Supported catalyst component, supported catalyst, preparation process, polymerization process, complex compounds, and their preparation

IS 2 188 751 T3

DESCRIPTION

Supported catalyst component, supported catalyst, preparation process, polymerization process, complex compounds, and their preparation.

This invention relates to a supported catalyst component comprising a support material, an organometallic compound and an activator compound, to a supported catalyst comprising said supported catalyst component and a transitionon metal compound, to a process for preparing such a component. from supported catalyst and catalyst, to a polymerization process using such supported catalyst, to complex compounds for use as activator compounds, and to a process for preparing such complex compounds.

Fundamentals of the invention

Ionic, homogeneous or unsupported transition metal catalysts are known for their high catalytic activity in olefin polymerizations. Under polymerization conditions in which the polymer is formed as solid particles, these homogeneous (soluble) catalysts form polymer deposits on the walls and stirrers of the reactor whose deposits must be removed frequently because they prevent an efficient heat exchange necessary for cooling. of the reactor contents and cause excessive wear of the moving parts in the reactor. The polyomers produced by these soluble catalysts also have a low bulk density that limits the commercial utility of both the polymer and the process. In order to solve these problems, various supported ionic catalysts have been proposed for use in particle-forming polymerization processes.

WO-91/09882 describes an ionic metallocene supported catalyst prepared by combining: i) a bis (cyclopentadienyl) metalic compound containing at least one ligand capable of reacting with a protoon, ii) an activating component comprising a cation capable of donating a proton and a bulky, liable anion capable of stabilizing the metallic cation formed as a result of the reaction between the metal compound and the activator component, and iii) a catalyst support material. The support material can be subjected to chemical or chemical dehydration treatment. In some of the examples triethylaluminum was added for this purpose. The maximum bulk density presented in the examples of WO91 / 09882 is 0.17 g / cm³ and the efficiency of the catalyst is not satisfactory.

WO-94/03506 describes a supported ionic catalyst prepared by combining: i) a monocyclopentadienyl metal compound, ii) an activator component comprising a cation that will react irreversibly with at least one ligand contained in said metal compound and an anion, said anion being an anionic, non-nucleophilic, chemically stable complex, and iii) a catalyst support material, optionally followed by prepolymerization of said supported catalyst system with an olephonic monomer. The support material can be treated with a hydrolyzable orgaonic additive, preferably a Group 13 alkyl compound, such as triethylaluminum. The catalyst efficiencies obtained in WO-94/03506 are, however, very low. WO-94/03509 suggests the use of ionic supported catalysts, as described in WO-94/03506 for use in a gas phase polymerization process.

WO-93/21238 describes tris (pentafluorophenyl) borane complexes of water, alcohols, mercaptans, silanols, oximes and mixtures thereof. These neutral complexes can be converted into acid salts of their conjugated bases by reaction with amines. These complexes and acid salts thereof together with Group 4 transition metal compounds, especially metallocenes, were described as useful as homogeneous olefin polymerization catalysts.

WO-93/11172 relates to polyonic transition metal catalyst compositions. It is suggested that polyanionic activators be used to prepare an improved performance catalyst system by immobilizing the catalyst on a support material. It is believed, however, that the explanations in WO-93/11172 are not sufficient to prepare a supported catalyst based on surface hydroxyl groups containing support materials. Figure 1, Formula 3 and page 26, line 25 suggest the use of so-called alcohol functional synthons in the manufacture of polyanionic activators. Various methods are suggested to prepare catalyst supports based on polyanionic activators prepared from alcohol functional synthons, as discussed below. In a first method (page 26, lines 32-36 and Fig. 1 Formula 6) the alcohol functional synthon is converted to a silyl halide analog by treatment with R'jSi Cl4-j (j = 0 to 3). As indicated in oil, HCl is released which should be adsorbed by a tertiary amine. This, however, damaged the by-product R3NH.Cl. The ammonium chloride formed is therefore not an activating compound

ES 2 188 751 T3 suitable for a transition metal catalyst because the chloride anion is not a non-coordinating anion that is typically required for such a type of catalyst, and the catalyst prepared therefore did not have substantial catalytic activity . The compound of Formula 6 can be reacted with a hydroxylated substrate such as solid gel, alumina or metallic oxides (page 34, lines 25-28 and Figure 1 route C). When the compound of Formula 6 is used, equivalents of HCl can be liberated, which compound and the possibly suggested by-product ammonium chloride will provide catalytic systems with only negligible catalytic activities.

On page 32, lines 11-18, further methods are suggested for preparing catalyst supports from synthons with alcohol functions: acid-catalyzed dehydration of hydroxylated surfaces (such as amorphous solid), and esterification or transesterification of discrete or polymeric materials that They contain more than one carboxylic acid or ester per molecule, polymer chain, or particle. All of these reactions release water, which is a poison for transition metal catalysts.

An additional method is described from page 34, page 34, page 35, page 37 and page 37, page 16 to page 38, page 14, as well as in Figure 8. According to that method, a support material is provided with anioonic functionalities by reacting a silane halide or silane alkooxide coupling agent with a hydroxylated surface of solid. In page 35, lines 33-37 it is suggested to mask or protect reactive functionalities such as hydroxyl functions (in solid). On page 37, lines 20-31 this is explained further and it is indicated that part of the hydroxyl functions can be masked and the remaining part can be converted into said anioonic functionalities. This will allow to vary or adjust the concentration of anionic functionalities (for the last one). In this context a mixture of trimethoxy bromophenylsilane and trimethoxy phenylsilane is mentioned. Accordingly, the hydroxyl functionalities that are masked or protected are not used to prepare anionic functionalities. Furthermore, the use of silane halides or silane alkoxides to react with surface hydroxyl groups would result in by-product hydrogen halides and alcohols that are catalyst poisons. Accordingly, none of the suggested methods are believed to give effective supported catalysts.

It would be desirable to provide a supported catalyst and supported catalyst component thereof, and a polymerization process that is capable of producing polyomers with good catalytic efficiencies, thereby avoiding or reducing some of the disadvantages that occur in the prior art.

Summary of the invention

In one aspect of the present invention a supported catalyst component is provided comprising: (a) a support material, a reaction product of an organometallic compound in which the metal is selected from: magnesium, zinc, aluminum, tin and lead , and (b) an activator compound comprising: b.1) a cation that is capable of reacting with a transition metal compound to form a catalytically active transition metal complex, and b.2) a compatible anion that has up to 100 non-hydrogenic aotoms and contains al minus one substituent comprising an active hydrogen residue.

In a second aspect there is provided a supported catalyst comprising the supported catalyst component of the invention and (c) a transitional metal compound containing a substituent capable of reacting with an activating compound (b) to thereby form a catalytically active transition metal complex.

In a further aspect the invention provides a process for preparing a supported catalyst component comprising combining a support material (a), an organometaolic compound in which the metal is selected from: magnesium, zinc, aluminum, tin and lead, and a activator compound (b) comprising: b.1) a cation that is capable of reacting with a transition metal compound to form a catalytically active transition metal complex, and b.2) a compatible anion that has up to 100 non-hydrogen aotoms and contains al minus one substituent comprising an active hydrogen residue.

In another aspect of the invention there is provided a process for preparing a supported catalyst comprising the process for preparing the supported catalyst component of the present invention and the further step of adding a transition metal compound (c) containing a capable substituent of reacting with activator compound (b) to thereby form a catalytically active transitionon metal complex.

IS 2 188 751 T3

In yet a further aspect the present invention provides an adduct of an organometholic compound in which the metal is selected from: magnesium, zinc, aluminum, tin and lead, and an activating compound comprising: b.1) a cation that is capable of reacting with a transition metal compound to form a catalytically active transition metal complex, and b.2) a compatible anion that has up to 100 non-hydrogen atoms and contains al minus one substituent comprising an active hydrogen residue, obtained by combining the organometallic compound and the activating compound in a suitable diluent or solvent, optionally followed by removal of the solvent or diluent.

In yet another aspect the invention provides an additional polymerization process in which one or more additional polymerizable monomers are contacted with a supported catalyst according to the present invention under additional polymerization conditions.

In yet a further aspect, a complex compound is provided comprising a charge balancing cation and a compatible anion corresponding to Formula (I):

[M '^{m +}Qn (Gq (T-Pr) r) z]^d- (I) in which:

M 'is a metal or metalloid selected from Groups 5-15 of the Periodic Table of the Elements;

Q independently in each case is selected from the group consisting of: hydride, dihydrocarbylamido, halide, hydrocarbyloxide, hydrocarbyl and substituted hydrocarbyl radicals, including halo-substituted hydrocarbyl radicals and hydrocarbyl- and halohydrocarbyl-substituted organometalloid radicals, the hydrocarbyl part having from 1 to 20 carbons with the condition that Q is not halide in more than one case;

G is a polyvalent hydrocarbon radical, having r + 1 valences, attached to M 'and T;

TesO, S, NRoPR, enlosqueRes a hydrocarbon radical, a trihydrocarbylsilyl radical, a trihydrocarbylgermyl radical, or hydrogen;

Pr is hydrogen H or a protecting group; m is an integer number from 1 to 7; integer nesunnuomer from 0 to 7; qes1;

whole resunnuomer of1a3; z is an integer number from 1 to 8; whole desunnuomer from 1 to 7; and n + zm = d.

According to a further aspect the present invention provides a method for preparing a complex compound containing an anion corresponding to Formula (I).

[M '^{m +}Qn (Gq (T-Pr) r) z]^d- (I) in which:

M 'is a metal or metalloid selected from Groups 5-15 of the Periodic Table of the Elements;

Q independently in each case is selected from the group consisting of: hydride, dihydrocarbylamido, halide, hydrocarbyl oxide, hydrocarbyl and substituted hydrocarbyl radicals, including halo-substituted hydrocarbyl radicals, and hydrocarbyl- and halohydrocarbyl-substituted organometalloid radicals, the hydrocarbyl part having from 1 to 20 carbons provided that Q is halide in no more than one case;

IS 2 188 751 T3

G is a polyvalent hydrocarbon radical, having r + 1 valences, attached to M 'and T;

T is O, S, NR or PR, where R is a hydrocarbyl radical, a trihydrocarbylsilyl radical, a trihydrocarbylgermyl radical, or hydrogen;

Pr is hydrogen H or a protecting group; m is an integer from 1 to 7; integer nesunnuomer from 0 to 7; q is the integer number 0 or or 1; r is an integer number from 1 to 3; z is an integer number from 1 to 8; whole desunnuomer from 1 to 7; and n + zm = d; and a load balancing cation;

in which complex compound the anion and cation are contained in such relative amounts to provide a neutral compound, comprising the steps of combining in a suitable solvent or diluent a compound M '^{m +} Qm with a compound of the formula Z¹(Gq (T-Pr) r), where Z¹ is [M'X "]⁺ or [M "]⁺ yM'is a group 2 element, M 'is a group 1 element and X is halogen, G, T, Pr, q and r have the same meaning as given for Formula (I), optionally followed by recovery of the product complex.

Detailed description of the invention

All references herein to elements or metals belonging to a certain Group refer to the Periodic Table of the Elements published and copyrighted by CRC Press, Inc., 1989. Also, any reference to the Group or Groups will be referred to the Group or Groups as reflected in this Periodic Table of the Elements using the IUPAC system for group numbering.

Surprisingly, it has been found that a complex compound containing at least one substituent comprising an active hydrogen moiety as specified herein, can be attached to the support and is capable of activating transition metal catalysts typically employed in processes of polymerization by addition. This is surprising since it is known that active hydrogen-containing compounds tend to deactivate topical transition metal catalysts, especially transition metal catalysts containing a cyclopentadienyl moiety or a derivative thereof. The supported catalysts present can be used to produce polyomers with satisfactory catalytic efficiencies.

An additional benefit is that the formation of polymer deposits on the walls or other moving parts of the reactor is avoided; and the polyomers are in the form of powder or in loose or particulate granules, when a polymerization process that forms particles is used, such as a process of polymerization in suspension or in gas phase, so that the polyomers can be easily transported , and polyomers of improved bulk density are obtained in such particle-forming polymerization processes. In accordance with the present invention the improved bulk densities, for ethylene-based polyomers and interpolymers, are preferably bulk densities of at least about 0.20 g / cm³, and more preferably at least about 0.25 g / cm³. In the supported catalyst components and catalysts, the activating complexes are well dispersed throughout the porous structure of the porous support material, which is one of the important factors in maintaining both a long period and a high level of catalytic efficiency. During the formation of the polymer in the supported catalyst particles, the particles tend to fragment and therefore create fresh surface available for the growth of the polymer. The presence of catalytically active groups on such a fresh surface is highly desirable to provide good catalytic efficiencies and polymer morphology.

IS 2 188 751 T3

Suitable support materials for use in the present invention include porous resinous materials, for example, polyolefins such as polyethylenes and polypropylenes or styrene-divinylbenzene copolymers, solid inorganic ioxides including Group 2, 3, 4, 13 or 14 metal oxides, such as solid, alumina, magnesium oxide, titanium oxide, thorium oxide, as well as mixed solid oxide. OR^or Suitable mixed solid oxides include those of solid and one or more Group 2 or 13 metal oxides, such as mixed solid-magnesia or solid-alumina oxides. Preferred support materials are solid, alumina and mixed solid oxides and one or more Group 2 or 13 metal oxides. Preferred examples of such mixed oxides are solid alumina oxides. The most preferred support material is solid. The shape of the solid particles is not chromic and the solid can be in granular, spherical, agglomerated, pyrolyzed or other forms. Suitable solices include those available from Grace Davison (a division of WR Grace & Co.) under the designations SD 3216.30; SP-9-10046, Davison Syloid 245, Davison 948 and Davison 952, from Degussa AG under the designation Aerosil 812, and from Crossfield under the designation ES 70X.

Suitable support materials for the present invention preferably have a surface area, as determined by nitrogen porosimetry using the BET method, of 10 to about 1,000 µm.²/ g, and preferably about 100 to 600 µm²/ g. The pore volume of the support, as determined by nitrogen adsorption, is topically up to 5 cm³/ g, advantageously between 0.1 and 3 cm³/ g, preferably about 0.2 to 2 cm³/ g. The mean particle size is not critical but is typically 0.5 to 500 µm, preferably 1 to 200 µm, more preferably 100 µm.

The support material can be subjected to a thermal treatment and / or chemical treatment to reduce the water content or the hydroxyl content of the support material. Both dehydrated support materials and support materials containing small amounts of water can be used. Typical pretreatments are carried out at a temperature of 30 ° C to 1,000 ° C for a duration of 10 minutes to 50 hours in an inert atmosphere or at reduced pressure. Topical support materials have a surface hydroxyl content of 0.1 micromoles, preferably 5 micromoles, more preferably 0.05 mmol to no more than 5 mmol of hydroxyl groups per g of solid support, more preferably 0.5 to 2 mmol per gram. The hydroxyl content can be determined by known techniques, such as infrared spectroscopy and titration techniques using a metal alkyl or metal hydroxide, for example, by adding an excess of dialkyl magnesium to a suspension of the solid support and determining the amount of dialkyl magnesium remaining in it. solved by known techniques. This last method is based on the reaction of S-OH + MgR₂ S-OMgR + RH, where S is the solid support.

The support material is treated with the organometallic compound. Suitable organometaolic compounds are those comprising Group 2-13 metals, germanium, tin and lead, and at least two substituents selected from: hydride, hydrocarbyl radicals, trihydrocarbylsilyl radicals and trihydrocarbylgermyl radicals. Additional substituents preferably comprise one or more substituents selected from: hydride, hydrocarbyl radicals, trihydrocarbyl substituted silyl radicals, trihydrocarbyl substituted germyl radicals and hydrocarbyl-, trihydrocarbylsilyl- or trihydrocarbylgermyl-substituted metalloid radicals.

The terminology "metalloid" as used herein includes non-metals such as boron, phosphorus, and the like that exhibit semi-metallic characteristics.

Examples of such organometaolic compounds include organomagnesium, organozinc, organoalumonic, organotin and organopluombic compounds, and mixtures thereof. Alumoxanes are additional suitable organometaolic compounds. Preferred examples are alumoxanes and compounds represented by the following formulas: MgR¹2, ZnR¹2, AlR¹xR²and, in which R¹ independently in each case it is a hydride, a hydrocarbyl radical, a trihydrocarbylsilyl radical, a trihydrocarbylgermyl radical or a trihydrocarbyl-, trihydrocarbylsilyl- or trihydrocarbylgermyl-substituted metalloid radical, R²independently is the same as R¹, xes2oó3, yes0oó1 and the sum of x and y is 3, and mixtures thereof. Examples of suitable hydrocarbyl moieties are those having 1 to 20 carbon atoms in the hydrocarbyl part thereof, such as: alkyl, aryl, alkaryl or aralkyl. Preferred radicals include: methyl, ethyl, n- or isopropyl, n-, sec- or tert-butyl, phenyl, and benzyl. Preferably, the aluminum component is selected from the group consisting of alumoxane and aluminum compounds of the formula AlR¹x where R¹ independently in each case is hydride or a hydrocarbyl radical having 1 to 20 carbon atoms, and x is 3. Suitable trihydrocarbylaluminum compounds are trialkyl or triarylaluminum compounds in which each alkyl or aryl group has 1 to 10 carbon atoms. carbon, or mixtures thereof, and preferably trialkylaluminum compounds such as trimethyl,

ES 2 188 751 T3 triethyl, triisobutylaluminum.

Alumoxanes (also referred to as aluminoxanes) are oligomeric or polymeric aluminum oxycompounds containing alternating chains of aluminum and oxygen atoms, whereby aluminum carries a substituent, preferably an alkyl group. The structure of alumoxane is believed to be represented by the following general formulas: (-Al (R) -O)_m, for a cyclic alumoxane and R₂AlO (-Al (R) -O) m-AlR2 for a linear compound, wherein R is, independently in each case, a C1-C10 hydrocarbyl, preferably alkyl or halide and m is an integer number ranging from 1 to about 50, preferably at least about 4. Alumoxanes are topically the reaction products of water and an aluminum alkyl, which in addition to an alkyl group may contain halide or alkoxide groups. By reacting various different alkylaluminum compounds, such as, for example, trimethylaluminum and triisobutylaluminum, so-called modified or mixed alumoxanes are rendered with water. Preferred alumoxanes are methylalumoxane and methylalumoxane modified with minor amounts of other lower alkyl groups such as isobutyl. Alumoxanes normally contain minor to substantial amounts of the starting alkylaluminum compound.

The way alumoxane is prepared is not chromatic. When prepared by reaction between water and alkylaluminum, water can be combined with alkylaluminum in various ways, such as liquid, vapor or solid, for example in the form of water of crystallization. In US Pat. No. 4,542,199 describes particular techniques for the preparation of compounds of the alumoxane type, by contacting an alkylaluminum compound with an inorganic salt containing water of crystallization. In a particular preferred embodiment, an alkylaluminum compound is contacted with a regenerable water-containing substance such as alumina, solid or other hydrated substance. This is described in European Patent Application No.^° 338.044.

The supported catalyst component and the supported catalyst of the present invention normally comprise a support material combined or treated with the organometallic compound, preferably an aluminum component, and containing at least 0.1 micromoles of organometaolic compound per g of support material, topically at least 5 micromoles per g of support material, advantageously at least 0.5 percent by weight of the metal, preferably aluminum, expressed in grams of metal, preferably aluminum, or atoms per g of support material. Preferably, the amount of metal, advantageously aluminum, is at least 2 percent by weight, and usually no more than 40 percent by weight, and more preferably no more than 30 percent by weight. With too large amounts of metal, preferably aluminum, the supported catalyst becomes expensive. With amounts too low the efficiency of the catalyst drops to fall below acceptable levels.

The supported catalyst component and the supported catalyst of the present invention preferably contain a treated support material (a) comprising a support material and an alumoxane in which no more than about 10 percent of the aluminum present in the treated support material is extractable in one hour of extraction with toluene of 90^°C using approximately 10 ml of toluene per gram of pretreated carrier material. More preferably, no more than about 9 percent of the aluminum present in the supported catalyst component is extractable, and preferably no more than about 8 percent. This is especially advantageous when the supported catalyst component or catalyst prepared hereby is used in a polymerization process using a diluent or solvent that can extract unfixed alumoxane from the support material. It has been found that when the amount of extractables is below the levels given above, the amount of alumoxane that can diffuse into the polymerization solvent or diluent, if used, is so low that no appreciable amount of polymer was formed in the diluent, compared to the polymer formed on the support material. If too much polymer is formed in the diluent, the bulk density of the polymer drops below acceptable levels and can cause greasing problems in the reactor.

The toluene extraction test is carried out as follows: Approximately 1 g of supported catalyst component or supported catalyst, with a known aluminum content, is added to 10 ml of toluene and the mixture is then heated to 90^°C in an inert atmosphere. The suspension is stirred well at this temperature for 1 hour. After the suspension is filtered applying reduced pressure to favor the filtration stage. The solids are washed twice with approximately 3 to 5 ml of toluene a90.^°C per gram of solids. Solids dry after 120^°C for 1 hour, and subsequently the aluminum content of the solids is measured. The difference between the initial aluminum content and the aluminum content after extraction divided by the initial aluminum content and multiplied by 100%, gives the amount of extractable aluminum.

IS 2 188 751 T3

Aluminum content can be determined by suspending approximately 0.5 g of supported catalyst component or supported catalyst component in 10 ml of hexane. The suspension is treated with 10 to 15 ml of 6N sulfuric acid, followed by the addition of a known excess of EDTA. The amount of excess EDTA is then back titrated with zinc chloride.

Without wishing to be bound by theory, it is believed that the activator compound used in the present invention reacts with the organometallic compound, preferably aluminum component, through the active hydrogen-containing substituent. It is believed that an R group¹ of the organometallic compound, preferably aluminum component, combines with the active hydrogen moiety of the activator compound to liberate a neutral orgaonic compound, for example an alkane, or hydrogen gas coupling, whereby, chemically the metal, preferably aluminum atom with the residue of the activator compound. It is therefore believed that the activator becomes chemically bound to the support material after the support material has been treated with the organometallic compound or adduct of the organometaolic compound and the activator compound. On addition of the transitional metal compound, a supported catalyst with improved properties is formed.

The useful activator compound in the present invention contains a compatible anion having up to 100, and preferably up to 50 aotoms that are not hydrogen and having at least one substituent comprising an active hydrogen moiety, corresponding to the formula

Gq (TH) r in which G is a polyvalent hydrocarbon radical, T is O, S, NR or PR, in which R is a hydrocarbyl radical, a trihydrocarbylsilyl radical, a trihydrocarbylgermyl or hydrogen radical, H is hydrogenous, qes0oo , and preferably 1, and r is an integer number from 1 to 3, preferably 1. The polyvalent hydrocarbon radical G has r + 1 valences, one valence being with a metal or metalloid of Groups 5-15 of the Periodic Table of the Elements in the compatible anioon, the other valence or valences of G being attached to groups TH. Preferred examples of G include divalent hydrocarbon radicals such as: alkylene, arylene, aralkylene or alkarylene radicals containing 1 to 20 carbon atoms, more preferably 2 to 12 carbon atoms. Suitable examples of G include: phenylene, biphenylene, naphthylene, methylene, ethylene, 1,3-propylene, 1,4-butylene, phenylmethylene (-C6H4-CH2-). The polyvalent hydrocarbyl part G can also be substituted with radicals that do not interfere with the coupling function of the active hydrogen moiety. Preferred examples of such non-interfering substituents are alkyl- or aryl-substituted alkyl, aryl, silyl and germyl radicals, and fluoro substituents.

The group TH in the previous formula can therefore be a group: -OH, -SH, -NRH or -PRH, in which R is preferably a C1-18 hydrocarbyl radical, preferably a C1-10 hydrocarbyl radical or hydrogen, and H is hydrogenic. Preferred R groups are: alkyls, cycloalkyls, aryls, arylalkyls or alkylaryls of 1 to 18 carbon atoms, more preferably those of 1 to 12 carbon atoms. The groups: -OH, -SH, -NRH or -PRH can be part of a larger functionality such as, for example, C (O) -OH, C (S) -SH, C (O) -NRH and C ( O) -PRH. Most preferably, the group TH is a hydroxy group, -OH, or an amino group, -NRH.

Highly preferred substituents Gp (TH) r comprising an active hydrogen moiety including groups: hydroxy- and amino-substituted aryl, aralkyl, alkaryl or alkyl, and the most preferred are the hydroxyphenyls, especially the 3- and 4-hydroxyphenyl groups, hydroxytolyls, hydroxybenzyl (hydroxymethylphenyl), hydroxybiphenyls, hydroxynaphthyls, hydroxycyclohexyl, hydroxymethyl and hydroxymethyl groups. corresponding amino-substituted groups, especially those substituted with -NRH in which R is an alkyl or aryl radical having 1 to 10 carbon atoms, such as for example: methyl, ethyl, propyl, isopropyl, n-, iso- or tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl, phenyl, benzyl, tolyl, xylyl, naphthyl and biphenyl.

The compatible anion containing the substituent containing an active hydrogen moiety may further comprise a uonic element from Groups 5-15 or a plurality of elements from Groups 5-15, but is preferably a uonic coordination complex comprising a load-bearing metal or metalloid nucleus, whose anion is bulky. A compatible anion specifically refers to an anion that when functioning as a charge balancing anion in the catalyst system of this invention, does not transfer an anioonic substituent or fragment thereof to the transition metal cation whereby a compound of neutral transition metal and a neutral metal by-product. "Compatible anions" are anions that do not degrade to neutrality when the initially formed complex decomposes and do not interfere with subsequent desired polymerizations. Preferred anions are those that contain a uonic coordination complex comprising a charge-bearing metal or metalloid nucleus carrying a substituent containing an active hydrogen moiety.

ES 2 188 751 T3 whose anion is relatively large (bulky), capable of stabilizing the active catalytic species (the transition metal cation) that is formed when the activating compound and the transition metal compound are combined and said anion will be sufficiently It is ready to be replaced by olephonic, diolephonic and acetyloenically unsaturated compounds or other neutral Lewis bases such as ethers, nitriles and the like. Suitable metals for activator compound anions include, but are not limited to, aluminum, gold, platinum, and the like. Suitable metalloids include, but are not limited to, boron, phosphorus, silicon, and the like. Activator compounds containing anions comprising a coordination complex containing an aotomic boron uonic and a substituent comprising an active hydrogen moiety are preferred.

Preferably, compatible anions containing a substituent comprising an active hydrogen moiety can be represented by the following general Formula (I):

[M '^{m +}Qn (Gq (TH) r) z]^d- (I) in which:

M 'is a metal or metalloid selected from Groups 5-15 of the Periodic Table of the Elements;

Q independently in each case is selected from the group consisting of: hydride, dihydrocarbylamido, preferably dialkylamido, halide, hydrocarbyloxide, preferably alkooxide and arylooxide, hydrocarbyl and substituted hydrocarbyl radicals, including halo-substituted hydrocarbyl radicals, and hydrocarbyl- and halohydrocarbyl-substituted organometalloid radicals , the hydrocarbyl part having from 1 to 20 carbons with the condition that in no more than one case Q is halide;

G is a polyvalent hydrocarbon radical, with r + 1 valences and preferably divalent, attached to

My T;

T is O, S, NR, or PR, where R is a hydrocarbon radical, a trihydrocarbylsilyl radical, a trihydrocarbylgermyl or hydrogenic radical;

m is an integer number from 1 to 7, preferably 3; integer nesunnuomer from 0 to 7, preferably 3; q is the integer number 0 or 1, preferably 1; r is an integer number from 1 to 3, preferably 1; z is an integer number from 1 to 8, preferably 1; Integer desunnuomer from 1 to 7, preferably 1; and n + zm = d.

Preferred boron-containing anions, which are particularly useful in this invention, can be represented by the following general Formula (II):

[BQ4-Z '(Gq (TH) r) z']^d- (II) in which:

B is boron in a valence state of 3;

z 'is an integer number from 1-4, preferably 1;

des1; and

Q, G, T, H, q and r are as defined for Formula (I). Preferably, z 'is 1, q is 1, and r is 1.

Illustrative, but not limiting, examples of activator compound anions for use in the present invention are boron-containing anions such as triphenyl (hydroxyphenyl) borate, diphenyldi (hydroxyphenyl) borate, triphenyl (2,4-dihydroxyphenyl) borate, tri (p - tolyl) (hydroxyphenyl) borate, tris - (pentafluorophenyl) (hydro9

ES 2 188 751 T3 xiphenyl) borate, tris - (2,4-dimethylphenyl) (hydroxyphenyl) borate, tris - (3,5-dimethylphenyl) (hydroxyphenyl) borate, tris - (3,5-di-trifluoromethylphenyl) (hydroxyphenyl) ) borate, tris (pentafluorophenyl) (2-hydroxyethyl) borate, tris (pentafluorophenyl) (4-hydroxybutyl) borate, tris (pentafluorophenyl) (4-hydroxycyclohexyl) borate, tris (pentafluorophenyl) (4 - (4) - hydroxyphenyl) ) borate, tris (pentafluorophenyl) (6-hydroxy-2-naphthyl) borate and the like. A highly preferred activator complex is tris (pentafluorophenyl) (4-hydroxyphenyl) borate. Other preferred anions of activator compounds are the aforementioned borates in which the hydroxy functionality is replaced by an amino NHR functionality in which R is preferably methyl, ethyl or tert-butyl.

The cationic part b.1) of the activator compound to be used together with the compatible anion b.2) can be any cation that is capable of reacting with the transition metal compound to form a catalytically active transition metal complex, especially a cationic transition metal complex. The cations b.1) and the anions b.2) are used in such ratios that a neutral activator compound is given. Preferably the cation is selected from the group consisting of Bronsted acid cations, carbonium cations, silylium cations, and cationic oxidizing agents.

Broonsted acid cations can be represented by the following general formula:

(LH)⁺ in which:

L is a neutral Lewis base, preferably a Lewis base containing nitrogen, phosphorus or sulfur; and (LH)⁺ It is a Broonsted acid. Broonsted acid cations are believed to react with the transition metal compound by transferring a protoon from said cation, the proton of which combines with one of the ligands in the transition metal compound to release a neutral compound.

Illustrative, but not limiting, examples of Broonsted acidic cations of activator compounds to be used in the present invention are trialkylsubstituted ammonium cations such as triethylammonium, tripropylammonium, tri (n-butyl) ammonium, trimethylammonium, tributylammonium and tri (n-octyl) ammonium. . Also suitable are N, N-dialkylanilinium cations such as: N, N-dimethylanilinium; N, N-diethylanilinium; N, N2,4,6-pentamethylanilinium; N, N-dimethylbenzylammonium and the like; dialkylammonium cations such as di (isopropyl) ammonium, dicyclohexylammonium, and the like; and triarylphosphonium cations such as triphenylphosphonium, tri (methylphenyl) phosphonium, tri (dimethylphenyl) phosphonium, dimethylsulfonium, diethylsulfonium, and diphenylsulfonium.

A second type of suitable cations correspond to the formula © +, in which © + is a stable carbonium or silyl ion containing up to 30 atoms that are not hydrogen, the cation being capable of reacting with a substituent of the transition metal compound. and converting it to a catalytically active transition metal complex, especially a cationic transition metal complex. Suitable examples of cations include: tropilium, triphenylmethylium, benzene (diazonium). Silylium salts have been previously described generically in J. Chem. Soc. Chem. Comm., 1993, 383-384, as well as Lambert, JB, et al., Organometallics, 1994, 13, 2430-2443. Preferred silylium cations are: triethylsilylium and trimethylsilylium and ether substituted adducts thereof.

Another type of suitable cation comprises a cationic oxidizing agent represented by the formula:

_Ox^{e +} in which Ox^{e +} is a cationic oxidizing agent with a charge of e⁺, and is an integer number from 1 to 3.

Examples of cationic oxidizing agents include: ferrocene, hydrocarbyl substituted ferrocene, Ag⁺ yPb²⁺.

The amount of activator compound in the supported catalyst component and the supported catalyst is not chromic, but topically varies from 0.1; preferably 1 to 2,000 micromoles of activator compound per gram of treated support material. Preferably, the supported catalyst or component contains 10 to 1,000 micromoles of activator compound per gram of treated support material.

The supported catalyst component of the present invention as such or in suspension in a diluent can be stored or transported under inert conditions, or it can be used to generate the supported catalyst of the present invention.

IS 2 188 751 T3

Suitable transitionon metal compounds for use in the supported catalyst of the present invention are those that contain a substituent capable of reacting with activator compound (b) to thereby form a catalytically active transitional metal complex. The transition metal compounds can be derived from any transition metal including the Lantoanides, preferably from Groups 3, 4, 5 and 6, but preferably from transition metals from Groups 3 or 4 of the Lantoanides, whose transition metals are tin in the formal oxidation state +2, +3 or +4. The transition metals preferably contain at least one π-linked anionic ligand group which may be an anionic, π-linked, delocalized, colic or non-colic ligand group. Examples of such a π-linked anionic ligand group are conjugated or unconjugated coclic or noncoclic dienyl groups, allyl groups, aryl groups, as well as substituted derivatives of such groups.

By the terminology "derivative" when used to describe the above substituted, delocalized π-linked groups, it is meant that each atom in the delocalised π-linked group can be independently substituted with a radical selected from the group formed. by: halogen, hydrocarbyl, halohydrocarbyl and hydrocarbyl substituted metalloid radicals in which the metalloid is selected from Group 14 of the Periodic Table of the Elements. Included within the terminology "hydrocarbyl" are C1-20 linear, branched and coclic alkyl radicals, C6-20 aromatic radicals, C7-20 alkyl substituted aromotic radicals and C7-20 aryl substituted alkyl radicals. In addition, two or more of such radicals may together form a fused ring system or a hydrogenated fused ring system. Suitable hydrocarbyl-substituted organometalloid radicals include mono-, di- and tri-substituted organometalloid radicals of Group 14 elements in which each hydrocarbyl group contains from 1 to 20 carbon atoms. More particularly, suitable hydrocarbyl-substituted organometalloid radicals include: trimethylsilyl, triethylsilyl, ethyldimethylsilyl, methyldiethylsilyl, triphenylgermyl, trimethylgermyl, and the like.

Preferred delocalized π-linked anionic groups include substituted cyclopentadienyl and cyclopentadienyl groups. Especially preferred are: cyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl, tetrahydrofluorenyl and octahydrofluorenyl. Other examples of preferred anioonic ligand groups are: pentadienyl, cyclohexadienyl, dihydroanthracenyl, hexahydroanthracenyl and decahydroanthracenyl groups and methyl-substituted derivatives thereof.

Suitable transition metal compounds (c) may be: a cyclopentadienyl or substituted cyclopentadienyl derivative of any transition metal including Lantoanides, but preferably Group 3, 4 or Lantaonide transition metals. Suitable transitional metal compounds for use in the present invention are substituted, bridged or non-bridged mono-, bis- and tri-cyclopentadienyl or cyclopentadienyl transition metal compounds.

Suitable non-bridged, transitional metal derivatives of monocyclopentadienyl or mono (substituted cyclopentadienyl) are represented by the general Formula (3):

CpMXn (3) in which Cp is cyclopentadienyl or a derivative thereof, M is a Group 3, 4 or 5 transition metal having a formal oxidation state of +2, +3 or +4, X independently in each case represents an anionic ligand group (other than an anioonic ligand group, π-bonded, aromatic, colic) selected from the group of radicals: hydrocarbyl, hydrocarbylene (including hydrocarbyanyl), hydrocarbyloxy, hydride, halo, silyl, germyl, amido, and siloxy, having up to 50 non-hydrogenic aotoms, provided that at least one X is selected from the group: a hydride radical, hydrocarbyl radical, substituted hydrocarbyl radical or organometalloid radical, and n, a nuomer equal to one less than the formal oxidation state of M, is 1, 2 or 3, preferably 3. Preferably, at least one X is a hydrocarbyl radical having 1 to 20 carbon atoms, a substituted hydrocarbyl radical having 1 to 20 carbon atoms in which one or more of the hydrogen atoms are replaced with an atom of halogen, or an organometaloid radical comprising a Group 14 element in which each hydrocarbyl substituent contained in the organic part of said organometalloid, independently, it contains from 1 to about 20 carbon atoms.

Suitable bridged monocyclopentadienyl or mono (substituted cyclopentadienyl) transition metal compounds include so-called restricted geometry complexes. Examples of such complexes and methods for their preparation are described in U.S. Patent Application Serial No. 545,403, filed July 3, 1990 (corresponding to EP-A-416,815), Application for US Patent No.^° Serial No. 241,523, filed May 12, 1994 (corresponding to WO-95/00526), ​​as well as US Patents 5,055,438, 5,057,475, 5,096,867, 5,064,802,

IS 2 188 751 T3

5,132,380 and 5,374,696.

More particularly, preferred bridged transition metal, monocyclopentadienyl or mono (substituted cyclopentadienyl) compounds correspond to Formula (IV):

<img file="ES2188751T3_D0001.tif" />

in which:

M is a Group 3-5 metal, especially a Group 4 metal, particularly titanium;

Cp * is a substituted cyclopentadienyl group attached to Z 'and, in an η bond mode⁵, M or such a group is further substituted with one to four substituents selected from the group consisting of: hydrocarbyl, silyl, germyl, halo, hydrocarbyloxy, amine and mixtures thereof, said substituent having up to 20 non-hydrogen atoms, or optionally , two such additional substituents together cause Cp * to have a fused ring structure;

Z 'is a divalent residue other than an anioonic, π-bonded, coyclic or non-coyclic ligand, said Z' comprising boron, or a member of Group 14 of the Periodic Table of the Elements, and optionally nitrogen, phosphorus, sulfur or oxygen, said residue having up to 20 non-hydrogen atoms and optionally Cp * and Z 'together form a fused ring system;

X has the same meaning as in Formula (III); and nes1 or 2 depending on the valence of M.

Consistent with the previous explanation, M is preferably a Group 4 metal, especially titanium; n is 1 or 2; and X is a monovalent ligand group of up to 30 atoms that are not hydrogenic, most preferably C1-20 hydrocarbyl.

When n is 1 and the Group 3-5 metal (preferably Group 4 metal) was in the +3 formal oxidation state, X is preferably a stabilizing ligand.

By the terminology "stabilizing ligand" is meant that the ligand group stabilizes the metal complex through either:

1) a chelating bond of nitrogen, phosphorus, oxygen or sulfur, or

2) a bond η³ with a delocalized, resonant π-electroonic structure.

Examples of stabilizing ligands of group 1) include silyl, hydrocarbyl, amido or phosphido ligands substituted with one or more ether, thioether, amino or phosphine, alifaotic or aromatic functional groups, especially such amino or phosphine groups which are tertiary, substituted, having said Stabilizing ligand for non-hydrogen atoms. Preferred group 1) maos stabilizing ligands are 2-dialkylaminobenzyl or 2- (dialkylaminomethyl) phenyl groups containing 1 to 4 carbons in the alkyl groups.

Examples of stabilizing ligands of group 2) include C3-10 hydrocarbyl groups containing ethyloenic unsaturations such as allyl, 1-methylallyl, 2-methylallyl, 1,1-dimethylallyl or 1,2,3-trimethylallyl groups.

Even more preferred, such coordination metal complexes correspond to Formula (V):

IS 2 188 751 T3

<img file="ES2188751T3_D0002.tif" />

wherein R 'in each case independently is selected from the group consisting of: hydrogen, hydrocarbyl, silyl, germyl, cyano, halo and combinations thereof, having up to 20 non-hydrogen atoms, or two R' groups together form a divalent derivative thereof;

X has the same meaning as defined for Formula (III);

Y is a divalent ammonium ligand group comprising nitrogen, phosphorus, oxygen or sulfur and having up to 20 non-hydrogenic atoms, said Y being attached to Z and M through said nitrogen, phosphorus, oxygen or sulfur, and optionally Y and Z together form a fused ring system;

M is a Group 4 metal, especially titanium;

Z is SiR *₂, CR *₂, SiR *₂Sir*₂, * pn * γφ * _pd *

CR₂CR ₂, CR = CR,

CR^*2SiR^*2, GeR^*2, BR^* oBR^*2;

in which:

R * in each case independently is selected from the group consisting of: hydrogen, hydrocarbyl, silyl, halogenated alkyl, halogenated aryl groups that have up to 20 atoms that are not hydrogenic, and mixtures thereof, or two or more R * groups of Z , or a group R * of Z together with Y form a fused ring system; and nes1óo2.

Furthermore, preferably, Y is -O-, -S-. -NR *, -PR * -. It is highly preferable that Y is a nitrogen- or phosphorus-containing group corresponding to the formula -N (R ') - or -P (R') -, where R 'is as described above, that is, an amido group or phosphide.

The most highly preferred coordination metal complexes correspond to Formula (VI):

<img file="ES2188751T3_D0003.tif" />

in which:

M is titanium;

R 'in each case independently is selected from the group consisting of: hydrogen, silyl, hydrocarbyl, and combinations thereof having up to 10 carbon or silicon atoms, or two R' groups of the substituted cyclopentadienyl moiety joined together;

E is silicon or carbon;

X independently in each case is: hydride, alkyl, aryl, up to 10 carbons;

ES 2 188 751 T3 m is 1 or 2; and n is 1 or 2.

Examples of the above most highly preferred coordination metal compounds include compounds where the R 'in the amido group is: methyl, ethyl, propyl, butyl, pentyl, hexyl, (including isomers), norbornyl, benzyl, phenyl, and cyclododecyl; (ER'2) m is dimethylsilane or 1,2-ethylene; R 'in the cyclic group linked by π bond, independently in each case, is: hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, norbornyl, benzyl and phenyl, or two R' groups are joined to form a residue: indenyl , tetrahydroindenyl, fluorenyl, or octahydrofluorenyl; and X is: methyl, ethyl, propyl, butyl, pentyl, hexyl, norbornyl, benzyl, and phenyl.

Transition metal compounds in which the transition metal was in the +2 formal oxidation state include complexes that contain one and only one group linked by π bond, anionic, delocalized, colic, said complexes corresponding to Formula (VII ):

<img file="ES2188751T3_D0004.tif" />

\

- M- X · (VII) in which:

M is titanium or zirconium in the +2 formal oxidation state;

L is a group that contains a π system, anionic, delocalized, colic, through which the group is attached to M, and whose group is also attached to Z;

Z is a residue linked to M by a σ bond, which comprises boron, or a member of Group 14 of the Periodic Table of the Elements, and which also comprises: nitrogen, phosphorus, sulfur or oxygen, said residue having up to 60 atoms that they are not hydrogenic; Y

X * a neutral diene, conjugated or unconjugated, optionally substituted with one or more hydrocarbyl groups, said X having up to 40 carbon atoms and forming a π-complex with M.

Preferred transition metal compounds of Formula (VII) include those in which Z, M and X * are as previously defined; and L is a C5H4 group attached to Z and attached in an η bonding mode⁵ a M or is such a group with η bond⁵ substituted with one to four substituents independently selected from: hydrocarbyl, silyl, germyl, halo, cyano, and combinations thereof, said substituents having up to 20 non-hydrogenic atoms, and optionally, two such substituents (except cyano or halo) together they cause a fused ring structure.

The preferred +2 masses transition metal compounds according to the present invention correspond to Formula (VIII):

<img file="ES2188751T3_D0005.tif" />

in which:

R 'in each case is independently selected from: hydrogen, hydrocarbyl, silyl, germyl, halo, cyano and combinations thereof, said R' having up to 20 non-hydrogen aotoms, and optionally, two R 'groups (where R' is not hydrogenic, halo or cyano) together they form a divalent derivative thereof attached to adjacent positions of the cyclopentadienyl ring to form a structure of

ES 2 188 751 T3 fused ring;

X * is an η-bonded diene group⁴ neutral having up to 30 non-hydrogen atoms, which forms a π-complex with M;

Y is -O-, -S-, -NR * -, -PR * -;

M is titanium or zirconium in the +2 formal oxidation state;

Z * is SiR^*2, CR^*2, SiR^*2SiR^*2, CR^*2CR^*2, CR^*= CR^*, CR^*2SiR^*two oGeR^*two; in which:

R * in each case is independently: hydrogen, or a member selected from: hydrocarbyl, silyl, halogenated alkyl, halogenated aryl, and combinations thereof, said R * having up to 10 non-hydrogenic aotoms, and optionally, two R * groups of Z * (when R * is not hydrogen) or an R * group of Z * and an R * group of Y form a ring system.

Preferably, R 'independently in each case is: hydrogenic, hydrocarbyl, silyl, halo and combinations thereof said R' having up to 10 non-hydrogenic aotoms, or two R 'groups (when R' is not hydrogenic or halo) together they form a divalent derivative thereof; Most preferably, R 'is: hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, (including where appropriate all isoomers), cyclopentyl, cyclohexyl, norbornyl, benzyl or phenyl or two R' groups (except hydrogen) they are joined together, thereby the entire C5R'4 group being, for example, an indenyl, tetrahydroindenyl, fluorenyl, tetrahydrofluorenyl or octahydrofluorenyl group.

Preferably further, at least one of R 'or R * is an electron donating moiety. By the terminology "electron donor" it is meant that the remainder is more electron donor than hydrogen. Therefore, highly preferred Y is a nitrogen- or phosphorus-containing group corresponding to the formula -N (R ") - or -P (R") -, where R "is C1-10 hydrocarbyl.

Examples of suitable X * groups include: s - trans - η⁴ - 1,4-diphenyl-1,3-butadiene; s - trans - η⁴ 3-methyl-1,3-pentadiene; s - trans - η⁴ - 1,4-dibenzyl-1,3-butadiene; s - trans - η⁴ - 2,4-hexadiene; s - trans - η⁴ - 1,3-pentadiene; s - trans - η⁴ - 1,4-ditolyl-1,3-butadiene; s - trans - η⁴ - 1,4 bis (trimethylsilyl) -1,3-butadiene; s - cis - η⁴ - 1,4-d phenyl-1,3- butadiene; s - cis - η⁴ -3-methyl-1,3pentadiene; s - cis - η⁴ - 1,4-dibenzyl-1,3-butadiene; s - cis - η⁴ - 2,4-hexadiene; s - cis - η⁴ -1,3-pentadiene; s - cis - η⁴ - 1,4-ditolyl-1,3-butadiene; ys - cis - η⁴ - 1,4-bis (trimethylsilyl) -1,3-butadiene, said s-cis diene group forming a π-complex as defined herein with the metal.

Highly preferred +2 plus transition metal compounds are amidosilane or amidoalkanediyl compounds of Formula VIII) wherein:

-Z * -Y- is - (ER ”'²) mN (R ") - and R 'in each case independently is selected from: hydrogen, silyl, hydrocarbyl and combinations thereof, said R' having up to 10 carbon or silicon atoms, or two of such R 'groups in the substituted cyclopentadienyl group (when R 'is not hydrogenic) together form a divalent derivative thereof attached to adjacent positions on the cyclopentadienyl ring;

R "is C1-10 hydrocarbyl;

R "'is independently in each case hydrogen or C1-10 hydrocarbyl; E is independently in each case silicon or carbon; and mes1oó2.

Examples of metal complexes according to the present invention include compounds where R "is: methyl, ethyl, propyl, butyl, pentyl, hexyl (including all isoomers of the foregoing where applicable), cyclododecyl, norbornyl, benzyl, or phenyl ; (ER "'2) m is dimethylsilane or ethanediyl; and the delocalized π-linked cocyclic group is cyclopentadienyl, tetramethylcyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, tetrahydrofluorenyl, or octahydrofluorenyl.

Suitable bis (cyclopentadienyl) derivatives of transition metals include the compounds of titanium, zirconium and hafnium and can be represented by the following general Formulas (IX) - (XII):

ES 2 188 751 T3 (A-Cp) MX1X2 (IX) (A-Cp) MX'1^—X2 '(X) (A-Cp) ML (XI) (Cp *) (CpR) MX1 (XII) in which: M is a Group 4 metal that is, titanium (Ti), zirconium (Zr) and hafnium (Hf); (A-Cp) is either (Cp) (Cp *) or Cp-A'-Cp * and Cp and Cp * are the same or different cyclopentadienyl radicals, as well as substituted derivatives of cyclopentadienyl radicals, and A 'is a bridged group covalent containing a Group 14 element; L is an olefin, diolefin, or aryne ligand; at least one of X1 and X2 is a hydride radical, hydrocarbyl radical, substituted hydrocarbyl radical or organometaloid radical, the other of X1 and X2 being a hydride radical, hydrocarbyl radical, substituted hydrocarbyl radical, organometalloid radical, or a hydrocarbyloxy radical; preferably one or both, X1 and X2, are a hydrocarbyl radical having 1 to about 20 carbon atoms, substituted hydrocarbyl radical having 1 to about 20 carbon atoms in which one or more of the hydrogen atoms are replaced with a halogen atom, an organometaloid radical comprising a Group 14 element in which each of the hydrocarbyl substituents contained in the organic part of said organometaloid, independently, contains from 1 to about 20 carbon atom; X'1 and X'2 are together and bind to the metal atom to form a metalacycle, in which the metal, X'1 and X'2 form a hydrocarbocolic ring containing from about 3 to about 20 carbon atoms; and R is a substituent, preferably a hydrocarbyl substituent, having 1 to 20 carbon atoms on one of the cyclopentadienyl radicals, which is also attached to the metal atom.

When X1 and X2 are not both a hydride radical, hydrocarbyl radical, substituted hydrocarbyl radical, or organometalloid radical, one of these may be a hydrocarbyloxy radical having 1 to 20 carbon atoms. Suitable examples of hydrocarbyloxy radicals include alkyloxy, aryloxy, aralkyloxy and alkaryloxy radicals, having 1 to 20 carbon atoms, more preferably alkyl radicals having 1 to 6 carbon atoms, and aryl, aralkyl and alkaryl radicals having 6 at 10 carbon atoms, even more preferably isopropyloxy, n-butyloxy or tert-butyloxy.

Examples of such transition metal bis (cyclopentadienyl) derivatives and methods for their preparation are described in US patent 5,384,299 (corresponding to EP-A-277,004) and US patent application. .US. N^° No. 459,921, filed January 2, 1990 (corresponding to WO-91/09882).

Suitable tri-cyclopentadienyl or substituted cyclopentadienyl transition metal compounds include those containing a bridging group linking two cyclopentadienyl groups and groups without such bridges.

Suitable unbridged tri-cyclopentadienyl transition metal derivatives are represented by the general Formula (XIII):

CpsMXn (XIII) where Cp, M and X are as defined for Formula (III) and n "is three less than the formal oxidation state of M and is 0 or 1, preferably 1. Preferred ligand groups X are : hydrocarbyl, hydrocarbyloxy, hydride, halo, silyl, germyl, amido and siloxy.

Typically, the ratio of moles of activator compound (b) to atom-grams of transition metal in compound (c) in the supported catalyst is 0.05: 1 to 100: 1, preferably 0.5: 1 to 20: 1 and preferably 1: 1 to 5: 1 moles of activator compound per atom-gram of transition metal in the transition metal compound. At too low ratios the supported catalyst will not be very active, while at too high ratios the catalyst becomes less economical due to the relatively high cost associated with the use of large amounts of activator compound.

The supported catalyst component of the present invention can be prepared by combining the support material with the organometallic compound, preferably an aluminum component, and the activator compound. The order of addition is not chromic. The organometallic compound can be combined either first with the support material or with the activator compound, and the activator compound or the support material can be added later. A preferred embodiment comprises treating the support material first with the organometallic compound, preferably the aluminum component by combining the organometallic compound in a suitable solvent, such as a hydrocarbon solvent,

ES 2 188 751 T3 with the support material. The temperature, pressure and contact time for this treatment are not critical, but usually range from -20 ° C to about 150 ° C, from subatmospheric to 10 bar, more preferably at atmospheric pressure, for 5 minutes to 48 hours. Usually the suspension is shaken. After this treatment the solids are topically separated from the solvent. Any excess organometaolic compound could then be removed by techniques known in the art. This method is especially suitable for obtaining support material with relatively low metal, preferably aluminum, loads.

According to a preferred embodiment, the support material is first subjected to a heat treatment at a temperature in the range of 100 ° C to 1,000 ° C, preferably from about 200 ° C to about 850 ° C. Typically, this treatment is carried out from about 10 minutes to about 72 hours, preferably from about 0.5 hours to 24 hours. The heat treated support material is then combined with the organometallic compound, preferably AlR'3 in which R 'has the meaning defined hereinbefore in a suitable solvent or diluent, preferably one in which the organometallic compound is soluble. Topical solvents are hydrocarbon solvents having 5 to 12 carbon atoms, preferably aromotic solvents such as toluene and xylenes, or aliphatic solvents with 6 to 10 carbon atoms, such as hexane, heptane, octane, nonane, decane and isoomers of the same, cycloalifaotic solvents of 6 to 12 carbon atoms such as cyclohexane or mixtures of any of these.

The support material is combined with the organomethyl compound at a temperature of -20 ° C to 150 ° C, preferably 20 ° C to 100 ° C. The contact time is not critical and can range from 5 minutes to 72 hours, and is preferably 0.5 hours to 36 hours. Agitation is preferably applied. The treated support material is therefore preferably contacted afterwards with the activator compound.

An alternative treatment of the support material, suitable to obtain alumoxane fillers attached to the support material, involves one or both of the following steps A and B:

A. heating a support material containing alumoxane in an inert atmosphere for a period and at a temperature sufficient to fix alumoxane to the support material;

B. subjecting the alumoxane-containing support material to one or more washing steps to remove unbound alumoxane from the support material;

thereby selecting the conditions in heating stage A and washing stage B such that a treated support material is formed in which no more than about 10 percent of the aluminum present in the treated support material c is extractable in a hour of extraction with toluene at 90 ° C using approximately 10 ml of toluene per gram of supported catalyst component. High amounts of alumoxane bound to the support material are obtained using first heating stage A, optionally followed by washing stage B.

In this process, the alumoxane treated support material can be obtained by combining an alumoxane in a diluent with a support material containing from zero to no more than 20 percent by weight of water, preferably from zero to no more than 6 weight percent water, based on total weight of carrier material and water. Although support materials that do not contain substantially water perform well with respect to the catalytic properties of the supported catalyst, it has been found that support materials that contain relatively small amounts of water can be used without problem in the present process. The water-containing support materials, when combined under ideal conditions with the same amount of alumoxane, give in the present process a supported catalyst component with a slightly higher aluminum content than the substantially water-free support material. It is believed that the water reacts with the residual amounts of alkylaluminum present in the alumoxane to convert the alkylaluminum into extra alumoxane. An additional advantage is that less aluminum alkyl was lost in this way in waste or recycle streams. It is desirable to use the alumoxane in dissolved form.

Alternatively, the pretreated alumoxane support material can be obtained by combining in a diluent, a support material containing from 0.5 to 50 percent by weight of water, preferably from 1 to 20 percent by weight of water, based on the total weight of support material and water, with a compound of the formula R "_n* AlX "_3-n* where R "independently in each case is a hydrocarbyl radical, X" is halogen or hydrocarbyloxy, and n * is an integer number from 1 to 3. Preferably, n * is 3. R "independently in each case is preferably a radical alkyl, advantageously containing 1 to 12 carbon atoms. Preferred alkyl radicals are: methyl, ethyl, propyl,

ES 2 188 751 T3 isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, hexyl, isohexyl, heptyl, octyl and cyclohexyl. Highly preferred compounds of formula R "_n* AlX "₃__n* They are: trimethylaluminum, triethylaluminum and triisobutylaluminum. When the alumoxane is prepared in situ by reacting the compound of formula R "_n* AlX "₃__n* with water, the molar ratio of R "_n* AlX "₃__n* a water is typically 10: 1 to 1: 1, preferably 5: 1 to 1: 1.

The support material is added to the alumoxane or compound of the formula R "_neither!AlX "_3-n*, preferably dissolved in a solvent, most preferably a hydrocarbon solvent, or the solution of alumoxane or compound of formula R is added "_neither!AlX "_3-n* to the support material. The support material can be used as such in dry form or in suspension in a hydrocarbon diluent. Both aliphatic and aromatic hydrocarbons can be used. Suitable alifaotic hydrocarbons include, for example, pentane, isopentane, hexane, heptane, octane, isooctane, nonane, isononane, decane, cyclohexane, methylcyclohexane, and combinations of two or more of such diluents. Suitable examples of aromatic diluents are: benzene, toluene, xylene, and other alkyl or halogen substituted aromaotic compounds. Most preferably, the diluent is an aromatic hydrocarbon, especially toluene. Suitable concentrations of solid support in the hydrocarbon medium range from about 0.1 to about 15, preferably from about 0.5 to about 10, more preferably from about 1 to about 7 percent by weight. Contact time and temperature are not chromatic. Preferably the temperature is 0 ° C to 60 ° C, more preferably 10 ° C to 40 ° C. The contact time is 15 minutes to 40 hours, preferably 1 to 20 hours.

Before subjecting the alumoxane treated support material to the heating step or washing step, the diluent or solvent is preferably separated to obtain a loose powder or granules. This is preferably done by applying a technique that only separates the liquid and leaves the aluminum compounds in the solids, such as applying heat, reduced pressure, evaporation, or a combination thereof. If desired, the diluent removal can be combined with the heating step, although care should be taken that the diluent separates gradually.

The heating step and / or the washing step are conducted in such a way that a very large proportion (more than about 90 percent by weight) of the alumoxane remaining in the support material is fixed. Preferably a heating step is used, more preferably a heating step followed by a washing step is used. When used in the preferred combination, both steps cooperate so that the alumoxane binds to the support material in the heating step, while the washing step removes the alumoxane that does not bind to a substantial degree. The upper temperature for the thermal treatment was preferably below the temperature at which the support material begins to agglomerate and form lumps that are difficult to redispersion, and below the decomposition temperature of the alumoxane. When the transition metal compound c) is added before the thermal treatment, the heating temperature should be below the decomposition temperature of the transition metal compound. Preferably, the thermal treatment is carried out at a temperature of 75^°C to 250^°C for a period of 15 minutes to 24 hours. Most preferably, the thermal treatment is carried out at a temperature of 160^°C to 200^°C for a period of 30 minutes to 4 hours. Good results have been obtained even if heated for 8 hours at 100^°Cooked as though heated for 2 hours at 175^°C. By means of preliminary experiments, a person skilled in the art will be able to define the thermal treatment conditions that will provide the desired result. It is also observed that the longer the thermal treatment takes, the greater the amount of alumoxane fixed to the support material. The thermal treatment is carried out under reduced pressure or in an inert atmosphere, such as nitrogen gas, or both but preferably under reduced pressure. Depending on the conditions in the heating step, the alumoxane can be attached to the support material to such a high degree that a washing step can be omitted.

In the washing step, the number of washes and the solvent used are such that sufficient amounts of unfixed alumoxane are removed. The wash conditions should be such that the unfixed alumoxane is soluble in the wash solvent. The support material containing alumoxane, preferably already subjected to a thermal treatment, is preferably subjected from one to five washing steps using an aromatic hydrocarbon solvent at a temperature of 0^°C to 110^°C. Maós preferably, the temperature is 20^°C to 100^°C. Examples of preferred aromaotic solvents include toluene, benzene, and xylenes. Most preferably, the aromatic hydrocarbon solvent is toluene. At the end of the wash treatment, the solvent is removed by a technique that also removes the alumoxane dissolved in the solvent, such as by filtration or decantation. Preferably, the wash solvent is removed to provide a loose powder or granules.

The organometallic compound treated support material is then topically resuspended

ES 2 188 751 T3 in a suitable diluent and combined with the activator compound. The activator compound is preferably used in a diluent. Suitable diluents include hydrocarbon and halogenated hydrocarbon diluents. Any type of solvent or diluent can be used that does not react with the catalyst components in a way that adversely affects the catalytic properties. Preferred diluents are aromatic hydrocarbons such as toluene, benzene, and xylenes and aliphatic hydrocarbons such as hexane, heptane, and cyclohexane. Preferred halogenated hydrocarbons include methylene chloride and carbon tetrachloride. The temperature is not critical but normally varies between -20 ° C and the decomposition temperature of the activator. Topical contact times vary from a few minutes to several days. Stirring of the reaction mixture is preferred. Advantageously, the activator compound dissolves, using heat to promote dissolution where desired. It may be desirable to carry out contact between the organometaolic treated support material and the activator compound at elevated temperatures. Preferably, such elevated temperatures are 45^°C to 120^°C.

Instead of first treating the support material with the organometallic compound, preferably the aluminum component, and subsequently adding the activator compound, the organometallic compound, preferably the aluminum component, and the activator compound can be combined in a suitable diluent before adding or combine the reaction mixture to or with the support material.

Without wishing to be bound by theory, it is believed that an orgaonic group of the organometaolic compound reacts with the active hydrogen moiety contained in the activator anion b.2) to form a reaction product (also hereinafter referred to as "adduct" ). For example, when the organometaolic compound is trialkylaluminum AlR3 and the active hydrogen-containing moiety is represented by G-OH, the reaction product is believed to comprise GO-AlR2 while additionally forming an alkane by-product RH. This GO-AlR2 adduct when combined with the hydroxyl group-containing support material, Si-OH in case of a solid support material, is believed to form Si-O-Al (R) -OG together with RH alkane as a by-product. This method of preparing the supported catalyst component has been found to be very smooth and provides catalysts and catalyst precursors or components with desirable properties. Topical ratios to be used in this reaction are from about 1: 1 to about 20: 1 moles of organometallic compound to mole equivalents of active hydrogen residues contained in the activator anion b.2).

The amount of adduct, formed by combining the organometallic compound with the activator compound, to be combined with the support material is not chromic. Preferably, the amount is not greater than that which can be attached to the support material. Topically, this is determined by the amount of hydroxyls in the support material. The amount of adduct to be used is preferably no more than the equivalent amount of such hydroxyl groups. Less than the equivalent amount is preferably used, more preferably the ratio between moles of adduct and moles of surface reactive groups such as hydroxyl was between 0.01 and 1, even more preferably between 0.02 and 0.8. Before adding the transition metal compound it is preferred, especially when less than an equivalent amount of adduct is added, with respect to the surface reactive groups, to add an additional amount of organometaolic compound to the reaction product of support material and the adduct to separate any remaining surface reactive groups, which may otherwise react with the transition metal and therefore require larger amounts of it to achieve the same catalytic activity. Before combining with the transition metal compound, the supported catalyst component can be washed, if desired, to remove any excess adduct or organometallic compound.

The supported catalyst component comprising the support material, organometaolic compound, and the activator can be isolated to obtain a loose powder or granules by separation from the liquid medium preferably using filtration or evaporation techniques.

Although the transition metal compound can be combined with the activator compound, or the adduct of the organometallic compound and the activator compound, prior to combining the activator compound or its adduct with the support material, this results in reduced catalytic efficiencies. Preferably, the transition metal is first combined with the support material treated with the organometaolic component and before adding the activator compound, or the transition metal is added after the treated support material and the activator have been combined, or after that the activating adduct and the support material have been combined. Most preferably, the transition metal compound c) is added to the reaction product of the support material treated with the organometaolic compound and the activator compound, or after the activator adduct and the support material have been combined.

The transition metal compound is preferably used dissolved in a suitable solvent, such as a hydrocarbon solvent, advantageously a C5-10 aliphatic or cycloaliphatic hydrocarbon or a

ES 2 188 751 T3 C6-10 aromatic hydrocarbon. The contact temperature is not chromatic as long as it is below the decomposition temperature of the transition metal and activator. Good results are obtained in a temperature range from 0 ° C to 100 C. All steps in the present process should be conducted in the absence of oxygen and moisture.

In the combination of the transition metal compound with the supported catalyst component, the supernatant liquid is topically colorless indicating that the transition metal compound, the solution of which is topically colored, substantially remains with the solid supported catalyst.

The supported catalyst obtained by combining the support material, the organometaolic compound, the activator and the transition metal can be stored or transported in the form of loose granules under inert conditions after removal of the solvent.

The supported catalysts of the present invention can be used in an additive polymerization process in which one or more additive polymerizable monomers are contacted with the supported catalyst of the invention under additional polymerization conditions.

Suitable additionally polymerizable monomers include ethyloenically unsaturated monoomers, acetyloenic compounds, conjugated or unconjugated dienes, polyenes, and carbon monoxide. Preferred monoomers include olefins, for example alpha olefins having 2 to about 20, preferably about 2 to about 12, more preferably about 2 to about 8 carbon atoms and combinations of two or more of such alpha olefins. Particularly suitable alpha-olefins include, for example, ethylene, propylene, 1-butene, 1-pentene, 4-methylpentene-1, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1- undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, or combinations thereof. Preferably, the alpha-olefins are: ethylene, propene, 1-butene, 4-methylpentene-1, 1-pentene, 1-hexene, 1-octene and combinations of ethylene and / or propene with one or more of such other alpha- olefins. Suitable dienes include those with 4 to 30 carbon atoms, especially those with 5 to 18 carbon atoms. Topical of these are α, ω-dienes, α-internal dienes, including the dienes that are typically used to prepare EPDM-type elastomers. Typical examples include: 1,3-butadiene, 1,3- and 1,4-pentadiene, 1,3-,

1,4- and 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, and lower alkyl substituted anaologs of any of these. Other preferred monoomers include: styrene, halo- or alkyl-substituted styrenes, tetrafluoroethylene, vinylcyclobutene, dicyclopentadiene, and ethylidenenorbornenes. Suitable addition polymerizable monoomers also include any mixture of the monomers mentioned above.

The supported catalyst can be formed in situ in the polymerization mixture by introducing into said mixture both a supported catalyst component of the present invention, and its components, as well as a suitable transition metal compound c).

The supported catalyst can be used as is or after prior polymerization. The prepolymerization can be carried out by any known method such as by contacting a small amount of monomers, preferably alpha-olefins, with the supported catalyst.

The catalyst can be used in the polymerization reaction at a concentration of 10^-9 a10^-3moles, on a transition metal basis, per liter of diluent or reaction volume, but preferably used in a concentration of less than 10^-5, preferably 10^-8 a9x10^-6 moles per liter of diluent or reaction volume.

The supported catalyst can be used advantageously in a high pressure solution, suspension or gas phase polymerization process. A high pressure process is normally carried out at temperatures from 100 ° C to 400 ° C and at pressures above 500 bar. A topically slurry process uses an inert hydrocarbon diluent and temperatures from about 0 ° C to a temperature just below the temperature at which the resulting polymer becomes substantially soluble in an inert polymerization medium. Preferred temperatures are about 30 ° C, preferably about 60 ° C to about 115 ° C, preferably about 100 ° C. The solution process is carried out at temperatures from the temperature at which the resulting polymer is soluble in an inert solvent up to about 275 ° C. Normally, the solubility of the polymer depends on its density. For ethylene copolymers with densities of 0.86 g / cm³, solution polymerization can be achieved at temperatures as low as about 60 ° C. Preferably, solution polymerization temperatures range from about 75 ° C, more preferably from about 80 ° C, and typically from about 130 ° C to about 260 ° C, more preferably from about 170 ° C. Most preferably, the temperatures

ES 2 188 751 T3 in a tin solution process between approximately 80^°C and 150^°C. As inert solvents hydrocarbons and preferably aliphatic hydrocarbons are used topically. The processes in solution and in suspension are normally carried out at pressures between approximately 1 and 100 bar. Topical operating conditions for gas phase polymerizations are 20^°C to 100^°C, preferably more than 40^°C a80^°C. In gas phase processes the pressure is topically subatmospheric at 100 bar.

Preferably for use in gas phase polymerization processes, the support has a mean particle diameter of from about 20 to about 200 µm, more preferably from about 30 µm to about 150 µm, and most preferably from about 50 µm to about 100 µm. . Preferably for use in suspension polymerization processes, the support has a mean particle diameter of from about 1 µm to about 200 µm, more preferably from about 5 µm to about 100 µm, and most preferably from about 20 µm to about 80 µm. . Preferably for use in high pressure or solution polymerization processes, the support has a mean particle diameter of from about 1 µm to about 40 µm, more preferably from about 2 µm to about 30 µm, and most preferably from about 3 µm to about 40 µm. approximately 20 μm.

Additional details for polymerization conditions in a gas phase polymerization process can be found in US Patents 4,588,790, 4,543,399, 5,352,749, 5,405,922, in US Patent Application Serial No. .N^° No. 926,009 filed August 5, 1992 (corresponding to WO-94/03509 and US Patent Application No.^° Serial 122,582, filed September 17, 1993 (corresponding to WO-95/07942). Gas phase processes in which condensed monomer or inert diluent is present are preferred.

The supported catalysts of the present invention, also when used in a slurry or gas phase process, are not only capable of producing ethylene copolymers of densities typical for high density polyethylene, in the range of 0.970 to 0.940 g / cm³, but surprisingly, they also allow the production of copolymers with substantially lower densities. Copolymers with densities lower than 0.940 g / cm can be prepared³ and especially lower than 0.930 g / cm³ below 0.880g / cm³ or lower, while maintaining good bulk density properties and avoiding or substantially eliminating reactor greasing. The present invention is capable of producing olefin polymers and copolymers with weight average molecular weights of more than 30,000, preferably more than 50,000, more preferably more than 100,000 to 1,000,000 and even greater. Topical Mw / Mn molecular weight distributions range from 1.5 to 15, or even higher, preferably between 2.0 and 8.0.

Impurity scavengers that serve to protect the supported catalyst from catalyst poisons such as water, oxygen and polar compounds can be used in the polymerization process of the present invention. These scavengers can normally be used in amounts that depend on the amounts of impurities. Topical scavengers include organometaolic compounds, and preferably trialkylaluminum or boron compounds and alumoxanes.

Molecular weight control agents, such as hydrogen or other chain transfer agents, can also be used in the present polymerization process. The polymers that are prepared according to such a polymerization process can be combined with any conventional additives, such as UV stabilizers, antioxidants, anti-slip or antiblocking agents, which can be added in conventional ways, for example downstream of the polymerization reactor, or in an extrusion or molding step.

At or after separation of the polymerization mixture or product from the polymerization reactor, the supported catalyst can be deactivated by exposure to air or water, or through any other catalytic deactivation agent or process.

In the complex compounds of the present invention, preferably the compatible anioonic part b.2) corresponds to the general Formula (I):

[M '^{m +}Qn (Gq (T-Pr) r) z]^d- (I) in which:

M ', Q, G, T, m, n, q, r, z and d have the same definitions as in formula 1, and

IS 2 188 751 T3

Pr is hydrogen H or a protecting group. Preferred charge balancing cations and protecting groups are illustrated hereinafter.

Complex compounds containing anions b.2) can be prepared by combining a neutral compound, such as M '^m+ Q_m wherein M ', Q and m have the same meaning as in Formula (I), with an active metal derivative of the substituent comprising an active hydrogen residue, such as a lithium or Grignard derivative thereof, for example Z (Gq (TH) r), where Z is: Li⁺, MgCl⁺, MgBr⁺ oMgI⁺, and G, T, H, q and r have the same meanings as in Formula (I). The TH group can be protected during preparation by methods well known to those skilled in the art. For example, a hydroxy moiety can be protected by a trimethylsilyl group. The method for preparing the complex compounds, therefore, comprises combining in a suitable solvent or diluent a compound M '^{m +}Qm with a compound of the formula Z '(Gq (T-Pr) r), where Z' is [M'X "]⁺ or [M "]⁺and M 'is a Group 2 element, M "is a Group 1 element and X is halogen, G, T, Pr, q and r have the same meaning as given for Formula (I), optionally followed by recovery of complex product.

Suitable examples of protecting groups Pr include: trialkylsilyl, triarylsilyl and mixtures thereof, preferably trimethylsilyl, tert-butyldimethylsilyl, triisopropylsilyl, tert-butyldiphenylsilyl and phenyldimethylsilyl; preferably the protecting group contains a bulky substituent, such as tert-butyl or phenyl, to stabilize the resulting protecting group during subsequent metallaceton reaction.

The reaction between compound M '^{m +} Qm and Z¹(Gq (T-Pr) r) is carried out topically in an ether or any other organic diluent that does not adversely affect the desired reaction, and mixtures thereof. AND^or Preferred teres are tetrahydrofuran and diethyl ether. The temperature is not chromic and was topically in the range of -20 ° C to 100 ° C. The reaction mixture is preferably stirred and reacted for a period between 5 minutes and 72 hours.

It has been found advantageous to use a molar excess of compound Z¹(Gq (T-Pr) r) with respect to compound M '^{m +} Qm. Such excess is preferably 1.1 to 3 mole equivalents, more preferably 1.5 to 2.5 mole equivalents of Z¹(Gq (T-Pr) r) per mole of M '^{m +} Qm. Preferably, the reaction mixture is heated to a temperature between 40 ° C and 100 ° C, more preferably between 50 ° C and 95 ° C. The use of such process conditions was found to increase the conversion based on compound M '^{m +} Qm up to 90% and higher. As the compound M '^{m +} Qm is usually the most expensive reactant, it is highly desirable to increase the reaction yield with respect to this compound.

The product complex is then preferably recovered, for example by decantation, filtration, advantageously followed by washing, preferably with a hydrocarbon, and drying.

The protecting group Pr when present in the product complex is preferably removed by conventional methods, such as reacting the product complex with water, alcohol, orgaonic acids such as acetic acid, orgaonic anhydride compounds such as acetic anhydride, containing iron trichloride. , and tetrahydrocarbylammonium fluorides, such as Bu4NF. It has been found advantageous to use the hydrogen fluoride adduct of a tertiary amine. This adduct is capable of removing protecting groups, also those containing bulky ligands, such as tert-butyl or phenyl, and thereby give a by-product ammonium cation which is a cation that can react with the transition metal compound to give a catalytically active complex. It is preferred to use this adduct rather than using a compound such as Bu4NF, because the Bu4N cation left as a by-product can render the less effective activating anion. Most preferably the HF adduct of such a tertiary amine is used, which corresponds to the desired ammonium ion of the activator compound. For example, triethylamine would give a triethylammonium cation. Topically, the adduct comprises 1 to 3 moles of HF per mole of amine, preferably 2.

The product complex is preferably subjected to a cation exchange reaction with a further complex compound comprising a cation capable of reacting with a transition metal compound to form a catalytically active transition metal complex and a charge balancing anion, wherein the cation and anion are contained in such relative amounts to provide a neutral complex compound. The cation capable of reacting with a transition metal compound to form a catalytically active transition metal complex is preferably selected from the group: Bronsted acid cations, carbonium cations, silylium cations and cationic oxidizing agents. The charge balance anion is preferably a halide, sulfate, nitrate or phosphate.

The complex compounds used in the cation exchange reaction are known compounds.

ES 2 188 751 T3 or can be prepared according to conventional processes. The cation exchange can be carried out in a suspension or solution or on a cation exchange column. The cation exchange reaction and the removal of optional protecting Pr groups can be carried out simultaneously.

The product of the cation exchange reaction is recovered, for example by decantation or filtration, and is preferably washed with a hydrocarbon. Subsequently, the complex product can be dried using conventional methods, such as applying reduced pressure, heat, using absorbent solvents or a combination of these.

All reactions are preferably carried out in an inert atmosphere in the absence of oxygen and moisture.

Compounds M '^{m +} Qm are known compounds or can be prepared according to conventional methods. Compounds of formula Z¹(Gq (T-Pr) r) are prepared topically by reacting X "(Gq (T-Pr) r) or H (Gq (T-Pr) r), where X" has the same definition as given above herein, H is hydrogen and T-Pr is TH or a protected TH group, with M "or M ', respectively, where M" and M' are a Group 2 element and a Group 1 element, respectively. The starting compounds X "(Gq (T-Pr) r) and H (Gq (T-Pr) r) can be prepared according to conventional methods of orgaonic synthesis.

Having described the invention, the following examples are provided as a further illustration thereof and should not be construed as limiting. Unless otherwise indicated, all parts and percentages are on a weight basis.

Examples

The bulk density of the polyomers produced in the present examples was determined according to ASTM 1895. The aluminum content in the support material was determined by treatment with sulfuric acid, followed by addition of EDTA and back titration with zinc chloride, as described above.

Example 1

Activator preparation

A. To a solution of 4-BrMg (C6H4) OSiMe3 (ca. 20 mmol, prepared according to the procedure described in J. Org. Chem., 25, 1063 (1960), but using 1,2-dibromoethane instead of methyl iodide to initiate the reaction) in tetrahydrofuran (20 ml) was added slowly, with vigorous stirring, a solution of tris (pentafluorophenyl) borane (4.3 grams, 8.4 mmol) in hexane (200 ml). A viscous solid separated, and the mixture was stirred for 16 hours. The top layer was decanted after the solid and the residue was washed with two 200 ml portions of hexane. The residue was vacuum dried for 16 hours to yield a pale yellow microcrystalline solid. The solid was quenched with a solution of triethylammonium chloride in distilled water (85 mmol in 200 ml) and the mixture was stirred for 1 hour. The solution was decanted from the solid and the residue was treated with a second part of triethylammonium chloride in distilled water (85 mmol in 200 ml). After stirring for 1 hour the solution was decanted and the solid was washed with two 200 ml portions of distilled water. The residue was dissolved in a mixture of methanol (80 ml) and water (4 ml) and stirred for 16 hours. The solvents were then removed under reduced pressure and the solid was dried in vacuo for 16 hours to yield 3.6 grams (60% yield based on tris (pentafluorophenyl) borane) of a very pale yellow microcrystalline solid. It was found that the solid analyzed by NMR spectroscopy of¹³C and ¹⁹F was triethylammonium tris (pentafluorophenyl) (4-hydroxyphenyl) borate [NEt3H] [(HOC6H4) B (C6F5) 3]. NMR data indicated that the compound was 95% pure.¹⁹F NMR (tetrahydrofuran, ppm): -127.1 (doublet, 2F, ortho); -163.8 (triplet, 1F, para); -165.9 (triplet, 2F, meta).¹³C NMR (tetrahydrofuran d-8, ppm): 150.5; J = 235 Hz; 138.7; J = 230 Hz; 140.0; J = 245 Hz; 130, broad; 155.8; 135.8; 115.0; 49.0; 11.0.

B. To a solution of 28.7 g (0.16 mole) of p-bromophenol and 25.0 g (0.17 mole) of tert-butyldimethylsilyl chloride in THF was added 35 ml (0.25 mole) of triethylamine. A white precipitate formed and the mixture was refluxed. After 4 hours a sample was analyzed by GCMS (Gas Chromatography-Mass Spectroscopy) and this indicated that the reaction was complete. The precipitate was removed by filtration and washed with THF. THF was evaporated from the filtrate and the resulting orange-brown oil was vacuum distilled to yield 44.1 g (93%) of a colorless liquid with a boiling point.

ES 2 188 751 T3 of 75^°Ca76^°C at 0.15 mm Hg. GCMS showed that the 4-bromophenoxy-tert-butyldimethylsilane product was more than 99% pure.

A solution containing 92 mmol of tert-BuMe2SiOC6H4MgBr was prepared from 26.4 grams (92 mmol) of tert-BuMe2 SiOC6H4Br and 2.7 grams (110 mmol) of Mg in 100 ml of THF. The Grignard solution was decanted from excess Mg. Approximately 37 mmol of B (C6F5) 3 was dissolved in THF (100 ml) and the resulting solution was added to the Grignard reagent solution. The clear homogeneous solution was heated for 40 minutes in a water bath at 80^°C. Anaolysis ¹⁹F NMR indicated a quantitative conversion to the desired borate.

The reaction mixture was allowed to cool to room temperature and a solution of 33 grams (250 mmol) of Et3NHCl in water was added. THF was evaporated until the water began to distill. Then dichloromethane (200 ml) was added and the aqueous phase was separated. The dichloromethane phase was washed with two 100 ml parts of water and two 100 ml parts of water containing CO2 (solid CO2 was added to the two phase system until the pH was 7). The dichloromethane solution was dried over sodium sulfate, filtered and evaporated, resulting in an oil. Yield 45 grams. A spectrum¹H NMR of this material showed the presence of tert-BuMe2SiOC6H4B (C6F5) 3.Et3NH and tert-BuMe2 SiOC6H5 in approximately a 1: 1 molar ratio. The oil was stirred with pentane (100 ml) for 15 minutes. The pentane was decanted and the procedure was repeated with another three 100 ml portions of pentane. The resulting oil was dried in vacuo (0.1 mbar) to yield a beige foam. The yield was 33 grams (quantitative). The specters¹Hy¹⁹F NMR showed that the material was almost pure tert-BuMe2 SiOC6H4B (C6F5) 3 .Et3NH.

grams (20.7 mmol) of this product were dissolved in THF (100 ml). To this solution, a mixture of Et3N.3HF (5 grams, 31.3 mmol) and Et3N (3.1 grams, 31.3 mmol) (effectively Et3N.2HF) was added. After 14 hours the spectra¹Hy¹⁹F NMR of the entire mixture showed that deprotection was complete and that no side products were formed. THF was evaporated and 100 ml of 0.5 M NaOH and 200 ml of diethyl ether were added to the residue. The aqueous phase was separated and the ether was washed with three 50 ml parts of 0.5 M NaOH, two 50 ml parts of water and two 50 ml parts of water containing CO2. The ether was dried over sodium sulfate, filtered and evaporated. The residue was dissolved in 50 ml of dichloromethane and evaporated again (repeated three times). The resulting beige foam was vacuum dried (0.1 mbar) overnight to yield 12.8 g of HOC6H4B (C6F5) 3 .Et3NH (approximately 90% yield based on B (C6F5) 3). The specters¹Hy¹⁹F NMR showed that the compound was pure. ¹⁹F NMR (THF-d8 solvent) ppm: -126.5 (doublet, 2F, ortho); -163.0 (triplet, 1F, para); -165.5 (double, 2F, goal).¹H NMR (THF-d8 solvent): 1.25 (triplet, 9H); 3.15 (quartet, 6H); 6.35; 7.05 (AB, 4H); 7.05 (broad, 2H).

C. The starting compound 4-bromo-N-methylaminobenzene was synthesized from N-methylaminobenzene according to Organic Synthesis, Vol. 55, p. 20 - 24.

The next step in the synthesis method is a modified version of that given in J. Org. Chem., 40, 1090, 1975. To a solution of 18.6 g (0.1 mole) of 4-bromo-N-methylaminobenzene in 200 ml of THF was added to 0^°C a solution of 67 ml of 1.5 molar n-butyllithium in hexane. A pale yellow precipitate formed. After 10 minutes a solution of 15.1 g (0.1 mole) of tert-butyldimethylsilyl chloride in 20 ml of THF was added. The temperature of the reaction mixture was allowed to rise to room temperature and the mixture was then refluxed for 6 hours. The solvents were evaporated and distillation of the residue gave 2.0 g (93%) of a yellow liquid of 4-bromo-N-tert-butyldimethylsilyl-N-methylaminobenzene at a distillation temperature of 100^°C to 110^°Ca0.3mm of Hg. The purity determined by GCMS was at least 99.5%.

To 2.4 g (0.1 mol) of magnesium filings, approximately 10% of a solution of 28.0 g (93 mmol) of 4-bromo-N-tert-butyldimethylsilyl-N-methylaminobenzene in 100 ml of THF. 1,2-Dibromoethane (100 ml) was added and the reaction started by heating to reflux temperature. The remainder of the aniline solution was added within 40 minutes and the mixture was heated at regular times to keep the reaction going. Once addition was complete the mixture was refluxed for 2 hours. A sample was quenched with water and analyzed by GCMS: major peak: M = 221 (N-tert-butyldimethylsilyl-N-methylaminobenzene).

To the THF solution of Grignard's reagent was added at room temperature with vigorous stirring 780 ml of a solution containing 31.2 mmol of tris (pentafluorophenyl) boron in heptane. The reaction mixture was stirred for 16 hours at room temperature. A viscous material was removed. The top layer was decanted and the precipitate washed with three 100 ml portions of hexane. The residue was dried

ES 2 188 751 T3 in vacuo (0.1 mm Hg) for a few hours to give a white foam. This magnesium bromide (4-N-tert-butyldimethylsilyl-N-methylaminophenyl) tris (pentafluorophenyl) borate product was used for the next step without further purification.

To the reaction product of the previous step, a solution of 60 g of triethylammonium chloride in 100 ml of demineralized water was added. The mixture was stirred for 2 hours and a homogeneous emulsion formed. The reaction mixture was extracted with four 50 ml portions of dichloromethane and the combined dichloromethane extracts were washed three times with 50 ml demineralized water. The dichloromethane was dried over magnesium sulfate. Filtration and evaporation of the solvent gave the product (4-N-tert-butyldimethylsilyl-N-methylaminophenyl) -tris (pentafluorophenyl) triethylammonium borate.

The product from the previous reaction step was dissolved in a mixture of 150 ml of methanol, 50 ml of water and 2 g of triethylammonium chloride and stirred for 16 hours at room temperature. Methanol was evaporated and 100 ml of demineralized water was added to the residue. The suspension was extracted with four 30 ml portions of dichloromethane and the combined dichloromethane extracts were dried over magnesium sulfate. After filtration and evaporation of the solvent, 19.6 g (76%) of a dark brown powder remained. For further purification the product was washed three times with toluene. To remove the last traces of toluene, the material was mixed twice with 40 ml of dichloromethane and the solvent was evaporated. In the course of this treatment the material became less soluble in this solvent. For the last purification step, the product was mixed with 100 ml of dichloromethane and heated. After cooling, the material was filtered on a Buchner funnel to give after vacuum drying 12.8 g (50%) of the product (4-N-methylaminophenyl) tris- (pentafluorophenyl) borate of pure triethylammonium.

¹H-NMR (THF-d8 and acetone-d6): 1.20 (triplet, 9H); 2.70 (singlet, 3H); 3.10 (quartet, 6H); 5.90 (broad, 2H); 6.35; 7.15 (AB, 4H).

¹³C-NMR (THF-d8): 148.9 (J = 238); 138.3 (J = 233); 136.9 (J = 263); 129.0 (wide); 146.5; 134.2; 111.8, 47.1, 31.0, 9.0.

¹⁹F-NMR (THF-d8 + benzene-d6): -127.0 (doublet, 2F, ortho); -163.0 (triplet, 1F, para); -165.5 (triplet, 2F, meta).

D. Triethylammonium tris (pentafluorophenyl) (4-hydroxymethylphenyl) borate was prepared analogously to the procedure in Example 1A using 4-MgBr (C6H4) CH2OSi (tert-Bu) Me2 prepared by reacting 4-bromobencholic alcohol with tert-BuMe2SiCl, and converting the reaction product with magnesium in the Grignard reagent.

E. HCl salts of the amines trioctylamine, dimethyl-n-octylamine, dimethylphenylamine, and benzyldimethylamine were prepared quantitatively by conducting hydrogen chloride gas through a diethyl ether solution of the amine until the pH became acidic (about 5 minutes). The solid material, in each case isolated by filtration, was washed with diethyl ether and dried under vacuum.

Triethylammonium tris (pentafluorophenyl) (4-hydroxylphenyl) borate (1.4 grams, 2 mmol) was dissolved in 25 ml of dichloromethane. An ion exchange reaction was carried out by stirring this solution six times with a solution of 4 mmol of the respective HCl salt of the above amines in 20 ml of water. The dichloromethane solution was washed five times with 20 ml portions of water and then dried over magnesium sulfate. The mixture was filtered, and the filtrate was evaporated to dryness in vacuo to obtain the appropriate ammonium salt. The yield in each case was 90% and the multinuclear NMR spectroscopy was in complete agreement with the proposed structures.

Example 2

Preparation of Support Material Treated with Aluminum Component

A. A 250 ml flask was charged with 5 g of granular solid SD 3216.30 (with a specific surface area of ​​approximately 300 μm²/ g, a pore volume of approximately 1.5 cc / g, and an average particle size of 45 micrometers) available from Grace GmbH, which had been heated to 250^°C for 3 hours in vacuo to give a final water content of less than 0.1 weight percent as determined by differential scanning calorimetry. 101 g of a 10 weight percent solution of methylalumoxane (MAO) in toluene, available from Witco GmbH, was added and the mixture was stirred for 16 hours at room temperature. After this time the toluene separated or under pressure reduced to 20^°C, and the solids were vacuum dried for 16 hours at 20^°C to yield a loose powder or granules. Dust

ES 2 188 751 T3 heated up to 175^°C for two hours under vacuum. The powder was resuspended in toluene (130 ml) and the mixture was heated to 90^°C and stirred for 1 hour. The mixture was filtered and the resulting solid was washed with two 50 ml portions of fresh toluene at 90^°C. The support was then dried under vacuum at 120^°C for 1 hour. 11.1 g of support were obtained having an aluminum content of 23.8%.

B. A 250 ml flask was charged with 5 g of SD 3216.30 granular silica available from Grace GmbH which had been heated to 250^°C for 3 hours in vacuo to give a final water content of less than 0.1 weight percent as determined by differential scanning calorimetry. 101 g of a 10 weight percent MAO solution in toluene were added and the mixture was stirred for 16 hours. The solid material was isolated by filtration and then resuspended in toluene (80 ml) and the mixture was heated to 90^°C and stirred for 1 hour. The mixture was filtered and the resulting solid was washed with two 50 ml portions of fresh toluene at 90^°C. The support was then dried under vacuum at 120^°C for 1 hour. 6.7 g of support were obtained with an aluminum content of 13.6%.

C. A 250 ml flask was charged with 5 g of granular solid SD 3216.30 available from Grace GmbH containing 2.8% water, and 101 g of a 10 weight percent MAO solution in toluene was added and stirred the mixture for 16 hours. The solid material was isolated by decantation and then resuspended in toluene (80 ml) and the mixture heated to 90^°C and stirred for 1 hour. The mixture was filtered and the resulting solid was washed with two 50 ml portions of fresh toluene at 90^°C. The support was then dried under vacuum at 120^°C for 1 hour. 7.3 g of support were obtained with an aluminum content of 15.4%.

D. A 250 ml flask was charged with 10 g of granular solid SD 3216.30 available from Grace GmbH which had been heated to 250^°C for 3 hours in vacuo to give a final water content of less than 0.1 weight percent, as determined by differential scanning calorimetry. 36 g of a 10 weight percent MAO solution in toluene were added and the mixture was stirred for 16 hours. The solid material was isolated by filtration and then resuspended in toluene (100 ml) and the mixture was heated to 90 ° C.^°C and stirred for 1 hour. The mixture was filtered and the resulting solid was washed with two 50 ml portions of fresh toluene at 90^°C. The support was then dried under vacuum at 120^°C for 1 hour. 13.1 g of support were obtained with an aluminum content of 12.3%.

E. A 250 ml flask was charged with 10 g of granular solid SD 3216.30 available from Grace GmbH which had been heated to 250^°C for 3 hours in vacuo to give a final water content of less than 0.1 weight percent, as determined by differential scanning calorimetry. 72 g of a 10 weight percent MAO solution in toluene were added and the mixture was stirred for 16 hours. The solid material was isolated by filtration and then resuspended in toluene (100 ml) and the mixture was heated to 90^°C and stirred for 1 hour. The mixture was filtered and the resulting solid was washed with two 50 ml portions of fresh toluene at 90^°C. The support was then dried under vacuum at 120^°C for 1 hour. 13.3 g of support were obtained with an aluminum content of 11.4%.

F. A 250 ml flask was charged with toluene (50 ml) and trimethylaluminum (13.5 ml, 0.141 mol). 5 grams of solid SP-9-10046 (available from Grace Davison) with a water content of

4.5% by weight, based on the combined weights of water and support, and the mixture was stirred for 16 hours. The mixture was filtered and the support washed with toluene (50 ml, approximately 100^°C) and dried under high vacuum. 5.2 grams of support with aluminum content of 7.3% by weight were obtained.

G. A 250 ml flask was charged with toluene (50 ml) and triethylaluminum (11 ml, 0.08 mole). 6.3 grams of solid SP-9-10046 with a water content of 4.5% by weight were added and the mixture was stirred for 1 hour. The mixture was filtered and the support washed with toluene (50 ml, approximately 100^°C) and dried under high vacuum. 6.3 grams of support with aluminum content of 5.3% by weight were obtained.

H. A 250 ml flask was charged with toluene (50 ml) and triethylaluminum (7 ml, 0.051 mol). 5 grams of solid SP-9-10046 that had been treated at 250 ° C for 3 hours under vacuum were added and the mixture was stirred for 16 hours. The mixture was filtered and the support washed with toluene (50 ml, approximately 100^°C) and dried under high vacuum. 5.1 grams of support with an aluminum content of 4.7% by weight were obtained.

Supported Catalyst Preparation

Example 3

Two grams of the support treated as described in Example 2A was suspended in toluene (20

ES 2 188 751 T3 ml) and triethylammonium tris (pentafluorophenyl) (4-hydroxyphenyl) borate prepared in Example 1 (0.224 g, 0.32 mmol) in toluene (10 ml) was added thereto. The mixture was stirred for 16 hours and then filtered and washed with toluene (3x10 ml) and dried in vacuo at 20^°C. 1 g of the solid was suspended in toluene (15 ml) and the mixture was stirred for a few minutes. An alotquot of 0.56 ml of a dark orange-brown 0.0714 M solution (40 micromoles) of [(tert-butylamido) (dimethyl) (tetramethyl-n⁵cyclopentadienyl) silane] dimethyltitanium (hereinafter MCpTi) in ISOPAR solution^TM E (Trademark of Exxon Chemical Company) and the mixture was stirred for a few minutes, filtered, washed with toluene (2x10 ml) and vacuum dried to give a bright yellow supported catalyst. The supported catalyst was resuspended in 10 ml of hexane for use in a suspension polymerization reaction.

Example 4

0.5 grams of the support treated as described in Example 2A was suspended in toluene (10 ml) and stirred for a few minutes. This suspension was added to a mixture of triethylammonium tris (pentafluorophenyl) (4-hydroxyphenyl) borate prepared in Example 1 (0.042 g; 60 micromoles) in toluene (10 ml) and the mixture was stirred for 16 hours. The solids were filtered and washed with 2x10 ml of toluene and resuspended in toluene (10 ml). 20 micromoles of MCpTi were added in ISOPAR E to give a yellow-brown solid phase and a colorless supernatant. The mixture was stirred for a few minutes before use in a polymerization reaction.

Example 5

The procedure of Example 4 was repeated except that 0.028 grams (40 micromoles) of triethylammonium tris (pentafluorophenyl) (4-hydroxyphenyl) borate was used. A supported catalyst was obtained consisting of a yellow-brown solid phase and a colorless supernatant.

Example 6

The procedure of Example 4 was repeated except that 0.014 grams (20 micromoles) of triethylammonium tris (pentafluorophenyl) (4-hydroxyphenyl) borate was used. A supported catalyst was obtained consisting of a yellow-brown solid phase and a colorless supernatant.

Example 7

0.25 grams of the support treated as described in Example 2B was suspended in toluene (5 ml) and stirred for a few minutes. This suspension was added to a mixture of triethylammonium tris (pentafluorophenyl) (4-hydroxyphenyl) borate (0.014 g; 20 micromoles) in toluene (5 ml) and the mixture was stirred for 16 hours. The toluene was filtered off and the solids were washed with 2x10 ml of toluene and resuspended in toluene (10 ml). 10 micromoles of MCpTi were added in ISOPAR^TM E and the mixture was stirred for a few minutes before use in a polymerization reaction. A supported catalyst was obtained consisting of a yellow-brown solid phase and a colorless supernatant. Example 8

The procedure of Example 7 was repeated except that prior to the addition of the transition metal compound, the supported catalyst component comprising the treated solid and triethylammonium tris (pentafluorophenyl) (4-hydroxyphenyl) borate was not washed with toluene.

Example 9

The procedure of Example 7 was repeated except that prior to the addition of the transition metal compound, the supported catalyst component comprising the treated solid and the triethylammonium tris (pentafluorophenyl) (4-hydroxyphenyl) borate was not washed with toluene. . 0.028 g (40 micromoles) was also used instead of 0.014 g of triethylammonium tris (pentafluorophenyl) (4-hydroxyphenyl) borate.

Example 10

The procedure of Example 9 was repeated except that half the amount of the final supported catalyst, containing approximately 5 micromoles of MCpTi, was used in a polymerization reaction.

IS 2 188 751 T3

Example 11

The procedure of Example 9 was repeated except that the support treated as in Example was used.

2 C.

Example 12

The procedure of Example 9 was repeated except that the support treated as in Example was used.

2D.

Examples 13 and 14

The procedure of Example 9 was repeated except that the support treated as in Example was used.

2E.

Examples 15 and 16

The procedure of Example 9 was repeated except that the support treated as in Example 2E was used and 0.021 g (30 micromoles) of triethylammonium tris (pentafluorophenyl) (4-hydroxyphenyl) borate was used. Example 17

0.25 grams of the support treated as described in Example 2E was suspended in toluene (5 ml) and stirred for a few minutes. 10 micromoles of MCpTi in ISOPAR E were added and the mixture was stirred for 15 minutes. The mixture was added to 0.028 g (40 micromoles) of triethylammonium tris (pentafluorophenyl) (4-hydroxyphenyl) borate in toluene (10 ml) and the mixture was stirred for 16 hours to yield a supported catalyst comprising a yellow-brown solid phase and a colorless supernatant. Example 18

0.014 g (20 micromoles) of triethylammonium tris (pentafluorophenyl) (4-hydroxyphenyl) borate was added to toluene (10 ml) and the mixture was stirred for a few minutes. 20 micromoles of MCpTi in ISOPAR E were added and the mixture was stirred for 30 minutes. The color changed from yellow to red. 0.5 grams of the support treated as described in Example 2A in toluene (10 ml) was added and the mixture was stirred for 16 hours.

Example 19

Preparation of Supported Catalysts

1.5 grams of the supported catalyst components prepared in Examples 2F (Example 19A), 2.G (Example 19B), and 2.H (Example 19C) were suspended in toluene (20 ml) and the mixture was stirred for about minutes to disperse the support. The suspension was added to a solution of triethylammonium tris (pentafluorophenyl) (4-hydroxyphenyl) borate (0.084 g, 0.120 mmol) in toluene (60 ml) which had been previously heated to a temperature of 65^°Ca70^°C. The mixture was stirred for 30 minutes at this temperature and then heating was discontinuous and the mixture was allowed to cool to room temperature. Stirring was continued for an additional 16 hours. A 0.84 ml aliquot of a 0.0714 M dark violet (60 micromoles) solution of titanium, (N-1,1-dimethylethyl) dimethyl (1- (1,2,3,4,5-eta ) 2,3,4,5-tetramethyl-2,4-cyclopentadien-1-yl) silanaminate)) (2-) N) - (η⁴-1,3-pentadiene) (hereinafter MCpTi (II)) in ISOPAR^TM E (trademark of Exxon Chemical Company) and the mixture was stirred for about 1 hour to yield a green supported catalyst. The catalyst was used as such in a suspension polymerization.

Example 20

Supported Catalyst Preparation

Triethylammonium tris (pentafluorophenyl) (4-hydroxyphenyl) borate (0.0707 g, 0.1 mmol) was dissolved in toluene (100 ml) by heating the mixture at 70 ° C for 15 minutes. Triethylaluminum solution (50 ml of 0.002 M toluene solution, 0.1 mmol) was added and the mixture was stirred for 5 minutes. 1 gram of SP-9-10046 solid that had been treated at 250^°C for 3 hours under vacuum in toluene (20 ml) for 15 minutes and then this suspension was added to the adduct solution of

ES 2 188 751 T3 borate / triethylaluminum and the mixture was stirred for 5 minutes at a temperature of 70 ° C. Triethylaluminum (0.24 ml, 2 mmol) was added and the mixture was stirred for an additional 5 minutes at 70 ° C. The mixture was filtered and the support was washed once with toluene (100 ml, 70 ° C) and twice with 100 ml of boiling hexane. The support was then dried under reduced pressure. 0.25 grams of the support was suspended in hexane (10 ml) and 0.14 ml of a 0.0714 M solution of MCpTi (II) (10 micromoles) in hexane was added. The mixture was stirred for 16 hours to yield a supported catalyst consisting of a green solid phase and a colorless supernatant. The catalyst was used as such in a suspension polymerization.

Example 21

Supported Catalyst Preparation

1.5 grams of a pretreated support prepared as in Example 2H was suspended in toluene (20 ml) for a few minutes to disperse the support. The suspension was added to a mixture of triethylammonium tris (pentafluorophenyl) (4- ((N-methyl) amino) phenyl) borate (0.087 g, 0.120 mmol) in toluene (40 ml) which was previously heated to a temperature of 65 ° C to 70 ° C. The mixture was stirred for 30 minutes at this temperature and then the heating was removed and the mixture was allowed to cool to room temperature. Stirring was continued for an additional 16 hours. A 0.84 ml aliquot of a 0.0714 M (60 micromoles) solution of MCpTi (II) in hexane was added and the mixture was stirred for approximately 16 hours to yield a green / brown supported catalyst. The catalyst was used as such in a suspension polymerization.

Example 22

Supported Catalyst Preparation

30 grams of SiO were suspended₂ SP-9-10046 treated at 250 ° C for 2 hours under vacuum in toluene (300 ml) and a solution of triethylaluminum (30 ml; 0.22 mol) in toluene (200 ml) was added. The mixture was stirred for 1 hour, filtered, washed with two 100 ml portions of fresh toluene and dried in vacuo. Toluene (200 ml) was added to 20 grams of the resulting powder. The mixture was stirred for a few minutes to disperse the support. This suspension was added to a solution of triethylammonium tris (pentafluorophenyl) (4-hydroxyphenyl) borate (1.125 g, 1.6 mmol) in toluene (200 ml) which had been heated to 70 ° C and stored at 70 ° C for 30 minutes. . In the addition, the heating was removed and the mixture was stirred at room temperature for 16 hours.

A 40 ml aliquot of the resulting suspension (containing approximately 1 gram of the support) was removed and 0.47 ml of a 0.0855 M solution of bis (indenyl) zirconium dimethyl (Witco GmbH) (40 micromoles of Zr). The mixture was stirred for a few minutes to yield an orange supported catalyst. An alloyquot of this supported catalyst containing 14 micromoles of zirconium was used as such in a suspension polymerization.

Example 23

Supported Catalyst Preparation

20 grams of SiO were suspended₂ (SP-9-10046) treated at 250 ° C for 2 hours under vacuum in toluene (300 ml) and triethylaluminum (20 ml; 0.147 mol) was added. The mixture was stirred for 1 hour, filtered, washed with two 100 ml portions of fresh toluene and vacuum dried. To 1.5 grams of the resulting powder, toluene (20 ml) was added. The mixture was stirred for a few minutes to disperse the support. This suspension was added to a solution of triethylammonium tris (pentafluorophenyl) (4-hydroxymethylphenyl) borate (0.086 g, 0.12 mmol) in toluene (40 ml), which had been heated to 70 ° C and stored at 70 ° C for 1 hour. In the addition, the heating was removed and the mixture was stirred at room temperature for 16 hours. 0.84 ml of a 0.0714 M solution of MCpTi (II) (60 micromoles of Ti) was added and the mixture was stirred for 1 hour to yield a green-brown supported catalyst. An alloquot of this supported catalyst containing 10 micromoles of titanium was used as total in a suspension polymerization.

Example 24

Ethylene / 1-octene copolymerization in suspension phase

A catalyst was prepared as in Example 19C. 20 micromoles of catalyst were used, based

ES 2 188 751 T3 in titanium, in a suspension polymerization. 250 ml of 1-octene was added to the reactor. An ethylene / 1-octene copolymer of density 0.9376 g / cm was prepared³.

Example 25-26

Supported catalyst preparation

30 grams of SiO2 (SP-9-10046) treated at 250^°C for 2 hours in vacuo in toluene (300 ml) and triethylaluminum (30 ml; 0.22 mol) was added. The mixture was stirred for 1 hour, filtered, washed with two 100 ml portions of fresh toluene and vacuum dried.

Toluene (20 ml) was added to 3 grams of the resulting powder. The mixture was stirred for a few minutes to disperse the support. This suspension was added to a solution of triethylammonium tris (pentafluorophenyl) (4-hydroxyphenyl) borate (0.126 g, 0.18 mmol) in toluene (40 ml) which had been heated to 80^°C and saved at 80^°C for 1 hour. In addition, heating was discontinuous and the mixture was stirred at room temperature for 16 hours. 1.68 ml of 0.0714 M MCpTi (II) solution was added and the mixture was stirred for 1 hour to yield a green supported catalyst.

Another 3 gram portion of the resulting powder was treated according to the same procedure, even using 0.105 grams; 0.15 mmol of borate that had been heated to 70^°C and saved at 70^°C for 1 hour.

Alloquots of the resulting supported catalysts containing 10 micromoles of titanium were used, as such, in a suspension polymerization.

Comparative Example 1

0.5 grams of solid SD 3216.30 (dehydrated for 3 hours at 250^°Calvacóo) in toluene (10 ml), stirred for a few minutes and then added to triethylammonium tris (pentafluorophenyl) (4-hydroxyphenyl) borate (0.028 g; 40 micromoles) in toluene (10 ml) and the mixture was stirred for 16 hours . 20 micromoles of MCpTi were added in ISOPAR E to give a pale yellow solid phase and a colorless supernatant.

Comparative Example 2

Triethylammonium tris (pentafluorophenyl) (4-hydroxyphenyl) borate (0.014 g; 20 micromoles) in 10 ml of toluene was treated with 20 micromoles of MCpTi in ISOPAR E. The resulting red mixture was stirred for a few minutes and then used as such in a polymerization reaction.

Example 27

Polymerization Performances

A 10 liter autoclave reactor was charged with 6 liters of anhydrous hexane, 1 liter of hydrogen gas and the contents of the reactor were heated to 80^°C, unless otherwise stated, temperature at which the polymerization mixture was maintained during polymerization. Ethylene was then added to increase the pressure to the desired operating level of 10 bar, unless otherwise stated. A supported catalyst sample prepared as in the previous examples and comparative examples was added to the reactor through a pressure addition cylinder in the amounts indicated in the table below. Ethylene was supplied to the reactor continuously to keep the pressure constant. After the desired reaction time, the ethylene line was blocked and the contents of the reactor were emptied into a sample container. Hexane was removed from the polymer and the polymer was dried overnight and then weighed to determine catalyst efficiencies. In none of the inventive examples did substantial reactor thickening occur and all of the examples gave a polymer in the form of loose powder or granules.

The table summarizes the specific conditions and results of suspension polymerizations with the supported catalyst prepared above.

Example 28

Continuous Polymerizations in Suspension Phase

IS 2 188 751 T3

20 grams of SiO2-treated triethylaluminum (prepared as in Example 22) was suspended in toluene (200 ml) and the mixture was heated to 80 ° C. In a separate container, triethylammonium tris (pentafluorophenyl) (4-hydroxyphenyl) borate was added (1.125 g, 1.6 mmol) to toluene (400 ml) and the mixture was heated to 80 ° C and stored at 80 ° C for 1 hour. The borate solution was added to the support suspension and the mixture was stirred and stored at 80 ° C for 2 hours. The mixture was allowed to cool and stir overnight. Toluene was decanted from the support and replaced with hexane (800 ml). This procedure was repeated. 8 mmol of MMAO type 3A (20 weight percent solution in AKZO heptane) was added and the mixture was stirred for 15 minutes. 11.2 ml of a 0.0714 M solution of MCpTi (Il) was added and the mixture was stirred for 2 hours before use. The support contained a boron loading of 80 micromoles / g and a titanium loading of 40 micromoles / g.

Isopentane, ethylene, 1-butene (if required), hydrogen and supported catalyst were continuously fed to a 10 L tank reactor, with continuous stirring, and the slurry product formed was continuously separated. The total pressure in all the polymerization runs was 15 bar and the temperature was kept at 70 ° C. The withdrawn suspension was fed to an expansion tank to remove the diluent and the loose, dry polymer powder or granules were collected. In a first embodiment, the following conditions were used: isopentane flow of 2,500 g / hour; ethylene flow from

1,200 g / hour; hydrogen flow of 0.4 l / hour; temperature of 70 ° C to produce a product with a bulk density of 0.354 g / cm³, and a melt flow onyx, measured at 190 ° C and a load of 21.6 kg of 1.4 g / 10 minutes, with an efficiency of 1,500,000 g PE / g Ti. In a second embodiment the following conditions were used: isopentane flow of 2,500 g / h; ethylene flow of 800 g / hour; butene flow of 42.5 g / h; hydrogen flow of 0.45 l / hour; temperature of 70 ° C to produce a product with a volumetric density of 0.300 g / cm³, a density of 0.9278 g / cm³, a butene content of 1.42% in moles and a melt flow index, measured at 190 ° C and a load of 2.16 kg of 0.85 g / 10 minutes, with an efficiency of 650,000 g PE / g You.

Example 29

Solution Phase Polymerizations

30 grams of SiO were suspended₂ (SP-9-10046) treated at 250 ° C for 3 hours under vacuum in toluene (300 ml) and triethylaluminum (30 ml; 0.22 mol) was added. The mixture was stirred for 1 hour, filtered, washed with two 100 ml portions of fresh, dry toluene in vacuo. Toluene (150 ml) was added to 10 grams of the resulting powder. The mixture was stirred for a few minutes to disperse the support. This suspension was added to a solution of triethylammonium tris (pentafluorophenyl) (4-hydroxyphenyl) borate (0.565 g; 0.8 mmol) in toluene (250 ml) that had been treated at 70 ° C and stored at 70 ° C for 1 hour. In the addition, the heating was removed and the mixture was stirred at room temperature for 16 hours. A 50 ml aliquot of the suspension was treated with 0.7 ml of a 0.0714 M solution of MCpTi (II) (50 micromoles of Ti) followed by 500 micromoles of MMAO and the mixture was stirred for 1 hour to yield a green-brown supported catalyst. Alloquots of this supported catalyst containing 2 and 1.25 micromoles of titanium, respectively, were used.

A 3 liter autoclave reactor was charged with the desired amount of 1-octene followed by a sufficient amount of ISOPAR^TM E to give a total volume of 1,500 ml. 300 ml of hydrogen gas was added and the contents of the reactor were heated to the desired temperature. Enough ethylene was added thereafter to bring the system pressure to 30 bar. A supported catalyst was added to initiate polymerization and ethylene was continuously supplied to the reactor upon request. After 10 minutes the ethylene line was blocked and the contents of the reactor were emptied into a sample container. The polymer was dried overnight and then weighed to determine catalyst efficiencies. The specific conditions were: Run 1: 121 ml of octene; temperature of 130 ° C; to give 82 g of product (efficiency 854,000 based on PE / g Ti) of a melt onyx (at 190 ° C / 2.16 kg load) of 3.8 and a density of 0.9137. Run 2: 450 ml octene; temperature of 80 ° C; to give 47 g of product (efficiency 785,000 based on PE / g Ti) with a melt index (190 ° C / 2.16 kg) of 1.66 g / 10 minutes and a density of 0.8725 g / cm³.

IS 2 188 751 T3

<td>Density volumetric (g / cm³)</td><td> 0,30</td><td> 0,30</td><td> 0,28</td><td> 0,26</td><td> 0,29</td><td> 0,24</td><td> 0,24</td><td>h- CM or'</td><td>CM CM OR</td><td> 0,22</td><td> 0,23</td><td>or CM or'</td><td> 0,21</td><td> 0,23</td>

<td>Effectiveness (AIXgPEZ gAI / h)</td><td> 4.874</td><td> 7.289</td><td>SB9Z</td><td> 3.950</td><td> 12.941</td><td> 22.794</td><td>6SZ0S</td><td> 16.412</td><td> 25.455</td><td> 26.667</td><td>S OR or θ '</td><td> 42.105</td><td> 36.934</td><td> 21.404</td>

<td>3 or g S lü &lt;£ S α</td><td> 2.373</td><td> 3.540</td><td> 3.742</td><td> 1.923</td><td> 2.486</td><td> 4.379</td><td> 9.752</td><td> 3.730</td><td>8S8S</td><td> 00</td><td> 6.039</td><td> 6.357</td><td> 5.576</td><td> 3.231</td>

<td>Effectiveness (Ti) (g PE / g Ti / h)</td><td> 605.428</td><td> 902.923</td><td> 954.610</td><td> 490.605</td><td> 918.580</td><td> 1.617.954</td><td> 3.602.981</td><td> 1.377.871</td><td> 2.045.929</td><td> 1.711.900</td><td> 2.379.958</td><td> 2.505.219</td><td> 2.197.561</td><td> 1.273.486</td>

<td>I gave up I lie (g)</td><td> 870</td><td> 865</td><td> 945</td><td> 235</td><td> 099</td><td> 775</td><td> 1.093</td><td> 330</td><td> 980</td><td>or CN 00</td><td> 1.140</td><td> 0004</td><td> 0004</td><td> 610</td>

<td>Weather (min)</td><td> 45</td><td> 60</td><td> 62</td><td>OR co</td><td> 90</td><td> 60</td><td> 38</td><td> 60</td><td> 60</td><td>OR co</td><td> 60</td><td>OR IO</td><td> 57</td><td> 60</td>

<td>[Tinimoles MCpTi added to reactor</td><td> 40</td><td> 20</td><td> 20</td><td> 20</td><td>or</td><td>or</td><td>OR t—</td><td>it</td><td>or</td><td>or T "</td><td>or</td><td>or</td><td>or</td><td>OR</td>

<td>Activator/ MCpTi [mol / atomog]</td><td></td><td>CO</td><td>CM</td><td></td><td>CM</td><td>CM</td><td></td><td></td><td>'t</td><td></td><td></td><td></td><td>CO</td><td>co</td>

<td>μπιοΓ activator / g treated support</td><td> 160</td><td> 120</td><td> [- 09</td><td> 40</td><td> 80</td><td> 80</td><td> 160</td><td> 160</td><td>δ T—</td><td> 160</td><td> 160</td><td> 160</td><td> 120</td><td> 120</td>

<td>[To the]% weight in medium</td><td> 23,8</td><td> 23,8</td><td> 23,8</td><td> 23,8</td><td> 13,6</td><td>CD co' T "</td><td>CO co' ▼ *</td><td> 13,6</td><td> 15,4</td><td> 12,3</td><td> 11.4</td><td></td><td> 11.4</td><td></td>

<td>Catalyst of Ex. No.</td><td>CO</td><td></td><td>m</td><td>CD</td><td></td><td> 00</td><td>a&gt;</td><td>OR τ—</td><td></td><td>CM</td><td>CO</td><td></td><td></td><td>CD T—</td>

IS 2 188 751 T3

<td>Density volumetric (g / cm³)</td><td> 0,21</td><td> 0,26</td><td> 0,21</td><td> 0,25</td><td> 0,21</td><td> 0,26</td><td> 0,18</td><td>h- τ- ο '</td><td> 0,14</td><td>or or'</td><td> 0,24</td><td> 0,21</td><td> 1</td><td> 1</td>

<td>Effectiveness (AI) (gPE / gAI / h)</td><td> 20.081</td><td> 1.597</td><td> 51.141</td><td> 75.815</td><td> 57.291</td><td>nm</td><td>nm</td><td> 26.857</td><td>8 or or CO</td><td> 23.773</td><td> 120.000</td><td> 65999</td><td></td><td>t</td>

<td>3 or w O ¡S 52. ™%</td><td> 3.032</td><td>778 I</td><td> 4.413</td><td> 4.824</td><td> 3.160</td><td>nm</td><td>nm</td><td> 1.594</td><td> 4.747</td><td> 1.512</td><td> 7.121</td><td> 5 590</td><td></td><td> 1</td>

<td>Effectiveness (Ti) (g PE / g Ti / h)</td><td> 1.194.797</td><td> 198.330</td><td> 1.948.500</td><td> 2.097.170</td><td> 1.405.367</td><td> 939.457</td><td> 683.242</td><td> 368.916</td><td> 2.087.682</td><td> 657.620</td><td> 3.131.524</td><td> 2.313.644</td><td> 1</td><td></td>

<td>I gave up I lie (9)</td><td> 620</td><td>190 I</td><td> 350</td><td> 1.105</td><td> 460</td><td> 450</td><td> 300</td><td> 470</td><td> 200</td><td>OR 3</td><td> 500</td><td> 1.570</td><td> 1</td><td> &lt;</td>

<td>Weather (min) 1</td><td> 65</td><td> 60</td><td> 45</td><td> 66</td><td></td><td> 60</td><td> 55</td><td> 60</td><td>OJ t—</td><td> 80</td><td> 20</td><td> 85</td><td> 20</td><td> 20</td>

<td>[Tifpmoles MCpTi added to reactor</td><td>OR T * "</td><td> 20</td><td>in</td><td>OR</td><td>or</td><td>or</td><td>or</td><td>T</td><td>or</td><td> 20</td><td>OR</td><td>OR</td><td> 20</td><td> 20</td>

<td>Activator⁶/ MCpTi [mol / atomog]</td><td>Μ¹</td><td>CM</td><td>OJ</td><td>CM</td><td>I HEARD</td><td> 2,5</td><td>I HEARD</td><td>OJ</td><td>CM</td><td>OJ</td><td>m T-</td><td> 1,25</td><td>CM</td><td></td>

<td>pmol^b activator / g treated support</td><td> 160</td><td> 80</td><td> 80</td><td> 80</td><td> 80</td><td> 100</td><td> 80</td><td> 80</td><td> 80</td><td> 80</td><td> 60</td><td> 50</td><td> 80</td><td></td>

<td>[To the]% weight in medium</td><td>X.</td><td> 23,8</td><td> 7,3</td><td> 5,3</td><td>V</td><td>nm</td><td>nm</td><td>YOU</td><td> 5,0</td><td> 5,3</td><td> 5,0</td><td> 5,0</td><td>OR</td><td> 1</td>

<td>Catalyst from Ex. No.</td><td>N</td><td> 00</td><td>i or</td><td>i OR) T-</td><td>or to a&gt; t—</td><td>0 or I HEARD</td><td>or* T— I HEARD</td><td>0 * OJ OJ</td><td>to" 0 CO OJ</td><td>c OJ</td><td>0 * m I HEARD</td><td>0 co I HEARD</td><td>Comp. 1</td><td>Comp. two</td>

ES 2 188 751 T3 pressure was 15 bar.

b All the ratios and amounts given refer to the ratios / amounts used in the preparation of the supported catalysts according to the particular examples.

c The temperature was 60 ° C.

d The temperature was 40 ° C and the pressure was 7 bar.

e The temperature was 40 ° C and the pressure 6 bar.

f 100 micromoles of AKZO Type 3A MMAO was added to the polymerization reactor before the catalyst.

g 100 micromoles of AKZO Type 3A MMAO was added to the polymerization reactor prior to catalyst.

h The temperature was 30 ° C.

100 micromoles of (i-Bu) 3Al were added to the polymerization reactor before the catalyst.