WO2009013197A1 - Preparation of activating supports - Google Patents

Preparation of activating supports Download PDF

Info

Publication number
WO2009013197A1
WO2009013197A1 PCT/EP2008/059283 EP2008059283W WO2009013197A1 WO 2009013197 A1 WO2009013197 A1 WO 2009013197A1 EP 2008059283 W EP2008059283 W EP 2008059283W WO 2009013197 A1 WO2009013197 A1 WO 2009013197A1
Authority
WO
WIPO (PCT)
Prior art keywords
support
trimethylsilyl
activating
group
tri
Prior art date
Application number
PCT/EP2008/059283
Other languages
French (fr)
Inventor
Abdelkrim El Kadib
Karine Molvinger
Daniel Brunel
Floran Prades
Sabine Sirol
Original Assignee
Total Petrochemicals Research Feluy
Centre National De La Recherche Scientifique (Cnrs)
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 Total Petrochemicals Research Feluy, Centre National De La Recherche Scientifique (Cnrs) filed Critical Total Petrochemicals Research Feluy
Priority to EP08786177A priority Critical patent/EP2170511A1/en
Priority to CN2008801003372A priority patent/CN101765461B/en
Priority to KR1020107001618A priority patent/KR101166400B1/en
Priority to US12/670,235 priority patent/US8394737B2/en
Publication of WO2009013197A1 publication Critical patent/WO2009013197A1/en

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
    • B01J31/1625—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups
    • B01J31/1633—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups covalent linkages via silicon containing groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • B01J31/146—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of boron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0209—Impregnation involving a reaction between the support and a fluid
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
    • C08F4/16—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen of silicon, germanium, tin, lead, titanium, zirconium or hafnium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/10—Polymerisation reactions involving at least dual use catalysts, e.g. for both oligomerisation and polymerisation
    • B01J2231/12—Olefin polymerisation or copolymerisation
    • B01J2231/122—Cationic (co)polymerisation, e.g. single-site or Ziegler-Natta type
    • 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
    • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not

Definitions

  • the present invention discloses the preparation of solid activating systems for the polymerisation of olefins.
  • the present invention relates to an activating support for immobilising metallocene or post-metallocene complexes, in order to promote heterogeneous polymerisation of ethylene and alpha-olefins .
  • catalysts are however not adapted to heterogeneous polymerisation, such as suspension or gas phase polymerisation. These processes offer many advantages, among others, they allow the preparation of a polymer in granular form having a defined particles size distribution.
  • That activating agent however also exhibits disadvantageous features such as superstoechiometric quantities of MAO ranging from MAO:catalyst precursor ratios of 10 2 :1 to 10 4 :1. Consequently, there is a great need to develop new activating agents that can either replace MAO or decrease its necessary quantities, (see for example E. Y.-X. Chen, T.J. Marks, "Cocatalysts for metal-catalyzed polymerization: Activators, Activation processes, and structure-activity relationships" in Chem. Rev., 100, 1391 -1434, 2000).
  • Nicholls "Base-free cationic 14-electron titanium and zirconium alkyls: in situ generation, solution structures, and olefin polymerization activity” in Angew. Chem. Int. Engl., 29, 780- 782, 1990 ; X. Yang, CL. Stern, T.J. Marks "Cation-Ike homogeneous olefin polymerization catalysts based upon zirconocene alkyls and tris- (pentafluorophenyl)borane" in J. Am. Chem. So ⁇ , 113, 3623-25, 1991 ; M. Bochmann, S.J.
  • Another goal of this invention is the preparation of heterogeneous olefin polymerisation catalytic systems having hardened catalyst grains for use in gas phase or slurry polymerisation processes and then to provide a method for preparing polymers having improved morphology, thereby reducing reactor fouling (see for example E. M. Carnahan, G. B. Jacobsen “Supported metallocene catalysts” CATTECH, in Kluwer Academic/Plenum Publishers, vol 4, n°1 , 74-88, 2000 ; G. Fink, B. Steinmetz, J. Zechlin, C. Przybyla,
  • the heterogeneisation can optionaly be performed by the covalent anchorage of the metallocene complexes on mineral oxide supports as described for example in EP-A- 293815, or in US-A-5262498, or in US-A-5688880, or in US-A-5854362, or in US-A- 5399636 or in H. G. Alt, P. Schertl, A. Koppl, "Polymerization of ethylene with metallocene/methylaluminoxane catalysts supported on polysiloxane microgels and silica.” in J. Organometal. Chem., 568, 263-269, 1998, or in M. Galan-Fereres, T. Koch, E. Hey-Hawkins, M.S.
  • the catalyst component can also be deposited on polymer supports as described for example in T. R. Boussie, C. Coutard, H. Turner, V. Murphy, T.S. Powers, "Solid- phase synthesis and encoding strategies for olefin polymerization catalyst libraries" in Angew. Chem. Int. Engl., 37, 3272-75, 1998 or in T.R. Boussie, V. Murphy, K.A. Hall,
  • Another strategy concerns the covalent anchorage of dimethyanilinium cations on polymeric support which had to be achieved in order to allow immobilisation of the perfluorinated borate anions by ionic linkage as described in WO 98/55518 and in US-A-6228795.
  • Kaneko and Sato (US-A-5807938) have anchored the p-trimethoxysily- (N,N-dimethylanilium) on a silica surface to afford an activated support for olefin polymerisation by addition of Li tetrakis(pentafluorophenyl)borate. They also claims the use of dimethyldimethoxysilane as co-grafting agent.
  • metals can be selected from aluminium, titanium, zirconium or nickel.
  • DMAF dimethylaluminium fluoride
  • the present invention relates to :
  • the present invention discloses a method for preparing an activating support that comprises the steps of: a) providing a support prepared from silica or from mixed mineral oxides based on silica; b) grafting on the surface of the support of step a) a mixture of silylating agents comprising a functional ised silylating agent of formula YsSi — L — NR' 2 wherein each R' is independently selected from alkyl, aryl, alkylaryl or arylalkyl, and a structurally similar non functionalised silylating agent Y 3 Si — L, said functional ised and non functionalised silylating agents being in a ratio ranging between 1 :1 and 1 :19 and wherein each Y is independently selected from alkoxy, halogen or hydrogen and wherein L is a rigid linker group, preferably an aromatic group and more preferably a phenyl group
  • step b) adding to the intermediate support of step b) a non-nucleophile trimethylsilylating agent selected from thmethylphenoxysilane, phenyldimethylphenoxysilane, hexamethyldisiloxane, 1 ,1 ,3,3- tetramethyldisiloxane, trimethylsilyl methanesulfonate, trimethylsilyl trifluoromethanesulfonate, thmethylsilyl-p-toluenesulfonate, hexamethyldisilazane, N,N-bis(trimethylsilyl) urea, N,O-bis(thmethylsilyl) acetamide, N-trimethylsilyl acetamide, N-methyl-N- trimethylsilyltrifluoroacetamide, N-trimethylsilylimidazole, N- trimethylsilylthiazole, N-trimethylsilyloxazole or thalkylhalogens
  • step d) protonating the intermediate amine-grafted supports of step c) with an acid AH in order to form the protonated intermediate supports
  • A is triflate CF 3 SO 2 O (OTf) or halogen
  • step d) adding a borate or aluminate XM to the intermediate support of step d) wherein X is Al- or B-containing activating group and M is a metal Group 1 of the Periodic Table, in order to provide activating support S ac t
  • the present invention discloses a method for preparing an activating support that comprises the steps of: a) providing a support prepared from silica or from mixed mineral oxides based on silica; b) grafting on the surface of the support of step a) a mixture of silylating agents comprising a functional ised silylating agent of formula YsSi — L — CH 2 — Z and a structurally similar non functionalised silylating agent Y 3 Si — L, said functionalised and non functionalised silylating agents being in a ratio ranging between 1 :1 and 1 :19 and wherein each Y is independently selected from alkoxy, halogen or hydrogen, L is a rigid linker group and Z is a leaving group, in order to prepare modified support
  • step b) adding to the modified support of step b) a non-nucleophile trimethylsilylating agent selected from trimethylphenoxysilane, phenyldimethylphenoxysilane, hexamethyldisiloxane, 1 ,1 ,3,3-tetramethyldisiloxane, trimethylsilyl methanesulfonate, trimethylsilyl trifluoromethanesulfonate, trimethylsilyl-p- toluenesulfonate, hexamethyldisilazane, N,N-bis(thmethylsilyl) urea, N 1 O- bis(thmethylsilyl) acetamide, N-trimethylsilyl acetamide, N-methyl-N- trimethylsilyltrifluoroacetamide, N-trimethylsilylimidazole, N-trimethylsilylthiazole, N-trimethylsilyloxazole or trialkylhalogensilanes such
  • step a) adding to the passivated support of step c) a secondary amine of formula
  • R is alkyl group having from 1 to 6 carbon atoms or substituted or unsubstituted aryl group and Ar is substituted or unsubstituted aryl group, in order to provide intermediate support
  • A is triflate CF 3 SO 2 O (OTf) or halogen; f) adding a borate or aluminate XM to the intermediate support of step d) wherein X is Al- or B-containing activating group and M is a metal Group 1 of the Periodic Table, in order to provide activating support S ac t
  • the support is preferably selected from SiO 2 , SiO 2 / AI 2 O 3 , SiO 2 / TiO 2 , SiO 2 / ZrO 2 , SiO 2 / LnO x wherein Ln stands for lanthanides.
  • R' is alkyl group having from 1 to 6 carbon atoms or aryl group. More preferably, R' is methyl, butyl or phenyl. Most preferably it is phenyl.
  • At least one of R' and L must be aryl group.
  • Leaving group Z is preferably selected from halogen, paratoluenesulfonate, triflate and diazonium.
  • X is preferably selected from tetrakis-(pentafluoroaryl)borate or tetrakis- (pentafluoroaryl)aluminate.
  • M is lithium.
  • the support can also be modified in order to tailor its characteristics such as its specific surface area, its pore volume, its acidity or its hydrophobic or hydrophilic character.
  • the method for preparing an activating support comprises the steps of: a) providing a support selected from Si ⁇ 2, SiO 2 / AI2O3, SiO 2 / TiO 2 , SiO 2 / ZrO 2 , SiO 2 / LnO x ; b) grafting on the surface of the support of step a) a mixture of para- aminophenylsilane and of phenylsilane chains in a ratio ranging from 1 :1 to 1 :19; c) N-alkylating the amino-groups of the support of step b) in order to prepare an intermediate support bearing grafted para- ⁇ /, ⁇ /-dialkyl-aminophenylsilane and phenylsilane in a ratio ranging from 1 :1 to 1 :19
  • step c) adding to the intermediate support of step c) a trimethylsilylating agent such as for example trimethylsilylimidazole or hexamethyldisilazane
  • a trimethylsilylating agent such as for example trimethylsilylimidazole or hexamethyldisilazane
  • the amount of trimethylsilylating agent is selected to provide at least 5 equivalents of silanol with respect to silanol present in starting silica-based support; e) prtonating the intermediate amine grafted support of step d) with an acid AH to
  • A is Otf or halogen; f) adding a borate or aluminate XM to the intermediate supports of step e) wherein X is an activating group containing Al " or B " , and M is a metal Group 1 of the Periodic Table, in order to provide activating support
  • the method for preparing an activating support comprises the steps of: a) providing a support selected from SiO 2 , SiO 2 / AI 2 O 3 , SiO 2 / TiO 2 , SiO 2 / ZrO 2 , SiO 2 / LnO x ; b) grafting on the surface of the support of step a) a functionalised silylating agent of formula (RO) 3 Si — Ar — CH 2 — X or a mixture of silylating agents comprising a functionalised silylating agent of formula (RO) 3 Si — Ar — CH 2 — X and a structurally similar non functionalised silylating agent (RO) 3 Si — Ar, being in a ratio ranging between 1 :1 and 1 :19 and wherein OR is an alkoxy group, Ar is an aromatic group, preferably a phenyl ring and X is an halogen, in order to prepare modified support
  • step e) adding to the modified supports of step e) a non-nucleophile trimethylsilylating agent of formula
  • step a) wherein the amount of trimethylsilylating agent is selected to provide at least 5 equivalents of silanol with respect to silanol present in the starting silica- based support of step a);
  • R is alkyl group having from 1 to 6 carbon atoms or substituted or unsubstituted aryl group, preferably an alkyl group and Ar is an aromatic group in order to provide intermediate supports
  • A is OTf or halogen
  • step e) adding a borate or aluminate: XM to the intermediate supports of step e) wherein X is an activating group containing Al " or B " , and M is a metal Group 1 of the Periodic Table, in order to provide activating support
  • the present invention also discloses the activating supports obtainable by the method of the present invention.
  • metallocene or late transition metal complex catalyst components prepared by any method known in the art can be deposited on the activating support of the present invention in order to provide active catalyst systems without addition of conventional activating agents such as aluminoxanes or boron- based compounds.
  • Preferred metallocene catalyst components according to the present invention include compounds based on bridged bisindenyl, bistetrahydroindenyl or cyclopentadienyl-fluorenyl ligands. The metallocene catalyst component must be fully alkylated.
  • Late transition metal complexes of the present invention preferably include ⁇ -diimine Ni complexes as disclosed by Brookhart in WO96/ 23010 or bis(imino)pyridyl Iron(ll) or Cobalt(ll) complexes as disclosed by Bristovsek et al. (GJ. P.
  • Late transition components must also be fully alkylated. If not an alkylating agent such as aluninium alkyl must be added in order alkylate the compound.
  • the present invention thus discloses a method for preparing an active catalyst system by the steps of: a) providing an activating support as described hereabove; b) impregnating a fully alkylated metallocene or post-metallocene catalyst component onto the activating support; c) optionally adding a scavenger; d) retrieving an active catalyst system.
  • the scavenger is an aluminium alkyl. It is preferably selected from thisobutyl aluminium (TIBAL), thethylaluminium (TEAL) or thmethylaluminium.
  • the active catalyst systems of the present invention are used for the oligomerisation or the homo- or co-polymerisation of ethylene and alpha-olefins. They have the advantage of being very efficient without the need to add costly and dangerous material such as methylaluminoxane.
  • the present invention thus discloses a method for oligomehsing or homo- or co- polymerising that comprises the steps of: a) injecting the active catalyst system of the present invention into the reactor; b) injecting the monomer and optional comonomer simultaneously with or after the catalyst system; c) optionally injecting a scavenger; d) maintaining under polymerization conditions; e) retrieving a polymer.
  • the monomer is preferably ethylene or propylene.
  • the comonomer is preferably ethylene, propylene or 1 -hexene.
  • the starting silica support used in all examples was from Grace Davison (G5H, Surface area: 513 m 2 .g "1 ; porous volume : 1.8 mL.g "1 Supported ammonium.
  • Example 1 preparation of sample (AEiP-A/B) or grafting para- aminophenylthmethoxysilane on silica.
  • the first step was the anchoring of paraaminophenyltrimethoxysilane (4.43 g, 0.02 mol) on activated silica. It was carried out under toluene reflux (60 0 C for 6h and 120 0 C for 1 h) and the reaction was catalysed by a ternary system consisting of water (373 ⁇ l_), paratoluene sulfonic acid (195.88 mg) and ammonium fluoride
  • the fourth step was the quaternisation of the resulting tertiary amines by protonation with trifluoromethane sulfonic acid.
  • 300 mg of prepared material were activated under vacuum at room temperature for 2 hours.
  • Toluene (8 ml_) was then added.
  • the suspension was stirred for 10 mn and a solution of trifluoromethanesulfonic acid (150 ⁇ l_ diluted in 2 ml_ of toluene) was added.
  • the mixture was stirred at room temperature for 24 hours.
  • the solution was filtered, washed several times with toluene, and tetrahydrofurane (THF). The material was dried for 2 hours.
  • the fifth step was the introduction of the borate group: it was carried out by exchange reaction with OSO 2 CF 3 (OTf) anion.
  • Compound B(C 6 Fs) 4 Li was synthetised by reacting C 6 F 5 Li (138 ⁇ l_, 1.26 mmol) with B(C 6 Fs) 3 (0.65g, 1.26 mmol). It was then reacted with R 3 N + H, OTf to form R 3 N + H, B(C 6 F 5 ) 4 with release of LiOTf.
  • the resulting material was analysed and had the following properties: SBET : 1 18 m 2 /g.
  • ATG 1.93 % (H 2 O) ; 37.06 % (organic moieties) ; 60.59 % (SiO 2 ).
  • Example 2 preparation of sample (AE?P-A/B) or grafting and dispersing para- aminophenyltrimethoxysilane on silica.
  • AE2P-A/B preparation of sample (AE 3 P-AZB) or grafting and paramethylchlorophenylthmethoxysilane on silica.
  • the silanols were passivated by reaction with N 1 O- bistrimethylsilyltrifluoroacetamide that was selected because it was not very nucleophile and thus not likely to initiate the substitution of chlorine.
  • 5.75 g of the material prepared in the first step were heated at a temperature of 150°C for a period of time of 16h. 60 ml_ of toluene were then added. After stirring for 15 minutes, N, O- bis(trimethylsilyl)trifluoroacetamide (4.40 ml_) was introduced dropwise as silylating agent.
  • N-methylaniline (5.4 ml_) was first synthetised. It was then mixed with thethylamine (5.4 ml_) and added to a suspension of activated chlorobenzene supported silica (5.44 g of activated support in 50 ml_ of toluene). The mixture was heated at a temperature of 80 0 C for a period of time of 36h. The nucleophilic reaction between secondary amine and chloride as leaving group resulted in the formation of the corresponding tertiary amine with elimination of HCI. The latter was then neutralised with thethylamine leading precipitation of chlorhydrate.
  • the tertiary amines were quaternised by protonation with trifluoromethane sulfonic acid (HOTf).
  • HATf trifluoromethane sulfonic acid
  • the tertiary amino supported silica 1.5 g was activated under vacuum at room temperature for 3 hours and toluene (20 ml_) was then added.
  • a solution of thfluoromethanesulfonic acid (0.45 ml_) in 5 ml_ of toluene was added dropwise. The mixture was stirred for 24 hours at room temperature.
  • the solution was filtered and washed with toluene and tetrahydrofurane.
  • the material was then dried under vacuum for 4 hours.
  • Example 4 preparation of sample (AE 4 P-AZB) or grafting and dispersing paramethylchlorophenyltrimethoxysilane on silica.
  • the activating supports of examples 1 to 4 were used to polymerise ethylene under the following conditions, using a metallocene complex: SPEC Solvent: 20 ml_ of heptane Scavenger: 1 ml_ of triisobutylaluminiunn (TIBAL)

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

The present invention discloses a method for preparing an activating support and its use to activate metallocene or post-metallocene catalyst component for use in the oligomerisation and polymerisation of ethylene and alpha-olefins.

Description

PREPARATION OF ACTIVATING SUPPORTS.
The present invention discloses the preparation of solid activating systems for the polymerisation of olefins. Particularly, the present invention relates to an activating support for immobilising metallocene or post-metallocene complexes, in order to promote heterogeneous polymerisation of ethylene and alpha-olefins .
The polymerisation of olefins in the presence of single site complexes has mostly been described in homogeneous catalysis. In that type of polymerisation, the catalyst, the olefin monomer and the resulting polymer are all present in the same liquid phase, typically a solvent.
These catalysts are however not adapted to heterogeneous polymerisation, such as suspension or gas phase polymerisation. These processes offer many advantages, among others, they allow the preparation of a polymer in granular form having a defined particles size distribution.
It is known in the art of homogeneous olefin polymerisation catalysis to use metallocene complexes or α-diimine or 2,6-bis(imino)pyridyl complexes of latetransition metal in combination with a selected activator. The most commonly used activating agent is alkylaluminoxane and most preferably methylaluminoxane (MAO) as it promotes high catalytic activity (see for example H. Sinn, W. Kaminsky, H.J. Wollmer, R. Woldt, "Living polymers" with Ziegler catalysts of high productivity. "in Angew. Chem, 92, 396-402, 1980). That activating agent however also exhibits disadvantageous features such as superstoechiometric quantities of MAO ranging from MAO:catalyst precursor ratios of 102 :1 to 104:1. Consequently, there is a great need to develop new activating agents that can either replace MAO or decrease its necessary quantities, (see for example E. Y.-X. Chen, T.J. Marks, "Cocatalysts for metal-catalyzed polymerization: Activators, Activation processes, and structure-activity relationships" in Chem. Rev., 100, 1391 -1434, 2000). It has now been found that the propylene polymerisation activity of rac- ethylenebis(indenyl)methylzirconium cation stabilised by tetrakis(pentafluorophenyl)borate anion through reaction of rac- ethylenebis(indenyl)dimethylzirconium with trityl tetrakis(pentafluorophenyl)borate in the ratio 1 :1 was six times greater than the activity of ethylenebis(indenyl)dichlorozirconium :MAO system with a ratio 1 :2500 (J.C.W. Chien, W.M. Tsai, M. D. Rausch, "Isospecific polymerization of propylene catalyzed by rac-ethylenebis(indenyl)methylzirconium cation." J. Am. Chem. Soα, 113, 8570-1 , 1991 ). In addition, it has a highest stereospecificity. The use of borane-based organic Lewis acid to activate metallocenes as polymerisation catalysts in homogeneous conditions has been studied by several groups, particularly to elucidate mechanism of arene -metal coordination (M. Bochman, A.J. Jaggar, J. C. Nicholls, "Base-free cationic 14-electron titanium and zirconium alkyls: in situ generation, solution structures, and olefin polymerization activity" in Angew. Chem. Int. Engl., 29, 780- 782, 1990 ; X. Yang, CL. Stern, T.J. Marks "Cation-Ike homogeneous olefin polymerization catalysts based upon zirconocene alkyls and tris- (pentafluorophenyl)borane" in J. Am. Chem. Soα, 113, 3623-25, 1991 ; M. Bochmann, S.J. Lancaster "Base-free cationic 14-electron alkyls of Ti, Zr and Hf as polymerisation catalysts: a comparison" in J. Organometallic Chem., 434, C1 -C5, 1992 ; L. Jia, X. Yang, CL. Stern, T.J. Marks, "Cationic metallocene polymerization catalysts based on tetrakis(pentafluorophenyl)borate and its derivatives. Probing the limits of anion "noncoordination" via a synthetic, solution dynamic, structural, and catalytic olefin polymerization study" in Organometallics, 16, 842-57, 1997 ; M. Vathauer, W. Kaminsky "Extremely active polymerizations of propene by bi- indenylzirconocenes and tetra(pentafluorophenyl)-borate" in Polymer, 42, 4017-24, 2001 ; M.J. Drewitt, M. Niedermann, R. Kumar, M. C. Baird " A study of representative alcohol, alkoxide, thiol and thiolate complexes of B(CeFs)3; their roles as activators of zirconocene olefin polymerization initiators" in Inorg. Chimica Acta, 335, 43-51 , 2002). The question of dormant sites has also been addressed (see for example CL. Landis, D. R. Sillars, J. M. Batterton, "Reactivity of secondary metallocene alkyls and the question of dormant sites in catalytic alkene polymerization" in J. Am. Chem. Soα, 126, 8890-91 , 2004). It has been shown that the active (Cp2 alkylmetal)+ species was directly formed by reaction of Cp2dialkylmetal not only with B(CeFs)3 or [CPh3]+ " [B(C6Fs)4], but also with [HNMe2Ph]+ [BPh4] (see for example the publications of Bochman et al. already cited hereabove). Another goal of this invention is the preparation of heterogeneous olefin polymerisation catalytic systems having hardened catalyst grains for use in gas phase or slurry polymerisation processes and then to provide a method for preparing polymers having improved morphology, thereby reducing reactor fouling (see for example E. M. Carnahan, G. B. Jacobsen "Supported metallocene catalysts" CATTECH, in Kluwer Academic/Plenum Publishers, vol 4, n°1 , 74-88, 2000 ; G. Fink, B. Steinmetz, J. Zechlin, C. Przybyla,
B. Tesche, "Propene polymerization with silica-supported metallocene/MAO catalysts", in Chem. Rev., 100, 1377- 90, 2000).
The heterogeneisation can optionaly be performed by the covalent anchorage of the metallocene complexes on mineral oxide supports as described for example in EP-A- 293815, or in US-A-5262498, or in US-A-5688880, or in US-A-5854362, or in US-A- 5399636 or in H. G. Alt, P. Schertl, A. Koppl, "Polymerization of ethylene with metallocene/methylaluminoxane catalysts supported on polysiloxane microgels and silica." in J. Organometal. Chem., 568, 263-269, 1998, or in M. Galan-Fereres, T. Koch, E. Hey-Hawkins, M.S. Eisen, Moris, "Synthesis and olefin polymerization using supported and non-supported geometry constrained titanium complexes." in J. Organometal. Chem. 580, 145-155, 1999. Similarly, the anchorage of post- metallocene complexes on mineral oxides has been disclosed for example in P. Preishuber-Pflugl, M. Brookhart, "Highly active supported nickel diimine catalysts for polymerization of ethylene" in Macromolecules, 35, 6074-6076, 2002, or in F.A.R. Kaul, GT. Puchta, H. Schneider, F. Bielert, D. Mihalios, W.A. Herrmann, " Immobilization of bis(imino)pyridyliron(ll) complexes on silica." In Organometallics, 74-82, 2002, or in I. Kim, B. H. Han, C-S. Ha, J.-K. Kim, H. Suh, "Preparation of Silica-Supported Bis(imino)pyhdyl Iron(ll) and Cobalt(ll) Catalysts for Ethylene Polymerization". In Macromolecules, 36, 6689-6691 , 2003.
The catalyst component can also be deposited on polymer supports as described for example in T. R. Boussie, C. Coutard, H. Turner, V. Murphy, T.S. Powers, "Solid- phase synthesis and encoding strategies for olefin polymerization catalyst libraries" in Angew. Chem. Int. Engl., 37, 3272-75, 1998 or in T.R. Boussie, V. Murphy, K.A. Hall,
C. Coutard, C. Dales, M. Petro, E. Carlson, H. W. Turner, T.S. Powers, "Parallel solid-phase synthesis, screening and encoding strategies for olefin polymerization catalysts" in Tetrahedron, 55, 11699-710, 1999 or in C. Liu, G. Jin, "Polymer- incorporated iron catalysts for ethylene polymerization-a new approach to immobilize iron olefin catalysts on polystyrene chains." in New J. Chem., 26, 1485-1489, 2002. Another strategy concerns the covalent anchorage of dimethyanilinium cations on polymeric support which had to be achieved in order to allow immobilisation of the perfluorinated borate anions by ionic linkage as described in WO 98/55518 and in US-A-6228795.
In parallel, Kaneko and Sato (US-A-5807938) have anchored the p-trimethoxysily- (N,N-dimethylanilium) on a silica surface to afford an activated support for olefin polymerisation by addition of Li tetrakis(pentafluorophenyl)borate. They also claims the use of dimethyldimethoxysilane as co-grafting agent.
These catalytic systems using supported activators are less active than equivalent homogeneous systems and the polymer properties are thereby degraded.
A new generation of solid activating supports has been developed and is described for example in Marks (J. Am. Chem. Soα, 120, 13533, 1998): it concerns sulfated zircone particles or also by McDaniel (WO-9960033, WO-0123433, WO-0123434, WO-0144309, WO-0149747 et US-A-6548441 ) or by Saudemont (FR-A-2765225). All these activators are solids having surface acid sites that are responsible for the activation.
These acid sites are metals combined with halides such as fluor or chlorine; metals can be selected from aluminium, titanium, zirconium or nickel.
The equivalent species in homogeneous catalysis are very poor activating species.
Compounds such as dimethylaluminium fluoride (DMAF) are used as activators in combination with thethylaluminium for the stereospecific polymerisation of propylene with compounds of the metallocene family with low productivity as described by Zambelli (Macromolecules 1989, 22, 2186). They do not activate metallocene complexes.
There is thus a need to develop new activating supports efficient in producing active single site catalyst systems and that do not require the use of methylaluminoxane. It is an aim of the present invention to prepare new species of activating support.
It is another aim of the present invention to prepare very active single site supported catalyst systems that do not require the use of methylaluminoxane.
It is also an aim of the present invention to prepare polymers that have regular grain size.
Any one of these aims is at least partially fulfilled by the present invention.
The present invention relates to :
1 - the dilution of the grafted p-N- dialkylanilinium silane with phenylsilane as dispersing agent .
2- other modes of anchorage of different derivatives of anilinium cations on silica surface with optional dispersion and residual silanol passivation.
Accordingly, in a first embodiment, the present invention discloses a method for preparing an activating support that comprises the steps of: a) providing a support prepared from silica or from mixed mineral oxides based on silica; b) grafting on the surface of the support of step a) a mixture of silylating agents comprising a functional ised silylating agent of formula YsSi — L — NR'2 wherein each R' is independently selected from alkyl, aryl, alkylaryl or arylalkyl, and a structurally similar non functionalised silylating agent Y3Si — L, said functional ised and non functionalised silylating agents being in a ratio ranging between 1 :1 and 1 :19 and wherein each Y is independently selected from alkoxy, halogen or hydrogen and wherein L is a rigid linker group, preferably an aromatic group and more preferably a phenyl group
Figure imgf000007_0001
c) adding to the intermediate support of step b) a non-nucleophile trimethylsilylating agent selected from thmethylphenoxysilane, phenyldimethylphenoxysilane, hexamethyldisiloxane, 1 ,1 ,3,3- tetramethyldisiloxane, trimethylsilyl methanesulfonate, trimethylsilyl trifluoromethanesulfonate, thmethylsilyl-p-toluenesulfonate, hexamethyldisilazane, N,N-bis(trimethylsilyl) urea, N,O-bis(thmethylsilyl) acetamide, N-trimethylsilyl acetamide, N-methyl-N- trimethylsilyltrifluoroacetamide, N-trimethylsilylimidazole, N- trimethylsilylthiazole, N-trimethylsilyloxazole or thalkylhalogensilanes such as thmethylchlorosilane, triethylchlorosilane, tri-n-propylchlorosilane, tri-i- propylchlorosilane, tri-n-butylchlorosilane, tri-i-butylchlorosilane, tri-s- butylchlorosilane, t-butyldimethyl chlorosilane, cyclohexyldimethylchlorosilane, dicyclohexylmethylchlorosilane, thcyclohexylchlorosilane, phenyldimethylchlorosilane or N,O-bis(trimethylsilyl)trifluoroacetamide, preferably N,O-bis(trimethylsilyl)trifluoroacetamide in order to passivate the residual silanol or silane-silanol groups leading to intermediate support S
Figure imgf000007_0002
d) protonating the intermediate amine-grafted supports of step c) with an acid AH in order to form the protonated intermediate supports
Figure imgf000008_0001
wherein A is triflate CF3SO2O (OTf) or halogen;
e) adding a borate or aluminate XM to the intermediate support of step d) wherein X is Al- or B-containing activating group and M is a metal Group 1 of the Periodic Table, in order to provide activating support Sact
Figure imgf000008_0002
with release of MA
f) retrieving an activating support.
In a second embodiment, the present invention discloses a method for preparing an activating support that comprises the steps of: a) providing a support prepared from silica or from mixed mineral oxides based on silica; b) grafting on the surface of the support of step a) a mixture of silylating agents comprising a functional ised silylating agent of formula YsSi — L — CH2 — Z and a structurally similar non functionalised silylating agent Y3Si — L, said functionalised and non functionalised silylating agents being in a ratio ranging between 1 :1 and 1 :19 and wherein each Y is independently selected from alkoxy, halogen or hydrogen, L is a rigid linker group and Z is a leaving group, in order to prepare modified support
Figure imgf000009_0001
c) adding to the modified support of step b) a non-nucleophile trimethylsilylating agent selected from trimethylphenoxysilane, phenyldimethylphenoxysilane, hexamethyldisiloxane, 1 ,1 ,3,3-tetramethyldisiloxane, trimethylsilyl methanesulfonate, trimethylsilyl trifluoromethanesulfonate, trimethylsilyl-p- toluenesulfonate, hexamethyldisilazane, N,N-bis(thmethylsilyl) urea, N1O- bis(thmethylsilyl) acetamide, N-trimethylsilyl acetamide, N-methyl-N- trimethylsilyltrifluoroacetamide, N-trimethylsilylimidazole, N-trimethylsilylthiazole, N-trimethylsilyloxazole or trialkylhalogensilanes such as trimethylchlorosilane, triethylchlorosilane, tri-n-propylchlorosilane, tri-i-propylchlorosilane, tri-n- butylchlorosilane, tri-i-butylchlorosilane, tri-s-butylchlorosilane, t-butyldimethyl chlorosilane, cyclohexyldimethylchlorosilane, dicyclohexylmethylchlorosilane, tricyclohexylchlorosilane, phenyldimethylchlorosilane or N1O- bis(trimethylsilyl)trifluoroacetamide, preferably N1O- bis(trimethylsilyl)trifluoroacetamide of formula
Figure imgf000009_0002
to passivate the residual silanol or silane-silanol groups leading to intermediate support
Figure imgf000009_0003
with release of CF3-C(O)NH2 and wherein the amount of thmethylsilylating agent is selected to provide at least 5 equivalents of silanol with respect to the silanol present in the starting silica- based support of step a); d) adding to the passivated support of step c) a secondary amine of formula
SN-Ar H
wherein R is alkyl group having from 1 to 6 carbon atoms or substituted or unsubstituted aryl group and Ar is substituted or unsubstituted aryl group, in order to provide intermediate support
Figure imgf000010_0001
with release of ZH d) protonating the intermediate amine-grafted supports of step c) with an acid AH in order to form the protonated intermediate supports
Figure imgf000010_0002
wherein A is triflate CF3SO2O (OTf) or halogen; f) adding a borate or aluminate XM to the intermediate support of step d) wherein X is Al- or B-containing activating group and M is a metal Group 1 of the Periodic Table, in order to provide activating support Sact
Figure imgf000011_0001
with release of MA g) retrieving an activating support.
The support is preferably selected from SiO2, SiO2/ AI2O3, SiO2/ TiO2 , SiO2/ ZrO2 , SiO2/ LnOx wherein Ln stands for lanthanides.
Preferably, R' is alkyl group having from 1 to 6 carbon atoms or aryl group. More preferably, R' is methyl, butyl or phenyl. Most preferably it is phenyl.
Linker group L is preferably phenyl group = -C6H4-
At least one of R' and L must be aryl group.
Leaving group Z is preferably selected from halogen, paratoluenesulfonate, triflate and diazonium.
X is preferably selected from tetrakis-(pentafluoroaryl)borate or tetrakis- (pentafluoroaryl)aluminate.
Preferably M is lithium. The support can also be modified in order to tailor its characteristics such as its specific surface area, its pore volume, its acidity or its hydrophobic or hydrophilic character.
Preferably, in the first embodiment according to the present invention the method for preparing an activating support comprises the steps of: a) providing a support selected from Siθ2, SiO2/ AI2O3, SiO2/ TiO2 , SiO2/ ZrO2 , SiO2/ LnOx; b) grafting on the surface of the support of step a) a mixture of para- aminophenylsilane and of phenylsilane chains in a ratio ranging from 1 :1 to 1 :19; c) N-alkylating the amino-groups of the support of step b) in order to prepare an intermediate support bearing grafted para-Λ/,Λ/-dialkyl-aminophenylsilane and phenylsilane in a ratio ranging from 1 :1 to 1 :19
Figure imgf000012_0001
d) adding to the intermediate support of step c) a trimethylsilylating agent such as for example trimethylsilylimidazole or hexamethyldisilazane
Figure imgf000012_0002
wherein the amount of trimethylsilylating agent is selected to provide at least 5 equivalents of silanol with respect to silanol present in starting silica-based support; e) prtonating the intermediate amine grafted support of step d) with an acid AH to
Figure imgf000012_0003
form the protonated intermediate support
wherein A is Otf or halogen; f) adding a borate or aluminate XM to the intermediate supports of step e) wherein X is an activating group containing Al" or B", and M is a metal Group 1 of the Periodic Table, in order to provide activating support
Figure imgf000013_0001
with release of MA; g) retrieving an activating support.
Preferably, in the second embodiment according to the present invention the method for preparing an activating support comprises the steps of: a) providing a support selected from SiO2, SiO2/ AI2O3, SiO2/ TiO2 , SiO2/ ZrO2 , SiO2/ LnOx; b) grafting on the surface of the support of step a) a functionalised silylating agent of formula (RO)3Si — Ar — CH2 — X or a mixture of silylating agents comprising a functionalised silylating agent of formula (RO)3Si — Ar — CH2 — X and a structurally similar non functionalised silylating agent (RO)3Si — Ar, being in a ratio ranging between 1 :1 and 1 :19 and wherein OR is an alkoxy group, Ar is an aromatic group, preferably a phenyl ring and X is an halogen, in order to prepare modified support
Figure imgf000013_0002
c) adding to the modified supports of step e) a non-nucleophile trimethylsilylating agent of formula
Figure imgf000014_0001
to provide passivated supports
Figure imgf000014_0002
wherein the amount of trimethylsilylating agent is selected to provide at least 5 equivalents of silanol with respect to silanol present in the starting silica- based support of step a);
d) adding to the passivated supports of step e) a secondary amine of formula
R.
N-Ar H
wherein R is alkyl group having from 1 to 6 carbon atoms or substituted or unsubstituted aryl group, preferably an alkyl group and Ar is an aromatic group in order to provide intermediate supports
Figure imgf000014_0003
e) protonating the intermediate amine-grafted supports of step d) with an acid AH to form protonate intermediate supports
Figure imgf000015_0001
wherein A is OTf or halogen
f) adding a borate or aluminate: XM to the intermediate supports of step e) wherein X is an activating group containing Al" or B" , and M is a metal Group 1 of the Periodic Table, in order to provide activating support
Figure imgf000015_0002
g) retrieving an activating support.
The present invention also discloses the activating supports obtainable by the method of the present invention.
These new activating supports are suitable for preparing catalyst systems based on single site catalyst components. Metallocene or late transition metal complex catalyst components prepared by any method known in the art can be deposited on the activating support of the present invention in order to provide active catalyst systems without addition of conventional activating agents such as aluminoxanes or boron- based compounds. Preferred metallocene catalyst components according to the present invention include compounds based on bridged bisindenyl, bistetrahydroindenyl or cyclopentadienyl-fluorenyl ligands. The metallocene catalyst component must be fully alkylated. Amongst the most preferred catalyst components, one can cite ethylene-bistetrahydroindenyl zirconium dimethyl, ethylene-(2-Me-4-t- But-cyclopentadienyl)(3-6,di-t-But-fluorenyl) zirconium dimethyl or ethylene-bis(2- Me,4-Ph-indenyl) zirconium dimethyl. Late transition metal complexes of the present invention preferably include α-diimine Ni complexes as disclosed by Brookhart in WO96/ 23010 or bis(imino)pyridyl Iron(ll) or Cobalt(ll) complexes as disclosed by Bristovsek et al. (GJ. P. Bhstovsek, V.C. Gibson, B.S. Kimberley, P.J. Maddox, S.J. Mc Tavish, G.A. Solan, A.J. P. White, D.J.J. Williams, in Chem. Commun., 849-50, 1998) or in Small et al. (B. L. Small, M. Brookhart, A.M.A. Bennett, in J. Am. Chem. Soα, 120, 4049, 1998). Late transition components must also be fully alkylated. If not an alkylating agent such as aluninium alkyl must be added in order alkylate the compound.
The present invention thus discloses a method for preparing an active catalyst system by the steps of: a) providing an activating support as described hereabove; b) impregnating a fully alkylated metallocene or post-metallocene catalyst component onto the activating support; c) optionally adding a scavenger; d) retrieving an active catalyst system.
The scavenger is an aluminium alkyl. It is preferably selected from thisobutyl aluminium (TIBAL), thethylaluminium (TEAL) or thmethylaluminium.
The active catalyst systems of the present invention are used for the oligomerisation or the homo- or co-polymerisation of ethylene and alpha-olefins. They have the advantage of being very efficient without the need to add costly and dangerous material such as methylaluminoxane.
The present invention thus discloses a method for oligomehsing or homo- or co- polymerising that comprises the steps of: a) injecting the active catalyst system of the present invention into the reactor; b) injecting the monomer and optional comonomer simultaneously with or after the catalyst system; c) optionally injecting a scavenger; d) maintaining under polymerization conditions; e) retrieving a polymer.
The monomer is preferably ethylene or propylene. The comonomer is preferably ethylene, propylene or 1 -hexene.
Examples.
The starting silica support used in all examples was from Grace Davison (G5H, Surface area: 513 m2.g"1 ; porous volume : 1.8 mL.g"1 Supported ammonium.
Example 1 : preparation of sample (AEiP-A/B) or grafting para- aminophenylthmethoxysilane on silica.
5g of Grace Davison were heated under vacuum at a temperature of 1500C for
24h. The first step was the anchoring of paraaminophenyltrimethoxysilane (4.43 g, 0.02 mol) on activated silica. It was carried out under toluene reflux (600C for 6h and 1200C for 1 h) and the reaction was catalysed by a ternary system consisting of water (373 μl_), paratoluene sulfonic acid (195.88 mg) and ammonium fluoride
(38.18 mg) in order to obtain a good and even surface coverage.
The textural properties of resulting hybrid material was analysed by nitrogen adsorption desorption (SBET= 296 m2/g). The amount of grafting organic was evaluated by TG analysis (4.18 10~3 mol/g).
The second step was the passivation of silanols: it was carried out by reaction of 6.43 g of the material obtained hereabove with 4.20 ml_ of trimethylsilylimidazole in 60 ml_ of toluene.The mixture was heated for a period of time of 16h at a temperature of 60°C. After filtration, the material was washed several times with toluene, methanol and diethyl ether and then treated with soxhlet extractor for 16hours. After heating for two hours, the material was analysed (SBET = 296 m2/g). The amount of grafting organic was evaluated by TG analysis (4.18 10~3 mol/g). SBET : 231 m2/g. TGA: 1.86 % (H2O) ; 23.15 % (organic part) ; 74.21 % (SiO2). The grafting of aromatic group and the passivation were evidenced by CP 13C NMR: 1.29 (SiMe3), 115.33, 136.15, 148.85 (aromatic carbon). The third step was the alkylation of primary amines: it was carried out by reaction of passivated material. 5.96 g were heated at a temperature of 1500C under vacuum before use and methanol (40 ml_) was added. After stirring for 5 mn, 36 g of paraformaldehyde (excess) were also added. The solution was heated for a period of time of 2 hours at a temperature of 65 0C. The mixture was then cooled at 00C. The addition of NaBH4 (11 g) was performed. The reaction was very exothermic. After stirring for a period of time of 12 hours, the solution was hydrolysed by addition of ice, filtered and washed with methanol, toluene and diethylether. The material was treated with soxhlet to remove the physisorbed compounds. Lastly, the material was dried at a temperature of 60°C for a period of time of 2 hours. The characteristics of the resulting material were as follows: SBET: 226 m2/g.
TG analysis : 3.86 % (H2O) ; 29.22 % (organic moieties) ; 66.19 % (Silica). 13C NMR : 1.21 (SiMe3), 52.33 (N(CH3)2), 1 14.12, 135.67, 148.73 (aromatic carbons )
The fourth step was the quaternisation of the resulting tertiary amines by protonation with trifluoromethane sulfonic acid. To perform this reaction, 300 mg of prepared material were activated under vacuum at room temperature for 2 hours. Toluene (8 ml_) was then added. The suspension was stirred for 10 mn and a solution of trifluoromethanesulfonic acid (150 μl_ diluted in 2 ml_ of toluene) was added. The mixture was stirred at room temperature for 24 hours. The solution was filtered, washed several times with toluene, and tetrahydrofurane (THF). The material was dried for 2 hours.
The fifth step was the introduction of the borate group: it was carried out by exchange reaction with OSO2CF3 (OTf) anion. Compound B(C6Fs)4Li was synthetised by reacting C6F5Li (138 μl_, 1.26 mmol) with B(C6Fs)3 (0.65g, 1.26 mmol). It was then reacted with R3N+H, OTf to form R3N+H, B(C6F5)4 with release of LiOTf. The resulting material was analysed and had the following properties: SBET : 1 18 m2/g. ATG : 1.93 % (H2O) ; 37.06 % (organic moieties) ; 60.59 % (SiO2).
13 C NMR: 0.59 (SiMe3); 48.23 (HN(CH3)2); 114.12, 135.67, 136.02, 137.72, 138.05, 139.68, 139.60, 147.95, 148.73 (aromatic carbons).
yde
Figure imgf000019_0001
AE1 P-A/B
Example 2: preparation of sample (AE?P-A/B) or grafting and dispersing para- aminophenyltrimethoxysilane on silica.
The procedure was the same as that disclosed in example 1 except that in the first step, para-aminophenyltrimethoxysilane and phenylthmethoxy silane were simultaneously added to the silica support in a ratio of 1 to 4 in order to separate the ammoniums.
Figure imgf000019_0002
AE2P-A/B Example 3: preparation of sample (AE3P-AZB) or grafting and paramethylchlorophenylthmethoxysilane on silica.
In the first step, starting from 5g of Grace Davison silica support activated at 1500C for 12h, anchoring of parabenzylthmethoxysilane chloride (4.48 ml_, 0.019 mol) was carried out under toluene ((600C for 6h and 120°C for 1 h) and the reaction was catalysed by a ternary system consisting of water (373 μl_), paratoluene sulfonic acid (195.88 mg) and ammonium fluoride (38.18 mg) in order to obtain a good and even surface coverage. The resulting material was then filtered and washed several times with toluene, methanol and diethylether. Finally, the material was dried at 1000C for 2h. The textural properties of resulting hybrid material were determined by nitrogen adsorption desorption (SBET= 413 m2/g). The amount of grafting organic was evaluated from TG analysis: 2.15% (H2O) ; 20.84 % ( organic moities) ; 77.01 % (SiO2).
In the second step, the silanols were passivated by reaction with N1O- bistrimethylsilyltrifluoroacetamide that was selected because it was not very nucleophile and thus not likely to initiate the substitution of chlorine. 5.75 g of the material prepared in the first step were heated at a temperature of 150°C for a period of time of 16h. 60 ml_ of toluene were then added. After stirring for 15 minutes, N, O- bis(trimethylsilyl)trifluoroacetamide (4.40 ml_) was introduced dropwise as silylating agent. The mixture was heated at a temperature of 60°C fo a period of time of 16h.Tthe solution was filtered and washed with toluene, methanol and diethylether. The material was treated with soxhlet extractor with 1 :1 of dichloromethane: diethylether for 16h. The solid was dried at a temperature of 1000C for a period of time of 2 hours. The textural and structural analyses were then performed. The results were as follows:
SBET : 368 m2/g. TG analysis: 0.97 % (H2O) ; 20.57 % (organic moieties) ; 77.72 % (SiO2). 13C NMR : 0.41 (SiMe3), 43.87 (CH2CI), 127.50, 134.42 (aromatic carbon).
In the third step, N-methylaniline (5.4 ml_) was first synthetised. It was then mixed with thethylamine (5.4 ml_) and added to a suspension of activated chlorobenzene supported silica (5.44 g of activated support in 50 ml_ of toluene). The mixture was heated at a temperature of 800C for a period of time of 36h. The nucleophilic reaction between secondary amine and chloride as leaving group resulted in the formation of the corresponding tertiary amine with elimination of HCI. The latter was then neutralised with thethylamine leading precipitation of chlorhydrate. The material was filtered and washed with toluene, methanol, dimethylformamide (to remove chlorhydrate from silica), pentane and diethylether. The solid was treated with soxhlet for 12hours. The obtained material was dried at a temperature of 1000C for a period of time of 2 hours and analysed. The results were as follows: SBET : 375 m2/g. TG analysis : 1.70 % (H2O) ; 22.35 % (organic moieties) ; 75.24 % (SiO2).
In the fourth step, the tertiary amines were quaternised by protonation with trifluoromethane sulfonic acid (HOTf). To perform this reaction, the tertiary amino supported silica (1.5 g) was activated under vacuum at room temperature for 3 hours and toluene (20 ml_) was then added. After stirring for 15 minutes, a solution of thfluoromethanesulfonic acid (0.45 ml_) in 5 ml_ of toluene was added dropwise. The mixture was stirred for 24 hours at room temperature. The solution was filtered and washed with toluene and tetrahydrofurane. The material was then dried under vacuum for 4 hours.
In the fifth step, the introduction of the borate group was carried out exactly as in example 1.
Figure imgf000022_0001
AE3P-A/B
Example 4: preparation of sample (AE4P-AZB) or grafting and dispersing paramethylchlorophenyltrimethoxysilane on silica.
The procedure was the same as that disclosed in example 3 except that in the first step, paramethylchlorophenyltrimethoxysilane and phenyltrimethoxy silane were simultaneously added to the silica support in a ratio of 1 to 4 in order to further separate the ammoniums.
Figure imgf000022_0002
AE4P-A/B
Polymerisation of ethylene.
The activating supports of examples 1 to 4 were used to polymerise ethylene under the following conditions, using a metallocene complex: SPEC Solvent: 20 ml_ of heptane Scavenger: 1 ml_ of triisobutylaluminiunn (TIBAL)
Pressure: 15 bars of ethylene
Temperature: 50 0C
Polymerisation time: 30 minutes
Stirring was carried out at 1000 rpm.
The polymerization results are displayed in Table I.
TABLE I.
Figure imgf000023_0001

Claims

CLAIMS. 23
1. A method for preparing an activating support that comprises the steps of: a) providing a support prepared from silica or from mixed mineral oxides based on silica; either b) grafting on the surface of the support of step a) a mixture of silylating agents comprising a functionalised silylating agent of formula Y3Si-L- NR'2 wherein each R' is independently selected from alkyl, aryl, alkylaryl or alkylaryl, and a structurally similar non functionalised silylating agent Y3Si — L, said functionalised and non functionalised silylating agents being in a ratio ranging between 1:1 and 1:19 and wherein each Y is independently selected from alkoxy, halogen or hydrogen, L is a rigid linker group and with the restriction that either L or R' is aryl group
Figure imgf000024_0001
c) adding to the intermediate support of step b) a non-nucleophile trimethylsilylating agent selected from trimethylphenoxysilane, phenyldimethylphenoxysilane, hexamethyldisiloxane, 1,1,3,3- tetramethyldisiloxane, trimethylsilyl methanesulfonate, trimethylsilyl trifluoromethanesulfonate, trimethylsilyl-p-toluenesulfonate, hexamethyldisilazane, N,N-bis(trimethylsilyl) urea, N,O-bis(trimethylsilyl) acetamide, N-trimethylsilyl acetamide, N-methyl-N- trimethylsilyltrifluoroacetamide, N-trimethylsilylimidazole, N- trimethylsilylthiazole, N-trimethylsilyloxazole or trialkylhalogensilanes such as trimethylchlorosilane, triethylchlorosilane, tri-n- propylchlorosilane, tri-i-propylchlorosilane, tri-n-butylchlorosilane, tri-i- butylchlorosilane, tri-s-butylchlorosilane, t-butyldimethyl chlorosilane, cyclohexyldimethylchlorosilane. dicyclohexylmethylchlorosilaoe,
RECTIFIED SHEET (RULE 91) ISA/EP tricyclohexylchlorosilane, phenyldimethylchlorosilane or N1O- . bis(trimethylsilyl)trifluoroacetamide, preferably N1O- bis(trimethylsilyl)trifluoroacetamide in order to passivate the residual silanol or silane-silanol groups leading to intermediate support S
Figure imgf000025_0001
d) protonating the intermediate amine-grafted supports of step c) with an acid AH in order to form the protonated intermediate supports
Figure imgf000025_0002
wherein A is triflate CF3SO2O (OTf) or halogen;
e) adding a borate or aluminate XM to the intermediate support of step d) wherein X is Al- or B-containing activating group and M is a metal Group 1 of the Periodic Table, in order to provide activating support Sact
Figure imgf000025_0003
with release of MA
f) retrieving an activating support.
2. A method for preparing an activating support that comprises the steps of:
RECTIFIED SHEET (RULE 91) ISA/EP a) providing a support prepared from silica or from mixed mineral oxides based on silica; b) grafting on the surface of the support of step a) a mixture of silylating agents comprising a functionalised silylating agent of formula Y3Si-L — CH2 — Z and a structurally similar non functionalised silylating agent Y3Si — L1 said functionalised and non functionalised silylating agents being in a ratio ranging between 1:1 and 1:19 and wherein each Y is independently selected from alkoxy, halogen or hydrogen, L is a rigid linker group and Z is a leaving group in order to prepare modified support
Figure imgf000026_0001
C) adding to the modified support of step d) a non-nucleophile trimethylsilylating agent selected from trimethylphenoxysilane, phenyldimethylphenoxysilane, hexamethyldisiloxane, 1 ,1 ,3,3-tetramethyldisiloxane, trimethylsilyl methanesulfonate, trimethylsilyl trifluoromethanesulfόnate, trimethylsilyl-p- toluenesulfonate, hexamethyldisilazane, N,N-bis(trimethylsilyl) urea, N1O- bis(trimethylsilyl) acetamide, N-trimethylsilyl acetamide, N-methyl-N- trimethylsilyltrifluoroacetamide, N-trimethylsilylimidazole, N- trimethylsilylthiazole, N-trimethylsilyloxazole or trialkylhalogensilanes such as trimethylchlorosilane, triethylchlorosilane, tri-n-propylchlorosilane, tri-i- propylchlorosilane, tri-n-butylchlorosilane, tri-i-butylchlorosilane, tri-s- butylchlorosilane, t-butyldimethyl chlorosilane, cyclohexyldimethylchlorosilane, dicyclohexylmethylchlorosilane, tricyclohexylchlorosilane, phenyldimethylchlorosϋane or N,0-bis(trimethylsilyl)trifluoroacetamide, preferably N,O-bis(trimethylsilyl)trifluoroacetamide in order to passivate the residual silanol or silane-sϋanol groups leading to intermediate support S in order to provide passivated support
Figure imgf000026_0002
RECTIFIED SHEET (RULE 91) ISA/EP with release of CF3-C(O)NH2 and wherein the amount of trimethylsilylating agent is selected to provide at least 5 equivalents of silanol with respect to silanol present in the starting silica-based support of step a);
d) adding to the passivated support of step e) a secondary amine of formula
Figure imgf000027_0001
wherein R is alkyl group having from 1 to 6 carbon atoms or substituted or unsubstituted aryl group and Ar is substituted or unsubstituted aryl group in order to provide intermediate support
Figure imgf000027_0002
e) protonating the intermediate amine-grafted supports of step d) with acid AH in order to form the protonated intermediate supports
Figure imgf000027_0003
wherein A is triflate (OTf) or halogen;
f) adding a borate or aluminate XM to the intermediate support of step g) wherein X is Al- or B-containing activating group and M is a metal Group 1 of the Periodic Table, in order to provide activating supports Sact
RECTIFIED SHEET (RULE 91) ISA/EP
Figure imgf000028_0001
g). retrieving activating supports
3. The method of claim 1 or claim 2 wherein linker group L is phenyl group -C6H4-.
4. The method of claim 2 or claim 3 wherein leaving group Z is selected from halogen, paratoluenesulfonate, triflate or diazonium.
5. The method of any one of claims 1 to 4 wherein X is selected from tetrakis- (pentafluoroaryl)borate or tetrakis-(pentafluoroaryl)aluminate.
6. The method of any one of the preceding claims wherein M is lithium.
7. The method of any one of the preceding claims wherein the support is selected from SiO2, SiO2Z AI2O3, SiO2/ TiO2 , SiO2/ ZrO2 , SiO2/ LnOx wherein Ln stands for lanthanides.
8. The method of any one of the preceding claims wherein the non-nucleophile trimethylsilylating agent is N,O-bis(trimethylsilyl)trifluoroacetamide.
9. An activating support obtainable by the method of any one of claims 1 to 8.
10. An active catalyst system comprising the activating support of claim 9 and one or more metallocene and/or post-metallocene component.
11. A method for preparing the active catalyst system of claim 10 that comprises the steps of: a) providing the activating support of any one of claims 1 to 8; b) impregnating a fully alkylated metallocene or post-metallocene catalyst component onto the activating support; c) optionally adding a scavenger;
RECTIFIED SHEET (RULE 91) ISA/EP d) retrieving an active catalyst system.
12. The method of claim 11 wherein the catalyst component is a metallocene component selected from ethylene-bistetrahydroindenyl zirconiumdimethyl.
13. The method of claim 12 or claim 13 wherein the scavenger is aluminium alkyl selected from trimethyl aluminium, triethyl aluminium or triisoutyl aluminium.
14. A method for oligomerising or homo- or co-polymerising ethylene and alpha-olefins that comprises the steps of a) injecting the active catalyst system of claim 9 into the reactor; b) injecting the monomer and optional comonomer simultaneously with or after the catalyst system; c) optionally injecting a scavenger; d) maintaining under polymerisation conditions; e) retrieving a polymer.
15. The method of claim 14 wherein the monomer is ethylene or propylene and the comonomer, if present, is ethylene, propylene or 1-hexene.
RECTIFIED SHEET (RULE 91) ISA/EP
PCT/EP2008/059283 2007-07-24 2008-07-16 Preparation of activating supports WO2009013197A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP08786177A EP2170511A1 (en) 2007-07-24 2008-07-16 Preparation of activating supports
CN2008801003372A CN101765461B (en) 2007-07-24 2008-07-16 Preparation of activating supports
KR1020107001618A KR101166400B1 (en) 2007-07-24 2008-07-16 Preparation of activating supports
US12/670,235 US8394737B2 (en) 2007-07-24 2008-07-16 Preparation of activating supports

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP07290930A EP2025403A1 (en) 2007-07-24 2007-07-24 Preparation of activating supports
EP07290930.2 2007-07-24

Publications (1)

Publication Number Publication Date
WO2009013197A1 true WO2009013197A1 (en) 2009-01-29

Family

ID=38846963

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2008/059283 WO2009013197A1 (en) 2007-07-24 2008-07-16 Preparation of activating supports

Country Status (5)

Country Link
US (1) US8394737B2 (en)
EP (2) EP2025403A1 (en)
KR (1) KR101166400B1 (en)
CN (1) CN101765461B (en)
WO (1) WO2009013197A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101845104A (en) * 2010-05-21 2010-09-29 北京化工大学 Olefin polymerization catalyst and preparation method thereof

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102875301B (en) * 2011-07-12 2015-06-10 中国石油化工股份有限公司 Method for catalytic dehydration of ethanol
CN104610480B (en) * 2013-11-05 2017-02-15 中国石油化工股份有限公司 Supported metallocene catalyst, preparation method and applications thereof
CN104610481B (en) * 2013-11-05 2017-02-15 中国石油化工股份有限公司 Supported metallocene catalyst for ethylene polymerization, preparation method and applications thereof
CN107556410A (en) * 2016-06-30 2018-01-09 中国石油化工股份有限公司 The preparation method of metallocene polypropylene catalyst
KR102214960B1 (en) * 2019-04-23 2021-02-10 효성화학 주식회사 Solid acids and manufacturing method of the same
JP2023103736A (en) * 2022-01-14 2023-07-27 ポリプラスチックス株式会社 Method for producing polyacetal polymer

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5834393A (en) * 1995-03-10 1998-11-10 The Dow Chemical Company Adduct of an organometal compound and a compatible anion, supported catalyst component supported catalyst processes for the preparation thereof
US20030088021A1 (en) * 1994-11-17 2003-05-08 The Dow Chemical Company High density ethylene homopolymers and blend compositions

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5643847A (en) * 1994-08-03 1997-07-01 Exxon Chemical Patents Inc. Supported ionic catalyst composition
FI970349A (en) * 1997-01-28 1998-07-29 Borealis As New activator systems for metallocene compounds

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030088021A1 (en) * 1994-11-17 2003-05-08 The Dow Chemical Company High density ethylene homopolymers and blend compositions
US5834393A (en) * 1995-03-10 1998-11-10 The Dow Chemical Company Adduct of an organometal compound and a compatible anion, supported catalyst component supported catalyst processes for the preparation thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
BOCHMANN M ET AL: "BASE-FREE CATIONIC 14-ELECTRON ALKYLS OF TI, ZR AND HF AS POLYMERISATION CATALYSTS: A COMPARISON", 1992, JOURNAL OF ORGANOMETALLIC CHEMISTRY, ELSEVIER-SEQUOIA S.A. LAUSANNE, CH, PAGE(S) C01-C05, ISSN: 0022-328X, XP001069148 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101845104A (en) * 2010-05-21 2010-09-29 北京化工大学 Olefin polymerization catalyst and preparation method thereof

Also Published As

Publication number Publication date
KR20100025005A (en) 2010-03-08
CN101765461B (en) 2012-09-05
KR101166400B1 (en) 2012-07-23
EP2170511A1 (en) 2010-04-07
US20110009582A1 (en) 2011-01-13
CN101765461A (en) 2010-06-30
US8394737B2 (en) 2013-03-12
EP2025403A1 (en) 2009-02-18

Similar Documents

Publication Publication Date Title
EP2683749B1 (en) Aluminoxane catalyst activators containing carbocation agents, and use thereof in polyolefin catalysts
US8394737B2 (en) Preparation of activating supports
JP3121838B2 (en) Supported ionic catalyst composition
PL186697B1 (en) Catalyst carrier supported components of a catalyst, supported catalyst, method of obtaining the both, polimerising process, complex compounds and production of them
WO2007106238A1 (en) Process for producing propylene copolymers
CN108264591B (en) Main catalyst of olefin polymerization catalyst, preparation method of main catalyst and olefin polymerization catalyst
AU784134B2 (en) Chemically-modified supports and supported catalyst systems prepared therefrom
JP2004504420A (en) Catalyst systems and their use in polymerization processes
JP2002519359A (en) Metal complexes containing one or more silsesquioxane ligands
WO2001036497A1 (en) Supported organometallic catalysts and their use in olefin polymerization
WO2007076398A2 (en) Catalyst activators, processes for making same, and use thereof in catalysts and polymerization of olefins
US20230151126A1 (en) Attenuated post-metallocene catalysts
US20230151127A1 (en) Attenuated hybrid catalysts
US6255245B1 (en) Process for the preparation of supported polymerization catalyst systems and use thereof in the homo-and co-polymerization of unsaturated monomers
US7452947B2 (en) Silica-supported polymerization catalyst
US8338324B2 (en) Activating supports based on phosphonium complexes
CN115703850B (en) Non-metallocene catalyst and preparation method and application thereof
CN117264097A (en) Bimetallic center heterogeneous catalyst composition and preparation method and application thereof
WO2021242792A1 (en) Attenuated post-metallocene catalysts
CN110028605A (en) Full heterocycle non-metallocene catalyst and preparation method and application

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 200880100337.2

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 08786177

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2008786177

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 20107001618

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 12670235

Country of ref document: US