KR102563683B1 - Process For preparing oligomer Using olefin - Google Patents

Abstract

The present invention comprises the steps of introducing a transition metal source, a heteroatom ligand, an organic ligand, or an oligomerization catalyst prepared therefrom into a reactor; Injecting an additive that is different from the following olefin or olefin mixture and is a hydrocarbon compound having at least one unsaturated bond; And introducing an olefin; provides a method for oligomerization of an olefin comprising a.

Description

Oligomerization method of olefin {Process For preparing oligomer Using olefin}

The present invention relates to a method for oligomerizing olefins, and more particularly, to a method for oligomerizing olefins using olefins, oligomerization catalysts, and specific additives.

Linear alpha-olefins are important materials used in comonomers, detergents, lubricants, plasticizers, etc., and are widely used commercially.

In particular, 1-hexene and 1-octene are very important commercial raw materials widely used in polymerization processes as monomers or comonomers for producing linear low-density polyethylene, and are obtained by purifying products produced by ethylene oligomerization.

However, conventional ethylene oligomerization reactions are inefficient in producing a significant amount of butene, higher oligomers and polyethylene together with 1-hexene and 1-octene. Since these conventional ethylene oligomerization technologies generally produce various α-olefins according to Schulze-Flory or Poisson product distribution, the yield of desired products is limited.

Recently, studies on producing 1-hexene by selectively trimerizing ethylene through transition metal catalysis or selectively tetramerizing 1-octene have been conducted. Most known transition metal catalysts are chromium is a catalyst.

International Patent Publication No. WO2002/04119 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, where 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 literature, (o-ethylphenyl) ₂ PN, a compound having no polar substituents on at least one of R ¹ , R ² , R ³ and R ⁴ , is a ligand that does not show catalytic activity for 1-hexene under catalytic conditions. The use of (Me)P(o-ethylphenyl) ₂ is disclosed (Antea Carter et al., Chem. Commun., 2002, p. 858 - 859).

Meanwhile, during oligomerization using an oligomerization catalyst and a cocatalyst, reaction dispersions such as polymers and waxes are usually generated, which causes problems during facility operation.

That is, polymer, a by-product, reduces facility operation time, and even stops operation due to clogging of pipes due to polymer. Considerable time and expense are required to remove it, so researches are being conducted to improve this.

International Patent Publication No. WO2011/048527 discloses an oligomerization method using a zinc compound, specifically diethyl zinc, as an additive during oligomerization as a way to solve this problem, and International Patent Publication No. WO2013/168103 Oligomerization processes using non-metallic oxygenating additives to reduce polymer formation are known.

However, there is still a need for research into a method for suppressing polymer formation during a satisfactory oligomerization reaction.

International Patent Publication No. WO 2002/04119 International Patent Publication No. WO 2011/048527 International Patent Publication No. WO 2013/168103

Antea Carter et al., Chem. Commun., 2002, p. 858 - 859

The present invention provides a method for oligomerizing olefins that drastically reduces the production of by-product polymers by adding specific additives during oligomerization of olefins.

The present invention provides an olefin oligomerization method capable of dramatically improving the olefin oligomerization process by reducing the production of polymers, particularly secondary polymers, which are unwanted by-products during olefin oligomerization. The oligomerization method,

Injecting a transition metal source and an organic ligand or an oligomerization catalyst prepared therefrom into a reactor;

Injecting an additive that is a hydrocarbon compound having one or more unsaturated bonds; and

Including the step of introducing olefin;

The additive according to an embodiment of the present invention may have a molecular weight of 35 to 330 and a boiling point of 50 °C to 350 °C.

Preferably, the additive according to an embodiment of the present invention may be a hydrocarbon compound having two or more double bonds.

Preferably, the hydrocarbon compound according to an embodiment of the present invention may be a cyclic compound or a compound having a double bond in the ring, and more preferably, the cyclic compound may be an alkyl-substituted compound.

Preferably, the additive according to one embodiment of the present invention is a substituted or unsubstituted cycloalkene, a substituted or unsubstituted cycloalkyne, a substituted or unsubstituted alkene, or a substituted or unsubstituted cycloalkene having the above molecular weight and boiling point. It may be a substituted alkyne.

Preferably, additives according to an embodiment of the present invention may be represented by Chemical Formulas 1 to 4 below.

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[In Formulas 1 to 4,

A is -C(R ⁹ )(R ¹⁰ )-,

Z is -C(R ¹⁷ )(R ¹⁸ )-;

is a double bond or a single bond,

R ¹ to R ³ , R ⁶ to R ¹⁰ , and R ¹¹ to R ¹⁸ are each independently hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl;

R ⁴ and R ⁵ are is not present when is a double bond, When is a single bond, each independently represents hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl;

n and m are independently of each other 0 to 5;

When n and m are 1, R ³ and R ⁹ and R ¹³ and R ¹⁷ may be linked by (C1-C3)alkylene with or without a fused ring to form an alicyclic ring, and R ²¹ to R ²⁶ and R ³¹ independently of each other are hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl;

R ³² is halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl.)

Preferably, Chemical Formula 1 according to an embodiment of the present invention may be represented by Chemical Formulas 11 to 13 below.

[Formula 11]

[Formula 12]

[Formula 13]

[In Chemical Formulas 11 and 13,

R ¹ to R ¹⁰ and R ^1a to R ^10a are each independently hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl;

is a double bond or a single bond,

s is an integer from 0 to 2.]

Preferably, additives according to an embodiment of the present invention may be represented by Chemical Formulas 21 to 24 below.

[Formula 21]

[Formula 22]

[Formula 23]

[Formula 24]

[In Chemical Formulas 21 to 24,

R ¹ , R ⁶ , R ^1a , R ^2a , R ^4a to R ^6a , R ¹² and R ¹⁶ are each independently hydrogen, halogen, (C1-C10)alkyl, (C2-C10)alkenyl, (C2-C10)alkynyl, (C1-C10)alkoxy, (C6- C20) Aryl, (C6-C20) Aryloxy , (C1-C10) Alkoxycarbonyl, (C1-C10) Alkylcarbonyloxy, (C2-C10) Alkenylcarbonyloxy, (C2-C10) Alkynylcarbo Nyloxy, (C3-C7) Cycloalkyl , (C3-C7) Heterocycloalkyl , (C1-C10) Alkylsilyl, (C6-C20) arylsilyl, (C2-C10) alkenylsilyl, (C2-C10) alkynylsilyl or (C3-C20) heteroaryl.]

Preferably, in Formulas 21 to 23, R ¹ , R ⁶ , R ^1a , R ^2a , R ^4a to R ^6a , R ¹² and R ¹⁶ may each independently be hydrogen, (C1-C10)alkyl or (C2-C10)alkenyl.

Preferably, the additive according to one embodiment of the present invention may be used in an amount of 1 to 1 x 10 ⁶ moles per mole of the transition metal of the oligomerization catalyst.

A transition metal source according to an embodiment of the present invention may be a transition metal inorganic salt, a transition metal organic salt, a transition metal coordination compound, or a complex of a transition metal and an organic metal.

The oligomerization catalyst according to an embodiment of the present invention is ML ¹ (L ² ) _p (X) _q or M ₂ X ¹ ₂ L ¹ ₂ (L ² ) _y (X) _z, (wherein M is a transition metal, L ¹ is a heteroligand, L ² is an organic ligand, X and X ¹ are each independently halogen, p is an integer greater than or equal to 0, q is an integer of (oxidation number of M - p), and y is 2 is an integer of the above, and z is an integer of (2 x oxidation number of M)-y-2).

Preferably, the heteroatom ligand according to an embodiment of the present invention may be (R) _n BCD (R) _m , wherein B and D are independently phosphorus, arsenic, antimony, oxygen, bismuth, sulfur, selenium and is any one selected from nitrogen, C is a linking group between B and D, R is the same or different and each independently selected from hydrocarbyl, heterohydrocarbyl, substituted hydrocarbyl and substituted heterohydrocarbyl groups, n and m may be determined by each valence and oxidation state of B or D, respectively.

In the method for preparing an olefin oligomerization method according to an embodiment of the present invention, a cocatalyst may be further included, and the cocatalyst may be an organic aluminum compound, an organic boron compound, or a mixture thereof.

Preferably, the olefin according to one embodiment of the method for preparing an oligomer from an olefin of the present invention is ethylene, and the oligomer may be 1-hexene, 1-octene or a mixture thereof.

The olefin oligomerization method of the present invention is a specific additive, specifically, a hydrocarbon compound having at least one unsaturated bond, which is different from the olefin or olefin mixture, during oligomerization of olefin, thereby reducing clogging of process equipment during the oligomerization process. It dramatically improves the oligomerization process by significantly suppressing the production of polymer, a by-product that reduces operating time.

In addition, the oligomerization method from olefins of the present invention suppresses the production of polymers, which are problematic in the process, by using specific additives, so that high yields of oligomers can be easily produced without an additional process of washing process equipment during the process. .

The present invention significantly reduces the formation of polymers, especially secondary polymers, which are by-products that cause problems such as reducing the operating time of process equipment due to clogging of process equipment and cleaning of process equipment during oligomerization of olefins. By providing a method for oligomerizing olefins using an additive, the method for oligomerizing olefins of the present invention comprises:

Injecting a transition metal source and a heteroatom ligand or an oligomerization catalyst prepared therefrom into a reactor;

Injecting an additive that is a hydrocarbon compound having an unsaturated bond, and

Including the step of introducing an olefin.

The oligomerization method of olefins of the present invention is different from the above olefins and includes as an additive a hydrocarbon compound having at least one unsaturated bond to suppress the production of by-products such as polymers and waxes generated during the oligomerization of olefins, resulting in an oligomerization process. has been dramatically improved.

That is, during the oligomerization of olefins, by-products such as non-liquid secondary polymers are usually accumulated in the process equipment, which reduces the operating time of the process equipment and even stops the operation of the process equipment to clean it. cause problems

Accordingly, the inventors of the present invention added one or more specific additives, which are different from the olefin and are hydrocarbon compounds having at least one unsaturated bond, to by-products such as secondary polymers generated during the olefin oligomerization process, thereby reducing the formation of by-products. The present invention was completed by finding that the problem during the process mentioned above was significantly improved by significantly reducing.

The secondary polymer produced during the olefin oligomerization process described in the present invention is a generic term for polymers that are not discharged during the process and remain in the process equipment, causing problems in process operation, unlike the primary polymer that floats in the process and is discharged during discharge.

Of course, the steps described in the present invention can be introduced into the reactor in any order, and preferably, the inside of the reactor is purged with a gas such as olefin, and then the first step and the second step are performed, followed by the third step.

The olefins described in this invention may be alone or in mixtures, and the additives in this invention should be different compounds from the olefins being oligomerized.

In addition, the additives described in the present invention must have at least one unsaturated bond, and these compounds may be used alone or in a mixture of two or more.

Preferably, the additive according to an embodiment of the present invention may be a hydrocarbon compound having two or more double bonds.

The hydrocarbon compound according to an embodiment of the present invention may preferably be a cyclic compound, and the cyclic compound may be an aliphatic cyclic compound such as cycloalkene or cycloalkyne.

The cyclic compound according to an embodiment of the present invention may be a compound having a double bond in the ring, and may be preferably substituted with alkyl.

Hydrocarbon compounds and cyclic compounds described in the present invention mean both substituted and unsubstituted compounds unless otherwise specified.

Preferably, the additive of the present invention is different from the olefin and olefin mixture, and is a hydrocarbon compound having at least one unsaturated bond, having a molecular weight of 35 to 330, a boiling point of 50 ° C to 350 ° C, and a carbon number of C3 to C50, preferably a carbon number of It may be a compound having a C3 to C30 molecular weight, a molecular weight of 50 to 200, a boiling point of 50 to 200°C, more preferably a C3 to C20 carbon number, a molecular weight of 80 to 150, and a boiling point of 60 to 190°C.

An additive according to an embodiment of the present invention is preferably a substituted or unsubstituted cycloalkene; A substituted or unsubstituted cycloalkyne; A substituted or unsubstituted alkene; or a substituted or unsubstituted alkyne;

More preferably, additives according to an embodiment of the present invention may be represented by Chemical Formulas 1 to 4 below.

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

(In Formulas 1 to 4,

A is -C(R ⁹ )(R ¹⁰ )-,

Z is -C(R ¹⁷ )(R ¹⁸ )-;

is a double bond or a single bond,

R ¹ to R ³ , R ⁶ to R ¹⁰ , and R ¹¹ to R ¹⁸ are each independently hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl;

R ⁴ and R ⁵ are is not present when is a double bond, When is a single bond, each independently represents hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl;

n and m are independently of each other 0 to 5;

When n and m are 1, R ³ and R ⁹ and R ¹³ and R ¹⁷ may be linked by (C1-C3)alkylene with or without a fused ring to form an alicyclic ring, and R ²¹ to R ²⁶ and R ³¹ independently of each other are hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl;

R ³² is halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl.)

Preferably, Chemical Formula 1 according to an embodiment of the present invention may be represented by Chemical Formulas 11 to 13 below.

[Formula 11]

[Formula 12]

[Formula 13]

[In Chemical Formulas 11 and 13,

R ¹ to R ¹⁰ and R ^1a to R ^10a are each independently hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl;

is a double bond or a single bond,

s is an integer from 0 to 2.]

Preferably, additives according to an embodiment of the present invention may be represented by Chemical Formulas 21 to 24 below.

[Formula 21]

[Formula 22]

[Formula 23]

[Formula 24]

[In Chemical Formulas 21 to 23,

R ¹ , R ⁶ , R ^1a , R ^2a , R ^4a to R ^6a , R ¹² and R ¹⁶ are each independently hydrogen, halogen, (C1-C10)alkyl, (C2-C10)alkenyl, (C2-C10)alkynyl, (C1-C10)alkoxy, (C6- C20) Aryl, (C6-C20) Aryloxy , (C1-C10) Alkoxycarbonyl, (C1-C10) Alkylcarbonyloxy, (C2-C10) Alkenylcarbonyloxy, (C2-C10) Alkynylcarbo Nyloxy, (C3-C7) Cycloalkyl , (C3-C7) Heterocycloalkyl , (C1-C10) Alkylsilyl, (C6-C20) arylsilyl, (C2-C10) alkenylsilyl, (C2-C10) alkynylsilyl or (C3-C20) heteroaryl.]

Preferably, in Formulas 21 to 23 according to an embodiment of the present invention, R ¹ , R ⁶ , R ^1a , R ^2a , R ^4a to R ^6a , R ¹² and R ¹⁶ may each independently be hydrogen, (C1-C10)alkyl or (C2-C10)alkenyl, and R ¹ , R ⁶ , R ^1a , R ^2a , R ^4a to R ^6a , R ¹² and R ¹⁶ may each independently be hydrogen, (C1-C7)alkyl or (C2-C7)alkenyl. Preferably, R ¹ to R ¹⁰ and R ¹¹ to R ¹⁸ in Formulas 1 and 2 according to an embodiment of the present invention are each independently hydrogen, (C1-C10)alkyl, (C2-C10)alkenyl, (C2 -C10)alkynyl, (C1-C10)alkoxy, (C6-C20)aryl, (C6-C20)aryloxy , (C1-C10)alkoxycarbonyl, (C1-C10)alkylcarbonyloxy, (C2- C10) alkenylcarbonyloxy, (C2-C10) alkynylcarbonyloxy, (C3-C7) cycloalkyl , (C3-C7) heterocycloalkyl , (C1-C10) alkylsilyl, (C6-C20) arylsilyl, (C2-C10) alkenylsilyl, (C2-C10) alkynylsilyl or (C3-C20) heteroaryl, preferably hydrogen, (C1-C10) alkyl, (C2-C10) alkenyl, (C2-C10) alkynyl, (C1-C10) alkoxy or (C6-C20) It may be aryl, more preferably hydrogen, (C1-C10)alkyl, (C2-C10)alkenyl or (C2-C10)alkynyl, and in terms of reaction effect, preferably hydrogen, (C1-C7)alkyl, (C2-C7)alkenyl or (C2-C7)alkynyl.

In Formula 3 according to an embodiment of the present invention, R ²¹ to R ²⁶ are each independently hydrogen, (C1-C10)alkyl, (C2-C10)alkenyl, (C2-C10)alkynyl, (C1-C10) ) May be alkoxy or (C6-C20) aryl, preferably hydrogen, (C1-C10) alkyl or (C2-C10) alkenyl, and may be hydrogen or (C1-C7) alkyl in terms of reaction effect .

In Formula 4 according to an embodiment of the present invention, R ³¹ are each independently hydrogen, halogen, (C1-C10)alkyl, (C2-C10)alkenyl, (C2-C10)alkynyl, (C1-C10) Alkoxy, (C6-C20)Aryl, (C6-C20)Aryloxy , (C1-C10)Alkoxycarbonyl, (C1-C10)Alkylcarbonyloxy, (C2-C10)alkenylcarbonyloxy, (C2- C10) Alkynylcarbonyloxy, (C3-C7) Cycloalkyl , (C3-C7) Heterocycloalkyl , (C1-C10) Alkylsilyl, (C6-C20) arylsilyl, (C2-C10) alkenylsilyl, (C2-C10) alkynylsilyl or (C3-C20)heteroaryl, R ³² is (C1-C10)alkyl, (C2-C10)alkenyl, (C2-C10)alkynyl, (C1-C10)alkoxy, (C6-C20)aryl, ( C6-C20) Aryloxy , (C1-C10) Alkoxycarbonyl, (C1-C10) Alkylcarbonyloxy, (C2-C10) Alkenylcarbonyloxy, (C2-C10) Alkynylcarbonyloxy, (C3 -C7) Cycloalkyl , (C3-C7) Heterocycloalkyl , (C1-C10) Alkylsilyl, (C6-C20) arylsilyl, (C2-C10) alkenylsilyl, (C2-C10) alkynylsilyl or It may be (C3-C20)heteroaryl, and preferably R ³¹ and R ³² may each independently be (C1-C10)alkyl.

The additive according to an embodiment of the present invention may be used in an amount of 1 to 1 x 10 ⁶ mol, preferably 1 to 1 x 10 ⁴ mol, based on 1 mol of the transition metal of the oligomerization catalyst.

As used herein, "hydrocarbyl" or "heterohydrocarbyl" means a radical having one bonding site derived from hydrocarbon or heterohydrocarbon, and "hydrocarbylene" means a radical having two bonding sites derived from hydrocarbon. It means a radical having, and the meaning of hetero means that carbon is substituted with one or more heteroatoms selected from O, S and N atoms.

"Substituted" as used herein refers to a group or moiety having one or more substituents attached to the structural backbone of the group or moiety, including but not limited to deuterium, hydroxy, halogen, carboxyl, Cyano, nitro, oxo (=0), thio (=S), alkyl, haloalkoxy, alkenyl, alkynyl, aryl, arylalkyl, cycloalkyl, cycloalkylalkyl, cycloalkenyl, amino, alkylamino, di It means that it is substituted with one or more substituents selected from alkylamino, heteroaryl, heterocyclylalkyl ring, heteroarylalkyl and heterocycloalkyl.

As used herein, "alkene" refers to a straight-chain, branched-chain, or cyclic hydrocarbon containing 2 to 10 carbon atoms and at least one carbon-to-carbon double bond, which falls within the range recognized by those skilled in the art.

As used herein, “alkyne” refers to a straight-chain, branched-chain, or cyclic hydrocarbon containing 2 to 10 carbon atoms and at least one carbon-to-carbon triple bond. of carbon atoms, preferably 2 to 7 carbon atoms.

"Cycloalkyl" as described in the present invention means a non-aromatic monocyclic or multicyclic ring system having 3 to 10 carbon atoms, and "heterocycloalkyl" as described in the present invention refers to carbon atoms and nitrogen, Cycloalkyl and heterocycloalkyl described herein as a substituted or unsubstituted non-aromatic 3 to 15 membered ring consisting of 1 to 5 heteroatoms selected from phosphorus, oxygen and sulfur are 3 to 10 membered rings, preferably 5 to 10 membered rings. It may be a 7-membered ring.

Substituents including "alkyl", "alkoxy" and other "alkyl" moieties described in the present invention include both straight-chain and branched forms, and contain 1 to 10 carbon atoms, preferably 1 to 7, more preferably 1 It has 5 to 5 carbon atoms.

In addition, "aryl" as described in the present invention is an organic radical derived from an aromatic hydrocarbon by the removal of one hydrogen, which is single or fused, preferably containing 4 to 7, preferably 5 or 6, ring atoms in each ring. It includes a ring system, and even includes a form in which a plurality of aryls are connected by single bonds. Specific examples include, but are not limited to, phenyl, naphthyl, biphenyl, anthryl, indenyl, fluorenyl, and the like.

"Heteroaryl" as described in the present invention includes 1 to 4 heteroatoms selected from B, N, O, S, P(=O), Si and P as aromatic ring skeletal atoms, and the remaining aromatic ring skeletal atoms are carbon It means a phosphorus aryl group, and is a 5- to 6-membered monocyclic heteroaryl, or a polycyclic heteroaryl condensed with one or more benzene rings, and may be partially saturated. In addition, the heteroaryl in the present invention includes a form in which one or more heteroaryls are connected by a single bond.

As used herein, the term "alkenyl", alone or as part of another group, means a straight-chain, branched-chain or cyclic hydrocarbon radical containing from 2 to 10 carbon atoms and at least one carbon-to-carbon double bond. A more preferred alkenyl radical is a lower alkenyl radical having from 2 to about 7 carbon atoms. Most preferred lower alkenyl radicals are those having from 2 to about 5 carbon atoms. Alkenyl groups may also be substituted at any available point of attachment. Examples of alkenyl radicals include ethenyl, propenyl, allyl, propenyl, butenyl and 4-methylbutenyl. The terms alkenyl and lower alkenyl include radicals having cis and trans orientations, or, alternatively, E and Z orientations.

As used herein, the term "alkynyl", alone or as part of another group, means a straight-chain, branched-chain or cyclic hydrocarbon radical containing from 2 to 10 carbon atoms and at least one carbon-to-carbon triple bond. A more preferred alkynyl radical is a lower alkynyl radical having from 2 to about 7 carbon atoms. Most preferred are lower alkynyl radicals having from 2 to about 5 carbon atoms. Examples of such radicals include propargyl, butynyl, and the like. Alkynyl groups may also be substituted at any available point of attachment.

As used herein, "cycloalkyl" refers to a non-aromatic monocyclic or multicyclic ring system having 3 to 10 carbon atoms, and monocyclic rings include, but are not limited to, cyclopropyl, cyclobutyl , cyclopentyl and cyclohexyl. Examples of polycyclic cycloalkyl groups include perhydronaphthyl, perhydroindenyl, and the like; Bridged polycyclic cycloalkyl groups include adamantyl and norbornyl, and the like.

As used herein, "heterocycloalkyl" refers to a substituted or unsubstituted non-aromatic 3 to 15 membered ring radical consisting of carbon atoms and 1 to 5 heteroatoms selected from nitrogen, phosphorus, oxygen and sulfur, and heterocycloalkyl The radicals may be monocyclic, bicyclic or tricyclic ring systems which may include fused, bridged or spiro ring systems, and the nitrogen, phosphorus, carbon, oxygen or sulfur atoms in heterocyclic ring radicals may be in various oxidation states. may be oxidized in some cases. Also, the nitrogen atom may be quaternized in some cases.

The alicyclic ring described in the present invention refers to a non-aromatic monocyclic or polycyclic ring system having 3 to 10 carbon atoms, and the carbon in the ring may have a carbon-carbon double bond or a carbon-carbon triple bond.

Hereinafter, the olefin oligomerization catalyst of the present invention will be described in detail.

The olefin oligomerization catalyst of the present invention may be directly prepared and used, or a commercially available oligomerization catalyst may be used, or components capable of preparing the oligomerization catalyst, that is, a transition metal source and a heteroatom ligand may be used.

The transition metal source according to an embodiment of the present invention may be a transition metal inorganic salt, a transition metal organic salt, a transition metal coordination compound, or a complex of a transition metal and an organometal, and the transition metal of the transition metal source is a group 4 or 5 group. , or a transition metal of Group 6, specifically chromium, molybdenum, tungsten, titanium, tantalum, vanadium or zirconium, preferably chromium.

The transition metal source may combine, for example, a transition metal and various organic ligands, and these organic ligands may be selected from the following structures.

(The R ⁴¹ to R ⁴⁵ are each independently hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl.)

The organic ligand may preferably be an acetylacetonato-based ligand represented by Chemical Formula 31 below.

[Formula 31]

(In Formula 31 above

R ⁴⁶ to R ⁴⁸ are each independently hydrogen, halogen, (C6-C20) aryl, (C6-C20) ar (C1-C10) alkyl, (C1-C10) alkyl, halo (C1-C10) alkyl, (C6 -C20) are (C2-C10) alkenyl, (C2-C10) alkenyl, (C6-C20) are (C2-C10) alkynyl, (C2-C10) alkynyl, (C1-C10) alkoxy, ( C6-C20) Aryloxy, (C1-C10) Alkylcarbonyloxy, (C2-C10) Alkenylcarbonyloxy, (C2-C10) Alkynylcarbonyloxy, (C3-C7) Cycloalkyl, (C1- C10) alkylsilyl, (C2-C10) alkenylsilyl, fluorine-substituted (C2-C10) alkynylsilyl, (C6-C20) arylsilyl, (C3-C20) heteroaryl or 5-7 membered heterocycloalkyl;

Aryl, aralkyl, alkyl, aralkenyl, alkenyl, aralkynyl, alkynyl, alkoxy, aryloxy , cycloalkyl , heteroaryl and heterocycloalkyl of R ⁴⁶ to R ⁴⁸ are (C1-C10)alkyl, (C2-C10) alkenyl, (C2-C10) alkynyl, (C1-C10) alkoxy, (C6-C20) aryl, (C6-C20) aryloxy, and may be further substituted with one or more selected from halogen. .)

Preferably, in Formula 31, R ⁴⁶ and R ⁴⁷ may each independently be hydrogen, halogen, or halo(C1-C10)alkyl, and R ⁴⁸ may be hydrogen or (C1-C10)alkyl.

The acetylacetonato-based ligand of Chemical Formula 31 according to an embodiment of the present invention may be selected from the following structures, but is not limited thereto.

As a specific example of the transition metal source, when the transition metal is chromium, chromium (III) acetylacetonate, chromium (III) chloride, chromium (III) naphthenate, chromium (III) 2-ethylhexanoate, chromium (III) It may be one or two or more selected from acetate, chromium (III) 2,2,6,6-tetramethylheptadionate, chromium (III) octanoate, and chromium hexacarbonyl, preferably chromium (III) acetyl acetonate or chromium(III) chloride.

Preferably, the heteroatom ligand according to an embodiment of the present invention may be (R) _n BCD (R) _m , wherein B and D are independently phosphorus, arsenic, antimony, oxygen, bismuth, sulfur, selenium and is any one selected from nitrogen, C is a linking group between B and D, R is the same or different and each independently selected from hydrocarbyl, heterohydrocarbyl, substituted hydrocarbyl and substituted heterohydrocarbyl groups, n and m may be determined by each valency and oxidation state of B or D, preferably, B and D are independently phosphorus, and C is alkylene or N(R') as a linking group between B and D (Where R' is alkyl), R is the same or different and each independently selected from hydrocarbyl, heterohydrocarbyl, substituted hydrocarbyl and substituted heterohydrocarbyl groups, and n and m are each B Or it may be determined by each valence and oxidation state of D.

The heteroatom ligand may be a P-C-C-P skeletal structure represented by Formula 32 or a P-N-P skeletal structure represented by Formula 33, but is not limited thereto.

[Formula 32]

[Formula 33]

(In Chemical Formulas 32 and 33,

R ⁵¹ to R ⁵⁴ are each independently hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, or substituted heterohydrocarbyl;

R ⁵⁵ and R ⁵⁶ are each independently hydrocarbyl or substituted hydrocarbyl, or R ⁵⁵ and R ⁵⁶ are bonded to each other as hydrocarbylene, substituted hydrocarbylene, heterohydrocarbylene, or substituted heterohydrocarbylene to form a ring can form.)

R ⁵¹ to R ⁵⁴ in Formulas 32 and 33 are each independently (C6-C20)aryl, (C6-C20)ar(C1-C10)alkyl, (C6-C20)ar(C2-C10)alkenyl, ( C6-C20)ar(C2-C10)alkynyl, (C1-C10)alkyl, (C2-C10)alkenyl, (C2-C10)alkynyl , (C1-C10)alkoxy, (C6-C20)aryloxy , (C1-C10) alkoxycarbonyl, (C1-C10) alkylcarbonyloxy, (C2-C10) alkenylcarbonyloxy, (C2-C10) alkynylcarbonyloxy, aminocarbonyl, (C1-C10) ) Alkylcarbonylamino, (C2-C10)alkenylcarbonylamino, (C2-C10)alkynylcarbonylamino, (C3-C7)cycloalkyl , thio(C1-C10)alkyl, thio(C2-C10) alkenyl, thio(C2-C10)alkynyl, (C1-C10)alkylsilyl, (C2-C10)alkenylsilyl; (C2-C10) alkynylsilyl, (C6-C20) arylsilyl, (C3-C20) heteroaryl, 5- to 7-membered heterocycloalkyl or -NR ⁶¹ R ⁶² , R ⁶¹ and R ⁶² are each independently as (C1-C10)alkyl, (C2-C10)alkenyl, (C2-C10)alkynyl, (C6-C20)aryl, di(C1-C10)alkylamino, di(C2-C10)alkenylamino or di(C2-C10)alkynylamino;

R ⁵⁵ and R ⁵⁶ are each independently (C6-C20) aryl, (C6-C20) ar (C1-C10) alkyl, (C6-C20) ar (C2-C10) alkenyl, (C6-C20) ar ( C2-C10)alkynyl, (C1-C10)alkyl, (C2-C10)alkenyl, (C2-C10)alkynyl, (C3-C7)cycloalkyl, (C3-C20)heteroaryl, 5-7 members 1-membered heterocycloalkyl, (C1-C10)alkoxy, (C6-C20)aryloxy, (C1-C10)alkoxycarbonyl, (C1-C10)alkylcarbonyloxy, (C2-C10)alkenylcarbonyloxy , (C2-C10) alkynylcarbonyloxy, aminocarbonyl, (C1-C10)alkylcarbonylamino, (C2-C10)alkenylcarbonylamino, (C2-C10)alkynylcarbonylamino, di( C1-C10)alkylamino, di(C2-C10)alkenylamino, di(C2-C10)alkynylamino, (C1-C10)alkylsilyl, (C2-C10)alkenylsilyl, (C2-C10)alky Nylsilyl or (C6-C20)arylsilyl, or R ⁵⁵ and R ⁵⁶ may be connected by (C3-C10)alkylene or (C3-C10)alkenylene to form a ring;

Aryl, aralkyl, aralkenyl, aralkynyl, alkyl, alkenyl, alkoxy, aryloxy, alkoxycarbonyl, alkylcarbonyloxy, alkenylcarbonyloxy, alkynylcarbonyloxy of R ⁵¹ to R ⁵⁴ , cycloalkyl, heteroaryl, heterocycloalkyl, and aryl, aralkyl, aralkenyl, aralkynyl, alkyl, alkenyl, cycloalkyl, heteroaryl, heterocycloalkyl, alkoxy, aryloxy of R ⁵⁵ and R ⁵⁶ , alkoxycarbonyl, alkylcarbonyloxy, alkenylcarbonyloxy, alkynylcarbonyloxy, aminocarbonyl, alkylcarbonylamino, alkenylcarbonylamino, alkynylcarbonylamino, dialkylamino, dialkenylamino , dialkynylamino, alkylsilyl, alkenylsilyl, alkynylsilyl or arylsilyl is (C1-C10)alkyl, (C2-C10)alkenyl, (C2-C10)alkynyl, (C1-C10)alkoxy, ( One or more from C6-C20)aryloxy, di(C1-C10)alkylamino, di(C2-C10)alkenylamino, di(C2-C10)alkynylamino and halogen may be further substituted.

Preferably, in Formulas 32 and 33, R ⁵¹ to R ⁵⁴ are each independently (C6-C20) aryl;

R ⁵⁵ and R ⁵⁶ may each independently be (C1-C10)alkyl.

In Formulas 32 and 33, specifically, R ⁵¹ to R ⁵⁴ are each phenyl, benzyl, biphenyl, naphthyl, anthracenyl, mesityl, xylyl, methyl, ethyl, ethenyl, ethynyl, n-propyl, i -propyl, propenyl, propynyl, n-butyl, t-butyl, butenyl, butynyl, methylphenyl, ethylphenyl, methoxyphenyl, ethoxyphenyl, isopropylphenyl, isopropoxyphenyl, t-butylphenyl, cumyl, methoxy, ethoxy, phenoxy, tolyloxy, dimethylaminophenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, ethylcyclohexyl or isopropylcyclohexyl, dimethylamino, thiomethyl, trimethyl silyl and dimethylhydrazyl;

R ⁵⁵ and R ⁵⁶ are each independently methyl, ethyl, ethenyl, ethynyl, n-propyl, i-propyl, propenyl, propynyl, n-butyl, t-butyl, i-butyl, butenyl, butynyl , phenyl, benzyl, tolyl, xylyl, methoxy, ethoxy, phenoxy, methylamino, dimethylamino, or R ⁵⁵ and R ⁵⁶ are propylene, butylene, pentylene or butenylene linked to 5 to 7 membered can form a ring.

The ligand of the PCCP skeleton structure of Formula 32 is (phenyl) ₂ P-CH (methyl) CH (methyl) -P (phenyl) ₂ , (4-methoxyphenyl) ₂ P-CH (methyl) CH (methyl) - P(4-methoxyphenyl) ₂ , (4-methylphenyl) ₂ P-CH(methyl)CH(methyl)-P(4-methylphenyl) ₂ , (4-ethylphenyl) ₂ P-CH(methyl)CH( Methyl)-P(phenyl) ₂ , (2-ethylphenyl) ₂ P-CH(methyl)CH(methyl)-P(2-ethylphenyl) ₂ , (2-isopropylphenyl) ₂ P-CH(methyl) CH(methyl)P-(2-isopropylphenyl) ₂ , (2-methylphenyl) ₂ P-CH(methyl)CH(methyl)P-(2-methylphenyl) ₂ , (2-ethylphenyl) ₂ P-CH (methyl)CH(methyl)-P(phenyl) ₂ , (3-methoxyphenyl) ₂ P-CH(methyl)CH(methyl)-P(3-methoxyphenyl) ₂ , (4-ethoxyphenyl) ₂ P-CH(methyl)CH(methyl)-P(2-ethoxyphenyl) ₂ ,(4-dimethylaminominephenyl) ₂ P-CH(methyl)CH(methyl)-P(4-dimethylaminophenyl) ₂ , (4-ethylcyclohexyl) ₂ P-CH(methyl)CH(methyl)-P(4-ethylcyclohexyl) ₂ , (2-methoxyphenyl) ₂ P-CH(methyl)CH(methyl)- P(2-methoxyphenyl) ₂ , (2-ethoxyphenyl) ₂ P-CH(methyl)CH(methyl)-P(2-ethoxyphenyl) ₂ , (2-dimethylaminophenyl) ₂ P-CH (Methyl)CH(methyl)-P(2-dimethylaminophenyl) ₂ , (2-ethylcyclohexyl) ₂ P-CH(methyl)CH(methyl)-P(2-ethylcyclohexyl) ₂ , (4- Ethylphenyl) ₂ P-CH(ethyl)CH(methyl)-P(4-ethylphenyl) ₂ , (4-methoxyphenyl) ₂ P-CH(ethyl)CH(methyl)-P(phenyl) ₂ , ( 2-ethylphenyl) ₂ P-CH(ethyl)CH(methyl)-P(2-ethylphenyl) ₂ , (4-ethylphenyl) ₂ P-CH(ethyl)CH(ethyl)-P(4-ethylphenyl) ) ₂ , (phenyl) ₂ P-CH(ethyl)CH(ethyl)-P(phenyl) ₂ , (2-ethylphenyl) ₂ P-CH(ethyl)CH(ethyl)-P(2-ethylphenyl) ₂ , (phenyl) ₂ P-CH (isopropyl) CH (methyl) -P (phenyl) ₂ , (4-methoxyphenyl) ₂ P-CH (isopropyl) CH (methyl) -P (4-methoxyphenyl) ) ₂ , (4-ethylphenyl) ₂ P-CH(isopropyl)CH(methyl)-P(4-ethylphenyl) ₂ , (2-ethylphenyl) ₂ P-CH(isopropyl)CH(methyl)- P(2-ethylphenyl) ₂ , (phenyl) ₂ P-CH(n-propyl)CH(methyl)-P(phenyl) ₂ , (4-methoxyphenyl) ₂ P-CH(n-propyl)CH( Methyl)-P(4-methoxyphenyl) ₂ , (4-ethylphenyl) ₂ P-CH(n-propyl)CH(methyl)-P(4-ethylphenyl) ₂ , (2-ethylphenyl) ₂ P -CH(n-propyl)CH(methyl)-P(2-ethylphenyl) ₂ , (phenyl) ₂ P-CH(isopropyl)CH(ethyl)-P(phenyl) ₂ , (4-methoxyphenyl) ₂ P-CH(isopropyl)CH(ethyl)-P(4-methoxyphenyl) ₂ , (4-ethylphenyl) ₂ P-CH(isopropyl)CH(ethyl)-P(4-ethylphenyl) ₂ , (2-ethylphenyl) ₂ P-CH(isopropyl)CH(ethyl)-P(2-ethylphenyl) ₂ , 1,2-di-(P(phenyl) ₂ )cyclohexane, 1,2-di -(P(4-methoxyphenyl) ₂ )cyclohexane, 1,2-di-(P(4-ethylphenyl) ₂ )cyclohexane, 1,2-di-(P(2-ethylphenyl) ₂ ) Cyclohexane, 1,2-di-(P(phenyl) ₂ )cyclopentane, 1,2-di-(P(4-methoxyphenyl) ₂ )cyclopentane, 1,2-di-(P(4- Ethylphenyl) ₂ )cyclopentane, 1,2-di-(P(2-ethylphenyl) ₂ )cyclopentane, (4-ethylphenyl) ₂ P-CH(dimethylamino)CH(dimethylamino)-P(4 -ethylphenyl) ₂ and (2-ethylphenyl) ₂ P-CH(dimethylamino)CH(dimethylamino)-P(2-ethylphenyl) ₂ , but is not limited thereto.

The ligands of the P-N-P skeleton structure of Formula 33 are (phenyl) 2PN (methyl) P (phenyl) 2, (phenyl) 2PN (pentyl) P (phenyl) 2, (phenyl) 2PN (phenyl) P (phenyl) 2, ( Phenyl)2PN(p-methoxyphenyl)P(phenyl)2, (phenyl)2PN(p-tbutylphenyl)P(phenyl)2, (phenyl)2PN((CH2)3-N-morpholine)P(phenyl) 2, (phenyl)2PN(Si(CH3)3)P(phenyl)2, (((phenyl)2P)2NCH2CH2)N, (ethyl)2PN(methyl)P(ethyl)2, (ethyl)2PN(isopropyl )P(phenyl)2, (ethyl)(phenyl)PN(methyl)P(ethyl)(phenyl), (ethyl)(phenyl)PN(isopropyl)P(phenyl)2, (phenyl)2P(=Se) N(isopropyl)P(phenyl)2, (phenyl)2PCH2CH2P(phenyl)2, (o-ethylphenyl)(phenyl)PN(isopropyl)P(phenyl)2, (o-methylphenyl)2PN(isopropyl) P(o-methylphenyl)(phenyl), (phenyl)2PN(benzyl)P(phenyl)2, (phenyl)2PN(1-cyclohexylethyl)P(phenyl)2, (phenyl)2PN[CH2CH2CH2Si(OMe3)] P(phenyl)2, (phenyl)2PN(cyclohexyl)P(phenyl)2, (phenyl)2PN(2-methylcyclohexyl)P(phenyl)2, (phenyl)2PN(allyl)P(phenyl)2, (2-naphthyl)2PN(methyl)P(2-naphthyl)2, (p-biphenyl)2PN(methyl)P(p-biphenyl)2, (p-methylphenyl)2PN(methyl)P(p -Methylphenyl)2, (2-thiophenyl)2PN(methyl)P(2-thiophenyl)2, (phenyl)2PN(methyl)N(methyl)P(phenyl)2, (m-methylphenyl)2PN(methyl) It may be selected from P(m-methylphenyl)2, (phenyl)2PN(isopropyl)P(phenyl)2 and (phenyl)2P(=S)N(isopropyl)P(phenyl)2, but is not limited thereto. don't

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

The olefin oligomerization catalyst according to the present invention may be mononuclear or dinuclear, specifically ML ¹ (L ² ) _p (X) _q or M ₂ X ¹ ₂ L ¹ ₂ (L ² ) _y (X) _{z ,} It may be represented by, wherein M is a transition metal, L ¹ is a heteroligand, L ² is an organic ligand, X and X ¹ are each independently a halogen, p is an integer of 0 or 1 or more, and q is ( M is an integer of oxidation number-p), y is an integer of 2 or greater, and z is an integer of (2 x oxidation number of M)-y-2.

Preferably, the oligomerization catalyst according to an embodiment of the present invention may be represented by Chemical Formula 34 or Chemical Formula 35, but is not limited thereto.

[Formula 24]

[Formula 25]

(In Chemical Formulas 24 to 25,

R ⁴⁶ to R ⁴⁸ are each independently hydrogen, halogen, (C6-C20) aryl, (C6-C20) are (C1-C10) alkyl, (C1-C10) alkyl, halo (C1-C10) alkyl, (C6 -C20) are (C2-C10) alkenyl, (C2-C10) alkenyl, (C6-C20) are (C2-C10) alkynyl, (C2-C10) alkynyl, (C1-C10) alkoxy, ( C6-C20) Aryloxy, (C1-C10) Alkylcarbonyloxy, (C2-C10) Alkenylcarbonyloxy, (C2-C10) Alkynylcarbonyloxy, (C3-C7) Cycloalkyl, (C1- C10) alkylsilyl, (C2-C10) alkenylsilyl, (C2-C10) alkynylsilyl, (C6-C20) arylsilyl, (C3-C20) heteroaryl or 5-7 membered heterocycloalkyl;

Aryl, aralkyl, alkyl, aralkenyl, alkenyl, aralkynyl, alkynyl, alkoxy, aryloxy , cycloalkyl , heteroaryl and heterocycloalkyl of R ⁴⁶ , R ^{47 and} R 48 are (C1-C10 ) further substituted with one or more selected from alkyl, (C2-C10)alkenyl, (C2-C10)alkynyl, (C1-C10)alkoxy, (C6-C20)aryl, (C6-C20)aryloxy and halogen can be,

R ⁵¹ to R ⁵⁴ are each independently (C6-C20) aryl, (C6-C20) ar (C1-C10) alkyl, (C6-C20) ar (C2-C10) alkenyl, (C6-C20) ar ( C2-C10)alkynyl, (C1-C10)alkyl, (C2-C10)alkenyl, (C2-C10)alkynyl , (C1-C10)alkoxy, (C6-C20)aryloxy , (C1-C10) Alkoxycarbonyl, (C1-C10)alkylcarbonyloxy, (C2-C10)alkenylcarbonyloxy, (C2-C10)alkynylcarbonyloxy, aminocarbonyl, (C1-C10)alkylcarbonylamino, (C2-C10)alkenylcarbonylamino, (C2-C10)alkynylcarbonylamino, (C3-C7)cycloalkyl , thio(C1-C10)alkyl, thio(C2-C10)alkenyl, thio(C2 -C10) alkynyl, (C1-C10) alkylsilyl, (C2-C10)alkenylsilyl; (C2-C10) alkynylsilyl, (C6-C20) arylsilyl, (C3-C20) heteroaryl, 5- to 7-membered heterocycloalkyl, or -NR ²¹ R ²² , and R ²¹ and R ²² are each independently as (C1-C10)alkyl, (C2-C10)alkenyl, (C2-C10)alkynyl, (C6-C20)aryl, di(C1-C10)alkylamino, di(C2-C10)alkenylamino or di(C2-C10)alkynylamino;

R ⁵⁵ and R ⁵⁶ are each independently (C6-C20) aryl, (C6-C20) ar (C1-C10) alkyl, (C6-C20) ar (C2-C10) alkenyl, (C6-C20) ar ( C2-C10)alkynyl, (C1-C10)alkyl, (C2-C10)alkenyl, (C2-C10)alkynyl, (C3-C7)cycloalkyl, (C3-C20)heteroaryl, 5-7 members 1-membered heterocycloalkyl, (C1-C10)alkoxy, (C6-C20)aryloxy, (C1-C10)alkoxycarbonyl, (C1-C10)alkylcarbonyloxy, (C2-C10)alkenylcarbonyloxy , (C2-C10) alkynylcarbonyloxy, aminocarbonyl, (C1-C10)alkylcarbonylamino, (C2-C10)alkenylcarbonylamino, (C2-C10)alkynylcarbonylamino, di( C1-C10)alkylamino, di(C2-C10)alkenylamino, di(C2-C10)alkynylamino, (C1-C10)alkylsilyl, (C2-C10)alkenylsilyl, (C2-C10)alkynylsilyl or (C6-C20)arylsilyl, or R ⁴⁵ and R ⁴⁶ may be connected by (C3-C10)alkylene or (C3-C10)alkenylene to form a ring;

Aryl, aralkyl, aralkenyl, aralkynyl, alkyl, alkenyl, alkoxy, aryloxy, alkoxycarbonyl, alkylcarbonyloxy, alkenylcarbonyloxy, alkynylcarbonyloxy of R ⁵¹ to R ⁵⁴ , cycloalkyl, heteroaryl, heterocycloalkyl, and aryl, aralkyl, aralkenyl, aralkynyl, alkyl, alkenyl, cycloalkyl, heteroaryl, heterocycloalkyl, alkoxy, aryloxy of R ⁵⁵ and R ⁵⁶ , alkoxycarbonyl, alkylcarbonyloxy, alkenylcarbonyloxy, alkynylcarbonyloxy, aminocarbonyl, alkylcarbonylamino, alkenylcarbonylamino, alkynylcarbonylamino, dialkylamino, dialkenylamino , dialkynylamino, alkylsilyl, alkenylsilyl, alkynylsilyl or arylsilyl is (C1-C10)alkyl, (C2-C10)alkenyl, (C2-C10)alkynyl, (C1-C10)alkoxy, ( one or more from C6-C20)aryloxy, di(C1-C10)alkylamino, di(C2-C10)alkenylamino, di(C2-C10)alkynylamino and halogen may be further substituted;

X is halogen; and

a is 0 or an integer from 1 to 3, and b and c are each independently an integer of 1 or 2.)

Preferably, in Formulas 33 to 34, R ⁴⁶ to R ⁴⁸ are each independently hydrogen, (C1-C10)alkyl or halo(C1-C10)alkyl, and R ⁵¹ to R ⁵⁴ are each independently (C6-C20)aryl is; R ⁵⁵ and R ⁵⁶ may each independently represent (C1-C10)alkyl, or R ⁵¹ to R ⁵⁴ may each independently represent (C6-C20)aryl; R ⁵⁵ and R ⁵⁶ may each independently represent (C1-C10)alkyl, and a may be a compound in which a is 0.

The cocatalyst included in the olefin oligomerization catalyst composition according to an embodiment of the present invention may be an organic aluminum compound, an organic aluminoxane, an organic boron compound, or a mixture thereof.

The organoaluminum compound according to an embodiment of the present invention is AlR ₃ (R are each independently (C1-C12)alkyl, (C2-C10)alkenyl, (C2-C10)alkynyl, (C1-C12)alkoxy or halogen.) or LiAlH ₄ and the like.

The organic aluminum compound according to the present invention is trimethylaluminum (TMA), triethylaluminum (TEA), triisobutylaluminum (TIBA), tri-n-octylaluminum, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum chloride, one or a mixture of two or more selected from diethylaluminum chloride, aluminum isopropoxide, ethylaluminum sesquichloride and methylaluminum sesquichloride.

An organoaluminoxane according to an embodiment of the present invention is widely known in the art as an oligomeric compound that can typically be prepared by adding water to water and an alkylaluminum compound, for example, trimethylaluminum. The resulting aluminoxane oligomer compounds may be linear, cyclic, caged or mixtures thereof.

Organic aluminoxanes include alkylaluminoxanes such as methylaluminoxane (MAO), ethylaluminoxane (EAO), tetraisobutylaluminoxane (TIBAO) and isobutylaluminoxane (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 hybrid alkyl groups such as isobutyl or n-octyl groups in addition to methyl groups.

As a specific example, one or a mixture of two or more selected from methyl aluminoxane (MAO), modified methyl aluminoxane (MMAO), ethyl aluminoxane (EAO), tetraisobutyl aluminoxane (TIBAO), and isobutyl aluminoxane (IBAO) can

Organoboron compounds as cocatalysts according to an embodiment of the present invention are boroxine, NaBH ₄ , triethyl borane, triphenylborane, triphenylborane ammonia complex, tributyl borate, triisopropyl borate, tris (pentafluorophenyl ) Borane, trityl (tetrapentafluorophenyl) borate, dimethylphenylammonium (tetrapentafluorophenyl) borate, diethylphenylammonium (tetrapentafluorophenyl) borate, methyldiphenylammonium (tetrapentafluorophenyl) It may be borate or ethyldiphenylammonium (tetrapentafluorophenyl) borate, and these organic boron compounds may be used in mixture with the above organic aluminum compounds.

The ratio of the olefin oligomerization catalyst and aluminoxane according to the present invention may be 1:1 to 10,000:1, preferably 1:1 to 1,000:1 based on the aluminum:transition metal molar ratio.

In addition, the present invention provides a method for producing oligomers from olefins in the presence of the olefin oligomerization catalyst composition of the present invention.

The oligomerization catalyst, cocatalyst, and additives, which are individual components of the olefin oligomerization catalyst composition disclosed in the present invention, may be mixed simultaneously or sequentially in an arbitrary order in the presence of a solvent to provide an olefin oligomerization catalyst composition. Mixing of the components of each catalyst composition can be performed at a temperature of -20 to 250 ° C., and the presence of olefins during mixing of the catalyst components can generally provide a protective effect, thereby providing improved catalyst performance. A more preferable temperature range is 20 to 100°C.

The oligomers prepared from the olefins, the reaction products disclosed herein, in particular 1-hexene or 1-octene, can be prepared in a homogeneous liquid phase in the presence of an inert solvent using conventional equipment and contact techniques with catalysts for the oligomerization of olefins, particularly ethylene, according to the invention. It can be prepared in a reaction, a two-phase liquid/liquid reaction, a bulk phase reaction in which the product olefin acts as the main medium, or a gas phase reaction.

The oligomer preparation method according to the present invention can be carried out in an inert solvent. That is, any inert solvent that does not react with the oligomerization catalyst, cocatalyst, and additives may be used, and the inert solvent may include an aliphatic hydrocarbon. The aliphatic hydrocarbon is a saturated aliphatic hydrocarbon, A linear saturated aliphatic hydrocarbon represented by C _n H _{2n +2} (where n is an integer from 1 to 15), an alicyclic saturated aliphatic hydrocarbon represented by C _m H _2m (where m is an integer from 3 to 8), and These include saturated aliphatic hydrocarbons in which one or two or more lower alkyl groups having 1 to 3 carbon atoms are substituted. Specifically, 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, but is not limited thereto.

The oligomerization reaction according to the production method of the present invention may be carried out at a temperature of 0 to 200 ° C, preferably at a temperature of 15 to 130 ° C, more preferably at a temperature of 30 to 70 ° C, and the reaction pressure is from atmospheric pressure to 100 ° C. bar, preferably atmospheric pressure to 80 bar pressure, more preferably atmospheric pressure to 60 bar pressure.

In a preferred embodiment of the present invention, the oligomerization reaction conditions can produce, for example, a yield of 1-hexene from ethylene of 50% by mass or more, preferably 70% by mass or more. Yield in this case means the number of grams of 1-hexene formed per 100 g of total reaction product formed.

In a preferred embodiment of the present invention, the oligomerization reaction conditions can produce, for example, a yield of 1-octene from ethylene of 30% by mass or more, preferably 50% by mass or more. Yield in this case means the number of grams of 1-octene formed per 100 g of total reaction product formed.

In the method of preparing an oligomer from an olefin of the present invention, the olefin may preferably be ethylene, and the oligomer may be 1-hexene, 1-octene or a mixture thereof.

The process for preparing oligomers from olefins according to the present invention can be carried out with 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 include a combination of a reactor, an olefin reactor and an inlet for the catalyst composition in the reactor, a line for discharging the oligomerization reaction product from the reactor, and at least one separator for separating the oligomerization reaction product, wherein the catalyst The composition is an olefin oligomerization catalyst composition disclosed in the present invention and may include a transition metal source and a heteroatom ligand or an oligomerization catalyst prepared therefrom, a cocatalyst, and an additive.

In the method for producing oligomers from olefins according to an embodiment of the present invention, the problems raised in the conventional process are improved by using the olefin oligomerization catalyst composition of the present invention, so that 1-hexene and 1-octene are easily produced in high yield. or mixtures thereof may be produced.

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.

[ Example One] oligomerization Preparation of Catalyst A

1 g (1.7 mmol) of bis-[(S,S)-(phenyl) ₂ PCH(methyl)CH(methyl)P(phenyl) ₂ dichloride(μ-chloride)chrome] prepared in Example 2 below After dissolving in 100 mL of chemical methane, 0.39 g (1.7 mmol) of sodium hexafluoroacetylacetonate was slowly added. After the reaction mixture was stirred for 3 hours, filtration was performed using a glass filter. The filtered liquid was freed of volatiles in vacuo to give a dried dark green solid. After washing twice with 50 mL of hexane, 1.22 g of the title compound was obtained (yield: 95%).

[ Example 2] Preparation of Oligomerization Catalyst B (bis-[(S,S)-(phenyl) ₂ PCH(methyl)CH(methyl)P(phenyl) ₂ dichloride(μ-chloride)chrome] ([CrCl Preparation of ₂ (μ-Cl){(P,P)-k2-(S,S)-((Ph) ₂ P(Me)CH-CH(Me)P(Ph) ₂ )}] ₂ )

After dissolving 1.1 g (3.0 mmol) of tritetrahydrofuran chromium trichloride (CrCl ₃ (THF) ₃ ) in 100 mL of dichloromethane, (S,S)-(phenyl) ₂ PCH(methyl)CH(methyl)P(phenyl) ) ₂ Ligand compound 1.28 g (3.0 mmol) was also dissolved in 50 mL of methane dichloride and added slowly. After stirring the reactant for another 3 hours, volatiles were removed by vacuum, and then 100 mL of MCH (methylcyclohexane) was added dropwise to obtain a blue solid as precipitate. After washing twice with 100 mL of MCH (methylcyclohexane), 1.58 g of the title compound was obtained (yield: 90%).

[ Example 3 to 12 and comparative example 1 to 3] of ethylene oligomerization reaction

A 2000 mL stainless steel pressure reactor was washed with nitrogen and vacuum, 760 g of methylcyclohexane was added, 4 mmol of MAO 3A was added, the temperature was raised to 60 ° C, and ethylene was injected to 18 bar. After preparing a mixed solution in which the oligomerization catalyst shown in Table 1, 3.1 mg (5.3 μmol-Cr), and additives were dissolved in 10 ml of methylcyclohexane in a glove box, it was taken out and injected into the reactor. Ethylene was charged to a pressure reactor at 20 bar and stirred at a stirring rate of 250 rpm. After 120 minutes, the ethylene feed to the reactor was stopped, stirring was stopped to stop the reaction, and the reactor was cooled down to 10°C.

After discharging excess ethylene in the reactor, ethanol was injected into the liquid contained in the reactor. The quenched product was analyzed by GC-FID. The remaining organic layer was filtered to isolate the solid wax/polymer product. After drying these solid products in an oven at 100 ° C. overnight, the results shown in Table 1 were obtained.

The reaction results are shown in Table 1 below.

[ Example 13 and comparative example 3] of ethylene oligomerization reaction

Examples 3 to 12 except for using 20 umol of Cr (acac) ₃ as a transition metal source and 2eq of PNP ligand as a heteroatomic ligand instead of the oligomerization catalysts A and B used in Examples 3 to 12 and Comparative Examples 1 to 2 And in the same manner as in Comparative Examples 1 and 2, the ethylene oligomerization reaction was performed, and the results are shown in Table 1 below.

catalyst additive LAO production amount
(C6+C8, g) LAO production amount
(C6/C8) Polymer ^c Activity (Kg/mol-Cr cat hr) Ratio ^a Ratio comparison to STD ^b type content 1st (g) 2nd (g) Example 3 A cyclohexene 100 385 0.94 0.44 0.20 36340 0.55 16% Example 4 A cyclohexene 2 381 0.93 0.5 0.40 35948 1.11 32% Example 5 A cyclohexene 50 375 0.93 0.4 0.23 35423 0.65 19% Example 6 A cyclohexene 600 276 0.86 0.25 0.19 26038 0.73 21% Example 7 A 1,3-butadiene 100 431 0.96 0.7 0.68 40660 1.67 48% Example 8 A 1,3-butadiene 600 443 One 0.75 0.65 41804 1.55 45% Example 9 A 3-hexane 100 375 0.9 0.56 0.60 35341 1.70 49% Example 10 A Dipentene 100 443 1.02 0.66 0.50 41825 1.20 35% Example 11 B cyclohexene 100 316 0.83 0.4 0.30 29780 1.01 30% Example 12 B cyclohexene 100 355 0.86 0.11 0.10 33476 0.30 9% Example 13 C ^d cyclohexene - 19 0.48 1.02 2.04 475 429.47 43% Example 14 A 1,3-cyclohexadiene 100 385 0.94 0.44 0.2 36340 0.55 16% Example 15 A α-Terpinene 100 410 1.01 0.43 0.35 38724 0.90 6% Example 16 A DPCD 100 380 0.71 0.41 0.96 35849 2.68 78% Example 17 A α-phellandrene 100 424 1,04 0.48 0.44 40024 1.10 32% Example 18 A γ-Terpinene 100 338 0.94 0.41 0.5 31876 1.57 45% Comparative Example 1 A - - 395 0.95 0.82 1.24 35889 3.46 100% Comparative Example 2 B - - 326 0.8 1.09 0.94 27656 3.40 100% Comparative Example 3 C ^d - - 17 0.50 1.5 4.2 425 988.23 100%

a Ratio : (2nd polymer /activity) ⅹ10 ⁵

b STD ratio comparison: Ratio value of the same catalyst under each condition/ STD Ratio value

- Since there is a difference in the amount of polymer produced depending on the amount of LAO produced, the ratio of polymer amount divided by activity was compared. That is, in Examples 3 to 10, Comparative Example 1 was the STD Ratio value, in Examples 11 to 12, Comparative Example 2 was the STD Ratio value, and in Example 13, Comparative Example 3 was the STD Ratio value.

c ^1st polymer: Suspended polymer in the solvent, discharged together with the solvent, ^2nd polymer: Polymer that has no fluidity in the solvent and requires additional high-temperature cleaning work

d cat: Polymerization by simply mixing Cr(acac) and PNP ligand with MCH and adding additives without synthesizing and separating the catalyst. Cr(acac)3 20 umol, PNP ligand 2eq, mMAO 3A 4mmol, C2 20 bar, MCH 760g, 120 min

Additives used in the present invention are as follows.

compound 1,3 CHD
(1,3-Cyclohexadiene) 1,4 CHD
(1,4-Cyclohexadiene) Cyclohexenes 2,3-Dimethyl-1,3-butadiene 3-hexane a-TP
(α-Terpinene) g-TP
(γ-Terpinene) Dipentene DPCD
(1,3-Dicyclopentadiene) α-phellandrene

As shown in Table 1, Examples 3 to 18 in which the olefin oligomerization reaction was carried out by including a specific additive, which is a hydrocarbon compound having at least one unsaturated bond and different from the olefin and olefin mixture used in the olefin oligomerization reaction. It can be seen that the amount of secondary polymer produced is significantly reduced, and a surprising result of a reduction of up to 90% or more compared to the comparative example without the additive can be obtained.

Therefore, the olefin oligomerization method of the present invention, which is different from the olefin and olefin mixture used in the olefin oligomerization reaction and includes a hydrocarbon compound having at least one unsaturated bond as an additive, causes clogging of process equipment. By-products such as secondary polymers and waxes are remarkably suppressed, so there is no need for cleaning of separate process equipment, and it is possible to efficiently produce oligomers from olefins because operating time and speed do not decrease.

Claims (18)

Injecting a transition metal source and a heteroatom ligand or an oligomerization catalyst prepared therefrom into a reactor;
Injecting an additive containing a hydrocarbon compound having an unsaturated bond, and
Including the step of introducing olefin,
The oligomerization catalyst is ML ¹ (L ² ) _p (X) _q or M ₂ X ¹ ₂ L ¹ ₂ (L ² ) _y (X) _z (wherein M is a transition metal, L ¹ is a heteroatom ligand, L ² is an organic ligand, X and X ¹ are each independently a halogen, p is an integer of 0 or 1 or greater, q is an integer of (oxidation number of M-p), y is an integer of 2 or greater, and z is ( Oxidation number of 2 x M) - is an integer of y) A method for oligomerizing olefins, characterized in that it is expressed. According to claim 1,
The additive is a method for oligomerizing olefins having a molecular weight of 35 to 330 and a boiling point of 50 ° C to 350 ° C. According to claim 1,
The method of oligomerizing olefins in which the additive is a hydrocarbon compound having two or more double bonds. According to claim 3,
The method of oligomerizing olefins in which the hydrocarbon compound is a cyclic compound. According to claim 4,
The method for oligomerizing olefins in which the cyclic compound is a compound having a double bond in the ring. According to claim 4,
The method for oligomerizing olefins in which the cyclic compound is a compound substituted with alkyl. According to claim 1,
wherein the additive is a substituted or unsubstituted cycloalkene, a substituted or unsubstituted cycloalkyne, a substituted or unsubstituted alkene, or a substituted or unsubstituted alkyne. According to claim 7,
The additive is an oligomerization method of an olefin represented by any one of Formulas 1 to 4.
[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[In Formulas 1 to 4,
A is -C(R ⁹ )(R ¹⁰ )-,
Z is -C(R ¹⁷ )(R ¹⁸ )-;
is a double bond or a single bond,
R ¹ to R ³ , R ⁶ to R ¹⁰ , and R ¹¹ to R ¹⁸ are each independently hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl;
R ⁴ and R ⁵ are is not present when is a double bond, is independently hydrogen, halogen hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl when is a single bond;
nm is independently of each other 0 to 5,
When n and m are 1, R ³ and R ⁹ and R ¹³ and R ¹⁷ may be connected by (C1-C3)alkylene with or without a fused ring to form an alicyclic ring;
R ²¹ to R ²⁶ and R ³¹ are each independently hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl;
R ³² is halogen hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl.) According to claim 8,
Formula 1 is an oligomerization method of an olefin represented by any one of Formulas 11 to 13 below.
[Formula 11]

[Formula 12]

[Formula 13]

[In Chemical Formulas 11 to 13,
R ¹ to R ¹⁰ and R ^1a to R ^10a are each independently hydrogen, halogen hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl;
is a double bond or a single bond,
s is an integer from 0 to 2.] According to claim 9,
The additive is an oligomerization method of an olefin represented by any one of Formulas 21 to 24.
[Formula 21]

[Formula 22]

[Formula 23]

[Formula 24]

[In Chemical Formulas 21 to 24,
R ¹ , R ⁶ , R ^1a , R ^2a , R ^4a to R ^6a , R ¹² and R ¹⁶ are each independently hydrogen, halogen, (C1-C10)alkyl, (C2-C10)alkenyl, (C2-C10) )alkynyl, (C1-C10)alkoxy, (C6-C20)aryl, (C6-C20)aryloxy , (C1-C10)alkoxycarbonyl, (C1-C10)alkylcarbonyloxy, (C2-C10) Alkenylcarbonyloxy, (C2-C10)alkynylcarbonyloxy, (C3-C7)cycloalkyl , (C3-C7)heterocycloalkyl , (C1-C10)alkylsilyl, (C6-C20) arylsilyl, (C2-C10) alkenylsilyl, (C2-C10) alkynylsilyl or (C3-C20) heteroaryl.] According to claim 10,
The above R ¹ , R ⁶ , R ^1a , R ^2a , R ^4a to R ^6a , R ¹² and R ¹⁶ are each independently hydrogen, (C1-C10)alkyl or (C2-C10)alkene. According to claim 1,
The method for oligomerizing olefins wherein the additive is used in an amount of 1 to 1×10 ⁶ moles based on 1 mole of the transition metal of the oligomerization catalyst. According to claim 1
The transition metal source is a transition metal inorganic salt, a transition metal organic salt, a transition metal coordination compound, or a complex of a transition metal and an organometallic oligomerization method of olefins. According to claim 1,
The heteroatom ligand is of the general formula (R) _n BCD (R) _m , wherein B and D are independently any one selected from phosphorus, arsenic, antimony, oxygen, bismuth, sulfur, selenium and nitrogen, and C is a linking group between B and D, R is the same or different and each independently selected from hydrocarbyl, heterohydrocarbyl, substituted hydrocarbyl and substituted heterohydrocarbyl groups, n and m are each of B or D Process for oligomerization of olefins, characterized in that each valency and oxidation state are determined. delete According to claim 1,
The method of oligomerization of olefins further comprising a cocatalyst. According to claim 16,
The method for oligomerizing olefins, characterized in that the cocatalyst is an organic aluminum compound, an organic aluminoxane, an organic boron compound, or a mixture thereof. According to claim 1,
Wherein the olefin is ethylene, and the oligomer is 1-hexene, 1-octene or a mixture thereof.