MXPA03009477A - Olefin polymerization catalyst. - Google Patents

Abstract

An olefin polymerization catalyst component is prepared by making a solution of a transition metal complex of a selected tridentate ligand, adsorbing the complex onto a silica or silica-alumina support, and separating the solution from the supported transition metal complex component, which is storage stable. Olefin polymerizations with this component may be carried out with high catalyst productivity using cocatalysts such as trialkylaluminum compounds.

Description

OLEFINES POLYMERIZATION CATALYST Field of the Invention The present invention relates to an olefin polymerization catalyst which contains a transition metal complex of a selected trident ligand, a method for preparing such catalyst and an olefin polymerization process for using such a catalyst. BACKGROUND OF THE INVENTION Polyolefins are important elements for commerce and many such polymers are prepared using a transition metal complex as part of the polymerization catalyst system. Currently, there is much interest in catalysts containing late transition metals, such as Fe, Co, Ni and Pd. A particular type of olefin polymerization catalyst contains what is considered to be a tridentate ligand, which is 2,6-pyridinedicarboxaldehydebisimine or 2,6-diacylpyridine-bisimine or a minor variation thereof, generally as an iron complex or cobalt. Such complexes and their use as olefin polymerization catalysts, especially ethylene polymerization catalysts, are described in US Patents 5,955,555, WO 9 912 981, WO 9 946 302, WO 9 946 303, WO 9 946 304, WO 0 015 646, WO 0 024 788, WO 0 032 641, WO 0 050 470, WO 0 069 869 and WO 0 069 923, Ref .: 149944 which, all have been incorporated herein by reference for all purposes, as if they were fully described. Variations of these complexes have also found use as "polymerization" catalysts for the dimerization and oligomerization of ethylene and other alpha-olefins, to produce internal alpha-olefins and olefins. See, for example, US 6 063 881, US 6 103 946, WO 0 055 216 and WO 0 073 249, all of which have also been incorporated herein by reference for all purposes, as if they were fully described. As regards all olefin polymerization catalysts, an important consideration is the total cost of the polymerization catalyst system per unit weight of polyolefin produced. Another important consideration is the shape of the polymer product obtained, that is, if it is obtained in an easy to use form such as relatively non-pulverized particles which flow well and preferably have a relatively high bulk density and if the reactor is clogged. polymerization. Sometimes the main cost of the polymerization catalyst is not in itself the cost of the transition metal complex, but rather the cost of catalyst preparation and / or the costs of other ingredients needed for the catalyst system. In the end it is particularly real for many so-called simple site catalysts such as metallocenes and many of the final transition metal containing catalysts where aluminoxanes, especially methylaluminoxane, have been found to provide superior results but are very expensive compared with other alkylaluminum compounds, thereby increasing the total cost of the catalyst system per unit weight of the polyolefin produced. This has generally been true with transition metal complexes of a 2,6-pyridinedicarboxaldehyde-bisimine or a 2,6-diacylpyridinebisimine, as described in the aforementioned incorporated references. Some exceptions have been noted, for example modifying the surface of a support for a supported catalyst, see for example WO 0 020 467, which is incorporated herein by reference for all purposes, as if they were fully described. Although the modified support described in this publication allows the use of alkylaluminum compounds other than aluminoxanes to achieve good polymerization results, the modification of the support itself adds significantly to the total cost of the polymerization catalyst · per unit weight of the polyolefin produced Summary of the Invention The present invention relates to a process for the preparation of a supported polymerization catalyst component, comprising the steps of: (a) dissolving a transition metal complex from a 2,6-pyridinedicarboxaldeh dobisimine or a 2,6-diacylpyridine-bisimine in a solvent to form a solution; (b) contacting said solution with a support which is an unmodified silica or a silica-alumina for a sufficient amount of time to allow at least part of the metal complex to be adsorbed on the support and (c) optionally separate the solution and the solvent of the support; with the proviso that substantially no activator is present during stages (a), (b) and (c). A catalyst obtainable or obtained by the above process is also included in this invention. The present invention further includes a process for the polymerization of one or more polymerizable defines comprising the steps of: (a) dissolving a transition metal complex of a 2,6-pyridinedicarboxaldehydebisimine or a 2,6-diacylpyridine-bisimine in a organic solvent to form a solution; (b) contacting said solution with a support, which is unmodified silica or. silica-alumina, for a sufficient amount of time to allow at least part of the metal complex to be adsorbed on the support and thereby form a supported catalyst component; (c) 'optionally separating said solution and solvent from said supported catalyst component; and (d) contacting, under polymerization conditions, said supported catalyst component with one or more polymerizable olefins and one or more activators, with the proviso that practically no activator is present during steps (a), (b) and (c). These and other aspects and advantages of the present invention will be more readily understood by those of ordinary skill in the art upon reading the following detailed description. It will be appreciated that certain aspects of the invention, which, for clarity, are described below in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various aspects of the invention which are, for brevity, described in the context of a single embodiment may also be provided separately or in any sub-combination. DETAILED DESCRIPTION OF THE PREFERRED MODALITIES Certain terms have been used in the present application. Some of them are: A "hydrocarbyl group" is a univalent group that contains only carbon and hydrogen. As examples of hydrocarbyls, unsubstituted alkyls, cycloalkyls and aryls may be mentioned. If not stated otherwise, it is preferred here that the hydrocarbyl groups contain from 1 to about 30 carbon atoms. By "substituted hydrocarbyl" is meant a hydrocarbyl group containing one or more (types of) substituents that do not substantially interfere with the operation of the polymerization catalyst system. Suitable substituents in some polymerizations may include some or all of halo, ester, keto (oxo), amino, imino, carboxyl, phosphite, phosphonite, phosphine, phosphinite, thioether, amide, nitrile and ether. Preferred substituents when present are halo, ester, amino, imino, carboxyl, phosphite, phosphonite, phosphine, phosphinite, thioether and amide. Which substituents are useful in polymerizations which may in some cases be determined by reference to previously incorporated publications. (for example US 5 955 555), as well as US 5 880 241 which is also incorporated herein by reference for all purposes as if they were fully described. If not stated otherwise, it is preferred that the hydrocarbyl groups contain from 1 to about 30 carbon atoms. Included in the meaning of "substituted" are chains or rings containing one or more heteroatoms, such as nitrogen, oxygen and / or sulfur and the free valency of the substituted hydrocarbyl can be for the heteroatom. In a substituted hydrocarbyl, all hydrogens may be substituted, as in trifluoromethyl.

By "functional group (inert)" is meant a different group of hydrocarbyl or substituted hydrocarbyl which is different from that which participates in the "adsorption" (defined below) of the complex in the support, inert under the process conditions at which the compound containing the group is subjected to. The functional group also does not substantially interfere with any process described herein such that the compound in which they are present may participate in it. Examples of functional groups include halo (fluorine, chlorine, bromine and iodine) and ether such as -OR30 wherein R30 is hydrocarbyl or substituted hydrocarbyl. In cases in which the functional group may be close to a transition metal atom (such as an iron atom), the functional group must not coordinate the transition metal atom more strongly than the groups in those compounds shown as coordinators of the transition metal atom that is, they should not displace the desired coordination groups. "Alkyl group" and the "substituted alkyl group" have their customary meaning (see above substituted hydrocarbyl substituted). Unless indicated otherwise, alkyl groups and substituted alkyl groups preferably have from 1 to about 30 carbon atoms.

By "aryl" is meant a monovalent aromatic group in which the free valence is for the carbon atom of an aromatic ring. An aryl may have one or more aromatic rings that may be fused, connected by single bonds or other groups. By "substituted aryl" refers to a substituted monovalent aromatic group as set forth in the above definition of "substituted hydrocarbyl". Similar to an aryl, a substituted aryl may have one or more aromatic rings that may be fused, connected by single bonds or other groups; however, when the substituted aryl has a heteroaromatic ring, the free valency in the substituted aryl group can be for a heteroatom (such as nitrogen) of the heteroaromatic ring in place of a carbon. By an "activator", "cocatalyst" or a "catalyst activator" is defined one or more compounds that react with a transition metal compound to form a catalyst species that can polymerize the polymerizable olefin (s) (s) Useful activators include alkylaluminum compounds, certain boron compounds and other hydride or alkylation forming compounds. Typically the transition metal compound used in the first process and in steps (a), (b) and (c) of the second process will not itself start a polymerization, but will require the use of one or more activators to prepare a active olefin polymerization catalyst.

By "practically no activator is present" it is understood that no activator is present other than, for example, at very low levels as might be typical for impurities in the different components. The intention is that no significant amount of activated catalyst species will be generated in the support preparation process by the interaction of the transition metal complex with an activator - this activation should preferably occur at or near the time when the catalyst in a polymerization process. By "unmodified support" (silica or silica-alumina) is defined a support that does not contain (either bound or simply on the surface) materials that are designed to bind or otherwise cause the transition metal complex to be Adhere to the support. Such materials include alkylaluminum compounds and other hydride-forming alkylation and formation compounds, Lewis acids (bound or unbonded to the surface of the support) and other similar compounds. Preferably the transition metal complex and more preferably the trident ligand therein, has not linked thereto a group that will react or can react with the support to bind covalently to that support. For example it is preferred that the ligand does not contain a hydroxyl group (alcohol) which reacts with the silica surface.

By an "alkylaluminum compound" is meant a compound having at least one alkyl group directly linked to aluminum. Other groups such as, for example, alkoxide, hydride and halogen, may also be linked to the aluminum atom in the compound. Alkylaluminum compounds are activators. By "silica" or "silica-alumina" is defined a silica or silica-alumina that may or may not have been dehydrated, by heating. Preferably the material has been dehydrated to some degree, preferably by heating, before taking part in any of the processes described herein. These materials are well known in the art of polymer catalyst supports, and frequently, and preferably have high porosity and / or surface area. They often also have a small and / or controlled particle size. By "polymerization" is meant, in the broadest context, which includes dimerization, oligomerization and polymerization (homopolymerization and copolymerization). By "polymerization conditions" it refers here to the conditions that cause the "polymerization" of olefins with catalysts that use the same transition metal trident complexes, modified as described here. In other words, the polymerization catalyst systems described herein can be used under the same conditions as those reported above for the same complexes. Such conditions may include temperature, pressure, suspending media, polymerization method such as gas phase, liquid phase, continuous, in batches and the like. The supported catalysts are particularly useful in liquid suspension polymerizations and gas phase polymerizations. By "adsorbed" herein is meant merely that a first substance is "attracted" to a second substance such that the first substance "sticks" to the second substance (at least in part) even though for example the first adsorbed substance may be in the presence of a solvent for that first substance. In the present, the word "adsorbed" has no connotation for the first substance to stick to the second substance. By "relatively uncoordinated" (or weakly coordinated) anions those anions are defined as generally referred to in the art in this manner and the ability to coordinate such anions is known and has been discussed in the literature, see for example W Beck. , et al., Chem. Rev., vol. 88 p. 1405-1421 (1988) and S. H. Stares, Chem Rev., vol. 93, p. 927-942 (1993), both have been incorporated herein by reference for all purposes as if they were fully described. Among such anions are those formed from aluminum compounds in the immediately preceding paragraph and X ", which includes R93A1X ~, R92AlClX ~, R9AlCl2X ~ and R9A10X ~", where R9 is alkyl. Other uncoordinated useful anions include BAF ". {BAF = tetrakis [3, 5-bis (trifluoromethyl) -phenyl] borate], SbF6 ~, PF6", BF4 ~, trifluoromstansulfonate, p-toluensulfonate, (RfS02) N ", and (C6F5) 4B ~ By a" trident "ligand is defined a ligand that is capable of being a trident ligand, that is, it has three sites, often heteroatom sites, that can simultaneously coordinate a metal atom of transition, preferably the three sites coordinate the transition metal.For "a primary carbon group" here is defined a group of the formula CH2, where the free valence is for any other atom and the bond represented by the solid line is for a ring atom of a substituted aryl to which the primary carbon group is attached, so that the free valence may be attached to a hydrogen atom, a halogen atom, a carbon atom, an oxygen atom, an atom of sulfur, etc. In other words, the free valence - pu ede be for hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group. Examples of primary carbon groups include -CH3, CH2CH (CH3) 2, -C¾C1, -CH2C6H5, -OC¾ and -C¾OCH3. By a "secondary carbon group" the group / s is defined CH \ wherein the bond represented by the solid line is for a ring atom of a substituted aryl to which the secondary carbon group is attached, and both free bonds represented by the dotted line are for an atom or atoms other than hydrogen. These atoms or groups may be the same or different. In other words, the free valencies represented by dotted lines can be hydrocarbyl, substituted hydrocarbyl or inert functional groups. Examples of secondary carbon groups include -CH (C¾) 2, -CHC 12, -OKCeHs, cyclohexyl, -CH (CH 3) OCH 3 and -CH = CCH 3. For a "tertiary carbon group" a group of the formula is defined wherein the bond represented by the solid line is for a ring atom of a substituted aryl to which the tertiary carbon group is attached, and the three free bonds represented by the dotted lines are for an atom or atoms other than hydrogen. In other words, the bonds represented by the dotted lines are for hydrocarbyl, substituted hydrocarbyl or inert functional groups. Examples of tertiary carbon groups include -C (CH3) 3, -C (C6H5) 3, -CC12, -CF3, -C (CH3) 20CH3, -C = CH, -C (CH3) 2CH = CH2, aryl and substituted aryl such as phenyl and 1-adamantyl.

The preferred 2,6-pyridinedicarboxaldehydebisimines and 2,6-diacyl pyridinebisimine are compounds of the formula (I) wherein: R1, R2, R3, R4 and R5 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group, with the proviso that either of two of R1, R2 and R3 are vicinal to each other, taken together they can form a ring; and R6 and R7 are aryl, substituted aryl or a functional group. Generally a transition metal complex of (I) will have the formula LMXmYn where L is a ligand of 2,6-pyridinedicarboxal-dehyidobisimine or a 2,6-diacylpyridin-bisimine ligand, M is the transition metal, X is a monoanion (a negative charge), Y is a relatively uncoordinated monoanion and m + n is equal to the oxidation state of M. Generally if all X's are monodentate anions, then n is zero and m is equal to the oxidation state of M If, for example, one of X is a bidentate monoanion, then generally n is one (if m + n is 2). Thus m may be an integer of 1 or more, while n may be 0 or an integer of 1 or more, preferably n is 0 or 1. Monodentalated monoanions include halide and carboxylate, while bidentate monoanions include acetylacetonate, allylic and benzyl monoanions. The relatively uncoordinated anions are defined above. When none of X or Y are a hydrocarbyl anion or hydride, they generally form an active polymerization (in the second process) at least X must be converted to a hydrocarbyl anion such as alkyl or hydride (other anions may also be active). This is usually achieved with an activator (cocatalyst) which can, for example, be rented to the metal. By "alkylating" it is meant herein that the cocatalyst reacts with the LXnYn to be alkylated to the metal (for example to give LM (alkyl) mYn), while optionally at the same time a relatively uncoordinated anion is formed by extracting one of the alkyl groups (especially if n is zero). "The formation of hydrides is analogous to alkylation, except that a hydride anion is used in place of an alkyl anion.Alternatively, as part of the catalyst system a second cocatalyst that is a neutral Lewis acid can be added to extract the group alkyl and form a relatively uncoordinated anion Motar that this is just a scenario to form an active olefin polymerization catalyst that can be used, depending on the particular metal complex used and the cocatalyst (s) used. the activator (cocatalyst) is either (1) a neutral Lewis acid that is both (i) capable of excreting an anion of the transition metal from the transition metal complex to form a weakly coordinated anion, and (ii) capable of rent or hydride the transition metal; or (2) a combination of (i) a neutral Lewis acid that is capable of extracting an anion of the transition metal from the transition metal complex to form a weakly coordinated anion, and (ii) another compound that is capable of forming hydrides or rent the transition metal. More preferably, the cocatalyst is an alkylation compound and a Lewis acid which can form a weakly coordinated anion. . . - Useful alkylation compounds include alkylaluminium compounds (which may also be hydride forming compounds if it contains hydrogen linked to aluminum), alkylinc compound and Grignard reagents. Preferred compounds which can both alkylate and form a relatively uncoordinated anion are alkylaluminum compounds such as trialkylium compounds which include trimethylaluminum, triethylaluminum, tri-n-butylaluminum and tri-i-butylaluminum; aluminum alkyl compounds such as diethylaluminum chloride, ethylaluminum chloride and ethylaluminum sesquichloride; and (alkoxy) (alkyl) aluminum compounds such as ethoxy-diethylaluminum. Aluminoxanes, such as methylaluminoxane, can also be used, but because of their cost (even though they may otherwise be very effective) they are not preferred. In (I) it is generally preferred that: R1, R2 and R3 are hydrogen; and / or R1 and R3 are hydrogen and R2 is trifluoromethyl; and / or R4 and R5 are each independently halogen, thioalkyl, hydrogen or alkyl containing from 1 to 6 carbon atoms, more preferably R4 and R5 are each independently hydrogen or methyl. In a preferred form of (I), Re and R7 are each independently a substituted aryl and, more preferably, a substituted phenyl. Even more preferably, R6 is Y wherein R8, R12, R13 and R17 are each independently hydrocarbyl, substituted hydrocarbyl or an inert functional group; Rs, R10, R11, R14, R15 and R1S are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group; and with the proviso that any two of R8, R9, R10, R11, R12, R13, R14, R15, R16 and R17 that are vicinal to each other, taken together can form a ring. In (VI) and (VII), it is preferred that: Rs, R10, R11, R14, R15 and R16 are each independently hydrogen, halogen or an alkyl containing from 1 to 6 carbon atoms and more preferably than each of these are hydrogen; and / or R 10 and R 15 are methyl, phenyl or substituted phenyl (such as a phenyl substituted with alkyl); and / or R8, R12, R13 and R17 are each independently halogen, phenyl, substituted phenyl or an alkyl containing from 1 to 6 carbon atoms, more preferably each independently being phenyl, substituted phenyl (eg, a substituted phenyl) with alkyl such as pt-butylphenyl) or an alkyl containing from 1 to 6 carbon atoms (such as i-propyl or t-butyl) (although it is not preferred when both of R8 and R12, or both of R13 and R17, they are t-butyl in the same compound).

The specific preferred compounds are (in combination with any of the variants for R1, R2, R3, R4 and R5 mentioned above) wherein Rs and R7 are, respectively (VI) and (VII), and: R9, R11, R14 Y R1S are hydrogen and R8, -R10, R12, R13, R15 and R17 are methyl; R, R10, R11, R14, R1S and R16 are hydrogen, R8 and R13 are chloro and R12 and R17 are methyl; R9, R10, R11, R14, R15, R16 and R17 are hydrogen and R8 and R13 are phenyl; R9, R10, R11, R14, R15, R16 and R17 are hydrogen and R8 and R13 are p-t-butylphenyl; R9, R10, R11, R14, R15 and R16 are hydrogen, and R8, R12, R13 and R17 are phenyl; R9, R10, R11, R14, R15 and R1S are hydrogen, and R8, R12, R13 and R17 are p-t-butylphenyl; R9, R10, R11, R14, R15 and R16 are hydrogen, and R8 and R13 are phenyl and R12 and R17 are halo; Rs, R10, R11, R14, R15 and R16 are hydrogen, and R8 and R13 are p-t-butylphenyl and R12 and R17 are halo; R9, R10, R11, R14, R15 and R16 are hydrogen, and R8, R12, R13 and R17 are i-propyl; and R9, R10, R11, R12, R14, R15, R1S and R17 are hydrogen, and R8 and R13 are t-butyl. In another preferred variant of (I), R6 and R7 are each independently a substituted 1-pyrroyl. More preferably in this case, R6 and R7 are respectively (VIII) and (IX), where: R18 and R21 correspond to the definitions of, and to the preferences for, R8 and R12 in (VI); R22 and R25 correspond to the definitions of, and to the preferences for, R13 and R17 in (VII); R19 and R20 correspond to the definitions of, and preferences for, R9 and R11 in (VI); and R23 and R24 correspond to the definitions of, and to the preferences for, R14 and R16 in (VII). In the "polymerizations" in which a dimer or oligomer is produced, Re and R7 are each independently independently a substituted aryl having a first ring atom linked to the imino nitrogen, with the proviso that: in Rs, a second atom of ring adjacent to the first ring atom is linked to a halogen, a primary carbon group, a secondary carbon group or a tertiary carbon group; and further with the proviso that at 6, when the second ring atom is linked to a halogen or a primary carbon group, none, one or two of the other ring atoms in Rs and R7 adjacent to the first ring atom are linked to a halogen or a primary carbon group, the remainder of the ring atoms adjacent to the first ring atom being linked to a hydrogen atom; or in R6, when the second ring atom is linked to a secondary carbon group, none, one or two of the other ring atoms in R6 and R7 adjacent to the first ring atom are linked to a halogen, a primary carbon group or a secondary carbon group, with the remainder of the ring atoms adjacent to the first ring atom linked to a hydrogen atom; or in R6, when the second ring atom is linked to a tertiary carbon group, none or one of the other ring atoms in R6 and R7 adjacent to the first ring atom are linked to a tertiary carbon group, the remainder of which ring atoms adjacent to the first ring atom linked to a hydrogen atom. By "a first ring atom in Rs and R7 bonded to an imino nitrogen atom" is meant the ring atom in these groups bonded to an imino. nitrogen shown in (I), for example (II) or (LID) the atoms shown in position 1 in the rings in (II) and (III) are the first atoms of the ring bonded to an imino carbon atom (other groups which may be substituted in the aryl groups are not shown). Ring atoms adjacent to the first ring atoms are shown, for example, in (IV) and (V), where the valences open to these adjacent atoms are shown by dotted lines (positions 2.6 in (IV) and positions 2, 5 in (V)).

In the preferred dimerization / gomerization modalities, R6 is (Vlla) wherein: R8 is a halogen, a primary carbon group, a secondary carbon group or a tertiary carbon group; and R9, R10, R11, R14, R15, R16 and R17 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group; with the proviso that: when R8 is halogen or a primary carbon group, none, one or two of R12, R13, and R17 are a halogen or a primary carbon group, with the remainder of R, R and R being hydrogen; or when R8 is a secondary carbon group, none or one of R12, R13, and R17 is a halogen, a primary carbon group or a secondary carbon group, the remainder of R12, R13 and R17 being hydrogen; or when R is a tertiary carbon group, none or one of R12, R13, and R17 is a tertiary carbon group, with the remainder of R12, R13 and R17 being hydrogen; and with the additional proviso that any two of R8, R9, R10, R11, R12, R13, R14, R15, Rie and R17 neighbor to each other, taken together can form a ring. In the above formulas (Via) and (Vlla), R8 corresponds to the second ring atom adjacent to the first ring atom linked to the imino nitrogen, and R12, R13 and R17 correspond to the other ring atoms adjacent to the first ring atom. In compounds (I) containing (Via) and (Vlla), it is particularly preferred that: if R8 is a primary carbon group, R13 is a primary carbon group, and R12 and R17 are hydrogen; or if R8 is a secondary carbon group, R13 is a primary carbon group or a secondary carbon group, more preferably a secondary carbon group and R12 and R17 are hydrogen; or if R8 is a tertiary carbon group (more preferably a trihalo tertiary carbon group such as a trihalomethyl), R13 is a tertiary carbon group (more preferably a trihaltetheryl group such as a trihalomethyl) and R12 and R17 are hydrogen; or if R8 is a halogen, R13 is halogen and R12 and R17 are hydrogen.

In all the preferred specific compounds (I) in which (Vía) and (Vlla) appear, it is preferred that R 1, R 2 and R 3 are hydrogen; and / or R4 and R5 are methyl. It is further preferred that: R9, R10, R11, R12, R14, R15, R1S and R17 are all hydrogen; R13 is methyl; and R8 is a primary carbon group, more preferably methyl; or R9, R10, R11, R12, R14, R15, R16 and R17 are all hydrogen; R13 is ethyl; and R8 is a primary carbon, more preferably ethyl, group; or R9, R10, R11, R12, R14, R15, R16 and R17 are all hydrogen; R13 is isopropyl; and R8 is a primary carbon group, more preferably isopropyl; or R9, R10, R11, R12, R14, R15, R16 and R17 are all hydrogen; R13 is n-propyl; and R8 is a primary carbon group, more preferably n-propyl; or R9, R10, R11, R12, R14, R15, Rie and R17 are all hydrogen; R13 is chlorine; and R8 is a halogen, more preferably chlorine; or R9, R10, R11, R12, R14, R15, R16 and R17 are all hydrogen; R 13 is trihalometyl, more preferably trifluoromethyl; and R8 is trihalomethyl, more preferably trifluoromethyl. In another preferred embodiment of (I), R6 and R7 are respectively (Villa) and (IXa), where: R18 corresponds to the definitions of, and preferences for, R8 (Vía); R19, R20 and R21 correspond respectively to the definitions of, and preferences for, RB, R10 and R32 in (Vía); and R22, R23, R24 and R25 correspond respectively to the definitions of, and preferences for, R13, R14, R16 and R17 in (Vlla). In the above formulas (Villa) and (IXa), R18 corresponds to the second ring atom adjacent to the first ring atom linked to the imino nitrogen, and R21, R22 and R25 correspond to the other ring atoms adjacent to the first ring atom. Any transition metal that forms an active polymerization catalyst can be used with (I). As examples of suitable transition metals, those found in Groups 3-12 of the Periodic Table (IUPAC) may be mentioned. Preferred are those of transition metals of Groups 8-10, more preferred are the transition metals of Groups 8 and 9, particularly Fe and Co are preferred and Fe is especially preferred. The compound (I) and its transition metal complexes can be prepared by the variety of methods described in the previously incorporated references, as well as by the methods described, for example, in WO9950273 and WO00 / 08034, both of which they have been incorporated herein by reference for all purposes as if they were fully described. Preferred monomers for the polymerization (including oligomerization) are ethylene and alpha-olefins of the formula R18CH = C¾ wherein R18 is n-alkyl, especially n-alkyl containing from 1 to 10 carbon atoms. Ethylene is preferred only to give a homopolymer of ethylene (or in the case of oligomerization, a series of alpha-olefins having the same number of carbon atoms), or a combination of ethylene with one or more alpha-olefins ( such as propylene, 1-hexen, 1-octene, 1-decene and / or 1-dodecene) to give an ethylene copolymer. In the processes of the present invention (both for preparing the supported catalyst component and the polymerization of one or more olefins), the transition metal complex is preferably initially dissolved in a solvent. It is preferred that the solvent does not substantially decompose the complex, since the solvent can additionally complex with the metal complex. Preferably the solvent is an aprotic solvent and not a protic solvent such as water, an alcohol or a carboxylic acid. Preferably, the complex should have a solubility of at least about 0.0001 g per 100 ml of solvent, more preferably at least about 0.01 g per 100 ml of solvent. Preferably, the solvent / complex combination is subsequently contacted with the silica or silica-alumina (collectively, the support) preferably under agitation, at which point the complex is at least partially adsorbed on the support. The adsorption can be relatively rapid, particularly if the complex has a relatively high solubility in the solvent. In this case the contact can be made in less than 1 hour. If the complex has a low solubility in the solvent (for example, not all transition metal can be dissolved at the time), more time (perhaps 10 hours or more) may be required to dissolve the complex and have adsorbed on the support. Moderate agitation is preferred to ensure mixing of the support with the solution. Frequently the complex has color, and one can judge the progress of the adsorption of the complex on the support visually. Sometimes not all transition metal complexes are adsorbed on the support. It is preferable that at least about 50%, more preferably at least 80% of the present complex be adsorbed. The unadsorbed complex can be recycled to be adsorbed on more support.

After the contact step, the solution and / or solvent can be separated from the support (and the adsorbed complex) by any standard method, for example by filtering the solvent support (and any inactive complex dissolved therein) by filtration. , or by centrifuging the mixture and separating the solid supernatant by decanting, the solvent is removed by evaporation, for example under vacuum. Preferably the solution is separated from the support as a liquid, by filtration or centrifugation as described above. It is desired that the support and the adsorbed complex can be washed with solvent to remove any non-adsorbed complex (some of the adsorbed complex can also be removed at this point) and / or the support and the adsorbed complex can be dried, by vacuum vaporization . However, preferably most, preferably > 90% of the solvent must not be separated from the supported complex by vaporization of the solvent (in other words, a physical separation of the solid support and the liquid solvent (solution) must be carried out). The supported catalyst can also be used in a polymerization process without separating it from the solvent / solution, but it is preferred that it be separated from the solvent / solution before being used in a polymerization. Preferably the ratio of the transition metal complex to the support in step (a) will be such that the final amount of the transition metal in the supported catalyst (measured as transition metal) is about 0.01 to about 5.0, more preferably about 0.02 to about 1.0 weight percent of the total weight of the supported catalyst component. Few experiments may be required to determine the exact conditions necessary to obtain a particular concentration of the transition metal in the supported catalyst component, with any particular group of transition metal complexes, solvent and support, however, this experimentation is well known within the ability of a person with ordinary experience in the field. Generally speaking, the higher the ratio of the transition metal complex to the support that is present in the first process, the greater the amount of the transition metal in the supported catalyst component. In order to ensure that the supported catalyst is as active as possible it is preferred that all stages (and storage), in which the transition metal complex (adsorbed or unadsorbed) is present, can be carried out under an inert atmosphere such as nitrogen or argon. It has been found that the supported catalyst component prepared by this process is stable at room temperature for extended periods. Also this catalyst does not need to contain materials that are considered inflammable or pyrophoric, and can be transported without extraordinary precautions by relatively cheap devices. This component of the supported catalyst can be used as part of a catalyst system for the polymerization of olefins, as described in the different previously incorporated publications. In the polymerization processes described above, a preferred molar ratio of the alkylation cocatalyst or hydride formation (preferably an alkyl aluminum compound or a dialkyl compound) to the "moles" of the transition metal is about 1 to about 2000 , more preferably about 5 to about 1000 and especially preferably about 30 to about 500 (Any of these minimum and maximum relationships can be in pairs one with respect to another). Generally this cocatalyst is also used simultaneously as a "purifier", this is a chemical compound that removes impurities in the polymerization system which are harmful to the polymerization process. Thus, the ratio of this cocatalyst to the transition metal will also depend to some degree on the level of harmful impurities in the second process.

If an additional Lewis acid is needed to extract this, an alkyl and form a relatively uncoordinated anion, generally speaking the molar ratio of this Lewis acid to the transition metal is generally about 1 about 5. it prefers that any of the cocatalysts used in the polymerization process be in contact with the supported catalyst prepared in the first process in the presence of olefin monomer (s) or that contact with the cocatalysts be carried out briefly before (less than 6). hours, more preferably less than 1 hour and especially preferably less than 5 minutes) of further contacting with the olefin monomer (s). In fact it is especially preferred that the cocatalyst (s) and the supported catalyst are in contact together in the polymerization vessel alone, or in a process line that is directed to the polymerization vessel. If the polymerization process takes place in the liquid phase, for example a suspension polymerization, the supported catalyst and any cocatalyst (s) can be added to the liquid suspension medium. If the polymerization is a gas phase polymerization the particulate supported catalyst can be fluidized by the gas and the cocatalyst (s) such as a trialkyl aluminum compound can be added as a vapor. For this purpose a relatively volatile alkylaluminium compound such as trimethylaluminum is often preferred. More than one transition metal compound can be used as the polymerization catalyst, one or both can be supported on the same support or on a different support. For more information on such catalyst mixtures, see WO 9946302 previously incorporated, as well as WO 9838228, WO 9950318 and WO 9957159, which are all also appended hereto by reference for all purposes as if they were fully described. Typical polymerization conditions can be used, for example, hydrogen can be used to control the molecular weight of the polyolefin. See, for example, WO 9946302, as well as WO 9962963, which is also incorporated by reference herein for all purposes as if fully described. In a preferred form of the polymerization process, the transition metal complex of the trident ligand oligomerizes ethylene to relatively pure α-olefins. For information on such oligomerizations see, for example, US 6063881, US 6103946, WO 0055216 and WO 0073249 previously incorporated, as well as WO 0076659, which is likewise incorporated by reference herein for all purposes as if fully described. If in addition a second transition metal compound is also present which is capable of copolymerizing ethylene and α-olefins, a branched polyethylene will be obtained. See, for example WO9950318 and WO 0055216 previously incorporated. In this case it is preferred that the second transition metal compound be in the same support as used in the first process and the oligomerization and polymerization catalysts can be placed on the support simultaneously (as in the first process, with the catalyst of additional polymerization also present). The morphology of the silica particles used as the support is frequently replicated in the polymer particles (including silica) obtained. The product of many of the following examples show such replication. It is believed that the replication of the silica support morphology shows a uniform deposition of the catalyst species in the absence of any deposited activated alkylaluminium compound, such as methylaluminoxane. In the examples and in the experimentation, the following abbreviations were used: acac-acetylacetonate ICP - Inductively Coupled Plasma Spectroscopy f .b. - round bottom THF - tetrahydrofuran In the examples all pressures are manometric. In the examples, the following transition metal complexes were used: 1 and 3 were prepared by the procedures described in previously incorporated US 5955555. EXAMPLE 1 1 was recrystallized from CH2C12. 1 (7.0 mg) was dissolved in anhydrous CH2C12 (7 mL) and silica (0.5 g Grade silica Grace 948 dehydrated Grade XPO-2402, dehydrated to 1 mmol OH group per gram of silica) was added. The resulting deep blue mixture was stirred for 30 min. The resulting solid was then filtered from a very pale blue filtrate, and dried. The production was 0.5 g of a light blue solid. Mass% Fe (ICP) = 0.14% EXAMPLE 2 Recrystallized 1 from ?? 2012. 1 (7.0 mg) was dissolved in anhydrous CH2Cl2 (7 mL) and silica-alumina [0.5 g, Grace M513-1.10 dehydrated at 200 ° C (flowing N2)] was added. The resulting deep blue mixture was stirred for 60 min. The resulting solid was then filtered from a colorless filtrate, washed with CH2C12 and dried. The production was 0.5 g of a gray / light blue solid. EXAMPLE 3 1 was recrystallized from CH2C12. 1 (7.0 mg) was dissolved in anhydrous CH2C12 (7 ml) and silica-alumina [0.5 g, Grace M513-1.10 dehydrated at 500 ° C (flowing N2)] was added. The resulting deep blue mixture was stirred for 60 min. The resulting solid was then filtered from a colorless filtrate, washed with CH2C12 and dried. Production 0.5 g of a light orange solid. EXAMPLE 4 1 was recrystallized from CH2C12. 1 (4.0 mg) was dissolved in anhydrous toluene (15 mL) and silica (0.25 g, silica 948 dehydrated Grace XPO-2402) was added. The resulting mixture was stirred overnight. The resulting solid was then filtered from an almost colorless filtrate, washed with toluene and pentane and dried. Production 0.5 g of a light blue solid. EXAMPLE 5 Unrecrystallized 1 (4.0 mg) was dissolved in anhydrous toluene (15 mL) and silica (0.25 g, silica 948 dehydrated Grace XPO-2402) was added. The resulting mixture was stirred overnight. The resulting solid was then filtered from an almost colorless filtrate, washed with toluene and pentane and dried. Production 0.5 g of a light blue solid. EXPERIMENT 1 Prepare 2 weighing (C27H31 3, 1.00 g, 397.56 g / mol, 2. 515 mmol) and Fe (acac) 2 (644 mg, 253.15 g / mol, 2.516 mmol) and [Na] [BAF] (2.24 g, 890 g / mol, 2.517 mmol, BAF = B (3.5- (CF3 ) 2C6H2] 4) in a vial and then placed in a 50 ml round bottom flask with a stir bar, THF (25 ml) was added to give a dark red solution which was stirred for 24 hours. was removed (the product is not completely soluble in THF) and the product was suspended in toluene and filtered through Celite®, the solvent was removed from the dark red solution, pentane was added to give a red precipitate which was filtered , rinsed, dried under vacuum to give 2. Elemental Analysis for: C64H5oBF24Fe 302 (1415.72 g / mol), Theory: C, 54.30; H, 3.56; N, 2.97 Experimental Result: C, 54.37; H, 3.58; N , 2.96 EXAMPLE 6 2 (19.6 mg) was dissolved in anhydrous toluene (7 ml) to give a yellow-orange solution and silica alumina [0.5 g, Grace dehydrated at 200 ° C (flowing N2)] was added. it is agitated or for 60 min The solid was then filtered from an almost colorless filtrate, washed with toluene and pentane and dried. Production 0.5 g of solid naranj a / beige.

EXAMPLE 7 3 (7.5 g) was dissolved in anhydrous CH2Cl2 (7 mL) to form a bright yellow solution and silica (0.5 g, silica 948 Grace dehydrated) was added. The resulting mixture was stirred for 60 min. The solid was then filtered off from a pale yellow filtrate, washed with toluene and pentane and dried Yield 0.5 g of lemon yellow solid EXAMPLE 8 In a dry box, a stainless steel cylinder (25 to 40 ml. volume) was charged with the product of Example 1 (75.8 mg) and another cylinder with 10 ml of a solution of triisobutylaluminum (1M solution in hexane, Aldrich) The cylinders were connected to the orifices of an autoclave reactor under a nitrogen purge of the connections The cylinder pressurization lines were also connected under purge Isobutane (1200 g, Matheson CP grade) were transferred into a cooled autoclave (-30 ° C) by pressure difference. Once the transfer was completed, the autoclave (Autoclave Engineers, stirred, 1-gal, 3.8 L) was heated to 20 ° C and stirred at 1000 rpm. The solvent was saturated with hydrogen at a pressure of 0.36 MPa (total pressure, including hydrogen). After saturation, the reactor was heated to 80 ° C and pressurized with ethylene at 1.4 MPa. The triisobutylaluminum solution was propelled to the reactor with ethylene followed by the catalyst of Example 1, also driven with ethylene. The final reactor pressure was 2.41 MPa and the ethylene feed was changed from the feed vessels to the side hole in the autoclave. The reaction was run for 3 hours. At the end of the polymerization, the reactor was slowly vented, followed by a nitrogen purge before opening the reactor. The polymer was dried overnight. The production of the polymer was 353 g, resulting in a catalyst efficiency of 4.65 kg PE / g catalyst (including support), or a polymerization rate of 1.55 kg PE / g catalyst. Or 1109 kg PE / g Fe .h. EXAMPLE 9 Following the same procedure as in Example 8, but with 5 ml of a solution of triisobutylaluminum and 75.5 mg of the supported catalyst of Example 1, the production of the polymer was 316 g, resulting in a catalyst efficiency of 4.18 kg PE / g of catalyst or a polymerization rate of 1.40 kg PE / g of catalyst. or 997 kg PE / g Fe.h. EXAMPLE 10 Following the same procedure as in Example 8, but with 15 ml of a solution of triisobutylaluminum and 78.0 mg of the supported catalyst of Example 1, the production of the polymer was 256 g, resulting in a catalyst efficiency of 3.28 kg PE / g of catalyst or a polymerization rate of 1.09 kg PE / g catalyst.ho 781 kg PE / g Fe.h.

EXAMPLE 11 - Following the same procedure as in Example 8, but with 10 ml of a solution of triisobutylaluminum and 75.8 mg of the supported catalyst of Example 2, the production of the polymer was 182 g, resulting in a catalyst efficiency of 2.4 kg PE / g of catalyst or a polymerization rate of 0.8 kg PE / g of ycatalyst. h or 572 kg PE / g Fe.h. EXAMPLE 12 Following the same procedure as in Example 8, but with 10 ml of a solution of triisobutylaluminum and 74.2 mg of the supported catalyst of Example 4, the production of the polymer was 380 g, resulting in a catalyst efficiency of 5.12 kg PE / g of catalyst or a polymerization rate of 1.71 kg PE / g catalyst.ho 1219 kg PE / g Fe.h. EXAMPLE 13 Following the same procedure as in Example 8, but with 10 ml of a solution of triisobutylaluminum and 75.4 mg of the supported catalyst of Example 4, the production of the polymer was 374 g, resulting in a catalyst efficiency of 4.96 kg PE / g of catalyst or a polymerization rate of 1.65 kg PE / g catalyst.ho 1181 kg PE / g Fe.h. EXAMPLE 14 Following the same procedure as in Example 8, but with 5 ml of a solution of triisobutylaluminum and 79.8 mg of the supported catalyst of Example 3, the production of the polymer was 51 g, resulting in a catalyst efficiency of 0.64 kg PE / g of catalyst or a polymerization rate of 0.21 kg PE / g of catalyst or 152 kg PE / g Fe.h. EXAMPLE 15 1 (7.0 mg) was weighed into a vial vial and distilled into approximately 10 ml of toluene and 0.5 g of silica gel (Grace Davidson 948) dehydrated at 0.76 mmol OH / g was added to the vial. The vial vial was shaken for 30 min. The mixture was filtered through a field glass frit and the solids were dried overnight under vacuum at room temperature. EXAMPLES 16-28 Following the same procedure as in Example 8, but using the catalyst prepared in Example 15 with different results of hydrogen in the production of the polymer shown below in the table.

Weight of Production Density Example Hydrogen Catalyst dry Apparent activity Kg PE / g Number kPag mg g Fe / hr 16 125 80.0 88.0 282 0.316 17 35 78.2 32.0 105 18 35 73.9 234.0 812 0.316 19 276 72.3 19.0 67 20 125 76.2 232.0 781 0.3097 twenty-one - . 21 - 74.9 260.0 890 0.404 22 35 75.5 154.0 523 0.304 23 125 75.2 174.0 593 0.313 24 245 76.1 118.0 398 0.289 572 76.9 31.0 103 0.259 26 125 79.9 273.0 876 0.325 27 207 76.7 230.0 769 0.319 28 69. 75.0 400.0 1368 0.367 It is noted that in relation to this date, the best method known by the applicant to carry out the aforementioned invention is that which is clear from the present description of the invention.

Claims (19)

1. CLAIMS Having described the invention as above, the content of the following claims is claimed as property: 1. A process for the preparation of a supported polymerization catalyst component, characterized in that it comprises: (a) dissolving an iron complex of a , 6-pyridinedicarboxaldehydebisimine or a 2,6-diacylpyridine-bisimine in a solvent to form a solution; and (b) contacting said solution with a support which is an unmodified silica or a silica-alumina for a sufficient amount of time to allow at least part of the metal complex to be adsorbed to the support, with the condition that virtually no activator is present during (a) and (b).
2. 2. The process according to claim 1, characterized in that it further comprises separating the solution and the solvent from the support and with the condition that practically no activator is present during the separation.
3. 3. The process according to claim 1, characterized in that step (b) is carried out with stirring.
4. 4. The process according to claim 1, characterized in that the transition metal complex has the formula LMXmYn wherein L is a ligand of 2,6-pyridinedicarboxaldehydebisimine or 2,6-diacylpyridinebisimine, M is the atom of iron, X is a monoanion, and is a relatively non-monoanion. coordinated and m + n is equal to the oxidation state of M.
5. 5. The process according to claim 4, characterized in that the ligand has the formula (I) wherein: R1, R2, R3, R4 and R5 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group, with the proviso that either of two of R1, R2 and R3 are vicinal to each other, taken together they can form a ring; and R6 and R7 are aryl, substituted aryl or a functional group.
6. 6. The process according to claim 5, characterized in that: R1, R2 and R3 are hydrogen; or R1 and R3 are hydrogen and R2 is trifluoromethyl; R4 and R5 are each independently hydrogen or methyl; wherein: R8, R12, R13 and R17 are each independently hydrocarbyl, substituted hydrocarbyl or an inert functional group; Rs, R10, R11, R14, R15 and R16 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group; and with the proviso that any two of R8, R9, R10, R11, R12, R13, R14, R15, R15 and R17 that are vicinal to each other, taken together can form a ring.
7. 7. The process according to claim 6, characterized in that: R1, R2 and R3 are hydrogen; R4 and R5 are hydrogen or methyl; Ra, R11, R14? Rb are hydrogen and RB 8, RD11U0, Rn "12, Rt-, 11J3, R," 15 and R17 are methyl; or R9, R10, R11, R14, R15 and R16 are hydrogen, R8 and R13 are chloro and R12 and R17 are methyl; or R9, R10, R11, R14, R15, R16 and R17 are hydrogen, and R8 and R13 are phenyl; or R9, R10, R11, R14, R15, Rie and R17 are hydrogen, and R8 and R13 are p-t-butylphenyl; or R9, R10, R11, R14, R15 and R16 are hydrogen, and R8, R12, R13 and R17 are phenyl; or R9, R10, R11, R14, R15 and R1S are hydrogen, and R8, R12, R13 and R17 are p-t-butylphenyl; or R9, R10, R11, R14, R15 and R16 are hydrogen, and R8 and R13 are phenyl and R12 and R17 are halo; or R9, R10, R11, R14, R15 and R16 are hydrogen, and R8 and R13 are p-t-butylphenyl and R12 and R17 are halo; or Rs, R10, R11, R14, R15 and R1S are hydrogen, and R8, R12, R13 and R17 are i-propyl; or R9, R10, R11, R12, R14, R15, R15 and R17 are hydrogen, and R8 and R13 are t-butyl.
8. 8. The process according to claim 5, characterized in that: R1, R2 and R3 are hydrogen; or R1 and R3 are hydrogen and R2 is trifluoromethyl; R4 and R5 are each independently hydrogen or methyl; R6 is wherein: R8 is a halogen, a primary carbon group, a secondary carbon group or a tertiary carbon group; and R > , R, i -, 14 R 1'5 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group; with the proviso that: when R8 is a halogen or a primary carbon group, none, one or two of R12, R13, and R17 are a halogen or a primary carbon group, the remainder of R12, R13 and R17 being hydrogen; or when R8 is a secondary carbon group, none or one of R12, R13, and R17 is a halogen, a primary carbon group or a secondary carbon group, the remainder of R12, R13 and R17 being hydrogen; or when R8 is a tertiary carbon group, none or one of R12, R13, and R17 is a tertiary carbon group, with the remainder of R12, R13 and R17 being hydrogen; and with the additional proviso that any two of R8, R9, R10, R11, R12, R13, R14, R15, R16 and R17 are vicinal to each other, taken together to form a ring.
9. 9. The process according to claim 8, characterized in that: R9, R10, R11, R12, R14, R15, R16 and R17 are all hydrogen, and R13 and R8 are methyl; or R9, R10, R11, R12, R14, R15, R16 and R17 are all hydrogen, and R8 and R13 are ethyl; or R9, R10, R11, R12, R14, R15, R1S and R17 are all hydrogen, and R8 and R13 are isopropyl; or Rs, R10, R11, R12, R14, R15, R16 and R17 are all hydrogen, and R8 and R13 are n-propyl; or R9, R10, R11, R12, R14, R15, R16 and R17 are all hydrogen, and R8 and R13 are chloro; or R9, R10, R11, R12, R1, R15, R1S and R17 are all hydrogen, and R8 and R13 are trifluoromethyl.
10. 10. A polymerization catalyst component characterized in that it is obtained by the process of claim 1.
11. 11. A process for the polymerization of one or more polymerizable olefins, characterized in that it comprises the steps of: (a) dissolving an iron complex of a 2,6-pyridinedicarboxaldehydebisimine or a 2,6-diacylpyridine bisimine in an organic solvent to form a solution; (b) contacting said solution with a support, which is a silica or a silica-alumina, for a sufficient amount of time to allow at least part of the metal complex to be adsorbed on the support, thereby forming a supported catalyst component; and (c) contacting, under polymerization conditions, said supported catalyst component with one or more polymerizable olefins and one or more activators, with the proviso that practically no activator is present during steps (a) and (b) .
12. 12. The process according to claim 11, characterized in that it further comprises separating the solution and the solvent from the supported catalyst component; and with the condition that practically no activator is present during the separation.
13. 13. The process according to claim 11, characterized in that step (b) is carried out with stirring.
14. The process according to claim 11, characterized in that the iron complex has the formula L XmYn wherein L is a ligand of 2,6-pyridinedicarboxaldehydebisimine or a ligand of 2,6-diacylpyridinbisimine, is an iron atom, X is a monoanion, and is a relatively uncoordinated monoanion m + n is equal to the oxidation state of M.
15. 15. The process according to claim 14 characterized in that the ligand has the formula (I) wherein: R1, R2, R3, R4 and R5 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group, with the proviso that either of two of R1, R2 and R3 are vicinal to each other, taken together they can form a ring; and Rs and R7 are aryl, substituted aryl or a functional group.
16. 16. The process according to claim 15, characterized in that: R1, R2 and R3 are hydrogen; or R1 and R3 are hydrogen and R2 is trifluoromethyl; R4 and Rs are each independently hydrogen or methyl; R6 is wherein R8, R12, R13 and R17 are each independently hydrocarbyl, substituted hydrocarbyl or an inert functional group; R9, R10, R11, R14, R15 and R16 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group; and with the proviso that any two of R8, R9, R10, R11, R12, R13, R14, R15, R1S and R17 that are vicinal to each other, taken together can form a ring.
17. 17. The process according to claim 16, characterized in that: R1, R2 and R3 are hydrogen; R4 and R5 are hydrogen or methyl; Rs, R11, R14 and R1S are hydrogen and R8, R10, R12, R13, R15 and R17 are methyl; or R9, R10, R11, R14, R15 and R16 are hydrogen, R8 and R13 are chloro and R12 and R17 are methyl; or R9, R10, R11, R14, R15, R16 and R17 are hydrogen, and R8 and R13 are phenyl; or R9, R10, R11, R14, R15, R16 and R17 are hydrogen, and R8 and R13 are p-t-butylphenyl; or R9, R10, R11, R14, R15 and R16 are hydrogen, and R8, R12, R13 and R17 are phenyl; or R9, R10, R11, R14, R15 and R1S are hydrogen, and R8, R12, R13 and R17 are p-t-butylphenyl; or R9, R10, R11, R14, R15 and R16 are hydrogen, and R8 and R13 are phenyl and R12 and R17 are halo; or R9, R10, R11, R14, R15 and R16 are hydrogen, and R8 and R13 are p-t-butylphenyl and R12 and R17 are halo; or R9, R10, R11, R1, R15 and R16 are hydrogen, and R8, R12, R13 and R17 are i-propyl; or R9, R10, R11, R12, R14, R15, R16 and R17 are hydrogen, and R8 and R13 are t-butyl.
18. 18. The process according to claim 15, characterized in that: R1, R2 and R3 are hydrogen; or R1 and R3 are hydrogen and R2 is trifluororneti1o; R4 and Rs are each independently hydrogen or methyl; R6 is in which R8 is a halogen, a primary carbon group, a secondary carbon group or a tertiary carbon group; and R9, R10, R11, R14, R, 15 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group; with the proviso that: when R8 is a halogen or a primary carbon group, none, one or two of R12, R13, and R17 are a halogen or a primary carbon group, the remainder of R22, R13 and R17 being hydrogen; or when R8 is a secondary carbon group, none or one of R12, R13, and R17 is a halogen, a primary carbon group or a secondary carbon group, the remainder of R12, R13 and R17 being hydrogen; or when R8 is a tertiary carbon group, none or one of R12, R13, and R17 is a tertiary carbon group, with the remainder of R12, R13 and R17 being hydrogen; and with the additional proviso that any two of R8, R9, R10, R11, R12, R13, R14, R15, R16 and R17 neighbors with respect to each other, taken together can form a ring.
19. 19. The process according to claim 18, characterized in that: R9, R10, R11, R12, R14, R15, R16 and R17 are all hydrogen, and R13 and R8 are methyl; or R9, R10, R11, R12, R14, R15, R16 and R17 are all hydrogen, and R8 and R13 are ethyl; or R9, R10, R11, R12, R14, R15, R16 and R17 are all hydrogen, and R8 and R13 are isopropyl; or R9, R10, R11, R12, R14, R15, R16 and R17 are all hydrogen, and R8 and R13 are n-propyl; or Rs, R10, R11, R12, R14, R15, R1S and R17 are all hydrogen, and R8 and R13 are chlorine; or R9, R10, R11, R12, R14, R15, R16 and R17 are all hydrogen, and R8 and R13 are trifluoromethyl.