WO2016195866A1 - Support de catalyseur à haute activité - Google Patents
Support de catalyseur à haute activité Download PDFInfo
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- WO2016195866A1 WO2016195866A1 PCT/US2016/029985 US2016029985W WO2016195866A1 WO 2016195866 A1 WO2016195866 A1 WO 2016195866A1 US 2016029985 W US2016029985 W US 2016029985W WO 2016195866 A1 WO2016195866 A1 WO 2016195866A1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
- C08F2410/06—Catalyst characterized by its size
-
- 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
- C08F4/65925—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 non-bridged
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
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- 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
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Definitions
- This invention relates to single site catalyst supportation methods to improve catalyst activity for olefin polymerization, e.g., propylene polymerization, and to the supported catalysts obtained by the methods.
- MCN methylalumoxane
- ZN Ziegler-Natta
- the iPP matrix of the ICP prepared using MCN has a low porosity, and is unable to hold a sufficiently high rubber content within the iPP matrix required for toughness and impact resistance.
- the MCN-ICP has an MWD that is too narrow to obtain sufficient crystalline, low molecular weight polymer required for stiffness. The formation of rubber in a separate phase outside the matrix is undesirable, e.g., it can result in severe reactor fouling.
- Pore structures in conventional iPP are understood to be generated from the fast crystallization of low molecular weight portions of the polymer that causes volumetric shrinkage during crystallization.
- Nello Pasquini (Ed.), Polypropylene Handbook, 2nd Edition, Hanser Publishers, Kunststoff, pp. 78-89 (2005), reports volumetric shrinkage processes only generate low porosities for limited rubber loadings, e.g., 7% porosity from a conventional ZN catalyst system, and 16% more is obtained through the treatment of the MgCl 2 -supported ZN system via controlled dealcoholation, allowing the iPP matrix to be filled with a rubber content nearing 25 wt%.
- Cecchin G.
- US 5,990,242 approaches this problem by using an ethylene/butene (or higher alpha- olefin) copolymer second component, rather than a propylene copolymer, prepared using a hafnocene type MCN.
- hafnium MCNs are generally useful for producing relatively higher molecular weight polymers; however, their activities are typically much lower than the more commonly used zirconocenes.
- the second component molecular weights and intrinsic viscosities are lower than desired for good impact strength.
- WO 2004/092225 discloses MCN polymerization catalysts supported on silica having a 10-50 ⁇ particle size (PS), 200-800 mVg surface area, and 0.9 to 2.1 mL/g pore volume, and shows an example of a 97 ⁇ PS, 643 m 2 /g surface area and 3.2 mL/g pore volume silica (p. 12, Table I, support E (MS3060)) used to obtain iPP (pp. 18-19, Tables V and VI, run 21).
- PS 10-50 ⁇ particle size
- MS3060 support E
- EP 1 380 598 discloses certain MCN catalysts supported on silica having a 2-12 ⁇ PS, 600-850 mVg surface area, and 0.1 to 0.8 mL/g pore volume, and shows an example of silica having a 6.9 ⁇ PS, 779 m 2 /g surface area and 0.23 mL/g pore volume (p. 25, Table 3, Ex. 16) to obtain polyethylene.
- EP 1 541 598 discloses certain MCN catalysts supported on silica having a 2 to 20 ⁇ particle size, 350-850 mVg surface area, and 0.1 to 0.8 mL/g pore volume (p. 4, lines 15-35), and shows an example of a 10.5 ⁇ particle size, 648 m 2 /g surface area and 0.51 mL/g pore volume silica (see p. 17, Example 12) for an ethylene polymerization.
- EP 1 205 493 describes a 1126 m 2 /g specific surface area (SA) and 0.8 cc/g structural porous volume (small pores only) silica support used with an MCN catalyst for ethylene copolymerization (Examples 1, 6, and 7).
- JP 2003073414 describes a 1 to 200 ⁇ particle size (PS), 500 m 2 /g or more SA, and 0.2 to 4.0 mL/g pore volume (PV) silica, but shows examples of propylene polymerization with certain MCNs where the silica has particle sizes of 12 ⁇ and 20 ⁇ .
- JP 2012214709 describes 1.0 to 4.0 ⁇ PS, 260 to 1000 mVg SA, and 0.5 to 1.4 mL/g PV silica used to polymerize propylene.
- high activity single site catalyst systems for olefin polymerization and processes to make and/or use the catalyst systems and/or to improve the polymerization activity of the catalyst systems, are presented.
- these catalyst systems can produce new propylene polymers having the benefits of metallocene (MCN) catalyzed polymers in addition to properties desirable for high impact strength or other applications.
- MCN metallocene
- these polymers can be economically produced using commercial-scale processes and conditions, with high catalyst activity.
- single site catalyst precursors such as MCNs, along with activators and or co-activators, are supported on high surface area supports (e.g., 10 m 2 /g or more) at elevated temperatures (e.g., above 40°C) to produce catalyst systems with excellent activity to form propylene polymers, e.g., isotactic polypropylene (iPP), which may be unimodal or bimodal in molecular weight distribution (MWD) and/or particle size distribution (PSD), porous (e.g., > 2%), and/or suitable for producing heterophasic copolymers, e.g., impact copolymers (ICP) with high rubber fill (e.g., > 15 wt%), and/or have an excellent balance of stiffness and toughness properties.
- iPP isotactic polypropylene
- MBD molecular weight distribution
- PSD particle size distribution
- porous e.g., > 2%
- heterophasic copolymers e.g.
- embodiments of the invention relate to a process comprising: supporting an activator for a single site catalyst precursor compound on a support, the support having an average particle size (PS) of from 5 ⁇ to 500 ⁇ , a specific surface area (SA) of 10 m 2 /g or more, a pore volume (PV) of from 0.1 to 4 mL/g, and a mean pore diameter (PD) of from 1 to 100 nm (10 to 200 A), and contacting the activator and the single site catalyst precursor compound to form a supported catalyst system, wherein the supporting, the contacting, or both, are at an elevated temperature, e.g., above 40°C.
- PS average particle size
- SA specific surface area
- PV pore volume
- PD mean pore diameter
- embodiments of the invention relate to the single site catalyst system comprising (a) the single site catalyst precursor compound; (b) the activator; and (c) the support.
- the catalyst system is prepared from a supportation process wherein the supporting of the activator on the support, the contacting of the supported activator and the catalyst precursor compound, or both, are at an elevated temperature, e.g., above 40°C.
- the support has an average PS of more than 30 ⁇ up to 200 ⁇ , SA of 200 m 2 /g or more, PV of from 0.5 to 2 mL/g, and mean PD of from 1 to 20 nm (10 to 200 A); e.g., PS more than 30 ⁇ up to 200 ⁇ , SA 650 m 2 /g or more, PV from 0.5 to 2 mL/g, and PD from 1 to 7 nm (10 to 70 A); or SA less than 650 m 2 /g, PD greater than 7 nm (70 A), or both.
- FIG. 1 is an electron micrograph showing D 150-60A silica comprising agglomerated primary particles.
- FIG. 2 is an electron micrograph showing PD 13054 silica comprising agglomerated primary particles.
- FIG. 3 is an electron micrograph showing a comparative MS 3050 silica.
- FIG. 4 is a graphical representation showing incremental intrusion (mL/g) versus pore size diameter ( ⁇ ) of the MCN-catalyzed PiPP4 produced according to Example 3.
- FIG. 5 is a graphical representation showing incremental intrusion (mL/g) versus pore size diameter ( ⁇ ) of the comparative MCN-catalyzed CiPP2 produced according to Example 3.
- FIG. 6 is a graphical representation showing incremental intrusion (mL/g) versus pore size diameter ( ⁇ ) of comparative Ziegler-Natta catalyzed CiPP3 produced according to Example 3.
- FIG. 7 is a graphical representation showing a typical particle size distribution (PSD) of CiPP6 particles produced using a catalyst supported on a comparative silica, showing a PSD from a heat-treated catalyst supportation process according to Example 6.
- PSD particle size distribution
- FIG. 8 is a graphical representation showing the PSD of PiPP12 particles produced using a supported catalyst prepared from a low temperature controlled process to inhibit support fragmentation according to Example 6.
- FIG. 9 is a graphical representation showing the PSD of PiPP13 particles produced using a supported catalyst prepared through a medium temperature treatment to control partial fragmentation of the support according to Example 6.
- FIG. 10 is a graphical representation showing the PSD of PiPP14 particles produced using supported catalyst prepared through a high temperature treatment to promote support fragmentation according to Example 6.
- FIG. 11 is a plot of the 4D gel permeation chromatograph (GPC-4D) for heterophasic copolymer ICP1 having about 40% ethylene-propylene rubber loading in a porous iPP matrix according to Example 7.
- GPC-4D gel permeation chromatograph
- 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
- peak value or maxima 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 multimodal distribution is one having two or more peaks, i.e., a distribution having a plurality of local maxima; a bimodal distribution has two inflection points; and a unimodal distribution has one peak or inflection point.
- particle size or diameter, and distributions thereof, are determined by laser diffraction using a MASTERSIZER 3000 (range of 1 to 3500 um) available from Malvern Instruments, Ltd. Worcestershire, England. 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 TRISTAR II 3020 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 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 external 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 corners 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, or a monolithic 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.
- FIGs. 1-2 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 D 150-60A silica, 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.
- FIG. 2 is an electron micrograph of PD 13054, showing interior agglomerates 10 comprised of around 5-50 ⁇ primary particles and encapsulating aggregate 14.
- 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.
- FIG. 3 shows a comparative support MS 3050, comprised of generally spherical particles 20 with an entirely aggregated or monolithic core 22, lacking the agglomerated primary particles and internal pore morphology of the FIG. 1-2 supports.
- 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 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.
- 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 monoliths, 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.
- catalyst productivity is a measure of how many grams of polymer (Pol or P) are produced using a polymerization catalyst comprising W g of catalyst (cat), over a period of time of T hours; and may be expressed by the following formula: P/(T x W) and expressed in units of grams polymer divided by the product of grams catalyst and time in hours (gPol gcarV. " 1 ).
- conversion is the amount of monomer that is converted to polymer product, and is reported as mol% and is calculated based on the polymer yield and the amount of monomer fed into the reactor.
- catalyst activity is a measure of how active the catalyst is and is reported as the mass of product polymer (P) produced per mole of catalyst (cat) transition metal used (kg P/mol cat), or per g of supported catalyst (including the support, activator, co- activator, etc.).
- 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.
- 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., to produce a multimodal and/or heterophasic polymer.
- continuous means a system that operates without interruption or cessation.
- 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 (PDI)
- Mw is g/mol and are determined by GPC-DRI as described below.
- 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 precursor, a catalyst precursor compound, a pre-catalyst compound, metallocene or MCN, metallocene compound, metallocene catalyst, metallocene catalyst compound, metallocene catalyst precursor 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., CpaZrC ⁇ , 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., [Cp 2 Zr ⁇ -Me) 2 AlMe 2 ] + to become capable of polymerizing olefin monomers.
- an activator e.g., MAO
- an active catalyst species e.g., [Cp 2 ZrMe] +
- a resting active catalyst species e.g., [Cp 2 Zr ⁇ -Me) 2 AlMe 2 ] + 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.
- compositionally different means the compositions in question differ by at least one atom.
- 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-dimemylsilylbis(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 e.g., comprising fill rubber, or produced with phased hydrogen supply, and/or produced after time period B when specified, 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 100 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., CF 3 ).
- halogen e.g., F, CI, Br, I
- halogen-containing group e.g., CF 3
- Silylcarbyl radicals are groups in which the silyl functionality is bonded directly to the indicated atom or atoms. Examples include S1H3, SiH 2 R*, SiHR*2, SiR*3, SiH 2 (OR*), SiH(OR*) 2 , Si(OR*) 3 , SiH 2 (NR* 2 ), SiH(NR* 2 ) 2 , Si(NR* 2 ) 3 , and the like, where 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, GeH 2 R*, GeHR* 2 , GeR* 3 , GeH 2 (OR*), GeH(OR*) 2 , Ge(OR*) 3 , GeH 2 (NR* 2 ), GeH(NR* 2 ) 2 , Ge(NR* 2 ) 3 , and the like, where 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 heteroatom 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, PbR*3 and the like, where 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.
- SC ⁇ Me mesylate
- S03(4-tosyl) tosylate
- SO3CF3 triflate
- S03(n-C4F9) nonaflate
- 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[6]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[6]thienyl has five bondable ring positions (at the carbon atoms) and one non- bondable ring position (the sulfur atom); cyclopenta[6]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 process, comprising: supporting an activator for a single site catalyst precursor compound on a support, the support having an average particle size (PS) of from 5 ⁇ to 500 ⁇ (e.g., 30 ⁇ to 500 ⁇ ), a specific surface area (SA) of 10 m 2 /g or more (e.g., 200 or 400 m 2 /g or more), a pore volume (PV) of from 0.1 to 4 mL/g (e.g., 0.5 to 2 mL/g), and a mean pore diameter (PD) of from 1 to 100 nm (e.g., 1 to 35 nm); and contacting the supported activator and a single site catalyst precursor compound to form a supported catalyst system; wherein the supporting, the contacting, or both, are at a temperature above 40°C (e.g., 100-130°C).
- PS average particle size
- SA specific surface area
- PV pore volume
- PD mean pore diameter
- the support has an average PS of more than 30 ⁇ up to 200 ⁇ , a specific SA of 650 m 2 /g or more, a PV of from 0.5 to 2 mL/g, and a mean PD of from 1 to 7 nm (10 to 70 A); alternately, SA less than 650 m 2 /g, or mean PD greater than 7 nm (70 A), or both.
- the support comprises agglomerates of a plurality of primary particles, and the process further comprises fragmenting the agglomerates.
- the catalyst system formed in the contacting has a bimodal particle size distribution comprised of at least about 5 vol% of the agglomerates and at least about 5 vol% of fragments of the agglomerates, based on the total volume of the supported catalyst system.
- the supporting and contacting are essentially free of fines formation.
- the support comprises a metal oxide, e.g., spray dried silica having an average particle size of more than 50 ⁇ , a specific surface area less than 1000 m 2 /g, or a combination thereof.
- a metal oxide e.g., spray dried silica having an average particle size of more than 50 ⁇ , a specific surface area less than 1000 m 2 /g, or a combination thereof.
- the activator comprises alumoxane, e.g., MAO or MMAO.
- the process further comprises contacting the supported activator with a co-activator selected from the group consisting of: trialkylaluminum, dialkylmagnesium, alkylmagnesium halide, and dialkylzinc.
- a co-activator selected from the group consisting of: trialkylaluminum, dialkylmagnesium, alkylmagnesium halide, and dialkylzinc.
- the supporting, the contacting, or both are at a temperature above 80°C, e.g., above 100°C up to 130°C.
- the single site catalyst precursor compound comprises a hafnocene and/or a zirconocene.
- the process further comprises contacting the supported catalyst system and propylene monomer under polymerization conditions to form a matrix of porous propylene polymer comprising at least 50 mol% propylene and a median PD less than 165 ⁇ as determined by mercury intrusion porosimetry; and dispersing active catalyst system sites within the matrix.
- the process comprises contacting the dispersed active catalyst system sites with one or more alpha-olefin monomers under polymerization conditions.
- a supported catalyst system is prepared by the process just described.
- the support has an average particle size of more than 30 ⁇ up to 200 ⁇ , a specific surface area of 650 mVg or more, a pore volume of from 0.5 to 2 mL/g, and a mean pore diameter of from 1 to 7 nm (10 to 70 A).
- the supported catalyst system comprises agglomerates of a plurality of primary particles, and a bimodal particle size distribution comprised of at least about 5 vol% of the catalyst system supported on the agglomerates and at least about 5 vol% of the catalyst system supported on the fragments of the agglomerates, based on the total volume of the supported catalyst system.
- 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 MCN 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 is preferably an inorganic oxide, has SA in the range of from about 10 to about 700 m 2 /g, PV in the range of from about 0.1 to about 4.0 mL/g, and average PS in the range of from about 5 to about 500 um. More preferably, the SA is in the range of from about 50 to about 1400 m 2 /g, PV from about 0.5 to about 3.5 mL/g and average PS from about 10 to about 200 ⁇ . Most preferably, the SA is in the range from about 100 to about 1000 m 2 /g, PV from about 0.8 to about 3.0 mL/g and average PS from about 30 to about 200 ⁇ .
- the mean PD in some embodiments of the invention is in the range of from 1 to 100 nm (10 to 1000 A), preferably 1 to 50 nm (10 to about 500 A), and most preferably 1 to 35 nm (10 to about 350 A).
- the catalyst support material is a high SA, spray dried silica.
- Some preferred support silicas are marketed under the tradenames GRACE 952 (also known as DAVISON 952) or GRACE 955 (also known as DAVISON 955) GRACE 948 (also known as DAVISON 948) by the Davison Chemical Division of W.R. Grace and Company; or D 150-60A or D 100-lOOA by the Asahi Glass Co., Ltd. or AGC Chemicals Americas, Inc.; or PD 13054 or PD 14024 by the PQ Corporation.
- 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 less than 5 vol% of primary particles (if present) and/or fines is generated, by total volume of the support material.
- the support material is 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 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 2 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;
- SA specific surface area
- PD mean pore diameter
- 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, SA, PV and PD characteristics, are preferably made from a process that agglomerates smaller primary particles, e.g., average PS in the range of 0.001-50 ⁇ , 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.
- the SA, PV, and mean PD are generally interrelated, in some embodiments, in that within certain ranges of these parameters the product of the mean PD and SA may be proportional to the PV.
- the PV, PD, and SA in some embodiments are preferably selected to balance the desired mechanical strength with the desired activator loading (and thus catalyst activity), i.e., high SA to accommodate high activator and catalyst loading, yet not too high so as to maintain sufficient strength to avoid fragmentation during calcination or from agitation and handling, while at the same time avoiding excessive strength, which might undesirably inhibit fragmentation during polymerization in some embodiments.
- the support materials in some embodiments of the invention have PS in the range of 30-200 um, SA 400-1000 m 2 /g, PV 0.5-2 mL/g, and mean PD 1-20 nm.
- Silicas which may be suitable according to some embodiments of the invention are commercially available under the trade designations D 150-60A, D 100-lOOA, D 70-120, PD 13054, PD 14024, and the like. This combination of property ranges is in contrast to most other silica supports used for MCN catalysts for iPP.
- the activity may be low; if the PV is too high, the particles may be mechanically fragile; if the PS and/or PV are too small, the result may be low activity, low porosity, low rubber fill, excess surface -deposited rubber, and/or reactor fouling; and if the PS is too large, heat removal is inefficient, monomer mobility into the interior of the polymer particle is limited, monomer concentration is insufficient, chain termination is premature, and/or low molecular weights result.
- agglomerates having, within the preferred ranges of SA > 400 m 2 /g and mean PD 1 - 20 nm, either a lower SA, e.g., less than 700 m 2 /g or less than 650 m 2 /g, and/or a higher mean PD, e.g., more than 7 nm or more than 8 nm, have higher strength and are more resistant to debris dominated fragmentation during the supportation process, which can thus be carried out at higher temperatures, and higher catalyst loadings can be achieved for higher catalyst activity.
- 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 silica fragmentation can be promoted, if desired, e.g., for higher catalyst activity, using supportation conditions that facilitate the essentially complete or partial fragmentation, e.g., at a temperature higher than about 40 or 60°C , such as for example, from greater than 80°C or greater than 100°C up to about 130°C.
- 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.
- contacting wet silica with an aluminum alkyl such as AlMe 3 usually diluted in an organic solvent such as toluene, forms in-situ MAO, and if desired additional MAO can be added to control the desired amount of MAO loaded on the support, in a manner otherwise similar as described below for dry silica.
- an aluminum alkyl such as AlMe 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.
- the support is treated with an organometallic compound to react with deprotonated reactive sites on the support surface.
- an organometallic activator such as MAO
- 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 40°C up to about 130 or 140°C, such as, for example: from about 60°C, or about 80°C up to about 100°C, or about 120°C, or about 130°C.
- the support may be susceptible to fragmentation during activator/catalyst precursor supportation (e.g., SA > 650 m 2 /g, PD ⁇ 7 nm)
- fragmentation can be controlled through the manipulation of reaction conditions to promote fragmentation such as at a higher reaction temperature, e.g., > 40°C , preferably > 60°C , to achieve
- vol% fragmented particles e.g., 5-80 vol% fragmented particles, such as 10-20 vol% fragmented particles, 20-70 vol% fragmented particles, 70-90 vol% fragmented particles,
- the time and temperature required to promote fragmentation of a support susceptible to fragmentation are inversely related, i.e., at a higher temperature, debris dominated fragmentation may require a shorter period of time.
- the support material is not 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 average PS or PS mode of the supported catalyst system material facilitates the formation of sufficiently large propylene 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.
- porous polypropylene 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 or sub-primary particle debris or fines, 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.
- the supported catalysts e.g., on silica with SA > about 650 m 2 /g and PD ⁇ about 70 A, are able to polymerize propylene to produce iPP resins with very high stiffness, e.g., up to 2200 MPa 1% secant flexural modulus.
- the supported catalysts e.g., on silica with balanced PS, SA, PV, and PD, such as, for example, PS 70-100 ⁇ , SA 400-650 mVg, PV 1.1-1.6 mL/g, and PD 90-120 A, and prepared under low fragmentation conditions, are able to polymerize propylene to produce iPP 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 with limited fragmentation as disclosed herein have been discovered to show improved ethylene-propylene (EP) rubber uptake.
- the mixtures of finished catalyst supported on fragmented and non-fragmented supports are bimodal in PSD, and different polypropylene properties are thereby achieved, and with the result that the different polypropylene properties can be balanced as desired.
- the PSD of the resulting iPP resin changes according to the PSD of the supported catalyst system, i.e., support fragments produce smaller iPP particles relative to the larger iPP particles formed from the larger more or less intact agglomerates.
- the non- fragmented support particles facilitate the formation of large PS, high PV, low PD, fillable polypropylene particles
- the fragments may facilitate a higher catalyst activity and formation of a polypropylene with smaller PS and higher stiffness, and thus the activity, porosity, rubber fill content and stiffness can be balanced by selecting the appropriate mix of fragmented and non-fragmented supports. For example, where higher catalyst activity, higher stiffness, smaller polypropylene PS and/or lower rubber fill content are desired, the proportion of fragmented support particles can be increased.
- CiPP6 obtained in Example 6 using a conventional catalyst with a relatively broad, unimodal PSD has a corresponding bell-shaped curve.
- the finished catalyst, supported on non- fragmented agglomerates obtains a PSD in the relatively large-size area of PiPP12 (FIG. 8), supported on a mix of non- fragmented agglomerates and fragments gives a bimodal distribution of both large and small PiPP13 particles (FIG. 9), and supported on debris dominated fragments obtains a small particle size dominated bell-shaped distribution of PiPP14 (FIG. 10).
- the PSD of PiPP12 from the catalyst prepared under reaction conditions of -20-0°C for 3 hours shows the majority as large particles from non-fragmented catalyst particles
- the PSD of PiPP13 from the catalyst prepared under reaction conditions of 80°C for 1 hour shows two modes, i.e., a smaller, second mode from the catalyst system fragments
- the PSD of PiPP 14 from the catalyst prepared under reaction conditions of 100°C for 3 hours shows the majority as relatively small particles from the catalyst system fragments.
- a bimodal catalyst system can be obtained according to the invention by blending two different support materials, prior to, during, or following the supportation procedure.
- supportation starting with a mixture of support materials where one is susceptible to fragmentation and another one is resistant to fragmentation may yield a supported catalyst system comprising both the larger fragmentation-resistant particles and the smaller fragmented particles; or a similar bimodal mixture can be obtained starting with the same (or different) support materials, with supportation of the activator and/or precursor compound (which may be the same or different) on one portion at fragmentation conditions and the other at non-fragmentation conditions, followed by admixing the two catalyst systems or supports either after the supportation process, or at a point in the supportation process after which fragmentation conditions are not encountered.
- high porosity iPP resins may be formed based on the support structure, independent of polymerization conditions utilized by other systems to gain iPP porosity, e.g., other systems that polymerize propylene under high hydrogen polymerization conditions to produce low molecular weight resins that crystallize and shrink to form limited pores.
- High stiffness and high porosity iPP resins according to the instant disclosure can be obtained, in some embodiments, regardless of the hydrogen concentration in the polymerization, and result in improved ICP.
- the catalyst system has a multimodal PSD, e.g., a bimodal PSD comprising relatively large and small particle size modes, such as, for example, wherein the large particle size mode comprises at least about 5 vol%, e.g., 80 vol% or more, and the low molecular weight mode comprises at least about 1 vol% (alternately at least about 2 vol%, at least about 3 vol%, at least about 5 vol%), based on the total volume of the catalyst system.
- a multimodal PSD e.g., a bimodal PSD comprising relatively large and small particle size modes, such as, for example, wherein the large particle size mode comprises at least about 5 vol%, e.g., 80 vol% or more, and the low molecular weight mode comprises at least about 1 vol% (alternately at least about 2 vol%, at least about 3 vol%, at least about 5 vol%), based on the total volume of the catalyst system.
- 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.
- R is C1-C40 hydrocarbyl such as C1-C12 alkyl for example
- M is a metal
- n is equal to the valence of M
- oxophilic species such as diethyl zinc and aluminum alkyls
- 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 MCN compound is then contacted with an organometallic- activator solution and/or organometallic-scavenger solution.
- Activators are compounds used to activate any one of the catalyst precursor compounds described above by converting the neutral catalyst precursor compound to a catalytically active catalyst compound cation.
- Non-limiting activators include alumoxanes, aluminum alkyls, ionizing activators, which may be neutral or ionic, and conventional-type cocatalysts.
- Preferred activators typically include alumoxane compounds, including modified alumoxane compounds, and ionizing anion precursor compounds that abstract a reactive, ⁇ -bound, metal ligand making the metal complex cationic and providing a charge- balancing noncoordinating or weakly coordinating anion.
- 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).
- WO 94/10180; WO 99/15534; halogenated MAO are described in US 7,960,488; US 7,355,058; US 8,354,485; dialkylaluminum cation enhanced MAO are described in
- the activator is an alumoxane
- some embodiments select the maximum amount of activator at a 5000-fold molar excess Al/M over the catalyst precursor compound (per metal catalytic site).
- the minimum activator-to-catalyst-compound is a 1 : 1 molar ratio.
- Alternate preferred ranges include from 1: 1 to 500: 1, alternately from 1 : 1 to 200: 1, alternately from 1 : 1 to 100: 1, or alternately from 1: 1 to 50: 1, e.g., 1: 1 to 10: 1 or 10: 1 to 50: 1.
- alumoxane is present at zero mole%, alternately the alumoxane is present at a molar ratio of aluminum to catalyst precursor compound transition metal less than 500: 1, or less than 300: 1, or less than 100: 1, or less than 1: 1.
- an ionizing or stoichiometric activator 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.
- 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 single site catalyst precursor compound is represented by the formula: R ⁇ (CpR"p)(CpR*q)M ⁇ Q r ; wherein 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; RA 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 terra-, tri-
- the single site catalyst precursor compound is represented by the formula:
- At least one of R 2 , R 3 , R 4 , R 5 , R 6 , R7, R8, R9 R1 R 13 is a cyclopropyl substituent 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 C ⁇ g alkyl groups, substituted or unsubstituted C i to C i g alkoxy groups, substituted or unsubstituted Cg to C 14 aryl groups, substituted or unsubstituted Cg to C 14 aryloxy groups, substituted or unsubstituted C2 to C ⁇ g alkenyl groups, substituted or unsubstituted C to C40 arylalkyl groups, substituted or unsubstituted C to C40 alkylaryl groups and substituted or unsubstituted C to C40 arylalkenyl groups; or optionally are joined together to form a C4 to
- R 14 , R 15 , and R 16 are each independently selected from hydrogen, halogen, Ci to C20 alkyl groups, Cg to C30 aryl groups, C i to C20 alkoxy groups, C2 to C20 alkenyl groups, C 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 M 3 is selected from carbon, silicon, germanium, and tin; or T is represented by the formula:
- R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , and R 24 are each independently selected from hydrogen, halogen, hydroxy, substituted or unsubstituted C i to C ⁇ g alkyl groups, substituted or unsubstituted Ci to C ⁇ Q alkoxy groups, substituted or unsubstituted Cg to C14 aryl groups, substituted or unsubstituted Cg to C14 aryloxy groups, substituted or unsubstituted C2 to C ⁇ Q alkenyl groups, substituted or unsubstituted C to C40 alkylaryl groups, substituted or unsubstituted C 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 , R 23 , and R 24 , including R 2
- one catalyst compound is used, e.g., where first and second (and or third) catalyst systems are present, the catalyst compounds are not different.
- 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 3 ⁇ 4 or 13 C 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 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, and alternatively 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, 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.
- 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 3 , R ⁇ , R6 5 R7 ⁇ R9 ⁇ R I I ⁇ R 12 ⁇ or R13 j S 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 ⁇ , R 4 , R ⁇ 5 R6 ⁇ R7 ⁇ R ⁇ , RIO, R11 ; R12 ⁇ or R13 ⁇ independently selected from hydrogen, methyl, ethyl, phenyl, benzyl, cyclobutyl, cyclopentyl, cyclohexyl, naphthyl, anthracenyl, carbazolyl, indolyl, pyrrolyl, cyclopenta[6]thiopheneyl, fluoro, chloro, bromo, iodo and isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, methylphenyl, dimethylphenyl, ethylphenyl, diethylphenyl, propylphenyl, dipropylphenyl, butylpheny
- T is a bridging group and comprises Si, Ge, or C, preferably T is dialkyl silicon or dialkyl germanium, preferably T is dimethyl silicon.
- 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 Si(CH 2 )5.
- each R2 and R ⁇ 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 R2 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 4 and R 10 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 R 8 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 4 and 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,
- R 2 , R 8 , R 4 , and R 10 are as described in the preceding sentence and R 3 , R 5 , R 6 , R 7 , R 9 , R 1 1 , R 12 , and R 13 are hydrogen.
- suitable MCN compounds are represented by the formula ( 1 ) :
- each A is a substituted monocyclic or polycyclic 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; and 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 C I -C I QO 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 represente
- each R1, R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , Rio, 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 , R 1 1 , Rl2 Rl3, 0 r Rl4 is a cyclopropyl substituent and in formula 2a and 2b at least one of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , or R 7 , is a cyclopropyl substituent; and provided that any adjacent R1 to R ⁇ 4 groups that are not a cyclopropyl substituent may form a
- 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[o]naphthyl, cyclopenta[6]naphthyl, heteropentalenyl, heterocyclopentapentalenyl, heteroindenyl, heterofluorenyl, heterocyclopentanaphthyl, heterocyclopentaindenyl, and heterobenzocy clopentaindenyl ligands .
- MCN compounds suitable for use herein may further include one or more of: dimethylsilylene-bis(2-cyclopropyl-4-phenylindenyl)zirconium dichloride; dimethylsilylene-bis(2- cyclopropyl-4-phenylindenyl)hafnium 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)hafnium 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-if any, 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. 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 3 ⁇ 4 or 13 C 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) is typically
- 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 50: 1.
- the particular ratio chosen will depend on the exact pre-catalysts chosen, the method of activation, and the end product desired.
- 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.
- 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 C ⁇ to C30 alkyl, alternately a C2 to C20 alkyl, alternately a C3 to C ⁇ 2 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-ethy
- Useful CTAs are typically present at from 10, or 20, or 50, or 100 equivalents to 600, or 700, or 800, or 1000 equivalents relative to the catalyst component.
- the CTA is preset at a catalyst complex-to-CTA molar ratio of from about 1 :3000 to 10: 1; alternatively 1 :2000 to 10: 1; alternatively 1: 1000 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; or/and alternatively l : 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 C ⁇ 2 alpha olefins, preferably ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, and isomers thereof.
- the monomer comprises propylene and optional co-monomer(s) comprising one or more of ethylene or C4 to C40 olefins, preferably C4 to C20 olefins, or preferably Cg to C ⁇ 2 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 co-monomer is present.
- Exemplary C2 to C40 olefin monomers and optional co-monomers include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, norbornadiene, 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, l-acetoxy-4-cyclooctene,
- one or more dienes are present in the polymer produced herein at up to 10 wt%, preferably at 0.00001 to 1.0 wt%, preferably 0.002 to 0.5 wt%, even more preferably 0.003 to 0.2 wt%, based upon the total weight of the composition.
- 500 ppm or less of diene is added to the polymerization, preferably 400 ppm or less, preferably or 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, vinylnorbornene, norbornadiene, 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 norbornadiene.
- olefins such as ethylene, propylene, 1-butene, 1-hexene, 4-methyl-l-pentene, and 1-octene, vinylcyclohexane, norbornene and norbornadiene.
- propylene and ethylene are polymerized.
- the butene source may be a mixed butene stream comprising various isomers of butene.
- the 1-butene monomers are expected to be preferentially consumed by the polymerization process.
- Use of such mixed butene streams will provide an economic benefit, as these mixed streams are often waste streams from refining processes, for example, C4 raffinate streams, and can therefore be substantially less expensive than pure 1-butene.
- the monomers comprise 0 wt% diene monomer in any stage, preferably in all stages.
- the co-monomer(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), based on the molecular.
- 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 A 1 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 propylene 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-stage process in three 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 propylene 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, liquid slurry or solution polymerization 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.
- 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 vol% 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.
- stage Al produces hPP
- stage B produces propylene copolymer, such as propylene-ethylene copolymer.
- stage A produces hPP
- stage B produces hPP.
- stage Al and stage A2 produce hPP and stage B produces propylene copolymer, such as propylene -ethylene copolymer.
- stage B produces hPP
- stage A produces propylene copolymer, such as propylene-ethylene copolymer.
- stage Al and stage A2 produce hPP.
- 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 C4.10 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, o
- Suitable diluents/solvents also include liquid olefins which may act as monomers or co-monomers including ethylene, propylene, 1-butene, 1-hexene, 1-pentene, 3 -methyl- 1-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 co-monomers 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. In embodiments, 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 USSN 61/896291, filed October 28, 2013, published as 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.
- A propylene and from about 0 wt% to 15 wt% C2 and/or C4 to C20 alpha olefins (alternately 0.5 to 10 wt%, alternately 1 to 5 wt%), based upon the weight of the monomer/co-monomer feeds (and optional 3 ⁇ 4), are contacted with the supported MCN catalyst(s) described herein under polymerization conditions to form Component A.
- the monomers preferably comprise propylene and optional co-monomers comprising one or more of ethylene and/or C4 to C20 olefins, preferably C4 to C ⁇ g olefins, or preferably Cg to C ⁇ 2 olefins.
- the C4 to C20 olefin monomers may be linear, branched, or cyclic.
- the C4 to C20 cyclic olefins may be strained or unstrained, monocyclic or polycyclic, and may optionally include heteroatoms and/or one or more functional groups.
- the monomer in stage A (or stages Al and A2) is propylene and no co-monomer is present.
- propylene and from about 0 wt% to 15 wt% C2 and/or C4 to C20 alpha olefins are contacted with the MCN catalyst(s) described herein under polymerization conditions to form Component B.
- the monomers preferably comprise propylene and optional co-monomers comprising one or more of ethylene and/or C4 to C20 olefins, preferably C4 to Ci g olefins, or preferably Cg to C ⁇ 2 olefins.
- the C4 to C20 olefin monomers may be linear, branched, or cyclic.
- the C4 to C20 cyclic olefins may be strained or unstrained, monocyclic or polycyclic, and may optionally include heteroatoms and/or one or more functional groups.
- the monomer in stage B is propylene and co-monomer is present.
- Component A propylene and optionally from about 1 wt% to 15 wt% (preferably 3 wt% to 10 wt%), based upon the weight of the monomer/co- monomer feeds, of one or more co-monomers (such as ethylene or C4 to C20 alpha olefins) are contacted in the presence of the MCN catalyst system(s) described herein and optional hydrogen/CTA, under polymerization conditions to form Component B intimately mixed with Component A which forms the propylene polymer composition.
- co-monomers such as ethylene or C4 to C20 alpha olefins
- the optional co-monomers may comprise one or more of ethylene and C3 to C20 olefins, preferably C4 to Ci g olefins, or preferably Cg to C ⁇ 2 olefins.
- the C4 to C20 olefin monomers may be linear, branched, or cyclic.
- the C4 to C20 cyclic olefins may be strained or unstrained, monocyclic or polycyclic, and may optionally include heteroatoms and/or one or more functional groups.
- Component A and propylene are contacted in the presence of the MCN catalyst system(s) described herein and hydrogen CTA, under polymerization conditions to form Component B intimately mixed with Component A which forms the propylene polymer composition.
- Component A and ethylene are contacted in the presence of the MCN catalyst system(s) described herein and hydrogen, under polymerization conditions to form Component B intimately mixed with Component A which forms the propylene polymer composition.
- the catalyst systems used in the stages may be the same or different and are preferably the same.
- the catalyst system used in Stage A (stages Al and A2) is transferred with the polymerizate (e.g., Component A) to Stage B, where it is contacted with additional monomer to form Component B, and thus the final propylene polymer composition.
- catalyst is provided to one, two or all three reaction zones.
- Stage A (stages Al and A2) produces a homopolypropylene
- Stage B produces a copolymer of ethylene-butene, ethylene-hexene, ethylene-octene, ethylene-propylene, ethylene-propylene-butene, ethylene-propylene-hexene, or ethylene-propylene-octene.
- 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 productivity of the catalyst system in a single stage or in all stages combined is at least 50 g(polymer)/g(cat)/hour, preferably 500 or more g(polymer)/g(cat)/hour, preferably 800 or more g(polymer)/g(cat)/hour, preferably 5000 or more g(polymer)/g(cat)/hour, preferably 50,000 or more g(polymer)/g(cat)/hour.
- the activity of the catalyst system in a single stage or in all stages combined is at least 50 kg P/mol cat, preferably 500 or more kg P/mol cat, preferably 5000 or more kg P/mol cat, preferably 50,000 or more kg P/mol cat.
- the catalyst system in a single stage or in all stages combined provides a catalyst activity of at least 800, or at least 1000, or at least 1500, or at least 2000, or at least 2500, or at least 3000, or at least 3500, or at least 4000 g propylene polymer produced per g of the supported catalyst compound (including support and activator) per hour.
- the MCN is a hafnocene compound and the catalyst activity is at least 800 or at least 1000 g propylene polymer produced per g of the supported catalyst compound.
- the conversion of olefin monomer is at least 10%, based upon polymer yield and the weight of the monomer entering the reaction zone, or 20% or more, or 30% or more, or 50% or more, or 80% or more.
- a "reaction zone”, also referred to as a "polymerization zone” is a vessel or portion thereof or combination of vessels, where the polymerization process takes place, for example, a batch reactor. When multiple reactors are used in either series or parallel configuration, each reactor is considered as a separate polymerization zone. For a multi-stage polymerization in both a batch reactor and a continuous reactor, each polymerization stage is considered as a separate polymerization zone.
- the polymerization occurs in two, three, four or more reaction zones.
- the conversion of olefin monomer is at least 10%, based upon polymer yield and the weight of the monomer entering all reaction zones, or 20% or more, or 30% or more, or 50% or more, or 80% or more.
- propylene is first polymerized and then modified with ethylene, ethylene polymers by blending and/or by modifying with ethylene/propylene copolymers.
- ICPs with ethylene content of greater than 30 wt% are achieved.
- the processes may comprise contacting ethylene and, optionally, a C2 to a C12 alpha-olefin comonomer under polymerization conditions in a first stage in the presence of a first MCN catalyst system to form Component A; contacting Component A of step a) with a C3 to a C12 alpha-olefin monomer under polymerization conditions in a second stage in the presence of a second MCN catalyst system to form Component B, wherein the first MCN catalyst system is present in both steps a and b and/or additional MCN catalyst is added to the reaction mixture between steps a and b and the first MCN catalyst system may be the same as the second MCN catalyst system; and obtaining an ethylene-based in-reactor composition comprising Component A and Component B, wherein the ethylene-based in-reactor composition has from greater than 20 mol% ethylene, based on the molecular weight of the ethylene-based in-reactor composition.
- the ethylene-based in-reactor composition may have a multimodal melting point.
- an ICP is provided that has an ethylene content of greater than 20 mol%, or greater than 30 mol%, or greater than about 40 mol%, or greater than about 50 mol%, or greater than about 65 mol%, or greater than 85 mol%, based on the molecular weight of the ICP.
- reaction sequence of step 1 and step 2 can be carried out immediately.
- the polymer products herein may comprise polypropylene, such as, for example, iPP, highly isotactic polypropylene, sPP, hPP, and RCP.
- the propylene polymer made in stage Al is iPP or highly isotactic polypropylene, preferably homopolypropylene.
- the propylene polymer made in stage A2 is propylene copolymer, preferably a copolymer of propylene and a C2 or C4 to C20 olefin, preferably ethylene).
- the propylene polymer made in stage A 1 is isotactic homopolypropylene or highly isotactic homopolypropylene.
- the propylene polymer made in stage A2 is ethylene-propylene rubber.
- the propylene polymer matrix has a porosity of 15% or more, e.g., from 20%, or 25%, or 30%, or 35%, or 40%; up to 85%, 80%, 75%, 70%, 60%, or 50%, based on the total volume of the propylene polymer matrix, determined by mercury infiltration porosimetry.
- the propylene polymer matrix has a median PD less than 165 ⁇ , e.g., between greater than 6 and less than 160 ⁇ , as determined by mercury intrusion porosimetry.
- the propylene polymer matrix has a median PD greater than 0.1, greater than 1, or greater than 2, or greater than 5, or greater than 6, or greater than 8, or greater than 10, or greater than 12, or greater than 15, or greater than 20 ⁇ ; up to less than 50, or less than 60, or less than 70, or less than 80, or less than 90, or less than 100, or less than 120, or less than 125, or less than 140, or less than 150, or less than 160, or less than 165 ⁇ .
- the propylene polymer has more than 5, or more than 10, or more than 15 regio defects per 10,000 propylene units, determined by 13 C NMR.
- the propylene polymer has a 1% Secant flexural modulus of at least 1000 MPa, e.g., at least 1300 MPa, or at least 1500 MPa, or at least 1700 MPa, or at least 1800 MPa, or at least 1900 MPa, or at least 2000 MPa, determined according to ASTM D 790 (A, 1.0 mm/min).
- the propylene polymer has a multimodal MWD. According to some embodiments of the invention, the propylene polymer has a multimodal PSD.
- the propylene polymer further comprises a second polymer at least partially filling the pores in the matrix.
- the second polymer can be a rubber fill material at least partially filling the pores, such as, for example, an ethylene-propylene copolymer, e.g., a copolymer of ethylene and from about 3 wt% to 75 wt% of one or more C3 to C20 alpha olefins by weight of the ethylene copolymer.
- the propylene polymer in which the pores are formed may conveniently be referred to herein as the "first polymer," without implying that the second polymer is necessarily present or, if present, that the first polymer is formed before the second polymer.
- the propylene polymer is heterophasic and/or an impact copolymer, for example, comprising a second polymer, e.g., fill rubber, disposed in the pores in an amount of at least 20, or at least 30, or at least 40, or at least 50, or at least 60, or at least 70, or at least 80, or up to 85 vol% or more, based on a total volume of the impact copolymer.
- a second polymer e.g., fill rubber
- the second polymer is disposed essentially entirely within the pores, i.e., an exterior surface of the polymer particle is essentially free of the second polymer so that the polymer particles remain free flowing and do not agglomerate and plug processing equipment such as reactors, lines, fittings, and/or valves used in their production.
- the propylene polymer is in a particulated form, such as, for example, wherein at least 95% by weight has a particle size greater than about 120 ⁇ , e.g., from 150, 200, 300, 400, or 500 ⁇ up to 10, 5 or 1 mm.
- the polymer is made with a single site catalyst system, e.g., it has properties or a combination of properties generally attributed to and/or which can be obtained by polymerization with a single site catalyst system as opposed to a Ziegler-Natta (ZN) catalyst system, such as higher Mw, lower PDI, lower cold xylene extractables, more uniformly distributed stereo irregularities, higher composition distribution breadth index (CBDI) in the case where a comonomer is present, between 5 and 200 regio defects per 10,000 propylene units, and the like.
- ZN Ziegler-Natta
- the polymer further comprises an active single site catalyst system, a residue of a single site catalyst system, or a combination thereof, wherein the single site catalyst system comprises a single site catalyst precursor compound, an activator for the precursor compound, and a support.
- the propylene polymer further comprises an active catalyst system comprising a single site catalyst precursor compound, an activator for the precursor compound, and a support distributed in a porous matrix of the propylene polymer.
- the matrix of the propylene polymer is comprised of a plurality of polymer subglobules defining interstitial spaces forming the pores in polymer globules.
- the matrix further comprises dispersed microparticles of a catalyst system comprising a single site catalyst precursor compound, an activator, and a support.
- the support comprises (1) silica agglomerates having an average PS of more than 30 ⁇ up to 200 ⁇ and comprising a plurality of primary particles having a relatively smaller average PS from 1 nm to 50 ⁇ , wherein the silica agglomerates have a surface area of 400 m 2 /g or more, a pore volume of from 0.5 to 2 mL/g, and a mean pore diameter of from 1 to 20 nm as determined by BET nitrogen adsorption; or (2) a plurality of free primary particles spaced apart from each other in the polymer subglobules, wherein the primary particles comprise one or more of the primary particles disagglomerated from the silica agglomerates; or (3) a combination thereof.
- the propylene polymer compositions produced herein may have a multimodal MWD of polymer species as determined by GPC-DRI.
- multimodal MWD is meant that the GPC-DRI trace has more than one peak or inflection point.
- the propylene polymer compositions produced herein may have a bimodal MWD of polymer species as determined by GPC-DRI.
- the propylene polymer compositions produced herein may have a unimodal MWD of polymer species as determined by GPC-DRI.
- the propylene polymer compositions produced herein may have a multimodal PSD as determined by laser diffraction.
- multimodal PSD is meant that the PSD curve with respect to volume has more than one peak or inflection point.
- the propylene polymer compositions produced herein may have a bimodal PSD as determined by laser diffraction.
- the propylene polymer compositions produced herein may have a unimodal PSD as determined by laser diffraction.
- the propylene polymer (the Al component) 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.
- the regio defects are determined using 13 ⁇ 4 NMR spectroscopy as described below.
- the propylene polymer composition produced herein particularly the composition produced after Stage Al and Stage A2 (the combined A1&A2 components), 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 less than 150 regio defects per 10,000 propylene units, alternatively more than 5 and less than 200 regio defects per 10,000 propylene units, alternatively more than 15 and less than 175 regio defects per 10,000 propylene units, alternatively more than 17 and less than 175 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 propylene polymer (Al) component 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 compositions produced herein 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 (Al) component can have a 1% secant flexural modulus from a low of about 1000 MPa, about 1100 MPa, about 1200 MPa, about 1250 MPa, about 1300 MPa, about 1400 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 D 790 (A, 1.0 mm/min), preferably from about 1100 MPa to about 2,200 MPa, about 1200 MPa to about 2,000 MPa, about 1400 MPa to about 2,000 MPa, or about 1500 MPa or more.
- 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 D 790(A, 1.0 mm/min).
- the propylene polymer compositions produced herein particularly the composition produced after Stage Al and Stage A2 (the combined A1&A2 components), preferably have a 1% secant flexural modulus from about 1000 MPa to about 3,000 MPa, about 1500 MPa to about 3000 MPa, about 1800 MPa to about 2,500 MPa, or about 1800 MPa to about 2,000 MPa.
- the propylene polymer (Al) component can have a melt flow rate (MFR, ASTM 1238, 230°C, 2.16 kg) from a low of about 0.1 dg/min, about 0.2 dg/min, about 0.5 dg/min, about 1 dg/min, about 15 dg/min, about 30 dg/min, or about 45 dg/min to a high of about 75 dg/min, about 100 dg/min, about 200 dg/min, or about 300 dg/min.
- MFR melt flow rate
- the polymer can have an MFR of about 0.5 dg/min to about 300 dg/min, 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.
- the propylene polymer compositions produced herein can have an MFR (ASTM 1238, 230°C, 2.16 kg) of from 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, preferably from about 50 to about 200 dg/min, preferably from about 55 to about 150 dg/min, preferably from about 60 to about 100 dg/min.
- MFR ASTM 1238, 230°C, 2.16 kg
- the propylene polymer (Al) component can have an Mw (as measured by GPC-DRI) 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, or alternately from 330,000 to 500,000 g/mol.
- Mw as measured by GPC-DRI
- the propylene polymer compositions produced herein can have an Mw (as measured by GPC-DRI) 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, or alternately from 330,000 to 500,000 g/mol.
- Mw as measured by GPC-DRI
- the propylene polymer (Al) component can have an Mw/Mn (as measured by GPC-DRI) of greater than 1 to 20, or 1.1 to 15, or 1.2 to 10, or 1.3 to 5, or 1.4 to 4.
- the propylene polymer compositions produced herein can have an Mw/Mn (as measured by GPC-DRI) of greater than 5 to 50, or 5.5 to 45, or 6 to 40, or 6.5 to 35, or 7 to 30.
- the propylene polymer compositions produced herein can have a total propylene content of at least 75 wt%, at least 80 wt%, at least 85 wt%, at least 90 wt%, or at least 95 wt%, or 100 wt% based on the weight of the propylene polymer composition.
- the propylene polymer compositions produced herein can have a total co-monomer content from 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 propylene polymer compositions produced herein can have a propylene meso diads content of 90% or more, 92% or more, about 94% or more, or about 96% or more.
- Polypropylene microstructure is determined according to the NMR procedure described below.
- the propylene polymer compositions produced herein can have a melting point (T m , DSC peak second melt) from at least 100°C to about 175°C, about 105°C to about 170°C, about 110°C to about 165°C, or about 115°C to about 155°C.
- T m melting point
- the propylene polymer compositions produced herein can have a crystallization point (Tc, DSC) of 115°C or more, preferably from at least 100°C to about 150°C, about 105°C to about 130°C, about 110°C to about 125°C, or about 115°C to about 125°C.
- Tc crystallization point
- the propylene polymer compositions produced herein can have a CDBI of 50% or more (preferably 60% or more, alternately 70% or more, alternately 80% or more, alternately 90% or more, alternately 95% or more).
- the propylene polymer compositions produced herein can have a multimodal (such as bimodal) MWD (Mw/Mn) distribution of polymer species.
- the propylene polymer composition produced herein has:
- regio defects sum of 2,1-erythro and 2,1-threo insertions and 3,1-isomerizations
- regio defects sum of 2,1-erythro and 2,1-threo insertions and 3,1-isomerizations
- 13 ⁇ 4 NMR spectroscopy or from 5 to 200, or from 10 to 200, or from 15 to 200, or from 17 to 175 regio defects per 10,000 propylene units, alternatively more than 5, or 10, or 20, or 30, or 40, but less than 200 regio defects, alternatively less than 150 regio defects per 10,000 propylene units.
- a median PD as determined by mercury intrusion porosimetry of less than 165 ⁇ or less than 160 ⁇ (or from 1, or 2, or 5, or 10 ⁇ up to 50, or 60, or 70, or 80, or 90, or 100, or 120, or 125, or 150, or 160, or 165 ⁇ ); and/or
- g a melt flow rate of 50 dg/min or more, as determined by ASTM D 1238, 230°C, 2.16 kg (or 60 dg/min or more, or 75 dg/min or more); and/or
- a multimodal Mw/Mn as determined by GPC-DRI, particularly the composition produced after stage A and stage B (the combined A&B components), or (ii) an Mw/Mn of greater than 1 to 5 (alternately 1.1 to 3, alternately 1.3 to 2.5), particularly the composition produced after stage A; i) a multimodal PSD; and/or
- a CDBI 50% or more (or 60% or more, alternately 70% or more, alternately 80% or more, alternately 90% or more, alternately 95% or more).
- propylene copolymer composition may have a melting point (Tm, DSC peak second melt) from at least 100°C to about 175°C, about 105°C to about 170°C, about 110°C to about 165°C, or about 115°C to about 155°C, and a crystallization point (Tc, DSC peak second melt) of 115°C or more, preferably from at least 100°C to about 150°C, about 105°C to about 130°C, about 110°C to about 125°C, or about 115°C to about 125°C.
- Tm melting point
- Tc DSC peak second melt
- the propylene polymer is heterophasic.
- the propylene polymer is an impact copolymer (ICP).
- the ICP comprises a blend of iPP (component A or the composition produced after stage Al and optionally stage A2 (the combined A1&A2 components) described above), preferably with a T m of 120°C or more, with a propylene polymer with a glass transition temperature (Tg) of -30°C or less and/or an ethylene polymer (component B).
- component A refers to the composition produced after stage A discussed in the preceding polymer product embodiments, as well as the composition produced after stage Al and stage Al and stage A2 (the combined A1&A2 components) described above.
- component A (or the combined A1&A2 component if present) comprises 60 to 95 wt% of the ICP, and component B 5 to 40 wt%, by total weight of components A (or the combined A1&A2 component if present) and B, or by total weight of the ICP.
- the iPP of component A (or the combined A1&A2 component if present) 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 matrix phase is comprised primarily of component A (or the combined A1&A2 component if present), while component (B) primarily comprises the dispersed phase or is co-continuous.
- the ICP comprises only two monomers: propylene and a single co-monomer 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 co-monomers chosen from among ethylene and C4 to Cg alpha-olefins, preferably two selected from ethylene, butene, hexene and octene.
- component A (or the combined A&B component if present) 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 160°C or more.
- component C has a Tg of -30°C or less, or -40°C or less, or -50°C or less.
- the (B) component has a heat of fusion (Hf) of 90°C or less (as determined by DSC).
- Hf heat of fusion
- the (B) component has an Hf of 70°C or less, preferably 50°C or less, preferably 35°C or less.
- the ICP produced from Stages A, combined A1&A2, and/or B is heterophasic, especially wherein the iPP is a continuous phase and the fill rubber is a dispersed or co-continuous phase.
- 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 (preferably primarily comprises) 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 co-monomer 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 phase comprises primarily one or more ethylene or propylene copolymer(s) with relatively high co-monomer 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).
- ICP in-situ ICP
- A optionally (A1&A2) and (C) 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 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 (A or A1&A2) matrix.
- a component (C) produced as a byproduct during this process, comprising primarily the non-propylene co-monomer (e.g., (C) will be an ethylene polymer if ethylene is used as the co-monomer).
- 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.
- the polymer composition produced herein is an in-situ-ICP.
- An "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.
- the regio defects are determined using 13 ⁇ 4 NMR spectroscopy as described below.
- the impact polymers produced typically have a heterophasic morphology such that the matrix phase is primarily propylene polymer having a Tm of 120°C or more and the dispersed phase is primarily an ethylene copolymer (such as EP Rubber) or propylene polymer typically having a Tg of -30°C or less.
- 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 co-monomer 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.
- impact copolymers comprise iPP (typically from stage A or A1&A2) and ethylene copolymer (typically from stage B) and typically have an ethylene copolymer (preferably ethylene propylene copolymer, preferably EP rubber) content in a range from a low of about 5 wt%, about 8 wt%, about 10 wt%, or about 15 wt%, or about 20 wt%, or about 30 wt%, or about 40 wt%, or about 50 wt%, to any higher upper limit of about 25 wt%, about 30 wt%, about 35 wt%, or about 40 wt%, or about 50 wt%, or about 60 wt%, or about 70 wt%, or about 75 wt%, or about 80 wt%, or about 85 wt% or higher.
- ethylene copolymer preferably ethylene propylene copolymer, preferably EP rubber
- the impact polymer can have an ethylene copolymer content of about 15 wt% to about 85 wt%, about 30 wt% to about 75 wt%, about 35 wt% to about 70 wt%, or about 40 wt% to about 60 wt%.
- the ICP has an ethylene copolymer content of at least about 25 wt%, at least about 30 wt%, at least about 35 wt%, or at least about 40 wt%, up to a high of about 50 wt%, 60 wt%, 70 wt%, 80 wt% or higher.
- impact copolymers comprise iPP (from stage A or A1&A2) and ethylene copolymer (from stage B), the impact copolymer can have a propylene content in the ethylene copolymer component from a low of about 25 wt%, about 85wt% or higher, or to about 37 wt%, or about 46 wt% to a high of about 73 wt%, or about 77 wt%, or about 80 wt%, based on the weight of the ethylene copolymer.
- the impact copolymer can have a propylene content of the ethylene copolymer component from about 25 wt% to about 80 wt%, about 10 wt% to about 75 wt%, about 35 wt% to about 70 wt%, or at least 40 wt% to about 80 wt%, based on the weight of the ethylene copolymer.
- 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.
- Hf heat of fusion
- the impact polymers produced herein have a 1% secant flexural modulus greater than about 300 MPa, or 500 MPa, or 700 MPa, or 1000 MPa, or 1500 MPa, or 2000 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 D 790 (A, 1.0 mm/min).
- the impact polymers produced herein may have an Mw (as measured by GPC-DRI) 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, or alternately from 330,000 to 500,000 g/mol.
- Mw as measured by GPC-DRI
- l ⁇ C-NMR Spectroscopy on Poly olefins Polypropylene microstructure is determined by l ⁇ C-NMR spectroscopy, including the concentration of isotactic and syndiotactic diads ([m] and [r]), triads ([mm] and [rr]), and pentads ([mmmm] and [rrrr]).
- concentration of isotactic and syndiotactic diads [m] and [r]
- triads [mm] and [rr]
- pentads [mmmm] and [rrrr]
- Signal-to-noise was enhanced by acquiring the spectra with nuclear Overhauser enhancement for 10 seconds before the acquisition pulse, and 3.2 second acquisition period, for an aggregate pulse repetition delay of 14 seconds. Free induction decays of 3400-4400 coadded transients were acquired at a temperature of 120°C. After Fourier transformation (256 K points and 0.3 Hz exponential line broadening), the spectrum is referenced by setting the dominant mmmm meso methyl resonance to 21.83 ppm.
- the regio defects each give rise to multiple peaks in the carbon NMR spectrum, and these are all integrated and averaged (to the extent that they are resolved from other peaks in the spectrum), to improve the measurement accuracy.
- the chemical shift offsets of the resolvable resonances used in the analysis are tabulated below. The precise peak positions may shift as a function of NMR solvent choice.
- the average integral for each defect is divided by the integral for one of the main propylene signals (CH3, CH, CH2), and multiplied by 10,000 to determine the defect concentration per 10,000 monomer units.
- Ethylene content in ethylene copolymers is determined by ASTM D 5017-96, except that the minimum signal-to-noise should be 10,000: 1.
- Propylene content in propylene copolymers is determined by following the approach of Method 1 in Di Martino and Kelchermans, J. Appl. Polym. Sci., 56, p. 1781 (1995), and using peak assignments from Zhang, Polymer, 45, p. 2651, (2004) for higher olefin co-monomers.
- 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.
- Tg is determined by DMA, according to the procedure set out in US 2008/0045638 at page 36, including any references cited therein.
- the support having an average particle size of from 5 ⁇ to 500 ⁇ , a specific surface area of 10 m 2 /g or more, a pore volume of from 0.1 to 4 mL/g, and a mean pore diameter of from 1 to 100 nm (10 to 200 A);
- Embodiment El wherein the support has average PS of more than 30 ⁇ up to 200 ⁇ , SA of 200 m 2 /g or more, PV of from 0.5 to 2 mL/g, and a mean PD of from 1 to
- the support comprises agglomerates of a plurality of primary particles (alternately primary particles having an average PS from 1 nm (alternately 1 or 5 ⁇ ) to 50 ⁇ (alternately 30 ⁇ )).
- Embodiment E3 wherein the catalyst system formed in the contacting has a bimodal particle size distribution comprised of at least about 5 vol% of the agglomerates and at least about 5 vol% of fragments of the agglomerates (alternately disagglomerated primary particles), based on the total volume of the supported catalyst system.
- the support has a mean PD greater than 2 nm (alternately greater than 3 nm, or greater than 4 nm, or greater than 5 nm, or greater than 6 nm, or greater than 7 nm, or greater than 8 nm; and/or less than 20 nm, or less than 15 nm, or less than 13 nm, or less than 12 nm, or less than 10 nm, or less than 8 nm, or less than 7 nm, or less than 6 nm).
- Embodiment E13 The process of Embodiment E12, wherein the temperature of the supporting, the contacting, or both, is above 60°C (alternately above 80°C, or above 100°C, or above 110°C, and/or up to 130°C).
- Embodiment El 4 further comprising (c) contacting the dispersed active catalyst system sites from (b) with one or more alpha-olefin monomers under polymerization conditions (alternately in one or more additional stages) to form a heterophasic copolymer.
- 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;
- RA is a structural bridge between two Cp moieties
- M4 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;
- n 1, 2, or 3, with the proviso that if m is 2 or 3, each Cp may be the same or different;
- each Q may be the same or different.
- 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 be the same or different;
- p 0, 1, 2, 3, or 4;
- q 1, 2, 3, or 4;
- RA is a structural bridge between the Cp moieties imparting stereorigidity to the metallocene compound
- 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 ⁇ ;
- (CpR*q) has bilateral or pseudobilateral symmetry; R*q is selected such that (CpR*q) forms a fluorenyl, alkyl substituted indenyl, or tetra-, tri-, or dialkyl substituted cyclopentadienyl radical; and (CpR"p) contains a bulky group in one and only one of the distal positions;
- A is chosen from group 4 metals, oxygen, or nitrogen, and R w is a methyl radical or phenyl radical, and v is the valence of A minus 1.
- M is a group 4, 5, or 6 metal
- T is a bridging group
- each X is, independently, an anionic leaving group
- each R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 1 1 , R 12 , and R 13 is, independently, halogen atom, hydrogen, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, substituted silylcarbyl, germylcarbyl, substituted germylcarbyl substituent or a - NR'2, -SR, -OR', -OSiR'3 or -PR'2 radical, wherein R' is one of a halogen atom, a C I -C I Q alkyl group, or a Cg-Ci 0 aryl group.
- each R' in the cyclopropyls substituent is, independently, hydrogen, a substituted hydrocarbyl group, an unsubstituted hydrocarbyl group, or a halogen.
- 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 C 1 to C ⁇ Q alkyl groups, substituted or unsubstituted C ⁇ to C ⁇ g alkoxy groups, substituted or unsubstituted Cg to C14 aryl groups, substituted or unsubstituted Cg to C14 aryloxy groups, substituted or unsubstituted C2 to C ⁇ g alkenyl groups, substituted or unsubstituted C to C40 arylalkyl groups, substituted or unsubstituted C to C40 alkylaryl groups and substituted or unsubstituted C to C40 arylalkenyl groups; or optionally are joined together to form a C4 to C40 alkanediyl group or a conjugated C4 to C40 diene ligand which is coordinated to M in a metallacyclopentene fashion; or optionally represent a conjugated diene, optionally, substitute
- R 3 , R 5 , R 6 , R 7 , R 9 , R 1 1 , R 12 and R 13 are each selected from the group consisting of hydrogen, halogen, hydroxy, substituted or unsubstituted C ⁇ to C ⁇ g alkyl groups, substituted or unsubstituted C ⁇ to C ⁇ g alkoxy groups, substituted or unsubstituted Cg to C14 aryl groups, substituted or unsubstituted Cg to C14 aryloxy groups, substituted or unsubstituted C2 to C ⁇ 0 alkenyl groups, substituted or unsubstituted C to C40 arylalkyl groups, substituted or unsubstituted C to C40 alkylaryl groups and C to C40 substituted or unsubstituted arylalkenyl groups; and
- T is selected from:
- R ⁇ 4 , Rl5, and Rl6 are each independently selected from hydrogen, halogen, C i to C20 alkyl groups, Cg to C30 aryl groups, C i 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 M 3 is selected from carbon, silicon, germanium, and tin; or
- T is represented by the formula:
- R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , and R 24 are each independently selected from hydrogen, halogen, hydroxy, substituted or unsubstituted C i to C ⁇ Q alkyl groups, substituted or unsubstituted Ci to C ⁇ g alkoxy groups, substituted or unsubstituted Cg to C 14 aryl groups, substituted or unsubstituted Cg to C 14 aryloxy groups, substituted or unsubstituted C2 to C ⁇ g alkenyl groups, substituted or unsubstituted C to C40 alkylaryl groups, substituted or unsubstituted C to C40 alkylaryl groups, and substituted or unsubstituted Cg to C40 arylalkenyl groups; optionally two or more adjacent radicals R ⁇ 7 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , and R 24 , including
- M 2 represents one or more carbon atoms, or a silicon, germanium, or tin atom.
- a single site catalyst system comprising:
- a support having an average PS of from 5 ⁇ to 500 ⁇ (alternately more than 30 ⁇ up to 200 ⁇ ), SA of 10 m /g or more (alternately 200 m /g or more, or 400 m /g or more), a PV of from 0.1 to 4 mL/g (alternately from 0.5 to 2 mL/g, or from 0.5 to 1.5 mL/g), and a mean PD of from 1 to 100 nm (alternately from 1 to 20 nm (10 to 200 A)).
- Embodiment E25 The catalyst system of Embodiment E23 or Embodiment E24, the support comprising agglomerates of a plurality of primary particles (alternately wherein the supported catalyst system has a bimodal particle size distribution comprised of at least about 5 vol% of the catalyst system supported on the agglomerates and at least about 5 vol% of the catalyst system supported on the fragments of the agglomerates, based on the total volume of the supported catalyst system).
- Embodiment E26 The catalyst system of Embodiment E25, wherein the primary particles have an average PS from 1 nm (alternately 1 or 5 ⁇ ) to 50 ⁇ (alternately 30 ⁇ ).
- Embodiment E27 The catalyst system of Embodiment E25 or Embodiment E26, wherein the agglomerates are at least partially encapsulated.
- E33 The catalyst system of any one of Embodiments E23 to E32, wherein the support has an average PS of more than 40 ⁇ (alternately more than 50 ⁇ , or more than 60 ⁇ , or more than 65 ⁇ , or more than 70 ⁇ , or more than 75 ⁇ , or more than 80 ⁇ , or more than 85 ⁇ , or more than 90 ⁇ , or more than 100 ⁇ , or more than 120 ⁇ ; and/or up to 200 ⁇ , or less than 180 ⁇ , or less than 160 ⁇ , or less than 150 ⁇ , or less than 130 ⁇ ).
- PS average PS of more than 40 ⁇ (alternately more than 50 ⁇ , or more than 60 ⁇ , or more than 65 ⁇ , or more than 70 ⁇ , or more than 75 ⁇ , or more than 80 ⁇ , or more than 85 ⁇ , or more than 90 ⁇ , or more than 100 ⁇ , or more than 120 ⁇ ; and/or up to 200 ⁇ , or less than 180 ⁇ , or less than 160 ⁇ , or less
- E34 The catalyst system of any one of Embodiments E23 to E33, wherein the SA is less than 1400 m 2 /g (alternately less than 1200 m 2 /g, or less than 1100 m 2 /g, or less than 1000 m 2 /g, or less than 900 m 2 /g, or less than 850 m 2 /g, or less than 800 m 2 /g, or less than 750 m 2 /g, or less than 700 m 2 /g, or less than 650 m 2 /g; and/or more than 500 m 2 /g, or more than 600 m 2 /g, or more than 650 m 2 /g, or more than 700 m 2 /g).
- E35 The catalyst system of any one of Embodiments E23 to E34, wherein the support has a mean PD greater than 2 nm (alternately greater than 3 nm, or greater than 4 nm, or greater than 5 nm, or greater than 6 nm, or greater than 7 nm, or greater than 8 nm; and/or less than 20 nm, or less than 15 nm, or less than 13 nm, or less than 12 nm, or less than 10 nm, or less than 8 nm, or less than 7 nm, or less than 6 nm).
- Embodiment E40 The catalyst system of Embodiment E40, wherein the co-activator is selected from 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, hexylmagnesium chloride, octylmagnesium chloride, methylmagnesium fluoride, ethylmagnesium fluoride, propylmagnes
- a polypropylene matrix having a porosity of at least 15% (alternately 20%, or 25%, or 30%, or 35%, or 40%; up to 85%, 80%, 75%, 70%, 60%, or 50%) based on the total volume of the propylene polymer matrix, and a median pore diameter of less than 165 ⁇ (alternately greater than 0.1, greater than 1, or greater than 2, or greater than 5, or greater than 6, or greater than 8, or greater than 10, or greater than 12, or greater than 15, or greater than 20 ⁇ ; up to less than 50, or less than 60, or less than 70, or less than 80, or less than 90, or less than 100, or less than 120, or less than 125, or less than 140, or less than 150, or less than 160 ⁇ ), as determined by mercury intrusion porosimetry; and
- Embodiment E49 The catalyst system of Embodiment E47 or Embodiment E48, wherein the propylene polymer has a 1% Secant flexural modulus of at least 1000 MPa (alternately at least 1300 MPa, or at least 1500 MPa, or at least 1700 MPa, or at least 1800 MPa, or at least 1900 MPa, or at least 2000 MPa), determined according to ASTM D 790 (A, 1.0 mm/min).
- E57 The catalyst system of any one of Embodiments E47 to E56, wherein the propylene polymer has an Mw (as measured by GPC-DRI) from 50,000 to 1,000,000 g/mol (alternately 80,000 to 1,000,000 g/mol, 100,000 to 800,000 g/mol, 200,000 to 600,000 g/mol, 300,000 to 500,000 g/mol, or 330,000 to 500,000 g/mol).
- Mw as measured by GPC-DRI
- Embodiments E23 to E58, wherein the single site catalyst precursor compound comprises zirconocene comprises zirconocene.
- MAO was obtained as a 30 wt% MAO in toluene solution from Albemarle (13.6 wt% Al or 5.04 mmol/g).
- Deuterated solvents were obtained from Cambridge Isotope Laboratories (Andover, MA) and dried over 3A molecular sieves. All 3 ⁇ 4 NMR data were collected on a Broker AVANCE III 400 MHz spectrometer running TopspinTM 3.0 software at room temperature (RT) using tetrachloroethane-d2 as a solvent (chemical shift of 5.98 ppm was used as a reference) for all materials.
- GPC-DRI Gel Permeation Chromatography-DRI
- Mw, Mn and Mw/Mn are determined by using a High temperature gel permeation chromatograph (Polymer Laboratories), equipped with a differential refractive index detector (DRI). Three Polymer Laboratories PLgel ⁇ Mixed-B columns are used. The nominal flow rate is 1.0 mL/min, and the nominal injection volume is 300 ⁇ .
- the various transfer lines, columns, and differential refractometer (the DRI detector) are contained in an oven maintained at 160°C.
- Solvent for the experiment is prepared by dissolving 6 grams of butylated hydroxytoluene as an antioxidant in 4 liters of Aldrich reagent grade 1,2,4-trichlorobenzene (TCB). The TCB mixture is then filtered through a 0.1 ⁇ Teflon filter. The TCB is then degassed with an online degasser before entering the GPC instrument. Polymer solutions are prepared by placing dry polymer in glass vials, adding the desired amount of TCB, then heating the mixture at 160°C with continuous shaking for about 2 hours. All quantities are measured gravimetrically. The injection concentration is from 0.5 to 2.0 mg/ml, with lower concentrations being used for higher molecular weight samples.
- the DRI detector Prior to running each sample the DRI detector is purged. Flow rate in the apparatus is then increased to 1.0 ml/minute, and the DRI is allowed to stabilize for 8 hours before injecting the first sample.
- 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. The Mw is calculated at each elution volume with following equation:
- 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 pre-determined concentration multiplied by injection loop volume. All molecular weights are reported in g/mol unless otherwise noted.
- MFR Melt Flow Rate
- DSC Differential Scanning Calorimetry
- the sample is equilibrated at -100°C before being heated to 220°C at a constant heating rate of 10°C/min (second heat).
- the exothermic peak of crystallization (first cool) is analyzed using the TA Universal Analysis software and the corresponding to 10°C/min cooling rate is determined.
- the endothermic peak of melting (second heat) is also analyzed using the TA Universal Analysis software and T m corresponding to 10°C/min heating rate is determined. Areas under the DSC curve are used to determine Hf, upon melting or H c , upon crystallization, and Tg.
- Capillary Rheology All capillary rheology tests on polymers were conducted with an ARC 2 rheometer at 200°C using a 1 mm die with a path length of 30 mm. The test conditions were reproduced according to ASTM D3835, Standard Test Method for Determination of Properties of Polymeric Materials by Means of a Capillary Rheometer, and the shear viscosity data were corrected using the Rabinowitsch correction factor to account for the velocity gradient at the die wall for non-Newtonian fluids.
- Mercury Porosimetry Mercury intrusion porosimetry was used to determine the porosity and the median PD of porous iPPs using an Autopore IV 9500 series mercury porosimeter, and unless indicated otherwise, an average Hg contact angle of 130.000°, an Hg surface tension of 485.000 dynes/cm, an evacuation pressure of 50 ⁇ Hg, and an Hg filling pressure of 3.65 kPa (0.53 psia) unless otherwise indicated.
- Raw silica was calcined in a CARBOLITE Model VST 12/600 tube furnace using a EUROTHERM 3216P 1 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.
- EXAMPLE 1 Supportation of MAO on Silica: Supported MAO (sMAO) was prepared at reaction initiation temperatures of -20°C to RT to reduce the risk of fragmentation of high SA, small PD silica upon reaction with MAO; or at temperatures up to 100°C or more, to facilitate higher MAO loading and/or stronger fixation to minimize MAO leaching from the support.
- the sMAO preparation conditions are listed in Table 2 below.
- sMAO Method I For low temperature sMAO preparation to minimize sMAO fragmentation (sMA02, sMA07), the following or a similar procedure was used. The silica was slurried in a reactor with 10X toluene - nota bene, all slurry and solvent liquid ratios are given as weight ratios relative to the starting silica material, e.g., raw silica or silica supported MAO and/or catalyst. The reactor was chilled in a freezer to -20°C and/or maintained at RT. The reactor was stirred at 500 rpm.
- sMAO Method II For partial fragmentation of sMAO (sMA03) and preparation of comparative, non-fragmented sMAO (CsMAOl, CsMA04), the following or a similar procedure was used. The silica was slurried in 4-5X toluene, chilled to -20°C, and 30 wt% MAO in toluene was added in two equal aliquots. The first aliquot was added under agitation, and the resultant slurry chilled in the freezer for about 5 minutes before addition of the second aliquot to maintain temperature below RT.
- the slurry was then allowed to stir for 2 hours at RT, filtered, reslurried in 3X toluene for 15 min and filtered a second time. Then the material was reslurried a second time in 3X toluene, stirred for 30 min at 80°C, filtered, reslurried a third time in 3X toluene, stirred at 80°C for 30 min, filtered, rinsed with 3X toluene, rinsed with 3X pentane, and dried under vacuum overnight.
- sMAO Method III For high temperature sMAO preparation (fragmented sMAOl; non-fragmented sMA04, sMA05, sMA06, sMA08; comparative CsMA02), the following or a similar procedure was used.
- the silica was slurried into 6X toluene in a reactor stirred at 500 rpm.
- the 30 wt% MAO solution was added slowly to the reactor to maintain the temperature below 40°C, then the reactor was stirred at 350 rpm at RT for 30 mins, and then heated at 100°C for 3 hours.
- the mixture was filtered through a medium frit, the wet solid was washed with 10X toluene, then 10X hexane, and dried under vacuum for 3 hours.
- CsMAO Method IV For comparative CsMA05, the following or a similar procedure was used. The silica was slurried into 6X toluene in a stirred reactor and chilled in the freezer. The 30 wt% MAO solution was added in 3 parts with the silica slurry returned to the freezer for a few minutes between additions. The slurry was stirred at RT for 2 hours, filtered, reslurried in 4X of toluene for 15 min at RT, and then filtered again. The solid was reslurried in 4X toluene at 80°C for 30 min and then filtered. The solid was reslurried in 4X toluene at 80°C for 30 min and then filtered a final time. The solid was washed with 2X toluene, then with pentane and dried under vacuum for 24 hours.
- EXAMPLE 2 Catalyst Supportation.
- the metallocene catalyst precursor compounds (MCN) and Ziegler-Natta catalysts (ZN) used in the examples and comparative examples below are identified in Table 3.
- the catalyst preparation/supportation conditions and yield of supported catalyst examples SCI - SC10 according to the present invention, and comparative examples CSC 1 and CSC2, are given in Table 4.
- Finished Catalyst Method II (SCat9, SCatl 1): MCN was preactivated by mixing with 40 eq. of MAO, and stirring for 1 hour at RT. Meanwhile, the sMAO was slurried in 20 mL of toluene and chilled in a freezer for 1 min. The preactivated MCN solution was then added to the chilled sMAO slurry, and the resulting mixture was allowed to stir for 1 hour, with cooling in the freezer for 1 minute out of every 10 minutes.
- the resulting slurry was heated to 40°C for 2 hours and filtered, reslurried in 20 mL toluene at 60°C over a period of 5 mins, stirred for 30 mins, and filtered again.
- the toluene wash was repeated twice, the solid material washed with 50 mL pentane, and dried under vacuum overnight to obtain a pink/purple solid.
- EXAMPLE 3 Preparation of porous iPP ("first stage reactor” or “Stage 1A and or IB"). Porous iPP was prepared according to embodiments of the present invention (PiPPl - PiPPl l) and according to comparatives (CiPP l - CiPP5) with the following representative procedure or similar. A 35 mL catalyst tube was loaded with 2 mL of 0.091M TNOAL (AkzoNobel) in hexane and injected into the reactor with nitrogen. The catalyst tube was then pressurized with hydrogen, which was then added to the reactor. Next, 600 mL of propylene was added to the reactor through the catalyst tube.
- TNOAL AkzoNobel
- the reactor was heated to 70°C with a stir rate of 500 rpm. Then, the supported or comparative catalyst was loaded into a second catalyst tube as a dry powder and inserted into the reactor along with 200 mL of propylene. The reactor was maintained at 70°C for 1 hour. Finally, the reactor was vented and polymer collected.
- the iPP polymerization data are shown in Table 5, mercury intrusion porosimetry data in Table 6A, and capillary rheology data and polymer characterizations in Table 6B.
- FIGs. 4, 5, and 6 Representative plots of incremental intrusion (mL/g) vs pore size diameter ( ⁇ ) are shown graphically in FIGs. 4, 5, and 6 for inventive sample PiPP4 and comparative samples CiPP2 and CiPP3. Statistically, the large pores indicated at the left sides of these incremental intrusion plots represent interstitial spaces between particles, and are accounted for in the reporting of the intrusion data. From FIG. 4, it is seen that the inventive PiPP4 has a relatively large number of pores in the 6-100 ⁇ range, and a median pore diameter of 12.2 ⁇ as reported in Table 6A.
- the inventive samples PiPPl, PiPP2, PiPP3, and PiPP4 have a porosity greater than 30% or greater than 40%, and the median pore diameters are in a suitable range, e.g., 10-100 ⁇ that will facilitate a relatively high rubber loading relative to iPP prepared using an MCN catalyst supported on a conventional silica support.
- capillary rheology confirms the MCN performance benefits of the inventive porous iPP, prepared with the inventive supports, on existing commercial processing equipment.
- inventive iPP can be prepared using a silica-supported MCN catalyst, thus providing a narrower molecular weight distribution, narrower composition distribution in the case of copolymers, lower extractables, processability and other advantages of an iPP prepared with a single site catalyst such as MCN, as compared to a similar iPP prepared using a ZN catalyst system.
- EXAMPLE 4 ICP Polymerization from Unimodal and Bimodal iPP.
- a unimodal or bimodal iPP prepolymer was prepared, then followed by addition of a comonomer to prepare an ICP heterophasic copolymer.
- Polymerization data for runs of the bimodal prepolymer, and ICP based on unimodal and bimodal iPP, are presented in Table 7.
- the catalyst tube and the 3 ml syringe were removed from the dry box and the catalyst tube attached to a 2L reactor while the reactor was being purged with nitrogen.
- the TNOAL was injected into the reactor via the scavenger port capped with a rubber septum, and the scavenger port valve was then closed.
- Propylene (1000 ml) was introduced to the reactor through a purified propylene line. The agitator was brought to 500 rpm. The mixture was allowed to mix for 5 minutes at RT. 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 RT.
- stage Al iPP prepolymer the reactor temperature was increased to and maintained at 70°C for the indicated time period.
- stage A2 iPP at the end of the A 1 stage, a 150 mL bomb with 0.207 MPa (30 psig) H 2 was opened to the reactor. A 0.220 MPa (31.9 psi) increase in reactor pressure and a 3°C increase in reactor temperature were observed. The reaction was allowed to run for the indicated time after the H 2 charge.
- Stage B ICP the agitator was set to 250 rpm 1 minute before the end of time period A2. At the end of the A2 period, using the reactor vent block valve, the reactor pressure was vented to 1.475 MPa (214 psig) while maintaining reactor temperature as close as possible to 70°C. The agitator was increased back up to 500 rpm. The reactor temperature was stabilized at 70°C with the reactor pressure reading 1.481 MPa (214.8 psig). Ethylene gas at 0.938 MPa (136 psi) was introduced into the reactor, targeting a total pressure of 2.41 MPa (350 psig). The reactor was held at this pressure for 20 minutes. Using the reactor vent block valve, the reactor was quickly vented to stop the polymerization. The reactor bottom was dropped and a polymer sample collected. After overnight drying, the sample was a free flowing ICP resin.
- ICP from Unimodal iPP (Runs 3-4, 6-8): iPP prepolymer was prepared generally as described above. After heating the reactor to 70°C, a 150 mL bomb filled with H 2 pressure as indicated in Table 7 was opened to the reactor. The reaction was allowed to run for Al time indicated after the H 2 charge. At 1 minute before the Al time, the agitator was set to 250 rpm. At the end of the A 1 time, using the reactor vent block valve, the reactor pressure was vented to 1.475 MPa (214 psi) while maintaining reactor temperature as close as possible to 70°C. The agitator was increased back up to 500 rpm.
- the reactor temperature was stabilized at 70°C with the reactor pressure reading 1.481 MPa (214.8 psi). Ethylene gas at 0.938 MPa (136 psig) was introduced to the reactor, targeting a total pressure of 2.413 MPa (350 psi). The reactor was held at this pressure for the B (ICP) stage time indicated. Using the vent block valve, the reactor was quickly vented to stop the polymerization. Dropped reactor bottom and collected sample. Using the reactor vent block valve, the reactor was quickly vented to stop the polymerization. The reactor bottom was dropped and a polymer sample collected. After overnight drying, the sample was a free flowing ICP resin.
- EXAMPLE 6 iPP from Controlled Fragmentation of Catalyst Support.
- MCN compounds were supported on sMAO prepared at varying temperature conditions and metal alkyl treatments to investigate catalyst activity and the PSD, stiffness, and other properties of the iPP and ICP made with the catalyst systems.
- the catalyst systems CSC3, SCat2, SCatl l, and SCatlA were used to prepare comparative and inventive porous iPP polymers CiPP6, PiPP12, PiPP13, and PiPP13, respectively, using the polymerization procedures of Example 3 at the polymerization conditions listed in Table 8 below.
- the median size of the CiPP6 particles produced using the conventionally supported MCN system has a bell-shaped unimodal PSD centered near 700 ⁇ .
- PiPP12 produced using a generally non-fragmented support that survived generally intact from MAO supportation conducted at ambient or below for 3 hours, produced relatively large iPP particles with very few if any particles less than 500 ⁇ , and most or all greater than about 600 ⁇ up to 1500 ⁇ or more.
- PiPP13 produced using a partially fragmented support from an MAO supportation reaction conducted at 80°C for 1 hour, produced a bimodal PSD comprising a small particle mode centered near 200 ⁇ and the larger particles having a size increasing from near 600 ⁇ up to 1000 ⁇ or more.
- PiPP14 produced using a fragmented support from an MAO supportation reaction conducted at 100°C for 3 hours, produced a PSD comprised mainly (>80 wt%) of small particles centered near 200 ⁇ , with only small amounts ( ⁇ 10 wt%) of larger particles in the 500 ⁇ to 1000 ⁇ range.
- EXAMPLE 7 iPP from Catalyst Supportation with and without TIBA Treatment.
- MAO was supported on D 150-60A silica using both high temperatures (100°C for 3 hours, for high loading (11.5 mmol Al/g silica) to gain iPP polymerization activity) and low temperatures ( ⁇ 30°C for 3 hours, for low loading (7 mmol Al/g silica) to build high porosity iPP resins), with and without TIBA treatment to investigate any activity enhancement.
- the MAO and MCN supportation procedures follow below, and the catalyst systems were used to prepare iPP and ICP using procedures similar to Examples 3-4.
- the wet cake was charged into a reactor with 7X toluene and stirred at 300 rpm. Then, 0.50 lg TIBA were added to the slurry, and after stirring for 15min, 0.139 g of MCN3 was added to the reactor. After stirring 1 hr at RT, the slurry was filtered through a coarse frit and washed twice with 8X toluene and twice with 8X hexane. The wet cake was dried under vacuum for 1 hr, yielding 7.04 g. This sCat was used to prepare ICP1 as indicated in Table 9.
- TIBA treatment increased the catalyst activity, considered to be attributable to the removal of possible hydroxyl groups which may have been uncovered during MAO supportation and/or support fragmentation.
- the polymer characterization and stiffness data are presented in Table 10. These data further confirm that the catalysts according to embodiments disclosed herein provide a significant improvement in the iPP and/or ICP stiffness characterized by 1% secant flex modulus stiffness, e.g., greater than about 1950 MPa, greater than about 2000 MPa, greater than about 2100 MPa, greater than about 2200MPa.
- Fig 11 is a GPC-4D chromatogram for ICP1 indicating the ethylene uptake is about 18-20 wt% and the EP rubber uptake is 37 wt%. Calculated from the yield data, the total EP rubber uptake is 44 wt%. Accordingly, 37 - 44 wt% EP rubber uptake may be achieved according to embodiments of the present invention, representing a vast improvement over impact copolymers produced using ZN catalyst systems known in the art, which typically require post reactor addition of plastomer to produce the ICP.
- EXAMPLE 8 High Temperature Supportation for Improved Catalyst Activity.
- sMAO-948 In a CELSTIR flask, 20.1925 g of silica CS 1 were slurried in 6X toluene and chilled in a freezer at -35°C for 5 minutes. Then, 50.6094 g MAO (30% in toluene) were slowly added to the slurry. The slurry was stirred for 2.25 hr while warming up to RT. The white solid was filtered and then reslurried in 4X toluene for 15 minutes. The slurry was filtered again, reslurried in 4X toluene and stirred for 30 minutes at 80°C.
- sCatl2 (Hf) In this supportation, 13.6 mg (0.0137 mmol) of MCN7 was dissolved in 2 mL of toluene with 0.1439 g MAO (30% in toluene) and stirred for lhr at RT. Then, 0.3459 g sMAO-948 was slurried in 20 mL of toluene. The catalyst solution was added to the slurry and stirred for 1 hr, with chilling 1 min of every 10 in the freezer. The slurry was placed in an oil bath and the temperature rapidly increased to 130°C and held for 4 hr. The slurry was quickly filtered and washed three times with 20 mL of toluene and twice with 20mL of pentane. The solid was dried under vacuum. Yield: 0.3318 g of yellowish solid.
- sCatl3 (Hf) In this supportation, 24.5 mg (0.0405 mmol) MCN8 was dissolved with 0.3521 g MAO (30% in toluene) in 3 mL toluene and stirred for 1 hr. Then, 1.0101 g sMAO-948 was slurried in 20 mL toluene. The catalyst was added to the slurry and stirred for 4 hr at 100°C. The solid was filtered, washed twice with 20 mL toluene and once with 20 mL of pentane. The solid was dried under vacuum. Yield: 0.9802 g of yellow powder.
- sCatl4 (Zr) In this supportation, 42.1 mg (0.0465 mmol) of MCN2 was dissolved with 0.4167 g MAO (30% in toluene) in 3 mL toluene and stirred for lhr. Then, 1.1636 g sMAO- 948 was slurried in 20 mL of toluene. The catalyst solution was added to the sMAO-948 slurry and stirred for 4 hr at 100°C. The solid was filtered, washed twice with 20 mL of toluene and once with 20 mL of pentane. The solid was dried under vacuum. Yield: 1.1712 g pink/purple solid.
- sCatl5 (Zr + TIBA): In this supportation, 3.1 g sMAO-D150-60A was slurried in 5 g toluene in a 20 mL vial. Then, 0.17 g neat TIBA (0.85 mmol) were added slowly to the slurry with vigorously shaking. The slurry was then placed on a shaker for 10 min. Gas evolution was observed. Next, 30 mg (0.051 mmol Zr) MCN5 was mixed into the slurry and the mixture was shaken for 2 hr at RT. The dark brown slurry was filtered, washed with 10 g toluene, 2x6 g hexane, and dried under vacuum for 2 hr. Yield: 3.08 g dark brown solid.
- SCatl6 (Zr) A 125 mL CELSTIR reactor was charged with 11 g sMAO-D150-60A along with 5X toluene. The mixture was stirred at 350 rpm. A 20 mL vial was charged with 6.0 g MAO (30% in toluene) and 0.130 g (0.22 mmol Zr) MCN5. The mixture in the vial was shaken well before it was added to the sMAO-D150-60A slurry.
- iPP Polymerization Propylene polymers were produced according to a general procedure for propylene polymerization, wherein batch propylene polymerizations were run in a 2 L autoclave reactor. All solvents, reactants, and gases were purified by passing through multiple columns containing 3-angstrom molecular sieves and oxygen scavengers. Typically, propylene, scavenger (tri-n-octylaluminum), and hydrogen, either initially or during the reaction, were added to the reactor. A slurry of the catalyst was pushed in with liquid propylene either at RT or reaction temperature as noted in Table 12. Polymerization was carried out for a set amount of time and then the reactor was cooled, depressurized, opened and the polymer collected. The reaction conditions and results are shown in Table 12.
- 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.
- Table 1 Silica Properties and Calcination Temperature
- Tc - Calcination temperature PS - average particle size (from manufacturer); SA - BET surface area (from manufacturer); PV - pore volume (from manufacturer);
- MCN is mixed with 40 eq.
- MAO 40: 1 Al:Zr
- RT a Pre-activation: MCN is mixed with 40 eq.
- MAO 40: 1 Al:Zr
- RT a Calculated based on charge materials
- c ⁇ RT chilled in the freezer inside the dry box, -20 to -35°C, and warming up at RT after taking out from the dry box for reagent addition.
- CiPP5 CSC6 52 2476 71.7 45 1148 181.5 68.81 2.63
- iPP H 2 is the iPP Stages I and II H 2 pressure in the 150mL bomb charged into the reactor; iPP 1 " T is the iPP Stages Al / A2 polymerization times; ICP Time is the Stage B time; a - too much catalyst charge caused melted polymer that likely decreased the activity; b - some melted ICP resins formed, the Cv is for the non- melted majority ICP resins; comparative example; serious reactor fouling was found; ' from RT recrystallization of iPP from ICP xylene solution obtained from 130°C 60 min heating, the actual Cv is typically 10-20 wt% higher.
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Abstract
Cette invention concerne des procédés de support de catalyseur à site unique impliquant un traitement à haute température (≥ 40 °C, par exemple, 100 à 130 °C) pour améliorer l'activité du catalyseur pour la polymérisation d'oléfines, par exemple, la polymérisation de propylène, et des systèmes de catalyseur supporté obtenus à l'aide des procédés, par exemple, des systèmes de catalyseurs à site unique supportés sur un support présentant une taille moyenne des particules (PS) élevée ≥ 30 µm, une grande surface active (SA ≥ 200 m2/g), un faible volume de pore (PV ≤ 2 ml/g), et une plage de diamètres moyens de pore de 1 ≤ PD ≤ 20 nm.
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