WO2016186287A1

WO2016186287A1 - Catalytic system for olefin oligomerization reaction and method for olefin oligomerization using same

Info

Publication number: WO2016186287A1
Application number: PCT/KR2015/014279
Authority: WO
Inventors: 박진영; 이용호; 이기수; 신은지; 사석필; 임슬기
Original assignee: 주식회사 엘지화학
Priority date: 2015-05-15
Filing date: 2015-12-24
Publication date: 2016-11-24

Abstract

The present invention relates to a catalytic system for an olefin oligomerization reaction and a method for olefin oligomerization and, more specifically, to a catalytic system for an olefin oligomerization reaction, which exhibits high activity in the olefin oligomerization reaction only through smaller amounts of a catalytic composition and a cocatalyst, by using catalytic active components supported on a support, thereby producing alpha-olefin more efficiently, and to a method for olefin oligomerization.

Description

[Name of invention]

Catalyst system for leulevine oligomerization reaction and method for leulevine oligomerization using the same [cross-reference with related application (s)]

This application claims the benefit of priority based on Korean Patent Application No. 10-2015-00683 No. 15 May 2015 and Korean Patent Application No. 10-2015-0185316 No. 23 December 2015. All content disclosed in the literature is included as part of this specification.

Technical Field

The present invention relates to a catalyst system for an olefin oligomerization reaction reaction and a method for olefin oligomerization, and more particularly, a ligand compound is supported on a support so that a lower amount of catalytically active ingredient and cocatalyst can be used in an olephine oligomerization reaction reaction. The present invention relates to an olefinic oligomerization reaction catalyst system and an olefin oligomerization method, which can exhibit high activity and thus enable more efficient preparation of alpha-olefins.

Background Art

Linear alpha-efin is used as a cleaning agent, lubricant, plasticizer, etc., and is especially used as a comonomer for controlling the density of polymers in the production of linear low-density polyethylene (LLDPE). . Conventional processes for the production of LLDPE include co-monomers such as alpha-olefins, for example, 1-nuxene and 1-octene, in order to control the density by forming branches in the polymer backbone with ethylene. Copolymerization with was made.

Therefore, in order to manufacture LLDPE having a high comonomer content, there is a problem that the price of the comonomer occupies a large part of the manufacturing cost. In order to solve this problem, various attempts have been made.

In addition, alpha-olefins have different application fields and market sizes. Because of this, the technology to produce various leupins at the same time is of great commercial importance. Recently, ethylene oligomerization reaction or polymerization reaction of ethylene is used to prepare 1-nuxene, 1-octene or polyethylene with specific selectivity. Much research has been done on creme catalyst technology.

[Content of invention]

[Problem to solve]

The present invention provides olefin oligomerization in olefin oligomerization reaction, which can realize high catalytic activity and selectivity for linear alpha-lepin, even when a relatively small amount of promoter is added, compared to a liquid catalyst system. It is to provide a catalyst system for the reaction.

In another aspect, the present invention to provide a method for olefin leolimerization using the catalyst system.

[Measures of problem]

The present invention is a ligand compound comprising at least one diphosphine group represented by the formula (1) in the molecule; Crum sauce; And a support, including a support for a lelpene oligomerization reaction system.

[Formula 1] _*

In Chemical Formula 1,

P is a phosphorus atom, N is a nitrogen atom,

R1 to R4 are each independently the same or differently have 1 to

20 is a hydrocarbyl group, a heterohydrocarbyl group, or a hydrocarboheteryl group, and * indicates that the group of Formula 1 is a monovalent linking group.

At this time, the ligand compound is a diphosphine represented by the formula (1) It includes two or more groups, the diphosphine group may be linked by a linker L.

And, L is a linker having 4 to 10 carbon atoms in the shortest distance connecting the diphosphine group, an aliphatic linking group having 2 to 20 carbon atoms, an alicyclic linking group having 3 to 20 carbon atoms, or an aromatic linking group having 6 to 20 carbon atoms It may be a flag.

According to one example, the diphosphine group, all of which can form a coordination bond with chromium.

Specifically, it may be preferable that the mole number ratio of the creme atom to the mole number of the ligand compound is one or more.

In addition, the leulevine oligomerization reaction catalyst system, may include an organic chromium compound having at least one creme complex group represented by the following formula (2) in the molecule.

[Formula 2]

★

In Chemical Formula 2,

P is a phosphorus atom, N is a nitrogen atom, Cr is a creme atom,

R1 to R4 are each independently the same or different and have a C1-C20 hydrocarbyl group, a heterohydrocarbyl group, or a hydrocarboheteryl group, and Y1 to Y3 are each independently the same or differently, A hydrogen atom, a halogen atom, a hydrocarbyl group having 1 to 10 carbon atoms, a heterohydrocarbyl group having 1 to 10 carbon atoms, or a hydrocarboheryl group,

* Indicates that the group of Formula 1 is a monovalent linking group.

According to another embodiment of the invention, the source of crumb is chromium (III) acetylacetonate, chromium chloride tetrahydrofuran, chromium (III) 2-ethylnucleoate chromium (III) acetate, chromium ( III) Butyrate, chromium (III) pentanoate, chromium (III) laurate, chromium (III) tris (2,2,6,6-tetramethyl -3.5- Heptanedionate), and at least one compound selected from the group consisting of chromium (III) stearate.

In addition, the olefinic oligomerization reaction catalyst system may further include a promoter supported on the support.

In this case, the promoter is trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, ethylaluminum sesquichloride, It may be at least one compound selected from the group consisting of diethylaluminum chloride, ethyl aluminum dichloride, methylaluminoxane, and modified methylaluminoxane.

Preferably, the cocatalyst may be supported at about 5 to about 15 mmol / g based on 1 g of the support.

On the other hand, according to another aspect of the present invention, there is provided a method for oligomerization of olefins comprising the step of undergoing the oligomerization reaction of the olefinic monomers in the presence of the catalyst system to form an alpha-olefin.

At this time, the olefin monomer may be preferably ethylene.

According to one embodiment of the invention, the oligomerization of the olefinic monomers may be carried out at a temperature of about 5 to about 200 ^° C and may be preferably carried out at a pressure of about 1 to about 300 bar.

【Effects of the Invention】

In the case of the olefinic oligomerization reaction catalyst system of the present invention, the catalyst metal and the cocatalyst component can be uniformly distributed throughout the support, thereby exhibiting high activity in a relatively small amount.

In addition, by using the supported catalyst in the solid phase, the catalyst can be easily separated from the liquid semicoagulant and the product, and the production of other isomers can be reduced, and since the production of the solid polyethylene occurs on the support, the surface of the reaction apparatus, etc. It can effectively prevent the parling phenomenon that may occur. [Brief Description of Drawings]

1 is a photograph observing the state of the half-unggi internal device after the ethylene oligomerization reaction in Example 1 and Comparative Example 1 according to the present invention.

Figure 2 is a photograph observed after drying the solid products obtained in Example 1 and Comparative Example 1 according to the present invention.

3 and 4, in Comparative Examples 2 and 4 according to the present invention, after the ethylene oligomerization reaction, respectively, is a photograph observing the state of the reaction apparatus and the inner wall state. [Specific contents to carry out invention]

The term ^' , as used herein, is merely used to describe exemplary embodiments and is not intended to limit the present invention. A singular expression includes a plural expression unless the context clearly indicates otherwise. As used herein, the terms "comprise,""comprise," or "have" are intended to indicate that the features, features, steps, components, or combinations thereof are present, one or more other features It is to be understood that the present invention does not exclude the possibility of adding or presenting numbers, steps, components, or combinations thereof.

As the invention allows for various changes and numerous embodiments, particular embodiments will be illustrated and described in detail below. However, this is not intended to limit the present invention to the specific form disclosed, it should be understood to include all modifications, equivalents, and substitutes included in the spirit and scope of the present invention. Throughout the present specification, "oligomerization" means that the olepin is polymerized. For example, depending on the number of repeats of the olefins to be polymerized, generically refers to multimerization, including trimerization or tetracycling reactions, in particular the 1-nucleene used herein as the main comonomer of LLDPE from ethylene And / or selectively preparing 1-octene.

And, in the entire specification, the hydrocarbyl group is a hydrocarbon Compounds collectively include, for example, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, a cycloalkyl group, and the like, and unless otherwise specified, include both straight and branched chains, and substituted and unsubstituted. Includes all of them.

And, throughout the specification, the alkylaryl group means an aryl group having at least one alkyl group as a substituent, and the aryl alkyl group means an alkyl group having at least one aryl group as a substituent

In addition, as used herein, a hetero element means nitrogen, oxygen, sulfur, or phosphorus, and a heterohydrocarbyl group refers to a hydrocarbyl group containing one or more hetero atoms. In the case of such a heterohydrocarbyl group, it means that the linking point to be functionalized is carbon, and in the case of being referred to as a heteryl group such as a 'hydrocarboheteryl group' or an 'organoheteryl group', the linking point to be functionalized is a hetero atom Means to be. Hereinafter, the present invention will be described in more detail. An olefin oligomerization reaction catalyst system according to an aspect of the present invention includes a ligand compound comprising at least one diphosphine group represented by Formula 1 in a molecule;

Lol til

And a support.

[Formula 1]

In Chemical Formula 1,

P is a phosphorus atom, N is a nitrogen atom,

R1 to R4 are each independently the same or different and have a C1-C0 hydrocarbyl group, a heterohydrocarbyl group, or a hydrocarboheteryl group, ^* Indicates that the group of Formula 1 is a monovalent linking group. The ligand compound contains a diphosphino moiety in the molecule and can provide a lone pair of electrons to a ligand such as a creme due to the rich electron density of nitrogen atoms and phosphorus atoms.

Due to these structural features, the electrical and steric properties of the entire ligand compound may change, the bond between the ligand and the chromium atom may change, the structure of the catalyst may be more stable, and the existing metallacycloheptane, or metallacyclononane Compared with the reaction mechanism by, it is possible to change the energy of the transition state, that is, the activation energy of the reaction, to form alpha-olefin with higher activity and selectivity.

Many existing organic stomite catalysts can produce alpha-olefins with high activity and selectivity in liquid phase reactions using MAO or borate cocatalysts. It was common for the activity to fall extremely.

However, the catalyst system according to one aspect of the present invention, even when supported on a support such as silica, can produce alpha-olefins with high activity and selectivity, and because it is a solid phase, it is a liquid half product and a product. It is easy to separate from the catalyst, thereby reducing the amount of isomers due to side effects or side reactions that may occur when the catalyst is not separated from the product.

In this way, since the catalyst system can be easily separated in the reaction system, by-products such as solid polyethylene due to the side reaction of the homogeneous liquid reaction reaction can be reduced.

And since the olefin oligomerization reaction can proceed in the pores and the like in the support, even if the solid polyethylene is produced, it is fixed in the support and can prevent the production of the solid polyethylene fish that is produced during the homogeneous liquid reaction. It is possible to effectively prevent problems such as fouling, pipe blockage, and the like, which may occur when these by-products remain in the reactor.

Furthermore, since the chromium and the promoter component, which are catalytically active components, are supported together in the same support, interaction between the catalyst and the promoter can easily occur, Relatively less than when used in catalyst form

Even if used, with high activity, it becomes possible to polymerize the linear alpha-olefin.

According to one embodiment of the invention, the ligand compound includes two or more diphosphine groups represented by the formula (1), ᅳ the diphosphine group may be linked to a linker L, for example, It may be represented by 1-1.

[Formula 1-1]

In Chemical Formula 2,

P is a phosphorus atom,

N is a nitrogen atom, P is a nitrogen atom,

R1 to R4 and R1 'to R4' are each independently the same or different and have a C1-C20 hydrocarbyl group, heterohydrocarbyl group, or hydrocarboheteryl group,

L is a C2-C30 hydrocarbyl or heterohydrocarbyl group connecting between two or more diphosphine groups.

More specifically, in Formulas 1 and 2, R1 to R4 and R1 'to R4' may be, for example, an aryl group having 6 to 20 carbon atoms, a heteroaryl group or an arylheteryl group; Or an alkylaryl group having 7 to 20 carbon atoms, a heteroalkylaryl group, an alkyl heteroaryl group, or an alkylaryl heteroaryl group.

The linking group (L) may be a hydrocarbyl group, a heterohydrocarbyl group, or a hydrocarbyl heterotyl group having various structures, and the number of atoms of the shortest distance between diphosphine groups may be 2 to 30 atoms. Specifically, for example, aliphatic linking group having 2 to 20 carbon atoms, heteroaliphatic group having 2 to 20 carbon atoms It may be a linking group, an alicyclic linking group having 3 to 20 carbon atoms, a heteroalicyclic linking group having 3 to 20 carbon atoms, an aromatic linking group having 6 to 20 carbon atoms, or a heteroaromatic linking group having 6 to 20 carbon atoms, and the structure thereof is not particularly limited. . In addition, when two or more groups selected from these linking groups are determined as the main chain, the main chain of the linking group may have substituents of various structures.

Non-limiting examples of the above-described linking group include those having the following structural formula. In the following examples, the diphosphine groups represented by Formula 1 are represented by [A], [Α ′], or [Α ″] for convenience, and each diphosphine group may be the same as or different from each other.

(i) when connecting a plurality of diphosphine groups with 2 or 3 carbon atoms:

(ii) connecting a plurality of diphosphine groups with four carbon atoms

As a more specific example, the connector (L) may be a 11 connector, a crab 2 connector, or a third connector described below.

The first linker may be four carbon atoms of the shortest distance between the diphosphine group, an aliphatic linker having 1 to 20 carbon atoms, an alicyclic linker having 3 to 20 carbon atoms, and an aromatic linking group having 6 to 20 carbon atoms, It may have the following structural formula.

In the structural formula * is a part connected to the diphosphine group represented by Formula 1,

RR is each independently an alkyl group having 1 to 5 carbon atoms,

n is the number of substitution substituted in each ring, may vary depending on the number of substitution within an integer range of 1 to 4,

The plurality of RRs coupled to the ring in one may be the same or different from each other. In this case, the ligand compound may have, for example, the following structural formula.

In addition, the second linking group has 5 to 8 carbon atoms at the shortest distance between the diphosphine groups, and is composed of an aliphatic linking group having 5 to 20 carbon atoms, or an aliphatic having 1 to 20 carbon atoms and an aromatic ring having 6 to 20 carbon atoms. It may be made of a linking group, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms at at least one end of the linking group. The crab coupler may specifically have the following structural formula.

In addition, the third connector, 4 to 23 carbons of the shortest distance between the diphosphine group, it may be represented by the formula (3).

[Formula 3]

In Chemical Formula 3,

Q means a diphosphine group, represented by Formula 1,

X is alkylene of 1 to 20 carbon atoms or arylene of 6 to 14 carbon atoms,

R 5 to R 14 are each independently the same or different and have an alkyl group of 1 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, an aryl group of 6 to 14 carbon atoms, an alkylaryl group of 7 to 18 carbon atoms, and 7 to 7 carbon atoms. 18 arylalkyl group or carbon number

It may be an alkoxyaryl group of 7 to 18.

In this case, a representative example of the ligand compound may have the following structural formula.

Due to the structure of the linking group, that is, the linker (L) as described above, the activity of the supported catalyst can be further improved, and may also be advantageous in terms of selectivity for linear alpha-lefin.

According to one embodiment of the invention, a non-covalent electron pair belonging to one or more diphosphine groups of two or more diphosphine groups included in the ligand compound may exist in the form of an organic crum compound, coordinated to the chromium atom. In addition, the diphosphine group, and all the keureum and ^■ may be desirable to form a coordination bond, and can, by mole of the mole number of contrast keureum atoms of the ligand compound for this ratio is 1 or more, preferably from about 1 To a molar ratio of about 2 to about 2.

For example, the catalyst system for the olefin oligomerization reaction may include an organic creme compound having at least one chromium complex group represented by the following formula (2) in a molecule.

[Formula 2]

*

In Chemical Formula 2,

P is a phosphorus atom, N is a nitrogen atom, Cr is a chromium atom,

R1 to R4 are each independently the same or different and have a C1-20 hydrocarbyl group, a heterohydrocarbyl group, or a hydrocarboheteryl group, and Y1 to Y3 are each independently the same or differently, A hydrogen atom, a halogen atom, a hydrocarbyl group having 1 to 10 carbon atoms, a heterohydrocarbyl group having 1 to 10 carbon atoms, or a hydrocarbohetyl group,

* Indicates that the group of Formula 1 is a monovalent linking group.

That is, in the form of an organic kneading compound in which a phosphorus valence of a diphosphine group forms a coordinating bond with one chromium, one molecule of the organic kneading compound has at least one catalytically active point for olefin oligomerization reaction, preferably 2 There may be more than one.

Accordingly, the activity of the catalyst and the selectivity to linear alpha-lefin can be further improved, the supporting efficiency is excellent, and the phenomenon that the catalyst component is separated from the support during reaction or separation can be reduced.

In this respect, the linker (L) is relatively flexible, so that each diphosphine group can be smoothly acting as a tethering and active point It may be more desirable to include aliphatic linkages. For example, in the case where the linking group is composed of aliphatic or aromatic only without containing aliphatic, the rigid bonds may cause extremely limited interactions, resulting in significantly lower catalytic activity and selectivity to linear alpha-olefins. It can also be degraded.

And, the ligand compound, based on the weight of the chromium in the coordinated state, based on 100 parts by weight of the support, about 0.5 to about 20 parts by weight, preferably about 1 to about 15 parts by weight more preferably about 1 To about 10 parts by weight.

According to one embodiment of the invention, the mole number ratio of the chromium atoms to the mole number of the ligand compound may be 1 or less, preferably, 1: 1 to 10: 1, preferably, 1: 1 to 5: 1 days Can be. The support has a specific surface area capable of sufficiently supporting the catalyst component, and a general support containing many pores therein may be used so that olefin oligomerization reaction can occur smoothly.

That is, the support may be any metal or nonmetal, a salt thereof, or an oxide, which is usually used in a supported catalyst, without particular limitation, and specifically, for example, silica, alumina, silica-alumina, silica-magnesia, etc. may be applied. However, the present invention is not necessarily limited thereto. Such a support may be dried at high temperatures and generally include materials such as oxides, carbonates, sulfates, or nitrates of metals, such as sodium oxide, potassium carbonate, barium sulfate, magnesium nitrate, and the like.

In addition, the surface of the support preferably contains less hydroxy groups, but it may not be possible to remove all hydroxy groups. Accordingly, it may be important to control the amount of hydroxy groups by adjusting drying conditions in preparing the support. . For example, such a hydroxy group may be about 10 mmol / g or less, preferably about 1 mmol / g or less, and more preferably about 0.5 mmol / g or less based on the mass of the support. In addition, in order to reduce side reactions of some of the hydroxy groups remaining after drying, a support which selectively removes only hydroxy groups while preserving supported siloxane groups may be used. In the catalyst system, the source of the crack may be an organic or inorganic chromium compound in which the oxidation state of the crack is from 0 to 6, for example chromium metal, or a compound in which any organic or inorganic radical is bonded to chromium. . Here, the organic radical may be an alkyl, alkoxy, ester, ketone, amido, carboxylate radical, etc. having 1 to 20 carbon atoms per radical, and the inorganic radical may be a halide, sulfate, oxide, or the like.

Specifically, for example, the chromium source may be chromium (III) acetylacetonate, chromium (ᅵ |) chloride tetrahydrofuran, chromium (III) 2-ethylnucleosanate, chromium (III) acetate, chromium (III) Consisting of butyrate, chromium (III) pentanoate, chromium (III) laurate, chromium (III) tris (2, 2, 6, 6-tetramethyl-3.5-heptanedionate), and chromium (III) stearate It may be one or more compounds selected from the group. According to another embodiment of the present invention, the catalyst system described above may further include a promoter supported on the support.

And, preferably, the cocatalyst is an organometallic compound containing a Group 13 metal, and can be applied without particular limitation, as long as it can be generally used when polymerizing leupine under a catalyst of a transition metal compound.

For example, the promoter may be at least one compound selected from the group consisting of compounds represented by Formulas 4 to 6 below:

[Formula 4]

-[AI (Rx) -O] _c- . In Formula 4, AI is aluminum,

Rx is the same as or different from each other, and each independently a halogen radical, a hydrocarbyl radical having 1 to 20 carbon atoms, or a hydrocarbyl radical having 1 to 20 carbon atoms substituted with halogen, c is an integer of 2 or more,

[Formula 5]

D (Ry) ₃

In Formula 5, D is aluminum or boron, Ry is 1 to carbon atoms A hydrocarbyl having 1 to 20 carbon atoms substituted with 20 hydrocarbyl or halogen,

[Formula 6]

[LH] ⁺ [Q (E) ₄ ] — in Formula 6,

L is a neutral Lewis base, [LH] ⁺ is Bronsted acid, Q is boron or aluminum in the +3 type oxidation state, each E is independently at least one hydrogen atom is halogen, a hydrocarbyl having 1 to 20 carbon atoms, An aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms which is unsubstituted or substituted with an alkoxy functional group or a phenoxy functional group.

According to one embodiment, the compound represented by Formula 4 may be alkyl aluminoxane, such as methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, butyl aluminoxane.

And, according to one embodiment, the compound represented by the formula (5) is trimethyl aluminum, triethyl aluminum, triisobutyl aluminum tripropyl aluminum, tributyl aluminum, dimethyl chloro aluminum dimethyl isobutyl aluminum, dimethyl ethyl aluminum, diethyl chloro Aluminum Triisopropyl Aluminum, Tri-S-Butyl Aluminum, Tricyclopentyl Aluminum Tripentyl Aluminum, Triisopentyl Aluminum, Trinuclear Aluminum Ethyl Dimethyl Aluminum, Methyl Diethyl Aluminum, Triphenyl Aluminum, Tri-P-allyl Aluminum, Dimethyl Aluminum mesoxide, dimethylaluminum oxide, trimethyl boron triethyl boron, triisobutyl boron, tripropyl boron, tributyl boron and the like. Further, according to one embodiment, the compound represented by the formula (6) is triethyl ammonium tetraphenyl boron, tributyl ammonium tetraphenyl boron, trimethyl ammonium tetraphenyl boron, tripropyl ammonium tetraphenyl boron, trimethyl ammonium Tetra (P-ryll) boron ， Tripropylammoniumtetra (P-lryl) boron, Triethylammoniumtetra (ο, ρ-dimethylphenyl) boron, Trimethylammoniumtetra (ο, ρ-dimethylphenyl) boron ， Tri Butyl ammonium tetra (Ρ-trifluoromethylphenyl) boron, trimethyl ammonium tetra (Ρ-trifluoromethylphenyl) boron,

Tributylammonium tetrapentafluorophenylboron, Ν, Ν- Diethylanilinium tetraphenyl boron, Ν, Ν-diethylanilinium tetraphenylboron, Ν, Ν-diethylanilinium tetrapentafluorophenylboron,

Diethyl ammonium tetrapentafluorophenyl boron, triphenyl phosphonium tetraphenyl boron, trimethyl phosphonium tetraphenyl boron, triethyl ammonium tetraphenyl aluminum, tributyl ammonium tetraphenyl aluminum, trimethyl ammonium tetraphenyl aluminum, tri Propyl Ammonium Tetraphenyl Aluminum, Trimethyl Ammonium Tetra (Ρ-rylryl) Aluminum, Tripropyl Ammonium Tetra (Ρ-rylryl) Aluminum, Triethyl Ammonium Tetra (ο, ρ-dimethylphenyl) Aluminum, Tributyl Ammonium Tetra (Ρ-trifluoromethylphenyl) aluminum, trimethylammonium tetra (Ρ-trifluoromethylphenyl) aluminum, tributylammonium tetrapentafluorophenylaluminum, Ν, Ν-diethylanilinium tetraphenylaluminum, Ν , Ν-diethylanilinium tetraphenylaluminum, Ν, Ν-diethylanilinium tetrapentafluorophenyl Aluminum,

Diethylammonium tetrapentafluorophenylaluminum,

Triphenylphosphonium tetraphenylaluminum, trimethylphosphonium tetraphenylaluminum, triphenylcarbonium tetraphenylboron, triphenylcarbonium tetraphenylaluminum, triphenylcarbonium tetra (Ρ-trifluoromethylphenyl) boron,

Triphenylcarbonium tetrapentafluorophenylboron and the like.

In addition, as a non-limiting example, the promoter may be an organoaluminum compound, an organoboron compound, an organic magnesium compound, an organozinc compound, an organolithium compound, or a combination thereof. According to one embodiment, the promoter is preferably an organoaluminum compound, more preferably trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum (triisobutyl aluminum), ethylaluminum sesquichloride, diethylaluminum chloride, ethyl aluminum dichloride, methylaluminoxane, and modified methylaluminoxane It may be one or more compounds selected from the group consisting of

When both the ligand compound and the promoter are supported on the support, The content is not particularly limited, but the molar ratio of the ligand compound and the cocatalyst may be about 1: 5 to 1: 1, and preferably about 1:10 to about 1: 250.

In addition, with respect to 100 parts by weight of the support, the promoter may be included in about 1 to about 1,000 parts by weight, preferably about 10 to about 100 parts by weight, more preferably about 40 to about 150 parts by weight. In a supported form, the ligand compound coordinated with the creme atom and the cocatalyst may be supported on a single support in a uniform composition, or may be supported and used on different supports, respectively.

In addition, the supporting method is also not particularly limited, and the promoter may be first supported on the support, and then the ligand compound coordinated with the chromium atom may be supported. In this case, the promoter may be supported by dividing the amount to be finally supported by two.

The loading of the promoter and ligand compound may proceed for about 1 to about 20 hours in the temperature range of about 20 to about 12 C C.

Specifically, the step of contacting the promoter with the support, supporting the promoter on the inside and the surface of the support; And adding, to the support on which the promoter is supported, a mixture including a ligand compound and a crum source to carry it.

In addition, in the step of supporting the promoter, the temperature can be divided into one or more times by varying the temperature at the time of adding the promoter, and each of the input temperature can be lowered sequentially from the initial input temperature, for example, From minus 50 ^° C. to about image 150 ^° C., it may proceed under progressively lower silver conditions. On the other hand, according to another aspect of the present invention, there is provided a method for oligomerization of an olefin comprising the step of forming an alpha-olefin by proceeding the oligomerization reaction of the olefin monomer in the presence of the catalyst system described above.

At this time, the olefin monomer may be preferably ethylene.

In general, olefin oligomerization reactions can be carried out using conventional equipment and contact techniques. May be applied. By way of non-limiting example, a typical olefin oligomerization reaction may be a homogeneous liquid reaction in the presence or absence of an inert solvent, or a slurry reaction in which the catalyst system is partially or completely insoluble, or the product alpha-olefin or polyethylene. It can be carried out in bulk or gaseous reactions which act as the main medium.

However, in the homogeneous liquid reaction, solid polyethylene is inevitably generated as a by-product, and since such solid polyethylene remains in a non-uniform form in the liquid phase of the reaction system, the efficiency of the oligomerization reaction is reduced, and the linear alpha-olefin Decreases the selectivity to, and may cause side effects such as fouling phenomenon.

However, according to the present invention, since the oligomerization reaction is carried out in the pores in the supported catalyst as a solid supported catalyst, the stability of the catalyst is very high, and even if solid polyethylene or the like is produced, the morphology of the oligomerization reaction can be maintained. .

In addition, since at least one of the diphosphine groups included in the ligand compound can be strongly tethered with the support to reduce leaching of the catalytically active component, it is possible to increase the efficiency of the reaction and to reduce the impurities content, As described above.

In addition, the leupin oligomerization reaction may be performed under an inert solvent. As a non-limiting example, the inert solvent may be benzene, toluene, xylene, cumene, chlorobenzene, dichlorobenzene, heptane, cyclonucleic acid, methylcyclonucleic acid, methylcyclopentane, n-nucleic acid, 1-nuxene, 1-octene, etc. have.

In addition, the olepin oligomerization reaction may be performed at a temperature of about 0 to about 2 ocrc, or about 0 to about 150 ^° C, or about 30 to about 100 ^° C, or about 50 to about 100 1. The reaction may also be carried out under a pressure of about 1 to about 300 bar, or 2 to about 150 bar. Hereinafter, the operation and effects of the invention will be described in more detail with reference to specific embodiments of the invention. However, these embodiments are only presented as an example of the invention, whereby the scope of the invention is not determined. <Example>

Support preparation

Silica (SP 952X, Grace Davison) was vacuum dried at a temperature of 200 ^° C. for 12 hours to prepare a support and stored in an argon atmosphere glove box. Catalyst system manufacturers

Manufacture

Under argon, 5 mmol of 3- (aminomethyl) 3,5,5-trimethylcyclonucleic amine and triethylamine (4-10 amine equivalents) were dissolved in 80 ml of dichloromethane using a flask.

While the flask was immersed in a water bath, Chloroditolyphosphine (4 equivalents to amine) was slowly added dropwise and stirred overnight.

After vacuum was removed to remove the solvent, THF was added, the mixture was sufficiently stirred, and triethylammonium chloride salt was removed with an air-free glass filter. The solvent was removed from the filtrate to obtain a ligand compound represented by the above structural formula.

To this ligand compound, trivalent chromium acetate (146.7 mg,

0.42 mmol) was prepared, and the flask was added so that the molar ratio of chromium to ligand compound was 2: 1, 65 ml of toluene was added thereto, followed by stirring to prepare an 11 mM organic cream complex.

7 g of the support prepared above was placed in a glass reactor at 40 ^° C., and supported by adding a methylaluminoxane (MAO) solution containing 77 mmol of aluminum to the toluene solution. The organic chromium complex prepared above was added thereto, and the reaction mixture was stirred for 2 hours and then stirred to remove the filtrate.

After washing with a sufficient amount of toluene and adding 100 ml of Hexane and stirring again, the slurry solution prepared was transferred to an argon-substituted flask, and the filtrate was removed and dried in vacuo to remove the supported catalyst in the form of a solid powder. Got it.

Manufacture

Instead of 3- (aminomethyl) 3,5,5-trimethylcyclonucleic amine, 2,6-diethylaniline was used, and 0.35 mmol as the chromium source was used, and the molar ratio of the ligand compound and the creme atom was 1: 1. A supported catalyst was prepared in the same manner as in Preparation Example 1, except that the supported catalyst was used.

Manufacture

Instead of 3- (aminomethyl) 3,5,5-trimethylcyclonucleic acid amine, P-lluidine was used, and 0.35 mm was used only as a creme source, and the molar ratio of ligand compound and creme atom was 1: 1. A supported catalyst was prepared in the same manner as in Preparation Example 1, except that the supported catalyst was used. Ethylene oligomer manufacturing

[Examples 1-3] The oligomerization reaction was carried out in a 600 ml metal alloy material reactor, equipped with a mechanical stirrer, capable of temperature control and driving at high pressure.

The supported catalyst prepared in Preparation Examples 1 to 3 was weighed 30 mg in a dry box and placed in a 50 ml glass bottle. It was sealed with a rubber diaphragm, taken out of the dry box, and prepared for injection into the reaction machine.

400 mL of nucleic acid (Hexane) containing I.Ommol triethylaluminum and the prepared supported catalyst were added without contacting the air, and the gaseous ethylene monomer was continuously injected at a pressure of 30 bar at 80 ^° C. The ligomerization reaction was performed for hours.

Thereafter, the stirring was stopped, and the reaction was terminated by evacuating the non-banung ethylene.

Then, a small amount of the liquid portion was taken from the inside of the reactor and quenched with water, and the organic layer was filtered with a PTFE syringe filter to perform GC analysis.

409ml of ethanol / HCI (10vol%) was added to the remaining reaction solution, followed by stirring to obtain a polymer. The polymer was dried in a 60 ^° C. vacuum oven for 12 hours or more and weighed.

[Comparative Examples 1 to 3]

The organic catalyst compounds prepared in Preparation Examples 1 to 3 were the same cocatalyst composition and reaction as in Example 1, except that they were used as a liquid catalyst and were subjected to a uniform liquid reaction without being supported on a support. As a condition, reaction was performed.

The above results are summarized in Table 1 below.

Table 1

Comparative Example 1 220 Liquid 5862 2.56 2.11 4.67 2.00 Example 2 220 Supported 2608 0.58 0.32 0.91 3.40 Comparative Example 2 220 Liquid 409 0.05 0.03 0.08 0.27 Example 3 220 Supported 3203 0.54 0.81 1.35 2.00 Comparative Example 3 220 Liquid 213 0.03 0.02 0.05 0.16 Referring to Table 1, despite the use of the same proportions of organic crout compounds and cocatalysts under the same conditions, when using a supported catalyst system, even when a relatively small amount of cocatalyst is used, the catalytic activity is reduced. It can be seen that very good, and the selection for the linear alpha-olefin is also high.

This is thought to be due to the fact that the promoter and the catalytically active component (ligand compound-crude complex) are supported together in one support, the distance is close, and the chromium and the promoter can be uniformly distributed throughout the support and the outside. do.

Also, in the case of the comparative example, the catalytic activity is in the example. In the case of a liquid catalyst system, in general, a cocatalyst (based on the weight of aluminum) should be used in an amount of at least 600 equivalents, preferably 900 to 1500 equivalents, compared to the number of moles of the bulk, in order to achieve some activity. It is thought to result from using only 220 equivalents.

1 is a photograph observing the state of the reaction apparatus after the ethylene oligomerization reaction, in Example 1 and Comparative Example 1 according to the present invention, respectively.

3 and 4 are photographs of the reactor internal apparatus and the inner wall state after the ethylene oligomerization reaction, respectively, in Comparative Examples 2 and 4 according to the present invention.

Referring to the drawings, it can be seen that in the case of the comparative example, the fouling phenomenon, in which the solid product, that is, the solid polyethylene, is entangled in the reaction apparatus and the inner wall, is severely generated. In contrast, in the case of the embodiment, despite the ethylene oligomerization reaction after the reaction, it can be seen that the internal device and the wall surface of the reaction vessel is kept clean. This means that when using a supported catalyst, the selectivity to ethylene oligomer is very high, even if some solid polyethylene is produced, It appears to exist only inside the support, effectively preventing the fouling phenomenon.

Referring to FIG. 2, in the case of the comparative example in which the liquid reaction was performed, the morphology of the solid product is uneven enough to be difficult to utilize, and the packed particles are not disintegrated with each other. On the other hand, in the case of Examples, it can be confirmed that obtained in the form of a uniform powder, and thus can be expected to have a higher utilization than in the case of the comparative example.

Claims

[Range of request]

[Claim 1]

Ligand compound containing at least one diphosphine group represented by the formula (1) in the molecule;

Crum sauce; And

A catalyst system for olepin oligomerization reaction, comprising a support:

[Formula 1]

*

In Chemical Formula 1,

P is a phosphorus atom, N is a nitrogen atom,

R1 to R4, each independently, same or differently, have 1 to C

20 is a hydrocarbyl group, a heterohydrocarbyl group, or a hydrocarboheteryl group, and * indicates that the group of Formula 1 is a monovalent linking group. [Claim 2]

The method of claim 1,

The ligand compound comprises two or more diphosphine groups represented by Formula 1,

The diphosphine group is linked by a linker L, olefin oligomerization reaction system.

[Claim 3]

The method of claim 2,

L is a linker having 4 to 10 carbon atoms in the shortest distance connecting the diphosphine group, an aliphatic linking group having 2 to 20 carbon atoms, a cycloaliphatic linking group having 3 to 20 carbon atoms, or an aromatic linking group having 6 to 20 carbon atoms, Leuplin oligomerized Semi-Catalytic Catalyst System.

[Claim 4]

The method of claim 2,

The diphosphine groups, all of which form creme and coordination bonds, catalyst system for olefin oligomerization reaction.

[Claim 5]

The method of claim 1,

The mole ratio of chromium atoms to mole number of the ligand compound is at least 1, the olephine oligomerization reaction system.

[Claim 6]

The method of claim 1,

An olefin oligomerization reaction catalyst system comprising an organic chromium compound having at least one chromium complex group represented by formula (2) in a molecule:

[Formula 2 ᅵ

_**

I

丫 3

In Chemical Formula 2,

P is a phosphorus atom, N is a nitrogen atom, Cr is a chromium atom,

R1 to R4 are each independently the same or different and have a C1-C20 hydrocarbyl group, heterohydrocarbyl group, or hydrocarboheteryl group,

Y1 to Y3 are each independently the same or differently represent a hydrogen atom, a halogen atom, a hydrocarbyl group having 1 to 10 carbon atoms, a heterohydrocarbyl group having 1 to 10 carbon atoms, or a hydrocarboheteryl group,

^* Indicates that the group of Formula 1 is a monovalent linking group. [Claim 7]

The method of claim 1,

The chromium source is chromium (IN) acetylacetonate, chromium (IN) chloride tetrahydrofuran, chromium (III) 2-ethylnucleonoate, chromium (III) acetate, chromium (III) butyrate, chromium (IN) pentano At least one compound selected from the group consisting of eight, chromium (III) laurate, chromium (III) tris (2,2,6,6-tetramethyl-3.5-heptanedionate), and chromium (III) stearate , Catalyst system for olepin oligomerization reaction.

[Claim 8]

The method of claim 1,

A catalyst system for an olefin oligomerization reaction system further comprising a promoter supported on the support.

[Claim 9]

The method of claim 8,

The promoter is trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, ethylaluminum sesquichloride, diethylaluminum Olefin oligomerization half, at least one compound selected from the group consisting of diethylaluminum chloride, ethyl aluminum dichloride, dimethylaluminoxane, and modified methylaluminoxane Grand catalyst system.

[Claim 10]

The method of claim 8,

The co-catalyst is an olefinic oligomerization reaction catalyst system, which is supported at 5 to 15 mmol / g with respect to 1 g of the support. [Claim 111]

A process for the oligomerization of an olefin comprising the step of subjecting the oligomerization reaction of an olefinic monomer in the presence of a catalyst system according to any one of claims 1 to 10 to form an alpha-olefin.

[Claim 12]

The method of claim 11,

Lyomericization of Ethylene.

[Claim 13]

The method of claim 11,

The oligomerization reaction of the olefinic monomers is carried out at a temperature of 5 to 20C C, oligomerization method of ethylene.

[Claim 14]

The method of claim 11,

The oligomerization reaction of the olefinic monomers is carried out at a pressure of 1 to 300 bar, ethylene oligomerization method of ethylene.