WO2001053361A1 - Catalyseurs de polymerisation d'olefines a geometrie contrainte ligatures au monocyclopentadienyle a substitution siloxy - Google Patents

Catalyseurs de polymerisation d'olefines a geometrie contrainte ligatures au monocyclopentadienyle a substitution siloxy Download PDF

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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
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group
compound
ring
transition metal
metallocene
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PCT/GB2001/000203
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English (en)
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Ove Andell
Janne Maaranen
Lasse Ketola
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Borealis Technology Oy
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Priority to AU2001228629A priority Critical patent/AU2001228629A1/en
Publication of WO2001053361A1 publication Critical patent/WO2001053361A1/fr

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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
    • 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:

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Abstract

L'invention concerne un composé procatalytique metallocène comprenant un groupe 3 à 7 de métal de transition ligaturé θ et σ par un groupe cyclopentadiényle monocyclique, homocyclique ou hétérocyclique à substitution siloxy. De tels composés peuvent être utilisés avec un cocatalyseur, c.-à-d. un alumoxane, pour la polymérisation d'oléfines.
PCT/GB2001/000203 2000-01-19 2001-01-19 Catalyseurs de polymerisation d'olefines a geometrie contrainte ligatures au monocyclopentadienyle a substitution siloxy WO2001053361A1 (fr)

Priority Applications (1)

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AU2001228629A AU2001228629A1 (en) 2000-01-19 2001-01-19 Siloxy-substituted monocyclopentadienyl ligated constrained geometry olefin polymerisation catalysts

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GB0001232A GB0001232D0 (en) 2000-01-19 2000-01-19 Polymerisation catalysts
GB0001232.8 2000-01-19

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WO2001053361A1 true WO2001053361A1 (fr) 2001-07-26

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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 (fr) * 2005-06-30 2007-01-03 Borealis Technology Oy Catalyseur

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998006728A1 (fr) * 1996-08-08 1998-02-19 The Dow Chemical Company Complexes metalliques contenant du cyclopentadienyle a substitution d'heteroatome en position 2 et procede de polymerisation d'olefine
WO1999061489A1 (fr) * 1998-05-25 1999-12-02 Borealis Technology Oy Composition de catalyseur de polymerisation olefinique sur support

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998006728A1 (fr) * 1996-08-08 1998-02-19 The Dow Chemical Company Complexes metalliques contenant du cyclopentadienyle a substitution d'heteroatome en position 2 et procede de polymerisation d'olefine
WO1999061489A1 (fr) * 1998-05-25 1999-12-02 Borealis Technology Oy Composition de catalyseur de polymerisation olefinique sur support

Cited By (6)

* 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 (fr) * 2005-06-30 2007-01-03 Borealis Technology Oy Catalyseur
WO2007003378A2 (fr) * 2005-06-30 2007-01-11 Borealis Technology Oy Catalyseur
WO2007003378A3 (fr) * 2005-06-30 2007-04-19 Borealis Tech Oy Catalyseur

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

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