JP2003327611A - Method for manufacturing carrier material for ethylene (co)polymerization catalyst - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for preparing a catalyst that exhibits a high activity against polymerization of ethylene and an α-olefin of a higher molecular weight and that is capable of synthesizing an ethylene polymer and copolymer having a relatively narrow molecular weight distribution and a homogeneous branched chain distribution. <P>SOLUTION: The method comprises steps of supplying porous silica with a particular pore volume, supplying an alumoxane solution of a volume which is the pore volume of silica or less in a sufficient amount for predetermined aluminum supply to contact with each other and impregnating the solution into the pore of silica. At least one of metallocene compounds is added to the alumoxane solution prior to the contact and is mixed with an effective amount of the alumoxane to activate the metallocene compound to produce the catalyst. After the contact, the dried particles of silica to be impregnated with the solid alumoxane is recovered. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a carrier material (carrier ma).
terial) manufacturing method. The invention is carried out especially in the presence of a catalyst comprising the transition metal metallocene,
It relates to the improvement of low pressure fluidized bed gas phase systems for the polymerization and copolymerization of ethylene. The present invention is directed to reactor plugging (or fouling) in a fluidized bed gas phase reactor used in the presence of a catalyst comprising a transition metal metallocene.
To maintain continuous operation of the distributor plate.

[0002]

BACKGROUND OF THE INVENTION Polyethylene is industrially produced in a solventless gas phase reaction by using selected chromium and titanium containing catalysts in a fluidized bed process under specified operating conditions. The products of the early manufacturing processes showed a moderate to wide molecular weight distribution. In order to be industrially useful in a gas phase fluidized bed process, the catalyst must be highly active with high catalyst productivity, since the gas phase process system does not include an operation to remove catalyst residues. is there. Therefore, the catalyst residue in the polymer product needs to be low so that it can remain in the polymer during fabrication and / or without creating undue problems for the final consumer. . To that end, the patent literature describes the development of new catalysts with high activity and correspondingly high productivity values.

[0003]

The use of transition metal metallocene compounds as catalysts for the polymerization and copolymerization of ethylene is one of these developments. Metallocenes can be described by the empirical formula Cp _m MA _n B _p . These compounds are methylalumoxane
moxane, MAO) to produce olefin polymers and copolymers, such as ethylene and propylene homopolymers, ethylene-butene and ethylene-hexene copolymers, and the like (US Pat. No. 4,542, No. 199 and No. 4,
404,344). Unlike traditional titanium- and vanadium-based Ziegler-Natta catalysts, metallocenes without titanium and vanadium components, such as zirconocene catalysts, have a very narrow molecular weight distribution (25 to 25% for titanium-based catalysts). 30 MF
A resin is prepared having a R (melt flow rate, measured as an MFR (I ₂₁ / I ₂ ) of 15-18) and a homogeneous short chain branching distribution.

When traditional titanium- and vanadium-based catalysts are used to copolymerize ethylene and higher alpha-olefins, the olefins are heterogeneously incorporated into the polymer chain, with most olefins being the shortest polymers. It exists in the chain. However, when a zirconocene catalyst is used, the distribution of branches is essentially independent of chain length. LL produced by zirconocene catalyst
DPE resins have excellent properties. These resins can be used to make films with fairly good transparency and impact strength. There is less extraction of such resin and the balance of film properties in the machine and cross directions is excellent.

More recently, metallocene catalysts containing another (second) transition metal, such as titanium, have been developed, as exemplified in US Pat. No. 5,032,562. Which produces a bimodal (bimodal) molecular weight distribution product with a high molecular weight component and a relatively lower molecular weight component. The development of catalysts capable of producing bimodal products in a single reactor is important per se. This development is to perform a bimodal process in which one molecular weight component is run in one reactor, that component is transferred to another reactor and another component of different molecular weight is produced to complete the polymerization. It also provides an industrially feasible alternative to processes that require two reactors per second.

Methylalumoxane (MAO) is used as a cocatalyst with a metallocene catalyst. Alumoxanes of this type are represented by R- (Al (R) -O) n-AlR ₂ (as oligomeric linear alumoxane) and (-Al- (R) -O-) m (as oligomeric cyclic alumoxane) Wherein n is 1 to 40, preferably 10 to 20,
m is 3 to 40, preferably 3 to 20, and R is C _1-.
It is a C ₈ alkyl group, preferably a methyl group. ] The oligomeric linear and / or cyclic alkylalumoxane represented by Methylalumoxane may be trimethylaluminum, water or a hydrated inorganic salt such as CuSO ₄ 5H ₂ O or Al ₂ (SO ₄ ) ₃ .5H ₂ O.
It is usually produced by reacting with. It is also possible to produce methylalumoxane in situ in the reactor by placing trimethylaluminum and water or a hydrated inorganic salt in the polymerization reactor. MAO is
It is a mixture of oligomers with a very broad molecular weight distribution and usually has an average molecular weight of about 1200. MA
O is generally kept in solution in toluene. M
The AO solution remains liquid at the fluidized bed reactor temperature,
MAO itself is a solid at room temperature.

Most of the experiments reported in the literature for methylalumoxane used with metallocene catalysts as cocatalysts are conducted in slurry or solution processes rather than gas phase fluidized bed reactor processes. .

It has been found that in order to activate the catalyst in a fluidized bed reactor it is necessary to contact the metallocene catalyst with the MAO cocatalyst while the MAO is in solution. Furthermore, it has been found that large-scale reactor plugging occurs when the MAO solution is fed directly into the gas phase reactor in sufficient quantities to provide this liquid contact. Clogging occurs because the MAO solution forms a liquid film on the inner wall of the reactor.

The catalyst is activated when it contacts this liquid film, and the activated catalyst reacts with ethylene to produce a polymer coating, which grows dimensionally larger until the reactor is plugged. Furthermore, since substantially all activation occurs at the walls, MAO is not homogeneously distributed on the catalyst particles. The resulting heterogeneous polymerization results in low catalyst activity and poor product properties.

[0010]

[Means for Solving the Problems] alumoxan
The disadvantages of using e or aluminoxane), in particular methylalumoxane, in the preparation of the catalyst are: (1) it is porous, has a particle size of 1 to 200 μm and an average diameter of 50 to 500 Angstroms,
And supplying silica having pores having a pore volume of 0.5 to 5.0 ml / g; (2) alumoxane of the formula (a) or (b) [provided that the formula (a) Is R- (Al (R) -O) n-AlR ₂ for an oligomeric linear alumoxane, and
Formula (b) is (-Al (R) -O-) m for an oligomeric cyclic alumoxane, where n is 1
To 40, m is 3 to 40, R is _{C 1} -C ₈ alkyl group. ] And a solvent for the alumoxane, wherein the volume of the solution ranges from a value less than the pore volume of silica to a maximum volume of the solution equal to the pore volume of silica. , The concentration of alumoxane is A
5 to 20 expressed as% by weight of l; solution in which alumoxane provides sufficient amount of aluminum to give an Al / silica (w / w) molar ratio of 0.10 to 0.40. (3) adding at least one metallocene compound to the above volume of solution prior to the contacting in step (4),
The metallocene compound has the formula: Cp _m MA _n B _p [wherein Cp is a cyclopentadienyl group or a substituted cyclopentadienyl group; m is 1 or 2; M is zirconium or hafnium. And each of A and B is selected from the group consisting of a halogen atom, a hydrogen atom and an alkyl group, provided that m + n + p is equal to the valence of the metal M. ] The metallocene compound is mixed with an amount of alumoxane effective to activate the metallocene compound to form a catalyst; (4) silica and the above solution in the above volume. Contact
Impregnating the pores of silica having a pore volume of 0.5-5.0 ml / g with a solution to contain alumoxane in the pores; (5) adding solid alumoxane after the contact. The solution is by a method of making a carrier material impregnated with alumoxane and its derivatives, comprising recovering dry particles of impregnating silica.

Advantageously, the alumoxane is methyl alumoxane. The method preferably further comprises heating the dry particles to remove the solvent from the pores under temperature conditions effective to prevent crosslinking of the alumoxane. The temperature is preferably in the range of 30 ° C or higher and 60 ° C or lower.

Prior to the contacting in step (4), at least one metallocene compound can be added to the above volume of solution, the metallocene having the formula: Cp _m MA _n B _{p where} Cp is A cyclopentadienyl group or a substituted cyclopentadienyl group; m is 1 or 2; M is zirconium or hafnium; and m + n + p is equal to the valence of the metal M, and A and Each of B is selected from the group consisting of halogen atoms, hydrogen atoms and alkyl groups. ] The metallocene compound is mixed with an amount of methylalumoxane effective to activate it to produce a catalyst.

The metallocene compounds include dihalides of bis (cyclopentadienyl) metal, hydride halides of bis (cyclopentadienyl) metal, monoalkyl monohalides of bis (cyclopentadienyl) metal, and bis (cyclo It may be selected from the group consisting of dialkyls of pentadienyl) metal and dihalides of bis (indenyl) metal, wherein the halide group (halogen) is chlorine and the alkyl group is C ₁ -C ₆ alkyl.

Metallocene compounds include bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) hafnium dichloride, bis (cyclopentadienyl) zirconium dimethyl, bis (cyclopentadienyl) hafnium dimethyl, bis (cyclo Pentadienyl) zirconium hydride chloride, bis (cyclopentadienyl) hafnium hydride chloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl)
Hafnium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, cyclopentadienylzirconium trichloride, bis (indenyl) zirconium dichloride, bis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride and Ethylene- [bis (4,5,6,7-tetrahydro-1-
More preferably, it is selected from the group consisting of indenyl)] zirconium dichloride.

It is preferred that the solution has a composition that provides a molar ratio of alumoxane (expressed as aluminum) to metallocene in the range of 50 to 500. 1μ of dry particles
It is preferable to exceed a particle size of m. It is preferred to screen the dry particles to separate dry particles characterized by a particle size of 1 to 200 μm.

Silica is used in an amount of 0.1 to 3.0 per 1 g of the carrier.
It is preferred to include reactive hydroxyl groups in the millimolar range, prior to contacting in step (4) Mg: OH
To have a molar ratio of 0.9: 1 to 4: 1 in the formula: R " _m MgR ' _n [wherein R" and R'are the same or different C ₂ -C ₈ alkyl groups. , M + n is equal to the valence of Mg, m and n are 0, 1 or 2, respectively. ] It is possible to react a reactive hydroxyl group with an organomagnesium compound represented by A non-metallocene transition metal can be added to the slurry after reacting the reactive hydroxyl groups and prior to contacting in step (4).

Suitably both R "and R'are n-butyl groups. The non-metallocene compound is preferably a tetravalent titanium compound and has a metallocene content of 0.01 to 0.50: It is desirable to provide the composition in an amount sufficient to provide a Ti ratio, Another aspect of the present invention provides a composition produced by a method as described above.

According to yet another aspect of the invention, 100-350 psi (690-690) effective for producing a resin in the presence of a catalyst at temperatures in the range of 30 ° -115 ° C.
A fluidized bed gas phase reactor process for producing a resin is provided under polymerization conditions comprising a pressure in the range of 2400 KPa), the catalyst comprises alumoxane and the fluidized bed comprises a composition as described above. The process comprises the steps of introducing a feed that can be polymerized to produce a resin; and monomeric trialkylaluminum free of water and oligomeric or polymeric reaction products of the trialkylaluminum. Is introduced as a co-catalyst.

Ethylene polymer and ethylene and 1
Copolymers with C ₃ -C ₁₀ α-olefins or higher can be prepared according to the present invention. Therefore, it may be a copolymer having two monomer units and a terpolymer having three monomer units. Specific examples of such polymers include ethylene / 1-butene copolymers, ethylene / 1-hexene copolymers and ethylene / 4-methyl-1-pentene copolymers.

Hydrogen can be used as a chain transfer agent in the polymerization reaction of the present invention. The hydrogen / ethylene ratio used varies from about 0 to about 2.0 moles of hydrogen per mole of ethylene in the gas phase. Any gas that is inert to the catalyst and reactants may be present in the gas stream.

Ethylene / 1-butene and ethylene / 1
-Hexene copolymers are the most preferred copolymers that are polymerized in the catalytic and invented methods of the present invention. It is preferred that ethylene copolymers made in accordance with the present invention contain at least about 80% by weight ethylene units. The promoters of the present invention can also be used with the catalyst precursors of the present invention to polymerize propylene and other α-olefins and their copolymerization.
Α-produced by the promoter and catalyst precursor of the present invention
The structure of the olefin polymer depends on the structure of the cyclopentadienyl ligand attached to the metal atom in the catalyst precursor molecule. The promoter composition of the present invention can also be used with the catalyst precursor of the present invention to polymerize cycloolefins such as cyclopentene.

[0022]

DETAILED DESCRIPTION OF THE INVENTION In one embodiment, the catalyst used in the present invention comprises ethylene and higher molecular weight α-
It is possible to synthesize ethylene polymers and copolymers which exhibit high activity for the polymerization of olefins and have a relatively narrow molecular weight distribution and a homogeneous branching distribution. The catalyst used in the present invention exhibits high activity for the copolymerization of ethylene and higher alpha-olefins, linear low density polyethylene with a relatively narrow molecular weight distribution and a homogeneous branching distribution. Can be synthesized. The molecular weight distribution, measured as MFR (melt flow rate), is in the range of 15-25. Branch distribution in ethylene copolymers is evaluated based on the melting point of the resin. A relatively homogeneous branching distribution is one in which the melting point is in the range 100-120 ° C, depending on the comonomer composition. In this embodiment, the catalyst of the present invention contains only one transition metal source, metallocene.

In another aspect of the present invention, the catalyst of the present invention exhibits high activity for the polymerization of ethylene and higher molecular weight α-olefins, with a broad molecular weight distribution and generally higher levels in resin blends. Ethylene polymers and copolymers with a bimodal molecular weight distribution having a molecular weight component and a relatively low molecular weight component can be synthesized. The molecular weight distribution of the bimodal resin, expressed as MFR, is about 110-140. In this aspect, the catalyst of the present invention comprises two transition metal compounds, only one of the transition metal compounds being a metallocene.

In another aspect of the present invention, the catalyst used in the present invention is ethylene and a higher molecular weight α.
-High activity for the copolymerization of olefins, linear low density polyethylenes with relatively narrow molecular weight distribution and homogeneous branching distribution can be synthesized. The molecular weight distribution ranges from 14 to 24, measured as MFR. In this embodiment, the catalyst of the present invention contains only one source of transition metal, the metallocene.

[0025] In the method according to one aspect of the fluidized bed reactor the present invention, in fact, the fluidized bed reaction system which can be used, shown in Figure 1. Referring to it, the reactor 10 consists of a reaction zone 12, a deceleration zone 14 and a distributor plate 20. Clogging can occur throughout the cold region (the region of the reactor below the temperature where any component in the gas phase reactor is in the liquid phase, but not in the gas phase), but due to flow restriction, the distributor plate is Clogging of the distributor plate is one of the easiest to detect because it causes a rapid increase in pressure drop across it. Such flow restrictions also cause changes in the fluidization pattern and contribute to plugging (fouling) of the reactor walls. The lowest temperature in the reactor loop is in the reactor inlet below the distributor plate. Other areas that represent the coldest part of the fluidized bed reactor system include the cooler and the pipe between the cooler and the bottom head.

The reaction zone 12 comprises polymerizable, growing polymer particles and a small amount of catalyst particles which are fluidized by a continuous flow of modifying gas phase components. In order to maintain a viable fluidized bed, the mass flow rate of gas through the bed should be greater than the minimum flow rate required for the flow, preferably about 1.5 of Gmf.
To about 10 times, more preferably about 3 to about 6 times Gmf. Gmf is used in its accepted form as an abbreviation for the minimum gas mass flow rate required to achieve fluidization (CY Wen.
n) and YH Yu, “Mechanics ·
Mechanics of Fluidizat
ion) ”, Chemical Engineering Progress Symposium Series (Chemical Engineering Progres
Symposium Series), Volume 62, 100-111
P., 1966). The distributor plate 20 serves the purpose of diffusing the recycled gas passing through the bed at a flow rate sufficient to maintain fluidization at the bottom of the bed. The fluidized state is that the gas flowing to and through the bed
High recycle flow rates, typically on the order of about 50 times the makeup gas supply flow rate.

Make-up gas is at a rate (flow rate) equal to the rate at which the reaction produces a granular polymer product.
Supplied to the floor at. Make-up gas composition is measured by a gas analyzer 16 located above the bed. The make-up gas composition is continuously adjusted to maintain an essentially steady state gaseous composition within the reaction zone.

The unreacted portion of the gas stream within the bed (recycled gas) passes through the deceleration zone 14 where the entrained particles are given the opportunity to descend back to the bed. The unreacted gas stream then passes through cyclone 22, through filter 24, through compressor 25, through heat exchanger 26, and then back to the bed. The distributor plate 20 serves the purpose of diffusing recycled gas through the bed at a flow rate sufficient to maintain fluidity. The plate may be a screen, a slotted plate, a perforated plate, a bubblecap type plate, etc. The elements of the plate may all be stationary, or the plate may be movable, as disclosed in US Pat. No. 3,298,792.

Ethylene is polymerized or copolymerized in the gas phase.
Conditions in Fluidized Bed Reactor for Use It is necessary to operate the fluidized bed reactor at a temperature below the sintering temperature of the polymer particles. For the production of ethylene copolymers in the process of the present invention, operating temperatures of about 30 ° C to 115 ° C are preferred, and about 75 ° C to 9 ° C.
Most preferred is an operating temperature of 5 ° C. About 75 ° C. to 90 ° to produce a product having a density of about 0.91 to 0.92.
A temperature of about 80 ° C to 100 ° C is used to produce a product having a density of about 0.92 to 0.94 and a density of about 0.94 to 0.96 is used. Temperatures of about 90 ° C. to 115 ° C. are used to produce the product having.

The fluidized bed reactor has approximately 1000 psi (6.
Operated at pressures up to 9 MPa), preferably about 150
Operating at pressures of ~ 350 psi (1 MPa to 2.4 MPa), operating at higher pressures in such ranges is advantageous for heat transfer, as increasing pressure increases the unit volumetric heat capacity of the gas.

The partially or fully activated catalyst is fed into the bed at a location above the distributor plate at a rate equal to its consumption rate. The catalyst used in the practice of the present invention is so active that feeding fully activated catalyst into the lower region of the distributor plate initiates polymerization there, eventually plugging the distributor plate. May be caused. By instead feeding into the bed, the distribution of the catalyst throughout the bed is promoted,
The formation of locally high catalyst concentrations is prevented.

The rate of polymer production in the bed is controlled by the rate (flow rate) of catalyst supply. If there is any change in the flow rate (ratio) of supplying the catalyst, the reaction heat generation amount (ratio) changes, so the temperature of the recycle gas is adjusted to adapt to the change in the heat generation amount. Full operation of both the fluidized bed and the recycled gas cooling system naturally requires the detection of temperature changes in the bed so that the operator can properly adjust the temperature of the recycled gas. .

Since the rate of heat production is directly related to the production of product, by measuring the temperature rise of the gas passing through the reactor (difference between inlet gas temperature and outlet gas temperature), at a constant gas velocity. The rate of formation of the granular polymer is known.

Under a given set of operating conditions, a fluidized bed is brought to an essentially constant height by withdrawing a portion of the bed as product at a rate equal to the rate (rate) of the particulate polymer product. Maintained.

Catalyst Composition A catalyst containing only one transition metal in the form of a metallocene is
It has an activity of at least about 3000 g (polymer) / g (catalyst) or about 1000 kg (polymer) / g (transition metal). A catalyst comprising two transition metals, one of which is in the form of metallocene and one of which is in the non-metallocene form, has at least about 2000 g (polymer) / g (catalyst) or about 100 kg (polymer) / g (Transition metal)
Has the activity of.

The catalyst used in the present invention comprises a cocatalyst comprising an aluminum alkyl compound, such as an alumoxane-free trialkylaluminum, and a catalyst precursor comprising a carrier, alumoxane and at least one metallocene. Comprising, in one aspect, the catalyst further comprises a non-metallocene transition metal source.

The carrier material is a solid, granular, porous, preferably inorganic substance such as an oxide of silicon and / or aluminum. The carrier material is preferably used in the form of a dry powder having an average particle size of about 1 micron to about 250 microns, preferably about 1 micron to about 200 microns, more preferably about 10 microns to about 150 microns. If desired, the support material to be treated may be sieved to also ensure that the catalyst-support containing composition is porous and has a mesh size greater than 150 mesh. This is highly desirable in embodiments of the invention where the catalyst contains only one transition metal in the form of a metallocene and is used to reduce gel and produce narrow molecular weight LLDPE. .

The surface area of the carrier is at least about 3 m ² /
g, preferably at least about 50 m ² / g and about 350
It can be up to m ² / g. The carrier material is preferably said to be dry, ie free of adsorbed water.
Drying of the carrier material can be accomplished by heating at about 100 ° C to about 1000 ° C, preferably about 600 ° C.
When the support is silica, it is at least 200 ° C, preferably about 200 ° C to about 850 ° C, most preferably about 600 ° C.
Heated to ℃.

In the most preferred embodiment, the support is silica (having at least some active hydroxyl groups), which is fluidized with nitrogen to about 600 ° C. prior to use in the first catalytic synthesis step. About 16
Dehydrated by heating for about 0.7 mmol /
A surface hydroxyl group concentration of g (mmols / g) was achieved. The most preferred embodiment of silica is high surface area amorphous silica (surface area = 300 m ² / g; pore volume 1.65).
cm ³ / g), which is WR Grace and Compan
y) Davison Chemical Division (Davison C
Chemical Division) is a substance sold under the trade name of Davison 952 or Davison 955. Silica is in the form of spherical particles, such as those obtained by the spray drying process.

To form the catalyst of the present invention, all catalyst precursor components can be dissolved with the alumoxane and impregnated into the support. In a unique method, in the method described below, the support material is impregnated with solid alumoxane, preferably methylalumoxane. Alumoxane This type of formula: R- (Al (R) -O ) ( as a linear alumoxane oligomer) n-AlR ₂ and (-Al- (R) -O-) m ( as cyclic alumoxane oligomer) [In the formula, n is 1 to 40, preferably 10 to 20,
m is 3 to 40, preferably 3 to 20, and R is C _1-.
It is a C ₈ alkyl group, preferably a methyl group. ] The oligomeric linear and / or cyclic alkylalumoxane represented by MAO is a mixture of oligomers with a very broad molecular weight distribution, usually around 120
It has an average molecular weight of 0. MAO is generally kept in solution in toluene. M at fluidized bed reactor temperature
The AO solution remains liquid, but MAO itself is a solid.

At any stage of preparing the catalyst,
The alumoxane may be impregnated into the support, but the preferred stage of incorporation of the alumoxane depends on the final catalyst sought to be synthesized. The volume of the solution comprising the solid alumoxane and its solvent can vary depending on the catalyst sought to be made. In a preferred embodiment, one of the controlling factors in incorporating alumoxane into the support material catalyst synthesis is the pore volume of silica. In this preferred embodiment, the process of impregnating the carrier material is by injecting the alumoxane solution in the alumoxane solution without forming a slurry of the carrier material, eg silica. The volume of the alumoxane solution is
It is sufficient to fill the pores of the carrier material without the formation of a slurry (the volume of the solution exceeds the pore volume of silica); therefore, the maximum volume of alumoxane solution is the carrier material sample. It is preferable not to exceed the total pore volume of The maximum volume of this alumoxane solution ensures that no silica slurry is formed.

Therefore, the pore volume of the carrier material is 1.65c.
When it is m ³ / g, the volume of alumoxane is 1.
65 cm ³ / g-equal to or less than the carrier material. As a result of this condition, the impregnated carrier material appears to dry immediately after impregnation, but the pores of the carrier are
Above all, it will be filled with the solvent.

The solvent may be removed from the alumoxane-impregnated pores of the support material by heating and / or under positive pressure generated by an inert gas such as nitrogen. If employed, the conditions in this step are controlled to reduce, if not eliminate, agglomeration of the impregnated carrier particles and / or alumoxane crosslinking. In this step, the solvent can be removed by performing evaporation at a relatively low heating temperature of about 40 ° C. or higher and about 50 ° C. or lower to prevent agglomeration of catalyst particles and crosslinking of alumoxane. Although it is possible to remove the solvent by evaporation at a relatively higher temperature than specified at temperatures in the range of about 40 ° C. and above and about 50 ° C. and below, in order to prevent agglomeration of the catalyst particles and alumoxane crosslinking , Must use very short heating time.

In a preferred embodiment, the metallocene is added to the alumoxane solution before the support is impregnated with the solution. The maximum volume of the alumoxane solution, which also contains the metallocene, is again the total pore volume of the support material sample. Of the aluminum supplied by the alumoxane represented as Al, the metallocene metal represented as M (eg Z
The molar ratio to r) is 50 to 500, preferably 75.
~ 300, most preferably 100-200. An added advantage of the present invention is that it is possible to directly control this Al: Zr ratio. In a preferred embodiment, the alumoxane and metallocene compound are used prior to their use in the infusion step.
Mix at a temperature of about 20 ° C to 80 ° C for 0.1 to 6.0 hours. The metallocene and alumoxane solvent may be any suitable solvent such as aromatic hydrocarbons, halogenated aromatic hydrocarbons, ethers, cyclic ethers or esters, preferably toluene.

The metallocene compound has the formula: Cp _m MA _n B _p [wherein Cp is an unsubstituted or substituted cyclopentadienyl group, M is zirconium or hafnium, A and B are halogen atoms, hydrogen Alternatively, it belongs to a group containing an alkyl group. ] Is shown. In the above metallocene compound formula, the preferred transition metal atom M is zirconium. In the formula of the metallocene compound above, the Cp group is an unsubstituted, 1-substituted or polysubstituted cyclopentadienyl group. The substituents on the cyclopentadienyl group may be linear C ₁ -C ₆ alkyl groups. The cyclopentadienyl group is a bicyclic or tricyclic group, for example, an indenyl group, a tetrahydroindenyl group, a part such as a fluorenyl group or a partially hydrogenated fluorenyl group, and a substituted bicyclic or tricyclic group. It may be part of a ring group. In the formula of the metallocene compound of the above, when m is equal to 2, the cyclopentadienyl groups is a polymethylene or dialkylsilane groups, such as -CH 2 _-, - CH ₂ -CH
_2- , -CR ₁ -CR ₂ -and -CR ₁ R ₂ -CR ₁ R _2-
[Wherein R ₁ and R ₂ are short chain alkyl groups or hydrogen. _{], - Si (CH 3)} 2 -, Si (CH 3) 2
_{-CH 2 -CH 2 -Si (CH 3} ) 2 - and may be cross-linked by the same cross-linkable group. When the substituents A and B in the formula of the metallocene compound above are halogen atoms, they belong to the group of fluorine, chlorine, bromine or iodine. In the formula of the metallocene compound above,
When the substituents A and B are alkyl groups, they are
A linear or branched C ₁ -C ₈ alkyl group, for example, methyl group, ethyl group, n-propyl group, isopropyl group,
It is preferably an n-butyl group, an isobutyl group, an n-pentyl group, an n-hexyl group or an n-octyl group.

Suitable metallocene compounds include bis (cyclopentadienyl) metal dihalides, bis (cyclopentadienyl) metal hydride halides, bis (cyclopentadienyl) metal monoalkyl monohalides, Included are bis (cyclopentadienyl) metal dialkyls and bis (indenyl) metal dihalides, where the metal is zirconium or hafnium and the halogen (or halide) group is chlorine, preferably an alkyl group Is C ₁ -C ₆ alkyl. To further illustrate, but not limited to, metallocenes include bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) hafnium dichloride, bis (cyclopentadienyl) zirconium dimethyl, bis (cyclopentadienyl). (Enyl) hafnium dimethyl, bis (cyclopentadienyl) zirconium hydride chloride, bis (cyclopentadienyl)
Hafnium hydride chloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) hafnium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, cyclopentadienylzirconium trichloride, bis Includes (indenyl) zirconium dichloride, bis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride and ethylene- [bis (4,5,6,7-tetrahydro-1-indenyl)] zirconium dichloride. .

The metallocene compounds used in this embodiment of the art can be used as crystalline solids, as solutions in aromatic hydrocarbons or in supported form. As mentioned above, the alumoxane may be impregnated into the support at any stage of the method of catalyst preparation.
When the catalyst comprises two transition metal components, one is a metallocene, one is a nonmetallocene (without an unsubstituted or substituted cyclopentadienyl group) and the hydroxyl group of the support material is an organomagnesium. After the reaction with the compound and the nonmetallocene transition metal compound, it is preferred to carry out the alumoxane impregnation according to the unique method described above. In this embodiment, the amount of Al supplied by the alumoxane is 50-500, preferably 100-300.
Is sufficient to provide a molar ratio of Al: transition metal (which is supplied by the metallocene) over the range of.
The carrier material having (OH) groups is slurried in a non-polar solvent and the resulting slurry is contacted with at least one organomagnesium composition having the empirical formula below. A slurry of carrier material in a solvent is added to the solvent in the solvent, preferably with stirring, and the mixture is added at about 25 ° C.
It is prepared by heating to about 70 ° C, preferably about 40 ° C to about 60 ° C. The temperature here is important for the subsequently added non-metallocene transition metal; that is, if the temperature in the slurry is about 90 ° C., deactivation of the subsequently added transition metal will occur. It
Subsequently, the slurry is contacted with the aforementioned organomagnesium composition, while heating is continued at the aforementioned temperature.

Organomagnesium composition (organomagn
esium composition) is an empirical formula: R " _m MgR ' _n [wherein R" and R'are the same or different C ₂ -C ₁₂
An alkyl group, preferably a C ₄ -C ₁₀ alkyl group, more preferably a C ₄ -C ₈ normal alkyl group, most preferably both R ″ and R ′ are n-butyl groups, m + n Is equal to the valence of Mg, m and n are 0, 1 or 2, respectively.]

Suitable non-polar solvents are all of the reactants used in the present invention, ie those in which the organomagnesium composition and the transition metal compound are at least partially soluble and which are liquid at the reaction temperature. Preferred non-polar solvents are alkanes such as hexane, n-
Various other materials can be used including heptane, octane, nonane and decane, but also cycloalkanes such as cyclohexane, aromatic compounds such as benzene, toluene and ethylbenzene. The most preferred non-polar solvent is cyclopentane. Prior to use, the non-polar solvent is purified, for example by silica gel and / or percolation through molecular sieves, to remove traces of water, oxygen, polar compounds and other substances which can adversely affect the catalytic activity.

In the most preferred embodiment of the synthesis of this catalyst, an excess of the organomagnesium composition in solution can react with other synthetic species and precipitate out of the support, either physically or on the support. It is important to add only the amount of chemically-deposited organomagnesium composition. The carrier drying temperature affects the number of carrier sites available for the organomagnesium composition-the higher the drying temperature, the lower the number of sites. Therefore, the exact molar ratio of the organomagnesium composition to the hydroxyl groups on the carrier will vary,
It is determined on a case-by-case basis to ensure that an amount of the organomagnesium composition is added to the solution such that it is deposited on the carrier without leaving excess organomagnesium composition in the solution. There must be.

Furthermore, it is believed that the molar amount of organomagnesium deposited on the support is greater than the molar amount of hydroxyl groups on the support. Therefore, the following molar ratio is
It is only a guideline and the exact amount of the organomagnesium composition in this embodiment must be controlled by the functional limitations mentioned above, i.e., not more than can be deposited on the carrier. I won't. If more than this is added to the solvent, the excess will react with the nonmetallocene transition metal compound, thereby forming a precipitate on the outside of the support,
This is detrimental to the synthesis of the catalyst of the invention and should be avoided. The amount of the organomagnesium composition that does not exceed the amount deposited on the carrier can be determined by any conventional method, for example, adding the organomagnesium composition to a slurry of the carrier in a solvent while stirring the slurry in the solvent. It can be measured by, for example, a method performed until the organomagnesium composition is detected as a solution.

For example, for a silica support heated at about 600 ° C., the amount of organomagnesium composition added to the slurry is such that the molar ratio of Mg to hydroxyl groups (OH) on the solid support is about 0. 5: 1 to about 4:
1, preferably about 0.8: 1 to about 3: 1, more preferably about 0.9: 1 to about 2: 1, most preferably about 1: 1. The organomagnesium composition is dissolved in a non-polar solvent to form a solution from which the organomagnesium composition is deposited on the carrier.

It is also possible to add an amount of the organomagnesium composition in excess of that which will cause it to adhere to the carrier, and then to remove the excess organomagnesium composition, for example by filtration and washing. However, this alternative method is less desirable than the preferred embodiment described above.

After the addition of the organomagnesium composition to the slurry is complete, the slurry is contacted with a nonmetallocene transition metal compound containing no substituted or unsubstituted cyclopentadienyl groups. Slurry temperature is about 25 ℃ ~
It should be maintained at about 70 ° C, preferably about 40 ° C to about 60 ° C. As mentioned above, at temperatures of this slurry of about 80 ° C. or higher, non-metallocene transition metal deactivation occurs. The non-metallocene transition metal compounds used in the present invention are provided by Fisher Scientific Company, Catalog No. 5-702-10, provided such compounds are soluble in non-polar solvents. , IVA and VA metal compounds of the Periodic Table of Elements, as published by 1978. Examples of such compounds are titanium and vanadium halides such as titanium tetrachloride, TiCl
₄ , vanadium tetrachloride, VCl ₄ , vanadium oxytrichloride, VOCl _3, etc., and titanium and vanadium alkoxides (wherein the alkoxide group component is 1
Has a branched or unbranched alkyl group having from about 20, preferably from about 1 to about 6 carbon atoms. ), Etc., but is not limited to these. A preferable transition metal compound is a titanium compound, and a preferable tetravalent titanium compound. The most preferred titanium compound is titanium tetrachloride. The amount of titanium or vanadium in non-metallocene form is in the Ti / Mg molar ratio in the range 0.5 to 2.0, preferably 0.75 to 1.50.

It is also possible to use mixtures of such nonmetallocene transition metal compounds, in general there being no restrictions on the transition metal compounds which can be included. The transition metal compounds that can be used alone can also be used in combination with other transition metal compounds.

The alumoxane-metallocene incorporation may be carried out directly in this slurry. Alternatively, according to the unique method of injecting alumoxane into the pores of the support as described above, after addition of the nonmetallocene transition metal compound,
The carrier slurry may be separated from the solvent to form a free flowing powder. The free-flowing powder can be impregnated by measuring the pore volume of the carrier and supplying an alumoxane (or metallocene-alumoxane) solution of a volume equal to or less than the pore volume of the carrier, Collect the dried catalyst precursor. The resulting free flowing powder (referred to herein as the catalyst precursor) is combined with an activator (sometimes referred to as a cocatalyst). The cocatalyst may be an alumoxane-free trialkylaluminum. Trimethylaluminum (TMA) is preferably the cocatalyst or activator. The amount of TMA activator is from about 10: 1 to about 1000: 1, preferably about 15: 1 to about 300: 1, most preferably about 20: 1.
An amount sufficient to provide an Al: Ti molar ratio of about 100: 1. The catalyst shows a high activity in the pilot plant for a long period of time and hardly deactivates.

The catalyst precursor of the present invention comprises a metallocene compound and an alumoxane and can be fed in particulate form to a fluidized bed reactor for vapor phase polymerization and copolymerization of ethylene. The co-catalyst or activator of the present invention is also fed to a fluidized bed reactor for ethylene polymerization and copolymerization in the absence of alumoxane solution.

The invention is illustrated by the examples below. Example 1 The titanium component of the catalyst was prepared using the chemical impregnation method.
The zirconium component of the catalyst was prepared using the physical impregnation method. Solution (A): 50 ml serum-bo
ttle) with 0.140 g of Cp ₂ ZrCl ₂ and then 10.2 g of methylalumoxane (13.2 wt% A
l) The solution was added. The solution was left at room temperature for 60 minutes, after which the entire contents were transferred to a silica slurry as described below.

1 with magnetic stirrer bar
To a 00 ml pear flask was added 3.0 g of Davison 955 silica calcined at 600 ° C., followed by the addition of about 20 ml of dry toluene.
The flask was placed in a 59 ° C. oil bath. Then 2.
9 ml of dibutyl magnesium (0.74 mmol / m
l) was added to the silica / toluene slurry. The contents of the flask were stirred for 25 minutes. Then 2.3 ml of 0.94
An M (molar concentration) titanium tetrachloride solution (heptane solution) was added to the flask. The slurry turned dark brown and stirring was continued for 25 minutes. Finally, the solution (A)
Of the slurry was transferred to the catalyst preparation flask, and the slurry was mixed with 10
Stir for minutes. After this time, all solvent was removed by evaporation under a nitrogen purge. The catalyst yield was 5.6 g and was a dark brown, free-flowing powder. The Al / Zr ratio was 104.

Example 2 An ethylene / 1-hexene copolymer was prepared using the catalyst of the previous example under polymerization conditions to produce a high density polyethylene (HDPE) having a flow index (I ₂₁ ) of about 6. 1.6 at 50 ° C. while purging with a small amount of nitrogen.
A liter stainless steel autoclave was charged with 0.750 liter dry heptane, 0.030 liter dry 1-hexene and 4.0 mmol trimethylaluminum (TMA). The reactor was closed, the stirring speed was set to about 900 rpm, the internal temperature was raised to 85 ° C, and the internal pressure was changed from 7 psi to 10 psi with hydrogen.
(48KPa to 69KPa). Ethylene was added and the reactor pressure was maintained at about 203 psi (1.4 MPa). Next, 0.0639 g of catalyst was forced into the reactor with ethylene, the temperature was raised and held at 95 ° C. Polymerization was continued for 60 minutes, then the ethylene feed was stopped and the reactor was cooled to room temperature. 78 g of polyethylene was obtained.

The molecular weight distribution (MWD) of this polymer was determined by gel permeation chromatography (Gel Permeation Chromatog).
Raphy, GPC) and the results showed that the polymer had a bimodal molecular weight distribution (bimodal MWD) (FIG. 2). FIG. 3 shows a GPC chromatogram of HDPE produced in a tandem gas phase reactor. A comparison of these GPC chromatograms reveals that the polymer produced in a single reactor is essentially the same as the polymer produced in two tandem reactors. Currently commercially available samples of HDPE with a bimodal molecular weight distribution are produced in a tandem reactor process. In this process, two reactors are operated in series, the catalyst is exposed to ethylene polymerization conditions in one reactor, and the resulting polymer-catalyst particles are transferred to a second reactor for further polymerization. . One of the main process differences in the two different reactors is the different amount of hydrogen in the two different reactors. Since hydrogen acts as a chain transfer agent, a relatively lower molecular weight product is obtained in a reactor containing more hydrogen; while a larger molecular weight product is obtained in a reactor containing less hydrogen. The product is obtained.

Example 3 This catalyst was prepared in two stages. 495 g of Davison pre-calcined with dry nitrogen for approximately 12 hours at 600 ° C
Grade 955 silica was added to a 2 gallon stainless steel autoclave under a small nitrogen purge to remove oxygen and moisture from the catalyst preparation vessel. Next, 4.0 liters of dry isopentane (IC
5) is added to the autoclave and silica / IC5 is added to about 10
Slurry at 0 rpm, internal temperature about 55-60 ℃
Held in. Then 469 ml of a 0.76 M solution of dibutylmagnesium in heptane was added to the silica / IC5 slurry and stirring was continued for 60 minutes. Next, 39.1 ml
The pure titanium tetrachloride of was diluted with about 40 ml of IC5, this solution was added to the autoclave, and stirring was continued for 60 minutes. Finally, the solvent was removed by nitrogen through a vent line to obtain 497 g of a brown, free-flowing powder. Ti was 2.62% by weight; Mg was 1.33% by weight, and the Ti / Mg molar ratio was 1.0.

Temperature-jacketed 492 g of the product of the first stage.
1.6 gallon glass feeler with hood and internal stirrer
The medium was added to the prepared vessel. The first stage product is 1.5
cm ^Three/ G (ie 738 cm^ThreePore volume)
It was estimated to have a product. Then made of stainless steel
Hoke bonb of 13.93g of (BuC
p)_TwoZrCl_Two(Zr34.4 mmol) and 71
7.5 ml of methylalumoxane (4.8M) toluene
The solution (Al 3,444 mmol) was added. (Remark:
The total volume of chillalumoxane / toluene solution is the first stage
Equal to or less than the total pore volume of the product
Absent. ) Next, a toluene solution containing methylalumoxane
And zirconium compound, and then this solution
To approximately 5 ml aliquot of first stage product in 90 minutes
Added; (during this time the first stage product was completely dried
The state remains and always consisted of a free-flowing powder).
Finally, the glass temperature at the jacket temperature of about 45 ° C for 5 hours
The chamber was purged with nitrogen. Yield: 877 g of free-flowing powder.
Ti is 1.85% by weight and Zr is 0.30% by weight.
I found out that

Example 4 The catalyst described in Example 3 was tested in a pilot plant fluidized bed gas phase reactor under the following conditions: ethylene 180 psi (1.2 MPa) hydrogen / ethylene 0.005-0.008 hexene / ethylene 0.015 The resin produced with a reactor temperature of 95 ° C. and a productivity of about 1400 g-polymer / g-catalyst had the following properties. Average particle size 0.017 inch (0.043 mm) Resin metal content 13.0 ppm HLMI (I21) 5.3 MFR (I21 / I2.16) 113 Density 0.949 g / cm ³

The GPC curve of this product is shown in FIG. 4 (solid line).
The results are shown in Fig. 4 and are compared with those of a tandem device industrially manufactured in a two-step process (dotted line in Fig. 4) in which components of different molecular weights are produced at each step. The film properties of the product of Example 4 (solid line in Example 4) are based on the industrially manufactured product (dotted line in Figure 4) OxyChem.
It is equivalent to L5005.

[0066]

[Table 1]

The GPC curve results in FIG. 4 show that the bimodal product of Example 4 (solid line) has a high molecular weight component with a molecular weight greater than that produced in the two reactor process of tandem type. Indicates. The film of Example 4 was
The gel content, if not included, is substantially reduced. The film of Example 4 had improved dirt
It has a dart impact.

Comparative Example 1 Ethylene partial pressure of 130 psi (900 KPa), 85 ° C.
The zirconium catalyst was tested in a slurry reactor at.
A hexene / ethylene gas ratio of 0.03 was used. MAO
/ Toluene solution (12 wt%, 2 ml) was added to the reactor. A productivity of 800 g-resin / g-catalyst / hr was measured. The same catalyst system was tested in a fluid bed reactor at 200 psi (1.4 MPa) ethylene partial pressure and 90 ° C. A hexene / ethylene gas ratio of 0.025 was used.
150-200 cm of 2 wt% MAO / toluene solution
A feed flow rate of ³ / hr was adopted. The MAO solution was added below the distributor plate. The catalyst productivity was 220 g-resin / g-catalyst / hr even at very high MAO / toluene feed rates. Furthermore, just 18 hours after starting the MAO supply,
It was necessary to shut down the reactor due to plate clogging. This comparative example shows that it is more effective to activate the zirconium catalyst before introducing it into the gas phase reactor. It also illustrates the problem of clogging that occurs when the MAO solution is added to the gas phase reactor.

Comparative Example 2 A titanium / zirconium mixed metal catalyst was tested in a fluidized bed reactor. 150 psi (1 MPa), 90 ° C,
A hexene / ethylene gas ratio of 0.04 was employed and the hydrogen to ethylene gas ratio was 0.045. A 2 wt% MAO solution in toluene was added below the distributor plate in the fluid bed. Analysis of the resin flow index and GPC curves showed that the zirconium catalyst sites were active and the Ti: Zr productivity ratio was 7: 3. However, it was necessary to shut down the reactor within 24 hours due to a plugged distributor plate.

Comparative Example 3 The same titanium / zirconium catalyst used in Example 2 was tested in a fluidized bed reactor. 90 this reactor
The operation was performed at 150 ° C. and an ethylene partial pressure of 150 psi (1 MPa). Using a hexene: ethylene gas ratio of 0.03,
The hydrogen: ethylene ratio was 0.04. A 2 wt% solution of MAO in toluene was added directly to the bed at a flow rate of 200 cc / hr. The flow index and molecular weight distribution of the resin clearly showed that the zirconium sites were active and the Ti: Zr productivity ratio was 3: 7. During the course of this test run, it shut down due to the very large chunks that grew around the inlet section. This comparative example shows that the relative activity of the zirconocene catalyst is quite high when there is good contact between the MAO / toluene droplets and the catalyst sites. It also demonstrates that when the MAO solution is added directly to the fluidized bed of polymer in the reactor, plugging occurs.

Comparative Example 4 The catalysts used in Examples 2 and 3 were re-tested under the same conditions used in Example 3. The MAO feed flow rate was the same as well. During this test, 10 lb / h (4.5 Kg / h) was applied using an ultrasonic atomizer.
MAO was dispersed in the ethylene gas stream of r).
This atomizer uses MAO solution for very small droplets (4
0 micron). Toluene was evaporated from MAO using sufficient gas. This gas flow rate was measured in an off-line test using toluene alone. The resin produced during this test showed no evidence of activity from the zirconium site. Furthermore, after long-term operation,
There were no indications of reactor plugging. This comparative example
It has been demonstrated that it is the presence of liquid in the reactor that is responsible for both zirconium activation and reactor plugging.

[Brief description of drawings]

FIG. 1 is a schematic diagram of a fluidized bed reactor for vapor phase polymerization of ethylene.

FIG. 2 is a gel permeation chromatogram of the product of Example 2.

FIG. 3 is a gel chromatogram of a bimodal product produced in two reactors.

FIG. 4 is a gel chromatogram of the product of Example 4.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Frederick Yip-Quy Lo             United States 08818 New Jersey             ー, Edison, P / O Box             752 (72) Inventor Thomas Edward Nowrin             United States 08512 New Jersey             ー, Cranberry, Perrin Pass No. 7 (72) Inventor Ronald Stephen Shinomoto             United States 08817 New Jersey             ー, Edison, Rivendel Way             No. 406 (72) Inventor Pradeep Pandurang Sirod             car             United States 08873 New Jersey             ー, Somerset, Johnson Road 52             Turn F term (reference) 4J128 AA01 AB00 AC01 AC28 AD05                       BA01A BA01B BB01A BB01B                       BC15B BC25A CA28C EB02                       FA04 GB03

Claims (6)

[Claims] (1) Porous, having a particle size of 1 to 200 μm, an average diameter of 50 to 500 Å, and a pore volume of 0.5 to 5.0 ml / g.
(2) an alumoxane of formula (a) or (b) [wherein formula (a) is R- (Al (R) -O) n-AlR; ₂ , for linear oligomeric alumoxanes, and
Formula (b) is (-Al (R) -O-) m for an oligomeric cyclic alumoxane, where n is 1
To 40, m is 3 to 40, R is C ₁ -C ₈ alkyl group. ] And a solvent for the alumoxane, wherein the volume of the solution ranges from a value less than the pore volume of silica to a maximum volume of the solution equal to the pore volume of silica. , The concentration of alumoxane, expressed as% by weight of Al, is from 5 to 20, and the alumoxane provides a sufficient amount of aluminum to give an Al / silica (weight / weight) ratio of 0.10 to 0.40. performing the supply so as to supply; (3) prior to the contacting of step (4), to a solution of the above volume, the method comprising adding at least one metallocene compound, the metallocene compound has the formula: Cp _m MA _n B _p [wherein Cp is a cyclopentadienyl group or a substituted cyclopentadienyl group; m is 1 or 2; M is zirconium or hafnium; and m + n + Each of A and B is selected from the group consisting of a halogen atom, a hydrogen atom and an alkyl group, provided that p is equal to the valence of the metal M. ] The metallocene compound is mixed with an amount of alumoxane effective to activate the metallocene compound to form a catalyst; (4) silica and the above solution in the above volume. Contact
Impregnating the pores of silica having a pore volume of 0.5-5.0 ml / g with a solution to contain alumoxane in the pores; (5) adding solid alumoxane after the contact. A method of making a carrier material for an ethylene (co) polymerization catalyst impregnated with alumoxane and its derivative materials, comprising recovering dry particles of impregnated silica. 2. The metallocene compound is bis (cyclopentene).
Tadienyl) metal dihalide, bis (cyclopenta)
Dienyl) metal hydride halides, bis (cyclope
N-dienyl) metal monoalkyl monohalide, bi
Bis (cyclopentadienyl) metal dialkyl and bis
Selected from the group consisting of (indenyl) metal dihalides
Where the halide group is chlorine and the alkyl group is
C₁-C ₆The method of claim 1, wherein the method is alkyl. 3. The metallocene compound is bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) hafnium dichloride, bis (cyclopentadienyl) zirconium dimethyl, bis (cyclopentadienyl) hafnium dimethyl, bis. (Cyclopentadienyl) zirconium hydride chloride, bis (cyclopentadienyl) hafnium hydride chloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) hafnium dichloride, bis (n-butyl) Cyclopentadienyl) zirconium dichloride, cyclopentadienylzirconium trichloride, bis (indenyl) zirconium dichloride, bis (4,5,6,7-tetrahydro-1-indenyl 3. A process according to claim 2 which is selected from the group consisting of zirconium dichloride and ethylene- [bis (4,5,6,7-tetrahydro-1-indenyl)] zirconium dichloride. 4. The method of claim 3 wherein the solution has a composition that provides a molar ratio of alumoxane (expressed as aluminum) to metallocene in the range of 50 to 500. 5. A carrier material composition used as a catalyst for polymerization, which is obtained by the method according to any one of claims 1 to 4. 6. 100-35 at a temperature in the range of 30 ° C.-115 ° C. in the presence of a catalyst comprising alumoxane.
A fluidized bed gas phase reactor process for producing a resin under polymerization conditions comprising a pressure in the range of 0 psi (690 to 2400 KPa), the fluidized bed comprising the carrier material composition of claim 5. And
Introducing a feed capable of polymerizing to produce a resin; and free of oligomeric or polymeric reaction products of water and trialkylaluminum,
A process comprising introducing a monomeric trialkylaluminum as a cocatalyst.