KR102029087B1 - Novel transition metal compound - Google Patents

Abstract

The present invention relates to a novel transition metal compound represented by Formula 1, wherein the novel ligand compound and the transition metal compound according to the present invention are catalysts for polymerization in the preparation of olefin polymers having high crystallinity, high density and high molecular weight. It can be usefully used.

Description

New Transition Metal Compounds {NOVEL TRANSITION METAL COMPOUND}

The present invention relates to novel transition metal compounds.

Metallocene catalysts for olefin polymerization have been developed for a long time. Metallocene compounds are generally used by activation with aluminoxanes, boranes, borates or other activators. For example, a metallocene compound having a ligand including a cyclopentadienyl group and two sigma chloride ligands uses aluminoxane as an activator. When the chloride group of such a metallocene compound is substituted with another ligand (eg, benzyl or trimethylsilylmethyl group (—CH ₂ SiMe ₃ )), an example showing an effect such as increased catalytic activity has been reported.

Dow disclosed [Me ₂ Si (Me ₄ C ₅ ) NtBu] TiCl ₂ (Constrained-Geometry Catalyst, CGC) in U.S. Patent No. 5,064,802 in the early 1990s. The advantages over the known metallocene catalysts can be summarized in two main ways:

(1) to produce high molecular weight polymers with high activity even at high polymerization temperatures;

(2) The copolymerization of alpha-olefins with high steric hindrances such as 1-hexene and 1-octene is also excellent.

In addition, during the polymerization reaction, various characteristics of CGC are gradually known, and efforts to synthesize derivatives thereof and use them as polymerization catalysts have been actively conducted in academia and industry.

One approach has been to synthesize metal compounds in which various bridges and nitrogen substituents are introduced instead of silicon bridges and to polymerize them. Representative metal compounds known until recently are phosphorus, ethylene or propylene, methylidene and methylene bridges instead of CGC-structured silicon bridges, but polymerized against CGC when applied to ethylene polymerization or copolymerization of ethylene and alphaolefin. It did not show excellent results in terms of activity or copolymerization performance.

In another approach, many compounds composed of an oxido ligand instead of the amido ligand of CGC have been synthesized, and some polymerization has been attempted using the compound.

In addition, various asymmetric uncrosslinked metallocenes have been developed. For example, metallocenes composed of (cyclopentadienyl) (indenyl) and (cyclopentadienyl) (fluorenyl) metallocene, (substituted indenyl) (cyclopentadienyl), and the like are known. have.

However, in terms of commercial applications, the catalyst compositions of the non-crosslinkable metallocenes do not sufficiently exhibit the polymerization activity of olefins and have difficulty in polymerizing high molecular weight polyolefins.

U.S. Patent 5,064,802

The problem to be solved of the present invention is to provide a novel transition metal compound.

In order to solve the above problems, the present invention

It provides a transition metal compound represented by the formula (1):

[Formula 1]

In Chemical Formula 1,

R ₁ to R ₁₃ are each independently hydrogen, silyl, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, and arylalkyl having 7 to 20 carbon atoms. Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl having 1 to 20 carbon atoms; Two or more adjacent to each other of R ₁ to R ₁₃ may be connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms; The aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms;

Q ₁ to Q ₃ are each independently hydrogen, halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 6 to 20 carbon atoms, and arylalkyl having 7 to 20 carbon atoms. , Alkyl amido having 1 to 20 carbon atoms, aryl amido having 6 to 20 carbon atoms, or alkylidene having 1 to 20 carbon atoms;

M is Ti, Zr or hf.

The novel transition metal compound according to the present invention can be usefully used as a catalyst for the polymerization reaction in the preparation of olefin polymers having high crystallinity, high density and high molecular weight.

Hereinafter, the present invention will be described in more detail to aid in understanding the present invention.

The terms or words used in this specification and claims are not to be construed as limiting in their usual or dictionary meanings, and the inventors may appropriately define the concept of terms in order to best explain their invention in the best way possible. It should be interpreted as meaning and concept corresponding to the technical idea of the present invention based on the principle that the present invention.

The transition metal compound of the present invention is represented by the following formula (1).

[Formula 1]

In Chemical Formula 1,

R ₁ to R ₁₃ are each independently hydrogen, silyl, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, and arylalkyl having 7 to 20 carbon atoms. Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl having 1 to 20 carbon atoms; Two or more adjacent to each other of R ₁ to R ₁₃ may be connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms; The aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms;

Q ₁ to Q ₃ are each independently hydrogen, halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 6 to 20 carbon atoms, and arylalkyl having 7 to 20 carbon atoms. , Alkyl amido having 1 to 20 carbon atoms, aryl amido having 6 to 20 carbon atoms, or alkylidene having 1 to 20 carbon atoms;

M is Ti, Zr or hf.

In addition, Q ₁ to Q ₃ may be each independently hydrogen, alkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 6 to 20 carbon atoms, or arylalkyl having 7 to 20 carbon atoms.

In addition, each of R ₁ to R ₁₃ may independently be hydrogen, alkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, or arylalkyl having 7 to 20 carbon atoms; Two or more adjacent to each other of R ₁ to R ₁₃ may be connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms; The aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms.

In addition, R ₁₂ and R ₁₃ are connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms, and the aliphatic ring or aromatic ring is halogen, alkyl having 1 to 20 carbon atoms, or 6 carbon atoms. To aryl of 20 to 20.

In addition, the transition metal compound represented by Formula 1 may be a compound of Formula 2:

[Formula 2]

In Chemical Formula 2,

R ₁ to R ₁₁ , Q ₁ , Q ₂ , and M are as defined in Formula 1 above;

R ₁₄ to R ₁₆ are each independently halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms.

In one embodiment of the present invention, the compound of Formula 1 may be any one of the following compounds:

A)

및

And

B)

.

.

Each substituent defined in the present specification will be described in detail as follows.

As used herein, the term "halogen" means fluorine, chlorine, bromine or iodine, unless stated otherwise.

As used herein, the term 'alkyl' refers to a straight or branched chain hydrocarbon residue unless otherwise indicated.

As used herein, the term 'alkenyl' refers to a straight or branched alkenyl group unless otherwise indicated.

The branched chain is alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Or arylalkyl having 7 to 20 carbon atoms.

According to one embodiment of the present invention, the silyl group is trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, trihexylsilyl, triisopropylsilyl, triisobutylsilyl, triethoxysilyl, triphenylsilyl, tris ( Trimethylsilyl) silyl and the like, but are not limited to these examples.

According to an example of the present invention, the aryl group preferably has 6 to 20 carbon atoms, and specifically, phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilinyl, anisolyl, and the like, but is not limited thereto.

The alkylaryl group means an aryl group substituted by the alkyl group.

The arylalkyl group means an alkyl group substituted by the aryl group.

The ring (or heterocyclic group) means a monovalent aliphatic or aromatic hydrocarbon group having 5 to 20 carbon atoms and containing one or more hetero atoms, and may be a single ring or a condensed ring of two or more rings. In addition, the heterocyclic group may be substituted or unsubstituted with an alkyl group. Examples thereof include indolin, tetrahydroquinoline, and the like, but the present invention is not limited thereto.

The alkyl amino group means an amino group substituted by the alkyl group, and there are a dimethylamino group, a diethylamino group, and the like, but is not limited thereto.

According to one embodiment of the present invention, the aryl group preferably has 6 to 20 carbon atoms, specifically, phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilinyl, anisolyl, and the like, but is not limited thereto. no.

In the transition metal compound of the present invention, the ligand compound which binds to the transition metal may be represented by the following Chemical Formula 3, and may be prepared by the following preparation method. Specifically, the ligand compound represented by Formula 3 may be prepared by a method comprising the step of preparing a compound of Formula 3 by reacting a compound of Formula 4 with a compound of Formula 5 below.

[Formula 3]

[Formula 4]

[Formula 5]

Wherein R ₁ to R ₁₃ are each independently hydrogen, silyl, alkyl of 1 to 20 carbon atoms, alkenyl of 2 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, alkylaryl of 7 to 20 carbon atoms, and 7 to 20 carbon atoms. A metalloid radical of a Group 14 metal substituted with an arylalkyl of 1 or a hydrocarbyl having 1 to 20 carbon atoms; Two or more adjacent to each other of R ₁ to R ₁₃ may be connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms; The aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms; X is halogen.

In addition, each of R ₁ to R ₁₃ may independently be hydrogen, alkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, or arylalkyl having 7 to 20 carbon atoms; Two or more adjacent to each other of R ₁ to R ₁₃ may be connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms; The aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms.

In addition, R ₁₂ and R ₁₃ are connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms, and the aliphatic ring or aromatic ring is halogen, alkyl having 1 to 20 carbon atoms, or 6 carbon atoms. To aryl of 20 to 20.

The ligand compound represented by Formula 3 may be prepared by reacting the compound of Formula 4 with the compound of Formula 5.

Scheme 1

The compound of Formula 4 and the compound of Formula 5 may be reacted with a molar ratio of 1: 1 to 1: 1.6.

The reaction may be carried out in the presence of a palladium catalyst at base conditions, specifically, in the presence of a palladium catalyst and a phosphine ligand at base conditions, wherein the reaction may be carried out in an organic solvent such as toluene.

The palladium catalyst is tetrakis (triphenylphosphine) palladium [Pd (PPh ₃ ) ₄ ], palladium chloride (PdCl ₂ ), palladium acetate (Pd (OAc) ₂ ), bis (dibenzylideneacetone) palladium (Pd ( dba) ₂ ), dichloro [1,1'-bis (diphenylphosphino) ferrocene] palladium [PdCl ₂ (dppf)], tris (dibenzylideneacetone) dipalladium (0) [Pd ₂ (dba) ₃ ] And it may be at least one selected from the group consisting of Pd (tBu ₃ P ₂ ).

The phosphine ligands include bis (2-diphenylphosphinophenyl) ether, 4,5-bis (diphenylphosphino) -9,9-dimethylxanthene, cyclohexyl diphenyl phosphine, 1,1'- It may be one or more selected from the group consisting of bis (diphenylphosphino) ferrocene, 1,2-bis (diphenylphosphino) ether and 1,3-bis (diphenylphosphino) propane.

The type of the base for achieving the base conditions is not particularly limited, but specific examples include tBuOLi, potassium triphosphate (K ₃ PO ₄ ), potassium carbonate (K ₂ CO ₃ ), cesium carbonate (Cs ₂ CO ₃ ), and fluorinated Potassium (KF), sodium fluoride (NaF), cesium fluoride (CsF), tetrabutylammonium fluoride (TBAF), or mixtures thereof.

The reaction of step (1) may be carried out by a method of reacting for 1 to 48 hours in a temperature range of 60 to 150 ℃, specifically to a method for reacting for 6 to 18 hours in a temperature range of 70 to 120 ℃ Can be performed by

The compound of Chemical Formula 2 prepared through the above step may further undergo a recrystallization step. Thus, the method for preparing a transition metal compound according to an example of the present invention may further include recrystallizing the compound of Chemical Formula 2 after the above step. It can be included as.

The recrystallization may be performed using an organic solvent such as toluene, such as a reaction solvent, and purified through recrystallization to obtain a pure compound of Formula 2.

In addition, the transition metal compound represented by the formula (1) of the present invention comprises the steps of (a) preparing a compound of formula (6) by reacting a compound of the formula (b) reacting a compound of Formula 6 with a compound of Formula 7 to prepare a compound of Formula 8; And (c) reacting a compound of Formula 8 with a Grignard reagent of Formula 9 to produce a compound of Formula 1.

[Formula 1]

[Formula 3]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

Where

R ₁ to R ₁₃ are each independently hydrogen, silyl, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, and arylalkyl having 7 to 20 carbon atoms. Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl having 1 to 20 carbon atoms; Two or more adjacent to each other of R ₁ to R ₁₃ may be connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms; The aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms;

Q and Q ₁ to Q ₃ are each independently hydrogen, halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 6 to 20 carbon atoms, and having 7 to 20 carbon atoms. Arylalkyl, alkyl amido having 1 to 20 carbon atoms, aryl amido having 6 to 20 carbon atoms, or alkylidene having 1 to 20 carbon atoms;

M is Ti, Zr or hf;

X is halogen.

In addition, Q, Q ₁ to Q ₃ may be each independently hydrogen, alkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 6 to 20 carbon atoms, or arylalkyl having 7 to 20 carbon atoms.

In addition, each of R ₁ to R ₁₃ may independently be hydrogen, alkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, or arylalkyl having 7 to 20 carbon atoms; Two or more adjacent to each other of R ₁ to R ₁₃ may be connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms; The aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms.

In addition, R ₁₂ and R ₁₃ are connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms, and the aliphatic ring or aromatic ring is halogen, alkyl having 1 to 20 carbon atoms, or 6 carbon atoms. To aryl of 20 to 20.

(a) reacting a compound of formula 3 with an organolithium compound to prepare a compound of formula 6

In step (a), a compound of Formula 6 is prepared by reacting a compound of Formula 3 with an organolithium compound.

In the step (a), the compound of Formula 3 and the organolithium compound may be reacted with a molar ratio of 1: 0.9 to 1: 1.5, and specifically, may be reacted at a molar ratio of 1: 1 to 1: 1.2.

The reaction of step (a) may be carried out under an organic solvent such as toluene, diethoxyethane, ether, or by adding the organolithium compound to the compound of Formula 1 under an organic solvent.

The organolithium compound may be at least one selected from the group consisting of n-butyllithium, sec-butyllithium, methyllithium, ethyllithium, isopropyllithium, cyclohexylithium, allyllithium, vinyllithium, phenyllithium and benzyllithium. .

The reaction of step (a) is added to the compound of formula 1 in the temperature range of -20 ℃ to 50 ℃, and then heated to a temperature range of 60 ℃ to 150 ℃, 20 minutes to 12 hours It may be carried out by a method for reacting during the reaction, and specifically, after adding the organolithium compound to the compound of Formula 1 at a temperature range of 0 ° C to 40 ° C, the temperature is raised to a temperature range of 90 ° C to 100 ° C, and then 1 It can be carried out by a method for reacting for 6 hours.

(b) reacting a compound of Formula 6 with a compound of Formula 7 to produce a compound of Formula 8; And

In step (b), the compound of formula 6 is prepared by reacting the compound of formula 6 obtained in step (a) with the compound of formula 7.

In step (b), the compound of Formula 6 and the compound of Formula 7 may be reacted with a molar ratio of 1: 1 to 1: 1.8, and specifically, may be reacted at a molar ratio of 1: 1 to 1: 1.2. .

The reaction of step (b) is added to the compound of formula 7 to the compound of formula 6 in the temperature range of -80 ℃ to -20 ℃ under reflux conditions, and then heated to a temperature range of 0 ℃ to 140 ℃ , By reaction for 1 to 48 hours.

(c) reacting a compound of Formula 8 with a Grignard reagent of Formula 9 to produce a compound of Formula 1

In Formula 9, Q may be any one of Q ₁ to Q ₃ , and may be the same as or different from each other. Q ₁ to Q ₃ are as defined for Chemical Formula 1.

The transition metal compound represented by Chemical Formula 1 according to the present invention, when activated by reacting with an additional promoter and then applied to olefin polymerization, produces a polyolefin having high crystallinity, high density, and high molecular weight even at a high polymerization temperature. It is possible.

In particular, by using the catalyst composition containing the transition metal compound, it is possible to prepare a polymer having a narrow MWD compared to CGC, excellent copolymerizability, and high molecular weight even in a low density region.

More specifically, the transition metal compound according to the present invention alone or in addition to the transition metal compound in the form of a composition further comprising one or more of the cocatalyst compounds represented by the following formulas (10), (11) and (12), the polymerization reaction It can be used as a catalyst.

<Formula 10>

-[Al (R ₁₇ ) -O] _m-

In Chemical Formula 10,

R ₁₇ may be the same or different from each other, and each independently halogen; Hydrocarbons having 1 to 20 carbon atoms; Or a hydrocarbon having 1 to 20 carbon atoms substituted with halogen;

m is an integer of 2 or more;

<Formula 11>

J (R ₁₇ ) ₃

In Chemical Formula 11,

R ₁₇ is as defined in Formula 10 above;

J is aluminum or boron;

<Formula 12>

_{^{[EH] + [ZA 4]}} - or _{^{[E] + [ZA 4]}} -

In Chemical Formula 12,

E is a neutral or cationic Lewis base;

H is a hydrogen atom;

Z is a Group 13 element;

A may be the same or different from each other, and each independently is an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms, unsubstituted or substituted with one or more hydrogen atoms, halogen, hydrocarbon having 1 to 20 carbon atoms, alkoxy or phenoxy. .

Examples of the compound represented by Formula 10 include modified methyl aluminoxane (MMAO), methyl aluminoxane (MAO), ethyl aluminoxane, isobutyl aluminoxane, butyl aluminoxane, and the like, and more preferred compound is methyl aluminoxane.

Examples of the compound represented by Formula 11 include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethylchloro aluminum, triisopropyl aluminum, tri-s-butyl aluminum, tricyclopentyl aluminum , Tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl Boron, triethylboron, triisobutylboron, tripropylboron, tributylboron and the like, and more preferred compounds are selected from trimethylaluminum, triethylaluminum and triisobutylaluminum.

Examples of the compound represented by Formula 12 include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetra (p-tolyl) Boron, trimethylammonium tetra (o, p-dimethylphenyl) boron, tributylammonium tetra (p-trifluoromethylphenyl) boron, trimethylammonium tetra (p-trifluoromethylphenyl) boron, tributylammonium tetra Pentafluorophenylboron, N, N-diethylanilinium tetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron, ethylammonium tetrapentafluorophenylboron, triphenylphosphonium tetra Phenyl boron, trimethyl phosphonium tetraphenyl boron, triethyl ammonium tetraphenyl aluminum, tributyl ammonium tetraphenyl aluminum, trimethyl ammonium tetraphenyl aluminum, t Propyl Ammonium Tetraphenyl Aluminum, Trimethyl Ammonium Tetra (p-tolyl) Aluminum, Tripropyl Ammonium Tetra (p-tolyl) Aluminum, Triethyl Ammonium Tetra (o, p-dimethylphenyl) Aluminum, Tributyl Ammonium Tetra (p-trifluoromethylphenyl) aluminum, trimethylammonium tetra (p-trifluoromethylphenyl) aluminum, tributylammonium tetrapentafluorophenylaluminum, N, N-diethylanilinium tetraphenylaluminum, N, N-diethylanilinium tetrapentafluorophenylaluminum, diethylammonium tetrapentatetraphenylaluminum, triphenylphosphonium tetraphenylaluminum, trimethylphosphonium tetraphenylaluminum, tripropylammonium tetra (p-tolyl) boron , Triethylammonium tetra (o, p-dimethylphenyl) boron, tributylammonium tetra (p-trifluoromethylphenyl) boron, triphenylcarbonium tetra (p-trifluoro Butyl phenyl) boron and the like, triphenylamine car I phenylboronic as Titanium tetra-penta flow.

Preferably, alumoxane can be used, more preferably methylalumoxane (MAO) which is alkylalumoxane.

The catalyst composition may include the steps of: 1) contacting a transition metal compound represented by Formula 1 with a compound represented by Formula 10 or Formula 11 to obtain a mixture; And 2) it can be prepared by a method comprising the step of adding a compound represented by the formula (12) to the mixture.

In addition, the catalyst composition may be prepared by a method of contacting the transition metal compound represented by Formula 1 with the compound represented by Formula 10 as a second method.

In the case of the first method of the method for preparing the catalyst composition, the molar ratio of the transition metal compound represented by the formula (1) / compound represented by the formula (10) or formula (11) is preferably 1 / 5,000 to 1/2, more Preferably it is 1 / 1,000-1/10, Most preferably, it is 1/500-1/20. When the molar ratio of the transition metal compound represented by Formula 1 / compound represented by Formula 10 or Formula 11 is more than 1/2, the amount of the alkylating agent is very small so that alkylation of the metal compound may not proceed completely. In the case where the molar ratio is less than 1 / 5,000, alkylation of the metal compound is performed, but there is a problem that the activation of the alkylated metal compound is not completely performed due to a side reaction between the remaining excess alkylating agent and the activator of the compound of Formula 12. . In addition, the molar ratio of the transition metal compound represented by Formula 2 to the compound represented by Formula 12 is preferably 1/25 to 1, more preferably 1/10 to 1, and most preferably 1/5. To 1; When the molar ratio of the transition metal compound represented by Chemical Formula 2 to the compound represented by Chemical Formula 12 is greater than 1, the amount of the activator is relatively small, and thus the activity of the catalyst composition generated due to the incomplete activation of the metal compound. If the molar ratio is less than 1/25, the activation of the metal compound is completely made, but the excess of the activator, the cost of the catalyst composition is not economical or the purity of the resulting polymer is poor.

In the second method of preparing the catalyst composition, the molar ratio of the transition metal compound represented by Chemical Formula 1 / Compound 10 is preferably 1 / 10,000 to 1/10, more preferably 1 / 5,000 to 1/100, most preferably 1 / 3,000 to 1/500. If the molar ratio is greater than 1/10, the amount of the activator is relatively small, so that the activation of the metal compound is not fully performed, resulting in a decrease in the activity of the resulting catalyst composition. Although the activation is complete, there is a problem that the unit cost of the catalyst composition is not economical or the purity of the resulting polymer is inferior with the excess activator remaining.

In preparing the catalyst composition, a hydrocarbon solvent such as pentane, hexane, heptane, or the like, or an aromatic solvent such as benzene, toluene, or the like may be used.

In addition, the catalyst composition may include the transition metal compound and the cocatalyst compound in a form supported on a carrier.

Specifically, the polymerization reaction for polymerizing the olefinic monomer in the presence of the catalyst composition comprising the transition metal compound is a solution polymerization process, using one continuous slurry polymerization reactor, loop slurry reactor, gas phase reactor or a solution reactor, It may be carried out by a slurry process or a gas phase process. It can also proceed by homopolymerization with one olefin monomer or copolymerization with two or more monomers.

The polymerization of the polyolefin may be carried out by reacting at a temperature of about 25 to about 500 ℃ and about 1 to about 100 kgf / cm ² .

Specifically, the polymerization of the polyolefin may be carried out at a temperature of about 25 to about 500 ℃, preferably about 25 to 200 ℃, more preferably about 50 to 100 ℃. The reaction pressure can also be carried out at about 1 to about 100 kgf / cm ² , preferably at about 1 to about 50 kgf / cm ² , more preferably at about 5 to about 40 kgf / cm ² .

In addition, examples of the polymerizable olefin monomer using the transition metal compound and the promoter according to an embodiment of the present invention include ethylene, alpha-olefin, cyclic olefin, and the like, and a diene olefin having two or more double bonds. The monomer or the triene olefin monomer can also be polymerized.

In the polyolefin prepared according to the present invention, specific examples of the olefin monomers include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1- itocene and the like, may be a copolymer copolymerized by mixing two or more thereof.

The polyolefin may be a propylene polymer, but is not limited thereto.

The polymer may be either a homo polymer or a copolymer. When the olefin polymer is a copolymer of ethylene and other comonomers, the monomers constituting the copolymer consist of ethylene and propylene, 1-butene, 1-hexene, and 4-methyl-1-pentene, and 1-octene It is preferred that it is at least one comonomer selected from the group.

Hereinafter, preferred examples will be described to aid in understanding the present invention. The following examples are merely to illustrate the invention, but are not intended to limit the scope of the invention.

Synthesis of Ligands and Transition Metal Compounds

Organic reagents and solvents were purchased from Aldrich and Merck and purified using standard methods. At all stages of the synthesis, the contact between air and moisture was blocked to increase the reproducibility of the experiment. To verify the structure of the compounds, spectra and plots were obtained using 500 MHz nuclear magnetic resonance (NMR), respectively.

< Example >

Example 1

Synthesis of Ligand Compound

(1) Preparation of Catalyst

Pd (OAc) ₂ (0.376 g, 1.674 mmol, 1 eq) was added to benzoquinoline (0.3 g, 1.674 mmol, 1 eq) and CH ₃ OH was added (orange solution). It was stirred for 4 h at RT and filtered to give a yellow solid, which was washed with hexane. The product could be obtained in 470 mg, 82% yield.

1 H-NMR (CDCl ₃ ): 7.77 (s, 2H), 7.40 (d, 2H), 7.20 (m, 6H), 7.04 (d, 2H), 6.93 (d, 2H) 6.42 (m, 2H), 2.34 (s, 6H)

(2) Preparation of 10-bromobenzo [ h ] quinoline

NBS (3.147 g, 17.68 mmol, 1 eq) was added to benzoquinoline (3 g, 16.74 mmol, 1 eq), and the Pd catalyst (0.0575 g, 0.0837 mmol, 0.005 eq) prepared in step (1) was added thereto. CH ₃ CN was added (black solution). The mixture was stirred at 100 ° C. for 1.5 days, dried in vacuo to remove the solvent, and then precipitated with EtOH after flash chromatography. The product was obtained at 2.85 g, 66% yield.

1 H-NMR (CDCl ₃ ): 9.09 (s, 1H), 8.15 (d, 1H), 8.08 (d, 1H), 7.87 (d, 1H), 7.75 (d, 1H), 7.70 (d, 1H), 7.55 (m, 1 H), 7.45 (t, 1 H)

(3) Preparation of N- (2,6- diisopropylphenyl) benzo [h] quinolin-10-amine (N- (2,6-diisopropylphenyl) benzo [h] quinolin-10-amine)

To 10-bromobenzoquinoline (1 g, 3.874 mmol, 1 eq) prepared in step (2), NaOtBu (0.558 g, 5.811 mmol, 1 eq), Pd ₂ (dba) ₃ (0.32 g, 0.3487 mmol, 0.06 eq), 1,1'-ferrocenediyl-bis (diphenylphosphine) (DPPF, 0.3866 g, 0.697 mmol, 0.120 eq) was added. 2,6-diisopropyl aniline (1.236 g, 6.973 mmol, 1.2 eq) was added thereto, followed by vacuum, and anhydrous toluene (58.11 ml, 0.1 M) was added thereto. At this time, it reacted at 90 degreeC overnight. After the reaction was completed, EA / H ₂ O work-up was performed and H ₂ O was removed with Na ₂ SO ₄ . After silica filtration, a red oil was obtained, and the remaining 2,6-diisopropyl aniline was added to diethyl ether, and the vacuum drying was repeatedly removed, and the removal was confirmed by NMR. EtOH was added to precipitate a yellow solid precipitated, to obtain a yellow solid 1.16 g, yield 56%.

1 H-NMR (CDCl ₃ ): 8.84 (s, 1 H), 8.20 (d, 1 H), 7.76 (d, 1 H), 7.63 (d, 1 H), 7.47 (m, 1 H), 7.38 (m, 4 H), 7.16 (d, 1H), 6.44 (d, 1H), 3.23 (m, 2H), 1.18 (d, 6H), 1.11 (d, 6H)

Synthesis of Transition Metal Compound

N- (2,6-diisopropylphenyl) benzo [ h ] quinolin-10-amine (1 g, 2.821 mmol, 1 eq) and toluene (9.403 ml, 0.3 M), the ligands synthesized in step (3), were prepared. After stirring, n-BuLi (1.24 ml, 3.103 mmol, 2.1 eq) was added dropwise. HfCl ₄ (0.949 g, 2.962 mmol, 1.05 eq) was added and heated at 90-100 ° C. for 2 hr. After the reaction was completed, the temperature was lowered and MeMgBr (4.70 ml, 14.105 mmol, 3.5 eq, 3.0 M in DEE) was added and reacted at RT overnight. The solvent was filtered under vacuum dry celite. The filtered filtrate of celite was dried and hexane was added thereto, followed by stirring, followed by drying in vacuo. When a solid was obtained, pentane was added and precipitated to obtain a transition metal compound as a final product. The product could be obtained in 1.11 g, 68% yield.

1 H-NMR (CDCl ₃ ): 9.26 (s, 1H), 7.49 (m, 3H), 7.13 (m, 5H), 6.87 (d, 1H), 6.68 (d, 1H), 3.22 (m, 2H), 1.26 (d, 6H), 0.91 (d, 6H), 0.44 (s, 9H)

Example  2

<Production of Transition Metal Compound>

N- (2,6-diisopropylphenyl) benzo [ h ] quinolin-10-amine (0.6 g, 1.6925 mmol, 1 eq) and toluene (5.6416 ml, the ligands synthesized in step (3) of Example 1 0.3 M) was added, followed by stirring, and n-BuLi (0.745 ml, 1.86175 mmol, 2.1 eq) was added dropwise. ZrCl ₄ (0.414 g, 1.777 mmol, 1.05 eq) was added and heated at 90-100 ° C. for 2 hr. After the reaction was completed, the temperature was lowered, MeMgBr (2.82 ml, 8.4625 mmol, 3.5 eq, 3.0 M in DEE) was added and reacted at RT overnight. The solvent was filtered under vacuum dry celite. The filtered filtrate of celite was dried and hexane was added thereto, followed by stirring, followed by drying in vacuo. When a solid was obtained, pentane was added and precipitated to obtain a transition metal compound as a final product. The product was obtained in 443 mg, 53% yield.

1 H-NMR (CDCl ₃ ): 9.37 (s, 1H), 7.51 (m, 3H), 7.30 (m, 5H), 6.92 (d, 1H), 6.64 (d, 1H), 3.10 (m, 2H), 1.18 (d, 6H), 0.91 (d, 6H), 0.64 (s, 9H)

Example  3

<Production of Copolymer>

Toluene solvent (0.8 L), butene (3.0 M), and ethylene (35 bar) were added to a 2 L autoclave reactor, the pressure was increased to 500 psi with high pressure argon, and the reactor was preheated to 120 ° C. It was. 10 equivalents of dimethylanilinium tetrakis (pentafluorophenyl) borate cocatalyst of 5x10 ^-6 M was added to a reactor under high pressure argon pressure, and the transition metal compound prepared in Example 1 was treated with triisobutylaluminum compound ( 1 × 10 ^-6 M, 2.0 mL) was added to the catalyst storage tank and placed in a reactor under high pressure argon. The polymerization reaction was carried out for 10 minutes. The heat of reaction was removed through a cooling coil inside the reactor to keep the polymerization temperature as constant as possible. After the polymerization reaction was performed for 10 minutes, the remaining gas was drained, and then the polymer solution was discharged to the lower part of the reactor, and excess ethanol was added to cool, thereby inducing precipitation. After washing the obtained polymer with ethanol and acetone two to three times, and then dried in a 90 ° C vacuum oven for at least 12 hours, the physical properties were measured.

Melting point (Tm) was measured using TA Q100. The measurements were taken via a second melting, heating up to 10 ° C. per minute to eliminate the thermal history of the polymer. The results are shown in Table 1 below.

Example  4

<Production of Copolymer>

In Example 3, except that the transition metal compound prepared in Example 2 was used in place of the transition metal compound prepared in Example 1, to prepare a polymer in the same manner as in Example 3, melting point Was measured and shown in Table 1 together.

Example  5

<Production of Copolymer>

A polymer was prepared in the same manner as in Example 3, except that modified methylaluminoxane (MMAO) was used instead of dimethylanilinium tetrakis (pentafluorophenyl) borate as a cocatalyst. The catalyst activity and melting point at this time were measured and shown in Table 1 below.

Example  6

<Production of Copolymer>

A polymer was prepared in the same manner as in Example 4, except that modified methylaluminoxane (MMAO) was used instead of dimethylanilinium tetrakis (pentafluorophenyl) borate as a cocatalyst. The catalyst activity and melting point at this time were measured and shown in Table 1 below.

Promoter Catalytic activity
(KgPE / mmolhr) Melting point
(℃) Example 3 Dimethylanilinium tetrakis (pentafluorophenyl) borate
10 equivalents 0.1 108.2 Example 4 Dimethylanilinium tetrakis (pentafluorophenyl) borate
10 equivalents 0.14 - Example 5 Modified Methyl Aluminoxane (MMAO)
1000 equivalents 0.85 106.4 Example 6 Modified Methyl Aluminoxane (MMAO)
1000 equivalents 1.4 106.4

Claims (10)

A transition metal compound represented by Formula 1 below:
[Formula 1]

In Chemical Formula 1,
R ₁ to R ₁₃ are each independently hydrogen, silyl, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms or arylalkyl having 7 to 20 carbon atoms. ego; R ₁₂ and R ₁₃ may be linked to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms; The aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms;
Q ₁ to Q ₃ are each independently hydrogen, halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 6 to 20 carbon atoms, or aryl having 7 to 20 carbon atoms. Alkyl;
M is Ti, Zr or hf.
The method of claim 1,
Q ₁ to Q ₃ are each independently hydrogen, alkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 6 to 20 carbon atoms, or arylalkyl having 7 to 20 carbon atoms.
The method of claim 1,
R ₁ to R ₁₃ are each independently hydrogen, alkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, or arylalkyl having 7 to 20 carbon atoms; R ₁₂ and R ₁₃ may be linked to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms; The aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms.
The method of claim 1,
R ₁₂ and R ₁₃ are connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms, and the aliphatic ring or aromatic ring is halogen, alkyl having 1 to 20 carbon atoms, or 6 to 20 carbon atoms. A transition metal compound, which may be substituted with aryl.
The method of claim 1,
The transition metal compound represented by Formula 1 is a compound of Formula 2 below:
[Formula 2]

Where
R ₁ to R ₁₁ , Q ₁ , Q ₂ , and M are as defined in claim 1;
R ₁₄ to R ₁₆ are each independently halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms.
The method of claim 1,
Compound of Formula 1 is a transition metal compound of any one of the following compounds:
A)

And
B)

.
Catalyst composition comprising the transition metal compound according to claim 1.
A supported catalyst, wherein the catalyst composition according to claim 7 is supported on a carrier.
A polymer prepared using the catalyst composition according to claim 7.
The method of claim 9,
Wherein said polymer is a polyolefin-based polymer.