[go: up one dir, main page]

WO2001053361A1 - Siloxy-substituted monocyclopentadienyl ligated constrained geometry olefin polymerisation catalysts - Google Patents

Siloxy-substituted monocyclopentadienyl ligated constrained geometry olefin polymerisation catalysts Download PDF

Info

Publication number
WO2001053361A1
WO2001053361A1 PCT/GB2001/000203 GB0100203W WO0153361A1 WO 2001053361 A1 WO2001053361 A1 WO 2001053361A1 GB 0100203 W GB0100203 W GB 0100203W WO 0153361 A1 WO0153361 A1 WO 0153361A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
compound
ring
transition metal
metallocene
Prior art date
Application number
PCT/GB2001/000203
Other languages
French (fr)
Inventor
Ove Andell
Janne Maaranen
Lasse Ketola
Original Assignee
Borealis Technology Oy
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
Application filed by Borealis Technology Oy filed Critical Borealis Technology Oy
Priority to AU2001228629A priority Critical patent/AU2001228629A1/en
Publication of WO2001053361A1 publication Critical patent/WO2001053361A1/en

Links

Classifications

    • 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
    • C07F17/00—Metallocenes
    • 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
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • 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

Definitions

  • This invention relates to catalysts for olefin polymerisation, in particular to catalyst compounds containing metals ⁇ - and ⁇ -bonded by siloxycyclopentadienyl ligands, and their use in olefin polymerisation. 10
  • metals is here meant an ⁇ -ligand metal complex, e.g. an "open sandwich” or “half sandwich” compound in which the metal is complexed by a single ⁇ - ligand, a “sandwich” compound in which the metal is complexed by two or more ⁇ -ligands, a "handcuff"
  • Alumoxanes are compounds with alternating aluminium and oxygen atoms generally compounds of formula A or B
  • each R which may be the same or different, is a C ⁇ o alkyl group, and p is an integer having a value between 0 and 40) .
  • These compounds may be prepared by 35 reaction of an aluminium alkyl with water.
  • the production and use of alumoxanes is described in the patent literature, especially the patent applications of Texas Alkyls, Albemarle, Ethyl, Phillips, Akzo Nobel, Exxon, Idemitsu Kosan, Witco, BASF and Mitsui.
  • Methyl alumoxane (MAO) and butyl alumoxanes e.g. hexaisobutylalumoxane and tetraisobutylalumoxane are preferred for use according to the present invention.
  • metallocenes in which the metal is ⁇ -liganded by a siloxy-, homo or heterocyclic cyclopentadienyl group i.e. a cyclic ⁇ 5 -ligand substituted by a siloxy group but not carrying a fused ring, have surprisingly high activity with non- MAO alumoxanes .
  • the invention provides a metallocene procatalyst compound comprising a group 3 to 7 transition metal ⁇ - and ⁇ -liganded by a siloxy substituted, monocyclic, homo- or heterocyclic cyclopentadienyl group.
  • a group 3 (etc) metal is meant a metal in group 3 of the Periodic Table of the Elements, namely Sc, Y, etc.
  • the invention provides an olefin polymerisation catalyst system comprising or produced by reaction of (i) a metallocene procatalyst compound comprising a group 3 to 7 transition metal ⁇ - and ⁇ -liganded by a siloxy substituted, monocyclic, homo- or heterocyclic cyclopentadienyl group and (ii) a co-catalyst, eg an aluminium alkyl compound, in particular an alumoxane, especially an aluminium alkyl compound comprising alkyl groups containing at least two carbon atoms .
  • a metallocene procatalyst compound comprising a group 3 to 7 transition metal ⁇ - and ⁇ -liganded by a siloxy substituted, monocyclic, homo- or heterocyclic cyclopentadienyl group
  • a co-catalyst eg an aluminium alkyl compound, in particular an alumoxane, especially an aluminium alkyl
  • the invention provides a process for olefin polymerisation comprising polymerising an olefin in the presence of a metallocene compound comprising a group 3 to 7 transition metal ⁇ - and ⁇ -liganded by a siloxy substituted, monocyclic, homo- or heterocyclic cyclopentadienyl group.
  • the invention provides a process for the preparation of a metallocene procatalyst, said process comprising metallating with a group 3 to 7 transition metal a ligand comprising a monocyclic, homo- or heterocyclic cyclopentadienyl group substituted on the ⁇ -ring by a siloxy group and by a group capable /of ⁇ -bonding said metal .
  • the invention provides the use of a metallocene compound comprising a group 3 to 7 transition metal ⁇ - and ⁇ -liganded by a siloxy substituted, monocyclic, homo- or heterocyclic cyclopentadienyl group in olefin polymerization, especially ethylene or propylene, more especially ethylene, polymerisation or copolymerisation.
  • the invention provides an olefin polymer produced by a polymerisation catalysed by a metallocene compound comprising a group 3 to 7 transition metal ⁇ - and ⁇ -liganded by a siloxy substituted, monocyclic, homo- or heterocyclic cyclopentadienyl group.
  • ⁇ 5 ring of the cyclopentadienyl group is not fused to another ring, ie it cannot be a part of an indenyl or fluorenyl multi- ring structure.
  • the ⁇ 5 ring however may be substituted by cyclic groups or cyclic group containing substituents and the metal may be liganded by other ⁇ -ligands which are acyclic or multicyclic.
  • the ⁇ 5 -ligand with which the group 3 to 7 metal is complexed typically is a compound of formula IV
  • each R' which may be the same or different is a R + , OR + , SR + , NR + 2 or PR + 2 group where each R + is a C x _ 16 hydrocarbyl group, a tri-C,.
  • R' being a C 1 _ 12 hydrocarbyl group, eg a C 2 _ 8 alkyl or alkenyl group;
  • each R which may be the same or different is a ring substituent which does not form a bond to a metal ⁇ - bonded by the C 2 XYT ring and is other than a ring fused to the C 2 XYT ring (eg a R + , OR + , SR + , NR + 2 or PR + 2 group where each R + is a hydrocarbylsilyl group or a tri-C 1 _ a hydrocarbylsiloxy group or two R + groups together form a 3 to 6 atom bridge, preferably a hydrocarbyl bridge) or is an ⁇ - ligand linked to the C 2 XYT ring by a 1 to 3 atom bridge, and optionally substituted, eg by R + , OR + , SR + , NR + 2 or PR + 2 groups;
  • the ⁇ -bonding moiety R" ' is a divalent moiety bound to the cyclopentadienyl ring by a ⁇ -bond and capable of binding to a transition metal M via a ⁇ -bond, preferably via a M-heteroatom bond.
  • R" ' preferably comprises boron or a group 14 atom (eg C, Si or Ge) and a N, 0, S or P atom.
  • R" ' comprises a group R a R b with R a attached to the cyclopentadienyl ring and R D being capable of bonding to the metal M, where R a provides a 1 to 3 atom bridge of group 14 atoms, eg a group SiR c 2 , CR° 2 , , CR 2 SlR 2 , CR 2 Sl 2 CR 2 , SiR c 2 CR c 2 SiR c 2 , CR c 2 CR c 2 SiR c 2 , CR C 2 CR C 2 CR C 2 or GeR c 2 , R b is NR C , 0, S or PR 0 , and R c is hydrogen, hydrocarbyl, hydrocarbyloxy, silyl or halohydrocarbyl or two R c groups together form a homo- or heterocyclic ring, each R° containing up /to 20 non-hydrogen atoms.
  • R a provides a 1 to
  • R" ' groups include -Si(CH 3 ) 2 NR d groups where R d is a C__ ⁇ 12 hydrocarbyl group, eg
  • the group 3 to 7 transition metal may be ⁇ -liganded by one or two further ⁇ ligands. These may be cyclic or acyclic and may carry cyclic groups fused to an ⁇ 5 or ⁇ 4 cyclic or acyclic structure and may be bridged bis- ⁇ ("handcuff") ligands or bridged ⁇ - ⁇ ("scorpion") ligands.
  • such an ⁇ 5 or ⁇ 4 ligand group may be a homo- or heterocyclic cyclopentadienyl, indenyl or fluorenyl group, or an acyclic ⁇ 5 C 5 , ⁇ 5 -C 3 N 2 or ⁇ 4 C 2 N 2 group optionally carrying cyclic groups fused to the ⁇ 5 or ⁇ 4 skeleton.
  • Such further ⁇ ligands may optionally be substituted, eg by groups R".
  • Such further ⁇ -ligands include cyclopentadienyl, indenyl and fluorenyl ligands, especially siloxy substituted (eg R' 3 SiO-substituted) cyclopentadienyl or indenyl ligands.
  • a ⁇ -ligand moiety is meant a group bonded to the metal at one or more places via a single atom, eg a hydrogen, halogen, silicon, carbon, oxygen, sulphur or nitrogen atom.
  • metallocene pro catalyst of the invention may conveniently be a compound of formula V
  • q is 1, 2 or 3, generally being 1 when m is 1 ; M is a group 3 to 7 transition metal
  • L is a further/ ⁇ -ligand (eg as discussed above) ; r is zero, 1 or 2;
  • Z is a ⁇ -ligand (eg as discussed above) ; and s is zero or a positive integer having a value of up to 3 depending on the values of m, q and r and the oxidation state of metal M.
  • the metal M in the metallocene procatalysts of the invention is a group 3 to 7 transition metal, preferably a group 4 to 6 transition metal, eg a metal selected from Ti, Zr, Hf, V, Nb, Ta, Cr, Mo and W.
  • the metal is preferably Cr, Ti, Zr or Hf, particularly Cr if M is ⁇ -liganded by a single ⁇ -ligand group or Ti, Zr or Hf if M is ⁇ -liganded by one or more ⁇ -ligand groups
  • the siloxycyclopentadienyl ⁇ -ligand is especially preferably a ligand of formula VI
  • R' is as defined above; Y' is P, B, CH or C-CH 3 ; R ⁇ is H or CH 3 ; and R is a group R a R as defined above
  • R' 3 SiO groups in the metallocene procatalysts of the invention include
  • Typical examples of the metallocene procatalysts of the invention thus include:
  • siloxy- ⁇ -ligands examples include:
  • EP-B-129368 (Exxon) and EP-B-206794 (Exxon) . These include
  • cyclopentadienyl indenyl , fluorenyl , octahydrofluorenyl , methylcyclopentadienyl , 1 , 2-dimethylcyclopentadienyl , pentamethylcyclopentadienyl , pentyl-cyclopentadienyl , 2-dimethyl, tertbutylsiloxy-inden-1-yl , n-butylcyclopentadienyl , 1 , 3-dimethylcyclopentadienyl , 4 , 7-dimethylindenyl , 1, -ethyl-2-methylcyclopentadienyl, tetrahydroindenyl, and methoxycyclopentadienyl .
  • ⁇ -ligands examples include:
  • halogenides e/.g. chloride and fluoride
  • hydroge triC 1 _ 12 hydrocarbyl-silyl or -siloxy(e.g. trimethylsilyl)
  • tric e s hydrocarbylphosphimido e.g. triisopropylphosphimido
  • c ⁇ -i 2 hydrocarbyl or hydrocarbyloxy e.g. methyl, ethyl, phenyl, benzyl and methoxy
  • diCi-, 6 hydrocarbylamido e.g. dimethylamido and diethylamido
  • ring membered heterocyclyl eg pyrrolyl, furanyl and pyrrolidinyl
  • the siloxy cyclopentadienyl ⁇ - ⁇ -ligands used according to the invention may be prepared by reaction of a corresponding siloxycyclopentadiene with an organolithium compound, eg methyllithium or butyllithium.
  • the ligand can be metallated conventionally, eg by reaction with a halide of the metal M, preferably in an organic solvent, eg a hydrocarbon or a hydrocarbon/ether mixture .
  • the ⁇ - bonding group R" ' may be introduced by reacting a corresponding siloxycyclopentadiene with a compound such as a hydrocarbylaminosilyl halide or a hydrocarbylaminogermyl halide.
  • Bridged siloxy- cyclopentadienyl ligands may be constructed by reacting a siloxy-monocyclopentadienyl ligand with a bridging agent (eg Si(CH 3 ) 2 Cl 2 ) or with a bridging agent and a further ⁇ -ligand (eg a different cyclopentadienyl ligand or with an indenyl, fluorenyl , etc ligand).
  • ⁇ -ligands other than chlorine may be introduced by displacement of chlorine from an ⁇ -ligand metal chloride by reaction with appropriate nucleophilic reagent (e.g.
  • a reagent such as tetrakisdimethylamidotitanium or metal compounds with mixed chloro and dimethylamido ligands.
  • the olefin polymerisation catalyst system of the invention comprises (i) a siloxycyclopentadienyl metallocene and (ii) an aluminium alkyl compound, or the reaction product thereof.
  • the aluminium alkyl compound may be an aluminium trialkyl (eg triethylaluminium (TEA) ) or an aluminium dialkyl halide (eg diethyl aluminium chloride (DEAC) )
  • TEA triethylaluminium
  • DEAC aluminium dialkyl halide
  • it is preferably an alumoxane, particularly an alumoxane other than MAO, most preferably an isobutylalumoxane, eg TIBAO (tetraisobutylalu oxane) or HIBAO
  • alkylated metallocene procatalysts of the invention may be used with other cocatalysts, eg boron compounds such as B(C 6 F 5 ) 3 , C 6 H 5 N(CH 3 ) 2 H:B (C 6 F 5 ) __ , (C 6 H 5 ) 3 C:B(C 6 F 5 ) 4 or Ni (CN) 4 [B (C 6 F 5 ) 3 ] 4 2 ⁇ .
  • the metallocene procatalyst and cocatalyst may be introduced into the polymerization reactor separately or together or, more preferably they are pre-reacted and their reaction product is introduced into the polymerization reactor.
  • the procatalyst, procatalyst/cocatalyst mixture or a procatalyst/cocatalyst reaction product may be used in unsupporeted form i.e. metallocene and alumoxane can be precipitated without any actual carrier material and used as such.
  • the metallocene procatalyst or its reaction product with the cocatalyst is preferably introduced into the polymerization reactor in supported form, eg impregnated into a porous particulate support .
  • the particulate support material used is preferably an organic or inorganic material, e.g. a polymer (such as for example polyethylene, polypropylene, an ethylene-propylene copolymer, another polyolefin or polystyrene or a combination thereof) .
  • a polymer such as for example polyethylene, polypropylene, an ethylene-propylene copolymer, another polyolefin or polystyrene or a combination thereof
  • Such polymeric supports may be formed by precipitating a polymer or by a prepolymerization, eg of monomers used in the polymerization for which the catalyst is intended.
  • the support is especially preferably a metal or pseudo metal oxide such as silica, alumina or zirconia or a mixed oxide such as silica-alumina, in particular silica, alumina or silica-alumina.
  • the support material is acidic, e.g. having an acidity greater than or equal to silica, more preferably greater than or equal to silica-alumina and even more preferably greater than or equal to alumina.
  • the acidity of the support material can be studied and compared using the TPD (temperature programmed desorption of gas) method.
  • the gas used will be ammonia. The more acidic the support, the higher will be its capacity to adsorb ammonia gas. After being saturated with ammonia, the sample of support material is heated in a controlled fashion and the quantity of ammonia desorbed is measured as a function of temperature.
  • the support is a porous material so that the catalysts may be loaded into the pores of the support, e.g. using a process analogous to those described in W094/14856 (Mobil) , W095/12622 (Borealis) and WO96/00243 (Exxon) .
  • the particle size is not critical but is preferably in the range 5 to 200 ⁇ m, more preferably 20 to 80 ⁇ m.
  • the particulate support material is preferably calcined, ie heat treated, preferably under a non-reactive gas such as nitrogen.
  • This treatment is preferably at a temperature in excess of 100°C, more preferably 200°C or higher, e.g. 200-800°C, particularly about 300°C.
  • the calcination treatment is preferably effected for several hours, e.g. 2 to 30 hours, more preferably about 10 hours.
  • the support may also be treated with an alkylating agent before being loaded with the catalysts.
  • Treatment with the alkylating agent may be effected using an alkylating agent in a gas or liquid phase, e.g. in an organic solvent for the alkylating agent.
  • the alkylating agent may be any agent capable of introducing alkyl groups, preferably C x . 6 alkyl groups and most especially preferably methyl groups. Such agents are well known in the field of synthetic organic chemistry.
  • the alkylating agent is an organometallic compound, especially an organoaluminium compound (such as trimethylaluminium (TMA) , dimethyl aluminium chloride, triethylaluminium) or a compound such as methyl lithium, dimethyl magnesium, triethylboron, etc.
  • TMA trimethylaluminium
  • a compound such as methyl lithium, dimethyl magnesium, triethylboron, etc.
  • TMA trimethylaluminium
  • dimethyl aluminium chloride such as triethylaluminium
  • a compound such as methyl lithium, dimethyl magnesium, triethylboron, etc.
  • the quantity of alkylating agent used will depend upon the number of active sites on the surface of the carrier. Thus for example, for a silica support, surface hydroxyls are capable of reacting with the alkylating agent. In general, an excess of alkylating agent is preferably used with any unreacted alkylating agent subsequently being washed away
  • an organoaluminium alkylating agent is used, this is preferably used in a quantity sufficient to provide a loading of at least 0.1 mmol Al/g carrier, especially at least 0.5 mmol Al/g, more especially at least 0.7 mmol Al/g, more preferably at least 1.4 mmol Al/g carrier, and still more preferably 2 to 3 mmol Al/g carrier.
  • the surface area of the carrier is particularly high, lower aluminium loadings may be used.
  • particularly preferred aluminium loadings with a surface area of 300-400 m 2 /g carrier may range from 0.5 to 3 mmol Al/g carrier while at surface areas of 700-800 m 2 /g carrier the particularly preferred range will be lower.
  • the support is preferably removed from the treatment fluid and any excess treatment fluid is allowed to drain off.
  • the optionally alkylated support material is loaded with the catalysts, preferably using a solution of the catalyst (s) in an organic solvent therefor, e.g. as described in the patent publications referred to above.
  • the volume of catalyst solution used is from 50 to 500% of the pore volume of the carrier, more especially preferably 80 to 120%.
  • the concentration of catalyst compound in the solution used can vary from dilute to saturated depending on the amount of catalytically active sites that it is desired be loaded into the carrier pores.
  • the active metals are preferably loaded onto the support material at from 0.1 to 4%, preferably 0.5 to 3.0%, especially 1.0 to 2.0%, by weight metal relative to the dry weight of the support material .
  • the loaded support may be recovered for use in olefin polymerization, e.g. by separation of any excess catalyst solution and if desired drying of the loaded support, optionally at elevated temperatures, e.g. 25 to 80°C.
  • a cocatalyst e.g.- an alumoxane or an ionic catalyst activator (such as a boron or aluminium compound, especially a fluoroborate) may also be mixed with or loaded onto the catalyst support material.
  • This may be done subsequently or more preferably simultaneously to loading of the catalysts, for example by including the cocatalyst in the solution of the catalyst or, by contacting the catalyst loaded support material with a solution of the cocatalyst or catalyst activator, e.g. a solution in an organic solvent.
  • a solution of the cocatalyst or catalyst activator e.g. a solution in an organic solvent.
  • any such further material may be added to the catalyst loaded support material in the polymerization reactor or shortly before dosing of the catalyst material into the reactor.
  • an alternative to using an alumoxane is to use a fluoroborate catalyst activacor, especially a B(C 6 F 5 ) 3 or more especially a ⁇ B(C 6 F 5 ) 4 compound, such as C 6 H 5 N(CH 3 ) 2 H:B(C 6 F 5 ) 4 or (C 6 H 5 ) 3 C :B (C 6 F 5 ) 4 .
  • a fluoroborate catalyst activacor especially a B(C 6 F 5 ) 3 or more especially a ⁇ B(C 6 F 5 ) 4 compound, such as C 6 H 5 N(CH 3 ) 2 H:B(C 6 F 5 ) 4 or (C 6 H 5 ) 3 C :B (C 6 F 5 ) 4 .
  • Other borates of general formula (cation + ) a (borate " ) b where a and b are positive numbers, may also be used.
  • cocatalyst or catalyst activator it is preferably used in a mole ratio to the catalytically active metal of from 0.1:1 to 10000:1, especially 1:1 to 50:1, particularly 1:2 to 30:1. More particularly, where an alumoxane cocatalyst is used, then the aluminium: catalyst metal (M) molar ratio is conveniently 2:1 to 10000:1, preferably 50:1 to 400:1. Where a borane cocatalyst (catalyst activator) is used, the B:M molar ratio is conveniently 2:1 to 1:2, preferably 9:10 to 10:9, especially 1:1.
  • the B:M molar ratio is typically 1:2 to 500:1, however some aluminium alkyl would normally also be used.
  • ionic tetraaryl borate compounds it is preferred to use carbonium rather than ammonium counterions or to use B:M molar ratio 1:1 or below.
  • the support may be recovered and if desired dried before use in olefin polymerization.
  • the olefin polymerized in the method of the invention is preferably ethylene or an alp a-olefin or a mixture of ethylene and an ⁇ -olefin or a mixture of alpha olefins, for example C 2 _ 20 olefins, e.g. ethylene, propene, n-but-1-ene, n-hex-1-ene, 4-methyl-pent-1-ene, n-oct-1-ene- etc.
  • the olefins polymerized in the method of the invention may include any compound which includes unsaturated polymerizable groups.
  • unsaturated compounds such as C 6 _ 20 olefins (including cyclic and polycyclic olefins (e.g. norbornene)), and polyenes, especially C 6 -. 20 dienes, may be included in a comonomer mixture with lower olefins, e.g. C 2 _ 5 a ⁇ olefins.
  • the polymer being produced is a homopolymer it will preferably be polyethylene or polypropylene/ Where the polymer being produced is a copolymer it will likewise preferably be an ethylene or propylene copolymer with ethylene or propylene making up the major proportion (by number and more preferably by weight) of the monomer residues.
  • Comonomers such as C 4 _ 6 alkenes, will generally be incorporated to contribute to the mechanical strength of the polymer product .
  • the nature of the monomer/monomer mixture and the polymerization conditions may be changed during the polymerization process so as to produce a desired molecular weight distribution, e.g. a broad bimodal or multimodal molecular weight distribution (MWD) in the final polymer product.
  • a desired molecular weight distribution e.g. a broad bimodal or multimodal molecular weight distribution (MWD) in the final polymer product.
  • MWD molecular weight distribution
  • the higher molecular weight component contributes to the strength of the end product while the lower molecular weight component contributes to the processability of the product, e.g. enabling the product to be used in extrusion and blow moulding processes, for example for the preparation of tubes, pipes, containers, etc.
  • MWD control in the method of the invention may be acheived by controlling the monomer (e.g. ethylene) and preferably also hydrogen partial pressure) .
  • hydrogen concentration may be varied up to 5%, more preferably up to 1%, of the gas phase in the polymerisation reactor.
  • the polymerization reaction may be affected at atmospheric or subatmospheric monomer pressure to acheive low molecular weight polymer production by the titanium catalyst and at pressure in the range of atmospheres (e.g. 10 to 50 bar, preferably 20 to 45 bar) to acheive production of very high molecular weight polymers by the titanium catalyst.
  • Polymerization in the method of the invention may be effected in-' one or more, e.g. 1, 2 or 3, polymerization reactors, using conventional polymerization techniques, e.g. gas phase, solution phase, slurry or bulk polymerization, most preferably gas phase polymerization.
  • conventional polymerization techniques e.g. gas phase, solution phase, slurry or bulk polymerization, most preferably gas phase polymerization.
  • a combination of slurry (or bulk) and at least one gas phase reactor is often preferred, particularly with the reactor order being slurry (or bulk) then one or more gas phase .
  • the reaction temperature will generally be in the range 60 to 110°C (e.g. 85-110°C)
  • the reactor pressure will generally be in the range 5 to 80 bar (e.g. 50-65 bar)
  • the residence time will generally be in the range 0.3 to 5 hours (e.g. 0.5 to 2 hours) .
  • the diluent used will generally be an aliphatic hydrocarbon having a boiling point in the range -70 to +100°C. In such reactors, polymerization may if desired be effected under supercritical conditions .
  • the reaction temperature used will generally be in the range 60 to 115°C (e.g. 70 to 110°C)
  • the reactor pressure will generally be in the range 10 to 25 bar
  • the residence time will generally be 1 to 8 hours.
  • the gas used will commonly be a non-reactive gas such as nitrogen together with monomer (e.g. ethylene).
  • reaction temperature used will generally be in the range 130 to 270°C
  • reactor pressure will generally be in the range 20 to 400 bar
  • residence time will generally be in the range 0.1 to 1 hour.
  • the solvent used will commonly be a hydrocarbon with a boiling point in the range 80-200°C.
  • NMR spectra were recorded using a JEOL JNM-EX270 MHz FT- NMR spectrometer with trimethylsilane (TMS) as an internal reference .
  • TMS trimethylsilane
  • Direct inlet mass spectra were recorded using a VG TRIO 2 quadrupole mass spectrometer in electron impact ionization mode (70eV) .
  • GC-MS analysis was performed using a Hewlett Packard 6890/5973 Mass Selective Detector in electron impact ionization mode (70eV) , equipped with a silica capillary column (30m x 0.25 mm i.d).
  • Ligand preparation was based on known procedures, eg as described in Organometallics 15.: 5066-86 (1996) and in Bull. Soc. Chem. Fr 2981-91 (1970).
  • MAO (30wt% in toluene) and HIBAO (70wt% in toluene) from Albermarle were used.
  • n-Butyl lithium (22.3mL, 60.3mmol) was added dropwise over 5 minutes into a solution of tert .butylamine (4.41g, 60.3mmol) in 50mL of dry tetrahydrofuran (THF) at ambient temperature. The resulting solution was refluxed for 3 hours. Then dimethylsilyldichloride (7.4mL, 60.3mmol) dissolved in 50mL of dry THF was added over 10 minutes at 25oC. The solution was stirred overnight at 50oC and a whitish precipitate formed. The precipitate was filtered off and washed with 2x2OmL of THF.
  • THF dry tetrahydrofuran
  • Example 1 and MAO or HIBAO in an Al:Ti molar ratio of 1000:1.
  • the polymerization medium was pentane and polymerization was effected for 30 minutes with no hydrogen present and a 10 bar ethylene partial pressure. Further details of the polymerization procedure and the polymer products are set out in Table 1 below:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

The invention provides a metallocene procatalyst compound comprising a group 3 to 7 transition metal θ- and σ-liganded by a siloxy substituted, monocyclic, homo- or heterocyclic cyclopentadienyl group. Such compounds may be used together with a cocatalyst, e.g. an alumoxane, for olefin polymerization.

Description

SILOXY-SUBSTITUTED MONOCYCLOPENTADIENYL LIGATED CONSTRAINED GEOMETRY OLEFIN POL YMERISATION CATALYSTS
5 This invention relates to catalysts for olefin polymerisation, in particular to catalyst compounds containing metals η- and σ-bonded by siloxycyclopentadienyl ligands, and their use in olefin polymerisation. 10
In olefin polymerization, it has long been known to use as a catalyst system the combination of a metallocene procatalyst and an alumoxane co-catalyst.
15 By "metallocene" is here meant an η-ligand metal complex, e.g. an "open sandwich" or "half sandwich" compound in which the metal is complexed by a single η- ligand, a "sandwich" compound in which the metal is complexed by two or more η-ligands, a "handcuff"
20 compound" in which the metal is complexed by a bridged bis-η-ligand or a "scorpionate" compound in which the metal is complexed by an η-ligand linked by a bridge to a σ-ligand.
25 Alumoxanes are compounds with alternating aluminium and oxygen atoms generally compounds of formula A or B
R2A1- (O-AlR)p-O-AlRj (A)
RA1- (0-AlR)p-0-AlR (B)
30 V, O ^
where each R, which may be the same or different, is a C^o alkyl group, and p is an integer having a value between 0 and 40) . These compounds may be prepared by 35 reaction of an aluminium alkyl with water. The production and use of alumoxanes is described in the patent literature, especially the patent applications of Texas Alkyls, Albemarle, Ethyl, Phillips, Akzo Nobel, Exxon, Idemitsu Kosan, Witco, BASF and Mitsui.
Methyl alumoxane (MAO) and butyl alumoxanes (e.g. hexaisobutylalumoxane and tetraisobutylalumoxane are preferred for use according to the present invention.
We have now surprisingly found that metallocenes in which the metal is η-liganded by a siloxy-, homo or heterocyclic cyclopentadienyl group, i.e. a cyclic η5-ligand substituted by a siloxy group but not carrying a fused ring, have surprisingly high activity with non- MAO alumoxanes .
Thus viewed from one aspect the invention provides a metallocene procatalyst compound comprising a group 3 to 7 transition metal η- and σ-liganded by a siloxy substituted, monocyclic, homo- or heterocyclic cyclopentadienyl group.
By a group 3 (etc) metal is meant a metal in group 3 of the Periodic Table of the Elements, namely Sc, Y, etc.
Viewed from a further aspect the invention provides an olefin polymerisation catalyst system comprising or produced by reaction of (i) a metallocene procatalyst compound comprising a group 3 to 7 transition metal η- and σ-liganded by a siloxy substituted, monocyclic, homo- or heterocyclic cyclopentadienyl group and (ii) a co-catalyst, eg an aluminium alkyl compound, in particular an alumoxane, especially an aluminium alkyl compound comprising alkyl groups containing at least two carbon atoms .
Viewed from a still further aspect the invention provides a process for olefin polymerisation comprising polymerising an olefin in the presence of a metallocene compound comprising a group 3 to 7 transition metal η- and σ-liganded by a siloxy substituted, monocyclic, homo- or heterocyclic cyclopentadienyl group.
Viewed from a yet further aspect the invention provides a process for the preparation of a metallocene procatalyst, said process comprising metallating with a group 3 to 7 transition metal a ligand comprising a monocyclic, homo- or heterocyclic cyclopentadienyl group substituted on the η-ring by a siloxy group and by a group capable /of σ-bonding said metal .
Viewed from a further aspect the invention provides the use of a metallocene compound comprising a group 3 to 7 transition metal η- and σ-liganded by a siloxy substituted, monocyclic, homo- or heterocyclic cyclopentadienyl group in olefin polymerization, especially ethylene or propylene, more especially ethylene, polymerisation or copolymerisation.
Viewed from a yet further aspect the invention provides an olefin polymer produced by a polymerisation catalysed by a metallocene compound comprising a group 3 to 7 transition metal η- and σ-liganded by a siloxy substituted, monocyclic, homo- or heterocyclic cyclopentadienyl group.
By "monocyclic" it is meant that the η5 ring of the cyclopentadienyl group is not fused to another ring, ie it cannot be a part of an indenyl or fluorenyl multi- ring structure. The η5 ring however may be substituted by cyclic groups or cyclic group containing substituents and the metal may be liganded by other η-ligands which are acyclic or multicyclic.
The η5-ligand with which the group 3 to 7 metal is complexed typically is a compound of formula IV
Figure imgf000005_0001
where X, Y and T are ring carbons or ring heteroatoms, eg N, B or P atoms, two or three of X, Y and T preferably being ring carbons; each R', which may be the same or different is a R+, OR+, SR+, NR+ 2 or PR+ 2 group where each R+ is a Cx_16 hydrocarbyl group, a tri-C,.
8hydrocarbylsiLyl group or a tri-C1_8hydrocarbylsiloxy group, preferably R' being a C1_12 hydrocarbyl group, eg a C2_8 alkyl or alkenyl group;
each R", which may be the same or different is a ring substituent which does not form a bond to a metal η- bonded by the C2XYT ring and is other than a ring fused to the C2XYT ring (eg a R+, OR+, SR+, NR+ 2 or PR+ 2 group where each R+ is a
Figure imgf000005_0002
hydrocarbylsilyl group or a tri-C1_ahydrocarbylsiloxy group or two R+ groups together form a 3 to 6 atom bridge, preferably a hydrocarbyl bridge) or is an η- ligand linked to the C2XYT ring by a 1 to 3 atom bridge, and optionally substituted, eg by R+, OR+, SR+, NR+ 2 or PR+ 2 groups;
n is zero or a positive integer, eg having a value of 1, 2, 3 or 4, n preferably being non-zero; m is 1 or 2,preferably 1; and R"' is a group capable of σ-bonding a transition metal ion, eg a group defined as Z in WO98/06728.
In the ligand of formula IV, the σ-bonding moiety R" ' is a divalent moiety bound to the cyclopentadienyl ring by a σ-bond and capable of binding to a transition metal M via a σ-bond, preferably via a M-heteroatom bond. R" ' preferably comprises boron or a group 14 atom (eg C, Si or Ge) and a N, 0, S or P atom. Particularly preferably, R" ' comprises a group RaRb with Ra attached to the cyclopentadienyl ring and RD being capable of bonding to the metal M, where Ra provides a 1 to 3 atom bridge of group 14 atoms, eg a group SiRc 2, CR°2,
Figure imgf000006_0001
, CR 2SlR 2, CR 2Sl 2CR 2, SiRc 2CRc 2SiRc 2, CRc 2CRc 2SiRc 2, CRC 2CRC 2CRC 2 or GeRc 2, Rb is NRC, 0, S or PR0, and Rc is hydrogen, hydrocarbyl, hydrocarbyloxy, silyl or halohydrocarbyl or two Rc groups together form a homo- or heterocyclic ring, each R° containing up /to 20 non-hydrogen atoms. Thus the "scorpion tail" RaRb may contain as side chains silyl (eg trialkylsilyl) and halohydrocarbyl (eg CF3 or perfluoro- t-butyl) groups .
Particularly preferred R" ' groups include -Si(CH3)2NRd groups where Rd is a C__^12 hydrocarbyl group, eg
-Si (CH3)2-N-t. butyl
-Si (CH3) 2-N-cyclohexyl or
-Si (CH3) 2-N-benzyl .
Besides the η-ligand of formula IV, the group 3 to 7 transition metal may be η-liganded by one or two further η ligands. These may be cyclic or acyclic and may carry cyclic groups fused to an η5 or η4 cyclic or acyclic structure and may be bridged bis-η ("handcuff") ligands or bridged η-σ ("scorpion") ligands. Thus for example such an η5 or η4 ligand group may be a homo- or heterocyclic cyclopentadienyl, indenyl or fluorenyl group, or an acyclic η5 C5, η5-C3N2 or η4C2N2 group optionally carrying cyclic groups fused to the η5 or η4 skeleton. Such further η ligands may optionally be substituted, eg by groups R". Particular examples of such further η-ligands include cyclopentadienyl, indenyl and fluorenyl ligands, especially siloxy substituted (eg R'3SiO-substituted) cyclopentadienyl or indenyl ligands.
Examples of such further η-ligands abound in the patent literature relating to metallocene and pseudo metallocene olefin polymerization (pro) catalysts, in particular that deriving from Exxon, Hoechst, Phillips, Dow, Chisso, Mitsui, Fina, BASF, Mitsubishi, Mobil, Targor, DSM an'd Borealis, eg WO96/23010, WO98/49208, W099/12981, W099/19335, WO97/28170, EP-A-423101 and EP- A-537130 as well as "Metallocenes" , Vol 1, Togni and Halterman (Eds.), Wiley-VCH, 1998.
Besides η-ligands, the group 3 to 7 metal in the procatalyst of the invention may be coordinated by hydrogen atoms, hydrocarbyl σ-ligands (eg optionally substituted Cx_12 hydrocarbyl groups, such as C___ιz alkyl, alkenyl or alkynyl groups optionally substituted by fluorine and/or aryl (eg phenyl) groups) , by silane groups (eg Si(CH3)3), by halogen atoms (eg chlorine) , by Cι_8 hydrocarbylheteroatom groups, by tri- Ci.ghydrocarbylsilyl groups, by bridged bis-σ-liganding groups, by amine (eg N(CH3)2) or imine (eg N=C or N=P groups, eg (iPr)3P=N) groups, or by other σ-ligands known for use in metallocene (pro) catalysts.
By a σ-ligand moiety is meant a group bonded to the metal at one or more places via a single atom, eg a hydrogen, halogen, silicon, carbon, oxygen, sulphur or nitrogen atom.
Thus for example the metallocene pro catalyst of the invention may conveniently be a compound of formula V
Figure imgf000008_0001
where X, Y, T, R', R", R"', n and m are as defined above;
q is 1, 2 or 3, generally being 1 when m is 1 ; M is a group 3 to 7 transition metal
L is a further/ η-ligand (eg as discussed above) ; r is zero, 1 or 2;
Z is a σ-ligand (eg as discussed above) ; and s is zero or a positive integer having a value of up to 3 depending on the values of m, q and r and the oxidation state of metal M.
The metal M in the metallocene procatalysts of the invention is a group 3 to 7 transition metal, preferably a group 4 to 6 transition metal, eg a metal selected from Ti, Zr, Hf, V, Nb, Ta, Cr, Mo and W. However the metal is preferably Cr, Ti, Zr or Hf, particularly Cr if M is η-liganded by a single η-ligand group or Ti, Zr or Hf if M is η-liganded by one or more η-ligand groups
In the metallocene procatalysts of the invention, the siloxycyclopentadienyl η-ligand is especially preferably a ligand of formula VI
Figure imgf000008_0002
where R' is as defined above; Y' is P, B, CH or C-CH3; R^ is H or CH3; and R is a group RaR as defined above
Examples of suitable R'3SiO groups in the metallocene procatalysts of the invention include
Figure imgf000009_0001
Thus typical examples of ligands of formula IV include
Figure imgf000009_0002
Typical examples of the metallocene procatalysts of the invention thus include:
Figure imgf000010_0001
Examples of particular siloxy-η-ligands usable according to the invention include:
dimethylsilanediyl (2- triisopropylsiloxycyclopentadienyl) (N-tert .butylamido) , dimethylsilanediyl (2-triisopropylsiloxy-4-methyl- cyclopentadienyl) (N-tert .butylamido) , dimethylsilanediyl (2-triisopropylsiloxy-3,4-dimethyl- cyclopentadienyl) (N-tert .butylamido) , dimethylsilanediyl (2-triisopropylsiloxy-3 , 4 , 5-trimethyl- cyclopentadienyl) (N-tert .butylamido) , dimethylsilanediyl (2- tert .butyl, dimethylsiloxycyclopentadienyl) (N- tert .butylamido) , dimethylsilanediyl (2-tert .butyl , dimethylsiloxy-4-methyl- cyclopentadienyl) (N-tert .butylamido) , dimethylsilanediyl (2-tert .butyl, dimethylsiloxy-3 , 4- dimethyl-cyclopentadienyl) (N-tert .butylamido) , dimethylsilanediyl (2-tert .butyl, dimethylsiloxy-3 ,4,5- trimethyl-cyclopentadienyl) (N-tert .butylamido) , dimethylsilanediyl (2-trimethylsiloxycyclopentadienyl) (N- t .butylamido) , dimethylsilanediyl (2- t .butyl, dimethylsiloxycyclopentadienyl) (N-t .butylamido) , dimethylsilanediyl (2- t .butyl, dimethylsiloxyphospholyl) (N-t .butylamido) , dimethylsilanediyl (2-t .butyl, dimethylsiloxypyrrolyl) (N- t .butylamido) , and trimethylsilylmethylsilanediyl (2- trimethylsiloxycyclopentadienyl) (N- .butylamido) .
Examples of particular further η-ligands are well known from the technical and patent literature relating to metallocene olefin polymerization catalysts, e.g. EP-A-
35242 (BASF) , EP-A-129368 (Exxon) , EP-A-206794 (Exxon) , PCT/FI97/00049 (Borealis), EP-A-318048, EP-A-643084, EP-
A-69951, EP-A-410734, EP-A-128045, EP-B-35242 (BASF) ,
EP-B-129368 (Exxon) and EP-B-206794 (Exxon) . These include
cyclopentadienyl , indenyl , fluorenyl , octahydrofluorenyl , methylcyclopentadienyl , 1 , 2-dimethylcyclopentadienyl , pentamethylcyclopentadienyl , pentyl-cyclopentadienyl , 2-dimethyl, tertbutylsiloxy-inden-1-yl , n-butylcyclopentadienyl , 1 , 3-dimethylcyclopentadienyl , 4 , 7-dimethylindenyl , 1, -ethyl-2-methylcyclopentadienyl, tetrahydroindenyl, and methoxycyclopentadienyl .
Examples of σ-ligands include:
halogenides (e/.g. chloride and fluoride) , hydroge , triC1_12 hydrocarbyl-silyl or -siloxy(e.g. trimethylsilyl) , trices hydrocarbylphosphimido (e.g. triisopropylphosphimido) , c ι-i2 hydrocarbyl or hydrocarbyloxy (e.g. methyl, ethyl, phenyl, benzyl and methoxy) , diCi-,6 hydrocarbylamido (e.g. dimethylamido and diethylamido) , and
5 to 7 ring membered heterocyclyl (eg pyrrolyl, furanyl and pyrrolidinyl) .
The siloxy cyclopentadienyl η-σ-ligands used according to the invention may be prepared by reaction of a corresponding siloxycyclopentadiene with an organolithium compound, eg methyllithium or butyllithium. The ligand can be metallated conventionally, eg by reaction with a halide of the metal M, preferably in an organic solvent, eg a hydrocarbon or a hydrocarbon/ether mixture . The σ- bonding group R" ' may be introduced by reacting a corresponding siloxycyclopentadiene with a compound such as a hydrocarbylaminosilyl halide or a hydrocarbylaminogermyl halide. Bridged siloxy- cyclopentadienyl ligands may be constructed by reacting a siloxy-monocyclopentadienyl ligand with a bridging agent (eg Si(CH3)2Cl2) or with a bridging agent and a further η-ligand (eg a different cyclopentadienyl ligand or with an indenyl, fluorenyl , etc ligand). σ-ligands other than chlorine may be introduced by displacement of chlorine from an η-ligand metal chloride by reaction with appropriate nucleophilic reagent (e.g. methyl lithium or methylmagnesium chloride) or using, instead of a metal halide, a reagent such as tetrakisdimethylamidotitanium or metal compounds with mixed chloro and dimethylamido ligands.
As mentioned above, the olefin polymerisation catalyst system of the invention comprises (i) a siloxycyclopentadienyl metallocene and (ii) an aluminium alkyl compound, or the reaction product thereof. While the aluminium alkyl compound may be an aluminium trialkyl (eg triethylaluminium (TEA) ) or an aluminium dialkyl halide (eg diethyl aluminium chloride (DEAC) ) , it is preferably an alumoxane, particularly an alumoxane other than MAO, most preferably an isobutylalumoxane, eg TIBAO (tetraisobutylalu oxane) or HIBAO
(hexaisobutylalumoxane) . Alternatively however the alkylated (eg methylated) metallocene procatalysts of the invention (e.g. compounds of formula V wherein Z is alkyl) may be used with other cocatalysts, eg boron compounds such as B(C6F5)3, C6H5N(CH3) 2H:B (C6F5) __ , (C6H5)3C:B(C6F5)4 or Ni (CN) 4 [B (C6F5) 3] 4 2~ .
The metallocene procatalyst and cocatalyst may be introduced into the polymerization reactor separately or together or, more preferably they are pre-reacted and their reaction product is introduced into the polymerization reactor.
If desired the procatalyst, procatalyst/cocatalyst mixture or a procatalyst/cocatalyst reaction product may be used in unsupporeted form i.e. metallocene and alumoxane can be precipitated without any actual carrier material and used as such. However the metallocene procatalyst or its reaction product with the cocatalyst is preferably introduced into the polymerization reactor in supported form, eg impregnated into a porous particulate support .
However, the particulate support material used is preferably an organic or inorganic material, e.g. a polymer (such as for example polyethylene, polypropylene, an ethylene-propylene copolymer, another polyolefin or polystyrene or a combination thereof) . Such polymeric supports may be formed by precipitating a polymer or by a prepolymerization, eg of monomers used in the polymerization for which the catalyst is intended. However, the support is especially preferably a metal or pseudo metal oxide such as silica, alumina or zirconia or a mixed oxide such as silica-alumina, in particular silica, alumina or silica-alumina.
Particularly preferably, the support material is acidic, e.g. having an acidity greater than or equal to silica, more preferably greater than or equal to silica-alumina and even more preferably greater than or equal to alumina. The acidity of the support material can be studied and compared using the TPD (temperature programmed desorption of gas) method. Generally the gas used will be ammonia. The more acidic the support, the higher will be its capacity to adsorb ammonia gas. After being saturated with ammonia, the sample of support material is heated in a controlled fashion and the quantity of ammonia desorbed is measured as a function of temperature.
The support is a porous material so that the catalysts may be loaded into the pores of the support, e.g. using a process analogous to those described in W094/14856 (Mobil) , W095/12622 (Borealis) and WO96/00243 (Exxon) . The particle size is not critical but is preferably in the range 5 to 200 μm, more preferably 20 to 80 μm.
Before loading, the particulate support material is preferably calcined, ie heat treated, preferably under a non-reactive gas such as nitrogen. This treatment is preferably at a temperature in excess of 100°C, more preferably 200°C or higher, e.g. 200-800°C, particularly about 300°C. The calcination treatment is preferably effected for several hours, e.g. 2 to 30 hours, more preferably about 10 hours.
The support may also be treated with an alkylating agent before being loaded with the catalysts. Treatment with the alkylating agent may be effected using an alkylating agent in a gas or liquid phase, e.g. in an organic solvent for the alkylating agent. The alkylating agent may be any agent capable of introducing alkyl groups, preferably Cx.6 alkyl groups and most especially preferably methyl groups. Such agents are well known in the field of synthetic organic chemistry. Preferably the alkylating agent is an organometallic compound, especially an organoaluminium compound (such as trimethylaluminium (TMA) , dimethyl aluminium chloride, triethylaluminium) or a compound such as methyl lithium, dimethyl magnesium, triethylboron, etc. The quantity of alkylating agent used will depend upon the number of active sites on the surface of the carrier. Thus for example, for a silica support, surface hydroxyls are capable of reacting with the alkylating agent. In general, an excess of alkylating agent is preferably used with any unreacted alkylating agent subsequently being washed away.
Where an organoaluminium alkylating agent is used, this is preferably used in a quantity sufficient to provide a loading of at least 0.1 mmol Al/g carrier, especially at least 0.5 mmol Al/g, more especially at least 0.7 mmol Al/g, more preferably at least 1.4 mmol Al/g carrier, and still more preferably 2 to 3 mmol Al/g carrier. Where the surface area of the carrier is particularly high, lower aluminium loadings may be used. Thus for example particularly preferred aluminium loadings with a surface area of 300-400 m2/g carrier may range from 0.5 to 3 mmol Al/g carrier while at surface areas of 700-800 m2/g carrier the particularly preferred range will be lower.
Following treatment of the support material with the alkylating agent, the support is preferably removed from the treatment fluid and any excess treatment fluid is allowed to drain off.
The optionally alkylated support material is loaded with the catalysts, preferably using a solution of the catalyst (s) in an organic solvent therefor, e.g. as described in the patent publications referred to above. Preferably, the volume of catalyst solution used is from 50 to 500% of the pore volume of the carrier, more especially preferably 80 to 120%. The concentration of catalyst compound in the solution used can vary from dilute to saturated depending on the amount of catalytically active sites that it is desired be loaded into the carrier pores.
The active metals (ie. the metals of the catalysts) are preferably loaded onto the support material at from 0.1 to 4%, preferably 0.5 to 3.0%, especially 1.0 to 2.0%, by weight metal relative to the dry weight of the support material .
After loading of the catalysts onto the support material, the loaded support may be recovered for use in olefin polymerization, e.g. by separation of any excess catalyst solution and if desired drying of the loaded support, optionally at elevated temperatures, e.g. 25 to 80°C. As mentioned above, a cocatalyst, e.g.- an alumoxane or an ionic catalyst activator (such as a boron or aluminium compound, especially a fluoroborate) may also be mixed with or loaded onto the catalyst support material. This may be done subsequently or more preferably simultaneously to loading of the catalysts, for example by including the cocatalyst in the solution of the catalyst or, by contacting the catalyst loaded support material with a solution of the cocatalyst or catalyst activator, e.g. a solution in an organic solvent. Alternatively however any such further material may be added to the catalyst loaded support material in the polymerization reactor or shortly before dosing of the catalyst material into the reactor.
However, an alternative to using an alumoxane is to use a fluoroborate catalyst activacor, especially a B(C6F5)3 or more especially a ΘB(C6F5)4 compound, such as C6H5N(CH3)2H:B(C6F5)4 or (C6H5) 3C :B (C6F5) 4. Other borates of general formula (cation+)a (borate")b where a and b are positive numbers, may also be used.
Where such a cocatalyst or catalyst activator is used, it is preferably used in a mole ratio to the catalytically active metal of from 0.1:1 to 10000:1, especially 1:1 to 50:1, particularly 1:2 to 30:1. More particularly, where an alumoxane cocatalyst is used, then the aluminium: catalyst metal (M) molar ratio is conveniently 2:1 to 10000:1, preferably 50:1 to 400:1. Where a borane cocatalyst (catalyst activator) is used, the B:M molar ratio is conveniently 2:1 to 1:2, preferably 9:10 to 10:9, especially 1:1. When a neutral triarylboron type cocatalyst is used the B:M molar ratio is typically 1:2 to 500:1, however some aluminium alkyl would normally also be used. When using ionic tetraaryl borate compounds, it is preferred to use carbonium rather than ammonium counterions or to use B:M molar ratio 1:1 or below.
Where the further material is loaded onto the catalyst loaded support material, the support may be recovered and if desired dried before use in olefin polymerization.
The olefin polymerized in the method of the invention is preferably ethylene or an alp a-olefin or a mixture of ethylene and an α-olefin or a mixture of alpha olefins, for example C2_20 olefins, e.g. ethylene, propene, n-but-1-ene, n-hex-1-ene, 4-methyl-pent-1-ene, n-oct-1-ene- etc. The olefins polymerized in the method of the invention may include any compound which includes unsaturated polymerizable groups. Thus for example unsaturated compounds, such as C6_20 olefins (including cyclic and polycyclic olefins (e.g. norbornene)), and polyenes, especially C6-.20 dienes, may be included in a comonomer mixture with lower olefins, e.g. C2_5 a~ olefins.
In general, where the polymer being produced is a homopolymer it will preferably be polyethylene or polypropylene/ Where the polymer being produced is a copolymer it will likewise preferably be an ethylene or propylene copolymer with ethylene or propylene making up the major proportion (by number and more preferably by weight) of the monomer residues. Comonomers, such as C4_6 alkenes, will generally be incorporated to contribute to the mechanical strength of the polymer product .
Using the catalysts of the invention the nature of the monomer/monomer mixture and the polymerization conditions may be changed during the polymerization process so as to produce a desired molecular weight distribution, e.g. a broad bimodal or multimodal molecular weight distribution (MWD) in the final polymer product. In such a broad MWD product, the higher molecular weight component contributes to the strength of the end product while the lower molecular weight component contributes to the processability of the product, e.g. enabling the product to be used in extrusion and blow moulding processes, for example for the preparation of tubes, pipes, containers, etc.
MWD control in the method of the invention may be acheived by controlling the monomer (e.g. ethylene) and preferably also hydrogen partial pressure) . Typically hydrogen concentration may be varied up to 5%, more preferably up to 1%, of the gas phase in the polymerisation reactor. To acheive MWD control by varying monomer concentration the polymerization reaction may be affected at atmospheric or subatmospheric monomer pressure to acheive low molecular weight polymer production by the titanium catalyst and at pressure in the range of atmospheres (e.g. 10 to 50 bar, preferably 20 to 45 bar) to acheive production of very high molecular weight polymers by the titanium catalyst.
Polymerization in the method of the invention may be effected in-' one or more, e.g. 1, 2 or 3, polymerization reactors, using conventional polymerization techniques, e.g. gas phase, solution phase, slurry or bulk polymerization, most preferably gas phase polymerization.
In general, a combination of slurry (or bulk) and at least one gas phase reactor is often preferred, particularly with the reactor order being slurry (or bulk) then one or more gas phase . For slurry reactors, the reaction temperature will generally be in the range 60 to 110°C (e.g. 85-110°C) , the reactor pressure will generally be in the range 5 to 80 bar (e.g. 50-65 bar), and the residence time will generally be in the range 0.3 to 5 hours (e.g. 0.5 to 2 hours) . The diluent used will generally be an aliphatic hydrocarbon having a boiling point in the range -70 to +100°C. In such reactors, polymerization may if desired be effected under supercritical conditions .
For gas phase reactors, the reaction temperature used will generally be in the range 60 to 115°C (e.g. 70 to 110°C) , the reactor pressure will generally be in the range 10 to 25 bar, and the residence time will generally be 1 to 8 hours. The gas used will commonly be a non-reactive gas such as nitrogen together with monomer (e.g. ethylene).
For solution phase reactors, the reaction temperature used will generally be in the range 130 to 270°C, the reactor pressure will generally be in the range 20 to 400 bar and the residence time will generally be in the range 0.1 to 1 hour. The solvent used will commonly be a hydrocarbon with a boiling point in the range 80-200°C.
Generally the quantity of catalyst used will depend upon the nature of the catalyst, the reactor types and conditions and the properties desired for the polymer product. Conventional catalyst quantities, such as described in the publications referred to herein, may be used. L
All publications referred to herein are hereby incorporated by reference.
The invention will now be illustrated further by reference to the following non-limiting Examples and to the accompanying drawings in which:
The invention will now be illustrated further by reference to the following non-limiting Examples:
Ligand and complex synthesis
All operations are carried out in an argon or nitrogen atmosphere using standard Schlenk, vacuum and drybox techniques. Ether, tetrahydrofuran (THF) and toluene solvents were dried with potassium benzophenone ketyl and distilled under argon prior to use. Other solvents were dried using 13X+13A molecular sieves. All other chemicals were used as commercially available.
NMR spectra were recorded using a JEOL JNM-EX270 MHz FT- NMR spectrometer with trimethylsilane (TMS) as an internal reference .
Direct inlet mass spectra were recorded using a VG TRIO 2 quadrupole mass spectrometer in electron impact ionization mode (70eV) . GC-MS analysis was performed using a Hewlett Packard 6890/5973 Mass Selective Detector in electron impact ionization mode (70eV) , equipped with a silica capillary column (30m x 0.25 mm i.d).
Ligand preparation was based on known procedures, eg as described in Organometallics 15.: 5066-86 (1996) and in Bull. Soc. Chem. Fr 2981-91 (1970).
Alumoxanes
MAO (30wt% in toluene) and HIBAO (70wt% in toluene) from Albermarle were used.
Example 1
Dimethylsilanediyl (1- (2-t-butyldimethylsiloxy-3 , 4, 5- trimethylcyclopentadienyl) (N-tert .butylamido) titanium dichloride
Figure imgf000021_0001
(a) Synthesis of 2, 3 ,4-trimethyl-5-
(tert .butyl, dimethylsiloxy) -cyclopentadienyl lithium
7.06g (29.6mmol) of 2, 3 , 4-trimethyl-l- (tert.butyl, dimethylsiloxy) -cyclopentadiene (prepared analogously to the descriptions in Bull. Soc. Chem. Fr. 2981-2991(1970) and Organometallics 15:5066-5086 (1996) ) was dissolved in lOOmL of dry heptane at ambient temperature. 6.44mL (62.1mmol) of dimethoxyethane (DME) was added to the solution in one portion using a syringe. The solution was cooled to -40oC and 19.7mL (29.6mmol) of 1.5M tert.butyl lithium was added over five minutes. The light yellow mixture was stirred overnight at ambient temperature. After 16 hours stirring, a pale yellow precipitate had formed and this was filtered and washed with 3x8OmL of dry pentane . The solvents were removed under vacuum yielding a pale yellow solid. Yield 6.68g (92.4%).
-NMR (THF-d8) :δ 4.83 (s, IH) , 1.96 (s, 3H) , 1.92 (s, 3H) , 1.90(s,3H), 0,98(8, 9H) , 0.07(s, 6H) . The product decomposed during EIMS analysis .
(b) Synthesis of 1-chloro-N-t .butyl-1, 1- dimethylsilanamine
n-Butyl lithium (22.3mL, 60.3mmol) was added dropwise over 5 minutes into a solution of tert .butylamine (4.41g, 60.3mmol) in 50mL of dry tetrahydrofuran (THF) at ambient temperature. The resulting solution was refluxed for 3 hours. Then dimethylsilyldichloride (7.4mL, 60.3mmol) dissolved in 50mL of dry THF was added over 10 minutes at 25oC. The solution was stirred overnight at 50oC and a whitish precipitate formed. The precipitate was filtered off and washed with 2x2OmL of THF. The solvents were removed by distillation at atmospheric pressure and the product was further purified by distillation in vacuum to yield 10.45g of a hazy colorless liquid, 68.1% pure containing only THF as impurity. BP 75-89oC/lO-20mbar. Yield 7. lg (71.1%).
1H-NMR(C6D6) :δ 1.26 (s,9H), 0.46 (s.6H). 13C-NMR ( C6D6) : δ 33 . 45 , 26 . 14 , 4 . 77 .
(c) Synthesis of ( (2-tert .butyl, dimethylsiloxy-3 , 4, 5- trimethylcyclopentadienyl) -dimethylsilyl) tert .butylamine
1-Chloro-N-t .butyl-1, 1-dimethylsilanamine (4. Og, 16.36mmol, 68.1% purity) was dissolved in 60mL of dry THF and cooled to -70oC. 2, 3 , 4-Trimethyl-l- (t .butyl, dimethylsiloxy) cyclopentadienyl lithium was dissolved in 2|0OmL of dry THF using a 60oC heating bath. This solution was cooled to -70oC and added over 35 minutes to the silanamine solution. The mixture was allowed to warm to ambient temperature then heated to 70oC overnight. The solvents were removed under vacuum and the product extracted with 3x5OmL pentane and filtered. The solvents were removed under vacuum to give a pale yellow liquid. Yield 5.59g (93.1%). Purity according to 1H-NMR was 99%.
αH-NMR (CDC13) : δ 2.65 (s, IH) , 1.89 (s, 3H) , 1.75 (s, 3H) , 1.68 (s, 3H) , 1.15 (s, 9H) , 0.95 (s, 9H) , 0.13 (s, 3H) , 0.11 (s, 3H) , 0.08 (s, 3H) , -0.06 (s, 3H) . The GC/MS analysis showed the decomposition pattern of the parent ion of the title compound, C20H41NOSi2 corresponding to molecular weight M+=367.72 g rnol"1.
(d) Synthesis of N- (t. butyl) -N- (1- (2- ( (1-t .butyl) -1, 1- dimethylsilyloxy) -3,4, 5-trimethylcyclopentadienyl) -1,1- dimethylsilyl) -amine dilithium
3.2 mL (5.5 mmol) of 1.7M methyl lithium was added using a syringe at -30°C over 7 minutes into a solution of l.Og (2.7 mmol) of ( (2-tert-butyldimethylsiloxy) -3 , 4 , 5- trimethylcyclopentadienyl) -dimethylsilyl) tert- butylamine dissolved in 75 L of heptane to give a pale yellow precipitate. The mixture was warmed to ambient temperature and stirred overnight. All solvents were removed in a vacuum and the dilithium salt isolated in a quantitative yield. The crude product obtained was used in a subsequent reaction without further purification. 1H-NMR analysis showed multiple peaks at δ 0-2.6 ppm which were not identified. The air sensitive product decomposed during EIMS analysis
(e) Synthesis of N- ( ert-butyl) -N- (1- (2- ( (1- tert- butyl) -1, 1-dimethylsilyloxy) -3,4, 5-trimethylcyclopenta- dienyl) -1, 1-dimethylsilyl) amine titanium dichloride
1.04g (2.7 mmol) of N- ( tert-butyl) -N- (1- (2- ( (1- tert- butyl) -1, 1-dimethylsilyloxy) -3 , 4, 5-trimethylcyclopenta- dienyl) -1, 1-dimethylsilyl) amine dilithium salt dissolved in 30 mL of THF was added into a solution of 1.02g (2.7 mmol) of TiCl3(THF)3 dissolved in 100 mL of THF at 0°C over 10 minutes to give a dark solution which was stirred at ambient temperature for 3.5 hours. 0.65g (2.3 mmol) of PbCl2 was added in one portion to give a red mixture which was stirred overnight. Solvents were removed in vacuum and the product extracted with 30 mL of toluene and filtrated. The precipitate was washed with 2x30 ml more toluene and the solvents removed in vacuum. The product was purified by recrystallisation from 50 mL of heptane at -30°C. Yield 1. lg (84.1%) of brown-red solid. The compound decomposed during EIMS analysis.
XH-NMR (CDC13) : δ 2.35 (s, 3H) , 2.28 (s, 3H) , 2.01 (a, 3H) , 1.47 (s, 9H) , 1.24 (s, 9H) , 0.94 (s, 3H) , 0.87 (s, 3H) , 0.30 (m, 3H) , 0.25 (m, 3H) . Example 2
Ethylene polymerization
Ethylene was polymerized using the procatalyst of
Example 1 and MAO or HIBAO in an Al:Ti molar ratio of 1000:1. The polymerization medium was pentane and polymerization was effected for 30 minutes with no hydrogen present and a 10 bar ethylene partial pressure. Further details of the polymerization procedure and the polymer products are set out in Table 1 below:
CO c
CD CO
Figure imgf000026_0002
m
Figure imgf000026_0001
C m r

Claims

1. A metallocene procatalyst compound comprising a group 3 to 7 transition metal η- and σ-liganded by a siloxy substituted, monocyclic, homo- or heterocyclic cyclopentadienyl group.
2. A compound as claimed in claim 1 being a complex of a group 3 to 6 transition metal and a ligand compound of formula IV
Figure imgf000027_0001
(wherein X, Y and T are ring carbons or ring heteroatoms; each R', which may be the same or different is a R+, OR+, SR+, NR+ 2 or PR+ 2 group where each R+ is a C_-i6 hydrocarbyl group, a
Figure imgf000027_0002
group or a tri-C1_8hydrocarbylsiloxy group; each R", which may be the same or different is a ring substituent which does not form a bond to a metal η-bonded by the C2XYT ring and is other than a ring fused to the C2XYT ring or is an η-ligand linked to the C2XYT ring by a 1 to 3 atom bridge; n is zero or a positive integer; m is 1 or 2 ; and
R"' is a group capable of σ-bonding a transition metal ion.
3. A compound as claimed in claim 2 wherein R" ' is - Si(CH3)2NRd where Rd is a Cx.12 hydrocarbyl group.
4. A compound as claimed in either of claims 2 and 3 wherein X, Y and T are each carbon.
5. A compound as claimed in any one of claims 2 to 4 wherein m is 1 and n is 1, 2, 3 or 4.
6. A compound as claimed in claim 2 wherein said ligand is of formula VI
Figure imgf000028_0001
where R' is as defined in claim 2, Y' is P, B, CH or C- CH3, R* is H or CH3; and R"" is Ra Rb where Ra is a linker group providing a 1 to 3 atom chain of group 14 atoms between Rb and the C4Y' ring, and Rb is a group which σ- bonds the transition metal .
7. A compound as claimed in claim 6 wherein RaRb is - Si(CH3)2NRd where Rd is as defined in claim 3.
8. A compound as claimed in any one of the preceding claims wherein the metal is Cr, Ti, Zr or Hf .
9. An olefin polymerisation catalyst system comprising or produced by reaction of (±) a metallocene procatalyst compound comprising a group 3 to 7 transition metal η- and σ-liganded by a siloxy substituted, monocyclic, homo- or heterocyclic cyclopentadienyl group and (ii) a co-catalyst.
10. A catalyst system as claimed in claim 9 wherein said co-catalyst is an alumoxane.
11. A catalyst system as claimed in either of claims 9 and 10 comprising a porous particulate support material impregnated with said metallocene compound and cocatalyst or the reaction product thereof.
12. A catalyst system as claimed in any one of claims 9 to 11 wherein said metallocene compound is a compound as claimed in any one of claims 2 to 8.
13. A process for olefin polymerisation comprising polymerising an olefin in the presence of a metallocene compound comprising a group 3 to 7 transition metal η- and σ-liganded by a siloxy substituted, monocyclic, homo- or heterocyclic cyclopentadienyl group.
14. A proces^ for the preparation of a metallocene procatalyst, said process comprising metallating with a group 3 to 7 transition metal a ligand comprising a monocyclic, homo- or heterocyclic cyclopentadienyl group substituted on the η-ring by a siloxy group and by a group capable of σ-bonding said metal .
15. The use of a metallocene compound comprising a group 3 to 7 transition metal η- and σ-liganded by a siloxy substituted, monocyclic, homo- or heterocyclic cyclopentadienyl group in olefin polymerization, especially ethylene or propylene, more especially ethylene, polymerisation or copolymerisation.
16. An olefin polymer produced by a polymerisation catalysed by a metallocene compound comprising a group 3 to 7 transition metal η- and σ-liganded by a siloxy substituted, monocyclic, homo- or heterocyclic cyclopentadienyl group.
PCT/GB2001/000203 2000-01-19 2001-01-19 Siloxy-substituted monocyclopentadienyl ligated constrained geometry olefin polymerisation catalysts WO2001053361A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2001228629A AU2001228629A1 (en) 2000-01-19 2001-01-19 Siloxy-substituted monocyclopentadienyl ligated constrained geometry olefin polymerisation catalysts

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0001232A GB0001232D0 (en) 2000-01-19 2000-01-19 Polymerisation catalysts
GB0001232.8 2000-01-19

Publications (1)

Publication Number Publication Date
WO2001053361A1 true WO2001053361A1 (en) 2001-07-26

Family

ID=9883980

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB2001/000203 WO2001053361A1 (en) 2000-01-19 2001-01-19 Siloxy-substituted monocyclopentadienyl ligated constrained geometry olefin polymerisation catalysts

Country Status (3)

Country Link
AU (1) AU2001228629A1 (en)
GB (1) GB0001232D0 (en)
WO (1) WO2001053361A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6906153B2 (en) 2001-01-31 2005-06-14 Borealis Technology Oy Dual-site olefin polymerization catalyst composition
US7141690B2 (en) 2002-02-08 2006-11-28 Sumitomo Chemical Company, Limited Transition metal complexes, ligands, polymerization catalysts for olefins, and process for production of olefin polymers
EP1739103A1 (en) * 2005-06-30 2007-01-03 Borealis Technology Oy Catalyst

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998006728A1 (en) * 1996-08-08 1998-02-19 The Dow Chemical Company 2-heteroatom substituted cyclopentadienyl-containing metal complexes and olefin polymerization process
WO1999061489A1 (en) * 1998-05-25 1999-12-02 Borealis Technology Oy Supported olefin polymerization catalyst composition

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998006728A1 (en) * 1996-08-08 1998-02-19 The Dow Chemical Company 2-heteroatom substituted cyclopentadienyl-containing metal complexes and olefin polymerization process
WO1999061489A1 (en) * 1998-05-25 1999-12-02 Borealis Technology Oy Supported olefin polymerization catalyst composition

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6906153B2 (en) 2001-01-31 2005-06-14 Borealis Technology Oy Dual-site olefin polymerization catalyst composition
US7141690B2 (en) 2002-02-08 2006-11-28 Sumitomo Chemical Company, Limited Transition metal complexes, ligands, polymerization catalysts for olefins, and process for production of olefin polymers
US7241927B2 (en) 2002-02-08 2007-07-10 Sumitomo Chemical Company, Limited Transition metal complexes, ligands, catalysts for olefin polymerization, and process for production of olefin polymers
EP1739103A1 (en) * 2005-06-30 2007-01-03 Borealis Technology Oy Catalyst
WO2007003378A3 (en) * 2005-06-30 2007-04-19 Borealis Tech Oy Catalyst

Also Published As

Publication number Publication date
AU2001228629A1 (en) 2001-07-31
GB0001232D0 (en) 2000-03-08

Similar Documents

Publication Publication Date Title
RU2062649C1 (en) METHOD FOR PRODUCTION OF CATALYST FOR POLYMERIZATION AND COPOLYMERIZATION OF α-OLEFINS
RU2165435C2 (en) Catalyst composition used for polymerization of olefins
EP0632063B1 (en) Bimetallic metallocene alumoxane catalyst system and its use in the preparation of ethylene copolymers
JP2994746B2 (en) Monocyclopentadienyl transition metal olefin polymerization catalyst
EP1401880B1 (en) Metallocene catalysts containing an indenyl moiety substituted at the 4-, 5-, 6- or 7-position by a siloxy or germyloxy group
WO2001070395A2 (en) Polymerization catalysts comprising an open eta-5 ligand
WO2003010208A1 (en) Metallocene catalysts containing a cyclopentadienyl ligand substituted by a siloxy or germiloxy group containing an olefinic residue
JP2002504485A (en) Catalytic activators containing extended anions
KR20010013769A (en) Catalyst activator
EP1322678A2 (en) A catalyst system and its use in a polymerization process
WO2000009523A1 (en) Ansa-group-4-metal bis (.mu.-substituted) aluminum complexes
AU784134B2 (en) Chemically-modified supports and supported catalyst systems prepared therefrom
JP2003128720A (en) Solid cocatalyst component for olefin polymerization, catalyst for olefin polymerization and ionic compound
US6831187B2 (en) Multimetallic catalyst compositions for the polymerization of olefins
US6815514B2 (en) Catalysts
WO2001053362A1 (en) Metallocene catalysts comprising monocyclic siloxy substituted cyclopentadienyl group(s) for the polymerisation of olefins
JP3850048B2 (en) Organic transition metal compound and method for producing polyolefin using the same
JP2001512141A (en) Zwitterionic catalytic activator
WO2002102857A2 (en) Catalyst system and its use in a polymerization process
AU2002324444A1 (en) Catalyst system and its use in a polymerization process
JP2001500106A (en) Heterocyclic complex and olefin polymerization method
US7129305B2 (en) Heterocyclic-amide catalyst compositions for the polymerization of olefins
WO2001053361A1 (en) Siloxy-substituted monocyclopentadienyl ligated constrained geometry olefin polymerisation catalysts
JP3302415B2 (en) Internal olefin polymerization catalyst and method for producing internal olefin polymer
ES2351298T3 (en) METALOGEN CATALYSTS CONTAINING AN INDENILE REST REPLACED IN THE POSITION 4-, 5-, 6- OR 7-, WITH A SILOXI OR GERMILOXI GROUP.

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AT AU AZ BA BB BG BR BY BZ CA CH CN CR CU CZ CZ DE DE DK DK DM DZ EE EE ES FI FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ PL PT RO RU SD SE SG SI SK SK SL TJ TM TR TT TZ UA UG US UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP