KR20180067944A - Olefin copolymer - Google Patents

Abstract

The present invention relates to an olefin copolymer having a molecular weight of 100,000 to 300,000 g/mol, a molecular weight distribution (Mw/Mn) of 5 to 30, a density of 0.930 to 0.960 g/cm^3, MFRR_5/2.16 (a value obtained by dividing a melt flow index measured at 190°C under a load of 5 kg by a melt flow index measured at 190°C under a load of 2.16 kg according to ASTM D1238) of 1 to 10, and an integral value of 20% or more of an x-axis total integral value in the region where log Mw is 5.0 or more and less than 5.5 in a GPC curve graph, in which the x-axis is Log Mw and the y-axis is dw/dlogMw. The olefin copolymer can be preferably used as a food container, a bottle cap or the like which request stability and chemical resistance in a high-pressure and high-temperature environment.

Description

OLEFIN COPOLYMER < RTI ID = 0.0 >

The present invention relates to olefin copolymers.

Olefin polymerization catalyst systems can be classified into Ziegler-Natta and metallocene catalyst systems, both of which have been developed for their respective characteristics. Ziegler-Natta catalysts have been widely applied to commercial processes since the invention of the 50's. However, since the Ziegler-Natta catalyst is a multi-site catalyst having a plurality of active sites, the molecular weight distribution of the polymer is broad, The composition distribution is not uniform and there is a limit in securing desired physical properties.

On the other hand, the metallocene catalyst is composed of a combination of a main catalyst mainly composed of a transition metal compound and a cocatalyst, which is an organometallic compound mainly composed of aluminum. Such a catalyst is a single site catalyst as a homogeneous complex catalyst, . The polymer has a narrow molecular weight distribution according to the single active site property and a homogeneous composition distribution of the comonomer is obtained. According to the modification of the ligand structure and the polymerization conditions of the catalyst, the stereoregularity of the polymer, Crystallinity and so on.

U.S. Patent No. 5,914,289 discloses a method of controlling the molecular weight and molecular weight distribution of a polymer by using a metallocene catalyst supported on each support. However, the amount of the solvent used for preparing the supported catalyst and the preparation time are long , And the metallocene catalyst used had to be carried on the carrier, respectively.

Korean Patent Application No. 2003-12308 discloses a method for controlling the molecular weight distribution by carrying a double-nucleated metallocene catalyst and a single nuclear metallocene catalyst together with an activating agent in a carrier to change and polymerize the combination of catalysts in the reactor have. However, this method has a limitation in simultaneously realizing the characteristics of the individual catalysts, and also disadvantageously causes fouling in the reactor due to liberation of the metallocene catalyst portion in the carrier component of the finished catalyst.

Accordingly, there is a continuing need for a process for preparing an olefin polymer of desired properties by preparing a hybrid supported metallocene catalyst having excellent activity in order to solve the above-mentioned disadvantages.

On the other hand, the linear low density polyethylene is a resin which is produced by copolymerizing ethylene and an alpha olefin at a low pressure using a polymerization catalyst, has a short molecular weight distribution and a short chain length and has no long chain branch. Linear low density polyethylene film has high tensile strength and elongation as well as general polyethylene characteristics, and has excellent tear strength and falling impact strength. Therefore, it is used for stretch film and overlap film which are difficult to apply low density polyethylene or high density polyethylene .

However, linear low density polyethylene using 1-butene or 1-hexene as a comonomer is mostly prepared in a single gas phase reactor or a single loop slurry reactor, and productivity is high compared to the process using 1-octene comonomer. Due to limitations of catalyst technology and process technology, there is a problem that the physical properties are considerably weaker than when using 1-octene comonomer, and the molecular weight distribution is narrow, resulting in poor processability. Much effort has been made to improve these problems,

U.S. Patent No. 4,935,474 discloses a process for preparing polyethylene having a broad molecular weight distribution using two or more metallocene compounds. U.S. Patent No. 6,828,394 discloses a process for producing polyethylene which is excellent in processability using a mixture of a monomer having good comonomer binding property and a monomer having no comonomer binding property and is particularly suitable for a film. In addition, U.S. Patent No. 6,841,631 and U.S. Patent No. 6,894,128 disclose that a polyethylene having at least two kinds of metal compounds is used as a metallocene-based catalyst and has a molecular weight distribution of at least two, and is used for films, blow molding, It is reported that it is applicable. However, these products have improved processability, but the dispersed state of the unit particles in molecular weight is not uniform, so that the extrusion appearance is rough and the physical properties are not stable even under relatively good extrusion conditions.

Against this backdrop, there is a continuing need to produce better products with a balance between physical and processability, and further improvements are needed.

U.S. Patent No. 4,935,474 U.S. Patent No. 6,841,631 U.S. Patent No. 6,894,128

The present invention has excellent processability due to a wide range of melt flow index and melt flow rate ratio, and has high molecular weight, broad molecular weight distribution and high long chain side branch content, and therefore has excellent environmental stress cracking and processability and dimensional stability, A bottle cap and the like which are required to have stability and chemical resistance in a high temperature environment.

(Mw / Mn) of 5 to 30, a density of 0.930 to 0.960 g / cm3, an MFRR of _{5 / 2.16} (190 deg. C, according to ASTM D1238), a molecular weight of 100,000 to 300,000 g / And a melt flow index measured at a load of 5 kg divided by a melt flow index measured at 190 占 폚 under a load of 2.16 kg) is 1 to 10, and a log axis of the log axis is dw / dlogMw. Is in the range of 5.0 to less than 5.5, the integral value is not less than 20% of the total integral value of the x-axis.

Hereinafter, the olefin copolymer according to a specific embodiment of the present invention will be described in more detail.

According to one embodiment of the invention, and the above molecular weight from 100,000 to 300,000 g / mol, molecular weight distribution (Mw / Mn) of 5 to 30 and a density of 0.930 to _{0.960 g / ㎤, MFRR 5 /} 2.16 (ASTM D1238 , A melt flow index measured at 190 占 폚 under a load of 5 kg divided by a melt flow index measured at 190 占 폚 under a load of 2.16 kg) was 1 to 10, and the x-axis was log Mw and the y-axis was dw / dlogMw In the GPC curve graph, the integral value in the region where the log Mw is 5.0 or more and less than 5.5 is 20% or more of the integral value of the x-axis.

The inventors of the present invention newly synthesized olefin copolymers excellent in environmental stress cracking resistance and processability with a wide range of melt flow index and melt flow rate ratio, excellent processability, high molecular weight, broad molecular weight distribution and high long chain side chain content, In particular, the olefin copolymer of this embodiment has a characteristic that the integral value in the region where the log Mw is 5.0 or more and less than 5.5 in the GPC curve graph with the x-axis of log Mw and the y-axis of dw / dlogMw is 20% . Accordingly, the olefin copolymer can have properties of excellent environmental stress cracking resistance and stiffness, have excellent rigidity in a polymer injection product, have high dimensional stability such that the shape does not substantially change even after temperature and pressure change after injection .

 More specifically, in a GPC curve graph in which the x axis of the olefin copolymer is log Mw and the y axis is dw / dlogMw, the integral value in a region where log Mw is 5.0 or more and less than 5.5 is 20% To 30%.

If the ratio of the integral value of the x-axis to the total integrated value in the region where the log Mw is 5.0 or more and less than 5.5 in the GPC curve graph having the log axis of dw / dlogMw for the olefin copolymer is less than 20% , The rigidity of the olefin copolymer may be deteriorated or may be easily cracked. Accordingly, when the olefin copolymer is applied to a product such as a food container or a bottle cap, it may easily break or the product may be blown, It may be difficult to secure chemical resistance.

On the other hand, in a GPC curve graph in which the x axis of the olefin copolymer is log Mw and the y axis is dw / dlogMw, the integral value in the region where the log Mw is 4.5 or more and less than 5.0 may be 25% or more of the integral value of the x- have. In the GPC curve graph, a region having a log Mw of not less than 4.5 and less than 5.0 may relate to the stiffness and dimensional stability of the olefin copolymer, and the integral value in this region may be 25% or more of the integral value of the x- 40%, the olefin copolymer may satisfy the above-mentioned characteristics.

In the GPC curve graph in which the x axis of the olefin copolymer is log Mw and the y axis is dw / dlogMw, the ratio of the integral value and the log Mw in the region where the log Mw is 4.5 or more and 5.0 or less relative to the total integrated value of the x- The difference in the ratio of the integral value in the range of 5.0 to less than 5.5 may be 7% or less, or 1% to 7%.

As described above, in the GPC curve graph, the difference of the ratio of the integral value in the region where the log Mw is 4.5 or more and 5.0 or less and the ratio of the integral value in the region where the log Mw is 5.0 or more and less than 5.5 is 7% or less , Or 1% to 7%, the olefin copolymer can have a property that it has high rigidity required for a polymer injection product and does not break easily, and accordingly, a high rigidity container Or a high rigidity bottle cap or the like.

In the GPC curve graph in which the x-axis and the y-axis of the olefin copolymer are log Mw and dw / dlogMw, the ratio of the integral value and the log Mw in the region where the log Mw is 4.5 or more and less than 5.0, When the difference in the ratio of the integral value in the region below 5.5 is more than 7%, the olefin copolymer shows an excessively high double molecular weight distribution pattern or a multimolecular distribution pattern (Bimodality, multimodality) And it is difficult to apply to products such as a food container and a bottle cap because of the problems such as breakage easily due to a change in temperature or pressure, and the like.

In the above, Mw denotes a weight-average molecular weight, and w denotes a weight fraction. In addition, a GPC curve graph in which the x-axis is log Mw and the y-axis is dw / dlogMw can be defined based on the molecular weight measured through GPC or the like.

Meanwhile, more specific characteristics of the olefin copolymer of one embodiment are as follows.

The weight average molecular weight (Mw) of the olefin copolymer may be 100,000 to 300,000 g / mol. More preferably, the weight average molecular weight may be at least 120,000 g / mol, at least 130,000 g / mol, or at least 140,000 g / mol, at most 250,000 g / mol, or at most 220,000 g / mol, or at most 200,000 g / mol .

In the olefin copolymer, the olefin polymer according to the present invention may have a molecular weight distribution (Mw / Mn) of 5 to 30, or 7 to 20. The olefin-based polymer having such a broad molecular weight distribution can exhibit better processability.

The olefin copolymer may have a density of 0.930 to 0.960 g / cm < ³ > but is not limited thereto.

Further, the olefin copolymer may be a _.16 MFR ₂ of 0.01 to 1.0 g / 10min (the melt flow index measured at 190 ℃, 2.16 kg load in accordance with ASTM D1238). The MFR _{2 .16} and more preferably is, 0.05 g / 10min or higher, or 0.1 g / 10min or higher, 0.15 g / 10min and not more than, 0.9 g / 10min or less, or 0.8 g / 10min or less, or 0.6 g / 10min may be below have.

The olefin copolymer preferably has an MFRR of _{5 / 2.16} (a melt flow index measured at 190 占 폚 under a load of 5 kg divided by a melt flow index measured at 190 占 폚 under a load of 2.16 kg in accordance with ASTM D1238) of 1 to 10 Value. More preferably, the MFRR _{5 /2.16} may be 3 or more, or 3.2 or more, or 3.3 or more, 9 or less, or 9.5 or less, or 8 or less.

The spiral flow length (190 DEG C, 90 bar) shows the workability of the ethylene / alpha-olefin copolymer. The larger the value, the better the processability. For example, for the olefin copolymer, an ENGEL 150 ton injector is used and the spiral flow length (SF) measured with a mold thickness of 1.5 mm, an injection temperature of 190 DEG C, a mold temperature of 50 DEG C and an injection pressure of 90 bar : Spiral flow length) may be more than 13 cm or more than 15 cm.

In addition to the above mechanical properties and processability, the olefin copolymer is also characterized by excellent environmental stress crack resistance (ESCR).

In general, the processability and the environmental stress cracking property are conflicting physical properties. When the melt index is increased in order to improve processability, the environmental stress cracking property is lowered. However, the olefin copolymer satisfies both good processability and environmental stress cracking resistance.

The olefin copolymer may have an environmental stress cracking resistance (ESCR) of 200 hours or more, or 240 hours or more, or 300 hours or more as measured according to ASTM D 1693. When the environmental stress cracking resistance (ESCR) is 200 hours or more, the performance can be stably maintained in the state of use for the bottle cap. Therefore, the upper limit value is not substantially significant, but may be 1,000 hours or less, or 800 hours or less, . Since it exhibits a high performance environmental stress cracking property as described above, it can be molded into a food container product such as a bottle cap and can maintain its continuous performance even when it is used under high temperature and high pressure conditions.

The olefin copolymer may include a first metallocene catalyst comprising a transition metal compound represented by Formula 1 below; A second metallocene catalyst comprising a transition metal compound of Formula 2; And a third metallocene catalyst comprising a transition metal compound of formula (3), in the presence of a catalyst composition for the synthesis of an olefin copolymer.

Specifically, the olefin copolymer provided using the catalyst composition for synthesizing an olefin copolymer has excellent processability due to a wide melt flow index and a melt flow rate ratio, and has a high molecular weight, a broad molecular weight distribution and a high long chain side branch content, A spiral flow length of more than 13 cm or 15 cm or more at a high temperature of about 190 ° C and a pressure of about 90 bar and a spiral flow length of about 15 cm or more under a high temperature and a high pressure, 2% or less, indicating high form stability.

The olefin monomer may be ethylene, alpha-olefin, cyclic olefin, diene olefin having 2 or more double bonds or triene olefin, and more specific examples thereof include ethylene, propylene, 1-butene, 1-hexene, 1-heptene, 1-octene, 1-decene, Norbornene, ethylidene norbornene, phenyl norbornene, vinyl norbornene, dicyclopentadiene, 1,4-butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, Divinylbenzene, 3-chloromethylstyrene, and the like, and two or more of these monomers may be mixed and copolymerized.

The olefin-based polymer is more preferably an ethylene / alpha olefin copolymer, but is not limited thereto.

In the case where the olefin-based polymer is an ethylene / alpha olefin copolymer, the content of the alpha-olefin as the comonomer is not particularly limited and may be appropriately selected depending on the use, purpose and the like of the olefin-based polymer. More specifically, it may be more than 0 and 99 mol% or less.

The copolymerization or polymerization reaction can be homopolymerized with one olefin monomer or copolymerized with two or more monomers using one continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reactor or a solution reactor.

The copolymerization temperature may be about 25 to about 500 캜, preferably about 25 to about 200 캜, more preferably about 50 to about 150 캜. The polymerization pressure may be from about 1 to about 100 Kgf / cm ^2, preferably about 1 to about 50 Kgf / cm ^2, more preferably from about 5 to about 30 Kgf / cm ^2.

The catalyst composition for synthesizing an olefin copolymer may be prepared by reacting an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms such as pentane, hexane, heptane, nonane, decane and isomers thereof and an aromatic hydrocarbon solvent such as toluene, benzene, dichloromethane, Or a hydrocarbon solvent substituted with a chlorine atom, for example. The solvent used here is preferably used by removing a small amount of water or air acting as a catalyst poison by treating with a small amount of alkylaluminum, and it is also possible to use a further cocatalyst.

A first metallocene catalyst comprising a transition metal compound represented by the general formula (1) contained in the catalyst composition for synthesizing an olefin copolymer; A second metallocene catalyst comprising a transition metal compound of formula (2); And the transition metal compound of the formula (3) are as follows.

[Chemical Formula 1]

In Formula 1,

Wherein R ₁ to R ₄ are the same or different and each independently represents hydrogen, halogen, a straight or branched alkyl group having 1 to 20 carbon atoms, a straight or branched alkenyl group having 2 to 20 carbon atoms, a C1 to C20 alkylsilyl group , C1 to C20 silylalkyl groups, C1 to C20 alkoxysilyl groups, C1 to C20 linear or branched alkoxy groups, C6 to C20 aryl groups, C7 to C20 alkylaryl groups, or C7 to C20 arylalkyl groups Lt;

Wherein Q ₁ is an alkylene group having 4 to 20 carbon atoms, an alkenylene group having 4 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, a cycloalkylene group having 4 to 20 carbon atoms, , An aryl alkylene group having 7 to 22 carbon atoms, a cycloalkylalkylene group having 5 to 22 carbon atoms,

Wherein R ₅ to R ₁₁ are the same or different and each independently represents hydrogen, halogen, a straight or branched alkyl group having 1 to 20 carbon atoms, a straight or branched alkenyl group having 2 to 20 carbon atoms, a C1 to C20 alkylsilyl group , C1 to C20 silylalkyl groups, C1 to C20 alkoxysilyl groups, C1 to C20 linear or branched alkoxy groups, C6 to C20 aryl groups, C7 to C20 alkylaryl groups, or C7 to C20 arylalkyl groups Lt;

Two or more adjacent groups in one of the benzene rings of R ₅ to R ₁₁ may be connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring;

M ₁ is a Group 4 transition metal,

Y ₁ and Y ₂ are the same or different from each other and each independently represents a halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a nitro group, an amido group, a C1 to C20 alkylsilyl group , A C1 to C20 alkoxy group, or a C1 to C20 sulfonate group.

 (2)

In Formula 2,

M ₂ is a Group 4 transition metal,

X ₂₁ and X ₂₂ are the same or different from each other and each independently represents a halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a nitro group, an amido group, a C1 to C20 alkylsilyl group , A C1 to C20 alkoxy group, or a C1 to C20 sulfonate group,

Q _{2 is} carbon, silicon or germanium;

R ₂₁ and R ₂₂ are the same or different from each other and each independently represents hydrogen, halogen, C 1 to C 20 alkyl, C 2 to C 20 alkenyl, C 6 to C 20 aryl, C 7 to C 20 alkylaryl, C 7 to C 20 A C1 to C20 alkoxy group, a C2 to C20 alkoxyalkyl group, a C3 to C20 heterocycloalkyl group, or a C5 to C20 heteroaryl group;

One of C ₂₁ and C ₂₂ is represented by the following formula (2a), and the other is represented by the following formula (2b);

(2a)

(2b)

In the above formula (2a)

Z ₁ to Z ₉ are the same or different from each other and each independently represents hydrogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C1 to C20 alkoxy group, a C1 to C20 alkylsilyl group, a C1 to C20 silyl An alkyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group;

In the above formula (2b)

Z ₁₀ and Z ₁₂ to Z ₁₅ are hydrogen, halogen or an alkyl group having 1 to 3 carbon atoms,

Z ₁₁ represents a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C1 to C20 alkylsilyl group, a C1 to C20 silylalkyl group, a C1 to C20 alkoxysilyl group, a C1 to C20 ether group, A silyloxy group of C1 to C20, a C1 to C20 alkoxy group, a C2 to C20 alkoxyalkyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group,

(3)

In Formula 3,

M ₃ is a Group 4 transition metal,

X ₃₁ and X ₃₂ are the same or different and each independently represents a halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a nitro group, an amido group, a C1 to C20 alkylsilyl group , A C1 to C20 alkoxy group, or a C1 to C20 sulfonate group,

Q _{3 is} carbon, silicon or germanium;

R ₃₁ and R ₃₂ are the same or different and are each independently selected from the group consisting of hydrogen, halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, A C1 to C20 alkoxy group, a C2 to C20 alkoxyalkyl group, a C3 to C20 heterocycloalkyl group, or a C5 to C20 heteroaryl group;

C ₃₁ and One of C ₃₂ is represented by the following formula (3a) or (3b), and C ₃₁ and And the other of C ₃₂ is represented by the following formula (3c), (3d) or (3e).

[Chemical Formula 3]

(3b)

[Chemical Formula 3c]

(3d)

[Formula 3e]

In the above formulas (2a), (2b), (3a), (3b) and (3c), J ₁ to J ₃₁ and J ₁ 'to J ₁₃ ' are the same or different and each independently represents hydrogen, halogen, a C1 to C20 alkyl group, A C1 to C20 alkylsilyl group, a C1 to C20 silylalkyl group, a C1 to C20 alkoxysilyl group, a C1 to C20 alkoxy group, a C6 to C20 aryl group, a C7 to C20 alkenyl group, An alkylaryl group of C7 to C20, or an arylalkyl group of C7 to C20,

At least one of J ₉ to J ₁₃ and J ₉ 'to J ₁₃ ' is a C1 to C20 haloalkyl group,

Two or more adjacent groups in the aromatic ring of one of J ₁ to J ₃₁ and J ₁ 'to J ₁₃ ' may be connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring.

The transition metal compound of Formula 1 has a structure in which a transition metal is coordinated between two indene derivatives and Q ₁ of a specific structure has a structure in which the two indene derivatives are connected to each other. As the indene derivative has a structure in which Q ₁ of the specific structure has the above-described structure, monomers such as ethylene can easily access the center metal of the transition metal compound, thereby achieving a higher copolymerization activity, It is possible to produce an olefin polymer having a low molecular weight without lowering the reaction activity even when adjusting the MI and MFRR by introducing hydrogen.

The transition metal compound of the above formula (2) forms an indenoindole derivative and an indene derivative asymmetrically cross-linked by a bridge, and has a non-covalent electron pair capable of acting as a Lewis base in the ligand structure Exhibit high polymerization activity. In addition, an electronically rich indeno-naphthol derivative can stabilize beta-hydrogen of a chain of nitrogen molecules growing by hydrogen bonding to inhibit beta-hydrogen elimination to polymerize high molecular weight olefinic polymers. In addition, since it contains an indene derivative having relatively low steric hindrance, it exhibits high copolymerization activity and low hydrogen reactivity, so that an olefin polymer having a high molecular weight can be polymerized with high activity.

In particular, the transition metal compound of the above formula (2) has a structure in which a substituent (Z ₁₁ ) is present at a specific position of the indene derivative compound of the formula (2b), and an unsubstituted indene compound or a metallocene Compared to a compound, it can have excellent activity.

The transition metal compound of the above formula (3) forms an indenoindole derivative and a cyclopentadiene derivative asymmetrically cross-linked by a bridge, and a non-covalent electron pair capable of acting as a Lewis base in the ligand structure By weight, and is supported on the surface having the Lewis acid property of the carrier, and exhibits high polymerization activity even when carried. Also, the activity is high by including electronically enriched indenoindoles and cyclopentadienes, and excellent copolymerization and high activity are maintained due to the appropriate steric hindrance and the electronic effect of the ligand. In addition, it is possible to stabilize the beta-hydrogen of the polymer chain in which the nitrogen atom of the indane-indole derivative grows by hydrogen bonding to suppress the beta-hydrogen elimination and polymerize the ultra-high molecular weight polyolefin.

In particular, at least one of J ₉ to J ₁₃ and J ₉ 'to J ₁₃ ' in the transition metal compound of Formula 3 includes a C1 to C20 haloalkyl group. For example, fluoroalkyl groups, that is, CF 3, can stabilize beta-hydrogen of the growing chain by acting as nitrogen atoms of indenoindole derivatives by hydrogen bonding to further suppress beta-hydrogen elimination, The polyolefin polymerization of a molecular weight can be achieved more effectively. In other words, the basic skeleton of the indenoindole derivative and the cyclopentadiene derivative crosslinked asymmetrically by the bridge is maintained, and a substituent such as CF3, which is a stronger hydrogen bond acceptor, And stabilizes beta-hydrogen by bonding to enhance the action of inhibiting beta-hydrogen elimination, thereby enabling polymerization of ultrahigh molecular weight polyolefin.

In the present specification, an aryl alkylene group means a functional group having at least one aryl group and at least one alkylene group bonded, and the remaining one of the alkylene groups is bonded to indene. The cycloalkylalkylene group is a functional group having at least one cycloalkyl group and at least one alkylene group bonded to each other, and the remaining one of the alkylene groups is bonded to indene.

Specific examples of the transition metal compound represented by the above formula (1) are not limited to the above-described ranges of the above-mentioned chemical formula, but more preferred examples are as follows:

Wherein R ₁ to R ₂ are C1 to C20 alkylsilyl groups and C1 to C20 silylalkyl groups and R ₃ to R ₄ are arylene groups having 6 to 20 carbon atoms or arylene groups having 8 to 8 carbon atoms, and to 22 aryl di-alkylene group, wherein R ₅ to R ₁₁ is an alkyl group of straight or branched chain of hydrogen, halogen, C1 to C20, respectively, M ₁ is titanium, zirconium or hafnium, Y ₁ and Y ₂ represents halogen Lt; / RTI >

Specific examples of the transition metal compound of the above-mentioned formula (2) are not limited to the above-mentioned ranges of the above-mentioned formula, but more preferred examples are as follows:

Z ₁ to Z ₉ in formula (2a) each independently represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a tert- butyl group, a pentyl group, a hexyl group, a heptyl group, , A propylene group, a butenyl group, a phenyl group, a benzyl group, a naphthyl group, a methoxy group, an ethoxy group or a tert-butoxyhexyl group,

Z ₁₁ in the above formula (2b) is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, A benzyl group, a naphthyl group, a trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, a tributylsilyl group, a triisopropylsilyl group, a trimethylsilylmethyl group, a tert-butyldimethylsilylether group, Or a tert-butoxyhexyl group,

R ₂₁ and R ₂₂ in Formula 2 may be a methyl group or a tert-butoxyhexyl group.

Specific examples of the compound represented by the formula (2a) include, but are not limited to, compounds represented by one of the following structural formulas. The remaining reaction site of the cyclopentadienyl group in the following structural formula means a bonding site.

Specific examples of the compound represented by Formula 2b include compounds represented by one of the following structural formulas, but the present invention is not limited thereto. The remaining reaction site of the cyclopentadienyl group in the following structural formula means a bonding site.

More specific examples of the transition metal compound represented by the above formula (2) include, but are not limited to, compounds represented by one of the structural formulas.

Specific examples of the transition metal compound represented by the above-mentioned formula (3) are not limited to the above-mentioned ranges of the above-mentioned chemical formula, but more preferred examples are as follows:

J ₁ to J ₃₁ and J ₁ 'to J ₁₃ ' in the above formulas (3a), (3b), (3c), (3d) and (3e) each independently represent a hydrogen, a methyl group, an ethyl group, a propyl group, A halogen atom, a trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, a tributylsilyl group, a triisopropylsilyl group, a trimethylsilylmethyl group, a trimethylsilylmethyl group, a methoxy group , Ethoxy group, and at least one of J ₉ to J ₁₃ and J ₉ 'to J ₁₃ ' may be perfluoroalkyl having 1 to 3 carbon atoms.

R ₃₁ and R ₃₂ in Formula 3 are each independently hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, Methoxyhexyl group, 1-ethoxyethyl group, 1-methyl-1-methoxyethyl group, tetrahydropyranyl group, or tetrahydrofuranyl group.

Specific examples of the compound represented by the formula (3a) include, but are not limited to, compounds represented by the following structural formulas. The remaining reaction site of the cyclopentadienyl group in the following structural formula means a bonding site.

Specific examples of the compound represented by the above formula (3b) include, but are not limited to, compounds represented by the following structural formulas. The remaining reaction site of the cyclopentadienyl group in the following structural formula means a bonding site.

Specific examples of the compound represented by Formula 3c include compounds represented by one of the following structural formulas, but the present invention is not limited thereto. The remaining reaction site of the cyclopentadienyl group in the following structural formula means a bonding site.

Specific examples of the compound represented by the formula (3) include compounds represented by the following structural formulas, but are not limited thereto. The remaining reaction site of the cyclopentadienyl group in the following structural formula means a bonding site.

Specific examples of the compound represented by Formula 3e include compounds represented by the following structural formulas, but are not limited thereto. The remaining reaction site of the cyclopentadienyl group in the following structural formula means a bonding site.

More specific examples of the transition metal compound represented by the above formula (3) include, but are not limited to, compounds represented by a structural formula.

Meanwhile, in the catalyst composition for synthesizing an olefin copolymer, a first metallocene catalyst comprising the transition metal compound of Formula 1, a second metallocene catalyst comprising the transition metal compound of Formula 2, And the molar ratio of the third metallocene catalyst containing the transition metal compound is not limited to a large extent.

However, the above-mentioned effects, for example, the olefin copolymer produced using the catalyst composition have a wider melt flow index and a melt flow rate ratio, exhibit a higher molecular weight, a broad molecular weight distribution and a high long chain side chain content, In order to maximize effects such as high environmental stress cracking resistance, spiral flow length and excellent shape stability, the transition metal compound of the above formula (1) is contained relative to the second metallocene catalyst containing the transition metal compound of the above formula (2) The molar ratio of the first metallocene catalyst to the third metallocene catalyst comprising the transition metal compound of Formula 3 may be 1: 0.5 to 2: 1 to 5.

If the molar ratio of the second metallocene catalyst containing the transition metal compound of Formula 2 to the first metallocene catalyst containing the transition metal compound of Formula 1 is too low, The proportion of the olefin copolymer having a low molecular weight may be lowered and the processability of the final product may be lowered. If the molar ratio of the second metallocene catalyst containing the transition metal compound of Formula 2 to the first metallocene catalyst containing the transition metal compound of Formula 1 is too high, The lower the proportion of the olefin copolymer having the ethylene-propylene copolymer, the lower the environmental stress cracking property and the spiral flow length of the final product.

If the molar ratio of the third metallocene catalyst containing the transition metal compound of Formula 3 is too low relative to the first metallocene catalyst containing the transition metal compound of Formula 1, The proportion of the olefin copolymer having a molecular weight is lowered, so that the environmental stress cracking resistance and the spiral flow length of the final product may be lowered.

If the molar ratio of the third metallocene catalyst containing the transition metal compound of Formula 2 to the first metallocene catalyst containing the transition metal compound of Formula 1 is too high, The proportion of olefin copolymer is excessively high and the polymer tail is excessively increased, so that an excessively high pressure is required at the time of injection, which may result in deterioration of processability or deterioration of the quality of the final product.

The molar ratio between the second metallocene catalyst comprising the transition metal compound of Formula 2 and the transition metal compound of Formula 3 is not particularly limited, but is preferably used within the above-mentioned range to realize the effect .

The catalyst composition for synthesizing an olefin copolymer may further contain a cocatalyst or a carrier.

The cocatalyst is an organometallic compound containing a Group 13 metal, and is not particularly limited as long as it can be used when olefins are polymerized under a general metallocene catalyst.

Specifically, the promoter compound may include at least one of an aluminum-containing primary catalyst of the following general formula (6) and a boron-containing secondary catalyst of the general formula (7).

[Chemical Formula 6]

- [Al (X) -O-] _k-

In Formula 6, X is independently halogen, halogen-substituted or unsubstituted hydrocarbyl group having 1 to 20 carbon atoms, k is an integer of 2 or more,

 (7)

T ⁺ [BG ₄ ] ^-

In Formula (7), T ⁺ is a polyatomic ion of +1 valence, B is boron of +3 oxidation state, and G is each independently selected from the group consisting of hydride group, dialkylamido group, halide group, alkoxide group, aryloxide group, Carbocyclic group, halocarbyl group, and halo-substituted hydrocarbyl group, wherein G has not more than 20 carbons, but G is a halide group in at least one position.

By using such first and second co-catalysts, the molecular weight distribution of the finally produced polyolefin becomes more uniform, and the polymerization activity can be improved.

The first cocatalyst of formula (6) may be an alkylaluminoxane compound having a linear, circular or network-like repeating unit bonded thereto. Specific examples of the first catalyst include methylaluminoxane (MAO), ethylaluminium Isobutylaluminoxane, butylaluminoxane, and the like.

Also, the second cocatalyst of formula (7) may be a tri-substituted ammonium salt, or a dialkylammonium salt, or a borate compound in the form of a trisubstituted phosphonium salt. Specific examples of the second cocatalyst include trimethylammonium tetraphenylborate, methyl dioctadecylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate , Methyltetradecyclooctadecylammonium tetraphenylborate, N, N-dimethylanilinium tetraphenylborate, N, N-diethylanilinium tetraphenylborate, N, N-dimethyl (2,4,6-trimethylanilinium (Tetrafluoroborate) borate, trimethylammonium tetrakis (pentafluorophenyl) borate, methylditetradecylammonium tetrakis (pentaphenyl) borate, methyl dioctadecylammonium tetrakis (Pentafluorophenyl) borate, triphenyl ammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium (Pentafluorophenyl) borate, tri (sec-butyl) ammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (Pentafluorophenyl) borate, N, N-dimethyl (2,4,6-trimethylanilinium) tetrakis (pentafluorophenyl) borate, trimethylammonium tetrakis Tetrafluorophenyl) borate, triethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, tripropylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate , Tri (n-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, dimethyl (t-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) Borate, N, N-dimethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N, N-diethylanilinium tetrakis (2,3,4,6- Boronate in the form of a tri-substituted ammonium salt such as N, N-dimethyl- (2,4,6-trimethylanilinium) tetrakis- (2,3,4,6-tetrafluorophenyl) compound; A borate-based compound in the form of a dialkylammonium salt such as dioctadecylammonium tetrakis (pentafluorophenyl) borate, ditetradecylammonium tetrakis (pentafluorophenyl) borate or dicyclohexylammonium tetrakis (pentafluorophenyl) compound; (Pentafluorophenyl) borate or tri (2,6-, dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, methyl dioctadecylphosphonium tetrakis ) Borate and the like, and the like.

The mass ratio of the carrier to the total weight of the transition metal contained in the first metallocene compound, the second metallocene compound and the third metallocene compound may be 10 to 10,000. When the carrier and the metallocene compound are contained in the above mass ratio, they can exhibit an optimum shape.

In addition, the mass ratio of the cocatalyst compound to the carrier may be from 1: 1 to 1: 100.

When the cocatalyst and the metallocene compound are contained in the mass ratio, the activity and the polymer microstructure can be optimized.

On the other hand, the carrier may be a carrier containing a hydroxy group on its surface, preferably a carrier having a hydroxyl group and a siloxane group, which are dried and removed moisture from the surface, and have high reactivity.

Silica-alumina, silica-magnesia, and the like, which are usually dried at high temperature, and which are usually made of oxides such as Na ₂ O, K ₂ CO ₃ , BaSO ₄ , and Mg (NO ₃ ) ₂ , Sulfate, and nitrate components.

The drying temperature of the carrier is preferably 200 to 800, more preferably 300 to 600, and most preferably 300 to 400. When the drying temperature of the carrier is lower than 200, water is too much to react with the cocatalyst on the surface. When the drying temperature exceeds 800, pores on the surface of the carrier are combined to reduce the surface area, Only the siloxane group is left, and the reaction site with the co-catalyst is reduced, which is not preferable.

The amount of hydroxyl groups on the surface of the support is preferably from 0.1 to 10 mmol / g, more preferably from 0.5 to 5 mmol / g. The amount of the hydroxyl group on the surface of the carrier can be controlled by the preparation method and conditions of the carrier or by drying conditions such as temperature, time, vacuum or spray drying.

If the amount of the hydroxyl group is less than 0.1 mmol / g, the number of sites of reaction with the co-catalyst is small. If the amount is more than 10 mmol / g, the hydroxyl group may be present in the water other than the hydroxyl group present on the surface of the carrier particle. not.

On the other hand, the catalyst composition for synthesizing an olefin copolymer includes a step of supporting a promoter compound on a support, a step of adding a selected one of the first metallocene compound, the second metallocene compound and the third metallocene compound to the support Sequentially or simultaneously carrying two or more of the above metallocene compounds.

The order of supporting the first metallocene compound, the second metallocene compound, and the third metallocene compound may be changed as needed.

In the preparation of the catalyst composition for synthesizing an olefin copolymer, a hydrocarbon solvent such as pentane, hexane or heptane, or an aromatic solvent such as benzene or toluene may be used as a reaction solvent. In addition, the metallocene compound and the co-catalyst compound may be used in the form supported on silica or alumina.

The catalyst composition for synthesizing an olefin copolymer may itself be used for polymerization of an olefin-based monomer. The catalyst composition for synthesizing an olefin copolymer may be prepared by reacting with an olefin monomer to prepare a prepolymerized catalyst. For example, the catalyst may be used separately as ethylene, propylene, 1-butene, 1-hexene, It may be prepared by contacting with an olefin-based monomer to prepare a prepolymerized catalyst.

According to the present invention, it has excellent processability due to wide melt flow index and melt flow rate ratio, high molecular weight, broad molecular weight distribution and high long chain side branch content, so that it has excellent environmental stress cracking property and processability and dimensional stability, And an ethylene / alpha-olefin copolymer which can be preferably used as a food container, bottle cap or the like which requires stability and chemical resistance in a high temperature environment.

Brief Description of the Drawings Fig. 1 is a GPC curve graph in which the x-axis and y-axis of the olefin copolymer obtained in Examples 1 and 2 and Comparative Example 1 are log Mw and dw / dlogMw, respectively.

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

< Manufacturing example >

[ 1st Metallocene  Compound Manufacturing example ]

Manufacturing example  One

6.3 g (20 mmol) of 1,8-bis (bromomethyl) naphthalene and 8.3 g (40 mmol) of methyl TMS-Indene Lithium salt Dissolved in 80 mL of THF, added dropwise in a dry ice / acetone bath, and stirred overnight at room temperature. After completion of the stirring, the reaction product was extracted with ether / water, and the residual moisture of the organic layer was removed with MgSO ₄ , and the solvent was removed under vacuum decompression to obtain 11.1 g (20 mmol, Mw 556.93).

11 g of the obtained ligand compound was dissolved in a mixed solvent of 80 mL of toluene and 5 mL of Methyl Tertiary Butyl Ether (MTBE), 16.7 mL (41.6 mmol) of a 2.5 M n-butyllithium hexane solution was added dropwise and the mixture was stirred at room temperature. Then, 7.5 g (19.8 mmol) of ZrCl ₄ (THF) ₂ was added to 80 mL of toluene to prepare a slurry, which was then transferred in a dry ice / acetone bath and stirred at room temperature overnight.

After completion of the stirring, the slurry was filtered to remove LiCl, the toluene of the filtrate was removed by vacuum drying, and then 100 mL of hexane was added thereto, followed by sonication for 1 hour. The slurry was then filtered to obtain 4.5 g of a filtered solid metallocene compound (yield 62.3 mol%, yellow solid).

^{1 H NMR (500 MHz, CDCl} 3): 8.16 - 6.95 (14H, m), 5.99 (2H, d), 3.99 (2H, m), 3.83 (2H, m), 3.39 (2H, m), 0.15 ( 18H, d)

[ Second Metallocene  Compound Manufacturing example ]

Manufacturing example  2

One)  Preparation of ligand compounds

Add 3 g (10 mmol) of Indenoindole to a dry 250 mL schlenk flask and dissolve in 100 mL of hexane. Add 4.4 mL (11 mmol) of 2.5 M nBuLi hexane solution slowly, slowly add the reaction mixture to room temperature, .

Another 250 mL schlenk flask was placed in the glove box and 2.7 g (10 mmol) of (6-tert-butoxyhexyl) dichloro (methyl) silane was weighed out of the glove box. Then, 50 mL of hexene was added to the schlenk flask to dissolve the flask, and the flask was cooled to -78 ° C. Then, the lithiated solution of Indenoindole was injected through the cannula.

After the completion of the above injection, the temperature of the schlenk flask was raised to room temperature and stirred for one day. 2.1 g (10 mmol) of methyl TMS-indene lithium salt was dissolved in 100 mL of THF, Lt; / RTI &gt; After the completion of the stirring, the reaction product was extracted with ether / water, and the residual moisture of the organic layer was removed with MgSO ₄ , and the solvent was removed under vacuum decompression to obtain 7 g of a liquid ligand compound (10 mmol, Mw : 696.1).

^{1 H NMR (500 MHz, CDCl3} ): 7.86 - 7.11 (17H, m), 5.11-5.64 (3H, d), 4.16 (1H, m), 3.20 (2H, m), 1.61-1.47 (6H, m) , 1.15 (9H, s), 0.34 (3H, m)

2) Metallocene  Preparation of compounds

5.5 g (7.9 mmol) of the obtained ligand compound was dissolved in 80 mL of toluene, and 6.6 mL (16.6 mmol) of a 2.5 M n-butyllithium hexane solution was added dropwise thereto, followed by stirring at room temperature. Then, 3 g (7.9 mmol) of ZrCl ₄ (THF) ₂ was added to 80 mL of toluene to prepare a slurry, which was then transferred in a dry ice / acetone bath and stirred overnight at room temperature.

After completion of the stirring, the slurry was filtered to remove LiCl, the toluene of the filtrate was removed by vacuum drying, and then 100 mL of hexane was added thereto, followed by sonication for 1 hour. The slurry was then filtered to obtain 1.5 g (yield 23 mol%, red solid) of the filtered solid metallocene compound.

^{1 H NMR (500 MHz, CDCl} 3): 7.66 - 7.20 (17H, m), 6.15-5.71 (1H, d), 5.65 (2H, m), 3.76 (2H, m), 3.20 (2H, m), 1.51-1.29 (4H, m), 1.15 (3H, s), 0.01 (9H, s)

[ Third Metallocene  Compound Manufacturing example ]

Manufacturing example  3

1) Preparation of ligand compound

A solution of 2.9 g (7.4 mmol) of indole in 100 mL of hexane and 2 mL (16.8 mmol) of MTBE (methyl) was added to a solution of 8-methyl- 3.2 mmol (8.1 mmol) of 2.5 M n-BuLi hexane solution was added dropwise in a dryice / acetone bath and stirred overnight at room temperature. To another 250 mL schlenk flask, 2 g (7.4 mmol) of (6-tert-butoxyhexyl) dichloro (methyl) silane was dissolved in 50 mL of hexane and added dropwise in a dryice / (2- (trifluoromethyl) benzyl) -5,10-dihydroindeno [1,2-b] indole dropwise dropwise via cannula. After the completion of the addition, the mixture was slowly raised to room temperature and stirred at room temperature overnight. At the same time, 1.2 g (7.4 mmol) of fluorene was dissolved in 100 mL of THF. 3.2 mL (8.1 mmol) of 2.5 M n-BuLi hexane solution was added dropwise in a dryice / acetone bath and stirred overnight at room temperature.

A reaction solution (Si (4)) of 8-methyl-5- (2- (trifluoromethyl) benzyl) -5,10- dihydroindeno [ Solution) was NMR-sampled to confirm the completion of the reaction.

^{1 H NMR (500 MHz, CDCl} 3): 7.74-6.49 (11H, m), 5.87 (2H, s), 4.05 (1H, d), 3.32 (2H, m), 3.49 (3H, s), 1.50- 1.25 (8H, m), 1.15 (9H, s), 0.50 (2H, m), 0.17

After the synthesis was confirmed, the lithiated solution of fluorene was slowly added dropwise to the Si solution in a dryice / acetone bath and stirred overnight at room temperature. After the reaction, the residue was extracted with ether / water, and the residual moisture of the organic layer was removed with MgSO _{4. The} solvent was removed under reduced pressure to obtain 5.5 g (7.4 mmol) of an oily ligand compound. there was.

^{1 H NMR (500 MHz, CDCl} 3): 7.89-6.53 (19H, m), 5.82 (2H, s), 4.26 (1H, d), 4.14-4.10 (1H, m), 3.19 (3H, s), 2.40 (3H, m), 1.35-1.21 (6H, m), 1.14 (9H, s), 0.97-0.9 (4H, m), 0.34 (3H, t).

2) Metallocene  Preparation of compounds

The resulting ligand compound (5.4 g, Mw 742.00, 7.4 mmol) was dissolved in 80 mL of toluene and 3 mL (25.2 mmol) of MTBE. 7.1 mL (17.8 mmol) of 2.5 M n-BuLi hexane solution was added dropwise in a dry / Lt; / RTI &gt; A _{ZrCl 4 (THF) 2 3.0 g} (8.0 mmol) was placed in a slurry was put in a 80 mL of toluene. An 80 mL toluene slurry of ZrCl ₄ (THF) ₂ was transferred to a ligand-Li solution in a dry ice / acetone bath and stirred overnight at room temperature.

The reaction mixture was filtered to remove LiCl, the toluene of the filtrate was removed by vacuum drying, and then 100 mL of hexane was added thereto, followed by sonication for 1 hour. This was filtered to obtain 3.5 g (yield 52 mol%) of a purple metallocene compound as a filtered solid.

^{1 H NMR (500 MHz, CDCl} 3): 7.90-6.69 (9H, m), 5.67 (2H, s), 3.37 (2H, m), 2.56 (3H, s), 2.13-1.51 (11H, m), 1.17 (9 H, s).

[Preparation of hybrid supported catalyst Example ]

Example  One

To the 20L sus high pressure reactor was added 3.0 kg of toluene solution and the reactor temperature was maintained at 40. 1,000 g of silica (SYLOPOL 948, manufactured by Grace Davison), which was dehydrated by applying a vacuum for 12 hours at a temperature of 600, was charged into the reactor and the silica was thoroughly dispersed. The metallocene compound of Preparation Example 1, 0.1 mmol / g SiO ₂ , And the mixture was reacted by stirring at 40 for 2 hours. Thereafter, the stirring was stopped and settling was performed for 30 minutes, and the reaction solution was decanted.

Then, 3 kg of a 10 wt% methylaluminoxane (MAO) / toluene solution was added to the reactor, followed by stirring at 40 to 200 rpm for 12 hours. Then, the metallocene compound of Production Example 2 was dissolved in toluene at a ratio of 0.05 mmol / g SiO _2, and the mixture was reacted at 40 ° C and 200 rpm for 12 hours with stirring. Then, the metallocene compound of Production Example 3 was dissolved in toluene at a ratio of 0.15 mmol / g SiO _2, and the mixture was reacted at 40 ° C with stirring at 200 rpm for 12 hours.

Then, 3.0 kg of hexane was added to the reactor, the hexane slurry was transferred to a filter dryer, and the hexane solution was filtered. Dried under reduced pressure at 40 for 4 hours to prepare a SiO ₂ mixed supported catalyst of 1Kg.

Example  2

A supported catalyst was prepared in the same manner as in Example 1, except that the amounts of the metallocene compounds of Preparation Examples 1 to 3 were varied.

Comparative Example  One

The olefin copolymer (ME1000, manufactured by LG Chemical), which was prepared with a Ziegler-Natta catalyst, was used as Comparative Example 1.

< Experimental Example >

Ethylene-1- Hexen  Copolymerization

Each of the hybrid supported metallocene catalysts prepared in each of the above Examples was fed into a CSTR continuous polymerization reactor (reactor volume 50 L, reaction flow rate 7 m / s) to prepare an olefin polymer. 1-hexene was used as the comonomer, and the reactor pressure was maintained at 10 bar and the polymerization temperature was maintained at 90 ° C.

The polymerization conditions using the hybrid supported metallocene catalysts of Examples 1 to 3 are summarized in Table 1 below.

catalyst Polymerization conditions Pressure (bar)
/ Temperature (℃) Hydrogen
(g / hr) 1-hexene
(cc / min) Example 1 Production Example 1
0.10 mmol / gSiO ₂ 10/90 3.0 6 Production Example 2
0.05 mmol / g SiO ₂ Production Example 3
0.15 mmol / gSiO ₂ Example 2 Production Example 1
0.07 mmol / gSiO ₂ 10/90 3.0 6 Production Example 2
0.07 mmol / gSiO ₂ Production Example 2
0.15 mmol / gSiO ₂

Evaluation of physical properties of polymer

1) Density: ASTM 1505

2) Melt Index (MFR, 2.16 kg / 21.6 kg): Measuring temperature 190, ASTM 1238

3) MFRR _(0.6 MFR ₂₁ / MFR _{2 .16):} MFR is _0.6 to _21, a melt index (MI, 21.6kg load) divided by the rate MFR _{2 .16} (MI, 2.16kg load).

4) Molecular weight and molecular weight distribution: 1, 2, 4-Trichlorobenzene containing 0.0125% of BHT was dissolved in PL-SP260 for 160, 10 hours and pretreated. PL-GPC220 was used to measure the number average molecular weight The average molecular weight was measured. The molecular weight distribution is represented by the ratio of the weight average molecular weight to the number average molecular weight.

Using the measured GPC data, a GPC curve graph in which the x-axis is log Mw and the y-axis is dw / dlogMw is derived.

5) ESCR: Time to F50 (50% destruction) was measured under temperature 50 using 10% Igepal CO-630 Solution according to ASTM D 1693.

6) Spiral flow length (SF): An ENGEL 150-ton injection machine was used. The mold thickness was 1.5 mm, the injection temperature was 190 ° C, the mold temperature was 50 ° C, and the injection pressure was 90 bar.

7) Dimensional change ratio: Specimens were prepared from the olefin copolymers obtained in each of Examples and Comparative Examples, and the dimensional change rate was measured using dynamic mechanical analysis (DMA). Specifically, the olefin copolymer obtained in each of the examples and the comparative examples was pressed at 200 MPa at 20 MPa for about 5 minutes to prepare specimens (width 6 mm, thickness 0.3 mm) MPa for 20 minutes, and the step of raising the temperature and maintaining the temperature at 60 占 폚 and the pressure of 0.5 MPa for 10 minutes were repeated one cycle, and the four cycles were repeated. Strain was recorded at 32 ° C for each cycle. Finally, the dimensional change rate was determined as a value obtained by dividing the difference between the strain of the first cycle and the strain of the fourth cycle by the strain value of the first cycle * 100 (%).

catalyst MW
(Kg / mol) MWD MI MFRR density
(g / cm3) Dimensional change ratio (%) ESCR Spiral Example 1 141,941 7.3 0.31 3.35 0.949 2.02 360 15 Example 2 137,144 9.2 0.32 3.56 0.951 1.53 320 17 Comparative Example 1 138.940 12.2 0.9 4.0 0.952 4.35 50 13

As shown in Table 2, the olefin copolymers obtained by using the mixed metallocene catalysts of Examples 1 and 2 exhibited relatively high spiral flow lengths with an environmental stress cracking resistance of 300 hours or more and exhibited high temperature and high pressure conditions Showed a dimensional change ratio of about 2% or less and thus showed high dimensional stability.

On the other hand, as can be seen from FIG. 1, the olefin copolymer prepared in each of Examples 1 and 2 had a log Mw of 5.0 to less than 5.5 in a GPC curve graph in which the x axis was log Mw and the y axis was dw / dlogMw And the log Mw is 5.0 or more in relation to the ratio of the integral value in the region where the log Mw is 4.5 or more and less than 5.0 relative to the total integrated value of the x-axis. The difference in the ratio of the integral value in the region of less than 0.25% was confirmed to be 6.36% and 5.24%, respectively.

As described above, the olefin copolymers prepared in Examples 1 and 2 of Examples 1 and 2 exhibit the above-mentioned values in the GPC curve graphs in which the x-axis is log Mw and the y-axis is dw / dlogMw, The olefin copolymer exhibits a high stiffness required for a polymer injection product, can easily be broken, exhibits excellent dimensional stability with high pressure resistance and chemical resistance, and exhibits a significantly low strain rate due to changes in temperature and pressure .

That is, the olefin copolymers obtained by using the hybrid metallocene catalysts of Examples 1 and 2 have excellent processability due to wide melt flow rate and melt flow rate ratio, and have high molecular weight, broad molecular weight distribution and high long chain side chain content , As described above, is excellent in environmental stress cracking property and workability, and is excellent in stability in a high pressure and high temperature environment, and can be applied to a food container, a bottle cap and the like, thereby realizing excellent performance.

Claims (13)

A molecular weight of 100,000 to 300,000 g / mol,
A molecular weight distribution (Mw / Mn) of 5 to 30,
A density of 0.930 to 0.960 g / cm &lt; 3 &
MFRR _{5 /2.16} (a melt flow index measured at 190 占 폚 under a load of 5 kg divided by a melt flow index measured at 190 占 폚 under a load of 2.16 kg according to ASTM D1238) is 1 to 10,
in the GPC curve graph in which the x-axis is log Mw and the y-axis is dw / dlogMw, the integral value in the region where the log Mw is 5.0 or more and less than 5.5 is 20% or more of the integral value of the x-
Olefin copolymer.
The method according to claim 1,
the integral value in the region where the log Mw is 5.0 or more and less than 5.5 in the GPC curve graph in which the x-axis is log Mw and the y-axis is dw / dlogMw is 20% to 30% of the total x-axis integral value.
The method according to claim 1,
wherein an integral value in an area of log Mw of 4.5 or more and less than 5.0 in an GPC curve graph having an x-axis of log Mw and a y-axis of dw / dlogMw is 25% or more of the integral value of the x-axis.
The method of claim 3,
In the GPC curve graph where the x-axis is log Mw and the y-axis is dw / dlogMw,
wherein the difference in the ratio of the integral value in the region where the log Mw is equal to or more than 4.5 and less than 5.0 and the ratio of the integral value in the region where the log Mw is equal to or greater than 5.0 and less than 5.5 in relation to the x-axis total integration value is 7% or less.
The method according to claim 1,
MFR _{2 .16} 0.01 to 1.0 g / 10min of the olefin copolymer (a melt flow index measured at 190 ℃, 2.16 kg load in accordance with ASTM D1238) of the olefin copolymer.
The method according to claim 1,
Wherein the olefin copolymer measured according to ASTM D 1693 has an environmental stress cracking resistance (ESCR) of 200 hours or more.
The method according to claim 1,
The olefin copolymer
A first metallocene catalyst comprising a transition metal compound of Formula 1; A second metallocene catalyst comprising a transition metal compound of Formula 2; And a third metallocene catalyst comprising a transition metal compound represented by the following formula (3): &lt; EMI ID = 2.0 &gt;
Ethylene / alpha-olefin copolymer:
[Chemical Formula 1]

In Formula 1,
Wherein R ₁ to R ₄ are the same or different and each independently represents hydrogen, halogen, a straight or branched alkyl group having 1 to 20 carbon atoms, a straight or branched alkenyl group having 2 to 20 carbon atoms, a C1 to C20 alkylsilyl group , C1 to C20 silylalkyl groups, C1 to C20 alkoxysilyl groups, C1 to C20 linear or branched alkoxy groups, C6 to C20 aryl groups, C7 to C20 alkylaryl groups, or C7 to C20 arylalkyl groups Lt;
Wherein Q ₁ is an alkylene group having 4 to 20 carbon atoms, an alkenylene group having 4 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, a cycloalkylene group having 4 to 20 carbon atoms, , An aryl alkylene group having 7 to 22 carbon atoms, a cycloalkylalkylene group having 5 to 22 carbon atoms,
Wherein R ₅ to R ₁₁ are the same or different and each independently represents hydrogen, halogen, a straight or branched alkyl group having 1 to 20 carbon atoms, a straight or branched alkenyl group having 2 to 20 carbon atoms, a C1 to C20 alkylsilyl group , C1 to C20 silylalkyl groups, C1 to C20 alkoxysilyl groups, C1 to C20 linear or branched alkoxy groups, C6 to C20 aryl groups, C7 to C20 alkylaryl groups, or C7 to C20 arylalkyl groups Lt;
Two or more adjacent groups in one of the benzene rings of R ₅ to R ₁₁ may be connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring;
M ₁ is a Group 4 transition metal,
Y ₁ and Y ₂ are the same or different from each other and each independently represents a halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a nitro group, an amido group, a C1 to C20 alkylsilyl group , A C1 to C20 alkoxy group, or a C1 to C20 sulfonate group,
(2)

In Formula 2,
M ₂ is a Group 4 transition metal,
X ₂₁ and X ₂₂ are the same or different from each other and each independently represents a halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a nitro group, an amido group, a C1 to C20 alkylsilyl group , A C1 to C20 alkoxy group, or a C1 to C20 sulfonate group,
Q _{2 is} carbon, silicon or germanium;
R ₂₁ and R ₂₂ are the same or different from each other and each independently represents hydrogen, halogen, C 1 to C 20 alkyl, C 2 to C 20 alkenyl, C 6 to C 20 aryl, C 7 to C 20 alkylaryl, C 7 to C 20 A C1 to C20 alkoxy group, a C2 to C20 alkoxyalkyl group, a C3 to C20 heterocycloalkyl group, or a C5 to C20 heteroaryl group;
One of C ₂₁ and C ₂₂ is represented by the following formula (2a), and the other is represented by the following formula (2b);
(2a)

(2b)

In the above formula (2a)
Z ₁ to Z ₉ are the same or different from each other and each independently represents hydrogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C1 to C20 alkoxy group, a C1 to C20 alkylsilyl group, a C1 to C20 silyl An alkyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group;
In the above formula (2b)
Z ₁₀ and Z ₁₂ to Z ₁₅ are hydrogen, halogen or an alkyl group having 1 to 3 carbon atoms,
Z ₁₁ represents a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C1 to C20 alkylsilyl group, a C1 to C20 silylalkyl group, a C1 to C20 alkoxysilyl group, a C1 to C20 ether group, A silyloxy group of C1 to C20, a C1 to C20 alkoxy group, a C2 to C20 alkoxyalkyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group,
(3)

In Formula 3,
M ₃ is a Group 4 transition metal,
X ₃₁ and X ₃₂ are the same or different and each independently represents a halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a nitro group, an amido group, a C1 to C20 alkylsilyl group , A C1 to C20 alkoxy group, or a C1 to C20 sulfonate group,
Q _{3 is} carbon, silicon or germanium;
R ₃₁ and R ₃₂ are the same or different and are each independently selected from the group consisting of hydrogen, halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, A C1 to C20 alkoxy group, a C2 to C20 alkoxyalkyl group, a C3 to C20 heterocycloalkyl group, or a C5 to C20 heteroaryl group;
C ₃₁ and One of C ₃₂ is represented by the following formula (3a) or (3b), and C ₃₁ and And the other of C ₃₂ is represented by the following formula (3c), (3d) or (3e);
[Chemical Formula 3]

(3b)

[Chemical Formula 3c]

(3d)

[Formula 3e]

In the above formulas (2a), (2b), (3a), (3b) and (3c), J ₁ to J ₃₁ and J ₁ 'to J ₁₃ ' are the same or different and each independently represents hydrogen, halogen, a C1 to C20 alkyl group, A C1 to C20 alkylsilyl group, a C1 to C20 silylalkyl group, a C1 to C20 alkoxysilyl group, a C1 to C20 alkoxy group, a C6 to C20 aryl group, a C7 to C20 alkenyl group, An alkylaryl group of C7 to C20, or an arylalkyl group of C7 to C20,
At least one of J ₉ to J ₁₃ and J ₉ 'to J ₁₃ ' is a C1 to C20 haloalkyl group,
Two or more adjacent groups in the aromatic ring of one of J ₁ to J ₃₁ and J ₁ 'to J ₁₃ ' may be connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring.
8. The method of claim 7,
The alpha-olefin is preferably selected from the group consisting of propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-tetradecene, 1-hexadecene, and 1-aidocene.
8. The method of claim 7,
In Formula 1,
Wherein R ₁ to R ₂ are C1 to C20 alkylsilyl groups and C1 to C20 silylalkyl groups,
R ₃ to R ₄ are arylene groups having 6 to 20 carbon atoms and aryldialkylene groups having 8 to 22 carbon atoms,
Each of R ₅ to R ₁₁ is hydrogen, halogen, a straight or branched alkyl group having 1 to 20 carbon atoms,
M ₁ is titanium, zirconium or hafnium, Y ₁ and Y ₂ are halogen,
Ethylene / alpha-olefin copolymer.
8. The method of claim 7,
Z ₁ to Z ₉ in formula (2a) each independently represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a tert- butyl group, a pentyl group, a hexyl group, a heptyl group, , A propylene group, a butenyl group, a phenyl group, a benzyl group, a naphthyl group, a methoxy group, an ethoxy group or a tert-butoxyhexyl group,
Z ₁₁ in the above formula (2b) is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, A benzyl group, a naphthyl group, a trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, a tributylsilyl group, a triisopropylsilyl group, a trimethylsilylmethyl group, a tert-butyldimethylsilylether group, Or a tert-butoxyhexyl group,
Wherein R ₂₁ and R ₂₂ in Formula 2 are a methyl group or a tert-butoxyhexyl group,
Ethylene / alpha-olefin copolymer.
8. The method of claim 7,
J ₁ to J ₃₁ and J ₁ 'to J ₁₃ ' in the above formulas (3a), (3b), (3c), (3d) and (3e) each independently represent a hydrogen, a methyl group, an ethyl group, a propyl group, A halogen atom, a trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, a tributylsilyl group, a triisopropylsilyl group, a trimethylsilylmethyl group, a trimethylsilylmethyl group, a methoxy group , Ethoxy group,
At least one of J ₉ to J ₁₃ and J ₉ 'to J ₁₃ ' is perfluoroalkyl having 1 to 3 carbon atoms,
R ₃₁ and R ₃₂ in Formula 3 are each independently hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, Ethoxyethyl group, 1-methyl-1-methoxyethyl group, tetrahydropyranyl group, or tetrahydrofuranyl group,
Olefin copolymer.
8. The method of claim 7,
A first metallocene catalyst comprising a transition metal compound of Formula 1 and a third metallocene catalyst comprising a transition metal compound of Formula 3 relative to a second metallocene catalyst comprising a transition metal compound of Formula 2, Is in the range of 1: 0.5 to 2: 1 to 5.
8. The method of claim 7,
Wherein the catalyst composition for synthesizing an olefin copolymer further comprises a cocatalyst or a carrier.

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