EP1673400A1 - Procede de polymerisation et controle des proprietes d'une composition polymere - Google Patents

Procede de polymerisation et controle des proprietes d'une composition polymere

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Publication number
EP1673400A1
EP1673400A1 EP04818279A EP04818279A EP1673400A1 EP 1673400 A1 EP1673400 A1 EP 1673400A1 EP 04818279 A EP04818279 A EP 04818279A EP 04818279 A EP04818279 A EP 04818279A EP 1673400 A1 EP1673400 A1 EP 1673400A1
Authority
EP
European Patent Office
Prior art keywords
control agent
reactor
amount
polymer
another embodiment
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP04818279A
Other languages
German (de)
English (en)
Other versions
EP1673400A4 (fr
Inventor
Fred D. Ehrman
Pradeep P. Shirodkar
Robert L. Santana
Porter C. Shannon
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Univation Technologies LLC
Original Assignee
Univation Technologies LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US10/685,607 external-priority patent/US7238756B2/en
Priority claimed from US10/685,650 external-priority patent/US6828395B1/en
Application filed by Univation Technologies LLC filed Critical Univation Technologies LLC
Publication of EP1673400A1 publication Critical patent/EP1673400A1/fr
Publication of EP1673400A4 publication Critical patent/EP1673400A4/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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

Definitions

  • the present invention relates to the polymerization of olefins in a single reactor using bimetallic catalysts, and more particularly to the control of the flow index and/or amounts of polymer composition components ("split") by the addition of a control agent that, in certain embodiments, is selective for one catalyst component of the bimetallic catalyst composition.
  • Broad or bimodal molecular weight distribution polymer compositions are compositions that typically include one or more high molecular weight polymers and one or more low molecular weight polymers.
  • the weight fraction of the high molecular weight (“HMW”) polymer typically ranges from, for example, 0.10 to 0.90 for applications requiring broad molecular weight distribution polymers.
  • the relative amount of HMW polymer in the polymer composition can influence the rheological properties of the composition.
  • One such measurable rheological property of bimodal polymer compositions is its flow index ("FI", or I 21 , measured at 190°C, 21.6 kg according to ASTM D-1238).
  • the I 21 of the bimodal polymer composition in one embodiment, possesses an I 21 that is between 2 and 100 dg/min. This range represents a balance between processability (desiring relatively high I 1 ) on the one hand, and product (film, etc.) toughness (desiring relatively low I 21 ) on the other hand. Hence, it is necessary to control polymer composition I 21 in the polymerization reactor.
  • bimetallic catalyst compositions incorporate at least two, preferably two, metal centers, both of which may be the same or different metal with similar or differing coordination spheres, patterns of substitution at the metal center or ligands bound to the metal center.
  • one of the metal centers produces a low molecular weight (“LMW”) polymer while the other produces a HMW polymer in the single polymerization reactor, and desirably, although not necessarily, simultaneously.
  • LMW low molecular weight
  • WO 02/46246 to Mawson et al; US 6,420,474 and 6,569,963 to Nowlin et al. disclose the addition of an additional catalyst to adjust the relative amounts of HMW and LMW polymers in a polymer composition.
  • the products resulting therefrom, such as bimodal resins used to make films may still suffer from gel formation, the reaction process itself may be subject to fouling, which causes an undesirable need to shut down the polymerization reactor, and further, the procedure of adding a catalyst component can add cost and complexity to the process.
  • the present invention is directed to methods of controlling the rheological properties of a polymer composition generated by a bimetallic catalyst system in a single reactor, the control affected by the use of control agents; the control agents are added in an amount sufficient to alter the relative ratios, or "split" of the HMW and LMW polymer components of the polymer compositions. More particularly, the control agents are used as described herein to counter the rheological-altering influences in bimetallic catalyst systems of such compounds as alkanes and aluminum alkyls.
  • One aspect of the present invention is a method of producing a polymer composition in the presence of rheological-altering compounds comprising incorporating a high molecular weight polymer into a low molecular weight polymer to form the polymer composition in a single polymerization reactor in the presence of polymerizable monomers, a bimetallic catalyst composition and at least one control agent; wherein the control agent is added in an amount sufficient to control the level of incorporation of the high molecular weight polymer, the level of low molecular weight polymer, or both.
  • Figure 2 is a graphic representation of GPC data derived from runs 7 and 8 exemplifying the effects of an aluminum alkyl as described in the Examples.
  • substituted means that the group following that term possesses at least one moiety in place of one or more hydrogens in any position, the moieties selected from such groups as halogen radicals (esp., CI, F, Br), hydroxyl groups, carbonyl groups, carboxyl groups, amine groups, phosphine groups, alkoxy groups, phenyl groups, naphthyl groups, Ci to C 10 alkyl groups, C 2 to C 10 alkenyl groups, and combinations thereof.
  • halogen radicals esp., CI, F, Br
  • substituted alkyls and aryls includes, but are not limited to, acyl radicals, alkylamino radicals, alkoxy radicals, aryloxy radicals, alkylthio radicals, dialkylamino radicals, alkoxycarbonyl radicals, aryloxycarbonyl radicals, carbamoyl radicals, alkyl- and dialkyl- carbamoyl radicals, acyloxy radicals, acylamino radicals, arylamino radicals, and combinations thereof.
  • Group 3 to Group 12 atoms and a ligand or ligand atom (e.g., cyclopentadienyl, nitrogen, oxygen, halogen ions, alkyl, etc.), as well as the phrases "associated with”, “bonded to” and “bonding”, are not limited to representing a certain type of chemical bond, as these lines and phrases are meant to represent a "chemical bond”; a "chemical bond” defined as an attractive force between atoms that is strong enough to permit the combined aggregate to function as a unit, or "compound”.
  • a ligand or ligand atom e.g., cyclopentadienyl, nitrogen, oxygen, halogen ions, alkyl, etc.
  • the present invention is directed to a method of controlling the rheological properties of a polymer composition generated by a bimetallic catalyst system in a single reactor, the control affected by the use of "control agents”; the control agents are added in an amount sufficient to alter the relative ratios, or "split" of the HMW and LMW polymer components of the polymer compositions. More particularly, the present invention is directed to maintaining certain rheological properties of the polymer composition at a desirable "target", one such property being the I 21 of the polymer composition, the rheological properties being maintained at the target level by the addition of control agents.
  • control agents are used as described herein to counter unexpected rheological-altering influences in bimetallic catalyst systems of such compounds as alkanes (used, for example, as “condensing agents” as in US 5,462,999) and aluminum alkyls (used, for example, as activators such as in RE 33,683).
  • One aspect of the present invention is a method of producing a polymer composition in the presence of rheological-altering compounds comprising incorporating a high molecular weight polymer into a low molecular weight polymer to form the polymer composition in a single polymerization reactor in the presence of polymerizable monomers, a bimetallic catalyst composition and at least one control agent; wherein the control agent is added in an amount sufficient to control the level of incorporation of the high molecular weight polymer, the level of low molecular weight polymer, or both.
  • the "polymer composition” in one embodiment is a bimodal polymer composition, and in a more particular embodiment, a bimodal polyethylene composition wherein from greater than 80 wt% of the monomer derived units of the composition are ethylene and the remaining 0 to 20 wt% are derived from C 3 to C 1 olefins and diolefins, described further herein.
  • incorporación is not herein limited to any particular method of combining the HMW and LMW polymers, and may comprise any technique known in the art.
  • "incorporating” refers to the in situ blending of HMW and LMW polymers together as they are being formed in the polymerization reactor(s); and in yet a more particular embodiment, the in situ blending of HMW and LMW polymers together as they are being formed in a single polymerization reactor in a single stage process.
  • Another aspect of the present invention is a method of controlling the I 21 of a polymer composition in the presence of rheological-altering compounds comprising forming a high molecular weight polymer and a low molecular weight polymer in a single polymerization reactor in the presence of polymerizable monomers, a bimetallic catalyst composition and at least one control agent; wherein the control agent is added in an amount sufficient to control the level of incorporation of the high molecular weight polymer, the level of low molecular weight polymer, or both.
  • Yet another aspect of the invention is a method of producing a polymer composition in the presence of rheological-altering compounds comprising contacting a bimetallic catalyst composition, a control agent and polymerizable monomers in a single polymerization reactor; characterized in that the bimetallic catalyst composition comprises a first catalyst component and a second catalyst component, wherein the first catalyst component is capable of producing a low molecular weight polymer and the second catalyst component is capable of producing a high molecular weight polymer; wherein the control agent substantially alters the polymerization activity of the first or second catalyst component relative to the second or first catalyst component, respectively.
  • the control agent substantially lowers the polymerization productivity (or activity) of the second catalyst component relative to the first catalyst component.
  • the polymer compositions of the present invention include at least one low molecular weight (“LMW”) polymer and at least one high molecular weight (“HMW”) polymer, and in one embodiment include one of each.
  • LMW polymer and HMW polymers are incorporated into one another either sequentially or simultaneously in a single polymerization reactor, and are incorporated into one another simultaneously in a single polymerization reactor in a particular embodiment.
  • Polymerization reactors are well known in the art; preferable polymerization reactors include those capable of polymerizing olefins to form polyolefins such as polyethylene, polypropylene, etc., such as gas phase, and solution or slurry phase reactors.
  • the polymerization reactor is a fluidized-bed, gas phase reactor such as disclosed in WO 03/044061 and US 4,003,712, typically comprising at least one reactor, only one reactor in a particular embodiment, the reactor comprising a reaction zone and a velocity reduction zone or expanded region; the polymerization reactor further comprising at least one recycle line that is continuous from one portion, preferably a top portion of a vertical reactor, to another portion, preferably a bottom portion of a vertical reactor, having a heat exchanger therebetween.
  • the bimetallic catalyst composition and primary monomers, ethylene in a particular embodiment, as well as hydrogen and other gases, enter the reactor wherein the reaction zone comprises a bed of growing polymer particles maintained in a fluidized state.
  • unreacted gases flow through the fluidized bed of growing polymer particles, into the expanded region of the reactor where solid polymer particles are allowed to settle, then pass through the recycle line, wherein the gasses are cooled in a heat exchanger before reentering the reactor through a remaining portion of the recycle line.
  • the LMW polymer in one embodiment is a polyolefin, and more particularly, a polyethylene homopolymer or copolymer comprising from 0 to 10 wt% C 3 to C 10 ⁇ -olefin derived units, and more particularly, a homopolymer of ethylene or copolymer of ethylene and 1-butene, 1-pentene or 1-hexene derived units.
  • the LMW polymer can be characterized by a number of factors.
  • the weight average molecular weight of the LMW polymer ranges from 4,000 to 200,000 amu (Daltons) in one embodiment, and from 5,000 to 100,000 amu in another embodiment, and from 5,000 to 80,000 amu in another embodiment, and from 5,500 to 50,000 amu in yet another embodiment, and from 6,000 to 20,000 amu in yet another embodiment, wherein a desirable weight average molecular weight of the LMW polymer can comprise any combination of any upper limit with any lower limit described herein.
  • the HMW polymer in one embodiment is a polyolefin, and more particularly, a polyethylene homopolymer or copolymer comprising from 0 to 10 wt% C 3 to C 10 ⁇ -olefin derived units, and more particularly, a homopolymer of ethylene or copolymer of ethylene and 1-butene, 1-pentene or 1-hexene derived units.
  • the weight average molecular weight of the HMW polymer ranges from 50,000 to 1,000,000 amu (Daltons) in one embodiment, and ranges from 100,000 to 800,000 in another embodiment, and from 250,000 to 700,000 amu in another embodiment, and from 300,000 to 600,000 amu in yet another embodiment, wherein a desirable weight average molecular weight of the HMW polymer can comprise any combination of any upper limit with any lower limit described herein.
  • the polymer composition of the invention comprising at least the HMW and
  • LMW polymers can be described by any number of parameters; and in one embodiment possesses a "weight average” molecular weight distribution (Mw/Mn) of from 2.5 to 150, a "z- average” molecular weight distribution (Mz/Mw) of from 2 to 10, an I (190°C/2.16 kg) of from 0.01 to 10 g/10 cm, an I 21 (190°C/21.6 kg) of from 2 or 4 to 100 or 500 dg/min, and a density in the range of from 0.890 to 0.970 g/cm 3 .
  • Mw/Mn molecular weight distribution
  • Mz/Mw z- average molecular weight distribution
  • I 190°C/2.16 kg
  • I 21 190°C/21.6 kg
  • this parameter of the polymer composition of the invention is controlled by the introduction of a control agent in conjunction with a bimetallic catalyst composition into the polymerization reactor.
  • the polymer composition consists essentially of one HMW polymer and one LMW polymer.
  • rheological-altering compounds in the presence of rheological-altering compounds, it is meant that the polymerization process is taking place in a reactor wherein agents selected from aluminum alkyls and alkanes, in particular, C 4 to C 20 alkanes, are present in the reactor.
  • the aluminum alkyls are compounds comprising aluminum and alkyl groups, alkoxy groups, halogen groups, and mixtures thereof; and more particularly, aluminum alkyls are compounds of the formula A1R 3 , wherein each R is independently selected from the group consisting of halogens, C ⁇ to C 20 alkyls, C 6 to C 20 aryls, and Ci to C 20 alkoxys, and substituted versions thereof; and in a particular embodiment, the aluminum alkyl is trimethylaluminum ("TMA").
  • TMA trimethylaluminum
  • alkanes includes linear and branched alkanes. In one embodiment, the alkanes are selected from C 4 to C 1 alkanes, and in yet another embodiment, selected from pentane, hexane, and isomers and mixtures thereof.
  • the amount of alkane ranges from 0.1 to 50 wt% based on the primary monomer feed rate in one embodiment, and from 0.5 to 30 wt% in another embodiment, and from 1 to 20 wt% in yet another embodiment, and from 2 to 18 wt% in yet another embodiment, and from 5 to 12 wt% in yet another embodiment, wherein a desirable range of alkane comprises any combination of any upper wt% limit with any lower wt% limit described herein.
  • the amount of aluminum alkyl ranges from 1 to 500 wt ppm based on the primary monomer feed rate in one embodiment, and from 10 to 300 wt ppm in another embodiment, and from 20 to 200 wt ppm in yet another embodiment, and from 50 to 150 wt ppm in yet another embodiment, wherein a desirable range comprises any combination of any upper wt ppm limit with any lower wt ppm limit as described herein.
  • the control agent in one embodiment is any chemical compound having a reactive moiety capable of affecting the polymerization productivity of at least one catalyst component of the bimetallic catalyst composition. Examples of such include alcohols, ethers, thiols, amines nitrogen oxides, oxygen, and other oxygen or sulfur or nitrogen-containing compounds.
  • the control agent excludes water and carbon dioxide; however, in one embodiment, water is added to the polymerization reactor in addition to the control agent.
  • the control agent is not part of the bimetallic catalyst composition, but is a distinct component or composition added to the polymerization reactor separately; the control agent is introduced in a distinct physical location in the reactor relative to the introduction of the bimetallic catalyst composition to the polymerization reactor in a particular embodiment.
  • the bimetallic catalyst composition is introduced to the fluidized bed portion of a gas phase polymerization reactor and the control agent is introduced into the recycle line of the same reactor, either simultaneously or intermittently relative to the introduction of the catalyst.
  • control agent is in a nebulous or gaseous state at a temperature of from 70°C to 100°C and a pressure of from 10 to 80 bar (or from 1000 kPa to 7,900 kPa).
  • the control agent is selected from the group consisting of alcohols, ethers, aldehydes, ketones, amines (alkylamines, ammonia, and salts thereof), O , carbon monoxide, and mixtures thereof; and even more particularly, the control agent is selected from the group consisting of C 1 to C 10 alcohols, C 2 to C 16 ethers, C 2 to C 10 aldehydes, C 3 to C 16 ketones, ammonia and Ci to C 16 alkylamines, O 2 , carbon monoxide, and mixtures thereof; and yet even more particularly, the control agent is selected from the group consisting of Ci to C 10 alcohols, C 2 to C 10 ethers, O 2 , and mixtures thereof.
  • N is nitrogen and each of R 1 , R 2 , and R 3 are bound to the nitrogen and independently selected from hydrogen, halogens and alkyls; independently selected from hydrogen, chloride, bromide, and Ci to C 16 alkyls in a particular embodiment; wherein at least one R group is an alkyl group.
  • examples of such compounds include trimethylamine, triethylamine, tributylamine, dibutylaminechloride, dimethylaminehydride, and mixtures thereof.
  • the alkylamine useful in the present invention is not herein limited to its physical form, and includes salts of alkylamines. Further, ammonia is not limited to NH 3 , but includes its hydrated form and/or salts of ammonia (e.g., ammonium bromide, ammonium bicarbonate, ammonium alum, etc.).
  • Water may also be present (or added to the polymerization reactor) with the control agent in a particular embodiment; water is present from 1 to 50 wt ppm based on the flow rate of the primary monomer in one embodiment, and present from 2 to 40 wt ppm in another embodiment; and present from 3 to 30 wt ppm in yet another embodiment.
  • water can influence the HMW/LMW split and I 21 of the polymer composition (US 5,525,678), it has been unexpectedly found that a combination of water and a control agent also controls these parameters.
  • the control agent alone in the substantial absence of water is also useful.
  • substantially absence it is meant that water is not added to the reactor, and if present, is present to less than 1 wt ppm based on the flow rate of the primary monomer.
  • control agent is added in an amount sufficient to increase or decrease, decrease in a particular embodiment, the level of incorporation of the HMW polymer by from 0.5 to 50 wt% in one embodiment, and from 1 to 40 wt% in another embodiment, and from 2 to 30 wt% in yet another embodiment, and from 3 to 20 wt% in yet another embodiment, and from 4 to 10 wt% in yet another embodiment based on the total amount of polymer composition, wherein a desirable range of reduction comprises any combination of any upper wt% limit with any lower wt% limit described herein.
  • the control agent can also be characterized by the amount it influences the level of the LMW polymer of the polymer composition.
  • the level of the LMW polymer increases or decreases, preferably decreases, by from 0, or 1, or 2 or 5 to 10 or 15 or 20 wt% based on the total amount of polymer composition, upon introduction of a control agent to the polymerization reactor.
  • the control agent may influence the HMW polymer independent of the LMW polymer in one embodiment; in another embodiment, the HMW and LMW polymers are simultaneously influenced by the presence of the control agent.
  • the bimetallic catalyst composition comprises a metallocene, and another catalyst component selected from the group consisting of titanium and magnesium-containing Ziegler-Natta catalysts and metal-amido catalysts.
  • the bimetallic catalyst composition comprises a metallocene, and a titanium and magnesium-containing Ziegler-Natta catalyst.
  • the catalyst compounds may be supported, and in a particular embodiment, both catalyst components are supported, the support in a particular embodiment being an inorganic oxide support.
  • the process can also be carried out in reverse order, starting with an amount of control agent, with water optionally, followed by the decrease or removal of the control agent; and the individual elements of the method can be varied as described herein.
  • other agents that may have a reverse influence on the split and/or I 21 such as a C to Cio alkane or an aluminum alkyl, may be added simultaneously or intermittently to achieve a balance of I 21 and/or split in the polymer composition.
  • control agents is particularly characterized in maintaining target rheological properties of polymer compositions generated using bimetallic catalysts for use in a single reactor, and even more particularly, maintaining the target values in the presence of agents that might influence the rheological properties in such a manner as to move the rheological properties from their target values.
  • alkanes and aluminum alkyls can alter the split of polymer compositions produced using bimetallic catalyst compositions.
  • control agents and water are used to balance the effects of alkylaluminums and alkanes on the rheological properties of polymer compositions of the invention.
  • One aspect of such control includes a method of producing a polymer composition having a target I 21 comprising incorporating a high molecular weight polymer into a low molecular weight polymer to form the polymer composition in a single gas phase polymerization reactor in the presence of polymerizable monomers, a bimetallic catalyst composition and at least one control agent; wherein the control agent is added in an amount sufficient to control the weight average molecular weight of the high molecular weight polymer, the level of low molecular weight polymer, or both; and wherein the gas phase polymerization reactor comprises a fluidized bed and a fluidizing medium, the fluidizing medium comprises a compound selected from the group consisting of C to C 20 alkanes; and wherein as the amount of alkane increases in the reactor, the amount of control agent is increased in order to maintain the polymer composition at its target I 21 .
  • Another aspect of the invention includes a method of controlling the I 21 of a polymer composition having a target I 21 comprising forming a high molecular weight polymer and a low molecular weight polymer in a single gas phase polymerization reactor in the presence of polymerizable monomers, a bimetallic catalyst composition and at least one control agent; wherein the control agent is added in an amount sufficient to control the weight average molecular weight of the high molecular weight polymer, the level of low molecular weight polymer, or both; and wherein the gas phase polymerization reactor comprises a fluidized bed and a fluidizing medium, the fluidizing medium comprising a compound selected from the group consisting of C 4 to C 20 alkanes; and wherein as the amount of alkane increases in the reactor, the amount of control agent is increased in order to maintain the polymer composition at its target flow index.
  • Yet another aspect of the invention includes a method of producing a polymer composition having a target I 21 comprising contacting a bimetallic catalyst composition, a control agent and polymerizable monomers in a single gas phase polymerization reactor; characterized in that the bimetallic catalyst composition comprises a first catalyst component and a second catalyst component, wherein the first catalyst component is capable of producing a low molecular weight polymer and the second catalyst component is capable of producing a high molecular weight polymer; and wherein the control agent increases the polymerization activity of the second catalyst component relative to the first catalyst component; and wherein the gas phase polymerization reactor comprises a fluidized bed and a fluidizing medium, the fluidizing medium comprising a compound selected from the group consisting of C to C 20 alkanes; and wherein as the amount of alkane increases in the reactor, the amount of control agent is increased in order to maintain the polymer composition at its target flow index.
  • the bimetallic catalyst composition comprises a first catalyst component and a second catalyst component, wherein the first catalyst component is
  • the target I 21 of the polymer composition may vary depending upon the desired end use application. In one embodiment the target I 21 ranges from 3 to 100 dg/min, and ranges from 4 to 20 dg/min in another embodiment, and ranges from 10 to 50 dg/min in another embodiment, and ranges from 5 to 15 dg/min in yet another embodiment, and ranges from 8 to 40 dg/min in yet another embodiment. Whatever, the case, the I 21 of a given polymer composition being generated by a bimetallic catalyst composition under polymerization conditions may be controlled by a series of steps in sequence in any order or simultaneously, wherein
  • an addition or increase in alkane precipitates a need to introduce, increase or decrease control agent, water or both; and in another embodiment, a decrease in alkane precipitates a need to introduce, increase or decrease in control agent, water or both.
  • the introduction or increase in the level of alkane precipitates the need to introduce or increase the level of control agent or water.
  • the target I 21 ranges from 4 to 50 dg/min; the amount of alkane ranges from 0.5 or 1 or 2 to 8 or 10 wt% based on ethylene feed rate; the amount of water ranges from 1 to 50 wt ppm based on the feed rate of primary monomer, preferably ethylene; and the amount of control agent ranges from 0.1 to 40 wt ppm based on the feed rate of primary monomer.
  • the reactor operates in "condensed mode" such as described in US 5,462,999, with alkane entering the reactor at from 0.5 or 2 wt% to 18 or 50 wt% based on the total weight of the fluidizing medium. In such a condensed mode of operation, the amount of control agent or water may vary to counter the influence of the alkane on the I 21 .
  • an amount of an aluminum alkyl is introduced into the reactor. More particularly, the amount of aluminum alkyl once introduced may vary during the polymerization process. It has been found that the introduction, increase or decrease of aluminum alkyl influences the rheological properties of the polymer composition of the invention. Whatever, the case, the I 21 of a given polymer composition being generated by a bimetallic catalyst composition under polymerization conditions may be controlled by a series of steps in sequence in any order or simultaneously, wherein
  • an addition or increase in alkane precipitates a need to introduce, increase or decrease control agent, water or both; and in another embodiment, a decrease in alkane precipitates a need to introduce, increase or decrease in control agent, water or both.
  • the introduction or increase in the level of alkane precipitates the need to introduce or increase the level of control agent or water.
  • the target I 1 ranges from 4 to 20 dg/min; the amount of alkane ranges from 0.5 or 1 or 2 to 8 or 10 wt% based on primary monomer feed rate, preferably ethylene; the amount of control agent ranges from 1 to 50 wt ppm based on the feed rate of primary monomer; the amount of water ranges from 0.1 to 40 wt ppm based on the feed rate of primary monomer; and the amount of aluminum alkyl ranges from 50 to 200 wt ppm based on the feed rate of the primary monomer.
  • Particular embodiments represent examples of the influences of the various agents introduced into the polymerization reactor.
  • the I 21 decreases by from 2 to 50 % when the level of introduction of aluminum alkyl, control agent and water to the polymerization reactor remains constant.
  • the I 21 decreases by from 2 to 50 % when the level of introduction of aluminum alkyl, control agent and water to the polymerization reactor is constant.
  • the first catalyst component that is capable of producing the LMW polymer of the polymer composition is a metallocene in one embodiment.
  • Metallocene catalyst compounds are generally described throughout in, for example, 1 & 2 METALLOCENE-BASED POLYOLEFINS (John Scheirs & W. Kaminsky eds., John Wiley & Sons, Ltd. 2000); G.G. Hlatky in 181 COORDINATION CHEM. REV. 243-296 (1999) and in particular, for use in the synthesis of polyethylene in 1 METALLOCENE-BASED POLYOLEFINS 261-377 (2000).
  • the Cp ligands are one or more rings or ring system(s), at least a portion of which includes ⁇ -bonded systems, such as cycloalkadienyl ligands and heterocyclic analogues.
  • the ring(s) or ring system(s) typically comprise atoms selected from the group consisting of Groups 13 to 16 atoms, and more particularly, the atoms that make up the Cp ligands are selected from the group consisting of carbon, nitrogen, oxygen, silicon, sulfur, phosphorous, germanium, boron and aluminum and combinations thereof, wherein carbon makes up at least 50% of the ring members.
  • M is as described above; each X is bonded to M; each Cp group is chemically bonded to M; and n is 0 or an integer from 1 to 4, and either 1 or 2 in a particular embodiment.
  • the ligands represented by Cp A and Cp B in formula (I) may be the same or different cyclopentadienyl ligands or ligands isolobal to cyclopentadienyl, either or both of which may contain heteroatoms and either or both of which may be substituted by a group R.
  • Cp A and Cp B are independently selected from the group consisting of cyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, and substituted derivatives of each.
  • alkyl substituents R associated with formula (I) through (II) include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl, phenyl, methylphenyl, and tert-butylphenyl groups and the like, including all their isomers, for example tertiary-butyl, isopropyl, and the like.
  • radicals include substituted alkyls and aryls such as, for example, fluoromethyl, fluroethyl, difluroethyl, iodopropyl, bromohexyl, chlorobenzyl and hydrocarbyl substituted organometalloid radicals including trimethylsilyl, trimethylgermyl, methyldiethylsilyl and the like; and halocarbyl- substituted organometalloid radicals including tris(trifluoromethyl)silyl, methylbis(difluoromethyl)silyl, bromomethyldimethylgermyl and the like; and disubstituted boron radicals including dimethylboron for example; and disubstituted Group 15 radicals including dimethylamine, dimethylphosphine, diphenylamine, methylphenylphosphine, Group 16 radicals including methoxy, ethoxy, propoxy, phenoxy, methylsulfide and ethyl
  • substituents R include olefins such as but not limited to olefinically unsaturated substituents including vinyl-terminated ligands, for example 3-butenyl, 2-propenyl, 5-hexenyl and the like.
  • at least two R groups, two adjacent R groups in one embodiment, are joined to form a ring structure having from 3 to 30 atoms selected from the group consisting of carbon, nitrogen, oxygen, phosphorous, silicon, germanium, aluminum, boron and combinations thereof.
  • a substituent group R group such as 1-butanyl may form a bonding association to the element M.
  • Each X in the formula (I) and (II) is independently selected from the group consisting of: halogen ions, hydrides, Ci to C 12 alkyls, C 2 to C 12 alkenyls, C 6 to C 12 aryls, C 7 to C 20 alkylaryls, d to C 12 alkoxys, C 6 to C 16 aryloxys, C 7 to C 18 alkylaryloxys, Ci to C 12 fluoroalkyls, C 6 to C 12 fluoroaryls, and d to C 12 heteroatom-containing hydrocarbons and substituted derivatives thereof in a more particular embodiment; hydride, chloride, fluoride, methyl, phenyl, phenoxy, benzoxy, tosyl, fluoromethyls and fluorophenyls in yet a more particular embodiment; chloride, fluoride, Ci to C 6 alkyls, C 2 to C 6 alkenyls, C to C 18 alkylaryls, halogen
  • the metallocene catalyst component includes those of formula (I) where Cp A and Cp B are bridged to each other by at least one bridging group, (A), such that the structure is represented by formula (II):
  • bridged metallocenes These bridged compounds represented by formula (II) are known as "bridged metallocenes".
  • Cp A , Cp B , M, X and n in structure (II) are as defined above for formula (I); and wherein each Cp ligand is bonded to M, and (A) is chemically bonded to each Cp.
  • Non- limiting examples of bridging group (A) include divalent hydrocarbon groups containing at least one Group 13 to 16 atom, such as but not limited to at least one of a carbon, oxygen, nitrogen, silicon, aluminum, boron, germanium and tin atom and combinations thereof; wherein the heteroatom may also be Ci to C 12 alkyl or aryl substituted to satisfy neutral valency.
  • bridging group (A) is cyclic, comprising, for example 4 to 10, 5 to 7 ring members in a more particular embodiment, which may be substituted.
  • the ring members may be selected from the elements mentioned above, from one or more of B, C, Si, Ge, N and O in a particular embodiment.
  • Non-limiting examples of ring structures which may be present as or part of the bridging moiety are cyclobutylidene, cyclopentylidene, cyclohexylidene, cycloheptylidene, cyclooctylidene and the corresponding rings where one or two carbon atoms are replaced by at least one of Si, Ge, N and O, in particular, Si and Ge.
  • the bonding arrangement between the ring and the Cp groups may be either cis-, trans-, or a combination.
  • the ligands Cp A and Cp B of formulae (I) and (II) are different from each other in one embodiment, and the same in another embodiment.
  • Non-limiting examples of suitable metallocenes or first catalyst component include:
  • Such catalysts include those comprising Group 4, 5 or 6 transition metal oxides, alkoxides and halides, and more particularly oxides, alkoxides and halide compounds of titanium, zirconium or vanadium; optionally in combination with a magnesium compound, internal and/or external electron donors (alcohols, ethers, siloxanes, etc.), aluminum or boron alkyl and alkyl halides, and inorganic oxide supports.
  • the Ziegler-Natta catalyst is combined with a support material in one embodiment, either with or without the second catalyst component.
  • the first catalyst component can be combined with, placed on or otherwise affixed to a support in a variety of ways. In one of those ways, a slurry of the support in a suitable non-polar hydrocarbon diluent is contacted with an organomagnesium compound, which then dissolves in the non-polar hydrocarbon diluent of the slurry to form a solution from which the organomagnesium compound is then deposited onto the carrier.
  • the organomagnesium compound can be added to the slurry while stirring the slurry, until the organomagnesium compound is detected in the support solvent.
  • the organomagnesium compound can be added in excess of the amount that is deposited onto the support, in which case any undeposited excess amount can be removed by filtration and washing.
  • the amount of organomagnesium compound (moles) based on the amount of dehydrated silica (grams) generally range from 0.2 mmol/g to 2 mmol/g in a particular embodiment.
  • Suitable non-metallocene transition metal compounds are compounds of Group 4 and 5 metals that are soluble in the non-polar hydrocarbon used to form the silica slurry in a particular embodiment.
  • the first and second catalyst components may be contacted with the support in any order.
  • the first catalyst component is reacted first with the support as described above, followed by contacting this supported first catalyst component with a second catalyst component.
  • a support may also be present as part of the bimetallic catalyst system of the invention. Supports, methods of supporting, modifying, and activating supports for single-site catalyst such as metallocenes is discussed in, for example, 1 METALLOCENE-BASED POLYOLEFINS 173-218 (J. Scheirs & W. Kaminsky eds., John Wiley & Sons, Ltd. 2000).
  • support or “carrier”, as used herein, are used interchangeably and refer to any support material, a porous support material in one embodiment, including inorganic or organic support materials.
  • the support may be contacted with the other components of the catalyst system in any number of ways.
  • the support is contacted with the activator to form an association between the activator and support, or a "bound activator".
  • the catalyst component may be contacted with the support to form a "bound catalyst component”.
  • the support may be contacted with the activator and catalyst component together, or with each partially in any order.
  • the components may be contacted by any suitable means as in a solution, slurry, or solid form, or some combination thereof, and may be heated when contacted to from 25°C to 250°C.
  • the average pore size of the carrier of the invention typically has pore size in the range of from 10 to lOOOA, from 50 to 500A in another embodiment, and from 75 to 350A in yet another embodiment.
  • the support is an inorganic oxide having an average particle size of less than 50 ⁇ m or less than 35 ⁇ m and a pore volume of from 0.8 to 1 to 2 or 5 cm 3 /g.
  • Dehydration or calcining of the support may or may also be carried out. In one embodiment, the support is calcined prior to reaction with the fluorine or other support- modifying compound.
  • the support especially an inorganic support or graphite support, may be pretreated such as by a halogenation process or other suitable process that, for example, associates a chemical species with the support either through chemical bonding, ionic interactions, or other physical or chemical interaction.
  • the support is fluorided.
  • the fluorine compounds suitable for providing fluorine for the support are desirably inorganic fluorine containing compounds.
  • Such inorganic fluorine containing compounds may be any compound containing a fluorine atom as long as it does not contain a carbon atom.
  • inorganic fluorine containing compounds selected from the group consisting of NH 4 BF 4 , (NH 4 ) 2 SiF 6 , NH 4 PF 6 , NH 4 F, (NH 4 ) 2 TaF 7 , NH 4 NbF 4 , (NH 4 ) 2 GeF 6 , (NH 4 ) 2 SmF 6 , (NH 4 ) 2 TiF 6 , (NH 4 ) 2 ZrF 6 , MoF 6 , ReF 6 , GaF 3 , SO 2 ClF, F 2 , SiF 4 , SF 6 , C1F 3 , C1F 5 , BrF 5 , IF 7 , NF 3 , HF, BF 3 , NHF 2 and NH 4 HF 2 .
  • Another method of treating the support with the fluorine compound is to dissolve the fluorine in a solvent, such as water, and then contact the support with the fluorine containing solution (at the concentration ranges described herein).
  • a solvent such as water
  • silica is the support
  • the support and, for example, fluorine compounds are contacted by any suitable means such as by dry mixing or slurry mixing at a temperature of from 100°C to 1000°C in one embodiment, and from 200°C to 800°C in another embodiment, and from 300°C to 600°C in yet another embodiment, the contacting in any case taking place for between two to eight hours.
  • co-contact or "co-immobilize" more than one catalyst component with a support.
  • co-immobilization of catalyst components include two or more of the same or different metallocene catalyst components, one or more metallocene with a Ziegler-Natta type catalyst, one or more metallocene with a chromium or "Phillips" type catalyst, one or more metallocenes with a Group 15 containing catalyst (metal amido catalyst), and any of these combinations with one or more activators.
  • co-supported combinations include metallocene A/metallocene A; metallocene A/metallocene B; metallocene/Ziegler Natta; metallocene/Group 15 containing catalyst; metallocene/chromium catalyst; metallocene/Ziegler Natta/Group 15 containing catalyst; metallocene/chromium catalyst/Group 15 containing catalyst, any of the these with an activator, and combinations thereof.
  • the catalyst system of the present invention can include any combination of activators and catalyst components, either supported or not supported, in any number of ways.
  • the catalyst component may include any one or both of metallocenes and/or Group 15 containing catalysts components, and may include any combination of activators, any of which may be supported by any number of supports as described herein.
  • Non-limiting examples of catalyst system combinations useful in the present invention include MN + NCA; MN:S + NCA; NCA:S + MN; MN:NCA:S; MN + A1A; MN:S + A1A; A1A:S + MN; MN:A1A:S; A1A:S + NCA + MN; NCA:S + MN + A1A; G15 + NCA; G15:S + NCA; NCA:S + G15; G15:NCA:S; G15 + A1A; G15:S + A1A; A1A:S + G15; G15:A1A:S; A1A:S + G15; G15:A1A:S; A1A:S + NCA + G15; NCA:S + G15 + A1A; MN + NCA + G15; MN:S + NCA + G15; NCA:S + MN + G15; MN:NCA:S + G15; MN + G
  • Embodiments of such activators include Lewis acids such as cyclic or oligomeric poly(hydrocarbylaluminum oxides) and so called non-coordinating activators (“NCA”) (alternately, “ionizing activators” or “stoichiometric activators”), or any other compound that can convert a neutral metallocene catalyst component to a metallocene cation that is active with respect to olefin polymerization.
  • NCA non-coordinating activators
  • Lewis acids such as alumoxane (e.g., "MAO"), modified alumoxane (e.g., "TIBAO” or “MMAO”), and alkylaluminum compounds as activators, and/or ionizing activators (neutral or ionic) such as tri (n-butyl)ammonium tetrakis(pentafluorophenyl)boron and/or a trisperfluorophenyl boron metalloid precursors to activate desirable metallocenes described herein.
  • MAO and other aluminum-based activators are well known in the art.
  • the aluminum alkyl (“alkylaluminum”) activator may be described by the formula A1R ⁇ 3 , wherein R ⁇ is selected from the group consisting of Ci to C 20 alkyls, Ci to C 20 alkoxys, halogen (chlorine, fluorine, bromine) C 6 to C 20 aryls, C 7 to C 25 alkylaryls, and C 7 to C 25 arylalkyls.
  • Non-limiting examples of aluminum alkyl compounds which may be utilized as activators for the catalyst precursor compounds for use in the methods of the present invention include trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri- n-octylaluminum and the like.
  • the alkylaluminum compound, or mixture of compounds, such as trimethylaluminum or triethylaluminum is feed into the reactor in one embodiment at a rate of from 10 wt. ppm to 500 wt. ppm (weight parts per million alkylaluminum feed rate compared to ethylene feed rate), and from 50 wt. ppm to 400 wt. ppm in a more particular embodiment, and from 60 wt. ppm to 300 wt. ppm in yet a more particular embodiment, and from 80 wt. ppm to 250 wt. ppm in yet a more particular embodiment, and from 75 wt. ppm to 150 wt.
  • the alkylaluminum can be represented by the general formula A1R 3 , wherein each R is the same or different and independently selected from Ci to C 10 alkyls and alkoxys.
  • Examples of neutral ionizing activators include Group 13 tri-substituted compounds, in particular, tri-substituted boron, tellurium, aluminum, gallium and indium compounds, and mixtures thereof.
  • the three substituent groups are each independently selected from alkyls, alkenyls, halogen, substituted alkyls, aryls, arylhalides, alkoxy and halides.
  • the three groups are independently selected from halogen, mono or multicyclic (including halosubstituted) aryls, alkyls, and alkenyl compounds and mixtures thereof.
  • the three groups are selected from alkenyl groups having 1 to 20 carbon atoms, alkyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms and aryl groups having 3 to 20 carbon atoms (including substituted aryls), and combinations thereof.
  • the three groups are selected from alkyls having 1 to 4 carbon groups, phenyl, naphthyl and mixtures thereof.
  • the three groups are selected from highly halogenated alkyls having 1 to 4 carbon groups, highly halogenated phenyls, and highly halogenated naphthyls and mixtures thereof.
  • highly halogenated it is meant that at least 50% of the hydrogens are replaced by a halogen group selected from fluorine, chlorine and bromine.
  • the neutral stoichiometric activator is a tri-substituted Group 13 compound comprising highly fluorided aryl groups, the groups being highly fluorided phenyl and highly fluorided naphthyl groups.
  • Illustrative, not limiting examples of ionic ionizing activators include trialkyl- substituted ammonium salts such as triethylammonium tetra(phenyl)boron, tripropylammonium tetra(phenyl)boron, tri(n-butyl)ammonium tetra(phenyl)boron, trimethylammonium tetra(p- tolyl)boron, trimethylammonium tetra(o-tolyl)boron, tributylammonium tetra(pentafluorophenyl)boron, tripropylammonium tetra(o,p-dimethylphenyl)boron, tributylammonium tetra(m,m-dimethylphenyl)boron, tributylammonium tetra(p-tri- fluoromethylphenyl)boron, tributylammonium te
  • an alkylaluminum can be used in conjunction with a heterocyclic compound.
  • the heterocyclic compound includes at least one nitrogen, oxygen, and/or sulfur atom, and includes at least one nitrogen atom in a particular embodiment.
  • the heterocyclic compound includes 4 or more ring members in one embodiment, and 5 or more ring members in another embodiment.
  • the heterocyclic compound for use as an activator with an alkylaluminum may be unsubstituted or substituted with one or a combination of substituent groups.
  • suitable substituents include halogen, alkyl, alkenyl or alkynyl radicals, cycloalkyl radicals, aryl radicals, aryl substituted alkyl radicals, acyl radicals, aroyl radicals, alkoxy radicals, aryloxy radicals, alkylthio radicals, dialkylamino radicals, alkoxycarbonyl radicals, aryloxycarbonyl radicals, carbomoyl radicals, alkyl- or dialkyl- carbamoyl radicals, acyloxy radicals, acylamino radicals, aroylamino radicals, straight, branched or cyclic, alkylene radicals, or any combination thereof.
  • one or more positions on the heterocyclic compound are substituted with a halogen atom or a halogen atom containing group, for example a halogenated aryl group.
  • the halogen is selected from chlorine, bromine and fluorine, and selected from fluorine and bromine in another embodiment, and the halogen is fluorine in yet another embodiment.
  • Non-limiting examples of heterocyclic compounds that may be utilized with the activator of the invention include substituted and unsubstituted pyrroles, imidazoles, pyrazoles, pyrrolines, pyrrolidines, purines, carbazoles, indoles, phenyl indoles, 2,5-dimethylpyrroles, 3- pentafluorophenylpyrrole, 4,5,6,7-tetrafluoroindole or 3,4-difluoropyrroles.
  • the heterocyclic compound described above is combined with an alkylaluminum or an alumoxane to yield an activator compound which, upon reaction with a catalyst component, for example a metallocene, produces an active polymerization catalyst.
  • a catalyst component for example a metallocene
  • suitable alkylaluminums include trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, tri-iso- octylaluminum, triphenylaluminum, and combinations thereof.
  • the activator and catalyst component(s) are combined in mole ratios of activator to catalyst component from 1000:1 to 0.1 :1, and from 300:1 to 1:1 in another embodiment, and from 150:1 to 1:1 in yet another embodiment, and from 50:1 to 1:1 in yet another embodiment, and from 10:1 to 0.5:1 in yet another embodiment, and from 3:1 to 0.3:1 in yet another embodiment, wherein a desirable range may include any combination of any upper mole ratio limit with any lower mole ratio limit described herein.
  • the mole ratio of activator to catalyst component ranges from 2:1 to 100,000:1 in one embodiment, and from 10:1 to 10,000:1 in another embodiment, and from 50:1 to 2,000:1 in yet another embodiment.
  • the activator is a neutral or ionic ionizing activator such as a boron alkyl and the ionic salt of a boron alkyl
  • the mole ratio of activator to catalyst component ranges from 0.5:1 to 10:1 in one embodiment, and from 1:1 to 5:1 in yet another embodiment.
  • the polymerization process of the present invention may be effected as a continuous gas phase process such as a fluid bed process.
  • a fluid bed reactor for use in the process of the present invention typically comprises a reaction zone and a so-called velocity reduction zone.
  • the reaction zone comprises a bed of growing polymer particles, formed polymer particles and a minor amount of catalyst particles fluidized by the continuous flow of the gaseous monomer and diluent to remove heat of polymerization through the reaction zone.
  • some of the re-circulated gases may be cooled and compressed to form liquids that increase the heat removal capacity of the circulating gas stream when readmitted to the reaction zone.
  • a suitable rate of gas flow may be readily determined by simple experiment.
  • control agents of the present invention may be added to any part of the reactor system as described herein, and in a particular embodiment are introduced into the recycle line, and in even a more particular embodiment, introduced into the recycle line upstream of the heat exchanger.
  • the reactor temperature of the fluidized bed process herein ranges from 30°C or
  • a desirable temperature range comprises any upper temperature limit combined with any lower temperature limit described herein.
  • the reactor temperature is operated at the highest temperature that is feasible taking into account the sintering temperature of the polymer product within the reactor.
  • the polymerization temperature, or reaction temperature should be below the melting or "sintering" temperature of the polymer to be formed.
  • the upper temperature limit in one embodiment is the melting temperature of the polyolefin produced in the reactor.
  • the gas phase reactor pressure wherein gases may comprise hydrogen, ethylene and higher comonomers, and other gases, is between 1 (101 kPa) and 100 arm (10,132 kPa) in one embodiment, and between 5 (506 kPa) and 50 atm (5066 kPa) in another embodiment, and between 10 (1013 kPa) and 40 atm (4050 kPa) in yet another embodiment.
  • the polymerization is effected by a slurry polymerization process.
  • a slurry polymerization process generally uses pressures in the range of from 1 to 50 atmospheres and even greater and temperatures in the range of 0°C to 120°C, and more particularly from 30°C to 100°C.
  • a suspension of solid, particulate polymer is formed in a liquid polymerization diluent medium to which ethylene and comonomers and often hydrogen along with catalyst are added.
  • the suspension including diluent is intermittently or continuously removed from the reactor where the volatile components are separated from the polymer and recycled, optionally after a distillation, to the reactor.
  • Another desirable polymerization technique of the invention is referred to as a particle form polymerization, or a slurry process where the temperature is kept below the temperature at which the polymer goes into solution.
  • Other slurry processes include those employing a loop reactor and those utilizing a plurality of stirred reactors in series, parallel, or combinations thereof.
  • Non-limiting examples of slurry processes include continuous loop or stirred tank processes.
  • other examples of slurry processes are described in US 4,613,484 and 2 METALLOCENE-BASED POLYOLEFINS 322-332 (2000).
  • the process of the present invention is suitable for the production of homopolymers of olefins, particularly ethylene, and/or copolymers, terpoiymers, and the like, of olefins, particularly ethylene, and at least one or more other olefin(s).
  • olefins are ⁇ -olefins.
  • the olefins may contain from 2 to 16 carbon atoms in one embodiment; and in another embodiment, ethylene and a comonomer comprising from 3 to 12 carbon atoms in another embodiment; and ethylene and a comonomer comprising from 3 or 4 to 10 carbon atoms in yet another embodiment; and ethylene and a comonomer comprising from 4 to 8 carbon atoms in yet another embodiment.
  • Particularly preferred for preparation herein by the process of the present invention are polyethylenes.
  • Such polyethylenes are homopolymers of ethylene and interpolymers of ethylene and at least one ⁇ -olefin wherein the ethylene content is at least about 50%) by weight of the total monomers involved in one embodiment.
  • hydrogen gas is used in processes of the present invention to control the final properties of the polymer composition, such as described in POLYPROPYLENE HANDBOOK 76-78 (Hanser Publishers, 1996).
  • the amount of hydrogen used in the polymerization process of the present invention is an amount necessary to achieve the desired FI or MI of the final polyolefin resin.
  • a single polymer composition that includes polyolefins with at least one identifiable high molecular weight distribution and polyolefins with at least one identifiable low molecular weight distribution is considered to be a "bimodal" polyolefin, as that term is used herein.
  • Those high and low molecular weight polymers may be identified by deconvolution techniques known in the art to discern the two polymers from a broad or shouldered GPC curve of the bimodal polyolefins of the invention, and in another embodiment, the GPC curve of the bimodal polymers of the invention may display distinct peaks with a trough.
  • the bimodal polymers of the invention are characterized by a combination of features .
  • the bimodal polyolefins of the present invention also have an Mz value ranging from greater than 200,000 in one embodiment, and from greater than 800,000 in another embodiment, and from greater than 900,000 in one embodiment, and from greater than 1,000,000 in one embodiment, and greater than 1,100,000 in another embodiment, and from greater than 1,200,000 in yet another embodiment, and from less than 1,500,000 in yet another embodiment; wherein a desirable range of Mn, Mw or Mz comprises any combination of any upper limit with any lower limit as described herein.
  • the polymer compositions of the invention have a molecular weight distribution, a weight average molecular weight to number average molecular weight (M w /M n ), or "Polydispersity index", of from 2.5 to 150 in one embodiment, and from 10 to 90 in another embodiment, and from 15 to 80 in yet another embodiment, and from 20 to 70 in yet another embodiment, and from 25 to 60 in yet another embodiment, wherein a desirable embodiment comprises any combination of any upper limit with any lower limit described herein.
  • M w /M n weight average molecular weight to number average molecular weight
  • the polymer compositions also have a "z-average" molecular weight distribution (Mz/Mw) of from 2 to 20 in one embodiment, from 3 to 20 in another embodiment, and from 4 to 10 in another embodiment, and from 5 to 8 in yet another embodiment, and from 3 to 10 in yet another embodiment, wherein a desirable range may comprise any combination of any upper limit with any lower limit.
  • Mz/Mw z-average molecular weight distribution
  • MI MI, or I 2 as measured by ASTM-D-1238-E 190°C/2.16 kg
  • MI in the range from 0.01 dg/min to 1000 dg/min in one embodiment, and from 0.01 dg/min to 50 dg/min in another embodiment, and from 0.02 dg/min to 10 dg/min in another embodiment, and from 0.03 dg/min to 2 dg/min in yet another embodiment, wherein a desirable range may comprise any upper limit with any lower limit described herein.
  • the bimodal polyolefins of the invention possess a flow index (I 21 measured by ASTM-D-1238-F, 190 °C/21.6 kg) of from 1 to 1000 dg/min in one embodiment, and from 2 to 100 dg/min in another embodiment, and from 4 to 50 dg/min in yet another embodiment, and from 5 to 20 dg/min in yet another embodiment; wherein a desirable range may comprise any upper limit with any lower limit described herein.
  • the polymer compositions in certain embodiments have a melt index ratio
  • the individual polymers of the polymer composition may also be described by certain embodiments, and in one embodiment, the polymer composition comprises one or more HMW polymers and one or more LMW polymers; and in another embodiment, the polymer composition consists essentially of one HMW polymer and one LMW polymer.
  • the molecular weight distribution (Mw/Mn) of the HMW polymer ranges from 3 to 24, and ranges from 4 to 24 in another embodiment, and from 6 to 18 in another embodiment, and from 7 to 16 in another embodiment, and from 8 to 14 in yet another embodiment, wherein a desirable range comprises any combination of any upper limit with any lower limit described herein.
  • the HMW polymer has a weight average molecular weight ranging from 20,000 to 1,000,000 in one embodiment, and from 50,000 to 900,000 in another embodiment, and from 100,000 to 800,000 amu in another embodiment, and from 250,000 to 700,000 amu in another embodiment, wherein a desirable range comprises any combination of any upper limit with any lower limit described herein.
  • the weight fraction of the HMW polymer in the polymer composition ranges may be at any desirable level depending on the properties that are desired in the polymer composition; in one embodiment the HMW polymer weight fraction ranges from greater than 0.01 or 0.1 or 0.2 or 0.3 or 0.4 or 0.45 or 0.55 or 0.6 or 0.7 or 0.8 or 0.9 or 0.95, and less than from 0.99 or 0.9 or 0.8 or 0.7 or 0.65 or 0.6 or 0.55 or 0.5 or 0.45 or 0.4 or 0.3 or 0.2 or 0.1 or 0.05, wherein a desirable range of HMW polymer in the polymer composition comprises any combination of any upper limit with any lower limit described herein.
  • the weight fraction of HMW polymer ranges from 0.3 to 0.7; and from 0.4 to 0.6 in another particular embodiment, and ranges from 0.5 and 0.6 in yet another particular embodiment.
  • the molecular weight distribution (Mw/Mn) of the LMW polymer ranges from 1.8 to 6, and from 2 to 5 in another embodiment, and from 2.5 to 4 in yet another embodiment, wherein a desirable range comprises any combination of any upper limit with any lower limit described herein.
  • the LMW polymer has a weight average molecular weight ranging from 2,000 to 200,000 amu in one embodiment, and from 5,000 to 100,000 in another embodiment, and from 5,000 to 50,000 amu in yet another embodiment wherein a desirable range of LMW polymer in the polymer composition comprises any combination of any upper limit with any lower limit described herein.
  • the LMW polymer has an I 2 value of 5 from 0.1 to 10,000 dg/min in one embodiment, and from 1 to 5,000 dg/min in another embodiment, and from 100 to 3,000 dg/min in yet another embodiment; and an I 21 of from 0.001 to 100 dg/min in one embodiment, from 0.01 to 50 dg/min in another embodiment, and from 0.1 to 10 dg/min in yet another embodiment; wherein for the I 2 and I 21 values, a desirable range comprises any combination of any upper limit with any lower limit described herein.
  • the I 21 of the LMW polymer may be determined by any technique known in the art; and in one
  • compositions that can then be used in articles of manufacture.
  • additives include processing aids, antioxidants, nucleating agents, acid scavengers, plasticizers, stabilizers, anticorrosion agents, blowing agents, other ultraviolet light absorbers such as chain-breaking antioxidants, etc., quenchers, antistatic agents, slip agents, pigments, dyes and fillers and cure agents such as peroxide.
  • antioxidants and stabilizers such as organic phosphites, hindered amines, and phenolic antioxidants may be present in the polyolefin compositions of the invention from 0.001 to 5 wt% in one embodiment, and from 0.01 to 0.8 wt% in another embodiment, and from 0.02 to 0.5 wt% in yet another embodiment.
  • organic phosphites that are suitable are tris(2,4-di-tert-butylphenyl)phosphite (IRGAFOS 168)
  • Non-limiting examples of hindered amines include poly[2-N,N'-di(2,2,6,6-tetramethyl-4-piperidinyl)- hexanediamine-4-(l -amino- 1 , 1 ,3 ,3 -tetramethylbutane)symtriazine] (CHIMASORB 944); bis(l,2,2,6,6-pentamethyl-4-piperidyl)sebacate (T ⁇ NUVIN 770).
  • Fillers may be present from 0.1 to 50 wt% in one embodiment, and from 0.1 to
  • the polymer compositions of the present invention may also be blended with other polymers.
  • the polymer compositions described herein are blended with high pressure polymerized low density polyethylene, or with linear low density polyethylene in another embodiment, or with other polymers or elastomers, non-limiting examples of which include polypropylene, ethylene-propylene rubber, butyl rubber, high density polyethylene, polycarbonate, polyamides, and polystyrenes.
  • fibers include melt spinning, solution spinning and melt blown fiber operations for use in woven or non- woven form to make filters, diaper fabrics, hygiene products, medical garments, geotextiles, etc.
  • extruded articles include tubing, medical tubing, wire and cable coatings, pipe, geomembranes, and pond liners.
  • molded articles include single and multi- layered constructions in the form of bottles, tanks, large hollow articles, rigid food containers and toys, etc.
  • Further useful articles and goods may be formed economically or incorporate the polyolefins produced by the practice of our invention including: crates, containers, packaging material, labware, office floor mats, instrumentation sample holders and sample windows; liquid storage containers for medical uses such as bags, pouches, and bottles for storage and IV infusion of blood or solutions; wrapping or containing food preserved by irradiation, other medical devices including infusion kits, catheters, and respiratory therapy, as well as packaging materials for medical devices and food which may be irradiated by gamma or ultraviolet radiation including trays, as well as stored liquid, particularly water, milk, or juice, containers including unit servings and bulk storage containers.
  • the following examples relate to gas phase polymerization procedures carried out in a fluidized bed reactor, utilizing ethylene and either a hexene or butene comonomer, resulting in production of polyethylene.
  • the tables identify each run, along with the reported reaction conditions for each run. Various properties of the resulting product are also identified.
  • silica support material Davison Sylopol® 955 Silica is used.
  • the silicas are dehydrated at a temperature of 875°C.
  • a non-metallocene catalyst is combined with the dehydrated silica. That is, for each sample, 500 grams of the respective dehydrated silica is added into a 5-liter, 3-neck round bottom flask enclosed in an N 2 glove box.
  • Anhydrous hexane (2500 ml) is then added into the flask, making a silica/hexane slurry.
  • the slurry is heated to a temperature of about 54°C while under constant stirring, and 380 grams of a 15 wt.% solution of dibutyl magnesium is added to the slurry over a period of about 20 minutes. The slurry ⁇ s then allowed to stand for an additional 30 minutes.
  • Butanol (27.4 grams) is diluted to volume with hexane in a 125 ml volumetric flask. The entire 125 ml of diluted butanol solution is added dropwise into the flask containing the slurry, and then the slurry is held at a temperature of about 54°C for 30 minutes while under constant agitation. The amount of butanol may be varied, depending upon the desired concentrations.
  • Titanium tetrachloride (41.0 grams) is diluted to volume with hexane in a 125 ml volumetric flask. The entire 125 ml of diluted titanium tetrachloride solution is then added dropwise into the flask containing the slurry. Following the addition of the solution, the slurry is allowed to stand for about 30 minutes at a temperature of about 54°C. The slurry is then allowed to cool to ambient temperature.
  • the metallocene catalyst compound is then added to the sample of titanium tetrachloride-treated dehydrated silica.
  • About 13.72 grams of the metallocene bis-n-butyl-cyclopentadienyl zirconium difluoride is added into the MAO solution, and the mixture is stirred until all of the solids are dissolved.
  • the MAO/Metallocene mixture is slowly added into the flask containing the previously prepared titanium reaction slurry over a period of about one hour.
  • Toluene (50 ml) is used to wash the residual MAO/Metallocene mixture remaining in the flask into the flask containing the reaction slurry.
  • the Al/Zr molar ratio (Al from MAO) may range from about 90 to 110; the Ti/Zr molar ratio is about 6.
  • Each resulting mixture that included the respective bimetallic catalyst sample is then held at ambient temperature for a period of one hour. Afterward, each mixture is dried using a rotary vaporizer, followed by removing most of the hexanes using a vacuum pressure of 21 mmHg at a temperature of 52°C. The high boiling point toluene was subsequently removed using a vacuum pressure of 28 mmHg at a temperature of 70°C.
  • each run utilized a target reactor temperatures ("Bed Temperature"), typically, a reactor temperature of about 203°F or 95°C. During each run, reactor temperature was maintained at an approximately constant level by adjusting up or down the temperature of the recycle gas to accommodate any changes in the rate of heat generation due to the polymerization.
  • Bed Temperature target reactor temperatures
  • reactor temperature was maintained at an approximately constant level by adjusting up or down the temperature of the recycle gas to accommodate any changes in the rate of heat generation due to the polymerization.
  • Example 1 Impact of iC5 feed at 95°C reaction temperature. Table 1 shows a comparison between polyethylene production with and without feed of isopentane (iC5). These runs took place on the same reactor.
  • Run number 1 was done using iC5, with an iC5 feed rate equal to 4.2 wt% of the ethylene feed rate.
  • Run 2 was done using no iC5 feed, at the same reactor temperature of about 95°C. Without iC5 feed, a much lower water feed rate was required to maintain approximately the same resin FI. Normally, a decrease in water feed rate as seen between run 1 and 2, namely 19.8 to 14.5 wt ppm water feed rate, would cause an FI drop of at least 30%. However, the omission of iC5 feed for run 2 was sufficient to cause FI to be 7% higher in run 2. Isopentane feed significantly influenced the polymer FI, with higher iC5 feed rate giving lower FI.
  • Example 3 Impact of hexane feed at 95°C reaction temperature. Table 2 shows a comparison between polyethylene production with and without feed of hexane. These runs took place sequentially the same reactor. Run number 5 was done using hexane, with a hexane feed rate equal to 1.1 wt% of the ethylene feed rate. Run 6 was done using no hexane feed, at the same reactor temperature of about 95°C. Without hexane feed, a much lower water feed rate was required to maintain approximately the same resin FI. Normally, a decrease in water feed rate as seen between run 5 and 6, namely 26.4 to 16.3 wt ppm water feed rate, would cause an FI drop of at least 40%.
  • Example 4 Impact of TMA feed at 95°C reaction temperature. Tables 1 and 2 allow a comparison between polyethylene production comparing between 100 and 125 wt ppm trimethylaluminum (TMA) feed rate. These runs took place on the same reactor. Run number 2 was done using 100 ppm TMA feed rate. Run 6 was done using 125 ppm TMA feed rate, with other reaction variables except water feed rate at similar values. With higher TMA feed in run 6, a higher water feed rate still was not sufficient to raise resin FI.
  • TMA trimethylaluminum
  • Example 5 Impact of TMA feed with concurrent isopropyl alcohol feed.
  • LMW polymers can be controlled, and in particular, that the rheological properties of the resultant polymer composition can be controlled.
  • Another advantage of the present invention is the reduction of gels (spots of discontinuity wherein a portion of the polymer is immiscible in the surrounding bulk polymer) in the polymer compositions produced herein, and further in the films and other articles produced from the polymer compositions.
  • Another advantage is that the use of the control agents of the present invention also have been shown to reduce reactor fouling in gas phase reactors, thus increasing the utility of such a process as claimed herein.
  • Yet another advantage of the present invention is the ease of transition in the reactor from the bimetallic catalyst composition to, for example, a chromium catalyst which is known to be sensitive to alcohols and ether agents. Such a transition in the reactor from the bimetallic catalyst composition comprising a metallocene/Ziegler-Natta composition to a chromium oxide type catalyst was made without reduction in the expected activity and productivity of the chromium catalyst.
  • the polymer composition may be processed by any technique common in the art to produce a variety of products; processing techniques include injection molding, blow molding, roto-molding or formed into a sheet or tubing; wherein the polymer composition used to make these products may first be extruded and pelleted by techniques common in the art and blended with any combination of additives such as processing aids and antioxidants.
  • processing techniques include injection molding, blow molding, roto-molding or formed into a sheet or tubing; wherein the polymer composition used to make these products may first be extruded and pelleted by techniques common in the art and blended with any combination of additives such as processing aids and antioxidants.
  • One embodiment of the method of producing a polymer composition is as follows.
  • target I 21 value For a given polymerization run, a choice is made by the resin manufacturer to produce a polymer composition which possesses a desirable "target I 21 value", such as, for example, a range of from 5 to 15 dg/min for a composition to be made into certain desirable end products such as films, and a range of from 22 to 38 dg/min for a polymer composition to used in blow molding applications.
  • the target I 21 value is typically a range of values in practice, such as a range of +/- 2 to +/-10 dg/min about any value of from 3 to 100 or 200 dg/min, depending on the desired target value and the desired level of fluctuation in the actual target value in various batches of the polymer composition coming off the reactor.
  • control agent either as a liquid, nebulized solid, solution, or other form, is added to the reactor, preferably injected in the recycle line, in an amount sufficient to control the weight average molecular weight of the high molecular weight polymer, the level of low molecular weight polymer, or both.
  • control agent is chosen and added such that it alters, either by increasing or decreasing, the polymerization activity of one or both of the catalyst components of the bimetallic catalyst composition.
  • the gas phase polymerization reactor comprises a fluidized bed and a fluidizing medium, the fluidizing medium comprising an alkane selected from the group consisting of C 4 to C 20 alkanes.
  • the alkane is added to the reactor, and/or its concentration in the reactor is increased, there is typically a need to adjust the I 21 of the polymer composition, as it may vary as alkane concentration changes.
  • aluminum alkyls may be added to or taken away from the reactor, thus influencing the I 21 of the polymer composition. In either or both cases, the level of control agent will typically be adjusted to maintain the polymer composition at its target I 2 ⁇ .

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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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Abstract

L'invention concerne des procédés de contrôle des propriétés rhéologiques de compositions polymères comprenant au moins un polymère de poids moléculaire élevé et un polymère de faible poids moléculaire. Les compositions polymères sont produites par polymérisation de monomères dans un réacteur unique à l'aide d'une composition catalytique bimétallique. Un agent de contrôle tel que, par exemple, un alcool, de l'éther, de l'oxygène ou une amine, est ajouté au réacteur afin de contrôler les propriétés rhéologiques du réacteur. La polymérisation a lieu en présence de composés de modification des propriétés rhéologiques tels que des alcanes et des alkyles d'aluminium. Les agents de contrôle sont ajoutés en une quantité suffisante pour contrer les influences des composés de modification des propriétés rhéologiques.
EP04818279A 2003-10-15 2004-03-25 Procede de polymerisation et controle des proprietes d'une composition polymere Withdrawn EP1673400A4 (fr)

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US10/685,607 US7238756B2 (en) 2003-10-15 2003-10-15 Polymerization process and control of polymer composition properties
US10/685,650 US6828395B1 (en) 2003-10-15 2003-10-15 Polymerization process and control of polymer composition properties
PCT/US2004/009411 WO2005044863A1 (fr) 2003-10-15 2004-03-25 Procede de polymerisation et controle des proprietes d'une composition polymere

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DE102005035477A1 (de) * 2005-07-26 2007-02-01 Basell Polyolefine Gmbh Verfahren zur Steuerung der relativen Aktivität der unterschiedlichen aktiven Zentren von Hybridkatalysatoren
US20070049711A1 (en) 2005-09-01 2007-03-01 Chi-I Kuo Catalyst compositions comprising support materials having an improved particle-size distribution
ES2421887T3 (es) * 2007-03-30 2013-09-06 Univation Tech Llc Sistemas y métodos para fabricación de poliolefinas
US7888522B2 (en) 2007-04-26 2011-02-15 Georg-August-Universität Göttingen Stiftung Öffentlichen Rechts Oxygen-bridged bimetallic complex and polymerization process
TW200936619A (en) * 2007-11-15 2009-09-01 Univation Tech Llc Polymerization catalysts, methods of making, methods of using, and polyolefin products made therefrom
US20110256632A1 (en) * 2009-01-08 2011-10-20 Univation Technologies, Llc Additive for Polyolefin Polymerization Processes
BR112014016024B1 (pt) * 2011-12-31 2021-01-12 Univation Technologies, Llc aditivo de continuidade para processos de polimerização de poliolefinas
CA2938740C (fr) 2014-02-11 2022-06-21 Univation Technologies, Llc Production de produits de polyolefines
US9650459B2 (en) * 2015-09-09 2017-05-16 Chevron Phillips Chemical Company Lp Methods for controlling die swell in dual catalyst olefin polymerization systems
US9540457B1 (en) * 2015-09-24 2017-01-10 Chevron Phillips Chemical Company Lp Ziegler-natta—metallocene dual catalyst systems with activator-supports
WO2019162760A1 (fr) 2018-02-05 2019-08-29 Exxonmobil Chemical Patents Inc. A Corporation Of State Of Delaware Aptitude au traitement améliorée de lldpe par addition de polyéthylène haute densité de masse moléculaire ultra-élevée
EP4259669A1 (fr) * 2020-12-08 2023-10-18 ExxonMobil Chemical Patents Inc. Compositions de polyéthylène haute densité à ramification à longue chaîne
WO2024056725A1 (fr) 2022-09-15 2024-03-21 Basell Polyolefine Gmbh Composition de polyéthylène pour moulage par soufflage ayant un comportement de gonflement amélioré

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BRPI0415414A (pt) 2006-12-05
TW200523312A (en) 2005-07-16
EP1673401A4 (fr) 2007-07-11
EP1673401B1 (fr) 2015-10-21
WO2005044866A1 (fr) 2005-05-19
JP4343231B2 (ja) 2009-10-14
AR045632A1 (es) 2005-11-02
WO2005044863A1 (fr) 2005-05-19
JP4857115B2 (ja) 2012-01-18
AR045631A1 (es) 2005-11-02
RU2332426C2 (ru) 2008-08-27
CA2539030A1 (fr) 2005-05-19
JP2007508435A (ja) 2007-04-05
RU2331653C2 (ru) 2008-08-20
CA2538470A1 (fr) 2005-05-19
RU2006116442A (ru) 2007-11-20
BRPI0415341B1 (pt) 2014-02-04
EP1673401A1 (fr) 2006-06-28
TW200513470A (en) 2005-04-16

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