USOO6933353B2 (12) United States Patent (10) Patent No.: US 6,933,353 B2 Wan 45) Date of Patent: Aug. 23,9 2005

(54) OLEFIN POLYMERIZATION PROCESS 6,489,408 B2 12/2002 Mawson et al...... 526/68 6,524.986 B2 2/2003 Costa et al...... 502/109 (75) Inventor: Shaotian Wang, Mason, OH (US) 6,541,583 B2 4/2003 Meverden et al...... 526/127 6,559,251 B1 * 5/2003 Wang et al...... 526/127 (73) Assignee: Equistar Chemicals, LP, Houston, TX 6,765,074 B2 7/2004 Sartain ...... 526/153 (US) FOREIGN PATENT DOCUMENTS (*) Notice: Subject to any disclaimer, the term of this WO WO O1/53360 5/1999 patent is extended or adjusted under 35 WO WO 99/24446 7/2001 U.S.C. 154(b) by 92 days. OTHER PUBLICATIONS (21) Appl. No.: 10/614,615 Soga et al., Macromolecules 27 (1994) 7938–7940. Buu-Hoi and Xuong, J. Chem. Soc. (1952) 2225. (22) Filed: Jul. 7, 2003 Jingling et al., J. Organometal. Chem. 460 (1993) 191. (65) Prior Publication Data Noh, et al., J. Organometal. Chem, 518 (1996) 1. Noh, et al., J. Organometal. Chem, 580 (1999) 90. US 2005/0010004 A1 Jan. 13, 2005 * cited by examiner (51) Int. Cl...... C08F 4/44; CO8F 4/52 (52) U.S. Cl...... 526/114; 526/116; 526/161; Primary Examiner-David W. Wu 526/172; 526/148; 526/151; 526/130; 526/129; ASSistant Examiner-Rip A. Lee 526/348.5; 526/348.4; 526/348.6; 526/351; (74) Attorney, Agent, or Firm- John Tyrell; Jonathan L. 526/352; 526/348.2 Schuchardt (58) Field of Search ...... 526/114, 116, (57) ABSTRACT 526/172, 161, 113, 126,901, 943 A method for preparing a Supported organometallic complex (56) References Cited is disclosed. An organometallic complex is combined with a U.S. PATENT DOCUMENTS Support material that has been treated with an organozinc compound. The organometallic complex comprises a Group 4,370,456 A * 1/1983 George ...... 502/110 3 to 10 transition metal and an indenoindolyl ligand that is 6,177,527 B1 1/2001 Sishta et al...... 526/134 bonded to the transition metal. Also disclosed is a proceSS 6.211,311 B1 4/2001 Wang et al...... 526/1.31 for polymerizing an olefin using the Supported complex. 6,221,802 B1 4/2001 Costa et al...... 502/109 Organozinc treatment of the Support unexpectedly boosts 6,232.2606,440,889 B1 8/20025/2001 TsuieNagy et...... al...... 502/155... catalyst activity and polyolefin molecular weight. 6,451,724 B1 9/2002 Nifant’ev et al...... 502/103 6,476,173 B1 11/2002 Lin et al...... 526/351 21 Claims, No Drawings US 6,933,353 B2 1 2 OLEFIN POLYMERIZATION PROCESS They State that it is preferred not to use a Support, but give a long list of possible Supports including Silica with dieth ylzinc. No further teachings are found nor are the catalysts FIELD OF THE INVENTION used based upon indenoindolyl Systems. This invention relates to a process for polymerizing an Despite the considerable work that has been done with olefin with an activator and a Supported organometallic catalysts based upon indenoindolyl ligands there is a need complex. The proceSS gives improved catalyst activity and for improvement, especially with regard, to increasing activ polyolefins with increased molecular weight. ity and molecular weight. Organozinc compounds have apparently not been used in conjunction with organometallic BACKGROUND OF THE INVENTION complexes that incorporate indenoindolyl ligands. When Many olefin polymerization catalysts are known, includ organozinc compounds are mentioned for use in olefin ing conventional Ziegler-Natta catalysts. While these cata polymerizations with metallocene catalysts they act as chain lysts are inexpensive, they exhibit low activity and are transfer agents and reduce polyolefin molecular weight, the generally poor at incorporating C-olefin comonomers. To opposite of the effect I have found with complexes contain improve polymer properties, Single-site catalysts, in particu 15 ing indenoindolyl ligands. lar metallocenes are beginning to replace Ziegler-Natta catalysts. SUMMARY OF THE INVENTION Catalyst precursors that incorporate a transition metal and an indenoindolyl ligand are known. U.S. Pat. Nos. 6,232,260 In one aspect, the invention is a method for preparing a and 6,451,724 disclose the use of transition metal catalysts Supported organometallic complex. An organometallic com based upon indenoindolyl ligands, but have no examples pleX is combined with a Support material that has been using Supported catalysts. While they mention that Sup treated with an organozinc compound. The organometallic ported catalysts may be used, little information is given complex comprises a Group 3 to 10 transition metal and an about the preparation of the Supported catalysts. 25 indenoindolyl ligand that is bonded to the transition metal. WO 01/53360 discloses open architecture indenoindolyl In another aspect, the invention is a process for polymer catalysts that may be Supported. In the Single example izing an olefin. The Supported organometallic complex (Example 8) preparing a Supported catalyst, a Solution of the described above is mixed with an activator and an olefin, and catalyst is added to a polyethylene Support. the olefin is polymerized. Pretreatment of the support with U.S. Pat. No. 6,559,251 discloses a process for polymer an organozinc compound combined with the use of an izing olefins with a Silica-Supported, indenoindolyl Group indenoindolyl transition metal complex provides an unex 4-6 transition metal complex having open architecture. pected boost in both catalyst activity and polyolefin molecu U.S. Pat. No. 6,541,583 discloses a process for polymer lar weight. izing propylene in the presence of a Group 3–5 transition metal catalyst that has two non-bridged indenoindolyl ligands. None of the examples uses a Supported catalyst. 35 DETAILED DESCRIPTION OF THE They state that the catalyst can be immobilized on a Support INVENTION but give no process details. The invention includes a method for preparing a Sup U.S. Pat. No. 6,211,311 prepares supported catalysts ported organometallic complex. The complex contains a containing heteroatomic ligands. The Support is chemically Group 3 to 10 transition metal. Preferably the transition modified with an organoaluminum, organosilicon, organo 40 metal is a Group 3–5 transition metal, more preferably a magnesium or organoboron compound for improved cata Group 4 transition metal. Most preferably, the transition lyst Stability and activity. There is no indication that Zinc metal is Zirconium. compounds may be used, and there is no indication that increased polymer molecular weight may be obtained. The organometallic complex contains at least one inde 45 noindolyl ligand bonded to the transition metal. “Indenoin Pending application Ser. No. 10/123,774, filed Apr. 16, dolyl” ligands are conveniently generated by deprotonating 2002, discloses a process for polymerizing ethylene in the an indenoindole compound using a potent base. By “inde presence of a Silica-Supported Group 3-10 transition metal noindole compound, we mean an organic compound that catalyst that has two bridged indenoindolyl ligands. This has both indole and indene rings. The five-membered rings application teaches that the Silica can be chemically treated from each are fused, i.e., they share two carbon atoms. The and points to the above-mentioned U.S. Pat. No. 6,211,311. 50 rings can be fused Such that the indole nitrogen and the only Organozinc compounds Such as diethylzinc have been sp-hybridized carbon on the indenyl ring are “trans” to each used in olefin polymerizations as chain transfer agents to other. Such is the case in an indeno1,2-bindole ring System lower molecular weight. For example, U.S. Pat. Nos. 6,524, Such as: 986; 6,489,408; 6,476,173 and 6,221,802 mention the use of diethylzinc to control molecular weight by acting as a chain 55 transfer agent Similarly to how hydrogen is often used to lower molecular weight. None teaches treatment of a Support with an organozinc compound prior to combining it with an organometallic complex. Macromolecules 27 7938–7940 (1994) teaches polymer 60 ization of methyl methacrylate by dicyclopentadienyldim ethyl Zirconium by reacting the methyl methacrylate with diethylzinc prior to unsupported catalyst addition and poly merization. Suitable ring Systems also include those in which the U.S. Pat. No. 6,177.527 teaches an olefin polymerization 65 indole nitrogen and the sp-hybridized carbon of the indene proceSS using racemic and meSO Stereoisomers of a metal are beta to each other, i.e., they are on the same Side of the locene catalyst containing two cycloalkadienyl ligands. molecule. This is an indeno2,1-bindole ring System: US 6,933,353 B2 4 arylene, diarylene, polyarylene, cycloalkyl, adamantyl, aralkylene, alkenyl, and alkynyl. Specific examples of Suit able divalent linking groups are methylene, 1,2-ethenyl, 1,2-ethynyl, isopropylidene, 1,4-phenylene, C.C.'-xylyl, 4,4'- biphenylene, 1,3-adamantyl, 1,4-adamantyl, phenylboranyl, methylboranyl, dimethylsilyl, diphenylsily 1, b is (dimethylsilyl), oxybis(dimethylsilyl), and the like. These and other divalent linking groups are described in the background references. (For Some examples, see J. Orga nometal. Chem. 460 (1993) 191; 518 (1996) 1; 580 (1999) 90.) The ring atoms can be unsubstituted or substituted with The divalent linking group can link the indenoindolyl one or more groups Such as alkyl, aryl, aralkyl, halogen, ligand to a polymerization-stable ligand. Suitable Sillyl, nitro, dialkylamino, diarylamino, alkoxy, aryloxy, polymerization-stable ligands include cyclopentadienyl, thioether, or the like. Additional fused rings can be present, indenyl, fluorenyl, boraaryl, indenoindolyl, and the like. as long as an indenoindole moiety is present. 15 Bridged indenoindolyl ligands also include those used in Numbering of indenoindoles follows IUPAC Rule A-22. open architecture complexes. By “open architecture, we The molecule is oriented as shown below, and numbering is mean a complex having a fixed geometry that enables done clockwise beginning with the ring at the uppermost generation of a highly exposed active Site when the catalyst right of the Structure in a manner effective to give the lowest is combined with an activator. The metal of the complex is possible number to the heteroatom. Thus, 5,10 pi-bonded to the indenyl Cp ring and is also Sigma-bonded dihydroindeno1,2-bindole is numbered as follows: through two or more atoms to the indolyl nitrogen or the indenyl methylene carbon. Preferably, the metal is Sigma bonded to a heteroatom, i.e., oxygen, nitrogen, phosphorus, or Sulfur, most preferably, the metal is Sigma-bonded to nitrogen. The heteroatom is linked to the indenoindolyl 25 group through a bridging group, which is preferably dialkylsily l, diarylsily l, methylene, ethylene, isopropylidene, diphenylmethylene, or the like. Particularly preferred bridging groups are dimethylsilyl, methylene, ethylene, and isopropylidene. The bridging group is covalently bonded to either the indolyl nitrogen atom or the indenyl methylene carbon. Preferred bridged indenoindolyl ligands have a structure Selected from the group consisting of:

35

40

For correct nomenclature and numbering of these ring systems, see the Ring Systems Handbook (1998), a publica tion of Chemical Abstracts Service, Ring Systems File II: RF 45 33986-RF 66391 at RF 58952 and 58955. (Other examples of correct numbering appear in PCT Int. Appl. WO99/24446 and U.S. Pat. No. 6,440,889.) Methods for making indenoindole compounds are well known. Suitable methods and compounds are disclosed, for 50 example, in U.S. Pat. No. 6,232,260, the teachings of which are incorporated herein by reference, and references cited therein, including the method of Buu-Hoi and Xuong, J. Chem. Soc. (1952) 2225. Suitable procedures also appear in in which R is Selected from the group consisting of C-Co PCT Int. Appls. WO99/24446 and WO 01/53360. The indolyl nitrogen of each indenoindolyl group is 55 hydrocarbyl, dialkylboryl, trialkylsilyl, and divalent radicals typically Substituted with an alkyl, aryl, dialkylboryl, connected to a Second ligand; each R is independently trialkylsilyl, or a divalent linking group. Selected from the group consisting of C-C hydrocarbyl, Preferably, the indenoindolyl ligand is a bridged inde H, F, Cl and Br; R is Selected from the group consisting of noindolyl ligand. By “bridged indenoindolyl ligand, we C-Co hydrocarbyl, H and divalent radicals connected to a mean that the indenoindolyl group can be joined to a Second 60 Second ligand with the proviso that one of R or R is a ligand by a divalent linking group. A wide variety of linking divalent radical connected to a Second ligand wherein the groups are Suitable for use and are described in the art. The divalent radical is Selected from the group consisting of linking group can be a conjugated pi-electron System, but it hydrocarbyl and heteroatom containing alkylene radicals, need not be conjugated. Suitable divalent linking groups diorganosilyl radicals, diorganogermanium radicals and include dialkylsilyl, diarylsilyl, alkylboranyl, arylboranyl, 65 diorganotin radicals. Siloxy, polysiloxy, and hydrocarbyl groups. Preferred hydro Additionally, the complex includes ancillary ligands that carbyl groups are alkylene, dialkylene, polyalkylene, are bonded to the metal and satisfy the valence of the metal. US 6,933,353 B2 S 6 The ancillary ligands can be labile or polymerization-stable, -continued but usually at least one labile ligand (Such as halides, i alkoxys, aryloxys, alkyls, arylalkyls, aryls, dialkylaminos, * Y'S, or the like) is present. Particularly preferred labile ligands are halides, alkyls, arylalkyls (e.g., chloride, methyl, benzyl) N and aryloxys (e.g. phenoxy).

Preferably, the bridged indenoindolyl complex has the general Structure:

wherein M is a Group 3 to 10 transition metal; each L is independently Selected from the group consisting of halide, alkoxy, aryloxy, Siloxy, alkylamino, and C-Co hydrocar 15 byl, L' is Selected from the group consisting of alkylamido, Substituted or unsubstituted cyclopentadienyl, fluorenyl, indenyl, boraaryl, pyrrolyl, azaborolinyl and indenoindolyl, X satisfies the Valence of M, Rs is Selected from the group consisting of C-C hydrocarbyl and H; each R is inde pendently Selected from the group consisting of Rs, F, Cland Br; G is a divalent radical is Selected from the group consisting of hydrocarbyl and heteroatom containing alky lene radicals, diorganosilyl radicals, diorganogermanium radicals and diorganotin radicals. 25 The unsupported complexes can be made by any Suitable method; those skilled in the art will recognize a variety of acceptable Synthetic Strategies. Often, the Synthesis begins with preparation of the desired indenoindole compound from particular indanone and arylhydrazine precursors. Treatment with base gives a ligand precursor. The indenoin dole is linked with a Second polymerization-stable ligand to give a linked ligand precursor. The final step normally involves reaction of the ligand precursor with a transition metal Source to give the organometallic complex. The exact 35 Synthetic StepS and the Sequence used will normally depend wherein M is a Group 3 to 10 transition metal; each L is upon the other ligands used and the transition metal Source. independently Selected from the group consisting of halide, One aspect of the invention is a method for preparing a alkoxy, aryloxy, Siloxy, alkylamino, and C-Co hydrocar Supported organometallic complex. An organometallic com byl, L' is Selected from the group consisting of alkylamido, pleX as described above is combined with a Support material Substituted or unsubstituted cyclopentadienyl, fluorenyl, that has been treated with an organozinc compound. The indenyl, boraaryl, pyrrolyl, azaborolinyl and indenoindolyl, 40 organozinc compound is preferably a diarylzinc or a dialky 1zinc. DialkylzincS Such as dimethylzinc, diethylzinc or X satisfies the valence of M, R is selected from the group dibutylzinc are preferred. Of these, diethylzinc is most consisting of C-C hydrocarbyl, dialkylboryl and trialkyl preferred. The amount of organometallic complex added per silyl; each R is independently Selected from the group g Support material is preferably from 0.01 mmol per gram to consisting of C-Co hydrocarbyl, H, F, Cl and Br; G is a 45 0.8 mmol per gram. divalent radical is Selected from the group consisting of The Support material is preferably a porous material Such hydrocarbyl and heteroatom-containing alkylene radicals, as inorganic oxides and chlorides, and organic polymer diorganosilyl radicals, diorganogermanium radicals and resins. Preferred inorganic oxides include oxides of Group 2, 3, 4, 5, 13, or 14 elements. Preferred Supports include Silica, diorganotin radicals. 50 alumina, Silica-aluminas, magnesias, titania, Zirconia, mag nesium chloride, and crosslinked polystyrene. Most preferably, the Support is Silica. Other preferred bridged indenoindolyl complexes have Preferably, the Silica has a Surface area in the range of the general Structure: about 10 to about 1000 m /g, more preferably from about 50 to about 800 m/g and most preferably from about 200 to 55 about 700 m /g. Preferably, the pore volume of the silica is in the range of about 0.05 to about 4.0 mL/g, more prefer ably from about 0.08 to about 3.5 mL/g, and most preferably from about 0.5 to about 3.0 mL/g. Preferably, the average O particle size of the Silica is in the range of about 1 to about 60 500 um, more preferably from about 2 to about 200 um, and most preferably from about 5 to about 100 um. The average pore diameter is typically in the range of about 5 to about 1000 angstroms, preferably about 10 to about 500 angstroms, and most preferably about 20 to about 350 65 angstroms. Preferably, the Silica is dried before use, prefer ably at a temperature of from about 100° C. to about 800 C., more preferably from about 150° C. to about 600° C. US 6,933,353 B2 7 8 In a preferred method for making the organozinc-treated the organometallic complex is premixed with a Solution of Support, the Support material is dried, a Solution of the the activator, optionally a portion of the activator can be organozinc compound is mixed with the Support material, premixed and the remainder of the activator added to the and volatiles are removed. Mixing a Solution of the organ reactOr. Zinc compound with the support material for about 30 Preferably, a Scavenging amount of an alkyl aluminum minutes gives good results. An incipient-wetneSS technique compound Such as triethyl aluminum or triisobutyl alumi can also be used in which a concentrated Solution of the num is also added to the polymerization reactor. Preferably, organozinc compound is evenly distributed on the dry the alkyl aluminum compound is added to the reactor prior Support, and the resulting treated Support is a free-flowing to the addition of the Supported complex. powder. Preferably, the Support is treated with about 0.1 to A wide variety of olefin polymerization processes can be about 2 moles of organozinc compound per kg of Support. If used. Preferred processes are slurry, bulk, Solution, and the amount of organozinc compound is too low, the benefi gas-phase processes. A-slurry or gas-phase proceSS is pref cial effect is not seen and at very high levels, no further erably used. benefit is obtained. The polymerizations can be performed over a wide tem The Supported organometallic complex is preferably perature range, such as about -30° C. to about 280 C. A made by adding a Solution of the complex to the organozinc 15 treated Support material. Preferably, the mixture is Stirred in more preferred range is from about 10 C. to about 180 C.; an inert atmosphere at a temperature of from about 0° C. to most preferred is the range from about 30° C. to about 100 about 120° C., more preferably from about 20° C. to about C. Olefin partial preSSures normally range from about 15 40° C. The optimum stirring time will vary somewhat, psia to about 50,000 psia. More preferred is the range from depending upon the amounts of Solvent and Support about 15 psia to about 1000 psia. material, but should be long enough to ensure good mixing. Catalyst concentrations used for the olefin polymerization Preferably, the stirring time is from about 2 minutes to about depend on many factors. Preferably, however, the concen 120 minutes. Stirring longer than 120 minutes should not tration ranges from about 0.01 micromoles transition metal decrease activity, but it is unnecessary. Stirring 30 minutes per liter to about 100 micromoles per liter. Polymerization at room temperature is convenient and gives good results. times depend on the type of process, the catalyst Alternatively, an incipient-wetneSS technique can be used to 25 concentration, and other factors. Generally, polymerizations deposit the complex on the organozinc-treated Support. are complete within Several Seconds to Several hours. The invention includes an olefin polymerization process. The following examples merely illustrate the invention. Suitable olefins for the polymerization are C-Co C-olefins, Those skilled in the art will recognize many variations that Such as ethylene, propylene, 1-butene, 1-hexene and are within the Spirit of the invention and Scope of the claims. 1-octene, cyclic olefins Such as cyclopentene and cyclohex ene and nonconjugated dienes Such as ethylidene nor EXAMPLE 1. bornene and mixtures thereof. Preferred olefins are ethylene, propylene and mixtures thereof with C-olefins Such as Synthesis of 1,1-bis6-(2,5-dimethyl-5,6-dihydro 1-butene, 1-hexene and 1-octene. More preferably ethylene indeno2,1-b)indolylmethane Zirconium is copolymerized with a C-Co C-olefin. Most preferably, dichloride, 1-4 ethylene is copolymerized with 1-butene, 1-hexene or 35 1-octene. 1-4 Hydrogen is optionally used in the polymerization to HC regulate the molecular weight. The amount of hydrogen needed depends upon the desired polyolefin molecular weight and flow. Generally, as the amount of hydrogen is 40 increased, the polyolefin molecular weight decreases and the flow increases. For many applications, the polyolefin flow will be too low if the polymerization is done in the absence O of hydrogen. YCH, The olefin is polymerized in the presence of an activator. 45 Suitable activators include alumoxanes, alkyl aluminum compounds, organoboranes, ionic borates, ionic aluminates, HC ZrCl aluminoboronates and mixtures thereof. Examples include methyl alumoxane (MAO), polymeric MAO (PMAO), ethyl alumoxane, diisobutyl alumoxane, lithium tetrakis 50 (pentafluorophenyl) borate, dimethylanilinium tetrakis (pent a fluoro-phenyl)borate, trity 1 tetrak is (pentafluorophenyl)borate, tris(pentafluoro-phenyl)borane, triphenylborane, tri-n-octylborane, and the like, and mix tures thereof. Preferably, the activator is methylalumoxane. 55 Selection of activator depends on many factors including the CH organometallic complex used and the desired polymer prop erties. There are many Suitable ways to introduce the activator. (a) Preparation of 5,6-dihydro-2-methyl-indeno2,1-b For example, the activator can be added directly to the indole 1-1. A mixture of 2-indanone (51.0 g, 0.39 mol) and polymerization reactor. In one preferred embodiment, a 60 p-tolylhydrazine hydrochloride (61.4g, 0.39 mol) is dis Solution of the activator is added to the organozinc-treated Solved in glacial acetic acid (525 mL) and is vigorously Support material prior to the addition of the organometallic stirred and heated to reflux. The mixture turns red and is complex. More preferably, the organometallic complex is heated for 2 hours. After cooling to room temperature, it is premixed with a Solution of the activator prior to addition to poured into ice water (1 L). The precipitate is filtered to the organozinc-treated Support material. Preferably, the 65 afford a solid, which is washed with water (about 1 L). The organometallic complex and activator Solution are premixed Solid is dissolved in ethyl acetate (1.4 L), activated charcoal for a period of time between 1 minute and two hours. When is added, and the mixture is gently warmed. The mixture is US 6,933,353 B2 9 10 then cooled and filtered over a pad of Celite. The filtrate is 1-4 (13.8 mg, 0.019 mmole) is mixed with the diluted MAO dried over Sodium Sulfate, filtered, and is then concentrated Solution to make a deep green-blue Solution. This green-blue to 450 mL and cooled to -30° C. for 3 days. The crystalline solution is mixed further with 1.00 g of G955 silica solid is filtered and washed with chilled (-78° C) hexanes (available from Grace Davison) that had been calcined at (2x500 mL). The beige solid is collected and dried under 250 C. After stirring for 30 minutes at room temperature, vacuum (47.1 g, 56%). the volatiles are removed by vacuum to obtain 1.68 g of the (b) N-Methylation of 1-1 to give 1-2. A slurry of aqueous Supported catalyst as a dark green powder. sodium hydroxide (42 mL, 21.5 M, 903 mmol), CHNMe-Br (0.36 g., 0.97 mmol), and 1-1 (15.0 g, 68.4 EXAMPLE 4 mmol) is combined with toluene (50 mL). A solution of methyl iodide (8.0 mL, 129 mmol) in toluene (15 mL) is Copolymerization of Ethylene and 1-Hexene added dropwise at room temperature. The mixture is stirred Hydrogen is added (2.8 delta MPa from a 10-mL at room temperature for 2.5 hours and then refluxed for an stainless-steel cylinder pressurized initially to 4.5 MPa H) hour. The mixture turns red and is cooled to room tempera to a one-liter, StainleSS-Steel reactor which is then charged ture and filtered. The crystalline solid is washed with chilled 15 with 1-hexene (10 mL). Triisobutylaluminum (0.5 mL of 1.0 (-30° C) ethanol (200 mL) followed by chilled hexanes M solution in heptane, 0.5 mmol) and Stadis fatty amine (12 (200 mL) to afford a pale red solid (10.3 g, 65%). mg, product of AkzoNobel) in heptane solution (3.0 mL) are (c) Preparation of 1,1-bis6-(2,5-dimethyl-5,6-dihydro mixed in one Sidearm of the injector. This mixture is then indeno2,1-b)indolyl)methane 1-3. A slurry of 1-2 (9.32g, flushed into the reactor with nitrogen pressure and isobutane 39.9 mmol) in degassed DMF (150 mL) is warmed to 70° C., (about 400 mL) and then pressurized with ethylene to 2.4 and sodium ethoxide (1.37 g. 20.1 mmol) is added under MPa. The reactor contents are allowed to equilibrate at 80 nitrogen. The Solid dissolves to afford a dark orange Solu C. The Supported catalyst from Example 2 (29 mg) is loaded tion. Formaldehyde (1.6 mL, 37 wt % in HO, 20.8 mmol) into the other injector arm and then flushed into the reactor is added after an hour, and a precipitate formed after 20 min. with isobutane (90 mL) and nitrogen pressure. After 15 Solid ammonium chloride (2.55g, 47.7 mmol) is added, the minutes, more hydrogen is added (2.8 delta MPa from a mixture filtered, and the solid washed with DMF (50 mL) 25 10-mL stainless-steel cylinder pressurized initially to 4.5 followed by diethylether (50 mL). The solid is dissolved in MPa H). The polymerization proceeds for another 15 methylene chloride (1.3 L) and washed with water (1L). The minutes for a total of 0.5 hour. The reactor is vented and the layers are Separated, and the organics dried over Sodium polyolefin copolymer is collected and dried. Catalyst activ Sulfate and filtered. The volatiles are removed under reduced ity is 6.8 kg polyolefin perg Supported catalyst per hour. The pressure, and the Solid dried under vacuum (4.12 g, 42.8%). weight average (M) molecular weight and polydispersity (d) Preparation of 1,1-bis6-(2,5-dimethyl-5,6-dihydro (M/M) of the polymer are measured by gel permeation indeno2,1-b)indolyl)methane Zirconium dichloride, 1-4. A chromatography (GPC) using 1,3,5-trichlorobenzene at 145 mixture of 1-3 (2.18 g, 4.55 mmol) and diethylether (80 mL) C. to be 98,000 and 4.4. The melt index (MI) is measured is cooled to -78 C., and n-butyl lithium (4.0 mL, 2.5 M in according to ASTM D-1238, Condition E to be 0.1 dg/min. hexanes, 10.0 mmol) added by syringe. The cold bath is 35 removed, and a yellow solid formed upon warming to 23 C. COMPARATIVE EXAMPLE 5 The volatiles are removed after 18 hours, and the Solid washed with diethylether (20 mL) and dried under vacuum Copolymerization without Organozinc Compound (1.84g, 82.5%). The dianion (1.84g, 3.75 mmol) is added The polymerization procedure of Example 4 is generally to a solution of zirconium tetrachloride (0.88 g., 3.77 mmol) 40 followed with the Supported catalyst from Comparative in toluene (80 mL) and diethylether (30 mL) to afford a red Example 3. Catalyst activity is 4.0 kg polyolefin per g mixture, which is stirred overnight, filtered and dried under supported catalyst per hour, M=77,000; M/M=4.8; and vacuum (2.57 g., 78.2%). MI=0.7 dg/min. EXAMPLE 2 Example 4 shows that by treating a Support with an Preparation of Catalyst Supported on Diethylzinc 45 organozinc compound, the catalyst activity is increased, the molecular weight is increased and MI is decreased verSuS treated Silica Comparative Example 5. In a glove-box under nitrogen, 2.0 mL of 1.0 M dieth The preceding examples are meant only as illustrations. ylzinc in heptane is mixed with 2.00 g of G955 silica The following claims define the invention. (available from Grace Davison) having a surface area (BET) 50 I claim: of 280-355 m/g and a pore volume of 1.55–2.00 mL/g that 1. A process which comprises polymerizing an olefin in had been calcined at 250 C. After mixing at room tempera the presence of an activator and a Supported organometallic ture for about 0.5 hour, volatiles are removed by vacuum to complex, wherein the Supported organometallic complex is obtain 2.30 g of diethylzinc treated silica. prepared by treating a Support with about 0.1 to about 2 1.8 mL of 30% by weight methylalumoxane (MAO) in moles of an organozinc compound per kg Support and toluene is diluted by mixing with 3.6 mL toluene. Complex 55 combining the organozinc-treated Support with an organo 1-4 (13.8 mg, 0.019 mmole) is mixed with the diluted MAO metallic complex comprising a Group 3 to 10 transition Solution to make a deep green-blue Solution. This green-blue metal, M, and at least one indenoindolyl ligand that is solution is mixed further with 1.00 g of diethylzinc treated bonded to M. Silica prepared above. After Stirring for 30 minutes at room 2. The process of claim 1 wherein the Group 3 to 10 temperature, the Volatiles are removed by vacuum to obtain 60 transition metal is a Group 4 transition metal. 1.68 g of the Supported catalyst as a dark green powder. 3. The process of claim 1 wherein the activator is selected COMPARATIVE EXAMPLE 3 from the group consisting of alumoxanes, alkylaluminum compounds, organoboranes, ionic borates, ionic aluminates, Preparation of Catalyst Supported on Non-treated aluminoboronates and mixtures thereof. Silica 65 4. The process of claim 1 wherein some or all of the 1.8 mL of 30% by weight methylalumoxane (MAO) in activator is premixed with the organometallic complex, and toluene is diluted by mixing with 3.6 mL toluene. Complex this mixture is added to the organozinc-treated Support. US 6,933,353 B2 11 12 5. The process of claim 1 wherein the olefin is selected -continued from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 1-hexene and 1-octene and mixtures thereof. 6. The process of claim 5 wherein the olefin is ethylene in combination with a Second olefin Selected from the group consisting of 1-butene, 1-hexene and 1-octene. 7. The process of claim 1 wherein the organozinc com pound is Selected from the group consisting of dimethylzinc and diethylzino. 8. The process of claim 1 wherein the support is selected from the group consisting of Silicas, aluminas, and Silica aluminas. wherein M is a Group 3 to 10 transition metal; each L is 9. The process of claim 1 wherein the polymerization is independently Selected from the group consisting of halide, performed at a temperature within the range of about 300 alkoxy, aryloxy, Siloxy, alkylamino, and C-Co hydrocar C. to about 1000 C. 15 byl, L' is Selected from the group consisting of alkylamido, 10. A slurry polymerization process of claim 1. Substituted or unsubstituted cyclopentadienyl, fluorenyl, 11. A gas-phase polymerization process of claim 1. indenyl, boraaryl, pyrrolyl, azaborolinyl and indenoindolyl, 12. The process of claim 1 wherein the indenoindolyl X satisfies the Valence of M, R is Selected from the group ligand has a structure Selected from the group consisting of consisting of C-C hydrocarbyl, dialkylboryland trialkyl silyl; each R is independently selected from the group consisting of C-Co hydrocarbyl, H, F, Cl and Br; G is a divalent radical Selected from the group consisting of hydro carbyl and heteroatom containing alkylene radicals, diorga nosilyl radicals, diorganogermanium radicals and diorgano 25 tin radicals. 14. The process of claim 13 wherein L' is selected from the group consisting of Substituted or unsubstituted cyclopentadienyl, fluorenyl, indenyl, and indenoindolyl. 15. The process of claim 1 wherein the organometallic complex has a structure Selected from the group consisting of:

35

in which R is selected from the group consisting of C-Co 40 hydrocarbyl, dialkylboryl, trialkylsilyl and divalent radicals connected to a Second ligand; each R is independently Selected from the group consisting of C-C hydrocarbyl, H, F, Cl and Br; R is Selected from the group consisting of 45 C-Co hydrocarbyl, H and divalent radicals connected to a Second ligand wherein one of R or R is a divalent radical Selected from the group consisting of hydrocarbyl and heteroatom containing alkylene radicals, diorganosilyl radicals, diorganogermanium radicals and diorganotin radi 50 cals. 13. The process of claim 1 wherein the organometallic complex has a structure Selected from the group consisting of: 55 wherein M is a Group 3 to 10 transition metal; each L is independently Selected from the group consisting of halide, alkoxy, aryloxy, Siloxy, alkylamino, and C-Co hydrocar byl, L' is Selected from the group consisting of alkylamido, Substituted or unsubstituted cyclopentadienyl, fluorenyl, and 60 indenyl, boraaryl, pyrrolyl, azaborolinyl and indenoindolyl, X satisfies the valence of M, Rs is selected from the group consisting of C-so hydrocarbyl and H.; each R is inde pendently selected from the group consisting of Rs, F, Cland Br, G is a divalent radical Selected from the group consisting 65 of hydrocarbyl and heteroatom containing alkylene radicals, diorganosilyl radicals, diorganogermanium radicals and diorganotin radicals. US 6,933,353 B2 13 14 16. A method which comprises treating a Support with -continued about 0.1 to about 2 moles of an organozinc compound per kg Support and combining the treated Support with an organometallic complex comprising a Group 3 to 10 tran Sition metal, M, and at least one indenoindolyl ligand that is bonded to M. 17. The method of claim 16 wherein the support is Selected from the group consisting of Silicas, aluminas, and Silica-aluminas. 18. The method of claim 16 wherein the organozinc wherein M is a Group 4 transition metal; each L is inde compound is Selected from the group consisting of dimeth pendently Selected from the group consisting of halide, ylzinc and diethylzinc. alkoxy, aryloxy, Siloxy, alkylamino, and C-Co hydrocar 19. The method of claim 16 wherein the organometallic 15 byl, L' is Selected from the group consisting of alkylamido, Substituted or unsubstituted cyclopentadienyl, fluorenyl, complex has a structure Selected from the group consisting indenyl, boraaryl, pyrrolyl, azaborolinyl and indenoindolyl, of: X satisfies the valence of M, R is selected from the group consisting of C-C hydrocarbyl, dialkylboryland trialkyl silyl; each R is independently Selected from the group consisting of C-C hydrocarbyl, H., F, Cl and Br; G is a divalent radical Selected from the group consisting of hydro carbyl and heteroatom containing alkylene radicals, diorga and nosilyl radicals, diorganogermanium radicals and diorgano tin radicals. 20. The method of claim 16 wherein the complex is 25 premixed with an activator prior to combining with the organozinc-treated Support. 21. The method of claim 16 wherein the organozinc treated Support is combined with an activator prior to combining with the organometallic complex. k k k k k