MXPA00010918A - Copolymerization of olefins - Google Patents

Abstract

Ethylene and/or propylene, and&agr;-olefins may be copolymerized by contacting them with certain iron or cobalt complexes of selected 2,6-pyridinecarboxaldehydebis(imines) and 2, 6-diacylpyridinebis(imines). The polymers produced, some of which are novel, are useful as molding resins.

Description

COPOLIMERIZATION OF THE OLEFINS FIELD OF THE INVENTION The iron and cobalt complexes selected from the 2,6-pyridinecarboxaldehydebis (imines) and 2,6-diacylpyridinebis (amines) are catalysts for the copolymerization of ethylene and / or propylene and the α-olefins.

FIELD OF THE INVENTION The copolymers of ethylene and / or propylene and α-olefins, such as low density polyethylene (LLDPE) are a matter of importance in commerce, millions of tons are produced annually. These polymers are used in a large number of ways, such as for fiber, films, molding resins, etc. In most cases, ethylene and α-olefins are copolymerized using a catalyst, often a transition metal compound or complex. These catalysts can vary in the cost per unit weight of the polymer produced, the structure of the polymer produced, the possible need to remove the ßf.124151 catalyst from the polymer, the toxicity of the catalyst, etc. Due to the commercial importance of ethylene copolymerization, new polymerization catalysts are always being sought. B. L. Small, et al., J. Am. Chem. Soc., Vol. 120, p. 4049-4050 (1998), and G. J. P. Britovsek, et al., J. Chem. Soc., Chem. Commun., P. 849-850 (1998) report the homopolymerization of ethylene using catalysts containing Fe or Co complexes of the 2,6-pyridinecarboxaldehydebis (imines) and 2,6-diacylpyridinebis (amines). These catalysts are described similarly in 098/27124 for preparing homopolyethylenes, and in O98 / 30612 for preparing homopolypropylenes. The copolymerization of α-olefins and ethylene is not reported in these publications.

BRIEF DESCRIPTION OF THE INVENTION This invention relates to a first polymerization process, comprising, contacting, at a temperature of about -100 ° C to about +200 ° C, a compound of the formula: with one or both of ethylene and propylene, and an olefin of the formula H2C = CHR21 and: (a) a first compound, which is a neutral Lewis acid capable of subtracting X "an alkyl group or a hydride group of M for forming WX ", (WR20)" or WH "and which are capable of transferring an alkyl group or a hydride to M, provided that WX" is a weak coordination anion, or (b) a combination of a second compound which is capable of transferring an alkyl or hydride group to M and a third compound which is a neutral Lewis acid which is capable of subtracting X ~, a hydride or an alkyl group of M to form a weak coordinating anion; where: M is Co or Fe, each X is an anion; n is 1, 2 or 3 so that the total number of negative charges on the anion or anions is equal to the oxidation state of an atom of Fe or Co present in di); R1, R2 and R3 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group; R4 and R5 are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl; R6 and R7 are aryl or substituted aryl; R20 is alkyl; and R21 is alkyl. This invention also relates to a second polymerization process, comprising contacting, at a temperature of about -100 ° C to about +200 ° C, a complex of Co [II], Co [III], Fe [II] ] or Fe [III] of a tridentate ligand of the formula with one or both of ethylene and propylene, and an olefin of the formula H2C = CHRl2211 wherein: R1, R2 and R3 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group; R4 and R5 are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl; and R6 and R7 are aryl or substituted aryl; R21 is alkyl; and whenever an atom of Co [II], Co [III], Fe [II] or Fe [III] also has to bind to it in an empty coordination site or a ligand that can be displaced by ethylene, and a ligand that can be added to ethylene. This invention also relates to a third polymerization process, comprising, contacting, at a temperature of about -100 to about +200 ° C, one or both of ethylene and propylene, an olefin of the formula H2C = CHR21, and a compound of the formula: (VII) (IX) where: M is Co or Fe; R1, R2 and R3 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group; R4 and R5 are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl; and R6 and R7 are aryl or substituted aryl; R21 is alkyl; T1 is hydride or alkyl or any other anionic ligand in which ethylene or an α-olefin can be inserted; And it is a neutral ligand capable of being displaced by ethylene or a vacant coordination site; Q is a relatively non-coordinating anion; P is a divalent polyolefin group; and T2 is a final group.

DETAILS OF THE INVENTION Here, certain terms are used. Some of them are: • A "hydrocarbyl group" is a univalent group that contains only carbon and hydrogen. If not stated otherwise, it is preferred that the hydrocarbyl groups here contain 1 to about 30 carbon atoms. • By "substituted hydrocarbyl" is meant here a hydrocarbyl group which contains one or more substituent groups which are inert under the process conditions to which the compounds containing these groups are subjected. Substituent groups also do not interfere substantially with the process. If not stated otherwise, it is preferred that the substituted hydrocarbyl groups here contain 1 to about 30 carbon atoms. Included in the meaning of "substituted" are the heteroaromatic rings. All of the hydrogen atoms may be substituted, as in trifluoromethyl. • By "functional group (inert)" is meant here a different group of the hydrocarbyl or substituted hydrocarbyl which is inert under the process conditions to which the compound containing the group is subjected. The functional groups also do not interfere substantially with any process described herein because the compound in which they are present can take part. Examples of the functional groups include halo (fluoro, chloro, bromo and iodo), ethers such as -OR18 wherein R18 is hydrocarbyl or substituted hydrocarbyl. In cases in which the functional group may be close to a cobalt or iron atom, such as R4 and R5, the functional group should not coordinate with the metal atom more strongly than the groups in the compounds containing R4 and R5 , which are shown as coordinating for the metal atom, ie they must not displace the desired coordinating group. • "Alkyl aluminum compound" means a compound in which at least one alkyl group is attached to an aluminum atom. Other groups such as the alkoxide, the hydride, and the halogen can also be attached to the aluminum atoms in the compound. • "Neutral Lewis base" means a compound which is not an ion, which can act as a Lewis base. Examples of such compounds include ethers, amines, sulfides, and organic nitriles. • "Cationic Lewis acid" means a cation which can act as a Lewis acid. The examples of such cations are sodium and silver cations. • Relatively non-coordinating anions (or weak coordination) are those anions that are generally referred to in the art in this way, and the coordination capacity of such anions is known and described in the literature, see for example W. Beck., And collaborators, Chem. Rev., vol. 88 p. 1405-1421 (1988), and S. H. Stares, Chem. Rev., vol. 93, p. 927-942 (1993), both of which are included here for reference. Among such anions are those formed from the immediately preceding paragraph and X "aluminum compounds, which include R93A1X", R92A1C1X ", R9A1C12X", and "R9A10X" ", wherein R9 is alkyl, Other non-coordinating anions. Useful include BAF. " { BAF = tetraquis [3], 5-bis (trifluoromethyl) phenyl] borate), SbF6", PF6", and BF ", trifluoromethanesulfonate, p-toluenesulfonate, (RfS02) 2N, and (C6F5) 4B- • By an empty coordination site is meant a potential coordination site that does not have a ligand attached to it Therefore, if an ethylene molecule is in proximity to the empty coordination site, ethylene or another olefin molecule can coordinate with the metal atom. "divalent polyolefin" means a group -Z- which contains one or more repeating units of ethylene and / or of α-olefin • By a ligand that can be added to ethylene, propylene, or an α-olefin, it is understood a ligand coordinated to a metal atom in which an ethylene molecule (or a coordinated ethylene molecule) can be inserted to start or continue a polymerization, for example, this can take the form of the reaction (where L is a ligand) : .CHCH2 M > Note the similarity of the structure on the left-hand side of this equation with the compound (IX) (see below). The compounds useful as ligands here in the iron and cobalt complexes are the diimines of 2,6-pyridinecarboxaldehyde and 2,6-diacylpyridines of the general formula wherein R1, R2 and R3 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group, R4 and R5 are each independently hydrogen, hydrocarbyl, and an inert or substituted hydrocarbyl functional group, and R6 and R7 are aryl or substituted aryl. (IV) can be done by the reaction of a compound of the formula (SAW) with a compound of the formula H2NR6 or H2NR7, wherein R1, R2 and R3 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group, R4 and R5 are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl, R4 and R5 are each hydrocarbyl or substituted hydrocarbyl, and R6 and R7 are aryl or substituted aryl. These reactions are often catalyzed by carboxylic acids, such as formic acid. The preferred compounds of the formula (IV) and the compounds in which (IV) is a ligand are those of the compound (III) [Note that (III) is a subset of (IV)], if present in the compounds such as (I), (II), (IV), (VII), (IX) and (XII). In (III), and therefore in (I), (II), (IV), (VII), (IX) and (XII) corresponding to the formula of (III), it is preferred that: R1, R2 and R3 are hydrogen; and / or R1, R2: RJ are hydrogen and R 2 is trifluoromethyl; and / or R9, R10, R11, R14, R15 and R16 are each independently halogen, alkyl containing 1 to 6 carbon atoms, or hydrogen, and it is more preferred that each of these is hydrogen; and / or R10 and R15 are methyl; and / or R8 and R13 are each independently halogen, phenyl or alkyl containing 1 to 6 carbon atoms, and it is especially preferred that each of R8 and R13 is alkyl containing 1-6 carbon atoms and is more preferred than R8 and R13 are methyl; and / or R12 and R17 are each independently halogen, phenyl, hydrogen, or alkyl containing 1 to 6 carbon atoms, and it is especially preferred that each of R12 and R17 are alkyl containing 1-6 carbon atoms, and it is more preferred that R12 and R17 are methyl; and / or R4 and R5 are each independently halogen, thioalkyl, hydrogen or alkyl containing 1 to 6 carbon atoms, and it is especially preferred that R4 and R5 are each independently hydrogen or methyl, and / or R8, R10, R13 , R15 and R17 are hydrogen, and R9, R11 R14, and R16 are hydrocarbyl or substituted hydrocarbyl. Also in (III), and therefore in (I), (II), (IV), (VII), (IX) and (XII) that correspond to • the formula of (III), it is preferred that: R6 be R 'be R8 and R13 are each independently hydrogen, 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; R 2 R x are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group; and provided that any two of R8, R9, R10, R11, R12, R13, R14, R15, R16 and R17 that are neighbors to each other, taken together, form a ring. The specific preferred compounds (III) [and also in (I), (II), (IV), (VII), (IX) and (XII)] are: R1, R2, R3, R9, R11, R14 and R16 they are hydrogen, and R 4, R 5, R 8, R 10, R 12, R 13, R 15 and R 17 are methyl; R1, R2, R3, R9, R10, R11, R14, R15 and R16 are hydrogen, R8 and R13 are chloro, and R4, R5, R12 and R17 are methyl; R1, R2, R3, R9, R10, R11, R12, R14, R15, R16 and R17 are hydrogen, R4 and R5 are methyl, and R8 and R13 are phenyl; R1, R2, R3, R4, R5, R9, R10, R11, R14, R15, and R16 are hydrogen, and R8, R12, and R13 and R17 are i-propyl; and R1, R2, R3, R4, R5, R10, R8, R10, R13, R15 and R1 'are hydrogen, and R, 9, rRill, rR >; 14, and, R D 16 are trifluoromethyl. In the polymerization processes described herein, it can be observed from the results that it is preferred that there be at least some spherical crowding caused by the tridentate ligand around the Co or Fe atom. Therefore, it is preferred that the groups near the atom metallic are relatively large. It is relatively simple to control spherical crowding if (III) is the tridentate ligand, since the control of spherical crowding can be achieved simply by controlling the size of R8, R12, R13 and R16. These groups can also be part of the fused ring systems, such as 9-anthracenyl. In the first polymerization process it is preferred that X is chloro, bromo and tetrafluoroborate. It is also preferred that M is Fe [II] or Fe [III]. In the first polymerization process described herein a cobalt or iron [II] complex is contacted with ethylene, an α-olefin and a neutral Lewis acid W capable of subtracting X ", the hydride or the alkyl of (II) ) to form a weakly coordinating anion, and must alkylate or be able to add a hydride ion to the metal atom, or an additional alkylating agent or an agent capable of adding a hydride anion to the metal atom must be present. Neutral Lewis is originally discharged (ie, is not ionic.) Suitable neutral Lewis acids include SbF5, Ar3B (where Ar is aryl), and BF3, Suitable cationic Lewis acids or Bronsted acids include NaBAF , silver trifluoromethanesulfonate, HBF4, or [C6H5N (CH3) 2] + [B (C6F5) 4] ". In those cases in which (II) (and similar catalysts which require the presence of a neutral Lewis acid or a Bronsted or cationic Lewis acid, do not contain an alkyl or hydride group already attached to the metal atom, the neutral Lewis acid or a Bronsted or cationic Lewis acid also alkylates or adds a hydride to the metal or a separate alkylating or hydrating agent is present, ie, causes an alkyl or hydride group to become bound to the metal atom It is preferred that R20 contains 1 to 4 carbon atoms, and it is more preferred that R20 is methyl or ethyl, for example, aluminum alkyl compounds (see the next paragraph) can rent (II). However, not all aluminum alkyl compounds can be Lewis acids strong enough to subtract X ~ or an alkyl group of the metal atom. In this case a Lewis acid separated strong enough to do the subtraction or subtraction must be present. A preferred neutral Lewis acid, which can alkylate the metal, is a selected alkyl aluminum compound, such as R193A1, R19A1C12, R192A1C1, and "R19A10" (alkylaluminoxanes), wherein R19 is alkyl containing from 1 to 25 atoms of carbon, preferably 1 to 4 carbon atoms. Suitable aluminum alkyl compounds include methylaluminoxane (which is an oligomer with the general formula [MeA10] n), (C2H5) 2A1C1, C2HsAlCl2, and [(CH3) 2CHCH2] 3A1. Metal hydrides such as NaBH 4 can be used to bind the hydride groups to the metal M. In the second polymerization process described herein a cobalt or iron complex of (I) is added to either the polymerization process or formed in situ in the process. Indeed, more than one such complex can be formed during the course of the process, for example the formation of an initial complex and then the reaction of this complex to form a polymer with active ends containing such a complex. Examples of such complexes which can be initially formed in situ include (VII) (XII) wherein R1 to R7, and M are as defined above, T1 is hydride or alkyl or any other anionic ligand in which ethylene or an α-olefin can be inserted, and is a neutral ligand capable of being displaced by ethylene , "propylene" or an α-olefin, or a vacant coordination site, the "parallel lines" are an ethylene molecule coordinated to the metal, and Q is a relatively non-coordinating anion. Complexes can be added directly to the process or can be formed in situ. For example, (VII) can be formed by the reaction of (II) with a neutral Lewis acid such as an aluminum alkyl compound. Another method of forming such a complex in situ is to add a suitable iron or cobalt compound such as iron [II] acetylacetonate, (I) and an aluminum alkyl compound. Other metal salts in which acetylacetonate-like anions are present, and which can be removed by reaction with Lewis or Bronsted acid. For example, metal halides and carboxylates (such as acetates) can be used, particularly if they are slightly soluble in the process medium. It is preferred that these metal precursor salts are at least somewhat soluble in the process medium. After the polymerization has begun, the complex may be in a form such as (IX) wherein R1 to R7, M, and Q are as defined above, and P is a divalent polymer group containing repeating units derived from ethylene and / or propylene and / or an α-olefin, and T2 is a final or extreme group, for example the groups listed for T1 above. Those skilled in the art will note that (IX) is essentially a polymer that contains a so-called living or active end. It is preferred that M be in an oxidation state +2 in (VII), (VIII) and (IX). The compounds such as (VII), (IX) and (XII) may or may not be stable by departing from an environment similar to that of the polymerization process, but they may be detected by NMR spectroscopy, particularly one or both of 1H and 13C NMR, and particularly at lower temperatures. Such techniques, especially for the "intermediates" of polymerization of these types, are already known, see for example World Patent Application 96/23010, especially Examples 197-203, which is included herein for reference. (VII), (IX) and (XII) can also be used, in the absence of any "co-catalysts" or "activators" to polymerize ethylene in a third polymerization process. Except for the ingredients in the process, the process conditions for the third process, such as temperature, pressure, polymerization medium, etc., may be the same as for the first and second polymerization processes and the preferred conditions for these processes are also preferred for The third polymerization process. In all the polymerization processes here, the temperature at which the copolymerization of the ethylene is carried out is from about -100 ° C to about +200 ° C, preferably from about -60 ° C to about 150 ° C, more preferably about -50 ° C to about 100 ° C. For the copolymerization one or more α-olefins of the formula H2C = CHR21 can be used. It is preferred that R21 has 1 to 18 carbon atoms, more preferably 2 to 8 carbon atoms, and / or that R21 is n-alkyl. Since ethylene is polymerized considerably faster than propylene and most of the α-olefins by these catalysts, in order to obtain substantial incorporation of the α-olefin (s), the ethylene concentration in the polymerization must be relatively low compared with the concentration of propylene and α-olefin (s). This will more frequently encompass the use of ethylene at a low partial pressure, preferably less than 1.0 MPa, more preferably less than 500 kPa, and especially preferably less than 300 kPa (all of these partially ethylene pressures are absolute partial pressures) . If the α-olefin is a gas, its partial pressure must preferably be relatively high. If the α-olefin is used in the liquid phase, its liquid concentration must preferably be relatively high. The NMR analysis of the product copolymers shows that the final groups are both saturated and unsaturated (olefinic), although the saturated end groups usually exceed the unsaturated end groups. It is suspected that saturated end groups can arise through initiation and chain transfer involving the aluminum alkyl compounds present in the polymerization. The unsaturated end groups are believed to arise by means of a mechanism of the ß-hydride removal type. A small proportion of the olefinic ends appear to be internal olefins, but most of the olefinic ends are usually α-olefins (terminal olefins). It is preferred that the product copolymer have at least 0.5 mole percent (total), more preferably 0.75 mole percent (total), especially preferably 1 mole percent (total), and highly preferable at least about 2 mole percent (total) of the α-olefin (s) incorporated into the product copolymer. When l-hexene is a comonomer, the percentage incorporated against the short chain branches, assuming that all of such branches are butyl, is shown in the following Table.

In the copolymers of ethylene and H2C = CHR21 produced here the polymer will contain ramifications of -R21 and methyl branches. The total amount of H2C = CHR21 is taken as the total of the branches of -R21 in the polymer, calculated according to a suitable formula, for example branches per 1000 carbon atoms or the mole percent of H2C = CHR21 incorporated. It is believed that the methyl branches in the copolymer are associated with the end groups (but not the end groups themselves). For example, the extreme groups associated with the methyl branches are 'CH2CH (CH3) CH2CH2CH3 and CH2CH (CH3) CH2CH2CH2CH3 they are the groups associated with the methyl branching for 1-pentene and 1-hexene respectively (and similar structures for the higher and lower homologs), where "~" is the rest of the polymer chain. Such groups are detectable by 13 C-NMR because the methyl branches near the ends of the chain are somewhat different than the additional methyl branches in the interior of the polymer chain, see for example the Examples herein. Note that the group beyond the methine carbon atom (towards the end of the chain) is actually -R21. In other words, the methyl branching is fixed to the same carbon atom as a -R21 group. None of all the polymer chains have such chain ends, but usually at least some of them are present in these copolymers.

A preferred monomeric combination is ethylene and one or more olefins of the formula H2C = CHR21. During the polymerization process frequently some or most of the olefin comonomer H2C = CHR21 will remain unused in the polymerization. The test of this unused comonomer at the end of the polymerization process shows that it usually remains essentially unaltered (not isomerized), so that it can be recovered and recycled to the polymerization, if desired. This recycling can be carried out without purification, or the comonomer can be purified by being recycled to the polymerization, such as by distillation. The polymerization processes here can be operated in the presence of various liquids, particularly aprotic organic liquids. The catalyst system, ethylene, propylene, α-olefin, and polyolefin can be soluble or insoluble in these liquids, but obviously these liquids should not prevent the polymerization from occurring. Suitable liquids include alkanes, cycloalkanes, selected halogenated hydrocarbons, and aromatic hydrocarbons. Specific useful solvents include hexane, toluene and benzene.

The copolymerizations here can also be carried out initially in the solid state [assuming that (II), (III), (IV) or (VII) are a solid), for example, supporting (II), (III), (IV) or (VII) on a substrate such as silica or alumina or an organic substrate such as a polymer, activating it with Lewis acid (such as W, for example an alkylaluminium compound) or Bronsted acid and exposing it to an olefin The support may also be able to take the place of the Lewis or Bronsted acid, for example an acid clay such as montmorrillonite. Another method of manufacturing a supported catalyst is to initiate a polymerization or at least manufacture an iron or cobalt complex of another olefin or oligomer of an olefin such as l-hexene on a support such as silica or alumina. These "heterogeneous" catalysts can be used to catalyze the polymerization in the gas phase or the liquid phase. The gaseous phase is understood to mean that the monomers are transported to make contact with the catalyst particles while they are in the gas phase. Hydrogen can be used as a chain transfer agent in all of the polymerization processes described herein.

In all of the polymerization processes described herein, oligomers and copolymers of ethylene and / or propylene are made. They may vary in the molecular weight of the oligomers, from oils and waxes of lower molecular weight, to polyolefins of higher molecular weight. A preferred product is a polymer with a degree of polymerization (DP) of about 10 or greater, preferably about 40 or more. By "DP" is meant the average number of repeating units (monomeric) in a polymeric molecule. In the examples, the given pressures are gauge pressures. The methods of the NMR Analysis for the polymeric branching, and the notation used herein to describe the branching as determined by 13C NMR, are found in U.S. Pat. No. 5,880,241 (equivalent to World Patent Application 96/23010), which is hereby included for reference. The synthesis of the diimine ligands and their Co and Fe complexes are found in B. L. Small, et al., J. Am. Chem. Soc., Vol. 120, p. 4049-4050 (1998), and G. J. P. Britovsek, et al., J. Chem. Soc., Chem. Commun., P. 849-850 (1998), both of which are included for reference here. The following abbreviations and terms are used: DSC - Differential scanning calorimetry CG - gas chromatography GPC - gel permeation chromatography HOF - heat of fusion IBAO-0.65 - isobutylaluminoxane produced by the reaction of triisobutylaluminum with 0.65 equivalents of water MMAO- 3A - methylaluminoxane containing some isobutyl groups Mn - number average molecular weight MeOH - methanol PMAÓ - polymethylaluminoxane PMAO-IP - polymethylaluminoxane (Akzo, 12.8 weight percent aluminum in toluene) PDI - weight average molecular weight divided by molecular weight numerical average (Mn) TCB - 1, 2, 4-trichlorobenzene Tm - melting point Example 1 (XIII) In a drying box under a nitrogen atmosphere, (XIII) (8 mg, 0.015 mmol) is weighed into a Schlenk vessel and converted into a suspension in 20 ml of anhydrous toluene. The 1-octene (3 ml, dried by distillation from sodium) is added and the Schlenk container is sealed and removed from the drying box. The vessel was washed well with a stream of ethylene and pressurized at 35 kPa. The PMAO-IP (0.8 ml) was added and the solution turned orange and warmed. After 30 minutes the reaction was reduced by the addition of MeOH. The solid polymer was filtered, washed well with MeOH / 10% HCl, MeOH and finally with acetone and dried under vacuum. Production = 2.7 g of the white polymer. DSC (10 ° C / min, N2); Tm = 123.2 ° C, projection on the peak at 100 ° C. CPG (120 ° C, TCB); Mn = 1500, PDI = 5.6. The reduced melting point (from pure polyethylene) shows the incorporation of the comonomer.

Example 2 In a drying box under a nitrogen atmosphere, (XIII) (7.5 mg, 0.014 mmol) is weighed into a Schlenk vessel and converted into a suspension in 10 ml of anhydrous toluene. The l-hexene (3 ml, dried by distillation from sodium) is added and the Schlenk container is sealed and removed from the drying box. The vessel was washed well with a stream of ethylene and pressurized at 35 kPa. The PMAO-IP (0.8 ml) was added and the solution turned green and warmed. After 30 minutes the reaction was reduced by the addition of MeOH. The solid polymer was filtered, washed well with MeOH / 10% HCl, MeOH and finally with acetone and dried under vacuum. Production = 6.0 g of the white polymer. DSC (10 ° C / min, N2); Tm = 126.3 ° C, projection on the low temperature side of the peak. CPG (120 ° C, TCB); Mn = 2420, PDI = 8.0. The analysis of 13 C-NMR indicated a total of 2-5% in mol of l-hexene incorporation. The branch was > 75 of butyl branches (incorporation 1.2 or 2.1). Branches of amyl and methyl were also observed at low levels. No branching of ethyl or propyl was observed.

Example 3 In a drying box under a nitrogen atmosphere, (XIII) (2.0 mg) was weighed into a vessel and converted into a suspension in 35 ml of l-hexene (Aldrich, 99 +%, filtered through A1203 and it is stored on activated molecular sieves). The container was plugged and removed from the drying box. The PMAO-IP (1.0 ml) is added to 5 ml of anhydrous toluene and placed in an ampoule and removed from the drying box. The l-hexene suspension was placed in a stirred 100 ml Parr® autoclave under nitrogen atmosphere. The stirring was started and the reactor was heated to 50 ° C. The PMAO solution was then added to the reactor with 140 kPa of ethylene. After 10 minutes the reaction was decreased by the addition of MeOH. The solid polymer was filtered, washed well with MeOH / 10% HCl, MeOH and finally with acetone and dried under vacuum. Production = 7.8 g of white polymer. DSC (10 ° C / min, N2); Tm = 102.0 ° C, with a minor peak at 112.0 ° C. CPG (120 ° C, trichlorobenzene); Mn = 2534, PDI = 2.3. Analysis of 13 C-NMR (5 weight percent in TCB, 120 ° C) indicated a total of 3.9 mol% of l-hexene incorporation. Of this, the majority resulted from butyl ramifications (1.2 or 2.1 incorporation). The trace amounts of the amyl and methyl branches were also observed. No branching of either ethyl or propyl was observed. The observed MRI is subsequently given together with the assignments. The assignments of D, E and F are shown in the back structure, with "P" representing the rest of the polymer chain.

Example 4 In a drying box under a nitrogen atmosphere, (XIII) (6.1 g mg, 0.011 mmol) was weighed into a Schlenk vessel and converted into a suspension in 10 ml of anhydrous toluene. The l-hexene (5 ml, dried by distillation from sodium) and the anhydrous toluene (15 ml) were added and the Schlenk container is sealed and removed from the drying box. The vessel was cooled to 0 ° C and then washed well with a stream of ethylene and pressurized to 35 kPa. The PMAO-IP (0.9 ml) was added and the solution turned green and warmed. After 30 minutes the reaction was reduced by the addition of MeOH. The solid polymer was filtered, washed well with MeOH / 10% HCl, MeOH and finally with acetone and dried under vacuum. Production = 2.7 g of the white polymer. DSC (10 ° C / min, N2); Tm = 127.6 ° C, projection on the low temperature side of the peak. CPG (120 ° C, trichlorobenzene); Mn = 2120, PDI = 19.1. Analysis by 13 C-NMR indicated a total of 1.2 mol% of l-hexene incorporation.

Only the methyl and butyl branches were observed (1.2 or 2.1 incorporation).

Comparative Example A In a drying box under a nitrogen atmosphere, (XIII) (7.5 mg, 0.014 mmol) is weighed into a Schlenk vessel and converted into a suspension in 10 ml of anhydrous toluene. The anhydrous toluene (30 ml) is added and the Schlenk container is sealed and removed from the drying box. The vessel was cooled to 0 ° C and washed well with a stream of ethylene and pressurized to 35 kPa. The PMAO-IP (0.9 ml) was added and the solution turned orange and warmed. After 30 minutes the reaction was reduced by the addition of MeOH. The solid polymer was filtered, washed well with MeOH / 10% HCl, MeOH and finally with acetone and dried under vacuum. Production = 1.9 g of the white polymer. DSC (10 ° C / min, N2); Tm = 132.7 ° C. CPG (120 ° C, trichlorobenzene); Mn = 2900, PDI = 19.1.

Example 5 In a drying box under nitrogen, (XIII) (1.8 mg) is placed in l-hexene (25 ml, Aldrich 99 +%, filtered through activated A1203 and stored on activated molecular sieves) in a Hoke cylinder. and it is sealed. The PMAO-IP (0.9 ml) is placed in 2 ml of anhydrous toluene in an ampoule and sealed. The containers were removed from the drying box. The l-hexene suspension was placed in a stirred Parr® autoclave. Ethylene (70 kPa) is added, stirring is started and the mixture is heated to 75 ° C. The PMAO-IP solution is added to the reactor with an additional 160 kPa of ethylene. After 81 minutes the reaction is decreased by the addition of MeOH. The solid polymer is filtered, washed well with MeOH / 10% HCl, MeOH and finally acetone and dried under vacuum. Production = 1.61 g of the white polymer. DSC (10 ° C / min, N2); Tm (2 / o. Heating) = 115.5 ° C. CPG (135 ° C, TCB); Mn = 1090, PDI = 1.8. Analysis by 13 C-NMR indicated a total of 1.4 mol% of l-hexene incorporation. The observed number of short chain branches per 1000 groups of CH2 were methyl 1.9, butyl 7.1 and amyl 1.4.

(XIV) Example 6 In a drying box under nitrogen, (XIV) (6.0 mg) is placed in a Schlenk vessel and anhydrous toluene (5 ml) and l-hexene (10 ml, Aldrich 99 +%, filtered through A1203 are added) activated and stored on activated molecular sieves). The container is sealed and removed from the drying box. The vessel is washed with a stream of ethylene and the PMAO-IP (0.9 ml) is added. After 30 minutes the reaction was reduced by the addition of MeOH / 10% HCl. The solid polymer was filtered, washed well with MeOH / 10% HCl, MeOH and finally with acetone and dried under vacuum. Production = 2.43 g of the white polymer. DSC (10 ° C / min, N2); Tm (2 / o heating) = 123.1 ° C, 109.2 ° C (wide). CPG (135 ° C, TCB); Mn = 1620, PDI = 8.4. Analysis by 13 C-NMR indicated a total of 2.1 mol% of l-hexene incorporation. The observed number of short chain branches per 1000 groups of CH2 was 0.8 methyl, 10.5 butyl and 1.5 amyl.

Example 7 In a drying box under nitrogen, (XIII) (3.0 mg) is placed in a Schlenk vessel and anhydrous toluene (5 ml) and l-hexene (10 ml, Aldrich 99 +%, filtered through activated A203 and stored on activated molecular sieves) are added. The container was sealed and removed from the drying box. The vessel was washed with a stream of ethylene and MMAO-3A (0.45 ml, Akzo, 6.42 wt% Al in heptane) was added. After 30 minutes the reaction is decreased by the addition of MeOH / 10% HCl. The solid polymer was filtered, washed well with MeOH / 10% HCl, MeOH and finally with acetone and dried under vacuum. Production = 1.1 g of the white polymer. DSC (10 ° C / min, N2); Tm (2 / o heating) = 121.0 ° C, -80 ° C (wide). CPG (135 ° C, TCB); Mn = 1507, PDI = 6.6. Analysis by 13 C-NMR indicated a total of 6.4 mol% of l-hexene incorporation. The observed number of short chain branches per 1000 groups of CH2 was methyl 1.9, butyl 30.5 and amyl 0.5. In addition, the isobutyl ends are observed on the polymer (from • the MMAO activator), and in this case the isobutyl ends are not included in the total methyl branching.

Example 8 In a drying box under nitrogen, (XIII) (6.3 mg) is placed in a Schlenk vessel and anhydrous toluene (5 ml) and 1-heptene (10 ml, distilled from Na) are added. The vessel was washed with a stream of ethylene and the PMAO-IP (0.9 ml) was added. After 30 minutes the reaction was reduced by the addition of MeOH / 10% HCl. The solid polymer was filtered, washed well with MeOH / 10% HCl, MeOH and finally with acetone and dried under vacuum. Production = 0.87 g of the white polymer. DSC (10 ° C / min, N2); Tm (2 / o heating) = 122.3 ° C. CPG (135 ° C, TCB); Mn = 2680, PDI = 5.9. Analysis by 13 C-NMR (10% by weight in TCB, 120 ° C) indicated a total of 5.3% in mol of 1-heptene incorporation. The observed number of short chain branches per 1000 groups of CH2 was methyl 2.3 and amyl 24.6. The observed NMR is subsequently provided together with the assignments. The assignments of D, E and F are shown in the back structure, with "P" representing the rest of the polymer chain.

Comparative Example B In a drying box under nitrogen, (XIII) (6.3 mg) is placed in a Schlenk vessel and anhydrous toluene (15 ml) is added. The container is sealed and removed from the drying box. The vessel was washed with a stream of ethylene and the PMAO-IP (0.9 ml) was added. After 30 minutes the reaction was reduced by the addition of MeOH / 10% HCl. The solid polymer was filtered, washed well with MeOH / 10% HCl, MeOH and finally with acetone and dried under vacuum. Production = 1.1 g of the white polymer. DSC (10 ° C / min, N2); Tm (2 / o heating) = 127.2 ° C. CPG (135 ° C, TCB); Mn = 1220, PDI = 9.0. No branching was observed in the 13 C-NMR analysis.

Example 9 In a drying box under nitrogen, (XIV) (6.0 mg) is placed in a Schlenk vessel and anhydrous toluene (5 ml) and 1-heptene (10 ml, distilled from Na) are added. The container was sealed and removed from the drying box. The vessel was washed with a stream of ethylene and the PMAO-IP (0.9 ml) was added. After 30 minutes the reaction was reduced by the addition of MeOH / 10% HCl. The solid polymer was filtered, washed well with MeOH / 10% HCl, MeOH and finally with acetone and dried under vacuum. Production = 0.95 g of the white polymer. DSC (10 ° C / min, N2); Tm (2 / o heating) = 123.4 ° C, 110.6 ° C. CPG (135 ° C, trichlorobenzene); Mn = 2540,? DI = 5.3. Analysis by 13 C-NMR indicated a total of 3.0 mol% of 1-heptene incorporation. The observed number of short chain branches per 1000 groups of CH2 was methyl 0.7, and amyl 14.4.

Comparative Example C In a drying box under nitrogen, (XIV) (6.0 mg) is placed in a Schlenk vessel and anhydrous toluene (15 ml) is added. The container is sealed and removed from the drying box. The vessel was washed with a stream of ethylene and the PMAO-IP (0.9 ml) was added. After 30 minutes the reaction was reduced by the addition of MeOH / 10% HCl. The solid polymer was filtered, washed well with MeOH / 10% HCl, MeOH and finally with acetone and dried under vacuum. DSC (10 ° C / min, N2); Tm (2 / o warming) = 131.2 ° C. CPG (135 ° C, TCB); Mn = 1410, PDI = 20.0. No branching was observed in the 13 C-NMR analysis.

Example 10 In a drying box under nitrogen, (XIII) (6.1 mg) is placed in a Schlenk vessel and anhydrous toluene (5 ml) and 1-pentene (10 ml, filtered through AI2O3 and stored on activated molecular sieves) are added. The container was sealed and removed from the drying box. The vessel was washed with a stream of ethylene and the PMAO-IP (0.9 ml) was added. After 30 minutes the reaction was reduced by the addition of MeOH / 10% HCl. The solid polymer was filtered, washed well with MeOH / 10% HCl, MeOH and finally with acetone and dried under vacuum. Production = 0.82 g of the white polymer. DSC (10 ° C / min, N2); Tm (2 / o heating) = 117.8 ° C, -90 ° C (wide). CPG (135 ° C, TCB); Mn = 1028, PDI = 3.8. Analysis by 13 C-NMR indicated a total of 10.0% in mol of 1-pentene incorporation. The observed number of short chain branches per 1000 groups of CH2 was methyl 6.3, and propyl 50.9. GC analysis of the supernatant indicated a negligible isomerization of unreacted 1-pentene.

Example 11 In a drying box under nitrogen, (XIII) (1.4 mg) is placed in ~ 6 ml of anhydrous toluene in an ampule. The 1-pentene (30 ml, filtered through activated A1203 and stored on activated molecular sieves) anhydrous toluene (5 ml) and PMAO (0.5 ml, Akzo, 10.9% by weight of Al in toluene) are placed in a cylinder of Hoke and seal. The containers were removed from the drying box. The 1-pentene suspension was placed in a stirred 100 ml Parr® autoclave. Ethylene (41 kPa) is added, stirring is started. The catalyst solution is added to the reactor with an additional 0.70 kg / cm2 (10 psi) of ethylene. After 12 minutes the reaction is decreased by the addition of MeOH. The solid polymer is filtered, washed well with MeOH / 10% HCl, MeOH and finally with acetone and dried under vacuum. Production = 1.6 g of white polymer. DSC (10 ° C / min, N2); Tm (2 / o. Heating) = 123.6 ° C. Analysis by 13 C-NMR indicated a total of 0.8% in mol of 1-pentene incorporation.

Example 12 In a drying box under nitrogen, (XIII) (3 mg) is placed in a Schlenk container and anhydrous toluene (5 ml) and 1-pentene (10 ml, filtered through activated Al203 and stored on molecular sieves are added) activated). The container is sealed and removed from the drying box. The vessel was washed with a stream of ethylene and MMAO-3A (0.45 ml, Akzo, 6.42% by weight Al in heptane) was added. After 30 minutes the reaction was reduced by the addition of MeOH / 10% HCl. The solid polymer was filtered, washed well with MeOH / 10% HCl, MeOH and finally with acetone and dried under vacuum. Production = 1.9 g of the white polymer. DSC (10 ° C / min, N2); Tm (2 / o heating) = 128.0 ° C. CPG (135 ° C, TCB); Mn = 1716, PDI = 7.0. The analysis by 13 C-NMR (10 weight percent in TCB, 120 ° C) indicated a total of 4.5% in mol of incorporation of 1-? Entene. The observed number of short chain branches per 1000 groups of CH2 was methyl 2.4, propyl 21.7 and amyl 0.4. Any end groups of isopropyl or isobutyl present due to the initiator are not counted in the total methyl group. The observed NMR is subsequently given together with the assignments. The assignments of A, B, C, D, E and F are shown in the back structure, with "P" representing the rest of the polymer chain.

Example 13 In a drying box under nitrogen, (XIII) (3.0 mg) is placed in a Schlenk container and anhydrous toluene (5 ml) and 1-pentene (10 ml, filtered through activated A1203 and stored on molecular sieves are added) activated). The container was sealed and removed from the drying box. The vessel was washed with a stream of ethylene and AlEt3 (0.3 ml, 0.1M solution in toluene / hexane) and B (C6F5) 3 (0.0146 g in 0.5 ml of toluene) was added. After 30 minutes the reaction was reduced by the addition of 10% MeOH / HCl. The solid polymer was filtered, washed well with MeOH / 10% HCl, MeOH and finally with acetone and dried under vacuum. Production = 0.21 g of the white polymer. DSC (10 ° C / min, N2); Tm (2 / o heating) = 127.6 ° C. Analysis by 13 C-NMR indicated a total of 0.64% in mol of 1-pentene incorporation.

Example 14 In a drying box under nitrogen, (XIII) (3.0 mg) is placed in a Schlenk container and anhydrous toluene (5 ml) and 1-pentene (10 ml, filtered through activated A1203 and stored on molecular sieves are added) activated). The container was sealed and removed from the drying box. The vessel was washed with a stream of ethylene and the IBAO-0.65 (0.45 ml, Akzo, 3.5 wt% Al in toluene) was added. After 90 minutes the reaction was reduced by the addition of MeOH / 10% HCl. The solid polymer was filtered, washed well with MeOH / 10% HCl, MeOH and finally with acetone and dried under vacuum. DSC (10 ° C / min, N2); Tm (2 / o heating) = 115.5 ° C (bimodal). CPG (135 ° C, TCB); Mn = 1957, PDI = 8.9. Analysis by 13 C-NMR (10 weight percent in TCB, 140 ° C) indicated a total of 8.2% in mol of 1-pentene incorporation. The observed number of short chain branches per 1000 groups of CH2 was 3.4 methyl, and propyl 39.0. (The amyl not integrated due to overlap). Any end groups or ends of isopropyl or isobutyl present due to the initiator are not counted in the total of the methyl groups. The assignments of A, B, C, D, E and F are shown in the back structure, with "P" representing the rest of the polymer chain.

Note: The existence of the ramifications of Me implies that these do not arise from the activator.

Example 15 In a drying box under nitrogen, (XIII) (4.5 mg) is placed in a Schlenk vessel and anhydrous toluene (5 ml) and 4-methyl-1-pentene (10 ml, filtered through A1203 and it is stored on activated molecular sieves). The container was sealed and removed from the drying box. The vessel was washed with a stream of ethylene and the PMAO-IP (0.9 ml) was added. After 30 minutes the reaction was reduced by the addition of MeOH / 10% HCl. The solid polymer was filtered, washed well with MeOH / 10% HCl, MeOH and finally with acetone and dried under vacuum. Production = 4.65 g of the white polymer. DSC (10 ° C / min, N2); Tm (2 / o heating) = 121.4 ° C, 100.6 ° C (wide). CPG (135 ° C, TCB); Mn = 1740, PDI = 5.0. Analysis by 13 C-NMR indicated a total of 4.1% in mol of incorporation of 4-methyl-1-pentene.

Example 16 In a drying box under a nitrogen atmosphere, the iron dichloride complex of 2,6-diacetylpyridinbis (2,, 6-trimethylphenylamine) iron (1.5 mg, 2.86 μmol) is weighed in an ampoule and diluted to 10 ml with toluene (Aldrich, 99.8% Anhydrous). A 3 ml aliquot containing 0.45 mg (0.86 μmol) of the catalyst is transferred to the injector vessel with 50 ml of toluene. To a second vessel, 100 ml of 1-octene purified with CaH2 (Aldrich, 98%) were mixed with 2 ml of MMAO-3A (Akzo Nobel). These solutions were transferred by means of pressure to a Parr ® 600 ml autoclave reactor. The polymerization temperature was 120 ° C and the ethylene pressure was 860 kPa, adjusted by a pressure regulator. The polymerization was run for 30 minutes. The temperature of the reaction mixture is reduced with methanol to the reaction mixture. The solid polymer is filtered and washed with acetone. Production = 2.68 g, 'DSC (10 ° C / min, N2); Tm = 126.2 ° C, HOF = 212 J / g.

Example 17 In a drying box under a nitrogen atmosphere, a 3 ml aliquot of the same storage solution of Example 16 is diluted with 50 ml of toluene and transferred to the injector vessel. To the second vessel, 80 ml of 1-octene purified with CaH2 (Aldrich, 98%) was mixed with 2 ml of MMAO-3A (Akzo Nobel). These solutions were transferred by means of pressure to a Parr ® 600 ml autoclave reactor. The polymerization temperature was 60 ° C and the ethylene pressure was 860 kPa, adjusted by a pressure regulator. The polymerization was run for 30 minutes. The temperature of the reaction mixture is reduced with methanol to the reaction mixture. The solid polymer is filtered, washed with acetone, and dried under vacuum. Production = 38.9 g, DSC (10 ° C / min, N2); Tm = 132.7 ° C, HOF = 226 J / g.

Example 18 In a drying box under a nitrogen atmosphere, the iron complex dichloride of 2,6-diacetylpyridinbis. { (3,5-trifluoromethyl) phenylamine} ) Iron is weighed (6 mg, 9.7 μmol) and diluted to 100 ml with toluene (Aldrich, 99.8% Anhydrous) and seeded with 20 drops of methylene chloride (Aldrich). To this solution, 5.6 ml of MMA0-3A (Akzo Nobel) are added. This catalyst solution is transferred by means of a cannula to a feed container of a catalytic pump. The pumping speed was constant for 15 minutes, leading to 3.8 mg of the catalyst used. For the comonomer, 85 ml of the l-hexene purified by CaH2 (Aldrich, 99%) were transferred to the reactor through a feed vessel. A 500 ml Zipperclave® reactor was charged with 165 ml of hexane (Aldrich, anhydrous, 95% +). The polymerization was carried out at 50 ° C and 1.01 MPa of the ethylene pressure. After 30 minutes, the reaction is decreased with methanol. The solid polymer was filtered, washed with acetone and dried under vacuum. Production = 1.4 g, DSC (10 ° C / min, N2); Tm = 126.6 ° C, with a projection at approximately 118 ° C. HOF = 194 J / g. CPG PM = 11345, PDI = 7.44.

Comparative Example Example 18 above was repeated with the same solution of the iron complex available in the feed container of the catalyst pump. No comonomer was added to this example. The pumping rate of the catalyst was constant during the first 15 minutes of the run, leading to 2.3 mg of the catalyst used. A 500 ml Zipperclave® reactor was charged with 250 ml of hexane (Aldrich, anhydrous, 95%). The polymerization was carried out at 50 ° C and 1.01 MPa of the ethylene pressure. After 30 minutes, the reaction is reduced with methanol. The solid polymer is filtered, washed with acetone and dried under vacuum. Production = 3.4 g, DSC (10 ° C / minute): Tm = 130.3 ° C, HOF = 278 J / g. PM = 14434, PDI = 6.03.

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.

Having described the invention as above, property is claimed as contained in the following

Claims (31)

REIV »DICACIONES

1. A polymerization process, comprising the step of contacting, at a temperature of about -100 ° C to about +200 ° C, a compound of the formula: (II) with ethylene or propylene, and: (a) a first compound W, which is a neutral Lewis acid capable of subtracting or subtracting an X "of M to form WX", WR20 or WH and which are also capable of transferring a alkyl group or a hydride at M, provided that WX "is a weakly coordinating anion, or (b) a combination of a second compound which is capable of transferring an alkyl or hydride group to M and a third compound which is a neutral Lewis acid which is capable of subtracting or subtracting an X "of M to form a weak coordination anion; where: M is Co or Fe; each X is an anion; n is 1, 2 or 3 so that the total number of negative charges on the anion or anions is equal to the oxidation state of an atom of Fe or Co present in di); R1, R2 and R3 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group; R4 and R5 are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl; Rd and R7 are aryl or substituted aryl; R20 is alkyl; and R21 is alkyl; characterized in that the compound of the formula (II), and (a) or (b), is contacted with two or more monomers selected from the group consisting of: (i) ethylene, (ii) propylene and (iii) a olefin, other than propylene, of the formula H2C = CHR21, wherein R21 is an alkyl group, so that a copolymer of said two or more monomers is formed.

2. The process according to claim 1, characterized in that: R6 is R7 is R8 and R13 are each independently hydrogen, 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; R12 and R17 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group; and provided that any two of R8, R9, R10, R11, R12, R13, R14, R15, R16 and R17 that are close together, taken together form a ring.

3. The process in accordance with the • claim 2, characterized in that: R1, R2 and R3 are hydrogen; R9, R10, R11, R14, R15 and R16 are each independently halogen, alkyl containing 1 to 6 carbon atoms, or hydrogen; R8 and R13 are each independently halogen, phenyl or alkyl containing 1 to 6 carbon atoms; R12 and R17 are each independently halogen, phenyl, hydrogen, or alkyl containing 1 to 6 carbon atoms; and R 4 and R 5 are each independently hydrogen or alkyl containing 1 to 6 carbon atoms.

4. The process according to claim 1, characterized in that X is chloride, bromide, tetrafluoroborate, an alkyl group or a hydride.

5. The process according to claim 1, characterized in that the neutral Lewis acid is an aluminum alkyl compound.

6. The process according to claim 5, characterized in that the alkyl and aluminum compound is polymethylaluminoxane.

7. The process according to claim 1, characterized in that M is Fe.

8. The process according to claim 1, characterized in that the compound (II) is supported on a substrate.

9. A polymerization process, comprising the step of contacting, at a temperature of about -100 ° C to about +200 ° C, a complex of Co [II], Co [III], Fe [II] or Fe [ III] of a tridentate ligand of the formula with ethylene or propylene, where: R1, R and R are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group; R4 and R5 are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl; R6 and R7 are aryl or substituted aryl; and R21 is alkyl; and provided that an atom of Co [II], Co [III], Fe [II] or Fe [III] is also bound to it in an empty coordination site or a ligand that can be displaced by ethylene, and a ligand which can be added to the ethylene, characterized in that the complex is contacted with two or more monomers selected from the group consisting of: (i) ethylene, (ii) propylene and (iii) an olefin, different from propylene, of the formula H2C = CHR21, wherein R21 is an alkyl group, so that a copolymer of said two or more monomers is formed.

10. A process according to claim 9, characterized in that: R6 is R 'is R8 and R13 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group; R9, R10, R11, R14, R1S and R16 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group; R12 and R17 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group; and provided that any two of R8, R9, R10, R11, R12, R13, R14, R15, R16 and R17 that are neighbors to each other, taken together form a ring.

11. The process according to claim 10, characterized in that: R1, R2 and R3 are hydrogen; R9, R10, R11, R14, R15 and R16 are each independently halogen, alkyl containing 1 to 6 carbon atoms, or hydrogen; R8 and R13 are each independently halogen, phenyl or alkyl containing 1 to 6 carbon atoms; R12 and R17 are each independently halogen, phenyl, hydrogen, or alkyl containing 1 to 6 carbon atoms; and R4 and R5 are each independently halogen, thioalkyl, hydrogen or alkyl containing 1 to 6 carbon atoms.

12. The process according to claim 9, characterized in that the complex is a complex of Fe [II] or Fe [III].

13. The process according to claim 9, characterized in that said complex is supported on a substrate.

14. A polymerization process, comprising the step of contacting, at a temperature of about -100 ° C to about +200 ° C, ethylene or propylene, and a compound of the formula: (VII) (IX) where M is Co or Fe; R1, R2 and R3 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group; R4 and R5 are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl; R € and R 7 are aryl or substituted aryl; R21 is alkyl; T1 is hydride or alkyl or any other anionic ligand in which ethylene or an α-olefin can be inserted; And it is a neutral ligand capable of being displaced by ethylene or a vacant coordination site; Q is a relatively non-coordinating anion; P is a divalent polyolefin group; and T2 is an end or end group, characterized in that the compound of the formula (VII), (XII) or (IX) is contacted with two or more monomers selected from the group consisting of: (i) ethylene, (ii) propylene and (ii) an olefin, other than propylene, of the formula H2C = CHR21, wherein R21 is an alkyl group, so that a copolymer of said two or more monomers is formed.

15. The process according to claim 14, characterized in that the compound is (VII).

16. The process according to claim 14, characterized in that the compound is (IX).

17. The process according to claim 14, characterized in that the compound is (XII).

18. The process according to claim 14, characterized in that: R6 is R7 is R and R, 13 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group; R% Rio ?, R > ? 1? 1, R14, R15 and R16 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group; R12 and R17 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group; and provided that any two of R8, R9, R10, R11, R12, R13, R14, R15, R16 and R17 that are neighbors to each other, taken together form a ring.

19. The process according to claim 18, characterized in that: R1, R2 and R3 are hydrogen; R9, R10, R11, R14, R15 and R16 are each independently halogen, alkyl containing 1 to 6 carbon atoms, or hydrogen; R8 and R13 are each independently halogen, phenyl or alkyl containing 1 to 6 carbon atoms; R 2 R are each independently halogen, phenyl, hydrogen, or alkyl containing 1 to 6 carbon atoms; and R 4 and R 5 are each independently hydrogen or alkyl containing 1 to 6 carbon atoms.

20. The process according to claim 14, characterized in that M is Fe.

21. The process according to claim 14, characterized in that the compound (VII), (XII) or (IX) is supported on a substrate.

22. The process according to any of claims 1-21, characterized in that the ethylene is present.

23. The process according to claim 22, characterized in that the ethylene is present and the propylene is not present.

24. The process according to claim 23, characterized in that R21 is n-alkyl.

25. The process according to claim 22, characterized in that ethylene is present at a partial pressure of ethylene of less than 1 MPa.

26. The process according to claim 25, characterized in that the partial pressure of the ethylene is less than 500 kPa.

27. A copolymer of ethylene and one or more olefins of the formula H2C = CHR21, characterized in that the copolymer has methyl branches and branches of -R21, and where the total of the branches indicate an incorporation of H2C = CHR21 of at least 0.5 by cent in mol.

28. The copolymer according to claim 27, characterized in that the incorporation is at least 1 mol percent.

29. The copolymer according to claim 27 or 28, characterized in that each of the branches of the methyl is attached or attached to a carbon atom, and a group -R21 is also attached or attached to the carbon atom.

30. The copolymer according to claim 27 or 28, characterized in that R21 is the n-alkyl.

31. The copolymer according to claim 29, characterized in that R21 is n-alkyl.