Catalyst compositions and systems with extended life

Abstract

A Ziegler-Natta catalyst composition is disclosed that includes an internal electron donor and has improved polymerization kinetics, long life, improved stereoselectivity, and / or improved hydrogen response.

Description

[Technical Field]

[0001] (Related Applications) This application is based on and claims priority to U.S. Provisional Patent Application No. 62,902,048, filed September 18, 2019, the contents of which are incorporated herein by reference. [Background technology]

[0002] Polyolefin polymers are used in many different applications and fields. Polyolefin polymers are, for example, thermoplastic polymers that can be easily processed. Polyolefin polymers can also be recycled and reused. Polyolefin polymers are formed from hydrocarbons such as ethylene and alpha-olefins, which are obtained from petrochemicals and are abundantly available.

[0003] Polypropylene polymers, a type of polyolefin polymer, generally have a linear structure based on propylene monomers. Polypropylene polymers can have a variety of different stereospecific configurations. For example, polypropylene polymers can be isotactic, syndiotactic, and atactic. Isotactic polypropylene is perhaps the most common form and can be highly crystalline. Polypropylene polymers that can be produced include homopolymers, modified polypropylene polymers, and polypropylene copolymers, including polypropylene terpolymers. By modifying polypropylene or copolymerizing propylene with other monomers, a variety of different polymers can be produced with desired properties for specific applications. For example, polypropylene copolymers can be produced with elastomeric properties that significantly improve the impact strength of the polymer.

[0004] The global demand for olefin-based polymers continues to grow as the applications of these polymers become more diverse and sophisticated. Ziegler-Natta catalyst compositions for the production of olefin-based polymers are known. Ziegler-Natta catalyst compositions typically include a procatalyst containing a transition metal halide (i.e., titanium, chromium, or vanadium), a cocatalyst such as an organoaluminum compound, and optionally an external electron donor.

[0005] In light of the emerging performance of new applications for olefin-based polymers, the art recognizes a need for olefin-based polymers with improved variability properties. Furthermore, there is a need for improved Ziegler-Natta catalyst compositions that provide one or more advantages for further improving the polymer production process and / or polymer properties. In particular, there is a need for improved Ziegler-Natta catalyst compositions that have improved polymerization kinetics, excellent stereoselectivity, hydrogen response, and longer catalyst life while maintaining activity, particularly with respect to initial activity and / or prepolymerization activity. Summary of the Invention

[0006] Generally, the present disclosure relates to a catalyst system for producing polyolefin polymers. The catalyst system includes a catalyst composition containing an internal electron donor. The internal electron donor provides the catalyst composition with a relatively long life and a more uniform polymerization kinetic profile. The catalyst system of the present disclosure can produce polyolefin polymers with different desired properties.

[0007] For example, in one embodiment, the present disclosure relates to a catalyst composition for the stereoselective polymerization of olefins, such as propylene. The catalyst composition includes a combination of a magnesium moiety, a titanium moiety, and an internal electron donor. The internal electron donor has the following chemical structure: [ka]

[0008] wherein R1 and R4 are each a saturated or unsaturated hydrocarbyl group having 1 to 20 carbon atoms; at least one of R2 and R3 is hydrogen; at least one of R2 and R3 comprises a substituted or unsubstituted hydrocarbyl group having 5 to 15 carbon atoms, the hydrocarbyl group having a branched or straight chain structure or comprising a cycloalkyl group having 7 to 15 carbon atoms, for example, 7 to 15 carbon atoms; E1 and E2 are the same or different and are selected from the group consisting of alkyl having 1 to 20 carbon atoms, substituted alkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, substituted aryl having 6 to 20 carbon atoms, or an inert functional group having 1 to 20 carbon atoms, and optionally containing a heteroatom; and X1 and X2 are each O, S, an alkyl group, or NR5, wherein R5 is a hydrocarbyl group having 1 to 20 carbon atoms or hydrogen.

[0009] In one embodiment, at least one of R2 and R3 of the internal electron donor comprises a branched alkyl or alkenyl group. The branched alkyl or alkenyl group can contain, for example, from about 5 to about 10 carbon atoms. In one embodiment, at least one of R2 and R3 of the internal electron donor comprises a 3-pentyl group, a 2-pentyl group, a cycloheptyl group, or a cyclooctyl group.

[0010] R1 and R4 of the internal electron donor can be the same or different. In one embodiment, both R1 and R4 are linear hydrocarbyl groups. The hydrocarbyl groups can have, for example, from about 1 to about 8 carbon atoms. For example, R1 and R4 can include a C1-C8 alkyl group, a C2-C8 alkenyl group, or a mixture thereof. In one embodiment, R1 and R4 are the same and both include an alkyl group, such as a methyl or ethyl group.

[0011] In one embodiment, the internal electron donor is a non-phthalate, substituted phenylene aromatic diester. For example, E1 and E2 can both comprise a phenyl group.

[0012] The catalyst composition of the present disclosure can contain various other components. For example, the catalyst composition can include a co-catalyst. The co-catalyst can include a hydrocarbon aluminum compound such as triethylaluminum. The composition can also include a selectivity control agent. The selectivity control agent can include an alkoxysilane. For example, the selectivity control agent can include dicyclopentyldimethoxysilane, di-tert-butyldimethoxysilane, methylcyclohexyldimethoxysilane, methylcyclohexyldiethoxysilane, ethylcyclohexyldimethoxysilane, diphenyldimethoxysilane, diisopropyldimethoxysilane, di-n-propyldimethoxysilane, diisobutyldimethoxysilane, diisobutyldiethoxysilane, isobutylisopropyldimethoxysilane, di-n-butyldimethoxysilane, cyclopentyltrimethoxysilane, isopropyltrimethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, ethyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, diethylaminotriethoxysilane, cyclopentylpyrrolidinodimethoxysilane, bis(pyrrolidino)dimethoxysilane, bis(perhydroisoquinolino)dimethoxysilane, dimethyldimethoxysilane, or mixtures thereof.

[0013] In yet another embodiment, the catalyst composition may include an activity limiting agent. In one embodiment, the composition may contain an admixed external electron donor.

[0014] In addition to relating to catalyst compositions, the present disclosure also relates to a polymerization process for producing olefin polymers. The process includes polymerizing olefins in the presence of the above-described catalyst composition. In one embodiment, the olefin may include a combination of propylene and ethylene to form a propylene and ethylene copolymer. In one particular embodiment, for example, the process produces a heterophasic polymer. The heterophasic polymer may include a first polymer phase comprising a polypropylene homopolymer or an elastomeric propylene-ethylene copolymer, combined with a second polymer phase comprising an elastomeric propylene-ethylene copolymer.

[0015] The present disclosure is also directed to olefin polymers produced using the above catalyst compositions.

[0016] Other features and aspects of the disclosure are discussed in more detail below. DETAILED DESCRIPTION OF THE INVENTION

[0017] Those skilled in the art will appreciate that this discussion is a description of exemplary embodiments only and is not intended to limit the broader aspects of the present disclosure.

[0018] Generally, the present disclosure relates to a catalyst system for producing polyolefin polymers, particularly polypropylene polymers. The present disclosure also relates to a catalyst composition and a method for polymerizing and copolymerizing olefins using the catalyst composition. Generally, the catalyst composition of the present disclosure comprises a magnesium moiety, a titanium moiety, and an internal electron donor. The internal electron donor comprises a unique combination of substituents that have been found to significantly improve the performance of the catalyst composition.

[0019] More specifically, the internal electron donor of the present disclosure is a phenylene-substituted compound containing a relatively large ring or branched alkyl / alkylene. For example, the internal electron donor is believed to provide a catalyst composition with a surprisingly long lifespan, meaning that the catalyst exhibits catalytic activity in the reactor for an extended period of time, especially relative to previous catalysts. Although not yet known, it is believed that specific substitution patterns and functional groups provide lower activity during catalyst initiation, providing a more uniform polymerization kinetic profile that remains homogeneous for extended periods of time, instead of a kinetic profile characterized by high initiation activity and rapid catalyst activity decay. In this way, polymerization processes can be carried out in accordance with the present disclosure with better control and longer reaction times to form polymers with unique properties.

[0020] In addition to the above, the catalyst composition of the present disclosure can also provide various other benefits and advantages. For example, in some embodiments, the catalyst composition can provide improved prepolymerization reaction kinetics. For example, catalyst compositions made according to the present disclosure exhibit more stable kinetics that do not result in catalyst overheating during prepolymerization or the early stages of polymerization. For example, overheating can cause catalyst degradation and reduced efficiency, as well as morphology issues. However, the catalyst system of the present disclosure exhibits a more uniform kinetic profile that leads to increased polymerization efficiency over time.

[0021] Furthermore, in some processes, the catalyst composition may provide improved stereoselectivity and / or higher hydrogen response compared to previous non-phthalic acid catalysts. In one embodiment, for example, the catalyst composition may provide a rate profile similar to that of a phthalic acid-based catalyst without the need to incorporate a phthalic acid-based compound into the process.

[0022] As used herein, an internal electron donor is a compound added during the formation of a catalyst composition that donates electrons to one or more metals present in the resulting composition. The internal electron donor is believed to assist in regulating the formation of active sites, thus enhancing catalytic stereoselectivity. In one embodiment, the internal electron donor of the present disclosure has the following chemical formula: [ka]

[0023] wherein R1 and R4 are each a saturated or unsaturated hydrocarbyl group having 1 to 20 carbon atoms; at least one of R2 and R3 is hydrogen; at least one of R2 and R3 comprises a substituted or unsubstituted hydrocarbyl group having 5 to 15 carbon atoms, the hydrocarbyl group having a branched or straight chain structure, or comprising a cycloalkyl group having 5 to 15 carbon atoms, e.g., 7 to 15 carbon atoms, aryl, and substituted aryl groups; E1 and E2 are the same or different and are selected from the group consisting of alkyl having 1 to 20 carbon atoms, substituted alkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, substituted aryl having 6 to 20 carbon atoms, or an inert functional group having 1 to 20 carbon atoms, and optionally containing a heteroatom; and X1 and X2 are each O, S, an alkyl group, or NR5, wherein R5 is a hydrocarbyl group having 1 to 20 carbon atoms or hydrogen.

[0024] As used herein, the terms "hydrocarbyl" and "hydrocarbon" refer to substituents containing only hydrogen and carbon atoms, including branched or unbranched, saturated or unsaturated, cyclic, polycyclic, fused, or acyclic species, and combinations thereof. Non-limiting examples of hydrocarbyl groups include alkyl, cycloalkyl, alkenyl, alkadienyl, cycloalkenyl, cycloalkadienyl, aryl, aralkyl, alkylaryl, and alkynyl groups.

[0025] As used herein, the terms "substituted hydrocarbyl" and "substituted hydrocarbon" refer to a hydrocarbyl group substituted with one or more non-hydrocarbyl substituents. A non-limiting example of a non-hydrocarbyl substituent is a heteroatom. As used herein, "heteroatom" refers to an atom other than carbon or hydrogen. A heteroatom can be a non-carbon atom from Groups 13, 14, 15, 16, or 17 of the non-limiting examples of the periodic heteroatom table. These include halogens (F, Cl, Br, I), N, O, P, B, S, and Si. Substituted hydrocarbyl groups also include halohydrocarbyl groups and silicon-containing hydrocarbyl groups. As used herein, the term "halohydrocarbyl" group refers to a hydrocarbyl group substituted with one or more halogen atoms. As used herein, the term "silicon-containing hydrocarbyl group" refers to a hydrocarbyl group substituted with one or more silicon atoms. The silicon atom(s) may or may not be in a carbon chain.

[0026] In one embodiment, the internal electron donor described above may be combined with the magnesium and titanium moieties in forming the catalyst composition.

[0027] The internal electron donor, as shown above with respect to Formula I, includes R1-R4 groups that provide many of the advantages associated with the catalyst compositions of the present disclosure. In one embodiment, R1 and R4 are the same or very similar. In one embodiment, for example, R1 and R4 are linear hydrocarbyl groups. For example, R1 and R4 can include C1-C8 alkyl groups, C2-C8 alkenyl groups, or mixtures thereof. For example, in one embodiment, R1 and R4 can both include alkyl groups having the same carbon chain length or varying in carbon chain length by about 3 carbon atoms or less, e.g., about 2 carbon atoms or less.

[0028] In one embodiment, R4 is a methyl group and R1 is a methyl group, an ethyl group, a propyl group, or a butyl group, or vice versa. In another alternative embodiment, both R1 and R4 are methyl groups, both R1 and R4 are ethyl groups, both R1 and R4 are propyl groups, or both R1 and R4 are butyl groups.

[0029] In conjunction with the R1 and R4 groups described above, at least one of R2 or R3 is a larger or bulkier substituent than the R1 and R4 groups. The other of R2 or R3 can be hydrogen. The larger or bulkier group at R2 or R3 can be, for example, a hydrocarbyl group having a branched or linear structure, or a cycloalkyl group having 7 to 15 carbon atoms. The cycloalkyl group can be, for example, a cycloheptyl group or a cyclooctyl group. When either R2 or R3 has a branched or linear structure, the other can be a pentyl group, heptyl group, octyl group, nonyl group, decyl group, or the like. For example, R2 or R3 can be a 3-pentyl group or a 2-pentyl group.

[0030] Further examples of internal electron donors made in accordance with the present disclosure are shown below: In each of the structures below, R1-R4 may be substituted with any of the groups in any of the combinations described above. [ka]

[0031] wherein R6 to R15 may be the same or different, and each of R6 to R15 is selected from hydrogen, substituted hydrocarbyl groups having 1 to 20 carbon atoms, unsubstituted hydrocarbyl groups having 1 to 20 carbon atoms, alkoxyl groups having 1 to 20 carbon atoms, heteroatoms, and combinations thereof. [ka]

[0032] X1 and X2 above can be oxygen, sulfur, or nitrogen-containing groups. In one embodiment, for example, X1 is oxygen and X2 is sulfur. R5 and R6 can each independently comprise an alkyl group or an aryl group. R5 and R6 can each, for example, comprise a C1-C8 alkyl group. [ka]

[0033] wherein R16 and R17 are independently hydrogen or a C1-C20 hydrocarbyl group. In the above formula, X1 and X2 can be oxygen, sulfur, or nitrogen groups. Alternatively, one or both of X1 and X2 can be a hydrocarbyl group, such as an alkyl group containing 1 to 3 carbon atoms. X3 is an -OR group or an -NR1R2 group, where R, R1, or R2 is selected from a C1-C20 hydrocarbyl group optionally containing a heteroatom selected from halogen, phosphorus, sulfur, nitrogen, or oxygen. In one embodiment, X1 is a carbon atom and X3 is an ethyl group. [ka] In the formula, R5 can be an alkyl group or an aryl group, for example, R5 can be a C1 to C8 alkyl group. [ka] [ka]

[0034] wherein R18 is hydrogen or a hydrocarbyl group containing from about 1 to about 8 carbon atoms. [ka] [ka]

[0035] wherein R19, R20, and R21 are the same or different and may be selected from hydrocarbyl groups having from about 1 to about 15 carbon atoms, optionally containing a heteroatom selected from halogen, phosphorus, sulfur, nitrogen, or oxygen. R20 and R21 may be the same or different and may be fused together to form one or more cyclic groups.

[0036] The internal electron donor prepared according to the present disclosure is combined with a catalyst precursor. The catalyst precursor may include (i) magnesium, (ii) a transition metal compound of an element from Groups 4-8 of the Periodic Table, (iii) a halide, oxyhalide, and / or alkoxide of (i) and / or (ii), and (iv) a combination of (i), (ii), and (iii). Non-limiting examples of suitable catalyst precursors include halides, oxyhalides, and alkoxides of magnesium, manganese, titanium, vanadium, chromium, molybdenum, zirconium, hafnium, and combinations thereof.

[0037] In one embodiment, the preparation of the catalyst precursor involves halogenation of mixed magnesium and titanium alkoxides.

[0038] In one embodiment, the catalyst precursor is a magnesium moiety compound (MagMo), a mixed magnesium titanium compound (MagTi), or a benzoic acid-containing magnesium chloride compound (BenMag). In one embodiment, the catalyst precursor is a magnesium moiety ("MagMo") precursor. A MagMo precursor comprises a magnesium moiety. Non-limiting examples of suitable magnesium moieties include anhydrous magnesium chloride and / or its alcohol adducts, magnesium alkoxides or aryloxides, mixed magnesium alkoxyhalides, and / or carboxylated magnesium dialkoxides or aryloxides. In one embodiment, the MagMo precursor is a magnesium di(C 1-4 ) alkoxide. In a further embodiment, the MagMo precursor is diethoxymagnesium.

[0039] In one embodiment, the catalyst precursor is a mixed magnesium / titanium compound ("MAGTI"). A "MagTi precursor" is a compound of the formula Mg d Ti(OR e )fX g wherein R e is an aliphatic or aromatic hydrocarbon radical having 1 to 14 carbon atoms, or R' is an aliphatic or aromatic hydrocarbon radical having 1 to 14 carbon atoms, and each OR e The groups may be the same or different, X is independently chlorine, bromine, or iodine, preferably chlorine; d is 0.5 to 56, or 2 to 4; f is 2 to 116, or 5 to 15; and g is 0.5 to 116, or 1 to 3. The precursors are prepared by controlled precipitation by removing alcohol from the reaction mixture used in their preparation. In one embodiment, the reaction medium comprises a mixture of an aromatic liquid, particularly a chlorinated aromatic compound, most particularly chlorobenzene, and an alkanol, particularly ethanol. Suitable halogenating agents include titanium tetrabromide, titanium tetrachloride, or titanium trichloride, especially titanium tetrachloride. Removal of the alkanol from the solution used in the halogenation results in the precipitation of a solid precursor having a particularly desirable morphology and surface area. Furthermore, the resulting precursor is particularly uniform in particle size.

[0040] In one embodiment, the catalyst precursor is a benzoic acid-containing magnesium chloride material ("BenMag"). As used herein, "benzoic acid-containing magnesium chloride" ("BenMag") can be a catalyst containing a benzoic acid internal electron donor (i.e., a halogenated catalyst precursor). The BenMag material can also contain titanium moieties, such as titanium halides. The benzoic acid internal donor is unstable and can be replaced by other electron donors during catalyst and / or catalyst synthesis. Non-limiting examples of suitable benzoic acid groups include ethyl benzoate, methyl benzoate, ethyl p-methoxybenzoate, methyl p-ethoxybenzoate, ethyl p-ethoxybenzoate, and p-chlorobenzoate. In one embodiment, the benzoic acid group is ethyl benzoate. In one embodiment, the benzoglam catalyst precursor can be the product of halogenation of any catalyst precursor (i.e., a MagMo precursor or a MagTi precursor) in the presence of a benzoic acid compound.

[0041] In one embodiment, substantially spherical MgCl-nEtOH adducts can be formed by a spray crystallization process. In this process, MgCl-nROH melt (n is 1-6) is sprayed into a vessel at a temperature of 20-80°C while an inert gas is introduced into the vessel's upper portion. The molten droplets are transferred to a crystallization zone where an inert gas is introduced at a temperature of -50-20°C, causing the molten droplets to crystallize into spherical, non-agglomerated solid particles. The spherical MgCl is then classified into particles of a desired size. Particles of undesired sizes can be recycled. In a preferred embodiment for catalyst synthesis, the spherical MgCl precursor has an average particle size (Malvern diameter) of about 15-150 micrometers, preferably 20-100 micrometers, and most preferably 35-85 micrometers. 50 )

[0042] The spherical procatalyst precursor described above is referred to as a "spray crystallized" catalyst precursor. In one embodiment, the spray crystallized precursor can be dealcoholized. For example, the spray crystallization process can be subjected to a post-treatment process to remove ethanol. For example, the ethanol / magnesium chloride weight ratio can be less than about 3.5:1, such as from about 3:1 to about 1.75:1, for example, from about 2:1 to about 2.5:1.

[0043] In one embodiment, the catalyst precursor is converted to a solid catalyst by halogenation. Halogenation involves contacting the catalyst precursor with a halogenating agent in the presence of an internal electron donor. Halogenation converts magnesium moieties present in the catalyst precursor to a magnesium halide support on which titanium moieties (e.g., titanium halides) are deposited. Without wishing to be bound by any particular theory, it is believed that during halogenation, the internal electron donor (1) controls the location of titanium on the magnesium-based support, (2) promotes the conversion of the magnesium and titanium moieties to their respective halides, and (3) controls the crystallite size of the magnesium halide support during conversion. Thus, providing an internal electron donor results in a catalyst composition with improved stereoselectivity.

[0044] In one embodiment, the halogenating agent has the formula Ti(OR e ) f X h wherein R e and X is defined above, f is an integer from 0 to 3, h is an integer from 1 to 4, and +h is 4. In one embodiment, the halogenating agent is TiCl4. In a further embodiment, the halogenation is carried out in the presence of a chlorinated aromatic liquid or a non-chlorinated aromatic liquid such as dichlorobenzene, o-chlorotoluene, chlorobenzene, benzene, toluene, xylene, or mixtures thereof.

[0045] In one embodiment, the reaction mixture is heated during halogenation. The catalyst precursor and halogenating agent are initially contacted at a temperature below about 10°C, e.g., below about 0°C, e.g., below about -10°C, e.g., below about -20°C, e.g., below about -30°C. The initial temperature is generally above about -50°C, such as above about -40°C. The mixture is then heated at a rate of 0.1 to 10.0°C / min or 1.0 to 5.0°C / min. The internal electron donor may be added later, after the initial contact period between the halogenating agent and the catalyst precursor. The temperature for halogenation is from -40°C to 150°C (or any value or subrange therebetween), or from 0°C to 120°C. The halogenation may be continued for a period of 5 to 120 minutes, or from 10 to 50 minutes, in the substantial absence of the internal electron donor.

[0046] The manner in which the catalyst precursor, halogenating agent, and internal electron donor are contacted can vary. In one embodiment, the catalyst precursor is first contacted with a mixture containing the halogenating agent and the chlorinated aromatic compound. The resulting mixture can be stirred and optionally heated. The internal electron donor is then added to the same reaction mixture without isolating or recovering the precursor. The foregoing process can be carried out in a single reactor, with the addition of the various components controlled by automatic process control.

[0047] In one embodiment, the catalyst precursor is contacted with an internal electron donor before reacting with the halogenating agent.

[0048] The contact time between the catalyst precursor and the internal electron donor is at least 10 minutes, or at least 15 minutes, or at least 20 minutes, or at least 1 hour, at a temperature of at least -30°C, or at least -20°C, or at least 10°C, up to 150°C, up to 120°C, or up to 115°C, or up to 110°C.

[0049] In one embodiment, the catalyst precursor, internal electron donor, and halogenating agent are added simultaneously or substantially simultaneously.

[0050] The halogenation procedure can be repeated once, twice, three times, or more times as needed. In one embodiment, the resulting solid material is recovered from the reaction mixture and contacted multiple times in the absence (or presence) of the same (or different) internal electron donor component as the mixture of halogenating agent in the chlorinated aromatic compound at a temperature of at least about -20°C or at least about 0°C, or at least about 10°C up to about 150°C, or up to about 120°C, or up to about 115°C for at least about 10 minutes, or at least about 15 minutes, or at least about 20 minutes, and up to about 10 hours, or up to about 45 minutes, or up to about 30 minutes.

[0051] After the aforementioned halogenation procedure, the resulting solid catalyst composition is separated from the reaction medium used in the final process, for example, by filtration to produce a wet filter cake. The wet filter cake can then be washed with a rinse liquid diluent to remove unreacted TiCl4 and, if necessary, dried to remove residual liquid. Typically, the resulting solid catalyst composition is washed one or more times with a "wash liquid," which is a liquid hydrocarbon, such as isopentane, isooctane, isohexane, hexane, pentane, or an aliphatic hydrocarbon, such as octane. The solid catalyst composition can then be separated, dried, or slurried with a hydrocarbon, particularly a relatively heavy hydrocarbon such as mineral oil, for further storage or use.

[0052] In one embodiment, the resulting solid catalyst composition has a titanium content of about 1.0 weight percent to about 6.0 weight percent, or about 1.5 weight percent to about 4.5 weight percent, or about 2.0 weight percent to about 3.5 weight percent, based on the total solids weight. The weight ratio of titanium to magnesium in the solid catalyst composition is preferably about 1:3 to about 1:160, or about 1:4 to about 1:50, or about 1:6 to 1:30. In one embodiment, the internal electron donor may be present in the catalyst composition in a molar ratio of internal electron donor to magnesium of about 0.005:1 to about 1:1, or about 0.01:1 to about 0.4:1. The weight percentages are based on the total weight of the catalyst composition.

[0053] In one embodiment, the catalyst composition may be further treated by one or more of the following procedures, either before or after isolation of the solid catalyst composition: The solid catalyst composition may be contacted (halogenated) with an additional amount of a titanium halide compound.

[0054] Without wishing to be bound by any particular theory, it is believed that the desired modification of the catalyst composition results from (1) further halogenation by contacting the preformed catalyst composition with a titanium halide compound (particularly a solution thereof in a halohydrocarbon diluent), and / or (2) further washing of the preformed catalyst composition containing the halohydrocarbon at elevated temperatures (100-150°C) (possibly to remove certain inert or undesirable metal compounds that are soluble in said diluent). Thus, in one embodiment, the catalyst is contacted one or more times with a halogenating agent, such as a mixture of a titanium halide and a halohydrocarbon diluent, e.g., TiCl4 and chlorobenzene, before isolation or recovery. In another embodiment, the catalyst is washed one or more times with chlorobenzene or o-chlorotoluene at temperatures between 100-150°C before isolation or recovery.

[0055] The process for producing the catalyst composition may include two or more embodiments disclosed herein.

[0056] As described above, the catalyst composition can include a combination of a magnesium moiety, a titanium moiety, and an internal electron donor. The catalyst composition is produced by the aforementioned halogenation procedure, which converts the catalyst precursor and the internal electron donor into a combination of a magnesium moiety and a titanium moiety incorporating the internal electron donor. The catalyst precursor from which the catalyst composition is formed can be a magnesium moiety precursor, a mixed magnesium / titanium precursor, a benzoic acid-containing magnesium chloride precursor, or a spherical precursor.

[0057] In one embodiment, the magnesium moiety is a magnesium halide, hi another embodiment, the magnesium halide is magnesium chloride or a magnesium chloride alcohol adduct.

[0058] In one embodiment, the titanium moiety is a titanium halide, such as titanium chloride, hi another embodiment, the titanium moiety is titanium tetrachloride.

[0059] In another embodiment, the catalyst composition comprises a magnesium chloride support on which titanium chloride is deposited and on which an internal electron donor is incorporated.

[0060] The present disclosure is also directed to catalyst systems comprising the above-described catalyst composition in combination with various other catalyst components. For example, in one embodiment, the catalyst composition includes a cocatalyst. As used herein, a "cocatalyst" is a substance capable of converting a procatalyst into an active polymerization catalyst. The cocatalyst may include chlorides, alkyls, or halides, such as aryls, of aluminum, lithium, zinc, tin, cadmium, beryllium, magnesium, and combinations thereof. In one embodiment, the cocatalyst is a hydrocarbyl aluminum cocatalyst represented by the formula R3Al, where each R is an alkyl, cycloalkyl, aryl, or hydride radical, at least one R is a hydrocarbyl radical, and two or three R radicals can be combined into a cyclic radical to form a heterocyclic structure, where each R can be the same or different, and each R, which is a hydrocarbyl radical, has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. In further embodiments, each alkyl radical may be straight-chained or branched, and such hydrocarbyl radicals may be mixed radicals, i.e., the radical may contain alkyl, aryl, and / or cycloalkyl groups. Non-limiting examples of suitable radicals are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, 2-methylpentyl, n-heptyl, n-octyl, isooctyl, 2-ethylhexyl, 5,5-dimethylhexyl, n-nonyl, n-decyl, isodecyl, n-undecyl, n-decyl.

[0061] Non-limiting examples of suitable hydrocarbyl aluminum compounds are: triisobutylaluminum, tri-n-hexylaluminum, diisobutylaluminum chloride, di-n-hexylaluminum chloride, isobutylaluminum dichloride, n-hexylaluminum dichloride, diisobutylhexylaluminum, isobutyldihexylaluminum, trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, tri-n-octylaluminum, tri-n-decylaluminum, tri-n-dodecylaluminum. In one embodiment, the cocatalyst is selected from triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, diisobutylaluminum chloride, and di-n-hexylaluminum chloride.

[0062] In one embodiment, the co-catalyst has the formula R n AlX 3-n wherein n=1 or 2, R is alkyl, and X is a halide or alkoxide.

[0063] In one embodiment, the cocatalyst is triethylaluminum. The molar ratio of aluminum to titanium is from about 5:1 to about 1000:1, or from about 10:1 to about 200:1, or from about 15:1 to about 150:1, or from about 20:1 to about 100:1. In another embodiment, the molar ratio of aluminum to titanium is about 45:1.

[0064] In one embodiment, the catalyst composition includes a selectivity control agent. As used herein, a "selectivity control agent" is a compound that is added independently of the procatalyst formulation and contains at least one functional group capable of donating an electron to a metal atom. Without being bound by any particular theory, the selectivity control agent is believed to improve catalyst stereoselectivity (i.e., to reduce xylene-soluble material in the formant polymer).

[0065] In one embodiment, the selectivity control agent donor may be selected from one or more of the following: alkoxysilanes, amines, ethers, carboxylates, ketones, amides, carbamates, phosphines, phosphates, phosphites, sulfonates, sulfones, and / or sulfoxides.

[0066] In one embodiment, the selectivity control agent donor is an alkoxysilane. The alkoxysilane has the following general formula: SiR m (OR') 4-m (I) when R occurs independently at each occurrence, R is hydrogen or hydrocarbyl, or an amino group optionally substituted with one or more substituents containing one or more 14, 15, 16, or 17 heteroatoms, said R containing up to 20 atoms, not including hydrogen and halogen; and R' is C 1~4 alkyl group, and m is 0, 1, 2, or 3. In one embodiment, R is C 6~12 Aryl, alkyl or aralkyl, C 3~12 Cycloalkyl, C 3~12 Branched alkyl, or C 3~12 is a cyclic or acyclic amino group, and R' is C 1~4alkyl, and m is 1 or 2. Non-limiting examples of suitable silane compositions include dicyclopentyldimethoxysilane, di-tert-butyldimethoxysilane, methylcyclohexyldimethoxysilane, methylcyclohexyldiethoxysilane, ethylcyclohexyldimethoxysilane, diphenyldimethoxysilane, diisopropyldimethoxysilane, di-n-propyldimethoxysilane, diisobutyldimethoxysilane, diisobutyldiethoxysilane, isobutylisopropyldimethoxysilane, di-n-butyldimethoxysilane, cyclopentyltrimethoxysilane, isopropyltrimethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, ethyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, diethylaminotriethoxysilane, cyclopentylpyrrolidinodimethoxysilane, bis(pyrrolidino)dimethoxysilane, bis(perhydroisoquinolino)dimethoxysilane, and dimethyldimethoxysilane. In one embodiment, the silane composition is dicyclopentyldimethoxysilane (DCPDMS), methylcyclohexyldimethoxysilane (MChDMS), or n-propyltrimethoxysilane (NPTMS), and any combination thereof.

[0067] In one embodiment, the selectivity control agent can be a mixture of at least two alkoxysilanes. In further embodiments, the mixture can be dicyclopentyldimethoxysilane and methylcyclohexyldimethoxysilane, dicyclopentyldimethoxysilane and tetraethoxysilane, or dicyclopentyldimethoxysilane and n-propyltriethoxysilane.

[0068] In one embodiment, the selectivity control agent is selected from one or more of the following: benzoic acid, succinic acid, and / or diolesterol. In another embodiment, the selectivity control agent is a diether.

[0069] In one embodiment, the catalyst composition includes an activity limiting agent (ALA). As used herein, an "activity limiting agent" ("ALA") is a material that reduces catalyst activity at high temperatures (i.e., temperatures above about 85°C). The ALA inhibits or otherwise prevents polymerization reactor upsets and ensures continuity of the polymerization process. Typically, the activity of a Ziegler-Natta catalyst increases as the reactor temperature increases. Ziegler-Natta catalysts also typically maintain high activity near the melting point temperature of the produced polymer. Heat generated by an exothermic polymerization reaction can cause polymer particles to form aggregates, ultimately disrupting the continuity of the polymer production process. The ALA reduces catalyst activity at high temperatures, thereby reducing (or preventing) reactor upsets, particle agglomeration, and ensuring continuity of the polymerization process.

[0070] The activity limiting agent can be a carboxylic acid ester, a diether, a poly(alkene glycol), a poly(alkene glycol) ester, a diol ester, or a combination thereof. The carboxylic acid ester can be an aliphatic or aromatic, mono- or polycarboxylic acid ester. Non-limiting examples of suitable 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, propyl pivalate, and pentyl valerate.

[0071] Aliphatic carboxylic acid esters are C4 to C 30 It can be an aliphatic acid ester, can be a mono- or poly(2 or more) ester, can be linear or branched, can be saturated or unsaturated, or any combination thereof. 30 The aliphatic acid esters may also be substituted with substituents containing one or more Group 14, 15, or 16 heteroatoms. 30 Non-limiting examples of aliphatic acid esters include aliphatic C 4~30Monocarboxylic acid C 1~20 Alkyl ester, aliphatic C 8~20 Monocarboxylic acid C 1~20 Alkyl ester, aliphatic C 4~20 C of monocarboxylic and dicarboxylic acids 1~4 Allyl mono- and diesters, aliphatic C 8~20 C of monocarboxylic and dicarboxylic acids 1~4 Alkyl esters, and C 2~100 (Poly)glycol or C 2~100 (Poly)glycol ether C 4~20 In a further embodiment, C4 to C6 30 Aliphatic acid esters include laurates, myristates, palmitates, stearates, oleates, sebacates, (poly)(alkylene glycol) mono- or diacetates, (poly)(alkylene glycol) mono- or di-laurates, (poly)(alkylene glycol) mono- or di-laurates, (poly)(alkylene glycol) mono- or diolates, glyceryl tri(acetate), C2- 40 In a further embodiment, the glyceryl triesters of fatty carboxylic acids may be C4 to C6 glyceryl triesters of fatty carboxylic acids and mixtures thereof. 30 The aliphatic ester is isopropyl myristate or di-n-butyl sebacate.

[0072] In one embodiment, the activity limiting agent comprises a diether, which may be a 1,3-diether compound represented by structure (XV) below. [ka]

[0073] wherein R1-R4 are, independently of one another, alkyl, aryl, or aralkyl groups having up to 20 carbon atoms, optionally containing 14, 15, 16, or 17 heteroatoms, and R1 and R2 can be hydrogen atoms. The dialkyl ether can be linear or branched and can contain one or more of the following groups: alkyl, alicyclic, aryl, alkylaryl, or arylalkyl radicals having 1 to 18 carbon atoms, and hydrogen. R1 and R2 can be linked to form a ring structure, such as cyclopentadiene or fluorene.

[0074] In one embodiment, the activity limiting agent comprises a succinic acid composition having the following structure (XVI): [ka]

[0075] wherein R and R' may be the same or different, and R and / or R' may comprise one or more of the following groups: hydrogen, straight-chain or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl, or alkylaryl groups, optionally containing heteroatoms; and one or more ring structures may be formed via one or both of the 2- and 3-position carbon atoms.

[0076] In one embodiment, the activity limiting agent comprises a diol ester represented by the following structure (XVII): [ka]

[0077] wherein n is an integer from 1 to 5. R1 and R2 may be the same or different and each may be selected from hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, allyl, phenyl, or halophenyl groups. R3, R4, R5, R6, R7, and R8 may be the same or different and each may be selected from hydrogen, halogen, substituted, or unsubstituted hydrocarbyl having 1 to 20 carbon atoms. The R1-R6 groups may optionally contain one or more heteroatoms replacing carbon, hydrogen, or both, where the heteroatoms are selected from nitrogen, oxygen, sulfur, silicon, phosphorus, and halogen. R7 and R8 may be the same or different and may be attached to any of the 2-, 3-, 4-, 5-, and 6-position carbon atoms of either phenyl ring.

[0078] In one embodiment, the catalyst system comprises a mixed external electron donor, the mixed external electron donor comprising at least two of the following components: (1) a first selectivity control agent, (2) a second selectivity control agent, and (3) an activity limiting agent.

[0079] In one embodiment, the selectivity control agent and / or activity limiting agent can be added separately to the reactor. In another embodiment, the selectivity control agent and activity limiting agent can be premixed and then added to the reactor as a mixture. One or more selectivity control agents or one or more activity limiting agents can be used in the mixture. In one embodiment, the mixture is dicyclopentyldimethoxysilane and isopropyl myristate, dicyclopentyldimethoxysilane and poly(ethylene glycol) laurate, dicyclopentyldimethoxysilane and isopropyl myristate and poly(ethylene glycol) dioleate, methylcyclohexyldimethoxysilane and isopropyl myristate, n-propyltrimethoxysilane and isopropyl myristate, dimethyldimethoxysilane and methylcyclohexyl, isopropyl myristate, dicyclopentyldimethoxysilane and n-propyltriethoxysilane and isopropyl myristate, and dicyclopentyldimethoxysilane and tetraethoxysilane and isopropyl myristate, and combinations thereof.

[0080] In one embodiment, the catalyst composition comprises any of the aforementioned selectivity control agents in combination with any of the aforementioned activity limiting agents.

[0081] The catalyst composition may comprise two or more embodiments disclosed herein.

[0082] In one embodiment, a process for producing an olefin-based polymer is provided. The process comprises contacting an olefin with a catalyst composition under polymerization conditions. The catalyst composition comprises the substituted phenylene internal electron donor described above. The process further comprises forming the olefin-based polymer.

[0083] In one embodiment, the catalyst composition comprises a catalyst composition and a cocatalyst. The catalyst composition can be any catalyst composition disclosed herein. The catalyst composition can include a substituted phenylene compound as an internal electron donor. The cocatalyst can be any cocatalyst disclosed herein. The catalyst composition can optionally include a selectivity control agent and / or an activity limiting agent as previously disclosed.

[0084] In one embodiment, the olefin-based polymer can be a propylene-based olefin, an ethylene-based olefin, and combinations thereof. In one embodiment, the olefin-based polymer is a propylene-based polymer.

[0085] One or more olefin monomers can be introduced into the polymerization reactor to react with the catalyst to form a polymer or a fluidized bed of polymer particles. Non-limiting examples of suitable olefin monomers include ethylene, propylene, C 4~20 α-olefins, such as 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, etc., C 4~20 Diolefins, such as 1,3-butadiene, 1,3-pentadiene, norbornadiene, 5-ethylidene-2-norbornene (ENB) and dicyclopentadiene, styrene, o-methylstyrene, m-methylstyrene, and p-methylstyrene, divinylbenzene, vinylbiphenyl, vinylnaphthalene, and the like. 8~40 Vinyl aromatic compounds and halogen-substituted C 8~40 Vinyl aromatic compounds include, for example, chlorostyrene and fluorostyrene.

[0086] As used herein, "polymerization conditions" are the temperature and pressure parameters in a polymerization reactor suitable for promoting polymerization between the catalyst composition and the olefin to form the desired polymer. The polymerization process can be a gas phase, slurry, or bulk polymerization process operating in one or more reactors.

[0087] In one embodiment, polymerization occurs via gas-phase polymerization. As used herein, "gas-phase polymerization" refers to the passage of an ascending fluidizing medium, a fluidizing medium containing one or more monomers, in the presence of a catalyst through a fluidized bed of polymer particles maintained in a fluidized state by the fluidizing medium. "Fluidization," "fluidized," or "fluidizing" refers to a gas-solid contact process in which a bed of finely divided polymer particles is elevated and agitated by an upward flow of gas. Fluidization occurs in a bed of fine particles when the upward flow of fluid through the interstices of the particle bed reaches a pressure differential and frictional resistance increase that exceeds the particle weight. Thus, a "fluidized bed" is a plurality of polymer particles suspended in a fluidized state by the flow of the fluidizing medium. The "fluidizing medium" refers to one or more olefin gases, optionally a carrier gas (e.g., H2 or N2), and optionally a liquid (e.g., hydrocarbon) rising through a gas-phase reactor.

[0088] A typical gas-phase polymerization reactor (or gas-phase reactor) includes a vessel (i.e., reactor), a fluidized bed, a distribution plate, inlet and outlet piping, a compressor, a cycle gas cooler or heat exchanger, and a product discharge system. The vessel includes a reaction zone and a velocity 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.

[0089] In addition to gas-phase polymerization processes, the catalyst composition of the present disclosure can also be used in bulk-phase processes. In bulk polymerization processes, the catalyst composition is contacted with one or more liquid monomers, such as liquid propylene. Hydrogen can also be included in the reaction medium to control the molecular weight of the resulting polymer.

[0090] In one embodiment, the contacting occurs by feeding the catalyst composition to a polymerization reactor and introducing the olefin into the polymerization reactor. In one embodiment, the cocatalyst can be mixed (premixed) with the catalyst composition prior to introducing the catalyst composition into the polymerization reactor. In another embodiment, the cocatalyst is added to the polymerization reactor independently of the catalyst composition. The independent introduction of the cocatalyst into the polymerization reactor can occur simultaneously or substantially simultaneously with the catalyst composition feed.

[0091] In one embodiment, the polymerization process may include a prepolymerization step. Prepolymerization involves adding a catalyst composition to an olefin polymerization process, resulting in a low conversion of about 0.5 to about 1000 grams of polymer per gram of solid catalyst component after contact with a cocatalyst and a selectivity control agent and / or activity limiting agent. The prepolymerization step can be carried out as part of a continuous polymerization process or separately in a batch process. When carried out as part of a continuous process, the conversion of the prepolymerization catalyst component is preferably about 50 to about 500 grams of polymer per gram of solid catalyst component. The prepolymerization catalyst stream is then introduced into the main polymerization reaction zone and contacted with the remainder of the olefin monomer to be polymerized, optionally with additional amounts of one or more of the cocatalyst and selectivity control agent components. Prepolymerization results in a procatalyst composition combined with the cocatalyst and the selectivity control agent and / or activity limiting agent, which combination is dispersed in the matrix of the formant polymer. Optionally, additional amounts of the cocatalyst, selectivity control agent, and / or activity limiting agent may be added.

[0092] In one embodiment, the polymerization process may include a preactivation step. The preactivation step involves contacting the catalyst composition with a cocatalyst and a selectivity control agent and / or activity limiting agent. The resulting preactivation catalyst stream is then introduced into a polymerization reaction zone and contacted with the olefin monomer to be polymerized and, optionally, one or more selectivity control agent components. Prior to activation, the procatalyst composition is combined with the cocatalyst and the selectivity control agent and / or activity limiting agent. Optionally, an additional amount of the selectivity control agent and / or activity limiting agent may be added.

[0093] In one embodiment, the process includes mixing a selectivity control agent (and optionally an activity limiting agent) with the catalyst composition. The selectivity control agent forms a complex with the cocatalyst and can be mixed (premixed) with the catalyst composition prior to contact between the catalyst composition and the olefin. In another embodiment, the selectivity control agent and / or the activity limiting agent can be added independently to the polymerization reactor. In one embodiment, the selectivity control agent is dicyclopentyldimethoxysilane or n-propyltrimethoxysilane.

[0094] In another embodiment, the catalyst composition comprises dicyclopentyldimethoxysilane or n-propyltrimethoxysilane and an activity limiting agent such as isopropyl myristate.

[0095] In one embodiment, polypropylene homopolymer is produced in a first reactor. The contents of the first reactor are then transferred to a second reactor where ethylene is introduced, resulting in the production of propylene-ethylene copolymer in the second reactor.

[0096] In one embodiment, a polypropylene homopolymer is formed by introducing propylene and any of the catalyst composition, cocatalyst, selectivity control agent, and activity limiting agent into a first reactor. The polypropylene homopolymer is then introduced into a second reactor together with ethylene and, optionally, a selectivity control agent and / or activity limiting agent. The selectivity control agent and activity limiting agent may be the same or different from the respective components used in the first reactor. This produces a propylene-ethylene copolymer in the second reactor.

[0097] In one embodiment, the olefin is propylene. The process includes forming a propylene-based polymer having a melt flow rate (MFR) of from about 0.01 g / 10 min to about 800 g / 10 min, or from about 0.1 g / 10 min to about 200 g / 10 min, or from about 0.5 g / 10 min to about 150 g / 10 min. In a further embodiment, the propylene-based polymer is a polypropylene homopolymer.

[0098] In one embodiment, the olefin is propylene. The process includes forming a propylene-based polymer having a xylene solubles content of from about 0.5% to about 10%, or from about 1% to about 8%, or from about 1% to about 4%. In a further embodiment, the propylene-based polymer is a polypropylene homopolymer.

[0099] In one embodiment, the olefin is propylene. The process includes forming a propylene-based polymer having a polydispersity index (PDI) of from about 4 to about 15, or from about 4 to about 10, or from about 4 to about 8. In a further embodiment, the propylene-based polymer is a polypropylene homopolymer.

[0100] The present disclosure provides another process. In one embodiment, a polymerization process is provided, comprising contacting propylene and ethylene and / or 1-butene with a catalyst composition under polymerization conditions. The catalyst composition can be any catalyst composition disclosed herein. The process comprises forming a random propylene-based interpolymer having an MFR of from about 0.01 g / 10 min to about 200 g / 10 min, or from about 0.1 g / 10 min to about 100 g / 10 min, or from about 0.5 g / 10 min to about 70 g / 10 min. The formant propylene-based interpolymer has a xylene solubles content of from about 0.5% to about 40%, or from about 1% to about 30%, or from about 1% to about 20%.

[0101] The formant propylene-based interpolymers have a comonomer content, by weight percent relative to propylene, of from about 0.001% to about 20%, or from about 0.01% to about 15%, or from about 0.1% to about 10%.

[0102] The catalyst compositions and catalyst systems of the present disclosure are also well suited to producing impact polymers with rubber-like or elastomeric properties. These polymers are typically made in a two-reactor system, where it is desirable for the catalyst to maintain a high activity level. In one embodiment, for example, polymerization is carried out in two reactors connected in series. To form an active propylene-based polymer, a propylene homopolymer or propylene copolymer can be formed in a first reactor. The active propylene-based polymer from the first polymerization reactor is then introduced into a second polymerization reactor, where, under second polymerization conditions, a propylene impact copolymer is formed with at least one second monomer in the second reactor. In one embodiment, the process includes contacting the active propylene-based polymer with propylene and ethylene in the second polymerization reactor under polymerization conditions to form a discontinuous phase of a propylene / ethylene copolymer.

[0103] As noted above, the first phase polymer may comprise a polypropylene homopolymer. However, in an alternative embodiment, the first phase polymer may comprise a random copolymer of polypropylene.

[0104] The random copolymer may be a copolymer of propylene and an alpha-olefin, such as ethylene. The polypropylene random copolymer forms the matrix polymer in the polypropylene composition and may contain, for example, less than about 5 wt%, for example less than about 4 wt%, and generally more than about 0.5 wt%, for example more than about 1 wt%, for example more than about 1.5 wt%, for example more than about 2 wt%, or less than about 12 wt% of the alpha-olefin. The first phase polymer may have a xylene soluble content of less than about 12 wt%, for example less than about 10 wt%, for example less than about 8 wt%, for example less than about 6 wt%, for example less than about 4 wt%. The xylene soluble content is generally more than about 0.5 wt%, for example more than about 3 wt%.

[0105] In one embodiment, the polypropylene random copolymer or polypropylene homopolymer comprising the first phase polymer has a relatively high melt flow rate. For example, the first phase polymer can have a melt flow rate of greater than about 5 g / 10 min, e.g., greater than about 10 g / 10 min, e.g., greater than about 15 g / 10 min, e.g., greater than about 20 g / 10 min, e.g., about 25 g / 10 min. The melt flow rate of the first phase polymer is generally less than about 1000 g / 10 min, e.g., less than about 500 g / 10 min.

[0106] The second phase polymer is a propylene and alpha-olefin copolymer. However, the second phase polymer has elastomeric or rubber-like properties. Therefore, the second phase polymer can dramatically improve the impact resistance of the polymer.

[0107] The second phase polymer forming the dispersed phase in the polymer composition generally contains an alpha-olefin or ethylene in an amount greater than about 10 wt%, such as greater than about 12 wt%, for example greater than about 14 wt%, generally less than about 35 wt%, for example less than about 20 wt%, for example less than about 17 wt% or less. The second phase polymer can have a weight average molecular weight of at least about 130,000, for example at least about 140,000, for example at least about 150,000, and generally less than about 500,000.

[0108] In one embodiment, the olefin-based polymer (ie, propylene-based polymer) produced by any of the aforementioned processes comprises a substituted phenylene as described above.

[0109] The polymerization process may include two or more embodiments disclosed herein.

[0110] Without wishing to be bound by any particular theory, it is believed that the present catalyst compositions having substituted phenylene aromatic diester internal electron donors result in olefin-based polymers, high catalytic activity, and high stereoselectivity. Furthermore, the present substituted phenylene aromatic diesters advantageously provide the procatalyst composition(s), catalyst composition(s), and olefin-based polymer(s) with phthalate ester-free or phthalate ester and / or its derivatives-free or devoid properties. [Example]

[0111] General Procedure - Synthesis of Internal Electron Donors The internal electron donors used in the examples below were generally synthesized using the following methods. [ka]

[0112] Internal donors were generated by two different methods, representative examples of which are shown below.

[0113] Process Details: Method A

[0114] Synthesis of 4-bromo-3,6-dimethyl-1,2-phenylenedibenzoate (2)

[0115] An appropriate amine base is charged to a solution of 4-bromo-3,6-dimethyl-1,2-benzenediol (1) in an organic solvent. The reactor is cooled by contact with the acyl chloride and allowed to warm to room temperature. Upon completion, the reaction is quenched with water. The aqueous layer is separated and the organic fraction is neutralized. The solution is concentrated to yield an orange solid. The crude product is recrystallized in a hydrocarbon solvent. Filtration affords 4-bromo-3,6-dimethyl-1,2-phenylenedibenzoate (2) as an off-white solid.

[0116] Synthesis of 4-(3-pentyl)-3,6-dimethyl-1,2-phenylenedibenzoate

[0117] 4-Bromo-3,6-dimethyl-1,2-phenylenedibenzoate (2) is charged to an inert vessel with a palladium catalyst. The solid is dissolved in an ether solvent, and the appropriate transmetalation partner is introduced to the reaction. The reaction is heated and, upon completion, quenched and diluted in an organic solvent. The organic fraction is washed with subsequent portions of water. The product solution is then concentrated to a solid. The crude solid is recrystallized in an organic solvent. 4-(3-pentyl)-3,6-dimethyl-1,2-phenylenedibenzoate (ID-1) is isolated as a white solid.

[0118] Method B

[0119] Synthesis of 4-(3-(2,4-methyl-2-pentenyl))-3,6-dimethyl-2-hydroxybenzaldehyde (4)

[0120] 4-(3-(2,4-Methyl-2-pentenyl))-2,5-dimethylphenol (3). HMTA is dissolved in trifluoroacetic acid. The reaction is thoroughly heated, cooled, and then concentrated. An organic solvent and aqueous acid are added and heated for a period of time. Upon completion, the organic fraction is separated and concentrated to give 4-(3-(2,4-methyl-2-pentenyl))-3,6-dimethyl-2-hydroxybenzaldehyde (4).

[0121] Synthesis of 4-(3-(2,4-methyl-2-pentenyl))-3,6-dimethyl-1,2-benzenediol (5)

[0122] The previously prepared benzaldehyde (4) is dissolved in a combination of an ethereal solvent and water. The mixture is contacted with an aqueous base solution and an aqueous hydrogen peroxide solution. The reaction is heated to completion, cooled, and quenched with an acidic medium. The product layer is neutralized, dried, and concentrated to give 4-(3-(2,4-methyl-2-pentenyl))-3,6-dimethyl-1,2-benzenediol (5).

[0123] Synthesis of 4-(3-(2,4-methyl-2-pentenyl))-3,6-dimethyl-1,2-phenylenedibenzoate (ID-9)

[0124] An appropriate amine base is charged to a solution of compound (5) in an organic solvent. The reactor is cooled by contact with the acyl chloride and allowed to warm to room temperature. Upon completion, the reaction is quenched with water. The aqueous layer is separated. The organic fraction is neutralized. The solution is concentrated to yield an orange solid. The crude product is recrystallized in a hydrocarbon solvent. 4-(3-(2,4-methyl-2-pentenyl))-3,6-dimethyl-1,2-phenylenedibenzoate (ID-9) is isolated as an off-white solid.

[0125] General procedure - polymerization conditions

[0126] Homopolymerization at 70 °C. A 2 L stainless steel autoclave equipped with an overhead stirrer and thermostatic jacket was cooled to 20 °C and heated to 90 °C for 1 h before replacing the argon with propylene gas. o The reactor was purged with argon at 70°C. A cocatalyst solution was prepared by mixing 2.3 mmol of triethylaluminum and 0.078 mmol of dicyclopentyldimethoxysilane in 15 ml of hexane. 6 ml of the cocatalyst solution was added to Loading Tube A. The remainder was added to Loading Tube B using approximately 3 mg of solid catalyst. Hydrogen (57 mmol) was added to the reactor, and the contents of Loading Tube A were flushed into the reactor with 600 ml of propylene. The agitator was started, and the contents of Loading Tube B were flushed into the reactor with 450 ml of propylene. The reactor was heated to 70°C for 10 minutes, and the polymerization was continued for 1 hour. At the end of the polymerization, the agitator was turned off, and the unreacted propylene was vented while the reactor was cooled. The polymer was recovered and stored at 50°C for 1 hour before being weighed and analyzed. o The mixture was dried in a vacuum oven at 40°C.

[0127] When polymerizations were carried out in a 4 L autoclave, the same general procedure was followed except that 1400 mL and 600 mL of propylene were added to charged tubes A and B, respectively. The reagent amounts for the 4 L polymerization were 2,000 ml of propylene, 252 mmol of hydrogen, 3.4 mmol of triethylaluminum, 0.131 mmol of dicyclopentyldimethoxysilane, and 8.0 mg of catalyst.

[0128] Two-stage copolymerization. The procedure described for homopolymerization at 70°C was followed, except that after 45 minutes of polymerization, the reactor pressure was reduced to 200 psig. A 4 L autoclave was used, hydrogen was added (100 mmol), and ethylene was added to a reactor pressure of 300 psig while the reactor temperature was increased to 80°C. Polymerization continued in the gas phase at 80°C and 300 psig for 45 minutes, continuously feeding a 1 / 1 molar ethylene / propylene gas mixture. The results are collected in Table 4.

[0129] Low-Temperature Polymerization. The same general procedure described for the homopolymerization at 70°C was followed, except that the charge tubes A and B were added at the polymerization temperature and the polymerization was terminated after 30 minutes using a 2 L autoclave. The reagent amounts for the low-temperature polymerization were 1,050 ml of propylene, 21 mmol of hydrogen, 3.5 mmol of triethylaluminum, 0.175 mmol of dicyclopentyldimethoxysilane, and 20 mg of catalyst. The results are collected in Table 5.

[0130] Melt flow rates were measured at 230°C for propylene-based polymers according to the ASTM D1238-01 test method using a 2.16 kg weight. Xylene solubles (XS) were measured using a Crystex automated instrument by Polymer Char. The Crystex was calibrated with polypropylene homopolymer samples analyzed for XS according to the ASTM D5492-10 test method.

[0131] AMgCl2 * The EtOH adduct was prepared as previously described in U.S. Pat. No. 5,468,698. MgCl2 with an average particle size of 58 micrometers was used. * The EtOH adduct was used in Examples E-6 to E-13.

[0132] Example internal donor structures are shown in Table 1. [Example]

[0133] E-1 to E-5, E-14, and E-15. 4.0 g of MagTi support (U.S. Pat. Nos. 5,124,298 and 5,962,361) was added to a 100 ml Schlenk flask and slurried with 20 ml of monochlorobenzene (MCB). The slurry was transferred to a 1 L reactor at room temperature under pure N2. Another 20 ml of MCB was added to the support flask and used to rinse the remaining support into the reactor. Then, 40 ml (70 g) of TiCl4, either at room temperature or cooled to 10°C, was immediately added to the reactor. The slurry was heated to 25°C and stirred at this temperature for 5 minutes.

[0134] Next, 2.31–2.38 mmol of donor dissolved in 6.5–7.0 ml of monochlorobenzene (MCB) is added to the reactor. The temperature is then increased to 100°C (40 min) and held for 50 min. Stirring is stopped, and the slurry is allowed to settle while maintaining the reactor at 100°C. The supernatant is decanted, followed by the addition of 80 ml of a 50:50 volume mixture of TiCl4 and MCB. The reactor is heated to 115°C. During heating, 1.16–1.24 mmol of donor dissolved in 3.5 ml of MCB is added. The reaction mixture is held at 115°C for 25 min.

[0135] The stirring is stopped and the slurry is allowed to settle while the reactor is maintained at 115°C. The supernatant is decanted, followed by the addition of 80 ml of a 50:50 volume mixture of TiCl4 and MCB. The reactor is reheated to 115°C and held at this temperature for 25 minutes. The stirring is stopped and the slurry is allowed to settle while the reactor is maintained at 115°C. The supernatant is decanted.

[0136] The reactor temperature is set to 25°C. 100 ml of heptane is then added and stirred for 10 minutes before settling and decanting the wash. This is repeated four more times as the reactor cools, with the final two washes performed in the reactor at 25°C. The wet solid is dried under vacuum at 40°C for 2 hours. The catalyst composition and bulk polymerization test data are shown in Table 2.

[0137] E-6: 30 g of MgCl2 with an EtOH / Mg molar ratio of 3.1 and 80 ml of heptane * The EtOH precursor was added to a 1 L jacketed glass reactor with overhead stirring, and the mixture was cooled to -20 °C. 520 g of TiCl4 was pre-cooled to -20 °C, and stirring was continued for 1 h. The reactor temperature was increased to 20 °C at a rate of 0.33 °C / min. A solution of 2.25 g of ethyl benzoate in 10 ml of heptane was added via cannula. After the addition was complete, the reactor temperature was increased to 85 °C at a rate of 0.54 °C / min. During the temperature ramp, a solution of 5.4 g of ID-1 in 45 ml of toluene was metered in at a rate of 0.5 mL / min. After reaching 85 °C, stirring was continued for 1 h, after which the catalyst solid was allowed to settle, and the supernatant was decanted. 520 g of pre-heated TiCl4 was added, followed by a solution of 3.0 g of ID-1 in 23 ml of toluene. The mixture was stirred for 1 h, and then the precipitation and decantation process was repeated. The TiCl4 treatment was repeated at 130°C for 0.5 hours. After the settling and decanting steps, the reactor was cooled to 65°C. The catalyst solid was washed five times with heptane at 65°C, with each wash being 300 ml. The catalyst was then vacuum dried at 40°C for 4 hours. The catalyst composition and bulk polymerization test data are shown in Table 3.

[0138] E-7: 20 g of MgCl precursor containing an EtOH / Mg molar ratio of 2.2 and 73 ml of heptane was added to a 1 L jacketed glass reactor with overhead stirring, and the mixture was cooled to -20 °C. 350 g of TiCl pre-cooled to -20 °C was added, and stirring was continued for 1 h. The reactor temperature was increased to 20 °C at a rate of 0.33 °C / min. A solution of 1.2 g of ethyl benzoate in 5 ml of heptane was added via cannula. After the addition was complete, the reactor temperature was increased to 85 °C at a rate of 0.54 °C / min. During the temperature ramp, a solution of 1.8 g of ID-1 in 30 ml of toluene was metered in at a rate of 0.4 mL / min. After reaching 85 °C, stirring was continued for 1 h, after which the catalyst solid was allowed to settle, and the supernatant was decanted. 70 g of preheated TiCl4 and 140 g of toluene were added, followed by the addition of 0.8 g of ID-1 in 10 ml of toluene, and the mixture was stirred at 105 °C for 1 hour before the precipitation and decantation steps were repeated. The TiCl4 / toluene treatment was repeated at 120 °C for 1 hour. After precipitation and decantation, the reactor was cooled to 65 °C. The catalyst solid was washed five times with heptane at 65 °C, with 200 ml of each wash. The catalyst was then vacuum dried at 40 °C for 4 hours. The catalyst composition and bulk polymerization test data are listed in Table 3.

[0139] The same procedure as E-2 was followed by E-8, except that 1.5 g of ethyl benzoate was charged, and 1.8 g of ID-4 was used in the first charge and 1.2 g of ID-4 was used in the second charge. The same procedure as E-3 was used with ID-6, followed by E-9. The same procedure as E-1 was used with ID-7, followed by E-10. The same procedure as E-1 was used with ID-8, followed by E-11. The same procedure as E-3 was used with ID-7, followed by E-12. Catalyst compositions and bulk polymerization test data are listed in Table 3.

[0140] E-1: 20 g of MgCl precursor with a 3:3:1 EtOH / Mg molar ratio and 70 ml of octane were added to a 1 L jacketed glass reactor with overhead stirring, and the mixture was cooled to -20 °C. 520 g of TiCl was pre-cooled to -20 °C, and stirring was continued for 1 hour. The reactor temperature was increased to 20 °C at 0.44 °C / min. A solution of 5.48 g of ethyl benzoate in 7 ml of octane was added via cannula. After the addition was complete, the reactor temperature was increased to 105 °C at a rate of 0.95 °C / min, and stirring was continued for 1.5 hours, after which the catalyst solid was allowed to settle and the supernatant was decanted. 520 g of preheated TiCl was added, the reactor was heated to 115 °C, and a solution of 2.7 g of ID-1 in 10 ml of toluene was added. The reactor was stirred for 0.5 hours, after which the precipitation and decantation steps were repeated. The TiCl4 treatment was repeated for 0.5 hours at 125°C. After the settling and decanting steps, the reactor was cooled to 65°C. The catalyst solid was washed five times with heptane at 65°C, with each wash being 200 ml. The catalyst was dried under vacuum at 40°C for 4 hours. The catalyst composition and bulk polymerization test data are listed in Table 3.

[0141] C-1 Prepared according to US Patent Application Publication No. 2013 / 0261273 using internal donor ID-11 [Table 1-1] [Table 1-2] [Table 2] [Table 3] [Table 4] [Table 5]

[0142] These and other modifications and variations to the present invention are more particularly set forth in the appended claims and may be practiced by those skilled in the art without departing from the spirit and scope of the present invention. It should further be understood that aspects of the various embodiments may be interchanged in whole or in part. Moreover, those skilled in the art will appreciate that the foregoing description is by way of example only and is not intended to limit the invention as further set forth in such appended claims. The present invention includes the following aspects. [1] 1. A catalyst composition for the stereoselective polymerization of propylene, comprising: a combination of a magnesium moiety, a titanium moiety, and an internal electron donor, wherein the internal electron donor is: [ka] In the formula, R 1 and R 4 are each a hydrocarbyl group having 1 to 20 carbon atoms, and R 2 and R 3 At least one of R is hydrogen; 2 and R 3 at least one of E comprises a substituted or unsubstituted hydrocarbyl group having 5 to 15 carbon atoms, said hydrocarbyl group having a branched or straight chain structure or comprising a cycloalkyl group having 7 to 15 carbon atoms; 1 and E 2 are the same or different and are selected from the group consisting of alkyl having 1 to 20 carbon atoms, substituted alkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, substituted aryl having 6 to 20 carbon atoms, or an inert functional group having 1 to 20 carbon atoms, and optionally containing a heteroatom; X 1 and X 2 are O, S, or NR, respectively. 5 where R 5 is a hydrocarbyl group having 1 to 20 carbon atoms or is hydrogen. [2] R of the internal electron donor 2 and R 3 The catalyst composition according to [1], wherein at least one of the groups contains a branched alkyl group or an alkenyl group. [3] The catalyst composition according to [2], wherein the branched alkyl or alkenyl group contains 5 to 10 carbon atoms. [4] R of the internal electron donor 2 and R 3 The catalyst composition according to any one of [1] to [3], wherein at least one of the groups includes a 3-pentyl group, a 2-pentyl group, a cycloheptyl group, or a cyclooctyl group. [5] R 1 and R 4 The catalyst composition according to any one of [1] to [4], wherein are the same. [6] R 1 and R 4 The catalyst composition according to any one of [1] to [5], wherein is a linear hydrocarbyl group. [7] R 1 and R 4 The catalyst composition according to any one of [1] to [6], wherein comprises a C1 to C8 alkyl group, a C2 to C8 alkenyl group, or a mixture thereof. [8] The catalyst composition according to any one of [1] to [7], wherein the magnesium portion comprises a magnesium halide. [9] E 1 and E 2 The catalyst composition according to any one of [1] to [8], wherein both of the above contain a phenyl group.

[10] The catalyst composition according to any one of [1] to [9], further comprising a cocatalyst, optionally an activity limiting agent, and optionally a selectivity control agent.

[11]

[10] The catalyst composition according to

[10] , wherein the co-catalyst comprises a hydrocarbon aluminum co-catalyst such as triethylaluminum.

[12]

[10] The catalyst composition according to

[10] , wherein the selectivity control agent is present and comprises an alkoxysilane.

[13] The catalyst composition according to

[10] or

[12] , wherein the selectivity control agent comprises dicyclopentyldimethoxysilane, di-tert-butyldimethoxysilane, methylcyclohexyldimethoxysilane, methylcyclohexyldiethoxysilane, ethylcyclohexyldimethoxysilane, diphenyldimethoxysilane, diisopropyldimethoxysilane, di-n-propyldimethoxysilane, diisobutyldimethoxysilane, diisobutyldiethoxysilane, isobutylisopropyldimethoxysilane, di-n-butyldimethoxysilane, cyclopentyltrimethoxysilane, isopropyltrimethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, ethyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, diethylaminotriethoxysilane, cyclopentylpyrrolidinodimethoxysilane, bis(pyrrolidino)dimethoxysilane, bis(perhydroisoquinolino)dimethoxysilane, dimethyldimethoxysilane, or a mixture thereof.

[14] 10. The catalyst composition of claim 1, wherein the magnesium portion comprises a spray-crystallized magnesium halide compound comprising ethanol and magnesium chloride in a weight ratio of about 1.5:1 to about 3.1:1.

[15] 1. A polymerization process comprising: A polymerization process comprising polymerizing an olefin in the presence of a catalyst composition comprising the Ziegler-Natta catalyst composition according to any one of [1] to

[14] .

[16]

[15] The process according to

[15] , wherein the olefin comprises propylene to form a propylene homopolymer, or propylene and ethylene to form a propylene and ethylene copolymer.

[17] 16. The process according to claim 15, wherein the process produces a heterophasic polymer.

[18] 17. The process of claim 17, wherein the heterophasic polymer comprises a first polymer phase comprising a polypropylene homopolymer or a polypropylene random copolymer, and the heterophasic polymer further comprises a second polymer phase combined with the first polymer phase, the second polymer phase comprising an elastomeric propylene ethylene copolymer.

[19]

[18] The process of

[18] , wherein the first polymer phase is formed in a first reactor, the second polymer phase is formed in a second reactor, and the catalyst composition remains active in both the first reactor and the second reactor.

[20] An olefin polymer containing the catalyst composition according to any one of [1] to

[14] .

Claims

1. 1. A catalyst composition for the stereoselective polymerization of propylene, comprising: a combination of a magnesium moiety, a titanium moiety, and an internal electron donor, wherein the internal electron donor is: 【Chemical 1】 In the formula, R １ and R ４ are each a hydrocarbyl group having 1 to 4 carbon atoms, and R ２ and R ３ At least one of R ２ and R ３ at least one of E comprises a substituted or unsubstituted hydrocarbyl group having from 5 to 15 carbon atoms, said hydrocarbyl group having a branched or straight chain structure or comprising a cycloalkyl group having from 7 to 15 carbon atoms; １ and E ２ are the same or different and are selected from the group consisting of alkyl having 1 to 20 carbon atoms, substituted alkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, and substituted aryl having 6 to 20 carbon atoms; X １ and X ２ are O, S, or NR, respectively. ５ wherein R ５ is a hydrocarbyl group having 1 to 20 carbon atoms or is hydrogen.

2. R of the internal electron donor ２ and R ３ 10. The catalyst composition of claim 1, wherein at least one of comprises a branched alkyl or alkenyl group.

3. 3. The catalyst composition of claim 2, wherein the branched alkyl or alkenyl group contains from 5 to 10 carbon atoms.

4. R of the internal electron donor ２ and R ３ 4. The catalyst composition of claim 1, wherein at least one of: comprises a 3-pentyl group, a 2-pentyl group, a cycloheptyl group, or a cyclooctyl group.

5. R １ and R ４ The catalyst composition according to any one of claims 1 to 4, wherein are the same.

6. R １ and R ４ The catalyst composition according to any one of claims 1 to 5, wherein is a linear hydrocarbyl group.

7. R １ and R ４ The catalyst composition of any one of claims 1 to 6, wherein comprises a methyl group, an ethyl group, a propyl group, a butyl group, or a combination thereof.

8. 8. The catalyst composition of any one of claims 1 to 7, wherein the magnesium portion comprises a magnesium halide.

9. E １ and E ２ 9. The catalyst composition of claim 1, wherein both of the groups comprise a phenyl group.

10. 10. The catalyst composition of any one of claims 1 to 9, further comprising a cocatalyst, optionally an activity limiting agent, and optionally a selectivity control agent.

11. The catalyst composition of claim 10, wherein the co-catalyst comprises a hydrocarbyl aluminum co-catalyst.

12. 11. The catalyst composition of claim 10, wherein the selectivity control agent is present and comprises an alkoxysilane.

13. 13. The catalyst composition of claim 10 or 12, wherein the selectivity control agent comprises dicyclopentyldimethoxysilane, di-tert-butyldimethoxysilane, methylcyclohexyldimethoxysilane, methylcyclohexyldiethoxysilane, ethylcyclohexyldimethoxysilane, diphenyldimethoxysilane, diisopropyldimethoxysilane, di-n-propyldimethoxysilane, diisobutyldimethoxysilane, diisobutyldiethoxysilane, isobutylisopropyldimethoxysilane, di-n-butyldimethoxysilane, cyclopentyltrimethoxysilane, isopropyltrimethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, ethyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, diethylaminotriethoxysilane, cyclopentylpyrrolidinodimethoxysilane, bis(pyrrolidino)dimethoxysilane, bis(perhydroisoquinolino)dimethoxysilane, dimethyldimethoxysilane, or a mixture thereof.

14. 10. The catalyst composition of claim 1, wherein the magnesium portion comprises a spray-crystallized magnesium halide compound comprising ethanol and magnesium chloride in a weight ratio of 1.5:1 to 3.1:

1.

15. 1. A polymerization process comprising: A polymerization process comprising polymerizing an olefin in the presence of a catalyst composition comprising the Ziegler-Natta catalyst composition of any one of claims 1 to 14.

16. 16. The process of claim 15, wherein the olefin comprises propylene to form a propylene homopolymer, or propylene and ethylene to form a propylene and ethylene copolymer.

17. 17. The process of claim 16, wherein the process produces a heterophasic polymer.

18. 18. The process of claim 17, wherein the heterophasic polymer comprises a first polymer phase comprising a polypropylene homopolymer or a polypropylene random copolymer, the heterophasic polymer further comprising a second polymer phase combined with the first polymer phase, the second polymer phase comprising an elastomeric propylene ethylene copolymer.

19. 20. The process of claim 18, wherein the first polymer phase is formed in a first reactor and the second polymer phase is formed in a second reactor, and the catalyst composition remains active in both the first reactor and the second reactor.

20. An olefin polymer containing the catalyst composition of any one of claims 1 to 14.

21. The catalyst composition of claim 10, wherein the cocatalyst comprises triethylaluminum.

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