KR20100083076A - Catalystic composition comprising transition metalcompound and thermal resist olefin polymer using the same - Google Patents

Abstract

PURPOSE: A catalytic composition including a transition metal compound and a high thermal resistance olefin polymer using the same are provided to make an olefin compound with good heat resistance and a molecular weight of 5,000 ~ 30,000. CONSTITUTION: A catalytic composition includes a first transition metal compound remarked as a chemical formula 1, a second transition metal compound remarked as a chemical formula 2, a cocatalyst compound selected from a group consisting of compounds marked as a chemical formula 4 ~ 6 and a polymerization adjuvant of zinc or gallium compound containing hydrocarbyl substituent of carbon number 1 ~ 12. In the chemical formula 1, R1, R1', R2 and R2' are alkyl, aryl, alkylaryl of the carbon number 7 ~ 20, or a metalloid radical etc.

Description

Catalyst composition comprising a transition metal compound and a high heat-resistant olefin polymer using the same {CATALYSTIC COMPOSITION COMPRISING TRANSITION METALCOMPOUND AND THERMAL RESIST OLEFIN POLYMER USING THE SAME}

The present invention relates to a catalyst composition comprising a transition metal compound and a high heat-resistant olefin polymer using the same, and more particularly, a first transition metal compound, a second transition metal compound, a promoter compound, and a hydrocarbyl having 1 to 12 carbon atoms. A catalyst composition for olefin polymerization comprising a polymerization aid which is a zinc or gallium compound containing a substituent, and a low molecular weight olefin having a melting point of 100 to 140 ° C. and a molecular weight of 30,000 or less at a density of 0.9 g / cc or less prepared using the catalyst composition. It relates to a polymer.

In the case of general waxes (molecular weight of 30,000 or less), most products have little heat resistance due to low molecular weight.

In general, polyolefin waxes have various uses. For example, it can be applied to various fields such as automotive coating wax and processing aids and adhesives, pressure-sensitive adhesives. It can also be used as a medium pressure toner releasing agent, and can be applied to surfactants, silicone oil hardeners, various lubricants, emulsifying mold releasing agents, reactive intermediates, surfactants, and precision molding materials.

Waxes made using conventional Ziegler-Natta catalyst technology and metallocene technology have been limited in their use in applications where heat resistance is required as the melting point is 100 ° C. or less.

In general, the lower the molecular weight, the more active the movement of molecules in the same thermal environment as compared to the high molecular weight has a disadvantage that the melting point is low.

In order to solve the problems of the prior art as described above, an object of the present invention is to provide a novel catalyst composition for olefin polymerization and its preparation method.

In addition, an object of the present invention is to provide an olefin wax polymer and a method of producing the same by polymerizing an olefin monomer using the catalyst composition.

The above and other objects of the present invention can be achieved by the present invention described below.

In order to achieve the above object, the present invention provides a polymerization aid which is a zinc or gallium compound containing a first transition metal compound, a second transition metal compound, a cocatalyst compound, and a hydrocarbyl substituent having 1 to 12 carbon atoms. It provides a catalyst composition for olefin polymerization comprising and a method for producing the same.

The present invention also provides a low molecular weight olefin wax polymer having a density of 0.7 to 0.9 g / cc, a melting point of 100 to 140 ° C., a molecular weight of 5,000 to 30,000, and a method for producing the same, which are prepared by polymerizing an olefin monomer using the catalyst composition. do.

As described above, when the olefin monomer is polymerized using the catalyst composition according to the present invention, the olefin monomer has a density of 0.7 to 0.9 g / cc, a melting point of 100 to 140 ° C., a low molecular weight of 5,000 to 30,000, and excellent heat resistance. It has the effect of providing a polymer.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The present inventors have developed a technology capable of producing a polyolefin wax having excellent heat resistance even in a low molecular weight state through a novel catalyst system. Specifically, by applying a metallocene catalyst and adding a specific polymerization aid, it is possible to produce a wax having excellent heat resistance and a low density region (0.90 g / cc or less).

In general, when the molecular weight is lowered, the melting point is lowered because the movement of molecules is more active than the high molecular weight in the same thermal environment, but in the present invention, by applying a technique for controlling the sequence of molecular structure, it is possible to overcome this general idea. Could go over.

The catalyst composition for olefin polymerization according to the present invention includes a first transition metal compound represented by Formula 1 or Formula 2, a second transition metal compound represented by Formula 3, at least one promoter compound of Formulas 4 to 6, and It is characterized by including a polymerization aid which is a zinc or gallium compound containing a C1-C12 hydrocarbyl substituent.

(A) the first transition metal compound

The present invention provides a transition metal compound of Formula 1 below.

In Chemical Formula 1,

R1, R1 ', R2 and R2' are each independently hydrogen, alkyl of 1 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, alkenyl of 1 to 20 carbon atoms, alkylaryl of 7 to 20 carbon atoms, of 7 to 20 carbon atoms Arylalkyl, and metalloid radicals of a Group 14 metal substituted with hydrocarbyl, or two or more of them are linked to each other by an alkylidine including alkyl having 1 to 20 carbon atoms or aryl having 6 to 20 carbon atoms Or an aromatic ring,

R3 is an aliphatic ring having 1 to 20 carbon atoms,

R4, R4 ', R4' ', and R4' '' are each independently selected from hydrogen, a halogen radical, alkyl having 1 to 20 carbon atoms and aryl having 6 to 20 carbon atoms, or two R4 are linked to each other to be aliphatic or Formed with an aromatic ring,

E is a nitrogen or phosphorus atom,

M is a Group 4 transition metal,

Q ₁ and Q ₂ are each independently a halogen radical, alkyl having 1 to 20 carbon atoms, aryl amido having 6 to 20 carbon atoms, 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, and alkylidene having 1 to 20 carbon atoms.

In the transition metal compound represented by Formula 1, E is a nitrogen atom, and R 3 is preferably a cyclohexyl group.

In addition, the transition metal compound represented by Formula 1 is preferably a compound represented by the following formula (2).

In Chemical Formula 2,

R1, R1 ', R1' ', R1' '', R2, R2 ', R2' ', R2' '' are each independently hydrogen, alkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, and having 1 to C carbon atoms. Or a metalloid radical of a Group 14 metal substituted with alkenyl of 20, alkylaryl of 7 to 20 carbon atoms, arylalkyl of 7 to 20 carbon atoms, and hydrocarbyl, or at least two of them are alkyl of 1 to 20 carbon atoms Or are connected to each other by an alkylidine including aryl having 6 to 20 carbon atoms to form an aliphatic or aromatic ring,

R3, R3 'is an aliphatic ring having 1 to 20 carbon atoms,

R4, R4 ' Are each independently selected from hydrogen, a halogen radical, alkyl having 1 to 20 carbon atoms and aryl having 6 to 20 carbon atoms, or two R 4 are connected to each other to form an aliphatic or aromatic ring,

E is a nitrogen or phosphorus atom,

M is a Group 4 transition metal,

Q ₁ and Q ₂ are each independently a halogen radical, alkyl having 1 to 20 carbon atoms, aryl amido having 6 to 20 carbon atoms, 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, and alkylidene having 1 to 20 carbon atoms;

G is a covalent bridging group connecting the two phenylene rings, an epoxy group; Epithio group; Carbonyl group; Silane group; Disilane group; Substituted or unsubstituted C1-C60 hydrocarbylene group; Or a substituted or unsubstituted heterohydrocarbylene group having 1 to 60 carbon atoms including a Group 4B, Group 5B or Group 6B element.

The metalloid is an element in the form of a metal, and an element showing intermediate properties between a metal and a nonmetal, and arsenic, boron, silicon, tellurium, and the like, but are not limited thereto.

In the compound represented by Formula 2, E is nitrogen, and R 3 is preferably cyclohexyl.

The transition metal compound represented by Chemical Formula 1 has an amido group and an amino or alkoxy group connected by a phenylene bridge, so that the DME angle (angle formed by the diene-ME of the five-membered ring) is narrow and Q ₁ − that the monomer approaches. The MQ ₂ angle is kept wide to allow easy access of large monomers.

In addition, unlike the CGC structure connected by the silicon bridge, in the transition metal compound structure represented by Chemical Formula 1, for example, oxygen, phenylene bridge, and nitrogen together with metal sites form a stable and rigid hexagonal ring structure. .

Therefore, when these compounds are reacted with methylaluminoxane or a cocatalyst such as B (C ₆ F ₅ ) ₃ to be activated and then applied to the olefin polymerization, the characteristics such as high activity, high molecular weight and high copolymerization even at high polymerization temperature It would be possible to produce polyolefins having

Particularly, due to the structural characteristics of the catalyst, not only linear low density polyethylene having a density of 0.910 to 0.930 g / cc, but also a large amount of alpha-olefin can be introduced, so that an ultra low density polyolefin copolymer having a density of 0.7 to 0.910 g / cc can be prepared. have. In addition, various substituents may be introduced into the nitrogen atom, the oxygen atom, and the phenylene ring, which ultimately control the structure and physical properties of the polyolefin produced by easily controlling the electronic and three-dimensional environment around the metal.

The catalyst composition of the present invention is preferably used to prepare a catalyst for the polymerization of the olefin monomer, but is not limited thereto. It is applicable to all fields in which the transition metal compound may be used.

(B) a second transition metal compound

The present invention provides a transition metal compound of Formula 3 as a second transition metal compound.

In Chemical Formula 3,

M is a Group 4 to 10 metal in the Periodic Table of the Elements,

T is a nitrogen, oxygen or phosphorus containing group,

X is halogen, hydrocarbyl or hydrocarbyloxy,

i is 1 or 2,

N means nitrogen,

T and N are linked by bridging ligands A,

A is an alkyl, cycloalkyl, heteroalkyl, cycloheteroalkyl, aryl, and inert substituted derivative or divalent derivative thereof having 1 to 30 atoms excluding hydrogen.

Compounds of Formula 3 have been disclosed in several documents. See J. Am. Chem. Soc., 118, 267-268 (1996), J. Am. Chem. Soc., 117, 6414-6415 (1995), and Organometallics, 16, 1514-1516 (1997)].

In Formula 3, M may be preferably a Group 4 metal, Ni (II) or Pd (II), and most preferably zirconium.

By including not only the first transition metal compound of Formula 1 or Formula 2 but also the second transition metal compound of Formula 3 in the catalyst composition of the present invention, the density of the final polymer can be controlled and a high heat resistant polymer can be prepared. There is an advantage to being there.

(C) promoter compounds

The catalyst composition of the present invention includes at least one of the promoter compounds represented by the following formulas (4) to (6).

- [Al (R5) -O] a -

In Chemical Formula 4,

R 5 is selected from halogen radicals, hydrocarbyl having 1 to 20 carbon atoms and hydrocarbyl having 1 to 20 carbon atoms substituted with halogen,

a is an integer of 2-5.

J (R6) ₃

In Formula 5,

J is aluminum or boron,

R 6 is selected from halogen radicals, hydrocarbyl having 1 to 20 carbon atoms and hydrocarbyl having 1 to 20 carbon atoms substituted with halogen.

_{^{[LH] + [ZA 4]}} - or _{^{[L] + [ZA 4]}} -

In Formula 6,

L is a neutral or cationic Lewis acid,

H is a hydrogen atom,

Z is a Group 13 element selected from B, Al, Ga, In and Tl,

A is a halogen having a hydrogen valence of 1 or more; Hydrocarbyl having 1 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms or alkyl having 1 to 20 carbon atoms substituted with alkoxy having 1 to 20 carbon atoms or phenoxy having 6 to 20 carbon atoms.

Among the promoter compounds represented by Formulas 4 to 6, the compounds represented by Formulas 4 and 5 may be used as alkylating agents, and the compounds represented by Formula 6 may be used as activators.

The compound represented by Chemical Formula 4 is not particularly limited as long as it is an alkyl aluminoxane, but preferred examples thereof include methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, and butyl aluminoxane, and particularly preferred compound is methyl aluminoxane.

The compound represented by Formula 5 is not particularly limited as long as it is an alkyl metal compound, but preferred examples thereof include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum and 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, dimethylaluminum ethoxide, trimethylboron, triethylboron, triisobutylboron, tripropylboron, tributylboron and the like, particularly preferred compounds selected from trimethylaluminum, triethylaluminum and triisobutylaluminum do.

Examples of the compound represented by Formula 6 include triethylammonium tetra (phenyl) boron, tributylammonium tetra (phenyl) boron, trimethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, Trimethylammonium tetra (p-tolyl) boron, trimethylammonium tetra (o, p-dimethylphenyl) boron, tributylammonium tetra (p-trifluoromethylphenyl) boron, trimethylammonium tetra (p-trifluoro) Methylphenyl) boron, tributylammonium tetra (pentafluorophenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (pentafluorophenyl) boron, Diethyl ammonium tetra (pentafluorophenyl) boron, trimethyl phosphonium tetra (phenyl) boron, triethyl ammonium tetra (phenyl) aluminum, tributyl ammonium tetra (phenyl) aluminum, trimethyl ammonium tetra (phenyl) aluminum , Tripropylammon Umtetra (phenyl) aluminum, trimethylammoniumtetra (p-tolyl) aluminum, tripropylammoniumtetra (p-tolyl) aluminum, triethylammoniumtetra (o, p-dimethylphenyl) aluminum, tributylammoniumtetra (p-trifluoromethylphenyl) aluminum, trimethylammonium tetra (p-trifluoromethylphenyl) aluminum, tributylammonium tetra (pentafluorophenyl) aluminum, N, N-diethylanilinium tetra (phenyl) Aluminum, N, N-diethylanilinium tetra (phenyl) aluminum, N, N-diethylanilinium tetra (pentafluorophenyl) aluminum, diethylammonium tetra (pentafluorophenyl) aluminum, triphenyl Phosphonium tetra (phenyl) aluminum, trimethylphosphonium tetra (phenyl) aluminum, triethylammonium tetra (phenyl) aluminum, tributylammonium tetra (phenyl) aluminum, trimethylammonium tetra (phenyl) boron, tripropylammonium Tetra (phenyl) boron, trimethyl ammonium tetra (p-tolyl) boron, tripropyl ammonium tetra (p-tolyl) boron, triethyl ammonium tetra (o, p-dimethylphenyl) boron, trimethyl ammonium tetra (o , p-dimethylphenyl) boron, tributyl ammonium tetra (p-trifluoromethylphenyl) boron, trimethyl ammonium tetra (p-trifluoromethylphenyl) boron, tributyl ammonium tetra (pentafluorophenyl) boron , N, N-diethylanilinium tetra (phenyl) boron, triphenyl phosphonium tetra (phenyl) boron, triphenyl carbonium tetra (p-tripullomethylphenyl) boron, triphenyl carbonium tetra Pentafluorophenyl) boron, trityl tetra (pentafluorophenyl) boron, trityl tetrakis (pentafluorophenyl) borate and the like.

(D) polymerization aid

The catalyst composition of the present invention is characterized in that it comprises a polymerization aid as described below.

The polymerization aid according to the present invention is a zinc or gallium compound containing a hydrocarbyl substituent having 1 to 12 carbon atoms, and specifically includes one or more selected from the group consisting of dimethylzinc, diethylzinc, dimethylgallium, diethylgallium, and the like. do.

The polymerization aid may be included in the catalyst composition for olefin polymerization to finely control the crystal structure of the polymer produced by the transition metal compound, thereby allowing the polymer to have high crystallinity.

By adding such a polymerization aid to the catalyst composition of the present invention, the crystallinity of the polymer structure is increased and the comonomer content is increased to have a high melting point and a density of 0.7 to 0.90 g / cc. A high heat resistant olefin wax polymer can be produced.

The catalyst composition according to the present invention is present in an activated state by a reaction between a transition metal compound and a promoter, and is sometimes referred to as an activated catalyst composition. However, since it is known in the art that the catalyst composition for olefin polymerization is in an activated state, the term activated catalyst composition is not used separately herein.

The catalyst composition can be used for olefin homopolymerization or copolymerization.

<The catalyst composition of the present invention and its manufacturing method>

Catalyst composition according to the present invention

a) obtaining a mixture by contacting at least one of the first transition metal compound represented by Formula 1 or Formula 2 with the second transition metal compound represented by Formula 3, and the compounds represented by Formula 4 and Formula 5. ;

b) adding the compound represented by Chemical Formula 6 to the mixture a);

c) adding a polymerization aid which is a zinc or gallium compound containing a hydrocarbyl substituent having 1 to 12 carbon atoms to the b) mixture; It may be prepared by a manufacturing method including, but is not limited thereto.

In this case, the molar ratio of the first transition metal compound of Formula 1 to the second transition metal compound of Formula 3 is preferably 1: 1 to 1: 2. When the molar ratio of at least one compound of the transition metal compound of Formula 3 is less than 1: 1, there is a problem that the catalytic activity is lowered, and when it is greater than 1: 2, there is a problem that molecular weight control is difficult.

The molar ratio of the first transition metal compound of Formula 1 to at least one of the compounds represented by Formulas 4 and 5 is preferably 1:20 to 1: 2000. When the molar ratio of one or more compounds of the compounds represented by Formulas 4 and 5 is less than 1:20, the amount of the alkylating agent, which is a compound represented by Formula 4 or 5, is very small so that the alkylation of the metal compound may not be fully performed. In the case of exceeding 1: 2,000, the alkylation of the metal compound is performed, but the activation of the alkylated metal compound is not fully performed due to a side reaction between the remaining excess alkylating agent and the activator represented by Formula 6. There is.

In addition, the molar ratio of the first transition metal compound of Formula 1 to the compound represented by Formula 6 is preferably 1: 2 to 1: 5. When the ratio of the compound represented by Chemical Formula 6 is less than 1: 2, the amount of the activating agent, which is the compound represented by Chemical Formula 4, is relatively small, resulting in inferior activity of the catalyst composition generated due to incomplete activation of the metal compound. In addition, when it exceeds 1: 5, the metal compound is completely activated, but the excess amount of the activator causes a problem in that the cost of the catalyst composition is not economical and the purity of the resulting polymer is inferior.

The preferred blending molar ratio of the first transition metal compound of Formula 1 to the polymerization aid is 1:50 to 1: 1,000, more preferably 1: 100 to 1: 500. If the molar ratio of the polymerization aid is less than 1:50, there is a problem that the heat resistance is deteriorated. If the molar ratio of the polymerization aid is greater than 1: 1,000, the activity of the transition metal compound is greatly reduced, and the molecular weight and physical properties of the compound are lowered.

In preparing the catalyst composition for olefin polymerization, a reaction solvent may be a hydrocarbon solvent such as pentane, hexane, heptane, or an aromatic solvent such as benzene, toluene, etc., but is not necessarily limited thereto and may be used in the art. All solvents can be used.

In addition, the transition metal compounds of Formula 1 or Formula 2 and the cocatalyst compounds may be used in a form supported on silica or alumina.

<The olefin polymer using the catalyst composition of this invention, and its manufacturing method>

The present invention polymerizes the olefin monomer using the catalyst composition to provide an olefin wax polymer having a density of 0.7 to 0.9 g / cc, a melting point of 100 to 140 ° C., a low molecular weight of 5,000 to 30,000, and excellent heat resistance.

The olefin wax polymer can be either a homopolymer or a copolymer. When the olefin wax polymer is a copolymer of ethylene and other comonomers, the comonomers constituting the copolymer are ethylene and propylene, 1-butene, 1-hexene, and 4-methyl-1-pentene, and 1-octene It is preferably one or more selected from the group consisting of.

The present invention also provides a method for producing an olefin wax polymer using the catalyst composition and an olefin monomer.

The method for producing the olefin wax polymer of the present invention is preferably a solution process using the catalyst composition for olefin polymerization, and can also be applied to a slurry or gas phase process when such a composition is used together with an inorganic carrier such as silica.

The continuous polymerization process of the present invention may be composed of a catalytic process, a polymerization process, a solvent separation process, a recovery process step, and a brief outline is as follows.

(a) catalytic process

In the polymerization process of the present invention, the catalyst composition is an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms suitable for the olefin polymerization process, for example, pentane, hexane, heptane, nonane, decane, and isomers thereof and aromatic hydrocarbon solvents such as toluene and benzene. It can be injected by dissolving or diluting in a hydrocarbon solvent substituted with a chlorine atom such as dichloromethane or chlorobenzene. The solvent used herein is preferably used by removing a small amount of water or air that acts as a catalyst poison by treating a small amount of alkylaluminum, and may be carried out by further using a promoter.

(b) polymerization process

Examples of olefinic monomers that can be polymerized using the catalyst composition according to the present invention include ethylene, alpha-olefins, cyclic olefins, and the like, and diene olefin monomers or triene olefin monomers having two or more double bonds. Polymerization is possible.

In addition, in the present invention, in order to prepare an olefin polymer having a melting point of 100 ° C. or higher at a density of 0.9 g / cc or less by copolymerizing a monomer having high steric hindrance such as ethylene and 1-octene using the catalyst composition for olefin wax polymerization, 90 It is preferably prepared in a high temperature of ~ 150 ℃ and 10 ~ 1300 bar high pressure atmosphere.

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-eicosene, norbornene, norbornadiene, ethylidenenorbornene, phenylnorbornene, vinylnorbornene, dicyclopentadiene, 1, 4-butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, 3-chloromethylstyrene, and the like, and these monomers may be mixed and copolymerized. .

More specifically, the monomer constituting the copolymer is preferably at least one monomer selected from the group consisting of ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene.

Polymerization solvents of the present invention include aliphatic hydrocarbon solvents having 5 to 12 carbon atoms suitable for the olefin polymerization process, for example, pentane, hexane, heptane, nonane, decane, and their isomers and aromatic hydrocarbon solvents such as toluene and benzene, dichloro Hydrocarbon solvents substituted with chlorine atoms such as methane, chlorobenzene and the like. The solvent used herein is preferably used by removing a small amount of water, air, or the like acting as a catalyst poison by treating a small amount of alkylaluminum.

The solvent is introduced into the reactor at a temperature of -40 ~ 150 ℃ using a heater or a freezer and the polymerization is started with the monomer and the activating composition. Feeds to the reactor are passed through the mixture without additional pumping between the reactor arrangement, the pressure reducing means and the separator by means of a high capacity pump raising the feed pressure above 50 bar and feeding it through the movement of the pump.

The polymerization reaction temperature in the reactor is preferably made of a temperature of 70 ~ 200 ℃, more preferably 90 ~ 150 ℃.

The pressure in the reactor is preferably 10 to 1300 bar, more preferably may be a high pressure of 10 to 300 bar. The polymer reacted in the reactor is maintained at a concentration of less than 20% by weight in a solvent and is passed to the first solvent separation process for solvent removal after a short residence time. The residence time of the polymer in the reactor is preferably 5 to 30 minutes.

(c) solvent separation process

The solvent separation process is performed by changing the solution temperature and pressure to remove the solvent present with the polymer. The solvent separation process is performed by changing the solution temperature and pressure to remove the solvent present with the polymer exiting the reactor. The polymer solution transferred from the reactor was heated to 230 ° C. through a heater, and then the pressure was lowered through a pressure drop device to gasify the solvent in the first separator. At this time, the pressure in the separator is preferably about 5 to 10 bar, more preferably 7 to 8 bar. The temperature in the separator is preferably between 200 and 250 ° C, more preferably 230 ° C. The solvent gasified in the separator can be recycled to the condensed reactor in the overhead system. The first step of solvent separation yields a polymer solution concentrated up to 65%, which is transferred to the second separator by a transfer pump through a heater, where the separation of residual solvents takes place. In order to prevent the deformation of the polymer due to the high temperature while passing through the heater, a thermal stabilizer is added and a reaction inhibitor is injected into the heater together with the thermal stabilizer to suppress the reaction of the polymer due to the residual activity of the activator present in the polymer solution. do. The remaining solvent in the polymer solution injected into the second separator is finally completely removed by a vacuum pump, and the granulated polymer can be obtained by passing through the cooling water and the cutter. The solvent and other unreacted monomers vaporized in the second separation process can be sent to a recovery process for reuse after purification.

(d) recovery process

The organic solvent added to the polymerization process together with the raw material may be recycled to the polymerization process with 85% of the unreacted raw material in the primary solvent separation process. However, 15% of the solvent recovered in the secondary solvent separation process contains a large amount of water that acts as a catalyst poison in the solvent due to contamination due to incorporation of a reaction inhibitor to stop the catalytic activity and steam supply from a vacuum pump. It is good to be reused after purification.

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

The organic reagents and solvents used in the following Preparation Examples, Examples, and Comparative Examples were purchased from Aldrich and Merck and purified by standard methods.

At all stages of the synthesis, the contact between air and moisture was blocked to increase the reproducibility of the experiment. In addition, spectra and diagrams were obtained using a 400 MHz nuclear magnetic resonance (NMR) and x-ray spectrometer, respectively, to demonstrate the structure of the compound.

Preparation Examples 1 to 5 Preparation of First Transition Metal Compound (Preparation Example 5) According to the Present Invention

<Manufacture example 1>

4- (4- (cyclohexylamino) benzyl) -N-cyclohexylbenzeneamine

To 4 g of 4,4-methyleneaniline (20.175 mmol), 15.839 g of cyclohexanone (161.396 mmol), and molecular sieves (4A, 10.0 g) were added 30 mL of toluene solvent. The whole solution was reacted at 100 ° C. for 2 days.

After lowering the reaction solution to room temperature, the molecular sieves were filtered off and dried in vacuo at 60 ° C. to obtain a 4- (4- (cyclohexylideneamino) benzyl) -N-cyclohexylbenzeneamine compound.

The obtained compound was dissolved in 60 mL of methanol, and 4.576 g (121.047 mmol) of sodium borohydride was added thereto, followed by reaction at room temperature for 2 hours. The reaction solution was then neutralized with 80 mL of 1N potassium hydroxide (KOH) solution.

The aqueous layer was extracted with 120 mL of methylene chloride, dried over magnesium sulfate (MgSO ₄ ), and recrystallized with hexane and ethyl acetate solvent to obtain a white solid compound (3.765 g, 51%).

¹ H NMR (CDCl ₃ ): δ 1.17-1.26 (m, 4H, Cy-CH ₂ ), 1.26-1.35 (m, 2H, Cy-CH ₂ ), 1.40-1.49 (m, 4H, Cy-CH ₂ ) , 1.72-1.75 (m, 2H, Cy-CH ₂ ), 1.82-1.85 (m, 4H, Cy-CH ₂ ), 2.11-2.14 (m, 4H, Cy-CH ₂ ), 3.27-3.32 (m, 2H , Cy-CH), 3.38 (br s, 2H, NH), 3.84 (s, 2H, CH ₂ ), 6.59 (d, J = 8.0 Hz, 4H, C ₆ H ₄ -CH), 7.04 (d, J = 8.0 Hz, 4H, C ₆ H ₄ -CH) ppm,

<Manufacture example 2>

4- (3-bromo-4-cyclohexylamino) benzyl) -2-bromo-N-cyclohexylbenzeneamine

1.5 g (4.137 mmol) of 4- (4- (cyclohexylamino) benzyl) -N-cyclohexylbenzeneamine obtained in Preparation Example 1 was dissolved in 15 mL of methylene chloride, and the solution was cooled to 0 ° C. 1.322 mL (Br ₂ , 8.275 mmol) of bromine solution dissolved in 10 mL of methylene chloride was slowly added at 0 ° C. for 30 minutes to further react for 2 hours. 10 mL of 1N potassium hydroxide (KOH) solution was added thereto, and the aqueous layer was extracted with 40 mL of methylene chloride and dried over magnesium sulfate (MgSO ₄ ). Purification by column chromatography using hexane and ethyl acetate (20: 1) solvent to give a white solid compound (1.523g, 71%).

¹ H NMR (C ₆ D ₆ ): δ 0.93-1.16 (m, 10H, Cy-CH ₂ ), 1.39-1.42 (m, 2H, Cy-CH ₂ ), 1.50-1.54 (m, 4H, Cy-CH ₂ ), 1.79-1.82 (m, 4H, Cy-CH ₂ ), 3.03-3.05 (m, 2H, Cy-CH), 3.54 (s, 2H, CH ₂ ), 4.21 (s, 1H, NH), 4.23 (s, 1H, NH), 6.45 (d, J = 8.0 Hz, 2H, C ₆ H ₃ Br-CH), 6.89 (d, J = 8.0 Hz, 2H, C ₆ H ₃ Br-CH) 7.34 (s , 2H, C ₆ H ₃ Br-CH) ppm

<Manufacture example 3>

4- (3- (3,4-dimethylcyclopenta-1,3-dienone) -4- (cyclohexylamino) benzyl) -2- (3,4-dimethylcyclopenta-1,3-dienone) -N-cyclohexylbenzeneamine

1.378 g (2.650 mmol) of boron acid and 0.857 g of 4- (3-bromo-4-cyclohexylamino) benzyl) -2-bromo-N-cyclohexylbenzeneamine prepared in Preparation Example 2 (5.565 mmol), 0.843 g (7.951 mmol) of sodium carbonate (Na ₂ CO ₃ ), 0.123 g (0.106 mmol) of Pd (Ph ₃ ) ₄ was dissolved in 12 mL of dimethyl ether (DME) and 4 mL of water, followed by 40 at 95 ° C. The reaction was carried out for hours. After the reaction solution was cooled to room temperature, the organic layer was extracted with 30 mL of ethyl acetate. The resulting solution was dried over magnesium sulfate (MgSO ₄ ), and then purified by column chromatography using hexane and an ethyl acetate solvent (hexane volume: ethyl acetate volume = 3: 1) to give a yellow solid compound. (1.206g , 79%)

¹ H NMR (C ₆ D ₆ ): δ 0.74 (d, J = 6.Hz, 6H, CH ₃ ), 1.17-1.20 (m, 10H, Cy-CH ₂ ), 1.42-1.45 (m, 2H, Cy -CH ₂ ), 1.57-1.62 (m, 4H, Cy-CH ₂ ), 1.66 (s, 6H, CH ₃ ), 1.82 (dd, J = 2.0, 18.4 Hz, 2H, CH), 1.92-2.07 (m , 4H, Cy-CH ₂ ), 2.16-2.19 (m, 2H, CH), 2.41 (dd, J = 6.4, 21.6 Hz, 2H, CH), 3.18 (br s, 2H, N-CH), 3.98 ( s, 2H, Bridged-CH ₂ ), 6.74 (d, J = 8.0 Hz, 2H, C ₆ H ₃ -CH), 6.98 (d, J = 8.0 Hz, 2H, C ₆ H ₃ -CH) 7.21 (dd , J = 2.4, 8.0 Hz, 2H, C ₆ H ₃ -CH) ppm

&Lt; Preparation Example 4 &

4- (3- (2,3,5-trimethylcyclopenta-1,3-dienone) -4- (cyclohexylamino) benzyl) -2- (2,3,5-trimethylcyclopenta-1,3 -Diene) -N-cyclohexylbenzeneamine

3.744 g (15.203 mmol) of anhydrous cesium chloride (CeCl ₃ ) were dissolved in 30 mL of THF, and the solution was cooled to -78 ° C. 9.502 mL (15.203 mmol) of methyllithium (MeLi) was slowly added thereto and reacted at -78 ° C for 1 hour, and then 1.100 g (1.900 mmol) of the compound prepared in Preparation Example 3 was added thereto for 2 hours at -78 ° C. Reacted further. 30 mL of distilled water and 40 mL of ethyl acetate were added thereto, and the organic layer was extracted. Hydrochloric acid (HCl) was added thereto and reacted for 2 minutes, neutralized with sodium hydrogen carbonate (NaHCO ₃ ) base, and the organic layer obtained was dried over magnesium sulfate (MgSO ₄ ). The obtained oil was purified by column chromatography using hexane and ethyl acetate (hexane volume: ethyl acetate volume = 20: 1) solvent to obtain a white oil (0.502g, 46%).

¹ H NMR (C ₆ D ₆ ): δ 0.95-1.02 (m, 4H, Cy-CH ₂ ), 1.09-1.19 (m, 6H, Cy-CH ₂ ), 1.28-1.31 (m, 2H, Cy-CH ₂ ), 1.41-1.44 (m, 2H, Cy-CH ₂ ), 1.49-1.54 (m, 4H, Cy-CH ₂ ), 1.80 (s, 6H, CH ₃ ), 1.87 (s, 6H, CH ₃ ) , 1.89 (s, 6H, CH ₃ ), 1.93-1.97 (m, 2H, Cy-CH ₂ ), 2.66-2.81 (m, 4H, CH ₂ ), 3.14-3.21 (m, 2H, N-CH), 3.68 (s, 1H, NH), 3.70 (s, 1H, NH), 4.00 (s, 2H, Bridged-CH ₂ ), 6.71 (d, J = 8.0 Hz, 2H, C ₆ H ₃ -CH), 7.08 (d, J = 1.6 Hz, 2H, C ₆ H ₃ -CH), 7.22 (dd, J = 1.6, 8.0 Hz, 2H, C ₆ H ₃ -CH) ppm

Preparation Example 5 First Transition Metal Compound

Methylidene-bis- (3,4-phenylene (cyclohexylamido) (2,3,5-trimethylcyclopentadienyl) titanium dichloride)

4- (3- (2,3,5-trimethylcyclopenta-1,3-dienone) -4- (cyclohexylamino) benzyl) -2- (2,3,5-trimethyl obtained in Preparation Example 4 above A solution containing 1.1481 g (2.58 mmol) of cyclopenta-1,3-diene) -N-cyclohexylbenzeneamine, 1.271 g (5.67 mmol) of Ti (N (CH ₃ ) ₂ ) ₄ and 15 mL of toluene solvent was prepared. The reaction was carried out at 2 ° C for 2 days. The solvent was removed and extracted with pentane to give a red solid. The solid compound was dissolved in 15 mL of toluene and 1.996 g (15.46 mmol) of (CH ₃ ) ₂ SiCl ₂ was added. After stirring for 4 hours at room temperature, the solvent was removed and pentane was added and triturated to give a red solid compound (1.808 g, overall 87%).

¹ H NMR (C ₆ D ₆ ): δ 0.91-0.97 (m, 2H, Cy-CH ₂ ), 1.40-1.52 (m, 6H, Cy-CH ₂ ), 1.68-1.75 (m, 3H, Cy-CH ₂ ), 1.70 (s, 6H, CH ₃ ), 1.82 (s, 6H, CH ₃ ), 1.89-2.00 (m, 6H, Cy-CH ₂ ), 2.06-2.18 (m, 3H, Cy-CH ₂ ) , 2.13 (s, 6H, CH ₃ ), 3.95 (s, 2H, bridged-CH ₂ ), 5.50-5.61 (m, 2H, N-CH), 6.10 (s, 2H, Cp-H), 6.68 (d , J = 8.0 Hz, 2H, C ₆ H ₃ -CH), 7.04 (s, 2H, C ₆ H ₃ -CH), 7.09 (d, J = 8.0 Hz, 2H, C ₆ H ₃ -CH) ppm

EXAMPLES An olefin polymer was prepared using the prepared catalyst composition.

&Lt; Example 1 >

Ethylene and 1-octene copolymer (mole ratio of polymerization aid: transition metal compound = 50: 1)

1.0 L of hexane solvent and 144 mL of 1-octene were added to a 2 L autoclave reactor, and the reactor temperature was preheated to 90 ° C. Titanium compound treated with 125 mmol of a triisobutylaluminum compound in a 25 mL catalyst storage tank (wherein the titanium compound means the catalyst prepared in Preparation Example 5) 5.0 mmol and trityl tetrakis (pentafluorophenyl 25 mmol of borate cocatalyst was added sequentially. At this time, 5 mmol of the catalyst prepared in Preparation Example 5, 5 mmol of the aromatic dioxyimine complex of zirconium, which is a transition metal compound of Formula 3, using ethylene pressure of 30 bar and ethylene pressure was added to the catalyst tank. After 250 mmol of ethyl zinc was injected into the reactor, the copolymerization reaction was carried out for 10 minutes, and the remaining ethylene gas was removed and the polymer solution was added to an excess of ethanol to induce precipitation.

The obtained polymer was washed with ethanol and acetone two to three times, and then dried in an 80 ° C. vacuum oven for at least 12 hours. The measured polymer weights and physical properties are shown in Table 1.

<Example 2>

Ethylene and 1-octene copolymer (mole ratio of polymerization aid: transition metal compound = 100: 1)

A copolymer was prepared in the same manner as in Example 1 except that 500 mmol of diethylzinc, a polymerization aid, was prepared, and the measured values are shown in Table 1 below.

<Example 3>

Ethylene and 1-octene copolymer (polymerization aid: molar ratio of transition metal compound = 500: 1)

A copolymer was prepared in the same manner as in Example 1 except for injecting 2500 mmol of diethyl zinc, which was a polymerization aid, and the measured values are shown in Table 1 below.

<Example 4>

Ethylene and 1-octene copolymer (mole ratio of polymerization aid: transition metal compound = 1000: 1)

A copolymer was prepared in the same manner as in Example 1, except that 5000 mmol of diethylzinc, a polymerization aid, was prepared, and the measured values are shown in Table 1 below.

<Example 5>

A copolymer was prepared in the same manner as in Example 1 except that 25 mmol of MAO (methyl aluminum oxide) corresponding to the compound of Formula 4 was injected as a cocatalyst, and the measured values are shown in Table 1 below.

Comparative Example 1 Ethylene and 1-Octene Copolymer

1.0 L of hexane solvent and 144 mL of 1-octene were added to a 2 L autoclave reactor, and the reactor temperature was preheated to 90 ° C. Titanium compound treated with 125 mmol of a triisobutylaluminum compound in a 25 mL catalyst storage tank (wherein the titanium compound means the catalyst prepared in Preparation Example 5) 5.0 mmol and trityl tetrakis (pentafluorophenyl 25 mmol of borate cocatalyst was added sequentially. At this time, ethylene pressure 30 bar was added to the catalyst tank and 5 mmol of the catalyst prepared in Preparation Example 5 and the transition metal compound of Formula 6 were injected into the reactor using argon of high pressure, and then the copolymerization reaction was performed for 10 minutes. The remaining ethylene gas was withdrawn and the polymer solution was added to excess ethanol to induce precipitation.

The obtained polymer was washed two to three times with ethanol and acetone, and then dried in an 80 ° C. vacuum oven for at least 12 hours to prepare a copolymer. The weight and physical property values of the copolymer are shown in Table 1 below.

Comparative Example 2 Ethylene and 1-Octene Copolymer

1.0 L of hexane solvent and 144 mL of 1-octene were added to a 2 L autoclave reactor, and the reactor temperature was preheated to 90 ° C. Titanium compound treated with 125 mmol of a triisobutylaluminum compound in a 25 mL catalyst storage tank (wherein the titanium compound means the catalyst prepared in Preparation Example 5) 5.0 mmol and trityl tetrakis (pentafluorophenyl 25 mmol of borate cocatalyst was added sequentially. In this case, 30 mmol of ethylene pressure was added to the catalyst tank, and 5 mmol of the catalyst prepared in Preparation Example 5 and 250 mmol of diethyl zinc polymerization aid were introduced into the reactor using high-pressure argon. Ethylene gas was withdrawn and the polymer solution was added to excess ethanol to induce precipitation.

The obtained polymer was washed two to three times with ethanol and acetone, and then dried in an 80 ° C. vacuum oven for at least 12 hours to prepare a copolymer. The weight and physical property values of the copolymer are shown in Table 1 below.

[Property evaluation]

Molecular weight : The number average molecular weight (Mn) and the weight average molecular weight (Mw) were measured using gel permeation chromatography (GPC), and the weight average molecular weight was divided by the number average molecular weight.

* Melt index of polymer (Melt Index, MI) : measured by ASTM D-1238 (Condition E, 190 ° C, 2.16 Kg load).

* Melting point (Tm) of polymer : It was obtained using DSC (Differential Scanning Calorimeter) 2920 manufactured by TA. That is, the temperature was increased to 200 ° C., maintained at that temperature for 5 minutes and then lowered to 30 ° C., and the temperature was increased again to make the top of the DSC curve a melting point. At this time, the rate of temperature rise and fall is 10 ° C./min, and a melting point is obtained while the second temperature rises.

* Density of polymer : A sample treated with an antioxidant (1,000 ppm) was made into a sheet having a thickness of 3 mm and a radius of 2 cm with a 180 ° C press mold, and cooled to 10 ° C / min to be a METTLER ( Mettler) was measured on a balance.

Activity : The activity was calculated by measuring the mass of the obtained polymer.

Item Activity (Kg / mmol-Ti hr) Mw density Melting Point (℃) Example 1 160.21 25000 0.887 130.2 Example 2 157.32 21000 0.883 127.4 Example 3 148.31 18000 0.875 125.2 Example 4 58.81 16200 0.873 122.3 Example 5 147.23 22500 0.882 127.8 Comparative Example 1 140.21 78000 0.920 90.5 / 124.1 Comparative Example 2 133.84 120000 0.882 78.2

As shown in Table 1, when the olefin polymer was prepared using the catalyst composition according to the present invention (Examples 1 to 5), the catalyst composition without the polymerization aid was used (Comparative Example 1) and the second Compared to the case of using a catalyst composition without a transition metal compound (Comparative Example 2), an olefin polymer having a high molecular weight of 30,000 or less, a density of 0.7 to 0.9 g / cc and a melting viscosity of 100 to 140 ° C. or higher was used. It can be seen that it can be produced.

Although the present invention has been described in detail with reference to the described embodiments, it will be apparent to those skilled in the art that various modifications and variations are possible within the scope and spirit of the present invention, and such modifications and modifications fall within the scope of the appended claims. It is also natural.

Claims (26)

A first transition metal compound represented by Formula 1; A second transition metal compound represented by Formula 3 below; A cocatalyst compound selected from the group consisting of compounds represented by the following formulas 4 to 6; And A polymerization aid which is a zinc or gallium compound containing a hydrocarbyl substituent having 1 to 12 carbon atoms; Containing Catalyst composition. [Formula 1]

In Chemical Formula 1, R1, R1 ', R2 and R2' are each independently hydrogen, alkyl of 1 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, alkenyl of 1 to 20 carbon atoms, alkylaryl of 7 to 20 carbon atoms, of 7 to 20 carbon atoms Arylalkyl, and metalloid radicals of Group 14 metals substituted with hydrocarbyl, or at least two of them are linked to each other by alkylidines comprising alkyl having 1 to 20 carbon atoms or aryl having 6 to 20 carbon atoms; Formed of aliphatic or aromatic rings, R3 is an aliphatic ring having 1 to 20 carbon atoms, R4, R4 ', R4' ', and R4' '' are each independently selected from hydrogen, a halogen radical, alkyl having 1 to 20 carbon atoms and aryl having 6 to 20 carbon atoms, or two R4 are linked to each other to be aliphatic Or an aromatic ring, E is a nitrogen or phosphorus atom, M is a Group 4 transition metal, Q ₁ and Q ₂ are each independently a halogen radical, alkyl having 1 to 20 carbon atoms, aryl amido having 6 to 20 carbon atoms, 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, and alkylidene having 1 to 20 carbon atoms. (3)

In Chemical Formula 3, M is a Group 4 to 10 metal in the Periodic Table of the Elements, T is a nitrogen, oxygen or phosphorus containing group, X is halogen, hydrocarbyl or hydrocarbyloxy, i is 1 or 2, N means nitrogen, T and N are linked by bridging ligands A, A is an alkyl, cycloalkyl, heteroalkyl, cycloheteroalkyl, aryl, and inert substituted derivative or divalent derivative thereof having 1 to 30 atoms excluding hydrogen. [Formula 4] - [Al (R5) -O] a - In Chemical Formula 4, R 5 is selected from halogen radicals, hydrocarbyl having 1 to 20 carbon atoms and hydrocarbyl having 1 to 20 carbon atoms substituted with halogen, a is an integer of 2 to 5. [Formula 5] J (R6) ₃ In Formula 5, J is aluminum or boron, R 6 is selected from halogen radicals, hydrocarbyl having 1 to 20 carbon atoms and hydrocarbyl having 1 to 20 carbon atoms substituted with halogen. [Chemical Formula ^{6] [LH] + [ZA} 4] - or _{^{[L] + [ZA 4]}} - In Formula 6, L is a neutral or cationic Lewis acid, H is a hydrogen atom, Z is a Group 13 element selected from B, Al, Ga, In and Tl, A is a halogen having a hydrogen valence of 1 or more; Hydrocarbyl having 1 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms or alkyl having 1 to 20 carbon atoms substituted with alkoxy having 1 to 20 carbon atoms or phenoxy having 6 to 20 carbon atoms. The method of claim 1, In Chemical Formula 1, E is a nitrogen atom, and R3 is a cyclohexyl group. Catalyst composition. The method of claim 1, The first transition metal compound represented by Formula 1 is characterized in that the compound represented by the formula (2) Catalyst composition. [Formula 2]

In Chemical Formula 2, R1, R1 ', R1' ', R1' '', R2, R2 ', R2' ', R2' '' are each independently hydrogen, alkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, and having 1 to C carbon atoms. Or a metalloid radical of a Group 14 metal substituted with alkenyl of 20, alkylaryl of 7 to 20 carbon atoms, arylalkyl of 7 to 20 carbon atoms, and hydrocarbyl, or at least two of them are alkyl of 1 to 20 carbon atoms Or are connected to each other by an alkylidine including aryl having 6 to 20 carbon atoms to form an aliphatic or aromatic ring, R3, R3 'is an aliphatic ring having 1 to 20 carbon atoms, R4, R4 ' Are each independently selected from hydrogen, a halogen radical, alkyl having 1 to 20 carbon atoms and aryl having 6 to 20 carbon atoms, or two R 4 are connected to each other to form an aliphatic or aromatic ring, E is a nitrogen or phosphorus atom, M is a Group 4 transition metal, Q ₁ and Q ₂ are each independently a halogen radical, alkyl having 1 to 20 carbon atoms, aryl amido having 6 to 20 carbon atoms, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, and aryl having 6 to 20 carbon atoms. , Alkylaryl having 7 to 20 carbon atoms, arylalkyl having 7 to 20 carbon atoms, alkylidene having 1 to 20 carbon atoms; G is a covalent bridging group connecting the two phenylene rings, an epoxy group; Epithio group; Carbonyl group; Silane group; Disilane group; Substituted or unsubstituted C1-C60 hydrocarbylene group; Or a substituted or unsubstituted heterohydrocarbylene group having 1 to 60 carbon atoms including a Group 4B, Group 5B or Group 6B element. The method of claim 3, wherein In the compound represented by Formula 2, E is nitrogen, and R3 is cyclohexyl. Catalyst composition. The method of claim 1, The molar ratio of the first transition metal compound to the polymerization aid is 1:50 to 1: 900 Catalyst composition. The method of claim 1, The promoter compound is composed of a compound of Formula 4 or Formula 5, A molar ratio of the first transition metal compound to the compound represented by Formula 4 or Formula 5 is 1: 20 to 1: 2000 Catalyst composition. The method of claim 1, The promoter compound is composed of a mixture of Formula 4 or Formula 5, and Formula 6, The molar ratio of the first transition metal compound to the polymerization aid is from 1:50 to 1: 900, The molar ratio of the first transition metal compound to the compound represented by Formula 6 is 1: 2 to 1: 5 Catalyst composition. The method of claim 1, The polymerization aid is at least one selected from the group consisting of diethyl zinc, dimethyl zinc, dimethyl gallium and diethyl gallium Catalyst composition. The method of claim 1, The compound of Formula 4 is at least one member selected from the group consisting of methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane and butyl aluminoxane Catalyst composition. The method of claim 1, The compound of formula 5 is trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri-s-butylaluminum, tricyclopentylaluminum, tripentylaluminum , 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, triethyl Boron, triisobutyl boron, tripropyl boron and tributyl boron, characterized in that at least one member selected from the group consisting of Catalyst composition. The method of claim 1, The compound of formula 6 is triethyl ammonium tetra (phenyl) boron, tributyl ammonium tetra (phenyl) boron, trimethyl ammonium tetra (phenyl) boron, tripropyl ammonium tetra (phenyl) boron, trimethyl ammonium tetra ( p-tolyl) boron, trimethylammonium tetra (o, p-dimethylphenyl) boron, tributylammonium tetra (p-trifluoromethylphenyl) boron, trimethylammonium tetra (p-trifluoromethylphenyl) boron, tri Butyl ammonium tetra (pentafluorophenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (pentafluorophenyl) boron, diethyl ammonium tetra (Pentafluorophenyl) boron, trimethyl phosphonium tetra (phenyl) boron, triethyl ammonium tetra (phenyl) aluminum, tributyl ammonium tetra (phenyl) aluminum, trimethyl ammonium tetra (phenyl) aluminum, tripropyl ammonium Tetra (phenyl) al Aluminum, trimethylammonium tetra (p-tolyl) aluminum, tripropylammonium tetra (p-tolyl) aluminum, triethylammonium tetra (o, p-dimethylphenyl) aluminum, tributylammonium tetra (p-triflo) Romethylphenyl) aluminum, trimethylammonium tetra (p-trifluoromethylphenyl) aluminum, tributylammonium tetra (pentafluorophenyl) aluminum, N, N-diethylanilinium tetra (phenyl) aluminum, N, N -Diethylanilinium tetra (phenyl) aluminum, N, N-diethylanilinium tetra (pentafluorophenyl) aluminum, diethylammonium tetra (pentafluorophenyl) aluminum, triphenylphosphonium tetra (phenyl) Aluminum, trimethyl phosphonium tetra (phenyl) aluminum, triethyl ammonium tetra (phenyl) aluminum, tributyl ammonium tetra (phenyl) aluminum, trimethyl ammonium tetra (phenyl) boron, tripropyl ammonium tetra (phenyl) boron , Trimethylammonium tetra (p-tolyl) boron, tripropyl ammonium tetra (p-tolyl) boron, triethyl ammonium tetra (o, p-dimethylphenyl) boron, trimethylammonium tetra (o, p-dimethylphenyl ) Boron, tributyl ammonium tetra (p-trifluoromethylphenyl) boron, trimethyl ammonium tetra (p-trifluoromethylphenyl) boron, tributyl ammonium tetra (pentafluorophenyl) boron, N, N-di Ethylanilinium tetra (phenyl) boron, triphenylphosphonium tetra (phenyl) boron, triphenylcarbonium tetra (p-trifluoromethylmethyl) boron, triphenylcarbonium tetra (pentafluorophenyl) boron , Trityl tetra (pentafluorophenyl) boron and trityl tetrakis (pentafluorophenyl) borate, characterized in that at least one member selected from the group consisting of Catalyst composition. The method according to any one of claims 1 to 11, The catalyst composition is characterized in that it is used to prepare the olefin polymer Catalyst composition. a) contacting at least one of the first transition metal compound represented by the following Chemical Formula 1 with the second transition metal compound represented by the following Chemical Formula 3, and the compounds represented by the following Chemical Formula 4 and Chemical Formula 5 to obtain a mixture; b) adding a polymerization aid which is a zinc or gallium compound containing a hydrocarbyl substituent having 1 to 12 carbon atoms to the mixture; Characterized in that it comprises Process for preparing a catalyst composition. [Formula 1]

In Chemical Formula 1, R1, R1 ', R2 and R2' are each independently hydrogen, alkyl of 1 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, alkenyl of 1 to 20 carbon atoms, alkylaryl of 7 to 20 carbon atoms, of 7 to 20 carbon atoms Arylalkyl, and metalloid radicals of a Group 14 metal substituted with hydrocarbyl, or two or more of them are linked to each other by an alkylidine including alkyl having 1 to 20 carbon atoms or aryl having 6 to 20 carbon atoms Or an aromatic ring, R3 is an aliphatic ring having 1 to 20 carbon atoms, R4, R4 ', R4' ', and R4' '' are each independently selected from hydrogen, a halogen radical, alkyl having 1 to 20 carbon atoms and aryl having 6 to 20 carbon atoms, or two R4 are linked to each other to be aliphatic Or an aromatic ring, E is a nitrogen or phosphorus atom, M is a Group 4 transition metal, Q ₁ and Q ₂ are each independently a halogen radical, alkyl having 1 to 20 carbon atoms, aryl amido having 6 to 20 carbon atoms, 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, and alkylidene having 1 to 20 carbon atoms. (3)

In Chemical Formula 3, M is a Group 4 to 10 metal in the Periodic Table of the Elements, T is a nitrogen, oxygen or phosphorus containing group, X is halogen, hydrocarbyl or hydrocarbyloxy, i is 1 or 2, N means nitrogen, T and N are linked by bridging ligands A, A is alkyl, cycloalkyl, heteroalkyl, cycloheteroalkyl, aryl, and inertly substituted derivatives thereof or divalent derivatives thereof having 1 to 30 atoms excluding hydrogen. [Formula 4] - [Al (R5) -O] a - In Chemical Formula 4, R 5 is selected from halogen radicals, hydrocarbyl having 1 to 20 carbon atoms and hydrocarbyl having 1 to 20 carbon atoms substituted with halogen, a is an integer of 2 to 5. [Formula 5] J (R6) ₃ In Formula 5, J is aluminum or boron, R 6 is selected from halogen radicals, hydrocarbyl having 1 to 20 carbon atoms and hydrocarbyl having 1 to 20 carbon atoms substituted with halogen. The method of claim 13, Between step a) and b) c) adding a compound represented by the following Chemical Formula 6 to the mixture a); Characterized in that it further comprises Process for preparing a catalyst composition. [Chemical Formula ^{6] [LH] + [ZA} 4] - or _{^{[L] + [ZA 4]}} - In Formula 6, L is a neutral or cationic Lewis acid, H is a hydrogen atom, Z is a Group 13 element selected from B, Al, Ga, In and Tl, A is a halogen having a hydrogen valence of 1 or more; Hydrocarbyl having 1 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms or alkyl having 1 to 20 carbon atoms substituted with alkoxy having 1 to 20 carbon atoms or phenoxy having 6 to 20 carbon atoms. The method according to claim 13 or 14, The first transition metal compound represented by Formula 1 is characterized in that the compound represented by the formula (2) Process for preparing a catalyst composition. [Formula 2]

In Chemical Formula 2, R1, R1 ', R1' ', R1' '', R2, R2 ', R2' ', R2' '' are each independently hydrogen, alkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, and having 1 to C carbon atoms. Or a metalloid radical of a Group 14 metal substituted with alkenyl of 20, alkylaryl of 7 to 20 carbon atoms, arylalkyl of 7 to 20 carbon atoms, and hydrocarbyl, or at least two of them are alkyl of 1 to 20 carbon atoms Or are connected to each other by an alkylidine including aryl having 6 to 20 carbon atoms to form an aliphatic or aromatic ring, R3, R3 'is an aliphatic ring having 1 to 20 carbon atoms, R4, R4 ' Are each independently selected from hydrogen, a halogen radical, alkyl having 1 to 20 carbon atoms and aryl having 6 to 20 carbon atoms, or two R 4 are connected to each other to form an aliphatic or aromatic ring, E is a nitrogen or phosphorus atom, M is a Group 4 transition metal, Q ₁ and Q ₂ are each independently a halogen radical, alkyl having 1 to 20 carbon atoms, aryl amido having 6 to 20 carbon atoms, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, and aryl having 6 to 20 carbon atoms. , Alkylaryl having 7 to 20 carbon atoms, arylalkyl having 7 to 20 carbon atoms, alkylidene having 1 to 20 carbon atoms; G is a covalent bridging group connecting the two phenylene rings, an epoxy group; Epithio group; Carbonyl group; Silane group; Disilane group; Substituted or unsubstituted C1-C60 hydrocarbylene group; Or a substituted or unsubstituted heterohydrocarbylene group having 1 to 60 carbon atoms including a Group 4B, Group 5B or Group 6B element. The method according to claim 13 or 14, The transition metal compound of Formula 1, Formula 3, and the compound of Formula 4, Formula 5 is used in the form supported on silica or alumina Process for preparing a catalyst composition. The method of claim 14, The compound of formula 6 is characterized in that it is used in the form supported on silica or alumina Process for preparing a catalyst composition. The method of claim 15, The compound of Formula 2 is characterized in that it is used in the form supported on silica or alumina Process for preparing a catalyst composition. It is prepared by polymerizing an olefin monomer using the catalyst composition for olefin polymerization of claim 1, having a density of 0.7 to 0.9 g / cc, a melting point of 100 to 140 ° C, and a molecular weight (Mw) of 5,000 to 30,000. Olefin polymers. The method of claim 19, The olefin monomers are 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-eicosene, norbornene, norbonadiene, ethylidenenorbornene, phenylnorbornene, vinylnorbornene, dicyclopentadiene, 1,4-butadiene , 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene and 3-chloromethyl styrene, characterized in that at least one member selected from the group consisting of Olefin polymers. The method of claim 19, The olefin polymer is characterized in that the homopolymer or copolymer of the olefin monomer Olefin polymers. The method of claim 21, When the olefin polymer is a copolymer of ethylene and other comonomers, the comonomer is one or more selected from the group consisting of propylene, 1-butene, 1-hexene, and 4-methyl-1-pentene, and 1-octene Characterized Olefin polymers. Polymerizing the olefinic monomer in the presence of the catalyst composition for olefin polymerization of claim 1 to form an olefin polymer Process for preparing olefin polymer. The method of claim 23, The olefinic monomers are 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-eicosene, norbornene, norbonadiene, ethylidenenorbornene, phenylnorbornene, vinylnorbornene, dicyclopentadiene, 1,4- Butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene and 3-chloromethyl styrene characterized in that at least one member selected from the group consisting of Process for preparing olefin polymer. The method of claim 23, The olefin polymer is characterized in that the homopolymer or copolymer of the olefin monomer Process for preparing olefin polymer. The method of claim 25, When the olefin polymer is a copolymer of ethylene and other comonomers, the co-monomer is one or more selected from the group consisting of propylene, 1-butene, 1-hexene, and 4-methyl-1-pentene, and 1-octene Characterized Process for preparing olefin polymer.