WO2016197014A1 - Système catalytique contenant des supports à surface active élevée et polymérisation séquentielle pour produire des polymères hétérophasiques - Google Patents

Système catalytique contenant des supports à surface active élevée et polymérisation séquentielle pour produire des polymères hétérophasiques Download PDF

Info

Publication number
WO2016197014A1
WO2016197014A1 PCT/US2016/035854 US2016035854W WO2016197014A1 WO 2016197014 A1 WO2016197014 A1 WO 2016197014A1 US 2016035854 W US2016035854 W US 2016035854W WO 2016197014 A1 WO2016197014 A1 WO 2016197014A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
substituted
particle size
hydrocarbyl
support
Prior art date
Application number
PCT/US2016/035854
Other languages
English (en)
Inventor
Lubin Luo
Original Assignee
Exxonmobil Chemical Patents Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US15/142,321 external-priority patent/US9920176B2/en
Priority claimed from PCT/US2016/030036 external-priority patent/WO2016195868A1/fr
Application filed by Exxonmobil Chemical Patents Inc. filed Critical Exxonmobil Chemical Patents Inc.
Priority to US15/570,835 priority Critical patent/US10280235B2/en
Publication of WO2016197014A1 publication Critical patent/WO2016197014A1/fr

Links

Classifications

    • 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
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene
    • 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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65927—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2314/00—Polymer mixtures characterised by way of preparation
    • C08L2314/06—Metallocene or single site catalysts

Definitions

  • This invention relates to: USSN 15/142,021, filed April 29, 2016, which claims priority to and the benefit of 62/171,581 filed June 5, 2015; USSN 15/142,084, filed April 29, 2016, which claims priority to and the benefit of 62/171,590, filed June 5, 2015; USSN 15/142,268, filed April 29, 2016, which claims priority to and the benefit of 62/171,630, filed June 5, 2015; USSN 15/142,377, filed April 29, 2016, which claims priority to and the benefit of 62/171,616, filed June 5, 2015; this invention also relates to USSN 15/142,961, filed April 29, 2016, which claims priority to and the benefit of 62/205,977, filed August 17, 2015; and USSN 62/171,602, filed June 5, 2015; USSN 15/143,050, filed April 29, 2016, which claims priority to and the benefit of 62/206,004, filed August 17, 2015; and USSN 62/171,602, filed June 5, 2015; PCT/US2016/034755, filed May 27,
  • This invention relates to a catalyst system for making heterophasic copolymers, in particular heterophasic copolymers having a bimodal molecular weight distribution in the dispersed phase, and to a method of making such heterophasic copolymers.
  • heterophasic copolymers such as impact copolymers (ICP)
  • ICP impact copolymers
  • Homopolymers such as isotactic polypropylene, iPP
  • MWD molecular weight distribution
  • EPR ethylene propylene rubber
  • metallocenes immobilized on a conventional support (such as silica) coated with an activator (such as methylalumoxane, MAO), are typically not able to provide dispersed phases of EPR components (such as in the case of iPP/EPR impact copolymers), with sufficiently high molecular weight and/or rubber loadings under commercially relevant process conditions.
  • an activator such as methylalumoxane, MAO
  • isotactic polypropylene (iPP) matricies in impact copolymers prepared using metallocenes and or other single site catalysts typically have a low porosity, and are unable to hold a sufficiently high rubber (such as EPR) content within the iPP matrix required for toughness and impact resistance.
  • EPR often has an MWD that is too narrow to obtain a good balance between the desired melt flow rate for material processing and stiffness. This is thought to be due to formation of rubber in a separate phase outside the matrix, which is believed to result in reactor fouling.
  • Pore structures in conventional iPP are thought to be generated from the fast crystallization of low molecular weight portions of the polymer that causes volumetric shrinkage during crystallization. See Nello Pasquini (Ed.), Polypropylene Handbook, 2nd Edition, Hanser Publishers, Kunststoff, pp. 81-88 (2005). Likewise polymer particle morphology is thought to be directly related to catalyst support properties. See Cecchin, G. et al, Marcromol. Chem. Phys., vol. 202, p. 187, (2001).
  • Mw weight average molecular weight
  • the present invention provides a catalyst system that is capable of obtaining a dispersed phase in a heterophasic blend with controlled molecular weight, preferably having both high and low Mw portions, which is thought to influence the balance between toughness and processability in the final polymer.
  • the catalyst system comprises a single site catalyst, an activator, and a support, where the support has:
  • a multimodal particle size distribution comprising a first peak or inflection point having a peak particle size of 3 to 70 ⁇ and a second peak or inflection point having a peak particle size of greater than 70 to 200 ⁇ .
  • the support may comprise primary particles or agglomerated primary particles where the primary particles and/or the agglomerates, or both have an average pore diameter of 60 to 200 Angstrom; preferably, the support comprises agglomerated primary particles where the agglomerates have a narrow particle size distribution having D10 not smaller than 50% of D50 and D90 not larger than 150% of D50.
  • the present invention provides a method of making the catalyst system, comprising supporting an activator on the support described above to form a supported activator; and contacting the supported activator with a single site catalyst precursor compound to form the catalyst system.
  • the present invention provides a method of making a polyolefinic composition, comprising the steps of: (a) contacting a catalyst system as described herein, monomers, and optional comonomers under polymerization conditions to form a porous stiff polymer or copolymer matrix phase comprising at least 50 mol% propylene or ethylene and having a mean pore diameter less than 200 ⁇ as determined by mercury intrusion porosimetry to form a porous matrix phase; and (b) contacting the matrix phase formed in (a) with one or more olefin monomers, and optional comonomers, under polymerization conditions to form a heterophasic copolymer comprising a matrix phase and a dispersed phase.
  • FIG. 1 is an electron micrograph showing a support (PD 14024TM) comprising agglomerated primary particles.
  • mean refers to the statistical mean or average, i.e., the sum of a series of observations or statistical data divided by the number of observations in the series, and the terms mean and average are used interchangeably; "median” refers to the middle value in a series of observed values or statistical data arranged in increasing or decreasing order, i.e., if the number of observations is odd, the middle value, or if the number of observations is even, the arithmetic mean of the two middle values.
  • the mode also called peak value or maxima
  • the mode refers to the value or item occurring most frequently in a series of observations or statistical data, i.e., the inflection point.
  • An inflection point is that point where the second derivative of the curve changes in sign.
  • a peak particle size is the particle size occurring at the peak value.
  • a multimodal distribution is one having two or more peaks or inflection points, i.e., a distribution having a plurality of local maxima; a bimodal distribution has two peak or inflection points; and a unimodal distribution has one peak or inflection point.
  • a bimodal particle size distribution in graph of particle size vs. wt% particles would have two peaks or inflection points.
  • a multimodal particle size distribution in graph of particle size vs wt% particles would have at least two peaks or inflection points.
  • particle size (PS) or diameter, and distributions thereof are determined by laser diffraction using a MASTERSIZER 3000 (range of 1 to 3500 ⁇ ) available from Malvern Instruments, Ltd. Worcestershire, England or using a LS 13320 laser diffraction particle size analyzer with a Micro liquid module (particle size range 0.4 to 2000 ⁇ ) available from Beckman Coulter, Inc., CA, USA, in event of conflict between the results, the LS 13320 shall be used.
  • Average PS refers to the distribution of particle volume with respect to particle size.
  • particle refers to the overall particle body or assembly such as an aggregate, agglomerate or encapsulated agglomerate, rather than subunits or parts of the body such as the "primary particles” in agglomerates or the “elementary particles” in an aggregate.
  • the surface area (SA, also called the specific surface area or BET surface area), pore volume (PV), and mean or average pore diameter (PD) of catalyst support materials are determined by the Brunauer-Emmett-Teller (BET) method using adsorption-desorption of nitrogen (temperature of liquid nitrogen: 77 K) with a MICROMERITICS ASAP 2420 instrument after degassing of the powders for 4 hours at 350°C. More information regarding the method can be found, for example, in "Characterization of Porous Solids and Powders: Surface Area, Pore Size and Density " S. Lowell et al, Springer, 2004.
  • PV refers to the total PV, including both internal and external PV.
  • Mean PD refers to the distribution of total PV with respect to PD.
  • porosity of polymer particles refers to the volume fraction or percentage of PV within a particle or body comprising a skeleton or matrix of the matrix (typically propylene) polymer, on the basis of the overall volume of the particle or body with respect to total volume.
  • the porosity and median PD of polymer particles are determined using mercury intrusion porosimetry.
  • Mercury intrusion porosimetry involves placing the sample in a penetrometer and surrounding the sample with mercury. Mercury is a non- wetting liquid to most materials and resists entering voids, doing so only when pressure is applied. The pressure at which mercury enters a pore is inversely proportional to the size of the opening to the void.
  • the skeleton of the matrix phase of a porous, particulated material in which the pores are formed is inclusive of nonpolymeric and/or inorganic inclusion material within the skeleton, e.g., catalyst system materials including support material, active catalyst system particles, catalyst system residue particles, or a combination thereof.
  • total volume of a matrix refers to the volume occupied by the particles comprising the matrix phase, i.e., excluding interstitial spaces between particles but inclusive of interior pore volumes or internal porosity within the particles.
  • Internal or “interior” pore surfaces or volumes refer to pore surfaces and/or volumes defined by the surfaces inside the particle which cannot be contacted by other similar particles, as opposed to extemal surfaces which are surfaces capable of contacting another similar particle.
  • the porosity also refers to the fraction of the void spaces or pores within the particle or body regardless of whether the void spaces or pores are filled or unfilled, i.e., the porosity of the particle or body is calculated by including the volume of the fill material as void space as if the fill material were not present.
  • mercury intrusion porosimetry shall also include and encompass “as if determined by mercury intrusion porosimetry,” such as, for example, where the mercury porosimetry technique cannot be used, e.g., in the case where the pores are filled with a non-gaseous material such as a fill phase.
  • mercury porosimetry may be employed on a sample of the material obtained prior to filling the pores with the material or just prior to another processing step that prevents mercury porosimetry from being employed, or on a sample of the material prepared at the same conditions used in the process to prepare the material up to a point in time just prior to filling the pores or just prior to another processing step that prevents mercury porosimetry from being employed.
  • agglomerate refers to a material comprising an assembly, of primary particles held together by adhesion, i.e., characterized by weak physical interactions such that the particles can easily be separated by mechanical forces, e.g., particles joined together mainly at comers or edges.
  • primary particles refers to the smallest, individual disagglomerable units of particles in an agglomerate (without fracturing), and may in turn be an encapsulated agglomerate, an aggregate particle.
  • Agglomerates are typically characterized by having an SA not appreciably different from that of the primary particles of which it is composed.
  • Silica agglomerates are prepared commercially, for example, by a spray drying process.
  • FIG. 1 show examples of encapsulated agglomerates 10, which, as seen in the partially opened particles, are comprised of a plurality of primary particles 12.
  • FIG. 1 shows an electron micrograph of silica PD 14024TM(obtained from PQ Corporation, Malvern, Pennsylvania, USA), which appears as generally spherical particles or grains 10, which, as seen in a partially opened particle, are actually agglomerates comprised of a plurality of substructures or primary particles 12 within the outer spherical shell or aggregate surface 14 that partially or wholly encapsulates the agglomerates.
  • the example is shown for illustrative purposes only and the sizes of the particles shown may not be representative of a statistically larger sample; the majority of the primary particles in this or other commercially available silicas may be larger or smaller than the image illustrated, e.g., 2 ⁇ or smaller, depending on the particular silica production process employed by the manufacturer.
  • Aggregates are an assembly of elementary particles sharing a common crystalline structure, e.g., by a sintering or other physico-chemical process such as when the particles grow together. Aggregates are generally mechanically unbreakable, and the specific surface area of the aggregate is substantially less than that of the corresponding elementary particles.
  • An “elementary particle” refers to the individual particles or grains in or from which an aggregate has been assembled.
  • the primary particles in an agglomerate may be elementary particles or aggregates of elementary particles.
  • capsule or “encapsulated” or “microencapsulated” are used interchangeably herein to refer to an agglomerate in the 1-1000 ⁇ size range comprising an exterior surface that is coated or otherwise has a physical barrier that inhibits disagglomeration of the primary particles from the interior of the microencapsulated agglomerate.
  • the barrier or coating may be an aggregate, for example, of primary and/or elementary particles otherwise constituted of the same material as the agglomerate.
  • FIG. 1 shows an example of microencapsulated agglomerates 10 comprised of a plurality of primary particles 12 within an outer aggregate surface or shell 14 that partially or wholly encapsulates the agglomerates, in which the primary particles may be allowed to disagglomerate by fracturing, breaking, dissolving, chemically degrading or otherwise removing all or a portion of the shell 14.
  • the agglomerates 10 may typically have an overall size range of 1 - 300 ⁇ (e.g., 30-200 ⁇ ), the primary particles 12 a size range of 0.001 - 50 ⁇ (e.g., 50 - 400 nm or 1 - 50 ⁇ ), and the elementary particles a size range of 1 - 400 nm (e.g., 5-40 nm).
  • spray dried refers to metal oxide such as silica obtained by expanding a sol in such a manner as to evaporate the liquid from the sol, e.g., by passing the silica sol through a jet or nozzle with a hot gas.
  • Disagglomeration refers to the degradation of an agglomerate to release free primary particles and/or smaller fragments, which may also include reaction products and/or materials supported on a surface thereof, e.g., activator and/or catalyst precursor compounds supported thereon.
  • dispersion in a liquid is a typical process by which unencapsulated agglomerates may be disagglomerated.
  • disagglomeration may also form smaller agglomerates as the residues from which one or more primary particles has been released and/or as the result of re-agglomeration of free primary particles and/or smaller fragments.
  • Frracturing refers to the degradation of aggregates, primary particles, shells, or the like.
  • Framentation or “fragmenting” refers collectively to the release of relatively smaller particles whether by disagglomeration, fracturing, and/or some other process, as the case may be.
  • fragmentation is used herein to refer to the smaller particles including residue agglomerates and any new particles formed from the preceding larger particles resulting from fragmentation, including agglomerate residues of primary particles, free primary particles, fracturing residues, whether smaller or larger than the primary particles, and including any of such particles with or without supportation products thereon or therein.
  • Fragmentation especially where disagglomeration is a primary mechanism, may occur essentially without the formation of fines, i.e., the formation of less than 2 vol% fines, based on the total volume of the agglomerate.
  • fines generally refers to particles smaller than 0.5 ⁇ .
  • Fragmentation can occur by the external application of thermal forces such as high heat such as during calcination of support particles, and/or the presence of mechanical forces from crushing under compression or from the impact of moving particles into contact with other particles and/or onto fixed surfaces, sometimes referred to as "agitation fragmentation.” Fragmentation can also result in some embodiments herein from the insertion, expansion and/or other interaction of materials in connection with pores of the particles, such as, for example, when MAO is inserted or polymer is formed in the pores, and subunits of the support particle are broken off or the support particle otherwise expands to force subunits of the particle away from other subunits, e.g., causing a capsule to break open, forcing primary particles away from each other and/or fracturing primary particles, such as may occur during polymerization or during a heat treatment for catalyst preparation or activation.
  • This latter type of fragmentation is referred to herein as “expansion fragmentation” and/or “expansion disagglomeration” in the case of disag
  • chain transfer agent is hydrogen or an agent capable of hydrocarbyl and/or polymeryl group exchange between a coordinative polymerization catalyst and a metal center of the CTA during polymerization.
  • an "olefin,” alternatively referred to as “alkene,” is a linear, branched, or cyclic compound of carbon and hydrogen having at least one double bond.
  • ethylene shall be considered an a-olefin.
  • An “alkene” group is a linear, branched, or cyclic radical of carbon and hydrogen having at least one double bond.
  • a polymer or copolymer when referred to as comprising an olefin, the olefin present in such polymer or copolymer is the polymerized form of the olefin.
  • a copolymer when a copolymer is said to have an "ethylene" content of 35 wt% to 55 wt%, it is understood that the "mer” unit in the copolymer is derived from ethylene in the polymerization reaction and said derived units are present at 35 wt% to 55 wt%, based upon the weight of the copolymer.
  • a "polymer” has two or more of the same or different mer units.
  • a “homopolymer” is a polymer having mer units that are the same.
  • a “copolymer” is a polymer having two or more mer units that are different from each other.
  • a “terpolymer” is a polymer having three mer units that are different from each other.
  • "Different” as used to refer to mer units indicates that the mer units differ from each other by at least one atom or are different isomerically. Accordingly, the definition of copolymer, as used herein, includes terpolymers and the like.
  • An "ethylene polymer” or “polyethylene” or “ethylene copolymer” is a polymer or copolymer comprising at least 50 mol% ethylene derived units;
  • a "propylene polymer” or “polypropylene” or “propylene copolymer” is a polymer or copolymer comprising at least 50 mol% propylene derived units; and so on.
  • polypropylene is meant to encompass isotactic polypropylene (iPP), defined as having at least 10% or more isotactic pentads, highly isotactic polypropylene, defined as having 50% or more isotactic pentads, syndiotactic polypropylene (sPP), defined as having at 10% or more syndiotactic pentads, homopolymer polypropylene (hPP, also called propylene homopolymer or homopolypropylene), and so- called random copolymer polypropylene (RCP, also called propylene random copolymer).
  • iPP isotactic polypropylene
  • sPP syndiotactic polypropylene
  • hPP also called propylene homopolymer or homopolypropylene
  • RCP random copolymer polypropylene
  • an RCP is specifically defined to be a copolymer of propylene and 1 to 10 wt% of an olefin chosen from ethylene and C4 to Cg 1-olefins.
  • olefin chosen from ethylene and C4 to Cg 1-olefins.
  • isotactic polymers such as iPP
  • a polyolefin is "atactic,” also referred to as “amorphous” if it has less than 10% isotactic pentads and syndiotactic pentads.
  • ethylene-propylene rubber or "EP rubber” (EPR) mean a copolymer of ethylene and propylene, and optionally one or more diene monomer(s), where the ethylene content is from 35 to 85 mol%, the total diene content is 0 to 5 mol%, and the balance is propylene with a minimum propylene content of 15 mol%.
  • hetero-phase or “heterophasic” refers to the presence of two or more morphological phases in a composition comprising two or more polymers, where each phase comprises a different polymer or a different ratio of the polymers as a result of partial or complete immiscibility (i.e., thermodynamic incompatibility).
  • a common example is a morphology consisting of a continuous matrix phase and at least one dispersed or discontinuous phase. The dispersed phase takes the form of discrete domains (particles) distributed within the matrix (or within other phase domains, if there are more than two phases).
  • a co-continuous morphology where two phases are observed but it is unclear which one is the continuous phase, and which is the discontinuous phase, e.g., where a matrix phase has generally continuous internal pores and a fill phase is deposited within the pores, or where the fill phase expands within the pores of an initially globular matrix phase to expand the porous matrix globules, corresponding to the polymer initially formed on or in the support agglomerates, into subglobules which may be partially or wholly separated and/or co-continuous or dispersed within the fill phase, corresponding to the polymer formed on or in the primary particles of the support.
  • a polymer globule may initially have a matrix phase with a porosity corresponding to the support agglomerates, but a higher fill phase due to expansion of the fill phase in interstices between subglobules of the matrix phase.
  • the presence of multiple phases is determined using microscopy techniques, e.g., optical microscopy, scanning electron microscopy (SEM), or atomic force microscopy (AFM); or by the presence of two glass transition (Tg) peaks in a dynamic mechanical analysis (DMA) experiment; or by a physical method such as solvent extraction, e.g., xylene extraction at an elevated temperature to preferential separate one polymer phase; in the event of disagreement among these methods, DMA performed according to the procedure set out in US 2008/0045638 at page 36, including any references cited therein, shall be used.
  • microscopy techniques e.g., optical microscopy, scanning electron microscopy (SEM), or atomic force microscopy (AFM)
  • Tg glass transition
  • DMA dynamic mechanical analysis
  • An ICP may typically have a morphology such that the matrix phase comprises a higher proportion of the crystalline polymer, and a rubber is present in a higher proportion in a dispersed or co-continuous phase, e.g., a blend comprising 60 to 95 wt% of a matrix of iPP, and 5 to 40 wt% of an ethylene, propylene or other polymer with a Tg of -30°C or less.
  • the term “sequential polymerization” refers to a polymerization process wherein different polymers are produced at different periods of time in the same or different reactors, e.g., to produce a multimodal and/or heterophasic polymer.
  • gas phase polymerization slurry phase polymerization
  • homoogeneous polymerization process e.g., homogeneous polymerization process
  • bulk polymerization process e.g., continuous polymerization process.
  • continuous means a system that operates without interruption or cessation. For example, a continuous process to produce a polymer would be one where the reactants are continually introduced into one or more reactors and polymer product is continually withdrawn.
  • Mn is number average molecular weight
  • Mw is weight average molecular weight
  • Mz is z average molecular weight
  • wt% is weight percent
  • mol% is mole percent.
  • Molecular weight distribution also referred to as polydispersity index (PDI)
  • PDI polydispersity index
  • Me is methyl
  • Et is ethyl
  • Pr is propyl
  • cPr is cyclopropyl
  • nPr is n-propyl
  • iPr is isopropyl
  • Bu is butyl
  • nBu is normal butyl
  • iBu is isobutyl
  • sBu is sec-butyl
  • tBu is tert-butyl
  • Oct octyl
  • Ph is phenyl
  • Bn is benzyl
  • THF or thf is tetrahydrofuran
  • MAO is methylalumoxane
  • OTf is trifluoromethanesulfonate.
  • Ambient temperature also referred to herein as room temperature (RT) is 23°C ⁇ 3°C unless otherwise indicated.
  • a "catalyst system” is a combination of at least one catalyst precursor compound, at least one activator, an optional co-activator, and a support material.
  • a polymerization catalyst system is a catalyst system that can polymerize monomers to polymer.
  • the ionic form of the component is the form that reacts with the monomers to produce polymers.
  • the single site catalyst precursor compound may be described as a catalyst, a catalyst precursor, a catalyst precursor compound, a pre-catalyst compound, a catalyst compound, or a transition metal compound, or similar variation, and these terms are used interchangeably.
  • a catalyst precursor compound is a neutral compound without polymerization activity, e.g., Cp 2 ZrCl 2 , which requires an activator, e.g., MAO, to form an active catalyst species, e.g., [Cp 2 ZrMe] + , or a resting active catalyst species, e.g., to become capable of polymerizing olefin monomers.
  • a metallocene catalyst is defined as an organometallic compound (and may sometimes be referred to as such in context) with at least one ⁇ -bound cyclopentadienyl moiety (or substituted cyclopentadienyl moiety) and more frequently two ⁇ -bound cyclopentadienyl moieties or substituted cyclopentadienyl moieties.
  • Indene, substituted indene, fluorene, and substituted fluorene are all substituted cyclopentadienyl moieties.
  • cyclopentadiene differs from methyl cyclopentadiene in the presence of the methyl group.
  • bisindenyl zirconium dichloride is different from “(indenyl)(2-methylindenyl) zirconium dichloride” which is different from “(indenyl)(2- methylindenyl) hafnium dichloride.”
  • Catalyst compounds that differ only by isomer are considered the same for purposes of this invention, e.g., rac-dimethylsilylbis(2-methyl 4- phenyl)hafnium dimethyl is considered to be the same as meso-dimethylsilylbis(2-methyl 4- phenyl)hafnium dimethyl.
  • An organometallic compound is defined as a compound containing at least one bond between a carbon atom of an organic compound and a metal, and is typically, although not always, capable of deprotonating hydroxyl groups, e.g., from a support material.
  • a deprotonating agent is defined as a compound or system capable of deprotonating hydroxyl groups from the support, and may be an organometallic or another compound such as a metal amide, e.g., aluminum amide or lithium amide.
  • An "anionic ligand” is a negatively charged ligand, which donates one or more pairs of electrons to a metal ion.
  • a "neutral donor ligand” is a neutrally charged ligand, which donates one or more pairs of electrons to a metal ion.
  • cocatalyst and “activator” are used herein interchangeably and are defined to be any compound which can activate the catalyst precursor compound by converting a neutral catalyst precursor compound to a catalytically active catalyst compound cation.
  • non-coordinating anion NCA
  • compatible NCA
  • bulky activator molecular volume
  • molecular volume e.g., methanol
  • more bulky e.g., methanol
  • the heterophasic propylene polymer composition produced herein may be referred to herein as an impact copolymer, or a propylene impact copolymer, or an in-reactor propylene impact copolymer, or an in-reactor propylene impact copolymer composition, and such terms are used interchangeably herein.
  • hydrocarbyl radical is defined to be a radical, which contains hydrogen atoms and up to one hundred carbon atoms and which may be linear, branched, or cyclic, and when cyclic, aromatic or non-aromatic.
  • a substituted hydrocarbyl radical is a hydrocarbyl radical where at least one hydrogen has been replaced by a heteroatom or heteroatom-containing group.
  • Halocarbyl radicals are radicals in which one or more hydrocarbyl hydrogen atoms have been substituted with at least one halogen (e.g., F, CI, Br, I) or halogen- containing group (e.g., CF3).
  • Silylcarbyl radicals are groups in which the silyl functionality is bonded directly to the indicated atom or atoms. Examples include S1H3,
  • R* is independently a hydrocarbyl or halocarbyl radical and two or more R* may join together to form a substituted or unsubstituted saturated, partially unsaturated or aromatic cyclic or poly cyclic ring structure.
  • Germylcarbyl radicals are groups in which the germyl functionality is bonded directly to the indicated atom or atoms. Examples include GeH3,
  • R* is independently a hydrocarbyl or halocarbyl radical and two or more R* may join together to form a substituted or unsubstituted saturated, partially unsaturated or aromatic cyclic or poly cyclic ring structure.
  • Polar radicals or polar groups are groups in which a hetero-atom functionality is bonded directly to the indicated atom or atoms. They include heteroatoms of Groups 1-17 of the periodic table either alone or connected to other elements by covalent or other interactions, such as ionic, van der Waals forces, or hydrogen bonding.
  • Examples of functional groups include carboxylic acid, acid halide, carboxylic ester, carboxylic salt, carboxylic anhydride, aldehyde and their chalcogen (Group 14) analogues, alcohol and phenol, ether, peroxide and hydroperoxide, carboxylic amide, hydrazide and imide, amidine and other nitrogen analogues of amides, nitrile, amine and imine, azo, nitro, other nitrogen compounds, sulfur acids, selenium acids, thiols, sulfides, sulfoxides, sulfones, sulfonates, phosphines, phosphates, other phosphorus compounds, silanes, boranes, borates, alanes, aluminates.
  • chalcogen Group 14
  • Functional groups may also be taken broadly to include organic polymer supports or inorganic support material, such as alumina, and silica.
  • Preferred examples of polar groups include NR* 2 , OR*, SeR*, TeR*, PR* 2 , AsR* 2 , SbR* 2 , SR*, BR* 2 , SnR* 3 ,
  • R* is independently a hydrocarbyl, substituted hydrocarbyl, halocarbyl or substituted halocarbyl radical as defined above and two R* may join together to form a substituted or unsubstituted saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure.
  • An aryl group is defined to be a single or multiple fused ring group where at least one ring is aromatic.
  • aryl and substituted aryl groups include phenyl, naphthyl, anthracenyl, methylphenyl, isopropylphenyl, tert-butylphenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, carbazolyl, indolyl, pyrrolyl, and cyclopenta[Z>]thiopheneyl.
  • Preferred aryl groups include phenyl, benzyl, carbazolyl, naphthyl, and the like.
  • substituted cyclopentadienyl or “substituted indenyl,” or “substituted aryl”
  • substitution to the aforementioned is on a bondable ring position, and each occurrence is selected from hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, germylcarbyl, a halogen radical, or a polar group.
  • a “bondable ring position” is a ring position that is capable of bearing a substituent or bridging substituent.
  • cyclopenta[Z>]thienyl has five bondable ring positions (at the carbon atoms) and one non-bondable ring position (the sulfur atom); cyclopenta[Z>]pyrrolyl has six bondable ring positions (at the carbon atoms and at the nitrogen atom).
  • substituted indicates that a hydrogen group has been replaced with a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, germylcarbyl, a halogen radical, or a polar group.
  • methyl phenyl is a phenyl group having had a hydrogen replaced by a methyl group.
  • the present invention in some embodiments provides a catalyst system that can produce polyolefinic copolymers having balanced toughness and processability, in particular by controlling the molecular weight distribution of the dispersed phase (e.g., a fill rubber) in heterophasic copolymers.
  • the dispersed phase e.g., a fill rubber
  • the size of the matrix phase is catalyst support particle size dependent and can significantly affect the Mw of the dispersed phase, typically an EPR.
  • the larger the catalyst support particle the lower the Mw of the EPR under the same reaction conditions.
  • the inventors theorize that because a larger iPP matrix particle has longer pore channels, the heat removal in a larger iPP matrix particle may be less efficient than in a smaller matrix particle or the monomer mass transfer limit is easier to reach in the larger matrix particles than in the smaller matrix particles or both.
  • the iPP matrix particles are thought to replicate the support particles (e.g., larger support particles generate larger iPP matrix particles), the choice of support particle sizes can influence the Mw of EPR phase. Consequently, ICP properties, such as toughness and processability, can be enhanced.
  • the catalyst system comprises a single site catalyst, an activator, and a support having: A) an average particle size of more than 30 ⁇ up to 200 ⁇ ; B) a specific surface area of 400 to 800 m 2 /g; C) an average pore diameter of 60 to 200 Angstroms; and D) 10 to 90 wt% of particles having a size of from 3 to 70 ⁇ and 90 to 10 wt% of particles having a size of from 70 to 200 ⁇ , based upon the weight of the support.
  • the catalyst system comprises a single site catalyst, an activator, and a support having: A) an average particle size of more than 30 ⁇ up to 200 ⁇ ; B) a specific surface area of 400 to 800 m 2 /g; C) an average pore diameter of 60 to 200 Angstroms; and E) a multimodal particle size distribution comprising a first peak or inflection point having a peak particle size of 3 to 70 ⁇ and a second peak or inflection point having a peak particle size of greater than 70 to 200 ⁇ .
  • the catalyst system comprises a single site catalyst, an activator, and a support having: A) an average particle size of more than 30 ⁇ up to 200 ⁇ ; B) a specific surface area of 400 to 800 m 2 /g; C) an average pore diameter of 60 to 200 Angstrom; and D) 10 to 90 wt% of particles having a size of from 3 to 70 ⁇ and 90 to 10 wt% of particles having a size of from greater than 70 to 200 ⁇ , based upon the weight of the support; and E) a multimodal particle size distribution comprising a first peak or inflection point having a peak particle size of 3 to 70 ⁇ and a second peak or inflection point having a peak particle size of greater than 70 to 200 ⁇ , where the difference between the two peak sizes is at least 10 ⁇ , alternately at least 20 ⁇ , alternately at least 30 ⁇ , alternately at least 50 ⁇ , alternately at least 60 ⁇ , alternately at least 75 ⁇ , alternately at least
  • the support can comprise (1) 10-50 wt% of particles having a size of from 20 to 70 ⁇ , and (2) 50 to 10 wt% of particles having a size of from greater than 70 to 150 ⁇ .
  • the support of the catalyst system can have a multimodal, preferably bimodal, particle size distribution comprising a first peak or inflection point having a peak particle size of 40 to 70 ⁇ and a second peak or inflection point having a peak particle size of greater than 70 to 150 ⁇ .
  • the support can have an average particle size of 40 tol50 ⁇ , and/or a specific surface area of 400 m 2 /g to 800 m 2 /g, and/or a pore volume of from 0.5 to 3 mL/g, and/or a mean pore diameter of from 6 to 30 nm (60 to 300 A).
  • the support can comprise agglomerates of a plurality of primary particles, said primary particles having an average particle size from 0.01 to 30 ⁇ .
  • the primary particles in the agglomerates have a narrow particle size distribution with D 10 not smaller than 50% of D50 and D90 not large than 150% of D50, wherein D10, D50, and D90 represent the 10 th , 50 th , and 90 th percentile, respectively of the particle size (e.g., diameter) distribution.
  • a D90 of 10 microns means that 90 vol% of the particles have a diameter less than or equal to 10 microns.
  • the support comprises agglomerated primary particles with a narrow PSD having Di 0 not smaller than 80% of D 5 o and D 9 o not larger than 120% of D 5 o.
  • the primary particles in the agglomerates have a narrow particle size distribution with Di 0 not smaller than, 50%, or 60%, 70%, or 80% of D 50 and D 90 not large than 150%, 140%, 130%, or 120% of D 50 .
  • the polyolefinic copolymer comprises a heterophasic copolymer comprising a dispersed phase at least partially filling the pores of the matrix phase.
  • the catalyst systems and supports described herein are useful in a process to produce olefinic copolymers, e.g., impact copolymers.
  • the process is useful to control molecular weight attributes of the dispersed phase.
  • the process to polymerize monomers comprises: (a) contacting a catalyst system described herein and monomers (typically propylene) and optional comonomers (typically ethylene and or other C4 to C12 olefins) under polymerization conditions to form a porous, preferably stiff, polymer or copolymer matrix phase comprising at least 50 mol% propylene or ethylene and having a mean pore diameter of less than 200 ⁇ as determined by mercury intrusion porosimetry; and (b) contacting the matrix phase with one or more olefin monomers under polymerization conditions to form a heterophasic copolymer comprising a matrix phase and a dispersed phase, said dispersed phase typically filling the pores of the matrix phase; wherein the catalyst system comprises a single site catalyst, an activator, and a support where the support has:
  • a multimodal particle size distribution comprising a first peak or inflection point having a peak particle size of 3 to 70 ⁇ (alternately 30 to 70 ⁇ ) and a second peak or inflection point having a peak particle size of greater than 70 to 200 ⁇ (alternately 90 to 160 ⁇ ).
  • the present invention provides a method of making a catalyst system, comprising the steps of (a) providing a support described herein; (b) supporting an activator on the support to form a supported activator; and (c) contacting the supported activator with a single site catalyst precursor compound to form the catalyst system.
  • the present invention provides a process to make a stiff matrix phase (such as isotactic polypropylene, random copolymer polypropylene) comprising the steps of (a) contacting propylene and optional comonomer (such as ethylene and C4 to C 12 alpha olefin), and optional hydrogen, under polymerization conditions with a catalyst system comprising a single site catalyst precursor compound, an activator, and the support described herein, (b) polymerizing (a) for a time period, Al to form a first polymer comprising at least 80 mol% propylene; and (c) optionally adding additional alpha olefins to the polymerization after time period Al, and (d) then polymerizing in the presence of at least 1 mmol of the hydrogen or other chain transfer agent per mol of propylene present for a time period, A2, wherein the concentration of the hydrogen or other chain transfer agent, if present, during time period A2 is greater than the concentration of the hydrogen or other
  • time period Al is at least as long as time period A2 and/or the concentration of the hydrogen or other chain transfer agent during time period A2 is at least three times greater than the concentration of the hydrogen or other chain transfer agent in time period Al .
  • Time period B can be shorter or longer than time period Al, e.g., B is at least one quarter of Al (1/4A1), alternately B is at least one half of Al (1/2A1), alternately B is the same as Al, alternately B is at least two times Al (2A1), alternately B is at least 3A1. Alternately, B is 100 times Al or less, typically from 1/4A1 to 50A1, typically from 1/2A1 to 10A1.
  • the present invention provides a process to make a stiff matrix phase (such as ethylene polymer) comprising the steps of (a) contacting ethylene and optional comonomer (such as C3 to C 12 alpha olefin), and optional hydrogen or other chain transfer agent, under polymerization conditions with a catalyst system comprising a single site catalyst precursor compound, an activator, and the support described herein, (b) polymerizing (a) for a time period, Al to form a first polymer comprising at least 80 mol% ethylene; and (c) optionally adding additional alpha olefins (ethylene and optional C3 to C 12 alpha mono- and/or di-olefin) to the polymerization after time period Al, and (d) then polymerizing in the presence of at least 1 mmol of the hydrogen or other chain transfer agent per mol of propylene present for a time period, A2, wherein the concentration of the hydrogen or other chain transfer agent, if present, during time period A2 is greater
  • the support in (a) comprises agglomerates of a plurality of primary particles, and/or the propylene polymer matrix formed in (e) comprises a median PD less than 165 ⁇ , or less than 160 ⁇ , as determined by mercury intrusion porosimetry.
  • the catalyst system(s) may comprise one or more of any of the catalyst systems described herein.
  • the contacting of the propylene monomer with the catalyst system during time period Al, time period A2, or a combination thereof is carried out in a slurry.
  • the polymerization conditions during time period Al, time period A2, or a combination thereof comprise a pressure of from about 0.96 MPa (140 psi) to about 5.2 MPa (750 psi) and a temperature of from about 50°C to 100°C.
  • the process further comprises melt processing the propylene polymer at a shear rate of 1000 sec "1 or more.
  • the polyolefinic copolymers have a melt flow rate of in the range of 20 to 100 g/lOmin, and in the same or different embodiments a fill phase of a heterophasic copolymer having a multimodal molecular weight distribution, and/or the fill phase loading content is at least 20 wt%, e.g., at least 25 wt%, at least 30 wt%, at least 35 wt%, or at least 40 wt% based on the total weight of the matrix phase and the fill phase.
  • the heterophasic polymer produced comprises at least 20 wt% of the dispersed phase, preferably at least 25 wt%, at least 30 wt%, at least 35 wt%, at least 40 wt%, or at least 50 wt%, alternately from 20 wt% to 80 wt%, alternately from 30 wt% to 70 wt%, alternately from 35 wt% to 60 wt%, based on the total weight of the matrix phase and the dispersed phase.
  • the catalyst system may comprise porous solid particles as an inert support material to which the catalyst precursor compound and/or activator may be anchored, bound, adsorbed, or the like.
  • the support material is an inorganic oxide in a finely divided form.
  • Suitable inorganic oxide materials for use in catalyst systems herein include Groups 2, 4, 13, and 14 metal oxides, such as silica, alumina, magnesia, titania, zirconia, and the like, and mixtures thereof.
  • Other suitable support materials can be employed, for example, finely divided functionalized polyolefins, such as finely divided polyethylene or polypropylene.
  • Particularly useful supports include silica, magnesia, titania, zirconia, montmorillonite, phyllosilicate, zeolites, talc, clays, and the like. Also, combinations of these support materials may be used, for example, silica-chromium, silica-alumina, silica-titania, and the like.
  • the support material preferably comprises silica, e.g., amorphous silica, which may include a hydrated surface presenting hydroxyl or other groups which can be deprotonated to form reactive sites to anchor activators and/or catalyst precursors.
  • silica e.g., amorphous silica
  • Other porous support materials may optionally be present with the preferred silica as a co-support, for example, talc, other inorganic oxides, zeolites, clays, organoclays, or any other organic or inorganic support material and the like, or mixtures thereof.
  • the support materials of some embodiments of the invention unexpectedly, are generally resistant to agitation fragmentation or expansion fragmentation during calcination temperatures.
  • the support can be calcined essentially free of fragmentation, (i.e., the PS distribution is not changed significantly and/or is changed by less than 5 vol% of primary particles (if present) and/or fines generated, based on the total volume of the support material).
  • the support material is then contacted with the activator (described in more detail below, at least one single site catalyst precursor compound (described in more detail below), and/or cocatalyst (described in more detail below), and optionally a scavenger or co-activator (described in more detail below).
  • the activator described in more detail below, at least one single site catalyst precursor compound (described in more detail below), and/or cocatalyst (described in more detail below), and optionally a scavenger or co-activator (described in more detail below).
  • the support in, and/or used to prepare, the catalyst system preferably has or comprises the following:
  • a multimodal (typically a bimodal) particle size distribution having a first peak at a particle size of 3 - 70 ⁇ , or 10 - 70 ⁇ , or 30 - 70 ⁇ , or 40 - 70 ⁇ , or 50 - 70 ⁇ , and second peak at a particle size of greater than 70 - 200 ⁇ , or greater than 70 - 180 ⁇ , or greater than 70 - 160 ⁇ , or 90 - 160 ⁇ , or 100 - 150 ⁇ ;
  • SA specific surface area
  • a pore volume (PV) from at least 0.1 mL/g, or at least 0.15 mL/g, or at least 0.2 mL/g, or at least 0.25 mL/g, or at least 0.3 mL/g, or at least 0.5 mL/g; and/or up to 3.0 mL/g, or less than 2.0 mL/g, or less than 1.6 mL/g, or less than 1.5 mL/g, or less than 1.4 mL/g, or less than 1.3 mL/g; e.g., 0.5-2 mL/g or 0.5-1.5 mL/g or 1.1-1.6 mL/g;
  • PD mean pore diameter
  • agglomerates composed of a plurality of primary particles, the primary particles having an average PS of 10 nm to less than 30 ⁇ , or 1 ⁇ to less than 30 ⁇ ;
  • agglomerates of h wherein the primary particles are in narrow particle size distribution with D10 not smaller than 50% of D50 and D90 not larger than 150% of D50;
  • silica e.g., amorphous silica and/or silica having a hydrated surface
  • the support comprises an agglomerate of a plurality of primary particles, and in further embodiments the support is at least partially encapsulated. Additionally or alternatively, the support comprises a spray dried material, e.g., spray dried silica.
  • the support materials in addition to meeting the PS, PSD SA, and optinally PV and PSD characteristics, are preferably made from a process that agglomerates smaller primary particles, e.g., average PS in the range of 0.01-30 ⁇ , into the larger agglomerates with average PS in the range of 30-200 ⁇ , such as those from a spray drying process.
  • the larger particles i.e., the agglomerates
  • Either or both of the agglomerates and/or primary particles can have high or low sphericity and roundness, e.g., a Wadell sphericity of 0.8 or more, 0.85 or more, 0.9 or more, or 0.95 or more, or less than 0.95, less than 0.90, less than 0.85, or less than 0.8; and a Wadell roundness from 0.1 or less up to 0.9 or more.
  • agglomerates having, within the preferred ranges of SA > 400 m 2 /g and mean PD 6 - 20 nm, either a lower SA, e.g., less than 500 m 2 /g or less than 550 m 2 /g, and/or a higher mean PD, e.g., more than 13 nm or more than 15 nm, have higher mechanical strength and are more resistant to catalyst preparation or polymerization processes where strong agitation is present, e.g., a mechanical stirrer, which can thus be carried out under normal catalyst preparation or polymerization conditions, and higher activator and/or catalyst loadings can be achieved for higher catalyst activity.
  • a lower SA e.g., less than 500 m 2 /g or less than 550 m 2 /g
  • a higher mean PD e.g., more than 13 nm or more than 15 nm
  • agglomerates with SA greater than 650 m 2 /g or greater than 700 m 2 /g, and mean PD less than 8 nm or less than 7 nm can be prepared with minimal fragmentation with carefully controlled process conditions such as low supportation reaction temperatures, and yet may more readily fragment during polymerization, which can lead to relatively higher propylene polymer porosity and/or higher fill phase content in the case of heterophasic copolymers.
  • the PD when SA is in the range of about 650 or 700 m 2 /g or higher, to maintain mechanical strength the PD must be low, e.g., less than 7 nm, and the fragmentation of silica supported activator, e.g., silica supported MAO, can be promoted, if desired, using supportation conditions that facilitate the essentially complete or partial fragmentation, e.g., at a temperature higher than about 40 or 60°C, or can be limited by the reduction of MAO loading, and/or the reduction of MAO supportation reaction temperature, especially in the stage of MAO addition to the silica, e.g., ⁇ 0°C.
  • silica supported activator e.g., silica supported MAO
  • the support material may further comprise, in addition to or in combination with any one or more of the support materials or supported catalyst systems or mixtures described above, an optional second or co-support material, which may be designed to promote the polymerization of another propylene polymer or copolymer (as in a bimodal polypropylene) and/or another olefin polymer or copolymer, e.g., a rubber fill material or an EP rubber (as in an impact copolymer).
  • an optional second or co-support material which may be designed to promote the polymerization of another propylene polymer or copolymer (as in a bimodal polypropylene) and/or another olefin polymer or copolymer, e.g., a rubber fill material or an EP rubber (as in an impact copolymer).
  • the support material may further comprise, in addition to or in combination with any one or more of the support materials or supported catalyst systems or mixtures described above, an optional second or co-support material, which may be designed to promote the polymerization of another ethylene polymer or copolymer (as in a bimodal polyethylene) and/or another olefin polymer or copolymer, e.g., a rubber fill material or an EP rubber (as in an impact copolymer).
  • an optional second or co-support material which may be designed to promote the polymerization of another ethylene polymer or copolymer (as in a bimodal polyethylene) and/or another olefin polymer or copolymer, e.g., a rubber fill material or an EP rubber (as in an impact copolymer).
  • the support material can be used wet, i.e., containing adsorbed water, or dry, that is, free of absorbed water.
  • the amount of absorbed water can be determined by standard analytical methods, e.g., LOD (loss of drying) from an instrument such as LECO TGA 701 under conditions such as 300°C for 3 hours.
  • wet support material (without calcining) can be contacted with the activator or another organometallic compound as otherwise described below, with the addition of additional organometallic or other scavenger compound that can react with or otherwise remove the water, such as a metal alkyl.
  • an aluminum alkyl such as ⁇ 1 ⁇ 3
  • organic solvent such as toluene
  • Drying of the support material can be effected according to some embodiments of the invention by heating or calcining above about 100°C, e.g., from about 100°C to about 1000°C, preferably at least about 200°C.
  • the support material is silica, according to some embodiments of the invention it is heated to at least 130°C, preferably about 130°C to about 850°C, and most preferably at about 200-600°C; and for a time of 1 minute to about 100 hours, e.g., from about 12 hours to about 72 hours, or from about 24 hours to about 60 hours.
  • the calcined support material in some embodiments according to this invention comprises at least some groups reactive with an organometallic compound, e.g., reactive hydroxyl (OH) groups to produce the supported catalyst systems of this invention.
  • Activators are compounds used to activate any one of the catalyst precursor compounds described herein by converting the neutral catalyst precursor compound to a catalytically active catalyst compound cation.
  • Preferred activators include alumoxane compounds, including modified alumoxane compounds.
  • Alumoxanes are generally oligomeric, partially hydrolyzed aluminum alkyl compounds containing -Al(Rl)-0- sub-units, where Rl is an alkyl group, and may be produced by the hydrolysis of the respective trialkylaluminum compound.
  • alumoxane activators include methylalumoxane (MAO), ethylalumoxane, butylalumoxane, isobutylalumoxane, modified MAO (MMAO), halogenated MAO where the MAO may be halogenated before or after MAO supportation, dialkylaluminum cation enhanced MAO, surface bulky group modified MAO, and the like.
  • MMAO may be produced by the hydrolysis of trimethylaluminum and a higher trialkylaluminum such as triisobutylaluminum. Mixtures of different alumoxanes may also be used as the activator(s).
  • NCA non-coordinating anion
  • the term “non-coordinating anion” means an anion which either does not coordinate to a cation or which is only weakly coordinated to a cation thereby remaining sufficiently labile to be displaced by a neutral Lewis base.
  • NCA is also defined to include multicomponent NCA-containing activators, such as N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, that contain an acidic cationic group and the non- coordinating anion.
  • NCA is also defined to include neutral Lewis acids, such as tris(pentafluorophenyl)boron, that can react with a catalyst to form an activated species by abstraction of an anionic group.
  • NCA coordinates weakly enough that a neutral Lewis base, such as an olefinically or acetylenically unsaturated monomer can displace it from the catalyst center.
  • a neutral Lewis base such as an olefinically or acetylenically unsaturated monomer can displace it from the catalyst center.
  • Any metal or metalloid that can form a compatible, weakly coordinating complex may be used or contained in the noncoordinating anion. Suitable metals include, but are not limited to, aluminum, gold, and platinum. Suitable metalloids include, but are not limited to, boron, aluminum, phosphorus, and silicon.
  • the activator can be either neutral or ionic.
  • Non-coordinating anions are those which are not degraded to neutrality when the initially formed complex decomposes. Further, the anion will not transfer an anionic substituent or fragment to the cation so as to cause it to form a neutral transition metal compound and a neutral by-product from the anion.
  • Non-coordinating anions useful in this invention are those that are compatible, stabilize the transition metal cation in the sense of balancing its ionic charge at +1, and yet retain sufficient lability to permit displacement during polymerization.
  • NCA such as tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, a tris perfluorophenyl boron metalloid precursor or a tris perfluoronaphthyl boron metalloid precursor, polyhalogenated heteroborane anions (WO 98/43983), boric acid (US 5,942,459), or combination thereof. It is also within the scope of this invention to use neutral or ionic activators alone or in combination with alumoxane or modified alumoxane activators.
  • Boron-containing NCA activators represented by the formula below may be used: (Z) ( j + (A ⁇ -), wherein Z is (L-H) or a reducible Lewis Acid, L is a neutral Lewis base; H is hydrogen; (L-H) + is a Bronsted acid; A ⁇ - is a non-coordinating anion having the charge d-; and d is an integer from 1 to 3.
  • the cation component may include Bronsted acids such as protonated Lewis bases capable of protonating a moiety, such as an alkyl or aryl, from the bulky ligand metallocene containing transition metal catalyst precursor, resulting in a cationic transition metal species.
  • Bronsted acids such as protonated Lewis bases capable of protonating a moiety, such as an alkyl or aryl, from the bulky ligand metallocene containing transition metal catalyst precursor, resulting in a cationic transition metal species.
  • Lewis acid it may be represented by the formula: (Ar3C + ), where Ar is aryl or aryl substituted with a heteroatom, a Ci to C40 hydrocarbyl, or a substituted Ci to C40 hydrocarbyl, preferably the reducible Lewis acid is represented by the formula: (PI13C "1" ), where Ph is phenyl or phenyl substituted with a heteroatom, a Ci to C40 hydrocarbyl, or a substituted Ci to C40 hydrocarbyl.
  • the reducible Lewis acid may be triphenyl carbenium.
  • the anion component may include those having the formula
  • Each Q may be a fluorinated hydrocarbyl group having 1 to 20 carbon atoms, a fluorinated aryl group, or a pentafluoro aryl group.
  • suitable A ⁇ - components also include diboron compounds as disclosed in US 5,447,895, which is fully incorporated herein by reference.
  • the reducible Lewis acid is represented by the formula: (Ar3C+), where Ar is aryl or aryl substituted with a heteroatom, a Ci to C40 hydrocarbyl, or a substituted Ci to C40 hydrocarbyl, preferably the reducible
  • Lewis acid is represented by the formula: (PI13C+), where Ph is phenyl or phenyl substituted with a heteroatom, a Ci to C40 hydrocarbyl, or a substituted Ci to C40 hydrocarbyl.
  • a "Bulky activator” as used herein refers to anionic activators represented by the formula: where: each Ri is, independently, a halide, preferably a fluoride; each R2 is, independently, a halide, a to C20 substituted aromatic hydrocarbyl group or a siloxy group of the formula - O-Si-R g , where R a is a Ci to C20 hydrocarbyl or hydrocarbylsilyl group (preferably R21S a fluoride or a perfluorinated phenyl group); each R3 is a halide, to C20 substituted aromatic hydrocarbyl group or a siloxy group of the formula
  • R a is a Ci to C20 hydrocarbyl or hydrocarbylsilyl group (preferably R3 is a fluoride or a perfluorinated aromatic hydrocarbyl group); wherein R2 and R3 can form one or more saturated or unsaturated, substituted or unsubstituted rings (preferably R2 and R3 form a perfluorinated phenyl ring); L is a neutral Lewis base; (L-H) + is a Bronsted acid; d is 1, 2, or 3; wherein the anion has a molecular weight of greater than 1020 g/mol; and wherein at least three of the substituents on the B atom each have a molecular volume of greater than 250 cubic A, alternately greater than 300 cubic A, or alternately greater than 500 cubic A.
  • Molecular volume is used herein as an approximation of spatial steric bulk of an activator molecule in solution. Comparison of substituents with differing molecular volumes allows the substituent with the smaller molecular volume to be considered “less bulky” in comparison to the substituent with the larger molecular volume. Conversely, a substituent with a larger molecular volume may be considered “more bulky” than a substituent with a smaller molecular volume.
  • Molecular volume may be calculated as reported in "A Simple "Back of the Envelope” Method for Estimating the Densities and Molecular Volumes of Liquids and Solids," Journal of Chemical Education, Vol. 71, No. 11, November 1994, pp. 962-964.
  • V s is the sum of the relative volumes of the constituent atoms, and is calculated from the molecular formula of the substituent using the following table of relative volumes. For fused rings, the V s is decreased by 7.5% per fused ring.
  • Preferred activators include N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, N,N- dimethylanilinium tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium tetrakis(perfiuorophenyl)borate, N,N-dimethylanilinium tetrakis(3,5- bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5- bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluorophenyl)borate, [Ph 3 C+] [B(C 6 F 5 )
  • the activator comprises a triaryl carbonium (such as triphenylcarbenium tetraphenylborate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate).
  • a triaryl carbonium such as triphenylcarbenium tetraphenylborate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis-(2,3,4,6-tetra
  • the activator may comprise one or more of trialkylammonium tetrakis(pentafluorophenyl)borate, N,N-dialkylanilinium tetrakis(pentafluorophenyl)borate, N,N-dimethyl-(2,4,6-trimethylanilinium) tetrakis(pentafluorophenyl)borate, trialkylammonium tetrakis-(2,3,4,6-tetrafluorophenyl) borate, N,N-dialkylanilinium tetrakis- (2,3,4,6-tetrafluorophenyl)borate, trialkylammonium tetrakis(perfluoronaphthyl)borate, N,N- dialkylanilinium tetrakis(perfluoronaphthyl)borate, trialkylammonium tetrakis(perfiuor
  • NCA activator may be chosen from the activators described in US 6,211,105, which is incorporated by reference herein.
  • activators that are a combination of alumoxanes and NCAs (see, for example, US 5,153,157; US 5,453,410; EP 0 573 120; WO 94/07928; and WO 95/14044; which discuss the use of an alumoxane in combination with an ionizing activator).
  • Supportation 1) Activator supportation -
  • the support is treated with an organometallic compound to react with deprotonated reactive sites on the support surface.
  • the support is treated first with an organometallic activator such as MAO, and then the supported activator is treated with the MCN, optional metal alkyl co-activator, as in the following discussion for illustrative purposes, although the MCN and or co-activator can be loaded first, followed by contact with the other catalyst system components, especially where the activator is not an organometallic compound or otherwise reactive with the support surface.
  • the organometallic compound activator in this example
  • Suitable non-polar solvents are materials in which, other than the support material and its adducts, all of the reactants used herein, i.e., the activator, and the MCN compound, are at least partially soluble and which are liquid at reaction temperatures.
  • Preferred non-polar solvents are alkanes, such as isopentane, hexane, n-heptane, octane, nonane, and decane, although a variety of other materials including cycloalkanes, such as cyclohexane, aromatics, such as benzene, toluene, and ethylbenzene, may also be employed.
  • the mixture of the support material and activator (or other organometallic compound) in various embodiments of the invention may generally be heated or maintained at a temperature of from about -60°C up to about 130 or 140°C, such as, for example: about 40°C or below, about 23°C or below, about -20°C or below; from about 10°C or 20°C up to about 60°C or about 40°C; about 23°C or about 25°C or above; or from about 40°C, about 60°C, or about 80°C up to about 100°C, or about 120°C.
  • fragmentation can be controlled through the manipulation of reaction conditions to inhibit fragmentation such as at a lower reaction temperature, e.g., -60°C - 40°C, preferably -20°C - 30°C, to achieve ⁇ 10 vol% fragmented particles, preferably ⁇ 5 vol% fragmented particles; or to promote fragmentation such as at a higher reaction temperature, e.g., > 40°C, preferably > 60°C, to achieve > 10 vol% fragmented particles, e.g., 10-80 vol% fragmented particles, such as 10-20 vol% fragmented particles, 20-70 vol% fragmented particles, 70-90 vol% fragmented particles, >90 vol% fragmented particles, or the like.
  • the time and temperature required to promote fragmentation are inversely related
  • the support material is not significantly fragmented during supportation or other treatment prior to polymerization, i.e., the supported catalyst system has a PSD that is essentially maintained upon treatment with the organometallic compound and/or less than 5 vol% of fines is generated by volume of the total support material, e.g., where the support material is resistant to fragmentation, or supportation conditions are selected to inhibit fragmentation.
  • Maintaining a sufficiently large bimodal or multimodal average PS or PS modes of the supported catalyst system material facilitates the formation of sufficiently large matrix polymer particles rich with small pores, which can, for example, be readily filled with rubber fill, e.g., in making an ICP or other heterophasic copolymer.
  • an excess of porous polymer matrix phase fines e.g., 5 vol% or more smaller than 120 ⁇ , generally formed from smaller particles such as the primary particles of the support material agglomerates, sub-primary particle debris or fines, or the leaching of solid MAO, that may result from supported catalyst debris smaller than about ⁇ or about 0.4 ⁇ , may result in fouling or plugging of the reactor, lines or equipment during the polymerization of a rubber in the presence of the porous polypropylene or vice versa, and/or in the formation of non-particulated polymer.
  • NCAs (such as including perfluoro aromatic group containing boranes, borates, or aluminates) can be supported on a support based on reported methods, such as those described in US 5,643,847; US 7,012,121 ; US 7,928,172; US 7,897,707; and the like.
  • the supported catalysts e.g., on silica with balanced PS, PSD, SA, PV, and PD, such as, for example, PS 70-100 ⁇ , SA 400-650 m 2 /g, PV 1.1-1.6 mL/g, and PD 9-12 nm, and prepared under low fragmentation conditions, are able to polymerize monomers (such as propylene) to produce matrix phase resins, and/or having relatively high porosity, e.g., greater than 30%.
  • highly porous structures can house active catalytic species to continue polymerizing additional monomers to form second phase copolymers in heterophasic copolymers such as ICP with improved physical/chemical properties.
  • ICP resins prepared from the catalysts based on MAO supported on support materials as disclosed herein have been discovered to show improved ethylene-propylene (EP) rubber loading and balanced flexibility and process ability.
  • EP ethylene-propylene
  • the mixtures of finished supported catalysts having bimodal PSD lead to controllable fill phase properties with the result that the different fill phase properties can be balanced as desired through the selection of supports with different PSD modes.
  • the PSD of the resulting matrix phase resin changes according to the PSD of the supported catalyst system, i.e., support particles in the smaller PSD mode portion produce smaller matrix phase particles relative to the larger matrix phase particles formed from the support particles in the larger PSD mode portion.
  • Optional Scavengers or Co-Activators In addition to the activator compounds, scavengers or co-activators may be used. Suitable co-activators may be selected from the group consisting of: trialkylaluminum, dialkylmagnesium, alkylmagnesium halide, and dialkylzinc.
  • Aluminum alkyl or organoaluminum compounds which may be utilized as scavengers or co-activators include, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and the like.
  • the organometallic compound used to treat the calcined support material may be a scavenger or co-activator, or may be the same as or different from the scavenger or co-activator.
  • the co-activator is selected from the group consisting of: trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-octylaluminum, trihexylaluminum, and diethylzinc (alternately the group consisting of: trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, tri-n-octylaluminum, dimethylmagnesium, diethylmagnesium, dipropylmagnesium, diisopropylmagnesium, dibutyl magnesium, diisobutylmagnesium, dihexylmagnesium, dioctylmagnesium, methylmagnesium chloride, ethylmagnesium chloride, propylmagnesium chloride, isopropylmagnesium chloride, butyl magnesium chloride, isobutylmagnesium chloride, iso
  • the supported activator is optionally treated with another organometallic compound which is also selected as the scavenger, preferably a metal alkyl such as an aluminum alkyl, to scavenge any hydroxyl or other reactive species that may be exposed by or otherwise remaining after treatment with the first organometallic compound, e.g., hydroxyl groups on surfaces exposed by fragmentation may be reacted and thereby removed by contact of the fragments with an aluminum alkyl such as triisobutylaluminum (TIBA).
  • a metal alkyl such as an aluminum alkyl
  • Useful metal alkyls which may be used according to some embodiments of the invention to treat the support material have the general formula R n -M, wherein R is C1-C40 hydrocarbyl such as C1-C12 alkyl for example, M is a metal, and n is equal to the valence of M, and may include oxophilic species such as diethyl zinc and aluminum alkyls, such as, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and the like, including combinations thereof. Then the activator/support material is contacted with a solution of the catalyst precursor compound.
  • the supported activator is generated in situ.
  • the slurry of the support material is first contacted with the catalyst precursor compound for a period of time in the range of from about 0.5 hours to about 24 hours, from about 2 hours to about 16 hours, or from about 4 hours to about 8 hours, and the slurry of the supported catalyst compound is then contacted with an organometallic-activator solution and/or organometallic-scavenger solution.
  • Catalyst Compounds Single site catalyst compounds are useful herein. Typically single site catalyst compounds are transition metal containing compound that can be activated to form a 14- or 16-electorn cationic metal center with at least one metal-carbon or one metal-hydrogen ⁇ -bond.
  • the single-site catalyst compound may be one or more metallocenes represented by the following formula:
  • each Cp is a cyclopentadienyl moiety or a substituted cyclopentadienyl moiety substituted by one or more hydrocarbyl radicals having from 1 to 20 carbon atoms;
  • R ⁇ * is a structural bridge between two Cp rings when m is 2 or 3; is a transition metal selected from groups 4 or 5;
  • Q is a hydride or a hydrocarbyl group having from 1 to 20 carbon atoms or an alkenyl group having from 2 to 20 carbon atoms, or a halogen;
  • m is 1, 2, or 3, with the proviso that if m is 2 or 3, each Cp may be the same or different;
  • k is such that k + m is equal to the oxidation state of M ⁇ , with the proviso that if k is greater than 1, each Q may be the same or different.
  • the single site catalyst precursor compound is represented by the formula:
  • each Cp is a cyclopentadienyl moiety or substituted cyclopentadienyl moiety; each R* and R" is a hydrocarbyl group having from 1 to 20 carbon atoms and may the same or different; p is 0, 1, 2, 3, or 4; q is 1, 2, 3, or 4; R ⁇ * is a structural bridge between the Cp rings imparting stereorigidity to the metallocene compound; is a group 4, 5, or 6 metal; Q is a hydrocarbyl radical having 1 to 20 carbon atoms or is a halogen; r is s minus 2, where s is the valence of M ⁇ ; wherein (CpR*q) has bilateral or pseudobilateral symmetry; R*q is an alkyl substituted indenyl radical, or tetra-, tri-, or dialkyl substituted cyclopentadienyl radical; and (CpR"p) contains a bulky group in one and only one of the distal positions; wherein
  • the single site catalyst precursor compound is represented by the formula:
  • each R in the cyclopropyls substituent is, independently, hydrogen, a substituted hydrocarbyl group, an unsubstituted hydrocarbyl group, or a halogen.
  • the M is selected from titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, and tungsten; each X is independently selected from hydrogen, halogen, hydroxy, substituted or unsubstituted Ci to Ci Q alkyl groups, substituted or unsubstituted Ci to CI Q alkoxy groups, substituted or unsubstituted C6 to C14 aryl groups, substituted or unsubstituted C6 to C14 aryloxy groups, substituted or unsubstituted C2 to CI Q alkenyl groups, substituted or unsubstituted C7 to C40 arylalkyl groups, substituted or unsubstituted C7 to C40 alkylaryl groups and substituted or unsubstituted C7 to C40 arylalkenyl groups; or optionally are joined together to form a C4 to C40 alkan
  • R ⁇ , R ⁇ , R6, R7, R ⁇ , R11, R12 and R13 are eacn selected from the group consisting of hydrogen, halogen, hydroxy, substituted or unsubstituted Ci to Ci Q alkyl groups, substituted or unsubstituted Ci to CI Q alkoxy groups, substituted or unsubstituted C6 to Ci 4 aryl groups, substituted or unsubstituted C6 to Ci 4 aryloxy groups, substituted or unsubstituted C2 to Ci Q alkenyl groups, substituted or unsubstituted C7 to C40 arylalkyl groups, substituted or unsubstituted C7 to C40 alkylaryl groups, and C7 to C40 substituted or unsubstituted arylalkenyl groups; and T is selected from:
  • R 14 , R 15 , and R 16 are each independently selected from hydrogen, halogen, Ci to C20 alkyl groups, C6 to C30 aryl groups, Ci to C20 alkoxy groups, C2 to C20 alkenyl groups, C7 to C40 arylalkyl groups, Cg to C40 arylalkenyl groups and C7 to C40 alkylaryl groups, optionally R ⁇ 4 and R ⁇ , together with the atom(s) connecting them, form a ring; and is selected from carbon, silicon, germanium, and tin; or T is represented by the formula:
  • R.1 , Rl ⁇ , R19 5 R20 ⁇ R21 R22 R23 m( [ R24 ⁇ are g ⁇ independently selected from hydrogen, halogen, hydroxy, substituted or unsubstituted Ci to Ci Q alkyl groups, substituted or unsubstituted Ci to Ci Q alkoxy groups, substituted or unsubstituted C6 to Ci 4 aryl groups, substituted or unsubstituted C6 to Ci 4 aryloxy groups, substituted or unsubstituted C2 to Ci 0 alkenyl groups, substituted or unsubstituted C7 to C40 alkylaryl groups, substituted or unsubstituted C7 to C40 alkylaryl groups and substituted or unsubstituted Cg to C40 arylalkenyl groups; optionally two or more adjacent radicals R 17 , R 18 , R 19 , R 20 , R 21 , R 22 ,
  • one catalyst compound is used, e.g., where first and second (and or third) catalyst systems are present, the catalyst compounds are not different.
  • one catalyst compound is used for polymerization of the matrix phase and the same catalyst compound is used for the polymerization of the dispersed phase.
  • two or more different catalyst compounds are present in the catalyst systems used herein. In some embodiments, two or more different catalyst systems are present in the reaction zone where the process(es) described herein occur.
  • the two transition metal compounds should be chosen such that the two are compatible.
  • a simple screening method such as by 1H or 13 ⁇ 4 NMR, known to those of ordinary skill in the art, can be used to determine which transition metal compounds are compatible.
  • the two transition metal compounds pre-catalysts may be used in any ratio.
  • Preferred molar ratios of (A) transition metal compound to (B) transition metal compound fall within the range of (A:B) 1 : 1000 to 1000: 1 , alternatively 1 : 100 to 500: 1, altematively 1 : 10 to 200: 1 , alternatively 1 : 1 to 100: 1, and altematively 1 : 1 to 75 : 1 , and alternatively 5: 1 to 50: 1.
  • the particular ratio chosen will depend on the exact pre-catalysts chosen, the method of activation, and the end product desired. In a particular embodiment, when using the two pre-catalysts, where both are activated with the same activator.
  • Useful mole percentages are 10 to 99.9 mol% A to 0.1 to 90 mol% B, altematively 25 to 99 mol% A to 0.5 to 50 mol% B, alternatively 50 to 99 mol% A to 1 to 25 mol% B, and alternatively 75 to 99 mol% A to 1 to 10 mol% B.
  • M is Zr or Hf.
  • each X is, independently, selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, ethers, and a combination thereof, (two X's may form a part of a fused ring or a ring system), preferably each X is independently selected from halides and C ⁇ to C5 alkyl groups, preferably each X is a methyl group.
  • each R ⁇ , R6 R7 R9 R11 R12 OR R13 ⁇ independently, hydrogen or a substituted hydrocarbyl group or unsubstituted hydrocarbyl group, or a heteroatom, preferably hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, or an isomer thereof.
  • each R ⁇ , R4 5 R5 R6 R ⁇ , R9, RIO ⁇ R11 R12 OR R13 j S independently selected from hydrogen, methyl, ethyl, phenyl, benzyl, cyclobutyl, cyclopentyl, cyclohexyl, naphthyl, anthracenyl, carbazolyl, indolyl, pyrrolyl, cyclopenta[Z>]thiopheneyl, fluoro, chloro, bromo, iodo and isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, methylphenyl, dimethylphenyl, ethylphenyl, diethylphenyl, propylphenyl, dipropylphenyl, butylphenyl, dibuty
  • T is a bridging group and comprises Si, Ge, or C, preferably T is dialkyl silicon or dialkyl germanium, preferably T is dimethyl silicon.
  • R'2SiCR'2SiR' 2 , R'C CR'SiR' 2 , R'2CGeR'2, R'2GeGeR'2, R'2CGeR'2CR'2,
  • R'2GeCR'2GeR' 2 , R'2SiGeR'2, R'C CR'GeR' 2 , R'B, R 2 C-BR, R 2 C-BR-CR'2, R 2 C-0-
  • T is CH 2 , CH 2 CH 2 , C(CH 3 ) 2 , SiMe 2 , SiPh 2 , SiMePh, silylcyclobutyl (Si(CH 2 )3), (Ph) 2 C, (p-(Et) 3 SiPh) 2 C, cyclopentasilylene (Si(CH 2 )4), or
  • each R ⁇ and R8 is independently, a Ci to C20 hydrocarbyl, or a Ci to C20 substituted hydrocarbyl, Ci to C20 halocarbyl, Ci to C20 substituted halocarbyl, Ci to C20 silylcarbyl, Ci to C20 substituted silylcarbyl, Ci to C20 germylcarbyl, or Ci to C20 substituted germylcarbyl substituents.
  • each R ⁇ and R ⁇ is independently, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl or an isomer thereof, preferably cyclopropyl, cyclohexyl, (1-cyclohexyl methyl) methyl, isopropyl, and the like.
  • R ⁇ and are, independently, a substituted or unsubstituted aryl group.
  • Preferred substituted aryl groups include aryl groups where a hydrogen has been replaced by a hydrocarbyl, or a substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, substituted silylcarbyl, germylcarbyl, or substituted germylcarbyl substituents, a heteroatom or heteroatom-containing group.
  • R 2 and are a Ci to C20 hydrocarbyl, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl or an isomer thereof, preferably cyclopropyl, cyclohexyl, (1-cyclohexyl methyl) methyl, or isopropyl; and R ⁇ and RlO are independently selected from phenyl, naphthyl, anthracenyl, 2-methylphenyl, 3- methylphenyl, 4-methylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5- dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4,5- tri
  • R 2 , R&, R4 and RI O ⁇ are as described in the preceding sentence and R 3 , R 5 , R 6 , R 7 , R 9 , RH , R 12 , and R 13 are hydrogen.
  • suitable MCN compounds are represented by the formula (1):
  • each A is a substituted monocyclic or poly cyclic ligand that is pi-bonded to M and optionally includes one or more ring heteroatoms selected from boron, a group 14 atom that is not carbon, a group 15 atom, or a group 16 atom, and when e is 2 each A may be the same or different, provided that at least one A is substituted with at least one cyclopropyl substituent directly bonded to any sp 2 carbon atom at a bondable ring position of the ligand,
  • each R' is, independently, hydrogen, a substituted or unsubstituted hydrocarbyl group, or a halogen
  • M is a transition metal atom having a coordination number of n and selected from group 3, 4, or 5 of the Periodic Table of Elements, or a lanthanide metal atom, or actinide metal atom
  • n is 3, 4, or 5
  • each X is a univalent anionic ligand, or two X's are joined and bound to the metal atom to form a metallocycle ring, or two X's are joined to form a chelating ligand, a diene ligand, or an alkylidene ligand.
  • the MCN compound may be represented by the formula:
  • E is J-R" x _i _y
  • J is a heteroatom with a coordination number of three from group 15 or with a coordination number of two from group 16 of the Periodic Table of Elements
  • R" is a Ci -Ci oo substituted or unsubstituted hydrocarbyl radical
  • x is the coordination number of the heteroatom J where "x-l-y" indicates the number of R" substituents bonded to J
  • T is a bridging group between A and E, A and E are bound to M, y is 0 or 1
  • A, e, M, X, and n, are as defined above.
  • the MCN compound may be represented by one of the following formulae:
  • each R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 1 1 , R 12 , R 13 , or R 14 is, independently, hydrogen, a substituted hydrocarbyl group, an unsubstituted hydrocarbyl group, or a halide, provided that in formula la and lb, at least one of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R11, 1 , R1 3 . or R ⁇ 4 .
  • R1 is a cyclopropyl substituent and in formula 2a and 2b at least one of R1, R 2 , R 3 , R 4 , R 5 , R 6 . or R 7 , is a cyclopropyl substituent; and provided that any adjacent R1 to R1 4 groups that are not a cyclopropyl substituent, may form a fused ring or multicenter fused ring system where the rings may be aromatic, partially saturated, or saturated.
  • At least one A is monocyclic ligand selected from the group consisting of substituted or unsubstituted cyclopentadienyl. heterocyclopentadienyl, and heterophenyl ligands provided that when e is one, the monocyclic ligand is substituted with at least one cyclopropyl substituent, at least one A is a polycyclic ligand selected from the group consisting of substituted or unsubstituted indenyl, fluorenyl, cyclopenta[a]naphthyl, cyclopenta[Z>]naphthyl, heteropentalenyl, heterocyclopentapentalenyl, heteroindenyl, heterofluorenyl, heterocyclopentanaphthyl, heterocyclopentaindenyl, and heterobenzocyclopentaindenyl ligands.
  • Metallocene compounds suitable for use herein may further include one or more of: dimethylsilylene-bis(2-cyclopropyl-4-phenylindenyl)zirconium di chloride; dimethylsilylene-bis(2-cyclopropyl-4-phenylindenyl)hafhium dichloride; dimethylsilylene- bis(2-methyl-4-phenylindenyl)zirconium dichloride; dimethylsilylene-bis(2-methyl-4- phenylindenyl)hafnium dichloride; dimethylsilylene-bis(2-methyl-4- orthobiphenylindenyl)hafnium dichloride; dimethylsilylene-bis(2-methyl-4- orthobiphenylindenyl)zirconium dichloride; dimethylsilylene-(2-cyclopropyl-4- orthobiphenylindenyl)(2-methyl-4-3',5'-di-t- butylphenylindenyl)haihium dichlor
  • the molar ratio of rac to meso in the catalyst precursor compound is from 1 : 1 to 100: 1 , preferably 5: 1 to 90: 1 , preferably 7: 1 to 80: 1, preferably 5 : 1 or greater, or 7: 1 or greater, or 20: 1 or greater, or 30: 1 or greater, or 50: 1 or greater.
  • the MCN catalyst comprises greater than 55 mol% of the racemic isomer, or greater than 60 mol% of the racemic isomer, or greater than 65 mol% of the racemic isomer, or greater than 70 mol% of the racemic isomer, or greater than 75 mol% of the racemic isomer, or greater than 80 mol% of the racemic isomer, or greater than 85 mol% of the racemic isomer, or greater than 90 mol% of the racemic isomer, or greater than 92 mol% of the racemic isomer, or greater than 95 mol% of the racemic isomer, or greater than 98 mol% of the racemic isomer, based on the total amount of the racemic and meso isomer formed.
  • the bridged bis(indenyl)metallocene transition metal compound formed consists essentially of the racemic isomer.
  • Amounts of rac and meso isomers are determined by proton NMR. 1H NMR data are collected at 23°C in a 5 mm probe using a 400 MHz Bruker spectrometer with deuterated methylene chloride. (Note that some of the examples herein use deuterated benzene, but for purposes of the claims, methylene chloride shall be used.) Data is recorded using a maximum pulse width of 45°, 5 seconds between pulses and signal averaging 16 transients. The spectrum is normalized to protonated methylene chloride in the deuterated methylene chloride, which is expected to show a peak at 5.32 ppm.
  • two or more different MCN catalyst precursor compounds are present in the catalyst system used herein. In some embodiments, two or more different MCN catalyst precursor compounds are present in the reaction zone where the process(es) described herein occur.
  • the two transition metal compounds should be chosen such that the two are compatible.
  • a simple screening method such as by 1H or NMR, known to those of ordinary skill in the art, can be used to determine which transition metal compounds are compatible.
  • transition metal compounds it is preferable to use the same activator for the transition metal compounds, however, two different activators, such as two non-coordination anions, a non- coordinating anion activator and an alumoxane, or two different alumoxanes can be used in combination. If one or more transition metal compounds contain an X ligand which is not a hydride, hydrocarbyl, or substituted hydrocarbyl, then the alumoxane (or other alkylating agent) is typically contacted with the transition metal compounds prior to addition of the non- coordinating anion activator.
  • two different activators such as two non-coordination anions, a non- coordinating anion activator and an alumoxane, or two different alumoxanes can be used in combination. If one or more transition metal compounds contain an X ligand which is not a hydride, hydrocarbyl, or substituted hydrocarbyl, then the alumoxane (or other alkylating agent
  • the two transition metal compounds may be used in any ratio.
  • Preferred molar ratios of (A) transition metal compound to (B) transition metal compound fall within the range of (A:B) 1 : 1000 to 1000: 1 , alternatively 1 : 100 to 500: 1, alternatively 1 : 10 to 200: 1 , alternatively 1 : 1 to 100: 1, alternatively 1 : 1 to 75 : 1, and alternatively 5 : 1 to
  • useful mole percentages are 10 to 99.9 mol% A to 0.1 to 90 mol% B, alternatively 25 to 99 mol% A to 0.5 to 50 mol% B, alternatively 50 to 99 mol% A to 1 to 25 mol% B, and alternatively 75 to 99 mol% A to 1 to 10 mol% B.
  • the single-site catalyst precursor compound useful herein may be represented by the formula (I):
  • M is a group 4 transition metal (preferably Hf, Zr, or Ti, preferably Hf or Zr);
  • ⁇ and X 2 are, independently, a univalent Ci to C20 hydrocarbyl radical, a Ci to C20 substituted hydrocarbyl radical, a heteroatom or a heteroatom-containing group, or ⁇ and X 2 join together to form a C4 to C ⁇ 2 cyclic or poly cyclic ring structure (preferably benzyl, methyl, ethyl, chloro, bromo, and the like);
  • each R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 1 0 is, independently, a hydrogen, a Ci to C40 hydrocarbyl radical, a substituted Ci to C40 hydrocarbyl radical, a heteroatom, a heteroatom-containing group (alternately each R! , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 may be a functional group comprising of elements from groups 13 to 17), or two or more of
  • R 1 to R 10 may independently join together to form a C4 to C52 cyclic or poly cyclic ring structure, or a combination thereof (preferably H, methyl, ethyl, propyl and the like);
  • Q is a neutral donor group, preferably a neutral donor group comprising at least one atom from group 15 or 16;
  • J is a C7 to C60 fused poly cyclic (e.g., having at least 2 ring structures) group, which, optionally, comprises up to 20 atoms from groups 15 and 16, where at least one ring is aromatic and where at least one ring, which may or may not be aromatic, has at least 5 members (preferably J comprises a five-membered ring (which may be saturated or aromatic) that is fused to at least one other cyclic group and is preferably bound to the rest of the ligand through the five-membered ring); G is, independently, as defined for J, a hydrogen, a Ci to C6Q hydrocarbyl radical, a substituted hydrocarbyl radical, a heteroatom, or a heteroatom-containing group, or may independently form a C4 to C6Q cyclic or polycyclic ring structure with R6, R 7 5 or R 8 or a combination thereof; and
  • Y is a divalent Ci to C20 hydrocarbyl or a substituted divalent hydrocarbyl group.
  • the catalyst compound may be represented by either formula (II)
  • Q* is a group 15 or 16 atom (preferably N, O, S, or P);
  • z is 0 or 1;
  • J* is CR" or N
  • G* is CR" or N
  • R26, and R 2 ? is, independently, as defined for R1 above with respect to formula (I).
  • M may be Hf, Ti, or Zr.
  • each of ⁇ and is independently selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms (such as methyl, ethyl, ethenyl, and isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl), hydrides, amides, alkoxides having from 1 to 20 carbon atoms, sulfides, phosphides, halides, sulfoxides, sulfonates, phosphonates, nitrates
  • Y is a divalent Ci to C40 hydrocarbyl radical or divalent substituted hydrocarbyl radical comprising a portion that comprises a linker backbone comprising from 1 to 18 carbon atoms linking or bridging between Q and N.
  • Y is a divalent Ci to C40 hydrocarbyl or substituted hydrocarbyl radical comprising a portion that comprises a linker backbone comprising from 1 to 18 carbon atoms linking Q and N wherein the hydrocarbyl comprises O, S, S(O), S(0) 2 , Si(R) 2 , P(R), N or N(R), wherein each R is independently a Ci to Ci 8 hydrocarbyl.
  • Y is selected from the group consisting of ethylene (-CH 2 CH 2 -) and 1,2-cyclohexylene.
  • Y is -CH2CH2CH2- derived from propylene.
  • Y is selected form the group consisting of Ci to C20 alkyl groups, such as divalent methyl, ethyl, ethenyl and isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and eicosyl.
  • Ci to C20 alkyl groups such as divalent methyl, ethyl, ethenyl and isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, te
  • each R 1 , R 2 , R 3 , R 4 , R5, R6 5 R7 R8 R9 M( [ R10 j S; independently, a hydrogen, a Ci to C20 hydrocarbyl radical, a substituted Ci to C20 hydrocarbyl radical, or two or more of R1 to may independently join together to form a C4 to C62 cyclic or poly cyclic ring structure, or a combination thereof.
  • R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , and R 27 is, independently, hydrogen, a halogen, a Ci to C30 hydrocarbyl radical, a Ci to C20 hydrocarbyl radical, or a Ci to CI Q hydrocarbyl radical (such as methyl, ethyl, ethenyl and isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl).
  • a halogen such as methyl, ethyl, ethenyl and isomers of propyl, butyl
  • R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , and R 27 is, independently, a substituted Ci to C 30 hydrocarbyl radical, a substituted Ci to C20 hydrocarbyl radical, or a substituted Ci to C I Q hydrocarbyl radical (such as 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl, 4- methoxyphenyl, 4-trifluoromethylphenyl, 4-dimethylaminophenyl, 4-trimethylsilylphenyl, 4- triethylsilylphenyl, trifluoromethyl, fluoromethyl, trichloromethyl, chloromethyl, mesityl, methylthio, phenylthio, (trimethylsilyl)methyl, and (triphenylsilyl)methyl).
  • a substituted Ci to C 30 hydrocarbyl radical such as 4-fluorophenyl, 4-chlorophenyl, 4-bromoph
  • R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , and R 27 is a methyl radical, a fluoride, chloride, bromide, iodide, methoxy, ethoxy, isopropoxy, trifluoromethyl, dimethylamino, diphenylamino, adamantyl, phenyl, pentafluo henyl, naphthyl, anthracenyl, dimethylphosphanyl, diisopropylphosphanyl, diphenylphosphanyl, methylthio, and phenylthio or a combination thereof.
  • Q* is N, O, S, or P, preferably N, O, or S, preferably N or O, preferably N.
  • Q* is a group 15 atom
  • z is 1, and when Q* is a group 16 atom, z is 0.
  • Q is preferably a neutral donor group comprising at least one atom from group 15 or 16, preferably Q is NR'2, OR, SR', PR'2, where R is as defined for R 1 (preferably R is methyl, ethyl, propyl, isopropyl, phenyl, cyclohexyl or linked together to form a five-membered ring such as pyrrolidinyl or a six-membered ring such as piperidinyl), preferably the -(-Q-Y-)- fragment can form a substituted or unsubstituted heterocycle which may or may not be aromatic and may have multiple fused rings (for example, see compound 7-Zr, 7-Hf in the examples below).
  • Q is preferably an amine, ether, or pyridine.
  • G* and J* are the same, preferably G* and J* are N, alternately G* and J* are CR'", where each R'" is H or a Ci to Ci 2 hydrocarbyl or substituted hydrocarbyl (such as methyl, ethyl, ethenyl and isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, trifluoromethylphenyl, tolyl, phenyl, methoxyphenyl, tertbutylphenyl, fluorophenyl, diphenyl, dimethylaminophenyl, chlorophenyl, bromophenyl, iodophenyl, (trimethylsilyl)phenyl, (triethylsily
  • G and J are the same, preferably G and J are carbazolyl, substituted carbazolyl, indolyl, substituted indolyl, indolinyl, substituted indolinyl, imidazolyl, substituted imidazolyl, indenyl, substituted indenyl, indanyl, substituted indanyl, fluorenyl, or substituted fluorenyl.
  • G and J are different.
  • M is Zr or Hf
  • X 1 and X 2 are benzyl radicals; R1 is a methyl radical; R 2 through R 2 ⁇ are hydrogen; Y is ethylene (-CH 2 CH 2 -), Q*, G* and J* are N, and Rz* is methyl radical.
  • M is Zr or Hf
  • X 1 and X 2 are benzyl radicals; R ⁇ and R ⁇ are methyl radicals; R1 through R ⁇ , R ⁇ through
  • R6 and R ⁇ through RI O are hydrogen; and Y is ethylene, (-CH2CH2-), Q is an N-containing group, G and J are carbazolyl or fluorenyl. In a preferred combination, G and J are carbazolyl and Q is an amine group; or, G and J are substituted fluorenyl and Q is an amine, ether or pyridine.
  • the catalyst compound may also be represented by either formulas (IV) and (V) below:
  • Y is a Ci to C3 divalent hydrocarbyl
  • Q1 is NR'2, OR', SR', PR'2, where R is as defined for R1 with respect to formulas (I), (II), and (III) above (preferably R is methyl, ethyl, propyl, isopropyl, phenyl, cyclohexyl or linked together to form a five-membered ring such as pyrrolidinyl or a six-membered ring such as piperidinyl), alternately the -(-Q-Y-)- fragment can form a substituted or unsubstituted heterocycle which may or may not be aromatic and may have multiple fused rings, M is Zr, Hf or Ti and each X is, independently, as defined for ⁇ above with respect to formulas (I), (II), and (III), preferably each X is benzyl, methyl, ethyl, chloride, bromide, or alkoxide.
  • Chain Transfer Agents This invention further relates to methods to polymerize olefins using the above complex in the presence of a chain transfer agent ("CTA").
  • CTA can be any desirable chemical compound such as those disclosed in WO 2007/130306.
  • the CTA is selected from Group 2, 12, or 13, alkyl or aryl compounds; preferably zinc, magnesium or aluminum alkyls or aryls; preferably where the alkyl is a Ci to C30 alkyl, alternately a C2 to C20 alkyl, alternately a C3 to C 12 alkyl, typically selected independently from methyl, ethyl, propyl, butyl, isobutyl, tertbutyl, pentyl, hexyl, cyclohexyl, phenyl, octyl, nonyl, decyl, undecyl, and dodecyl; e.g., dialkyl zinc compounds, where the alkyl is selected independently from methyl, ethyl, propyl, butyl, isobutyl, tertbutyl, pentyl, hexyl, cyclohexyl, and phenyl, where di-ethylzin
  • Useful CTAs are typically present at from 10, or 20, or 50, or 100, equivalents to 600, or 700, or 800, or 1,000, equivalents relative to the catalyst component.
  • the CTA is preset at a catalyst complex-to-CTA molar ratio of from about 1 :3,000 to 10: 1; alternatively 1 :2,000 to 10: 1 ; alternatively 1 : 1,000 to 10: 1; alternatively, 1 :500 to 1 : 1 ; alternatively 1 :300 to 1 : 1 ; alternatively 1 :200 to 1 : 1; alternatively 1 : 100 to 1 : 1; alternatively 1 :50 to 1 : 1; and/or alternatively 1 : 10 to 1 : 1.
  • Monomers useful herein include substituted or unsubstituted C2 to
  • C40 alpha olefins preferably C2 to C20 alpha olefins, preferably C2 to C12 alpha olefins, preferably ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene and isomers thereof.
  • the monomer comprises propylene and optional comonomer(s) comprising one or more of ethylene or C4 to C40 olefins, preferably C4 to C20 olefins, or preferably C6 to C12 olefins.
  • the C4 to C40 olefin monomers may be linear, branched, or cyclic.
  • the C4 to C40 cyclic olefins may be strained or unstrained, monocyclic or polycyclic, and may optionally include heteroatoms and/or one or more functional groups.
  • the monomer is propylene and no comonomer is present.
  • Exemplary C2 to C40 olefin monomers and optional comonomers include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, norbomadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, substituted derivatives thereof, and isomers thereof, preferably hexene, heptene, octene, nonene, decene, dodecene, cyclooctene, 1,5-cyclooctadiene, l-hydroxy-4-cyclooctene, 1- acetoxy-4-cyclooctene, 5-
  • one or more dienes are present in the polymer produced herein at up to 10 weight %, preferably at 0.00001 to 1.0 weight %, preferably 0.002 to 0.5 weight %, even more preferably 0.003 to 0.2 weight %, based upon the total weight of the composition.
  • 500 ppm or less of diene is added to the polymerization, preferably 400 ppm or less, or preferably 300 ppm or less.
  • at least 50 ppm of diene is added to the polymerization, or 100 ppm or more, or 150 ppm or more.
  • Preferred diolefin monomers useful in this invention include any hydrocarbon structure, preferably C4 to C30, having at least two unsaturated bonds, wherein at least two of the unsaturated bonds are readily incorporated into a polymer by either a stereospecific or a non-stereospecific catalyst(s). It is further preferred that the diolefin monomers be selected from alpha, omega-diene monomers (i.e., di-vinyl monomers). More preferably, the diolefin monomers are linear di-vinyl monomers, most preferably those containing from 4 to 30 carbon atoms.
  • Examples of preferred dienes include butadiene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene, decadiene, undecadiene, dodecadiene, tridecadiene, tetradecadiene, pentadecadiene, hexadecadiene, heptadecadiene, octadecadiene, nonadecadiene, icosadiene, heneicosadiene, docosadiene, tricosadiene, tetracosadiene, pentacosadiene, hexacosadiene, heptacosadiene, octacosadiene, nonacosadiene, triacontadiene, particularly preferred dienes include 1,6-heptadiene, 1,7-octadiene, 1,8- nonadiene, 1,9-decadiene,
  • Preferred cyclic dienes include cyclopentadiene, vinylnorbomene, norbomadiene, ethylidene norbornene, divinylbenzene, dicyclopentadiene or higher ring containing diolefins with or without substituents at various ring positions.
  • the polymerization or copolymerization is carried out using olefins such as ethylene, propylene, 1-butene, 1-hexene, 4-methyl-l-pentene, and 1-octene, vinylcyclohexane, norbornene and norbomadiene.
  • olefins such as ethylene, propylene, 1-butene, 1-hexene, 4-methyl-l-pentene, and 1-octene, vinylcyclohexane, norbornene and norbomadiene.
  • propylene and ethylene are polymerized.
  • the monomers comprise 0 wt% diene monomer in any stage, preferably in all stages.
  • the comonomer(s) are present in the final propylene polymer composition at less than 50 mol%, preferably from 0.5 to 45 mol%, preferably from 1 to 30 mol%, preferably from 3 to 25 mol%, preferably from 5 to 20 mol%, preferably from 7 to 15 mol%, with the balance of the copolymer being made up of the main monomer (e.g., propylene).
  • the main monomer e.g., propylene
  • the polymer produced in stage A (and/or stages Al and A2, e.g., when polymer A is bimodal) is iPP, preferably isotactic homopolypropylene and the polymer produced in stage B comprises propylene and from 0.5 to 50 mol% (preferably from 0.5 to 45 mol%, preferably from 1 to 30 mol%, preferably from 3 to 25 mol%, preferably from 5 to 20 mol%, preferably from 7 to 15 mol%, with the balance of the copolymer being made up of propylene) of ethylene or C4 to C20 alpha olefin, preferably ethylene and butene, hexene, and/or octene.
  • 0.5 to 50 mol% preferably from 0.5 to 45 mol%, preferably from 1 to 30 mol%, preferably from 3 to 25 mol%, preferably from 5 to 20 mol%, preferably from 7 to 15 mol%, with the balance of the copolymer being made up of propylene
  • stage A may comprise a plurality of substages, e.g., stage Al, stage A2, etc. As used herein, stage A refers to all of the substages.
  • the polymer produced in stage Al is iPP, preferably isotactic homopolypropylene, and the polymer produced in stage A2 is an iPP.
  • the polymer produced in stage Al is iPP, preferably isotactic homopolypropylene
  • the polymer produced in stage A2 is an iPP
  • the polymer produced in stage B comprises propylene and from 0.5 to 50 mol% (preferably from 0.5 to 45 mol%, preferably from 1 to 30 mol%, preferably from 3 to 25 mol%, preferably from 5 to 20 mol%, preferably from 7 to 15 mol%, with the balance of the copolymer being made up of propylene) of ethylene and butene, or ethylene and hexene, or ethylene and octene.
  • the polymer compositions according to embodiments of the invention may be prepared using polymerization processes such as a two-stage process in two reactors or a three or more stage process in three or more reactors, although it is also possible to produce these compositions in a single reactor.
  • each stage may be independently carried out in either the gas, solution, or liquid slurry phase.
  • the first stage may be conducted in the gas phase, and the second in liquid slurry, or vice versa, and the, optional, third stage in gas or slurry phase.
  • each phase may be the same in the various stages.
  • the polymer compositions of this invention can be produced in multiple reactors, preferably two or three, operated in series, where component A (including components Al and A2 if present) is preferably polymerized first in a gas phase or liquid slurry process.
  • Component B (the polymeric material produced in the presence of component A) is preferably polymerized in a second reactor such as a gas phase or slurry phase reactor.
  • component A can be made in at least two reactors, stages Al and A2, in order to obtain fractions with different properties, e.g., varying molecular weights, polydispersities, melt flow rates, or the like, and therefore component B can be made in the third reactor in the presence of A (i.e., Al +A2).
  • stage is defined as that portion of a polymerization process during which one component of the in-reactor composition, component A (including components Al and A2 if present) or component B (or component C, if another stage is present), is produced.
  • component A including components Al and A2 if present
  • component B or component C, if another stage is present
  • One or multiple reactors may be used during each stage.
  • the same or different polymerization process may be used in each stage.
  • component A and/or Stage A may be referred to herein below as iPP and the stage producing the polypropylene
  • component Al and/or Stage Al may be referred to herein below as the first iPP mode and the stage producing the first polypropylene mode
  • component A2 and/or Stage A2 may be referred to herein below as the second iPP mode and the stage producing the second polypropylene mode
  • component B and/or Stage B may be referred to herein below as the rubber and the stage producing the rubber, it being understood that the polymers may be produced in any order or in the same reactor and/or series of reactors.
  • the stages of the processes of this invention can be carried out in any manner known in the art, in solution, in suspension or in the gas phase, continuously or batch wise, or any combination thereof, in one or more steps.
  • Homogeneous polymerization processes are useful.
  • a homogeneous polymerization process is defined to be a process where at least 90 wt% of the product is soluble in the reaction media.
  • a bulk homogeneous process is also useful, wherein for purposes herein a bulk process is defined to be a process where monomer concentration in all feeds to the reactor is 70 volume % or more.
  • no solvent or diluent may be present or added in the reaction medium, except for the small amounts used as the carrier for the catalyst system or other additives, or amounts typically found with the monomer; e.g., propane in propylene as is known in the art.
  • the term "gas phase polymerization” refers to the state of the monomers during polymerization, where the "gas phase” refers to the vapor state of the monomers.
  • a slurry process is used in one or more stages.
  • slurry polymerization process means a polymerization process where a supported catalyst is employed and monomers are polymerized on the supported catalyst particles, and at least 95 wt% of polymer products derived from the supported catalyst are in granular form as solid particles (not dissolved in the diluent).
  • Gas phase polymerization processes are particularly preferred and can be used in one or more stages.
  • an inert solvent or diluent may be used, for example, the polymerization may be carried out in suitable diluents/solvents.
  • suitable diluents/solvents for polymerization include non-coordinating, inert liquids.
  • Examples include straight and branched-chain hydrocarbons, such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof, such as can be found commercially (ISOPARTM); perhalogenated hydrocarbons, such as perfluorinated C4.1 0 alkanes, chlorobenzene, and aromatic and alkylsubstituted aromatic compounds, such as benzene, toluene, mesitylene, and xylene.
  • hydrocarbons such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane,
  • Suitable diluents/solvents also include liquid olefins which may act as monomers or comonomers including ethylene, propylene, 1-butene, 1-hexene, 1-pentene, 3-methyl-l- pentene, 4-methyl- 1-pentene, 1-octene, 1-decene, and mixtures thereof.
  • aliphatic hydrocarbon solvents are used as the solvent, such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof.
  • the diluent/solvent is not aromatic, preferably aromatics are present in the diluent/solvent at less than 1 wt%, preferably less than 0.5 wt%, preferably less than 0 wt% based upon the weight of the diluents/solvents. It is also possible to use mineral spirit or a hydrogenated diesel oil fraction as a solvent. Toluene may also be used. The polymerization is preferably carried out in the liquid monomer(s). If inert solvents are used, the monomer(s) is(are) typically metered in gas or liquid form.
  • the feed concentration of the monomers and comonomers for the polymerization is 60 vol% solvent or less, or 40 vol% or less, or 20 vol% or less, based on the total volume of the feedstream.
  • the polymerization is run in a bulk process.
  • polymerizations can be run at any temperature and/or pressure suitable to obtain the desired polymers.
  • Typical temperatures and/or pressures in any stage include a temperature greater than 30°C, or greater than 50°C, or greater than 65°C, or greater than 70°C, or greater than 75°C, alternately less than 300°C, or less than 200°C, or less than 150°C, or less than 140°C; and/or at a pressure in the range of from 100 kPa to 20 MPa, about 0.35 MPa to about 10 MPa, or from about 0.45 MPa to about 6 MPa, or from about 0.5 MPa to about 5 MPa.
  • polymerization in any stage may include a reaction run time up to 300 minutes, or in the range of from about 5 to 250 minutes, or from about 10 to 120 minutes.
  • the polymerization time for all stages is from 1 to 600 minutes, or 5 to 300 minutes, or from about 10 to 120 minutes.
  • Hydrogen and/or other CTA's may be added to one, two or more reactors or reaction zones.
  • hydrogen and/or CTA are added to control Mw and MFR of the polymer produced.
  • the overall pressure in the polymerization in each stage is at least about 0.5 bar, or at least about 2 bar, or at least about 5 bar.
  • pressures higher than about 100 bar, e.g., higher than about 80 bar and, in particular, higher than about 64 bar may not be utilized.
  • hydrogen is present in the polymerization reaction zone at a partial pressure of from 0.001 to 100 psig (0.007 to 690 kPa), or from 0.001 to 50 psig (0.007 to 345 kPa), or from 0.01 to 25 psig (0.07 to 172 kPa), or 0.1 to 10 psig (0.7 to 70 kPa).
  • hydrogen, and/or CTA may be added to the first reactor, a second, or third, or subsequent reactor, or any combination thereof.
  • hydrogen may be added to the first stage, and/or the second stage, and/or the third stage.
  • hydrogen is added in a higher concentration to the second stage as compared to the first stage. In an alternate embodiment of the invention, hydrogen is added in a higher concentration to the first stage as compared to the second stage.
  • stage hydrogen addition in impact copolymer production please see US 2015-0119537, incorporated herein by reference.
  • Polymerization processes of this invention can be carried out in each of the stages in a batch, semi-batch, or continuous mode. If two or more reactors (or reaction zones) are used, preferably they are combined so as to form a continuous process. In embodiments of the invention, polymerizations can be run at any temperature and/or pressure suitable to obtain the desired polymers. In embodiments of the invention, the process to produce the propylene polymer composition is continuous.
  • the catalyst systems used in the stages may be the same or different and are preferably the same.
  • the catalyst system used in the first stage(s) to produce the matrix is transferred with the polymerizate, where it is contacted with additional monomer to form the dispersed phase, and thus the final heterophasic polymer composition.
  • catalyst is provided to one, two or all stages of polymerization.
  • the first stage(s) to produce matrix polymer produces a homopolymer of ethylene or propylene or copolymer of propylene with less than 3 wt% ethylene or ethylene with less than 15 wt% propylene
  • the stage to produce the dispersed phase produces a copolymer of ethylene-propylene, ethylene-butene, ethylene- hexene, ethylene-octene, ethylene-propylene, ethylene-propylene-butene, ethylene- propylene-hexene, or ethylene-propylene-octene, with or without an optional diene.
  • scavenger such as trialkyl aluminum
  • scavenger is present at a molar ratio of scavenger metal to transition metal of 0: 1, alternately less than 100: 1, or less than 50: 1, or less than 15: 1, or less than 10: 1, or less than 1 : 1, or less than 0.1 : 1.
  • additives may also be used in the polymerization in any stage, as desired, such as one or more scavengers, promoters, modifiers, hydrogen, CTAs other than or in addition to hydrogen (such as diethyl zinc), reducing agents, oxidizing agents, aluminum alkyls, or silanes, or the like.
  • the dispersed phase (such as EPR in an iPP/EPR ICP) formed from a one-reactor one-catalyst polymerization process has a bimodal Mw/Mn. This is determined by extracting the dispersed phase (as described in the Experimental section below) testing the extracted material by GPC-4D.
  • the dipsersed phase in the heterophasic polymer compositions produced herein has a bimodal MWD as determined by GPC-4D.
  • the propylene polymer matrix phase advantageously has less than 200 regio defects (defined as the sum of 2,1-erythro and 2,1- threo insertions, and 3,1-isomerizations) per 10,000 propylene units, alternatively more than 5, 10, or 15 and less than 200 regio defects per 10,000 propylene units, alternatively more than 17 and less than 175 regio defects per 10,000 propylene units, alternatively more than 20 or 30 or 40, but less than 200 regio defects, alternatively less than 150 regio defects per 10,000 propylene units.
  • regio defects defined as the sum of 2,1-erythro and 2,1- threo insertions, and 3,1-isomerizations
  • regio defects and polypropylene microstructure are determined by l ⁇ C-NMR spectroscopy as described at Paragraph [0233]- [0237] page 49-50 of PCT/US2016/030036, which claims priority to USSN 62/171,602, filed June 5, 2015.
  • the propylene polymer matrix phase can have a melting point (Tm, DSC peak second melt) of at least 145°C, or at least 150°C, or at least 152°C, or at least 155°C, or at least 160°C, or at least 165°C, preferably from about 145°C to about 175°C, about 150°C to about 170°C, or about 152°C to about 165°C.
  • Tm melting point
  • the propylene polymer matrix phase can have a 1% secant flexural modulus from a low of about 1,000 MP a, about 1,100 MP a, about 1,200 MPa, about 1,250 MPa, about 1,300 MPa, about 1,400 MPa, or about 1,500 MPa to a high of about 1,800 MPa, about 2,100 MPa, about 2,600 MPa, or about 3,000 MPa, as measured according to ASTM D790 (A, 1.0 mm/min), preferably from about 1,100 MPa to about 2,200 MPa, about 1,200 MPa to about 2,000 MPa, about 1,400 MPa to about 2,000 MPa, or about 1500 MPa or more.
  • ASTM D790 ASTM D790
  • 1% Secant flexural modulus is determined by using an ISO 37-Type 3 bar, with a crosshead speed of 1.0 mm/min and a support span of 30.0 mm via an Instron machine according to ASTM D790 (A, 1.0 mm/min).
  • the propylene polymer matrix phase can have a melt flow rate (MFR, ASTM D1238, 230°C, 2.16 kg) from a low of about 1 dg/min to about 300 dg/min, about 5 dg/min to about 150 dg/min, about 10 dg/min to about 100 dg/min, or about 20 dg/min to about 60 dg/min.
  • MFR melt flow rate
  • the propylene polymer matrix phase can have an Mw (as measured by GPC-4D) from 50,000 to 1,000,000 g/mol, alternately from 80,000 to 1,000,000 g/mol, alternately from 100,000 to 800,000 g/mol, alternately from 200,000 to 600,000 g/mol, alternately from 300,000 to 550,000 g/mol, alternately from 330,000 to 500,000 g/mol.
  • Mw as measured by GPC-4D
  • the propylene polymer matrix phase can have an Mw/Mn (as measured by GPC-4D) of greater than 1 to 20, alternately 3 to 10.
  • the propylene polymer is heterophasic impact copolymer.
  • the ICP comprises a blend of iPP (component A or the composition produced after stage Al and optionally stage A2 described above), preferably having a T m of 120°C or more, with component B (a propylene polymer with a glass transition temperature (Tg) of -30°C or less and/or an ethylene polymer).
  • component A refers to the matrix polymer
  • component B refers to the dispersed polymer.
  • component A comprises 60 to 95 wt% of the ICP, and component B 5 to 40 wt%, by total weight of components A and B.
  • the iPP of component A may have any one, combination, or all of the properties of any of the iPP embodiments disclosed herein, and/or may be made by any of the processes described herein for producing iPP.
  • component B is an ethylene copolymer or an EP rubber, preferably with a Tg of -30°C or less.
  • the ICP comprises only two monomers: propylene and a single comonomer chosen from among ethylene and C4 to Cg alpha-olefins, preferably ethylene, butene, hexene or octene, more preferably ethylene.
  • the ICP comprises three monomers: propylene and two comonomers chosen from among ethylene and C4 to Cg alpha-olefins, preferably two selected from ethylene, butene, hexene, and octene.
  • component A has a T m of 120°C or more, or 130°C or more, or 140°C or more, or 150°C or more, or
  • component B has a Tg of -30°C or less, or -40°C or less, or
  • the component B has a heat of fusion (Hi) of 90°C or less (as determined by DSC).
  • Hi heat of fusion
  • the component B has an Hf of 70°C or less, preferably 50°C or less, preferably 35°C or less.
  • the impact polymers produced herein may have an Mw (as measured by GPC-4D) from 50,000 to 1,000,000 g/mol, alternately from 80,000 to 800,000 g/mol, alternately 100,000 to 600,000 g/mol, alternately 100,000 to 500,000 g/mol, alternately from 100,000 to 300,000 g/mol, or alternately from 100,000 to 2,500,000 g/mol.
  • the dispersed phase has a multimodal molecular weight distribution, e.g., a bimodal molecular weight distribution.
  • the filler rubber, e.g., EPR comprise one mode peaked at a molecular weight of less than 150,000 g/mol, e.g., 10,000 - 150,000 g/mol, or 20,000 - 130,000 g/mol, or 20,000 - 120,000 g/mol, or 30,000 - 100,000 g/mol, and one mode centered at a molecular weight of greater than 50,000 g/mol, e.g., 50,000 - 1,000,000 g/mol, or 50,000 - 500,000 g/mol, or 70,000 - 300,000 g/mol, or 80,000 - 200,000 g/mol.
  • the impact copolymer has a matrix phase comprising primarily a propylene polymer composition having a melting point (T m ) of 100°C or more, an MWD of 5 or more and a multimodal MWD, and the dispersed or fill phase comprises primarily a polyolefin having a Tg of -20°C or less.
  • the matrix phase comprises primarily homopolymer polypropylene (hPP) and/or random copolymer polypropylene (RCP) with relatively low comonomer content (less than 5 wt%), and has a melting point of 110°C or more (preferably 120°C or more, preferably 130°C or more, preferably 140°C or more, preferably 150°C or more, preferably 160°C or more).
  • hPP homopolymer polypropylene
  • RCP random copolymer polypropylene
  • the dispersed or fill phase comprises primarily one or more ethylene or propylene copolymer(s) with relatively high comonomer content (at least 5 wt%, preferably at least 10 wt%); and has a Tg of -30°C or less (preferably -40°C or less, preferably -50°C or less).
  • An "in-situ ICP” is a specific type of ICP which is a reactor blend of the (A) and (B) components of an ICP, meaning (A) optionally (A1&A2) and (B) were made in separate reactors (or reactions zones) physically connected in series, with the effect that an intimately mixed final product is obtained in the product exiting the final reactor (or reaction zone).
  • the components are produced in a sequential polymerization process, wherein (Al) is produced in a first reactor then is transferred to a second reactor where optionally (A2) is produced in a second reactor (or the combined A1&A2 components may be produced in one reactor), and the product is transferred to another reactor where (B) is produced and incorporated into the matrix.
  • a component (C) produced as a byproduct during this process, comprising primarily the non-propylene comonomer (e.g., (C) will be an ethylene polymer if ethylene is used as the comonomer).
  • an in-situ ICP is sometimes identified as “reactor-blend ICP” or a “block copolymer,” although the latter term is not strictly accurate since there is at best only a very small fraction of molecules that are (A)-(C) copolymers.
  • all of the polymerizations to make the ICP occur in the same reactor or reaction zone, preferably using one catalyst.
  • the polymer composition produced herein is an in-situ-ICP, preferably produced in one reactor or reaction zone, preferably using one catalyst.
  • ex-situ ICP is a specific type of ICP which is a physical blend of (A) and optionally (A1&A2) and (B), meaning (A) (A1&A2) and/or (B) were synthesized independently and then subsequently blended typically using a melt-mixing process, such as an extruder.
  • An ex-situ ICP is distinguished by the fact that (A) and/or (A1&A2), and (B) are collected in solid form after exiting their respective synthesis processes, and then combined; whereas for an in-situ ICP, (A) optionally (A1&A2) and (B) are combined within a common synthesis process and only the blend is collected in solid form.
  • the impact copolymer (the combination of A, optional A1&A2, and B components) advantageously has more than 15 and less than 200 regio defects (defined as the sum of 2,1-erythro and 2,1-threo insertions, and 3,1- isomerizations) per 10,000 propylene units, alternatively more than 17 and less than 175 regio defects per 10,000 propylene units, alternatively more than 20, or 30, or 40, but less than 200 regio defects, alternatively less than 150 regio defects per 10,000 propylene units.
  • regio defects defined as the sum of 2,1-erythro and 2,1-threo insertions, and 3,1- isomerizations
  • the regio defects are determined using NMR spectroscopy as described below.
  • the impact copolymers produced herein preferably have a total propylene content of at least 50 wt%, at least 75 wt%, at least 80 wt%, at least 85 wt%, at least 90 wt%, or at least 95 wt%, or 100 wt% based on the weight of the propylene polymer composition.
  • the impact copolymers produced herein preferably have a total comonomer content from about 0.1 wt% to about 75 wt%, about 1 wt% to about 35 wt%, about 2 wt% to about 30 wt%, about 3 wt% to about 25 wt%, or about 5 wt% to about 20 wt%, based on the total weight of the propylene polymer compositions, with the balance being propylene.
  • the impact copolymers produced herein preferably have a heat of fusion (Hf,
  • DSC second heat of 60 J/g or more, 70 J/g or more, 80 J/g or more, 90 J/g or more, about 95 J/g or more, or about 100 J/g or more.
  • the impact polymers produced herein have a 1% secant fiexural modulus greater than about 300 MPa, or 500 MPa, or 700 MPa, or 1,000 MPa, or 1,500 MPa, or 2,000 MPa, or from about 300 MPa to about 3,000 MPa, about 500 MPa to about 2,500 MPa, about 700 MPa to about 2,000 MPa, or about 900 MPa to about 2,000 MPa, as measured according to ASTM D790 (A, 1.0 mm/min).
  • Composition Distribution Breadth index is a measure of the composition distribution of monomer within the polymer chains. It is measured as described in WO 93/03093, specifically columns 7 and 8 as well as in Wild et al, J. Poly. Sci., Poly. Phys. Ed., Vol. 20, p. 441, (1982) and US 5,008,204, including that fractions having Mw below 15,000 g/mol are ignored when determining CDBI.
  • MAO was obtained as a 30 wt% MAO in toluene solution from Albemarle (13.5 wt% Al or 5.0 mmol/g).
  • the metallocene used for preparing catalysts Cat 1 to Cat 5 was rac-dimethylsilyl bis(2-methyl-4-(3',5'-di-tert-butyl-4'-methoxy- phenyl)-indenyl) zirconium dichloride (MCN2), and for Cat 6 to Cat 8 was rac-dimethylsilyl bis(2-cyclopropyl-4-(3',5'-di-tert-butylphenyl)-indenyl) zirconium dichloride (MCN1).
  • MFR Melt Flow Rate
  • GPC-4D Analysis for Molecular Weight Determination The moments of molecular weight (Mw, Mn, Mw/Mn, etc.) and the comonomer content (C2, C3, C6, etc.), were determined with using GPC-4D using a high temperature Gel Permeation Chromatograph (PolymerCharTM GPC-IR) equipped with a multiple-channel band filter based Infrared detector ensemble IR5, in which a broad-band channel is used to measure the polymer concentration while two narrow-band channels are used for characterizing composition. Three Agilent PLgel ⁇ Mixed-B LS columns are used to provide polymer separation.
  • PolymerCharTM GPC-IR Gel Permeation Chromatograph
  • TCB Reagent grade 1,2,4-trichlorobenzene
  • BHT butylated hydroxy toluene
  • the TCB mixture was filtered through a 0.1 ⁇ Teflon filter and degassed with an online degasser before entering the GPC instrument.
  • the nominal flow rate was 1.0 mL/min and the nominal injection volume was 200 ⁇
  • the whole system including transfer lines, columns, detectors were contained in an oven maintained at 145°C.
  • Given amount of polymer sample was weighed and sealed in a standard vial with 80 flow marker (heptane) added to it. After loading the vial in the autosampler, polymer was automatically dissolved in the instrument with 8 mL added TCB solvent.
  • the polymer was dissolved at 160°C with continuous shaking for about 1 to 2 hours.
  • the TCB densities used in concentration calculation are 1.463 g/ml at room temperature and 1.284 g/ml at 145°C.
  • the sample solution concentration was from 0.2 to 2.0 mg/ml, with lower concentrations being used for higher molecular weight samples.
  • the concentration, c, at each point in the chromatogram is calculated from the baseline-subtracted IR5 broadband signal, I, using the following equation:
  • a is the mass constant determined with PE or PP standards.
  • the mass recovery is calculated from the ratio of the integrated area of the concentration chromatography over elution volume and the injection mass which is equal to the predetermined concentration multiplied by injection loop volume.
  • the molecular weight is determined by combining universal calibration relationship with the column calibration which is performed with a series of monodispersed polystyrene (PS) standards.
  • PS monodispersed polystyrene
  • the comonomer composition is determined by the ratio of the IR detector intensity corresponding to CH 2 and CH 3 channel calibrated with a series of PE and PP homo/copolymer standards whose nominal value are predetermined by NMR.
  • Raw silica was calcined in a CARBOLITE Model VST 12/600 tube furnace using a EUROTHERM 3216P1 temperature controller, according to the following procedure.
  • the controller was programmed with the desired temperature profile.
  • a quartz tube was filled with 100 g silica, and a valve was opened and adjusted to flow the nitrogen through the tube so that the silica was completely fluidized.
  • the quartz tube was then placed inside the heating zone of the furnace.
  • the silica was heated slowly to the desired temperature and held at this temperature for at least 8 hours to allow complete calcination and removal of water or moisture. After the dehydration was complete, the quartz tube was cooled to ambient temperature.
  • Catalyst Cat 1 - Cat 5 Preparation: Catalysts Cat 1 to Cat 5 were prepared by the following procedure: 125rnL-500mL Cel-Stir reactors equipped with mechanical stirrers were used to prepare catalysts from lg to 20g scales. S I to S5 were slurried in toluene with 1 :5 weight ratio except for S4 that used 1 : 10 weight ratio. A dry box freezer was used to cool both silica toluene slurry and MAO 30% toluene solution, and during addition of MAO, except for S5, the temperature of the slurry was maintained lower than about 5°C.
  • MAO amounts based on mmol Al/g silica used for catalyst preparation are listed in Table 2.
  • the resulting mixture was allowed to stir at ambient temperature for 30 min, the mixture was heated to 100°C and maintained at that temperature for 3hr to form supported MAO (sMAO).
  • the sMAO mixture was then allowed to cool to ambient, except for preparation of Cat 5, TIBAL was added to the mixture for preparation of Cat 1 to Cat 4 in amounts based on 0.5mmol Al/g sMAO and the mixture was stirred for 30min.
  • the amount of metallocene compound based on Zr wt% charge listed in Table 2 was added as solid at once and stirred for 1-2 hr.
  • Catalyst slurry preparation Solid catalyst was mixed well with degased mineral oil as 5% slurry.
  • the agitator was brought to 500 rpm. The mixture was allowed to mix for 5 minutes at ambient temperature. The catalyst slurry in the catalyst tube was then flushed into the reactor with 250 ml propylene. The polymerization reaction was allowed to run for 5 minutes at ambient temperature.
  • ICP Polymerization at 1 minute less than the time mark for iPP piolymerization, e.g., 29 min for a 30 min iPP run, the agitator was set to 250 rpm. At the iPP time mark, e.g., 30min, using the reactor vent block valve, the reactor pressure was vented to 214 psig, while maintaining reactor temperature as close as possible to 70°C. The agitator was increased to 500 rpm. The reactor temperature was stabilized at 70°C with the reactor pressure kept at 214 psig. Then 136 psig of ethylene was introduced, via gas phase, targeting a desired total C3 and C 2 pressure of 350 psig. The reactor was kept under that pressure for 20 minutes.
  • compositions, an element or a group of elements are preceded with the transitional phrase “comprising,” it is understood that we also contemplate the same composition or group of elements with transitional phrases “consisting essentially of,” “consisting of,” “selected from the group of consisting of,” or “is” preceding the recitation of the composition, element, or elements and vice versa.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

La présente invention concerne des polymères de propylène ayant une distribution de poids moléculaire multimodale et des procédés de polymérisation du propylène utilisant des systèmes catalytiques à site unique dotés de supports ayant une distribution multimodale des tailles des particules comprenant un mode de crête à taille de particule de 3 à 70 µm, et un autre mode de crête à taille de particule de 70-200 µm, le support ayant également une taille de particule moyenne de plus de 30 µm jusqu'à 200 μm et une surface active de 400 à 800 m2/g.
PCT/US2016/035854 2015-06-05 2016-06-03 Système catalytique contenant des supports à surface active élevée et polymérisation séquentielle pour produire des polymères hétérophasiques WO2016197014A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US15/570,835 US10280235B2 (en) 2015-06-05 2016-06-03 Catalyst system containing high surface area supports and sequential polymerization to produce heterophasic polymers

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US201562171602P 2015-06-05 2015-06-05
US62/171,602 2015-06-05
US15/142,321 US9920176B2 (en) 2015-06-05 2016-04-29 Single site catalyst supportation
US15/142,321 2016-04-29
PCT/US2016/030036 WO2016195868A1 (fr) 2015-06-05 2016-04-29 Support de catalyseur à site unique
USPCT/US2016/030036 2016-04-29

Publications (1)

Publication Number Publication Date
WO2016197014A1 true WO2016197014A1 (fr) 2016-12-08

Family

ID=57442108

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2016/035854 WO2016197014A1 (fr) 2015-06-05 2016-06-03 Système catalytique contenant des supports à surface active élevée et polymérisation séquentielle pour produire des polymères hétérophasiques

Country Status (1)

Country Link
WO (1) WO2016197014A1 (fr)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9725537B2 (en) 2015-06-05 2017-08-08 Exxonmobil Chemical Patents Inc. High activity catalyst supportation
US9725569B2 (en) 2015-06-05 2017-08-08 Exxonmobil Chemical Patents Inc. Porous propylene polymers
US9738779B2 (en) 2015-06-05 2017-08-22 Exxonmobil Chemical Patents Inc. Heterophasic copolymers and sequential polymerization
US9809664B2 (en) 2015-06-05 2017-11-07 Exxonmobil Chemical Patents Inc. Bimodal propylene polymers and sequential polymerization
US9920176B2 (en) 2015-06-05 2018-03-20 Exxonmobil Chemical Patents Inc. Single site catalyst supportation
US10077325B2 (en) 2015-06-05 2018-09-18 Exxonmobil Chemical Patents Inc. Silica supports with high aluminoxane loading capability
US10280233B2 (en) 2015-06-05 2019-05-07 Exxonmobil Chemical Patents Inc. Catalyst systems and methods of making and using the same
US10280235B2 (en) 2015-06-05 2019-05-07 Exxonmobil Chemical Patents Inc. Catalyst system containing high surface area supports and sequential polymerization to produce heterophasic polymers
US10280240B2 (en) 2016-05-27 2019-05-07 Exxonmobil Chemical Patents Inc. Metallocene catalyst compositions and polymerization process therewith
US10294316B2 (en) 2015-06-05 2019-05-21 Exxonmobil Chemical Patents Inc. Silica supports with high aluminoxane loading capability
US10329360B2 (en) 2015-06-05 2019-06-25 Exxonmobil Chemical Patents Inc. Catalyst system comprising supported alumoxane and unsupported alumoxane particles
US10570219B2 (en) 2015-06-05 2020-02-25 Exxonmobil Chemical Patents Inc. Production of heterophasic polymers in gas or slurry phase
US10723821B2 (en) 2015-06-05 2020-07-28 Exxonmobil Chemical Patents Inc. Supported metallocene catalyst systems for polymerization
US10759886B2 (en) 2015-06-05 2020-09-01 Exxonmobil Chemical Patents Inc. Single reactor production of polymers in gas or slurry phase
CN114426609A (zh) * 2020-10-15 2022-05-03 中国石油化工股份有限公司 一种烯烃聚合用固体催化剂组分及催化剂体系

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5661098A (en) * 1995-11-24 1997-08-26 Novacor Chemicals Ltd. Supported monocyclopentadienyl zirconium catalyst
WO1999058582A1 (fr) * 1998-05-08 1999-11-18 Pq Holding, Inc. Catalyseurs de polymerisation d'olefines a supports specifiques en silice
US6174930B1 (en) * 1999-04-16 2001-01-16 Exxon Chemical Patents, Inc. Foamable polypropylene polymer
EP1234837A1 (fr) * 2001-02-13 2002-08-28 Fina Technology, Inc. Méthode pour la préparation de catalysateurs metallocénes
US6992153B1 (en) * 1999-03-09 2006-01-31 Basell Polyolefine Gmbh Multi-stage process for the (CO) polymerization of olefins
EP2258731A2 (fr) * 2008-03-28 2010-12-08 SK Energy Co., Ltd. Composition de catalyseur métallocène supportée et procédé d'élaboration de polyoléfine l'utilisant
WO2014016318A1 (fr) * 2012-07-27 2014-01-30 Total Research & Technology Feluy Procédé de préparation de résine de polyéthylène

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5661098A (en) * 1995-11-24 1997-08-26 Novacor Chemicals Ltd. Supported monocyclopentadienyl zirconium catalyst
WO1999058582A1 (fr) * 1998-05-08 1999-11-18 Pq Holding, Inc. Catalyseurs de polymerisation d'olefines a supports specifiques en silice
US6992153B1 (en) * 1999-03-09 2006-01-31 Basell Polyolefine Gmbh Multi-stage process for the (CO) polymerization of olefins
US6174930B1 (en) * 1999-04-16 2001-01-16 Exxon Chemical Patents, Inc. Foamable polypropylene polymer
EP1234837A1 (fr) * 2001-02-13 2002-08-28 Fina Technology, Inc. Méthode pour la préparation de catalysateurs metallocénes
EP2258731A2 (fr) * 2008-03-28 2010-12-08 SK Energy Co., Ltd. Composition de catalyseur métallocène supportée et procédé d'élaboration de polyoléfine l'utilisant
WO2014016318A1 (fr) * 2012-07-27 2014-01-30 Total Research & Technology Feluy Procédé de préparation de résine de polyéthylène

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10280235B2 (en) 2015-06-05 2019-05-07 Exxonmobil Chemical Patents Inc. Catalyst system containing high surface area supports and sequential polymerization to produce heterophasic polymers
US10570219B2 (en) 2015-06-05 2020-02-25 Exxonmobil Chemical Patents Inc. Production of heterophasic polymers in gas or slurry phase
US9725537B2 (en) 2015-06-05 2017-08-08 Exxonmobil Chemical Patents Inc. High activity catalyst supportation
US9809664B2 (en) 2015-06-05 2017-11-07 Exxonmobil Chemical Patents Inc. Bimodal propylene polymers and sequential polymerization
US9920176B2 (en) 2015-06-05 2018-03-20 Exxonmobil Chemical Patents Inc. Single site catalyst supportation
US10077325B2 (en) 2015-06-05 2018-09-18 Exxonmobil Chemical Patents Inc. Silica supports with high aluminoxane loading capability
US10119016B2 (en) 2015-06-05 2018-11-06 Exxonmobil Chemical Patents Inc. Heterophasic copolymers and sequential polymerization
US10280233B2 (en) 2015-06-05 2019-05-07 Exxonmobil Chemical Patents Inc. Catalyst systems and methods of making and using the same
US9738779B2 (en) 2015-06-05 2017-08-22 Exxonmobil Chemical Patents Inc. Heterophasic copolymers and sequential polymerization
US10759886B2 (en) 2015-06-05 2020-09-01 Exxonmobil Chemical Patents Inc. Single reactor production of polymers in gas or slurry phase
US10294316B2 (en) 2015-06-05 2019-05-21 Exxonmobil Chemical Patents Inc. Silica supports with high aluminoxane loading capability
US10287372B2 (en) 2015-06-05 2019-05-14 Exxonmobil Chemical Patents Inc. Bimodal propylene polymers and sequential polymerization
US10329360B2 (en) 2015-06-05 2019-06-25 Exxonmobil Chemical Patents Inc. Catalyst system comprising supported alumoxane and unsupported alumoxane particles
US9725569B2 (en) 2015-06-05 2017-08-08 Exxonmobil Chemical Patents Inc. Porous propylene polymers
US10723821B2 (en) 2015-06-05 2020-07-28 Exxonmobil Chemical Patents Inc. Supported metallocene catalyst systems for polymerization
US11492425B2 (en) 2016-05-27 2022-11-08 Exxonmobil Chemical Patents Inc. Metallocene catalyst compositions and polymerization process therewith
US11059918B2 (en) 2016-05-27 2021-07-13 Exxonmobil Chemical Patents Inc. Metallocene catalyst compositions and polymerization process therewith
US10280240B2 (en) 2016-05-27 2019-05-07 Exxonmobil Chemical Patents Inc. Metallocene catalyst compositions and polymerization process therewith
CN114426609A (zh) * 2020-10-15 2022-05-03 中国石油化工股份有限公司 一种烯烃聚合用固体催化剂组分及催化剂体系

Similar Documents

Publication Publication Date Title
US10280235B2 (en) Catalyst system containing high surface area supports and sequential polymerization to produce heterophasic polymers
WO2016197014A1 (fr) Système catalytique contenant des supports à surface active élevée et polymérisation séquentielle pour produire des polymères hétérophasiques
US10287372B2 (en) Bimodal propylene polymers and sequential polymerization
US11192961B2 (en) Production of heterophasic polymers in gas or slurry phase
US9920176B2 (en) Single site catalyst supportation
US10119016B2 (en) Heterophasic copolymers and sequential polymerization
US9725537B2 (en) High activity catalyst supportation
US9725569B2 (en) Porous propylene polymers
WO2016197037A1 (fr) Système catalyteur comprenant des particules d'alumosane supportées et non supportées
US10329360B2 (en) Catalyst system comprising supported alumoxane and unsupported alumoxane particles
US20200362071A1 (en) Single Reactor Production of Polymers in Gas or Slurry Phase
US20160355619A1 (en) Silica Supports With High Aluminoxane Loading Capability
WO2021247244A2 (fr) Procédé de production de vulcanisats thermoplastiques utilisant des systèmes catalyseurs supportés et compositions fabriquées à partir de ceux-ci
EP3303419A1 (fr) Copolymères hétérophasiques et polymérisation séquentielle
US11034827B2 (en) Heterophasic copolymers and polymerization methods
EP3303418A1 (fr) Polymères de propylène bimodaux et polymérisation séquentielle
WO2016195866A1 (fr) Support de catalyseur à haute activité
EP3303417A1 (fr) Polymères de propylène poreux
EP3303416A1 (fr) Support de catalyseur à site unique
WO2016195876A1 (fr) Supports en silice à haute capacité de charge d'aluminoxane
WO2016195875A1 (fr) Supports silice aptes à présenter des charges d'aluminoxane élevées

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16730955

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 15570835

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16730955

Country of ref document: EP

Kind code of ref document: A1