Method of obtaining linear alpha-olefins

FIELD: chemistry.

SUBSTANCE: invention concerns method of obtaining alpha-olefins, involving reaction of ethylene during oligomerisation in the presence of catalytic system obtained by mixing in situ of: metal salt based on Fe(III); ligand of bis-iminopyridine; and (c) co-catalyst, which is a product of reaction of water with one or more organoaluminum compound where one or more organoaluminum compound is selected out of: (i) βδ-forked compounds of formula (I): Al(CH2-CR1R2-CH2-CR4R5R6)xR3yHz, where R1 is linear or forked, saturated or non-saturated C1-C20-alkyl-, C3-C20-cycloalkyl-, C6-C20-aryl- or C7-C20-alkylaryl-radical; R2 is hydrogen or linear or forked, saturated or non-saturated C1-C20-alkyl-, C6-C20-aryl-, C7-C20-alkylaryl- or -arylalkyl-radical; R3 is linear or forked, saturated or non-saturated C1-C20-alkyl-, C3-C20-cycloalkyl-, C6-C20-aryl-, C7-C20-alkylaryl- or C7-C20-arylalkyl-radical; x is integer from 1 to 3; z is 0 or 1; y is 3-x-z; R4 and R5 are the same or differ, and are linear or forked, saturated or non-saturated C1-C20-alkyl-, C3-C20-cycloalkyl-, C6-C20-aryl-, C7-C20-arylalkyl- or -alkylaryl-radicals; R1 and R4 or R4 and R5 substitutes form optionally one or two rings with 3-6 carbon atoms; R6 is hydrogen or the same as R4 and R5; (ii) (βγ-forked compounds of formula (II): Al(CH2-CR1R2-CH2-CR4R5R6)xR3yHz, where R1, R2, R3, R4, R5, R6, x, y and z are defined as for the formula (I); R4 and R5 are the same or differ, and are linear or forked, saturated or non-saturated C1-C20-alkyl-, C3-C20-cycloalkyl-, C6-C20-aryl-, C7-C20-arylalkyl- or -alkylaryl-groups; R1 andR4 or R4 and R5 form optionally one or two rings with 3-6 carbon atoms; R6 is hydrogen or the same as R4 and R5 ; and their mixes where metal salt and ligand of bis-aryliminopyridine are mixed and are soluble in aliphatic or aromatic solvent.

EFFECT: extended lifetime and enhanced catalytic activity of catalytic systems at unchanged purity and alpha-olefin output.

8 cl, 1 tbl, 21 ex

 

The technical field to which the invention relates

The present invention relates to a method for producing linear alpha-olefins by oligomerization of ethylene to catalytic systems for use in the specified method.

Background of invention

There are various ways of getting higher linear alpha-olefins (for example, D. Vogt,Oligomerisation of ethylene to higher α-olefins in Applied Homogenous Catalysis with Organometallic compounds, Ed. B. Cornils, W.A. Herrmann, 2nd Edition, Vol. 1, Ch. 2.3.1.3, page 240-253, Wiley-VCh 2002). These industrial methods allow to obtain oligomeric products with a Poisson distribution or a distribution Schulz-Flory.

In order to obtain the Poisson distribution, in the oligomerization process should not be open circuit. But, on the contrary, in the method of the Schulz-Flory is an open circuit and does not depend on chain length. Stage oligomerization of ethylene, catalyzed by Nickel, according to the method, called Schell is a way of getting higher olefins (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 fraction of each of the olefin can be determined by calculation on the basis of the so-called K-factor. The K-factor, which is an indicator of the relative proportions of the resulting olefins, represents a molar ratio [(Cn+2]/[Cn], R is shitennou angle of slope of a plot of lg [C nmol.%] depending on n, where n represents the number of carbon atoms in particular the resulting olefin. The K-factor is the same characteristics for each n. By varying the ligand and regulation of the parameters of the reaction K-factor can be adjusted to higher or lower values. Thus, the method can work with the implementation of the production program with optimized economic benefit.

As the need for6-C18the fraction is much higher than it is in C>20-faction, means adapted to receive olefins with a lower number of carbon atoms. However, the formation of olefins with a higher number of carbon atoms is inevitable, and without further processing, the formation of these products is detrimental to the profitability of the way. To mitigate the negative impacts of olefins with a higher number of carbon atoms and low values With4-faction was developed for the processing technology of these threads and turning them into more valuable chemicals, such as C6-C18-olefins with internal double bonds, as practiced in the SHOP-fashion.

However, this technology is costly both from a capital investment perspective and from the point of view to operate the tion and, accordingly, it introduces additional cost. Therefore, considerable efforts are aimed at maintaining the olefin production with a high number of carbon atoms at an absolute minimum, i.e. no more than inherently associated with the K-factor method Schulz-Flory.

In this regard, a number of published patent applications describe catalytic system for the polymerization or oligomerization of 1-olefins, in particular ethylene, which (catalyst system) contain nitrogen-containing compounds of the transition metal. See, for example, the following patent applications, which are given here by reference in its entirety: WO 92/12162, WO 96/27439, WO 99/12981, WO 00/50470, WO 98/27124, WO 99/02472, WO 99/50273, WO 99/51550, EP-A-1127987, WO 02/12151, WO 02/06192, WO 99/12981, WO 00/24788, WO 00/08034, WO 00/15646, WO 00/20427 and WO 01/58874 and WO 03/000628.

In particular, the recently published application of the Shell company WO 01/58874, WO 02/00339, WO 02/28805 and WO 03/011876, each of which are hereby incorporated by reference in its entirety, consider new classes of catalysts based on complexes of bis-eminelton - iron dichloride, which are highly active in the oligomerization of olefins, especially ethylene, and which give linear alpha-olefins in a row With6-C30with the distribution of the Schulz-Flory, moreover, these linear alpha-olefins are of high purity.

Know the use of socializaton such as aluminum is salkil or alumoxane (the product of the interaction of water and aluminiumgie), for activation of catalysts for the oligomerization of olefins. One such socialization is MAO, i.e. methylalumoxane. Another such socialization is MMO, i.e. methylalumoxane modified isobutyl groups.

However, in experiments by oligomerization of ethylene in paraffin solvents using complexes of bis-eliminatedin-iron dichloride, MMAO as socializaton it was found that the lifetime of the catalyst is relatively low, with a concomitant formation of precipitation in time despite the use of the cushion of inert gas. Such destruction catalyst is especially difficult during continuous operation of the oligomerization of ethylene, since the precise dosing of these catalytic "solutions" or rather "always changing suspensions or suspensions becomes a difficult task.

One solution to this problem would be separate dosing of MMAO solution and the solution of the complex bis-eliminatedin-iron dichloride, and the mixture of the flows in the reactor oligomerization of ethylene. However, unfortunately, this option is complicated by the low solubility of the complexes of bis-eliminatedin - iron dichloride in aromatic and especially in aliphatic solvent.

Another solution to the problem of inaccurate dosing of the catalyst which was for the catalytic system in place, i.e. in the reactor oligomerization of ethylene, so that the components of the catalytic system is formed of a transparent and stable solution in an aliphatic or aromatic hydrocarbon solvent used in the reaction of oligomerization.

In the work Chemtech, July 1999, pages 24-28, Novel, hihly active iron and cobalt catalyst for olefin polymerisation" by Alison Bennet is considered that the mixture(ASAS)2, ligand bis-iminerva and methylalumoxane will polimerizuet ethylene with high output with the formation of plastic product, such product formed from the pre-catalytic complex and methylalumoxane.

The authors of the present invention found that Fe(III)(2,4-pentanedionate), denoted hereinafter as Fe(acac)3that is sparingly soluble in aliphatic solvents such as isooctane or heptane, is transformed into a transparent and stable solution with the introduction of approximately equimolar amount of the corresponding ligand of eliminatedin. It provides on location in the reactor oligomerization of the complex Fe(III)-bis-eliminatedin.

Using MAO as activator of the catalyst in the above receipt on the spot gives high initial activity of the catalyst, however, the service life of the catalyst is relatively short, especially at elevated temperatures in aliphatic races is vorites. This is a particular problem in the continuous oligomerization of ethylene, where the temperature is ideally located above 70°C, preferably from 80 to 120°C, in order to avoid blockage of the high molecular weight (>C20) alpha-olefins in the reactor when working with high concentrations of alpha-olefins in aliphatic solvents.

Therefore, in order to improve the service life of the catalyst, it is necessary to identify alternative socializaton in getting on the site of Fe-containing catalytic systems. It is important that this increase in the service life of the catalyst did not increase the cost of exit and purity alpha-olefins.

Now it was unexpectedly found that the use of selected βγand/or βδ-branched aluminiumtechnik or alumoxanes of socialization in getting to the place of complexes of bis-eminelton-Fe and-provides a catalytic system with longer lifetimes and higher catalytic activity. At the same time, the purity of the alpha-olefins and the release of alpha-olefins of the finished product are on the same level with products from MAO.

U.S. patent No. 6395668 considers catalytic system for polymerization of olefins containing product obtained by the reaction of (a) one or more compounds of a transition metal of groups 8 to 11 and (b) p is oduct the interaction of water and one or more alumoorganic compounds. All the examples here polymerization of ethylene using complex pre-catalyst bis-eminelton-iron. In this document there is no consideration of the receipt of linear alpha-olefins using the catalyst system, where the complex bis-eminelton-iron obtained on the spot.

Brief description of the invention

The present invention provides a method of obtaining alpha-olefins, containing the interaction of ethylene oligomerization conditions in the presence of a mixture containing:

(a) a salt of the metal based on Fe(II), Fe(III), Co(II) or(III);

(b) the ligand bis-eliminatedin;

(C) socialization, which is a product of the interaction of water with one or more alumoorganic compounds chosen from:

(i) βδ-branched compounds of formula (I):

Al(CH2-CR1R2-CH2-CR4R5R6)xR3yHz,

in which R1represents a linear or branched, saturated or unsaturated With1-C20-alkyl, C3-C20-cycloalkyl-From6-C20-aryl-, C7-C20-alkylaryl radical; R2represents hydrogen or linear or branched, saturated or unsaturated With1-C20-alkyl, C6-C20-aryl-, C7-C20-alkylaryl or arylalkyl-adical; R3represents a linear or branched, saturated or unsaturated With1-C20-alkyl, C3-C20-cycloalkyl-From6-C20-aryl-, C7-C20-alkylaryl or7-C20-arylalkyl radical; x is an integer from 1 to 3; z is 0 or 1; y is 3-x-z; R4and R5the same or different from each other, represent a linear or branched, saturated or unsaturated With1-C20-alkyl, C3-C20-cycloalkyl-From6-C20-aryl-, C7-C20-arylalkyl or alkylaryl-radical, the substituents R1and R4or R4and R5optional form one or two rings, having 3-6 carbon atoms; R6represents hydrogen or has the same meaning as R4and R5;

(ii) βγ-branched compounds of the formula (II):

Al(CH2-CR1R2-CR4R5R6)xR3yHz,

in which R1, R2, R3, R4, R5, R6x, y, and z are defined above in relation to formula (I),

and mixtures thereof,

where, when the salt of the metal and the ligand bis-eliminatedin mixed together, they are soluble in aliphatic or aromatic hydrocarbon solvent.

In another aspect of the present invention preduster is by catalytic system, a mixture in place (in situ):

(a) a metal salt based on Fe(II), Fe(III), Co(II) or(III);

(b) ligand bis-eliminatedin; and

(c) socializaton, which is a product of the interaction of water with one or more alumoorganic compounds chosen from:

(i) βδ-branched compounds of formula (I):

Al(CH2-CR1R2-CH2-CR4R5R6)xR3yHz,

in which R1represents a linear or branched, saturated or unsaturated With1-C20-alkyl, C3-C20-cycloalkyl-From6-C20-aryl-, C7-C20-alkylaryl radical; R2represents hydrogen or linear or branched, saturated or unsaturated With1-C20-alkyl, C6-C20-aryl-, C7-C20-alkylaryl or arylalkyl radical; R3represents a linear or branched, saturated or unsaturated With1-C20-alkyl, C3-C20-cycloalkyl-From6-C20-aryl-, C7-C20-alkylaryl or7-C20-arylalkyl radical; x is an integer from 1 to 3; z is equal to O or 1; y is 3-x-z; R4and R5the same or different from each other, represent a linear or branched, saturated or unsaturated With1With 20-alkyl, C3-C20-cycloalkyl-From6-C20-aryl-, C7-C20-arylalkyl or alkylaryl group; the substituents R1and R4or R4and R5optional form one or two rings, having 3-6 carbon atoms; R6represents hydrogen or has the same meaning as R4and R5;

(ii) βγ-branched compounds of the formula (II):

Al(CH2-CR1R2-CR4R5R6)xR3yHz,

in which R1, R2, R3, R4, R5, R6x, y, and z are defined above in relation to formula (I),

and mixtures thereof,

where, when the salt of the metal and the ligand bis-eliminatedin mixed together, they are soluble in aliphatic or aromatic hydrocarbon solvent.

Detailed description of the invention

The first major component of the catalytic system here is a salt of the metal based on Fe(II), Fe(III), Co(II) or(III).

Salt of the metal and the ligand bis-eliminatedin here are chosen so that, when they are mixed together, they are soluble in aliphatic or aromatic hydrocarbon solvent. The oligomerization reaction of ethylene is usually carried out in an aliphatic or aromatic hydrocarbon solvent.

As used here, the expression "when the ol metal and the ligand bis-eliminatedin mixed together, they are soluble in aliphatic or aromatic hydrocarbon solvent" means that the salt of the metal when mixed together with the ligand bis-eliminatedin in a molar ratio of 1:1,2 has a solubility in heptane at 25°C in the interval from 2 h/bn up to 200 ppm, preferably from 2 to 200 ppm, and more preferably from 20 to 200 ppm (wt/wt. with respect to the metal in solution). As an example, a mixture of 37 mg of Fe(acac)3and 57.5 mg of ligand And bis-eliminatedin obtained in the examples below (i.e. a mixture of metal salt and ligand bis-eliminatedin in a molar ratio of 1:1,2), forms an essentially clear solution and 169 grams of pure heptane at 25°C (representing 35 ppm (wt./wt.) Fe (metal) in heptane solution).

If this mixture forms an essentially clear solution in heptane, then it must also form an essentially clear solution in other aliphatic or aromatic hydrocarbon solvents commonly used in reactions of oligomerization of ethylene.

As used here, the term "essentially clear solution" means a visually clear solution, which does not increase sedimentation over time at room temperature. The term "essentially clear solution", as used here, is intended to cover both true solutions (which contain restorany the particles with an average particle diameter of from 0.1 to 1 nm, which cannot be defined microscopic or ultramicroscopic techniques and cannot be separated (ultra)filtration or dialysis), and colloidal solutions (which are particles with an average particle size of from 0.1 to 0.001 μm (=1 nm), which do not show sedimentation over time at room temperature).

It should be noted that within the borders of the present invention it is possible to use a salt of the metal, which, taken by itself, is insoluble or only sparingly soluble in aliphatic or aromatic solvent, provided that when it is mixed with a suitable ligand bis-eliminatedin, the mixture is soluble in aliphatic or aromatic solvent.

Non-limiting examples of suitable metal salts include carboxylates, carbamates, alcoholate, thiolate, catecholate, oxalates, dicarboxylate, trapolate, phosphinate, acetylacetonates, aminoacylation, bis-aminoacylation, the solubility of which can be adjusted by appropriate choice of substituents, as is well known to specialists in this field of technology.

The preferred metal salts for use here are optionally substituted acetylacetonates, also denoted as x,(x+2)-almandine, such as 2,4-almandine and 3.5-almandine. When AC is traceonly are substituted, preferred substituents are a1-C6-alkyl group, especially methyl. Examples of suitable acetylacetonates include 2,4-pentanedionate, 2,2,6,6-tetramethyl-3,5-heptanedione, 1-phenyl-1,3-butandione and 1,3-diphenyl-1,3-proportionate. The preferred acetylacetonates for use here are 2,4-pentanedionate.

Metal salt-based Fe(III) are especially preferred for use here.

Particularly preferred salt of the metal is Fe(III)(2,4-pentanedionate)3denoted here as Fe(acac)3. It should be noted that the salt of Fe(acac)3is only moderately soluble in aliphatic hydrocarbon solvent, but adding a suitable ligand bis-eliminatedin is formed essentially clear solution in aliphatic hydrocarbon solvent.

The second major component of the catalytic system is the ligand bis-eliminatedin.

As discussed above in relation to the metal salt, the ligand is selected so that, when the metal salt and the ligand bis-arylimine-pyridine are mixed together, they are soluble in aliphatic or aromatic solvent, as defined above.

Particularly suitable ligands bis-eliminatedin for use here include connection is ormula (III), below:

,

in which X represents carbon or nitrogen;

n is 0 or 1;

m is 0 or 1;

Z is a fragment of a π-coordination of the metal;

R7-R11, R13-R15and R18-R20each independently represent hydrogen, optionally substituted hydrocarbon, an inert functional group, or any two of R7-R11, R13-R15and R18-R20adjacent to each other, taken together, may form a ring;

R12represents hydrogen, optionally substituted hydrocarbon, an inert functional group, or taken together with R13or R10may form a ring;

R16represents hydrogen, optionally substituted hydrocarbon, an inert functional group, or taken together with R15or R10may form a ring;

R17represents hydrogen, optionally substituted hydrocarbon, an inert functional group, or taken together with R11or R18may form a ring; and

R21represents hydrogen, optionally substituted hydrocarbon, an inert functional group, or taken together with R11or R20may form a ring.

In relation to formula (III) leads the day higher, some terms are used as follows

The term "fragment π-coordination of the metal with respect to the group Z means that Z is a group together with the ring containing X is an atom, is a metallocene residue, or a sandwich, or a complex metal-arenas, which can be optionally substituted. The group Z contains a metal atom, which is connected coordinating π-communication with aromatic ring containing X is an atom. The group Z may also contain one or more ligands that are bound by the coordination bond with a metal atom, such as, for example, (CO) ligands, so that the Z-group forms a fragment of metal Fe(CO)x. Preferably, however, the Z-group are optionally substituted aromatic ring, which is connected coordinating π-communication with the metal. Specified optionally substituted aromatic ring may be any suitable monocyclic or polycyclic, aromatic or heteroaromatic ring having from 5 to 10 atoms, optionally containing 1 to 3 heteroatoms selected from N, O and S.

Preferably the aromatic ring is a monocyclic aromatic ring containing from 5 to 6 carbon atoms, such as phenyl or cyclopentadienyl. Non-restrictive examples of combinations of aromatic hydrocarbon rings containing X-atom, and fragments π-coordination of the metal include arrien, cobaltocene, nickelized, chromatin, Titanian, vanadocene, bis-bengalgram, bis-benzaiten and similar complexes heteroaryl-metal, monocationic arenas-manganese-Tris-carbonyl, arenas-butenedioic.

The term "hydrocarbon group" in relation to R7-R21groups of formula (III)above, means a group containing only carbon and hydrogen atoms. Unless otherwise specified, the number of carbon atoms is preferably in the range from 1 to 30, especially from 1 to 6. Hydrocarbon group can be saturated or unsaturated, aliphatic, cycloaliphatic or cycloaromatization, but preferably is aliphatic. Suitable hydrocarbon-groups include primary, secondary or tertiary carbon atom, such as described below.

The expression "optionally substituted hydrocarbon" to R7-R21groups of formula (III), above, is used to describe hydrocarbon groups, optionally containing one or more "inert" heteroaromatic functional groups. By "inert" is meant that the functional group does not interfere in any significant degree to the oligomerization. Non-limiting examples of such inert groups are fluoride, chloride, silane, stannane, ethers, alcoholate and amines with adequate toricheskim shielding, all well-known specialists in this field of technology. Some examples of such groups include methoxy and trimethylsiloxy. Specified optionally substituted hydrocarbon may include groups of primary, secondary and tertiary carbon atoms of the nature described below.

The term "inert functional group" in relation to R7-R21groups of formula (III)above, means a group other than optionally substituted hydrocarbon, which is inert in the conditions of the oligomerization here. By "inert" is meant that the functional group does not preclude in any significant degree to the oligomerization. Examples of inert functional groups that are suitable for use here include a halide, ethers, and amines, such as tertiary amines, especially fluorine and chlorine.

The term "group of primary carbon atom", as used here, means the group-CH2-R, in which R is selected from hydrogen, optionally substituted hydrocarbide or inert functional group. Examples of suitable groups of primary carbon atom include, but are not limited to,- CH3, -C2H5, -CH2Cl, -CH2OCH3, -CH2N(C2H5)2and-CH2Ph. Preferred groups of the primary carbon atom to use the are group, in which R is selected from hydrogen or unsubstituted With1-C6-hydrocarbide preferably, in which R represents hydrogen or C1-C3-alkyl.

The term "group secondary carbon atom", as used here, means the group-CH(R)2in which R is selected from optionally substituted hydrocarbide or inert functional group. Alternatively, two R groups may together represent the residue with a double bond, for example, =CH2or cycloalkyl group. Examples of groups, secondary carbon atom include, but are not limited to) -CH(CH3)2, -CHCl2, -CHPh2, -CH=CH2and cyclohexyl. Preferred groups, secondary carbon atom for use here are the groups in which R represents an unsubstituted With1-C6-hydrocarbon, preferably1-C3-alkyl.

The term "group tertiary carbon atom", as used here, means the group-C(R)3in which each R is independently selected from optionally substituted hydrocarbide or inert functional group. Alternatively, the three R groups may together represent the residue with a triple bond, for example, CCPh, or ring system containing tertiary carbon atoms, such as derivatives of adamantyl. Examples of groups of the tertiary carbon and the OMA include (but are not limited to)- (CH 3)3, -CCl3, -CCPh, 1-substituted- (CH3)2(Och3). Preferred groups of the tertiary carbon atom to use here are the groups in which each R represents an unsubstituted With1-C6-hydrocarbon preferably in which each R represents a C1-C3the alkyl group preferably in which each R represents methyl. In the case where each R represents a methyl group, the group is a tertiary carbon atom represents tert-butyl.

Specialists in the art will notice that the boundary conditions described above, the substituents R7-R21can be easily selected with the performance optimization of the catalytic system and its economic applications.

The preferred ligand bis-eliminatedin to use here is a ligand of formula (III)in which X represents S, m is 1 and n is 0, so that the ring containing X is an atom represents a 6-membered aromatic group.

Another preferred ligand bis-eliminatedin to use here is a ligand of formula (III)in which X represents S, m is 0 and n is 1, and the ring containing X is an atom with Z-group is a metallocene group.

Another predpochtitel the initial ligand bis-eliminatedin to use here is a ligand of formula (III), in which X represents N, m is 0 and n is 0, so that the ring containing X is an atom, is a 1-pyrrolyl group.

To limit products to oligomers, preferably, not more than one of R12, R16, R17and R21represented a group of the tertiary carbon atom. Also preferably, not more than two of R12, R16, R17and R21represented a group of secondary carbon atom.

Preferred ligands for use here is a ligand of formula (III) with the following ortho-substituents:

(i) R12, R16, R17and R21are each independently F or Cl;

(ii) R12and R16are a group of primary carbon atom, R17represents H or F, and R21represents H, F or primary carbon atom;

(iii) R12and R16are each independently H or F, R17and R21are each independently F, Cl or a group of primary carbon atom;

(iv) R12represents H or F, R16represents H, F or primary carbon atom, R17and R21represent groups of primary carbon atom;

(v) R12is a group of primary elivering carbon atom, R16represents hydrogen, R17and R21represent H, F, Cl, groups, primary or secondary carbon atom;

(vi) R12represents a group of the tertiary carbon atom, R16represents hydrogen, R17represents H, F, Cl, a group, a primary carbon atom, and R21represents H or F;

(vii) R12represents a group of the tertiary carbon atom, R16is a group of primary carbon atom, R17and R21represent H or F;

(viii) R12and R16represent H, F, Cl, a group, a primary carbon atom, a group, a secondary carbon atom, R17is a group of primary or secondary carbon atom, and R21represents N;

(ix) R12represent H, F, Cl, R16represents H, F, Cl or a group of primary carbon atom, R17represents a group of the tertiary carbon atom, and R21represents N;

(x) R12and R16represent H, F, Cl, R17represents a group of the tertiary carbon atom, and R21is a group of primary carbon atom.

In particular, the preferred ligands for ispolzovanie include ligands of the formula (III), in which R7-R9represent hydrogen, and in which R10and R11represent methyl, H, benzyl or phenyl, preferably methyl.

Particularly preferred ligands for use here include:

the ligand of formula (III)in which R7-R9represent hydrogen; R10and R11represent methyl; R12and R16represent methyl; R14represents methyl or hydrogen; R13and R15represent hydrogen; R17and R21represent hydrogen; R18, R19and R20are independently hydrogen, methyl or tert-butyl; X represents S; m is 1; n is 0;

the ligand of formula (III)in which R7-R9represent hydrogen; R10and R11represent methyl; R12, R14and R16represent methyl; R13and R15represent hydrogen; R17represents fluorine; and R18-R21represent hydrogen; X represents S; m is 1; n is 0;

the ligand of formula (III)in which R -R9represent hydrogen; R10and R11represent methyl; R13-R15and R18-R20represent hydrogen; R12, R16, R17and R21represent fluorine; X represents S; m is 1; n is 0;

the ligand of formula (III)in which R7-R9represent hydrogen; R10and R11represent methyl; R12,R14and R16represent methyl;R7and R15represent hydrogen; X represents S; m is 1; n is 0; R17,R18, R20and R21represent hydrogen; R19represents methoxy or trimethylsiloxy;

the ligand of formula (III)in which R7-R9represent hydrogen; R10and R11represent methyl; R12and R16represent methyl; R14represents methyl or hydrogen;R13and R15represent hydrogen; R17and R21represent hydrogen; R18,R19and R20represent independently researched the Simo hydrogen, methyl or fluorine; X represents S; m is 1; n is 0.

Ligands bis-eliminatedin for use here can be obtained using methods well known to experts in the art, such as described in patent documents WO 1/58874, WO 2/00339, WO 2/28805, WO 3/011876, WO 92/12162, WO 96/27439, WO 99/12981, WO 00/50470, WO 98/27124, WO 99/02472, WO 99/50273, WO 99/51550, EP-A-1127987, WO 02/12151, WO 02/06192, WO 99/12981, WO 00/24788, WO 00/08034, WO 00/15646, WO 00/20427 and WO 03/000628.

The third major component catalytic systems is the connection of socializaton, which is a product of the interaction of water with one or more alumoorganic compounds where one or more alumoorganic compounds chosen from:

(i) βδ-branched compounds of formula (I):

Al(CH2-CR1R2-CH2-CR4R5R6)xR3yHz,

in which R1represents a linear or branched, saturated or unsaturated With1-C20-alkyl, C3-C20-cycloalkyl-From6-C20-aryl-, C7-C20-alkylaryl radical; R2represents hydrogen or linear or branched, saturated or unsaturated With1-C20-alkyl, C6-C20-aryl-, C7-C20-alkylaryl or arylalkyl radical; R3represents a linear or rasvet is certain, saturated or unsaturated With1-C20-alkyl, C3-C20-cycloalkyl-From6-C20-aryl-, C7-C20-alkylaryl or7-C20-arylalkyl radical; x is an integer from 1 to 3; z is 0 or 1; y is 3-x-z; R4and R5the same or different from each other, represent a linear or branched, saturated or unsaturated With1-C20-alkyl, C3-C20-cycloalkyl-From6-C20-aryl-, C7-C20-arylalkyl or alkylaryl-radical, the substituents R1and R4or R4and R5optional form one or two rings, having 3-6 carbon atoms; R6represents hydrogen or has the same meaning as R4and R5;

(ii) βγ-branched compounds of the formula (II):

Al(CH2-CR1R2-CR4R5R6)xR3yHz,

in which R1, R2, R3, R4, R5, R6x, y, and z are defined above in relation to formula (I); the substituents R1and R4or R4and R5optionally form one or two rings, having 3-6 carbon atoms,

and mixtures thereof.

Connection socialization formulas (I) and (II) can be used in combination with other socialization, known in the art, such as lamorghini the definition connection other than having the formula (I) or (II).

Preferred socializaton for use here are socializaton obtained from compounds of formula (I) or (II)above, in which R1represents a C1-C5-alkyl group, preferably1-C3-alkyl, especially methyl or ethyl; R2represents hydrogen or C1-C5-alkyl group, preferably hydrogen; and R3represents a C1-C5-alkyl-group.

Also preferred socializaton for use here are socializaton obtained from compounds of formula (I) or (II)above, in which R4, R5and R6independently selected from hydrogen or C1-C5-alkyl, preferably independently selected from hydrogen or C1-C3-alkyl.

Particularly preferred socializaton for use here are socializaton obtained from compounds of formula (I) or (II)above in which x is equal to 3 and z is 0.

Suitable ORGANOMETALLIC compounds having the formula (I)include Tris(2,4,4-trimethylpentyl)aluminum, bis-(2,4,4-trimethylpentyl)aluminiumhydride, isobutyl-bis-(2,4,4-trimethylpentyl)aluminum, Diisobutyl-(2,4,4-trimethylpentyl)-aluminum, Tris(2,4-dimethylheptyl)aluminum and bis(2,4-di is milgate)aluminiumhydride.

Suitable ORGANOMETALLIC compounds having the formula (II)include Tris-(2,3-dimethylbutyl)aluminum, Tris(2,3,3-trimethylpentyl)aluminum, Tris(2,3-dimethylpentyl)-aluminum, Tris(2,3-diethylhexyl)aluminum, Tris(2,3-dimethylheptyl)aluminum, Tris(2-methyl-3-ethylphenyl)aluminum, Tris(2-methyl-3-ethylhexyl)aluminum, Tris(2-methyl-3-atergatis)-aluminum, Tris(2-methyl-3-propyloxy)aluminum, Tris(2-ethyl-3-methylbutyl)aluminum, Tris(2-ethyl-3-methylpentyl)aluminum, Tris(2,3-diethylphenyl)aluminum, Tris(2-propyl-3-methylbutyl)-aluminum, Tris-(2-isopropyl-3-methylbutyl)aluminum, Tris(2-isobutyl-3-methylpentyl)aluminum, Tris(2,3,3-trimethylpentyl)-aluminum, Tris(2,3,3-trimethylpentyl)aluminum, Tris(2-ethyl-3,3-dimethylbutyl)aluminum, Tris(2-ethyl-3,3-dimethylpentyl)-aluminum, Tris-(2-isopropyl-3,3-dimethylbutyl)aluminum, Tris(2-trimethylsilylpropyne)aluminum, Tris(2-methyl-3-phenylbutyl)-aluminum, Tris(2-ethyl-3-phenylbutyl)aluminum, Tris(2,3-di-methyl-3-phenylbutyl)aluminum, Tris(1-menthene-9-yl)aluminum and the corresponding compounds in which one of hydrocarbonrich groups replaced by hydrogen, and the corresponding compounds in which one or more hydrocarbonrich groups substituted isobutyl group.

Especially preferred socialization for use here are Tris(2,4,4-trimethylpentyl)aluminum (denoted hereinafter as "TIOAO") and Tris-(2,3-d is methylbutyl)aluminum (denoted hereinafter as "TDMBAO").

Connection socializaton get the introduction of a suitable quantity of water in the corresponding aluminiumalloy connection. Aluminiumallee compounds may be obtained by methods known in the art, and as described in WO 96/02580 and WO 99/21899.

The molar ratio of water to connection, aluminium when receiving alumoxane is preferably in the range from 0.01:1 to 2.0:1, more preferably from 0.02:1 to 1.2:1, even more preferably from 0.4:1 to 1:1, especially of 0.5:1.

In getting on the site of catalytic systems here are preferably used such levels of socializaton and metal salt that the atomic ratio Al/Fe and Al/Co is in the range from 0.1 to 106preferably from 10 to 105and more preferably from 102up to 104. Also preferably the molar ratio of the ligand bis-eliminatedin/Fe or ligand bis-eliminatedin/Co is in the range from 10-4up to 104preferably from 10-1to 10, more preferably from 0.5 to 2 and especially 1,2.

You can enter additional optional components of the catalytic system are, for example, acids and bases Lewis, such as described in WO 02/28805.

The oligomerization reaction

In the mixture of the reaction of oligomerization are typically used such quantities of catalytic components that were held from 10 -4up to 10-9gram-atom of transition metal atoms, in particular metal Fe(II) or Fe(III)per mole of ethylene, which must respond.

The oligomerization reaction can be most conveniently carried out in the temperature range from -100°C to +300°C, preferably in the temperature range from 0°C to 200°C and more preferably in the temperature range from 50°C to 150°C.

The oligomerization reaction can be most conveniently carried out at a pressure of from 0.01 to 15 MPa (0.1 to 150 bar), more preferably 1-10 MPa (10-100 bar), and most preferably 1.5 to 5 MPa (15-50 bar).

Optimal conditions of temperature and pressure used for a particular catalytic system for maximizing the yield of oligomer and minimize competing reactions, such as dimerization and polymerization, can be easily installed by an expert in the field of technology.

Conditions of temperature and pressure are preferably selected for execution of the production program with K-factor in the range of from 0.40 to 0.90, most preferably in the range from 0,60 to 0,80. It is assumed that in the present invention, the polymerization takes place when the production program has a K-factor over 0.9.

The oligomerization reaction can be carried out in the gas phase or liquid phase or in a mixed gazogidrat phase depending on the volatility of supply and product olefin is.

The oligomerization reaction is carried out in the presence of an inert hydrocarbon solvent, which may also be a carrier for the catalytic components and/or olefinic power. Suitable solvents include alkanes, alkenes, cycloalkanes and aromatic hydrocarbons. For example, solvents that can suitably be used in accordance with the present invention include heptane, isooctane, cyclohexane, benzene, toluene and xylene.

It was found that depending on the activity of the catalyst is suitable reaction time is from 0.1 to 10 hours the Reaction is preferably carried out in the absence of air or moisture.

The oligomerization reaction can be carried out in the usual way. It can be carried out in the reactor mixing, where the olefin and catalyst components are continuously fed into the reactor with a stirrer, and the reactant, product, catalyst and unused reagent pack are removed from the reactor with a stirrer with the Department of product and unused reagent, and optionally a catalyst is recycled back to the reactor with stirrer.

Alternatively, the reaction can be conducted in a batch reactor, the, where the precursors of the catalyst and olefin reagent loaded into the autoclave, and after interaction within a reasonable time, the product is separated from the reaction mixture tradition is authorized way, such as distillation.

After a suitable time of interaction of the oligomerization reaction may be terminated by rapid removal of ethylene in order to deactivate the catalytic system.

Preferably the present process is carried out in a continuous manner.

The resulting alpha-olefins have a chain length from 4 to 100 carbon atoms, preferably 4-30 carbon atoms, and most preferably from 4 to 20 carbon atoms.

Olefin products can be removed suitably by distillation and optionally separated when required, the distillation technique depending on the intended end use of olefins.

The present invention will be now illustrated in the following examples and the drawing, which should not be construed as limiting the scope of the present invention in any way.

Experimental part

Common procedures and characterization

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

The isooctane (2,4,4-trimethylpentane, purity 99.8%), dried prolonged purging with nitrogen, followed by passing through molecular sieves 4Å (final water content of about 1 ppm).

Anhydrous heptane (purity 99.8%, supplier f the RMA Aldrich), dried by passing through molecular sieves 4Å (final water content of about 3 ppm).

Ethylene (99.5 %purity) is cleaned by passing through a column containing molecular sieves 4Å and BTS catalyst (supplier - firm BASF), in order to reduce the water content and oxygen to <1 h/million

The obtained oligomers examine by gas chromatography (GC) (GC) to determine the distribution of the oligomer, with the use of device HP 5990 series II and the following chromatography conditions:

Column: HP-1 (crosslinked methylsiloxane), film thickness 0.25 µm, inner diameter 0.25 mm, length 60 m (by Hewlett Packad); injection temperature: 325°C; temperature definition: 325°C; initial temperature: 40°C for 10 min; the rate of temperature change: 10,0°C/min; final temperature: 325°C for 41,5 min; internal standard: n hexylbenzoyl.

The response characteristics of each of the linear alpha-olefins, internal hexene (CIS - and TRANS-2-hexene, CIS - and TRANS-3-hexene) and branched hexene (3-methyl-1-penten and 2-ethyl-1-butene) with respect to n-hexylbenzene (internal standard) is determined using a standard calibration mixture. Using the assumption that the response characteristics of branched and internal dodecanol are equal to the corresponding linear olefins.

Outputs4-C30-olefins receive according to GC-analysis, for which f is a torus and theoretical output With 4-C100-olefins, i.e. the total product of oligomerization (total product), determine the regression analysis using the6-C28-data. In the case of almost perfect distribution of the Schulz-Flory (standard error of the K-factor, defined regression analysis, <0.03), in the absence of education polyethylene is assumed that the number of above total product is equal to the flow rate of ethylene.

The relative amount of linear 1-hexene among all hexene isomers, the relative number of 1-dodecene among all isomers dodecene and the relative amount of 1-octadecene among all isomers of octadecene defined GC-analysis, used as a measure of the selectivity of the catalyst relative to the education of the linear alpha-olefin. The data in wt.%, in table 1, the alpha-olefin products based on it.

Under the frequency of transformation (TOF) (CPR) refers to the number of moles of ethylene oligomerization per hour, per mole of the compounds of iron.

The NMR data are obtained at room temperature using the instrument Varian 300 MHz or 400 MHz.

Salt of the metal used for the location of the catalyst is an Fe(III)(2,4-pentanedionate)3, commercially available from Aldrich company.

The ligand bis-iminerva used to obtain the location of the catalyst in the use of the Ah 1-17, represents 2-[1-(2,4,6-trimethylaniline)ethyl]-6-[1-(3,5-di-tert-butylbenzylamine)ethyl]pyridine (hereinafter "the ligand And"), which is produced in accordance with the method specified below, and which has the formula:

Getting 2-[1-(2,4,6-trimethylaniline)ethyl]-6-[1-(3,5-di-tert-butylbenzylamine)ethyl]pyridine

2-[1-(2,4,6-trimethylaniline)ethyl]-6-acetylpyridine (1.3 g, with 4.64 mmol), obtained in accordance with the method discussed in WO 02/28805, and 3,5-di-tert-butylaniline (1 g, to 4.87 mmol) was dissolved in 100 ml of toluene. To this solution add 4 Å molecular sieves. After maturation for 2 days the mixture is filtered. The solvent is removed in vacuum. The residue is washed with methanol and crystallized from ethanol. Obtain 1.1 g (51%) of 2-[1-(2,4,6-trimethylaniline)ethyl]-6-[1-(3,5-di-tert-butylbenzylamine)ethyl]pyridine.

1H-NMR (CDCl3)8,43 (d, 1H, Py-Hm), of 8.37 (d, 1H, Py-Hm), 7,87 (t, 1H, Py-Hp), 7,16 (t, 1H, ArH), 6.89 in (s, 2H, ArH), 6,69 (d, 2H, ArH), 2,42 (s, 3H, Me)to 2.29 (s, 3H, Me), 2,22 (s, 3H, Me), a 2.01 (s, 6H, Me), of 1.33 (s, 18H, But).

The ligand bis-iminerva used to obtain the location of the catalyst in examples 18-21, is a 2,6-bis-[1-(2,6-diftorhinolonom)ethyl]pyridine (hereinafter, the "ligand"), which is produced in accordance with the method discussed in WO 02/00339, and which has the formula below:

Alternatively, in experiments on oligomerization, described below, may be used any of the ligands discussed in WO 02/28805, WO 02/00339, WO 01/58874 or WO 03/011876.

Socializaton used in the experiments below, produced by adding 0.5 mol of water to 1 mol of the corresponding aluminiumgie in toluene at 0°C (it should be noted that the solvent in examples 11-19 used isooctane). Appropriate aluminiumgie used in the experiments below are in accordance with the methods described in US 6395668B1 or WO 99/21899, or they can be purchased from commercially available sources, as described below.

Socializaton used in the experiments below, are the following:

- TFPPAO used in comparative examples 12 and 19, are produced by adding 0.5 mol of water to 1 mol of Tris-[2-(4-forfinal)propyl]aluminium, the latter connection receive in accordance with the method discussed in US 6395668B1.

- TPPAO used in comparative example 15, are produced by adding 0.5 mol of water to 1 mol of Tris-(2-phenylpropyl)aluminium, the latter connection receive in accordance with the method discussed in US 6395668B1.

- TIBAO used in comparative example 17, are produced by adding 0.5 mol of water to 1 mol of Tris-(2-methylpropyl)aluminum (or triisobutylaluminum), the latter is its connection is commercially available from Aldrich company.

- TNOAO used in comparative example 4, 8, and 9, are produced by adding 0.5 mol of water to 1 mol of tri-n-octylamine, the latter compound is commercially available from Aldrich company (25 wt.% a solution of tri-n-octylamine in hexano).

- TDMBAO used in examples 2, 5 and 20, are produced by adding 0.5 mol of water to 1 mol of Tris-(2,3-dimethylbutyl)aluminium, the latter connection receive in accordance with the method discussed in WO 99/21899.

- TIOAO used in examples 3, 6 and 13, are produced by adding 0.5 mol of water to 1 mol of Tris-(2,4,4-trimethylpentyl)aluminum (or triisobutylaluminum), the latter compound is commercially available (7,49 wt.% Al) from the company Crompton GmbH, Ernst-Schering-Str. 14, D-59192 Bergkamen, Germany.

- TEA, used in comparative example 16, is triethylaluminium, which is used in non-hydrolyzed form and is commercially available from Aldrich company.

- MAO used in comparative examples 1, 7, 10, 11, 14, 18 and 21 is a modified methyl-alumoxane (MAO), in which about 25 % of methyl groups substituted isobutyl groups. Bought it as MMAO-3A in heptane ([Al]=6.42 per wt.%) from AKZO-NOBEL Chemicals B.V., Amersfoort, the Netherlands.

Experiments on oligomerization

Examples 1-10

Experiments on oligomerization 1-10 spend a 0.5-liter reactor made of stainless steel is. The reactor was cleaned with 70°C using 0.15 g of MMA and 125 ml of anhydrous heptane in an inert atmosphere for at least 30 minutes After draining the contents in the reactor is injected 125 ml of anhydrous heptane and designed socializaton with subsequent pressovaniem ethylene up to 16 bar at 40°C with the introduction of the mixture intended ligand (ligand a) and Fe(2,4-pentanedionate)3(entered Fe=0.25 µm; the molar ratio of ligand/Fe=1,2±0,1; the molar ratio of Al/Fe=700±50, unless specified otherwise). Each injection (4 ml in toluene) into the reactor injection system is accompanied by flushing the system with 2x4 ml of toluene. The total content of the solvent in the reactor after 2 injections of catalytic components is approximately 150 ml of a mixture of heptane/toluene=8/2 (wt./wt.).

After the initial ectothermy the reactor as fast as possible is brought to 70°regulation of temperature, pressure and flow rate of ethylene. When reaching the desired consumption of ethylene or consumption falls below 0.2 nl/min, the reaction being removed by rapid venting and subsequent removal of the product.

Examples 11-19

Examples 11-19 carried out in a 1-liter reactor using isooctane as a solvent in the reactor, solvent, catalytic component, the washing agent and the solvent used to obtain alumac the ANOVA. The amount of Fe(2,4-pentanedionate)3and solvent in twice the quantity specified above for the experiments in examples 1-10 above. Hence, the introduced Fe is 0.5 µmol; the total content of the solvent in the reactor after 2 injections of the catalytic components is approximately 310 ml of isooctane. The molar ratio of ligand/Fe is the same as in examples 1-10. The molar ratio of Al/Fe=700±50, unless otherwise noted. In example 14 the sequence of the introduction of socializaton and ligand/Fe(2,4-pentanedionate)3is the reverse.

Examples 20-21

Examples 20-21 carried out in a 1-liter reactor using heptane as a solvent in the reactor and toluene as a solvent of katalysator and leaching agent; the amount of Fe(2,4-pentanedionate)3and solvent in twice the quantity specified above for the experiments in examples 1-10 above. Alumoxanes socialization injected into two downloads: one before and one after the introduction of the mixture of the ligand/Fe(2,4-pentanedionate)3. Hence, the introduced Fe is 0.5 µmol; the total content of the solvent in the reactor after 3 injections of the catalytic components is approximately 340 ml of a mixture of heptane/toluene=7/3 (wt./wt.). The molar ratio of ligand/Fe is the same as in examples 1-10. The molar ratio of Al/Fe the examples 20 and 21 is 1700 and 1800, respectively, as shown in table 1.

The quantity and purity olefins determined by gas chromatography. The data presented in table 1 below.

From the experimental data, are shown in table 1, it can be seen that with the ligand 2-[1-(2,4,6-trimethylaniline)-ethyl]-6-[1-(3,5-di-tert-butylbenzylamine)ethyl]pyridine (ligand A) in a mixture of heptane/toluene 8/2 (wt./wt.) when using a molar ratio Al/Fe=1500 difference in the frequency of transformation (TOF)(CPR), K-factor and alpha-olefin between MAO, TDMBAO and TIOAO is small. Only TNOAO gives lower CPR, but the same product distribution and product purity (see examples 1, 2, 3, 4). When the ratio of Al/Fe=700 (mol./mol.), however, there was a notable difference between the activity of the catalyst originating from a variety of catalysts, as shown CPR to obtain this alpha-olefin and the drawing. It is seen that TDMBAO and TIOAO (βγ- and βδ-extensive socializaton respectively, are in the scope of the present invention) are better socialization (higher CPR and lower decomposition)than MAO and TNOAO (socializaton outside the scope of the present invention) (see examples 5, 6, 7 and 8). K-factors and their standard errors (the latter is a measure of subordination distribution Schulz-Flory) and purity of the alpha-olefin are on a par with the characteristics of the AMI, obtained MMO at equal final concentrations of AO.

In the drawing 1 shows in graphical form the comparative influence TDMBAO, MAO in examples 5 and 10, respectively, at a flow rate of ethylene in time for the molar ratio Al/Fe=700.

From comparative example 12, you can see that TFPPAO, β-alkyl-β-aryl-branched alumoxane (that ββ-branched socialization outside the scope of the invention), is socialization showing high CPR and very little decomposition at a ratio of Al/Fe=700, i.e., after the consumption of ethylene 100 normal liters (nl) the reaction continues at a steady flow rate of ethylene 4 nl/min, However, to obtain alpha-olefins TFPPAO is not enough good socialization as purity the alpha-olefin is lower than for other socialization in the scope of the present invention at a comparable molar ratios of Al/Fe (see examples 12 and 13, and examples 5 and 6). Related connection TFPPAO, namely TPPAO (also ββ-branched socialization outside the scope of the present invention) (see example 15), does not show any catalytic activity at all. The same is true for ββ-branched alumoxane TIBAO and the non-hydrolyzed triethylaluminum (tea) (see examples 17 and 16, respectively) (both are socializaton finding who I am outside the present invention).

From table 1 we can see that the ligand 2,6-bis-[1-(2,6-diftorhinolonom)ethyl]pyridine (ligand) in isooctane with TFPPAO (socialization outside the scope of the present invention) at a ratio of Al/Fe=700 represents the catalytic system, showing high activity and very little decomposition, although at the cost of purity alpha-olefin (see comparative example 19). Use TDMBAO (βγ-branched socializaton that are in the scope of the present invention) with the ligand In the network CPR comparable to CPR MMO, but to some extent the higher the purity of the alpha-olefin (cf alpha olefin fraction octadecanol for examples 20 and 21).

Thus, the results of examples 1-21 show that at low ratios of Al/Fe(700) βγ-branched alumoxane TDMBAO and βδ-branched alumoxane TIOAO are good socialization in getting to the place of Fe(II)-catalyst systems of the complex Fe(2,4-pentanedionate)3and the corresponding ligand, in particular, with ligand A. In particular, they are better catalysts than MAO, TRRO, TFPPAO, TIBAO, TNOAO and tea (which are not βγor βδ-branched). Use TDMBAO and TIOAO provides reception of alpha-olefins of high purity with an almost perfect distribution of the Schulz-Flory and low decomposition catalyst (high is reversine). Moreover, these socializaton have high solubility and stability in paraffin solvents.

In table 1 the letters a-j have the following meanings:

as the Reaction begins with ectothermy less than 3°C after heating to 60-65°C.

b Frequency transformation (CPR). The consumption of ethylene, obtained from the total product (C4-C100-olefins, as determined by regression analysis using the6-C28-GC-data), unless otherwise indicated.

with the Use of consumption of ethylene, defined as the flow from the firm Bronkhorst High-Tech B.V. Nijverheidsstraat 1a, 7261 AK Ruurlo, the Netherlands, type: F-201C-FA-00-Z).

d K-factor Schulz-Flory defined regression analysis6-C28-GC-data.

e K-factor Schulz-Flory defined regression analysis6-C16-GC-data.

f Low due to the presence of traces of hexanol (from socializaton TNOAO).

g Branched hexene, dodecene and octadecene=0,5, 2.6 and 5.0 wt.%; internal hexene, dodecene and octadecene=0,1, 0.2 and 0.2 wt.% respectively.

h Branched hexene, dodecene and octadecene=1,0, the 5.7 and 10.9 wt.% internal hexene, dodecene and octadecene=0,1, 0.2 and 0.2 wt.% respectively.

i Branched hexene, dodecene and octadecene=0,5, the 3.2 and 6.5 wt.%; internal hexene, dodecene and octadecene=0,1, 0.1 and 0.1 wt.% respectively.

j Branched hexene, dodeca the s and octadecene=0,7, the 3.6 and 6.7 wt.%; internal hexene, dodecene and octadecene=0,1, 0.2 and 0.2 wt.% respectively.

1. The method of obtaining alpha-olefins, including interaction of ethylene oligomerization conditions in the presence of a catalytic system obtained by mixing in situ:

(a) a salt of the metal-based Fe(III);

(b) the ligand bis-iminerva; and

(c) socialization, which is a product of the interaction of water with one or more alumoorganic compounds where one or more alumoorganic compounds selected from the

(i) βδ-branched compounds of formula (I)

Al(CH2-CR1R2-CH2-CR4R5R6)xR3yHz,

in which R1represents a linear or branched, saturated or unsaturated With1-C20-alkyl, C3-C20-cycloalkyl-From6-C20-aryl - or7-C20-alkylaryl radical;

R2represents hydrogen or linear or branched, saturated or unsaturated C1-C20-alkyl, C6-C20-aryl-, C7-C20-alkylaryl or arylalkyl radical;

R3represents a linear or branched, saturated or unsaturated With1-C20-alkyl, C3-C -cycloalkyl-From6-C20-aryl-, C7-C20-alkylaryl or7-C20-arylalkyl radical; x is an integer from 1 to 3; z is 0 or 1; y is 3-x-z;

R4and R5the same or different from each other, represent a linear or branched, saturated or unsaturated With1-C20-alkyl, C3-C20-cycloalkyl-From6-C20-aryl-, C7-C20-arylalkyl or alkylaryl radicals; the substituents R1and R4or R4and R5optional form one or two rings, having 3-6 carbon atoms;

R6represents hydrogen or has the same meaning as R4and R5;

(ii) βγ-branched compounds of the formula (II)

Al(CH2-CR1R2-CR4R5R6)xR3yHz,

in which R1, R2, R3, R4, R5, R6, x, y and z are defined above in relation to formula (I); R4and R5the same or different from each other, represent a linear or branched, saturated or unsaturated C1-C20-alkyl, C3-C20-cycloalkyl-From6-C20-aryl-, C7-C20-arylalkyl or alkylaryl; the substituents R1and R4or R4and R5neoba is consequently form one or two rings, having 3-6 carbon atoms;

R6represents hydrogen or has the same meanings as R4and R5;

and mixtures thereof;

where, when the salt of the metal and the ligand bis-eliminatedin mixed together, they are soluble in aliphatic or aromatic hydrocarbon solvent.

2. The method according to claim 1, in which in alumoorganic the compounds of formulas (I) and (II) R1represents a C1-C5-altergroup; R2represents hydrogen or C1-C5-altergroup; and R3represents a C1-C5-altergroup.

3. The method according to claim 1 or 2, in which alumoorganic compound is a Tris(2,4,4-trimethylpentyl)aluminum.

4. The method according to claim 1 or 2, in which alumoorganic compound is a Tris-(2,3-dimethylbutyl)aluminum.

5. The method according to claim 1, in which the ligand bis-eliminatedin selected from ligands having the formula (III)shown below

in which X represents carbon or nitrogen;

n is 0 or 1;

m is 0 or 1;

Z is a fragment of a π-coordination of the metal;

R7-R11, R13-R15and R18-R20each independently represent hydrogen, optionally substituted Hydra is Carmel, inert functional group, or any two of R7-R11, R13-R15and R18-R20adjacent to each other, taken together, may form a ring;

R12represents hydrogen, optionally substituted hydrocarbon, an inert functional group, or taken together with R15or R10may form a ring;

R16represents hydrogen, optionally substituted hydrocarbon, an inert functional group, or taken together with R15or R10may form a ring;

R17represents hydrogen, optionally substituted hydrocarbon, an inert functional group, or taken together with R11or R18may form a ring; and

R21represents hydrogen, optionally substituted hydrocarbon, an inert functional group, or taken together with R11or R20may form a ring.

6. The method according to claim 5, in which R7-R9represent hydrogen; R10and R11represent methyl; R12and R16represent methyl; R14represents methyl or hydrogen; R13and R15represent hydrogen; R17and R21represent hydrogen; R18, R19and R20are independently hydrogen, methyl and and tert-butyl; X represents S; m is 1; n is 0.

7. The method according to claim 1 or 5, in which the metal salt is an acetylacetonate.

8. The method according to claim 1 or 5 in which the salt of the metal is Fe(2,4-pentanedionate)3.



 

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FIELD: chemical industry, in particular two-component heterogeneous immobilized catalyst for ethylene polymerization.

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EFFECT: catalyst for producing polyethylene with various molecular weights, including short chain branches, from single ethylene as starting material.

7 cl, 5 tbl, 27 ex

The invention relates to a method for the polymerization of 1-olefins which can be used in catalytic systems and which include nitrogen-containing compounds of transition metals, including structural unit represented by the formula (V), where M represents Fe (II), Fe (III), Ru (II), Ru (III) or Ru (IV), X represents an atom of Cl or Br, T denotes the oxidation state of the transition metal M and b is the valency of the group X, the values of each of R1, R2, R3, R4and R6independently from each other selected from hydrogen, methyl, ethyl, n-propyl, n-butyl, n-hexyl, n-octyle, and values of each of R5and R7independently from each other selected from phenyl, 1-naphthyl, 2-naphthyl, 2-methylphenyl, 2-ethylphenyl, 2,6-diisopropylphenyl, 2,3-diisopropylphenyl, 2,4-diisopropylphenyl, 2,6-di-n-butylphenyl, 2,6-dimetilfenil, 2,3-dimetilfenil, 2,4-dimetilfenil, 2-tert-butylphenyl, 2,6-diphenylphenol, 2,4,6-trimetilfenil, 2,6-triptoreline, 4-bromo-2,6-dimetilfenil, 3,5-dichloro-2,6-diethylphenyl and 2,6-bis(2,6-dimetilfenil)phenyl, the cyclohexyl and pyridinyl

The invention relates to the field of chemical industry, in particular to the creation of more efficient new homogeneous catalysts based on the same-olefin to obtain a wide range of branched polyolefins from high molecular weight (hard) to elastomers of various molecular weights

The invention relates to a technology for syndiotactic 1,2-polybutadiene content of the vinyl groups of more than 85% and a crystallinity of 20 to 50% and can be used in the IC industry, rubber, Shoe, light, tire industry
The invention relates to the synthetic rubber industry, and in particular to methods of producing CIS-1,4-polybutadiene polymerization of butadiene-1,3 in the environment of the hydrocarbon solvent under the action of a catalyst containing a compound of cobalt, alkylalkoxysilane and water, using low temperature processing components

The invention relates to methods of producing CIS-1,4-polybutadiene and may find application in the synthetic rubber industry

FIELD: chemistry.

SUBSTANCE: present invention pertains to the method of obtaining ultra-high molecular polyethylene using Ziegler type catalyst, containing a transition metal compound on a magnesium-containing carrier. The described catalyst for obtaining ultra-high molecular polyethylene contains a vanadium compound (VCI4, VOCI3, V(OR)xCl3-x) on a magnesium-containing carrier, which is obtained from reaction of a solution of an organo-magnesium compound containing: Mg(C6H5)2n MgCl2 mR2O, where n=0.37-0.7, m=2, R2O is simple ether where R=i-Am, n-Bu, with a product of the reaction of alkylchloro silane containing: R'kSiCl4-k, where R is an alkyl or phenyl, k=0, 1, 2 and silicon tetraalkoxide Si(OEt)4. The organo-magnesium compound contains dialkylaromatic ester D. The ultra-high molecular polyethylene is obtained as a suspension in a medium of a hydrocarbon diluent using the catalyst described above, together with an organo-aluminium cocatalyst at high polymerisation temperatures (>70°C) in a hydrocarbon diluent medium.

EFFECT: increased output of the reactor.

4 cl, 7 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: polymerisation catalyst includes (1) compound of transition metal of formula A, and optionally (2) activating quantity of activator - Lewis acid; formula A, where Z represents five-member heterocyclic group, containing, at least, one carbon atom, at least, one nitrogen atom, and, at least, one other heteroatom, selected from nitrogen sulphur and oxygen, other atoms in ring being nitrogen or carbon atoms; M represents metal of groups 3-11 of periodic table or metal lantanide; E1 and E2 represent divalent groups, selected from (1) aliphatic hydrocarbon, (2) alicyclic hydrocarbon, (3) aromatic hydrocarbon, (4) alkyl-substituted aromatic hydrocarbon, (5) heterocyclic groups and (6) hetero-substituted derivatives of said groups from (1) to (5); D1 and D2 represent donor groups; X represents anion group; L represents neutral donor group; n=m=zero or one; y and z represent zero or integers.

EFFECT: high catalyst activity, ensuring novel complexes based on definite transition metals.

34 cl, 30 tbl, 15 dwg, 121 ex

FIELD: chemistry.

SUBSTANCE: invention pertains to making a new metallocene catalytic system for synthesis of polyolefins. Description is given of a metallocene system for synthesis of polyethylene and polypropylene, consisting of dimethylated metallocene IVB groups, cation-generating activator, triisobutylaluminium and a Lewis base, distinguished by that, the dimethylated metallocene IVB group is substituted or unsubstituted bridge bisindenyl or cyclopentadienylfluoronyl metallocene. The Lewis base is in form of alkylarylamine or triarylamine, in ratio of 0.1-10 mol/mol to a transition metal. Description is also given of the method of obtaining polyethylene and polypropylene in the presence of this catalytic system.

EFFECT: formation of a new catalytic metallocene system, providing for increase in activity of metallocene catalysts and the possibility of varying molecular mass properties of polyolefine.

4 cl, 1 tbl, 31 ex

FIELD: chemistry.

SUBSTANCE: invention relates to method of gas-phase polymerisation of production high density ethylene. Described is method of production of polyethylene with wide molecule-weight distribution by ethylene polymerisation in presence of polymerisation catalyst, method includes following stages in any general order: a) polyethylene polymerisation, optionally, with one or more α-olefine comonomers, having from 3 to 12 carbon atoms, in gas-phase reactor in presence of hydrogen; b) ethylene copolymerisation with one or more α-olefine comonomers, having from 3 to 12 carbon atoms, in other gas-phase reactor in presence of hydrogen amount less than at stage a), where, at least, in one said gas-phase reactors growing polymer particles flow upward through first polymerisation zone in conditions of fast pseudoliquefying or transportation, leave said first polymerisation zone and enter second polymerisation zone, through which they flow downward under impact of gravity.

EFFECT: production of polyethylene with improved mechanical properties and improved resistance to cracking under stress.

21 cl, 5 tbl, 2 dwg, 7 ex

FIELD: chemistry.

SUBSTANCE: invention pertains to polymerisation of olefins in a single reactor with use of bimetallic catalysts. Description of a method of regulating the flow index and/or splitting of molecular mass of the polymer composition is given. The method of obtaining the polymer composition involves obtaining a polymer with high molecular mass and a polymer with low molecular mass in form of a composition in one gas phase polymerisation reactor, capable of polymerisation of primary monomers, where the monomers capable of polymerisation are ethylene and olefin, chosen from a number of C3-C10 α-olefins, in one stage in the presence of a bimetallic catalyst composition and at least one regulating agent, under the condition that, the regulating agent does not contain CO2 and H2O. The regulating agent is added in quantity, sufficient for regulating the level of introduction of the polymer with high molecular mass and the level of the polymer with low molecular mass or both. The bimetallic catalytic composition is put into the psuedoliquid layer of the gas phase reactor with monomers and optionally, with components from 1 to 100 mass part./million quantity of water until obtaining a polymer composition, with flow index value I21 equal to A; with subsequent introduction of a continuous quantity of the regulating agent in quantity from 0.1 to 500 mass part/million in conversion to loading the primary monomer into the polymerisation reactor, so as to obtain a polymer composition, with flow index I21 equal to B; in which A and B differ by more than 2 dg/min or bigger value of flow index I21.

EFFECT: obtaining a method of polymerisation of olefins in one reactor with use of bimetallic catalysts with maintenance of good activity (productivity) of the catalyst.

16 cl, 3 tbl, 3 dwg, 2 ex

FIELD: chemistry.

SUBSTANCE: invention concerns an adduct of the formula MgCl2·(EtOH)m(ROH)n(H2O)P,where R is a hydrocarbon group C1-C15 different from ethyl, n and m indices are more than 0, complying with the equation (n+m) ≥ 0.7 and 0.05 ≤ n/(n+m) ≤ 0.95, and p is 0-0.7 if R is methyl and (n+m) is 0.7-1, n/(n+m) is 0.05-0.45.

EFFECT: catalyst components based on the claimed adducts can comprise olephine polymerisation catalysts characterised by improved activity in comparison to the catalysts based on the adducts obtained by earlier technologies.

22 cl, 3 tbl, 20 ex

FIELD: chemistry.

SUBSTANCE: polymer composition contains low- and high-molecular polyethylene components, the composition basically having a single peak of lamella width percentile curve and PENT greater than 1000 hours at 80°C and 2.4 MPa according to ASTM F1473. The process has several variants allowing production of tubes with enough viscosity to resist shock during laying or afterward; and with extra long working life under gas or water pressure, especially resistant to environmental stress cracking and to creep under internal pressure.

EFFECT: higher impact elasticity and longer working life of tubes.

37 cl, 5 dwg, 3 tbl, 7 ex

Catalyst system // 2326123

FIELD: chemistry.

SUBSTANCE: catalyst system is described. It consists of compounds with general formula I or its salt, bonded to a VIIIB metal, where A1 and A2, as well as A3, A4 and A5 (when present), K, D, E, X1-X4, Q1, Q2, M, L1 assume values given in the formula of invention.

EFFECT: system is suitable for carbonylation of ethenoid unsaturated compounds.

45 cl, 32 ex, 9 tbl

FIELD: catalysts, chemical technology.

SUBSTANCE: invention elates to catalytic compositions, methods for preparing such compositions, and to methods for preparing polymers based on thereof. Invention describes a composition of a spraying drying catalyst precursor and a method for preparing a spraying drying catalyst precursor wherein this composition comprises inert filling agent, magnesium, transient metal, solvent and one electron-donor compound. The composition of catalyst precursor doesn't contain practically other electron-donor compounds and the molar ratio of electron-donor compound to magnesium = 1.9 or less, and the composition comprises particles with particles size from about 10 mcm to about 200 mcm. Also, invention describes catalysts prepared from spraying drying catalyst precursors, and methods for polymerization using such catalysts. Invention provides the improved output and catalytic activity of catalyst.

EFFECT: improved properties of catalyst, improved method of polymerization.

29 cl, 4 tbl, 4 dwg, 5 ex

FIELD: polymerization catalysts.

SUBSTANCE: invention relates to a method for preparing supported titanium -manganese catalyst for synthesis of super-high molecular weight polyethylene via suspension ethylene polymerization process in hydrocarbon solvent. Titanium-containing catalyst supported by magnesium-containing carrier is prepared by reaction of organomagnesium compound Mg(C6H5)2•nMgCl2•mR2O, where n=0.37-0.7, m=2, R20 represents ether wherein R is i-amyl or n-butyl, with a silicon compound, namely product obtained by reaction of compound R'kSiCl4-k (R' is methyl or phenyl and k=0-1) with silicon tetraethoxide Si(OEt)4 at molar ratio R'kSiCl4-k/Si(OEt)4 = 6 to 40. Ethylene polymerization process in presence of above-defined catalyst in combination with co-catalyst is also described, wherein obtained super-high molecular weight polyethylene has loose density ≥ 0.39 g/cc.

EFFECT: increased molecular weight and loose density of polyethylene.

4 cl, 1 tbl, 8 ex

FIELD: polymerization catalysts.

SUBSTANCE: invention relates to catalytic systems for oligomerization of ethylene into linear α-olefins with high yield and very high selectivity as well as to preparation of these linear α-olefins. Catalytic system contains: (a) one or several catalysts based on iron or cobalt bis(arylimino)pyridine, said bis(arylimino)pyridine complexes containing ligands of general formula I: ; (b) first cocatalyst selected from aluminum alkyls, alumoxanes, and mixtures thereof; (c) second cocatalyst containing one or several compounds described by general formula ZnR'2, wherein R', identical or different, are selected from hydrogen, optionally substituted C1-C20-hydrocarbon, phenyl, Cl, Br, SR", NR"2, OH, OR", CN, wherein R", identical or different in the same molecule, are C1-C20-hydrocarbyls. α-olefins are obtained by reaction of ethylene under oligomerization conditions in presence of effective amount of above-defined catalytic system.

EFFECT: augmented assortment of polymerization catalysts.

20 cl, 1 tbl

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