KR20160062525A - Catalyst system for olefin oligomerization, and method for olefin oligomerization using the same - Google Patents

Abstract

The present invention relates to a catalyst system for olefin oligomerization and an olefin oligomerization method using the olefin oligomerization catalyst system. The olefin oligomerization catalyst system according to the present invention has excellent catalytic activity and high selectivity for 1-hexene, ≪ / RTI >

Description

TECHNICAL FIELD The present invention relates to a catalyst system for olefin oligomerization, and a method for olefin oligomerization using the catalyst system for olefin oligomerization.

The present invention relates to a catalyst system for olefin oligomerization, and an olefin oligomerization method using the same.

Linear alpha-olefins are widely used commercially as important materials for comonomers, detergents, lubricants, and plasticizers. Especially, 1-hexene and 1-octene are used in the production of linear low density polyethylene (LLDPE) It is widely used as a comonomer for controlling density.

Since alpha-olefins vary in application field or market size depending on the type of olefin, the technology capable of selectively producing a specific olefin is of great commercial significance. Recently, selective ethylene oligomerization has been used to produce 1-hexene or 1 - octene catalysts have been studied extensively.

Specifically, U.S. Patent No. 7361623 discloses a catalyst system for producing 1-hexene and 1-octene using chromium as a central metal, but the catalyst system can not consistently maintain the reaction activity depending on the reaction time, Is greatly reduced.

Korean Patent No. 10-0435513 discloses a catalyst system for the production of 1-hexene using chromium as a central metal. However, since the performance of the catalyst is exhibited under conditions of high temperature and high pressure, There is a limit.

Accordingly, there is a continuing need for a continuously increasing mass-increasing reaction activity and a high selectivity during the reaction in the production of alpha-olefins such as 1-octene or 1-hexene.

U.S. Patent No. 7361623 Korea Patent No. 10-0435513

The present invention provides a catalyst system for olefin oligomerization capable of oligomerization of olefins with high catalytic activity and selectivity, and an olefin oligomerization method using the same.

The present invention relates to a ligand compound represented by the following general formula (1): A transition metal source; And a cocatalyst, wherein the olefin oligomerization catalyst system comprises:

[Chemical Formula 1]

In Formula 1,

E ₁ to E ₃ each independently represent an element selected from the group consisting of boron (B), carbon (C), nitrogen (N), oxygen (O), silicon (Si), phosphorus (P) And at least one of E ₁ to E ₃ is an element selected from the group consisting of boron (B), nitrogen (N), oxygen (O), silicon (Si), phosphorus (P) ,

R ₁ to R _{12 each} represent a hydrogen atom, an alkyl (Alky) group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, a haloalkyl an arylalkyl group having 6 to 40 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an arylsilyl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, An alkoxy group having 1 to 20 carbon atoms, an alkylsiloxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a halogen (Halogen) group, or an amino group ego,

n and m are an integer of 0 to 20;

The present invention also provides an olefin oligomerization process comprising the step of mass-reacting olefins in the presence of the catalyst system for olefin oligomerization.

Hereinafter, a catalyst system for olefin oligomerization and a method for olefin oligomerization according to specific embodiments of the present invention will be described in detail.

The term " olefin oligomerization " used in the present invention means olefin polymerization. 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 present invention means to selectively produce 1-hexene or 1-octene from ethylene.

According to one embodiment of the present invention, a ligand compound represented by the following general formula (1); A transition metal source; And a cocatalyst, wherein the catalyst system for olefin oligomerization is provided:

[Chemical Formula 1]

In Formula 1,

E ₁ to E ₃ each independently represent an element selected from the group consisting of boron (B), carbon (C), nitrogen (N), oxygen (O), silicon (Si), phosphorus (P) And at least one of E ₁ to E ₃ is an element selected from the group consisting of boron (B), nitrogen (N), oxygen (O), silicon (Si), phosphorus (P) ,

R ₁ to R _{12 each} represent a hydrogen atom, an alkyl (Alky) group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, a haloalkyl an arylalkyl group having 6 to 40 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an arylsilyl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, An alkoxy group having 1 to 20 carbon atoms, an alkylsiloxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a halogen (Halogen) group, or an amino group ego,

n and m are an integer of 0 to 20;

The present inventors have found that the ligand compound having the above specific structure and the catalyst system for olefin oligomerization including a transition metal source and a cocatalyst can be easily controlled in the electronic and stereoscopic environment around the transition metal by appropriately controlling the substituent introduced into the ligand compound It is confirmed through experiments that oligomerization of olefins is possible with high catalytic activity and selectivity, and the invention is completed.

Particularly, the ligand compound includes two pentagonal rings, and these rings are heteroatoms such as boron (B), nitrogen (N), oxygen (O), silicon (Si), phosphorus (P) Due to such structural features, the ligand compound can be applied to oligomerization catalyst systems of olefins to exhibit a high oligomerization reaction activity, and in particular, can be used for the reaction of 1-hexene, 1-octene, etc. High selectivity can be shown. This is presumably due to the interaction between each adjacent chromium active point.

In the ligand compound represented by Formula 1, E ₁ to E ₃ are each independently selected from the group consisting of boron (B), carbon (C), nitrogen (N), oxygen (O), silicon (Si) , And sulfur (S). In the ligand compound, when the above-described hetero elements are introduced at the E ₁ to E ₃ positions, the hetero elements are electronically coupled with the central metal to stabilize the central metal, while increasing the electron density to 1-Hexene / 1-Octene Can be increased.

Particularly, at least one of E ₁ to E ₃ is an element selected from the group consisting of boron (B), nitrogen (N), oxygen (O), silicon (Si), phosphorus (P) And more preferably at least one of the above E ₁ to E ₃ may be phosphorus (P), nitrogen (N), oxygen (O), or sulfur (S).

In the general formula (1), R ₁ to R _{12 each} represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, An aryl group having 6 to 40 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an arylsilyl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, An alkoxy group of 1 to 20 carbon atoms, an alkyloxy group of 1 to 20 carbon atoms, an alkyloxy group of 1 to 20 carbon atoms, an aryloxy group of 6 to 20 carbon atoms, a halogen group, Or an amino group, and the aryl group may be substituted with at least one substituent selected from the group consisting of phenyl, biphenyl, triphenyl, triphenylene, naphthalenyl, anthracenyl, phenrenyl, phenanthrenyl, fluorenyl, pyrenyl, Aromatic hydrocarbons such as nyl, azulenyl, dibenzothiophenyl, dibenzofuranyl, dibenzoseleno Benzothiophenyl, benzoselenophenyl, carbazonyl, indolocarbazolyl, pyridylindolinyl, pyrrolodipyridinyl, pyrazolyl, imidazolyl, pyrazolyl, thiophenyl, Thiazolyl, oxazolyl, thiazolyl, oxadiazolinyl, oxatriazolyl, dioxazolyl, thiadiazolyl, pyridyl, pyridazinyl, pyrimidyl, pyrazinyl, triazinyl, oxazinyl, oxathiazinyl, oxa Benzothiazolyl, benzothiazolyl, quinolinin, isoquinolinyl, cinnolinyl, quinazolinyl, quinoxalinyl, quinoxalinyl, quinoxalinyl, quinoxalinyl, quinoxalinyl, Naphthyridyl, phthalazinyl, pteridinyl, xanthenyl, acridyl, phenazinyl, phenothiazinyl, phenoxazinyl, benzofuropyridyl, furodipyridyl, benzothienopyridyl, thienodipyridyl Aromatic heterocyclic compounds such as benzo-selenophenopyridyl and selenophenodipyridyl Groups and the like.

R ₁ to R ₁₂ in Formula 1 are hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, a haloalkyl group, or an aryl group, , A polyolefin having a high selectivity can be produced.

Specific examples of such ligand compounds are as follows:

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

Meanwhile, the transition metal source of the olefin oligomerization catalyst system in one embodiment of the present invention serves as a main catalyst, and a chromium precursor can be used. More specifically, chromium (III) acetylacetonate, chromium tristate tetrafluoride, And chromium (III) 2-ethylhexanoate.

Further, the promoter is an organometallic compound containing a Group 13 metal, and is not particularly limited as long as it can be used for mass-producing olefins under the catalyst of a transition metal compound. Specifically, the promoter may be at least one selected from the group consisting of compounds represented by the following formulas (2) to (4).

(2)

In Formula 2,

R < ₁₃ > are the same or different from each other and each independently represents an alkyl group having 1 to 10 carbon atoms, r is an integer of 1 to 70,

(3)

In Formula 3,

R ₁₄ to R ₁₆ are the same or different from each other and each independently represents hydrogen, halogen, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and at least one of R ₁₄ to R ₁₆ is a group having 1 to 10 carbon atoms Alkyl group,

[CD]

In Formula 4,

C is a proton-binding cation of a Lewis Base, a metal or nonmetal compound having oxidation potential, D is a compound of an element belonging to Groups 5 to 15 in the periodic table, In the absence, D is a Lewis Acid-like compound.

The cocatalysts represented by the above formulas (2) to (4) can serve to cationize or activate the central metal (M) of the transition metal compound as the main catalyst so that ethylene reacts well with the core metal.

The compound represented by Formula 2 may be selected from the group consisting of Methylaluminoxane, Ethylaluminoxane, Butylaluminoxane, Hexylaluminoxane, Octylaluminoxane, Decylaluminoxane, ) And the like.

In addition, the compound represented by Formula 3 may be a compound represented by Formula 3, such as trimethylaluminum, triethylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, Tridecylaluminum; Dimethyl aluminum methoxide, diethyl aluminum methoxide, dibutyl aluminum methoxide; Dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride; Methylaluminum dimethoxide, Ethylaluminum dimethoxide, Butylaluminum dimethoxide; Methyl aluminum dichloride, Ethylaluminum dichloride, Butylaluminum dichloride and the like may be used.

In addition, the compound represented by the general formula (4) may be a compound selected from the group consisting of trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tributylammonium tetraphenylborate, tetraphenylborate, trimethylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, (Pentafluorophenyl) borate, tributylammonium tetrakis (pentafluorophenyl) borate, anilinium tetraphenylborate, and the like. ate, anilinium tetrakis (pentafluorophenyl) borate, pyridinium tetraphenylborate, pyridinium tetrakis (pentafluorophenyl) borate, pyridinium tetrakis (pentafluorophenyl) borate, ferrocenium tetrakis (pentafluorophenyl) borate, silver tetra phenylborate, silver tetrakis (pentafluorophenyl) borate, ), Tris (pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane, ), Tris (2,3,4,5-tetraphenylphenyl) borane, tris (3,4,5-trifluorophenyl) borane Tris (3,4,5-trifluorophenyl) borane) or the like.

Alcohols may be used as a cocatalyst in the olefin oligomerization catalyst system of one embodiment, and more preferably, methyl aluminoxane (MAO) may be used.

The molar ratio of the ligand compound: transition metal source: cocatalyst is about 0.5: 1: 1 to about 10: 1: 10,000 for the olefin oligomerization catalyst system to increase the selectivity for the linear alpha olefin and increase the mass- And preferably from about 0.5: 1: 100 to about 5: 1: 3,000. However, the present invention is not limited thereto.

According to another embodiment of the present invention, there is provided a process for preparing an olefin oligomer comprising the step of mass-reacting an olefin in the presence of the catalyst system for olefin oligomerization. The use of the olefin oligomerization catalyst system of one embodiment can provide a method of oligomerization of olefins having improved activity and selectivity of the reaction. At this time, the olefin is preferably ethylene.

The olefin oligomerization according to the present invention can be carried out in the presence of an inert solvent in the presence or absence of an inert solvent using a conventional apparatus and contact technique with the catalyst system for olefin oligomerization, a slurry reaction in which the catalyst system is partially or completely dissolved , Two-phase liquid / liquid reactions, or bulk-phase or gas-phase reactions in which the product olefins act as the main medium, and a homogeneous liquid phase reaction is preferred.

The olefin oligomerization reaction can be carried out in any inert solvent that does not react with the catalyst compound and the activator. 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 solvent can be used by removing a small amount of water or air acting as catalyst poison by treating with a small amount of alkylaluminum.

The olefin oligomerization reaction may be carried out at a temperature of from about 0 ° C to about 200 ° C, preferably from about 30 ° C to about 150 ° C. In addition, the olefin oligomerization reaction can be carried out at a pressure of from about 1 bar to about 300 bar, preferably from about 10 bar to about 100 bar.

The use of a catalyst system comprising a ligand compound according to the present invention enables oligomerization of ethylene with high catalytic activity and selectivity compared to existing catalyst systems, and a more stable polymerization reaction is possible because of excellent catalyst stability.

The invention will be described in more detail in the following examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.

All synthetic reactions were conducted under an inert atmosphere such as nitrogen or argon, using standard Schlenk technology and Glove Box technology. In the following examples, ligands 1 and 2 were purchased from Strem and used without purification. The chromium reagent was purchased from Sigma-Aldrich and used without purification.

The ligand compounds used in the following examples are as follows:

Ligand  One

Ligand  2

Example  One: Trichlorotetra tetrahydrofuran chromium and Ligand  1 Oligomerization  Evaluation of Catalyst Properties

A 2 L stainless steel reactor was charged with nitrogen, 1 L of cyclohexane was added, 9.0 mmol of MAO (10 wt% in toluene, Albermale) was added and the temperature was raised to 45 ° C. In a glove box, 11 mg (0.030 mmol) of trichlorotetrahydrofuran chromium in 10 mL of toluene was taken in a 50 mL Schlenk vessel, and 19 mg (0.060 mmol) of ligand 1 was mixed, stirred at room temperature for 5 minutes, Respectively. The pressure reactor was charged with 30 bar of ethylene and stirred at a stirring speed of 300 rpm. After one hour, 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. After the excess ethylene was discharged from the reactor, ethanol containing 10 vol% hydrochloric acid was injected into the liquid contained in the reactor. A small amount of organic layer sample was passed over silica gel, dried and analyzed by GC-FID. The remaining organic layer was filtered to separate the solid wax / polymer product. These solid products were dried in an oven at 80 DEG C for 8 hours and then weighed to give polyethylene.

Example  2: Chromium (III) 2 - Ethyl hexanoate and Ligand  1 Oligomerization  Evaluation of Catalyst Properties

Except that 13 mg (0.030 mmol) of chromium (Ⅲ) 2-ethylhexanoate was used in place of 11 mg (0.030 mmol) of trichlorotrifluoroethane trichloride in tetrahydrofuran.

Example  3: Chromium (III) acetylacetonate and Ligand  1 Oligomerization  Evaluation of Catalyst Properties

Polyethylene was obtained in the same manner as in Example 1 except that 14 mg (0.030 mmol) of chromium (Ⅲ) acetylacetonate was used in place of 11 mg (0.030 mmol) of trichlorotrifluoroethane trichloride.

Example  4: Trichlorotetra tetrahydrofuran chromium and Ligand  2 Oligomerization  Evaluation of Catalyst Properties

Except that 22 mg (0.060 mmol) of the ligand 2 was used instead of 19 mg (0.060 mmol) of the ligand 1, to obtain polyethylene.

Example  5: Chromium (III) 2 - Ethyl hexanoate and Ligand  2 Oligomerization  Evaluation of Catalyst Properties

Polyethylene was obtained in the same manner as in Example 2 except that 22 mg (0.060 mmol) of the ligand 2 was used instead of 10 mg (0.060 mmol) of the ligand 1.

Example  6: Chromium (III) acetylacetonate and Ligand  2 Oligomerization  Evaluation of Catalyst Properties

Polyethylene was obtained in the same manner as in Example 3 except that 22 mg (0.060 mmol) of the ligand 2 was used instead of 10 mg (0.060 mmol) of the ligand 1.

Comparative Example  One

1-hexene was prepared in the same manner as in Example 1 using the TaCl ₅ catalyst of U.S. Patent No. 6344594.

The results of the production of 1-hexene and 1-octene using the catalysts prepared in the respective Examples and the catalysts of Comparative Examples are shown in Table 1 below.

Catalytic activity and analytical results Catalytic activity * Selectivity (wt%) 1-hexene 1-octene 1-decene Polyethylene (PE) Example 1 654 77.0 21.8 - 1.2 Example 2 772 71.0 27.5 - 1.5 Example 3 812 79.6 19.1 - 1.3 Example 4 1,231 81.2 17.9 - 0.9 Example 5 1,324 83.1 15.9 - 1.0 Example 6 1,455 81.5 16.7 - 1.8 Comparative Example 1 350 83.3 - 13.5 3.2

* Catalytic activity unit: g- (1-Hexene + 1-Octene) / mmol-Metal · h

As shown in the above Table 1, the experiments using the compounds according to the present invention show very high catalytic activity, produce very little polyethylene and have a remarkable selectivity for alpha-olefins (1-hexene and 1-octene) .

Claims (12)

A ligand compound represented by the following formula (1);
A transition metal source; And
A catalyst for olefin oligomerization comprising:
[Chemical Formula 1]

In Formula 1,
E ₁ to E ₃ each independently represent an element selected from the group consisting of boron (B), carbon (C), nitrogen (N), oxygen (O), silicon (Si), phosphorus (P) And at least one of E ₁ to E ₃ is an element selected from the group consisting of boron (B), nitrogen (N), oxygen (O), silicon (Si), phosphorus (P) ,
R ₁ to R _{12 each} represent a hydrogen atom, an alkyl (Alky) group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, a haloalkyl an arylalkyl group having 6 to 40 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an arylsilyl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, An alkoxy group having 1 to 20 carbon atoms, an alkylsiloxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a halogen (Halogen) group, or an amino group ego,
n and m are an integer of 0 to 20;
The method according to claim 1,
Wherein at least one of E ₁ to E ₃ in Formula 1 is phosphorus (P), nitrogen (N), oxygen (O), or sulfur (S).
The method according to claim 1,
R ₁ to R ₁₂ in Formula 1 are selected from the group consisting of hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, a haloalkyl group, and an aryl group. .
The olefin oligomerization catalyst system according to claim 1, wherein the ligand compound is selected from the group consisting of the following structural formulas:

,

,

,

,

,

,

,

,

, And

The method according to claim 1,
Wherein the transition metal source is at least one selected from the group consisting of chromium (III) acetylacetonate, chromium trichlorotris tetrafluoride, and chromium (III) 2-ethylhexanoate.
The method according to claim 1,
Wherein the promoter is at least one selected from the group consisting of compounds represented by the following formulas (2) to (4):
(2)

In Formula 2,
R < ₁₃ > are the same or different from each other and each independently represents an alkyl group having 1 to 10 carbon atoms, r is an integer of 1 to 70,
(3)

In Formula 3,
R ₁₄ to R ₁₆ are the same or different from each other and each independently represents hydrogen, halogen, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and at least one of R ₁₄ to R ₁₆ is a group having 1 to 10 carbon atoms Alkyl group,
[Chemical Formula 4]
[CD]
In Formula 4,
C is a hydrogen ion-binding cation of a Lewis base, an oxidizing metal or a nonmetal compound, D is a compound of an element belonging to Groups 5 to 15 on the periodic table, and D is a compound of a Lewis acid to be.
The method according to claim 6,
The compound represented by Formula 2 may be selected from the group consisting of Methylaluminoxane, Ethylaluminoxane, Butylaluminoxane, Hexylaluminoxane, Octylaluminoxane, and Decylaluminoxane. Lt; RTI ID = 0.0 > oligomerization < / RTI >
The method according to claim 6,
The compound represented by Formula 3 may be selected from the group consisting of trimethylaluminum, triethylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum; Dimethyl aluminum methoxide, diethyl aluminum methoxide, dibutyl aluminum methoxide; Dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride; Methylaluminum dimethoxide, Ethylaluminum dimethoxide, Butylaluminum dimethoxide; An olefin oligomerization catalyst system selected from the group consisting of methyl aluminum dichloride, ethylaluminum dichloride, and butylaluminum dichloride.
The method according to claim 6,
The compound represented by the general formula (4) may be at least one selected from the group consisting of trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tributylammonium tetraphenylborate, (Pentafluorophenyl) borate), triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (Pentafluorophenyl) borate, tributylammonium tetrakis (pentafluorophenyl) borate, anilinium tetraphenylborate, triphenylphosphine borate, Pyridinium tetrakis (pentafluorophenyl) borate, Pyridinium tetraphenylborate, Pyridinium tetrakis (pentafluorophenyl) borate, Pyridinium tetrakis (pentafluorophenyl) Ferrocenium tetrakis (pentafluorophenyl) borate, silver tetra phenylborate, silver tetrakis (pentafluorophenyl) borate, tris (pentafluorophenyl) borate, (Pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane, (2,3,4,5-tetraphenylphenyl) borane, and tris (3,4,5-trifluorophenyl) borane (Tris 3,4,5-trifluorophenyl) borane), < / RTI > Murray Purification catalyst system.
A process for the oligomerization of olefins comprising subjecting the olefins to a multiplication reaction in the presence of the catalyst system for olefin oligomerization of claim 1.
11. The method of claim 10,
Wherein the oligomerization reaction temperature is 0 to 200 < 0 > C.
11. The method of claim 10,
Wherein the oligomerization reaction pressure is 1 to 300 bar.