WO2019168249A1

WO2019168249A1 - Ligand, oligomerization catalyst comprising same, and method for producing ethylene oligomer by using oligomerization catalyst

Info

Publication number: WO2019168249A1
Application number: PCT/KR2018/012025
Authority: WO
Inventors: 이호성; 조용남
Original assignee: 에스케이이노베이션 주식회사; 에스케이종합화학 주식회사
Priority date: 2018-02-27
Filing date: 2018-10-12
Publication date: 2019-09-06
Also published as: WO2019168249A8

Abstract

The present invention relates to a ligand, an ethylene oligomerization catalyst comprising same, and a method for selectively producing 1-hexene or 1-octene from ethylene by using the catalyst. The ligand according to the present invention is a bis (diphenylphosphino) ethane with a phosphorus atom substituted with a fluoro-substituted phenyl, and when the ligand is used for ethylene oligomerization, the high temperature activity of the catalyst can be increased.

Description

Ligand, oligomerization catalyst comprising the same and method for producing ethylene oligomer using same

The present invention is a ligand for preparing a highly active and highly selective ethylene oligomerization catalyst for use in oligomerization reactions such as trimerization or tetramerization of ethylene, oligomerization catalyst comprising the same and 1-hexene or 1 using the same It relates to a production method of octene.

Oligomers, in particular 1-hexene and 1-octene, are important commercial raw materials widely used in the polymerization process as monomers or comonomers for the production of linear low density polyethylene, obtained by purifying products produced by oligomerization of ethylene. . However, the existing ethylene oligomerization reaction has been an inefficient aspect of producing a considerable amount of butenes, higher oligomers and polyethylene together with 1-hexene and 1-octene. This conventional oligomerization technique of ethylene generally produces a variety of α-olefins depending on the Schulze-Flory or Poisson product distribution, thus limiting the yield of the desired product.

Recently, research has been conducted on the production of 1-hexene by selectively trimerization of ethylene through transition metal catalysis or selectively tetramerization to produce 1-octene. Most known transition metal catalysts are chromium. System catalyst.

WO 02/04119 discloses a chromium-based catalyst using a ligand of the general formula (R ¹ ) (R ² ) XYX (R ³ ) (R ⁴ ) as an ethylene trimerization catalyst, wherein X is phosphorus, arsenic, or antimony, Y is a linking group such as -N (R ⁵ )-, and at least one of R ¹ , R ² , R ³ and R ⁴ has a polar or electron-donating substituent.

In another known document, the ortho position of a phenyl ring bonded to phosphorus, such as (o-methoxyphenyl) ₂ PN (Me) P (o-methoxyphenyl) ₂ , as a ligand exhibiting catalytic activity for 1-hexene under catalytic conditions It is known for PNP ligands to which methoxy, which is a polar substituent, is bound (Antea Carter et al., Chem. Commun., 2002, p. 858-859).

In addition, Korean Patent Publication No. 2006-0002741 uses a PNP ligand containing a nonpolar substituent on the ortho position of a phenyl ring attached to phosphorus such as (o-ethylphenyl) ₂ PN (Me) P (o-ethylphenyl) _2. It is known that excellent ethylene trimerization activity and selectivity are indeed possible.

On the other hand, WO 04/056479 discloses that the selectivity is improved by tetramerization of ethylene by a chromium-based catalyst containing a PNP ligand in which a phenyl ring attached to phosphorus is omitted. It is known, and (phenyl) ₂ PN (isopropyl) P (phenyl) ₂ and the like are disclosed as examples of the hetero atom ligands used in the tetramerization catalyst for these ethylene tetramerization.

This prior art has a selectivity of greater than 70% by mass of chromium-based catalysts containing heteroatom ligands having nitrogen and phosphorus as heteroatoms, tetramers of ethylene without polar substituents to hydrocarbyl or heterohydrocarbyl groups bonded to the phosphorus atom. It was disclosed that 1-octene can be produced.

However, the prior art is specifically related to the structure of a ligand containing a hetero atom in which form can be highly selectively tetramerized ethylene to produce 1-octene or ethylene trimerized to produce 1-hexene. Not only did we give a clear example, but PNPs such as (R ¹ ) (R ² ) P- (R ⁵ ) NP (R ³ ) (R ⁴ ) as ligands with 1-octene selectivity of about 70% by mass. Only the structure of the type skeleton is given, and the types of substituents that can be substituted in the heteroatom ligands are also limited.

On the other hand, in the catalyst system for tetramerization of ethylene, the catalytic activity is deteriorated at high reaction temperatures, and significant polymer by-products are formed, resulting in low selectivity and serious problems in the polymerization process.

Specifically, at high temperatures, the tetramerization catalyst system is inevitably interrupted due to a decrease in catalytic activity resulting in a decrease in the production and selectivity of olefins, especially 1-octene, and the formation of by-products resulting in clogging and fouling. This causes serious problems in the olefin polymerization process.

Therefore, there is an urgent need to develop an oligomerization catalyst having a structure capable of producing 1-hexene or 1-octene by oligomerizing high activity and high selectivity without degrading the olefin oligomerization catalytic activity at high temperature.

It is an object of the present invention to maintain a high activity in the oligomerization reaction such as trimerization or tetramerization of ethylene at high temperature, a novel ligand capable of producing high activity and high selective oligomer, ethylene oligomerization catalyst comprising the same and using the same It is to provide a method for producing an ethylene oligomer.

The present invention provides a novel ligand capable of oligomerizing ethylene at high temperatures and at high temperatures for use in oligomerization of olefins, specifically trimerization or tetramerization of ethylene. It is represented by Formula (1).

[Formula 1]

In Chemical Formula 1,

R ₁ is hydrocarbyl;

R ₂ and R ₃ are each independently hydrocarbyl;

p and q are each independently integers of 0 to 5;

m and n are each independently integers of 0 to 5, where 1 ≦ m + n ≦ 10.

In one embodiment of the present invention, the ligand may be represented by the following formula (2).

[Formula 2]

In Formula 2, R ₁ , m and n are the same as defined in Formula 1.

In one embodiment of the present invention, the ligand may be represented by the following formula (3), (4) or (5).

[Formula 3]

[Formula 4]

[Formula 5]

In Formulas 3 to 5, R ₁ , R ₂ , R ₃ , p, and q are the same as defined in Formula 1 above.

More preferably, in Chemical Formulas 3 to 5, R ₁ may be C1-C7 alkyl or C6-C12 aryl.

The present invention also provides an ethylene oligomerization catalyst comprising the ligand of Formula 1 and a transition metal.

In the oligomerization catalyst according to an embodiment of the present invention, the oligomerization catalyst may be mononuclear or dinuclear.

In the oligomerization catalyst according to an embodiment of the present invention, the transition metal is not particularly limited, but may be a Group 4, Group 5 or Group 6 transition metal.

In the oligomerization catalyst according to an embodiment of the present invention, the transition metal may be chromium, molybdenum, tungsten, titanium, tantalum, vanadium or zirconium.

In the oligomerization catalyst according to an embodiment of the present invention, the transition metal may be chromium.

In another aspect, the present invention provides a method for producing an ethylene oligomer using a catalyst composition comprising the ethylene oligomerization catalyst, it is possible to prepare an ethylene oligomer by contacting the ethylene oligomerization catalyst composition with ethylene.

In the method for preparing an ethylene oligomer according to an embodiment of the present invention, the catalyst composition may further include a promoter.

In the method for preparing an ethylene oligomer according to an embodiment of the present invention, the promoter may be an organoaluminum compound, an organic boron compound, an organic salt, or a mixture thereof, but is not limited thereto.

In the method for preparing an ethylene oligomer according to an embodiment of the present invention, the organoaluminum compound is an aluminoxane compound, AlR ₃ (wherein R is independently C 1 -C 12 alkyl, C 6 -C 20 aryl, C 2 -C 10 al Kenyl, C 2 -C 10 alkynyl, C 1 -C 12 alkoxy or halogen) or LiAlH ₄ , and the like, and the promoter may specifically be methylaluminoxane (MAO), modified methylaluminoxane (mMAO), Ethylaluminoxane (EAO), tetraisobutylaluminoxane (TIBAO), isobutylaluminoxane (IBAO), trimethylaluminum (TMA), triethylaluminum (TEA), triisobutylaluminum (TIBA), tri-n-octyl It may be aluminum, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum chloride, diethylaluminum chloride, aluminum isopropoxide, ethylaluminum sesquichloride or methylaluminum sesquichloride But, it is not limited.

In the method for preparing the ethylene oligomer according to an embodiment of the present invention, the ethylene oligomer may be 1-hexene, 1-octene or a mixture thereof.

In the method for producing the ethylene oligomer according to an embodiment of the present invention, an aliphatic hydrocarbon may be used as a reaction solvent.

In the method for preparing the ethylene oligomer according to an embodiment of the present invention, the aliphatic hydrocarbon is hexane, heptane, octane, nonene, decane, undecane, dodecane, tetradecane, 2,2-dimethylpentane, 2,3 -Dimethylpentane, 2,4-dimethylpentane, 3,3-dimethylpentane, 2,2,4-trimethylpentane, 2,3,4-trimethylpentane, 2-methylhexane, 3-methylhexane, 2,2- Dimethylhexane, 2,4-dimethylhexane, 2,5-dimethylhexane, 3,4-dimethylhexane, 2-methylheptane, 4-methylheptane, cyclohexane, methylcyclohexane, ethylcyclohexane, isopropylcyclohexane, It may be one or more selected from 1,4-dimethylcyclohexane and 1,2,4-trimethylcyclohexane, but is not limited thereto.

In the oligomerization catalyst according to the present invention, at least one fluorine is substituted for phenyl bonded to a phosphorus atom in bis (diphenylphosphino) ethene, and one carbon atom is substituted with a substituted or unsubstituted hydrocarbyl group other than hydrogen. It contains the ligand of the formula (1) of the asymmetric form is excellent in catalytic activity and selectivity even at high temperature during ethylene oligomerization.

In particular, when the fluorine is bonded to the ortho-position of phenyl in the ligand of Formula 1, it has excellent catalytic activity and selectivity at high temperature during ethylene oligomerization.

In addition, the oligomerization catalyst of the present invention is excellent in catalytic activity even at high temperatures, and does not require fouling and clogging caused by polymers, which are by-products during mass production of oligomers.

In addition, the oligomer manufacturing method of the present invention can produce the oligomer with high activity and high selectivity even at high temperature, and does not occur fouling and clogging, thereby making it possible to prepare the olefin in a very efficient process.

As used herein, "hydrocarbyl" or "heterohydrocarbyl" refers to a radical having one bonding position derived from a hydrocarbon or heterohydrocarbon, and "hetero" means that the carbon is selected from O, S and N atoms. It means substituted by one or more atoms.

As used herein, “substituted” refers to a group or moiety having one or more substituents attached to the structural backbone of the group or moiety. Non-limiting mentioned groups or structural skeletons include deuterium, hydroxy, halogen, carboxyl, cyano, nitro, oxo (= 0), thio (= S), alkyl, haloalkoxy, alkenyl, alkynyl, aryl, Aryloxy, alkoxycarbonyl, alkylcarbonyloxy, alkenylcarbonyloxy, alkynylcarbonyloxy, aminocarbonyl, alkylcarbonylamino, alkenylcarbonylamino, alkynylcarbonylamino, thioalkyl, thioal Kenyl, thioalkynyl, alkylsilyl, akenylsilyl, alkynylsilyl, arylsilyl, arylalkyl, arylalkenyl, arylalkynyl, cycloalkyl, cycloalkylalkyl, cycloalkenyl, amino, alkylamino, dialkylamino It means substituted by any one or more selected from heteroaryl, heterocyclylalkyl ring, heteroarylalkyl and heterocycloalkyl.

The "substituted" specifically refers to deuterium, hydroxy, halogen, carboxyl, cyano, nitro, oxo (= 0), thio (= S), C1-C10 alkyl, haloC1-C10 alkoxy, C2-C10 al. Kenyl, C2-C10 alkynyl, C6-C20 aryl, C6-C20 aryloxy, C1-C10 alkoxycarbonyl, C1-C10 alkylcarbonyloxy, C2-C10 alkenylcarbonyloxy, C2-C10 alkynylcarbonyl Oxy, aminocarbonyl, C1-C10 alkylcarbonylamino, C2-C10 alkenylcarbonylamino, C2-C10 alkynylcarbonylamino, thioC1-C10 alkyl, thioC2-C10 alkenyl, thioC2-C10 alky Nyl, C1-C10 Alkylsilyl, C2-C10 Alkenylsilyl, C2-C10 Alkynylsilyl, C6-C20 Arylsilyl, C6-C20 Aryl C1-C10 Alkyl, C6-C20 Aryl C2-C10 Alkenyl, C6-C20 Aryl C2-C10 alkynyl, C3-C10 cycloalkyl, C3-C10 cycloalkyl C1-C10 alkyl, C2-C10 cycloalkenyl, amino, C1-C10 alkylamino, diC1-C10 alkylamino, C6-C20 heteroaryl , C3-C20 heterocycloalkyl ring, C3-C10 heteroarylC1-C10 alkyl and C3-C10 heterocycloalkyl It means to be substituted with any one or more of the selected.

"Alkyl" as used herein is a monovalent straight or pulverized saturated hydrocarbon radical consisting solely of carbon and hydrogen atoms and is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, octyl, nonyl and the like. It includes, but is not limited to. In addition, the alkyl radicals described in this invention have 1 to 10 carbon atoms, preferably 1 to 7, more preferably 1 to 5 carbon atoms.

In addition, "aryl" described herein is a monovalent organic radical derived from an aromatic hydrocarbon by one hydrogen removal, each ring containing, for example, 4 to 7, preferably 5 or 6 ring atoms It includes a single or fused ring system, and includes a form in which a plurality of aryls are connected by a single bond. Specific examples include, but are not limited to, phenyl, naphthyl, biphenyl, anthryl, indenyl, fluorenyl, and the like. The aryl radicals described herein also have 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms.

In the present specification, "ethylene oligomerization" refers to small polymerization of ethylene and is called trimerization and tetramerization depending on the number of ethylene polymerized. In particular, it is meant herein to prepare 1-hexene, 1-octene or mixtures thereof which are the main comonomers of linear low density polyethylene (LLDPE) from ethylene.

As used herein, "oligomerization catalyst" is defined to include both the form of the ligand and the transition metal complex and the form of the ligand and the transition metal composition.

As used herein, "oligomerization catalyst composition" is defined as further comprising a cocatalyst or an additive in the above "oligomerization catalyst".

The present invention provides a ligand for preparing an oligomerization catalyst that maintains high activity even at a high temperature unlike a conventional catalyst, the ligand of the present invention is represented by the following formula (1).

[Formula 1]

In Chemical Formula 1,

R ₁ is substituted or unsubstituted hydrocarbyl;

R ₂ and R ₃ are each independently hydrocarbyl;

p and q are each independently integers of 0 to 5;

m and n are each independently integers of 0 to 5, where 1 ≦ m + n ≦ 10.

Unlike the prior art literatures, the ligand of the present invention is substituted with at least one fluorine in phenyl bonded to a phosphorus atom in bis (diphenylphosphino) ethene, and substituted in one carbon atom other than hydrogen or Asymmetrically substituted ligand of Formula 1 in which an unsubstituted hydrocarbyl group is substituted. Due to the ligand of Formula 1 including at least one fluorine-substituted phenyl, it has excellent catalytic activity and selectivity even at high temperature during ethylene oligomerization. Has an advantage.

In one embodiment of the present invention, preferably, the ligand may be represented by the following formula (2).

[Formula 2]

In Formula 2, R ₁ , m and n are the same as defined in Formula 1.

In one embodiment of the present invention, preferably the ligand may be represented by the following formula (3), (4) or (5).

[Formula 3]

[Formula 4]

[Formula 5]

More preferably, in one embodiment of the present invention, in Formula 1 or 2 m and n are each independently an integer of 0 to 1, may be 1≤m + n≤2, fluorine is substituted in the ortho-position Can be.

Specifically, in Formula 1 or 2, m may be 0 and n may be 1.

Specifically, in Formula 1 or 2, m may be 1 and n may be 0.

Specifically, in Formula 1 or 2, m may be 1 and n may be 1.

In one embodiment of the present invention, R ₂ and R ₃ may be each independently C1-C10 alkyl, C6-C20 aryl, C6-C20 arylC1-C10 alkyl or C1-C10 alkylC6-C20 aryl, p and q may each independently be an integer of 0 to 2.

More preferably, in one embodiment of the present invention, p and q may be each independently an integer of zero.

Preferably in one embodiment of the present invention, R ₁ may be C1-C10 alkyl, C6-C20 aryl, C6-C20 arylC1-C10 alkyl or C1-C10 alkylC6-C20 aryl, more preferably R ₁ may be C ₁ -C 7 alkyl or C 6 -C 12 aryl.

The ligand according to an embodiment of the present invention may be exemplified by the following structure, but is not limited thereto.

The transition metal is not particularly limited, but may be a Group 4, 5 or 6 transition metal, preferably selected from chromium, molybdenum, tungsten, titanium, tantalum, vanadium or zirconium, more preferably chromium to be.

The transition metal may be derived from a transition metal precursor.

The transition metal precursor is specifically a Group 4, Group 5 or Group 6 transition metal precursor, preferably may be selected from chromium, molybdenum, tungsten, titanium, tantalum, vanadium or zirconium precursors. More preferred.

The chromium precursor is not particularly limited, but is preferably selected from the group consisting of chromium (III) acetylacetonate, chromium trichloride tristetrahytrofuran and chromium (III) 2-ethylhexanoate.

The oligomerization catalyst according to the present invention may be a mononuclear or heteronuclear oligomerization catalyst in which a heteroatom ligand of Formula 1 is coordinated to a transition metal or transition metal precursor, and specifically ML ¹ (L) _a (X) _b or M It may be represented by ₂ X ¹ ₂ L ¹ ₂ (L) _y (X) _z , wherein M is a transition metal, L ¹ is a ligand of Formula 1, X and X ¹ are each independently from a transition metal precursor The functional group to be derived is, for example, halogen, L is an organic ligand, a is an integer of 0 or more, b is an integer of (oxidation number of a-M), y is an integer of 0 or more, and z is (2 x M May be an integer of) -2-y.

Even more preferably, the oligomerization catalyst according to the present invention coordinates a ligand having p and q 0 in chromium or chromium precursor in Chemical Formula 3, Chemical Formula 4 or Chemical Formula 5 so as to stably maintain the oligomerization activity, It is possible to prepare 1-hexene and 1-octene in high activity, high selectivity.

The oligomerization catalyst according to the present invention may be specifically exemplified by the following structure, but is not limited thereto.

(In the above structure, R ₁ is C1-C7 alkyl or C6-C12 aryl, X is halogen, L is organic ligand, a is an integer from 0 to 3, c and d are each independently 0 to 2 Is an integer.)

Specifically, the organic ligand L according to an embodiment of the present invention may be selected from the following structural formula, but is not limited thereto.

Wherein R ⁴¹ and R ⁴² are each independently hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, and R ⁴³ is hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or Substituted heterohydrocarbyl;

R ⁴⁴ and R ⁴⁵ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl.

Ligands constituting the oligomerization catalyst according to the present invention can be prepared using various methods known to those skilled in the art.

The oligomerization catalyst according to an embodiment of the present invention has excellent catalytic activity, very high selectivity upon oligomerization of olefins, control of catalyst input amount, and excellent activity is maintained even at high temperature, thus preventing clogging of the olefin manufacturing process and No fouling occurs, very economical and efficient.

In addition, the present invention provides a method for producing a high activity and highly selective 1-hexene or 1-octene from ethylene using a catalyst composition comprising the oligomerization catalyst, the ethylene oligomerization catalyst composition Contact may be made to the ethylene oligomer.

The ethylene oligomerization catalyst composition according to one embodiment of the present invention may further include a promoter for more effective activity and high selectivity.

The ethylene oligomerization catalyst composition may be an oligomerization catalyst system including an oligomerization catalyst and a promoter comprising a transition metal or a transition metal precursor and a ligand of Formula 1.

The cocatalyst may in principle be any compound that activates the transition metal complex to which the ligand of Formula 1 is coordinated. Cocatalysts can also be used in mixtures. Suitable compounds as cocatalysts include organoaluminum compounds, organic aluminoxanes, organoboron compounds, organic salts and the like.

Organoaluminum compounds suitable for use as activators in the ethylene oligomerization catalyst composition according to one embodiment of the present invention are AlR ₃ (wherein R is independently C 1 -C 12 alkyl, C 6 -C 20 aryl, C 2 -C 10 alkenyl , C 2 -C 10 alkynyl, C 1 -C 12 alkoxy or halogen) or LiAlH ₄ or the like.

The organoaluminum compound is trimethylaluminum (TMA), triethylaluminum (TEA), triisobutylaluminum (TIBA), tri-n-octylaluminum, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum chloride, diethylaluminum One, two or more mixtures selected from chloride, aluminum isopropoxide, ethylaluminum sesquichloride, methylaluminum sesquichloride, and aluminoxanes.

Organic aluminoxanes suitable for use as activators in the ethylene oligomerization catalyst composition according to one embodiment of the present invention are oligomeric compounds which can be prepared by adding water to water and alkylaluminum compounds, for example trimethylaluminum. The aluminoxane oligomeric compounds can be linear, cyclic, cages or mixtures thereof.

The organic aluminoxanes are alkylaluminoxanes such as methylaluminoxane (MAO), ethylaluminoxane (EAO), tetraisobutylaluminoxane (TIBAO) and isobutyl aluminoxane (IBAO) as well as modified alkyl aluminoxanes, such as For example, it may be selected from modified methylaluminoxane (MMAO). Modified methyl aluminoxanes (manufactured by Akzo Nobel) contain, in addition to methyl groups, mixed alkyl groups such as isobutyl or n-octyl groups. Specific examples include one or more mixtures selected from methyl aluminoxane (MAO), modified methyl aluminoxane (MMAO), ethyl aluminoxane (EAO) and tetraisobutyl aluminoxane (TIBAO), isobutyl aluminoxane (IBAO). Can be.

Organic boron compounds suitable for use as activators in the ethylene oligomerization catalyst composition according to one embodiment of the present invention are boroxine, NaBH ₄ , triethyl borane, triphenylborane, triphenylborane ammonia complex, tributylborate, triiso Propylborate, tris (pentafluorophenyl) borane, trityl (tetrapentafluorophenyl) borate, dimethylphenylammonium (tetrapentafluorophenyl) borate, diethylphenylammonium (tetrapentafluorophenyl) borate, methyldi Phenylammonium (tetrapentafluorophenyl) borate, ethyldiphenylammonium (tetrapentafluorophenyl) borate, or mixtures thereof, and the organoboron compounds thereof may be used in a mixture with the organoaluminum compounds.

Preferably the promoter is methylaluminoxane (MAO), modified methylaluminoxane (mMAO), ethylaluminoxane (EAO), tetraisobutylaluminoxane (TIBAO), isobutyl aluminoxane (IBAO), trimethylaluminum (TMA) , Triethylaluminum (TEA), triisobutylaluminum (TIBA), tri-n-octylaluminum, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum chloride, diethylaluminum chloride, aluminum isopropoxide, ethylaluminum It may be one or two or more mixtures selected from the group consisting of sesquichloride and methylaluminum sesquichloride, preferably methylaluminoxane (MAO) or modified methylaluminoxane (mMAO).

In one embodiment of the present invention, the ratio of the oligomerization catalyst and the promoter is 1: 1 to 10,000: 1 based on the molar ratio of metal to transition metal of the promoter, and more preferably 1: 1 to 2,000: 1. Preferably, the ratio of the oligomerization catalyst and the aluminoxane cocatalyst may be 1: 1 to 10,000: 1 based on the molar ratio of aluminum to transition metal, and more preferably 1: 1 to 1,000: 1. .

The ethylene oligomerization catalyst composition may further comprise other components possible as long as the ethylene oligomerization catalyst and promoter are not detrimental to the nature of the present invention.

The individual components of the ethylene oligomerization catalyst composition, the oligomerization catalyst and the promoter, can be combined simultaneously or sequentially in any order in the presence of a solvent to provide the active catalyst. The mixing of each component of the catalyst composition can be carried out at a temperature of -20 to 250 ° C., and the presence of the olefins during the mixing of each component can generally exhibit a protective effect to provide improved catalyst performance. The range of more preferable temperature is 20-160 degreeC.

The reaction products disclosed herein, in other words ethylene oligomers, in particular 1-hexene or 1-octene, are homogeneous in the presence of an inert solvent using conventional apparatus and contacting techniques with the oligomerization catalyst or oligomerization catalyst composition according to the invention. Liquid phase reactions or two-phase liquid / liquid reactions or product olefins may be prepared in bulk phase or gas phase reactions serving as the main medium, but homogeneous liquid phase reactions are preferred in the presence of an inert solvent.

The oligomer preparation method according to one embodiment according to the present invention may be performed in an inert solvent. That is, any inert solvent which does not react with the oligomerization catalyst and the promoter of the present invention may be used, and the inert solvent may be an aliphatic hydrocarbon in terms of improving the catalytic activity. The oligomerization catalyst system according to the present invention not only easily adjusts the amount of catalyst in the continuous dosing of the catalyst solution but also shows excellent catalytic activity.

The aliphatic hydrocarbon is preferably a saturated aliphatic hydrocarbon, Linear saturated aliphatic hydrocarbons represented by C _n H _2n ₊₂ (wherein n is an integer from 1 to 15), alicyclic saturated aliphatic hydrocarbons represented by C _m H _2m (wherein m is an integer from 3 to 8), and The lower alkyl group having 1 to 3 carbon atoms may include a linear or cyclic saturated aliphatic hydrocarbon substituted with one or more carbon atoms. Specifically listed, hexane, heptane, octane, nonene, decane, undecane, dodecane, tetradecane, 2,2-dimethylpentane, 2,3-dimethylpentane, 2,4-dimethylpentane, 3,3- Dimethylpentane, 2,2,4-trimethylpentane, 2,3,4-trimethylpentane, 2-methylhexane, 3-methylhexane, 2,2-dimethylhexane, 2,4-dimethylhexane, 2,5-dimethyl Hexane, 3,4-dimethylhexane, 2-methylheptane, 4-methylheptane, cyclohexane, methylcyclohexane, ethylcyclohexane, isopropylcyclohexane, 1,4-dimethylcyclohexane and 1,2,4-trimethyl At least one selected from cyclohexane is not limited thereto. More preferably, methylcyclohexane, cyclohexane, hexane or heptane is used as the saturated aliphatic hydrocarbon.

The oligomerization reaction according to one embodiment of the present invention may be carried out at a temperature of -20 to 250 ℃, preferably at a temperature of 20 to 160 ℃, more preferably at a temperature of 60 to 160 ℃, the reaction pressure is atmospheric pressure It can be carried out at a pressure of from 100 bar, preferably at a pressure of 10 to 70 bar.

In the method for preparing an oligomer according to an embodiment of the present invention, the oligomer may be 1-hexene, 1-octene or a mixture thereof.

In the method for preparing an oligomer according to an embodiment of the present invention, 1-octene is preferably at least 60% by weight, preferably at least 70% by weight, and more preferably, based on the total weight of the C8 product formed from ethylene through the oligomerization reaction. Can be obtained in an amount of at least 80 wt%. Yield in this case means the weight percent of 1-octene formed relative to the total weight of the C8 product formed.

In the method for preparing an oligomer according to an embodiment of the present invention, 1-hexene is 50 wt% or more, preferably 70 wt% or more, more preferably 1 to hexene relative to the total weight of the C6 product formed from ethylene through the oligomerization reaction. Can be obtained in more than 90% by weight. Yield in this case means the weight percent of 1-hexene formed relative to the total weight of the C6 product formed.

In the method for preparing an oligomer according to an embodiment of the present invention, different amounts of 1-butene, 2-hexene, 1-decene, methylcyclopentane, methylene in addition to 1-hexene or 1-octene depending on the oligomerization catalyst and reaction conditions Cyclopentane, propylcyclopentane and many higher oligomers and polyethylenes can be provided.

The oligomer preparation method according to one embodiment of the present invention can be carried out in a plant comprising any type of reactor. Examples of such reactors include, but are not limited to, batch reactors, semi-batch reactors and continuous reactors. The plant may comprise a reactor, an inlet of an olefin reactor and an oligomerization catalyst composition therein, a combination of the oligomerization reaction product from the reactor and a line for effluent and at least one separator for separating the oligomerization reaction product, In this case, the catalyst composition may include an oligomerization catalyst and a promoter disclosed in the present invention, or may include a transition metal or a transition metal precursor, a ligand of Formula 1, and a promoter.

The oligomerization catalyst or oligomerization catalyst composition according to the invention can be used to maintain the activity of the catalyst even at high temperatures during ethylene oligomerization to produce 1-hexene, 1-octene or mixtures thereof in high activity and high selectivity.

The following examples specifically illustrate the effects of the present invention. However, the following examples are only for illustrating the present invention and are not intended to limit the scope of the present invention.

리간드의 제조Preparation of Ligands

Preparation Example A Preparation of Chloro (2-Fluorophenyl) phenylphosphine

N, N - Of diethylaminochloro (phenyl) phosphine Produce

N, N-diethylaminochloro (phenyl) phosphine was prepared with reference to known literature (M. Oliana et. Al., J. Org. Chem., 2006, p. 2472-2479).

Dichloro (phenyl) phosphine (8.949 g, 50 mmol) was diluted in n-hexane (400 mL) in a flask dried under a nitrogen atmosphere, and diethylamine (7.314 g, 100 mmol) was slowly added at room temperature. The mixture was allowed to react for at least 1 hour and then filtered through celite to remove the volatiles under reduced pressure to obtain the title compound as a colorless transparent liquid (10.2 g, 94.6%).

¹ H NMR (500 MHz, C ₆ D ₆ ) δ 7.74 (m, 2H, aromatics), 7.10 (m, 2H, aromatics), 7.03 (m, 1H, aromatics), 2.85 (m, 4H, -CH _2- ), 0.79 (m, 6H, -CH ₃ ).

N, N - Diethyl -1- (2- Fluorophenyl )-One- Of phenylphosphineamine Produce

In a flask dried under a nitrogen atmosphere, 1-broro-2-fluorobenzene (7.0 g, 40 mmol) was diluted in anhydrous THF (30 mL), the temperature was lowered to -78 ° C, and 1.6M n-butyllithium (25.0 mL, 40 mmol, Aldrich) was added slowly. After the mixture was reacted for at least 1 hour while maintaining a low temperature, N, N-diethylaminochloro (phenyl) phosphine (8.195 g, 38 mmol) obtained above was added slowly, followed by at least 2 hours. The reaction temperature of the mixture was raised to room temperature, the volatiles were removed under reduced pressure, diluted with a hexane: dichloromethane (1: 1 v / v) solution, and filtered through silica to obtain the title compound as a colorless transparent liquid (8.967 g, 85.7%). .

¹ H NMR (500 MHz, C ₆ D ₆ ) δ 7.45 (m, 2H, aromatics), 7.34 (m, 1H, aromatics), 7.14 (m, 3H, aromatics), 6.94 (m, 3H, aromatics), 3.00 (m, 4H, -CH ₂ N), 0.83 (t, 6H, -CH ₃ ); ¹³ C NMR (600 MHz, CDCl ₃ ) δ 164.3, 138.8, 132.6, 131.2, 130.3, 128.0, 123.9, 115.0, 44.6, 14.4; ¹⁹ F NMR (500 MHz, C ₆ D ₆ ) δ −103.7; ³¹ P NMR (500 MHz, C ₆ D ₆ ) δ 49.7.

Of chloro (2-fluorophenyl) phenylphosphine Produce

In a flask dried under a nitrogen atmosphere, N, N-diethyl-1- (2-fluorophenyl) -1-phenylphosphinamine (8.967 g, 32.6 mmol) obtained above was added to anhydrous diethyl ether (70 mL). After dilution 1 M hydrogen chloride / diethyl ether (68.4 mL) was added slowly. After the mixture was reacted for at least 1 hour, activated alumina was filtered to obtain the title compound as a colorless transparent liquid (7.377 g, 94.9%).

¹ H NMR (500 MHz, C ₆ D ₆ ) δ 7.51 (m, 3H, aromatics), 6.97 (m, 3H, aromatics), 6.80 (m, 1H, aromatics), 6.73 (m, 1H, aromatics), 6.58 (m, 1H, aromatics); ¹³ C NMR (600 MHz, CDCl ₃ ) δ 164.4, 137.3, 132.5-128.9, 124.6, 115.4; ¹⁹ F NMR (500 MHz, C ₆ D ₆ ) δ −104.8; ³¹ P NMR (500 MHz, C ₆ D ₆ ) δ 71.4.

Preparation Example B Preparation of (2-Fluorophenyl) (phenyl) phosphine

In a flask dried under a nitrogen atmosphere, chloro (2-fluorophenyl) phenylphosphine (2.3863 g, 10 mmol) obtained in Preparation Example A was diluted in n-hexane (20 mL), followed by trimethyltin hydride (4.0163 g). , 11 mmol) was added slowly. The mixture was reacted for 30 minutes, and then filtered through celite to remove the volatiles under reduced pressure to obtain the title compound as a liquid (2.0418 g, 100%).

¹ H NMR (500 MHz, C ₆ D ₆ ) δ 7.37 (m, 2H, aromatics), 7.11 (m, 1H, aromatics), 6.97 (m, 3H, aromatics), 6.80 (m, 1H, aromatics), 6.68 (m, 1H, aromatics), 5.51-5.07 (d, 1H, -P).

Preparation Example 1 Preparation of Ligand (1)

(3,3-dimethyl-1- Butinyl )(2- Fluorophenyl ) Of phenylphosphine Produce

In a flask dried under a nitrogen atmosphere, 3,3-dimethyl-1-butyne (0.2875 g, 3.5 mmol, Aldrich) was diluted in anhydrous THF (6 mL), the temperature was lowered to -78 ° C, and 1.6M n-butyl Lithium (1.75 mL, 2.8 mmol, Aldrich) was added slowly. After the mixture was reacted for at least 1 hour while maintaining a low temperature, chloro (2-fluorophenyl) phenylphosphine (0.5345 g, 2.24 mmol) obtained in Preparation Example A was added slowly, followed by reaction for 2 hours or more. The reaction temperature of the mixture was raised to room temperature, the volatiles were removed under reduced pressure, diluted with hexane solution, filtered through celite and dried to give the title compound as a yellow solid (0.6214 g, 97.6%).

¹ H NMR (500 MHz, CDCl ₃ ) δ 7.68 (m, 3H, aromatics), 7.27 (m, 4H, aromatics), 7.13 (m, 1H, aromatics), 6.96 (m, 1H, aromatics); ¹³ C NMR (600 MHz, CDCl ₃ ) δ 165.1, 135.6, 133.1, 132.4, 130.9, 128.4, 124.4, 119.5, 115.2, 72.3, 30.8, 28.8; ¹⁹ F NMR (500 MHz, CDCl ₃ ) δ −105.5; ³¹ P NMR (500 MHz, CDCl ₃ ) δ −47.0; FT-ICR MS: m / z [M + H] ⁺ calcd for C ₁₈ H ₁₉ FP ⁺ : 285.1208; found: 285.1206.

Ligand ( 1) of Produce

(3,3-dimethyl-l-butynyl) (2-fluorophenyl) phenylphosphine (0.1422 g, 0.5 mmol), copper iodide (0.0048 g, 5 mol%) prepared above in a flask dried in a nitrogen atmosphere. ) And cesium carbonate (0.0163 g, 10 mol%) in dilute dimethylformamide (1 mL), then slowly add diphenylphosphine (0.1117 g, 0.6 mmol), then warm the temperature to 90 ° C. for 3 hours. Reacted. The mixture was purified by silica column with a solution of n-hexane: ethyl acetate (9: 1 v / v) to give ligand (1) as a colorless transparent oil (0.2236 g, 95.1%).

¹ H NMR (500 MHz, CDCl ₃ ) δ 7.70 (m, 1H, aromatics), 7.65 (m, 1H, aromatics), 7.46 (m, 4H, aromatics), 7.29 (m, 4H, aromatics), 7.21 (m , 4H, aromatics), 7.21-6.99 (m, 4H, aromatics), 6.85 (m, 1H, aromatics), 1.28 (s, 9H, -CH ₃ ); ¹³ C NMR (600 MHz, CDCl ₃ ) δ 165.2, 163.1, 138.9, 135.8, 134.1, 133.0, 128.6, 126.2, 123.8, 119.6, 115.2; ³¹ P NMR (500 MHz, CDCl ₃ ) δ −11.0, −39.0; FT-ICR MS: m / z [M.] ⁺ calcd for C ₃₀ H ₂₉ FP ₂ : 470.1729; found: 470.1718.

Preparation Example 2 Preparation of Ligand (2)

(2- Fluorophenyl ) (3- methyl -One- Butine Preparation of (phenyl) phosphine

The reaction was carried out in the same manner as the preparation of the ligand (1), except that 3-methyl-1-butane was used instead of 3,3-dimethyl-1-butane as a starting material, to obtain the title compound (80.93%). .

¹ H NMR (500 MHz, CDCl ₃ ) δ 7.62 (m, 3H, aromatics), 7.28 (m, 4H, aromatics), 7.09 (m, 1H, aromatics), 6.93 (m, 1H, aromatics), 2.77 (q , 1H, -CH-), 1.26 (d, 2H, -CH ₃ ); ¹³ C NMR (600 MHz, CDCl ₃ ) δ 165.1, 135.4, 133.2, 131.1, 128.9, 124.3, 116.8, 115.2, 73.2, 22.7, 22.0; ¹⁹ F NMR (500 MHz, CDCl ₃ ) δ −105.5; ³¹ P NMR (500 MHz, CDCl ₃ ) δ −46.5; FT-ICR MS: m / z [M + H] ⁺ calcd for C ₁₇ H ₁₇ FP ⁺ : 271.1052; found: 271.1049.

Ligand ( 2) Produce

(2-Fluorophenyl) (3-methyl-1-butyne) (phenyl) phosphine obtained above instead of (3,3-dimethyl-1-butynyl) (2-fluorophenyl) phenylphosphine as starting material The reaction was carried out in the same manner as in the preparation of the ligand (1), except that the ligand (2) was obtained (90.54%).

¹ H NMR (500 MHz, CDCl ₃ ) δ 7.30 (m, 18H, aromatics), 7.05 (m, 1H, aromatics), 6.98 (m, 1H, = CH-), 2.50 (m, 1H, -CH-) , 0.88 (t, 6H, -CH ₃ ); ¹³ C NMR (600 MHz, CDCl ₃ ) δ 165.3, 162.2, 138.9, 136.3, 134.8, 133.6, 132.2, 130.7, 128.4, 127.8, 126.3, 124.1, 115.6, 33.5, 24.1; ¹⁹ F NMR (500 MHz, CDCl ₃ ) δ −102.6; ³¹ P NMR (500 MHz, CDCl ₃ ) δ −4.9, −35.3; FT-ICR MS: m / z [M.] ⁺ calcd for C ₂₉ H ₂₇ FP ₂ : 456.1572; found: 456.1567.

Preparation Example 3 Preparation of Ligand (3)

(3- methyl -One- Butinyl ) Diphenylphosphine Produce

In a flask dried under a nitrogen atmosphere, 3-methyl-1-butyne (3.406 g, 50 mmol) was diluted in anhydrous diethyl ether (40 mL), the temperature was lowered to -78 ° C, and 1.6M n-butyllithium ( 26.5 mL, 42.5 mmol, Aldrich) was added slowly. The mixture was reacted for at least 1 hour while maintaining a low temperature, and then chlorodiphenylphosphine (8.44 g, 38.2 mmol) was added slowly, followed by at least 2 hours. The reaction temperature of the mixture was raised to room temperature, the volatiles were removed under reduced pressure, diluted with hexane solution, filtered through Celite and dried to give the title compound as a colorless liquid (8.9 g, 92.23%).

¹ H NMR (500 MHz, CDCl ₃ ) δ 7.59 (m, 4H, aromatics), 7.30 (m, 6H, aromatics), 2.77 (m, 1H, -CH-), 1.26 (d, 6H, -CH ₃ ) ; ¹³ C NMR (600 MHz, CDCl ₃ ) δ 137.1, 132.3, 128.6, 115.6, 74.7, 22.7, 21.9; ³¹ P NMR (500 MHz, CDCl ₃ ) δ −33.8; FT-ICR MS: m / z [M + H] ⁺ calcd for C ₁₇ H ₁₈ P ⁺ : 253.1146; found: 253.1143.

Ligand ( 3) Produce

In a flask dried in a nitrogen atmosphere, (3-methyl-1-butynyl) diphenylphosphine (0.1261 g, 0.5 mmol) prepared above, cuprous iodide (0.0048 g, 5 mol%) and cesium carbonate (0.0163 g , 10 mol%) was diluted in dimethylformamide (1 mL), and then slowly added (2-fluorophenyl) (phenyl) phosphine (0.1225 g, 0.6 mmol) prepared in Preparation Example B. It heated up to ° C and reacted for 3 hours. The mixture was purified by silica column with a solution of n-hexane: ethyl acetate (9: 1 v / v) to give ligand (3) as a colorless transparent oil (0.2282 g, 100.0%).

¹ H NMR (500 MHz, CDCl ₃ ) δ 7.24 (m, 17H, aromatics), 7.05 (m, 2H, aromatics), 6.95 (s, 1H, = CH-), 2.45 (s, 1H, -CH-) , 0.99 (t, 3H, -CH ₃ ), 0.83 (t, 3H, -CH ₃ ); ¹³ C NMR (600 MHz, CDCl ₃ ) δ 165.3, 161.6, 139.5, 134.3, 133.4, 132.8, 130.5, 128.3, 124.0, 115.2, 33.8, 24.1, 23.6; ¹⁹ F NMR (500 MHz, CDCl ₃ ) δ −101.6; ³¹ P NMR (500 MHz, CDCl ₃ ) δ −16.4, −26.9; FT-ICR MS: m / z [M.] ⁺ calcd for C ₂₉ H ₂₇ FP ₂ : 456.1572; found: 456.1570.

Preparation Example 4 Preparation of Ligand (4)

Method for preparing Ligand (3) except for using (2-fluorophenyl) (3-methyl-1-butyne) (phenyl) phosphine instead of (3-methyl-1-butynyl) diphenylphosphine as starting material The reaction was carried out in the same manner as to obtain the ligand (4) (63.99%).

¹ H NMR (500 MHz, CDCl ₃ ) δ 7.30-6.99 (m, 15H, aromatics), 7.10 (m, 3H, aromatics), 6.99 (s, 1H, = CH-), 2.47 (s, 1H, -CH -), 1.02 (t, 3H, -CH ₃ ), 0.86 (t, 3H, -CH ₃ ); ¹³ C NMR (600 MHz, CDCl ₃ ) δ 165.3, 163.4, 161.5, 138.6, 134.8, 133.5, 132.2, 130.8, 128.5, 125.8, 115.3, 33.9, 24.1; ¹⁹ F NMR (500 MHz, CDCl ₃ ) δ −101.6, −102.6; ³¹ P NMR (500 MHz, CDCl ₃ ) δ −17.0, −36.0; FT-ICR MS: m / z [M.] ⁺ calcd for C ₂₉ H ₂₆ F ₂ P ₂ : 474.1478; found: 474.1471.

Preparation Example 5 Preparation of Ligand (5)

(2- Fluorophenyl )(One- Hexanyl Preparation of (phenyl) phosphine

The reaction was carried out in the same manner as the preparation of the ligand (1), except that 1-hexane was used instead of 3,3-dimethyl-1-butane as the starting material, to obtain the title compound (79.45%).

¹ H NMR (500 MHz, CDCl ₃ ) δ 7.69-7.62 (m, 3H, aromatics), 7.32 (m, 4H, aromatics), 7.15 (t, 1H, aromatics), 6.97 (m, 1H, aromatics), 2.43 (t, 2H, -CH _2- ), 1.62 (q, 2H, -CH _2- ), 1.45 (q, 2H, -CH _2- ), 0.93 (t, 3H, -CH ₃ ); ¹³ C NMR (600 MHz, CDCl ₃ ) δ 165.1, 135.4, 133.3, 132.5, 131.1, 129.0, 124.1, 115.1, 111.6, 74.1, 30.5, 21.9, 20.0, 13.5; ¹⁹ F NMR (500 MHz, CDCl ₃ ) δ −105.5; ³¹ P NMR (500 MHz, CDCl ₃ ) δ −45.7; FT-ICR MS: m / z [M + H] ⁺ calcd for C ₁₈ H ₁₉ FP ⁺ : 285.1208; found: 285.1206.

Ligand ( 5) Produce

Ligand (1) except that (2-fluorophenyl) (1-hexynyl) (phenyl) phosphine was used instead of (3,3-dimethyl-1-butynyl) (2-fluorophenyl) phenylphosphine as starting material The reaction was carried out in the same manner as in the preparation of, to obtain the ligand (5) (51.01%).

¹ H NMR (500 MHz, CDCl ₃ ) δ 7.29-7.18 (m, 16H, aromatics), 7.10 (s, 1H, = CH-), 7.02 (m, 1H, aromatics), 6.95 (m, 1H, aromatics) , 2.12 (t, 2H, -CH _2- ), 1.24 (m, 2H, -CH _2- ), 1.10 (m, 2H, -CH _2- ), 0.69 (t, 3H, -CH ₃ ); ¹³ C NMR (600 MHz, CDCl ₃ ) δ 163.5, 156.5, 138.5, 136.3, 134.6, 133.2, 132.1, 130.6, 128.5, 127.9, 125.9, 115.5, 36.5, 30.9, 22.3, 13.7; ¹⁹ F NMR (500 MHz, CDCl ₃ ) δ −102.5; ³¹ P NMR (500 MHz, CDCl ₃ ) δ -7.9, -35.1; FT-ICR MS: m / z [M.] ⁺ calcd for C ₃₀ H ₂₉ FP ₂ : 470.1729; found: 470.1729.

Production Example 6 Preparation of Ligand (6)

One- Of hexynyldiphenylphosphine Produce

The reaction was carried out in the same manner as the preparation of the ligand (3), except that 1-hexane was used instead of 3-methyl-1-butane as the starting material, to obtain the title compound (8.6 g, 84.42%).

¹ H NMR (500 MHz, CDCl ₃ ) δ 7.60 (t, 4H, aromatics), 7.30 (m, 6H, aromatics), 2.44 (t, 2H, -CH _2- ), 1.60 (q, 2H, -CH ₂ -), 1.46 (m, 2H, -CH _2- ), 0.90 (t, 3H, -CH ₃ ); ¹³ C NMR (600 MHz, CDCl ₃ ) δ 137.0, 132.2, 128.4, 110.4, 75.6, 30.5, 21.9, 20.0, 13.5; ³¹ P NMR (500 MHz, CDCl ₃ ) δ −33.0; FT-ICR MS: m / z [M + H] ⁺ calcd for C ₁₈ H ₂₀ P ⁺ : 267.1303; found: 267.1300.

Ligand ( 6) Produce

The reaction proceeded in the same manner as in the preparation of the ligand (3), except that 1-hexynyldiphenylphosphine prepared above was used instead of (3-methyl-1-butynyl) diphenylphosphine as a starting material. 6) was obtained (0.1469 g, 62.43%).

¹ H NMR (500 MHz, CDCl ₃ ) δ 7.25 (m, 16H, aromatics), 6.99 (m, 4H, aromatics, = CH-), 2.13 (m, 2H, -CH _2- ), 1.26 (m, 2H , -CH _2- ), 1.10 (m, 2H, -CH _2- ), 0.70 (t, 3H, -CH ₃ ); ¹³ C NMR (600 MHz, CDCl ₃ ) δ 165.2, 155.5, 140.1, 139.3, 134.9, 134.0, 133.3, 130.5, 128.2, 124.0, 115.3, 37.0, 30.9, 22.4, 13.7; ¹⁹ F NMR (500 MHz, CDCl ₃ ) δ −102.3; ³¹ P NMR (500 MHz, CDCl ₃ ) δ −19.2, −26.2; FT-ICR MS: m / z [M.] ⁺ calcd for C ₃₀ H ₂₉ FP ₂ : 470.1729; found: 470.1721.

Preparation Example 7 Preparation of Ligand (7)

(2- Fluorophenyl ) (Phenyl) ( Phenylethynyl Preparation of phosphine

The reaction was carried out in the same manner as the preparation of the ligand (1), except that ethynylbenzene was used instead of 3,3-dimethyl-1-butane as the starting material, to obtain the title compound (70.95%).

¹ H NMR (500 MHz, CDCl ₃ ) δ 7.72 (m, 3H, aromatics), 7.54 (m, 2H, aromatics), 7.36 (m, 7H, aromatics), 7.17 (m, 1H, aromatics), 7.00 (m , 1H, aromatics); ¹³ C NMR (600 MHz, CDCl ₃ ) δ 165.1, 134.6, 132.8, 131.8, 129.2, 128.2, 124.5, 122.5, 115.4, 108.6, 84.2; ¹⁹ F NMR (500 MHz, CDCl ₃ ) δ −105.1; ³¹ P NMR (500 MHz, CDCl ₃ ) δ −45.9; FT-ICR MS: m / z [M + H] ⁺ calcd for C ₂₀ H ₁₅ FP ⁺ : 305.0895; found: 305.0894.

Ligand ( 7) Produce

Ligand (1) except for using (2-fluorophenyl) (phenyl) (phenylethynyl) phosphine in place of (3,3-dimethyl-1-butynyl) (2-fluorophenyl) phenylphosphine as starting material The reaction was carried out in the same manner as in the preparation of, to obtain the ligand (7) (97.13%).

¹ H NMR (500 MHz, CDCl ₃ ) δ 7.40-6.90 (m, 25H, aromatics, ═CH—); ¹³ C NMR (600 MHz, CDCl ₃ ) δ 165.2, 155.7, 145.9, 142.3, 139.1, 135.8, 133.3, 128.3, 126.8, 115.6; ¹⁹ F NMR (500 MHz, CDCl ₃ ) δ −102.3; ³¹ P NMR (500 MHz, CDCl ₃ ) δ −4.9, −25.9; FT-ICR MS: m / z [M.] ⁺ calcd for C ₃₂ H ₂₅ FP ₂ : 490.1416; found: 490.1418.

Preparation Example 8 Preparation of Ligand (8)

Of diphenyl (phenylethynyl) phosphine Produce

The title compound was obtained in the same manner as in the preparation of the ligand (3), except that ethynylbenzene was used instead of 3-methyl-1-butyne as the starting material (7.865 g, 92.29%).

¹ H NMR (500 MHz, CDCl ₃ ) δ 7.68 (m, 4H, aromatics), 7.54 (m, 2H, aromatic), 7.35 (m, 9H, aromatics); ¹³ C NMR (600 MHz, CDCl ₃ ) δ 136.3, 132.6, 131.8, 128.9, 128.5, 122.7, 107.7, 85.8; ³¹ P NMR (500 MHz, CDCl ₃ ) δ −33.4; FT-ICR MS: m / z [M + H] ⁺ calcd for C ₂₀ H ₁₆ P ⁺ : 287.0990; found: 287.0987.

Ligand ( 8) Produce

The reaction was carried out in the same manner as in the preparation of the ligand (3), except that diphenyl (phenylethynyl) phosphine prepared above was used instead of (3-methyl-1-butynyl) diphenylphosphine as a starting material. , Ligand (8) was obtained (0.2113 g, 86.16%).

¹ H NMR (500 MHz, CDCl ₃ ) δ 7.40-6.79 (m, 25H, aromatics, ═CH—); ¹³ C NMR (600 MHz, CDCl ₃ ) δ 165.3, 154.8, 145.3, 142.1, 138.5, 133.4, 132.5, 128.3, 123.8, 114.9; ¹⁹ F NMR (500 MHz, CDCl ₃ ) δ −102.2; ³¹ P NMR (500 MHz, CDCl ₃ ) δ −25.9; FT-ICR MS: m / z [M.] ⁺ calcd for C ₃₂ H ₂₅ FP ₂ : 490.1416; found: 490.1415.

Preparation Example 9 Preparation of Ligand (9)

The reaction was carried out in the same manner as in the preparation of the ligand (3), except that (2-fluorophenyl) (phenyl) (phenylethynyl) phosphine was used instead of (3-methyl-1-butynyl) diphenylphosphine as a starting material. Proceeded to yield ligand (9) (0.244 g, 99.9%).

¹ H NMR (500 MHz, CDCl ₃ ) δ 7.42-6.77 (m, 24H, aromatics); ¹³ C NMR (600 MHz, CDCl ₃ ) δ 165.4, 154.9, 143.9, 142.1, 137.9, 133.5, 132.5, 130.5, 128.5, 127.9, 125.1, 124.2, 115.7, 124.2, 115.7, 114.8; ¹⁹ F NMR (500 MHz, CDCl ₃ ) δ −102.2; ³¹ P NMR (500 MHz, CDCl ₃ ) δ −16.8, −35.0; FT-ICR MS: m / z [M.] ⁺ calcd for C ₃₂ H ₂₄ F ₂ P ₂ : 508.1321; found: 508.1322.

촉매의 제조 및 에틸렌 Preparation of Catalysts and Ethylene 올리고머화Oligomerization 반응 reaction

Example 1

Tritetrahydrofuran chromium trichloride (CrCl ₃ (THF) ₃ ) (237 mg, 0.63 μmol) was dissolved in dichloromethane (2.0 mL), followed by ligand (1) (Preparation Example 1) (298 mg, 0.63 μmol). (1.0 mL) was added slowly. The reaction was stirred for an additional hour and then filtered using a 0.45 μm syringe filter. The filtered liquid was removed in vacuo to give a dried blue solid (390 mg, 97.9%), which was named oligomerization catalyst I.

Meanwhile, the 2.1 L autoclave reactor was washed with nitrogen and vacuum, 1.0 L of methylcyclohexane was added, and 1.0 mL (1.87 mmol) of mMAO-3A (7 wt% -Al) sold by Akzo Nobel was added, followed by 500 Stirred at a stirring speed of rpm. In a glove box, 1.9 mg (3 μmol) of the oligomerization catalyst I prepared above was added to 10 mL of methylcyclohexane in 20 mL of vial, and dispersed, and then charged into the autoclave reactor. The temperature in the autoclave reactor was raised to 100 ° C., and ethylene was charged to 30 bar to start the oligomerization reaction. The reactor was cooled with a cooling coil inside the reactor to maintain a constant temperature of 100 ° C. throughout the operation. After 60 minutes, the ethylene feed to the reactor was stopped, the stirring was stopped to stop the reaction, and after the excess ethylene was discharged in the reactor, the reactor was cooled to 10 ° C. or less. After the reaction was discharged into a discharge vessel containing 1.5 mL of 2-ethylhexanol, a small amount of the organic layer sample was passed through a micron syringe filter and analyzed by GC-FID. The remaining organic layer was filtered to separate the solid wax / polymer product. After drying these solid products overnight in an oven at 100 ° C., the obtained product was recorded. The product distribution of this example by GC analysis is summarized in Table 1 below.

Example 2

The catalyst II was prepared in the same manner as in Example 1 using the ligand (2) instead of the ligand (1), and then the oligomerization reaction was performed in the same manner as in Example 1. The product distribution of this example is summarized in Table 1 below.

Example 3

Using Ligand (3) instead of Ligand (1), Catalyst III was prepared in the same manner as in Example 1, and oligomerization was carried out in the same manner as in Example 1. The product distribution of this example is summarized in Table 1 below.

Example 4

Using the ligand (4) instead of the ligand (1) to prepare a catalyst IV in the same manner as in Example 1, the oligomerization reaction was carried out in the same manner as in Example 1. The product distribution of this example is summarized in Table 1 below.

Example 5

The catalyst V was prepared in the same manner as in Example 1 using the ligand (5) instead of the ligand (1), and then the oligomerization reaction was performed in the same manner as in Example 1. The product distribution of this example is summarized in Table 1 below.

Example 6

Using the ligand (6) instead of the ligand (1) to prepare a catalyst VI in the same manner as in Example 1, oligomerization reaction was carried out in the same manner as in Example 1. The product distribution of this example is summarized in Table 1 below.

Example 7

Instead of ligand (1), catalyst (VII) was prepared using ligand (7) in the same manner as in Example 1, and then oligomerization reaction was performed in the same manner as in Example 1. The product distribution of this example is summarized in Table 1 below.

Example 8

Instead of ligand (1), catalyst (VIII) was prepared using ligand (8) in the same manner as in Example 1, followed by oligomerization reaction in the same manner as in Example 1. The product distribution of this example is summarized in Table 1 below.

Example 9

Using Ligand (9) instead of Ligand (1), Catalyst IX was prepared in the same manner as in Example 1, followed by an oligomerization reaction in the same manner as in Example 1. The product distribution of this example is summarized in Table 1 below.

Comparative Example 1

The catalyst A was prepared in the same manner as in Example 1 using the ligand (A) having the following structure instead of the ligand (1), and then the oligomerization reaction was performed in the same manner as in Example 1. The product distribution of this comparative example is summarized in Table 1 below.

Comparative Example 2

The catalyst B was prepared in the same manner as in Example 1 using the ligand (B) having the following structure instead of the ligand (1), and then the oligomerization reaction was performed in the same manner as in Example 1. The product distribution of this comparative example is summarized in Table 1 below.

Comparative Example 3

The catalyst C was prepared in the same manner as in Example 1 using the ligand (C) having the following structure instead of the ligand (1), and then the oligomerization reaction was performed in the same manner as in Example 1. The product distribution of this comparative example is summarized in Table 1 below.

[Comparative Example 4]

The catalyst D was prepared in the same manner as in Example 1 using the ligand (D) having the following structure instead of the ligand (1), and then the oligomerization reaction was performed in the same manner as in Example 1. The product distribution of this comparative example is summarized in Table 1 below.

	전체 활성(kg/g-Cr/h)Total activity (kg / g-Cr / h)	생성물product
	전체 활성(kg/g-Cr/h)Total activity (kg / g-Cr / h)	C6(중량%)C6 (% by weight)	C6 중 1-헥센(중량%)1-hexene (wt%) in C6	C8(중량%)C8 (wt%)	C8 중 1-옥텐(중량%)1-octene in weight percent C8	C10-C14(중량%)C10-C14 (% by weight)	폴리머(중량%)Polymer (% by weight)
실시예1Example 1	16631663	80.380.3	98.098.0	15.915.9	93.293.2	3.73.7	0.10.1
실시예2Example 2	12781278	74.474.4	95.895.8	21.721.7	94.594.5	3.53.5	0.40.4
실시예3Example 3	32463246	75.475.4	97.697.6	19.419.4	97.397.3	4.74.7	0.50.5
실시예4Example 4	29142914	84.184.1	98.698.6	11.811.8	98.098.0	3.53.5	0.60.6
실시예5Example 5	11421142	71.571.5	95.695.6	21.921.9	97.297.2	4.54.5	2.12.1
실시예6Example 6	21402140	70.270.2	96.896.8	24.924.9	83.783.7	4.04.0	0.90.9
실시예7Example 7	10081008	72.272.2	94.994.9	23.323.3	93.693.6	3.83.8	0.70.7
실시예8Example 8	20682068	75.975.9	96.796.7	19.619.6	95.595.5	4.14.1	0.40.4
실시예9Example 9	18751875	82.282.2	98.398.3	11.411.4	94.594.5	4.24.2	2.22.2
비교예1Comparative Example 1	11561156	57.757.7	88.888.8	37.937.9	96.796.7	3.93.9	0.50.5
비교예2Comparative Example 2	523523	54.954.9	91.191.1	37.137.1	95.195.1	4.34.3	3.73.7
비교예3Comparative Example 3	386386	57.057.0	86.086.0	39.639.6	96.896.8	2.52.5	0.90.9
비교예4Comparative Example 4	335335	48.948.9	92.292.2	47.647.6	95.695.6	2.32.3	1.21.2

From the results of Table 1, in the oligomerization reaction of ethylene, the oligomerization catalyst of the present invention is substituted with fluorine at the ortho-position of phenyl bonded to phosphorus atom in bis (diphenylphosphino) ethene, and at one carbon atom. In addition to hydrogen, it contains a ligand of the asymmetric form substituted with a hydrocarbyl group, it can be seen that it has a very good activity at high temperatures in comparison with the comparative example.

In particular, the oligomerization catalyst of the present invention exhibited at least 3.04 times more catalytic activity at a higher temperature than the catalyst of Comparative Example 4 containing a PNP ligand bonded to a phosphorus atom of phenyl substituted with fluorine at the ortho-position.

The oligomerization catalyst of the present invention remains catalytically active even at high temperatures, there are few by-products and there is no clogging and fouling, and thus it is very economical because the operation of the polymerization process for removing them is not necessary.

Furthermore, the oligomerization catalyst of the present invention is very excellent in catalytic activity even at high temperature, and has the advantage of preparing oligomers even when using a small amount of catalyst and a small amount of promoter in the oligomerization process of the olefin, but also active at high temperatures. This does not decrease and excellent selectivity, it is possible to manufacture 1-hexene or 1-octene from ethylene with high selectivity.

Although described in detail with respect to embodiments of the present invention as described above, those of ordinary skill in the art, without departing from the spirit and scope of the invention as defined in the appended claims Various modifications may be made to the invention. Therefore, changes in the future embodiments of the present invention will not be able to escape the technology of the present invention.

Claims

Ligand represented by the following formula (1).

[Formula 1]

In Chemical Formula 1,

R 1 is substituted or unsubstituted hydrocarbyl;

R 2 and R 3 are each independently hydrocarbyl;

p and q are each independently integers of 0 to 5;

m and n are each independently integers of 0 to 5, where 1 ≦ m + n ≦ 10.
The method of claim 1,

Ligand represented by the following formula (2).

[Formula 2]

In Formula 2, R 1 , m and n are the same as defined in Formula 1 of claim 1.
The method of claim 1,

Ligands represented by the following formula (3), (4) or (5).

[Formula 3]

[Formula 4]

[Formula 5]

In Formulas 3 to 5, R 1 , R 2 , R 3 , p and q are the same as defined in Formula 1 of claim 1.
The method of claim 3,

R 1 is C 1 -C 7 alkyl or C 6 -C 12 aryl.
A ligand according to any one of claims 1 to 4; And

Transition metals;

Ethylene oligomerization catalyst comprising a.
The method of claim 5,

Ethylene oligomerization catalysts that are mononuclear or dinuclear.
The method of claim 5,

The transition metal is an ethylene oligomerization catalyst of a Group 4, Group 5 or Group 6 transition metal.
The method of claim 7, wherein

The transition metal is chromium, molybdenum, tungsten, titanium, tantalum, vanadium or zirconium.
The method of claim 8,

The transition metal is chromium ethylene oligomerization catalyst.
A method for preparing an ethylene oligomer comprising contacting ethylene with a catalyst composition comprising the ethylene oligomerization catalyst of claim 5.
The method of claim 10,

The catalyst composition is a method for producing an ethylene oligomer further comprises a promoter.
The method of claim 11,

The cocatalyst is an organic aluminum compound, an organic aluminoxane, an organic boron compound, an organic salt, or a mixture thereof.
The method of claim 12,

The promoter is methylaluminoxane (MAO), modified methylaluminoxane (mMAO), ethylaluminoxane (EAO), tetraisobutylaluminoxane (TIBAO), isobutyl aluminoxane (IBAO), trimethylaluminum (TMA), tri Ethylaluminum (TEA), triisobutylaluminum (TIBA), tri-n-octylaluminum, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum chloride, diethylaluminum chloride, aluminum isopropoxide, ethylaluminum sesqui A process for preparing an ethylene oligomer, which is one or two or more mixtures selected from the group consisting of chloride and methylaluminum sesquichloride.
The method of claim 13,

The ethylene oligomer is 1-hexene or 1-octene.
The method of claim 10,

Process for producing ethylene oligomer using aliphatic hydrocarbon as reaction solvent.
The method of claim 15,

The aliphatic hydrocarbons are hexane, heptane, octane, nonene, decane, undecane, dodecane, tetradecane, 2,2-dimethylpentane, 2,3-dimethylpentane, 2,4-dimethylpentane, 3,3-dimethylpentane , 2,2,4-trimethylpentane, 2,3,4-trimethylpentane, 2-methylhexane, 3-methylhexane, 2,2-dimethylhexane, 2,4-dimethylhexane, 2,5-dimethylhexane, 3,4-dimethylhexane, 2-methylheptane, 4-methylheptane, cyclohexane, methylcyclohexane, ethylcyclohexane, isopropylcyclohexane, 1,4-dimethylcyclohexane and 1,2,4-trimethylcyclohexane Method for producing an ethylene oligomer is at least one selected from.