WO2002083751A1 - Olefin polymerization catalyst - Google Patents
Olefin polymerization catalyst Download PDFInfo
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- WO2002083751A1 WO2002083751A1 PCT/US2002/012680 US0212680W WO02083751A1 WO 2002083751 A1 WO2002083751 A1 WO 2002083751A1 US 0212680 W US0212680 W US 0212680W WO 02083751 A1 WO02083751 A1 WO 02083751A1
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- 0 Cc1c(C)c(*=C)c(*)c(*)c1* Chemical compound Cc1c(C)c(*=C)c(*)c(*)c1* 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/06—Cobalt compounds
- C07F15/065—Cobalt compounds without a metal-carbon linkage
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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
- C08F4/70—Iron group metals, platinum group metals or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/02—Iron compounds
- C07F15/025—Iron compounds without a metal-carbon linkage
-
- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/11—Compounds covalently bound to a solid support
Definitions
- This invention concerns an olefin polymerization catalyst which contains a transition metal complex of a selected tridentate ligand, a method for preparing such a catalyst, and an olefin polymerization process for utilizing such a catalyst.
- polyolefins are important items of commerce, and many such polymers are made using as part of the polymerization catalyst system a transition metal complex. Recently, there has been much interest in catalysts containing late transition metals, such as Fe, Co, Ni and Pd.
- catalysts containing late transition metals such as Fe, Co, Ni and Pd.
- One particular type of olefin polymerization catalyst contains what is believed to be a tridentate ligand which is a 2 , 6-pyridinedicarbox- aldehydebisimine or a 2 , 6-diacylpyridinebisimine or minor variation thereof, typically as an iron or cobalt complex.
- an important consideration is the overall cost of the polymerization catalyst system per unit weight of polyolefin produced. Another important consideration is the form of the polymer product obtained, that is whether it is obtained in an easy to use form such as relatively nondusting particles which flow well and preferably have a relatively high bulk density, and whether fouling of the polymerization reactor (s) occurs .
- the main cost of the polymerization catalyst is not the transition metal complex itself, but the cost of preparing the catalyst and/or costs of other ingredients needed for the catalyst system.
- the latter is particularly true for many of the so-called single site catalysts such as metallocenes and many late transition metal-containing catalysts where aluminoxanes , especially methylaluminoxane, have been found to give superior results but are very expensive compared to other alkylaluminum compounds, thereby increasing the total catalyst system cost per unit weight of polyolefin produced.
- transition metal complexes of a 2 , 6-pyridinedicarboxaldehydebisimine or a 2 , 6-diacylpyridinebisimine such as disclosed in the aforementioned incorporated references.
- Some exceptions have been noted, for example by modifying the surface of a support for a supported catalyst, see for instance WO 0020467, which is incorporated by reference herein for all purposes as if fully set forth.
- the modified support disclosed in this publication allows the use of alkylaluminum compounds other than aluminoxanes to achieve good polymerization results, modification of the support itself adds significantly to the overall polymerization catalyst cost per unit weight of polyolefin produced.
- This invention concerns, a process for the preparation of a supported polymerization catalyst component, comprising the steps of: (a) dissolving a transition metal complex of a 2 , 6-pyridinedicarboxaldehydebisimine or a 2,6- diacylpyridinebisimine in a solvent to form a solution; (b) contacting said solution with a support which is an unmodified silica or a silica-alumina for a sufficient amount of time to allow at least part of said metal complex to be adsorbed onto said support; and (c) optionally separating said solution and solvent from said support ,- provided that substantially no activator is present during steps (a) , (b) and (c) .
- Also included in this invention is a catalyst obtainable or obtained by the above process .
- This invention further includes a process for the polymerization of one or more polymerizable olefins, comprising the steps of:
- hydrocarbyl group is a univalent group containing only carbon and hydrogen.
- hydrocarbyls may be mentioned unsubstituted alkyls, cycloalkyls and aryls. If not otherwise stated, it is preferred that hydrocarbyl groups herein contain 1 to about 30 carbon atoms.
- substituted hydrocarbyl herein is meant a hydrocarbyl group that contains one or more (types of) substituents that do not substantially interfere with the operation of the polymerization catalyst system.
- Suitable substituents in some polymerizations may include some or all of halo, ester, keto (oxo) , amino, imino, carboxyl, phosphite, phosphonite, phosphine, phosphinite, thioether, amide, nitrile, and ether.
- Preferred substituents when present are halo, ester, amino, imino, carboxyl, phosphite, phosphonite, phosphine, phosphinite, thioether, and amide.
- substituted hydrocarbyl groups herein contain 1 to about 30 carbon atoms. Included in the meaning of "substituted” are chains or rings containing one or more heteroatoms, such as nitrogen, oxygen and/or sulfur, and the free valence of the substituted hydrocarbyl may be to the heteroatom. In a substituted hydrocarbyl, all of the hydrogens may be substituted, as in trifluoromethyl .
- (inert) functional group herein is meant a group other than hydrocarbyl or substituted hydrocarbyl that is, other than participating in “adsorption” (defined below) of the complex on the support, inert under the process conditions to which the compound containing the group is subjected.
- the functional groups also do not substantially interfere with any process described herein that the compound in which they are present may take part in. Examples of functional groups include halo (fluoro, chloro, bromo and iodo) , and ether such -OR 30 wherein R 30 is hydrocarbyl or substituted hydrocarbyl.
- the functional group may be near a transition metal atom (such as an iron atom)
- the functional group should not coordinate to the transition metal atom more strongly than the groups in those compounds which are shown as coordinating to the transition metal atom, that is they should not displace the desired coordinating groups.
- alkyl group and "substituted alkyl group” have their usual meaning (see above for substituted under substituted hydrocarbyl) . Unless otherwise stated, alkyl groups and substituted alkyl groups preferably have 1 to about 30 carbon atoms.
- aryl is meant a monovalent aromatic group in which the free valence is to the carbon atom of an aromatic ring.
- An aryl may have one or more aromatic rings which may be fused, connected by single bonds or other groups .
- substituted aryl is meant a monovalent aromatic group substituted as set forth in the above definition of “substituted hydrocarbyl” . Similar to an aryl, a substituted aryl may have one or more aromatic rings which may be fused, connected by single bonds or other groups; however, when the substituted aryl has a heteroaromatic ring, the free valence in the substituted aryl group can be to a heteroatom (such as nitrogen) of the heteroaromatic ring instead of a carbon .
- activator cocatalyst or a “catalyst activator” is meant one or more compounds that react with a transition metal compound to form a catalyst species that can polymerize the polymerizable olefin(s).
- Useful activators include alkylaluminum compounds, certain boron compounds, and other alkylating or hydriding compounds.
- the transition metal compound used in the first process, and in steps (a) , (b) and (c) of the second process will not by itself start a polymerization, but will require the use of one or more activators to make an active olefin polymerization catalyst.
- substantially no activator is present is meant that no activator is present other than, for example, at very low levels as might be typical for impurities in the various components.
- the intention is that no significant amounts of activated catalyst species are generated in the supportation process by the interaction of the transition metal complex with an activator - this activation should preferably occur at or close to the time the catalyst is used in a polymerization process.
- an “unmodified" support (silica or silica- alumina) is meant a support that does not contain (either bonded or simply on the surface) materials which are designed to bond or otherwise cause the transition metal complex to adhere to the support.
- materials include alkylaluminum compounds and other alkylating and hydriding compounds, Lewis acids (bound or unbound to the surface of the support) , and other similar compounds.
- the transition metal complex, and more preferably the tridentate ligand therein does not have bonded to it a group which will or may react with the support to covalently bond to that support.
- the ligand does not contain a hydroxyl (alcohol) group which reacts with the silica surface.
- alkylaluminum compound a compound which has at least one alkyl group bound directly to aluminum. Other groups such as, for example, alkoxide, hydride and halogen, may also be bound to aluminum atoms in the compound. Alkylaluminum compounds are activators .
- sica " or silica-alumina is meant a silica or a silica-alumina that may or may not have been dehydrated, as by heating. Preferably the material has been dehydrated to some extent, preferably by heating, before taking part in any of the processes described herein. These materials are well known in the art of polymer catalyst supports, and often, and preferably have high porosity and/or surface area. They often also have a small and/or controlled particle size .
- polymerization is meant, in its broadest context, to include dimerization, oligomerization and polymerization (both homopolymerization and copolymerization) .
- polymerization conditions conditions for causing olefin “polymerization” with catalysts using the same transition metal tridentate complexes, modified as described herein.
- the polymerization catalyst systems described herein may be used under the same conditions as previously reported for the same complexes.
- Such conditions may include temperature, pressure, suspending media, polymerization method such as gas phase, liquid phase, continuous, batch, and the like. Supported catalysts are particularly useful in liquid suspension polymerizations and gas phase polymerizations .
- adsorbed herein is merely meant that a first substance is “attracted” to a second substance so that so that the first substance "sticks” to the second substance (at least in part) even though for example the adsorbed first substance may be in the presence of a solvent for that first substance.
- the word “adsorbed” herein has no connotation as to why the first substance sticks to the second substance.
- relatively noncoordinating or “weakly coordinating” anions are meant those anions as are generally referred to in the art in this manner, and the coordinating ability of such anions is known and has been discussed in the literature, see for instance W. Beck., et al . , Chem. Rev. , vol. 88 p. 1405-1421 (1988), and S. H. Stares, Chem. Rev. , vol. 93, p. 927-942 (1993), both of which are hereby incorporated by reference herein for all purposes as if fully set forth.
- Such anions are those formed from the aluminum compounds in the immediately preceding paragraph and X", including R 9 3 A1X ⁇ , R 9 2 A1C1X ⁇ , R 9 A1C1 2 X-, and "R 9 AlOX”” , wherein R 9 is alkyl.
- a tridentate ligand is meant a ligand that is capable of being a tridentate ligand, that is it has three sites, often heteroatom sites, that can coordinate to a transition metal atom simultaneously. Preferably all three sites do coordinate to the transition metal .
- a "primary carbon group” herein is meant a group of the formula -CH 2 , wherein the free valence is to any other atom, and the bond represented by the solid line is to a ring atom of a substituted aryl to which the primary carbon group is attached.
- the free valence may be bonded to a hydrogen atom, a halogen atom, a carbon atom, an oxygen atom, a sulfur atom, etc.
- the free valence may be to hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group.
- Examples of primary carbon groups include -CH 3 ,
- both free bonds represented by the dashed lines are to an atom or atoms other than hydrogen.
- These atoms or groups may be the same or different.
- the free valences represented by the dashed lines may be hydrocarbyl, substituted hydrocarbyl or inert functional groups.
- tertiary carbon group a group of the formula
- the bond represented by the solid line is to a ring atom of a substituted aryl to which the tertiary carbon group is attached, and the three free bonds represented by the dashed lines are to an atom or atoms other than hydrogen.
- the bonds represented by the dashed lines are to hydrocarbyl, substituted hydrocarbyl or inert functional groups.
- Preferred 2 , 6 -pyridinedicarboxaldehydebisimines and 2 , 6 -diacylpyridinebisimine are compounds of the formula (I )
- R 1 , R 2 , R 3 , R 4 and R 5 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group, provided that any two of R 1 , R 2 and R 3 vicinal to one another, taken together may form a ring; and
- R 6 and R 7 are aryl, substituted aryl or a functional group.
- a transition metal complex of (I) will have the formula LMX m Y n wherein L is the 2,6- pyridinedicarboxal-dehydebisimine or a 2,6- diacylpyridinebisimine ligand, M is the transition metal, X is a monoanion (one negative charge) , Y is a relatively noncoordinating monoanion, and m+n is equal to the oxidation state of M. Typically if all of X are monodentate anions, then n is zero, and m is equal to the oxidation state of M. If for example one of X is a bidentate monoanion, then usually n is one (if m+n is 2) . Therefore m may be an integer of 1 or more, while n may be 0 or an integer of 1 or more, preferably n is 0 or 1.
- Monodentate monoanions include halide and carboxylate, while bidentate monoanions include acetylacetonate, allylic and benzylic monoanions.
- Relatively noncoordinating anions are defined above.
- X nor Y are a hydrocarbyl anion or hydride, typically to form an active polymerization (in the second process) at least X must be converted to a hydrocarbyl anion such as alkyl or hydride (other anions may also be active) . This is usually achieved with an activator (cocatalyst) which can, for example, alkylate the metal .
- alkylate herein is meant the cocatalyst reacts with LMX m Y n to alkylate the metal (for example to give LM (alkyl) m Y n ) , while optionally at the same time forming a relatively noncoordinating anion by abstracting one of the alkyl groups
- “Hydriding” is analogous to alkylating, except using a hydride anion instead of an alkyl anion.
- a second cocatalyst which is a neutral Lewis acid may be added to abstract the alkyl group and form a relatively noncoordinating anion. Note that this is just one scenario to form an active olefin polymerization catalyst that can be used, depending on the particular metal complex used and the cocatalyst (s) used.
- the activator is either (1) a neutral Lewis acid which is both (i) capable of abstracting an anion from said transition metal of said transition metal complex to form a weakly coordinating anion, and (ii) capable of alkylating or hydriding said transition metal; or (2) a combination of (i) a neutral- Lewis acid which is capable of abstracting an anion from said transition metal of said transition metal complex to form a weakly coordinating anion, and (ii) another compound which is capable of alkylating or hydriding said transition metal .
- the cocatalyst is an alkylating compound and a Lewis acid which can form a weakly coordinating anion.
- Useful alkylating compounds include alkylaluminum compounds (which can also be hydriding compounds if they contain hydrogen bound to aluminum) , alkylzinc compounds, and Grignard reagents.
- alkylaluminum compounds such as trialkylaluminum compounds including trimethylaluminum, triethylaluminum, tri-n- butylaluminum and tri-i-butylaluminum; alkylhaloaluminum compounds such as diethylaluminum chloride, ethylaluminum chloride and ethylaluminum sesquichloride; and (alkoxy) (alkyl) aluminum compounds such as ethoxydiethylaluminum.
- Aluminoxanes such as methylaluminoxane, may also be used, but because of their cost (even though they may be very effective otherwise) they are not preferred.
- R 1 , R 2 and R 3 are hydrogen; and/or
- R 1 and R 3 are hydrogen, and R 2 is trifluoromethyl ;
- R 4 and R 5 are each independently halogen, thioalkyl , hydrogen or alkyl containing 1 to 6 carbon atoms, more preferably R 4 and R 5 are each independently hydrogen or methyl . ,
- R 6 and R 7 are each independently a substituted aryl and, more preferably, a substituted phenyl . Still more preferably, R 6 is
- R 8 , R 12 , R 13 and R 17 are each independently hydrocarbyl, substituted hydrocarbyl or an inert functional group;
- R 9 , R 10 , R 11 , R 14 , R 15 and R 16 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group; and provided that any two of R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 and R 17 that are vicinal to one another, taken together may form a ring.
- R 9 , R 10 , R 11 , R 14 , R 15 and R 16 are each independently hydrogen, halogen, or an alkyl containing 1 to 6 carbon atoms, and more preferably that each of these is hydrogen; and/or
- R 10 and R 15 are methyl, phenyl or substituted phenyl (such as an alkyl substituted phenyl) ; and/or R 8 , R 12 , R 13 and R 17 are each independently halogen, phenyl, substituted phenyl or an alkyl containing 1 to 6 carbon atoms, more preferably that each is independently phenyl, substituted phenyl (e.g., an alkyl substituted phenyl such as p-t-butylphenyl) or an alkyl containing 1-6 carbon atoms (such as i-propyl or t-butyl) (although it is not preferred when both R 8 and R 12 , or both R 13 and R 17 , are t-butyl in the same compound) .
- R 8 , R 12 , R 13 and R 17 are each independently halogen, phenyl, substituted phenyl or an alkyl containing 1 to 6 carbon atoms, more preferably that each
- R 6 and R 7 are, respectively, (VI) and (VII) , and:
- R 9 , R 11 , R 14 and R 16 are hydrogen, and R 8 , R 10 , R 1 , R 13 , R 15 and R 17 are methyl; R 9 , R 10 , R 11 , R 14 , R 15 and R 16 are hydrogen, R 8 and
- R 13 are chloro, and R 12 and R 17 are methyl
- R 9 , R 10 , R 11 , R 14 , Ri5 # R16 an R i7 are hydrogen, and R 8 and R 13 are phenyl;
- R 9 , R 10 , R 11 , R 14 , Ri5 # 16 anc j R1 7 are hydrogen, and R 8 and R 13 are p-t-butylphenyl ;
- R 9 , R 10 , R 11 , R 14 , R i s and R 16 are hydrogen, and R 8 , R 12 , R 13 and R 17 are phenyl;
- R 9 , R 10 , R 11 , R 14 , R 15 and R 16 are hydrogen, and R 8 and R 13 are p-t-butylphenyl, and R 12 and R 17 are halo;
- R 9 , R 10 , R 11 , R 14 , R 15 and R 16 are hydrogen, and R 8 , R 12 , R 13 and R 17 are i-propyl;
- R 9 , R 10 , R 11 , R 12 , R 14 , R 15 , R 16 and R 17 are hydrogen, and R 8 and R 13 are t-butyl.
- R 6 and R 7 are each independently a substituted 1-pyrroyl. More preferably in this instance, R 6 and R 7 are, respectively
- R 18 and R 21 correspond to the definitions of, and preferences for, R 8 and R 12 in (VI) ;
- R 22 and R 25 correspond to the definitions of, and preferences for, R 13 and R 17 in (VII) ;
- R 19 and R 20 correspond to the definitions of, and preferences for, R 9 and R 11 in (VI) ;
- R 23 and R 24 correspond to the definitions of, and preferences for, R 14 and R 16 in (VII) .
- R 6 and R 7 are preferably each independently a substituted aryl having a first ring atom bound to the imino nitrogen, provided that: in R 6 , a second ring atom adjacent to said first ring atom is bound to a halogen, a primary carbon group, a secondary carbon group or a tertiary carbon group; and further provided that in R 6 , when said second ring atom is bound to a halogen or a primary carbon group, none, one or two of the other ring atoms in R 6 and R 7 adjacent to said first ring atom are bound to a halogen or a primary carbon group, with the remainder of the ring atoms adjacent to said first ring atom being bound to a hydrogen atom; or in R 6 , when said second ring atom is bound to a
- the atoms shown in the 1-position in the rings in (II) and (III) are the first ring atoms bound to an imino carbon atom (other groups which may be substituted on the aryl groups are not shown) .
- Ring atoms adjacent to the first ring atoms are shown, for example, in (IV) and (V) , where the open valencies to these adjacent atoms are shown by dashed lines (the 2 , 6-positions in (IV) and the 2 , 5-positions in (V)).
- R 5 is
- R 8 is a halogen, a primary carbon group, a secondary carbon group or a tertiary carbon group; and R 9 , R 10 , R 11 , R 14 , R 15 , R 16 and R 17 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group; provided that : when R 8 is a halogen or primary carbon group none, one or two of R 12 , R 13 and R 17 are a halogen or a primary carbon group, with the remainder of R 12 , R 13 and R 17 being hydrogen; or when R 8 is a secondary carbon group, none or one of R 12 , R 13 and R 17 is a halogen, a primary carbon group or a secondary carbon group, with the remainder of R 12 , R 13 and R 17 being hydrogen; or when R 8 is a tertiary carbon group, none or one of R 12 , R 13 and R 17 is tertiary carbon group, with the remainder of R 12 , R 13 and R 17 being hydrogen; and further
- R 8 corresponds to the second ring atom adjacent to the first ring atom bound to the imino nitrogen
- R 12 , R 13 and R 17 correspond to the other ring atoms adjacent to the first ring atom.
- R 8 is a primary carbon group, R 13 is a primary carbon group, and R 12 and R 17 are hydrogen; or if R 8 is a secondary carbon group, R 13 is a primary carbon group or a secondary carbon group, more preferably a secondary carbon group, and R 12 and R 17 are hydrogen; or if R 8 is a tertiary carbon group (more preferably a trihalo tertiary carbon group such as a trihalomethyl) , R 13 is a tertiary carbon group (more preferably a trihalotertiary group such as a trihalomethyl) , and R 12 and R 17 are hydrogen; or if R 8 is a halogen, R 13 is a halogen, and R 12 and R 17 are hydrogen .
- R 8 is a halogen, R 13 is a halogen, and R 12 and R 17 are hydrogen.
- R 1 , R 2 and R 3 are hydrogen; and/or R 4 and R 5 are methyl. It is further preferred that:
- R 9 , R 10 , R 11 , R 12 , R 14 , R 15 , R 1S and R 17 are all hydrogen; R 13 is methyl; and R 8 is a primary carbon group, more preferably methyl; or
- R 9 , R 10 , R 11 , R 12 , R 14 , R 15 , R 16 and R 17 are all hydrogen;
- R 13 is ethyl; and
- R 8 is a primary carbon group, more preferably ethyl; or
- R 9 , R 10 , R ⁇ ⁇ , R 12 , R 14 , R 15 , R 16 and R 17 are all hydrogen;
- R 13 is isopropyl; and
- R 8 is a primary carbon group, more preferably isopropyl; or
- R 9 , R 10 , R 11 , R 12 , R 14 , R 15 , R 16 and R 17 are all hydrogen;
- R 13 is n-propyl; and
- R 8 is a primary carbon group, more preferably n-propyl; or
- R 9 , R 10 , R 11 , R 12 , R 14 , R 15 , R 16 and R 17 are all hydrogen;
- R 13 is chloro; and
- R 9 , R 10 , R 11 , R 12 , R 14 , R 15 , R 15 and R 17 are all hydrogen;
- R 13 is trihalomethyl, more preferably trifluoromethyl ;
- R 8 is a trihalomethyl, more preferably trifluoromethyl .
- R 6 and R 7 are, respectively
- R1 8 corresponds to the definitions of, and preferences for, R 8 (Via) ;
- R 19 , R 20 and R 21 correspond respectively to the definitions of, and preferences for, R 9 , R 10 and R 12 in (Via) ;
- R 22 , R 23 , R 24 and R 25 correspond respectively to the definitions of, and preferences for, R 13 , R 14 , R 16 and R 17 in (Vila) .
- R 18 corresponds to the second ring atom adjacent to the first ring atom bound to the imino nitrogen
- R 21 , R 22 and R 25 correspond to the other ring atoms adjacent to the first ring atom.
- Any transition metal which forms an active polymerization catalyst with (I) may be used.
- suitable transition metal may be mentioned those found in Groups 3-12 of the Periodic Table (IUPAC) .
- Groups 8-10 transition metals Preferred are the Groups 8-10 transition metals, more preferred are the Groups 8 and 9 transition metals, particularly preferred are Fe and Co, and Fe is especially preferred.
- Compound (I) and its transition metal complexes may be prepared by the variety of methods disclosed in the previously incorporated references, as well as by the procedures disclosed, for example, in WO9950273 and WO00/08034, both of which are also incorporated by reference herein for all purposes as if fully set forth.
- Preferred is ethylene alone to give an ethylene homopolymer (or in the case of oligomerization, a series of alpha-olefins having an even number of carbon atoms) , or a combination of ethylene with one or more alpha-olefins (such as propylene, 1-hexene, 1-octene, 1-decene and/or 1-dodecene) to give an ethylene copolymer.
- alpha-olefins such as propylene, 1-hexene, 1-octene, 1-decene and/or 1-dodecene
- the transition metal complex is preferably initially dissolved in a solvent. It is preferred that the solvent not substantially decompose the complex, although the solvent may additionally complex with the metal complex.
- the solvent is an aprotic solvent, and not a protic solvent such as water, an alcohol or a carboxylic acid.
- the complex should have a solubility of at least about 0.0001 g per 100 ml of solvent, more preferably at least about 0.01 g per 100 ml of solvent.
- the solvent/complex combination is then brought into contact with the silica or silica- alumina (collectively, the support) , preferably under agitation, at which point the complex becomes at least partially adsorbed on the support.
- Adsorption may be relatively fast, particularly if the complex has a relatively high solubility in the solvent. In this case the contacting may be done for less than 1 hour. If the complex has a low solubility in the solvent (for example not all the transition metal may dissolve at once) , more time (perhaps about 10 hours or more) may be needed to dissolve the complex and have it adsorbed onto the support. Mild agitation to ensure mixing of the support with the solution is preferred.
- the complex is colored, and one can judge the progress of the adsorption of the complex onto the support visually.
- the transition metal complex will be adsorbed onto the support. It is preferable that at least about 50%, more preferably at least about 80% of the complex present is adsorbed. Unadsorbed complex may be recycled to be adsorbed onto more support .
- the solution and/or solvent may be separated from the support (and adsorbed complex) by any standard method, for example filtering off the support from the solvent (and any still complex dissolved therein) , or centrifuging the mixture and decanting the supernatant away from the solid, the solvent removed by evaporation, for example under vacuum.
- the solution is separated from the support as a liquid, as by filtration or centrifuging as described above.
- the support and adsorbed complex may be washed with solvent to remove any unadsorbed complex (some adsorbed complex may also be removed at this point) , and/or the support and adsorbed complex may be dried, as by vaporization under vacuum.
- the majority, preferably >90%, of the solvent should not be separated from the supported complex by vaporizing the solvent (in other words a physical separation of the solid support and the liquid solvent (solution) should be carried out) .
- the supported catalyst may also be used in a polymerization process without separating it from the solvent/solution, but it is preferred that it is separated from the solvent/solution before use in a polymerization.
- the ratio of transition metal complex to support in step (a) will be such that the final amount of transition metal on the supported catalyst (measured as transition metal) is about 0.01 to about 5.0, more preferably about 0.02 to about 1.0 weight percent of the total weight of the supported catalyst component.
- the supported catalyst component made by this procedure is stable at room temperature for extended periods. Also this catalyst need not contain materials that are considered flammable or pyrophoric, and it may be shipped without extraordinary precautions by relatively cheap means.
- This supported catalyst component can be used as part of a catalyst system for the polymerization of olefins, as disclosed in the various previously incorporated publications.
- a preferred molar ratio of the alkylating or hydriding cocatalyst (preferably an alkylaluminum compound or a dialkylzinc compound) to "moles" of transition metal is about 1 to about 2000, more preferably about 5 to about 1000, and especially preferably about 30 to about 500 (any of these minimum and maximum ratios may be paired with each other) .
- this cocatalyst is also simultaneously used as a scavenger, that is a chemical compound which removes impurities in the polymerization system which are deleterious to the polymerization process.
- the ratio of this cocatalyst to transition metal will also depend to some extent on the level of deleterious impurities in the second process.
- the molar ratio of this Lewis acid to transition metal is typically about 1 to about 5.
- any cocatalysts used in the polymerization process contact the supported catalyst made in the first process in the presence of olefin monomer (s), or the contacting with the cocatalysts be carried out shortly before (less than 6 hours, more preferably less than 1 hour, and especially preferably less than 5 minutes) additionally contacting with the olefin monomer (s) .
- the cocatalyst (s) and supported catalyst be contacted together in the polymerization vessel itself, or in a process line leading to the polymerization vessel. If the polymerization process takes place in liquid phase, for example a suspension polymerization, the supported catalyst and any cocatalyst (s) can be added to the suspending liquid medium.
- the particulate supported catalyst may be fluidized by the gas and the cocatalyst (s) such as a trialkylaluminum compound may be added as a vapor.
- the cocatalyst such as a trialkylaluminum compound
- a relatively volatile alkylaluminum compound such as trimethylaluminum is often favored.
- More than one transition metal compound may be used as the polymerization catalyst, one or both may be supported on the same support or a different support.
- Typical polymerization conditions may be used, for example, hydrogen may be used to control the molecular weight of the polyolefin. See, for example, previously incorporated WO 9946302, as well as WO 9962963 which is also incorporated by reference herein for all purposes as if fully set forth.
- the transition metal complex of the tridentate ligand oligomerizes ethylene to relatively pure ⁇ - olefins .
- oligomerizations see, for example, previously incorporated US 6063881, US 6103946, WO 0055216 and WO 0073249, as well as WO 0076659 which is also incorporated by reference for all purposes as if fully set forth.
- a' second transition metal compound which is capable of copolymerizing ethylene and ⁇ -olefins is also present, a branched polyethylene will be obtained. See, for example, previously incorporated WO 9950318 and WO 0055216.
- the second transition metal compound is on the same support as is used in the first process, and the oligomerization and polymerization catalysts may be placed on the support simultaneously (as in the first process, with the additional polymerization catalyst also present) .
- the morphology of the silica particles used as the support is often replicated in the polymer particles (including silica) obtained.
- the product of many of the Examples below show such replication.
- the replication of the silica support morphology is believed to show a uniform deposition of the catalyst species in the absence of any deposited activating aluminum alkyl compound, such as methylaluminoxane .
- EXAMPLE 2 1 was recrystallized from CH 2 C1 2 . 1 (7.0 mg) was dissolved in anhydrous CH 2 C1 2 (7 ml) and silica alumina [0.5g, Grace M513-1.10 dehydrated at 200°C (flowing N 2 ) ] was added. The resulting deep blue mixture was agitated for 60 min. The resulting solid was then filtered from the colorless filtrate, washed with CH 2 C1 2 and dried. Yield 0.5 g light blue/grey solid.
- EXAMPLE 3 1 was recrystallized from CH 2 C1 2 . 1 (7.0 mg) was dissolved in anhydrous CH 2 C1 2 (7 ml) and silica alumina [0.5g, Grace M513-1.10 dehydrated at 500°C (flowing N 2 )] was added. The resulting deep blue mixture was agitated for 60 min. The resulting solid was then filtered from the colorless filtrate, washed with CH 2 C1 2 and dried. Yield 0.5 g light orange solid.
- EXAMPLE 4 1 was recrystallized from CH 2 C1 2 . 1 (4.0 mg) was dissolved in anhydrous toluene (15 ml) and silica (0.25 g, Grace XPO-2402 dehydrated 948 silica) was added. The resulting mixture was agitated overnight. The resulting solid was then filtered from the almost colorless filtrate, washed with toluene and pentane and dried. Yield 0.5 g light blue solid.
- EXAMPLE 5
- THF was removed (product is not completely soluble in THF) , and the product suspended in toluene and filtered through Celite®. The solvent was removed from the dark red solution, pentane added to give a red precipitate which was filtered, rinsed and dried under vacuum to give' 2.
- EXAMPLE 8 In a dry box, a stainless cylinder (25 to 40 ml volume) were charged with the product of Example 1 (75.8 mg) and another cylinder with 10 ml of a solution of triisobutylaluminum (1M solution in hexane, Aldrich) . The cylinders were connected to the autoclave reactor ports under nitrogen purge of the connections. Cylinder pressurization lines were also connected under purge .
- Isobutane (1200 g, Matheson C.P. grade) was transferred into a cooled autoclave (-30°C) by pressure difference. Once the transfer was completed, the autoclave (Autoclave Engineers, agitated, 1-gal, 3.8 L) was heated to 20°C and stirred at 1000 rpm. The solvent was saturated with hydrogen at a pressure of 0.36 MPa (total pressure, including hydrogen) . After saturation, the reactor was heated to 80°C and pressurized with ethylene to 1.4 MPa. The triisobutylaluminum solution was pushed into the reactor with ethylene followed by the catalyst from Example 1, also pushed with ethylene.
- the final reactor pressure was 2.41 MPa and the ethylene feed was switched from the feed vessels to the side port in the autoclave.
- the reaction was run for 3 h.
- the reactor was vented slowly, followed by a nitrogen purge prior to opening of the reactor.
- the polymer was dried overnight.
- the polymer yield was 353 g, resulting in a catalyst efficiency of 4.65 kg PE/g catalyst (including support), or a polymerization rate of 1.55 kg PE/g catalyst -h or 1109 kg PE/g Fe-h.
- Example 8 Following the same procedure as in Example 8, but with 5 ml of triisobutylaluminum solution and 75.5 mg of supported catalyst from Example 1, the polymer yield was 316 g, resulting in a catalyst efficiency of 4.18 kg PE/g Catalyst, or a polymerization rate of 1.40 kg PE/g catalyst-h or 997 kg PE/g Fe-h.
- Example 4 Following the same procedure as in Example 8, but with 10 ml of triisobutylaluminum solution and 75.4 mg of the supported catalyst of Example 4, the polymer yield was 374 g, resulting in a catalyst efficiency of 4.96 kg PE/g catalyst, or a polymerization rate of 1.65 kg PE/g catalyst-h or 1181 kg PE/g Fe-h.
- EXAMPLE 14 Following the same procedure as in Example 8, but with 5 ml of triisobutylaluminum solution and 79.8 mg of the supported catalyst of Example 3, the polymer yield was 51 g, resulting in a catalyst efficiency of 0.64 kg PE/g catalyst, or a polymerization rate of 0.21 kg PE/g catalyst-h or 152 kg PE/g Fe-h.
- EXAMPLE 15 1 (7.0 mg) was weighted into a scintillation vial and dissolved in about 10 ml of toluene, and 0.5 g of silica gel (Grace Davidson 948) dehydrated to 0.76 mmol OH/g was added to the vial . The vial was shaken for 30 min. The mixture was filtered through a course glass frit and the solids were dried overnight in vacuum at room temperature .
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Abstract
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Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
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MXPA03009477A MXPA03009477A (en) | 2001-04-17 | 2002-04-16 | Olefin polymerization catalyst. |
CA002441415A CA2441415A1 (en) | 2001-04-17 | 2002-04-16 | Olefin polymerization catalyst |
BR0208868-1A BR0208868A (en) | 2001-04-17 | 2002-04-16 | Process for the preparation of catalyst component, catalyst component and polymerization process |
EP02736597A EP1379560A1 (en) | 2001-04-17 | 2002-04-16 | Olefin polymerization catalyst |
JP2002582100A JP2004528446A (en) | 2001-04-17 | 2002-04-16 | Olefin polymerization catalyst |
KR10-2003-7013543A KR20030090751A (en) | 2001-04-17 | 2002-04-16 | Olefin Polymerization Catalyst |
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US28428301P | 2001-04-17 | 2001-04-17 | |
US60/284,283 | 2001-04-17 | ||
US28555401P | 2001-04-20 | 2001-04-20 | |
US60/285,554 | 2001-04-20 |
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PCT/US2002/012680 WO2002083751A1 (en) | 2001-04-17 | 2002-04-16 | Olefin polymerization catalyst |
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EP (1) | EP1379560A1 (en) |
JP (1) | JP2004528446A (en) |
KR (1) | KR20030090751A (en) |
CN (1) | CN1541229A (en) |
BR (1) | BR0208868A (en) |
CA (1) | CA2441415A1 (en) |
MX (1) | MXPA03009477A (en) |
WO (1) | WO2002083751A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2006094302A1 (en) * | 2005-03-04 | 2006-09-08 | E.I. Dupont De Nemours And Company | Supported olefin polymerization catalysts |
US7442819B2 (en) | 2004-07-09 | 2008-10-28 | E. I. Du Pont De Nemours And Company | Catalysts for olefin polymerization or oligomerization |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1997048736A1 (en) * | 1996-06-17 | 1997-12-24 | Exxon Chemical Patents Inc. | Supported late transition metal catalyst systems |
WO1998027124A1 (en) * | 1996-12-17 | 1998-06-25 | E.I. Du Pont De Nemours And Company | Polymerization of ethylene with specific iron or cobalt complexes, novel pyridinebis(imines) and novel complexes of pyridinebis(imines) with iron and cobalt |
WO2001023444A1 (en) * | 1999-09-29 | 2001-04-05 | E.I. Du Pont De Nemours And Company | Polymerization of olefins with bimetallic polymerisation catalyst system |
-
2002
- 2002-04-16 CA CA002441415A patent/CA2441415A1/en not_active Abandoned
- 2002-04-16 JP JP2002582100A patent/JP2004528446A/en active Pending
- 2002-04-16 EP EP02736597A patent/EP1379560A1/en not_active Withdrawn
- 2002-04-16 KR KR10-2003-7013543A patent/KR20030090751A/en not_active Application Discontinuation
- 2002-04-16 BR BR0208868-1A patent/BR0208868A/en not_active IP Right Cessation
- 2002-04-16 CN CNA028084799A patent/CN1541229A/en active Pending
- 2002-04-16 WO PCT/US2002/012680 patent/WO2002083751A1/en not_active Application Discontinuation
- 2002-04-16 MX MXPA03009477A patent/MXPA03009477A/en not_active Application Discontinuation
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1997048736A1 (en) * | 1996-06-17 | 1997-12-24 | Exxon Chemical Patents Inc. | Supported late transition metal catalyst systems |
WO1998027124A1 (en) * | 1996-12-17 | 1998-06-25 | E.I. Du Pont De Nemours And Company | Polymerization of ethylene with specific iron or cobalt complexes, novel pyridinebis(imines) and novel complexes of pyridinebis(imines) with iron and cobalt |
US5955555A (en) * | 1996-12-17 | 1999-09-21 | E.I. Du Pont De Nemours And Company | Polymerization of ethylene |
WO2001023444A1 (en) * | 1999-09-29 | 2001-04-05 | E.I. Du Pont De Nemours And Company | Polymerization of olefins with bimetallic polymerisation catalyst system |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7442819B2 (en) | 2004-07-09 | 2008-10-28 | E. I. Du Pont De Nemours And Company | Catalysts for olefin polymerization or oligomerization |
US7683149B2 (en) | 2004-07-09 | 2010-03-23 | E. I. Du Pont De Nemours And Company | Catalysts for olefin polymerization or oligomerization |
WO2006094302A1 (en) * | 2005-03-04 | 2006-09-08 | E.I. Dupont De Nemours And Company | Supported olefin polymerization catalysts |
Also Published As
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EP1379560A1 (en) | 2004-01-14 |
MXPA03009477A (en) | 2004-12-06 |
CA2441415A1 (en) | 2002-10-24 |
JP2004528446A (en) | 2004-09-16 |
KR20030090751A (en) | 2003-11-28 |
BR0208868A (en) | 2004-04-27 |
CN1541229A (en) | 2004-10-27 |
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