Europaisches Patentamt (19) European Patent Office

Office europeenpeen des brevets ^ £P 0 744 414 B1

(12) EUROPEAN PATENT SPECIFICATION

(45) Date of publication and mention (51) intci.e: C08F 10/00, C08F 4/602, of the grant of the patent: C07F 5/06 14.07.1999 Bulletin 1999/28

(21) Application number: 96107520.7

(22) Date of filing: 10.05.1996

(54) Aluminoxanate compositions Aluminoxanate-Zusammensetzungen Compositions d'aluminoxanate

(84) Designated Contracting States: • Wiegand, Karl E. BE DE FR GB IT NL Baton Rouge, LA 70820 (US)

(30) Priority: 26.05.1995 US 452170 (74) Representative: Schwabe - Sandmair - Marx Stuntzstrasse 16 (43) Date of publication of application: 81677 Miinchen (DE) 27.11.1996 Bulletin 1996/48 (56) References cited: (73) Proprietor: ALBEMARLE CORPORATION EP-A- 0 360 492 US-A- 5 157 137 Baton Rouge, Louisiana 70801 (US) • DATABASE WPI Derwent Publications Ltd., (72) Inventors: London, GB; AN 72-441 72t XP002012495 • Sangokoya, Samuel A. "Organic cpds production..." & Baton Rouge, LA 70815 (US) JP-A-470 240 01 1 (SHOWA DENKO) • Howie, Milham S. • DATABASE WPI Derwent Publications Ltd., Baton Rouge, LA 70810 (US) London, GB; AN 72-56272t XP002012496 • Simms, Patrick G. "Organo-aluminium cpds used as Baton Rouge, LA 70817 (US) polymerization catalysts" & JP-A-47 024 011 (SHOWA DENKO)

DO ^-

^> ^> Is- Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice the Patent Office of the Notice of shall be filed in o to European opposition to European patent granted. opposition a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. a. 99(1) European Patent Convention). LU

Printed by Jouve, 75001 PARIS (FR) 1 EP0 744 414 B1 2

Description 5,157,008. Besides MAO, non-limiting examples of hy- drocarbylaluminoxanes for use in the invention include [0001] The invention relates generally to aluminoxane ethylaluminoxanes (EAO), isobutylaluminoxanes derivatives which are useful components of olefin po- (IBAO), n-propylaluminoxanes, n-octylaluminoxanes, lymerization catalysts and more particularly to alumi- 5 and the like. The hydrocarbylaluminoxanes can also noxanate compositions which are the reaction products contain up to about 20 mole percent (based on alumi- of aluminoxanes, such as methylaluminoxane, and cer- num) of moieties derived from amines, alcohols, ethers, tain salts of polyoxy-compounds such as sodium alumi- esters, phosphoric and carboxylic acids, thiols, alkyl dis- nate and lithium silicate. iloxanes and the like to improve activity, solubility and/ [0002] Aluminoxanes are used in combination with 10 or stability. various types of metallocenes and/or transition metal [0007] The aluminoxanes can be prepared as known compounds to catalyze olefin oligomerization and po- in the art by the partial hydrolysis of trialkylaluminum lymerization. These catalyst components can be sup- compounds. The trialkylaluminum compounds can be ported on inert solid carriers such as metal oxides, for hydrolyzed by adding either free water or water contain- example silica or alumina, for use in heterogeneous and 15 ing solids, which can be either hydrates or porous ma- gas phase polymerizations. It has now been found that terials which have absorbed water. Because it is difficult aluminoxanes can be reacted with certain salts of poly- to control the reaction by adding water per se, even with oxy-compounds to form novel catalyst compositions vigorous agitation of the mixture, the free water is pref- which are useful in making polymeric olefinic products. erably added in the form of a solution or a dispersion in The polymers also have unique properties. 20 an organic solvent. Suitable hydrates include salt hy- [0003] In accordance with this invention there is pro- drates such as, for example, CuS04»5H20, Al2 vided an aluminoxanate composition comprising the re- (S04)3»18H20, FeS04»7H20, AICI3»6H20, Al action product of an aluminoxane and a salt selected (N03)3»9H20, MgS04»7H20, MgCI2»6H20, from the group consisting of alkali metal, alkaline earth ZnS04»7H20, Na2SO4»10H2O, Na3P04»12H20, Li- metal, ammonium, phosphonium and sulfonium salts of 25 Br»2H20, LiCI-1 H20, Lil»2H20, Lil»3H20, KF»2H20, Na- Group 1 3 to 1 6 element containing polyoxy-compounds, Br»2H20 and the like and alkali or alkaline earth metal which product contains from about 0.01 to 5.0 moles of hydroxide hydrates such as, for example, NaOH»H20, salt per mole of aluminum in said aluminoxane. NaOH»2H20, Ba(OH)2»8H20, KOH»2H20, [0004] Also provided is an olefin polymerization cata- CsOH»1H20, LiOH»1H20 and the like. Mixtures of any lyst comprising (a) the solid reaction product of an alu- 30 of the above hydrates can be used. The mole ratios of minoxane and an alkali metal, alkaline earth metal, am- free water or water in the hydrate or in porous materials monium, phosphonium or sulfonium salt of a Group 13 such as alumina or silica to total alkyl aluminum com- to 16 element containing polyoxy-compound, and (b) a pounds in the mixture can vary widely, such as for ex- transition, lanthanide or actinide metal compound. ample from 2:1 to 1:4 with ratios of from 4:3 to 1:3.5 [0005] Also provided is a process for polymerizing an 35 being preferred. olefin comprising contacting an olefin with the catalyst, [0008] Such hydrocarbylaluminoxanes and process- as defined above, under polymerization conditions. es for preparing hydrocarbylaluminoxanes are de- [0006] Hydrocarbylaluminoxanes may exist in the scribed, for example, in U.S. Patent Nos. 4,908,463; form of linear or cyclic polymers with the simplest mon- 4,924,018; 5,003,095; 5,041,583; 5,066,631; omeric compounds being a tetraalkylaluminoxane such 40 5,099,050; 5,157,008; 5,157,137; 5,235,081; as tetramethylaluminoxane, (CH3)2AIOAI(CH3)2, or 5,248,801, and 5,371,260. The methylaluminoxanes tetraethylaluminoxane, (C2H5)2AIOAI(C2H5)2. The com- contain varying amounts, of from 5 to 35 mole percent, pounds preferred for use in olefin polymerization cata- of the aluminum value as unreacted trimethylaluminum. lysts are oligomeric materials, sometimes referred to as Preferably the aluminum content as trimethylaluminum polyalkylaluminoxanes, which usually contain about 4 45 is less than about 23 mole percent of the total aluminum to 20 of the repeating units: value, and more preferably less than about 20 mole per- cent. [0009] The hydrocarbylaluminoxanes are reacted n with certain salts of polyoxy-compounds to form novel so I aluminoxane compositions which are referred to herein {A1-0-) as aluminoxanates. When these aluminoxanates are combined with metallocenes and/or other transition metal compounds, solid granular olefin polymerization where R is C-|-C10 alkyl and especially preferred are catalysts are typically formed which are, in effect, solid polymethylaluminoxanes (MAOs). The methylalumi- 55 catalyst compositions useful as heterogeneous polym- noxanes can contain some higher alkyl groups to im- erization catalysts for slurry, bulk or gas phase process- prove their solubility. Such modified methylaluminox- es. anes are described, for example, in U.S. Patent No. [0010] The salts of polyoxy-compounds for use in

2 3 EP0 744 414 B1 4 forming the compositions of the invention include alkali with 20°C to 100°C being preferred. metal, alkaline earth metal (Groups 1 and 2 elements of [0013] A notable result of methylaluminoxanate for- the new IUPAC notation for the Periodic Table, for ex- mation is that the solid product contains no trimethyla- ample, Li, Na, K, Cs, Mg, Ca, Ba), and ammonium, luminum as indicated by pyridine titration. It should also phosphonium, or sulfonium salts of Group 13 to 16 ele- s be noted that the variability in trimethylaluminum con- ment containing polyoxy-compounds, for example, tent of methylaluminoxane is probably the major source polyoxy-compounds which contain elements such as Al, of inconsistency in previously known supported catalyst B, Ga, C, Si, Ge, P, As, S and Se, which salts can be systems. Therefore, this invention provides a means to either anhydrous or moderately hydrated (1 to 6 weight avoid this inconsistency. percent H20). Non-limiting examples of such salts in- 10 [0014] The aluminoxanates can be used in combina- elude NaAI02, LiAI02, Na2C03, Na3P04, Li2SD3, tion with metallocenes and/or transition metal com- Na2Si03, Li2(C02)2, LiB02, Li2B407, LiN03, K2As04, pounds to provide olefin polymerization catalysts. As LiAI(Si03)2, LiC6H5C02, NaCF3C02, Mg(C2H302)2, used in this application, the term "metallocene" includes NH4AI(S04)2, (NH4)2B407, (PH4)2S04, (NH4)2Se03, metal derivatives which contain at least one cyclopen- and the like. The ammonium, phosphonium and sulfo- 15 tadienyl moiety. Suitable metallocenes are well known nium salt cations can include their organosubstituted in the art include the metallocenes of Groups 3, 4, 5, 6, analogs, for example, tetraalkyl, tetra (mixed) alkyl, lanthanide and actinide metals, for example, the metal- tetraaryl, and tetra (aryl, alkyl) substituted cations such locenes which are described in U.S. Patent Nos. as tetraethylammonium, tetraphenylammonium, 2,864,843; 2,983,740;2,983,740 4,665,046 4,665,046; 4,874,880;4,874,880 tetrabenzylammonium, dimethyldiphenylammonium as 20 4,892,851; 4,931,4174,931,417; 4,952,713 4,952,713; 5,017,7145,017,714; well as the corresponding phosphonium and sulfonium 5,026,798; 5,036,0345,036,034; 5,064,802 5,064,802; 5,081,2315,081,231; analogs. Some of these salts are not readily available 5,145,819; 5,162,2785,162,278; 5,245,019 5,245,019; 5,268,4955,268,495; but can be derived from the more readily available spe- 5,276,208; 5,304,5235,304,523; 5,324,800 5,324,800; 5,329,0315,329,031; cies by ion exchange reactions. 5,329,033; 5,330,948, 5,347,025; 5,347,026; and [0011] When the salt is allowed to react with an alu- 25 5,347,752. minoxane in an inert organic solvent, typically there is [0015] Non-limiting illustrative examples of such met- transient formation of a second liquid phase and the re- allocenes are bis(cyclopentadienyl)zirconium dimethyl, action product turns into an insoluble solid on standing. bis(cyclopentadienyl)zirconium dichloride, bis(cy- A particulate solid (granular or powder) results when the clopentadienyl)zirconium monomethylmonochloride, solvent is removed. The compositions are believed to 30 bis(cyclopentadienyl)titanium dichloride, bis(cyclopen- be about one to one molar reaction products of salt and tadienyl)titanium difluoride, cyclopentadienylzirconium aluminoxane but the metal salt can be combined in pro- tri-(2-ethylhexanoate), bis(cyclopentadienyl)zirconium portions of from 0.01 to 5.0 moles per mole of aluminum hydrogen chloride, bis(cyclopentadienyl)hafnium in the aluminoxane, preferably from 0. 1 to 3.0 moles per dichloride, racemic and meso dimethylsilanylene-bis mole and, more preferably, 0.8 to 1 .2 moles per mole of 35 (methylcyclopentadienyl)hafnium dichloride, racemic aluminum in the aluminoxane. dimethylsilanylene-bis(indenyl)hafnium dichloride, ra- [0012] Any inert organic solvent or solvent mixture cemic ethylene-bis(indenyl)zirconium dichloride, (r|5-in- can be used as the reaction medium. Non-limiting ex- denyl)hafnium trichloride, (r|5-C5lv1e5)hafnium trichlo- amples of solvents include aliphatic hydrocarbons such ride, racemic dimethylsilanylene-bis(indenyl)thorium as pentane, isopentane, hexane, cyclohexane, hep- 40 dichloride, racemic dimethylsilanylene-bis(4,7-dime- tane, octane, decane, dodecane, hexadecane, octade- thyl-1-indenyl)zirconium dichloride, racemic dimethylsi- cane and the like, with those having carbon numbers of lanylene-bis(indenyl)uranium dichloride, racemic 5 to 10 being preferred, and aromatic hydrocarbons dimethylsilanylene-bis(2, 3, 5-trimethyl-1 -cyclopentadi- such as benzene, chlorobenzene, , , enylzirconium dichloride, racemic dimethylsilanylene and the like, with those having carbon numbers 45 (3-methylcyclopentadienyl)hafnium dichloride, racemic of 6 to 20 being preferred. The aromatic solvents are dimethylsilanylene-bis(1 -(2-methyl-4-ethyl)indenyl) zir- preferred. The amount of solvent used is not critical and conium dichloride; racemic dimethylsilanylene-bis usually depends on the concentration of aluminoxane (2-methyl-4,5,6,7-tetrahydro-1 -indenyl) zirconium solutions used, which is generally chosen to be from 5 dichloride, bis(pentamethylcyclopentadienyl)thorium to 50 weight percent and preferably from 1 0 to 35 weight so dichloride, bis(pentamethylcyclopentadienyl)uranium percent. The most preferred concentration is from 15 to dichloride, (tert-butylamido)dimethyl(tetramethyl-r|5-cy- 30 weight percent. The salt can be added directly or as clopentadienyl)silanetitanium dichloride, (tert-butylami- a slurry in the same or different solvent as the aluminox- do)dimethyl(tetramethyl-ri5-cyclopentadienyl)si- ane. The form of and order of addition of reactants is not lanechromium dichloride, (tert-butylamido)dimethyl(- critical. For example, the aluminoxane, solid or solution, 55 ri5-cyclopentadienyl)silanetitanium dichloride, (tert- can be added to a slurry of the salt in a solvent or the butylamido)-dimethyl(tetramethyl-ri5-cyclopentadienyl) solid salt or slurry be added to an aluminoxane solution. silanemethyltitanium bromide, (tert-butylamido)-(te- The reaction temperature can range from 0°C to 1 50°C tramethyl-ri5-cyclopentadienyl)-1 ,2-ethanediyluranium

3 5 EP0 744 414 B1 6 dichloride, (tert-butylamido)(tetramethyl-r|5-cyclopenta- 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, dienyl)-1 ,2-ethanediyltitanium dichloride, (methylami- 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, do)(tetramethyl-r|5-cyclopentadienyl)-1 ,2-ethanediyl- and 1-octadecene. Polymerization of ethylene or copo- cerium dichloride, (methylamido)(tetramethyl-r|5-cy- lymerization with ethylene and an a-olefin having 3 to clopentadienyl)-1 ,2-ethanediyltitanium dichloride, 5 10 carbon atoms is preferable. Such polymerizations (ethylarnido)(tetramethyl-ri5-cyclopentadienyl)methyl- may be performed in either the gas or liquid phase (e. enetitanium dichloride, (tert-butylamido)dibenzyl(te- g. in a solvent, such as toluene, or in a diluent, such as tramethyl-ri5-cyclopentadienyl)-silanebenzylvanadium heptane). The polymerization can be conducted at con- chloride, (benzylamido)dimethyl(indenyl)silanetitanium ventional temperatures (e.g., 0° to 250°C) and pres- dichloride, and (phenylphosphido)dimethyl(tetramethyl- 10 sures (e.g., ambient to 50 kg/cm2) using conventional ri5-cyclopentadienyl)silanebenzyltitanium chloride. procedures as to molecular weight regulation and the [0016] Suitable transition metal compounds include like. Under certain conditions, broad molecular weight the well known Ziegler-Natta catalyst compounds of polyolefins are obtained. Polymerization conditions Group 4-6 metals. Non-limiting illustrative examples of could be adjusted however to obtain other molecular such transition metals include TiCI4, TiBr4, Ti is weight distributions. (OC2H5)3CI, Ti(OC2H5)CI3, Ti(OC4H9)3CI, Ti [0022] The invention is further illustrated by, but is not (OC3H7)2CI2, Ti(OC17)2Br2, VCI4, VOCI3,VO(OC2H5)3, intended to be limited to, the following examples. The ZrCI4, ZrCI3(OC2H5), Zr(OC2H5)4 and ZrCI(OC4H9)3 examples were carried out under inert atmospheric con- and the like. ditions using Schlenk glassware and vacuum line in con- [0017] The molar proportions of metallocene and/or 20 junction with a N2-drybox. Solvents were distilled using transition metal compound in the catalyst composition standard methods. Filtration and vacuum distillation to the aluminum derived from the aluminoxane in the were done inside a N2-drybox and distillates were col- aluminoxanate are selected to provide the desired de- lected in a trap at -78°C. Salts of polyoxycompounds gree of polymerization activity and generally range from were purchased from commercial sources. Methylalu- 1 X 1 0"1 to 1 X 1 0"4 to 1 and preferably from 2 X 1 0"1 to 25 minoxane (MAO) was obtained from stocksolutions pro- 5 X 10"4 to 1. duced and marketed by Albemarle Corporation. [0018] A surprising advantage of using aluminate salts, such as sodium or lithium aluminate is that the alu- Example 1 minum in the aluminate contributes to the catalytic ac- tivity of the aluminoxane-aluminate composition. This 30 Aluminoxane-aluminate Composition contribution is about equivalent to that of the aluminum in MAO thereby allowing the use of only about one-half [0023] A toluene solution of MAO (64 grams, 377 the amount of the more expensive MAO in order to ob- mmol Al) having less than 22 percent of the total alumi- tain the same activity. num value as TMA, was placed in a reaction bottle. [0019] The aluminoxanates and metal compound can 35 Then, NaAI02 (15.5 grams, 1 88 mmol) was slowly add- be added separately to the polymerization reactor but ed in batches during about 15 minutes. During addition, are preferably prereacted. The aluminoxanates can be the mixture became exothermic with some gas evolu- reacted with the metallocenes and/or transition metal tion. The original solid-liquid slurry slowly turned into a compounds in any inert organic solvent, such as those two phase liquid slurry. The dense lower layer slowly defined above for the aluminoxane-salt reaction. The re- 40 turned thicker and thicker and finally to solid slurry action temperature can range from 0°C to 150°C. Pre- again. The solid in the final product is about double the ferred reaction temperatures range from 20°C to 1 00°C. initial solid reagent. At this point the mixture was heated [0020] In an alternate way of preparing the catalyst with stirring for two hours at 70°C (oil bath). The mixture compositions of the invention, the metallocene can be was filtered and the solid product was washed with tol- premixed with the salt of the polyoxy-compound before 45 uene. Analysis showed that the liquid washings con- the salt and aluminoxane are reacted. Also, the alumi- tained 143 mmol Al and the dried solid product con- noxane and metallocene can be combined and then re- tained 365 mmol Al. One would not expect to lose much acted with the salt of the polyoxy-compound. The salts of the original aluminum value in NaAI02 (188 mmol), of the polyoxy-compound can be activated prior to re- therefore 177 mmol Al is postulated to have come from action with the catalyst components by treatment with a so MAO. The new product, methylaluminoxane-aluminate Lewis acid such as a trialkylaluminum, an alkylalumi- composition is, therefore, composed of almost equal num halide or a polysiloxane. amounts of aluminum from MAO and from NaAI02. [0021] The catalysts are effective to produce olefin [0024] Further analysis showed weight percent Al = polymers and especially ethylene polymers, propylene 34, gas evolution = 9.1 mmol/gram, methane evolution polymers and ethylene/a-olefin copolymers. Examples 55 = 8.9 mmol/gram, and TMA content = 0.0 mmol/gram (i. of olefins that can be polymerized in the presence of the e., no titratable TMA content by the pyridine method.) catalysts of the invention include a-olefins having 2 to 20 carbon atoms such as ethylene, propylene,

4 7 EP0 744 414 B1 8

Example 2 Example 5

Aluminoxane-silicate Composition Ethylene Polymerization

[0025] MAO solution (70 grams, 336 mmol Al), having 5 [0028] A 600 ml autoclave charged with dry toluene less than 22 percent of the total aluminum value as TMA, (300 ml) and supported catalyst system, methylalumi- was placed in a reaction bottle. Solid lithium silicate noxane-aluminate/ zirconocene dichloride composition (Li2Si03, 30.2 grams, 336 mmol) was slowly added in [1 gram, 12 mmol total Al (i.e. from MAO and from batches, while stirring during about 20 minutes. The NaAI02), 0.01 mmol Zr]. The slurry was heated to 70°C mixture was stirred at room temperature for one hour 10 and then ethylene was admitted for 20 minutes at 60 and then heated at 80°C (oil bath) for two hours. Hep- psi. At the end of reaction, the content of the autoclave tane (100 ml) was added and suddenly the product be- was poured into a beaker and an equal volume of meth- came oily to give a lower dense slurry (transient liquid anol was added. The polyethylene was collected by fil- clathrate formation). The oily product was then heated tration followed by further washings with methanol. The at 90°C (oil bath) for another two hours to give a solid is dried polyethylene product was 34 grams which corre- cake at the bottom of the flask. The upper liquid layer sponds to 2.8 x 104 grams PE/g. Zr.atm.hr. A GPC pol- was decanted. Heptane (400 ml) was added to the solid ymer analysis showed a bimodal molecular weight dis- cake and was also broken into pieces using a spatula. tribution. The polymerization process, therefore, pro- The mixture was again heated for another two hours at vides a unique polymer without the use of dual catalysts. 90°C (oil bath) and then filtered hot. The solid product 20 Also, the activity of the catalyst is substantially the same was washed several times with hot heptane and then as that which is obtained using 12 mmol total Al from vacuum dried to give free flowing solid product. 77 per- MAO in place of the methylaluminoxane-aluminate. cent of the original aluminum value was incorporated in- to the new compound, methylaluminoxane-silicate com- position. Analysis showed 15 weight percent Al, 13 25 Claims weight percent Li and no trimethylaluminum content. 1. An aluminoxanate composition comprising the re- Example 3 action product of an aluminoxane and a salt select- ed from alkali metal, alkaline earth metal, ammoni- Metallocene/MAO-Aluminate Composition 30 urn, phosphonium and sulfonium aluminates, boro- nates and silicates which product contains from [0026] The product of Example 1 (8 grams, 100 mmol 0.01 'to 5.0 moles of salt per mole of aluminum in Al) was suspended in heptane (100 ml). Then zir- said aluminoxane. conocene dichloride (1 mmol) was added. The mixture was stirred at room temperature overnight. The color- 35 2. The composition of claim 1 wherein said aluminox- less slurry slowly turned orange and then orange brown. ane is a polymethylaluminoxane. The mixture was filtered to obtain yellow brown solid product. The solid was vacuum dried to obtain 7.8 grams 3. The composition of claim 2 wherein said polymeth- of product. Analyses of product gave 33.7 weight per- ylaluminoxane contains less than 23% of the total cent Al, 1 4.6 weight percent Na and 1 .5 weight percent 40 aluminum as trimethylaluminum and the aluminox- of Zr. anate compositions contains no trimethylaluminum.

Example 4 4. The composition of claim 1 wherein said aluminox- ane is a polymethylaluminoxane and said salt is an Metallocene/MAO-Silicate Composition 45 aluminate.

[0027] The product of Example 2(10 grams, 55 mmol 5. The composition of claim 4 wherein the salt is se- Al) was suspended in heptane (100 grams). Then zir- lected from sodium or lithium aluminate. conocene dichloride (1.7 mmol) was added. The slurry slowly turned yellowish and was stirred overnight to ob- so 6. The composition of claim 1 wherein the product tain brown solid product. The slurry was filtered and then contains from 0.8 to 1 .2 moles of salt per mole of vacuum dried to give 10.3 grams of product. Analyses aluminum. of product gave 1 6.6 weight percent Al, 8.56 weight per- cent Li and 1 .69 weight percent Zr. 7. An olefin polymerization catalyst comprising (a) the 55 reaction product as claimed in claim 1, and (b) a metallocene.

8. The catalyst of claim 7 wherein said aluminoxane

5 9 EP0 744 414 B1 10

is a methylaluminoxane, said reaction product con- 7. Olefinpolymerisationskatalysator, der (a) das Reak- tains from 0.1 to 3.0 moles of salt per mole of alu- tionsprodukt nach Anspruch 1 und (b) ein Metallo- minum in said aluminoxane and the molar portion cen enthalt. of the metallocene per mole of aluminum derived from said methylaluminoxane is from 1 X 10_1 to 1 5 8. Katalysator nach Anspruch 7, in dem das Alu- X 10-4 minoxan ein Methylaluminoxan ist, das Reaktions- produkt 0,1 bis 3,0 Mol Salz pro Mol Aluminium im 9. An olefin polymerization catalyst comprising the re- Aluminoxan enthalt und der molare Anteil des Me- action product as claimed in claim 1 , and a transi- tallocens pro Mol Aluminium, das vom Methylalu- tion, lanthanide or actinide metallocene compound 10 minoxan abgeleitet ist, 1 x 10_1 bis 1 x 10"4 betragt. or a Ziegler-Natta catalyst compound of a Group 4-6 metal. 9. Olefinpolymerisationskatalysator, der das Reakti- onsprodukt nach Anspruch 1 und eine Ubergangs-, 10. An olefin polymerization process comprising con- Lanthanoid- oder Actinoidmetallocenverbindung tacting an a-olefin having from 2 to 20 carbon at- is oder eine Ziegler-Natta-Katalysatorverbindung ei- oms, including mixtures thereof, under polymeriza- nes Metalls der Gruppe 4 bis 6 umfaBt. tion conditions with a catalyst comprising the solid reaction product as claimed in claim 1 , and a tran- 10. Olefinpolymerisationsverfahren, bei dem man ein sition, lanthanide or actinide metallocene com- a-Olefin mit 2 bis 20 Kohlenstoffatomen pound or a Ziegler-Natta catalyst compound of a 20 einschlieBlich deren Mischungen unter Polymerisa- Group 4-6 metal. tionsbedingungen mit einem Katalysator in Kontakt bringt, der das teste Reaktionsprodukt nach An- 11. The process of claim 10, wherein said salt is an alu- spruch 1 und eine Ubergangs-, Lanthanoid- oder minate and the polymer has a bimodal molecular Actinoidmetallocenverbindung oder eine Ziegler- weight distribution. 25 Natta-Katalysatorverbindung eines Metalls der Gruppe 4 bis 6 umfaBt.

Patentanspriiche 11. Verfahren nach Anspruch 10, bei dem das Salz ein Aluminat ist und das Polymer eine bimodale Mole- 1. Aluminoxanatzusammensetzung, die das Reakti- so kulargewichtsverteilung aufweist. onsprodukt aus einem Aluminoxan und einem aus Alkalimetall-, Erdalkalimetall-, Ammonium-, Phos- phonium- und Sulfoniumaluminaten, -boronaten Revendications und -silicaten ausgewahlten Salz umfaBt, wobei das Produkt 0,01 bis 5,0 Mol Salz pro Mol Alumini- 35 1. Composition d'aluminoxanate comportant le pro- um im Aluminoxan enthalt. duit de reaction d'un aluminoxane et d'un sel choisi parmi les aluminates, borates et silicates de metaux 2. Zusammensetzung nach Anspruch 1, in der das alcalins, de metaux alcalino-terreux, d'ammonium, Aluminoxan ein Polymethylaluminoxan ist. de phosphonium et de sulfonium, lequel produit 40 contient de 0,01 a 5,0 moles de sel par mole d'alu- 3. Zusammensetzung nach Anspruch 2, in der das Po- minium contenu dans ledit aluminoxane. lymethylaluminoxan weniger als 23 % des gesam- ten Aluminiums als enthalt und 2. Composition selon la revendication 1 , dans laquelle die Aluminoxanatzusammensetzung kein Trime- ledit aluminoxane est un polymethylaluminoxane. thylaluminium enthalt. 45 3. Composition selon la revendication 2, dans laquelle 4. Zusammensetzung nach Anspruch 1, in der das ledit polymethylaluminoxane contient moins de Aluminoxan ein Polymethylaluminoxan und das 23% de I'aluminium total sous la forme de trimethy- Salz ein Aluminat ist. laluminium, et les compositions d'aluminoxanate ne so contiennent pas de trimethylaluminium. 5. Zusammensetzung nach Anspruch 4, in der das Salz aus Natrium- oder Lithiumaluminat ausgewahlt 4. Composition selon la revendication 1 , dans laquelle wird. ledit aluminoxane est un polymethylaluminoxane et ledit sel est un aluminate. 6. Zusammensetzung nach Anspruch 1, in der das 55 Produkt 0,8 bis 1 ,2 Mol Salz pro Mol Aluminium ent- 5. Composition selon la revendication 4, dans laquelle halt. le sel est choisi parmi I'aluminate de sodium ou de lithium.

6 11 EP0 744 414 B1

6. Composition selon la revendication 1 , dans laquelle le produit contient de 0,8 a 1 ,2 mole de sel par mole d'aluminium.

7. Catalyseur de polymerisation d'olefinescomportant s (a) le produit de reaction selon la revendication 1 et (b) un metallocene.

8. Catalyseur selon la revendication 7, dans lequel le- dit aluminoxane est un methylaluminoxane, ledit 10 produit de reaction contient de 0,1 a 3,0 moles de sel par mole d'aluminium dans ledit aluminoxane, et la proportion molaire du metallocene par mole d'aluminium provenant dudit methylaluminoxane est comprise entre 1 x 10"1 et 1 x 10"4. 15

9. Catalyseur de polymerisation d'olefines comportant le produit de reaction selon la revendication 1 , et un compose metallocene d'un metal de transition, lan- thanide ou actinide ou un compose catalyseur de 20 Ziegler-Natta d'un metal des groupes 4-6.

10. Procede de polymerisation d'olefinescomportant la mise en contact d'une a-olefine comptant de 2 a 20 atomes de carbone, y compris des melanges de eel- 25 le-ci, dans des conditions de polymerisation, avec un catalyseur comportant le produit solide de reac- tion selon la revendication 1 , et un compose metal- locene d'un metal de transition, lanthanide ou acti- nide ou un catalyseur de Ziegler-Natta constitue 30 d'un compose d'un metal des groupes 4-6.

1 1 . Procede selon la revendication 1 0, dans lequel ledit sel est un aluminate et le polymere presente une distribution bimodale du poids moleculaire. 35

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