CA2241091C - Polyalkylaluminoxane compositions formed by non-hydrolytic means - Google Patents

Abstract

The present invention relates to a process which comprises the non-hydrolyti c transformation of an aluminoxane precursor composition, comprising carbon-to-oxygen bonds which can be alkylated by an alkylaluminum moiety, into a catalytically useful aluminoxane composition. In one embodiment of this invention, the catalytically useful aluminoxane composition is a polymethylaluminoxane composition substantially free of trimethylaluminum. The intermediate precursor is formed by the reaction of a trialkylaluminum compound, or a mixture of trialkylaluminum compounds, and a compound containing a carbon-to-oxygen bon d, such as an alcohol, ketone, carboxylic acid, or carbon dioxide. Either unsupported or supported polymethylaluminoxane compositions can be formed.

Description

POLYALKYLALUMINOXANE COMPOSITIONS
FORMED BY NON-HYDROLYTIC MEANS
f Background of the Invention The present invention relates to a novel synthesis of aluminoxanes by non-hydrolytic means and to novel aluminoxane compositions. Aluminoxanes are well known as components for olefin polymerization catalysts.
Aluminoxane compounds are chemical species that incorporate A1-O-A1 moieties. While a wide range of aluminoxane species are known, their exact structures are not precisely known. The following structures (where R is alkyl and X is an integer of from about 1 to about 40) have been depicted:
R2A1-p-Alga (R2A1-o-A1R2) 2 R- (RAlO) X-A1R2 (RAlO)x Cyclic and cage cluster structures have also been proposed. Such materials, as would be recognized by the person of ordinary skill in the art are complex mixtures of various species which can easily undergo dynamic exchange reactions and structural rearrangements. A
recent review of these materials was authored by S.
Pasynkiewicz and appears in Polyhedron, Vol. 9, pp. 429-453 (1990).
Methylaluminoxanes, sometimes termed "polymethylaiumin-oxanes" (PMAOs) are well known materials with wide utility in olefin polymerization using single-site, or metallocene-based, polymerization catalyst systems (See, for example, Col. 1, Lines 14-29 of U.S.
Patent No. 4,960,878 to C. C. Crapo et al.). PMAOs are conventionally prepared by controlled hydrolysis of trimethylaluminum (TMAL). Generally, hydrolysis occurs ' with some loss of aluminum to insoluble species.
Generally, PMAOs also have very low solubility in aliphatic solvents, which limits their utility, as well as poor storage stability for solutions containing them.
(See, for example, Col. 1, lines 30-46 of U.S. Patent No.
4,960,878). Finally, it is generally polymethylaluminoxanes that have been the most useful products of this general class of material: other alkylaluminoxanes do not work as well. Since- TMAL is an expensive starting material, the resulting PMAO is expensive.
The problems of low yield, poor solubility, poor storage stability, and expensive reagents in preparation of PMAO have previously been attacked, with only limited success, in several ways. One method was to make predominantly PMAO, but include some components from hydrolysis of other alum:i.num alkyls, to form the so-called "modified methylaluminoxane" (MMAO). This yields predominantly methyl-containing aluminoxanes in improved yields, with improved solution storage stability as well as improved solubility in aliphatic solvents, at lower cost. However, since alkyl groups other than methyl are present, these materials axe not always as effective as conventional PMAO. ' The prior art contains certain disclosures which are deemed to be particularly germane to the present invention, including a series of related publications by T. Mole and coworkers (E. A. Jeffrey et al., Aust. J.
Chem. 1970, 23, 715-724; A. Meisters et al., Journal of . the Chemical Society, Chem. Comm. 1972, 595-596; D. W.
Harney et al., Aust. J. Chem. 1974, 27, 1639-7.653; A.
~ 5 Meisters et al., Aust. J. Chem. 1974, 27, 1655-1663; and A, Meisters et al., Aust. J. Chem. 1974, 27, 1665-1672) which describe the exhaustive methylation of oxygen-containing organic substrates by trimethylaluminum (hereinafter abbreviated as "TMAL" for simplicity). Some of the reactions that these publications report are listed hereinbelaw:
Ph3COH > Ph3CMe ( 1 ) Excess TMAL, 19 hrs., 80 °C
Ph2 (Me) COH > Ph2CMe2 (2) Excess TMAL, 20 hrs., 85 °C
Ph (Me) 2COH > PhCMe3 (3) Excess TMAL, 18 hrs., 110 °C
Me3COH > GMe4 (4 ) Excess TMAL, 42 hrs., 120 °C
(4-Me-Ph) 2C0 >(4-Me-Ph) 2CMe2 (5) Excess TMAL, trace benzoic acid, 2 hrs., I70 °C

_ _..

PhC (O) Me > PhCMes ( 6) "
Excess TMAL, 65 hrs., 122 °C
Me2C0 > ~~ ( 7 ) Excess TMAL, 80 hrs., 175 °C
PhC02H > PhCMe3 ( 8 ) Excess fMAL, 24 hrs . , 130-150 °C
MeC02H > CMe4 ( g ) Excess TMAL, 23 hrs., 130 °C
This work focused on conversion of the organic substrates, and only speculates occasionally on the aluminum containing products formed. Some of the comments they do make include, e.g., Equation (6) of Meisters et al.(Aust. J. Chem.
1974, 27, 1655-1663) which shows [MezAlOAIMe2] as a speculative product; as well as Equation (6) of Meisters et al. (Aunt. J.
Chem. 1974 , 27 , 1665-1672 ) which al so shows [MezA1.0A1Me2 ] as a speculative product. Another relevant comment made in these disclosures is that these reactions do not remain homogeneous tree the footnote on page 1643 of Harney et. al, Aust. J.
Chem. 1974, 27, 1639-1653).

Another relevant comment appears in Comprehensive Organometallic Chemistry II, E.W. Abel et al., eds., New . York NY, Pergamon, 1995, Vol. 1, p. 452 where several preparations of aluminoxanes are given, including those ~ 5 set forth in Equations (54)-(57) and Scheme 8.
Aluminoxanes of these preparative methods, however, are said to be unsuitable as cocatalysts for single-site catalysts.
Another problem well known in the art a.s the inevitable presence of trimethylaluminum (TMAL) in the polymethyl-aluminoxane (PMAO) product. In particular, L.
Resconi et al, Macromol. 1990, 23, 4489-4491 and the references cited therein show that PMAO prepared in the normal manner contains both methylaluminoxane species as well TMAL species. These researchers based their conclusion on, among other things, the presence of two signals in the iH NMR of PMAO. Fig. 1, which forms a part of the present specification, illustrates the 1H NMR of commercially available PMAO with the spectrum being composed of both a broad peak, attributed to methylaluminoxane species, and a distinct second peak, attributed to trimethylaluminum species. M.S. Howie, "Methylaluminoxane and Other Aluminoxanes-Synthesis, Characterization and Production", Proceedings, MetCon '93, pp. 245-266, Catalyst Consultants Inc., Houston, TX 1993, has also noted that PMAO invariably contains TMAL. For .instance, on page 247 it is stated that "MAO always contains some amount of TMA". Further, Howie notes that "total removal of TMA from MAO has not been demonstrated, and reduction to low levels creates other problems".

Summary of the Tnvention The present invention, in one embodiment, relates to a novel composition which is a catalytically useful composition comprising alkylaluminoxane which is substantially free of trialkylaluminum content. The 1H NMR
of the product of this invention, for example, does not Separately distinguish TMAT~ as a species which is present therein.
This invention also relates to a process for forming 95 aluminoxanes from a particular type of aluminoxane precursor composition, which will be described in greater detail below, using non-hydrolytic means (e. g., by thermal and/or catalytic means). The intermediate aluminoxane precursor composition, which is ultimately capable of being transformed by the aforementioned non-hydrolytic means to the desired aluminoxane product, is formed by treating a trialkylaluminum compound, or mixtures thereof, with a reagent that contains a carbon-oxygen bond. This treatment to form the intermediate aluminoxane precursor composition is followed by the aforementioned non-hydrolytic transformation of the intermediate aluminoxane precursor composition to give a catalytically useful aluminoxane composition. It should be clearly understood that the process described herein can be used to form the novel type of alkylaluminoxane referred to in the first paragraph of this section of the specification as well as conventional polymethylaluminoxane compositions that are not substantially free of TMAL as a species which is present therein as measured by the iH NMR spectrum of the . product. It should also be recognized that the process described herein is useful for the formation of S alkylaluminoxanes, in general, as well as the formation of polymethylaluminoxane. In most cases it may be desirable to obtain a polymethylaluminoxane product with a low free TMAr. content. However, the amount of free TMAIt remaining in the aluminoxane composition may be adjusted from very low levels to over 50~ by controlling the stoichiometry and reaction conditions in the process.
The present invention, in a preferred embodiment, enables one to produce polymethylaluminoxane compositions of improved solution stability which also have the desirable feature of compatibility with aliphatic hydrocarbon solvents, such as hexane, heptane, octane or decane. The process allows for high recoveries (yields) of aluminum values in making the desired product. Also, the process produces an methylaluminoxane product giving high activities in polymerization of olefin monomer(s).
Description of the Drawings The Drawings which form a portion of this Specification are provided herewith to further illustrate certain attributes of the present invention. Fig. 1 illustrates the 1H NMR of conunercially available PMAO with the spectrum being composed of both a broad peak, attributed to methylaluminoxane species, and a distinct second peak, attributed to trimethylaluminum species.
Fig. 2 shows a novel PMAO product that can be made, in accordance with one particular embodiment of the process WO 97!23288 PCT/LJS96/19980 of the present invention, which is easily handled and which performs well, but which is substantially free of TMAL as a species that can be separately distinguished by 1H NMR .
Description of Preferred Embodiments As just mentioned, preferred embodiments of the present invention relate to (1) a process for forming, by the non-hydrolytic conversion of suitably constituted 1~ alkylaluminoxane precursor compositions, catalytically useful methylaluminoxane compositions, and (2) polymethylaluminoxane compositions which are substantially free of trimethylaluminum content and which are catalytically useful methylaluminoxane compositions.
The intermediate precursor composition is an organoaluminum composition which is constituted such that it contains alkyl groups, initially bound to aluminum which are capable of alkylation of groups, also contained in the precursor, which contain a carbon-to-oxygen bond.
When the alkylation of such carbon-oxygen containing groups occurs, the oxygen atoms contained in such groups in the precursor are incorporated into alkylaluminum moieties during that part of the present process in which the intermediate precursor is transformed to the desired aluminoxane product.
It will be appreciated by a person of ordinary skill in the art that there are many ways of forming the intermediate precursor composition which must contain some amount of alkylaluminum groups as well as some carbon which is chemically bound to oxygen and susceptible to alkylation by an alkylaluminum group. For the purposes of ' S illustrating the nature of these precursor compositions, the following discussion will provide examples of methods for forming suitable compositions of that type. This discussion, however, should not be construed as limiting the present invention to the particular methods which may be exemplified herein, for example, for preparing the preferred aluminoxane precursor composition, which may incorporate a wide range of chemical species therein without precisely known chemical structure. For instance, as will become apparent from the following description, if a ketone, such as benzophenone, is reacted with a trialkylaluminum compound, such as trimethylaluminum, an addition reaction will occur. The result will be a.
composition containing alkylaluminum groups (in this case, methylaluminum) and functional groups where carbon is also bound to oxygen (in this case, a 1,1-Biphenyl-ethoxy functional group):
Me3Al + 0 . 8 R2C=O > Me2 _ 2A1 ( OC ( Ph ) ~Me ) o _ a Analogous precursor compositions can be formed in alternative ways, as will be described in more detail below. As another example, a salt metathesis reaction can be depicted as follows:
Me2 . 2A1 Cl o . a + 0 . 8 NaOC ( Ph ) 2Me >
Me2_2A1 (OC (Ph) 2Me) 0.8 + O . 8 NaCl WO 97!23288 PCTIUS96/19980 As earlier mentioned, the precursor intermediate composition can be formed by using a reagent, containing a carbon-to-oxygen chemical bond. Suitable reagents which can be used can be selected from the alcohols, the ketones, and the carboxylic acids as representative examples. A
particularly suitable inorganic reagent which has been found to work is carbon dioxide.
In the preferred embodiment of the present invention, this precursor composition is formed by treating trimethylaluminum with an oxygenated organic compound such as an alcohol, ketone, carboxylic acid or carbon dioxide. In the case of carboxylic acids or carbon dioxide, some aluminoxane moieties will form (see, for example, U.S. Patent Serial No. 5,728,855). In all these cases, as is well known in the art (see~for instance, the citations to exhaustive methylation given above, and references cited therein), alkoxyaluminum or arylalkoxyaluminum moieties will be formed. The following equations represent possible, non-limiting, examples of the reactions of trimethylaluminum and oxygenated organic molecules to form alkoxyaluminum or arylalkoxyaluminum-based aluminoxane precursor compositions (R and R' being the same or different and being selected from alkyl and/or aryl and TMAL indicating 2~ trimethylaluminum):
ROH + 2 Me3A1 > MeH + MesAl.z (OR) (I) ROH + Me3Al. > MeH + 1 /2 (Me,Al2 (OR) 2) ( I I ) RC ( O ) R' + 2 Me3Al. > MesAl. Z ( OCMeRR' ) ( I i i ) RCO2H + 3 Me3Al. >
1/2 (Me9A1.2 (OCMe2R) 2) + IMe2AlOA1Me2~ (IV) The most preferred embodiment of the present invention is to use a carboxylic acid or carbon dioxide as they form both a methylaluminoxane precursor containing the alkoxyaluminum or arylalkoxyaluminum moieties and the desired methylaluminoxane products.
Once this preferred methylaluminoxane precursor composition is formed, the key component of the present invention is the thermal and/or catalytic transformation of this precursor to form the desired catalytically useful methylaluminoxane composition. While the prior art teaches that these precursor compositions can be transformed to form exhaustively methylated organic derivatives, it does not disclose the formation of catalyticaily active aluminoxane compositions, nor does it teach the proper conditions to form such a catalytically useful composition comprising methy-laluminoxane. A recent review.in the prior art (Comprehensive Organometallic Chemistry II, Vol. 1, p. 452) suggests, in fact, that polymethylaluminoxane processes based on carboxylic acid reagents "do not produce aiuminoxanes suitable for catalytic applications". The prior art additionally fails to a recognize the aliphatic hydrocarbon solubility and improved storage stability characteristics of the preferred products of the process of the present invention as well as the possibility of manufacturing the novel low TMAL-containing product of certain embodiments of the instant invention. The prior art appears to be silent on exhaustive methylation of carbon dioxide. Furthermore, as the Examples provided hereinbelow illustrate, we have discovered conditions where this reaction remains homogeneous, in contrast to the heterogeneous examples of the prior art.
The present invention has also discovered that formation of PMAO, for example, by the present invention yields, in certain embodiments, a product substantially free of TMAI, since separate signals for PMAO and TMAL are not observed in the 1H NMR spectrum of the product.
The process of the present invention produces high recoveries of aluminum as compared to hydrolytic processes for making aluminoxanes as conventionally known to the art. The process of the present invention also is capable of producing polymethylaluminoxane with improved storage stability as compared to hydrolytic processes for making aluminoxanes as conventionally known to the art. Finally, the process of this invention is capable of producing polymethylaluminoxane in high yield in the presence of aliphatic solvents, unlike hydrolytic processes for making aluminoxanes as conventionally known i.n the art.
The preferred method for transforming the methylaluminoxane precursor is to optionally add, or form in situ, a catalytically effective amount of methylaluminoxane with the precursor and heat the material at the lowest temperature sufficient to effect conversion to the desired methylaluminoxane composition in a WO 97!23288 PCT/US96I1998fl reasonable amount of time. This reaction can also be facilitated by increasing the concentration of ~ organometallic species by removing, or limiting in other ways, the amount of solvent, if solvent, which is an optional ingredient at this point in the process, is present.
The present invention, in its most preferred embodiment is a navel process, for forming catalytically useful polymethylaluminoxane with the resulting, polymethylaluminoxane composition, in certain embodiments being a novel polymethylaluminoxane composition which is substantially free of trimethylaluminum. This process comprises the thermal andfor catalytic transformation of an appropriately constituted precursor composition as earlier described. A preferred method for preparing the precursor composition is treatment of trimethylaluminum with a carboxylic acid or with carbon dioxide. However, as will be appreciated by a person of ordinary skill in the art, there are many other methods which can be used to prepare the precursor composition which is transformed into the desired final product.
If desired, supported polyalkylaluminoxane compositions can be prepared by conducting the aforementioned reaction in the presence of a suitable support material. Alternatively, supported alkylaluminoxanes may also be prepared by forming the alkylaluminoxanes of this invention in a discrete, separate step and subsequently allowing the a alkylaluminoxane to react with the support material..
Oxidic support materials, such as silica, are especially preferred. It is preferred to have the alkylaluminoxane in a suitable, heated solvent at a temperature high enough (e. g. , at least 85°C, preferably about 100°C) so that the alkylaluminoxane is in soluble form and, after being combined with the support material, will come out of ' solution and contact that support as the total system is alloowed to cool.
It has now discovered that the non-hydrolytic PMAO
("PMAO-IP") of the present invention has surprising advantages over conventional, hydrolytically prepared PMAO
in the preparation of the aforementioned supported methylaluminoxanes ("SMAO"). PCT Patent Publication No.
WO 96/16092 describes a supported catalyst component prepared by heating a support material containing aluminoxane under an inert atmosphere and at a temperature sufficient to fix aluminoxane to the support material.
In this publication the alum:i.noxane and support are first contacted in a diluent or solvent, which is removed prior to the heat treatment step. This disclosure relies upon the use of an aluminoxane which is prepared by the controlled hydrolysis of trimethylaluminum species. The instant application discloses novel, non-hydrolytic routes to aluminoxanes, which have not previously been applied to the problem of preparing a supported catalyst component.
Surprisingly, in accordance with the present invention, it has been found that the utilization of non-hydrolytic polymethylaluminoxane (PMAO-IP), instead of conventional, hydrolytic, polymethylaluminoxane (PMAO), allows for the preparation of a supported aluminoxane catalyst component with high recovery of aluminum, with low extractable aluminum, with superior ability to bind a transition metal component, and which can be converted to a catalyst With superior polymerization activity. When a corresponding supported aiuminoxane catalyst component is prepared from conventional, hydrolytically prepared PMAO, poor recoveries of aluminum were observed, and the resulting ' supported aluminoxane catalyst component had an inferior ability to bind zirconium, for example.
S As will be appreciated by the person of ordinary skill in the art, the aluminoxane products that can be made by the process of the present invention are useful as cocatalysts in those single-site (metallocene-based) catalyst systems which are useful in the polymerization of olefin monomers in a manner analogous to that in current use with the aluminoxane compositions that are currently known and used in that manner.
The present invention will be further illustrated by the Examples which follow.

a EXAMPhES
Standard air-free glovebox and Schlenk line techniques were used. Polymerization tests were conducted in hexane at 85 °C, under a total pressure of 150 psig (ethylene + hexane + hydrogen), using rac-ethylenebisindenylzirconium dichloride:trimethylaluminum 1:30 as the catalyst precursor component with the 90 aluminoxane present at 1000:1 Al:Zr. Trimethylaluminum (37.2 wt ~ Al) and polymethylaluminoxane (PMAO) in toluene (9.0 wt ~ Al) were obtained from Akzo Nobel Chemicals Inc., Deer Park TX, and used as received. Benzophenone and benzoic acid were obtained from Aldrich Chemical Co., placed under a nitrogen atmosphere, and otherwise used as received.
r A solution of trimethylaluminum (2.00 g trimethylaluminum, 15.6 g toluene) was treated with a solution of benzophenone (4.02 g benzophenone, 15.6 g toluene), and the resulting mixture heated at 60 °C for one and one half hours to give a solution of alkylaluminum arylalkoxides with the overall composition ( (CsHS) 2MeC0) o.8A1Me2.2. Analysis of this product by 1H NMR
showed it to be a mixture of the discrete compounds:
( (C6H5) 2MeC0) lAlMe2 and ( (CsH~) 2MeC0) ~A12Me5. This product could be heated, as is, for many hours at 60 °C and remain unchanged according to 1H NMR.
A catalytic amount of PMAO (0.35 g, 9.0 wt ~ A1) was 'i5 added to the alkylaluminum arylalkoxide solution, and the mixture heated at 60 °C for 3.2 hours. At the end of this time, analysis by 1H NMR showed that alkoxy aluminum species were no longer present, and that aluminoxane moieties were present. An ethylene polymerization test, which normally yields about 700 kg PE/g Zr hr with conventional PMAO prepared by Akzo Nobel Chemicals Inc., gave 1380 kg PE/g Zr hr using this polymethylaluminoxane instead.

A solution of trimethylaluminum (2.00 g trimethylaluminum, 3.10 g toluene) was treated with a solution of benzoic acid (1.35 g of benzoic acid in I8.4 g of toluene) at 0 °C.
Methane gas was evolved. Analysis by IH NMR showed this mixture to contain PhMeaCOAl and Me-Al and A1-O A1 moieties. When this mixture was heated at 80°C for twenty-four hours, no change occurred.
A catalytic amount of PMAO (0.83 g, 9.0 wt ~ A1) was added to the alkylaluminum alkoxide and aluminoxane solution, and solvent removed in vacuo, to give a clear, slightly viscous liquid. This liquid was heated at 80°C
for 1 hr and 55 minutes, to give a clear, amorphous, toluene soluble solid. Analysis by ~H NMR showed that alkoxy aluminum species were no longer present, and that aluminoxane moieties were present. As no insoluble aluminum-containing byproducts were formed, this preparation gave a quantitative yield of catalytically useful polymethyl-alumi.noxane. In an accelerated aging test, conducted at 50°C, the polymethylaluminoxane prepared by this Example remained clear, homogeneous and free of gels for up to ten days, while a conventional, hydrolytically prepared, commercial PMAO showed gel formation within three to five days at the same temperature. An ethylene polymerization test gave 680 kg PEjg Zr hr using this polymethylaluminoxane. -WO 97!23288 PCT/IJS96/19980 ' TMAL (15.00 g) was mixed with toluene (9.25 g) and was then reacted with carbon dioxide (3.74 g) at room temperature to form an alkoxyaluma.num and alkylaluminoxane-containing PMAO precursor composition.
This mixture was heated at 100° C for twenty-four hours to give a clear, viscous liquid whose 1H NMR showed it to have been converted to PMAO. Alkoxyaluminum species were no longer detectable by NMR analysis. As no insoluble aluminum-containing byproducts were formed, this preparation gave a quantitative yield of catalytically useful polymethylaluminoxane. A polymerization test with this material yielded 2400 kg PE/g Zr hr in a thirty minute test.

EXAMP7~E 4 Using the same procedure that is described in Example 2, TMAL (8.00 g) in 9.51 g of toluene was treated with neat benzoic acid (5.40 g) to give an arylalkoxyaluminum-containing methylaluminoxane precursor. Heating of this mixture at 80°C for five hours gave conversion to PMAO. As no insoluble aluminum-containing byproducts were formed, this preparation gave a quantitative yield of aatalytically useful polymethylaluminaxane.
Fig. 1 shows the Me-AZ region of a 1H NMR spectrum of conventional PMAO obtained from a commercial source. The 95 spectrum clearly contains two signals, a broad signal due to methylalumi.noxane species, and a sharper signal due to trimethylaluminum species. Fig. 2 shows the same region of the spectrum of PMAO prepared in this Example. Unlike the commercially available PMAO, the material of this invention shows only one broad signal in the depicted region. The product is substantially free of TMAL in that no distinct ~H NMR signal from TMAL is discernible.

A solution of trimethylaluminum (8.0 g in 4.94 g of decane) was treated with carbon dioxide (1.9 g of carbon dioxide) over a period of eight hours. Analysis by 1H NMR
showed this mixture to contain (CH3)3C0-Al, CH3-A1, and A1-O-Al moieties. Heating this sample at 100°C for twenty-four hours caused no change in the iH NMR spectrum.
However, when heated for five hours at 120°C, the reaction mixture became slightly hazy, forming a viscous liquid after cooling. Since it was not necessary to separate solid, aluminum-containing byproducts from this product, this preparation gave a quantitative yield of catalytically useful polymethylaluminoxane. Analysis by 1H
NMR showed signals due to decane solvent, traces of residual t-butoxy signals, and a broad signal due to methylaluminoxane species.
An ethylene polymerization test gave 1100 kg PE/g Zr/hr using the polymethylaluminoxane prepared in this Example.

WO 97lZ3288 PCT/US96/19980 All manipulations in these Examples were conducted with the best available air-free techniques, including Schlenk line manipulations and inert atmosphere glove-box techniques. On-line monitoring of the box atmosphere generally showed 0.1-1.5 ppm oxygen (with brief excursions to 2-6 ppm when opening the ante-chamber door) and 0.5-3 ppm water (with excursions to about 6 ppm).
Polymerization tests were conducted in a jacketed one liter stainless steel ZIPPERCLAVE autoclave from Autoclave Engineers. The polymerization reactions were conducted with 150 psig ethylene supplied on demand to a reactor charged with 25-50 mg of the catalyst (containing 1-2 micromoles Zr, depending on expected activity and planned test duration), 500 mL hexane, and 2 mmole TEAL (present as a scavenger). Prior to each polymerization test, the reactor body was removed and oven dried for one hour at 100°C-120°C (with water drained from the heating/cooling jacket). The reactor was always reassembled while the body was still hot from the oven, and purged with nitrogen for 15-30 minutes while the reactor cooled somewhat.
After purging, the recirculating bath was reconnected, and the reactor heated to 50°C. The reactor Was pre-treated with TEAL (0.2 mmole) in hexane (300 mL).
xs Prior to use, DAVISON 948 micro-spherical silica was dehydrated by calcination in a nitrogen fluidized bed.
Table 1 summarizes silica used in this work.
Non-hydrolytically prepared polymethylalumi.noxane (PMAO-IP) was prepared according to the general teachings of Example 3 contained herein.

Table 1. Calcination results.
a Calcinationwt. lossResidual Temp. C (~) OH
mmole/g ' Silica 200 C 3.9 1.52 A

Silica 400 C 6.z 1.06 B

Silica 400 C 5.5 1.06 C

Silica 600 C 7.1 0.65 D

Silica 600 C 6.2 0.71 E

General Procedure for Making SMAO: This is the procedure used for all the samples in Tables 2 and 3. A
three-neck glass reactor (250 mL), equipped with gas inlet, fritted-glass barrier gas-outlet, temperature sensor and overhead stirrer (crescent-shaped paddle) was placed under a nitrogen atmosphere and charged with 10.11 g silica (Silica D). Toluene (45 g) was added to form a slurry, and stirring was begun. An aliquot of PMAO-IP
solution (14.91 g, 14.8 wt ~ A1) was then added, dropwise, over 0.5 hour with stirring at 23-24°C. After the addition was completed, the reaction mixture was heated to 100°C in order to inure solubilization of the PMAO-IP, and was held at that temperature for one hour. After the reaction mixture had cooled back to room temperature, it was transferred via a 1/4 inch outer diameter polyethylene tube cannula to a bottom-fritted three-neck glass reactor (250 mL), equipped with gas inlet, fritted-glass barrier gas-outlet, and temperature sensor. The supernate was removed, and the SMAO product was isolated by filtration through the bottom frit. The filtrate was collected and was set aside for analysis. The SMAO was then vacuum dried in a bath at 50°C to obtain a free-flowing powder.
The results are sun~narized in Tables 2 and 3 which follow:

N 'd:M r M
N ' rN ~ CM

r rr r r O

ri O
Q ~ ~!W~ ~-~-ui~ ON ~ ,~

Nr a N

dl Q
~

N ~ ~N CVT.

~ ~ ~~ c~0~ c t00 I-' N

~
~

N
~
Q' O O ~ U
Q C
~
N
..
.

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o O M r00M M ~ CW
'~if i i a .
~
~
N
' ' uc c c~ ~N
- rr r r o ~ a ~ ~
o c ~r y ~ t COCDO o o Q..,-~
N
X

O c'a 'v as Cl~ .r-1C 'O, ~ aa a a ',-'- N
~--' ...:
~
~
L
o ai O o O OO O O _ M M00r O r- -p O ~' O O ' O
~
f1 c Q aQ a a ~ cn 0 00 v o 0 Q

~ ~ Qa a.~
-t ~
tn a ~

, , ~ m .C~ O a m a's ~
'o ~
~

Q Q TU
a ~ ~ W ~

-o m ca a~
~

(/~ ~ o oo o r' ~ c c a~c a a N
r Nr-a- o o o C~

C
i ~

Q G?D Llll1J4-1 N~tch.-M ~ t O ~ ~ N'_N dvM n ~ ~ ~ ~ C

_ U ~~ ~ ~ a ~ ~ re-r r r tnu Wninin'cn~ E' cg. ~ a ~
_ ~ c ~

~

(n OPt00000N N E ~ ~ 3 p~~ r a-~-r a ~ ,.,.~ a,O a a' 0 00 0 0 0 ~
~ ".. _ ~

cua~a~a.>~ _ _ ~ ~ ~ E
E

_ _ J Ca O (~

E EE E
E c ccacaE '~ X co~ aoo> .~ o ' o ~
a a ~ X~ x N a~ iua~a~a~a~a>o ~
uJu~ -- - - - ~ ~o t U 1 EE E E E E ~
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O ~
~ ' O w. t ' H C~ U y!JJ! ~ UJ U
( C IL U !.L I-Llt L1J N (h C tW

Conversion to catalyst:
The SMAO samples in Table 3 were converted to single-site based ethylene polymerization catalysts by allowing up to 1 Zr:100 A1 to bind with the SMAO from a solution of a bis-indenyl dimethylzirconium (BIZ-M) in toluene. A 250 mL catalyst preparation flask (3 neck flask with bottom frit), with an ace-threaded gas inlet adapter containing a thermocouple, a stopper, and a fritted gas adapter, was set up and was tested for vacuum. Working in the glovebox, the apparatus was charged with 5 grams of the selected SMAO sample, and the central stopper was replaced With an overhead stirring shaft. At the same time, one lO g, and three 15 gram charges of dry toluene were set up in serum-capped sample vials. Also prepared at this time was a 50 mL septum bottle with BIZ-M (usually about 100 mg) and a small stir bar. Enough toluene (typically 30 g) was added to obtain complete dissolution.
Working on a Schlenk line, the first 10 g charge of toluene was used to slurry the silica. Gentle stirring was then begun. Enough BIZ-M solution to provide 1 Zr:100 A1 in the SMAO sample was then added, and the mixture was heated to 50°C for one hour and was then filtered. The catalyst was then washed with two of the 15 g toluene charges. All the filtrates were combined.
The stirrer was replaced with a stopper, and the catalyst was vacuum dried at room temperature until ~~fountaining" of catalyst (due to out-gassing of solvent vapors) was no longer observed (generally less than thirty minutes). After this, the catalyst was dried for an additional thirty minutes at room temperature, and then thirty more minutes at 35 °C. Tables 4-6 which follow gives a summary of the catalyst preparations and performance data:

O

M~ M N N
D

H

C

O

V tor M 0fCOP

tdtittnd'sh11~

G
rN M

N N

L
L

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MO O

d O O fl-a ~"'Pr r r r r C
O

N
T

y L -.R-. N ..' N p_ O 0. U
E

fI. cO O cN0 dJ
,a,CO0OCO~ ~ ~ t .~w 1~.V V V V V

_ .~, ~ ~
O
cE

~ L

-.Z,~.tN ~ c~cc~ N
~ ~~

o~aso00~~ of ~

.: -~L
P0saDO M d' NM M efetd'~ cB
00 0 0 0 0 ~
'~
c~E'O~ N
~

c /~
,-1 ?~ U ~ ~

ca a ~
N
t 0 ..

MM O O O O
fl) -O p O O ~
a a ~
y Y

O _ OC p) N N

V V V V _ __ ' E

v a PcDeta0M tt~
~

OO 1'CDC107t /i ~ L O C ~ c .

E o .E E o E

Ofet070tM O c N c c O
Q M

~ a-r r M ch r a0P r r r r N

_ r N M ~tttf~

r.s r P r P P

f!t O1C!C>'C1CX O cE O ~ ~
~

M
U (~W W W W W ~, t~! '~c""' upc u L
~~o ~

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~, a a c8 ~ O~ ~i>'i>K>K ~ U ti. U U ti U
ca H fI~ C7W tLtittit1.lJ ~ ~~ ~ d, (n WO 97/23288 PCT/US96/1998~
Table 6. Summary of oertormance results.
SMAO Cat. Activity D10 PBD
Sam Sam !e k PEI hr D50 /mL
to D90 microns Com Com B 0.5 -- - - 0.39 A

Ex.6 Ex.11 0.6 306 388 468 0.32 Ex. Ex.12 0.T -- -- 0.34 T

Ex.8 Ex.13 0.65 - - --- 0.34 Ex. Ex. 14 1.6 432 507 573 0.36 Ex. Ex. 15 1.3 _ 451 492 0.36 10-~ 392 The data show above shows that PMAO-IP binds more completely to calcined silica than conventional PMAO-IP, allows for the preparation of SMAO With a higher aluminum loading, and results in SMAO that binds more completely to zirconium species thereby forming a more active catalyst.
The foregoing Examples, since they merely illustrate certain embodiments of the present invention, should not be construed in a limiting sense. The scope of protection sought is set forth in the claims which follow.

Claims (13)

The embodiments of the present invention in which an exclusive property or privilege is claimed are defined as follows:

1. A process which comprises a thermal and/or catalytic transformation of an aluminoxane precursor composition, which comprises an organoaluminium composition with alkylaluminium moieties and groups containing a carbon-to-oxygen bond, in which process the oxygen atoms contained in said groups are incorporated into the alkylaluminium moieties to form a composition comprising catalytically useful alkylaluminoxane moieties.

2. The process of claim 1 wherein the aluminoxane precursor composition is formed by the reaction of a trialkylaluminum compound, or a mixture of trialkylaluminum compounds, and a compound containing a carbon-to-oxygen bond.

3. The process of claim 1 wherein the aluminoxane precursor composition is formed by the reaction of a trialkylaluminum compound, or a mixture of trialkylaiuminum compounds, and carbon dioxide.

4. The process of claim 2 or 3, wherein the mixture of trialkylaluminum compounds comprises trimethylaluminum and one or more trialkylaluminum compounds comprising an alkyl group which comprises two or more carbon atoms.

5. The process of claim 1 wherein the groups containing a carbon-to-oxygen bond are selected from the group consisting of alcohols, ketones, and carboxylic acids.

6. The process of any one of claims 1 to 5, wherein the precursor composition is thermally transformed.

7. A product formed by the process defined in any one of claims 1 to 6.

8. A polymethylaluminoxane product formed by the process defined in any one of claims 1 to 6.

9. A supported product formed by the process defined in any one of claims 1 to 6.

10. A supported polymethylaluminoxane product formed by the process defined in any one of claims 1 to 6.

11. A silica-supported polymethylaluminoxane product formed by the process defined in any one of claims 1 to 6.

12. A catalyst composition for use in the polymerisation of olefins which comprises the aluminoxane, optionally on a support, formed by the process defined in any one of claims 1 to 6.

13. A catalyst composition for use in the polymerisation of olefins which comprise a polymethylaluminoxane, optionally on a support, formed by the process defined in any one of claims 1 to 6.