US007 1931 OOB2

(12) United States Patent (10) Patent No.: US 7,193,100 B2 Sangokoya et al. (45) Date of Patent: Mar. 20, 2007

(54) HALOALUMINOXANE COMPOSITIONS, 5,556,821. A * 9/1996 Aida et al...... 502,113 THEIR PREPARATION, AND THEIR USE IN 5,731,253 A 3/1998 Sangokoya CATALYSIS 5,831, 109 A 11/1998 Smith et al. 5,936,060 A 8/1999 Schmiegel (75) Inventors: Samuel A. Sangokoya, Baton Rouge, 6,046,347 A 4/2000 Jones et al. LA (US); Lubin Luo, Baton Rouge, LA 6,060,418 A 5/2000 Sangokoya c. r: 2C, 6,063,726 A * 5/2000 Kioka et al...... 5O2/117 (US); Steven P. Diefenbach, Baton 6,153,550 A 1 1/2000 Kissin Rouge, LA (US); Jamie R. Strickler, 6,153,551 A 1 1/2000 Kissin et al. Baton Rouge, LA (US); Christopher G. 6,194,340 B1 2/2001 Sangokoya Bauch, Prairieville, LA (US) 6,211,111 B1 4/2001 Chen et al. 6,306,986 B1 10/2001 Teasley (73) Assignee: Albemarle Corporation, Richmond, 6,437.205 B1 8, 2002 Miller et al. VA (US) FOREIGN PATENT DOCUMENTS (*) Notice: Subject to any disclaimer, the term of this JP 49293, 1992 2, 1992 patent is extended or adjusted under 35 RU 4646O2 3, 1975 U.S.C. 154(b) by 21 days. WO WO 03/082466 A1 10, 2003 WO WO O3,082879 A1 10, 2003 (21) Appl. No.: 10/751,144 OTHER PUBLICATIONS (22) Filed: Dec. 31, 2003 Sato, H., et al., Studies on Nickel-Containing Zieler-Type Catalysts. I. New Catalysts for High-cis-1,4-polybutadiene, Bull. Chem. Soc. (65) Prior Publication Data Jpn. 65, 1992, pp. 1299-1306. Siergiejczyk, et al., “Reactions of methylaluminium halides with US 2005/O143254 A1 Jun. 30, 2005 lead oxide'. Polimery. Tworzywa Wielkoczasteczkowe, 1986, pp. 397-398. (51) Int. Cl. C07F 5/06 (2006.01) * cited by examiner CSF 4/602 (2006.01) Primary Examiner Caixia Lu (52) U.S. Cl...... r r 556/179; 556/180; 526/165 (74) Attorney, Agent, or Firm—Marcy M. Hoefling (58) Field of Classification Search ...... 556/179, 556/180, 526,165 (57) ABSTRACT See application file for complete search history. (56) References Cited Novel haloaluminoxane compositions have been formed. The halogen is fluorine, chlorine, and/or bromine, and the U.S. PATENT DOCUMENTS amount of halogen atoms present in said composition is in the range of about 0.5 mole % to about 15 mole % relative 5, 120,696 A 6, 1992 Tsutsui et al. to aluminum atoms. 5,235,081 A 8/1993 Sangokoya 5,329,032 A 7, 1994 Tran et al. 5,416.229 A 5, 1995 Tran et al. 32 Claims, 1 Drawing Sheet U.S. Patent Mar. 20, 2007 US 7,193,100 B2

Figure 1. US 7,193,100 B2 1. 2 HALOALUMINOXANE COMPOSITIONS, the novel compositions of the invention also perform as well THEIR PREPARATION, AND THEIR USE IN as, if not better than, nonhalogenated aluminoxanes when CATALYSIS used as cocatalysts in the polymerization of olefins. In the haloaluminoxane compositions of the invention, one or The work leading to the invention described in this patent more halogen atoms are believed to be bonded directly to the application was performed pursuant to a contract with an aluminoxane. agency of the United States Government. The contract is The fluoroaluminoxane compositions of this invention, Cooperative Agreement No. 70NANBOH3049 between the chloroaluminoxane compositions of this invention, and Albemarle Corporation and the National Institute of Stan the bromoaluminoxane compositions of this invention show dards and Technology of the United States Department of 10 improved characteristics as compared to certain aluminox Commerce (Advanced Technology Program). anes. The fluoroaluminoxane compositions are more pre ferred because the fluoroaluminoxanes show a greater TECHNICAL FIELD degree of enhancement than do the chloroaluminoxanes and bromoaluminoxanes, when compared to the properties of This invention relates to new fluoroaluminoxane compo 15 corresponding nonhalogenated aluminoxanes. However, it is sitions, new chloroaluminoxane compositions, and new bro to be understood that the degree of enhancement in the moaluminoxane compositions that are of particular utility in characteristics of the chloroaluminoxanes and bromoalumi the formation of new catalyst systems, to methods for the noxanes of this invention is also desirable. preparation of these haloaluminoxane compositions and Unlike certain aluminoxanes which often tend to haze or catalyst systems, to the use of Such catalyst systems in the form gels during storage especially when at elevated tem polymerization (homopolymerization and copolymeriza peratures, the fluoroaluminoxane compositions of this tion) of olefins, dienes, or the like. invention, chloroaluminoxane compositions of this inven tion, and bromoaluminoxane compositions of this invention BACKGROUND have significantly reduced tendencies toward gel formation 25 when in solution in an aromatic solvent. Partially hydrolyzed aluminum alkyl compounds known These new fluoroaluminoxane compositions, chloroalu as aluminoxanes (a.k.a. alumoxanes) are effective in acti minoxane compositions, and bromoaluminoxane composi vating metallocenes for polymerization of olefins. Methyla tions are useful as activators or cocatalysts with a wide luminoxane (a.k.a. methylalumoxane) has become the alu variety of transition metal catalysts for forming olefin minum co-catalyst of choice in the industry. It is available 30 homopolymers or copolymers. Because the fluoroaluminox commercially in the form of 10 to 30 wt % solutions in an anes, chloroaluminoxanes, and bromoaluminoxanes of this aromatic solvent, typically toluene. invention are used as cocatalysts, the fluoroaluminoxanes, Modifications to methylaluminoxane have been reported. chloroaluminoxanes, and bromoaluminoxanes are some For example, U.S. Pat. No. 5,329,032 discloses the use of times referred to as cocatalysts in this document. Hereinaf organic groups having electron-rich heteroatoms, such as 35 ter, the fluoroaluminoxanes, chloroaluminoxanes, and bro oxygen or nitrogen, in methylaluminoxane to increase the moaluminoxanes are referred to collectively as stability of methylaluminoxane. The organic groups haloaluminoxanes, with the understanding that the halogen attached to the heteroatom were believed to provide the may be fluorine, chlorine, and/or bromine. The invention observed increases in solubility of the methylaluminoxane. also includes haloaluminoxane compositions that have mix Fluorine species have been reported in aluminoxanes; 40 tures of two or more halogens, in which there at least two again, these fluorine species are part of an organic group, different elements of halogen present in the haloaluminox which organic group is attached to the aluminum site. See ane composition. U.S. Pat. No. 6,153,550, where pentafluorophenyl moieties Aluminoxanes are also called alumoxanes. Thus, the are attached to the aluminoxane, and see U.S. Pat. No. terms fluoroalumoxane and fluoroalumoxane are considered 6,211,111 B1 for additional fluoroaromatic moieties 45 to be synonymous with the term fluoroaluminoxane. Analo attached to aluminoxanes. gously for the chloroaluminoxanes, the terms chloroalumox Chlorinated hydrocarbons, particularly dichlorobenzene, ane and chloro alumoxane are considered to be synonymous have been reported to minimize gel formation when mixed with the term chloroaluminoxane. Similarly for the bromoa with aluminoxanes. No reaction of the chlorinated hydro luminoxanes, the terms bromoalumoxane and bromo alu carbons with the aluminoxanes was contemplated or 50 moxane are considered to be synonymous with the term reported; see Japanese Laid-open Patent 49293 (1992). bromoaluminoxane. Halogenated aluminoxanes have been reported in U.S. This invention provides two novel types of species. One Pat. No. 6,306,986 B1 (referred to therein as alkylhaloalu of these species is an ionic haloaluminoxane complex, minoxanes). These halogenated aluminoxanes are required which, without wishing to be bound by theory, is believed to to have a high degree of halogenation, and are not derived 55 be comprised of an organic cation and an aluminum anion from a pre-made aluminoxane. site of the aluminoxane, where one of the species coordi nated to the aluminum anion site is a halogen atom. It is to SUMMARY OF THE INVENTION be understood that the ionic complexes are thought to exist only at the Small number of aluminum anion sites of the Pursuant to this invention, simple, rapid, and low cost 60 aluminoxane, in particular those aluminum sites to which a process technology is provided for producing novel fluo halogen atom is coordinated. For simplicity, the entire roaluminoxane compositions, novel chloroaluminoxane species containing these ionic complexes is referred to as an compositions, and novel bromoaluminoxane compositions. ionic haloaluminoxane complex. Such compositions typically have considerable stability The other novel species of this invention is a partially under inert, anhydrous conditions, while maintaining their 65 halogenated aluminoxane, which is believed to be com solubility in hydrocarbon solvents, especially aromatic prised of a neutral aluminoxane where halogen atoms are hydrocarbon solvents. In addition to these desirable features, coordinated to Some of the aluminum atoms of the alumi US 7,193,100 B2 3 4 noxane. The term haloaluminoxane is used to refer to both O ionic haloaluminoxane complexes and to partially haloge (iv) at least one tin compound of the formula R'SnX. nated aluminoxanes. where n=1–3, X is, independently, fluorine, chlorine or In one of its embodiments this invention provides a bromine, and where R' is, independently, a hydrocarbyl haloaluminoxane composition wherein the halogen is fluo- 5 group having from one to about twenty carbon atoms; rine, chlorine, and/or bromine. The amount of halogenatoms present in the haloaluminoxane composition is in the range O of about 0.5 mole % to about 15 mole % relative to (v) at least one hydrocarbyl aluminum halide of the aluminum atoms. These haloaluminoxane compositions can formula R"AlX, where m 1 or 2, where X is, indepen be formed from components comprising (a) at least one 10 dently, fluorine, chlorine or bromine, and where R" is, aluminoxane and (b) at least one halogenation agent. The independently, a hydrocarbyl group having from one to halogenation agent is about twenty carbon atoms; (i) at least one halohydrocarbon of the formula RCX, O where n=1–3, X is, independently, fluorine, chlorine or (vi) mixtures of any two or more of (i)–(v), bromine, and where R is, independently, a hydrogen atom or 15 wherein the amount of halogenatoms is in the range of about a hydrocarbyl group having from one to about twenty carbon 0.5 mole 96 to about 15 mole % relative to aluminum atoms, atoms; Such that a haloaluminoxane composition is formed. O Another process for preparing haloaluminoxanes of the (ii) at least one siloxane having at least one labile halogen invention comprises contacting at least one aluminum atom in the molecule, wherein each halogen atom is, inde hydrocarbyl with at least one halogenation agent during the pendently, fluorine, chlorine, or bromine; hydrolysis of the aluminum hydrocarbyl. Again, the amount of halogen atoms is in the range of about 0.5 mole % to O about 15 mole % relative to aluminum atoms, such that a (iii) at least one silane of the formula R', SiX, where haloaluminoxane composition is formed. n=1-3, X is, independently, fluorine, chlorine or bromine, 25 Another embodiment of this invention is a composition and where R' is, independently, a hydrocarbyl group having formed from interaction between components comprising (I) from one to about twenty carbon atoms; either a haloaluminoxane wherein the amount of halogen O atoms is in the range of about 0.5 mole % to about 15 mole (iv) at least one tin compound of the formula RSnX, % relative to aluminum atoms, or where n=1–3, X is, independently, fluorine, chlorine or 30 (a) at least one aluminoxane and (b) at least one haloge bromine, and where R' is, independently, a hydrocarbyl nation agent, wherein the amount of halogen atoms is in the group having from one to about twenty carbon atoms; range of about 0.5 mole % to about 15 mole % relative to O aluminum atoms; (v) at least one hydrocarbyl aluminum halide of the 35 and (II) at least one catalyst compound or complex of a formula R"AIX, where m=1 or 2, where X is, indepen transition metal of Groups 3 to 11 including the lanthanide dently, fluorine, chlorine or bromine, and where R" is, series and the actinide series. Other embodiments relate to independently, a hydrocarbyl group having from one to polymerization processes in which a haloaluminoxane com about twenty carbon atoms; position of this invention is employed as an activator or 40 co-catalyst. O This invention also involves, inter alia, as especially (vi) mixtures of any two or more of (i)–(v). preferred embodiments thereof, a catalyst composition com An alternative method for forming the compositions of prised of a reaction product of a halide or pseudohalide the invention is to have the halogenation agent present (alkoxide, oxyhalide, etc.), or other Ziegler-Natta transition during the formation of the desired aluminoxane, i.e., during as metal catalyst compound and a haloaluminoxane composi the hydrolysis of the aluminum hydrocarbyl(s) used to form tion of this invention. the aluminoxane. Methods for producing Such catalyst compositions and In still another embodiment, this invention provides pro methods of polymerizing or copolymerizing olefinic mono cess technology by which Such haloaluminoxanes can be mers using Such catalyst compositions form still further prepared. Such a process comprises mixing, in an inert, so embodiments of this invention. anhydrous environment, (a) at least one aluminoxane and (b) These and other embodiments and features of this inven at least one halogenation agent which is tion will be still further apparent from the ensuing descrip (i) at least one halohydrocarbon of the formula RCX. tion and appended claims. where n=1–3, X is, independently, fluorine, chlorine or bromine, and where R is, independently, a hydrogen atom or ss BRIEF DESCRIPTION OF THE DRAWING a hydrocarbyl group having from one to about twenty carbon atoms; FIG. 1 is an enlarged postulated Schematic representation O of one of the preferred blue-colored ionic fluoroaluminoxane (ii) at least one siloxane having at least one labile halogen complexes of this invention. 60 atom in the molecule, wherein each halogen atom is, inde FURTHER DETAILED DESCRIPTION OF THIS pendently, fluorine, chlorine, or bromine; INVENTION O (iii) at least one silane of the formula R', SiX, where To form the novel fluoroaluminoxane, chloroaluminox n=1-3, X is, independently, fluorine, chlorine or bromine, 65 ane, and/or bromoaluminoxane compositions of this inven and where R' is, independently, a hydrocarbyl group having tion, an aluminoxane is reacted with at least one halogena from one to about twenty carbon atoms; tion agent. Such halogenation agent is US 7,193,100 B2 5 6 (i) at least one halohydrocarbon of the formula RCX, ity to be isolatable in the form of solids, which ion pairs are where n=1–3, X is, independently, fluorine, chlorine or intermediates in the synthesis of partially chlorinated alu bromine, and where R is, independently, a hydrogen atom or minoxanes. Additionally, this invention makes possible the a hydrocarbyl group having from one to about twenty carbon preparation of bromoaluminoxane ion pairs (hereinafter atoms; referred to as ionic bromoaluminoxane complexes), which O ion pairs are intermediates in the synthesis of partially (ii) at least one siloxane having at least one labile halogen brominated aluminoxanes. However, to date, an ionic bro atom in the molecule, wherein each halogen atom is, inde moaluminoxane complex has not been isolated. pendently, fluorine, chlorine, or bromine; Without being bound by theory, it is believed that the 10 halogenation agent acts as the cationic counterpart to the O anionic aluminum center in the ionic haloaluminoxane com (iii) at least one silane of the formula R', SiX, where plex. The available experimental evidence, especially proton n=1-3, X is, independently, fluorine, chlorine or bromine, and fluorine NMR, suggests that the ionic fluoroaluminox and where R' is, independently, a hydrocarbyl group having anes of this invention are composed of a fluoroaluminoxane from one to about twenty carbon atoms; 15 monovalent anion site complexed or coordinated to a uni valent cation formed from the halogenation agent. Note FIG. O 1 for a depiction of a proposed structure of one such (iv) at least one tin compound of the formula RSnX, complex, which has been observed to be blue in toluene where n=1–3, X is, independently, fluorine, chlorine or solution. It is believed that fluorine is transferred to alumi bromine, and where R' is, independently, a hydrocarbyl num, forming a fluorine-aluminum bond, and an alkyl group group having from one to about twenty carbon atoms; is transferred to the fluorination agent. In the same manner, O again without wishing to be bound by theory, the available (v) at least one hydrocarbyl aluminum halide of the experimental evidence for the ionic chloroaluminoxane formula R"AIX, where m=1 or 2, where X is, indepen complexes also indicates a chloroaluminoxane monovalent dently, fluorine, chlorine or bromine, and where R" is, 25 anion site complexed or coordinated to a univalent cation independently, a hydrocarbyl group having from one to formed from the chlorination agent. Again, it is believed that about twenty carbon atoms; chlorine is transferred to aluminum, forming a chlorine aluminum bond, and an alkyl group is transferred to the O aromatic compound. Similarly for bromine, the experimen (vi) mixtures of any two or more of (i)–(v). 30 tal evidence Suggests a bromoaluminoxane monovalent The amount of halogen atoms is in the range of about 0.5 anion site complexed or coordinated to a univalent cation mole 96 to about 15 mole 96 relative to aluminum atoms. The formed from the bromination agent. reaction is conducted in an inert, anhydrous environment Some of these ionic haloaluminoxane complexes have Such as in an anhydrous liquid aromatic hydrocarbon Sol been observed to be thermal and light sensitive. Under vent. Such as one or more of benzene, toluene, Xylene, 35 ambient conditions without exclusion of light, the blue color mesitylene, ethylbenzene, diethylbenzene, 1,2,4-triethyl of Some of these complexes lasts from hours to days, benzene, 1,3,5-triethylbenzene, amylbenzene, tetrahy depending on the halogen content. The blue color faded dronaphthalene, and the like. away faster at higher temperature, with exposure to light, or As mentioned above, the compositions of the invention in contact with a polar solvent Such as tetrahydrofuran may also be formed by having the halogenation agent 40 (THF). Some of the ionic haloaluminoxane complexes show present during the hydrolysis of the aluminum decreased solubility in aromatic hydrocarbons, presumably hydrocarbyl(s) used to form the aluminoxane. due to the ionic character of the complex. Increased stability is tested on a sample as a 30 wt % In experimental work conducted to date, ionic haloalu solution in toluene. The sample is stored indoors for 18 days minoxane complexes formed from siloxanes, silanes, and tin at about 25°C., followed by outdoor storage at about 20–50° 45 compounds have not been isolated, nor have attempts been C. for 12 days. If gel formation has increased by five-fold or made to isolate Such complexes. It is theorized that ionic less, based on the weight percent gel found on the 30th day haloaluminoxane complexes are formed as intermediates in (in comparison to the amount of gel present initially), the the synthesis of partially halogenated aluminoxanes in the haloaluminoxane is generally considered to be of increased case of siloxanes, silanes, and tin compounds, but that the stability. 50 ionic haloaluminoxane complexes proceed to the end prod It is preferred that the haloaluminoxane components as uct because the respective cations formed are unstable well as the resultant haloaluminoxane compositions be (relative to some of the carbon cations formed when a handled in an inert, moisture-free, oxygen free environment halohydrocarbon is the halogenation agent). However, it is Such as argon, nitrogen or helium because of the sensitivity contemplated that ionic haloaluminoxane complexes formed 55 from siloxanes, silanes, and tin compounds, if isolatable, of Such components and compositions to moisture and probably require carefully controlled conditions, e.g., low OXygen. temperatures (for example, circa -78° C.) and/or careful Compounds of the Invention selection of a solvent that would stabilize the ionic complex. This invention makes possible the preparation of certain The existence of Such ionic complexes is Supported by the stable fluoroaluminoxane ion pairs (hereinafter referred to as 60 yellow color observed during the synthesis of the partially ionic fluoroaluminoxane complexes), Some of which have fluorinated aluminoxanes utilizing a siloxane, which yellow sufficient stability to be isolatable in the form of solids, color is believed to be an ionic haloaluminoxane complex. which ion pairs are believed to be intermediates in the It is not known whether hydrocarbyl aluminum halides form synthesis of partially fluorinated aluminoxanes. Similarly, ionic haloaluminoxane complexes. this invention also makes possible the preparation of certain 65 Mixing of an aluminoxane with at least one halogenation stable chloroaluminoxane ion pairs (hereinafter referred to agent in an inert, anhydrous environment Such as in an as ionic chloroaluminoxane complexes) of Sufficient stabil anhydrous liquid aromatic hydrocarbon solvent, preferably US 7,193,100 B2 7 8 in the absence of heat, is generally sufficient to form an ionic ane, partially fluorinated n-hexylaluminoxane, partially flu haloaluminoxane complex. These mixtures, containing com orinated n-octylaluminoxane, partially fluorinated phenyla plexes of the invention, are also deemed compositions of the luminoxane, partially chlorinated methylaluminoxane, invention. partially chlorinated ethylaluminoxane, partially chlorinated Another type of haloaluminoxane of this invention is a n-propylaluminoxane, partially chlorinated n-butylalumi partially halogenated aluminoxane. These compositions noxane, partially chlorinated isobutylaluminoxane, partially have been observed to be clear yellow, clear green, or chlorinated n-hexylaluminoxane, partially chlorinated n-oc colorless in toluene solution. This type of haloaluminoxane tylaluminoxane, partially chlorinated phenylaluminoxane, is believed to be an aluminoxane in which fluorine, chlorine, partially brominated methylaluminoxane, partially bromi or bromine is bound to some of the aluminum atoms. 10 nated ethylaluminoxane, partially brominated n-propylalu Partially halogenated aluminoxanes can be formed by heat minoxane, partially brominated n-butylaluminoxane, par ing or aging a mixture containing an ionic haloaluminoxane tially brominated isobutylaluminoxane, partially brominated complex. For the halogenation agents for which an ionic n-hexylaluminoxane, partially brominated n-octylaluminox intermediate is not observed, the aluminoxane and haloge ane, and partially brominated phenylaluminoxane. Also nation agent are contacted to form the partially halogenated 15 included as partially halogenated aluminoxanes are those aluminoxane. For at least some siloxanes, silanes, and tin that have two or more different elements of halogen (e.g., compounds, heating or aging is unnecessary. When the fluorine and chlorine; fluorine and bromine; chlorine and halogenation agent is a halohydrocarbon, silane, or tin bromine; fluorine, chlorine, and bromine). compound, the major by-product of the formation of a Aluminoxane compositions are generally obtained by partially halogenated aluminoxane is normally an organic hydrolyzing aluminum compounds such as alkyl aluminum compound analogous to that of the halogenation agent, in compounds with water e.g., by direct water addition, contact which it appears that the sites of the halogenation agent with a water-wet material Such as a solvent containing water formerly having halogen atoms now contain hydrocarbyl or a Solid Substrate Such as a porous catalyst Support wet groups, presumably from the aluminoxane. with or soaked in water, or via salt hydrate addition. The It appears that the by-products formed during preparation 25 resulting products, depending on the amount of added water, of the partially halogenated aluminoxane do not bind to the are dimeric or complex mixtures of oligomeric aluminox partially halogenated aluminoxane when halohydrocarbons, aS. silanes, or tin compounds are used in the preparation of the Non-limiting examples of aluminoxanes that can be used partially halogenated aluminoxanes. to make the haloaluminoxanes of this invention include When siloxanes are used in the preparation of the partially 30 methylaluminoxane, ethylaluminoxane, n-propylaluminox halogenated aluminoxanes, the siloxane by-product appears ane, n-butylaluminoxane, isobutylaluminoxane, n-hexylalu to remain associated with the partially halogenated alumi minoxane, n-octylaluminoxane, decylaluminoxane, dodecy noxane. An advantage to this is that the presence of this laluminoxane, tetradecylaluminoxane, siloxane by-product increases the solubility of the partially hexadecylaluminoxane, octadecylaluminoxane, phenylalu halogenated aluminoxane. The siloxane by-product does not 35 appear to adversely affect the properties of the partially minoxane, tolylaluminoxane, and the like. Mixtures of alu halogenated aluminoxane. minoxanes may also be used. When the halogenation agent is a hydrocarbyl aluminum Preferred aluminoxanes are those in which the hydrocar byl groups are saturated, particularly those aluminoxanes in halide, the “hydrocarbyl aluminum portion of the molecule which the hydrocarbyl groups have from one to about becomes bound to, and part of the aluminoxane moiety. The 40 twenty carbon atoms. More preferred are aluminoxanes in aluminum from the hydrocarbyl aluminum halide that which the saturated hydrocarbyl groups have from one to becomes part of the aluminoxane is indistinguishable from about six carbon atoms. Even more preferred are methyla the aluminum already present as part of the aluminoxane, luminoxane, ethylaluminoxane, n-butylaluminoxane, and and is thus an inexpensive method for increasing the alu iso-butylaluminoxane. Highly preferred are methylalumi minum content of an aluminoxane while halogenating the 45 aluminoxane. noxane and ethylaluminoxane. The most highly preferred As previously mentioned, the amount of halogen atoms in aluminoxane is methylaluminoxane. the haloaluminoxane is in the range of about 0.5 mole % to The methylaluminoxane may contain up to about 15 mole about 15 mole 96 relative to aluminum atoms. At a mole ratio percent (based on aluminum) of moieties formed from of less than about 0.5%, the formed haloaluminoxanes have 50 amines, alcohols, ethers, esters, phosphoric and carboxylic properties similar to aluminoxanes. Above a mole ratio of acids, thiols, alkyl disiloxanes, and the like to improve their about 15 mole %, solid formation tendencies increase. activity, solubility, and/or stability. A preferred type of Preferred mole ratios of halogen atoms to aluminum atoms moiety is a bulky phenol. Suitable bulky phenols include are in the range of about 2 mole percent to about 10 mole 2,6-dimethyl-4-(1,1-dimethylpropyl)phenol. 2,6-diisobutyl percent halogen (relative to aluminum). More preferred is 55 4-methylphenol. 2,6-diisopropylphenol. 2,4,6-triisopropy ratio of about 2 mole percent to about 6 mole percent lphenol. 2,6-diisobutylphenol. 2,4,6-triisobutylphenol. 2.6- halogen atoms to aluminum atoms. The optimum mole ratio di-tert-butylphenol. 2,4,6-tri-tert-butylphenol, and the like. may vary with the particular haloaluminoxane. Experimen It is preferred that such phenols are reacted with the trialky tal results indicate that the reaction of the halogenation agent laluminum compound prior to the formation of the alumi with the aluminoxane is stoichiometric, i.e., most or all of 60 OXa. the labile halogen atoms appear to transfer to the aluminox Concentrations of aluminoxanes are typically in the range a. of about 10 wt % aluminoxane to about 50 wt % aluminox Partially halogenated aluminoxanes of this invention ane. Preferably, the concentration of the aluminoxane solu include, but are not limited to, partially fluorinated methy tion is in the range of about 10 wt % to about 30 wt %. laluminoxane, partially fluorinated ethylaluminoxane, par 65 Usually, the aluminoxane is in a hydrocarbon solvent, pref tially fluorinated n-propylaluminoxane, partially fluorinated erably an aromatic hydrocarbon solvent. Most preferably, n-butylaluminoxane, partially fluorinated isobutylaluminox the aluminoxane is in toluene. US 7,193,100 B2 10 The halogenation agents that can be used in forming the particular, this highly preferred group of halohydrocarbons haloaluminoxanes of the invention contain labile halogen can be represented by the formula: atoms, i.e., halogen atoms that can react with aluminum sites in the aluminoxane. Non-labile halogen atoms may also be ArG present in the halogenation agent. For example, halogen atoms directly bound to aromatic rings have been observed where Ar is an aromatic hydrocarbon ring system, which to be non-labile, i.e., Such halogen atoms remain bound to typically contains up to about 25 carbon atoms, preferably the aromatic ring when a halogenation agent containing Such up to about 12 carbon atoms, and most preferably 6 carbon a moiety is brought into contact with an aluminoxane. Only atoms in the ring system (i.e., excluding X and excluding those halogen atoms that are labile are considered in deter 10 any Substituents that may be present on the ring(s)): G is mining the mole percent of halogen atoms relative to alu —CX. —CX-R, or—CXR, in which X is, independently, a fluorine atom, chlorine atom, or bromine atom, and in minum atoms in the partially halogenated aluminoxane. which R is, independently, a hydrogen atom or C. alkyl When R of the halohydrocarbon, R' of the silane or tin group; and n is 1 to 5, preferably 1 to 3, more preferably 1 compound, or R" of the hydrocarbyl aluminum halide is an or 2, and most preferably 1. G is preferably a trihalomethyl aryl group, and the aryl group has a —OH, -SH, or—NH 15 group as a substituent on the aromatic ring, the —OH, -SH, group. or NH group will react with the aluminoxane before the When there are substituents on the aromatic ring(s) other labile halogen atoms do, resulting in the binding of the than hydrogen and the group(s) containing labile halogen halogenation agent to the aluminoxane, followed by the atom(s), it is preferred that these other such substituents are reaction of the labile halogen atoms with the aluminoxane. electron-donating Substituents. Halogenation agents con This may be advantageous when the presence of Such taining aromatic groups having electron-withdrawing Sub species improves the solubility and/or stability of the prod stituents on the ring, Such as fluorine, were observed to have uct haloaluminoxane and/or the activity imparted to a poly slower reaction rates than halogenation agents with aromatic merization by the use of Such a haloaluminoxane as a groups having only hydrogen atoms as Substituents. In turn, cocatalyst. The need for labile halogen atoms in the halo 25 halogenation agents containing aromatic groups having genation agent excludes Such moieties as pentafluorophenol, electron-donating substituents were observed to have faster reaction rates than halogenaton agents in which there were which does not have labile halogen atoms. only hydrogen atoms on the aromatic ring. Typical electron Haloaluminoxanes having two or more different types donating Substituents include hydrocarbyloxy groups and (elements) of halogen can be prepared. One way to obtain hydrocarbyl groups. Such haloaluminoxanes is to use a mixture of halogenation 30 agents, where at least one halogenation agent has labile Suitable halohydrocarbons having an aryl group include halogen atom(s) of one element, and at least one halogena C.C.C.-trifluorotoluene, C.C.-difluorotoluene, C-fluorotolu tion agent has labile halogen atom(s) of another element. ene, octafluorotoluene, 1,2-di(fluoromethyl)benzene, 1,3-di Another method for preparing haloaluminoxanes having two (fluoromethyl)benzene, 1,4-di(fluoromethyl)benzene, 1,2- or more different halogen elements is to use one or more 35 bis(difluoromethyl)benzene, 1,3-bis(difluoromethyl) halogenation agents in which there are halogenatoms of two benzene, 1,4-bis(difluoromethyl)benzene, 1,3-bis or more different elements of halogen. Labile fluorine atoms (trifluoromethyl)benzene, 1,3,5-tris(trifluoromethyl) normally react faster with the aluminoxane than do labile benzene, 4-methyl-1-(trifluoromethyl)benzene, 3-methyl-1- chlorine or bromine atoms. (trifluoromethyl)benzene, 1,3-bis(trifluoromethyl)-4- 40 methylbenzene, 1,4-bis(trifluoromethyl)-2-methylbenzene, One type of halogenation agent that can be used to form 1-ethyl-3,5-bis(trifluoromethyl)benzene, 1-isopropyl-4-(tri the haloaluminoxanes of this invention is a halohydrocarbon fluoromethyl)benzene, 1-(fluoromethyl)-4-fluoro-2-(trifluo of the formula RCX, where n=1–3, X is, independently, romethyl)benzene, 1-(fluoromethyl)-2,4-bis(trifluorom fluorine, chlorine or bromine, and where R is, independently, ethyl)benzene, 1-(1-fluoroethyl)benzene, 1.2- a hydrogenatom or a hydrocarbyl group having from one to 45 difluoroethylbenzene, 3,3'-bis(trifluoromethyl)biphenyl, about twenty carbon atoms. R can be a straight chain, 4,4'-bis(trifluoromethyl)biphenyl, 2,2'-bis(fluoromethyl)bi branched, cycloalkyl, aryl, or araalkyl group. When only one phenyl, 3-(difluoromethyl)biphenyl, 1-(trifluoromethyl) R is a hydrocarbyl group, the hydrocarbyl group is prefer naphthalene, 2-(trifluoromethyl)naphthalene, 1-(difluorom ably an aryl group. Halohydrocarbons in which all R are ethyl)naphthalene, 2-(difluoromethyl)naphthalene, hydrogen atoms are not preferred, because Such halohydro 50 1-(fluoromethyl)naphthalene, 1.8-bis(fluoromethyl)-naph carbons tend to react slowly with the aluminoxane, and thalene, 1-(fluoromethyl)-2-(methyl)naphthalene, 1-isobu frequently the reaction does not go to completion, i.e., the tyl-2-trifluoromethyl-naphthalene, 1-methyl-4-trifluorom yields are low. ethyl-naphthalene, 1-n-butyl-5-trifluoromethyl-naphthalene, A preferred type of halohydrocarbon is a tertiary halohy 1-(trifluoromethyl)anthracene, 2-(difluoromethyl)an drocarbon; a more preferred type of halohydrocarbon is that 55 thracene, 9-(fluoromethyl)anthracene, 9,10-bis(trifluorom in which at least one R is an aryl group. Less preferred are ethyl)anthracene, 9-(trifluoromethyl)-phenanthrene, triph secondary and primary halohydrocarbons, because they pro enylfluoromethane, difluorodiphenylmethane, C.C.C.- vide less stability to the believed cationic species of the ionic trichlorotoluene, C.C.-dichlorotoluene, C-chlorotoluene, 1.3- aluminoxane complexes, or to the intermediate in the for bis(trichloromethyl)-4-methylbenzene, 1,4-bis mation of the partially halogenated aluminoxane. 60 (trichloromethyl)-2-methylbenzene, 4-methyl-1- A highly preferred type of halohydrocarbon is one in (trichloromethyl)benzene, 3-methyl-1 (trichloromethyl) which at least one R is an aryl group, especially a phenyl benzene, octachlorotoluene, 1,2-di(chloromethyl)benzene, group. When at least one R is an aryl group, tertiary 1,3-di(chloromethyl)benzene, 1,4-di(chloromethyl)benzene, halohydrocarbons are not especially preferred, i.e., a pri 1,3,5-tris(trichloromethyl)benzene, 1-ethyl-3,5-bis(trichlo mary halohydrocarbon in which one R is an aryl group and 65 romethyl)benzene, 1-isopropyl-4-(trichloromethyl)benzene, the other R(s) are hydrogen atoms, or all of the other 1-(chloromethyl)-4-chloro-2-(trichloromethyl)benzene, Substituents are halogen atoms, are also highly preferred. In 1-(chloromethyl)-2,4-bis(trichloromethyl)benzene, 1-(1- US 7,193,100 B2 11 12 chloroethyl)benzene, 1,2-dichloroethylbenzene, 3,3'-bis luoromethyl)benzene, 1-(tribromomethyl)-3- (trichloromethyl)biphenyl, 4,4'-bis(trichloromethyl)biphe (trichloromethyl)-5-(trifluoromethyl)benzene, 1-ethyl-3- nyl, 2,2'-bis(chloromethyl)-biphenyl, 3-(dichloromethyl) (trichloromethyl)-5-(trifluoromethyl)benzene, biphenyl, 1-(trichloromethyl)naphthalene, 1-(chloromethyl)-4-chloro-2-(tribromomethyl)-benzene, 2-(trichloromethyl)naphthalene, 1-(dichloromethyl)naph 1-(fluoromethyl)-2,4-bis(trichloromethyl)benzene, 1-(1- thalene, 2-(dichloromethyl)-naphthalene, 1-(chloromethyl) bromoethyl)-3-(1-fluoroethyl)-benzene, 1-(1,2-dichloroet naphthalene, 1.8-bis(chloromethyl)-naphthalene, 1-(chlo hyl)-4-(1-fluoroethyl)benzene, 1-trichloromethyl-4-trifluo romethyl)-2-(methyl)naphthalene, 1-isobutyl-2- romethyl-2,3,5,6-tetrachlorobenzene, 3-(trichloromethyl)- trichloromethylnaphthalene, 1-methyl-4- 3'-(trifluoromethyl)biphenyl, 4-(dichloromethyl)-4 trichloromethylnaphthalene, 1-n-butyl-5-trichloromethyl 10 (difluoromethyl)-biphenyl, 2-(chloromethyl)-2'- naphthalene, 1-(trichloromethyl)-anthracene, (fluoromethyl)biphenyl, 1-(trichloromethyl)-2- 2-(dichloromethyl)anthracene, 9-(chloromethyl)anthracene, (trifluoromethyl)naphthalene, 1-(difluoromethyl)-2- 9,10-bis(trichloromethyl)anthracene, 9-(trichloromethyl) (dichloromethyl)-naphthalene, 1-(bromomethyl)-8- phenanthrene, triphenylchloromethane, dichlorodiphenyl (fluoromethyl)naphthalene, 9-(trifluoromethyl)-10 methane, C.C.C.-tribromotoluene, C.C.-dibromotoluene, 15 C.-bromotoluene, 1,2-di(bromomethyl)benzene, 1,3-di(bro (trichloromethyl)anthracene, and the like. Mixtures of two momethyl)benzene, 1,4-di(bromomethyl)benzene, 1,3-bis or more of the foregoing halohydrocarbons may also be (tribromomethyl)benzene, 1,3,5-tris(tribromomethyl)ben used. Zene, 4-methyl-1-(tribromomethyl)benzene, 3-methyl-1- Preferred halohydrocarbons are tert-butyl fluoride, tert (tribromomethyl)benzene, 1,3-bis(tribromomethyl)-4- butyl chloride, tert-butyl bromide, C.C.C.-trifluorotoluene, methylbenzene, 1,4-bis(tribromomethyl)-2-methylbenzene, 4-methyl-1-(trifluoromethyl)benzene, 3-methyl-1-(trifluo 1-ethyl-3,5-bis(tribromomethyl)benzene, 1-isopropyl-4-(tri romethyl)benzene, triphenylfluoromethane, C.C.C.-trichlo bromomethyl)benzene, 1-(bromomethyl)-2-(tribromom rotoluene, 4-methyl-1-(trichloromethyl)benzene, 3-methyl ethyl)benzene, 1-(bromomethyl)-2,4-bis(tribromomethyl) 1-(trichloromethyl)benzene, triphenylchloromethane, C.C. benzene, 1-(1-bromoethyl)-benzene, 1.2- 25 O-tribromotoluene, 4-methyl-1-(tribromomethyl)benzene, dibromoethylbenzene, 3,3'-bis(tribromomethyl)biphenyl, 3-methyl-1-(tribromomethyl)-benzene, and triphenylbro 4,4'-bis(tribromomethyl)biphenyl, 2,2'-bis(bromomethyl)bi momethane. More preferred are C.C.C.-trifluorotoluene, phenyl, 3-(dibromomethyl)biphenyl, 1-(tribromomethyl) 4-methyl-1-(trifluoromethyl)benzene, C.C.C.-trichlorotolu naphthalene, 2-(tribromomethyl)naphthalene, 1-(dibromom ene, triphenylchloromethane, C.C.C.-tribromotoluene, and ethyl)-naphthalene, 2-(dibromomethyl)-naphthalene, 30 triphenylbromomethane. The most preferred halohydrocar 1-(bromomethyl)naphthalene, 1.8-bis(bromomethyl)naph bons are C.O.C.-trifluorotoluene, 4-methyl-1-(trifluorom thalene, 1-(bromomethyl)-2-(methyl) naphthalene, 1-isobu ethyl)benzene, triphenylchloromethane, and O.O.C.-tribro tyl-2-tribromomethyl-naphthalene, 1-methyl-4-tribromom motoluene. ethyl-naphthalene, 1-n-butyl-5-tribromomethyl Another type of halogenation agent that can be used to naphthalene, 1-(tribromomethyl)anthracene, 35 form the haloaluminoxanes of this invention is at least one 2-(dibromomethyl)anthracene, 9-(bromomethyl)anthracene, siloxane having at least one labile halogen atom in the 9,10-bis(tribromomethyl)anthracene, 9-(tribromomethyl) molecule, wherein each halogen atom is, independently, phenanthrene, triphenylbromomethane, dibromodiphenyl fluorine, chlorine, or bromine. These siloxanes have hydro methane, and the like. Mixtures of two or more of the carbyl groups which preferably contain from about 1 to 30 foregoing halohydrocarbons may also be used. 40 carbon atoms and include linear and/or branched alkyl Suitable halohydrocarbons which do not have an aryl groups which contain from about 1 to 24 carbon atoms, group include tert-butyl fluoride (2-methyl-2-fluoropro cycloalkyl groups which contain from about 3 to 24 carbon pane), 3-methyl-3-fluoropentane, 3-methyl-3-fluorohexane, atoms, and alkylaryl or aryl groups which contain from 1-methyl-1-fluorocyclohexane, 1,3-difluoro-1,3,5-methyl about 6 to 30 carbon atoms. At least one hydrocarbyl group cyclooctane, 2-methyl-2-fluoroheptane, 1,2-difluoro-1-me 45 of the siloxane contains at least one labile halogen atom. The thylcyclooctane, 2-methyl-2-chloropropane, tert-butyl chlo siloxanes are chosen from disiloxanes and linear or cyclic ride, 3-methyl-3-chloropentane, 3-chlorohexane, 3-methyl polysiloxanes. The siloxanes contain the Si-O-Si bond 3-chlorohexane, 1-methyl-1-chlorocyclohexane, 1,3- and are substantially free of Si OH bonds. The siloxanes dichloro-1,3,5-methylcyclooctane, 2-methyl-2- can contain mixed hydrocarbyl groups. The polysiloxanes chloroheptane, 1,2-dichloro-1-methylcyclooctane, 50 have a linear, or branched, or cyclic backbone of alternating 2-methyl-2-bromopropane, tert-butyl bromide, 3-methyl-3- silicon and oxygen atoms. If the polysiloxane is acyclic, it bromopentane, 2-bromohexane, 3-bromohexane, 3-methyl can be represented by the empirical formula, SiO, 3-bromohexane, 1-methyl-1-bromocyclohexane, 1,3-di wherein n is at least 3 (preferably in the range of 3 to 6, and bromo-1,3,5-methylcyclooctane, 2-methyl-2- most preferably in the range of 3 to 4), and wherein the bromoheptane, 1,2-dibromo-1-methylcyclooctane, and the 55 oxygen atoms are always individually disposed between and like. Mixtures of two or of the foregoing halohydrocarbons connected to two silicon atoms as a —Si-O-Si-moiety. may also be used. The cyclic polysiloxanes can be represented by the empirical Suitable halohydrocarbons which have at least two dif formula SiO, where n is as defined above, and wherein, as ferent elements of halogen that may be used include, but are in the case of the acyclic polysiloxanes, the oxygen atoms not limited to, 1-chloro-3-fluoro-1,3,5-methylcyclooctane, 60 are always individually disposed between and connected to 2-bromo-1-fluoro-1-methylcyclooctane, 2-chloro-1-fluoro two silicon atoms as a Si-O Si moiety. Whether 1-methylcyclooctane, 1-(trichloromethyl)-4-(trifluorom cyclic or acyclic, the backbone of a polysiloxane containing ethyl)benzene, 1-(dichloromethyl)-3-(dibromomethyl)-ben 4 or more silicon atoms can be branched on one or more of Zene, 1-(bromomethyl)-2-(fluoromethyl)benzene, the silicon atoms of the backbone. In Such case, the silicon 1-(chloromethyl)-4-(trifluoromethyl)-benzene, 1-(dichlo 65 atom that carries the branch is bonded to three or four romethyl)-3-(fluoromethyl)benzene, 1-(bromomethyl)-3,5- separate oxygenatoms, and each Such oxygenatom is in turn bis(trifluoromethyl)benzene, 1-(chloromethyl)-3,5-bis(trif. bonded to an additional separate silicon atom. US 7,193,100 B2 13 14 Non-limiting examples of siloxanes include (trifluorom ethyl)bis(fluoromethyl)tetramethyltrisiloxane, (3,3,3- ethyl)pentamethyldisiloxane, tris(fluoromethyl)trimethyld trichloropropyl)(3,3,3-trifluoropropyl)hexamethyltrisilox isiloxane, (2,2-difluoroethyl)pentaethyldisiloxane, bis(1,2- ane, (m-trichloromethylphenyl)(m-trifluoromethylphenyl) difluoroethyl)triethyldisiloxane, bis(trifluoromethyl) hexaphenylcyclotetrasiloxane, and the like. Mixtures of two tetramethyldisiloxane, (trifluoromethyl) or more of the foregoing siloxanes may also be used. trimethyldicyclohexyldisiloxane, tetramethylbis(2.2- Preferred siloxanes are trisiloxanes and tricyclosiloxanes. difluorocyclohexyl)-disiloxane, tetramethylbutyl (4.4.4- Also preferred are siloxanes with at least one 3,3,3-trihalo trifluorobutyl)disiloxane, bis(p-trifluoromethylphenyl)- propyl group. Preferred siloxanes include 3,3,3-trifluoropro tetraphenyldisiloxane, diphenyltrimethyl(difluoromethyl) pylheptamethyltrisiloxane, 3,3,3-trifluoropropylheptameth disiloxane, tetraphenylbis-(fluoromethyl)disiloxane, bis 10 ylcyclotrisiloxane, trimethyl(3,3,3-trifluoropropyl) (difluoromethyl)tetramethylcyclotrisiloxane, tetra cyclopolysiloxane, tetramethyl(3,3,3-trifluoropropyl) (fluoromethyl)tetramethyltrisi loxane, 3,3,3- cyclopolysiloxane, polymethyl(3,3,3-trifluoropropyl) trifluoropropylheptamethyltrisiloxane, bis(3,3,3- siloxane. polydimethylsiloxane-co-methyl(3,3,3- trifluoropropyl)hexamethyltrisiloxane, 3,3,3- trifluoropropyl)siloxane: 3,3,3- trifluoropropylheptamethylcyclotrisiloxane, 15 trichloropropylheptamethyltrisiloxane, 3,3,3- (trifluoromethyl)heptamethylcyclotetrasiloxane, bis(m-trif. trichloropropylheptamethylcyclotrisiloxane, trimethyl(3.3, luoromethylphenyl)-hexaphenylcyclotetrasiloxane, trime 3-trichloropropyl)cyclopolysiloxane, tetramethyl(3,3,3- thyl(3,3,3-trifluoropropyl)cyclopolysiloxane, tetramethyl trichloropropyl)cyclopolysiloxane. polymethyl(3,3,3- (3,3,3-trifluoropropyl)cyclopolysiloxane, polymethyl(3.3, trichloropropyl)siloxane, polydimethylsiloxane-co-methyl 3-trifluoropropyl)siloxane, polydimethylsiloxane-co (3,3,3-trichloropropyl)siloxane: 3,3,3- methyl(3,3,3-trifluoropropyl)siloxane, (trichloromethyl) tribromopropylheptamethyltrisiloxane, 3,3,3- pentamethyldisiloxane, tris(chloromethyl) tribromopropylheptamethylcyclotrisiloxane, trimethyl(3.3, trimethyldisiloxane, 2.2-(dichloroethyl) 3-tribromopropyl)cyclopolysiloxane, tetramethyl(3,3,3- pentaethyldisiloxane, bis(1,2-dichloroethyl) tribromopropyl)cyclopolysiloxane, polymethyl(3,3,3- triethyldisiloxane, bis(trichloromethyl) 25 tribromopropyl)siloxane, and polydimethylsiloxane-co tetramethyldisiloxane, (trichloromethyl) methyl(3,3,3-tribromopropyl)siloxane. More preferred are trimethyldicyclohexyldisiloxane, tetramethylbis(2.2- 3,3,3-trifluoropropylheptamethyltrisiloxane, 3,3,3-trifluoro dichlorocyclohexyl)disiloxane, tetramethylbutyl (4.4.4- propylheptamethylcyclotrisiloxane, polymethyl(3,3,3-trif trichlorobutyl)disiloxane, bis(p-trichloromethylphenyl) luoropropyl)siloxane, 3,3,3-trichloropropylheptamethyl tetraphenyldisiloxane, diphenyltrimethyl(dichloromethyl) 30 trisiloxane, 3,3,3- disiloxane, tetraphenylbis(chloromethyl)disiloxane, bis trichloropropylheptamethylcyclotrisiloxane, polymethyl(3. (dichloromethyl)tetramethylcyclotrisiloxane, tetra 3,3-trichloropropyl)siloxane, 3,3,3- (chloromethyl)tetramethyltrisiloxane, 3,3,3- tribromopropylheptamethyltrisiloxane, 3,3,3- trichloropropylheptamethyltrisiloxane, bis(3,3,3- tribromopropylheptamethylcyclotrisiloxane, and poly trichloropropyl)hexamethyltrisiloxane, 3,3,3- 35 methyl(3,3,3-tribromopropyl)siloxane. The most preferred trichloropropylheptamethylcyclotrisiloxane, siloxanes are polymethyl(3,3,3-trifluoropropyl)siloxane. (trichloromethyl)heptamethylcyclotetrasiloxane, bis(m- polymethyl(3,3,3-trichloropropyl)siloxane, and polyme trichloromethylphenyl)hexaphenylcyclotetrasiloxane, tri thyl(3,3,3-tribromopropyl)siloxane. methyl(3,3,3-trichloropropyl)cyclopolysiloxane, tetrame Still another type of halogenation agent that may be used thyl(3,3,3-trichloropropyl)cyclopolysiloxane, polymethyl 40 in forming the haloaluminoxanes of the invention is at least (3,3,3-trichloropropyl)siloxane, polydimethylsiloxane-co one silane of the formula R'SiX, where n=1–3, X is, methyl(3,3,3-trichloropropyl)siloxane, (tribromomethyl) independently, fluorine, chlorine or bromine, and where R' pentamethyldisiloxane, (2,2-dibromoethyl) is, independently, a hydrocarbyl group having from one to pentaethyldisiloxane, tetramethylbis(2.2- about twenty carbon atoms. Each R' can be a straight chain, dibromocyclohexyl)disiloxane, bis(p- 45 branched, cycloalkyl, aryl, or araalkyl group. R' is preferably tribromomethylphenyl)tetraphenyldisiloxane, bis an aryl group; when R is an aryl group, it preferably has (dibromomethyl)tetramethylcyclotrisiloxane, bis(3,3,3- from six to about twenty carbon atoms; it is more preferred tribromopropyl)hexamethyltrisiloxane, 3,3,3- that the aryl group is a phenyl group. More preferably, R' is tribromopropylheptamethyltrisiloxane, 3,3,3- a straight chain or branched hydrocarbyl group, and when R' tribromopropylheptamethylcyclotrisiloxane, trimethyl(3.3, 50 is a straight chain or branched hydrocarbyl group, it pref 3-tribromopropyl)-cyclopolysiloxane, tetramethyl(3,3,3- erably has from one to about twelve carbon atoms; more tribromopropyl)cyclopolysiloxane, polymethyl(3,3,3- preferably, R has from one to about six carbon atoms; the tribromopropyl)siloxane, and polydimethylsiloxane-co most preferred straight chain or branched hydrocarbyl group methyl(3,3,3-tribromopropyl)siloxane, and the like. is a methyl group. Mixtures of two or more of the foregoing siloxanes may also 55 Silanes that can be used as halogenation agents include, be used. but are not limited to, trimethylfluorosilane, dimethyldifluo Suitable siloxanes having two or more different elements rosilane, diethyldifluorosilane, diisopropyldifluorosilane, of halogen include, but are not limited to, (fluoromethyl) tert-butyltrifluorosilane, dicyclobutyldifluorosilane, tripen (chloromethyl)(bromomethyl)trimethyldisiloxane, (2.2- tylfluorosilane, dicyclohexyldifluorosilane, triheptylfluo dichloroethyl)(2,2-difluoroethyl)tetraethyldisiloxane, (1.2- 60 rosilane, dicyclooctylidifluorosilane, triphenylfluorosilane, dichloroethyl)(1,2-difluoroethyl)triethyldisiloxane, diphenyldifluorosilane, phenyltrifluorosilane, phenyldim (trichloromethyl)(tribromomethyl)tetramethyldisiloxane, ethylfluorosilane, diphenylmethylfluorosilane, phenylmeth tetramethyl(2,2-dichlorocyclohexyl)(2,2-difluorocyclo yldifluorosilane, phenyldiisopropylfluorosilane, tritolylfluo hexyl)disiloxane, (p-tribromomethylphenyl)(p-trifluorom rosilane, ditolyldifluorosilane, trimethylchlorosilane, ethylphenyl)tetraphenyldisiloxane, tetraphenyl(chlorom 65 dimethyldichlorosilane, methyltrichlorosilane, triethylchlo ethyl) (fluoromethyl)disiloxane, (dichloromethyl) rosilane, diethyldichlorosilane, ethyltrichlorosilane, di-n- difluoromethyl)tetraethylcyclotrisiloxane, bis(chlorom propyldichlorosilane, triisopropylchlorosilane, isobutyl US 7,193,100 B2 15 16 trichlorosilane, dipentyldichlorosilane, nylfluorochlorostannane, diphenylfluorobromoStannane, cyclohexyltrichlorosilane, dicycloheptyldichlorosilane, and the like. Preferred tin compounds are triphenylfluo dodecyltrichlorosilane, tert-butyldimethylchlorosilane, rostannane, triphenylchlorostannane, dichlorodimethylstan octylmethyldichlorosilane, dimethyloctadecylchlorosilane, nane, and triphenylbromoStannane. Highly preferred are tin chlorodimethyl-tert-hexylsilane, benzyltrichlorosilane, compounds of the formula (CH),SnX, where n=1-3, and triphenylchlorosilane, diphenyldichlorosilane, phenyl X is, independently, fluorine, chlorine or bromine. trichlorosilane, phenyldimethylchlorosilane, diphenylmeth ylchlorosilane, phenylmethyldichlorosilane, phenyldiiso Still another type of halogenation agent that can be used propylchlorosilane, tert-butyldiphenylchlorosilane, in forming the haloaluminoxanes of this invention include a tritolylchlorosilane, ditolyldichlorosilane, trimethylbro 10 hydrocarbyl aluminum halide of the formula R"AIX, mosilane, dimethyldibromosilane, methyltribromo silane, where m=1 or 2, where X is, independently, fluorine, chlo triethylbromosilane, diisopropyldibromosilane, n-propyltri rine or bromine, and where R" is, independently, a hydro bromosilane, tert-butyltribromosilane, dicyclopentyldibro carbyl group having from one to about twenty carbon atoms. mosilane, trihexylbromosilane, cycloheptyltribromosilane, R" can be a straight chain, branched, cycloalkyl, aryl, or dioctyldibromosilane, triphenylbromosilane, diphenyldibro 15 araalkyl group. Preferably, R" is a straight chain; the straight mosilane, phenyltribromosilane, phenyldimethylbromosi chain preferably has from one to about ten carbon atoms. lane, tolyltribromosilane, phenylisopropyldibromosilane, Hydrocarbyl aluminum halides that can be used as halo naphthyltribromosilane, phenylchlorodifluorosilane, phe genation agents include, but are not limited to, methylalu nyldichlorofluorosilane, phenyldibromochlorosilane, diphe minum difluoride, dimethylaluminum fluoride, ethylalumi nylbromofluorosilane, phenylmethylchlorofluorosilane, U difluoride, diethylaluminum fluoride, diphenylchlorofluorosilane, phenylisopropylchlorofluo isopropylaluminum difluoride, diisopropylaluminum fluo rosilane, ditolylchlorofluorosilane, tolylbromodichlorosi ride, n-butylaluminum difluoride, isobutylaluminum difluo lane, and ditolylbromofluorosilane. Preferred silanes are ride, diisobutylaluminum fluoride, dipentylaluminum fluo triphenylfluorosilane, triphenylchlorosilane, and triphenyl ride, cyclohexylaluminum difluoride, diheptylaluminum bromosilane. Highly preferred are silanes of the formula 25 (CH),SiX, where n=1-3, and X is, independently, fluo fluoride, dicyclooctylaluminum fluoride, nonylalumium dif rine, chlorine or bromine; especially preferred of these is luoride, decylaluminum difluoride, diundecylaluminum trimethylfluorosilane. fluoride, phenylaluminum difluoride, diphenylaluminum Yet another type of halogenation agent that can be used in fluoride, tolylaluminum difluoride, ditolylaluminum fluo forming the haloaluminoxanes of this invention is a tin 30 ride, methylaluminum dichloride, dimethylaluminum chlo compound of the formula R'SnX, where n=1–3, X is, ride, ethylaluminum dichloride, diethylaluminum chloride, independently, fluorine, chlorine or bromine, and where R' diisopropylaluminum chloride, di-n-butylaluminum chlo is, independently, a hydrocarbyl group having from one to ride, isobutylaluminum dichloride, pentylaluminum dichlo about twenty carbon atoms. R' can be a straight chain, ride, dicyclohexylaluminum chloride, heptylaluminum branched, cycloalkyl, aryl, or araalkyl group. Preferably, R' 35 dichloride, cyclooctylaluminum chloride, dinonylalumium is an aryl group, or, more preferably, a straight chain or chloride, didecylaluminum chloride, undecylaluminum branched hydrocarbyl group. When R' is an aryl group, it chloride, phenylaluminum dichloride, diphenylaluminum preferably has from six to about twenty carbon atoms; it is chloride, tolylaluminum dichloride, ditolylaluminum chlo more preferred that the aryl group is a phenyl group. When ride, methylaluminum dibromide, dimethylaluminum bro R" is a straight chain or branched hydrocarbyl group, it 40 mide, ethylaluminum dibromide, diethylaluminum bromide, preferably has from one to about twelve carbon atoms; more isopropylaluminum dibromide, isobutylaluminum dibro preferably, R has from one to about six carbon atoms; the mide, diisobutylaluminum bromide, pentylaluminum bro most preferred straight chain or branched hydrocarbyl group mide, cyclohexylaluminum bromide, heptylaluminum is a methyl group. dibromide, cyclooctylaluminum bromide, dinonylalumium Tin compounds that can be used as halogenation agents 45 include trimethylfluorostannane, diethylfluorostannane, di bromide, decylaluminum dibromide, undecylaluminum bro n-propyldifluorostannane, tri-n-butyl-fluorostannane, dipen mide, phenylaluminum dibromide, diphenylaluminum bro tyldifluorostannane, cyclohexyltrifluorostannane, dihep mide, tolylaluminum dibromide, and ditolylaluminum bro tyldifluorostannane, trioctylfluorostannane, mide. didodecyldifluorostannane, dichlorodimethylstannane, 50 Preferred hydrocarbyl aluminum halides are methylalu trichloromethylstannane, triethylchlorostannane, diisopro minum difluoride, dimethylaluminum fluoride, methylalu pyldichlorostannane, dicyclobutyldichlorostannane, cyclo minum dichloride, dimethylaluminum chloride, methylalu pentyltrichlorostannane, trihexylchlorostannane, dicyclo minum dibromide, and dimethylaluminum bromide. More heptyldichlorostannane, octyltrichlorostannane, preferred are methylaluminum difluoride and dimethylalu dinonyldichlorostannane, decyltrichlorostannane, dimeth 55 minum fluoride. yldibromostannane, bromotriethylstannane, tribromoethyl Finally, as alluded to above, mixtures of two or more Stannane, cyclopropyltribromostannane, di-n-butyldibro halogenation agents may be used. This includes mixtures of modstannane, pentyltribromostannane, different halogenation agents within the same type, mixtures dihexyldibromostannane, trihepylbromoStannane, dicy of halogenation agents of different types, and mixtures of at clooctly dibromoStannane, dimethylchlorobromostannane, 60 least two different halogenation agents within the same type diethylfluorobromostannane, isopropylfluorodichlorostan with at least one halogenation agent of a different type. nane, fluorotriphenylstannane, difluorodiphenylstannane, Mixtures may be used in which the halogen elements in the trifluorophenylstannane, fluorotritolylstannane, chlorotriph halogenation agents are the same or different. It may be enylstannane, dichlorodiphenylstannane, trichlorophenyl advantageous to use a mixture of halogenation agents, Stannane, dichloroditolylstannane, bromotriphenylstannane, 65 depending on the desired product haloaluminoxane and the dibromodiphenylstannane, tribromophenylstannane, tolyl properties thereof (e.g., degree of halogenation, Solubility, tribromostannane, phenyldichlorobromostannane, diphe and stability). US 7,193,100 B2 17 18 Process for Producing Haloaluminoxanes nation agent, the mixture of aluminoxane and halogenation The formation of these haloaluminoxane compositions is agent is usually heated or aged. When preparing a partially generally rapid, and the by-products of the formation do not halogenated aluminoxane from a halohydrocarbon the tem appear to adversely affect the properties of the desired perature is preferably in the range of about 30° to about 80° haloaluminoxane composition. 5 C. Aging or adding heat to the process to form a partially A process for producing the new haloaluminoxanes of this halogenated aluminoxane is usually not necessary when invention comprises mixing, in an inert, anhydrous environ using a siloxane, silane, tin compound, or hydrocarbyl ment, (a) at least one aluminoxane and (b) at least one aluminum compound as the halogenation agent. halogenation agent which is While the order of addition is generally not believed to be (i) at least one halohydrocarbon of the formula RCX, 10 important, it is preferred to add the halogenation agent to the where n=1–3, X is, independently, fluorine, chlorine or aluminoxane solution, especially when the halogenation bromine, and where R is, independently, a hydrogen atom or agent is a halohydrocarbon. a hydrocarbyl group having from one to about twenty carbon As mentioned previously, the reaction of the aluminoxane atoms; and the halogenation agent can be quite rapid, and is often 15 finished in a few minutes on the laboratory scale. For O example, in a lab-scale reaction of methylaluminoxane with (ii) at least one siloxane having at least one labile halogen C.C.C.-trifluorotoluene (6-64 ppm in F NMR: 2–4 mol % atom in the molecule, wherein each halogen atom is, inde fluorine relative to aluminum) at ambient temperature, the pendently, fluorine, chlorine, or bromine; fluorine atoms of the C.C.C.-trifluorotoluene became unde O tectable by "F NMR in less than 5 minutes. At larger scales, (iii) at least one silane of the formula RSiX, where longer times may be necessary for the reaction to complete, n=1-3, X is, independently, fluorine, chlorine or bromine, due to the greater length of time needed to achieve thorough and where R' is, independently, a hydrocarbyl group having mixing of the aluminoxane and halogenation agent. It has from one to about twenty carbon atoms; been observed on the laboratory scale that siloxanes react 25 more slowly with aluminoxanes than do some of the halo O hydrocarbons. (iv) at least one tin compound of the formula RSnX, where n=1–3, X is, independently, fluorine, chlorine or As described briefly above, another process for preparing bromine, and where R' is, independently, a hydrocarbyl haloaluminoxanes of the invention comprises contacting at group having from one to about twenty carbon atoms; least one aluminum hydrocarbyl with at least one haloge 30 nation agent during the hydrolysis of the aluminum hydro O carbyl. halogenation agent which is (v) at least one hydrocarbyl aluminum halide of the (i) at least one halohydrocarbon of the formula RCX, formula R"AIX, where m=1 or 2, where X is, indepen where n=1–3, X is, independently, fluorine, chlorine or dently, fluorine, chlorine or bromine, and where R" is, bromine, and where R is, independently, a hydrogen atom or independently, a hydrocarbyl group having from one to 35 a hydrocarbyl group having from one to about twenty carbon about twenty carbon atoms; atoms; O O (vi) mixtures of any two or more of (i)–(v), (ii) at least one siloxane having at least one labile halogen atom in the molecule, wherein each halogen atom is, inde Such that a haloaluminoxane composition is formed. The 40 amount of halogen atoms is in the range of about 0.5 mole pendently, fluorine, chlorine, or bromine; % to about 15 mole % relative to aluminum atoms. O The aluminoxane and the halogenation agents are as (iii) at least one silane of the formula R', SiX, where described above for the compositions of this invention. n=1–3, X is, independently, fluorine, chlorine or bromine, Typically, the inert, anhydrous environment is an anhy 45 and where R' is, independently, a hydrocarbyl group having drous liquid hydrocarbon solvent, preferably an aromatic from one to about twenty carbon atoms; hydrocarbon. The aromatic hydrocarbon is usually one or more of benzene, toluene, Xylene, mesitylene, ethylbenzene, O diethylbenzene, 1,2,4-triethylbenzene, 1,3,5-triethylben (iv) at least one tin compound of the formula R'SnX, Zene, amylbenzene, tetrahydronaphthalene, and the like. 50 where n=1–3, X is, independently, fluorine, chlorine or Mixtures of solvents may be used. Toluene is a particularly bromine, and where R' is, independently, a hydrocarbyl preferred aromatic solvent. group having from one to about twenty carbon atoms; Even though the reaction is exothermic, cooling is not O usually necessary. Reactions of halogenation agents having (v) at least one hydrocarbyl aluminum halide of the fluorine atom(s) are more exothermic than those using 55 formula R"AIX, where m=1 or 2, where X is, indepen halogenation agents having chlorine or bromine atom(s). dently, fluorine, chlorine or bromine, and where R" is, Cooling of the reaction medium, e.g., with an ice bath or independently, a hydrocarbyl group having from one to recirculating coolant, dilution of the aluminoxane solution, about twenty carbon atoms; and dilution of the halogenation agent, are acceptable meth O ods for absorbing the heat of reaction. A preferred method is 60 dilution of the halogenation agent; such measures are less (vi) mixtures of any two or more of (i)–(v), preferred when the halogenation agent is a siloxane with Such that a haloaluminoxane composition is formed, and the labile halogen atom(s) because Such reactions tend to be less amount of halogen atoms is in the range of about 0.5 mole exothermic than those utilizing halohydrocarbons. Gener % to about 15 mole % relative to aluminum atoms. ally, to form the ionic haloaluminoxane complexes, excess 65 As described above, methods for hydrolysis of aluminum heat should be avoided. In preparations of partially haloge hydrocarbyls to form aluminoxanes are well known in the nated aluminoxanes with a halohydrocarbon as the haloge art. In the preparation of haloaluminoxane compositions US 7,193,100 B2 19 20 during the hydrolysis of aluminum hydrocarbyls, the pref The amount of halogen atoms in either the haloaluminoxane erences for halogenation agents is the same as detailed composition or in the ratio of (a) to (b) is in the range of above. about 0.5 mole % to about 15 mole % relative to aluminum Aluminum hydrocarbyls that can be used in the hydrolysis atOmS. include, but are not limited to, trimethylaluminum, eth Generally, the addition of heat is to be avoided during this yldimethylaluminum, triethylaluminum, tri-n-propylalumi process when forming a Supported ionic haloaluminoxane num, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexy complex. Operations for forming a Supported partially halo laluminoxane, tri-n-octylaluminum, tridecylaluminum, genated aluminoxane may be carried out at temperatures in tridodecylaluminum, tris(tetradecy)laluminum, tri(hexade the range of about 20 to about 80° C., and preferably at cyl)aluminum, tri(octadecyl)aluminum, triphenylaluminum, 10 temperatures in the range of about 25 to about 60° C. tritolylaluminum, and the like. Mixtures of two or more However, Suitable temperatures outside these ranges are aluminum hydrocarbyls may be used. permissible. Preferred aluminum hydrocarbyls are those in which the Optionally, these Supported haloaluminoxanes (both ionic hydrocarbyl groups are Saturated, particularly those alumi haloaluminoxane complexes and partially halogenated alu noxanes in which the hydrocarbyl groups have from one to 15 minoxanes) can be recovered from the mixture formed (e.g., about twenty carbon atoms. More preferred are aluminum by filtration), and if desired, can be washed with a liquid hydrocarbyls in which the saturated hydrocarbyl groups diluent inert to the haloaluminoxane, and also can then be have from one to about six carbon atoms. Even more dried, if desired. Thus when a catalyst Support material Such preferred are trimethylaluminum, triethylaluminum, tri-n- as silica or a porous polyolefin Support is used informing the butylaluminum, and triiso-butylaluminum. Highly preferred Supported haloaluminoxane, the liquid diluent used in the are trimethylaluminum and triethylaluminum. The most formation and the liquid diluent used in the optional Subse highly preferred aluminum hydrocarbyl is trimethylalumi quent washing of the recovered Supported haloaluminoxane l, can be an aromatic solvent. Other types of diluents such as Supported Compositions and Cocatalysts of this Invention at least one liquid paraflinic or cycloparaffinic hydrocarbon 25 or a mixture of either or both with an aromatic solvent can This invention also provides new Supported haloalumi be used for Such washing, if desired. noxanes. These Supported haloaluminoxanes include both Catalyst Support materials used in the practice of this Supported ionic haloaluminoxane complexes and Supported invention may be any finely divided inorganic Solid Support, partially halogenated aluminoxanes. Instead of isolating the Such as talc, clay, silica, alumina, silica-alumina, or mixtures haloaluminoxanes of this invention as particulate solids, the 30 thereof or a particulate resinous Support material Such as haloaluminoxanes can be deposited on a Support. spheroidal, particulate, or finely-divided polyethylene, poly To produce the new supported haloaluminoxanes of this invention involves a process comprising A) contacting a vinylchloride, polystyrene, or the like. Preferred support haloaluminoxane composition with a Support material, or B) materials are inorganic particulate solid catalyst Supports or contacting a Support material with (a) and (b). Such that a carrier materials such as magnesium halides, or the like, and Supported haloaluminoxane is formed. Here, (a) is at least 35 particularly inorganic oxides, aluminum silicates, or inor one aluminoxane and (b) is at least one halogenation agent ganic compositions containing inorganic oxides. Such as which is kaolinite, attapulgite, montmorillonite, illite, bentonite, hal (i) at least one halohydrocarbon of the formula RCX, loysite, and similar refractory clays. Inorganic oxides that where n=1–3, X is, independently, fluorine, chlorine or may be employed either alone or in combination with silica, 40 alumina, or silica-alumina are magnesia, titania, Zirconia, bromine, and where R is, independently, a hydrogen atom or and the like. The inorganic oxides may be dehydrated to a hydrocarbyl group having from one to about twenty carbon remove water. If desired, the residual surface hydroxyl atoms; groups in the inorganic Solid porous Support may be O removed by additional heating or by reaction with chemical (ii) at least one siloxane having at least one labile halogen 45 dehydrating agents such as lithium alkyl, silylchloride, alu atom in the molecule, wherein each halogen atom is, inde minum alkyls, or preferably with a haloaluminoxane of this pendently, fluorine, chlorine, or bromine; invention. As an alternative, the Support material may be chemically O dehydrated. Chemical dehydration is accomplished by slur (iii) at least one silane of the formula RSiX, where 50 rying the Support in an inert low boiling solvent such as, for n=1-3, X is, independently, fluorine, chlorine or bromine, example, heptane, in the presence of the dehydrating agent and where R' is, independently, a hydrocarbyl group having Such as for example, triethylaluminum in a moisture and from one to about twenty carbon atoms; oxygen-free atmosphere. O Preferred catalyst Support materials are inorganic oxides. (iv) at least one tin compound of the formula RSnX, 55 More preferred Supports are silica, alumina, and silica where n=1–3, X is, independently, fluorine, chlorine or alumina. Particularly preferred as the support material is bromine, and where R' is, independently, a hydrocarbyl particulate silica, especially porous particulate silica. group having from one to about twenty carbon atoms; The specific particle size, Surface area and pore Volume of O the inorganic Support material determine the amount of (v) at least one hydrocarbyl aluminum halide of the 60 inorganic Support material that is desirable to employ in formula R"AIX, where m=1 or 2, where X is, indepen preparing the catalyst compositions, as well as affecting the dently, fluorine, chlorine or bromine, and where R" is, properties of polymers formed with the aid of the catalyst independently, a hydrocarbyl group having from one to compositions. These properties are frequently taken into about twenty carbon atoms; consideration in choosing an inorganic Support material for 65 use in a particular aspect of the invention. A Suitable O inorganic Support such as silica typically will have a particle (vi) mixtures of any two or more of (i)–(v). diameter in the range of 0.1 to 600 microns, preferably in the US 7,193,100 B2 21 22 range of 0.3 to 100 microns; a surface area in the range of The new haloaluminoxanes are so effective as cocatalysts 50 to 1000 m/g, preferably in the range of 100 to 500 m/g: that they can be used with any known transition metal and a pore volume in the range of about 0.3 to 5.0 cc/g, catalyst compound in which the transition metal thereof is a preferably in the range of 0.5 to 3.5 cc/g. It is also desirable Group 3 to 10 transition metal of the Periodic Table includ to employ supports with pore diameters in the range of about ing compounds of a metal of the lanthanide or actinide 50 to about 500 angstroms. To ensure its use in dehydrated series. The Periodic Table referred to herein is that appearing form the support material may be heat treated at 100–1000 on page 27 of the Feb. 4, 1985 issue of Chemical & C. for a period of 1-100 hours, preferably 3–24 hours. The Engineering News. Suitable catalyst compounds can also be treatment may be carried out in a vacuum or while purging described as d- and f-block metal compounds. See, for with a dry inert gas Such as nitrogen. 10 example, the Periodic Table appearing on page 225 of Moeller, et al., Chemistry, Second Edition, Academic Press, Transition Metal Catalyst Compounds copyright 1984. As regards the metal constituent, preferred Also provided by this invention are new polymerization are compounds of Fe, Co, Ni, Pd, and V. More preferred are catalyst compositions in which the cocatalyst used is a new compounds of the metals of Groups 4–6 (Ti, Zr, Hf, V, Nb, haloaluminoxane of this invention. These new polymeriza 15 Ta, Cr, Mo, and W), and most preferred are the Group 4 tion catalyst compositions can be used in Solution polymer metals, especially titanium, Zirconium, or hafnium. izations or they can be used in Supported form in slurry or Thus the transition metal catalyst compounds used in this gas phase polymerizations. These catalytic systems can be invention can be one or more of any Ziegler-Natta catalyst used for the polymerization of olefins and/or other mono compound, any metallocene, any compound of constrained mers which on polymerization result in formation of poly geometry, any late transition metal complex, or any other merized ethylene linkages. transition metal compound or complex reported in the Typically unsupported catalysts are formed by mixing or literature or otherwise generally known in the art to be an otherwise interacting a haloaluminoxane of this invention effective catalyst compound when Suitably activated, includ with the transition metal catalyst compound in an inert ing mixtures of at least two different types of such transition aromatic Solvent. The resultant unsupported reaction prod 25 metal compounds or complexes, such as for example a uct, which is an embodiment of this invention and an active mixture of a metallocene and a Ziegler-Natta olefin poly olefin polymerization catalyst, can be formed using various merization catalyst compound. proportions of these components. For example, the molar Among the transition metal compounds of the metals of ratio of aluminum to transition metal can be in the range of Groups 3, 4, 5, and 6 which can be used as the transition about 20:1 to about 2000:1, and preferably is in the range of 30 metal component of the catalyst compositions of and used in about 20:1 to about 500:1. this invention are the compounds of Such metals as scan One type of the polymerization catalysts of this invention dium, titanium, zirconium, hafnium, cerium, vanadium, nio is an unsupported reaction product between (i) at least one bium, tantalum, chromium, molybdenum, tungsten, thorium catalyst compound or complex of a transition metal of and uranium often referred to as Ziegler-Natta type olefin Groups 3 to 10 of the Periodic Table including the lanthanide 35 polymerization catalysts. Preferred compounds of this type and actinide series, and (ii) at least one haloaluminoxane of can be represented by the formula MX (OR), in which M this invention. One way of producing these new catalyst represents the transition metal atom or a transition metal compositions is to form a catalyst in solution by bringing atom cation containing one or two oxygen atoms such as together either in a polymerization reactor or Zone or in a Vanadyl, Zirconyl, or uranyl. X represents a halogen atom, separate vessel, at least (i) a catalyst compound or complex 40 OR represents a hydrocarbyloxy group having up to about of a transition metal of Groups 3 to 10 of the Periodic Table 18 carbon atoms, preferably up to about 8 carbon atoms, and including the lanthanide and actinide series, (ii) a haloalu more preferably alkyl of up to about 4 carbon atoms, such minoxane of this invention, and (iii) a polymerization sol as an alkyl, cycloalkyl, cycloalkylalkyl, aryl, or aralkyl, vent. These components can be fed separately in any order group and n and m are positive integers except that either or any two of them can be premixed and fed as a mixture, 45 one of them (but not both) can be zero, and where n+m is the with the other component being fed before, during or after valence state of the transition metal. Illustrative of some of the feeding of Such mixture to the polymerization reactor or the transition metal compounds which can he used are, for Zone or to the separate vessel. If a separate vessel is used, the example, titanium dibromide, titanium tribromide, titanium catalyst formed therein is promptly delivered into the poly tetrabromide, titanium dichloride, titanium trichloride, tita merization reactor or Zone. In all cases the customary inert 50 nium tetrachloride, titanium trifluoride, titanium tetrafluo atmospheres and anhydrous polymerization conditions ride, titanium diiodide, titanium triiodide, titanium tetraio should be observed. The resultant mixture formed in this dide, Zirconium dibromide, Zirconium tribromide, Zirconium operation is a solution of a catalyst of this invention in which tetrabromide, zirconium dichloride, zirconium trichloride, polymerization of the monomer or combination of mono Zirconium tetrachloride, Zirconium tetrafluoride, Zirconium mers is carried out. 55 tetraiodide, hafnium tetrafluoride, hafnium tetrachloride, For the ionic haloaluminoxane complexes, the ionic com hafnium tetrabromide, hafnium tetraiodide, hafnium trichlo plex can be formed and then mixed with the transition metal ride, hafnium tribromide, hafnium triiodide, vanadium catalyst compound, or prepared in situ in the presence of the dichloride, vanadium trichloride, vanadium tetrachloride, transition metal catalyst compound. Vanadium tetrabromide, Vanadium tribromide, Vanadium For the partially halogenated aluminoxane, the partially 60 dibromide, Vanadium trifluoride, Vanadium tetrafluoride, halogenated aluminoxane is normally and preferably pre Vanadium pentafluoride, Vanadium diiodide, Vanadium tri pared and then mixed with the transition metal catalyst iodide, Vanadium tetraiodide, Vanadyl chloride, Vanadyl compound. Alternatively, the partially halogenated alumi bromide, niobium pentabromide, niobium pentachloride, noxane can be formed in the presence of the transition metal niobium pentafluoride, tantalum pentabromide, tantalum catalyst compound, because by-products of the preparation 65 pentachloride, tantalum pentafluoride, chromous bromide, of the partially halogenated aluminoxane generally do not chromic bromide, chromous chloride, chromic chloride, interfere with the polymerization. chromous fluoride, chromic fluoride, molybdenum dibro US 7,193,100 B2 23 24 mide, molybdenum tribromide, molybdenum tetrabromide, Metallocene structures in this specification are to be molybdenum dichloride, molybdenum trichloride, molybde interpreted broadly, and include structures containing 1, 2, 3 num tetrachloride, molybdenum pentachloride, molybde or 4 Cp or substituted Cp rings. Thus metallocenes suitable num hexafluoride, lanthanum trichloride, cerous fluoride, for use in this invention can be represented by Formula (I): cerous chloride, cerous bromide, cerous iodide, ceric fluo ride, uranium trichloride, uranium tetrachloride, uranium BCpMXY (I) tribromide, uranium tetrabromide, thorium tetrachloride, where Cp, independently in each occurrence, is a cyclopen thorium tetrabromide, and the like. Among the hydrocarby tadienyl-moiety-containing group which typically has in the loxides and mixed halide/hydrocarbyloxides of the transi range of 5 to about 24 carbon atoms; B is a bridging group tion metals are Ti(OCH), Ti(OCH)Cl. Ti(OCH).Br. 10 or ansa group that links two Cp groups together or alterna Ti(OCH)I, Ti(OCHs), Ti(OCH)Cl. Ti(OCH)Cl. tively carries an alternate coordinating group Such as alky Ti(OCHs).Br. Ti(OCH)Br, Ti(OCH)I, Ti(OCH.) laminosilylalkyl, silylamido, alkoxy, siloxy, aminosilyla Cl, Ti(O-iso-CH2)C1, Ti(O-iso-CH2)C1, Ti(O-iso lkyl, or analogous monodentate hetero atom electron CH2)Cl. Ti(OCH) Cl, Ti(OCH)Cl. Ti(OCH)Cl. donating groups; M is a d- or f-block metal atom; each X and Ti(OCHs)Cl. Ti(O-p-CHCH)Cl. Ti(OCH)Cl. 15 each Y is, independently, a group that is bonded to the d- or Ti(OCH)Cl. Ti(O-cyclo-CH)Cl. Ti(OCH2).Br. f-block metal atom; a is 0 or 1; b is a whole integer from 1 Ti(O-2-Ethex), Ti(OCH2)C1, Ti(OCH).Br. to 3 (preferably 2); c is at least 2; d is 0 or 1. The sum of b, Zr(OCHs), Zr(OCHo), Zr(OCH), ZrCl(OCHs), c, and d is sufficient to form a stable compound, and often ZrCl(OCHs), ZrCl(OCHs), ZrCl(OCH), ZrCl is the coordination number of the d- or f-block metal atom. (OCH), ZrCl(OCH), Hf(OCH), Hf(OCH)Cl. Cp is, independently, a cyclopentadienyl, indenyl, fluo VO(OCH), VOCl(OCH), VOCl(OCH), VOC1 renyl or related group that can U-bond to the metal, or a (OCH), VOCl(O-iso-CH4), VOCl(OCH), VOCl, hydrocarbyl-, halo-, halohydrocarbyl-, hydrocarbylmetal (OCH), VOC1(OCH), VOC1(O-iso-CH), VOBr loid-, and/or halohydrocarbylmetalloid-substituted deriva (OCH), VOBr(OCH), VOBr(O-iso-CH), VOBr, tive thereof. Cp typically contains up to 75 non-hydrogen (OCH), VOBr.(O-iso-CH2), VOBr,(OCH), VOBr.(O- 25 iso-CH), VOI(OCH), VOI(OCHs), VOI(OCH), atoms. B., if present, is typically a silylene (—SiR ). VOI(O-cyclo-CHs), VOI(OCH), VOI(O-cyclo benzo (CH4), Substituted benzo, methylene (-CH2—), CH), Cr(O-iso-CH), Mo(OCHs), and the like. Car substituted methylene, ethylene ( CHCH ), or substi boxylic acid salts and various chelates of the transition metal tuted ethylene bridge. M is preferably a metal atom of can also be used but in general are less preferred. A few 30 Groups 4–6, and most preferably is a Group 4 metal atom, non-limiting examples of Such salts and chelates include especially hafnium, and most especially Zirconium. X can be Zirconyl acetate, uranyl butyrate, chromium acetate, chro a divalent substituent such as an alkylidene group, a cyclo mium(III) oxy-2-ethylhexanoate, chromium(III) 2-ethylhex metallated hydrocarbyl group, or any other divalent chelat anoate, chromium(III) dichloroethylhexanoate, chromium ing ligand, two loci of which are singly bonded to M to form (II) 2-ethylhexanoate, titanium(IV) 2-ethylhexanoate, bis(2. 35 a cyclic moiety which includes M as a member. Each X, and 4-pentanedionate)titanium oxide, bis(2.4-pentanedionate) if present Y, can be, independently in each occurrence, a titanium dichloride, bis(2.4-pentanedionate)titanium halogen atom, a hydrocarbyl group (alkyl, cycloalkyl, alk dibutoxide, Vanadyl acetylacetonate, chromium acetylaceto enyl, cycloalkenyl, aryl, aralkyl, etc.), hydrocarbyloxy, nate, niobium acetylacetonate, Zirconyl acetylacetonate, (alkoxy, aryloxy, etc.) siloxy, amino or Substituted amino, chromium octylacetoacetate, and the like. Also, transition 40 hydride, acyloxy, triflate, and similar univalent groups that metal alkyls such as tetramethyl titanium, methyl titanium form stable metallocenes. The sum of b, c, and d is a whole trichloride, tetraethyl Zirconium, tetraphenyl titanium, and number, and is often from 3–5. When M is a Group 4 metal the like can be used. or an actinide metal, and b is 2, the Sum of c and d is 2, c Preferred transition metal compounds of the well-known being at least 1. When M is a Group 3 or Lanthanide metal, Ziegler-Natta catalyst compounds are those of the Group 4 45 and b is 2. c is 1 and d is zero. When M is a Group 5 metal, metals, including the alkoxides, halides, and mixed halide/ and b is 2, the Sum of c and d is 3, c being at least 2. alkoxide compounds. More preferred are TiCl, ZrC1, Also useful in this invention are compounds analogous to HfCl4, and TiCl, with TiCl, being most preferred. Such those of Formula (I) where one or more of the Cp groups are more preferred compounds can be used in chelated form in replaced by cyclic unsaturated charged groups isoelectronic order to facilitate solubility. Suitable chelated catalysts of 50 with Cp, such as borabenzene or substituted borabenzene, this type are known and reported in the literature. azaborole or substituted azaborole, and various other iso Metallocenes are another broad class of olefin polymer electronic Cp analogs. See for example Krishnamurti, et al., ization catalyst compounds with which the haloaluminox U.S. Pat. Nos. 5,554,775 and 5,756,611. anes of this invention can be used in forming novel highly In one preferred group of metallocenes, b is 2, i.e., there effective catalysts of this invention. As used herein, the term 55 are two cyclopentadienyl-moiety containing groups in the "metallocene' includes metal derivatives which contain at molecule, and these two groups can be the same or they can least one cyclopentadienyl moiety. Suitable metallocenes are be different from each other. well known in the art and include the metallocenes of Another Sub-group of useful metallocenes which can be Groups 3, 4, 5, 6, lanthanide and actinide metals, for used in the practice of this invention are metallocenes of the example, the metallocenes which are described in U.S. Pat. 60 type described in WO 98/32776 published Jul. 30, 1998. Nos. 2,864,843; 2,983,740; 4,665,046; 4,874,880; 4,892, These metallocenes are characterized in that one or more 851; 4,931417; 4,952,713; 5,017,714; 5,026,798; 5,036, cyclopentadienyl groups in the metallocene are substituted 034; 5,064,802; 5,081,231; 5,145,819; 5,162,278: 5,245, by one or more polyatomic groups attached via a N, O, S, or 019; 5,268,495; 5,276,208; 5,304,523: 5,324,800; 5,329, Patom or by a carbon-to-carbon double bond. Examples of 031: 5,329,033; 5,330,948,5,347,025; 5,347,026; and 5,347, 65 Such substituents on the cyclopentadienyl ring include 752, whose teachings with respect to Such metallocenes are OR, SR, NR, -CH=, CR=, and - PR, where incorporated herein by reference. R can be the same or different and is a substituted or US 7,193,100 B2 25 26 unsubstituted C-C hydrocarbyl group, a tri-C-Cs hydro bis(diethylcyclopentadienyl)Zirconium dimethyl: carbylsilyl group, atri-C-Cs hydrocarbyloxysilyl group, a bis(methyl-n-butylcyclopentadienyl)Zirconium dimethyl; mixed C-Cs hydrocarbyl and C-Cs hydrocarbyloxysilyl bis(n-propylcyclopentadienyl)Zirconium dimethyl; group, a tri-C-Cs hydrocarbylgermyl group, a tri-C-Cs bis(2-propylcyclopentadienyl)Zirconium dimethyl; hydrocarbyloxygermyl group, or a mixed C-Cs hydrocar bis(methylethylcyclopentadienyl)Zirconium dimethyl: byl and C-Cs hydrocarbyloxygermyl group. bis(indenyl)Zirconium dimethyl; Examples of metallocenes to which this invention is bis(methylindenyl)Zirconium dimethyl; applicable include Such compounds as: dimethylsilylenebis(indenyl)Zirconium dimethyl: bis(cyclopentadienyl)Zirconium dimethyl; dimethylsilylenebis(2-methylindenyl)Zirconium dimethyl; bis(cyclopentadienyl)Zirconium dichloride; bis(cyclopenta 10 dimethylsilylenebis(2-ethylindenyl)Zirconium dimethyl: dienyl)Zirconium monomethylmonochloride; dimethylsilylenebis(2-methyl-4-phenylindenyl)Zirconium bis(cyclopentadienyl)titanium dichloride; dimethyl: bis(cyclopentadienyl)titanium difluoride; 1.2-ethylenebis(indenyl)Zirconium dimethyl: cyclopentadienylzirconium tri-(2-ethylhexanoate); 1.2-ethylenebis(methylindenyl)Zirconium dimethyl; bis(cyclopentadienyl)Zirconium hydrogen chloride; 15 2.2-propylidenebis(cyclopentadienyl)(fluorenyl)Zirconium bis(cyclopentadienyl)hafnium dichloride; dimethyl: racemic and meso dimethylsilanylene-bis(methylcyclopen dimethylsilylenebis(6-phenylindenyl)Zirconium dimethyl; tadienyl)hafnium dichloride; bis(methylindenyl)Zirconium benzyl methyl: racemic dimethylsilanylene-bis(indenyl)hafnium dichloride; ethylenebis 2-(tert-butyldimethylsiloxy)-1-indenylzirco racemic ethylene-bis(indenyl)Zirconium dichloride; nium dimethyl; (m-indenyl)hafnium trichloride; dimethylsilylenebis(indenyl)chlorozirconium methyl: (m-CMes)hafnium trichloride; 5-(cyclopentadienyl)-5-(9-fluorenyl)1-hexene Zirconium racemic dimethylsilanylene-bis(indenyl)thorium dichloride; dimethyl: racemic dimethylsilanylene-bis(4,7-dimethyl-1-indenyl)Zir dimethylsilylenebis(2-methylindenyl)hafnium dimethyl: conium dichloride; 25 dimethylsilylenebis(2-ethylindenyl)hafnium dimethyl; racemic dimethyl-silanylene-bis(indenyl)uranium dichlo dimethylsilylenebis(2-methyl-4-phenylindenyl)hafnium ride; dimethyl: racemic dimethylsilanylene-bis(2,3,5-trimethyl-1-cyclopen 2.2-propylidenebis(cyclopentadienyl)(fluorenyl)hafnium tadienyl)Zirconium dichloride; dimethyl: racemic dimethyl-silanylene(3-methylcyclopentadienyl) 30 bis(9-fluorenyl)(methyl)(vinyl)silane Zirconium dimethyl, hafnium dichloride; bis(9-fluorenyl)(methyl)(prop-2-enyl)silane Zirconium dim racemic dimethylsilanylene-bis(1-(2-methyl-4-ethyl)inde ethyl, nyl)Zirconium dichloride; bis(9-fluorenyl)(methyl)(but-3-enyl)silane zirconium dim racemic dimethylsilanylene-bis(2-methyl-4,5,6,7-tetrahy ethyl, dro-1-indenyl)Zirconium dichloride; 35 bis(9-fluorenyl)(methyl)(hex-5-enyl)silane Zirconium dim bis(pentamethylcyclopentadienyl)thorium dichloride; ethyl, bis(pentamethylcyclopentadienyl)uranium dichloride; bis(9-fluorenyl)(methyl)(oct-7-enyl)silane zirconium dim (tert-butylamido)dimethyl(tetramethyl-m-cyclopentadi ethyl, enyl)silanetitanium dichloride; (cyclopentadienyl)(1-allylindenyl)Zirconium dimethyl, (tert-butylamido)dimethyl(tetramethyl-m-cyclopentadi 40 bis(1-allylindenyl)Zirconium dimethyl, enyl)silane chromium dichloride; (9-(prop-2-enyl)fluorenyl)(cyclopentadienyl)Zirconium (tert-butylamido)dimethyl(-m-cyclopentadienyl)silanetita dimethyl, nium dichloride; (9-(prop-2-enyl)fluorenyl)(pentamethylcyclopentadienyl) (tert-butylamido)dimethyl(tetramethyl-m-cyclopentadi Zirconium dimethyl, enyl)silanemethyltitanium bromide: 45 bis(9-(prop-2-enyl)fluorenyl)Zirconium dimethyl, (tert-butylamido)(tetramethyl-m-cyclopentadienyl)-1,2- (9-(cyclopent-2-enyl)fluorenyl)(cyclopentadienyl)Zirco ethanediyluranium dichloride; nium dimethyl, (tert-butylamido)(tetramethyl-m-cyclopentadienyl)-1,2- bis(9-(cyclopent-2-enyl)(fluorenyl)Zirconium dimethyl, ethanediyltitanium dichloride; 5-(2-methylcyclopentadienyl)-5 (9-fluorenyl)-1-hexene Zir (methylamido)(tetramethyl-m-cyclopentadienyl)-1,2- 50 conium dimethyl, ethanediylcerium dichloride; 1-(9-fluorenyl)-1-(cyclopentadienyl)-1-(but-3-enyl)-1-(me (methylamido)(tetramethyl-m-cyclopentadienyl)-1,2- thyl)methane Zirconium dimethyl, ethanediyltitanium dichloride; 5-(fluorenyl)-5-(cyclopentadienyl)-1-hexene hafnium dim (ethylamido)(tetramethyl-m-cyclopentadienyl)methyleneti ethyl, tanium dichloride; 55 (9-fluorenyl)(1-allylindenyl)dimethylsilane zirconium dim (tert-butylamido)dibenzyl (tetramethyl-m-cyclopentadi ethyl, enyl)-silanebenzylvanadium chloride; 1-(2,7-di(alpha-methylvinyl)(9-fluorenyl)-1-(cyclopentadi (benzylamido)dimethyl(indenyl)silanetitanium dichloride; enyl)-1,1-dimethylmethane Zirconium dimethyl, (phenylphosphido)dimethyl(tetramethyl-m-cyclopentadi 1-(2,7-di(cyclohex-1-enyl)(9-fluorenyl))-1-(cyclopentadi enyl)silanebenzyltitanium chloride; 60 enyl)-1,1-methane Zirconium dimethyl, rac-dimethylsilylbis(2-methyl-1-indenyl)Zirconium dim 5-(cyclopentadienyl)-5-(9-fluorenyl)-1-hexene titanium ethyl: dimethyl, rac-ethylenebis(1-indenyl)Zirconium dimethyl: 5-(cyclopentadienyl)-5-(9-fluorenyl)1-hexene titanium dim bis(methylcyclopentadienyl)titanium dimethyl; ethyl, bis(methylcyclopentadienyl)Zirconium dimethyl; 65 bis(9-fluorenyl)(methyl)(vinyl)silane titanium dimethyl, bis(n-butylcyclopentadienyl)Zirconium dimethyl; bis(9-fluorenyl)(methyl)(prop-2-enyl)silane titanium dim bis(dimethylcyclopentadienyl)Zirconium dimethyl; ethyl, US 7,193,100 B2 27 28 bis(9-fluorenyl)(methyl)(but-3-enyl)silane titanium dim fluoro C.-diimine-based nickel and palladium complexes ethyl, such as described by Johnson et al. in J. Am. Chem. Soc., bis(9-fluorenyl)(methyl)(hex-5-enyl)silane titanium dim 1995, 117, 6414, see also Brown et al. WO97/17380; nickel ethyl, complexes such as described by Johnson et al. in U.S. Pat. bis(9-fluorenyl)(methyl)(oct-7-enyl)silane titanium dim No. 5,714,556: cobalt(III)cyclopentadienyl catalytic sys ethyl, tems such as described by Schmidt et al. in J. Am. Chem. (cyclopentadienyl)(1-allylindenyl) titanium dimethyl, Soc., 1985, 107, 1443, and by Brookhart et al. in Macro bis(1-allylindenyl)titanium dimethyl, molecules, 1995, 28, 5378; anfluoro phosphorus, oxygen (9-(prop-2-enyl)fluorenyl)(cyclopentadienyl)hafnium dim donors ligated to nickel(II) such as described by Klabunde ethyl, 10 in U.S. Pat. Nos. 4,716,205, 4,906,754, 5,030,606, and (9-(prop-2-enyl)fluorenyl)(pentamethylcyclopentadienyl) 5,175.326; Group 8–10 transition metal complexes coordi hafnium dimethyl, nated with a bidentate ligand such as described in WO bis(9-(prop-2-enyl)fluorenyl) hafnium dimethyl, 98/40374; transition metal complexes with bidentate ligands (9-(cyclopent-2-enyl)fluorenyl)(cyclopentadienyl) hafnium containing pyridine or quinoline moieties such as described dimethyl, 15 in U.S. Pat. No. 5,637,660; quinolinoxy or pyridinoxy bis(9-(cyclopent-2-enyl)(fluorenyl)hafnium dimethyl, substituted Group 4 transition metal trihalides such as 5-(2-methylcyclopentadienyl)-5 (9-fluorenyl)-1-hexene described in U.S. Pat. No. 6,020.493; nickel complexes such hafnium dimethyl, as described by bis(ylide)nickel complexes such as 5-(fluorenyl)-5-(cyclopentadienyl)-1-octene hafnium dim described by Starzewski et al. in Angew. Chem. Int. Ed. ethyl, Engl., 1987, 26, 63, and U.S. Pat. No. 4,691,036; neutral N, (9-fluorenyl)(1-allylindenyl)dimethylsilane hafnium dim O, P, or S donor ligands in combination with a nickel(0) ethyl. compound and an acid such as described in WO 97/02298; (tert-butylamido)dimethyl(tetramethylcyclopentadienyl)si aminobis(imino)phosphorane nickel catalysts such as lane titanium (1,3-pentadiene); described by Fink et al. in U.S. Pat. No. 4,724.273. (cyclopentadienyl)(9-fluorenyl)diphenylmethane Zirconium 25 Illustrative, non-limiting additional examples of various dimethyl: types of transition metal compounds that can be employed (cyclopentadienyl)(9-fluorenyl)diphenylmethane hafnium include the following: dimethyl: 2,6-bis-1-(1-methylphenylimino)ethylpyridine iron II dimethylsilanylene-bis(indenyl) thorium dimethyl: chloride; dimethylsilanylene-bis(4,7-dimethyl-1-indenyl)Zirconium 30 2,6-bis 1-(1-ethylphenylimino)ethylpyridine iron IIIchlo dimethyl: ride; dimethylsilanylene-bis(indenyl) uranium dimethyl: 2,6-bis 1-(1-isopropylphenylimino)ethylpyridine iron III dimethylsilanylene-bis(2-methyl-4-ethyl-1-indenyl)Zirco chloride; nium dimethyl; 2,6-bis-(1-(2-methylphenylimino)ethyl)pyridine iron(II) dimethylsilanylene-bis(2-methyl-4,5,6,7-tetrahydro-1-inde 35 chloride; nyl)Zirconium dimethyl; N,N'-ditrimethylsilyl)benzamidinato copper(II): (tert-butylamido)dimethyl(tetramethyl-m-cyclopentadi tridentate Schiffbase complexes of cobalt and iron described enyl)silane titanium dimethyl; by Mashima in Shokubai 1999, vol. 41, p. 58: (tert-butylamido)dimethyl(tetramethyl-m-cyclopentadi nickel compounds of the type described in U.S. Pat. No. enyl)silane chromium dimethyl; 40 5,880,323; (tert-butylamido)dimethyl(tetramethyl-m-cyclopentadi nickel(II)acetylacetonate; enyl)silane titanium dimethyl; bis(acetonitrile)dichloro palladium(II): (phenylphosphido)dimethyl(tetramethyl-m-cyclopentadi bis(acetonitrile)bis(tetrafluoroborate)palladium(II): enyl)silane titanium dimethyl; and (2,2'-bipyridine)dichloro palladium(II): dimethylsilanediylbis(indenyl)scandium methyl. 45 bis(cyclooctadienyl) nickel(0); palladium(II)acetylacetonate; In many cases the metallocenes such as referred to above bis(salicylaldiminato) complexes of the type described by will exist as racemic mixtures, but pure enantiomeric forms or mixtures enriched in a given enantiomeric form can be Matsui et al. in Chemistry Letters 2000, pp. 554–555; used. 50 cobalt dioctoate; Other organometallic catalytic compounds with which the cobaltocene; haloaluminoxanes of this invention can be used in forming (cyclopentadienyl)(triphenylphosphino)cobalt(II) diiodide: novel catalysts of this invention are the late transition metal and catalyst described, for example, in U.S. Pat. No. 5,516.739 nickel compounds of the type described in JP 09-272709. to Barborak, et al.; U.S. Pat. No. 5,561,216 to Barborak, et 55 Preferred transition metal compounds which can be used al.; U.S. Pat. No. 5,866,663 to Brookhart, et al; U.S. Pat. No. in forming the catalysts of this invention are transition metal 5,880,241 to Brookhart, etal; and U.S. Pat. No. 6,114,483 to compounds which can be represented by the formula: Coughlin, et al. Such catalysts are sometimes referred to MX,Y, herein collectively as “a Brookhart-type late transition metal catalyst compound or complex”. 60 where M is a transition metal of Group 4 to 8 including the Other transition metal catalyst compounds and catalyst lanthanide series and actinide series, and preferably of complexes that can be used in the practice of this invention Group 4 to 6, of the Periodic Table, and Y is, independently, include catfluoro nickel, palladium, iron, and cobalt com a halide or pseudohalide, n is the Valence of M, and m is an plexes containing dimine and bisoxazoline ligands such as integer of from 0 to n-1. Of the pseudohalides, preferred are described in Johnson et al. WO 96/23010; palladium and 65 alkoxide or oxyhalide groups. Pseudohalides, which is a nickel catalysts containing selected bidentate phosphorus term of art, refers to anfluoro moieties which as salt-like containing ligands such as described in EP 381,495; cat anions which are non-halogenides. Non-limiting examples US 7,193,100 B2 29 30 of Suitable pseudohalide groups are oxyhalide groups, itself a liquid, the Supported catalyst of this invention can be hydrocarbyloxy groups (-OR groups such as alkoxy, ary made for example by contacting or mixing the Supported loxy, cycloalkoxy, arylalkoxy, etc.), amido groups (—NR), haloaluminoxane of this invention with the liquid transition hydrocarbylthio groups (—SR groups), and the like. Most metal catalyst compound or complex. preferred are compounds of the above formula wherein M is One method involves mixing a transition metal catalyst a Group 4 metal. Non-limiting examples of Suitable transi compound with a catalyst Support and then contacting the tion metal compounds include, for example, transition metal resultant Supported transition metal catalyst compound with halides and oxyhalides such as titanium dibromide, titanium a haloaluminoxane of this invention. This less preferred tribromide, titanium tetrabromide, titanium dichloride, tita method for forming the catalyst composition comprises first nium trichloride, titanium tetrachloride, titanium trifluoride, 10 contacting the transition metal catalyst compound and the titanium tetrafluoride, titanium diiodide, titanium tetraio catalyst Support material, preferably in the presence of a dide, Zirconium dibromide, Zirconium tribromide, Zirconium Solvent or diluent. The Supported transition metal catalyst tetrabromide, zirconium dichloride, zirconium trichloride, compound may then be mixed with the haloaluminoxane. Zirconium tetrachloride, Zirconium tetrafluoride, Zirconium Instead, the ionic haloaluminoxane complex or partially tetraiodide, hafnium tetrafluoride, hafnium tetrachloride, 15 halogenated aluminoxane can be formed in situ by mixing hafnium tetrabromide, hafnium tetraiodide, hafnium trichlo the Supported transition metal catalyst compound with the ride, hafnium tribromide, hafnium triiodide, hafnium oxy aluminoxane and the halogenation agent. The order in which chloride, Vanadium dichloride, Vanadium trichloride, vana the aluminoxane and the halogenation agent are mixed with dium tetrachloride, Vanadium trifluoride, vanadium the Supported transition metal catalyst compound is not tetrafluoride, Vanadium pentafluoride, Vanadium triiodide, important. It is not preferred to make the partially haloge Vanadium oxytrichloride, Vanadium oxytribromide, niobium nated aluminoxane in the presence of the Supported transi pentabromide, niobium pentachloride, niobium pentafluo tion metal catalyst compound. ride, tantalum pentabromide, tantalum pentachloride, tanta Another method involves mixing together a transition lum pentafluoride, chromous bromide, chromic bromide, metal catalyst compound and a haloaluminoxane of this chromous chloride, chromic chloride, chromous fluoride, 25 invention and then contacting the resultant mixture with a chromic fluoride, molybdenum dibromide, molybdenum tri catalyst Support. In this method of forming the catalyst bromide, molybdenum tetrabromide, molybdenum dichlo composition, the transition metal compound and a haloalu ride, molybdenum trichloride, molybdenum tetrachloride, minoxane of this invention are combined in a first step in a molybdenum pentachloride, molybdenum hexafluoride, lan Suitable solvent such as an aromatic solvent to produce a thanum trichloride, cerous fluoride, cerous chloride, cerous 30 solution of the reaction product. In a variation of this bromide, cerous iodide, ceric fluoride, uranium trichloride, method, the ionic haloaluminoxane complex or partially uranium tetrachloride, uranium tribromide, uranium tetra halogenated aluminoxane can be formed in the presence of bromide, thorium tetrachloride, thorium tetrabromide, and the transition metal compound. Holding times to allow for the like. Among Suitable alkoxides and mixed halide/alkox the completion of the reaction may range from about 10 ides of the transition metals are Ti(OCH), Ti(OCH), 35 seconds to about 60 minutes depending on the reaction Ti(OCHs)Cl. Ti(OCHs)Cl. Ti(O-iso-CH2)C1, variables. The solution produced by combining the transi Ti(OCH)Cl. Ti(OCH2)Cl. Ti(O-iso-CH2)Cl. tion metal compound and haloaluminoxane of this invention Ti(OCHs).Br. Zr(OCHs), Zr(OCHo), Zr(OCH), or by forming the haloaluminoxane in the presence of the ZrCl(OCHs), ZrCl(OCH), Hf(OCH), Hf(OCH) transition metal compound is then contacted with the Sup Cl, VO(OCH) Cr(O-iso-CH), Mo(OCH), and the 40 port. The method of contact may vary, but it is preferred that like. Other transition metal compounds which may be used the Support be added to the catalyst solution with vigorous include amides such as Ti(NMe), Zr(NMe), Ti(NEt), stirring. Contact times may vary from about 10 seconds to Zr(NEt), and Ti(NBu), carboxylic acid salts such as about 60 minutes or longer. The solvent can then be titanium oxalate, cobalt acetate, chromium acetate, nickel removed, typically by applying a vacuum. formate, thallium oxalate, and uranyl formate. Among the 45 Still another method, a preferred method of forming the more preferred transition metal compounds are the halides, catalyst compositions of this invention, involves depositing oxyhalides, alkoxides, and mixed halide-alkoxides of the the haloaluminoxane of this invention on a catalyst Support Group 4 to 6 metals, and more particularly of the metals of and then mixing the resultant Supported aluminoxane with Groups 4 and 5. Among especially preferred transition metal the transition metal catalyst compound. This method com compounds are the trivalent or tetravalent Group 4 metal 50 prises contacting a haloaluminoxane of this invention and halides, particularly the chlorides, and the Vanadium oxy catalyst Support material for example as a slurry in a Suitable halides, particularly vanadium oxytrichloride. The Periodic inert diluent, prior to mixing with the transition metal Table referred to is that appearing on page 27 of the Feb. 4, catalyst compound. For the partially halogenated aluminox 1985 issue of Chemical & Engineering News. anes and the ionic haloaluminoxane complexes, the alumi Another type of these new catalyst compositions is a 55 noxane and the halogenation agent may be reacted prior to Supported catalyst composition of this invention. These contact with the catalyst Support material; alternatively, compositions are reaction products between (i) a catalyst again for the partially halogenated aluminoxanes and the compound or complex of a transition metal of Groups 3 to ionic haloaluminoxane complexes, the aluminoxane may be 10 of the Periodic Table including the lanthanide and contacted with the catalyst support material followed by the actinide series, (ii) a haloaluminoxane of this invention, and 60 reaction of the aluminoxane and the halogenation agent. As (iii) catalyst Support or carrier material. These catalyst in their respective syntheses, heat or aging is usually compositions can be formed in various ways. Each method required to make the partially halogenated aluminoxane, and is typically conducted in the presence of an inert liquid is avoided when making ionic haloaluminoxane complexes. medium which can be a liquid transition metal compound or The resultant Supported haloaluminoxane of this inven complex, but which typically is an inert liquid diluent Such 65 tion preferably after recovery and washing with an inert as a paraflinic, cycloparaflinic or aromatic hydrocarbon. solvent or diluent is contacted with or in a solution of the When the transition metal catalyst compound or complex is transition metal compound in a suitable anhydrous inert US 7,193,100 B2 31 32 solvent, preferably with agitation. In this way the haloalu moisture-free, oxygen-free environment such as argon, minoxane and the transition metal compound can interact to nitrogen or helium because of the sensitivity of the catalyst produce an active Supported catalyst composition. components to moisture and oxygen. Suitable solvents and/or diluents include, but are not In one method of forming a modified Supported catalyst, necessarily limited to, Straight and branched-chain hydro the haloaluminoxane of this invention and the modifier are carbons such as isobutane, butane, pentane, hexane, heptane, combined in a first step in a Suitable solvent such as an octane and the like; cyclic and alicyclic hydrocarbons such aromatic solvent to produce a solution or slurry. The tran as cyclohexane, cycloheptane, methylcyclohexane, methyl sition metal compound is then added to this solution. When cyclopentane and the like; and aromatic and alkyl-substi the haloaluminoxane is a partially halogenated aluminoxane, tuted aromatic compounds Such as benzene, toluene, Xylene 10 these combined steps may be carried out in the temperature and the like. Mixtures of different types of such hydrocar range of about -100 to about 300° C., and preferably in the bons can also be used. Such as a mixture of one or more range of about 0 to about 100° C. Holding times to allow for acyclic aliphatic hydrocarbons and one or more the completion of the reaction may range from about 10 cycloaliphatic hydrocarbons; a mixture of one or more seconds to about 60 minutes depending on the reaction acyclic aliphatic hydrocarbons and one or more aromatic 15 variables. The solution produced by combining the transi hydrocarbons; a mixture of one or more cycloaliphatic tion metal compound, the haloaluminoxane of this inven hydrocarbons and one or more aromatic hydrocarbons; or a tion, and the modifier can then be contacted with the Support, mixture of one or more acyclic aliphatic hydrocarbons, one or preferably the haloaluminoxane of this invention is in the or more cycloaliphatic hydrocarbons, and one or more presence of the Support as formed and thus is Supported on aromatic hydrocarbons. the inorganic catalyst Support ab initio. This Supported Once all of the components for making the Supported haloaluminoxane of this invention is then treated with the catalyst are present together, the mixture thereof may be modifier and then with the transition metal compound in a heated. Temperatures in the range of about 20 to about 100° Suitable inert organic medium Such as an aromatic Solvent to C. are typically used, but higher or lower temperatures can produce a slurry of active modified catalyst of this invention. be used if desired. 25 For the partially halogenated aluminoxanes, in these opera In all cases, a catalytically-active catalyst composition is tions contact temperatures may range from about 0 to about formed by interaction between a haloaluminoxane of this 100° C. depending upon the solvents used. Contact times invention and one or more transition metal compounds of may vary from about 10 seconds to about 60 minutes or Groups 3 to 10 including the lanthanide series and the longer. actinide series, and this catalyst composition is Supported on 30 Regardless of the method used in forming the modified the catalyst Support or carrier used. The catalyst Support or catalyst, the solvent or diluent can be removed, typically by carrier material used in this process can be any particulate applying a vacuum, in order to isolate the catalyst. The material useful as a catalyst Support or carrier Such as a Solution may or may not be heated in order to aid in the porous spheroidal or particulate organic resinous Support or removal of the solvent. Alternatively the active catalyst a porous inorganic Support, and preferably is a particulate 35 slurry, with some of the solvent/diluent stripped away if inorganic catalyst Support Such as an inorganic oxide or an desired, can be used as a component in conducting the inorganic material comprised of one or more oxides. Various polymerization. Another variant is to replace the original ratios of Supported haloaluminoxane of this invention to the solvent/diluent with another inert liquid diluent such as a liquid transition metal catalyst compound or complex can be paraffinic hydrocarbon to thereby provide a slurry of active used. For example these components can be proportioned 40 catalyst for use in the polymerization. Such that the mole ratio of aluminum to transition metal is In accordance with this invention, optimum results are in the range of about 20:1 to about 2000:1, and preferably in generally obtained wherein the molar ratio of haloalumi the range of about 20:1 to about 200:1. noxane of this invention to transition metal compound is It is preferred that the catalyst components as well as the from about 1.1 to about 20,000:1, preferably from about resultant catalyst compositions be handled in an inert, mois 45 10:1 to about 1000:1, and the molar ratio of haloaluminox ture-free, oxygen free environment Such as argon, nitrogen ane of this invention to modifier is from about 1:1 to about or helium because of the sensitivity of the catalyst compo 20,000:1, preferably from about 10:1 to about 1000:1. The nents and catalyst compositions to moisture and oxygen. concentration of transition metal compound on the Support Regardless of the method used in the preparation, the is typically between 0.01 wt % to about 100 wt %, preferably active Supported catalyst can be recovered by evaporation of 50 about 0.1 wt % to about 20 wt % based upon the weight of the solvent to obtain a free-flowing solid or alternatively, the the Support. active Supported catalyst can be maintained in its slurry state The Supported catalyst Systems of this invention are for direct use. Another variant is to replace the original useful in producing olefin polymers and especially ethylene solvent/diluent with another inert liquid diluent such as a polymers, propylene polymers, ethylenefol-olefin copoly paraffinic hydrocarbon to thereby provide a slurry of active 55 mers, styrene polymers and copolymers and the like. catalyst for use in the polymerization. In conducting the polymerizations pursuant to this inven Modified supported catalysts of this invention can be tion, the catalyst components can be used in solution or prepared by combining in any order at least one transition deposited on a solid Support. When used in Solution poly metal compound, at least one haloaluminoxane of this merization, the solvent can be, where applicable, a large invention, at least one modifier, and the Support in one or 60 excess quantity of the liquid olefinic monomer. Typically, more suitable solvents or diluents. A modifier may be however, an ancillary inert Solvent, typically a liquid paraf defined as a compound containing a Lewis acid or basic finic or aromatic hydrocarbon Solvent is used, such as functionality, Such as, for example, tetraethoxysilane, phe heptane, isooctane, decane, toluene, Xylene, ethylbenzene, nyltri (ethoxy)silane, bis-tert-butylhydroxytoluene (BHT), mesitylene, or mixtures of liquid paraflinic hydrocarbons N,N-dimethylaniline and the like. Suitable solvents and/or 65 and/or liquid aromatic hydrocarbons. diluents are the same as those described above. It is pre Polymers can be produced pursuant to this invention by ferred that these catalyst components be handled in an inert, homopolymerization of olefins, typically 1-olefins (also US 7,193,100 B2 33 34 known as C.-olefins) such as ethylene, propylene, 1-butene, alkyl is preferably employed as a solution in a suitable dry styrene, or copolymerization of two or more copolymeriZ liquid hydrocarbon Solvent Such as toluene or Xylene. Con able monomers, at least one of which is typically a 1-olefin. centrations of such solutions in the range of about 5x10 The other monomer(s) used in forming Such copolymers can molar are conveniently used. But Solutions of greater or be one or more different 1-olefins and/or a diolefin, and/or 5 lesser concentrations can be used, if desired. Polymer prod a acetylenic monomer. Olefins that can be polymerized in uct can be withdrawn continuously or semi-continuously at the presence of the catalyst compositions of this invention a rate that maintains a constant product inventory in the include C-olefins having 2 to 20 carbon atoms such as reactOr. ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pen In general, the polymerizations and copolymerizations tene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 10 conducted pursuant to this invention are carried out using a 1-hexadecene, and 1-octadecene. Normally, the hydrocar catalytically effective amount of a novel catalyst composi bon monomers used. Such as 1-olefins, diolefins and/or tion of this invention, which amount may be varied depend acetylene monomers, will contain up to about 10 carbon ing upon Such factors such as the type of polymerization atoms per molecule. Preferred 1-olefin monomers for use in being conducted, the polymerization conditions being used, the process include ethylene, propylene, 1-butene, 3-methyl- 15 and the type of reaction equipment in which the polymer 1-butene, 4-methyl-1-pentene, 1-hexene, and 1-octene. It is ization is being conducted. In many cases, the amount of the particularly preferred to use Supported or unsupported cata catalyst of this invention used will be such as to provide in lysts of this invention in the polymerization of ethylene, or the range of about 0.000001 to about 0.01 percent by weight propylene, or ethylene and at least one C-C 1-olefin of transition, lanthanide, or actinide metal based on the copolymerizable with ethylene. Typical diolefin monomers 20 weight of the monomer(s) being polymerized. which can be used to form terpolymers with ethylene and After polymerization and deactivation of the catalyst in a propylene includebutadiene, hexadiene, norbornadiene, and conventional manner, the product polymer can be recovered similar copolymerizable diene hydrocarbons. 1-Heptyne and from the polymerization reactor by any suitable means. 1-octyne are illustrative of Suitable acetylenic monomers When conducting the process with a slurry or dispersion of which can be used. 25 the catalyst in a liquid medium the product typically is Often the monomer used is a 1-alkene monomer whereby recovered by a physical separation technique (e.g., decan a homopolymer is prepared. In other frequent cases a tation, etc.). The recovered polymer is usually washed with mixture of a 1-alkene monomer Such as ethylene and at least one or more suitably volatile solvents to remove residual one monomer copolymerizable therewith is used whereby a polymerization solvent or other impurities, and then dried, copolymer is produced. 30 typically under reduced pressure with or without addition of Polymerization of ethylene or copolymerization with eth heat. When conducting the process as a gas phase polymer ylene and an O-olefin having 3 to 10 carbon atoms may be ization, the product after removal from the gas phase reactor performed in either the gas or liquid phase (e.g., in a solvent, is typically freed of residual monomer by means of a Such as toluene, or heptane). The polymerization can be nitrogen purge, and may possibly be used without further conducted at conventional temperatures (e.g., 0° to 120° C.) 35 catalyst deactivation or catalyst removal. and pressures (e.g., ambient to 50 kg/cm) using conven When preparing polymers pursuant to this invention con tional procedures as to molecular weight regulations and the ditions may be used for preparing unimodal or multimodal like. polymer types. For example, mixtures of catalysts of this The heterogeneous catalysts of this invention can be used invention formed from two or more different metallocenes in polymerizations conducted as slurry processes or as gas 40 having different propagation and termination rate constants phase processes. By “slurry' in this connection is meant that for ethylene polymerizations can be used in preparing poly the particulate catalyst is used as a slurry or dispersion in a mers having broad molecular weight distributions of the Suitable liquid reaction medium which may be composed of multimodal type. one or more ancillary solvents (e.g., liquid aliphatic or The foregoing operations described herein are conducted aromatic hydrocarbons, etc.) or an excess amount of liquid 45 under conventional inert atmospheres using Suitably anhy monomer to be polymerized in bulk. Generally speaking, drous materials. these polymerizations are conducted at one or more tem The following examples are presented for purposes of peratures in the range of about 0 to about 160° C. and under illustration, and are not intended to impose limitations on the atmospheric, Subatmospheric, or Superatmospheric condi scope of this invention. All experiments of these Examples tions. Preferably polymerizations conducted in a liquid 50 were carried out under inert atmosphere conditions, using reaction medium containing a slurry or dispersion of a Schlenk glassware and vacuum line, in conjunction with a catalyst of this invention are conducted at temperatures in nitrogen drybox. Solvents were dried using standard meth the range of about 40 to about 110°C. Typical liquid diluents ods. Filtration and vacuum distillation were done inside the for Such processes include isobutane, pentane, isopentane, nitrogen drybox and distillates collected in a trap at -78°C. hexane, heptane, toluene, and like materials. Typically, when 55 The samples for 'F NMR analysis were either in THF-d8 or conducting gas phase polymerizations, Superatmospheric in toluene-d8, each typically containing 0.05–0.4 wt % pressures are used, and the reactions are conducted at fluorine. Aluminoxanes were obtained from Stock solutions temperatures in the range of about 50 to about 160° C. These manufactured by Albemarle Corporation. gas phase polymerizations can be performed in a stirred or In the Examples, methylaluminoxane is sometimes abbre fluidized bed of catalyst in a pressure vessel adapted to 60 viated as MAO: the product of a reaction between MAO and permit the separation of product particles from unreacted a halohydrocarbon containing fluorine is sometimes abbre gases. Thermostated ethylene, comonomer, hydrogen and an viated as F-MAO. Similarly, the product of a reaction inert diluent gas such as nitrogen can be introduced or between MAO and a halohydrocarbon containing chlorine is recirculated to maintain the particles at the desired polymer sometimes abbreviated as Cl-MAO, and a product of a ization reaction temperature. An aluminum alkyl Such as 65 reaction between MAO and a halohydrocarbon containing triethylaluminum may be added as a scavenger of water, bromine is sometimes abbreviated as Br-MAO. The product oxygen and other impurities. In such cases the aluminum of a reaction between MAO and either a fluorosilicone US 7,193,100 B2 35 36 (fluorosiloxane) or a polyfluorosilicone (polyfluorosiloxane) The resultant deep blue slurry was stirred for 20 min then is sometimes abbreviated as FSi-MAO. TMA is an abbre heated to 84° C. and stirred for 10 mins, resulting in an viation for trimethylaluminum; PE is sometimes used as an almost colorless, clear solution. Yield: 21.3 g. "H NMR abbreviation for polyethylene. (THF-d8, 25° C., 400 MHz): 8-0.5 ppm (broad, CH of MAO); 8-0.8 ppm (s. Al(CH)); 8 1.4 ppm (s. CHC(C EXAMPLE 1. H)); Ö 1.7–1.8 ppm (multi-singlet, p-, m-, and o-CHCHC(CH)2CHs); 6 2.3 ppm (s. CHCHs); Ö Synthesis of Ionic Fluoroaluminoxane Complex and 7.0–7.5 ppm (m, CHCHC(CH)), p-, m-, and o-CHC F-MAO from Neat MAO HC(CH),CH). 'FNMR(THF-d8, 25° C., 400 MHz): 10 8-140 ppm (broad, F Al of F-MAO). The side products of In the drybox, solid MAO (0.20 g) was dissolved in CD the reaction were CHC(CH), p-, m-, and o-CHCHC (0.80 g) in a 4 mL vial and CHCF (0.0120 g) was mixed (CH)CHs, and this was confirmed by GC-MS. with 0.80 g CD in another vial. The CHCF (0.20 g; based on 2 mol % F on Al) in CD was dropwise added to EXAMPLE 4 the MAO CD solution with vigorous shaking. The color 15 less Solution changed to brown, then quickly changed to Synthesis of F-MAO with 4 mol % F Relative to deep blue. The blue material was transferred to an NMR tube Aluminum for NMR analysis. The NMR tube was then placed in an 86° C. oil bath for 1 min. The blue-colored substance in the In the drybox with N atmosphere, MAO (30% in toluene: 20.0 g) was placed in an 4 oz reaction bottle. Some of the NMR tube became colorless. THF-d8 was added for better CHCF stock Solution made in Example 2 (4.1 g) was resolution. No new species formed after heat treatment added dropwise to the vigorously stirring MAO solution. except with THF-d8 giving sharpened peaks of Al-Me The resultant deep blue slurry was stirred for 28 min then species and better resolution. Some chemical shifts also heated to 84° C. and stirred for 9 mins, resulting in a light changed due to the addition of THF-d8 in CD solution. "H yellow, clear solution. Yield: 22.9 g, "H NMR (THF-d8, 25° NMR (THF-d8, 25°C., 400 MHz): 8-0.5 ppm (broad, CH 25 C., 400 MHz): 8-0.5 ppm (broad, CH of MAO); 8-0.8 ppm of MAO); 8-0.8 ppm (s. Al(CH)); 8 1.4 ppm (s. CHC(C (S, Al(CH3)); Ö 1.4 ppm (S, CHC(CH)); Ö 1.7–1.8 ppm H)); 61.7–1.8 ppm (multi-singlet, p-, m-, and (multi-singlet, p-, m-, and o-CHCHC(CH3)2CHs); 6 2.3 o-CHCHC(CH)2CHs); 6 2.3 ppm (s. CHCHs); 8 ppm (S, CHCHs); Ö 7.0–7.5 ppm (m, CHCHs. C 7.0–7.5 ppm (m, CHCHs. CHC(CH)), p-, m-, and His C(CH2)4), p-, m-, and O-CHCHC(CH4)2CHs). F o-CHCHC(CH),CH). 'F NMR (THF-d8, 25°C., 400 30 NMR (THF-d8, 25° C., 400 MHz): 8-140 ppm (broad, MHz): 8-140 ppm (broad, F. All of F-MAO). The side F Al of F-MAO). The side products of the reaction were products of the reaction were CHC(CH), p-, m-, and CHC(CH), p-, m-, and o-CHCHC(CH3)2CHs. o-CHCHC(CH)2CHs. EXAMPLE 5 EXAMPLE 2 35 Synthesis of F-MAO with 6 mol % F Relative to Synthesis of F-MAO with 0.5 mol % F Relative to Aluminum Aluminum In the drybox with N atmosphere, MAO (30% in toluene: 30.0 g) was placed in an 8 oz reaction bottle. A CHCF, CHCF was degassed with N for 30 min before it was 40 toluene solution (4.44 g; 10%; 1.76 g CHCF+15.84 g taken into the drybox. In the drybox with N atmosphere, a toluene) was added dropwise to the vigorously stirring MAO 20 mL vial was charged with CHCF (0.46 g) and toluene solution. The resultant deep blue slurry was stirred for 20 (10.02 g) to make a 4.4 wt % stock solution of CHCF. min then heated to 84° C. and stirred for 20 mins, resulting MAO (30% in toluene; 20.3 g) was placed in an 4 oz in a light green, clear solution. Yield: 33.3 g. "H NMR reaction bottle. Some of the CHCF stock solution (0.493 45 (THF-d8, 25° C., 400 MHz): 8-0.5 ppm (broad, CH of g) was added dropwise to the vigorously stirring MAO MAO); 8-0.8 ppm (s. Al(CH)); 8 1.4 ppm (s. CHC(C solution. The resultant deep blue slurry was heated to 84°C. H)); 8 1.7–1.8 ppm (multi-singlet, p-, m-, and and stirred for 9 min, resulting in an almost colorless, clear o-CHCHC(CH)2CHs); 6 2.3 ppm (S, CHCHs); Ö solution. Yield: 19.75 g. "H NMR (THF-d8, 25° C., 400 7.0–7.5 ppm (m, CHCHCHC(CH)), p-, m-, and MHz): 8-0.5 ppm (broad, CH of MAO); 8-0.8 ppm (s. 50 o-CHCHC(CH),CH). 'F NMR (THF-d8, 25°C., 400 Al(CH3)); Ö 1.4 ppm (S, CHC(CH)); Ö 1.7–1.8 ppm MHz): 8-140 ppm (broad, F. All of F-MAO). The side (multi-singlet, p-, m-, and o-CHCHC(CH3)2CHs); 6 2.3 products of the reaction were CHC(CH), and p-, m-, and ppm (S, CHCHs); Ö 7.0–7.5 ppm (m, CHCHs. C o-CHCHC(CH)2CHs. HC(CH)), p-, m-, and O-CHCHC(CH2)CHs). 'F EXAMPLE 6 NMR (THF-d8, 25° C., 400 MHz): 8-140 ppm (broad, 55 F Al of F-MAO). The side products of the reaction were Synthesis of Ionic Fluoroaluminoxane Complex and CHC(CH), p-, m-, and o-CHCHC(CH3)2CHs. F-MAO with 12 mol % F Relative to Al EXAMPLE 3 In the drybox with N atmosphere, MAO (30% in toluene: 60 30.1 g) was placed in an 8 oz reaction bottle. A toluene Synthesis of F-MAO with 2 mol % F Relative to solution of CHCF (4.6%; 0.925 g CHCF +18.0 g tolu Aluminum ene) was added dropwise to the vigorously stirring MAO Solution through a dropping funnel. The resultant deep blue In the drybox with N atmosphere, MAO (30% in toluene: slurry was divided in two portions: 29.0 g was set aside; the 20.0 g) was placed in an 4 oz reaction bottle. Some of the 65 rest was stirred for 20 min then heated to 84° C. and stirred CHCF stock solution made in Example 2 (2.0 g) was for 30 mins, resulting in a light green, clear Solution with added dropwise to the vigorously stirring MAO solution. colorless solid material at the bottom. NMR analysis for the US 7,193,100 B2 37 38 solution phase showed similar F" and H spectra to those an oil bath. This experiment used the ionic fluoroaluminox containing 0.5–6-mol % F relative to aluminum. The fluo ane complex from Example 6. Because significant precipi rine content in Solution phase was much lower than 12 mol tate formed, the blue solution phase was sampled for NMR % F charge, i.e., the 29.0 g F-MAO slurry (without heat treatment) for Supported catalyst preparation contained only analysis to quantify the F content. Quantitative F NMR 10.5 mol % F and the Solution from the rest of the F-MAO analysis showed only 10.5 mol % F relative to A1. The blue after heat treatment contained only 8.1 mol % F. The side slurry (29.0 g) was weighed into a beaker and transferred to products of the reaction were CHC(CH), and p-, m-, and the flask. The beaker was washed with 40 g toluene, which o-CHCHC(CH)2CHs and this was confirmed by GC was added to the deep blue slurry. While the overhead stirrer MS. was turned on, 10.0 g silica was added at once and the 10 resultant slurry was allowed to stir at room temperature for EXAMPLE 7 60 min. The mixture still retained its deep blue color.

Supporting of Ionic Fluoroaluminoxane Complex EXAMPLE 11 with 2 mol % F Relative to Al on Silica 15 In the drybox with N atmosphere, MAO (30% in toluene: Supporting of F-MAO with 2 mol % and 4 mol % 3.2 g) was placed in a 20 mL vial with a magnetic stirring F Relative to A1 on Silica bar. Silica (2.2 g) was added at once to the vigorously stirring MAO solution. Then a toluene solution of CHCF In the drybox, the oven dried 300 mL flask, condenser, (0.050 g CHCF in 3.0 g toluene) was added dropwise to overhead stirrer and septum were assembled and placed in the vigorously stirring MAO/silica slurry. The resultant deep an oil bath. F-MAO with 2 mol % F relative to aluminum blue slurry was allowed to stir for 15 min. The slurry was then filtered through a coarse frit. The filtrate was colorless (30% in toluene; 18.0 g) made according to Example 3 was and clear. The deep blue solids were dried under vacuum for weighed into a beaker then transferred to the 300 mL flask. one hour. The deep blue color changed to purple blue. Yield: The beaker was washed with 45g toluene, which was added 3.2g. 25 to the F-MAO solution. While the overhead stirrer was turned on, 10.0 g silica was added at once and the resultant EXAMPLE 8 slurry was allowed to stir at room temperature for 60 min. The same procedure was followed, using F-MAO with 4 Supporting of Ionic Fluoroaluminoxane Complex mol % Frelative to aluminum (30% in toluene; 20.5 g) made with 2 mol % F Relative to Al on Silica 30 according to Example 4. The amount of wash toluene was 32 g, and 10.2 g of silica were used. In the drybox, the oven dried 300 mL flask, condenser, overhead stirrer and septum were assembled. 30.0 g MAO (30% in toluene) was weighed into a 4 oz reaction bottle EXAMPLE 12 with a magnetic stirring bar. CHCF (0.147 g in 3.1 g 35 toluene) was then dropwise added to the vigorously stirring Supporting of F-MAO with 6 mol % F Relative to MAO solution. Some of this blue slurry material (19.0 g) All on Silica was weighed into a beaker and transferred to the 300 mL flask. The beaker was washed with 35 g toluene, which was In the drybox, the oven dried 300 mL flask, condenser, added to the deep blue slurry. While the overhead stirrer was 40 overhead stirrer and septum were assembled and placed in turned on, 10.0 g silica was added at once and the resultant an oil bath. MAO (30% in toluene; 18.5 g) was weighed into slurry was allowed to stir at room temperature for 60 min. a beaker then transferred to the 300 mL flask. The beaker The mixture still retained a deep blue color. was washed with 40 g toluene, which was added to the MAO EXAMPLE 9 solution. While the overhead stirrer was turned on, CHCF 45 (0.288 g. in 3 g toluene) was slowly added to the MAO Solution with a glass pipette. Then the blue mixture was Supporting of Ionic Fluoroaluminoxane Complex heated to 80° C. for 30 min. The resultant solution was light with 6 mol % F Relative to Al on Silica green. The solution was allowed to cool to below 50° C. In the drybox, the oven dried 300 mL flask, condenser, Then 10.0 g silica was added at once and the resultant slurry overhead stirrer and septum were assembled. 30.0 g MAO 50 was allowed to stir at room temperature for 60 min. (30% in toluene) was weighed into a 4 oz reaction bottle with a magnetic stirring bar. CHCF solution (0.441 g in EXAMPLE 13 9.2 g toluene) was then dropwise added to the vigorously stirring MAO solution. Some of this blue slurry material Stability Tests of F-MAO (19.0 g) was weighed into a beaker and transferred to the 300 55 mL flask. The beaker was washed with 40 g toluene, which The stability of some fluoroaluminoxanes prepared was added to the deep blue slurry. While the overhead stirrer according to the methods described in Examples 2–6 were was turned on, 10.0 g silica was added at once and the tested and compared to a regular MAO sample. Results are resultant slurry was allowed to stir at room temperature for summarized in Table 1. All samples were stored in carbon 60 min. The mixture still retained a deep blue color. 60 steel containers. Indoor conditions were about 25°C. in the EXAMPLE 10 drybox; outdoor conditions were between approximately 20 and 50° C. (typical Southern U.S. Summer weather) in a Supporting of Ionic Fluoroaluminoxane Complex metal cabinet. The MAO content of all solutions was 30% with 12 mol % F Relative to Al on Silica when reacted with CFCHs. For comparison, note that fresh 65 (non-fluorinated) MAO has a gel content of 1.5 wt %. The In the drybox, the oven dried 300 mL flask, condenser, fluorine content in Table 1 is mole percent relative to overhead stirrer and septum were assembled and placed in aluminum. US 7,193,100 B2 40

TABLE 1. Day 18, Day 30, Day 60, Day 75, Day 110, indoor outdoor outdoor outdoor outdoor Gel Gel Gel Gel Gel Substance F content content content content content content MAO 0.0 mol%. 13.7 wt % solidified F-MAO 2.0 mol%. 1.3 wt % 4.4 wt %. 11.0 wt % 22.9 wt % F-MAO 4.0 mol% 0.9 wt % O.8 wt % 1.5 wt % 1.9 wt % 1.6 w %

EXAMPLE 1.4 EXAMPLE 16

Stability Test of MAO Toluene Solution with 15 Synthesis of F-MAO from CHC(CH) and p-, m-, o-CHCHC(CH),CHs 4-methyl-O.O.C.-trifluorotoluene (MTFT) To verify whether the side products CHC(CH) and p-, In the drybox, a 4 mL vial was charged with MTFT m-, o-CHCHC(CH)CHs also play roles in the MAO (p-(CF)(CH)CH, 0.016 g) and toluene (0.16 g). MAO gel reduction, a MAO 30% toluene solution was mixed with (30% in toluene; 1.5 g) was placed in a 20 mL vial with a the F-MAO side products CHC(CH) and p-, m-, magnetic stirring bar. The MTFT solution was then dropwise o-CHCHC(CH)2CHs from the reaction of MAO with added to the vigorously stirring MAO solution. Next, the (CF)CHs. resulting deep blue slurry was heated in an 84° C. oil bath for 12 min to obtain an almost colorless, clear Solution. (CF)CHs (27.3 g) in toluene (26.2 g) was added drop 25 wise to a vigorously stirring MAO solution (30 wt %, 124.5 Yield: 1.5 g. "H NMR (THF-d8, 25° C., 400 MHz): 8-0.5 g) in toluene. The resulting slurry was filtered. The filtrate (broad, MAO); 8-0.8 (s, Al(CH)); 8 1.4 (s. containing CHC(CH) and p-, m-, o-CHCHC(CH) 4-CHCHC(CH)); 8 1.7 1.9 (multi-singlet, CHs was treated with silica (12 g) for 30 min. H NMR (4-CHCH),C(CH) and isomers); Ö 2.2 (multi-singlet, showed about 0.2 wt % F-MAO/MAO. More silica (4 g) was 30 (4-CHCH),C(CH) and isomers); 6 2.3 (S, CHCHs); Ö added. After stirring for 15 minutes, "H NMR showed no 7.0–7.7 (m, aromatic protons). 'F NMR (THF-d8, 25°C., detectable F-MAO/MAO. The silica-treated filtrate (5 g) 400 MHz): 8-140 (broad, F Al of F-MAO). The major was added to the MAO solution (11 g), concentrated from 16 side product of the reaction was 4—CHCHC(CH). g MAO 30% solution to make a 30% MAO solution containing the amount of CHC(CH) and p-, m-, 35 EXAMPLE 17 o-CHCHC(CH)2CHs similar to the amount present in a F-MAO solution with 2 mol % F per Al from the reaction of Synthesis of F-MAO from (CH)SiF MAO with (CF)CHs. This MAO solution formed gel after a week and completely solidified after a month, similar to a In the drybox, a 4 mL vial was charged with triphenylsilyl regular 30% MAO toluene solution. 40 fluoride (0.012 g) and MAO (30% in toluene, 0.2 g) and shaken well, resulting in a colorless, clear Solution. Yield: EXAMPLE 1.5 0.212 g. H1 NMR (THF-d8, 25° C., 400 MHz): 8-0.5 (broad, MAO); 8-0.8 (s, Al(CH)); 8 0.8 (s, (CHs).SiC NMR Scale Synthesis of F-MAO from 45 H.); 6 2.3 (s. CHCHs); 8 7.2-7.5 (m. CHCHs, and (C hexafluoro-p-Xylene and from hexafluoro-m-Xylene Hs).SiCH). F NMR (THF-d8, 25°C., 400 MHz): 8-140 (broad, 1F, —Al(F)—O—). The side product of the reaction In the drybox, solid MAO (0.10 g) was dissolved in was (CHs).SiCH. CD(0.5 mL) in a 4 mL vial. To this MAO solution was dropwise added hexafluoroparaxylene (p-(CF).C.H. 50 EXAMPLE 1.8 0.012 g). The resultant deep blue slurry was shaken well. Then small portion of this blue slurry was transferred to Synthesis of F-MAO from Octafluorotoluene another 4 mL vial containing few drops of THF-d8. The deep blue color immediately disappeared. All solids dissolved, In the drybox, a 4 mL vial was charged with MAO (30% resulting in a light yellow solution. Major H NMR peaks 55 in toluene: 0.2g). To this MAO solution was dropwise added octafluorotoluene (0.012 g). The mixture was shaken well, (THF-d8, 25°C., 400 MHz): 8-0.5 (broad, MAO); 8-0.8 (s, resulting in a pink solution with Small amount of crystal-like Al(CH3)); 6 2.3 (S. CHCHs); Ö 7.2-7.5 (m, aromatic solids. The pink color became more intense with time. A protons). 'F NMR (THF-d8, 25° C., 400 MHz): 8-140 small amount of this pink slurry was added to THF-d8 in a (broad, F. All of F-MAO). The side products have not been 60 4 mL vial. The pink color faded immediately, resulting in a completely identified. The same procedure was followed to colorless solution. The rest of the pink slurry changed to prepare F-MAO from the reaction of MAO (30% in toluene, colorless solution as well after one hour. Major H NMR 0.20 g) with hexafluorometaxylene (m-(CF).C.H.0.012 peaks (THF-d8, 25°C., 400 MHz): 8-0.5 (broad, MAO); g). H NMR peaks for major components were the same as 6-0.8 (s, Al(CH)); 6 2.3 (s, CHCHs); 8 7.2-7.5 (m, with hexafluoroparaxylene. The side products have not been 65 aromatic protons). 'F NMR (THF-d8, 25° C., 400 MHz): completely identified. 'F NMR showed -140 ppm broad 8-140 (broad, F. All of F-MAO). The side products have peak (F Al of F-MAO) as the sole fluorinated species. not been completely identified. US 7,193,100 B2 41 42 EXAMPLE 19 to the MAO solution. The exothermic reaction took place at once, resulting a colorless solution. "H NMR (THF-d8, 25°, Synthesis of Cl-MAO from C.C.C.-trichlorotoluene 400 MHz): 8-0.5 (broad, MAO); 8-0.8 (s, TMA): 8 0.0 (s, Sn(CH), very intense 'Sn satellites were observed); & 2.3 In the drybox, a 20 mL vial was charged with 14 g MAO 5 (s. CHCHs); 8 7.0–7.7 (m, aromatic protons). The side (30% in toluene) and CHCCls (0.185g) and shaken well, product of the reaction was Sn(CH). resulting in a deep blue slurry. The blue color faded com pletely overnight. Yield: 14.2g. "H NMR (THF-d8, 25°, 400 EXAMPLE 24 MHz): 8 -0.5 (broad, MAO); 8-0.8 (s, TMA); 8 1.4 (s, CHC(CH)); 8 1.8 (s, 4 CHCHC(CH),CHs); 6 2.2 (S, 4-CHCHC(CH)2CHs); 6 2.3 (S, CHCHs); Ö 10 Synthesis of Partially Fluorinated Modified 7.0–7.7 (m, aromatic protons). The major side products of Methylaluminoxane from C.C.C.-trifluorotoluene the reaction were CHC(CH) and p-, m-, and o-CHCHC(CH)2CHs. In the drybox. 2,6-di(butyl)-4-methylphenol (BHT, 0.33 15 g; 10 mol %) in toluene (0.65 g) was added dropwise to EXAMPLE 20 MAO solution (30% in toluene: 3.0 g) in a 20 mL vial. The Synthesis of C1-MAO from Benzylchloride solution was stirred for 1 min. Next, CFCHs (0.044 g; 6 mol % F relative to aluminum) was added at once to the In the drybox, 4 pipette of MAO (30% in toluene) was modified MAO solution. A greenish brown slurry was placed in a 4 mL vial. One drop of CHCHCl was added immediately obtained. The resultant slurry was placed in an to the MAO solution. The exothermic reaction took place at 86° C. oil bath for 10 min. The greenish brown slurry once, resulting a red-orange slurry. The color faded very became a clear brown solution. Major H NMR peaks fast. After about 5 min, the color slurry became an almost (THF-d8, 25° C., 400 MHz): 8-0.5 ppm (broad, CH of colorless solution. H NMR (THF-d8, 25°, 400 MHz): 8-0.5 MAO); 8-0.8 (s, Al(CH)); 8 1.4 (s. CHC(CH)); 8 (broad, MAO); 8-0.8 (s. TMA); 6 2.2–2.3 (multi-singlet, p 25 1.7–1.8 (multi-singlet, Bu of BHT, p-, m-, and m-, and o-CHCHCH2CHs); 6 2.3 (S, CHCHs); 6 3.8 o-CHCHC(CH)2CHs); 6 2.2–2.3 (multi-singlet, C (m, p-, m-, and o-CHCHCHCHs. CHCHCHs); 8 HCHs and Me of BHT); 8 7.0–7.5 (m, aromatic protons). 7.0–7.7 (m, aromatic protons). The side products of the 'F NMR (THF-d8, 25°C., 400 MHz): 8-140 (broad, F Al reaction p-, m-, and o-CHCHCHCHs and CHC of F-MAO). HCHs were confirmed by GC-MS. 30 EXAMPLE 21 COMPARATIVE EXAMPLE 1. Synthesis of Br-MAO from Benzylbromide Attempted Synthesis of Cl-MAO from 1,2-dichlorobenzene In the drybox, MAO (30% in toluene, 0.4 g) was placed 35 in a 4 mL vial. One drop of CHCHBr was added to the In the drybox, a 4 mL vial was charged with MAO solids MAO solution. The exothermic reaction took place at once, (0.2 g), toluene (0.5 g), and 1,2-dichlorobenzene (0.04 g). resulting a red-orange slurry. The color faded very fast. After The mixture was shaken well, resulting in a colorless, clear about 5 min, the color slurry became a light brown solution. Solution. The Solution was allowed to sit at room tempera H NMR (THF-d8, 25°, 400 MHz): 8-0.5 (broad, MAO); 40 ture for 12 days. Both on the day the reaction was initially 6-0.8 (s, TMA); 6 2.2–2.3 (multi-singlet, p-, m-, and o-C mixed and at the end of 12 days, no significant reaction HCHCHCHs); 6 2.3 (S. CHCHs); 6 3.8 (m, p-, m-, between 1,2-dichlorobenzene and MAO was detected based and o-CHCHCH2CHs. CHCH2CHs); 8 7.0–7.7 (m, on "H NMR spectra. The solution was almost completely aromatic protons). The side products of the reaction p-, m-, gelled after 12 days. and o-CHCHCH2CHs and CHCH2CHs were con 45 firmed by GC-MS. Attempted syntheses of fluorinated aluminoxane, F-MAO, at ambient conditions as described in Example 2, EXAMPLE 22 using CHF, 1.4-CF.H. C.F. or CF (CF) CF instead of CFCHs did not result in any observable reaction. Synthesis of C1-MAO from Trityl Chloride 50 EXAMPLE 25 In the drybox, 4 pipette of MAO (30% in toluene) was placed in a 4 mL vial. One drop of (CHs)CC1 was added Polymerization with Unsupported F-MAO as to the MAO solution. The exothermic reaction took place at Cocatalyst once, resulting a red slurry. The color faded very fast. After about 20 min, the color slurry became an almost colorless 55 solution. "H NMR (THF-d8, 25°, 400 MHz): 8-0.5 (broad, For homogeneous ethylene polymerizations, tests were MAO); 8-0.8 (s, TMA); 8 2.2 (s, (CHs). CCH); 6 2.3 (s. carried out in a 2 L autoclave using cyclohexane as the CHCHs); 8 7.0–7.7 (m, aromatic protons). The side prod solvent. The reaction temperature was maintained at 135° uct of the reaction, (CHS)-CCH, was confirmed by GC C., and the pressure was maintained at 140 psig. The MS. 60 F-MAO was prepared from MAO and CFCHs according to the procedure similar to Example 2. The metallocene, EXAMPLE 23 rac-1,2-bis(indenyl-ethylene-zirconium dichloride toluene solution and F-MAO solution, through separated inlets, were Synthesis of Cl-MAO from (CH)SnCl simultaneously added to the autoclave, following by the 65 introduction of high pressure ethylene gas. Polymerization In the drybox, 4 pipette of MAO (30% in toluene) was was conducted for 30 minutes. Results are summarized in placed in a 4 mL vial. One drop of (CH) SnCl was added Table 2. US 7,193,100 B2 43 44 dichloride as a toluene solution and the Cl-MAO solution, TABLE 2 were added simultaneously to the autoclave, through sepa rate inlets, followed by the introduction of high pressure F content Activity (relative (1000 kg ethylene gas. A run using F-MAO in place of the Cl-MAO Run Activator to Al) Al content Zr content PE.g. Zrthr) was also performed for comparison between the two (F-MAO and Cl-MAO). Results are summarized in Table 4. compar- MAO O mol % 0.981 mmol 2.15 Jumo .1 ative 1a F-MAO 0.5 mol % 0.966 mmol 2.15 Jumo O TABLE 4 1b F-MAO 0.5 mol % 0.980 mmol 2.15 Jumo .1 X content Activity 2a F-MAO 1.0 mol % 0.962 mmol 2.15 Jumo O 10 2b F-MAO 1.0 mol % 0.964 mmol 2.15 Jumo .1 (relative (kg PE/ 3a F-MAO 2 mol % 0.998 mmol 2.15 Jumo 3 Run Activator to Al) Al content Zr content g Zrthr) 3b F-MAO 2 mol % 0.962 mmol 2.15 Jumo .4 comparative MAO O mol % 0.841 mmol 2.15 pmol 479.4 4a F-MAO 4 mol % 0.958 mmol 2.15 mo 3 1 F-MAO 4 mol % 0.890 mmol 2.15 pmol 883.3 4b F-MAO 4 mol % 0.976 mmol 2.15 mo .4 2 C-MAO 4 mol % 0.867 mmol 2.15 pmol 518.2 Sal F-MAO 6 mol % 0.944 mmol 2.15 Jumo 5 15 3 C-MAO 4 mol % 0.847 mmol 2.15 pmol 486.5 Sb F-MAO 6 mol % 0.994 mmol 2.15 Jumo 5 6a F-MAO 12 (8.1) 0.964 mmol 2.15 Jumo .4 no 90 6b F-MAO 12 (8.1) 0.959 mmol 2.15 Jumo .4 no 90 EXAMPLE 28 * A precipitate formed; the solution did not contain expected Al or F prod ucts. The number in parentheses is the amount of fluorine in the solution Synthesis of FSi-MAO with 2 mol % F Relative to phase, as determined by NMR. Aluminum

EXAMPLE 26 Methylaluminoxane (MAO) solution in toluene (30%, 25 40.4 g, 214.1 mmol All) was placed in a reaction bottle. Polymerization with Unsupported F-MAO as Polymethyltrifluoropropylsiloxane (PMTFPS, 0.24g, 4.28 Cocatalyst mmol F) was slowly added to the bottle at room temperature. Initially, the silicone was insoluble or rather immiscible. For homogeneous ethylene polymerizations, tests were Dissolution slowly occurred with an exothermic reaction. carried out in a 2 L autoclave using cyclohexane as the 30 The solution turned yellowish. The mixture was stirred at solvent. The reaction temperature was maintained at 70°C., room temperature overnight. The resulting solution was and the pressure was maintained at 50 psig. The F-MAO was colorless and remained gel-free in the drybox for over six synthesized from MAO and CFCHs according to the months. procedure similar to Example 2. The metallocene, rac-1,2- bis indenyl-ethylene-zirconium dimethyl toluene solution 35 EXAMPLE 29 and F-MAO solution, through separated inlets, were simul taneously added to the autoclave, followed by the introduc Synthesis of FSi-MAO with 4 mol % F Relative to tion of high pressure ethylene gas. Polymerization was Aluminum conducted for 30 minutes, except for Run 3a, which was stopped after 16 minutes due to too rapid reaction that froze 40 MAO in toluene (30%, 40.5 g. 214.6 mmol Al) was the stirrer. Results are summarized in Table 3. treated with fluorosilicone (PMTFPS, 0.49 g, 8.58 mmol F) as described in Example 28. After stirring overnight at room TABLE 3 temperature, the mixture remained only slightly yellowish. F content Activity The yellow color disappeared after about 2 days. The (relative (kg PE/ 45 Solution remained colorless and gel-free for over six months Run Activator to Al) Al content Zr content g Zrthr) at room temperature in the drybox under a nitrogen atmo comparative MAO O mol % 0.931 mmol 2.15 pmol 603 sphere. comparative MAO Omol % 0.895 mmol 2.15 pmol 709 1a. F-MAO 2 mol % 0.901 mmol 2.15 pmol 759 EXAMPLE 30 1b F-MAO 2 mol % 0.895 mmol 2.15 pmol 681 50 2a F-MAO 4 mol % 0.862 mmol 1.08 Imol 1336 3a F-MAO 6 mol % 0.935 mmol 2.16 mol. 2088* Synthesis of FSi-MAO with 6 mol % F Relative to 3b F-MAO 6 mol % 1.02 mmol 1.08 Imol 1456 Aluminum *Too active to control reaction temperature; the stirrer was frozen after 16 MAO in toluene (30%, 41.7 g. 221.01 mmol All) was minutes. 55 treated with fluorosilicone (PMTFPS, 0.75 g. 6 mole % F) as described in Example 28. The yellow color remained for EXAMPLE 27 a couple of days, after which the product remained colorless and gel-free for over six months. Polymerization with Unsupported Cl-MAO as Cocatalyst 60 EXAMPLE 31 Homogeneous ethylene polymerization tests were carried Synthesis of FSi-MAO with 10 mol % F Relative out in a 2 L autoclave using cyclohexane as the solvent. The to Aluminum reaction temperature was maintained at 70° C., and the pressure was maintained at 140 psig. The Cl-MAO was 65 MAO in toluene (30%, 39.8 g. 210.9 mmol Al) was synthesized from MAO and CCICHs in Example 19. The allowed to react with fluorosilicone (PMTFPS, 1.2g, 10 metallocene, rac-1,2-bis indenyl-ethylene-zirconium mole % F) as described in Example 28. US 7,193,100 B2 45 46 EXAMPLE 32 mixture was then heated at 80°C. for 2 hours with vigorous stirring. The light yellow color became lighter and lighter. Synthesis of FSi-MAO with 12 mol % F Relative The mixture was then cooled to room temperature and to Aluminum filtered through a medium frit, resulting a foamy filtrate. MAO in toluene (30%.38.9 g, 206.2 mmol Al) and EXAMPLE 37 fluorosilicone (PMTFPS, 1.4g, 12 mole % F) were allowed to react to produce a bright yellow solution product. Supporting of FSi-MAO with 12 mol % F relative to Al on Silica 10 EXAMPLE 33 In the drybox, MAO (30%; 59.9 g) was weighed into an Synthesis of FSi-MAO with 6 mol % F Relative to 8 oz bottle with a magnetic stirring bar. Polymethyl(3,3,3- Aluminum trifluoropropyl)siloxane (1.20 g) was added to the MAO 15 Solution at once. The resultant cloudy solution was allowed MAO in toluene (30%, 76.9 g, 384.5 mmol Al) was to stir overnight at room temperature. After overnight stir treated with monomeric fluorosilicone, trifluoropropylhep ring, the cloudy solution had turned light yellow and clear. tamethyltrisiloxane (TFPHMTS, 2.45 g, 6 mole % F). The The reaction bottle was then placed in an oil bath set at 80° exothermic reaction produced a yellowish solution product. C. for 120 min with vigorous stirring. The yellowish solution The yellow solution was heated at 80° C. and then allowed became almost colorless. The reaction bottle was then to cool to room temperature overnight. The resulting color removed from the oil bath and allowed to cool to room less solution was filtered through a medium frit. temperature. The solution was filtered through a medium frit glass filter. An oven dried 300 mL flask, condenser, overhead EXAMPLE 34 25 stirrer and septum were assembled and placed in the oil bath. The FSi-MAO (17.7 g), silica (10.1 g), and toluene (45 g) Synthesis of FSi-MAO with 4.5 mol % F Relative were charged into the flask; the mixture was stirred at room to Aluminum temperature for 60 min.

30 MAO in toluene (30%, 85.5 g., 442.9 mmol Al) was EXAMPLE 38 allowed to react with a cyclic fluorosilicone, methyltrifluo Polymerization with Unsupported FSi-MAO as ropropylcyclotrisiloxane (MTFPCTS, 1.04g, 4.5 mole % F). Cocatalyst The resulting yellow solution was heated at 80° C. for 4 hours and then allowed to cool to RT overnight. The 35 For homogeneous ethylene polymerizations, tests were resulting colorless Solution was filtered through a medium carried out in a 2 L autoclave using cyclohexane as the frit. solvent. The reaction temperature was maintained at 135° C., and the pressure was maintained at 140 psig. The EXAMPLE 35 FSi-MAO was synthesized from MAO and polymethyl(3. 40 3,3-trifluoropropyl)siloxane according to the procedure of Supporting of FSi-MAO on Silica Example 34. The metallocene, rac-1,2-bis indenyl-ethyl ene-zirconium dichloride toluene solution and FSi-MAO Solution, through separated inlets, were simultaneously Silica was calcined at 600° C. An FSi-MAO solution from added to the autoclave, followed by the introduction of high each of Examples 27 to 31 was used to prepare silica 45 pressure ethylene gas. Polymerization was conducted for 30 Supported cocatalyst systems. Silica (2 g) was suspended in minutes. Results are summarized in Table 5. toluene (20g). FSi-MAO solution (17 mmol All) was added to the slurry in a reaction bottle. The bottle was placed on a TABLE 5 shaker for about 2 hours. The mixture was filtered. The solid 50 F content Activity residue was washed with toluene and cyclohexane. The (relative (1000 kg supported FSi-MAO was vacuum dried in the under N in Run Activator to Al) Al content Zr content PE.g. Zrthr) the drybox overnight at room temperature. compar- MAO O mol % 0.981 mmol 2.15 Imol 1.1 ative EXAMPLE 36 55 1a FSi-MAO 2 mol % 0.961 mmol 2.15 mol 1.4 1b FSi-MAO 2 mol % 0.959 mmol 2.15 mol 1.4 Synthesis of FSi-MAO with 1.5 mol % F Relative to Aluminum EXAMPLE 39 MAO in toluene (60 g, 30 wt %; 300 mmol All) was placed 60 in a 250 mL reaction bottle. Polymethyl(3,3,3-trifluoropro Synthesis of F-MAO with 10 mol % F from pyl)siloxane (0.9 g, 4.5 mmol. 1.5 mol % F per Al) was (CH)AlF added at once. Slowly, the reaction became exothermic. Potassium fluoride (KF, 15.7g, 270 mmol) was suspended Initially the silicone was insoluble in toluene and caused the 65 in toluene (50 g). Dimethylaluminum chloride (50 g of 50 wt cloudy look of the solution. The mixture was allowed to stir % solution in toluene, 270 mmol All) was slowly added in overnight. It then became slightly yellow but clear. The aliquots over 50 minutes. Addition was controlled such that US 7,193,100 B2 47 48 the reaction temperature (isotherm) was kept at about 50° C. pendently, fluorine, chlorine or bromine, and where R" is, After addition, the mixture was stirred for another one hour. independently, a hydrocarbyl group having from one to The reaction was monitored by H-1 NMR by the disappear about twenty carbon atoms; ance of Me-AlCl peak and appearance of Me—AlF peak. O The product, dimethylaluminum fluoride in toluene, was (vi) mixtures of any two or more of (i)–(v). used as stock solution. ab) A composition as in aa) wherein (b) is a halohydro MAO in toluene (45g, 225 mmol All) was treated at room carbon which can be represented by the formula: temperature with enough of the stock solution of dimethy ArG laluminum fluoride in toluene(2.08 g, 11.25 mmol All) to add 5 mol % (CH)AlF to the MAO. The amount of toluene 10 where Ar is an aromatic hydrocarbon ring system, G is solution of CH)AlFadded depends on the concentration of —CX. —CXR, or —CXR, in (CH)AlF. The mixture is stirred at room temperature for which X is, independently, a fluorine atom, chlorine atom, about two hours. A broad Al-F peak in F-19 NMR is or bromine atom, and in indicative of the desired product. Clarification of gelled which R is, independently, a hydrogen atom or C. alkyl MAO was observed during this process. It is advisable 15 group; and n is 1 to 5. however to use fresh MAO in order to assure better solution ac) A composition as in ab) wherein said haloaluminoxane stability. This procedure was repeated, using enough of the is an ionic haloaluminoxane complex. stock solution of (CH)AlF in toluene to add 10 mol % ad) A composition as in ab) wherein said haloaluminox (CH)AlF to the MAO. ane is a partially halogenated aluminoxane. ae) A composition as in ab) wherein said aromatic com EXAMPLE 40 pound is C.C.C.-trichlorotoluene. af) A composition as in ae) wherein said haloaluminoxane Synthesis of C1-MAO from CHCl, is an ionic chloroaluminoxane complex. ag) A composition as in ae) wherein said haloaluminoxane A 30 wt % solution of MAO in toluene (5.0 g; 25 mmol 25 is a partially chlorinated aluminoxane. Al) was placed in a 20 mL vial with a stirring bar. Neat ah) A composition as in aa) wherein said haloaluminoxane CHCl (0.0845 g; 1.0 mmol Cl) was added at once and is a partially halogenated aluminoxane. stirred at room temperature for 30 minutes; the temperature ai) A composition as in ah) wherein (b) is a siloxane with of the mixture increased. "H NMR (400 MHz, 25° C., at least one 3,3,3-trihalopropyl group. THF-d8) showed incomplete reaction to Cl-MAO, with 30 a) A composition as in ai) wherein said 3.3,3-trihalopro unreacted CHCl (5.3 ppm). The solution was light yellow. pyl group is a 3.3,3-trifluoropropyl group A complicated mixture of organic by-products was ak) A composition as in ab)–aj) wherein said aluminoxane observed. The TMA (-0.8 ppm) present in the MAO reacted is methylaluminoxane, ethylaluminoxane, n-butylalu faster with the CHCl than MAO did. Applying heat did not minoxane, or isobutylaluminoxane. drive the reaction to the desired product. 35 al) A composition as in ab) wherein said aluminoxane is Further embodiments of the invention include: methylaluminoxane: aa) A haloaluminoxane composition wherein the halogen wherein G is —CX; and wherein said haloaluminoxane is fluorine, chlorine, and/or bromine, and wherein the composition is an ionic haloaluminoxane complex. amount of halogen atoms present in said composition is am) A composition as in ab) wherein said aluminoxane is in the range of about 0.5 mole % to about 15 mole % 40 methylaluminoxane; wherein G is —CX, and wherein relative to aluminum atoms, which composition is said haloaluminoxane composition is a partially halo formed from components comprising genated aluminoxane. (a) at least one aluminoxane and an) A composition as in all) or am) wherein X is fluorine. (b) at least one halogenation agent which is ao) A composition as in aa) wherein said aluminoxane is (i) at least one halohydrocarbon of the formula RCX, 45 methylaluminoxane; wherein (b) is C.C.C.-trichloro where n=1–3, X is, independently, fluorine, chlorine or toluene or triphenylchloromethane; and wherein said bromine, and where R is, independently, a hydrogen atom haloaluminoxane composition is an ionic chloroalumi or a hydrocarbyl group having from one to about twenty noxane complex. carbon atoms; ap) A composition as in aa) wherein said aluminoxane is 50 methylaluminoxane; wherein (b) is C.C.C.-trichloro O toluene or triphenylchloromethane; and wherein said (ii) at least one siloxane having at least one labile halogen haloaluminoxane composition is a partially chlorinated atom in the molecule, wherein each halogen atom is, aluminoxane. independently, fluorine, chlorine, or bromine; aq) A composition as in any of aa) to ap) wherein the O 55 amount of halogen atoms present in said composition is (iii) at least one silane of the formula R', SiX, where in the range of about 2 mole % to about 10 mole % n=1–3, X is, independently, fluorine, chlorine or bromine, Relative to Aluminum atoms. and where R' is, independently, a hydrocarbyl group ar) A composition as in any of aa) to ap) wherein the having from one to about twenty carbon atoms, amount of halogen atoms present in said composition is O 60 in the range of about 2 mole % to about 6 mole % (iv) at least one tin compound of the formula RSnX, Relative to Aluminum atoms. where n=1–3, X is, independently, fluorine, chlorine or as) A Supported haloaluminoxane composition which is bromine, and where R' is, independently, a hydrocarbyl formed from components comprising group having from one to about twenty carbon atoms; (a) at least one aluminoxane and O 65 (b) at least one halogenation agent which is (v) at least one hydrocarbyl aluminum halide of the (i) at least one halohydrocarbon of the formula RCX, formula R"AIX, where m=1 or 2, where X is, inde where n=1–3, X is, independently, fluorine, chlorine or US 7,193,100 B2 49 50 bromine, and where R is, independently, a hydrogen atom bh) A composition as in as) wherein said aluminoxane is or a hydrocarbyl group having from one to about twenty methylaluminoxane; wherein (b) is C.C.C.-trichloro carbon atoms; toluene or triphenylchloromethane; wherein said inor O ganic oxide is silica; and wherein said haloaluminoxane (ii) at least one siloxane having at least one labile halogen 5 composition is an ionic chloroaluminoxane complex. atom in the molecule, wherein each halogen atom is, bi) A composition as in as) wherein said aluminoxane is independently, fluorine, chlorine, or bromine; methylaluminoxane; wherein (b) is C.C.C.-trichloro O toluene or triphenylchloromethane; wherein said inor (iii) at least one silane of the formula RSiX, where ganic oxide is silica; and wherein said haloaluminoxane n=1–3, X is, independently, fluorine, chlorine or bromine, 10 composition is a partially chlorinated aluminoxane. and where R' is, independently, a hydrocarbyl group b) A process which comprises mixing, in an inert, anhy having from one to about twenty carbon atoms, drous environment, O (a) at least one aluminoxane and (iv) at least one tin compound of the formula R'SnX. (b) at least one halogenation agent which is where n=1–3, X is, independently, fluorine, chlorine or 15 (i) at least one halohydrocarbon of the formula RCX, bromine, and where R' is, independently, a hydrocarbyl where n=1–3, X is, independently, fluorine, chlorine or group having from one to about twenty carbon atoms; bromine, and where R is, independently, a hydrogen atom O or a hydrocarbyl group having from one to about twenty (v) at least one hydrocarbyl aluminum halide of the carbon atoms; formula R"AIX, where m=1 or 2, where X is, inde O pendently, fluorine, chlorine or bromine, and where R" is, (ii) at least one siloxane having at least one labile halogen independently, a hydrocarbyl group having from one to atom in the molecule, wherein each halogen atom is, about twenty carbon atoms; independently, fluorine, chlorine, or bromine; O O (vi) mixtures of any two or more of (i)–(V), and 25 (iii) at least one silane of the formula R', SiX, where (c) a Support or carrier which is an inorganic oxide. n=1–3, X is, independently, fluorine, chlorine or bromine, at) A composition as in as) wherein (b) is a halohydro and where R' is, independently, a hydrocarbyl group carbon which can be represented by the formula: having from one to about twenty carbon atoms, ArG O 30 (iv) at least one tin compound of the formula R'SnX. where Ar is an aromatic hydrocarbon ring system, G is where n=1–3, X is, independently, fluorine, chlorine or —CX. —CXR, or —CXR, in bromine, and where R' is, independently, a hydrocarbyl which X is, independently, a fluorine atom, chlorine atom, group having from one to about twenty carbon atoms; or bromine atom, and in O which R is, independently, a hydrogen atom or C. alkyl 35 (v) at least one hydrocarbyl aluminum halide of the group; and n is 1 to 5. formula R"AIX, where m=1 or 2, where X is, inde au) A composition as in at) wherein said haloaluminoxane pendently, fluorine, chlorine or bromine, and where R" is, is an ionic haloaluminoxane complex. independently, a hydrocarbyl group having from one to av) A composition as in at) wherein said haloaluminoxane about twenty carbon atoms; is a partially halogenated aluminoxane. 40 O aw) A composition as in as) wherein said aromatic com (vi) mixtures of any two or more of (i)–(v), pound is C.C.C.-trichlorotoluene or triphenylchlo romethane. wherein the amount of halogenatoms is in the range of about ax) A composition as in aw) wherein said haloaluminox 0.5 mole 96 to about 15 mole % relative to aluminum atoms, ane is an ionic chloroaluminoxane complex. 45 Such that a haloaluminoxane composition is formed. ay) A composition as in aw) wherein said haloaluminox bk) A process according to b) wherein (b) is a halohy ane is a partially chlorinated aluminoxane. drocarbon which can be represented by the formula: aZ) A composition as in as) wherein said haloaluminoxane is a partially halogenated aluminoxane. ArG, ba) A composition as in az) wherein (b) is a siloxane with 50 where Ar is an aromatic hydrocarbon ring system, G is at least one 3,3,3-trihalopropyl group. —CX. —CX-R, or —CXR, in bb) A composition as in ba) wherein said 3,3,3-trihalo which X is, independently, a fluorine atom, chlorine atom, propyl group is a 3.3,3-trifluoropropyl group or bromine atom, and in bc) A composition as in aq)-bb) wherein said aluminox which R is, independently, a hydrogen atom or C. alkyl ane is methylaluminoxane, ethylaluminoxane, n-buty 55 group; and n is 1 to 5. laluminoxane, or isobutylaluminoxane. bl) A process according to bk) wherein said haloalumi bd) A composition as in at) wherein said aluminoxane is noxane is an ionic haloaluminoxane complex. methylaluminoxane; wherein G is —CX, and wherein bm) A process according to bk) wherein said haloalumi said haloaluminoxane composition is an ionic haloalu noxane is a partially halogenated aluminoxane. minoxane complex. 60 bn) A process according to bk) wherein said aromatic be) A composition as in at) wherein said aluminoxane is compound is C.C.C.-trichlorotoluene. methylaluminoxane; wherein G is —CX, and wherein bo) A process according to bn) wherein said haloalumi said haloaluminoxane composition is a partially halo noxane is an ionic fluoroaluminoxane complex. genated aluminoxane. bp) A process according to bn) wherein said haloalumi bf) A composition as in bd) or be) wherein X is fluorine. 65 noxane is a partially fluorinated aluminoxane. bg) A composition as in any of as)-bf) wherein said bq.) A process according to b) wherein said haloalumi inorganic oxide is silica. noxane is a partially halogenated aluminoxane. US 7,193,100 B2 51 52 br) A process according to ba) wherein (b) is a siloxane ch) A process according to ce) wherein said aromatic with at least one 3,3,3 compound is C.C.C.-trichlorotoluene. bs) A process according to br) wherein said 3,3,3-triha ci) A process according to ch) wherein said haloalumi lopropyl group is a 3,3,3-trifluoropropyl group noxane is an ionic fluoroaluminoxane complex. bt) A process according to bk)—bs) wherein said alumi c) A process according to ch) wherein said haloalumi noxane is methylaluminoxane, ethylaluminoxane, noxane is a partially chlorinated aluminoxane. n-butylaluminoxane, or isobutylaluminoXanc. ck) A process according to ca) wherein said haloalumi bu) A process according to bk) wherein said aluminoxane noxane is a partially halogenated aluminoxane. is methylaluminoxane; wherein G is —CX., and cl) A process according to ck) wherein (b) is a siloxane wherein said haloaluminoxane composition is an ionic 10 with at least one 3,3,3-trihalopropyl group. haloaluminoxane complex. cm) A process according to cl) wherein said 3.3,3-triha bv) A process according to bk) wherein said aluminoxane lopropyl group is a 3.3,3-trifluoropropyl group is methylaluminoxane; wherein G is —CX3; and cn) A process according to ce)-cm) wherein said alumi wherein said haloaluminoxane composition is a par noxane is methylaluminoxane, ethylaluminoxane, tially halogenated aluminoxane. 15 n-butylaluminoxane, or isobutylaluminoxane. bw) A process according to bu) or bv) wherein Xis co) A process according to ce) wherein said aluminoxane fluorine. is methylaluminoxane; wherein G is —CX, and bX) A process according to any of b)-bw) wherein said wherein said haloaluminoxane composition is an ionic inert, anhydrous environment is an aromatic hydrocar haloaluminoxane complex. bon. cp) A process according to ce) wherein said aluminoxane by) A process according to bX) wherein said aromatic is methylaluminoxane; wherein G is —CX; and hydrocarbon is toluene. wherein said haloaluminoxane composition is a par bZ) A process according to bk) wherein said inert, anhy tially halogenated aluminoxane. drous environment is toluene; wherein said aluminox cq) A process according to co) or cp) wherein X is ane is methylaluminoxane; wherein G is —CX3; and 25 fluorine. wherein said haloaluminoxane composition is an ionic cr) A process according to any of cd)-cq) wherein said haloaluminoxane complex. inert, anhydrous environment is an aromatic hydrocar ca) A process according to bk) wherein said inert, anhy bon. drous environment is toluene; wherein said aluminox cs) A process according to cr) wherein said aromatic ane is methylaluminoxane; wherein G is —CX3; and 30 hydrocarbon is toluene. wherein said haloaluminoxane composition is a par ct) A process as in any of cd)—cs) wherein said inorganic tially chlorinated aluminoxane. oxide is silica. cb) A process according to b) wherein said inert, anhy cu) A process according to ce) wherein said inert, anhy drous environment is toluene; wherein said aluminox drous environment is toluene; wherein said aluminox 35 ane is methylaluminoxane; wherein G is —CX: ane is methylaluminoxane; wherein (b) is a.a.a-trichlo wherein said inorganic oxide is silica; and wherein said rotoluene or triphenylchloromethane; and wherein said haloaluminoxane composition is an ionic haloalumi haloaluminoxane composition is an ionic chloroalumi noxane complex. noxane complex. cv.) A process according to cd) wherein said inert, anhy cc) A process according to b) wherein said inert, anhy 40 drous environment is toluene; wherein said aluminox drous environment is toluene; wherein said aluminox ane is methylaluminoxane; wherein G is —CX, ane is methylaluminoxane; wherein (b) is a.a.a-trichlo wherein said inorganic oxide is silica; and wherein said rotoluene or triphenylchloromethane; and wherein said haloaluminoxane composition is a partially haloge haloaluminoxane composition is a partially chlorinated nated aluminoxane. aluminoxane. 45 cw) A process according to ca) wherein said inert, anhy cd) A process according to b) further comprising forming drous environment is toluene; wherein said aluminox a Supported haloaluminoxane by ane is methylaluminoxane, wherein (b) is C.C.C.- A) contacting a Support or carrier which is an inorganic trichlorotoluene or triphenylchloromethane; wherein oxide with (a) and (b). said inorganic oxide is silica; and wherein said haloa O 50 luminoxane composition is an ionic chloroaluminoxane B) contacting said haloaluminoxane composition with a complex. Support or carrier which is an inorganic oxide, cX) A process according to cd) wherein said inert, anhy Such that a Supported haloaluminoxane is formed. drous environment is toluene; wherein said aluminox ce) A process according to cd) wherein (b) is a halohy ane is methylaluminoxane, wherein (b) is C.C.C.- drocarbon which can be represented by the formula: 55 trichlorotoluene or triphenylchloromethane; wherein ArG said inorganic oxide is silica; and wherein said haloa luminoxane composition is a partially chlorinated alu where Ar is an aromatic hydrocarbon ring system, G is minoxane. —CX. —CX-R, or —CXR, in cy) A composition formed from interaction between com which X is, independently, a fluorine atom, chlorine atom, 60 ponents comprising or bromine atom, and in (I) either a haloaluminoxane wherein the amount of halogen which R is, independently, a hydrogen atom or C. alkyl atoms is in the range of about 0.5 mole % to about 15 group; and n is 1 to 5. mole % relative to aluminum atoms, or cf) A process according to ce) wherein said haloalumi (a) at least one aluminoxane and noxane is an ionic haloaluminoxane complex. 65 (b) at least one halogenation agent which is cg) A process according to ce) wherein said haloalumi (i) at least one halohydrocarbon of the formula RCX, noxane is a partially halogenated aluminoxane. where n=1–3, X is, independently, fluorine, chlorine or US 7,193,100 B2 53 54 bromine, and where R is, independently, a hydrogen atom dk) A composition as in CZ) wherein said aluminoxane is or a hydrocarbyl group having from one to about twenty methylaluminoxane; wherein G is —CX; and wherein carbon atoms; said haloaluminoxane composition is a partially halo O genated aluminoxane. (ii) at least one siloxane having at least one labile halogen 5 dl) A composition as in di) or dk) wherein X is fluorine. atom in the molecule, wherein each halogen atom is, dim) A composition as in cy) wherein said aluminoxane is independently, fluorine, chlorine, or bromine; methylaluminoxane; wherein (b) is C.C.C.-trichloro O toluene or triphenylchloromethane; and wherein said (iii) at least one silane of the formula R', SiX, where haloaluminoxane composition is an ionic chloroalumi n=1–3, X is, independently, fluorine, chlorine or bromine, 10 noxane complex. and where R' is, independently, a hydrocarbyl group dn) A composition as in cy) wherein said aluminoxane is having from one to about twenty carbon atoms; methylaluminoxane; wherein (b) is C.C.C.-trichloro O toluene or triphenylchloromethane; and wherein said (iv) at least one tin compound of the formula RSnX, haloaluminoxane composition is a partially chlorinated where n=1–3, X is, independently, fluorine, chlorine or 15 aluminoxane. bromine, and where R' is, independently, a hydrocarbyl do) A composition as in any of cy)-dn) Supported on a group having from one to about twenty carbon atoms; catalyst Support or carrier. O dp) A composition as in do) wherein said catalyst Support (v) at least one hydrocarbyl aluminum halide of the or carrier is an inorganic oxide. formula R"AIX, where m=1 or 2, where X is, inde dq) A composition as in dip) wherein said inorganic oxide pendently, fluorine, chlorine or bromine, and where R" is, is silica, alumina, or silica-alumina. independently, a hydrocarbyl group having from one to dr) A composition as in any of cy)-dq) wherein said about twenty carbon atoms; transition metal compound is comprised of a halide of O 25 a transition metal of Group 4. (vi) mixtures of any two or more of (i)–(v), ds) A composition as in dr) wherein said transition metal wherein the amount of halogen atoms is in the range of is Zirconium. about 0.5 mole % to about 15 mole % relative to alumi dt) A process for forming a catalyst composition which num atoms; comprises interacting, in an inert aromatic solvent, and 30 components comprising (II) at least one catalyst compound or complex of a transition (I) either a haloaluminoxane wherein the amount of halogen metal of Groups 3 to 11 including the lanthanide series atoms is in the range of about 0.5 mole % to about 15 and the actinide series. mole % relative to aluminum atoms, or CZ) A composition as in cy) wherein (b) is a halohydro (a) at least one aluminoxane and carbon which can be represented by the formula: 35 (b) at least one halogenation agent which is ArG (i) at least one halohydrocarbon of the formula RCX. where n=1–3, X is, independently, fluorine, chlorine or where Ar is an aromatic hydrocarbon ring system, G is bromine, and where R is, independently, a hydrogen atom —CX. —CX-R, or —CXR, in or a hydrocarbyl group having from one to about twenty which X is, independently, a fluorine atom, chlorine atom, 40 carbon atoms; or bromine atom, and in O which R is, independently, a hydrogen atom or C. alkyl (ii) at least one siloxane having at least one labile halogen group; and n is 1 to 5. atom in the molecule, wherein each halogen atom is, da) A composition as in CZ) wherein said haloaluminoxane independently, fluorine, chlorine, or bromine; is an ionic haloaluminoxane complex. 45 db) A composition as in CZ) wherein said haloaluminox O ane is a partially halogenated aluminoxane. (iii) at least one silane of the formula R', SiX, where dc) A composition as in CZ) wherein said aromatic com n=1–3, X is, independently, fluorine, chlorine or bromine, pound is C.C.C.-trichlorotoluene. and where R' is, independently, a hydrocarbyl group dd) A composition as in dc) wherein said haloaluminox 50 having from one to about twenty carbon atoms; ane is an ionic chloroaluminoxane complex. O de) A composition as in dc) wherein said haloaluminox (iv) at least one tin compound of the formula R'SnX, ane is a partially chlorinated aluminoxane. where n=1–3, X is, independently, fluorine, chlorine or df) A composition as in cy) wherein said haloaluminoxane bromine, and where R' is, independently, a hydrocarbyl is a partially halogenated aluminoxane. 55 group having from one to about twenty carbon atoms; dg) A composition as in dif) wherein (b) is a siloxane with O at least one 3,3,3-trihalopropyl group. (v) at least one hydrocarbyl aluminum halide of the dh) A composition as in cy) wherein said 3,3,3-trihalo formula R"AIX, where m=1 or 2, where X is, inde propyl group is a 3.3,3-trifluoropropyl group 60 pendently, fluorine, chlorine or bromine, and where R' is, di) A composition as in cy)-dh) wherein said aluminoxane independently, a hydrocarbyl group having from one to is methylaluminoxane, ethylaluminoxane, n-butylalu about twenty carbon atoms; minoxane, or isobutylaluminoxane. O d) A composition as in cz) wherein said aluminoxane is (vi) mixtures of any two or more of (i)–(v), methylaluminoxane; wherein G is —CX, and wherein 65 wherein the amount of halogen atoms is in the range of said haloaluminoxane composition is an ionic haloalu about 0.5 mole % to about 15 mole % relative to alumi minoxane complex. num atoms; US 7,193,100 B2 55 56 and em) A process according to el) wherein (b) is a halohy (II) at least one catalyst compound or complex of a transition drocarbon which can be represented by the formula: metal of Groups 3 to 11 including the lanthanide series ArG and the actinide series. du) A process according to dt) wherein (b) is a halohy where Ar is an aromatic hydrocarbon ring system, G is drocarbon which can be represented by the formula: —CX. —CXR, or -CXR, in which X is, independently, a fluorine atom, chlorine atom, ArG or bromine atom, and in where Ar is an aromatic hydrocarbon ring system, G is which R is, independently, a hydrogen atom or C alkyl —CX. —CXR, or CXR, in 10 group; and n is 1 to 5. which X is, independently, a fluorine atom, chlorine atom, en) A process according to em) wherein said haloalumi or bromine atom, and in noxane is an ionic haloaluminoxane complex. which R is, independently, a hydrogen atom or C. alkyl eo) A process according to em) wherein said haloalumi group; and n is 1 to 5. noxane is a partially halogenated aluminoxane. dv) A process according to du) wherein said haloalumi 15 ep) A process according to em) wherein said aromatic noxane is an ionic haloaluminoxane complex. compound is C.C.C.-trichlorotoluene. dw) A process according to du) wherein said haloalumi eq) A process according to ep) wherein said haloalumi noxane is a partially halogenated aluminoxane. noxane is an ionic chloroaluminoxane complex. dx) A process according to du) wherein said aromatic er) A process according to ep) wherein said haloalumi compound is C.C.C.-trichlorotoluene. noxane is a partially chlorinated aluminoxane. dy) A process according to dx) wherein said haloalumi es) A process according to el) wherein said haloalumi noxane is an ionic chloroaluminoxane complex. noxane is a partially halogenated aluminoxane. dZ) A process according to dx) wherein said haloalumi et) A process according to es) wherein (b) is a siloxane noxane is a partially chlorinated aluminoxane. with at least one 3,3,3-trihalopropyl group. ea) A process according to dt) wherein said haloalumi 25 eu) A process according to et) wherein said 3,3,3-triha noxane is a partially halogenated aluminoxane. lopropyl group is a 3.3,3-trifluoropropyl group. eb) A process according to ea) wherein (b) is a siloxane ev) A process according to em)-eu) wherein said alumi with at least one 3,3,3-trihalopropyl group. noxane is methylaluminoxane, ethylaluminoxane, ec) A process according to eb) wherein said 3,3,3-triha n-butylaluminoxane, or isobutylaluminoxane. lopropyl group is a 3,3,3-trifluoropropyl group 30 ew) A process according to el) wherein said aluminoxane ed) A process according to any of du)-ec) wherein said is methylaluminoxane; wherein G is CX; and aluminoxane is methylaluminoxane, ethylaluminox wherein said haloaluminoxane composition is an ionic ane, n-butylaluminoxane, or isobutylaluminoxane. haloaluminoxane complex. ee) A process according to du) wherein said aluminoxane 35 ex) A process according to el) wherein said aluminoxane is methylaluminoxane; wherein G is CX; and is methylaluminoxane; wherein G is CX; and wherein said haloaluminoxane composition is an ionic wherein said haloaluminoxane composition is a par haloaluminoxane complex. tially halogenated aluminoxane. ef) A process according to du) wherein said aluminoxane ey) A process according to ew) or ex) wherein the halogen is fluorine. is methylaluminoxane; wherein G is CX; and 40 wherein said haloaluminoxane composition is a par eZ) A process according to el) wherein said aluminoxane tially halogenated aluminoxane. is methylaluminoxane; wherein (b) is C.C.C.-trichloro toluene or triphenylchloromethane; and wherein said eg) A process according to ee) or ef) wherein X is fluorine. haloaluminoxane composition is an ionic chloroalumi eh) A process according to dt) wherein said aluminoxane noxane complex. is methylaluminoxane; wherein (b) is C.O.C.-trichloro 45 fa) A process according to el) wherein said aluminoxane toluene or triphenylchloromethane; and wherein said is methylaluminoxane; wherein (b) is C.O.C.-trichloro haloaluminoxane composition is an ionic chloroalumi toluene or triphenylchloromethane; and wherein said noxane complex. haloaluminoxane composition is a partially chlorinated ei) A process according to dt) wherein said aluminoxane aluminoxane. is methylaluminoxane; wherein (b) is C.C.C.-trichloro 50 toluene or triphenylchloromethane; and wherein said fb) A process according to any of el) fa) wherein said haloaluminoxane composition is a partially chlorinated transition metal compound is comprised of a halide of aluminoxane. a transition metal of Group 4. e) A process according to any of dt)-ei) wherein said fe) A process according to fb) wherein said transition 55 metal is zirconium. transition metal compound is comprised of a halide of fol) A process according to any of el)-fc) wherein said a transition metal of Group 4. inert, anhydrous environment is an aromatic hydrocar ek) A process according to ej) wherein said transition bon. metal is zirconium. fe) A process according to fa) wherein said aromatic el) A process according to dt) further comprising forming 60 hydrocarbon is toluene. a supported catalyst composition by ff) A process as in any of el)-fe) wherein said catalyst A) contacting a support material with (I) and (II), Support or carrier is an inorganic oxide. B) contacting (I) with a support material, fg) A process as in f) wherein said inorganic oxide is a C) contacting (II) with a support material, or silica, alumina, or silica-alumina catalyst support or D) contacting said catalyst composition with a support 65 carrier. material, fh) A process as in fg) wherein said inorganic oxide is Such that a supported haloaluminoxane is formed. silica. US 7,193,100 B2 57 58 fi) A process of producing a polyolefin polymer, which fr) A process according to fa) wherein said 3,3,3-trihalo process comprises polymerizing at least one polymer propyl group is a 3.3,3-trifluoropropyl group izable olefinic monomer in the presence of a catalyst fs) A process according to any of f)-fr) wherein said composition comprised of aluminoxane is methylaluminoxane, ethylaluminox (I) either a haloaluminoxane, wherein the amount of halogen 5 ane, n-butylaluminoxane, or isobutylaluminoxane. atoms is in the range of about 0.5 mole % to about 15 ft) A process according to f) wherein said aluminoxane is mole % relative to aluminum atoms, or methylaluminoxane; wherein G is —CX; and wherein (a) at least one aluminoxane and said haloaluminoxane composition is an ionic haloalu (b) at least one halogenation agent which is minoxane complex. (i) at least one halohydrocarbon of the formula RCX, 10 fu) A process according to f) wherein said aluminoxane where n=1–3, X is, independently, fluorine, chlorine or is methylaluminoxane; wherein G is —CX, and bromine, and where R is, independently, a hydrogen atom wherein said haloaluminoxane composition is a par or a hydrocarbyl group having from one to about twenty tially halogenated aluminoxane. carbon atoms; fv) A process according to ft) or fu) wherein the halogen O 15 is fluorine. (ii) at least one siloxane having at least one labile halogen fw) A process according to fi) wherein said aluminoxane atom in the molecule, wherein each halogen atom is, is methylaluminoxane; wherein (b) is C.C.C.-trichloro independently, fluorine, chlorine, or bromine; toluene or triphenylchloromethane; and wherein said O haloaluminoxane composition is an ionic chloroalumi (iii) at least one silane of the formula R', SiX, where noxane complex. n=1–3, X is, independently, fluorine, chlorine or bromine, fx) A process according to fi) wherein said aluminoxane and where R' is, independently, a hydrocarbyl group is methylaluminoxane; wherein (b) is C.C.C.-trichloro having from one to about twenty carbon atoms; toluene or triphenylchloromethane; and wherein said O haloaluminoxane composition is a partially chlorinated (iv) at least one tin compound of the formula RSnX, 25 aluminoxane. where n=1–3, X is, independently, fluorine, chlorine or fy) A process according to any of fi)—fx) wherein said bromine, and where R' is, independently, a hydrocarbyl transition metal compound is comprised of a halide of group having from one to about twenty carbon atoms; a transition metal of Group 4. O fz) A process according to fy) wherein said transition (v) at least one hydrocarbyl aluminum halide of the 30 metal is Zirconium. formula R"AIX, where m=1 or 2, where X is, inde ga) A process as in any of fi)—fz) wherein ethylene or pendently, fluorine, chlorine or bromine, and where R" is, propylene is subjected to homopolymerization. independently, a hydrocarbyl group having from one to gb) A process as in any offi)—fz) wherein ethylene and at about twenty carbon atoms; least one alpha-olefin having in the range of 3 to about O 35 8 carbon atoms are subjected to copolymerization. (vi) mixtures of any two or more of (i)–(v), gc) A process as in any of fi)—fz) wherein said catalyst wherein the amount of halogen atoms is in the range of composition is Supported on a catalyst Support or about 0.5 mole % to about 15 mole % relative to alumi carrier. num atoms; gd) A process as in gc) wherein said catalyst Support or and 40 carrier is an inorganic oxide. (II) at least one catalyst compound or complex of a transition ge) A process as in god) wherein said inorganic oxide is metal of Groups 3 to 11 including the lanthanide series silica, alumina, or silica-alumina. and the actinide series. gf) A process as in ga) wherein said catalyst composition f) A process according to fi) wherein (b) is a halohydro is Supported on an inorganic oxide. carbon which can be represented by the formula: 45 gg) A process as in gif) wherein said inorganic oxide is ArG silica, alumina, or silica-alumina. where Ar is an aromatic hydrocarbon ring system, G is gh) A process as in gb) wherein said catalyst composition —CX. —CX-R, or —CXR, in is Supported on an inorganic oxide. which X is, independently, a fluorine atom, chlorine atom, 50 gi) A process as in gh) wherein said inorganic oxide is or bromine atom, and in silica, alumina, or silica-alumina. which R is, independently, a hydrogen atom or C. alkyl g) A composition as in ah) wherein said halogenation group; and n is 1 to 5. agent is a silane, and wherein said silane has the fk) A process according to f) wherein said haloalumi formula (CH), SiX, where n=1-3, and X is, inde noxane is an ionic haloaluminoxane complex. 55 pendently, fluorine, chlorine or bromine. fl) A process according to f) wherein said haloaluminox gk) A composition as in g) wherein said aluminoxane is ane is a partially halogenated aluminoxane. methylaluminoxane, ethylaluminoxane, n-butylalumi fm) A process according to f) wherein said aromatic noxane, or isobutylaluminoxane. compound is C.C.C.-trichlorotoluene. gl) A composition as in az) wherein said halogenation fin) A process according to fm) wherein said haloalumi 60 agent is a silane, and wherein said silane has the noxane is an ionic chloroaluminoxane complex. formula (CH), SiX, where n=1-3, and X is, inde fo) A process according to fm) wherein said haloalumi pendently, fluorine, chlorine or bromine. noxane is a partially chlorinated aluminoxane. gm) A composition as in gl) wherein said aluminoxane is fp) A process according to fi) wherein said haloaluminox methylaluminoxane, ethylaluminoxane, n-butylalumi ane is a partially halogenated aluminoxane. 65 noxane, or isobutylaluminoxane. f) A process according to fp) wherein (b) is a siloxane gn) A process as in bq) wherein said halogenation agent with at least one 3,3,3-trihalopropyl group. is a silane, and wherein said silane has the formula US 7,193,100 B2 59 60 (CH), SiX, where n=1-3, and X is, independently, O fluorine, chlorine or bromine. (v) at least one hydrocarbyl aluminum halide of the go) A process as in gn) wherein said aluminoxane is formula R"AIX, where m=1 or 2, where X is, inde methylaluminoxane, ethylaluminoxane, n-butylalumi pendently, fluorine, chlorine or bromine, and where R" is, noxane, or isobutylaluminoxane. 5 independently, a hydrocarbyl group having from one to gp) A process as inck) wherein said halogenation agent is about twenty carbon atoms; a silane, and wherein said silane has the formula O (CH), SiX, where n=1-3, and X is, independently, (vi) mixtures of any two or more of (i)–(v). fluorine, chlorine or bromine. gq) A process as in gp) wherein said aluminoxane is 10 and methylaluminoxane, ethylaluminoxane, n-butylalumi (c) a source of water. noxane, or isobutylaluminoxane. ha) A composition as in gZ) wherein (b) is a halohydro gr) A composition as in dif) wherein said halogenation carbon which can be represented by the formula: agent is a silane, and wherein said silane has the ArG formula (CH), SiX, where n=1-3, and X is, inde 15 pendently, fluorine, chlorine or bromine. where Ar is an aromatic hydrocarbon ring system, G is gS) A composition as in gr) wherein said aluminoxane is —CX. —CX-R, or —CXR, in methylaluminoxane, ethylaluminoxane, n-butylalumi which X is, independently, a fluorine atom, chlorine atom, noxane, or isobutylaluminoxane. or bromine atom, and in gt) A process as in dz) wherein said halogenation agent is which R is, independently, a hydrogen atom or C alkyl a silane, and wherein said silane has the formula group; and n is 1 to 5. (CH), SiX, where n=1-3, and X is, independently, hb) A composition as in ha) wherein said haloaluminox fluorine, chlorine or bromine. ane is an ionic haloaluminoxane complex. gu) A process as in gt) wherein said aluminoxane is hc) A composition as in ha) wherein said haloaluminox methylaluminoxane, ethylaluminoxane, n-butylalumi 25 ane is a partially halogenated aluminoxane. noxane, or isobutylaluminoxane. hd) A composition as in ha) wherein said aromatic com gv) A process as in es) wherein said halogenation agent is pound is C.C.C.-trichlorotoluene. a silane, and wherein said silane has the formula he) A composition as in hd) wherein said haloaluminox (CH), SiX, where n=1-3, and X is, independently, ane is an ionic chloroaluminoxane complex. fluorine, chlorine or bromine. 30 hf) A composition as inhd) wherein said haloaluminoxane gw) A process as in gv) wherein said aluminoxane is is a partially chlorinated aluminoxane. methylaluminoxane, ethylaluminoxane, n-butylalumi hg) A composition as in gZ) wherein said halgenation noxane, or isobutylaluminoxane. agent is a halohydrocarbon, and wherein said halohy gX) A process as in fp) wherein said halogenation agent is drocarbon is one in which at least one R is an aryl a silane, and wherein said silane has the formula 35 group. (CH), SiX, where n=1-3, and X is, independently, hh) A composition as in hg) wherein said halohydrocar fluorine, chlorine or bromine. bon is C.C.C.-trifluorotoluene. gy) A process as in gX) wherein said aluminoxane is hi) A composition as in gZ) wherein said haloaluminoxane methylaluminoxane, ethylaluminoxane, n-butylalumi is a partially halogenated aluminoxane. noxane, or isobutylaluminoxane. 40 h) A composition as in hi) wherein (b) is at least one gZ) A haloaluminoxane composition wherein the halogen siloxane, silane, tin compound, or hydrocarbyl alumi is fluorine, chlorine, and/or bromine, and wherein the num halide. amount of halogen atoms present in said composition is hk) A composition as in hj) wherein said halogenation in the range of about 0.5 mole % to about 15 mole % agent is a silane. relative to aluminum atoms, which composition is 45 hl) A composition as in hj) wherein said halogenation formed from components comprising agent is a silane, and wherein said silane is triph (a) at least one aluminum hydrocarbyl and enylfluorosilane or trimethylfluorosilane. (b) at least one halogenation agent which is him) A composition as in hj) wherein said halogenation (i) at least one halohydrocarbon of the formula RCX. agent is a siloxane, and wherein said siloxane is a where n=1–3, X is, independently, fluorine, chlorine or 50 bromine, and where R is, independently, a hydrogen atom trisiloxane or a tricyclosiloxane. or a hydrocarbyl group having from one to about twenty hn) A composition as in hj) wherein said halogenation agent is a siloxane, and wherein said siloxane is 3.3, carbon atoms; 3-trifluoropropylheptamethyltrisiloxane, 3,3,3-trifluo O ropropylheptamethylcyclotrisiloxane, or polymethyl (ii) at least one siloxane having at least one labile halogen 55 atom in the molecule, wherein each halogen atom is, (3,3,3-trifluoropropyl)siloxane. independently, fluorine, chlorine, or bromine; ho) A composition as in hj) wherein (b) is a siloxane with O at least one 3,3,3-trihalopropyl group. (iii) at least one silane of the formula R', SiX, where hp) A composition as in ho) wherein said 3,3,3-trihalo n=1–3, X is, independently, fluorine, chlorine or bromine, 60 propyl group is a 3.3,3-trifluoropropyl group and where R' is, independently, a hydrocarbyl group hq) A composition as in ha)-hp) wherein said aluminum having from one to about twenty carbon atoms, hydrocarbyl is trimethylaluminum, triethylaluminum, O tri-n-butylaluminum, or triisobutylaluminum. (iv) at least one tin compound of the formula RSnX, hr) A composition as in ha) wherein said aluminoxane is where n=1–3, X is, independently, fluorine, chlorine or 65 methylaluminoxane; wherein G is —CX, and wherein bromine, and where R' is, independently, a hydrocarbyl said haloaluminoxane composition is an ionic haloalu group having from one to about twenty carbon atoms; minoxane complex. US 7,193,100 B2 61 62 hs) A composition as in ha) wherein said aluminoxane is halogenation agent is a siloxane; and wherein said methylaluminoxane; wherein G is —CX, and wherein siloxane is a trisiloxane or a tricyclosiloxane. said haloaluminoxane composition is a partially halo il) A composition as inii) wherein said halogenation agent genated aluminoxane. is a siloxane, and wherein said siloxane is 3,3,3- ht) A composition as in hr) or hs) wherein X is fluorine. trifluoropropylheptamethyltrisiloxane, 3,3,3-trifluoro hu) A composition as in gZ) wherein said aluminum propylheptamethylcyclotrisiloxane, or polymethyl(3. hydrocarbyl is trimethylaluminum; wherein (b) is C.O., 3,3-trifluoropropyl)siloxane. O-trichlorotoluene or triphenylchloromethane; and im) A composition as in ii) wherein said aluminum wherein said haloaluminoxane composition is an ionic hydrocarbyl is trimethylaluminum, triethylaluminum, chloroaluminoxane complex. 10 tri-n-butylaluminum, or triisobutylaluminum. hV) A composition as in gZ) wherein said aluminum in) A composition as in ii) wherein said aluminum hydro hydrocarbyl is trimethylaluminum; wherein (b) is C.O., carbyl is trimethylaluminum; wherein said halogena O-trichlorotoluene or triphenylchloromethane; and tion agent is a siloxane, wherein said siloxane is wherein said haloaluminoxane composition is a par polymethyl(3,3,3-trifluoropropyl)siloxane, and tially chlorinated aluminoxane. 15 wherein said Support is silica. hw) A composition as in any of gZ) to hV) wherein the io) A process which comprises mixing, in an inert envi amount of halogen atoms present in said composition is ronment, in the range of about 2 mole % to about 10 mole % (a) at least one aluminum hydrocarbyl and relative to aluminum atoms. (b) at least one halogenation agent which is hx) A composition as in any of gZ) to hV) wherein the (i) at least one halohydrocarbon of the formula RCX, amount of halogen atoms present in said composition is where n=1–3, X is, independently, fluorine, chlorine or in the range of about 2 mole % to about 6 mole % bromine, and where R is, independently, a hydrogen atom relative to aluminum atoms. or a hydrocarbyl group having from one to about twenty hy) A composition as in gZ) wherein the amount of carbon atoms; halogen atoms present in said composition is in the 25 O range of about 2 mole % to about 10 mole % relative (ii) at least one siloxane having at least one labile halogen to aluminum atoms. atom in the molecule, wherein each halogen atom is, hz) A composition as in gZ) wherein the halogen is independently, fluorine, chlorine, or bromine; fluorine. O ia) A composition as in gZ) wherein the hydrocarbyl 30 (iii) at least one silane of the formula RSiX, where groups of said aluminoxane are saturated, and have n=1–3, X is, independently, fluorine, chlorine or bromine, from one to about twenty carbon atoms. and where R is, independently, a hydrocarbyl group ib) A composition as in gZ) wherein said aluminum having from one to about twenty carbon atoms, hydrocarbyl is trimethylaluminum, triethylaluminum, O tri-n-butylaluminum, or triisobutylaluminum. 35 (iv) at least one tin compound of the formula R'SnX. ic) A composition which comprises a haloaluminoxane where n=1–3, X is, independently, fluorine, chlorine or composition as in gZ) Supported on a catalyst Support or bromine, and where R' is, independently, a hydrocarbyl carrier. group having from one to about twenty carbon atoms; id) A composition as in gZ) wherein said haloaluminoxane O composition is Supported on a catalyst Support or 40 (v) at least one hydrocarbyl aluminum halide of the carrier, and wherein said inorganic Support or carrier is formula R"AIX, where m=1 or 2, where X is, inde silica, alumina, or silica-alumina. pendently, fluorine, chlorine or bromine, and where R" is, ie) A composition as in id) wherein said aluminum independently, a hydrocarbyl group having from one to hydrocarbyl is trimethylaluminum, triethylaluminum, about twenty carbon atoms; tri-n-butylaluminum, or triisobutylaluminum. 45 O if) A composition as in id) wherein (b) is at least one (vi) mixtures of any two or more of (i)–(v), halohydrocarbon, and wherein said halohydrocarbon is one in which at least one R is an aryl group. and ig) A composition as in id) wherein said aluminum (c) a source of water, hydrocarbyl is trimethylaluminum, triethylaluminum, 50 wherein the amount of halogen atoms is in the range of tri-n-butylaluminum, or triisobutylaluminum, wherein about 0.5 mole % to about 15 mole % relative to alumi (b) is at least one halohydrocarbon, and wherein said num atoms, such that a haloaluminoxane composition is halohydrocarbon is one in which at least one R is an formed. aryl group. ip) A process according to io) wherein (b) is a halohy ih) A composition as in ig) wherein said halohydrocarbon 55 drocarbon which can be represented by the formula: is C.C.C.-trifluorotoluene, and wherein said catalyst ArG Support or carrier is silica. ii) A composition as in id) wherein said haloaluminoxane where Ar is an aromatic hydrocarbon ring system, G is composition is a partially halogenated aluminoxane. —CX. —CX-R, or —CXR, in i) A composition as in ii) wherein said aluminum hydro 60 which X is, independently, a fluorine atom, chlorine atom, carbyl is trimethylaluminum, triethylaluminum, tri-n- or bromine atom, and in butylaluminum, or triisobutylaluminum, and wherein which R is, independently, a hydrogen atom or C. alkyl said inorganic Support or carrier is silica, alumina, or group; and n is 1 to 5. silica-alumina. iq) A process according to ip) wherein said haloalumi ik) A composition as in ii) wherein said aluminum hydro 65 noxane is an ionic haloaluminoxane complex. carbyl is trimethylaluminum, triethylaluminum, tri-n- ir) A process according to ip) wherein said haloaluminox butylaluminum, or triisobutylaluminum; wherein said ane is a partially halogenated aluminoxane. US 7,193,100 B2 63 64 is) A process according to ip) wherein said aromatic where Ar is an aromatic hydrocarbon ring system, G is compound is C.C.C.-trifluorotoluene or C.C.C.-trichlo —CX. —CXR, or —CXR, in rotoluene. which X is, independently, a fluorine atom, chlorine atom, it) A process according to is) wherein said haloaluminox or bromine atom, and in ane is an ionic haloaluminoxane complex. which R is, independently, a hydrogen atom or C. alkyl iu) A process according to is) wherein said haloalumi group; and n is 1 to 5. noxane is a partially halogenated aluminoxane. jl) A process according to jk) wherein said haloaluminox iv) A process according to io) wherein said halogenation ane is an ionic haloaluminoxane complex. agent is a halohydrocarbon, and wherein at least one R jm) A process according to jk) wherein said haloalumi is an aryl group. 10 noxane is a partially halogenated aluminoxane. iw) A process according to io) wherein said haloalumi jn) A process according to jk) wherein said aromatic noxane is a partially halogenated aluminoxane. compound is C.C.C.-trifluortoluene or C.C.C.-trichloro iX) A process according to io) wherein said halogenation toluene. agent is a siloxane; and wherein siloxane is a trisilox jo) A process according to jn) wherein said haloalumi ane or a tricyclosiloxane. 15 noxane is an ionic haloaluminoxane complex. iy) A process according to ix) wherein said siloxane is jip) A process according to jn) wherein said haloalumi 3,3,3-trifluoropropylheptamethyltrisiloxane, 3,3,3-trif noxane is a partially halogenated aluminoxane. luoropropylheptamethylcyclotrisiloxane, or polyme jq) A process according to i) wherein said haloaluminox thyl(3,3,3-trifluoropropyl)siloxane. ane is a partially halogenated aluminoxane. jr) A process according to jq) wherein (b) is a siloxane iZ) A process according to iw) wherein (b) is a siloxane with at least one 3,3,3-trihalopropyl group. with at least one 3,3,3-trihalopropyl group. jS) A process according to jr) wherein said 3,3,3-trihalo ja) A process according to iz) wherein said 3.3,3-trihalo propyl group is a 3.3,3-trifluoropropyl group propyl group is a 3.3,3-trifluoropropyl group it) A process according to jk) is) wherein said aluminum b) A process according to ip) ja) wherein said aluminum 25 hydrocarbyl is trimethylaluminum, triethylaluminum, hydrocarbyl is trimethylaluminum, triethylaluminum, tri-n-butylaluminum, or triisobutylaluminum. tri-n-butylaluminum, or triisobutylaluminum. ju) A process according to jk) wherein said aluminum jc) A process according to ip) wherein said aluminum hydrocarbyl is trimethylaluminum; wherein G is hydrocarbyl is trimethylaluminum; wherein G is —CX, and wherein said haloaluminoxane composi —CX, and wherein said haloaluminoxane composi 30 tion is an ionic haloaluminoxane complex. tion is an ionic haloaluminoxane complex. iv) A process according to jk) wherein said aluminum jd) A process according to ip) wherein said aluminum hydrocarbyl is trimethylaluminum; wherein G is hydrocarbyl is trimethylaluminum; wherein G is —CX, and wherein said haloaluminoxane composi —CX, and wherein said haloaluminoxane composi tion is a partially halogenated aluminoxane. tion is a partially halogenated aluminoxane. 35 jw) A process according to ju) or iv) wherein X is fluorine. je) A process according to by) or bw) wherein X is jX) A process as in any of ) w) wherein said inorganic fluorine. oxide is silica. jf) A process according to ip) wherein said aluminum jy) A process according to i) wherein said aluminum hydrocarbyl is trimethylaluminum; wherein G is hydrocarbyl is trimethylaluminum; wherein G is —CX, and wherein said haloaluminoxane composi 40 —CX, wherein said inorganic oxide is silica; and tion is a partially chlorinated aluminoxane. wherein said haloaluminoxane composition is a par jg) A process according to io) wherein said aluminum tially halogenated aluminoxane. hydrocarbyl is trimethylaluminum; wherein (b) is C.O., jZ) A process according to i) wherein said aluminum O-trichlorotoluene or triphenylchloromethane; and hydrocarbyl is trimethylaluminum; wherein (b) is C.O., wherein said haloaluminoxane composition is an ionic 45 O-trichlorotoluene or triphenylchloromethane; wherein chloroaluminoxane complex. said inorganic oxide is silica; and wherein said haloa h) A process according to io) wherein said aluminoxane luminoxane composition is an ionic chloroaluminoxane is methylaluminoxane; wherein (b) is C.C.C.-trichloro complex. toluene or triphenylchloromethane; and wherein said ka) A process according to i) wherein said aluminoxane haloaluminoxane composition is a partially chlorinated 50 is methylaluminoxane; wherein (b) is C.C.C.-trichloro aluminoxane. toluene or triphenylchloromethane; wherein said inor ji) A process according to io) wherein said halogenation ganic oxide is silica; and wherein said haloaluminoxane agent is a silane, and wherein said silane is triph composition is a partially chlorinated aluminoxane. enylfluorosilane or trimethylfluorosilane. It is to be understood that the reactants and components 55 referred to by chemical name or formula anywhere in this ii) A process according to io) further comprising forming document, whether referred to in the singular or plural, are a Supported haloaluminoxane by identified as they exist prior to coming into contact with A) contacting a Support or carrier which is an inorganic another Substance referred to by chemical name or chemical oxide with (a) and (b). type (e.g., another reactant, a solvent, or etc.). It matters not O 60 what preliminary chemical changes, transformations and/or B) contacting said haloaluminoxane composition with a reactions, if any, take place in the resulting mixture or Support or carrier which is an inorganic oxide, Solution or reaction medium as Such changes, transforma Such that a Supported haloaluminoxane is formed. tions and/or reactions are the natural result of bringing the jk) A process according to i) wherein (b) is a halohydro specified reactants and/or components together under the 65 conditions called for pursuant to this disclosure. Thus the carbon which can be represented by the formula: reactants and components are identified as ingredients to be ArG brought together in connection with performing a desired US 7,193,100 B2 65 66 chemical operation or reaction or in forming a mixture to be 5. A composition according to claim 2 wherein (b) is at used in conducting a desired operation or reaction. Also, least one halohydrocarbon. even though an embodiment may refer to Substances, com 6. A composition according to claim 2 wherein the amount ponents and/or ingredients in the present tense (“is com of halogen atoms present in said haloaluminoxane compo prised of, “comprises', 'is', etc.), the reference is to the sition is in the range of about 2 mole % to about 10 mole % Substance, component or ingredient as it existed at the time relative to aluminum atoms. just before it was first contacted, blended or mixed with one 7. A composition according to claim 6 wherein (b) is at or more other Substances, components and/or ingredients in least one siloxane, silane, tin compound, or hydrocarbyl accordance with the present disclosure. aluminum halide. Except as may be expressly otherwise indicated, the 10 8. A composition according to claim 2 wherein the hydro article “a” or “an' if and as used herein is not intended to carbyl groups of said aluminoxane are saturated, and have limit, and should not be construed as limiting, the descrip from one to about twenty carbon atoms. tion to a single element to which the article refers. Rather, 9. A composition according to claim 2 wherein said the article “a” or “an' if and as used herein is intended to aluminoxane is methylaluminoxane, ethylaluminoxane, cover one or more such elements, unless the text expressly 15 n-butylaluminoxane, or isobutylaluminoxane. indicates otherwise. 10. A composition according to claim 5 wherein said Each and every patent or other publication or published halohydrocarbon is one in which at least one R is an aryl document referred to in any portion of this specification is group. incorporated in toto into this disclosure by reference, as if 11. A composition according to claim 10 wherein said fully set forth herein. halohydrocarbon is C.C.C.-trifluorotoluene. The invention claimed is: 12. A composition according to claim 5 wherein said 1. Ahaloaluminoxane composition wherein the halogen is aluminoxane is methylaluminoxane, ethylaluminoxane, fluorine, chlorine, or bromine, wherein the amount of halo n-butylaluminoxane, or isobutylaluminoxane, and wherein gen atoms present in said composition is in the range of said halohydrocarbon is one in which at least one R is an aryl about 0.5 mole % to about 10 mole % relative to aluminum 25 group. atoms, and wherein said composition is formed from an 13. A composition according to claim 5 wherein said aluminoxane and at least one halogenation agent. aluminoxane is methylaluminoxane, ethylaluminoxane, 2. A composition according to claim 1 wherein said n-butylaluminoxane, or isobutylaluminoxane, and wherein composition is formed from components comprising said halohydrocarbon is C.C.C.-trifluorotoluene. (a) at least one aluminoxane and 30 14. A composition according to claim 13 wherein the (b) at least one halogenation agent which is amount of halogen atoms present in said haloaluminoxane is (i) at least one halohydrocarbon of the formula RCX. in the range of about 2 mole % to about 10 mole % relative n, where n=1–3, X is, independently, fluorine, chlo to aluminum atoms. rine or bromine, and where R is, independently, a 15. A composition according to claim 13 wherein the hydrogen atom or a hydrocarbyl group having from 35 amount of halogen atoms present in said haloaluminoxane is one to about twenty carbon atoms; in the range of about 2 mole % to about 6 mole % relative O to aluminum atoms. (ii) at least one siloxane having at least one labile 16. A composition according to claim 7 wherein said halogen atom in the molecule, wherein each halogen halogenation agent is a silane. atom is, independently, fluorine, chlorine, or bro 40 mine; 17. A composition according to claim 7 wherein said O halogenation agent is a silane, and wherein said silane is (iii) at least one silane of the formula R', SiX, where triphenylfluorosilane or trimethylfluorosilane. n=1–3, X is, independently, fluorine, chlorine or 18. A composition which comprises a haloaluminoxane bromine, and where R' is, independently, a hydro 45 composition as in claim 2 Supported on a catalyst Support or carbyl group having from one to about twenty carbon carrier. atoms, 19. A composition as in claim 18 wherein said inorganic O Support or carrier is silica, alumina, or silica-alumina. (iv) at least one tin compound of the formula R'SnX. 20. A composition according to claim 18 wherein said n, where n=1–3, X is, independently, fluorine, chlo 50 aluminoxane is methylaluminoxane, ethylaluminoxane, rine or bromine, and where R' is, independently, a n-butylaluminoxane, or isobutylaluminoxane. hydrocarbyl group having from one to about twenty 21. A composition according to claim 18 wherein (b) is at carbon atoms; least one halohydrocarbon, and wherein said halohydrocar O bon is one in which at least one R is an aryl group. (v) at least one hydrocarbyl aluminum halide of the 55 22. A composition according to claim 18 wherein said formula R"AIX, where m=1 or 2, where X is, aluminoxane is methylaluminoxane, ethylaluminoxane, independently, fluorine, chlorine or bromine, and n-butylaluminoxane, or isobutylaluminoxane, wherein (b) is where R" is, independently, a hydrocarbyl group at least one halohydrocarbon, and wherein said halohydro having from one to about twenty carbon atoms; carbon is one in which at least one R is an aiyl group. O 60 23. A composition according to claim 22 wherein said (vi) mixtures of any two or more of (i)–(v). halohydrocarbon is C.C.C.-trifluorotoluene, and wherein said 3. A composition according to claim 1 wherein the amount catalyst Support or carrier is silica. of halogen atoms present in said composition is in the range 24. A composition according to claim 7 wherein said of about 2 mole % to about 10 mole 96 relative to aluminum aluminoxane is methylaluminoxane, ethylaluminoxane, atOmS. 65 n-butylaluminoxane, or isobutylaluminoxane; wherein said 4. A composition according to claim 2 wherein the halo halogenation agent is a siloxane; and wherein said siloxane gen is fluorine. is a trisiloxane or a tricyclosiloxane. US 7,193,100 B2 67 68 25. A composition according to claim 7 wherein said n-butylaluminoxane, or isobutylaluminoxane; wherein said halogenation agent is a siloxane, and wherein said siloxane halogenation agent is a siloxane; and wherein said siloxane is 3,3,3-trifluoropropyiheptamethyltrisiloxane, 3,3,3-trifluo is a trisiloxane or a tricyclosiloxane. ropropyiheptamethylcyclotrisiloxane, or polymethyl(3,3,3- 30. A composition according to claim 27 wherein said trifluoropropyl)siloxane. halogenation agent is a siloxane, and wherein said siloxane 26. A composition according to claim 25 wherein said is 3,3,3-trifluoropropylheptamethyltrisiloxane, 3.3.3 -trif aluminoxane is methylaluminoxane, ethylaluminoxane, luoropropylheptamethylcyclotrisiloxane, or polymethyl(3. n-butylaluminoxane, or isobutylaluminoxane. 3,3-trifluoropropyl)siloxane. 27. A composition according to claim 18 wherein the amount of halogen atoms present in said haloaluminoxane 10 31. A composition according to claim 30 wherein said composition is in the range of about 2 mole % to about 10 aluminoxane is methylaluminoxane, ethylaluminoxane, mole % relative to aluminum atoms. n-butylaluminoxane, or isobutylaluminoxane. 28. A composition according to claim 27 wherein said 32. A composition according to claim 27 wherein said aluminoxane is methylaluminoxane, ethylaluminoxane, aluminoxane is methylaluminoxane; wherein said haloge n-butylaluminoxane, or isobutylaluminoxane, and wherein 15 nation agent is a siloxane, wherein said siloxane is poly said inorganic Support or carrier is silica, alumina, or silica methyl(3,3,3-trifluoropropyl)siloxane, and wherein said alumina. Support is silica. 29. A composition according to claim 27 wherein said aluminoxane is methylaluminoxane, ethylaluminoxane,