KR20180009179A - Process For preparing oligomer Using olefin - Google Patents

Abstract

Provided is an olefin oligomerization method comprising the following steps: inputting transition metal supply sources, hetero atom ligands and organic ligands or an oligomerization catalyst manufactured therefrom to a reactor; inputting an additive which is a hydrocarbon compound being different from olefin or an olefin mixture and having at least one unsaturated bond; and inputting olefin. According to the present invention, production of polymers which are by-products is significantly reduced by adding a specific additive during oligomerization of olefin.

Description

Process for preparing oligomer using olefin < RTI ID = 0.0 >

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

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

Especially, 1-hexene and 1-octene are obtained as a monomer or comonomer for producing linear low-density polyethylene, which is a very important commercial raw material widely used in polymerization processes and which is produced by oligomerization reaction of ethylene.

However, the conventional ethylene oligomerization reaction has the ineffectiveness of producing a large amount of butene, high-grade oligomer and polyethylene together with 1-hexene and 1-octene. This conventional oligomerization technique of ethylene generally produces various? -Olefins according to Schulze-Flory or Poisson product distribution, so that the yield of desired products is limited.

Recently, studies have been conducted on the production of 1-octene by selectively trimerizing ethylene through transition metal catalysis to produce 1-hexene or selectively tetramerize it. Most of the known transition metal catalysts are chromium Based catalyst.

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, wherein X And 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-withdrawing substituent.

Another known literature in the R ^1, R ^2, R ³ and R ⁴ which does not have a polar substituent on at least one of the compounds as a ligand which does not exhibit catalytic activity for 1-hexene under catalytic conditions (o- ethylphenyl) ₂ PN (Me) P (o-ethylphenyl) ₂ (Antea Carter et al., Chem. Commun., 2002, p 858-859).

On the other hand, during the oligomerization reaction using an oligomerization catalyst and a promoter, reaction dispersions such as polymers and wax are generated, which causes problems in operation of the equipment.

That is, the polymer as a by-product reduces the operation time of the equipment, and the operation is stopped due to the clogging of the pipe due to the polymer, and it takes considerable time and expense to remove the polymer.

International Patent Publication No. WO2011 / 048527 discloses an oligomerization method using an oligomerization zinc compound, specifically diethylzinc as an additive, in International Patent Publication No. WO2013 / 168103 Discloses an oligomerization process that reduces polymer formation using non-metallic oxygen containing additives.

However, there is still a need for studies on methods of inhibiting polymer formation during satisfactory oligomerization reactions.

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

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

The present invention provides a method of oligomerizing an olefin which significantly reduces the production of a by-product polymer by adding a specific additive during the oligomerization of the olefin.

The present invention provides a method for oligomerization of olefins which can remarkably improve the oligomerization process of olefins by reducing the production of polymers, particularly secondary polymers, which are undesired byproducts of oligomerization of olefins, The oligomerization method includes,

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

The additive being a hydrocarbon compound having at least one unsaturated bond; And

And an olefin feedstock;

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

Preferably, the additive according to one 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, a compound having a double bond in a ring, and more preferably, a cyclic compound may be a compound substituted with an alkyl.

Preferably, the additive according to one embodiment of the present invention is a substituted or unsubstituted cycloalkene, substituted or unsubstituted cycloalkyne, substituted or unsubstituted alkene, substituted or unsubstituted alkynylene, substituted or unsubstituted cycloalkene, Lt; / RTI >

Preferably, the additive according to one embodiment of the present invention may be represented by the following formulas (1) to (4).

[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

[In formulas (1) to (4)

A represents ^{-C (R 9) (R 10} ) - , and

Z is ^{-C (R 17) (R 18} ) - , and

는 이중결합 또는 단일결합이며,

Is a double bond or a single bond,

R ¹ to R ³ , R ⁶ to R ¹⁰ and R ¹¹ to R ¹⁸ independently of one another are hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl,

가 이중결합인 경우 존재하지 않거나,

가 단일결합인 경우 서로 독립적으로 수소, 할로겐, 하이드로카빌, 치환된 하이드로카빌, 헤테로하이드로카빌 또는 치환된 헤테로하이드로카빌이며;R ⁴ and R ⁵ is

Is not present when it is a double bond,

Are independently of each other hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl when they are single bonds;

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 contain a fused ring, or (C1-C3) connected as an alkylene containing no may form an alicyclic ring, R ²¹ to R ²⁶ and R ³¹ independently of one another are hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl,

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

Preferably, formula (1) according to one embodiment of the present invention may be represented by the following formulas (11) to (13).

(11)

[Chemical Formula 12]

[Chemical Formula 13]

[In the above formulas (11) and (13)

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

는 이중결합 또는 단일결합이며,

Is a double bond or a single bond,

and s is an integer of 0 to 2.]

Preferably, the additive according to one embodiment of the present invention may be represented by the following formulas (21) to (24).

[Chemical Formula 21]

[Chemical Formula 22]

(23)

≪ EMI ID =

[In the above formulas 21 to 24,

R ¹ , R ⁶ , R ^1a , R ^2a , R ^4a To R ^6a, R ¹² and R ¹⁶ independently represent hydrogen, deuterium, halogen, (C1-C10) alkyl, (C2-C10) alkenyl, (C2-C10) alkynyl, (C1-C10) alkoxy, (C6- C20) aryl, (C6-C20) aryloxy, (C1-C10) alkoxycarbonyl, (C1-C10) alkyl-carbonyl-oxy, (C2-C10) alkenyl-carbonyl-oxy, (C2-C10) alkynyl carbonyl (C3-C7) cycloalkyl , (C3-C7) heterocycloalkyl , (C1-C10) alkylsilyl, (C6-C20) arylsilyl, (C2-C10) alkenylsilyl, (C2-C10) alkynylsilyl or (C3-C20) heteroaryl.]

Preferably, R ¹ , R ⁶ , R ^1a , R ^2a , R ^4a R ^6a , R ¹² and R ¹⁶ may be, independently of each other, hydrogen, (C 1 -C 10) alkyl or (C 2 -C 10) 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 relative to 1 mole of transition metal of the oligomerization catalyst.

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 organometallic compound.

The oligomerization catalyst according to one embodiment of the present invention may be a compound of the formula ML ¹ (L ² ) _p (X) _q or M ₂ X ¹ ₂ L ¹ ₂ (L ² ) _y (X) _z , L ¹ is a hetero ligand, L ² is an organic ligand, X and X ¹ are each independently halogen, p is 0 or an integer of 1 or more, q is an integer of (oxidation p of M) And z is an integer of (2 x 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 selected from the group consisting of arsenic, antimony, oxygen, bismuth, Nitrogen, C is a linking group between B and D, and R are the same or different and are each independently selected from hydrocarbyl, heterohydrocarbyl, substituted hydrocarbyl and substituted heterohydrocarbyl groups, n and m may be determined to be each valence of B or D and an oxidation state, respectively.

In the method of 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 organoaluminum compound, an organic boron compound, or a mixture thereof.

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

The method of oligomerization of olefins according to the present invention differs from a specific additive in the oligomerization of olefins, specifically, a mixture of olefins or olefins, and the addition of a hydrocarbon compound having at least one unsaturated bond results in clogging of the process equipment during the oligomerization process Remarkably suppresses the production of a polymer as a by-product for reducing the operating time, and dramatically improves the oligomerization process.

In addition, the method of oligomerization from olefins of the present invention can easily produce oligomers having a high yield without using an additional step of washing process equipments in the process step by suppressing the production of polymers which are problematic in the process by using specific additives .

The object of the present invention is to provide a polymer which is a by-product, which causes problems such as reducing the operating time of the process equipment due to clogging of process equipment during oligomerization of olefins and cleaning of process equipment, The present invention provides a method for oligomerization of an olefin using an additive,

Introducing a transition metal source and a heteroatomic ligand or an oligomerization catalyst prepared therefrom into the reactor,

Adding an additive which is a hydrocarbon compound having an unsaturated bond, and

And introducing olefin.

The method for oligomerization of olefins of the present invention is different from the above olefins and includes a hydrocarbon compound having at least one unsaturated bond as an additive to inhibit the production of byproducts such as polymers and waxes produced during the oligomerization of olefins, .

That is, byproducts such as secondary polymers, which are not flowable, are deposited in the process equipment during the oligomerization of olefins, which can reduce the operating time of process equipment and even cause severe Causing problems.

Therefore, the present inventors have found that by-products such as the secondary polymer produced during the olefin oligomerization process are different from the olefin, and that by-products are formed by adding one or more specific additives which are hydrocarbon compounds having at least one unsaturated bond And the problem of the above-mentioned process is remarkably improved, thereby completing the present invention.

The second polymer produced in the olefin oligomerization process according to the present invention is generally referred to as a polymer which, unlike the first polymer that is suspended in the process and discharged at the time of discharge, does not discharge in the process but remains in the process facility and causes problems in the process operation.

The process according to the present invention may be carried out in any order regardless of the order. Preferably, the inside of the reactor is purged with a gas such as olefin, and the first and second steps are followed by the third step.

The olefin described in the present invention may be a single or a mixture, and the additive of the present invention should be a compound different from the oligomerized olefin.

Also, the additives described in the present invention should have at least one unsaturated bond, and these compounds may be used singly or as a mixture of two or more.

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

The hydrocarbon compound according to one embodiment of the present invention may be preferably a cyclic compound, and the cyclic compound may be a cycloalkene or cycloalkene which is an aliphatic cyclic compound.

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.

The hydrocarbon compound, ring compound described in the present invention means both substituted or unsubstituted, unless otherwise specified.

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

The additive according to one embodiment of the present invention is preferably a substituted or unsubstituted cycloalkene; Substituted or unsubstituted cycloalkyne; A substituted or unsubstituted alkene; Or substituted or unsubstituted alkyne.

More preferably, the additive according to one embodiment of the present invention may be represented by the following formulas (1) to (4).

[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

(In the formulas (1) to (4)

A represents ^{-C (R 9) (R 10} ) - , and

Z is ^{-C (R 17) (R 18} ) - , and

는 이중결합 또는 단일결합이며,

Is a double bond or a single bond,

R ¹ to R ³ , R ⁶ to R ¹⁰ and R ¹¹ to R ¹⁸ independently of one another are hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl,

가 이중결합인 경우 존재하지 않거나,

가 단일결합인 경우 서로 독립적으로 수소, 할로겐, 하이드로카빌, 치환된 하이드로카빌, 헤테로하이드로카빌 또는 치환된 헤테로하이드로카빌이며;R ⁴ and R ⁵ is

Is not present when it is a double bond,

Are independently of each other hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl when they are single bonds;

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 contain a fused ring, or (C1-C3) connected as an alkylene containing no may form an alicyclic ring, R ²¹ to R ²⁶ and R ³¹ independently of one another are hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl,

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

Preferably, formula (1) according to one embodiment of the present invention may be represented by the following formulas (11) to (13).

(11)

[Chemical Formula 12]

[Chemical Formula 13]

[In the above formulas (11) and (13)

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

는 이중결합 또는 단일결합이며,

Is a double bond or a single bond,

and s is an integer of 0 to 2.]

Preferably, the additive according to one embodiment of the present invention may be represented by the following formulas (21) to (24).

 [Chemical Formula 21]

[Chemical Formula 22]

(23)

≪ EMI ID =

[In the above formulas 21 to 23,

R ¹ , R ⁶ , R ^1a , R ^2a , R ^4a To R ^6a, R ¹² and R ¹⁶ independently represent hydrogen, deuterium, halogen, (C1-C10) alkyl, (C2-C10) alkenyl, (C2-C10) alkynyl, (C1-C10) alkoxy, (C6- C20) aryl, (C6-C20) aryloxy, (C1-C10) alkoxycarbonyl, (C1-C10) alkyl-carbonyl-oxy, (C2-C10) alkenyl-carbonyl-oxy, (C2-C10) alkynyl carbonyl (C3-C7) cycloalkyl , (C3-C7) heterocycloalkyl , (C1-C10) alkylsilyl, (C6-C20) arylsilyl, (C2-C10) alkenylsilyl, (C2-C10) alkynylsilyl or (C3-C20) heteroaryl.]

Preferably, R ¹ , R ⁶ , R ^1a , R ^2a , and R ^4a in Formulas 21 to 23 according to an embodiment of the present invention To R ^6a, R ¹² and R ¹⁶ are independently from each other hydrogen, (C1-C10) alkyl or (C2-C10) alkenyl can be ^{imidazol, R 1, R 6, R} 1a, R 2a, R 4a R ^6a , R ¹² and R ¹⁶ are independently of each other hydrogen, (C 1 -C 7) alkyl or (C 2 -C 7) alkenyl. Preferably, R ¹ to R ¹⁰ and R ¹¹ to R ¹⁸ in the general formulas (1) and (2) according to an embodiment of the present invention are independently hydrogen, (C 1 -C 10) alkyl, (C 2 -C 10) alkenyl, (C1-C10) alkynyl, (C1-C10) alkoxy, (C6-C20) aryl, (C6-C20) aryloxy , (C3-C7) cycloalkyl , (C3-C7) heterocycloalkyl , (C1-C10) alkylsilyl, (C6-C20) arylsilyl, (C2-C10) alkenylsilyl, (C2-C10) alkynylsilyl or (C3-C20) heteroaryl, and is preferably hydrogen, (C1-C10) alkyl, (C2-C10) alkenyl, (C2- (C1-C10) alkyl, (C2-C10) alkenyl or (C2-C10) alkynyl in view of the reaction effect, more preferably hydrogen, (C2-C7) alkenyl or (C2-C7) alkynyl.

In the formula (3), R ²¹ to R ²⁶ independently represent hydrogen, (C 1 -C 10) alkyl, (C 2 -C 10) alkenyl, (C 2 -C 10) alkynyl, (C1-C10) alkoxy or (C6-C20) aryl, preferably hydrogen, (C1-C10) alkyl or .

In formula (4), R ³¹ independently represents hydrogen, halogen, (C 1 -C 10) alkyl, (C 2 -C 10) alkenyl, (C 2 -C 10) alkynyl, (C2-C10) alkenyloxy, (C2-C10) alkenylcarbonyloxy, (C2-C10) arylcarbonyloxy , C10) alkynylcarbonyloxy, (C3-C7) cycloalkyl , (C3-C7) heterocycloalkyl , (C1- (C6-C20) arylsilyl, (C2-C10) alkenylsilyl, (C2-C10) alkynylsilyl or (C3-C20), and 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) alkyl-carbonyl-oxy, (C2-C10) alkenyl-carbonyl-oxy, (C2-C10) alkynyl-carbonyl-oxy, (C3 -C7) cycloalkyl , (C3-C7) heterocycloalkyl , (C1-C10) alkylsilyl, (C6-C20) arylsilyl, (C2-C10) alkenylsilyl, (C2-C10) alkynylsilyl or May be (C3-C20) may be a heteroaryl group, preferably R ³¹ and R ³² are independently (C1-C10) alkyl with one another.

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, per mol of the transition metal of the oligomerization catalyst.

&Quot; Hydrocarbyl "or" heterohydrocarbyl "as used in the present invention means a radical having one bonding position derived from a hydrocarbon or a heterohydrocarbon, and" hydrocarbylene " And the meaning of hetero means that carbon is substituted by one or more heteroatoms selected from O, S and N atoms.

Refers to a group or moiety having one or more substituents attached to the structural or structural skeleton of a moiety or moiety, and includes, but is not limited to, a moiety or moiety having one or more substituents such as deuterium, hydroxy, halogen, (= O), thio (= S), alkyl, haloalkoxy, alkenyl, alkynyl, aryl, arylalkyl, cycloalkyl, cycloalkylalkyl, cycloalkenyl, amino, alkylamino, di Substituted by one or more substituents selected from alkyl, alkoxy, alkylthio, alkylamino, heteroaryl, heterocyclylalkyl, heteroarylalkyl and heterocycloalkyl.

As used herein, the term "alkene " means a straight-chain, branched or cyclic hydrocarbon containing from 2 to 10 carbon atoms and at least one carbon to carbon double bond in a per senable range.

The term "alkyne " as used in the present invention means a straight chain, branched or cyclic hydrocarbon containing 2 to 10 carbon atoms and at least one carbon to carbon triple bond. The alkenes and alkynes described in the present invention have 2 to 10 Of carbon atoms, preferably 2 to 7 carbon atoms.

&Quot; Cycloalkyl "as used herein refers to a non-aromatic monocyclic or multicyclic ring system having from 3 to 10 carbon atoms, wherein" heterocycloalkyl " The cycloalkyl and heterocycloalkyl described in the present invention as a substituted or unsubstituted nonaromatic 3 to 15 membered ring consisting of 1 to 5 heteroatoms selected from phosphorus, oxygen and sulfur is preferably a 3- to 10-membered ring, It can be a seven-member ring.

The substituents comprising the "alkyl", "alkoxy" and other "alkyl" moieties described in the present invention include both straight and branched forms and are those having 1 to 10 carbon atoms, preferably 1 to 7 carbon atoms, more preferably 1 Lt; / RTI > to 5 carbon atoms.

"Aryl" according to the present invention is an organic radical derived from aromatic hydrocarbons by the removal of one hydrogen, in which each ring is optionally substituted by a single or fused ring containing from 4 to 7, preferably 5 or 6 ring atoms A ring system, and 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.

"Heteroaryl" as used herein includes 1-4 heteroatoms selected from B, N, O, S, P (= O), Si and P as aromatic ring backbone atoms, and the remaining aromatic ring backbone atoms are carbon Means a 5 to 6 membered monocyclic heteroaryl and a polycyclic heteroaryl condensed with at least one benzene ring and may be partially saturated. The heteroaryl in the present invention also includes a form in which one or more heteroaryl is connected to a single bond.

The term "alkenyl ", alone or as part of another group described in the present invention, means a straight, branched or cyclic hydrocarbon radical containing from 2 to 10 carbon atoms and at least one carbon to carbon double bond. More preferred alkenyl radicals are lower alkenyl radicals having from 2 to about 7 carbon atoms. The most preferred lower alkenyl radical is a radical having from 2 to about 5 carbon atoms. The alkenyl group 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 cis and trans orientation, or alternatively, radicals having an E and Z orientation.

The term "alkynyl ", alone or as part of another group described in the present invention, means a straight, branched or cyclic hydrocarbon radical containing from 2 to 10 carbon atoms and at least one carbon to carbon triple bond. More preferred alkynyl radicals are lower alkynyl radicals having from 2 to about 7 carbon atoms. Most preferred is a lower alkynyl radical having from 2 to about 5 carbon atoms. Examples of such radicals include propargyl, butynyl, and the like. The alkynyl group may also be substituted at any available attachment point.

"Cycloalkyl" as used in the present invention means a non-aromatic monocyclic or multicyclic ring system having from 3 to 10 carbon atoms, and the ring ring includes, but is not limited to, cyclopropyl, cyclobutyl , Cyclopentyl, and cyclohexyl. Examples of polycyclic cycloalkyl groups include perhydronaphthyl, perhydroindenyl, and the like; Branched polycyclic cycloalkyl groups include adamantyl and norbornyl and the like.

"Heterocycloalkyl" as used herein means a substituted or unsubstituted, non-aromatic 3 to 15 membered ring radical consisting of carbon atoms and from 1 to 5 heteroatoms selected from nitrogen, phosphorus, oxygen and sulfur and includes heterocycloalkyl The radical may be a fused, bridged or cyclic, bicyclic or tricyclic ring system which may include a spiro ring system, and the nitrogen, phosphorus, carbon, oxygen or sulfur atom in the heterocyclic ring radical may be in various oxidation states If desired. In addition, the nitrogen atom can optionally be quaternized.

The alicyclic ring described in the present invention means 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 catalysts of the present invention may be prepared by direct use or commercially available oligomerization catalysts, or may use constituents capable of producing oligomerization catalysts, that is, transition metal sources and heteroatoms.

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 organometallic, wherein the transition metal of the transition metal source is a Group 4, , Or a transition metal of Group 6, and may specifically be chromium, molybdenum, tungsten, titanium, tantalum, vanadium or zirconium, preferably chromium.

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

Wherein each of R ⁴¹ to R ⁴⁵ is independently hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl.

The organic ligand may preferably be an acetylacetonate ligand represented by the following formula (31).

(31)

(Formula 31)

R ⁴⁶ to R ⁴⁸ each independently represent hydrogen, halogen, (C 6 -C 20) aryl, (C 6 -C 20) aryl (C 1 -C 10) alkyl, (C 1 -C 10) (C2-C10) alkenyl, (C2-C10) alkenyl, (C2-C10) alkynyl, (C2-C10) alkynylcarbonyloxy, (C3-C7) cycloalkyl, (C1-C10) alkylcarbonyloxy, C10) alkylsilyl, (C2-C10) alkenylsilyl, (C2-C10) alkynylsilyl substituted with fluorine, (C6-C20) arylsilyl, (C3-C20) heteroaryl or 5 to 7 membered heterocycloalkyl;

The aryl, aralkyl, alkyl, aralkenyl, alkenyl, aralkynyl, alkynyl, alkoxy, aryloxy , cycloalkyl , heteroaryl and heterocycloalkyl of R ⁴⁶ to R ⁴⁸ are independently selected from the group consisting of (C1- (C2-C10) alkenyl, (C2-C10) alkynyl, (C1-C10) alkoxy, (C6-C20) aryl, (C6-C20) aryloxy and halogen. .)

Preferably, R ⁴⁶ and R ⁴⁷ in Formula 31 may each independently be hydrogen, halogen or halo (C 1 -C 10) alkyl, and R ⁴⁸ may be hydrogen or (C 1 -C 10) alkyl.

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

Specific examples of the transition metal source include chromium (III) chloride, chromium (III) naphthenate, chromium (III) 2-ethylhexanoate, chromium (III) acetylacetonate, chromium 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 selected from the group consisting of arsenic, antimony, oxygen, bismuth, Nitrogen, C is a linking group between B and D, and R are the same or different and are each independently selected from hydrocarbyl, heterohydrocarbyl, substituted hydrocarbyl and substituted heterohydrocarbyl groups, n and m may each be determined to be each valence and oxidation state of B or D, preferably B and D are independently phosphorus, and C is a linking group between B and D, (Where R 'is alkyl) and R is the same or different and is independently selected from hydrocarbyl, heterohydrocarbyl, substituted hydrocarbyl, and substituted heterohydrocarbyl groups , And n and m may be determined to be each valence and oxidation state of B or D, respectively.

The heteroatom ligand may be a P-C-C-P skeleton structure represented by the following formula (32) or a P-N-P skeleton structure represented by the following formula (33), but is not limited thereto.

(32)

(33)

(In the above 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 with a hydrocarbylene, a substituted hydrocarbylene, a heterohydrocarbylene, or a substituted heterohydrocarbylene, Can be formed.

In the formulas (32) and (33), R ⁵¹ to R ⁵⁴ are each independently selected from the group consisting of (C 6 -C 20) aryl, (C 6 -C 20) C6-C20) aralkyl (C2-C10) alkynyl, (C1-C10) alkyl, (C2-C10) alkenyl, (C2-C10) alkynyl, (C1-C10) alkoxy, (C6-C20) aryloxy , (C1-C10) alkoxycarbonyl, (C1-C10) alkyl-carbonyl-oxy, (C2-C10) alkenyl-carbonyl-oxy, (C2-C10) alkynyl-carbonyl-oxy, amino-carbonyl, (C1-C10 (C2-C10) alkenylcarbonylamino, (C2-C10) alkynylcarbonylamino, (C3-C7) cycloalkyl , thio (C1- Alkenyl, thio (C2-C10) alkynyl, (C1-C10) alkylsilyl, (C2-C10) alkenylsilyl, Each (C2-C10) alkynyl, silyl, is (C6-C20) arylsilyl, (C3-C20) heteroaryl, a 5-to 7-membered heterocycloalkyl or -NR ⁶¹ R ⁶² a, R ⁶¹ and R ⁶² independently (C2-C10) alkenyl, (C2-C10) alkynyl, (C6-C20) aryl, di Di (C2-C10) alkynylamino;

R ⁵⁵ and R ⁵⁶ are each independently selected from the group consisting of (C 6 -C 20) aryl, (C 6 -C 20) aryl (C 6 -C 20) alkyl, (C 6 -C 20) (C2-C10) alkynyl, (C3-C20) heteroaryl, 5 to 7 membered heteroaryl, (C 1 -C 10) alkoxycarbonyl, (C 1 -C 10) alkylcarbonyloxy, (C 2 -C 10) alkenylcarbonyloxy, (C 1 -C 10) alkoxycarbonyl, (C2-C10) alkynylcarbonyloxy, aminocarbonyl, (C1-C10) alkylcarbonylamino, (C2-C10) alkenylcarbonylamino, (C2-C10) alkynylamino, (C1-C10) alkylsilyl, (C2-C10) alkenylsilyl, carbonyl silyl or (C6-C20) aryl, or silyl group, R ⁵⁵ and R ⁵⁶ are connected to a (C3-C10) alkylene or (C3-C10) alkenylene may form a ring;

Examples of the above-mentioned R ⁵¹ to R ⁵⁴ include aryl, aralkyl, aralkenyl, aralkynyl, alkyl, alkenyl, alkoxy, aryloxy, alkoxycarbonyl, alkylcarbonyloxy, alkenylcarbonyloxy, alkynylcarbonyloxy , cycloalkyl, heteroaryl, heterocycloalkyl, and R ⁵⁵ and the aryl of R ^56, aralkyl, aralkyl, alkenyl, aralkyl, alkynyl, alkyl, alkenyl, cycloalkyl, heteroaryl, heterocycloalkyl, alkoxy, aryloxy Alkoxycarbonyl, alkoxycarbonyl, alkylcarbonyloxy, alkenylcarbonyloxy, alkynylcarbonyloxy, aminocarbonyl, alkylcarbonylamino, alkenylcarbonylamino, alkynylcarbonylamino, dialkylamino, dialkenylamino (C1-C10) alkenyl, (C2-C10) alkynyl, (C1-C10) alkoxy, (C2-C10) alkenylamino, di (C2-C10) alkynylamino, and halogen May be further substituted.

Preferably, R ⁵¹ to R ⁵⁴ in the general formulas (32) and (33) are each independently (C 6 -C 20) aryl;

R ⁵⁵ and R ⁵⁶ may each independently be (C 1 -C 10) alkyl.

In the formulas (32) and (33), specifically, R ⁵¹ to R ⁵⁴ each represent a phenyl group, a benzyl group, a biphenyl group, a naphthyl group, an anthracenyl group, a mesityl group, a xylyl group, a methyl group, an ethyl group, Propyl, n-butyl, t-butyl, butenyl, butynyl, methylphenyl, ethylphenyl, methoxyphenyl, ethoxyphenyl, isopropylphenyl, isopropoxyphenyl, But are not limited to, methoxy, ethoxy, phenoxy, tolyloxy, dimethylaminophenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, ethylcyclohexyl or isopropylcyclohexyl, dimethylamino, Silyl and dimethylhydrazyl;

R ⁵⁵ and R ⁵⁶ are each independently selected from the group consisting of methyl, ethyl, ethenyl, ethynyl, n-propyl, i-propyl, propenyl, propynyl, n-butyl, R ⁵⁵ and R ⁵⁶ are connected to each other by a propylene, butylene, pentylene or butenylene group to form a 5- to 7-membered monocyclic or bicyclic A ring can be formed.

PCCP ligand of the skeleton of the general 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-isopropyl-phenyl) 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-dimethylamino-phenyl Min) ₂ P-CH (methyl) CH (methyl) -P (4-dimethylaminophenyl) _2, (4-ethyl-cyclohexyl) ₂ P-CH (methyl) CH (methyl) -P (4-ethyl-cyclohexyl) _2, (2-methoxyphenyl) ₂ P-CH (methyl) CH (methyl) - P (2-methoxyphenyl) _2, (2-phenyl) ₂ P-CH (methyl) CH (methyl) -P (2- Ethoxyphenyl) _2, (2-dimethylamino-phenyl) ₂ P-CH (methyl) CH (methyl) -P (2-dimethylaminophenyl) _2, (2-ethyl-cyclohexyl) ₂ P-CH (methyl) CH ( methyl) -P (2- ethyl-cyclohexyl) _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- profile Phil) 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) but can be selected from the _second, the But it is not limited.

The ligands of the PNP skeleton structure of Formula 33 are represented by (phenyl) 2PN (methyl) P (phenyl) 2, (phenyl) 2PN (pentyl) Phenyl) 2PN ((p-methoxyphenyl) P (phenyl) 2, (phenyl) 2PN (pt butylphenyl) 2 (phenyl) 2PN (methyl) P (ethyl) 2, (ethyl) 2PN (isopropyl) 2PN (Si (CH3) P (phenyl) 2 (phenyl) 2P (= ethyl) (phenyl) PN (methyl) P (ethyl) (Isopropyl) P (phenyl) 2, (o-methylphenyl) 2PN (isopropyl) P (phenyl) 2, (phenyl) 2PCH2CH2P (Phenyl) 2PN (benzyl) P (phenyl) 2, (phenyl) 2PN (1-cyclohexylethyl) P (phenyl) 2PNCH2CH2CH2Si (OMe3) P (phenyl) 2, (phenyl) 2PN (cyclohexyl) P (phenyl) 2, (phenyl) 2PN (2-methylcyclohexyl) (2-naphthyl) 2PN (methyl) P (2-naphthyl) 2, (p- P (2-thiophenyl) 2, (phenyl) 2PN (methyl) P (methylphenyl) P (phenyl) 2P (methyl) P (phenyl) 2P (methyl) P (phenyl) = S) N (isopropyl) P (phenyl) 2, but is not limited thereto.

Heteroatomic ligands constituting the oligomerization catalyst of olefins according to the present invention can be prepared using a variety of methods known to those skilled in the art.

The oligomerization catalyst of olefins according to the present invention may be mononuclear or binuclear, and specifically ML ¹ (L ² ) _p (X) _q or M ₂ X ¹ ₂ L ¹ ₂ (L ² ) _y (X) _{z ,} can be displayed in, and wherein M is a transition metal, and L ¹ is a hetero ligand, L ² is an organic ligand, and is a halogen independently X and X ^1, and p is 0 or an integer of 1 or more, q is ( Y is an integer of 2 or more, and z is an integer of -y-2 (oxidation number of 2 x M).

Preferably, the oligomerization catalyst according to one embodiment of the present invention may be represented by the following general formula (34) or (35), but is not limited thereto.

≪ EMI ID =

(25)

(In the above formulas 24 to 25,

R ⁴⁶ to R ⁴⁸ are each independently selected from the group consisting of hydrogen, halogen, (C 6 -C 20) aryl, (C 6 -C 20) aryl (C 1 -C 10) alkyl, (C2-C10) alkenyl, (C2-C10) alkenyl, (C2-C10) alkynyl, (C2-C10) alkynylcarbonyloxy, (C3-C7) cycloalkyl, (C1-C10) alkylcarbonyloxy, C10) alkylsilyl, (C2-C10) alkenylsilyl, (C2-C10) alkynylsilyl, (C6-C20) arylsilyl, (C3-C20) heteroaryl or 5 to 7 membered heterocycloalkyl;

Wherein R ^46, R ⁴⁷ and the aryl of R ^48, aralkyl, alkyl, aralkyl, alkenyl, alkenyl, aralkyl, alkenyl, alkynyl, alkoxy, aryloxy, cycloalkyl, heteroaryl and heterocycloalkyl is (C1-C10 (C6-C60) alkoxy, (C6-C60) aryl, (C6-C60) aryloxy and halogen, Lt; / RTI >

R ⁵¹ to R ⁵⁴ are each independently selected from the group consisting of (C 6 -C 20) aryl, (C 6 -C 20) aryl (C 6 -C 20) alkyl, (C 6 -C 20) 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, (C2-C10) alkenylcarbonylamino, (C2-C10) alkynylcarbonylamino, (C3-C7) cycloalkyl , thio (C1-C10) alkynyl, (C1-C10) alkylsilyl, (C2-C10) alkenylsilyl, (C 2 -C 10) alkynylsilyl, (C 6 -C 20) arylsilyl, (C 3 -C 20) heteroaryl, 5- to 7-membered heterocycloalkyl or -NR ²¹ R ²² , R ²¹ and R ²² are each independently (C2-C10) alkenyl, (C2-C10) alkynyl, (C6-C20) aryl, di Di (C2-C10) alkynylamino;

R ⁵⁵ and R ⁵⁶ are each independently selected from the group consisting of (C 6 -C 20) aryl, (C 6 -C 20) aryl (C 6 -C 20) alkyl, (C 6 -C 20) (C2-C10) alkynyl, (C3-C20) heteroaryl, 5 to 7 membered heteroaryl, (C 1 -C 10) alkoxycarbonyl, (C 1 -C 10) alkylcarbonyloxy, (C 2 -C 10) alkenylcarbonyloxy, (C 1 -C 10) alkoxycarbonyl, (C2-C10) alkynylcarbonyloxy, aminocarbonyl, (C1-C10) alkylcarbonylamino, (C2-C10) alkenylcarbonylamino, (C2-C10) alkynylamino, (C1-C10) alkylsilyl, (C2-C10) alkenylsilyl, (C2-C10) alkynyl, silyl or (C6-C20) aryl, or silyl group, R ⁴⁵ and R ⁴⁶ are connected to a (C3-C10) alkylene or (C3-C10) alkenylene may form a ring;

Examples of the above-mentioned R ⁵¹ to R ⁵⁴ include aryl, aralkyl, aralkenyl, aralkynyl, alkyl, alkenyl, alkoxy, aryloxy, alkoxycarbonyl, alkylcarbonyloxy, alkenylcarbonyloxy, alkynylcarbonyloxy , cycloalkyl, heteroaryl, heterocycloalkyl, and R ⁵⁵ and the aryl of R ^56, aralkyl, aralkyl, alkenyl, aralkyl, alkynyl, alkyl, alkenyl, cycloalkyl, heteroaryl, heterocycloalkyl, alkoxy, aryloxy Alkoxycarbonyl, alkoxycarbonyl, alkylcarbonyloxy, alkenylcarbonyloxy, alkynylcarbonyloxy, aminocarbonyl, alkylcarbonylamino, alkenylcarbonylamino, alkynylcarbonylamino, dialkylamino, dialkenylamino (C1-C10) alkenyl, (C2-C10) alkynyl, (C1-C10) alkoxy, (C2-C10) alkenylamino, di (C2-C10) alkynylamino, and halogen Lt; / RTI > may be further substituted;

X is halogen; And

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

Preferably, each of R ⁴⁶ to R ⁴⁸ is independently hydrogen, (C 1 -C 10) alkyl or halo (C 1 -C 10) alkyl, and R ⁵¹ to R ⁵⁴ each independently represents (C 6 -C 20) aryl ; R ⁵⁵ and R ⁵⁶ are each independently (C 1 -C 10) alkyl, or R ⁵¹ to R ⁵⁴ are each independently (C 6 -C 20) aryl; R ⁵⁵ and R ⁵⁶ are each independently (C 1 -C 10) alkyl, and a is 0.

The promoter contained in the olefin oligomerization catalyst composition according to an embodiment of the present invention may be an organoaluminum compound, an organoaluminoxane, an organoboron compound, or a mixture thereof.

The organoaluminum compound according to one embodiment of the present invention is an organoaluminum compound according to one embodiment of the present invention comprises AlR ₃ wherein each R is independently selected from the group consisting of (C 1 -C 12) alkyl, (C 2 -C 10) alkenyl, (C 2 -C 10) alkynyl, Halogen or a compound of LiAlH ₄ or the like.

The organoaluminum compound according to the present invention can be synthesized by reacting trimethylaluminum (TMA), triethylaluminum (TEA), triisobutylaluminum (TIBA), tri-n-octylaluminum, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum chloride, Diethyl aluminum chloride, aluminum isopropoxide, ethyl aluminum sesquichloride, and methyl aluminum sesquichloride.

Organoaluminoxanes according to one embodiment of the present invention are well known in the art as oligomeric compounds that can be prepared by adding water to water and an alkylaluminum compound such as trimethylaluminum in the art. The resulting aluminoxane oligomer compound may be linear, cyclic, cage or a mixture thereof.

Organic aluminoxanes include alkylaluminoxanes such as methylaluminoxane (MAO), ethylaluminoxane (EAO), tetraisobutylaluminoxane (TIBAO) and isobutylaluminoxane (IBAO) as well as modified alkylaluminoxanes, For example, modified methylaluminoxane (MMAO). The modified methyl aluminoxane (manufactured by Akzo Nobel) contains a mixed alkyl group such as isobutyl or n-octyl group in addition to the methyl group.

 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 .

The organoboron compound as a promoter according to an embodiment of the present invention may be selected from boroxine, NaBH ₄ , triethylborane, triphenylborane, triphenylborane ammonia complex, tributylborate, triisopropylborate, tris (pentafluorophenyl ) Borane, triethyl (tetrapentafluorophenyl) borate, dimethylphenylammonium (tetrapentafluorophenyl) borate, diethylphenylammonium (tetrapentafluorophenyl) Borate or ethyldiphenylammonium (tetrapentafluorophenyl) borate, and these organoboron compounds can be used as a mixture with the organoaluminum compounds described above.

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

The present invention also provides a process for preparing oligomers from olefins in the presence of the olefin oligomerization catalyst composition of the present invention.

The oligomerization catalysts, cocatalysts and additives, which are the individual components of the olefinic oligomerization catalyst composition disclosed in the present invention, can be compounded sequentially or simultaneously in any order in the presence of a solvent to provide an olefin oligomerization catalyst composition. The mixing of the components of each catalyst composition can be carried out at a temperature of -20 to 250 캜 and the presence of the olefin during the mixing of the catalyst components generally provides a protective effect and can provide improved catalyst performance. A more preferable temperature range is 20 to 100 占 폚.

Oligomers, especially 1-hexene or 1-octene, prepared from olefins, which are the reaction products disclosed in the present invention, can be prepared by reacting an olefin according to the invention, in particular ethylene, with an oligomerization catalyst in the presence of an inert solvent, Reaction, a two-phase liquid / liquid reaction, a bulk phase reaction in which the product olefin acts as the main medium, or a gaseous reaction.

The method for preparing oligomers 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 aliphatic hydrocarbons. The aliphatic hydrocarbon is a saturated aliphatic hydrocarbon, A linear saturated aliphatic hydrocarbon represented by C _n H _{2n +2} (wherein n is an integer of 1 to 15), an alicyclic saturated aliphatic hydrocarbon represented by C _m H _2m (wherein m is an integer of 3 to 8) And saturated aliphatic hydrocarbons in which one or two or more lower alkyl groups having 1 to 3 carbon atoms are substituted. Specific examples thereof include hexane, heptane, octane, nonene, decane, undecane, dodecane, tetradecane, 2,2-dimethylpentane, 2,3-dimethylpentane, Trimethyl pentane, 2-methylhexane, 3-methylhexane, 2,2-dimethylhexane, 2,4-dimethylhexane, 2,5-dimethyl But are not limited to, hexane, 3,4-dimethylhexane, 2-methylheptane, 4-methylheptane, cyclohexane, methylcyclohexane, ethylcyclohexane, isopropylcyclohexane, Cyclohexane, but are not limited thereto.

The oligomerization reaction according to the preparation method of the present invention can 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, bar, preferably at atmospheric pressure to a pressure of 80 bar, more preferably at atmospheric pressure to 60 bar.

In a preferred embodiment of the present invention, the oligomerization reaction conditions include, for example, 1-hexene yield from ethylene of not less than 50% by mass, preferably not less than 70% by mass. In this case, the yield means the number of grams of 1-hexene formed per 100 g of the total reaction product formed.

In a preferred embodiment of the present invention, the oligomerization reaction conditions can be, for example, a yield of 1-octene from ethylene of not less than 30% by mass, preferably not less than 50% by mass. In this case, the yield means the number of grams of 1-octene formed per 100 g of the total reaction product formed.

In the process for preparing the oligomer from the 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 comprise a reactor, an olefin reactor in the reactor, an inlet for the catalyst composition, a line for draining the oligomerization reaction product from the reactor, and at least one separator for separating the oligomerization reaction product, The composition may comprise transition metal sources and heteroatomic ligands or oligomerization catalysts, cocatalysts and additives made therefrom with the olefinic oligomerization catalyst compositions disclosed herein.

The method of preparing an oligomer from olefins according to an embodiment of the present invention improves the problems raised in the prior art process by using the olefin oligomerization catalyst composition of the present invention and can easily produce 1-hexene, 1-octene Or a mixture thereof.

The following examples illustrate the effects of the present invention in detail. However, the following examples are intended to illustrate the present invention and are not intended to limit the scope of the present invention.

[ Example  One] Oligomerization  Preparation of Catalyst A

Prepared in Example 2 Bis - [(S, S) - ( phenyl) ₂ PCH (methyl) CH (methyl) P (phenyl) ₂ dichloride (μ- chloride) chromium] 1 g (1.7 mmol) of dibasic After dissolving in 100 mL of methane, 0.39 g (1.7 mmol) of sodium hexafluoroacetylacetonate was gradually added. The reaction was stirred for an additional 3 hours and then filtered using a glass filter. The filtered liquid was stripped of the volatiles in vacuo to give a dried dark green solid. And washed with 50 mL of hexane twice to obtain 1.22 g (yield 95%) of the title compound.

Example 2 Preparation of the oligomerization catalyst B (bis - [(S, S) - ( phenyl) ₂ PCH (methyl) CH (methyl) P (phenyl) ₂ dichloride (μ- chloride) chromium] ([CrCl _{2 (μ-Cl) {(} P, P) -k2- (S, S) - ((Ph) 2 P (Me) CH-CH (Me) P (Ph) 2)} Preparation of] ₂₎

Three tetrahydrofuran trichloride, chromium _{(CrCl 3 (THF) 3)} 1.1 g (3.0 mmol) of dichloride was dissolved in methane 100 mL (S, S) - ( phenyl) ₂ PCH (methyl) CH (methyl) P (phenyl ) ₂ ligand compound (1.28 g, 3.0 mmol) was dissolved in 50 mL of dichloromethane, followed by slow addition. After the reaction was stirred for 3 hours, the volatiles were removed by vacuum, and 100 mL of MCH (methylcyclohexane) was added dropwise to obtain a blue solid by precipitation. And washed twice with 100 mL of MCH (methylcyclohexane) to obtain 1.58 g (yield 90%) of the title compound.

[ Example  3 to 12 and Comparative Example  1 to 3] ethylene Oligomerization  reaction

2000 mL stainless steel pressure reactor was cleaned 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. 3.1 mg (5.3 μmol-Cr) of the oligomerization catalyst described in the following Table 1 and additives dissolved in 10 ml of methylcyclohexane were prepared in a glove box, and then taken out and injected into the reactor. The pressure reactor was charged with 20 bar of ethylene and stirred at a stirring speed of 250 rpm. After 120 minutes, the ethylene feed to the reactor was stopped, the stirring was stopped to stop the reaction and the reactor was cooled to below 10 < 0 > C.

Ethanol was injected into the liquid contained in the reactor after releasing excess ethylene in the reactor. The quenched product was analyzed by GC-FID. The remaining organic layer was filtered to separate the solid wax / polymer product. These solid products were dried overnight in a 100 < 0 > C oven, and the results were as shown in Table 1 below.

The results of the reaction are shown in Table 1 below.

[ Example  13 and Comparative Example  3] ethylene Oligomerization  reaction

Examples 3 to 12 were repeated except that 20 umol of Cr (acac) ₃ was used as a transition metal instead of the oligomerization catalysts A and B used in Examples 3 to 12 and Comparative Examples 1 to 2, and 2eq of PNP ligand was used as a heteroatomic ligand. And Comparative Examples 1 and 2, the oligomerization reaction of ethylene was carried out. The results are shown in Table 1 below.

catalyst additive LAO yield
(C6 + C8, g) LAO yield
(C6 / C8) Polymer ^c Activity (Kg / mol-Cr cat hr) Ratio ^a STD to Ratio comparison ^b Kinds 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-hexyne 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 alpha-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 / STD ratio value of the same catalyst in each condition

- Since the amount of polymer produced varies depending on the amount of LAO produced, the amount of polymer is compared with the activity divided by the activity. That is, in Examples 3 to 10, STD Ratio values were used for Comparative Example 1, STD Ratio values for Comparative Examples 2 to 12, and STD Ratio values for Comparative Example 3.

c 1 ^st polymer: Pollutant in solvent is discharged as solvent, 2 ^nd polymer: Polymer which has no fluidity in solvent and needs additional high temperature cleaning

d cat: A simple mixture of Cr (acac) and PNP ligand with MCH without polymerization and isolation. Cr (acac) 3 20 umol, PNP ligand 2 eq, mMAO 3A 4 mmol, C2 20 bar, MCH 760 g, 120 min

The additives used in the present invention are as follows.

compound 1,3 CHD
(1,3-Cyclohexadiene)

1,4 CHD
(1,4-Cyclohexadiene)

Cyclohexene

2,3-Dimethyl-1,3-butadiene

3-hexyne

a-TP
(α-Terpinene)

g-TP
(γ-Terpinene)

Dipentene

DPCD
(1,3-Dicyclopentadiene)

alpha -phellandrene

As shown in Table 1, in Examples 3 to 18 in which the olefin oligomerization reaction was carried out by using a specific additive which is different from the olefin and olefin mixture used in the olefin oligomerization reaction and is a hydrocarbon compound having at least one unsaturated bond Shows a remarkable decrease in the amount of the secondary polymer produced. In comparison with the comparative example in which the additives are not included, it is possible to obtain remarkable results in which the amount of the secondary polymer is reduced by 90% or more.

The method of oligomerization of the olefin of the present invention, which is different from the olefin and olefin mixture used in the olefin oligomerization reaction and contains as a additive a hydrocarbon compound having at least one unsaturated bond, It is possible to remarkably suppress the production of by-products such as secondary polymers and waxes, to eliminate the necessity of washing the separate process equipment, and to reduce the operation time and the speed, and to produce oligomers efficiently from olefins.

Claims (18)

Introducing a transition metal source and a heteroatomic ligand or an oligomerization catalyst prepared therefrom into the reactor,
Adding an additive comprising a hydrocarbon compound having an unsaturated bond, and
RTI ID = 0.0 > of olefins. ≪ / RTI > The method according to claim 1,
Wherein the additive has a molecular weight of from 35 to 330 and a boiling point of from 50 캜 to 350 캜. The method according to claim 1,
Wherein the additive is a hydrocarbon compound having two or more double bonds. The method of claim 3,
Wherein the hydrocarbon compound is a cyclic compound. 5. The method of claim 4,
Wherein said cyclic compound is a compound having a double bond in the ring. 5. The method of claim 4,
Wherein the cyclic compound is a compound substituted with an alkyl. The method according to claim 1,
Wherein the additive is a substituted or unsubstituted cycloalkene, a substituted or unsubstituted cycloalkene, a substituted or unsubstituted alkene, or a substituted or unsubstituted alkyne. 8. The method of claim 7,
Wherein the additive is an oligomerization of olefins represented by the following general formulas (1) to (4).
[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

[In formulas (1) to (4)
A represents ^{-C (R 9) (R 10} ) - , and
Z is ^{-C (R 17) (R 18} ) - , and

Is a double bond or a single bond,
R ¹ to R ³ , R ⁶ to R ¹⁰ and R ¹¹ to R ¹⁸ independently of one another are hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl,
R ⁴ and R ⁵ is

Is not present when it is a double bond,

Are independently of each other hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl;
n is independently from 0 to 5,
When n and m are 1, R ³ and R ⁹ and R ¹³ and R ¹⁷ may be linked together with a (C 1 -C 3) alkylene with or without a fused ring to form an alicyclic ring,
R ²¹ to R ²⁶ and R ³¹ independently of one another are hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl,
R ³² is a halogenated hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl.) 9. The method of claim 8,
Wherein the formula (1) is represented by the following formulas (11) to (13).
(11)

[Chemical Formula 12]

[Chemical Formula 13]

[In the above formulas 11 to 13,
R ¹ to R ¹⁰ and R ^1a to R ^10a independently of one another are hydrogen, halogen hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl;

Is a double bond or a single bond,
and s is an integer of 0 to 2.] 10. The method of claim 9,
Wherein the additive is an oligomerization of olefins represented by the following general formulas (21) to (24).
[Chemical Formula 21]

[Chemical Formula 22]

(23)

≪ EMI ID =

[In the above formulas 21 to 24,
R ¹ , R ⁶ , R ^1a , R ^2a , R ^4a To R ^6a, R ¹² and R ¹⁶ independently represent hydrogen, deuterium, halogen, (C1-C10) alkyl, (C2-C10) alkenyl, (C2-C10) alkynyl, (C1-C10) alkoxy, (C6- C20) aryl, (C6-C20) aryloxy, (C1-C10) alkoxycarbonyl, (C1-C10) alkyl-carbonyl-oxy, (C2-C10) alkenyl-carbonyl-oxy, (C2-C10) alkynyl carbonyl (C3-C7) cycloalkyl , (C3-C7) heterocycloalkyl , (C1-C10) alkylsilyl, (C6-C20) arylsilyl, (C2-C10) alkenylsilyl, (C2-C10) alkynylsilyl or (C3-C20) heteroaryl.] 11. The method of claim 10,
R ¹ , R ⁶ , R ^1a , R ^2a , R ^4a Wherein R ^6a , R ¹² and R ¹⁶ are independently of each other hydrogen, (C 1 -C 10) alkyl or (C 2 -C 10) alkene. The method according to claim 1,
Wherein the additive is used in an amount of 1 to 1 x ¹⁰ < ⁶ > mol per mol of the transition metal of the oligomerization catalyst. The method of claim 1, wherein
Wherein the transition metal source is a transition metal inorganic salt, a transition metal organic salt, a transition metal coordination compound, or a complex of transition metal and organometallic olefin. The method according to claim 1,
Wherein the heteroatom ligand is a general formula _{(R) n BCD (R)} m , and, here, B and D are independently selected from phosphorus, arsenic, antimony, oxygen, bismuth, any one selected from sulfur, selenium and nitrogen, C Is a linking group between B and D, wherein R is the same or different and is independently selected from hydrocarbyl, heterohydrocarbyl, substituted hydrocarbyl and substituted heterohydrocarbyl groups, n and m are each independently selected from the group consisting of B or D ≪ / RTI > wherein each valence is determined to be in the valence state and in the oxidation state. The method according to claim 1,
Wherein said oligomerization catalyst is _{^{ML 1 (L 2) p (}} X) q or _{^{M 2 X 1 2 L 1 2}} (L 2) y (X) and _z, (formula M is a transition metal, L ¹ is a hetero ligand, L ² is an organic ligand, and X is a halogen, each independently, and X ^1, and p is 0 or an integer of 1 or more, q is an integer, y is an integer of 2 or more of (-p oxidation number of M), z is ( 2 x M) -y). ≪ / RTI > The method according to claim 1,
Wherein the process further comprises a cocatalyst. 17. The method of claim 16,
Wherein the cocatalyst is an organoaluminum compound, an organoaluminoxane, an organoboron compound or a mixture thereof. The method according to claim 1,
Wherein the olefin is ethylene and the oligomer is 1-hexene, 1-octene, or mixtures thereof.