WO2000032653A1 - Nitrogen substituted phosphinimine ligand - Google Patents
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- WO2000032653A1 WO2000032653A1 PCT/CA1999/001016 CA9901016W WO0032653A1 WO 2000032653 A1 WO2000032653 A1 WO 2000032653A1 CA 9901016 W CA9901016 W CA 9901016W WO 0032653 A1 WO0032653 A1 WO 0032653A1
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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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/02—Ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S526/901—Monomer polymerized in vapor state in presence of transition metal containing catalyst
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S526/943—Polymerization with metallocene catalysts
Definitions
- This invention relates to a catalyst for olefin polymerization.
- the catalyst is an organometallic complex of a group 4 metal.
- the catalyst contains a cyclopentadienyl type ligand and a heterosubstituted phosphinimine ligand.
- the heterosubstituted phosphinimine ligand may be conveniently and inexpensively synthesized and is comparatively non- pyrophoric.
- Olefin polymerization catalysts having a cyclopentadienyl ligand and a conventional phosphinimine ligand are disclosed in a copending and commonly assigned patent application (Stephen et al).
- the catalysts of the Stephen et al disclosure are highly active for ethylene (co)polymerization, particularly when used in combination with an alumoxane, or an "ionic activator" (or both).
- heterosubstituted phosphinimine ligands may be easily synthesized and can be used as a component of a highly active ethylene polymerization catalyst system.
- the present invention provides a catalyst component for olefin polymerization comprising an organometallic complex defined by the formula:
- Cp is selected from cyclopentadienyl, substituted cyclopentadienyl, indenyl, substituted indenyl, fluorenyl, and substituted fluorenyl; M is a metal selected from titanium, zirconium and hafnium; X is an activatable ligand and n is selected from 1 and 2; said HPI is a heterosubstituted phosphinimine ligand which is bonded to the metal M and wherein said HPI is defined by the formula: ( 1 )a (H 1 ) b
- R 1 is independently selected from the group consisting of a hydrogen atom, a halogen atom, C 1 - 20 hydrocarbyl radicals which are unsubstituted by or further substituted by a halogen atom, a d-s alkoxy radical, a C ⁇ -io aryl or aryloxy radical, a silyl radical of the formula:
- each R 2 is independently selected from the group consisting of hydrogen, a C-i- ⁇ alkyl or alkoxy radical, C ⁇ -io aryl or aryloxy radicals, and a germanyl radical of the formula:
- Prior art phosphinimines generally involve pyrophoric phosphine precursors in their synthesis.
- the phosphine precursors of the heterosubstituted phosphinimines used in the present invention mitigate this disadvantage because they may be readily synthesized from less pyrophoric precursors, as illustrated in the examples. This reduces the likelihood of process fires during commercial manufacture of the phosphinimine ligands.
- the present catalyst components may be used in combination with an activator to provide an olefin polymerization catalyst system.
- Alumoxanes, "ionic activators” and/or combinations of the two may be used as activators.
- the catalyst components of this invention are defined by the formula: HPI
- Cp — M — (X) n wherein is a group 4 metal selected from titanium, zirconium and hafnium; HPI is a heterosubstituted phosphinimine ligand (as described in section 1.2); Cp is a cyclopentadienyl ligand (as described in section 1.3); each X is independently an activatable ligand (and each is preferably a simple monoanionic ligand such as an alkyl or halide - as described in section 1.4); and n is 1 or 2 as defined by the formula, depending upon the valence of the metal M and the anionic ligand(s) as described in section 1.4.
- Preferred catalysts are monocyclopentadienyl complexes of titanium (IV) having two, monoanionic activatable ligands (i.e. n is 2).
- the catalyst component of this invention must contain a heterosubstituted phosphinimine ligand which is covalently bonded to the metal.
- This ligand is defined by the formula:
- each R 1 is independently selected from the group consisting of a hydrogen atom, a halogen atom, C1-20 hydrocarbyl radicals which are unsubstituted by or further substituted by a halogen atom, a C ⁇ -8 alkoxy radical, a C 6- ⁇ o aryl or aryloxy radical, a silyl radical of the formula:
- each R 2 is independently selected from the group consisting of hydrogen, a C ⁇ -8 alkyl or alkoxy radical, C 6 - ⁇ o aryl or aryloxy radicals, and a germanyl radical of the formula:
- H 1 is a heterosubstituent which is characterized by having a nitrogen atom that is bonded to the phosphorus atom via a single covalent bond.
- the nitrogen atom is then substituted either with two substituents (which are bonded to the nitrogen via single bonds) or one substituent (bonded to the nitrogen via a double bond).
- the substituents on the nitrogen atom are not particularly critical to the success of this invention. However, for reasons of cost and convenience, it is preferred that each R 1 substituent on the nitrogen atom is independently selected from hydrocarbyl and silyl (and, as will be appreciated by those skilled in the art, the hydrocarbyl and/or silyl substituents may also be substituted).
- Hydrocarbyl groups are particularly preferred R 1 substituents.
- the sum of a+b is 3 when all three substituents on the phosphorus atoms are singly bonded to it.
- cyclopentadienyl-type ligand is meant to convey its conventional meaning, namely a ligand having a five carbon ring which is bonded to the metal via eta-5 bonding.
- cyclopentadienyl-type includes unsubstituted cyclopentadienyl, substituted cyclopentadienyl, unsubstituted indenyl, substituted indenyl, unsubstituted fluorenyl and substituted fluorenyl.
- An exemplary list of substituents for a cyclopentadienyl ligand includes the group consisting of C- ⁇ - 10 hydrocarbyl radical (which hydrocarbyl substituents are unsubstituted or further substituted); a halogen atom, C ⁇ -8 alkoxy radical, a C ⁇ -io aryl or aryloxy radical; an amido radical which is unsubstituted or substituted by up to two C- ⁇ - 8 alkyl radicals; a phosphido radical which is unsubstituted or substituted by up to two C ⁇ -8 alkyl radicals; silyl radicals of the formula -Si-(R 2 ) 3 wherein each R 2 is independently selected from the group consisting of hydrogen, a C ⁇ -8 alkyl or alkoxy radical C ⁇ -io aryl or aryloxy radicals; germanyl radicals of the formula Ge-(R 2 ) 3 wherein R 2 is as defined directly above. It is preferred to use
- activatable ligand refers to a ligand which may be activated by a cocatalyst (also known as an "activator” to facilitate olefin polymerization).
- exemplary activatable ligands are independently selected from the group consisting of a hydrogen atom, a halogen atom, a C-M O hydrocarbyl radical, a CMO alkoxy radical, a C 5- ⁇ o aryl oxide radical; each of which said hydrocarbyl, alkoxy and aryl oxide radicals may be unsubstituted by or further substituted by a halogen atom, a C ⁇ -8 alkyl radical, a C ⁇ -8 alkoxy radical, a C ⁇ -io aryl or aryl oxy radical, an amido radical which is unsubstituted or substituted by up to two C ⁇ -8 alkyl radicals; a phosphido radical which is unsubstituted or substituted by up to two C1-8
- the number of activatable ligands depends upon the valency of the metal and the valency of the activatable ligand.
- the preferred catalyst metals are group 4 metals in their highest oxidation state (i.e. 4 + ) and the preferred activatable ligands are monoanionic.
- the preferred catalyst components contain one phosphinimine ligand, one cyclopentadienyl ligand and two (monoanionic) activatable ligands bonded to the group 4 metal.
- the metal of the catalyst component may not be in the highest oxidation state.
- a titanium (III) component would contain only one monoanionic activatable ligand.
- the catalyst components described in part 1 above are used in combination with an "activator” (which may also be referred to by a person skilled in the art as a “cocatalyst”) to form an active catalyst system for olefin polymerization.
- an "activator” which may also be referred to by a person skilled in the art as a “cocatalyst”
- Simple aluminum alkyls and alkoxides may provide comparatively weak cocatalytic activity under certain mild polymerization conditions.
- the preferred activators are alumoxanes and so- called ionic activators, as described below.
- the alumoxane activator may be of the formula:
- each R 4 is independently selected from the group consisting of C- ⁇ - 20 hydrocarbyl radicals and m is from 0 to 50, preferably R 4 is a C ⁇ - alkyl radical and m is from 5 to 30.
- Methylalumoxane (or "MAO") is the preferred alumoxane.
- Alumoxanes are well known as activators for metallocene-type catalysts.
- Activation with alumoxane generally requires a molar ratio of aluminum in the activator to (group 4) metal in the catalyst from 20:1 to 1000:1. Preferred ratios are from 50:1 to 250:1.
- Ionic activators are also well known for metallocene catalysts. See, for example, USP 5,198,401 (Hlatky and Turner). These compounds may be selected from the group consisting of:
- R 7 is a pentafluorophenyl radical
- R 5 is a triphenylmethyl cation
- Z is a nitrogen atom
- R 8 is a C- ⁇ - 4 alkyl radical or R 8 taken together with the nitrogen atom forms an anilinium radical which is substituted by two C ⁇ - 4 alkyl radicals.
- the "ionic activator” may abstract one or more activatable ligands so as to ionize the catalyst center into a cation but not to covalently bond with the catalyst and to provide sufficient distance between the catalyst and the ionizing activator to permit a polymerizable olefin to enter the resulting active site.
- ionic activators include: 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-trifluoromethylphenyl)boron, tributylammonium tetra(pentafluorophenyl)boron, tri(n-butyl)ammonium te
- Readily commercially available ionic activators include: N,N- dimethylaniliniumtetrakispentafluorophenyl borate, triphenylmethylium tetrakispentafluorophenyl borate, and trispentafluorophenyl borane. 3. Homogeneous or Heterogeneous Catalyst
- the catalyst system of this invention is preferably used in a homogeneous form in solution polymerization (where the term “homogeneous” means that the catalyst and cocatalyst/activator are soluble in, or miscible with, the polymerization solvent).
- homogeneous means that the catalyst and cocatalyst/activator are soluble in, or miscible with, the polymerization solvent.
- the catalyst when employed in a slurry or gas phase polymerization, it is highly preferred to use the catalyst in a heterogeneous or "supported form”. It is also highly preferred that the catalyst does not cause reactor fouling.
- heterogeneous catalysts may be grouped into three main categories:
- These catalysts are prepared by depositing the catalyst component and a cocatalyst on a very porous metal oxide support.
- the catalyst and cocatalyst are substantially contained within the pore structure of the metal oxide particle. This means that a comparatively large metal oxide particle is used (typically particle size of from 40 to 80 microns).
- the preparation of this type of supported catalyst is described in USP 4,808,561 (Welborn, to Exxon). 0 3.3. Filled/Spray Dried Catalysts
- Friable catalyst particles lead to the formation of "fines" in the polyethylene product, and may also aggravate reactor fouling problems.
- the catalysts of this invention are suitable for use in any conventional olefin polymerization process, such as the so-called "gas phase”, “slurry”, “high pressure” or “solution” polymerization processes.
- the polymerization process according to this invention uses ethylene and may include other monomers which are copolymerizable therewith such as other alpha olefins (having from three to ten carbon atoms, preferably butene, hexene or octene) and, under certain conditions, dienes such as hexadiene isomers, vinyl aromatic monomers such as styrene or cyclic olefin monomers such as norbornene.
- alpha olefins having from three to ten carbon atoms, preferably butene, hexene or octene
- dienes such as hexadiene isomers
- vinyl aromatic monomers such as styrene or cyclic olefin monomers such as norbornene.
- the present invention may also be used to prepare elastomeric co- and terpolymers of ethylene, propylene and optionally one or more diene monomers.
- elastomeric polymers will contain about 50 to abut 75 weight % ethylene, preferably about 50 to 60 weight % ethylene and correspondingly from 50 to 25% of propylene.
- a portion of the monomers, typically the propylene monomer, may be replaced by a conjugated diolefin.
- the diolefin may be present in amounts up to 10 weight % of the polymer although typically is present in amounts from about 3 to 5 weight %.
- the resulting polymer may have a composition comprising from 40 to 75 weight % of ethylene, from 50 to 15 weight % of propylene and up to 10 weight % of a diene monomer to provide 100 weight % of the polymer.
- the dienes are dicyclopentadiene, 1 ,4-hexadiene, 5-methylene-2-norbornene, 5- ethylidene-2-norbornene and 5-vinyl-2-norbornene.
- Particularly preferred dienes are 5-ethylidene-2-norbornene and 1 ,4-hexadiene.
- the polyethylene polymers which may be prepared in accordance with the present invention typically comprise not less than 60, preferably not less than 70 weight % of ethylene and the balance one or more C - ⁇ 0 alpha olefins, preferably selected from the group consisting of 1 -butene, 1 - hexene and 1 -octene.
- the polyethylene prepared in accordance with the present invention may be linear low density polyethylene having density from about 0.910 to 0.935 g/cc.
- the present invention might also be useful to prepare polyethylene having a density below 0.910 g/cc - the so- called very low and ultra low density polyethylenes.
- the most preferred polymerization process of this invention encompasses the use of the novel catalysts (together with a cocatalyst) in a medium pressure solution process.
- the term "medium pressure solution process” refers to a polymerization carried out in a solvent for the polymer at an operating temperature from 100 to 320°C (especially from 120 to 220°C) and a total pressure of from 3 to 35 mega Pascals. Hydrogen may be used in this process to control (reduce) molecular weight.
- Optimal catalyst and cocatalyst concentrations are affected by such variables as temperature and monomer concentration but may be quickly optimized by non-inventive tests. Further details concerning the medium pressure polymerization process are well known to those skilled in the art and widely described in the open and patent literature.
- the catalyst of this invention may also be used in a slurry polymerization process or a gas phase polymerization process.
- the typical slurry polymerization process uses total reactor pressures of up to about 50 bars and reactor temperature of up to about 200°C.
- the process employs a liquid medium (e.g. an aromatic such as toluene or an alkane such as hexane, propane or isobutane) in which the polymerization takes place. This results in a suspension of solid polymer particles in the medium.
- Loop reactors are widely used in slurry processes. Detailed descriptions of slurry polymerization processes are widely reported in the open and patent literature.
- a fluidized bed gas phase polymerization reactor employs a "bed" of polymer and catalyst which is fluidized by a flow of monomer which is at least partially gaseous. Heat is generated by the enthalpy of polymerization of the monomer flowing through the bed. Unreacted monomer exits the fluidized bed and is contacted with a cooling system to remove this heat. The cooled monomer is then re-circulated through the polymerization zone together with "make-up" monomer to replace that which was polymerized on the previous pass.
- the "fluidized” nature of the polymerization bed helps to evenly distribute/mix the heat of reaction and thereby minimize the formation of localized temperature gradients (or "hot spots").
- An alternative (and preferable) approach to high monomer flow is the use of an inert condensable fluid which will boil in the fluidized bed (when exposed to the enthalpy of polymerization), then exit the fluidized bed as a gas, then come into contact with a cooling element which condenses the inert fluid. The condensed, cooled fluid is then returned to the polymerization zone and the boiling/condensing cycle is repeated.
- condensed mode operation alkanes such as butane, pentanes or hexanes
- alkanes such as butane, pentanes or hexanes
- Preferred Polymerization Temperatures about 75°C to about
- Pressure up to about 1000 psi (with a preferred range of from about 100 to 350 psi for olefin polymerization).
- Part A Catalyst Component Synthesis
- Part B Solution Polymerization
- Part C Gel Phase Polymerization
- GPC Gel permeation chromatography
- Polymer densities were measured using pressed plaques (ASTM method D-1928-90), with a densitometer.
- Ph phenyl
- Mw weight average molecular weight
- Mn number average molecular weight
- PE polyethylene
- Pentamethylcvclopentadienvir(dimethylamino)di-t- tBu 2 (Me 2 N)P N-SiMe 3 (527mg, 1.91 mmol) and Cp * TiCI3 (563 mg, 1.95 mmol) were combined and toluene (20 mL) was added. The reaction mixture was heated at 90°C for 60 minutes and was then cooled.
- the catalyst solutions were pumped to the reactor independently and in some cases were mixed before entering the polymerization reactor (as indicated in the examples). Because of the low solubility of the catalysts, activators and MAO in cyclohexane, solutions were prepared in purified xylene.
- the catalyst was activated in-situ (in the polymerization reactor) at the reaction temperature in the presence of the monomers.
- the polymerizations were carried out in cyclohexane at a pressure of 1500 psi. Ethylene was supplied to the reactor by a calibrated thermal mass flow meter and was dissolved in the reaction solvent prior to the polymerization reactor.
- comonomer for example 1 -octene
- ethylene conversion is a dependent variable controlled by the catalyst concentration, reaction temperature, catalyst activity, etc.
- the internal reactor temperature is monitored by a thermocouple in the polymerization medium and can be controlled at the required set point to +/- 0.5°C own stream of the reactor the pressure was reduced from the reaction pressure (1500 psi) to atmospheric.
- the solid polymer was then recovered as a slurry in the condensed solvent and was dried by evaporation before analysis.
- the ethylene conversion was determined by a dedicated on line gas chromatograph by reference to propane which was used as an internal standard.
- the average polymerization rate constant was calculated based on the reactor hold-up time, the catalyst concentration in the reactor and the ethylene conversion and is expressed in l/(mmol * min).
- Average polymerization rate (kp) (0/(100-Q)) x (1/[TM]) x (1/HUT) where: Q is the percent ethylene conversion.
- [TM] is the catalyst concentration in the reactor expressed in mM.
- HUT is the reactor hold-up time in minutes.
- the supported catalysts were prepared by initially supporting MAO on a silica support, followed by deposition of the catalyst component. All the polymerization experiments described below were conducted using a semi-batch, gas phase polymerization reactor of total internal volume of 2.2 L.
- the reaction gas mixtures (an ethylene/butene mixture containing 4 mole % butene and 96 mole % ethylene) was measured to the reactor on a continuous basis using a calibrated thermal mass flow meter, following passage through purification media as described above.
- a pre-determined mass of the catalyst sample as added to the reactor under the flow of the inlet gas with no pre-contact of the catalyst with any reagent, such as a catalyst activator.
- the catalyst was activated in-situ (in the polymerization reactor) at the reaction temperature in the presence of the monomers, using a metal alkyl complex which has been previously added to the reactor to remove adventitious impurities. Purified and rigorously anhydrous sodium chloride was used as a catalyst dispersing agent.
- the internal reactor temperature is monitored by a thermocouple in the polymerization medium and can be controlled at the required set point to +/- 1.0°C.
- the duration of the polymerization experiment was one hour. Following the completion of the polymerization experiment, the polymer was separated from the sodium chloride and the yield determined.
- Table 2 illustrates data concerning the Al/transition metal ratios of the supported catalyst; polymer yield and polymer properties.
- This invention provides technology which is useful for the preparation of ethylene polymers, especially copolymers of ethylene and alpha olefins.
- the ethylene (co)polymers may be used in a wide variety of applications including extruded goods, injection molded goods and blow molded goods.
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Abstract
Description
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Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
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DE69939026T DE69939026D1 (en) | 1998-11-26 | 1999-11-01 | Stickstoffsubstituierte phosphiniminligand |
EP99952203A EP1135421B1 (en) | 1998-11-26 | 1999-11-01 | Nitrogen substituted phosphinimine ligand |
AU64573/99A AU6457399A (en) | 1998-11-26 | 1999-11-01 | Nitrogen substituted phosphinimine ligand |
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CA002254841A CA2254841C (en) | 1998-11-26 | 1998-11-26 | Nitrogen substituted phosphinimine ligand |
CA2,254,841 | 1998-11-26 |
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WO2000032653A1 true WO2000032653A1 (en) | 2000-06-08 |
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PCT/CA1999/001016 WO2000032653A1 (en) | 1998-11-26 | 1999-11-01 | Nitrogen substituted phosphinimine ligand |
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US (1) | US6234950B1 (en) |
EP (1) | EP1135421B1 (en) |
AT (1) | ATE399800T1 (en) |
AU (1) | AU6457399A (en) |
CA (1) | CA2254841C (en) |
DE (1) | DE69939026D1 (en) |
WO (1) | WO2000032653A1 (en) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
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EP1162214A1 (en) * | 2000-06-08 | 2001-12-12 | Nova Chemicals (International) S.A. | Process to prepare ethylene propylene elastomer |
WO2005014674A2 (en) * | 2003-08-04 | 2005-02-17 | Dsm Ip Assets B.V. | Process for the preparation of a polyolefin |
WO2005014601A3 (en) * | 2003-08-04 | 2005-11-03 | Dsm Ip Assets Bv | Process for the preparation of a polyolefin |
WO2006054048A1 (en) | 2004-11-18 | 2006-05-26 | Ineos Europe Limited | Supported polymerisation catalysts |
EP1731536A1 (en) | 2005-06-09 | 2006-12-13 | Innovene Manufacturing France SAS | Supported polymerisation catalysts |
WO2007075299A2 (en) * | 2005-12-16 | 2007-07-05 | Dow Global Technologies Inc. | Polydentate heteroatom ligand containing metal complexes, catalysts and methods of making and using the same |
WO2007137395A1 (en) * | 2006-05-30 | 2007-12-06 | Nova Chemicals (International) S.A. | Supported polymerization catalysts |
WO2012080314A2 (en) | 2010-12-15 | 2012-06-21 | Ineos Europe Ag | Activating supports |
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US8497330B2 (en) * | 1997-12-08 | 2013-07-30 | Univation Technologies, Llc | Methods for polymerization using spray dried and slurried catalyst |
US20060293470A1 (en) * | 2005-06-28 | 2006-12-28 | Cao Phuong A | Polymerization process using spray-dried catalyst |
US6242545B1 (en) * | 1997-12-08 | 2001-06-05 | Univation Technologies | Polymerization catalyst systems comprising substituted hafinocenes |
CA2347410C (en) * | 2001-05-11 | 2009-09-08 | Nova Chemicals Corporation | Solution polymerization process catalyzed by a phosphinimine catalyst |
US7683140B2 (en) * | 2004-05-20 | 2010-03-23 | Univation Technologies, Llc | Method for determining temperature value indicative of resin stickiness from data generated by polymerization reaction monitoring |
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JP2010502813A (en) * | 2006-09-07 | 2010-01-28 | ユニベーション・テクノロジーズ・エルエルシー | Method for determining temperature values indicative of resin tack from data generated by polymerization reaction monitoring |
WO2008030294A1 (en) * | 2006-09-07 | 2008-03-13 | Univation Technologies, Llc | Methods for on-line determination of degree of resin stickiness using a model for depression of melt initiation temperature |
CA3039379A1 (en) * | 2019-04-08 | 2020-10-08 | Nova Chemicals Corporation | New phosphinimide catalysts for olefin polymerization |
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EP0881233A1 (en) * | 1997-05-30 | 1998-12-02 | Nova Chemicals (International) SA | High temperature solution polymerization process |
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- 1999-11-01 AT AT99952203T patent/ATE399800T1/en not_active IP Right Cessation
- 1999-11-01 DE DE69939026T patent/DE69939026D1/en not_active Expired - Lifetime
- 1999-11-01 EP EP99952203A patent/EP1135421B1/en not_active Expired - Lifetime
- 1999-11-01 AU AU64573/99A patent/AU6457399A/en not_active Abandoned
- 1999-11-15 US US09/439,767 patent/US6234950B1/en not_active Expired - Lifetime
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EP0881233A1 (en) * | 1997-05-30 | 1998-12-02 | Nova Chemicals (International) SA | High temperature solution polymerization process |
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EP1162214A1 (en) * | 2000-06-08 | 2001-12-12 | Nova Chemicals (International) S.A. | Process to prepare ethylene propylene elastomer |
US7547751B2 (en) | 2003-08-04 | 2009-06-16 | Dsm Ip Assets B.V. | Process for the preparation of a polyolefin |
WO2005014601A3 (en) * | 2003-08-04 | 2005-11-03 | Dsm Ip Assets Bv | Process for the preparation of a polyolefin |
WO2005014674A3 (en) * | 2003-08-04 | 2005-11-17 | Dsm Ip Assets Bv | Process for the preparation of a polyolefin |
WO2005014674A2 (en) * | 2003-08-04 | 2005-02-17 | Dsm Ip Assets B.V. | Process for the preparation of a polyolefin |
CN1860142B (en) * | 2003-08-04 | 2010-12-01 | 帝斯曼知识产权资产管理有限公司 | Process for the preparation of a polyolefin |
WO2006054048A1 (en) | 2004-11-18 | 2006-05-26 | Ineos Europe Limited | Supported polymerisation catalysts |
EP1731536A1 (en) | 2005-06-09 | 2006-12-13 | Innovene Manufacturing France SAS | Supported polymerisation catalysts |
WO2007075299A2 (en) * | 2005-12-16 | 2007-07-05 | Dow Global Technologies Inc. | Polydentate heteroatom ligand containing metal complexes, catalysts and methods of making and using the same |
WO2007075299A3 (en) * | 2005-12-16 | 2008-05-02 | Dow Global Technologies Inc | Polydentate heteroatom ligand containing metal complexes, catalysts and methods of making and using the same |
EP2359930A1 (en) * | 2005-12-16 | 2011-08-24 | Dow Global Technologies LLC | A polymer prepared in the presence of metal complexes bearing a polydentate heteroatom ligand |
WO2007137395A1 (en) * | 2006-05-30 | 2007-12-06 | Nova Chemicals (International) S.A. | Supported polymerization catalysts |
WO2012080314A2 (en) | 2010-12-15 | 2012-06-21 | Ineos Europe Ag | Activating supports |
Also Published As
Publication number | Publication date |
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DE69939026D1 (en) | 2008-08-14 |
EP1135421B1 (en) | 2008-07-02 |
AU6457399A (en) | 2000-06-19 |
US6234950B1 (en) | 2001-05-22 |
EP1135421A1 (en) | 2001-09-26 |
ATE399800T1 (en) | 2008-07-15 |
CA2254841C (en) | 2007-02-06 |
CA2254841A1 (en) | 2000-05-26 |
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