KR20190106796A - Supported hybrid metallocene catalyst, and preparation method of polyolefin using the same - Google Patents

Abstract

The present invention relates to a supported hybrid metallocene catalyst and a method for manufacturing polyolefin using the same. By using the supported hybrid metallocene catalyst of the present invention, polyolefin having both excellent processability and physical properties such as drop impact strength or the like can be manufactured. To this end, the supported hybrid metallocene catalyst comprises at least one first transition metal compound, at least one second transition metal compound and a carrier supporting the first and second transition metal compounds.

Description

Hybrid supported metallocene catalyst and method for producing polyolefin using same {SUPPORTED HYBRID METALLOCENE CATALYST, AND PREPARATION METHOD OF POLYOLEFIN USING THE SAME}

The present invention relates to a hybrid supported metallocene catalyst and a method for producing a polyolefin using the same.

Olefin polymerization catalyst systems can be classified into Ziegler-Natta and metallocene catalyst systems, and these two highly active catalyst systems have been developed for their respective characteristics. The Ziegler-Natta catalyst has been widely applied to existing commercial processes since the invention in the 50s, but is characterized by a wide molecular weight distribution of the polymer because it is a multi-site catalyst having multiple active sites. There is a problem that there is a limit in securing the desired physical properties because the composition distribution is not uniform.

Meanwhile, the metallocene catalyst is composed of a combination of a main catalyst composed mainly of a metallocene compound and a cocatalyst composed of an organometallic compound composed mainly of aluminum. Such a catalyst is a homogeneous complex catalyst and is a single site catalyst. ), The molecular weight distribution is narrow according to the characteristics of the single active site, the homogeneous composition distribution of the comonomer is obtained, and the stereoregularity, copolymerization properties, molecular weight of the polymer according to the ligand structure modification of the catalyst and the change of polymerization conditions. , Crystallinity and so on.

U. S. Patent No. 5,032, 562 describes a process for preparing a polymerization catalyst by supporting two different transition metal catalysts on one supported catalyst. It is a method of producing a bimodal distribution polymer by supporting a titanium (Ti) -based Ziegler-Natta catalyst that generates a high molecular weight and a zirconium (Zr) -based metallocene catalyst that produces a low molecular weight on one support As a result, the supporting process is complicated, and the morphology of the polymer is degraded due to the promoter.

US Pat. No. 5,525,678 describes a method of using a catalyst system for olefin polymerization in which a high molecular weight polymer and a low molecular weight polymer can be simultaneously polymerized by simultaneously supporting a metallocene compound and a nonmetallocene compound on a carrier. This has the disadvantage that the metallocene compound and the non-metallocene compound must be separately supported, and the carrier must be pretreated with various compounds for the supporting reaction.

U. S. Patent No. 5,914, 289 describes a method for controlling the molecular weight and molecular weight distribution of a polymer using a metallocene catalyst supported on each carrier, but the amount of solvent used and the time required for preparing the supported catalyst are high. The hassle of having to support the metallocene catalyst to be used on the carrier, respectively.

In addition, linear low density polyethylene (LLDPE) is produced by copolymerizing ethylene and alpha olefin at low pressure using a polymerization catalyst, and has a narrow molecular weight distribution, a short length branch of a constant length, and no long chain branching resin. to be. In addition to the properties of general polyethylene, LLDPE film has high breaking strength and elongation, and excellent tear strength and drop impact strength, so that the use of stretch films and overlap films that are difficult to apply to existing low density polyethylene or high density polyethylene is increasing. have. However, LLDPE has poor blown film processability compared to excellent mechanical properties. Generally, a blown film is a film produced by blowing air into a molten plastic and inflating it, also called an inflation film.

Factors to be considered when processing blown films should be considered bubble stability, processing load, etc., In order to produce a polyolefin with excellent processability, a method of manufacturing a film by blending low density polyethylene (LDPE) in LLDPE Is being used. However, even a very small amount of LDPE causes a problem of significantly lowering the mechanical properties of the conventional LLDPE.

Therefore, in order to solve the above disadvantages, there is a continuous need for a method of preparing an olefin polymer having a desired physical property by preparing a hybrid supported metallocene catalyst having excellent activity.

However, among all these attempts, there are only a few catalysts actually applied in commercial plants, and there is still a need for catalysts that exhibit improved polymerization performance.

The present invention is to provide a mixed supported metallocene catalyst capable of producing a polyolefin excellent in processability and exhibiting excellent properties such as drop impact strength.

The present invention, at least one first transition metal compound selected from the compound represented by the formula (1); At least one second transition metal compound selected from compounds represented by Formula 2; And a carrier supporting the first and second transition metal compounds, wherein the first and second transition metal compounds are included in a molar ratio of 1.2: 1 to 7.5: 1. To provide.

[Formula 1]

In Chemical Formula 1,

Q ₁ and Q ₂ are the same as or different from each other, and each independently halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkoxyalkyl group, C6 to C20 aryl group, C7 to C20 alkylaryl Or an arylalkyl group of C7 to C20;

T ₁ is carbon, silicon, or germanium;

M ₁ is a Group 4 transition metal;

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

R ₁ to R ₁₄ are the same as or different from each other, and are each independently hydrogen, halogen, an alkyl group of C1 to C20, a haloalkyl group of C1 to C20, an alkenyl group of C2 to C20, an alkylsilyl group of C1 to C20, and C1 to C20 silylalkyl group, C1 to C20 alkoxysilyl group, C1 to C20 alkoxy group, C6 to C20 aryl group, C7 to C20 alkylaryl group, or C7 to C20 arylalkyl group, or R ₁ to R ₁₄ Two or more adjacent to each other are connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring;

[Formula 2]

In Chemical Formula 2,

Q ₃ and Q ₄ are the same as or different from each other, and each independently halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkoxyalkyl group, C6 to C20 aryl group, C7 to C20 alkylaryl Or an arylalkyl group of C7 to C20;

T ₂ is carbon, silicon, or germanium;

M ₂ is a Group 4 transition metal;

X ₃ and X ₄ are the same as or different from each other, and each independently halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C6 to C20 aryl group, nitro group, amido group, C1 to C20 alkylsilyl group , A C1 to C20 alkoxy group, or a C1 to C20 sulfonate group;

R ₁₅ to R ₂₈ are the same as or different from each other, and are each independently hydrogen, halogen, C1 to C20 alkyl group, C1 to C20 haloalkyl group, C2 to C20 alkenyl group, C2 to C20 alkoxyalkyl group, C1 to C20 Alkylsilyl group, C1 to C20 silylalkyl group, C1 to C20 alkoxysilyl group, C1 to C20 alkoxy group, C6 to C20 aryl group, C7 to C20 alkylaryl group, or C7 to C20 arylalkyl group Provided that R ₂₀ and R ₂₄ are the same as or different from each other, and each independently an alkyl group of C1 to C20, or two or more adjacent to each other of R ₁₅ to R ₂₈ are connected to each other to be substituted or unsubstituted aliphatic or aromatic To form a ring,

Provided that at least one of Q ₃ , Q ₄ , R ₂₆ , and R ₂₇ is an alkoxyalkyl group of C 2 to C 20.

In addition, the present invention provides a method for producing a polyolefin comprising the step of polymerizing the olefin monomer in the presence of the hybrid supported metallocene catalyst.

In the present invention, terms such as first and second are used to describe various components, and the terms are used only for the purpose of distinguishing one component from other components.

Also, the terminology used herein is for the purpose of describing example embodiments only and is not intended to be limiting of the invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. As used herein, the terms "comprise", "comprise" or "have" are intended to indicate that there is a feature, number, step, component, or combination thereof, that is, one or more other features, It should be understood that it does not exclude in advance the possibility of the presence or addition of numbers, steps, components, or combinations thereof.

As the invention allows for various changes and numerous modifications, particular embodiments will be illustrated and described in detail below. However, this is not intended to limit the present invention to the specific disclosed form, it should be understood to include all modifications, equivalents, and substitutes included in the spirit and scope of the present invention.

Hereinafter, a hybrid supported metallocene catalyst and a method for preparing polyolefin using the same according to specific embodiments of the present invention will be described in detail.

According to one embodiment of the invention,

At least one first transition metal compound selected from compounds represented by Formula 1;

At least one second transition metal compound selected from compounds represented by Formula 2; And

A carrier supporting the first and second transition metal compounds;

Including,

The first and second transition metal compound comprises a molar ratio of 1.2: 1 to 7.5: 1,

Hybrid supported metallocene catalysts may be provided:

[Formula 1]

In Chemical Formula 1,

Q ₁ and Q ₂ are the same as or different from each other, and each independently halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 to C2 alkoxyalkyl group, C6 to C20 aryl group, C7 to C20 alkylaryl Or an arylalkyl group of C7 to C20;

T ₁ is carbon, silicon, or germanium;

M ₁ is a Group 4 transition metal;

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

R ₁ to R ₁₄ are the same as or different from each other, and are each independently hydrogen, halogen, an alkyl group of C1 to C20, a haloalkyl group of C1 to C20, an alkenyl group of C2 to C20, an alkylsilyl group of C1 to C20, and C1 to C20 silylalkyl group, C1 to C20 alkoxysilyl group, C1 to C20 alkoxy group, C6 to C20 aryl group, C7 to C20 alkylaryl group, or C7 to C20 arylalkyl group, or R ₁ to R ₁₄ Two or more adjacent to each other are connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring;

[Formula 2]

In Chemical Formula 2,

Q ₃ and Q ₄ are the same as or different from each other, and each independently halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkoxyalkyl group, C6 to C20 aryl group, C7 to C20 alkylaryl Or an arylalkyl group of C7 to C20;

T ₂ is carbon, silicon, or germanium;

M ₂ is a Group 4 transition metal;

X ₃ and X ₄ are the same as or different from each other, and each independently halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C6 to C20 aryl group, nitro group, amido group, C1 to C20 alkylsilyl group , A C1 to C20 alkoxy group, or a C1 to C20 sulfonate group;

R ₁₅ to R ₂₈ are the same as or different from each other, and are each independently hydrogen, halogen, C1 to C20 alkyl group, C1 to C20 haloalkyl group, C2 to C20 alkenyl group, C2 to C20 alkoxyalkyl group, C1 to C20 Alkylsilyl group, C1 to C20 silylalkyl group, C1 to C20 alkoxysilyl group, C1 to C20 alkoxy group, C6 to C20 aryl group, C7 to C20 alkylaryl group, or C7 to C20 arylalkyl group Provided that R ₂₀ and R ₂₄ are the same as or different from each other, and each independently an alkyl group of C1 to C20, or two or more adjacent to each other of R ₁₅ to R ₂₈ are connected to each other to be substituted or unsubstituted aliphatic or aromatic To form a ring,

Provided that at least one of Q ₃ , Q ₄ , R ₂₆ , and R ₂₇ is an alkoxyalkyl group of C 2 to C 20.

In the hybrid supported metallocene catalyst according to the present invention, the substituents of Chemical Formulas 1 and 2 will be described in detail below.

The alkyl group of C1 to C20 includes a linear or branched alkyl group, specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, An octyl group etc. are mentioned, but it is not limited to this.

The alkenyl group of C2 to C20 includes a straight or branched alkenyl group, and specifically, may include an allyl group, ethenyl group, propenyl group, butenyl group, pentenyl group, and the like, but is not limited thereto.

The C6 to C20 aryl groups include monocyclic or condensed aryl groups, and specifically include phenyl groups, biphenyl groups, naphthyl groups, phenanthrenyl groups, and fluorenyl groups, but are not limited thereto.

Examples of the alkoxy group for C1 to C20 include a methoxy group, an ethoxy group, a phenyloxy group, a cyclohexyloxy group, and the like, but are not limited thereto.

The alkoxyalkyl group of C2 to C20 is a functional group in which at least one hydrogen of the alkyl group as described above is substituted with an alkoxy group, specifically, a methoxymethyl group, methoxyethyl group, ethoxymethyl group, iso-propoxymethyl group, iso-propoxy Alkoxyalkyl groups such as ethyl group, iso-propoxypropyl group, iso-propoxyhexyl group, tert-butoxymethyl group, tert-butoxyethyl group, tert-butoxypropyl group and tert-butoxyhexyl group; Or an aryloxyalkyl group such as a phenoxyhexyl group, but is not limited thereto.

The C7 to C20 arylalkyl group includes a functional group in which at least one hydrogen of the alkyl group as described above is substituted with an aryl group, and specifically includes a phenylmethyl group, phenylethyl group, biphenylmethyl group, naphthylmethyl group, and the like. It is not limited only to this.

Examples of the C7 to C20 alkylaryl group include a functional group in which at least one hydrogen of the aryl group is substituted with an alkyl group, and specifically includes methylphenyl group, ethylphenyl group, methylbiphenyl group, methylnaphthyl group, and the like. However, the present invention is not limited thereto.

Examples of the alkenyl group of C2 to C20 include one or more forms in which two carbons of the alkyl groups as described above are connected by a double bond, and the same as described above in the alkyl group except for including the double bond Can be defined.

The C1 to C20 alkylsilyl group or C1 to C20 alkoxysilyl group is a functional group in which 1 to 3 hydrogens of -SiH ₃ are substituted with 1 to 3 alkyl or alkoxy groups as described above, specifically, methylsilyl group, di Alkylsilyl groups such as methylsilyl group, trimethylsilyl group, dimethylethylsilyl group, diethylmethylsilyl group or dimethylpropylsilyl group; Alkoxy silyl groups, such as a methoxy silyl group, a dimethoxy silyl group, a trimethoxy silyl group, or a dimethoxyethoxy silyl group; Alkoxy alkyl silyl groups, such as a methoxy dimethyl silyl group, a diethoxy methyl silyl group, or a dimethoxy propyl silyl group, are mentioned, but it is not limited to this.

The C1 to C20 silylalkyl group is a functional group in which at least one hydrogen of the alkyl group as described above is substituted with a silyl group, and specifically -CH ₂ -SiH ₃ , methylsilylmethyl group or dimethylethoxysilylpropyl group, and the like. However, the present invention is not limited thereto.

The halogen may be fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).

The sulfonate group has a structure of —O—SO ₂ —R ^′ , and R ^′ may be an alkyl group having 1 to 20 carbon atoms. Specifically, the C1 to C20 sulfonate group may include a methanesulfonate group or a phenylsulfonate group, but is not limited thereto.

In addition, in the present specification, that two substituents adjacent to each other are connected to each other to form an aliphatic or aromatic ring means that the atom (s) of the two substituents and the valences (atoms) to which the two substituents are bonded are connected to each other to form a ring. Means that. Specifically, examples of R _a and R _b or R _a or R _a and R _{b '} of —NR _a R _b or —NR _{a ′} R _{b ′} connected to each other to form an aliphatic ring include a piperidinyl group and the like. For example, R _a and R _b of -NR _a R _b or -NR _{a '} R _b' or R _{a '} and R _{b '} are linked to each other to form an aromatic ring include a pyrrolyl group and the like. It can be illustrated.

The above-mentioned substituents are optionally a hydroxyl group within the range to exhibit the same to similar effects as the desired effect; halogen; Alkyl or alkenyl, aryl, alkoxy groups; An alkyl group or an alkenyl group, an aryl group, an alkoxy group containing at least one hetero atom of the group 14 to 16 hetero atoms; Silyl groups; Alkylsilyl group or alkoxysilyl group; Phosphine groups; Phosphide groups; Sulfonate groups; And it may be substituted with one or more substituents selected from the group consisting of sulfone groups.

Examples of the Group 4 transition metal include titanium (Ti), zirconium (Zr), hafnium (Hf), and the like, but are not limited thereto.

Conventionally, an olefin polymer prepared by using a catalyst on which one type of transition metal compound is supported exhibited poor bubble stability. For this reason, the olefin polymer manufactured using the catalyst in which one type of transition metal compound was carried was difficult to form a film stably when processed by a melt blown method or the like.

However, using the hybrid supported catalyst according to an embodiment of the present invention can maintain the processability of the olefin polymer and ensure excellent drop impact strength, it is possible to manufacture an olefin polymer excellent in high processability, especially melt blow processability .

Specifically, in the hybrid supported catalyst according to an embodiment of the present invention, the first transition metal compound includes a long chain branch (LCB) and is easy to prepare a low molecular weight olefin polymer, and the second transition metal The compound contains less amount of long chain branches compared to the first transition metal compound and is easier to prepare relatively high molecular weight olefin polymers. In particular, there are many long chain branches in the polymer and the melt strength increases when the molecular weight is large. However, in the case of the first transition metal compound, there are limitations in improving bubble stability because the molecular weight is low compared to the long chain branches.

In the present invention, the first metallocene compound that contains a relatively large long chain branch and produces a low molecular weight polymer, and the second metallocene that produces a relatively large short chain branch (SCB) and a high molecular weight polymer The mixed strength of the compound was improved to improve melt strength while maintaining excellent transparency. By hybridly supporting the two metallocene compounds, the long-chain branching present in the polymer is located on a relatively low molecular weight side, so that transparency is not deteriorated.

In particular, the hybrid supported catalyst of the present invention is characterized in that the long chain branch produced by the first transition metal compound of Formula 1 and the long chain branch produced by the second transition metal compound of Formula 2 are entangled with each other at the molecular level. The entanglement between the long chain branches increases the melt strength because a large force is required to release in the molten state. Melt blending of the homopolymers of each catalyst did not show an improvement in the melt strength, indicating that the melt strength was effective when entangled from the polymerization step by the hybrid supported catalyst.

More specifically, in the hybrid supported catalyst according to an embodiment of the present invention, the first metallocene compound represented by Formula 1 is a different ligand, and the transition metal compound is a cyclopentadienyl ligand and a tetrahydroindenyl ligand. It includes, The ligands are cross-linked by -Si (Q ₁ ) (Q ₂ )-, and has a structure in which M ₁ (X ₁ ) (X ₂ ) is present between the ligands. Polymerization of the catalyst of this structure provides a polymer having a small amount of long chain branching and a relatively narrow molecular weight distribution (PDI, MWD, Mw / Mn) and a melt flow rate ratio (MFRR).

Specifically, the cyclopentadienyl ligand in the structure of the transition metal compound represented by Formula 1, for example, may affect the olefin polymerization activity.

In particular, R ₁₁ to R ₁₄ of the cyclopentadienyl ligand are each independently a transition metal compound of Formula 1 when any one of an alkyl group of C1 to C20, an alkoxy group of C1 to C20 and an alkenyl group of C2 to C20 The catalyst obtained from the above may exhibit higher activity in the olefin polymerization process, and when R ₁₁ to R ₁₄ are each independently any one of a methyl group, an ethyl group, a propyl group and a butyl group, the hybrid supported catalyst is a polymerization process of an olefin monomer. Can exhibit very high activity.

In addition, by having a non-covalent electron pair that can act as a Lewis base to the tetrahydroindenyl ligand structure in the structure of the transition metal compound represented by the formula (1), it is possible to exhibit a stable, high polymerization activity, and the tetrahydroindenyl The ligand can, for example, easily adjust the molecular weight of the olefin polymer produced by adjusting the degree of steric hindrance effect according to the type of substituted functional group.

Specifically, in Formula 1, R ₁ may be any one of hydrogen, an alkyl group of C1 to C20, an alkoxy group of C1 to C20, and an alkenyl group of C2 to C20. More specifically, in Formula 1, R ₁ may be hydrogen or an alkyl group of C1 to C20, and R ₂ to R ₁₀ may each be hydrogen. In this case, the hybrid supported catalyst can provide an olefin polymer having excellent processability.

In addition, in the structure of the transition metal compound represented by Formula 1, the cyclopentadienyl ligand and the tetrahydroindenyl ligand may be crosslinked by -Si (Q ₁ ) (Q ₂ )-to exhibit excellent stability. . In order to more effectively secure this effect, Q ₁ and Q ₂ may each independently be either an alkyl group of C1 to C20 or an aryl group of C6 to C20. More specifically, Q ₁ and Q ₂ are each independently a transition metal compound wherein any one of a methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, t-butyl group, phenyl group, and benzyl group Can be used.

M ₁ (X ₁ ) (X ₂ ) present between the cyclopentadienyl ligand and tetrahydroindenyl ligand in the structure of the transition metal compound represented by Formula 1 may affect the storage stability of the metal complex. Can be. In order to more effectively secure this effect, X ₁ and X ₂ may each independently be any one of halogen, C 1 to C 20 alkyl group and C 1 to C 20 alkoxy group. More specifically, X ₁ and X ₂ may be each independently a halogen or an alkyl group of C1 to C20, or may be F, Cl, Br or I. And M ₁ is Ti, Zr or Hf; Zr or Hf; Or Zr.

Specifically, Q ₁ and Q ₂ may be an alkyl group of C1 to C20 or an aryl group of C6 to C20, or may be an alkyl group of C1 to C6 or an aryl group of C6 to C12, respectively. For example, Q ₁ and Q ₂ may each be methyl, ethyl, n-propyl, iso-propyl, hexyl, or phenyl.

Specifically, T ₁ may be carbon, silicon, or germanium, for example silicon.

Specifically, R ₁ to R ₁₄ may each be hydrogen, an alkyl group of C1 to C20, or an aryl group of C6 to C20. More specifically, R ₁ may be hydrogen or an alkyl group of C1 to C20, or may be hydrogen or an alkyl group of C1 to C3. For example, R ₁ may be hydrogen or methyl. In addition, R ₂ to R ₁₀ may each be hydrogen. R ₁₁ to R ₁₄ may each be hydrogen or an alkyl group of C1 to C20, or may be hydrogen or an alkyl group of C1 to C3. For example, R ₁₁ to R ₁₄ can each be hydrogen or methyl.

As an example, as a first transition metal compound capable of providing an olefin polymer having increased drop impact strength and high short chain branching content and having excellent blown film processability, the compound of Formula 1 is represented by the following structural formulae. It may be a compound, but is not limited thereto.

,

,

,

,

,

,

,

,

,

,

,

.

,

,

,

.

Ph in the above structural formula represents a phenyl group.

The first transition metal compound represented by Chemical Formula 1 may be synthesized by applying known reactions. Specifically, a tetrahydroindenyl derivative and a cyclopentadiene derivative may be prepared by connecting a bridge compound to prepare a ligand compound, and then performing metallation by adding a metal precursor compound, but is not limited thereto. For more detailed synthesis methods, see Examples.

On the other hand, in the hybrid supported catalyst according to an embodiment of the present invention, the transition metal compound represented by the formula (2) is a different ligand to have a cyclopentadienyl ligand and substituents (R ₂₀ and R ₂₄ ) at a specific position And a different ligand is cross-linked by -Si (Q ₃ ) (Q ₄ )-and has a structure in which M ₂ (X ₃ ) (X ₄ ) is present between the different ligands. . If a transition metal compound having such a specific structure is activated by a suitable method and used as a catalyst in the polymerization reaction of an olefin, long chain branching is possible. As such, by introducing substituents (R ₂₀ and R ₂₄ ) at specific positions of the indene derivative of the general formula (2), polymerization activity is higher than that of an unsubstituted indene compound or a metallocene compound containing an indene compound substituted at another position. This can have high characteristics.

Particularly, in the case of the second metallocene compound represented by Chemical Formula 2, the molecular weight is about 15 to 550,000 when homopolymerized and has a short chain branch (SCB) so that a narrow molecular weight distribution is applied to the hybrid catalyst. While having a property that can improve the workability.

Specifically, the cyclopentadienyl ligand in the structure of the transition metal compound represented by Formula 2, for example, may affect the olefin polymerization activity.

In particular, each of R ₂₅ to R ₂₈ of the cyclopentadienyl ligand is independently hydrogen, C 1 to C 20 alkyl group, C 2 to C 20 alkoxyalkyl group, or C 6 to C 20 aryl group of Formula 1 The catalyst obtained from the transition metal compound may exhibit higher activity in the olefin polymerization process, wherein R ₂₅ and R ₂₈ are each hydrogen, and R ₂₆ and R ₂₇ are each independently hydrogen, an alkyl group of C1 to C20, or C2 to C20 In the case of the alkoxyalkyl group, the hybrid supported catalyst may exhibit very high activity in the polymerization process of the olefin monomer.

In addition, the indenyl ligand in the structure of the transition metal compound represented by Chemical Formula 2 may, for example, easily adjust the molecular weight of the olefin polymer prepared by controlling the degree of steric hindrance effect according to the type of the substituted functional group. have.

Specifically, a phenyl group is substituted at the 4th position of the indenyl group, and R ₂₀ , which is a para position of the phenyl group, may be a C1 to C20 alkyl group, and a substituent R ₂₄ at the 6th position of the indenyl group may also be C1. It is preferable to have an alkyl groupyl of C20 to the aspect of raising the molecular weight. In particular, R ₂₀ and R ₂₄ may each independently be an alkyl group of C1 to C4, R ₂₀ may preferably be a methyl group, an ethyl group, n-propyl group, iso-propyl group, etc., and R ₂₄ is preferably May be a t-butyl group. In this case, the hybrid supported catalyst can provide an olefin polymer having excellent copolymerizability.

The remaining substituents R ₁₅ to R ₁₉ and R ₂₁ to R ₂₃ of the indenyl group are each independently hydrogen, halogen, C1 to C20 alkyl group, C1 to C20 haloalkyl, C2 to C20 alkenyl group, C2 to C20 Alkoxyalkyl group, C1 to C20 alkylsilyl group, C1 to C20 silylalkyl group, C1 to C20 alkoxysilyl group, C1 to C20 alkoxy group, C6 to C20 aryl group, C7 to C20 alkylaryl group, or C7 To arylalkyl group of C20.

In addition, in the structure of the transition metal compound represented by Formula 2, the cyclopentadienyl ligand and indenyl ligand may be crosslinked by -Si (Q ₃ ) (Q ₄ )-to exhibit excellent stability. In order to more effectively secure this effect, each of Q ₃ and Q _{4 may} be independently an alkyl group of C1 to C20 or an alkoxyalkyl group of C2 to C20. More specifically, Q ₃ and Q ₄ are each independently methyl, ethyl, n-propyl, iso-propyl, n-butyl, t-butyl, methoxymethyl, methoxyethyl, ethoxymethyl, iso A transition metal compound which is any one of -propoxymethyl group, iso-propoxyethyl group, iso-propoxyhexyl group, tert-butoxymethyl group, tert-butoxyethyl group and tert-butoxyhexyl group can be used.

In particular, the transition metal compound represented by Formula 2 is any one or more of the substituents R ₂₆ , R ₂₇ of the cyclopentadiene (Cp), or the substituents Q ₃ , Q ₄ of the silyl group is an alkoxyalkyl group of C 2 to C 20, specifically Any one or more of Q ₃ , Q ₄ , R ₂₆ , and R ₂₇ may be a C6 to C12 alkoxyalkyl group, and iso-propoxyethyl group, iso-propoxypropyl group, iso-propoxyhexyl group, tert-butoxyethyl group, tert-butoxypropyl group, tert-butoxyhexyl group, and the like. More specifically, any one or more of Q ₃ , Q ₄ , R ₂₆ , and R ₂₇ may be a tert-butoxyhexyl group. As described above, when the transition metal compound represented by Chemical Formula 2 has at least one alkoxyalkyl group, the leaching phenomenon does not occur between the precursor and the carrier due to the chemical reaction between the alkoxyalkyl group and the carrier, and thus is well supported. Activity may increase due to this.

This may affect the copolymerizability of the alpha olefin comonomers such as 1-butene or 1-hexene, wherein the alkoxyalkyl group of C2 to C20 is less than or equal to C4. This is because when the short alkyl group chain is used, the copolymerization with respect to the alpha olefin comonomer is lowered while maintaining the overall polymerization activity, thereby making it possible to prepare a polyolefin having a controlled copolymerization degree without deteriorating other physical properties. In particular, in order to increase the copolymerizability with respect to the alpha olefin comonomer, the alkoxyalkyl group has a long alkyl group chain of C5 to C20, for example, t-butoxy hexyl group is added to the alpha olefin comonomer. It is more desirable because there is no space limitation.

Specifically, Q ₃ and Q ₄ may each be a C1 to C20 alkyl group or a C2 to C20 alkoxyalkyl group, or may be a C1 to C6 alkyl group or a C6 to C12 alkoxyalkyl group. For example, Q ₃ and Q ₄ are methyl, ethyl, n-propyl, iso-propyl, hexyl, iso-propoxyethyl group, iso-propoxypropyl group, iso-propoxyhexyl group, tert-butoxyethyl group, tert, respectively. -Butoxypropyl group, or tert-butoxyhexyl group.

Specifically, T ₂ may be carbon, silicon, or germanium, for example silicon.

Specifically, M ₂ may be Ti, Zr or Hf, or Zr or Hf, or Zr.

Specifically, X ₃ and X ₄ may each independently be a halogen, an alkyl group of C1 to C20, and an alkoxy group of C1 to C20. More specifically, X ₁ and X ₂ may be each independently a halogen or an alkyl group of C1 to C20, or may be F, Cl, Br or I.

Specifically, R ₁₅ to R ₁₉ , R ₂₁ to R ₂₃ , and R ₂₅ to R ₂₈ may each be hydrogen, a C1 to C20 alkyl group, a C2 to C20 alkoxyalkyl group, or a C6 to C20 aryl group. In addition, R ₂₀ and R ₂₄ may be the same as or different from each other, and each independently may be hydrogen or an alkyl group of C1 to C20.

More specifically, R ₂₀ and R ₂₄ may each be hydrogen or an alkyl group of C1 to C4, for example hydrogen, methyl, iso-propyl, or tert-butyl. In addition, R ₂₅ and R ₂₈ may each be hydrogen. R ₂₆ and R ₂₇ may each be hydrogen, a C1 to C20 alkyl group, or a C2 to C20 alkoxyalkyl group, or may each be hydrogen, a C1 to C3 alkyl group, or a C6 to C12 alkoxyalkyl group. For example, R ₂₆ and R ₂₇ can each be hydrogen, methyl, or tert-butoxyhexyl. In addition, R ₁₅ to R ₁₉ and R ₂₁ to R ₂₃ may each be hydrogen.

In addition, M ₂ (X ₃ ) (X ₄ ) present between the cyclopentadienyl ligand and tetrahydroindenyl ligand in the structure of the transition metal compound represented by Formula 2 affects the storage stability of the metal complex. Can have To more effectively secure this effect, X ₃ and X ₄ may each independently be any one of halogen, an alkyl group of C1 to C20 and an alkoxy group of C1 to C20. More specifically X ₃ and X ₄ may each independently be F, Cl, Br or I, and M ₂ is Ti, Zr or Hf; Zr or Hf; Or Zr.

Meanwhile, specific examples of the second transition metal compound represented by Chemical Formula 2 may include a compound represented by the following structural formula, but the present invention is not limited thereto.

,

,

,

,

,

.

,

.

As such, the hybrid supported metallocene catalyst of the embodiment may include the first and second metallocene compounds, thereby preparing a polyolefin having not only excellent processability but also excellent physical properties, particularly drop impact strength.

In particular, the mixing mole ratio of the first metallocene compound and the second metallocene compound should be about 1.2: 1 to 7.5: 1, specifically 1.5: 1 to 7.0: 1, or 1.8: 1 to 6.5: 1. Or 3.5: 1 to 6.2: 1. The mixing molar ratio of the first metallocene compound and the second metallocene compound is controlled in terms of physical properties to satisfy both physical properties and processability by controlling the molecular weight, the amount of SCB (short chain branch) and LCB (long chain branch). Should be at least 1.2: 1 and at most 7.5: 1 in terms of processability.

On the other hand, the first and second transition metal compound has the above-described structural characteristics can be stably supported on the carrier.

As the carrier, a carrier containing a hydroxyl group or a siloxane group may be used. Specifically, the carrier may be a carrier containing a highly reactive hydroxyl group or siloxane group by drying at a high temperature to remove moisture on the surface. More specifically, silica, alumina, magnesia, or a mixture thereof may be used as the carrier, and among these, silica may be more preferable. The carrier may be dried at high temperature, for example, silica, silica-alumina, silica-magnesia, etc. dried at high temperature may be used, and these are usually Na ₂ O, K ₂ CO ₃ , BaSO ₄ and Mg ( Oxides, carbonates, sulfates, nitrates, such as NO ₃ ) _2, and the like.

The drying temperature of the carrier is preferably about 200 to 800 ° C, more preferably about 300 to 600 ° C, and most preferably about 300 to 400 ° C. If the drying temperature of the carrier is less than about 200 ° C., there is too much moisture to react with the surface water and the promoter, and if it exceeds about 800 ° C., the pores on the surface of the carrier are combined to reduce the surface area, and also the surface is hydroxy. It is not preferable because there are not many groups and only siloxane groups are left to decrease the reaction site with the promoter.

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

If the amount of the hydroxy group is less than about 0.1 mmol / g, the reaction site with the promoter is small. If the amount of the hydroxy group is greater than about 10 mmol / g, it may be due to moisture other than the hydroxyl group present on the surface of the carrier particle. Not desirable

In addition, in the mixed-supported metallocene catalyst of the embodiment, as a co-catalyst supported on a carrier for activating the metallocene compound, it is an organometallic compound containing a Group 13 metal, and under a general metallocene catalyst It will not be specifically limited if it can be used when superposing | polymerizing an olefin.

Specifically, the cocatalyst compound may include at least one of an aluminum-containing first cocatalyst of Formula 3, and a borate-based second cocatalyst of Formula 4 below.

[Formula 3]

R _a- [Al (R _b ) -O] _n -R _c

In Chemical Formula 3,

R _a , R _b , and R _c are the same as or different from each other, and are each independently hydrogen, halogen, a C1 to C20 hydrocarbyl group, or a C1 to C20 hydrocarbyl group substituted with halogen;

n is an integer of 2 or more;

[Formula 4]

T ⁺ [BG ₄ ] ^-

In Formula 4, T ⁺ is a + monovalent polyatomic ion, B is boron in a +3 oxidation state, and G is independently a hydride group, a dialkylamido group, a halide group, an alkoxide group, an aryl oxide group, Selected from the group consisting of hydrocarbyl groups, halocarbyl groups and halo-substituted hydrocarbyl groups, wherein G has up to 20 carbons, but at less than one position G is a halide group.

The first cocatalyst of Chemical Formula 3 may be an alkylaluminoxane compound having a repeating unit bonded in a linear, circular, or reticular form. Specific examples of the first cocatalyst include methylaluminoxane (MAO) and ethylalumina. Noxic acid, isobutyl aluminoxane, or butyl aluminoxane etc. are mentioned.

In addition, the second cocatalyst of Formula 4 may be a borate-based compound in the form of a trisubstituted ammonium salt, or a dialkyl ammonium salt, a trisubstituted phosphonium salt. Specific examples of the second cocatalyst include trimetalammonium tetraphenylborate, methyldioctadecylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate , Methyltetracyclocyclodecylammonium tetraphenylborate, N, N-dimethylaninium tetraphenylborate, N, N-diethylaninium tetraphenylborate, N, N-dimethyl (2,4,6-trimethylaninynium Tetraphenylborate, trimethylammonium tetrakis (pentafluorophenyl) borate, methylditetradecylammonium tetrakis (pentaphenyl) borate, methyldioctadecylammonium tetrakis (pentafluorophenyl) borate, triethylammonium, tetra Kis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammo Tetrakis (pentafluorophenyl) borate, Tri (tert-butyl) ammoniumtetrakis (pentafluorophenyl) borate, N, N-dimethylaninium tetrakis (pentafluorophenyl) borate, N, N-di Ethylanylnium tetrakis (pentafluorophenyl) borate, N, N-dimethyl (2,4,6-trimethylaninynium) tetrakis (pentafluorophenyl) borate, trimethylammoniumtetrakis (2,3,4, 6-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-dimethylaninium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N, N-diethylaninynium tetrakis (2,3,4,6-tetrafluoro Borates in the form of trisubstituted ammonium salts, such as rophenyl) borate or N, N-dimethyl- (2,4,6-trimethylaninynium) tetrakis- (2,3,4,6-tetrafluorophenyl) borate compound; Borate type in the form of dialkyl ammonium salt, such as dioctadecyl ammonium tetrakis (pentafluorophenyl) borate, ditetradecyl ammonium tetrakis (pentafluorophenyl) borate, or dicyclohexyl ammonium tetrakis (pentafluorophenyl) borate compound; Or triphenylphosphonium tetrakis (pentafluorophenyl) borate, methyldioctadecylphosphonium tetrakis (pentafluorophenyl) borate or tri (2,6-, dimethylphenyl) phosphonium tetrakis (pentafluorophenyl And a borate compound in the form of a trisubstituted phosphonium salt such as) borate.

In the hybrid supported metallocene catalyst of the above embodiment, the mass ratio of the total transition metal to the carrier included in the first metallocene compound and the second metallocene compound may be 1:10 to 1: 1000. When the carrier and the metallocene compound are included in the mass ratio, an optimal shape can be exhibited.

In addition, the mass ratio of the promoter compound to the carrier may be 1: 1 to 1: 100. When the cocatalyst and the carrier are included in the mass ratio, the active and polymer microstructures can be optimized.

The hybrid supported metallocene catalyst of the above embodiment can be used for polymerization of olefinic monomers as such. In addition, the hybrid supported metallocene catalyst may be prepared and used as a prepolymerized catalyst by contact reaction with an olefinic monomer. For example, the catalyst may be used separately from olefins such as ethylene, propylene, 1-butene, 1-hexene, 1-octene, and the like. It can also be prepared and used as a prepolymerized catalyst by contacting the system monomer.

On the other hand, the hybrid supported metallocene catalyst of the embodiment, the step of supporting the promoter on the carrier; Supporting the first and second metallocene compounds on the carrier on which the promoter is supported; It may be prepared by a manufacturing method comprising a.

In this case, the first and second metallocene compounds may be supported one by one in sequence, or two may be supported together. At this time, the supporting order is not limited, but by first supporting the second metallocene catalyst having a relatively poor morphology, the shape of the hybrid supported metallocene catalyst may be improved, and accordingly, After supporting the strong catalyst, the first metallocene catalyst may be sequentially supported.

In the above method, the supporting conditions are not particularly limited and can be carried out in a range well known to those skilled in the art. For example, it is possible to proceed by using a high temperature support and a low temperature support as appropriate, for example, the support temperature is possible in the range of about -30 ℃ to 150 ℃, preferably room temperature (about 25 ℃) to about 100 ℃ More preferably from room temperature to about 80 ° C. The supporting time can be appropriately adjusted according to the amount of the metallocene compound to be supported. The reacted supported catalyst can be used by filtering or removing the reaction solvent by distillation under reduced pressure, and, if necessary, by using a Soxhlet filter with an aromatic hydrocarbon such as toluene.

In addition, the preparation of the supported catalyst may be performed under a solvent or a solvent-free. When a solvent is used, usable solvents include aliphatic hydrocarbon solvents such as hexane or pentane, aromatic hydrocarbon solvents such as toluene or benzene, hydrocarbon solvents substituted with chlorine atoms such as dichloromethane, ethers such as diethyl ether or THF Most organic solvents, such as a solvent, acetone, and ethyl acetate, are mentioned, and hexane, heptane, toluene, or dichloromethane is preferable.

On the other hand, according to another embodiment of the present invention, there may be provided a method for producing a polyolefin comprising the step of polymerizing the olefin monomer in the presence of the hybrid supported metallocene catalyst.

And, the olefin monomer is ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dode Sen, 1-tetradecene, 1-hexadecene, 1-aitocene, norbornene, nobornadiene, ethylidene nobodene, phenyl nobodene, vinyl nobodene, dicyclopentadiene, 1,4-butadiene, 1, It may be at least one selected from the group consisting of 5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene and 3-chloromethyl styrene. Specifically, the olefinic monomer may be at least one of ethylene, propylene, 1-butene, and 1-hexene.

For the polymerization reaction of the olefin monomer, various polymerization processes known as the polymerization reaction of the olefin monomer, such as a continuous solution polymerization process, bulk polymerization process, suspension polymerization process, slurry polymerization process or emulsion polymerization process may be employed. This polymerization reaction can be carried out at a temperature of about 25 to 500 ° C., or about 25 to 200 ° C., or about 50 to 150 ° C., and under a pressure of about 1 to 100 bar or about 10 to 80 bar.

In addition, in the polymerization reaction, the hybrid supported metallocene catalyst may be used in a dissolved or diluted state in a solvent such as pentane, hexane, heptane, nonane, decane, toluene, benzene, dichloromethane, chlorobenzene, and the like. At this time, by treating the solvent with a small amount of alkylaluminum or the like, a small amount of water or air which may adversely affect the catalyst can be removed in advance.

In addition, the olefin polymer prepared by the method as described above may exhibit excellent blown film processability without increasing molecular weight distribution as it is prepared using the hybrid supported catalyst described above, and may exhibit high drop impact strength.

Specifically, the olefin polymer may have a molecular weight distribution (MWD) of 2.5 to 4.0, more specifically 2.8 to 3.7, more specifically 2.8 to 3.4. In addition, the olefin polymer may have a drop impact strength of 800 g or more or 800 g to 1800 g, or 900 g or more, or 900 g to 1600 g, measured according to ASTM D1709 A.

In addition, the olefin polymer may have the above-described molecular weight distribution and drop impact strength characteristics and at the same time have a weight average molecular weight of 10,000 g / mol to 5,000,000 g / mol, more specifically 50,000 g / mol to 250,000 g / mol.

The olefin polymer has a melt index (MI) of 0.5 g / 10 min to 1.5 g / 10 min, more specifically 0.85 g / 10 min to 1.4 g /, measured according to ASTM D1238 specification under a temperature of 190 ° C. and a load of 2.16 kg. It can be 10min. In addition, the olefin polymer has a melt flow rate (MFR21.6) measured under a temperature of 190 ° C. and a load of 21.6 kg according to ISO 1133, and a melt flow rate (MFR2. The melt flow index (MFRR, 21.6 / 2.16) divided by 16) may be 30 to 90, more specifically 30 to 50.

In addition, when the polymer to be polymerized using the hybrid supported catalyst described above is, for example, an ethylene-alpha olefin copolymer, preferably an ethylene-1-hexene copolymer, the above-described physical properties can be more suitably satisfied.

When using the hybrid supported metallocene catalyst according to the present invention, it is excellent in workability, there is a feature capable of producing a polyolefin appearing to an excellent degree such as drop impact strength.

1 is a graph measuring drop impact strength, FT-IR, and processing load of an olefin polymer prepared through a polymerization process using the hybrid supported metallocene catalyst of Examples 1 to 3 and Comparative Example 3 of the present invention. It is shown.

The invention is explained in more detail in the following examples. However, the following examples are merely to illustrate the invention, but the content of the present invention is not limited by the following examples.

< Example >

< Metallocene  Compound Synthesis Example >

Synthesis Example  One: First transition  Metal compound

Preparation of 1-1 Ligand Compound

Tetramethylcyclopentadiene (TMCP) was used as tetramethylcyclopentyl-Li salts (TMCP-Li salts) after filtering by lithiation with n-BuLi (1 equivalent) in THF (0.4 M). Indene was lithiated with Hexane (0.5 M) n-BuLi (1 equivalent), filtered and used as Ind-Li salts. In a 250 mL Schlenk flask, 50 mmol of tetramethylcyclopentyl-Li salts (TMCP-Li salts) and about 100 mL of tetrahydrofuran (THF) were added under Ar. 1 equivalent of dichloromethyl- (iso-propyl) silane was added at -20 ° C. After about 6 hours, 3 mol% of CuCN and Ind-Li salts (50 mmol, MTBE 1M solution) were added at -20 ° C and reacted for about 12 hours. The organic layer was separated with water and Hexane to obtain a ligand.

1-2 Metallocene  Preparation of the compound

50 mmol of the ligand compound synthesized in 1-1 was added to a dried 250 mL Schlenk flask, dissolved in 100 mL of MTBE under Ar, and 2 equivalents of n-BuLi were added dropwise at -20 ° C. After about 16 hours, a Ligand-Li solution was added to ZrCl ₄ (THF) ₂ (50 mmol, MTBE 1 M solution). After the reaction for about 16 hours, the solvent was removed, dissolved in methylene chloride (MC) and filtered to remove LiCl. After removing the solvent of the filtrate, about 50 mL of MTBE and about 100 mL of Hexane were added and stirred for about 2 hours to obtain a solid metallocene catalyst precursor.

The metallocene catalyst precursor (20 mmol) obtained above, 60 mL of DCM, and 5 mol% of a Pd / C catalyst were charged in an argon atmosphere. The argon inside the high pressure reactor was replaced with hydrogen three times and filled with hydrogen to bring the pressure to about 20 bar. Stirring at 35 ° C. for 24 hours completes the reaction. Substitute the inside with argon and transfer the DCM solution to the schlenk flask under argon atmosphere. This solution was passed through celite under argon to remove the Pd / C catalyst and to dry the solvent to obtain a solid catalyst precursor.

¹ H NMR (500 MHz, C6D6): 0.62 (3H, s), 0.98 (3H, d), 1.02 (3H, d), 1.16 (2H, dd), 1.32-1.39 (3H, m), 1.78 (3H , s), 1.81 (3H, s), 1.84-1.94 (3H, m), 2.01 (3H, s), 2.03 (1H, m), 2.04 (3H, s), 2.35 (2H, m), 2.49- 2.55 (1 H, m), 3.13-3.19 (1 H, m), 5.27 (1 H, d), 6.75 (1 H, d).

Synthesis Example  2: First transition  Metal compound

Preparation of 2-1 Ligand Compound

Tetramethylcyclopentadiene (TMCP) was used as tetramethylcyclopentyl-Li salts (TMCP-Li salts) after filtering by lithiation with n-BuLi (1 equivalent) in THF (0.4 M). Indene was lithiated with Hexane (0.5 M) n-BuLi (1 equivalent), filtered and used as Ind-Li salts. In a 250 mL Schlenk flask, 50 mmol of tetramethylcyclopentyl-Li salts (TMCP-Li salts) and 100 mL of tetrahydrofuran (THF) were added under Ar. 1 equivalent of dichloromethylphenyl silane was added at -20 ° C. After about 6 hours, 3 mol% of CuCN and Ind-Li salts (50 mmol, MTBE 1M solution) were added at -20 ° C and reacted for about 12 hours. The organic layer was separated with water and Hexane to obtain a ligand.

2-2 Metallocene  Preparation of the compound

50 mmol of the ligand compound synthesized in 2-1 was added to a dried 250 mL Schlenk flask, dissolved in about 100 mL of MTBE under Ar, and 2 equivalents of n-BuLi were added dropwise at -20 ° C. After about 16 hours, a Ligand-Li solution was added to ZrCl ₄ (THF) ₂ (50 mmol, MTBE 1 M solution). After the reaction for about 16 hours, the solvent was removed, dissolved in methylene chloride (MC) and filtered to remove LiCl. After removing the solvent of the filtrate, about 50 mL of MTBE and about 100 mL of Hexane were added and stirred for about 2 hours to obtain a solid metallocene catalyst precursor.

The metallocene catalyst precursor (20 mmol) obtained above, 60 mL of DCM, and 5 mol% of a Pd / C catalyst were charged in an argon atmosphere. The argon inside the high pressure reactor was replaced with hydrogen three times and filled with hydrogen to bring the pressure to about 20 bar. Stirring at about 35 ° C. for about 24 hours completes the reaction. After replacing the inside with argon, the DCM solution was transferred to the schlenk flask under argon atmosphere. The solution was passed through celite under argon to remove the Pd / C catalyst, and the solvent was dried to obtain a metallocene compound (A, B form) having different stereoisomers at a ratio of 1.3: 1.

¹ H NMR (500 MHz, CDCl ₃ ):

Form A: 0.88 (3H, s), 1.43-1.50 (1H, m), 1.52-1.57 (1H, m), 1.60 (3H, s), 1.62-1.68 (1H, m), 1.87-1.95 (1H, m), 1.95-2.00 (1H, m), 2.00 (3H, s), 2.06 (3H, s), 2.08 (3H, s), 2.41-2.47 (1H, m), 2.72-2.78 (1H, m) , 3.04-3.10 (1H, m), 5.62 (1H, d), 6.73 (1H, d), 7.49 (3H, m), 7.87 (2H, m)

Form B: 0.99 (3H, s), 1.42 (3H, s), 1.60-1.67 (2H, m), 1.90-1.98 (1H, m), 1.95 (3H, s), 2.06 (3H, s), 2.06 -2.10 (1H, m), 2.11 (3H, s), 2.44-2.49 (1H, m), 2.66-2.70 (1H, m), 2.74-2.79 (1H, m), 3.02-3.11 (1H, m) , 5.53 (1H, d), 6.74 (1H, d), 7.48 (3H, m), 7.88 (2H, m).

Synthesis Example  3: Second transition  Metal compound

Preparation of 3-1 Ligand Compound

11.618 g (40 mmol) of 4- (4- (tert-butyl) phenyl) -2-isopropyl-1H-indene was added to a dried 250 mL schlenk flask, and 100 mL of THF was injected under argon. After cooling the diethylether solution to 0 ℃, 18.4 mL (46 mmol) of 2.5 M nBuLi hexane solution was slowly added dropwise. The reaction mixture was slowly raised to room temperature and stirred until the next day. In another 250 mL schlenk flask, 12.0586 g of dichloromethyltethersilane (40 mmol, calculated at 90% purity) and a solution of 100 mL of Hexane were prepared. The Schlenk flask was cooled to -30 ° C, and a lithiated solution was added dropwise thereto. After the injection, the mixture was slowly raised to room temperature and stirred for one day. The next day, 33.6 mL of NaCp in 2M THF was added dropwise and stirred for one day. Then, 50 mL of water was added to the flask to quench, and the organic layer was separated and dried over MgSO ₄ . As a result, 23.511 g (52.9 mmol) of oil were obtained (NMR purity purity / wt% = 92.97%. Mw = 412.69).

3-2 Metallocene  Preparation of the compound

Ligated in an oven dried 250 mL schlenk flask, dissolved in 80 mL of toluene and 19 mL of MTBE (160 mmol, 4 equiv.), And then added 2.1 equivalent of nBuLi solution (84 mmol, 33.6 mL) to lithiation until the next day. One equivalent of ZrCl ₄ (THF) ₂ was taken in a glove box and placed in a 250 mL schlenk flask to prepare a suspension containing Ether. After cooling both flasks to -20 ℃, ligand anion was slowly added to the Zr suspension. After the injection was over, the reaction mixture was slowly raised to room temperature. After stirring for one day, MTBE in the mixture was filtered directly under argon with a Schlenk Filter to remove LiCl generated after the reaction. After removal, the remaining filtrate was removed by vacuum depressurization, and a small amount of pentane was added to a small amount of dichloromethane as a reaction solvent. The reason for adding pentane at this time is that the synthesized catalyst precursor promotes crystallization because of poor solubility in pentane. The slurry was filtered under argon to determine whether the remaining filter cake and filtrate were catalytically synthesized through NMR, respectively, and weighed and sampled in a glove box to confirm the yield and purity (Mw = 715.04).

¹ H NMR (500 MHz, CDCl ₃ ): 0.60 (3H, s), 1.01 (2H, m), 1.16 (6H, s), 1.22 (9H, s), 1.35 (4H, m), 1.58 (4H, m), 2.11 (1H, s), 3.29 (2H, m), 5.56 (1H, s), 5.56 (2H, m), 5.66 (2H, m), 7.01 (2H, m), 7.40 (3H, m ), 7.98 (2H, m)

Synthesis Example  4: Second transition  Metal compound

Preparation of 4-1 Ligand Compound

6-tert-butoxyhexyl chloride and sodium cyclopentadiene (2 equivalents) were added under THF, followed by stirring. After completion of the reaction, the solution was worked up with water and excess cyclopentadiene was distilled off. 27 mL of toluene was added to 4.45 g (20 mmol) of 6-tert-butoxyhexylcyclopentadiene obtained by the above procedure. The temperature was lowered to -20 ° C and 8.8 mL (22 mmol) of 2.5 M n-BuLi Hexane solution was added dropwise and stirred overnight at room temperature.

5.8 g (20 mmol) of 4- (4- (tert-butyl) phenyl) -2-isopropyl-1H-indene was added to a dried 250 mL Schlenk flask, and 33 mL of MTBE was added thereto. The temperature was lowered to -20 ° C and 8.8 mL (22 mmol) of 2.5M n-BuLi Hexane solution was added dropwise and stirred overnight at room temperature. The temperature was lowered to -20 ℃ and 1.5 equivalents of dichlorodimethyl silane was added. The mixture was stirred at room temperature overnight and distilled to remove excess dichlorodimethyl silane.

A solution lithiated with 6-tert-butoxyhexylcyclopentadiene was added to the flask and stirred overnight. The ligand synthesized by this process was worked up to obtain a ligand compound.

4-2 Metallocene  Preparation of the compound

11.4 g (20 mmol) of the ligand compound synthesized in 4-1 was dissolved in 50 mL of toluene, and about 16.8 mL (42 mmol) of 2.5M nBuLi hexane solution was added dropwise, followed by stirring at room temperature overnight. 20 mmol of ZrCl ₄ (THF) ₂ was added and stirred overnight. When the reaction was completed, Filtration was performed to remove LiCl. All solvents were removed, crystallized with Hexane, and purified to obtain metallocene compounds having different stereoisomers (A, B form) at a ratio of 1.3: 1.

¹ H NMR (500 MHz, C ₆ D ₆ ):

Form A: 0.58 (3H, s), 0.55 (3H, s), 0.93-0.97 (3H, m), 1.12 (9H, s), 1.28 (9H, s), 1.27 (3H, d), 1.35-1.42 (1H, m), 1.45-1.62 (4H, m), 2.58-2.65 (1H, m), 2.67-2.85 (2H, m), 3.20 (2H, t), 5.42 (1H, m), 5.57 (1H , m), 6.60 (1H, m), 6.97 (1H, dd), 7.27 (1H, d), 7.39-7.45 (4H, m), 8.01 (2H, dd)

Form B: 0.60 (3H, s), 0.57 (3H, s), 0.93-0.97 (3H, m), 1.11 (9H, s), 1.28 (9H, s), 1.32 (3H, d), 1.35-1.42 (1H, m), 1.45-1.62 (4H, m), 2.58-2.65 (1H, m), 2.67-2.85 (2H, m), 3.23 (2H, t), 5.24 (1H, m), 5.67 (1H , m), 6.49 (1H, m), 6.97 (1H, dd), 7.32 (1H, d), 7.39-7.45 (4H, m), 8.01 (2H, dd)

compare Synthesis Example  One: First transition  Metal compound

Preparation of 5-1 Ligand Compound

3.7 g (40 mmol) of 1-chlorobutane was added to a dried 250 mL Schlenk flask and dissolved in 40 mL of THF. 20 mL of sodium cyclopentadienylide THF solution was slowly added thereto, followed by stirring for one day. 50 mL of water was added to the reaction mixture for quenching, extraction with ether (50 mL x 3), and the combined organic layers were washed with brine. The remaining moisture with MgSO ₄ was dried, filtered and the solvent was removed under vacuum reduced pressure to yield 2-butyl-cyclopenta-1,3-diene, a dark brown viscous form, in quantitative yield.

5-2 Metallocene  Preparation of the compound

About 4.3 g (23 mmol) of the ligand compound synthesized in 5-1 was added to a dried 250 mL Schlenk flask and dissolved in about 60 mL of THF. To this was added about 11 mL of n-BuLi 2.0M hexane solution (28 mmol) and stirred for one day, and the solution was then dispersed in about 50 mL of ether with 3.83 g (10.3 mmol) of ZrCl ₄ (THF) ₂ . Was added slowly at -78 ° C.

When the reaction mixture was raised to room temperature, the pale yellow suspension turned from a pale yellow suspension into a suspension form. After stirring for one day, the solvents of the reaction mixture were all dried, and about 200 mL of hexane was added to sonication to settle. The hexane solution in the upper layer was collected by decantation with cannula. The hexane solution obtained by repeating this process twice was dried under vacuum reduced pressure to confirm that bis (3-butyl-2,4-dien-yl) zirconium (IV) chloride, a pale yellow solid, was produced.

¹ H NMR (500 MHz, CDCl ₃ ): 0.91 (6H, m), 1.33 (4H, m), 1.53 (4H, m), 2.63 (4H, t), 6.01 (1H, s), 6.02 (1H, s ), 6.10 (2H, s), 6.28 (2H, s)

compare Synthesis Example  2: Second transition  Metal compound

Preparation of 6-1 Ligand Compound

5.5688 g (20 mmol) of tertbutylfluorene was added to a dried 250 mL schlenk flask, and 80 mL of diethylether was injected under argon. After cooling the diethylether solution to 0 ℃ 9.6 mL (24 mmol) of 2.5 M nBuLi hexane solution was slowly added dropwise. The reaction mixture was slowly raised to room temperature and stirred until the next day. In another 250 mL schlenk flask, a solution of 7.2 mL (60 mmol) of dimethyldichlorosilane and 80 mL of Hexane was prepared. The Schlenk flask was cooled to -78 ° C, and a lithiated solution was added dropwise thereto. After the injection, the mixture was slowly raised to room temperature and stirred for one day. At the same time, 20 mmol of tether Cyclopentadienylide was cooled to 0 ° C. in diethylether solvent, and 9.6 mL (24 mmol) of 2.5 M nBuLi hexane solution was slowly added dropwise to carry out Lithiation reaction for one day. The following day, chloro (2,7-di-tert-butyl-9H-fluoren-9-yl) dimethylsilane and Lithiated tether cyclopentadienylide flasks were combined with Cannula at room temperature. The direction to pass to the cannula does not affect the experiment. After stirring for one day, 50 mL of water was added to the flask to quench and the organic layer was separated and dried over MgSO ₄ . As a result, 11.204 g (20.12 mmol, 100.6%) of oil were obtained (NMR purity purity / wt% = 100%. Mw = 556.95).

¹ H NMR (500 MHz, CDCl ₃ ): -0.46 (3H, s), 0.02 (3H, s), 0.89 (9H, s), 1.38 (8H, m), 1.52 (2H, m), 3.32 (2H , m), 3.89 (1H, s), 3.99 (1H, s), 5.65 (1H, s), 6.05 (1H, s), 6.44 (1H, s), 7.37 (2H, m), 7.54 (2H, m), 7.74 (2H, m)

6-2 Metallocene  Preparation of the compound

The ligand compound synthesized in 6-1 was added to a 250 mL schlenk flask dried in an oven, dissolved in Ether, and then 2.1 equivalent of nBuLi solution (42 mmol, 16.8 mL) was added to lithiation until the next day. One equivalent of ZrCl ₄ (THF) ₂ was taken in a glove box and placed in a 250 mL schlenk flask to prepare a suspension containing Ether. After cooling both flasks to -20 ℃, ligand anion was slowly added to the Zr suspension. After the injection was over, the reaction mixture was slowly raised to room temperature. After stirring for one day, Ether in the mixture was filtered directly under argon with Schlenk Filter to remove LiCl produced after the reaction. After removal, the remaining filtrate was removed by vacuum depressurization and pentane was added to the volume of the reaction solvent. The reason for adding pentane at this time is that the synthesized catalyst precursor promotes crystallization because of poor solubility in pentane. (When recrystallization with hexane, it was soluble and recrystallization with pentane.) The pentane solution was stored in a freezer at -30 ℃ for 1 day to crystallize. The slurry was filtered under argon, filtered and the filtered solid and filtrate All evaporated under vacuum reduced pressure. The filter cake and filtrate remaining on the above were checked for catalyst synthesis through NMR, respectively, and weighed and sampled in a glove box to confirm yield and purity. After confirmation, the recrystallization process was repeated twice to obtain 1.91 g of Filter cake (Mw = 717.06, Yield: 13.3%).

¹ H NMR (500 MHz, CDCl ₃ ): 1.13 (3H, s), 1.14 (3H, s), 1.15 (9H, s), 1.24 (4H, m), 1.43 (18H, s), 1.44 (4H, m), 2.34 (1H, m), 2.43 (1H, m), 3.26 (2H, t), 5.32 (1H, s), 5.60 (1H, s), 6.24 (1H, s), 7.37 (1H, s ), 7.44 (1H, s), 7.66 (2H, d), 7.99 (2H, m)

compare Synthesis Example  3: Second transition  Metal compound

7-1 Preparation of Ligand Compound

3.663 g (30 mmol) of tetramethylcyclopentadienylide was added to a dried 250 mL schlenk flask, and 80 mL of THF was injected under argon. After cooling the diethylether solution to 0 ℃ 14.4 mL (36 mmol) of 2.5 M nBuLi hexane solution was slowly added dropwise. The reaction mixture was slowly raised to room temperature and stirred until the next day. All solvents were distilled and filtered in Hexane to obtain 2.502 g (19.526 mmol) of tetramethyl cyclopentadieny litium salt (TmCpLi salt). In another 250 mL schlenk flask, a solution of 7.56 g (58.6 mmol) of dichlorodimethylsilane and 80 mL of Hexane was prepared, and the Schlenk flask was cooled to −30 ° C., and then a lithiated solution was added dropwise thereto. After the injection, the mixture was slowly raised to room temperature and stirred for one day. At the same time, 19.526 mmol of 4- (4- (tert-butyl) phenyl) -2-methyl-1H-indene was cooled to 0 ° C. in THF solvent and then slowly added dropwise 9.0 mL (22.5 mmol) of 2.5 M nBuLi hexane solution During the Lithiation reaction. The next day the two flasks were combined with Cannula at room temperature. The direction to pass to the cannula does not affect the experiment. After stirring for one day, 50 mL of water was added to the flask to quench and the organic layer was separated and dried over MgSO ₄ . As a result, 9.187 g (19.597 mmol, 100.4%) of oil was obtained (NMR-based purity (wt%) = 100%. Mw = 468.8).

7-2 Metallocene  Preparation of the compound

In a 250 mL schlenk flask dried in an oven, the ligand compound synthesized in 7-1 was dissolved in 60 mL of methyl tert-butyl ether (MTBE), and 2.1 equivalents of n-BuLi solution (41.15 mmol, 16.5 mL) was added and lithiation was performed until the next day. One equivalent of ZrCl ₄ (THF) ₂ was taken in a glove box and placed in a 250 mL schlenk flask to prepare a suspension containing Ether. After cooling both flasks to -20 ℃, ligand anion was slowly added to the Zr suspension. After the injection, the reaction mixture is slowly raised to room temperature. After stirring for one day, MTBE in the mixture was filtered directly under argon with a Schlenk Filter to remove LiCl generated after the reaction. After the removal, the remaining filtrate was removed by vacuum depressurization, and a small amount of pentane was added to a small amount of dichloromethane as a reaction solvent. The reason for adding pentane at this time is that the synthesized catalyst precursor promotes crystallization because of poor solubility in pentane. The slurry was filtered under argon to determine whether the remaining filter cake and filtrate were catalytically synthesized through NMR, respectively, and weighed and sampled in a glove box to confirm yield and purity. If dichloromethane (DCM) is not completely removed, it may affect the production of the supported catalyst later, and it was confirmed that almost no dichloromethane remained by repeating the distillation process by adding hexane (Hx, Hexane). 2.596 g of the product was confirmed, and NMR analysis showed that DCM contained 2.02 wt% and Hx 1.32 wt%. Mw = 628.91. Yield: 20.5% Purity (wt%): 96.65%

¹ H NMR (500 MHz, CDCl ₃ ): 0.75 (3H, s), 0.82 (3H, s), 0.93 (3H, t), 1.21 (9H, s), 1.27 (3H, m), 1.82 (6H, m), 1.84 (3H, s), 1.99 (3H, s), 2.91 (1H, m), 6.91 (1H, m), 7.41-7.48 (5H, m), 8.00 (2H, m)

compare Synthesis Example  4: second transition metal compound

8-1 Preparation of Ligand A

4.0 g (30 mmol) of 1-benzothiophene was dissolved in THF to prepare a 1-benzothiophene solution. And 14 mL (36 mmol, 2.5 M in hexane) of n-BuLi solution and 1.3 g (15 mmol) of CuCN were added to the 1-benzothiophene solution.

Then, 3.6 g (30 mmol) of tigloyl chloride was slowly added to the solution at -80 ° C, and the obtained solution was stirred at room temperature for about 10 hours.

Thereafter, 10% HCl was poured into the solution to quench the reaction, and the organic layer was separated with dichloromethane to give a beige solid (2E) -1- (1-benzothien-2-yl) -2- Methyl-2-buten-1-one was obtained.

¹ H NMR (CDCl ₃ ): 7.85-7.82 (m, 2H), 7.75 (m, 1 H), 7.44-7.34 (m, 2 H), 6.68 (m, 1H), 1.99 (m, 3H), 1.92 (m , 3H)

A solution of 5.0 g (22 mmol) of (2E) -1- (1-benzothien-2-yl) -2-methyl-2-buten-1-one prepared above in 5 mL of chlorobenzene was vigorously heated. 34 mL of sulfuric acid was slowly added to the solution with gentle stirring. The solution was then stirred at room temperature for about 1 hour. Thereafter, ice water was poured into the solution, and the organic layer was separated with an ether solvent to give a yellow solid of 1,2-dimethyl-1,2-dihydro-3H-benzo [b] cyclopenta [d] thiophen-3-one. 4.5 g (91% yield) was obtained.

¹ H NMR (CDCl ₃ ): 7.95-7.91 (m, 2H), 7.51-7.45 (m, 2H), 3.20 (m, 1H), 2.63 (m, 1H), 1.59 (d, 3H), 1.39 (d , 3H)

Dissolve 2.0 g (9.2 mmol) of 1,2-dimethyl-1,2-dihydro-3H-benzo [b] cyclopenta [d] thiophen-3-one in a mixed solvent of 20 mL of THF and 10 mL of methanol. To the solution was added 570 mg (15 mmol) of NaBH ₄ at 0 ° C. The solution was then stirred at room temperature for about 2 hours. Thereafter, HCl was added to the solution to adjust the pH to 1, and the organic layer was separated with an ether solvent to obtain an alcohol intermediate.

The solution was prepared by dissolving the alcohol intermediate in toluene. Then, 190 mg (1.0 mmol) of p-toluenesulfonic acid was added to the solution, and the mixture was refluxed for about 10 minutes. The resulting reaction mixture was separated by column chromatography, orange-brown in color, liquid 1,2-dimethyl-3H-benzo [b] cyclopenta [d] thiophene (ligand A) 1.8 g (9.0 mmol, 98 % yield).

¹ H NMR (CDCl ₃ ): 7.81 (d, 1H), 7.70 (d, 1H), 7.33 (t, 1H), 7.19 (t, 1H), 6.46 (s, 1H), 3.35 (q, 1H), 2.14 (s, 3H), 1.14 (d, 3H)

8-1 Preparation of Ligand B

13 mL (120 mmol) of t-butylamine and 20 mL of ether solvent were added to a 250 mL schlenk flask, and (6-tert-butoxyhexyl) dichloro (methyl) silane 16 was added to the flask and another 250 mL schlenk flask. g (60 mmol) and 40 mL of an ether solvent were added to prepare a t-butylamine solution and a (6-tert-butoxyhexyl) dichloro (methyl) silane solution, respectively. The t-butylamine solution was cooled to −78 ° C., and then (6-tert-butoxyhexyl) dichloro (methyl) silane solution was slowly injected into the cooled solution, which was stirred at room temperature for about 2 hours. It was. The resulting white suspension was filtered to give an ivory color and liquid 1- (6- (tert-butoxy) hexyl) -N- (tert-butyl) -1-chloro-1-methylsilaneamine (ligand) B) was obtained.

¹ H NMR (CDCl ₃ ): 3.29 (t, 2H), 1.52-1.29 (m, 10H), 1.20 (s, 9H), 1.16 (s, 9H), 0.40 (s, 3H)

8-3 Crosslinking of Ligands A and B

1.7 g (8.6 mmol) of 1,2-dimethyl-3H-benzo [b] cyclopenta [d] thiophene (ligand A) was added to a 250 mL schlenk flask, and 30 mL of THF was added to prepare a ligand A solution. Prepared. After cooling the ligand A solution to -78 ° C, 3.6 mL (9.1 mmol, 2.5 M in hexane) of n-BuLi solution was added to the ligand A solution, which was stirred overnight at room temperature to give a purple-brown solution. Got it. Solution A was prepared by replacing the solvent of the purple-brown solution with toluene, and dissolving 39 mg (0.43 mmol) of CuCN in 2 mL of THF.

Meanwhile, Solution B prepared by injecting 1- (6- (tert-butoxy) hexyl) -N- (tert-butyl) -1-chloro-1-methylsilaneamine (ligand B) and toluene into a 250 mL schlenk flask. Was cooled to -78 ° C. The solution A prepared above was slowly injected into the cooled solution B. And the mixture of solution A and B was stirred overnight at room temperature. The resulting solid was filtered to remove the brownish, viscous liquid 1- (6- (tert-butoxy) hexyl) -N- (tert-butyl) -1- (1,2-dimethyl 4.2 g (> 99% yield) of -3H-benzo [b] cyclopenta [d] thiophen-3-yl) -1-methylsilamine (crosslinked product of ligands A and B) were obtained.

In order to confirm the structures of the crosslinked products of the ligands A and B, the crosslinked product was lithiated at room temperature, and then H-NMR spectra were obtained using a sample dissolved in a small amount of pyridine-D5 and CDCl ₃ .

¹ H NMR (pyridine-D5 and CDCl ₃ ): 7.81 (d, 1H), 7.67 (d, 1H), 7.82-7.08 (m, 2H), 3.59 (t, 2H), 3.15 (s, 6H), 2.23 -1.73 (m, 10H), 2.15 (s, 9H), 1.91 (s, 9H), 1.68 (s, 3H)

8-4 Metallocene  Preparation of the compound

In a 250 mL schlenk flask, 1- (6- (tert-butoxy) hexyl) -N- (tert-butyl) -1- (1,2-dimethyl-3H-benzo [b] cyclopenta [d] 4.2 g (8.6 mmol) of thiophen-3-yl) -1-methylsilaneamine (crosslinked product of ligands A and B) were added, and 14 mL of toluene and 1.7 mL of n-hexane were added to the flask to dissolve the crosslinked product. I was. After cooling this solution to -78 ° C, 7.3 mL (18 mmol, 2.5 M in hexane) of n-BuLi solution was injected into the cooled solution. The solution was then stirred at room temperature for about 12 hours. Subsequently, 5.3 mL (38 mmol) of trimethylamine was added to the solution, and the solution was stirred at about 40 ° C. for about 3 hours to prepare Solution C.

Meanwhile, 2.3 g (8.6 mmol) of TiCl ₄ (THF) ₂ and 10 mL of toluene were added to a 250 mL schlenk flask prepared separately, to prepare a solution D in which TiCl ₄ (THF) ₂ was dispersed in toluene. The solution C prepared before the solution D was slowly injected at −78 ° C., and the mixture of solutions C and D was stirred at room temperature for about 12 hours. Thereafter, the solution was depressurized to remove the solvent, and the solute obtained was dissolved in toluene. The solid not dissolved in toluene was filtered off and the solvent was removed from the filtered solution to obtain 4.2 g (83% yield) of the first transition metal compound in the form of a brown solid.

¹ H NMR (CDCl ₃ ): 8.01 (d, 1H), 7.73 (d, 1H), 7.45-7.40 (m, 2H), 3.33 (t, 2H), 2.71 (s, 3H), 2.33 (d, 3H ), 1.38 (s, 9H), 1.18 (s, 9H), 1.80-0.79 (m, 10H), 0.79 (d, 3H)

<Mixed support Metallocene  Preparation of the catalyst Example >

Example  One

(1) carrier preparation

Silica (SP 952, manufactured by Grace Davision) was dehydrated and dried at 600 ° C. under vacuum for 12 hours.

(2) Preparation of promoter-supported carrier

20 g of dried silica was placed in a glass reactor, and a methylaluminoxane (MAO) solution containing aluminum in an amount of 13 mmol was added to the toluene solution. The reaction was slowly stirred at 40 ° C. for 1 hour. After the reaction was completed, the reaction mixture was washed several times with a sufficient amount of toluene until the unreacted aluminum compound was completely removed, and the remaining toluene was removed under reduced pressure at 50 ° C. As a result, 32 g of the promoter supported carrier (MAO / SiO ₂ ) were obtained (Al content in the supported catalyst = 17 wt%).

(3) Preparation of Hybrid Supported Metallocene Catalyst

12 g of the promoter-supported carrier (MAO / SiO ₂ ) prepared above was placed in a glass reactor, and then 70 mL of toluene was added and stirred. As a first transition metal compound, a solution prepared by dissolving the compound prepared in Synthesis Example 1 (0.06 mmol) and the compound prepared in Synthesis Example 3 (0.01 mmol) in toluene was added to the glass reactor, followed by 2 hours at 40 ° C. The reaction was stirred while stirring. Thereafter, the reaction product was washed with a sufficient amount of toluene and then vacuum dried to obtain a hybrid supported metallocene catalyst as a solid powder. At this time, the mixing molar ratio of the first metallocene compound and the second metallocene compound was 6: 1.

Example  2

A hybrid supported metallocene catalyst was prepared in the same manner as in Example 1 except that the metallocene compound molar ratios of Synthesis Example 1 (0.04 mmol) and Synthesis Example 3 (0.01 mmol) were used differently from 4: 1. It was.

Example  3

A hybrid supported metallocene catalyst was prepared in the same manner as in Example 1, except that the metallocene compound molar ratios of Synthesis Example 1 (0.2 mmol) and Synthesis Example 3 (0.1 mmol) were used in different amounts of 4: 1. It was.

Example  4

A hybrid supported metallocene catalyst was prepared in the same manner as in Example 2, except that the metallocene compounds of Synthesis Example 1 (0.4 mmol) and Synthesis Example 4 (0.1 mmol) were used.

Example  5

A hybrid supported metallocene catalyst was prepared in the same manner as in Example 2, except that the metallocene compounds of Synthesis Example 2 (0.40 mmol) and Synthesis Example 4 (0.1 mmol) were used.

Comparative example  One

The supported metallocene catalyst was prepared in the same manner as in Example 1, except that only the metallocene compound of Synthesis Example 1 (0.1 mmol) was used without adding the second metallocene compound.

Comparative example  2

The supported metallocene catalyst was prepared in the same manner as in Example 1, except that only the metallocene compound of Synthesis Example 3 (0.1 mmol) was used without adding the first metallocene compound.

Comparative example  3

A hybrid supported metallocene catalyst was prepared in the same manner as in Example 1, except that the molar ratio of the metallocene compound of Synthesis Example 1 (0.8 mmol) and Synthesis Example 3 (0.1 mmol) was changed to 8: 1. It was.

Comparative example  4

A hybrid supported metallocene catalyst was prepared in the same manner as in Example 2, except that the metallocene compound of Synthesis Example 1 (0.4 mmol) and Comparative Synthesis Example 1 (0.1 mmol) were used.

Comparative example  5

The metallocene compound of Synthesis Example 1 (0.1 mmol) and Synthesis Example 2 (0.2 mmol) was used, except that the molar ratio of the metallocene compound was 1: 2, in the same manner as in Example 1 A hybrid supported metallocene catalyst was prepared.

Comparative example  6

A hybrid supported metallocene catalyst was prepared in the same manner as in Example 5, except that the metallocene compound of Synthesis Example 2 (0.4 mmol) and Comparative Synthesis Example 2 (0.1 mmol) were used.

Comparative example  7

A hybrid supported metallocene catalyst was prepared in the same manner as in Example 1, except that the molar ratio of the metallocene compound of Synthesis Example 1 (0.11 mmol) and Synthesis Example 3 (0.1 mmol) was changed to 1.1: 1. It was.

Comparative example  8

A hybrid supported metallocene catalyst was prepared in the same manner as in Example 1, except that the metallocene compounds of Comparative Synthesis Example 1 (0.06 mmol) and Synthesis Example 3 (0.01 mmol) were used.

Comparative example  9

A hybrid supported metallocene catalyst was prepared in the same manner as in Example 1, except that the metallocene compound of Synthesis Example 1 (0.06 mmol) and Comparative Synthesis Example 3 (0.01 mmol) was used.

Comparative example  10

A hybrid supported metallocene catalyst was prepared in the same manner as in Example 1, except that the metallocene compound of Synthesis Example 1 (0.06 mmol) and Comparative Synthesis Example 4 (0.01 mmol) was used.

< Test Example : Olefin Polymer Manufacturing>

Ethylene-1- Hexene  Copolymerization

The supported catalyst (90 mg) prepared in Examples 1 to 5 was quantified in a dry box, placed in a 50 mL glass bottle, sealed with a rubber septum, and taken out of the dry box to prepare a catalyst to be injected. The polymerization was carried out in a 2 L autoclave high pressure reactor equipped with a mechanical stirrer and temperature controlled and available at high pressure.

2 mL of triethylaluminum (1M in Hexane) was added to the reactor, 0.6 kg of hexane was added thereto, and the temperature was raised to 80 ° C. while stirring at 500 rpm. The mixed supported metallocene catalyst (90 mg) and hexane (20 mL) prepared above were added to a vial, and 50 g of 1-hexene and 0.2 kg of hexane were added thereto. When the internal temperature of the reactor reached 80 ° C., the reaction was carried out for 1 hour while stirring at 500 rpm under ethylene pressure of 30 bar. The polymer obtained after completion of the reaction was first removed hexane through a filter, and then dried for 3 hours at 80 ℃ oven to obtain an ethylene-1 hexene copolymer.

The polymerization conditions using the supported catalysts of Examples 1 to 5 are collectively shown in Table 1 below.

Example 1 Example 2 Example 3 Example 4 Example 5 Support form concoction
Support concoction
Support concoction
Support concoction
Support concoction
Support Metallocene
Compound composition Synthesis Example 1
Synthesis Example 3 Synthesis Example 1
Synthesis Example 3 Synthesis Example 1
Synthesis Example 3 Synthesis Example 1
Synthesis Example 4 Synthesis Example 2
Synthesis Example 4 Transition metal
compound
Rate (molar ratio) 6: 1 4: 1 2: 1 4: 1 4: 1 Polymerization temperature
(℃) 85 85 85 85 85 Polymerization pressure (bar) 40 40 40 40 40 Polymerization time (min) 30 30 30 30 30 Hydrogen input amount (wt%) 0.175 0.18 0.19 0.18 0.18 1-hexene (g) 50 50 50 50 50

On the other hand, using the supported catalyst prepared in Comparative Examples 1 to 10, an ethylene-1 hexene copolymer was obtained by the same method as the polymerization process carried out using the supported catalyst of the previous embodiment.

The polymerization conditions using the supported catalysts of Comparative Examples 1 to 10 are collectively shown in Table 2 below.

Comparative example
One Comparative example
2 Comparative example
3 Comparative example
4 Comparative example
5 Comparative example
6 Comparative example
7 Comparative example
8 Comparative example
9 Comparative example
10 Support
shape Exclusive
Support Exclusive
Support concoction
Support concoction
Support concoction
Support concoction
Support concoction
Support concoction
Support concoction
Support concoction
Support Metallocene
compound
Furtherance Synthesis Example 1 Synthesis Example 3 Synthesis Example 1
Synthesis Example 3 Synthesis Example 1
compare
Synthesis Example 1 Synthesis Example 1 Synthesis Example 2 Synthesis Example 2
compare
Synthesis Example 2 Synthesis Example 1 Synthesis Example 3 compare
Synthesis Example 1
Synthesis Example 3 Synthesis Example 1
compare
Synthesis Example 3 Synthesis Example 1
compare
Synthesis Example 4 Transition metal
compound
Rate (molar ratio) - - 8: 1 4: 1 1: 2  4: 1 1.1: 1 6: 1 6: 1 6: 1 Polymerization temperature
(℃) 85 85 85 85 85 85 85 85 85 85 Polymerization pressure
(bar) 40 40 40 40 40 40 40 40 40 40 Polymerization time (min) 30 30 30 30 30 30 30 30 30 30 Hydrogen input amount (wt%) - - 0.17 0.16 0.13 0.18 0.21 0.175 0.175 0.175 1-hexene (g) 50 50 50 50 50 50 50 50 50 50

As described above, the activity of the catalyst in the polymerization process using the supported catalysts of Examples and Comparative Examples and the physical properties of the prepared ethylene-1 hexene copolymer are shown in Table 3 below.

(1) Catalytic Activity (kgPE / gCat): Activity of the catalyst used in each Example and Comparative Examples by measuring the mass of the catalyst used in the synthesis reaction of the Examples and Comparative Examples and the mass of the polymer produced from the reaction ) Was calculated.

(2) Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn, PDI): Pretreatment by dissolving 10 mg of sample in 1,2,4-Trichlorobenzene containing 0.0125% BHT for 10 hours using PL-SP260 for 10 hours Then, the number average molecular weight (Mn) and the weight average molecular weight (Mw) were measured at a measurement temperature of 160 ° C using PLGPC220. PDI is expressed as the ratio (Mw / Mn) of the weight average molecular weight and the number average molecular weight.

(3) Melt Index (MI _2.16 ) and Melt Flow Index (MFRR _{21 .6 / 2.16} ): Melt Index (MI _{2. 16} ) is in accordance with ASTM D1238 (Condition E, 190 ° C, 2.16kg Load) Measured. Melt flow index _{(Melt Flow Rate Ratio, MFRR 21} .6 / 2. 16) was calculated by dividing the MFR _{21 .6} to MFR _{2 .16,} MFR _{21 .6} is the temperature, and 21.6 kg of 190 ℃ according to ISO 1133 measured under a load and, MFR _{2 .16} is measured under a load of 2.16 kg and a temperature of 190 ℃ according to ISO 1133.

(4) Melting point (Tm): The melting point of the polymer was measured using a differential scanning calorimeter (DSC, device name: DSC 2920, manufacturer: TA instrument). Specifically, the polymer was heated to 220 ° C. and then maintained at that temperature for 5 minutes, cooled to 20 ° C. again, and then increased in temperature, wherein the rate of rise and fall of the temperature was adjusted to 10 ° C./min, respectively. It was.

(5) SCB (short chain branch, FT-IR): The short chain branch (SCB) value is measured by measuring the complex viscosity according to frequency using TA instrument's ARES (advanced rheometric expansion system) and using Van Gurp- The plateau delta value, which is the mean value of the plateau section, in the palmen plot was calculated.

Specifically, the measurement sample was a gap of 2.0mm by using parallet plates of 25.0mm diameter at 190 ℃. The measurement was performed in the dynamic strain frequency sweep mode, measuring 5% strain, 0.05 rad / s to 500 rad / s, and 10 points in each decade. Power law fitting was performed using TA Orchestrator, a measurement program.

(5) Drop impact strength (g): Drop impact strength was measured by measuring at least 20 times per film sample according to the ASTM D1709 A standard related to impact resistance.

(6) Processing load (bar): With respect to extrusion processability, the resins prepared in Examples and Comparative Examples were subjected to cylinder-1 / -2 / -3 / die = 180/185/185 using a Haake extruder. The processing load (bar) was measured at / 190 and 40 rpm speed.

activation
(kgPE / gCat) MI _2.16 MFRR
(21.6 / 2.16) Mw
(× 10 ³
g / mol) PDI Tm
(℃) SCB
(FT-IR) Drop Impact Strength ^*
(g) Processing
Load (bar) Example 1 5.2 0.88 27.5 103 2.9 117.1 18.6 910 310 Example 2 5.6 0.91 24.2 102 2.8 116.5 19.2 1,100 320 Example 3 4.5 0.9 23.9 97 3 117.3 20.7 1,400 324 Example 4 5.3 0.95 24.3 101 2.8 117.3 19.1 1,040 318 Example 5 5.1 0.9 24.6 95 2.9 117.5 18.8 1,000 328 Comparative Example 1 3.5 1.8 46.3 278 3.5 129.6 11.2 200 283 Comparative Example 2 5.3 0.4 19.7 421 2.3 128.7 16.8 610 381 Comparative Example 3 4.9 0.8 34.1 110 2.8 120.8 17.4 760 305 Comparative Example 4 4.4 0.8 23.2 105 2.7 116.3 18.3 730 336 Comparative Example 5 3.6 1.31 35.6 94 3.9 127 14.5 500 295 Comparative Example 6 3.3 1.08 23.6 98 2.8 128.1 12.6 550 365 Comparative Example 7 3.7 0.91 21.4 113 3.3 128.9 14.1 590 376 Comparative Example 8 6.4 0.83 18.9 107 2.8 117.8 14.2 890 396 Comparative Example 9 2.4 0.85 29.4 107 3.0 117.6 14.9 620 310 Comparative Example 10 3.6 0.54 28.6 135 4.1 115.6 18.1 690 330 ^* MI 1.0 conversion value

On the other hand, using the hybrid supported metallocene catalyst of Examples 1 to 3 and Comparative Example 3, the graph of the drop impact strength, FT-IR, processing load for the olefin polymer prepared through the polymerization process is shown in Figure 1 It was. As shown in Figure 1, when the polymerization is carried out using the catalyst of Examples 1 to 3, the processability is maintained by the LCB expression by the first transition metal compound selected from the compound represented by the formula (1), It can be seen that a product having excellent drop impact strength according to SCB increase can be obtained by the second transition metal compound selected from the compounds represented by 2. Accordingly, it can be seen that when Examples 1 to 3 catalysts are used, all of the excellent processability can be secured together with the improvement of physical properties in a trade-off relationship.

In addition, from the results of Table 3, it was confirmed that Examples 1 to 5 can obtain an excellent drop impact strength due to many short-chain branches while maintaining workability by long-chain branches. Specifically, Examples 1 to 5, while implementing a high drop impact strength of 910 g to 1400 g, while maintaining the processing load as low as 310 to 328 bar, it can be seen that it is possible to produce a polymer that satisfies both physical properties and processability .

In particular, Example 1 exhibited excellent drop impact strength in the presence of more than 18.5 short chain branches. In addition, in Example 2, it can be seen that the number of short chain branches increased as the ratio of Synthesis Example 3 producing a large number of short chain branches and a high molecular weight polymer was controlled by controlling the transition metal compound molar ratio. Example 3 In addition, as in Example 2, the number of short chain branches was further increased according to the control of the molar ratio of the transition metal compound, and thus the drop impact strength was excellent. Example 4 is a case where the synthesis example 4 is applied, it can be seen that the drop impact strength is excellent by generating a number of short-chain branches. In Example 5, it can be seen that excellent physical properties were maintained through hybridization with the synthesis example for producing many short-chain branches, even though the metallocene compound for producing long-chain branches was changed.

On the contrary, in Comparative Example 1, only the transition metal of Synthesis Example 1 corresponding to Formula 1 produced a polymer, and thus a long chain branch was included, so that the processing load was excellent, but the drop impact strength was greatly reduced. In addition, when the polymer is produced only by the transition metal of Synthesis Example 3 corresponding to Chemical Formula 2 as in Comparative Example 2, a problem arises in that the processing load increases due to the absence of long chain branching. As shown in Comparative Example 3, when the ratio of the transition metal ratios of Synthesis Example 1 and Synthesis Example 3 to 8: 1, physical properties did not improve. In case of using the transition metal compound of Comparative Synthesis Example 1, which does not correspond to Formula 2, even though the transition metal compound of Synthesis Example 1 was maintained in Comparative Example 4, the drop impact strength was not excellent enough and the processing load increased. Appeared. Also in the case of Comparative Example 5, in the case of using the transition metal compound of Synthesis Example 2 which is not a compound corresponding to the formula (2), while maintaining the transition metal compound of Synthesis Example 1 similarly to Comparative Example 4, the number and falling of short chain branches The problem was that the impact strength was significantly lowered. In addition, in the case of using the transition metal compound of Comparative Synthesis Example 2, which does not correspond to the formula (2) in the case of Comparative Example 6, even if the ratio of the transition metal compound is maintained, short chain branch is not sufficiently formed and accordingly the drop impact strength Showed a low problem. In the case of Comparative Example 7, the hydrogen input increased with the change of the ratio of the transition metal compound, resulting in problems such as deterioration of activity and physical properties and increase in processing load. In the case of Comparative Examples 8 to 10, while changing the transition metal compound of the supported catalyst, problems such as deterioration of physical properties such as catalyst activity and hardness, or increase in processing load appeared.

Claims (12)

At least one first transition metal compound selected from compounds represented by Formula 1;
At least one second transition metal compound selected from compounds represented by Formula 2; And
A carrier supporting the first and second transition metal compounds;
Including,
Wherein the first and second transition metal compounds are included in a molar ratio of 1.2: 1 to 7.5: 1,
Hybrid Supported Metallocene Catalysts:
[Formula 1]

In Chemical Formula 1,
Q ₁ and Q ₂ are the same as or different from each other, and each independently halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkoxyalkyl group, C6 to C20 aryl group, C7 to C20 alkylaryl Or an arylalkyl group of C7 to C20;
T ₁ is carbon, silicon, or germanium;
M ₁ is a Group 4 transition metal;
X ₁ and X ₂ are the same as or different from each other, and each independently halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C6 to C20 aryl group, nitro group, amido group, C1 to C20 alkylsilyl group , A C1 to C20 alkoxy group, or a C1 to C20 sulfonate group;
R ₁ to R ₁₄ are the same as or different from each other, and each independently hydrogen, halogen, C1 to C20 alkyl group, C1 to C20 haloalkyl group, C2 to C20 alkenyl group, C1 to C20 alkylsilyl group, C1 to C20 Is a silylalkyl group, C1 to C20 alkoxysilyl group, C1 to C20 alkoxy group, C6 to C20 aryl group, C7 to C20 alkylaryl group, or C7 to C20 arylalkyl group, or R ₁ to R ₁₄ Two or more adjacent to each other are connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring;
[Formula 2]

In Chemical Formula 2,
Q ₃ and Q ₄ are the same as or different from each other, and each independently halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkoxyalkyl group, C6 to C20 aryl group, C7 to C20 alkylaryl Or an arylalkyl group of C7 to C20;
T ₂ is carbon, silicon, or germanium;
M ₂ is a Group 4 transition metal;
X ₃ and X ₄ are the same as or different from each other, and each independently halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C6 to C20 aryl group, nitro group, amido group, C1 to C20 alkylsilyl group , A C1 to C20 alkoxy group, or a C1 to C20 sulfonate group;
R ₁₅ to R ₂₈ are the same as or different from each other, and are each independently hydrogen, halogen, C1 to C20 alkyl group, C1 to C20 haloalkyl group, C2 to C20 alkenyl group, C2 to C20 alkoxyalkyl group, C1 to C20 Alkylsilyl group, C1 to C20 silylalkyl group, C1 to C20 alkoxysilyl group, C1 to C20 alkoxy group, C6 to C20 aryl group, C7 to C20 alkylaryl group, or C7 to C20 arylalkyl group Provided that R ₂₀ and R ₂₄ are the same as or different from each other, and each independently an alkyl group of C1 to C20, or two or more adjacent to each other of R ₁₅ to R ₂₈ are connected to each other to be substituted or unsubstituted aliphatic or aromatic To form a ring,
Provided that at least one of Q ₃ , Q ₄ , R ₂₆ , and R ₂₇ is an alkoxyalkyl group of C 2 to C 20.
The method of claim 1,
Q ₁ and Q ₂ are the same as or different from each other, and are each independently an alkyl group of C1 to C20, or an aryl group of C6 to C20;
T ₁ is carbon, silicon, or germanium;
M ₁ is Ti, Zr, or Hf,
X ₁ and X ₂ are the same as or different from each other, and each independently a halogen or an alkyl group of C1 to C20,
R ₁ to R ₁₄ are the same as or different from each other, and each independently hydrogen, an alkyl group of C1 to C20, or an aryl group of C6 to C20,
Hybrid supported metallocene catalysts.
The method of claim 1,
R ₁ is hydrogen or an alkyl group of C1 to C20,
R ₂ to R ₁₀ are each hydrogen,
R ₁₁ to R ₁₄ are the same as or different from each other, and each independently hydrogen or an alkyl group of C1 to C20,
Hybrid supported metallocene catalysts.
The method of claim 1,
The first transition metal compound is any one of the compounds represented by the following structural formula,
Hybrid Supported Metallocene Catalysts:

,

,

,

,

,

,

,

.
The method of claim 1,
Q ₃ and Q ₄ are the same as or different from each other, and are each independently a C1 to C20 alkyl group or a C2 to C20 alkoxyalkyl group;
T ₂ is carbon, silicon, or germanium;
M ₂ is Ti, Zr, or Hf,
X ₃ and X ₄ are the same as or different from each other, and each independently a halogen or an alkyl group of C1 to C20,
R ₁₅ to R ₁₉ , R ₂₁ to R ₂₃ , and R ₂₅ to R ₂₈ are the same as or different from each other, and each independently hydrogen, an alkyl group of C1 to C20, an alkoxyalkyl group of C2 to C20, or an aryl group of C6 to C20 ego,
R ₂₀ and R ₂₄ are the same as or different from each other, and each independently hydrogen or an alkyl group of C1 to C20,
Hybrid supported metallocene catalysts.
The method of claim 1,
R ₁₅ to R ₁₉ and R ₂₁ to R ₂₃ are each hydrogen,
R ₂₀ and R ₂₄ are the same as or different from each other, and are each independently hydrogen or an alkyl group of C1 to C4,
R ₂₅ and R ₂₈ are each hydrogen,
R ₂₆ and R ₂₇ are the same as or different from each other, and are each independently hydrogen, an alkyl group of C1 to C20, or an alkoxyalkyl group of C2 to C20,
Hybrid supported metallocene catalysts.
The method of claim 1,
At least one of Q ₃ , Q ₄ , R ₂₆ , and R ₂₇ is an iso-propoxyethyl group, iso-propoxypropyl group, iso-propoxyhexyl group, tert-butoxyethyl group, tert-butoxypropyl group, Or a tert-butoxyhexyl group,
Hybrid supported metallocene catalysts.
The method of claim 1,
The second transition metal compound is any one of the compounds represented by the following structural formula,
Hybrid Supported Metallocene Catalysts:

,

,

,

.
The method of claim 1,
The carrier comprises any one or a mixture of two or more selected from the group consisting of silica, alumina, and magnesia,
Hybrid supported metallocene catalysts.
The method of claim 1,
Further comprising at least one cocatalyst selected from the group consisting of compounds represented by formulas (3) and (4),
Hybrid Supported Metallocene Catalysts:
[Formula 3]
R _a- [Al (R _b ) -O] _n -R _c
In Chemical Formula 3,
R _a , R _b , and R _c are the same as or different from each other, and are each independently hydrogen, halogen, a C1 to C20 hydrocarbyl group, or a C1 to C20 hydrocarbyl group substituted with halogen;
n is an integer of at least 2;
[Formula 4]
T ⁺ [BG ₄ ] ^-
In Chemical Formula 4,
T ⁺ is a + monovalent polyatomic ion, B is boron in +3 oxidation state, G is independently a hydride group, a dialkylamido group, a halide group, an alkoxide group, an aryl oxide group, a hydrocarbyl group, a halo A carbyl group and a halo-substituted hydrocarbyl group,
G has up to 20 carbons, but at less than one position G is a halide group.
A process for producing an olefin polymer, comprising the step of polymerizing the olefin monomer in the presence of the hybrid supported metallocene catalyst according to claim 1.
The method of claim 11,
The olefin monomer is 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-aitocene, norbornene, norbornadiene, ethylidene nobodene, phenyl nobodene, vinyl nobodene, dicyclopentadiene, 1,4-butadiene, 1,5 At least one member selected from the group consisting of -pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene and 3-chloromethylstyrene,
Process for producing olefin polymer.

Images