JP4977322B2 - A new catalyst structure for olefin polymerization. - Google Patents

Description

Cross-reference of related applications

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

The present invention relates to catalyst components, catalyst systems, olefin polymerization, polymer compositions, and articles made from such polymer compositions. In particular, the invention relates to a catalyst having C ₁ , C ₂ or _CS symmetry.

  As is well known, there are various methods and catalysts for producing polyolefins. Traditional Ziegler-Natta catalyst systems use transition metal compounds co-catalyzed with aluminum alkyl.

  In the 1980's, metallocene catalysts for olefin polymerization were commercialized that contained metallocene and aluminum alkyl components, and the transition metal compound had two or more cyclopentadienyl (Cp) ring ligands. Accordingly, titanocene, zirconocene and hafnocene have all been used as transition metal components in metallocene-containing catalyst systems for the production of polyolefins. The metallocene catalyst can use alumoxane as a cocatalyst rather than aluminum alkyl to provide a highly active metallocene catalyst system for the production of polyolefins.

  In addition to Ziegler-Natta and metallocene catalysts, a number of "non-metallocene" type catalysts have been suggested for olefin polymerization. Specifically, for example, in Non-Patent Document 1, Britovsek et al., Group 3 metal catalysts such as scandium and yttrium complexes; Rare earth metal catalysts such as lanthanides and actinides stabilized by substituted cyclopentadienyl ligands Catalytic Group 4 metal complexes including carbon-based ligands (such as alkyl ligands, allyl ligands, Cp analogs), nitrogen-based ligands (single or other coordination) Including amide ligands in combination with ligands, such as amidinate ligands alone or in combination with other ligands, and β-diketimate ligands, and oxygen-based ligands alone Or other alkoxide ligands in combination with other ligands, such as bis-alkoxides with further donors; And an overview of the number of olefin catalyst system comprising a Group 13 metal catalyst; metal complex; 5 metal catalyst; Group 6 metal catalyst; Group 8 metal catalyst; 9 group metal catalyst; 10 metal catalyst.

  In addition, Britovsek et al. Disclose specific iron and cobalt catalysts for the polymerization of ethylene.

(Patent Document 1) discloses selected iron complexes of 2,6-pyridinecarboxaldehyde bis (imine) and 2,6-diacylpyridine bis (imine) as catalysts for propylene polymerization. (Patent Document 2) discloses a catalyst complex having a bridge comprising a heteroatom-crosslinkable R group R ⁵ and R ⁷ , and these complexes are particularly useful for the polymerization of ethylene alone or ethylene and higher 1-olefins. It is taught that it is useful for copolymerization with (page 2, lines 28-29). The bridged R groups R ⁵ and R ⁷ are independently selected from hydrogen, halogen, and hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl. There is no teaching or suggestion to make the chiral complex suitable for the production of high tacticity, crystalline polypropylene.

The following patents disclose bridged metallocene catalyst systems: (Patent Document 3); (Patent Document 4); (Patent Document 5); (Patent Document 6); (Patent Document 7); (Patent Document 8); Document 9); (Patent Document 10); and (Patent Document 11).
WO98 / 30612 (released July 16, 1998) WO99 / 12981 (released March 18, 1999) US Pat. No. 5,145,819 (issued to Winter et al. On September 8, 1992) US Pat. No. 5,158,920 (issued to Razavi et al. On October 27, 1992) US Pat. No. 5,243,001 (issued to Winter et al. On Sep. 7, 1993) US Pat. No. 6,002,033 (issued to Razavi et al. On Dec. 14, 1999) US Pat. No. 6,066,588 (issued to Razavi et al. On May 23, 2000) US Pat. No. 6,177,529B1 (issued to Razavi et al. On January 23, 2001) US Pat. No. 6,194,343 B1 (issued to Collins et al. On Feb. 27, 2001) US Pat. No. 6,211,110B1 (issued to Santi et al. On April 3, 2001) US Pat. No. 6,268,518B1 (issued to Resconi et al. On July 31, 2001) The Search for New-Generation Olefin Polymerization Catalysts: Life Beyond Metallocenes, Angew. Chem. Int. Ed. 1999, 38, 428-447 Iron and Cobalt Ethylene Polymerization Catalyzing Bearing 2,6-Bis (Imino) Pyridyl Ligands; Synthesis, Structures, and Polymerization Studies, J. MoI. Am. Chem. Soc. 1999, 121, 8728-8740.

  However, in spite of the above advances, to catalyst compositions, methods of making such compositions, polymerization methods using such compositions, polymer compositions, and articles made from such polymer compositions There is a need in the industry.

  According to one aspect of the invention, the formula

(Wherein M is a metal; each X is an atom or group bonded to M by a covalent bond or an ionic bond and may be the same or different; R ₁ and R ₂ are the same; Or each may be different and is a substituted or unsubstituted cyclopentadienyl or aromatic ring; R _B is a structural bridge between the cyclopentadienyl or aromatic rings R ₁ and R ₂ And comprising at least one heteroatom that imparts steric rigidity to said ring and is bonded to M, wherein each of R ₁ and R ₂ is bonded to the same or different heteroatom of R _B. this heteroatom is bound to M; Z is the coordination number of M, and 4 is greater than or equal to 4; m is the bonding number between heteroatoms M and R _B, And To give the body rigidity is greater than 2 or equal to 2; and _R 1, _{R 2} and _{R B} is selected to provide the _C 1, _{C 2} or _{C S} symmetry catalyst component)
A cross-linking compound is provided. The catalyst component can be chiral or achiral. In some embodiments, it may be desirable to have a catalyst component that is chiral.

According to another aspect of the present invention, the metal compound of formula M (X) ₂ is represented by the formula

(Where R _B , R ₁ and R ₂ are as defined above)
There is provided a method of producing a bridged metallocene compound comprising contacting with a crosslinking compound of:

  According to another aspect of the invention, the formula

(Where M, X, R ₁ , R ₂ , m and Z are as defined above)
There is provided a catalyst system comprising an activated bridged metallocene compound having:

  According to yet another aspect of the invention, the activator is of the formula

(Where M, X, R ₁ , R ₂ , m and Z are as defined above)
There is provided a method of making a catalyst system comprising contacting a bridged metallocene compound having:

  According to yet another embodiment of the present invention, the olefin monomer or mixture of monomers is represented by the formula

(Where M, X, R ₁ , R ₂ , m and Z are as defined above)
There is provided a method of forming a polyolefin comprising contacting in the presence of an activated bridged metallocene compound having:

For all of the above aspects, various further aspects are provided by varying M, X, R ₁ , R ₂ , m and Z as described in the detailed description.

  In one embodiment of the present invention, the bridged metallocene catalyst component of the present invention has the formula

(Wherein M is a metal; each X is an atom or group bonded to M by a covalent bond or an ionic bond and may be the same or different; R ₁ and R ₂ are the same; Or each may be different and is a substituted or unsubstituted cyclopentadienyl or aromatic ring; R _B is a structural bridge between the cyclopentadienyl or aromatic rings R ₁ and R ₂ And comprising at least one heteroatom that imparts steric rigidity to said ring and is bonded to M, wherein each of R ₁ and R ₂ is bonded to the same or different heteroatom of R _B. this heteroatom is bound to M; Z is the coordination number of M, and 4 is greater than or equal to 4; m is the bonding number between heteroatoms M and R _B, And Number of bonds around is an ≧ 2 to impart m steric rigidity to not exceed the coordination number Z; R _1, R ₂ and R _B C _1, C ₂ or the catalyst component is selected so as to provide a C _S symmetry)
Can be represented by: The catalyst component can be chiral or achiral. In some embodiments, it may be desirable to have a catalyst component that is chiral.

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

By way of non-limiting example, R ₁ and R ₂ may be selected from any substituted or unsubstituted cyclopentadienyl or aromatic ring known in the art to be useful in metallocene catalysts. Non-limiting examples of hydrocarbon groups 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 are (C ₅ (R ′) ₄ ) (where each R ′ may be the same or each may be different, and R ′ is hydrogen Or a cyclopentadienyl or aromatic ring in the form of a substituted or unsubstituted hydrocarbyl group having 1-20 carbon atoms.

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

R _B acts as a structural bridge between the cyclopentadienyl or aromatic rings R ₁ and R ₂ and imparts steric rigidity to the ring and n heteroatoms (“HA”) attached to M. ). The number of heteroatoms attached to M can be n ≧ 1, n ≧ 2, and in some embodiments it may be desirable to have n ≧ 3. Examples of suitable structural bridge R _B is shown in Example.

Useful heteroatoms in the structural bridge R _B include any “coordinating” bond, ie, anything that can be coordinated to the metal M by a bond formed by donation of a lone pair from the heteroatom. If the R _B may comprise one or more heteroatoms bonded to M, it may be the same heteroatom or different hetero atoms. Non-limiting examples of suitable heteroatoms include O, N, S, and P. In some embodiments, this heteroatom is desirably N.

R ₁ is bonded to the hetero atom of R _B , and this hetero atom is also bonded to M directly or indirectly through a different hetero atom. Similarly, R ₂ is bonded to the heteroatom of R _B, this heteroatom also binds indirectly M through directly or different hetero atoms. R ₁ and R ₂ may be bonded to the same heteroatom, which may be bonded to M, or may be bonded to a different heteroatom, which may be bonded to M. The structure of the R ₁ -R ₂ -R _B moiety can be is any one which does not disturb the symmetry of the catalyst. For example, the R ₁ -R ₂ -R _B moiety may have the following configuration, and still be within the scope of the claims of the present invention.

In certain embodiments, bridging groups having 4 heteroatoms are within the scope of the invention. According to one aspect of the present _invention, R 1, _{R 2,} and _{R B} is selected to provide a catalyst component having a _C 1, _{C 2} or _{C S} symmetry. Any configuration of R _1, R _2, and R _B to be useful in the catalyst manufacturer can not impair the known C _1, C ₂ or C _S symmetry may be used according to the invention. The catalyst component can be chiral or achiral. In some embodiments, it may be desirable to have a catalyst component that is chiral.

Each X may be an atom or group known for use in catalysis and is generally bound to M by a covalent or ionic bond. Usually each X is the same, but may be the same or different. By way of non-limiting example, X can be a halide, sulfate, nitrate, thiolate, thiocarboxylate, BF ₄ ⁻ , PF ₆ ⁻ , hydride, hydrocarbyl oxide, carboxylate, substituted or unsubstituted hydrocarbyl, and heterohydrocarbyl. Can be selected. Non-limiting examples of such atoms or groups are chloride, bromide, methyl, ethyl, propyl, butyl, octyl, decyl, phenyl, benzyl, methoxide, ethoxide, isopropoxide, toxylate, triflate, formate, acetate , Phenoxide and benzoate. If X is a halide or _C 1 _{-C 20} hydrocarbyl, which may be desirable. In some embodiments, it is desirable for X to be chloride. This crosslinked catalyst component is generally prepared by contacting the crosslinked intermediate with a compound in the form of M (X) ₂ . Further details are given in the examples.

  The present invention includes one or more of the above-mentioned crosslinked catalyst components and one or more activators and / or cocatalysts (as described in more detail below) or reaction products of activators and / or cocatalysts, Further included is a catalyst system comprising, for example, methylaluminoxane (MAO) and optionally an alkylating / scavenging agent such as a trialkylaluminum compound such as triethylaluminum (TEAL). The metallocene catalyst component described above may be supported as is known in the metallocene art. Typical carriers can be carriers such as talc, inorganic oxides, clays and clay minerals, ion-exchanged layered compounds, diatomaceous earth, silicates, zeolites or resinous carrier materials such as 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. Nonmetallocene transition metal compounds such as titanium tetrachloride can also be incorporated into the supported catalyst component. The inorganic oxide used as the support has an average particle size of 30-600 microns, preferably in the range of 30-100 microns, a surface area of 50-1,000 square meters per gram, preferably 100-400 square meters per gram, And a pore volume of 0.5-3.5 cc / g, desirably about 0.5-2 cc / g.

  The crosslinked catalyst of the present invention can be used in combination with some form of activator to produce an active catalyst system. The term “activator” is defined herein as any compound or component or combination of compounds or components capable of enhancing the ability of one or more catalysts to polymerize olefins to polyolefins. Alkylalumoxanes such as methylalumoxane (MAO) are commonly used as metallocene activators. Generally, the alkylalumoxane contains about 5-40 repeat units.

  Alumoxane solutions, in particular methylalumoxane solutions, are available from commercial sources as solutions having various concentrations. There are a variety of methods for producing alumoxanes, non-limiting examples of which are U.S. Pat. Nos. 4,665,208, 4,952,540, each incorporated herein by reference in its entirety. 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, EP0 279 586, EP-A-0 594 218 and WO 94/10180 (as used herein, unless otherwise specified, "solution" is any mixture containing a suspension). It is).

  An ionization activator can also be used to activate the crosslinked catalyst. These activators are neutral or ionic or are compounds such as tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate that ionizes the neutral catalyst compound. Such ionized compounds contain active protons, or are associated with the remaining ions of the ionized compound, but may contain some other cations that are non-coordinating or simply loosely coordinated. A combination of activators, such as a combination of alumoxane and ionization activator, may also be used. See for example WO 94/07928.

  Initial studies have described ionic catalysts for coordination polymerization consisting of metallocene cations activated by non-coordinating anions in EP-A-0 277 003, EP-A-0 277 004 and US Pat. No. 5,198. 401 and WO-A-92 / 00333, which is incorporated herein by reference. These protonate metallocenes (bis Cp and mono Cp) with anion precursors, abstract alkyl / hydride groups from transition metals, thereby making them cationic and making them charge balanced by non-coordinating anions A desirable manufacturing method is taught. Suitable ionic salts include, but are not limited to, tetrakis substituted borates or aluminum salts with aryl fluoride components such as phenyl, biphenyl and naphthyl.

  The term non-coordinating anion (NCA) means an anion that does not coordinate to the cation or only weakly coordinates to the cation and is sufficiently unstable to substitution with a neutral Lewis base. A suitable non-coordinating anion is one that does not decompose and become neutral when the initially formed complex decomposes. Furthermore, the anion transfers an anionic substituent or fragment to the cation and does not form a neutral four-coordinated metallocene compound and neutral by-product from the anion.

  The use of ionized ionic compounds that do not contain active protons but are capable of generating both active metallocene cations and non-coordinating anions is also known. See, for example, EP-A-0 426 637 and EP-A-0 573 403, which are incorporated herein by reference. A further method for producing this ionic catalyst is to use an ionized anion precursor that initially is a neutral Lewis acid but forms a cation and an anion during the ionization reaction with the metallocene compound. See, for example, the use of tris (pentafluorophenyl) borane, see EP-A-0 520 732 (incorporated herein by reference). An ionic catalyst for addition polymerization can also be produced by oxidizing the metal center of the transition metal compound with an anionic precursor containing a metallic oxidizing group together with an anionic group. See EP-A-0 495 375 (incorporated herein by reference).

  If the metal ligand contains a halogen moiety that does not ionize and extract under standard conditions (eg, bis-cyclopentadienyl zirconium dichloride), these may be organometallic compounds such as lithium or aluminum hydride or alkyl, It can be converted by known alkylation reactions with alkylalumoxanes, Grignard reagents and the like. EP-A-0 500 944 and EP-A1-0 570 982 for processes in the system describing reacting an alkylaluminum compound with a dihalo-substituted metallocene compound before or with the addition of an activated anionic compound. See (incorporated herein by reference).

  Desirable methods for supporting an ionic catalyst comprising a metallocene cation and NCA are described in US Pat. Nos. 5,643,847; 6,143,686; and 6,228,795 (all hereby incorporated by reference). Which is incorporated in the specification in its entirety). These NCA loading methods use neutral anion precursors that are sufficiently strong Lewis acids to react with hydroxyl-reactive functional groups present on the silica surface so that the Lewis acid becomes covalently bonded. In general.

  In addition, if the activator for the metallocene supported catalyst composition is NCA, NCA is desirably first added to the support composition followed by the bridged metallocene catalyst. When the activator is MAO, desirably the MAO and the bridged metallocene catalyst are dissolved together in solution. The support is then contacted with a MAO / metallocene catalyst solution. Other methods and order of addition will be apparent to those skilled in the art.

  The catalyst of the present invention can be used for the polymerization of α-olefins having at least 2 carbon atoms or the copolymerization of mixtures of α-olefins. For example, the catalysts of the present invention can be useful for the catalyst of ethylene, propylene, butylene, pentene, hexene, 4-methylpentene and mixtures thereof. The catalyst of the present invention can be used in the polymerization of propylene to produce polypropylene such as, for example, highly crystalline polypropylene.

The polymerization conditions and, where applicable, prepolymerization conditions are known in the art and need not be discussed in detail herein. In general, the polymerization is carried out by contacting either an α-olefin monomer or a mixture of α-olefins together under polymerization conditions in the presence of the catalyst system described above. The following examples are presented as specific embodiments of the invention and to demonstrate their practice and advantages.
[Example]
These examples are provided merely to illustrate some aspects of the present invention and are not intended to limit or limit the specification or the claims. In these examples, all handling of air / moisture sensitive materials was done in a conventional vacuum / inert atmosphere line using standard Schlenk line technology.

  The procedure described in WO 99/12981 was used for the synthesis of ligand intermediate A of the formula as shown below.

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 absolute ethanol (25 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 78 ° C. to give Intermediate A as pale yellow crystals (80%). The calculated values for the intermediate C33H43N3 are C82.3%; H8.9%; N8.7%. The measured results of the intermediate produced were C81.9%; H8.5%; N8.7%. The result of fast atom bombardment mass spectrometry (FABMS) is M + (481). The results of NMR analysis are as follows: ¹ HNMR (CDCl ₃ ): 8.6B7.9 [m, 3H, C5H3N], 7.2B6.9 [m, 6H, C6 (CHMe2) H3], 2.73 [sept, 4H , CHMe2], 2.26 [s, 6H, C5H3N (CMeNAr) 2] and 1.16 [m, 24H, CHMe2].

  250 mg, 1.09 equivalents of Intermediate A, and 95 mg of FeCl 2 .4H 2 O were weighed into a 10 ml Schlenk flask containing a stir bar. The flask was placed on a Schlenk manifold, replaced with argon three times, and 10 ml of tetrahydrofuran (THF) was added with stirring. After 2 hours, THF was removed under vacuum. The resulting deep blue solid (formula below) was washed twice with ether and dried under vacuum.

This example demonstrates the creation of a ligand with C ₂ / Class A symmetry. The same general synthesis follows Example 1 except that 2,6-diisopropylaniline is replaced by indene.

  1-Amino-indene (18.4 mmol) was added to a solution of 2,6-diacetylpyridine (9.2 mmol) in absolute 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 the solution was cooled to room temperature and filtered to give the intermediate shown below.

By using the same general synthesis as in Example 2, the catalyst from the ligand of Example 3 (intermediate with symmetry C ₂ / Class A) was synthesized and the catalyst components shown below were give.

This example demonstrates the creation of a ligand with C ₂ / Class B symmetry. The first part of the synthesis for this ligand is different from that of Example 1 above. The first part of the synthesis starts with reducing the diacetylpyridine to the diamine by using the Leuckart-Wallach reaction. In Scheme 1 below, the general reaction for the reduction of carbonyl to amine is shown.

  This example illustrates the reduction of a carbonyl to an amine, especially the synthesis of 1-phenylethylamine (Vogel's Practical Organic Chemistry, including qualitative organic analysis, 4th Ed, Furniss, BS et al., School of Chemistry Polymers Polychemistry Longman Scientific and Technical, 1978). 126 g (2.0 mol) ammonium formate, 72 g (0.6 mol) acetophenone and several pieces of porous porcelain are added to a 250 ml flask equipped with a Claisen still head fitted with a short fractionation column; A thermometer extending almost to the bottom of the flask was inserted and a short condenser was placed in the side arm for down distillation. The flask was heated (either with a heating mantle or in an air batch); the mixture initially melted into two layers and distillation occurred. The mixture became homogeneous at 150-155 ° C. and the reaction occurred with some foaming. Heating was continued until the temperature reached 185 ° C (about 2 hours); acetophenone, water and ammonium carbonate distill off. Heating was discontinued at 185 ° C., the upper layer of acetophenone was separated from the distillate and returned to the flask without drying. The mixture was heated at 180-185 ° C. for 3 hours and cooled; acetophenone may be recovered from the distillate by extraction with a 20 ml quantity of toluene. The reaction mixture was transferred to a 250 ml separatory funnel and shaken with two 75 ml volumes of water to remove formamide and ammonium formate. The crude (1-phenylethyl) formamide was transferred to the original reaction flask and the aqueous layer was extracted with two 20 ml volumes of toluene. The toluene extract was transferred to the flask and 75 ml of concentrated hydrochloric acid and a few pieces of porous porcelain were added. The mixture was carefully heated until about 40 ml of toluene was collected and gently boiled under reflux for an additional 40 minutes; except for a few layers of unaltered acetophenone, hydrolysis was reduced to 1-phenylethylamine hydrochloride. Proceeds quickly to salt. The reaction mixture was cooled and acetophenone was removed by extraction with four 20 ml portions of toluene. This acid aqueous solution was transferred to a 500 ml round bottom flask equipped with a steam distillation apparatus, 62.5 g of sodium hydroxide solution was carefully added to 125 ml of water and steam distilled: the volume remained approximately constant. The distillation flask was heated. Most of the amine was contained in the first 500 ml distillate; if the distillate becomes slightly slightly alkaline, the operation is discontinued. The distillate was extracted with five 25 ml quantities of toluene, and the extract was dried over sodium hydroxide pellets and fractionated. Toluene is distilled at 111 ° C., followed by phenylethylamine. The latter was collected as a fraction with a boiling point of 180-190 ° C (most of this product was distilled at 184-186 ° C (3)); the yield was 43 g (59%).

This example illustrates 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 a 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. This white solid was washed with a small amount of water. The dioxime was dried overnight under vacuum to give a white powder (1.08 g; 5.6 mmol; 92%) that was used without further purification. The results of NMR analysis were as follows: ¹ HNMR (CD ₂ Cl ₂ ), δ: 7.81 (d, 2H, Hmeta, J = 7.8 Hz), 7.70 (t, 1H, Hpara, J = 7.8 Hz) 2.79 (s, 2H, OH), 2.33 (s, 6H, Me).

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

Synthesis of 2,6- (1,1′-diethylamino) -pyridine (diamine). The 2,6- (1,1′-diethylhydroxyimino) -pyridine (500 mg; 2.6 mmol) was placed under argon and added to a flask equipped with a magnetic stirrer and ethanol (10 mL) and acetic acid Dissolved in (6 mL). Zinc powder (6 g; 94 mmol) was added dropwise over 10 minutes. A white precipitate appeared after 1 hour of stirring. 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 under vacuum. A small amount of water was added and evaporated to remove any residual acetic acid. The mixture was made strongly basic (pH> 12) by adding saturated aqueous potassium hydroxide (approximately 56 mL) until all Zn (OH) ₂ was redissolved. The aqueous layer was transferred to a separatory funnel and extracted with four 20 mL portions of diethyl ether. The combined organic fractions were dried over MgSO ₄ and the solvent removed in vacuo to give a colorless oil (310 mg; 1.87 mmol; 72%). As a result of NMR analysis, ¹ HNMR (CD ₂ Cl ₂ ), δ: 7.59 (t, 1H, Hpara, J = 7.8 Hz), 7.14 (d, 2H, Hmeta, 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).

This example gives the ligand for the catalyst having symmetry C ₂ / class B by reacting the diamine obtained in Example 7 with a ketone (Scheme 4).

This example illustrates the synthesis of a bis-imine for a C ₂ / Class B symmetry catalyst (Scheme 5) based on the reaction of a diamine with β-tetralone.

In a 100 mL round bottom flask equipped with a stir bar, the diamine (0.50 g, 3.03 mmol) and the β-tetralone (0.85 mL, 6.43 mmol) are added to the flask at 25 ° C., and The mixture yielded a clear dark yellow liquid. The flask was then placed under vacuum and replaced with argon three times and then left under argon. After stirring for 10 minutes, the mixture produced a pale yellow solid tar that became very difficult to stir. 25 mL of ethanol was added to help stir the mixture. A clear yellow-orange solution was obtained. After stirring at 25 ° C. for 2 hours, the solvent was removed under vacuum to give a pale yellow foamy solid. 1H-NMR analysis showed that this product was mostly the desired bis-imine ligand (78% yield). The results of NMR analysis are as follows: ¹ HNMR (300 MHz, CD ₂ C1 ₂ , 35 ° C.), δ: 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).

This example bis for C _{2 /} Class B symmetry of catalyst based on the reaction of a diamine with cyclohexanone (Scheme 6) - illustrates the synthesis of the imine. The procedure described in Example 9 was used for the synthesis of bis-imine.

This example illustrates the synthesis of bis-imines for C2 / class B symmetry catalysts based on the reaction of diamines with mesitylaldehyde (Scheme 7). The procedure described in Example 9 was used for the synthesis of bis-imine. Bis-imine: NMR analysis results are as follows: ¹ HNMR (300 MHz, CD ₂ Cl ₂ , 35 ° C.), δ: 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).

Another catalyst synthesis procedure for producing symmetrical C ₂ / Class B catalysts is the same procedure described in WO 98/30612 (in this structure the position of the R group and the double bond are different. And is shown in the following reaction formula.

The ligand of Example 9 (1.05 equivalents) and the metal salt in hydrated or anhydrous form were added together into a Schlenk flask under an inert atmosphere and then charged with THF. The mixture is stirred for several hours or until no detectable unreacted salt is observed. The mixture is filtered in air, the solid is washed with Et ₂ O and dried under vacuum.

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

To synthesize ligands for C ₂ / Class C symmetry catalysts, a procedure similar to that used for C ₂ / Class B symmetry is used. The difference is that only one acetyl group is reduced on 2,6-diacetylaniline. The general procedure for this synthesis is shown in the following formula where only one of the acetyls is reduced to an amine.

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

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

  Next, the catalyst is synthesized by the procedure described in Example 13.

Single bond, by simply using different R groups attached to the nitrogen atom having a double bond, or one single bond and one double bond, may be obtained even symmetry with respect to C1 and C _S. Table 1 summarizes some examples for different symmetries for the structures shown in Table 1.

  Any patents, patent applications, articles, books, articles, and any other publications cited herein are hereby incorporated by reference for all of these teachings or suggestions.

Structure of the solid state of the X-ray data iron complex iron complexes of C ₂ symmetry are those determined by X-ray diffraction method of a single crystal. The selected crystallographic data is summarized in Table 2 and the structure is described by the formula of Example 4 and shown in the table below.

  While exemplary embodiments of the present invention have been described with specific examples, it is understood that various other modifications will be apparent to and can be readily made by those skilled in the art without departing from the scope of the invention. It will be. Therefore, it is not intended that the appended claims be limited to the examples and descriptions described herein, which are treated as equivalents by those skilled in the art to which this invention pertains. It is intended to be construed as including all features of patentable novelty that exist in the present invention, including all such features.

Claims (6)

formula
(Wherein M is a transition metal selected from the group consisting of Fe, Co and Ni ; each X is an atom or group bonded to M and is the same or different; R ₁ and R ₂ are the same or different, and (C ₅ (R ′) ₄ ) (wherein each R ′ may be the same or each may be different, and R ′ may be hydrogen or 1- a substituted or unsubstituted hydrocarbyl group) having 20 carbon atoms; R _B is a structural bridge between R ₁ and R _2, and three heteroatoms bonded to M, in thisゝThe heteroatom is selected from the group consisting of O, N, S, and P, wherein each of R ₁ and R ₂ is bonded to the same or different heteroatom of R _B , Also binds to M; Z is the coordination number of M, and from 4 Greater than or equal to 4; m is the number of bonds between the heteroatoms of M and R _B and m ≧ 2; and R ₁ , R ₂ and R _B are C ₁ , C ₂ or Cs Selected to give symmetry)
A catalyst system for olefin polymerization comprising: R ₁ Is bonded to one of said heteroatoms and R ₂ The catalyst system according to claim 1, wherein is bonded to a different one of the heteroatoms. R ₁ Is bonded to one of the three heteroatoms and R ₂ Is R ₁ Bonded to a heteroatom different from the heteroatom to which is bonded;
The catalyst system according to claim 1, wherein M is selected from Fe, Co and Ni. 4. A catalyst system according to claim 3, wherein each X is independently selected from the group consisting of halides and substituted or unsubstituted hydrocarbons. Activator formula
(Wherein M is a transition metal selected from the group consisting of Fe, Co and Ni; each X is an atom or group bonded to M and is the same or different; R ₁ And R ₂ Are the same or different and (C _Five (R ’) _Four Where each R ′ may be the same or each may be different and R ′ is hydrogen or a substituted or unsubstituted hydrocarbyl group having 1-20 carbon atoms). Yes; R _B Is R ₁ And R ₂ A structural bridge between and comprising three heteroatoms bonded to M, R ₁ And R ₂ Each is R _B The same or different heteroatoms, wherein the heteroatoms are selected from the group consisting of O, N, S, and P, the heteroatoms are also bound to M; Z is the coordination of M Is a number and greater than or equal to 4; m is M and R _B The number of bonds between the heteroatoms and m ≧ 2; and R ₁ , R ₂ And R _B Is C in the catalyst component ₁ , C ₂ Or selected to give Cs symmetry)
A process for producing a catalyst system for olefin polymerization comprising contacting with a crosslinking compound having. formula
(Wherein M is a transition metal selected from the group consisting of Fe, Co and Ni; each X is an atom or group bonded to M and is the same or different; R ₁ And R ₂ Are the same or different and (C _Five (R ’) _Four Where each R ′ may be the same or each may be different and R ′ is hydrogen or a substituted or unsubstituted hydrocarbyl group having 1-20 carbon atoms). Yes; R _B Is R ₁ And R ₂ Comprising three heteroatoms bonded to M, wherein the heteroatoms are selected from the group consisting of O, N, S, and P, and R ₁ And R ₂ Each is R _B Are bonded to the same or different heteroatoms, the heteroatoms are also bonded to M; Z is the coordination number of M and is greater than or equal to 4; m is M and R _B The number of bonds between the heteroatoms and m ≧ 2)
A catalyst system for olefin polymerization comprising: