KR20160123213A - Method for continuously preparing olefin oligomer - Google Patents

Abstract

The present invention relates to a continuous process for preparing olefin oligomers. The present invention provides a continuous process for the preparation of olefin oligomers which can exhibit high and stable catalytic activity and high selectivity for 1-hexene and 1-octene in a continuous oligomerization reaction of olefins.

Description

METHOD FOR CONTINUOUSLY PREPARING OLEFIN OLIGOMER [0002]

The present invention relates to a continuous process for preparing olefin oligomers, and more particularly, to a process for continuously producing olefin oligomers with improved efficiency using a catalyst system for olefin oligomerization.

This application claims the benefit of priority based on Korean Patent Application No. 10-2015-0053169 dated April 15, 2015, and Korean Patent Application No. 10-2015-0146843 dated October 21, 2015, and the Korean Patent Application The entire contents of which are incorporated herein by reference.

Linear alpha-olefins such as 1-hexene, 1-octene and the like are used as detergents, lubricants, plasticizers and the like. Especially, as a monomer for controlling the density of polymers in the production of linear low density polyethylene (LLDPE) Is used.

In the production of conventional linear low density polyethylene (LLDPE), alpha-olefins such as 1-hexene and 1-octene are added to form a branch in the polymer backbone together with ethylene to control the density. To allow copolymerization with the comonomer.

Therefore, there is a limit in that the cost of the comonomer is a large part of the manufacturing cost for the production of LLDPE having a high content of comonomer. Various attempts have been made to solve these problems.

In addition, since the application fields and the market sizes of the alpha-olefins are different depending on the type, the technology capable of selectively producing a specific alpha-olefin is commercially important. In this connection, there is a great deal of research on a catalyst system for producing 1-hexene or 1-octene through selective ethylene oligomerization.

Existing commercial production methods for producing 1-hexene or 1-octene include Shell Higher Olefin Process of Shell Chemical and Ziegler Process of Chevron Phillips, A wide range of alpha-olefins can be produced.

However, the method of preparing olefin oligomers using the existing catalyst system has a limitation in that the reaction activity is unstable during olefin oligomerization reaction of olefins, and the selectivity to 1-octene or 1-hexene is not exhibited, .

The present invention is to provide a continuous process for preparing olefin oligomers which can exhibit high and stable catalytic activity and high selectivity for 1-hexene and 1-octene in the continuous oligomerization reaction of olefins.

According to the present invention,

An oligomerization reaction step of an olefin in which an olefin monomer is contacted with the catalyst system in the presence of a catalyst system comprising a ligand compound represented by the following formula (1), (2) or (3), a transition metal source and a cocatalyst; And

A purification step of separating the olefin oligomer from the product of the oligomerization reaction

A process for the continuous preparation of an olefin oligomer, comprising:

[Chemical Formula 1]

In Formula 1,

Each of R ¹¹ to R ¹⁴ is independently a C _6-20 aryl group or a C _7-20 alkylaryl group, and R ¹⁵ is a C _1-20 alkyl group;

When R ¹⁵ is a methyl group, R ¹⁶ is a C _2-3 alkyl group, a C _2-3 alkenyl group, a C _1-3 heteroalkyl group, a C _1-3 heteroalkenyl group, a C _4-20 alkyl group, a C _4-20 A C _4-20 arylalkyl group, a C _4-20 arylalkenyl group, a C _4-20 heteroalkyl group, a C _4-20 heteroalkenyl group, a C _4-20 heteroarylalkyl group, a C _4-20 heteroarylalkenyl group, A C _3-20 cycloalkyl group, a C _3-20 cycloalkyl group, a C _3-20 cycloalkenyl group, a C _3-20 arylcycloalkyl group, a C _3-20 arylcycloalkenyl group, a C _3-20 heterocycloalkyl group, a C _3-20 heterocycloalkenyl group, a C _A C _3-6 heteroarylcycloalkyl group, a C _3-20 heteroarylcycloalkenyl group, a C _6-20 aryl group, a C _6-20 heteroaryl group, a C _7-20 alkylaryl group, or a C _7-20 heteroalkylaryl group ;

When R ¹⁵ is a C _2-20 alkyl group, R ¹⁶ is a C _2-20 alkyl group, a C _2-20 alkenyl group, a C _2-20 arylalkyl group, a C _2-20 arylalkenyl group, a C _1-20 heteroalkyl group , A C _1-20 heteroalkenyl group, a C _1-20 heteroarylalkyl group, a C _1-20 heteroarylalkenyl group, a C _3-20 cycloalkyl group, a C _3-20 cycloalkenyl group, a C _3-20 arylcycloalkyl group, a C _3-20 aryl cycloalkenyl group, C _3-20 heterocycloalkyl group, C _3-20 heteroaryl cycloalkenyl group, C _3-20 heteroaryl, cycloalkyl, C _3-20 heteroaryl, cycloalkenyl group, C _6-20 aryl group, , A C _6-20 heteroaryl group, a C _7-20 alkylaryl group, or a C _7-20 heteroalkylaryl group;

Wherein R ¹⁷ to R ¹⁹ are each independently, hydrogen, C _1-20 alkyl, C _1-20 alkenyl, C _1-20 arylalkyl, C _1-20 arylalkenyl group, C _3-20 cycloalkyl group, C _{3 A} cycloalkenyl group, a C _3-20 arylcycloalkyl group, a C _3-20 arylcycloalkenyl group, a C _6-20 aryl group, or a C _7-20 alkylaryl group;

(2)

(3)

In the general formulas (2) and (3)

R ²¹ to R ²⁴ each independently represent a C _1-10 alkyl group; A C _3-6 cycloalkyl group which is unsubstituted or substituted with a C _1-10 alkyl group or a C _1-10 alkoxy group; A C _6-20 aryl group unsubstituted or substituted with a C _1-10 alkyl group or a C _1-10 alkoxy group; Or an unsubstituted or substituted C _1-10 alkyl group or a C _1-10 alkoxy group-substituted C _5-20 heteroaryl group,

R ²⁵ is a C _1-10 alkyl group; A C _3-6 cycloalkyl group which is unsubstituted or substituted with a C _1-10 alkyl group or a C _1-10 alkoxy group; A C _6-20 aryl group unsubstituted or substituted with a C _1-10 alkyl group or a C _1-10 alkoxy group; Or C _5-10 heteroaryl which is unsubstituted or substituted with a C _1-10 alkyl group or a C _1-10 alkoxy group,

X ² is a direct binding or a C _1-5 alkylene group, respectively.

Hereinafter, a method of continuously producing an olefin oligomer according to an embodiment of the present invention will be described in detail.

Prior to that, and unless explicitly stated throughout the present specification, the terminology is used merely to refer to a specific embodiment and is not intended to limit the present invention.

The singular forms as used herein include plural forms as long as the phrases do not expressly contradict it.

Means that a particular feature, region, integer, step, operation, element and / or component is specified, and that other specific features, regions, integers, steps, operations, elements, components and / And the like.

As used herein, the term " oligomerization " of an olefin refers to a reaction in which the olefin is polymerized. It is called "trimerization" and "tetramerization" according to the number of olefins to be polymerized, and is collectively referred to as "multimerization". In particular, the oligomerization reaction of olefins in the present invention means a reaction for selectively forming 1-hexene and 1-octene as the main comonomers of LLDPE from ethylene.

On the other hand, as a result of continuous research by the present inventors, it has been found that when oligomerization of an olefin monomer is carried out in the presence of a catalyst system containing a ligand compound represented by the following general formula (1), (2) Lt; RTI ID = 0.0 > 1-hexene < / RTI > and 1-octene.

According to one embodiment of the invention,

An oligomerization reaction of an olefin in which an olefin monomer is brought into contact with the catalyst system in the presence of a catalyst system comprising a ligand compound represented by the formula (1), (2) or (3), a transition metal source and a cocatalyst; And

A purification step of separating the olefin oligomer from the product of the oligomerization reaction

≪ RTI ID = 0.0 > a < / RTI > continuous process for preparing an olefin oligomer.

The selective oligomerization reaction of olefins is closely related to the catalyst system used. The catalyst system used in the oligomerization reaction of olefins comprises a transition metal source and a cocatalyst that serve as the main catalyst wherein the structure of the active catalyst can be varied according to the chemical structure of the ligand compound bonded to the transition metal source , And thus selectivity of olefins may vary.

The ligand compounds represented by the above formulas (1), (2) and (3) have a diphosphino aminyl moiety and can provide a steric bulk to enable selective oligomerization of olefins.

The ligand compounds represented by the above formula (1) are obtained by substituting R ¹⁵ and R ^16, which satisfy the specific conditions, on the 2-carbon and 6-carbon positions based on the positions of the diphosphinoaminyl residues, And the selectivity of 1-hexene and 1-octene can be increased.

The ligand compound represented by the general formula (2) or (3) is characterized in that the d-phosphinoaminyl residue and the -X ² -R ²⁵ group are trans-substituted. Although not to be bound by theory, the cis form and the trans form may exhibit different reactivity during oligomerization of olefins, respectively, due to the difference in coordination form with the transition metal depending on the structure of the ligand. The trans-type ligand compound represented by Formula 2 or 3 can increase the activity of oligomerization of olefins and increase the selectivity of 1-hexene and 1-octene.

In particular, the ligand compounds represented by the above formula (1), (2) or (3) enable the catalyst system to exhibit a high and stable catalytic activity and high selectivity to 1-hexene and 1-octene in the continuous oligomerization reaction of olefins , Such catalyst systems enable the expression of high productivity in the continuous production of olefin oligomers.

First, the catalyst system used in the oligomerization reaction step of the olefin will be described in more detail.

The catalyst system includes the ligand compound represented by Chemical Formula 1, Chemical Formula 2 or Chemical Formula 3, a transition metal source and a cocatalyst.

[The ligand compound represented by the formula (1)

The ligand compound represented by the above formula (1) is a compound in which R ¹⁵ and R ¹⁶ are substituted at the 2-carbon and 6-carbon positions with respect to the position of the diphosphinoaminyl residue,

[Chemical Formula 1]

In Formula 1,

Each of R ¹¹ to R ¹⁴ is independently a C _6-20 aryl group or a C _7-20 alkylaryl group, and R ¹⁵ is a C _1-20 alkyl group;

When R ¹⁵ is a methyl group, R ¹⁶ is a C _2-3 alkyl group, a C _2-3 alkenyl group, a C _1-3 heteroalkyl group, a C _1-3 heteroalkenyl group, a C _4-20 alkyl group, a C _4-20 A C _4-20 arylalkyl group, a C _4-20 arylalkenyl group, a C _4-20 heteroalkyl group, a C _4-20 heteroalkenyl group, a C _4-20 heteroarylalkyl group, a C _4-20 heteroarylalkenyl group, A C _3-20 cycloalkyl group, a C _3-20 cycloalkyl group, a C _3-20 cycloalkenyl group, a C _3-20 arylcycloalkyl group, a C _3-20 arylcycloalkenyl group, a C _3-20 heterocycloalkyl group, a C _3-20 heterocycloalkenyl group, a C _A C _3-6 heteroarylcycloalkyl group, a C _3-20 heteroarylcycloalkenyl group, a C _6-20 aryl group, a C _6-20 heteroaryl group, a C _7-20 alkylaryl group, or a C _7-20 heteroalkylaryl group ;

When R ¹⁵ is a C _2-20 alkyl group, R ¹⁶ is a C _2-20 alkyl group, a C _2-20 alkenyl group, a C _2-20 arylalkyl group, a C _2-20 arylalkenyl group, a C _1-20 heteroalkyl group , A C _1-20 heteroalkenyl group, a C _1-20 heteroarylalkyl group, a C _1-20 heteroarylalkenyl group, a C _3-20 cycloalkyl group, a C _3-20 cycloalkenyl group, a C _3-20 arylcycloalkyl group, a C _3-20 aryl cycloalkenyl group, C _3-20 heterocycloalkyl group, C _3-20 heteroaryl cycloalkenyl group, C _3-20 heteroaryl, cycloalkyl, C _3-20 heteroaryl, cycloalkenyl group, C _6-20 aryl group, , A C _6-20 heteroaryl group, a C _7-20 alkylaryl group, or a C _7-20 heteroalkylaryl group;

Wherein R ¹⁷ to R ¹⁹ are each independently, hydrogen, C _1-20 alkyl, C _1-20 alkenyl, C _1-20 arylalkyl, C _1-20 arylalkenyl group, C _3-20 cycloalkyl group, C _{3 A} C _3-20 arylcycloalkyl group, a C _3-20 arylcycloalkenyl group, a C _6-20 aryl group, or a C _7-20 alkylaryl group.

That is, when R ¹⁵ in the formula 1 is a methyl group, the R ¹⁶ has an asymmetric structure with the R ¹⁵ .

Specifically, when R ¹⁵ in the general formula (1) is a methyl group, R ¹⁶ represents a C _2-3 alkyl group, a C _2-3 alkenyl group, a C _1-3 heteroalkyl group, a C _1-3 heteroalkenyl group, a C _{4- 20} alkyl group, C _4-20 alkenyl, C _4-20 arylalkyl, C _4-20 arylalkenyl group, C _4-20 heterocyclic group, C _4-20 heteroaryl alkenyl, C _4-20 heteroaryl group, C _{4 -20} heteroaryl alkenyl, C _3-20 cycloalkyl, C _3-20 cycloalkenyl group, C _3-20 cycloalkyl aryl, aryl C _3-20 cycloalkenyl group, C _3-20 heterocycloalkyl group, C _{3- A} C _3-20 heteroarylcycloalkyl group, a C _3-20 heteroarylcycloalkenyl group, a C _6-20 aryl group, a C _6-20 heteroaryl group, a C _7-20 alkylaryl group, or C _7-20 heteroalkyl aryl groups.

Preferably, when R ¹⁵ in the general formula (1) is a methyl group, R ¹⁶ represents a C _2-3 alkyl group, a C _2-3 alkenyl group, a C _1-3 heteroalkyl group, a C _1-3 heteroalkenyl group, a C _{6 -20} aryl group, a C _6-20 heteroaryl group, a C _7-20 alkylaryl group, or a C _7-20 heteroalkylaryl group.

In the formula 1, when R ¹⁵ is a C _2-20 alkyl group, R ¹⁶ has a symmetrical or asymmetric structure with respect to the R ¹⁵ within the following range.

Specifically, when R ¹⁵ in the formula (1) is a C _2-20 alkyl group, R ¹⁶ represents a C _2-20 alkyl group, a C _2-20 alkenyl group, a C _2-20 arylalkyl group, a C _2-20 arylalkenyl group , C _1-20 heteroaryl group, C _1-20 heteroaryl alkenyl, C _1-20 heteroaryl group, C _1-20 heteroaryl, alkenyl, C _3-20 cycloalkyl, C _3-20 cycloalkenyl group, C _{3 A C3-20} cycloalkylalkenyl group, a _C3-20 cycloalkylalkenyl group, a _C3-20 heterocycloalkyl group, a _C3-20 heterocycloalkenyl group, a _C3-20 heteroarylcycloalkyl group, a _C3-20 heteroarylcycloalkenyl group , A C _6-20 aryl group, a C _6-20 heteroaryl group, a C _7-20 alkylaryl group, or a C _7-20 heteroalkylaryl group.

Preferably, when R ¹⁵ in the general formula (1) is a C _2-20 alkyl group, R ¹⁶ is preferably a C _2-20 alkyl group, a C _2-20 alkenyl group, a C _2-20 arylalkyl group, a C _2-20 arylalkene C _1-20 heteroalkyl group, C _1-20 heteroalkenyl group, C _1-20 heteroarylalkyl group, C _6-20 aryl group, C _6-20 heteroaryl group, C _7-20 alkylaryl group, or C _7-20 heteroalkyl aryl groups.

In Formula 1, R ¹¹ to R ¹⁴ are each a phenyl group, and R ¹⁷ to R ¹⁹ are each preferably hydrogen or a methyl group.

Representative examples of the ligand compound represented by the above formula (1) are as follows:

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Due to the above-mentioned structural features of the ligand compound represented by the formula (1), the catalyst system containing the ligand compound can exhibit oligomerization reaction activity of a high olefin according to various conditions such as electron and steric environment around the transition metal, 1-hexene, 1-octene, and the like.

In particular, the catalyst system comprising the ligand compound represented by the above formula (1) can suppress the formation of the 1-hexene isomer which greatly affects the product even in a small amount in the oligomerization reaction of the olefin, Can be suitably used for the process.

Further, since the catalyst system comprising the ligand compound represented by Formula 1 promotes the formation of 1-hexene and inhibits the formation of 1-hexene isomer, the process for separating the 1-hexene isomer in the continuous production process of olefin oligomer And thus energy savings.

As a non-limiting example, the ligand compound represented by Formula 1 may be synthesized by the following reaction scheme 1:

[Reaction Scheme 1]

In the above Reaction Scheme 1, G ¹ may be a phenyl group having R ¹⁵ to R ¹⁹ in Formula 1, and G ² and G ³ may be groups corresponding to R ¹¹ to R ¹⁴ in Formula 1, respectively.

The above reaction scheme 1 is an example of synthesizing the ligand compound represented by the above formula (1), in which amine and phosphine react to form a depospinoaminyl residue. That is, the reaction scheme 1 is a reaction in which an amine is a nucleophilic agent to displace and substitute a leaving group represented by X of a phosphine. The X is not particularly limited as long as it is a functional group which is easily stably released after being released, and is preferably a halogen group such as Cl, Br or I.

[The ligand compound represented by the general formula (2) or (3)

The ligand compound represented by the above-mentioned general formula (2) or (3) is characterized in that the d-phosphinoaminyl residue and the -X ² -R ²⁵ group are substituted in trans form:

(2)

(3)

In the general formulas (2) and (3)

R ²¹ to R ²⁴ each independently represent a C _1-10 alkyl group; A C _3-6 cycloalkyl group which is unsubstituted or substituted with a C _1-10 alkyl group or a C _1-10 alkoxy group; A C _6-20 aryl group unsubstituted or substituted with a C _1-10 alkyl group or a C _1-10 alkoxy group; Or an unsubstituted or substituted C _1-10 alkyl group or a C _1-10 alkoxy group-substituted C _5-20 heteroaryl group,

R ²⁵ is a C _1-10 alkyl group; A C _3-6 cycloalkyl group which is unsubstituted or substituted with a C _1-10 alkyl group or a C _1-10 alkoxy group; A C _6-20 aryl group unsubstituted or substituted with a C _1-10 alkyl group or a C _1-10 alkoxy group; Or C _5-10 heteroaryl which is unsubstituted or substituted with a C _1-10 alkyl group or a C _1-10 alkoxy group,

X ² is a direct binding or a C _1-5 alkylene group, respectively.

R ²¹ to R ²⁴ in Formula 2 or Formula 3 are preferably the same as each other, and more preferably each may be a phenyl group.

The -X ² -R ²⁵ group is a group in which the compound of formula (2) or (3) has a trans form due to steric hindrance with a depospinoaminyl residue. Therefore, the larger the size of the -X ² -R ²⁵ group, the easier the formation of the trans-type compound.

Preferably, R ²⁵ in Formula 2 or Formula 3 is independently selected from the group consisting of ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, neopentyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, Cyclohexyl, or phenyl.

Preferably, X ² in Formula 2 or 3 may be a direct bond or a methylene group, respectively.

Preferably, each of R ²⁵ is a C _3-6 cycloalkyl group or a C _6-20 aryl group, and each of X ² may be a methylene group.

Also, preferably, each of R ²⁵ is a C _1-10 alkyl group or a C _3-6 cycloalkyl group, and each of X ² may be a direct bond.

Representative examples of the ligand compound represented by the above formula (2) or (3) are as follows:

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As a non-limiting example, the ligand compounds represented by Formula 2 or Formula 3 may be synthesized in the same manner as in Scheme 2 below:

[Reaction Scheme 2]

In the above Reaction Scheme 2, X ² and R ²¹ to R ²⁵ are as defined above, and X 'means a substituent which is removed upon reaction with an amine of the starting material, respectively. X 'is not particularly limited as long as it is a functional group which is stable and easily released after being released, and may be preferably a halogen group such as Cl, Br,

The order of the first and second steps in Scheme 2 may be reversed and the second step may be omitted if X'-PR ²¹ R ²² and X'-PR ²³ R ²⁴ are the same compound. As a solvent for the reaction, dichloromethane is preferable, and the reaction is preferably carried out in the presence of triethylamine.

According to the first reaction in Reaction Scheme 2, the amine group of the compound represented by Formula (a), which is the starting material, reacts with the compound represented by Formula (b) to form a compound represented by Formula (c).

Then, by the second reaction, the amine group of the compound represented by the formula (c) and the compound represented by the formula (d) can be reacted to form a compound represented by the formula (2) or (3). At this time, a trans type compound is produced by the steric hindrance of the -X ² -R ²⁵ group of the compound represented by the formula (c), like the compound represented by the formula (2) or (3) Not manufactured.

Further, since unreacted materials (compounds represented by the chemical formulas a, b and d), intermediates (compounds represented by the chemical formula c) and other salt compounds remain in the final product, a step of removing it from the product is further performed . The removal can be carried out by a method commonly used in the art. For example, in order to remove the salt compound, a polar solvent (for example, THF) is first added to remove and remove the solvent, and then a solvent (for example, acetonitrile) capable of dissolving the remaining substances other than the compounds represented by the formulas (2) And then removing and removing it.

[Transition metal source]

The transition metal source included in the catalyst system may be a compound acting as a main catalyst, and may be in a state of coordination bonding with the above-mentioned ligand compound. For example, phosphorus (P) of the diphosphinoamyl moiety in the ligand compound described above may act as an active point with which the transition metal source is coordinated.

Preferably, the transition metal source is an organic or inorganic chromium compound having an oxidation state of 0 to 6 of chromium, for example a chromium metal, or a compound wherein any organic or inorganic radical is bonded to chromium. Here, the organic radical may be an alkyl, alkoxy, ester, ketone, amido radical, etc. having from 1 to 20 carbon atoms per radical. The inorganic radical may be a halide, a sulfate, an oxide, or the like.

Specifically, the transition metal source is selected from the group consisting of chromium (III) acetylacetonate, chromium (III) chloride tetrahydrofuran, chromium (III) 2- ethylhexanoate, chromium (III) (III) benzoyl acetonate, chromium (III) hexafluoro-2,4-pentene indionate, chromium (III) acetate hydroxide, chromium (III) acetate , Chromium (III) butyrate, chromium (III) pentanoate, chromium (III) laurate, and chromium (III) stearate.

[Co-catalyst]

The cocatalyst is an organometallic compound capable of activating a complex by the above-described ligand compound and a transition metal source.

Preferably, the cocatalyst may be at least one compound selected from the group consisting of compounds represented by the following formulas (4) to (6):

[Chemical Formula 4]

- [Al (R < ⁴¹ >) - O] _c-

In Formula 4,

R ⁴¹ is the same or different and each is independently a halogen radical, C _1-20 hydrocarbyl radical or a halogen a C _1-20 hydrocarbyl radical substituted with one another,

c is an integer of 2 or more;

[Chemical Formula 5]

D ( ^R51 ) ₃

In Formula 5,

D is aluminum or boron,

R ⁵¹ is C _1-20 hydrocarbyl or C _1-20 hydrocarbyl substituted with halogen;

[Chemical Formula 6]

[LH] ⁺ [Q (E) ₄ ] ^-

In Formula 6,

L is a neutral Lewis base, [LH] ⁺ is a Bronsted acid,

Q is boron or aluminum in the +3 oxidation state form, E are each independently one or more hydrogen atoms (atomic value) halogen, C _1-20 hydrocarbyl, alkoxy functional groups, or substituted or unsubstituted phenoxy functional group C _{6- 20} aryl group or a C _1-20 alkyl group.

Specifically, the compound represented by Formula 4 may be an alkyl aluminoxane such as methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, and butyl aluminoxane.

The compound represented by the above-mentioned general formula (5) may be used in combination with one or more compounds selected from the group consisting of trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, dimethylisobutylaluminum, dimethylethylaluminum, diethylchloroaluminum, , Tri-s-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri-p-tolylaluminum, dimethylaluminum methoxide , Dimethyl aluminum ethoxide, trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron, tributyl boron and the like.

The compound represented by Formula 6 is preferably selected from the group consisting of triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetra (p-tolyl) boron, (O, p-dimethylphenyl) boron, tributylammonium tetra (p-tolyl) boron, triethylammoniumtetra (P-trifluoromethylphenyl) boron, tributylammonium tetrapentafluorophenylboron, N, N-diethylanilinium tetraphenylboron, N, N-diethyl Anilinium tetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium tetraphenylboron, trimethylphosphonium tetraphenyl (P-tolyl) aluminum, trimethylammonium tetraphenyl aluminum, trimethylammonium tetraphenyl aluminum, trimethylammonium tetraphenyl aluminum, trimethylammonium tetraphenyl aluminum, tributylammonium tetraphenyl aluminum, (p-tolyl) aluminum, triethylammoniumtetra (o, p-dimethylphenyl) aluminum, tributylammoniumtetra (ptrifluoromethylphenyl) aluminum, trimethylammoniumtetra (ptrifluoromethylphenyl) aluminum , Tributylammonium tetrapentafluorophenyl aluminum, N, N-diethylanilinium tetraphenyl aluminum, N, N-diethylanilinium tetraphenyl aluminum, N, N-diethylanilinium tetrapentafluoride Phenyl aluminum, diethylammonium tetrapentafluorophenyl aluminum, triphenylphosphonium tetraphenyl aluminum, trimethylphosphonium tetraphenyl aluminum , Triphenylcarbonium tetraphenylboron, triphenylcarboniumtetraphenylaluminum, triphenylcarboniumtetra (p-trifluoromethylphenyl) boron, triphenylcarbonium tetrapentafluorophenylboron, etc. .

The promoter may be an organoaluminum compound, an organoboron compound, an organomagnesium compound, an organozinc compound, an organolithium compound, or a mixture thereof.

In particular, the promoter is preferably an organoaluminum compound, more preferably trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, Ethylaluminum sesquichloride, diethylaluminum chloride, ethyl aluminum dichloride, methylaluminoxane, and modified methylaluminoxane, which are known to those skilled in the art. ≪ / RTI >

In particular, as the cocatalyst, modified methylaluminoxane (MMAO), which is a compound in which a part of the methyl group of the methylaluminoxane is substituted with another alkyl group, may be used. For example, the modified methylaluminoxane may be a compound in which 40 mol% or less, or 5 mol% to 35 mol%, of the methyl group in the methylaluminoxane is substituted with a linear or branched alkyl group having 3 to 10 carbon atoms. Examples of the commercially available modified methylaluminoxane include MMAO-12, MMAO-3A and MMAO-7.

The content ratio of the above-described components constituting the catalyst system can be determined in consideration of catalytic activity and selectivity to linear alpha-olefin.

In one example, the molar ratio of the ligand compound included in the catalyst system: the transition metal of the transition metal source to the metal of the cocatalyst is 0.1: 1: 1 to 10: 1: 10000, or 0.5: 1: : 1: 3000 may be advantageous for the expression of catalytic activity and selectivity.

The above-mentioned components constituting the catalyst system can be added simultaneously and in any order and mixed in the presence of a suitable solvent. Examples of the solvent include heptane, toluene, cyclohexane, methylcyclohexane, 1-hexene, 1-octene, diethyl ether, tetrahydrofuran, acetonitrile, dichloromethane, chloroform, chlorobenzene, methanol and acetone .

On the other hand, according to an embodiment of the present invention, the oligomerization reaction step of the olefin can be carried out by contacting the olefin monomer with the catalyst system in the presence of the catalyst system described above.

The oligomerization reaction step of the olefin may be carried out in a reactor suitable for a continuous process and preferably a reaction system comprising at least one reactor selected from the group consisting of a continuous stirred reactor (CSTR) and a plug flow reactor (PFR) . ≪ / RTI >

In the oligomerization reaction of the olefin, gaseous ethylene may be preferably used as the olefin monomer.

The oligomerization reaction of the olefin can be carried out in the presence of an inert solvent in the presence of an inert solvent, homogeneous liquid phase reaction, slurry reaction in which the catalyst system is partially or completely dissolved, a two-phase liquid / Liquid reaction, or bulk-phase or gas-phase reaction in which the product alpha-olefin acts as the main medium. Preferably, the oligomerization reaction step of the olefin may be advantageously carried out in a homogeneous liquid phase reaction in a continuous process.

The oligomerization of the olefin may be carried out in any inert solvent that does not react with the catalyst system. Suitable inert solvents include, but are not limited to, benzene, toluene, xylene, cumene, heptane, cyclohexane, methylcyclohexane, methylcyclopentane, hexane, pentane, butane and isobutane. At this time, the inert solvent is preferably used after removing a small amount of water or air acting as a catalyst poison by treating with a small amount of alkylaluminum.

The weight ratio of [olefin monomer] / [inert solvent] per unit time in the oligomerization reaction of the olefin is preferably 0.1 to 3, or 0.5 to 2, or 1 to 2, from the viewpoint of securing reaction efficiency.

The flow rate of the olefin monomer and the inert solvent can be appropriately controlled according to the scale of the reaction system in which the oligomerization reaction of the olefin is carried out. For example, the olefin monomer and the inert solvent may be introduced at a flow rate of 0.1 to 2 kg / hr in the weight ratio described above, respectively.

The oligomerization reaction of the olefin may be carried out at a temperature of 5 to 200 ° C, preferably 30 to 150 ° C. The oligomerization reaction of the olefin may be carried out under a pressure of 1 to 300 bar, preferably 2 to 150 bar.

The range of the temperature and pressure conditions may be a condition suitable for the oligomerization reaction of olefins. When the olefins are oligomerized in the temperature range and the pressure range, the selectivity to the desired alpha-olefin may be excellent, Can be reduced and the operation efficiency of the continuous process can be increased and the cost can be reduced.

On the other hand, a purification step of separating the olefin oligomer from the product of the oligomerization reaction of the olefin is carried out.

The purification step is not particularly limited, and the components contained in the product of the oligomerization reaction of the olefin are sequentially separated using a conventional separation column, and the desired olefin oligomer (for example, 1-hexene and 1-octene) Can be obtained.

As a non-limiting example, the oligomerization reaction step and the purification step of the olefin according to the continuous production method of the olefin oligomer may be carried out according to the process shown in FIG.

Specifically, the above reaction system is subjected to the oligomerization reaction step of the olefin under the above-described reaction conditions by continuously feeding a feed containing the above-described catalyst system, olefin monomer (preferably gaseous ethylene) and a solvent. The product of the oligomerization reaction of the continuously discharged olefins in the reaction system is transferred to a cold flash reactor where some hot gaseous compounds are liquefied. Unreacted ethylene (C2) in the product of the oligomerization reaction of the olefin is recovered in the ethylene separation column and recycled as part of the feed. After the ethylene separation column, a polymer such as ethylene dimer (C4), trimer (C6) and tetramer (C8) are sequentially separated and the desired 1-hexene (1-C6) and 1-octene (1-C8) can be obtained.

The continuous process for preparing olefin oligomers according to the present invention exhibits high and stable catalytic activity and high selectivity for 1-hexene and 1-octene in the continuous oligomerization reaction of olefins, thereby enabling improved productivity and stable process operation.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a process diagram schematically showing a method for continuously producing an olefin oligomer according to an embodiment of the present invention. FIG.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. However, the following embodiments are intended to illustrate the invention, but the invention is not limited thereto.

Synthetic example  One

2-Ethyl-6-methylaniline (10 mmol) and triethylamine (3 equiv. To amine) were dissolved in dichloromethane (80 mL) under argon atmosphere. While the flask was immersed in a water bath, chlorodiphenylphosphine (20 mmol) was slowly added thereto and stirred overnight. After the solvent is evaporated under vacuum, another solvent (diethyl ether, tetrahydrofuran or hexane) is added, and the mixture is stirred sufficiently. Triethylammonium chloride (triethylammonium chloride salt) was removed. The solvent was removed from the filtrate to obtain a ligand compound of the above formula.

^{31 P NMR (202 MHz, CDCl} 3): 59.2 (s).

Synthetic example  2

A ligand compound of the above formula was obtained in the same manner as in Synthesis Example 1, except that 2,6-diethylaniline was used instead of 2-ethyl-6-methylaniline.

^{31 P NMR (202 MHz, CDCl} 3): 56.3 (s).

Synthetic example  3

A ligand compound of the above formula was obtained in the same manner as in Synthesis Example 1 except that 2-methoxy-6-methylaniline was used instead of 2-ethyl-6-methylaniline.

^{31 P NMR (202 MHz, CDCl} 3): 59.6 (s).

Synthetic example  4

Except that 2,4-dimethyl-6-phenylaniline was used in place of 2-ethyl-6-methylaniline to obtain the ligand compound of the above formula .

^{31 P NMR (202 MHz, CDCl} 3): 65.5 (s).

compare Synthetic example  One

A ligand compound of the above formula was obtained in the same manner as in Synthesis Example 1 except that 2,6-dimethylaniline was used instead of 2-ethyl-6-methylaniline.

^{31 P NMR (202 MHz, CDCl} 3): 56.1 (s).

compare Synthetic example  2

A ligand compound of the above formula was obtained in the same manner as in Synthesis Example 1 except that 2-methylaniline was used in place of 2-ethyl-6-methylaniline.

^{31 P NMR (202 MHz, CDCl} 3): 61.7 (s).

Synthetic example  5

및

And

2-benzylcyclohexaneamine (10 mmol) and triethylamine (2-10 equiv. To 2-benzylcyclohexaneamine) were dissolved in dichloromethane (80 mL) under argon atmosphere. While the flask was immersed in a water bath, chlorodiphenylphosphine (1.5-2.0 equiv. To 2-benzylcyclohexaneamine) was slowly added thereto and stirred overnight. After removing the solvent by vacuum drying, THF was added and the mixture was sufficiently stirred and triethylammonium chloride salt was removed with an air-free glass filter. After the solvent was dried in the filtrate, acetonitrile was added thereto and sufficiently stirred to obtain a white solid ligand compound by an air-free glass filter. In this process, compounds other than the ligand compound were dissolved in acetonitrile and separated into filtrate.

^{31 P NMR (202 MHz, CDCl} 3): 56.5 (s), 54.9 (s).

Synthetic example  6

및

And

Except that [1,1'-bi (cyclohexan)] - 2 -amine ([1,1'-bi (cylcohexan)] - 2 -amine was used in place of 2-benzylcyclohexaneamine. The ligand compound of the above formula was obtained in the same manner as in 5.

^{31 P NMR (202 MHz, CDCl} 3): 53.9 (s), 49.6 (s).

Synthetic example  7

및

And

A ligand compound of the above formula was obtained in the same manner as in Synthesis Example 5 except that 2- (cyclohexylmethyl) cyclohexaneamine was used in place of 2-benzylcyclohexaneamine.

^{31 P NMR (202 MHz, CDCl} 3): 52.9 (s), 48.4 (s).

Synthetic example  8

및

And

A ligand compound of the above formula was obtained in the same manner as in Synthesis Example 5 except that 2-isopropylcyclohexaneamine was used instead of 2-benzylcyclohexaneamine.

^{31 P NMR (202 MHz, CDCl} 3): 62.0 (s), 51.3 (s).

compare Synthetic example  3

A ligand compound of the above formula was obtained in the same manner as in Synthesis Example 5 except that cyclohexaneamine was used instead of 2-benzylcyclohexaneamine. The process of separating the remaining compounds other than the ligand compound by adding acetonitrile is omitted.

^{31 P NMR (202 MHz, CDCl} 3): 49.5 (s)

Example  1 to 10

A reaction system as shown in Fig. 1 equipped with a 2 L capacity CSTR was prepared. CSTR with nitrogen atmosphere was continuously charged with methylcyclohexane ('MCH') of [X] kg / hr and ethylene ('C2') of [Y] kg / hr as shown in the following Table 1, Respectively.

Separately, a ligand compound according to Synthesis Example 1 and Cr (acac) ₃ were added to a pressure-resistant container having a capacity of 10 L so that the molar ratio of the ligand compound: Cr was about 0.55: 1, and then a main catalyst adequately diluted in methylcyclohexane Solution (0.05 mM based on Cr) was prepared. A co-catalyst solution (0.05 M based on Al) diluted with methylcyclohexane was prepared as MMAO as a cocatalyst.

The catalyst solution ('MMAO') was added to the CSTR at a rate of [Z] mL / min while the main catalyst solution ('Catal.') The oligomerization reaction of ethylene was continuously carried out at a rate of [C] mL / min according to the amount of the catalyst solution.

At this time, the reaction temperature was adjusted to keep the temperature at 60 ° C by continuously introducing the refrigerant into the reactor jacket. The product discharged from the CSTR was transferred to a low-temperature flash reactor so that some high-temperature gaseous compounds were liquefied.

50 mL of the product discharged in a flash reactor was discharged under the condition that the reaction was stable for about 2 hours, quenched with water, and the organic layer was filtered with a PTFE syringe filter to perform GC analysis. The results are shown in Table 2 below.

Unreacted ethylene in the product of the oligomerization reaction was recovered in an ethylene separation column and recycled as a feed of the CSTR. Subsequently, the dimer (C4), trimer (C6) and tetramer (C8) of ethylene were separated in each multimeric separation column, and the recovered solvent was recycled as a feed of the CSTR. Then, the desired 1-hexene (1-C6) and 1-octene (1-C8) were obtained from the fractions of the recovered multimer.

Example C2
(kg / hr) MCH
(kg / hr) Catal.
(mL / min) MMAO
(mL / min) One 1.50 1.0 3.0 5.4 2 1.75 1.17 3.5 6.3 3 1.75 1.0 4.0 7.2 4 1.75 1.5 4.0 7.2 5 1.75 1.5 3.0 5.4 6 2.00 1.5 3.0 5.4 7 1.75 1.0 3.0 5.4 8 1.75 1.0 2.0 3.6 9 1.75 1.0 2.5 4.5 10 1.75 1.2 3.0 5.4

Example activation 1-C ₆ 1-C ₈ C ₁₀ -C ₄₀ HAO C ₆ -iso C ₂ Conv. P.R. One 119.9 40.0 45.9 11.8 85.9 1.6 71.9 1.08 2 127.8 39.1 47.2 11.6 86.3 1.5 76.7 1.15 3 101.0 40.2 45.6 12.7 85.9 1.6 69.3 1.21 4 103.2 41.7 44.9 11.1 86.6 1.6 70.8 0.83 5 125.9 39.7 48.2 10.0 87.9 1.5 64.8 0.76 6 83.0 42.6 48.4 7.1 91.0 1.4 37.4 0.50 7 134.5 37.1 49.0 11.7 86.1 1.6 69.2 1.21 8 171.7 30.0 57.9 9.8 87.9 1.6 58.9 1.03 9 153.4 32.4 54.6 10.6 87.1 1.7 65.8 1.15 10 119.8 41.5 47.5 8.8 89.0 1.5 61.6 0.90

In Table 2, the items are as follows.

* Activity (ton / mol Cr / hr)

* 1-C ₆ : Content of 1-hexene in the product (wt%)

* 1-C ₈ : Content of 1-octene in the product (wt%)

* C ₁₀ -C ₄₀ : content (wt%) of a compound having 10 to 40 carbon atoms

* HAO: Content of 1-hexene and 1-octene in the product (wt%)

* C ₆ -iso: content of C6 isomers (wt%) excluding 1-hexene in the product

* C ₂ Conv: conversion of ethylene (%)

* P.R .: Product Ratio (Products / Solvent (w / w))

Example  11 to 13

The oligomerization reaction of ethylene was carried out in the same manner as in Example 1, except that the ligand compound according to Synthesis Example 5 was applied and adjusted to the contents shown in Table 3 below. The results are shown in Table 4 below .

Example C2
(kg / hr) MCH
(kg / hr) Catal.
(mL / min) MMAO
(mL / min) 11 1.50 1.0 3.0 5.4 12 1.75 1.17 3.5 6.3 13 1.75 1.0 4.0 7.2

Example activation 1-C ₆ 1-C ₈ C ₁₀ -C ₄₀ HAO C ₆ -iso C ₂ Conv. P.R. 11 84.4 55.7 36.2 6.9 91.9 0.96 50.6 0.51 12 38.5 53.7 39.4 5.7 93.1 1.00 26.9 0.18 13 82.3 55.2 35.1 8.6 90.3 0.89 49.4 0.43

The items in Table 4 are shown in Table 2 above.

Referring to Tables 2 and 4, it was confirmed that the C6-iso content of Examples 1 to 13 was high while HAO selectivity was high.

Claims (11)

An oligomerization reaction step of an olefin in which an olefin monomer is contacted with the catalyst system in the presence of a catalyst system comprising a ligand compound represented by the following formula (1), (2) or (3), a transition metal source and a cocatalyst; And
A purification step of separating the olefin oligomer from the product of the oligomerization reaction of the olefin
≪ RTI ID = 0.0 >:< / RTI >
[Chemical Formula 1]

In Formula 1,
Each of R ¹¹ to R ¹⁴ is independently a C _6-20 aryl group or a C _7-20 alkylaryl group, and R ¹⁵ is a C _1-20 alkyl group;
When R ¹⁵ is a methyl group, R ¹⁶ is a C _2-3 alkyl group, a C _2-3 alkenyl group, a C _1-3 heteroalkyl group, a C _1-3 heteroalkenyl group, a C _4-20 alkyl group, a C _4-20 A C _4-20 arylalkyl group, a C _4-20 arylalkenyl group, a C _4-20 heteroalkyl group, a C _4-20 heteroalkenyl group, a C _4-20 heteroarylalkyl group, a C _4-20 heteroarylalkenyl group, A C _3-20 cycloalkyl group, a C _3-20 cycloalkyl group, a C _3-20 cycloalkenyl group, a C _3-20 arylcycloalkyl group, a C _3-20 arylcycloalkenyl group, a C _3-20 heterocycloalkyl group, a C _3-20 heterocycloalkenyl group, a C _A C _3-6 heteroarylcycloalkyl group, a C _3-20 heteroarylcycloalkenyl group, a C _6-20 aryl group, a C _6-20 heteroaryl group, a C _7-20 alkylaryl group, or a C _7-20 heteroalkylaryl group ;
When R ¹⁵ is a C _2-20 alkyl group, R ¹⁶ is a C _2-20 alkyl group, a C _2-20 alkenyl group, a C _2-20 arylalkyl group, a C _2-20 arylalkenyl group, a C _1-20 heteroalkyl group , A C _1-20 heteroalkenyl group, a C _1-20 heteroarylalkyl group, a C _1-20 heteroarylalkenyl group, a C _3-20 cycloalkyl group, a C _3-20 cycloalkenyl group, a C _3-20 arylcycloalkyl group, a C _3-20 aryl cycloalkenyl group, C _3-20 heterocycloalkyl group, C _3-20 heteroaryl cycloalkenyl group, C _3-20 heteroaryl, cycloalkyl, C _3-20 heteroaryl, cycloalkenyl group, C _6-20 aryl group, , A C _6-20 heteroaryl group, a C _7-20 alkylaryl group, or a C _7-20 heteroalkylaryl group;
Wherein R ¹⁷ to R ¹⁹ are each independently, hydrogen, C _1-20 alkyl, C _1-20 alkenyl, C _1-20 arylalkyl, C _1-20 arylalkenyl group, C _3-20 cycloalkyl group, C _{3 A} cycloalkenyl group, a C _3-20 arylcycloalkyl group, a C _3-20 arylcycloalkenyl group, a C _6-20 aryl group, or a C _7-20 alkylaryl group;
(2)

(3)

In the general formulas (2) and (3)
R ²¹ to R ²⁴ each independently represent a C _1-10 alkyl group; A C _3-6 cycloalkyl group which is unsubstituted or substituted with a C _1-10 alkyl group or a C _1-10 alkoxy group; A C _6-20 aryl group unsubstituted or substituted with a C _1-10 alkyl group or a C _1-10 alkoxy group; Or an unsubstituted or substituted C _1-10 alkyl group or a C _1-10 alkoxy group-substituted C _5-20 heteroaryl group,
R ²⁵ is a C _1-10 alkyl group; A C _3-6 cycloalkyl group which is unsubstituted or substituted with a C _1-10 alkyl group or a C _1-10 alkoxy group; A C _6-20 aryl group unsubstituted or substituted with a C _1-10 alkyl group or a C _1-10 alkoxy group; Or C _5-10 heteroaryl which is unsubstituted or substituted with a C _1-10 alkyl group or a C _1-10 alkoxy group,
X ² is a direct binding or a C _1-5 alkylene group, respectively.
The method according to claim 1,
Wherein the oligomerization reaction step of the olefin is carried out under a reaction system comprising at least one reactor selected from the group consisting of a continuous stirred tank reactor (CSTR) and a plug flow reactor (PFR).
The method according to claim 1,
Wherein the oligomerization reaction step of the olefin is carried out at a temperature of 5 to 200 DEG C and a pressure of 1 to 300 bar.
The method according to claim 1,
Wherein R ¹¹ to R ¹⁴ are each a phenyl group, and R ¹⁷ to R ¹⁹ are each hydrogen or a methyl group.
The method according to claim 1,
When R ¹⁵ in the formula (1) is a methyl group, R ¹⁶ represents a C _2-3 alkyl group, a C _2-3 alkenyl group, a C _1-3 heteroalkyl group, a C _1-3 heteroalkenyl group, a C _6-20 aryl group , A C _6-20 heteroaryl group, a C _7-20 alkylaryl group, or a C _7-20 heteroalkylaryl group.
The method according to claim 1,
When the R ¹⁵ of the general formula (1) is C _2-20 alkyl, wherein R ¹⁶ is C _2-20 alkyl, C _2-20 alkenyl, C _2-20 arylalkyl, C _2-20 arylalkenyl group, C _{1 A} C _1-20 heteroalkyl group, a C _1-20 heteroalkenyl group, a C _1-20 heteroarylalkyl group, a C _6-20 aryl group, a C _6-20 heteroaryl group, a C _7-20 alkylaryl group, or a C _7-20 hetero Lt; / RTI > is an alkylaryl group.
The method according to claim 1,
Wherein R ²¹ to R ²⁴ in Formula 2 or Formula 3 are each a phenyl group.
The method according to claim 1,
R ²⁵ in the above formula (2) or (3) is a cyclohexyl group substituted with ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, neopentyl, cyclopropyl, ≪ / RTI > or phenyl.
The method according to claim 1,
The transition metal source is selected from the group consisting of chromium (III) acetylacetonate, chromium (III) chloride tetrahydrofuran, chromium (III) 2- ethylhexanoate, chromium (III) tris (2,2,6,6- Heptadienoate), chromium (III) benzoyl acetonate, chromium (III) hexafluoro-2,4-pentene indinate, chromium (III) acetate hydroxide, chromium (III) acetate, chromium Wherein the at least one compound is at least one compound selected from the group consisting of III) butyrate, chromium (III) pentanoate, chromium (III) laurate, and chromium (III) stearate.
The method according to claim 1,
The cocatalyst may be selected from the group consisting of trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, ethylaluminum sesquichloride, diethyl aluminum Continuous production of oligomeric oligomers, which is at least one compound selected from the group consisting of diethylaluminum chloride, ethyl aluminum dichloride, methylaluminoxane, and modified methylaluminoxane. Way.
The method according to claim 1,
Wherein the olefin monomer comprises gaseous ethylene.

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