KR20050085108A - New catalyst structure for olefin polymerization - Google Patents

Abstract

A catalyst comprising e.g. a pyridine bisimine ligand bonded to a transition metal by at least two heteroatoms of the ligand, the ligand having at least two aromatic groups or cyclopentadienyl groups on different heteroatoms of the ligand. The transition metal compound, its preparation, preparation and use of the catalyst in an olefin polymerization catalyst are also disclosed.

Description

NEW CATALYST STRUCTURE FOR OLEFIN POLYMERIZATION}

Cross References to Related Applications

This application claims priority from US patent application Ser. No. 10 / 301,884, filed Nov. 21, 2002 and patent application Ser. No. 10 / 692,068, filed Oct. 23, 2003.

Technical Field

The present application relates to catalyst components, catalyst systems, olefin polymerizations, polymer compositions, and articles made from such polymer compositions. More particularly, the present invention relates to catalysts with C ₁ , C ₂ or C _S symmetry.

As is well known, several processes and catalysts exist for the production of polyolefins. Conventional Ziegler-Natta catalyst systems utilize transition metal compounds cocatalyzed by aluminum alkyl.

In the 1980s, metallocene catalysts were commercialized for olefin polymerization, which included metallocene and aluminum alkyl components together with transition metal compounds having at least two cyclopentadienyl (Cp) ring ligands. Thus, titanocene, zirconocene and hafnocene have all been used as transition metal components in such metallocenes including catalyst systems for the production of polyolefins. The metallocene catalyst may be co-promoted with alumoxane rather than aluminum alkyl to provide a highly active metallocene catalyst system for the production of polyolefins.

In addition to Ziegler-Natta catalysts and metallocene catalysts, a number of "non-metallocene" type catalysts have been proposed for the polymerization of olefins. In particular, see, eg, The Search for New-Generation Olefin Polymerization Catalysts: Life Beyond Metallcenss , Angew. Chem. Int. Ed. In 1999, 38, 428-447, Britovsek et al. Review a number of olefin catalyst systems: group 3 metal catalysts such as scandium and yttrium complexes; Rare earth metal catalysts, such as lanthanide and actinide-based catalysts, stabilized with substituted cyclopentadienyl ligands; Carbon-based ligands (such as alkyl ligands, allyl ligands, Cp analogs), such as amide ligands combined with or alone with other ligands, amidate ligands combined with or alone with other ligands, and β-diketimate ligands Cation group 4 metal complexes comprising a nitrogen-based ligand and an oxygen-based ligand (such as an alkoxide ligand in combination with or alone with another ligand, such as a bis-alkoxide with addition donor); Neutral group 4 metal complexes; Group 5 metal catalysts; Group 6 metal catalysts; Group 8 metal catalysts; Group 9 metal catalysts; Group 10 metal catalysts; Group 13 metal catalyst.

Additionally, Iron and Cobalt Ethylene Polymerization Catalysts Bearing 2,6-bis (Imino) Pyridyl Ligands; Synthesis, Structures, and Polymerization Studies , Am. Chem. Soc. In 1999, 121, 8728-8740, Britovsek et al. Found some iron and cobalt for the polymerization of ethylene.

WO 98/30612, published July 16, 1998, selected iron complexes of 2,6-pyridinecarboxaldehydebis (imine) and 2,6-diacyclylpyridinebis (imine) as catalysts for the polymerization of propylene. To start. WO 99/12981, published March 18, 1999, discloses catalyst composites having bridges comprising heteroatoms bridging the R groups R ⁵ and R ⁷ , these complexes being “especially ethylene only As useful for polymerizing or interpolymerizing ethylene and higher 1-olefins (lines 2, lines 28-29). Bridged R groups R ⁵ and R ⁷ are independently selected from hydrogen, halogen, and hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl. Creating chiral composites suitable for the production of high tacticity, crystallinity polypropylene is not taught or suggested.

The following patent discloses a bridged metallocene catalyst system: US Pat. No. 5,145,819, issued September 8, 1992 to Winter et al .; US Patent No. 5,158,920, issued to Razavi on October 27, 1992; US Patent No. 5,243,001 issued to Winter et al. On September 7, 1993; US Patent No. 6,002,033, issued to Razavi et al. On December 14, 1999; US Patent No. 6,066,588, issued to Razavi et al. On May 23, 2000; US Patent No. 6,177,529 B1, issued to Razavi et al. On January 23, 2001; US Patent No. 6,194,343 B1, issued February 27, 2001 to Collins et al .; US Patent 6,211,110 B1, issued April 3, 2001 to Santi et al .; And US Pat. No. 6,268,518 B1, issued July 31, 2001 to Resconi et al.

However, despite the above developments, there is still a need in the art for catalyst composition for methods of making such compositions, polymerization methods using such components, polymer compositions, and items made from such polymer compositions. .

Summary of the Invention

According to one embodiment of the present invention, a bridged compound is provided having the formula:

Where M is a metal; Each X is an atom or group covalently or ionically bonded to M and may be the same or separate; R ₁ and R ₂ may be the same or separate and are substituted or unsubstituted cyclopentadienyl or aromatic rings; R _B is a cyclopentadaenyl or structural bridge between aromatic rings R ₁ and R ₂ and imparts stereorigidity to the rings and comprises at least one heteroatom bonded to M, each R ₁ and R ₂ is the same as the R _B, or separate from, and coupled to a hetero atom which is also bonded to M; Z is the coordination number of M and is at least 4; m is the number of bonds between the heteroatoms of M and R _B , and is 2 or more to impart steric stiffness; And R ₁ , R ₂ , and R _B are selected to provide C ₁ , C ₂ or C _S symmetry to the catalyst component. The catalyst component may be chiral or non-chiral. In some embodiments, it may be desirable to have a catalytic component that is chiral.

According to another embodiment of the present invention, there is provided a method of making a bridged metallocene compound comprising contacting a metal compound of formula M (X) ₂ with a bridged compound of the formula:

Wherein R _B , R ₁ and R ₂ are as defined above.

According to another embodiment of the present invention, there is provided a catalyst system comprising an activated bridged metallocene compound having the formula:

Where M, X, R ₁ , R ₂ , m and Z are as defined above.

According to yet another embodiment of the present invention, a method of making a catalyst system comprising contacting an active agent with a bridged metallocene compound having the formula:

Where M, X, R ₁ , R ₂ , m and Z are as defined above.

According to another embodiment of the present invention, there is provided a method of forming a polyolefin comprising contacting an olefin monomer or mixture of monomers in the presence of an activated bridged metallocene compound having the formula:

Where M, X, R ₁ , R ₂ , m and Z are as defined above.

With respect to all of the above embodiments, more various embodiments are provided by changing M, X, R ₁ , R ₂ , m and Z as detailed in the detailed description.

details

In one embodiment of the invention the bridged metallocene catalyst component of the present invention can be represented by the following formula.

Where M is a metal; Each X is an atom or group covalently or ionically bonded to M and may be the same or separate; R ₁ and R ₂ may be the same or separate and are substituted or unsubstituted cyclopentadienyl or aromatic rings; R _B is cyclopentadaenyl or a structural bridge between the aromatic rings R ₁ and R ₂ and imparts stereostericity to the rings and comprises at least one heteroatom bonded to M, each of R ₁ and R ₂ Is bonded to the same or separate hetero atom of R _B , which is also bonded to M; Z is the coordination number of M and is at least 4; m is the number of bonds between the heteroatom (s) of M and R _B , and is 2 or more to impart steric stiffness; Because the number of bonds around M cannot exceed its coordination number Z; R ₁ , R ₂ , and R _B are selected to provide C ₁ , C ₂ or C _S symmetry to the catalyst component. The catalyst component may be chiral or non-chiral. In some embodiments, it may be desirable to have a catalytic component that is chiral.

The metal M of the present invention may be any suitable metal useful as the metal component in the metallocene catalyst. As a non-limiting example, M may be selected from any of the metals known in the art to be useful as metal components in metallocene catalysts. M will be chosen to have a coordination number Z, at least equal to the number of substituents attached to M, which is the number of m of R _B heteroatom-to-metal bond plus 2 (relative to both X). M can be selected from transition metals, lanthanides and actinides. M can be selected from group 3d, 4d or 5d transition metals, such as Fe, Co, Ni, Ru, Rh, Pd, Os, Ir and Pt. In some embodiments M may be preferably selected from Fe, Co and Ni. R ₁ and R ₂ may be the same or separate and may be generally described as substituted or unsubstituted cyclopentadienyl or aromatic rings.

As a non-limiting example, R ₁ and R ₂ may be selected from any substituted or unsubstituted cyclopentadienyl or aromatic rings known in the art as useful in metallocene catalysts. Non-limiting examples of hydrocarbon radicals suitable for use as R ₁ and R ₂ are shown in the examples below. As a non-limiting example, R ₁ and R ₂ may be described as cyclopentadienyl or aromatic rings of form (C ₅ (R ′) ₄ ), where R ′ may be the same or separate and R ′ is Substituted or unsubstituted hydrocarbyl radical having hydrogen or 1-20 carbon atoms.

Non-limiting examples of hydrocarbyl radicals suitable for use as R 'include unsubstituted and substituted alkyl, alkenyl, aryl, alkylaryl or arylalkyl radicals. More specific non-limiting examples of suitable hydrocarbyl radicals include unsubstituted and substituted methyl, ethyl, propyl, butyl, amyl, isoamyl, hexyl, isobutyl, heptyl, octyl, nonyl, decyl, cetyl, phenyl, Methylene, ethylene, propylene, and other similar groups.

R _B acts as a structural bridge between cyclopentadienyl or aromatic rings R ₁ and R ₂ and imparts steric stiffness to the rings and includes n heteroatoms (“HA”) bonded to M. It may be desirable for the number of heteroatoms bonded to M to have n ≧ 1, n ≧ 2, and in some embodiments n ≧ 3. Examples of suitable structural bridges R _B are provided in the embodiments.

Heteroatoms useful in structural bridges R _B include any that can be coordinated to the metal M by "coordinating" bonds, which are bonds formed by giving lone pairs of electrons from heteroatoms. If R _B comprises one or more heteroatoms bonded to M, they may be the same heteroatom or separate heteroatoms. Non-limiting examples of suitable heteroatoms include O, N, S and P. In some embodiments, the heteroatoms are preferably N.

R ₁ is bonded directly or indirectly to a heteroatom of R _B , which is also a heteroatom which is also bonded to M, via a separate heteroatom. Similarly, R ₂ is also bonded directly or indirectly through a separate heteroatom to a heteroatom of R _B which is also a heteroatom which is also bonded to M. R ₁ and R ₂ may be bonded to the same heteroatom, also bonded to M, or may be bonded to separate heteroatoms, also bonded to M. The structure of the R ₁ -R ₂ -R _B moiety can be any that does not interfere with the symmetry of the catalysts. For example, the R ₁ -R ₂ -R _B moiety can have the following structure, which is also within the scope of the claims of the present invention:

In some embodiments, a bridging group having four heteroatoms is within the scope of the present invention. According to one embodiment of the invention, R ₁ , R ₂ and R _B are selected to provide a catalyst component with C ₁ , C ₂ or C _S symmetry. Certain configurations of R ₁ , R _2, and R _B that do not disrupt the C ₁ , C _2, or C _S symmetry, which are known to be useful to those of ordinary skill in the art of preparing catalysts, are associated with the present invention. Can be used. The catalyst component may be chiral or non-chiral. In some embodiments, it may be desirable to have a catalytic component that is chiral.

Each X may be an atom or group known to be used with the catalyst and is generally covalently or ionic bonded to M. Each X may be the same or separate, but generally each X is the same. Non-limiting as embodiments, X is a halide, sulphate, nitrate, thiolate, _{^{thioether-carboxylate, BF 4 -, PF 6 -}} , hydride, hydrocarbyl oxide, carboxylate, substituted or unsubstituted dihydro- Carbyl, and heterohydrocarbyl. Non-limiting examples of such atoms or groups include chloride, bromide, methyl, ethyl, propyl, butyl, octyl, decyl, phenyl, benzyl, methoxide, ethoxide, isopropoxide, toxylate, triflate, formate , Acetates, phenoxides and benzoates. It may be preferred when X is a halide or C ₁ to C ₂₀ hydrocarbyl. In some embodiments, it is preferred that X is chloride. Bridged catalyst components are generally made by contacting a bridged intermediate with a compound of the form M (X) ₂ . More details are provided in the embodiments.

The invention relates to the reaction product and optionally to one or more of the aforementioned bridging catalyst components and one or more active agents and / or cocatalysts (described in more detail below) or active agents and / or promoters such as, for example, methylaluminoxane (MAO) It further comprises a catalyst system comprising an alkylation / scavenging agent such as triethylaluminum compound such as triethylaluminum (TEAL). The metallocene catalyst component described above may also be supported as is known in the metallocene technology. Typical supports may be supports such as talc, inorganic oxides, clays, and clay minerals, ion exchanged layered compounds, resin support materials such as diatomaceous earth, silicates, zeolites or polyolefins. Specific inorganic oxides include silica and alumina, used alone or in combination with other inorganic oxides such as magnesia, titania, zirconia and the like. Non-metallocene transition metal compounds, such as titanium tetrachloride, can be incorporated into the supported catalyst components. Inorganic oxides used as support agents have an average particle size over 30-600 microns, preferably 30-100 microns, 50-1,000 square meters per gram, preferably 100-400 square meters per gram, and 0.5-3.5 cc / g, preferably having a pore volume of about 0.5-2 cc / g.

The bridged catalyst of the present invention may be used in combination with some form of active agent to make an active catalyst system. The term "active agent" is defined herein to be any compound or component, or combination of compounds or components, which may enhance the ability of one or more catalysts to polymerize olefins into polyolefins. Alkylalumoxanes such as methylalumoxane (MAO) are commonly used as metallocene activators. Generally alkylalumoxanes comprise between about 5 and 40 repeat units.

Alumoxane solutions, especially methylalumoxane solutions, can be obtained commercially as solutions with varying concentrations. There are various methods of making alumoxane, and non-limiting examples are disclosed in US Pat. Nos. 4,665,208, 4,952,540, 5,091,352, 5,206,199, 5,204,419, 4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,308,815, 5,329,032, 5,248,801, 5,235,081, 5,103, 031 and EP-A-0 561 476, EP 0 279 586, EP-A-0 594 218 and WO 94 / Described in 10180, each of which is fully incorporated herein by reference. (As used herein, unless otherwise stated, "solution" refers to any mixture including suspension.)

Ionizing activators can also be used to activate the bridged catalyst. These active agents are neutral or ionic, or are compounds such as tri (n-butyl) ammonium tetrakis (pentaflurophenyl) borate, which ionize neutral catalyst compounds. Such ionizing compounds may include active protons, or some other cation associated with, but not coordinating to, or loosely coordinating with the remaining ions of the ionizing compound. Combinations of active agents, such as alumoxane and ionizing active agent combinations, may also be used. See WO 94/07928.

The description of ionic catalysts for coordination polymerization, including metallocene cations activated by non-coordinating anions, is incorporated herein by reference EP-A-0 277 003, EP-A-0 277 004 and US Patent 5,198,401 and WO-A-92 / 00333. These teach the preferred method of preparation, where metallocenes (bisCp and monoCp) are protonated by anionic precursors, alkyl / hydrides to non-coordinate anions to cation and charge-balance The group is extracted from the transition metal. Suitable ionic salts include, but are not limited to, aluminum salts with fluoride aryl-substituents such as phenyl, biphenyl and naphthyl or tetrakis-substituted borates.

The term noncoordinating anion (NCA) refers to an anion that is not coordinating to a cation or weakly coordinating to a cation and remains sufficiently unstable to be replaced by a neutral Lewis base. Compatible noncoordinating anions are those that do not degrade to neutrality when the initially formed complex decomposes. In addition, the anion will not transfer anion substituents or fragments to the cation to form neutral four-coordinate metallocene compounds and neutral by-products from the anion.

The use of ionizing compounds, including both active but capable of producing active metallocene cations and uncoordinated anions, is also known. See, eg, EP-A-0 426 637 and EP-A-0 573 403 (incorporated herein by reference). An additional method of making ionic catalysts is using ionized anion precursors that initially form neutral Lewis acids but form cations and anions during ionization reactions with metallocene compounds, such as the use of tri (pentafluorophenyl) boranes. . See EP-A-0 520 732 (incorporated herein by reference). Ion catalysts for further polymerization may also be prepared by oxidation of the metal center of the transition metal compound by an anion precursor comprising a metal oxide group together with the anion group. See EP-A-0 495 375 (incorporated herein by reference).

If the metal ligands contain halogen moieties that cannot be ionized under standard conditions (eg, bis-cyclopentadienyl zirconium dichloride), they are lithium or aluminum hydrides or alkyl, alkylalumoxanes, Grignards It can be converted by a known alkylation reaction with an organometallic compound such as a reagent (Grignard reagent). EP-A-0 500 944 (incorporated herein by reference) regarding an in situ process that describes the reaction of a dihalo-substituted metallocene compound with an alkyl aluminum compound before or with activation of the anionic compound. And EP-A1-0 570 982.

Preferred methods for supporting ionic catalysts comprising metallocene cations and NCA are described in US Pat. No. 5,643,847 (all incorporated herein by reference); No. 6,143,686; And 6,228,795. These NCA support methods generally involve the use of neutral anion precursors, which are strong enough Lewis acids to react with the hydroxyl reactive functionality present on the silica surface, so that the Lewis acids are covalently bound.

Additionally, when the activator for the metallocene supported catalyst composition is NCA, the NCA is added first to the support composition, followed by the bridged metallocene catalyst. If the active agent is MAO, preferably the MAO and bridged metallocene catalyst are dissolved together in solution. The support is then contacted with the MAO / metallocene catalyst solution. Other methods and order of addition will be apparent to those skilled in the art.

The catalyst of the invention can be used for the polymerization of α-olefins or mixtures of α-olefins with at least two carbon atoms. For example, the present catalyst may be useful for catalyzing ethylene, propylene, butylene, pentene, hexene, 4-methylpentene and mixtures thereof. The catalyst of the present invention can be used for the polymerization of propylene to produce polypropylene, such as, for example, high crystallinity polypropylene.

 Polymerization and pre-polimerization conditions are known in the art where applicable and need not be described in detail herein. In general, the polymerization is carried out by bringing together the α-olefin monomer or mixture of α-olefins together in the presence of the above-described catalyst system under polymerization conditions. The following examples are given as specific embodiments of the invention and demonstrate the practice and advantages of the invention.

These embodiments are merely provided to illustrate some embodiments of the invention and are not intended to limit the scope of the specification or claims. In these embodiments, all manipulations of air / humidity-sensitive materials were performed in conventional vacuum / inert atmosphere using standard Schlenk line techniques.

Example 1

Procedures such as those described in WO 99/12981 were used for the synthesis of ligand intermediate A of the formula:

2,6-Diisopropylaniline (3.46 ml, 18.4 mmol) was added dropwise to a solution of 2,6-diacetylpyridine (1.5 g, 9.2 mmol) in pure ethanol (25 ml). A few drops of glacial acetic acid were added and the solution was refluxed for 48 hours. Concentration of the solution to half volume and cooling to 78 ° C. resulted in intermediate A as pale yellow crystals (80%). The calculated value for the intermediate C ₃₃ H ₄₃ N ₃ is C 82.3%; H 8.9%; N 8.7%. Fast atom bombardment mass spectrometry (FABMS) results are M + (481). NMR analysis showed 1H NMR (CDCl ₃ ): 8.6 B 7.9 [m, 3H, C ₅ H ₃ N], 7.2 B 6.9 [m, 6H, C ₆ (CHMe ₂ ) H ₃ ], 2.73 [sept, 4H, CHMe ₂ ], 2.26 [s, 6H, C ₅ H ₃ N (CMeNAr) ₂ ] and 1.16 [m, 24H, CHMe ₂ ].

Example 2

250 mg, 1.09 eq. Of Intermediate A and 95 mg of FeCl ₂ .4H ₂ O were metered into a 10 ml Schlenk flask with stirbar. The flask was placed on a Schlenk manifold, backfilled three times with argon, and 10 ml of tetrahydrofuran (THF) was added during stirring. After 2 hours, THF was removed under vacuum. The resulting dark blue solid (of the following formula) was washed twice with ether and dried under vacuum.

Example 3

This example shows the generation of ligands with C ₂ / class A symmetry. The same general synthesis follows Example 1, except that 2,6-diisopropylaniline is replaced with indine.

1-amino-indine (18.4 mmol) was added to a solution of 2,6-diacetylpyridine (9.2 mmol) in pure ethanol (50 ml). A few drops of glacial acetic acid were added and the solution was refluxed for 48 hours. The solution was concentrated to half volume and cooled to room temperature and filtered to yield the following intermediate.

Example 4

The catalyst from the ligand of Example 3 (intermediate with symmetric C ₂ / class A) was synthesized using the same general synthesis as in Example 2, providing the following catalyst components.

Example 5

This example shows the generation of ligands with C2 / class B symmetry. The first part of this ligand differs from that of Example 1 above. The first part of the synthesis begins with the reduction to the diamine of diacetylpyridine using the Leckart-Wallach reaction. In the scheme below, the general reaction is shown in terms of the reduction to the amine of carbonyl.

Scheme 1. Reduction of Carbonyl Compounds with Amines (Roichardt-Balach Reaction):

Example 6

This example is reduced to an amine of carbonyl, specifically, 1-phenylethylamine (Vogel's Practical Organic Chemistry including qualitative organic analysis, 4 ^th Ed, Furniss, BS, et al., School of Chemistry Thames Polytechnic Longman Scientific and Technical, 1978). 250 with Claisen still-head with short fractionating column of 126 g (2.0 mol) ammonium formate, 72 g (0.6 mol) acetophenone and several porous porcelain chips added to ml flask; A thermometer extending to the bottom of the flask was inserted and a short condenser was installed for the distillation down to the side arm. The flask was heated (with a heating mantle or in an air batch); First the mixture melts into two layers and distillation takes place. The mixture became homogeneous at 150-155 ° C. and the reaction occurred with some bubbles. Heating continued until the temperature reached 185 ° C. (about 2 hours); Acetophenone, water and ammonium carbonate distillation. Heating was stopped at 185 ° C., and the top layer of acetophenone was separated from the distillate and recovered without drying into a flask. The mixture was heated at 180-185 ° C. for 3 hours and allowed to cool; Acetophenone can be recovered from the distillate by extraction with 20 ml portion of toluene. The reaction mixture was transferred to a 250 ml separation funnel and shaken with two 75 ml portions of water to remove formamide and ammonium formate. Crude (1-phenylethyl) formamide was transferred to the original reaction flask and the aqueous layer was extracted with two 20 ml portions of toluene. Toluene extract was delivered to the flask and 75 ml of concentrated hydrochloric acid and several porous porcelain chips were added. The mixture was heated carefully until about 40 ml of toluene was collected and slowly boiled under reflux for an additional 40 minutes; Hydrolysis proceeded rapidly with 1-phenylethylamine hydrochloride except for a small layer of constant acetophenone. The reaction mixture was allowed to cool and acetophenone was removed by extraction with four 20 ml portions of toluene. Aqueous acid solution was transferred to a 500 ml round bottom flask prepared for stream distillation, a solution of 62.5 g of sodium hydroxide was carefully added to 125 ml water, and the stream was distilled: the distillation flask was volume Heated to remain almost constant. Most of the amine was contained in 500 ml of the first distillate; The operation was stopped when the distillate was slightly alkaline. The distillate was extracted with five 25 ml portions of toluene, the extract was dried over sodium hydroxide pellets and fractionally distilled. Toluene was distilled at 111 ° C. and was accompanied by phylethylamine. The latter was collected as a fraction of bp 180-190 ° C. (most of the product was distilled at 184-186 ° C. (3); yield was 43 g (59%)).

Example 7

This example shows the synthesis of 2,6- (1,1'-diethylhydroxyimino) -pyridine (dioxime) (Scheme 2). Hydroxylamine hydrochloride (0.98 g; 14.1 mmol) and pyridine (5 mL) were placed in the flask under argon and equipped with a magnetic stirrer. 2,6-Diacetylpyridine (1.0 g; 6.1 mmol) was added and the mixture was refluxed for 8 hours and stirred at room temperature for 2 days. Pyridine was removed under vacuum. Water (20 mL) was added to the residue. The white solid was washed with a small amount of water. Dioxime was dried overnight under vacuum to give a white powder (1.08 g; 5.6 mmol; 92%), which was used without further purification. Results of NMR analysis were: ¹ H NMR (CD ₂ Cl ₂ ), γ: 7.81 (d, 2H, H meta, J = 7.8 Hz), 7.70 (t, 1H, H para, J = 7.8 Hz), 2.79 (s , 2H, OH), 2.33 (s, 6H, Me).

Scheme 2. Synthesis of Dioxime

Example 8

Reduction with diamine of dioxime as obtained in Example 7 is provided using the following synthetic procedure (Scheme 3).

Synthesis of 2,6- (1,1'-diethylamino) -pyridine (diamine). 2,6- (1,1'-Diethylhydroxyimino) -pyridine (500 mg; 2.6 mmol) was added to a flask equipped with a magnetic stirrer, placed under argon, with ethanol (10 mL) and acetic acid (6 mL ). Zinc powder (6 g; 94 mmol) was added dropwise over 10 minutes. After stirring for 1 hour a white precipitate appeared. The mixture was stirred at room temperature for 24 hours. Undissolved zinc was removed by filtration and washed with a small amount of ethanol. The filtrate was concentrated in vacuo. A small portion of water was added and evaporated to remove any remaining acetic acid. The mixture was made into a strong base (pH> 12) by adding saturated aqueous potassium hydroxide solution (about 56 mL) until all Zn (OH) ₂ was redissolved. The aqueous layer was transferred to a separatory funnel and extracted with 4 portions of diethyl ether (20 mL). The combined organic fractions were dried over MgSO ₄ and the solvent was removed under vacuum to give a colorless oil (310 mg; 1.87 mmol; 72%). NMR analysis results are: ¹ H NMR (CD ₂ Cl ₂ ), γ: 7.59 (t, 1H, H para, J = 7.8 Hz), 7.14 (d, 2H, H meta, J = 7.8 Hz), 4.07 (q , 2H, CH , J = 6.6 Hz), 1.79 (s, 4H, NH ₂ ), 1.38 (d, 6H, Me, J = 6.6 Hz).

Scheme 3. Synthesis of Diamine

Example 9

This example reacts a diamine as obtained in Example 7 with a ketone to provide a ligand for a catalyst with symmetric C ₂ / class B (Scheme 4).

Scheme 4. Synthesis of Ligands for Catalysts with Symmetric C ₂ / Class B

Example 10

This example shows the synthesis of bis-imines on catalysts with C ₂ / class B symmetry based on the reaction of diamines with β-tetralone (Scheme 5).

In a 100 mL round bottom flask equipped with a stir bar, diamine (0.50 g, 3.03 mmol) and β-tetralol (0.85 mL, 6.43 mmol) were added to the flask at 25 and the mixture produced a clear dark yellow liquid. The flask was then placed under vacuum and backfilled with argon three times and placed under argon. After stirring for 10 minutes, the mixture produced a pale yellow solid tar, which made the stirring very difficult. 25 mL of ethanol was added to aid in stirring the mixture. A clear orange yellow solution was obtained. After stirring at 25 ° C. for 2 hours, the solvent was removed under vacuum and the remaining pale yellow foam solid was obtained. 1 H-NMR analysis indicated that the product was the most desired bisimine ligand (78% yield). NMR analysis results are: ¹ H NMR (300 MHz, CD ₂ Cl ₂ , 35 ° C.), γ: 7.63 (t, 1H), 7.21 (d, 4H), 6.96 (t, 4H), 6.80 (t, 2H) , 6.77 (m, 2H), 5.14 (d, 2H), 4.64 (d, 2H), 2.80 (t, 4H), 2.36 (t, 4H), 1.55 (d, 6H, Me).

Scheme 5. Synthesis of Bis-Imine Using β-Tetralone

Example 11

This example shows the synthesis of bis-imines on catalysts with C ₂ / class B symmetry based on the reaction of diamines with cyclohexanone (Scheme 6). The same procedure as described in Example 6 was used for the synthesis of bis-imines.

Scheme 6. Synthesis of Bis-Imine Using Cyclohexanone

Example 12

This example shows the synthesis of bis-imines on a catalyst with C ₂ / class B symmetry based on the reaction of diamine with mesitylaldehyde (Scheme 7). The procedure as described in Example 9 was used for the synthesis of bis-imines. Bis-imine: NMR analysis results are: ¹ H NMR (300 MHz, CD ₂ Cl ₂ , 35 ° C.), γ: 8.7 (s, 2H, HCN), 7.66 (t, J = 7.8 Hz, 1H, Hpara), (d, J = 7.8 Hz, 2H, Hmeta), 6.88 (s, 4Hmeta, Mes), 4.63 (q, J = 6.6 Hz, 2H, HCH ₃ ), 2.42 (s, 12H, CH ₃ ortho, Mes), 2.28 (s, 6H, CH ₃ para, Mes), 1.63 (d, J = 6.6 Hz, 6H, Me).

Scheme 7. Synthesis of bis-imines using mesaldehyde

Example 13

Another catalyst synthesis procedure for producing a catalyst with C ₂ / class B is the same procedure as described in WO 98/30612 (except for the location of the double bond in the structure with other R groups) and is represented by the following scheme:

The ligand of Example 9 (1.05 eq.) And the metal salts in either the hydrated or anhydrous form were added together to the Schlenk flask under inert atmosphere and then changed to THF. The mixture is stirred for several hours until no unreacted salts are observed. The mixture is filtered in air and the solid is washed with Et ₂ O and dried in vacuo.

Example 14

To synthesize ligands for catalysts with C _S / class B symmetry or C ₁ / class B symmetry, a procedure similar to that used for C ₂ / class B symmetry is used. The only exception is the reaction of two different ketones with diamine. General procedure for this synthesis is shown in the following formula (Scheme 8).

Scheme 8. Synthesis of Ligands for Catalysts with C _S / Type B Symmetry

Example 15

To synthesize a structure with C ₂ / class C symmetry, a procedure similar to that used for C ₂ / class B symmetry is used. The only exception is that one acetyl group is reduced on 2,6-diacetylanaline. The general procedure for this synthesis is shown in the following formula, where only one acetyl is reduced to amine.

Example 16

In this example, the amine of Example 14 is reacted with a ketone to provide an R group double bond for nitrogen.

Example 17

In this example, the amine is reacted with the mono-acetyl intermediate of Example 15 to provide a single bond to the R group for nitrogen, as shown in the formula below.

Example 18

The catalyst is synthesized according to the procedure described in Example 13.

Using a single bond, a double bond, or another R group bonded to a nitrogen atom with one single bond and one double bond, symmetry with respect to C ₁ and C _S can also be obtained. Some embodiments of other symmetry are summarized in Table 1 with respect to structures such as those shown in Table 1.

Any patents, patent applications, articles, books, articles, and any other publications cited herein are hereby incorporated by reference for teaching or suggestive purposes.

Table 1. Example of symmetry

C ₂  X-ray data of symmetric iron complex

The solid state structure of the iron composite is determined by single crystal X-ray diffraction. Selected crystallographic data is summarized in Table 2, and the structure is depicted in the formula from Example 4 and shown in the table below.

Table 2. Selected lengths and angles of C ₂ symmetrical iron composites

Complex 1: 2,6- [bis-1- (1-indanylimino) ethyl] pyridine iron (II) chloride

Complex 2: 2,6-bis [1- (1-naphthylimino) ethyl] pyridine iron dichloride

* Compounds 1 and 2 have the formula shown above.

Molecular structure of 2,6- [bis-1- (1-indanylimino) ethyl] pyridine iron (II) chloride (complex 1)

Figure 2. Molecular structure of 2,6-bis [1- (1-naphthylimino) ethyl] pyridine iron dichloride (Compound 2)

While exemplary embodiments of the invention have been described in particular, it will be understood that various other modifications will be apparent and may be readily made by those skilled in the art without departing from the scope of the invention. Accordingly, the scope of the claims appended hereto is not to be limited to the embodiments and detailed description set forth herein, but the claims include all patentable novel features present in the present invention and are known to those skilled in the art to which this invention pertains. It is intended to be interpreted to include all features which should be treated as equivalent to them.

Claims (20)

Bridged compounds having the formula: Where M is a metal; Each X is an atom or group covalently or ionically bonded to M and may be the same or separate; R ₁ and R ₂ may be the same or separate and are substituted or unsubstituted cyclopentadienyl or aromatic rings; R _B is cyclopentadaenyl or a structural bridge between the aromatic rings R ₁ and R ₂ and imparts stereostericity to the rings and comprises at least one heteroatom bonded to M, each of R ₁ and R ₂ Is bonded to the same or separate heteroatom of R _B ; Z is the coordination number of M and is at least 4; m is the number of bonds between the heteroatoms of M and R _B , and is 2 or more to impart steric rigidity; And R ₁ , R ₂ , and R _B are selected to provide C ₁ , C ₂ or C _S symmetry to the catalyst component. The bridged compound of claim 1, wherein M is selected from the group consisting of transition metals and lanthanide metals, and heteroatoms are selected from the group consisting of O, N, S and P. The bridged compound of claim 1, wherein R _B comprises at least three heteroatoms, R ₁ is bonded to one of the heteroatoms, and R ₂ is bonded to the other of the heteroatoms. The bridged compound of claim 1, wherein M is selected from Fe, Co, and Ni. The compound of claim 1, wherein M is Fe, R _B comprises three heteroatoms bonded to M, R ₁ is bonded to one of three heteroatoms, and R ₂ is a heteroatom to which R ₁ is bonded To heteroatoms and other; M is a bridged compound selected from Fe, Co and Ni. The bridged compound of claim 5, wherein each X is independently selected from halides and substituted or unsubstituted hydrocarbons. A method of making a bridged compound comprising contacting a metal compound of formula M (X) ₂ with a bridged compound R _B having the formula: Where M is a metal; Each X is an atom or group covalently or ionically bonded to M and may be the same or separate; R ₁ and R ₂ may be the same or separate and are substituted or unsubstituted cyclopentadienyl or aromatic rings; R _B is cyclopentadaenyl or a structural bridge between aromatic rings R ₁ and R ₂ and imparts stereosteric rigidity to the rings and comprises at least one heteroatom suitable for bonding to M, each of R ₁ and R ₂ is bonded to the same or separate heteroatom of R _B ; And R ₁ , R ₂ , and R _B are selected to provide C ₁ , C ₂ or C _S symmetry to the bridged metallocene compound. 8. The method of claim 7, wherein M is selected from the group consisting of transition metals and lanthanide series metals, and heteroatoms are selected from the group consisting of O, N, S and P. 8. The bridged compound of claim 7, wherein R _B comprises three heteroatoms, R ₁ is bonded to one of three heteroatoms, and R ₂ is bonded to the other of the three heteroatoms. Way. 8. The method of claim 7, wherein M is selected from Fe, Co, and Ni. 8. The heteromorphic compound of claim 7 wherein M is Fe, R _B comprises at least 3 heteroatoms, R ₁ is bonded to one of 3 heteroatoms, and R ₂ is a heteroatom different from the heteroatom to which R ₁ is bonded Is bonded to an atom; M is a method for making a bridged compound selected from Fe, Co and Ni. The method of claim 11, wherein each X is independently selected from halides and substituted or unsubstituted hydrocarbons. A catalyst system comprising an activated bridged compound having the formula: Where M is a metal; Each X is an atom or group covalently or ionically bonded to M and may be the same or separate; R ₁ and R ₂ may be the same or separate and are substituted or unsubstituted cyclopentadienyl or aromatic rings; R _B is cyclopentadaenyl or a structural bridge between the aromatic rings R ₁ and R ₂ and imparts stereostability to the ring and comprises at least one heteroatom bonded to M, each R ₁ and R ₂ is R _B The same or separate, to a heteroatom which is also bound to M; Z is the coordination number of M and is at least 4; m is the number of bonds between the heteroatoms of M and R _B , and is 2 or more to impart steric stiffness; And R ₁ , R ₂ , and R _B are selected to provide C ₁ , C ₂ or C _S symmetry to the catalyst component. The catalyst system of claim 13, wherein M is selected from the group consisting of transition metals and lanthanide metals, and heteroatoms are selected from the group consisting of O, N, S and P. The catalyst system of claim 13, wherein R _B comprises at least three heteroatoms bonded to M, R ₁ is bonded to one of the heteroatoms, and R ₂ is bonded to the other of the heteroatoms. The catalyst system of claim 13, wherein M is selected from Fe, Co, and Ni. The hetero atom of claim 13, wherein M is Fe, R _B comprises three heteroatoms bonded to M, R ₁ is bonded to one of three heteroatoms, and R ₂ is a heteroatom to which R ₁ is bonded To heteroatoms and other; M is a catalyst system selected from Fe, Co and Ni. 18. The catalyst system of claim 17, wherein each X is independently selected from halides and substituted or unsubstituted hydrocarbons. A method of making a catalyst system comprising contacting an active agent with a bridged compound having the formula Where M is a metal; Each X is an atom or group covalently or ionically bonded to M and may be the same or separate; R ₁ and R ₂ may be the same or separate and are substituted or unsubstituted cyclopentadienyl or aromatic rings; R _B is cyclopentadaenyl or a structural bridge between the aromatic rings R ₁ and R ₂ and imparts stereosterility to the rings and comprises at least one heteroatom bonded to M, each R ₁ and R ₂ is The same or separate R _B is bonded to a heteroatom also bonded to M; Z is the coordination number of M and is at least 4; m is the number of bonds between the heteroatoms of M and R _B , and is 2 or more to impart steric rigidity; And R ₁ , R ₂ , and R _B are selected to provide C ₁ , C ₂ or C _S symmetry to the catalyst component. A method of forming a polyolefin comprising contacting an olefin monomer or a mixture of monomers in the presence of an activated bridged compound having the formula: Where M is a metal; Each X is an atom or group covalently or ionically bonded to M and may be the same or separate; R ₁ and R ₂ may be the same or separate and are substituted or unsubstituted cyclopentadienyl or aromatic rings; R _B is cyclopentadaenyl or a structural bridge between the aromatic rings R ₁ and R ₂ and imparts stereosterility to the rings and comprises at least one heteroatom bonded to M, each R ₁ and R ₂ is The same or separate R _B is bonded to a heteroatom also bonded to M; Z is the coordination number of M and is at least 4; m is the number of bonds between the heteroatoms of M and R _B , and is 2 or more to impart steric stiffness; And R ₁ , R ₂ , and R _B are selected to provide C ₁ , C ₂ or C _S symmetry to the catalyst component.