CATALYST SYSTEM FOR THE POLYMERIZATION OF AN OLEFINE, ITS PREPARATION PROCESS, POLYOLEFINE AND THE S

专利摘要:
catalyst system for the polymerization of an olefin. the present invention relates to a process for preparing a suitable catalyst system for polymerization of olefin, comprising the steps of: a) providing the pro-catalyst obtainable by a process comprising the steps: i) contacting a compound r4zmgx4 2-z with a silane compound containing alkoxy or aryloxy to give a first intermediate reaction product; ii) optionally contacting the solid product obtained in step i) with at least one activating compound selected from the group formed by the activating electron and metal alkoxide donor compounds; iii) contacting the first or second intermediate reaction products obtained, respectively, in step i) or ii), with a ti compound containing halogen and, optionally, internal electron donor to obtain the pro-catalyst; b) contact the pro-catalyst with a cocatalyst and at least diethylaminotrietoxysilane as an external donor. the invention further relates to a catalyst system obtained or obtainable by the process of the present invention and to a process for the preparation of a polyolefin by contacting at least one olefin with the catalyst system according to the invention. in addition, the invention relates to the polyolefin obtained or obtainable by the process for preparing a polyelefin according to the present invention and for a composition comprising a propylene-ethylene copolymer and a molded article thereof. in addition, the invention relates to the use of polyolefin.
公开号:BR112016014027B1
申请号:R112016014027-3
申请日:2014-12-19
公开日:2021-03-23
发明作者:Aurora Alexandra Batinas-Geurts；Martin Alexander Zuideveld；Raymond Gerlofsma；Henrica Norberta Alberta Maria Steenbakkers-Menting；Peter Degenhart
申请人:Sabic Global Technologies B.V.；Saudi Basic Industries Corporation；
IPC主号:

专利说明:

[0001] [001] The present invention relates to a catalyst system comprising a pro-catalyst, a cocatalyst and one or more external electron donors.
[0002] [002] The catalyst system of the present invention is suitable for the polymerization of olefins. The invention also relates to a process for obtaining a polyolefin by applying said catalyst system and to a polyolefin obtainable by said process. In addition, the present invention relates to the use of said polyolefin.
[0003] [003] Catalyst systems and their components that are suitable for the preparation of a polyolefin are generally known. One type of such catalyst is generally referred to as Ziegler-Natta catalysts. The term "Zieger-Natta" is known in the art and typically refers to catalyst systems that comprise a solid catalyst compound that contains transition metal (also typically referred to as a pro-catalyst); an organometallic compound (also typically referred to as a cocatalyst) and, optionally, one or more electron donor compounds (for example, external electron donors).
[0004] [004] The solid catalyst compound containing a transition metal comprises a transition metal halide (e.g., titanium halide, chromium halide, hafnium halide, zirconia halide, vanadium halide) supported on a metal component or metalloid (for example, a magnesium compound or a silica compound. An overview of such types of catalysts is given, for example, by Pullukat and R. Hoff in Catal. Rev. - Sci. Eng. 41, vol. 3 and 4, 389-438, 1999. The preparation of such a pro-catalyst is described, for example, in W096 / 32427 A1.
[0005] [005] EP 1 783 145 describes an external dialkylamine trialkoxysilane donor and its use in olefin polymerization using catalysts. US 2005/202958 describes an external dialkylamine trialkoxysilane donor and its use in olefin polymerization using catalysts. WO 2013/019351 describes semicrystalline polyolefin compositions comprising a thermoplastic crystallizable polyolefin and one or more dialkyl bis-oxalamide compounds. EP 1 270 651 describes polymeric films that comprise random polypropylene copolymers.
[0006] [006] Polyolefins are known to emit volatiles. The volatile fraction of a polymer is associated with the content of oligomers. Volatile emissions from polymers are associated with environmental and health risks. Therefore, there is an ongoing need in the industry to reduce the volatile fraction in polymers.
[0007] [007] For polyolefins, it is important to be able to adjust the properties of polyolefin materials and in particular to obtain combinations of desirable properties and to reduce unwanted properties, depending on the intended application. This is a problem, since optimizing a polyolefin property usually results in a decrease in other properties or the occurrence of unwanted side effects. With respect to volatiles, it is desirable to reduce the volatile fraction in a polymer while the mechanical properties are maintained.
[0008] [008] Another problem that can occur with polymers is "blooming". Blooming is not desired, as it will negatively affect the optical appearance of an article prepared with said composition. Another problem that can occur is static electricity which is discussed in detail below.
[0009] [009] Therefore, it is an object of the invention to provide an improved catalyst system for the polymerization of olefins and a process for preparing such a system.
[0010] [0010] It is an additional objective of the present invention to provide a pro-catalyst that shows better performance in the polymerization of olefins.
[0011] [0011] It is another objective of the invention to reduce the volatiles in polyolefins and / or to reduce the static effect. It is of particular interest to reduce volatiles while the mechanical properties of the polyolefin are maintained.
[0012] [0012] It is another objective of the invention to provide a catalyst system that reduces or prevents blooming in polyolefins. It is of particular interest to reduce blooming while other parameters of the polymer are controlled, such as the fraction soluble in xylene, which affects certain mechanical properties of the polymer.
[0013] [0013] One or more of the aforementioned objectives of the present invention are achieved by the various aspects of the present invention.
[0014] [0014] The present invention relates to the use of alkoxy alkylaminosilanes, especially diethylamino triethoxysilane (DEATES) as internal donors in a Ziegler-Natta catalyst system.
[0015] [0015] It has been surprisingly discovered by the present inventors that the external donor according to the present invention shows a reduced and reduced static emission. Summary of the Invention
[0016] [0016] In a first aspect, the present invention relates to a process for the preparation of a suitable catalyst system for the polymerization of an olefin, said process comprising the steps of: A) supply the said pro-catalyst obtainable through a process that comprises the steps of: contacting a compound R4zMgX42-z with a silane compound containing alkoxy or aryloxy to give a first intermediate reaction product, a solid Mg (OR1) xX12-x, where: R4 is equal to R1 which is a linear hydrocarbyl group , branched or cyclic independently selected from the alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups and one or more combinations thereof; wherein said hydrocarbyl group may be substituted or unsubstituted, may contain one or more heteroatoms and preferably has between 1 and 20 carbon atoms; X4 and X1 are each selected independently from the group consisting of fluoride (F-), chloride (Cl-), bromide (Br-) or iodide (I-), preferably chloride; z is in the range of greater than 0 and less than 2, with 0 <z <2; optionally contact the Mg (OR1) xX2-x obtained in step i) with at least one activating compound selected from the group formed by the electron donating and metal alkoxide activating compounds of the formula M1 (OR2) vw (OR3) w or M2 ( OR2) vw (R3) w to obtain a second intermediate product; where M1 is a metal selected from the group consisting of Ti, Zr, Hf, Al or Si; M2 is a metal that is Si; v is the valence of M1 or M2; R2 and R3 are each, a linear, branched or cyclic hydrocarbyl group independently selected from the alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups and one or more combinations thereof; wherein said hydrocarbyl group may be substituted or unsubstituted, may contain one or more heteroatoms and preferably has between 1 and 20 carbon atoms; contacting the first or second intermediate reaction products obtained, respectively, in step i) or ii), with a Ti compound containing halogen and, optionally, an internal electron donor to obtain said pro-catalyst; B) contacting said pro-catalyst with a cocatalyst and the at least one external electron donor is diethylaminotrietoxysilane (DEATES) according to formula III.
[0017] [0017] In one embodiment, said process is essentially phthalate free.
[0018] [0018] In an embodiment of said process, the optional internal electron donor is an aminobenzoate according to Formula XI.
[0019] [0019] In an embodiment of said process, said optionally one or more internal electron donors is activated by an activator, preferably when the activator is a benzamide according to Formula X:
[0020] [0020] In one embodiment, the benzamide according to formula X is present in the pro-catalyst in an amount between 0.1 to 4% by weight as determined using HPLC, for example, between 0.1 to 3.5% by weight, for example between 0.1 to 3% by weight, for example between 0.1 to 2.5% by weight, for example between 0.1 to 2% by weight, for example between 0.1 to 1, 5% by weight.
[0021] [0021] In another aspect, the present invention relates to a catalyst system obtained or obtainable by the process of the present invention.
[0022] [0022] In another aspect, the present invention relates to a process for preparing polyolefin by contacting at least one olefin with the catalyst system according to the invention, wherein the olefin is preferably propylene or a mixture of propylene and ethylene.
[0023] [0023] In another aspect, the present invention relates to a polyolefin obtained or obtainable by the process for the preparation of a polyolefin according to the present invention, preferably a polypropylene of a propylene-ethylene copolymer.
[0024] [0024] In another aspect, the present invention relates to a composition comprising a propylene-ethylene copolymer that has a content soluble in xylene (XS) less than 7.5% by weight, in which XS is measured according to with ASTM D 5492-10 and which has an increase in efflorescence over 21 days at 50 ° C of less than 12, for example, less than 11, where the increase in efflorescence over 21 days at 50 ° C is the difference between the efflorescence value of the sample before heating and the efflorescence value after heating at 50 ° C for 21 days and in which the opcity value is measured in a BYK Gardner according to ASTM D 1003-00 , procedure A, in which the amount of ethylene in the propylene-ethylene copolymer is in the range of 1 to 8% by weight, based on the propylene-ethylene copolymer.
[0025] [0025] In one embodiment, the present invention relates to a composition comprising a propylene-ethylene copolymer that has a content soluble in xylene (XS) less than 7.5% by weight, in which XS is measured according to with ASTM D 5492-10.
[0026] [0026] In one embodiment, the present invention relates to a composition that has an increase in efflorescence over 21 days at 50 ° C of less than 12, in which the increase in efflorescence over 21 days at 50 ° C is the difference between the efflorescence value of the sample before heating and the efflorescence value after heating at 50 ° C for 21 days and in which the efflorescence value is measured in a BYK Gardner according to ASTM D 1003-00 , procedure A.
[0027] [0027] In one embodiment, the present invention relates to a composition that has an increase in efflorescence over 21 days at 50 ° C of less than 11.
[0028] [0028] In one embodiment, the present invention relates to a composition in which the amount of ethylene in the propylene-ethylene copolymer is in the range of 1 to 8% by weight based on the propylene-ethylene copolymer.
[0029] [0029] In another aspect, the present invention relates to a formatted article comprising the polyolefin or the composition according to the present invention.
[0030] [0030] In another aspect, the present invention relates to the use of said polyolefin.
[0031] [0031] These aspects and modalities will be described in more detail below.
[0032] [0032] The catalyst system provided by the present invention provides polyolefins that have a reduced volatile fraction when compared to corresponding polymers produced using the reference catalyst systems. In particular, the catalyst system is capable of reducing volatiles in polyolefins while retaining the desired mechanical properties, in particular the mechanical strength.
[0033] [0033] The catalyst system provided by the present invention also provides polyolefins that exhibit reduced efflorescence, when compared to corresponding polymers produced using the reference catalyst systems. In particular, efflorescence while controlling the soluble fraction of xylene that affects certain mechanical properties of the polymer. Definitions
[0034] [0034] The following definitions are used in the present description and in the claims to define the subject in question. Other expressions not mentioned below are intended to have the commonly accepted meaning in the field.
[0035] [0035] "Ziegler-Natta catalyst" as used in the present description means: a solid catalyst compound containing a transition metal comprising a transition metal halide selected from a titanium halide, chromium halide, hafnium halide, zirconia halide, vanadium halide, supported on a metal or metalloid compound (for example, a magnesium compound or a silica compound).
[0036] [0036] "Ziegler-Natta catalytic species" or "catalytic species" as used in this description means: a species containing a transition metal comprising a transition metal halide selected from a titanium halide, chromium halide, hafnium halide, zirconia halide, vanadium halide.
[0037] [0037] "Internal donor" or "internal electron donor" or "ID" as used in this description means: a compound that donates an electron that contains one or more oxygen (O) and / or nitrogen (N) atoms. This ID is used as a reagent in the preparation of the solid pro-catalyst. An internal donor is commonly described in the prior art for the preparation of a Ziegler-Natta catalyst system supported by a solid for olefin polymerization; that is, by contacting a support containing magnesium with a Ti compound containing halogen and an internal donor.
[0038] [0038] "External donor" or "external electron donor" or "ED" as used in the present description means: an electron donating compound used as a reagent in the polymerization of olefins. An ED is an added compound independent of the pro-catalyst. It is not added during the formation of the pro-catalyst. It contains at least one functional group that is capable of donating at least one pair of electrons to a metal atom. ED can influence the properties of the catalyst, its non-limiting examples affecting the stereoselectivity of the catalyst system in the polymerization of olefins that have 3 or more carbon atoms, sensitivity to hydrogen, sensitivity to ethylene, the randomness of the comonomer incorporation and productivity of the catalyst.
[0039] [0039] "Activator" as used in the present description means: an electron donor compound containing one or more oxygen (O) and / or nitrogen (N) atoms, which is used during the synthesis of the pro-catalyst before or simultaneously adding an internal donor.
[0040] [0040] "Activating compound" as used in the present description means: a compound used to activate the solid support before contacting it with the catalyst species.
[0041] [0041] "Modifier" or "transition metal or Group 13 modifier" as used in the present description means: a metal modifier comprising a metal selected from the metals in Group 13 of the Periodic Table of the Elements and transition metals of the IUPAC. Where the description of the terms metal modifier or metal based modifier is used, it is understood as a transition metal or Group 13 modifier.
[0042] [0042] "Pro-catalyst" or "catalyst component" as used in the present description has the same meaning: a component of a catalyst composition that comprises a solid support, a catalytic species that contains a transition metal and optionally one or more donors internal.
[0043] [0043] "Halide" as used in the present description means: an ion selected from the group of fluoride (F-), chloride (Cl-), bromide (Br-) or iodide (I-).
[0044] [0044] "Halogen" as used in the present description means: an atom selected from the group of: fluorine (F), chlorine (Cl), bromine (Br) or iodide (I).
[0045] [0045] "Heteroatom" as used in this description means: an atom other than carbon or hydrogen. However, as used here - unless otherwise specified, as below, - when "one or more heteroatoms" are used, it means one or more of: F, Cl, Br, I, N, O, P, B , S or Si.
[0046] [0046] "Heteroatoms selected from group 13, 14, 15, 16 or 17 of the IUPAC Periodic Table of Elements" as used in this description means: a heteroatom 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, CI, Br, I, At [ Group 17].
[0047] [0047] "Hydrocarbyl" as used in the present description means: a substituent containing hydrogen and carbon atoms or a linear, branched or cyclic saturated or unsaturated aliphatic radical, such as alkyl, alkenyl, alkenyl and alkenyl; alicyclic radical, such as cycloalkyl, cycloalkylenyl, cycloalkenyl; aromatic radical such as a monocyclic or polycyclic radical, as well as combinations thereof, such as alkaryl or aralkyl.
[0048] [0048] "Substituted hydrocarbyl" as used in the present description means: a hydrocarbyl group that is substituted by one or more non-hydrocarbyl substituent groups. An example of a non-hydrocarbyl substituent is a heteroatom. Examples are the alkoxycarbonyl groups (i.e., carboxylate). When, in the present description, "hydrocarbyl" is used, it can also be "substituted hydrocarbyl", unless otherwise stated.
[0049] [0049] "Alkyl" as used in the present description means: an alkyl group that has a functional group or side chain that consists of carbon and hydrogen atoms that have only single bonds. An alkyl group can be linear or branched and can be unsubstituted or substituted. It may or may not contain heteroatoms such as oxygen (O), nitrogen (N), phosphorus (P), silicon (Si) or sulfur (S). An alkyl group also comprises arylalkyl groups in which one or more hydrogen atoms in the alkyl group have been replaced by aryl groups,
[0050] [0050] "Aryl" as used in the present description means: an aryl group that has a functional group or side chain derived from an aromatic ring. An aryl group can be unsubstituted or substituted with straight or branched hydrocarbyl groups. It may or may not contain heteroatoms such as oxygen (O), nitrogen (N), phosphorus (P), silicon (Si) or sulfur (S). An aryl group also encompasses alkaryl groups in which one or more hydrogen atoms in the aromatic ring have been replaced by alkyl groups.
[0051] [0051] "Alkoxide" or "alkoxy" as used in the present description means: a functional group or side chain obtained from an alkyl alcohol. It consists of alkyl attached to a negatively charged oxygen atom.
[0052] [0052] "Aryloxide" or "aryloxy" or "phenoxide" as used in the present description means: a functional group or side chain obtained from an aryl alcohol. It consists of an aryl attached to a negatively charged oxygen atom.
[0053] [0053] "Grignard reagent" or "Grignard compound" as used in the present description means: a compound or a mixture of compounds of the formula R4zMgX42-z (R4, z and X4 are as defined below) or it can be a complex that has more Mg clusters, for example, R4Mg3Cl2.
[0054] [0054] "Polymer" as used in the present description means: a chemical compound that comprises repeated structural units, where the structural units are the monomers.
[0055] [0055] "Olefin" as used in the present description means: an alkene.
[0056] [0056] "Olefin-based polymer" or "polyolefin" as used in the present description means: a polymer of one or more alkenes.
[0057] [0057] "Propylene based polymer" as used in the present description means: a propylene polymer and, optionally, a comonomer.
[0058] [0058] "Polypropylene" as used in the present description means: a propylene polymer.
[0059] [0059] "Copolymer" as used in the present description means: a polymer prepared from two or more different monomers.
[0060] [0060] "Monomer" as used in the present description means: a chemical compound that can be subjected to polymerization.
[0061] [0061] "Thermoplastic" as used in the present description means: able to soften or melt when heated and to harden again when cooled.
[0062] [0062] "Polymer composition" as used in the present description means: a mixture of two or more polymers or one or more polymers and one or more additives.
[0063] [0063] "Mw" and "Mn" in the context of the present invention means the proportion of the weighted average molecular weight Mw and the average numerical molecular weight Mn of a sample, as measured according to ASTM D6474-12.
[0064] [0064] "PDI" in the context of the present invention means the ratio between the weighted average molecular weight Mw and the average numerical molecular weight Mn of a sample, as measured according to ASTM D6474-12. As used here, the expressions "PDI" and "polydispersity index" are alternative.
[0065] [0065] "MWD" in the context of the present invention means the distribution of the molecular weight of a sample, as represented by the ratio between the weighted average molecular weight Mw and the average numerical molecular weight Mn of a sample, as measured according to ASTM D6474 -12. As used here, the expressions "MWD" and "molecular weight distribution" are alternatives.
[0066] [0066] "XS" as used in the present description means: the fraction soluble in xylene in terms of percentage of polymer that does not precipitate after cooling a polymer solution in xylene, said polymer solution having been subjected to reflux conditions , below the reflux temperature, which is equal to the boiling temperature of xylene, to 25 ° C. XS is measured according to ASTM D5492-10. As used here, the expressions "XS" and "fraction soluble in xylene" are alternatives.
[0067] [0067] "Efflorescence" as used in the description means the dispersion of light by a specimen responsible for the reduction in contrast of the objects visualized through it. Efflorescence is expressed as the percentage of transmitted light that is scattered such that its direction deviates at more than a specific 2.5 ° angle from the direction of the incident light beam. Efflorescence is measured according to ASTM D1003-00, procedure A.
[0068] [0068] "Increase in efflorescence" as used in this description means the difference in efflorescence between a measurement in a sample in accordance with ASTM D1003-00, procedure A, when prepared and a measurement in the same said sample in accordance with ASTM D1003-00, procedure A, after exposing said sample to a temperature of 50 ° C for a period of 21 days. As used here, the expressions "increased efflorescence" and "opacity" are alternatives.
[0069] [0069] "Impact" or "impact performance" or "impact resistance" as used in this description is measured by the IZod RT impact test according to ISO 180 / A at room temperature expressed in kJ / m2 on bars of polypropylene that have a dimension of 65 x 12.7 x 3.2 mm (prepared by injection molding at a melting temperature of 240 ° C and a mold temperature of 45 ° C) using type A fittings.
[0070] [0070] "Flexural modulus" in the context of the present invention means the modulus of elasticity according to ASTM D790-10, measured according to procedure A.
[0071] [0071] "Polymerization conditions" as used in the present description mean: temperature and pressure parameters within a suitable polymerization reactor to promote polymerization between the catalyst composition and an olefin to form the desired polymer. These conditions depend on the type of polymerization used.
[0072] "Production rate" or "yield" as used in the present description means: the amount of kilograms of polymer produced per gram of catalyst composition consumed in the polymerization reactor per hour, unless otherwise stated.
[0073] [0073] "MFR" as used in the present description means the melt flow rate as measured according to ISO 1133: 2005, at 230 ° C under a load of 2.16 kg. As used here, the expressions "MFR", "melt flow rate" and "melt flow rate" are alternatives.
[0074] [0074] Unless otherwise stated, when it is determined that any R group is "independently selected from", it means that when several of the same 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 R2M, where R is independently selected from ethyl or methyl, both groups R can be ethyl, both groups R can be methyl or one group R can be ethyl and the other group R can be methyl.
[0075] [0075] The present invention will be described in more detail below. All of the modalities described with respect to one aspect of the present invention are also applicable to the other aspects of the invention, unless otherwise stated.
[0076] [0076] As determined above, the external donor DEATES according to the present invention shows a better result with respect to the emission in the polyolefins produced using that donor in a catalyst system, in other words it exhibits a lower emission.
[0077] [0077] Another advantage of the present invention is that the external donor according to the invention shows a better result with respect to efflorescence in the polyolefins produced using that donor in a catalyst system. They show a better effect with respect to static.
[0078] [0078] The present invention relates to dialkylamino-alkoxysilanes, especially diethylaminotrietoxysilane as an external donor. One of the functions of an external donor compound is to affect the stereoselectivity of the catalyst system in the polymerization of olefins that have three or more carbon atoms. Therefore, it can also be referred to as a selectivity control agent. In addition to DEATES, one or more additional external donors can be used in the preparation of a catalyst system according to the present invention.
[0079] [0079] Mixtures of external donors may be present and may include between about 0.1 mol% to about 99.9 mol% of a first external donor (DEATES) and between about 99.9 mol% to about 0.1 mol% of a second external donor or an additional alkoxysilane described below (for example, an alkyl trialoxysilane or dialkylamine trialkoxysilane). The combination of DEATES with other donors can also be used. In one embodiment, DEATES is the only external donor used.
[0080] [0080] The molar ratio of aluminum / external donor in the polymerization catalyst system is preferably between 0.1 and 200; more preferably between 1 and 100. In a Ti-based catalyst, the molar ratio of Si / Ti in the catalyst system can vary between 0.1 to 40, preferably between 0.1 to 20, even more preferably between 1 to 20 and the more preferably between 2 to 10.
[0081] [0081] EP1538167 and EP1783145 describe a type of Ziegler-Natta catalyst comprising an organo-silicon compound as an external donor which is represented by the formula Si (ORc) 3 (NRdRe), where Rc is a hydrocarbon group which has 1 to 6 carbon atoms, Rd is a hydrocarbon group that has 1 to 12 carbon atoms or hydrogen atom and Re is a hydrocarbon group that has 1 to 12 carbon atoms used as an external electron donor.
[0082] [0082] Another example of an additional suitable external donor according to the present invention is a compound according to Formula III. DEATES also complies with Formula III as discussed below: (R90) 2N-A-Si (OR91) 3 Formula III
[0083] [0083] The groups R90 and R91 are each, independently, an alkyl having between 1 and 10 carbon atoms. Said alkyl group can be linear, branched or cyclic. Said alkyl group can be substituted or unsubstituted. Preferably, said hydrocarbyl group has between 1 and 8 carbon atoms, even more preferably between 1 and 6 carbon atoms, even more preferably between 2 and 46 carbon atoms. Preferably, each R90 is ethyl. Preferably, each R91 is ethyl. A is a direct bond between nitrogen and silicon (in other words, it is not present) or an alkyl spacer that has 1 to 10 carbon atoms. A is preferably a direct link.
[0084] [0084] The external donor that is present in the catalyst system according to the present invention is diethylamino-triethoxysilane (DEATES) in which A is a direct bond, each R90 is ethyl and each R91 is ethyl in Formula II.
[0085] [0085] The present invention relates to a Ziegler-Natta type catalyst. A pro-catalyst of the Ziegler-Natta type generally comprises a solid support, a catalytic species that contains a transition metal and optionally one or more internal donors. The present invention furthermore relates to a catalyst system comprising a pro-catalyst of the Ziegler-Natta type, a cocatalyst and optionally an external electron donor. The expression "Ziegler-Natta" is known in the art.
[0086] [0086] The solid catalyst compound containing a transition metal comprises a transition metal halide (for example, titanium halide, chromium halide, hafnium halide, zirconia halide or vanadium halide) supported on a metal compound or metalloid (for example, a magnesium compound or a silica compound).
[0087] [0087] Specific examples of various types of Ziegler-Natta catalyst as described below, for example, as described in EP 1 273 595 of Borealis Technology, EP 0 019 330 from Dow, US 5,093,415 from Dow and US 6,825,146 of Dow.
[0088] [0088] As comparative examples, pro-catalysts are used according to prior art documents.
[0089] [0089] US 4,771,024 (see Pro-catalyst IV in the Examples of the present description) describes the preparation of a catalyst in column 10, row 61 to column 11, row 9. The "silica catalyst fabrication" section is incorporated in this application by reference. The process comprises combining the dried silica with a solution of carbonated magnesium (magnesium diethoxide in ethanol was bubbled with CO2). The solvent was evaporated at 85 ° C. The resulting solid was washed and a 50:50 mixture of titanium tetrachloride and chlorobenzene was added to the solvent along with ethyl benzoate. The mixture was heated to 100 ° C and the liquid filtered. Again, TiCl4 and chlorobenzene were added, followed by heating and filtration. A final addition of TiCl4 and chlorobenzene and benzoyl chloride was performed, followed by heating and filtration. After washing, the catalyst was obtained.
[0090] [0090] WO03 / 068828 (see Pro-catalyst III in the Examples of the present description) describes the preparation of a catalyst component on page 91 "preparation of solid catalyst components", the section of which is incorporated in the present application by reference. Magnesium chloride, toluene, chloropropane epoxy and tributyl phosphate were added under nitrogen to a reactor, followed by heating. Then, phthalic anhydride was added. The solution was cooled to -25 ° C and TiCl4 was added by dripping, followed by heating. An internal donor was added (1,3-diphenyl-1,3-propylene glycol dibenzoate, 2-methyl-1,3-diphenyl-1,3-propylene glycol dibenzoate, 1,3-diphenyl-1 dipropionate, 3-propylene glycol or 1,3-diphenyl-2-methyl-1,3-propylene glycol dipropionate) and after stirring, a solid was obtained which was washed. The solid was treated with TiCl4 in toluene twice, followed by washing to obtain a catalyst component.
[0091] [0091] US 4,866,022 (see Pro-catalyst II in the Examples of the present description) describes a catalyst component comprising a product formed by: A. forming a solution of a species containing magnesium from magnesium carbonate or carboxylate magnesium; B. precipitate solid particles from such a solution containing magnesium by treatment with a transition metal halide and an organosilane that has the formula: RnSiR'4-n, where n = 0 to 4 and where R is hydrogen or an alkyl, a haloalkyl or aryl radical that contains about ten carbon atoms or a halosylyl or haloalkylsilyl radical that contains one to about eight carbon atoms and R 'is OR or a halogen; C. precipitating such solid particles from a mixture containing a cyclic ether; and D. treating the precipitated particles with a transition metal compound and an electron donor. That process for the preparation of a catalyst is incorporated in the present application by reference.
[0092] [0092] The present invention is related to the so-called TiNo catalyst. It is a magnesium-based titanium halide catalyst, optionally comprising one or more internal donors. During the production process of polyolefins that use TiNo as a pro-catalyst, under certain conditions, static electricity may occur in the reactor, leading to undesirable static effects, such as a more problematic process due to the adherence of a sprayed product on the agitator and / or in the reactor wall (also known as inlay and / or lamination of the reactor). It was surprisingly discovered by the present inventors that the use of the electron donor DEATES containing N according to the present invention, shows a reduction in static during the polymerization reaction.
[0093] [0093] "Static" as used in this description means: effects of static electricity that can occur during the polymerization process in the reactor, causing the catalyst particles to stick to parts of the reactor such as the walls of the reactor and the equipment agitation.
[0094] [0094] The pro-catalyst of the Ziegler-Natta type in the catalyst system according to the present invention is obtained by the process as described in WO 2007/134851 A1. In Example I, the process is described in more detail. Example I, including all sub-examples (IA-IE) of WO 2007/134851 is incorporated into the present description. More details about the different modalities are described from page 3, line 29 to page 14 line 29 of WO 2007/134851. These modalities are incorporated by reference in the present description. This process produces the so-called pro-catalyst TiNo (see Pro-catalyst I in the Examples of the present description).
[0095] [0095] In the following part of the description, the different steps and phases of the process for the preparation of the pro-catalyst according to the present invention will be discussed.
[0096] [0096] The process for preparing a pro-catalyst according to the present invention comprises the following steps: -Phase A): preparation of a solid support for the pro-catalyst; -Phase B): optional activation of said solid support obtained in phase A) using one or more activating compounds to obtain an activated solid support; -Phase C): contact said solid support obtained in Phase A or said solid support activated from Phase B) with a catalytic species, in which Phase C) comprises one of the following: contacting said solid support obtained in Phase A or said solid support activated from Phase B) with a catalytic species to obtain said pro-catalyst; or contacting said solid support obtained in Phase A or said solid support activated in Phase B) with a catalytic species and one or more internal donors to obtain said pro-catalyst; or contacting said solid support obtained in Phase A or said solid support activated in Phase B) with a catalytic species and one or more internal donors to obtain an intermediate product; or contacting said solid support obtained in Phase A or said solid support activated from Phase B) with a catalytic species and an activator to obtain an intermediate product; -Phase D) optional: modify said intermediate product obtained in Phase C), in which phase D) comprises one of the following: modifying said intermediate product obtained in Phase C) with a Group 13 or transition metal modifier in the event that an internal donor was used during phase C), in order to obtain a pro-catalyst; modify said intermediate product obtained in Phase C) with a Group 13 or transition metal modifier and one or more internal donors in the event that an activator was used during phase C) in order to obtain a pro-catalyst ;
[0097] [0097] The pro-catalyst thus prepared can be used in the polymerization of olefins using an external donor (DEATES) and a cocatalyst.
[0098] [0098] The various steps used to prepare the catalyst according to the present invention are described in more detail below. Phase A: Preparation of a solid support for the catalyst
[0099] [0099] Preferably, a support containing magnesium is used in the process of the present invention. Said support containing magnesium is known in the art as a typical component of a Ziegler-Natta pro-catalyst. The following description explains the process for preparing the magnesium-based substrate. Other supports can be used.
[0100] [00100] The synthesis of supports containing magnesium, such as magnesium halide compounds, alkyl magnesium and aryl magnesium and also magnesium alkoxy and aryloxy magnesium for the production of polyolefin, particularly for the production of polypropylenes, is described, for example, in US4978648, WO096 / 32427A1, WO01 / 23441 A1, EP1283 222A1, EP1222 214B1; US5077357; US5556820; US4414132; US5106806 and US5077357, but the present case is not limited to the description of those documents.
[0101] [00101] Preferably, the process for preparing the solid support for the pro-catalyst according to the present invention comprises the following steps: step o) which is optional and step i). Step o) preparation of the Grignard reagent (optional)
[0102] [00102] A Grignard reagent, R4zMgX42-z used in step i) can be prepared by contacting metallic magnesium with an organic halide R4X4, as described in WO 96/32427 A1 and WO01 / 23441 A1. All forms of metallic magnesium can be used, but preferably finely divided metallic magnesium is used, for example, powdered magnesium. For a quick reaction, it is preferable to heat the magnesium under nitrogen before use.
[0103] [00103] R4 is a hydrocarbyl group independently selected from alkyl, alkenyl, aryl, aralkyl, alkylaryl or alkoxycarbonyl groups, wherein said hydrocarbyl group can be linear, branched or cyclic and can be substituted or unsubstituted; said hydrocarbyl group preferably has between 1 to 20 carbon atoms or combinations thereof. The R4 group can contain one or more heteroatoms.
[0104] [00104] X4 is selected from the group consisting of fluoride (F-), chloride (Cl-), bromide (Br-) or iodide (I-).
[0105] [00105] The z value is in a range greater than 0 and less than 2: 0 <z <2. Combinations of two or more organic halides can also be used.
[0106] [00106] Magnesium and organic halide R4X4 can be reacted with each other without the use of a separate dispersant; the organic halide R4X4 is then used in excess.
[0107] [00107] The organic halide R4X4 and magnesium can also be brought into contact with each other and an inert dispersant. Examples of such dispersants are: aliphatic, alicyclic or aromatic dispersants that contain from 4 to 20 carbon atoms.
[0108] [00108] Preferably, in this step o) of the preparation of R4zMgX42-z, an ether can also be added to the reaction mixture. Examples of ethers are: diethyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether, diisoamyl ether, diallyl ether, tetrahydrofuran and anisol. Dibutyl ether and / or diisoamyl ether are preferably used. Preferably, an excess of chlorobenzene is used as the organic halide R4X4. Therefore, chlorobenzene serves as a dispersant as well as the organic halide R4X4.
[0109] [00109] The organic halide / ether ratio acts on the pro-catalyst activity. The volume ratio of chlorobenzene / dibutyl ether can vary, for example, between 75:25 and 35:65, preferably between 70:30 and 50:50.
[0110] [00110] Small amounts of iodine and / or alkyl halide can be added to make the reaction between the magnesium metal and the organic halide R4X4 occur at a high rate. Examples of alkyl halides are butyl chloride, butyl bromide and 1,2-dibromoethane. When the organic halide R4X4 is an alkyl halide, iodine and 1,2 dibromoethane are preferably used.
[0111] [00111] The reaction temperature for step o) of preparation of R4zMgX42-z is normally between 20 and 150 ° C; the reaction time is normally between 0.5 and 20 hours. After the reaction for the preparation of R4zMgX42-z is complete, the dissolved reaction product can be separated from the solid waste products. The reaction can be mixed. The agitation speed can be determined by the person skilled in the art and must be sufficient to agitate the reagents. Step 1) Reaction of a Grignard compound with a silane compound
[0112] [00112] Step i): contact a compound R4zMgX42-z - where R4, X4 and z are as discussed above - with a silane compound containing alkoxy or aryloxy to give a first intermediate reaction product. Said first intermediate reaction product is a solid support containing magnesium. It should be noted that with "containing alkoxy or aryloxy" it is understood to contain OR1. In other words, said silane compound containing alkoxy- or aryloxy- comprises at least one OR1 group. R1 is selected from the group consisting of a linear, branched or cyclic hydrocarbyl group independently selected, for example, from the alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups and one or more combinations thereof; wherein said hydrocarbyl group may be substituted or unsubstituted, may contain one or more heteroatoms and preferably has between 1 and 20 carbon atoms.
[0113] [00113] In step i), a first intermediate reaction product is prepared by contacting the following reagents: * a Grignard reagent - which is a compound or a mixture of compounds of formula R4zMgX42-z and * a silane compound containing alkoxy- or aryloxy. Examples of such reagents are described, for example, in WO 96/32427 A1 and WO01 / 23441 A1.
[0114] [00114] The compound R4zMgX42-z used as a starting product, is also referred to as a Grignard compound. In R4zMgX42-z, X4 is preferably chlorine or bromine, more preferably chlorine.
[0115] [00115] R4 can be an alkyl, aryl, aralkyl, alkoxide, phenoxide, etc. or their mixtures. Suitable examples of the R4 group are methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, hexyl, cyclohexyl, octyl, phenyl, tolyl, xylyl, mesity, benzyl, phenyl, naphthyl, thienyl, indolyl. In a preferred embodiment of the invention, R4 represents an aromatic group, for example, a phenyl group.
[0116] [00116] Preferably, as the Grignard compound R4zMgX42-z used in step i), a phenyl Grignard or butyl Grignard is used. The selection of phenyl Grignard or butyl Grignard depends on the requirements.
[0117] [00117] When a Grignard compound is used, a compound according to the formula R4zMgX42-z is desired. When phenyl Grignard is used, a compound according to the formula R4zMgX42-z wherein R4 is phenyl, for example, PhMgCl, is desired. When butyl Grignard is used, a compound according to the formula R4zMgX42-z wherein R4 is butyl, for example, BuMgCl or n-BuMgCl, is desired.
[0118] [00118] An advantage of using phenyl Grignard is that it is more active than butyl Grignard. Preferably, when butyl Grignard is used, an activation step that uses an aliphatic alcohol, such as methanol, is carried out in order to increase the activity. Such an activation step may not be necessary with the use of Grignard phenyl. A disadvantage of using phenyl Grignard is that the remaining benzene products may be present and that it is more expensive and therefore less commercially interesting.
[0119] [00119] An advantage of using butyl Grignard is that it is free of benzene and is commercially more interesting due to the lower price. A disadvantage of using butyl Grignard is that in order to have a high activity, an activation step is necessary.
[0120] [00120] The process for preparing a pro-catalyst for use in an embodiment of the present invention can be carried out using any Grignard compound, but the two set out above are the two most preferred.
[0121] [00121] In the Grignard compound of the formula R4zMgX42-z, z is preferably about 0.5 to 1.5.
[0122] [00122] The compound R4zMgX42-z can be prepared in an optional step (step o) which is discussed above, preceding step i) or can be obtained from a different process.
[0123] [00123] It is explicitly noted that it is possible that the Grignard compound used in step i) may alternatively have a different structure, for example, it may be a complex. Such complexes are already known to the person skilled in the art; a particular example of such complexes is PhenylI4Mg3Cl2.
[0124] [00124] The alkane- or aryloxy-containing silane used in step i) is preferably a compound or mixture of compounds with the general formula Si (OR5) 4-nR6n, in which it should be noted that the group R5 is the same as the group R1. The R1 group originates from the R5 group during the synthesis of the first intermediate reaction product.
[0125] [00125] R1 is a hydrocarbyl group independently selected, for example, from the alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups and one or more combinations of these. Said hydrocarbyl group can be linear, branched or cyclic. Said hydrocarbyl group can be substituted or unsubstituted. Said hydrocarbyl group may contain one or more heteroatoms. Preferably, said hydrocarbyl group has between 1 and 20 carbon atoms, but preferably between 1 to 12 carbon atoms, even more preferably between 1 and 6 carbon atoms. Preferably said hydrocarbyl group is an alkyl group, preferably having between 1 to 20 carbon atoms, more preferably between 1 to 12 carbon atoms, more preferably between 1 to 6 carbon atoms, such as, for example, methyl, ethyl, n-propyl, i-propyl, isopropyl, n-butyl, i-butyl, t-butyl sec-butyl, pentyl or hexyl; more preferably, selected from ethyl and methyl.
[0126] [00126] R6 is a hydrocarbyl group independently selected, for example, from the alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups and one or more combinations thereof. Said hydrocarbyl group can be linear, branched or cyclic. Said hydrocarbyl group can be substituted or unsubstituted. Said hydrocarbyl group may contain one or more heteroatoms. Preferably, said hydrocarbyl group has between 1 and 20 carbon atoms, but preferably between 1 to 12 carbon atoms, even more preferably between 1 and 6 carbon atoms. Preferably said hydrocarbyl group is an alkyl group, preferably having between 1 to 20 carbon atoms, more preferably between 1 to 12 carbon atoms, more preferably between 1 to 6 carbon atoms, such as, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl or cyclopentyl.
[0127] [00127] The value of n is in the range of 0 to 4, preferably 0 to 1, inclusive.
[0128] [00128] Examples of suitable silane compounds include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltributoxysilane, phenyltriethoxy-silane, diethyldiphenoxysilane, n-propyltriethoxysilane, diisopropylthiethyl-methyl-methoxy-methyl-methoxy-methoxy silane, phenyl-trimethoxysilane, diphenyl-dimethoxysilane, trifluoropropylmethyl-dimethoxysilane, bis (perhydroisoquinoline) -dimethoxysilane, dicyclohexyldimethoxy silane, dinorbornyl-dimethoxysilane, di (n-propyl) dimethoxysilane (di) butyl) dimethoxysilane and / or di (iso-butyl) dimethoxysilane.
[0129] [00129] Preferably, tetraethoxysilane is used as the silane compound in the preparation of the compound containing solid Mg during step i) in the process according to the present invention.
[0130] [00130] Preferably, in step i) the silane compound and the Grignard compound are introduced simultaneously into a mixing device to result in particles of the first reaction intermediate product having an advantageous morphology. This, for example, is described in WO 01/23441 A1. Here, "morphology" refers not only to the particle shape of the solid magnesium compound and the catalyst made from it, but also to the particle size distribution (also characterized as an interval, that is, an indicator as to the amplitude of the distribution particle size as measured according to ISO 13320: 2009), its fines content, powder fluidity and concentrate density (ie the weight per unit volume of a material, including the voids inherent in the material when tested ; measured as the apparent density according to ASTM D1895-96 Re-approved 2010-e1, test method A) of the catalyst particles. Furthermore, it is well known that a polyolefin powder produced in the polymerization process using a catalyst system based on such a pro-catalyst, has a similar morphology to that of the pro-catalyst (the so-called "replication effect"; see, for example , S. van der Ven, Polypropylene and other Polyolefins, Elsevier 1990, p. 8-10). Consequently, almost round polymer particles are obtained with a length / diameter (I / D) ratio of less than 2 and with good fluidity of the powder.
[0131] [00131] As discussed above, the reagents are introduced simultaneously. By "introduced simultaneously" it is understood that the introduction of the Grignard compound and the silane compound is done in such a way that the molar ratio of Mg / Si does not vary substantially during the introduction of these compounds into the mixing device, as described in WO 01/23441 A1.
[0132] [00132] The silane compound and the Grignard compound can be fed continuously or in batches to the mixing device. Preferably, both compounds are introduced continuously into the mixing device.
[0133] [00133] The mixing device can take several forms; it can be a device in which the silane compound is pre-mixed with the Grignard compound, the mixing device can also be a stirred reactor, in which the reaction between the compounds occurs. The separate components can be fed into the mixing device by means of peristaltic pumps.
[0134] [00134] Preferably, the compounds are pre-mixed before the mixture is introduced into the reactor for step i). Thus, a pro-catalyst is formed with a morphology that leads to polymer particles with the best morphology (high density of the concentrate, limited particle size distribution, (virtually) without fines, excellent fluidity).
[0135] [00135] The molar ratio between Si / Mg during step i) can vary between 0.2 to 20. Preferably, the molar ratio between Si / Mg is from 0.4 to 1.0.
[0136] [00136] The pre-mixing period of the reagents in the reaction step indicated above can vary between wide limits, for example, 0.1 to 300 seconds. Preferably, pre-mixing is carried out for 1 to 50 seconds.
[0137] [00137] The temperature during the premixing stage of the reagents is not specifically critical and can, for example, vary between 0 and 80 ° C; preferably, the temperature is between 10 ° C and 50 ° C.
[0138] [00138] The reaction between said reagents can, for example, occur at a temperature between -20 ° C and 100 ° C; for example, at a temperature between 0 ° C to 80 ° C. The reaction time is, for example, between 1 and 5 hours.
[0139] [00139] The speed of mixing during the reaction depends on the type of reactor used and the scale of the reactor used. The mixing speed can be determined by the person skilled in the art. As a non-limiting example, mixing can be performed at a mixing speed between 250 to 300 rpm. In one embodiment, when a stirring blade is used, the mixing speed is between 220 and 280 rpm and when a propeller stirrer is used, the mixing speed is between 270 and 330 rpm. The speed of the mixer can be increased during the reaction. For example, during feeding, the agitation speed can be increased every hour by 20 to 30 rpm.
[0140] [00140] The first intermediate reaction product obtained from the reaction between the silane compound and the Grignard compound is generally purified by decantation or filtration followed by washing with an inert solvent, for example, a hydrocarbon solvent with, for example , 1 to 20 carbon atoms, such as pentane, that-pentane, hexane or heptane. The solid product can be stored and used later as a suspension in said inert solvent. Alternatively, the product can be dry, preferably partially dry and preferably under moderate conditions; for example, at ambient temperature and pressure.
[0141] [00141] The first intermediate reaction product obtained by this step i) may comprise a compound of the formula Mg (OR1) xX12-x, in which:
[0142] [00142] R1 is a hydrocarbyl group independently selected, for example, from the alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups and one or more combinations thereof. Said hydrocarbyl group can be linear, branched or cyclic. Said hydrocarbyl group can be substituted or unsubstituted. Said hydrocarbyl group may contain one or more heteroatoms. Preferably, said hydrocarbyl group has between 1 and 20 carbon atoms, but preferably between 1 to 12 carbon atoms, even more preferably between 1 and 6 carbon atoms. Preferably said hydrocarbyl group is an alkyl group, preferably having between 1 to 20 carbon atoms, more preferably between 1 to 12 carbon atoms, more preferably between 1 to 6 carbon atoms. Most preferably, it is selected from ethyl and methyl.
[0143] [00143] X1 is selected from the group consisting of fluoride (F-), chloride (Cl-), bromide (Br-) or iodide (I-). Preferably, X1 is chloride or bromide and more preferably, X1 is chloride.
[0144] [00144] The value of x is in a range greater than 0 and less than 2: 0 <x <2. The value for x is preferably between 0.5 and 1.5. Phase B: Activation of said solid support for the catalyst
[0145] [00145] This step of activating said solid support for the pro-catalyst is an optional step that is not necessary, but is preferred, in the present invention. If this activation step is carried out, preferably the process of activating said solid support comprises the following step ii). This phase can comprise one or more stages. Step ii): activation of the solid magnesium compound
[0146] [00146] Step ii): contact the Mg (OR1) xX12-x solid with at least one activation compound selected from the group formed by the activating compounds of electron donors and metal alkoxide of formula M1 (OR2) vw (OR3) w or M2 (OR2) vw (OR3) w where:
[0147] [00147] R2 is a hydrocarbyl group independently selected, for example, from the alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups and one or more combinations thereof. Said hydrocarbyl group can be linear, branched or cyclic. Said hydrocarbyl group can be substituted or unsubstituted. Said hydrocarbyl group may contain one or more heteroatoms. Preferably, said hydrocarbyl group has between 1 and 20 carbon atoms, but preferably between 1 to 12 carbon atoms, even more preferably between 1 and 6 carbon atoms. Preferably said hydrocarbyl group is an alkyl group, preferably having between 1 to 20 carbon atoms, more preferably between 1 to 12 carbon atoms, more preferably between 1 to 6 carbon atoms, such as, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, pentyl or hexyl; most preferably, selected between ethyl and methyl.
[0148] [00148] R3 is a hydrocarbyl group independently selected, for example, from the alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups and one or more combinations thereof. Said hydrocarbyl group can be linear, branched or cyclic. Said hydrocarbyl group can be substituted or unsubstituted. Said hydrocarbyl group may contain one or more heteroatoms. Preferably, said hydrocarbyl group has between 1 and 20 carbon atoms, but preferably between 1 to 12 carbon atoms, even more preferably between 1 and 6 carbon atoms. Preferably said hydrocarbyl group is an alkyl group, preferably having between 1 to 20 carbon atoms, more preferably between 1 to 12 carbon atoms, more preferably between 1 to 6 carbon atoms; more preferably selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl and cyclopentyl.
[0149] [00149] M1 is a metal selected from the group consisting of Ti, Zr, Hf, Al or Si; v is the valence of M1; M2 is a metal that is Si; v is the valence of M2 and w is less than v.
[0150] [00150] Electron donors and compounds of the formula M1 (OR2) v-w (OR3) w or M2 (OR2) v-w (OR3) w can also be referred to as activator compounds.
[0151] [00151] In this step, one or both types of activating compounds (ie electron donor or activating metal alkoxides) can be used.
[0152] [00152] The advantage of using this activation step before contacting the solid support with the titanium compound containing halogen (phase C of the process) is that a higher yield of polyolefins per gram of pro-catalyst is obtained. In addition, the sensitivity to ethylene of the catalyst system in the copolymerization of propylene and ethylene is also increased due to this activation step. This activation step is described in detail in WO2007 / 134851 by the present applicant.
[0153] [00153] Examples of suitable activating electron donors that can be used in step ii) are known to the person skilled in the art and described here below, that is, include carboxylic acids, carboxylic acid anhydrides, carboxylic acid esters, acid halides carboxylics, alcohols, ethers, ketones, amines, amides, nitriles, aldehydes, alkoxides, sulfonamides, thio ethers, thio esters and other organic compounds that contain one or more heteroatoms, such as nitrogen, oxygen, sulfur and / or phosphorus.
[0154] [00154] Preferably, an alcohol is used as the activating electron donor in step ii). More preferably, the alcohol is a straight or branched aliphatic or aromatic alcohol that has 1 to 12 carbon atoms. Even more preferably, the alcohol is selected from methanol, ethanol, butanol, isobutanol, hexanol, xylene and benzyl alcohol. Most preferably, the alcohol is ethanol or methanol, preferably ethanol.
[0155] [00155] Carboxylic acids suitable as an activating electron donor can be aliphatic or (partially) aromatic. Examples include formic acid, acetic acid, propionic acid, butyric acid, isobutanoic acid, acrylic acid, methacrylic acid, maleic acid, fumaric acid, tartaric acid, monocarboxylic cyclohexanoic acid, dicarboxylic cis-1,2-cyclohexanoic acid, phenylcarboxylic acid, toluenecarboxylic acid, naphthalene carboxylic acid, phthalic acid, isophthalic acid, terephthalic acid and / or trimellitic acid.
[0156] [00156] The above mentioned carboxylic acid anhydrides can be cited as examples of carboxylic acid anhydrides, such as acetic acid anhydride, butyric acid anhydride and methacrylic acid anhydride.
[0157] [00157] Suitable examples of esters of the aforementioned carboxylic acids are formats, for example, butyl formate; acetates, for example, ethyl acetate and butyl acetate; acrylates, for example, ethyl acrylate, methyl methacrylate and isobutyl methacrylate; benzoate, for example, methyl benzoate and ethyl benzoate; methyl-p-toluate; ethyl naphthalate and phthalates, for example, monomethyl phthalate, dibutyl phthalate, diisobutyl phthalate, diallyl phthalate and / or diphenyl phthalate.
[0158] [00158] Suitable examples of carboxylic acid halides as electron activating donors are the carboxylic acid halides mentioned above, for example, acetyl chloride, acetyl bromide, propionyl chloride, butanoyl chloride, butanoyl iodide, benzoyl bromide , p-toluyl chloride and / or phthaloyl dichloride.
[0159] [00159] Suitable alcohols are straight or branched aliphatic alcohols such as 1 to 12 C atoms or aromatic alcohols. Examples include, methanol, ethanol, butanol, isobutanol, hexanol, xylenol and benzyl alcohol. Alcohols can be used alone or in combination. Preferably, the alcohol is ethanol or hexanol.
[0160] Examples of suitable ethers are diethers, such as 2-ethyl-2-butyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane and / or 9,9-bis (methoxymethyl) ) fluorene. Cyclic ethers such as tetrahydrofuran (THF) or tri-ethers can be used.
[0161] [00161] Suitable examples of other organic compounds that contain a heteroatom for use as an activating electron donor include 2,2,6,6-tetramethyl piperidine, 2,6-dimethylpiperidine, pyridine, 2-methylpyridine, 4-methylpyridine, imidazole, benzonitrile, aniline, diethylamine, dibutylamine, dimethylacetamide, thiophenol, 2-methyl thiophene, isopropyl mercaptan, diethylthioether, diphenylthioether, tetrahydrofuran, dioxane, dimethyl ether, diethyl ether, anisol, acetone, triphenylphenylphosphine, triphenylphenylphosphine and triphenylphenyl
[0162] [00162] Examples of metal alkoxides suitable for use in step ii) are the metal alkoxides of the formulas: M1 (OR2) vw (OR3) w or M2 (OR2) vw (OR3) w where M1, M2, R2, R3, v and w are as defined here. R2 and R3 can also be groups of aromatic hydrocarbons, optionally substituted, for example, with alkyl groups and can contain, for example, between 6 to 20 carbon atoms. R2 and R3 preferably comprise 1 to 12 or 1 to 8 carbon atoms. In preferred embodiments, R2 and R3 are ethyl, propyl or butyl; more preferably all groups are ethyl groups.
[0163] [00163] Preferably, M1 in said activating compound is Ti or Si. Compounds containing Si suitable as activating compounds are the same as listed above for step i).
[0164] [00164] The value of w is preferably 0, the activating compound being, for example, a titanium tetraloxide containing 4 to 32 carbon atoms in total from four alkoxy groups. The alkoxide groups in the compound can be the same or they can differ independently. Preferably, at least one of the alkoxy groups in the compound is an ethoxy group. Most preferably the compound is a tetraloxide, such as titanium tetraloxide.
[0165] [00165] A combination of a compound of M1 (OR2) vw (OR3) w or M2 (OR2) vw (OR3) w with an electron donor is preferably as an activating compound to obtain the catalyst system which, for example, shows high activity and from which sensitivity to ethylene can be affected by the selection of the internal donor; which is specifically advantageous in the preparation of copolymers of, for example, propylene and ethylene.
[0166] [00166] Preferably, a Ti-based compound, for example, titanium tetraethoxide, is used together with an alcohol, such as ethanol or hexanol or with an ester compound, such as ethyl acetate (EA), ethyl benzoate (EB) or a phthalate ester or together with an ether, such as dibutyl ether (DBE) or pyridine.
[0167] [00167] If two or more activating compounds are used in step ii), their order of addition is not critical, but it can affect the performance of the catalyst depending on the compounds used. A person skilled in the art can optimize his order of addition based on some experiments. The compounds of step ii) can be added together or sequentially.
[0168] [00168] Preferably, an electron donor compound is added first to the compound with the formula Mg (OR1) xX12-x, where afterwards a compound of the formula M1 (OR2) vw (OR3) w or M2 (OR2) vw (OR3) w as defined here is added. The activating compounds are preferably added slowly, for example, over a period of 0.1 to 6, preferably over 0.5-4 hours, most preferably over 1 to 2.5 hours, each.
[0169] [00169] The first intermediate reaction product that is obtained in step i) can be contacted - when more than one activating compound is used - in any sequence with the activating compounds. In one embodiment, an activating electron donor is added first to the first intermediate reaction product and then the compound M1 (OR2) v-w (OR3) w or M2 (OR2) v-w (OR3) w is added; in that order, no agglomeration of solid particles is observed. The compounds in step ii) are preferably added slowly, for example over a period of 0.1 to 6, preferably over 0.5-4 hours, most preferably over 1 to 2.5 hours, each.
[0170] [00170] The molar ratio of the activating compound to Mg (OR1) xX12-x can vary between wide limits and, for example, is between 0.02 and 1.0. Preferably, the ratio is between 0.05 and 0.5, more preferably between 0.06 and 0.4 or even between 0.07 and 0.2.
[0171] [00171] The temperature of step ii) can be in the range between -20 ° C to 70 ° C, preferably between -10 ° C to 50 ° C, more preferably in the range between -5 ° C to 40 ° C and more preferably in the range between 0 ° C and 30 ° C.
[0172] [00172] Preferably, at least one of the reaction components is fed at a time, for example, for 0.1 to 6, preferably for 0.5 to 4 hours, more particularly for 1 to 2.5 hours. The reaction time after the activating compounds have been added is preferably between 0 and 3 hours.
[0173] [00173] The mixing speed during the reaction depends on the type and scale of the reactor used. The mixing speed can be determined by the person skilled in the art and must be sufficient to stir the reagents.
[0174] [00174] The inert dispersant used in step ii) is preferably a hydrocarbon solvent. The dispersant can 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, heptane being most preferred.
[0175] [00175] Starting from a product that contains solid Mg of controlled morphology obtained in step i), said morphology is not negatively affected during the treatment with the activating compound during step ii). The second intermediate solid reaction product obtained in step ii) is considered to be an adduct of the compound containing MG and the at least one activating compound as defined in step ii) and is still of controlled morphology.
[0176] [00176] The second solid reaction intermediate product obtained after step ii) can be a solid and can be further washed, preferably also with the solvent used as an inert dispersant and stored and used later as a suspension in said inert solvent. Alternatively, the product can be dried, preferably partially dried, preferably slowly and under moderate conditions; for example, at ambient temperature and pressure. Phase C: Contact said solid support with the catalytic species and optionally one or more internal donors and / or activator
[0177] [00177] Phase C: contact the solid support with the catalytic species. This step can take different forms, such as i) contacting said solid support with the catalytic species to obtain said pro-catalyst; ii) contacting said solid support with the catalytic species and one or more internal donors to obtain said pro-catalyst; iii) contacting said solid support with the catalytic species and one or more internal donors to obtain an intermediate product; iv) contacting said solid support with the catalytic species and an activating donor to obtain an intermediate product.
[0178] [00178] The contact of the solid support with the catalytic species can comprise several stages (for example, I, II and / or III). During each of these consecutive stages the solid support is contacted with said catalytic species. In other words, the addition or reaction of said catalytic species can be repeated one or more times. The same or a different catalytic species can be used during these stages.
[0179] [00179] These stages can be divided during Phase C (for example, step iii) and Phase D (for example, step v) or step v-a) and v-b). It is possible that Phase C comprises one or more stages and that Phase D also comprises one or more stages.
[0180] [00180] For example, during stage I in phase C (step ii), the solid support (first intermediate) or the activated solid support (second intermediate) is contacted first with said catalytic species and optionally subsequently with one or more donors internal and optionally an activator. When a second stage is present, during stage II (in Stage C or Stage D), the intermediate product obtained from stage I will be contacted with an additional catalytic species that may be the same or different from the catalytic species added during the first stage and, optionally, one or more internal donors and optionally an activator.
[0181] [00181] In the case where the three stages are present, in one embodiment, stage III is v) of Stage D which is preferably a repetition of stage I or can comprise the contact of the product obtained from stage II with both, a catalytic species (which can be the same or different as above) and one or more internal donors. In other words, an internal donor can be added during each of these stages or during two or more of these stages. When an internal donor is added during more than one stage, it can be an equal or different internal donor. In one embodiment stage I is stage iii) of Stage C, stage II is stage v-a) of Stage D and stage III is stage v-b) of Stage D.
[0182] [00182] An activator according to the present invention - if used - can be added during stage I or stage II or stage III. An activator can also be added during more than one stage.
[0183] [00183] Preferably, the process of contacting the solid support with the catalytic species and an internal donor comprises the following step iii). Step iii) reaction of the solid support with a transition metal halide
[0184] [00184] Step iii) reaction of the solid support with the transition metal halide (for example, titanium halide, chromium, hafnium, zirconia or vanadium), but preferably titanium halide. In the discussion below only the process for a titanium-based Ziegler-Natta pro-catalyst is described, however, the present invention is also applicable to other types of Ziegler-Natta pro-catalysts.
[0185] [00185] Step iii): contact the first or second intermediate reaction product, obtained in step i) or ii), respectively, with a Ti compound containing halogen and optionally an internal electron donor or activator to obtain a third intermediate product .
[0186] [00186] Step iii) can be performed after i) on the first intermediate product or after step ii) on the second intermediate product.
[0187] [00187] The molar ratio in step ii) of the transition metal to magnesium is preferably between 10 and 100, most preferably between 10 and 50.
[0188] [00188] Preferably, an internal electron donor is also present during step iii). Mixtures of internal electron donors can also be used. Examples of internal electron donors are described below.
[0189] [00189] The molar ratio of the internal electron donor to magnesium can vary between wide limits, for example, between 0.02 and 0.75. Preferably, this molar ratio is between 0.05 and 0.4; more preferably between 0.1 and 0.4; and most preferably between 0.1 and 0.3.
[0190] [00190] During contact of the first or second intermediate products and the titanium compound containing halogen, an inert dispersant is preferably used. The dispersant is preferably chosen such that virtually all formed side products are dissolved in the dispersant. Suitable dispersants include, for example, aliphatic and aromatic hydrocarbons and halogenated aromatic solvents with, for example, 4 to 20 carbon atoms. Examples include toluene, xylene, benzene, heptane, o-chlorotoluene and chlorobenzene.
[0191] [00191] The reaction temperature during step iii) is preferably between 0 ° C and 150 ° C and more preferably between 100 ° C and 140 ° C. Most preferably, the reaction temperature is between 110 ° C and 125 ° C.
[0192] [00192] The reaction time during step iii) is preferably between 10 minutes and 10 hours. In the event that several stages are present, each stage can have a reaction time between 10 minutes and 10 hours. The reaction time can be determined by the person skilled in the art based on the type and scale of the reactor and the catalyst systems.
[0193] [00193] The speed of mixing during the reaction depends on the type of reactor used and the scale of the reactor used. The mixing speed can be determined by the person skilled in the art and must be sufficient to stir the reagents.
[0194] The obtained reaction product can be washed, generally with an aliphatic or aromatic hydrocarbon or a halogenated aromatic compound, to obtain the pro-catalyst of the invention. If desired, the reaction and subsequent purification steps can be repeated one or more times. A final wash is preferably carried out with an aliphatic hydrocarbon to result in a suspended or at least partially dry pro-catalyst as described above for the other steps.
[0195] [00195] Optionally, an activator is present during stage iii) of Phase C instead of an internal donor; this is explained in more detail in the activators section.
[0196] [00196] The molar ratio of the activator to magnesium can vary between wide limits, for example, between 0.02 and 0.5. Preferably, this molar ratio is between 0.05 and 0.4; more preferably between 0.1 and 0.3 and most preferably between 0.1 and 0.2.
[0197] [00197] Phase D: Modify said pro-catalyst with a metal-based modifier.
[0198] [00198] This D-phase is optional in the present invention. In a preferred process for modifying the supported pro-catalyst, this phase comprises the following step:
[0199] [00199] Step iv) modify the third intermediate product with a metal modifier to provide a modified intermediate product.
[0200] [00200] After step iv) - if this is done - an additional step of contacting the intermediate product with a catalytic species (in other words, an additional stage):
[0201] [00201] Step v) contact said intermediate product with a titanium halide and, optionally, one or more internal donors and / or activators to obtain the present pro-catalyst. In the case where no activator is used during Phase C, an activator is used during Phase v) of Phase D.
[0202] [00202] The order of addition, that is, the order of the first stage iv) and the subsequent stage v), is considered to be very important for the formation of the correct clusters of Group 13 or transition metal and titanium that form the catalytic center more active and modified.
[0203] [00203] Each of these steps is described in more detail below.
[0204] [00204] It should be noted that steps iii), iv) and v) (ie phases C and D) are preferably carried out in the same reactor, that is, in the same reaction mixture, one following the other directly.
[0205] [00205] 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. Step iv): modification with Group 13 or transition metal
[0206] [00206] The modification with Group 13 or transition metal, preferably aluminum, ensures the presence of Group 13 or transition metal in the pro-catalyst, in addition to magnesium (from the solid support) and titanium (from the titanization treatment) ).
[0207] [00207] Without wishing to be linked to any particular theory, the present inventors believe that a possible explanation is that the presence of Group 13 or transition metal increases the reactivity of the active site and, therefore, increases the yield of the polymer.
[0208] [00208] Step iv) comprises modifying the third intermediate product obtained in step iii) with a modifier that has the formula M (p) Xp, preferably MX3, where M is a metal selected from Group 13 metals and metals from transition from the periodic table of IUPAC elements, p is the oxidation state of M and where X is a halide to provide a modified intermediate product. In the case of the oxidation state of M, for example, aluminum, being three, M (p) is Al (III) there are three monovalent halides of X, for example, AlCl3 or AIF3. In the case of the oxidation state of M, for example, copper, to be two, M (p) is Cu (II) and there are two monovalent halides of X, CuBr2 or CuCl2.
[0209] [00209] Step iv) is preferably 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 trichloride and a solvent, for example chlorobenzene, is added to the reactor after step iii) has been carried out. After the reaction is complete, a solid is allowed to settle, which can be obtained by decanting or filtering, and optionally purified or a suspension of the solid in the solvent can be used for the next step, that is, step v).
[0210] [00210] The metal modifier is preferably selected from the group of aluminum modifiers (eg aluminum halides), boron modifiers (eg boron halides), gallium modifiers (eg gallium halides), modifiers zinc (for example, zinc halides), copper modifiers (for example, copper halides), thallium modifiers (for example, thallium halides), indium modifiers (for example, indium halides), vanadium modifiers (for example, vanadium halides), chromium modifiers (for example, chromium halides) and iron modifiers (for example, iron halides).
[0211] [00211] 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, fluoride copper, thallium trichloride, thallium tribromide, thallium triiodide, thallium trifluoride, thallium chloride, thallium bromide, thallium iodide, thallium fluoride, indium trichloride, indium trichloride, indium triiodide , vanadium trichloride, vanadium tribromide, vanadium triiodide, vanadium trifluoride, chromium trichloride, chromium dichloride, chromium tribromide, chromium dibromide, iron dichloride, iron trichloride, tribro iron methane, iron dichloride, iron triiodide, iron diiodide, iron trifluoride and iron difluoride.
[0212] [00212] The amount of metal halide added during step iv) can vary according to the desired amount of metal present in the pro-catalyst. It can vary, for example, between 0.1 to 5% by weight based on the total weight of the support, preferably between 0.5 and 1.5% by weight.
[0213] [00213] The metal halide is preferably mixed with a solvent before addition to the reaction mixture. The solvent for this step can be selected from, for example, aliphatic and aromatic hydrocarbons and halogenated aromatic solvents with, 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 of these.
[0214] [00214] The duration of the modification step can vary between 1 minute and 120 minutes, preferably between 40 and 80 minutes, more preferably between 50 and 70 minutes. This time is dependent on the concentration of the modifier, the temperature, the type of solvent used, etc.
[0215] [00215] The modification step is preferably carried out at elevated temperatures (for example, between 50 and 120 ° C, preferably between 150 to 300 rpm, more preferably about 200 rpm).
[0216] [00216] The weight / volume ratio of the metal halide and the solvent in step iv) is between 0.01 gram - 0.1 gram: 5.0 - 100 ml.
[0217] [00217] The modified intermediate product is present in the solvent. It can be kept in this solvent after the next step v) is performed directly. However, it can be isolated and / or purified. The solid can be allowed to settle by stopping the stirring. The supernatant can be removed by decanting. On the other hand, filtration 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 another solvent selected from the same group described above. The solid can be resuspended or it can be dried or partially dried for storage.
[0218] [00218] Subsequent to this step, step v) is carried out to produce the pro-catalyst according to the present invention. Step v): titanization of the intermediate product
[0219] [00219] This step is very similar to step iii). It refers to the additional titanization of the modified intermediate product. It is an additional stage of contact with the catalytic species (that is, titanization in this modality).
[0220] [00220] Step v): contact said intermediate product modified in step iv) as a titanium compound containing halogen to obtain the pro-catalyst. When an activator is used during step iii), an internal donor is used in this step.
[0221] [00221] Step v) is preferably carried out directly after step iv), more preferably in the same reactor and preferably in the same reaction mixture.
[0222] [00222] In one embodiment, at the end of step iv) or at the beginning of step v), the supernatant is removed from the modified solid intermediate product obtained in step iv) by filtration or decantation. To the remaining solid, a mixture of titanium halide (eg, tetrachloride) and a solvent (eg, chlorobenzene) can be added. The reaction mixture is subsequently maintained at an elevated temperature (for example, between 100 and 130 ° C, such as 115 ° C) for a certain period of time (for example, between 10 and 120 minutes, such as between 20 and 60 minutes, for example, 30 minutes, after which the solid substance is allowed to deposit by stopping the stirring.
[0223] [00223] The molar ratio of the transition metal to magnesium is between 10 and 100, more preferably between 10 and 50.
[0224] [00224] Optionally, an internal electron donor is also present during this stage. Mixtures of internal electron donors can also be used. Examples of internal electron donors are described below. The molar ratio of internal electron donor to magnesium can vary between wide limits, for example, 0.02 and 0.75. Preferably, this molar ratio is between 0.05 and 0.4; more preferably between 0.1 and 0.4; and most preferably between 0.1 and 0.3.
[0225] [00225] The solvent for this step can be selected, for example, from aliphatic and aromatic hydrocarbons and halogenated aromatics with, for example, 4 to 20 carbon atoms. The solvent can also be a mixture of two or more of these.
[0226] [00226] According to a preferred embodiment of the present invention, that step v) is repeated, in other words, the supernatant is removed as described above and a mixture of titanium halide (for example, tetrachloride) and a solvent (for example , chlorobenzene) is added. The reaction is continued at elevated temperatures for a period of time that may be the same or different from the period of time in which the first step v) is carried out.
[0227] [00227] The step can be performed with agitation. 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 the person skilled in the art. This can be the same as discussed above for step iii).
[0228] [00228] Therefore, step v) can be considered to consist of at least two substeps in this modality, being: va) contacting said modified intermediate product obtained in step iv) with titanium tetrachloride - optionally using an internal donor - to obtain a pro-catalyst partially treated with titanium; (this can, for example, be considered to be stage II as discussed above for a three stage Stage C) vb) contacting said pro-catalyst partially treated with titanium obtained in step va) with titanium tetrachloride to obtain the pro-catalyst (this can, for example, be considered to be stage III as discussed above for a three-stage Phase C ).
[0229] [00229] Additional substeps may be present to increase the number of titanation steps to four or more (for example, stages IV, V, etc.)
[0230] [00230] The solid substance (pro-catalyst) obtained is washed several times with solvent (for example, heptane), preferably at an elevated temperature, for example between 40 and 100 ° C depending on the boiling point of the solvent used, preferably between 50 and 70 ° C. After that, the pro-catalyst suspended in solvent is obtained. The solvent can be removed by filtration or decantation. The pro-catalyst can be used as such, moistened by the solvent, or suspended in the solvent or it can be dried first, preferably partially dried, for storage. Drying can be carried out, for example, by a flow of nitrogen under low pressure for several hours.
[0231] [00231] The titanation step (that is, the contact step with the titanium halide) according to the present invention is divided into two parts and a modification step with a Group 13 or transition metal is introduced between the two parts or stages of titanation. Preferably, the first part of the titanation comprises a single titanation step and the second part of the titanation comprises the subsequent two titanation steps. But different procedures can be used. When this modification is carried out before the titanation stage, the increase in activity was greater, as noted by the inventors. When this modification is carried out after the titanation step, the increase in activity was less as observed by the present inventors.
[0232] [00232] In summary, one embodiment of the present invention comprises the following steps: i) preparation of the first reaction intermediate product; ii) activation of the solid support to provide a second intermediate reaction product; iii) first titanation or Stage I to supply the third intermediate reaction product; iv) modification to supply the modified intermediate product; v) second titanation or Stage M / MI to supply the pro-catalyst. The pro-catalyst is combined with DEATES as an external donor to prepare the catalyst system according to the present invention.
[0233] [00233] The pro-catalyst can have a content of titanium, hafnium, zirconia, chromium or vanadium (preferably titanium) between about 0.1% by weight to about 6.0% by weight, based on the total weight of solids or between about 1.0% by weight to about 4.5% by weight, or between about 1.5% by weight to about 3.5% by weight. The weight percentage is based on the total weight of the pro-catalyst.
[0234] [00234] The weight ratio of titanium, hafnium, zirconia, chromium or vanadium (preferably titanium) to magnesium in the solid pro-catalyst can be between about 1: 3 and about 1: 160 or between about 1: 4 and about 1:50 or between about 1: 6 and 1:30.
[0235] [00235] The solid catalyst compound containing a transition metal according to the present invention comprises a transition metal halide (e.g., titanium halide, chromium halide, hafnium halide, zirconia halide or vanadium halide) supported on a metal or metalloid compound (for example, a magnesium compound or a silica compound).
[0236] [00236] Preferably, a support based on magnesium or containing magnesium is used in the present invention. Such a support is prepared from support precursors containing magnesium, such as magnesium halides, alkyl magnesium and aryl magnesium and also magnesium alkoxy and magnesium aryloxy compounds.
[0237] [00237] Support can be activated using activation compounds as described in more detail above under Phase B.
[0238] [00238] The catalyst can be activated during Phase C as discussed above for the process. This activation increases the yield of the catalyst composition resulting in the polymerization of olefin.
[0239] [00239] Various activators can be used, such as benzamides, alkyl benzoate and monoesters. Each of these will be discussed below.
[0240] [00240] A benzamide activator has a structure according to Formula X:
[0241] [00241] R70 and R71 are each independently selected from hydrogen or an alkyl. Preferably, said alkyl has between 1 and 6 carbon atoms, more preferably between 1 to 3 carbon atoms. More preferably, R70 and R71 are each independently selected from hydrogen or methyl.
[0242] [00242] R72, R73, R74, R75, R76 are each independently selected from hydrogen, a heteroatom (preferably a halide) or a hydrocarbyl group selected for example from the groups alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl and one or more combinations of these. Said hydrocarbyl group can be linear, branched or cyclic. Said hydrocarbyl group can be substituted or unsubstituted. Said hydrocarbyl group may contain one or more heteroatoms. Preferably said hydrocarbyl group has between 1 and 10 carbon atoms, more preferably between 1 to 8 carbon atoms, even more preferably between 1 and 6 carbon atoms.
[0243] [00243] Suitable non-limiting examples of "benzamides" include benzamides (R70 and R71 are both hydrogens and each of R72, R73, R74, R75, R76 are hydrogens) also denoted as BA-2H or methylbenzamide (R70 is hydrogen; R71 is methyl and each of R72, R73, R74, R75, R76 are hydrogens) also denoted as BA-HMe or dimethylbenzamide (R70 and R71 are methyl and each of R72, R73, R74, R75, R76 is hydrogen) denoted as BA-2Me. Other examples include monoethylbenzamide, diethylbenzamide, methyl ethylbenzamide, 2- (trifluoromethyl) -benzamide, N, N-dimethyl-2- (trifluoromethyl) benzamide, 3- (trifluoromethyl) benzamide, N, N-dimethyl-3- (trifluoromethyl) benzamide, 2,4-dihydroxy-N- (2-hydroxyethyl) benzamide, N- (1 H-benzotriazol-1-ylmethyl) benzamide, 1 - (4-ethylbenzoyl) piperazine, 1-benzoylpiperidine.
[0244] [00244] It has been surprisingly discovered by the present inventors that when added to the benzamide activator during the first stage of the process together with the catalytic species or directly after the addition of the catalytic species (for example, within 5 minutes), an even greater increase in yield it is observed compared when the activator is added during stage II or stage III of the process.
[0245] [00245] It has been surprisingly discovered by the present inventors that the benzamide activator having two alkyl groups (e.g., dimethylbenzamide or diethylbenzamide, preferably dimethylbenzamide) provides a greater increase in yield than benzamide or monoalkyl benzamide.
[0246] [00246] Without wishing to be attached to any particular theory, the present inventors believe that the fact that the most effective activation is achieved when the benzamide activator is added during stage I has the following reason. It is considered that the benzamide activator will bind to the catalytic species and is later replaced by the internal donor when the internal donor is added.
[0247] [00247] Alkyl benzoates can be used as activators. The activator can therefore be selected from the group of alkyl benzoates which has an alkyl group which has between 1 and 10, preferably between 1 and 6 carbon atoms. Examples of suitable alkyl benzoate are methyl benzoate, ethyl benzoate according to Formula II, n-propyl benzoate, isopropyl benzoate, n-butyl benzoate, 2-butyl benzoate, t-butyl benzoate.
[0248] [00248] More preferably, the activator is ethyl benzoate. In an even more preferred embodiment, ethyl benzoate as an activator is added during step iii) and an internal benzamide donor is added during step v), most preferably 4- [benzoyl (methyl) amino] pentan- 2-line according to Formula XII:
[0249] [00249] Monoesters can be used as activators. The monoester according to the present invention can be any ester of a monocarboxylic acid known in the art. The structures according to Formula V are also monoesters, but are not explained in this section, see the section on Formula V. The monoester can have Formula XXIII. R94-CO-OR95 Formula XXIII
[0250] [00250] R94 and R95 are each independently a hydrocarbyl group selected for example from the alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups and one or more combinations thereof. Said hydrocarbyl group can be linear, branched or cyclic. Said hydrocarbyl group can be substituted or unsubstituted. Said hydrocarbyl group may contain one or more heteroatoms. Preferably said hydrocarbyl group has between 1 and 10 carbon atoms, more preferably between 1 to 8 carbon atoms, even more preferably between 1 and 6 carbon atoms. When R94 is an aryl, this structure is similar to Formula V. Examples of aromatic monoesters are discussed with reference to Formula V.
[0251] [00251] Preferably, said monoester is an aliphatic monoester. Suitable examples of monoesters include formats, for example, butyl format; acetates, for example, ethyl acetate, amyl acetate and butyl acetate; acrylates, for example, ethyl acrylate, methyl methacrylate and isobutyl methacrylate. Most preferably, the aliphatic monoester is an acetate. Most preferably, the aliphatic monoester is ethyl acetate.
[0252] [00252] In one embodiment, the monoester used in step iii) is an aliphatic monocarboxylic acid ester between 1 and 10 carbon atoms, where R94 is an aliphatic hydrocarbyl group.
[0253] [00253] The molar ratio between the monoester in step iii) and Mg can vary between 0.05 to 0.5, preferably between 0.1 to 0.4 and most preferably between 0.15 to 0.25.
[0254] [00254] Monoester is not used as a stereospecific agent, as common internal donors are known to be in the prior art. The monoester is used as an activator.
[0255] [00255] Without being bound by any theory, the inventors believe that the monoester used in the process according to the present invention participates in the formation of magnesium halogen crystallites (eg, MgCU) during the interaction of the support containing Mg with the titanium halogen (for example, TiCl4). The monoester can form intermediate complexes with halogen compounds of Ti and Mg (for example, TiCl4, TiCl3 (OR), MgCl2, MgCl (OEt), etc.), assist in removing titanium products from solid particles to the mother liquid and affect the activity of the final catalyst. Therefore, the monoester according to the present invention can also be referred to as an activator.
[0256] [00256] As used here, an "internal electron donor" or an "internal donor" is a compound added during the formation of the pro-catalyst that donates a pair of electrons to one or more metals present in the resulting pro-catalyst. Not linked to any particular theory, it is considered that the internal electron donor assists in regulating the formation of active sites, thereby intensifying the stereoselectivity of the catalyst.
[0257] [00257] The internal electron donor can be any compound known in the art to be used as an internal electron donor. Suitable examples of internal donors include aromatic acid esters, such as monocarboxylic acid ester or dicarboxylic acid esters (e.g., ortho-dicarboxylic acid esters such as phthalic acid esters), (N-alkyl) amidobenzoates, 1,3 -dieters, silyl esters, fluorenes, succinates and / or their combinations.
[0258] [00258] The use of so-called internal phthalate-free donors is preferred due to increasingly stringent government regulations around the maximum phthalate content of polymers. This leads to an increasing demand for phthalate-free catalyst compositions. In the context of the present invention, "essentially phthalate-free" from "phthalate-free" means having a phthalate content of less than, for example, 150 ppm, alternatively less than, for example, 100 ppm, alternatively less than, for example, example, 100 ppm, alternatively less than, for example, 50 ppm, alternatively less than, for example, 20 ppm.
[0259] [00259] An aromatic acid ester can be used as an internal donor.
[0260] [00260] As used here, an "aromatic acid ester" is an ester of monocarboxylic acid (also called "benzoic acid ester" as shown in Formula V, an ester of dicarboxylic acid (for example, an o-dicarboxylic acid also called "phthalic acid ester") as shown in Formula VI:
[0261] [00261] R30 is selected from a hydrocarbyl group selected, for example, from the alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups and one or more combinations of these. Said hydrocarbyl group can be linear, branched or cyclic. Said hydrocarbyl group can be substituted or unsubstituted. Said hydrocarbyl group may contain one or more heteroatoms. Preferably said hydrocarbyl group has between 1 and 10 carbon atoms, more preferably between 1 to 8 carbon atoms, even more preferably between 1 and 6 carbon atoms. Examples of hydrocarbyl groups include alkyl, cycloalkyl, alkenyl, alkadienyl, cycloalkenyl, cycloalkylenyl, aryl, aralkyl, alkylaryl and alkenyl groups.
[0262] [00262] R31, R32, R33, R34, R35 are each independently selected from hydrogen, a heteroatom (preferably a halide) or a hydrocarbyl group selected for example from the groups alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl and one or more combinations of these. Said hydrocarbyl group can be linear, branched or cyclic. Said hydrocarbyl group can be substituted or unsubstituted. Said hydrocarbyl group may contain one or more heteroatoms. Preferably said hydrocarbyl group has between 1 and 10 carbon atoms, more preferably between 1 to 8 carbon atoms, even more preferably between 1 and 6 carbon atoms.
[0263] [00263] Non-limiting examples of "benzoic acid esters" include an alkyl p-alkoxybenzoate (such as ethyl p-methoxybenzoate, methyl p-ethoxybenzoate, ethyl p-ethoxybenzoate), an alkyl benzoate (such as benzoate of ethyl, methyl benzoate), an alkyl p-halobenzoate (ethyl p-chlorobenzoate, ethyl p-bromobenzoate) and benzoic anhydride. The benzoic acid ester is preferably selected from ethyl benzoate, benzoyl chloride, ethyl p-bromobenzoate, n-propyl benzoate and benzoic anhydride. The benzoic acid ester is most preferably ethyl benzoate,
[0264] [00264] R40 and R41 are each independently a hydrocarbyl group selected for example from the alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups and one or more combinations thereof. Said hydrocarbyl group can be linear, branched or cyclic. Said hydrocarbyl group can be substituted or unsubstituted. Said hydrocarbyl group may contain one or more heteroatoms. Preferably said hydrocarbyl group has between 1 and 10 carbon atoms, more preferably between 1 to 8 carbon atoms, even more preferably between 1 and 6 carbon atoms. Examples of suitable hydrocarbyl groups include alkyl, cycloalkyl, alkenyl, alkadienyl, cycloalkenyl, cycloalkylenyl, aryl, aralkyl, alkylaryl and alkynyl groups.
[0265] [00265] R42, R43, R44, R45 are each independently selected from hydrogen, a halide or a hydrocarbyl group selected for example from the alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups and one or more combinations of these . Said hydrocarbyl group can be linear, branched or cyclic. Said hydrocarbyl group can be substituted or unsubstituted. Said hydrocarbyl group may contain one or more heteroatoms. Preferably said hydrocarbyl group has between 1 and 10 carbon atoms, more preferably between 1 to 8 carbon atoms, even more preferably between 1 and 6 carbon atoms.
[0266] [00266] Suitable non-limiting examples of phthalic acid esters include dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-t phthalate -butyl, diisoamyl phthalate, di-t-amyl phthalate, dineopentyl phthalate, di-2-ethylhexyl phthalate, di-2-ethylldecyl phthalate, bis (2,2,2-trifluorethyl) phthalate, 4- diisobutyl t-butylphthalate and diisobutyl 4-chlorophthalate. The phthalic acid ester is preferably di-n-butyl phthalate or diisobutyl phthalate.
[0267] [00267] As used here, a di-ether "can be a 1,3-di (hydrocarbon) propane compound, optionally substituted in position 2 represented by Formula VII,
[0268] [00268] R51 and R52 are each independently selected from a hydrogen or a hydrocarbyl group selected, for example, from the alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups and one or more combinations thereof. Said hydrocarbyl group can be linear, branched or cyclic. Said hydrocarbyl group can be substituted or unsubstituted. Said hydrocarbyl group may contain one or more heteroatoms. Preferably said hydrocarbyl group has between 1 and 10 carbon atoms, more preferably between 1 to 8 carbon atoms, even more preferably between 1 and 6 carbon atoms. Examples of suitable hydrocarbyl groups include alkyl, cycloalkyl, alkenyl, alkadienyl, cycloalkenyl, cycloalkadienyl, aryl, aralkyl, alkylaryl and alkenyl groups.
[0269] [00269] R53 and R54 are each independently a hydrocarbyl group selected for example from the alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups and one or more combinations thereof. Said hydrocarbyl group can be linear, branched or cyclic. Said hydrocarbyl group can be substituted or unsubstituted. Said hydrocarbyl group may contain one or more heteroatoms. Preferably said hydrocarbyl group has between 1 and 10 carbon atoms, more preferably between 1 to 8 carbon atoms, even more preferably between 1 and 6 carbon atoms.
[0270] [00270] Suitable examples of dialkyl diether compounds include 1,3-dimethoxypropane, 1,3-diethoxypropane, 1,3-dibutoxypropane, 1-methoxy-3-ethoxypropane, 1-methoxy-3-butoxypropane, 1-methoxy-3 -cyclohexoxypropane, 2,2-dimethyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane, 2,2-di-n-butyl-1,3-dimethoxypropane, 2,2-diiso-butyl - 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-d imetoxypropane, 2- (pt-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-dimethoxy propane, 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-t-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-cyclohexyl methyl-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-dicylopentyl-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 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 their combinations.
[0271] [00271] Examples of preferred ethers are diethyl ether, dibutyl ether, diisoamyl ether, anisol 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:
[0272] [00272] As used here, a "succinic acid ester" is a 1,2-dicarboxyethane and can be used as an internal donor, according to Formula VIII:
[0273] [00273] R60 and R61 are each independently a hydrocarbyl group selected for example from the alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups and one or more combinations thereof. Said hydrocarbyl group can be linear, branched or cyclic. Said hydrocarbyl group can be substituted or unsubstituted. Said hydrocarbyl group may contain one or more heteroatoms. Preferably said hydrocarbyl group has between 1 and 10 carbon atoms, more preferably between 1 to 8 carbon atoms, even more preferably between 1 and 6 carbon atoms.
[0274] [00274] R62, R63, R64, R65 are each independently selected from hydrogen or a hydrocarbyl group selected from the alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups and one or more combinations of these. Said hydrocarbyl group can be linear, branched or cyclic. Said hydrocarbyl group can be substituted or unsubstituted. Said hydrocarbyl group may contain one or more heteroatoms. Preferably said hydrocarbyl group has between 1 and 20 carbon atoms.
[0275] [00275] More preferably, R62, R63, R64, R65 are selected independently from the group consisting of hydrogen, C1-C10 straight and branched alkyl; C3-C10 cycloalkyl; C6-C10 aryl; and C7-C10 alkaryl and aralkyl.
[0276] [00276] Even more preferably, R62, R63, R64, R65 are selected independently from the group consisting of hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, t - butyl, phenyl, trifluoromethyl and halophenyl. More preferably, one of R62 and R63 is selected from methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, t-butyl, while the other is a hydrogen atom; and one of R64 and R64 is selected from methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, t-butyl, while the other is a hydrogen atom.
[0277] [00277] Suitable examples of succinic acid ester include diethyl 2,3-diisopropylsuccinate, diethyl 2,3-di-n-propylsuccinate, diethyl 2,3-diisobutylsuccinate, 2,3-di-sec -diethyl butylsuccinate, dimethyl 2,3-diisopropylsuccinate, dimethyl 1,2,3-di-n-propylsuccinate, dimethyl 2,3-diisobutylsuccinate. Dimethyl 2,3-di-sec-butyl succinate.
[0278] [00278] Examples of other organic compounds that contain a heteroatom are thiophenol, 2-methylthiophene, isopropyl mercaptan, diethylthioether, diphenylthioether, tetrahydrofuran, dioxane, anisol, acetone, triphenylphosphine, triphenylphosphite, diethylphosphate and diphenylphosphate.
[0279] [00279] The silyl ester as an internal donor can be any silyl ester or silyl diol ester known in the art, for example, as described in US 2010/0130709.
[0280] [00280] When an aminobenzoate (AB) according to formula XI is used as an internal donor, this ensures better control of stereochemistry and allows the preparation of polyolefins that have a wider molecular weight distribution.
[0281] [00281] Aminobenzoates suitable as internal donors according to the present invention are the compounds represented by Formula XI:
[0282] [00282] Where R80 is an aromatic group, selected from aryl or alkylaryl groups and can be substituted or unsubstituted. Said aromatic group may contain one or more heteroatoms. Preferably, said aromatic group has between 6 and 20 carbon atoms. It should be noted that the two groups R80 can be the same, but they can also be different.
[0283] [00283] R80 can be the same or different from any of R81 - R87 and is preferably a substituted or unsubstituted aromatic hydrocarbyl having 6 to 10 carbon atoms.
[0284] [00284] More preferably, R80 is selected from the group consisting of C6-C10 unsubstituted or substituted aryl with, for example, an acyl halide or an alkoxide; and C7-C10 alkaryl and aralkyl group; for example, 4-methoxyphenyl, 4-chlorophenyl, 4-methylphenyl.
[0285] [00285] Particularly preferred, R80 is a substituted or unsubstituted phenyl, benzyl, naphthyl, ortho-tolyl, para-tolyl or anisole group. Most preferably, R80 is phenyl.
[0286] [00286] R81, R82, R83, R84, R85 and R86 are each independently selected from hydrogen or a hydrocarbyl group selected from the alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups and one or more combinations of these. Said hydrocarbyl group can be linear, branched or cyclic. Said hydrocarbyl group can be substituted or unsubstituted. Said hydrocarbyl group may contain one or more heteroatoms. Preferably said hydrocarbyl group has between 1 and 20 carbon atoms.
[0287] [00287] More preferably, R81, R82, R83, R84, R85 and R86 are independently selected from a group consisting of hydrogen, C1-C10 straight and branched alkyl; C3-C10 cycloalkyl; C6-C10 aryl; and C7-C10 alkaryl and an aralkyl group.
[0288] [00288] Even more preferably, R81, R82, R83, R84, R85 and R86 are independently selected from a group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, phenyl, trifluorfenyl and halophenyl.
[0289] [00289] More preferably, R81, R82, R83, R84, R85 and R86 are each hydrogen, methyl, ethyl, propyl, t-butyl, phenyl or trifluoromethyl.
[0290] [00290] Preferably, R81, R82 are each a hydrogen atom.
[0291] [00291] More preferably, R81, R82 are each a hydrogen atom and each of R83, R84, R85 and R86 is independently selected from a group consisting of hydrogen, C1-C10 straight and branched alkyl; C3-C10 cycloalkyl; C6-C10 aryl; and C7-C10 alkaryl and an aralkyl group.
[0292] [00292] Preferably, at least one from R83 and R84 and at least one from R85 and R86 is a hydrocarbyl group that has at least one carbon atom, being selected from the group as defined above.
[0293] [00293] Preferably, when at least one of R83 and R84 and one of R85 and R86 is a hydrocarbyl group that has at least one carbon atom, then the other at least one R83 and R84 and one of R85 and R86 is each , hydrogen atoms.
[0294] [00294] Most preferably, when at least one of R83 and R84 and one of R85 and R86 is a hydrocarbyl group that has at least one carbon atom, then the other at least one R83 and R84 and one of R85 and R86 is each a hydrogen atom and R81 and R82 are each hydrogen atoms.
[0295] [00295] More preferably, R85 and R86 are selected from the group consisting of C1-C10 alkyl, such as a methyl, ethyl, propyl, isopropyl, butyl, t-butyl, phenyl, trifluoromethyl and halophenyl group and most preferably, a of R83 and R84 and one of R85 and R86 is methyl.
[0296] [00296] R87 is a hydrogen or a hydrocarbyl group, for example, between the alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups and one or more combinations of these. Said hydrocarbyl group can be linear, branched or cyclic. Said hydrocarbyl group can be substituted or unsubstituted. Said hydrocarbyl group may contain one or more heteroatoms. Preferably said hydrocarbyl group has between 1 and 20 carbon atoms, more preferably between 1 and 10 carbon atoms. R87 can be the same or different from any of R81, R82, R83, R84, R85 and R86 with the proviso that R87 is not a hydrogen atom.
[0297] [00297] More preferably, R87 is selected from the group consisting of straight and branched C1-C10 alkyl; C3-C10 cycloalkyl; C6-C10 aryl; and C7-C10 alkaryl and an aralkyl group.
[0298] [00298] Even more preferably, R87 is selected from a group consisting of methyl, ethyl, propyl, isopropyl, butyl, t-butyl, phenyl, benzyl, substituted benzyl and halophenyl groups.
[0299] [00299] Most preferably, R87 is methyl, ethyl, propyl, isopropyl, phenyl or benzyl; and even more preferably, R87 is methyl, ethyl or propyl.
[0300] [00300] Without being limited to this, particular examples of compounds of the formula (XI) are the structures as illustrated in formulas (XII) - (XXII). For example, the structure in Formula (XII) can correspond to 4- [benzoyl (methyl) amino] pentan-2-yl benzoate; Formula (XI II) to 3- [benzoyl (cyclohexyl) amino] -1-phenylbutyl benzoate; Formula (XIV) to 3- [benzoyl (propan-2-yl) amino] -1-phenylbutyl benzoate; Formula (XV) to 4- [benzoyl (propan-2-yl) amino] pentan-2-yl benzoate; Formula (XVI) to 4- [benzoyl (methyl) amino] -1,1,1-trifluoropentan-2-yl benzoate; Formula (XVII) to 3- (methylamino) -1,3-diphenylpropan-1-ol dibenzoate; Formula (XVIII) to 2,2,6,6-tetramethyl-5- (methylamino) heptan-3-ol dibenzoate; Formula (XIX) to 4- [benzoyl (ethyl) amino] pentan-2-yl benzoate; Formula (XX) to 3- (methyl) amino-propan-1-ol dibenzoate; Formula (XXI) to 3- (methyl) amino-2,2-dimethylpropan-1-ol dibenzoate; Formula (XXII) to 4- (methylamino) pentan-2-yl bis (4-methoxy) benzoate).
[0301] [00301] It was surprisingly discovered that the catalyst composition that comprises the compound of formula (XI) as an internal electron donor shows better stereochemical control and allows for the preparation of polyolefins, particularly propylene that have a broader molecular weight distribution and greater isotacticity.
[0302] [00302] Preferably, the catalyst composition according to the invention comprises the compound having formula (XI) as the only internal electron donor in the Ziegler-Natta catalyst composition.
[0303] [00303] The compounds of formulas (XII), (XIX), (XXII) and (XVIII) are the most preferred internal electron donors in the catalyst composition according to the present invention, since they allow the preparation of polyolefins that have a wider molecular weight distribution and greater isotacticity.
[0304] [00304] The compound according to formula (XI) can be made by any method known in the art. In this regard, reference is made to J. Chem. Soc. Perkin trans. I 1994, 537-543 and Org. Synth.1967, 47, 44. These documents describe step a) of contacting a 2,4-diketone substituted with a substituted amine in the presence of a solvent to give a β-enaminoketone; followed by step b) of contacting the β-enaminoketone with a reducing agent in the presence of a solvent to give γ-amino alcohol. The substituted 2,4-diketone and the substituted amine can be applied in step a) in amounts ranging from 0.5 to 2.0 moles, preferably between 1.0 to 1.2 moles. The solvent in steps a) and b) can be added in an amount of 5 to 15 volumes, based on the total amount of the diketone, preferably 3 to 6 volumes. The molar ratio of β-enaminoketone in step b) can be 0.5 to 6, preferably from 1 to 3. The molar ratio of reducing agent to β-enaminoketone in step b) can be between 3 to 8, preferably between 4 to 6; the reducting agent can be selected from the group comprising metallic sodium, NaBH4 in acetic acid, Ni-Al alloy. Preferably, the reducing agent is sodium metal because it is an inexpensive reagent.
[0305] [00305] The γ-amino alcohol that can be used to make the compound (XI) can be synthesized as described in the literature and also mentioned here above or that compound can be purchased directly commercially and used as a starting compound in a reaction to obtain the compound represented by the formula (XI). In particular, γ-amino alcohol can be reacted with a substituted or unsubstituted benzoyl chloride compound in the presence of a base to obtain the compound represented by formula (XI) (also referred to here as step c), regardless of whether γ- amino alcohol was synthesized as described in the literature or commercially acquired). The molar ratio between substituted or unsubstituted benzoyl chloride and γ-amino alcohol can vary between 2 to 4, preferably 2 to 3. The base can be any basic chemical compound that is capable of deprotonating γ-amino alcohol. Said base can have a pKa of at least 5; or at least 10 or preferably between 5 and 40, where pKa is a constant already known to the person skilled in the art as the negative ka acid dissociation constant algorithm. Preferably, the base is pyridine; a trialkylamine, for example, triethylamine; or a metal hydroxide, for example, NaOH, KOH. Preferably, the base is pyridine. The molar ratio between the base and the γ-amino alcohol can vary from 3 to 10, preferably from 4 to 6.
[0306] [00306] The solvent used in any of steps a), b) and c) can be selected from any of the organic solvents such as toluene, dichloromethane, 2-propanol, cyclohexane or mixtures of any organic solvent. Preferably, toluene is used in each of steps a), b) and c). More preferably, a mixture of toluene and 2-propanol is used in step b). The solvent in step c) can be added in an amount of 3 to 15 volumes, preferably 5 to 10 volumes based on γ-amino alcohol.
[0307] [00307] The reaction mixture in any of steps a), b) and c) can be stirred using any type of conventional stirrer for more than about an hour, preferably for more than about 3 hours and most preferably for more than about 10 hours, but less than about 24 hours. The reaction temperature for any of steps a) and b) can be room temperature, that is, between about 15 to about 30 ° C, preferably between about 20 to about 25 ° C. The reaction temperature in step c) can vary between 0 and 10 ° C, preferably between 5 and 10 ° C. The reaction mixture in any of steps a), b) and c) can be refluxed for more than about 10 hours, preferably for more than about 20 hours, but less than about 40 hours or until the reaction complete (the completion of the reaction can be measured by Gas Chromatography, GC).
[0308] [00308] The reaction mixture from steps a) and b) can then be allowed to cool to room temperature, that is, at a temperature between about 15 to about 30 ° C, preferably between about 20 to about 25 ° Ç. The solvent and any excess components can be removed in any of steps a), b) and c) by any method known in the art, such as evaporation or washing. The product obtained in any of steps b) and c) can be separated from the reaction mixture by any method known in the art, such as by extraction over metal salts, for example, sodium sulfate.
[0309] [00309] The molar ratio of the internal donor of formula (XI) to magnesium can be 0.02 to 0.5. Preferably, this molar ratio is between 0.05 to 0.2.
[0310] [00310] A benzamide can be used as an internal donor. Suitable compounds have a structure according to formula X:
[0311] [00311] R70 and R71 are each independently selected from hydrogen or an alkyl. Preferably, said alkyl has between 1 and 6 carbon atoms, more preferably between 1 to 3 carbon atoms. More preferably, R70 and R71 are each independently selected from hydrogen or methyl.
[0312] [00312] R72, R73, R74, R75, R76 are each independently selected from hydrogen, a heteroatom (preferably a halide) or a hydrocarbyl group selected for example from the groups alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl and one or more combinations of these. Said hydrocarbyl group can be linear, branched or cyclic. Said hydrocarbyl group can be substituted or unsubstituted. Said hydrocarbyl group may contain one or more heteroatoms. Preferably said hydrocarbyl group has between 1 and 10 carbon atoms, more preferably between 1 to 8 carbon atoms, even more preferably between 1 and 6 carbon atoms.
[0313] [00313] Suitable non-limiting examples of "benzamides" include benzamides (R70 and R71 are both hydrogens and each of R72, R73, R74, R75, R76 are hydrogens) also denoted as BA-2H or methylbenzamide (R70 is hydrogen; R71 is methyl and each of R72, R73, R74, R75, R76 are hydrogens) also denoted as BA-HMe or dimethylbenzamide (R70 and R71 are methyl and each of R72, R73, R74, R75, R76 is hydrogen) denoted as BA-2Me. Other examples include monoethylbenzamide, diethylbenzamide, methyl ethylbenzamide, 2- (trifluoromethyl) -benzamide, N, N-dimethyl-2- (trifluoromethyl) benzamide, 3- (trifluoromethyl) benzamide, N, N-dimethyl-3- (trifluoromethyl) benzamide, 2,4-dihydroxy-N- (2-hydroxyethyl) benzamide, N- (1H-benzotriazol-1-ylmethyl) benzamide, 1 - (4-ethylbenzoyl) piperazine, 1-benzoylpiperidine.
[0314] [00314] As discussed in WO 2013124063, 1,5-diesters according to formula XXV can be used as internal donors. These 1.5 diesters have two chiral centers without their C2 and C4 carbons. There are 4 isomers, which are the meso-isomer 2R, 4S, the meso-isomer 2S, 4R and the isomers 2S, 4S and 2R, 4R. A mixture of all of them is called a "rac" diester.
[0315] [00315] R15 is a hydrocarbyl group independently selected, for example, from the alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups and one or more combinations thereof. Said hydrocarbyl group can be linear, branched or cyclic. Said hydrocarbyl group can be substituted or unsubstituted. Said hydrocarbyl group may contain one or more heteroatoms. Preferably, said hydrocarbyl group has between 1 and 20 carbon atoms.
[0316] [00316] R16 and R17 are different with respect to each other. Both groups R16 can be the same or different. Both groups R17 can be the same or different. Groups R16 and R17 are selected independently from the group consisting of hydrogen, halogen and a hydrocarbyl group independently selected, for example, from the alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups and one or more combinations of these. Said hydrocarbyl group can be linear, branched or cyclic. Said hydrocarbyl group can be substituted or unsubstituted. Said hydrocarbyl group may contain one or more heteroatoms. Preferably, said hydrocarbyl group has between 1 and 20 carbon atoms.
[0317] [00317] An example of a compound according to formula XXV is pentanediol dibenzoate.
[0318] [00318] The compound according to formula XXV has two stereocenters (in C2 and C4), comprises two of the so-called stereocenters each giving rise to two different configurations and, therefore, a total of four stereoisomers. There are two sets of diastereomers (or diastereoisomers), each comprising two enantiomers. The enantiomers differ in both stereocenters and are, therefore, mirror images of each other.
[0319] [00319] Groups R16 and R17 can be switched. In other words, the mirror image of the Formula XXV compound that has the two R17 groups on the left side of the structure. The compound in formula XXV is the meso-isomer (2R, 4S) while the mirror image (not shown) is the meso-isomer (2S, 4R). The compound of formula XXV is a meso-isomer, that is, it contains two stereocenters (chiral centers), but it is not chiral.
[0320] [00320] The following two other isomers are possible: an isomer (2S, 4S) (not shown), an isomer (2R, 4R) (not shown). R and S illustrate the chiral centers of the molecules, as known to the person skilled in the art. When a mixture of 2S, 4S and 2R, 4R is present, this is called "rac". These internal donors are described in detail in WO 2013/124063 which shows Fisher's projections of all isomers.
[0321] [00321] In one embodiment, at least one group R16 and R17 can be selected from the group consisting of hydrogen, halogen, C1-C10 straight and branched alkyl; C3-C10 cycloalkyl; C6-C10 aryl; and C7-C10 alkaryl and an aralkyl group. More preferably, at least one group of R16 and R17 is selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, phenyl and halophenyl.
[0322] [00322] Preferably, any of R16 and R17 represents hydrogen. More preferably, R16 and R17 represent a methyl or ethyl group. It is particularly preferred when any one of R16 and R17 represents hydrogen and the other R16 and R17 represent a methyl or ethyl group.
[0323] [00323] Preferably, R15 is selected independently from groups containing benzene ring, such as phenyl, phenyl substituted by aquyl, alkoxy or halogen; optionally, the carbon atoms on the benzene ring being replaced by an oxygen and / or nitrogen heteroatom; alkenyl or phenyl substituted alkenyl, such as vinyl, propenyl, styryl; alkyl such as methyl, ethyl, propyl, etc.
[0324] [00324] More preferably, R15 represents a phenyl group. Particularly preferred is meso pentane-2,4-diol dibenzoate (mPDDB).
[0325] [00325] The catalyst system according to the present invention includes a cocatalyst. As used here, a "co-catalyst" is a well-known expression in the Ziegler-Natta catalyst technique and is recognized to be a substance capable of converting the pro-catalyst into an active polymerization catalyst. Generally, the cocatalyst is an organo-metallic compound that contains a metal of group 1, 2, 12 or 13 of the Periodic System of Elements (Handbook of Chemistry and Physics, 70th Edition, CRC Press, 1989-1990).
[0326] [00326] The cocatalyst can include any compounds known in the art to be used as "co-catalysts" such as hydrides, alkyls or aryl of aluminum, lithium, zinc, tin, cadmium, beryllium, magnesium and combinations thereof. The cocatalyst can be an aluminum hydrocarbyl cocatalyst represented by the formula R203Al.
[0327] [00327] R20 is independently selected from hydrogen, halogen or a hydrocarbyl independently selected, for example, from the groups alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl and one or more combinations of these. Said hydrocarbyl group can be linear, branched or cyclic. Said hydrocarbyl group can be substituted or unsubstituted. Said hydrocarbyl group may contain one or more heteroatoms. Preferably, said hydrocarbyl group has between 1 and 20 carbon atoms, more preferably between 1 to 12 carbon atoms, even more preferably between 1 and 6 carbon atoms. Provided that at least one R20 is a hydrocarbyl group. Optionally, two or three R20 groups are joined in a heterocyclic structure that forms a cyclic radical.
[0328] [00328] Non-limiting examples of suitable R20 groups are: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, neopentyl, hexyl, 2-methylpentyl, heptila, octyl, isooctyl, 2-ethylhexyl, 5, 5-dimethylhexyl, nonyl, decyl, isodecyl, undecyl, dodecyl, phenyl, phenethyl, methoxyphenyl, benzyl, tolyl, xylyl, naphthyl, methylnaphthyl, cyclohexyl, cycloheptyl, and cyclooctyl.
[0329] [00329] Suitable examples of aluminum hydrocarbyl compounds as cocatalysts include triisobutyl (TIBA), trihexylaluminum, diisobutylaluminum hydride (DIBALH), dihexylaluminum hydride, isobutylaluminium hydride, hexylaluminium d-hydride, diisobutylhexylaluminum, diisobutylaluminum, isisylutylalethylaluminum, , triethyl aluminum, tripropyl aluminum, triisopropyl aluminum, tri-n-butyl aluminum, trioctyl aluminum, tridecyl aluminum, tridodecyl aluminum, tribenyl aluminum, triphenyl aluminum, trinaftilalumin, and tritolylalumin. In one embodiment, the cocatalyst is selected from triethyl aluminum, triisobutylaluminum, trihexylalumin, diisobutylaluminum hydride, dihexylaluminum hydride. More preferably, trimethyl aluminum, triethyl aluminum, triisobutyl aluminum and / or trioctyl aluminum. Most preferably, triethyl aluminum (abbreviated as TEAL).
[0330] [00330] The cocatalyst can also be an aluminum hydrocarbyl compound represented by the formula R21mAIX213-m.
[0331] [00331] R21 is an alkyl group. Said alkyl group can be linear, branched or cyclic. Said alkyl group can be substituted or unsubstituted. Preferably, said alkyl group has between 1 and 20 carbon atoms, more preferably between 1 to 12 carbon atoms, even more preferably between 1 and 6 carbon atoms.
[0332] [00332] Non-limiting examples of suitable R21 groups are: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, neopentyl, hexyl, 2-methylpentyl, heptila, octyl, isooctyl, 2-ethylhexyl, 5, 5-dimethylhexyl, nonila, decila, isodecila, undecila and dodecila.
[0333] [00333] X21 is selected from the group consisting of fluoride (F-), chloride (Cl-), bromide (Br-) or iodide (I-) or an alkoxide (RO-). The value of m is preferably 1 or 2.
[0334] [00334] Non-limiting examples of alkyl aluminum compounds suitable for the cocatalyst include tetraethyl dialuminoxane, methylaluminoxane, isobutylaluminoxane, tetraisobutyl dialuminoxane, diethyl aluminumethoxide, diisobutylaluminium chloride, methylaluminum chloride, diethyl chloride and ethylaluminum chloride dimethylaluminum.
[0335] [00335] Non-limiting examples of suitable compounds include tetraethyldialuminoxane, methylaluminoxane, isobutylaluminoxane, tetraisobutyldialuminoxane, diethylaluminium ethoxide, diisobutylaluminium chloride, methylaluminium dichloride, diethylaluminium chloride and ethylaluminum chloride. Preferably, the cocatalyst is triethyl aluminum.
[0336] [00336] Preferably, the cocatalyst is triethyl aluminum. The molar ratio of aluminum to titanium can be between about 5: 1 to about 500: 1 or between about 10: 1 to about 200: 1 or between about 15: 1 to about 150: 1 or between about from 20: 1 to about 100: 1. The molar ratio of aluminum to titanium is preferably about 45: 1.
[0337] [00337] The invention relates to a process for making the catalyst system by contact with a Ziegler-Natta type catalyst, a cocatalyst and an external electron donor according to the present invention. The pro-catalyst, the cocatalyst and the external donor can be contacted in any way known to the person skilled in the art; and as also described here, more specifically as in the Examples.
[0338] [00338] The invention further relates to a process for making a polyolefin by contacting an olefin with the catalyst system according to the present invention. The pro-catalyst, the cocatalyst, the external donor and the olefin can be contacted in any way known to the person skilled in the art; and as also described here.
[0339] [00339] For example, the external donor in the catalyst system according to the present invention can be complexed with the cocatalyst and mixed with the pro-catalyst (premix) before contact between the catalyst composition and the olefin. The external donor can also be added independently to the polymerization reactor. The pro-catalyst, the cocatalyst and the external donor can be mixed or combined in another way before addition to the polymerization reactor.
[0340] [00340] The contact of the olefin with the catalyst system according to the present invention can be done under standard conditions of polymerization, known to the person 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 here.
[0341] [00341] The polymerization process can be a gas phase, suspension or mass polymerization process, which operates in one or more than one reactor. One or more olefin monomers can be introduced into a polymerization reactor to react with the catalyst composition and to form an olefin-based polymer (or a fluid bed of polymer particles).
[0342] [00342] In the case of polymerization in a suspension (liquid phase), a dispersing agent is present. Suitable dispersing agents include, for example, propane, n-butane, isobutane, n-pentane, isopentane, hexane (for example, iso- or n-), heptane (for example, iso- or n), octane, cyclohexane, benzene, toluene, xylene, liquid propylene and / or mixtures thereof. Polymerization such as, for example, polymerization temperature and time, monomer pressure, prevention of catalyst contamination, choice of polymerization medium in suspension processes, the use of additional ingredients (such as hydrogen) to control the molar mass of the polymer and other conditions are well known to those skilled in the art. The polymerization temperature can vary within wide limits and is, for example, for the polymerization of propylene, between 0 ° C and 120 ° C, preferably between 40 ° C and 100 ° C. The pressure during the (co) polymerization of propylene is, for example, between 0.1 and 6 Mpa, preferably between 1 to 4 Mpa.
[0343] [00343] Various types of polyolefins are prepared such as homopoliolefins, random copolymers and heterophasic polyolefin. For the latter, especially for heterophasic polypropylene, the following is observed.
[0344] [00344] Copolymers of heterophasic propylene are generally prepared in one or more reactors, by the polymerization of propylene and optionally one or more other olefins, for example, ethylene, in the presence of a catalyst and subsequent polymerization of a mixture of propylene-α-oefin . The resulting polymeric materials can show multiple phases (depending on the proportion of the monomer), but the specific morphology generally depends on the method of preparation and the proportion of the monomer. The heterophasic propylene copolymers used in the process according to the present invention can be produced using any conventional technique known to the person skilled in the art, for example multi-stage polymerization process, such as mass polymerization, gas phase polymerization, polymerization suspension, solution polymerization or any combination thereof. Any conventional catalyst systems, for example, Ziegler-Natta or metallocene, can be used. Such techniques and catalysts are described, for example, in WO06 / 010414; Polypropylene and other Polyolefins, by Ser van der Ven, Studies in Polymer Science 7, Elsevier 1990; WO06 / 010414, US4399054 and US4472524.
[0345] [00345] The molar mass of the polyolefin obtained during polymerization can be controlled by the addition of hydrogen or any other agent known to be suitable for the purpose during polymerization. Polymerization can be carried out continuously or in batches. The suspension, mass and gas phase polymerization processes, multistage processes of each of these types of polymerization processes or combinations of the different types of polymerization processes in a multistage process are contemplated in these. Preferably, the polymerization process is a single-stage or multistage gas-phase process, for example, a two-stage gas-phase process, for example, where each stage, a gas-phase process is used or includes a reactor separate (small) polymerization process.
[0346] [00346] Examples of gas phase polymerization processes include both agitated bed reactor and fluidized bed reactor systems; such processes are well known in the art. Typical gas phase olefin polymerization reactor systems typically comprise a reaction vessel to which olefin monomers and a catalyst system can be added and which contain an agitated bed of growing polymer particles. Preferably, the polymerization process is a single-stage or multistage gas phase process, for example, 2-stage, gas-phase process in which each stage is a gas-phase process.
[0347] [00347] As used here, "gas phase polymerization" is the pathway of an upward fluidizing medium, the fluidizing medium containing one or more monomers, in the presence of a catalyst through a fluidized bed of polymer particles held in a fluidized state by the fluid medium aided by mechanical agitation. Examples of gas phase polymerization are fluidized bed, horizontal stirred bed and vertical stirred bed.
[0348] [00348] "Fluidized bed", "fluidized" or "fluidized" and a gas-solid contacting process, in which the bed of finely divided polymeric particles is raised and agitated by an increasing flow of gas optionally aided by mechanical agitation. In an "agitated bed", the gas velocity upwards is less than the fluidization threshold.
[0349] [00349] A typical gas phase polymerization reactor (or gas phase reactor) includes a vessel (ie the reactor), the fluidized bed, a product discharge system and can include a mechanical stirrer, a distribution plate , an inlet and outlet pipe, a compressor, a cycle gas cooler or heat exchanger. The vessel may include a reaction zone and may include a speed reduction zone, which is located above the reaction zone (i.e., the bed). The fluid medium can include propylene gas and at least one other gas such as an olefin and / or a gaseous vehicle such as hydrogen or nitrogen. Contact can occur by feeding the catalyst composition into the polymerization reactor and introducing the olefin into the polymerization reactor. In one embodiment, the process includes contacting the olefin with a cocatalyst. The cocatalyst can be mixed with the pro-catalyst (pre-mix) before the introduction of the pro-catalyst in the polymerization reactor. The cocatalyst can also be added to the polymerization reactor independently of the pro-catalyst. The independent introduction of the cocatalyst in the polymerization reactor can (substantially) occur simultaneously with the supply of the pro-catalyst.
[0350] [00350] The olefin according to the invention can be selected from mono- and di-olefins containing 2 to 40 carbon atoms. Suitable olefin monomers include alpha-olefins, such as ethylene, propylene, alpha-olefins that have between 4 and 20 carbon atoms (i.e., C4-20), such as 1-butene, -pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene and the like; C4-C20 diolefins, such as 1,3-butadiene, 13-pentadiene, norbornadiene, 5-vinyl-2-norbornene (VNB), 1,4-hexadiene, 5-ethylidene-2-norbornene (ENB) and dicyclopentadiene; aromatic vinyl compounds having between 8 and 40 carbon atoms (i.e., C8-C40) including styrene, o-, m- and p-methylstyrene, divinylbenzene, vinylbiphenyl, vinylnaphthalene; aromatic vinyl compounds C8-C40 substituted with halogen such as chloro-styrene and fluor-styrene.
[0351] [00351] Preferably, the olefin is propylene or a mixture of propylene and ethylene, to result in a propylene-based polymer, such as a propylene homopolymer or propylene-olefin copolymer. The olefin can be an alpha-olefin that has up to 10 carbon atoms, such as ethylene, butane, hexane, heptane and octene. A propylene copolymer is understood to include both so-called random copolymers that typically have a relatively low comonomer content, for example, up to 10 mol%, as well as so-called impact PP copolymers or heterophasic PP copolymers, which comprise high comonomer contents, for example, between 5 and 80 mol%, more typically between 10 to 60 mol%. Impact PP copolymers are actually mixtures of different propylene polymers; such copolymers can be made in one or two reactors and can be mixtures of a first component with low comonomer content and high crystallinity and a second component with high comonomer content that has low crystallinity or even elastic properties. Such random and impact copolymers are well known to those skilled in the art. A random propylene-ethylene copolymer can be produced in a reactor. Impact PP copolymers can be produced in two reactors: the polypropylene homopolymer can be produced in a first reactor; the contents of the first reactor are subsequently transferred to a second reactor in which ethylene (and optionally propylene) is introduced. This results in the production of propylene-ethylene copolymer (i.e., an impact copolymer) in the second reactor.
[0352] [00352] The present invention also relates to a polyolefin, preferably a polypropylene obtained or obtainable by the process which comprises contacting an olefin, preferably propylene or a mixture of propylene and ethylene with the pro-catalyst according to the present invention. The terms polypropylene polymer or propylene based are used here alternatively. The polypropylene can be a propylene homopolymer or a mixture of propylene and ethylene, such as a propylene-based copolymer, for example, heterophasic propylene-olefin copolymer; random propylene-olefin copolymer, preferably the olefin in the propylene-based copolymers being a C2 or C4-C6 olefin, such as ethylene, butylene, pentene or hexene. Such propylene-based copolymers are known to the person skilled in the art; they are also described above.
[0353] [00353] The present invention also relates to a polyolefin, preferably a polymer based on propylene obtained or obtainable by the process as described here above, comprising contacting propylene or a mixture of propylene and ethylene with a catalyst system according to the present invention.
[0354] [00354] In one embodiment, the present invention relates to the production of a polypropylene homopolymer. For such a polymer, properties such as isotacticity and stiffness and emission may be important.
[0355] [00355] In an embodiment according to the present invention, a (random) copolymer of propylene and ethylene monomers is obtained. For such a polymer, properties such as XS and reduced haze increase after a while may be important.
[0356] [00356] In an embodiment according to the present invention, a heterophasic polypropylene having a matrix phase or any polypropylene homopolymer or a random propylene and ethylene copolymer and a dispersed phase of ethylene propylene rubber. This is called "impact polypropylene". For such a polymer, properties such as stiffness (reported as a flexural modulus) and impact can be important.
[0357] [00357] The comonomer content used in the addition to propylene (for example, ethylene or C4-C6 olefin) can vary between 0 and 8% by weight based on the total weight of the polymer, preferably between 1 and 4% by weight.
[0358] [00358] The "comonomer content" or "C2" content in the context of the present invention means the percentage by weight (% by weight) respectively, of the comonomer or ethylene incorporated in the total weight of the polymer obtained and measured with FT-IR. The FT-IR method was calibrated using NMR data.
[0359] [00359] Various properties of polymers are discussed here.
[0360] [00360] The polyolefin, preferably the polypropylene according to the present invention has a molecular weight distribution greater than 3.5, preferably greater than 4, more preferably greater than 4.5 and for example, below 10 or below 9 or even below 6. The molecular weight distribution of the polyolefins, preferably of the polypropylene according to the present invention, is, for example, between 3.5 and 9, preferably between 4 and 6, more preferably between 4.5 and 6.
[0361] [00361] Xylene-soluble fraction (XS) is preferably between about 0.5% by weight to about 10% by weight, or between about 1% by weight to about 8% by weight, or between 2 and 6 % by weight, or between about 1% by weight to about 5% by weight. Preferably the amount of xylene (XS) is less than 6% by weight, preferably less than 5% by weight, more preferably less than 4% by weight or even less than 3% by weight and most preferably less than than 2.7% by weight.
[0362] The production rate is preferably between about 1 kg / g / h to about 100 kg / g / h, or between about 10 kg / g / h to about 40 kg / g / h.
[0363] [00363] MFR is preferably between about 0.01 g / 10 min to about 2000 g / 10 min, or between about 0.01 g / 10 min to about 1000 g / 10 min; or between about 0.1 g / 10 min to about 500 g / 10 min, or between about 0.5 g / 10 min to about 150 g / 10 min, or between about 1 g / 10 min to about 100 g / 10 min.
[0364] [00364] The olefin polymer obtained in the present invention is considered to be a thermoplastic polymer. The thermoplastic polymer composition according to the invention can also contain one or more usual additives, such as those mentioned above, including stabilizers, for example, thermal stabilizers, antioxidants, UV stabilizers; dyes, such as pigments and inks; clarifiers; surface tension modifiers; lubricants; flame retardants; mold release agents; fluidity-improving agents; plasticizers; anti-aesthetic agents; impact modifiers; expansion agents; fillers and reinforcing agents; and / or components that enhance the interfacial bond between the polymer and the filler, such as a maleatated polypropylene, in the case of the thermoplastic polymer it is a polypropylene composition. The person skilled in the art can select any suitable combination of additives and amounts of additives without undue experimentation.
[0365] [00365] The amount of additives depends on their type and function; it is typically between 0 to about 30% by weight; preferably between 0 to about 20% by weight; more preferably between 0 to about 10% by weight and most preferably between 0 to about 5% by weight based on the total weight of the composition. The sum of all components in a process to form polyolefins, preferably propylene-based polymers or their compositions must add up to 100% by weight.
[0366] [00366] The thermoplastic polymer composition of the invention can be obtained by mixing one or more of the thermoplastic polymers with one or more additives using any suitable medium. Preferably, the thermoplastic polymer composition of the invention is made in a way that allows easy processing into a molded article in a subsequent step, such as in the form of a pellet or granule. The composition can be a mixture of different particles or pellets; as a mixture of a thermoplastic polymer and a master batch of the nucleating agent composition or a mixture of pellets of a thermoplastic polymer comprising one of the two nucleating agents and a particulate comprising the other nucleating agent, possibly polymer pellets thermoplastic which comprise said nucleating agent. Preferably, the thermoplastic polymer composition of the invention is in the form of a pellet or granule as obtained by mixing all the components in a device such as an extruder; the advantage being a composition with homogeneous and well-defined concentrations of nucleating agents (and other components).
[0367] [00367] The invention also relates to the use of polyolefins, preferably the propylene-based polymers (also called polypropylenes) according to the invention in injection molding, blow molding, extrusion molding, compression molding, casting, molding by thin-wall injection, etc., for example, in food contact applications.
[0368] [00368] Additionally, the invention relates to a molded article comprising the polyolefin, preferably the propylene-based polymer according to the present invention.
[0369] [00369] The polyolefin, preferably the propylene-based polymer according to the present invention can be transformed into (semi) finished molded articles using a variety of processing techniques. Examples of suitable processing techniques include injection molding, injection and compression molding, thin wall injection molding, extrusion and compression and extrusion molding. Injection molding is widely used to produce articles such as, for example, lids and closures, batteries, buckets, containers, automotive exterior parts such as bumpers, automotive interior parts such as instrument panels or automotive parts under the hood. Extrusion is, for example, widely used to produce articles such as stems, sheets, films and pipes. Thin-wall injection molding can, for example, be used to make thin-walled packaging applications for both food and non-food segments. This includes buckets and containers and packaging for margarine and dairy cups.
[0370] [00370] It is noted that the invention relates to all possible combinations of characteristics cited in the claims. The features described in the description can also be combined.
[0371] [00371] Although the invention has been described in detail for purposes of illustration, it is understood that such details are only for that purpose and variations can be made by those skilled in the art without departing from the spirit and scope of the invention as defined in the claims .
[0372] [00372] It should be noted that the invention relates to all possible combinations of characteristics described herein; in particular, those combinations of features that are present in the claims are preferred.
[0373] [00373] It should also be noted that the expression "comprising" does not exclude the presence of other elements. However, it should also be understood that a description of a product that comprises certain components also describes a product that consists of those components. Similarly, it should also be understood that the description of a process that comprises certain steps also describes a process that consists of those steps.
[0374] [00374] The invention will be further clarified with the following examples, without being limited to them. EXAMPLES
[0375] [00375] Dimethylamino triethoxysilane (DEATES) is an external electron donor that has been synthesized according to Example 1 of US 7,238,758 B2 which is incorporated by reference. Preparation of the pro-catalyst I Formation of the Grignard stage
[0376] [00376] A flask under agitation, equipped with a reflux condenser and a funnel, was filled with magnesium powder (24.3 g). The flask was placed under nitrogen. Magnesium was heated to 80 ° C for one hour, after which dibutyl ether (DBE) (150 ml), iodine (0.03 g) and n-chlorobutane (4 ml) were successively added. After the color of the iodine had disappeared, the temperature was raised to 80 ° C and a mixture of n-chlorobutane (110 ml) and DBE (750 ml) was slowly added over 2.5 hours. By decanting, the colorless solution above the precipitate, a solution of butylmagnesium chloride (reaction product from step A) with a concentration of 1.0 mol of Mg / l was obtained. B. Preparation of the intermediate reaction product
[0377] [00377] 250 ml of dibutyl ether were introduced into a 1 L reactor equipped with a stirring propeller and two deflectors. The reactor had the thermostat set to 35 ° C and the agitation speed was maintained at 200 rpm. Then 360 ml of a cooled solution (to 15 ° C) of the Grignard reaction product as prepared in A and 180 ml of a cooled solution (to 15 ° C) of 38 ml of tetraethoxysilane (TES) in 142 ml of DBE were fed to the reactor for 400 min with preliminary mixing in a mini-mixer of 0.15 ml volume, which was cooled to 15 ° C by means of cold water circulating in the mini-mixer liner. The pre-mixing time was 18 seconds in the mini-mixer and in the connection tube between the mini-mixer and the reactor. The stirring speed of the mini-mixer was 1000 rpm. After completion of the addition, the reaction mixture was maintained at 35 ° C for 0.5 hours. Then, the reactor was heated to 60 ° C and maintained at that temperature for 1 hour. Then the stirrer was stopped and the solid substance was allowed to settle. The supernatant was removed by decantation. The solid substance was washed three times using 300 ml of heptane. As a result, a solid white reaction product was obtained and suspended in 200 ml of heptane.
[0378] [00378] Under an atmosphere of inert nitrogen at 20 ° C, a 250 ml glass vial equipped with a mechanical stirrer is filled with a suspension of 5 g of the reaction product from step B dispersed in 60 ml of heptane. Subsequently, a solution of 0.86 ml of methanol (MeOH / Mg = 0.5 ml) in 20 ml of heptane is added under stirring for one hour. After keeping the reaction mixture at 20 ° C for 30 minutes, the suspension was allowed to warm slowly to 30 ° C for 30 min and maintained at that temperature for another two hours. Finally, the supernatant liquid is decanted from the solid reaction product which was washed once with 90 ml of heptane at 30 ° C. C. Preparation of the Pro-catalyst Component
[0379] [00379] A reactor was placed under nitrogen and 125 ml of titanium tetrachloride was added to it. The reactor was heated to 90 ° C and a suspension, containing about 5.5 g of the support obtained in step C in 15 ml of heptane, was added to it with stirring. The reaction mixture was maintained at 90 ° C for 10 min. Then, ethyl benzoate (EB) was added (molar ratio of EB / Mg = 0.15). The reaction mixture was maintained for 60 min. Then the stirring was stopped and the solid substance was allowed to settle. The supernatant was removed by decantation, after which the solid product was washed with chlorobenzene (125 ml) at 90 ° C for 20 min. The washing solution was removed by decanting, after which the mixture of titanium tetrachloride (62.5 ml) and chlorobenzene (62.5 ml) was added. Then, di-n-butyl phthalate (DNB) (molar ratio of DNB / Mg = 0.15) in 3 ml of chlorobenzene was added to the reactor and the temperature of the reaction mixture was increased to 115 ° C. The reaction mixture was maintained at 115 ° C for 30 min. After that, stirring was stopped and the solid substance was allowed to settle. The supernatant was removed by decanting, after which a mixture of titanium tetrachloride (62.5 ml) and chlorobenzene (62.5 ml) was added. The reaction mixture was maintained at 115 ° C for 30 min, after which the solid substance was allowed to settle. The supernatant was removed by decanting and the solid was washed five times using 150 ml of heptane at 60 ° C, after which the pro-catalyst component, suspended in heptane, was obtained. Preparation of Pro-catalyst II (Comparative)
[0380] [00380] Pro-catalyst II was prepared according to the method described in US 4,866,022. This patent describes a component comprising a product formed by: A. forming a solution of a species containing magnesium from magnesium carbonate or magnesium carboxylate; B. precipitate the solid particles of such a solution containing magnesium by treatment with a transition metal halide and an organosilane that has the formula: RnSiR'4-n, where n = 0 to 4 and where R is hydrogen or a alkyl, haloalkyl or aryl radical containing one to about ten carbon atoms or a halosylyl radical or haloalkylsilyl radical containing one to about eight carbon atoms and R 'is OR or a halogen; C. precipitating such solid particles again from a mixture containing a cyclic ether; and D. treating the precipitated particles again with a transition metal compound and an electron donor. That process for the preparation of a catalyst component is incorporated in the present application by reference. Preparation of Pro-catalyst III (Comparative)
[0381] [00381] WO03 / 068828 describes a process for the preparation of a catalyst component on page 91 "preparation of solid catalyst components", the section of which is incorporated in the present application by reference. Magnesium chloride, toluene, chloropropane epoxy and tributyl phosphate were added under nitrogen to a reactor, followed by heating. Then, phthalic anhydride was added. The solution was cooled to -25 ° C and TiCl4 was added by dripping, followed by heating. An internal donor was added (1,3-diphenyl-1,3-propylene glycol dibenzoate, 2-methyl-1,3-diphenyl-1,3-propylene glycol dibenzoate, 1,3-diphenyl-1 dipropionate, 3-propylene glycol or 1,3-diphenyl-2-methyl-1,3-propylene glycol diproprionate) and after stirring, a solid was obtained and washed. The solid was treated twice with a toluene solution, TiCl4, followed by washing with toluene to obtain said catalyst component. Preparation of Pro-catalyst IV (Comparative)
[0382] [00382] US 4,771,024 describes the preparation of a pro-catalyst in column 10, row 61 through column 11, row 9. The section "making the catalyst on silica" is incorporated in the present application by reference. The process comprises combining dry silica with a solution of carbonated magnesium (magnesium diethoxide in ethanol was bubbled with CO2). The solvent was evaporated at 85 ° C. The resulting solid was washed and a 50:50 mixture of titanium tetrachloride and chlorobenzene was added to the solvent along with ethyl benzoate. The mixture was heated to 100 ° C and the liquid filtered. Again, TiCl4 and chlorobenzene were added, followed by heating and filtration. A final addition of TiCl4 and chlorobenzene and benzoyl chloride was performed, followed by heating and filtration. After washing, the pro-catalyst was obtained. Batch Production of Propylene Homopolymers
[0383] [00383] Propylene polymerization experiments (Table 1) were performed using the pro-catalyst i described above. Triethyl aluminum was used as a cocatalyst and DiPDMS and DEATES were used as external donors. The experiments were carried out in different molar proportions of H2 / C3.
[0384] [00384] The polymerization reaction was carried out in a stainless steel reactor with a volume of 1800 mL. Under a nitrogen atmosphere, the cocatalyst (TEAL) and the pro-catalyst synthesized according to the procedure described above and the external electron donor were fed into the reactor as heptane solutions or suspensions. 10 to 15 mg of pro-catalyst were employed. The molar ratio of cocatalyst to titanium (from the pro-catalyst) was adjusted to 160 and the Si / Ti ratio was adjusted to 9. During this dosing, the reactor temperature was kept below 30 ° C. Subsequently, the reactor was pressurized using an adjusted proportion of propylene and hydrogen and the temperature and pressure were raised to its set point (70 ° C and 20 barg). After the pressure point had been reached, polymerization was continued for 60 minutes (i.e., polymerization time = 60 minutes). During the polymerization reaction, the composition of propylene gas and hydrogen was controlled using mass flow meters and online GC control. After reaching the polymerization time, the reactor was depressurized and cooled to ambient conditions. The propylene polymer thus obtained was removed from the reactor and stored in aluminum bags. Batch Production of Propylene-Ethylene Copolymers
[0385] [00385] The copolymerization of propylene and ethylene was carried out in a stainless steel reactor with a volume of 1800 mL. The cocatalyst (TEAL), pro-catalyst and external electron donor (silane compound) components were dosed as heptane solutions or suspensions to the reactor, which is under a nitrogen atmosphere, while the reactor temperature is maintained below 30 ° C. Subsequently, the reactor was pressurized using a proportion of propylene, ethylene and hydrogen and the temperature and pressure were raised to its set point (60 ° C and 20 barg). After the pressure point had been reached, polymerization was continued for 75 minutes. During the polymerization reaction, the composition of the propylene, ethylene and hydrogen gas buffer was controlled using mass flow meters and online GC control. After reaching the polymerization time, the reactor was depressurized and cooled to ambient conditions. The random propylene-ethylene copolymer thus obtained was removed from the reactor and stored in aluminum bags.
[0386] - rendimento de PP, kg/g de cat é a quantidade de polipropileno obtida por grama de componente catalisador. - H2/C3 é a proporção molar de hidrogênio para propileno no tampão de gás do reator, medida pela cromatografia a gás online. - Conteúdo de oligômeros se refere à quantidade em ppm em uma amostra de polímero dos oligômeros de alfa-olefina C2-C33, que tipicamente se originam do material de baixo peso molecular na composição polimérica. Uma amostra pesada de 50 a 100 mg do filamento de polímero produzido foi carregada em um tubo de material inerte. Esse tubo foi rapidamente purgado em temperatura ambiente usando hélio. O tubo foi aquecido a 200°C e um veículo gasoso foi passado sobre a amostra de polímero fundido por 30 minutos. Depois de sair do tubo, o veículo gasoso foi passado através de uma câmara fria, que condensou os componentes voláteis liberados do polímero. Subsequentemente, a câmara fria foi rapidamente aquecida para 250°C e os voláteis foram injetados em uma coluna CP-SIL5 GC (25 metros). A identificação dos componentes individuais foi realizada usando um detector de MS e a quantificação foi realizada usando um detector de FID. Tabela 1. Resultados de um lote de homopolimerização de propileno
[0387] [00387] Table 1 above shows that, comparing homopolymers made using pro-catalyst I and external DEATES donor, homopolymer compositions with lower oligomer content in similar MFR are provided and that homopolymers with high MFR can be made by applying a proportion of H2 / C3 in the reactor. Semi-continuous Preparation of Propylene Homopolymer and Heterophasic Copolymer
[0388] [00388] Gas phase polymerizations were carried out in a set of two cylindrical reactors, horizontal in series, in which a propylene homopolymer was formed in the first reactor and an ethylene-propylene copolymer rubber in the second to prepare an impact copolymer . The first reactor was operated continuously, the second reactor in batch mode. In the synthesis of the homopolymer, the polymer was loaded into the secondary reactor covered with nitrogen. The first reactor was equipped with a gaseous effluent port for recycling the reactor gas through a condenser and back through a recycling line to the nozzles in the reactor. Both reactors had a volume of one gallon (3.8 liters), measuring 10 cm in diameter and 30 cm in length. In the first reactor, liquid propylene was used as a coolant; for the synthesis of copolymers, the temperature in the second reactor was kept constant with a cooling jacket. Pro-catalysts I and II were introduced into the first reactor as a suspension of 5 to 7 weight percent in hexane through a liquid catalyst-propylene addition nozzle.
[0389] [00389] The external donor and TEAL in hexane were fed to the first reactor through a different liquid propylene addition nozzle. For the production of a heterophasic polymer, an Al / Mg ratio of 9 and an Al / Si ratio of 13.5 was used.
[0390] [00390] During the operation, the polypropylene powder produced in the first reactor passed through a reservoir and was discharged through a powder discharge system in the second reactor. The polymeric bed in each reactor was agitated by the blades coupled to a longitudinal axis inside the reactor, which was rotated at about 50 rpm in the first and about 75 rpm in the second reactor. The reactor temperature and pressure were maintained at 61 ° C and 2.2 Mpa in the first and for the synthesis of the copolymer at 66 ° C and 2.2 Mpa in the second reactor. The production rate was about 200 to 250 g / h in the first reactor in order to obtain a stable process. For homopolymer synthesis, the hydrogen concentration in the gas effluent was controlled in order to obtain the desired fluidity index (MFR) ratio. For the synthesis of copolymer, hydrogen was fed to the reactor to control the flow rate of the homopolymer powder and copolymer powder. The composition of ethylene-propylene copolymer (RCC2) was controlled by adjusting the proportion of ethylene and propylene (C2 / C3) in the recycling gas in the second reactor based on gas chromatography analysis. In this regard, RCC2 is the amount of ethylene incorporated in the rubber fraction (weight percentage) and RC is the amount of rubber incorporated in the impact copolymer (weight percentage). RC and RCC2 were measured by IR spectroscopy, which was calibrated using 13C-NMR according to known procedures.
[0391] - Al/Mg é a proporção molar de alumínio (do co-catalisador) para o magnésio (do pró-catalisador) adicionados ao reator. - Si/Mg é a proporção molar de silício (do doador externo) para o magnésio (do pró-catalisador) no reator. - Si/Ti é a proporção molar de silício (do doador externo) para o titânio (do pró-catalisador) no reator. - H2/C3 é a proporção molar de hidrogênio para propileno no tampão de gás do reator, medida pela cromatografia a gás online. Tabela 2. Dados da homopolimerização semicontínua usando o pró-catalisador I.
[0392] [00392] Table 2 shows that in the case of DEATES, a much lower proportion of H2 / C3 in the reactor can be applied to obtain a homopolymer with a larger MFR. Table 3. Semi-continuous production of heterophasic polypropylene using pro-catalyst I.
[0393] [00393] Table 3 shows that for the production of heterophasic polypropylene, a much lower proportion of H2 / C3 can be used with the use of the DEATES donor instead of DiPDMS and, therefore, heterophasic polypropylenes with higher MFR can be made using this donor. In addition, the proportion of C2 / C3 in the second reactor can be much lower in the second reactor using the DEATES donor in order to obtain a high RCC2 in the ethylene-propylene copolymer that is made in the second reactor. Therefore, DEATES shows a greater sensitivity to hydrogen and greater to ethylene. Property Valuation
[0394] [00394] For the evaluation of the properties, the polymer powder was pre-mixed with the additives (quantities in the final product: 2500 ppm of thermal stabilizer, 2500 ppm of process stabilizer, 900 ppm of Ca stearate, 1000 ppm of agent antistatic and 2500 ppm clarifier) and mixed in a mini-mixer to give the polymeric composition. The following properties of the polymeric composition were measured:
[0395] [00395] * Haze plates: the polymer composition was injection molded at a melting temperature of 220 ° C and a mold temperature of 20 ° C.
[0396] [00396] * Bars for mechanical properties (for determining the bending modulus and Izod) were prepared from the polymer composition by injection molding under the following conditions: Drum temperature = 230 ° C, mold temperature = 45 ° Ç. Table 4. Properties of the composition comprising the propylene-ethylene copolymers prepared using different pro-catalysts. For all examples, DEATES was used as the external donor
[0397] [00397] The MWD was determined for Example n °. 5, being 5.1; for Example 8. being 4.7 and for Example no. 9, being 6.2.
[0398] [00398] The mol / mol ratio of Al / Ti was 50 for Examples 1,2, 3, 4, 7, 8 and 9; it was 100 for Example No. 5 and was 160 for Example No. 6.
[0399] [00399] As can be seen from Table 4 above, with the use of the pro-catalyst prepared by the process of claim 6, a composition can be obtained, the composition of which shows a low soluble content in xylene in combination with low blooming, while mechanical properties are maintained. Blooming is not desired, as it will negatively affect the optical appearance of an article prepared with said composition.
[0400] [00400] Therefore, the invention also relates to a composition comprising a propylene-ethylene copolymer that has a content soluble in xylene (XS) less than 7.5% by weight, in which the XS is measured according to ASTM D 5492-10 and that has an increase in haze after 21 days at 50 ° C less than 12, for example, less than 11, where the increase in haze after 21 days at 50 ° C is the difference between the haze value of the sample before heating and the haze value after heating the sample to 50 ° C for 21 days and where the haze value is measured in a BYK Gardner according to ASTM D 1003-00, in that the amount of ethylene in the propylene-ethylene copolymer is in the range of 1 to 8% by weight, preferably in the range of 2 to 6, for example, in the range of 3 to 4.5% by weight based on the propylene copolymer -ethylene. Preferably, said composition has a molecular weight distribution in the range of 4 to 6.5, for example in the range of 5 to 6 and / or preferably said composition has a fluidity index measured according to ISO 1133: 2005 to 230 ° C with a load of 2.16 kg in the range between 5 to 100, for example in the range between 10 to 100, for example, in the range between 10 to 35, where the molecular weight distribution (MWD) was determined by chromatography permeation in Waters gel at 150 ° C combined with a Viscotek 100 differential viscometer. The chromatograms were run at 140 ° C using 1,2,4-trichlorobenzene as a solvent with a flow rate of 1 ml / min. The refractive index detector was used to collect the signal for molecular weights.
[0401] [00401] The static was observed visually by inspecting the reactor wall. The following criteria are used: no static observed, meaning that the polymer powder was not visible on the stirrer or on the reactor walls (after opening the reactor) observed static, meaning that the polymer powder was visible on the agitator and / or on the reactor walls (after the reactor was opened)
[0402] [00402] When DEATES is used for the polymerization of a polyolefin, preferably a propylene polymer, the static in the reactor is significantly reduced.
[0403] [00403] Such a composition can be suitably used in injection molding, for example, for the manufacture of molded articles.

权利要求:
Claims (10)
[0001]
Process for the preparation of a suitable catalyst system for the polymerization of an olefin, characterized by the fact that the process comprises the steps of: (A) providing said pro-catalyst obtainable through a process that comprises the steps of: (i) contacting a compound R4zMgX42-z with a silane compound containing alkoxy or aryloxy to give a first intermediate reaction product, being a Mg (OR1) xX12-x solid, where: R4 is equal to R1 which is a linear, branched or cyclic hydrocarbyl group having between 1 and 20 carbon atoms and independently selected from the alkyl, alkenyl, aryl, aralkyl or alkylaryl groups and one or more combinations thereof; wherein said hydrocarbyl group can be substituted or unsubstituted, it can contain one or more heteroatoms and; X4 and X1 are each selected independently from the group consisting of fluoride (F-), chloride (Cl-), bromide (Br-) or iodide (I-), preferably chloride; z is in the range of greater than 0 and less than 2, with 0 <z <2; (ii) optionally contact the solid Mg (OR1) xX2-x obtained in step (i) with at least one activating compound selected from the group formed by the electron donating and metal alkoxide activating compounds of formula M1 (OR2) vw (OR3 ) w or M2 (OR2) vw (R3) w to obtain a second intermediate product; where M1 is a metal selected from the group consisting of Ti, Zr, Hf, Al or Si; M2 is a metal that is Si; v is the valence of M1 or M2; R2 and R3 are each, a linear, branched or cyclic hydrocarbyl group having between 1 and 20 carbon atoms and independently selected from the alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups and one or more combinations thereof; wherein said hydrocarbyl group can be substituted or unsubstituted, it can contain one or more heteroatoms; (iii) contacting the first or second intermediate reaction products obtained, respectively, in step (i) or (ii), with a Ti compound containing halogen and, optionally, an internal electron donor to obtain said pro-catalyst ; (B) contacting said pro-catalyst with a cocatalyst and at least one external electron donor which is in accordance with Formula III (R90) 2N-Si (OR91) 3, where each of R90 and R91 is ethyl , being diethylaminotrietoxysilane.
[0002]
Process according to claim 1, characterized by the fact that the process is essentially phthalate free.
[0003]
Process according to claim 1 or 2, characterized by the fact that the optional internal electron donor is an aminobenzoate according to formula XI,
[0004]
Process according to claim 3, characterized in that the optional internal electron donor is selected from the group consisting of 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, 4- (methylamino) pentan-2-yl bis (4-methoxy) benzoate), 3- [benzoyl (cyclohexyl) amino] -1- benzoate phenylbutyl, 3 [benzoyl (propan-2-yl) amino] -1-phenylbutyl, 4- [benzoyl (methyl) amino] -1,1,1 -trifluopentan-2-yl, 3- (methylamino) -1 dibenzoate -1 , 3-diphenylpropan-1-ol, 3- (methyl) amino-propan-1-ol dibenzoate; 3- (methyl) amino-2,2-dimethylpropan-1-ol and 4- (methylamino) pentan-2-yl-bis- (4-methoxy) benzoate dibenzoate).
[0005]
Process according to any one of claims 1 to 4, characterized in that the optionally one or more internal electron donors are activated by an activator, preferably in which the activator is a benzamide according to formula X,
[0006]
Process according to claim 5, characterized by the fact that the activator is N, N-dimethylbenzamide.
[0007]
Process according to any one of claims 1 to 4, characterized in that the benzamide according to formula X is present in the pro-catalyst in an amount between 0.1 to 4% by weight, as determined using HPLC, by for example, between 0.1 to 3.5% by weight, for example between 0.1 to 3% by weight, for example between 0.1 to 2.5% by weight, for example between 0.1 to 2.0 % by weight, for example between 0.1 to 1.5% by weight.
[0008]
Catalyst system, characterized by the fact that it is obtained or obtainable by the process as defined in any one of claims 1 to 7.
[0009]
Process for preparing a polyolefin, characterized in that it contacts at least one olefin with the catalyst system as defined in claim 8, wherein the olefin is preferably propylene or a mixture of propylene and ethylene.
[0010]
Polyolefin, characterized in that it is obtained or obtainable by the process for the preparation of a polyolefin as defined in claim 9, preferably a polypropylene of a propylene-ethylene copolymer.

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WO2020069853A1|2018-10-02|2020-04-09|Sabic Global Technologies B.V.|Method for the manufacture of a polyolefin compound|

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US20210403691A1|2018-11-19|2021-12-30|Sabic Global Technologies B.V.|Food packaging comprising a polymer composition and use of said polymer composition for manufacturing of food packaging|

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WO2021043784A1|2019-09-06|2021-03-11|Sabic Global Technologies B.V.|Healthcare article comprising a random propylene-ethylene copolymer.|

法律状态:
2019-12-31| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-11-17| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2021-02-09| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-03-23| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 19/12/2014, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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EP13199169.7|2013-12-20|

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EP13199169|2013-12-20|

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EP14170828.9|2014-06-02|

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EP14170828|2014-06-02|

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PCT/EP2014/078795|WO2015091981A2|2013-12-20|2014-12-19|Catalyst system for polymerisation of an olefin|

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