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WO2000004059A1 - Co-catalyseurs a base d'acide de lewis, sur support, destines a la polymerisation d'olefines - Google Patents

Co-catalyseurs a base d'acide de lewis, sur support, destines a la polymerisation d'olefines Download PDF

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Publication number
WO2000004059A1
WO2000004059A1 PCT/US1999/015733 US9915733W WO0004059A1 WO 2000004059 A1 WO2000004059 A1 WO 2000004059A1 US 9915733 W US9915733 W US 9915733W WO 0004059 A1 WO0004059 A1 WO 0004059A1
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Prior art keywords
transition metal
ligands
group
ligand
polymerization
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George Rodriguez
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ExxonMobil Chemical Patents Inc
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Exxon Chemical Patents Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • 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
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • 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
    • C08F4/65927—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 two cyclopentadienyl rings being mutually bridged

Definitions

  • This invention relates to the supported ionic catalyst systems based on transition metal compounds activated by aryl-group containing Lewis acids that are capable of providing insertion polymerization catalysts and to the preparation of olefin polymers
  • Group 13 based Lewis acids having fluorinated aryl substituents are known to be capable of activating transition metal compounds into olefin polymerization catalysts
  • Trisperfluorophenylborane is demonstrated in EP 0 425 697 and EP 0 520 732 to be capable of ionizing cyclopentadienyl derivatives of transition metals by abstracting a ligand and providing a stabilizing, compatible noncoordinating anion See also, Marks, et al, J Am Chem Soc 1991, 113, 3623-3625
  • the term "noncoordinating anion” is now accepted terminology in the field of olefin polymerization, both by coordination or insertion polymerization and carbocationic polymerization See, for example, EP 0 277 004, U S patent 5,198,401, and Baird, Michael C , et al, J. Am. Chem. Soc.
  • noncoordinating anions are described to function as electronic stabilizing cocatalysts, or counterions, for cationic metallocene complexes which are active for olefin polymerization
  • noncoordinating anion as used here applies both to truly noncoordinating anions and coordinating anions that are at most weakly coordinated to the cationic complexes so as to be labile to replacement by olefinically or acetylenically unsaturated monomers
  • organometallic transition metal cations are stabilized in an active polymerization state by compatible, non-coordinating anions is a well-recognized field in the chemical arts
  • organometalhc transition metal cations are the chemical derivatives of organometalhc transition metal compounds having both ancillary ligands which help stabilize the compound in an active electropositive state and labile ligands at least one of
  • This invention addresses transition metal organometalhc catalyst compounds comprising the reaction product of a suitable transition metal organometalhc compound and a support bound bisaryl boron compound wherein both aryl ligands are halogenated, and processes for the preparation of polyolefins from one or more olefinic monomers comprising combining said olefins with this transition metal organometalhc catalyst compound.
  • the invention provides an olefin polymerization catalyst which is the reaction product of 1) transition metal compounds having ancillary, stabilizing ligands and at least two labile ligands suitable for insertion of olefins and capable of abstraction or removal so as to form active cationic transition metal centers and 2) a support bound, neutral Lewis acid comprising a boron atom having two halogenated aryl ligands and a third ligand which is an heteroatom covalently bonded to a polymeric or metal/metalloid oxide support.
  • These Lewis acid activators and the organometalhc catalyst precursor compounds combine to form active ionic catalysts for olefin polymerization by ligand abstraction.
  • the invention includes a suitable method for preparing polymers and copolymers of two or more monomers by contacting the active catalyst with insertion polymerizable monomers, those having accessible olefinic unsaturation.
  • Lewis acid compounds of the invention are those olefin catalyst activator Lewis acids based on boron metalloid centers and having two bulky, electron-withdrawing ligands such as the halogenated aryl ligands of tris(perfluorophenyl)borane. These bulky ligands should be those sufficient to allow the Lewis acids to function as electronically stabilizing, compatible noncoordinating anions. Stable ionic complexes are achieved when the anions are not readily hydrolyzed and will not be a suitable ligand donor to the strongly Lewis acidic cationic organometalhc transition metal cations used in insertion polymerization, i.e., inhibit ligand transfer that would neutralize the cations and render them inactive for polymerization.
  • the Lewis acids fitting this description can be described by the following formula:
  • R is a monoanionic ligand
  • B is boron
  • ArHal is a halogenated C 6 aromatic or higher carbon number polycyclic aromatic hydrocarbon or aromatic ring assembly in which two or more rings (or fused ring systems) are joined directly to one another or together.
  • Suitable R ligands include: hydride; substituted or unsubstituted C, to C 30 hydrocarbyl aliphatic or aromatic groups, substituted meaning that at least one hydrogen on a carbon atom is replaced with a hydrocarbyl, halide, halocarbyl, hydrocarbyl or halocarbyl substituted organometalloid, dialkylamido, alkoxy, aryloxy, alkysulfido, arylsulfido, alkylphosphido, alkylphosphido or other anionic substituent; fluoride; bulky alkoxides, where bulky refers to C 4 and higher number hydrocarbyl groups, e.g., up to about C 20 , such as tert-butoxide and 2,6-dimethylphenoxide, and 2,6-di(tert- butyl)phenoxide; -SR; -NR 2 , and -PR 2 , where each R is independently a
  • Lewis acidic bisaryl boron compounds according to the above formula can be prepared or synthesized in accordance with methods known in the art In particular, methods of preparing (C 6 F 5 ) 2 BH are specifically taught in U S patent 5,496,960 Generally, the starting material is the Lewis acidic chlorine analog, (C 6 F 5 ) 2 BC1, and reaction with less Lewis acidic organometalhc/metalloid compounds, e g , ClHS ⁇ Me 2 or (Bu) 3 SnD (where Bu is butyl and Me is methyl), was reported to yield the hydride or deute ⁇ de products respectively In a similar manner, replacing the H or D group in the Lewis acidic organometalhc/metalloid compounds with another anionic ligand according to the definition of R above, can be utilized to prepare other suitable Lewis acidic bisaryl boron compounds according to this description Replacing the C 6 F 5 groups on (C 6 F 5 ) 2 BC1 with other halogenated aryl groups permits the preparation of invention compounds with the full range
  • noncoordinating anion as used for the invention compounds is art recognized to mean an anion which either does not coordinate to said transition metal cation or which is only weakly coordinated to said cation thereby remaining sufficiently labile to be displaced by a neutral Lewis base
  • “Compatible” noncoordinating anions are those which are not degraded to neutrality when the complexes between them and the transition-metal cationic catalyst compounds are formed Further, the anion will not transfer an anionic substituent or fragment to the cation so as to cause it to form a neutral four coordinate metal compound and a neutral by-product from the anion
  • Noncoordinating anions useful in accordance with this invention are those which are compatible, stabilize the invention transition metal cation in the sense of balancing its ionic charge, yet retain sufficient lability to permit displacement by an olefinically unsaturated monomer during polymerization Additionally, being support bonded, the anions useful in this invention will be of sufficient molecular size to partially inhibit or help to prevent neutralization of the invention transition-metal cation by
  • the metal or metalloid oxide supports of the invention include any metal/metalloid oxides having surface hydroxyl groups exhibiting a pK a equal to or less than that observed for amorphous silica, l e , pK a less than or equal to about 11
  • covalently bound anionic activator the Lewis acid is believed to form initially a dative complex with a silanol group (which acts as a Lewis base) thus forming a formally dipolar (zwitte ⁇ onic) Bronsted acid structure bound to the metal/metalloid of the metal oxide support
  • the proton of the Bronsted acid appears to protonate the R-group of the Lewis acid, abstracting it, at which time the Lewis acid becomes covalently bonded to the oxygen atom
  • the R group of the Lewis acid then becomes R -O-, where R is a suitable support substrate, e g , silica
  • R is a suitable support substrate, e g , silica
  • metal oxide compositions may additionally contain oxides of other metals, such as those of Al, K, Mg, Na, Si, Ti and Zr and should preferably be treated by thermal and/or chemical means to remove water and free oxygen Typically such treatment is in a vacuum in a heated oven, in a heated fluidized bed or with dehydrating agents such as organo silanes, siloxanes, alkyl aluminum compounds, etc
  • dehydrating agents such as organo silanes, siloxanes, alkyl aluminum compounds, etc
  • the level of treatment should be such that as much retained moisture and oxygen as is possible is removed, but that a chemically significant amount of hydroxyl functionality is retained Thus calcining at up to 800 °C, or more up to a point prior to decomposition of the support material, for several hours is permissible, and if higher loading of supported anionic activator is desired, lower calcining temperatures for lesser times will be suitable
  • the tailoring of hydroxyl groups available as attachment sites in this invention can also be accomplished by the pre-treatment, prior to addition of the Lewis acid, with a less than stoichimet ⁇ c amount of the chemical dehydrating agents
  • those used will be used sparingly and will be those having a single ligand reactive with the silanol groups (e g , (CH3)4S ⁇ Cl), or otherwise hydrolyzable, so as to minimize interference with the reaction of the transition metal catalyst compounds with the bound activator
  • difunctional coupling agents e g , (CH3)3S ⁇ Cl2
  • may be employed to cap hydrogen bonded pairs of silanol groups which are present under the less severe calcining conditions See, e g , "Investigation of Quantitative SiOH Determination by the Silane Treatment of Disperse Silica", Gorski, et al, Journ of Colloid and Interface Science, Vol 126, No 2, Dec 1988, for discussion of the effect of silane
  • Polymeric supports are preferably hydroxyl-functional-group-contaimng polymeric substrates, but may be any of the primary alkyl amines, secondary alkyl amines, and others, where the groups are structurally incorporated in a polymeric chain and capable of a acid-base reaction with the Lewis acid such that a ligand filling one coordination site of the boron is protonated and replaced by the polymer incorporated functionality
  • preferred heteratoms constituting the third ligand of the bisaryl boron compounds of the invention will be Group 15 or 16 heteroatoms, most preferably oxygen or nitrogen
  • Organometalhc transition metal compounds suitable as olefin polymerization catalysts by coordination or insertion polymerization in accordance with the invention will include the known transition metal compounds useful in traditional Ziegler-Natta coordination polymerization and as well the metallocene compounds similarly known to be useful in coordination polymerization, when such compounds are capable of catalytic activation by the cocatalyst activators described for the invention These will typically include Group 3-10 transition metal compounds having bulky ancillary ligands not prone to abstraction and two labile metal ligands which can be abstracted by the cocatalyst activators Labile ligands include hydrocarbyl ligands, such as hydride or alkyl, and hyrocarbylsilyl, such as t ⁇ methylsilyl Ligands capable of abstraction and transition metal compounds comprising them include those described in the background art, see for example US patents 5, 198,401 and 5,278,119.
  • metal ligands include halogen, amido or alkoxy moieties (for example, biscyclopentadienyl zirconium dichloride) which are not capable of abstraction with the activating cocatalysts of the invention, they can be converted via known alkylation reactions with organometalhc compounds such as lithium or aluminum hydrides or alkyls, alkylalumoxanes, Grignard reagents, etc. See also EP-A1-0 570 982 for the reaction of organoaluminum compounds with dihalo-substituted metallocene compounds prior to addition of activating anion compounds. All documents are incorporated by reference for purposes of U.S. patent practice.
  • Such metallocene compounds can be described for this invention as mono- or biscyclopentadienyl substituted Group 3, 4, 5, 6, 9, or 10 transition metal compounds wherein the ancillary ligands may be themselves substituted with one or more groups and may be bridged to each other, or may be bridged through a heteroatom to the transition metal.
  • the size and constituency of the ancillary ligands and bridging elements are not critical to the preparation of the ionic catalyst systems of the invention but should be selected in the literature described manner to enhance the polymerization activity and polymer characteristics being sought.
  • the cyclopentadienyl rings when bridged to each other, will be lower alkyl-substituted (C ⁇ -C 6 ) in the 2 position (without or without a similar 4-position substitutent in the fused ring systems) and may additionally comprise alkyl, cycloalkyl, aryl, alkylaryl and or arylalkyl substituents, the latter as linear, branched or cyclic structures including multi-ring structures, for example, those of U.S.
  • Metallocene compounds suitable for the preparation of linear polyethylene or ethylene-containing copolymers are essentially any of those known in the art, see again EP-A- 277,004, WO-A-92/00333 and U S patents 5,001,205, 5,198,401, 5,304,614, 5,308,816, and 5,324,800 for specific listings Selection of metallocene compounds for use to make isotactic or syndiotactic polypropylene, and their syntheses, are well-known in the art, specific reference may be made to both patent literature and academic, see for example Journal of Organometalhc Chemistry 369, 359-370 (1989) Typically those catalysts are stereorigid asymmetric, chiral or bridged chiral metallocenes See, for example, U S patent 4,892,851, U S patent 5,017,714, U S patent 5,296,434, U S patent 5,278,264, WO-A-(PCT/US92
  • Non-limiting representative metallocene compounds include mono- cyclopentadienyl compounds such as pentamethylcyclopentadienyltitanium isopropoxide, pentamethylcyclopentadienyltribenzyl titanium, dimethylsilyltetramethylcyclopentadienyl-tert-butylamido titanium dichloride, pentamethylcyclopentadienyl titanium trimethyl, dimethylsilyltetramethylcyclopentadienyl-tert-butylamido zirconium dimethyl, dimethylsilyltetramethylcyclopentadienyl-dodecylamido hafnium dihydride, dimethylsilyltetramethylcyclopentadienyl-dodecylamido hafnium dimethyl, unbridged biscyclopentadienyl compounds such as bis(l,3-butyl, methylcyclopentadienyl) zirconium dimethyl,
  • Representative traditional Ziegler-Natta transition metal compounds include tetrabenzyl zirconium, tetra bis(trimethylsiylmethyl) zirconium, oxotris(trimethlsilylmethyl) vanadium, tetrabenzyl hafnium, tetrabenzyl titanium, bis(hexamethyl disilazido)dimethyl titanium, tris(trimethyl silyl methyl) niobium dichloride, tris(trimethylsilylmethyl) tantalum dichloride.
  • the important features of such compositions for coordination polymerization are the ligand capable of abstraction and that ligand into which the ethene (olefinic) group can be inserted. These features enable the abstraction of the transition metal compound and the concomitant formation of the ionic catalyst composition of the invention
  • Additional organometalhc transition metal compounds suitable as olefin polymerization catalysts in accordance with the invention will be any of those Group 3-10 that can be converted by ligand abstraction into a catalytically active cation and stabilized in that active electronic state by a noncoordinating or weakly coordinating anion sufficiently labile to be displaced by an olefinically unsaturated monomer such as ethylene
  • Exemplary compounds include those described in the patent literature
  • U S patent 5,318,935 describes bridged and unbridged bisamido transition metal catalyst compounds of Group 4 metals capable of insertion polymerization of ⁇ -olefins
  • International patent publication WO 96/23010 describes dnmine nickel and palladium compounds suitable for ionic activation and olefin polymerization Transition metal polymerization catalyst systems from Group 5-10 metals wherein the active transition metal center is in a high oxidation state and stabilized by low coordination number polyamonic ancillary ligand systems are described in US patent 5,502,124 and
  • the total catalyst system can additionally comprise one or more scavenging compounds
  • scavenging compounds is meant to include those compounds effective for removing polar impurities from the reaction environment. Impurities can be inadvertently introduced with any of the polymerization reaction components, particularly with solvent, monomer and catalyst feed, and adversely affect catalyst activity and stability. Impurities can result in decreased, variable or even elimination of catalytic activity.
  • the polar impurities, or catalyst poisons include water, oxygen, metal impurities, etc. Preferably steps are taken before provision of such into the reaction vessel, for example by chemical treatment or careful separation techniques after or during the synthesis or preparation of the various components; some minor amounts of scavenging compound can still normally be used in the polymerization process itself.
  • the scavenging compound will be an organometalhc compound such as the Group 13 organometalhc compounds of U.S. patents 5,153,157, 5,241,025 and WO- A-93/14132, WO-A-94/07927, and that of WO-A-95/07941.
  • organometalhc compounds such as the Group 13 organometalhc compounds of U.S. patents 5,153,157, 5,241,025 and WO- A-93/14132, WO-A-94/07927, and that of WO-A-95/07941.
  • Exemplary compounds include triethyl aluminum, triethyl borane, triisobutyl aluminum, methylalumoxane, isobutyl aluminoxane, and tri(n-octyl)aluminum.
  • scavenging compounds having C3-C12 bulky, or C8-C20 linear, hydrocarbyl substituents covalently bound to the metal or metalloid center are preferred to minimize adverse interaction with the active catalyst.
  • the amount of scavenging agent to be used with supported transition-metal cation-non- coordinating anion pairs is minimized during polymerization reactions to that amount effective to enhance activity.
  • the polymerization medium can be either a liquid monomer, like propylene, or a hydrocarbon solvent or diluent, advantageously aliphatic paraffin such as propane, isobutane, hexane, heptane, cyclohexane, etc or an aromatic one such as toluene
  • the polymerization temperatures may be those considered low, e g , less than 50 °C, preferably 0 °C - 30 °C, or may be in a higher range, such as up to about 150 °C, preferably from 50 °C up to about 80 °C, or at any ranges between the end points indicated Pressures can vary from about 100 to about 700 psia (0 76-4 8 Mpa) Additional description is given in U S patents 5,274,056 and 4, 182,810 and WO 94/21962 which are incorporated by reference for purposes of U S patent practice
  • unsaturated monomers that is olefinically or ethylemcally unsaturated monomers, may be polymerized so as to form polymer products having molecular weights
  • Suitable olefinically unsaturated monomers include ethylene, C 3 -C 20 linear or branched ⁇ -olefins, C 4 -C 20 cyclic olefins, C 4 -C 20 non-conjugated diolefms, C 4 -C 2 o geminally disubstituted olefins, C -C 0 styremc olefins or C 20 -C ⁇ 0 oo oc -olefin macromers
  • the polymer products will be any of polyethylene homopolymers and copolymers, particularly, polyethylene plastics, plastomers and elastomers, polypropylene homopolymers and copolymers, including atactic, syndiotactic or isotactic polypropy
  • the supported catalyst according to the invention will be useful for industrial means of preparing addition or insertion polymers derived from olefinically unsaturated monomers.
  • catalysts will be particularly suitable for use in gas phase or slurry processes, such as those practiced industrially worldwide, largely in accordance with the description above of these processes.
  • Such polymer manufacturing processes are responsible for large amounts of plastic, thermoplastic elastomers and elastomers for films, fibers, packaging, adhesive substrates and molded articles in common use.
  • the methodology of the invention can be readily extended to exploit combinatorial methods of catalyst evaluation.
  • the polymeric supported activators are valuable intermediates for the construction and screening of libraries useful for optimization of new single-site catalyst systems capable of activation by ligand abstraction.
  • Lewis Acid A (vide supra) A yellow to orange color change was observed immediately after the solution containing the transition metal compound was added to the slurry of the Silica Bound Lewis Acid A In this connection, it is important to notice that this is the same color change observed when (CH 3 ) 2 Si(2-methyl-4-phenylindene)Zr(CH 3 ) 2 is activated with similar discrete activators (e g B( F 5 ) 3 or [(C 6 H 5 )NH(CH 3 ) 2 ][B(C 6 F 5 ) 4 ]) After stirring for 30 minutes the orange solid was collected by vacuum filtration, washed with two 5 ml portions of dry toluene, and dried under reduced pressure for 20 minutes
  • the polymerization described below was carried out in a 1 -liter autoclave reactor equipped with a mechanical stirrer, an external water-steam jacket for temperature control, two inlet ports for catalyst or scavenger delivery, and pressure controlled supply of propylene or nitrogen Prior to the polymerization reaction the reactor was dried by heating the reactor body to 110° C for 30 minutes under a constant nitrogen purge This procedure allows for degassing the reactor as well Into the reactor was added 200 ml of dry toluene, 1 0 ml of a 10 wt% triisobutylaluminum solution (toluene), and 100 ml of propylene The reactor was brought to 70° C A 50 mg portion of Catalysts A described in example 3 was pressurized into the reactor with 100 ml of pressurized propylene A slight exotherm (2° C) was observed immediately after the catalyst was added to the reactor The temperature of the reactor was maintained at 70° C After 10 minutes of reaction time the temperature was reduced to 30° C and the
  • the polymerization described below was carried out in a 1 -liter autoclave reactor equipped with a mechanical stirrer, an external water-steam jacket for temperature control, two inlet ports for catalyst or scavenger delivery, and pressure controlled supply of propylene or nitrogen Prior to the polymerization reaction the reactor was dried by heating the reactor body to 110° C for 30 minutes under a constant nitrogen purge Into the reactor was added 1 0 ml of a 10 wt% triisobutylaluminum solution (toluene), and 200 ml of propylene The reactor was brought to 70° C A 50 mg portion of Catalysts B described in example 4 was pressurized into the reactor with 200 ml of pressurized propylene A slight exotherm (1° C) was observed immediately after the catalyst was added The temperature of the reactor was maintained at 70° C After 30 minutes of reaction time the temperature was reduced to 30° C and the pressure in the reactor was removed by ventilation The polymer was collected as a wet solid and dried for 24 hours in a

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Abstract

L'invention concerne un catalyseur de polymérisation d'oléfines, lequel est le produit de réaction entre: 1) des composés de métaux de transition possédant des ligands de stabilisation auxiliaires, ainsi qu'au moins deux ligands labiles, conçus pour l'insertion d'oléfines et capables de s'abstraire ou s'enlever, de manière à former des centres de métaux de transition, cationiques et actifs, et 2) un acide de Lewis lié sur support et comprenant un atome de bore possédant deux ligands aryles halogénés ainsi qu'un troisième ligand représenté par un hétéroatome lié de manière covalente à un support d'oxyde métallique/métalloïde. Dans certains modes de réalisation, on décrit la polymérisation d'oléfines. L'invention concerne encore un procédé de polymérisation de monomères alcéniques, consistant à mettre en contact un ou plusieurs de ces monomères avec le catalyseur de l'invention.
PCT/US1999/015733 1998-07-16 1999-07-12 Co-catalyseurs a base d'acide de lewis, sur support, destines a la polymerisation d'olefines Ceased WO2000004059A1 (fr)

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Cited By (5)

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WO2005075526A3 (fr) * 2004-01-16 2005-11-03 Exxonmobil Chem Patents Inc Hydrophobisation et silice destine a un catalyseur supporte
US6982307B2 (en) 2000-08-22 2006-01-03 Rohm And Haas Company Matrix and process for polyolefin production
US7847038B2 (en) 2007-07-13 2010-12-07 Exxonmobil Chemical Patents Inc. Preparation of supported silyl-capped silica-bound anion activators and associated catalysts
WO2013070601A2 (fr) 2011-11-08 2013-05-16 Univation Technologies, Llc Procédés de préparation d'un système catalyseur
EP3309182A2 (fr) 2007-11-15 2018-04-18 Univation Technologies, LLC Catalyseurs de polymérisation, leurs procédés de fabrication, leurs procédés d'utilisation et produits polyoléfiniques fabriqués à partir de ceux-ci

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Cited By (8)

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