Process for forming Ziegler-Natta catalyst components

Abstract

A process for forming a Ziegler-Natta catalyst component is employed in which a particular combination of washing steps is employed to provide a catalyst of the present invention that is capable of synthesizing polypropylene having an elevated melting temperature, reduced XCS content, and is capable of more efficiently maintaining catalytic activity over sequential polymerization processes.

Description

[Technical Field]

[0001] The present invention relates to a process for forming a Ziegler-Natta catalyst component involving a particular combination of washing steps, a Ziegler-Natta composition comprising the Ziegler-Natta catalyst component, and a process for (co)polymerizing propylene in the presence of a Ziegler-Natta catalyst system comprising the Ziegler-Natta catalyst composition. [Background technology]

[0002] Ziegler-Natta (ZN) type polyolefin catalysts are well known in the polymer art, and generally, this type of catalyst comprises (a) at least a catalytic component formed from a transition metal compound from Groups 4 to 6 of the Periodic Table (IUPAC, Nomenclature of Inorganic Chemistry, 1989), a metal compound from Groups 1 to 3 of the Periodic Table (IUPAC), and optionally a compound from Group 13 of the Periodic Table (IUPAC) and / or an internal donor compound. ZN catalysts may also comprise (b) additional catalytic component(s), such as a cocatalyst and / or an external donor.

[0003] A wide variety of Ziegler-Natta catalysts have been developed to meet different requirements in reaction properties and to produce poly(α-olefin) resins with desired physical and mechanical properties. Various methods for preparing ZN catalysts are known in the prior art. In one known method, supported ZN catalyst systems are prepared by impregnating catalyst components into a particulate support material. In WO 01 / 55230, the catalyst components are supported on a porous, inorganic or organic particulate support material, such as silica.

[0004] In another well-known method, the support material is based on one of the catalyst components, a magnesium compound such as MgCl. This type of support material can also be formed in a variety of ways. European Patent Application Publication No. 713886 to Japan Polyolefins describes the formation of an MgCl adduct with an alcohol, which is then emulsified, and the final mixture is quenched to cause the droplets to solidify. Alternatively, European Patent Application Publication No. 856013 to BP discloses the formation of a solid Mg-based support in which a Mg component-containing phase is dispersed in a continuous phase and the dispersed Mg phase is solidified by adding this two-phase mixture to a liquid hydrocarbon. The formed solid support particles are typically treated with a transition metal compound and, optionally, other compounds to form an active catalyst.

[0005] Thus, in the case of external supports, some examples of which are disclosed above, the morphology of the support is one of the determining factors of the morphology of the final catalyst.

[0006] WO 00 / 08073 and WO 00 / 08074 describe further methods for producing solid ZN catalysts, in which a solution of a Mg-based compound and one or more additional catalyst compounds is formed, and the reaction product is precipitated from the solution by heating the system. Furthermore, EP 926165 discloses another precipitation method, in which a mixture of MgCl and a Mg alkoxide is precipitated with a Ti compound to obtain a ZN catalyst.

[0007] EP 83074 and EP 83073 to Montedison disclose a method for producing a ZN catalyst or its precursor, in which an emulsion or dispersion of Mg and / or Ti compounds is formed in an inert liquid medium or in an inert gas phase, and this system is reacted with an Al-alkyl compound to precipitate a solid catalyst. According to the examples, the emulsion is then added to a larger amount of Al compound in hexane and pre-polymerized to cause precipitation.

[0008] In the polymerization process, this eventually leads to undesirable and harmful defects such as clogging on the walls of the reactor and in lines and further equipment such as extruders, the formation of polymer layers, as well as poor flowability of the polymer powder and other polymer handling problems.

[0009] EP 1 403 292 A1, EP 0 949 280 A1, U.S. Pat. No. 4,294,948, U.S. Pat. No. 5,413,979 and U.S. Pat. No. 5,409,875 and EP 1 273 595 A1 describe processes for the preparation of olefin polymerization catalyst components or olefin polymerization catalysts and processes for the preparation of olefin polymers or copolymers.

[0010] Although numerous alternative ZN catalyst formulations have been developed, there remains a need for access to additional catalysts that allow the production of polypropylene with finely tuned mechanical properties, particularly enhanced crystallinity, associated with increased melting temperatures and reduced XCS content. Furthermore, it is desirable to have catalysts that exhibit as little loss of activity as possible during each step of the sequential polymerization process. Especially if such a modified method results from a simple change to just one step of the catalyst preparation, this modification could be readily applied to a wide range of existing catalyst preparation processes. [Prior art documents] [Patent documents]

[0011] [Patent Document 1] International Publication No. 01 / 55230 Brochure [Patent Document 2] European Patent Application Publication No. 713886 [Patent Document 3] European Patent Application Publication No. 856013 [Patent Document 4] International Publication No. 00 / 08073 Brochure [Patent Document 5] International Publication No. 00 / 08074 Brochure [Patent Document 6] European Patent Application Publication No. 926165 [Patent Document 7] European Patent Application Publication No. 83074 [Patent Document 8] European Patent Application Publication No. 83073 [Patent Document 9] European Patent Application Publication No. 1403292A1 [Patent Document 10] European Patent Application Publication No. 0949280A1 [Patent Document 11] U.S. Patent No. 4,294,948 [Patent Document 12] U.S. Patent No. 5,413,979 [Patent Document 13] U.S. Patent No. 5,409,875 [Patent Document 14] European Patent Application Publication No. 1273595A1 Summary of the Invention [Means for solving the problem]

[0012] The present invention is based on the discovery that modifying the washing step during the catalyst preparation process can make it possible to provide a catalyst with improved properties for the polymerization of propylene.

[0013] Accordingly, the present invention provides a process for forming a Ziegler-Natta catalyst component, comprising: a) providing a solution of at least one magnesium component; b) adding the solution from step a) to a titanium (IV) compound, thereby obtaining solid catalyst component particles as a suspension; c) recovering the solid catalyst component particles from the suspension obtained from step b); d) washing the solid catalyst component particles; e) recovering the solid catalyst component particles of the olefin polymerization catalyst component; in the given order, wherein an internal electron donor (ID) is added in any step prior to step c), wherein the internal electron donor (ID) is a non-phthalic acid internal electron donor; The washing step d) is d1) one or more washes with a wash solution of an aromatic and / or aliphatic hydrocarbon, preferably selected from toluene, hexane or pentane, and optionally an internal electron donor (ID), d2) one or more washes with a titanium tetrachloride and internal electron donor (ID) wash solution; and d3) one or more washes with a washing solution of an aromatic and / or aliphatic hydrocarbon, preferably selected from toluene, hexane or pentane; in the order stated, wherein at least one of the one or more washes with a titanium tetrachloride and internal electron donor (ID) wash solution in step d2) is carried out at a temperature in the range of 80 to 120°C, more preferably in the range of 85 to 120°C, even more preferably in the range of 85 to 115°C, even more preferably in the range of 90 to 110°C, and most preferably in the range of 95 to 105°C.

[0014] In a further aspect, the present invention is directed to a Ziegler-Natta catalyst composition comprising a Ziegler-Natta catalyst component obtainable by the process according to the present invention.

[0015] In another aspect, the present invention is directed to a process for the production of a polypropylene composition comprising the polymerization of propylene, optionally with a comonomer selected from a C2 or C4 to C12 alpha olefin, in the presence of a Ziegler-Natta catalyst system comprising the Ziegler-Natta catalyst composition according to the present invention, a cocatalyst (Co), and optionally an external donor (ED).

[0016] In yet another aspect, the present invention provides a process for producing a polypropylene composition, comprising: a) providing a solution of at least one magnesium component; b) adding the solution from step a) to a titanium (IV) compound, thereby obtaining solid catalyst component particles; c) recovering the solid catalyst component particles from the solution obtained from step b); d) washing the solid catalyst component particles; e) recovering the solid catalyst component particles of the olefin polymerization catalyst component; in the order listed, wherein an internal electron donor (ID) is added in any step prior to step c), wherein the internal electron donor (ID) is a non-phthalic acid internal electron donor; The washing step d) is d1) one or more washes with a wash solution of an aromatic and / or aliphatic hydrocarbon, preferably selected from toluene, hexane or pentane, and optionally an internal electron donor (ID), d2) one or more washes with a titanium tetrachloride and internal electron donor (ID) wash solution; and d3) one or more washes with a washing solution of an aromatic and / or aliphatic hydrocarbon, preferably selected from toluene, hexane or pentane; in the order stated, wherein at least one of the one or more washes with a titanium tetrachloride and internal electron donor (ID) wash solution in step d2) is carried out at a temperature in the range of 80 to 120°C, more preferably in the range of 85 to 120°C, even more preferably in the range of 85 to 115°C, even more preferably in the range of 90 to 110°C, and most preferably in the range of 95 to 105°C; the process further comprising the step of polymerizing propylene, optionally with a comonomer selected from a C2 or C4 to C12 alpha olefin, in the presence of a Ziegler-Natta catalyst system comprising a Ziegler-Natta catalyst composition comprising the solid catalyst component recovered in step e), a cocatalyst (Co) and optionally an external donor (ED).

[0017] In a final aspect, the present invention is directed to the use of the Ziegler-Natta catalyst composition according to the invention, optionally together with a cocatalyst (Co) and optionally an external donor (ED), for the polymerization of propylene with a comonomer selected from C2 or C4 to C12 alpha-olefins.

[0018] definition Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although any methods and materials similar or equivalent to those described herein can be used in the practice for testing of the present invention, the preferred materials and methods are described herein. In describing and claiming the present invention, the following terminology will be used in accordance with the definitions set out below.

[0019] Unless expressly stated otherwise, use of the terms "a," "an," etc. refers to one or more.

[0020] Propylene homopolymer is a polymer essentially consisting of propylene monomer units. Due to impurities, particularly in commercial polymerization processes, propylene homopolymer may contain up to 1.0 mol% comonomer units, preferably up to 0.5 mol%, more preferably up to 0.1 mol%, even more preferably up to 0.05 mol%, and most preferably up to 0.01 mol% comonomer units. It is particularly preferred that propylene is the only detectable monomer.

[0021] Propylene random copolymers are copolymers of propylene monomer units and comonomer units, preferably selected from ethylene and C4 to C12 α-olefins, in which the comonomer units are randomly distributed along the polymer chain. Propylene random copolymers can contain comonomer units from one or more comonomers with different amounts of carbon atoms. In the following, amounts are given in weight percent unless otherwise specified.

[0022] In the context of the present invention, a washing step is a step in which catalyst particles are contacted with a washing solution for a specific period of time, usually with stirring. After this period, the suspension is allowed to settle (settling) and the washing solution is removed. Fresh washing solution is added for further washing. Therefore, those skilled in the art will understand that two successive washes with the same specific washing solution are not the same as a single washing step of twice the duration, because the second specific washing uses fresh washing solution rather than the potentially contaminated solution present at the end of the first washing.

[0023] Furthermore, in the context of the present invention, when a cleaning solution is specified as a component A cleaning solution or a component A and component B cleaning solution, it is assumed that no further components other than the specified components are present. In other words, a "component A cleaning solution" should be interpreted as a "cleaning solution consisting of component A." This definition is specific to the term "cleaning solution." On the other hand, the term "solution of component A" implies the presence of at least one solvent in addition to component A. [Brief explanation of the drawings]

[0024] [Figure 1] Scanning electron microscope (SEM) and optical microscope (LM) images of comparative catalyst particles and catalyst particles of the present invention [Figure 2] Molecular weight distribution of polypropylene polymerized with the catalyst of the present invention or the comparative catalyst [Figure 3] Scanning electron microscope (SEM) and optical microscope (LM) images of polymer particles obtained using comparative catalysts and catalysts of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0025] Catalyst preparation The process of the present invention is a process for forming a Ziegler-Natta catalyst component, comprising the steps of: a) providing a solution of at least one magnesium component; b) adding the solution from step a) to a titanium (IV) compound, thereby obtaining solid catalyst component particles as a suspension; c) recovering the solid catalyst component particles from the suspension obtained from step b); d) washing the solid catalyst component particles; e) recovering the solid catalyst component particles of the olefin polymerization catalyst component; in the order listed, wherein an internal electron donor (ID) is added in any step prior to step c), wherein the internal electron donor (ID) is a non-phthalic acid internal electron donor; The washing step d) is d1) one or more washes with a wash solution of an aromatic and / or aliphatic hydrocarbon, preferably selected from toluene, hexane or pentane, and optionally an internal electron donor (ID), d2) one or more washes with a titanium tetrachloride and internal electron donor (ID) wash solution; and d3) one or more washes with a washing solution of an aromatic and / or aliphatic hydrocarbon, preferably selected from toluene, hexane or pentane; in the order listed, wherein at least one of the one or more washes with the titanium tetrachloride and internal electron donor (ID) wash solution in step d2) is conducted at a temperature in the range of 80 to 120°C, more preferably in the range of 85 to 120°C, even more preferably in the range of 85 to 115°C, even more preferably in the range of 90 to 110°C, and most preferably in the range of 95 to 105°C.

[0026] In its simplest form, the washing step d) comprises: d1) one wash with a wash solution of aromatic and / or aliphatic hydrocarbons, preferably selected from toluene, hexane or pentane, and optionally an internal electron donor (ID), d2) one wash with a titanium tetrachloride and internal electron donor (ID) wash solution; and d3) one or more washes with a washing solution of an aromatic and / or aliphatic hydrocarbon, preferably selected from toluene, hexane or pentane; The method includes the steps of:

[0027] However, the washing solution of step d1) is a washing solution of an internal electron donor (ID) and an aromatic and / or aliphatic hydrocarbon, preferably selected from toluene, hexane or pentane, and therefore step d) comprises: d1) one or more washes with a wash solution of an internal electron donor (ID) and an aromatic and / or aliphatic hydrocarbon, preferably selected from toluene, hexane or pentane; d2) one or more washes with a titanium tetrachloride and internal electron donor (ID) wash solution; and d3) one or more washes with a washing solution of an aromatic and / or aliphatic hydrocarbon, preferably selected from toluene, hexane or pentane; in the order listed.

[0028] Similarly, step d2) comprises two or more washes with a wash solution of titanium tetrachloride and an internal electron donor (ID), and thus the washes of step d) comprise: d1) one or more washes with a wash solution of an aromatic and / or aliphatic hydrocarbon, preferably selected from toluene, hexane or pentane, and optionally an internal electron donor (ID), d2) two or more washes with titanium tetrachloride and internal electron donor (ID) wash solutions; and d3) one or more washes with a washing solution of an aromatic and / or aliphatic hydrocarbon, preferably selected from toluene, hexane or pentane; in the order listed.

[0029] The washing solution of step d1) is a washing solution of an internal electron donor (ID) and an aromatic and / or aliphatic hydrocarbon, preferably selected from toluene, hexane or pentane, and step d2) comprises two or more washes with a washing solution of titanium tetrachloride and an internal electron donor (ID), so that the washing of step d) is d1) one or more washes with a wash solution of an internal electron donor (ID) and an aromatic and / or aliphatic hydrocarbon, preferably selected from toluene, hexane or pentane; d2) two or more washes with titanium tetrachloride and internal electron donor (ID) wash solutions; and d3) one or more washes with a washing solution of an aromatic and / or aliphatic hydrocarbon, preferably selected from toluene, hexane or pentane; It is even more preferred that the composition comprises in the order listed.

[0030] In such embodiments, it is preferred that at least two of the two or more washes with the titanium tetrachloride and internal electron donor (ID) wash solution in step d2) are carried out at a temperature in the range of 80 to 120°C, more preferably in the range of 85 to 120°C, even more preferably in the range of 85 to 115°C, even more preferably in the range of 90 to 110°C, and most preferably in the range of 95 to 105°C.

[0031] In a further preferred embodiment, all of the washes with the titanium tetrachloride and internal electron donor (ID) wash solution of step d2) are carried out at a temperature in the range of 80 to 120° C., more preferably in the range of 85 to 120° C., even more preferably in the range of 85 to 115° C., even more preferably in the range of 90 to 110° C., and most preferably in the range of 95 to 105° C. This requirement may apply equally to embodiments in which there is more than one wash with the titanium tetrachloride and internal electron donor (ID) wash solution of step d2), or indeed to embodiments in which there is more than one wash with the titanium tetrachloride and internal electron donor (ID) wash solution of step d2).

[0032] The washing step d) is d4) one or more washes with an internal electron donor (ID) and a wash solution of an aromatic and / or aliphatic hydrocarbon, preferably selected from toluene, hexane or pentane. It is more preferred that the method further comprises the step of: wherein step d4) is carried out after step d2) and before step d3).

[0033] In such an embodiment, the washing in step d) comprises: d1) one or more washes with a wash solution of an aromatic and / or aliphatic hydrocarbon, preferably selected from toluene, hexane or pentane, and optionally an internal electron donor (ID), d2) one or more washes with a titanium tetrachloride and internal electron donor (ID) wash solution; d4) one or more washes with a wash solution of an internal electron donor (ID) and an aromatic and / or aliphatic hydrocarbon, preferably selected from toluene, hexane or pentane, and d3) one or more washes with a washing solution of an aromatic and / or aliphatic hydrocarbon, preferably selected from toluene, hexane or pentane; The method includes the steps of:

[0034] The washing step d) is d1) one or more washes with a wash solution of an internal electron donor (ID) and an aromatic and / or aliphatic hydrocarbon, preferably selected from toluene, hexane or pentane; d2) one or more washes with a titanium tetrachloride and internal electron donor (ID) wash solution; d4) one or more washes with a wash solution of an internal electron donor (ID) and an aromatic and / or aliphatic hydrocarbon, preferably selected from toluene, hexane or pentane, and d3) one or more washes with a washing solution of an aromatic and / or aliphatic hydrocarbon, preferably selected from toluene, hexane or pentane; It is even more preferred to include the steps of in the order listed.

[0035] Alternatively, the washing in step d) may be d1) one or more washes with a wash solution of an aromatic and / or aliphatic hydrocarbon, preferably selected from toluene, hexane or pentane, and optionally an internal electron donor; d2) two or more washes with titanium tetrachloride and internal electron donor (ID) wash solutions; d4) one or more washes with a wash solution of an internal electron donor (ID) and an aromatic and / or aliphatic hydrocarbon, preferably selected from toluene, hexane or pentane, and d3) one or more washes with a washing solution of an aromatic and / or aliphatic hydrocarbon, preferably selected from toluene, hexane or pentane; Preferably, the method comprises the steps of:

[0036] The washing step d) is d1) one or more washes with a wash solution of an internal electron donor (ID) and an aromatic and / or aliphatic hydrocarbon, preferably selected from toluene, hexane or pentane; d2) two or more washes with titanium tetrachloride and internal electron donor (ID) wash solutions; d4) one or more washes with a wash solution of an internal electron donor (ID) and an aromatic and / or aliphatic hydrocarbon, preferably selected from toluene, hexane or pentane, and d3) one or more washes with a washing solution of an aromatic and / or aliphatic hydrocarbon, preferably selected from toluene, hexane or pentane; Even more preferably, it comprises the steps of in the order listed.

[0037] The washing step d) is d1) one or more washes with a wash solution of an aromatic and / or aliphatic hydrocarbon, preferably selected from toluene, hexane or pentane, and optionally an internal electron donor (ID), d2) two or more washes with titanium tetrachloride and internal electron donor (ID) wash solutions; d4) one or more washes with a wash solution of an internal electron donor (ID) and an aromatic and / or aliphatic hydrocarbon, preferably selected from toluene, hexane or pentane, and d3) one or more washes with a washing solution of an aromatic and / or aliphatic hydrocarbon, preferably selected from toluene, hexane or pentane; in the order described, wherein all of the washings with the titanium tetrachloride and internal electron donor (ID) washing solution in step d2) are carried out at a temperature in the range of 80 to 120°C, more preferably in the range of 85 to 120°C, even more preferably in the range of 85 to 120°C, still more preferably in the range of 90 to 110°C, and most preferably in the range of 95 to 105°C.

[0038] The washing step d) is d1) one or more washes with a wash solution of an internal electron donor (ID) and an aromatic and / or aliphatic hydrocarbon, preferably selected from toluene, hexane or pentane; d2) two or more washes with titanium tetrachloride and internal electron donor (ID) wash solutions; d4) one or more washes with a wash solution of an internal electron donor (ID) and an aromatic and / or aliphatic hydrocarbon, preferably selected from toluene, hexane or pentane, and d3) one or more washes with a washing solution of an aromatic and / or aliphatic hydrocarbon, preferably selected from toluene, hexane or pentane; in the order described, wherein all of the washings with the titanium tetrachloride and internal electron donor (ID) washing solution in step d2) are carried out at a temperature in the range of 80 to 120°C, more preferably in the range of 85 to 120°C, even more preferably in the range of 85 to 120°C, still more preferably in the range of 90 to 110°C, and most preferably in the range of 95 to 105°C.

[0039] It is particularly preferred that the solvent used in step d1) and optional step d4) is toluene.

[0040] Therefore, the washing step d) preferably comprises: d1) one or more washes with toluene and optionally an internal electron donor (ID) wash solution; d2) one or more washes with a titanium tetrachloride and internal electron donor (ID) wash solution; d4) optionally one or more washes with an internal electron donor (ID) and toluene wash solution; and d3) one or more washes with a washing solution of an aromatic and / or aliphatic hydrocarbon, preferably selected from toluene, hexane or pentane; The method includes the steps of:

[0041] More preferably, the washing in step d) is d1) one or more washes with a wash solution of internal electron donor (ID) and toluene; d2) one or more washes with a titanium tetrachloride and internal electron donor (ID) wash solution; d4) optionally one or more washes with an internal electron donor (ID) and toluene wash solution; and d3) one or more washes with a washing solution of an aromatic and / or aliphatic hydrocarbon, preferably selected from toluene, hexane or pentane; The method includes the steps of:

[0042] The washing step d) is d1) one or more washes with a wash solution of internal electron donor (ID) and toluene; d2) two or more washes with titanium tetrachloride and internal electron donor (ID) wash solutions; d4) one or more washes with toluene and optionally an internal electron donor (ID) wash solution; and d3) one or more washes with a washing solution of an aromatic and / or aliphatic hydrocarbon, preferably selected from toluene, hexane or pentane; in the order described, wherein all of the washings with the titanium tetrachloride and internal electron donor (ID) washing solution in step d2) are carried out at a temperature in the range of 80 to 120°C, more preferably in the range of 85 to 120°C, even more preferably in the range of 85 to 115°C, even more preferably in the range of 90 to 110°C, and most preferably in the range of 95 to 105°C.

[0043] The washing step d) is d1) one or more washes with a wash solution of internal electron donor (ID) and toluene; d2) two or more washes with titanium tetrachloride and internal electron donor (ID) wash solutions; d4) one or more washes with a wash solution of internal electron donor (ID) and toluene; and d3) one or more washes with a washing solution of an aromatic and / or aliphatic hydrocarbon, preferably selected from toluene, hexane or pentane; in the order described, wherein all of the washings with the titanium tetrachloride and internal electron donor (ID) washing solution in step d2) are carried out at a temperature in the range of 80 to 120°C, more preferably in the range of 85 to 120°C, even more preferably in the range of 85 to 115°C, even more preferably in the range of 90 to 110°C, and most preferably in the range of 95 to 105°C.

[0044] In each of these embodiments in which step d) further comprises step d4), the amount of internal electron donor (ID) and donor present in the wash solution of aromatic and / or aliphatic hydrocarbon, preferably selected from toluene, hexane, or pentane, is such that the molar ratio between the amount of internal electron donor (ID) and the amount of magnesium in the Ziegler-Natta catalyst component ([ID] / [Mg]) is in the range of 0.01 to 0.20, more preferably in the range of 0.02 to 0.15, and most preferably in the range of 0.03 to 0.10.

[0045] The amount of magnesium in the Ziegler-Natta catalyst is assumed to be equal to the amount of magnesium used in the preceding catalyst preparation step that introduces magnesium; i.e., it may be assumed that all of the magnesium used in the catalyst preparation is ultimately present in the Ziegler-Natta catalyst.

[0046] Without wishing to be bound by theory, it is believed that the higher the temperature in the one or more washes with titanium tetrachloride and internal electron donor (ID) wash solution in step d2), the more donor must be present in step d4).

[0047] In each of the above-described embodiments, the internal donor (ID) used in steps d1) (if a donor is present), d2), d4) (if this step is present) and any steps prior to step c) is a non-phthalate internal donor.

[0048] The non-phthalic internal donors used in these steps can be the same or different, or can be a mixture of non-phthalic internal donors.

[0049] In one preferred embodiment, the non-phthalic internal donor in each of steps d1) (if a donor is present), d2), d4) (if this step is present) and any steps prior to step c) is the same non-phthalic internal donor, either a single non-phthalic internal donor or a mixture of non-phthalic internal donors, most preferably a single non-phthalic internal donor.

[0050] It is particularly preferred that the non-phthalic internal electron donor is a non-phthalic diester or a mixture of non-phthalic diesters, and most preferably a single non-phthalic diester.

[0051] More preferably, the non-phthalic internal electron donor is a monounsaturated diester or a mixture of monounsaturated diesters, and most preferably a single monounsaturated diester.

[0052] In particular, the non-phthalic internal electron donor is preferably selected from the group of maleic acid esters, citraconic acid esters, cyclohexene-1,2-dicarboxylic acid esters (cyclohexene-1,2-dicarboxylates), and derivatives and / or mixtures of any of these.

[0053] Most preferably, the non-phthalic acid electron donor is a citraconic acid ester internal electron donor.

[0054] The magnesium component of step a) may be any magnesium-containing compound, but is preferably selected from magnesium halides, magnesium alkoxides, and mixtures thereof.

[0055] In one particularly preferred embodiment, the magnesium component is a magnesium alkoxide.

[0056] Step a) in which a solution of at least one magnesium component is provided can be carried out according to any known method for providing a solution of at least one magnesium component known in the art.

[0057] Suitable methods include methods a1) to a5). a1) providing a solution of at least one magnesium alkoxy compound (Ax) which is the reaction product of a magnesium compound (MgC) and a monohydric alcohol (A) which contains at least one ether moiety in addition to the hydroxyl moiety, optionally in an organic liquid reaction medium, or a2) a solution, optionally in an organic liquid reaction medium, of at least one magnesium alkoxy compound (Ax') which is the reaction product of a magnesium compound (MgC) with a mixture of monohydric alcohols (A) as defined above and monohydric alcohols (B) of formula ROH, where R is a linear or branched alkyl group of 2 to 16 carbon atoms, or a3) optionally providing a solution of a mixture of said magnesium alkoxy compound (Ax) and a magnesium alkoxy compound (Bx) which is the reaction product of a magnesium compound (MgC) with said monohydric alcohol (B) in an organic liquid reaction medium, or a4) Formula Mg(OR 1 ) n (OR 2 ) m X 2-n-m Magnesium alkoxy compounds or magnesium alkoxides Mg(OR 1 ) n’ X 2-n’ and Mg(OR 2 )m’ X 2-m’ A solution of a mixture, where X is a halogen, and R 1 and R 2 are different linear or branched alkyl groups having 2 to 16 carbon atoms, 0 ≦ n < 2, 0 ≦ m < 2 and 0 < n + m ≦ 2, and 0 < n’ ≦ 2 and < m’ ≦ 2, to provide a solution. a5) A solution containing Mg dihalide in an alcohol mixture containing at least a monohydric alcohol (A1) of the formula ROH (and optionally an alcohol (A2) containing another oxygen-containing functional group other than a hydroxyl group in addition to the hydroxyl group), where R is selected from hydrocarbyls having 3 to 16 C atoms, to provide a solution. a6) To provide a solution containing Mg dihalide in an organic solvent.

[0058] In one preferred embodiment, step a) is a1) To provide a solution of at least one magnesium alkoxy compound (Ax) which is a reaction product of a magnesium compound (MgC) in an optional organic liquid reaction medium and a monohydric alcohol (A) containing at least one ether moiety in addition to the hydroxyl moiety, or a) A solution of at least one magnesium alkoxy compound (Ax’) which is a reaction product of a magnesium compound (MgC) in an optional organic liquid reaction medium and an alcohol mixture of the above monohydric alcohol (A) and a monohydric alcohol (B) of the formula ROH, where R is a linear or branched alkyl group having 2 to 16 carbon atoms, or a3) To provide a solution of a mixture of a magnesium alkoxy compound (Ax) and a magnesium alkoxy compound (Bx) which is a reaction product of the above magnesium compound (MgC) and the above monohydric alcohol (B) in an optional organic liquid reaction medium, or a4) The magnesium alkoxy compound of the formula Mg(OR 1 ) n (OR 2 ) m X 2-n-m or the magnesium alkoxide Mg(OR 1 ) n’X 2-n’ and Mg(OR 2 ) m’ X 2-m’ in a solution of a mixture, where X is a halogen, and R 1 and R 2 are different linear or branched alkyl groups having 2 to 16 carbon atoms, 0 ≦ n < 2, 0 ≦ m < 2 and 0 < n + m ≦ 2, and 0 < n' ≦ 2 and 0 < m' ≦ 2, to provide a solution a5) A solution containing Mg dihalide in an alcohol mixture containing at least a monohydric alcohol (A1) of the formula ROH (and optionally an alcohol (A2) containing another oxygen-containing functional group other than a hydroxyl group in addition to the hydroxyl group), where R is selected from hydrocarbyls having 3 to 16 C atoms, to provide a solution a6) To provide a solution containing Mg dihalide in an organic solvent consisting of, and in addition, the non-phthalic acid internal electron donor according to the present invention may be added at any stage

[0059] Thus, the internal donor (ID) or its precursor is preferably added to the solution of step a) or to the titanium(IV) compound before adding the solution of step a

[0060] According to the above procedure, the Ziegler-Natta catalyst component can be obtained by a precipitation method or an emulsion coagulation method depending on the physical conditions, especially the temperature used in steps b) and c). The emulsion is also referred to as a liquid / liquid two-phase system in the present application

[0061] In both methods (precipitation or emulsion coagulation), the chemical nature of the catalyst is the same

[0062] In the precipitation method, a combination of the solution of step a) and at least one titanium(IV) compound in step b) is carried out, and the entire reaction mixture is maintained in a temperature range of at least 50 °C, more preferably 55 to 110 °C, more preferably 70 to 100 °C, to ensure complete precipitation (step c) of the catalyst component in the form of solid particles

[0063] In the emulsion coagulation process in step b), the solution from step a) is typically added to at least one titanium(IV) compound at low temperature, for example, from -10 to less than 50°C, preferably from -5 to 30°C. During stirring of the emulsion, the temperature is typically maintained at from -10 to less than 40°C, preferably from -5 to 30°C. The droplets of the dispersed phase of the emulsion form the active catalyst composition. Coagulation of the droplets (step c) is suitably carried out by heating the emulsion to a temperature of 70 to 150°C, preferably from 80 to 110°C.

[0064] In the present invention, it is preferred to use a catalyst prepared by the emulsion coagulation method.

[0065] In a preferred embodiment in step a), a solution of a2) or a3), ie a solution of (Ax') or a solution of a mixture of (Ax) and (Bx), especially a solution of a2), is used.

[0066] The magnesium alkoxy compounds as defined above can be prepared in situ in the first step, step a), of the catalyst preparation process by reacting a magnesium compound with an alcohol as described above, or they can be separately prepared magnesium alkoxy compounds, or they can be commercially available as readily available magnesium alkoxy compounds and can be used as such in the catalyst preparation process of the present invention.

[0067] A specific example of the alcohol (A) is a glycol monoether. Preferred alcohols (A) are C2-C4 glycol monoethers in which the ether moiety contains 2 to 18 carbon atoms, preferably 4 to 12 carbon atoms. Preferred examples include 2-(2-ethylhexyloxy)ethanol, 2-butyloxyethanol, 2-hexyloxyethanol, 1,3-propylene glycol monobutyl ether, and 3-butoxy-2-propanol, with 2-(2-ethylhexyloxy)ethanol, 1,3-propylene glycol monobutyl ether, and 3-butoxy-2-propanol being particularly preferred.

[0068] Exemplary monohydric alcohols (B) are of the formula ROH, where R is a linear or branched C-C 16 Alkyl groups, preferably C4 to C 10 More preferably, it is a C6 to C8 alkyl group. The most preferred monohydric alcohol is 2-ethyl-1-hexanol or octanol.

[0069] Preferably, a mixture of Mg alkoxy compounds (Ax) and (Bx) or a mixture of alcohols (A) and (B) is used, respectively, in a molar ratio of Bx:Ax or B:A of 10:1 to 1:10, more preferably 6:1 to 1:6, most preferably 4.1 to 1:4.

[0070] The magnesium alkoxy compound may be the reaction product of an alcohol as defined above with a magnesium compound selected from dialkylmagnesium, alkylmagnesium alkoxide, magnesium dialkoxide, alkoxymagnesium halide, and alkylmagnesium halide. Additionally, magnesium dialkoxide, magnesium diaryloxide, magnesium aryloxyhalide, magnesium aryloxide, and magnesium alkylaryloxide can be used. The alkyl groups may be the same or different C1-C 20 Alkyl, preferably C2-C 10The alkyl group can be an alkyl. When used, typical alkylalkoxy magnesium compounds are ethyl magnesium butoxide, butyl magnesium pentoxide, octyl magnesium butoxide, and octyl magnesium octoxide. Preferably, dialkyl magnesiums are used. The most preferred dialkyl magnesiums are butyloctyl magnesium or butylethyl magnesium.

[0071] The magnesium compound is combined with the alcohol (A) and the alcohol (B) and the formula R"(OH) m It is also possible to obtain the magnesium alkoxide compound by reacting with a polyhydric alcohol (C) of the formula (I). When used, preferred polyhydric alcohols are those in which R" is a linear, cyclic or branched C2-C 10 It is an alcohol which is a hydrocarbon group and m is an integer of 2 to 6.

[0072] Thus, the magnesium component in step a) is selected from the group consisting of magnesium dihalides, magnesium dialkoxides, diaryloxymagnesiums, alkyloxymagnesium halides, aryloxymagnesium halides, alkylmagnesium alkoxides, arylmagnesium alkoxides, and alkylmagnesium aryloxides. Additionally, mixtures of magnesium dihalides and magnesium dialkoxides can be used.

[0073] The solvent used in the preparation of the catalyst may be selected from aromatic and aliphatic linear, branched and cyclic hydrocarbons, or mixtures thereof, having 5 to 20 carbon atoms, more preferably 5 to 12 carbon atoms. Suitable solvents include benzene, toluene, cumene, xylene, pentane, hexane, heptane, octane and nonane. Heptane, hexane and pentane are particularly preferred.

[0074] The reaction for preparing the magnesium component may be carried out at a temperature of 40 to 70° C. The most suitable temperature is selected depending on the Mg compound and alcohol used.

[0075] Most preferably, the titanium (IV) compound is a titanium (IV) halide such as TiCl4.

[0076] In the emulsification method, a two-phase liquid-liquid system may be formed by simple stirring and, optionally, the addition of (further) solvents and / or additives, such as turbulence minimizing agents (TMA) and / or emulsion stabilizers, such as emulsifiers and / or surfactants, which are used to facilitate the formation of and / or stabilize emulsions, as known in the art. Preferably, the surfactant is an acrylic or methacrylic polymer. Particularly preferred are unbranched C methacrylates, such as poly(hexadecyl) methacrylate, poly(octadecyl) methacrylate, etc. 12 ~C 20 (meth)acrylates, and mixtures thereof. When used, the turbulence minimizing agent (TMA) is preferably selected from α-olefin polymers of α-olefin monomers having 6 to 20 carbon atoms, such as polyoctene, polynonene, polydecene, polyundecene, or polydodecene, or mixtures thereof. Most preferred is polydecene.

[0077] The solid particulate product obtained by the precipitation or emulsion coagulation process is washed in accordance with washing step d) described above and below.

[0078] The aluminum compound can also be added during catalyst synthesis. The catalyst can be further dried, such as by evaporation or flushing with nitrogen, or can be slurried in an oily liquid without any drying step.

[0079] In some embodiments, after step e), the Ziegler-Natta catalyst component is further modified with a polymer nucleating agent obtained by polymerizing a vinyl monomer of formula (I). H2C=CH-CHR 1 R 2 (I) In the formula, R 1 and R 2 independently represent a lower alkyl group containing 1 to 4 carbon atoms, or together with the carbon atom to which they are attached form an optionally substituted saturated, unsaturated or aromatic ring or fused ring system, which ring or fused ring moiety contains 4 to 20 carbon atoms, preferably R 1 and R 2 together with the carbon atoms to which they are attached form a 5- to 12-membered saturated, unsaturated or aromatic ring or fused ring system.

[0080] Preferably, R 1 and R 2 form, together with the C atom to which they are attached, a 5- or 6-membered saturated, unsaturated or aromatic ring, or independently represent a lower alkyl group containing 1 to 4 carbon atoms.

[0081] Preferred vinyl compounds for the preparation of the polymer nucleating agents used according to the invention are in particular vinylcycloalkanes, in particular vinylcyclohexane (VCH), vinylcyclopentane, and vinyl-2-methylcyclohexane, 3-methyl-1-butene, 3-ethyl-1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene or mixtures thereof.

[0082] VCH is a particularly preferred monomer.

[0083] The polymeric nucleating agent is preferably incorporated into the catalyst component by the so-called BNT technique, as described below.

[0084] With regard to the BNT technology, reference is made to WO 99 / 24478, WO 99 / 24479 and especially WO 00 / 68315, according to which a catalyst component is modified by polymerizing a vinyl compound in the presence of the above-mentioned catalyst system, which comprises in particular a specific catalyst component, an external donor and a cocatalyst.

[0085] General conditions for catalyst modification, such as liquid media and process parameters, are also disclosed in WO 99 / 24478, WO 99 / 24479, and especially WO 00 / 68315, which are incorporated herein by reference for the modification of polymerization catalysts.

[0086] The weight ratio of the vinyl compound to the polymerization catalyst in the polymerization catalyst modification step is preferably 0.3 or more and 40 or less, for example, 0.4 to 20, more preferably 0.5 to 15, for example, 0.5 to 2.0.

[0087] In addition to oil, suitable media for the reforming process include low viscosity aliphatic inert organic solvents such as pentane and heptane. Additionally, small amounts of hydrogen can be used during reforming.

[0088] The polymeric nucleating agent is usually present in the final product in an amount greater than 10 ppm, typically greater than 15 ppm (based on the weight of the polypropylene composition). Preferably, the agent is present in the polypropylene composition in the range of 10 to 1000 ppm, more preferably greater than 15 to 500 ppm, for example, 20 to 100 ppm.

[0089] Polymerization of the catalyst with the vinyl compound is carried out until the concentration of unreacted vinyl compound is less than about 0.5% by weight, preferably less than 0.1% by weight.

[0090] This polymerization step is usually carried out in a prepolymerization step prior to the polymerization process used to produce polyolefins, preferably polypropylene.

[0091] Ziegler-Natta catalyst composition The present invention is further directed to a Ziegler-Natta catalyst composition obtainable by the above catalyst preparation process.

[0092] If the Ziegler-Natta catalyst component obtained in step e) is further modified with a polymer nucleating agent obtained by polymerizing a vinyl monomer of formula (I), the Ziegler-Natta catalyst composition comprises, or more preferably consists of, this modified catalyst component.

[0093] Unless further modified, the Ziegler-Natta catalyst composition comprises, and more preferably consists of, the Ziegler-Natta catalyst components described above and below.

[0094] In particular, it is preferred that the titanium content of the Ziegler-Natta catalyst component, and more preferably the Ziegler-Natta catalyst composition, is in the range of 1.00 to 2.40 wt %, more preferably in the range of 1.30 to 2.20 wt %, and most preferably in the range of 1.50 to 2.00 wt %.

[0095] Furthermore, it is preferred that the weight ratio of titanium to magnesium ([Ti] / [Mg]) in the Ziegler-Natta catalyst component, more preferably in the Ziegler-Natta catalyst composition, is in the range of 0.06 to 0.14, more preferably in the range of 0.07 to 0.13, and most preferably in the range of 0.08 to 0.12.

[0096] It is also preferred that the magnesium content of the Ziegler-Natta catalyst component, and more preferably the Ziegler-Natta catalyst composition, is in the range of 11.0 to 24.0 wt %, more preferably in the range of 14.0 to 22.0 wt %, and most preferably in the range of 17.0 to 20.0 wt %.

[0097] It is further preferred that the internal donor content of the Ziegler-Natta catalyst component, more preferably the Ziegler-Natta catalyst composition, is in the range of 10.0 to 23.0 wt %, more preferably in the range of 13.0 to 20.0 wt %, and most preferably in the range of 15.0 to 18.0 wt %.

[0098] Preferably, the weight ratio of titanium to internal donor ([Ti] / [ID]) in the Ziegler-Natta catalyst component, more preferably in the Ziegler-Natta catalyst composition, is in the range of 0.06 to 0.13, more preferably in the range of 0.07 to 0.12, and most preferably in the range of 0.08 to 0.11.

[0099] It is also preferred that the weight ratio of magnesium to internal donor ([Mg] / [ID]) in the Ziegler-Natta catalyst component, more preferably the Ziegler-Natta catalyst composition, is in the range of 1.00 to 1.50, more preferably in the range of 1.00 to 1.35, and most preferably in the range of 1.05 to 1.20.

[0100] The Ziegler-Natta catalyst component, more preferably the Ziegler-Natta catalyst composition, is desirably in the form of particles generally having an average particle size range of 5 to 200 μm, preferably 10 to 100 μm. The particles are compact and have low porosity, and have a particle size of 20 g / m or less. 2 less than 10 g / m 2 has a surface area of ​​less than

[0101] Detailed descriptions of the preparation of the catalysts are disclosed in WO 2012 / 007430, EP 2610271, EP 2610270 and EP 2610272.

[0102] All preferred embodiments and fallback ranges expressed in the sections above and below apply mutatis mutandis to the Ziegler-Natta catalyst component and / or Ziegler-Natta catalyst composition.

[0103] Polymerization Process The present invention is also directed to a process for the production of a polypropylene composition using the catalyst of the present invention, and the use of such catalyst for such a process.

[0104] In one embodiment, the present invention is directed to a process for the production of a polypropylene composition comprising the polymerization of propylene, optionally with a comonomer selected from a C2 or C4 to C12 alpha olefin, in the presence of a Ziegler-Natta catalyst system comprising the Ziegler-Natta catalyst composition of the present invention, a cocatalyst (Co), and optionally an external donor (ED).

[0105] In another embodiment, the present invention provides a process for producing a polypropylene composition comprising: a) providing a solution of at least one magnesium component; b) adding the solution from step a) to a titanium (IV) compound, thereby obtaining solid catalyst component particles; c) recovering the solid catalyst component particles from the solution obtained from step b); d) washing the solid catalyst component particles; e) recovering the solid catalyst component particles of the olefin polymerization catalyst component; in the order listed, wherein an internal electron donor (ID) is added in any step prior to step c), wherein the internal electron donor (ID) is a non-phthalic acid internal electron donor; The washing step d) is d1) one or more washes with a wash solution of an aromatic and / or aliphatic hydrocarbon, preferably selected from toluene, hexane or pentane, and optionally an internal electron donor (ID), d2) one or more washes with a titanium tetrachloride and internal electron donor (ID) wash solution; and d3) one or more washes with a washing solution of an aromatic and / or aliphatic hydrocarbon, preferably selected from toluene, hexane or pentane; in the order stated, wherein at least one of the one or more washes with a titanium tetrachloride and internal electron donor (ID) wash solution in step d2) is carried out at a temperature in the range of 80 to 120°C, more preferably in the range of 85 to 120°C, even more preferably in the range of 85 to 115°C, even more preferably in the range of 90 to 110°C, and most preferably in the range of 95 to 105°C; the process further comprising the step of polymerizing propylene, optionally with a comonomer selected from a C2 or C4 to C12 alpha olefin, in the presence of a Ziegler-Natta catalyst system comprising a Ziegler-Natta catalyst composition comprising the solid catalyst component recovered in step e), a cocatalyst (Co) and optionally an external donor (ED).

[0106] Furthermore, the present invention is directed to the use of the Ziegler-Natta catalyst composition according to the present invention, optionally together with a cocatalyst (Co) and optionally an external donor (ED), for the polymerization of propylene with a comonomer selected from C2 or C4 to C12 alpha-olefins.

[0107] Suitable external donors (ED) include certain silanes, ethers, esters, amines, ketones, heterocyclic compounds, and blends thereof. It is particularly preferred to use silanes. R a p R b q Si(OR c ) (4-p-q) It is most preferred to use silanes of the formula: a , R b and R c represents a hydrocarbon radical, particularly an alkyl or cycloalkyl group, and p and q are numbers ranging from 0 to 3, and the sum of p+q is 3 or less. a , R b and R ccan be selected independently of each other and may be the same or different. Specific examples of such silanes include (tert-butyl)Si(OCH), (cyclohexyl)(methyl)Si(OCH), (phenyl)Si(OCH) and (cyclopentyl)Si(OCH), or silanes of the general formula Si(OCH2CH3)3(NR 3 R 4 ) where R 3 and R 4 may be the same or different and represent a hydrocarbon group having 1 to 12 carbon atoms.

[0108] R 3 and R 4 R is independently selected from the group consisting of a linear aliphatic hydrocarbon group having 1 to 12 carbon atoms, a branched aliphatic hydrocarbon group having 1 to 12 carbon atoms, and a cyclic aliphatic hydrocarbon group having 1 to 12 carbon atoms. 3 and R 4 are particularly preferably independently selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, octyl, decanyl, iso-propyl, iso-butyl, iso-pentyl, tert-butyl, tert-amyl, neopentyl, cyclopentyl, cyclohexyl, methylcyclopentyl, and cycloheptyl.

[0109] More preferably, R 1 and R 2 and even more preferably, both R 3 and R 4 are both ethyl groups.

[0110] Particularly preferred external donors (ED) are di-cyclopentyl-dimethoxysilane donors (D-donors) or cyclohexylmethyldimethoxysilane donors (C-donors).

[0111] In addition to the Ziegler-Natta catalyst composition and optional external donor (ED), a cocatalyst should be used. This cocatalyst is preferably a compound of Group 13 of the Periodic Table (IUPAC), for example, an organoaluminum such as an aluminum alkyl, an aluminum halide (aluminum halide), or an aluminum compound such as an aluminum alkyl halide compound. Thus, in one specific embodiment, the cocatalyst (Co) is a trialkylaluminum, such as triethylaluminum (TEAl), a dialkylaluminum chloride, or an alkylaluminum dichloride, or a mixture thereof. In one specific embodiment, the cocatalyst (Co) is triethylaluminum (TEAl).

[0112] Advantageously, the triethylaluminum (TEAl) has a hydride content, expressed as AlH3, of less than 1.0% by weight relative to the triethylaluminum (TEAl), more preferably the hydride content is less than 0.5% by weight, and most preferably the hydride content is less than 0.1% by weight.

[0113] Preferably, the ratio between the cocatalyst (Co) and the external donor (ED) [Co / ED] and / or the ratio between the cocatalyst (Co) and titanium [Co / Ti] should be carefully selected.

[0114] Therefore, (a) The molar ratio of cocatalyst (Co) to external donor (ED) [Co / ED] must be in the range of 5 to 45, preferably in the range of 5 to 35, more preferably in the range of 5 to 25, and optionally (b) The molar ratio of the cocatalyst (Co) to titanium [Co / Ti] must be in the range of more than 70 to 500, preferably in the range of 80 to 300, and even more preferably in the range of 90 to 200.

[0115] The polymerization process for the production of polypropylene may be a continuous or batch process, utilizing known methods, operating in the liquid phase, optionally in the presence of an inert diluent, or in the gas phase, or by mixed liquid-gas techniques.

[0116] The polymerization process may be a single-stage or multi-stage polymerization process such as gas phase polymerization, slurry polymerization, solution polymerization, or a combination thereof.

[0117] For the purposes of this invention, "slurry reactor" means any reactor operating in bulk or slurry in which the polymer is formed in particulate form, such as a continuous or simple batch stirred tank reactor or loop reactor. "Bulk" refers to polymerization in a reaction medium containing at least 60% by weight of monomer. According to a preferred embodiment, the slurry reactor comprises a bulk loop reactor. "Gas phase reactor" means any mechanically mixed reactor or fluidized bed reactor. Preferably, the gas phase reactor comprises a mechanically agitated fluidized bed reactor using a gas flow rate (gas velocity) of at least 0.2 m / s.

[0118] Polypropylene can be produced, for example, in one or two slurry bulk reactors, preferably in one or two loop reactors, or in a combination of one or two loop reactors and at least one gas phase reactor, processes which are well known to those skilled in the art.

[0119] Preferably, the reactors used are selected from the group of loop reactors and gas-phase reactors, in particular the process employs at least one loop reactor and at least one gas-phase reactor, it is also possible to use several reactors of each type in series, for example one loop reactor and two or three gas-phase reactors, or two loop reactors and one gas-phase reactor.

[0120] If the polymerization is carried out in one or two loop reactors, it is preferably carried out in a liquid propylene mixture at a temperature in the range of 20 to 100°C. Preferably, the temperature is in the range of 60 to 80°C. The pressure is preferably 5 to 60 bar. Comonomers, if added, can be fed to either reactor. The molecular weight of the polymer chains, and therefore the melt flow rate of the polypropylene, is adjusted by adding hydrogen.

[0121] The gas-phase reactor may be a conventional fluidized bed reactor, although other types of gas-phase reactors can be used. In a fluidized bed reactor, the bed consists of the polymer particles that are formed and growing and the still active catalyst with the polymer fraction. The bed is kept in a fluidized state by introducing a gaseous component, e.g., monomer, at a flow rate that causes the particles to act as a fluid. The fluidizing gas can contain an inert carrier gas, such as nitrogen, or hydrogen as a modifier. The fluidized gas-phase reactor can be equipped with a mechanical mixer.

[0122] The gas phase reactor used can be operated in the temperature range of 50 to 110°C, preferably 60 to 90°C, and at a reaction pressure of 5 to 40 bar.

[0123] Suitable processes are disclosed, inter alia, in WO 98 / 58976, EP 887380 and WO 98 / 58977.

[0124] In any polymerization process, it is also possible to use a comonomer selected from the group of ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene, etc., and mixtures thereof.

[0125] In addition to the actual polymerization reactor used to produce the propylene homopolymer or copolymer, the polymerization configuration may also include several additional reactors, such as pre-reactors and / or post-reactors, including any reactor for pre-polymerizing the reforming catalyst with propylene and / or ethylene or other 1-olefins, if desired.

[0126] Post-reactors include reactors used to modify and improve the properties of the polymer product (see below). All reactors in the reactor system are preferably arranged in series.

[0127] If desired, the polymerization product can be fed to a gas-phase reactor where a rubbery copolymer is provided by (co)polymerization to produce a modified polymerization product. This polymerization reaction provides polymerization product properties, such as improved impact strength. The process of providing an elastomer can be carried out in various ways. Thus, preferably, the elastomer is produced by copolymerizing at least propylene and ethylene into an elastomer.

[0128] The polymerization product of the present invention from the reactor, the so-called reactor powder in the form of polypropylene powder, fluff, spheres, etc., is typically melt-blended with additives, auxiliary agents such as fillers and reinforcing agents, and / or other polymers conventionally used in the art, compounded, and pelletized. Suitable additives include antioxidants, acid scavengers, antistatic agents, flame retardants, light and heat stabilizers, lubricants, optionally additional nucleating agents, clarifying agents, pigments, and other colorants, including carbon black. Fillers such as talc, mica, and wollastonite can also be used. [Example]

[0129] 1. Definition / Measurement method The following definitions of terms and determination methods apply to the above summary of the invention and the following examples, unless otherwise defined.

[0130] MFR2 (230°C) was measured in accordance with ISO1133 (230°C, 2.16 kg load).

[0131] Xylene solubles (XCS, wt%): The cold xylene solubles (XCS) content was determined at 25°C according to ISO 16152; 1st edition; 2005-07-01.

[0132] Melting temperature (T m ): Differential scanning calorimetry (DSC) analysis was performed on 5-7 mg samples using a TA Instrument Q2000 DSC. DSC was performed in a heat / cool / heat cycle at a scan rate of 10 °C / min in the temperature range of -30 to +225 °C according to ISO 11357 / Part 3 / Method C2. Crystallization temperature and heat of crystallization (H c ) is determined from the cooling process, and the melting temperature and heat of fusion (H f ) is determined from the second heating step (however, only the melting temperature is given in relation to the examples below).

[0133] Molecular Weight Distribution - GPC: Molecular weight averages (Mz, Mw, Mn), molecular weight distribution (MWD), and the breadth of the molecular weight distribution, expressed as the polydispersity index PDI = Mw / Mn (Mn is the number average molecular weight and Mw is the weight average molecular weight), were determined by gel permeation chromatography (GPC) according to ISO 16014-1:2003, ISO 16014-2:2003, ISO 16014-4:2003, and ASTM D 6474-12 using the following equation:

number

[0134] Fixed elution volume interval ΔV i In contrast, A i and M i are the elution volume V, respectively. i where σ is the slice area of ​​the chromatographic peak associated with σ and σ is the molecular weight (MW) of the polyolefin, and N is equal to the number of data points obtained from the chromatogram between the integration limits.

[0135] A high-temperature GPC system equipped with an infrared (IR) detector (IR4 or IR5, PolymerChar, Valencia, Spain) and equipped with 3 Agilent PLgel Olexis and 1 Agilent PLgel Olexis Guard columns was used. 1,2,4-Trichlorobenzene (TCB) stabilized with 250 mg / L of 2,6-di-tert-butyl-4-methyl-phenol was used as the solvent and mobile phase. The chromatographic system was operated at 160 °C with a constant flow rate of 1 mL / min. 200 μL of sample solution was injected per analysis. Data collection was performed using Agilent Cirrus software version 3.3 or PolymerChar GPC-IR control software.

[0136] The column set was calibrated using universal calibration (according to ISO 16014-2:2003) with 19 narrow MWD polystyrene (PS) standards ranging from 0.5 kg / mol to 11,500 kg / mol. The PS standards were dissolved at room temperature for several hours. Conversion of polystyrene peak molecular weights to polyolefin molecular weights was performed using the Mark Houwink equation and the following Mark Houwink constants: K PS =19×10 -3 mL / g, α PS =0.655 K PE =39×10 -3 mL / g, α PE =0.725 K PP =19×10 -3 mL / g, α PP =0.725

[0137] Third order polynomial fitting was used to fit the calibration data.

[0138] All samples were prepared in the concentration range of 0.5-1 mg / ml and dissolved at 160°C for 2.5 hours for PP and 3 hours for PE under continuous gentle shaking.

[0139] Scanning Electron Microscopy - SEM Scanning electron microscopy (SEM) was performed using an FEI Quanta 200 FEG microscope. Catalyst particles were attached to a sample holder using carbon or copper conductive adhesive. If necessary, sections of the catalyst particles were cut using a microtome blade. Samples were sputter-coated with Au / Pd in ​​an Agar Auto sputter coater. Images were typically acquired using an Everhart-Thornley detector (ETD) with settings of 1.5-3 kV accelerating voltage, high vacuum mode, 10 mm working distance, and a 3.0 spot size. Images were collected at 1024 × 884 pixels at magnifications ranging from 60x to 6000x.

[0140] Polymer imaging by optical microscopy Equipment: Leica MZ16 Instructions: The sample is mixed well in a plastic bag with a spoon. An aliquot of approximately 5 mL is taken for imaging. The sample is placed on black matte paper in a Petri dish. Images are taken at various magnifications (0.71, 1.0, 1.25, 1.6, 2.0, 2.5, 3.2, 4.0, 5.0, and 6.3).

[0141] Catalyst imaging by optical microscopy Equipment: Polyvar microscope Description: The oil slurry sample is mixed thoroughly using a carousel mixer for approximately 30 minutes. An aliquot of approximately 0.5 ml is taken into a 3 ml syringe with a 2 mm needle and diluted with approximately 1 ml of clean oil. The sample is mixed by tilting it several times in the syringe. Two drops of the diluted sample are placed on a microscope glass and a coverslip is placed on top, avoiding air bubbles between the glass plates. Several images are taken with 4x, 10x and 25x objectives.

[0142] ZNPP - ID, 2-EHA, PGBE, and HC Content - GC-FID: A 60-90 mg portion of the dried catalyst, sampled in an inert solution in a crimp-cap glass vial, was dissolved and extracted with a mixture of 5 mL of dichloromethane and 1.0 mL of a distilled, deionized solution of the internal standard (0.71% v / v). The mixture was sonicated for 30 minutes to ensure complete dissolution, after which the phases were allowed to settle. The organic phase was sampled and filtered into an instrument vial using a 0.45 μm syringe filter. GC analysis was performed using an Agilent 7890B gas chromatograph system equipped with a flame ionization detector. The column used was a ZB-5HT Inferno 15 m x 320 μm x 0.25 μm column with a 1.5 m x 320 μm x 0 μm precolumn restriction capillary. The initial oven temperature was set at 40°C for 3 minutes, after which the ramp program consisted of a first ramp to 70°C at 5°C / min, a second ramp to 330°C at 40°C / min, and a third ramp to 350°C at 20°C / min with a 1-minute hold time. The injection volume was 1 μL, and the split ratio was 1:20. The carrier gas was 99.995% He. The inlet and FID were operated at 280°C and 370°C, respectively. The signal from the FID in the chromatogram was integrated and calculated for a series of standardized samples using the response ratio between the signal for the analyte and the internal standard. Two parallel measurements were performed from each sample, and the internal donor content was reported as the average of the two replicates.

[0143] ZNPP - Al, Ti, and Mg Content - ICP OES: Test portions of 20-50 mg of dried ZN catalyst were inertly sampled in crimp-cap glass vials. A 5 mL volume of HNO3 (65%) and distilled, deionized water was added to the sample vial, and the mixture was stirred until the catalyst was completely dissolved. The sample solution was transferred to a 100 mL volumetric flask and filled to the mark with distilled, deionized water.

[0144] Elemental analysis was performed using a Thermo Scientific iCAP 6300 Radial inductively coupled plasma-optical emission spectrometer (ICP-OES). The instrument was calibrated for Al, Ti, and Mg using a blank (a solution of 5% HNO3) and five standards of Al, Ti, and Mg at 0.5, 1, 10, 50, and 100 mg / L in a solution of 5% HNO3 in deionized water. Magnesium content was monitored at 285.213 nm, and titanium content at 336.121 nm. Aluminum content was monitored at 167.079 nm for Al concentrations between 0 and 10 wt% in the test portion, and at 396.152 nm for Al concentrations above 10 wt%. Reported values ​​are the average of three consecutive aliquots taken from the same sample and are related to the original catalyst sample by entering the original mass of the test portion and the dilution amount into the software.

[0145] Particle Size Distribution - Malvern PSD Analysis ZNPP - Particle Size Distribution - Automated Image Analysis Prepare the test solution by adding white mineral oil to an inertly sampled test portion of the ZN catalyst powder so that the final mixture maintains a concentration of approximately 0.5-0.7 wt%. After carefully mixing the test solution, take a portion and place it in a measuring cell appropriate for the instrument. Automated image analysis was performed using a Malvern Morphologi 3G system. The measurement cell was placed on the microscope stage. A transmitted light source was used, and the illumination intensity and focus level were adjusted before each run. Partially overlapping microscope image frames were recorded by a CCD camera, and the images were saved in the system's proprietary software via a microscope with a sufficient working distance for the objective and 5x magnification. The collected images were analyzed by the software, in which particles were individually identified by comparison with the background using a predefined grayscale setting for the material. A classification scheme was applied to the individually identified particles to include only images of sample material particles in the analysis. Particle diameter (particle size) is calculated as the circular equivalent (CE) diameter. The size range of particles included in the distribution is 6.5 to 420 μm. The distribution is calculated as a statistical descriptor calculated based on the numerical moment ratio density function distribution and the numerical distribution. The numerical distribution can be recalculated for each bin size to estimate the volume-transformed distribution. All graphical representations are based on 11-point smoothing functions, and population statistical descriptors are based on unsmoothed curves. Particle size distributions are reported using statistical descriptors, where d90 denotes the particle diameter at 90% cumulative size, d10 denotes the particle diameter at 10% cumulative size, and d50 denotes the particle diameter at 50% cumulative size. The mode is determined manually as the peak of the smoothed frequency curve. The span is calculated as (CE D[x,0.9]-CE D[x,0.1]) / CE D[x,0.5].

[0146] Chemicals used in the examples 2-Ethyl-hexanol - CAS No. 104-76-7 Propylene glycol butyl monoether - CAS number 5131-66-8, provided by Sigma-Aldrich Bis(2-ethylhexyl) citraconic acid - CAS number 1354569-12-2 Viscoplex 1-254 - Provided by RohMax Additives GmbH Triethylaluminum (TEAl) as a 0.62 M solution in n-heptane was obtained from Chemtura and used "as is." Dicyclopentyldimethoxysilane (Donor D) - CAS number 126990-35-0 was obtained from Wacker with 99.0% purity and diluted with n-heptane to prepare a 0.3 M solution. MEHO+ is a mixture of magnesium compounds (33% magnesium bis(2-ethylhexoxide) and magnesium bis(1-butoxypropan-2-olate) in n-heptane / toluene (8:2 wt. ratio)) with a Mg content of 3.2 wt. % and was obtained from Albemarle and used “as is.”

[0147] 2. Experiment a) Catalyst preparation Invention Example 1 16.1 kg of MEHO+ (33 wt % in n-heptane / toluene) was added to a 90 L reactor equipped with a mechanical stirrer at 14° C. 0.15 kg of Viscoplex 1-254 was added with mixing (200 rpm), followed by stirring for 120 minutes, after which 2.9 kg of bis(2-ethylhexyl) citraconic acid was added with mixing, followed by stirring for 30 minutes.

[0148] 21.4 kg of titanium tetrachloride was added to a 90 L reactor equipped with a mechanical stirrer at 14°C. The mixing speed was adjusted to 280 rpm. 19.6 kg of the Mg complex prepared above was added within 190 minutes, maintaining the temperature at 14°C. 0.47 kg of Viscoplex 1-254 was added. 12.6 kg of heptane was then added to form an emulsion. Mixing was continued at 14°C for 120 minutes, after which the reactor temperature was steadily increased to 90°C over 75 minutes. The reaction mixture was stirred at 90°C for an additional 60 minutes. Stirring was then stopped, and the reaction mixture was allowed to settle at 85°C for 90 minutes.

[0149] The solid material was washed seven times. Washing was carried out for 30 minutes with stirring at 280 rpm. After stopping the stirring, the reaction mixture was allowed to settle for 90 minutes, followed by siphoning to remove the washing solution. As a rule, siphoning was carried out at the temperature of the next washing step.

[0150] Wash 1: Washed at 80°C with a mixture of 24.9 kg toluene and 0.37 kg donor. Cleaning 2: Cleaned at 100°C with a mixture of 24.9 kg TiCl4 and 0.49 kg donor. Cleaning 3: Cleaned at 100°C with a mixture of 24.9 kg TiCl4 and 0.49 kg donor. Wash 4: Washed with 24.9 kg toluene and 0.37 kg donor at 80°C. Wash 5: Washed with 27.0 kg of heptane at 75°C. Wash 6: Wash with 30.3 kg of heptane at 55°C. Wash 7.3 Washed with 0.3 kg of heptane at 55°C.

[0151] After the final siphoning step, white oil (Primol 325) was added at a stirring rate of 300 rpm at 55° C. The resulting suspension was then dried under vacuum at 55° C. for 240 minutes at a stirring rate of 100 rpm to obtain an air-sensitive catalyst slurry.

[0152] Invention Example 2 The same procedure as in Inventive Example 1 was used, except that after the first addition of heptane, mixing was continued for 120 minutes at 14°C, and then the reactor temperature was increased to 90°C at a constant rate over 400 minutes.

[0153] Comparative Example 1 The same procedure as in Inventive Example 1 was used, except that the temperature in Wash 2 was 80° C., Wash 3 was omitted, and no donor was used in Wash 4.

[0154] Comparative Example 2 The same procedure as in Comparative Example 1 was used, except that 6 kg of heptane was added in the very first addition of heptane, after which mixing was continued for 120 minutes at 14°C, after which the reactor temperature was increased to 90°C at a constant rate over 45 minutes.

[0155] The properties of the catalyst particles thus obtained are summarized in Table 1.

[0156] [Table 1]

[0157] The catalyst of the present invention exhibits a high catalytic yield similar to that of the comparative catalyst, but has a slightly lower titanium and donor content, a slightly higher magnesium content, and a slightly larger median particle size (d50).

[0158] FIG. 1 further shows that the catalyst particles of the present invention exhibit a similar spherical morphology to the comparative catalyst particles, but, unlike CE1 in particular, exhibit a more compact internal morphology with less internal voids or surface disruptions.

[0159] b) Polymerization To evaluate the performance of each catalyst, propylene polymerizations were carried out over each catalyst using exactly the same conditions, as described below.

[0160] A 21.3 L autoclave reactor equipped with a helical stirrer was purged with propylene, charged with 5300 g of liquefied propylene, and maintained at 20° C. with stirring at 350 rpm. 1.22 ml of TEAl (0.582 M in heptane) was injected into the reactor for scavenging purposes and flushed with an additional 250 g of propylene. 3 L of hydrogen was fed to the reactor, and the reactor was stirred for 20 minutes.

[0161] Meanwhile, 59 mg of donor (D) (0.3 M in n-heptane) and 246 mg of TEAl (0.58 M in heptane) were mixed for 7 minutes ([TEAl] / [D] molar ratio 8.3:1) and then added to 38 mg of the solid catalyst precursor (supplied as a white oil slurry) from step a) ([TEAl] / [Ti] molar ratio 100:1; [D] / [Ti] molar ratio 12:1) to form a Ziegler-Natta catalyst system. Sufficient n-heptane was added to obtain a TEAl concentration of 0.1 M. These components were allowed to contact for a total of 10 minutes.

[0162] The resulting Ziegler-Natta catalyst system slurry was injected into the reactor and flushed with an additional 450 g of propylene. The temperature was increased to 80 °C over 20 minutes and maintained at this temperature for 60 minutes, while maintaining a stirring speed of 350 rpm. During the temperature increase, 9.8 L of hydrogen was added over 17 minutes. During the bulk polymerization at 80 °C, no additional propylene or hydrogen was added to the reactor.

[0163] After the bulk phase, the agitation speed was reduced to 100 rpm, and the reactor was then purged to a pressure of 0.5 barg. The reactor agitation speed was again increased to 350 rpm, and the reactor was charged with propylene and hydrogen ([H] / [C] = 10 mol / kmol) while the temperature and pressure increased until they reached 80 °C and 20 barg. Once the reactor temperature and pressure conditions were reached, the reaction conditions were held constant for 180 minutes, during which time the pressure was maintained constant by appropriately adjusting the monomer feed. Unreacted propylene and hydrogen were purged from the reactor to 0.5 barg at an agitation speed of 100 rpm. Residual gases were removed from the reactor by treating it with several nitrogen / vacuum flushing cycles at 30 °C, after which the polymer powder was collected, dried, and weighed.

[0164] The MFR2, XCS, Tm and catalyst productivity data for each of the inventive and comparative catalysts are shown in Table 2.

[0165] [Table 2]

[0166] As can be seen from the data in Table 2, the catalyst of the present invention can produce propylene homopolymers with lower MFR2, lower XCS content, and higher melting temperatures, which indicate higher molecular weight h-PP with higher crystallinity (see also Figure 2). Furthermore, the GPR split is significantly higher than that of the comparative catalyst, indicating that the activity of the catalyst experiences less decay throughout the process. This is particularly important for multi-stage sequential polymerization processes that may include three, four, or more sequential polymerization steps.

[0167] Without wishing to be bound by theory, it is believed that the higher washing temperatures during the titanium tetrachloride washes (Wash 2 and Wash 3) result in a modified crystalline structure on the surface of the catalyst particles, which affects the catalytic properties and results in the effects shown in Table 2.

[0168] FIG. 2 confirms the data in Table 2, which shows the higher average molecular weight of h-PP obtained using the catalysts of the present invention, and FIG. 3 shows that the polymer particles obtained with catalyst IE1 exhibit spherical particle morphology with negligible particle breakage and no polymer fines, IE2 and CE2 show negligible breakage and some polymer fines, and CE1 exhibits both significant polymer breakage and some polymer fines.

Claims

1. 1. A method for forming a Ziegler-Natta catalyst component, comprising: a) providing a solution of at least one magnesium component; b) adding the solution from step a) to a titanium (IV) compound, thereby obtaining solid catalyst component particles as a suspension; c) recovering the solid catalyst component particles from the suspension obtained from step b); d) washing the solid catalyst component particles; e) recovering the solid catalyst component particles of the olefin polymerization catalyst component; in the order listed, wherein an internal electron donor (ID) is added in any step prior to step c), said internal electron donor (ID) being a non-phthalic acid internal electron donor; The washing step d) is d1) one or more washes with a wash solution of aromatic and / or aliphatic hydrocarbons and optionally an internal electron donor (ID), d2) one or more washes with a wash solution consisting only of titanium tetrachloride and an internal electron donor (ID); and d3) One or more washes with aromatic and / or aliphatic hydrocarbon wash solutions in the order listed, wherein at least one of the one or more washes with said washing solution of step d2) is performed at a temperature in the range of 85 to 120°C.

2. The aromatic and / or aliphatic hydrocarbon of step d1) is selected from toluene, hexane, or pentane; 2. The process according to claim 1, wherein the aromatic and / or aliphatic hydrocarbons of step d3) are selected from toluene, hexane or pentane.

3. The method described in claim 1, wherein at least one of the one or more washes with the cleaning solution in step d2) is carried out at a temperature in the range of 90 to 110°C.

4. 2. The method of claim 1, wherein the washing solution of step d1) is a washing solution of an internal electron donor (ID) and an aromatic and / or aliphatic hydrocarbon.

5. 10. The method of claim 1, wherein step d2) comprises washing two or more times with the washing solution of step d2).

6. 10. The method of claim 1, wherein all of the washings with the washing solution of step d2) are carried out at a temperature in the range of 85 to 120°C.

7. The washing step d) is d4) One or more washes with an internal electron donor (ID) and an aromatic and / or aliphatic hydrocarbon wash solution.

2. The method of claim 1, further comprising the steps of: d4) being performed after d2) and before d3).

8. 8. The method according to claim 7, wherein the molar ratio ([ID] / [Mg]) between the amount of internal electron donor (ID) added in step d4) and the amount of magnesium in the Ziegler-Natta catalyst component is in the range of 0.01 to 0.

20.

9. The method described in claim 7, wherein the molar ratio ([ID] / [Mg]) between the amount of internal electron donor (ID) added in step d4) and the amount of magnesium in the Ziegler-Natta catalyst component is in the range of 0.03 to 0.

10.

10. 10. The method of claim 1, wherein the non-phthalic internal electron donor is a non-phthalic diester.

11. 11. The method of claim 10, wherein the non-phthalic internal electron donor is selected from the group consisting of maleic acid esters, citraconic acid esters, cyclohexene-1,2-dicarboxylic acid esters, and derivatives and / or mixtures of any of these.

12. The method of claim 10, wherein the non-phthalic acid internal electron donor is a citraconic acid ester internal electron donor.

13. After step e), the Ziegler-Natta catalyst component is further modified with a polymer nucleating agent obtained by polymerizing a vinyl monomer of formula (I), H ２ C=CH-CHR １ R ２ (I) In the formula, R １ and R ２ independently represent a lower alkyl group containing 1 to 4 carbon atoms, or together with the carbon atom to which they are attached form an optionally substituted saturated, unsaturated or aromatic ring or fused ring system, said ring or fused ring moiety containing 4 to 20 carbon atoms The method of claim 1.

14. The method of claim 13, wherein R 1 and R 2 together with the carbon atoms to which they are attached form a 5- to 12-membered saturated, unsaturated, or aromatic ring or fused ring system.

15. 1. A method for producing a polypropylene composition, comprising: a) providing a solution of at least one magnesium component; b) adding the solution from step a) to a titanium (IV) compound, thereby obtaining solid catalyst component particles; c) recovering the solid catalyst component particles from the solution obtained from step b); d) washing the solid catalyst component particles; e) recovering the solid catalyst component particles of the olefin polymerization catalyst component; in the order listed, wherein an internal electron donor (ID) is added in any step prior to step c), said internal electron donor (ID) being a non-phthalic acid internal electron donor; The washing step d) is d1) one or more washes with a wash solution of aromatic and / or aliphatic hydrocarbons and optionally an internal electron donor (ID), d2) one or more washes with a wash solution consisting only of titanium tetrachloride and an internal electron donor (ID); and d3) One or more washes with aromatic and / or aliphatic hydrocarbon wash solutions in the order listed, wherein at least one of the one or more washes with said washing solution of step d2) is carried out at a temperature in the range of 85 to 120°C; further comprising the step of polymerizing propylene with a comonomer optionally selected from a C2 or C4 to C12 alpha olefin in the presence of a Ziegler-Natta catalyst system comprising a Ziegler-Natta catalyst composition comprising the solid catalyst component recovered in step e), a cocatalyst (Co), and optionally an external donor (ED). method.

16. The method of claim d1), wherein the aromatic and / or aliphatic hydrocarbon is selected from toluene, hexane, or pentane; 16. The method according to claim 15, wherein the aromatic and / or aliphatic hydrocarbons of step d3) are selected from toluene, hexane or pentane.

17. The method of claim 15, wherein at least one of the one or more washes with the cleaning solution in step d2) is carried out at a temperature in the range of 90 to 110°C.

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