WO1997014700A1

WO1997014700A1 - Liquid clathrate aluminoxane compositions

Info

Publication number: WO1997014700A1
Application number: PCT/US1996/016694
Authority: WO
Inventors: Samuel A. Sangokoya
Original assignee: Albemarle Corporation
Priority date: 1995-10-19
Filing date: 1996-10-17
Publication date: 1997-04-24
Also published as: EP0882054A1; US5670682A; JP2002515026A; CA2235314A1

Abstract

Stable liquid clathrate aluminoxane compositions are obtained by the reaction, in aromatic solvents, of aluminoxanes such as, methylaluminoxane, with organic, inorganic or organometallic compounds, such as salts, which can dissociate or partially dissociate into cationic and anionic species (M-X species).

Description

LIQUID CLATHRATE ALUMINOXANE COMPOSITIONS

This invention relates generally to aluminoxane compositions and more specifically to stable, liquid clathrate aluminoxane compositions obtained by the reaction in aromatic solvents of aluminoxanes, especially methylaluminoxane, with organic or inorganic compounds, especially salts which can dissociate or partially dissociate into cationic and anionic species (M-X species). In another aspect, the invention relates to insoluble solid aluminoxane-MX salt compositions. Furthermore, the invention relates to polymerization catalyst compositions which could optionally be supported on inert solid carriers.

Aluminoxanes are generally prepared by the hydrolysis of aluminum alkyls either by direct water addition or by treatment with salt hydrates. Aluminoxanes are used in combination with various types of metallocenes and/or transition metal compounds to catalyze olefin oligomerization and polymerization. These catalyst components can be supported on solid carriers such as metal oxides, for example silica or alumina, for use in heterogeneous and gas phase polymerizations.

Methylaluminoxane (MAO) is the most useful of all aluminoxanes for polymerization applications. However, certain limitations are associated with regular methylaluminoxane solutions. Such limitations include poor solubility, especially in aliphatic solvents, instability, and gel formation.

The present invention relates to the alleviation of most if not all ofthe present problems associated with the industrial use of methylaluminoxanes as co-catalyst components.

A copending U.S. patent application, Serial No. 08/452,170, filed May 26, 1995, describes the formation of aluminoxanate compositions which are the reaction products of aluminoxanes, such as methylaluminoxane, and certain salts of polyoxy-compounds such as sodium aluminate and lithium silicate. These materials are obtained by the formation of only a transient liquid clathrate which quickly turns to solid aluminoxane compositions described as aluminoxanates. The present invention forms stable, liquid clathrate aluminoxane compositions.

The stable, liquid clathrate aluminoxane compositions show remarkable solubility and stability with no sign of gel formation even at higher concentrations than commercially available methylaluminoxane solutions. This permits the shipment and storage and use of concentrated (30 to 60 weight percent) MAO solutions.

In accordance with the invention there is provided a stable, liquid clathrate composition which comprises the reaction product, in an aromatic solvent, of an aluminoxane and an organic, inorganic or organometallic compound which is effective to form a stable, liquid clathrate composition with said aluminoxane. Also provided is a process for preparing a methylaluminoxane composition which is substantially free of trimethylaluminum comprising (a) reacting a solution of methylaluminoxane, which contains a trimethylaluminum component, in an aromatic solvent with an organic, inorganic or organometallic compound which is effective to form a stable liquid clathrate composition with said methylaluminoxane so as to form a lower liquid methylaluminoxane containing clathrate layer and an upper, aromatic solvent layer which contains said trimethylaluminum component, and (b) separating said clathrate layer from said aromatic solvent layer.

Further, there is provided particulate solid aluminoxane-MX salt compositions obtained by removal ofthe aromatic inclusion solvent from the dense lower liquid layer of the liquid clathrate composition. Also, in accordance with the present invention polymerization catalyst systems are prepared using either the liquid clathrate aluminoxane salt compositions or the particulate solid aluminoxane-MX salt compositions, which can optionally be supported on solid carriers, in combination with co-catalysts such as metallocenes or transition or lanthanide metal compounds such as Ziegler Natta type catalysts.

Figure 1 is a graph showing three superimposed NMR spectra obtained from samples of a methylaluminoxane/toluene solution, a methylaluminoxane/toluene/KCl liquid clathrate solution and a methy laluminoxane/toluene LiCl mixed clathrate solution.

Conventional methylaluminoxane solutions can be vacuum stripped to obtain solid methylaluminoxane. It is believed that this material exhibits fouling problems in slurry or particle form polymerization due to the presence of a significant amount of soluble aluminum compounds. The inventive solid aluminoxane salt compositions are virtually insoluble in aliphatic hydrocarbons and thus offer significant improvements with respect to reactor fouling. Hydrocarbylaluminoxanes may exist in the form of linear or cyclic polymers with the simplest monomeric compounds being a tetraalkylaluminoxane such as tetramethylaluminoxane, (CH₃)₂A10A1(CH₃)₂, or tetraethylaluminoxane, (C_jH^_jAlOAl- (C₂H₅)₂. The compounds preferred for use in olefin polymerization catalysts are oligomeric materials, sometimes referred to as polyalkylaluminoxanes, which usually contain 4 to 20 of the repeating units:

R

where R is C,-C,₀ alkyl and is preferably methyl. The exact structure of aluminoxanes

has not been defined and they may contain linear, cyclic and/or cross-linked species.

Methyl-aluminoxanes (MAOs) normally have lower solubility in organic solvents than

higher alkylaluminoxanes and the methylaluminoxane solutions tend to be cloudy or

gelatinous due to the separation of particles and agglomerates. In order to improve the

solubility ofthe methylaluminoxane, higher alkyl groups, e.g. C₂ to C₂₀ can be included

such as by hydrolyzing a mixture of trimethylaluminum with a C₂ to C₂₀ alkylaluminum

compound such as, for example, triethyl-aluminum, tri-n-propylaluminum, triisobutyl-

aluminum, tri-n-hexylaluminum, tri-n-octylaluminum or a triarylaluminum. Such mixed

methyl-higher alkyl or aryl aluminoxanes are included in the term "methylaluminoxane"

as used herein. Such modified methylaluminoxanes are described, for example, in U.S.

Patent No. 5,157,008. Besides MAO, non-limiting examples of hydrocarbyl¬

aluminoxanes for use in the invention include ethylaluminoxanes (EAO), isobutyl- aluminoxanes (IBAO), n-propylalurninoxanes, or n-octylaluminoxanes, phenylalumin-

oxanes. The hydrocarbylaluminoxanes can also contain up to 20 mole percent (based

on aluminum) of moieties derived from amines, alcohols, ethers, esters, phosphoric and

carboxylic acids, thiols, aryl disiloxanes, or alkyl disiloxanes to further improve activity, solubility and/or stability.

The aluminoxanes can be prepared as known in the art by the partial hydrolysis

of hydrocarbylaluminum compounds. Any hydrocarbylaluminum compound or mixture

of compounds capable of reacting with water to form an aluminoxane can be used. This

includes, for example, trialkylaluminum, triarylaluminum, or mixed alkyl aryl

aluminum, . The hydrocarbylaluminum compounds can be hydrolyzed by adding either

free water or water containing solids, which can be either hydrates or porous materials

which have absorbed water. Because it is difficult to control the reaction by adding

water per se, even with vigorous agitation of the mixture, the free water is preferably

added in the form of a solution or a dispersion in an organic solvent. Suitable hydrates

include salt hydrates such as, for example, CuSO₄*5H₂O, AJ (SQ ) *18H O,

FeS0₄«7H₂O, A1C1 •6₂H O, Al^O ) f 9H O, MgSQ «7H O,₂ MgCl «6H O,

ZnSO₄*7H₂O, Na₂SO₄*10H₂O, Na₃PO₄»12H₂O, LiBr»2H₂O, LiCl* lH₂O, LiI*2H₂O,

LiI«3H₂O, KF»2HjO, or NaBr«2Ii O and alkali or alkaline earth metal hydroxide

hydrates such as, for example, NaOH»H₂0, NaOH«2H O, Ba(OH) »8H O, KOH»2H₂O, CsOH»lH₂O, orLiOH»lHp. Mixtures of any of the above hydrates can

be used. The mole ratios of free water or water in the hydrate or in porous materials

such as alumina or silica to total alkyl aluminum compounds in the mixture can vary widely, such as for example from 2:1 to 1 :4 with ratios of from 4:3 to 1 :3.5 being

preferred.

Such hydrocarbylaluminoxanes and processes for preparing hydrocarbyl¬

aluminoxanes are described, for example, in U.S. Patent Nos. 4,908,463; 4,924,018;

5,003,095; 5,041,583; 5,066,631 ; 5,099,050; 5,157,008; 5,157,137; 5,235,081 ;

5,248,801, and 5,371,260. The methylaluminoxanes contain varying amounts, of from

5 to 35 mole percent, ofthe aluminum value as unreacted trimethylaluminum (TMA).

The process ofthe invention removes most of this unreacted trimethylaluminum which

can be recovered and re-used in making additional methylaluminoxane. The novel, liquid clathrate aluminoxane compositions are prepared by the

reaction ofthe aluminoxanes, especially methylaluminoxane, with organic, inorganic or

organometallic compounds, and especially salts, which are potentially capable of

dissociating or partially dissociating into cationic and anionic species (M-X species).

Such reactions are characterized by the formation of two stable immiscible organic

layers when carried out in an aromatic solvent. The appearance ofthe immiscible layers

is termed liquid clathrate formation.

The reactions of trialkylaluminums with M-X species to produce the liquid

clathrate phenomenon have been described by such authors as Atwood ( Coordination

Chemistry of Aluminum VCH Publishers, Inc. 1993, p. 197), Robinson (Coordination

Chemistry Reviews, 112 (1992) 227) and Sangokoya (J. Incl. Phenom., 6 (1988) 263).

The reaction of MAO with M-X species was initially carried out in toluene in

order to remove the TMA content via formation of a TMA liquid clathrate. Surprisingly,

MAO was found to be more reactive towards M-X species than TMA. By analysis, the upper solvent layer consists mainly of TMA and toluene, while the lower liquid clathrate

layer contains mainly MAO-MX and toluene with almost no titratable TMA content as

shown by pyridine titration. This lower layer represents the stable, liquid clathrate

aluminoxane salt composition embodiment ofthe invention.

MX compounds which are effective in forming stable, liquid clathrates with

aluminoxanes are organic, inorganic or organometallic compounds which can potentially

dissociate or partially dissociate into cationic and anionic components, especially in the

presence of aluminoxanes. Non-limiting examples are alkali and alkaline earth halides

or pseudo-halides such as KCl, KF, KOSiR₃, NaB0₄, or NaF. Pseudo-halides, which

is term of art, are M-X salts where the anionic moieties are non-halogenides. The reactions of the compounds with MAO in aromatic solvents lead to the formation of

liquid clathrate compositions. Other examples of MX compounds include metal

hydrides such as KH, LiH and alkyl, aryl and alkyl-aryl ammonium, phosphonium,

sulfonium and other organometallic salts of halides and pseudo halides such as Me₄NCl,

MePh₃PBr, NaBPh₄, KB(C₆F₅)₄, LiRyM, which will effectuate liquid clathrate formation

by their reactions with MAO in aromatic solvents.

Also within the scope of this invention are organic, inorganic or organometallic

materials which are not regarded as MX compounds per se but by virtue of their reaction

with MAO act like MX compounds by the formation of stable, liquid clathrate

aluminoxane compositions. A representative example of such compounds is triphenyl¬

phosphine oxide. Such compounds and their reaction products with aluminuminoxanes

are included in the terms "MX compounds", "MX species" and "MX salt composi¬

tions". Non-limiting examples of suitable aromatic solvents include, toluene, benzene,

xylenes, ethylbenzene, cumene, mesitylene, or cymene. The preferred solvent is toluene.

The clathrate forming compounds are preferably added in excess to the amount

that dissolves to form the clathrate with the extra amount being easily removed, such as

by filtration. Stoichiometric or lesser amounts are effective to form stable clathrates,

depending upon the compound. Preferably, amounts of from 0.01 to 0.5 moles of

compound per mole of aluminum in the aluminoxane composition are added and more

preferably from 0.05 to 0.2 moles. The starting concentration of aluminoxane in solvent

is not particularly critical and usually ranges from 5 to 30 weight percent solution. As

described herein, the weight percent of aluminoxane in the solutions is based on the total

weight of aluminoxane and any unreacted trialkylaluminum in the solution. An

advantage of the clathrates of the invention is that commercial MAO solutions are

usually available as 5-20 wt. percent solutions in toluene. At higher concentrations, the

inevitable limitations associated with solubility, stability and gel formation become

extremely pronounced. Consequently, the transportation costs of the less concentrated

solutions, especially to distant overseas places, significantly increase catalyst cost which in turn will push up polymer cost. In contrast, the inventive liquid clathrate

aluminoxane-MX salt compositions can contain MAO in high concentrations, e.g. 30-60

wt. percent depending on the nature ofthe MX species. Furthermore, even at these high

concentrations, the inventive liquid clathrate MAO-MX compositions are appreciably

much more stable with respect to solubility, stability and gel formation compared to conventional MAO solutions. The reaction temperature is chosen to provide a stable, liquid clathrate. By a

stable liquid clathrate is meant that the two immiscible liquid layer systems remain intact

such that the upper solvent layer can be separated from the lower clathrate layer.

Although the use of ambient temperatures is most convenient (i.e. from 15 to 30°C),

some compounds require elevated temperatures of up to 80°C or higher in order to form

a stable, liquid clathrate. A suitable temperature for any particular compound can be

experimentally determined.

Removal of solvent from the dense lower liquid clathrate layer such as by

vacuum distillation or the addition of excess non-aromatic solvent results in the isolation

of solid, particulate aluminoxane salt compositions. The solid, particulate MAO-MX salt compositions are virtually insoluble in aliphatic hydrocarbons. When introduced

into aromatic solvents, the novel MAO-MX salt will incorporate as much solvent as

required to reform a liquid clathrate (inclusion solvent) which separates out from the rest

ofthe solvent resulting again in two immiscible liquid layers.

The aluminoxane MX composition can be used in combination with

metallocenes and/or transition metal compounds to provide olefin polymerization

catalysts.

A notable result of liquid clathrate formation is that the aluminoxane-MX

product contains essentially no trimethylaluminum as indicated by pyridine titration.

It should also be noted that the variability in trimethylaluminum content of methyl¬

aluminoxane is probably the major source of inconsistency in previously known

supported catalyst systems. Therefore, this invention provides a means to avoid this

inconsistency. As used in this application, the term "metallocene" includes metal derivatives

which contain at least one cyclopentadienyl moiety. Suitable metallocenes are well

known in the art include the metallocenes of Groups 3, 4, 5, 6, lathanide and actinide

metals, for example, the metallocenes which are described in U.S. Patent Nos.

2,864,843; 2,983,740; 4,665,046; 4,874,880; 4,892,851 ; 4,931,417; 4,952,713;

5,017,714; 5,026,798; 5,036,034; 5,064.802; 5,081,231 ; 5,145,819; 5,162,278; 5,245,019; 5,268,495; 5,276,208; 5,304.523; 5,324,800; 5,329,031; 5,329,033;

5,330,948, 5,347,025; 5,347,026; and 5,347,752.

Non-limiting illustrative examples of such metallocenes are bis(cyclopenta-

dienyl)zirconium dimethyl, bis(cyclopentadienyl)zirconium dichloride, bis(cyclopenta-

dienyl)zirconium monomethylmonochloride, bis(cyclopentadienyl)titanium dichloride,

bis(cyclopentadienyl)titanium difluoride, cyclopentadienylzirconium tri-(2-ethyl-

hexanoate), bis(cyclopentadienyl)zirconium hydrogen chloride, bis(cyclopentadienyl)-

hafhium dichloride, racemic and meso dimethylsilanylene-bis(methylcyclopentadienyl)-

hafnium dichloride, racemic dimethylsilanylene-bis(indenyl)hafnium dichloride, racemic ethylene-bis(indenyl)zirconium dichloride, (η⁵-indenyl)hafhium trichloride, (η⁵-C₅Me₅)-

hafriium trichloride, racemic dimethylsilanylene-bis(indenyl)thorium dichloride, racemic

dimethylsilanylene-bis(4,7-dimethyl-l-indenyl)zirconium dichloride, racemic dimethyl-

silanylene-bis(indenyl)uranium dichloride. racemic dimethylsilanylene-bis(2,3,5-tri-

methyl- 1 -cyclopentadienyl)zirconium dichloride, racemic dimethy lsilanylene(3 -methy 1-

cyclopentadienyl)hafnium dichloride, racemic dimethylsilanylene-bis(l-(2-methyl-4-

ethylindenyl zirconium dichloride; racemic dimethylsilanylene-bis(2-methyl-4,5,6,7-

tetrahydro-1 -indenyl)-zirconium dichloride. bis(pentamethylcyclopentadienyl)thorium dichloride, bis(pentamethylcyclopentadienyl)uranium dichloride, (tert-butylamido)-

dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanetitanium dichloride, (tert-butylamido)-

dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanechromiumdichloride,(tert-butylamido)- dimethyl(-η⁵-cyclopentadienyl)silanetitanium dichloride, (tert-butylamido)dimethyl-

(tetramethyl-η⁵-cyclopentadienyl)silanemethyltitanium bromide, (tert-butylamido)-

(tetramethyl-η⁵-cyclopentadienyl)- 1 ,2-ethanediy luranium dichloride, (tert-butylamido)-

(tetramethyl-η⁵-cyclopentadienyl)-l ,2-ethanediyltitanium dichloride, (methylamido)-

(tetramethyl-η⁵-cyclopentadienyl)-l,2-ethanediylcerium dichloride, (methylamido)-

(tetramethyl-η⁵-cyclopentadienyl)-l,2-ethanediyltitanium dichloride, (ethylamido)-

(tetramethyl-η⁵-cyclopentadienyl)methylenetitanium dichloride, (tert-butylamido)-

dibenzyl(tetramethyl-η⁵-cyclopentadienyl)-silanebenzylvanadium chloride, (benzyl- amido)dimethyl(indenyl)silanetitanium dichloride, and (phenylphosphido)dimethyl-

(tetramethyl-η⁵-cyclopentadienyl)silanebenzyltitanium chloride.

Suitable transition metal or lathanide compounds include the well known

Ziegler-Natta catalyst compounds of Group 4-6 metals. Non-limiting illustrative

examples of such compounds include TiCl₄, TiBς , Ti(OC H j) Cl, Ti(OC H )C1 ,

Ti(OC₄H₉)₃Cl, Ti(O? J^ ^ QI , Ti(qC₂ ) Br , YCl , V₃OCl Vp(p H ) ₄ ZrCl ,

ZrCl₃(OC₂H₅), or Zr(OC₂H₅)₄ and ZrCl(OC₄H₉)₃.

The molar proportions of metallocene and/or transition metal or lathanide

compound in the catalyst composition to the aluminum derived from the aluminoxane

in the aluminoxane-MX composition are selected to provide the desired degree of

polymerization activity and generally range from 1 X 10^"1 to 1 X \0^A to 1 and preferably

from 2 X 10 ¹ to 5 X 10- to l. Either the liquid clathates or the solid aluminoxane-MX compositions can be

used to prepare catalysts.

The metallocenes or transition or lanthanide compounds can be supported on the

novel aluminoxane compositions. Also, the reaction of MAO-MX compositions with

metallocene could be carried out in the presence of other organic or inorganic substrates

such as silica, alumina and other support substrates which are known in the art as

suitable support materials. The aluminoxane-MX composition can be initially reacted

with the metallocenes and then with the support substrate or the aluminoxane-MX

compositions can be reacted with the support substrate and then with the metallocenes

and vice versa. In addition, the original aluminoxane compound can be initially

modified by treatment with an R₃A1 compound or mixtures thereof or treated with other

reagents which do not result in an appreciable deterioration of the polymerization

capability ofthe aluminoxane before being treated with the MX species in order to form

the aluminoxane- MX clathrate compositions.

The catalysts are effective to produce olefin polymers and especially ethylene

polymers, propylene polymers and ethylene/α-olefin copolymers. Examples of olefins

that can be polymerized in the presence of the catalysts of the invention include α-

olefins having 2 to 20 carbon atoms such as ethylene, propylene, 1 -butene, 1 -hexene, 4-

methyl-1 -pentene, 1-octene, 1-decene, 1 -dodecene, 1 -tetradecene, 1-hexadecene, and 1-

octadecene. Polymerization of ethylene or copolymerization with ethylene and an α-

olefin having 3 to 10 carbon atoms is preferable. Such polymerizations may be

performed in either the gas or liquid phase (e.g. in a solvent, such as toluene, or in a

diluent, such as heptane). The polymerization can be conducted at conventional temperatures (e.g., 0° to 250°C) and pressures (e.g., ambient to 50 kg/cm²) using

conventional procedures as to molecular weight regulation.

The invention is further illustrated by, but is not intended to be limited to, the following examples.

All experiments were performed under inert atmosphere condition. Schlenk vacuum

line and glasswares, in conjunction with dry N2-box were employed to handle all air sensitive materials. Reagents were obtained from commercial sources without further

purification. Aluminoxane samples were obtained from stock solutions produced by

Albemarle Coφoration. Solvents were dried and distilled by standard methods.

Example 1 : MAO/Tol/KCl

A solution of methylaluminoxane (135g, 648 mmol Al) in toluene (Tol) was placed

in a reaction bottle. Potassium chloride (2.42g, 32.4 mmol) was added and the mixture was

stirred at room temperature. After one hour, clathrate formation was observed. Within three

hours, all solid (KCl) dissolved. More KCl (1.21g) was then added and the mixture was

stirred at room temperature overnight. Again, all solid dissolved. More KCl (1.21g) was

then added, almost all of which reacted within a few hours. The total amount of KCl added was 10 mole percent ofthe total aluminum value ofthe original MAO solution.

The liquid, two phase system was filtered through a medium frit to remove any

unreacted KCl. Then the clathrate solution was separated using a separating funnel. The

dense lower phase contained no TMA by pyridine titration. The lighter upper phase was

shown by gas evolution measurement to contain mostly TMA (gas/Al ratio ~ 3). Furthermore, proton NMR ofthe upper layer showed only the TMA peak, the broad

MAO peak was not observed.

Example 2. MAO/Tol/KF

MAO/Tol (87g, 382 mmol Al) was placed in a reaction bottle and then treated with

potassium fluoride (KF, 2.22g, 38.2 mmol). The mixture was stirred at room temperature

overnight (15 hours). All the solid appeared to have dissolved with formation of liquid

clathrate. The mixture was filtered through a coarse frit.

Example 3. MAO/Tol/NaF

A reaction bottle was filled with MAO solution (91g, 400 mmol Al) in toluene and

sodium fluoride (NaF, 1.7g, 40 mmol) was added. The mixture was stirred ovemight at

room temperature. A liquid clathrate resulted, but the lower layer was extremely thick, and

some unreacted NaF could be seen at the bottom. The syrupy lower layer was too thick to

be filtered. It was, therefore, decanted to remove the unreacted NaF. The resulting product

was heated at 80°C (oil bath) for six hours. While hot, the lower layer was free flowing, but

as soon as it cooled down, it became syrupy again.

Example 4. MAO/To1/Me,NCl

A toluene solution of MAO (51.3g, 178 mmol Al) was treated with tetramethyl¬

ammonium chloride (Me₄NCl, 2.93g, 26.8 mmol). The mixture was stirred at room

temperature overnight. A condensed methylaluminoxane-amine complex composition resulted. The two layer liquid system was filtered to give a lower dense layer which

contained all the MAO product (23g) and the upper layer which contained all the TMA.

Example 5. MAO/Tol/MePruPBr

Methyltriphenylphosphonium bromide (MePh₃PBr. 5.93g, 16.6 mmol) was added to

an MAO solution (47.7g, 166 mmol Al) in toluene. After stirring for 2 hours, a three layered liquid clathrate resulted. More toluene (40 ml) was added. The mixture was then stirred

overnight to give only a two layer clathrate solution. The mixture was filtered and separated

to give a viscous lower layer (27g) and a non-viscous upper layer (47g).

The proton NMR ofthe upper layer showed only TMA and no phosphine or MAO.

Example 6. MAO/Tol/NaBPh,

An MAO solution (80g, 352 mmol Al) in toluene was treated with sodium

tetraphenylborate (NaBPh₄, 3g, 8.8 mmol) and the mixture was stirred ovemight. No

clathrate was formed and only a fraction ofthe solid borate dissolved. On heating at 80°C

(oil bath) for one hour, all the solid dissolved but no clathrate was formed. When the

mixture was allowed to cool to room temperature, still no clathrate formation was observed.

More borate salt (3g) was added such that total amount of borate salt is 5 mole percent of

the total aluminum value in the original MAO solution. The mixture was heated at 90°C (oil

bath) for two hours and most of the solid dissolved but no clathrate was observed while hot.

On cooling overnight, clathrate formation was observed. The mixture was filtered to remove

any solid residue. Example 7. MAO/Tol KOSiMe,

To a solution of MAO (109g, 525 mmol Al) was added potassium trimethylsilanolate

(KOSiMe₃, 5.1g, 39.4 mmol) in batches. Some gas evolution was observed. The reaction

was also exothermic. This mixture was stirred at room temperature overnight and a two

liquid layer system resulted. The lower dense layer seemed to contain some solid residue.

The mixture was filtered to give clear, liquid two layer system. The lower layer contained

the condensed methylaluminoxane silanolate complex composition.

Example 8. MAO/Tol/KH

A toluene solution of MAO (86g, 353 mmol Al) was placed in a reaction bottle and

potassium hydride (KH, 0.8g, 20 mmol) was added in batches. Slowly, the solid KH

dissolved and a liquid clathrate separated to give a condensed methylaluminoxane complex composition within 30 minutes. The mixture was stirred at room temperature overnight (14

hours). Almost all the solid dissolved. The mixture was filtered to remove any solid residue.

Example 9. MAO/Toι7Ph3P«»

An MAO solution (71g, 291 mmol Al) was placed in a reaction bottle.

Triphenylphosphine oxide (6.5g, 23.3 mmol) was added. The mixture was stirred at room

temperature to give liquid clathrate formation containing the new condensed methyl-

aluminoxane phosphonium complex composition. The mixture was filtered to remove any

trace of solid residue. Comparative Examples

Comparative Example 1. MAO Tol/LiCl

An MAO solution (225g, 1080 mmol Al) was treated with lithium chloride (4.6g, 108

mmol). The mixture was stirred at room temperature for 4 days and no clathrate was formed.

Then the mixture was heated at 90°C (oil bath) for 2 hours and still no clathrate was formed.

The mixture was filtered through a medium frit. ICP analysis showed that lithium had been

incoφorated into the MAO product (228 ppm) while the product appeared to be more stable to gel formation no clathrate formation was observed.

Comparative Example 2. MAO/Tol/LiF

A toluene solution of MAO (94.7g, 454.6 mmol Al) was placed in a reaction bottle

and then lithium fluoride (LiF, 1.18g, 45.46 mmol) was added. The mixture was stirred at

room temperature for 3 days. No clathrate formation was observed. However, ICP analysis,

Li-7 and F-19 NMR confirmed incoφoration of LiF into the MAO composition (646 ppm

Li by ICP).

Example 10. MAO/Tol LiCl (Excess LiCl and Heart

This experiment showed that clathrate formation could be forced by using excess LiCl

and heating over a long period. However, the clathrate formation was not as clear cut as in

the regular clathrate compositions as described above.

Methylaluminoxane solution (98g, 441 mmol Al) was treated with LiCl (3.8g, 88

mmol) and then heated at 90°C for 24 hours. No clathrate was seen when hot. On cooling,

a small amount of lower phase separated. Analysis, however, did not show the usual clear cut separation of MAO and TMA. Thus, pyridine titration showed the presence of TMA both

in the lower and upper phases.

Furthermore, Al-27 NMR confirmed the mixed clathrate formation composed of

MAO/TMA complex ( 159 ppm) and MAO LiCl complex (- 13 ppm). Note that regular MAO

solution in toluene usually shows a peak at 155 ppm referenced to extemal IM A1C1₃ solution

in water.

Example 11. MAO/Tol/LiH (Supported on Silica')

Lithium hydride (0.2g, 25 mmol) was added in batches, to an MAO solution in toluene (71g,

291 mmol Al). Suφrisingly, no gas evolution was evident. The mixture was stirred

overnight at room temperature. A lower thick and almost immobile phase separated. The

clathrate composition was then heated at 80°C for 2 hours. On cooling to room temperature, silica gel (14g) was added in batches. As the silica reacted with the lower phase, the later

slowly became mobile again and the stirrer bar started to turn again., The mixture was stirred

overnight at room temperature after which, the mixture was heated at 60°C for one hour.

Additional solvent (heptane, 50 ml) was added in order to allow quantitative transfer to another reaction bottle. At this point, the mixture was heated at 80°C for 2 hours and then

filtered to obtain the clathrate composition supported on silica.

Reactions with Metallocene

Example 12

The product of Example 1 was treated with zirconocene dichloride (3.5g, 12 mmol

Zr). The clear solution slowly turned colored on stirring at room temperature. After a few hours, all the solid dissolved and the upper layer had a darker orange brown color while the

dense lower layer was only yellowish. The mixture was stirred overnight (14 hours) at room

temperature. Reversed coloration was observed, the dense lower layer became dark orange

while the upper layer turned only slightly yellowish. The mixture was filtered to remove any

solid residue. The dense lower layer was separated using a separatory funnel to give 39g

dark orange dense solution. Heptane (80g) was then added to give a yellowish brown slurry. After stirring for one hour, the mixture was filtered to give yellowish brown solid product

(23 g). This was then dried in vacuo to give 20g solid product. Analysis by ICP showed Al/Zr = 58 and Al/K = 12.

Example 13

The product of Example 2 was treated with zirconocene chloride (0.2g, 0.68 mmol

Zr) as described in Example 10. After drying, a yellowish powder (19g) was recovered.

Example 14

The product of Example 7 was allowed to react with zirconocene dichloride (1.5g,

5.1 mmol Zr) as described in Example 10, to give, on drying, orange brown powder (28g).

Analysis by ICP gave Al/Zr = 87 ad Al/K = 14.

Example 15

The product of Example 6 was treated with zirconocene dichloride (0.2g, 0.68 mmol

Zr) as described in Example 10 above to give dried orange brown powder. Example 16. Ethylene Polymerization In order to demonstrate the utility of these novel aluminoxane compositions, the products of Examples 14 and 15 were used in ethylene polymerization.

The polymerization tests were conducted in a Parr reactor (600 ml) containing heptane (300 ml) at 90 psi of ethylene pressure and 90° C during a period of 30 minutes.

Solid catalyst (0.2g) was used in each case to obtain 16g and 21 g of polymer respectively in the presence of TMA (2 mmol). The calculated specific activities for the polymerization reactions were 2.11 and 2.74 x 10⁴gPE/mol Zr-Atm-hr respectively. The above polymerization conditions for these novel catalyst compositions have not been optimized. Further appreciation of the invention is graphically illustrated by the Al-27 NMR spectra of Figure 1. The spectra were obtained using an aluminum background free probe described by Dr. L. S. Simeral in Applied Spectroscopy Vol. 47, p. 1954 (1994).

Curve o is Al-27 NMR spectrum of regular MAO (MAO/TMA complex) solution in toluene. The major peak is a 155 ppm relative to extemal IM A1C1₃ in H₂O. Curve • is the spectrum of MAO/KC1 clathrate solution with the only peak at -10 ppm. The designation LL means lower layer.

Curve D is the spectrum of MAO/LiCl mixed complex formation (clathrate) with 2 major peaks at 159 ppm and -13 ppm. The former peak corresponds to MAO/TMA complex and the later peak corresponds to MAO/LiCl complex, both complexes being present in the lower layer of the mixed liquid clathrate formation.

Claims

C AIMS

1. A liquid clathrate composition which comprises the reaction product, in an aromatic solvent, of an aluminoxane and an organic, inorganic or organometallic compound which is effective to form a stable, liquid clathrate composition with said aluminoxane.

2. The composition of claim 1 wherein said compound is an organic , inorganic or organometallic salt which can at least partially dissociate into cationic and anionic species in said solvent.

3. An aluminoxane clathrate composition which comprises methylaluminoxane, M-X species derived from an organic, inorganic or organometallic compound which is effective to form a stable clathrate with said methylaluminoxane, and an aromatic inclusion solvent.

4. The composition of claim 3 wherein said memylaluminoxane is a oligomeric methylaluminoxane and said compound is an organic, inorganic or organometallic salt or

hydride..

5. The composition of claim 4 wherein said salt is selected from the group consisting of KCl, KF, NaF, KH, LiH, KOSiR₃, NaBPh₄, Me₄NCl, MePh₃PBr, and KB(C₅F₅)₄.

6. A solid, methy laluminoxane-MX salt composition obtained by removing the aromatic inclusion solvent from the clathrate composition of claim 3.

7. A process for preparing a methylaluminoxane composition which is substantially free of trimethylaluminum comprising (a) reacting a solution of trimethyl¬ aluminum and methylaluminoxane in an aromatic solvent with an organic, inorganic or organometallic compound which is effective to form a stable, liquid clathrate with said methylaluminoxane so as to form a lower, liquid methylaluminoxane containing clathrate layer and an upper, aromatic solvent layer which contains said trimethylaluminum, and (b) separating said clathrate layer from said aromatic solvent layer.

8. An olefin polymerization catalyst comprising (a) the reaction product of a liquid clathrate composition comprising an aluminoxane, M-X species derived from an organic, inorganic or organometallic compound which is effective to form a stable clathrate, and an aromatic inclusion solvent and (b) a co-catalyst which includes a metallocene and/or a Ziegler-Natta catalyst compound of a Group 4-6 metal or lathanide element.

9. The catalyst of claim 8 wherein said cocatalyst includes a metallocene and said aluminoxane is a methylaluminoxane.

10. The catalyst of claim 8 wherein said organic, inorganic or organometallic compound is a salt which can at least partially dissociate into cationic and anionic species in said aromatic inclusion solvent in the presence of methylaluminoxane.

11. The catalyst of claim 8 which has been supported on a solid carrier.

12. An olefin polymerization catalyst comprising (a) a solid aluminoxane-MX salt composition which is obtained by removing the aromatic inclusion solvent from the composition of claim 3 and (b) a co-catalyst which includes a metallocene and/or a Ziegler-

Natta catalyst compound of a Group 4-6 metal or lanthanide element.

13. The catalyst of claim 12 wherein said co-catalyst includes a metallocene and said aluminoxane is a methylaluminoxane.

14. The catalyst of claim 8 wherein said aluminoxane is an oligomeric methylaluminoxane.

15. The catalyst of claim 12 wherein said aluminoxane is an oligomeric methy laliiminoxane .

16. The clathrate composition of claim 1 which has been supported on a solid carrier.