Method for production of higher alpha-olefins and/or alkyl-branched alpha-olefins and composition based on the same

FIELD: petroleum chemistry.

SUBSTANCE: claimed method includes oligomerization of one or more alpha-olefins with ethylene in presence of metal-containing catalytic system, using one or more bisaryl pyrimidine-MXa complex and/or one or more [bisaryl pyrimidine-MYpLb+]q- complex. Process is carried out at ethylene pressure less than 2.5 MPa.

EFFECT: method for production of target product of increased yield.

10 cl, 1 tbl, 3 dwg, 17 ex

 

The present invention relates to a method of cooligomerization ethylene and alpha-olefins and to the compositions of the products obtained in this invention.

There are various ways of getting higher linear alpha-olefins (for example, D. Vogt, Oligomerisation of ethylene to higher α-olefins in Applied Homogeneous Catalysis with Organometallic Compounds " Ed. B. Cornils, W. A. Herrmann Vol. 1, Ch. 2.3.1.3, page 245, VCH 1996).

These commercial methods allow to obtain the distribution of oligomeric products or Poisson, or by the Schulz-Flory. In order to obtain the Poisson distribution, while oligomerization should not occur breakage of the circuit. However, in contrast, in the method of the Schulz-Flory chain termination occurs and it does not depend on chain length. Catalyzed by Ni phase oligomerization of ethylene in the way of getting higher olefins Shell company (SHOP) is a typical example of the way Schulz-Flory.

In the method of the Schulz-Flory usually get a wide range of oligomers, where the content of the fractions of each of the olefin can be determined by calculation on the basis of the so-called K-factor. The K-factor, which indicates the relative proportion of olefinic products, represents a molar ratio [(Cn+2]/[Cn]calculated from the slope of a plot for log[Cnmol.%] depending on n, where n represents the number of carbon atoms in a specific olefin is the first product. The K-factor, by definition, represents the same value for each n. As a result of changes of the ligand and adjust the parameters of the reaction can lead To factor to higher or lower values. Thus, it is possible to manage the process for obtaining a certain set of products with optimized economic profitability.

In WO-A-99/02472 describes new catalysts for the oligomerization of ethylene based on iron, which are characterized by high activity and high selectivity to linear alpha-olefins. Base catalysts are complexes of iron and selected 2,6-pyridinedicarboxylate or selected 2,6-decylpyridinium.

In the present invention, the term "bis(eiliminate)pyridine" or, briefly, "basarilarinizin" is used to describe both classes of ligands.

At the same time pending European patent application No. 00301036.0 same applicants such systems are additionally superior, in particular, with respect to the distribution of oligomeric products.

It has been shown that catalysts based on basarilarinizin-FeCl2have a high reactivity towards ethylene, but as it was found that the reactivity towards other olefins such as propylene or higher alpha-olefins, the lower is several orders of magnitude.

B.L. Small and M. Brookhart described in the work of J. Am. Chem. Soc. 1998, 120, 7143-7144 that the oligomerization of ethylene at a pressure of 400 lb/in2(2.76 MPa) in the presence of a mixture with a volume ratio of 1-pentene to toluene 50:50) as solvent and catalyst on the basis of basarilarinizin-FeCl2resulted in only about 3 mol.% oligomers with an odd number of carbon atoms, thus, shows very high selectivity of this catalyst in the implementation of ethylene in comparison with alpha-olefins.

Additional experiments in this paper with another catalyst based on basarilarinizin-FeCl2showed a higher selectivity for the introduction of ethylene compared with the introduction of alpha-olefins were obtained only traces (<1%) of odd oligomers.

The high selectivity of these catalysts in relation to ethylene was confirmed by studies V.C. Gibson et al., described in Chem. Eur. J. 2000, 6, 2221-2231.

There is therefore nothing surprising in the fact that the use of such catalytic systems was focused on the products and the ways in which the quality of raw materials were ethylene and where, preferably, the products are no or few branches, for example, upon receipt of a linear alpha-olefins.

For oligomerization main one hundred the AI reactions - growth stage circuit and phase of the open circuit is balanced in such a way that the formed products with reduced molecular weight, that is, in other words, the number of products with high molecular weights is minimal.

From a simplified point of view we can assume that the chain growth occurs as a result of the introduction of ethylene into the bonding metal-hydrogen (for the first monomer, leading to metallating compounds) and metal-carbon (for the second monomer and the next).

A common phenomenon is the opportunity to participate in reactions with ties metal-hydrogen and metal-carbon other olefins along with ethylene. In particular, reactivity have monosubstituted alpha-olefins. The result of the reaction is influenced by the structure of the active intermediates, the manner in which alpha-olefins react with them, and the way that educated Metallurgie compounds react further.

In reactions oligomerization of ethylene formation of by-products, such as branched olefins, 2,2-substituted alpha-olefins (olefin vinylidene type) and olefins with internal double bonds, can be easily explained by the existence of these intermediates. It should be obvious that, given the distribution of oligomeric alpha-olefins, obrazu what's oligomerization ethylene, you can get a wide range of products that will result in the loss of quality products and to a waste of valuable ethylene feedstock. However, the catalysts that combine specific reactivity against alpha-olefins with suitability for oligomerization of ethylene, would be of great importance when creating new technologies for the production of alpha-olefins of alternative feedstock or receive (mixtures) alpha-olefin products with special structures designed to achieve the desired properties.

For example, 1-hexene, 1-octene or 1-mission as a result of homologation of 1-butene with ethylene can be assumed for systems that after breakage of the chain start with "1,2"-implementation of 1-butene in a bonding metal-hydrogen (formed after breakage of the chain), but then before the breakage of the circuit does not react significantly with any other olefin than ethylene. Thus, cheap 1-butene produced in the refinery, can be turned into high-value alpha-olefins.

Another interesting possibility is the formation of alternativley alpha-olefins with a well-defined structure of branching, which is a consequence of the properties of the catalyst and the reaction conditions. For example, methylresorufin the alpha-olefins can be obtained, using the system, which, after breakage of the circuit, preferably, start with "2,1"-introduction of the olefin in the bonding metal-hydrogen and which are then in front of the open circuit does not react significantly with any other olefin than ethylene.

In the present invention under "methylresorufin alpha olefin" refers to an olefin formed in the "2,1"-the introduction of alpha-olefin formally link the metal-hydrogen system, and that in the future this system before open circuit does not react significantly with any other olefin than ethylene. Alternatively, this "2,1"-introduction of the olefin in the bonding metal-hydrogen can be explained by the chain termination in the result of the migration of hydrogen to the coordinated olefin with obtaining metal(2-alkyl) compounds as the starting compound for the oligomerization. In the following text, for the sake of simplicity, the presentation will follow the mechanism mentioned first.

Getting8-C16methylresorufin alpha-olefins is of great economic importance, because they can serve as a source of raw materials for the alkylation of benzene, representing thus the source material to get vysokorazvityh surface-active substances on the basis of alkylbenzenesulfonates, and the quality is as feedstock for processes of hydroformylation, leading to vysokorazvityh surface-active substances on the basis of alcohols and their derivatives.

In addition, if, for example, as a "solvent" at the (co)oligomerization of ethylene to use 1-of the mission, only one process will result in a linear 1-alkenes in C4-C10the range, as well as linear and/or branched 1-alkenes in the range of >C12.

Along with products with specific methyl branching economic interest and products with specific ethyl branching. As can be predicted, the preference ethyl branching will be confirmed in catalytic systems, in which the reaction of chain transfer preferably occurs in Monomeric ethylene. In the resulting metallating connections chain growth can take place as a result of implementing any additional ethylene or other olefin co monomer.

In the present invention under "etilizotiurony alpha olefin" refers to an olefin formed in the "1,2"-the introduction of alpha-olefin formally in a bonding metal-ethyl systems, and then after that this system before open circuit does not react significantly with any other olefin than ethylene.

To ascertain whether the place during oligomerizes and ethylene proposed reactions and the formation of the desired molecular structures, as described above, hampered by the fact that the same product can be obtained in more than one way reaction.

For example, linear alpha olefins can be obtained not only by pure oligomerization of ethylene, but also as a result of homologation ethylene smaller alpha-olefin, obtained through "1.2"-implementation.

A more detailed understanding of the products and stages of the reaction can be obtained from experiments on cooligomerization, in which the co monomer is an alpha olefin with an odd number of carbon atoms. The result of the comparison products with odd and even number of carbon atoms and obtain characteristics of the processes of oligomerization of ethylene, which take place in the presence of alpha-olefins with an odd number of carbon atoms allows to obtain information about the implementation of olefins in the product. For example, the oligomerization of ethylene in the presence of 1-Heptene can lead to normal With2nalpha-olefins, and linear odd-numbered alpha olefins starting from 1 nonene,9. The ratio between the amounts of odd and even linear olefins is a measure of the relative reactivity of ethylene and alpha-olefins in the first stage of growth chain in experiments.

Important information regarding the structures (by -) products in the processes of oligomerization of ethylene can get the e l e C conducting the reaction in the presence of a large excess of a specific alpha-olefin, for example, by cooligomerization. This has the effect of simplifying usually the distribution of oligomers due to a single olefin with the same reactivity. As a result, after that become apparent education (side) products due to the implementation of the obtained on the basis of a single co monomer alpha-olefins and the output of well-defined structures.

The characteristics of the data structures to obtain relatively easily, even if present in small quantities, after comparison1The h and13C-NMR spectra of samples with different levels of (by -) products. From literature is known and can be used characteristic NMR resonances for unsaturated end groups in the alpha-olefins, 2,2-disubstituted alpha-olefins (olefin vinylidene type), for a single methyl and ethyl groups along the aliphatic chain.

The presence of 2,2-disubstituted alpha-olefins can be explained by "1,2"-the introduction of alpha-olefin in connection metal-carbon of a growing chain with subsequent chain termination (β-H elimination). The existence of a distribution methylresorufin alpha-olefin corresponds to a growth chain in which the first reaction stage includes "2,1"-in edrene of co monomer formally in the metal hydride to obtain metal(2-alkyl) intermediate compounds, which subsequently undergoes the processes of oligomerization of ethylene. Similarly the existence of a distribution for etilatsetatnyj alpha-olefins can be explained on the basis of this assumption that chain termination occurs as a result of transport of hydrogen in a coordinated Monomeric ethylene with getting metallating compounds as starting materials for the process of oligomerization, in which the first stage is a "1,2"-introduction of the alpha-olefin in this connection, the metal-ethyl, resulting in metal(3-alkyl) intermediate, which subsequently undergoes oligomerization of ethylene. Needless to say that the type of the observed side products should have a similar structure for alpha-olefin co monomer with an odd and an even number of carbon atoms.

Now surprisingly been found that the regulation of the reaction conditions, in particular, when used in the reaction of cooligomerization ethylene suitable olefins in appropriate concentrations and special catalytic systems on the basis of basarili.personele used in the present invention can significantly increase the formation of linear alpha-olefins as a result of homologation using ethylene smaller linearifolia-olefins and education alternativley, in particular methylresorufin and/or etilatsetatnyj, alpha-olefins.

Under "alternativley alpha-olefin in the present invention, preferably, means "metallizovannyj alpha-olefin", "iteratively alpha-olefin or combination thereof.

It should be appreciated that while alkylamine alpha-olefins of the present invention can be obtained by hypothetical mechanisms described above, it is not excluded that the above-mentioned olefins can be obtained and alternative reaction mechanism.

The General structure "alternativley alpha-olefins" is described by the formula below:

C=C[C-C]n[-C]m(R16)-R

where R16=methyl; n=0, 1, 2, and so on; m=1; R=optionally substituted hydrocarbon, preferably containing from 1 to 30 carbon atoms, or R16=ethyl; n=0, 1, 2, and so on; m=0; R=optionally substituted hydrocarbon, preferably containing from 1 to 30 carbon atoms.

The present invention provides a method of obtaining a higher linear alpha olefins and/or alternativley alpha-olefins, which includes cooligomerization one or more alpha-olefins with ethylene in the presence of metalloceramic catalytic system that uses one or more complexes basarilarinizin MXandand/or one or the number of complexes [basarilarinizin-MY p·Lb+][NC-]qand mentioned binaryoperation complexes containing the ligand described by the formula:

where M represents a metal atom selected from Fe or Co; and is 2 or 3; X is a halide, optionally substituted hydrocarbon, alkoxide, amide, or hydride; Y is a ligand, which can allow to pass to the introduction of the olefin; NC-represents gecoordineerde anion; p+q is 2 or 3 in accordance with the formal oxidation state of the above-mentioned metal atom; L is a neutral molecule donor Lewis; b=0, 1, or 2; each of R1-R5independently of the other represents hydrogen, optionally substituted hydrocarbon, an inert functional group, or any two of R1-R3, vicinal to each in relation to one another taken together may form a ring; each Z, which may be identical or different, represents an optionally substituted aromatic hydrocarbon ring; optionally substituted polyaromatic hydrocarbon fragment; optionally substituted heterogeneously fragment or optionally substituted aromatic hydrocarbon ring in combination with the metal, and the above-mentioned long is Ino substituted aromatic hydrocarbon ring π -coordinated with the metal; and the above-mentioned method implemented at a pressure of ethylene, less than 2.5 MPa.

In a preferred implementation of the present invention proposes a method of obtaining higher linear alpha olefins and/or alternativley alpha-olefins, which includes cooligomerization one or more alpha-olefins with ethylene in the presence of metalloceramic catalytic system that uses one or more complexes basarilarinizin MXandand/or one or more complexes [basarilarinizin-MYp·Lb+][NC-]qand mentioned binaryoperation complexes containing the ligand described by the formula:

where M represents a metal atom selected from Fe or Co; and is 2 or 3; X is a halide, optionally substituted hydrocarbon, alkoxide, amide, or hydride; Y is a ligand, which can allow to pass to the introduction of the olefin; NC-represents gecoordineerde anion; p+q is 2 or 3, in accordance with the formal oxidation state of the above-mentioned metal atom; L is a neutral molecule donor Lewis; b=0, 1, or 2; each of R1-R10independently of the other represents hydrogen, optionally substituted hydrocarbo is l, inert functional group, or any two of R1-R3, R6-R10, vicinal to each in relation to one another taken together may form a ring; R6may be taken together with R4with the formation of the ring; R10may be taken together with R4with the formation of the ring; Z represents an optionally substituted aromatic hydrocarbon ring; optionally substituted polyaromatic hydrocarbon fragment; optionally substituted heterogeneously fragment or optionally substituted aromatic hydrocarbon ring in combination with the metal, and mentioned optionally substituted aromatic hydrocarbon ring π-coordinated with the metal; and the above-mentioned method implemented at a pressure of ethylene, less than 2.5 MPa.

In a preferred implementation of the present invention proposes a method of obtaining higher linear alpha olefins and/or alternativley alpha-olefins, which includes cooligomerization one or more alpha-olefins with ethylene in the presence of metalloceramic catalytic system that uses one or more complexes basarilarinizin MXandand/or one or more complexes [basarilarinizin-MYp·Lb+][NC-]qand referred to binaryoperation complexes containing the ligand, described by the formula:

where M represents a metal atom selected from Fe or Co; and is 2 or 3; X is a halide, optionally substituted hydrocarbon, alkoxide, amide, or hydride; Y is a ligand, which can allow to pass to the introduction of the olefin; NC-represents gecoordineerde anion; p+q is 2 or 3 in accordance with the formal oxidation state of the above-mentioned metal atom; L is a neutral molecule donor Lewis; b=0, 1, or 2; each of R1-R5, R7-R9and R12-R14independently of the other represents hydrogen, optionally substituted hydrocarbon, an inert functional group, or any two of R1-R3, R7-R9and R12-R14, vicinal to each in relation to one another taken together may form a ring; R6represents hydrogen, optionally substituted hydrocarbon, an inert functional group, or taken together with R7or R4, forms a ring; R10represents hydrogen, optionally substituted hydrocarbon, an inert functional group, or taken together with R9or R4, forms a ring; R11represents hydrogen, optionally substituted hydrocarbon, an inert functional of the ing group or taken together with R5or R12form a ring; and R15represents hydrogen, optionally substituted hydrocarbon, an inert functional group, or taken together with R5or R14form a ring; and the above-mentioned method implemented at a pressure of ethylene, less than 2.5 MPa.

In one implementation of the present invention used in metalloceramic catalytic system uses one or more complexes basarilarinizin MXandand a second connection, which is able to convey optionally substituted hydrocarbon or hydride group to a metal atom M selected from Fe or Co, and which is also able to detach from the above-mentioned metal atom of the group X-.

In another implementation of the present invention used in metalloceramic catalytic system uses one or more complexes basarilarinizin MXandand a second connection, which is able to convey optionally substituted hydrocarbon or hydride group to a metal atom M selected from Fe or Co, and a third connection, which is able to detach from the above-mentioned metal atom of the group X-.

In the present invention, some terms are used as follows:

Under the "higher" higher linear alpha olefins and higher alkalmazott the military alpha-olefins refers to molecules, containing from 4 to 30 carbon atoms.

Examples of optionally substituted aromatic hydrocarbon ring, and optionally substituted polyaromatic hydrocarbon fragments include phenyl, naphthyl, anthracene, phenantrene and the like and their substituted derivatives.

The term "optionally substituted aromatic hydrocarbon ring in combination with the metal, and mentioned optionally substituted aromatic hydrocarbon ring π-coordinated with the metal includes metallocene fragments and sandwich and metallrente complexes. Thus, a specialist in the relevant field should be appreciated that the metal may not necessarily be additionally π-coordinated with another optionally substituted aromatic hydrocarbon ring, which may be different from optionally substituted aromatic hydrocarbon ring in Z, which is directly related to iminobis a nitrogen atom, and/or coordinated with other ligands, is widely known at the present level of technology. In addition, it should be appreciated that, optionally substituted aromatic hydrocarbon ring in Z, which is directly related to iminobis a nitrogen atom and which is also π-coordinated with the metal may contain in the ring one or a number of the heteroatoms, that is, so that the said optionally substituted aromatic hydrocarbon ring will be an optionally substituted aromatic heterocyclic group. Similarly another optionally substituted aryl group, which may optionally be π-coordinated metal, may contain in the ring one or more heteroatoms. The above-mentioned metal atom in a convenient case may be iron, cobalt, Nickel, chromium, titanium and vanadium. Examples of such links include radical derived from ferrocene, cobaltocene, nickelocene, chromocene, titanocene, vanadocene, bis-π-eenvandaag complex, mono-π-arthritisonline complex and similar heteroaromatics complexes, that is, bis - or mono-π-Tien - or-Perrault or chromium complexes.

The term "heterogeneous" means hydrocarbonous group, optionally containing one or more heteroatoms. Mentioned heteroatoms in heterogeneously group, preferably linked at least two carbons. Preferred heteroatoms are nitrogen, oxygen and sulphur.

Mentioned heterogeneously group may be an optionally substituted aromatic heterocyclic fragment; not necessarily samewe the hydrated polyaromatic heterocyclic fragment; optionally substituted aliphatic heterocyclic fragment or optionally substituted aliphatic heterogeneously fragment.

Examples heterogeneously groups include 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, furyl, thienyl, indanyl, imidazolyl, triazolyl, oxazolyl, isoxazolyl, carbazolyl, triazolyl, benzothiazolyl, thiadiazolyl, pyrimidinyl, pyridyl, pyridazinyl and the like and their substituted derivatives.

Gidrolabilna group: a group that contains only carbon and hydrogen. Unless approved another, the number of carbon atoms, preferably, will be in the range from 1 to 30.

In the present invention, the phrase "optionally substituted hydrocarbon" is used to describe hydrocarbonrich groups, optionally containing one or more "inert" heteroaromatic functional groups. The term "inert" is meant that the functional group is not involved in any significant degree in the process of cooligomerization. Non-limiting examples of such inert groups are fluoride, chloride, silane, stannane, ethers, and amines with the corresponding steric protection, all well known to experts in the relevant field. Mentioned optionally substituted hydrocarbon may include stereoselectivity, secondary and tertiary carbon atom of the group are described below nature.

Inert functional group: group other than optionally substituted hydrocarbide, which is inert in the conditions of implementation of the method. The term "inert" is meant that the functional group to any significant degree is not involved in the process of cooligomerization. Examples of inert functional groups include halide, ethers, and amines, in particular tertiary amines.

Group containing a primary carbon atom group-CH2-R, where R can be hydrogen, optionally substituted hydrocarbon, an inert functional group. Examples of groups containing a primary carbon atom include-CH3- 2H5, -CH2Cl, -CH2Och3, -CH2N(C2H5)2, -CH2Ph.

Group containing a secondary carbon atom group-CH-R2where R may be optionally substituted hydrocarbon, an inert functional group. Examples of groups containing a secondary carbon atom include-CH(CH3)2, -CHCl2, -CHPh2, -CH=CH2, cyclohexyl.

Group containing a tertiary carbon atom: the group-S-R3where R may be optionally substituted hydrocarbon, an inert functional group. Examples of groups containing t is etiony carbon atom, include- (CH3)3, -CCl3- ≡CPh, 1-substituted- (CH3)2(Och3).

By "ligand, which can allow to pass to the introduction of the olefin" refers to a ligand that is coordinated with a metal ion with the formation of such an Association, in which to initiate or continue the reaction cooligomerization can be embedded molecule of ethylene or alpha-olefin. In the complexes [basarilarinizin-MYp·Lb+][NC-]qof the present invention, Y may be a hydride, alkyl or any other anionic ligand, which can allow to pass to the introduction of the olefin.

Under "gecoordineerde anion" means an anion which, essentially, is not coordinated with the metal atom M Coordinarussia anions (NC-), which can suitably be used include voluminous anions, such as tetrakis [3,5-bis(trifluoromethyl)phenyl]borate (BAF-), (C6F5)4B-and anions aluminiumtechnik compounds, including R3AlX-, R2AlClX-, RAlCl2X-and RAlOX-"where R represents hydrogen, optionally substituted hydrocarbon or an inert functional group, and X represents a halide, alkoxide or oxygen.

Specialists in the relevant field should be appreciated is that, in the range of boundary conditions described here and earlier in this document, the substituents R1-R15you can easily choose to optimize the operating characteristics of the catalytic system and its economical application.

The substituents R1-R5, R7-R9, R12-R14can independently from each other to be connected together to form a cyclic structure.

In one implementation of the present invention, each of R1-R5, R7-R9and R12-R14independently of the other represents hydrogen, optionally substituted hydrocarbon, an inert functional group, or any two of R1-R3, R7-R9and R12-R14, vicinal to each in relation to one another taken together may form a ring; R6represents a group containing a primary carbon group containing a secondary carbon or a group containing a tertiary carbon; and with the proviso that:

if R6represents a group containing a primary carbon, none of R10, R11and R15does not represent a group containing a primary carbon, or one or two of R10, R11and R15represent a group containing a primary carbon, and other groups of R10, R11and R1 represent hydrogen;

if R6represents a group containing a secondary carbon, none of R10, R11and R15does not represent a group containing a primary carbon, or a group containing a secondary carbon, or one of R10, R11and R15represents a group containing a primary carbon, or a group containing a secondary carbon, and other groups of R10, R11and R15represent hydrogen;

if R6represents a group containing a tertiary carbon, all groups of R10, R11and R15represent hydrogen; and

any two of R6, R7, R8, R9, R10, R11, R12, R13, R14and R15, vicinal to one another taken together may form a ring.

In yet another implementation of the present invention, each of R1-R5, R7-R9and R12-R14independently of the other represents hydrogen, optionally substituted hydrocarbon, an inert functional group, or any two of R1-R3, R7-R9and R12-R14, vicinal to each in relation to one another taken together may form a ring; R6represents hydrogen, optionally substituted hydrocarbon, inert function of the national group, or, taken together with R7or R4, forms a ring; R10represents hydrogen, optionally substituted hydrocarbon, an inert functional group, or taken together with R9or R4forms a ring together with R7or R4, forms a ring; R11and R15independently from each other represent hydrogen or an inert functional group.

In another implementation of the present invention, each of R1-R5, R7-R9and R12-R14independently of the other represents hydrogen, optionally substituted hydrocarbon, an inert functional group, or any two of R1-R3, R7-R9and R12-R14, vicinal to each in relation to one another taken together may form a ring; R6, R10, R11and R15identical and each of them is selected from fluorine or chlorine.

In another embodiment of the method of the present invention binaryoperation complexes used in this invention contain a ligand described by formula (IV):

where each And1-A6independently represents a carbon, nitrogen, oxygen, or sulfur; a group of atoms

not necessarily the absence of the painted, so1will be directly linked And5; and each of R1-R12, R14-R15and, if, R13independently of the other represents hydrogen, optionally substituted hydrocarbon, an inert functional group, or any two of R1-R15, vicinal to each in relation to one another taken together may form a ring; with the proviso that, if a1-A5and, if available, And6all are carbon, the atoms will be cyclopentadienyls or aryl part π-coordinated metal.

In a preferred implementation of the present invention, in formula (IV) each of R1-R3, R7-R9, R12, R14and, if, R13independently of the other represents hydrogen, optionally substituted hydrocarbon, an inert functional group, or any two of R1-R3, R7-R9, R12-R14, vicinal to each in relation to one another taken together may form a ring; and

a) R6is an inert functional group, or optionally substituted hydrocarbon, and R10, R11and R15independently from each other represent hydrogen or halide; or

b) R11is an inert functional is the group or optionally substituted hydrocarbon, and R6, R10and R15independently from each other represent hydrogen or halide; or

(C) each of R6and R10independently from each other represents an inert functional group, or a group containing a primary or secondary carbon atom, with the proviso that R6and R10not represent both a group containing a secondary carbon atom, and R11and R15independently from each other represent hydrogen or halide; or

d) each of R11and R15independently is an inert functional group, or a group containing a primary or secondary carbon atom, with the proviso that R11and R15not represent both a group containing a secondary carbon atom, and R6and R10independently from each other represent hydrogen or halide; or

e) R6taken together with R7forms a ring, R10represents a group containing a primary carbon atom, an inert functional group, or hydrogen, and R11and R15independently from each other represent hydrogen or halide; or

f) R11taken together with R12forms a ring, R15represents a group containing a primary carbon atom, an inert functional group, or waters of the genus, and R6and R10independently from each other represent hydrogen or halide; or

g) R6and R10taken together with R7and R9accordingly, form a ring, and R11and R15independently from each other represent hydrogen or halide; or

h) R11and R15taken together with R12and R14accordingly, form a ring, and R6and R10independently from each other represent hydrogen or halide.

In the formula (IV), the substituents R1-15in case there are, independently from each other to be associated with the formation of cyclic structures. Examples of such structures include communication, for example, R6c R7with the formation of the base naftilos patterns or tetrahydronaphthalene fragment.

In addition, any specialist, well versed in the basic principles of homogeneous catalysis, easy should be appreciated that in all of the above-mentioned ligands, designed for use in binaryoperation complexes used in the method of the present invention, variations of the substituents R1-5, R7-9and R12-14in the case of their availability, can be chosen in such a way as to improve other desirable properties of the precursors of catalysts and catalytic systems, such as solubility in non-polar solution is the teli or expansion of the range of suitable starting compounds during their synthesis.

Preferred implementations of the present invention using the ligands corresponding to the formula (I), and their derivatives, which contain the following group R:

R1-R3represent hydrogen; and/or R4and R5represent methyl, hydrogen, benzyl or phenyl, preferably methyl, phenyl or hydrogen.

Preferred implementations of the present invention using the ligands corresponding to formula (I), (II), (III) and (IV) and derivatives thereof, which contain the following group R:

R1-R3represent hydrogen; and/or R4and R5represent methyl, hydrogen, benzyl or phenyl, preferably methyl, phenyl or hydrogen.

Preferred options for implementation are the ligands corresponding to (IV), and their derivatives, which contain the following group R:

R1-R3represent hydrogen; and/or

R4and R5represent methyl, hydrogen or phenyl, preferably methyl; and/or the group

no, a1-A5represent carbon atoms, thus forming cyclopentadienide part of ferrocenyl fragment; or

And3represents a nitrogen atom, a group

the lack is, and1And2And4And5represent carbon atoms, thus forming 1-pyrrolidine ring; and/or

the combination of orthogonality, in which R6represents methyl, ethyl, isopropyl, phenyl, tertiary butyl or associated with R7with the formation of naftilos structure; R10represents hydrogen, fluoride, or chloride; R11and R15independently of one another represent hydrogen, fluoride or chloride, and/or

the combination of orthogonality, in which R6and R10independently of one another represent methyl, ethyl or connected with R7and R9accordingly, with the formation of anthracene structure, and preferably, R6and R10represent methyl; R11and R15independently of one another represent hydrogen, fluoride, or chloride.

Particularly preferably, if the formula (IV) R11and R15independently from each other represent hydrogen or fluoride.

Preferred ligands include:

the ligand described by formula (II), where R1-R3represent hydrogen; R4and R5represent methyl; R6, R8, R10represent methyl; R7, R9represent hydrogen, and Z is a 1-pyrrolyl;

the ligand described by formula(II), where R1-R3represent hydrogen; R4and R5represent methyl; R6, R8, R10represent methyl; R7and R9represent hydrogen, and Z represents a ferrocenyl;

the ligand described by formula (III), where R1-R3represent hydrogen; R4and R5represent methyl; R6, R8and R10represent methyl; R7and R9represent hydrogen; R11and R15represent hydrogen; R12and R14represent hydrogen; and R13represents tert-butyl;

the ligand described by formula (III), where R1-R3represent hydrogen; R4and R5represent methyl; R6and R7taken together form a six-membered aromatic ring; R8and R10represent hydrogen; R9represents hydrogen; R11and R15represent hydrogen; R12and R14represent hydrogen; and R13represents tert-butyl;

the ligand described by formula (III), where R1-R3represent hydrogen; R4and R5represent methyl; R6represents tert-butyl; R7-R10represent hydrogen; R11and R15represent hydrogen; Rsub> 12and R14represent hydrogen; and R13represents tert-butyl;

the ligand described by formula (III), where R1-R3represent hydrogen; R4and R5represent methyl; R6, R8and R10represent methyl; R7and R9represent hydrogen; R11represents fluorine; and R12-R15represent hydrogen;

the ligand described by formula (III), where R1-R3represent hydrogen; R4and R5represent methyl; R6represents tert-butyl; R7-R10represent hydrogen; R11, R13and R15represent hydrogen; and R12and R14represent methyl;

the ligand described by formula (III), where R1-R3represent hydrogen; R4and R5represent methyl; R6and R10represent fluorine; R7-R9represent hydrogen; R12and R15represent methyl; and R11, R13and R14represent hydrogen;

the ligand described by formula (III), where R1-R3represent hydrogen; R4and R5represent methyl; R7-R9and R12-R14represent hydrogen; and R6, R10, R11and R15not only is jut a fluorine; and

the ligand described by formula (III), where R1-R3represent hydrogen; R4and R5represent methyl; R7-R10represent hydrogen; R6represents methyl; R11-R14represent hydrogen; and R15represents methyl.

In the complex basarilarinizin MXandX in a convenient case can be a halide, preferably chloride.

In a preferred embodiment, the implementation of complex basarilarinizin MXandthe atom of the metal is Fe, and "a" is 2. In another preferred embodiment, the implementation of the atom, M represents Fe, and "a" is equal to 3.

Compounds that are capable of transmitting to the metal atom M is optionally substituted hydrocarbon or hydride group and which is also able to detach from the metal atom M group X-include aluminiumallee compounds such as alkylalkoxy and alkylhalogenide. The preferred connection is methylalumoxane.

Compounds that are capable of transmitting to the metal atom M is optionally substituted hydrocarbon or hydride group include aluminiumallee connections, including alkylalkoxy, liteally compounds, Grignard reagents, olomoucine and cinchocaine connection.

Compounds which way the s to detach from the metal atom M group X -include a strong neutral Lewis acid, such as SbF5BF3and Ar3B, where Ar represents an aryl group, very dilatory in its electronic density, such as C6F5or 3,5-(CF3)2C6H3.

A molecule is a neutral donor Lewis - is a compound that in an appropriate case can serve as the Foundation Lewis, such as ethers, amines, sulfides and organic NITRILES.

The use of molecules donors (Lewis bases, such as triethylamine or 2,6-di-tert-butylpyridinium, and/or molecules of acceptors (Lewis acid), such as diethylzinc can have a positive effect on the selectivity of the method cooligomerization ethylene.

In addition, a Lewis acid such as triisobutylaluminum (TIBA), can improve the continuous version of cooligomerization of ethylene using a catalyst based on Fe or Co, making it possible to obtain a stable and transparent solutions of precursors of catalysts, in contrast to the activated using MAO and solubilizing solutions of precursors of catalysts, which can become cloudy upon standing.

In the complex [basarilarinizin-MYp·Ln+][NC-]qcorresponding to the present invention, L may predstavljati a neutral molecule donor Lewis, can be substituted ethylene, or vacant coordination position.

In the complex [basarilarinizin-MYp·Ln+][NC-]qcorresponding to the present invention, the metal atom M, preferably, is Fe, and the formal oxidation state of the above-mentioned metal atom may be equal to 2 or 3.

The catalytic system can be formed by mixing together the complex and optional additional compounds, preferably in a solvent such as toluene or isooctane.

The molar ratio of the complex MHn, the second connection and optional third connection in the present invention is not limited.

There is the possibility of increasing the flexibility of reactions cooligomerization in the use of a mixture of one or more catalyst systems of the present invention.

In the reaction mixture to cooligomerization usually use such amount of the catalytic system, to one mole reacts ethylene and/or alpha-olefin having from 10-4up to 10-9gram atom of the metal M, in particular of metal is Fe[II] or [III].

In case the reaction cooligomerization can be carried out in the temperature range from -100 to 300°preferably in the range from 0 to 200°and more site is preferably in the range from 50 to 150° C.

The reaction cooligomerization preferably carried out at a pressure of ethylene, less than 2.0 MPa (20 bar absolute pressure), and more preferably at a pressure of ethylene in the range from 0.1 MPa (1 bar (absolute pressure)) up to 1.6 MPa (16 bar (absolute pressure)).

Alpha-olefin of comonomer in General is present with a concentration greater than 1 mol·l-1preferably with a concentration of greater than 2.5 mol·l-1and more preferably with a concentration greater than 5 mol·l-1.

Conditions for temperature and pressure, preferably, choose to obtain a set of products with K-factor in the range from 0.40 to 0.90, preferably in the range from 0.45 to 0.90. As considered in the present invention, polymerization occurred when the set of products is characterized by a K-factor greater than 0.9.

The reaction cooligomerization can be carried out in the gas phase or in the liquid phase or in a mixed gas-liquid phase depending on the volatility of olefinic feedstock and products.

The reaction cooligomerization can be carried out in the presence of an inert solvent, which can also act as a carrier for the catalyst and/or olefin feedstock. Suitable solvents include alkanes, alkenes, cycloalkanes and aromatic hydrocarbons.

N the example, solvents that can be used in an appropriate case, include hexane, isooctane, benzene, toluene and xylene.

It was found that suitable are the reaction times in the range from 0.1 to 10 hours depending on the activity of the catalyst. The reaction is preferably carried out in the absence of air or water.

The reaction cooligomerization can be performed in the usual way. It can be done in the reactor mixing, where the reactor mixing continuously add olefins and catalysts or precursors of catalysts and reactants, products, catalysts and unused reactants from the reactor mixing away, separating the products and sending catalysts and unused reagents back for recycling to the reactor mixture.

Alternatively, the reaction can be carried out in a batch reactor, the, where the precursors of catalysts and olefin reactants are loaded into the autoclave, and after completion of the reaction within a reasonable period of time, the products isolated from the reaction mixture by usual method such as distillation.

After a suitable reaction time reaction cooligomerization you can stop in the rapid removal of ethylene from purge to deactivate the catalytic system.

The resulting composition products can content the th linear alpha olefins and/or alkylamine alpha-olefins.

In a preferred implementation, the composition of the products may contain linear alpha olefins and/or methyl-branched alpha-olefins and/or etilatsetatnyj alpha-olefins, that is, for example, where R16represents methyl or ethyl.

The composition of the products of the present invention in General will contain more than 5 wt.%, preferably more than 10 wt.%, more preferably more than 15 wt.%, and most preferably more than 25 wt.% alternativley alpha-olefins in the total weight linear alpha-olefins and alternativley alpha-olefins in the composition of products.

Mentioned linear alpha olefins and/or alkylamine alpha-olefins may have a chain length in the range from 4 to 100 carbon atoms, preferably from 4 to 30 carbon atoms, and most preferably from 4 to 20 carbon atoms.

Olefin products can easily extract by distillation, and then to divide, as it is desirable, using methods of distillation, depending on the intended end use of olefins.

Hereinafter the present invention will be illustrated in the following examples, which in no way should be construed as limiting the scope of the present invention, with reference to the accompanying drawings, where:

figure 1 represents graficheskoe representation for the regression analysis to example 4;

figure 2 is a GC-chromatogram for the product from example 5; and

figure 3 represents the portion of the chromatogram for gas chromatography (GC) of the product from example 9.

General methods and characterization

All operations with the catalytic systems were carried out in nitrogen atmosphere. All used solvents were dried using standard techniques.

Anhydrous toluene (degree of purity 99.8%) (from Aldrich) was dried over molecular sieves 4TH (final water content of approximately 3 million-1).

Ethylene (purity of 99.5%) was cleaned by passing through a column containing molecular sieves 4E and BTS catalyst (BASF), in order to reduce the water content and oxygen to <1 million-1.

1-octene (content of 1-octene 99.8%, and the remaining part is formed 0.1% of 1-hexene and 0.1% 1-mission) and 1-hexadecene (table of contents 1-hexadecene 94,1%; the remaining part is formed of 3.6% 1-tetradecene and 2.3% 1 octadecene) consisted of alpha-olefins SHOP, obtained from Shell Chemicals, and purified by processing primary aluminum oxide and subsequently drying over molecular sieves 4E in nitrogen atmosphere. 1-hepten (content of 1-Heptene 99,3%; the remaining part is formed of Heptene isomers) was obtained from Aldrich and used after drying over molecular sieves 4TH in the atmosphere AZ is the same.

1-aminonaphthalene, 2,6-diacetylpyridine, 3,5-dimethylaniline, 2,5-dimethylaniline, 2,4,6-trimethylaniline, 2-tert-butylaniline, 4-tert-butylaniline, 2,6-diptiranjan, 2-ftoranila and anhydrous ferric chloride(II) available from Aldrich company. 1 - aminopyrrolo acquired the company TCI, Japan.

Ferroceramic received in accordance with a method described in the literature (D. van Leusen and B. Hessen, Organometallics, 2001, 20, 224-226).

In order to assess the distribution of oligomers using gas chromatography (GC), have established the characteristics of the obtained oligomers using a HP 5890 series II and the following conditions for chromatography:

Column: HP-1 (crosslinked methylsiloxane), film thickness=0.25 μm, inner diameter=0.25 mm, length 60 m (according to Hewlett Packard); temperature injection: 325°C; temperature detection: 325°C; initial temperature: 40°C for 10 minutes; the rate of temperature programming: 10,0°C/min; final temperature: 325°With over 41.5 minutes; internal standard: n hexylbenzoyl. The response factors for even linear alpha-olefins relative to n-hexylbenzene (internal standard) were determined using standard calibration mixture. The response factors for the branched alpha-olefins with an even number of carbon atoms, linear and branched alpha-olefins with an odd number the volume of carbon was assumed equal in magnitude current for even linear alpha-olefins with the same or similar number of carbon atoms. Outputs4-C30olefins were obtained from analysis by GC method, the results of which were determined K-factors (linear connections), using regression analysis, generally using10-C28data for linear alpha-olefins. For cooligomerization of Athena/1-octene content of 1-octene was calculated according to the regression analysis for linear alpha-olefins in the range From10-C28. For cooligomerization of Athena/1-hexadecene contents 1-hexadecene was calculated according to the regression analysis for linear alpha-olefins in the range From18-C28.

The relative amount of linear (Lin.) 1-hexene among all hexene isomers and the relative amount of linear (Lin.) 1-dodecene among all isomers dodecene found from the analysis method GC, used as a measure of the selectivity of the catalyst in respect to the education of linear alpha-olefins.

Outputs the branched C10-C30alpha-olefins in the case of cooligomerization of Athena/1-octene or branched C18-C30alpha-olefins in the case of cooligomerization of Athena/1-hexadecene received from the analysis method GC, the results of which were determined K-factors (branched compounds), using regression analysis. If cooligomerization of Athena and 1-Heptene outputs odd LINEST is x and branched C 9-C29alpha-olefins were obtained from analysis by GC method, the results of which were determined by their K-factor for linear connections and their K-factor for the branched compounds, using regression analysis.

The mass ratio alkylresorcinol 1-undecene (undecanol) and alternativley and linear 1-undecanol, the mass ratio alkylresorcinol 1-dodecene (dodecanol) and alternativley and linear 1-dodecene and mass ratio alkylresorcinol 1 eicosene (Aksenov) and alternativley and linear 1-eicosanol defined from the analysis method GC, used as a measure of the selectivity of the catalyst in relation to education alternativley alpha-olefins.

Data NMR spectroscopy was obtained at room temperature using the apparatus Varian with a frequency of 300 or 400 MHz. The classification structures of linear alpha-olefins and by-products were obtained by comparing spectra1The h and13C-NMR samples of the reaction mixture containing various amounts of the various components. The characteristic resonances for olefins and linear and branched aliphatic groups was taken from the literature. For more evidence of the structure where it was deemed necessary, used methods, enabling them to identify connectivity of carbon is the carbon in the structure.

The components of the catalyst

1. Getting chloride complex of 2,6-bis[1-(2-methylphenylimino)ethyl]peridiniales[II] (X).

Complex X received in accordance with the method described in WO-A-99/02472.

2. Getting 2-[1-(2,4,6-trimethylaniline)ethyl]-6-acetylpyridine (1).

In 450 ml of toluene was dissolved 2,6-diacetylpyridine (7,3 g, with 44.8 mmol) and 2,4,6-trimethylaniline (5,74 g, 42,55 mmol). To this solution was added molecular sieves 4E and a small amount of p-toluensulfonate acid (0.22 mmol). The mixture was boiled in a flask under reflux for 16 hours. After filtration the solvent was removed in vacuum. Several kristallizatsii from ethanol gave 3.42 g (28.7 per cent) monoimine (1).

1H-NMR (CDCl3) δ 8,55 (d, 1H, Py-Hm), 8,11 (d, 1H, Py-Hm), 7,92 (t, 1H, Py-Hp), 6.89 in (s, 2H, ArH), 2,77 (s, 3H, Me), and 2.27 (s, 3H, Me), 2,22 (s, 3H, Me)to 1.99 (s, 6H, Me).

3. Getting 2-[1-(2,4,6-trimethylaniline)ethyl]-6-[1-(4-tert-butylbenzylamine)ethyl]pyridine (2).

In 100 ml of toluene was dissolved monoimine (1, 2.8 g, 10 mmol) and 4-tert-butylaniline (1,49 g, 10 mmol). To this solution was added molecular sieves 4E and a small amount of p-toluensulfonate acid (0.1 mmol). After standing the mixture for 5 days when adding an additional amount of molecular sieves 4E mixture was boiled in a flask with reflux condenser in ECENA 2 hours. After filtration the solvent was removed in vacuum. The residue was washed with methanol and recrystallized from ethanol. Output mixed diimine (2) 2.4 g (58%).

1H-NMR (CDCl3) δ 8,42 (d, 1H, Py-Hm), a 8.34 (d, 1H, Py-Hm), 7,86 (t, 1H, Py-Hp), 7,38 (d, 2H, ArH), 6.89 in (s, 2H, ArH), is 6.78 (d, 2H, ArH), 2,42 (s, 3H, Me)to 2.29 (s, 3H, Me), 2,22 (s, 3H, Me), from 2.00 (s, 6H, Me), of 1.34 (s, 9H, But).

4. Obtaining complex chloride 2-[1-(2,4,6-trimethylaniline)ethyl]-6-[1-(4-tert-butylbenzylamine)ethyl]peridiniales[II] (3).

In an inert atmosphere to 420 mg FeCl2(3.3 mmol) in 150 ml dichloromethane was added a solution of 1.5 g diimine (2, 3.6 mmol) in 100 ml of dichloromethane. The mixture was stirred for one week. Educated blue precipitate was isolated using filtration, and dried under vacuum. The output of the complex of iron (3) 1.5 g (84%).

1H-NMR (Cl2CDCDCl2, broad signals) δ 79,3 (1H, Py-Hm), with 77.7 (1H, Py-Hm), 27,0 (1H, Py-Hp), 20,7 (3H, Me), 17,3 (6H, Me), 15,0 (2H, ArH), and 14.3 (2H, ArH), 1,2 (9H, But), -2,6 (3H, MeC=N), -17,9 (2H, o-ArH), -32,1 (3H, MeC=N).

5. Obtaining 2,6-bis[1-(2,6-diftorhinolonom)ethyl]pyridine (4).

In 50 ml of toluene was dissolved 2,6-diacetylpyridine (1,76 g to 10.8 mmol) and 2,6-diferencia (2,94 g of 22.8 mmol). To this solution was added molecular sieves 4E. After standing the mixture for 3 days adding additional quantities forefront of the lar sieves 4E mixture was filtered. The solvent was removed in vacuum. The residue was led from ethanol. Output 4: 1 g (24%).

1H-NMR (CDCl3) δ 8,44 (d, 2H, Py-Hm), of 7.90 (t, 1H, Py-Hp), 7,05 (m, 2H, ArH) of 6.96 (m, 4H, ArH), is 2.44 (s, 6H, Me).19F-NMR (CDCl3) δ -123,6.

6. The chloride complex of 2,6-bis[1-(2,6-diftorhinolonom)-ethyl]peridiniales[II] (5).

In an inert atmosphere in 50 ml of THF was dissolved 493 g diimine (4, of 1.27 mmol). Added FeCl2(162 mg, 1.28 mmol) in 10 ml of THF. After stirring for 16 hours at room temperature the solvent was removed in vacuum. Was added toluene (100 ml). The blue precipitate was isolated using filtration, washed his pentane and dried under vacuum. Allocated 0.5 g (76%) of iron complex 5.

1H-NMR (Cl2CDCDCl2, broad signals) δ 75,5 (2H, Py-Hm), 39,6 1H, Py-Hp), 15,7 (4H, ArH), -11,6 (2H, ArH), -22,4 (6N, MeC=N).19F-NMR (Cl2CDCDCl2) δ -70,3.

7. An alternative option for obtaining a chloride complex of 2,6-bis[1-(2,6-diftorhinolonom)ethyl]peridiniales[II] (5').

In an inert atmosphere to a solution of 260 mg diimine (4, 0.67 mmol) in a mixture solvent consisting of 10 ml of toluene and 6 ml of pentane was slowly added a solution of 60 mg FeCl2(0.47 mmol) in 0.5 ml of ethanol. The resulting blue precipitate was isolated using centrifugation, three times washed it in the toluene and dried under vacuum. The output of the iron complex 5' 210 mg (87%).

1H-NMR (CD2Cl2, broad signals) δ 76,7 (2H, Py-Hm), 37,6 (1H, Py-Hp), 16,8 (4H, ArH), -10,2 (2H, ArH), -20,3 (6H, MeC=N).19F-NMR (CD2Cl2) δ -75.

8. Getting 2-[1-(1-naphthylamine)ethyl]-6-acetylpyridine (6).

In 100 ml of toluene was dissolved 2,6-diacetylpyridine (5.49 g, 33.6 mmol) and 1-aminonaphthalene (4.8 g, a 33.5 mmol). To this solution was added molecular sieves 4E. After standing the mixture for 20 hours at room temperature the mixture was filtered. The solvent was removed in vacuum. The resulting mixture of 2,6-diacetylpyridine, 2,6-bis[1-(1-naphthylamine)ethyl]pyridine and 2-[1-(1-naphthylamine)ethyl]-6-acetylpyridine was dissolved in 50 ml of THF. In the selective complexation with the metal halide was removed dimineralising by-product 2,6-bis[1-(1-naphthylamine) ethyl]pyridine. In an inert atmosphere was added FeCl2(0,79 g, 6,23 mmol). After stirring for 16 hours at room temperature the solvent was removed in vacuum. To the resulting mixture were added toluene (100 ml). The precipitated complex was filtered through a small layer of silicon dioxide to obtain a yellow solution. The solvent was removed in vacuum. Crystallization from ethanol gave 3.25 g of 2-[1 - 1 naphthylamine)ethyl]-6-acetylpyridine(6) (33,6%).

1H-NMR (CDC 3) δ 8,65 (d, 1H, Py-Hm), of 8.15 (d, 1H, Py-Hm), to 7.95 (t, 1H, Py-Hp), 7,87 (d, 1H, ArH), 7,76 (d, 1H, ArH), to 7.64 (d, 1H, ArH), 7,4-7,6 (m, 3H, ArH), PC 6.82 (d, 1H, ArH), and 2.79 (s, 3H, Me), of 2.38 (s, 3H, Me).

9. Getting 2-[1-(1-naphthylamine)ethyl]-6-[1-(4-tert-butylbenzylamine)ethyl]pyridine (7).

In 50 ml of toluene was dissolved monoimine (6, 1,25 g, 4,34 mmol) and 4-tert-butylaniline (0.65 g, 4,34 mmol). To this solution was added molecular sieves (4E). After standing the mixture for 16 hours the mixture was filtered. The solvent was removed in vacuum. The residue was recrystallized from ethanol. Output mixed diimine (7 a purity of 96% according to analysis by NMR) of 0.44 g (24%).

1H-NMR (CDCl3) δ 8,51 (d, 1H, Py-Hm), scored 8.38 (d, 1H, Py-Hm), to $ 7.91 (t, 1H, Py-Hp), 7,86 (d, 1H, ArH), 7,78 (d, 1H, ArH), 7,63 (d, 1H, ArH), 7,4-7,6 (m, 5H, ArH), 6.8 or 6.9 (m, 3H, ArH), 2,43 (s, 3H, Me), is 2.37 (s, 3H, Me), of 1.34 (s, 9H, But).

10. Obtaining complex chloride 2-[1-(1-naphthylamine)ethyl]-6- [1-(4-tert-butylbenzylamine)ethyl]peridiniales[II] (8).

In an inert atmosphere to 130 mg FeCl2(1,03 mmol) in 20 ml dichloromethane was added a solution of 440 mg diimine (7, 1.05 mmol) in 5 ml of dichloromethane. The mixture was stirred for 9 days. Add 10 ml of pentane resulted in the receipt of blue precipitate, which was isolated using centrifugation, and dried in vacuum. The output of the iron complex (8) 480 mg (85%). In the analysis of m is Todd 1H-NMR (Cl2CDCDCl2has been widely signals, the classification of which after that are not conducted.

11. Getting 2-[1-(2-tert-butylaniline)ethyl]-6 - acetylpyridine (9).

In 100 ml of toluene was dissolved 2,6-diacetylpyridine (4,37 g, 26,78 mmol) and 2-tert-butylaniline (4.0 g, 26.8 mmol). To this solution was added molecular sieves (4E). After standing the mixture for 20 hours at room temperature the mixture was filtered. The solvent was removed in vacuum.

The resulting mixture of 2,6-diacetylpyridine, 2,6-bis[1-(2-tert-butylaniline)ethyl]pyridine and 2-[1-(2-tert - butylaniline)ethyl]-6-acetylpyridine was dissolved in 50 ml of THF. In the selective complexation with the metal halide was removed dimineralising by-product 2,6-bis[1-(2-tert-butylaniline)ethyl]pyridine.

In an inert atmosphere was added FeCl2(0,79 g, 6,23 mmol). After stirring for 16 hours at room temperature the solvent was removed in vacuum.

To the resulting mixture were added toluene (100 ml). The precipitated complex was filtered through a small layer of silicon dioxide to obtain a yellow solution. The solvent was removed in vacuum.

Crystallization from ethanol gave 2.8 g of 2-[1-(2-tert-butylaniline)ethyl]-6-acetylpyridine(9) (36%).

1H-NMR (CDCl3) δ 8,48 (d, 1H, Py-Hm/sub> ), 8,10 (d, 1H, Py-Hm),

to 7.93 (t, 1H, Py-Hp), 7,41 (d, 1H, ArH), 7,17 (t, 1H, ArH), 7,07 (t, 1H, ArH), 6,51 (d, 1H, ArH), 2,77 (s, 3H, Me), of 2.38 (s, 3H, Me), of 1.33 (s, 9H, But).

12. Getting 2-[1-(2-tert-butylaniline)ethyl]-6-[1-(4-tert-butylbenzylamine)ethyl]pyridine (10).

In 25 ml of toluene was dissolved monoimine (9, 1.06 g, 3.6 mmol) and 4-tert-butylaniline (0.56 g, 3.75 mmol). To this solution was added molecular sieves (4E). After standing the mixture for 60 hours, the mixture was filtered. The solvent was removed in vacuum. The residue was recrystallized from ethanol. Output mixed diimine (10) 0,81 g (53%).

1H-NMR (CDCl3) δ at 8.36 (d, 1H, Py-Hm), a 8.34 (d, 1H, Py-Hm), 7,88 (t, 1H, Py-Hp), and 7.4 (m, 3H, ArH), 7,18 (t, 1H, ArH), 7,07 (t, 1H, ArH), is 6.78 (d, 2H, ArH), is 6.54 (d, 1H, ArH), 2,42 (s, 3H, Me), of 2.38 (s, 3H, Me), to 1.35 (s, 9H, But), of 1.34 (s, 9H, But).

13. Obtaining complex chloride 2-[1-(2-tert-butylaniline)ethyl]-6-[1-(4-tert-butylbenzylamine)ethyl]peridiniales[II] (11).

In an inert atmosphere to 182 mg FeCl2(1.44 mmol) in 20 ml dichloromethane was added a solution of 640 mg diimine (10, 1.5 mmol) in 10 ml of dichloromethane. The mixture was stirred for 16 hours. Add 20 ml of pentane resulted in the receipt of a blue precipitate. Isolation and drying in vacuum allowed to obtain 650 mg (82%) of iron complex (11).

1H-NMR (CD2Cl2), broad signals) δ 81,9 (1H, P-H m), 77,5 (1H, Py-Hm), 30,4 (1H, Py-Hp), and 16.4 (1H, ArH), 13,8 (2H, ArH), and 6.3 (1H, ArH), 1,5 (N, But), 1,1 (N, But), of-1.0 (3H, MeC=N), is-12.7 (1H, ArH), -21,3 (2H, ArH), -33,1 (3H, MeC=N), -33,7 (1H,-ArH).

14. Getting 2-[1-(2-tert-butylaniline)ethyl]-6-[1-(3,5-dimethylphenylimino)ethyl]pyridine (12).

In 25 ml of toluene was dissolved monoimine (9, 1.13 g, a 3.87 mmol) and 3,5 dimethylaniline (0.5 g, 4,13 mmol). To this solution was added molecular sieves (4E). After standing the mixture for 60 hours, the mixture was filtered. The solvent was removed in vacuum. The residue was recrystallized from ethanol. Output mixed diimine (12) of 0.79 g (52%).

1H-NMR (CDCl3) δ of 8.37 (d, 1H, Py-Hm), 8,32 (d, 1H, Py-Hm), 7,87 (t, 1H, Py-Hp), 7,42 (d, 1H, ArH), 7,18 (t, 1H, ArH), 7,07 (t, 1H, ArH), 6,76 (s, 1H, ArH), is 6.54 (d, 1H, ArH), 6,46 (s, 2H, ArH), is 2.40 (s, 3H, Me), 2,39 (s, 3H, Me), of 2.33 (s, 3H, Me), of 1.36 (s, 9H, But).

15. Obtaining complex chloride 2-[1-(2-tert-butylaniline)ethyl]-6-[1-(3,5-dimethylphenylimino)ethyl]peridiniales[II] (13).

In an inert atmosphere to 187 mg FeCl2(1.48 mmol) in 20 ml dichloromethane was added a solution of 617 mg diimine (12, 1.55 mmol) in 10 ml of dichloromethane. The mixture was stirred for 16 hours. Add 20 ml of pentane resulted in the receipt of a blue precipitate. Cooling to -30°resulted in the receipt of the second portion of the blue precipitate. Isolation and drying in vacuum allowed the floor is icy 660 mg (85%) of iron complex (13).

1H-NMR (CD2Cl2, broad signals) δ 81,5 (1H, Py-Hm), 76,9 (1H, Py-Hm), 37,6 (1H, Py-Hp), 16,1 (1H, ArH), 1,2 (1H, ArH), and 1.0 (9H, But), -2,7 (3H, MeC=N)-5,6 (6H, Me), -11,7 (1H, ArH), -13,5 (1H, ArH), -25,6 (2H, ArH), -35,7 (3H, MeC=N), -37,4 (1H,-ArH).

16. Getting 2-[1-(2,4,6-trimethylaniline)ethyl]-6-[1-(2 - ftorpirimidinu)ethyl]pyridine (14).

In 50 ml of toluene was dissolved monoimine (1, 1.0 g, of 3.57 mmol) and 2-ftoranila (398 mg, of 3.57 mmol). To this solution was added molecular sieves 4E. After standing the mixture for 20 hours adding additional quantities of molecular sieves, the mixture was filtered. The solvent was removed in vacuum and the oily residue was heated in ethanol (50°). Yellow solids, which were planted after cooling at -20°C, was filtered and dried under vacuum. Output mixed diimine (14) 300 mg (23%).

1H-NMR (CDCl3) δ to 8.45 (d, 1H, Py-Hm), scored 8.38 (d, 1H, Py-Hm), 7,88 (t, 1H, Py-Hp), and 7.1 (m, 4H, ArH), 6,93 (DD, 2H, ArH), 6.89 in (s, 2H, ArH), is 2.41 (s, 3H, Me)to 2.29 (s, 3H, Me), 2,22 (s, 3H, Me), from 2.00 (s, 6H, Me).19F-NMR (CDCl3) δ -126,8.

17. Obtaining complex chloride 2-[1-(2,4,6-trimethylaniline)ethyl]-6-[1-(2-ftorpirimidinu)ethyl]peridiniales[II] (15).

In an inert atmosphere to 87 mg FeCl2(0.67 mmol) in 20 ml dichloromethane was added a solution of 270 mg diimine (14, to 0.72 mmol) in 5 ml of dichloromethane. The mixture displaced ivali for 20 hours. Add 10 ml of pentane resulted in the receipt of blue precipitate, which was isolated by centrifugation and dried in vacuum. The output of the iron complex (15) 175 mg (51%).

1H-NMR (CD2Cl2, broad signals, selected data) δ 84,5 (1H, Py-Hm), 80,4 (1H, Py-Hm)and 21.2 (1H, Py-Hp), and 4.5 (3H, Mec=N), -24,5 (1H, o-ArH), -38,1 (3H, MeC=N).19F-NMR (CD2Cl2) δ -95,0.

18. Getting 2-[1-(2,4,6-trimethylaniline)ethyl]-6-[1-(1 - pyrrolidino)ethyl]pyridine (16).

In 50 ml of toluene was dissolved monoimine ((1), 3.0 g, is 10.7 mmol) and 1-aminopyrrolo (1.0 g, 12,18 mmol). To this solution was added molecular sieves (4E). After standing the mixture for 40 hours, the mixture was filtered. The solvent was removed in vacuum. The precipitate was recrystallized from ethanol. Output mixed diimine (16) of 1.85 g (50%).

1H-NMR (CDCl3) δ 8,42 (d, 1H, Py-Hm), 8,29 (d, 1H, Py-Hm), 7,86 (t, 1H, Py-Hp), 6,93 (m, 2H, pyrrole-H), to 6.88 (s, 2H, ArH), of 6.26 (m, 2H, pyrrole-H), to 2.67 (s, 3H, Me), of 2.28 (s, 3H, Me), measuring 2.20 (s, 3H, Me), from 2.00 (s, 6H, Me).

19. Obtaining complex chloride 2-[1-(2,4,6-trimethylaniline)ethyl]-6-[1-(1-pyrrolidino)ethyl]peridiniales[II] (17).

In an inert atmosphere to a solution of 400 mg diimine ((16), to 1.16 mmol) in a mixture of solvents formed by 10 ml of toluene and 6 ml of pentane was slowly added a solution of 103 mg FeCl2(0.81 mmol) in 0.7 metanol. Green-brown precipitate was isolated by centrifugation, three times washed with toluene and dried under vacuum. The output of the complex of iron (17) 375 mg (98%).

1H-NMR (CD2Cl2wide signals, not included) δ 88,1 (1H), 72,4 (1H), and 29.9 (3H), 19.5CM (3H)AND 16.9 (6N), AND 13.5 (2N), 8-8 (2N), AND 5.8 (2H), 2,9 (1H), -45,1 (3H).

20. Getting 2-[1-(2,6-diftorhinolonom)ethyl]-6-acetylpyridine (18).

In 50 ml of toluene was dissolved 2,6-diacetylpyridine (Android 4.04 g of 24.7 mmol) and 2,6-diptiranjan (3.2 g, to 24.7 mmol). To this solution was added molecular sieves (4E). After standing the mixture for 5 days at room temperature the mixture was filtered. The solvent was removed in vacuum. From the resulting mixture of 2,6-diacetylpyridine, monoimine and diimine. The most significant part of 2,6-diacetylpyridine was removed as a result of sublimation in vacuum at 80-90°C. According to the data obtained by the analysis method1H-NMR, the residue contained 0.35 mmol 2,6-diacetylpyridine, 1.28 mmol diimine and 5.46 mmol monoimine. This mixture was brought into reaction with 162 mg (1.28 mmol) FeCl2in 10 ml of THF to remove diimine. After stirring for 16 hours at room temperature the solvent was removed in vacuum. To the resulting mixture were added toluene (50 ml). The precipitated complex was filtered through a small layer of silicon dioxide with p is the receiving yellow solution. The solvent was removed in vacuum. Crystallization from ethanol gave 1.35 g of 2-[1-(2,6-diftorhinolonom)ethyl]-6-acetylpyridine(18) (19,8%).

1H-NMR (CDCl3) δ charged 8.52 (d, 1H, Py-Hm), to 8.12 (d, 1H, Py-Hm),

a 7.92 (t, 1H, Py-Hp), 7,03 (m, 1H, ArH), 6,97 (m, 2H, ArH), 2,77 (s, 3H, Me), 2,43 (s, 3H, Me).19F-NMR (CDCl3) δ -123,6.

21. Getting 2-[1-(2,6-diftorhinolonom)ethyl]-6-[1-(2,5-dimethylphenylimino)ethyl]pyridine (19).

In 25 ml of toluene was dissolved monoimine (18, 0,86 g of 3.13 mmol) and 2,5-dimethylaniline (0.40 g, 3.3 mmol). To this solution was added molecular sieves (4E). After standing the mixture for 3 days the mixture was filtered. The solvent was removed in vacuum. The residue was led from ethanol. Allocated a mixture of 2-[1-(2,6 - diftorhinolonom)ethyl]-6-[1-(2,5-dimethylphenylimino)ethyl]pyridine and 2,6-bis{2-[1-(2,5-dimethylphenylimino)ethyl]}pyridine. In THF of 2,6-bis{2-[1-(2,5-dimethylphenylimino)ethyl]}pyridine and FeCl2received the coordination compound. The solvent was removed in vacuum. To the resulting mixture were added toluene (10 ml). The precipitated complex was filtered through a small layer of silicon dioxide to obtain a yellow solution. The solvent was removed in vacuum. Crystallization from ethanol gave 40 mg (3%) 2-[1-(2,6-diftorhinolonom)ethyl]-6-[1-(2,5-dimethylphenylimino)ethyl]pyridine (19).

1H-NMR (CDCl3) δ to 8.41 (d, 2H, Py-Hmp), of 6.8 to 7.2 (m, 5H, ArH), of 6.50 (s, 1H, ArH), is 2.44 (s, 3H, Me), 2,32

(s, 6H, Me), was 2.05 (s, 3H, Me).19F-NMR (CDCl3) δ -123,4.

22. Obtaining complex chloride 2-[1-(2,6-diftorhinolonom)ethyl]-6-[1-(2,5-dimethylphenylimino)ethyl]peridiniales[II] (20).

In an inert atmosphere to 11 mg FeCl2(0,086 mmol) in 10 ml dichloromethane was added a solution of 35 mg diimine (19, 0,093 mmol) in 5 ml of dichloromethane. The mixture was stirred for 16 hours. After adding 5 ml of pentane, the resulting blue precipitate was isolated by centrifugation, washed with pentane and dried under vacuum. The output of the complex iron 20 40 mg (90%).

1H-NMR (Cl2CDCDCl2, broad signals) δ 78,6 (1H, Py-Hm), 75,0 (1H, Py-Hm), to 37.9 (1H, Py-Hp), 19,8 (1H, ArH), 16,6 (3H, Me) 15,8 (1H, ArH), 15,6 (1H, ArH), -8,2 (3H, Me) -9,7 (1H, ArH), -10,8 (3H, MeC=N), -15,7 (1H, ArH), -22,4 (1H, ArH), -29,8 (3H, MeC=N).19F-NMR (Cl2CDCDCl2) δ 62,7 million tons and -67,4.

23. Getting 2-[1-(2,4,6-trimethylaniline)ethyl]-6-[1-(ferrocenylimino)ethyl]pyridine (21).

In 40 ml of toluene was dissolved monoamin 2-[1-(2,4,6-trimethylaniline)ethyl]-6-acetylpyridine (1,263 mg of 0.94 mmol) and ferroceramic (280 mg, of 1.03 mmol). To this solution was added molecular sieves (4E). After standing the mixture for 16 hours the mixture was filtered. The solvent was removed in vacuum. The residue was recrystallized from ethanol. Output the mixed diamine 21 180 mg (41%).

1H-NMR (CD2Cl2) δ at 8.36 (DD, 2H, Py-Hm), a 7.85 (t, 1H, Py-Hp), to 6.88 (s, 2H, ArH), to 4.46 (t, 2H, CpH), 4,25 (t, 2H, CpH), 4,20 (s, 5H, CpH), to 2.55 (s, 3H, Me), and 2.27 (s, 3H, Me), measuring 2.20 (s, 3H, Me), to 1.98 (s, 6H, Me).

24. Obtaining complex chloride 2-[1-(2,4,6-trimethylaniline)ethyl]-6-[1-(ferrocenylimino)ethyl]peridiniales[II] (22).

In an inert atmosphere to 41 mg FeCl2(0.32 mmol) in 5 ml dichloromethane was added a solution of 153 mg diimine (21, 0.33 mmol) in 5 ml of dichloromethane. The mixture was stirred for 16 hours. Blue-gray precipitate was isolated by centrifugation, washed with hexane and dried in vacuum. The output of the iron complex 22 170 mg (89%).

1H-NMR (CD2Cl2, broad signals, selected data) δ 88,6 (1H, Py-Hm), 76,7 (1H, Py-Hm), 21,3 (3H, Me), and 16.3 (6H, Me), 2,8

(5H, CpH), -11,5 (3H, Mec=N).

25. Methylalumoxane (MAO).

Used a solution of MAO in toluene (Eurecen AL 5100/10T, party: V; [Al]=4,88 wt.%, TMA=35.7 wt.% (by calculation), molecular weight=900 g/mol) was obtained from Witco GmbH, Bergkamen, Germany.

Obtaining catalytic system

The receipt of the catalyst was performed in a nitrogen atmosphere in a space suit Braun MB 200-G.

The complex of iron (usually about 10 mg) were placed in a glass flask, sealed membrane; injected with a solution of MAO (4.0 g) of the above mentioned brands and spent stirring for 2 minutes. In General when you learn this led to the obtaining of a solution with a dark color, which sometimes contained some amount of sediment. After this was added toluene (9.0 g) and the solution was stirred for 10 minutes Immediately after that part of the solution used in the reaction of oligomerization (see table 1 for information on the quantities used).

Experiments on oligomerization

Experiments on the oligomerization was carried out in a steel autoclave with a volume of 1 liter, equipped with a jacket cooling with a heating/cooling bath, (from Julabo, model # ATS-2), a turbine stirrer/pneumatic agitation and partitions. In order to remove from the reactor traces of water, it was evacuated during the night when the <10 PA at 70°C. Spent catching impurities in the reactor, by 250 ml of toluene and MAO (solution containing 0.3-1.2 g), followed by stirring for 30 minutes at 70°C in an atmosphere of nitrogen at a pressure of 0.4-0.5 MPa. The contents of the reactor were discharged through the drain hole in the bottom of the autoclave. The reactor was evacuated to 0.4 kPa, was carried out by loading approximately 250 ml of toluene, 1-Heptene, 1-octene or 1-hexadecene (the exact number is given in table 1), were heated to 40°and was filed under the pressure of ethylene at a pressure specified in table 1 or in the description of the experiment. After that, the reactor with the aid of toluene was introduced rest the R. MAO (typically 0.5 g) (total injected volume was 30 ml, the methodology used was similar to the method of catalyst injection box; see below) and stirring at 800 rpm was continued for 30 minutes. The catalytic system obtained as described above, and in such numbers as described in table 1, was introduced into the reactor mixture through a system of injection box using toluene (total injected volume was 30 ml: was injectible solution of the catalyst, diluted with toluene to 10 ml, and the system injector twice washed using 10 ml of toluene). The addition of a solution of the catalyst led to the production of heat (generally 5-20° (C)that has reached its maximum within 1 minute, and then quickly installed temperature and pressure are listed in table 1. Temperature and pressure were monitored throughout the reaction, and besides, tracked and expenditure of ethylene, while maintaining the pressure of ethylene constant. After spending a certain amount of the ethylene oligomerization stopped, quickly removing ethylene scavenging, decanter product mix combined flask, using the drain hole at the base of the autoclave. Getting a mixture of air led to a rapid deactivation of the catalyst.

After adding to the crude product n-hexylbenzene (0.5-3.5 g) as an internal standard using g the gas chromatography was determined by the number of 4-C30olefins, according to which, using regression analysis, was determined (observed) K-factor Schulz-Flory for a linear connection, in the General case using10-C28data for linear alpha-olefins. The term "observed" in this case means that there is a small deviation from the distribution of the Schulz-Flory. For cooligomerization of Athena/1-octene content of 1-octene was calculated from the regression analysis for linear alpha - olefins in the C10-C28range. For cooligomerization of Athena/1 - hexadecene contents 1-hexadecene was calculated from the regression analysis for linear alpha-olefins in the C18-C28range. The data are shown in table 1.

The amount of solid phase in the product was determined as follows. The crude reaction product was centrifuged at 4000 rpm for 30 minutes, after which the transparent top layer decantation. The bottom layer consisting of a solid olefin, toluene and minor amounts of liquid olefins, mixed with 500 ml of acetone, using a stirrer with large shear forces (Ultra-Turrax type TR 18-10). The mixture was centrifuged under the above conditions. The bottom layer was mixed with 200 ml of acetone and filtered through a glass filter (porosity P3). The solid product was dried for 24 hours at 7° With at <1 kPa, weighed and the content of fractions <32was determined using gas chromatography of a solution of the solid phase in 1,2-dichlorobenzene or 1,2,4-trichlorobenzene. The amount of solid phase, are shown in table 1, are selected solid phase with the number of carbon atoms >30.

The relative amount of linear (Lin.) 1-hexene among all hexene isomers and the relative amount of linear (Lin.) 1-dodecene among all isomers dodecene was evaluated using the analysis method GC, and these values are given in table 1.

Outputs the branched C10-C30alpha-olefins in the case of cooligomerization of Athena/1-octene or branched C18-C30alpha-olefins in the case of cooligomerization of Athena/1-hexadecene and outputs the odd-numbered linear and branched C9-C29alpha-olefins in the case of cooligomerization of Athena and 1-Heptene were obtained using the analysis method GC. K-factors for linear connections and/or K-factors for branched compounds, respectively, were determined using regression analysis. These data are shown in table 1 and/or in the detailed description of experiments.

The mass ratio alkylresorcinol 1-undecene (undecanol) and alternativley and linear 1-undecanol, the mass ratio alternativley 1-dodecene (dodecanol) and al is resutling and linear 1-dodecene and mass ratio alkylresorcinol 1 eicosene (Aksenov) and alternativley and linear 1-eicosanol, some of the analysis method GC, is given in table 1.

Example 1

The iron complex 3, pre-activated by the method described in "Obtaining the catalytic system used in a steel autoclave with a volume of 1 liter, loaded with 0.5 g of MAO and toluene (total volume of 310 ml), in the experiment by oligomerization of ethylene at a pressure of ethylene of 1.6 MPa. After spending ethylene in the number 118,2 g the reaction was stopped and received by 110.6 g is linear With4-C30alpha-olefins and 2.5 g of the solid phase fraction >30. The full amount of the product of the oligomerization of ethylene 113,1 g slightly less than the number filed ethylene, which was ascribed to the loss of volatile part 1-butene and the formation of small amounts of by-products.

Linear alpha-olefins was characterized by an almost perfect distribution of the Schulz-Flory (S-F) with K-factor equal to 0.72, in accordance with the results obtained from the regression analysis by using the contents With10-C28fractions determined using an analysis method GC (regression statistics: R2=1,00; standard error=0.01 to 10 observations).

The number (frequency) speed of response (T.O.F.) was 4,E+07 mol of ethylene/mol Fe·h.

The degree of purity (linear) 1-hexene and 1-dodecene was equal and 97.7 to 99.5 wt.% respectively. The number of times tsennogo 12alpha-olefin and a branched C20alpha-olefin were at the level of <2 <3 wt.% respectively.

The details of the example 1 are shown in table 1.

Example 2

Example 2 is a repetition of example 1 except that a part of the toluene was replaced with 1-hepten. The expenditure of ethylene equal to 118,3 g, resulted in obtaining 110,3 g is linear With4-C30alpha-olefins with an even number of carbon atoms, and in addition, provided 2.0 g of the solid phase fraction >30. In addition to these products, the analysis method GC revealed the distribution of education linear and branched alpha-olefins with an odd number of carbon atoms. The odd number (C9-C29linear alpha-olefins was equal to 1.7 g, while the number of odd branched alpha-olefins was equal to 1.1,

For linear C10-C28alpha-olefins was the distribution of the Schulz-Flory in accordance with the results obtained from the regression analysis, with K-factor (even linear connection), equal to 0.69 (R2=1,00; the RMSE <0,01 to 10 observations). Regression analysis for linear C9-C21alpha-olefins with an odd number of carbon atoms and branched C9-C21alpha-olefins with an odd number of carbon atoms resulted in the distribution of XUL is a-Flory, have To (odd linear connection) was equal to 0.70 (R2=1,00; RMS error=0,02 7 observations), and (odd branched compound) was equal to 0.68 (R2=1,00; RMS error=0,02 7 observations), respectively.

T.O.F. was equal to 2,13TH+07 mol of ethylene/mol Fe·h.

The degree of purity linear (Lin.) 1-hexene and 1-dodecene was equal 99,0 and 96.1 wt.% respectively.

The details of the example 2 are shown in table 1.

Example 3

Example 3 is a repetition of example 2, but 1-hepten was replaced with 1-octene. After you have used up to 118.0 g of ethylene, the reaction was stopped, receiving and 125.4 g is linear With4-C30alpha-olefins and 9.7 g of the solid phase fraction >30. Excessive obtaining linear alpha-olefins is attributed to the inclusion in the final products of the original 1-octene, as illustrated in example 2.

For linear alpha-olefins was the distribution of the Schulz-Flory K-factor equal to 0.73, in accordance with the results obtained from the regression analysis by using the contents With10-C28fractions determined using an analysis method GC (regression statistics: R2=1,00; RMS error=0.02 for 10 observations).

T.O.F. was equal to 3,43TH+07 mol of ethylene/mol Fe·h.

The degree of purity of linear 1-GE is sung and linear 1-dodecene was equal to 99.5 and 91.9 wt.% respectively.

Data GC and NMR showed that the by-products are mostly metyrosine (IU-branched) alpha-olefins, for which the K-factor is equal to 0.71 (R2=0,98; standard error=0.06 to 10 observations).

Details of the reaction are shown in table 1.

Example 4

Example 4 is a repetition of example 3, but in this case using 1-hexadecene instead of 1-octene. The number of linear alpha-olefins exceeded the quantity of ethylene: 116,3 against 111,5 g, respectively. For linear alpha-olefins was the distribution of the Schulz-Flory K-factor equal to 0.72, in accordance with the results obtained from the regression analysis by using the contents With18-C28fractions determined using an analysis method GC (regression statistics: R2=1,00; standard error=0.01 to 6 observations), as shown in figure 1. From the results shown in this figure, it is clear that there is a 1,2-introduction 1-hexadecene, as confirmed by the example 2.

T.O.F. was equal to 1,E+06 mol of ethylene/mol Fe·h.

The degree of purity of linear 1-hexene and 1-dodecene was equal to 99.6 and 97.9 wt.% respectively. The number alkylresorcinol20alpha-olefin was equal to 11 wt.%, whereas in the absence of monomer 1-hexadecene watching what I < 3 wt.%, see example 1.

Data GC and NMR showed that the by-products are mostly metyrosine alpha-olefins, for which the K-factor equal to 0.70 (R2=0,99; RMS error=0,04 6 observations).

Details of the reaction are shown in table 1.

Example 5

Example 5 is a repetition of example 2, but in this case, at higher concentrations of 1-Heptene and at a lower pressure of ethylene equal to 0.7 MPa, which illustrates the effect of changing the concentration of olefins. In addition to linear alpha-olefins with an even number of carbon atoms, the analysis method GC showed a distribution in the formation of linear and branched alpha-olefins with an odd number of carbon atoms (see figure 2, which shows the chromatogram for GC). The odd number (C9-C29linear alpha-olefins were equal to 11.9 g, while the number of odd methylresorufin alpha-olefins was equal to 6.6, For a line With10-C28alpha-olefins was the distribution of the Schulz-Flory in accordance with the results obtained from the regression analysis, with K-factor for even a linear connection, is 0.64 (R2=1,00; the RMSE <0,01 to 10 observations). Regression analysis for linear C9-C29alpha-olefins with an odd number of atoms angle of the ode and methylresorufin 9-C29alpha-olefins with an odd number of carbon atoms resulted in the distribution of the Schulz-Flory, have To (odd linear connection) was is 0.64, (R2=1,00; RMS error=0,01 11 observations), and (odd branched compound) was equal to 0.63 (R2=1,00; standard error=0.03 in 11 observations), respectively.

Additional details are given in table 1.

Example 6

Example 6 is a repetition of example 3, but at a different pressure of ethylene equal to 0.7 MPa, which illustrates the effect of changes in the concentration of olefins. After you have used up to 68.8 g of ethylene, the reaction was stopped, getting to 85.8 g is linear With4-C30alpha-olefins and 3.6 g of a solid phase fraction >30. Excessive obtaining linear alpha-olefins is attributed to the inclusion in the final products of the original 1-octene, as illustrated in examples 2, 4 and 5.

For linear alpha-olefins was the distribution of the Schulz-Flory K-factor equal to 0.70, in accordance with the results obtained from the regression analysis by using the contents With10-C28fractions determined using an analysis method GC (regression statistics: R2=1,00; RMS error=0.02 for 10 observations).

T.O.F. was equal to 1,10E+07 mol of ethylene/mol the Fe· hour.

The degree of purity of linear 1-hexene and 1 linear-dodecene was equal to 99.2 and 84.7 wt.% respectively. Data GC and NMR showed that the by-products are mostly metyrosine alpha-olefins, for which the K-factor equal to 0.70 (R2=1,00; standard error=0.04 to 10 observations).

Details concerning reactions and products are shown in table 1.

Example 7

Example 7 is a repeat of example 6, but with a different concentration of 1-octene, which illustrates the effect of changes in the concentration of olefins. The results are similar to those for example 6. Details concerning reactions and products are shown in table 1.

The next series of experiments demonstrates the influence of catalytic systems with different bisimilarity ligands.

Example 8

The iron complex X (obtained in accordance with WO-A-99/02472) used in the reaction, is almost identical to the reaction of example 6. The output of the linear alpha-olefins in the C4-C30range accounted for 96.9 g, which exceeded the expenditure of ethylene, corresponding 68,7 g, indicating that the inclusion in products 1-octene.

The degree of purity of linear 1-hexene was 98,0 wt.%, and the content alkylresorcinol 1-dodecene corresponded to 14 wt.%. Data GC and NMR showed that the by-products are basically the methyl - and etilatsetatnyj (Me - and Et-branched) alpha-olefin ratio, approximately equal to 1:1. Details of the reaction are shown in table 1.

Example 9

The iron complex 5 was used in the experiment cooligomerization 1-octene at a pressure of ethylene equal to 0.7 MPa, and under conditions similar to the conditions of example 7. The output of the linear alpha-olefins in the C4-C30range equal to 60.2 g, exceeded the consumption of ethylene, corresponding to 53.5,

The degree of purity of linear 1-hexene stood at 94.7 wt.%, and the content alkylresorcinol 1-dodecene corresponded to 28 wt.%. Data GC and NMR showed that the by-products comprise mainly of methyl - and etilatsetatnyj alpha-olefins with a ratio of approximately 1:1 (see figure 3 with the above chromatogram for GC, where a is vinylidene olefin, represents olefins with internal double bonds, C and D represent etilatsetatnyj olefins). Details of the reaction are shown in table 1.

Example 10

Example 10 is a repetition of example 9, but in this case using the iron complex 5'. The results are similar to those of example 9. Details are given in table 1.

Example 11

The iron complex 8 was used in the experiment cooligomerization 1-octene, almost identical to the experiment of example 7. The output of the linear alpha-olefins in the C4-C30the range is the area made 73.6 g, that exceeded the consumption of ethylene, corresponding 68,6,

The degree of linearity of the fraction of 1-hexene was to 96.8 wt.%, and the content alkylresorcinol 1-dodecene corresponded to 20 wt.%. Data GC and NMR showed that the by-products comprise mainly of methyl - and etilatsetatnyj alpha-olefins with a ratio of approximately 1:1. Details of the reaction are shown in table 1.

Example 12

The iron complex 11 was used in the experiment cooligomerization 1-octene, almost identical to the experiment of example 7. The total yield of products was >75,6 g, which exceeded the consumption of ethylene, corresponding to 68.8, the Degree of purity of linear 1-hexene was 99.2 wt.%, and the content alkylresorcinol 1-dodecene corresponded to 5 wt.%. Data GC and NMR showed that the by-products are mostly metyrosine alpha-olefins. Details of the reaction are shown in table 1.

Example 13

The iron complex 13 was used in the experiment cooligomerization 1-octene under conditions similar conditions to example 7. The degree of purity of linear 1-hexene was 98,8 wt.%, and the content alkylresorcinol 1-dodecene corresponded to 4 wt.%. Data GC and NMR showed that the by-products are mostly metyrosine alpha-olefins. Details of the reaction are shown in table 1

Example 14

The iron complex 15 was used in the experiment cooligomerization 1-octene under conditions almost identical to the conditions of example 6. The degree of purity of linear 1-hexene was 99.1 wt.%, and the content alkylresorcinol 1-dodecene corresponded to 16 wt.%. Data GC and NMR showed that the by-products are mostly metyrosine alpha-olefins. Details of the reaction are shown in table 1.

Example 15

The iron complex 17 was used in the experiment cooligomerization 1-octene in conditions almost identical to the conditions of example 7. The output of the linear alpha-olefins in the C4-C30the range was 69.5 g, which exceeded the consumption of ethylene, corresponding 49,8, the Degree of purity of linear 1-hexene was 98.4 wt.%, and the content alkylresorcinol 1-dodecene corresponded to 17 wt.%. Data GC and NMR showed that the by-products comprise mainly of methyl - and etilatsetatnyj alpha-olefins with a ratio of approximately 1:1. Details of the reaction are shown in table 1.

Example 16

The iron complex 20 was used in the experiment cooligomerization 1-octene under conditions almost identical to the conditions of example 6. The degree of purity of linear 1-hexene was of 97.8 wt.%, and the content alkylresorcinol 1-dodecene corresponded to 21 wt.%. Data GC and NMR p is Casali, what by-products are mostly Me - and Et-branched alpha-olefins with a ratio of approximately 1:1. Details of the reaction are shown in table 1.

Example 17

The iron complex 22 was used in the experiment by oligomerization of 1-octene under conditions almost identical to the conditions of example 6. The K-factor was very small, which suggests that a significant portion of the ethylene turned into a 1-butene, which is involved in cooligomerization. It reflected the degree of purity 1-hexene, equal to 54.4 wt.%. The rest is mainly represented branched hexene. The content of branched 1-dodecene corresponded to 33 wt.%. The analysis method GC testified that by-products are mostly Me - and Et-branched alpha-olefins with a ratio of approximately 1:1. Details of the reaction are shown in table 1.

[Al]/[Fe] (mol/mol)
Table 1
Number exampleApp.1PR1PRPR2PR1PRPR
The iron complex/ (consumption in nmol)3 (215)3 (518)3 (225)3 (2166)3 (3150)3 (198)3 (507)
460021004400210065050002200
Reaction time (min)25233378406843
Pressure Athena (MPa)1,61,61,61,60,70,70,7
The consumption of toluene (ml)310290601502306090
Consumption of 1-octene (ml)034126025022601262256
Consumption of Athena (g)118,2118,3118,0111,568,868,868,7
Linear product <32(g)110,6110,331,74125,4116,357,6311,9485,879,7
Extensive product <32(g)N. O.1,145,52,26,648,79,3
Selected solid phase >30(g)2,52,0the 9.77,30,33,62,4
T.O.F. (mol2=/mol Fe·h)4,65 E+072,13 E+073,43 E+071,42 E+061,16 E+061,10 E+076,67 E+06
(Line connection)0,720,6930,7040,730,720,6430,6440,700,69
The degree of purity Lin. 1-C6= (wt.%)99,599,099,599,699,099,2of 99.1
The degree of purity Lin. 1-C12= (wt.%)97,796,191,997,998,084,783,3
(Branched connection)N. O.0,680,710,700,630,700,70
Branched 1-C12= (wt.%)<240671153861415

TABLE 1 (continued)
Number examplePR7PRPRProverbs 11PRPRPR
The iron complex/ (feed in nmol)X7(562)5 (1920)5' (1780)8 (3510)11 (2540)13 (3170)15 (672)
[Al]/[Fe] (mol/mol)19009009006007006001700
Reaction time (min)18697459586220
Pressure Athena (MPa)0,70,70,70,70,70,70,7
Submission of toluene (ml)6012090909015060
Submission of 1-octene (ml)247243230254242261260
Spending Athena (g)68,753,580,468,668,833,668,4
Linear PR is the product of a < With32(g)96,960,291,573,655,129,149,4
Selected solid phase >30(g)5,9<0,1<0,17,620,511,79,0
T.O.F. (mol2=/mol Fe·h)the 1.44 E+078,70 E+051.31 E+067,12 E+051,00 E+063,66 E+051,11 E+07
(Line connection)0,700,460,440,730,820,820,76
The degree of purity Lin. 1-C6= (wt.%)98,094,792,596,899,298,8of 99.1
The degree of purity Lin. 1-C12= (wt.%)82,0to 66.365,575,994,394,982,6
Branched 1-C12= (wt.%)142829205416

TABLE 1 (continued)
Number examplePRPR
The iron complex/(feed in nmol)17 (353)20 (984)22 (4230)
[Al]/[Fe] (mol/mol)29001300600
Reaction time (min)425945
Pressure Athena (MPa)0,70,70,7
Submission of toluene (ml)906060
Submission of 1-octene (ml)255234237
Spending Athena (g)49,842,264,8
Linear product <32(g)69,565,030,8
Selected solid phase >30(g)2,11,5<0,1
T.O.F. (mol2=/mol Fe·h)7,19 E+061,54 E+065,47 E+05
(Line connection)0,660,590,2
The degree of purity Lin. 1-C6= (wt.%)98,5of 97.854,4
The degree of purity Lin. 1-C12= (wt.%)79,4to 75.261,1
Branched 1-C12= (wt.%)172133

The experiments were conducted at 70°With 1-octene/toluene using a steel autoclave of 1 liter, unless another.

N. O.=not determined.

1Instead of 1-octene was used 1-hepten.

2Instead of 1-octene was used 1-hexadecene.

3Refers to alpha-olefins with an even number of carbon atoms.

4Refers to alpha-olefins with an odd number of carbon atoms.

5The mass ratio alternativley 1-C20= alternativley and linear 1-C20=, wt.%.

6The mass ratio alternativley 1-C11= alternativley and linear 1-C11=, wt.%.

7The catalyst obtained in accordance with WO-A-99/02472.

1. A method of obtaining a higher linear alpha olefins and/or alternativley alpha-olefins, which includes cooligomerization one or more alpha-olefins with ethylene in the presence of metalloceramic catalytic system that uses one or more complexes basarilarinizin MXandand/or one or more complexes [basarilarinizin-MYp·Lb+]NC-]qand mentioned binaryoperation complexes containing the ligand described what armoloy

where M represents a metal atom selected from Fe or Co;

and is 2 or 3;

X is a halide, optionally substituted hydrocarbon, alkoxide, amide, or hydride;

Y is a ligand, which can allow to pass to the introduction of the olefin;

NC-represents gecoordineerde anion;

p+q is 2 or 3 in accordance with the formal oxidation state of the above-mentioned metal atom;

L is a neutral molecule donor Lewis;

b=0, 1, or 2;

each of R1-R5independently of the other represents hydrogen, optionally substituted hydrocarbon, an inert functional group, or any two of R1-R3, vicinal to each in relation to one another taken together may form a ring;

each Z, which may be identical or different, represents an optionally substituted aromatic hydrocarbon ring; optionally substituted polyaromatic hydrocarbon fragment; optionally substituted heterogeneously fragment or optionally substituted aromatic hydrocarbon ring in combination with the metal, and mentioned optionally substituted aromatic hydrocarbon is also π -coordinated with the metal and the above-mentioned method implemented at a pressure of ethylene, less than 2.5 MPa.

2. The method according to claim 1, where the said ligand is described by the formula

where each of R1-R10independently of the other represents hydrogen, optionally substituted hydrocarbon, an inert functional group, or any two of R1-R3, R1-R10, vicinal to each in relation to one another taken together may form a ring;

R6may be taken together with R4with the formation of the ring;

R10may be taken together with R4with the formation of the ring;

Z represents an optionally substituted aromatic hydrocarbon ring; optionally substituted polyaromatic hydrocarbon fragment; optionally substituted heterogeneously fragment or optionally substituted aromatic hydrocarbon ring in combination with the metal, and mentioned optionally substituted aromatic hydrocarbon ring π-coordinated with the metal.

3. The method according to claim 1 or 2, where the said ligand is described by the formula

where each of R1-R5, R7-R9and R12-R14independently of the other represents salavtore, optionally substituted hydrocarbon, an inert functional group, or any two of R1-R3, R7-R9and R12-R14, vicinal to each in relation to one another taken together may form a ring;

R6represents hydrogen, optionally substituted hydrocarbon, an inert functional group, or taken together with R7or R4, forms a ring;

R10represents hydrogen, optionally substituted hydrocarbon, an inert functional group, or taken together with R9or R4, forms a ring;

R11represents hydrogen, optionally substituted hydrocarbon, an inert functional group, or taken together with R5or R12, forms a ring;

R15represents hydrogen, optionally substituted hydrocarbon, an inert functional group, or taken together with R5or R14forms a ring.

4. The method according to claim 3, where each of R1-R5, R7-R9and R12-R14independently of the other represents hydrogen, optionally substituted hydrocarbon, an inert functional group, or any two of R1-R3, R7-R9and R12-R14, vicinal to each in relation to one another, taken together, can obrazovym the th ring; R6represents a group containing a primary carbon group containing a secondary carbon or a group containing a tertiary carbon, and with the proviso that:

if R6represents a group containing a primary carbon, none of R10, R11and R15does not represent a group containing a primary carbon, or one or two of R10, R11and R15represent a group containing a primary carbon, and other groups of R10, R11and R15represent hydrogen;

if R6represents a group containing a secondary carbon, none of R10, R11and R15does not represent a group containing a primary carbon, or a group containing a secondary carbon, or one of R10, R11and R15represents a group containing a primary carbon, or a group containing a secondary carbon, and other groups of R10, R11and R15represent hydrogen;

if R6represents a group containing a tertiary carbon, all groups of R10, R11and R15represent hydrogen; and

any two of R6, R7, R8, R9, R10, R11, R12, R13, R14and R15, vicinal friend against friend, took the s together may form a ring.

5. The method according to claim 3, where each of R1-R5, R7-R9and R12-R14independently of the other represents hydrogen, optionally substituted hydrocarbon, an inert functional group, or any two of R1-R3, R7-R9and R12-R14, vicinal to each in relation to one another taken together may form a ring; R6represents hydrogen, optionally substituted hydrocarbon, an inert functional group, or taken together with R7or R4, forms a ring; R10represents hydrogen, optionally substituted hydrocarbon, an inert functional group, or taken together with R9or R4, forms a ring; R11and R15independently from each other represent hydrogen or an inert functional group.

6. The method according to claim 3, where each of R1-R5, R7-R9and R12-R14independently of the other represents hydrogen, optionally substituted hydrocarbon, an inert functional group, or any two of R1-R3, R7-R9and R12-R14, vicinal to each in relation to one another taken together may form a ring; R6, R10, R11and R15identical and each is selected from fluorine or chlorine.

7. The method according to any one of claims 1 to 6, where the alpha-olefin of comonomer in General is present in concentrations greater than 1 mol/l-1.

8. A composition comprising linear alpha olefins and/or alkylamine alpha-olefins, obtained by the method according to any one of claims 1 to 7.

9. The composition of claim 8, where said composition comprises more than 5 wt.% alternativley alpha-olefins in the total weight linear alpha-olefins and alternativley alpha-olefins in the composition of products.

10. The composition of claim 8 or 9 where the above-mentioned alkylamine alpha-olefins are methyl - and/or etilatsetatnyj alpha-olefins.

The priority according to claim 1 from 03.10.2000 except for the sign with respect to such values of Z, as the "optionally substituted aromatic uglevodoroda ring π-coordinated with the metal"with priority from 01.08.2001, p.2 from 01.08.2001, p-6 from 03.10.2000, according to claims 7 to 19 from 03.10.2000 except for the combination of characteristics, which includes the above feature, which has priority 01.08.2001, installed according to correspondence from 31.10.2005.



 

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