WO2014123668A1 - Activateurs de polymérisation pour catalyseurs ziegler-natta supportés - Google Patents

Activateurs de polymérisation pour catalyseurs ziegler-natta supportés Download PDF

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WO2014123668A1
WO2014123668A1 PCT/US2014/011474 US2014011474W WO2014123668A1 WO 2014123668 A1 WO2014123668 A1 WO 2014123668A1 US 2014011474 W US2014011474 W US 2014011474W WO 2014123668 A1 WO2014123668 A1 WO 2014123668A1
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ethylene
copolymer
halocarbon
catalyst
process according
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Sudhin Datta
Mosha H. ZHAO
Zerong Lin
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ExxonMobil Chemical Patents Inc
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ExxonMobil Chemical Patents Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/001—Multistage polymerisation processes characterised by a change in reactor conditions without deactivating the intermediate polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Ethylene-propylene or ethylene-propylene-diene copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/01—Additive used together with the catalyst, excluding compounds containing Al or B
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/02—Heterophasic composition

Definitions

  • Embodiments provided herein generally relate to processes for making impact copolymers. More particularly, embodiments provided herein relate to processes for making impact copolymers using two or more polymerization stages.
  • a variety of polymerization processes can be used to prepare the crystalline polypropylene polymer and the secondary polymer, such as gas phase, slurry, liquid, and/or solution polymerization. It is also quite common to make the constituent polymers in two different polymerization processes, for example, slurry phase for the polymerization of the polypropylene polymer and gas phase for the polymerization of the ethylene copolymer.
  • the composition, composition distribution, amount, molecular weight, and/or molecular weight distribution of the secondary polymer primarily determines the engineering properties of the ICP. Accordingly, control over the secondary polymer is desirable in order to control the properties of the ICP produced via the two stage polymerization process.
  • One problem encountered in a two stage or two step polymerization process that uses gas phase polymerization for the secondary ethylene copolymer is that the catalyst, e.g., titanium catalyst, tends to degrade in activity and/or selectivity toward the polymerization of the secondary polymer. As such, the amount of the secondary polymer made in the second polymerization stage is typically less than desired. Additionally, degradation of the catalyst's selectivity toward a particular copolymer causes the secondary copolymer to have a range of molecular weights, varying composition, and/or other varying properties that cannot be controlled.
  • the catalyst e.g., titanium catalyst
  • the process for making an impact copolymer can include contacting polypropylene particles having a weight average particle size along the longest cross-sectional length thereof of from 0.05 mm to 5 mm and a pore volume of 5% to 80%, one or more halocarbon compounds, ethylene, and at least one comonomer with one another under conditions sufficient to polymerize the ethylene and the at least one comonomer to produce an impact copolymer comprising the polypropylene particles and an ethylene copolymer.
  • the process for making an impact copolymer can include combining propylene with a Ziegler-Natta catalyst or a single site catalyst in a polymerization reactor at conditions sufficient to produce polypropylene particles having a weight average particle size along the longest cross-sectional length thereof of 0.05 mm to 5 and a pore volume of 5% to 80%.
  • the polypropylene particles can be combined with a halocarbon compound to produce halocarbon-containing polypropylene particles having at least a portion of the halocarbon compound within the pores of the polypropylene particles.
  • Ethylene and at least one comonomer can be combined with the halocarbon-containing polypropylene particles and the catalyst.
  • Figure 4 is a graphical representation of the effect chlorocyclohexane (CCH) had on the ethylene-copolymer content over a range of homopolymer melt flow rates versus comparative ethylene-copolymers made in the absence of chlorocyclohexane.
  • CCH chlorocyclohexane
  • the in-situ polymerization of the impact copolymer can employ any appropriate polymerization catalyst or combination of catalysts capable of polymerizing the monomer component(s) of the polypropylene component and the ethylene copolymer component.
  • the catalyst can be or include one or more Ziegler-Natta and/or one or more single- site, e.g., metallocene, polymerization catalysts.
  • the catalyst(s) can be supported, e.g., for use in heterogeneous catalysis processes, or unsupported, e.g., for use in homogeneous catalysis processes.
  • the polypropylene polymer and the ethylene copolymer can be made with a common supported Ziegler-Natta or single-site catalyst.
  • the catalyst is or includes a Ziegler- Natta catalyst
  • contacting the catalyst with the halocarbon compound can reverse the reduction that can occur in the transition metal component during polymerization.
  • the reversal in the reduction of the transition metal component can be such that a larger fraction of the reactivated transition metal atoms are of the same chemical identity, which can result in the polymerization of the ethylene copolymer having a more uniform or similar composition and/or molecular weight.
  • the halocarbon compound also reacts with excess tri alkyl aluminum that may be present in the vicinity of the catalyst to attenuate the reactivity of the trialkyl aluminum toward the reduction of the Ziegler-Natta catalyst.
  • the halocarbon is believed to slow the reduction of the Ziegler-Natta catalyst and reactivate the Ziegler-Natta catalyst by oxidation caused by the transfer of a halogen to the catalyst.
  • Suitable acyl halide compounds can be represented by the general formula R ⁇ (CO)X ⁇ n , where R is a chemical fragment of valence n (preferably R is a hydrocarbyl group and n is 1, 2, 3, 4, 5 or 6) and X is a halogen, preferably CI.
  • R groups may be selected from the group consisting of: substituted alkyls, unsubstituted alkyls, (preferably the alkyls are CI to C20 alkyls) substituted aromatics (such as substituted phenyl or benzyl groups), and unsubstituted aromatics (such as phenyl or benzyl).
  • Illustrative acyl halide compounds can include, but are not limited to, benzoyl chloride, acetyl chloride, or any mixture thereof.
  • the impact copolymer can have an ethylene copolymer content from a low of 5 wt%, 8 wt%, 10 wt%, 15 wt%, 25 wt%, 35 wt%, or 45 wt% to a high of 55 wt%, 65 wt%, 75 wt%, or 85 wt%, based on the combined weight of the polypropylene polymer and the ethylene copolymer.
  • the amount of the ethylene copolymer can be such that the impact copolymer contains from 5 wt% to 85 wt% of the ethylene copolymer, based on the combined weight of the polypropylene polymer and the ethylene copolymer.
  • the impact polymer can have an ethylene copolymer content of 5 wt% to 80 wt%, 5 wt% to 60 wt%, 5 wt% to 50 wt%, 5 wt% to 40 wt%, 6 wt% to 35 wt%, 7 wt% to 30 wt%, or 8 wt% to 30 wt%, based on the combined weight of the polypropylene polymer and the ethylene copolymer.
  • the catalyst activity during polymerization of the ethylene copolymer can be such that the instantaneous polymerization rate in grams per minute of the ethylene copolymer decreases by less than 50%, less than 45%, less than 40%, less than 35%, less than 30%, less than 25%, less than 20%, less than 15%, less than 10%, less than 8%, less than 7%, less than 6%, less than 5%, less than 4%, less than 3%, less than 2%, or less than 1% over a time period of at least 10 minutes after the instantaneous polymerization rate reaches a maximum after start of the polymerization compared to the same catalyst and polymerization system in the absence of the halocarbon.
  • the polymerization of propylene and, if present, any other monomer(s) to produce the polypropylene polymer can form polypropylene particles having a weight average particle size along the longest cross-sectional length thereof from a low of 0.01 mm, 0.05 mm, 0.1 mm, 0.3 mm, or 0.5 mm to a high of 2 mm, 3 mm, 4 mm, 5 mm, or 6 mm.
  • the polypropylene particles can have a weight average particle size along the longest cross- sectional length thereof of from 0.05 mm to 5 mm, 0.1 mm to 4 mm, 1 mm to 4.5 mm, 1.5 mm to 3 mm, 2 mm to 4 mm, or 0.2 mm to 3.5 mm.
  • the polypropylene particles can also have one or more pores at least partially formed therein and/or therethrough.
  • the polypropylene particles can have a pore volume of less than 80%, less than 75%, less than 70%, less than 60%, less than 50%, or less than 40%.
  • the polypropylene particles can have a pore volume from a low of 5%, 10%, 15%, or 20% to a high of 55%, 65%, 75%, 80%, 85%, or 90%.
  • the polypropylene particles have a pore volume of less than 80%.
  • the catalyst resides, occupies or at least partially resides or occupies within the pores or along the inner walls of the pores that are at least partially formed in or through the polypropylene particles. Accordingly, it is believed that the polymerization of the ethylene and the at least one comonomer, or at least a majority of the polymerization of the ethylene and the at least one comonomer, occurs within the pores of the polypropylene particles as opposed to outside or external the polypropylene particles.
  • halocarbon compounds capable of flowing into the pores of the polypropylene particles can have a greater influence on the catalyst activity and/or the polymerization of the ethylene and the one or more monomers to produce the copolymer component as compared to those that are not capable of flowing into the pores of the polypropylene particles.
  • one or more inert solvents can also be introduced to the polymerization process that can further increase or enhance the concentration of the halocarbon compound and/or the ethylene and/or the at least one other comonomer within the pores of the polypropylene particles.
  • the inert solvent can be mixed, blended, combined, or otherwise contacted with the halocarbon compound and introduced to the polymerization process as a mixture.
  • the inert solvent and the halocarbon compound can be introduced to the polymerization process independent one another.
  • the inert solvent and/or the halocarbon compound can be combined with the polypropylene particles prior to, during, and/or after the addition of the ethylene and the at least one comonomer.
  • the inert solvent and/or the halocarbon compound can be combined with the propylene and present during the polymerization of the propylene to produce the polypropylene particles.
  • the presence of the inert solvent and/or the halocarbon compound creates, induces, promotes, forms, or otherwise causes an increased presence or concentration of the ethylene and/or the comonomer within the pores of the polypropylene particles.
  • the inert solvent can be combined with the polypropylene particles in an amount greater than 0.5 times, or greater than 0.65 times, or greater than 0.75 times to less than 1.4 times, less than 1.25 times, or less than 1.15 times the pore volume of the polypropylene particles.
  • the homopolymer can be atactic polypropylene, isotactic polypropylene, highly isotactic polypropylene, syndiotactic polypropylene, and blends thereof.
  • the polypropylene copolymer can be a polypropylene homopolymer (HPP), a random copolymer (RCP), a statistical copolymer, a block copolymer, and blends thereof.
  • the polypropylene polymer can have ratio of the weight average molecular weight (Mw) to number average molecular weight (Mn) or (Mw/Mn) from a low of 1, 1.5, or 2 to a high of 20, 30, or 40.
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • Mw/Mn number average molecular weight
  • the polypropylene polymer can have an Mw/Mn of 1.4 to 20, or 1.6 to 10, or 1.8 to 3.5, or 1.8 to 2.5.
  • the polypropylene polymer can have a melt flow rate (MFR) from a low of 1 dg/min, 15 dg/min, 30 dg/min, or 45 dg/min to a high of 75 dg/min, 100 dg/min, 200 dg/min, or 300 dg/min.
  • MFR melt flow rate
  • the polypropylene polymer can have an MFR of 1 dg/min to 300 dg/min, 5 dg/min to 150 dg/min, or 10 dg/min to 100 dg/min, or 20 dg/min to 60 dg/min.
  • the polypropylene polymer can have a melting point (Tm, peak second melt) of at least 100°C, or at least 1 10°C, or at least 120°C, or at least 130°C, or at least 140°C, or at least 150°C, or at least 160°C, or at least 165°C.
  • Tm melting point
  • the polypropylene polymer can have a melting point from at least 100°C to 175°C, or 170°C to 165°C, or 160°C to 145°C.
  • the polypropylene polymer can have a crystallization temperature (Tc, peak) of at least 70°C, or at least 90°C, or at least 110°C, or at least 130°C.
  • Tc crystallization temperature
  • the polypropylene polymer can have a crystallization temperature from at least 70°C to 75°C, or 80°C to 90°C, or 110°C to 130°C, or 120°C to 150°C.
  • the polypropylene polymer can have a crystallinity from a low of 5%, 12%, 22%, 33%, or 44% to a high of 60%, 68%, 78%, or 83%.
  • the polypropylene polymer can have a crystallinity of 5% to 80%, 10% to 75%, 20% to 70%, 30% to 65%, or 40% to 60%.
  • the polypropylene polymer can have a heat deflection temperature (HDT) from a low of 45°C, 50°C, 55°C, or 65°C to a high of 100°C, 1 15°C, 130°C, or 140°C, as measured according to ASTM D 648 (0.45 MPa).
  • HDT heat deflection temperature
  • the polypropylene polymer can have a heat deflection temperature from 45°C to 140°C, 60°C to 135°C, or 75°C to 125°C, as measured according to ASTM D 648 (0.45 MPa).
  • the polypropylene polymer can have a Gardner impact strength at 23°C of 30 KJ/m 2 to 1,300 KJ/m 2 , 40 KJ/m 2 to 800 KJ/m 2 , or 50 KJ/m 2 to 600 KJ/m 2 , as measured according to ASTM D 5420 (GC).
  • a Gardner impact strength at 23°C 30 KJ/m 2 to 1,300 KJ/m 2 , 40 KJ/m 2 to 800 KJ/m 2 , or 50 KJ/m 2 to 600 KJ/m 2 , as measured according to ASTM D 5420 (GC).
  • the polypropylene polymer can have a 1% secant flexural modulus from a low of 300 MPa, 500 MPa, 800 MPa, or 1,000 MPa to a high of 1,700 MPa, 2, 100 MPa, 2,600 MPa, or 3, 100 MPa, as measured according to ASTM D 790 (A, 1.3 mm/min).
  • the polypropylene polymer can have a flexural modulus from 300 MPa to 3,000 MPa, 600 MPa to 2,500 MPa, 800 MPa to 2,000 MPa, or 1,000 MPa to 1,500 MPa, as measured according to ASTM D 790 (A, 1.3 mm/min).
  • the polypropylene polymer can have a propylene meso diads of 90% or more, 92% or more, 94% or more, 95% or more, 96% or more, 97% or more, or 98% or more.
  • the isotacticity of the polypropylene polymer can be measured by 13 C NMR.
  • suitable techniques for measuring the isotacticity of the polypropylene polymer can be as discussed and described in US: 4,950,720. Expressed another way, the isotacticity of the polypropylene polymer, as measured by 13 C NMR, and expressed as pentad content, is greater than 93% or 95%, or 97% in certain embodiments.
  • alpha olefin is a linear, branched, or cyclic compound of carbon and hydrogen having at least one double bond.
  • alkene is a linear, branched, or cyclic compound of carbon and hydrogen having at least one double bond.
  • olefin including, but not limited to, ethylene, propylene, and butene
  • the olefin present in such polymer or copolymer is the polymerized form of the olefin.
  • ethylene polymer is a polymer comprising at least 50 mol% of ethylene
  • propylene polymer is a polymer having at least 50 mol% of propylene
  • a butene polymer is a polymer comprising at least 50 mol% butene
  • alpha-olefin is an olefin having a double bond at the alpha (or 1-) position.
  • a “linear alpha-olefin” or “LAO” is an olefin with a double bond at the alpha position and a linear hydrocarbon chain.
  • a-olefin includes C2-C20 olefins.
  • Non-limiting examples of a-olefins include ethylene, propylene, 1 -butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene 1-dodecene, 1- tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1- nonadecene, 1-eicosene, 1-heneicosene, 1-docosene, 1-tricosene, 1-tetracosene, 1- pentacosene, 1-hexacosene, 1-heptacosene, 1-octacosene, 1-nonacosene, 1-triacontene, 4- methyl- 1-pentene, 3 -methyl- 1-pentene, 5 -methyl- 1-n
  • the ethylene copolymer can have an ethylene content from a low of 20 wt%, 35 wt%, 40 wt%, or 45 wt% to a high of 65 wt%, 70 wt%, 80 wt%, or 85 wt%, based on the combined weight of the ethylene monomer and the one or more comonomers, e.g., propylene, polymerized to produce the ethylene copolymer.
  • the one or more comonomers e.g., propylene
  • the comonomer content, e.g., propylene, in the ethylene copolymer can be from a low of 15 wt%, 20 wt%, 25 wt%, or 20 wt% to a high of 50 wt%, 60 wt%, 70 wt%, or 80 wt%.
  • the comonomer content, e.g., propylene, in the ethylene copolymer can be at least 15 wt%, at least 20 wt%, at least 25 wt%, at least 30 wt%, or at least 35 wt%, based on the combined weight of the ethylene monomer and the comonomer(s) polymerized to produce the ethylene copolymer.
  • the ethylene copolymer can have a comonomer, e.g., propylene, content from a low of 15 wt%, 20 wt%, or 25 wt% to a high of 50 wt%, 77 wt%, or 80 wt%, based on the combined weight of the ethylene monomer and the propylene monomer polymerized to produce the ethylene copolymer.
  • a comonomer e.g., propylene
  • the ethylene copolymer can have a comonomer, e.g., propylene, content from 25 wt% to 80 wt%, 10 wt% to 75 wt%, 35 wt% to 70 wt%, or at least 40 wt% to 80 wt%, based on the combined weight of the ethylene monomer and the propylene monomer polymerized to produce the ethylene copolymer.
  • a comonomer e.g., propylene
  • the ethylene copolymer can have a non-conjugated diene or termonomer content of 15 wt% or less, 12 wt% or less, 9 wt% or less, 6 wt% or less, 3 wt% or less, or 1 wt% or less.
  • the ethylene copolymer can have a non-conjugated diene content of 2 wt% to 14 wt%, 6 wt% to 13 wt%, 4 wt% to 8 wt%, or 1 wt% to 11 wt%.
  • Particularly preferred ethylene copolymers can contain no diene.
  • the ethylene copolymer can have an ethylene or propylene crystallinity, if measurable, of less than 10 wt%, less than 7.5 wt%, less than 5 wt%, less than 2.5 wt%, or less than 1 wt%. In at least one example, the ethylene copolymer can have an ethylene or propylene crystallinity that is undetectable. In a preferred embodiment, the ethylene copolymer has a crystallinity, as determined by DSC, of less than 20 %, preferably less than 10%, preferably less than 5%, preferably less than 1%.
  • the ethylene copolymer can have a melting point (T m , peak first melt), if detected, of 60°C or less, 50°C or less, 40°C or less, or 35°C or less.
  • T m melting point
  • the ethylene copolymer can have a glass transition temperature (T g ) of -30°C or less, -40°C or less, -50°C or less, or - 60°C or less.
  • the ethylene copolymer can have a weight average molecular weight (Mw) from a low of 50 kg/mol, 75 kg/mol, 150 kg/mol, or 300 kg/mol to a high of 600 kg/mol, 900 kg/mol, 1,300 kg/mol, 2,000 kg/mol, 2,500 kg/mol, or 3,000 kg/mol.
  • Mw weight average molecular weight
  • the ethylene copolymer can have a Mw of 50 kg/mol to 3,000 kg/mol, 100 kg/mol to 2,000 kg/mol, or 200 kg/mol to 1,000 kg/mol.
  • the ethylene copolymer can have a ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) or (Mw/Mn) from a low of 1, 1.5, or 2 to a high of 20, 30, or 40.
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • Mw/Mn number average molecular weight
  • the ethylene copolymer can have an Mw/Mn of 1.4 to 20, or 1.6 to 10, or 1.8 to 3.5, or 1.8 to 2.5.
  • the impact copolymer includes the polypropylene polymer, the ethylene copolymer, and a second polypropylene polymer, with no other components being present
  • the impact copolymer can have a total propylene content of at least 75 wt%, at least 80 wt%, at least 85 wt%, at least 90 wt%, or at least 95 wt%, based on the combined weight of the polypropylene polymer, the ethylene copolymer, and the second polypropylene polymer or said another way the total weight of the impact copolymer.
  • the impact copolymer can have a total comonomer content from a low of 1 wt%, 5 wt%, 9 wt%, or 12 wt% to a high of 18 wt%, 23 wt%, 28 wt%, or 35 wt%, based on the total weight of the impact copolymer.
  • the impact copolymer can have a total comonomer content of 1 wt% to 35 wt%, 2 wt% to 30 wt%, 3 wt% to 25 wt%, or 5 wt% to 20 wt%, based on the total weight of the impact copolymer.
  • the impact copolymer can have a propylene content of the ethylene copolymer component from a low of 25 wt%, 37 wt%, or 46 wt% to a high of 73 wt%, 77 wt%, or 80 wt%, based on the based on a weight of the ethylene copolymer.
  • the impact copolymer can have a propylene content of the ethylene copolymer component from 25 wt% to 80 wt%, 10 wt% to 75 wt%, 35 wt% to 70 wt%, or at least 40 wt% to 80 wt%, based on the weight of the ethylene copolymer.
  • the impact copolymer can have a weight average molecular weight (Mw) from a low of 20 kg/mol, 50 kg/mol, 75 kg/mol, 150 kg/mol, or 300 kg/mol to a high of 600 kg/mol, 900 kg/mol, 1,300 kg/mol, or 2,000 kg/mol.
  • Mw weight average molecular weight
  • the ethylene copolymer can have a Mw of 50 kg/mol to 3,000 kg/mol, 100 kg/mol to 2,000 kg/mol, or 200 kg/mol to 1,000 kg/mol.
  • the impact copolymer can have a melting point (Tm, peak second melt) of at least 100°C, or at least 110°C, or at least 120°C, or at least 130°C, or at least 140°C, or at least 150°C, or at least 160°C, or at least 165°C.
  • Tm melting point
  • the impact copolymer can have a melting point from at least 100°C to 175°C, 105°C to 165°C, 105°C to 145°C, or 100°C to 155°C.
  • the impact copolymer can have a heat of fusion (Hf, DSC second heat) from a high of 60 J/g, 75 J/g, 85 J/g, or 95 J/g to a low of 20 J/g, 30 J/g, 40J/g, or about50J/g.
  • the impact copolymer can have a heat of fusion of 60 J/g or more, 70 J/g or more, 80 J/g or more, 90 J/g or more, 95 J/g or more, or 100 J/g or more.
  • the impact copolymer can have glass transition temperature (Tg) of the ethylene copolymer component of -20°C or less, -30°C or less, -40°C or less, or -50°C or less.
  • Tg glass transition temperature
  • the impact copolymer can have a notched Izod impact strength at 23°C from a low of 3 KJ/m 2 , 6 KJ/m 2 , 12 KJ/m 2 or 18 KJ/m 2 to a high of 30 KJ/m 2 , 35 KJ/m 2 , 45 KJ/m 2 , 55 KJ/m 2 , or 65 KJ/m 2 , as measured according to ASTM D 256 (Method A).
  • the impact copolymer can have a Gardner impact strength at -30°C from a low of 2 KJ/m 2 , 3 KJ/m 2 , 6 KJ/m 2 , 12 KJ/m 2 , or 20 KJ/m 2 to a high of 55 KJ/m 2 , 65 KJ/m 2 , 75 KJ/m 2 , 85 KJ/m 2 , 95 KJ/m 2 , or 105 KJ/m 2 , as measured according to ASTM D 5420 (GC).
  • GC ASTM D 5420
  • the impact copolymer can have a Gardner impact strength at -30°C of 2 KJ/m 2 to 100 KJ/m 2 , 3 KJ/m 2 to 80 KJ/m 2 , or 4 KJ/m 2 to 60 KJ/m 2 , as measured according to ASTM D 5420 (GC).
  • GC ASTM D 5420
  • the impact copolymer can have a heat deflection temperature (HDT) from a low of 75°C, 83°C, 87°C, or 92°C to a high of 95°C, 100°C, 105°C, or aboutl20°C, as measured according to ASTM D 648 (0.45 MPa).
  • HDT heat deflection temperature
  • the impact copolymer can have a heat deflection temperature of 80°C or more, 85°C or more, 90°C or more, or 95°C or more, as measured according to ASTM D 648 (0.45 MPa).
  • the impact copolymer can have an MFR from 6 dg/min to 200 dg/min; a 1% Secant Flexural Modulus greater than 820 MPa, and an Izod Impact at 25°C of greater than 26 KJ/m 2 .
  • the impact copolymer can have an ethylene copolymer concentration of at least 10 wt% to about35 wt%, based on the combined weight of the polypropylene polymer and the ethylene copolymer, a notched Izod impact strength at 23°C of at least 5 KJ/m 2 to 75 KJ/m 2 , and a flexural modulus less than 1,200 MPa to 1,900 MPa.
  • the impact copolymer can have an ethylene copolymer concentration of at least 15wt% to 25 wt%, based on the combined weight of the polypropylene polymer and the ethylene copolymer, a notched Izod impact strength at 23 °C of at least 15 KJ/m 2 to 65 KJ/m 2 , and a flexural modulus less than 1,300 MPa to 1,800 MPa.
  • the impact copolymer can have an ethylene copolymer having a weight average molecular weight of at least 30 kg/mol to 200 kg/mol, a notched Izod impact strength at 23 °C of at least 5 KJ/m 2 to 75 KJ/m 2 , and an MFR at 230°C of from 10 to 75.
  • the impact copolymer can have an ethylene copolymer having a weight average molecular weight of at least 10 kg/mol to 35 kg/mol, a notched Izod impact strength at 23°C of at least 5 KJ/m 2 to 75 KJ/m 2 , and an MFR at 230°C of from 10 to 75.
  • the impact copolymer can have an ethylene copolymer having a weight average molecular weight of at least 45 kg/mol to 150 kg/mol, a notched Izod impact strength at 23°C of at least 15 KJ/m 2 to 65 KJ/m 2 , and a and an MFR at 230°C of between 10 to 75.
  • the impact copolymer can have an ethylene copolymer having a weight average molecular weight of at least 35 kg/mol to 250 kg/mol, a notched Izod impact strength at 23°C of at least 15 KJ/m 2 to 65 KJ/m 2 , and an MFR at 230°C of from 10 to 75.
  • Additives such as antioxidants and stabilizers (including UV stabilizers and other UV absorbers, such as chain-breaking antioxidants), fillers (such as mineral aggregates, fibers, clays, and the like), nucleating agents, slip agents, block, antiblock, pigments, dyes, color masterbatches, waxes, processing aids (including pine or coal tars or resins and asphalts), neutralizers (such as hydro talcite), adjuvants, oils, lubricants, low molecular weight resins, surfactants, acid scavengers, anticorrosion agents, cavitating agents, blowing agents, quenchers, antistatic agents, cure or cross linking agents or systems (such as elemental sulfur, organo-sulfur compounds, and organic peroxides), fire retardants, coupling agents (such as silane), and combinations thereof may also be present in the impact copolymer compositions described herein.
  • additives such as antioxidants and stabilizers (including UV stabilizers and other UV absorbers, such as chain-breaking antioxidants
  • additives used in polypropylene and polypropylene blends are described in POLYPROPYLENE HANDBOOK 2 nd ED., N. Pasquini, ed. (Hanser Publishers, 2005).
  • the additives may be present in the typically effective amounts well known in the art, preferably at 0.001 to 50 wt% (preferably 0.01 to 20 wt%, preferably 0.1 to 10 wt%, preferably 0.1 to 1 wt%), based upon the weight of the composition.
  • Pigments, dyes, and other colorants may be present from 0.01 to 10 wt% (preferably 0.1 to 6 wt%).
  • additives include, for example, stabilizers, surfactants, antioxidants, anti-ozonants (e.g., thioureas), fillers, colorants, nucleating agents, anti-block agents, UV-blockers/absorbers, coagents (cross-linkers and cross-link enhancers), hydrocarbon resins (e.g., OpperaTM resins), and slip additives and combinations thereof.
  • Primary and secondary antioxidants include, for example, hindered phenols, hindered amines, and phosphates.
  • Slip agents include, for example, oleamide and erucamide.
  • fillers include carbon black, clay, talc, calcium carbonate, mica, silica, silicate, and combinations thereof.
  • Other additives include dispersing agents and catalyst deactivators such as calcium stearate, hydrotalcite, and calcium oxide, and/or other acid neutralizers known in the art.
  • cross-linkers and cross-link enhancers are absent from the propylene impact copolymers.
  • the "value" at infinite dilution can be determined by extrapolation.
  • the homopolymer portion is initially produced and the intrinsic viscosity of that portion is measured directly.
  • the intrinsic viscosity of the elastomeric portion cannot be measured directly.
  • the impact copolymer described in its various embodiments, can be further characterized by possessing an Instrumented Impact (5 mph at -29°C) of greater than 47 J, a Tensile at Yield of greater than 21.4 MPa, a Gardner Impact (-29°C) of greater than 34 N-m, or a combination of any two or more of these properties.
  • catalystst and “catalyst compound” are defined to mean a compound capable of initiating catalysis.
  • the catalyst may be described as a catalyst precursor, a pre-catalyst compound, or a transition metal compound, and these terms are used interchangeably.
  • a catalyst compound may be used by itself to initiate catalysis or may be used in combination with an activator to initiate catalysis. When the catalyst compound is combined with an activator to initiate catalysis, the catalyst compound is often referred to as a pre-catalyst or catalyst precursor.
  • a "catalyst system” is a combination of at least one catalyst compound, an optional activator, an optional co-activator, and an optional support material, where the system can polymerize monomers to polymer.
  • catalyst systems are described as comprising neutral stable forms of the components, it is well understood by one of ordinary skill in the art, that the ionic form of the component is the form that reacts with the monomers to produce polymers.
  • a "scavenger” is a compound that is typically added to facilitate polymerization by scavenging impurities. Some scavengers may also act as activators and may be referred to as co-activators. A co-activator, that is not a scavenger, may also be used in conjunction with an activator in order to form an active catalyst. In some embodiments, a co-activator can be pre-mixed with the catalyst compound to form an alkylated catalyst compound, also referred to as an alkylated compound.
  • useful Ziegler-Natta catalysts are typically composed of a transition metal compound from groups 4, 5, 6 and/or 7 (preferably group 4) and an organometallic compound of a metal from groups 11, 12 and/or 13 (preferably group 13) of the periodic table.
  • a transition metal compound from groups 4, 5, 6 and/or 7 (preferably group 4)
  • an organometallic compound of a metal from groups 11, 12 and/or 13 (preferably group 13) of the periodic table.
  • Well-known examples include TiCl3-Et 2 AlCl, AlR ⁇ -TiCL j , where Et is an ethyl group and R represents an alkyl group, typically a CI to C20 alkyl group, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl and the like.
  • These catalysts include mixtures of halides of transition metals, especially titanium, chromium, vanadium, and zirconium, with organic derivatives of nontransition metals, particularly alkyl aluminum compounds.
  • transition metals especially titanium, chromium, vanadium, and zirconium
  • organic derivatives of nontransition metals particularly alkyl aluminum compounds.
  • the Ziegler-Natta catalyst can be combined with one or more co-catalysts.
  • One particularly suitable co-catalyst can include an organoaluminum compound that is halogen free.
  • Suitable halogen free organoaluminum compounds can include, but are not limited to, branched unsubstituted alkylaluminum compounds of the formula AIR 3 , where R denotes an alkyl radical having 1 to 20 carbon atoms (preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl and the like), such as for example, trimethylaluminum, triethylaluminum, triisobutylaluminum and tridiisobutylaluminum.
  • the cocatalyst are readily available and amply disclosed in the prior art including those disclosed in US 4,990,477.
  • the same or different Ziegler-Natta catalyst(s) can be used in both the initial and subsequent polymerization steps.
  • the solid catalyst is a magnesium supported T1CI4 catalyst and the organoaluminum co-catalyst is triethylaluminum.
  • Electron donors can also be used in the formation of ZieglerNatta catalysts and catalyst systems.
  • an internal electron donor can be used in the formation reaction of the catalyst as the transition metal halide reacts with the metal hydride or metal alkyl.
  • Examples of internal electron donors can include, but are not limited to, amines, amides, ethers, esters, aromatic esters, ketones, nitriles, phosphines, stilbenes, arsines, phosphoramides, thioethers, thioesters, aldehydes, alcoholates, salts of organic acids, or any mixture or combination thereof.
  • an external electron donor can also be used in combination with the catalyst.
  • External electron donors often affect the level of stereoregularity in polymerization reactions.
  • Another use for an electron donor in the catalyst system can be as an external electron donor and stereoregulator in the polymerization reaction.
  • the same compound can be used in both instances, although typically they are different.
  • Preferred External electron donor materials can include, but are not limited to, organic silicon compounds, e.g., tetraethoxysilane (TEOS) and dicyclopentydimethoxysilane (DCPMS). Internal and external-type electron donors are discussed and described, for example, in US 4,535,068.
  • organic silicon compounds as external electron donors are described, for example, in US 4,218,339; 4,395,360; 4,328, 122; 4,473,660; 6,133,385; and 6, 127,303.
  • Particularly useful electron donors include external electron donors used as stereoregulators, in combination with ZieglerNatta catalysts.
  • a particularly useful Ziegler-Natta catalyst can be a magnesium chloride supported titanium catalyst selected from the group of THC-C type catalyst solid systems available from Toho Titanium Corporation of Japan.
  • Particularly preferred donor systems can include those discussed and described in US 6,087,495.
  • the donor can be or include a blend of propyltriethoxysilane (PTES) and dicyclopentyldimethoxysilane (DCPMS), typically a 95/5 mole% blend.
  • PTES propyltriethoxysilane
  • DCPMS dicyclopentyldimethoxysilane
  • Another useful donor is methylcyclohexyl di- methoxysilane (MCMS).
  • a particular Ziegler-Natta catalyst may produce better results when paired with a particular group of electron donors. Examples of this paring of catalyst and electron donors are disclosed in US 4,562, 173 and 4,547,552.
  • a mixed catalyst can also be used to produce the linear polyethylene.
  • the mixed catalyst can be a bimetallic catalyst composition or a multi-catalyst composition.
  • bimetallic catalyst composition and “bimetallic catalyst” include any composition, mixture, or system that includes two or more different catalyst components, each having a different metal group.
  • multi-catalyst composition and “multi- catalyst” include any composition, mixture, or system that includes two or more different catalyst components regardless of the metals.
  • the terms "bimetallic catalyst composition,” “bimetallic catalyst,” “multi-catalyst composition,” and “multi-catalyst” will be collectively referred to herein as a “mixed catalyst” unless specifically noted otherwise.
  • the mixed catalyst includes at least one metallocene catalyst component and at least one non-metallocene component.
  • a gaseous stream containing one or more monomers is continuously cycled through a fluidized bed in the presence of a catalyst under reactive conditions.
  • the gaseous stream is withdrawn from the fluidized bed and recycled back into the reactor.
  • polymer product is withdrawn from the reactor and fresh monomer is added to replace the polymerized monomer.
  • Illustrative gas phase polymerization processes can be as discussed and described in US 4,543,399; 4,588,790; 5,028,670; 5,317,036; 5,352,749; 5,405,922; 5,436,304; 5,453,471 ; 5,462,999; 5,616,661 ; and 5,668,228.
  • the reactor pressure in a gas phase process can vary from 69 kPa to 3,450 kPa, 690 kPa to 3,450 kPa, 1,380 kPa to 2,759 kPa, or 1,724 kPa to 2,414 kPa.
  • the reactor temperature in the gas phase process can vary from 30°C to 120°C, preferably from 60°C to 1 15°C, more preferably in the range of from 70°C to 110°C, and most preferably in the range of from 70°C to 95°C. In another embodiment, when high density polyethylene is desired the reactor temperature is typically between 70°C and aboutl05°C.
  • the reactor can be capable of producing more than 227 kilograms polymer per hour (kg/hr) to 90,900 kg/hr or higher, preferably greater than 455 kg/hr, more preferably greater than 4,540 kg/hr, even more preferably greater than 11,300 kg/hr, still more preferably greater than 15,900 kg/hr, still even more preferably greater than 22,700 kg/hr, and preferably greater than 29,000 kg/hr to greater than 45,500 kg/hr, and most preferably over 45,500 kg/hr.
  • the catalyst system is in liquid, suspension, dispersion, and/or slurry form and can be introduced into the gas phase reactor into a resin particle lean zone.
  • Introducing a liquid, suspension, dispersion, and/or slurry catalyst system into a fluidized bed polymerization into a particle lean zone can be as discussed and described in US 5,693,727.
  • a slurry polymerization process generally operates at a pressure range between 103 kPa to 5,068 kPa or even greater and a temperature from 0°C to 120°C.
  • a suspension of solid, particulate polymer is formed in a liquid polymerization diluent medium to which monomer and comonomers along with catalyst are added.
  • the suspension including diluent is intermittently or continuously removed from the reactor where the volatile components are separated from the polymer and recycled, optionally after a distillation, to the reactor.
  • the liquid diluent employed in the polymerization medium is typically an alkane medium having from 3 to 7 carbon atoms, preferably a branched alkane.
  • the medium employed can be liquid under the conditions of polymerization and relatively inert.
  • a propane medium When used the process can be operated above the reaction diluent critical temperature and pressure.
  • a hexane or an isobutane medium is employed.
  • a preferred polymerization technique referred to as a particle form polymerization or a slurry process
  • a particle form polymerization or a slurry process can include maintaining the temperature below the temperature at which the polymer goes into solution.
  • Such technique is well known in the art, and can be as discussed and described in US 3,248,179.
  • the preferred temperature in the particle form process can be from 20°C to 1 10°C.
  • Two preferred polymerization processes for the slurry process can include those employing a loop reactor and those utilizing a plurality of stirred reactors in series, parallel, or combinations thereof.
  • Non-limiting examples of slurry processes include continuous loop or stirred tank processes.
  • other examples of slurry processes can be as discussed and described in US 4,613,484.
  • the slurry process can be carried out continuously in a loop reactor.
  • the catalyst as a slurry in mineral oil and/or paraffinic hydrocarbon or as a dry, free flowing powder, can be injected regularly to the reactor loop, which can be filled with a circulating slurry of growing polymer particles in a diluent containing monomer and comonomer.
  • Hydrogen optionally, can be added as a molecular weight control.
  • the reactor can be operated at a pressure of 3,620 kPa to 4,309 kPa and at a temperature from 60°C to 115°C depending on the desired polymer melting characteristics.
  • the reactor used in the slurry process can produce greater than 907 kg/hr, more preferably greater than 2,268 kg/hr, and most preferably greater than 4,540 kg/hr polymer. In another embodiment the slurry reactor can produce greater than 6,804 kg/hr, preferably greater than 11,340 kg/hr to 45,500 kg/hr.
  • the reactor used in the slurry process can be at a pressure from 2,758 kPa to 5,516 kPa, preferably 3, 103 kPa to 4,827 kPa, more preferably from 3,448 kPa to 4,482 kPa, most preferably from 3,620 kPa to 4,309 kPa.
  • the concentration of the predominant monomer in the reactor liquid medium in the slurry process can be from 1 wt% to 30 wt%, preferably from 2 wt% to 15 wt%, more preferably from 2.5 wt% to 10 wt%, most preferably from 3 wt% to 20 wt%.
  • Typical scavengers include trimethyl aluminum, tri-ethyl aluminum, tri- isobutyl aluminum, tri-n-octyl aluminum, and an excess of alumoxane and/or modified alumoxane.
  • the upper pressure limit is not critically constrained but typically can be 200 MPa or less, preferably, 120 MPa or less.
  • Temperature control in the reactor can generally be obtained by balancing the heat of polymerization and with reactor cooling by reactor jackets or cooling coils to cool the contents of the reactor, auto refrigeration, pre-chilled feeds, vaporization of liquid medium (diluent, monomers or solvent) or combinations of all three. Adiabatic reactors with pre-chilled feeds can also be used.
  • the purity, type, and amount of solvent can be optimized for the maximum catalyst productivity for a particular type of polymerization.
  • the solvent can be also introduced as a catalyst carrier.
  • the solvent can be introduced as a gas phase or as a liquid phase depending on the pressure and temperature.
  • the solvent can be kept in the liquid phase and introduced as a liquid.
  • Solvent can be introduced in the feed to the polymerization reactors.
  • the polymerization process can be described as a continuous, non-batch process that, in its steady state operation, is exemplified by removal of amounts of polymer made per unit time, being substantially equal to the amount of polymer withdrawn from the reaction vessel per unit time.
  • substantially equal we intend that these amounts, polymer made per unit time, and polymer withdrawn per unit time, are in ratios of one to other, of from 0.9: 1; or 0.95: 1 ; or 0.97: 1 ; or 1 : 1. In such a reactor, there will be a substantially homogeneous monomer distribution.
  • the mean residence time of the catalyst and polymer in the reactor generally can be from 5 minutes to 8 hours, and preferably from 10 minutes to 6 hours, more preferably from 10 minutes to 1 hour.
  • comonomer such as ethylene
  • main monomer such as a propylene
  • any optional diene monomers present can be added to the reaction vessel in an amount to maintain a differential pressure in excess of the combined vapor pressure of the main monomer (such as a propylene) and any optional diene monomers present.
  • the polymerization process can be carried out at a pressure of ethylene of from 68 kPa to 6,800 kPa, most preferably from 272 to 5,440 kPa).
  • the polymerization is generally conducted at a temperature of from 25°C to 250°C, preferably from 75°C to 200°C, and most preferably from 95°C to 200°C.
  • a sequential polymerization process is used and the first polymerization is a slurry process to produce homopolymer followed by another slurry reactor for impact copolymer production.
  • Impact copolymers can be produced by first making homopolypropylene in a slurry reactor, and transferring the homopolypropylene to another slurry reactor where copolymers are produced with the presence of homopolypropylene.
  • Fluorocarbon can be introduced into the first reactor, the second reactor or both.
  • the two (or more ) polymerizations can occur in the same reactor but in different reaction zones.
  • another preferred embodiment is process to prepare impact copolymers comprising producing a semi-crystalline polymer in a first reaction zone and then transferring the semi-crystalline polymer to a second reaction zone where a low crystallinity polymer can be produced in the presence of the semi-crystalline polymer.
  • first reactor and second reactor can be reaction zones in the same reactor.
  • Reactors where multiple reaction zones are possible include SpherizoneTM type reactors and those described in US 6,413,477.
  • the impact copolymer can be produced in situ within three reactors, where a first polypropylene is produced in a first reactor, a second polypropylene is produced in a second reactor, and the ethylene copolymer or elastomeric polymer is produced in a third reactor, with each reactor associated in series.
  • the impact copolymer can be produced in situ within three reactors, where the first polypropylene is produced in the first reactor with a first catalyst composition and the second polypropylene is produced in the second reactor with a second catalyst composition, where the first and second catalyst compositions differ from one another, and the elastomeric polymer is produced in the third reactor, each reactor associated in series.
  • the catalyst composition can be modified by changing the identity and/or amount of the transition metal component or the electron donors and/or co-catalysts used in conjunction with the transition metal component.
  • a desirable catalyst composition arrangement can be as discussed and described in WO99/20663A2, where sequential electron donors are used to modify the catalyst composition from one reactor to another, the sequential donors being different compounds or mixtures of compounds.
  • a titanium-magnesium based Ziegler-Natta catalyst can be used in all of the reactors, the same titanium-magnesium composition in a particular embodiment, but the aluminum-alkoxy/alkyl "electron donor" compound used in the first reactor can be different than the aluminum- alkoxy/alkyl compound used in the second reactor.
  • the ratio of a mixture of aluminum-alkoxy/alkyl compounds can be changed in going from the first to the second reactor. In this manner, the isotacticity and/or MFR of the first and second polypropylenes can be tailored.
  • one or more chain terminating agent(s) e.g., hydrogen
  • MFR molecular weight
  • the chain terminating agents can be used as a means of adjusting the MFR of components of the impact copolymer either alone or in conjunction with other means.
  • the process of producing the impact copolymer can include contacting a catalyst with propylene, a first amount of a chain terminating agent, and optionally one or more comonomers, e.g., ethylene and/or C4 to C12 a-olefins, in a first reactor to form a first polypropylene comprising no more than 5 wt% of ethylene and/or a-olefin derived units, based on the weight of the first polypropylene.
  • comonomers e.g., ethylene and/or C4 to C12 a-olefins
  • the catalyst and the first polypropylene can be contacted with propylene, a second amount of a chain terminating agent, and optionally one or more comonomers, e.g., ethylene and/or C4 to C12 a-olefins in a second reactor to form a second polypropylene comprising no more than 5 wt% of ethylene and/or a-olefin derived units, based on the weight of the second polypropylene.
  • the second amount of chain terminating agent can be greater than the first amount of chain terminating agent.
  • the catalyst composition, the first polypropylene, and the second polypropylene can be contacted with propylene and ethylene in a third reactor to form an ethylene-propylene copolymer that includes from 35 wt% or 40 wt% or 45 wt% to 60 wt% or 65 wt%, or 70 wt% ethylene-derived units, based on the weight of the impact copolymer.
  • the first amount of the chain terminating agent can be added to the one or more reactors and/or one or more stages within the reactor(s) such that the first polypropylene has an MFRi from a low of 8 dg/min, 15 dg/min, or 18 dg/min to a high of 33 dg/min, 35 dg/min, or 40 dg/min.
  • the second amount of chain terminating agent can be added (in certain embodiments) such that the second polypropylene has an MFR 2 from a low of 50 dg/min, 65 dg/min, or 70 dg/min to a high of 100 dg/min, 120 dg/min, or 190 dg/min.
  • the second amount of chain terminating agent in certain embodiments can be greater than the first amount of chain terminating agent such that the MFRi of the first polypropylene is at least 30% less, at least 35% less, at least 40% less, at least 45% less, or at least 50% less than the MFR2 of the second polypropylene.
  • the chain terminating agent(s) can be added to the reactor(s) such that MFR 2 /MFR 1 is from a low of 2, 2.5, or 3 to a high of 4, 4.5, 5, or 6 in certain embodiments, and greater than 1.5, greater than 2.0, greater than 2.5, or greater than 3 in other embodiments.
  • the amount of chain terminating agent can be varied by any suitable means in the reactor(s), and in one embodiment the amount of the first chain terminating agent can be less than 2,000 mol ppm or less than 1,800 mol ppm as measured in the first propylene feed to the reactor, and the amount of the second chain terminating agent can be greater than 2,500 mol ppm or greater than 2,800 mol ppm as measured in the second propylene feed to the reactor.
  • catalyst components, propylene, chain terminating agent, and any other optional monomers can be fed to a first loop reactor for a first homopolymerization or copolymerization process.
  • the high heat removal capability of the loop reactor can cause or facilitate turbulent mixing of the slurry and the large surface-to-volume ratio of the reactor can enable high specific outputs.
  • Operating conditions are typically in the range of 60°C to 80°C, 500 psi to 700 psi, and an amount of chain terminating agent, hydrogen in a preferred embodiment, of less than 2,000 mol ppm or less than 1,800 mol ppm as measured in the propylene feed to the reactor, and within the range from 1,000 mol ppm, 1, 100 mol ppm, or 1,200 mol ppm to 1,800 mol ppm, or 2,000 mol ppm in another embodiment.
  • the polymer produced from the first reactor (along with residual chain terminating agent and monomers) can be transferred to a second loop reactor where the operating conditions can be the same or different with respect to the first loop reactor.
  • the polypropylene slurry Upon exiting the second loop reactor, the polypropylene slurry can be depressurized and flashed at a pressure that allows for recycle of the vaporized monomer(s) by condensation using cooling water or other cooling means, and can be sufficient for gas phase polymerization.
  • the polypropylene and catalyst composition mixture can be transferred to a gas phase reactor.
  • the ethylene copolymer or elastomeric polymer can be produced within this gas phase reactor in certain embodiments.
  • the ethylene copolymer, an ethylene-propylene copolymer in a preferred embodiment can be produced in a particular embodiment by use of a fluidized bed gas phase reactor operating at a temperature from a low of 50°C, 60°C, or 70°C to a high of 80°C, 90°C, 100°C, 110°C, or 120°C, and pressures from a low of 100 psi, 125 psi, or 150 psi to a high of 200 psi, 250 psi, or 300 psi.
  • Polymer exiting the polymerization section can pass through a low pressure separator, in which the remaining monomer can be separated for recycle.
  • a steam treatment vessel for deactivation of the residual catalyst can present in certain embodiments.
  • a small fluid bed dryer or other drying means can also be present. An example of such a process can include the so called "Spheripol" reactor process.
  • the catalyst composition can be any suitable catalyst composition known for polymerizing olefins to produce polyolefins and is desirably a composition that can control the isotacticity of the polymers that are produced.
  • suitable catalysts compositions include Ziegler-Natta catalysts, metallocene catalysts, chromium catalysts, metal-imide/amine coordination catalysts, and combinations of such catalysts each with its desirable co-catalyst and/or electron donor or other modifying agent known in the art.
  • An example of certain desirable catalyst compositions can be as discussed and described in WO99/20663, e.g., a Ziegler-Natta catalyst composition using any one of a combination of aluminum alkyl donor systems.
  • a sequential polymerization process can be used and the first polymerization can be a slurry process to produce homopolymer followed by a gas- phase process for producing the impact copolymer.
  • the slurry process can be a loop reactor or a CSTR type of reactor.
  • the first reaction stage can include one or two tubular loop reactors where bulk polymerization of homopolymers can be carried out in liquid propylene.
  • the catalyst e.g., a prepolymerized catalyst, and liquid propylene, and hydrogen for controlling molecular weight can be fed into the reactor.
  • the homopolymer in liquid propylene inside the loops can be continuously discharged to a separation unit.
  • Unreacted propylene can be recycled to the reaction medium while the polymer can be transferred to one or two gas phase reactors where ethylene, propylene, and hydrogen can be added to produce the impact copolymers.
  • the granules can be discharged to the monomer flashing and recovery section and sent to a monomer stripping system. After the drying unit, the granular resin can be conveyed to an extrusion system for stabilization, and pelletization.
  • LTlJavg ⁇ c _ where the summations are over the chromotographic slices, i, between the integration limits.
  • M v is the viscosity-average molecular weight based on molecular weights determined by LS analysis.
  • the "mm triad tacticity index" of a polymer is a measure of the relative isotacticity of a sequence of three adjacent propylene units connected in a head-to-tail configuration. More specifically, the mm triad tacticity index (also referred to as the "mm Fraction") of a polypropylene homopolymer or copolymer is expressed as the ratio of the number of units of meso tacticity to all of the propylene triads in the copolymer: + ⁇ PPP(mm)

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Abstract

L'invention concerne des procédés de production de copolymères résistants aux chocs. L'éthylène et au moins un copolymère peuvent être polymérisés en présence d'un ou de plusieurs catalyseurs, d'une ou de plusieurs particules de polypropylène, et d'un ou de plusieurs composés (hydro)halogénocarbonés pour produire un copolymère résistant aux chocs qui contient les particules de polypropylène et un copolymère d'éthylène.
PCT/US2014/011474 2013-02-06 2014-01-14 Activateurs de polymérisation pour catalyseurs ziegler-natta supportés Ceased WO2014123668A1 (fr)

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