KR20180053037A - Catalystic composition comprising transition metal compound, and for preparing polymers using the same - Google Patents

Abstract

The present invention relates to a catalyst composition comprising a transition metal compound and a dialkylzinc compound, and a method for manufacturing a polymer using the same. To manufacture an olefin-based polymer having high crystallinity, high density, and high molecular weight, the catalyst composition according to the present invention comprises a transition metal compound having a high comonomer incorporation effect and a dialkylzinc compound, so that a polymer exhibiting a high melt index (MI) due to chain transfer of the polymer can be manufactured.

Description

TECHNICAL FIELD [0001] The present invention relates to a catalyst composition containing a transition metal compound and a method for producing the polymer using the catalyst composition,

The present invention relates to a catalyst composition comprising a transition metal compound and a process for producing a polymer using the same. More particularly, the present invention relates to a catalyst composition comprising a transition metal compound and a dialkylzinc compound, A catalyst composition and a method for producing a polymer using the same.

Dow, in the early 1990s, [Me ₂ Si (Me ₄ C ₅ ) N t Bu] TiCl ₂ (U.S. Patent No. 5,064,802) discloses that the CGC is superior to conventional metallocene catalysts in the copolymerization reaction of ethylene and alpha-olefins (hereinafter referred to as " Constrained-Geometry Catalyst " (1) high molecular weight polymers exhibiting high activity even at high polymerization temperatures; (2) alpha-olefins with high steric hindrance such as 1-hexene and 1-octene; The copolymerization is also excellent. In addition, various characteristics of CGC were gradually known during the polymerization reaction, and efforts to synthesize the derivative and use it as a polymerization catalyst have actively been made in academia and industry.

One approach has been attempted to synthesize and polymerize metal compounds in which various other bridges and nitrogen substituents have been introduced instead of silicon bridges. Representative metal compounds known until recently are as follows (Chem. Rev. 2003, 103, 283).

(1), ethylene or propylene (2), methylidene (3), and methylene (4) bridges were introduced in place of the silicon bridge of the CGC structure, Or in the case of copolymerization with an alpha-olefin, no improvement in terms of activity or copolymerization performance versus CGC was obtained.

In addition, as another approach, a large amount of compounds composed of oxydolides were synthesized instead of the amido ligands of CGC, and some polymerization using the compounds was attempted. The examples are summarized as follows.

Compound (5) is reported by T. J. Marks et al. In which Cp (cyclopentadiene) derivatives and oxydolides are crosslinked by ortho-phenylene groups (Organometallics 1997, 16, 5958). Compounds having the same cross-linking and polymerization using them have also been reported by Mu et al. (Organometallics 2004, 23, 540). Also, Rothwell et al. (Chem. Commun. 2003, 1034) have reported that an indenyl ligand and an oxydol ligand are bridged by the same ortho-phenylene group. Compound (6) is reported by Whitby et al. (Organometallics 1999, 18, 348) in which a cyclopentenylidene ligand and an oxydoligand are bridged by three carbon atoms (Syndiotactic ) Was reported to exhibit activity in polystyrene polymerization. Similar compounds have also been reported by Hessen et al. (Organometallics 1998, 17, 1652). Compound (7) is reported by Rau et al. And is characterized in that it exhibits activity in ethylene polymerization and ethylene / 1-hexene copolymerization at high temperature and high pressure (210, 150 MPa) (J. Organomet. Chem. 2000, 608, 71). Then, the catalyst synthesis (8) having similar structure and the high temperature and high pressure polymerization using the same were patented by Sumitomo Co. (US Patent No. 6,548,686). However, among the above attempts, only a few catalysts have actually been applied to commercial plants. Therefore, a catalyst showing improved polymerization performance is required, and a method of simply producing such catalysts is required.

US Patent No. 5,064,802 US Patent No. 6,548,686

 Chem. Rev. 2003, 103, 283  Organometallics 1997, 16, 5958  Organometallics 2004, 23, 540  Chem. Commun. 2003, 1034  Organometallics 1999, 18, 348  Organometallics 1998, 17, 1652  J. Organomet. Chem. 2000, 608, 71

It is an object of the present invention to provide a catalyst composition comprising a transition metal compound and a dialkylzinc compound.

Another object of the present invention is to provide a method for producing a polymer using the catalyst composition.

In order to solve the above problems,

There is provided a catalyst composition comprising a transition metal compound of the formula 1 and a dialkylzinc compound of the formula 2:

In Formula 1,

R ₁ to R ₉ each independently represent 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, arylalkyl having 7 to 20 carbon atoms , Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl having from 1 to 20 carbon atoms;

Two or more adjacent ones of R ₁ to R ₈ 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;

n is 1 or 2;

Q ¹ and Q ² 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, arylalkyl having 7 to 20 carbon atoms , Alkylamido having 1 to 20 carbon atoms, arylamido having 6 to 20 carbon atoms, or alkylidene having 1 to 20 carbon atoms;

M is Ti, Zr or Hf;

(2)

In Formula 2,

R < ₁₀ & And each R < ₁₁ > is independently an alkyl having 1 to 20 carbon atoms.

In order to solve the above-mentioned other problems,

And a method for producing a polymer using the catalyst composition.

Since the catalyst composition according to the present invention contains a transition metal compound having a high comonomer incorporation effect and a dialkylzinc compound in the production of an olefinic polymer having high crystallinity, high density and high molecular weight, Polymers that exhibit a high melt index (MI) due to chain transfer can be prepared.

The catalyst composition according to the present invention comprises a transition metal compound represented by the following formula (1) and a dialkylzinc compound represented by the following formula (2).

[Chemical Formula 1]

In Formula 1,

R ₁ to R ₉ each independently represent 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, arylalkyl having 7 to 20 carbon atoms , Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl having from 1 to 20 carbon atoms;

Two or more adjacent ones of R ₁ to R ₈ 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;

n is 1 or 2;

Q ¹ and Q ² 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, arylalkyl having 7 to 20 carbon atoms , Alkylamido having 1 to 20 carbon atoms, arylamido having 6 to 20 carbon atoms, or alkylidene having 1 to 20 carbon atoms;

M is Ti, Zr or Hf;

(2)

In Formula 2,

R < ₁₀ & And each R < ₁₁ > is independently an alkyl having 1 to 20 carbon atoms.

The transition metal compound of Formula 1 included in the catalyst composition is capable of chain transfer by a cjain shuttling agent so that the dialkyl zinc of Formula 2 included in the catalyst composition acts as a chain shuttling agent , A polymer having a high melt index (MI) and a melting temperature (Tm) can be produced. In addition, the transition metal compound of the above formula (1) can be used as a catalyst for making a block copolymer since chain transfer by a chain shuttling agent is possible.

According to an embodiment of the present invention, Q ¹ and Q ² are each independently selected from the group consisting of hydrogen, halogen, alkyl having 1 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.

According to an embodiment of the present invention, R ₁ to R ₉ are each independently selected from the group consisting of hydrogen, alkyl of 1 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, alkylaryl of 7 to 20 carbon atoms, Arylalkyl having 7 to 20 carbon atoms;

Two or more adjacent ones of R ₁ to R ₈ 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 of 1 to 20 carbon atoms, or aryl of 6 to 20 carbon atoms.

According to an embodiment of the present invention, the compound of Formula 1 may be any of the compounds represented by the formulas.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Chemical Formula 1-6]

[Chemical Formula 1-7]

[Chemical Formula 1-8]

[Chemical Formula 1-9]

[Chemical Formula 1-10]

[Formula 1-11]

[Formula 1-12]

[Formula 1-13]

[Chemical Formula 1-14]

[Chemical Formula 1-15]

[Chemical Formula 1-16]

[Formula 1-17]

[Chemical Formula 1-18]

[Chemical Formula 1-19]

[Chemical Formula 1-20]

[Formula 1-21]

[Formula 1-22]

In addition, specific substituents and combinations thereof of the compounds of formula (2) in addition to the above-mentioned formulas (2a) to (2v) are shown in Tables 1 to 5 below.

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

The term " halogen ", as used herein, unless otherwise indicated, means fluorine, chlorine, bromine or iodine.

The term " alkyl ", as used herein, unless otherwise indicated, means a linear or branched hydrocarbon residue.

The term " alkenyl ", as used herein, unless otherwise indicated, means a straight chain or branched chain alkenyl group.

Wherein the branched chain is selected from the group consisting of alkyl of 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 selected from the group consisting of trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, trihexylsilyl, triisopropylsilyl, triisobutylsilyl, triethoxysilyl, triphenylsilyl, tris Silyl) silyl, and the like, but are not limited to these examples.

According to an embodiment of the present invention, the aryl group preferably has 6 to 20 carbon atoms, and specifically includes phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilinyl, anisolyl, and the like.

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 at least one hetero atom, and may be a single ring or a condensed ring of two or more rings. The heterocyclic group may be substituted or unsubstituted with an alkyl group. Examples thereof include indoline, tetrahydroquinoline and the like, but the present invention is not limited thereto.

The alkylamino group means an amino group substituted by the alkyl group, and includes, but is not limited to, dimethylamino group, diethylamino group, and the like.

According to an embodiment of the present invention, the aryl group preferably has 6 to 20 carbon atoms, and specifically includes phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilinyl, anisolyl and the like, no.

The transition metal compound represented by Formula 1 may be prepared using a ligand compound represented by Formula 3 below.

(3)

In Formula 3, R ₁ to R ₉ each independently represent 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, Lt; / RTI > is an arylalkyl of 1 to 20 carbon atoms, or a metalloid radical of a Group 14 metal substituted with a hydrocarbyl of 1 to 20 carbon atoms; Two or more adjacent ones of R ₁ to R ₈ 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; n is 1 or 2;

In Formula 3, R ₁ to R ₉ each independently represent 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 Have; Two or more adjacent ones of R ₁ to R ₈ 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 of 1 to 20 carbon atoms, or aryl of 6 to 20 carbon atoms.

In one embodiment of the invention, the ligand compound of Formula 3 may be any of the following compounds:

[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

[Chemical Formula 3-4]

[Formula 3-5]

[Chemical Formula 3-6]

[Chemical Formula 3-7]

[Chemical Formula 3-8]

[Chemical Formula 3-9]

[Chemical Formula 3-10]

[Formula 3-11]

The ligand compound of the present invention can be prepared by the following process: (1) reacting a compound of the following formula (4) with a compound of the following formula (5) 6 < / RTI > And (2) reacting a compound represented by the following formula (6) with a compound represented by the following formula (7) to prepare a compound represented by the following formula (3).

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

[Chemical Formula 6]

Wherein R ₁ to R ₉ are each independently selected from the group consisting of 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, Arylalkyl of 7 to 20 carbon atoms, or a metalloid radical of a Group 14 metal substituted with hydrocarbyl of 1 to 20 carbon atoms; Two or more adjacent ones of R ₁ to R ₈ 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; n is 1 or 2;

In the above formulas 3 to 6, R ₁ to R ₉ are each independently selected from the group consisting of hydrogen, alkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, arylalkyl having 7 to 20 carbon atoms Lt; / RTI > Two or more adjacent ones of R ₁ to R ₈ 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 of 1 to 20 carbon atoms, or aryl of 6 to 20 carbon atoms.

(1) reacting a compound of formula (4) with a compound of formula (5) to prepare a compound of formula

[Reaction Scheme 1]

In step (1), the compound of formula (4) is reacted with the compound of formula (5) to prepare a compound of formula (6).

The reaction of step (1) may be carried out in the presence of a palladium catalyst under basic conditions, and the reaction may be carried out in an organic solvent such as toluene.

The palladium catalyst may be at least one selected from the group consisting of tetrakis (triphenylphosphine) palladium [Pd (PPh ₃ ) ₄ ], palladium chloride (PdCl ₂ ), palladium acetate (Pd (OAc) ₂ ), bis (dibenzylideneacetone) palladium dba) ₂ ) and Pd (tBu ₃ P ₂ ).

The base for achieving the above basic conditions is not particularly limited, but specific examples thereof include tBuOLi, potassium tris (K ₃ PO ₄ ), potassium carbonate (K ₂ CO ₃ ), cesium carbonate (Cs ₂ CO ₃ ) Potassium fluoride (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 at a temperature of 0 ° C to 140 ° C, specifically at a temperature of 40 ° C to 100 ° C for 1 to 48 hours, specifically 2 to 12 hours.

The compound of formula (4) and the compound of formula (5) may be added to the respective solvents separately and then mixed again. After the mixing, the palladium catalyst may be added. For example, the compound of Formula 4 may be added to a mixed solvent of water and alcohol such as ethanol, and the compound of Formula 5 may be added to a solvent such as toluene.

In this case, the compound of Formula 4 may be prepared by the reaction shown in Reaction Scheme 2 below.

[Reaction Scheme 2]

Wherein R ₆ to R ₉ and n are the same as defined in the above formula (4).

The compound of formula (4-1) is placed in an organic solvent such as hexane and n-BuLi is added at a temperature range of -80 ° C to 0 ° C. In this case, the n-BuLi may be reacted at a molar ratio of 1: 1 to 1: 2 with respect to the compound of Formula 3-1, and specifically at a molar ratio of 1: 1.1 to 1: 1.2. After the addition of n-BuLi, the reaction was carried out at room temperature for 1 to 48 hours, followed by filtration. The solvent was then added to the obtained compound, and CO ₂ was bubbled at a temperature of -160 ° C. to -20 ° C., -2 can be obtained. T-BuLi is added to the obtained compound of formula (4-2) and the reaction is carried out at a temperature ranging from -80 ° C to 0 ° C to obtain the compound of formula (4-3). After adding 2-isopropyloxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane to the compound of Formula 4-3 at a temperature of -150 ° C to -20 ° C, The reaction is allowed to proceed by gradually raising the temperature to room temperature to obtain the compound of formula (4). At this time, HCl and ethyl acetate (EA) are added, and the organic layer is washed with NaOH and NaHCO _3, and dried with MgSO ₄ .

(2) reacting the compound of formula (6) with the compound of formula (7) to prepare the compound of formula

[Reaction Scheme 3]

In step (2), the compound of formula (6) is reacted with the compound of formula (7) to produce the compound of formula (3).

In step (2), R ₂ is introduced into the compound of formula (6) by reacting the compound of formula (6) with the organolithium compound of formula (7).

In the above step (2), the compound of formula (6) and the compound of formula (7) may be reacted at a molar ratio of 1: 1 to 1: 3 and specifically at a molar ratio of 1: 1 to 1: 2 .

The reaction of step (2) may be carried out by adding the compound of formula (7) to the compound of formula (6) in a temperature range of -160 ° C to -20 ° C and then performing the reaction. The compound of Formula 6 may be added to the compound of Formula 6 at a temperature of 40 占 폚 to react. The reaction may be carried out in an organic solvent such as diethyl ether and quenched by NH ₄ Cl or the like after completion of the reaction.

The compound of formula 3 prepared through steps (1) and (2) may be further subjected to (3) recrystallization step, so that after step (2), (3) Step < / RTI >

The recrystallization may be carried out using an organic solvent such as toluene, such as a reaction solvent, and purified through recrystallization to obtain a pure compound of formula (3).

The transition metal compound represented by formula (1) of the present invention may be prepared by (a) reacting the ligand compound of formula (3) with an organolithium compound to prepare a compound of formula (8); And (b) reacting a compound of formula (8) with a compound of formula (9) to prepare a compound of formula (1).

[Chemical Formula 1]

(3)

[Chemical Formula 8]

[Chemical Formula 9]

In the above formulas,

R ₁ to R ₉ each independently represent 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, arylalkyl having 7 to 20 carbon atoms , Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl having from 1 to 20 carbon atoms; Two or more adjacent ones of R ₁ to R ₈ 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; n is 1 or 2;

Q ¹ and Q ² 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, 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;

X is halogen;

M is Ti, Zr or Hf.

Each of R ₁ to R ₉ 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 ones of R ₁ to R ₈ 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 of 1 to 20 carbon atoms, or aryl of 6 to 20 carbon atoms.

The process for preparing a transition metal compound of the present invention may further comprise the step of reacting the compound of Formula 1 with a Grignard reagent of Formula 10 below.

[Chemical formula 10]

Wherein Q is selected from the group consisting of hydrogen, 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, arylalkyl having 7 to 20 carbon atoms, An alkylamido of 1 to 20 carbon atoms, an arylamido of 6 to 20 carbon atoms, or an alkylidene of 1 to 20 carbon atoms.

In this case, the compound of Chemical Formula 1 in which the compound of Formula 1 is reacted with the Grignard reagent of Chemical Formula 10 may be Q ¹ , Q ² or all of them may be halogen. That is, in one embodiment of the present invention, when Q ¹ , Q ² , or both of them are halogen, Q ¹ , Q ² , or both of them are halogen, In this case, Q ¹ , Q ² , or both of them in the formula (1) may be substituted with the Q in the halogen through an additional reaction with the Grignard reagent of the formula (10).

(a) reacting a compound of formula (3) with an organolithium compound to produce a compound of formula (8)

In step (a), the compound of formula (3) is reacted with an organolithium compound to prepare a compound of formula (8).

In the above step (1), the compound of Formula 3 and the organolithium compound may be reacted at a molar ratio of 1: 1 to 1: 3, and more specifically, at a molar ratio of 1: 1 to 1: 2.

The reaction of step (1) may be carried out in an organic solvent such as diethoxyethane and ether, and may be carried out by adding the organic lithium compound to the compound of formula (3) in an organic solvent.

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

The reaction of step (a) is carried out by adding the organolithium compound to the compound of formula (1) in a temperature range of -78 ° C to 0 ° C, and then performing the reaction for 1 to 6 hours, specifically for 1 to 4 hours . At this time, the reaction temperature may be less than 20 ° C, specifically, -78 ° C to 0 ° C.

(b) reacting a compound of formula (8) with a compound of formula (9) to produce a compound of formula (1); And

In step (b), the compound of formula (8) obtained in step (a) is reacted with the compound of formula (9) to prepare a compound of formula (1).

In the above step (b), the compound of formula (8) and the compound of formula (9) may be reacted at a molar ratio of 1: 0.8 to 1: 1.8, specifically 1: 1 to 1: 1.2 .

The reaction of step (b) may be carried out by raising the temperature to a temperature in the range of 40 ° C to 140 ° C, specifically in the range of 70 ° C to 120 ° C, and then conducting the reaction for 1 to 48 hours, And the reaction in step (a) and step (b) may be performed in one step.

That is, the reaction of steps (a) and (b) may be carried out by adding the compound of formula (8) to the compound of formula (1) in a temperature range of -20 ° C to 30 ° C, The reaction is carried out by raising the temperature to a temperature range of from 70 to 120 캜, specifically from 70 캜 to 120 캜, for 1 to 48 hours, specifically for from 1 to 4 hours.

Thus, the transition metal compound of Formula 1 can be prepared.

Further, when Q ¹ , Q ² or all of them are halogen in the transition metal compound of Formula 1, an additional reaction may be performed with the Grignard reagent of Formula 10. At this time, the reaction between the transition metal compound of Formula 1 and the Grignard reagent of Formula 10 may be performed according to the known Grignard reaction.

The transition metal compound prepared according to the additional reaction may be represented by any of the following formulas (1a) to (1c).

[Formula 1a]

[Chemical Formula 1b]

[Chemical Formula 1c]

The dialkylzinc compound of formula (2) may be at least one member selected from the group consisting of diethyl zinc, dipropyl zinc, dibutyl zinc and ethyl propyl zinc. More specifically, the dialkyl zinc compound of formula (2) Ethyl < / RTI >

The dialkylzinc compound of Formula 2 may be mixed in an amount of 1 to 200 equivalents based on 1 equivalent of the transition metal compound of Formula 1. Specifically, the dialkylzinc compound may be used in an amount of 10 to 100? Can be mixed in an amount of?

The catalyst composition may further comprise a cocatalyst. As the cocatalyst, those known in the art can be used.

For example, the catalyst composition may further include at least one of the following formulas (11) to (13) as a cocatalyst.

(11)

_{- [Al (R 12) -O} ] a -

In the formula (11), each R ₁₂ is independently a halogen radical; A hydrocarbyl radical having from 1 to 20 carbon atoms; Or a hydrocarbyl radical having 1 to 20 carbon atoms substituted with halogen; a is an integer of 2 or more;

[Chemical Formula 12]

D (R _{12) 3}

In Formula 12, D is aluminum or boron; R < ₁₂ > are each independently as defined in the above formula (11);

[Chemical Formula 13]

^{[LH] + [Z (A} ) 4] - or ^{[L] + [Z (A} ) 4] -

Wherein L is a neutral or cationic Lewis acid; H is a hydrogen atom; Z is a Group 13 element; A is independently an aryl having 6 to 20 carbon atoms or an alkyl having 1 to 20 carbon atoms in which at least one hydrogen atom may be substituted with a substituent; The substituent is halogen, hydrocarbyl of 1 to 20 carbon atoms, alkoxy of 1 to 20 carbon atoms, or aryloxy of 6 to 20 carbon atoms.

The catalyst composition may be prepared by mixing a transition metal compound represented by the formula (1), a dialkylzinc compound represented by the formula (2), and a compound represented by the formula (11) or (12) to obtain a mixture; And adding the compound represented by Formula 13 to the mixture.

Alternatively, the catalyst composition may further comprise a step of mixing and contacting the transition metal compound represented by the formula (1), the dialkylzinc compound represented by the formula (2), and the compound represented by the formula (13) And can be produced by a production method.

When the transition metal compound represented by the formula (1) and the dialkylzinc compound represented by the formula (2) are contacted with the compound represented by the formula (11) or (12) to obtain a mixture, the transition metal compound represented by the formula The molar ratio of the dialkylzinc compound represented by the formula (2) to the compound represented by the formula (11) or (12) may be 1: 2 to 1: 5,000 and may be 1:10 to 1: 1,000, More specifically from 1:20 to 1: 500.

The molar ratio of the transition metal compound represented by Formula 1 to the dialkyl zinc compound represented by Formula 2 may be 1: 1 to 1:25, 1:10, more specifically from 1: 1 to 1: 5.

When the molar ratio of the transition metal compound represented by the formula (1) and the dialkylzinc compound represented by the formula (2) to the compound represented by the formula (11) or (12) is less than 1: 2, the amount of the alkylating agent is very small, There is a problem in that the alkylation is not completely progressed, and when the ratio is more than 1: 5,000, the alkylation of the metal compound is carried out but the activation of the alkylated metal compound is completely completed due to the side reaction between the excess of the alkylating agent and the activating agent There is a problem that can not be supported. When the ratio of the transition metal compound represented by the formula (1) and the compound represented by the formula (13) to the dialkyl zinc compound represented by the formula (2) is less than 1: 1, the amount of the activator is relatively small, The catalytic activity of the resulting catalyst composition is inferior. When the ratio exceeds 1:25, the activation of the metal compound is completely carried out. However, since the excess amount of the activator is insufficient for the catalyst composition, There is a problem in that the purity of the polymer becomes poor.

On the other hand, when the catalyst composition is prepared by contacting the transition metal compound represented by the formula (1) and the dialkylzinc compound represented by the formula (2) with the compound represented by the formula (13) The molar ratio of the transition metal compound and the compound represented by the formula (13) to the dialkyl zinc compound represented by the formula (2) may be 1: 1 to 1: 500, and may be 1: 1 to 1:50, More specifically from 1: 2 to 1:25. When the molar ratio is less than 1: 1, the amount of the activating agent is relatively small and the activation of the metal compound is not achieved completely. Therefore, there is a problem that the activity of the catalyst composition is low. When the molar ratio is more than 1: 500, However, there is a problem that the unit cost of the catalyst composition is insufficient due to the excess amount of the remaining activator, or the purity of the produced polymer is lowered.

As the reaction solvent, hydrocarbon solvents such as pentane, hexane, heptane and the like and aromatic solvents such as benzene, toluene and the like may be used in the preparation of the composition, but not always limited thereto, and all solvents usable in the related art are used .

The transition metal compound represented by the formula (1) and the dialkylzinc compound represented by the formula (2) and the cocatalyst may be also supported on a carrier. As the carrier, silica or alumina can be used.

The compound represented by the formula (11) is not particularly limited as long as it is alkylaluminoxane. Specific examples thereof include methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, and butyl aluminoxane, and more specific examples thereof include methyl aluminoxane.

The compound represented by the formula (12) is not particularly limited and specific examples thereof include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethyl chloro aluminum, triisopropyl 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 Trimethylboron, triethylboron, triisobutylboron, tripropylboron, or tributylboron. More specific examples thereof include trimethylaluminum, triethylaluminum, and triisobutylaluminum.

Examples of the compound represented by Formula 13 include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetra (p-tolyl) boron, trimethylammonium tetra (p-dimethylphenyl) boron, tributylammonium tetra (ptrifluoromethylphenyl) boron, trimethylammonium tetra (p-trifluoromethylphenyl) boron, tributylammonium tetrapentafluorophenylboron, N, N -Diethylanilinium tetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium tetraphenylboron, trimethylphosphonium tetraphenylboron, dimethyl Anilinium tetrakis (pentafluorophenyl) borate, triethylammonium tetraphenyl aluminum, tributylammonium tetraphenyl aluminum, Trimethylammonium tetra (p-tolyl) aluminum, tripropylammonium tetra (p-tolyl) aluminum, triethylammonium tetra (o, p-dimethylphenyl) aluminum, tri (P-trifluoromethylphenyl) aluminum, trimethylammonium tetra (ptrifluoromethylphenyl) aluminum, tributylammonium tetrapentafluorophenyl aluminum, N, N-diethylaniliniumtetraphenylaluminum, N, N-diethylanilinium tetrapentafluorophenyl aluminum, diethylammonium tetrapentatetraprapaluminum aluminum, triphenylphosphonium tetraphenyl aluminum, trimethylphosphonium tetraphenyl aluminum, tripropylammonium tetra (p-tolyl) boron, tri (O, p-dimethylphenyl) boron, triphenylcarbeniumtetra (p-trifluoromethylphenyl) boron or triphenylcarbamate A titanium tetra-pentafluoropropane, and the like phenylboronic.

A catalyst composition comprising at least one olefin monomer and at least one olefin monomer, wherein the catalyst composition comprises at least one compound selected from the group consisting of the transition metal compound represented by Formula 1, the dialkylzinc compound represented by Formula 2, and the compound represented by Formula 11 to Formula 13, Copolymers can be prepared.

The most preferred preparation process using the catalyst composition may be a solution process, and the catalyst composition may also be applied to slurry or gas phase processes when used in combination with an inorganic carrier such as silica.

In the above production process, the activated catalyst composition may be prepared by reacting an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms suitable for the olefin polymerization process, such as pentane, hexane, heptane, nonane, decane and isomers thereof and an aromatic hydrocarbon solvent such as toluene, Dichloromethane, chlorobenzene, or the like, or may be injected by dilution. The solvent used herein is preferably used by removing a small amount of water or air acting as a catalyst poison by treating with a small amount of an alkylaluminum, and further using a co-catalyst.

Examples of the olefin-based monomer polymerizable with the metal compound and the cocatalyst include ethylene, alpha-olefin, and cyclic olefin. Diene olefin-based monomers or triene olefin-based monomers having two or more double bonds Monomers and the like can also be polymerized. Specific examples of the monomer include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, Butene, dicyclopentadiene, 1,4-butadiene, 1,4-butadiene, 1,3-butadiene, 1,3-butadiene, 5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, 3-chloromethylstyrene, and the like. These two or more monomers may be mixed and copolymerized.

Particularly, in the production process of the present invention, the catalyst composition has a high molecular weight in the copolymerization reaction of a monomer having a large steric hindrance such as ethylene and 1-octene even at a high reaction temperature of 90 or more and an ultra low density copolymer having a polymer density of 0.91 g / Can be produced.

The polymer produced by the process of the present invention may have a density of less than 0.91 g / cc, specifically less than 0.89 g / cc, and more specifically less than 0.884 g / cc.

In addition, the polymer produced by the production process of the present invention has two melting temperatures (Tm) obtained in the DSC curve (Tm1 and Tm2), and therefore the crystal is melted and crystallized at different temperatures, Can be increased.

The polymer produced by the production method of the present invention has a Tm1 in the range of -30 to 90 and a Tm2 in the range of -10 to 140 in the range of the density of 0.85 to 0.91 g / cc.

Specifically, the polymer produced by the production method of the present invention may have a Tm1 in the range of 60 to 117 and a Tm2 in the range of 110 to 122 in the range of the density of 0.85 to 0.91 g / cc.

Tm used herein means the temperature at the peak of each peak in the temperature-heat flow graph of a differential scanning calorimeter (DSC).

In addition, the polymer produced by the production method of the present invention has two crystallization temperatures (Tc) (Tc1 and Tc2) obtained from the DSC curve, and thus the crystal is melted and crystallized at different temperatures, Can be increased.

In the present specification, the crystallization temperature means a temperature at which crystallization occurs in which the arrangement of the material structure irregularly changes in a regular manner by the attraction between molecules / atoms, and can be analyzed through, for example, differential scanning calorimetry (DSC) .

The polymer produced by the production method of the present invention may have a Tc1 in the range of 20 to 80 and a Tc2 in the range of 50 to 110 in the range of the density of 0.85 to 0.91 g / cc.

Specifically, the polymer produced by the production method of the present invention may have a Tc1 ranging from 45 to 78 and a Tc2 ranging from 75 to 97 in the range of the density of 0.85 to 0.91 g / cc.

Hereinafter, the present invention will be described more specifically based on the following examples. These examples are provided to aid understanding of the present invention and the scope of the present invention is not limited thereto.

Organic reagents and solvents were purchased from Aldrich unless otherwise noted and purified by standard methods. At every stage of the synthesis, the contact between air and moisture was blocked to improve the reproducibility of the experiment. Compounds in which R < 1 > to R < 6 > in the ketone compounds of formula (7) are methyl are described in Organometallics 2002, 21, 2842-2855.

Production Example 1

≪ Synthesis of ligand compound >

Preparation of 2- methyl -8- (4,4,5,5- tetramethyl- 1,3,2 -dioxaborolan -2-yl) -1,2,3,4- tetrahydroquinoline

2-methyl-THQ (10 g, 67.925 mmol, 1 eq) was added to a Schlenk flask followed by vacuum drying. To this was added hexane (226 mL, 0.3 M) (29.89 mL, 74.718 mmol, 1.1 eq, 2.5 M in hexane). This was reacted at room temperature overnight, and then the lithium compound was filtered. Diethyl ether (113.21 mL, 0.4 M) was added to the lithium compound thus obtained (10.40 g, 67.925 mmol, 1 eq) and bubbled CO ₂ at -78 ° C. It was left at room temperature overnight and then THF (1.1 eq, 5.388 g, 74.72 mmol) was added at -20 < 0 > C. To this was added t-BuLi (47.6 mL, 74.72 mmol, 1.1 eq, 1.7 M) and the mixture was reacted at -20 ° C for 2 hours. 2-Isopropyl-4,4,5,5-tetramethyl- , 2-dioxaborolane (31.6 g, 169.8 mmol, 2.5 eq) at -78 < 0 > C. After the temperature was gradually raised to room temperature, 1M aqueous HCl solution and EA were added at 0 ° C. The organic layer was washed with 1 M NaOH and 1 M NaHCO _3, and dried over MgSO ₄ . A yellow solid product was obtained in a yield of 9.9 g, 53.4%.

_{1H-NMR (CDCl 3):} 7.45 (d, 1H), 7.01 (d, 1H), 6.52 (t, 1H), 5.83 (s, 1H), 3.48 (m, 1H), 2.80 (m, 2H), (S, 3 H), 1.91 (m, 1 H), 1.58 (m,

Preparation of N- (2,6 -diisopropylphenyl ) -1- (6- (2- methyl- 1,2,3,4- tetrahydroquinolin- 8- yl) pyridin-

Toluene (13.33 mL) was added to the N- (2,6-diisopropylphenyl) -1- (6-bromopyridin-2-yl) methanimine (3 g, 8.69 mmol, 1 eq) stirring while separately, _{Na 2 CO 3 (2.303 g,} 21.725 mmol, 2.5 eq) and THQ- beam Rolando (2.373 g, 8.69 mmol, 1 eq) with H ₂ O (2.66 mL) and EtOH (2.66 mL) 1 : 1 and stirred.

Br- placed a toluene solution of the imine THQ- beam _{Pd (PPh 3) 4 (0.0301} g, 0.026 mmol, 0.3 mol% Pd) to the rear here moved with a solution of Rolando. The mixture was stirred at 70 DEG C for 4 hours and then cooled to room temperature. The organic layer was extracted with toluene / salt water (brine) and dried to a moisture Na ₂ SO _4. The product was obtained in 3.08 g, 86% yield.

(D, 2H), 7.19 (t, 1H), 7.13 (m, 3H), 6.94 (s, 1H) (d, IH), 6.64 (m, IH), 3.30 (m, IH), 3.16 (m, 2H), 2.72 m, 1 H), 1.19 (m, 12H), 1.05 (d, 3H)

2,6-diisopropyl -N - ((2-isopropyl-phenyl) - (6- (2-methyl-1,2,3,4-tetrahydroquinolin-8-yl) pyridin-2-yl) methyl) Manufacture of aniline

To THF (13.122 mL) was added 1-Br-2-isopropylbenzene (1.306 g, 6.561 mmol, 2.7 eq) and t-BuLi (8.36 mL) was added at -78 ° C. After reacting for 2 hours, the temperature was raised to room temperature to prepare lithium cumene. (2,6-diisopropylphenyl) -1- (6- (2-methyl-1,2,3,4-tetrahydroquinolin-8-yl) pyridin- Diethyl ether (24.3 mL) was added to methanimine (1 g, 2.43 mmol, 1 eq), and the lithium cumene was added dropwise at -78 째 C. It was up (work-up) - the temperature was raised to room temperature, quench (quench) and the work in Ether / H ₂ O with 1 N NH ₄ Cl after which the reaction overnight. The water was dried with Na ₂ SO ₄ and the solvent was vacuum dried with a rotary evaporator. Yellow oil, 1.48 g, was obtained in quantitative yield.

1 H-NMR (toluene-d8): 8.30-5.60 (m, 15H), 4.73-2.59 (m,

≪ Synthesis of transition metal compound >

The resulting ligand, 2,6-diisopropyl-N - ((2-isopropylphenyl) (6- (2-methyl-1,2,3,4-tetrahydroquinolin- 2-yl) methyl) aniline (1.21 g, 2.27 mmol, 1 eq) and toluene (7.567 mL, 0.3 M) were added to the solution and stirred. Then n-BuLi (1.907 mL, 4.767 mmol, 2.1 eq) was added dropwise. HfCl ₄ (0.7634 g, 2.3835 mmol, 1.05 eq) was added and heated at 90-100 ° C for 2 hours. After the reaction was completed, the reaction mixture was cooled to room temperature and MeMgBr (2.65 mL, 7.945 mmol, 3.5 eq, 3.0 M in DEE) was added thereto overnight. The solvent was vacuum dried and then filtered. The celite-filtered filtrate was dried, and hexane was added thereto, followed by stirring, followed by vacuum drying, followed by addition of pentane, stirring and vacuum drying. When a solid was obtained, it was precipitated with pentane to obtain a yellow solid catalyst in a yield of 320 mg, 19%.

(M, 3H), 7.07 (m, 3H), 6.86 (d, IH) (t, 1H), 6.69 (t, IH), 6.60 (d, IH), 6.523 (s, IH), 4.82 (m, 1H), 2.79 (m, 1H), 2.79 (m, 1H) , 6H), 0.93 (d, 3H), 0.71 (d, 3H)

Production Example 2

≪ Synthesis of ligand compound >

Preparation of 2- methyl -8- (4,4,5,5- tetramethyl- 1,3,2 -dioxaborolan -2-yl) -1,2,3,4- tetrahydroquinoline

2-methyl-THQ (10 g, 67.925 mmol, 1 eq) was added to a Schlenk flask followed by vacuum drying. To this was added hexane (226 mL, 0.3 M) (29.89 mL, 74.718 mmol, 1.1 eq, 2.5 M in hexane). This was reacted at room temperature overnight, and then the lithium compound was filtered. Diethyl ether (113.21 mL, 0.4 M) was added to the lithium compound thus obtained (10.40 g, 67.925 mmol, 1 eq) and bubbled CO ₂ at -78 ° C. It was left at room temperature overnight and then THF (1.1 eq, 5.388 g, 74.72 mmol) was added at -20 < 0 > C. To this was added t-BuLi (47.6 mL, 74.72 mmol, 1.1 eq, 1.7 M) and the mixture was reacted at -20 ° C for 2 hours. 2-Isopropyl-4,4,5,5-tetramethyl- , 2-dioxaborolane (31.6 g, 169.8 mmol, 2.5 eq) at -78 < 0 > C. After the temperature was gradually raised to room temperature, 1M aqueous HCl solution and EA were added at 0 ° C. The organic layer was washed with 1 M NaOH and 1 M NaHCO _3, and dried over MgSO ₄ . A yellow solid product was obtained in a yield of 9.9 g, 53.4%.

_{1H-NMR (CDCl 3):} 7.45 (d, 1H), 7.01 (d, 1H), 6.52 (t, 1H), 5.83 (s, 1H), 3.48 (m, 1H), 2.80 (m, 2H), (S, 3 H), 1.91 (m, 1 H), 1.58 (m,

Preparation of N- (2,6 -diisopropylphenyl ) -1- (6- (2- methyl- 1,2,3,4- tetrahydroquinolin- 8- yl) pyridin-

Toluene (13.33 mL) was added to the N- (2,6-diisopropylphenyl) -1- (6-bromopyridin-2-yl) methanimine (3 g, 8.69 mmol, 1 eq) stirring while separately, _{Na 2 CO 3 (2.303 g,} 21.725 mmol, 2.5 eq) and THQ- beam Rolando (2.373 g, 8.69 mmol, 1 eq) with H ₂ O (2.66 mL) and EtOH (2.66 mL) 1 : 1 and stirred.

Br- placed a toluene solution of the imine THQ- beam _{Pd (PPh 3) 4 (0.0301} g, 0.026 mmol, 0.3 mol% Pd) to the rear here moved with a solution of Rolando. The mixture was stirred at 70 DEG C for 4 hours and then cooled to room temperature. The organic layer was extracted with toluene / salt water (brine) and dried to a moisture Na ₂ SO _4. The product was obtained in 3.08 g, 86% yield.

(D, 2H), 7.19 (t, 1H), 7.13 (m, 3H), 6.94 (s, 1H) (d, IH), 6.64 (m, IH), 3.30 (m, IH), 3.16 (m, 2H), 2.72 m, 1 H), 1.19 (m, 12H), 1.05 (d, 3H)

≪ Synthesis of ligand compound >

Preparation of 2,6 -diisopropyl- N - ((6- (2- methyl- 1,2,3,4- tetrahydroquinolin- 8-yl) pyridin - 2 -yl) (naphthyl) methyl) aniline

The ligand precursor N- (2,6-diisopropylphenyl) -1- (6- (2-methyl-1,2,3,4-tetrahydroquinolin-8-yl) pyridine 2-yl) methanimine (1.5 g, 3.644 mmol, 1 eq) was dissolved in diethyl ether (36.44 mL) and the temperature was lowered to -78 ° C. 1-Bromonaphthalene (2.04 g, 9.84 mmol, 2.7 eq) was dissolved in THF (19.68 mL) and t-BuLi (12.53 mL, 19.68 mmol, 5.4 eq) was added to perform lithium substitution reaction. When the lithium substitution reaction is completed, it is reacted with N- (2,6-diisopropylphenyl) -1- (6- (2-methyl-1,2,3,4-tetrahydroquinolin- Yl) methane imine, and quenched with 1 N NH ₄ Cl at the end of the reaction and worked up with diethyl ether and water. This gave 1.93 g of the product, yellow oil, in 98% yield.

(M, 15H), 4.45-1.20 (10H, m), 1.09-0.38 (m, 15H)

≪ Synthesis of transition metal compound >

The ligand thus prepared, 2,6-diisopropyl-N - ((6- (2-methyl-1,2,3,4-tetrahydroquinolin-8-yl) pyridin- ) (1.13 g, 2.0935 mmol, 1 eq) and toluene (6.98 mL, 0.3 M) were added to the solution, and then n-BuLi (1.76 mL, 4.396 mmol, 2.1 eq) was added dropwise. HfCl ₄ (0.704 g, 2.198 mmol, 1.05 eq) was added and heated at 90-100 ° C for 2 hours.

After the reaction was completed, the reaction mixture was cooled to room temperature and MeMgBr (2.44 mL, 7.33 mmol, 3.5 eq, 3.0 M in DEE) was added thereto. The solvent was vacuum dried and then filtered. The product was obtained as a yellow solid in 210 mg, 13% yield.

(M, 2H), 4.87 (m, 1H), 3.27-8.11 (m, 7H), 1.30-0.0

Comparative Preparation Example 1

<Synthesis of tert-butyl (dimethyl (2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl) silyl) amino) dimethyltitanium>

A comparative ligand compound (2.36 g, 9.39 mmol / 1.0 eq) and 50 mL (0.2 M) of MTBE were added to a 100 mL Schlenk flask and stirred. N-BuLi (7.6 mL, 19.25 mmol / 2.05 eq, 2.5 M in THF) was added at -40 ° C, and the reaction was allowed to proceed at room temperature overnight. Then, MeMgBr (6.4 mL, 19.25 mmol / 2.05 eq, 3.0 M in diethyl ether) was slowly added dropwise at -40 ° C and then TiCl ₄ (9.4 mL, 9.39 mmol / 1.0 eq, 1.0 M in toluene) And reacted overnight at room temperature. The reaction mixture was then filtered through Celite using hexane. After drying the solvent, a yellow solid was obtained in a yield of 2.52 g (82%).

_{^{1 H-NMR (in CDCl 3}} , 500 MHz):

2H), 2.17 (s, 6H), 1.92 (s, 6H), 1.57 (s, 9H), 0.48 (s, 6H), 0.17 (s, 6H).

Comparative Production Example 2

&Lt; Preparation of ligand and transition metal compound >

8- (l, 2-Dimethyl-lH- Benzo [b] cyclopenta [d] thiophene Yl) -2- methyl -1,2,3,4- Tetrahydroquinoline (8- (1,2-dimethyl-1H-benzo [b] cyclopenta [d] thiophen-3-yl) -2-methyl-1,2,3,4-tetrahydroquinoline

N BuLi (14.9 mmol, 1.1 eq) was slowly added dropwise to a solution of 2-methyl-1,2,3,4-tetrahydroquinoline (2 g, 13.6 mmol) in ether (10 mL) at -40 ° C . After slowly raising the temperature to room temperature, the mixture was stirred at room temperature for 4 hours. The temperature was again lowered to -40 ° C and CO ₂ (g) was injected and the reaction was maintained at low temperature for 0.5 hour. The temperature was gradually raised, and residual CO ₂ (g) was removed through a bubbler. THF (17.6 mmol, 1.4 mL, t BuLi (10.4 mmol, 1.3 eq) was added at -20 ° C and the mixture was aged at low temperature for 2 hours at -20 ° C. The ketone (1.9 g, 8.8 mmol) was dissolved in diethyl ether The reaction mixture was stirred for 12 hours at room temperature, and 10 mL of water was added thereto. The mixture was stirred for 2 minutes with hydrochloric acid (2N, 60 mL), and the organic solvent was extracted and neutralized with aqueous NaHCO ₃ solution The solvent was extracted and the water was removed with MgSO _{4. A} yellow oil was obtained via a silica gel column (1.83 g, 60% yield).

^{_{1 H NMR (C 6 D 6}} ): δ 1.30 (s, 3H, CH 3), 1.35 (s, 3H, CH 3), 1.89 ~ 1.63 (m, 3H, Cp-H quinoline-CH 2), 2.62 ~ 2.60 (m, 2H, quinoline- CH 2), 2.61 ~ 2.59 (m, 2H, quinoline-NCH 2), 2.70 ~ 2.57 (d, 2H, quinoline-NCH 2), 3.15 ~ 3.07 (d, 2H, quinoline- _{NCH 2), 3.92 (broad,} 1H, NH), 6.79 ~ 6.76 (t, 1H, aromatic), 7.00 ~ 6.99 (m, 2H, aromatic), 7.30 ~ 7.23 (m, 2H, aromatic), 7.54 ~ 7.53 ( m, 1H, aromatic), 7.62-7.60 (m, 1H, aromatic) ppm

8- (l, 2-Dimethyl-lH- Benzo [b] cyclopenta [d] thiophene Yl) -2- methyl -1,2,3,4- Tetrahydroquinoline - titanium dimethyl (8- (1,2- dimethyl -1H- benzo [b] cyclopenta [d] thiophene -3-yl) -2-methyl-1,2,3,4-tetrahydroquinoline-titanium dimethyl) compound

To this ligand (1.0 g, 2.89 mmol) was added n BuLi (3.0 mmol, 2.1 eq) slowly at -20 &lt; 0 &gt; C. Yellow slurry was observed to form and slowly warmed to room temperature and then stirred at room temperature for 12 hours. TiCl ₄ DME (806 mg, 2.89 mmol, 1.0 eq) was added dropwise and the mixture was stirred at room temperature for 12 hours. After removal of the solvent, it was extracted with toluene to give a red solid (700 mg, 52% yield). Methyl magnesium bromide (2.0 eq.) Was slowly added dropwise to the solution obtained by dissolving the red solid in 50 mL of THF at room temperature, stirred for 12 hours at room temperature, and then the solvent was removed and extracted with hexane to obtain a reddish-brown solid (560 mg, 80% yield).

¹ H NMR (CDCl ₃ ) mixture of isomers:? - 7.1 (d, 1H, Ar-H), 6.84 (t, 1H, J = 7.5 Hz, Ar- Hz, Ar-H), 6.98 (d, 1H, Ar-H), 2.6 ~ 2.7 (m, 2H, Piperidine-CH 2), 2.3 ~ 2.4 (m, 2H, Piperidine-CH 2), 1.63 ~ 1.69 ( _{m, 2H, Piperidine-CH 2} ), 1.50 ~ 1.55 (m, 2H, Piperidine-CH 2), 1.71 ~ 1.80 (m, 2H, Piperidine-CH 2), 1.56 ~ 1.61 (m, 2H, Piperidine-CH 2 ), 5.42 (m, 1H, Piperidine-CH), 1.15 (d, 3H, J = 6.5Hz, Piperidine-CH 3), 1.13 (d, 3H, J = 6.5Hz, Piperidine-CH 3), 7.84 (d 1H, J = 8 Hz, Ar-H), 7.83 (d, 1H, J = 8 Hz, Ar- 7.23 (d, 1H, J = 8Hz, Ar-H), 7.25 (d, 1H, J = 8Hz, Ar-H), 2.38 (s, 3H, Cp-CH 3), 2.41 (s, 3H, Cp- _{CH 3), 1.72 (s,} 3H, Cp-CH 3), 1.64 (s, 3H, Cp-CH 3), 0.68 (s, 3H, Ti-CH 3), 0.73 (s, 3H, Ti-CH 3 ), 0.18 (s, 3H, Ti-CH 3), 0.05 (s, 3H, Ti-CH 3) ppm

Comparative Production Example 3

&Lt; Preparation of ligand compound >

Synthesis of N-tert-butyl-1- (1,2-dimethyl-3H-benzo [b] cyclopenta [d] thiophen-3-yl)

To a 100 mL Schlenk flask was added 4.65 g (15.88 mmol) of chloro-1- (1, 2-dimethyl-3H-benzo [b] cyclopenta [d] thiophen- And 80 mL of THF was added thereto. TBuNH ₂ (4eq, 6.68 mL) was added at room temperature and reacted at room temperature for 3 days. After the reaction, the THF was removed, and the solution was filtered with hexane. After drying the solvent, a yellow liquid was obtained in a yield of 4.50 g (86%).

¹ H-NMR (in CDCl ₃ , 500 MHz): 7.99 (d, IH), 7.83 (d, IH), 7.35 (dd, IH), 7.24 s, 3H), 2.17 (s, 3H), 1.27 (s, 9H), 0.19 (s, 3H), -0.17 (s, 3H).

The ligand compound (1.06 g, 3.22 mmol / 1.0 eq) prepared above and 16.0 mL (0.2 M) of MTBE were added to a 50 mL Schlenk flask and stirred beforehand. N-BuLi (2.64 mL, 6.60 mmol / 2.05 eq, 2.5 M in THF) was added at -40 ° C, and the mixture was reacted at room temperature overnight. Then, MeMgBr (2.68 mL, 8.05 mmol / 2.5 eq, 3.0 M in diethyl ether) was slowly added dropwise at -40 ° C and then TiCl ₄ (2.68 mL, 3.22 mmol / 1.0 eq, 1.0 M in toluene) The reaction was allowed to proceed overnight at room temperature. The reaction mixture was then filtered through Celite using hexane. After drying the solvent, a brown solid was obtained in a yield of 1.07 g (82%).

¹ H-NMR (in CDCl ₃ , 500 MHz): 7.99 (d, IH), 7.68 (d, IH), 7.40 (dd, s, 3H), 2.05 (s, 3H), 1.54 (s, 9H), 0.58 (s, 3H), 0.57 (s, 3H), 0.40 (s,

Comparative Production Example 4

The compound of Comparative Preparation Example 4 was prepared according to the method described in Korean Patent Publication No. 2014-0075966.

Examples 1 and 2 and Comparative Examples 1 to 4

After adding triisobutylaluminum compound (0.3 mmol), hexane solvent and 1-octene as scavenger to the 2L autoclave reactor in the amounts shown in Table 6, diethylzinc was added in an amount of 100 equivalents based on the amount of catalyst introduced in the following table , And the temperature of the reactor was preheated to 120. At the same time, the reactor was pre-filled with ethylene to a pressure of 35 bar. The transition metal compounds prepared in the above Production Examples or Comparative Production Examples, which were treated with triisobutylaluminum compound (10 equivalents based on the catalyst) in the reactor, were charged into the amounts shown in Table 6 in the amounts shown in Table 6, and dimethylanilinium The tetrakis (pentafluorophenyl) borate (AB) cocatalyst was added to the reactor under high-pressure argon pressure in the order shown in Table 6 below. Then, the copolymerization reaction was carried out for 10 minutes. Next, the remaining ethylene gas was removed and the polymer solution was added to excess ethanol to induce precipitation. The precipitated polymer was washed with ethanol and acetone two to three times, respectively, and then dried for more than 12 hours in an 80 oven oven to measure the physical properties.

Reference Examples 1 and 2, Comparative Examples 1-1 to 4-1

Copolymerization was carried out in the same manner as in Examples 1 and 2 and Comparative Examples 1 to 4 except that no diethylzinc was added to obtain a copolymer, and the properties were measured.

Property evaluation

&Lt; Melt index of polymer &

The melt index (MI) of the polymer was measured by ASTM D-1238 (condition E, 190, 2.16 Kg load).

<Crystallization Temperature and Melting Temperature of Polymer>

The crystallization temperature (Tc) and the melting temperature (Tm) of the polymer were measured using a differential scanning calorimeter (DSC) 6000 manufactured by PerkinElmer. Specifically, the measurement container is charged with about 0.5 mg to 10 mg of the sample, and the flow rate of the nitrogen gas is set to 20 mL / min. To keep the thermal history of the polyolefin resin the same, / min. After cooling the sample at a rate of 10 ° C / min from 150 ° C to -100 ° C, the sample was further cooled from -100 ° C to 150 ° C at a rate of 10 ° C / min , The peak of the heating curve of the heat flow measured by DSC, that is, the endothermic peak temperature at the time of heating can be measured as the melting temperature.

&Lt; Polymer density &

The density of the polymer is determined by measuring the sample at 190 Lt; RTI ID = 0.0 &gt; mm, &lt; / RTI &gt; 2 mm in thickness with a press mold and annealed at room temperature for 24 hours and then measured on a Mettler balance.

Cat.
(compound)
(μmol) Diethyl
zinc
(μmol) 1-octene charge
(mL) density
(g / cc) Melt Index
(g / 10 min) Example 1 Production Example 1
(4) 400 170 0.884 4.12 Reference example
One Production Example 1
(4) - 170 0.877 0.03 Example 2 Production Example 2
(4) 400 200 0.883 3.20 Reference Example 2 Production Example 2
(4) - 200 0.873 0.08 Comparative Example
One Comparative Preparation Example 1
(One) 100 200 0.888 0.23 Comparative Example
1-1 Comparative Preparation Example 1
(One) - 200 0.889 0.80 Comparative Example
2 Comparative Production Example 2
(One) 100 170 0.866 0.01 Comparative Example
2-1 Comparative Production Example 2
(One) - 170 0.864 0.02 Comparative Example 3 Comparative Production Example 3
(One) 100 200 0.879 0.05 Comparative Example 3-1 Comparative Production Example 3
(One) - 200 0.879 0.14 Comparative Example 4 Comparative Production Example 4
(One) 100 170 0.864 11.10 Comparative Example 4-1 Comparative Production Example 4
(One) - 170 0.862 19.67

Polymerization conditions: hexane (1.0 L), ethylene (35 bar), 120 占 폚, Tc: crystallization temperature, Tm: melting temperature, MWD: molecular weight distribution (weight average molecular weight / number average molecular weight)

As shown in Table 6, in Examples 1 and 2, a copolymer having a high density and a high melt index could be produced by using the catalyst prepared in Preparation Example 1 and diethylzinc together. On the other hand, the copolymers prepared in Comparative Examples 1 to 4 had low densities when the densities were similar to each other, when the densities were similar or when the densities were similar, when compared with the copolymers prepared in Examples 1 and 2.

The reason why the copolymers prepared in Examples 1 and 2 have a high density and a high melt index together is that the diethylzinc acts as a chain shuttling agent, As a result, it was confirmed that the transition metal compounds obtained in Production Examples 1 and 2 used in Examples 1 and 2 were capable of chain transfer.

The evidence that the transition metal compounds obtained in Production Examples 1 and 2 as described above are capable of chain transfer can be confirmed by comparing the results of Reference Examples 1 and 2 and Comparative Examples 1-1 to 4-1 together.

Example 1 and Reference Example 1 use the same catalyst (the compound of Preparation Example 1), different polymerization conditions are the same, and there is a difference only in whether diethylzinc is used. In the case of Example 1 in which diethylzinc is used together , The density was increased and the melt index was greatly increased as compared with Reference Example 1 in which diethylzinc was not used. This tendency was the same in the results of Example 2 and Reference Example 2 in which the compound of Preparation Example 2 was used as a catalyst.

On the other hand, in the case of Comparative Example 1 and Comparative Example 1-1, the same catalyst (the compound of Comparative Preparation Example 1) was used in the same manner, and the other polymerization conditions were the same and only diethylzinc was used, In Comparative Example 1-1 using diethylzinc, the density was lowered and the melt index was reduced compared to Comparative Example 1 in which diethylzinc was not used. On the other hand, in the case of Comparative Example 2 and Comparative Example 2-1, in Comparative Example 2-1 in which diethylzinc was used, the density was slightly increased and the melt index was reduced compared with Comparative Example 2 in which diethylzinc was not used In the case of Comparative Example 3 and Comparative Example 3-1, it can be seen that the density is not changed and the melt index is reduced. In the case of Comparative Example 4 and Comparative Example 4-1, the density was slightly increased and the melt index was reduced.

The increase in the melt index is an index indicating that the molecular weight of the polymer is decreased. As in the case of Examples 1 and 2, the large increase in the melt index is due to the addition of diethylzinc, And chain transfer occurs in the production of the polymer.

As a result, it was confirmed that the diethylzinc acting as a chain shuttling agent exhibited a difference in the chain transfer effect depending on the type of catalyst. From this, it was confirmed that the transition metal compound And the dialkyl zinc of formula (2) can act as a catalyst and a chalcyl shuttling agent.

As described above, the catalyst composition of the present invention can be used as a catalyst for making a block copolymer since chain transfer of the polymer by the chain shuttling agent is possible.

Claims (14)

1. A catalyst composition comprising a transition metal compound represented by the following formula (1) and a dialkylzinc compound represented by the following formula (2):
[Chemical Formula 1]

In Formula 1,
R ₁ to R ₉ each independently represent 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, arylalkyl having 7 to 20 carbon atoms , Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl having from 1 to 20 carbon atoms;
Two or more adjacent ones of R ₁ to R ₈ 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;
n is 1 or 2;
Q ¹ and Q ² 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, arylalkyl having 7 to 20 carbon atoms , Alkylamido having 1 to 20 carbon atoms, arylamido having 6 to 20 carbon atoms, or alkylidene having 1 to 20 carbon atoms;
M is Ti, Zr or Hf;
(2)

In Formula 2,
R &lt; ₁₀ & And each R &lt; ₁₁ &gt; is independently an alkyl having 1 to 20 carbon atoms.
The method according to claim 1,
Wherein Q ¹ and Q ² are each independently hydrogen, halogen, alkyl of 1 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, alkylaryl of 6 to 20 carbon atoms, or arylalkyl of 7 to 20 carbon atoms.
The method according to claim 1,
Each of R ₁ to R ₉ is 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;
Two or more adjacent ones of R ₁ to R ₈ 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;
Wherein the aliphatic ring or aromatic ring may be substituted with halogen, alkyl of 1 to 20 carbon atoms, or aryl of 6 to 20 carbon atoms.
The method according to claim 1,
Wherein the compound of Formula 1 is any one of compounds represented by the following formulas.
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Chemical Formula 1-6]

[Chemical Formula 1-7]

[Chemical Formula 1-8]

[Chemical Formula 1-9]

[Chemical Formula 1-10]

[Formula 1-11]

[Formula 1-12]

[Formula 1-13]

[Chemical Formula 1-14]

[Chemical Formula 1-15]

[Chemical Formula 1-16]

[Formula 1-17]

[Chemical Formula 1-18]

[Chemical Formula 1-19]

[Chemical Formula 1-20]

[Formula 1-21]

[Formula 1-22]

The method according to claim 1,
Wherein the dialkylzinc compound represented by Formula 2 is at least one member selected from the group consisting of diethylzinc, dipropylzinc, dibutylzinc, and ethylpropylzinc.
The method according to claim 1,
Wherein the dialkylzinc compound represented by the formula (2) is mixed in an amount of 1 to 200 equivalents based on 1 equivalent of the transition metal compound of the formula (1).
The method according to claim 1,
Wherein the catalyst composition further comprises at least one cocatalyst.
8. The method of claim 7,
Wherein the cocatalyst comprises at least one selected from compounds represented by the following general formulas (11) to (13).
(11)
_{- [Al (R 12) -O} ] a -
In the formula (11), each R ₁₂ is independently a halogen radical; A hydrocarbyl radical having from 1 to 20 carbon atoms; Or a hydrocarbyl radical having 1 to 20 carbon atoms substituted with halogen; a is an integer of 2 or more;
[Chemical Formula 12]
D (R _{12) 3}
In Formula 12, D is aluminum or boron; R &lt; ₁₂ &gt; are each independently as defined in the above formula (11);
[Chemical Formula 13]
^{[LH] + [Z (A} ) 4] - or ^{[L] + [Z (A} ) 4] -
In Formula 13, L is a neutral or cationic Lewis acid; H is a hydrogen atom; Z is a Group 13 element; A is independently an aryl having 6 to 20 carbon atoms or an alkyl having 1 to 20 carbon atoms in which at least one hydrogen atom may be substituted with a substituent; The substituent is halogen, hydrocarbyl of 1 to 20 carbon atoms, alkoxy of 1 to 20 carbon atoms, or aryloxy of 6 to 20 carbon atoms.
The method according to claim 1,
Wherein the catalyst composition further comprises a reaction solvent.
A supported catalyst in which the catalyst composition according to claim 1 is supported on a carrier.
A process for preparing a polymer using the catalyst composition according to claim 1.
12. The method of claim 11,
Wherein the polymer is a homopolymer or copolymer of a polyolefin.
A process for producing a polymer using the supported catalyst according to claim 10.
12. The method of claim 11,
Wherein the polymer is a homopolymer or copolymer of a polyolefin.