TW201323430A - Process for recycling of free ligand from their corresponding metallocene complexes - Google Patents

Abstract

An efficient and economical process to recover ligands from metallocene complexes, where the free ligand recovered may be recycled to produce additional metallocene and metallocene complexes.

Description

Method for recovering free ligands from corresponding metallocene complexes Field of invention

The examples disclosed herein are generally directed to a method of recovering a ligand from a metallocene complex. More specifically, the embodiments disclosed herein are directed to an efficient and economical process for recovering a ligand from a metallocene complex wherein the recovered free ligand can be regenerated to produce additional molybdenum. metal.

Background of the invention

The conventional synthesis of an ansa-metallocene complex typically forms a non-image isomer of these complexes. Unfortunately, for most complexes, only one of these non-image isomers can be used to make polypropylene having desirable properties such as isotacticity. Since the other non-image isomer has an adverse effect on the polymerization process or the formed polymer, it is typically necessary to separate the undesired metallocene complex from the desired metallocene complex and discard. In some cases, using this mode will result in a loss of 50% or more of the total metallocene yield.

As described in EP 1392710 B1, the synthesis of metallocenes can involve multiple steps involving the reaction of a metal compound such as a metal alkoxide or metal halide with a cyclopentadienyl-metal compound. The reaction forms a large amount of inorganic by-products (salts) mixed with the basket-type metallocene, which is itself a mixture of non-image isomers. And then from the inorganic by-products and organic by-products in a multi-step process (which includes the undesired non-mirror The desired metallocene is separated in the isomer). A similar method for the manufacture of the desired metallocene product is also disclosed in EP 1963 339 B1 and US 5,770, 072.

These references also describe useful methods for recovering unreacted ligands from the racemic form of the metallocene and/or recovering the ligands. However, such methods, such as those described in EP 1392710 B1, are difficult to classify, which merely means decomposing the meso-form of the metallocene, or requiring harsh conditions and/or via, such as in EP19633339B1. The above-mentioned decomposition products are densely purified by extensive chromatography using the resources described above.

Summary of invention

The embodiments disclosed herein provide an efficient and economical method for recovering a ligand from a metallocene complex wherein the free ligand can be recovered from the undesired non-image isomer at high yields. And regenerated to produce additional metallocene. The method includes controlled decomposition of the metallocene complex via a protic species, separation of the inorganic decomposition products and other impurities, and recovery of the ligand for regeneration and reuse.

In one aspect, the embodiments disclosed herein relate to a method for recovering a ligand from a metallocene complex, the method comprising: contacting a composition comprising a protic compound under reaction conditions A metallocene complex containing a ligand to decompose the metallocene complex and form a reaction product comprising a free ligand and an inorganic decomposition product; the free ligand is recovered from the reaction product.

In another aspect, the embodiments disclosed herein relate to a method for making a metallocene catalyst, the method comprising: synthesizing one containing a basket-type metallocene complex of a racemic form of a metallocene and a mixture of racemic forms of the metallocene, the synthesis comprising reacting a ligand with a metal compound; separating the basket-type metallocene Recycling a fraction containing the meso form of the metallocene complex and a fraction containing the racemic form of the metallocene complex; contacting the composition containing the protonic compound under the reaction conditions At least a portion of the fraction in the meso form of the metallocene complex to decompose the metallocene complex and form a reaction product comprising a free ligand and an inorganic decomposition product; recovering the freedom from the reaction product The ligand is coordinated and at least a portion of the free ligand is recovered in the synthetic step.

Other aspects and advantages are apparent from the following description and the appended claims.

2‧‧‧metallocene complexes containing a ligand

4‧‧‧Protonic composition

6, 38‧‧‧ decomposition stage

8, 40‧‧‧Reaction products containing free ligands and inorganic decomposition products

10. 42‧‧‧Separation/recycling phase

12‧‧‧Free seat

14, 46‧‧‧Inorganic decomposition products

22‧‧‧Metal compounds

24‧‧‧With seat

26‧‧‧ Metallocene synthesis stage

28‧‧‧Products comprising a binding ligand comprising a basket-type metallocene complex

30‧‧‧Separation phase

32‧‧‧ fractions containing metallocene complexes of the desired form

34‧‧‧ fractions containing the undesired form of metallocene complex

36‧‧‧Composition containing a protic substance

44‧‧‧ fractions containing the free ligand

48‧‧‧ new matching seats

50‧‧‧ stage

52‧‧‧metallocene catalyst system

54‧‧‧polymerization products

56‧‧‧Polymerization stage

1 is a simplified block flow diagram of a method for recovering a ligand from a metallocene complex according to embodiments disclosed herein.

2 is a simplified block flow diagram of a method for efficiently and economically producing a metallocene complex according to embodiments disclosed herein.

Detailed description of the preferred embodiment

In one aspect, the embodiments herein are generally directed to a method for recovering a ligand from a metallocene complex. More specifically, the embodiments disclosed herein are directed to an efficient and economical method for recovering a ligand from a metallocene complex, wherein the free ligand can be derived from the undesired non-image isomerism. The material is recovered in high yield for regeneration to produce additional metallocene. In addition to other steps that may be employed, the method includes controlled decomposition of the metallocene complex via a protic composition, separation of the inorganic decomposition products and other impurities, and recovery of the ligand for regeneration and reuse. For the purposes of the present invention, this reaction, referred to as a controlled decomposition or decomposition reaction, utilizes the general principle of the presence of protonic species which can transfer a proton to the organic portion of the organometallic compound, in many The carbon-metal bond in the organometallic compound (such as a metallocene complex) can be split, thereby regenerating the original organic molecule which originally produced the organic portion of the organometallic compound. In the reaction formula 1, a diagram showing the decomposition of the meso form of the metallocene complex using a proton substance HX as defined below. The metallocene complex can be reacted in a racemic form, or a mixture of racemic and meso forms. The free ligand is recovered and separated by a by-product containing the metal represented by the formula "X ₂ M ¹ R ¹ R ² ". The precise chemical structure of such by-products is unknown and independent of the present invention, and mixtures containing different species may be present.

Such groups M ¹ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ^3′ , R ^4′ , R ^5′ , R ^6′ , R ^{7 '} and R ^{8 '} are the same as those described in the following patents, but are not limited to the following: U.S. Patent Nos. 7,285,608, 7,169,864, 7,842,764, EP 1692144, WO 09/054832, and WO 10/077230, the disclosure of which is incorporated herein by reference.

Reaction formula 1

The reaction of the metallocene complex with the protic species can form different heterostructures of the ligand. Possible heterogeneous examples of the ligand formed during this decomposition reaction are shown in Formulas 1 (a) to (c). Any of the isomers formed or mixtures thereof can be used to produce the original metallocene complex in racemic or meso form.

Referring now to Figure 1, a simplified block flow diagram of a method for recovering a ligand from a metallocene complex according to one of the embodiments disclosed herein is set forth. In the decomposition stage 6, a metallocene complex 2 containing a ligand is contacted with an aprotic composition 4 comprising a protic substance. Contacting the metallocene complex 2 with the protonic composition 4 to form a reaction product containing a free ligand and an inorganic decomposition product under conditions sufficient to decompose at least a portion of the metallocene complex . The reaction product 8 is then subjected to a separation/recovery stage 10 in which the free ligand 12 is separated from the inorganic decomposition product 14.

Although the method of Figure 1 illustrates the method in a simplified block flow diagram, it is worth noting that the decomposition stage 6 and the separation/recovery stage 10 It can be carried out in the same or separate containers. Moreover, the decomposition stage 6 and the separation/recovery stage 10 illustrated may include one or more internal steps for forming the desired products, examples of which may be detailed below.

Proton composition

In certain embodiments, the protic composition can be a homophasic mixture of one or more protic materials. In other embodiments, the protic composition can be an in-phase mixture of one or more protic materials and one or more aprotic materials. In still other embodiments, the protic composition can be a multi-phase system comprising one or more protic materials and one or more aprotic materials. In certain preferred embodiments, the protic composition comprises an inert aprotic material (such as toluene) and a protic material (such as ethanol), wherein the aprotic and protic compounds are And choose: the desired decomposition reaction and accelerate the separation and recovery of the ligand.

Protonic substance

The protic materials useful in the embodiments disclosed herein may include water, mineral acids, organic acids, alcohols, ammonium salts containing at least one hydrogen atom bonded to nitrogen, sulfonic acid, sulfinic acid, mercaptan, phosphorus. An organic derivative of oxyacid, and the like.

Examples of the mineral acid which may be a protic substance in the examples disclosed herein may include, among others, hydrochloric acid, nitric acid, phosphoric acid, boric acid, hydrofluoric acid, and hydrobromic acid. Examples of organic acids which may, among other things, be protic substances in the examples disclosed herein may include acetic acid, formic acid, citric acid, oxalic acid, tartaric acid, propionic acid, butyric acid, isobutyric acid, valeric acid, Isobutyric acid, caproic acid, 4-methylpentanoic acid, heptanoic acid, oleic acid, lactic acid, benzoic acid, succinic acid, and stearic acid.

Examples of the alcohol which can be used as the protic substance in the examples disclosed herein may include methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, and tert-butanol, and higher alcohols. Various isomers. Examples of ammonium salts containing at least one nitrogen-bonded hydrogen atom as protonic substances in the examples disclosed herein may include, among other things, ammonium carbonate, ammonium chloride, ammonium acetate, ammonium urinate, formic acid. Ammonium, ammonium thiosulfate, and ammonium nitrate.

The sulfonic acid which may be a protic substance in the examples disclosed herein may include various compounds having the general formula RS(=O) ₂ OH wherein R is an alkyl group or an aryl group. Examples of sulfonic acids which may be used in the examples disclosed herein may include, among others, alkylbenzene sulfonic acids such as p-toluenesulfonic acid and dodecylbenzenesulfonic acid, ethanesulfonic acid, and methanesulfonic acid. The sulfinic acid which may be a protic material in the examples disclosed herein may include various sulfur-containing oxyacids having the formula RSO(OH) wherein R is an alkyl group or an aryl group. Sulfonates and sulfinates can also be used.

A combination of two or more of the above protons can also be used. The preferred combination of protic or protic compounds for the decomposition of the metallocene complex can depend on the particular metallocene complex and/or subsequent steps to recover the ligand.

Aprotic substance

Aprotic materials useful in the embodiments disclosed herein can include linear hydrocarbons, branched chain hydrocarbons, cyclic hydrocarbons, and aromatic hydrocarbons, or combinations thereof. Examples of aprotic materials may include, among others, propane, Butane, isobutane, pentane, 2-methylbutane, neopentane, cyclopentane, hexane, 2-methylpentane, 3-methylpentane, heptane, 2-methylhexyl Alkanes, 3-methylhexane, cyclohexane, octane, isooctane, decane, isodecane, decane, benzene, toluene, and xylene. In certain embodiments, the aprotic material can include toluene, dichloromethane, or a combination thereof.

Decomposition of the metallocene complex

Decomposition of the metallocene complex can be carried out by contacting the metallocene complex with a protonic composition as described above. The reaction conditions suitable for decomposing the metallocene complex into the corresponding ligand and a metal compound may depend on the stability of the metallocene complex, the stability of the ligand itself, and the metallocene. The solubility of the complex in an organic or inorganic solvent, the solubility of the ligand in an organic or inorganic solvent, the particular proton (group) used, and among other factors, affects the economics of the process. the elements of.

The metallocene complex may be carried out in the solid phase of the metallocene complex, such as in a suspension, or in the partial or total dissolution of the metallocene complex system in the protic composition. Contact of the composition with the composition containing the protonic compound. In certain embodiments, if the metallocene is in a solid phase, the contact of the metallocene complex can be carried out and heating to a decomposition reaction temperature can result in dissolution of the metallocene complex.

The decomposition reaction can generally take place at ambient temperature or below ambient temperature, but under these conditions, depending on the precise nature of the metallocene, a reaction time in excess of 10 or even 24 hours may be required. In order to ensure that the metallocene complex reacts with the protic substance at a economical rate (i.e., below 24 hours or preferably below 10 hours or even better below 5) The reaction is carried out at an elevated temperature. The boiling point of the mixture of solvents and/or protic materials used generally sets a natural limit to the maximum temperature at which the decomposition reaction takes place. However, a reasonably fast reaction rate has been obtained at temperatures below the boiling point of the decomposition mixture.

The economical reaction of the protic species with the metallocene complex can be carried out, for example, at temperatures ranging from about 0 °C to about 200 °C. In certain embodiments, the reaction temperature may range from about 20 °C to about 160 °C, and in other embodiments may range from about 50 °C to about 120 °C.

The decomposition reactions can be carried out under a slight vacuum, under normal pressure, or under high pressure. In certain embodiments, the metallocene complex can be blended with the protic composition at the boiling point of the mixture, preferably under reflux. The reaction of the metallocene complex with the protic material can be carried out, ranging from about 1 minute to about 24 hours, such as from about 2 hours to about 12 hours.

As described above, the protic composition may be an in-phase or multi-phase composition. Furthermore, the metallocene complex can be first dissolved or suspended in an aprotic solvent such as toluene. It is necessary to sufficiently agitate or stir to bring the protic composition into proper contact with the metallocene complex to carry out a decomposition reaction.

In certain embodiments, the decomposition of a metallocene complex is carried out as follows: A) wherein the protic composition comprises a) an aprotic species, such as toluene, wherein the metallocene complex can be at room temperature or Dissolving at a slight elevated temperature (eg, <100 ° C), and b) an alcohol as the protic material or a mixture comprising one or more alcohols; and B) at reflux of the mixture, under reflux.

Separation/recycling of the ligand

After the metallocene complex is decomposed, depending on the reaction conditions, the protic composition, and the metallocene complex used, the reaction product formed may include the ligand, a metal compound (such as a metal salt), and Various reaction products. In certain embodiments, no reaction byproducts are present. The free ligand can then be recovered from the decomposition reaction product.

Separation and recovery of the ligand can be carried out using a variety of techniques, and such techniques can include one or more of the following: phase separation (such as where a heterogeneous proton composition is used), precipitation, crystallization, segmentation Crystallization, filtration, solvent removal (filtration), washing, and, if necessary, recrystallization to increase the purity of the recovered ligand.

For example, in an embodiment in which an in-phase proton composition comprising an aprotic solvent is used, the decomposition reaction product can be made with an alcohol (which can be the same or different from the proton species used to carry out the decomposition reaction) mixing. In the case of sufficient amount, the added alcohol acts as an anti-solvent which can cause precipitation of the ligand. In other embodiments, the composition can be boiled to remove a portion of the aprotic solvent, thereby allowing concentration of the ligand within the added alcohol and causing precipitation of the ligand. The precipitated ligand can then be recovered by, for example, filtration.

As another example, in embodiments in which a heterogeneous protic composition is used, the organic phase comprising the free ligand can be separated from the remainder. After phase separation, the organic phase can be subjected to solvent extraction and, if necessary, dried to remove water. The solvent can then be removed from the composition, such as by using a vacuum, which will form a thick containing the free ligand. Solid product.

As noted above, the decomposition of the metallocene and the separation and recovery of the free ligand can be recovered to have greater than 75% purity (in certain embodiments), greater than 85% purity (in other embodiments), and greater than 90%. A crude ligand product of purity (in other examples). The impurities in the original product may consist of the zigzag-containing fragment of the complex, a ligand fragment formed by a side reaction during the decomposition reaction, or other compound. The crude ligand product can be regenerated without further purification to produce additional metallocene products. In other embodiments, the crude ligand product can be purified via recrystallization reaction, chromatography, extraction, or other standard methods for purifying chemical compounds to increase the purity of the ligand to greater than, for example, 95. %. As used herein, "coarse ligand product" refers to a ligand that can be isolated from the reaction/separation purification sequence without further purification (eg, recrystallization). The purity of the original product is usually sufficient to allow it to be used in the synthesis of new metallocenes as it is.

An economical method for purifying a metallocene ligand as described in the present invention is a method of performing a recrystallization reaction from a hot alcohol. Other purification methods are well known to those of ordinary skill in the art.

After recovery, at least a portion of the free ligand can be fed to a process for making a metallocene complex. For example, the recovered ligand can be obtained from the meso form of the metallocene complex, and the method for producing the metallocene complex can be used to produce meso and exogenous complexes containing the metallocene complex. A basket-type metallocene complex of a mixture in the form of a spin. Since the different metals, bridging agents, and other components can be varied, the same or different metallocene complexes can be used (rather than the method of recovering the free ligand) The free ligand is recovered in the metallocene complex prepared in the base.

Referring now to Figure 2, there is illustrated a simplified block flow diagram of a method for efficiently and economically producing a metallocene complex according to embodiments disclosed herein, including from such metallocene complexes. The ligand is recovered in the desired form. Moreover, although illustrated in a simplified block flow diagram, each of the stages may be performed in one or more containers and may include one or more unillustrated internal steps.

In the process for making a metallocene complex, a metal compound 22 (such as a metal alkoxide or metal halide) can be combined with a ligand 24 (such as cyclopentadiene) in the metallocene synthesis stage 26. Base-metal compound) reaction. The synthesis of the metallocene complex can be carried out to produce a binding ligand comprising a basket-type metallocene complex (which can be a racemic form of the metallocene complex and the metallocene complex) Product 28 of the mixture in meso form.

The product 28 can then be fed to a separation stage 30 to separate the basket-type metallocene complex into one or more fractions comprising the desired form and the undesired form of the metallocene. In certain embodiments, the desired form of the metallocene can be in the racemic form, and the undesired form of the metallocene can be in the meso form. Separation stage 30 can also include one or more steps for separating reaction byproducts and impurities from the metallocene complex. After separation, fraction 32 containing the metallocene complex of the desired form, and fraction 34 containing the metallocene complex of the undesired form are recovered.

The composition comprising the proton-containing material 36 can then be contacted with a fraction comprising the undesired form of the metallocene complex in the decomposition stage 38. (group) 34. Contacting the metallocene complex 34 with the composition of the proton-containing substance 36 to form a free ligand and inorganic decomposition under conditions sufficient to decompose at least a portion of the metallocene complex The reaction product 40 of the product. The reaction product 40 is then subjected to a separation/recovery stage 42 in which a fraction 44 containing the free ligand is separated from the inorganic decomposition product 46.

The recovered free ligand 44 can then be recycled to the metallocene synthesis step 26. If necessary, the fraction 44 containing the free ligand can be treated to increase the purity of the ligand prior to recycling. For example, the crude ligand can be recovered by dissolving in a hot alcohol such as ethanol or isopropanol and recrystallizing from the hot alcohol to obtain a ligand product having a purity of 95% or higher. In certain embodiments, the recovered free ligand can be combined with a new ligand 48 to form a combined ligand feed 24.

Processing of the fraction (group) 32 comprising the desired metallocene can then be carried out in stage 50 to form the desired metallocene catalyst system. Stage 50 can include any number of steps commonly used to form a metallocene catalyst system, such as carrying the metallocene on a support structure, activating the metallocene catalyst, and/or contacting the molybdenum with a cocatalyst, among other steps Metal or the supported metallocene. If appropriate or preferred, such activation and contacting steps can be carried out in a vessel, in a first-class conduit, or in a polymerization reactor. A suitably activated metallocene catalyst system 52 can then be used to form polymerization reaction products 54, such as polyethylene, polypropylene, or other various polymers, in polymerization stage 56.

Metallocene synthesis

Typical metallocene synthesis methods can be used and combined as shown in Figure 2 The recycle of the ligand is illustrated to carry out the synthesis of the metallocene complex using the recovered and recycled ligand according to the examples disclosed herein. The synthesis of such metallocene complexes is well known per se (U.S. Patent No. 4,752,597; U.S. Patent No. 5,017,714; European Patent No. EP-A-320,762; EP-A-416,815; EP-A-537,686; EP -A-669,340; HH Brintzinger et al; Angew. Chem., 107 (1995), 1255; HH Brintzinger et al; J. Organomet. Chem., 232 (1982), 233). Such metallocene complex compounds can be prepared, for example, by reacting a cyclopentadienyl metal compound with a halide of a transition metal such as titanium, zirconium, and hafnium.

It is also well known that the basic properties of such metallocenes, such as polymerization activity, stereoselectivity, positional selectivity, and maximum available polymer molecular weight, can be systematically controlled by the specific substitution pattern of the ligand sphere. For example, using a typical value for a PP wax of 37,500 g/mole (R=H) to 197,500 g/mole (R=methyl) is described via the use of dimethylformamidine bis(2-R-fluorenyl) The molecular weight Mw of the polypropylene produced by zirconium dichloride (European Patent No. EP 0 485 822 B1, U.S. Patent No. 5,243,001).

In terms of stereoselectivity, positional selectivity, and control of polymer molecular weight, the polymerization of a fluorenyl ligand at position 4 has also been found to be effective. For example, EP 0 576 970 (U.S. Patent No. 5,770,753) describes the metallocenes: dimethylformamidine bis(2-ethyl-1-indenyl)zirconium dichloride (as the stereo- and positional choice) The measured molecular weight of the polymer (450,000 g/mole) and the melting point of the polymer (147 ° C)) and dimethylformamidine bis(2-ethyl-4-phenyl-1-indenyl) dichloride Zirconium (polymer molecular weight is 1,790,000 g/mole and the melting point of the polymer is 162 ° C).

The control utility of the unit bridging the thiol-based ligands has also been described. For example, EP 0 284 708 B1 (U.S. Patent No. 6,117,957) describes a method for controlling the molecular weight of a polymer and the melting point of a polymer by means of a bridged variable ("It has been found that changing the structure and composition of the bridge can result in such polymer products. The change in melting point and molecular weight"). Similar results are published in EP 0 336 128 B1 (U.S. Patent No. 5,679,812) and EP 0 344 887 (U.S. Patent No. 5,017,714).

Such metallocenes having standard bridging groups (such as dimethylformamidine bridging groups), which are described in the literature and in certain instances, have been used in the industry, and the like generally have significant disadvantages. For example, the metallocene bridged by the process can be isolated in pure racemic ("ruc") form at an unacceptably high yield loss and high cost of by-products and used in all modern polymerization processes. The carrier manufacturing steps required to prevent metal scale formation from metallocenes can be made more complicated by the unsatisfactory solubility properties of these compounds. The method according to the embodiments disclosed herein can reduce some of these disadvantages, improve the yield of the desired catalyst based on a new ligand, and reduce the cost of the metallocene synthesis.

Ligand and metallocene complexes

The method of separating and recovering a ligand according to the embodiments disclosed herein can thus be used to improve the economics of the method of making such metallocenes, among other things, including one or more of the following patents. Methods described in U.S. Patent Nos. 7,285,608; 7,232,869; No. 7,169,864; 4,530,914; 4,542,199; Nos. 4, 769, 910; 4, 769, 910; 4, 808, 561; 4, 871, 705; 4, 931, 417; 4, 933, 403; 4, 937, 299; 5, 017, 714; 5, 026, 798; 5, 057, 475; 5, 120, 867; 5, 132, 381; 5, 145, 819 , No. 5, 198, 401; No. 5, 198, 401; No. 5, 243, 022; No. 5, 276, 208; No. 5, 278, 119; No. 5, 296, 434; No. 5,304, 614; No. 5,324,800; No. 5,328, 969; No. 5,329,033; Nos. 5, 371, 790; 5, 416, 790; 5, 416, 305; 5, 455, 366; 5, 510, 502; 5, 532, 396; 5, 543, 373; 5, 554, 704; 5, 576, 260; 5, 612, 428; 5, 616, 663; 5, 616, 747; No. 5, 635, 254; No. 5,852,142; 5,929,264; 5,932,669; 6,017,841; 6,051,522 No. 6,051, 727; No. 6, 087, 291; No. 6, 087, 291; No. 6,100, 214; No. 6,114, 479; No. 6, 117, 955; No. 6, 124, 230; No. 6,140, 432; No. 6, 194, 341; No. 6, 218, 558; No. 6, 228, 795; No. 6, 242, 544, No. 6, 245, 706 No. 6,252,097, 6,255,506; 6,255,515; 6,376,407; 6,376,408; 6,376,409; 6,376,410; 6,376,411; 6,376,412; 6,376,413; 6,376,627; 6,380,120; No. 6,380,121; No. 6,380,122; No. 6,380,123; No. 6,380,124 No. 6,380,330; No. 6,380,331; No. 6,380,334; No. 6,399,723; No. 6,444,606; No. 6,469,114, and U.S. Patent Application Publication No. 2001021755; No. 20030149199; European Patent EP 576 970; EP 611 773, EP 320 762; EP 0 416 815; EP 0 537 686; EP 0 669 340; WO 97/32906; WO 98/22486; WO 00/12565; WO 01/48034; WO 03/045964; WO 03/106470, WO 09 /054832; WO 10/077230. The synthesis of such metallocene complexes described in these publications and other patents can be carried out by methods known per se.

For example, but not limited to, as described in U.S. Patent Nos. 7,285,608; 7, 169, 864, 7, 842, 764, EP 1 692 144, WO 09/054832, and WO 10/077230, each of which is incorporated herein by reference. The undesired non-mirromeric isomer of the metallocene compound recovers the ligand. The chemical reaction system depends on the organic ligand used to split the metallocene complex and regenerate the metallocene complex. Many organometallic compounds, including metallocene complexes, are inherently sensitive to protic materials, so it is believed that the scope of the invention can be extended to virtually any metallocene structure and is not only the examples described in the above references.

Non-limiting examples of more preferred metallocene compounds of the invention are as follows: A-(2-isopropyl-4-(p-isopropyl-phenyl)indolyl) (2-methyl-4-(pair -isopropyl-phenyl)indenyl)zirconium dichloride, A-(2-isopropyl-4-(p-t-butyl-phenyl)indenyl)(2-methyl-4-() p-T-butyl-phenyl)indenyl)zirconium dichloride, A-(2-isopropyl-4-(p-tert-butyl-phenyl)indenyl) (2,7-dimethyl 4-(p-tert-butyl-phenyl)indenyl)zirconium dichloride, A-(2-isopropyl-4-(p-tert-butyl-phenyl)indenyl) (2 ,5,6,7-tetramethyl-4-(p-t-butyl-phenyl)indenyl)zirconium dichloride, A-(2-isopropyl-6-methyl-4-(pair -T-butyl-phenyl)indenyl)(2,6-dimethyl-4-(p-t-butyl-phenyl)indenyl)zirconium dichloride, A-(2-isopropyl -4-(p-t-butyl-phenyl)indenyl)(2-methyl-4-(p-t-butyl-phenyl)indenyl)zirconium dichloride, A-(2-iso Propyl-4-(p-cyclohexyl-phenyl)indenyl)(2-methyl-4-(p-cyclohexyl-phenyl)indenyl)zirconium dichloride, A-(2-isopropyl -4-(p-trimethylformamidinyl, phenyl)indenyl)(2-methyl-4-(p-trimethylformamido-phenyl)indenyl)zirconium dichloride, A- (2-isopropyl-4-(p-adamantane) (phenyl-phenyl) indenyl) (2-methyl-4-(p-adamantyl-phenyl)indenyl)zirconium dichloride, A-(2-isopropyl-4-(p-para ( Trifluoromethyl)methyl-phenyl)indenyl)(2-methyl-4-(p-cis(trifluoromethyl)methyl-phenyl)indolyl)zirconium dichloride, A-(2 -isopropyl-4-phenyl-indenyl)(2-methyl-4-(p-tert-butyl-phenyl)indenyl)zirconium dichloride, A-(2-isopropyl-4 -(p-tert-butyl-phenyl)indenyl)(2-methyl-4-phenyl-indenyl)zirconium dichloride, A-(2-isopropyl-4-(p-third) Butyl-phenyl)indenyl)(2,7-dimethyl-4-phenyl-indenyl)zirconium dichloride, A-(2-isopropyl-4-(p-tert-butyl-) Phenyl) indenyl) (2,5,6,7-tetramethyl-4-phenyl-indenyl)zirconium dichloride, A-(2-isopropyl-6-methyl-4-(pair -T-butyl-phenyl)indenyl)(2,6-dimethyl-4-phenyl-indenyl)zirconium dichloride, A-(2-isopropyl-4-phenyl-fluorenyl) (2,7-Dimethyl-4-(p-t-butyl-phenyl)indenyl)zirconium dichloride, A-(2-isopropyl-4-phenyl-indenyl) (2) ,5,6,7-tetramethyl-4-(p-t-butyl-phenyl)indenyl)zirconium dichloride, A-(2-isopropyl-6-methyl-4-phenyl - mercapto) (2,6-dimethyl-4-(p-tert-butyl-phenyl)indenyl)zirconium dichloride, A-(2-isopropyl-4- (p-tert-butyl-phenyl)indenyl)(2-methyl-4-(4-naphthyl)indenyl)zirconium dichloride, A-(2-isopropyl-4-(4- Naphthyl)-fluorenyl)fluorenyl)(2-methyl-4-(p-tert-butyl-phenyl)indenyl)zirconium dichloride, A-bis(4-naphthyl-fluorenyl) Zirconium chloride, A-bis(2-methyl-benzo-indenyl)zirconium dichloride, A-bis(2-methyl-indenyl)zirconium dichloride, A-bis(2-methyl-4 -(1-naphthyl)-fluorenyl)zirconium dichloride, A-bis(2-methyl-4-(2-naphthyl)-fluorenyl)zirconium dichloride, A-bis(2-methyl -4-Phenyl-fluorenyl)zirconium dichloride, A-bis(2-methyl-4-tert-butyl-fluorenyl)zirconium dichloride, A-bis(2-methyl-4-iso Propyl-fluorenyl)zirconium dichloride, A-bis(2-methyl-4-ethyl-indenyl)zirconium dichloride, A-bis(2-methyl-4-dihydroanthracene-fluorenyl) Zirconium dichloride, A-bis(2,4-dimethyl-indenyl)zirconium dichloride, A-bis(2-ethyl-indenyl)zirconium dichloride, A-double (2-B) 4-ethyl-indenyl)zirconium dichloride, A-bis(2-ethyl-4-phenyl-indenyl)zirconium dichloride, A-bis(2-methyl-4,6- Diisopropyl-indenyl)zirconium dichloride, A-bis(2-methyl-4,5-diisopropyl-indenyl)zirconium dichloride, A-bis(2,4,6-three Methyl-fluorenyl) zirconium dichloride, A-bis(2,5,6-trimethyl-indenyl) zirconium dichloride A-bis(2,4,7-trimethyl-indenyl)zirconium dichloride, A-bis(2-methyl-5-isobutyl-indenyl)zirconium dichloride, A-double (2 -Methyl-5-tert-butyl-fluorenyl)zirconium dichloride, A-bis(2-methyl-4-(tris-butyl-phenyl)-fluorenyl)zirconium dichloride, A - bis(2-methyl-4-(4-methyl-phenyl)-fluorenyl) zirconium dichloride, A-bis(2-methyl-4-(4-ethyl-phenyl)-fluorene Zirconium dichloride, A-bis(2-methyl-4-(4-trifluoromethyl-phenyl)-fluorenyl) zirconium dichloride, A-bis(2-methyl-4-() 4-methoxy-phenyl)-fluorenyl) zirconium dichloride, A-bis(2-ethyl-4-(4-t-butyl-phenyl)-fluorenyl) zirconium dichloride, A - bis(2-ethyl-4-(4-methyl-phenyl)-indenyl) zirconium dichloride, A-bis(2-ethyl-4-(4-ethyl-phenyl)-fluorene Zirconium dichloride, A-bis(2-ethyl-4-(4-trifluoromethyl-phenyl)-fluorenyl) zirconium dichloride, A-bis(2-ethyl-4-( 4-methoxy-phenyl)-fluorenyl) zirconium dichloride, A-bis(2-methyl-4-(4-tris-butyl-phenyl)-indenyl) zirconium dimethyl, A-bis(2-methyl-4-(4-methyl-phenyl)-indenyl)zirconium dimethyl, A-bis(2-methyl-4-(4-ethyl-phenyl)- Mercapto)zirconium dimethyl, A-bis(2-methyl-4-(4-trifluoromethyl-phenyl)-indenyl)zirconium dimethyl, A-bis(2-A 4-(4-methoxy-phenyl)-indenyl)zirconium dimethyl, A-bis(2-ethyl-4-(4-t-butyl-phenyl)-indenyl)zirconium Methyl, A-bis(2-ethyl-4-(4-methyl-phenyl)-fluorenyl)zirconium dimethyl, A-bis(2-ethyl-4-(4-ethyl-benzene) Zirconium dimethyl, A-bis(2-ethyl-4-(4-trifluoromethyl-phenyl)-indenyl)zirconium dimethyl, A-bis(2-ethyl 4-(4-methoxy-phenyl)-indenyl)zirconium dimethyl, A-bis(2-isopropyl-4-(t-butyl-phenyl)-fluorenyl) dichloride Zirconium, A-bis(2-isopropyl-4-(4-methyl-phenyl)-indenyl) zirconium dichloride, A-bis(2-isopropyl-4-(4-ethyl-) Phenyl)-fluorenyl)zirconium dichloride, A-bis(2-isopropyl-4-(4-trifluoromethyl-phenyl)-fluorenyl)zirconium dichloride, A-bis(2- Isopropyl-4-(4-C4-methoxy-phenyl)-indenyl)zirconium dichloride, A-bis(2-isopropyl-4-(4'-tert-butyl-phenyl) )-fluorenyl)zirconium dichloride, A-bis(2-isopropyl-4-(4'-tert-butyl-phenyl)-fluorenyl)phosphonium dichloride, A-bis (2-iso) Propyl-4-(4'-tert-butyl-phenyl)-indenyl) titanium dichloride, A-bis(2-isopropyl-4-(4'-methyl-phenyl)-fluorene Zirconium dichloride, A-bis(2-isopropyl-4-(4'-n-propyl-phenyl)-fluorenyl)zirconium dichloride, A-bis(2- Propyl-4-(4'-n-butyl-phenyl)-indenyl)zirconium dichloride, A-bis(2-isopropyl-4-(4'-hexyl-phenyl)-fluorenyl Zirconium dichloride, A-bis(2-isopropyl-4-(4'-t-butyl-phenyl)-fluorenyl)zirconium dichloride, A-bis(2-isopropyl-4) -Phenyl)-fluorenyl)zirconium dichloride, A-bis(2-isopropyl-4-(4'-methyl-phenyl)-fluorenyl)zirconium dichloride, A-bis(2- Isopropyl-4-(4'-ethyl-phenyl)-indenyl)zirconium dichloride, A-bis(2-isopropyl-4-(4'-n-propyl-phenyl)- Mercapto)zirconium dichloride, A-bis(2-isopropyl-4-(4'-n-butyl-phenyl)-fluorenyl)zirconium dichloride, A-bis(2-isopropyl 4-(4'-hexyl-phenyl)-fluorenyl)zirconium dichloride, A-bis(2-isopropyl-4-(4'-pentyl-phenyl)-fluorenyl) dichloride Zirconium, A-bis(2-isopropyl-4-(4'-cyclohexyl-phenyl)-fluorenyl)zirconium dichloride, A-bis(2-isopropyl-4-(4'- Dibutyl-phenyl)-fluorenyl)zirconium dichloride, A-bis(2-isopropyl-4-(4'-tert-butyl-phenyl)-fluorenyl)zirconium dichloride, A - bis(2-methyl-4-(4'-tert-butyl-phenyl)-fluorenyl)zirconium dichloride, A-bis(2-methyl-4-(4'-t-butyl) -Phenyl)-fluorenyl) ruthenium dichloride, A-bis(2-methyl-4-(4'-tert-butyl-phenyl)-fluorenyl) titanium dichloride, A - bis(2-methyl-4-(4'-methyl-phenyl)-fluorenyl)zirconium dichloride, A-bis(2-methyl-4-(4'-n-propyl-benzene) Base)-fluorenyl) zirconium dichloride, A-bis(2-methyl-4-(4'-n-butyl-phenyl)-fluorenyl) zirconium dichloride, A-bis (2-A) 4-(4'-hexyl-phenyl)-fluorenyl) zirconium dichloride, A-bis(2-methyl-4-(4'-second-butyl-phenyl)-fluorenyl) Zirconium dichloride, A-bis(2-ethyl-4-phenyl-indenyl)zirconium dichloride, A-bis(2-ethyl-4-(4'-methyl-phenyl)-fluorene Zirconium dichloride, A-bis(2-ethyl-4-(4'-ethyl-phenyl)-fluorenyl)zirconium dichloride, A-bis(2-ethyl-4-(4) '-N-propyl-phenyl)-fluorenyl) zirconium dichloride, A-bis(2-ethyl-4-(4'-n-butyl-phenyl)-fluorenyl) zirconium dichloride , A-bis(2-ethyl-4-(4'-hexyl-phenyl)-fluorenyl)zirconium dichloride, A-bis(2-ethyl-4-(4'-pentyl-phenyl) )-fluorenyl)zirconium dichloride, A-bis(2-ethyl-4-(4'-cyclohexyl-phenyl)-fluorenyl)zirconium dichloride, A-bis(2-ethyl-4) -(4'-Second-butyl-phenyl)-indenyl)zirconium dichloride, A-bis(2-ethyl-4-(4'-t-butyl-phenyl)-fluorenyl) Zirconium chloride, A-bis(2-n-propyl-4-phenyl)-indenyl) zirconium dichloride, A-bis(2-n-propyl-4-(4'-methyl-benzene) Base)-mercapto)dichloro Zirconium, A-bis(2-n-propyl-4-(4'-ethyl-phenyl)-indenyl)zirconium dichloride, A-bis(2-n-propyl-4-(4') -iso-propyl-phenyl)-indenyl)zirconium dichloride, A-bis(2-n-propyl-4-(4'-n-butyl-phenyl)-fluorenyl) dichloride Zirconium, A-bis(2-n-propyl-4-(4'-hexyl-phenyl)-fluorenyl)zirconium dichloride, A-bis(2-n-propyl-4-(4'-) Cyclohexyl-phenyl)-fluorenyl)zirconium dichloride, A-bis(2-n-propyl-4-(4'-t-butyl-phenyl)-fluorenyl)zirconium dichloride, A - bis(2-n-propyl-4-(4'-tert-butyl-phenyl)-indenyl)zirconium dichloride, A-bis(2-n-butyl-4-phenyl)- Mercapto)zirconium dichloride, A-bis(2-n-butyl-4-(4'-methyl-phenyl)-fluorenyl)zirconium dichloride, A-bis(2-n-butyl) 4-(4'-ethyl-phenyl)-indenyl)zirconium dichloride, A-bis(2-n-butyl-4-(4'-n-propyl-phenyl)-fluorenyl Zirconium dichloride, A-bis(2-n-butyl-4-(4'-iso-propyl-phenyl)-indenyl)zirconium dichloride, A-bis(2-n-butyl) 4-(4'-n-butyl-phenyl)-indenyl)zirconium dichloride, A-bis(2-n-butyl-4-(4'-hexyl-phenyl)-fluorenyl) Zirconium dichloride, A-bis(2-n-butyl-4-(4'-cyclohexyl-phenyl)-fluorenyl)zirconium dichloride, A-bis(2-n-butyl-4- (4'-second dick (phenyl-phenyl)-fluorenyl) zirconium dichloride, A-bis(2-n-butyl-4-(4'-tert-butyl-phenyl)-fluorenyl) zirconium dichloride, A- Bis(2-hexyl-4-phenyl-indenyl)zirconium dichloride, A-bis(2-hexyl-4-(4'-methyl-phenyl)-fluorenyl)zirconium dichloride, A- Bis(2-hexyl-4-(4'-ethyl-phenyl)-indenyl)zirconium dichloride, A-bis(2-hexyl-4-(4'-n-propyl-phenyl)- Mercapto)zirconium dichloride, A-bis(2-hexyl-4-(4'-iso-propyl-phenyl)-fluorenyl)zirconium dichloride, A-bis(2-hexyl-4-() 4'-n-butyl-phenyl)-fluorenyl) zirconium dichloride, A-bis(2-hexyl-4-(4'-n-hexyl-phenyl)-fluorenyl) zirconium dichloride, A-bis(2-hexyl-4-(4'-cyclohexyl-phenyl)-fluorenyl)zirconium dichloride, A-bis(2-hexyl-4-(4'-secondbutyl-phenyl) )-fluorenyl)zirconium dichloride, A-bis(2-hexyl-4-(4'-tert-butyl-phenyl)-fluorenyl)zirconium dichloride, A-bis(2-methyl- 4-(4'-tert-butyl-phenyl)-indenyl zirconium bis(dimethylamine), A-bis(2-ethyl-4-(4'-tert-butyl-phenyl)-fluorene Zirconium dibenzyl, A-bis(2-methyl-4-(4'-tert-butyl-phenyl)-indenyl)zirconium dimethyl, A-(2-methyl-4-indole And azapentalene (2-methyl-4-(4'-methyl-phenyl)-fluorenyl) zirconium dichloride, A-( 2-methyl-5-indolocyclopentadienyl) (2-methyl-4-(4'-methyl-phenyl)-fluorenyl) zirconium dichloride, A-(2-methyl-6 - indole cyclopentadienyl) (2-methyl-4-(4'-methyl-phenyl)-fluorenyl) zirconium dichloride, A-(2-methyl-4-indolocyclopentane (2-methyl-4-(4'-ethyl-phenyl)-indenyl) zirconium dichloride, A-(2-methyl-4-thiocyclopentadiene) (thiapentalene) 2-Methyl-4-(4'-n-propyl-phenyl)-indenyl)zirconium dichloride, A-(2-methyl-4-indolocyclopentadiene) (2-methyl 4-(4'-isopropyl-phenyl)-indenyl)zirconium dichloride, A-(2-methyl-6-indolocyclopentadienyl) (2-methyl-4-(4) '-Isopropyl-phenyl)-fluorenyl)zirconium dichloride, A-(2,5-dimethyl-6-thienecyclopentadienyl) (2-methyl-4-(4'-) Isopropyl-phenyl)-fluorenyl)zirconium dichloride, A-(2-methyl-6- And oxapentalene (2-methyl-4-(4'-isopropyl-phenyl)-indenyl) zirconium dichloride, A-(2-methyl-6-indolocyclopentyl Diene) (2-methyl-4-(4'-n-butyl-phenyl)-fluorenyl)zirconium dichloride, A-(2-methyl-5-thienecyclopentadiene) 2-methyl-4-(4'-n-butyl-phenyl)-indenyl)zirconium dichloride, A-(2-methyl-4- And cyclopentadienyl) (2-methyl-4-(4'-n-butyl-phenyl)-fluorenyl) zirconium dichloride, A-(2-methyl-4-thiocyclopentane Alkene (2-methyl-4-(4'-t-butyl-phenyl)-indenyl)zirconium dichloride, A-(2-methyl-4- And cyclopentadienyl) (2-methyl-4-(4'-t-butyl-phenyl)-indenyl) zirconium dichloride, A-(2-methyl-4-indolocyclopentane (Alkyl) (2-methyl-4-(4'-tert-butyl-phenyl)-indenyl) zirconium dichloride, A-(2-methyl-6-indolocyclopentadiene) (2 -Methyl-4-(4'-tert-butyl-phenyl)-indenyl)zirconium dichloride, A-(2-methyl-4-indolocyclopentadiene) (2-methyl- 4-(4'-n-pentyl-phenyl)-fluorenyl)zirconium dichloride, A-(2-methyl-N-phenyl-6-indolocyclopentadiene) (2-methyl -4-(4'-n-pentyl-phenyl)-fluorenyl) zirconium dichloride, A-(2-methyl-4- And cyclopentadienyl) (2-methyl-4-(4'-n-pentyl-phenyl)-fluorenyl)zirconium dichloride, A-(2-methyl-4-indolocyclopentane ((2-methyl-4-(4'-n-hexyl-phenyl)-fluorenyl) zirconium dichloride, A-(2-methyl-4-thiacyclopentadienyl) (2- Methyl-4-(4'-n-hexyl-phenyl)-indenyl)zirconium dichloride, A-(2-methyl-6-thiaxetene) (2-methyl-4-) (4'-n-hexyl-phenyl)-indenyl) zirconium dichloride, A-(2,5-dimethyl-4-thiacyclopentadienyl) (2-methyl-4-(4) '-n-hexyl-phenyl)-fluorenyl) zirconium dichloride, A-(2,5-dimethyl-6-thienecyclopentadienyl) (2-methyl-4-(4'-) n-Hexyl-phenyl)-indenyl) zirconium dichloride, A-(2,5-dimethyl-6-thienecyclopentadienyl) (2-methyl-4-(4'-cyclohexyl) -Phenyl)-fluorenyl)zirconium dichloride, A-(2-methyl-4-indolocyclopentadienyl) (2-methyl-4-(4'-trimethylformamidinyl-benzene) Base)-fluorenyl) zirconium dichloride, A-(2-methyl-4-thiocyclopentadienyl) (2-methyl-4-(4'-trimethylformamidinyl-phenyl) - mercapto) zirconium dichloride, A-(2-methyl-5-thiacyclopentadienyl) (2-methyl-4-(4'-trimethylformamido-phenyl)-fluorene Zirconium dichloride, A-(2-methyl-6-thienecyclopentadienyl) (2-methyl-4-(4'-trimethylformamidinyl) -Phenyl)-fluorenyl)zirconium dichloride, A-(2,5-dimethyl-4-indolocyclopentadienyl) (2-methyl-4-(4'-adamantyl-benzene) Base)-fluorenyl) zirconium dichloride, A-(2-methyl-4-thiocyclopentadienyl) (2-methyl-4-(4'-adamantyl-phenyl)-fluorenyl Zirconium dichloride, A-(2-methyl-6-thienecyclopentadienyl) (2-methyl-4-(4'-adamantyl-phenyl)-fluorenyl) zirconium dichloride , A-(2,5-dimethyl-4-thiacyclopentadienyl) (2-methyl-4-(4'-adamantyl-phenyl)-fluorenyl)zirconium dichloride, A -(2-methyl-4-indolocyclopentadienyl) (2-methyl-4-(4'-tris(trifluoromethyl)methyl-phenyl)-indenyl)zirconium dichloride, A-(2,5-dimethyl-4-indolocyclopentadienyl) (2-methyl-4-(4'-para(trifluoromethyl)methyl-phenyl)-indenyl) Zirconium chloride, A-(2-methyl-4-thiocyclopentadienyl) (2-methyl-4-(4'-para(trifluoromethyl)methyl-phenyl)-fluorenyl) Zirconium dichloride, A-(2-methyl-6-thiacyclopentadienyl) (2-methyl-4-(4'-para(trifluoromethyl)methyl-phenyl)-fluorenyl) Zirconium dichloride, A-(2-methyl-4-indenecyclopentadienyl) (2-ethyl-4-(4'-t-butyl-phenyl)-fluorenyl) dichloride Zirconium, A-(2-methyl-5-indolocyclopentadienyl) (2-n-butyl-4-(4'-tert-butyl-phenyl)-fluorenyl) Zirconium chloride, A-(2-methyl-N-phenyl-6-indolocyclopentadienyl) (2-methyl-4-(4'-t-butyl-phenyl)-fluorenyl) Zirconium dichloride, A-(2-methyl-4-indenecyclopentadienyl) (2-methylindenyl) zirconium dichloride, A-(2-methyl-N-phenyl-4- (cyclopentadiene) (2-methylindenyl) zirconium dichloride, A-(2-methyl-4-thiocyclopentadienyl) (2-methylindenyl) zirconium dichloride, A-(2-methyl-5-thienecyclopentadienyl)(2-methylindenyl)zirconium dichloride, A-(2-methyl-6-thiacyclopentadiene) (2- Methyl fluorenyl) zirconium dichloride, A-(2-methyl-4-indenecyclopentadienyl) (fluorenyl) zirconium dichloride, A-(2-methyl-5-indolocyclopentyl Diene) (fluorenyl) zirconium dichloride, A-(2-methyl-6-indenecyclopentadienyl) (fluorenyl) zirconium dichloride, A-(2-methyl-N-phenyl -4-indolocyclopentadiene) (fluorenyl) zirconium dichloride, A-(2-methyl-N-phenyl-5-fluorenylcyclopentadienyl) (fluorenyl) zirconium dichloride, A-(2-methyl-N-phenyl-6-indolocyclopentadienyl) (fluorenyl) zirconium dichloride, A-(2,5-dimethyl-N-phenyl-6-fluorene And cyclopentadienyl (fluorenyl) zirconium dichloride, A-(2-methyl-4-thiocyclopentadienyl) (fluorenyl) zirconium dichloride, A-(2-methyl-5 -thilylcyclopentadienyl)(fluorenyl)zirconium dichloride, A-(2-A -6-thiatocyclopentadienyl)(fluorenyl)zirconium dichloride, A-(2,5-dimethyl-4-thiacyclopentadienyl)(fluorenyl)zirconium dichloride, A- (2-methyl-4-indolocyclopentadienyl) (2-methyl-4-phenyl-indenyl) zirconium dichloride, A-(2-methyl-5-indolocyclopentadiene (2-methyl-4-phenyl-indenyl)zirconium dichloride, A-(2-methyl-6-indolocyclopentadienyl) (2-methyl-4-phenyl-fluorenyl) Zirconium dichloride, A-(2-methyl-N-phenyl-4-indolocyclopentadienyl) (2-methyl-4-phenyl-indenyl) zirconium dichloride, A-( 2-methyl-N-phenyl-5-indolocyclopentadienyl) (2-methyl-4-phenyl-indenyl) zirconium dichloride, A-(2-methyl-4-thiazide Cyclopentadienyl)(2-methyl-4-phenyl-indenyl)zirconium dichloride, A-(2-methyl-5-thiacyclopentadiene) (2-methyl-4-benzene) Base-fluorenyl) zirconium dichloride, A-(2-methyl-6-thiocyclopentadienyl) (2-methyl-4-phenyl-indenyl) zirconium dichloride, A-(2 -methyl-4- And cyclopentadienyl) (2-methyl-4-phenyl-indenyl) zirconium dichloride, A-(2-methyl-4-indolocyclopentadiene) (2-methyl-4, 5-Benzo-indenyl)zirconium dichloride, A-(2-methyl-N-phenyl-4-indolocyclopentadienyl) (2-methyl-4,5-benzo-fluorenyl) Zirconium dichloride, A-(2-methyl-N-phenyl-5-fluorenylcyclopentadienyl) (2-methyl-4,5-benzo-indenyl) zirconium dichloride, A -(2-methyl-N-phenyl-6-indolocyclopentadienyl) (2-methyl-4,5-benzo-indenyl) zirconium dichloride, A-(2-methyl- 4-thiatocyclopentadienyl) (2-methyl-4,5-benzo-indenyl)zirconium dichloride, A-(2-methyl-5-thienecyclopentadiene) (2- Methyl-4,5-benzo-indenyl)zirconium dichloride, A-(2-methyl-6-thiacyclopentadienyl) (2-methyl-4,5-benzo-indenyl) ) Zirconium dichloride, A-(2-methyl-4- And cyclopentadienyl) (2-methyl-4,5-benzo-indenyl) zirconium dichloride, A-(2-methyl-5- And cyclopentadienyl) (2-methyl-4,5-benzo-indenyl) zirconium dichloride, A-(2-methyl-6- And cyclopentadienyl) (2-methyl-4,5-benzo-indenyl) zirconium dichloride, A-bis(2-methyl-4-indenecyclopentadienyl) zirconium dichloride, A-bis(2-methyl-N-phenyl-4-indolocyclopentadienyl) zirconium dichloride, A-bis(2-methyl-4-thiocyclopentadiene) zirconium dichloride , A-bis[2-tert-butylmethyl-4-(1-naphthyl)-fluorenyl]zirconium dichloride, A-bis[2-t-butylmethyl-4-(2-naphthyl)-anthracene Zirconium dichloride, A-bis[2-tert-butylmethyl-4-(4-methyl-phenyl)-indenyl]zirconium dichloride, A-bis[2-t-butylmethyl-4 -(4-biphenyl)-fluorenyl]zirconium dichloride, A-bis[2-tert-butylmethyl-4-(4-ethyl-phenyl)-fluorenyl]zirconium dichloride, A- Bis[2-t-butylmethyl-4-(4-n-propyl-phenyl)-indenyl]zirconium dichloride, A-bis[2-t-butylmethyl-4-(4-iso-propane) -Phenyl)-indenyl]zirconium dichloride, A-bis[2-tert-butylmethyl-4-(4-t-butyl-phenyl)-indenyl]zirconium dichloride, A-double [2-Tertibutylmethyl-4-(4-t-butyl-phenyl)-indenyl]zirconium dichloride, A-bis[2-t-butylmethyl-4-(4-cyclohexyl-benzene) Base)-fluorenyl] zirconium dichloride, A-bis[2-tert-butylmethyl-4-(4-trimethylformamidinyl-phenyl)-indenyl]zirconium dichloride, A-bis[2-tert-butylmethyl-4-(4-adamantyl-phenyl)-indenyl]zirconium dichloride, A-bis[2-t-butylmethyl-4-(3-biphenyl) Base)-fluorenyl]zirconium dichloride, A-bis[2-tert-butylmethyl-4-(3,5-dimethyl-phenyl)-indenyl]zirconium dichloride, A-double [2 -T-butylmethyl-4-(3,5-di-(trifluoromethyl)-phenyl)-indenyl]zirconium dichloride, A-bis[2-t-butylmethyl-4-(3, 5-bitriphenyl)-fluorenyl]zirconium dichloride, A-bis[2-cyclopentylmethyl-4-(1-naphthyl)-fluorenyl]zirconium dichloride, A-bis[2- Cyclopentylmethyl-4-(2-naphthyl)-fluorenyl]zirconium dichloride, A-bis[2-cyclopentylmethyl-4-(4-methyl-phenyl)-fluorenyl] Zirconium dichloride, A-bis[2-cyclopentylmethyl-4-(4-biphenyl)-indenyl]zirconium dichloride, A-bis[2-cyclopentylmethyl-4-( 4-ethyl-phenyl)-fluorenyl]zirconium dichloride, A-bis[2-cyclopentylmethyl-4-(4-n-propyl-phenyl)-indenyl]zirconium dichloride , A-bis[2-cyclopentylmethyl-4-(4-iso-propyl-phenyl)-indenyl]zirconium dichloride, A-bis[2-cyclopentylmethyl-4-( 4-tert-butyl-phenyl)-indenyl]zirconium dichloride, A-bis[2-cyclopentylmethyl-4-(4-secondbutyl-phenyl)-fluorenyl]dichloride Zirconium, A-bis[2-cyclopentylmethyl-4-(4-cyclohexyl- Base)-fluorenyl]zirconium dichloride, A-bis[2-cyclopentylmethyl-4-(4-trimethylformamidinyl-phenyl)-indenyl]zirconium dichloride, A-double [2-Cyclopentylmethyl-4-(4-adamantyl-phenyl)-indenyl]zirconium dichloride, A-bis[2-cyclopentylmethyl-4-(3-biphenyl) )-fluorenyl]zirconium dichloride, A-bis[2-cyclopentylmethyl-4-(3,5-dimethyl-phenyl)-fluorenyl]zirconium dichloride, A-double [2 -cyclopentylmethyl-4-(3,5-di-(trifluoromethyl)-phenyl)indenyl]zirconium dichloride, A-bis[2-cyclopentylmethyl-4-(3) ,5-bitriphenyl)-fluorenyl]zirconium dichloride, A-bis[2-cyclohexylmethyl-4-(1-naphthyl)-fluorenyl]zirconium dichloride, A-bis[2- Cyclohexylmethyl-4-(2-naphthyl)-fluorenyl]zirconium dichloride, A-bis[2-cyclohexylmethyl-4-(4-methyl-phenyl)-fluorenyl]dichloride Zirconium, A-bis[2-cyclohexylmethyl-4-(4-biphenyl)-fluorenyl]zirconium dichloride, A-bis[2-cyclohexylmethyl-4-(4-ethyl -phenyl)-fluorenyl]zirconium dichloride, A-bis[2-cyclohexylmethyl-4-(4-n-propyl-phenyl)-fluorenyl]zirconium dichloride, A-double [2 -cyclohexylmethyl-4-(4-isopropyl-phenyl)-indenyl]zirconium dichloride, A-bis[2-cyclohexylmethyl-4-(4-tert-butyl-phenyl) )-fluorenyl]zirconium dichloride, A-bis[2-cyclohexyl 4-(4-tert-butyl-phenyl)-indenyl]zirconium dichloride, A-bis[cyclohexylmethyl-4-(4-cyclohexyl-phenyl)-indenyl]dichloride Zirconium, A-bis[cyclohexylmethyl-4-(4-trimethylformamidinyl-phenyl)-indenyl]zirconium dichloride, A-bis[cyclohexylmethyl-4-(4- Adamantyl-phenyl)-fluorenyl]zirconium dichloride, A-bis[cyclohexylmethyl-4-(3-biphenyl)-indenyl]zirconium dichloride, A-bis[cyclohexyl 4-(3,5-dimethyl-phenyl)-indenyl]zirconium dichloride, A-bis[cyclohexylmethyl-4-(3,5-di-(trifluoromethyl)- Phenyl)-fluorenyl]zirconium dichloride, A-bis[2-cyclohexylmethyl-4-(3,5-triphenyl)-fluorenyl]zirconium dichloride, A-bis[2-ring Heptylmethyl-4-(1-naphthyl)-fluorenyl]zirconium dichloride, A-bis[2-cycloheptylmethyl-4-(2-naphthyl)-fluorenyl]zirconium dichloride , A-bis[2-cycloheptylmethyl-4-(4-methyl-phenyl)-indenyl]zirconium dichloride, A-bis[2-cycloheptylmethyl-4-(4- Biphenyl)-fluorenyl]zirconium dichloride, A-bis[2-cycloheptylmethyl-4-(4-ethyl-phenyl)-indenyl]zirconium dichloride, A-double [2 -cycloheptylmethyl-4-(4-n-propyl-phenyl)-indenyl]zirconium dichloride, A-bis[2-cycloheptylmethyl-4-(4-isopropyl-benzene) Base)-fluorenyl]zirconium dichloride, A-double [2- Heptylmethyl-4-(4-t-butyl-phenyl)-indenyl]zirconium dichloride, A-bis[2-cycloheptylmethyl-4-(4-second butyl-benzene) Base)-fluorenyl]zirconium dichloride, A-bis[2-cycloheptylmethyl-4-(4-cyclohexyl-phenyl)-fluorenyl]zirconium dichloride, A-bis[2-ring Heptylmethyl-4-(4-trimethylformamidinyl-phenyl)-indenyl]zirconium dichloride, A-bis[2-cycloheptylmethyl-4-(4-adamantyl- Phenyl)-fluorenyl]zirconium dichloride, A-bis[2-cycloheptylmethyl-4-(3-biphenyl)-indenyl]zirconium dichloride, A-bis[2-cycloheptane Methyl 4-(3,5-dimethyl-phenyl)-indenyl]zirconium dichloride, A-bis[2-cycloheptylmethyl-4-(3,5-di-(three) Fluoromethyl-phenyl)-fluorenyl]zirconium dichloride, A-bis[2-cycloheptylmethyl-4-(3,5-biphenyl)-fluorenyl]zirconium dichloride, A- Bis[2-adamantylmethyl-4-(1-naphthyl)-fluorenyl]zirconium dichloride, A-bis[2-adamantylmethyl-4-(2-naphthyl)-fluorenyl ] Zirconium dichloride, A-bis[2-adamantylmethyl-4-(4-methyl-phenyl)-indenyl]zirconium dichloride, A-bis[2-adamantylmethyl- 4-(4-biphenyl)-indenyl]zirconium dichloride, A-bis[2-adamantylmethyl-4-(4-ethyl-phenyl)-indenyl]zirconium dichloride, A-bis[2-adamantylmethyl-4-(4-positive-propyl) -phenyl)-fluorenyl]zirconium dichloride, A-bis[2-adamantylmethyl-4-(4-isopropyl-phenyl)-indenyl]zirconium dichloride, A-double [ 2-adamantylmethyl-4-(4-t-butyl-phenyl)-indenyl]zirconium dichloride, A-bis[2-adamantylmethyl-4-(4-second dibutyl) -Phenyl)-indenyl]zirconium dichloride, A-bis[2-adamantylmethyl-4-(4-cyclohexyl-phenyl)-indenyl]zirconium dichloride, A-double [ 2-adamantylmethyl-4-(4-trimethylformamidinyl-phenyl)-indenyl]zirconium dichloride, A-bis[2-adamantylmethyl-4-(4-golden Alkyl-phenyl)-fluorenyl]zirconium dichloride, A-bis[2-adamantylmethyl-4-(3-biphenyl)-indenyl]zirconium dichloride, A-double [2 -adamantylmethyl-4-(3,5-dimethyl-phenyl)-indenyl]zirconium dichloride, A-bis[2-adamantylmethyl-4-(3,5-di -(Trifluoromethyl-phenyl)-indenyl]zirconium dichloride, A-bis[2-adamantylmethyl-4-(3,5-biphenyl)-indenyl]zirconium dichloride , A-bis[2-trimethylformamidinylmethyl-4-(4-t-butyl-phenyl)-indenyl]zirconium dichloride, A-bis[2-(2-methoxy) -2-methyl-propyl)-4-(4-t-butyl-phenyl)-indenyl]zirconium dichloride, A-bis[2-(2,6-dimethyl-benzyl) -4-(4-tert-butyl-phenyl)- Mercapto]zirconium dichloride, A-bis[2-(2,4,6-trimethyl-benzyl)-4-(4-t-butyl-phenyl)-indenyl]zirconium dichloride , A-bis[2-bicyclo[2.2.1]heptylmethyl-4-(1-naphthyl)-fluorenyl]zirconium dichloride, A-bis[2-bicyclo[2.2.1]heptyl 4-(2-naphthyl)-fluorenyl]zirconium dichloride, A-bis[2-bicyclo[2.2.1]heptylmethyl-4-(4-methyl-phenyl)-fluorenyl ] Zirconium dichloride, A-bis[2-bicyclo[2.2.1]heptylmethyl-4-(4-biphenyl)-indenyl]zirconium dichloride, A-bis[2-bicyclo[2.2 .1]heptylmethyl-4-(4-ethyl-phenyl)-indenyl]zirconium dichloride, A-bis[2-bicyclo[2.2.1]heptylmethyl-4-(4- n-Propyl-phenyl)-indenyl]zirconium dichloride, A-bis[2-bicyclo[2.2.1]heptylmethyl-4-(4-isopropyl-phenyl)-indenyl] Zirconium chloride, A-bis[2-bicyclo[2.2.1]heptylmethyl-4-(4-t-butyl-phenyl)-indenyl]zirconium dichloride, A-bis[2-bicyclic [2.2.1] Heptylmethyl-4-(4-t-butyl-phenyl)-indenyl]zirconium dichloride, A-bis[2-bicyclo[2.2.1]heptylmethyl-4 -(4-cyclohexyl-phenyl)-indenyl]zirconium dichloride, A-bis[2-bicyclo[2.2.1]heptylmethyl-4-(4-trimethylformamidinyl-phenyl )-fluorenyl]zirconium dichloride, A-bis[2-bicyclo[2.2.1]heptylmethyl-4-(4-gold) Alkyl-phenyl)-fluorenyl]zirconium dichloride, A-bis[2-bicyclo[2.2.1]heptylmethyl-4-(3-biphenyl)-indenyl]zirconium dichloride, A-bis[2-bicyclo[2.2.1]heptylmethyl-4-(3,5-dimethyl-phenyl)-fluorenyl]zirconium dichloride, A-bis[2-bicyclo[2.2. 1]Heptylmethyl-4-(3,5-di-(trifluoromethyl)-phenyl)-indenyl]zirconium dichloride, A-bis[2-bicyclo[2.2.1]heptyl 4-(3,5-bitriphenyl)-indenyl]zirconium dichloride, A-bis[2-cyclohexylmethyl-4-(1-naphthyl)-6-methyl-indenyl] Zirconium dichloride, A-bis[2-cyclohexylmethyl-4-(2-naphthyl)-6-methyl-indenyl]zirconium dichloride, A-bis[2-cyclohexylmethyl-4 -(4-Methyl-phenyl)-6-methyl-indenyl]zirconium dichloride, A-bis[2-cyclohexylmethyl-4-(4-biphenylyl)-6-methyl- Mercapto]zirconium dichloride, A-bis[2-cyclohexylmethyl-4-(4-ethyl-phenyl)-6-methyl-indenyl]zirconium dichloride, A-bis[2- Cyclohexylmethyl-4-(4-n-propyl-phenyl)-6-methyl-indenyl]zirconium dichloride, A-bis[2-cyclohexylmethyl-4-(4-isopropyl) -phenyl)-6-methyl-indenyl]zirconium dichloride, A-bis[2-cyclohexylmethyl-4-(4-t-butyl-phenyl)-6-methyl-indenyl ] Zirconium dichloride, A-bis[2-cyclohexylmethyl-4-(4-second butyl-phenyl)- 6-Methyl-fluorenyl]zirconium dichloride, A-bis[2-cyclohexylmethyl-4-(4-cyclohexyl-phenyl)-6-methyl-indenyl]zirconium dichloride, A - bis[2-cyclohexylmethyl-4-(4-trimethylformamidinyl-phenyl)-6-methyl-indenyl]zirconium dichloride, A-bis[2-cyclohexylmethyl- 4-(4-adamantyl-phenyl)-6-methyl-indenyl]zirconium dichloride, A-bis[2-cyclohexylmethyl-4-(3-biphenyl)-6- Base-fluorenyl] zirconium dichloride, A-bis[2-cyclohexylmethyl-4-(3,5-dimethyl-phenyl)-6-methyl-indenyl]zirconium dichloride, A - bis[2-cyclohexylmethyl-4-(3,5-di-(trifluoromethyl)-phenyl)-6-methyl-indenyl]zirconium dichloride, A-bis[2-ring Hexylmethyl-4-(3,5-biphenyl)-6-methyl-indenyl]zirconium dichloride, A-bis[2-cyclohexylmethyl-4-(1-naphthyl)-7 -methyl-indenyl]zirconium dichloride, A-bis[2-cyclohexylmethyl-4-(2-naphthyl)-7-methyl-indenyl]zirconium dichloride, A-double [2 -cyclohexylmethyl-4-(4-methyl-phenyl)-7-methyl-indenyl]zirconium dichloride, A-bis[2-cyclohexylmethyl-4-(4-biphenyl) )-7-methyl-indenyl]zirconium dichloride, A-bis[2-cyclohexylmethyl-4-(4-ethyl-phenyl)-7-methyl-indenyl]zirconium dichloride , A-bis[2-cyclohexylmethyl-4-(4-n-propyl-phenyl)-7 -methyl-indenyl]zirconium dichloride, A-bis[2-cyclohexylmethyl-4-(4-iso-propyl-phenyl)-7-methyl-indenyl]zirconium dichloride, A-bis[2-cyclohexylmethyl-4-(4-t-butylphenyl)-7-methyl-indenyl]zirconium dichloride, A-bis[2-cyclohexylmethyl-4- (4-second butylphenyl)-7-methyl-indenyl]zirconium dichloride, A-bis[2-cyclohexylmethyl-4-(4-cyclohexyl-phenyl)-7- Base-fluorenyl] zirconium dichloride, A-bis[2-cyclohexylmethyl-4-(4-trimethylformamido-phenyl)-7-methyl-indenyl]zirconium dichloride, A-bis[2-cyclohexylmethyl-4-(4-adamantyl-phenyl)-7-methyl-indenyl]zirconium dichloride, A-bis[2-cyclohexylmethyl-4- (3-biphenyl)-7-methyl-indenyl]zirconium dichloride, A-bis[2-cyclohexylmethyl-4-(3,5-dimethyl-phenyl)-7- Base-fluorenyl]zirconium dichloride, A-bis[2-cyclohexylmethyl-4-(3,5-di-(trifluoromethyl)-phenyl-7-methyl-indenyl]dichloride Zirconium, A-bis[2-cyclohexylmethyl-4-(3,5-biphenyl)-7-methyl-indenyl]zirconium dichloride, A-bis[2-[(1-A) Cyclohexyl)methyl]-4-(t-butylphenyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-methylcyclopentyl)methyl]-4 -(T-butylphenyl)-1-indenyl]zirconium dichloride, A- [2-[(1-Methylcycloheptyl)methyl]-4-(t-butylphenyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-methyl) Cyclodecyl)methyl]-4-(t-butylphenyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-methylcyclooctyl)methyl]-4 -(T-butylphenyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-ethylcyclohexyl)methyl]-4-(t-butylphenyl)- 1-indenyl]zirconium dichloride, A-bis[2-[(1-ethylcyclopentyl)methyl]-4-(t-butylphenyl)-1-indenyl]zirconium dichloride , A-bis[2-[(1-ethylcycloheptyl)methyl]-4-(t-butylphenyl)-1-indenyl]zirconium dichloride, A-bis[2-[( 1-ethylcyclodecyl)methyl]-4-(t-butylphenyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-ethylcyclooctyl)) 4-(t-butylphenyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-ethylcyclobutyl)methyl]-4-(third Phenylphenyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-propylcyclohexyl)methyl]-4-(t-butylphenyl)-1-indenyl] Zirconium dichloride, A-bis[2-[(1-propylcyclopentyl)methyl]-4-(t-butylphenyl)-1-indenyl]zirconium dichloride, A-double [ 2-[(1-propylcycloheptyl)methyl]-4-(t-butylphenyl)-1-indenyl]zirconium dichloride, A-bis[2- [(1-propylcyclodecyl)methyl]-4-(t-butylphenyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-propylcyclooctyl) )methyl]-4-(t-butylphenyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-propylcyclobutyl)methyl]-4-( Tributylphenyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-propylcyclopropyl)methyl]-4-(t-butylphenyl)-1- Mercapto]zirconium dichloride, A-bis[2-[(1-methylcyclohexyl)methyl]-4-(1-naphthyl)-1-indenyl]zirconium dichloride, A-double [ 2-[(1-Methylcyclopentyl)methyl]-4-(1-naphthyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-methylcycloheptyl) )methyl]-4-(1-naphthyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-methylcyclodecyl)methyl]-4-(1-naphthalene) Base)-1-indenyl]zirconium dichloride, A-bis[2-[(1-methylcyclooctyl)methyl]-4-(1-naphthyl)-1-indenyl] dichloride Zirconium, A-bis[2-[(1-ethylcyclohexyl)methyl]-4-(1-naphthyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1- Ethylcyclopentyl)methyl]-4-(1-naphthyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-ethylcycloheptyl)methyl]-4 -(1-Naphthyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-ethylcyclodecyl)methyl]-4-(1-naphthyl)-1-anthracene Zirconium dichloride, A-bis[2-[(1-ethyl) Octyl)methyl]-4-(1-naphthyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-ethylcyclobutyl)methyl]-4-(1) -naphthyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-propylcyclohexyl)methyl]-4-(1-naphthyl)-1-indenyl]dichloride Zirconium, A-bis[2-[(1-propylcyclopentyl)methyl]-4-(1-naphthyl)-1-indenyl]zirconium dichloride, A-bis[2-[( 1-propylcycloheptyl)methyl]-4-(1-naphthyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-propylcyclodecyl)methyl] 4-(1-naphthyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-propylcyclooctyl)methyl]-4-(1-naphthyl)-1 - mercapto] zirconium dichloride, A-bis[2-[(1-propylcyclobutyl)methyl]-4-(1-naphthyl)-1-indenyl]zirconium dichloride, A- Bis[2-[(1-propylcyclopropyl)methyl]-4-(1-naphthyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-methyl ring) Hexyl)methyl]-4-phenyl-1-indenyl]zirconium dichloride, A-bis[2-[(1-methylcyclopentyl)methyl]-4-phenyl-1-indenyl ] Zirconium dichloride, A-bis[2-[(1-methylcycloheptyl)methyl]-4-phenyl-1-indenyl]zirconium dichloride, A-bis [2-[(1) -Methylcyclodecyl)methyl]-4-phenyl-1-indenyl]zirconium dichloride, A-bis[2-[(1-methylcyclooctyl)methyl]-4-phenyl -1-mercapto]zirconium dichloride, A-double [2-[(1-B) Cyclohexyl)methyl]-4-phenyl-1-indenyl]zirconium dichloride, A-bis[2-[(1-ethylcyclopentyl)methyl]-4-phenyl-1-indole Zirconium dichloride, A-bis[2-[(1-ethylcycloheptyl)methyl]-4-phenyl-1-indenyl]zirconium dichloride, A-bis[2-[( 1-ethylcyclodecyl)methyl]-4-phenyl-1-indenyl]zirconium dichloride, A-bis[2-[(1-ethylcyclooctyl)methyl]-4-benzene 1,1-mercapto]zirconium dichloride, A-bis[2-[(1-ethylcyclobutyl)methyl]-4-phenyl-1-indenyl]zirconium dichloride, A-double [2-[(1-propylcyclohexyl)methyl]-4-phenyl-1-indenyl]zirconium dichloride, A-bis[2-[(1-propylcyclopentyl)methyl] -4-Phenyl-1-indenyl]zirconium dichloride, A-bis[2-[(1-propylcycloheptyl)methyl]-4-phenyl-1-indenyl]zirconium dichloride , A-bis[2-[(1-propylcyclodecyl)methyl]-4-phenyl-1-indenyl]zirconium dichloride, A-bis[2-[(1-propylcyclooctane) Methyl]-4-phenyl-1-indenyl]zirconium dichloride, A-bis[2-[(1-propylcyclobutyl)methyl]-4-phenyl-1-indenyl ] Zirconium dichloride, A-bis[2-[(1-propylcyclopropyl)methyl]-4-phenyl-1-indenyl]zirconium dichloride, A-bis [2-[(1) -Methylcyclohexyl)methyl]-4-(2-naphthyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-methylcyclopentyl)methyl]-4 -(2-naphthalene )-1-indenyl]zirconium dichloride, A-bis[2-[(1-methylcycloheptyl)methyl]-4-(2-naphthyl)-1-indenyl]zirconium dichloride , A-bis[2-[(1-methylcyclodecyl)methyl]-4-(2-naphthyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1- Methylcyclooctyl)methyl]-4-(2-naphthyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-ethylcyclohexyl)methyl]-4- (2-Naphthyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-ethylcyclopentyl)methyl]-4-(2-naphthyl)-1-indenyl ] Zirconium dichloride, A-bis[2-[(1-ethylcycloheptyl)methyl]-4-(2-naphthyl)-1-indenyl]zirconium dichloride, A-double [2] -[(1-ethylcyclodecyl)methyl]-4-(2-naphthyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-ethylcyclooctyl) Methyl]-4-(2-naphthyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-ethylcyclobutyl)methyl]-4-(2-naphthyl) )-1-indenyl]zirconium dichloride, 3-bis[2-[(1-propylcyclohexyl)methyl]-4-(2-naphthyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-propylcyclopentyl)methyl]-4-(2-naphthyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-propyl) Cycloheptylheptyl)methyl]-4-(2-naphthyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-propylcyclodecyl)methyl]-4- (2-Naphthyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-propyl ring) Methyl]-4-(2-naphthyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-propylcyclobutyl)methyl]-4-(2- Naphthyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-propylcyclopropyl)methyl]-4-(2-naphthyl)-1-indenyl]dichloride Zirconium, A-bis[2-[(1-methylcyclohexyl)methyl]-4-(4-methyl-phenyl)-1-indenyl]zirconium dichloride, A-bis[2- [(1-Methylcyclopentyl)methyl]-4-(4-methyl-phenyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-methylcycloheptane) Methyl]-4-(4-methyl-phenyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-methylcyclodecyl)methyl]-4- (4-methyl-phenyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-methylcyclooctyl)methyl]-4-(4-methyl-phenyl) )-1-indenyl]zirconium dichloride, A-bis[2-[(1-ethylcyclohexyl)methyl]-4-(4-methyl-phenyl)-1-indenyl]dichloride Zirconium, A-bis[2-[(1-ethylcyclopentyl)methyl]-4-(4-methyl-phenyl)-1-indenyl]zirconium dichloride, A-double [2 -[(1-ethylcycloheptyl)methyl]-4-(4-methyl-phenyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-ethyl ring) Mercapto)methyl]-4-(4-methyl-phenyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-ethylcyclooctyl)methyl]-4 -(4-Methyl-phenyl)-1-indenyl]zirconium dichloride, A- [2-[(1-ethylcyclobutyl)methyl]-4-(4-methyl-phenyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-propyl) Cyclohexyl)methyl]-4-(4-methyl-phenyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-propylcyclopentyl)methyl]- 4-(4-Methyl-phenyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-propylcycloheptyl)methyl]-4-(4-methyl- Phenyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-propylcyclodecyl)methyl]-4-(4-methyl-phenyl)-1-indenyl ] Zirconium dichloride, A-bis[2-[(1-propylcyclooctyl)methyl]-4-(4-methyl-phenyl)-1-indenyl]zirconium dichloride, A- Bis[2-[(1-propylcyclobutyl)methyl]-4-(4-methyl-phenyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1- Propylcyclopropyl)methyl]-4-(4-methyl-phenyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-methylcyclohexyl)methyl] 4-(3,5-Dimethyl-phenyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-methylcyclopentyl)methyl]-4-(3) ,5-dimethyl-phenyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-methylcycloheptyl)methyl]-4-(3,5-dimethyl -Phenyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-methylcyclononyl)methyl]-4-(3,5-dimethyl-phenyl) -1-mercapto]zirconium dichloride, A-bis[2-[(1-methylcyclooctyl) Methyl]-4-(3,5-dimethyl-phenyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-ethylcyclohexyl)methyl]- 4-(3,5-Dimethyl-phenyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-ethylcyclopentyl)methyl]-4-(3, 5-Dimethyl-phenyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-ethylcycloheptyl)methyl]-4-(3,5-dimethyl -Phenyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-ethylcyclononyl)methyl]-4-(3,5-dimethyl-phenyl)- 1-indenyl]zirconium dichloride, A-bis[2-[(1-ethylcyclooctyl)methyl]-4-(3,5-dimethyl-phenyl)-1-indenyl] Zirconium dichloride, A-bis[2-[(1-ethylcyclobutyl)methyl]-4-(3,5-dimethyl-phenyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-propylcyclohexyl)methyl]-4-(3,5-dimethyl-phenyl)-1-indenyl]zirconium dichloride, A-bis[2- [(1-propylcyclopentyl)methyl]-4-(3,5-dimethyl-phenyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-propyl) Cycloheptylheptyl)methyl]-4-(3,5-dimethyl-phenyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-propylcyclodecyl) Methyl]-4-(3,5-dimethyl-phenyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-propylcyclooctyl)methyl]-4 -(3,5-Dimethyl-phenyl)-1-indenyl]zirconium dichloride, A- [2-[(1-propylcyclobutyl)methyl]-4-(3,5-dimethyl-phenyl)-1-indenyl]zirconium dichloride, A-bis[2-[( 1-propylcyclopropyl)methyl]-4-(3,5-dimethyl-phenyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-methyl ring) Hexyl)methyl]-4-(4-trimethylformamidinyl-phenyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-methylcyclopentyl)methyl) ]-4-(4-trimethylformamido-phenyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-methylcycloheptyl)methyl]-4- (4-trimethylformamidinyl-phenyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-methylcyclodecyl)methyl]-4-(4-tri) Methylforminyl-phenyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-methylcyclooctyl)methyl]-4-(4-trimethylformane) -Phenyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-ethylcyclohexyl)methyl]-4-(4-trimethylformamidinyl-phenyl) -1-mercapto]zirconium dichloride, A-bis[2-[(1-ethylcyclopentyl)methyl]-4-(4-trimethylformamidinyl-phenyl)-1-pyrene Zirconium dichloride, A-bis[2-[(1-ethylcycloheptyl)methyl]-4-(4-trimethylformamidinyl-phenyl)-1-indenyl]dichloride Zirconium, A-bis[2-[(1-ethylcyclodecyl)methyl]-4-(4-trimethylformamidinyl-phenyl)-1- Mercapto]zirconium dichloride, A-bis[2-[(1-ethylcyclooctyl)methyl]-4-(4-trimethylformamidinyl-phenyl)-1-indenyl] Zirconium chloride, A-bis[2-[(1-ethylcyclobutyl)methyl]-4-(4-trimethylformamidinyl-phenyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-propylcyclohexyl)methyl]-4-(4-trimethylformamido-phenyl)-1-indenyl]zirconium dichloride, A-double [2 -[(1-propylcyclopentyl)methyl]-4-(4-trimethylformamidinyl-phenyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1 -propylcycloheptyl)methyl]-4-(4-trimethylformamidinyl-phenyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-propyl ring) Mercapto)methyl]-4-(4-trimethylformamidinyl-phenyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-propylcyclooctyl)- 4-(4-trimethylformamidinyl-phenyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-propylcyclobutyl)methyl]-4 -(4-trimethylformamidinyl-phenyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-propylcyclopropyl)methyl]-4-(4- Trimethylmethyl decyl-phenyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-methylcyclohexyl)methyl]-4-(4-ethyl-phenyl) )-1-indenyl]zirconium dichloride, A-bis[2-[(1-methylcyclopentyl)methyl]-4-(4- -Phenyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-methylcycloheptyl)methyl]-4-(4-ethyl-phenyl)-1- Mercapto]zirconium dichloride, A-bis[2-[(1-methylcyclodecyl)methyl]-4-(4-ethyl-phenyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-methylcyclooctyl)methyl]-4-(4-ethyl-phenyl)-1-indenyl]zirconium dichloride, A-bis[2-[( 1-ethylcyclohexyl)methyl]-4-(4-ethyl-phenyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-ethylcyclopentyl)) 4-(4-ethyl-phenyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-ethylcycloheptyl)methyl]-4-(4- Ethyl-phenyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-ethylcyclodecyl)methyl]-4-(4-ethyl-phenyl)-1 -fluorenyl]zirconium dichloride, A-bis[2-[(1-ethylcyclooctyl)methyl]-4-(4-ethyl-phenyl)-1-indenyl]zirconium dichloride , A-bis[2-[(1-ethylcyclobutyl)methyl]-4-(4-ethyl-phenyl)-1-indenyl]zirconium dichloride, A-bis[2-[ (1-propylcyclohexyl)methyl]-4-(4-ethyl-phenyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-propylcyclopentyl)) Methyl]-4-(4-ethyl-phenyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-propylcycloheptyl)methyl]-4-(4) -ethyl-phenyl)-1-indenyl]zirconium dichloride, A- [2-[(1-propylcyclodecyl)methyl]-4-(4-ethyl-phenyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-propyl) Cyclooctyl)methyl]-4-(4-ethyl-phenyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-propylcyclobutyl)methyl] 4-(4-ethyl-phenyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-propylcyclopropyl)methyl]-4-(4-ethyl -Phenyl)-1-indenyl]zirconium dichloride, A-bis[2-[(5-methyl-1,3-dioxan-5-yl)methyl]-4-( Tert-butylphenyl)-1-indenyl]zirconium dichloride, A-bis[2-[(5-ethyl-1,3-dioxan-5-yl)methyl]- 4-(T-butylphenyl)-1-indenyl]zirconium dichloride, A-bis[2-[(2,2,5-trimethyl,-1,3-dioxane) -5-yl)methyl]-4-(t-butylphenyl)-1-indenyl]zirconium dichloride, A-bis[2-[(2,2-dimethyl-5-ethyl) -1,3-dioxan-5-yl)methyl]-4-(t-butylphenyl)-1-indenyl]zirconium dichloride, A-bis[2-[(3) -methyloxoquinone (oxetan-3-yl)methyl]-4-(t-butylphenyl)-1-indenyl]zirconium dichloride, A-bis[2-[(3-ethyl) Oxa-3-yl)methyl]-4-(t-butylphenyl)-1-indenyl]zirconium dichloride, A-bis[2-[(1-methylcyclohex-3-ene) -1-yl)methyl]-4-(t-butylphenyl) -1-indenyl]zirconium dichloride, A-bis[2-[(1-ethylcyclohex-3-en-1-yl)methyl]-4-(t-butylphenyl)-1 - fluorenyl] zirconium dichloride.

A is dimethyldecanediyl, diethyldecanediyl, dipropyl Decanediyl, dibutyldecanediyl, dipentyldecanediyl, dihexyldecanediyl, diheptyldecanediyl, dioctyldecanediyl, dinonyldecanediyl, dinonyldecane , undecyldecanediyl, bis-dodecyldecyl, dimethyldecanediyl, diethyl decyl, dipropyldecanediyl, dibutyldecanediyl, dipentane Alkanediyldiyl, dihexyldecanediyl, diheptyldecanediyl, dioctyldecanediyl, dinonyldecanediyl, dinonyldecanediyl, bis-decyl Alkyldiyl or bis-dodecyldiyldiyl, hexyl(methyl)decanediyl, ethyl(methyl)decanediyl, ethyl(methyl)decanediyl, propyl(methyl) Decanediyl, 3,3,3-trifluoropropyl(methyl)decanediyl, propyl(ethyl)decanediyl, butyl(methyl)decanediyl, butyl(ethyl)decane Base, butyl (propyl) decanediyl, pentyl (methyl) decanediyl, pentyl (ethyl) decanediyl, pentyl (propyl) decanediyl, pentyl (butyl) decane Base, hexyl (methyl) decanediyl, hexyl (ethyl) decane diyl or hexyl (propyl) decane , hexyl (butyl)decanediyl or hexyl(pentyl)decanediyl, the explanation for the list of bridging elements A is as follows: the nomenclature of a substituent on the bridging atom is also meant to include all structural isomers. Just as it is clearly named. For example, dibutylnonanediyl includes both bis(n-butyl)decanediyl, di(t-butyl)decanediyl, di(t-butyl)decanediyl, or a mixture of these structural isomers. . Similarly, the nomenclature of the amyl decanediyl group also includes, for example, the hexa(cyclopentyl)decanediyl or the hexyl (meth)decanediyl group also includes, for example, a cyclohexyl(methyl)decanediyl group.

Supported metallocene complex and polymerization method

The metallocene complexes comprising the recovered and recycled ligands prepared according to the embodiments disclosed herein can be used to produce at least one A metallocene complex, at least one cocatalyst, and a catalyst system that may optionally employ one of the carriers. The catalyst system can be used in the polymerization of olefins. A variety of different processes for the manufacture of supported catalysts and the use of such catalyst systems for the polymerization of olefins are known, in addition to many of the other patents described above, such as, for example, WO 94/28034, WO 94/14856, WO. 98/01481, WO 00/05277, WO 09/054832, and WO 10/077230, and U.S. Patent Nos. 7,285, 608, 7, 232, 869, 7, 169, 864, incorporated herein by reference.

Instance General principle

The manufacture and processing of such organometallic compounds is carried out in a dry nitrogen atmosphere using Schlenk technology or in a hand-held work box. All solvents were washed with nitrogen and dried on molecular sieves prior to use.

The characteristics of organic and organometallic compounds are represented by 1H-NMR spectroscopy and gas chromatography. Since the mixture of isomers is present in the recycled ligands, the 1 H-NMR spectrum of the ligands shows many overlapping signals from different species and complicates the detailed interpretation of the spectra. Therefore, gas chromatography was used for the work for confirming and determining the purity of each of the compounds. For the confirmation of the compound, a sample of each of the pure ligands was used.

The gas chromatograph used was an Agilent 7890A with an autosampler and a J & W HP-5 or as an alternative to the J & W DB-1ht column.

The characteristics of the produced polymer are represented by DSC and MFR analysis.

Use the following abbreviation: GC = gas chromatography.

MFR = melt flow rate measured at 230 ° C using 2.16 kg load (ISO 1133).

Tm = polymer melting point (° C.) measured by differential scanning calorimetry (DSC, ISO 3146) using a first heating/cooling/second heating rate of 20 ° C/min.

Example A: Free recovery from dimethyl decanediyl-bis(2-((1-methylcyclohexyl)methyl)-4-(4'-t-butylphenyl)indenyl)zirconium dichloride Coordinator

In a 3-neck bottom flask equipped with a reflux condenser, a dropping funnel and a thermometer, 14.57 g of the metallocene dimethyl decanediyl-bis-(2-((1-methylcyclohexyl)) was mixed with 145 ml of toluene. Methyl)-4-(4'-t-butylphenyl)-indenyl)zirconium dichloride and 14.6 ml of ethanol was added. The resulting suspension was warmed to 78 ° C by an oil bath. As the temperature rises, a clear bridge red solution gradually forms. Stirring was continued for 2 hours at 78 °C. During this stirring, the deep orange-red solution of the solution gradually became almost colorless. The latter indicates that the decomposition of the complex has been completed. For the purposes of this test, 365 grams of ethanol was added to the mixture via the dropping funnel and the ethanol/toluene azeotrope was distilled off (theoretical composition: 68% ethanol, 32% toluene, boiling temperature 76.7 ° C). After removing 319 grams of azeotrope, another 365 grams of ethanol was added and distillation continued until about 200 milliliters of total volume remained in the reaction flask. 365 grams of methanol was added to the reaction mixture with stirring, and the stirring rate was maintained to maintain micro-boiling under reflux of the mixture. The resulting mixture has a slightly turbid appearance and is stirred for about 5 to 10 minutes at a final temperature (about 64.7 ° C = boiling point of methanol). After that, abort The stirrer was allowed to cool to room temperature. A colorless precipitate formed which was then filtered, washed with a small portion of methanol and dried in vacuo at 60 °C.

9.28 grams of a ligand in the form of a mixture of isomers with a purity of at least 94% was recovered. This yield is equivalent to 76.6% of the theoretical maximum recoverable amount. According to the GC data, the mother liquor contains other ligands which can be recovered, at least in part, by cooling the mother liquor to -20 ° C at night and then filtering the precipitate.

Example B: Recovery of free ligands from cyclohexyl(methyl)decanediylbis(2-methyl-4-(4'-t-butyl-phenyl)indenyl)zirconium dichloride

10.0 g of metallocene cyclohexyl(methyl)decanediylbis(2-methyl-4-(4'-t-butylphenyl)indenyl)zirconium dichloride was dissolved in 100 ml of dichloromethane and 100 ml of 10% aqueous HCl and 10 ml of ethanol were added. The resulting biphasic mixture was stirred at room temperature and took a night. In the meantime, the deep orange color of the organic phase gradually turns bright yellow. The aqueous phase remains colorless. No precipitate was seen in the two phases. The two phases were separated and the aqueous phase was extracted with 20 mL of dichloromethane. The combined organic phases were dried over magnesium sulfate and the solvent was removed in vacuo.

Yield: 6.90 g (86.1% of the maximum recoverable amount) of crude cyclohexyl (methyl)nonanediyl bis(2-methyl-4-(4'-tert-butyl-benzene) as a mixture of isomers Base) 茚). The crude product had a purity of >85% (determined by GC) according to GC analysis. The crude product can be recrystallized from a hot alcohol such as ethanol or isopropanol and a ligand with a purity >95% (determined by GC) can be obtained.

Example C: Recovery of free ligands from dimethyl decanediyl-bis-(2-methyl-4,5-benzofluorenyl) zirconium dichloride

13.4 grams of metallocene dimethyl decane diyl-bis-(2-methyl -4,5-Benzinofluorenyl)zirconium dichloride, 135 ml of toluene, and 13.5 ml of ethanol were placed in a 3-neck round bottom flask equipped with a reflux condenser, a dropping funnel and a thermometer. The resulting suspension was allowed to warm to an internal temperature of 90 ° C and maintained at this temperature, which took an hour. The mixture is stirred at elevated temperature and after a period of time, a clear orange solution is formed. Thereafter, 13.4 ml of ethanol was added to the reaction mixture, and the internal temperature was lowered to 80 ° C and stirring was continued for further 3 hours. In the meantime, the color of the reaction mixture gradually changed from the initial bright orange color to a deep red color. After cooling to room temperature, the organic phase was washed twice with 150 mL of 10% HCl and once with 150 mL of demineralized water. The organic phase of the corresponding free ligand containing > 85% purity (based on GC, without solvent considerations) was isolated and dried over magnesium sulfate and the solvent was removed in vacuo. The resulting oily residue still contained a small amount of toluene and then dissolved in 20 ml of hot ethanol until a clear reddish solution was formed, and the mixture was crystallized at -18 ° C for 60 hours. After filtration, the filter cake was washed twice with a small portion of cold methanol and then dried under vacuum at elevated temperature.

Recovery of 3.06 g (31.7% of the maximum recoverable amount) of dimethyl decanediyl-bis-(2-methyl-4,5-benzene in the form of a mixture of isomers with a purity of 91% (determined by GC) And 茚). More of the ligand can be obtained by a series of concentration and cooling of the mother liquor or by replacing the mother liquor with another alcohol such as methanol or ethanol.

Example D: Recovery from dimethyl decanediyl-bis-(2-(cyclohexylmethyl)-4-(4'-tris-butylphenyl)-1-indenyl)zirconium dichloride Coordinator

Making 11.0 g of metallocene dimethyl decanediyl-bis-(2-(cyclohexyl) Methyl)-4-(4'-t-butylphenyl)-1-indenyl)zirconium dichloride was dissolved in 100 ml of dichloromethane and 100 ml of 10% aqueous HCl and 1 ml of ethanol were added. The resulting mixture was stirred at room temperature and took a night. In the meantime, the deep orange color of the organic phase gradually turned bright yellow. The aqueous phase remains colorless. No precipitate was seen in the two phases. Each phase was separated and the organic phase was extracted with a small amount of dichloromethane. The organic phases of the combined bodies were dried over magnesium sulfate and the solvent was removed in vacuo.

Yield: 7.70 g (85% of the maximum recoverable amount) of crude dimethylnonanediyl-bis-(2-(cyclohexylmethyl)-4-(4'-third) as a mixture of isomers -butylphenyl)-1-indole) and its purity >90% (determined by GC). The crude product can be recrystallized from a hot alcohol such as ethanol or isopropanol and the ligand having a purity of >95% (determined by GC) can be obtained.

Synthesis of metallocene complexes Example E: Dimethyldecanediyl-bis-(2-((1-methylcyclohexyl)methyl)-4-(4'-tris-butylphenyl)-indenyl)zirconium dichloride Synthesis method

Add 5.6 g (6.4) millimolar of 50 ml of anhydrous diethyl ether to a 100 ml round bottom flask, 1:1 mixture of the second ring and the new ligand) bis[4-(4-t-butylbenzene) Base]]-2-[(1-methyl-cyclohexyl)methyl]-1H-indol-1-yl]-dimethyldecane. The initial suspension was converted to a clear orange solution about 20 minutes after the addition of 5.3 ml of n-butyllithium (2.5 M in toluene, 2.05 equivalents) at room temperature. The mixture was stirred at this temperature for a night and then cooled to 0 °C. After adding 1.51 g (1 equivalent) of zirconium tetrachloride and warming to room temperature, stirring was continued for 5 hours. The crude reaction mixture was filtered on a pad of EtOAc (EtOAc). The filter cake was extracted once with 16 ml of hot toluene, once with 10 ml of hot toluene, once with 8 ml of hot toluene and once with 6 ml of hot toluene. From the filtrate, 1.50 g of the metallocene having a racemic/mesotropy ratio of 5:1 was obtained. For further r/m enrichment, the product was recrystallized from toluene. ¹ H-NMR (500 MHz, CDCl ₃ , ppm): δ = 7.61 (m, 2 H, aromatic), 7.53 (m, 4H, aromatic), 7.40 (m, 2+4H, aromatic), 7.33 (m, 2H, aromatic), 7.05 (m, 2H, aromatic), 6.91 (s, 2H, decyl-H), 2.65 and 2.23 (2 × "d", 2 × 2H, decyl-C H ₂ ), 1.48-1.08 (multiple m's, 20 H, ring), 1.35 (s, 6H, C H _3Si ), 1.32 (s, 18H, C(C H ₃ ) ₃ ), 0.75 (s, 6H, C H ₃ ).

Example F: Synthesis of cyclohexyl (methyl)decanediylbis(2-methyl-4-(4'-t-butyl-phenyl)indenyl)zirconium dichloride

10.0 g (15.3 mmol) of cyclohexyl(methyl)decanediylbis(2-methyl-4-(4'-t-butylphenyl)indole) was introduced into 100 ml of diethyl ether and placed in a chamber. 12.3 ml of n-butyllithium solution (2.5 M in toluene) was added under temperature. After the addition was completed, the mixture was stirred at this temperature for a night. It was allowed to cool to 0 ° C and then 3.59 g (15.3 mmol) of zirconium tetrachloride was added portion by portion. The solution was stirred at room temperature for 2 hours. The precipitate formed was separated by filtration through a G3 sintered glass filter and washed twice with 10 ml of diethyl ether. The residue containing the desired product and LiCl is then dried in a vacuum taken from the oil pump. The crude product was taken up in dichloromethane, filtered and then the solvent was removed to yield 6.65 g of the metalloc. ¹ H-NMR (400 MHz, CDCl ₃ , ppm): 7.40-6.97 (m, 16H, aromatic-H), 2.22 (s, 6H, CH ₃ ), 2.19-1.46 (m, 11H, aliphatic-H ), 1.32 (s, 18H, tert-butyl), 1.27 (s, 3H, CH ₃ ).

Example G: Synthesis of dimethyl decanediyl-bis-(2-methyl-4,5-benzofluorenyl) zirconium dichloride

Dispose of 7.0 g (16.8 mmol, 1:1 mixture of recycled and new ligand) dimethyl bis (2-methyl-4,5) in 13.5 mL of n-butyllithium solution (2.5 M in toluene) A solution of -benzo-indenyl)decane in 70 ml of tetrahydrofuran was stirred at room temperature for 16 hours. The reaction solution was cooled to 0 ° C and 3.92 g (16.8 mmol) of zirconium tetrachloride was added portion by portion. After the addition was completed, the solution was allowed to warm to room temperature and stirred at this temperature for 2 hours. The precipitate formed was filtered through a G3 sintered glass filter and the residue was washed once with 12 ml of diethyl ether. The residue was then dried under vacuum and 5.6 g of the desired product was obtained which had a racemic: meso ratio of about 1:1. It is necessary to separate the isomers in the next step to obtain a selective catalyst for the polymerization of propylene. ¹ H-NMR (400 MHz, CDCl ₃ , ppm): 7.85-7.10 (m, 14H, A-H), 2.25 (s, 6H, CH ₃ ), 1.30 (s, 6 H, CH ₃ ).

Example H: Synthesis of dimethyl decanediyl-bis-(2-cyclohexylmethyl)-4-(4'-t-butylphenyl)-1-indenyl)zirconium dichloride

10.0 g (13.4 mmol) of dimethylbis-(2-(cyclohexylmethyl)-4-(4'-tert-butylphenyl)-1-indenyl) decane was dissolved in 100 ml of diethyl ether. in. 10.8 ml of n-butyllithium (2.5 M in toluene) was added at room temperature, and the mixture was stirred at room temperature overnight. Then 3.13 grams (13.4 millimoles) of zirconium tetrachloride was added in one portion. The orange suspension was stirred at room temperature for 5 hours and the solid was isolated by filtration. It was washed with 2 portions of 15 ml portions of diethyl ether and dried in vacuo to give a crude compound that was still containing lithium chloride (racemic/meso = 1.5:1). The racemic complex was isolated by fractional crystallization from toluene. Yield: 4.1 g (33%) in the form of a bright yellow powder. ¹ H-NMR (400 MHz, CDCl ₃ ): δ = 7.61 (d, 2H, aromatic), 7.57, 7.44 (2×d, 8H, aromatic), 7.36 (d, 2H, aromatic), 7.22, 7.15, 7.07 (3 × m, 10H, aromatic + plus benzene), 6.94 (s, 2H, decyl-H), 2.64 ("dd", 2H, fluorenyl-C H ₂ ), 2.34 (s, toluene) ), 2.13 ("dd", 2H, thiol-C H ₂ ), 1.75-1.45 (m, 10H, aliphatic), 1.33 (s, 18H, C(C H ₃ ) ₃ ), 1.31 (s, 6H) , Si(C H ₃ ) ₂ ), 1.12-0.76 (m, 12H, aliphatic) ppm.

Example Ia: Method for preparing cerium oxide treated by methylaluminoxane

Slowly add 76 ml of a 30% by weight solution of methylaluminoxane in toluene (Albemarle Corporation) to 30.0 g of cerium oxide (Grace XPO2107, dried at 180 ° C and 1 mbar for 16 hours at room temperature, LOD < 0.5 weight % and LOI = 2.6% by weight) in a stirred suspension in 150 ml of toluene. During this addition, the temperature must not exceed 30 °C. After the addition was completed, the mixture was stirred at room temperature for half an hour, then heated and allowed to reflux for 4 hours. After cooling to room temperature, the solvent was separated by filtration. The residue was washed with 2 portions each of 150 ml of toluene and 3 portions of 150 ml of hexanes and dried in vacuo to constant weight. The methyl aluminoxane-treated cerium oxide in the form of a free-flowing powder was obtained in a yield of 48.8 g.

Example Ib: Method for preparing cerium oxide treated by methylaluminoxane

31 ml of a 30% by weight solution of methylaluminoxane in benzene (Albemarle Corporation) to 30 g of cerium oxide (Grace XPO2107, dried at 180 ° C and 1 mbar for 16 hours, LOD < 0.5) was slowly added at room temperature. Stirring suspension in 154 ml of toluene with % by weight and LOI = 2.6% by weight) Inside. During this addition, the temperature must not exceed 30 °C. After the addition was completed, the mixture was stirred at room temperature for 2 hours and separated by filtration. The residue was washed with 2 portions each of 154 ml of toluene and 3 portions of 154 ml of hexanes and dried in vacuo to constant weight. The methylmagnesium oxide treated cerium oxide in the form of a free flowing powder was obtained in a yield of 42 grams.

Example J: One with racemic dimethylnonanediyl-bis-(2-((1-methylcyclohexyl)methyl)-4-(4'-tri-butylphenyl)-fluorenyl) Method for preparing zirconium dichloride supported metallocene catalyst

10.0 g of the methylaluminoxane-treated cerium oxide prepared in Example Ib was placed in a sintered glass to serve as a column having a smooth surface. A very small amount of toluene was added and the treated cerium oxide was carefully stirred through a spatula to remove any air pockets within the column. Excess toluene was removed by filtration to leave a smooth surface. In a separate flask, 336 mg of rac-dimethyl decanediyl-bis-(2-((1-methylcyclohexyl)methyl)-4-(4'-tert-butylbenzene) The zirconium dichloride (manufactured in Example E) was mixed with 27 ml of toluene and 13.6 ml of a 30% by weight solution of methylaluminoxane in toluene (Albemarle Corporation). The slurry was stirred at room temperature and took an hour to obtain an orange solution. This solution was then carefully added to the top of the methylaluminoxane-treated cerium oxide and slowly filtered off over about 30 minutes. When the surface of the coloring solution reaches the top of the cerium oxide, the filtration method is aborted and the filter cake is carefully and thoroughly stirred via a spatula. The catalyst was then allowed to stand for one hour. The residual solvent was filtered off and the catalyst was washed twice with iso-hexane (20 mL) and dried to dryness. The catalyst was obtained in the form of a free flowing orange powder in a yield of 11.6 g.

Example K: A supported metallocene having a racemic-cyclohexyl(methyl)decanediylbis(2-methyl-4-(4'-t-butylphenyl)indenyl)zirconium dichloride Catalyst preparation method

10.0 g of the methylaluminoxane-treated cerium oxide prepared in Example Ia was placed in a sintered glass filter to serve as a column having a smooth surface. In a separate flask, 252 mg of racemic cyclohexyl(methyl)decanediylbis(2-methyl-4-(4'-tert-butyl-phenyl)indenyl)zirconium dichloride (Prepared in Example F) was mixed with 25.2 ml of methane, and 2.9 ml of a 30% by weight solution of methylaluminoxane in toluene (Albemarle Corporation). The slurry was stirred at room temperature and took one hour to obtain a dark colored solution. This solution was carefully added on top of the methylaluminoxane-treated cerium dichloride and slowly filtered off over about 30 minutes. When the surface of the coloring solution reaches the top of the cerium oxide, the filtration method is terminated and the filter cake is carefully and thoroughly stirred via a spatula. The catalyst was then allowed to stand for one hour. The residual solvent was filtered off and the catalyst was dried to constant weight in a stream of nitrogen. The catalyst was obtained in the form of a free-flowing powder in a yield of 11.4 g.

Example L: Process for the preparation of a supported metallocene catalyst having racemic dimethylnonanediyl-bis-(2-methyl-4,5-benzofluorenyl)zirconium dichloride

10.0 of the methyloxoxane-treated cerium oxide prepared in Example Ia was placed in a sintered glass filter to serve as a column having a smooth surface. In a separate flask, 179 mg of rac-dimethyl decanediylbis(2-methyl-4,5-benzoindolyl)zirconium dichloride (made in Example G) and 25 Methanol toluene, and 2.8 ml of methylaluminoxane in a 30% by weight solution in toluene (Albemarle Corporation) were mixed. Stirring the slurry at room temperature, time consuming One hour to get a deep red solution. This solution was then carefully added to the top of the methylaluminoxane-treated cerium oxide and slowly filtered off over about 30 minutes. When the surface of the coloring solution reaches the top of the ceria, the filtration method is stopped and the filter cake is carefully and thoroughly stirred via a spatula. The catalyst was then allowed to stand for one hour. The residual solvent was filtered off and the catalyst was dried to constant weight in a nitrogen wash. The catalyst was obtained in the form of a free-flowing powder in a yield of 9.6 g.

Example M: One having racemic-dimethyldecanediyl-bis-(2-(cyclohexylmethyl)-4-(4'-tri-butylphenyl)indenyl)zirconium dichloride Process for carrying metallocene catalyst

10.0 g of the methylaluminoxane-treated cerium oxide prepared in Example Ib was placed in a sintered glass to serve as a column having a smooth surface. A very small amount of toluene was added and the treated cerium oxide was carefully stirred through a spatula to remove any air pockets within the column. Excess toluene was removed by filtration to leave a smooth surface. In a separate flask, 326 mg of rac-dimethyldecanediyl-bis-(2-(cyclohexylmethyl)-4-(4'-tert-butylphenyl)-1-pyrene Zirconium dichloride (made in Example H) was mixed with 27 ml of toluene and 13.6 ml of a 30% by weight solution of methylaluminoxane in toluene (Albemarle Corporation). The slurry was stirred at room temperature and took an hour to obtain an orange solution. This solution was then carefully added to the top of the methylaluminoxane-treated cerium oxide and slowly filtered off over about 30 minutes. When the surface of the coloring solution reaches the top of the cerium oxide, the filtration method is aborted and the filter cake is carefully and thoroughly stirred via a spatula. The catalyst was then allowed to stand for one hour. The residual solvent is filtered off and the catalyst is subjected to dissimilar The alkane (20 mL) was washed twice and dried to constant weight in a nitrogen wash. The catalyst was obtained in the form of a free flowing reddish powder in a yield of 12.0 g.

Comparative Example N:

A catalyst was prepared according to the procedure of Example J. According to example E The procedure used is to use only the non-recycled ligand to produce the metallocene racemic-dimethyldecanediyl-bis-(2-((1-methylcyclohexyl)methyl)-4-() 4'-Butylphenyl)-fluorenyl) zirconium dichloride.

Comparative Example O:

A catalyst was prepared according to the procedure of Example K. According to the procedure given in Example F, only the non-recycled ligand was used to make the metallocene racemic-cyclohexyl(methyl)nonanediyl bis(2-methyl-4-(4'-) Ternyl butyl phenyl) fluorenyl) zirconium dichloride.

Comparative Example P:

A catalyst was prepared according to the procedure of Example L. According to the procedure given in Example G, the metallocene racemic-dimethyldecanediyl-bis-(2-methyl-4,5-benzopyrene) was prepared using only the non-recycled ligand. Base) zirconium dichloride.

Comparative Example Q:

A catalyst was prepared according to the procedure of Example M. According to the procedure given in Example H, only the non-recycled ligand was used to make the metallocene racemic-dimethyldecanediyl-bis-(2-(cyclohexylmethyl)-4-(). 4'-Tertiary butylphenyl)indenyl)zirconium dichloride.

Experimental polymerization

Using the catalyst prepared in Example JQ, the test polymerization was carried out according to the following procedure: 100 g of a metallocene polymer seed bed, 1 cm ³ of triisobutylaluminum (10 wt% solution in heptane, if necessary) ), 24.3 mmol of hydrogen and 1500 cm ³ of liquid propylene are charged into a coil 5 provided within an autoclave decimeter of washing of a stirrer and a nitrogen dry scrubber ^3. The mixture was stirred at 20 ° C for at least 5 minutes (mixer speed 200 rpm). Then about 40-70 mg of metallocene catalysts has been carried in suspension by the white oil of 5 cm ³ and 1500 cm ³ of liquid propylene of injection. The reactor was heated to an internal temperature of 65 ° C in 11 minutes. The polymerization was carried out at 65 ° C and took 60 minutes. The polymerization was terminated by releasing the monomer and cooling the reactor. The polymer is discharged and dried.

Results: The results of these polymerizations are summarized in Table 1. According to the results obtained, the catalyst productivity of a catalyst prepared using a specific metallocene synthesized from a mixture of new and recycled ligands and a corresponding metallocene synthesized using only a new ligand is The properties of the polymers are virtually identical.

The test results obtained by the polymerizations prove that at least at least Part of the catalyst made from the metallocene complex synthesized from the recycled ligand material does not differ from the catalyst obtained from the metallocene made only from the new ligand. The small differences in activity and polymer properties in the above table are within the range of frequent experimental errors.

As noted above, the methods disclosed herein can be used to efficiently and economically recover a ligand from a metallocene complex. The method of decomposing the metallocene complex using a protic compound to form a reaction product containing a free ligand can advantageously improve the production of the free ligand from the metallocene complex via decomposition under mild conditions. Yield. The methods disclosed herein may additionally or additionally include one or more of the following advantages: by each ligand, the yield of the desired metallocene complex or metallocene catalyst may be increased; the economy of the metallocene manufacture may be improved And/or can produce economically enforceable properties of metallocenes that are typically not manufacturable due to excessive loss of the ligand.

For example, in prior methods, 50% or more of the total metallocene yield was typically lost due to the separation and disposal of undesired non-image isomers. Moreover, most of the cost of making such metallocene complexes is believed to be due to the synthesis of such ligands used during the synthesis of the metal complex. According to the embodiments disclosed herein, the recovery and reuse of the ligand can thereby reduce the cost of the coordination of the ligand, and can reduce the amount of material disposed (eg, reduced coordination of the ligand), thereby significantly improving the metallocene. The economics of the synthesis method. The method disclosed herein provides an efficient way to regenerate a portion of the raw materials used in the manufacture of metallocenes, and can be recycled in large quantities. The ligand is lost due to the formation of the multi-metallocene non-image isomer.

While the disclosure includes a limited number of embodiments, those skilled in the art will appreciate that the embodiments of the present invention can be devised without departing from the scope of the disclosure. Therefore, the scope should be limited only by the scope of the additional patent application.

2‧‧‧metallocene complexes containing a ligand

4‧‧‧Protonic composition

6‧‧‧ decomposition stage

8‧‧‧Reaction products containing free ligands and inorganic decomposition products

10‧‧‧Separation/recycling phase

12‧‧‧Free seat

14‧‧‧Inorganic decomposition products

Claims (15)

A method for recovering a ligand from a metallocene complex, the method comprising: contacting a metallocene complex containing a ligand with a protonic composition under the reaction conditions to decompose the zeolite The metal complex forms a reaction product containing a free ligand and an inorganic decomposition product; the free ligand is recovered from the reaction product. The method of claim 1, further comprising feeding at least a portion of the recovered free ligand to a meso form for producing the metallocene complex and the metallocene is mismatched The method of the racemic form of an ansa-metallocene complex in a racemic form. The method of claim 2, further comprising separating the basket-type metallocene complex to recover a fraction containing the meso form of the metallocene complex, and a metallocene-containing complex. Fractions in racemic form. The method of claim 3, further comprising at least one of: carrying the racemic form of the metallocene; activating the racemic form of the metallocene; and using the racemic form of the metallocene Feeded into a polymerization process. The method of claim 3, further comprising feeding at least a portion of the fraction containing the meso form of the metallocene complex to the contacting step. A method for making a metallocene catalyst, the method comprising: Synthesis of a basket-type metallocene complex comprising a mixture of the racemic form of the metallocene complex and the meso form of the metallocene complex, the synthetic step comprising reacting a ligand with a metal compound Reaction; separating the basket-type metallocene complex to recover a fraction containing the meso form of the metallocene complex, and a fraction containing the racemic form of the metallocene complex; under reaction conditions Using a protonic composition to contact at least a portion of the fraction containing the meso form of the metallocene complex to contact the metallocene complex and form a reaction containing free ligands and inorganic decomposition products a product; recovering the free ligand from the reaction product; and recycling at least a portion of the recovered free ligand to the synthesis step. The method of claim 6, further comprising forming a metallocene catalyst system comprising one or more of the following steps: supporting the racemic form of the metallocene complex; and activating the metallocene complex Racemic form; contact with the metallocene complex in a racemic form with a cocatalyst. The method of claim 6 or 7, further comprising purifying the recovered free ligand before recycling to the synthesizing step. The method of any one of claims 1 to 8, wherein the protic composition comprises a protic substance comprising one of: water, mineral acid, organic acid, alcohol, or At least one ammonium salt of a hydrogen atom combined with nitrogen, a sulfonic acid, a sulfinic acid, a mercaptan, an organic acid of an oxo acid A combination of organisms, phosphorus, and the like. The method of any one of claims 1 to 9, wherein the protic composition is an in-phase mixture containing one or more protic substances, or one or more protic substances and one or more aprotic substances In-phase mixture. The method of any one of claims 1 to 9, wherein the protic composition is a multiphase system comprising one or more protic substances and one or more aprotic materials. The method of claim 10, wherein the aprotic substance comprises at least one of toluene, dichloromethane, a linear hydrocarbon, a branched chain hydrocarbon, and the like. The method of any one of claims 1 to 12, wherein the decomposition reaction conditions comprise a temperature in the range from 50 ° C to 100 ° C. The method of any one of claims 1 to 13, wherein the protic composition comprises a) an aprotic substance suitable for dissolving the metallocene complex, and b) one or more alcohols Protonic substance. The method of claim 14, wherein the decomposition reaction is carried out at a boiling point of the mixture under reflux.