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US20060281879A1 - Catalyst compositions comprising small silica support materials and methods of use in polymerization reactions - Google Patents

Catalyst compositions comprising small silica support materials and methods of use in polymerization reactions Download PDF

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Publication number
US20060281879A1
US20060281879A1 US11/151,097 US15109705A US2006281879A1 US 20060281879 A1 US20060281879 A1 US 20060281879A1 US 15109705 A US15109705 A US 15109705A US 2006281879 A1 US2006281879 A1 US 2006281879A1
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US
United States
Prior art keywords
catalyst
compound
microns
silica
silica support
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Abandoned
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US11/151,097
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English (en)
Inventor
Maria Apecetche
Phuong Cao
Michael Awe
Ann Schoeb-Wolters
Ryan Impelman
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Univation Technologies LLC
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Univation Technologies LLC
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Application filed by Univation Technologies LLC filed Critical Univation Technologies LLC
Priority to US11/151,097 priority Critical patent/US20060281879A1/en
Assigned to UNIVATION TECHNOLOGIES, LLC reassignment UNIVATION TECHNOLOGIES, LLC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: IMPELMAN, RYAN W., APECETCHE, MARIA A., CAO, PHUONG A., SCHOEB-WOLTERS, ANN M., AWE, MICHAEL D.
Priority to PCT/US2006/020327 priority patent/WO2006138036A1/fr
Priority to CN2006800171121A priority patent/CN101189272B/zh
Priority to JP2008516892A priority patent/JP2008544040A/ja
Priority to RU2008101446/04A priority patent/RU2403266C2/ru
Priority to KR1020087000875A priority patent/KR20080019060A/ko
Priority to US11/441,505 priority patent/US7259125B2/en
Priority to CA2610843A priority patent/CA2610843C/fr
Priority to BRPI0611761-9A priority patent/BRPI0611761A2/pt
Priority to EP06771229.9A priority patent/EP1891125B1/fr
Publication of US20060281879A1 publication Critical patent/US20060281879A1/en
Priority to US11/825,867 priority patent/US7381780B2/en
Priority to ZA200708935A priority patent/ZA200708935B/xx
Priority to US12/148,152 priority patent/US8012903B2/en
Abandoned legal-status Critical Current

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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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • 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
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • 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
    • C08F4/02—Carriers therefor
    • 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
    • C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
    • C08F4/652—Pretreating with metals or metal-containing compounds
    • C08F4/654—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof

Definitions

  • the present invention relates to a polymerization process using improved catalyst compositions.
  • the catalyst compositions of the present invention relate to a Ziegler-Natta type catalyst compound that includes a small silica support material, and demonstrate improved productivity.
  • Ziegler-Natta catalyst systems are utilized extensively in commercial processes that produce high density and low-density polyethylenes in a variety of molecular weights. Production rates in certain gas phase reactors may be limited in their ability to discharge from the reactor the polymer particles that are produced during the reaction. In certain of such cases, an increase in the bulk density of the polymer particles may increase the production rate of the reactor. Generally, Ziegler-Natta catalysts that have increasing activity and productivity, and that are used in gas phase operations. may tend to produce polymer products that have decreasing bulk density. If a reactor is limited in its ability to discharge the polymer product, the use of a high activity catalyst may result in a decrease in the bulk density of the polymer product.
  • FIG. 1 is an exemplary process flow diagram for an exemplary reaction system with which an exemplary catalyst system of the present invention may be employed.
  • FIG. 2 is an exemplary silica dehydration profile used in certain exemplary embodiments of the present invention.
  • FIG. 3 illustrates particle size distributions for a sample of Davison 955 silica and a sample of Ineos ES757 silica.
  • FIG. 4 illustrates particle size distributions for a sample of Davison 955 silica that was screened through 325 mesh.
  • FIG. 5 is a graphical illustration of ethylene flow versus reaction time for certain exemplary polymerization processes employing exemplary catalyst systems that used a variety of exemplary support materials.
  • FIG. 6 is a graphical illustration of the results of a statistical analysis of the activity demonstrated by exemplary laboratory-prepared catalyst precursors.
  • FIG. 7 is a graphical illustration of the relationship between catalyst system productivity and polymer product bulk density for certain exemplary catalyst systems.
  • FIG. 8 is a graphical illustration of the relationship between catalyst system productivity and polymer product bulk density for certain exemplary catalyst systems.
  • polymers e.g., ethylene homopolymers and copolymers
  • polymers readily can be produced with desirable physical properties and catalyst system productivities in a low pressure gas phase fluid bed reaction process in the presence of a specific high productivity catalyst that is impregnated on a porous particulate silica having a particle size in a particular range, as is also detailed below.
  • the compounds used to form the catalysts of the present invention include at least one titanium compound, at least one magnesium compound, at least one electron donor compound, at least one activator compound and at least one silica material, exemplary embodiments of which are illustrated below.
  • the titanium compound has the formula Ti(OR) a X b wherein
  • the titanium compounds individually may be present in the catalysts of the present invention, or the titanium compounds may be present in combinations thereof.
  • a nonlimiting list of suitable titanium compounds includes TiCl 3 , TiCl 4 , Ti(OCH 3 )Cl 3 , Ti(OC 6 H 5 )Cl 3 , Ti(OCOCH 3 )Cl 3 and Ti(OCOC 6 H 5 )Cl 3 .
  • the magnesium compound has the formula MgX 2 wherein
  • Such magnesium compounds may be present individually in the catalysts of the present invention, or the magnesium compounds may be present in combinations thereof.
  • a nonlimiting list of suitable magnesium compounds includes MgCl 2 , MgBr 2 and MgI 2 .
  • the magnesium compound may be anhydrous MgCl 2 .
  • the magnesium compound may be present in the catalysts of the present invention in an amount in the range of from 0.5 to 56 moles of magnesium compound per mole of titanium compound.
  • the magnesium compound may be present in the catalysts of the present invention in an amount in the range of from 1.5 to 11 moles of magnesium compound per mole of titanium compound.
  • the magnesium compound may be present in the catalysts of the present invention in an amount in the range of from 1.5 to 7 moles of magnesium compound per mole of titanium compound.
  • the titanium compound and the magnesium compound may be used in a form that will facilitate their dissolution in the electron donor compound, as described herein below.
  • the electron donor compound generally may be any organic compound that is liquid at 25° C., and that may be capable of dissolving both the titanium compound and the magnesium compound.
  • the electron donor compound may be a Lewis base.
  • suitable electron donor compounds includes such compounds as alkyl esters of aliphatic and aromatic carboxylic acids, aliphatic ethers, cyclic ethers and aliphatic ketones.
  • suitable electron donor compounds may be alkyl esters of C 1 to C 4 saturated aliphatic carboxylic acids; alkyl esters Of C 7 to C 8 aromatic carboxylic acids; C 2 to C 8 , and preferably C 3 to C 4 , aliphatic ethers; C 3 to C 4 cyclic ethers, and, in certain embodiments, C 4 cyclic mono- or di-ethers; C 3 to C 6 , and, in certain embodiments, C 3 to C 4 , aliphatic ketones.
  • the electron donor compound may be methyl formate, ethyl acetate, butyl acetate, ethyl ether, hexyl ether, tetrahydrofuran, dioxane, acetone or methyl isobutyl ketone, among others.
  • the electron donor compounds may be present individually in the catalysts of the present invention, or they may be present in combinations thereof. Generally, the electron donor compound may be present in the range of from 2 to 85 moles of the electron donor compound per mole of the titanium compound. In certain embodiments, the electron donor compound may be present in the catalysts of the present invention in an amount in the range of from 3 to 10 moles of the electron donor compound per mole of the titanium compound.
  • the activator compound generally has the formula Al(R′′) c X′ d H e wherein
  • activator compounds may be present individually in the catalysts of the present invention, or they may be present in combinations thereof.
  • a nonlimiting list of suitable activator compounds includes Al(C 2 H 5 ) 3 , Al(C 2 H 5 ) 2 Cl, Al(i ⁇ C 4 H 9 ) 3 , Al 2 (C 2 H 5 ) 3 Cl 3 , Al(i ⁇ C 4 H 9 ) 2 H, Al(C 6 H 13 ) 3 , Al(C 8 H 17 ) 3 , Al(C 2 H 5 ) 2 H and Al(C 2 H 5 ) 2 (OC 2 H 5 ).
  • the activator compound may be present in the catalysts of the present invention in an amount in the range of from 10 to 400 moles of activator compound per mole of the titanium compound, and in certain embodiments may be present in the range of from 15 to 60 moles of the activator compound per mole of the titanium compound, and in certain embodiments may be present in the range of from 2 to 7 moles of the activator compound per mole of the titanium compound.
  • the silica support that may be employed in the catalysts of the present invention generally has a particle size distribution within the range of from 2 microns to 100 microns, and a median particle size in the range of from 20 microns to 50 microns. In certain exemplary embodiments, the silica support has a particle size distribution within the range of from 2 microns to 80 microns. In certain exemplary embodiments, the silica support has a median particle size in the range of from 20 microns to 35 microns, and in the range of from 20 to 30 microns in certain exemplary embodiments.
  • the silica support has a particle size distribution in which no more than 10% of the particles have a size below 10 microns, and no more than 10% of the particles have a size greater than 50 microns. In certain exemplary embodiments, the silica support has a particle size distribution in which no more than 10% of the particles have a size below 12 microns, and no more than 8% of the particles have a size greater than 50 microns.
  • the productivity of the supported catalyst generally increases, as does the FAR value of film formed from resin produced by the supported catalyst. In certain exemplary embodiments, this may be accompanied by an increase in the bulk density and a decrease in the average particle size of such resin.
  • the silica supports used in the improved catalysts of the present invention may facilitate, inter alia, greater productivity from the improved catalysts as well as the production of polymers having greater bulk density.
  • the improved catalysts of the present invention comprising these silica supports may have a productivity (as based on a mass balance) that is at least 3,000 pounds polymer per pound of catalyst per hour; and that is at least 4,500 pounds polymer per pound of catalyst per hour in certain exemplary embodiments, and that is at least 6,000 pounds polymer per pound of catalyst per hour in certain exemplary embodiments, and that is at least 7,000 pounds polymer per pound of catalyst per hour in certain exemplary embodiments; and that is at least 9,000 pounds polymer per pound of catalyst per hour in certain exemplary embodiments.
  • the polymers produced from the processes of the present invention that employ improved catalysts that include these silica supports may have a settled bulk density of at least 21.5 pound per cubic foot in certain exemplary embodiments; and at least 22.5 pound per cubic foot in certain exemplary embodiments, and at least 23.5 pound per cubic foot in certain exemplary embodiments; and at least 24.0 pound per cubic foot in certain exemplary embodiments.
  • Certain exemplary embodiments of the polymers produced from the processes of the present invention that employ improved catalysts that include these silica supports may have even greater settled bulk densities.
  • the silica support employed in the present invention has an average pore diameter of greater than 100 Angstrom units, and in certain exemplary embodiments, greater than 150 Angstrom units. It also may be desirable for such silica support to have a surface area of ⁇ 200 square meters per gram, and in certain exemplary embodiments, ⁇ 250 square meters per gram. In certain exemplary embodiments, the average pore volume of such silica support ranges from 1.4 ml/gram to 1.8 ml/gram.
  • the silica support generally should be dry, that is, free of absorbed water. Drying of the silica support generally is performed by heating it at a temperature of ⁇ 600° C.
  • the improved catalysts of the present invention may be prepared by first preparing a precursor composition from the titanium compound, the magnesium compound, and the electron donor compound, as described below, then impregnating the silica support with the precursor composition, and then treating the impregnated precursor composition with an activator compound as described below.
  • the precursor composition may be formed by dissolving the titanium compound and the magnesium compound in the electron donor compound at a temperature in the range of from 20° C. up to the boiling point of the electron donor compound.
  • the titanium compound can be added to the electron donor compound before, or after, the addition of the magnesium compound, or concurrent therewith.
  • the dissolution of the titanium compound and the magnesium compound may be facilitated by stirring, and in some instances by refluxing, these two compounds in the electron donor compound.
  • the precursor composition may be isolated by crystallization or by precipitation with a C 5 to C 8 aliphatic or aromatic hydrocarbon such as hexane, isopentane or benzene.
  • the crystallized or precipitated precursor composition may be isolated, generally in the form of fine, free-flowing particles having an average particle size in the range of from 10 to 100 microns.
  • the precursor composition has the formula: Mg m Ti 1 (OR) n X p [ED] q wherein:
  • the precursor composition then may be impregnated, in a weight ratio of about 0.003 to 1, and, in certain exemplary embodiments, about 0.1 to 0.33, parts of the precursor composition into one part by weight of the carrier material.
  • the silica support Before being impregnated, the silica support is dehydrated at 600 ° C., and also is treated with an aluminum alkyl compound (e.g., “TEAL”).
  • TEAL aluminum alkyl compound
  • Dehydrated silica supports that have been treated with TEAL may be referred to herein as TEAL-on-silica, or “TOS.”
  • the impregnation of the dehydrated, activated silica support (e.g., the TOS) with the precursor composition may be accomplished by dissolving the precursor composition in the electron donor compound, and by then admixing the dehydrated, activated silica support with the precursor composition to impregnate the dehydrated, activated silica support.
  • the electron donor compound then may be removed by drying at temperatures of ⁇ 60° C.
  • the silica support also may be impregnated with the precursor composition by adding the silica support to a solution of the chemical raw materials used to form the precursor composition in the electron donor compound, without isolating the precursor composition from such solution.
  • the excess electron donor compound then may be removed by drying, or by washing and drying at temperatures of ⁇ 60° C.
  • the precursor composition will be fully or completely activated, e.g., it will be treated with sufficient activator compound to transform the Ti atoms in the precursor composition to an active state.
  • Suitable activators include, but are not limited to, tri-n-hexyl aluminum, triethyl aluminum, diethyl aluminum chloride, trimethyl aluminum, dimethyl aluminum chloride, methyl aluminum dichloride triisobutyl aluminum, tri-n-butyl aluminum, diisobutyl aluminum chloride, isobutyl aluminum dichloride, (C 2 H 5 )AlCl 2 , (C 2 H 5 O)AlCl 2 , (C 6 H 5 )AlCl 2 , (C 6 H 5 O)AlCl 2 , (C 6 H 12 O)AlCl 2 and the corresponding bromine and iodine compounds).
  • the precursor composition first may be partially activated outside the polymerization reactor with enough activator compound so as to provide a partially activated precursor composition having an activator compound/Ti molar ratio of >0 to ⁇ 10:1, and, in certain exemplary embodiments, from 4 to 8:1.
  • This partial activation reaction may be carried out in a hydrocarbon solvent slurry followed by drying of the resulting mixture (to remove the solvent), at temperatures between 20 to 80° C., and, in certain exemplary embodiments, between 50 to 70° C.
  • the solvent for the activator(s) should be non-polar and capable of dissolving the activator(s), but not the precursor composition.
  • hydrocarbon solvents such as isopentane, hexane, heptane, toluene, xylene, naptha and aliphatic mineral oils such as but not limited to KaydolTM, HydrobriteTM 550 and the like.
  • the resulting product is a free-flowing solid particulate material that readily may be fed to the polymerization reactor.
  • the partially activated and impregnated precursor composition may be fed to the polymerization reactor where the activation may be completed with additional activator compound, which may be the same or a different compound.
  • the additional activator compound and the partially activated impregnated precursor composition optionally may be fed to the reactor through separate feed lines.
  • the additional activator compound may be sprayed into the reactor in either undiluted form (e.g., “neat”), or in the form of a solution of the additional activator compound in a hydrocarbon solvent (e.g., isopentane, hexane, or mineral oil). Such solution may contain about 2 to 30 weight percent of the activator compound.
  • the additional activator compound may be added to the reactor in such amounts as to provide, along with the amounts of activator compound and titanium compound fed with the partially activated and impregnated precursor composition, a total Al/Ti molar ratio in the reactor of ⁇ 10 to 400, and, in certain exemplary embodiments, from 15 to 60.
  • the additional amounts of activator compound added to the reactor may react with, and complete the activation of, the titanium compound in the reactor.
  • discrete portions of the partially activated precursor composition impregnated on the silica support are continuously fed to the reactor, along with discrete portions of additional activator compound, during the continuing polymerization process, and may replace active catalyst sites that are expended during the course of the reaction.
  • the polymerization reaction may be conducted by contacting a stream of monomer(s), in a gas phase process (such as in the fluid bed process described below), and substantially in the absence of catalyst poisons (e.g., moisture, oxygen, CO, CO 2 , and acetylene) with a catalytically effective amount of the completely activated precursor composition at a temperature and at a pressure sufficient to initiate the polymerization reaction.
  • catalyst poisons e.g., moisture, oxygen, CO, CO 2 , and acetylene
  • Table 1 below provides a listing of the amounts, in moles, of various comonomers that may be copolymerized with ethylene in order to provide polymers having a desired density range (e.g., within the range of from 0.91 to 0.97) at any given melt index. Table 1 also indicates the relative molar concentration, of such comonomers to ethylene, which may be present in the recycled gas stream of monomers under reaction equilibrium conditions in the reactor.
  • the reactor 1 generally includes a reaction zone 2 and a velocity-reduction zone 3 .
  • the reaction zone 2 includes a bed of growing polymer particles, formed polymer particles and a minor amount of catalyst particles fluidized by the continuous flow of gaseous components in the form of make-up feed and recycle gas through the reaction zone 2 .
  • the mass gas flow rate through the bed generally will be above the minimum flow required for fluidization, and, in certain exemplary embodiments, may be in the range of from 1.5 to 10 times G mf and, in certain exemplary embodiments, in the range of from 3 to 6 times G mf .
  • G mf is used in the accepted form as the abbreviation for the minimum mass gas flow required to achieve fluidization, as may be set forth further in, for example, C. Y. Wen and Y. H. Yu, “Mechanics of Fluidization,” Chemical Engineering Progress Symposium Series, Vol. 62, p. 100-111 (1966).
  • the bed will contain particles that may prevent the formation of localized “hot spots” and that may entrap and distribute the particulate catalyst throughout the reaction zone 2 .
  • the reactor 1 usually may be charged with a base of particulate polymer particles before gas flow is initiated. Such particles may be identical in nature to the polymer to be formed, or may be different therefrom.
  • the particulate polymer particles provided as a base may be withdrawn with the desired formed polymer particles as the first product.
  • a fluidized bed of the desired polymer particles supplants the start-up bed.
  • the partially activated precursor composition (impregnated on the SiO 2 support) used in the fluidized bed may be stored for service in a reservoir 4 under a blanket of a gas that is inert to the stored material, such as nitrogen or argon.
  • Fluidization is achieved by a high rate of gas recycle to and through the bed, typically in the order of about 50 times the rate of feed of make-up gas.
  • the fluidized bed has the general appearance of a dense mass of viable particles in possible free-vortex flow as created by the percolation of gas through the bed.
  • the pressure drop through the bed may be equal to, or slightly greater than, the mass of the bed divided by the cross-sectional area, and thus may depend on the geometry of the reactor 1 .
  • Make-up gas may be fed to the bed at a rate equal to the rate at which particulate polymer product is withdrawn.
  • the composition of the make-up gas may be determined by a gas analyzer 5 positioned above the bed.
  • the gas analyzer 5 may determine the composition of the gas being recycled, and the composition of the make-up gas may be adjusted accordingly to maintain an essentially steady state gaseous composition within the reaction zone 2 .
  • the recycle gas and, where desired, part of the make-up gas may be returned over gas recycle line 6 to the reactor 1 at point 7 below the bed.
  • a gas distribution plate 8 may be located at this point above the point of return to aid in fluidizing the bed.
  • the portion of the gas stream that does not react in the bed constitutes the recycle gas which is removed from the reaction zone 2 , preferably by passing it into a velocity reduction zone 3 above the bed where entrained particles may be given an opportunity to drop back into the bed.
  • the recycle gas then may be compressed in a compressor 9 and then passed through a heat exchanger 10 wherein the heat of reaction may be removed from it before it is returned to the bed.
  • the temperature of the bed is controlled at an essentially constant temperature under steady state conditions by constantly removing heat of reaction. No noticeable temperature gradient exists within the upper portion of the bed. A temperature gradient will exist in the bottom of the bed in a layer of about 6 to 12 inches, between the temperature of the inlet gas and the temperature of the remainder of the bed.
  • the recycle gas is then returned to the reactor 1 at its base 7 and to the fluidized bed through distribution plate 8 .
  • the compressor 9 also can be placed downstream of the heat exchanger 10 .
  • the distribution plate 8 may play an important role in the operation of the reactor 1 .
  • the fluidized bed contains growing and formed particulate polymer particles as well as catalyst particles. As the polymer particles are hot and possibly active, it may be well to prevent them from settling, for if a quiescent mass is allowed to exist, any active catalyst contained therein may continue to react and cause fusion. Diffusing recycle gas through the bed at a rate sufficient to maintain fluidization throughout the bed is, therefore, beneficial.
  • the distribution plate 8 serves this purpose, and may be a screen, slotted plate, perforated plate, a plate of the bubble cap type and the like. The elements of the distribution plate 8 all may be stationary, or the distribution plate 8 may be of the mobile type disclosed in U.S. Pat. No. 3,298,792.
  • the mobile elements of the distribution plate 8 may be used to dislodge any polymer particles entrapped in or on the distribution plate 8 .
  • Hydrogen may be used as a chain transfer agent in the polymerization reaction of the present invention.
  • the ratio of hydrogen/ethylene monomer employed generally will vary between 0 to 2.0 moles of hydrogen per mole of the ethylene monomer in the gas stream.
  • the activator compound may be added to the reaction system downstream from heat exchanger 10 .
  • the activator compound may be fed into the gas recycle system from dispenser 11 through line 12 .
  • the zinc compound would be introduced into the reactor 1 , preferably in the form of a dilute solution (2 to 30 weight percent) in a hydrocarbon solvent or absorbed on a solid diluent material, such as silica, in amounts of 10 to 50 weight percent. These compositions tend to be pyrophoric.
  • the zinc compound may be added alone, or with any additional portions of the activator compound that are to be added to the reactor 1 , from a feeder (not shown) which could be positioned adjacent dispenser 11 .
  • the fluid bed reactor 1 will be operated at a temperature below the sintering temperature of the polymer particles to ensure that sintering will not occur.
  • an operating temperature of 30 to 150° C. generally may be employed.
  • temperatures of 70 to 95° C. may be used to prepare products having a density in the range of from 0.91 to 0.92, and temperatures in the range of from 80 to 100° C. may be used to prepare products having a density in the range of >0.92 to 0.94.
  • the fluid bed reactor 1 is operated at pressures of up to 1000 psi, and in certain exemplary embodiments may be operated at a pressure of from 150 to 400 psi, with operation at the higher pressures in such ranges favoring heat transfer, because, inter alia, an increase in pressure increases the unit volume heat capacity of the gas.
  • the partially activated and SiO 2 supported precursor composition is injected into the bed at a rate equal to its consumption at a point 13 that is above the distribution plate 8 .
  • the catalyst may be injected at a point in the bed where good mixing of polymer particles occurs.
  • the injection of the catalyst at a point above the distribution plate 8 may be beneficial because, inter alia, the catalysts used in the practice of the invention are highly active, such that injection of the catalyst into the area below the distribution plate 8 may cause polymerization to begin there and eventually cause plugging of the distribution plate 8 .
  • Injection into the viable bed aids in distributing the catalyst throughout the bed and tends to preclude the formation of localized spots of high catalyst concentration which may result in the formation of “hot spots.” Injection of the catalyst into the reactor 1 above the bed may result in excessive catalyst carryover into the recycle line where polymerization may begin and plugging of the line and heat exchanger 10 eventually may occur.
  • a gas that is inert to the catalyst such as nitrogen or argon, may be used to carry the partially reduced precursor composition, and any additional activator compound or non-gaseous chain transfer agent that is used, into the bed.
  • the production rate of the bed is controlled by the rate of catalyst injection.
  • the production rate may be increased by simply increasing the rate of catalyst injection, and may be decreased by reducing the rate of catalyst injection.
  • the temperature of the recycle gas entering the reactor 1 may be adjusted upwards and downwards to accommodate the change in rate of heat generation. This facilitates the maintenance of an essentially constant temperature in the bed.
  • Complete instrumentation of both the fluidized bed and the recycle gas cooling system may be useful to facilitate, inter alia, the detection of any temperature change in the bed so as to enable the operator to make a suitable adjustment in the temperature of the recycle gas.
  • the fluidized bed is maintained at essentially a constant height by withdrawing a portion of the bed as product at a rate equal to the rate of formation of the particulate polymer product. Because the rate of heat generation is directly related to product formation, a measurement of the temperature rise of the gas across the reactor 1 (the difference between inlet gas temperature and exit gas temperature) may be determinative of the rate of particulate polymer formation at a constant gas velocity.
  • the particulate polymer product may be continuously withdrawn at a point 14 at or close to the distribution plate 8 and in suspension with a portion of the gas stream that may be vented as the particles settle to minimize further polymerization and sintering when the particles reach their ultimate collection zone.
  • the suspending gas may also be used to drive the product of one reactor to another reactor.
  • the particulate polymer product conveniently may be withdrawn through the sequential operation of a pair of timed valves 15 and 16 defining a segregation zone 17 . While valve 16 is closed, valve 15 may be opened to emit a plug of gas and product to the zone 17 between it and valve 15 , which then may be closed. Valve 16 then may be opened to deliver the product to an external recovery zone. Valve 16 then may be closed to await the next product recovery operation.
  • the vented gas containing unreacted monomers may be recovered from zone 17 through line 18 and recompressed in compressor 19 and returned directly, or through a purifier 20 , over line 21 to gas recycle line 6 at a point upstream of the recycle compressor 9 .
  • the fluidized bed reactor 1 is equipped with an adequate venting system to allow venting of the bed during start up and shut down.
  • the reactor 1 does not require the use of stirring means and/or wall scraping means.
  • the recycle gas line 6 and the elements therein e.g., compressor 9 , heat exchanger 10 ) generally should have smooth surfaces, and should be devoid of unnecessary obstructions so as not to impede the flow of recycle gas.
  • the highly active catalyst system of this invention may yield a fluid bed product having an average particle size of from 0.01 to 0.04 inches, and, in certain exemplary embodiments, from 0.02 to 0.03 inches, in diameter wherein the catalyst residue may be very low.
  • the polymer particles are relatively easy to fluidize in a fluid bed.
  • the feed stream of gaseous monomer, with or without inert gaseous diluents, may be fed into the reactor at a space time yield of about 2 to 10 pounds/hour/cubic foot of bed volume.
  • virgin resin or polymer as used herein means polymer, in granular form, as it is recovered from the polymerization reactor.
  • the catalysts of the present invention also may be used in the gas phase reaction process and apparatus disclosed in U.S. Pat. No. 4,255,542, which corresponds to European Patent Application No. 79101169.5, which was filed Apr. 17, 1979 and which was published on Oct. 31, 1979 as Publication No. 4966. These references disclose the use of an entirely straight sided fluid bed reactor that employs heat exchange means within the reactor.
  • the polymers that may be prepared with the catalysts of the present invention include, inter alia, copolymers that include a major mol percent (e.g., ⁇ 90%) of ethylene, and a minor mol percent (e.g., ⁇ 10%) of one or more C 3 to C 8 alpha olefins.
  • a major mol percent e.g., ⁇ 90%) of ethylene
  • a minor mol percent e.g., ⁇ 10%
  • the C 3 to C8 alpha olefins will not contain any branching on any of their carbon atoms that may be closer than the fourth carbon atom from the double bond.
  • C 3 to C 8 alpha olefins examples include, but are not limited to, propylene, butene-1, pentene-1, hexene-1, 4-methyl pentene-1, heptene-1 and octene-1.
  • the C 3 to C 8 alpha olefins may include propylene, butene-1, hexene-1, 4-methyl pentene-1 and octene-1.
  • the polymers that may be prepared with the catalysts of the present invention generally have a molecular weight distribution (Mw/Mn) in the range of from 2.5 to 6.0. In certain exemplary embodiments of the present invention, the polymers may have a molecular weight distribution in the range of from 2.7 to 4.1.
  • MFR melt flow ratio
  • the polymers that may be prepared with the catalysts of the present invention generally have a density in the range of from ⁇ 0.91 to ⁇ 0.97. In certain exemplary embodiments, the polymers may have a density in the range of from ⁇ 0.916 to ⁇ 0.935. In certain exemplary embodiments, the density of certain exemplary copolymers that may be prepared with the catalysts of the present invention, at a given copolymer melt index level, may be regulated by, inter alia, the amount of the one or more C 3 to C 8 comonomers that may be copolymerized with the ethylene.
  • the ethylene generally will homopolymerize with the catalysts of the present invention, thereby providing homopolymers.
  • the homopolymers produced in accordance with the present invention may have a density of ⁇ 0.96.
  • the density of the polymers that may be prepared with the catalysts of the present invention progressively may be lowered through the addition of progressively larger amounts of one or more C 3 to C8 comonomers.
  • the amount of each of the various C 3 to C 8 comonomers that may be used to provide a copolymer having a desired density generally will vary from comonomer to comonomer, under the same reaction conditions. Thus, for an operator to provide a copolymer having the same given density at a given melt index level, the operator generally may add larger molar amounts of the different C 3 to C 8 comonomers, in the following order: C 3 >C 4 >C 5 >C 6 >C 7 >C 8 .
  • the polymers that may be prepared with the catalysts of the present invention generally have a standard or normal load melt index in the range of from ⁇ 0.01 to about 100. In certain exemplary embodiments, the polymers may have a standard or normal load melt index in the range of from 0.5 to 80. The polymers may have a high load melt index (HLMI) in the range of from 11 to 2000.
  • the melt index of the polymers that may be prepared with the catalysts of the present invention may be a function of a variety of factors including, inter alia, the temperature of the polymerization reaction, the density of the copolymer, the ratio of hydrogen to ethylene monomer present during the reaction, and the ratio of C 3 to C 8 comonomer to ethylene monomer present during the reaction.
  • an operator may increase the melt index of the polymers by, inter alia, increasing the polymerization temperature, and/or by decreasing the density of the copolymer, and/or by increasing the hydrogen/ethylene monomer ratio, and/or by increasing the ratio of C 3 to C 8 comonomer to ethylene monomer.
  • an operator optionally may include other chain transfer agents (e.g., dialkyl zinc compounds) to further increase the melt index of the polymers.
  • the polymers of the present invention generally have an unsaturated group content of ⁇ 1.
  • the polymers of the present invention may have an unsaturated group content in the range of from ⁇ 0.1 to ⁇ 0.3 carbon-carbon double bond per 1000 carbon atoms.
  • the polymers of the present invention generally have a residual catalyst content, which may vary depending on the productivity of the catalyst system.
  • a catalyst system having a productivity level of ⁇ 100,000 pounds of polymer per pound of residual metal in the polymer the polymers of the present invention produced through a process using such catalyst system may have a residual catalyst content, expressed in terms of parts per million (ppm) of titanium metal, in the range of from >0 to ⁇ 10 ppm.
  • the residual catalyst content may be in the range of from >0 to ⁇ 5 ppm.
  • the residual catalyst content in the polymers produced therefrom may be in the range of from >0 to ⁇ 2 ppm.
  • the homopolymers and copolymers of the present invention are readily produced by the processes of the present invention at productivities of up to 500,000 pounds of polymer per pound of residual metal in the polymer.
  • the polymers of the present invention generally are granular materials that have an average particle size in the range of from 0.01 to 0.06 inches in diameter. In certain embodiments, the polymers have an average particle size in the range of from 0.02 to 0.03 inches, in diameter. The particle size may be an important factor for the purposes of readily fluidizing the polymer particles in a fluid bed reactor.
  • the granular copolymers and homopolymers of the present invention have a bulk density in the range of from 19 pounds per cubic foot to 35 pounds per cubic foot. Expressed in different units, the granular copolymers and homopolymers of the present invention have a bulk density in the range of from 0.304 gram per cubic centimeter to 0.561 gram per cubic centimeter.
  • the polymers of the present invention may be useful in a variety of manners, including, but not limited to, the production of film therefrom, as well as in other molding applications.
  • an operator may elect to use embodiments of the polymers of the present invention that have a density in the range of from ⁇ 0.916 to ⁇ 0.935, and in certain embodiments, a density in the range of from ⁇ 0.917 to ⁇ 0.928, a molecular weight distribution (Mw/Mn) in the range of from ⁇ 2.7 to ⁇ 4.1, and in certain embodiments, a molecular weight distribution (Mw/Mn) in the range of from ⁇ 2.8 to ⁇ 3.1; and a standard melt index in the range of from >0.5 to ⁇ 5.0, and in certain embodiments, a standard melt index in the range of from ⁇ 0.7 to ⁇ 4.0.
  • the films that may be produced from the polymers of the present invention may have a thickness in the range of from >0 to ⁇ 10 mils, and in certain embodiments, a thickness in the range of from >0 to ⁇ 5 mils, and in certain embodiments, a thickness in the range of from >0 to ⁇ 1 mil.
  • an operator may elect to use embodiments of the polymers of the present invention that have a density in the range of from ⁇ 0.920 to ⁇ 0.940, and in certain exemplary embodiments, a density in the range of from ⁇ 0.925 to ⁇ 0.930; a molecular weight distribution Mw/Mn in the range of from ⁇ 2.7 to ⁇ 3.6, and in certain embodiments a molecular weight distribution Mw/Mn in the range of from ⁇ 2.8 to ⁇ 3.1; and a standard melt index in the range of from ⁇ 2 to ⁇ 100, and in certain embodiments a standard melt index in the range of from ⁇ 8 to ⁇ 80.
  • thermocouples For laboratory-prepared precursors, silicas first were dehydrated under nitrogen flow in a laboratory Carbolite Vertical Furnace, Model No. VST 12/32/400/2408 CP-FM supplied by Carbolite, Inc., provided with a quartz glass tube of 3.0 cm outer diameter and 70 cm in total length, and two thermocouples. One thermocouple was placed in a thermowell within the quartz glass tube, while the other was affixed to the skin of the quartz glass tube by placing it between the two folding halves of the furnace, then clamping the folding halves shut. The thermocouples were hooked up to a Nomad OM-SP1700 data logger supplied by Omega Engineering. A collection flask for excess blowout silica was attached at the top of the tube, which in turn was attached to a bubbler via a glass elbow.
  • silica was poured via a funnel into the quartz glass tube to fill the tube about 2 ⁇ 3 full within the heating zone.
  • a preset program was started to begin the dehydration, using a Eurotherm 2408 Programmable Temperature Controller.
  • a typical ramp and soak profile is shown in FIG. 2 .
  • the gas flow in this case nitrogen was preset to about 50-100 cubic centimeters per minute.
  • the silica was discharged into a clean, dry, N 2 -purged bottle and maintained in an inert atmosphere.
  • the data logger information was downloaded to a computer file.
  • the hydroxyl content of the three silicas then was characterized by titration with TiCl 4 in a hexane solution. After washing and drying of the treated silica, the titanium content of the treated silica (a measure of the presence of hydroxyl groups in the silica) was determined by a spectrophotometric method. The hydroxyl content of the three silicas is reported in the table below. The hydroxyl content was determined by TiCl 4 titration that binds to the surface OH-groups. The final titanium content, measured by a spectrophotometric method, is an indication of the OH-group content at a given dehydration temperature of the silica. TABLE 3 Hydroxyl Content at 600° C. as determined by TiCl 4 Silica Type titration (mmol OH/g) Davison 955 0.59 Screened Davison-955 0.55 Ineos ES757 0.59
  • the silicas used as support material in the three laboratory-scale catalyst precursors have a particle size distribution shown in Tables 4 and 5 below, and in FIGS. 3 and 4 .
  • the median particle size was determined to be 18 micrometers.
  • the compound referred to as [TiCl 3 , 0.33 AlCl 3 ] is a mixed compound that is obtained by the reduction of TiCl 3 with metallic aluminum; the mixed compound thus contains 1 molecule of AlCl 3 per 3 molecules of TiCl 3 .
  • the operation was carried out in a “dry box.” The flask was then placed in an oil bath over a stir/heating plate inside a hood. The septum was replaced by a condenser with a glass joint and provided with circulating cold water and a small N 2 flow through it. The oil bath was heated at 80° C., resulting in an internal temperature between 70 and 72° C. The system was maintained under stirring for about 2 hours until all solids dissolved in the refluxing THF.
  • the solution was allowed to cool down, and was transferred to another oven-dried, air-free 100 ml Schlenk flask provided with stir bar and rubber septum containing 5.0 grams of laboratory TOS slurried in 20 ml of THF. (The transfer of solution was performed inside the dry box.)
  • the flask was placed in the oil bath and the mixture was stirred for about 30 minutes at 80° C., then flushed with a N 2 vent for about 4-5 hours until most of the THF evaporated.
  • the resulting catalyst precursors further were dried for 4 hours under vacuum (mechanical pump, 10 ⁇ 5 mmHg) in a water bath at 45° C.
  • Precursor 1 comprised Davison 955 silica, had a magnesium/titanium ratio of 3, and is taken as a control.
  • Precursor 2 comprised Ineos ES-757 silica, and had a magnesium/titanium ratio of 3.
  • Precursor 3 comprised screened Davison 955 silica, and had a magnesium/titanium ratio of 3.
  • an amount of ethanol ranging within EtOH/Mg mole ratios of from about 0.5 to about 2 was added to the THF solvent.
  • the light pink free-flowing powder precursors were then ready to be tested in polyethylene polymerization reactions.
  • a one liter stirred stainless steel jacketed reactor-autoclave equipped with a stirrer and a thermocouple was used for the polymerization reactions with Precursors 1-3.
  • the reactor was thoroughly dried under a nitrogen purge at elevated temperatures (>100° C.) before each run.
  • About 40 mL of dry, degassed 1-hexene (a co-monomer) was added via syringe to the empty reactor that was cooled at 60° C. after purging, or, in certain experiments, 40 mL of condensed 1-butene was loaded to reactor by an automated injection pump.
  • About 500 mL of dry degassed isobutane was converted into liquid in a pressure tower and fed to the reactor.
  • TEAL tri-ethyl aluminum alkyl
  • the polymerization reaction then was initiated by introducing 0.04 grams of laboratory catalyst precursor by means of a pressure injection device, which further will be described.
  • the final pressure of the reactor was 380 psi.
  • Ethylene was allowed to flow to maintain its partial pressure of 125 psi.
  • the reactor operative variables e.g., temperature, pressure and ethylene flow
  • the reactor was recorded along the reaction time, and stored in a computer through a data acquisition system. After a reaction period of 30 minutes, the ethylene flow was stopped, and the reactor was depressurized to ambient pressure while the temperature of the reactor was reduced to about 45° C., at which point the reactor was opened.
  • the mass of polymer produced by the reaction was determined after allowing all of the remaining comonomer to evaporate, until the polymer weight stabilized for a desired period of time, which generally was in the range of from 1 to 4 hours.
  • the catalyst injection system used to conduct these experiments consists of a 5 mL stainless steel cylinder provided with valves and connectors in its extremes, coupled to a 50 mL cylinder that is attached via a flexible metal tubing to a 500 mL stainless steel bomb.
  • the stainless steel bomb is capable of holding up to 400 psi of N 2 .
  • the catalyst precursor first was weighed and placed inside the 5 mL cylinder. About 5 mL of isopentane was placed in the 50 mL cylinder. The cylinders then were coupled through the connectors, but valves (resembling globe valves) isolated the content of each from the other. All these operations were carried out inside a dry box.
  • the device After loading the catalyst, the device was removed from the dry box and connected to a reactor port through the small cylinder. In a nearly vertical position, the 5 mL-50 mL cylinders tandem was connected through the extreme of the large cylinder to the bomb pressurized with N 2 at 400 psi by a flexible metal tubing. The bomb was isolated from the cylinders by another valve, such that the bomb could be pressurized either before or after being connected to the cylinders. Through a fast, and coordinated, opening/closing of valves, the nitrogen confined in the bomb pushed the isopentane contained in the large cylinder through the small cylinder, thus impelling the catalyst to the reactor. It was proved that the catalyst was quantitatively transferred into the pressurized reactor.
  • FIG. 5 depicts a plot of ethylene flow versus reaction time that was obtained during laboratory isobutane slurry polymerizations.
  • FIG. 5 displays the ethylene flow (as recorded by a computer-controlled Hastings mass flow meter Model HFC 202) versus reaction time.
  • the ethylene flow is expressed as standard liters per minute (SLPM), which is the volume occupied by a given mass of gas at standard temperature and pressure (e.g., 0 degrees C. and 1 atmosphere of pressure).
  • SLPM standard liters per minute
  • the representation of the ethylene flow during the reaction time may be referred to as the “kinetic profile.”
  • a statistical analysis of the laboratory polymerization results (performed using software supplied by JMP Software) established the standard deviation and confidence interval by analyzing the variance (anova). The analysis of the variance checks whether differences among the means exist.
  • the results in Table 9 are from a comparison of means made by using the Tukey-Kramer HSD (“Honestly Significant Difference”).
  • the Tukey-Kramer HSD is a test that is sized for all differences among the means.
  • the means comparison made by using the Tukey-Kramer HSD criteria determines that levels not connected by the same letter are significantly different.
  • Example 1 demonstrates, inter alia, that laboratory catalyst precursors prepared with silica support materials that have a smaller particle size and a narrower particle size distribution may demonstrate desirable productivity and may be useful in polymerization processes to generate polymer products having desirable physical properties.
  • Scaled-up catalyst compositions were prepared in a pilot plant laboratory using a jacketed vessel (that may be referred to as a mix tank) according to the procedure set forth below.
  • the capacity of the mix tank is on the order of about 2 pounds of catalyst material.
  • Silica dehydrated at 600° C. has a hydroxyl nominal concentration of 0.7 mmole OH/gram.
  • the TEAL-on-Silica (“TOS”) prepared for these scaled-up batches has a target aluminum loading of 0.5 mmole/gram. As TEAL reacts with hydroxyl according to a 1-to-1 molar ratio, then about 0.2 mmole OH/gram will remain unreacted on the TOS.
  • silica were charged to the mix tank, for ES 757 silica and Davison 955-600 silica. About 3.5 liters of isopentane then were added, after which about 0.59 grams of 10% TEAL in isopentane (0.93 ml) were added for every gram of silica charged.
  • the TEAL reacts exothermically with the silica to form ethane. Accordingly, the TEAL charge was metered so as to keep the reactor temperature under a target setting of 35° C.
  • the foregoing mixture was mixed for 30 minutes at a pressure of 10 psig. Drying was initiated by heating the jacket to 60° C. and reducing the internal reactor pressure to 5 psig. A nitrogen sweep was initiated.
  • the mix tank contents were discharged.
  • the target aluminum loading for the scaled-up TEAL-on-Silica was 0.5 mmole/gram silica.
  • Scaled-up catalyst precursors were prepared according to the following procedure. About 3,500 grams of tetrahydrofuran (THF) was charged to the mix tank. The water content of the THF was less than 40 ppm of water. Magnesium chloride (MgCl 2 ) was added to the dry THF. The mix tank was pressurized to 5 psig and heated until the contents reached a temperature of 60° C. Stirring at 150 rpm was initiated. About 38.6 grams of ethanol were added, which dissolves the MgCl 2 almost instantly. Mixing continued for about 30 minutes, after which about 66.8 grams of TiCl 3 , 0.33 AlCl 3 were charged. The mixture was mixed for an hour. The mix tank then was cooled so that the temperature of the contents fell below 50° C. About 800 grams of scaled-up TOS was charged and mixed for about 30 minutes.
  • THF tetrahydrofuran
  • the contents of the mix tank then were dried by heating the jacket of the mix tank to about 85° C., and reducing the internal pressure within the jacket by an incremental inch of pressure at a time until the pressure reached ⁇ 5 inches of mercury. The internal pressure then was reduced to full vacuum, and a nitrogen sweep was initiated. When the temperature of the contents stabilized between 80 and 83° C. for three hours, the mix tank was pressurized to 5 psig, and cooled to below 40° C., at which point the scaled-up catalyst was discharged.
  • the catalyst precursors prepared as described above then were converted into catalyst compositions by treatment with at least one, and no more than two, activators.
  • the relative amounts of the activator(s) were varied with respect to Ti content, to provide an Al:Ti molar ratio of about 1 to 5 of each one of the activators.
  • Different catalyst formulations were prepared by varying the relative amounts of the selected activators, one of them containing an halogen atom, in such a way that their respective Al/Ti molar ratios were within the range of from 1 to 5.
  • a total of 9 different catalyst formulations were prepared, comprising precursors prepared with both Davison 955 and ES757 silicas.
  • the catalyst formulations comprising precursors prepared with Davison 955 silicas were labeled as A, C, D and E.
  • the catalyst formulations comprising precursors prepared with Ineos ES757 silicas were labeled as A1, C1, D1, and E1.
  • a one liter stirred stainless steel jacketed reactor-autoclave equipped with a stirrer and a thermocouple was used for the polymerization reactions.
  • the reactor was thoroughly dried under a purge of nitrogen at 100° C. for 1 hour and cooled down to 45° C. before each run.
  • About 0.8 mL of heptane dilute solution (1.54 M) of TEAL then was added to the reactor to act as cocatalyst and passivate any impurities.
  • 0.15 gram catalyst was charged.
  • the reactor then was sealed, and 1500 or 3000 cubic centimeters of hydrogen was charged as indicated in the tables that follow, after which the reactor was heated to 65° C. At this point, ethylene flow was initiated, and continued until the reactor reached polymerization conditions of 200 psi at 85° C.
  • Ethylene was allowed to flow to maintain the reactor pressure at 200 psi during the 30 minute reaction period. Ethylene uptake is measured through a computer-controlled flow meter. The temperature of the reactor was reduced to 45° C. while the reactor was depressured to ambient pressure, after which the reactor was opened. After allowing the solvent to evaporate, the mass of polymer produced from the reaction was determined. The polymer produced from the reaction then was characterized to determine a number of parameters, including Melt Flow Index (MI), High Load Melt Flow (HLM), and bulk density (BD).
  • MI Melt Flow Index
  • HLM High Load Melt Flow
  • BD bulk density
  • Tables 10 and 11 below set forth certain parameters determined from laboratory ethylene homo-polymerizations conducted as set forth above with experimental scaled-up improved precursors.
  • Table 12 sets forth certain parameters determined from laboratory ethylene homo-polymerizations conducted as set forth above with scaled-up catalyst formulations at activation Al/Ti ratios located in the low end and in the medium end of the 1 to 5 range are compared to parameters of conventional Control Catalysts 1 and 4 (medium Al/Ti ratio range, e.g., containing an Al/Ti ratio that is about 2.5) and Control Catalysts 2 and 3 (at the lower end of the Al/Ti ratio range, e.g., containing an Al/Ti ratio that is close to 1) at comparable Al/Ti ratios.
  • conventional Control Catalysts 1 and 4 medium Al/Ti ratio range, e.g., containing an Al/Ti ratio that is about 2.5
  • Control Catalysts 2 and 3 at the lower end of the Al/Ti ratio range, e.g., containing an Al/Ti ratio that is close to 1 at comparable Al/Ti ratios.
  • Example 2 demonstrates, inter alia, that the improved experimental catalysts prepared using supports that use ES757 silica having a smaller particle size and narrower particle size distribution appear to demonstrate a desirable productivity-vs.-bulk-density relationship, which may correlate across a variety of magnesium-to-titanium ratios.
  • Sample catalyst compositions prepared in the manner described above were reacted in a polymerization process in a pilot plant reactor.
  • Polymerization was conducted in a 24 inch diameter gas-phase fluidized bed reactor operating at approximately 300 psig total pressure.
  • the reactor bed weight was approximately 500-600 pounds.
  • Fluidizing gas was passed through the bed at a velocity of approximately 2.0 feet per second.
  • the fluidizing gas exiting the bed entered a resin-disengaging zone located at the upper portion of the reactor.
  • the fluidizing gas then entered a recycle loop and passed through a water-cooled heat exchanger and cycle gas compressor.
  • the shell side water temperature was adjusted to maintain the reaction temperature to the specified value.
  • Ethylene, hydrogen, 1-hexene and nitrogen were fed to the cycle gas loop just upstream of the compressor at quantities sufficient to maintain the desired gas concentrations.
  • Triethylaluminum cocatalyst was fed to the reactor in quantities sufficient to support reaction.
  • Gas concentrations were measured by an on-line vapor fraction analyzer.
  • the catalyst was fed to the reactor bed through a stainless steel injection tube at a rate sufficient to maintain the desired polymer production rate. Nitrogen gas was used to disperse the catalyst into the reactor. Product was withdrawn from the reactor in batch mode into a purging vessel before it was transferred into a product drum. Residual catalyst and cocatalyst in the resin were deactivated in the product drum with a wet nitrogen purge.

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BRPI0611761-9A BRPI0611761A2 (pt) 2005-06-13 2006-05-26 composições catalisadoras compreendendo pequenos materiais de suporte de sìlica e métodos de uso nas reações de polimerização
EP06771229.9A EP1891125B1 (fr) 2005-06-13 2006-05-26 Compositions catalytiques comprenant des matériaux de support de petite taille à base de silice, et procédés d'utilisation de ces compositions dans des réactions de polymérisation
KR1020087000875A KR20080019060A (ko) 2005-06-13 2006-05-26 소형 실리카 담지 물질을 포함하는 촉매 조성물 및 중합반응에서의 사용 방법
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EP1565262A4 (fr) * 2002-11-26 2009-11-11 Univation Tech Llc Procedes de formation d'une composition de catalyse activee et supportee
US12319774B1 (en) 2024-01-23 2025-06-03 Chevron Phillips Chemical Company Lp Particle size control of silyl chromate catalysts and uses thereof in fluidized bed reactors

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US8012903B2 (en) 2011-09-06
CA2610843C (fr) 2014-01-07
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CN101189272A (zh) 2008-05-28
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US20060281880A1 (en) 2006-12-14
WO2006138036A1 (fr) 2006-12-28
RU2403266C2 (ru) 2010-11-10
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