ES2350468T3 - OLEFIN TRETRAMERIZATION. - Google Patents

Abstract

Process for oligomerization of olefins that includes the step of contacting an olefinic feed stream with a catalyst system that includes the combination of: a chromium compound; and a heteroatomic ligand described by the following general formula (R1) (R2) A-B-C (R3) (R4) in which A and C are independently selected from the group consisting of phosphorus, arsenic, antimony, bismuth and nitrogen; B is a linking group between A and C; and each of R1, R2, R3 and R4 is independently selected from the group consisting of a non-aromatic group, an aromatic group and a heteroaromatic group, of which at least one of R1, R2, R3 and R4 is substituted with a polar substituent; and wherein at least one of R1, R2, R3 and R4, if aromatic, is substituted with a polar substituent on a 2nd atom or an additional atom of the atom attached to A or C and provided that any of the polar substituents on R1, R2, R3 and R4, if aromatic, are not on the atom adjacent to the atom attached to A or C.

Description

Tetramerization of olefins.

Field of the Invention

This invention relates to oligomerization. of ethylene. More particularly, the invention relates to a tetramerization process, to a catalyst system for the tetramerization of olefins and the identification and use of ligands for a catalyst system for tetramerization of olefins

Background of the invention

This invention defines a method and system. of catalyst, which facilitates the production of 1-octene in high selectivity, while avoiding the joint production of significant amounts of butenes, other octene isomers, specific higher oligomers and polyethylene. The catalyst system can also be used for tetramerization of other olefins, especially α-olefins.

Despite the well-known value of 1-octene, the technique does not teach a commercially successful process for tetramerization of ethylene to selectively produce 1-octene. Conventional ethylene oligomerization technologies produce a range of α olefins following a product distribution either from Poisson or from Schulz-Flory. By definition, these mathematical distributions limit the mass% of the tetramer that can be formed and make a product distribution. In this aspect, it is known from the prior art (U.S. Patent 6,184,428) that a nickel catalyst comprising a chelating ligand, preferably 2-diphenylphosphinobenzoic acid (DPPBA), a nickel compound, preferably NiCl2 .6H_ { 2} O, and a catalyst activator, preferably sodium tetraphenylborate, catalyze the oligomerization of ethylene to produce a mixture of linear olefins. It is claimed that the selectivity towards C8 linear α-olefins is 19%. Similarly, it is reported that the Shell higher olefin process (SHOP procedure, " Shell Higher Olefins Process ", US patents 3,676,523 and 3,635,937) using a similar catalyst system typically produces 11% by mass of 1-octene in your product mix (Chem Systems PERP reports 90-1, 93-6 and 94 / 95S12).

Ziegler type technologies based on trialkylaluminum catalysts, independently developed  by Gulf Oil Chemicals Company (Chevron, for example Danish patent 1,443,927) and Ethyl Corporation (BP / Amoco, for example patent U.S. 3,906,053), are also used commercially for oligomerize ethylene to olefin mixtures that contain notified 13-25% by mass of 1-octene (Chem Systems PERP reports 90-1, 93-6, and 94 / 95S12).

The prior art also teaches that chromium-based catalysts containing heteroatomic ligands with both phosphorus and nitrogen heteroatoms selectively catalyze the trimerization of ethylene to 1-hexene. Examples of such heteroatomic ligands for the trimerization of ethylene include bis (2-diethylphosphino-ethyl) amine (WO 03/053891, fully incorporated herein by reference) as well as ( or -methoxyphenyl) 2} PN (methyl) P ( or -methoxyphenyl) 2 (WO 02/04119, fully incorporated herein by reference). Both catalyst processes and systems are very specific for the production of 1-hexene and only produce 1-octene as an impurity (usually less than 3% by mass of the product mixture as disclosed by WO 02/04119 ). The coordination phosphorus heteroatoms in ( or -methoxyphenyl) 2 PN (methyl) P ( or -methoxyphenyl) 2 (WO 02/04119) are separated by a nitrogen atom. It is believed that the nitrogen atom does not coordinate, at least in the absence of an activator, with chromium and that without any additional electron donor atom on the ligand which is a bidentate system. In addition, it is argued that electron or polar donor substituents in the ortho position of the phenyl groups help form a tridentate system, which is generally believed to potentiate selectivity towards 1-hexene formation as reiterated by the inventor of the WO 02/04119 in Chem. Commun., 2002, 858-859 stating "This has led us to raise the hypothesis that the potential of ortho-methoxy groups to act as pending donors and increase the coordination saturation of the chromium center it's an important factor. " To support their hypothesis, the authors of Chem. Commun., 2002, 858-859 showed that the use of ( p -methoxyphenyl) 2 PN (methyl) P ( p -methoxyphenyl) 2, a compound without no ortho-polar substituent of this type on at least one of R 1, R 2, R 3 and R 4, as ligand under catalytic conditions, did not result in catalytic activity towards α-olefins. WO 02/04119 (example 16) teaches the production of octenes using a catalyst system and an olefin trimerization process. In this case, 1-butene was trimerized together with two ethylene molecules to give 25% octenes. However, the nature of these octenes was not disclosed and the applicant believes that they consist of a mixture of linear and branched octenes.

The prior art teaches that they cannot high selectivities of 1-octene are achieved since the expansion of the seven-member metalacycle reaction generally accepted for trimerization of ethylene (Chem. Commun., 1989, 674) to a nine-member metalacycle which is unlikely to occur (Organometallics, 2003, 22, 2564; Angew Chem. Int. Ed., 2003, 42 (7), 808). It is argued that the nine member ring is the medium size ring minus favored and therefore must be disadvantaged in relation to the seven-member ring (Organometallics, 2003, 22, 2564). Further, it is also stated by the same authors that, "if a nine-member ring, it would be more likely to grow to a ring of eleven or thirteen members ... In other words, one never I would expect too much an octet, but the formation of some dean or dodecene (linear) would be more reasonable. "

Despite teaching otherwise, the applicant has now found a procedure to produce selectively a tetramerized olefin. The applicant has found further that chromium-based catalysts can be used containing heteroatomic ligands mixed with both nitrogen heteroatoms as phosphorus, with substituents polar on hydrocarbyl or heterohydrocarbyl groups on phosphorus atoms, to selectively tetramerize ethylene to 1-octene often in excess of 60% by mass of selectivity. This high selectivity of 1-octene through trimerization technologies or conventional single stage ethylene oligomerization that as maximum produce 25% by mass of 1-octene.

Summary of the invention

This invention relates to a process. to selectively produce tetrameric products as defined in claim 1.

This invention specifically relates to a procedure to selectively produce tetrameric products such as 1-octene from olefins such as ethylene.

The invention relates to a method for selectively produce tetrameric products using a system of Chromium catalyst containing a heteroatomic ligand.

According to the invention, a process for the tetramerization of olefins as defined  in claim 1 wherein the product of the process of tetramerization is an olefin and constitutes more than 30% of the product stream of the process.

According to the invention, the process of tetramerization includes the step of contacting a current olefinic feed with a catalyst system that includes chromium and a heteroatomic ligand as defined in the claim 1 and wherein the product of the process of tetramerization is an olefin and constitutes more than 30% of the product stream of the process.

In this specification,% will be understood That is a mass%.

The term "tetramerization" refers to generally to the reaction of four, and preferably four identical olefinic monomer units to produce an olefin linear and / or branched.

By heteroatomic means a ligand that contains at least two heteroatoms, which can be the same or different, phosphorus heteroatoms can be selected, arsenic, antimony, bismuth or nitrogen.

It will be understood that the supply current includes an olefin that will be tetramerized and can be introduced into the process according to the invention in a continuous or discontinuous

It will be understood that the product stream includes a tetramer, tetramer that is produced according to the invention in a continuous or discontinuous way.

The supply current may include a α-olefin and the product stream can include at least 30%, preferably at least 35%, of a tetramerized α-olefin monomer.

The procedure may include a procedure for the tetramerization of α-olefins. With the term α-olefins means all hydrocarbon compounds with double terminal bonds. This definition includes ethylene, propylene, 1-butene, isobutylene, 1-pentene, 1-hexene, 1-octene and the like.

The procedure may include a procedure for the tetramerization of α-olefins for selectively produce products from α-olefin tetramers.

The olefinic feed current can include ethylene and the product stream may include at least 30% of 1-octene. The procedure can be a procedure for tetramerization of ethylene.

The invention allows the selection of ligand, catalyst system and / or conditions of procedure to give a product current of more than 40%, 50% or 60% α-olefins. Can be preferable, depending on the additional use of the current of product, have such high selectivities of the α-olefin.

The olefinic feed current can include ethylene and the ratio of (C 6 {+ C 8}) :( C_ {4} + C 10) in the product stream may be more than 2.5: 1.

The olefinic feed current can include ethylene and the ratio of C 8: C 6 in the stream of Product is more than 1.

Ethylene can be contacted with the catalyst system at a pressure greater than 100 kPa (1 barg) and preferably greater than 1000 kPa (10 barg), more preferably greater than 3000 kPa (30 barg).

A and / or C can be an electron donor potential for coordination with the transition metal.

An electron donor or donor substituent of electrons is defined as the entity that donates used electrons in the formation of chemical bonds, including covalent bonds dative

The heteroatomic ligand is described by the following general formula

(R 1) (R 2) A-B-C (R 3) (R 4)

in the that

A and C are independently selected from group consisting of phosphorus, arsenic, antimony, bismuth and nitrogen; B is a linking group between A and C; Y

each of R 1, R 2, R 3 and R 4 are independently selected from the group consisting of a non-aromatic group, an aromatic group and a heteroaromatic group, of which at least one of R1, R2, R3 and R4 is substituted with a polar substituent; and in which at least one of R 1, R 2, R 3 and R 4, if aromatic, is substituted with a polar substituent on a 2nd atom or atom additional atom attached to A or C and provided that any of the polar substituents on R 1, R 2, R 3 and R 4, if they are aromatic, they are not on the atom adjacent to the atom attached to A or C.

Any polar substituent on one or more of R 1, R 2, R 3 and R 4 can be a donor of electrons

Polar is defined by the IUPAC as an entity with a permanent electric dipole moment. Substituents Polar include methoxy, ethoxy, isopropoxy, alkoxy C 3 -C 20, phenoxy, pentafluorophenoxy, trimethylsiloxy, dimethylamino, methylsulfanyl, tosyl, methoxymethyl, methylthiomethyl, 1,3-oxazolyl, methoxymethoxy, hydroxyl, amino, phosphino, arsino, stibino, sulfate, nitro and the like.

Any of the groups R1, R2, R 3 and R 4 can be independently linked to one or more between yes or to the binding group B to form a cyclic structure together with A and C, A and B or B and C.

R1, R2, R3 and R4 can independently selected from a group comprising a group benzyl, phenyl, tolyl, xylyl, mesityl, biphenyl, naphthyl, anthracenyl, methoxy, ethoxy, phenoxy, tolyloxy, dimethylamino, diethylamino, methylethylamino, thiophenyl, pyridyl, thioethyl, thiophenoxy, trimethylsilyl, dimethylhydracil, methyl, ethyl, ethenyl, propyl, butyl, propenyl, propynyl, cyclopentyl, cyclohexyl, ferrocenyl and tetrahydrofuranyl.

Preferably, R 1, R 2, R 3, R 4 can be independently selected from a group that it comprises a phenyl, tolyl, biphenyl, naphthyl, thiophenyl group and ethyl.

A and / or C can be independently oxidized by S, Se, N or O, when the valence of A and / or C allows such oxidation.

A and C can be independently phosphorus or phosphorus oxidized by S or Se or N or O.

B can be selected from the group consisting of an organic binding group comprising a hydrocarbylene, a substituted hydrocarbylene, a heterohydrocarbylene or a substituted heterohydrocarbylene; an inorganic union group that comprises a single atom binding spacer; and a group that it comprises methylene, dimethylmethylene, 1,2-ethylene, 1,2-phenylene, 1,2-propylene, 1,2-catecholate, -N (CH 3) - N (CH 3) -, -B (R 5) -, -Si (R 5) 2 -, -P (R 5) - and -N (R 5) - in which R 5 is hydrogen, a hydrocarbyl or substituted hydrocarbyl, a substituted heteroatom and a halogen.

Preferably, B can be -N (R 5) - and R 5 is a hydrocarbyl or a substituted hydrocarbyl group. R 5 may be hydrogen or may be selected from the groups that consist of alkyl, substituted alkyl, aryl, aryl groups substituted, aryloxy, substituted aryloxy, halogen, alkoxycarbonyl, carbonyloxy, alkoxy, aminocarbonyl, carbonylamino, dialkylamino, silyl or derivatives thereof, and aryl substituted with any of these substituents. Preferably, R 5 can be an isopropyl group, a group 1-cyclohexylethyl, a group 2-methylcyclohexyl or a group 2-octyl.

B can be selected to be a spacer of a single atom. A single atom binding spacer is defined as a substituted or unsubstituted atom that binds directly with A and C.

The ligand can also contain multiple units (R) n A-B-C (R) m. Non-limiting examples of such ligands include ligands. dendrimeric as well as ligands in which the individual units they are coupled either through one or more of the R groups or to through union group B. The most specific examples, but not limiting, such ligands may include 1,2-di- (N (P (4-methoxyphenyl) 2) 2) -benzene, 1,4-di- (N (P (4-methoxyphenyl) 2) 2) -benzene, N (CH 2 CH 2 N (P (4-methoxyphenyl) 2) 2) 3  Y 1,4-di- (P (4-methoxyphenyl) N (methyl) P (4-methoxyphenyl) 2) -benzene.

The ligands can be prepared using procedures known to a person skilled in the art and procedures disclosed in the published literature. Examples of ligands are: (3-methoxyphenyl) 2 PN (methyl) P (3-methoxyphenyl) 2, (4-methoxyphenyl) 2 PN (methyl) P (4-methoxyphenyl) 2 2, (3-methoxyphenyl) 2 PN (isopropyl) P (3-methoxyphenyl) 2, (4-methoxyphenyl) 2
PN (isopropyl) P (4-methoxyphenyl) 2, (4-methoxyphenyl) 2 PN (2-ethylhexyl) P (4-methoxyphenyl) 2, (3-methoxyphenyl) (phenyl) PN (methyl) P
(phenyl) 2 and (4-methoxyphenyl) (phenyl) PN (methyl) P (phenyl) 2, (3-methoxyphenyl) (phenyl) PN (methyl) P (3-methoxyphenyl) (phenyl) , (4-methoxyphenyl) (phenyl) PN (methyl) P (4-methoxyphenyl) (phenyl), (3-methoxyphenyl) 2 PN (methyl) P (phenyl) 2 and (4-methoxyphenyl) 2 PN (methyl) P (phenyl) 2, (4-methoxyphenyl) 2 PN (1-cyclohexylethyl) P (4-methoxyphenyl) 2, (4-methoxyphenyl) 2 2 PN (2-methylcyclohexyl) P (4-methoxyphenyl) 2, (4-methoxyphenyl) 2 PN (decyl) P (4-methoxyphenyl) 2, (4-methoxyphenyl) 2 PN (pentyl) P (4-methoxyphenyl) 2, (4-methoxyphenyl) 2 PN (benzyl) P (4-methoxyphenyl) 2, (4-methoxyphenyl) 2 PN (phenyl) P (4-methoxyphenyl) 2, (4-fluorophenyl) 2 PN (methyl) P (4-fluorophenyl) 2, (2-fluorophenyl) 2 PN (methyl ) P (2-fluorophenyl) 2, (4-dimethylamino-phenyl) 2 PN (methyl) P (4-dimethylamino-phenyl) 2, (4-methoxyphenyl) 2 PN (allyl) P (4-methoxyphenyl) 2, (phenyl) 2 PN (isopropyl) P (2-methoxyphenyl) 2, (4- (4-methoxyphenyl) -phenyl) 2 PN (isopropyl) P (4- (4-methoxyphenyl) phenyl) 2 and (4-methoxyphenyl) (phenyl) PN (isopropyl) P (phenyl) 2.

The catalyst system may include a activator and the procedure may include the stage of combining in any order a heteroatomic ligand with a chromium compound and an activator

The process may include the step of generating a heteroatomic coordination complex in situ from a transition metal compound and a heteroatomic ligand. The process may include the step of adding a preformed coordination complex, prepared using a heteroatomic ligand and a transition metal compound, to a reaction mixture, or the step of adding a heteroatomic ligand and a metal compound separately to the reactor. of transition so that a heteroatomic coordination complex of an in situ transition metal is generated. By generating a complex of heteroatomic coordination in situ it is meant that the complex is generated in the medium in which the catalysis takes place. Normally, the heteroatomic coordination complex is generated in situ . Typically, the transition metal compound, and the heteroatomic ligand, combine (both in situ and ex situ ) to provide metal / ligand ratios of from about 0.01: 100 to 10,000: 1, and preferably, from about 0 , 1: 1 to 10: 1.

The transition metal is chromium.

The chromium compound that, after mixing with the heteroatomic ligand and an activator, catalyzes tetramerization of ethylene according to the invention, it can be an organic salt or simple inorganic, a coordination or organometallic complex and it can be selected from any one of a group comprising complex of tris-tetrahydrofuran-trichloride chromium, (benzene) tricarbonyl-chromium, octanoate chrome (III), hexacarbonyl-chromium, acetylacetonate of chromium (III) and chromium (III) 2-ethylhexanoate. Preferred chromium compounds include chromium acetylacetonate  (III) and chromium (III) 2-ethylhexanoate.

The heteroatomic ligand can be modified to bind a polymer chain so that the resulting heteroatomic coordination complex of the transition metal is soluble at elevated temperatures, but becomes insoluble at 25 ° C. This approach would allow recovery of the complex from the reaction mixture for reuse and has been used for another catalyst as described by DE Bergbreiter et al ., J. Am. Chem. Soc., 1987, 109, 177 -179. In a similar line, these transition metal complexes can also be immobilized by binding the heteroatomic ligands for example to a skeleton of silica, silica gel, polysiloxane, alumina or the like as demonstrated, for example, by C. Yuanyin et al . , Chinese J. React. Pol., 1992, 1 (2), 152-159 to immobilize platinum complexes.

The activator for use in the procedure it can be in principle any compound that generates a catalyst  active when combined with the heteroatomic ligand and the transition metal compound. Mixtures of activators Suitable compounds include compounds of organoaluminum, organoboro compounds, organic salts, such such as methylmagnesium bromide and methyl lithium, salts and acids inorganic, such as tetrafluoroboric acid etherate, silver tetrafluoroborate, sodium hexafluoroantimoniate and Similar.

Suitable organoaluminum compounds include compounds of formula AlR 3, wherein each R is independently a C 1 -C 12 alkyl, an oxygen-containing moiety or a halide, and compounds such as LiAlH 4 and the like Examples include trimethylaluminum (TMA), triethylaluminum (TEA), tri-isobutylaluminum (TIBA), tri- n- octylaluminum, methylaluminium dichloride, ethylaluminium dichloride, dimethylaluminium chloride, diethylaluminium chloride, aluminum isopropyloxide, aluminum sesopropyloxide, aluminum sesopropyloxide, aluminum Methylaluminum sesquichloride and aluminoxanes. Aluminoxanes are well known in the art as normally oligomeric compounds that can be prepared by the controlled addition of water to an alkylaluminum compound, for example trimethylaluminum. Such compounds may be linear, cyclic, cage or mixtures thereof. Mixtures of different aluminoxanes can also be used in the process.

Examples of suitable organoboro compounds they are boroxins, NaBH_4, triethylborane, tris (pentafluorophenyl) borane, tributyl borate and Similar.

The activator can also be or contain a compound that acts as an oxidizing or reducing agent, such as sodium or metallic zinc and the like, or oxygen and the like.

The trigger can be selected from alkylaluminoxanes such as methylaluminoxane (MAO) and ethylaluminoxane (EAO) as well as modified alkyl aluminoxanes such as modified methylaluminoxane (MMAO). Methylaluminoxane Modified (a commercial product of Akzo Nobel) contains groups modifiers such as isobutyl groups or n-octyl, in addition to methyl groups.

Transition metal and aluminoxane can combine in proportions to provide Al / metal ratios of from about 1: 1 to 10,000: 1, preferably from about 1: 1 to 1000: 1, and more preferably from 1: 1 up to 300: 1.

The procedure may include the stage of add a trialkylaluminum compound to the catalyst system in amounts of between 0.01 and 1000 moles per mole of alkylaluminoxane.

It should be noted that aluminoxanes also they generally contain considerable amounts of the compounds of corresponding trialkylaluminum used in its preparation. The presence of these compounds of trialkylaluminum in aluminoxanes upon incomplete hydrolysis with Water. Any amount of a trialkylaluminum compound cited in this description is additional to compounds of Alkylaluminum contained within the aluminoxanes.

The procedure may include the stage of mix the catalyst system components to any temperature between -20 ° C and 250 ° C in the presence of an olefin. He applicant has found that the presence of an olefin can stabilize the catalyst system.

The individual components of the system catalyst described herein can be combined simultaneously or sequentially in any order, and in the presence or absence of a solvent, in order to give an active catalyst. Mixing of catalyst components can be carried out. at any temperature between -20ºC and 250ºC. The presence of a olefin during mixing of the catalyst components generally provides a protective effect that can give as result improved catalyst performance. The interval of Preferred temperature may be between 20 ° C and 100 ° C.

The catalyst system, according to the invention, or its individual components, can also be immobilized by supporting them on a support material, for example, silica, alumina, MgCl2, zircona or mixtures thereof, or on a polymer, for example polyethylene, polypropylene, polystyrene or poly (amino styrene). The catalyst can be formed in situ in the presence of the support material, or the support can be impregnated or mixed previously, simultaneously or sequentially, with one or more of the catalyst components. In some cases, the support material can also act as a component of the activator. This approach would also facilitate the recovery of the catalyst from the reaction mixture for reuse. The concept, for example, was successfully demonstrated with a chromium-based ethylene trimerization catalyst from T. Monoi and Y. Sasaki, J. Mol. Cat.A: Chem., 1987, 109, 177-179. In some cases, the support can also act as a catalyst component, for example when such supports contain aluminoxane functionalities or when the support can perform chemical functions similar to an aluminoxane, which is for example the case with IOLA? ( a commercial product of Grace
Davison).

The reaction products or in other words olefin oligomers, as described herein document, can be prepared using the catalyst system given to know by reaction in a homogeneous liquid phase in the presence or absence of an inert solvent, and / or by reaction in suspension when the catalyst system is in a form that has little or no solubility, and / or a reaction liquid / liquid in two phases, and / or a mass phase reaction in which the pure reagent and / or product olefins serve as dominant medium, and / or gas phase reaction, using techniques of contact and conventional equipment.

Therefore, the procedure can also carried out in an inert solvent. Any can be used inert solvent that does not react with the activator. These inert solvents can include any aromatic hydrocarbon and unsaturated aliphatic and saturated aliphatic and hydrocarbon halogenated Typical solvents include, but are not limited to, benzene, toluene, xylene, cumene, heptane, methylcyclohexane, methylcyclopentane, cyclohexane, 1-hexene, 1-octene, ionic liquids and the like.

The procedure can be carried out at pressures from atmospheric up to 500 barg. Pressures are preferred of ethylene in the range of 10-70 barg. The particularly preferred pressures range from 30-50 barg.

The procedure can be carried out at temperatures from -20ºC-250ºC. They prefer temperatures in the range of 15-130 ° C. The particularly preferred temperatures range from 35-100 ° C.

In a preferred embodiment of the invention, the heteroatomic coordination complex and conditions of reaction are selected in such a way that the yield of 1-octene from ethylene is greater than 30% in mass, preferably greater than 35% by mass. In this sense, yield refers to grams of 1-octene formed by 100 g of total reaction product formed.

In addition to 1-octene, the procedure can also produce different amounts of 1-butene, 1-hexene, methylcyclopentane, methylcyclopentane, propylcyclopentane, propylenecyclopentane and specific higher oligomers, depending on the nature of the heteroatomic ligand and the reaction conditions Several of these products cannot train through trimerization and oligomerization technologies of conventional ethylene in the yields observed in the present invention

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Although the catalyst, its products reaction, solvents, reagents and individual components are they usually use only once, any of these materials can, and in fact it is preferred that it be recirculated to some degree with In order to minimize production costs.

The procedure can be carried out in a plant that includes any type of reactor. Examples of such reactors include, but are not limited to, discontinuous reactors, semi-continuous reactors and continuous reactors. The plant can include, in combination a) a reactor, b) at least one pipe of entrance into this reactor for the olefin reagent and the catalyst system, c) effluent pipes from this reactor for oligomerization reaction products and d) at least a separator to separate the reaction products from desired oligomerization, in which the catalyst system can include a heteroatomic coordination complex of a compound of transition metal and an activator, as described in the present document

In another embodiment of the procedure, they can combine the reactor and a separator to facilitate formation simultaneous reaction products and the separation of these reactor compounds. The principle of the procedure is known commonly as reactive distillation. When the system Catalyst has no solubility in the solvent or reaction products, and is fixed in the reactor so that it does not come out of the reactor with the product of the reactor, the solvent and the olefin unreacted, the principle of the procedure is commonly known as catalytic distillation.

According to a further aspect of the invention, provides a catalyst system according to claim 30, for the tetramerization of olefins. The catalyst system can include a heteroatomic ligand as described above and chrome. The catalyst system may include also an activator as described above.

A and / or C can be an electron donor potential for coordination with the transition metal.

An electron donor or donor substituent of electrons is defined as the entity that donates used electrons in the formation of chemical bonds, including covalent bonds dative

Any polar substituent on one or more of R 1, R 2, R 3 and R 4 can be a donor of electrons

Polar is defined as an entity with a moment permanent electric dipole. Polar substituents include methoxy, ethoxy, isopropoxy, alkoxy C 3 -C 20, phenoxy, pentafluorophenoxy, trimethylsiloxy, dimethylamino, methylsulfanyl, tosyl, methoxymethyl, methylthiomethyl, 1,3-oxazolyl, methomethoxy, hydroxyl, amino, phosphino, arsino, stibino, sulfate, Nitro and the like.

Any of the groups R1, R2, R 3 and R 4 can be independently linked to one or more each other or to the binding group B to form a cyclic structure together with A and C, A and B or B and C.

R1, R2, R3 and R4 can independently selected from a group comprising a group benzyl, phenyl, tolyl, xylyl, mesityl, biphenyl, naphthyl, anthracenyl, methoxy, ethoxy, phenoxy, tolyloxy, dimethylamino, diethylamino, methylethylamino, thiophenyl, pyridyl, thioethyl, thiophenoxy, trimethylsilyl, dimethylhydracil, methyl, ethyl, ethenyl, propyl, butyl, propenyl, propynyl, cyclopentyl, cyclohexyl, ferrocenyl and tetrahydrofuranyl; and at least one of R 1, R 2, R 3 and R 4 is substituted with a polar substituent Preferably, R1, R2, R3 and R 4 can be independently selected from a group that it comprises a phenyl, tolyl, biphenyl, naphthyl, thiophenyl group and ethyl; and at least one of R 1, R 2, R 3 and R 4 is substituted with a polar substituent.

A and / or C can be independently oxidized by S, Se, N or O, when the valence of A and / or C allows such oxidation.

A and C can be independently phosphorus or phosphorus oxidized by S or Se or N or O.

B can be selected from the group consisting of an organic binding group comprising a hydrocarbylene, a substituted hydrocarbylene, a heterohydrocarbylene or a substituted heterohydrocarbylene; an inorganic union group that comprises a single atom binding spacer; and a group that it comprises methylene, dimethylmethylene, 1,2-ethylene, 1,2-phenylene, 1,2-propylene, 1,2-catecholate, -N (CH 3) - N (CH 3) -, -B (R 5) -, -Si (R 5) 2 -, -P (R 5) - and -N (R 5) - in which R 5 is hydrogen, a hydrocarbyl or substituted hydrocarbyl, a substituted heteroatom and a halogen.

Preferably, B may be -N (R 5) - and R 5 is a hydrocarbyl or a substituted hydrocarbyl group. R 5 may be hydrogen or may be selected from the groups consisting of alkyl, substituted alkyl, aryl, substituted aryl, aryloxy, substituted aryloxy, halogen, alkoxycarbonyl, carbonyloxy, alkoxy, aminocarbonyl, carbonylamino, dialkylamino, silyl or derivatives groups thereof, and aryl substituted with any of these substituents. Preferably, R 5 may be an isopropyl group, a 1-cyclohexylethyl group, a 2-methylcyclohexyl group or a 2- group
octyl.

B can be selected to be a spacer of a single atom. A single atom binding spacer is defined as a substituted or unsubstituted atom that binds directly with A and C.

The ligand can also contain multiple units (R) n A-B-C (R) m. Non-limiting examples of such ligands include ligands. dendrimeric as well as ligands in which the individual units they are coupled either through one or more of the R groups or to through union group B. The most specific examples, but not limiting, such ligands may include 1,2-di- (N (P (4-phenyl) 2) 2) -benzene, 1,4-di- (N (P (4-methoxyphenyl) 2) 2) -benzene, N (CH 2 CH 2 N (P (4-methoxyphenyl) 2) 2) 3  Y 1,4-di- (P (4-methoxyphenyl) N (methyl) P (4-methoxyphenyl) 2) -benzene.

The ligands can be prepared using procedures known to a person skilled in the art and procedures disclosed in the published literature. Examples of ligands are: (3-methoxyphenyl) 2 PN (methyl) P (3-methoxyphenyl) 2, (4-methoxyphenyl) 2 PN (methyl) P (4-methoxyphenyl) 2 2, (3-methoxyphenyl) 2 PN (isopropyl) P (3-methoxyphenyl) 2, (4-methoxyphenyl) 2
PN (isopropyl) P (4-methoxyphenyl) 2, (4-methoxyphenyl) 2 PN (2-ethylhexyl) P (4-methoxyphenyl) 2, (3-methoxyphenyl) (phenyl) PN (methyl) P
(phenyl) 2 and (4-methoxyphenyl) (phenyl) PN (methyl) P (phenyl) 2, (3-methoxyphenyl) (phenyl) PN (methyl) P (3-methoxyphenyl) (phenyl) , (4-methoxyphenyl) (phenyl) PN (methyl) P (4-methoxyphenyl) (phenyl), (3-methoxyphenyl) 2 PN (methyl) P (phenyl) 2 and (4-methoxyphenyl) 2 PN (methyl) P (phenyl) 2, (4-methoxyphenyl) 2 PN (1-cyclohexylethyl) P (4-methoxyphenyl) 2, (4-methoxyphenyl) 2 2 PN (2-methylcyclohexyl) P (4-methoxyphenyl) 2, (4-methoxyphenyl) 2 PN (decyl) P (4-methoxyphenyl) 2, (4-methoxyphenyl) 2 PN (pentyl) P (4-methoxyphenyl) 2, (4-methoxyphenyl) 2 PN (benzyl) P (4-methoxyphenyl) 2, (4-methoxyphenyl) 2 PN (phenyl) P (4-methoxyphenyl) 2, (4-fluorophenyl) 2 PN (methyl) P (4-fluorophenyl) 2, (2-fluorophenyl) 2 PN (methyl ) P (2-fluorophenyl) 2, (4-dimethylamino-phenyl) 2 PN (methyl) P (4-dimethylamino-phenyl) 2, (4-methoxyphenyl) 2 PN (allyl) P (4-methoxyphenyl) 2, (phenyl) 2 PN (isopropyl) P (2-methoxyphenyl) 2, (4- (4-methoxyphenyl) -phenyl) 2 PN (isopropyl) P (4- (4-methoxyphenyl) phenyl) 2 and (4-methoxyphenyl) (phenyl) PN (isopropyl) P (phenyl) 2.

The transition metal is chromium.

Chromium can be derived from a compound of Chromium selected from a simple organic or inorganic salt, a coordination complex or organometallic, which can be selected of a group comprising complex of tris-tetrahydrofuran-trichloride chromium, (benzene) tricarbonyl-chromium, octanoate of chromium (III), chromium (III) acetylacetonate, hexacarbonyl chromium and 2-ethylhexanoate of chrome (III). Preferred chromium compounds include chromium (III) acetylacetonate and 2-ethylhexanoate chrome (III).

The transition metal compound and the ligand heteroatomic may have metal / ligand ratios from about 0.01: 100 to 10,000: 1, and preferably, from approximately 0.1: 1 to 10: 1.

The catalyst system may also include an activator as described above.

The activator can in principle be any compound that generates an active catalyst when combined with the heteroatomic ligand and transition metal compound. Too mixtures of activators can be used. Suitable compounds include organoaluminum compounds, organoboro compounds, organic salts, such as methylmagnesium bromide and methyl lithium, salts and inorganic acids, such as acid etherate tetrafluoroboric, silver tetrafluoroborate, hexafluoroantimonate of sodium and the like.

The trigger can be selected from alkylaluminoxanes such as methylaluminoxane (MAO) and ethylaluminoxane (EAO) as well as modified alkyl aluminoxanes such as modified methylaluminoxane (MMAO). Methylaluminoxane Modified (a commercial product of Akzo Nobel) contains groups modifiers such as isobutyl groups or n-octyl, in addition to methyl groups. The metal of transition and aluminoxane can be in such proportions in relationship with each other that provide Al / metal ratios of from about 1: 1 to 10,000: 1, preferably from about 1: 1 to 1000: 1, and more preferably from 1: 1 up to 300: 1.

The catalyst system may also include a trialkylaluminum compound in amounts between 0.01 and 100 moles per mole of aluminoxane.

The invention also extends to uses. according to claims 50 and 51.

Examples of embodiment of the invention

The invention will now be described with reference. to the following examples that are not intended in any way to limit The scope of the invention. It is possible that Individual components of the examples may be omitted or replace and, although not necessarily ideal, it is possible to possibility that the invention can still be realized and these components should not be taken as essential for operation of the invention.

In the following examples they were carried out all procedures in inert conditions, using reagents pre-dried Chemicals were obtained from Sigma-Aldrich or Strem Chemicals unless it set otherwise. All trialkylaluminum compounds and aluminoxane and solutions thereof were obtained from Crompton Gmbh, Akzo Nobel and Albemarle Corporation. In all the examples, the molar mass of methylaluminoxane (MAO) was taken as 58.016 g / mol, corresponding to the unit (CH 3 -Al-O), in order to calculate the molar amounts of MAO used in the preparation of the catalysts described in the examples below. From similarly, the molar mass of ethylaluminoxane (EAO) was taken as 72,042 g / mol, corresponding to the building block (CH 3 CH 2 Al-O), and that of methylaluminoxane modified prepared from a 70:30 mixture of trimethylaluminum and tri-isobutylaluminum as 70.7 g / mol corresponding to the unit (Me_ {0.70} isonBu_ {0.30} -Al-O). Oligomerization products of ethylene were analyzed by CG-EM and CG-FID.

The mixed heteroatomic PNP ligands were prepared by reacting phosphine amines and chlorides, R2 PCl, as described in (a) Ewart et al , J. Chem. Soc. 1964, 1543; (b) Dossett, SJ et al , Chem. Commun., 2001, 8, 699; (c) Balakrishna, MS et al , J. Organomet. Chem. 1990, 390, 2, 203). The respective phosphine chlorides, R2 PCl, were prepared as described in the literature (Casalnuovo, AL et al , J. Am. Chem. Soc. 1994, 116, 22, 9869; Rajanbabu, TV et al , J. Org. Chem. 1997, 62, 17, 6012).

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Example one

Ligand Preparation (4-methoxyphenyl) 2 PN (isopropyl) P (4-phenyl) 2

Example 1st)

Preparation of dichloride N, N-diisopropylphosphoramide

Diisopropylamine (70 ml, 0.50 mol) was added in toluene (80 ml) to a solution of PCl3 (21.87 ml, 0.25 moles) in toluene (80 ml) at -10 ° C. The mixture was stirred for two hours and then allowed to warm to room temperature. Be stirred the solution for another hour after what was filtered through from a bed of celite. The product was obtained (35 g, 0.17 mol, 68%) after solvent removal. 31 P {H NMR: 170 ppm.

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Example 1 B)

Preparation of bromide 4-methoxyphenyl magnesium

Magnesium chips were treated (9.11 g, 0.375 moles) with 4-bromoanisole (9.39 ml, 75 mmol) in THF (100 ml). A vigorous reaction ensued that cooled in a bath of ice. Once the reaction had dissipated, the heat was heated. reaction mixture at reflux for 2 hours producing the reagent from Grignard.

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Example 1 C)

Chloride Preparation bis (4-methoxyphenyl) phosphorus

Grignard reagent was added to dichloride N, N-diisopropylphosphoramide (6.64 ml, 36 mmol) in THF (100 ml) at 0 ° C. After stirring at room temperature during overnight, the mixture was diluted with cyclohexane (200 ml) and bubbled Dry HCl gas through the solution for 0.5 hours. Behind the filtration of the precipitate, the solvent was removed giving a mixture of bromide and phosphine chloride in a yield of 80% This crude product was not isolated and everything was used in the following stage.

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Example 1d)

Preparation of (4-methoxyphenyl) 2 PN (isopropyl) P (4-methoxyphenyl) 2

To a solution of the chloride of bis (4-methoxyphenyl) crude phosphorus (28.8 mmoles calculated from the crude reaction mixture) in DCM (80 ml) and triethylamine (15 ml) at 0 ° C isopropylamine was added (1.11 ml, 13 mmol). The reaction was stirred for 30 min. after what The ice bath was removed. After stirring for a total of 14 hours, the solution was filtered to remove triethylammonium salt formed. The product was isolated after crystallization in a 77% yield. 31 P {H} NMR: 47.4 ppm (singlet large).

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Example 2

Tetramerization reaction of ethylene using acetylacetonate Cr (III), (4-methoxyphenyl) 2 PN (methyl) P (4-methoxy- phenyl) 2 and MAO

A solution of 30.0 mg of (4-methoxyphenyl) 2 PN (methyl) P (4-methoxyphenyl) 2 (0.066 mmol) in 10 ml of toluene at a solution of 11.5 mg of chromium (III) acetylacetonate (0.033 mmol) in 10 ml toluene in a container of Schlenk. The mixture was stirred for 5 min. to room temperature and then transferred to a reactor at 300 ml pressure (autoclave) containing a mixture of toluene (80 ml) and MAO (methylaluminoxane, 9.9 mmol) at 60 ° C. He charged pressure reactor with ethylene after which the temperature was maintained from the reactor at 65 ° C, while the ethylene pressure was maintained at 30 barg. Full mixing was guaranteed at all times by 1100 rpm mixing speeds using a drag agitator Of gas. The reaction was terminated after 30 minutes interrupting the ethylene feed to the reactor and cooling the reactor up to below 10 ° C. After releasing the excess ethylene from the autoclave, extinguished the liquid contained in the autoclave with ethanol followed by 10% hydrochloric acid in water. Nonano was added as a standard internal for the analysis of the liquid phase by CG-FID. A small sample of the layer was dried organic over anhydrous sodium sulfate and then analyzed through CG-FID. The rest of the layer was filtered Organic to isolate solid polymer / wax products. Be dried these solid products overnight in an oven to 100 ° C and then weighed to produce 0.2254 g of polyethylene. The GC analysis indicated that the reaction mixture contained 38.50 g of oligomers. The product distribution of this example is summarized in table 1.

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Example 3

Tetramerization reaction of ethylene using acetylacetonate Cr (III), (3-methoxyphenyl) 2 PN (methyl) P (3-methoxy- phenyl) 2 and MAO

A solution of 30.0 mg of (3-methoxyphenyl) 2 PN (methyl) P (3-methoxyphenyl) 2 (0.066 mmol) in 10 ml of toluene at a solution of 11.5 mg of chromium (III) acetylacetonate (0.033 mmol) in 10 ml of toluene in a Schlenk bowl. The mixture was stirred for 5 min. to room temperature and then transferred to a reactor at 300 ml pressure (autoclave) containing a mixture of toluene (80 ml) and MAO (methylaluminoxane, 9.9 mmol) at 60 ° C. He charged pressure reactor with ethylene after which the temperature was maintained from the reactor at 65 ° C, while the ethylene pressure was maintained at 30 barg. Full mixing was guaranteed at all times by 1100 rpm mixing speeds using a drag agitator Of gas. The reaction was terminated after 30 minutes interrupting the ethylene feed to the reactor and cooling the reactor up to below 10 ° C. After releasing the excess ethylene from the autoclave, extinguished the liquid contained in the autoclave with ethanol followed by 10% hydrochloric acid in water. Nonano was added as a standard internal for the analysis of the liquid phase by CG-FID. A small sample of the layer was dried organic over anhydrous sodium sulfate and then analyzed through CG-FID. The rest of the layer was filtered Organic to isolate solid polymer / wax products. Be dried these solid products overnight in an oven to 100 ° C and then weighed to produce 1.2269 g of polyethylene. The GC analysis indicated that the reaction mixture contained 9.71 g of oligomers. The product distribution of this example is summarized in table 1.

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Example 4

Tetramerization reaction of ethylene using acetylacetonate Cr (III), (4-methoxyphenyl) 2 PN (isopropyl) P (4-methoxyphenyl) 2  and MAO

A solution of 36.1 mg of (4-methoxyphenyl) 2 PN (isopropyl) P (4-methoxyphenyl) 2 (0.066 mmol) in 10 ml of toluene at a solution of 11.5 mg of chromium (III) acetylacetonate (0.033 mmol) in 10 ml of toluene in a Schlenk bowl. The mixture was stirred for 5 min. to room temperature and then transferred to a reactor at 300 ml pressure (autoclave) containing a mixture of toluene (80 ml) and MAO (methylaluminoxane, 9.9 mmol) at 60 ° C. He charged pressure reactor with ethylene after which the temperature was maintained from the reactor at 65 ° C, while the ethylene pressure was maintained at 30 barg. Full mixing was guaranteed at all times by 1100 rpm mixing speeds using a drag agitator Of gas. The reaction was terminated after 30 minutes interrupting the ethylene feed to the reactor and cooling the reactor up to below 10 ° C. After releasing the excess ethylene from the autoclave, extinguished the liquid contained in the autoclave with ethanol followed by 10% hydrochloric acid in water. Nonano was added as a standard internal for the analysis of the liquid phase by CG-FID. A small sample of the layer was dried organic over anhydrous sodium sulfate and then analyzed through CG-FID. The rest of the layer was filtered Organic to isolate solid polymer / wax products. Be dried these solid products overnight in an oven to 100 ° C and then weighed to produce 0.7105 g of polyethylene. The GC analysis indicated that the reaction mixture contained 61.33 g of oligomers. The product distribution of this example is summarized in table 1.

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Example 5

Tetramerization reaction of ethylene using acetylacetonate Cr (III), (4-methoxyphenyl) 2 PN (isopropyl) P (4-methoxyphenyl) 2  and MAO

A solution of 36.1 mg of (4-methoxyphenyl) 2 PN (isopropyl) P (4-methoxyphenyl) 2 (0.066 mmol) in 10 ml of toluene at a solution of 11.5 mg of chromium (III) acetylacetonate (0.033 mmol) in 10 ml of toluene in a Schlenk bowl. The mixture was stirred for 5 min. to room temperature and then transferred to a reactor at 300 ml pressure (autoclave) containing a mixture of toluene (80 ml) and MAO (methylaluminoxane, 9.9 mmol) at 40 ° C. He charged pressure reactor with ethylene after which the temperature was maintained from the reactor at 45 ° C, while the ethylene pressure was maintained at 45 barg. Full mixing was guaranteed at all times by 1100 rpm mixing speeds using a drag agitator Of gas. The reaction was terminated after 12 minutes interrupting the ethylene feed to the reactor and cooling the reactor up to below 10 ° C. After releasing the excess ethylene from the autoclave, extinguished the liquid contained in the autoclave with ethanol followed by 10% hydrochloric acid in water. Nonano was added as a standard internal for the analysis of the liquid phase by CG-FID. A small sample of the layer was dried organic over anhydrous sodium sulfate and then analyzed through CG-FID. The rest of the layer was filtered Organic to isolate solid polymer / wax products. Be dried these solid products overnight in an oven to 100 ° C and then weighed to produce 2.3010 g of polyethylene. The GC analysis indicated that the reaction mixture contained 73.53 g of oligomers. The product distribution of this example is summarized in table 1.

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Example 6

Tetramerization reaction of ethylene using acetylacetonate Cr (III), (4-methoxyphenyl) 2 PN (isopropyl) P (4-methoxyphenyl) 2  and MAO

A solution of 16.4 mg of (4-methoxyphenyl) 2 PN (isopropyl) P (4-methoxyphenyl) 2 (0.03 mmol) in 10 ml of cyclohexane at a solution of 5.2 mg of chromium (III) acetylacetonate (0.015 mmol) in 10 ml of cyclohexane in a Schlenk container. The mixture was stirred for 5 min. at room temperature and then transferred to a reactor at 300 ml pressure (autoclave) containing a mixture of cyclohexane (80 ml) and MAO (methylaluminoxane in toluene, 4.5 mmol) at 40 ° C. The pressure reactor was charged with ethylene after which kept the reactor temperature at 45 ° C while maintaining ethylene pressure at 45 barg. Full mixing guaranteed at all times by mixing speeds of 1100 rpm using a gas drag agitator. The reaction was terminated after 11 minutes interrupting the ethylene feed to the reactor and cooling the reactor to below 10 ° C. After releasing the ethylene in excess of the autoclave, the contained liquid was extinguished in the autoclave with ethanol followed by 10% hydrochloric acid in Water. Nonano was added as an internal standard for the analysis of the liquid phase by CG-FID. He dried a small sample of the organic layer over anhydrous sodium sulfate and It was then analyzed using CG-FID. Leaked the rest of the organic layer to isolate polymer products / from solid wax. These solid products were dried overnight in an oven at 100 ° C and then weighed producing 1.9168 g of polyethylene. GC analyzes indicated that the reaction mixture It contained 62.72 g of oligomers. The product distribution of This example is summarized in Table 1.

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Example 7

Tetramerization reaction of ethylene using acetylacetonate Cr (III), (4-methoxyphenyl) 2 PN (isopropyl) P (4-methoxyphenyl) 2  and MAO

A solution of 9.8 mg of (4-methoxyphenyl) 2 PN (isopropyl) P (4-methoxyphenyl) 2 (0.018 mmol) in 10 ml of toluene at a solution of 5.2 mg of chromium (III) acetylacetonate (0.015 mmol) in 10 ml of toluene in a Schlenk bowl. The mixture was stirred for 5 min. to room temperature and then transferred to a reactor at 300 ml pressure (autoclave) containing a mixture of toluene (80 ml) and MAO (methylaluminoxane, 4.5 mmol) at 40 ° C. He charged pressure reactor with ethylene after which the temperature was maintained from the reactor at 45 ° C, while the ethylene pressure was maintained at 45 barg. Full mixing was guaranteed at all times by 1100 rpm mixing speeds using a drag agitator Of gas. The reaction was terminated after 21 minutes interrupting the ethylene feed to the reactor and cooling the reactor up to below 10 ° C. After releasing the excess ethylene from the autoclave, extinguished the liquid contained in the autoclave with ethanol followed by 10% hydrochloric acid in water. Nonano was added as a standard internal for the analysis of the liquid phase by CG-FID. A small sample of the layer was dried organic over anhydrous sodium sulfate and then analyzed through CG-FID. The rest of the layer was filtered Organic to isolate solid polymer / wax products. Be dried these solid products overnight in an oven to 100 ° C and then weighed to produce 0.8280 g of polyethylene. The GC analysis indicated that the reaction mixture contained 69.17 g of oligomers. The product distribution of this example is summarized in table 1.

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Example 8

Tetramerization reaction of ethylene using CrCl 3 .THF 3, (4-methoxyphenyl) 2 PN (isopropyl) P (4-methoxyphenyl) 2  and MAO

A solution of 9.8 mg of (4-methoxyphenyl) 2 PN (isopropyl) P (4-methoxyphenyl) 2 (0.018 mmol) in 10 ml of toluene at a solution of 5.6 mg of CrCl 3 .THF 3 (0.015 mmol) in 10 ml of toluene in a Schlenk vessel The mixture was stirred for 5 min. to room temperature and then transferred to a reactor at 300 ml pressure (autoclave) containing a mixture of toluene (80 ml) and MAO (methylaluminoxane, 4.5 mmol) at 40 ° C. He charged pressure reactor with ethylene after which the temperature was maintained from the reactor at 45 ° C, while the ethylene pressure was maintained at 45 barg. Full mixing was guaranteed at all times by 1100 rpm mixing speeds using a drag agitator Of gas. The reaction was terminated after 30 minutes interrupting the ethylene feed to the reactor and cooling the reactor up to below 10 ° C. After releasing the excess ethylene from the autoclave, extinguished the liquid contained in the autoclave with ethanol followed by 10% hydrochloric acid in water. Nonano was added as a standard internal for the analysis of the liquid phase by CG-FID. A small sample of the layer was dried organic over anhydrous sodium sulfate and then analyzed through CG-FID. The rest of the layer was filtered Organic to isolate solid polymer / wax products. Be dried these solid products overnight in an oven to 100 ° C and then weighed to produce 1.0831 g of polyethylene. The GC analysis indicated that the reaction mixture contained 42.72 g of oligomers. The product distribution of this example is summarized in table 1.

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Example 9

Tetramerization reaction of ethylene using Cr (III) 2-ethylhexanoate, (4-methoxyphenyl) 2 PN (isopropyl) P (4-methoxyphenyl) 2  and MAO

A solution of 9.8 mg of (4-methoxyphenyl) 2 PN (isopropyl) P (4-methoxyphenyl) 2 (0.018 mmol) in 10 ml of toluene at a solution of 10.2 mg of Cr (III) 2-ethylhexanoate (70% in oil mineral, 0.015 mmol) in 10 ml of toluene in a container of Schlenk The mixture was stirred for 5 min. at room temperature and It was then transferred to a 300 ml pressure reactor (autoclave) containing a mixture of toluene (80 ml) and MAO (methylaluminoxane, 4.5 mmol) at 40 ° C. The pressure reactor was charged with ethylene after which kept the reactor temperature at 45 ° C while maintained ethylene pressure at 45 barg. Mixing was guaranteed complete at all times by mixing speeds of 1100 rpm using a gas drag agitator. The reaction was terminated after 30 minutes interrupting the ethylene feed to the reactor  and cooling the reactor to below 10 ° C. After releasing the ethylene in excess of the autoclave, the contained liquid was extinguished in the autoclave with ethanol followed by 10% hydrochloric acid in Water. Nonano was added as an internal standard for the analysis of the liquid phase by CG-FID. He dried a small sample of the organic layer over anhydrous sodium sulfate and It was then analyzed using CG-FID. Leaked the rest of the organic layer to isolate polymer products / from solid wax. These solid products were dried overnight in an oven at 100 ° C and then weighed to produce 1.52 g of polyethylene. GC analyzes indicated that the reaction mixture contained 61.27 g of oligomers. The product distribution of This example is summarized in Table 1.

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Example 10

Tetramerization reaction of ethylene using Cr octanoanoate (III), (4-methoxyphenyl) 2 PN (isopropyl) P (4-methoxyphenyl) 2  and MAO

A solution of 9.8 mg of (4-methoxyphenyl) 2 PN (isopropyl) P (4-methoxyphenyl) 2 (0.018 mmol) in 10 ml of toluene at a solution of 10.3 mg of Cr (III) octanoate (70% in toluene, 0.015 mmol) in 10 ml of toluene in a Schlenk container. The mixture was stirred for 5 min. at room temperature and then transferred to a reactor at 300 ml pressure (autoclave) containing a mixture of toluene (80  ml) and MAO (methylaluminoxane, 4.5 mmol) at 40 ° C. He charged pressure reactor with ethylene after which the temperature was maintained from the reactor at 45 ° C, while the ethylene pressure was maintained at 45 barg. Full mixing was guaranteed at all times by 1100 rpm mixing speeds using a drag agitator Of gas. The reaction was terminated after 40 minutes interrupting the ethylene feed to the reactor and cooling the reactor up to below 10 ° C. After releasing the excess ethylene from the autoclave, extinguished the liquid contained in the autoclave with ethanol followed by 10% hydrochloric acid in water. Nonano was added as a standard internal for the analysis of the liquid phase by CG-FID. A small sample of the layer was dried organic over anhydrous sodium sulfate and then analyzed through CG-FID. The rest of the layer was filtered Organic to isolate solid polymer / wax products. Be dried these solid products overnight in an oven to 100 ° C and then weighed to produce 0.3773 g of polyethylene. The GC analysis indicated that the reaction mixture contained 18.91 g of oligomers. The product distribution of this example is summarized in table 1.

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Example eleven

Tetramerization reaction of ethylene using acetylacetonate Cr (III), (4-methoxyphenyl) 2 PN (isopropyl) P (4-methoxyphenyl) 2  and MAO

A solution of 6.6 mg of (4-methoxyphenyl) 2 PN (isopropyl) P (4-methoxyphenyl) 2 (0.012 mmol) in 10 ml of toluene at a solution of 3.5 mg of chromium (III) acetylacetonate (0.015 mmol) in 10 ml of toluene in a Schlenk bowl. The mixture was stirred for 5 min. to room temperature and then transferred to a reactor at 300 ml pressure (autoclave) containing a mixture of toluene (80 ml) and MAO (methylaluminoxane, 3.0 mmol) at 40 ° C. He charged pressure reactor with ethylene after which the temperature was maintained from the reactor at 45 ° C, while the ethylene pressure was maintained at 45 barg. Full mixing was guaranteed at all times by 1100 rpm mixing speeds using a drag agitator Of gas. The reaction was terminated after 30 minutes interrupting the ethylene feed to the reactor and cooling the reactor up to below 10 ° C. After releasing the excess ethylene from the autoclave, extinguished the liquid contained in the autoclave with ethanol followed by 10% hydrochloric acid in water. Nonano was added as a standard internal for the analysis of the liquid phase by CG-FID. A small sample of the layer was dried organic over anhydrous sodium sulfate and then analyzed through CG-FID. The rest of the layer was filtered Organic to isolate solid polymer / wax products. Be dried these solid products overnight in an oven to 100 ° C and then weighed to produce 1.3958 g of polyethylene. The GC analysis indicated that the reaction mixture contained 54.52 g of oligomers. The product distribution of this example is summarized in table 1.

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Example 12

Tetramerization reaction of ethylene using acetylacetonate Cr (III), (4-methoxyphenyl) 2 PN (isopropyl) P (4-methoxyphenyl) 2  and MAO

A solution of 9.8 mg of (4-methoxyphenyl) 2 PN (isopropyl) P (4-methoxyphenyl) 2 (0.018 mmol) in 10 ml of toluene at a solution of 5.2 mg of chromium (III) acetylacetonate (0.015 mmol) in 10 ml of toluene in a Schlenk bowl. The mixture was stirred for 5 min. to room temperature and then transferred to a reactor at 300 ml pressure (autoclave) containing a mixture of toluene (80 ml) and MAO (methylaluminoxane in toluene, 2.25 mmol) at 40 ° C. Be loaded the pressure reactor with ethylene after which the reactor temperature at 45 ° C while the pressure was maintained of ethylene at 45 barg. Full mixing was guaranteed throughout moment by mixing speeds of 1100 rpm using a gas drag agitator. The reaction was terminated after 15 minutes interrupting the ethylene feed to the reactor and cooling the reactor to below 10 ° C. After releasing the ethylene in excess of the autoclave, the contained liquid was extinguished in the autoclave with ethanol followed by 10% hydrochloric acid in Water. Nonano was added as an internal standard for the analysis of the liquid phase by CG-FID. He dried a small sample of the organic layer over anhydrous sodium sulfate and It was then analyzed using CG-FID. Leaked the rest of the organic layer to isolate polymer products / from solid wax. These solid products were dried overnight in an oven at 100 ° C and then weighed to produce 0.5010 g of polyethylene. GC analyzes indicated that the reaction mixture It contained 70.87 g of oligomers. The product distribution of this example is summarized in table 1.

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Example 13

Tetramerization reaction of ethylene using acetylacetonate Cr (III), (4-methoxyphenyl) 2 PN (isopropyl) P (4-methoxyphenyl) 2  and MMAO-3A

A solution of 16.4 mg of (4-methoxyphenyl) 2 PN (isopropyl) P (4-methoxyphenyl) 2 (0.03 mmol) in 10 ml of toluene at a solution of 5.2 mg of chromium (III) acetylacetonate (0.015 mmol) in 10 ml of toluene in a Schlenk bowl. The mixture was stirred for 5 min. to room temperature and then transferred to a reactor at 300 ml pressure (autoclave) containing a mixture of toluene (80 ml) and MMAO-3A (methylaluminoxane modified in heptanes, 4.5 mmol) at 40 ° C. The pressure reactor was charged with ethylene after which the reactor temperature was maintained at 45 ° C, while the ethylene pressure was maintained at 45 barg. Be guaranteed complete mixing at all times through speeds 1100 rpm mixing using a gas drag agitator. Be the reaction ended after 22 minutes interrupting the feeding of ethylene to the reactor and cooling the reactor to below 10 ° C After releasing the ethylene in excess of the autoclave, it was extinguished the liquid contained in the autoclave with ethanol followed by acid 10% hydrochloric in water. Nonano was added as internal standard for the analysis of the liquid phase by CG-FID. A small sample of the organic layer was dried over sulfate of anhydrous sodium and then analyzed by CG-FID. The rest of the organic layer was filtered to isolate the products Solid polymeric / wax. These solid products were dried overnight in an oven at 100 ° C and then weighed producing 1.76 g of polyethylene. GC analyzes indicated that The reaction mixture contained 50.42 g of oligomers. The Product distribution of this example is summarized in the table one.

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Example 14

Tetramerization reaction of ethylene using acetylacetonate Cr (III), (4-methoxyphenyl) 2 PN (isopropyl) P (4-methoxyphenyl) 2  and EAO / TMA

A solution of 36.1 mg of (4-methoxyphenyl) 2 PN (isopropyl) P (4-methoxyphenyl) 2 (0.066 mmol) in 10 ml of toluene at a solution of 5.2 mg of chromium (III) acetylacetonate (0.015 mmol) in 10 ml of toluene in a Schlenk bowl. The mixture was stirred for 5 min. to room temperature and then transferred to a reactor at 300 ml pressure (autoclave) containing a mixture of toluene (80 ml), EAO (ethylaluminoxane in toluene, 33 mmol) and TMA (trimethylaluminum, 8.25 mmol) at 40 ° C. The reactor was charged to pressure with ethylene after which the temperature of the reactor at 45 ° C, while ethylene pressure was maintained at 45 barg Full mixing was guaranteed at all times by 1100 rpm mixing speeds using a drag agitator Of gas. The reaction was terminated after 60 minutes interrupting the ethylene feed to the reactor and cooling the reactor up to below 10 ° C. After releasing the excess ethylene from the autoclave, extinguished the liquid contained in the autoclave with ethanol followed by 10% hydrochloric acid in water. Nonano was added as a standard internal for the analysis of the liquid phase by CG-FID. A small sample of the layer was dried organic over anhydrous sodium sulfate and then analyzed through CG-FID. The rest of the layer was filtered Organic to isolate solid polymer / wax products. Be dried these solid products overnight in an oven to 100 ° C and then weighed to produce 0.189 g of polyethylene. The GC analysis indicated that the reaction mixture contained 40.97 g of oligomers. The product distribution of this example is summarized in table 1.

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Example fifteen

Tetramerization reaction of ethylene using acetylacetonate Cr (III), (4-methoxyphenyl) 2 PN (isopropyl) P (4-methoxyphenyl) 2  and MAO in the presence of H2

A solution of 16.4 mg of (4-methoxyphenyl) 2 PN (isopropyl) P (4-methoxyphenyl) 2 (0.03 mmol) in 10 ml of toluene at a solution of 5.2 mg of chromium (III) acetylacetonate (0.015 mmol) in 10 ml of toluene in a Schlenk bowl. The mixture was stirred for 5 min. to room temperature and then transferred to a reactor at 300 ml pressure (autoclave) containing a mixture of toluene (80 ml) and MAO (methylaluminoxane in toluene, 4.5 mmol) at 40 ° C. The pressure reactor was first charged with hydrogen until a pressure of approximately 2.5 barg and later with ethylene up to 45 barg after which the temperature of the reactor at 45 ° C, while ethylene pressure was maintained at 45 barg Full mixing was guaranteed at all times by 1100 rpm mixing speeds using a drag agitator Of gas. The reaction was terminated after 15 minutes interrupting the ethylene feed to the reactor and cooling the reactor up to below 10 ° C. After releasing the excess ethylene from the autoclave, extinguished the liquid contained in the autoclave with ethanol followed by 10% hydrochloric acid in water. Nonano was added as a standard internal for the analysis of the liquid phase by CG-FID. A small sample of the layer was dried organic over anhydrous sodium sulfate and then analyzed through CG-FID. The rest of the layer was filtered Organic to isolate solid polymer / wax products. Be dried these solid products overnight in an oven to 100 ° C and then weighed to produce 1.2060 g of polyethylene. GC analyzes indicated that the reaction mixture contained 81.51 g of oligomers. The product distribution of this example It is summarized in table 1.

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Reference

Example 16

Tetramerization reaction of ethylene using acetylacetonate Cr (III), (phenyl) 2 PN (isopropyl) P (2-methoxyphenyl) 2  and MAO

The reference example is out of reach of the invention.

A solution of 32.2 mg of (phenyl) 2 PN (isopropyl) P (2-methoxyphenyl) 2 (0.066 mmol) in 10 ml of toluene at a solution of 11.5 mg of chromium (III) acetylacetonate (0.033 mmol) in 10 ml of toluene in a Schlenk bowl. The mixture was stirred for 5 min. to room temperature and then transferred to a reactor at 300 ml pressure (autoclave) containing a mixture of toluene (80 ml) and MAO (methylaluminoxane in toluene, 4.5 mmol) at 40 ° C. In First, the pressure reactor was charged with ethylene after which the reactor temperature was maintained at 45 ° C while maintained the ethylene pressure at 4500 kPa (45 barg). The complete mixing at all times through mixing speeds 1100 rpm using a gas drag agitator. The reaction after 15 minutes interrupting ethylene feed to the reactor and cooling the reactor to below 10 ° C. After release the ethylene in excess of the autoclave, the liquid was extinguished contained in the autoclave with ethanol followed by hydrochloric acid 10% in water. Nonano was added as an internal standard for the Liquid phase analysis using CG-FID. Dried up a small sample of the organic layer over sodium sulfate anhydrous and then analyzed by CG-FID. Be filtered the rest of the organic layer to isolate the products Solid polymeric / wax. These solid products were dried overnight in an oven at 100 ° C and then weighed producing 6.82 g of polyethylene. GC analyzes indicated that The reaction mixture contained 38.33 g of oligomers. The Product distribution of this example is summarized in the table one.

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TABLE 1 Tetramerization rounds of ethylene: Examples 2-16

one

Claims (51)

1. Procedure for oligomerization of olefins that includes the step of contacting a current of olefinic feed with a catalyst system that includes the combination of:

a compound of chrome; Y

a ligand heteroatomic described by the following formula general

(R 1) (R 2) A-B-C (R 3) (R 4)

in the that

A and C are independently selected from the group consisting of phosphorus, arsenic, antimony, bismuth and nitrogen;

B is a group of union between A and C; Y

each one of R1, R2, R3 and R4 are independently selected of the group consisting of a non-aromatic group, an aromatic group and a heteroaromatic group, of which at least one of R1, R 2, R 3 and R 4 is substituted with a substituent polar; and wherein at least one of R1, R2, R3 and R 4, if aromatic, is substituted with a polar substituent on a 2nd atom or an additional atom of the atom attached to A or C and provided that any of the polar substituents on R1, R 2, R 3 and R 4, if aromatic, are not on the atom adjacent to the atom attached to A or C.

2. Method according to claim 1, in which up to four of R 1, R 2, R 3 and R 4 have substituents on the atom adjacent to the atom attached to A or C. 3. Method according to claim 1, which it is a tetramerization procedure and in which each of R 1, R 2, R 3 and R 4 is aromatic, including heteroaromatic, but not all of R1, R2, R3 and R 4 are substituted with a substituent on an atom adjacent to the atom attached to A or C. 4. Method according to claim 3, in which no more than two of R 1, R 2, R 3 and R 4 have substituents on the atom adjacent to the atom attached to A or C. 5. Procedure according to any one of the claims 1 to 4, wherein each polar substituent on one or more than R 1, R 2, R 3 and R 4 is a donor of electrons 6. Procedure according to any one of the claims 3 or 4, wherein the supply current includes an α-olefin and the stream of product includes at least 30% of a monomer of tetramerized α-olefin. 7. Method according to claim 6, in which the olefinic feed stream includes ethylene and the product stream includes at least 30% of 1-octene. 8. Procedure according to any one of the claims 1 to 7, wherein the supply current olefinic includes ethylene and in which the ratio of (C6 + C_ {8}) :( C_ {4} + C_ {10}) in the product stream is over 2.5: 1 9. Procedure according to any one of the claims 1 or 3, wherein the supply current Olefinic includes ethylene and in which the ratio of C 8: C 6 in the product stream is more than 1. 10. Procedure according to any one of the claims 1 to 9, wherein the pressure is greater than 100 kPa (1 barg) 11. Procedure according to any one of the claims 7 to 9, wherein ethylene is contacted with the catalyst system at a pressure of more than 1000 kPa (10 barg) 12. Procedure according to any one of the claims 1 to 11, wherein A and / or C are a donor of potential electrons for coordination with chromium. 13. Procedure according to any one of the claims 1 to 12, wherein B is selected from the group that It consists of an organic binding group comprising a hydrocarbylene, a substituted hydrocarbylene, a heterohydrocarbileno or a substituted heterohydrocarbileno; a group inorganic junction comprising a junction spacer of a single atom; and a group comprising methylene, dimethylmethylene, 1,2-ethylene, 1,2-phenylene, 1,2-propylene, 1,2-catecholate, -N (CH 3) - N (CH 3) -, -B (R 5) -, -Si (R 5) 2 -, -P (R 5) - and -N (R 5) - in which R 5 is hydrogen, a hydrocarbyl or substituted hydrocarbyl, a heteroatom substituted and a halogen. 14. Method according to claim 13, in the one that B is a single-junction junction spacer. 15. Method according to claim 13, in where B is -N (R 5) -, in which R 5 is selected from the groups consisting of hydrogen, alkyl, alkyl groups substituted, aryl, substituted aryl, aryloxy, aryloxy substituted, halogen, alkoxycarbonyl, carbonyloxy, alkoxy, aminocarbonyl, carbonylamino, dialkylamino, silyl or derivatives of the same, and aryl substituted with any of these substituents 16. Procedure according to any one of the claims 1 to 15, wherein A and / or C are oxidized independently by S, Se, N or O, in which the valence of A and / or C allows such oxidation. 17. Procedure according to any one of the claims 1 to 15, wherein A and C are independently phosphorus or phosphorus oxidized by S or Se or N or O. 18. Method according to claim 1, in which R 1, R 2, R 3 and R 4 are selected regardless of the group consisting of benzyl, phenyl group, tolyl, xylyl, mesityl, biphenyl, naphthyl, anthracenyl, methoxy, ethoxy, phenoxy, tolyloxy, dimethylamino, diethylamino, methylethylamino, thiophenyl, pyridyl, thioethyl, thiophenoxy, trimethylsilyl, dimethylhydracil, methyl, ethyl, ethenyl, propyl, butyl, propenyl, propynyl, cyclopentyl, cyclohexyl, ferrocenyl and tetrahydrofuranyl; and at least one of R1, R 2, R 3 and R 4 is substituted with a substituent polar. 19. The method of claim 1, wherein the ligand is selected from the group consisting of (3-methoxyphenyl) 2 PN (methyl) P (3-methoxyphenyl) 2, (4-methoxyphenyl) _ {2 PN (methyl) P (4-methoxyphenyl) 2, (3-methoxyphenyl) 2 PN (isopropyl) P (3-methoxyphenyl) 2, (4-methoxyphenyl) 2 PN (isopropyl) P (4-methoxyphenyl) 2, (4-methoxyphenyl) 2 PN (2-ethylhexyl) P (4-methoxyphenyl) 2,
(3-methoxyphenyl) (phenyl) PN (methyl) P (phenyl) 2, (4-methoxyphenyl) (phenyl) PN (methyl) P (phenyl) 2, (3-methoxyphenyl) (phenyl) PN (methyl) P
(3-methoxyphenyl) (phenyl), (4-methoxyphenyl) (phenyl) PN (methyl) P (4-methoxyphenyl) (phenyl), (3-methoxyphenyl) 2 PN (methyl) P (phenyl) 2, (4-methoxyphenyl) 2 PN (methyl) P (phenyl) 2, (4-methoxyphenyl) 2 PN (1-cyclohexylethyl) P (4-methoxyphenyl) 2 , (4-methoxyphenyl) 2 PN (2-methylcyclohexyl) P (4-methoxyphenyl) 2, (4-methoxyphenyl) 2 PN (decyl) P (4-methoxyphenyl) 2 , (4-methoxyphenyl) 2 PN (pentyl) P (4-methoxife-
nil) 2, (4-methoxyphenyl) 2 PN (benzyl) P (4-methoxyphenyl) 2, (4-methoxyphenyl) 2 PN (phenyl) P (4-methoxyphenyl) ) 2, (4-fluorophenyl) 2 PN
(methyl) P (4-fluorophenyl) 2, (2-fluorophenyl) 2 PN (methyl) P (2-fluorophenyl) 2, (4-dimethylamino-phenyl) 2 PN (methyl) P (4-dimethylamino-phenyl) 2, (4-methoxyphenyl) 2 PN (allyl) P (4-methoxyphenyl) 2, (4- (4-methoxyphenyl) -phenyl ) 2 PN (isopropyl) P (4- (4-methoxyphenyl) -phenyl) 2 and (4-methoxyphenyl) (phenyl) PN (isopropyl) P (phenyl) 2. 20. Procedure according to any one of the claims 1 to 19, wherein the catalyst system is prepare by combining the heteroatomic ligand in any order with the chromium compound and an activator. 21. Method according to claim 20, which includes the stage of adding a coordination complex preformed, prepared using the heteroatomic ligand and the chromium compound, to a reaction mixture containing the activator. 22. The method of claim 20, which includes the step of generating a heteroatomic coordination complex in situ from the chromium compound and a heteroatomic ligand. 23. Procedure according to any one of the claims 1 to 22, wherein the chromium compound is select from the group consisting of an inorganic salt, a salt organic, a coordination complex and a complex organometallic 24. Method according to claim 23, in which the chromium compound is selected from the group consisting in complex of tris-tetrahydrofuran-trichloride chromium, (benzene) tricarbonyl-chromium, octanoate of chromium (III), chromium (III) acetylacetonate, hexacarbonyl chromium and 2-ethylhexanoate of chrome (III). 25. Method according to claim 24, in which the chromium compound is selected from a complex selected from chromium (III) acetylacetonate and Chromium (III) 2-ethylhexanoate. 26. Procedure according to any one of the claims 1 to 25, wherein the chromium of the chromium compound and the heteroatomic ligand combine to provide a reason chrome / ligand from about 0.01: 100 to 10000: 1. 27. Procedure according to any one of the claims 20 to 22, wherein the catalyst system includes an activator selected from the group consisting of a organoaluminum compound, an organoboro compound, a salt organic, such as methylmagnesium bromide and methyl lithium, a salt and an inorganic acid, such as tetrafluoroboric acid etherate, Silver tetrafluoroborate and sodium hexafluoroantimoniate. 28. Method according to claim 27, in which the activator is an alkylaluminoxane. 29. Method according to claim 28, in which the chromium compound and aluminoxane are combined in proportions to provide an Al / chrome ratio of from approximately 1: 1 to 10,000: 1.

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30. Tetramerization catalyst system which includes the combination of:

a compound of chrome; Y

a ligand heteroatomic described by the following formula general

(R 1) (R 2) A-B-C (R 3) (R 4)

in the that

A and C are independently selected from the group consisting of phosphorus, arsenic, antimony, bismuth and nitrogen;

B is a group of union between A and C; Y

each one of R1, R2, R3 and R4 are independently selected of the group consisting of a non-aromatic group, an aromatic group and a heteroaromatic group, of which at least one of R1, R 2, R 3 and R 4 is substituted with a substituent polar;

and in which at minus one of R 1, R 2, R 3 and R 4, if aromatic, is substituted with a polar substituent on a 2nd atom or a additional atom of the atom attached to A or C and provided that any of polar substituents on R 1, R 2, R 3 and R 4, if aromatic, is not on the atom adjacent to the atom attached to A or C.

31. Catalyst system according to claim 30, wherein each of R 1, R 2, R 3 and R 4 is aromatic, including heteroaromatic, but not all of R1, R2, R3 and R4 are substituted with a substituent on an atom adjacent to the atom attached to A or C. 32. Catalyst system according to claim 31, wherein no more than two of R1, R2, R 3 and R 4 have substituents on the atom adjacent to the atom attached to A or C. 33. Catalyst system according to any one of claims 30 to 32, wherein each polar substituent on one or more of R 1, R 2, R 3 and R 4 is a donor of electrons 34. Catalyst system according to any one of claims 30 to 33, wherein A and / or C are a donor of potential electrons for coordination with chromium. 35. Catalyst system according to any one of claims 30 to 34, wherein B is selected from group consisting of an organic binding group comprising a hydrocarbylene, a substituted hydrocarbylene, a heterohydrocarbileno and a substituted heterohydrocarbileno; a group inorganic junction comprising a junction spacer of a single atom; and a group comprising methylene, dimethylmethylene, 1,2-ethylene, 1,2-phenylene, 1,2-propylene, 1,2-catecholate, -N (CH 3) - N (CH 3) -, -B (R 5) -, -Si (R 5) 2 -, -P (R 5) - and -N (R 5) - in which R 5 is hydrogen, a hydrocarbyl or substituted hydrocarbyl, a heteroatom  substituted and a halogen. 36. Catalyst system according to claim 35, wherein B is a single-junction spacer atom. 37. Catalyst system according to claim 35, wherein B is selected to be -N (R 5) -, in which R 5 is selected from the groups which consist of hydrogen, alkyl, substituted alkyl groups, aryl, substituted aryl, aryloxy, substituted aryloxy, halogen, alkoxycarbonyl, carbonyloxy, alkoxy, aminocarbonyl, carbonylamino, dialkylamino, silyl or derivatives thereof, and aryl substituted with any of these substituents. 38. Catalyst system according to any one of claims 30 to 37, wherein A and / or C are oxidized independently by S, Se, N or O, in which the valence of A and / or C allows such oxidation. 39. Catalyst system according to any one of claims 30 to 37, wherein A and C is independently phosphorus or phosphorus oxidized by S or Se or N u OR. 40. The catalyst system according to any one of claims 30 to 39, wherein the ligand is selected from the group consisting of (3-methoxyphenyl) 2 PN (methyl) P (3-methoxyphenyl) 2 , (4-methoxyphenyl) 2 PN (methyl) P (4-methoxyphenyl) 2, (3-methoxyphenyl) 2 PN (isopropyl) P (3-methoxyphenyl) 2, ( 4-methoxyphenyl) 2 PN (isopropyl) P (4-methoxyphenyl) 2, (4-methoxyphenyl) 2 PN (2-ethylhexyl) P (4-methoxyphenyl) 2, ( 3-methoxyphenyl) (phenyl) PN (methyl) P (phenyl) 2, (4-methoxyphenyl) (phenyl) PN (methyl) P (phenyl) 2, (3-methoxyphenyl) (phenyl) PN (methyl) P (3-methoxyphenyl) (phenyl), (4-methoxyphenyl) (phenyl) PN (methyl) P (4-methoxyphenyl) (phenyl), (3-methoxyphenyl) 2 PN (methyl) P ( phenyl) 2, (4-methoxyphenyl) 2 PN (methyl) P (phenyl) 2, (4-methoxyphenyl) 2 PN (1-cyclohexylethyl) P (4-methoxife-
nil) 2, (4-methoxyphenyl) 2 PN (2-methylcyclohexyl) P (4-methoxyphenyl) 2, (4-methoxyphenyl) 2 PN (decyl) P (4- methoxyphenyl) 2, (4-methoxyphenyl) 2 PN (pentyl) P (4-methoxyphenyl) 2, (4-methoxyphenyl) 2 PN (benzyl) P (4-methoxyphenyl) 2, (4-methoxyphenyl) 2 PN (phenyl) P (4-metho-
xiphenyl) 2, (4-fluorophenyl) 2 PN (methyl) P (4-fluorophenyl) 2, (2-fluorophenyl) 2 PN (methyl) P (2-fluorophenyl) _ {2}, (4-dimethylamino-fe-
nil) 2 PN (methyl) P (4-dimethylamino-phenyl) 2, (4-methoxyphenyl) 2 PN (allyl) P (4-methoxyphenyl) 2, (4- (4-methoxyphenyl) -phenyl) 2 PN (isopropyl) P (4- (4-methoxyphenyl) -phenyl) 2 and (4-methoxyphenyl) (phenyl) PN (isopropyl) P (phenyl) _ {2}. 41. Catalyst system according to any one of claims 30 to 40, wherein the chromium compound is select from the group consisting of an inorganic salt, a salt organic, a coordination complex and a complex organometallic 42. Catalyst system according to claim 41, wherein the chromium compound is selected from the group consisting of complex of tris-tetrahydrofuran-trichloride chromium, (benzene) tricarbonyl-chromium, octanoate of chromium (III), chromium (III) acetylacetonate, hexacarbonyl-chromium and Chromium (III) 2-ethylhexanoate. 43. Catalyst system according to claim 42, wherein the chromium is selected from a complex selected from chromium (III) acetylacetonate and Chromium (III) 2-ethylhexanoate. 44. Catalyst system according to any one of claims 30 to 43, wherein the chromium of the compound Chromium and heteroatomic ligand combine to provide a chromium / ligand ratio of from about 0.01: 100 to 10000: 1. 45. Catalyst system according to any one of claims 30 to 44, which includes an activator. 46. Catalyst system according to claim 45, wherein the activator is selected from the group consisting of an organoaluminum compound, a compound of organoboro, an organic salt, such as methylmagnesium bromide and methyllithium, a salt and an inorganic acid, such as acid etherate tetrafluoroboric, silver tetrafluoroborate and sodium hexafluoroantimoniate. 47. Catalyst system according to claim 46, wherein the activator is a alkylaluminoxane. 48. Catalyst system according to claim 47, wherein the alkylaluminoxane is selected from the group consisting of methylaluminoxane (MAO), ethylaluminoxane (EAO), modified alkylaluminoxanes (MMAO) and mixtures of same. 49. Catalyst system according to claim 47 or claim 48, wherein the chromium and the aluminoxane combine in proportions to provide a reason Al / chrome from about 1: 1 to 10,000: 1. 50. Use of a catalyst system according to a any one of claims 30 to 49 for tetramerization of olefins 51. Use of a catalyst system according to a any one of claims 30 to 49 for tetramerization of ethylene.