of the general formula Si(OR 5 ) 4-n R 6 n a compound or a mixture of compounds,

[0205] It should be noted that R 5 Group and R 1During the synthesis of the first intermediate reaction product, R 1 The group is derived from R 5 Group.

[0206] R 5 It is a hydrocarbyl group, which is independently selected from an alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkaryl group and one or more combinations thereof. The hydrocarbyl group may be linear, branched or cyclic. The hydrocarbyl group may be substituted or unsubstituted. The hydrocarbyl group may contain one or more heteroatoms. Preferably, the hydrocarbyl group has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, even more preferably 1 to 6 carbon atoms. Preferably, the hydrocarbyl group is an alkyl group, preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, even more preferably 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl or hexyl; most preferably, selected from ethyl and methyl.

[0207] R 6 It is a hydrocarbyl group, which is independently selected from an alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkaryl group and one or more combinations thereof. The hydrocarbyl group may be linear, branched or cyclic. The hydrocarbyl group may be substituted or unsubstituted. The hydrocarbyl group may contain one or more heteroatoms. Preferably, the hydrocarbyl group has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, even more preferably 1 to 6 carbon atoms. Preferably, the hydrocarbyl group is an alkyl group, preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, even more preferably 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl or cyclopentyl.

[0208] The value of n is in the range of 0 to 4, preferably n is 0 to and including 1.

[0209] Examples of suitable silane compounds include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltributoxysilane, phenyltriethoxysilane, diethyldiphenoxysilane, n-propyltriethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, n-propyltrimethoxysilane, cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxysilane, isobutylisopropyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, trifluoropropylmethyldimethoxysilane, bis(perhydroisoquinolinyl)dimethoxysilane, dicyclohexyldimethoxysilane, dinorbornyldimethoxysilane, di(n-propyl)dimethoxysilane, di(isopropyl)dimethoxysilane, di(n-butyl)dimethoxysilane and / or di(isobutyl)dimethoxysilane.

[0210] Preferably, in the process according to the invention, tetraethoxysilane is used as silane compound in the preparation of the solid Mg-containing compound during step i).

[0211] Preferably, in step i), silane compound and Grignard compound are introduced into mixing device simultaneously so as to cause the particle of the first intermediate reaction product with favorable morphology. This is described in WO 01 / 23441A1 for example. Here, "morphology" not only relates to the shape of the particle of solid Mg compound and the catalyst obtained therefrom, but also relates to the particle size distribution (also characterized by span) of catalyst particles, its fine particle content, powder fluidity, and bulk density. In addition, it is known that the polyolefin powder produced by the catalyst system based on such protocatalyst in polymerization process has a morphology similar to the protocatalyst (so-called "copy effect", for example, see S. van der Ven, Polypropylene and other Polyolefins, Elsevier 1990, pp. 8-10). Therefore, the almost round polymer particles with a length / diameter ratio (I / D) less than 2 and good powder fluidity are obtained.

[0212] As discussed above, the reactants are preferably introduced simultaneously. "Introduced simultaneously" means that the Grignard compound and the silane compound are introduced such that the molar ratio Mg / Si does not substantially change during the introduction of these compounds into the mixing device, as described in WO 01 / 23441 A1.

[0213] The silane compound and the Grignard compound can be introduced into the mixing device continuously or intermittently. Preferably, the two compounds are introduced into the mixing device continuously.

[0214] The mixing device can have various forms; it can be a mixing device in which the silane compound is premixed with the Grignard compound, or it can be a stirred reactor in which the reaction between the compounds takes place. The individual components can be metered into the mixing device by means of a peristaltic pump.

[0215] Preferably, the compounds are premixed and then the mixture is introduced into the reactor for step i). In this way, the morphology of the procatalyst formed leads to polymer particles with optimal morphology (high bulk density, narrow particle size distribution, (almost) no fines, excellent flowability).

[0216] During step i), the Si / Mg molar ratio may be in the range of 0.2 to 20. Preferably, the Si / Mg molar ratio is from 0.4 to 1.0.

[0217] The time for premixing the reactants in the above reaction step can vary within wide limits, for example from 0.1 to 300 seconds. Preferably, premixing is performed for 1 to 50 seconds.

[0218] The temperature during the premixing step of the reactants is not particularly critical and may, for example, be in the range of 0 to 80°C, with temperatures preferably being between 10°C and 50°C.

[0219] The reaction between the reactants can be carried out, for example, at a temperature of -20°C to 100°C, for example, at a temperature of 0°C to 80°C. The reaction time is, for example, 1 to 5 hours.

[0220] The mixing speed during the reaction depends on the type of reactor used and the scale of the reactor used. The mixing speed can be determined by those skilled in the art. As a non-limiting example, mixing can be carried out with a mixing speed of 250 to 300 rpm. In one embodiment, the mixing speed is 220 to 280 rpm when using a paddle stirrer, and 270 to 330 rpm when using a propeller stirrer. During the reaction, the mixing speed can be increased. For example, during metered addition, the mixing speed can increase by 20-30 rpm per hour.

[0221] Preferably, BuMgCl is the Grignard reagent used in step i).

[0222] The first intermediate reaction product obtained by the reaction between the silane compound and the Grignard compound is usually purified by decantation or filtration and then by flushing with an inert solvent, wherein the inert solvent is, for example, a hydrocarbon solvent with, for example, 1 to 20 carbon atoms, such as pentane, isopentane, hexane or heptane. The solid product can be stored and further used in the form of a suspension in the inert solvent. Alternatively, the product can be dried, preferably partially dried, and preferably under mild conditions, for example, at ambient temperature and pressure.

[0223] The first intermediate reaction product obtained by step i) may include a formula of Mg(OR 5 ) x X 1 2-x A compound wherein:

[0224] R 1 It is a hydrocarbyl group, which is independently selected from an alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkaryl group and one or more combinations thereof. The hydrocarbyl group may be linear, branched or cyclic. The hydrocarbyl group may be substituted or unsubstituted. The hydrocarbyl group may contain one or more heteroatoms. Preferably, the hydrocarbyl group has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, even more preferably 1 to 6 carbon atoms. Preferably, the hydrocarbyl group is an alkyl group, preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, even more preferably 1 to 6 carbon atoms. More preferably, the hydrocarbyl group is selected from ethyl and methyl.

[0225] X 1 is selected from fluoride ion (F-), chloride ion (Cl-), bromide ion (Br-), or iodide ion (I-). Preferably, X 1 is chloride ion or bromide ion, and more preferably, X 1 is chloride ion.

[0226] The value of x ranges from greater than 0 and less than 2: 0 < z < 2. The value of x is preferably from 0.5 to 1.5.

[0227] Step C: Activation of the solid support:

[0228] The method for activating the solid support includes the following step ii). This step may include one or more stages.

[0229] Step ii) Activation of solid magnesium compound

[0230] Step ii): Contacting solid Mg(OR 5 ) x X 1 2-x with at least one activating compound selected from the group consisting of metal alkoxide compounds formed by an activating electron donor and formula M 1 (OR 6 ) v-w (OR 7 ) w or M 2 (OR 6 ) v-w (R 7 ) w wherein:

[0231] R 6 is a hydrocarbon group independently selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl, or alkaryl groups and one or more combinations thereof. The hydrocarbon group may be linear, branched, or cyclic. The hydrocarbon group may be substituted or unsubstituted. The hydrocarbon group may contain one or more heteroatoms. Preferably, the hydrocarbon group has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, even more preferably 1 to 6 carbon atoms. Preferably, the hydrocarbon group is an alkyl group, preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, even more preferably 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, or hexyl; most preferably selected from ethyl and methyl.

[0232] R 7It is a hydrocarbyl group independently selected from an alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkaryl group and one or more combinations thereof. The hydrocarbyl group may be linear, branched or cyclic. The hydrocarbyl group may be substituted or unsubstituted. The hydrocarbyl group may contain one or more heteroatoms. Preferably, the hydrocarbyl group has 1 to 20 carbon atoms, more preferably 1 to 2 carbon atoms, even more preferably 1 to 6 carbon atoms. Preferably, the hydrocarbyl group is an alkyl group, preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, even more preferably 1 to 6 carbon atoms; most preferably selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl and cyclopentyl.

[0233] M 1 is a metal selected from Ti, Zr, Hf, Al or Si; v is M 1 The valence of 2 is metal Si; v is M 2 The valence and w of are less than v.

[0234] Electron donor and formula M(OR 6 ) v-w (OR 7 ) w and M(OR 6 ) v-w (R 7 ) w The compound may also be referred to herein as an activating compound.

[0235] In this step, one or two types of activating compounds (ie, activating electron donors or metal alkoxides) may be used.

[0236] The use of this activation step before contacting the solid support with the halogen-containing titanium compound (process step C) has the advantage that a higher polyolefin yield is obtained per gram of procatalyst. In addition, in the copolymerization of propylene and ethylene, the ethylene sensitivity of the catalyst system is also increased due to this activation step. This activation step is disclosed in detail in WO 2007 / 134851 of the applicant.

[0237] Examples of suitable activating electron donors that can be used in step ii) are known to those skilled in the art and are described below, namely including carboxylic acids, carboxylic anhydrides, carboxylic esters, carboxylic halides, alcohols, ethers, ketones, amines, amides, nitriles, aldehydes, alkoxides, sulfonamides, thioethers, thioesters and other organic compounds containing one or more heteroatoms (such as nitrogen, oxygen, sulfur and / or phosphorus).

[0238] Preferably, an alcohol is used as an activating electron donor in step ii). More preferably, the alcohol is a linear or branched aliphatic or aromatic alcohol having 1 to 12 carbon atoms. Even more preferably, the alcohol is selected from methanol, ethanol, butanol, isobutanol, hexanol, xylenol and benzyl alcohol. Most preferably, the alcohol is ethanol or methanol, preferably ethanol.

[0239] Suitable carboxylic acids as activating electron donors may be aliphatic or (partially) aromatic. Examples include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, acrylic acid, methacrylic acid, maleic acid, fumaric acid, tartaric acid, cyclohexanemonocarboxylic acid, cis-1,2-cyclohexanedicarboxylic acid, phenylcarboxylic acid, toluenecarboxylic acid, naphthalenecarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid and / or trimellitic acid.

[0240] Anhydrides of the above-mentioned carboxylic acids may be mentioned as examples of the carboxylic anhydride, such as acetic anhydride, butyric anhydride, and methacrylic anhydride.

[0241] Suitable examples of esters of the above carboxylic acids are formates such as butyl formate; acetates such as ethyl acetate and butyl acetate; acrylates such as ethyl acrylate, methyl methacrylate and isobutyl methacrylate; benzoates such as methyl benzoate and ethyl benzoate; methyl p-toluate; ethyl-naphthate and phthalates such as monomethyl phthalate, dibutyl phthalate, diisobutyl phthalate, diallyl phthalate and / or diphenyl phthalate.

[0242] Examples of suitable carboxylic acid halides as activating electron donors are halides of the abovementioned carboxylic acids, for example acetyl chloride, acetyl bromide, propionyl chloride, butyryl chloride, butyryl iodide, benzoyl bromide, p-phenylacetyl chloride and / or phthaloyl dichloride.

[0243] Suitable alcohols are linear or branched aliphatic alcohols with 1 to 12 C atoms, or aromatic alcohols. Examples include methanol, ethanol, butanol, isobutanol, hexanol, xylenol and benzyl alcohol. The alcohols can be used alone or in combination. Preferably, the alcohol is ethanol or hexanol.

[0244] Examples of suitable ethers are ethyl ether, butyl ether, isoamyl ether, anisole and ethylphenyl ether, 2,2-diisobutyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2-ethyl-2-butyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane and / or 9,9-bis(methoxymethyl)fluorene (flu). Cyclic ethers such as tetrahydrofuran (THF) or trisethers may also be used.

[0245] Suitable examples of other organic compounds containing heteroatoms that are activating electron donors include 2,2,6,6-tetramethylpiperidine, 2,6-dimethylpiperidine, pyridine, 2-methylpyridine, 4-methylpyridine, imidazole, benzonitrile, aniline, diethylamine, dibutylamine, dimethylacetamide, thiophenol, 2-methylthiophene, isopropyl mercaptan, diethyl sulfide, diphenyl sulfide, tetrahydrofuran, dioxane, methyl ether, ethyl ether, anisole, acetone, triphenylphosphine, triphenyl phosphite, diethyl phosphate and / or diphenyl phosphate.

[0246] Examples of suitable metal alkoxides used in step ii) are metal alkoxides of the formula: 1 (OR 6 ) v-w (OR 7 ) w and M 2 (OR 6 ) v-w (R 7 ) w , where M 1 、M 2 , R 6 , R 7 , v and w are as defined herein. 6 and R 7 It may also be an aromatic hydrocarbyl group which may be optionally substituted, for example, by an alkyl group and may contain, for example, 6 to 20 carbon atoms. 6 and R 7 Preferably contains 1-12 or 1-8 carbon atoms. In a preferred embodiment, R 6 and R 7 is ethyl, propyl or butyl; more preferably all the groups are ethyl groups.

[0247] Preferably, M in the activating compound 1 is Ti or Si. Si-containing compounds suitable as activating compounds are the same as listed above for step i).

[0248] The value of w is preferably 0, and the activating compound is, for example, a tetraalkoxytitanium having four alkoxy groups with a total of 4 to 32 carbon atoms. The four alkoxy groups in the compound may be the same or independently different. Preferably, at least one of the alkoxy groups in the compound is an ethoxy group. More preferably, the compound is a tetraalkoxide, such as tetraethoxytitanium.

[0249] In the preferred method of preparing the procatalyst, either a single activating compound or a mixture of two or more compounds may be used.

[0250] Compound M 1 (OR 6 )v-w (OR 7 ) w or M 2 (OR 6 ) v-w (R 7 ) w Combination with electron donors is preferred as activating compound to obtain, for example, catalyst systems which show high activity, and the ethylene sensitivity of the catalyst system can be influenced by the choice of the internal donor; this is particularly advantageous when preparing, for example, copolymers of propylene and ethylene.

[0251] Preferably, the Ti-based compound (eg, tetraethoxytitanium) is used together with an alcohol (eg, ethanol or hexanol) or with an ester compound (eg, ethyl acetate, ethyl benzoate, or phthalate) or together with an ether (eg, butyl ether) or with pyridine.

[0252] If two or more activating compounds are used in step ii), the order in which they are added is not critical, but may affect the catalyst performance depending on the compounds used. A person skilled in the art may optimize their order of addition based on some experiments. The compounds of step ii) may be added together or sequentially.

[0253] Preferably, the electron donor compound is first added to the 5 ) x X 1 2-x Then add a compound of formula M as defined herein 1 (OR 6 ) v-w (OR 7 ) w or M 2 (OR 6 ) v-w (R 7 ) w The activating compounds are preferably each added slowly, for example over a period of 0.1-6 hours, preferably over a period of 0.5-4 hours, most preferably over a period of 1-2.5 hours.

[0254] When more than one activating compound is used, the first intermediate reaction product obtained in step i) can be contacted with the activating compounds in any order. In one embodiment, the activating electron donor is first added to the first intermediate reaction product, and then compound M is added. 1 (OR 6 ) v-w (OR 7 ) w or M 2 (OR 6 ) v-w (R7 ) w ; No agglomeration of the solid particles is observed in this sequence. The compounds in step ii) are preferably added individually slowly, for example over a period of 0.1-6 hours, preferably over a period of 0.5-4 hours, most preferably over a period of 1-2.5 hours.

[0255] Activating compounds and Mg(OR 5 ) x X 1 2-x The molar ratio of may vary between wide limits, for example from 0.02 to 1.0. Preferably, the molar ratio is from 0.05 to 0.5, more preferably from 0.06 to 0.4, even from 0.07 to 0.2.

[0256] The temperature in step ii) may be in the range of -20 to 70°C, preferably -10 to 50°C, more preferably in the range of -5 to 40°C, and most preferably in the range of 0 to 30°C.

[0257] Preferably, at least one of the reaction components is metered in time, for example over a period of 0.1 to 6 hours, preferably over a period of 0.5 to 4 hours, more particularly over a period of 1-2.5 hours.

[0258] The reaction time after the activating compound has been added is preferably from 0 to 3 hours.

[0259] The mixing speed during the reaction depends on the type of reactor used and the scale of the reactor used. The mixing speed can be determined by one skilled in the art and should be sufficient to agitate the reactants.

[0260] The inert dispersant used in step ii) is preferably a hydrocarbon solvent. The dispersant may be, for example, an aliphatic or aromatic hydrocarbon having 1 to 20 carbon atoms. Preferably, the dispersant is an aliphatic hydrocarbon, more preferably pentane, isopentane, hexane or heptane, most preferably heptane.

[0261] Starting from the solid Mg-containing product obtained in step i) with controlled morphology, said morphology is not negatively affected during the treatment with the activating compound in step ii). The solid second intermediate reaction product obtained in step ii) is considered to be an adduct of the Mg-containing compound and at least one activating compound defined in step ii) and still has controlled morphology.

[0262] The second intermediate reaction product obtained after step ii) can be solid and can be further washed, preferably with a solvent (the solvent also serves as an inert dispersant); then stored and further used in the form of a suspension in the inert solvent. Alternatively, the product can be dried, preferably partially dried, preferably slowly and under mild conditions, for example at ambient temperature and pressure.

[0263] Step D: Contacting the solid support with a catalytic species and one or more internal donors or activators:

[0264] This step can take different forms, such as i) contacting the solid support with a catalytic species and one or more internal donors to obtain the procatalyst; ii) contacting the solid support with a catalytic species and one or more internal donors to obtain an intermediate product; iii) contacting the solid support with a catalytic species and an activator donor to obtain an intermediate product.

[0265] Step D may comprise several stages. During each of these successive stages, the solid support is contacted with the catalytic species. In other words, the addition or reaction of the catalytic species may be repeated one or more times.

[0266] For example, during stage I of step D, the solid support (first intermediate) or activated solid support (second intermediate) is first contacted with the catalytic species and then optionally with one or more internal donors. When there is a second stage, during stage II, the intermediate product obtained from stage I will be contacted with additional catalytic species (the catalytic species may be the same or different from the catalytic species added during the first stage) and optionally one or more internal donors. In the case where there are three stages, stage III is preferably a repetition of stage II or may include contacting the product obtained from stage II with both the catalytic species (the catalytic species may be the same or different from the above) and one or more internal donors. In other words, the internal donor may be added during each of these stages or during two or more of these stages. When the internal donor is added during more than one stage, it may be the same or different internal donor.

[0267] The activator according to the invention may be added during stage I or stage II or stage III. It is also possible to add the activator during more than one stage.

[0268] Preferably, the method of contacting the solid support with the catalytic species and the internal donor comprises the following step iii).

[0269] Step iii) reacting the solid support with a transition metal halide

[0270] Step iii) involves reacting the solid support with a transition metal halide (e.g. titanium, chromium, hafnium, zirconium or vanadium) but preferably a titanium halide. In the following discussion only methods for titanium based Ziegler Natta procatalysts are disclosed, however the present application is also applicable to other types of Ziegler Natta procatalysts.

[0271] Step iii) further involves contacting the first intermediate reaction product or the second intermediate reaction product obtained in step i) or ii) respectively with a halogen-containing Ti compound and an internal electron donor or activator to obtain a third intermediate product.

[0272] Step iii) may be performed on the first intermediate product after step i), or on the second intermediate product after step ii).

[0273] The molar ratio of transition metal to magnesium in step iii) is preferably from 10 to 100, most preferably from 10 to 50.

[0274] Preferably, an internal electron donor is also present during step iii).It is also possible to use mixtures of internal electron donors.

[0275] The molar ratio of the internal electron donor relative to magnesium can vary between wide limits, for example from 0.02 to 0.75. Preferably, the molar ratio is from 0.05 to 0.5; more preferably from 0.1 to 0.4; and most preferably from 0.1 to 0.3.

[0276] During contacting the second intermediate product with the halogen-containing titanium compound, an inert dispersant is preferably used. The dispersant is preferably selected so that almost all of the by-products formed are dissolved in the dispersant. Suitable dispersants include, for example, aliphatic and aromatic hydrocarbons and halogenated aromatic solvents having, for example, 4 to 20 carbon atoms. Examples include toluene, xylene, benzene, heptane, o-chlorotoluene and chlorobenzene.

[0277] The reaction temperature during step iii) is preferably 0°C to 150°C, more preferably 50°C to 150°C, and more preferably 100°C to 140°C. Most preferably, the reaction temperature is 110°C to 125°C.

[0278] The reaction time during step iii) is preferably 10 minutes to 10 hours. In the case of several stages, each stage may have a reaction time of 10 minutes to 10 hours. The reaction time can be determined by those skilled in the art based on the reactor and the original catalyst.

[0279] The mixing speed during the reaction depends on the type of reactor used and the scale of the reactor used. The mixing speed can be determined by one skilled in the art and should be sufficient to agitate the reactants.

[0280] The reaction product obtained can be washed, usually with an inert aliphatic or aromatic hydrocarbon or a halogenated aromatic compound, to obtain the procatalyst of the present invention. If desired, the reaction and subsequent purification steps can be repeated one or more times. Preferably, a final wash with an aliphatic hydrocarbon results in a suspended or at least partially dried procatalyst, as described above for the other steps.

[0281] Optionally, during step iii) of step D, an activator is present instead of an internal donor

[0282] In some embodiments, the optional activator is the same as the activator used during the previous step. In some embodiments, the optional activator is different from the activator used during the previous step. However, it is separated from the same list.

[0283] The molar ratio of the optional activator relative to magnesium can vary between wide limits, for example from 0.02 to 0.5. Preferably, the molar ratio is from 0.05 to 0.4; more preferably from 0.1 to 0.3; and most preferably from 0.1 to 0.2.

[0284] Step E: Modification of the Catalyst with a Metal-Based Modifier

[0285] This step E is optional in the present invention. In a preferred method for modifying a supported catalyst, this step comprises the following steps:

[0286] step iv) modifying the third intermediate product with a metal modifier to produce a modified intermediate product;

[0287] Step v) contacting the modified intermediate product with a titanium halide and optionally one or more internal donors to obtain the procatalyst of the present invention.

[0288] The order of addition, ie the order of the first step iv) and the subsequent step v), is believed to be very important for the formation of the correct clusters of Group 13 or transition metals and titanium forming modified and more active catalytic centres.

[0289] Each of these steps is disclosed in more detail below.

[0290] It should be noted that steps iii), iv) and v) (ie steps D and E) are preferably carried out in the same reactor, ie directly one after the other in the same reaction mixture.

[0291] Preferably, step iv) is carried out directly after step iii) in the same reactor. Preferably, step v) is carried out directly after step iv) in the same reactor.

[0292] Step iv): Group 13 or transition metal modification

[0293] Modification with a Group 13 or transition metal, preferably aluminum, ensures that a Group 13 or transition metal is present in the procatalyst in addition to magnesium (from the solid support) and titanium (from the titanation treatment).

[0294] Without wishing to be bound by any particular theory, the inventors believe that one possible explanation is that the presence of the Group 13 or transition metal increases the reactivity of the active sites and thus increases the yield of polymer.

[0295] Step iv) comprises modifying the third intermediate product obtained in step iii) with a modifying agent having the formula MX3, wherein M is a metal selected from Group 13 metals or transition metals of the IUPAC Periodic Table, and wherein X is a halide ion to produce a modified intermediate product.

[0296] Preferably, step iv) is carried out directly after step iii), more preferably in the same reactor and preferably in the same reaction mixture. In one embodiment, a mixture of aluminum chloride and a solvent (e.g. chlorobenzene) is added to the reactor after step iii) has been carried out. After the reaction has been completed, the solid is allowed to settle, the solid can be obtained by decantation or filtration and optionally purified, or a suspension of the solid in a solvent can be used in the subsequent step, i.e. step v).

[0297] The metal modifier is preferably selected from aluminum modifiers (e.g., aluminum halides), boron modifiers (e.g., boron halides), gallium modifiers (e.g., gallium halides), zinc modifiers (e.g., zinc halides), copper modifiers (e.g., copper halides), thallium modifiers (e.g., thallium halides), indium modifiers (e.g., indium halides), vanadium modifiers (e.g., vanadium halides), chromium modifiers (e.g., chromium halides), and iron modifiers (e.g., iron halides).

[0298] Examples of suitable modifiers are aluminum trichloride, aluminum tribromide, aluminum triiodide, aluminum trifluoride, boron trichloride, boron tribromide, boron triiodide, boron trifluoride, gallium trichloride, gallium tribromide, gallium triiodide, gallium trifluoride, zinc dichloride, zinc dibromide, zinc diiodide, zinc difluoride, copper dichloride, copper dibromide, copper diiodide, copper difluoride, copper chloride, copper bromide, copper iodide, copper fluoride, thallium trichloride, Thallium tribromide, thallium triiodide, thallium trifluoride, thallium chloride, thallium bromide, thallium iodide, thallium fluoride, indium trichloride, indium tribromide, indium triiodide, indium trifluoride, vanadium trichloride, vanadium tribromide, vanadium triiodide, vanadium trifluoride, chromium trichloride, chromium dichloride, chromium tribromide, chromium dibromide, iron dichloride, iron trichloride, iron tribromide, iron dichloride, iron triiodide, iron diiodide, iron trifluoride and iron difluoride.

[0299] The amount of metal halide added during step iv) can vary depending on the amount of metal desired to be present in the procatalyst. It may, for example, be in the range of 0.1 to 5% by weight, preferably 0.5 to 1.5% by weight, based on the total weight of the support, directly after step iii) in the same reactor.

[0300] The metal halide is preferably mixed with a solvent and then added to the reaction mixture. The solvent used in this step can be selected from, for example, aliphatic and aromatic hydrocarbons and halogenated aromatic solvents, which have, for example, 4 to 20 carbon atoms. Examples include toluene, xylene, benzene, decane, o-chlorotoluene and chlorobenzene. The solvent can also be a mixture of two or more thereof.

[0301] The duration of the modification step may vary from 1 minute to 120 minutes, preferably from 40 to 80 minutes, more preferably from 50 to 70 minutes. This time depends on the concentration of the modifying agent, the temperature, the type of solvent used, etc.

[0302] The modification step is preferably carried out at elevated temperature (eg 50 to 120°C, preferably 90 to 110°C).

[0303] The modification step can be carried out while stirring. The mixing speed during the reaction depends on the type of reactor used and the scale of the reactor used. The mixing speed can be determined by those skilled in the art. As a non-limiting example, it is possible to mix with a stirring speed of 100 to 400 rpm, preferably 150 to 300 rpm, more preferably about 200 rpm.

[0304] The weight / volume ratio of the metal halide and the solvent in step iv) is 0.01 g-0.1 g: 5.0-100 ml.

[0305] The modified intermediate product is present in a solvent. It can be kept in the solvent and then directly proceed to step v). However, it can also be separated and / or purified. The solid can be allowed to settle by stopping stirring. The supernatant can then be removed by decantation. In addition, filtering of the suspension is also possible. The solid product can be washed once or several times with the same solvent used during the reaction or with another solvent selected from the same group described above. The solid can be resuspended or can be dried or partially dried for storage.

[0306] After this step, step v) is carried out to produce the procatalyst according to the present invention.

[0307] Step v): Titanation of the intermediate product

[0308] This step is very similar to step iii). It involves an additional titanation of the modified intermediate product.

[0309] Step v) involves contacting said modified intermediate product obtained in step iv) with a halogen-containing titanium compound so as to obtain the procatalyst according to the present invention. When an activator is used during step iii), an internal donor is used during this step.

[0310] Preferably step v) is carried out directly after step iv), more preferably in the same reactor and preferably in the same reaction mixture.

[0311] In one embodiment, at the end of step iv) or at the beginning of step v), the supernatant is removed from the solid modified intermediate obtained in step iv) by filtering or by decantation. A mixture of titanium halide (e.g., tetrachloride) and solvent (e.g., chlorobenzene) can be added to the remaining solid. The reaction mixture is then maintained at an elevated temperature (e.g., 100 to 130° C., e.g., 115° C.) for a certain time (e.g., 10 to 120 minutes, e.g., 20 to 60 minutes, e.g., 30 minutes). The solid material is then allowed to settle by stopping stirring.

[0312] The molar ratio of transition metal to magnesium is preferably from 10 to 100, most preferably from 10 to 50.

[0313] Optionally, an internal electron donor is also present during this step. Mixtures of internal electron donors may also be used. The molar ratio of the internal electron donor relative to magnesium may vary between wide limits, for example from 0.02 to 0.75. Preferably, the molar ratio is from 0.05 to 0.4; more preferably from 0.1 to 0.4; most preferably from 0.1 to 0.3.

[0314] The solvent used in this step can be selected from, for example, aliphatic and aromatic hydrocarbons and halogenated aromatic solvents, which have, for example, 4 to 20 carbon atoms. The solvent can also be a mixture of two or more thereof.

[0315] According to a preferred embodiment of the invention, step v) is repeated, in other words, the supernatant is removed as described above and a mixture of titanium halide (e.g. tetrachloride) and solvent (e.g. chlorobenzene) is added. The reaction is continued at elevated temperature for a certain time, which may be the same or different from the time for which step v) was carried out for the first time.

[0316] The steps can be carried out while stirring. The mixing speed during the reaction depends on the type of reactor used and the scale of the reactor used. The mixing speed can be determined by those skilled in the art. It can be the same as discussed above for step iii).

[0317] Therefore, in this embodiment step v) can be considered to consist of at least two sub-steps, the sub-steps being:

[0318] va) contacting said modified intermediate product obtained in step iv) with titanium tetrachloride (optionally using an internal donor) to obtain a partially titanated procatalyst;

[0319] vb) contacting the partially titanated procatalyst obtained in step va) with titanium tetrachloride to obtain a procatalyst.

[0320] There may be additional sub-steps increasing the number of titanization steps to more than four.

[0321] The solid material (procatalyst) obtained is washed several times with a solvent (e.g. heptane), preferably at an elevated temperature, e.g. 40 to 100° C., the elevated temperature depending on the boiling point of the solvent used, preferably 50 to 70° C. The procatalyst suspended in the solvent is then obtained. The solvent can be removed by filtering or decantation. The procatalyst can be used as such in a form moistened with the solvent or suspended in the solvent, or it can be first dried, preferably partially dried, for storage. The drying can be carried out for several hours, for example, by a low-pressure nitrogen stream.

[0322] Thus, in this embodiment, the entire titanation process includes three periods of titanium halide addition, wherein the first addition period is separated from the second and third addition periods by modification with the metal halide.

[0323] It can be said that the difference between the prior art and the present invention is that the titanation step (i.e. the step of contacting with the titanium halide) according to the present invention is divided into two parts and the Group 13 or transition metal modification step is introduced between the two parts or stages of the titanation. Preferably, the first part of the titanation comprises a single titanation step and the second part of the titanation comprises two subsequent titanation steps. When the modification is carried out before the titanation step, as observed by the inventors, the increase in activity is less. When the modification is carried out after the titanation step, as observed by the inventors, the increase in activity is less.

[0324] Briefly, embodiments of the present invention include the following steps: i) preparing a first intermediate reaction product; ii) activating a solid support to produce a second intermediate reaction product; iii) a first titanation or stage I to produce a third intermediate reaction product; iv) modification to produce a modified intermediate product; v) a second titanation or stage II / III to produce a procatalyst.

[0325] The procatalyst may have a titanium, hafnium, zirconium, chromium or vanadium (preferably titanium) content of from about 0.1 wt % to about 6.0 wt %, or from about 1.0 wt % to about 4.5 wt %, or from about 1.5 wt % to about 3.5 wt %, based on the total weight of solids.

[0326] The weight ratio of titanium, hafnium, zirconium, chromium or vanadium (preferably titanium) to magnesium in the solid procatalyst may be from about 1:3 to about 1:160, or from about 1:4 to about 1:50, or from about 1:6 to 1:30. The weight percentages are based on the total weight of the procatalyst.

[0327] The transition metal-containing solid catalyst compound according to the present invention comprises a transition metal halide (eg, titanium halide, chromium halide, hafnium halide, zirconium halide, vanadium halide) supported on a metal or metalloid compound (eg, a magnesium compound or a silicon dioxide compound).

[0328] Preferably, a magnesium-based support or a magnesium-containing support is used in the present invention. Such supports are prepared from magnesium-containing support precursors, such as magnesium halides, alkyl magnesiums and aryl magnesiums, and alkoxy magnesium and aryloxy magnesium compounds.

[0329] The support may be activated using an activating compound as described in more detail in step C above.

[0330] The catalyst system according to the present invention includes a cocatalyst. "Cocatalyst" as used herein is a well-known term in the Ziegler-Natta catalyst field and is recognized as a substance capable of converting the original catalyst into an active polymerization catalyst. Typically, the cocatalyst is an organometallic compound containing a metal from Group 1, 2, 12 or 13 of the periodic table (Handbook of Chemistry and Physics, 70th edition, CRC Press, 1989-1990).

[0331] The promoter may include any compound known in the art to be used as a "promoter", such as hydrides, alkylates or arylates of aluminum, lithium, zinc, tin, cadmium, beryllium, magnesium, and combinations thereof. The promoter may be a compound of formula R 20 Hydrocarbyl aluminum co-catalyst represented by 3Al.

[0332] R 20 is independently selected from hydrogen or a hydrocarbon group selected from an alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkaryl group and one or more combinations thereof. The hydrocarbon group may be linear, branched or cyclic. The hydrocarbon group may be substituted or unsubstituted. The hydrocarbon group may contain one or more heteroatoms. Preferably, the hydrocarbon group has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, even more preferably 1 to 6 carbon atoms. Provided that at least one R 20 is a hydrocarbon group. Optionally, two or three R 20 The groups are connected into cyclic groups to form heterocyclic structures.

[0333] Suitable R 20 Non-limiting examples of radicals are: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, 2-methylpentyl, heptyl, octyl, isooctyl, 2-ethylhexyl, 5,5-dimethylhexyl, nonyl, decyl, isodecyl, undecyl, dodecyl, phenyl, phenethyl, methoxyphenyl, benzyl, tolyl, xylyl, naphthyl, methylnaphthyl, cyclohexyl, cycloheptyl, and cyclooctyl.

[0334] Suitable examples of hydrocarbyl aluminum compounds as cocatalysts include triisobutylaluminum, trihexylaluminum, diisobutylaluminum hydride, dihexylaluminum hydride, isobutylaluminum dihydride, hexylaluminum dihydride, diisobutylhexylaluminum, isobutyldihexylaluminum, trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, trioctylaluminum, tridecylaluminum, tridodecylaluminum, tribenzylaluminum, triphenylaluminum, trinaphthylaluminum, and tritolylaluminum. In one embodiment, the cocatalyst is selected from triethylaluminum, triisobutylaluminum, trihexylaluminum, diisobutylaluminum hydride, and dihexylaluminum hydride. More preferably, trimethylaluminum, triethylaluminum, triisobutylaluminum, and / or trioctylaluminum. Most preferably, triethylaluminum (TEAL for short).

[0335] The co-catalyst may also be a 21 m AIX 21 3-m Represented by the hydrocarbyl aluminum compound.

[0336] R 21 is an alkyl group. The alkyl group may be linear, branched or cyclic. The alkyl group may be substituted or unsubstituted. Preferably, the alkyl group has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, even more preferably 1 to 6 carbon atoms.

[0337] Suitable R 21 Non-limiting examples of the radical are: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, 2-methylpentyl, heptyl, octyl, isooctyl, 2-ethylhexyl, 5,5-dimethylhexyl, nonyl, decyl, isodecyl, undecyl and dodecyl.

[0338] X 21 Selected from fluoride ion (F-), chloride ion (Cl-), bromide ion (Br-) or iodide ion (I-) or alkoxide (RO - ). The value of m is preferably 1 or 2.

[0339] Non-limiting examples of suitable alkylaluminum halide compounds for the cocatalyst include tetraethyldialuminoxane, methylaluminoxane, isobutylaluminoxane, tetraisobutyldialuminoxane, diethylaluminum ethoxide, diisobutylaluminum chloride, methylaluminum dichloride, diethylaluminum chloride, ethylaluminum dichloride, and dimethylaluminum chloride.

[0340] Non-limiting examples of suitable compounds include tetraethyldialuminoxane, methylaluminoxane, isobutylaluminoxane, tetraisobutyldialuminoxane, diethylaluminum ethoxide, diisobutylaluminum chloride, methylaluminum dichloride, diethylaluminum chloride, ethylaluminum dichloride, and dimethylaluminum chloride.

[0341] Preferably, the cocatalyst is triethylaluminum. The molar ratio of aluminum to titanium can be from about 5:1 to about 500:1 or from about 10:1 to about 200:1 or from about 15:1 to about 150:1 or from about 20:1 to about 100:1. The molar ratio of aluminum to titanium is preferably about 45:1.

[0342] One of the functions of the external donor compound is to influence the stereoselectivity of the catalyst system in the polymerization of olefins having three or more carbon atoms. It is therefore also called a selectivity control agent.

[0343] Examples of external donors suitable for use in the present invention are: alkoxysilanes, 1,3-diethers, benzoates, alkylaminoalkoxysilanes, alkylalkoxysilanes, imidosilanes and alkylimidosilanes, preferably n-propyltrimethoxysilane (nPTMS), n-propyltriethoxysilane (nPEMS), diisobutyldimethoxysilane (DiBDMS), tert-butylisopropyldimethoxysilane (tBiPDMS), cyclohexylmethyldimethoxysilane (CHMDMS), dicyclopentyldimethoxysilane (DCPDMS), di(isopropyl)dimethoxysilane (DiPDMS) or di(isobutyl)dimethoxysilane (diBDMS).

[0344] In one embodiment, an external electron donor and / or an activity limiting agent (ALA) may be added separately to the reactor to reduce thermal runaway of the catalyst. The activity limiting agent may be selected from esters, amines, nitriles, amides, and one or more combinations thereof. Suitable esters for use as ALA include aliphatic or aromatic, mono- or poly-carboxylic acid esters, for example, ethyl and methyl benzoate, ethyl p-methoxybenzoate, methyl p-ethoxybenzoate, ethyl p-ethoxybenzoate, ethyl acrylate, methyl methacrylate, ethyl acetate, octyl acetate, ethyl p-chlorobenzoate, hexyl p-aminobenzoate, isopropyl naphthoate, n-pentyl methylbenzoate, ethyl cyclohexanecarboxylate, amyl valerate, propyl pivalate, isopropyl myristate, di-n-butyl sebacate, (poly)(alkylene glycol) mono- or di-acetate, (poly)(alkylene glycol) mono- or dimyristate, (poly)(alkylene glycol) mono- or di-laurate, (poly)(alkylene glycol) mono- or di-oleate, tri(acetate)glyceryl, triglycerides of C2-10 aliphatic carboxylic acids, and mixtures thereof. Suitable amines for use as ALA include, but are not limited to, aminobenzoates, aliphatic amines such as N,N,N'N'-tetramethylethylenediamine; cycloaliphatic amines such as 1,2,4-trimethylpiperazine, 2,3,4,5-tetraethylpiperidine, and phthalates such as dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-tert-butyl phthalate, diisoamyl phthalate, di-tert-amyl phthalate, dineopentyl phthalate, di(2-ethylhexyl)phthalate, and di(2-ethyldecyl)phthalate, and mixtures thereof. Suitable nitriles for use as ALA include, but are not limited to, aromatic and aliphatic nitriles such as alkane nitriles such as trimethylacetonitrile, and mixtures thereof. Suitable amides for use as ALA include, but are not limited to, aromatic and aliphatic amides, such as N,N-dimethylbenzamide, and mixtures thereof.

[0345] In another embodiment, the external electron donor and the activity limiting agent may be premixed together and then added to the reactor as a mixture. More than one external electron donor or more than one activity limiting agent may be used in the mixture.

[0346] In one embodiment, the mixture is dicyclopentyldimethoxysilane and isopropyl myristate, dicyclopentyldimethoxysilane and poly(ethylene glycol) laurate, diisopropyldimethoxysilane and isopropyl myristate, dicyclopentyldimethoxysilane and isopropyl myristate and poly(ethylene glycol) dioleate, diisobutyldimethoxysilane and isopropyl myristate, methylcyclohexyldimethoxysilane and isopropyl myristate, n-propyltrimethoxysilane and isopropyl myristate, dimethyldimethoxysilane and methylcyclohexyldimethoxysilane and isopropyl myristate, dicyclopentyldimethoxysilane and n-propyltriethoxysilane and isopropyl myristate, and dicyclopentyldimethoxysilane and tetraethoxysilane and isopropyl myristate, and combinations thereof.

[0347] The aluminum / external donor molar ratio in the polymerization catalyst system is preferably from 0.1 to 200; more preferably from 1 to 100.

[0348] A mixture 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.

[0349] When a silane external donor is used, the Si / Ti molar ratio in the catalyst system may be in the range of 0.1 to 40, preferably 0.1 to 20, even more preferably 1 to 20, and most preferably 2 to 10.

[0350] The monocarboxylic acid esters (also known as "benzoates") shown in formula (VI) can be used as external donors.

[0351]

[0352] R 30 Selected from hydrocarbyl groups, which are independently selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkaryl groups and one or more combinations thereof. The hydrocarbyl group can be linear, branched or cyclic. The hydrocarbyl group can be substituted or unsubstituted. The hydrocarbyl group can contain one or more heteroatoms. Preferably, the hydrocarbyl group has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, even more preferably 1 to 6 carbon atoms. Suitable examples of hydrocarbyl groups include alkyl, cycloalkyl, alkenyl, diene, cycloalkenyl, cycloalkadienyl, aryl, aralkyl, alkaryl and alkynyl groups.

[0353] R 31 , R 32 , R 33 , R 34 , R 35Each independently selected from hydrogen, heteroatom (preferably halogen) or hydrocarbyl group, the hydrocarbyl group is selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkaryl group and one or more combinations thereof. The hydrocarbyl group can be linear, branched or cyclic. The hydrocarbyl group can be substituted or unsubstituted. The hydrocarbyl group can contain one or more heteroatoms. Preferably, the hydrocarbyl group has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, even more preferably 1 to 6 carbon atoms.

[0354] Suitable non-limiting examples of "benzoic acid esters" include alkyl p-alkoxybenzoates (e.g., ethyl p-methoxybenzoate, methyl p-ethoxybenzoate, ethyl p-ethoxybenzoate), alkyl benzoates (e.g., ethyl benzoate, methyl benzoate), alkyl p-halobenzoates (ethyl p-chlorobenzoate, ethyl p-bromobenzoate), and benzoic anhydride. Benzoic acid esters are preferably selected from ethyl benzoate, benzoyl chloride, ethyl p-bromobenzoate, n-propyl benzoate, and benzoic anhydride. Benzoic acid esters are more preferably ethyl benzoate.

[0355] The "diether" may be a 1,3-di(hydrocarbyloxy)propane compound optionally substituted at the 2-position represented by formula (VII), which may be used as an external donor,

[0356]

[0357] R 51 and R 52 Each independently selected from hydrogen or a hydrocarbyl group, the hydrocarbyl group is selected from an alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkaryl group and one or more combinations thereof. The hydrocarbyl group can be linear, branched or cyclic. The hydrocarbyl group can be substituted or unsubstituted. The hydrocarbyl group can contain one or more heteroatoms. Preferably, the hydrocarbyl group has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, even more preferably 1 to 6 carbon atoms. Suitable examples of hydrocarbyl groups include alkyl, cycloalkyl, alkenyl, diene, cycloalkenyl, cycloalkadienyl, aryl, aralkyl, alkaryl and alkynyl groups.

[0358] R 53 and R 54 Each independently selected from hydrogen, halogen or hydrocarbyl group, the hydrocarbyl group is selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkaryl group and one or more combinations thereof. The hydrocarbyl group can be linear, branched or cyclic. The hydrocarbyl group can be substituted or unsubstituted. The hydrocarbyl group can contain one or more heteroatoms. Preferably, the hydrocarbyl group has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, even more preferably 1 to 6 carbon atoms.

[0359] Suitable examples of the dialkyl diether compound include 1,3-dimethoxypropane, 1,3-diethoxypropane, 1,3-dibutoxypropane, 1-methoxy-3-ethoxypropane, 1-methoxy-3-butoxypropane, 1-methoxy-3-cyclohexyloxypropane, 2,2-dimethyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane, 2,2-di-n-butyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2-ethyl-2-n-butyl-1,3-dimethoxypropane, 2-n-propyl-2-cyclopentyl-1,3-dimethoxypropane, 2,2-dimethyl-1,3-diethoxypropane, 2-n-propyl-2-cyclohexyl-1,3-dimethoxypropane, and 2,2-dimethyl-1,3-diethoxypropane. 3-diethoxypropane, 2-(2-ethylhexyl)-1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2-n-butyl-1,3-dimethoxypropane, 2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-1,3-dimethoxypropane, 2-phenyl-1,3-diethoxypropane, 2-cumyl-1,3-diethoxypropane, 2-(2-phenylethyl)-1,3-dimethoxypropane, 2-(2-cyclohexylethyl)-1,3-dimethoxypropane, 2-(p-chlorophenyl)-1,3-dimethoxypropane, 2-(diphenylmethyl)-1,3-dimethoxypropane, 2-(1-naphthyl)-1,3-dimethoxypropane, 2-(fluorophenyl)-1,3 -dimethoxypropane, 2-(1-decahydronaphthyl)-1,3-dimethoxypropane, 2-(p-tert-butylphenyl)-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-di-n-propyl-1,3-dimethoxypropane, 2-methyl-2-n-propyl-1,3-dimethoxypropane, 2-methyl-2-benzyl-1,3-dimethoxypropane, 2-methyl-2-ethyl-1,3-dimethoxypropane, 2-methyl-2-phenyl-1,3-dimethoxypropane, 2-methyl-2-cyclohexyl-1,3-dimethoxypropane, 2,2-bis(p-chlorophenyl)-1,3-dimethoxypropane, 2,2-bis(2-cyclohexylethyl)-1,3-dimethoxypropane, 2-methyl-2-isobutyl-1,3-dimethoxypropane, 2-methyl-2-(2-ethylhexyl)-1,3-dimethoxypropane, 2-methyl-2-isopropyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2,2-dibenzyl-1,3-dimethoxypropane, 2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-diethoxypropane, 2,2-diisobutyl-1,3-di-n-butoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2,2-di-sec-butyl-1,3-dimethoxypropane, 2,2-di-tert-butyl-1,3-dimethoxypropane, 2,2-dineopentyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2-phenyl-2-benzyl-1,3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane, 2-isopropyl-2-(3,7-dimethyloctyl)-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclohexylmethyl-1,3-dimethoxypropane, 2,2-diisopentyl-1,3-dimethoxypropane Methoxypropane, 2-isopropyl-2-cyclohexyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclopentyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2-n-heptyl-2-n-pentyl-1,3-dimethoxypropane, 9,9-bis(methoxymethyl)fluorene (flu), 1,3-dicyclohexyl-2,2-bis(methoxymethyl)propane, 3,3-bis(methoxymethyl)-2,5-dimethylhexane, or any combination of the foregoing. In one embodiment, the external electron donor is 1,3-dicyclohexyl-2,2-bis(methoxymethyl)propane, 3,3-bis(methoxymethyl)-2,5-dimethylhexane, 2,2-dicyclopentyl-1,3-dimethoxypropane, and combinations thereof. ,

[0360] Preferred ethers are exemplified by ethyl ether, butyl ether, isoamyl ether, anisole and ethylphenyl ether, 2,3-dimethoxypropane, 2,3-dimethoxypropane, 2-ethyl-2-butyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane and 9,9-bis(methoxymethyl)fluorene (flu) of formula (VIII):

[0361]

[0362] Documents EP1538167 and EP1783145 disclose Ziegler-Natta catalyst types, which contain as external donors an organosilicon compound represented by the formula Si(ORc)3(NRdRe), wherein Rc is a hydrocarbon group having 1 to 6 carbon atoms, Rd is a hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom, and Re is a hydrocarbon group having 1 to 12 carbon atoms, which serves as an external electron donor.

[0363] Another example of a suitable external donor according to the present invention is a compound according to formula (IX):

[0364] (R 90 )2N-A-Si(OR 91 )3

[0365] Formula (IX)

[0366] R 90 and R 91The groups are each independently an alkyl group having 1 to 10 carbon atoms. The alkyl group may be linear, branched or cyclic. The alkyl group may be substituted or unsubstituted. Preferably, the hydrocarbyl group has 1 to 8 carbon atoms, even more preferably 1 to 6 carbon atoms, even more preferably 2 to 4 carbon atoms. Preferably, each R 90 Preferably, each R 91 A is a direct bond between nitrogen and silicon or a spacer selected from an alkyl group having 1 to 10 carbon atoms, preferably a direct bond.

[0367] An example of such an external donor is diethylaminotriethoxysilane (DEATES), where A is a direct bond and each R 90 For ethyl and each R 91 It is ethyl.

[0368] Alkylalkoxysilanes according to formula (X) can be used as external donors.

[0369] (R 92 )Si(OR 93 )3

[0370] Formula (X)

[0371] R 92 and R 93 The groups are each independently an alkyl group having 1 to 10 carbon atoms. The alkyl group may be linear, branched or cyclic. The alkyl group may be substituted or unsubstituted. Preferably, the hydrocarbyl group has 1 to 8 carbon atoms, even more preferably 1 to 6 carbon atoms, even more preferably 2 to 4 carbon atoms. Preferably, all three R 93 Preferably, R 93 Preferably, R 92 It is ethyl or propyl, more preferably n-propyl.

[0372] Examples are n-propyltriethoxysilane (nPTES) and n-propyltrimethoxysilane (nPTMS).

[0373] Typical external donors known in the art (for example, as disclosed in WO2006 / 056338A1, EP1838741B1, US6395670B1, EP398698A1, WO96 / 32426A) are those having the general formula Si(OR a ) 4-n R b n An organosilicon compound, wherein n may be 0 to 2, and R a and R bEach of which independently represents an alkyl or aryl group, which optionally contains one or more heteroatoms, such as O, N, S or P, and has, for example, 1 to 20 carbon atoms; such as n-propyltrimethoxysilane (nPTMS), n-propyltriethoxysilane (nPEMS), diisobutyldimethoxysilane (DiBDMS), tert-butylisopropyldimethoxysilane (tBiPDMS), cyclohexylmethyldimethoxysilane (CHMDMS), dicyclopentyldimethoxysilane (DCPDMS), di(isopropyl)dimethoxysilane (DiPDMS) or di(isobutyl)dimethoxysilane (diBDMS).

[0374] Amidosilanes according to formula (XI) can be used as external donors.

[0375] Si(L) n (OR 11 ) 4-n

[0376] Formula (XI)

[0377] in,

[0378] Si is a silicon atom having a valence of 4+;

[0379] O is an oxygen atom having a valence of 2 and O is bonded to Si via a silicon-oxygen bond;

[0380] n is 1, 2, 3 or 4;

[0381] R 11 is selected from linear, branched and cyclic alkyl groups having up to 20 carbon atoms and aromatic substituted and unsubstituted hydrocarbon groups having 6 to 20 carbon atoms; two R 11 The groups may be linked and together may form a ring structure; and

[0382] L is a group represented by formula (XII)

[0383]

[0384] in,

[0385] L is bonded to the silicon atom via a nitrogen-silicon bond;

[0386] L has a single substituent on the nitrogen atom, wherein the single substituent is an imine carbon atom; and

[0387] X and Y are each independently selected from:

[0388] a) Hydrogen atom;

[0389] b) a group containing a heteroatom selected from Group 13, 14, 15, 16 or 17 of the IUPAC Periodic Table of the Elements, through which X and Y are each independently bonded to the imine carbon atom of formula XII, wherein the heteroatom is substituted by linear, branched and cyclic alkyl groups having up to 20 carbon atoms, optionally containing heteroatoms selected from Group 13, 14, 15, 16 or 17 of the IUPAC Periodic Table of the Elements; and / or aromatic substituted and unsubstituted hydrocarbon groups having 6 to 20 carbon atoms, optionally containing heteroatoms selected from Group 13, 14, 15, 16 or 17 of the IUPAC Periodic Table of the Elements;

[0390] c) linear, branched and cyclic alkyl groups having up to 20 carbon atoms, optionally containing heteroatoms selected from Group 13, 14, 15, 16 or 17 of the IUPAC Periodic Table of the Elements; and

[0391] d) aromatic substituted and unsubstituted hydrocarbon groups having 6 to 20 carbon atoms, optionally containing heteroatoms selected from Group 13, 14, 15, 16 or 17 of the IUPAC Periodic Table of Elements.

[0392] R 11 Selected from linear, branched and cyclic alkyl groups having up to 20 carbon atoms.

[0393] R 12 Selected from linear, branched and cyclic hydrocarbon groups, which are independently selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkaryl groups and one or more combinations thereof. The hydrocarbon group may be substituted or unsubstituted. The hydrocarbon group may contain one or more heteroatoms. Preferably, the hydrocarbon group has 1 to 20 carbon atoms.

[0394] Preferably, R 11 It is selected from linear, branched and cyclic alkyl groups having up to 20 carbon atoms, preferably 1 to 10 carbon atoms or 3 to 10 carbon atoms, more preferably 1 to 6 carbon atoms.

[0395] R 11 Suitable examples of include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, isobutyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl and cyclohexyl. More preferably, R 11 is a linear alkyl group having 1 to 10, even more preferably 1 to 6 carbon atoms. Most preferably, R 11 It is methyl or ethyl.

[0396] R 12Suitable examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, isobutyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, cyclohexyl, unsubstituted or substituted phenyl.

[0397] Specific examples include the following compounds: 1,1,1-triethoxy-N-(2,2,4,4-tetramethylpentane-3-ylidene)silaneamine (all R 11 = ethyl and both X and Y are tert-butyl); 1,1,1-trimethoxy-N-(2,2,4,4-tetramethylpentane-3-ylidene)silanamine (all R 11 The group is methyl, and X and Y are tert-butyl), N,N,N',N'-tetramethylguanidine triethoxysilane (all R 11 group is ethyl, and both X and Y are dimethylamino).

[0398] Alkylimidosilanes according to formula (XIII) can be used as external donors.

[0399] Si(L) n (OR 11 ) 4-n-m (R 12 ) m :Formula (XIII)

[0400] in,

[0401] Si is a silicon atom having a valence of 4+;

[0402] O is an oxygen atom having a valence of 2 and O is bonded to Si via a silicon-oxygen bond;

[0403] n is 1, 2, 3 or 4;

[0404] m is 0, 1, or 2,

[0405] n+m≤4,

[0406] R 11 selected from linear, branched and cyclic alkyl groups having up to 20 carbon atoms and aromatic substituted and unsubstituted hydrocarbon groups having from 6 to 20 carbon atoms; and

[0407] R 12 Selected from linear, branched and cyclic alkyl groups having up to 20 carbon atoms and aromatic substituted and unsubstituted hydrocarbon groups having from 6 to 20 carbon atoms;

[0408] L is a group represented by formula (XIV)

[0409]

[0410] in,

[0411] L is bonded to the silicon atom via a nitrogen-silicon bond;

[0412] L has a single substituent on the nitrogen atom, wherein the single substituent is an imine carbon atom; and

[0413] X and Y are each independently selected from:

[0414] a) Hydrogen atom;

[0415] b) a group containing a heteroatom selected from Group 13, 14, 15, 16 or 17 of the IUPAC Periodic Table of the Elements, through which X and Y are each independently bonded to the imine carbon atom of Formula XIV, wherein the heteroatom is substituted by linear, branched and cyclic alkyl groups having up to 20 carbon atoms, optionally containing heteroatoms selected from Group 13, 14, 15, 16 or 17 of the IUPAC Periodic Table of the Elements; and / or aromatic substituted and unsubstituted hydrocarbon groups having 6 to 20 carbon atoms, optionally containing heteroatoms selected from Group 13, 14, 15, 16 or 17 of the IUPAC Periodic Table of the Elements;

[0416] c) linear, branched and cyclic alkyl groups having up to 20 carbon atoms, optionally containing heteroatoms selected from Group 13, 14, 15, 16 or 17 of the IUPAC Periodic Table of the Elements; and

[0417] d) aromatic substituted and unsubstituted hydrocarbon groups having 6 to 20 carbon atoms, optionally containing heteroatoms selected from Group 13, 14, 15, 16 or 17 of the IUPAC Periodic Table of Elements.

[0418] R 11 Selected from linear, branched and cyclic alkyl groups having up to 20 carbon atoms.

[0419] R 12 Selected from linear, branched and cyclic hydrocarbon groups, which are independently selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkaryl groups and one or more combinations thereof. The hydrocarbon group may be substituted or unsubstituted. The hydrocarbon group may contain one or more heteroatoms. Preferably, the hydrocarbon group has 1 to 20 carbon atoms.

[0420] Preferably, R 11 It is selected from linear, branched and cyclic alkyl groups having up to 20 carbon atoms, preferably 1 to 10 carbon atoms or 3 to 10 carbon atoms, more preferably 1 to 6 carbon atoms.

[0421] R 11 Suitable examples of include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, isobutyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl and cyclohexyl. More preferably, R11 is a linear alkyl group having 1 to 10, even more preferably 1 to 6 carbon atoms. Most preferably, R 11 It is methyl or ethyl.

[0422] R 12 Suitable examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, isobutyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, cyclohexyl, unsubstituted or substituted phenyl.

[0423] According to formula (XV): Z n Si(OR 11 ) 4-n Formula (XVI): Z n Si(OR 11 ) 4-n-m (R 12 ) m The alkoxysilane halides are used to prepare acyliminosilane and alkylacyliminosilane respectively.

[0424] In the alkoxysilane halides represented by formulae (XV) and (XVI), Z is a halogen group, and more preferably a chlorine group; n=1, 2 or 3.

[0425] In a first specific example, the external donor may have a structure corresponding to Formula XIII, wherein n=1, m=2, X=Y=phenyl, two R 12 The group is methyl, and R 11 It is butyl.

[0426] In a second specific example, the external donor can have a structure corresponding to Formula XIII, wherein n=4, m=0, X=methyl, and Y=ethyl.

[0427] In a third specific example, the external donor may have a structure corresponding to Formula XIII, wherein n=1, m=1, X=phenyl, Y=-CH2-Si(CH3)3, and R 12 =R 11 =Methyl.

[0428] In a fourth specific example, the external donor may have a structure corresponding to Formula XIII, wherein n=1, m=1, X=-NH-C=NH(NH2)-, Y=-NH-(CH2)3-Si(OCH2CH3)3, and R 12 =-(CH2)3-NH2; R 11 =ethyl.

[0429] The additional compound(s) in the external donor according to the present invention may be one or more alkoxysilanes. The alkoxysilane compound may have any of the structures disclosed herein. The alkoxysilane is described by formula (XV)

[0430] S i 7 r (OR 8 ) 4-r

[0431] Formula (XV)

[0432] R 7 is independently a hydrocarbon group selected from an alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkaryl group and one or more combinations thereof. The hydrocarbon group may be linear, branched or cyclic. The hydrocarbon group may be substituted or unsubstituted. The hydrocarbon group may contain one or more heteroatoms. Preferably, the hydrocarbon group has 1 to 20 carbon atoms, more preferably 6 to 12 carbon atoms. For example, R 7 It can be a C6-12 aryl, alkyl or aralkyl group, a C3-12 cycloalkyl group, a C3-12 branched alkyl group, or a C3-12 cyclic or non-cyclic amino group. The value of r can be 1 or 2.

[0433] For SiNR 7 r(OR 8 ) 4-r , R 7 It may also be hydrogen.

[0434] R 8 is independently selected from hydrogen or a hydrocarbon group, the hydrocarbon group being selected from an alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkaryl group and one or more combinations thereof. The hydrocarbon group may be linear, branched or cyclic. The hydrocarbon group may be substituted or unsubstituted. The hydrocarbon group may contain one or more heteroatoms. Preferably, the hydrocarbon group has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, even more preferably 1 to 6 carbon atoms. For example, R 8 It may be a C1-4 alkyl group, preferably a methyl group or an ethyl group.

[0435] Non-limiting examples of suitable silane compounds include tetramethoxysilane (TMOS or tetramethyl orthosilicate), tetraethoxysilane (TEOS or tetraethyl orthosilicate), methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, ethyltributoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltripropoxysilane, n-propyltributoxysilane. Oxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, isopropyltripropoxysilane, isopropyltributoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, phenyltributoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, diethylaminotriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyl Diethyldipropoxysilane, diethyldibutoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-n-propyldipropoxysilane, di-n-propyldibutoxysilane, diisopropyldimethoxysilane, diisopropyldiethoxysilane, diisopropyldipropoxysilane, diisopropyldibutoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldipropoxysilane, diphenyldibutoxysilane, dicyclopentyldimethoxysilane silane, dicyclopentyldiethoxysilane, diethyldiphenoxysilane, di-tert-butyldimethoxysilane, methylcyclohexyldimethoxysilane, ethylcyclohexyldimethoxysilane, isobutylisopropyldimethoxysilane, tert-butylisopropyldimethoxysilane, trifluoropropylmethyldimethoxysilane, bis(perhydroisoquinolinyl)dimethoxysilane, dicyclohexyldimethoxysilane, dinorbornyldimethoxysilane, cyclopentylpyrrolidinyldimethoxysilane and bis(pyrrolidinyl)dimethoxysilane.

[0436] In one embodiment, the silane compound used for the additional external donor is dicyclopentyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, methylcyclohexyldimethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, dimethylaminotriethoxysilane, and one or more combinations thereof.

[0437] The present invention also relates to a method for preparing a catalyst system by contacting a Ziegler-Natta type procatalyst, a cocatalyst and an external electron donor. The procatalyst, the cocatalyst and the external donor can be contacted in any manner known to those skilled in the art; and as described herein, more specifically in the manner described in the examples.

[0438] The present invention further relates to a process for preparing polyolefins by contacting an olefin with a catalyst system according to the present invention. The procatalyst, cocatalyst, external donor and olefin may be contacted in any manner known to those skilled in the art; and are contacted as described herein.

[0439] For example, the external donor in the catalyst system according to the present invention can be complexed with the cocatalyst and mixed with the procatalyst (premixed) before contact between the procatalyst and the olefin. The external donor can also be added to the polymerization reactor independently. The procatalyst, cocatalyst and external donor can be mixed or otherwise combined before adding to the polymerization reactor.

[0440] Contacting of olefins with the catalyst system according to the invention can be accomplished under standard 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 and references cited therein.

[0441] The polymerization process may be a gas phase, slurry or bulk polymerization process operated in one or more than one reactor.One or more olefin monomers may be introduced into a polymerization reactor to react with the procatalyst and form an olefin-based polymer (or a fluidized bed of polymer particles).

[0442] In the case of slurry (liquid phase) polymerization, there is a dispersant. Suitable dispersants include, for example, propane, n-butane, isobutane, n-pentane, isopentane, hexane (e.g., isohexane or n-hexane), heptane (e.g., isoheptane or n-heptane), octane, cyclohexane, benzene, toluene, xylene, liquid propylene and / or mixtures thereof. Polymerizations such as polymerization temperature and time, monomer pressure, avoidance of catalyst contamination, selection of polymerization medium in slurry processes, use of additional components (e.g., hydrogen) to control polymer molar mass, and other conditions are known to those skilled in the art. The polymerization temperature can vary within wide limits, and for example, for propylene polymerization, is 0° C. to 120° C., preferably 40° C. to 100° C. The pressure during (propylene) (co)polymerization is, for example, 0.1 to 6 MPa, preferably 1 to 4 MPa.

[0443] Several types of polypropylene are produced, such as homoolefins, random copolymers and heterophasic polyolefins. For heterophasic polyolefins, in particular heterophasic polypropylene, the following is observed.

[0444] The heterophasic propylene copolymers are typically prepared by polymerization of propylene and optionally one or more other olefins (e.g. ethylene) followed by polymerization of a propylene-α-olefin mixture in the presence of a catalyst in one or more reactors. The resulting polymeric material may exhibit multiple phases (depending on the monomer ratios), but the specific morphology generally depends on the preparation method and the monomer ratios. The heterophasic propylene copolymers used in the process according to the invention may be produced using any conventional technique known to the skilled person, such as multistage process polymerization, such as bulk polymerization, gas phase polymerization, slurry polymerization, solution polymerization or any combination thereof. Any conventional catalyst system may be used, such as Ziegler-Natta or metallocene. Such techniques and catalysts are described, for example, in WO06 / 010414; Ser van der Ven, Polypropylene and other Polyolefins, Studies in Polymer Science 7, Elsevier 1990; WO06 / 010414, US4399054 and US4472524.

[0445] The molar mass of the polyolefin obtained during the polymerization can be controlled by adding hydrogen or any other known reagent suitable for the purpose during the polymerization.Polymerization can be carried out in continuous mode or intermittent mode.Consider slurry, body and gas phase polymerization process herein, the multistage process of each of these types of polymerization process, or the combination of different types of polymerization process in the multistage process.Preferably, the polymerization process is a single-stage gas phase process or a multistage (for example two-stage) gas phase process, for example wherein in each stage, use a gas phase process or comprise a separate (small-scale) prepolymerization reactor.

[0446] Examples of gas phase polymerization processes include both stirred bed reactors and fluidized bed reactor systems; such processes are well known in the art. A typical gas phase olefin polymerization reactor system typically includes a reactor vessel to which (one or more) olefin monomers and a catalyst system can be added, and which contains a stirred bed of growing polymer particles. Preferably, the polymerization process is a single stage gas phase process or a multistage (e.g., two stage) gas phase process, wherein a gas phase process is used in each stage.

[0447] As used herein, "gas phase polymerization" is a process in which an ascending fluidizing medium (the fluidizing medium containing one or more monomers) is passed through a fluidized bed of polymer particles in the presence of a catalyst, the polymer particles being maintained in a fluidized state by the fluidizing medium, optionally with the aid of mechanical agitation. Examples of gas phase polymerization are fluidized beds, horizontal stirred beds, and vertical stirred beds.

[0448] "Fluid bed", "fluidized" or "fluidization" is a gas-solid contact process in which a bed of finely divided polymer particles is raised and stirred by an upward gas flow, optionally assisted by mechanical agitation. In a "stirred bed", the upward gas velocity is below the fluidization threshold.

[0449] Typical gas phase polymerization reactor (or gas phase reactor) comprises container (i.e. reactor), fluidized bed, product discharge system and can comprise mechanical agitator, distribution plate, inlet pipe and outlet pipe, compressor, circulating gas cooler or heat exchanger.Container can comprise reaction zone and can comprise deceleration zone, and described deceleration zone is located above reaction zone (i.e. bed).Fluidized medium can comprise propylene gas and at least one other gas (such as olefin) and / or carrier gas (such as hydrogen or nitrogen).Contact can be occurred by feeding procatalyst to polymerization reactor and introducing olefin into polymerization reactor.In one embodiment, method comprises contacting olefin with cocatalyst.Before procatalyst is introduced into polymerization reactor, cocatalyst can be mixed (premixed) with procatalyst.Cocatalyst can also be added to polymerization reactor independently of procatalyst.Introducing cocatalyst into polymerization reactor independently can occur (substantially) simultaneously with the feeding of procatalyst.External donor can also be present during polymerization method.

[0450] The olefins according to the invention may be chosen from mono- and di-olefins containing from 2 to 40 carbon atoms. Suitable olefin monomers include α-olefins such as ethylene, propylene, α-olefins having 4 to 20 carbon atoms (i.e., C4-20), such as 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, etc.; C4-C20 dienes such as 1,3-butadiene, 1,3-pentadiene, norbornadiene, 5-vinyl-2-norbornene (VNB), 1,4-hexadiene, 5-ethylidene-2-norbornene (ENB) and dicyclopentadiene; vinyl aromatic compounds having 8 to 40 carbon atoms (i.e., C8-C40), including styrene, o-methylstyrene, m-methylstyrene and p-methylstyrene, divinylbenzene, vinylbiphenyl, vinylnaphthalene; and halogen-substituted C8-C40 vinyl aromatic compounds such as chlorostyrene and fluorostyrene.

[0451] Preferably, the olefin is propylene or a mixture of propylene and ethylene, thereby forming a propylene-based polymer, such as a propylene homopolymer or a propylene-olefin copolymer. The olefin can be an alpha-olefin with up to 10 carbon atoms, such as ethylene, butane, hexane, heptane, octene. Propylene copolymers are meant herein to include so-called random copolymers typically having a relatively low comonomer content (e.g., up to 10 mol%) and so-called impact PP copolymers or multiphase PP copolymers containing a higher comonomer content (e.g., 5 to 80 mol%, more typically 10 to 60 mol%). Impact PP copolymers are actually blends of different propylene polymers; such copolymers can be made in one or two reactors and can be a blend of a first component with a low comonomer content and a high crystallinity and a second component with a high comonomer content and a low crystallinity or even rubber properties. Such random and impact copolymers are well known to those skilled in the art. Propylene-ethylene random copolymers can be made in one reactor. Impact PP copolymers can be produced in two reactors: a polypropylene homopolymer can be produced in a first reactor; the contents of the first reactor are then transferred to a second reactor, into which ethylene (and optionally propylene) is introduced. This results in the production of a propylene-ethylene copolymer (i.e., an impact copolymer) in the second reactor.

[0452] The present invention also relates to a polyolefin, preferably polypropylene, obtained or obtainable by a process comprising contacting an olefin, preferably propylene or a mixture of propylene and ethylene, with a procatalyst according to the present invention. The terms polypropylene and propylene-based polymers are used interchangeably herein. Polypropylene can be a propylene homopolymer or a mixture of propylene and ethylene, such as a propylene-based copolymer, for example a heterophasic propylene-olefin copolymer; a random propylene-olefin copolymer, preferably a propylene-based copolymer in which the olefin is a C2 or C4-C6 olefin, such as ethylene, butene, pentene or hexene. Such propylene-based (co)polymers are known to those skilled in the art; they are also described herein above.

[0453] The present invention also relates to a polyolefin, preferably a propylene-based polymer, obtained or obtainable by the process described herein above comprising contacting propylene or a mixture of propylene and ethylene with the catalyst system according to the present invention.

[0454] In one embodiment, the present invention is directed to producing homopolymers of polypropylene.For such polymers, properties such as isotacticity and stiffness and emission may be important.

[0455] In one embodiment according to the invention, (random) copolymers of propylene and ethylene monomers are obtained.For such polymers, properties like XS and reduced haze increase over time may be important.

[0456] In one embodiment according to the invention, the heterophasic polypropylene has a matrix phase of a homopolymer of polypropylene or a random copolymer of propylene and ethylene and a dispersed phase of ethylene propylene rubber. This is called "impact polypropylene". For such polymers, properties such as stiffness and impact resistance may be important.

[0457] The content of comonomers used in addition to propylene, for example ethylene or C4-C6-olefins, can vary from 0 to 8% by weight, preferably from 1 to 4% by weight, based on the total weight of the polymer.

[0458] The C2 content is expressed as the weight percentage (wt%) of ethylene introduced into the total polymer weight obtained and measured using FT-IR. The FT-IR method is calibrated using NMR data.

[0459] Several polymer properties are discussed here.

[0460] The polyolefin, preferably polypropylene according to the present invention has a molecular weight distribution higher than 2, preferably higher than 4, more preferably higher than 4.5 and for example lower than 12, lower than 10 or lower than 9 or even lower than 6. The polyolefin, preferably polypropylene according to the present invention has a molecular weight distribution of for example from 3 to 9.

[0461] The xylene soluble fraction (XS) is preferably from about 0.5 wt % to about 10 wt %, or from about 1 wt % to about 8 wt %, or from 1 to 6 wt %, or from about 1 wt % to about 5 wt %. Preferably, the xylene amount (XS) is below 6 wt %, preferably below 5 wt %, most preferably below 4 wt %.

[0462] The production rate is preferably about 1 kg / g / hr to about 100 kg / g / hr, or about 10 kg / g / hr to about 80 kg / g / hr.

[0463] The MFR is preferably about 0.01 g / 10 min to about 2000 g / 10 min, or about 0.01 g / 10 min to about 1000 g / 10 min; or about 0.1 g / 10 min to about 500 g / 10 min, or about 0.5 g / 10 min to about 200 g / 10 min.

[0464] The olefin polymers obtained in the present invention are considered to be thermoplastic polymers. The thermoplastic polymer composition according to the present invention may also contain one or more common additives, such as those mentioned above, including stabilizers, such as heat stabilizers, antioxidants, UV stabilizers; colorants, such as pigments and dyes; clarifying agents; surface tension modifiers; lubricants; flame retardants; mold release agents; flow improvers; plasticizers; antistatic agents; impact modifiers; foaming agents; fillers and reinforcing agents; and / or components that enhance the interfacial bonding between the polymer and the filler, such as maleated polypropylene, in the case where the thermoplastic polymer is a polypropylene composition. Any suitable combination of additives and amounts of additives can be easily selected by those skilled in the art without undue experimentation.

[0465] The amount of additives depends on their type and function; typically 0 to about 30 wt% based on the total composition; preferably 0 to about 20 wt%; more preferably 0 to about 10 wt%, and most preferably 0 to about 5 wt%. The sum of all components added in the process to form a polyolefin, preferably a propylene-based polymer or a composition thereof should add up to 100 wt%.

[0466] The thermoplastic polymer composition of the present invention can be obtained by mixing one or more thermoplastic polymers with one or more additives using any suitable means. Preferably, the thermoplastic polymer composition of the present invention is prepared in a form that allows easy processing into a shaped article in a subsequent step, such as a pellet or granular form. The composition can be a mixture of different particles or pellets; such as a blend of a masterbatch of a thermoplastic polymer and a nucleating agent composition, or a blend of a pellet of a thermoplastic polymer containing one of the two nucleating agents and a granular material containing another nucleating agent (which may be a pellet of a thermoplastic polymer containing the other nucleating agent). Preferably, the thermoplastic polymer composition of the present invention is in the form of pellets or granules obtained by mixing all the components in an apparatus such as an extruder, which is advantageous in that the composition has a uniform and well-defined concentration of the nucleating agent (and other components).

[0467] The present invention also relates to the use of the polyolefin according to the present invention, preferably a propylene based polymer (also known as polypropylene), in injection molding, blow molding, extrusion, compression molding, casting, thin wall injection molding, etc., e.g. in food contact applications.

[0468] Furthermore, the present invention relates to shaped articles comprising the polyolefin, preferably a propylene based polymer, according to the present invention.

[0469] According to the polyolefin of the present invention, preferably propylene-based polymers can be transformed into shaped (semi-) finished products using various processing techniques. The example of suitable processing technology includes injection molding, injection compression molding, thin-wall injection molding, extrusion and extrusion compression molding. Injection molding is widely used in the production of articles, such as covers and hoods, batteries, buckets, containers, automotive exterior parts such as bumpers, automotive interior parts such as dashboards, or automotive parts under the hood. Extrusion is widely used in the production of articles, such as rods, sheets, films and pipes. Thin-wall injection molding can be used, for example, to prepare thin-wall packaging applications for both food and non-food fields. This includes buckets and containers and white fat / margarine basins and milk cups.

[0470] It is noted that the invention relates to all possible combinations of features recited in the claims. Features described in the specification may additionally be combined.

[0471] Although the present invention has been described in detail for purposes of illustration, it should be understood that such details are for illustration purposes only and variations may be made therein by one skilled in the art without departing from the spirit and scope of the invention as defined in the claims.

[0472] It is further noted that the present invention relates to all possible combinations of features described herein, preference being given to those combinations of features which are present in the claims.

[0473] It is also noted that the term "comprising" does not exclude the presence of other elements. However, it is also understood that a description of a product comprising certain components also discloses a product consisting of these components. Similarly, it is also understood that a description of a method comprising certain steps also discloses a method comprising these steps.

[0474] The present invention will be further illustrated by the following examples, but the present invention is not limited thereto.

[0475] Example

[0476] Step A. Preparation of Grignard Reagent Solution

[0477] Example 1

[0478] This synthesis stage is carried out as described in EP 1 222 214 B1, but using higher concentrations of magnesium and butyl chloride.A stirred flask of 1500 ml volume equipped with a reflux condenser and a funnel is filled with magnesium powder (35.5 g, 1.46 mol).The flask is placed under nitrogen.

[0479] (i) Magnesium is heated at 80°C for 1 hour, after which a mixture of 150 ml of butyl ether (DBE) and 4 ml of n-chlorobutane is added. The temperature is raised to 75°C and iodine (0.03 g) is added to the reaction mixture. After the color of the iodine has disappeared, the temperature is raised to 80°C and a mixture of 148 ml of n-chlorobutane and 750 ml of butyl ether is slowly added over 3 hours at a molar ratio of Mg / BuCl=1. The concentration of magnesium and BuCl calculated relative to butyl ether is 1.62 mol / l. During the metered addition of n-chlorobutane and butyl ether, the temperature of the reaction mixture is maintained in the range of 78-80°C.

[0480] (ii)+(iii) The reaction mixture was stirred at 80°C for a further hour and then the temperature was raised to 110°C for 1 hour.

[0481] (iv) The reaction mixture was maintained at this temperature for 2 hours. Stirring and heating were stopped and the solid matter was allowed to settle for 24 hours.

[0482] (v) By decanting the solution above the precipitate, a clear solution of butylmagnesium chloride in butyl ether having a concentration of 1.33 mol / l was obtained (Product A).

[0483] The yield of BuMgCl calculated at the molar ratio BuMgCl / BuCl×100 is 90%. The solution is stable during 3 months of storage at room temperature. After 3 months of storage, the solution was reanalyzed, showing a solution concentration equal to 1.33 mol / l (+ / - 0.025 mol / l). The preparation data of the BuMgCl solution and the concentration, yield and stability results of the solution obtained are listed in Table 1.

[0484] Comparative Example 1

[0485] The preparation of the solution of BuMgCl was carried out as described in EP 1 222 214 B1.

[0486] Magnesium powder (24.3g) is loaded into a stirred flask of 1500ml volume equipped with a reflux condenser and a funnel. The flask is placed under nitrogen. Magnesium is heated at 80°C for 1 hour, and a mixture of dibutyl ether (100ml) and n-chlorobutane (4ml) is added afterwards. The temperature is raised to 75°C, and iodine (0.03g) is added to the reaction mixture. After the color of iodine has disappeared, the temperature is raised to 78°C, and a mixture of n-chlorobutane (100ml) and dibutyl ether (796ml) is slowly added within 3 hours. The temperature of the reaction mixture is 78-80°C. The concentration of magnesium and BuCl calculated relative to dibutyl ether is 1.11mol / l. The reaction mixture is stirred for another 3 hours at 78-80°C. Then stirring and heating are stopped, and a small amount of solid matter is allowed to settle for 24 hours. The transparent and stable solution of 1.0mol / l is obtained by decantation. After 3 months of storage at room temperature, it is found that the solution is stable. Reanalysis of the solution after 3 months storage showed a solution concentration equal to 1.0 mol / l.

[0487] Comparative Example 2

[0488] The preparation of the solution of BuMgCl was carried out as described in Comparative Example 1, except that higher concentrations of magnesium and butyl chloride were used as in Example 1, and after the metering phase, the reaction mixture was stirred for another 3 hours at 80°C. After 24 hours of precipitation, a turbid solution with a concentration of 1.3 mol / l was obtained. The solution was found to be unstable. During further storage, the solution gradually clarified with precipitation of fine sediments at the bottom of the container and on the walls. After 3 months of storage at room temperature, the concentration of the solution dropped to 1.18 mol / l. The preparation data of the BuMgCl solution and the concentration, yield and stability results of the obtained solution are listed in Table 1.

[0489] Example 2

[0490] The preparation of the solution of BuMgCl was carried out as described in Example 1, except that 45.6 g of magnesium powder (1.88 moles) and 196 ml of BuCl (1.88 moles) were used. The concentration of magnesium and BuCl calculated relative to butyl ether was 2.09 mol / l. As a result, a transparent and stable solution of BuMgCl with a concentration of 1.54 mol / l was prepared. After 3 months of storage at room temperature, the concentration of the solution did not change. The preparation data of the BuMgCl solution and the concentration, productivity and stability results of the solution obtained are listed in Table 1.

[0491] Example 3

[0492] The preparation of the solution of BuMgCl was carried out as described in Example 1, except that 45.6 g of magnesium powder (1.88 moles) and 196 ml of BuCl (1.88 moles) were used and the reaction mixture was kept at 80° C. for 1 hour after the metering phase, then the temperature was raised to 100° C. (instead of 110° C.) for 1 hour and the reaction mixture was kept at 100° C. for 2 hours. As a result, a slightly turbid solution of BuMgCl with a concentration of 1.58 mol / l was prepared. After one week of storage at room temperature, the concentration of the solution was reduced to 1.42 mol / l. After 3 months of storage, the concentration of the solution was reduced to 1.30 mol / l. The preparation data of the BuMgCl solution and the concentration, productivity and stability results of the obtained solutions are listed in Table 1.

[0493] Example 4

[0494] To prepare the solution of BuMgCl, the solution prepared in Example 3 with a concentration of 1.58 mol / l was used. After 24 hours of settling and analysis of the solution, the reaction mixture from Example 3 was stirred again and half of the suspension was placed in another reactor and subjected to a further heat treatment at a temperature of 110° C. for 5 hours. As a result, after 24 hours of settling, a transparent and stable solution with a concentration of 1.54 was obtained. Reanalysis of the solution after 3 months of storage showed a solution concentration equal to 1.53 mol / l.

[0495] Example 5

[0496] The preparation of a solution of BuMgCl was carried out as described in Example 2 (using 45.6 g of magnesium powder (1.88 moles) and 196 ml of BuCl (1.88 moles), except that the metering stage was carried out at 90° C. After the color of iodine had disappeared, the temperature was raised to 90° C. and a mixture of n-chlorobutane and butyl ether (192 ml of BuCl and 750 ml of DBE) was slowly added over 3 hours. The reaction mixture was stirred at 90° C. for another 2 hours, then the temperature was raised to 110° C. for 0.5 hour, and the reaction mixture was kept at this temperature for 2 hours. As a result, a transparent and stable solution of BuMgCl with a concentration of 1.42 mol / l was prepared. After 3 months of storage at room temperature, the concentration of the solution did not change.

[0497] Comparative Example 3

[0498] The preparation of a solution of BuMgCl was carried out as described in Example 5, except that the metering phase was carried out at 100° C. instead of 90° C. Afterwards, the temperature was raised to 110° C. for 0.5 h and the reaction mixture was stirred at 110° C. for a further 2 h. As a result, a clear and stable solution of BuMgCl with a much lower concentration than in Example 5, namely 0.84 mol / l, was prepared. After 3 months of storage at room temperature, the concentration of the solution had not changed.

[0499] Example 6

[0500] The preparation of the solution of BuMgCl was carried out as described in Example 1, except that 59.3 g of magnesium powder (2.44 moles) and 254 ml of BuCl (2.44 moles) were used. The concentration of magnesium and BuCl calculated relative to butyl ether was 2.71 mol / l. As a result, a transparent and stable solution of BuMgCl with a concentration of 1.90 mol / l was prepared. After 1 week of storage at room temperature, the concentration of the solution dropped to 1.86 mol / l. When stored for another 3 months, the concentration of the solution was slightly reduced to 1.84 mol / l.

[0501] Comparative Example 4

[0502] The preparation of the solution of BuMgCl was carried out as described in Example 1, except that 70g of magnesium powder (2.88 moles) and 299ml of BuCl (2.88 moles) were used. The concentration of magnesium and BuCl calculated relative to butyl ether was 3.2mol / l. As a result, a turbid solution of BuMgCl with a concentration of 2.3mol / l was prepared. The amount of precipitate in this synthesis was significantly higher than in the previous synthesis. When the solution was stored for 1 month, a significant amount of sediment was observed on the glass wall of the container and at the bottom. The concentration of the solution was reduced to 2.1mol / l. After storing for another 2 months, the concentration of the solution was reduced to 1.92mol / l.

[0503] Example 7

[0504] The preparation of the BuMgCl solution was carried out on a pilot scale in a 16 1 stainless steel reactor.

[0505] (i) 486 g of magnesium powder (20 moles of Mg) are loaded into the reactor. The reactor is purged with argon at a temperature of 85° C. for 2 hours, after which a mixture of dibutyl ether (1.4 l) and BuCl (80 ml) is added. The temperature is raised to 75° C., and iodine (0.7 g) is added to the reaction mixture. After the color of the iodine has disappeared, the temperature is raised to 80° C., and a mixture of n-chlorobutane (2 l) and dibutyl ether (8 l) is slowly added over 3 hours. The molar ratio of Mg / BuCl is 1, and the concentration of magnesium and BuCl calculated relative to dibutyl ether is 2.13 mol / l. During the metered addition, the temperature of the reaction mixture is maintained in the interval of 78-80° C.

[0506] (ii) The reaction mixture was stirred at 80°C for a further 1.5 hours.

[0507] After (iii)+(iv), the temperature was raised to 110°C for 0.5 hours and the reaction mixture was kept at this temperature for 3 hours. Stirring and heating were then stopped and a small amount of solid material was allowed to settle for 24 hours.

[0508] (v) By decanting the solution above the precipitate, a clear solution of MgBuCl in butyl ether having a concentration of 1.60 mol / l was obtained (Product A).

[0509] The yield of BuMgCl calculated at the molar ratio BuMgCl / BuCl×100 was 92%. The solution was stable during storage for 3 months at room temperature. Reanalysis of the solution after 3 months of storage showed a solution concentration equal to 1.6 mol / l (+ / - 0.025 mol / l).

[0510] Comparative Example 5

[0511] The preparation of the solution of BuMgCl was carried out as described in Example 2, except that after the metering phase the reaction mixture was kept at 80° C. for 1 hour and then the temperature was raised to 130° C. (instead of 110° C.). As a result, a solution of BuMgCl with a concentration of 1.24 mol / l was prepared. The amount of precipitate in this synthesis was higher than in Example 2, and the yield of BuMgCl was significantly lower. During storage for a further 3 months, the concentration of the solution did not change.

[0512] Example 8

[0513] The preparation of the solution of BuMgCl was carried out as described in Example 6, except that 65.6g of magnesium powder (2.7 moles) and 280ml of BuCl (2.7 moles) were used and the reaction mixture was kept at a higher temperature. The concentration of magnesium and BuCl calculated relative to butyl ether was 3.0mol / l. During the metered addition, the temperature of the reaction mixture was maintained in the interval of 78-80°C. The reaction mixture was stirred at 80°C for another 1 hour. Afterwards, the temperature was raised to 110°C for 2 hours, and the reaction mixture was kept at this temperature for 4 hours. As a result, a transparent and metastable solution of BuMgCl with a concentration of 2.08mol / l was prepared. After 3 months of storage at room temperature, the solution concentration dropped to 1.97mol / l, and after 6 months of storage at room temperature, the concentration of the solution slowly dropped to 1.92mol / l. After additional storage, the concentration of the solution did not change.

[0514] Example 9

[0515] The preparation of the solution of BuMgCl was carried out as described in Example 8, except that the temperature was raised to 120°C for 2 hours and the reaction mixture was kept at this temperature for 2.5 hours. As a result, a transparent and metastable solution of BuMgCl with a concentration of 2.05 mol / l was prepared. After 3 and 6 months of storage at room temperature, the solution concentration dropped to 1.95 and 1.87 mol / l, respectively. After additional storage, the concentration of the solution did not change. In this experiment, the yield of BuMgCl was lower than that in Example 8.

[0516] Example 10

[0517] The preparation of the solution of BuMgCl was carried out as described in Example 8, except that the amount of Mg and BuCl was reduced, i.e., 60.1 g of magnesium powder (2.475 moles) and 257 ml of BuCl (2.475 moles) were used. The concentration of magnesium and BuCl calculated relative to butyl ether was 2.75 mol / l. As a result, a transparent and stable solution of BuMgCl with a concentration of 1.91 mol / l was prepared. The concentration of the solution did not change during storage at room temperature for 3 and 6 months.

[0518] Examples 11-20 and Comparative Examples 6-8

[0519] The preparation of the supports and catalysts in these examples was carried out according to the same procedure described in EP 1661917 A using the BuMgCl solutions prepared in Examples 1-10 and Comparative Examples 1, 2 and 4. The BuMgCl solutions from Comparative Examples 3 and 5 were not used to prepare the catalysts because these experiments had low BuMgCl yields.

[0520] Step B. Preparation of carrier:

[0521] The preparation of solid product B is similar to the process described in EP 1 222 214 B1, wherein the reagent load is increased, except that the temperature is 35° C. and the metering time is 6 hours in the metering stage. 350 ml of butyl ether (DBE) is introduced into a 1700 ml reactor. The reactor is equipped with a paddle stirrer and baffles and is thermostated at 35° C. 540 ml of a solution of product A obtained in step A and 270 ml of a solution of tetraethoxysilane (TES) in DBE (270 ml solution, in all embodiments, the molar ratio of Si / Mg is Si / Mg=0.75, except that in Example 15, the molar ratio of Si / Mg is 0.5 instead of 0.75) are cooled to 5° C. and then metered into the reactor simultaneously by a mixing device provided with a jacket having a volume of 0.45 ml. The metering continues for 6 hours. The mixing device (micro mixer) is cooled to 5° C. by means of cold water circulating in the device jacket. The contact time of reagent (product A and TES) in the micro mixer and in the connecting pipe between the micro mixer and the reactor is 18.7s. The stirring speed in the reactor is 260rpm at the beginning of metering, and gradually increases to 360rpm at the end of the metering stage. After completing metering, the reaction mixture is heated to 60°C in 30min and kept at this temperature for 1 hour. Then stop stirring and allow the solid product to settle. Remove the supernatant by decantation. The solid material is washed three times with 800ml of heptane at 60°C. As a result, a solid product B suspended in heptane is obtained. Then, just half of the carrier suspension is loaded onto the filter, washed with isopentane, and dried at 50°C in an argon stream. Therefore, the amount of the carrier obtained in the synthesis is determined. The average amount of the carrier in the synthesis is 110g+ / -3g per 1mol of BuMgCl used. The data of the carrier yield in the synthesis are shown in Table 2. For premixing of reagents during the preparation of product B, a micromixer equipped with a stirrer and a jacket was used as shown in Example 1 of EP 1 222 214 B1. The volume of the micromixer was 3.0 ml, the volume of the line between the micromixer and the reactor was 0.6 ml, and the premixing time was about 9.3 s.

[0522] Step C. Activation of the carrier

[0523] According to the procedure described in Example 4 of EP 1661917A1, the support activation of product B is carried out with ethanol and tetraethoxytitanium (TET), wherein the reagent load is increased. At 0°C in an inert nitrogen atmosphere, a 0.5l glass flask equipped with a mechanical stirrer is filled with a slurry of 5g of product B dispersed in 100ml of heptane. Subsequently, a solution of 0.96ml of ethanol in 20ml of heptane is added at 0°C within 1 hour to obtain a ratio of ethanol / Mg=0.4. The reaction mixture is kept at 0°C for 30min. The temperature is then raised to 20°C, and a solution of 0.944g of tetraethoxytitanium (TET / Mg=0.1) in 20ml of heptane is added within 1 hour. Afterwards, the slurry is heated to 30°C within 30min and kept at this temperature for another 3 hours. Finally, the supernatant is decanted from the solid reaction product, and the solid reaction product is washed once with 150ml of heptane at 30°C. As a result, about 6g of product C (activated support) is obtained.

[0524] Step D. Preparation of Procatalyst

[0525] The glass reactor that volume is 0.3l is placed under nitrogen, and 125ml of titanium tetrachloride is added to the reactor. Under stirring, a suspension of solid product C containing about 6g in 15ml heptane is added to the reactor. Then during 1 hour, the reaction mixture is heated to 100°C, and then 1.6ml of dibutyl phthalate is added to the reactor (DBP / Mg=0.15). Then the reaction mixture is heated to 115°C and kept at 115°C for 105min. Then stirring is stopped, and the solid product is precipitated. The supernatant is removed by decantation, and then the solid product is washed with chlorobenzene (125mL) at 100°C for 20min. Then the washing solution is removed by decantation, and then a mixture of titanium tetrachloride (62.5ml) and chlorobenzene (62.5ml) is added. The reaction mixture is kept at 115°C for 30min, and then the solid product is precipitated, and the last treatment is repeated once more. The obtained solid product was washed five times with 150 ml of heptane at 60° C. to obtain a solid procatalyst suspended in heptane.

[0526] Step E. Polymerization of Propylene

[0527] The polymerization of propylene was carried out in a stainless steel reactor (volume 0.7 l) in heptane (300 ml), at a temperature of 70° C., a total pressure of 0.7 MPa and in the presence of hydrogen (55 ml), in the presence of a procatalyst system comprising the procatalyst component obtained according to step C, triethylaluminum and cyclohexylmethyldimethoxysilane (C-donor), for 1 hour. The concentration of the procatalyst 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.

[0528] Table 2 shows the data on the performance of the procatalyst in propylene polymerization.

[0529] Abbreviations and measurement methods:

[0530] - Yield of BuMgCl (%): The yield of BuMgCl was calculated as the molar ratio of the amount of MgBuCl obtained to the amount of initial BuCl present.

[0531] - Yield of vector (g): The yield of vector (Ysupp., g) was determined by the following procedure:

[0532] After the synthesis is complete, the total volume of the support deposit (Vsupp.) is determined. A certain volume of the support suspension (Vsampl., usually 30-50% of the total deposit volume) is placed in a pre-weighed measuring container. After sedimentation, the free liquid phase is decanted and the support is dried in a vacuum at room temperature to a constant weight (Psampl.). The yield of the support is determined by the ratio: Ysupp. = Psampl / Vsampl. * Vsupp. Typically, from 1 molar BuMgCl solution, 110 + / - 3 g of support are obtained.

[0533] - The stability of the BuMgCl solution was evaluated qualitatively (visually, by the formation of sediment during storage of the solution for 1, 3 and 6 months), as was the quantitative change in the concentration of the BuMgCl solution during this period. The quantitative analysis was performed by taking a sample of the BuMgCl solution, decomposing the sample with a 5% sulfuric acid solution and analyzing the aqueous solution by the ICP method.

[0534] - PP yield (kg / g cat) is the amount of polypropylene obtained per gram of catalyst component.

[0535] "Bulk density" (BD): The mass of particles of a polymer divided by the total volume occupied by these particles. It is measured according to ASTM D 1895.

[0536] The "span value" represents an indication of the width of the particle size distribution measured according to ISO 13320:2009. The span value is calculated as follows:

[0537] Span value = (d90-d10) / d50

[0538] wherein d90 is equal to x90 as defined in ISO 13320:2009, d10 is equal to x10 as defined in ISO 13320:2009, and d50 is equal to x50 as defined in ISO 13320:2009.

[0539] Average Particle Size (APS): The average particle size of the catalyst was measured using a test method based on ASTM standard test method D4464-201.

[0540] Table 1

[0541]

[0542]

[0543] 1 The concentrations of magnesium and BuCl were calculated relative to butyl ether.

[0544] 2 The stability of the BuMgCl solution was qualitatively assessed from the formation of precipitates during storage of the solution for 3 months and the quantitative changes in the concentration of the BuMgCl solution during this time.

[0545] Table 2

[0546]

[0547] 3 Amount of support obtained in the synthesis (from 1 molar BuMgCl solution, 110 + / - 3 g of support were obtained).

[0548] 4 Amount of the fraction of PP powder with a size less than 0.1 mm, in wt%.

[0549] Table 1 shows different conditions for preparing BuMgCl in terms of time and temperature in the metering phase and the holding phase. Table 1 also shows the improved stability, yield and concentration (when measured after 3 months storage) of the butylmagnesium chloride prepared according to the invention.

[0550] Table 2 shows that the BuMgCl solutions obtained according to Table 1 lead to higher yields of solid support and PP. In addition, the use of catalysts prepared using these stable BuMgCl solutions leads to PP powders with good morphology, such as high bulk density, narrow particle size distribution and low fine powder content.

[0551] It is evident from the above results that processes carried out at higher temperatures allow for the formation of higher BuMgCl concentrations. Furthermore, applying higher temperatures or producing higher BuMgCl concentrations results in the formation of complexes that remain more stable during subsequent storage under normal conditions.

Claims

1. A method for preparing a procatalyst for preparing a catalyst composition for olefin polymerization, the method comprising the following steps: a. Provided by R 4 z MgX 4 2-z A magnesium-based support prepared from a solution of Where R 4 is independently selected from a linear, branched or cyclic hydrocarbon group, which is independently selected from an alkyl, alkenyl, aryl, aralkyl or alkaryl 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, 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 in the range of greater than 0 and less than 2, and is 0 <z<2; b. optionally activating the magnesium-based support using an activator; c. contacting the magnesium-based support with a Ziegler-Natta type catalytic species and one or more internal donors; wherein the R is prepared by a method comprising the following steps 4 z MgX 4 2-z Solution: (i) reacting magnesium powder with an organic halide in the presence of an organic solvent at a temperature of T1; (ii) stirring the reaction mixture obtained in step (i) at T1 for at least 1 hour; (iii) raising the temperature of the reaction mixture obtained in step (ii) to temperature T2; (iv) stirring the reaction mixture obtained in step (iii) at T2 for at least 1 hour; (v) decanting or filtering the reaction mixture obtained in step (iv) to obtain R 4 z MgX 4 2-z Clear solutions in organic solvents; Among them, T1 is in the range of 70℃-90℃, and T2 is in the range of T1+30℃ to T1+40℃.

2. The method according to claim 1, wherein magnesium and R 4 X 4 The concentration relative to the organic solvent is 1 to 4 mol / l, preferably 1 to 3.5 mol / l, and more preferably 1 to 3 mol / l.

3. The method according to any one of claims 1 to 2, wherein the organic solvent is selected from diethyl ether, isopropyl ether, butyl ether, isobutyl ether, isoamyl ether, allyl ether, tetrahydrofuran, anisole and octyl ether or a combination thereof, preferably the organic solvent is butyl ether; and The organic halide is R 4 X 4 ; Where R 4 independently selected from linear, branched or cyclic hydrocarbon groups, independently selected from alkyl, alkenyl, aryl, aralkyl or alkaryl groups 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, and; X 4 Independently selected from fluoride ion (F-), chloride ion (Cl-), bromide ion (Br-) or iodide ion (I-); preferably, the organic halide is selected from butyl chloride, butyl bromide and 1,2-dibromoethane or a combination thereof.

4. according to the method described in any one of claims 1-3, wherein the activator is selected from benzamide, alkyl benzoate, monoester or any combination thereof, preferably the activator is benzamide, alkyl benzoate or a combination thereof.

5. The method according to any one of claims 1 to 4, wherein the method comprises the following steps: A) providing the procatalyst by a method comprising the steps of: i) contacting the magnesium-based support with an alkoxy- or aryloxy-containing silane compound to produce a first intermediate reaction product, which is solid Mg(OR 5 ) x X 1 2-x ,in: R 5 is a linear, branched or cyclic hydrocarbon group independently selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkaryl groups 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; wherein R 4 is a linear, branched or cyclic hydrocarbon group independently selected from an alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkaryl 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, preferably R 4 is butyl; wherein X 2 and X 1 Each is independently selected from fluoride ion (F-), chloride ion (Cl-), bromide ion (Br-) or iodide ion (I-), preferably chloride ion; z is in the range of greater than 0 and less than 2, and is 0 <z<2; ii) optionally subjecting the solid Mg(OR) obtained in step i) to 5 ) x X 1 2-x contacting with at least one activating compound to obtain a second intermediate product, wherein the activating compound is selected from the group consisting of an activating electron donor and a 1 (OR 6 ) v-w (OR 7 ) w or M 2 (OR 6 ) v-w (R 7 ) w A group formed by metal alkoxide compounds; wherein: M 1 is a metal selected from Ti, Zr, Hf, Al or Si; v is M 1 The valence of M 2 is metal Si; v is M 2 The valence of 6 and R 7 Each is a linear, branched or cyclic hydrocarbon group independently selected from an alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkaryl 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; wherein w is less than v, preferably v is 3 or 4; iii) contacting the first intermediate reaction product or the second intermediate reaction product obtained in step i) or ii) respectively with a halogen-containing Ti compound and the internal donor.

6. The method according to any one of claims 1 to 5, wherein the internal donor is selected from aminobenzoates, succinates, silyl esters, silyl glycol esters, diethers, phthalates or any combination thereof.

7. The method according to any one of claims 1 to 6, wherein the preferred internal donor is an aminobenzoate represented by formula (I) or a diether represented by formula (II) or a combination thereof, in: R 80 are independently selected from substituted or unsubstituted aryl, aralkyl or alkaryl groups and one or more combinations thereof, and R 81 , R 82 , R 83 , R 84 , R 85 and R 86 each independently selected from hydrogen or a linear, branched or cyclic hydrocarbyl group selected from an alkyl, alkenyl, aryl, aralkyl or alkaryl group and one or more combinations thereof, preferably having 1 to 20 carbon atoms; Where R 87 is selected from hydrogen, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, phenyl, benzyl, substituted benzyl and halophenyl groups; and Where R 88 is selected from hydrogen or a linear, branched or cyclic hydrocarbon group, the hydrocarbon group being selected from an alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkaryl group and one or more combinations thereof, preferably having 1 to 20 carbon atoms, and more preferably R 88 is phenyl; Where R 51 and R 52 are each independently selected from hydrogen or a hydrocarbyl group selected from an alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkaryl group and one or more combinations thereof, R 53 and R 54 Each is independently selected from hydrogen, halogen or a hydrocarbon group selected from an alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkaryl group and one or more combinations thereof.

8. The method according to any one of claims 1 to 7, wherein the internal donor is selected from 1,3-dimethoxypropane, 1,3-diethoxypropane, 1,3-dibutoxypropane, 1-methoxy-3-ethoxypropane, 1-methoxy-3-butoxypropane, 1-methoxy-3-cyclohexyloxypropane, 2,2-dimethyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane, 2,2-di-n-butyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2-ethyl-2-n-butyl-1,3-dimethoxypropane, 2-n-propyl-2-cyclopentyl-1,3-dimethoxypropane, 2,2-dimethyl-1,3-diethoxypropane, 2 -n-propyl-2-cyclohexyl-1,3-diethoxypropane, 2-(2-ethylhexyl)-1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2-n-butyl-1,3-dimethoxypropane, 2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-1,3-dimethoxypropane, 2-phenyl-1,3-diethoxypropane, 2-cumyl-1,3-diethoxypropane, 2-(2-phenylethyl)-1,3-dimethoxypropane, 2-(2-cyclohexylethyl)-1,3-dimethoxypropane, 2-(p-chlorophenyl)-1,3-dimethoxypropane, 2-(diphenylmethyl)-1,3-dimethoxypropane, 2-(1-naphthyl)-1,3-dimethoxypropane, 2-(Fluorophenyl)-1,3-dimethoxypropane, 2-(1-decahydronaphthyl)-1,3-dimethoxypropane, 2-(p-tert-butylphenyl)-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-di-n-propyl-1,3-dimethoxypropane, 2-methyl-2-n-propyl-1,3-dimethoxypropane, 2-methyl-2-benzyl-1,3-dimethoxypropane, 2-methyl-2-ethyl-1,3-dimethoxypropane, 2-methyl-2-phenyl-1,3-dimethoxypropane, 2-methyl-2-cyclohexyl-1,3-dimethoxypropane, 2,2-bis(p-chlorophenyl)-1,3-dimethoxypropane, 2,2-bis(2-cyclohexylethyl)-1 ,3-dimethoxypropane, 2-methyl-2-isobutyl-1,3-dimethoxypropane, 2-methyl-2-(2-ethylhexyl)-1,3-dimethoxypropane, 2-methyl-2-isopropyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2,2-dibenzyl-1,3-dimethoxypropane, 2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-diethoxypropane, 2,2-diisobutyl-1,3-di-n-butoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2,2-di-sec-butyl-1,3-dimethoxypropane, 2,2-di-tert-butyl-1,3-dimethoxypropane, 2,2-Di-neopentyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2-phenyl-2-benzyl-1,3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane, 2-isopropyl-2-(3,7-dimethyloctyl)-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclohexylmethyl-1,3-dimethoxypropane 2,2-diisopentyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclohexyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclopentyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2-n-heptyl-2-n-pentyl-1,3-dimethoxypropane, 9,9-bis(methoxymethyl)fluorene, 1,3-dicyclohexyl-2,2-bis(methoxymethyl)propane, 3,3-bis(methoxymethyl) -2,5-dimethylhexane, 4-[benzoyl (methyl) amino] pentane-2-yl benzoate; 2,2,6,6-tetramethyl-5-(methylamino) heptane-3-ol dibenzoate; 4-[benzoyl (ethyl) amino] pentane-2-yl benzoate, 4-(methylamino) pentane-2-yl bis(4-methoxy) benzoate), 3-[benzoyl (cyclohexyl) amino]-1-phenylbutyl benzoate, 3-[benzoyl (propane-2- [(methyl)amino]-1-phenylbutyl benzoate, 4-[benzoyl (methyl)amino]-1,1,1-trifluoropentane-2-yl benzoate, 3-(methylamino)-1,3-diphenylpropane-1-ol dibenzoate, 3-(methyl)amino-propane-1-ol dibenzoate; 3-(methyl)amino-2,2-dimethylpropane-1-ol dibenzoate and 4-(methylamino)pentane-2-yl bis(4-methoxy)benzoate) or any combination thereof.

9. The method of any one of claims 1-8, wherein the method is substantially free of phthalates.

10. The method according to any one of claims 1 to 9, wherein the R 4 z MgX 4 2-z The concentration of the clear solution in the organic solvent is at most 3 mol / l, or from 1 to 2.5 mol / l, or from 1 to 2 mol / l.

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