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    • 专利摘要:
    hydrocarbon insoluble solid catalyst component, method for polymerizing an olefin and compound a hydrocarbon insoluble solid catalyst component, useful in the polymerization of olefins, said catalyst component containing magnesium, titanium and halogen, and also containing an internal electron donor with structure: [r1-0-c (o) -o-jxr2, where r1 is independently, at each occurrence, an aliphatic or aromatic hydrocarbon, or substituted hydrocarbon group of 1 to 20 carbon atoms; x is 2-4; and r2 is an aliphatic or aromatic hydrocarbon, or substituted hydrocarbon group containing from 1 to 20 carbon atoms, as long as there are 2 atoms in the shortest chain that connects a first group r1-0-c (o) -0- and a second group r1-0-c (0) -0-.
    公开号:BR112012013286B1
    申请号:R112012013286-5
    申请日:2010-11-30
    公开日:2020-03-10
    发明作者:Joseph N. Coalter；Tak W. Leung；Tao Tao；Kuanqiang Gao
    申请人:W. R. Grace & Co. - Conn；
    IPC主号:
    专利说明:

    “HYDROCARBON INSOLUBLE SOLID CATALYST COMPONENT AND METHOD FOR POLYMERIZING AN OLEPHINE” [001] The present invention relates to components useful in catalysts for propylene polymerization, and particularly to electron donor components used in combination with supported catalyst components containing magnesium and titanium.
    Background and summary of the invention [002] The use of solid catalyst components for polymerization of transition metal-based olefin is well known in the art, including such solid components supported on a metal oxide, halide or other salt such as widely described components of magnesium-containing titanium halide catalyst. Such catalyst components are generally referred to as "supported". Although many catalytic processes and systems for polymerization and copolymerization have been described to polymerize or copolymerize alpha-olefins, it is advantageous to adapt a catalytic process and system to obtain a specific set of properties of a resulting polymer or copolymer product. For example, in certain applications, a combination of acceptably high activity, good morphology, desired particle size distribution, acceptable bulk density, and the like, are required, along with polymer characteristics, such as stereospecificity, molecular weight distribution, and similar.
    [003] Typically, the supported catalyst components useful for polymerizing propylene and higher alpha-olefins, as well as for polymerizing propylene and higher olefins with smaller amounts of ethylene and other alpha-olefins contain an internal electron donating component. Such an internal electron donor is an integral part of the supported solid catalyst component and is distinguished from an external electron donor component, which, together with an alkyl aluminum component, typically comprises the catalytic system. Although the internal electron donor is an integral part of the supported solid component, the internal electron donor can be combined with the supported solid component shortly before the combination is contacted with an olefin monomer or in the presence of an olefin monomer. The external electron donor is commonly referred to as a selectivity control agent (or "SCA") and the supported catalyst component is commonly referred to as a pro-catalyst.
    [004] The selection of the internal electron donor can affect the catalytic performance and the resulting polymer formed from a catalytic system. Generally, internal electron donors have been described as useful in the preparation of supported stereospecific catalyst components, including organic components containing oxygen, nitrogen, sulfur and / or phosphorus. Such compounds include organic acids, organic acid anhydrides, organic acid esters, alcohols, ethers, aldehydes, ketones, amines, amine oxides, amides, thiols, various phosphoric acid esters and amides, and the like. Mixtures of organic electron donors have been described as useful when incorporated into the supported catalyst components. Examples of organic electron donors include dicarboxy esters, such as alkyl phthalate and succinate esters.
    [005] In current practice, alkyl phthalate esters are commonly used as internal electron donors in catalytic systems for propylene polymerization. However, certain environmental issues have been raised related to the continued use of phthalate derivatives in applications where human contact is expected.
    [006] Specific uses of propylene polymers depend on the physical properties of the polymer, such as molecular weight, viscosity, stiffness, flexural modulus, and polydispersity index (molecular weight distribution (Mw / Mn)). In addition, the morphology of the polymer or copolymer is often critical and typically depends on the morphology of the catalyst. A good polymer morphology generally involves uniformity in particle size and shape, resistance to friction and an acceptably high apparent density. The minimization of very small (fine) particles is typically important, especially in gas phase polymerizations or copolymerizations, to avoid obstruction in the transfer or recycling line.
    [007] The state of the art currently recognizes a finite set of compounds suitable for use as internal electron donors in supported catalyst components. With the continued diversification and sophistication of applications for olefin-based polymers, the state of the art recognizes the need for olefin-based polymers with improved and varied properties. Internal electron donors would be desirable in supported catalyst components that contribute to strong catalytic activity and high hydrogen response during polymerization. Internal electron donors in supported catalyst components that produce propylene-based polymers with high isotacticity, commonly expressed as a soluble fraction in xylenes (XS) and / or final melting temperature (TMF), are also desired.
    [008] The invention described relates to the use of an internal modifier (internal electron donor) in a catalyst component for propylene polymerization, which contains at least two carbonate functionalities.
    [009] Consequently, an embodiment of the invention consists of a solid catalyst component, insoluble in hydrocarbon and useful in the polymerization of olefins, said catalyst component containing magnesium, titanium and halogen, and further containing an internal electron donor comprising a compound with the following structure: [R1-OC (O) -O-] xR2 where R1 is independently at each occurrence, an aliphatic or aromatic hydrocarbon, or substituted hydrocarbon group containing from 1 to 20 carbon atoms; x is 2-4; and R2 is an aliphatic or aromatic hydrocarbon, or substituted hydrocarbon group containing from 1 to 20 carbon atoms, provided that there are 2 atoms in the shortest chain connecting a first group R1-OC (O) -O and a second group R1-OC ( O) -O-.
    [0010] Preferably, R2 is a 1,2-substituted phenyl moiety. More preferably, each R1 is an aromatic or aliphatic hydrocarbon group. More preferably, each R1 is ethyl or phenyl.
    [0011] Preferably, R2 is a 1,2- or 3,4-substituted naphthyl moiety. More preferably, each R1 is an aromatic or aliphatic hydrocarbon group. More preferably, each R1 is ethyl or phenyl.
    [0012] Preferably, R2 is a straight or branched chain alkyl moiety, as long as there are 2 atoms in the shortest chain that connects a first group R1-OC (O) -O- and a second group R1-OC (O) - THE-. More preferably, each R1 is an aromatic or aliphatic hydrocarbon group. More preferably, each R1 is ethyl or phenyl.
    [0013] Preferably, the catalyst component is optionally combined with a simple SCA component, a mixed SCA component, or an activity limiting agent. More preferably, the mixed SCA component contains an activity limiting agent or an organic ester as a component.
    [0014] Preferably, a compound suitable for use as an internal electron donor is provided with the following structure: [R1-OC (O) -O-] xR2 where R1 is independently at each occurrence, an aliphatic or aromatic hydrocarbon, or substituted hydrocarbon group containing from 1 to 20 carbon atoms; x is 2-4; and R2 is a substituted phenyl or naphthyl group, the substituent being not an additional fused aromatic ring, containing 1 to 20 carbon atoms, as long as there are 2 atoms in the shortest chain that connects a first Ri-OC (O) group -O- and a second group Ri-OC (O) -O-.
    Detailed description of the invention Definitions [0015] All references to the Periodic Table of Elements cited here refer to the Periodic Table of Elements published and protected by copyright by CRC Press, Inc.2003. Also, any references to a Group or Groups refer to the Group or Groups that appear in the Periodic Table of the Elements, using the IUPAC system to enumerate the groups. Unless otherwise stated, implicit in the context, or common in the state of the art, all parts and percentages are by weight. For the purposes of American patent practice, the contents of any patent, patent application, or publication cited herein are hereby incorporated by reference in their entirety (or the equivalent American version thereof so incorporated by reference), especially with respect to the description of synthetic techniques, definitions (as long as they do not contradict any definition provided here) and general knowledge of the state of the art.
    [0016] The term "comprising" and its derivatives, is not intended to exclude the presence of any additional component, step or procedure, whether or not they are described in the present invention. For the avoidance of doubt, all compositions claimed herein using the term "comprising" may include any additive, adjuvant or additional compound, whether polymeric or otherwise, unless stated otherwise. On the contrary, the term "consisting essentially of" excludes any other component, step or procedure from the scope of any subsequent quotation, with the exception of those that are essential to operability. The term "consisting of", excludes any component, step or procedure not specifically described or listed. The term "or", unless otherwise stated, refers to the related members individually, as well as in any combination.
    [0017] Any numerical range mentioned here includes values from the lowest value to the maximum value, in increments of one unit, as long as there is a separation of at least 2 units between any lower value and any higher value. As an example, if it is mentioned that the amount of a component, or the value of a compositional or physical property, such as, for example, the amount of a mixing component, softening temperature, melting index, etc. is between 1 and 100, it is intended to state that all individual values, such as 1,2, 3, etc., and all sub-ranges, such as 1 to 20, 55 to 70, 197 to 100, etc. , are expressly listed in this report. For values that are less than one, a unit is considered to be 0.0001, 0.001, 0.01 or 0.1, as appropriate. These are just examples of what is specifically intended, and all possible combinations of numerical values between the lowest value and the highest value listed should be considered as expressly cited in the present invention. In other words, any numerical range cited in the present invention includes any value or subrange in the cited range. Numerical ranges have been cited, as discussed here, as well as reference melting index, melt flow rate, and other properties.
    [0018] The term "composition", as used herein, includes a mixture of materials comprising the composition, as well as reaction products and decomposition products formed with the materials of the composition.
    [0019] The terms "mixture" or "polymeric mixture", as used herein, is a mixture of two or more polymers. Such a mixture may or may not be miscible (not separated into phases at the molecular level). Such a mixture may or may not be separated into phases. Such a mixture may or may not contain one or more domain configurations, as determined based on transmission electron electroscopy, light scattering, x-ray scattering, and other methods known in the art.
    [0020] The term "polymer" is a macromolecular compound prepared by polymerizing monomers of the same or a different type. "Polymer" includes homopolymers, copolymers, terpolymers, interpolymers and so on. The term "interpolymer" means a polymer prepared by polymerizing at least two types of monomers or comonomers. It includes, although it is not restricted to copolymers (which generally refers to polymers prepared with two different types of monomers or comonomers. It includes, although it is not restricted to copolymers (which generally refers to polymers prepared with two different types of monomers) or comonomers, terpolymers, tetrapolymers and the like.
    [0021] The term "interpolymer", as used herein, refers to polymers prepared through the polymerization of at least two different types of monomers. The generic term interpolymer thus includes copolymers, generally used to refer to polymers prepared with two different types of monomers and polymers prepared with more than two different types of monomers.
    [0022] The term "olefin-based polymer" is a polymer containing, in polymerized form, a majority weight percentage of an olefin, for example, ethylene or propylene, based on the total weight of the polymer. Non-restrictive examples of olefin-based polymers include ethylene-based polymers and propylene-based polymers.
    [0023] The term "ethylene-based polymer", as used herein, refers to an interpolymer comprising a majority by weight of polymerized ethylene monomer (based on the total weight of polymerizable monomers), and optionally can comprise at least one polymerized comonomer.
    [0024] The term "propylene-based polymer", as used herein, refers to a polymer that comprises a majority weight percentage of polymerized propylene monomer (based on the total amount of polymerizable monomers) and optionally can comprise at least least one polymerized comonomer.
    [0025] As used herein, the term "hydrocarbyl" and "hydrocarbon" refer to substituents containing only hydrogen and carbon atoms, including branched and unbranched, saturated or unsaturated, cyclic, polycyclic, fused or acyclic species and combinations thereof . Non-restrictive examples of hydrocarbyl groups include alkyl, cycloalkyl, alkenyl, alkadienyl, cycloalkenyl, cycloalkylenyl, aryl, aralkyl, alkylaryl, and alkynyl groups.
    [0026] As used herein, the terms "substituted hydrocarbyl" and "substituted hydrocarbon" refer to a hydrocarbyl group that is substituted with one or more non-hydrocarbyl substituent groups. A non-restrictive example of a non-hydrocarbyl substituent group is a heteroatom. As used herein, the term "heteroatom" refers to an atom other than a carbon or hydrogen. The heteroatom can be a non-carbon atom of groups IV, V, VI and VII of the Periodic Table of the Elements. Non-restrictive examples of heteroatoms include: halogens (F Cl, Br, I), N, O, P, B, S and Si. A substituted hydrocarbyl group also includes a halohydrocarbyl group and a hydrocarbyl group containing silicon. As used herein, the term "halohydrocarbyl" group refers to a hydrocarbyl group that is substituted with one or more halogen atoms.
    [0027] The term "alkyl", as used herein, refers to an acyclic hydrocarbon radical, branched, unbranched, saturated or unsaturated. Non-restrictive examples of suitable alkyl radicals include, for example, methyl, ethyl, n-propyl, i-propyl, 2-propenyl (or allyl), vinyl, n-butyl, t-butyl, i-butyl (or 2-methylpropyl ), etc. Alkyls have 1 to 20 carbon atoms.
    [0028] The term "substituted alkyl", as used herein, refers to an alkyl described in which one or more hydrogen atoms attached to any alkyl carbon is substituted with another group such as halogen, aryl, substituted aryl, cycloalkyl , substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, halogen, haloalkyl, hydroxy, amino, phosphide, alkoxy, amino, uncle, nitro, other groups containing heteroatom, and combinations thereof. Suitable substituted alkyls include, for example, benzyl, trifluoromethyl and the like.
    [0029] The term "aryl", as used herein, refers to an aromatic substituent which can be a single aromatic ring or multiple aromatic rings that are fused together, covalently bonded or linked to a common group such as methylene or ethylene moiety . The aromatic ring (s) may include phenyl, naphthyl, anthracenyl, and biphenyl, among others. Aryls have 6 to 20 carbon atoms.
    [0030] The term "carbonate", as used herein, refers to a functional group in a larger molecule that contains a carbon atom attached to three oxygen atoms, one of which is double-bonded. Such compounds are also known as organocarbonates or carbonate esters.
    [0031] The supported catalyst components of the present invention contain at least one internal electron donor comprising electron donor substituents comprising a dicarbonate. Dicarbonates are defined as those compounds that correspond to the following structure: [R1-O-C (O) -O] xR2 where R1 is independently at each occurrence, an aliphatic or aromatic hydrocarbon, or substituted hydrocarbon group containing from 1 to 20 carbon atoms; x is 2-4; and R2 is an aliphatic or aromatic hydrocarbon, or substituted hydrocarbon group containing from 1 to 20 carbon atoms, provided that there are 2 atoms in the shortest chain connecting a first group R1-OC (O) -O and a second group R1-OC ( O) -O-.
    [0032] It is preferable that x is equal to 2, and as a result, in the broadest sense of the invention, that the term "dicarbonate" is used to generically describe these compounds, even if compounds with 3 or even 4 carbonate groups are envisaged .
    [0033] For many applications, it is preferred that the group R1 is an aliphatic or aromatic hydrocarbon group. It is also preferred that such an aliphatic group has a relatively smaller extent, for example, 1-6 carbon atoms, and that such a group is relatively compact, with, for example, having 6-10 carbon atoms.
    The groups R2 in the dicarbonates useful in the present invention are those with 2 atoms in the shortest chain between 2 carbonate groups. Preferably, these bonding atoms are carbon atoms, although hetero atoms such as oxygen, nitrogen, silicon or phosphorus can also be used. It should be understood that the term 2 bonding atoms refers only to the atoms in the shortest chain between the carbonate groups and that the R2 groups are typically much larger, as they contain atoms that do not directly link the carbonate groups. Preferred R2 groups include phenyls, where the linking atoms are adjacent on the ring, and naphthalene, where the linking groups are adjacent on one of the fused rings. Such phenyls or naphthalenes can advantageously contain alkyl groups or other substituents.
    [0035] The hydrocarbons useful in the present invention can be replaced with atoms other than carbon or hydrogen. For example, alkyl groups used in the present invention can be substituted with compatible groups containing hetero atoms, including nitrogen, oxygen, phosphorus, silicon and halogens. Thus, a hydrocarbon group used in the present invention can be replaced with an ether, amine, amide, chlorine, bromine or silyl group, for example. Similarly, cyclic structures that can be incorporated into donor compounds as part of the R1 or R2 groups may contain heteroatoms, such as nitrogen, oxygen, silicon and phosphorus.
    Non-restrictive examples of some specific dicarbonates for use in the present invention include those described below, and their substituted derivatives: [0036] Dicarbonate materials suitable for use as internal electron donors in the present invention can be prepared according to methods known in the art. state of the art. An appropriate method for preparing a true dicarbonate (that is, when x = 2) involves reacting a diol with at least two molar equivalents of a substituted chloroformate. Thus, the reaction can be described as follows: R2 (OH) 2 + 2 CI-C (O) -ORi -y [Ri-O-C (O) -O-] 2R2 where Ri and R2 are as described above. An appropriate base may be present to sequester the hydrochloric acid released during the reaction. A suitable variation of this method consists of first reacting the diol with a suitable base to perform partial or complete deprotonation, followed by treatment with at least 2 molar equivalents of a substituted chloroformate.
    [0037] The dicarbonates of the present invention are useful as internal electron donors in supported high-activity Ziegler-Natta catalysts containing titanium commonly used in the manufacture of polypropylene.
    [0038] The supported components containing titanium useful in the present invention are generally supported on compounds containing magnesium and insoluble in hydrocarbon in combination with an electron donating compound. Such a supported catalyst component containing titanium for olefin polymerization is formed by reacting a titanium (IV) halide, an organic electron donor compound and a magnesium-containing compound. Optionally, such a supported reaction product containing titanium can also be treated or modified by additional chemical treatment with electron donors or additional Lewis acid species. The resulting supported components containing titanium are also referred to as "supported catalyst components" or "pro-catalysts." [0039] Suitable compounds containing magnesium include magnesium halides; a reaction product of a magnesium halide, such as magnesium chloride or magnesium bromide with an organic compound, such as an alcohol or an ester of organic acid, or with an organometallic metal compound of Groups I-III; magnesium alcoholates; mixed magnesium / titanium halide alcoholates; or magnesium alkyl.
    [0040] Examples of supported catalyst components are prepared by reacting a magnesium chloride, magnesium alkoxide chloride or aryloxy magnesium chloride, or mixed magnesium / titanium halide alcoholate with a titanium halide, such as titanium tetrachloride, and additional incorporation of an electron donating compound. In a preferred preparation, the magnesium-containing compound is dissolved, or is in the form of a paste, in a compatible liquid medium, such as hydrocarbon or halogenated hydrocarbon to produce appropriate catalyst component particles.
    The possible supported catalyst components listed above are only illustrative of many possible solid catalyst components containing magnesium, based on titanium halide and insoluble in hydrocarbons, useful in the present invention and known in the art. The present invention is not restricted to a specific supported catalyst component.
    [0042] Supported catalyst components known in the art can be used with the internal donors described in the present invention. Typically, the internal electron donor material of the present invention is incorporated into the supported solid catalyst component during the formation of such a component. Typically, such an internal electron donor material is added with or in a separate step, during treatment of a solid material containing magnesium with an appropriate titanium source, such as a titanium (IV) compound. Such magnesium-containing material is typically in the form of discrete particles and may contain other materials such as transition metals and organic compounds. Likewise, a mixture of magnesium chloride, titanium tetrachloride and the internal donor can be formed into a catalyst component supported by a ball mill.
    Magnesium Source [0043] The magnesium source is preferably in the form of a supported catalyst component precursor, prepared according to any of the procedures described, for example, in U.S. Pat. 4,540,679; 4,612,299; 4,866,022; 4,946,816; 5,034,361; 5,066,737; 5,082,907; 5,106,806; 5,146,028; 5,151,399; 5,229,342; and 7,491,781, the descriptions of which have been incorporated herein by reference. The source of magnesium may be a magnesium halide, alkyl, aryl, alkaryl, alkoxide, alkaryloxide or aryloxide, its alcoholic adducts, its carbonated derivatives, or its sulfonated derivatives, although it is preferably an alcoholic adduct of a magnesium halide, a magnesium dialkoxide, carbonated magnesium dialkoxide, carbonated magnesium diaryloxide, or mixed magnesium / titanium halide alcoholate. Magnesium compounds containing an alkoxide group and an aryloxide group can also be used, as well as magnesium compounds containing a halogen in addition to an alkoxide, alkaryloxide or aryloxide group. The alkoxide groups, when present, most appropriately contain 1 to 8 carbons, preferably 2 to 6 carbon atoms. The aryloxide groups, when present, most appropriately contain 6 to 10 carbons. When halogen is present, it is preferably chlorine.
    [0044] Among the magnesium dialkoxides and diaryloxides that can be used are those of the formula Mg (OC) (O) (OR3) to (OR) 4) 2-a where R3 and R4 are alkyl, alkaryl or aryl groups, and a is about 0.1 to 2. The most preferred magnesium compound containing a carbonate group is carbonated magnesium diethoxide (CMEO), Mg (OC) (O) (OEt) 2. Optionally, magnesium can be halogenated with an additional halogenating agent, such as, for example, thionyl chloride or alkyl chlorosilanes, prior to contact with the tetravalent titanium source.
    [0045] A slightly different type of magnesium source is described by the general formula Mg4 (OR5) 6 (R6OH) wA, where each R5 or R6 is a lower alkyl of up to and including 4 carbon atoms and A is one or more anions with a total charge of -2. The manufacture of this magnesium source is described in U.S. Patent No. 4,710,482 to Job, which is incorporated herein by reference.
    [0046] Another especially preferred source of magnesium is that containing portions of magnesium and titanium and probably portions of at least some of halide, alkoxide and a phenolic compound. Such complex pro-catalyst precursors are produced by contacting a magnesium alkoxide, a titanium alkoxide, a titanium halide, a phenolic compound, and an alkane. See U.S. Patent No. 5,077,357 to Job, which is incorporated herein by reference.
    [0047] Another useful source of magnesium is a mixed magnesium / titanium compound ("MagTi"). The "MagTi precursor" has the formula MgbTi (OR7) cX1d where R7 is an aliphatic or aromatic hydrocarbon radical having from 1 to 14 carbon atoms or COR8, where R8 is an aliphatic or aromatic hydrocarbon radical having from 1 to 14 carbon atoms ; each OR7 group is the same or different; X1 is independently chlorine, bromine or iodine, preferably chlorine; b is 0.5 to 56, or 2 to 4; c is 2 to 116 or 5 to 15; and d is 0.5 to 116 or 1 to 3. These precursors are prepared through controlled precipitation by removing an alcohol from the reaction mixture used in its preparation. As such, a reaction medium comprises a mixture of an aromatic liquid, especially a chlorinated aromatic compound, most especially chlorobenzene, with an alkanol, especially ethanol. Suitable halogenating agents include titanium tetrabromide, titanium tetrachloride or titanium trichloride, especially titanium tetrachloride. The removal of alkanol from the solution used in the halogenation results in the precipitation of the solid precursor, especially having the desired morphology and surface area. In addition, the resulting precursors are particularly uniform in particle size.
    [0048] An additional useful source of magnesium is a magnesium chloride material containing benzoate ("BenMag"). As used herein, a "magnesium chloride containing benzoate" ("BenMag") can be a supported catalyst component (i.e., a supported halogenated catalyst component precursor) that contains an internal benzoate electron donor. The BenMag material can also include a titanium portion, such as titanium halide. The internal benzoate donor is labile and can be replaced with other electron donors during the synthesis of supported catalyst component and / or catalyst. Non-restrictive examples of suitable benzoate groups include ethyl benzoate, methyl benzoate, ethyl p-methoxybenzoate, methyl p-ethoxybenzoate, ethyl p-ethoxybenzoate, ethyl p-chlorobenzoate. A preferred benzoate group is ethyl benzoate. Non-restrictive examples of BenMag pro-catalyst precursors include catalysts of the brands SHACTM103 and SHACTM 310 from The Dow Chemical Company, Midland, Michigan. The BenMag supported catalyst component precursor may be a halogenation product of a supported catalyst component precursor (eg, a magnesium dialcoxide, a carbonated magnesium dialcoxide, or a MagTi precursor) in the presence of a benzoate compound.
    Titanium source [0049] The titanium source for the supported catalyst component is preferably a tetravalent titanium that contains at least two halogen atoms and preferably contains four halogen atoms, for example, Ti (OR9) cX24-e, where R9 it is a hydrocarbon, and X2 is a halide and e is 0 to 2. Most preferably, these halogen atoms are chlorine atoms. Titanium compounds containing up to two alkoxy, alkaryloxy or aryloxy groups can be used. The alkoxy groups, when present, most appropriately contain from 1 to 8 carbon atoms, preferably from 2 to 6 carbon atoms. The aryloxy or alkaryloxy groups, when present, are most appropriately containing 6 to 12 carbon atoms, preferably 6 to 10 carbon atoms. Examples of alkoxy or aryloxy-titanium halides include titanium diethoxy dibromide, titanium isopropoxy triiodide, titanium dihexoxy chloride, and phenoxy titanium trichloride. The most preferred titanium source is TiCl4.
    [0050] Fabrication of Supported Catalyst Component [0051] The magnesium compound is preferably reacted (i.e. halogenated) with the tetravalent titanium halide in the presence of an internal electron donor and optionally a halohydrocarbon. Optionally, an inert hydrocarbon solvent or diluent may also be present. Various methods for preparing supported catalyst components are known in the art. Some of these methods are described, for example, in US Patent Nos. 4,442,276; 4,460,701; 4,547,476; 4,816,433; 4,829,037; 4,927,797; 4,990,479; 5,066,738; 5,028,671; 5,153,158; 5,247,031 and 5,247,032. Regardless of the method of formation, the supported catalyst components of the present invention include the internal electron donor material described in the present invention.
    [0052] When optionally used, the halohydrocarbon used can be aromatic, aliphatic or alicyclic. Most preferably, the halogen of the halohydrocarbon is chlorine. Aromatic halohydrocarbons are preferred, particularly those containing 6 to 12 carbon atoms, preferably 6 to 10 carbon atoms. Preferably, such halohydrocarbons contain 1 or 2 halogen atoms, although more may be present, if desired. Suitable aromatic halohydrocarbons include, but are not limited to, chlorobenzene, bromobenzene, dichlorobenzene, dichlorodibromobenzene, chlorotoluene, dichlorotoluene, and chloronaphthalene. Aliphatic halohydrocarbons contain from 1 to 12 carbon atoms, preferably from 1 to 9 carbon atoms and at least 2 halogen atoms. Suitable aliphatic hydrocarbons include, but are not limited to, dibromomethane, trichloromethane, 1,2-dichloroethane, trichloroethane, dichlorofluoroethane, hexachloroethane, trichloropropane, chlorobutane, dichlorobutane, chloropentane, trichlorofluoro chloride, tetrachloro, tetrachloro, tetrachloro. The alicyclic hydrocarbons that can be used contain from 3 to 12 carbon atoms, and preferably from 3 to 9 carbon atoms, and at least 2 halogen atoms. Suitable alicyclic halohydrocarbons include dibromocyclobutane and trichlorocyclohexane.
    [0053] The optional inert hydrocarbon diluent can be aliphatic, aromatic or alicyclic. Some representative diluents are isopentane, n-octane, isooctane, xylene or toluene.
    [0054] The halogenation of the magnesium compound with the halogenated tetravalent titanium halide is carried out using an excess of titanium halide. At least 2 moles of titanium halide should be used per mole of the magnesium compound. Preferably from about 4 moles to about 100 moles of titanium halide are used per mole of magnesium compound, and most preferably from about 4 moles to about 20 moles of titanium halide are employed per mole of magnesium compound .
    [0055] When optionally employed, halohydrocarbon is used in an amount sufficient to dissolve the titanium halide and the internal electron donor, and to properly disperse the magnesium compound. Generally, the dispersion contains from about 0.005 to about 2.0 moles of the solid magnesium compound per mole of the halohydrocarbon, preferably from about 0.01 to about 1.0 moles of the solid magnesium compound per mole of the halohydrocarbon. The internal electron donor is employed in an amount sufficient to provide a molar ratio of said compound to the titanium halide of about 0.0005: 1 to about 2.0: 1, preferably from about 0.001: 1 to about 0.1: 1. About 1: 100 to 100: 1 in volume of halohydrocarbon can be used for optional diluent.
    [0056] Halogenation can be conducted at a temperature of up to 150 ° C, preferably from about 80 ° C to about 140 ° C. Generally, the reaction is allowed to proceed for a period of 0.1 to 6 hours, preferably between about 0.5 to about 3.5 hours. For convenience, halogenation is generally conducted at atmospheric pressure, although a pressure range can be employed, for example, 0.5 atm (50,700 Pa) to 5 atm (507,000 Pa). The halogenated product, like the starting magnesium compound, is a solid material that can be isolated from the liquid reaction medium by drying, filtering, decanting, evaporating, distilling or any appropriate method.
    [0057] After separation, the halogenated product (also called halogenation supported catalyst component) can be treated one or more times with additional tetravalent titanium halide to remove residual alkoxy and / or aryloxy groups and maximize catalytic or other activity desired properties. Preferably, the halogenated product is treated at least twice with separate portions of the tetravalent titanium halide. Generally, the reaction conditions employed to treat the halogenated product with the titanium halide are the same or similar to those employed during the initial halogenation of the magnesium compound, and the internal electron donor may or may not be present during the treatment (s) (s). When optionally employed, halohydrocarbon is typically used to dissolve the titanium halide and to disperse the solid halogenated product. If desired, the halogenated product can be treated with the acid halide before or after being treated with the titanium compound for the second time. 5 mmol to 200 mmol of the acid halide per mol of magnesium are generally employed in the halogenated product (i.e., supported catalyst component). Suitable acid halides include benzoyl chloride, phthaloyl dichloride, 2,3-naphthalenedicarboxylic acid dichloride, endo-5-norbornene-2,3-dicarboxylic acid dichloride, maleic acid dichloride, citraconic acid dichloride and the like. A useful procedure for treating the halogenated product with acid halides is described in U.S. Patent No. 6,825,146.
    [0058] After the supported catalyst component has been treated one or more times with an additional tetravalent titanium halide, it is separated from the liquid reaction medium, and preferably washed with an inert hydrocarbon such as isopentane, isooctane, isohexane, hexane, pentane , heptane or octane to remove unreacted titanium compounds, or other impurities. The supported catalyst component can then be dried, or can be converted into a paste in a hydrocarbon, especially a relatively heavy hydrocarbon such as mineral oil for storage or later use. If dried, the drying process can be by filtration, evaporation, heating or other methods known in the art.
    [0059] Without being bound by any specific theory, it is believed that (1) additional halogenation by contacting the supported catalyst component previously formed with a titanium halide compound, especially a solution of it in halohydrocarbon diluent and / or (2) additional washing of the previously formed supported catalyst component with a halohydrocarbon at an elevated temperature (100 ° C to 150 ° C) results in desirable modification of the supported catalyst component, possibly by removing certain inactive metal compounds that are soluble in the previously mentioned diluent. Consequently, the supported catalyst component can be contacted with a halogenating agent, such as a mixture of a titanium halide and a halohydrocarbon diluent, such as TiCl4 and chlorobenzene, one or more times before isolation or recovery. Correspondingly, the supported catalyst component can be washed at a temperature between 100 ° C to 150 ° C with a halohydrocarbon such as chlorobenzene or o-chlorotoluene one or more times, before isolation or recovery.
    [0060] The properly supported catalyst component final product has a titanium content of about 0.5 weight percent to about 6.0 weight percent, or about 1.0 weight percent at about 5.0 percent by weight. The weight ratio of titanium to magnesium in the supported solid catalyst component is suitably between 1: 3 and about 1: 160 or between about 1: 4 and about 1:50, or between about 1: 6 and 1:30. The internal electron donor is present in the catalyst component supported at an internal electron donor to magnesium molar ratio of about 0.001: 1 to about 10.0: 1, or from about 0.01: 1 to about 0 , 4: 1. The weight percentage is based on the total weight of the supported catalyst composition.
    [0061] The internal electron donor useful in the present invention can be combined with additional internal electron donors, such as ethers, esters, amines, imines, nitriles, phosphines, stylbines, arsines, polyhydrocarbyl phosphonates, phosphinates, dialkylphthalates, phosphates or phosphine oxides, or alkyl aralkyl phthalates, where the alkyl portion contains from 1 to 10, preferably from 2 to 6 carbon atoms, and the aralkyl portion contains from 7 to 10, preferably from 7 to 8 carbon atoms, or an alkyl ester of an aromatic monocarboxylic acid, where the monocarboxylic acid portion contains from 6 to 10 carbon atoms and the alkyl portion contains from 1 to 6 carbon atoms. Such a combination or incorporation of additional internal electron donors can occur in any of the steps that employ the titanium compound.
    [0062] Prepolymerization or encapsulation of the catalyst or supported catalyst component of the present invention can also be conducted before being used in the polymerization or copolymerization of alpha-olefins. A particularly useful prepolymerization procedure is described in U.S. Patent No. 4,579,836, which is incorporated herein by reference.
    Catalyst [0063] The catalyst for olefin polymerization (or "catalyst composition") includes the supported catalyst component described above, a cocatalyst, and optionally a selectivity control agent (also known as "SCA", "external donor" or "external electron donor"), and optionally an activity limiting agent (or "ALA").
    Cocatalyst [0064] The cocatalyst can be selected from any of the known catalytic activators for olefin polymerization, although organoaluminium compounds are preferred. Such cocatalysts can be used individually or in combination. Suitable organoaluminium cocatalysts have the formula Al (R10) fX3gHh, where: X3 is F, Cl, Br, I or OR10 and R10 are saturated hydrocarbon radicals containing from 1 to 14 carbon atoms, whose radicals can be the same or different, and , if desired, substituted with any substituent that is inert under the reaction conditions employed during polymerization, f is 1 to 3, g is 0 to 2, h is 0 or 1, and f + g + h = 3. Trialkylaluminium compounds are particularly preferred, especially those where each alkyl group contains from 1 to 6 carbon atoms, for example, Al (CH3) 3, Al (C2H5) 3, Al (i-C4Hg) 3, and Al ( C6Hn) 3.
    SCA
    [0065] Without being bound by any specific theory, it is believed that the provision of one or more SCA (selectivity control agent) in the catalyst composition may affect the following properties of the forming polymer: tactility level (ie, soluble material in xylene), molecular weight (ie melt flow), molecular weight distribution (MWD), melting point, and / or oligomer level. SCA, also known as external donor or external electron donor, used in the invention is typically known in the state of the art. SCAs known in the art include, but are not restricted to silicon compounds, carboxylic acid esters (especially diesters), monoethers, diethers (eg 1,3-dimethoxy propane or 2,2-diisobutyl-1,3- dimethoxy propane), and amines (eg, tetramethylpiperidine).
    [0066] Preferably, the silicon compounds employed as SCAs contain at least one silicon-oxygen-carbon bond. Suitable silicon compounds include those having the formula R11iSiYjX4k, where: R11 is a hydrocarbon radical containing from 1 to 20 carbon atoms, Y is -OR12 or -OCOR12, where R12 is a hydrocarbon radical containing from 1 to 20 carbon atoms , X4 is hydrogen or halogen, i is an integer having a value from 0 to 3, j is an integer having a value from 1 to 4, k is an integer having a value from 0 to 1, and preferably 0 and i + k + k = 4. Preferably, R11 and R12 are C1-C10 alkyl, aryl or aralkyl linkers. Each R11 and R12 can be the same or different and, if desired, replaced with any substituent that is inert under the reaction conditions employed during polymerization. Preferably, R12 contains from 1 to 10 carbon atoms when it is aliphatic and can be sterically hindered or cycloaliphatic, and from 6 to 10 carbon atoms, when it is aromatic.
    [0067] Examples of R11 include cyclopentyl, t-butyl, isopropyl, cyclohexyl or methyl cyclohexyl. Examples of R12 include methyl, ethyl, butyl, isopropyl, phenyl, benzyl and t-butyl. Examples of X4 are Cl and H. Preferred silicon SCAs are alkylalkoxysilanes such as diethyldiethoxysilane, diphenyl dimethoxy silane, diisobutylmethoxysilane, cyclohexylmethyldimethoxysilane, n-propyltrimethoxysilane or dicyclopentyl dimethoxysilane.
    [0068] Silicon compounds in which two or more silicon atoms are linked together by an oxygen atom, that is, siloxanes or polysiloxanes, can also be used, as long as the necessary silicon-oxygen-carbon bond is also present. Other preferred SCAs are esters of aromatic monocarboxylic or dicarboxylic acids, particularly alkyl esters, such as PEEB, DIBP and methyl paratoluate.
    [0069] The SCA is provided in an amount sufficient to provide from about 0.01 mol to about 100 moles per mole of titanium in the pro-catalyst. It is preferred that the SCA be provided in an amount sufficient to provide from about 0.5 mol to about 70 moles per mole of titanium in the pro-catalyst, with about 8 moles to about 50 moles being more preferred.
    [0070] Non-restrictive examples of silicon compounds suitable for SCA include those mentioned in US 7,491,670, WO2009 / 029486 or WO2009 / 029487 and any combinations thereof.
    [0071] The SCA can be a mixture of at least 2 silicon compounds (ie, a mixed SCA or external mixed electron donor, or "MEED"). A MEED can comprise two or more of any of the SCA compounds mentioned above. A preferred mixture can be dicyclopentyldimethoxysilane and methylcyclohexyldimethoxysilane, dicyclopentyldimethoxysilane and tetraethoxysilane or dicyclopentyldimethoxysilane and n-propyltriethoxysilane.
    ALLAH
    [0072] The catalyst composition can also include an activity limiting agent (ALA). As used herein, an "activity limiting agent" ("ALA") is a material that reduces catalytic activity at elevated temperature (i.e., temperature greater than about 85 ° C). An ALA inhibits or otherwise prevents the interruption / failure of the polymerization reactor, ensuring continuity of the polymerization process. Typically, the activity of Ziegler-Natta catalysts increases as the temperature of the reactor increases. Ziegler-Natta catalysts also typically maintain high activity close to the melting point temperature of the polymer produced. The heat generated by the exothermic polymerization reaction can cause polymer particles to form agglomerates, which can ultimately lead to the interruption of the continuity of the polymer production process. ALA reduces catalytic activity at elevated temperature, thus avoiding breakdowns in the reactor, reducing (or preventing) particle agglomeration and ensuring continuity of the polymerization process.
    [0073] ALA may or may not be a component of SCA and / or MEED. The activity limiting agent can be a carboxylic acid ester, a diether, a poly (alkylene glycol), a diol ester, and combinations thereof. The carboxylic acid ester can be an aliphatic or aromatic mono or polycarboxylic acid ester. Non-restrictive examples of monocarboxylic acid esters include ethyl and methyl benzoate, ethyl p-methoxybenzoate, methyl p-ethoxybenzoate, ethyl p-ethoxybenzoate, ethyl acrylate, methyl methacrylate, ethyl acetate, ethyl p-chlorobenzoate , hexyl p-aminobenzoate, isopropyl naphthenate, n-amyl toluate, ethyl cyclohexanoate and propyl pivalate.
    [0074] Non-restrictive examples of suitable ALAs include those described in EO2009085649, WO2009029487, WO2009029447, or WO2005030815, and combinations thereof.
    [0075] SCA and / or ALA can be added to the reactor separately. Alternatively, SCA and ALA can be mixed together in advance and then added to the catalyst composition and / or to the reactor as a mixture. In the mix, more than one SCA or more than one ALA can be used. A preferred mixture is didiclopentyldimethoxysilane and isopropyl myristate, dicyclopentyldimethoxysilane and poly (ethylene glycol) laurate, dicyclopentyldimethoxysilane and isopropyl myristate and poly (ethylene glycol) dioleate; and methylcyclohexyldimethoxysilane and isopropyl myristate, dicyclopentyldimethoxysilane and n-propyltriethoxysilane and isopropyl myristate, and dicyclopentyldimethoxysilane and tetraethoxysilane and isopropyl myristate, and combinations thereof.
    [0076] The catalyst composition can include any of the SCAs and MEEDs previously mentioned in combination with any of the activity-limiting agents (or ALAs) mentioned above.
    Preparation of the catalyst and catalyst composition [0077] The components of the catalyst for olefin polymerization can be contacted by mixing in a suitable reactor outside the system in which the olefin is to be polymerized and the catalyst thus produced is subsequently introduced into the polymerization reactor. Pre-mixed components can be dried after contact or left in the contact solvent. Alternatively, however, the catalyst components can be introduced separately into the polymerization reactor. Alternatively, two or more of the components can be mixed partially or completely with each other (eg, pre-mixing SCA and cocatalyst or pre-mixing SCA and ALA) before being introduced into the polymerization reactor. Another alternative is to contact the supported catalyst component with an organoaluminium compound before reaction with the other catalyst components. A different alternative is to prepolymerize a small amount of olefin with the catalyst components or place any of the components on a support (eg, silica or a non-reactive polymer).
    Polymerization [0078] One or more olefinic monomers can be introduced into a polymerization reactor to react with the catalyst and form a polymer, or a fluidized bed of polymeric particles. Non-restrictive examples of suitable olefinic monomers include ethylene, propylene, C4-20 α-olefins, such as 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1 -decene, 1-dodecene and the like; C4-20 diolefins, such as 1,3-butadiene, 1,3-pentadiene, norbornadiene, 5-ethylidene-2-norbornene (ENB) and dicyclopentadiene; aromatic C8-10 vinyl compounds including styrene, o-, m- and p-methylstyrene, divinylbenzene, vinylbiphenyl, vinylnaphthalene, and halogen substituted C8-40 aromatic compounds such as chloro-styrene and fluoro-styrene.
    [0079] As used herein, "polymerization conditions" are temperature and pressure parameters in an appropriate polymerization reactor to promote polymerization between the catalyst composition and an olefin to form the desired polymer. The polymerization process can be a gas phase, paste or mass polymerization process, operating in one or more of a polymerization reactor. Consequently, the polymerization reactor can be a gas phase polymerization reactor, a liquid phase polymerization reactor, or a combination thereof.
    [0080] It is understood that the supply of hydrogen in the polymerization reactor is a component of the polymerization conditions. During polymerization, hydrogen is a chain transfer agent and affects the molecular weight (and hence the melt flow rate) of the resulting polymer.
    [0081] Polymerization can occur through gas phase polymerization. As used herein, "gas phase polymerization" is the passage of an upward fluidizing medium, such medium containing one or more monomers, in the presence of a catalyst through a fluidized bed of polymeric particles maintained in a fluidized state by the fluidizing medium. "Fluidification", "fluidized" or "fluidizing" is a gas-solid contact process in which a bed of finely divided polymeric particles is suspended and agitated by an upward stream of gas. Fluidization occurs in a bed of particulates when an upward flow of fluid through the interstices of the bed of particles reaches a pressure differential and an increase in resistance to friction that exceeds the weight of the particulate. Thus, a "fluidized bed" is a plurality of polymeric particles suspended in a fluidized state through a stream of a fluidizing medium. A "fluidizing medium" is one or more olefin gas, optionally a carrier gas (such as H2 or N2) and optionally, a liquid (such as a hydrocarbon) that rises through the gas phase reactor.
    [0082] A typical gas phase polymerization reactor (or gas phase reactor) includes a container (ie the reactor), the fluidized bed, a distribution plate, inlet and outlet piping, a compressor, a water cooler cycle gas or a heat exchanger, and a product discharge system. The container includes a reaction zone and a speed reduction zone, each located above the distribution plate. The bed is located in the reaction zone. In one embodiment, the fluidizing medium includes propylene gas and at least one other gas such as an olefin and / or a carrier gas such as hydrogen or nitrogen.
    [0083] The contact of the catalyst and the olefin occurs by feeding the catalyst composition into a polymerization reactor and introducing the olefin into the polymerization reactor. The cocatalyst can be mixed with the supported catalyst component (premix) before introducing the supported catalyst component into the polymerization reactor. The cocatalyst can also be added to the polymerization reactor regardless of the supported catalyst component. The independent introduction of the cocatalyst into the polymerization reactor can occur simultaneously, or substantially simultaneously, with the supply of the supported catalyst component.
    [0084] The polymerization process can include a prepolymerization step. Prepolymerization includes contacting a small amount of the olefin with the pro-catalyst composition, after the supported catalyst component has been contacted with the cocatalyst and the SCA and / or the activity limiting agent. The resulting pre-activated catalyst stream is then introduced into the polymerization reaction zone and contacted with the remainder of the olefin monomer to be polymerized, and optionally with one or more of the SCA components and / or the activity limiting agent components. .
    [0085] Prepolymerization results in the supported catalyst component being combined with the cocatalyst and with the SCA and / or the activity limiting agent, the combination being dispersed in a matrix of the forming polymer. Optionally, additional amounts of the SCA and / or the activity limiting agent can be added.
    [0086] The polymerization process may include a pre-activation step. Pre-activation includes contacting the supported catalyst component with the cocatalyst and the SCA and / or activity limiting agent. The resulting pre-activated catalyst stream is subsequently introduced into the polymerization reaction zone and contacted with the olefin monomer to be polymerized, and optionally with one or more of the SCA components. Pre-activation results in the supported catalyst component being combined with the cocatalyst and the SCA and / or the activity limiting agent. Optionally, additional amounts of the SCA and / or the activity limiting agent can be added.
    [0087] The process may include mixing the SCA (and optionally the activity limiting agent) with the supported catalyst component. The SCA can be complexed with the cocatalyst and mixed with the supported catalyst component (premix) before contact between the catalyst composition and the olefin. The SCA and / or the activity limiting agent can be added independently to the polymerization reactor. Preferred SCAs include dicyclopentyldimethoxysilane or n-propyltrimethoxysilane.
    A preferred catalyst composition includes an SCA such as dicyclopentyldimethoxysilane and / or n-propyltrimethoxysilane and / or methylcyclohexyldimethoxysilane and an activity limiting agent such as isopropyl myristate.
    [0089] The olefin can be propylene where the process includes forming a propylene-based polymer having a melt flow rate (MFR) of about 0.01g / 10 min to about 800g / 10 min or about 0 , 1g / 10 min at about 200g / 10 min, or from about 0.5g / 10 min to about 150g / 10 min. In addition, the propylene-based polymer is a polypropylene homopolymer.
    [0090] The olefin can be propylene, the process including forming a propylene-based polymer having a xylene-soluble content of about 0.5% to about 10% or about 1% to about 8 %, or from about 1% to about 4%. In addition, the propylene-based polymer is a polypropylene homopolymer.
    [0091] The present description provides another process for producing an olefin-based polymer. The olefin can be propylene and a mixture of at least one other suitable olefin comonomer wherein the process includes forming a propylene-based interpolymer. The preferred comonomer is ethylene and / or 1-butene and the forming interpolymer has a melt flow rate (MFR) of about 0.01 g / 10 min to about 200 g / 10 min, or about 0.1 g / 10 min to about 100g / 10 min, or about 0.5g / 10 min to about 70g / 10 min. In addition, the preferred propylene-based interpolymer is a random copolymer.
    [0092] The olefin can be propylene and a mixture of at least one other appropriate olefin comonomer, wherein the process includes forming a propylene-based interpolymer. The preferred comonomer is ethylene and / or 1-butene and the forming interpolymer has a soluble content in xylene of about 0.5% to about 40%, or about 1% to about 30% or about 1% to about 20%. In addition, the preferred propylene-based interpolymer is a random copolymer.
    [0093] The olefin may be propylene and a mixture of at least one other appropriate olefin comonomer, wherein the process includes forming a propylene-based interpolymer. The preferred comonomer is ethylene and / or 1-butene and the forming interpolymer has a comonomer content in weight percent to propylene of about 0.001% to about 20% or about 0.01% to about 15 %, or from about 0.1% to about 10%. In addition, the preferred propylene-based interpolymer is a random copolymer.
    [0094] The present description provides another process for producing an olefin-based polymer. A process for producing an olefin-based polymer is provided and includes contacting propylene with a catalyst composition comprising a dicarbonate to form a propylene-based polymer. The contact between propylene and the catalyst composition occurs in a first polymerization reaction under polymerization conditions. The process also includes contacting ethylene and optionally at least one other olefin in the presence of the propylene-based polymer. The contact between the ethylene, the olefin (s) and the propylene-based polymer occurs in a second polymerization reactor under polymerization conditions and forms a propylene impact copolymer.
    [0095] The first reactor and the second reactor can operate in series, and the effluent from the first reactor (ie, the propylene-based polymer) is loaded into the second reactor. The additional olefin monomer is added to the second polymerization reactor to proceed with the polymerization. The additional catalyst composition (and / or any combination of individual catalyst components - i.e., supported catalyst component, cocatalyst, EED or MEED, ALA) can be added to the second polymerization reactor. The additional catalyst composition / components added to the second reactor can be the same or different from the catalyst composition / components introduced into the first reactor.
    [0096] The propylene-based polymer produced in the first reactor is a propylene homopolymer. The propylene homopolymer is charged to the second reactor where ethylene and propylene are contacted with each other in the presence of the propylene homopolymer. This forms a propylene impact copolymer having a continuous propylene homopolymer phase (or matrix) and a discontinuous phase (or rubber phase) selected from a propylene based copolymer (i.e., a propylene / ethylene copolymer) or a ethylene-based copolymer (ie an ethylene / propylene copolymer). The discontinuous phase is dispersed in the continuous phase.
    [0097] The propylene impact copolymer can have an Fc value of about 1% by weight to about 50% by weight, or from about 10% by weight to about 40% by weight, or about 20 % by weight to about 30% by weight. As used here, the term "fraction copolymer" ("Fc") is the percentage by weight of the discontinuous phase present in the heterophasic copolymer. The Fc value is based on the total weight of the propylene impact copolymer.
    [0098] The propylene impact copolymer can have an Fc value of about 1% by weight to about 100% by weight, or from about 20% by weight to about 90% by weight, or about 30 % by weight to about 80% by weight or from about 40% by weight to about 60% by weight. As used herein, "ethylene content" ("Ec") is the weight percentage of ethylene present in the discontinuous phase of the propylene impact copolymer. The Ec value is based on the total weight of the discontinuous (or rubbery) phase.
    TEST METHODS
    [0099] The Polydispersity Index (PDI) is measured with an AR-G2 rheometer, which is a dynamic spectrometer for voltage control manufactured by TA Instruments, using a method according to Zeichner G.R., Patel P.D. (1981). "A Comprehensive Study of Polypropylene Melt Rheology" Proc. of the 2nd. World Congress of Chemical Eng., Montreal, Canada. An ETC oven is used to control the temperature at 180 ° C ± -0.1 ° C. Nitrogen is purged inside the oven to protect the sample from degradation by oxygen and moisture. A pair of cone sample holders and a 25 mm diameter plate are used. The samples are molded by compression on 50mm x 100mm x 2mm plates. The samples are cut into 19mm squares and loaded in the center of the bottom plate. Upper cone geometry: cone angle: 5:42:20 (degrees: min: sec); (2) diameter: 25mm; (3) truncation gap (149 microns). The geometry of the bottom plate is a 25mm cylinder. Test procedure: (i) the cone and plate sample holder is heated in the ETC oven at 180 ° C for 2 hours. Then the gap is zeroed under the blanket of nitrogen gas. (ii) the cone is lifted to a height of 2.5 mm and the sample is loaded to the top of the bottom plate. (iii) timing starts for 2 minutes. (iv) the upper cone is immediately lowered to lightly touch the top of the sample, observing normal force. (v) after two minutes, the sample is pressed down against the 165 micron gap ("gap") by lowering the upper cone. (vi) normal force is observed when, at a normal force up to <0.05 Newton, the excess sample is removed from the edge of the cone and plate sample holder with a spatula. (vii) the upper cone is lowered again until the truncation opening of 149 microns. (viii) an Oscillatory Frequency Scan test is conducted under these conditions:. Test delay at 180 ° C for 5 minutes. . Frequencies: 628.3 r / s to 0.1 r / s. . Data acquisition rate: 5 points / ten. Voltage: 10% (ix) when the test is completed the crossing module (Gc) is detected through the Rheology Advantage data analysis program provided by TA Instruments. (x) PDI = 100,000 - Gc (in Pa units).
    [00100] The melt flow rate (MFR) or "Melt Flow" is measured according to the test method ASTM D 1238-01 at 230 ° C with a weight of 2.16 kg for propylene-based polymers .
    [00101] Soluble in xylene (XS) are measured according to the procedure described below. A total of 0.4g of polymer is dissolved in 20 ml of xylenes with stirring at 130 ° C for 30 minutes. The solution is then cooled to 25 ° C and after 30 minutes the fraction of insoluble polymer is filtered. The resulting filtrate is analyzed using Flow Injection Polymer Analysis using a Viscotek ViscoGEL H-100-3078 column with a mobile THF phase flowing at 1.0 ml / min. The column is coupled to a Viscotek Model 302 triple detector device, with light scattering detectors, viscometer and refractometer operating at 45 ° C. The calibration of the instrument was maintained with Viscotek PolyCAL ™ polystyrene standards.
    [00102] The final melting point, T mf or ("TMF") is the temperature to melt the most preferred crystal in the sample, being considered as a measure of the isotacticity and inherent crystallisability of the polymer. The test is conducted using a TA Q100 Differential Scanning Calorimeter. A sample is heated from 0 ° C to 240 ° C at a rate of 80 ° C / min, cooled at the same rate to 0 ° C and then heated again at the same rate to 150 ° C for 5 minutes and heated to 150 ° C at 180 ° C to 1.25 ° C / min. The Tmf is determined from this last cycle by calculating the beginning of the baseline at the end of the heating curve. Test procedure for TMF: (1) calibrate the instrument with high purity indium in accordance with the standard. (2) purge the instrument head / cell with a constant flow rate of 50ml / min of nitrogen continuously. (3) sample preparation: mold by compression 1.5 g of powder sample using a 30-G302H-18-CX Compression Molder (30 ton): (a) heat the mixture to 230 ° C for 2 minutes per contact; (b) compress the sample at the same temperature with 20 tones of pressure for 1 minute; (c) cool the sample to 45 ° F and maintain for 2 minutes with 20 ton of pressure; (d) cut the plate in 4 of approximately the same size, stack them and repeat steps (a) - (c) to homogenize the sample. (4) weigh a portion of the sample (preferably between 5 to 8 mg) from the sample plate and seal it in a standard aluminum sample container. Place the sealed container containing the sample on the sample side of the instrument head / cell and place an empty sample container on the reference side. When using the autosampler, weigh several different specimens and adjust the machine to operate in sequence. (5) Measurements: (i) data storage: off (ii) 80.00 ° C / min ramp at 240.0 ° C (iii) isothermal for 1.00 min (iv) 80.00 ° C / min ramp at 0 , 00 ° C. (v) isothermal for 1.00 min (vi) ramp 80.00 ° C / min at 150.00 ° C. (vii) isothermal for 5.00 min (viii) data storage: connected (ix) ramp 1.25 ° C / min at 180.00 ° C (x) end of the method. (6) Calculation: Tmf is determined by intercepting two lines. Draw a line from the high temperature baseline. Draw another line from and through the deflection of the curve near the end of the curve on the high temperature side. The following examples serve to illustrate the present invention, although they are not intended to restrict its scope, as defined in the claims.
    EXAMPLES
    [00103] General procedure for the preparation of 5-ter-butyl-3-methyl-1,2-phenylene diethyl dicarbonate (ID-1), 5-ter-butyl-3-methyl-1,2-phenylene diphenyl dicarbonate (ID-2) and 3,5-diisopropyl-1,2-phenylene diethyl dicarbonate (ID-3): the appropriate catacol (30 mmol), pyridine (4.8 g, 60 mmol, 2.0 equiv.) and anhydrous methylene chloride (60 ml). The flask was immersed in an ice-water bath and appropriate chloroformate (60 mmol, 2 equiv.) Was added dropwise. The temperature of the mixture was raised to room temperature and stirred overnight. The precipitate was filtered and washed with additional methylene chloride. The combined filtrate was washed with water, saturated NH4Cl or 1N HCl (aqueous) solutions, water, saturated sodium bicarbonate, and brine accordingly, and dried over magnesium sulfate. After filtration, the filtrate was concentrated, and the residue purified by recrystallization or by flash column chromatography on silica gel.
    [00104] 5-ter-butyl-3-methyl-1,2-phenylene diethyl dicarbonate (ID-1): Prepared from 5-ter-butyl-3-methylbenzene-1m2-diol and ethyl chloroformate; purified by flash column chromatography on silica gel to produce a sticky colorless oil (81.4%): 1H NMR (500 MHz, CDCls, ppm) δ 7.09-7.11 (m, 2H), 4, 32 (q, 2H, J = 9.0 Hz), 4.31 (q, 2H, J = 9.0 Hz), 2.25 (s, 3H), 1.38 (t, 3H, J = 9 , 0 Hz), 1.37 (t, 3H, J = 9.0 Hz), 1.29 (s, 9H).
    5-ter-butyl-3-methyl-1,2-phenylene diphenyl dicarbonate (ID-2): prepared from 5-ter-butyl-3-methylbenzene-1,2-diol and phenyl chloroformate; purified by recrystallization from ethanol to produce a white solid (75.2%): 1H NMR (500 MHz, CDCls, ppm) δ 7.35-7.38 (m, 4H), 7.23-7.28 ( m, 7H), 7,167.17 (m, 1H), 2.36 (s, 3H), 1.32 (s, 9H).
    3,5-Diisopropyl-1,2-phenylene diethyl dicarbonate (ID-3): Prepared from 3,5-diisopropylbenzene-1,2-diol and ethyl chloroformate; purified by flash column chromatography on silica gel to produce a yellow oil (59.1%): 1H NMR (500 MHz, CDCls) δ 7.02 (s, 1H), 6.98 (s, 1H), 4.32 (q, 2H, J = 7.0 Hz), 4.31 (q, 2H, J = 7.0 Hz), 3.11 (heptat, 1H, J = 7.3 Hz), 2, 89 (heptat, 1H, J = 7.0 Hz), 1.38 (t, 3H, J = 7.3 Hz), 1.37 (t, 3H, J = 7.0 Hz), 1.24 ( d, 6H, J = 7.0 Hz), 1.22 (d, 6H, J = 7.5 Hz).
    [00105] Internal donor structures that have been obtained commercially (diisobutyl phthalate and diethyl carbonate) or prepared as described herein, are shown in Table 1.
    Table 1 - Internal Donor Structure used in the Examples Preparation of supported catalyst components [00106] Under nitrogen, 3.0g of MagTi (magnesium alcoholate / mixed titanium halide; CAS # 173994-66-6, see American patent No. 5,077,357), the amount of internal electron donor indicated in Table 2 below and 60ml of a 50/50 (vol / vol) mixture of titanium tetrachloride and chlorobenzene are loaded into a container equipped with an integral filter. After heating at 115 ° C for 60 minutes with stirring, the mixture is filtered. The solids are treated with an additional 60ml of fresh mixed titanium tetrachloride / chlorobenzene 50/50 (vol / vol) and optionally (as shown in table 2 below), a second internal electron donor charge at 115 ° C for 30 minutes with agitation. The mixture is filtered. The solids are again treated with 60ml of fresh mixed titanium tetrachloride / chlorobenzene 50/50 (vol / vol) at 115 ° C for 30 minutes with stirring. The mixture is filtered. At room temperature, the solids are washed three times with 70 ml of isooctane, and then dried under a stream of nitrogen. The solid catalyst components are collected in the form of powders and a portion is mixed with mineral oil to produce a 5.4% by weight paste. The identification of the internal electron donor used, its quantities, and addition timing are detailed below (Table 2).
    Table 2 - Quantities of Internal Donors used for Catalyst Components ._________________ Supported _____________________.
    Generation of Active Catalyst [00107] In a glove box under an inert atmosphere, the active catalyst mixture is prepared by pre-mixing the quantities indicated in Tables 3-4 of external donor (if present), triethyl aluminum (in the form of a solution 0.28M), supported catalyst component (in the form of a 5.45% mineral oil slurry) and 5-10 ml of isooctane diluent (optional) for 20 minutes. After preparation and without exposure to air, the active catalyst mixture is injected into the polymerization reactor as described below.
    Polymerization of Propylene in Batch Reactor (Homopolymer) [00108] The polymerizations are carried out in a stirred 3.8L stainless steel autoclave. Temperature control is maintained by heating or cooling an integrated reactor jacket using circulated water. The top of the reactor is opened after each operation so that the contents can be emptied after leaving the volatiles. All chemical substances used for polymerization or preparation of the catalyst are passed through purification columns to remove impurities. Propylene and solvents are passed through 2 columns, the first containing alumina, the second containing a purification reagent (Q5TM from Engelhard Corporation). Nitrogen and hydrogen gases are passed through a simple column containing Q5TM reagent.
    [00109] After connecting the top of the reactor to the body, the reactor is purged with nitrogen, while it is heated to 140 ° C and then during cooling to approximately 30 ° C. The reactor is then charged with a solution of diethyl aluminum chloride in isooctane (1% by weight) and stirred for 15 minutes. This scanning solution is then blasted into a recovery tank and the reactor is loaded with ~ 1375 g of propylene. The appropriate amount of hydrogen is added using a mass flow meter (see tables 3-5) and the reactor is brought to 62 ° C. The active catalyst mixture is injected as a paste in oil or light hydrocarbon and the injector is irrigated with isooctane three times to ensure complete release. After catalyst injection, the reactor temperature is raised to 67 ° C for 5 minutes, or maintained at 67 ° C via cooling in the case of large exotherms. After an operating time of 1 hour, the reactor is cooled to room temperature, ventilated and its contents discharged. The polymer weights are measured after drying overnight, or even constant weight in a ventilated hood.
    Table 3 - Results of Polymerization at 0.14 mol% (H2 / C3) Conditions: 200mg of catalyst paste; 0.15 mmol of external donor; _________________________________ 1.5 mmol Al_____________________________ * = comparative; it is not an example of the invention. "-" = not determined The analysis of the data in Table 3 reveals the following: A. The XS of the polymer of catalysts employing any of the dicarbonate donors of the invention is much less than when using the comparative monocarbonate catalyst (Comp .2). B. When using NPTMS as an external donor, the MPT of the catalyst polymer employing the inventor's donor (ID-1; Cat 1-2) is higher than when using the comparative catalyst (Comp.1a). C. When using NPTMS as an external donor, the polymer XS of the two catalysts employing donors of the invention (ID-1) is less than when using the comparative catalyst (Comp.1a or Comp.2). D. When using NCDPDMS as an external donor, the polymer catalyst MF employed by any of the donors of the invention is higher than when using the comparative catalyst (Comp. 1a). E. The efficiency of the catalysts of the invention is strong (> 14 kg PP / g catalyst). F. The efficiency of the invention catalyst employing the invention donor (ID-2 or ID-3) is higher than when using comparative catalysts (Comp. 1a or Comp.2).
    Table 4 - Polymerization Results at 0.82 mol% (H2 / C3) Conditions: 200mg of catalyst paste; 0.15 mmol of external donor; ___________________________ 1.5 mmol Al ____________________ * = comparative; not an example of the invention. hmf = polymer has "high melt flow" and produces a PDI measurement that needs to be extrapolated. "-" = not determined The analysis of the data in Table 4 reveals the following: A. The XS of the catalyst polymer employing the inventor's donor (ID-1; Cat 1-2) is less than when using the comparative catalyst . B. The PDI of the polymer of catalysts employing the donor of the invention (ID-1) is narrower than when using the comparative catalyst. C. The increase in polymer MF of catalysts employing any of the donors of the invention is substantial compared to when using the comparative catalyst. Therefore, polymeric resin with higher MF can be prepared without cracking. D. The efficiency of the catalysts of the invention is very strong, (> 29 kg PP / g catalyst).
    权利要求:
    Claims (13)
    [1]
    1. Solid catalyst component insoluble in hydrocarbon, useful in the polymerization of olefins, CHARACTERIZED by the fact that it contains magnesium, titanium, and halogen, and also contains an internal electron donor having the following structure: [R1-OC (O) -O -] xR2 where R1 is independently at each occurrence, an aliphatic or aromatic hydrocarbon, or a substituted hydrocarbon group containing from 1 to 20 carbon atoms; x is 2-4; and R2 is an aliphatic or aromatic hydrocarbon, or a substituted hydrocarbon group containing from 1 to 20 carbon atoms, as long as there are 2 atoms in the shortest chain that connects a first group R1-OC (O) -O and a second group R1- OC (O) -O-.
    [2]
    2. Catalyst component, according to claim 1, CHARACTERIZED by the fact that each R1 is an aliphatic hydrocarbon.
    [3]
    3. Catalyst component, according to claim 1, CHARACTERIZED by the fact that each R1 is an aromatic hydrocarbon.
    [4]
    4. Catalyst component, according to claim 1, CHARACTERIZED by the fact that each R2 is a 1,2-substituted phenyl moiety.
    [5]
    5. Catalyst component according to claim 1, CHARACTERIZED by the fact that R2 is a 1,2- or 3,4-substituted naphthyl portion.
    [6]
    6. Catalyst component, according to claim 1, CHARACTERIZED by the fact that R2 is a straight or branched chain alkyl moiety, as long as there are 2 atoms in the shortest chain that connects a first group R1-OC (O) -O - and a second group R1-OC (O) -O-.
    [7]
    7. Catalyst component according to any one of claims 4 to 6, CHARACTERIZED by the fact that each R1 is an aliphatic or aromatic hydrocarbon group.
    [8]
    8. Catalyst component according to any one of claims 4 to 6, CHARACTERIZED by the fact that each R1 is ethyl or phenyl.
    [9]
    9. Catalyst component, according to claim 1, CHARACTERIZED by the fact that the internal electron donor comprises one of the following compounds: 5-ter-butyl-3-methyl-1,2-phenylene diethyl dicarbonate, diphenyl dicarbonate 5-ter-butyl-3-methyl-1,2-phenylene, or 3,5-diisopropyl-1,2-phenylene diethyl dicarbonate.
    [10]
    10. Catalyst component according to any one of claims 1 to 9, CHARACTERIZED by the fact that it is optionally combined with a simple SCA component, a mixed SCA component, or an activity limiting agent.
    [11]
    11. Catalyst component according to claim 10, CHARACTERIZED by the fact that the mixed SCA component contains an activity limiting agent or an organic ester as a component.
    [12]
    12. Catalyst component, according to claim 11, CHARACTERIZED by the fact that it is optionally combined with an organoaluminium compound.
    [13]
    13. Method for polymerizing an olefin CHARACTERIZED by the fact that it comprises contacting the olefin with a catalyst component as defined in any one of claims 1 to 12.
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    CN102762603B|2014-11-26|
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    US8263520B2|2012-09-11|
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    US20110130530A1|2011-06-02|
    WO2011068770A1|2011-06-09|
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    法律状态:
    2018-01-30| B25C| Requirement related to requested transfer of rights|Owner name: DOW GLOBAL TECHNOLOGIES LLC (US) |
    2018-05-15| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-05-22| B25A| Requested transfer of rights approved|Owner name: W. R. GRACE AND CO. - CONN (US) |
    2019-05-28| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|
    2019-08-06| B15K| Others concerning applications: alteration of classification|Free format text: AS CLASSIFICACOES ANTERIORES ERAM: C08F 4/651 , C08F 110/06 , C07C 68/02 , C07C 69/96 , B01J 31/02 , C08F 4/646 Ipc: C07C 69/96 (1974.07), C08F 4/646 (1990.01), C08F 4 |
    2019-08-13| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2020-02-18| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-03-10| 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 30/11/2010, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US26593109P| true| 2009-12-02|2009-12-02|
    US61/265,931|2009-12-02|
    PCT/US2010/058262|WO2011068770A1|2009-12-02|2010-11-30|Two atom bridged dicarbonate compounds as internal donors in catalysts for polypropylene manufacture|
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