JP2006511625A - Tetramerization of olefins - Google Patents

Abstract

The present invention describes an olefin tetramerization process wherein the product stream of the process contains more than 30% tetramer olefins. The method includes contacting the olefin feed stream with a catalyst system containing a transition metal compound and a heteroatom ligand.

Description

  The present invention relates to ethylene oligomerization. More particularly, the present invention relates to the identification and use of ligands for tetramerization processes, olefin tetramerization catalyst systems, and olefin tetramerization catalyst systems.

  The present invention defines methods and catalyst systems that promote the production of 1-octene with high selectivity while avoiding significant amounts of butene, other octene isomers, particularly polymeric oligomers and polyethylene by-products. The catalyst system can also be used for the tetramerization of other olefins, in particular α-olefins.

Despite the well-known utility of 1-octene, the art does not teach a commercially successful method for tetramerization of ethylene that selectively produces 1-octene. . Conventional ethylene oligomerization techniques produce a series of α-olefins that follow either a Schulz-Flory or Poisson product distribution. By definition, these mathematical distributions limit the mass% of tetramer that can be formed to distribute the product. In this context, the chelating ligand is preferably 2-diphenylphosphinobenzoic acid (DPPBA), the nickel compound is preferably NiCl ₂ .6H ₂ O, and the catalyst activator is preferably sodium tetraphenylborate. It is known from the prior art (US Pat. No. 6,184,428) that the nickel catalyst comprising catalyzes the oligomerization of ethylene resulting in a mixture of linear olefins. The selectivity for linear C ₈ α-olefin is said to be 19%. Similarly, the Shell Higher Olefins Process (SHOP method, US Pat. Nos. 3,676,523 and 3,635,937) using a similar catalyst system is 11% by weight of 1-% in the product mixture. Octene is generally reported to occur (Chem Systems PERP report, 90-1, 93-6 and 94 / 95S12).

  Ziegler-type technology based on trialkylammonium catalysts uniquely developed by the Gulf Oil Chemical Company (Chevron, eg, German Patent No. 1443927) and Ethyl Corporation (BP / Amoco, eg, US Pat. No. 3,906,053) is also available. , Which has been used commercially to oligomerize ethylene to a mixture of olefins containing 13-25% by weight of 1-octene, reportedly (Chem Systems PERP Report, 90-1, 93-6). And 94 / 95S12).

The prior art also teaches that chromium-based catalysts containing heteroatom ligands with both phosphorus and nitrogen heteroatoms selectively catalyze ethylene trimerization to 1-hexene. is doing. The above heteroatom ligands for the trimerization of ethylene include bis (2-diethylphosphino-ethyl) amine (WO 03/053891, hereby incorporated by reference in its entirety) and ( o-methoxyphenyl) ₂ PN (methyl) P (o-methoxyphenyl) ₂ (WO 02/04119, which is hereby incorporated by reference in its entirety). Both of these catalyst systems and methods are very specific for the production of 1-hexene and 1-octene is only produced as an impurity (generally produced as disclosed by WO 02/04119). Less than 3% by weight of the product mixture). The two heteroatoms of phosphorus coordinated to (o-methoxyphenyl) ₂ PN (methyl) P (o-methoxyphenyl) ₂ (WO02 / 04119) are separated from each other by one nitrogen atom. The nitrogen atom is not coordinated to chromium unless at least an activator is present, and is considered to be bidentate if the ligand has no additional electron donating atoms. In addition, it has been argued that polar or electron donating substituents in the ortho position of the phenyl group help to form a tridentate system, “This allows the orthomethoxy group to act as a pendant donor, It was assumed that the potential to increase coordination saturation is an important factor. " Commun. , 2002, 858-859, as repeated by the inventors of WO 02/04119, it is generally believed to increase the selectivity of 1-hexene formation. Chem. Commun. , 2002, 858-859, in order to support their hypothesis, as a ligand under catalytic conditions, any of the above orthosides on at least one of R ¹ , R ² , R ³ and R ⁴ compounds without polar substituent, showed that even using - - (phenyl p- methoxy) _2, the catalytic activity for α- olefin not introduce any (p- methoxyphenyl) ₂ PN (methyl) P. WO 02/04119 (Example 16) teaches a process and catalyst system for producing octene using olefin trimerization. In this example, 1-butene is trimerized with two ethylene molecules to yield 25% octene. However, the nature of these octenes is not disclosed and the applicant believes that they consist of a mixture of linear and branched octenes.

  The prior art is unlikely to expand the commonly accepted 7-membered metallacycle reaction intermediate for ethylene trimerization (Chem. Commun., 1989, 674) to 9-membered metallacycles (Organometrics, 2003, 22, 2564; Angew. Chem. Int. Ed., 2003, 42 (7), 808) teaches that high 1-octene selectivity cannot be achieved. It has been argued that the 9-membered ring is the least preferred medium size ring and therefore should be sparse compared to the 7-membered ring (Organometrics, 2003, 22, 2564). In addition, “If a 9-membered ring is formed, it is likely to grow to an 11-membered or 13-membered ring. In other words, not many octenes are expected, but a significant amount of (directly "Chain) decene or dodecene makes more sense," said the same author.

  In spite of its exact opposite teaching, the Applicant has now found a way to selectively produce tetramerized olefins. Applicants further note that chromium-based catalysts containing mixed heteroatom ligands with both nitrogen and phosphorus heteroatoms having polar substituents on the hydrocarbyl or heterohydrocarbyl group on the phosphorus atom are often 60 It has been found that ethylene can be used to selectively tetramerize to 1-octene with a selectivity greater than% by weight. This high degree of 1-octene selectivity cannot be achieved by conventional one-stage ethylene oligomerization or trimerization techniques that only yield up to 25% by weight of 1-octene.

  The present invention relates to a method for selectively producing a tetramer product.

  The present invention particularly relates to a method for selectively producing a tetramer product such as 1-octene from an olefin such as ethylene.

  The present invention relates to a method for selectively producing a tetramer product using a transition metal catalyst system containing a heteroatom ligand.

  According to a first aspect of the present invention, an olefin tetramerization process, wherein the product of the tetramerization process is an olefin, produced over 30% of the product stream of the process.

According to a second aspect of the present invention, the tetramerization process comprises contacting the olefin feed stream with a catalyst system comprising a transition metal and a heteroatom ligand, the tetramerization process. The product of is an olefin and produces over 30% of the product stream of the process.
In this specification,% is mass%.

  The term “tetramerization” generally refers to a reaction in which four, preferably four, identical olefin monomer units yield linear and / or branched olefins.

  Heteroatomic means a ligand containing at least two heteroatoms, which may be the same or different, the heteroatoms being phosphorus, arsenic, antimony, sulfur, oxygen, It can be selected from bismuth, selenium or nitrogen.

  The feed stream contains olefins to be tetramerized and can be introduced into the process according to the invention in a continuous or batch fashion.

  The product stream contains tetramers, which are produced in a continuous or batch fashion according to the present invention.

  The feed stream can contain α-olefins and the product stream can contain at least 30%, preferably at least 35% tetramerized α-olefin monomers.

  The method includes a method of tetramerizing α-olefin. The term α-olefin refers to all hydrocarbon compounds having a terminal double bond. This definition includes ethylene, propylene, 1-butene, isobutylene, 1-pentene, 1-hexene, 1-octene and the like.

  The method can include a method of tetramerization of α-olefins that selectively yields a tetrameric α-olefin product.

  The olefin feed stream can comprise ethylene and the product stream can comprise at least 30% 1-octene. The method may be a method for tetramerization of ethylene.

  The present invention makes it possible to select the ligand, catalyst system and / or processing conditions to produce a product stream exceeding 40%, 50% or 60% α-olefin. Depending on the more advanced use of the product stream, it may be desirable to have such a high selectivity for α-olefins.

The olefin feed stream can comprise ethylene and the ratio of (C ₆ + C ₈ ) :( C ₄ + C ₁₀ ) in the product stream can exceed 2.5: 1.

The olefin feed stream can comprise ethylene and the ratio of C ₈ : C _{6 in} the product stream is greater than 1.

  Ethylene can be contacted with the catalyst system at a pressure above 1 barg, preferably above 10 barg, more preferably above 30 barg.

The heteroatom ligand is represented by the following general formula (R) _n ABC (R) _m (wherein A and C are independently phosphorus, arsenic, antimony, oxygen, bismuth, sulfur, selenium). And B is a linking group between A and C, and R is from either a homo or heterohydrocarbyl group in which at least one R group is substituted with a polar substituent. Independently selected, and n and m can be represented by the respective valences and oxidation states of A and C).

A and / or C can be a potential electron donor for coordination with the transition metal.
An electron donor or electron donating substituent is defined as an entity that donates electrons used in the formation of chemical bonds including donating covalent bonds.

The heteroatom ligand is represented by the following general formula (R ¹ ) (R ² ) ABC (R ³ ) (R ⁴ ) (where A and C are independently phosphorus, arsenic, antimony, , Bismuth and nitrogen, B is a linking group between A and C, and R ¹ , R ² , R ³ and R ⁴ are independently a non-aromatic group and a heterocyclic group Selected from aromatic groups including aromatic, wherein at least one of R ¹ , R ² , R ³ and R ⁴ is substituted with a polar substituent.

In some embodiments of the method aspects of the present invention, up to four of R ¹ , R ² , R ^3, and R ⁴ have substituents on atoms adjacent to atoms bonded to A or C. Can have.

In addition to at least one of R ¹ , R ² , R ^3, and R ⁴ that is substituted by a polar substituent, each R ¹ , R ² , R ^3, and R ⁴ is an aromatic, including a heterocyclic aromatic Preferably, but not all R ¹ , R ² , R ³ and R ⁴ are optional on the atom adjacent to the atom bound to A or C, if they are all aromatic Is substituted by a substituent of

In addition to at least one of R ¹ , R ² , R ³ and R ⁴ substituted by polar substituents, no more than two R ¹ , R ² , R ³ and R ⁴ are all aromatic In some cases, it may have a substituent on the atom adjacent to the atom bonded to A or C.

If R ¹ , R ² , R ³ and R ⁴ are all aromatic, then any polar substituents there may not be on the atom adjacent to the atom bound to A or C preferable.

When at least one of R ¹ , R ² , R ^3, and R ⁴ is aromatic, it can be substituted with a polar substituent on an atom that is second or more away from the atom bound to A or C.

Any of the polar substituents on one or more of R ¹ , R ² , R ³ and R ⁴ can be electron donating.

Polarity is defined by IUPAC as an entity with an invariant electric dipole moment. The polar substituent, methoxy, ethoxy, _isopropoxy, C 3 _{-C 20} alkoxy, phenoxy, pentafluorophenoxy, trimethylsiloxy, dimethylamino, methylsulfanyl, tosyl, methoxymethyl, methylthiomethyl, 1,3-oxazolyl, Metometokishi , Hydroxyl, amino, phosphino, arsino, stivino, sulfate, nitro and the like.

Any of the groups R ¹ , R ² , R ³ and R ⁴ is independently bonded to one or more of each other or to the linking group B, together with A and C, A and B or B and C A ring structure can be formed.

R ¹ , R ² , R ³ and R ⁴ are independently benzyl, phenyl, tolyl, xylyl, mesityl, biphenyl, naphthyl, anthracenyl, methoxy, ethoxy, phenoxy, tolyloxy, dimethylamino, diethylamino, methylethylamino, It can be selected from the group consisting of thiophenyl, pyridyl, thioethyl, thiophenoxy, trimethylsilyl, dimethylhydrazyl, methyl, ethyl, ethenyl, propyl, butyl, propenyl, propynyl, cyclopentyl, cyclohexyl, ferrocenyl and tetrahydrofuranyl groups. Preferably, R ¹ , R ² , R ³ and R ⁴ can be independently selected from the group consisting of phenyl, tolyl, biphenyl, naphthyl, thiophenyl and ethyl groups.

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

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

B is an organic linking group including hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl and substituted heterohydrocarbyl; inorganic linking group including single atom bond; ionic bond and methylene, dimethylmethylene, 1,2-ethane, 1,2-phenylene , 1,2-propane, 1,2-catechol, 1,2-dimethylhydrazine, -B (R ⁵ )-, -Si (R ⁵ ) _2- , -P (R ⁵ )-and -N (R ⁵ )-(R ⁵ is hydrogen, hydrocarbyl or substituted hydrocarbyl, substituted heteroatom or halogen). Preferably B is —N (R ⁵ ) —, where R ⁵ is a hydrocarbyl or substituted hydrocarbyl group. R ⁵ is hydrogen or an alkyl, substituted alkyl, aryl, substituted aryl, aryloxy, substituted aryloxy, halogen, nitro, alkoxycarbonyl, carbonyloxy, alkoxy, aminocarbonyl, carbonylamino, dialkylamino, silyl group Or it can be selected from the group consisting of derivatives thereof and aryl substituted by any of these substituents. Preferably, R ⁵ can be an isopropyl, 1-cyclohexylethyl, 2-methylcyclohexyl or 2-octyl group.

  B can be selected to be a single atom spacer. Single atom bonded spacers are defined as substituted or unsubstituted atoms that are directly bonded to A and C.

The ligand can also contain a plurality of (R) _nABC (R) _m units. Non-limiting examples of such ligands include dendrimer ligands as well as ligands in which individual units are linked either by one or more R groups or by a linking group B. More specific examples of the ligand include, but are not limited to, 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} and 1,4-di - (P (4-methoxyphenyl) N ( Mention may be made of methyl) P (4-methoxyphenyl) ₂ ) -benzene.

The ligand can be prepared by procedures known to those skilled in the art and disclosed in published literature. Examples of ligands, _{(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 and (4-methoxyphenyl) (phenyl) PN (methyl) P (phenyl) ₂ , (3 -Methoxyphenyl) (phenyl) PN (methyl) P (3-methoxyphenyl) (phenyl), (4-methoxyphenyl) ( Eniru) 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 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} There is.

  The catalyst system can include an activator, and the method can include combining the heteroatom ligand with the transition gold compound and the activator in any order.

  The method can include generating a heteroatom coordination complex in situ from the transition metal compound and the heteroatom ligand. The method involves adding a preformed coordination complex to the reaction mixture, prepared using a heteroatom ligand and a transition metal compound, or generating a heteroatom coordination complex of a transition metal in situ. As such, it can include adding the heteroatom ligand and the transition metal compound separately to the reactor. The generation of a heteroatom coordination complex in situ means that the complex is generated in a medium in which a catalytic reaction occurs. In general, heteroatom coordination complexes are generated in situ. Generally, the transition metal compound and the heteroatom ligand provide a metal / ligand ratio of about 0.01: 100 to 10,000: 1, preferably about 0.1: 1 to 10: 1. To match (both in situ and ex situ).

  The transition metal can be selected from any one of the group consisting of chromium, molybdenum, tungsten, titanium, tantalum, vanadium and zirconium, preferably chromium.

  Transition metal compounds that catalyze the tetramerization of ethylene according to the present invention by mixing with heteroatom ligands and activators can be single inorganic salts, or organic salts, coordination complexes or organometallics. Complex comprising chromium trichloride tris-tetrahydrofuran complex, (benzene) -tricarbonyl chromium, chromium octanoate (III), hexacarbonyl chromium, acetylacetonate chromium (III) and 2-ethylhexanoate chromium (III) Any one of the groups can be selected. Preferred transition metal precursors include chromium (III) acetylacetonate and chromium (III) 2-ethylhexanoate.

  The heteroatom ligand can be attached to the polymer chain so that the resulting heteroatom coordination complex of the transition metal can be modified to be soluble at high temperatures but insoluble at 25 ° C. . This approach allows the complex to be recovered from the reaction mixture for reuse. E. Bergbreiter et al. Am. Chem. Soc. 1987, 109, 177-179 and has been used for other catalysts. In the same context, these transition metal complexes are also described in, for example, C.I. Yuanyin et al., Chinese J. et al. React. Pol. 1992, 1 (2), 152-159, by attaching a heteroatom ligand to, for example, silica, silica gel, polysiloxane, alumina skeleton, etc., as shown for the fixation of platinum complexes. It can also be fixed.

  The activator for use in the present method can in principle be any compound that produces an active catalyst when combined with a heteroatom ligand and a transition metal compound. Mixtures of activators can also be used. Suitable compounds include organoaluminum compounds, organoboron compounds, organic salts (such as methyllithium bromide and methylmagnesium bromide), inorganic acids and inorganic salts (tetrafluoroborate etherate, silver tetrafluoroborate and hexafluoroantimony). Acid sodium etc.).

Suitable organoaluminum compounds include compounds of formula AlR ₃ where R is independently a C ₁ -C ₁₂ alkyl, oxygen-containing moiety or halide, and compounds such as LiAlH _4. Can be mentioned. Examples include trimethyl aluminum (TMA), triethyl aluminum (TEA), triisobutyl aluminum (TIBA), tri-n-octyl aluminum, methyl aluminum dichloride, ethyl aluminum dichloride, dimethyl aluminum chloride, diethyl aluminum chloride, aluminum iso Examples include propoxide, ethylaluminum sesquichloride, methylaluminum sesquichloride, and aluminoxane. Aluminoxanes are generally well known in the art as oligomeric compounds that can be prepared by controlled addition of water to alkylaluminum compounds such as trimethylaluminum. The compound can be linear, cyclic, caged or mixtures thereof. Mixtures of different aluminoxanes can also be used in the present method.

Examples of suitable organoboron compounds include boroxine, NaBH ₄ , triethylboron, tris (pentafluorophenyl) boron, tributylborate and the like.

  The activator can also be or contain a compound that acts as a reducing or oxidizing agent, such as sodium or zinc metal, or oxygen, for example.

  The activator can be selected from alkylaluminoxanes such as methylaluminoxane (MAO) and ethylaluminoxane (EAO) and modified alkylaluminoxanes such as modified methylaluminoxane (MMAO). Modified methylaluminoxane (commercial product from Akzo Nobel) contains a modified group such as an isobutyl group or an n-octyl group in addition to a methyl group.

  The transition metal and aluminoxane are combined in a ratio that provides an Al / metal ratio of about 1: 1 to 10,000: 1, preferably about 1: 1 to 1000: 1, more preferably 1: 1 to 300: 1. be able to.

  The method can include adding to the catalyst system an amount of trialkylaluminum compound between 0.01 and 1000 moles per mole of alkylaluminoxane.

  It should be noted that aluminoxanes generally contain substantial amounts of the corresponding trialkylaluminum compounds that are also used in their preparation. The presence of these trialkylaluminum compounds in the aluminoxane is believed to be due to their incomplete hydrolysis with water. Any amount of trialkylaluminum compound indicated in this disclosure is to be added to the alkylaluminum compound included in the aluminoxane.

  The method includes mixing the components of the catalyst system in the presence of an olefin at any temperature between -20 ° C and 250 ° C. The Applicant has found that the catalyst system can be stabilized by the presence of olefins.

  The individual components of the catalyst system described herein can be combined to produce an active catalyst simultaneously or sequentially in any order, in the presence or absence of a solvent. The mixing of the catalyst components can be performed at any temperature between -20 ° C and 250 ° C. The presence of olefins in the mixture of catalyst components generally provides a protective effect that results in improved catalyst performance. A preferred temperature range is between 20 ° C and 100 ° C.

The catalyst system according to the invention or its individual components can also be applied to support materials such as silica, alumina, MgCl ₂ , zirconia or mixtures thereof, or polymers such as polyethylene, polypropylene, polystyrene or poly (amino It can also be fixed by being supported on styrene. The catalyst can be formed in situ in the presence of a support material, or the support can be pre-impregnated or mixed with one or more catalyst components simultaneously or sequentially. In some cases, the carrier material can act as a component of an activator. This approach also facilitates recovery of the catalyst for reuse from the reaction mixture. The concept is, for example, T.W. Monoi and Y.M. According to Sasaki, J. et al. Mol. Cat. A: Chem. 1987, 109, 177-179, shows successful examples of chromium-based ethylene trimerization catalysts. In some cases, the carrier can also act as a catalyst component, for example, if the carrier contains an aluminoxane functional group or if the carrier can perform a similar chemical function as an aluminoxane, This is the case, for example, with IOLA ™ (commercial product from Grace Davison).

  The reaction products described in this specification, in other words olefin oligomers, can be used in homogeneous liquid phase reactions in the presence or absence of inert solvents and / or catalyst systems using the disclosed catalyst systems. Reaction in the form of a slightly soluble or insoluble form, and / or a two-phase liquid / liquid reaction, and / or a bulk phase in which the reagent itself and / or the product olefin serves as the main medium Reactions and / or gas phase reactions can be prepared using conventional equipment and contact techniques.

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

  The method can be carried out at atmospheric pressure to 500 barg. An ethylene pressure in the range of 10 to 70 barg is preferred. A particularly preferred pressure is in the range of 30 to 50 barg.

  The method can be performed at a temperature in the range of -20 ° C to 250 ° C. A temperature in the range of 15 ° C to 130 ° C is preferred. A particularly preferred temperature is in the range of 35 ° C to 100 ° C.

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

  In addition to 1-octene, the process also includes varying amounts of 1-butene, 1-hexene, methylcyclopentane, methylenecyclopentane, propylcyclopentane, depending on the nature of the heteroatom ligand and the reaction conditions. Propylene cyclopentane and certain polymeric oligomers can also be produced. Some of these products cannot be formed in the yields found in the present invention by conventional ethylene oligomerization and trimerization techniques.

  The catalyst, its individual components, reagents, solvents and reaction products are generally adopted on a single use basis, but any of these materials should be recycled to some extent to minimize production costs. Is possible and actually preferred.

  The method can be carried out in factory equipment including any type of reactor. Examples of such reactors include, but are not limited to, batch reactors, semi-batch reactors, and continuous reactors. The plant equipment includes: a) a reactor; b) at least one inlet line to the reactor for the olefin reactant and catalyst system; and c) from the reactor for the oligomerization reaction product. At least one for separating the desired oligomerization reaction product comprising a discharge line and d) a catalyst system comprising a heteroatom coordination complex of the transition metal precursor and activator described herein. A combination with a separator can be included.

  In other embodiments of the method, the reactor and separator can be combined to facilitate simultaneous formation of reaction products and separation of these compounds from the reactor. This process principle is generally known as reactive distillation. If the catalyst system is not soluble in the solvent or reaction product and is fixed in the reactor so that it does not exit the reactor with the reactor product, solvent and unreacted olefin, then the process principle is generally the catalyst Known as distillation.

  According to a further aspect of the present invention, there is provided a catalyst system for tetramerization of olefins as noted above. The catalyst system includes the heteroatom ligand and transition metal noted above. The catalyst system can also include an activator as noted above.

The heteroatom ligand is represented by the following general formula (R) _n ABC (R) _m (wherein A and C are independently phosphorus, arsenic, antimony, oxygen, bismuth, sulfur, selenium). And B is a linking group between A and C, R is independently selected from either a homo- or heterohydrocarbyl group, and at least one R group is a polar substituent And n and m can be represented by the respective valences and oxidation states of A and C).

A and / or C can be a potential electron donor to coordinate with the transition metal.
An electron donor or electron donating substituent is defined as an entity that donates an electron used in a chemical bond including a donor bond and a covalent bond.

The heteroatom ligand is represented by the following general formula (R ¹ ) (R ² ) ABC (R ³ ) (R ⁴ ) (where A and C are independently phosphorus, arsenic, antimony, , Bismuth and nitrogen, B is a linking group between A and C, and R ¹ , R ² , R ³ and R ⁴ are independently a non-aromatic group and a heterocyclic group Selected from aromatic groups including aromatic, wherein at least one of R ¹ , R ² , R ³ and R ⁴ is substituted with a polar substituent.

In addition to at least one of R ¹ , R ² , R ^3, and R ⁴ that is substituted by a polar substituent, each R ¹ , R ² , R ^3, and R ⁴ is an aromatic, including a heterocyclic aromatic Preferably, but not all R ¹ , R ² , R ³ and R ⁴ are optional on the atom adjacent to the atom bound to A or C, if they are all aromatic Is substituted by a substituent of

In addition to at least one of R ¹ , R ² , R ³ and R ⁴ substituted by polar substituents, no more than two R ¹ , R ² , R ³ and R ⁴ are all aromatic In some cases, it may have a substituent on the atom adjacent to the atom bonded to A or C.

If R ¹ , R ² , R ³ and R ⁴ are all aromatic, then any polar substituents there may not be on the atom adjacent to the atom bound to A or C preferable.

Any polar substituent on one or more of R ¹ , R ² , R ³ and R ⁴ is electron donating.

Polarity is defined as an entity that has an invariant electric dipole moment. The polar substituent, methoxy, ethoxy, _isopropoxy, C 3 _{-C 20} alkoxy, phenoxy, pentafluorophenoxy, trimethylsiloxy, dimethylamino, methylsulfanyl, tosyl, methoxymethyl, methylthiomethyl, 1,3-oxazolyl, Metometokishi , Hydroxyl, amino, phosphino, arsino, stivino, sulfate, nitro and the like.

Any of the groups R ¹ , R ² , R ³ and R ⁴ can be linked to one or more of each other or independently of the linking group B to form a cyclic structure with A and C, A and B or B and C Can be formed.

R ¹ , R ² , R ³ and R ⁴ are independently benzyl, phenyl, tolyl, xylyl, mesityl, biphenyl, naphthyl, anthracenyl, methoxy, ethoxy, phenoxy, tolyloxy, dimethylamino, diethylamino, methylethylamino, It can be selected from the group consisting of thiophenyl, pyridyl, thioethyl, thiophenoxy, trimethylsilyl, dimethylhydrazyl, methyl, ethyl, ethenyl, propyl, butyl, propenyl, propynyl, cyclopentyl, cyclohexyl, ferrocenyl and tetrahydrofuranyl groups. Preferably, R ¹ , R ² , R ³ and R ⁴ can be independently selected from the group consisting of phenyl, tolyl, biphenyl, naphthyl, thiophenyl and ethyl groups.

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

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

B is an organic linking group including hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl and substituted heterohydrocarbyl; inorganic linking group including single atom bond; ionic bond and methylene, dimethylmethylene, 1,2-ethane, 1,2-phenylene , 1,2-propane, 1,2-catechol, 1,2-dimethylhydrazine, -B (R ⁵ )-, -Si (R ⁵ ) _2- , -P (R ⁵ )-and -N (R ⁵ )-(R ⁵ is hydrogen, hydrocarbyl or substituted hydrocarbyl, substituted heteroatom or halogen). Preferably B is —N (R ⁵ ) —, where R ⁵ is a hydrocarbyl or substituted hydrocarbyl group. R ⁵ is hydrogen, or alkyl, substituted alkyl, aryl, substituted aryl, aryloxy, substituted aryloxy, halogen, nitro, alkoxycarbonyl, carbonyloxy, alkoxy, aminocarbonyl, carbonylamino, dialkylamino, silyl It can be selected from the group consisting of groups or derivatives thereof, and aryl substituted by any of these substituents. Preferably R ⁵ may be an isopropyl, 1-cyclohexylethyl, 2-methylcyclohexyl or 2-octyl group.

  B can be selected to be a single atom spacer. Single atom bonded spacers are defined as substituted or unsubstituted atoms that are directly bonded to A and C.

The ligand can also contain a plurality of (R) _nABC (R) _m units. Non-limiting examples of such ligands include dendrimer ligands as well as ligands in which individual units are linked either by one or more R groups or by a linking group B. More specific, non-limiting examples of the above ligands 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} and 1,4-di - (P (4-methoxyphenyl) N (methyl) P (4-methoxyphenyl) ₂ ) -benzene.

The ligand can be prepared by procedures known to those skilled in the art and disclosed in published literature. Examples of ligands, _{(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 and (4-methoxyphenyl) (phenyl) PN (methyl) P (phenyl) ₂ , (3 -Methoxyphenyl) (phenyl) PN (methyl) P (3-methoxyphenyl) (phenyl), (4-methoxyphenyl) ( Eniru) 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 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} There is.

  The transition metal can be selected from any one of the group consisting of chromium, molybdenum, tungsten, titanium, tantalum, vanadium and zirconium, preferably chromium.

  The transition metal can be derived from a transition metal compound selected from a single inorganic or organic salt, coordination complex or organometallic complex, chromium trichloride tris-tetrahydrofuran complex, (benzene) -tricarbonylchromium , Chromium (III) octoate, chromium (III) acetylacetonate, chromium hexacarbonyl and chromium (III) 2-ethylhexanoate. Preferred transition metal compounds include chromium (III) acetylacetonate and chromium (III) 2-ethylhexanoate.

The transition metal compound and the heteroatom ligand can have a metal / ligand ratio of about 0.01: 100 to 10,000: 1, preferably about 0.1: 1 to 10: 1.
The catalyst system can also include an activator as described above.

  The activator can in principle be any compound that produces an active catalyst when combined with a heteroatom ligand and a transition metal compound. Mixtures of activators can also be used. Suitable compounds include organoaluminum compounds, organoboron compounds, organic salts (such as methyllithium bromide and methylmagnesium bromide), inorganic acids and inorganic salts (tetrafluoroborate etherate, silver tetrafluoroborate and hexafluoroantimony). Acid sodium etc.).

  The activator can be selected from alkylaluminoxanes such as methylaluminoxane (MAO) and ethylaluminoxane (EAO) and modified alkylaluminoxanes such as modified methylaluminoxane (MMAO). Modified methylaluminoxane (commercial product from Akzo Nobel) contains a modified group such as an isobutyl group or an n-octyl group in addition to a methyl group. The transition metal and the aluminoxane provide an Al / metal ratio of about 1: 1 to 10,000: 1, preferably about 1: 1 to 1000: 1, more preferably 1: 1 to 300: 1 relative to each other. It can be a ratio to do.

  The catalyst system can also comprise an amount between 0.01 and 100 moles of trialkylaluminum compound per mole of aluminoxane.

  According to a further aspect of the present invention there is provided a ligand as described above for the catalyst system described above for olefin tetramerization.

  The present invention also extends to the identification and use of ligands suitable for use in olefin tetramerization processes and catalyst systems.

[Example]
The invention will now be described with reference to the following examples which are in no way intended to limit the scope of the invention. The individual components of the examples may possibly be omitted or replaced, and although not necessarily ideal, the present invention may still be practiced, so that these components are essential for the function of the present invention. Should not be considered.

In the following examples, all procedures were performed under inert conditions using pre-dried reagents. Chemicals were obtained from Sigma-Aldrich or Strem Chemicals unless otherwise stated. Trialkylaluminum and aluminoxane compounds and their solutions were all obtained from Crompton Gmbh, Akzo Nobel and Albemarle Corporation. In all embodiments, in order to calculate the molar amounts of MAO used in the preparation of the catalyst described in the Examples below, the molar mass of methylaluminoxane (MAO) is corresponding to the (CH 3 _-Al-O) units Thus, it was regarded as 58.016 g / mol. Similarly, the molar mass of ethylaluminoxane (EAO) is 72.042 g / mol, corresponding to the (CH ₃ CH ₂ -Al—O) component, from a 70:30 mixture of trimethylaluminum and triisobutylaluminum. That of the prepared modified methylaluminoxane was considered to be 70.7 g / mol corresponding to (Me _0.70 isoBu _0.30 -Al-O) units. The ethylene oligomerization product was analyzed by GC-MS and GC-FID.

Mixed heteroatom PNP ligands are described in (a) Ewart et al. Chem. Soc. 1964, 1543, (b) Dossett, S .; J. et al. Et al., Chem. Commun. 2001, 8, 699, (c) Balakrishna, M .; S. J. et al. Organomet. Chem. 1990, 390, 2, 203) by reacting an amine with phosphine chloride R ₂ PCl. Each phosphine chloride R ₂ PCl is 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).

Preparation of (4-methoxyphenyl) ₂ PN (isopropyl) P (phenyl) ₂ ligand Example 1a): Preparation of N, N-diisopropylphosphoramide dichloride Diisopropylamine (70 ml, 0.005 ml) in toluene (80 ml). 50 mol) of _PCl 3 _(21.87ml, was added at -10 ° C. to a solution in toluene (80 ml) of 0.25 mol). The mixture was stirred for 2 hours and then allowed to warm to room temperature. The solution was stirred for an additional hour and then filtered through a pad of celite. The solvent was removed to give the product (35 g, 0.17 mol, 68%). ³¹ P {H} NMR: 170 ppm

Example 1b): Preparation of 4-methoxyphenylmagnesium bromide Magnesium shavings (9.11 g, 0.375 mol) were treated with 4-bromoanisole (9.39 ml, 75 mmol) in THF (100 ml). . A vigorous reaction occurred and was cooled in an ice bath. When the reaction was over, the reaction mixture was heated under reflux for 2 hours to give a Grignard reagent.

Example 1c): Preparation of bis (4-methoxyphenyl) phosphorous chloride The Grignard reagent was added at 0 ° C. to N, N-diisopropylphosphoramide dichloride (6.64 ml, 36 mmol) in THF (100 ml). After stirring overnight at room temperature, the mixture was diluted with cyclohexane (200 ml) and dry HCl gas was bubbled through the solution for 0.5 h. After the precipitate was filtered, the solvent was removed and a mixture of phosphine chloride and bromide was obtained in 80% yield. All of this crude product was used in the next step without isolation.

Example 1d) :( _{4-methoxyphenyl)} 2 PN (isopropyl) P _{(4-methoxyphenyl) 2} Preparation DCM (80 ml) and the crude bis triethylamine (15 ml) (4-methoxyphenyl) phosphorus chloride (crude reaction To a 0 ° C. solution of 28.8 mmol) calculated from the mixture was added isopropylamine (1.11 ml, 13 mmol). The reaction was stirred for 30 minutes, after which the ice bath was removed. After stirring for a total of 14 hours, the solution was filtered to remove the triethylammonium salt formed. The product was crystallized and isolated in 77% yield. ³¹ P {H} NMR: 47.4 ppm (wide singlet).

Tetramerization reaction of ethylene using Cr (III) acetylacetonate, (4-methoxyphenyl) ₂ PN (methyl) P (4-methoxyphenyl) ₂ and MAO In a Schlenk tube, 30.0 mg of (4- A solution of methoxyphenyl) ₂ PN (methyl) P (4-methoxyphenyl) ₂ (0.066 mmol) in 10 ml of toluene was added to 11.5 mg of chromium (III) acetylacetonate (0.033 mmol) in 10 ml of toluene. In the solution. The mixture was stirred at ambient temperature for 5 minutes and then transferred to a 300 ml pressure reactor (autoclave) containing a 60 ° C. mixture of toluene (80 ml) and MAO (methylaluminoxane, 9.9 mmol). The pressure reactor was charged with ethylene, after which the reactor temperature was maintained at 65 ° C while the ethylene pressure was maintained at 30 barg. A gas-entrained stirrer was used to ensure complete mixing from beginning to end with a mixing speed of 1100 RPM. The reaction was terminated after 30 minutes by cutting off the ethylene feed to the reactor and the reactor was cooled below 10 ° C. After releasing excess ethylene from the autoclave, the liquid contained in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water. Nonane was added as an internal standard for analysis by GC-FID in the liquid phase. A small sample of the organic layer was dried over anhydrous sodium sulfate and subsequently analyzed by GC-FID. The remainder of the organic layer was filtered to isolate a solid wax / polymer product. These solid products were dried in an oven at 100 ° C. overnight and subsequently weighed to give a yield of 0.2254 g of polyethylene. GC analysis indicated that the reaction mixture contained 38.50 g of oligomer. The product distribution for this example is summarized in Table 1.

Tetramerization reaction of ethylene using Cr (III) acetylacetonate, (3-methoxyphenyl) ₂ PN (methyl) P (3-methoxyphenyl) ₂ and MAO In a Schlenk tube, 30.0 mg of (3- A solution of methoxyphenyl) ₂ PN (methyl) P (3-methoxyphenyl) ₂ (0.066 mmol) in 10 ml of toluene was added to 11.5 mg of chromium (III) acetylacetonate (0.033 mmol) in 10 ml of toluene. In the solution. The mixture was stirred at ambient temperature for 5 minutes and then transferred to a 300 ml pressure reactor (autoclave) containing a 60 ° C. mixture of toluene (80 ml) and MAO (methylaluminoxane, 9.9 mmol). The pressure reactor was charged with ethylene, after which the reactor temperature was maintained at 65 ° C while the ethylene pressure was maintained at 30 barg. A gas-entrained stirrer was used to ensure complete mixing from beginning to end with a mixing speed of 1100 RPM. The reaction was terminated after 30 minutes by cutting off the ethylene feed to the reactor and the reactor was cooled below 10 ° C. After releasing excess ethylene from the autoclave, the liquid contained in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water. Nonane was added as an internal standard for analysis by GC-FID in the liquid phase. A small sample of the organic layer was dried over anhydrous sodium sulfate and subsequently analyzed by GC-FID. The remainder of the organic layer was filtered to isolate a solid wax / polymer product. These solid products were dried in an oven at 100 ° C. overnight and subsequently weighed to give a yield of 1.2269 g of polyethylene. GC analysis showed that the reaction mixture contained 9.71 g of oligomer. The product distribution for this example is summarized in Table 1.

Tetramerization reaction of ethylene using Cr (III) acetylacetonate, (4-methoxyphenyl) ₂ PN (isopropyl) P (4-methoxyphenyl) ₂ and MAO In a Schlenk tube, 36.1 mg of (4- A solution of methoxyphenyl) ₂ PN (isopropyl) P (4-methoxyphenyl) ₂ (0.066 mmol) in 10 ml of toluene was added to 11.5 mg of chromium (III) acetylacetonate (0.033 mmol) in 10 ml of toluene. In the solution. The mixture was stirred at ambient temperature for 5 minutes and then transferred to a 300 ml pressure reactor (autoclave) containing a 60 ° C. mixture of toluene (80 ml) and MAO (methylaluminoxane, 9.9 mmol). The pressure reactor was charged with ethylene, after which the reactor temperature was maintained at 65 ° C while the ethylene pressure was maintained at 30 barg. A gas-entrained stirrer was used to ensure complete mixing from beginning to end with a mixing speed of 1100 RPM. The reaction was terminated after 30 minutes by cutting off the ethylene feed to the reactor and the reactor was cooled below 10 ° C. After releasing excess ethylene from the autoclave, the liquid contained in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water. Nonane was added as an internal standard for analysis by GC-FID in the liquid phase. A small sample of the organic layer was dried over anhydrous sodium sulfate and subsequently analyzed by GC-FID. The remainder of the organic layer was filtered to isolate a solid wax / polymer product. These solid products were dried in an oven at 100 ° C. overnight and subsequently weighed to give a yield of 0.7105 g of polyethylene. GC analysis showed that the reaction mixture contained 61.33 g of oligomer. The product distribution for this example is summarized in Table 1.

Tetramerization reaction of ethylene using Cr (III) acetylacetonate, (4-methoxyphenyl) ₂ PN (isopropyl) P (4-methoxyphenyl) ₂ and MAO In a Schlenk tube, 36.1 mg of (4- A solution of methoxyphenyl) ₂ PN (isopropyl) P (4-methoxyphenyl) ₂ (0.066 mmol) in 10 ml of toluene was added to 11.5 mg of chromium (III) acetylacetonate (0.033 mmol) in 10 ml of toluene. In the solution. The mixture was stirred at ambient temperature for 5 minutes and then transferred to a 300 ml pressure reactor (autoclave) containing a 40 ° C. mixture of toluene (80 ml) and MAO (methylaluminoxane, 9.9 mmol). 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. A gas-entrained stirrer was used to ensure complete mixing from beginning to end with a mixing speed of 1100 RPM. The reaction was terminated after 12 minutes by cutting off the ethylene feed to the reactor and the reactor was cooled below 10 ° C. After releasing excess ethylene from the autoclave, the liquid contained in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water. Nonane was added as an internal standard for analysis by GC-FID in the liquid phase. A small sample of the organic layer was dried over anhydrous sodium sulfate and subsequently analyzed by GC-FID. The remainder of the organic layer was filtered to isolate a solid wax / polymer product. These solid products were dried in an oven at 100 ° C. overnight and subsequently weighed to give a yield of 2.3010 g of polyethylene. GC analysis indicated that the reaction mixture contained 73.53 g of oligomer. The product distribution for this example is summarized in Table 1.

Tetramerization reaction of ethylene using Cr (III) acetylacetonate, (4-methoxyphenyl) ₂ PN (isopropyl) P (4-methoxyphenyl) ₂ and MAO In a Schlenk tube, 16.4 mg of (4- A solution of methoxyphenyl) ₂ PN (isopropyl) P (4-methoxyphenyl) ₂ (0.03 mmol) in 10 ml cyclohexane was added to 5.2 mg chromium (III) acetylacetonate (0.015 mmol) in 10 ml cyclohexane. In the solution. The mixture was stirred at ambient temperature for 5 minutes and then transferred to a 300 ml pressure reactor (autoclave) containing a 40 ° C. mixture of cyclohexane (80 ml) and MAO (methylaluminoxane in toluene, 4.5 mmol). 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. A gas-entrained stirrer was used to ensure complete mixing from beginning to end with a mixing speed of 1100 RPM. The reaction was terminated after 11 minutes by cutting off the ethylene feed to the reactor and the reactor was cooled below 10 ° C. After releasing excess ethylene from the autoclave, the liquid contained in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water. Nonane was added as an internal standard for analysis by GC-FID in the liquid phase. A small sample of the organic layer was dried over anhydrous sodium sulfate and subsequently analyzed by GC-FID. The remainder of the organic layer was filtered to isolate a solid wax / polymer product. These solid products were dried in an oven at 100 ° C. overnight and subsequently weighed to give a yield of 1.9168 g of polyethylene. GC analysis showed that the reaction mixture contained 62.72 g of oligomer. The product distribution for this example is summarized in Table 1.

Tetramerization reaction of ethylene using Cr (III) acetylacetonate, (4-methoxyphenyl) ₂ PN (isopropyl) P (4-methoxyphenyl) ₂ and MAO In a Schlenk tube, 9.8 mg of (4- A solution of methoxyphenyl) ₂ PN (isopropyl) P (4-methoxyphenyl) ₂ (0.018 mmol) in 10 ml of toluene was added to 5.2 mg of chromium (III) acetylacetonate (0.015 mmol) in 10 ml of toluene. In the solution. The mixture was stirred at ambient temperature for 5 minutes and then transferred to a 300 ml pressure reactor (autoclave) containing a 40 ° C. mixture of toluene (80 ml) and MAO (methylaluminoxane, 4.5 mmol). 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. A gas-entrained stirrer was used to ensure complete mixing from beginning to end with a mixing speed of 1100 RPM. The reaction was terminated after 21 minutes by cutting off the ethylene feed to the reactor and the reactor was cooled below 10 ° C. After releasing excess ethylene from the autoclave, the liquid contained in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water. Nonane was added as an internal standard for analysis by GC-FID in the liquid phase. A small sample of the organic layer was dried over anhydrous sodium sulfate and subsequently analyzed by GC-FID. The remainder of the organic layer was filtered to isolate a solid wax / polymer product. These solid products were dried in an oven at 100 ° C. overnight and subsequently weighed to give a yield of 0.8280 g of polyethylene. GC analysis showed that the reaction mixture contained 69.17 g of oligomer. The product distribution for this example is summarized in Table 1.

Tetramerization reaction of ethylene using CrCl ₃ THF ₃ , (4-methoxyphenyl) ₂ PN (isopropyl) P (4-methoxyphenyl) ₂ and MAO In a Schlenk tube, 9.8 mg of (4-methoxyphenyl) A solution of ₂ PN (isopropyl) P (4-methoxyphenyl) ₂ (0.018 mmol) in 10 ml of toluene was added to a solution of 5.6 mg CrCl ₃ THF ₃ (0.015 mmol) in 10 ml of toluene. . The mixture was stirred at ambient temperature for 5 minutes and then transferred to a 300 ml pressure reactor (autoclave) containing a 40 ° C. mixture of toluene (80 ml) and MAO (methylaluminoxane, 4.5 mmol). 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. A gas-entrained stirrer was used to ensure complete mixing from beginning to end with a mixing speed of 1100 RPM. The reaction was terminated after 30 minutes by cutting off the ethylene feed to the reactor and the reactor was cooled below 10 ° C. After releasing excess ethylene from the autoclave, the liquid contained in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water. Nonane was added as an internal standard for analysis by GC-FID in the liquid phase. A small sample of the organic layer was dried over anhydrous sodium sulfate and subsequently analyzed by GC-FID. The remainder of the organic layer was filtered to isolate a solid wax / polymer product. These solid products were dried in an oven at 100 ° C. overnight and then weighed to give a yield of 1.0831 g of polyethylene. GC analysis indicated that the reaction mixture contained 42.72 g of oligomer. The product distribution for this example is summarized in Table 1.

Tetramerization reaction of ethylene using Cr (III) 2-ethylhexanoate, (4-methoxyphenyl) ₂ PN (isopropyl) P (4-methoxyphenyl) ₂ and MAO In a Schlenk tube, 9.8 mg of A solution of (4-methoxyphenyl) ₂ PN (isopropyl) P (4-methoxyphenyl) ₂ (0.018 mmol) in 10 ml of toluene was added to 10.2 mg of Cr (III) 2-ethylhexanoate (mineral oil). In 70 ml, 0.015 mmol) in 10 ml of toluene. The mixture was stirred at ambient temperature for 5 minutes and then transferred to a 300 ml pressure reactor (autoclave) containing a 40 ° C. mixture of toluene (80 ml) and MAO (methylaluminoxane, 4.5 mmol). 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. A gas-entrained stirrer was used to ensure complete mixing from beginning to end with a mixing speed of 1100 RPM. The reaction was terminated after 30 minutes by cutting off the ethylene feed to the reactor and the reactor was cooled below 10 ° C. After releasing excess ethylene from the autoclave, the liquid contained in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water. Nonane was added as an internal standard for analysis by GC-FID in the liquid phase. A small sample of the organic layer was dried over anhydrous sodium sulfate and subsequently analyzed by GC-FID. The remainder of the organic layer was filtered to isolate a solid wax / polymer product. These solid products were dried in an oven at 100 ° C. overnight and subsequently weighed to give a yield of 1.52 g of polyethylene. GC analysis indicated that the reaction mixture contained 61.27 g of oligomer. The product distribution for this example is summarized in Table 1.

Tetramerization reaction of ethylene using Cr (III) octanoate, (4-methoxyphenyl) ₂ PN (isopropyl) P (4-methoxyphenyl) ₂ and MAO In a Schlenk tube, 9.8 mg of (4- A solution of methoxyphenyl) ₂ PN (isopropyl) P (4-methoxyphenyl) ₂ (0.018 mmol) in 10 ml of toluene was added to 10.3 mg of Cr (III) octanoate (70% in toluene, 0.015 mmol). ) In 10 ml of toluene. The mixture was stirred at ambient temperature for 5 minutes and then transferred to a 300 ml pressure reactor (autoclave) containing a 40 ° C. mixture of toluene (80 ml) and MAO (methylaluminoxane, 4.5 mmol). 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. A gas-entrained stirrer was used to ensure complete mixing from beginning to end with a mixing speed of 1100 RPM. The reaction was terminated after 40 minutes by cutting off the ethylene feed to the reactor and the reactor was cooled below 10 ° C. After releasing excess ethylene from the autoclave, the liquid contained in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water. Nonane was added as an internal standard for analysis by GC-FID in the liquid phase. A small sample of the organic layer was dried over anhydrous sodium sulfate and subsequently analyzed by GC-FID. The remainder of the organic layer was filtered to isolate a solid wax / polymer product. These solid products were dried in an oven at 100 ° C. overnight and subsequently weighed to give a yield of 0.3773 g of polyethylene. GC analysis indicated that the reaction mixture contained 18.91 g of oligomer. The product distribution for this example is summarized in Table 1.

Tetramerization reaction of ethylene using Cr (III) acetylacetonate, (4-methoxyphenyl) ₂ PN (isopropyl) P (4-methoxyphenyl) ₂ and MAO In a Schlenk tube, 6.6 mg of (4- A solution of methoxyphenyl) ₂ PN (isopropyl) P (4-methoxyphenyl) ₂ (0.012 mmol) in 10 ml of toluene was added to 3.5 mg of chromium (III) acetylacetonate (0.015 mmol) in 10 ml of toluene. In the solution. The mixture was stirred at ambient temperature for 5 minutes and then transferred to a 300 ml pressure reactor (autoclave) containing a 40 ° C. mixture of toluene (80 ml) and MAO (methylaluminoxane, 3.0 mmol). 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. A gas-entrained stirrer was used to ensure complete mixing from beginning to end with a mixing speed of 1100 RPM. The reaction was terminated after 30 minutes by cutting off the ethylene feed to the reactor and the reactor was cooled below 10 ° C. After releasing excess ethylene from the autoclave, the liquid contained in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water. Nonane was added as an internal standard for analysis by GC-FID in the liquid phase. A small sample of the organic layer was dried over anhydrous sodium sulfate and subsequently analyzed by GC-FID. The remainder of the organic layer was filtered to isolate a solid wax / polymer product. These solid products were dried in an oven at 100 ° C. overnight and subsequently weighed to give a yield of 1.3958 g of polyethylene. GC analysis indicated that the reaction mixture contained 54.52 g of oligomer. The product distribution for this example is summarized in Table 1.

Tetramerization reaction of ethylene using Cr (III) acetylacetonate, (4-methoxyphenyl) ₂ PN (isopropyl) P (4-methoxyphenyl) ₂ and MAO In a Schlenk tube, 9.8 mg of (4- A solution of methoxyphenyl) ₂ PN (isopropyl) P (4-methoxyphenyl) ₂ (0.018 mmol) in 10 ml of toluene was added to 5.2 mg of chromium (III) acetylacetonate (0.015 mmol) in 10 ml of toluene. In the solution. The mixture was stirred at ambient temperature for 5 minutes and then transferred to a 300 ml pressure reactor (autoclave) containing a 40 ° C. mixture of toluene (80 ml) and MAO (methylaluminoxane, 2.25 mmol). 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. A gas-entrained stirrer was used to ensure complete mixing from beginning to end with a mixing speed of 1100 RPM. The reaction was terminated after 15 minutes by cutting off the ethylene feed to the reactor and the reactor was cooled below 10 ° C. After releasing excess ethylene from the autoclave, the liquid contained in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water. Nonane was added as an internal standard for analysis by GC-FID in the liquid phase. A small sample of the organic layer was dried over anhydrous sodium sulfate and subsequently analyzed by GC-FID. The remainder of the organic layer was filtered to isolate a solid wax / polymer product. These solid products were dried in an oven at 100 ° C. overnight and subsequently weighed to give a yield of 0.5010 g of polyethylene. GC analysis showed that the reaction mixture contained 70.87 g of oligomer. The product distribution for this example is summarized in Table 1.

Tetramerization reaction of ethylene using Cr (III) acetylacetonate, (4-methoxyphenyl) ₂ PN (isopropyl) P (4-methoxyphenyl) ₂ and MMAO-3A In a Schlenk tube, 16.4 mg ( _{4-methoxyphenyl)} 10ml of 2 PN (isopropyl) P _{(4-methoxyphenyl)} 2 (a solution in toluene of 10ml of 0.03 mmol), chromium 5.2 mg (III) acetylacetonate (0.015 mmol) To a solution of toluene in toluene. The mixture was stirred at ambient temperature for 5 minutes, followed by addition to a 300 ml pressure reactor (autoclave) containing a 40 ° C. mixture of toluene (80 ml) and MMAO-3A (modified methylaluminoxane in heptane, 4.5 mmol). Moved. 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. A gas-entrained stirrer was used to ensure complete mixing from beginning to end with a mixing speed of 1100 RPM. The reaction was terminated after 22 minutes by cutting off the ethylene feed to the reactor and the reactor was cooled below 10 ° C. After releasing excess ethylene from the autoclave, the liquid contained in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water. Nonane was added as an internal standard for analysis by GC-FID in the liquid phase. A small sample of the organic layer was dried over anhydrous sodium sulfate and subsequently analyzed by GC-FID. The remainder of the organic layer was filtered to isolate a solid wax / polymer product. These solid products were dried in an oven at 100 ° C. overnight and subsequently weighed to give a yield of 1.76 g of polyethylene. GC analysis indicated that the reaction mixture contained 50.42 g of oligomer. The product distribution for this example is summarized in Table 1.

Tetramerization reaction of ethylene using Cr (III) acetylacetonate, (4-methoxyphenyl) ₂ PN (isopropyl) P (4-methoxyphenyl) ₂ and EAO / TMA In a Schlenk tube, 36.1 mg ( 4-Methoxyphenyl) ₂ PN (isopropyl) P (4-methoxyphenyl) ₂ (0.066 mmol) in 10 ml of toluene was added to 5.2 mg of chromium (III) acetylacetonate (0.015 mmol) in 10 ml. To a solution of toluene in toluene. The mixture was stirred at ambient temperature for 5 minutes, followed by 300 ml pressure reaction containing a mixture of toluene (80 ml) and EAO (ethylaluminoxane in toluene, 33 mmol) and TMA (trimethylaluminum, 8.25 mmol) at 40 ° C. Transferred to a vessel (autoclave). 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. A gas-entrained stirrer was used to ensure complete mixing from beginning to end with a mixing speed of 1100 RPM. The reaction was terminated after 60 minutes by cutting off the ethylene feed to the reactor and the reactor was cooled below 10 ° C. After releasing excess ethylene from the autoclave, the liquid contained in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water. Nonane was added as an internal standard for analysis by GC-FID in the liquid phase. A small sample of the organic layer was dried over anhydrous sodium sulfate and subsequently analyzed by GC-FID. The remainder of the organic layer was filtered to isolate a solid wax / polymer product. These solid products were dried in an oven at 100 ° C. overnight and subsequently weighed to give a yield of 0.189 g of polyethylene. GC analysis showed that the reaction mixture contained 40.97 g of oligomer. The product distribution for this example is summarized in Table 1.

Tetramerization reaction of ethylene using Cr (III) acetylacetonate, (4-methoxyphenyl) ₂ PN (isopropyl) P (4-methoxyphenyl) ₂ and MAO in the presence of H _{2 in} a Schlenk tube. A solution of 16.4 mg (4-methoxyphenyl) ₂ PN (isopropyl) P (4-methoxyphenyl) ₂ (0.03 mmol) in 10 ml toluene was added 5.2 mg chromium (III) acetylacetonate (0 .015 mmol) in 10 ml of toluene. The mixture was stirred at ambient temperature for 5 minutes and then transferred to a 300 ml pressure reactor (autoclave) containing a 40 ° C. mixture of toluene (80 ml) and MAO (methylaluminoxane in toluene, 4.5 mmol). The pressure reactor was initially charged with hydrogen to a pressure of about 2.5 barg, followed by ethylene to 45 barg, after which the reactor temperature was maintained at 45 ° C. while maintaining the ethylene pressure at 45 barg. A gas-entrained stirrer was used to ensure complete mixing from beginning to end with a mixing speed of 1100 RPM. The reaction was terminated after 15 minutes by cutting off the ethylene feed to the reactor and the reactor was cooled below 10 ° C. After releasing excess ethylene from the autoclave, the liquid contained in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water. Nonane was added as an internal standard for analysis by GC-FID in the liquid phase. A small sample of the organic layer was dried over anhydrous sodium sulfate and subsequently analyzed by GC-FID. The remainder of the organic layer was filtered to isolate a solid wax / polymer product. These solid products were dried in an oven at 100 ° C. overnight and subsequently weighed to give a yield of 1.2060 g of polyethylene. GC analysis showed that the reaction mixture contained 81.51 g of oligomer. The product distribution for this example is summarized in Table 1.

Tetramerization reaction of ethylene using Cr (III) acetylacetonate, (phenyl) ₂ PN (isopropyl) P (2-methoxyphenyl) ₂ and MAO In a Schlenk tube, 32.2 mg of (phenyl) ₂ PN ( A solution of isopropyl) P (2-methoxyphenyl) ₂ (0.066 mmol) in 10 ml toluene was added to a solution of 11.5 mg chromium (III) acetylacetonate (0.033 mmol) in 10 ml toluene. . The mixture was stirred at ambient temperature for 5 minutes and then transferred to a 300 ml pressure reactor (autoclave) containing a 40 ° C. mixture of toluene (80 ml) and MAO (methylaluminoxane in toluene, 4.5 mmol). The pressure reactor was initially charged with ethylene, after which the reactor temperature was maintained at 45 ° C while the ethylene pressure was maintained at 45 barg. A gas-entrained stirrer was used to ensure complete mixing from beginning to end with a mixing speed of 1100 RPM. The reaction was terminated after 15 minutes by cutting off the ethylene feed to the reactor and the reactor was cooled below 10 ° C. After releasing excess ethylene from the autoclave, the liquid contained in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water. Nonane was added as an internal standard for analysis by GC-FID in the liquid phase. A small sample of the organic layer was dried over anhydrous sodium sulfate and subsequently analyzed by GC-FID. The remainder of the organic layer was filtered to isolate a solid wax / polymer product. These solid products were dried in an oven at 100 ° C. overnight and subsequently weighed to give a yield of 6.82 g of polyethylene. GC analysis showed that the reaction mixture contained 38.33 g of oligomer. The product distribution for this example is summarized in Table 1.

Claims (86)

  A process for tetramerizing olefins, wherein the product stream of said process contains more than 30% tetrameric olefins.   2. The method of claim 1 comprising contacting the olefin feed stream with a catalyst system containing a transition metal compound and a heteroatom ligand. The heteroatom ligand is represented by the following general formula (R) _nABC (R) _m (wherein A and C are independently phosphorus, arsenic, antimony, oxygen, bismuth, sulfur, selenium). And B is a linking group between A and C, R is the same or different, and each R is independently from either a homo or heterohydrocarbyl group. And n and m for each R are independently determined by the respective valences and oxidation states of A and C, wherein at least one of R is substituted with a polar substituent. Or the method of 2. 4. The method of claim 3, wherein the ligand comprises a plurality of (R) _nABC (R) _m . The method includes contacting an olefin feed stream with a catalyst system comprising a transition metal and a heteroatom ligand, wherein the tetramer is an olefin and comprises 30% of the product stream of the method. The heteroatom ligand has the following general formula (R ¹ ) (R ² ) ABC (R ³ ) (R ⁴ ) (wherein 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 R ¹ , R ² , R ³ and R ⁴ are independently non- Selected from aromatic groups and aromatic groups including heteroaromatics, wherein at least one of R ¹ , R ² , R ³ and R ⁴ is substituted by a polar substituent) 4. The method according to any one of items 3. R ^{1, R 2,} The method of claim 5, up to four of R ³ and R ⁴ have substituents on the atom adjacent to the atom bound to A or C. Each R ¹ , R ² , R ³ and R ⁴ is an aromatic, including a heterocyclic aromatic, but not all R ¹ , R ² , R ³ and R ⁴ are bonded to A or C The method according to claim 5 or 6, wherein the method is substituted by an arbitrary substituent on an atom adjacent to the atom. The method of claim 7, more than two R ^1, R ^2, R ³ and R ⁴ has a substituent on the atom adjacent to the atom bound to A or C. R ^{1, R 2,} R ³ and any polar substituents on R ⁴ A method according to claim 7 or claim 8 is not on atoms adjacent to atom bound to A or C. 8. At least one of R ¹ , R ² , R ³ and R ⁴ is substituted with a polar substituent on an atom two or more away from the atom bonded to A or C. 10. The method according to any one of items 9. One or more of R ^1, R ^2, any polar substituents on R ³ and R ^4, method according to any one of claims 3 to 5 and 7 to 10 are electron-donating.   12. A process according to any one of claims 1 to 5 and 7 to 11 wherein the feed stream comprises alpha-olefin and the product stream comprises at least 30% tetramerized alpha-olefin monomer.   13. A process as claimed in any one of claims 1 to 5 and 7 to 12, wherein the olefin feed stream comprises ethylene and the product stream comprises at least 30% 1-octene.   The process of any one of claims 1-5 and 7-12, wherein the olefin feed stream comprises ethylene and the product stream comprises at least 40% 1-octene.   13. A process according to any one of claims 1-5 and 7-12, wherein the olefin feed stream comprises ethylene and the product stream comprises at least 50% 1-octene.   13. A process according to any one of claims 1 to 5 and 7 to 12, wherein the olefin feed stream comprises ethylene and the product stream comprises at least 60% 1-octene. The olefin feed stream comprises ethylene, and the ratio of (C ₆ + C ₈ ) :( C ₄ + C ₁₀ ) in the product stream is greater than 2.5: 1. The method according to item. Wherein wherein the olefin feed stream to ethylene, C ₈ of the product _stream: The method according to any one of the ratio of C ₆ is greater than one claims 1 to 5 and 7 to 17.   19. A process according to any one of claims 12 to 18 wherein ethylene is contacted with the catalyst system at a pressure above 10 barg.   20. A method according to any one of claims 3-5 and 7-19, wherein A and / or C are potential electron donors for coordination with the transition metal. B is an organic linking group comprising hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl and substituted heterohydrocarbyl; an inorganic linking group comprising a single atom bond; an ionic bond and methylene, dimethylmethylene, 1,2-ethane, 1,2-phenylene, 1,2-propane, 1,2-catechol, 1,2-dimethylhydrazine, -B (R ⁵ )-, -Si (R ⁵ ) _2- , -P (R ⁵ )-and -N (R ⁵ ) - (R ⁵ is hydrogen, hydrocarbyl or substituted hydrocarbyl, a heteroatom and a halogen to substituted) according to any one of claims 3 to 5 and 7 to 20 is selected from any one of the group consisting of the method of.   The method of any one of claims 3-5 and 7-21, wherein B is selected to be a single atom spacer. B is —N (R ⁵ ) — (R ⁵ is hydrogen or alkyl, substituted alkyl, aryl, substituted aryl, aryloxy, substituted aryloxy, halogen, nitro, alkoxycarbonyl, carbonyloxy, alkoxy, aminocarbonyl And carbonylamino, dialkylamino, silyl groups or derivatives thereof, and aryl groups substituted by any of these substituents). The method of any one of these.   24. Any of claims 3 to 5 and 7 to 23, wherein A and / or C are independently oxidized with S, Se, N or O (the valence of A and / or C enables the oxidation). The method according to claim 1.   25. A method according to any one of claims 3 to 5 and 7 to 24, wherein A and C are independently phosphorus or phosphorus oxidized with S or Se or N or O. R ¹ , R ² , R ³ and R ⁴ are independently benzyl, phenyl, tolyl, xylyl, mesityl, biphenyl, naphthyl, anthracenyl, methoxy, ethoxy, phenoxy, tolyloxy, dimethylamino, diethylamino, methylethylamino, Claims 3 to 5 and selected from the group consisting of thiophenyl, pyridyl, thioethyl, thiophenoxy, trimethylsilyl, dimethylhydrazyl, methyl, ethyl, ethenyl, propyl, butyl, propenyl, propynyl, cyclopentyl, cyclohexyl, ferrocenyl and tetrahydrofuranyl groups 26. The method according to any one of 7 to 25. 27. Any one of claims 3 to 5 and 7 to 26, wherein R ¹ , R ² , R ³ and R ⁴ are independently selected from the group consisting of phenyl, tolyl, biphenyl, naphthyl, thiophenyl and ethyl groups. The method described. The ligand may be (3-methoxyphenyl) ₂ PN (methyl) P (3-methoxyphenyl) ₂ , (4-methoxyphenyl) ₂ PN (methyl) P (4-methoxyphenyl) ₂ , (3-methoxy Phenyl) 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-methoxy Phenyl) (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 PN (2-methylcyclohexyl) P (4-methoxyphenyl) ₂ , (4-methoxy Phenyl) 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- _Ruorofeniru) 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- The group consisting of (4-methoxyphenyl) -phenyl) ₂ PN (isopropyl) P (4- (4-methoxyphenyl) -phenyl) ₂ and (4-methoxyphenyl) (phenyl) PN (isopropyl) P (phenyl) ₂ 28. A method according to any one of claims 2 to 5, 7 to 23 and 25 to 27, selected from any one of the following.   29. A method according to any one of claims 1 to 5 and 7 to 28 comprising combining the heteroatom ligand with the transition metal compound and the activator in any order.   29. Any of claims 2-5 and 7-28 comprising the step of adding a preformed coordination complex prepared using a heteroatom ligand and a transition metal precursor to a reaction mixture containing an activator. 2. The method according to item 1.   31. The method of claim 30, comprising the step of forming a heteroatom coordination complex in situ from the transition metal compound and the heteroatom ligand.   32. A method according to any one of claims 2-5 and 7-31, wherein the transition metal is selected from any one of the group consisting of chromium, molybdenum, tungsten, titanium, tantalum, vanadium and zirconium.   33. A method according to any one of claims 2 to 5 and 7 to 32, wherein the transition metal is chromium.   32. A method according to any one of claims 29 to 31 wherein the transition metal compound is selected from the group consisting of inorganic salts, organic salts, coordination complexes and organometallic complexes.   The transition metal compound is composed of chromium trichloride tris-tetrahydrofuran complex, (benzene) tricarbonyl chromium, chromium octanoate (III), chromium acetylacetonate (III), hexacarbonyl chromium and chromium 2-ethylhexanoate (III). 35. The method of claim 34, wherein the method is selected from any one of the groups.   36. A method according to any one of claims 29 to 31 and 33 to 35, wherein the transition metal compound is selected from a complex selected from chromium (III) acetylacetonate and chromium (III) 2-ethylhexanoate.   A transition metal derived from a transition metal compound and a heteroatom ligand are combined to provide a metal / ligand ratio of about 0.01: 100 to 10,000: 1. The method according to any one of the above.   38. The method of claim 37, wherein the transition metal compound and the heteroatom ligand are combined to provide a metal / ligand ratio of about 0.1: 1 to 10: 1.   The catalyst system is an organoaluminum compound, an organoboron compound, an organic salt (such as methyl lithium bromide and methyl magnesium bromide), an inorganic acid and an inorganic salt (tetrafluoroborate etherate, silver tetrafluoroborate and hexafluoroantimonic acid) 39. A method according to any one of claims 29 to 38 comprising an activator selected from any one of the group consisting of sodium and the like.   32. A process according to any one of claims 29 to 31 wherein the activator is selected from alkylaluminoxanes.   41. The method of claim 40, wherein the alkylaluminoxane, or mixture thereof, is selected from the group consisting of methylaluminoxane (MAO), ethylaluminoxane (EAO) and modified alkylaluminoxanes (MMAO).   42. The method of claim 39 or claim 41, wherein the transition metal and aluminoxane are combined in a ratio that provides an Al / metal ratio of about 1: 1 to 10,000: 1.   43. The method of claim 42, wherein the transition metal and aluminoxane are combined in a ratio that provides an Al / metal ratio of about 1: 1 to 1000: 1.   44. The method of claim 43, wherein the transition metal and aluminoxane are combined in a ratio that provides an Al / metal ratio of about 1: 1 to 300: 1.   45. A process according to any one of claims 42 to 44 comprising the step of adding to the catalyst system an amount of trialkylaluminum compound between 0.01 and 100 moles per mole of alkylaluminoxane.   46. A process according to any one of claims 2 to 5 and 7 to 45, comprising mixing the components of the catalyst system at any temperature between -20C and 250C in the presence of olefins.   47. A process according to any one of claims 2 to 5 and 7 to 46, wherein the product stream is contacted with the catalyst system at a temperature in the range between 15C and 130C.   48. A process according to any one of claims 1-5 and 7-47, wherein methylcyclopentane and methylenecyclopentane are formed as products and independently constitute at least 1% of the product stream of the process. Transition metal and the following general formula (R) _n ABC (R) _m , wherein A and C are independently from phosphorus, arsenic, antimony, oxygen, bismuth, sulfur, selenium, and nitrogen Selected from the group consisting of: B is a linking group between A and C; R is the same or different; each R is independently selected from either a homo or heterohydrocarbyl group; N and m for R are independently determined by the respective valences and oxidation states of A and C, wherein at least one of R is substituted with a polar substituent) A tetramerization catalyst system. 50. The catalyst system of claim 49, wherein the ligand comprises a plurality of (R) _nABC (R) _m . Transition metal and the following general formula (R ¹ ) (R ² ) ABC (R ³ ) (R ⁴ ) wherein A and C are independently phosphorus, arsenic, antimony, bismuth and nitrogen B is a linking group between A and C and R ¹ , R ² , R ³ and R ⁴ independently comprise a non-aromatic group and a heterocyclic aromatic 51. A heteroatom ligand selected from aromatic groups and represented by: at least one of R ¹ , R ² , R ³ and R ⁴ is substituted with a polar substituent. A catalyst system according to claim 1. Each R ¹ , R ² , R ³ and R ⁴ is an aromatic, including a heterocyclic aromatic, but not all R ¹ , R ² , R ³ and R ⁴ are bonded to A or C 52. The catalyst system according to claim 50 or claim 51, wherein the catalyst system is substituted by an arbitrary substituent on an atom adjacent to the atom. More than two R ^1, R ^2, R ³ and R ^4, the catalyst system according to claim 51 or claim 52 having a substituent on the atom adjacent to the atom bound to A or C. R ^{1, R 2,} R ³ and any polar substituents on R ⁴ is, catalyst system according to claim 52 not on atoms adjacent to atom bound to A or C. 55. Any of claims 52 to 54, wherein at least one of R ¹ , R ² , R ³ and R ⁴ is substituted with a polar substituent on an atom two or more away from the atom bonded to A or C. 2. The catalyst system according to item 1. R ^{1, R} 2, ^{R 3} and one or any polar substituent of the plurality on ^{R 4} is, catalyst system according to claim 49 or 56 Noizuraka 1 wherein an electron-donating.   57. The catalyst system according to any one of claims 49 to 56, wherein A and / or C is a potential electron donor for coordination with a transition metal. B is an organic linking group comprising hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl and substituted heterohydrocarbyl; an inorganic linking group comprising a single atom bond; an ionic bond and methylene, dimethylmethylene, 1,2-ethane, 1,2-phenylene, 1,2-propane, 1,2-catechol, 1,2-dimethylhydrazine, -B (R ⁵ )-, -Si (R ⁵ ) _2- , -P (R ⁵ )-and -N (R ⁵ ) - (R ⁵ is hydrogen, hydrocarbyl or substituted hydrocarbyl, a heteroatom or a halogen to substituted) catalyst system according to any one of claims 49 to 57 selected from any one of the group consisting of.   59. A catalyst system according to any one of claims 49 to 58, wherein B is selected to be a single atom spacer. B is —N (R ⁵ ) — (R ⁵ is hydrogen or alkyl, substituted alkyl, aryl, substituted aryl, aryloxy, substituted aryloxy, halogen, nitro, alkoxycarbonyl, carbonyloxy, alkoxy, aminocarbonyl 60. selected from the group consisting of aryl, carbonylamino, dialkylamino, silyl groups or derivatives thereof, and aryl substituted by any of these substituents. The catalyst system according to item.   61. Any one of claims 50 to 60, wherein A and / or C are independently oxidized with S, Se, N or O (the valence of A and / or C enables said oxidation). The catalyst system according to item.   61. A catalyst system according to any one of claims 50 to 60, wherein A and C are independently phosphorus or phosphorus oxidized with S or Se or N or O. R ¹ , R ² , R ³ and R ⁴ are independently benzyl, phenyl, tolyl, xylyl, mesityl, biphenyl, naphthyl, anthracenyl, methoxy, ethoxy, phenoxy, tolyloxy, dimethylamino, diethylamino, methylethylamino, 63. The method of claims 49 to 62, selected from the group consisting of thiophenyl, pyridyl, thioethyl, thiophenoxy, trimethylsilyl, dimethylhydrazyl, methyl, ethyl, ethenyl, propyl, butyl, propenyl, propynyl, cyclopentyl, cyclohexyl, ferrocenyl and tetrahydrofuranyl groups A catalyst system according to any one of the preceding claims. The R ^{1, R} 2, ^{R 3} and ^{R 4,} independently, phenyl, tolyl, biphenyl, naphthyl, catalyst system according to any one of claims 49 to 63 selected from the group consisting of thiophenyl and ethyl group . The ligand may be (3-methoxyphenyl) ₂ PN (methyl) P (3-methoxyphenyl) ₂ , (4-methoxyphenyl) ₂ PN (methyl) P (4-methoxyphenyl) ₂ , (3-methoxy Phenyl) 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-methoxy Phenyl) (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 PN (2-methylcyclohexyl) P (4-methoxyphenyl) ₂ , (4-methoxy Phenyl) 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- _Ruorofeniru) 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- The group consisting of (4-methoxyphenyl) -phenyl) ₂ PN (isopropyl) P (4- (4-methoxyphenyl) -phenyl) ₂ and (4-methoxyphenyl) (phenyl) PN (isopropyl) P (phenyl) ₂ 65. The catalyst system according to any one of claims 50 to 60 and 62 to 64, selected from any one of the following.   66. A catalyst system according to any one of claims 49 to 65, wherein the transition metal is selected from any one of the group consisting of chromium, molybdenum, tungsten, titanium, tantalum, vanadium and zirconium.   67. A catalyst system according to any one of claims 49 to 66, wherein the transition metal is chromium.   68. The catalyst system of claim 67, wherein the transition metal compound is derived from a transition metal precursor selected from the group consisting of inorganic salts, organic salts, coordination complexes, and organometallic complexes.   The transition metal compound is composed of chromium trichloride tris-tetrahydrofuran complex, (benzene) tricarbonyl chromium, chromium octanoate (III), acetylacetonate chromium (III), hexacarbonyl chromium and 2-ethylhexanoate chromium (III). 69. The catalyst system of claim 68, selected from the group.   70. The catalyst system according to any one of claims 49 to 69, wherein the transition metal is selected from a complex selected from chromium (III) acetylacetonate and chromium (III) 2-ethylhexanoate.   68. The claim 68 or claim 68, wherein the transition metal derived from the transition metal compound and the heteroatom ligand are combined to provide a metal / ligand ratio of about 0.01: 100 to 10,000: 1. 69. The catalyst system according to 69.   72. The catalyst of claim 71, wherein the transition metal compound and heteroatom ligand are combined to provide a metal / ligand ratio of about 0.1: 1 to 10: 1.   73. A catalyst system according to any one of claims 49 to 72 comprising an activator.   The activator is an organoaluminum compound, an organoboron compound, an organic salt (such as methyllithium bromide and methylmagnesium bromide), an inorganic acid and an inorganic salt (tetrafluoroborate etherate, silver tetrafluoroborate and hexafluoroantimony) 74. The catalyst system of claim 73, selected from any one of the group consisting of sodium acid and the like.   75. A catalyst system according to claim 73 or claim 74, wherein the activator is selected from alkylaluminoxanes.   76. The catalyst system of claim 75, wherein the alkylaluminoxane, or mixture thereof, is selected from the group consisting of methylaluminoxane (MAO), ethylaluminoxane (EAO), and modified alkylaluminoxanes (MMAO).   76. The catalyst system of claim 74 or claim 75, wherein the transition metal and the aluminoxane are combined in a ratio that provides an Al / metal ratio of about 1: 1 to 10,000: 1.   78. The catalyst system of claim 77, wherein the transition metal and the aluminoxane are combined in a ratio that provides an Al / metal ratio of about 1: 1 to 1000: 1.   79. The catalyst system of claim 78, wherein the transition metal and the aluminoxane are combined in a ratio that provides an Al / metal ratio of about 1: 1 to 300: 1.   80. A catalyst system according to any one of claims 75 to 79 comprising a trialkylaluminum compound in an amount between 0.01 and 100 moles per mole of alkylaluminoxane.   Use of the tetramerization catalyst system according to any one of claims 49 to 80 for the tetramerization of olefins.   Use of the tetramerization catalyst system according to any one of claims 49 to 80 for the tetramerization of ethylene.   Use of a ligand for the tetramerization process according to any one of claims 1 to 5 and 7 to 48.   Use of a ligand for a tetramerization catalyst system according to any one of claims 49 to 80.   Process for the tetramerization of olefins substantially as described herein. Olefin tetramerization catalyst system substantially as herein described.